Lithium (N-carbonyl)sulfonamide compound, additive for lithium secondary battery, non-aqueous electrolyte for lithium secondary battery, lithium secondary battery precursor, lithium secondary battery, and method for producing lithium secondary battery

Abstract

The lithium (N-carbonyl) sulfonamide compound is represented by the following formula (I). In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group. 1 and L 2 Each represents a single bond or -O-. Among them, excluding L 1 and L 2 Each is a single bond.

Description

Technical Field

[0001] The present disclosure relates to a lithium (N-carbonyl)sulfonamide compound, an additive for a lithium secondary battery, a non-aqueous electrolyte for a lithium secondary battery, a lithium secondary battery precursor, a lithium secondary battery, and a method for producing a lithium secondary battery. Background Art

[0002] Lithium secondary batteries have attracted attention as high-energy-density batteries.

[0003] Patent Document 1 discloses a compound used as a salt in an electrolyte composition. The compound specifically disclosed in Patent Document 1 is lithium trifluoromethylcarbonyltrifluoromethylsulfonamide.

[0004] Patent Document 1: Japanese Patent Application No. 2020-515558 Summary of the Invention

[0005] Problems to be solved by the invention

[0006] However, in a lithium secondary battery obtained by adding lithium trifluoromethylcarbonyltrifluoromethylsulfonamide disclosed in Patent Document 1 to a non-aqueous solvent, there is a concern that DC resistance may increase and discharge capacity may decrease when charging or discharging is performed in a high-temperature environment.

[0007] In view of the above situation, the present disclosure aims to provide a lithium (N-carbonyl) sulfonamide compound, an additive for a lithium secondary battery, a non-aqueous electrolyte for a lithium secondary battery, a lithium secondary battery precursor, a lithium secondary battery, and a method for manufacturing a lithium secondary battery, which can suppress an increase in DC resistance and a decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment.

[0008] Means for solving problems

[0009] Means for solving the above-mentioned problems include the following embodiments.

[0010] <1> A lithium (N-carbonyl)sulfonamide compound represented by the following formula (I).

[0011] [Chemical Formula 1]

[0012]

[0013] [In formula (I),

[0014] R 1 and R 2Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).

[0015] L 1 and L 2 Each represents a single bond or -O-. 1 and L 2 Each is a single bond. ]

[0016] <2> An additive for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I).

[0017] [Chemical Formula 2]

[0018]

[0019] [In formula (I),

[0020] R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom. However, trifluoromethyl group is excluded.), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom.), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom.), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.).

[0021] L 1 and L 2 Each represents a single bond or -O-.]

[0022] <3> As mentioned above <2> The additive for lithium secondary battery, wherein the aforementioned R 1 And the aforementioned R 2 Each of the above-mentioned alkyl, alkenyl, alkynyl, or aryl groups is replaced by an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the above-mentioned alkyl group may be substituted with a halogen atom), the above-mentioned alkenyl, alkynyl, aryl, an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above-mentioned aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom,

[0023] Exclude R 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0024] <4> A non-aqueous electrolyte for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I).

[0025] [Chemical Formula 3]

[0026]

[0027] [In formula (I),

[0028] R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom. However, trifluoromethyl group is excluded.), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom.), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom.), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.).

[0029] L 1 and L 2 Each represents a single bond or -O-.]

[0030] <5> As mentioned above <4> The non-aqueous electrolyte for lithium secondary battery, wherein the aforementioned R 1 And the aforementioned R 2 Each of the above-mentioned alkyl, alkenyl, alkynyl, or aryl groups is replaced by an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the above-mentioned alkyl group may be substituted with a halogen atom), the above-mentioned alkenyl, alkynyl, aryl, an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above-mentioned aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom,

[0031] Exclude R 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0032] <6> As mentioned above <4> or <5> The non-aqueous electrolyte for lithium secondary batteries further contains an electrolyte,

[0033] The aforementioned electrolyte is at least one selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium hexafluorotantalate (LiTaF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N).

[0034] <7> As mentioned above <4> ~ <6> The non-aqueous electrolyte for lithium secondary batteries according to any one of the preceding claims, wherein the lithium (N-carbonyl)sulfonamide compound (I)

[0035] The aforementioned R 1 represents the aforementioned aryl group,

[0036] The aforementioned L 1 represents a single bond,

[0037] The aforementioned R 2 represents the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned alkynyl group, the aforementioned aryl group, or the aforementioned aralkyl group,

[0038] The aforementioned L 2 Indicates -O-.

[0039] <8> As mentioned above <4> ~ <6> The non-aqueous electrolyte for lithium secondary batteries according to any one of the preceding claims, wherein the lithium (N-carbonyl)sulfonamide compound (I)

[0040] The aforementioned R 1 represents the aforementioned alkyl group,

[0041] The aforementioned L 1 represents a single bond,

[0042] The aforementioned R 2 represents the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned alkynyl group, the aforementioned aryl group, or the aforementioned aralkyl group,

[0043] The aforementioned L 2 Indicates -O-.

[0044] <9> As mentioned above <4> ~ <6> The non-aqueous electrolyte for lithium secondary batteries according to any one of the preceding claims, wherein the lithium (N-carbonyl)sulfonamide compound (I)

[0045] The aforementioned R 1 represents a fluorine atom,

[0046] The aforementioned L 1 represents a single bond,

[0047] The aforementioned R 2 represents the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned alkynyl group, the aforementioned aryl group, or the aforementioned aralkyl group,

[0048] The aforementioned L 2 Indicates -O-.

[0049] <10> As mentioned above <4> ~ <9> The non-aqueous electrolyte for a lithium secondary battery according to any one of the preceding claims comprises a compound (II) which is at least one selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate.

[0050] <11> As mentioned above <4> ~ <10> The non-aqueous electrolyte solution for a lithium secondary battery described in any one of the preceding claims contains a compound (III) represented by the following formula (III).

[0051] [Chemical Formula 4]

[0052]

[0053] [In formula (III),

[0054] M is an alkali metal,

[0055] Y is a transition element, a Group 13 element, a Group 14 element, or a Group 15 element of the periodic table,

[0056] b is an integer from 1 to 3,

[0057] m is an integer from 1 to 4,

[0058] n is an integer from 0 to 8,

[0059] q is 0 or 1,

[0060] R 3 is an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure, and when q is 1 and m is 2 to 4, m R 3 Each can be bonded. ),

[0061] R 4is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure, and when n is 2 to 8, n R 4 Each may be bonded to form a ring. ),

[0062] Q 1 and Q 2 are each independently an oxygen atom or a carbon atom.]

[0063] <12> As mentioned above <4> ~ <11> The non-aqueous electrolyte solution for a lithium secondary battery described in any one of the preceding claims contains a compound (IV) represented by the following formula (IV).

[0064] [Chemical Formula 5]

[0065]

[0066] [In formula (IV),

[0067] R 5 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms,

[0068] R 6 is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a group represented by formula (iv-1), or a group represented by formula (iv-2),

[0069] * indicates the bonding position,

[0070] In formula (iv-1), R 61 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an oxymethylene group,

[0071] In formula (iv-2), R 62 It is an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.

[0072] <13> As mentioned above <4> ~ <12> The non-aqueous electrolyte for lithium secondary batteries described in any one of the preceding claims, wherein the content of the lithium (N-carbonyl)sulfonamide compound (I) is 0.01% by mass or more and 5% by mass or less based on the total amount of the non-aqueous electrolyte for lithium secondary batteries.

[0073] <14> A lithium secondary battery precursor comprising:

[0074] housing, and

[0075] The positive electrode, negative electrode, separator, and electrolyte contained in the housing;

[0076] The positive electrode is a positive electrode that can absorb and release lithium ions.

[0077] The aforementioned negative electrode is a negative electrode that can absorb and release lithium ions.

[0078] The aforementioned electrolyte is the aforementioned <4> ~ <13> The non-aqueous electrolyte solution for lithium secondary batteries described above.

[0079] <15> As mentioned above <14> In the lithium secondary battery precursor, the positive electrode comprises a lithium-containing composite oxide represented by the following formula (C1) as a positive electrode active material.

[0080] LiNi a Co b Mn c O2…Formula (C1)

[0081] [In formula (C1), a, b, and c are each independently greater than 0 and less than 1, and the total of a, b, and c is greater than or equal to 0.99 and less than or equal to 1.00.]

[0082] <16> A method for manufacturing a lithium secondary battery, comprising the following steps:

[0083] Prepare the above <14> or <15> The lithium secondary battery precursor process, and

[0084] The lithium secondary battery precursor is subjected to charging and discharging steps.

[0085] <17> Lithium secondary battery, which is the aforementioned <14> or <15> The lithium secondary battery precursor is obtained by charging and discharging.

[0086] Effects of the Invention

[0087] According to the present disclosure, a lithium (N-carbonyl) sulfonamide compound, an additive for a lithium secondary battery, a non-aqueous electrolyte for a lithium secondary battery, a lithium secondary battery precursor, a lithium secondary battery, and a method for manufacturing a lithium secondary battery can be provided, which can suppress an increase in DC resistance and a decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] [ Figure 1 ] is a schematic cross-sectional view showing a laminated battery as an example of a precursor of a lithium secondary battery of the present disclosure.

[0089] [ Figure 2 ] is a schematic cross-sectional view showing a button-type battery as another example of a lithium secondary battery precursor of the present disclosure. DETAILED DESCRIPTION

[0090] In this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0091] In this specification, when the composition contains a plurality of substances belonging to each component, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified.

[0092] In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0093] Hereinafter, embodiments of the lithium (N-carbonyl)sulfonamide compound, lithium secondary battery additive, lithium secondary battery non-aqueous electrolyte, lithium secondary battery precursor, lithium secondary battery, and lithium secondary battery manufacturing method according to the present disclosure will be described with reference to the accompanying drawings. In the drawings, identical or corresponding parts are denoted by the same reference numerals and description thereof will not be repeated.

[0094] [Lithium (N-carbonyl) sulfonamide compounds]

[0095] (Compound (A))

[0096] The lithium (N-carbonyl)sulfonamide compound of the present disclosure is described.

[0097] The lithium (N-carbonyl)sulfonamide compound of the present disclosure is a novel compound represented by the following formula (I) (hereinafter, sometimes referred to as "compound (A)").

[0098] [Chemical Formula 6]

[0099]

[0100] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).

[0101] L 1 and L 2 Each represents a single bond or an ether bond (-O-). 1 and L 2 Each is a single bond.

[0102] The lithium (N-carbonyl)sulfonamide compound (i.e., compound (A)) of the present disclosure is represented by the above-mentioned formula (I). Therefore, when added to a non-aqueous electrolyte for a lithium secondary battery (hereinafter sometimes referred to as "non-aqueous electrolyte") and used, it is possible to suppress an increase in DC resistance and a decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment.

[0103] For details about lithium secondary batteries, refer to Figure 1 and Figure 2 And it will be described in the following text.

[0104] The reason why the above-mentioned effects are achieved can be presumed as follows.

[0105] It is believed that when a lithium secondary battery is manufactured using a non-aqueous electrolyte solution to which the lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) of the present disclosure is added, a reaction product is generated near the surface of the negative electrode of the lithium secondary battery during its manufacturing process (e.g., the aging process described later), and a component of the decomposition product of the reaction product is generated. The reaction product refers to a product obtained by the reaction of the lithium (N-carbonyl) sulfonamide compound with a compound (e.g., LiF) generated by the electrolyte. Such reaction products, etc., adhere to the surface of the negative electrode to form an SEI (Solid Electrolyte Interphase) film (hereinafter referred to as the "negative electrode SEI film."). It is believed that this component moves to the vicinity of the positive electrode surface during the manufacturing process, adheres to the positive electrode surface to form an SEI film (hereinafter referred to as the "positive electrode SEI film."). As a result, the stability of the lithium secondary battery in a high temperature environment can be improved. For example, the dissolution of the metal element in the positive electrode active material is suppressed. It is believed that as a result, even if the lithium secondary battery is stored in a high temperature environment, the increase in the DC resistance of the lithium secondary battery is suppressed.

[0106] The formation of the positive electrode SEI film is thought to continue during the storage period of the lithium secondary battery. Therefore, the rate of increase in the DC resistance of the lithium secondary battery relative to the storage period is thought to be reduced during the storage of the lithium secondary battery.

[0107] In addition, as mentioned above, the stability of the lithium secondary battery using the lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) of the present disclosure is excellent even in a high temperature environment. That is, it is believed that even if the lithium secondary battery is stored in a high temperature environment, side reactions that are not the original battery reaction are not easy to proceed. Battery reaction refers to the reaction of lithium ions entering and exiting (embedding) in the positive electrode and the negative electrode. Side reactions include the reduction decomposition reaction of the electrolyte caused by the negative electrode, the oxidation decomposition reaction of the electrolyte caused by the positive electrode, the dissolution of metal elements in the positive electrode active material, etc. As a result, the decomposition reaction of the non-aqueous electrolyte is suppressed. It is believed that as a result, even if the lithium secondary battery is stored in a high temperature environment, the discharge capacity of the lithium secondary battery is not easy to decrease.

[0108] For the above reasons, if the lithium (N-carbonyl)sulfonamide compound of the present disclosure (i.e., compound (A)) is added to a non-aqueous electrolyte and used, the increase in DC resistance and the decrease in discharge capacity of the lithium secondary battery can be suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0109] Hereinafter, when the negative electrode SEI film and the positive electrode SEI film are not distinguished from each other, they are simply referred to as “SEI film”.

[0110] In formula (I), R 1 and R 2 The "alkyl group having 1 to 10 carbon atoms" referred to in each example is a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of the "alkyl group having 1 to 10 carbon atoms" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 1-methylpentyl, neopentyl, 1-ethylpropyl, hexyl, 3,3-dimethylbutyl, heptyl, octyl, nonyl, and decyl. Among these, the "alkyl group having 1 to 10 carbon atoms" is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0111] At least one hydrogen atom in the "alkyl group having 1 to 10 carbon atoms" may be substituted with a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

[0112] In the "alkyl group having 1 to 10 carbon atoms", the number of hydrogen atoms substituted by halogen atoms is not particularly limited and can be appropriately selected depending on the number of carbon atoms in the alkyl group, but is preferably 1 to 7.

[0113] In formula (I), R 1 and R 2The "alkenyl group having 2 to 10 carbon atoms" represented in each case is a straight-chain or branched alkenyl group having 2 to 10 carbon atoms. Examples of the "alkenyl group having 2 to 10 carbon atoms" include vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, and 5-hexenyl. Among these, the "alkenyl group having 2 to 10 carbon atoms" is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 to 3 carbon atoms.

[0114] At least one hydrogen atom of the "alkenyl group having 2 to 10 carbon atoms" may be substituted with a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

[0115] In the "alkenyl group having 2 to 10 carbon atoms", the number of hydrogen atoms substituted by halogen atoms is not particularly limited and can be appropriately selected depending on the number of carbon atoms in the alkenyl group, but is preferably 1 to 7.

[0116] In formula (I), R 1 and R 2 The "alkynyl group having 2 to 10 carbon atoms" represented in each case is a straight-chain or branched alkynyl group having 2 to 10 carbon atoms. Examples of the "alkynyl group having 2 to 10 carbon atoms" include ethynyl, propargyl (2-propynyl), 2-butynyl, 3-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, and 5-hexynyl. Among these, the "alkynyl group having 2 to 10 carbon atoms" is preferably an alkynyl group having 2 to 6 carbon atoms, and more preferably an alkynyl group having 2 to 3 carbon atoms.

[0117] At least one hydrogen atom in the "alkynyl group having 2 to 10 carbon atoms" may be substituted with a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

[0118] In the "alkynyl group having 2 to 10 carbon atoms", the number of hydrogen atoms substituted by halogen atoms is not particularly limited and can be appropriately selected depending on the number of carbon atoms in the alkynyl group, but is preferably 1 to 7.

[0119] In formula (I), for R 1 and R 2 At least one hydrogen atom of the "aryl" represented by each may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.

[0120] The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. In the "aryl group", the number of hydrogen atoms substituted by a halogen atom is not particularly limited, but is preferably 1 to 5.

[0121] The alkyl group of the alkoxy group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and pentyloxy. Among these, the alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group and an ethoxy group. In the "aryl group", the number of hydrogen atoms substituted by the alkoxy group having 1 to 6 carbon atoms is not particularly limited, but is preferably 1 to 3.

[0122] The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl. Among these, the alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. In the "aryl group", the number of hydrogen atoms substituted by the alkyl group having 1 to 6 carbon atoms is not particularly limited, but is preferably 1 to 3.

[0123] In formula (I), L 1 and L 2 Each represents a single bond or -O-. 1 and L 2 In other words, excluding L 1 is a single bond and L 2 For a single bond. 1 Preferably represents a single bond, L 2 Preferably it represents -O-.

[0124] Specific examples of lithium (N-carbonyl)sulfonamide compounds (ie, compound (A)) include synthetic compounds (I-1) to (I-41) synthesized in the examples described below (excluding synthetic compound (I-9)).

[0125] (Compound (B))

[0126] The lithium (N-carbonyl) sulfonamide compound of the present disclosure may also be the following lithium (N-carbonyl) sulfonamide compound,

[0127] In the above-mentioned lithium (N-carbonyl) sulfonamide compound (ie, compound (A)),

[0128] The aforementioned R 1And the aforementioned R 2 Each of the above-mentioned alkyl, alkenyl, alkynyl, or aryl groups is replaced by the above-mentioned alkyl, alkenyl, alkynyl, aryl, aralkyl having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above-mentioned aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom,

[0129] Instead of excluding L 1 and L 2 When each is a single bond,

[0130] Excluding R 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L2 are each a single bond.

[0131] In other words, the lithium (N-carbonyl)sulfonamide compound of the present disclosure may be a novel compound represented by the following formula (I) (hereinafter, sometimes referred to as "compound (B)").

[0132] [Chemical Formula 7]

[0133]

[0134] In formula (I), R 1 and R 2 Each of them represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom), an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the aforementioned aralkyl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom.

[0135] L 1 and L 2 Each represents a single bond or -O-. 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0136] When the lithium (N-carbonyl)sulfonamide compound of the present disclosure (ie, compound (B)) is added to a non-aqueous electrolyte solution, the increase in DC resistance and the decrease in discharge capacity can be suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0137] The reason for the above effect is presumably the same as the reason why, when compound (A) is added to a non-aqueous electrolyte, an increase in DC resistance and a decrease in discharge capacity can be suppressed even when a lithium secondary battery is stored in a high-temperature environment.

[0138] In compound (B), in formula (I), R 1 and R 2 The "alkyl group having 1 to 10 carbon atoms" represented by each is the same as the alkyl group exemplified as the "alkyl group having 1 to 10 carbon atoms" in compound (A).

[0139] In compound (B), in formula (I), R 1 and R 2 The "alkenyl group having 2 to 10 carbon atoms" represented by each is the same as the alkenyl group exemplified as the "alkenyl group having 2 to 10 carbon atoms" in compound (A).

[0140] In compound (B), in formula (I), R 1 and R 2 The "alkynyl group having 2 to 10 carbon atoms" represented by each is the same as the alkynyl group exemplified as the "alkynyl group having 2 to 10 carbon atoms" in compound (A).

[0141] In compound (B), in formula (I), R 1 and R 2 The "aryl group" represented by each is the same as the aryl group exemplified as the "aryl group" in compound (A).

[0142] In compound (B), in formula (I), R 1 and R 2 The "aralkyl group having 7 to 16 carbon atoms" referred to herein is an aralkyl group having 7 to 16 carbon atoms and including an aryl group. At least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.

[0143] The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. In the "aralkyl group", the number of hydrogen atoms substituted by a halogen atom is not particularly limited, but is preferably 1 to 5.

[0144] The alkyl group of the alkoxy group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and pentyloxy. Among these, the alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group and an ethoxy group. In the "aralkyl" group, the number of hydrogen atoms substituted by the alkoxy group having 1 to 6 carbon atoms is not particularly limited, but is preferably 1 to 3.

[0145] The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl. Among these, the alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. In the "aralkyl group," the number of hydrogen atoms substituted by the alkyl group having 1 to 6 carbon atoms is not particularly limited, but is preferably 1 to 3.

[0146] The aralkyl group having 7 to 16 carbon atoms is preferably an aralkyl group containing an aryl group substituted with an alkylene group having 1 to 6 carbon atoms. The aryl group substituted with an alkylene group having 1 to 6 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.

[0147] Specific examples of the "aralkyl group having 7 to 16 carbon atoms" include benzyl, phenylethyl, and naphthylmethyl.

[0148] In compound (B), in formula (I), as R 1 and R 2 The "halogen atom" represented by each is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, further preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

[0149] In formula (I), L 1 and L 2 Each represents a single bond or -O-. 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0150] Among them, L 1 Preferably represents a single bond, L 2 Preferably it represents -O-.

[0151] Specific examples of the lithium (N-carbonyl)sulfonamide compound (ie, compound (B)) include synthetic compounds (I-1) to (I-48) synthesized in the examples described below.

[0152] [Additives for lithium secondary batteries]

[0153] (Additive (A))

[0154] The additive for lithium secondary batteries of the present disclosure (hereinafter, sometimes simply referred to as “additive”) will be described.

[0155] The additive of the present disclosure contains a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I) (hereinafter, sometimes referred to as "compound (C)").

[0156] [Chemical Formula 8]

[0157]

[0158] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom. However, trifluoromethyl group is excluded.), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom.), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom.), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.).

[0159] L 1 and L 2 Each represents a single bond or -O-.

[0160] In the present disclosure, "excluding trifluoromethyl" in the alkyl group having 1 to 10 carbon atoms means excluding R 1 For trifluoromethyl, L 1 is a single bond, R 2 is trifluoromethyl, and L 2 For the case of a single bond.

[0161] Hereinafter, the additive containing the compound (C) may be referred to as "additive (A)".

[0162] The additive (A) of the present disclosure contains a lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (C)). Therefore, when added to a non-aqueous electrolyte and used, it is possible to suppress an increase in DC resistance and a decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment.

[0163] The reason for achieving the above effect is presumably the same as the reason why, when the lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (A)) of the present disclosure is added to a non-aqueous electrolyte and used, the increase in DC resistance and the decrease in discharge capacity of the lithium secondary battery can be suppressed even when the battery is stored in a high-temperature environment.

[0164] The additive (A) of the present disclosure is suitable as an additive for a non-aqueous electrolyte solution of a lithium secondary battery.

[0165] As R 1 、R 2 , L 1 , and L 2 , except from R 1 and R 2 Excluding the trifluoromethyl group, L 1 and L 2 In addition to the fact that each may be a single bond, examples include the above-mentioned lithium (N-carbonyl) sulfonamide compound (ie, compound (A)) and R 1 、R 2 , L 1 , and L 2 The groups exemplified are the same groups.

[0166] (Additive (B))

[0167] The additives of the present disclosure may also be the following additives for lithium secondary batteries:

[0168] Among the above-mentioned additives for lithium secondary batteries (ie, additive (A)),

[0169] The aforementioned R 1 And the aforementioned R 2 Each of the above-mentioned alkyl, alkenyl, alkynyl, or aryl groups is replaced by an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the above-mentioned alkyl group may be substituted with a halogen atom), the above-mentioned alkenyl, alkynyl, aryl, an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above-mentioned aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom,

[0170] Exclude R1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0171] In other words, the lithium secondary battery additive of the present disclosure may be an additive containing a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I) (ie, compound (B)) (hereinafter sometimes referred to as "additive (B)").

[0172] [Chemical Formula 9]

[0173]

[0174] In formula (I), R 1 and R 2 Each of them represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom), an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the aforementioned aralkyl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom.

[0175] L 1 and L 2 Each represents a single bond or -O-. 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0176] The additive (B) of the present disclosure contains a lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)). Therefore, when added to a non-aqueous electrolyte and used, it is possible to suppress an increase in DC resistance and a decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment.

[0177] The reason for the above effect is presumably the same as the reason why, when the additive (A) is added to a non-aqueous electrolyte, an increase in DC resistance and a decrease in discharge capacity can be suppressed even when a lithium secondary battery is stored in a high-temperature environment.

[0178] The additive (B) of the present disclosure is suitable as an additive for a non-aqueous electrolyte solution of a lithium secondary battery.

[0179] The lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)) contained in the additive (B) of the present disclosure may be the same compounds as those exemplified as the above-mentioned lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)).

[0180] [Non-aqueous electrolyte for lithium secondary batteries]

[0181] (Non-aqueous electrolyte (A))

[0182] The non-aqueous electrolyte solution for lithium secondary batteries of the present disclosure will be described.

[0183] The non-aqueous electrolyte of the present disclosure can be used as an electrolyte for lithium secondary batteries.

[0184] The non-aqueous electrolyte of the present disclosure contains a lithium (N-carbonyl)sulfonamide compound (I) (ie, compound (C)) represented by the following formula (I).

[0185] [Chemical Formula 10]

[0186]

[0187] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom. However, trifluoromethyl group is excluded.), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom.), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom.), or an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.).

[0188] L 1 and L 2 Each represents a single bond or -O-.

[0189] In the present disclosure, "wherein, excluding trifluoromethyl" means: excluding R from formula (I) 1 For trifluoromethyl, L 1 is a single bond, R 2 is trifluoromethyl, and L 2 For the case of a single bond.

[0190] Hereinafter, the nonaqueous electrolyte solution containing the compound (C) may be referred to as "nonaqueous electrolyte solution (A)".

[0191] The nonaqueous electrolyte solution (A) of the present disclosure contains the lithium (N-carbonyl)sulfonamide compound (I) (ie, compound (C)). Therefore, even when the lithium secondary battery is stored in a high-temperature environment, an increase in DC resistance and a decrease in discharge capacity can be suppressed.

[0192] The reason for achieving the above effect is presumably the same as the reason why, when the lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (A)) of the present disclosure is added to a non-aqueous electrolyte and used, the increase in DC resistance and the decrease in discharge capacity of the lithium secondary battery can be suppressed even when the battery is stored in a high-temperature environment.

[0193] The lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (C)) contained in the non-aqueous electrolyte (A) of the present disclosure may be the same compounds as those exemplified as the lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (C)) contained in the additive (A) of the present disclosure.

[0194] (Non-aqueous electrolyte (B))

[0195] The non-aqueous electrolyte of the present disclosure may also be the following non-aqueous electrolyte for lithium secondary batteries:

[0196] In the above-mentioned non-aqueous electrolyte solution for lithium secondary batteries (ie, non-aqueous electrolyte solution (A)),

[0197] The aforementioned R 1 And the aforementioned R 2 Each of the above-mentioned alkyl, alkenyl, alkynyl, or aryl groups is replaced by an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the above-mentioned alkyl group may be substituted with a halogen atom), the above-mentioned alkenyl, alkynyl, aryl, an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above-mentioned aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom,

[0198] Exclude R 1 is a halogen atom and L 1 In the case of -O-, R2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0199] In other words, the non-aqueous electrolyte of the present disclosure may also be an additive (hereinafter sometimes referred to as "non-aqueous electrolyte (B)") containing a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I) (i.e., "compound (B)").

[0200] [Chemical Formula 11]

[0201]

[0202] In formula (I), R 1 and R 2 Each of them represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkyl group may be substituted by a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkenyl group may be substituted by a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the aforementioned alkynyl group may be substituted by a halogen atom), an aryl group (at least one hydrogen atom of the aforementioned aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the aforementioned aralkyl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or a halogen atom.

[0203] L 1 and L 2 Each represents a single bond or -O-. 1 is a halogen atom and L 1 In the case of -O-, R 2 is a halogen atom and L 2 For -O-, and R 1 and R 2 Each is the aforementioned alkyl group or the aforementioned aryl group and L 1 and L 2 Each is a single bond.

[0204] The nonaqueous electrolyte solution (B) of the present disclosure can suppress an increase in DC resistance and a decrease in discharge capacity even when a lithium secondary battery is stored in a high-temperature environment.

[0205] The reason for the above effect is presumably the same as the reason why, when the non-aqueous electrolyte (A) is added to the non-aqueous electrolyte, the increase in DC resistance and the decrease in discharge capacity can be suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0206] The lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)) contained in the non-aqueous electrolyte (B) of the present disclosure may be the same compounds as those exemplified as the lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)) described above.

[0207] Hereinafter, compound (C) or compound (B) is simply referred to as "lithium (N-carbonyl)sulfonamide compound (I)".

[0208] Hereinafter, the additive (A) or the additive (B) is simply referred to as "additive".

[0209] Hereinafter, the non-aqueous electrolyte solution (A) or the non-aqueous electrolyte solution (B) will be simply referred to as the "non-aqueous electrolyte solution".

[0210] (Compounds containing an aromatic group)

[0211] The lithium (N-carbonyl)sulfonamide compound (I) is preferably a compound containing an aryl group.

[0212] By using a compound containing an aryl group as the non-aqueous electrolyte of the present disclosure, an increase in DC resistance and a decrease in discharge capacity can be further suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0213] The compound containing an aryl group is represented by formula (I),

[0214] R 1 represents an aryl group (at least one hydrogen atom of the aryl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms),

[0215] L 1 represents a single bond,

[0216] R 2 represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkenyl group may be substituted with a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkynyl group may be substituted with a halogen atom), an aryl group (at least one hydrogen atom of the aryl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).

[0217] L 2 Indicates -O-.

[0218] Specific examples of compounds containing aromatic groups include synthetic compounds (I-1) to (I-9), synthetic compound (I-24), synthetic compound (I-25), synthetic compound (I-30) to (I-32), synthetic compound (I-38) to (I-40), synthetic compound (I-47), and synthetic compound (I-48), etc., which are synthesized in the examples described later.

[0219] (Compounds containing an alkyl group)

[0220] The lithium (N-carbonyl)sulfonamide compound (I) is preferably a compound containing an alkyl group.

[0221] By using an alkyl group-containing compound as the non-aqueous electrolyte of the present disclosure, an increase in DC resistance and a decrease in discharge capacity can be further suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0222] The compound containing an alkyl group is represented by formula (I),

[0223] R 1 represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the alkyl group may be substituted by a halogen atom),

[0224] L 1 represents a single bond,

[0225] R 2 represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkenyl group may be substituted with a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkynyl group may be substituted with a halogen atom), an aryl group (at least one hydrogen atom of the aryl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).

[0226] L 2 Indicates -O-.

[0227] Specific examples of compounds containing alkyl groups include synthetic compounds (I-10) to (I-23), synthetic compounds (I-26) to (I-29), synthetic compounds (I-33) to (I-37), and synthetic compound (I-41), which are synthesized in the examples described later.

[0228] (Compounds containing fluorine atoms)

[0229] The lithium (N-carbonyl)sulfonamide compound (I) is preferably a compound containing a fluorine atom.

[0230] By including a fluorine-containing compound in the non-aqueous electrolyte of the present disclosure, an increase in DC resistance and a decrease in discharge capacity can be further suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0231] The compound containing a fluorine atom is represented by formula (I),

[0232] R 1 represents a fluorine atom,

[0233] L 1 represents a single bond,

[0234] R 2 represents an alkyl group having 1 to 10 carbon atoms (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), an alkenyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkenyl group may be substituted with a halogen atom), an alkynyl group having 2 to 10 carbon atoms (at least one hydrogen atom of the alkynyl group may be substituted with a halogen atom), an aryl group (at least one hydrogen atom of the aryl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms), or an aralkyl group having 7 to 16 carbon atoms (at least one hydrogen atom of the aromatic ring in the above aralkyl group may be substituted with a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms).

[0235] L 2 Indicates -O-.

[0236] Specific examples of the fluorine atom-containing compound include Synthetic Compound (I-42) to Synthetic Compound (I-46) synthesized in the Examples described below.

[0237] From the viewpoint of further improving the dissociation property of the electrolyte and the mobility of ions, the intrinsic viscosity of the non-aqueous electrolyte is preferably 10.0 mPa·s or less at 25°C.

[0238] It should be noted that when analyzing the non-aqueous electrolyte solution collected from a disassembled lithium secondary battery, the amount of lithium (N-carbonyl)sulfonamide compound (I) may be less than the amount added to the non-aqueous electrolyte solution. Even in this case, as long as even a small amount of lithium (N-carbonyl)sulfonamide compound (I) is detected in the non-aqueous electrolyte solution extracted from the lithium secondary battery, the electrolyte solution of the lithium secondary battery is included in the scope of the non-aqueous electrolyte solution of the present disclosure.

[0239] The content of the lithium (N-carbonyl)sulfonamide compound (I) is preferably 0.01% by mass to 5.0% by mass, more preferably 0.05% by mass to 3.0% by mass, further preferably 0.10% by mass to 1.5% by mass, and particularly preferably 0.20% by mass to 1.5% by mass, relative to the total amount of the non-aqueous electrolyte.

[0240] If the content of the lithium (N-carbonyl)sulfonamide compound (I) is within the above range, the lithium secondary battery can operate without impairing the conductivity of lithium cations in the SEI film. In addition, as the SEI film contains a phosphoric acid structure, the battery characteristics of the lithium secondary battery are improved.

[0241] If the content of the lithium (N-carbonyl) sulfonamide compound (I) is within the above range, the SEI film contains a sufficient amount of structures derived from the lithium (N-carbonyl) sulfonamide compound (I). As a result, a thermally and chemically stable inorganic salt or polymer structure is easily formed. Therefore, at high temperatures, the dissolution of components of the SEI film that damage the durability of the SEI film and the denaturation of the SEI film are unlikely to occur. As a result, the durability of the SEI film and the characteristics of the lithium secondary battery after high-temperature storage are improved.

[0242] <Lithium Fluorophosphate Compound (II)>

[0243] The nonaqueous electrolyte of the present disclosure preferably contains at least one compound (II) selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate (hereinafter sometimes referred to as "lithium fluorophosphate compound (II)").

[0244] Lithium difluorophosphate is represented by the following formula (II-1), and lithium monofluorophosphate is represented by the following formula (II-2).

[0245] [Chemical Formula 12]

[0246]

[0247] By including a lithium fluorophosphate compound (II) in addition to a lithium (N-carbonyl)sulfonamide compound (I) in the non-aqueous electrolyte of the present disclosure, a decrease in discharge capacity and an increase in DC resistance of the lithium secondary battery can be further suppressed during charge and discharge cycles even after storage in a high-temperature environment.

[0248] When the non-aqueous electrolyte contains the lithium fluorophosphate compound (II), the content of the lithium fluorophosphate compound (II) is preferably 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and even more preferably 0.1% by mass to 2% by mass, relative to the total amount of the non-aqueous electrolyte.

[0249] When the content of the lithium fluorophosphate compound (II) is within the above range, the solubility of lithium fluorophosphate in the non-aqueous solvent can be ensured, and the DC resistance of the lithium secondary battery can be further reduced.

[0250] The non-aqueous electrolyte of the present disclosure preferably contains a compound (III) represented by the following formula (III) (hereinafter referred to as "cyclic dicarbonyl compound (III)").

[0251] [Chemical Formula 13]

[0252]

[0253] In formula (III),

[0254] M is an alkali metal,

[0255] Y is a transition element, a Group 13 element, a Group 14 element, or a Group 15 element of the periodic table,

[0256] b is an integer from 1 to 3,

[0257] m is an integer from 1 to 4,

[0258] n is an integer from 0 to 8,

[0259] q is 0 or 1,

[0260] R 3 is an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure, and when q is 1 and m is 2 to 4, m R 3 Each can be bonded. ),

[0261] R 4 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms (these groups may contain a substituent or a heteroatom in the structure, and when n is 2 to 8, n R 4 Each may be bonded to form a ring. ),

[0262] Q 1 and Q 2are each independently an oxygen atom or a carbon atom.

[0263] By including a cyclic dicarbonyl compound (III) in addition to the lithium (N-carbonyl)sulfonamide compound (I) in the non-aqueous electrolyte of the present disclosure, a decrease in discharge capacity and an increase in DC resistance of the lithium secondary battery can be further suppressed during charge and discharge cycles even after storage in a high-temperature environment.

[0264] This effect is presumably achieved based on the following reasons.

[0265] By making the non-aqueous electrolyte contain a cyclic dicarbonyl compound (III) in addition to the lithium (N-carbonyl) sulfonamide compound (I), the SEI film etc. will also contain a bond from the cyclic dicarbonyl compound (III) in addition to the above-mentioned reaction product etc. Thereby, it is easy to form a thermally stable and chemically stable inorganic salt or polymer structure. Therefore, at high temperatures, it is not easy to dissolve the components of the SEI film etc. that damage the durability of the SEI film etc., and denaturation of the SEI film etc. As a result, even in the charge and discharge cycle after long-term storage in a high temperature environment, the reduction in discharge capacity of the lithium secondary battery and the increase in DC resistance are further suppressed.

[0266] M is an alkali metal. Examples of the alkali metal include lithium, sodium, and potassium. Among them, M is preferably lithium.

[0267] Y is a transition element, a Group 13 element, a Group 14 element, or a Group 15 element of the periodic table. Y is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf, or Sb, and more preferably Al, B, or P. When Y is Al, B, or P, the synthesis of the anionic compound becomes relatively easy, and the production cost can be suppressed.

[0268] b represents the valence of the anion and the number of cations. b is an integer of 1 to 3, preferably 1. When b is 3 or less, the salt of the anionic compound is easily dissolved in the mixed organic solvent.

[0269] m and n are values ​​related to the number of ligands. m and n are determined by the type of M. m is an integer of 1 to 4. n is an integer of 0 to 8.

[0270] q is 0 or 1. When q is 0, the chelate ring becomes a five-membered ring, and when q is 1, the chelate ring becomes a six-membered ring.

[0271] R 3represents an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms. These alkylene groups, halogenated alkylene groups, arylene groups or halogenated arylene groups may contain substituents or heteroatoms in their structures. Specifically, substituents may be contained in place of the hydrogen atoms of these groups. Examples of substituents include halogen atoms, chain or cyclic alkyl groups, aryl groups, alkenyl groups, alkoxy groups, aryloxy groups, sulfonyl groups, amino groups, cyano groups, carbonyl groups, acyl groups, amide groups or hydroxyl groups. It may also be a structure in which nitrogen atoms, sulfur atoms or oxygen atoms are introduced in place of the carbon elements of these groups. When q is 1 and m is 2 to 4, the m R 3 As an example of such a ligand, there can be mentioned ethylenediaminetetraacetic acid.

[0272] R 4 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms. These alkyl groups, halogenated alkyl groups, aryl groups or halogenated aryl groups may be combined with R 3 Similarly, when the structure contains a substituent or a heteroatom, and n is 2 to 8, n R 4 Each of them may be bonded to form a ring. 4 , preferably an electron-withdrawing group, particularly preferably a fluorine atom.

[0273] Q 1 and Q 2 Each independently represents O or C. That is, the ligand is bonded to Y through these hetero atoms.

[0274] Specific examples of the cyclic dicarbonyl compound (III) include compounds represented by the following formulae (III-1) to (III-2).

[0275] Hereinafter, the compound represented by formula (III-1) may be referred to as "lithium bisoxalatoborate (III-1)".

[0276] [Chemical Formula 14]

[0277]

[0278] When the non-aqueous electrolyte contains the cyclic dicarbonyl compound (III), the content of the cyclic dicarbonyl compound (III) is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5.0% by mass, further preferably 0.10% by mass to 3.0% by mass, and particularly preferably 0.10% by mass to 2.0% by mass, relative to the total amount of the non-aqueous electrolyte.

[0279] When the content of the cyclic dicarbonyl compound (III) is within the above range, the lithium secondary battery can operate without impairing the conductivity of lithium cations in the SEI film, etc. In addition, as the SEI film, etc. contain a cyclic dicarbonyl structure, the battery characteristics of the lithium secondary battery are improved.

[0280] If the content of the cyclic dicarbonyl compound (III) is within the above range, the SEI film, etc., contains a sufficient amount of a structure primarily composed of a cyclic dicarbonyl structure. This facilitates the formation of a thermally and chemically stable inorganic salt or polymer structure. Therefore, at high temperatures, dissolution of components of the SEI film, etc., which could impair the durability of the SEI film, etc., and denaturation of the SEI film, etc., are less likely to occur. As a result, the durability of the SEI film, etc., and the properties of the lithium secondary battery after high-temperature storage are improved.

[0281] The non-aqueous electrolyte solution of the present disclosure preferably contains a compound (IV) represented by the following formula (IV) "(hereinafter referred to as "cyclic sulfur-containing ester compound (IV)")."

[0282] [Chemical Formula 15]

[0283]

[0284] In formula (IV),

[0285] R 5 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms,

[0286] R 6 is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a group represented by formula (iv-1), or a group represented by formula (iv-2),

[0287] * indicates the bonding position,

[0288] In formula (iv-1), R 61 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an oxymethylene group,

[0289] In formula (iv-2), R 62 It is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

[0290] By including a cyclic sulfur-containing ester compound (IV) in addition to a lithium (N-carbonyl)sulfonamide compound (I), the non-aqueous electrolyte of the present disclosure can suppress a decrease in discharge capacity and an increase in DC resistance of a lithium secondary battery even during long-term storage in a high-temperature environment.

[0291] This effect is presumably achieved based on the following reasons.

[0292] In the case of manufacturing a lithium secondary battery using the non-aqueous electrolyte of the present disclosure, in its manufacturing process (for example, an aging process described later), the reaction product includes a product obtained by reacting a cyclic sulfur-containing ester compound (IV) with a compound (for example, LiF) produced by an electrolyte. Thus, the stability of the lithium secondary battery in a high temperature environment can be further improved. It is believed that as a result, even if the lithium secondary battery is stored in a high temperature environment, the increase in the DC resistance of the lithium secondary battery is further suppressed. In addition, the decomposition reaction of the non-aqueous electrolyte is further suppressed. It is believed that as a result, even if the lithium secondary battery is stored in a high temperature environment, the discharge capacity of the lithium secondary battery is less likely to decrease.

[0293] In formula (IV), R 5 An alkylene group having 2 to 3 carbon atoms, a vinylene group, or an oxygen atom is preferred, a 1,3-propylene group, a vinylene group, or an oxygen atom is more preferred, and an oxygen atom is particularly preferred.

[0294] R of the cyclic sulfur-containing ester compound (IV) 5 Oxygen atoms are preferred. This facilitates the formation of a thermally and chemically stable inorganic salt structure. Therefore, at high temperatures, dissolution of components of the SEI film, which could impair the durability of the SEI film, and denaturation of the SEI film, are less likely to occur. As a result, the durability of the SEI film and the battery characteristics of the lithium secondary battery are improved.

[0295] In formula (IV), R 6 Preferred are groups represented by formula (iv-1) or groups represented by formula (iv-2).

[0296] In formula (iv-1), R 61 It is preferably an alkylene group having 1 to 3 carbon atoms, an alkenylene group having 1 to 3 carbon atoms, or an oxymethylene group, and more preferably an oxymethylene group.

[0297] In formula (iv-2), R 62 It is preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and more preferably a propyl group.

[0298] Specific examples of the cyclic sulfur-containing ester compound (IV) include compounds represented by formula (IV-1) and formulas (IV-1) to (IV-4).

[0299] Hereinafter, the compound represented by formula (IV-1) may be referred to as "cyclic sulfur-containing ester compound (IV-1)".

[0300] [Chemical Formula 16]

[0301]

[0302] The non-aqueous electrolyte solution may contain only one type of cyclic sulfur-containing ester compound (IV), or may contain two or more types of cyclic sulfur-containing ester compounds (IV).

[0303] When the non-aqueous electrolyte contains the cyclic sulfur-containing ester compound (IV), the content of the cyclic sulfur-containing ester compound (IV) is preferably 0.01% by mass to 5.0% by mass, more preferably 0.05% by mass to 3.0% by mass, and even more preferably 0.10% by mass to 2.0% by mass, relative to the total amount of the non-aqueous electrolyte.

[0304] When the content of the cyclic sulfur-containing ester compound (IV) is within the above range, the lithium secondary battery can operate without impairing the lithium ion conductivity of the SEI film, etc. In addition, as the SEI film, etc. contain the cyclic sulfur-containing ester structure, the battery characteristics of the lithium secondary battery are improved.

[0305] When the content of the cyclic sulfur-containing ester compound (IV) is within the above range, the SEI film, etc., contains a sufficient amount of the cyclic sulfur-containing ester structure. This facilitates the formation of a thermally and chemically stable inorganic salt or polymer structure. Therefore, at high temperatures, the dissolution of components of the SEI film, etc., which could impair the durability of the SEI film, etc., and the denaturation of the SEI film, etc., are less likely to occur. As a result, the durability of the SEI film, etc., and the battery characteristics of the lithium secondary battery are improved.

[0306] <Other additives>

[0307] The non-aqueous electrolyte of the present disclosure may also contain other additives.

[0308] There are no particular limitations on other additives, and any known additives can be used.

[0309] As other additives, for example, the additives described in paragraphs 0042 to 0055 of JP-A-2019-153443 can be used.

[0310] <Non-aqueous solvent>

[0311] The non-aqueous electrolyte generally contains a non-aqueous solvent. As the non-aqueous solvent, various known non-aqueous solvents can be appropriately selected. The non-aqueous solvent may be only one or two or more.

[0312] Examples of the non-aqueous solvent include cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, fluorine-containing chain carbonates, aliphatic carboxylates, fluorine-containing aliphatic carboxylates, γ-lactones, fluorine-containing γ-lactones, cyclic ethers, fluorine-containing cyclic ethers, chain ethers, fluorine-containing chain ethers, nitriles, amides, lactams, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, and dimethyl sulfoxide phosphoric acid.

[0313] Examples of the cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).

[0314] Examples of the fluorine-containing cyclic carbonates include fluoroethylene carbonate (FEC) and the like.

[0315] Examples of the chain carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), and dipropyl carbonate (DPC).

[0316] Examples of the aliphatic carboxylic acid esters include methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylbutyrate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl isobutyrate, and ethyl trimethylbutyrate.

[0317] Examples of the γ-lactones include γ-butyrolactone and γ-valerolactone.

[0318] Examples of the cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane.

[0319] Examples of the chain ethers include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, 1,2-dimethoxyethane, and 1,2-dibutoxyethane.

[0320] Examples of the nitriles include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile.

[0321] Examples of amides include N,N-dimethylformamide.

[0322] Examples of the lactams include N-methylpyrrolidone, N-methyloxazolidinone, and N,N′-dimethylimidazolidinone.

[0323] The nonaqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, and fluorine-containing chain carbonates.

[0324] In this case, relative to the total amount of the nonaqueous solvent, the total ratio of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, and fluorine-containing chain carbonates is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, further preferably 80% by mass or more and 100% by mass or less.

[0325] The nonaqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.

[0326] In this case, relative to the total amount of nonaqueous solvent, the total ratio shared by cyclic carbonates and linear carbonates in nonaqueous solvent is preferably more than 50 mass % and less than 100 mass %, more preferably more than 60 mass % and less than 100 mass %, further preferably more than 80 mass % and less than 100 mass %.

[0327] The content of the nonaqueous solvent is preferably 60% to 99% by mass, more preferably 70% to 97% by mass, and even more preferably 70% to 90% by mass, based on the total amount of the nonaqueous electrolyte.

[0328] From the viewpoint of further improving the dissociation property of the electrolyte and the mobility of ions, the intrinsic viscosity of the nonaqueous solvent is preferably 10.0 mPa·s or less at 25°C.

[0329] <Electrolyte>

[0330] The non-aqueous electrolyte generally contains an electrolyte.

[0331] The term "electrolyte" for lithium secondary batteries refers to the substance that carries the electrolyte between the positive and negative electrodes. Electrolytes are highly soluble in non-aqueous solvents and exhibit a high degree of dissociation in these solvents. In most cases, lithium salts are used as electrolytes.

[0332] The electrolyte preferably contains at least one of a lithium salt containing fluorine (hereinafter sometimes referred to as a “fluorine-containing lithium salt”) and a lithium salt not containing fluorine.

[0333] Examples of the fluorine-containing lithium salt include inorganic acid anion salts and organic acid anion salts.

[0334] Examples of the inorganic acid anion salt include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), and lithium hexafluorotantalate (LiTaF 6 ).

[0335] Examples of organic acid anion salts include lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N).

[0336] Among them, the fluorine-containing lithium salt is preferably a lithium salt other than the lithium (N-carbonyl) sulfonamide compound (I) represented by formula (I). In other words, the fluorine-containing lithium salt is preferably at least one selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium hexafluorotantalate (LiTaF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N). The fluorine-containing lithium salt is particularly preferably lithium hexafluorophosphate (LiPF6).

[0337] Examples of fluorine-free lithium salts include lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium decachlorodecaborate (Li2B 10 Cl 10 )wait.

[0338] When the electrolyte contains a fluorine-containing lithium salt, the content ratio of the fluorine-containing lithium salt relative to the total amount of the electrolyte is preferably 50 mass % to 100 mass %, more preferably 60 mass % to 100 mass %, and even more preferably 80 mass % to 100 mass %.

[0339] When the fluorine-containing lithium salt includes lithium hexafluorophosphate (LiPF6), the content ratio of lithium hexafluorophosphate (LiPF6) relative to the total amount of the electrolyte is preferably 50 mass% or more and 100 mass% or less, more preferably 60 mass% or more and 100 mass% or less, and further preferably 80 mass% or more and 100 mass% or less.

[0340] When the nonaqueous electrolyte solution contains an electrolyte, the concentration of the electrolyte in the nonaqueous electrolyte solution is preferably 0.1 mol / L to 3 mol / L, and more preferably 0.5 mol / L to 2 mol / L.

[0341] When the non-aqueous electrolyte contains lithium hexafluorophosphate (LiPF6), the concentration of lithium hexafluorophosphate (LiPF6) in the non-aqueous electrolyte is preferably 0.1 mol / L to 3 mol / L, more preferably 0.5 mol / L to 2 mol / L.

[0342] <Other ingredients>

[0343] The non-aqueous electrolyte may contain other components as needed.

[0344] As other components, acid anhydride etc. are mentioned.

[0345] [Lithium secondary battery precursor]

[0346] Next, the lithium secondary battery precursor of the present disclosure will be described.

[0347] The lithium secondary battery precursor of the present disclosure comprises a housing, a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode, negative electrode, separator, and electrolyte are housed in the housing. The positive electrode is a positive electrode capable of absorbing and releasing lithium ions. The negative electrode is a negative electrode capable of absorbing and releasing lithium ions. The electrolyte is the non-aqueous electrolyte of the present disclosure.

[0348] The lithium secondary battery precursor refers to a lithium secondary battery before charging and discharging. That is, in the lithium secondary battery precursor, the negative electrode does not include a negative electrode SEI film, and the positive electrode does not include a positive electrode SEI film.

[0349] <Housing>

[0350] The shape of the housing is not particularly limited and can be appropriately selected depending on the application of the lithium secondary battery precursor of the present disclosure. Examples of the housing include a housing composed of a laminate film and a housing composed of a battery case and a battery case cover.

[0351] <Positive electrode>

[0352] The positive electrode is a positive electrode that can store and release lithium ions. The positive electrode preferably contains at least one positive electrode active material that can store and release lithium ions.

[0353] The positive electrode includes a positive electrode current collector and a positive electrode mixture material layer. The positive electrode mixture material layer is provided on at least a portion of the surface of the positive electrode current collector.

[0354] As the material of the positive electrode current collector, for example, a metal or an alloy can be mentioned. Specifically, as the material of the positive electrode current collector, aluminum, nickel, stainless steel (SUS), copper, etc. can be mentioned. Among them, from the perspective of the balance between the high conductivity and the cost, aluminum is preferred. Here, "aluminum" refers to pure aluminum or an aluminum alloy. As the positive electrode current collector, aluminum foil is preferred. The material of the aluminum foil is not particularly limited, and A1085 material, A3003 material, etc. can be mentioned.

[0355] The positive electrode mixture material layer contains a positive electrode active material and a binder.

[0356] The positive electrode active material is not particularly limited as long as it can occlude and release lithium ions, and can be appropriately adjusted depending on the application of the lithium secondary battery precursor and the like.

[0357] As the positive electrode active material, for example, a first oxide, a second oxide, etc. can be mentioned. The first oxide contains lithium (Li) and nickel (Ni) as constituent metal elements. The second oxide contains Li, Ni, and at least one of metal elements other than Li and Ni as constituent metal elements. As metal elements other than Li and Ni, for example, transition metal elements, typical metal elements, etc. can be mentioned. For the second oxide, it is preferred that as metal elements other than Li and Ni, it is preferably contained in a proportion equal to or less than Ni in terms of atomic number. Metal elements other than Li and Ni can be, for example, at least one selected from the group consisting of Co, Mn, Al, Cr, Fe, V, Mg, Ca, Na, Ti, Zr, Nb, Mo, W, Cu, Zn, Ga, In, Sn, La, and Ce. These positive electrode active materials can be used alone or in combination.

[0358] The positive electrode active material preferably includes a lithium-containing composite oxide (hereinafter sometimes referred to as "NCM") represented by the following formula (C1). The lithium-containing composite oxide (C1) has the advantages of high energy density per unit volume and excellent thermal stability.

[0359] LiNi a Co b Mn c O2…Formula (C1)

[0360] In formula (C1), a, b, and c are each independently greater than 0 and less than 1, and the total of a, b, and c is 0.99 or more and 1.00 or less.

[0361] As a specific example of NCM, LiNi 0.33 Co 0.33 Mn 0.33 O2、LiNi 0.5 Co 0.3 Mn 0.2 O2、LiNi 0.5 Co 0.2 Mn 0.3 O2、LiNi 0.6 Co 0.2 Mn 0.2 O2、LiNi 0.8 Co 0.1 Mn 0.1 O2, etc.

[0362] The positive electrode active material may include a lithium-containing composite oxide (hereinafter sometimes referred to as “NCA”) represented by the following formula (C2).

[0363] Li t Ni 1-x-y Cox Al y O2…Formula (C2)

[0364] In formula (C2), t is 0.95 to 1.15, x is 0 to 0.3, y is 0.1 to 0.2, and the total of x and y is less than 0.5.

[0365] As a specific example of NCA, LiNi 0.8 Co 0.15 Al 0.05 O2, etc.

[0366] In the case where the positive electrode in the lithium secondary battery precursor of the present disclosure comprises a positive electrode collector and a positive electrode mixture material layer containing a positive electrode active material and a binder, the content of the positive electrode active material in the positive electrode mixture material layer is preferably 10% by mass to 99.9% by mass, more preferably 30% by mass to 99.0% by mass, further preferably 50% by mass to 99.0% by mass, and particularly preferably 70% by mass to 99.0% by mass, relative to the total amount of the positive electrode mixture material layer.

[0367] As the binder, for example, polyvinyl acetate, polymethyl methacrylate, nitrocellulose, fluororesin, rubber particles etc. can be mentioned. As fluororesin, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), vinylidene fluoride-hexafluoropropylene copolymer etc. can be mentioned. As rubber particles, styrene-butadiene rubber particles, acrylonitrile rubber particles etc. can be mentioned. Among them, from the viewpoint of improving the oxidation resistance of the positive electrode mixture material layer, fluororesin is preferably used. The binder can be used alone as one, or two or more can be used in combination as needed.

[0368] From the perspective of the simultaneous realization of the physical properties (for example, electrolyte permeability, peel strength, etc.) of the positive electrode mixture material layer and the battery performance, relative to the total amount of the positive electrode mixture material layer, the content of the binder in the positive electrode mixture material layer is preferably 0.1% by mass or more and 4% by mass or less. If the content of the binder is 0.1% by mass or more, the adhesion between the positive electrode mixture material layer and the positive electrode current collector and the adhesion between the positive electrode active material are further improved. If the content of the binder is 4% by mass or less, the amount of the positive electrode active material in the positive electrode mixture material layer can be increased, and therefore the discharge capacity is further improved.

[0369] The positive electrode mixture material layer preferably contains a conductive additive.

[0370] As the material of the conductive auxiliary agent, known conductive auxiliary agents can be used. As known conductive auxiliary agents, preferably carbon materials with conductivity. As conductive carbon materials, graphite, carbon black, conductive carbon fibers, fullerenes, etc. can be mentioned. These can be used alone or in combination of two or more. As conductive carbon fibers, carbon nanotubes, carbon nanofibers, carbon fibers, etc. can be mentioned. As graphite, for example, artificial graphite, natural graphite, etc. can be mentioned. As natural graphite, for example, flaky graphite, block graphite, earthy graphite, etc. can be mentioned.

[0371] The conductive auxiliary agent may be made of a commercially available product. Examples of commercially available carbon black include TOKA BLACK #4300, #4400, #4500, and #5500 (manufactured by Tokai Carbon Co., Ltd., furnace black), PRINTEX L (manufactured by Degussa, furnace black), Raven 7000, 5750, 5250, 5000 ULTRA III, and 5000 ULTRA, Conductex SC ULTRA, Conductex 975 ULTRA, and PUER BLACK 100, 115, and 205 (manufactured by Columbia, furnace black), and #2350, #2400B, #2600B, #30050B, #3030B, #3230B, #3350B, #3400B, and #5400B (manufactured by Mitsubishi Chemical Corporation, furnace black), MONARCH 1400, 1300, 900, Vulcan XC-72R, Black Pearls 2000, LITX-50, LITX-200, etc. (manufactured by Cabot Corporation, furnace black), Ensaco 250G, Ensaco 260G, Ensaco 350G, Super-P (manufactured by TIMCAL), KETJEN BLACK EC-300J, EC-600JD (manufactured by Akzo), DENKA BLACK, DENKABLACK HS-100, FX-35 (manufactured by Denka Co., Ltd., acetylene black), etc.

[0372] The positive electrode mixture material layer may also contain other components, such as thickeners, surfactants, dispersants, wetting agents, and defoaming agents.

[0373] <Negative electrode>

[0374] The negative electrode is a negative electrode that can store and release lithium ions. The negative electrode preferably contains at least one negative electrode active material that can store and release lithium ions.

[0375] The negative electrode more preferably includes a negative electrode current collector and a negative electrode mixture material layer, wherein the negative electrode mixture material layer is provided on at least a portion of the surface of the negative electrode current collector.

[0376] The material of the negative electrode current collector is not particularly limited, and any known material can be used, for example, a metal or an alloy. Specifically, the material of the negative electrode current collector includes aluminum, nickel, stainless steel (SUS), nickel-plated steel, copper, etc. Among them, copper is preferably used as the material of the negative electrode current collector from the perspective of processability. Copper foil is preferably used as the negative electrode current collector.

[0377] The negative electrode mixture material layer contains a negative electrode active material and a binder.

[0378] The negative electrode active material is not particularly limited as long as it is a material that can absorb and release lithium ions. The negative electrode active material is preferably at least one selected from the group consisting of, for example, metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, oxides that can be doped and dedoped with lithium ions, transition metal nitrides that can be doped and dedoped with lithium ions, and carbon materials that can be doped and dedoped with lithium ions. Among them, the negative electrode active material is preferably a carbon material that can be doped and dedoped with lithium ions (hereinafter referred to as "carbon material").

[0379] Examples of the carbon material include carbon black, activated carbon, graphite materials, and amorphous carbon materials. One of these carbon materials may be used alone, or two or more may be mixed. The form of the carbon material is not particularly limited, and examples thereof include fibrous, spherical, potato-like, and flaky shapes. The particle size of the carbon material is not particularly limited, but is preferably 5 μm to 50 μm, more preferably 20 μm to 30 μm.

[0380] Examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) calcined at 1500° C. or lower, and mesophase pitch carbon fibers (MCF).

[0381] Examples of graphite materials include natural graphite and artificial graphite. Examples of artificial graphite include graphitized MCMB and graphitized MCF. The graphite material may contain boron. The graphite material may also be coated with a metal or amorphous carbon. Examples of the metal coating the graphite material include gold, platinum, silver, copper, and tin. The graphite material may also be a mixture of amorphous carbon and graphite.

[0382] The negative electrode mixture material layer preferably contains a conductive auxiliary agent. Examples of the conductive auxiliary agent include the same conductive auxiliary agents as those exemplified as the conductive auxiliary agents that can be contained in the positive electrode mixture material layer.

[0383] The negative electrode mixture material layer may contain other components in addition to the above components. Examples of other components include thickeners, surfactants, dispersants, wetting agents, and defoaming agents.

[0384] <Diaphragm>

[0385] Examples of separators include porous resin plates. Materials for the porous resin plates include resins and nonwoven fabrics containing the resins. Examples of resins include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polyester, cellulose, and polyamide.

[0386] The separator is preferably a single-layer or multi-layer porous resin sheet. The porous resin sheet is primarily composed of one or more polyolefin resins. The separator is preferably 5 μm to 30 μm thick. The separator is preferably positioned between the positive and negative electrodes.

[0387] [An example of a lithium secondary battery precursor]

[0388] Reference Figure 1 An example of the lithium secondary battery precursor 1 according to the embodiment of the present disclosure will be described in detail. Figure 1 This is a cross-sectional view of a lithium secondary battery precursor 1 according to an embodiment of the present disclosure.

[0389] The lithium secondary battery precursor 1 is a stacked type. Figure 1 As shown, in a lithium secondary battery precursor 1, a battery element 10 is enclosed within an external package 30. The external package 30 is formed of a laminate film. A positive electrode lead 21 and a negative electrode lead 22 are each attached to the battery element 10. The positive electrode lead 21 and the negative electrode lead 22 are each led outward from the interior of the external package 30 in opposite directions.

[0390] like Figure 1 As shown, battery element 10 is composed of a stack of a positive electrode 11, a separator 13, and a negative electrode 12. Positive electrode 11 is formed by forming positive electrode mixture layers 11B on both principal surfaces of a positive electrode current collector 11A. Negative electrode 12 is formed by forming negative electrode mixture layers 12B on both principal surfaces of a negative electrode current collector 12A. Positive electrode mixture layer 11B formed on one principal surface of positive electrode current collector 11A of positive electrode 11 faces negative electrode mixture layer 12B formed on one principal surface of negative electrode current collector 12A of negative electrode 12 adjacent to positive electrode 11, with separator 13 interposed therebetween.

[0391] The non-aqueous electrolyte of the present disclosure is injected into the exterior packaging body 30 of the lithium secondary battery precursor 1. The non-aqueous electrolyte of the present disclosure permeates the positive electrode mixture layer 11B, the separator 13, and the negative electrode mixture layer 12B. In the lithium secondary battery precursor 1, a single cell layer 14 is formed by the adjacent positive electrode mixture layer 11B, the separator 13, and the negative electrode mixture layer 12B. It should be noted that the positive electrode and the negative electrode can also be products formed by forming active material layers on one side of each collector.

[0392] It should be noted that in this embodiment, the lithium secondary battery precursor 1 is a stacked type, but this disclosure is not limited thereto. For example, a wound type may also be employed. A wound type is formed by stacking the positive electrode, separator, negative electrode, and separator in this order and winding them into layers. Wound types include cylindrical and square types.

[0393] In this embodiment, if Figure 1 As shown, the positive and negative lead wires each protrude from the interior of the external package 30 toward the exterior in a direction opposite to the exterior package 30, but the present disclosure is not limited thereto. For example, the positive and negative lead wires each protrude from the interior of the external package 30 toward the exterior in the same direction as the exterior package 30.

[0394] As an example of a lithium secondary battery according to an embodiment of the present disclosure described below, a lithium secondary battery is provided in which an SEI film is formed on the surfaces of the positive electrode mixture layer 11B and the negative electrode mixture layer 12B in the lithium secondary battery precursor 1 by charging and discharging the lithium secondary battery precursor 1.

[0395] As another example of the lithium secondary battery precursor of the present disclosure, a button-type battery can also be mentioned.

[0396] Figure 2 This is a schematic perspective view showing an example of a button-type battery as another example of a lithium secondary battery precursor of the present disclosure.

[0397] Figure 2 In the button-type battery shown, a disc-shaped negative electrode 42, a separator 45 filled with a non-aqueous electrolyte, a disc-shaped positive electrode 41, and, if necessary, stainless steel or aluminum separators 47 and 48 are stacked in this order and housed between a positive electrode case 43 (hereinafter also referred to as the "battery case") and a sealing plate 44 (hereinafter also referred to as the "battery case cover"). The positive electrode case 43 and the sealing plate 44 are sealed by caulking with a gasket 46.

[0398] In this example, as the nonaqueous electrolyte injected into the separator 45 , the nonaqueous electrolyte of the present disclosure is used.

[0399] [Lithium secondary battery]

[0400] Next, a lithium secondary battery according to an embodiment of the present disclosure will be described.

[0401] The lithium secondary battery of this embodiment comprises a housing, a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode, negative electrode, separator, and electrolyte are housed in the housing. The positive electrode is a positive electrode capable of absorbing and releasing lithium ions. The negative electrode is a negative electrode capable of absorbing and releasing lithium ions. The electrolyte is the non-aqueous electrolyte described in this disclosure. The negative electrode includes a negative electrode SEI film. The positive electrode includes a positive electrode SEI film.

[0402] The lithium secondary battery according to this embodiment differs from the lithium secondary battery precursor according to this embodiment primarily in that the negative electrode includes a negative electrode SEI film, and the positive electrode includes a positive electrode SEI film. That is, the lithium secondary battery according to this embodiment is identical to the lithium secondary battery precursor according to this embodiment except for the first and second points. Therefore, the following description of the components of the lithium secondary battery according to this embodiment other than the first and second points will be omitted.

[0403] Regarding the first point, the phrase "the negative electrode includes a negative electrode SEI film" encompasses a first negative electrode configuration and a second negative electrode configuration when the negative electrode includes a negative electrode current collector and a negative electrode mixture layer. The first negative electrode configuration refers to a configuration in which a negative electrode SEI film is formed on at least a portion of the surface of the negative electrode mixture layer. The second negative electrode configuration refers to a configuration in which a negative electrode SEI film is formed on the surface of a negative electrode active material, which is a constituent material of the negative electrode mixture layer.

[0404] Regarding the second point, the phrase "the positive electrode includes a positive electrode SEI film" includes a first positive electrode form and a second positive electrode form when the positive electrode includes a positive electrode current collector and a positive electrode mixture material layer. The first positive electrode form refers to a form in which a positive electrode SEI film is formed on at least a portion of the surface of the positive electrode mixture material layer. The second positive electrode form refers to a form in which a positive electrode SEI film is formed on the surface of a positive electrode active material that is a constituent material of the positive electrode mixture material layer.

[0405] The SEI film contains, for example, at least one selected from the group consisting of a decomposition product of the lithium (N-carbonyl)sulfonamide compound (I), a reaction product of the lithium (N-carbonyl)sulfonamide compound (I) and an electrolyte, and a decomposition product of the reaction product.

[0406] The composition of the negative electrode SEI film may be the same as or different from that of the positive electrode SEI film. The thickness of the negative electrode SEI film may be the same as or different from that of the positive electrode SEI film.

[0407] The lithium secondary battery of the present disclosure can be obtained by charging and discharging the lithium secondary battery precursor of the present disclosure. In other words, the lithium secondary battery of the present disclosure can be obtained by performing the aging process described below.

[0408] [Method for producing lithium (N-carbonyl) sulfonamide compounds]

[0409] Next, the method for producing the lithium (N-carbonyl)sulfonamide compound of the present disclosure will be described.

[0410] The method for producing a lithium (N-carbonyl) sulfonamide compound comprises a first step described below and a second step described below. The first step and the second step are performed sequentially to obtain the lithium (N-carbonyl) sulfonamide compound of the present disclosure.

[0411] <First Step>

[0412] In the first step, a sulfonamide compound is reacted with a carboxylic acid chloride or a carboxylic acid anhydride in a solvent, and the generated salt is removed and then subjected to column chromatography to obtain a (N-carbonyl)sulfonamide compound.

[0413] The sulfonamide compound, the carboxylic acid chloride, and the carboxylic acid anhydride can each be appropriately selected depending on the type of the (N-carbonyl)sulfonamide compound to be produced.

[0414] Examples of the sulfonamide compound include trifluoromethanesulfonamide, methanesulfonamide, phenoxymethylsulfonamide, ethyl sulfamate, and 2,2,2-trifluoroethyl sulfamate.

[0415] Examples of the carboxylic acid chloride include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, phenyl chloroformate, and acetyl chloride.

[0416] Examples of the carboxylic anhydride include trifluoroacetic anhydride, acetic anhydride, trichloroacetic anhydride, di-tert-butyl dicarbonate, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

[0417] Examples of the solvent include non-aqueous solvents. Examples of the non-aqueous solvent include tetrahydrofuran, diethyl ether, dimethoxyethane, 1,4-dioxane, acetone, ethyl acetate, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, pentane, hexane, heptane, octane, nonane, decane, toluene, xylene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, propylbenzene, isopropylbenzene (also known as cumene), cyclohexylbenzene, tetralin, mesitylene, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Xylene includes o-xylene, m-xylene, and p-xylene.

[0418] The reaction in the first step can be carried out under any conditions, either normal pressure or reduced pressure. To prevent the incorporation of components (e.g., moisture) that hinder the formation of the (N-carbonyl)sulfonamide compound, the reaction in the first step is preferably carried out under an inert atmosphere. Components that hinder the formation of the (N-carbonyl)sulfonamide compound include water. Examples of the inert atmosphere include nitrogen atmosphere and argon atmosphere.

[0419] The reaction temperature in the first step is preferably from -20°C to 60°C, more preferably from 0°C to 40°C, and even more preferably from 10°C to 30°C. When the reaction temperature is 60°C or lower, decomposition of the sulfonamide as a raw material and the carboxylic acid chloride or carboxylic anhydride as a reactant is suppressed, and the yield of the (N-carbonyl)sulfonamide compound is likely to increase.

[0420] From the viewpoint of efficiently proceeding the reaction, the reaction time in the first step is preferably from 30 minutes to 12 hours, and more preferably from 1 hour to 6 hours.

[0421] <Second step>

[0422] In the second step, a lithium salt compound and a (N-carbonyl)sulfonamide compound are reacted in a solvent to obtain a lithium (N-carbonyl)sulfonamide compound.

[0423] Examples of the lithium salt compound include lithium bis(trimethylsilyl)amide, lithium chloride, lithium carbonate, lithium hydroxide, lithium methoxide, lithium ethoxide, and lithium tert-butoxide. Among these, the lithium salt compound is preferably lithium bis(trimethylsilyl)amide, lithium chloride, lithium carbonate, or lithium hydroxide, and more preferably lithium bis(trimethylsilyl)amide.

[0424] The reaction in the second step can be carried out under any conditions, either normal pressure or reduced pressure. From the perspective of preventing the incorporation of components (e.g., water) that hinder the formation of the lithium (N-carbonyl) sulfonamide compound, the reaction in the second step is preferably carried out under an inert atmosphere. Components that hinder the formation of the lithium (N-carbonyl) sulfonamide compound include water. Examples of the inert atmosphere include nitrogen atmosphere and argon atmosphere.

[0425] The reaction temperature in the second step is preferably -20°C to 60°C, more preferably 0°C to 40°C, and even more preferably 10°C to 30°C.

[0426] From the viewpoint of efficiently proceeding the reaction, the reaction time in the second step is preferably from 30 minutes to 12 hours, and more preferably from 1 hour to 6 hours.

[0427] The method for removing the lithium (N-carbonyl) sulfonamide compound from the product is not particularly limited and can be appropriately adjusted according to the state of the product obtained. In the case of obtaining only the lithium (N-carbonyl) sulfonamide compound, the lithium (N-carbonyl) sulfonamide compound is removed in a manner without implementing special treatment. In the case where a slurry in which the lithium (N-carbonyl) sulfonamide compound is dispersed in a solvent is a product, the lithium (N-carbonyl) sulfonamide compound is removed by separating the solvent from the slurry and drying it. In the case where a solution in which the lithium (N-carbonyl) sulfonamide compound is dissolved in a solvent is a product, the lithium (N-carbonyl) sulfonamide compound is removed by distilling the solvent from the solution by utilizing heating and concentration. In the case where a solution in which the lithium (N-carbonyl) sulfonamide compound is dissolved in a solvent is a product, the lithium (N-carbonyl) sulfonamide compound is precipitated by adding a solvent in which the lithium (N-carbonyl) sulfonamide compound does not dissolve to the solution, then separating the solvent from the solution and drying it to remove the lithium (N-carbonyl) sulfonamide compound.

[0428] The lithium (N-carbonyl)sulfonamide compound removed from the product may be subjected to a drying treatment. The drying treatment is not particularly limited, and examples thereof include static drying using a tray dryer, fluidized drying using a conical dryer, drying using a hot plate, an oven, or the like, and drying using a dryer such as a desiccator to supply warm or hot air.

[0429] The pressure when drying the lithium (N-carbonyl) sulfonamide compound removed from the product can be any pressure between normal pressure and reduced pressure. The drying temperature when drying the lithium (N-carbonyl) sulfonamide compound removed from the product is preferably 20°C to 100°C, more preferably 40°C to 80°C, and even more preferably 50°C to 70°C. A drying temperature of 20°C or higher provides excellent drying efficiency. A drying temperature of 100°C or lower suppresses decomposition of the generated lithium (N-carbonyl) sulfonamide compound, making it easier and more stable to remove the lithium (N-carbonyl) sulfonamide compound.

[0430] The lithium (N-carbonyl)sulfonamide compound obtained from the product may be used as it is, or may be dispersed or dissolved in a solvent and used, or may be mixed with other substances and used.

[0431] [Method for producing lithium (N-carbonyl)sulfonamide compound (I)]

[0432] Next, the method for producing the lithium (N-carbonyl)sulfonamide compound (I) of the present disclosure will be described.

[0433] In the method for producing the lithium (N-carbonyl) sulfonamide compound (I) of the present disclosure, L in formula (1) can be used. 1 and L 2 The same method as the above-mentioned method for producing lithium (N-carbonyl)sulfonamide compound (I) is followed except that a sulfonamide compound, carboxylic acid chloride, carboxylic acid anhydride, etc. are selected so that each can be in the form of a single bond. Thus, lithium (N-carbonyl)sulfonamide compound (I) is obtained.

[0434] [Method for producing non-aqueous electrolyte]

[0435] Next, the method for producing the non-aqueous electrolyte solution of the present disclosure will be described.

[0436] The method for producing a non-aqueous electrolyte solution of the present disclosure includes a synthesis step, a dissolution step, and a mixing step. The dissolution step and the mixing step are performed sequentially. The synthesis step only needs to be performed before the mixing step.

[0437] In the synthesis step, a lithium (N-carbonyl)sulfonamide compound (I) is synthesized.

[0438] The synthesis process can be performed in the same manner as in the above-mentioned method for producing the lithium (N-carbonyl)sulfonamide compound (I).

[0439] In the dissolving step, the electrolyte is dissolved in a non-aqueous solvent to obtain a solution. Preferably, the conductivity of the obtained non-aqueous electrolyte solution is lower than the conductivity of the solution before adding the lithium (N-carbonyl)sulfonamide compound (I).

[0440] In the mixing step, the lithium (N-carbonyl) sulfonamide compound (I) and other additives used as needed are added to the solution and mixed. Thus, a non-aqueous electrolyte is obtained. The non-aqueous electrolyte obtained by the method for producing a non-aqueous electrolyte according to this embodiment can more effectively reduce the DC resistance in a lithium secondary battery.

[0441] It should be noted that the method for producing the non-aqueous electrolyte solution of the present disclosure includes a synthesis step, a dissolution step, and a mixing step, but the present disclosure is not limited thereto.

[0442] [Method for producing a lithium secondary battery precursor]

[0443] Next, a method for producing a lithium secondary battery precursor of the present disclosure will be described.

[0444] The method for manufacturing a lithium secondary battery precursor of the present disclosure includes a first preparation step, a second preparation step, a third preparation step, a storage step, and an injection step. The storage step and the injection step are performed sequentially. The first preparation step, the second preparation step, and the third preparation step are each performed before the storage step.

[0445] In the first preparation step, a positive electrode is prepared.

[0446] Examples of methods for preparing the positive electrode include applying a positive electrode mixture slurry on the surface of a positive electrode current collector and drying the mixture. The positive electrode mixture slurry contains a positive electrode active material and a binder.

[0447] The solvent contained in the positive electrode mixture material slurry is preferably an organic solvent, and examples of the organic solvent include N-methyl-2-pyrrolidone (NMP).

[0448] There are no particular limitations on the coating method for the positive electrode mixture material slurry; examples include slot die coating, slide coating, curtain coating, and gravure coating. There are no particular limitations on the drying method for the positive electrode mixture material slurry; examples include drying with warm air, hot air, or low-humidity air; vacuum drying; and drying with infrared radiation (e.g., far-infrared radiation). The drying time is not particularly limited, but is preferably between 1 minute and 30 minutes. The drying temperature is not particularly limited, but is preferably between 40°C and 80°C.

[0449] The dried product obtained by applying the positive electrode mixture slurry to the positive electrode current collector and drying it is preferably subjected to a pressurization process. This reduces the porosity of the positive electrode active material layer. Examples of pressurization methods include die pressing and roller pressing.

[0450] In the second preparation step, a negative electrode is prepared.

[0451] Examples of methods for preparing the negative electrode include applying a negative electrode mixture slurry on the surface of the negative electrode current collector and drying the mixture. The negative electrode mixture slurry contains a negative electrode active material and a binder.

[0452] Examples of the solvent contained in the negative electrode mixture material slurry include water and water-miscible liquid media. If the solvent contained in the negative electrode mixture material slurry includes a water-miscible liquid media, the coating properties on the negative electrode current collector can be improved. Examples of water-miscible liquid media include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, phosphoric acid esters, ethers, and nitriles.

[0453] The coating method, drying method, and pressurizing treatment of the negative electrode mixture material slurry may be the same methods as those exemplified as the coating method, drying method, and pressurizing treatment of the positive electrode mixture material slurry.

[0454] In the third preparation step, a non-aqueous electrolyte solution is prepared. The method for preparing the non-aqueous electrolyte solution is the same as the method described in the above-mentioned method for producing the non-aqueous electrolyte solution.

[0455] In the housing step, the positive electrode, the negative electrode, and the separator are housed in the case.

[0456] For example, in the housing step, a battery element is fabricated using the positive electrode, negative electrode, and separator. Next, the positive electrode current collector is electrically connected to the positive electrode lead, and the negative electrode current collector is electrically connected to the negative electrode lead. The battery element is then housed in a case and secured.

[0457] The method for electrically connecting the positive electrode current collector and the positive electrode lead is not particularly limited, and examples thereof include ultrasonic welding and resistance welding. The method for electrically connecting the negative electrode current collector and the negative electrode lead is not particularly limited, and examples thereof include ultrasonic welding and resistance welding.

[0458] Hereinafter, the state in which the positive electrode, the negative electrode, and the separator are housed in the case is referred to as an "assembly."

[0459] In the injection step, the nonaqueous electrolyte of the present disclosure is injected into the interior of the assembly. This allows the nonaqueous electrolyte to penetrate the positive electrode mixture layer, the separator, and the negative electrode mixture layer, resulting in a lithium secondary battery precursor.

[0460] [Method for manufacturing lithium secondary battery]

[0461] Next, a method for manufacturing the lithium secondary battery of the present disclosure will be described.

[0462] The method for manufacturing a lithium secondary battery of the present disclosure includes a fourth preparation step and an aging step. The fourth preparation step and the aging step are performed sequentially.

[0463] In the fourth preparation step, a lithium secondary battery precursor is prepared. The method for preparing the lithium secondary battery precursor is the same as the method described in the method for producing the lithium secondary battery precursor.

[0464] In the aging step, the lithium secondary battery precursor is aged to form a negative electrode SEI film and a positive electrode SEI film, thereby obtaining a lithium secondary battery.

[0465] The aging treatment includes charging and discharging the lithium secondary battery precursor at a temperature of 25° C. to 70° C. Specifically, the aging treatment includes a first charging stage, a first holding stage, a second charging stage, a second holding stage, and a charge-discharge stage.

[0466] In the first charging stage, the lithium secondary battery precursor is charged in an environment of 25°C to 70°C. In the first holding stage, the lithium secondary battery precursor after the first charging stage is held in an environment of 25°C to 70°C. In the second charging stage, the lithium secondary battery precursor after the first holding stage is charged in an environment of 25°C to 70°C. In the second holding stage, the lithium secondary battery precursor after the second charging stage is held in an environment of 25°C to 70°C. In the charge and discharge stage, the lithium secondary battery precursor after the second holding stage is subjected to a combination of one or more charges and discharges in an environment of 25°C to 70°C.

[0467] The lithium secondary battery obtained by the method for producing a lithium secondary battery of the present disclosure can more effectively suppress an increase in DC resistance and a decrease in discharge capacity even when stored in a high-temperature environment.

[0468] Example

[0469] Hereinafter, embodiments of the present disclosure will be described in detail with reference to examples. However, it should be noted that the present disclosure is not limited in any way by the description of these examples.

[0470] [Synthesis of lithium (N-carbonyl) sulfonamide compound (I)]

[0471] Synthetic compounds (I-1) to (I-48) represented by the following formula (I) were synthesized as follows.

[0472] R in the formula (I) of each of the synthetic compounds (I-1) to (I-48) is 1 、R 2 、L 1 , and L 2 Shown in Table 1 and Table 2.

[0473] [Chemical Formula 17]

[0474]

[0475] [Table 1]

[0476]

[0477] [Table 2]

[0478]

[0479] [Table 3]

[0480]

[0481] [Synthesis example 1]

[0482] Lithium butoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-5)] was synthesized as follows.

[0483] [Chemical Formula 18]

[0484]

[0485] <First Step: Synthesis of Butoxycarbonyltoluenesulfonamide>

[0486] A 200 mL four-necked flask, purged with nitrogen and connected to a condenser coil, was charged with p-toluenesulfonyl isocyanate (3.94 g, 20 mmol), dibutyltin dilaurate (0.126 g, 0.2 mmol), and dichloromethane (100 mL) as a solvent. n-Butanol (1.78 g, 24 mmol) was added while maintaining the mixture at room temperature. The mixture was stirred at reflux (40°C) and allowed to react. After 4 hours, the reaction was terminated and the mixture was cooled to room temperature.

[0487] The obtained reaction product was then washed by adding 100 mL of distilled water and 10 mL of ethyl acetate to the reaction solution, and extracting and washing was performed using a separating funnel.

[0488] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0489] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent composed of hexane and ethyl acetate.

[0490] Thus, butoxycarbonyltoluenesulfonamide (5.27 g, 19.42 mmol, yield 97%) was obtained as a first white solid.

[0491] The following shows the first white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0492] 1 H-NMR: δ0.82 (t, J=7.2Hz, 3H), 1.10-1.30 (m, 2H), 1.38-1.53 ​​(m, 2H), 2.40 (s, 3H), 3.97 (t, J=6.5Hz, 2H), 7.44 (d, J=8.1Hz, 2H), 7.78 (d, J=8.4Hz, 2H), 11.89 (br, 1H)

[0493] <Second Step: Synthesis of Lithium Butoxycarbonyltoluenesulfonamide (I-5)>

[0494] In a 200 mL four-necked flask purged with nitrogen, butoxycarbonyl toluenesulfonamide (3.11 g, 11.46 mmol) and tetrahydrofuran (50 mL) as a solvent were placed, and the temperature was kept at -20 degrees. Lithium bis(trimethylsilyl)amide (1.3 M, 1.3 mol / dm 3 ), and tetrahydrofuran solution (8.8 mL, 11.46 mmol), returned to room temperature, stirred for 6 hours to react, and a second white solid precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained second white solid was distilled off under reduced pressure.

[0495] Thus, lithium butoxycarbonyltoluenesulfonamide (2.17 g, 7.83 mmol, yield 68%) was obtained as a second white solid.

[0496] The following shows the second white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0497] 1 H-NMR: δ0.84 (t, J=7.3Hz, 3H), 1.16-1.45 (m, 4H), 2.31 (s, 3H), 3.64 (t, J=6.5Hz, 2H), 7.15 (d, J=8.4Hz, 2H), 7.58 (d, J=8.1Hz, 2H)

[0498] As described above, based on the results of Synthesis Example 1, lithium butoxytoluenesulfonamide was obtained according to the following reaction pathway [Synthetic Compound (I-5)].

[0499] [Chemical Formula 19]

[0500]

[0501] [Synthesis example 2]

[0502] The lithium methoxycarbonyl trifluoromethanesulfonamide represented by the following structural formula [Synthetic Compound (I-10)] was synthesized as follows.

[0503] [Chemical Formula 20]

[0504]

[0505] <First Step: Synthesis of Methoxycarbonyl Trifluoromethanesulfonamide>

[0506] In a 200 mL four-necked flask purged with nitrogen, trifluoromethanesulfonamide (5.01 g, 33.6 mmol), pyridine (6.38 g, 81 mmol), 4-dimethylaminopyridine (0.99 g, 8.1 mmol), and tetrahydrofuran (50 mL) as a solvent were placed. The mixture was kept at 0°C and methyl chloroformate (7.62 g, 81 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove the hydrochloride, and the resulting solution was washed. That is, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0507] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0508] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0509] Thus, methoxycarbonyl trifluoromethylsulfonamide (3.12 g, 33.6 mmol, yield 44.8%) was obtained as a third white solid.

[0510] The following shows the structure of the third white solid: 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0511] 1 H-NMR: δ3.51 (s, 3H), 10.00 (br, 2H)

[0512] <Second Step: Synthesis of Lithium Methoxycarbonyl Trifluoromethanesulfonamide (I-10)>

[0513] A 200 mL four-necked flask purged with nitrogen was charged with methoxycarbonyl trifluoromethylsulfonamide (1.90 g, 9.17 mmol) and diethyl ether (50 mL) as a solvent. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (7.1 mL, 9.17 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (50 mL) was added at room temperature to precipitate a fourth white solid from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting fourth white solid was distilled off under reduced pressure.

[0514] Thus, lithium methoxycarbonyl trifluoromethylsulfonamide (0.99 g, 4.65 mmol, yield 51%) was obtained as a fourth white solid.

[0515] The following shows the fourth white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0516] 1 H-NMR: δ 3.40 (s, 3H)

[0517] As described above, based on the results of Synthesis Example 2, methoxycarbonyl trifluoromethylsulfonamide lithium was obtained according to the following reaction pathway [Synthetic Compound (I-10)].

[0518] [Chemical Formula 21]

[0519]

[0520] [Synthesis example 3]

[0521] Lithium methoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-1)] was synthesized as follows.

[0522] [Chemical Formula 22]

[0523]

[0524] <First Step: Synthesis of Methoxycarbonyltoluenesulfonamide>

[0525] Synthesis was carried out by the same method as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that n-butanol was replaced with methanol (1.28 g, 40 mmol).

[0526] Thus, methoxycarbonyltoluenesulfonamide (4.33 g, 18.89 mmol, yield 94%) was obtained as the fifth white solid.

[0527] The following shows the fifth white solid1 The measurement results were obtained by H-NMR (DMSO-d6).

[0528] 1 H-NMR: δ2.31 (s, 3H), 3.24 (s, 3H), 7.15 (d, J = 7.8Hz, 2H), 7.59 (d, J = 7.8Hz, 2H)

[0529] <Second Step: Synthesis of Lithium Methoxycarbonyltoluenesulfonamide (I-1)>

[0530] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound I-5) using methoxycarbonyltoluenesulfonamide (1.52 g, 6.63 mmol), tetrahydrofuran (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.1 mL, 6.63 mmol).

[0531] Thus, lithium methoxycarbonyltoluenesulfonamide (0.99 g, 4.20 mmol, yield 63%) was obtained as the sixth white solid.

[0532] The following shows the sixth white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0533] 1 H-NMR: δ2.31 (s, 3H), 3.25 (s, 3H), 7.16 (d, J = 7.8Hz, 2H), 7.59 (d, J = 7.8Hz, 2H)

[0534] [Synthesis example 4]

[0535] Lithium ethoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-2)] was synthesized as follows.

[0536] [Chemical Formula 23]

[0537]

[0538] <First Step: Synthesis of Ethoxycarbonyltoluenesulfonamide>

[0539] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that n-butanol was replaced with ethanol (1.84 g, 40 mmol).

[0540] Thus, ethoxycarbonyltoluenesulfonamide (4.47 g, 18.37 mmol, yield 92%) was obtained as the seventh white solid.

[0541] The following shows the seventh white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0542] 1 H-NMR: δ1.00 (t, J=7.0Hz, 3H), 2.23 (s, 3H), 3.68 (q, J=7.0Hz, 2H), 7.15 (d, J=8.1Hz, 2H), 7.58 (d, J=7.8Hz, 2H)

[0543] <Second Step: Synthesis of Lithium Ethoxycarbonyltoluenesulfonamide (I-2)>

[0544] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using ethoxycarbonyltoluenesulfonamide (3.24 g, 13.32 mmol), tetrahydrofuran (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (10.2 mL, 13.32 mmol).

[0545] Thus, lithium ethoxycarbonyltoluenesulfonamide (1.14 g, 4.56 mmol, yield 34%) was obtained as the eighth white solid.

[0546] The following shows the eighth white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0547] 1 H-NMR: δ1.01 (t, J=7.0Hz, 3H), 2.31 (s, 3H), 3.68 (q, J=7.3Hz, 2H), 7.15 (d, J=7.8Hz, 2H), 7.58 (d, J=8.1Hz, 2H)

[0548] [Synthesis example 5]

[0549] Lithium propoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-3)] was synthesized as follows.

[0550] [Chemical Formula 24]

[0551]

[0552] <First Step: Synthesis of Propylcarbonyltoluenesulfonamide>

[0553] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that p-toluenesulfonyl isocyanate (4.75 g, 24.09 mmol) was used and n-propanol (1.74 g, 28.9 mmol) was replaced with n-butanol.

[0554] Thus, propylcarbonyltoluenesulfonamide (5.70 g, 22.15 mmol, yield 92%) was obtained as a ninth white solid.

[0555] The following shows the ninth white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0556] 1 H-NMR: δ0.79 (t, J=7.4Hz, 3H), 1.32-1.48 (m, 2H), 2.40 (s, 3H), 3.92 (t, J=6.8Hz, 2H), 7.43 (d, J=8.6Hz, 2H), 7.78 (d, J=8.4Hz, 2H), 11.88 (br, 1H)

[0557] <Second Step: Synthesis of Lithium Propoxycarbonyltoluenesulfonamide (I-3)>

[0558] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using propylcarbonyltoluenesulfonamide (5.70 g, 22.15 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (17.0 mL, 22.15 mmol).

[0559] Thus, lithium propoxycarbonyltoluenesulfonamide (3.66 g, 13.90 mmol, yield 63%) was obtained as the tenth white solid.

[0560] The following shows the 10th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0561] 1 H-NMR: δ0.79 (t, J=7.4Hz, 3H), 1.32-1.48 (m, 2H), 2.30 (s, 3H), 3.58 (t, J=6.8Hz, 2H), 7.15 (d, J=8.1Hz, 2H), 7.58 (d, J=8.4Hz, 2H)

[0562] [Synthesis Example 6]

[0563] Lithium isopropoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-4)] was synthesized as follows.

[0564] [Chemical Formula 25]

[0565]

[0566] <First Step: Synthesis of Isopropylcarbonyltoluenesulfonamide>

[0567] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that n-butanol was replaced with isopropyl alcohol (2.40 g, 40 mmol).

[0568] Thus, isopropylcarbonyltoluenesulfonamide (4.55 g, 17.68 mmol, yield 88%) was obtained as the 11th white solid.

[0569] The following shows the 11th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0570] 1 H-NMR: δ1.10 (d, J=5.94Hz, 6H), 2.40 (s, 3H), 4.72 (sept, J=6.2Hz, 1H), 7.43 (d, J=8.4Hz, 2H), 7.78 (d, J=8.1Hz, 2H), 11.77 (br, 1H)

[0571] <Second Step: Synthesis of Lithium Isopropoxycarbonyltoluenesulfonamide (I-4)>

[0572] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using isopropoxycarbonyltoluenesulfonamide (5.55 g, 21.57 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (16.6 mL, 21.57 mmol).

[0573] Thus, lithium isopropoxycarbonyltoluenesulfonamide (5.46 g, 20.74 mmol, yield 96%) was obtained as the 12th white solid.

[0574] The following shows the 12th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0575] 1H-NMR: δ1.00 (d, J=6.2Hz, 3H), 2.31 (s, 3H), 4.44 (sept, J=6.1Hz, 1H), 7.15 (d, J=7.8Hz, 2H), 7.58 (d, J=8.4Hz, 2H)

[0576] [Synthesis Example 7]

[0577] Lithium tert-butoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-6)] was synthesized as follows.

[0578] [Chemical Formula 26]

[0579]

[0580] <First Step: Synthesis of tert-Butylcarbonyltoluenesulfonamide>

[0581] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that n-butanol was replaced with tert-butyl butyl alcohol (1.78 g, 24 mmol).

[0582] Thus, tert-butylcarbonyltoluenesulfonamide (4.53 g, 16.70 mmol, yield 83%) was obtained as the 13th white solid.

[0583] The following shows the 13th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0584] 1 H-NMR: δ1.29 (s, 9H), 2.41 (s, 3H), 7.44 (d, J=8.4Hz, 2H), 7.76 (d, J=8.1Hz, 2H), 11.53 (br, 1H)

[0585] <Second Step: Synthesis of Lithium tert-Butoxycarbonyltoluenesulfonamide (I-6)>

[0586] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using tert-butylcarbonyltoluenesulfonamide (2.06 g, 7.59 mmol), tetrahydrofuran (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.8 mL, 7.59 mmol).

[0587] Thus, lithium tert-butoxycarbonyltoluenesulfonamide (2.0 g, 7.21 mmol, yield 95%) was obtained as the 14th white solid.

[0588] The following shows the 14th white solid1 The measurement results were obtained by H-NMR (DMSO-d6).

[0589] 1 H-NMR: δ1.20 (s, 9H), 2.30 (s, 3H), 7.14 (d, J = 8.1Hz, 2H), 7.56 (d, J = 8.1Hz, 2H)

[0590] [Synthesis example 8]

[0591] Lithium 2,2,2-trifluoroethoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-7)] was synthesized as follows.

[0592] [Chemical Formula 27]

[0593]

[0594] <First Step: Synthesis of 2,2,2-trifluoroethoxycarbonyltoluenesulfonamide>

[0595] In the first step of Synthesis Example 1 (Synthesis of Compound (I-5)), p-toluenesulfonyl isocyanate (4.73 g, 24.0 mmol) was used and n-butanol was replaced with 2,2,2-trifluoroethanol (2.40 g, 24.0 mmol).

[0596] Thus, 2,2,2-trifluoroethoxycarbonyltoluenesulfonamide (5.12 g, 17.22 mmol, yield 72%) was obtained as the 15th white solid.

[0597] The following shows the 15th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0598] 1 H-NMR: δ2.41 (s, 3H), 4.71 (q, J=9.2Hz, 2H), 7.45 (d, J=8.4Hz, 2H), 7.79 (d, J=8.4Hz, 2H)

[0599] <Second Step: Synthesis of Lithium (2,2,2-Trifluoroethoxy)toluenesulfonamide (I-7))

[0600] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using 2,2,2-trifluoroethoxycarbonyltoluenesulfonamide (5.80 g, 19.51 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (15.0 mL, 19.51 mmol).

[0601] Thus, lithium (2,2,2-trifluoroethoxy)carbonyltoluenesulfonamide (4.98 g, 16.43 mmol, yield 84%) was obtained as the 16th white solid.

[0602] The following shows the 16th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0603] 1 H-NMR: δ2.31 (s, 3H), 4.29 (q, J=9.5Hz, 2H), 7.18 (d, J=8.1Hz, 2H), 7.60 (d, J=8.1Hz, 2H)

[0604] [Synthesis Example 9]

[0605] The lithium phenoxycarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-8)] was synthesized as follows.

[0606] [Chemical Formula 28]

[0607]

[0608] <First Step: Synthesis of Phenoxycarbonyltoluenesulfonamide>

[0609] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that p-toluenesulfonyl isocyanate (8.32 g, 42.2 mmol) was used and n-butanol was replaced with phenol (4.40 g, 46.7 mmol).

[0610] Thus, phenoxycarbonyltoluenesulfonamide (10.33 g, 35.50 mmol, yield 84%) was obtained as the 17th white solid.

[0611] The following shows the 17th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0612] 1 H-NMR: δ2.41 (s, 3H), 7.05 (d, J=8.6Hz, 2H), 7.20-7.30 (m, 1H), 7.36 (d, J=7.6Hz, 2H), 7.46 (d, J=7.8Hz, 2H), 7.83 (d, J=7.8Hz, 2H)

[0613] <Second Step: Synthesis of Lithium Phenoxycarbonyltoluenesulfonamide (I-8)>

[0614] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using phenoxycarbonyltoluenesulfonamide (2.70 g, 9.27 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.1 mL, 9.27 mmol).

[0615] Thus, lithium phenoxycarbonyltoluenesulfonamide (2.0 g, 6.80 mmol, yield 73%) was obtained as the 18th white solid.

[0616] The following shows the 18th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0617] 1 H-NMR: δ2.32 (s, 3H), 6.88 (d, J=8.1Hz, 2H), 7.03 (t, J=4.1, 1H), 7.10-7.30 (m, 4H), 7.63 (d, J=8.1Hz, 2H)

[0618] [Synthesis Example 10]

[0619] Lithium 2-methoxyethylcarbonyltoluenesulfonamide represented by the following structural formula [Synthetic Compound (I-9)] was synthesized as follows.

[0620] [Chemical Formula 29]

[0621]

[0622] <First Step: Synthesis of 2-Methoxyethylcarbonyltoluenesulfonamide>

[0623] The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthesis of Compound (I-5)) except that p-toluenesulfonyl isocyanate (4.14 g, 21.0 mmol) was used and n-butanol was replaced with 2-methoxyethanol (1.60 g, 21.0 mmol).

[0624] Thus, 2-methoxyethylcarbonyltoluenesulfonamide (5.63 g, 20.60 mmol, yield 98%) was obtained as the 19th white solid.

[0625] The following shows the 19th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0626] 1H-NMR: δ2.40 (s, 3H), 3.35-3.50 (m, 2H), 4.00-4.15 (m, 2H), 7.43 (d, J=8.1Hz, 2H), 7.78 (d, J=8.4Hz, 2H), 11.99 (br, 1H)

[0627] <Second Step: Synthesis of Lithium 2-Methoxyethylcarbonyltoluenesulfonamide (I-9)>

[0628] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using 2-methoxyethylcarbonyltoluenesulfonamide (5.63 g, 20.60 mmol), tetrahydrofuran (100 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (15.8 mL, 20.60 mmol).

[0629] Thus, lithium 2-methoxyethylcarbonyltoluenesulfonamide (5.45 g, 19.52 mmol, yield 95%) was obtained as the 20th white solid.

[0630] The following shows the 20th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0631] 1 H-NMR: δ2.31 (s, 3H), 3.21 (s, 3H), 3.30-3.40 (m, 2H), 3.70-3.80 (m, 2H), 7.16 (d, J = 8.1Hz, 2H), 7.59 (d, J = 7.8Hz, 2H)

[0632] [Synthesis Example 11]

[0633] Ethoxycarbonyl trifluoromethanesulfonamide lithium represented by the following structural formula [Synthetic Compound (I-11)] was synthesized as follows.

[0634] [Chemical formula 30]

[0635]

[0636] <First Step: Synthesis of Ethoxycarbonyl Trifluoromethanesulfonamide>

[0637] The synthesis was carried out in the same manner as in the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), except that methyl chloroformate was replaced with ethyl chloroformate (8.56 g, 79 mmol).

[0638] Thus, ethoxycarbonyl trifluoromethylsulfonamide (3.12 g, 33.6 mmol, yield 45%) was obtained as the 21st white solid.

[0639] The following shows the 21st white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0640] 1 H-NMR: δ1.28 (t, J=4.2Hz, 3H), 4.32 (q, J=4.3Hz, 2H), 12.04 (br, 2H)

[0641] <Second Step: Synthesis of Lithium Ethoxycarbonyl Trifluoromethanesulfonamide (I-11)>

[0642] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using ethoxycarbonyl trifluoromethylsulfonamide (2.01 g, 9.04 mmol), diethyl ether (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.0 mL, 9.04 mmol).

[0643] Thus, ethoxycarbonyl trifluoromethylsulfonamide lithium (1.43 g, 6.30 mmol, yield 70%) was obtained as the 22nd white solid.

[0644] The following shows the 22nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0645] 1 H-NMR: δ1.10 (t, J=7.0Hz, 3H), 3.83 (q, J=7.0Hz, 2H)

[0646] [Synthesis Example 12]

[0647] The lithium propoxycarbonyl trifluoromethanesulfonamide represented by the following structural formula [Synthetic Compound (I-12)] was synthesized as follows.

[0648] [Chemical Formula 31]

[0649]

[0650] <First Step: Synthesis of Propoxycarbonyl Trifluoromethanesulfonamide>

[0651] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (4.30 g, 28.8 mmol), pyridine (4.56 g, 57.7 mmol), 4-dimethylaminopyridine (0.71 g, 5.8 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert methyl chloroformate into propyl chloroformate (7.07 g, 57.7 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[0652] Thus, propoxycarbonyl trifluoromethylsulfonamide (6.40 g, 27.2 mmol, yield 94%) was obtained as the 23rd white solid.

[0653] The following shows the 23rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0654] 1 H-NMR: δ0.87 (t, J=7.3Hz, 3H), 1.30-1.55 (m, 2H), 3.86 (t, J=6.3Hz, 2H)

[0655] <Second Step: Synthesis of Lithium Propoxycarbonyl Trifluoromethanesulfonamide (I-12)>

[0656] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using propoxycarbonyl trifluoromethylsulfonamide (3.28 g, 13.95 mmol), diethyl ether (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (10.7 mL, 13.95 mmol).

[0657] Thus, lithium propoxycarbonyl trifluoromethylsulfonamide (2.13 g, 8.83 mmol, yield 63%) was obtained as the 24th white solid.

[0658] The following shows the 24th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0659] 1 H-NMR: δ0.85 (t, J=7.3Hz, 3H), 1.35-1.60 (m, 2H), 3.75 (t, J=6.6Hz, 2H)

[0660] [Synthesis Example 13]

[0661] Isopropoxycarbonyl trifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-13)] was synthesized as follows.

[0662] [Chemical Formula 32]

[0663]

[0664] <First Step: Synthesis of Isopropoxycarbonyl Trifluoromethanesulfonamide>

[0665] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (4.30 g, 28.8 mmol), pyridine (4.56 g, 57.7 mmol), 4-dimethylaminopyridine (0.71 g, 5.8 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert methyl chloroformate into isopropyl chloroformate (7.07 g, 57.7 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[0666] Thus, isopropoxycarbonyltrifluoromethylsulfonamide (5.56 g, 23.6 mmol, yield 82%) was obtained as the 25th white solid.

[0667] The following shows the 25th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0668] 1 H-NMR: δ1.14 (d, J=4.3Hz, 3H), 1.16 (d, J=4.3Hz, 3H), 4.60-4.80 (m, 1H)

[0669] <Second Step: Synthesis of Lithium Isopropoxycarbonyl Trifluoromethanesulfonamide (I-13)>

[0670] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using isopropoxycarbonyltrifluoromethylsulfonamide (3.38 g, 14.37 mmol), diethyl ether (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (11.0 mL, 14.37 mmol).

[0671] Thus, lithium isopropoxycarbonyl trifluoromethylsulfonamide (2.55 g, 10.58 mmol, yield 74%) was obtained as the 26th white solid.

[0672] The following shows the 26th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0673] 1 H-NMR: δ1.10 (d, J=6.2Hz, 6H)

[0674] [Synthesis Example 14]

[0675] Butoxycarbonyl trifluoromethanesulfonamide lithium represented by the following structural formula [Synthetic Compound (I-14)] was synthesized as follows.

[0676] [Chemical Formula 33]

[0677]

[0678] <First Step: Synthesis of Butoxycarbonyl Trifluoromethanesulfonamide>

[0679] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (5.0 g, 33.5 mmol), pyridine (5.31 g, 67.1 mmol), 4-dimethylaminopyridine (0.82 g, 6.7 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert methyl chloroformate into butyl chloroformate (9.16 g, 67.1 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[0680] Thus, butoxycarbonyltrifluoromethylsulfonamide (7.32 g, 29.4 mmol, yield 88%) was obtained as the 27th white solid.

[0681] The following shows the 27th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0682] 1 H-NMR: δ0.88 (t, J=4.6Hz, 3H), 1.12-1.14 (m, 2H), 1.40-1.60 (m, 2H), 3.88 (t, J=6.6Hz, 2H), 8.94 (br, 1H)

[0683] <Second Step: Synthesis of Lithium Butoxycarbonyl Trifluoromethanesulfonamide (I-14)>

[0684] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using butoxycarbonyltrifluoromethylsulfonamide (2.50 g, 10.03 mmol), diethyl ether (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.7 mL, 10.03 mmol).

[0685] Thus, lithium butoxycarbonyl trifluoromethylsulfonamide (2.21 g, 8.66 mmol, yield 86%) was obtained as the 28th white solid.

[0686] The following shows the 28th white solid 1The measurement results were obtained by H-NMR (DMSO-d6).

[0687] 1 H-NMR: δ0.87 (t, J=7.2Hz, 3H), 1.15-1.55 (m, 4H), 3.79 (t, J=6.6Hz, 2H)

[0688] [Synthesis Example 15]

[0689] Phenoxycarbonyl trifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-15)] was synthesized as follows.

[0690] [Chemical Formula 34]

[0691]

[0692] <First Step: Synthesis of Phenoxycarbonyl Trifluoromethanesulfonamide>

[0693] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (3.0 g, 20.1 mmol), pyridine (3.18 g, 40.2 mmol), 4-dimethylaminopyridine (0.49 g, 4.0 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into phenyl chloroformate (3.15 g, 20.1 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[0694] Thus, phenoxycarbonyl trifluoromethylsulfonamide (1.83 g, 6.8 mmol, yield 34%) was obtained as the 29th white solid.

[0695] The following shows the 29th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0696] 1 H-NMR: δ6.70-6.85 (m, 3H), 7.16 (t, J=7.8Hz, 2H), 9.33 (br, 1H)

[0697] <Second Step: Synthesis of Lithium Phenoxycarbonyl Trifluoromethanesulfonamide (I-15)>

[0698] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using phenoxycarbonyl trifluoromethylsulfonamide (1.73 g, 6.43 mmol), diethyl ether (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (4.9 mL, 6.43 mmol).

[0699] Thus, phenoxycarbonyl trifluoromethylsulfonamide lithium (0.78 g, 2.83 mmol, yield 44%) was obtained as the 30th white solid.

[0700] The following shows the 30th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0701] 1 H-NMR: δ5.98 (t, J=6.9Hz, 1H), 6.23 (d, J=7.6Hz, 2H), 6.76 (t, J=7.4Hz, 2H)

[0702] [Synthesis Example 16]

[0703] Lithium methoxycarbonylmethylsulfonamide represented by the following structural formula [Synthetic Compound (I-16)] was synthesized as follows.

[0704] [Chemical Formula 35]

[0705]

[0706] <First Step: Synthesis of Methoxycarbonylmethanesulfonamide>

[0707] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), methyl chloroformate (19.87 g, 210 mmol), triethylamine (21.28 g, 210 mmol), 4-dimethylaminopyridine (2.57 g, 21 mmol), and tetrahydrofuran (200 mL) as a solvent were used to convert trifluoromethanesulfonamide into methanesulfonamide (10 g, 105 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[0708] Thus, methoxycarbonylmethylsulfonamide (0.65 g, 4.24 mmol, yield 4%) was obtained as the 31st white solid.

[0709] The following shows the 31st white solid 1 The measurement results were obtained by H-NMR (CD3OD-d4).

[0710] 1 H-NMR: δ3.24(s, 3H), 3.77(s, 3H)

[0711] <Second Step: Synthesis of Lithium Methoxycarbonylmethanesulfonamide (I-16)>

[0712] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using methoxycarbonylmethylsulfonamide (0.50 g, 3.25 mmol), tetrahydrofuran (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.5 mL, 3.25 mmol).

[0713] Thus, lithium methoxycarbonylmethylsulfonamide (0.31 g, 1.96 mmol, yield 60%) was obtained as the 32nd white solid.

[0714] The following shows the 32nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0715] 1 H-NMR: δ2.61(s, 3H), 3.27(s, 3H)

[0716] [Synthesis Example 17]

[0717] Lithium tert-butoxycarbonylmethylsulfonamide represented by the following structural formula [Synthetic Compound (I-17)] was synthesized as follows.

[0718] [Chemical Formula 36]

[0719]

[0720] <First step: Synthesis of tert-butoxycarbonylmethylsulfonamide)

[0721] In the first step of Synthesis Example 16 (synthesis of compound (I-16)), methanesulfonamide (4.0 g, 42.1 mmol), triethylamine (5.11 g, 210 mmol), 4-dimethylaminopyridine (0.62 g, 5.1 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert methyl chloroformate into di-tert-butyl dioxide (9.18 g, 42.1 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 16.

[0722] Thus, tert-butoxycarbonylmethylsulfonamide (5.22 g, 26.7 mmol, yield 64%) was obtained as the 33rd white solid.

[0723] The following shows the 33rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0724] 1 H-NMR: δ1.44(s, 9H), 3.20(s, 3H)

[0725] <Second Step: Synthesis of Lithium tert-Butoxycarbonylmethanesulfonamide (I-17)>

[0726] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using tert-butoxycarbonylmethylsulfonamide (5.0 g, 25.6 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (19.7 mL, 25.6 mmol).

[0727] Thus, lithium tert-butoxycarbonyl trifluoromethylsulfonamide (4.91 g, 24.5 mmol, yield 95%) was obtained as the 34th white solid.

[0728] The following shows the 34th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0729] 1 H-NMR: δ1.30 (s, 9H), 2.64 (s, 3H)

[0730] [Synthesis Example 18]

[0731] The lithium phenoxycarbonylmethylsulfonamide represented by the following structural formula [Synthetic Compound (I-18)] was synthesized as follows.

[0732] [Chemical Formula 37]

[0733]

[0734] <First Step: Synthesis of Phenoxycarbonylmethylsulfonamide>

[0735] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), methanesulfonamide (3.0 g, 31.5 mmol), pyridine (4.99 g, 63.1 mmol), 4-dimethylaminopyridine (0.77 g, 6.3 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into phenyl chloroformate (5.93 g, 37.8 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[0736] Thus, phenoxycarbonylmethylsulfonamide (3.25 g, 15.1 mmol, yield 48%) was obtained as the 35th white solid.

[0737] The following shows the 35th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0738] 1H-NMR: δ3.31 (s, 3H), 7.22 (d, J=8.4Hz, 2H), 7.25-7.50 (m, 3H)

[0739] <Second Step: Synthesis of Lithium Phenoxycarbonylmethylsulfonamide (I-18)>

[0740] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using phenoxycarbonylmethylsulfonamide (2.11 g, 9.8 mmol), tetrahydrofuran (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.5 mL, 9.8 mmol).

[0741] Thus, lithium phenoxycarbonylmethylsulfonamide (1.96 g, 8.9 mmol, yield 90%) was obtained as the 36th white solid.

[0742] The following shows the 36th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0743] 1 H-NMR: δ3.31 (s, 3H), 6.97 (d, J=8.6Hz, 2H), 7.06 (t, J=7.3Hz, 1H), 7.28 (t, J=7.8Hz, 2H)

[0744] [Synthesis Example 19]

[0745] Lithium acetylethoxysulfonamide represented by the following structural formula [Synthetic Compound (I-19)] was synthesized as follows.

[0746] [Chemical Formula 38]

[0747]

[0748] <First Step: Synthesis of Acetoethoxysulfonamide>

[0749] According to the patent document (International Publication No. 2017 / 156179), acetylethoxysulfonamidoethyl was synthesized.

[0750] A 200 mL four-necked flask purged with nitrogen was charged with chlorosulfonyl isocyanate (7.08 g, 50 mmol) and dichloromethane (100 mL) as a solvent. The temperature was maintained at 0°C, and acetic acid (3.0 g, 50 mmol) was added. The mixture was returned to room temperature and stirred for 6 hours to allow the reaction to proceed. After the reaction was completed, the solvent was concentrated and removed to obtain a white solid. Tetrahydrofuran (50 mL) was added to the four-necked flask to prepare a first reaction solution, which was then maintained at 0°C.

[0751] Separately, ethanol (2.92 g, 63.5 mmol), pyridine (5.02 g, 63.5 mmol), and 4-dimethylaminopyridine (0.78 g, 6.4 mmol) were added to tetrahydrofuran (50 mL) to prepare a second reaction solution. This second reaction solution was added to the four-necked flask containing the first reaction solution at 0°C over 10 minutes, then returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove the hydrochloride, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0752] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0753] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0754] Thus, acetylethoxysulfonamide (2.87 g, 17.2 mmol, yield 56%) was obtained as the 37th white solid.

[0755] The following shows the 37th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0756] 1 H-NMR: δ1.28 (d, J=4.3Hz, 3H), 2.02 (s, 3H), 4.27 (q, J=4.3Hz, 2H), 12.04 (br, 1H)

[0757] <Second Step: Synthesis of Lithium Acetylethoxysulfonamide (I-19)>

[0758] A 200 mL four-necked flask purged with nitrogen was charged with acetylethoxysulfonamide (1.74 g, 10.4 mmol) and tetrahydrofuran (30 mL) as a solvent. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (8.0 mL, 10.4 mmol) was added over 5 minutes. The mixture was returned to room temperature and stirred for 3 hours to react. Then, n-hexane (30 mL) was added to precipitate a white solid No. 38 from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid No. 38 was distilled off under reduced pressure.

[0759] Thus, lithium acetylethoxysulfonamide (0.22 g, 1.27 mmol, yield 12%) was obtained as the 38th white solid.

[0760] The following shows the 38th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0761] 1 H-NMR: δ1.13 (t, J=7.2Hz, 3H), 1.71 (s, 3H), 3.86 (q, J=7.3Hz, 2H)

[0762] [Synthesis Example 20]

[0763] Ethoxysulfonyl-2,2,2-trifluoroacetylamide lithium represented by the following structural formula [Synthetic Compound (I-20)] was synthesized as follows.

[0764] [Chemical Formula 39]

[0765]

[0766] <First Step: Synthesis of Ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide>

[0767] According to the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, p. 677-680), ethyl sulfamate (6.45 g, 51.5 mmol, yield 62%) was synthesized.

[0768] In a 200 mL four-necked flask purged with nitrogen, ethyl sulfamate (2.05 g, 16.4 mmol), pyridine (1.56 g, 19.7 mmol), 4-dimethylaminopyridine (0.24 g, 2.0 mmol), and tetrahydrofuran (30 mL) as a solvent were placed. The mixture was kept at 0°C and trifluoroacetic anhydride (4.13 g, 19.7 mmol) was added over 10 minutes. The mixture was returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove the hydrochloride, and the resulting solution was washed. That is, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0769] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0770] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0771] Thus, ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (1.22 g, 5.52 mmol, yield 34%) was obtained as the 39th white solid.

[0772] The following shows the 39th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0773] 1 H-NMR: δ1.18 (t, J=4.5Hz, 3H), 3.98 (q, J=7.0Hz, 2H), 8.38 (br, 1H)

[0774] <Second Step: Synthesis of Lithium Ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (I-20))

[0775] In a 200 mL four-necked flask purged with nitrogen, ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (1.0 g, 4.5 mmol) and tetrahydrofuran (20 mL) as a solvent were placed. The temperature was maintained at -20 degrees Celsius. After adding a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (3.5 mL, 4.5 mmol) over 5 minutes, the mixture was returned to room temperature and stirred for 3 hours to react. Then, n-hexane (20 mL) was added to remove a white solid from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting solid was distilled off under reduced pressure.

[0776] Thus, lithium ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (0.12 g, 0.53 mmol, yield 12%) was obtained as the 40th white solid.

[0777] The following shows the 40th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0778] 1 H-NMR: δ1.08 (dt, J=7.0Hz, 1.1Hz, H), 3.68 (dq, J=7.0Hz, 1.1Hz, 2H)

[0779] [Synthesis Example 21]

[0780] Lithium propionyl-(2,2,2-trifluoroethoxy)sulfonamide represented by the following structural formula [Synthetic Compound (I-21)] was synthesized as follows.

[0781] [Chemical Formula 40]

[0782]

[0783] <First Step: Synthesis of Propionyl-(2,2,2-trifluoroethoxy)sulfonamide>

[0784] According to the patent document (International Publication No. 2017 / 156179), propionyl-(2,2,2-trifluoroethoxy)sulfonamide was synthesized.

[0785] A 200 mL four-necked flask purged with nitrogen was charged with chlorosulfonyl isocyanate (14.15 g, 100 mmol) and dichloromethane (100 mL) as a solvent. The temperature was maintained at 0°C, and propionic acid (7.41 g, 100 mmol) was added. The mixture was returned to room temperature and stirred for 6 hours to allow the reaction to proceed. After the reaction was completed, the solvent was concentrated and removed to obtain a white solid. Tetrahydrofuran (100 mL) was added to the four-necked flask to prepare a third reaction solution, which was then maintained at 0°C.

[0786] Separately, 2,2,2-trifluoroethanol (12.0 g, 120 mmol), triethylamine (20.24 g, 200 mmol), and 4-dimethylaminopyridine (2.44 g, 20 mmol) were added to tetrahydrofuran (100 mL) to prepare a fourth reaction solution. The fourth reaction solution was added to a four-necked flask containing the third reaction solution at 0°C over 10 minutes, then returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove the hydrochloride, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0787] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0788] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0789] Thus, propionyl-(2,2,2-trifluoroethoxy)sulfonamide (11.63 g, 49.5 mmol, yield 50%) was obtained as the 41st white solid.

[0790] The following shows the 41st white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0791] 1 H-NMR: δ1.00 (t, J=7.4Hz, 3H), 2.32 (q, J=7.8Hz, 2H), 4.93 (q, J=8.6Hz, 2H)

[0792] <Second Step: Synthesis of Lithium Propionyl-(2,2,2-trifluoroethoxy)sulfonamide (I-21)>

[0793] A 200 mL four-necked flask purged with nitrogen was charged with propionyl-(2,2,2-trifluoroethoxy)sulfonamide (1.75 g, 7.4 mmol) and tetrahydrofuran (30 mL) as a solvent. The mixture was kept at -20 degrees Celsius and, over 5 minutes, a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (5.7 mL, 7.4 mmol) was added. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (30 mL) was added to precipitate a white solid (No. 42) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 42) was removed by distillation under reduced pressure.

[0794] Thus, lithium propionyl-(2,2,2-trifluoroethoxy)sulfonamide (0.79 g, 3.28 mmol, yield 44%) was obtained as the 42nd white solid.

[0795] The following shows the 42nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0796] 1 H-NMR: δ0.91 (t, J=7.6Hz, 3H), 1.98 (q, J=7.6Hz, 2H), 4.44 (q, J=6.5Hz, 2H)

[0797] [Synthesis Example 22]

[0798] Benzoyl-(2,2,2-trifluoroethoxy)sulfonamide lithium represented by the following structural formula [Synthetic Compound (I-22)] was synthesized as follows.

[0799] [Chemical Formula 41]

[0800]

[0801] <First Step: Synthesis of Benzoyl-(2,2,2-trifluoroethoxy)sulfonamide>

[0802] According to the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, p. 677-680), 2,2,2-trifluoroethylaminosulfate (12.4 g, 69.2 mmol, yield 69%) was synthesized.

[0803] In a 200 mL four-necked flask purged with nitrogen, 2,2,2-trifluoroethyl ethyl sulfamate (2.50 g, 14.0 mmol), triethylamine (2.82 g, 27.9 mmol), 4-dimethylaminopyridine (0.34 g, 2.8 mmol), and tetrahydrofuran (50 mL) as a solvent were placed. The mixture was kept at 0°C and benzoyl chloride (2.35 g, 16.8 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove the hydrochloride, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0804] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0805] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0806] Thus, benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (3.22 g, 11.37 mmol, yield 81%) was obtained as the 43rd white solid.

[0807] The following shows the 43rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0808] 1 H-NMR: δ5.01 (q, J=8.6Hz, 2H), 7.52 (t, J=7.8Hz, 2H), 7.65 (t, J=7.0Hz, 1H), 7.94 (d, J=8.4Hz, 2H)

[0809] <Second Step: Synthesis of Lithium Benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (I-22)>

[0810] Benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (2.06 g, 7.3 mmol) and tetrahydrofuran (20 mL) as a solvent were placed in a 200 mL four-necked flask purged with nitrogen. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (5.6 mL, 7.3 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (20 mL) was added to precipitate a white solid (No. 44) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 44) was distilled off under reduced pressure.

[0811] Thus, lithium benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (1.13 g, 3.9 mmol, yield 54%) was obtained as the 44th white solid.

[0812] The following shows the 44th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0813] 1 H-NMR: δ4.58 (q, J=8.9Hz, 2H), 7.52 (t, J=7.8Hz, 2H), 7.25-7.50 (m, 3H), 7.93 (d, J=7.6Hz, 2H)

[0814] [Synthesis Example 23]

[0815] Benzoylethoxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-23)] was synthesized as follows.

[0816] [Chemical Formula 42]

[0817]

[0818] <First Step: Synthesis of Benzoylethoxysulfonamide>

[0819] In the first step of Synthesis Example 20 (Synthesis of Compound (I-20)), ethyl aminosulfate (2.02 g, 16.1 mmol), 4-dimethylaminopyridine (0.39 g, 3.2 mmol), and tetrahydrofuran (30 mL) as a solvent were used, trifluoroacetic anhydride was changed to benzoyl chloride (2.72 g, 19.4 mmol), and pyridine was changed to triethylamine (3.27 g, 32.3 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 20.

[0820] Thus, benzoylethoxysulfonamide (1.95 g, 16.14 mmol, yield 53%) was obtained as the 45th white solid.

[0821] The following shows the 45th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0822] 1 H-NMR: δ1.32 (t, J=7.2Hz, 2H), 4.38 (q, J=7.3Hz, 2H), 7.53 (t, J=7.6Hz, 2H), 7.60 (t, J=7.4Hz, 2H), 7.92 (d, J=7.4Hz, 2H), 12.48 (br, 1H)

[0823] <Second Step: Synthesis of Lithium Benzoylethoxysulfonamide (I-23)>

[0824] Benzoylethoxysulfonamide (1.74 g, 7.6 mmol) and tetrahydrofuran (20 mL) as a solvent were placed in a 200 mL four-necked flask purged with nitrogen. The mixture was kept at -20°C and, over 5 minutes, a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (5.8 mL, 7.6 mmol) was added. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (20 mL) was added to precipitate a white solid (No. 46) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 46) was distilled off under reduced pressure.

[0825] Thus, lithium benzoylethoxysulfonamide (1.29 g, 5.5 mmol, yield 72%) was obtained as the 46th white solid.

[0826] The following shows the 46th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0827] 1 H-NMR: δ1.17 (t, J=7.2Hz, 2H), 3.96 (t, J=7.0Hz, 2H), 7.25-7.45 (m, 3H), 7.91 (d, J=7.0Hz, 2H)

[0828] [Synthesis Example 24]

[0829] Acetylphenoxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-24)] was synthesized as follows.

[0830] [Chemical Formula 43]

[0831]

[0832] <First Step: Synthesis of Phenylsulfamate>

[0833] According to the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, p. 677-680), aminosulfonyl chloride was synthesized.

[0834] A fifth reaction solution was prepared by placing sulfamoyl chloride (32.1 g, 278 mmol) and tetrahydrofuran (300 mL) as a solvent in a 200 mL four-necked flask purged with nitrogen, and the temperature was maintained at 0°C.

[0835] Separately, phenol (26.2 g, 278 mmol) and sodium hydride (6.67 g, 278 mmol) were added to tetrahydrofuran (100 mL) at 0°C to prepare a sixth reaction solution. The sixth reaction solution was added to the four-necked flask in which the fifth reaction solution was prepared at 0°C over 30 minutes, then returned to room temperature and stirred for 6 hours to react. The resulting reaction solution was then filtered to remove salts, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and extraction and washing were performed using a separatory funnel.

[0836] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0837] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0838] Thus, phenyl sulfamate (18.5 g, 107 mmol, yield 38%) was obtained as the 47th white solid.

[0839] The following shows the 47th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0840] 1 H-NMR: δ1.41 (t, J=7.0Hz, 3H), 4.29 (q, J=7.3Hz, 2H), 4.91 (br, 2H)

[0841] The reaction formula in the first step of Synthesis Example 24 is shown below.

[0842] [Chemical Formula 44]

[0843]

[0844] <Second step: Synthesis of acetylphenoxysulfonamide)

[0845] In the first step of Synthesis Example 2 (synthesis of compound (I-10)), pyridine (4.99 g, 63.1 mmol), 4-dimethylaminopyridine (0.77 g, 6.3 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methanesulfonamide into phenyl aminosulfonate (2.68 g, 15.5 mmol), and methyl chloroformate into acetyl chloride (1.46 g, 18.6 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[0846] Thus, acetylphenoxysulfonamide (2.11 g, 9.8 mmol, yield 63%) was obtained as a black solid.

[0847] The black solid is shown below 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0848] 1 H-NMR: δ2.05 (s, 3H), 7.27 (t, J=8.6Hz, 2H), 7.35-7.60 (m, 3H), 12.44 (br, 1H)

[0849] <Third Step: Synthesis of Lithium Acetylphenoxysulfonamide (I-24)>

[0850] A 200 mL four-necked flask purged with nitrogen was charged with acetylphenoxysulfonamide (2.11 g, 9.8 mmol) and tetrahydrofuran (20 mL) as a solvent. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (7.5 mL, 9.8 mmol) was added over 5 minutes. The mixture was returned to room temperature and stirred for 3 hours to react. Then, n-hexane (20 mL) was added to precipitate a white solid (No. 48) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 48) was distilled off under reduced pressure.

[0851] Thus, lithium acetylphenoxysulfonamide (1.83 g, 8.27 mmol, yield 84%) was obtained as the 48th white solid.

[0852] The following shows the 48th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0853] 1 H-NMR: δ1.72 (s, 3H), 7.05-7.20 (m, 3H), 7.30 (t, J=5.1Hz, 2H)

[0854] [Synthesis Example 25]

[0855] Benzoylphenoxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-25)] was synthesized as follows.

[0856] [Chemical Formula 45]

[0857]

[0858] <First Step: Synthesis of Phenylsulfamate>

[0859] Phenyl sulfamate was obtained by the same method as in the first step of Synthesis Example 24 (Synthesis of Compound (I-24)).

[0860] <Second Step: Synthesis of Benzoylphenoxysulfonamide>

[0861] The 49th white solid was synthesized by the same method as the second step in Synthesis Example 24 (synthesis of compound (I-24)), using phenylaminosulfonate (4.10 g, 23.7 mmol), 4-dimethylaminopyridine (0.58 g, 5.8 mmol), and tetrahydrofuran (50 mL) as a solvent, changing acetyl chloride to benzoyl chloride (3.99 g, 28.4 mmol), and changing pyridine to triethylamine (4.79 g, 47.3 mmol). Otherwise, the same method as the first step in Synthesis Example 24 was used to synthesize the 49th white solid.

[0862] Thus, benzoylphenoxysulfonamide (4.93 g, 17.8 mmol, yield 75%) was obtained as the 49th white solid.

[0863] The following shows the 49th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0864] 1 H-NMR: δ7.29 (d, J=8.4Hz, 2H), 7.30-7.70 (m, 6H), 7.89 (d, J=7.3Hz, 2H)

[0865] <Third Step: Synthesis of Lithium Benzoylphenoxysulfonamide (I-25)>

[0866] Benzoylphenoxysulfonamide (3.12 g, 11.25 mmol) and tetrahydrofuran (30 mL) as a solvent were placed in a 200 mL four-necked flask purged with nitrogen. The mixture was kept at -20°C and, over 5 minutes, a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (8.7 mL, 11.25 mmol) was added. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (30 mL) was added to precipitate a white solid from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid was distilled off under reduced pressure.

[0867] Thus, lithium benzoylphenoxysulfonamide (2.04 g, 7.20 mmol, yield 64%) was obtained as the 50th white solid.

[0868] The following shows the 50th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0869] 1 H-NMR: δ7.05-7.45 (m, 8H), 7.90 (d, J=7.6Hz, 2H)

[0870] [Synthesis Example 26]

[0871] Ethoxycarbonylethoxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-26)] was synthesized as follows.

[0872] [Chemical Formula 46]

[0873]

[0874] <First Step: Synthesis of Ethoxycarbonylethoxysulfonamide>

[0875] In the four-necked bottle of 500mL that nitrogen replaces, is connected with serpentine condenser pipe, chlorosulfonyl isocyanate (4.00g, 28.3mmol) and dichloromethane (100mL) as solvent are loaded, remain at room temperature, add ethanol (3.26g, 70.8mmol) and triethylamine (2.86g, 28.3mmol), stir and react in reflux temperature. After 4 hours, stopped reaction, cool to room temperature.Then, obtained reaction product is cleaned. That is, for reaction solution, add distilled water 100mL, add ethyl acetate 100mL, utilize separating funnel to carry out extraction cleaning.

[0876] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0877] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0878] Thus, ethoxycarbonylethoxysulfonamide (5.27 g, 11.3 mmol, yield 40%) was obtained as the 51st white solid.

[0879] The measurement results of the 51st white solid obtained by 1H-NMR (CDCl 3 ) are shown below.

[0880] 1H-NMR: δ1.32 (t, J=7.0Hz, 3H), 1.44 (t, J=7.0Hz, 3H), 4.28 (q, J=7.0Hz, 3H), 4.47 (q, J=7.0Hz, 3H), 7.53 (br, 1H)

[0881] The reaction formula in the first step of Synthesis Example 26 is shown below.

[0882] [Chemical Formula 47]

[0883]

[0884] <Second Step: Synthesis of Lithium Ethoxycarbonylethoxysulfonamide (I-26)>

[0885] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using ethoxycarbonylethoxysulfonamide (1.02 g, 5.17 mmol), tetrahydrofuran (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.50 mL, 4.55 mmol).

[0886] Thus, lithium ethoxycarbonylethoxysulfonamide (258 mg, 1.29 mmol, yield 25%) was obtained as the 52nd white solid.

[0887] The following shows the 52nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0888] 1 H-NMR: δ1.07 (t, J=7.3Hz, 3H), 1.13 (t, J=7.3Hz, 3H), 3.77 (q, J=7.3Hz, 3H), 3.85 (q, J=7.3Hz, 3H)

[0889] [Synthesis Example 27]

[0890] Ethoxycarbonyl-2,2,2-trifluoroethoxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-27)] was synthesized as follows.

[0891] [Chemical Formula 48]

[0892]

[0893] <First Step: Synthesis of Ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide>

[0894] According to the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, p. 677-680), 2,2,2-trifluoroethylaminosulfate (12.4 g, 69.2 mmol, yield 69%) was synthesized.

[0895] In the first step of Synthesis Example 22 (Synthesis of Compound (I-22)), 2,2,2-trifluoroethylaminosulfonate (2.55 g, 14.2 mmol), 4-dimethylaminopyridine (0.35 g, 2.85 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert benzoyl chloride into ethyl chloroformate (3.09 g, 28.5 mmol) and triethylamine into pyridine (2.25 g, 28.5 mmol). Except for this, the 53rd white solid was synthesized by the same method as the first step of Synthesis Example 22.

[0896] Thus, ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (2.28 g, 9.08 mmol, yield 64%) was obtained as the 53rd white solid.

[0897] The following shows the 53rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0898] 1 H-NMR: δ1.22 (t, J=7.0Hz, 3H), 4.17 (q, J=6.8Hz, 2H), 4.93 (q, J=8.4Hz, 2H)

[0899] <Second Step: Synthesis of Lithium Ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (I-27)>

[0900] A 200 mL four-necked flask purged with nitrogen was charged with ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (2.0 g, 7.96 mmol) and tetrahydrofuran (30 mL) as a solvent. The temperature was maintained at -20°C, and lithium bis(trimethylsilyl)amide (1.3 M) and a tetrahydrofuran solution (6.1 mL, 7.96 mmol) were added over 5 minutes. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (30 mL) was added to precipitate a white solid from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid was distilled off under reduced pressure.

[0901] Thus, lithium ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.95 g, 7.58 mmol, yield 95%) was obtained as the 54th white solid.

[0902] The following shows the 54th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0903] 1H-NMR: δ1.08 (t, J=4.5Hz, 3H), 3.81 (q, J=6.8Hz, 2H), 4.40 (q, J=9.2Hz, 2H)

[0904] [Synthesis Example 28]

[0905] Lithium (2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide represented by the following structural formula was synthesized as follows [Synthetic Compound (I-28)].

[0906] [Chemical Formula 49]

[0907]

[0908] <First Step: Synthesis of 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide>

[0909] In a 100 mL four-necked flask purged with nitrogen and connected to a serpentine condenser, 2,2,2-trifluoroethanol (5.73 g, 57.3 mmol) and chlorobenzene (13 mL) as a solvent were placed, kept at room temperature, chlorosulfonyl isocyanate (4.05 g, 28.6 mmol) was added, and the mixture was stirred at reflux temperature to react. After 12 hours, the reaction was stopped and cooled to room temperature. The reaction solution was concentrated under reduced pressure, and the resulting crude product was separated and purified by flash column chromatography using hexane / ethyl acetate solvent.

[0910] Thus, 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (7.34 g, 24.1 mmol, yield 84%) was obtained as a first colorless transparent oil.

[0911] The following shows the first colorless transparent oil 1 The measurement results were obtained by H-NMR (CDCl3).

[0912] 1 H-NMR: δ4.59 (d, J=8.1Hz, 2H), 4.73 (d, J=7.6Hz, 2H), 8.28 (br, 1H)

[0913] <Second Step: Synthesis of Lithium (2,2,2-Trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide (I-28)>

[0914] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.50 g, 4.92 mmol), tetrahydrofuran (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.75 mL, 4.88 mmol).

[0915] Thus, lithium (2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.51 g, 4.85 mmol, yield 99%) was obtained as the 55th white solid.

[0916] The following shows the 55th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0917] 1 H-NMR: δ4.43 (q, J=9.5Hz, 2H), 4.44 (q, J=9.0Hz, 2H)

[0918] [Synthesis Example 29]

[0919] Benzoyl-(2,2,2-trifluoroethoxy)sulfonamide lithium represented by the following structural formula [Synthetic Compound (I-29)] was synthesized as follows.

[0920] [Chemical Formula 50]

[0921]

[0922] <First Step: Synthesis of Phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide>

[0923] According to the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, p. 677-680), 2,2,2-trifluoroethylaminosulfate (12.4 g, 69.2 mmol, yield 69%) was synthesized.

[0924] In the first step of Synthesis Example 27 (Synthesis of Compound (I-27)), 2,2,2-trifluoroethylaminosulfonate (3.19 g, 17.81 mmol), pyridine (2.82 g, 35.6 mmol), 4-dimethylaminopyridine (0.44 g, 3.56 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert ethyl chloroformate into phenyl chloroformate (3.35 g, 21.4 mmol). Except for this, the 56th white solid was synthesized by the same method as the first step of Synthesis Example 27.

[0925] Thus, phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.97 g, 6.58 mmol, yield 37%) was obtained as the 56th white solid.

[0926] The following shows the 56th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0927] 1 H-NMR: δ4.66 (q, J=8.6Hz, 2H), 6.75 (d, J=8.6Hz, 2H), 7.00-7.40 (m, 3H), 8.00 (br, 1H)

[0928] <Second Step: Synthesis of Lithium Phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (I-29)>

[0929] A 200 mL four-necked flask purged with nitrogen was charged with phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.97 g, 6.58 mmol) and tetrahydrofuran (30 mL) as a solvent. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (5.1 mL, 6.58 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (30 mL) was added to precipitate a white solid (No. 57) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 57) was distilled off under reduced pressure.

[0930] Thus, phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide lithium (1.71 g, 5.60 mmol, yield 85%) was obtained as the 57th white solid.

[0931] The following shows the 57th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0932] 1 H-NMR: δ4.47 (q, J=8.9Hz, 2H), 6.99 (d, J=8.4Hz, 2H), 7.11 (t, J=7.6Hz, 2H), 7.31 (t, J=5.0Hz, 2H)

[0933] [Synthesis Example 30]

[0934] Ethoxycarbonyl-p-tolyloxysulfonamide lithium represented by the following structural formula [Synthetic Compound (I-30)] was synthesized as follows.

[0935] [Chemical Formula 51]

[0936]

[0937] <First Step: Synthesis of p-Tolyloxycarbonylchlorosulfonamide>

[0938] With reference to non-patent literature (Picard, JA et al., J. Med. Chem., 1996, 39, 1243), p-tolyloxycarbonyl chlorosulfonamide was synthesized.

[0939] A 100 mL four-necked flask connected to a serpentine condenser and purged with nitrogen was charged with p-cresol (7.04 g, 65.1 mmol) and chlorobenzene (20 mL) as a solvent. The mixture was kept at room temperature, and chlorosulfonyl isocyanate (9.21 g, 65.1 mmol) was added. The mixture was stirred at room temperature for 1 hour to react, whereupon a white solid, No. 58, precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid, No. 58, was distilled off under reduced pressure.

[0940] Thus, p-tolyloxycarbonylchlorosulfonamide (14.6 g, 58.5 mmol, yield 90%) was obtained as the 58th white solid.

[0941] The following shows the 58th white solid 1 The measurement results were obtained by H-NMR (CDCl3).

[0942] 1 H-NMR: δ2.37 (s, 3H), 7.09 (d, J=8.5Hz, 2H), 7.22 (d, J=8.5Hz, 2H)

[0943] <Second Step: Synthesis of Ethoxycarbonyl-p-Tolyloxysulfonamide>

[0944] Ethoxycarbonyl-p-tolyloxysulfonamide was synthesized with reference to non-patent literature (Picard, JA et al., J. Med. Chem., 1996, 39, 1243).

[0945] In a 100mL four-necked bottle substituted with nitrogen and connected to a serpentine condenser, tolyloxycarbonyl chlorosulfonamide (5.00g, 20.0mmol) and chlorobenzene (30mL) as a solvent were loaded and reacted at reflux temperature for 12 hours. The mixture was then cooled to room temperature, and ethanol (1.85g, 40.2mmol) was added, which was stirred at room temperature and reacted. After 2 hours, the reaction was stopped and the resulting reaction product was cleaned. That is, 30mL of distilled water was added to the reaction solution, 30mL of ethyl acetate was added, and a separating funnel was used for extraction and cleaning.

[0946] The above-mentioned water washing was repeated twice, and magnesium sulfate was added to the obtained organic layer to dry it, and then it was concentrated under reduced pressure.

[0947] The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent.

[0948] Thus, ethoxycarbonyl-p-tolyloxysulfonamide (4.03 g, 15.5 mmol, yield 78%) was obtained as a second colorless transparent oil.

[0949] The following shows the second colorless transparent oil 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0950] 1 H-NMR: δ1.23 (t, J=7.0Hz, 3H), 2.32 (s, 3H), 4.20 (q, J=7.0Hz, 2H), 7.14 (d, J=8.4Hz, 2H), 7.30 (d, J=8.4Hz, 2H)

[0951] <Third Step: Synthesis of Lithium Ethoxycarbonyl-p-Tolyloxysulfonamide (I-30)>

[0952] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using ethoxycarbonyl-p-tolyloxysulfonamide (2.54 g, 9.80 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.30 mL, 9.49 mmol).

[0953] Thus, lithium ethoxycarbonyl-p-tolyloxysulfonamide (1.11 g, 4.19 mmol, yield 43%) was obtained as a white solid No. 59.

[0954] The following shows the 59th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0955] 1 H-NMR: δ1.07 (t, J=7.0Hz, 3H), 2.26 (s, 3H), 3.80 (q, J=7.0Hz, 2H), 7.02 (d, J=8.6Hz, 2H), 7.09 (d, J=8.6Hz, 2H)

[0956] As described above, based on the results of Synthesis Example 30, ethoxycarbonyl-p-tolyloxysulfonamide lithium [Synthetic Compound (I-30)] was obtained according to the following reaction pathway.

[0957] [Chemical Formula 52]

[0958]

[0959] [Synthesis Example 31]

[0960] Lithium p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide represented by the following structural formula was synthesized as follows [Synthetic Compound (I-31)].

[0961] [Chemical Formula 53]

[0962]

[0963] <First Step: Synthesis of p-Tolyloxycarbonylchlorosulfonamide>

[0964] p-Tolyloxycarbonylchlorosulfonamide was synthesized by the same method as in the first step of Synthesis Example 30 (Synthesis of Compound (I-30)).

[0965] <Second Step: Synthesis of p-Tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide>

[0966] The reaction was carried out by the same method as the second step in Synthesis Example 30 (Synthesis of Compound (I-30)) using p-tolyloxycarbonylchlorosulfonamide (1.50 g, 6.01 mmol), chlorobenzene (10 mL) as a solvent, and 2,2,2-trifluoroethanol (0.60 g, 6.00 mmol).

[0967] Thus, p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (1.01 g, 3.22 mmol, yield 54%) was obtained as a third colorless transparent oil.

[0968] The following shows the third colorless transparent oil 1 The measurement results were obtained by H-NMR (CDCl3).

[0969] 1 H-NMR: δ2.37 (s, 3H), 4.62 (q, J=8.1Hz, 2H), 7.20 (m, 4H)

[0970] <Third Step: Synthesis of Lithium p-Tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (I-31)>

[0971] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (1.01 g, 3.22 mmol), tetrahydrofuran (15 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.30 mL, 2.99 mmol).

[0972] Thus, lithium p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (350 mg, 1.10 mmol, yield 34%) was obtained as the 60th white solid.

[0973] The following shows the 60th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0974] 1 H-NMR: δ2.26 (s, 3H), 4.43 (q, J=9.2Hz, 2H), 7.03 (d, J=8.6Hz, 2H), 7.10 (d, J=8.6Hz, 2H)

[0975] [Synthesis Example 32]

[0976] The lithium p-tolyloxycarbonyl-p-tolyloxysulfonamide represented by the following structural formula [Synthetic Compound (I-32)] was synthesized as follows.

[0977] [Chemical Formula 54]

[0978]

[0979] <First Step: Synthesis of p-tolyloxycarbonyl-p-tolyloxysulfonamide>

[0980] A fourth colorless transparent oil was synthesized by the same method as in the first step of Synthesis Example 28 (Synthesis of Compound (I-28)) except that p-cresol (6.20 g, 57.3 mmol) was replaced with trifluoroethanol.

[0981] Thus, p-tolyloxycarbonyl-p-tolyloxysulfonamide (9.10 g, 28.3 mmol, yield 99%) was obtained as the fourth colorless transparent oil.

[0982] The following shows the fourth colorless transparent oil 1 The measurement results were obtained by H-NMR (CDCl3).

[0983] 1H-NMR: δ2.37 (s, 3H), 2.38 (s, 3H), 7.05 (d, J=6.8Hz, 2H), 7.21 (m, 6H)

[0984] <Second Step: Synthesis of p-Tolyloxycarbonyl-p-Tolyloxysulfonamide Lithium (I-32)>

[0985] The reaction was carried out by the same method as the second step in Synthesis Example 1 (Synthesis of Compound (I-5)) using p-tolyloxycarbonyl-p-tolyloxysulfonamide (1.20 g, 3.73 mmol), tetrahydrofuran (20 mL) as a solvent, lithium bis(trimethylsilyl)amide (1.3 M), and tetrahydrofuran solution (2.60 mL, 3.38 mmol).

[0986] Thus, p-tolyloxycarbonyl-p-tolyloxysulfonamide lithium (798 mg, 2.42 mmol, yield 65%) was obtained as the 61st white solid.

[0987] The following shows the 61st white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0988] 1 H-NMR: δ2.27 (s, 3H), 2.28 (s, 3H), 6.82 (d, J=8.6Hz, 2H), 7.10 (m, 6H)

[0989] [Synthesis Example 33]

[0990] 4-Methylphenoxycarbonyltrifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-33)] was synthesized as follows.

[0991] [Chemical Formula 55]

[0992]

[0993] <First Step: Synthesis of 4-Methylphenoxycarbonyltrifluoromethylsulfonamide>

[0994] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (2.0 g, 13.4 mmol), pyridine (2.12 g, 26.8 mmol), 4-dimethylaminopyridine (0.33 g, 2.7 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into 4-methylphenyl chloroformate (2.52 g, 14.8 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[0995] Thus, 4-methylphenoxycarbonyltrifluoromethylsulfonamide (1.02 g, 3.6 mmol, yield 27%) was obtained as the fifth colorless transparent oil.

[0996] The following shows the fifth colorless transparent oil 1 The measurement results were obtained by H-NMR (DMSO-d6).

[0997] 1 H-NMR: δ6.61-6.66(m, 2H), 6.92-6.97(m, 2H), 9.06(br, 1H)

[0998] <Second Step: Synthesis of 4-Methylphenoxycarbonyltrifluoromethylsulfonamide Lithium (I-33)>

[0999] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using 4-methylphenoxycarbonyltrifluoromethylsulfonamide (1.02 g, 3.60 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.8 mL, 3.60 mmol).

[1000] Thus, 4-methylphenoxycarbonyl trifluoromethylsulfonamide lithium (0.76 g, 2.63 mmol, yield 73%) was obtained as the 62nd white solid.

[1001] The following shows the 62nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1002] 1 H-NMR: δ6.18-6.34(m, 2H), 6.58-6.66(m, 2H)

[1003] [Synthesis Example 34]

[1004] 4-Methoxyphenoxycarbonyl trifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-34)] was synthesized as follows.

[1005] [Chemical Formula 56]

[1006]

[1007] <First Step: Synthesis of 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide>

[1008] In the first step of Synthesis Example 2 (synthesis of compound (I-10)), trifluoromethanesulfonamide (1.60 g, 10.7 mmol), pyridine (1.70 g, 21.5 mmol), 4-dimethylaminopyridine (0.26 g, 2.1 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into 4-methoxyphenyl chloroformate (2.40 g, 12.9 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[1009] Thus, 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (1.55 g, 5.2 mmol, yield 48%) was obtained as the 63rd white solid.

[1010] The following shows the 63rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1011] 1 H-NMR: δ3.65 (s, 3H), 6.55-6.78 (m, 4H), 8.86 (br, 1H)

[1012] <Second Step: Synthesis of Lithium 4-Methoxyphenoxycarbonyl Trifluoromethylsulfonamide (I-34)>

[1013] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (0.95 g, 3.16 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.4 mL, 3.16 mmol).

[1014] Thus, lithium 4-methoxyphenoxycarbonyl trifluoromethylsulfonamide (0.79 g, 2.58 mmol, yield 82%) was obtained as the 64th white solid.

[1015] The following shows the 64th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1016] 1 H-NMR: δ3.55(s, 3H), 6.13-6.28(m, 2H), 6.43-6.52(m, 2H)

[1017] [Synthesis Example 35]

[1018] 4-Chlorophenoxycarbonyl trifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-35)] was synthesized as follows.

[1019] [Chemical Formula 57]

[1020]

[1021] <First Step: Synthesis of 4-chlorophenoxycarbonyltrifluoromethylsulfonamide>

[1022] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (2.0 g, 13.4 mmol), pyridine (2.12 g, 26.8 mmol), 4-dimethylaminopyridine (0.33 g, 2.7 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into 4-chlorophenyl chloroformate (3.07 g, 16.1 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[1023] Thus, 4-chlorophenoxycarbonyltrifluoromethylsulfonamide (1.54 g, 5.1 mmol, yield 38%) was obtained as the sixth colorless transparent oil.

[1024] The following shows the sixth colorless transparent oil 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1025] 1 H-NMR: δ6.74-6.79(m, 2H), 7.17-7.22(m, 2H)

[1026] <Second Step: Synthesis of Lithium 4-Chlorophenoxycarbonyl Trifluoromethylsulfonamide (I-35)>

[1027] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using 4-chlorophenoxycarbonyltrifluoromethylsulfonamide (1.54 g, 5.07 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.9 mL, 5.07 mmol).

[1028] Thus, lithium 4-chlorophenoxycarbonyl trifluoromethylsulfonamide (0.65 g, 2.10 mmol, yield 41%) was obtained as the 65th yellow solid.

[1029] The following shows the 65th yellow solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1030] 1 H-NMR: δ6.40-6.46(m, 2H), 6.84-6.90(m, 2H)

[1031] [Synthesis Example 36]

[1032] 4-Fluorophenoxycarbonyltrifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-36)] was synthesized as follows.

[1033] [Chemical Formula 58]

[1034]

[1035] <First Step: Synthesis of 4-fluorophenoxycarbonyltrifluoromethylsulfonamide>

[1036] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (1.94 g, 13.0 mmol), pyridine (2.06 g, 26.0 mmol), 4-dimethylaminopyridine (0.32 g, 2.6 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into 4-fluorophenyl chloroformate (2.50 g, 14.3 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 2.

[1037] Thus, 4-fluorophenoxycarbonyltrifluoromethylsulfonamide (2.02 g, 7.0 mmol, yield 54%) was obtained as the seventh colorless transparent oil.

[1038] The following shows the seventh colorless transparent oil 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1039] 1 H-NMR: δ6.71-6.76(m, 2H), 6.94-7.01(m, 2H), 9.34(br, 1H)

[1040] <Second Step: Synthesis of Lithium 4-Fluorophenoxycarbonyltrifluoromethylsulfonamide (I-36)>

[1041] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using 4-fluorophenoxycarbonyltrifluoromethylsulfonamide (2.02 g, 7.03 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.4 mL, 7.03 mmol).

[1042] Thus, lithium 4-fluorophenoxycarbonyl trifluoromethylsulfonamide (0.91 g, 3.10 mmol, yield 44%) was obtained as the 66th white solid.

[1043] The following shows the 66th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1044] 1 H-NMR: δ6.21-6.31(m, 2H), 6.58-6.68(m, 2H)

[1045] [Synthesis Example 37]

[1046] Allyloxycarbonyl trifluoromethylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-37)] was synthesized as follows.

[1047] [Chemical Formula 59]

[1048]

[1049] <First Step: Synthesis of Allyloxycarbonyl Trifluoromethylsulfonamide>

[1050] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), trifluoromethanesulfonamide (2.50 g, 16.8 mmol), pyridine (2.65 g, 33.5 mmol), 4-dimethylaminopyridine (0.41 g, 3.4 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert methyl chloroformate into allyl chloroformate (2.43 g, 20.1 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[1051] Thus, allyloxycarbonyl trifluoromethylsulfonamide (2.46 g, 10.6 mmol, yield 63%) was obtained as the 67th white solid.

[1052] The following shows the 67th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1053] 1 H-NMR: δ4.25-4.50(m, 2H), 4.95-5.32(m, 2H), 5.70-5.98(m, 1H), 9.66(br, 1H)

[1054] <Second Step: Synthesis of Lithium Allyloxycarbonyl Trifluoromethanesulfonamide (I-37)>

[1055] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using allyloxycarbonyl trifluoromethylsulfonamide (2.20 g, 9.44 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.3 mL, 9.44 mmol).

[1056] Thus, allyloxycarbonyl trifluoromethylsulfonamide lithium (1.58 g, 6.63 mmol, yield 70%) was obtained as the 68th white solid.

[1057] The following shows the 68th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1058] 1 H-NMR: δ4.25-4.40(m, 2H), 5.00-5.30(m, 2H), 5.85-5.96(m, 1H)

[1059] [Synthesis Example 38]

[1060] Lithium butoxycarbonyl-4-fluorophenylsulfonamide represented by the following structural formula [Synthetic Compound (I-38)] was synthesized as follows.

[1061] [Chemical Formula 60]

[1062]

[1063] <First Step: Synthesis of Butoxycarbonyl-4-fluorophenylsulfonamide>

[1064] In the first step of Synthesis Example 14 (synthesis of compound (I-14)), butyl chloroformate (2.34 g, 17.1 mmol), 4-dimethylaminopyridine (0.41 g, 3.4 mmol), and tetrahydrofuran (30 mL) as a solvent were used, trifluoromethanesulfonamide was changed to 4-fluorobenzenesulfonamide (2.50 g, 14.3 mmol), and pyridine was changed to triethylamine (2.89 g, 28.5 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 14.

[1065] Thus, butoxycarbonyl-4-fluorophenylsulfonamide (1.13 g, 4.1 mmol, yield 29%) was obtained as the 69th white solid.

[1066] The following shows the 69th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1067] 1 H-NMR: δ0.82 (t, J=7.0Hz, 3H), 1.05-1.30 (m, 2H), 1.35-1.55 (m, 2H), 3.98 (t, J=6.6Hz, 2H), 7.38-7.58 (m, 2H), 7.84-8.04 (m, 2H), 12.06 (br, 1H)

[1068] <Second Step: Synthesis of Lithium Butoxycarbonyl-4-fluorophenylsulfonamide (I-38)>

[1069] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using butoxycarbonyl-4-fluorophenylsulfonamide (1.01 g, 3.67 mmol), diethyl ether (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.8 mL, 3.67 mmol).

[1070] Thus, lithium butoxycarbonyl-4-fluorophenylsulfonamide (0.77 g, 2.72 mmol, yield 74%) was obtained as the 70th white solid.

[1071] The following shows the 70th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1072] 1 H-NMR: δ0.84 (t, J=7.2Hz, 3H), 1.15-1.30 (m, 2H), 1.30-1.45 (m, 2H), 3.65 (t, J=6.6Hz, 2H), 7.10-7.25 (m, 2H), 7.65-7.80 (m, 2H)

[1073] [Synthesis Example 39]

[1074] The lithium methoxycarbonyl-4-trifluoromethylphenylsulfonamide represented by the following structural formula [Synthetic Compound (I-39)] was synthesized as follows.

[1075] [Chemical Formula 61]

[1076]

[1077] <First Step: Synthesis of Methoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide>

[1078] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), methyl chloroformate (2.64 g, 28.0 mmol), 4-dimethylaminopyridine (0.61 g, 5.0 mmol), and tetrahydrofuran (100 mL) as a solvent were used to convert trifluoromethanesulfonamide into 4-(trifluoromethyl)benzenesulfonamide (5.24 g, 23.3 mmol), and pyridine into triethylamine (2.82 g, 28.0 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[1079] Thus, methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (5.30 g, 18.7 mmol, yield 80%) was obtained as the 71st white solid.

[1080] The following shows the 71st white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1081] 1 H-NMR: δ3.65 (s, 3H), 8.04 (d, J=9.1Hz, 2H), 8.18 (d, J=9.1Hz, 2H)

[1082] <Second Step: Synthesis of Lithium Methoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide (I-39)>

[1083] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.80 g, 6.36 mmol), tetrahydrofuran (30 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (4.64 mL, 6.03 mmol).

[1084] Thus, lithium methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (0.44 g, 1.52 mmol, yield 24%) was obtained as the 72nd white solid.

[1085] The following shows the 72nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1086] 1 H-NMR: δ2.31 (s, 3H), 7.65 (d, J=8.9Hz, 2H), 7.70 (d, J=8.9Hz, 2H)

[1087] [Synthesis Example 40]

[1088] Lithium methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide represented by the following structural formula [Synthetic Compound (I-40)] was synthesized as follows.

[1089] [Chemical Formula 62]

[1090]

[1091] <First Step: Synthesis of Methoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide>

[1092] In the first step of Synthesis Example 2 (Synthesis of Compound (I-10)), methyl chloroformate (1.18 g, 12.5 mmol), 4-dimethylaminopyridine (0.13 g, 1.0 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert trifluoromethanesulfonamide into 4-(trifluoromethoxy)benzenesulfonamide (2.50 g, 10.4 mmol), and pyridine into triethylamine (1.26 g, 12.5 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 2.

[1093] Thus, methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.10 g, 10.4 mmol, yield 100%) was obtained as the 73rd white solid.

[1094] The following shows the 73rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1095] 1 H-NMR: δ3.65 (s, 3H), 7.63 (d, J=9.3Hz, 2H), 8.10 (d, J=9.3Hz, 2H), 8.32 (br, 1H)

[1096] <Second Step: Synthesis of Lithium Methoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide (I-40)>

[1097] The reaction was carried out by the same method as the second step in Synthesis Example 2 (Synthesis of Compound (I-10)) using methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.10 g, 10.4 mmol), tetrahydrofuran (40 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.57 mL, 9.84 mmol).

[1098] Thus, lithium methylcarbonyl 4-(trifluoromethoxy)phenylsulfonamide (0.40 g, 1.31 mmol, yield 13%) was obtained as the 74th white solid.

[1099] The following shows the 74th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1100] 1 H-NMR: δ2.36 (s, 3H), 7.42 (d, J=9.0Hz, 2H), 7.74 (d, J=9.0Hz, 2H)

[1101] [Synthesis Example 41]

[1102] The lithium phenoxycarbonylethoxysulfonamide represented by the following structural formula [Synthetic Compound (I-41)] was synthesized as follows.

[1103] [Chemical Formula 63]

[1104]

[1105] <First Step: Synthesis of Phenoxycarbonylethoxysulfonamide>

[1106] In the first step of Synthesis Example 20 (Synthesis of Compound (I-20)), ethyl aminosulfate (1.80 g, 14.4 mmol), 4-dimethylaminopyridine (0.39 g, 3.2 mmol), and tetrahydrofuran (30 mL) as a solvent were used, trifluoroacetic anhydride was changed to phenyl chloroformate (2.70 g, 17.3 mmol), and pyridine was changed to triethylamine (2.91 g, 28.8 mmol). Except for this, the synthesis was carried out by the same method as the first step of Synthesis Example 20.

[1107] Thus, phenoxycarbonylethoxysulfonamide (2.19 g, 8.93 mmol, yield 62%) was obtained as the 75th white solid.

[1108] The following shows the 75th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1109] 1 H-NMR: δ1.43 (t, J=7.2Hz, 3H), 4.52 (q, J=7.2Hz, 2H), 7.12-7.46 (m, 5H)

[1110] <Second Step: Synthesis of Lithium Phenoxycarbonylethoxysulfonamide (I-41)>

[1111] A 200 mL four-necked flask purged with nitrogen was charged with phenoxycarbonylethoxysulfonamide (2.19 g, 8.9 mmol) and tetrahydrofuran (20 mL) as a solvent. The temperature was maintained at -20°C, and a solution of lithium bis(trimethylsilyl)amide (1.3 M) in tetrahydrofuran (6.9 mL, 8.9 mmol) was added over 5 minutes. The mixture was then returned to room temperature and stirred for 3 hours to react. Then, n-hexane (20 mL) was added to precipitate a white solid (No. 76) from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent in the resulting white solid (No. 76) was distilled off under reduced pressure.

[1112] Thus, lithium phenoxycarbonylethoxysulfonamide (2.11 g, 8.4 mmol, yield 94%) was obtained as the 76th white solid.

[1113] The following shows the 76th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1114] 1 H-NMR: δ1.16 (t, J=7.0Hz, 3H), 3.93 (q, J=7.3Hz, 2H), 6.92-7.12 (m, 3H), 7.24-7.34 (m, 2H)

[1115] [Synthesis Example 42]

[1116] Fluorosulfonylmethoxycarbonylamide lithium represented by the following structural formula [Synthetic Compound (I-42)] was synthesized as follows.

[1117] [Chemical Formula 64]

[1118]

[1119] <First Step: Synthesis of Fluorosulfonylmethoxycarbonylamide>

[1120] A 100 mL four-necked flask connected to a condenser coil and purged with nitrogen was charged with chlorosulfonyl isocyanate (9.72 g, 68.7 mmol) and acetonitrile (25 mL) as a solvent and cooled to 0°C. Methanol (2.00 g, 62.4 mmol) was added and the mixture was stirred at room temperature for 1 hour to react. Potassium difluoride (5.85 g, 74.9 mmol) was then added and the mixture was further stirred and reacted. The reaction was terminated after 2 hours.

[1121] The obtained reaction product was then washed by adding 50 mL of distilled water and 50 mL of hexane / ethyl acetate to the reaction solution, and extracting and washing was performed using a separatory funnel.

[1122] The above water washing was repeated twice, and all organic phases were combined and washed with saturated brine (20 mL). Magnesium sulfate was added to the obtained organic phase to dry it, and then concentrated under reduced pressure. Thus, a crude product of fluorosulfonylmethoxycarbonylamide (9.63 g) was obtained.

[1123] <Second Step: Synthesis of Lithium Fluorosulfonylmethoxycarbonylamide>

[1124] In a 100 mL four-necked flask purged with nitrogen, the crude product fluorosulfonylmethoxycarbonylamide (4.50 g) and methanol (25 mL) as a solvent were placed, and lithium carbonate (2.33 g, 31.5 mmol) was added, followed by stirring for 1 hour to react. The reaction solution was concentrated under reduced pressure, and ethyl acetate (20 mL) was added to prepare a suspension. The suspension was filtered using diatomaceous earth, and the filtrate was concentrated under reduced pressure. Dichloromethane (20 mL) was added, and when stirred at room temperature for 1 hour, a white solid precipitated. The solution was filtered under reduced pressure, and the residual solvent of the obtained white solid was distilled off under reduced pressure. Thus, lithium fluorosulfonylmethoxycarbonylamide (3.30 g, 20.2 mmol, 70% yield for 2 steps) was obtained as a white solid 77.

[1125] The following shows the 77th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1126] 1 H-NMR: δ 3.41 (s, 3H)

[1127] As described above, based on the results of Synthesis Example 42, lithium fluorosulfonylmethoxycarbonylamide was obtained according to the following reaction pathway [Synthetic Compound (I-42)].

[1128] [Chemical Formula 65]

[1129]

[1130] [Synthesis Example 43]

[1131] Fluorosulfonylethoxycarbonylamide lithium represented by the following structural formula [Synthetic Compound (I-43)] was synthesized as follows.

[1132] [Chemical Formula 66]

[1133]

[1134] <First Step: Synthesis of Fluorosulfonylethoxycarbonylamide>

[1135] In the first step of Synthesis Example 42 (Synthesis of Compound (I-42)), chlorosulfonyl isocyanate (8.45 g, 59.7 mmol), potassium difluoride (5.09 g, 65.2 mmol), and acetonitrile (25 mL) as a solvent were used, and ethanol (2.50 g, 54.3 mmol) was replaced with methanol. Synthesis was carried out by the same method as Synthesis Example 42. Thus, a crude product, fluorosulfonylethoxycarbonylamide (9.29 g), was obtained.

[1136] <Second Step: Synthesis of Lithium Fluorosulfonylethoxycarbonylamide>

[1137] The reaction was carried out by the same method as the second step in Synthesis Example 42 (Synthesis of Compound (I-42)) using the crude product fluorosulfonylethoxycarbonylamide (4.50 g), lithium carbonate (2.14 g, 29.0 mmol), and methanol (25 mL) as a solvent.

[1138] Thus, lithium fluorosulfonylethoxycarbonylamide (2.29 g, 12.9 mmol, 49% yield over two steps) was obtained as the 78th white solid.

[1139] The following shows the 78th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1140] 1 H-NMR: δ1.10 (t, J=6.8Hz, 3H), 3.84 (q, J=6.8Hz, 2H)

[1141] [Synthesis Example 44]

[1142] Fluorosulfonylpropoxycarbonylamide lithium represented by the following structural formula [Synthetic Compound (I-44)] was synthesized as follows.

[1143] [Chemical Formula 67]

[1144]

[1145] <First Step: Synthesis of Fluorosulfonylpropoxycarbonylamide>

[1146] In the first step of Synthesis Example 42 (Synthesis of Compound (I-42)), chlorosulfonyl isocyanate (7.77 g, 54.9 mmol), potassium difluoride (4.68 g, 59.9 mmol), and acetonitrile (25 mL) as a solvent were used, and n-propanol (3.00 g, 49.9 mmol) was replaced with methanol. Synthesis was carried out by the same method as Synthesis Example 42, thereby obtaining a crude product of fluorosulfonylpropoxycarbonylamide (9.24 g).

[1147] <Second Step: Synthesis of Lithium Fluorosulfonylpropoxycarbonylamide>

[1148] The reaction was carried out by the same method as the second step in Synthesis Example 42 (Synthesis of Compound (I-42)) using the crude product fluorosulfonylpropoxycarbonylamide (4.00 g) obtained in the first step, lithium carbonate (1.76 g, 23.8 mmol), and methanol (20 mL) as a solvent.

[1149] Thus, lithium fluorosulfonylpropoxycarbonylamide (1.76 g, 9.21 mmol, 43% yield over two steps) was obtained as the 79th white solid.

[1150] The following shows the 79th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1151] 1 H-NMR: δ0.88 (t, J=7.6Hz, 3H), 1.46-1.55 (m, 2H), 3.76 (t, J=6.8Hz, 2H)

[1152] [Synthesis Example 45]

[1153] Fluorosulfonylbutoxycarbonylamide lithium represented by the following structural formula [Synthetic Compound (I-45)] was synthesized as follows.

[1154] [Chemical Formula 68]

[1155]

[1156] <First Step: Synthesis of Fluorosulfonylbutoxycarbonylamide>

[1157] In the first step of Synthesis Example 42 (Synthesis of Compound (I-42)), chlorosulfonyl isocyanate (5.11 g, 36.1 mmol), potassium difluoride (3.08 g, 39.4 mmol), and acetonitrile (15 mL) as a solvent were used, and n-butanol (2.43 g, 32.8 mmol) was replaced with methanol. Synthesis was carried out by the same method as in Synthesis Example 42. Thus, a crude product of fluorosulfonylbutoxycarbonylamide (6.53 g) was obtained.

[1158] <Second Step: Synthesis of Lithium Fluorosulfonylbutoxycarbonylamide>

[1159] The reaction was carried out by the same method as the second step in Synthesis Example 42 (Synthesis of Compound (I-42)) using the crude product fluorosulfonylbutoxycarbonylamide (3.39 g), lithium carbonate (1.38 g, 18.7 mmol), and methanol (15 mL) as a solvent.

[1160] Thus, lithium fluorosulfonylbutoxycarbonylamide (2.50 g, 12.2 mmol, 72% yield over two steps) was obtained as the 80th white solid.

[1161] The following shows the 80th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1162] 1H-NMR: δ0.88 (t, J=7.6Hz, 3H), 1.26-1.35 (m, 2H), 1.43-1.50 (m, 2H), 3.80 (t, J=6.4Hz, 3H)

[1163] [Synthesis Example 46]

[1164] Fluorosulfonylbenzyloxycarbonylamide lithium represented by the following structural formula [Synthetic Compound (I-46)] was synthesized as follows.

[1165] [Chemical Formula 69]

[1166]

[1167] <First Step: Synthesis of Fluorosulfonylbenzyloxycarbonylamide>

[1168] In the first step of Synthesis Example 42 (Synthesis of Compound (I-42)), chlorosulfonyl isocyanate (3.97 g, 28.1 mmol), potassium difluoride (2.34 g, 30.0 mmol), and acetonitrile (15 mL) as a solvent were used, and benzyl alcohol (2.70 g, 25.0 mmol) was replaced with methanol. Synthesis was carried out by the same method as in Synthesis Example 42. Thus, a crude product of fluorosulfonylbenzyloxycarbonylamide (5.82 g) was obtained.

[1169] <Second Step: Synthesis of Lithium Fluorosulfonylbenzyloxycarbonylamide>

[1170] The reaction was carried out by the same method as the second step in Synthesis Example 42 (Synthesis of Compound (I-42)) using the crude product fluorosulfonylbenzyloxycarbonylamide (3.52 g), lithium carbonate (2.03 g, 27.5 mmol), and methanol (15 mL) as a solvent.

[1171] Thus, lithium fluorosulfonylbenzyloxycarbonylamide (2.67 g, 11.2 mmol, 74% yield over two steps) was obtained as the 81st white solid.

[1172] The following shows the 81st white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1173] 1 H-NMR: δ4.91 (s, 2H), 7.25-7.37 (m, 5H)

[1174] [Synthesis Example 47]

[1175] Butoxycarbonyl-4-trifluoromethylphenylsulfonamide lithium represented by the following structural formula [Synthetic Compound (I-47)] was synthesized as follows.

[1176] [Chemical Formula 70]

[1177]

[1178] <First Step: Synthesis of Butoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide>

[1179] In the first step of Synthesis Example 39 (Synthesis of Compound (I-39)), 4-(trifluoromethyl)benzenesulfonamide (2.40 g, 10.7 mmol), triethylamine (1.30 g, 12.79 mmol), 4-dimethylaminopyridine (0.16 g, 1.28 mmol), and tetrahydrofuran (50 mL) as a solvent were used to convert methyl chloroformate into butyl chloroformate (1.46 g, 10.7 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 39.

[1180] Thus, butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.80 g, 5.53 mmol, yield 52%) was obtained as the 82nd white solid.

[1181] The following shows the 82nd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1182] 1 H-NMR: δ0.80 (t, J=7.4Hz, 3H), 1.15-1.21 (m, 2H), 1.40-1.50 (m, 2H), 4.00 (t, J=6.6Hz, 3H), 8.02-8.15 (m, 4H)

[1183] <Second Step: Synthesis of Lithium Butoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide (I-47)>

[1184] The reaction was carried out by the same method as the second step in Synthesis Example 39 (Synthesis of Compound (I-39)) using butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.64 g, 5.03 mmol), tetrahydrofuran (20 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.87 mL, 5.03 mmol).

[1185] Thus, lithium butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.22 g, 3.68 mmol, yield 73%) was obtained as the 83rd white solid.

[1186] The following shows the 83rd white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1187] 1 H-NMR: δ0.82 (d, J=7.2Hz, 3H), 1.15-1.28 (m, 2H), 1.32-1.41 (m, 2H), 3.65 (t, J=6.6Hz, 2H), 7.72-7.78 (m, 2H), 7.87-7.93 (m, 2H)

[1188] [Synthesis Example 48]

[1189] Lithium butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide represented by the following structural formula [Synthetic Compound (I-48)] was synthesized as follows.

[1190] [Chemical Formula 71]

[1191]

[1192] <First Step: Synthesis of Butoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide>

[1193] In the first step of Synthesis Example 47 (Synthesis of Compound (I-47)), butyl chloroformate (1.59 g, 11.6 mmol), triethylamine (1.41 g, 13.9 mmol), 4-dimethylaminopyridine (0.17 g, 1.40 mmol), and tetrahydrofuran (30 mL) as a solvent were used to convert 4-(trifluoromethyl)benzenesulfonamide into 4-(trifluoromethoxy)benzenesulfonamide (2.80 g, 11.6 mmol). Except for this, the product was synthesized by the same method as the first step of Synthesis Example 47.

[1194] Thus, butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.06 g, 8.97 mmol, yield 77%) was obtained as the 84th white solid.

[1195] The following shows the 84th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1196] 1 H-NMR: δ0.81 (d, J=7.2Hz, 3H), 1.12-1.24 (m, 2H), 1.40-1.50 (m, 2H), 3.99 (t, J=6.6Hz, 2H), 7.62-7.68 (m, 2H), 8.00-8.06 (m, 2H)

[1197] <Second Step: Synthesis of Lithium Butoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide (I-40)>

[1198] The reaction was carried out by the same method as the second step in Synthesis Example 47 (Synthesis of Compound (I-47)) using butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.06 g, 8.97 mmol), tetrahydrofuran (50 mL) as a solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (6.90 mL, 8.97 mmol).

[1199] Thus, lithium butylcarbonyl 4-(trifluoromethoxy)phenylsulfonamide (2.66 g, 7.66 mmol, yield 85%) was obtained as the 85th white solid.

[1200] The following shows the 85th white solid 1 The measurement results were obtained by H-NMR (DMSO-d6).

[1201] 1 H-NMR: δ0.83 (d, J=7.4Hz, 3H), 1.17-1.27 (m, 2H), 1.32-1.42 (m, 2H), 3.65 (t, J=6.6Hz, 2H), 7.32-7.38 (m, 2H), 7.78-7.85 (m, 2H)

[1202] [Example 1]

[1203] A non-aqueous electrolyte solution was obtained by the following operation.

[1204] <Preparation of non-aqueous electrolyte>

[1205] Ethylene carbonate (hereinafter referred to as EC), dimethyl carbonate (hereinafter referred to as DMC), and ethyl methyl carbonate (EMC) were mixed at a volume ratio of EC:DMC:EMC = 30:35:35 to obtain a mixed solvent as a non-aqueous solvent.

[1206] LiPF 6 as an electrolyte was dissolved in the obtained mixed solvent so that the concentration in the finally obtained non-aqueous electrolyte solution became 1 mol / L, thereby obtaining an electrolyte solution.

[1207] Hereinafter, the obtained electrolyte solution is referred to as a "basic electrolyte solution."

[1208] As an additive, lithium butoxycarbonyltoluenesulfonamide (I-5) represented by the following formula (I-5) synthesized in Synthesis Example 1 was added to the basic electrolyte solution so that the content (mass %) relative to the total amount of the final non-aqueous electrolyte solution became the content described in Table 4. Thus, a non-aqueous electrolyte solution was obtained.

[1209] [Chemical Formula 72]

[1210]

[1211] A button-type battery (hereinafter also simply referred to as a "battery") serving as a precursor of a lithium secondary battery was produced as follows.

[1212] <Production of positive electrode>

[1213] Adding Li(Ni) as the positive electrode active material 0.5 Co 0.2 Mn 0.3 A mixture was prepared by mixing 2,4-dimethyl-1,2-dioxane (1,2-dioxane) with 1,2-dioxane (1,2-dioxane) and 1,2-dioxane (1,2-dioxane) as a mixture of ...94 mass % carbon black (3 mass %) as a conductive additive, and polyvinylidene fluoride (PVdF) (3 mass %) as a binder. The obtained mixture was dispersed in N-methylpyrrolidone solvent to obtain a positive electrode mixture slurry.

[1214] As a positive electrode current collector, an aluminum foil having a thickness of 20 μm was prepared.

[1215] The obtained positive electrode mixture slurry is applied to aluminum foil, dried, and then rolled using a press to obtain a sheet-shaped positive electrode. The positive electrode is composed of a positive electrode current collector and a positive electrode active material layer.

[1216] <Production of negative electrode>

[1217] Graphite (96% by mass) as a negative electrode active material, carbon black (1% by mass) as a conductive aid, 1% by mass (in terms of solid content) of sodium carboxymethyl cellulose dispersed in pure water as a thickener, and 2% by mass (in terms of solid content) of styrene-butadiene rubber (SBR) dispersed in pure water as a binder are mixed to obtain a negative electrode mixture material slurry.

[1218] As a negative electrode current collector, a copper foil having a thickness of 10 μm was prepared.

[1219] The obtained slurry is applied to a copper foil, dried, and then rolled using a press to obtain a sheet-shaped negative electrode. The negative electrode is composed of a negative electrode current collector and a negative electrode active material layer.

[1220] The non-aqueous electrolyte solution obtained in the above-mentioned production of the non-aqueous electrolyte solution is prepared.

[1221] As a separator, a porous polyethylene film was prepared.

[1222] <Production of button-type batteries>

[1223] The negative electrode, the positive electrode, and the separator were punched into discs with a diameter of 14 mm, 13 mm, and 17 mm, respectively. Thus, a button-shaped negative electrode, a button-shaped positive electrode, and a button-shaped separator were obtained.

[1224] The button-shaped negative electrode, button-shaped separator, and button-shaped positive electrode were stacked in this order in a stainless steel battery case (size: 2032). Next, 20 μL of nonaqueous electrolyte was injected into the battery case, immersing the separator, positive electrode, and negative electrode in the nonaqueous electrolyte.

[1225] Next, an aluminum plate (thickness 1.2 mm, diameter 16 mm) and a spring were placed on the positive electrode, and the battery case cover was caulked with a polypropylene gasket interposed therebetween to seal the battery.

[1226] Through the above method, we can obtain Figure 2 The coin-shaped lithium secondary battery precursor has the structure shown. The dimensions of the lithium secondary battery precursor are 20 mm in diameter and 3.2 mm in height.

[1227] [Comparative Example 1, Comparative Example 2, Examples 2 to 49]

[1228] In the preparation of the above nonaqueous electrolyte, the same operation as in Example 1 was carried out except that the additives listed in Table 4 were added so that the contents (mass %) relative to the total amount of the finally obtained nonaqueous electrolyte became the contents listed in Table 4, to obtain a lithium secondary battery precursor.

[1229] In Comparative Example 2, lithium trifluoromethylcarbonyl trifluoromethylsulfonamide (C-1) represented by the following formula (C-1) was used.

[1230] [Chemical Formula 73]

[1231]

[1232] 〔Evaluation Test〕

[1233] The obtained lithium secondary battery precursor was subjected to the following aging treatment to obtain a first battery. The obtained first battery was subjected to the following initial charge and discharge treatment to obtain a second battery. The obtained second battery was subjected to the following treatment for DC resistance evaluation to obtain a third battery. The obtained third battery was subjected to a high-temperature storage treatment to obtain a fourth battery. The obtained fourth battery was subjected to the following post-charge and discharge treatment to obtain a fifth battery.

[1234] The capacity after high-temperature storage, the resistance after high-temperature storage, and the resistance increase rate were measured using the following measurement methods using the obtained first to fifth batteries.

[1235] <Aging treatment>

[1236] The lithium secondary battery precursor was subjected to the following aging treatment to obtain a first battery.

[1237] The battery precursor was charged at a temperature range of 25-70°C at a cut-off voltage of 1.5V to 3.5V, followed by a rest period of 5-50 hours. Next, the battery precursor was charged at a temperature range of 25-70°C at a cut-off voltage of 3.5V to 4.2V, followed by a hold period of 5-50 hours. Next, the battery precursor was charged to 4.2V at a temperature range of 25-70°C, followed by discharge to 2.5V.

[1238] <Initial Charge and Discharge Processing>

[1239] The first battery was subjected to the following initial charge and discharge treatment to obtain a second battery.

[1240] The first battery was kept in a temperature environment of 25°C for 12 hours. Next, the first battery was charged at a charging rate of 0.2C with a constant current constant voltage (0.2C-CCCV) until it reached 4.2V (SOC (State Of Charge) 100%), followed by a rest for 30 minutes, and then discharged at a discharge rate of 0.2C with a constant current (0.2C-CC) until it reached 2.5V. This was repeated for three cycles to stabilize the battery. Then, the first battery was charged at a charging rate of 0.2C with a constant current constant voltage (0.5C-CCCV) until it reached 4.2V, followed by a rest for 30 minutes, and then discharged at a discharge rate of 1C with a constant current (1C-CC) until it reached 2.5V. Thus, the second battery was obtained.

[1241] <Processing for DC resistance evaluation>

[1242] The second battery was subjected to the following treatment for evaluating direct current resistance to obtain a third battery.

[1243] The treatment for DC resistance evaluation was performed at a temperature of 25°C. The second battery was subjected to CC discharge at a discharge rate of 0.2C to 2.5V and CCCV charge at a charge rate of 0.2C to 3.7V. "CCCV charge" refers to constant current constant voltage charging.

[1244] Next, the second battery was discharged at a discharge rate of 0.2 C for 10 seconds and charged at a charge rate of 0.2 C for 10 seconds. "CC10s discharge" refers to discharging at a constant current for 10 seconds. "CC10s charge" refers to charging at a constant current for 10 seconds.

[1245] Next, the second battery was discharged at a discharge rate of 0.5C for 10 seconds and charged at a charge rate of 0.2C for 25 seconds. Next, the second battery was discharged at a discharge rate of 1C for 10 seconds and charged at a charge rate of 0.2C for 50 seconds. Next, the second battery was discharged at a discharge rate of 2C for 10 seconds and charged at a charge rate of 0.2C for 100 seconds. This produced a third battery.

[1246] <High-temperature storage treatment>

[1247] The third battery was subjected to the following high-temperature storage treatment to obtain a fourth battery.

[1248] The third battery was charged with a constant current at a charge rate of 0.2 C to 4.2 V in a temperature environment of 25° C. The charged battery was then left to stand for 14 days in an atmosphere of 60° C. Thus, a fourth battery was obtained.

[1249] <Post-charge and discharge treatment>

[1250] The fourth battery was subjected to the following post-charge and discharge treatment to obtain a fifth battery.

[1251] The fourth battery was allowed to dissipate heat in a 25°C temperature environment and then subjected to the first discharge, the first charge, and the second discharge. The first discharge represented constant current discharge (1C-CC) at a discharge rate of 1C to 2.5V. The first charge represented constant current constant voltage charge (0.2C-CCCV) at a charge rate of 0.2C to 4.2V. The second discharge represented constant current discharge (1C-CC) at a discharge rate of 1C to 2.5V. This produced a fifth battery.

[1252] <Method for measuring capacity after high-temperature storage>

[1253] As shown in the following formula (X1), the relative value of the discharge capacity of the fourth battery of each example relative to the discharge capacity of the fourth battery of Comparative Example 1 is referred to as "capacity after high-temperature storage [%]." The capacity after high-temperature storage represents the capacity obtained after the second discharge in the above-described later charge-discharge treatment.

[1254] Capacity after high-temperature storage [relative value; %] = (discharge capacity of the fourth battery [mAh / g] / discharge capacity of the fourth battery of Comparative Example 1 [mAh / g]) × 100 (X1)

[1255] <Method for measuring electrical resistance after high-temperature storage>

[1256] As shown in the following formula (X2), the relative value of the direct current internal resistance of the fifth battery to the direct current internal resistance (DCIR) of the fifth battery of Comparative Example 1 was defined as "resistance after high-temperature storage [%]".

[1257] Resistance after high-temperature storage [relative value; %] = (DC resistance of the fifth battery [Ω] / DC resistance of the fifth battery of Comparative Example 1 [Ω]) × 100 ... (X2)

[1258] The DC resistance was measured using the following method. The fifth battery was subjected to the same DC resistance evaluation process as described above. The DC resistance (Ω) of the fifth battery was determined based on the voltage drop (= voltage before discharge start - voltage 10 seconds after discharge start) resulting from "CC10s discharge" at each discharge rate of 0.2C to 1C and the current values ​​(i.e., current values ​​corresponding to discharge rates of 0.2C to 1C).

[1259] <Measurement Method of Resistance Increase Rate>

[1260] As shown in the following formula (X3), the relative value of the resistance increase rate with respect to the resistance increase rate of Comparative Example 1 was referred to as "resistance increase rate [%]."

[1261] Resistance increase rate [relative value; %] = (resistance increase rate / resistance increase rate of comparative example 1) × 100 ... (X3)

[1262] In formula (X3), the resistance increase rate is obtained by dividing the DC resistance (Ω) of the fourth battery by the DC resistance (Ω) of the second battery. The DC resistance (Ω) of the fourth battery and the DC resistance (Ω) of the second battery are each measured using the same method as that used to measure the DC resistance (Ω) of the fifth battery in the above-mentioned method for measuring resistance after high-temperature storage.

[1263] The above relative value of the DC resistance of the fifth battery after the high-temperature storage test corresponds to the rate of increase (%) of DC resistance due to storage (hereinafter also referred to as the "resistance increase rate"). The increase rate here is an increase rate in the following manner: a case where there is neither an increase nor a decrease is represented as 100%, an increase is represented as greater than 100%, and a decrease is represented as less than 100%.

[1264] The reason for focusing on the resistance increase rate is that, in battery performance, while a low resistance value itself is an important performance, a reduced resistance increase rate due to degradation during storage is also extremely important performance.

[1265] [Table 4]

[1266]

[1267] In Table 4, “-” means that the corresponding component is not contained. “The content of each additive” represents the content (mass %) of the additive relative to the total amount of the non-aqueous electrolyte for lithium secondary batteries. “(I)” represents a lithium (N-carbonyl) sulfonamide compound (I). “(II)” represents a lithium fluorophosphate compound (II). “(C-1)” represents a trifluoromethylcarbonyl trifluoromethylsulfonamide lithium (C-1). “(III)” represents a cyclic dicarbonyl compound (III). “(IV)” represents a cyclic sulfur-containing ester compound (IV). “(I-1)” represents a methoxycarbonyl toluenesulfonamide lithium (I-1). “(I-2)” represents an ethoxycarbonyl toluenesulfonamide lithium (I-2). “(I-4)” represents an isopropoxycarbonyl toluenesulfonamide lithium (I-4). “(I-5)” represents a butoxycarbonyl toluenesulfonamide lithium (I-5). “(I-10)” represents a methoxycarbonyl trifluoromethylsulfonamide lithium (I-10). "(I-11)" represents lithium ethoxycarbonyl trifluoromethylsulfonamide (I-11). "(I-12)" represents lithium propoxycarbonyl trifluoromethylsulfonamide (I-12). "(I-13)" represents lithium isopropoxycarbonyl trifluoromethylsulfonamide (I-13). "(I-14)" represents lithium butoxycarbonyl trifluoromethylsulfonamide (I-14). "(I-16)" represents lithium methoxycarbonyl methylsulfonamide (I-16). "(I-23)" represents lithium benzoylethoxysulfonamide (I-23). ​​"(I-27)" represents lithium ethoxycarbonyl-2,2,2-trifluoroethoxysulfonamide (I-27). "(I-28)" represents lithium (2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide (I-28). "(I-30)" represents lithium ethoxycarbonyl-p-tolyloxysulfonamide (I-30). "(I-34)" represents lithium 4-methoxyphenoxycarbonyl trifluoromethylsulfonamide (I-34). "(I-37)" represents lithium allyloxycarbonyl trifluoromethylsulfonamide (I-37). "(I-39)" represents lithium methoxycarbonyl-4-trifluoromethylphenylsulfonamide (I-39). "(I-42)" represents lithium fluorosulfonylmethoxycarbonylamide (I-42). "(I-43)" represents lithium fluorosulfonylethoxycarbonylamide (I-43). "(I-44)" represents lithium fluorosulfonylpropoxycarbonylamide (I-44). "(I-45)" represents lithium fluorosulfonylbutoxycarbonylamide (I-45). "(I-46)" represents lithium fluorosulfonylbenzyloxycarbonylamide (I-46). "(II-1)" represents lithium difluorophosphate (II-1). "(III-1)" represents lithium bis(oxalatoborate) (III-1). "(IV-1)" represents a cyclic sulfur-containing ester compound (IV-1).

[1268] The non-aqueous electrolytes of Examples 1 to 49 contained the lithium (N-carbonyl)sulfonamide compound (I). Consequently, the lithium secondary batteries of Examples 1 to 49 maintained a capacity of 100% or greater after high-temperature storage, a resistance of 100% or less, and a resistance increase rate of 100% or less after high-temperature storage. In other words, the lithium secondary batteries of Examples 1 to 49 were able to suppress increases in DC resistance and decreases in discharge capacity even when stored in a high-temperature environment.

[1269] On the other hand, the non-aqueous electrolyte of Comparative Example 2 contained lithium trifluoromethylcarbonyl trifluoromethylsulfonamide (C-1) and did not contain lithium (N-carbonyl)sulfonamide compound (I). Therefore, the capacity of the lithium secondary battery of Comparative Example 2 after high-temperature storage was 100%, the resistance after high-temperature storage was 106%, and the resistance increase rate was 102%. In other words, the lithium secondary battery of Comparative Example 2 failed to suppress the increase in DC resistance and the decrease in discharge capacity when stored in a high-temperature environment.

[1270] The disclosed contents of Japanese patent application No. 2021-044154 filed on March 17, 2021, and the disclosed contents of Japanese patent application No. 2021-143890 filed on September 3, 2021, are all incorporated into this specification by reference.

[1271] All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each document, patent application, and technical standard were specifically and individually indicated.

Claims

1. A lithium (N-carbonyl)sulfonamide compound represented by the following formula (I), [Chemical Formula 1] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group, wherein At least one hydrogen atom of the alkyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkenyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkynyl group may be substituted by a halogen atom, and at least one hydrogen atom of the aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; L 1 and L 2 Each represents a single bond or -O-; wherein, excluding L 1 and L 2 Each is a single bond.

2. An additive for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I), [Chemical Formula 2] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group, wherein At least one hydrogen atom of the alkyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkenyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkynyl group may be substituted by a halogen atom, at least one hydrogen atom of the aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, R 1 and R 2 These two are not trifluoromethyl; L 1 and L 2 Each represents a single bond or -O-; wherein, excluding L 1 and L 2 Each is a single bond.

3. An additive for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I), [Chemical Formula 2] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group, an aralkyl group having 7 to 16 carbon atoms, or a halogen atom, wherein At least one hydrogen atom of the alkyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkenyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkynyl group may be substituted by a halogen atom, at least one hydrogen atom of the aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. L 1 Represents a single bond, L 2 Indicates -O-.

4. A non-aqueous electrolyte for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I), [Chemical Formula 3] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group, wherein At least one hydrogen atom of the alkyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkenyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkynyl group may be substituted by a halogen atom, at least one hydrogen atom of the aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, R 1 and R 2 These two are not trifluoromethyl; L 1 and L 2 Each represents a single bond or -O-; wherein, excluding L 1 and L 2 Each is a single bond.

5. A non-aqueous electrolyte for a lithium secondary battery, comprising a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I), [Chemical Formula 3] In formula (I), R 1 and R 2 Each represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group, an aralkyl group having 7 to 16 carbon atoms, or a halogen atom, wherein At least one hydrogen atom of the alkyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkenyl group may be substituted by a halogen atom, at least one hydrogen atom of the alkynyl group may be substituted by a halogen atom, at least one hydrogen atom of the aryl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms, and at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted by a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; L 1 Represents a single bond, L 2 Indicates -O-.

6. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, further comprising an electrolyte, The electrolyte is at least one selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), lithium hexafluorotantalate (LiTaF6), lithium trifluoromethanesulfonate (Li CF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N).

7. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, wherein In the lithium (N-carbonyl) sulfonamide compound (I), The R 1 represents the aryl group, The L 1 represents a single bond, The R 2 represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, The L 2 Indicates -O-.

8. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, wherein In the lithium (N-carbonyl) sulfonamide compound (I), The R 1 represents the alkyl group, The L 1 represents a single bond, The R 2 represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, The L 2 Indicates -O-.

9. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, wherein In the lithium (N-carbonyl) sulfonamide compound (I), The R 1 represents a fluorine atom, The L 1 represents a single bond, The R 2 represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, The L 2 Indicates -O-. 10 . The non-aqueous electrolyte for a lithium secondary battery according to claim 4 , comprising compound (II), wherein the compound (II) is at least one selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate.

11. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, comprising a compound (III) represented by the following formula (III): [Chemical Formula 4] In formula (III), M is an alkali metal, Y is a transition element, a Group 13 element, a Group 14 element, or a Group 15 element of the periodic table, b is an integer from 1 to 3, m is an integer from 1 to 4, n is an integer from 0 to 8, q is 0 or 1, R 3 is an alkylene group having 1 to 10 carbon atoms, a halogenated alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, which may contain a substituent or a heteroatom in the structure. When q is 1 and m is 2 to 4, m R 3 Each can be bonded, R 4 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms, and these groups may contain a substituent or a heteroatom in the structure. When n is 2 to 8, n R 4 Each may be bonded to form a ring, Q 1 and Q 2 are each independently an oxygen atom or a carbon atom.

12. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, comprising a compound (IV) represented by the following formula (IV): [Chemical Formula 5] In formula (IV), R 5 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms, R 6 is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a group represented by formula (iv-1), or a group represented by formula (iv-2), * indicates the bonding position, In formula (iv-1), R 61 is an oxygen atom, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an oxymethylene group, In formula (iv-2), R 62 It is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

13. The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, wherein The content of the lithium (N-carbonyl)sulfonamide compound (I) is 0.01% by mass or more and 5% by mass or less relative to the total amount of the non-aqueous electrolyte for lithium secondary batteries.

14. A lithium secondary battery precursor comprising: housing, and A positive electrode, a negative electrode, a separator, and an electrolyte contained in the housing; The positive electrode is a positive electrode that can absorb and release lithium ions. The negative electrode is a negative electrode that can absorb and release lithium ions. The electrolyte solution is the non-aqueous electrolyte solution for a lithium secondary battery according to any one of claims 4 to 13.

15. The lithium secondary battery precursor according to claim 14, wherein The positive electrode comprises a lithium-containing composite oxide represented by the following formula (C1) as a positive electrode active material, LiNi a Co b Mn c O2…Formula (C1) In formula (C1), a, b, and c are each independently greater than 0 and less than 1, and the total of a, b, and c is 0.99 to 1.

00.

16. A method for manufacturing a lithium secondary battery, comprising the following steps: a step of preparing the lithium secondary battery precursor according to claim 14 or claim 15, and The lithium secondary battery precursor is subjected to charging and discharging steps. 17 . A lithium secondary battery obtained by charging and discharging the lithium secondary battery precursor according to claim 14 or 15 .

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