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 manufacturing a lithium secondary battery

Abstract

A lithium (N-carbonyl)sulfonamide compound represented by formula (I).　In formula (I), R1 and R2 each represent a C1-10 alkyl group, a C2-10 alkenyl group, a C2-10 alkynyl group, or an aryl group. L1 and L2 each represent a single bond or -O-. This excludes, however, the case in which L1 and L2 are each a single bond.

Description

[Technical Field]

[0001] This disclosure relates to lithium (N-carbonyl) sulfonamide compounds, additives for lithium secondary batteries, non-aqueous electrolytes for lithium secondary batteries, lithium secondary battery precursors, lithium secondary batteries, and methods for producing lithium secondary batteries. [Background technology]

[0002] Lithium-ion batteries are attracting 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: Special Publication No. 2020-515558 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in lithium secondary batteries in which lithium trifluoromethylcarbonyltrifluoromethylsulfonamide disclosed in Patent Document 1 is added to a non-aqueous solvent, there was a risk that the DC resistance would increase and the discharge capacity would decrease when charging or discharging was performed in a high-temperature environment.

[0006] In view of the above circumstances, this disclosure aims to provide a lithium (N-carbonyl) sulfonamide compound, an additive for lithium secondary batteries, a non-aqueous electrolyte for lithium secondary batteries, a lithium secondary battery precursor, a lithium secondary battery, and a method for manufacturing a lithium secondary battery, which can suppress the increase in DC resistance and the decrease in discharge capacity even when lithium secondary batteries are stored in a high-temperature environment. [Means for solving the problem]

[0007] The following embodiments are included as means for solving the above problems.

[0008] <1> A lithium (N-carbonyl) sulfonamide compound represented by the following formula (I).

[0009] [ka]

[0010] [In formula (I), R 1 and R 2 Each of these 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), or 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). L 1 and L 2 Each of these represents a single bond or -O-. However, L 1 and L 2 Except when each of them is a single bond. <2> An additive for lithium secondary batteries containing a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I).

[0011] [ka]

[0012] [In formula (I), R 1 and R 2Each of them 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, provided that a trifluoromethyl group is excluded), 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), or 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). L 1 and L 2 Each of them represents a single bond or -O-. <3> In the additive for a lithium secondary battery described in <2>, said R 1 and said R 2 each represents instead of the alkyl group, the alkenyl group, the alkynyl group, or the aryl group, 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), the alkenyl group, the alkynyl group, the aryl group, 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), or a halogen atom, R 1 is a halogen atom, and L 1 is -O-, and the case where R 2 is a halogen atom, and L 2 is -O-, and the case where R 1 and R 2 each is the alkyl group or the aryl group, and L 1 and L[[ID=3�]] 2 each is a single bond are excluded, an additive for a lithium secondary battery. <4> A non-aqueous electrolyte for a lithium secondary battery containing a lithium (N-carbonyl)sulfonamide compound (I) represented by the following formula (I).

[0013] [ka]

[0014] [In formula (I), R 1 and R 2 Each of these 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, except for the trifluoromethyl group), 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), or 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). L 1 and L 2 Each of these represents a single bond or an -O- bond. <5> The aforementioned <4> In the non-aqueous electrolyte for lithium secondary batteries described above, The aforementioned R 1 and R 2 Each of them is, In place of the alkyl group, alkenyl group, alkynyl group, or aryl group, A C1-C10 alkyl group (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), the alkenyl group, the alkynyl group, the aryl group, a C7-C16 aralkyl group (at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, a C1-C6 alkoxy group, or a C1-C6 alkyl group), or a halogen atom. R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2Each of them is the alkyl group or the aryl group, and L 1 and L 2 A non-aqueous electrolyte for lithium secondary batteries, excluding cases where each of the bonds is a single bond. <6> It further contains electrolytes, The electrolyte is at least one selected from the group consisting of lithium hexafluoride phosphate (LiPF6), lithium tetraborate (LiBF4), lithium hexafluoride arsenate (LiAsF6), lithium tantalate hexafluoride (LiTaF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N). <4> or <5> Non-aqueous electrolyte for lithium secondary batteries as described above. <7> The lithium (N-carbonyl) sulfonamide compound (I) is The aforementioned R 1 This represents the aryl group, Said L 1 This represents a single bond, The aforementioned R 2 This represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, Said L 2 The above represents -O- <4> ~ <6> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <8> The lithium (N-carbonyl) sulfonamide compound (I) is The aforementioned R 1 However, representing the alkyl group, Said L 1 However, this represents a single bond, The aforementioned R 2 However, it represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, Said L 2 However, the above represents -O- <4> ~ <6> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <9> The lithium (N-carbonyl) sulfonamide compound (I) is The aforementioned R1 However, it represents a fluorine atom, Said L 1 However, this represents a single bond, The aforementioned R 2 However, it represents the alkyl group, the alkenyl group, the alkynyl group, the aryl group, or the aralkyl group, Said L 2 However, the above represents -O- <4> ~ <6> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <10> The above includes compound (II), which is at least one compound selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate. <4> ~ <9> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <11> The above includes compound (III) represented by the following formula (III), <4> ~ <10> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following.

[0015] [ka]

[0016] [In formula (III), M is an alkali metal, Y is a transition element, a group 13, group 14, or group 15 element of the periodic table. b is an integer between 1 and 3. m is an integer between 1 and 4. n is an integer between 0 and 8. q is either 0 or 1, R 3 This 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 substituents or heteroatoms in their structure, and when q is 1 and m is 2 to 4, there are m R 3 They may be joined together.) R 4This includes halogen atoms, C1-C10 alkyl groups, C1-C10 halogenated alkyl groups, C6-C20 aryl groups, or C6-C20 halogenated aryl groups (these groups may contain substituents or heteroatoms in their structure, and if n is 2-8, there are n R 4 They may each be joined together to form a ring. Q 1 , and Q 2 These are, independently, either an oxygen atom or a carbon atom. <12> The above includes compound (IV) represented by the following formula (IV). <4> ~ <11> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following.

[0017] [ka]

[0018] [In formula (IV), R 5 This 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 This 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 This 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 This is an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. <13> 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. <4> ~ <12> A non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <14> The case and The case contains a positive electrode, a negative electrode, a separator, and an electrolyte, Equipped with, The positive electrode is a positive electrode capable of intercalating and releasing lithium ions. The aforementioned negative electrode is a negative electrode capable of intercalating and releasing lithium ions. The electrolyte, <4> ~ <13> A lithium secondary battery precursor, which is a non-aqueous electrolyte for lithium secondary batteries as described in any one of the following. <15> The positive electrode contains a lithium-containing composite oxide represented by the following formula (C1) as the positive electrode active material. <14> A lithium secondary battery precursor as described above. LiRing 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 sum of a, b, and c is between 0.99 and 1.00.] <16> The aforementioned <14> or <15> The process of preparing the lithium secondary battery precursor described above, The process involves charging and discharging the lithium secondary battery precursor. A method for manufacturing lithium secondary batteries, including [the specified component]. <17> The aforementioned <14> or <15> A lithium secondary battery obtained by subjecting the lithium secondary battery precursor described above to charging and discharging. [Effects of the Invention]

[0019] According to this disclosure, a lithium (N-carbonyl) sulfonamide compound, an additive for lithium secondary batteries, a non-aqueous electrolyte for lithium secondary batteries, a lithium secondary battery precursor, a lithium secondary battery, and a method for manufacturing a lithium secondary battery are provided that can suppress an increase in DC resistance and a decrease in discharge capacity even when lithium secondary batteries are stored in a high-temperature environment. [Brief explanation of the drawing]

[0020] [Figure 1] This is a schematic cross-sectional view showing a laminate-type battery, which is an example of a lithium secondary battery precursor of the present disclosure. [Figure 2]This is a schematic cross-sectional view showing a coin-type battery, which is another example of a lithium secondary battery precursor in this disclosure. [Modes for carrying out the invention]

[0021] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, the amount of each component in a composition means the total amount of any multiple substances present in the composition, unless otherwise specified. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, provided that their intended purpose is achieved.

[0022] Hereinafter, embodiments of the lithium (N-carbonyl) sulfonamide compound, additive for lithium secondary batteries, non-aqueous electrolyte for lithium secondary batteries, lithium secondary battery precursor, lithium secondary battery, and method for manufacturing a lithium secondary battery according to this disclosure will be described with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals and will not be repeated in the description.

[0023] [Lithium (N-carbonyl) sulfonamide compound] (Compound (A)) The lithium (N-carbonyl) sulfonamide compounds of this disclosure are described below.

[0024] The lithium (N-carbonyl) sulfonamide compound disclosed herein is a novel compound represented by the following formula (I) (hereinafter sometimes referred to as "compound (A)").

[0025] [ka]

[0026] In formula (I), R 1 and R 2Each of these 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), or 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). L 1 and L 2 Each of these represents a single bond or an ether bond (-O-). However, L 1 and L 2 Except when each of them is a single bond.

[0027] The lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) of this disclosure is the above As it is represented by formula (I), when added to a non-aqueous electrolyte for lithium secondary batteries (hereinafter sometimes referred to as "non-aqueous electrolyte"), it can suppress the increase in DC resistance and the decrease in discharge capacity even when lithium secondary batteries are stored in a high-temperature environment. Details of lithium secondary batteries will be described later with reference to Figures 1 and 2.

[0028] The reason for the above effect is presumed to be as follows: When a lithium secondary battery is manufactured using a non-aqueous electrolyte to which the lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) of this disclosure is added, it is thought that reaction products are generated near the surface of the negative electrode of the lithium secondary battery during the manufacturing process (for example, the aging process described later), and further, components that are decomposition products of the reaction products are generated. The reaction products are those produced by the reaction between the lithium (N-carbonyl) sulfonamide compound and a compound (e.g., LiF) derived from the electrolyte. Such reaction products adhere to the negative electrode surface and form an SEI (Solid Electrolyte Interphase) film (hereinafter referred to as the "negative electrode SEI film"). It is thought that this component moves to the vicinity of the positive electrode surface during the manufacturing process, adheres to the positive electrode surface, and forms an SEI film (hereinafter referred to as the "positive electrode SEI film"). This enhances the stability of the lithium secondary battery in high-temperature environments. For example, the elution of metal elements in the positive electrode active material is suppressed. As a result, even if the lithium secondary battery is stored in a high-temperature environment, it is thought that the increase in the DC resistance of the lithium secondary battery is suppressed. The formation of the positive electrode SEI film is thought to continue even during the storage period when lithium secondary batteries are stored. Therefore, the rate of increase in the DC resistance of lithium secondary batteries with respect to the storage period is thought to be reduced when lithium secondary batteries are stored.

[0029] Furthermore, as described above, the stability of lithium secondary batteries using the lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) of this disclosure is excellent even in high-temperature environments. In other words, even if lithium secondary batteries are stored in high-temperature environments, it is thought that side reactions other than the original battery reaction will not proceed easily. The battery reaction involves the movement (intercalation) of lithium ions into and out of the positive and negative electrodes. Side reactions include the reductive decomposition reaction of the electrolyte by the negative electrode, the oxidative decomposition reaction of the electrolyte by the positive electrode, and the dissolution of metal elements in the positive electrode active material. As a result, the progress of the decomposition reaction of the non-aqueous electrolyte is suppressed. Consequently, even if lithium secondary batteries are stored in high-temperature environments, it is thought that the discharge capacity of the lithium secondary batteries will not decrease easily.

[0030] For the reasons stated above, when the lithium (N-carbonyl) sulfonamide compound of this 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 can be suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0031] Hereafter, when the negative electrode SEI film and the positive electrode SEI film are not distinguished, they will simply be referred to as "SEI film."

[0032] In formula (I), R 1 and R 2 Each of the "C1-C10 alkyl groups" represented is a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of "C1-C10 alkyl groups" 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 groups. Among these, C1-C6 alkyl groups are preferred, and C1-C3 alkyl groups are more preferred. At least one hydrogen atom of the "alkyl group having 1 to 10 carbon atoms" may be substituted with a halogen atom. Preferred halogen atoms are fluorine, chlorine, bromine, or iodine; more preferably fluorine, chlorine, or bromine; even more preferably fluorine or chlorine; and particularly preferably fluorine. In the "alkyl group having 1 to 10 carbon atoms," the number of hydrogen atoms substituted for the halogen atom is not particularly limited and can be appropriately selected according to the number of carbon atoms in the alkyl group, with 1 to 7 being preferred.

[0033] In formula (I), R 1 and R 2Each of the "C2-C10 alkenyl groups" is a linear or branched alkenyl group having 2 to 10 carbon atoms. Examples of "C2-C10 alkenyl groups" include vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, and 5-hexenyl groups. Among these, "C2-C10 alkenyl groups" are preferably C2-C6 alkenyl groups, and more preferably C2-C3 alkenyl groups. At least one hydrogen atom of the "alkenyl group having 2 to 10 carbon atoms" may be substituted with a halogen atom. Preferred halogen atoms are fluorine, chlorine, bromine, or iodine; more preferably fluorine, chlorine, or bromine; even more preferably fluorine or chlorine; and particularly preferably fluorine. 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 according to the number of carbon atoms in the alkenyl group, with 1 to 7 being preferred.

[0034] In formula (I), R 1 and R 2 Each of the terms "C2-C10 alkynyl group" refers to a linear or branched alkynyl group having 2 to 10 carbon atoms. Examples of "C2-C10 alkynyl groups" include ethynyl group, propargyl group (2-propynyl group), 2-butynyl group, 3-butynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, and 5-hexynyl group. Among these, "C2-C10 alkynyl groups" are preferably C2-C6 alkynyl groups, and more preferably C2-C3 alkynyl groups. At least one hydrogen atom of the "alkynyl group having 2 to 10 carbon atoms" may be substituted with a halogen atom. Preferred halogen atoms are fluorine, chlorine, bromine, or iodine; more preferred are fluorine, chlorine, or bromine; even more preferred are fluorine or chlorine; and particularly preferred is fluorine. In the "alkynyl group having 2 to 10 carbon atoms," the number of hydrogen atoms substituted for halogen atoms is not particularly limited and can be appropriately selected according to the number of carbon atoms in the alkynyl group, with 1 to 7 being preferred.

[0035] In formula (I), R 1 and R 2 At least one hydrogen atom of the "aryl group" represented by each of the above is , It may be substituted with a rogen atom, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. 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; even more preferably a fluorine atom or a chlorine atom; and particularly preferably a fluorine atom. In the "aryl group," the number of hydrogen atoms substituted for the halogen atom is not particularly limited, but is preferably 1 to 5. The alkoxy group having 1 to 6 carbon atoms may have a linear, branched, or cyclic alkyl group. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, and pentyloxy groups. Among these, alkoxy groups having 1 to 3 carbon atoms are preferred, with methoxy and ethoxy groups being more preferred. 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 1 to 3 is preferred. The C1-C6 alkyl group may be linear, branched, or cyclic. Examples of C1-C6 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. Among these, C1-C6 alkyl groups are preferably C1-C3 alkyl groups, with methyl and ethyl groups being more preferred. In the "aryl group," the number of hydrogen atoms substituted by the C1-C6 alkyl group is not particularly limited, but 1 to 3 is preferred.

[0036] In formula (I), L 1 and L 2Each of them represents a single bond or -O-. However, L 1 and L 2 except when each of them is a single bond. In other words, L 1 is a single bond and L 2 is a single bond are excluded. Among them, L 1 preferably represents a single bond, and L 2 preferably represents -O-.

[0037] Specific examples of the lithium (N-carbonyl)sulfonamide compound (that is, compound (A)) include synthetic compounds (I-1) to synthetic compound (I-41) (excluding synthetic compound (I-9)) synthesized in the examples described later.

[0038] (Compound (B)) The lithium (N-carbonyl)sulfonamide compound of the present disclosure is In the above-mentioned lithium (N-carbonyl)sulfonamide compound (that is, compound (A)), each of the R 1 and the R 2 is instead of the alkyl group, the alkenyl group, the alkynyl group, or the aryl group, the alkyl group, the alkenyl group, the alkynyl group, the aryl group, 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), or a halogen atom, ​​​​​​​​​​​​​​​​​​​​​​It may also be a lithium (N-carbonyl) sulfonamide compound, excluding the case where each of them is a single bond.

[0039] 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)").

[0040] [Chemical formula]

[0041] 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 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), 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), or a halogen atom. L 1 and L 2 each represents a single bond or -O-. However, the case where R 1 is a halogen atom and L 1 is -O-, the case where R 2 is a halogen atom and L 2 is -O-, and the case where each of R 1 and R 2 is the alkyl group or the aryl group and each of L 1 and L 2 is a single bond are excluded.

[0042] When the lithium (N-carbonyl) sulfonamide compound (i.e., compound (B)) of this disclosure is used by being added to a non-aqueous electrolyte, it can suppress the increase in DC resistance and the decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment. The reason for the above effects is presumed to be the same as the reason why, when compound (A) is added to a non-aqueous electrolyte, the increase in DC resistance and the decrease in discharge capacity can be suppressed even when lithium secondary batteries are stored in a high-temperature environment.

[0043] In compound (B), in formula (I), R 1 and R 2 The "alkyl groups with 1 to 10 carbon atoms" represented in each of the above are the same as those exemplified as "alkyl groups with 1 to 10 carbon atoms" in compound (A). In compound (B), in formula (I), R 1 and R 2 The "alkenyl groups with 2 to 10 carbon atoms" represented in each of the above are the same as those exemplified as "alkenyl groups with 2 to 10 carbon atoms" in compound (A). In compound (B), in formula (I), R 1 and R 2 The "alkynyl groups with 2 to 10 carbon atoms" represented in each of the above are the same as those exemplified as "alkynyl groups with 2 to 10 carbon atoms" in compound (A). In compound (B), in formula (I), R 1 and R 2 The "aryl group" represented in each of these is the same as the "aryl group" exemplified in compound (A).

[0044] In compound (B), in formula (I), R 1 and R 2 Each of the terms "aralkyl group having 7 to 16 carbon atoms" is an aralkyl group having 7 to 16 carbon atoms and containing 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. 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; even more preferably a fluorine atom or a chlorine atom; and particularly preferably a fluorine atom. In the "aralkyl group," the number of hydrogen atoms substituted for the halogen atom is not particularly limited, but 1 to 5 is preferred. The alkoxy group having 1 to 6 carbon atoms may have a linear, branched, or cyclic alkyl group. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, and pentyloxy groups. Among these, alkoxy groups having 1 to 3 carbon atoms are preferred, with methoxy and ethoxy groups being more preferred. 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 1 to 3 is preferred. The C1-C6 alkyl group may be linear, branched, or cyclic. Examples of C1-C6 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. Among these, C1-C6 alkyl groups are preferably C1-C3 alkyl groups, with methyl and ethyl groups being more preferred. In the "aralkyl group," the number of hydrogen atoms substituted by the C1-C6 alkyl group is not particularly limited, but 1 to 3 is preferred. As the aralkyl group having 7 to 16 carbon atoms, an aralkyl group consisting of an aryl group substituted with an alkylene group having 1 to 6 carbon atoms is preferred. As the aryl group substituted with an alkylene group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of "aralkyl groups with 7 to 16 carbon atoms" include the benzyl group, the phenylethyl group, or the naphthylmethyl group.

[0045] In compound (B), in formula (I), R 1 and R 2The "halogen atoms" represented in each of these are preferably fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, more preferably fluorine atoms, chlorine atoms, or bromine atoms, even more preferably fluorine atoms or chlorine atoms, and particularly preferably fluorine atoms.

[0046] In formula (I), L 1 and L 2 Each of these represents a single bond or an -O-. However, R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2 Each of them is the alkyl group or the aryl group, and L 1 and L 2 Except for the case where each of them is a single bond. Among them, L 1 It is preferable that this represents a single bond, L 2 It is preferable to represent -O-.

[0047] Specific examples of lithium (N-carbonyl) sulfonamide compounds (i.e., compound (B)) include synthetic compounds (I-1) to (I-48) synthesized in the examples described later.

[0048] [Additives for lithium secondary batteries] (Additive (A)) The lithium secondary battery additives described herein (hereinafter sometimes simply referred to as "additives") will be explained below.

[0049] The additives of this disclosure include a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I) (hereinafter sometimes referred to as "compound (C)").

[0050] [ka]

[0051] In formula (I), R1 and R 2 Each of these 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, except for the trifluoromethyl group), 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), or 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). L 1 and L 2 Each of these represents either a single bond or an -O- bond.

[0052] In this disclosure, "except for the trifluoromethyl group" in alkyl groups having 1 to 10 carbon atoms means R 1 is a trifluoromethyl group, L 1 is a single bond, R 2 is a trifluoromethyl group, and L 2 We show that the case where the bond is a single bond is excluded from equation (I).

[0053] Hereafter, additives containing compound (C) may be referred to as "additive (A)".

[0054] Since additive (A) of the present disclosure contains a lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (C)), when added to a non-aqueous electrolyte, it can suppress the increase in DC resistance and the decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment. The reason for the above-mentioned effect is presumed to be the same as the reason why, when the lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (A)) of this disclosure is added to a 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.

[0055] Additive (A) of the present disclosure is suitable as an additive for the non-aqueous electrolyte of a lithium secondary battery.

[0056] R 1 , R 2 , L 1 , and L 2 For example, R 1 and R 2 The trifluoromethyl group has been removed from L 1 and L 2 Aside from the fact that each of them may be a single bond, the R of the lithium (N-carbonyl) sulfonamide compound (i.e., compound (A)) described above is the same. 1 , R 2 , L 1 , and L 2 Examples similar to those given as illustrations can be cited.

[0057] (Additive (B)) The additives of this disclosure are, in the above-mentioned additives for lithium secondary batteries (i.e., additive (A)), The aforementioned R 1 and R 2 Each of them is, In place of the alkyl group, alkenyl group, alkynyl group, or aryl group, A C1-C10 alkyl group (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), the alkenyl group, the alkynyl group, the aryl group, a C7-C16 aralkyl group (at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, a C1-C6 alkoxy group, or a C1-C6 alkyl group), or a halogen atom. R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2 Each of them is the alkyl group or the aryl group, and L 1 and L 2It may also be an additive for lithium secondary batteries in which the cases where each of the following is a single bond are excluded.

[0058] In other words, the additive for lithium secondary batteries of this disclosure may be an additive (hereinafter sometimes referred to as "additive (B)") comprising a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I) (i.e., compound (B)).

[0059] [ka]

[0060] In formula (I), R 1 and R 2 Each of these 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), 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), or a halogen atom. L 1 and L 2 Each of these represents a single bond or an -O-. However, R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2 Each of them is the alkyl group or the aryl group, and L 1 and L 2 Except for the case where each of them is a single bond.

[0061] Since the additive (B) of this disclosure contains a lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (B)), when added to a non-aqueous electrolyte, it can suppress the increase in DC resistance and the decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment. The reason for the above effects is presumed to be the same as the reason why, when additive (A) is added to a non-aqueous electrolyte, the increase in DC resistance and the decrease in discharge capacity can be suppressed even when lithium secondary batteries are stored in a high-temperature environment.

[0062] Additive (B) of the present disclosure is suitable as an additive for the non-aqueous electrolyte of a lithium secondary battery.

[0063] Addition of this disclosure Agent The lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (B)) contained in (B) is the same as the example lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (B)) described above.

[0064] [Nonaqueous electrolyte for lithium secondary batteries] (Non-aqueous electrolyte (A)) This disclosure describes the non-aqueous electrolyte for lithium secondary batteries.

[0065] The non-aqueous electrolyte of this disclosure is used as an electrolyte for lithium secondary batteries.

[0066] The non-aqueous electrolyte of this disclosure comprises a lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (C)) represented by the following formula (I).

[0067] [ka]

[0068] In formula (I), R 1 and R 2Each of these 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, except for the trifluoromethyl group), 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), or 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). L 1 and L 2 Each of these represents either a single bond or an -O- bond.

[0069] In this disclosure, "except for the trifluoromethyl group" means R 1 is a trifluoromethyl group, L 1 is a single bond, R 2 is a trifluoromethyl group, and L 2 We show that the case where the bond is a single bond is excluded from equation (I).

[0070] Hereinafter, a non-aqueous electrolyte containing compound (C) may be referred to as "non-aqueous electrolyte (A)".

[0071] Since the non-aqueous electrolyte (A) of this disclosure contains a lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (C)), it is possible to suppress the increase in DC resistance and the decrease in discharge capacity even when the lithium secondary battery is stored in a high-temperature environment. The reason for the above-mentioned effect is presumed to be the same as the reason why, when the lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (A)) of this disclosure is added to a 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.

[0072] The lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (C)) contained in the non-aqueous electrolyte (A) of this disclosure is similar to those exemplified as the lithium (N-carbonyl) sulfonamide compound (I) (i.e., compound (C)) contained in the additive (A) of this disclosure described above.

[0073] (Non-aqueous electrolyte (B)) The non-aqueous electrolyte of this disclosure is In the non-aqueous electrolyte for lithium secondary batteries described above (i.e., non-aqueous electrolyte (A)), The aforementioned R 1 and R 2 Each of them, In place of the alkyl group, alkenyl group, alkynyl group, or aryl group, A C1-C10 alkyl group (at least one hydrogen atom of the alkyl group may be substituted with a halogen atom), the alkenyl group, the alkynyl group, the aryl group, a C7-C16 aralkyl group (at least one hydrogen atom of the aromatic ring in the aralkyl group may be substituted with a halogen atom, a C1-C6 alkoxy group, or a C1-C6 alkyl group), or a halogen atom. R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2 Each of them is the alkyl group or the aryl group, and L 1 and L 2 It may also be a non-aqueous electrolyte for lithium secondary batteries, in which the cases where each of the bonds is a single bond are excluded.

[0074] In other words, the non-aqueous electrolyte of this disclosure may be an additive containing a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I) (i.e., "compound (B)") (hereinafter sometimes referred to as "non-aqueous electrolyte (B)").

[0075] [ka]

[0076] In formula (I), R 1 and R 2 Each of these 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), 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), or a halogen atom. L 1 and L 2 Each of these represents a single bond or an -O-. However, R 1 is a halogen atom, and L 1 When is -O-, and R 2 is a halogen atom, and L 2 When is -O-, and R 1 and R 2 Each of them is the alkyl group or the aryl group, and L 1 and L 2 Except for the case where each of them is a single bond.

[0077] The non-aqueous electrolyte (B) of this disclosure can suppress an increase in DC resistance and a decrease in discharge capacity even when lithium secondary batteries are stored in a high-temperature environment. The reason for the above effects is presumed to be the same as the reason why, when a non-aqueous electrolyte (A) is added to a non-aqueous electrolyte, the increase in DC resistance and the decrease in discharge capacity can be suppressed even when lithium secondary batteries are stored in a high-temperature environment.

[0078] 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 as those exemplified as the above-mentioned lithium (N-carbonyl)sulfonamide compound (I) (i.e., compound (B)).

[0079] Hereinafter, the compound (C) or the compound ( B ) is simply referred to as "lithium (N-carbonyl)sulfonamide compound (I)". Hereinafter, the additive (A) or the additive (B) is simply referred to as "additive". Hereinafter, the non-aqueous electrolyte (A) or the non[[ID=illl]] water aqueous electrolyte (B) is simply referred to as "non-aqueous electrolyte".

[0080] (aryl group-containing compound) The lithium (N-carbonyl)sulfonamide compound (I) is preferably an aryl group-containing compound. [[ID=!20]] Since the non-aqueous electrolyte of the present disclosure is an aryl group-containing compound, 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 more suppressed.

[0081] The aryl group-containing compound is represented by the formula (I), 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), L 1 represents a single bond, R 2is 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), L 2 represents -O-.

[0082] Specific examples of the aryl group-containing compound include synthetic compounds (I-1) to synthetic compound (I-9), synthetic compound (I-24), synthetic compound (I-25), synthetic compounds (I-30) to synthetic compound (I-32), synthetic compounds (I-38) to synthetic compound (I-40), synthetic compound (I-47), and synthetic compound (I-48) synthesized in the examples described later, and the like.

[0083] (alkyl group-containing compound) The lithium (N-carbonyl)sulfonamide compound (I) is preferably an alkyl group-containing compound. Since the non-aqueous electrolyte of the present disclosure is an alkyl group-containing compound, 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 more suppressed.

[0084] The alkyl group-containing compound is represented by the formula (I), R 1 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), L 1 represents a single bond, R 2However, it 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), L 2 However, this represents -O-.

[0085] Specific examples of alkyl group-containing compounds 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.

[0086] (Fluorine atom-containing compounds) Lithium (N-carbonyl) sulfonamide compound (I) is preferably a compound containing a fluorine atom. Because the non-aqueous electrolyte of this disclosure contains a fluorine atom-containing compound, the increase in DC resistance and the decrease in discharge capacity can be further suppressed even when the lithium secondary battery is stored in a high-temperature environment.

[0087] Fluorine atom-containing compounds are represented by formula (I), R 1 However, it represents a fluorine atom, L 1 However, it represents a single bond, R 2However, it 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). L 2 However, this represents -O-.

[0088] Specific examples of fluorine atom-containing compounds include synthetic compounds (I-42) to (I-46) synthesized in the examples described later.

[0089] The intrinsic viscosity of the non-aqueous electrolyte is preferably 10.0 mPa·s or less at 25°C, from the viewpoint of further improving the dissociation properties of the electrolyte and the mobility of ions.

[0090] Furthermore, when analyzing non-aqueous electrolytes collected from disassembled lithium secondary batteries, the amount of lithium (N-carbonyl) sulfonamide compound (I) may be less than the amount added to the non-aqueous electrolyte. Even in this case, if even a small amount of lithium (N-carbonyl) sulfonamide compound (I) is detected in the non-aqueous electrolyte extracted from the lithium secondary battery, the electrolyte of that lithium secondary battery is included within the scope of non-aqueous electrolytes as defined in this disclosure.

[0091] The content of lithium (N-carbonyl) sulfonamide compound (I) is preferably 0.01% to 5.0% by mass, more preferably 0.05% to 3.0% by mass, even more preferably 0.10% to 1.5% by mass, and particularly preferably 0.20% to 1.5% by mass, based on the total amount of the non-aqueous electrolyte. If the content of lithium (N-carbonyl) sulfonamide compound (I) is within the above range, the lithium secondary battery can operate without the SEI film impairing the conductivity of the lithium cation. Furthermore, the battery characteristics of the lithium secondary battery are improved as the SEI film includes a phosphate structure. If the content of lithium (N-carbonyl) sulfonamide compound (I) is within the above range, the SEI film contains a sufficient amount of structures derived from lithium (N-carbonyl) sulfonamide compound (I). This facilitates the formation of thermally and chemically stable inorganic salt or polymer structures. Therefore, at high temperatures, the leaching of SEI film components that impair the durability of the SEI film, and the deterioration of the SEI film, are less likely to occur. As a result, the durability of the SEI film and the high-temperature storage characteristics of lithium secondary batteries are improved.

[0092] <Lithium Fluorophosphate Compound (II)> The non-aqueous electrolyte of this disclosure preferably contains compound (II), which is at least one compound selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate (hereinafter sometimes referred to as "lithium fluorophosphate compound (II)"). Lithium difluorophosphate is represented by the following formula (II-1), and lithium monofluorophosphate is represented by the following formula (II-2).

[0093] [ka]

[0094] The non-aqueous electrolyte of this disclosure contains a lithium fluorophosphate compound (II) in addition to a lithium (N-carbonyl) sulfonamide compound (I), which further suppresses the decrease in discharge capacity and increase in DC resistance of the lithium secondary battery even after charge-discharge cycles following storage in a high-temperature environment.

[0095] When the non-aqueous electrolyte contains a 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 still more preferably 0.1% by mass to 2% by mass with respect to the total amount of the non-aqueous electrolyte. When the content of the lithium fluorophosphate compound (II) is within the above range, the solubility of the lithium fluorophosphate in the non-aqueous solvent can be ensured, and the DC resistance of the lithium secondary battery can be further reduced.

[0096] 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)").

[0097]

Chemical formula

[0098] 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 of 1 to 3, m is an integer of 1 to 4, n is an integer of 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 (these groups may contain a substituent or a hetero atom in the structure, and when q is 1 and m is 2 to 4, m R 3 may be bonded to each other.). R 4This includes halogen atoms, C1-C10 alkyl groups, C1-C10 halogenated alkyl groups, C6-C20 aryl groups, or C6-C20 halogenated aryl groups (these groups may contain substituents or heteroatoms in their structure, and if n is 2-8, there are n R 4 They may each be joined together to form a ring. Q 1 , and Q 2 These are, independently, either an oxygen atom or a carbon atom.

[0099] The non-aqueous electrolyte of this disclosure contains a cyclic dicarbonyl compound (III) in addition to a lithium (N-carbonyl) sulfonamide compound (I), which further suppresses the decrease in discharge capacity and increase in DC resistance of the lithium secondary battery even after charge-discharge cycles following storage in a high-temperature environment. This effect is presumed to be due to the following reasons: The non-aqueous electrolyte contains a cyclic dicarbonyl compound (III) in addition to the lithium (N-carbonyl) sulfonamide compound (I). As a result, the SEI film and the like may contain bonds derived from the cyclic dicarbonyl compound (III) within its interior, in addition to the reaction products mentioned above. This facilitates the formation of thermally and chemically stable inorganic salt or polymer structures. Therefore, at high temperatures, the elution of components of the SEI film and the like, which would impair the durability of the SEI film, and the deterioration of the SEI film and the like are less likely to occur. Consequently, even after long-term storage in a high-temperature environment, the decrease in discharge capacity and increase in DC resistance of the lithium secondary battery are more suppressed during charge-discharge cycles.

[0100] M is an alkali metal. Examples of alkali metals include lithium, sodium, and potassium. Of these, M is preferably lithium. Y is a transition element, a group 13, group 14, or group 15 element of the periodic table. Preferably, Y is 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 manufacturing costs can be reduced. b represents the valency of the anion and the number of cations. b is an integer between 1 and 3, and is preferably 1. If b is 3 or less, the salt of the anionic compound is easily soluble in the mixed organic solvent. m and n are values ​​related to the number of ligands. Each of m and n is determined by the type of M. m is an integer from 1 to 4. n is an integer from 0 to 8. q is either 0 or 1. When q is 0, the chelate ring is a five-membered ring, and when q is 1, the chelate ring is a six-membered ring. R 3 represents 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 structure. Specifically, substituents may be included instead of hydrogen atoms in these groups. Examples of substituents include halogen atoms, linear 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. These groups may also have structures in which nitrogen atoms, sulfur atoms, or oxygen atoms are introduced instead of carbon atoms. When q is 1 and m is 2 to 4, there are m R 3 These components may be bonded together. An example of such a ligand is ethylenediaminetetraacetic acid. R 4R represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl halide having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl halide having 6 to 20 carbon atoms. These alkyl groups, alkyl halides, aryl groups, or aryl halides are R 3 Similarly, the structure may contain substituents and heteroatoms, and when n is 2 to 8, there are n R 4 These may each be joined to form a ring. 4 As such, electron-withdrawing groups are preferred, and fluorine atoms are particularly preferred. Q 1 , and Q 2 These are, independently, O, or C This represents the ligands bonding to Y via these heteroatoms.

[0101] Specific examples of cyclic dicarbonyl compounds (III) include the compounds represented by the following formulas (III-1) to (III-2). Hereinafter, the compound represented by formula (III-1) may be referred to as "lithium bisoxalate borate (III-1)".

[0102] [ka]

[0103] When the non-aqueous electrolyte contains a cyclic dicarbonyl compound (III), the content of the cyclic dicarbonyl compound (III) is preferably 0.01% to 10% by mass, more preferably 0.05% to 5.0% by mass, even more preferably 0.10% to 3.0% by mass, and particularly preferably 0.10% to 2.0% by mass, based on the total amount of the non-aqueous electrolyte. If the content of cyclic dicarbonyl compound (III) is within the above range, the lithium secondary battery can operate without the SEI film, etc., impairing the conductivity of the lithium cation. Furthermore, the battery characteristics of the lithium secondary battery are improved as the SEI film, etc., includes a cyclic dicarbonyl structure. If the content of cyclic dicarbonyl compound (III) is within the above range, the SEI film, etc., contains a sufficient amount of a structure mainly composed of cyclic dicarbonyl structures. This facilitates the formation of thermally and chemically stable inorganic salt or polymer structures. Therefore, at high temperatures, the elution of components of the SEI film, etc., which impairs the durability of the SEI film, etc., and the deterioration of the SEI film, etc., are less likely to occur. As a result, the durability of the SEI film, etc., and the characteristics of lithium secondary batteries after high-temperature storage are improved.

[0104] The non-aqueous electrolyte of this disclosure preferably contains compound (IV) represented by the following formula (IV) (hereinafter referred to as "cyclic sulfur-containing ester compound (IV)").

[0105] [ka]

[0106] In formula (IV), R 5 This 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 This 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 This 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 This is an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.

[0107] The non-aqueous electrolyte of this disclosure contains a cyclic sulfur-containing ester compound (IV) in addition to a lithium (N-carbonyl) sulfonamide compound (I), which makes it possible to suppress the decrease in discharge capacity and increase in DC resistance of the lithium secondary battery even when stored for a long period of time in a high-temperature environment. This effect is presumed to be due to the following reasons: When a lithium secondary battery is manufactured using the non-aqueous electrolyte of this disclosure, the reaction products in the manufacturing process (for example, the aging process described later) include products resulting from the reaction between a cyclic sulfur-containing ester compound (IV) and a compound derived from the electrolyte (for example, LiF). This further enhances the stability of the lithium secondary battery under high-temperature conditions. As a result, even when the lithium secondary battery is stored under high-temperature conditions, the increase in the DC resistance of the lithium secondary battery is expected to be more suppressed. Furthermore, the progress of the decomposition reaction of the non-aqueous electrolyte is further suppressed. As a result, even when the lithium secondary battery is stored under high-temperature conditions, the discharge capacity of the lithium secondary battery is expected to decrease less.

[0108] In formula (IV), R 5 It is preferably an alkylene group, vinylene group, or oxygen atom having 2 to 3 carbon atoms, more preferably a trimethylene group, vinylene group, or oxygen atom, and particularly preferably an oxygen atom.

[0109] Cyclic sulfur-containing ester compounds (IV) are R 5 However, it is preferable that the atom be an oxygen atom. This facilitates the formation of a thermally and chemically stable inorganic salt structure. Therefore, at high temperatures, the elution of components of the SEI film, which impairs the durability of the SEI film, and the deterioration 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.

[0110] In formula (IV), R 6 It is preferable that the group is represented by formula (iv-1) or formula (iv-2). In formula (iv-1), R 61 The group 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. 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.

[0111] Specific examples of cyclic sulfur-containing ester compounds (IV) include the compound represented by formula (IV-1), and formulas (IV-1) to (IV-4). Hereinafter, compounds represented by formula (IV-1) may be referred to as "cyclic sulfur-containing ester compounds (IV-1)".

[0112] [ka]

[0113] The non-aqueous electrolyte may contain only one cyclic sulfur-containing ester compound (IV), or it may contain two or more.

[0114] When the non-aqueous electrolyte contains a cyclic sulfur-containing ester compound (IV), the content of the cyclic sulfur-containing ester compound (IV) is preferably 0.01% to 5.0% by mass, more preferably 0.05% to 3.0% by mass, and even more preferably 0.10% to 2.0% by mass, based on the total amount of the non-aqueous electrolyte. If the content of cyclic sulfur-containing ester compound (IV) is within the above range, the lithium secondary battery can operate without the SEI film impairing the conductivity of lithium ions. Furthermore, the inclusion of a cyclic sulfur-containing ester structure in the SEI film improves the battery characteristics of the lithium secondary battery. If the content of cyclic sulfur-containing ester compound (IV) is within the above range, the SEI film, etc., contains a sufficient amount of cyclic sulfur-containing ester structure. This facilitates the formation of thermally and chemically stable inorganic salt or polymer structures. Therefore, at high temperatures, the elution of components of the SEI film, etc., which impairs the durability of the SEI film, etc., and the deterioration 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 lithium secondary batteries are improved.

[0115] <Other additives> The non-aqueous electrolyte of this disclosure may contain other additives. Other additives are not particularly limited, and any known additives can be used as desired. Other additives that can be used include, for example, those described in paragraphs 0042 to 0055 of Japanese Patent Publication No. 2019-153443.

[0116] <Non-aqueous solvent> Non-aqueous electrolytes generally contain a non-aqueous solvent. Various known non-aqueous solvents can be appropriately selected. There may be only one non-aqueous solvent or two or more.

[0117] Examples of non-aqueous solvents include cyclic carbonates, fluorinated cyclic carbonates, linear carbonates, fluorinated linear carbonates, aliphatic carboxylic acid esters, fluorinated aliphatic carboxylic acid esters, γ-lactones, fluorinated γ-lactones, cyclic ethers, fluorinated cyclic ethers, linear ethers, fluorinated linear ethers, nitriles, amides, lactams, nitromethane, nitroethane, sulfolanes, trimethyl phosphate, dimethyl sulfoxide, and dimethyl sulfoxide phosphate. Examples of cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Examples of fluorine-containing cyclic carbonates include fluoroethylene carbonate (FEC). Examples of linear carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), and dipropyl carbonate (DPC). Examples of 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. Examples of γ-lactones include γ-butyrolactone and γ-valerolactone. Examples of cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane. Examples of linear ethers include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, 1,2-dimethoxyethane, and 1,2-dibutoxyethane. Examples of nitriles include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile. Examples of amides include N,N-dimethylformamide. Examples of lactam compounds include N-methylpyrrolidinone, N-methyloxazolidinone, and N,N'-dimethylimidazolidinone.

[0118] The non-aqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates, fluorine-containing cyclic carbonates, linear carbonates, and fluorine-containing linear carbonates. In this case, the total proportion of cyclic carbonates, fluorinated cyclic carbonates, linear carbonates, and fluorinated linear carbonates is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass, relative to the total amount of the non-aqueous solvent.

[0119] The non-aqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates and linear carbonates. In this case, the total proportion of cyclic carbonates and linear carbonates in the non-aqueous solvent 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, and even more preferably 80% by mass or more and 100% by mass or less, relative to the total amount of the non-aqueous solvent.

[0120] The content of the non-aqueous solvent is preferably 60% to 99% by mass, more preferably 70% to 97% by mass, and even more preferably 70% to 90% by mass, relative to the total amount of the non-aqueous electrolyte.

[0121] The intrinsic viscosity of the non-aqueous solvent is preferably 10.0 mPa·s or less at 25°C, from the viewpoint of further improving the dissociation of the electrolyte and the mobility of ions.

[0122] <Electrolytes> Non-aqueous electrolytes generally contain electrolytes.

[0123] The "electrolyte" in lithium-ion batteries refers to the substance responsible for carrier transport between the positive and negative electrodes. Electrolytes have high solubility in non-aqueous solvents and a high degree of dissociation in non-aqueous solvents. In most cases, lithium salts are used as the electrolyte.

[0124] The electrolyte preferably contains at least one of a lithium salt containing fluorine (hereinafter sometimes referred to as "fluorinated lithium salt") and a lithium salt that does not contain fluorine.

[0125] Examples of fluorinated lithium salts include inorganic acid anionic salts and organic acid anionic salts. Examples of inorganic acid anionic salts include lithium hexafluoride phosphate (LiPF6), lithium borate tetrafluoride (LiBF4), lithium arsenate hexafluoride (LiAsF6), and lithium tantalate hexafluoride (LiTaF6). Examples of organic acid anionic salts include lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N). In particular, the fluorinated lithium salt is preferably a lithium salt other than the lithium (N-carbonyl) sulfonamide compound (I) represented by formula (I). In other words, the fluorinated lithium salt is preferably at least one selected from the group consisting of lithium hexafluoride phosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium hexafluoride arsenate (LiAsF6), lithium hexafluoride tantalate (LiTaF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C2F5SO2)2N). Lithium hexafluoride phosphate (LiPF6) is particularly preferred as the fluorinated lithium salt.

[0126] Lithium salts that do not contain fluorine include lithium perchlorate (LiClO4), lithium aluminate tetrachloride (LiAlCl4), and lithium decachlorodecaborate (Li2B 10 Cl 10 ) are some examples.

[0127] When the electrolyte contains a fluorinated lithium salt, the content of the fluorinated lithium salt is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass, relative to the total amount of the electrolyte. When the fluorinated lithium salt contains lithium hexafluoride phosphate (LiPF6), the content of lithium hexafluoride phosphate (LiPF6) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass, relative to the total amount of the electrolyte.

[0128] When the non-aqueous electrolyte contains an electrolyte, the concentration of the electrolyte in the non-aqueous electrolyte is preferably 0.1 mol / L or more and 3 mol / L or less, more preferably 0.5 mol / L or more and 2 mol / L or less.

[0129] When the non-aqueous electrolyte contains lithium hexafluoride phosphate (LiPF6), the concentration of lithium hexafluoride phosphate (LiPF6) in the non-aqueous electrolyte is preferably 0.1 mol / L or more and 3 mol / L or less, more preferably 0.5 mol / L or more and 2 mol / L or less.

[0130] <Other ingredients> The non-aqueous electrolyte may contain other components as needed. Other components include acid anhydrides.

[0131] [Precursor for lithium secondary batteries] Next, the lithium secondary battery precursor of this disclosure will be described.

[0132] The lithium secondary battery precursor of this disclosure comprises a case, a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode, negative electrode, separator, and electrolyte are housed in the case. The positive electrode is a positive electrode capable of intercalating and releasing lithium ions. The negative electrode is a negative electrode capable of intercalating and releasing lithium ions. The electrolyte is a non-aqueous electrolyte of this disclosure.

[0133] A lithium secondary battery precursor refers to a lithium secondary battery before charging and discharging. In other words, in a lithium secondary battery precursor, the negative electrode does not contain a negative electrode SEI film, and the positive electrode does not contain a positive electrode SEI film.

[0134] <Case> The shape of the case is not particularly limited and can be appropriately selected depending on the application of the lithium secondary battery precursor disclosed herein. Examples of cases include cases including a laminate film, and cases consisting of a battery can and a battery can lid.

[0135] <Positive electrode> The positive electrode is a positive electrode capable of intercepting and releasing lithium ions. Preferably, the positive electrode contains at least one positive electrode active material capable of intercepting and releasing lithium ions.

[0136] The positive electrode comprises a positive electrode current collector and a positive electrode composite layer. The positive electrode composite layer is provided on at least a portion of the surface of the positive electrode current collector.

[0137] Examples of materials for the positive electrode current collector include metals and alloys. More specifically, examples of positive electrode current collector materials include aluminum, nickel, stainless steel (SUS), and copper. Among these, aluminum is preferred from the viewpoint of balancing high conductivity and cost. Here, "aluminum" means pure aluminum or aluminum alloy. Aluminum foil is preferred as the positive electrode current collector. The material of the aluminum foil is not particularly limited, and examples include A1085 material and A3003 material.

[0138] The positive electrode composite layer contains a positive electrode active material and a binder.

[0139] The positive electrode active material is not particularly limited as long as it is a material capable of intercalating and releasing lithium ions, and can be appropriately adjusted depending on the application of the lithium secondary battery precursor.

[0140] Examples of positive electrode active materials include primary oxides and secondary oxides. Primary oxides consist of lithium (Li) and nickel (Ni) as constituent metal elements. Secondary oxides contain Li, Ni, and at least one other metal element as constituent metal elements. Examples of metal elements other than Li and Ni include transition metal elements and typical metal elements. Preferably, the secondary oxide contains the metal element other than Li and Ni in an amount equivalent to or less than Ni in terms of atomic number. The metal element other than Li and Ni may be 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 may be used individually or in combination.

[0141] The positive electrode active material preferably contains 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 advantage of having a high energy density per unit volume and excellent thermal stability. LiRing a Co b Mn c O2… Formula (C1) In equation (C1), a, b, and c are each independently greater than 0 and less than 1, and the sum of a, b, and c is between 0.99 and 1.00. A specific example of NCM is LiNi 0.33 Co 0.33 Mn 0.33 O2, LiLiLi 0.5 Co 0.3 Mn 0.2 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0142] The positive electrode active material may contain a lithium-containing composite oxide represented by the following formula (C2) (hereinafter sometimes referred to as "NCA"). Li t Ni 1-x-y Co x Al y O2… Formula (C2) In equation (C2), t is between 0.95 and 1.15, x is between 0 and 0.3, y is between 0.1 and 0.2, and the sum of x and y is less than 0.5. A specific example of NCA is Li Ni 0.8 Co 0.15 Al 0.05 Examples include O2.

[0143] In the lithium secondary battery precursor of this disclosure, if the positive electrode comprises a positive electrode current collector and a positive electrode composite layer containing a positive electrode active material and a binder, the content of the positive electrode active material in the positive electrode composite layer is preferably 10% to 99.9% by mass, more preferably 30% to 99.0% by mass, even more preferably 50% to 99.0% by mass, and particularly preferably 70% to 99.0% by mass, based on the total amount of the positive electrode composite layer.

[0144] Examples of binders include polyvinyl acetate, polymethyl methacrylate, nitrocellulose, fluororesins, and rubber particles. Examples of fluororesins include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and vinylidene fluoride-hexafluoropropylene copolymer. Examples of rubber particles include styrene-butadiene rubber particles and acrylonitrile rubber particles. Among these, fluororesins are preferred from the viewpoint of improving the oxidation resistance of the positive electrode composite layer. One type of binder can be used alone, and two or more types can be used in combination as needed. The binder content in the positive electrode composite layer is preferably 0.1% by mass or more and 4% by mass or less relative to the total amount of the positive electrode composite layer, from the viewpoint of balancing the physical properties of the positive electrode composite layer (e.g., electrolyte permeability, peel strength, etc.) and battery performance. When the binder content is 0.1% by mass or more, the adhesion of the positive electrode composite layer to the positive electrode current collector and the bonding of the positive electrode active materials to each other are further improved. When the binder content is 4% by mass or less, the amount of positive electrode active material in the positive electrode composite layer can be increased, thus further improving the discharge capacity.

[0145] The positive electrode composite layer preferably contains a conductive additive. As the material for the conductive additive, known conductive additives can be used. Among the known conductive additives, conductive carbon materials are preferred. Examples of conductive carbon materials include graphite, carbon black, conductive carbon fibers, and fullerenes. These can be used alone or in combination of two or more types. Examples of conductive carbon fibers include carbon nanotubes, carbon nanofibers, and carbon fibers. Examples of graphite include artificial graphite and natural graphite. Examples of natural graphite include flake graphite, lump graphite, and earthy graphite. The material of the conductive additive may be a commercially available product. Examples of commercially available carbon blacks include Tokai Carbon #4300, #4400, #4500, #5500, etc. (Tokai Carbon Co., Ltd., Furnace Black), Printex L, etc. (Degussa Co., Ltd., Furnace Black), Raven 7000, 5750, 5250, 5000ULTRAIII, 5000ULTRA, etc., Conductex SC ULTRA, Conductex 975ULTRA, etc., PUER BLACK100, 115, 205 etc. (Columbian brand, Furnace Black), #2350, #2400B, #2600B, #30050B, #3030B, #3230B, #3350B, #3400B, #5400B etc. (Mitsubishi Chemical Corporation, Furnace Black), MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, Examples include LITX-50, LITX-200 (Cabot Furnace Black), Ensaco 250G, Ensaco 260G, Ensaco 350G, Super-P (TIMCAL), Ketjenblack EC-300J, EC-600JD (Akzo), Denka Black, Denka Black HS-100, FX-35 (Denka Acetylene Black).

[0146] The positive electrode composite layer may contain other components. These other components include thickeners, surfactants, dispersants, wetting agents, and defoaming agents.

[0147] <Negative electrode> The negative electrode is a negative electrode capable of intercepting and releasing lithium ions. Preferably, the negative electrode contains at least one negative electrode active material capable of intercepting and releasing lithium ions.

[0148] The negative electrode more preferably comprises a negative electrode current collector and a negative electrode composite layer. The negative electrode composite layer is provided on at least a portion of the surface of the negative electrode current collector.

[0149] There are no particular restrictions on the material of the negative electrode current collector; any known material can be used, such as metal or alloy. Specifically, examples of materials for the negative electrode current collector include aluminum, nickel, stainless steel (SUS), nickel-plated steel, and copper. Among these, copper is preferred as the material for the negative electrode current collector from the viewpoint of processability. Copper foil is preferred as the negative electrode current collector.

[0150] The negative electrode composite layer contains a negative electrode active material and a binder.

[0151] The negative electrode active material is not particularly limited as long as it is a material capable of intercalating and releasing lithium ions. Preferably, the negative electrode active material is 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 these, the negative electrode active material is preferably a carbon material capable of doping and dedoping with lithium ions (hereinafter referred to as "carbon material").

[0152] Examples of carbon materials include carbon black, activated carbon, graphite materials, and amorphous carbon materials. These carbon materials may be used individually or in mixtures of two or more. The form of the carbon material is not particularly limited and can be fibrous, spherical, potato-shaped, or flake-shaped. The particle size of the carbon material is not particularly limited, but is preferably 5 μm to 50 μm, and more preferably 20 μm to 30 μm. Examples of amorphous carbon materials include hard carbon, coke, mesocarbon microbeads (MCMB) fired at temperatures below 1500°C, and mesophase pitch carbon fiber (MCF). Examples of graphite materials include natural graphite and artificial graphite. Examples of artificial graphite include graphitized MCMB and graphitized MCF. Graphite materials may contain boron. Graphite materials may be coated with metal or amorphous carbon. Examples of metals used to coat the graphite material include gold, platinum, silver, copper, and tin. Graphite materials may also be mixtures of amorphous carbon and graphite.

[0153] The negative electrode composite layer preferably contains a conductive additive. Examples of conductive additives include those similar to those exemplified as conductive additives that may be included in the positive electrode composite layer.

[0154] The negative electrode composite layer may contain other components in addition to the above-mentioned components. Examples of other components include thickeners, surfactants, dispersants, wetting agents, and defoaming agents.

[0155] <Separator> Examples of separators include porous resin plates. Materials for the porous resin plates include resin, nonwoven fabrics containing this resin, and others. Examples of resins include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polyester, cellulose, and polyamide. In particular, the separator is preferably a porous resin sheet with a single-layer or multi-layer structure. The porous resin sheet is mainly made of one or more types of polyolefin resin. The thickness of the separator is preferably 5 μm to 30 μm. The separator is preferably placed between the positive electrode and the negative electrode.

[0156] [An example of a lithium secondary battery precursor] An example of a lithium secondary battery precursor 1 according to an embodiment of this disclosure will be specifically described with reference to Figure 1. Figure 1 is a cross-sectional view of a lithium secondary battery precursor 1 according to an embodiment of this disclosure.

[0157] The lithium secondary battery precursor 1 is of the stacked type. As shown in Figure 1, in the lithium secondary battery precursor 1, the battery element 10 is sealed inside the outer casing 30. The outer casing 30 is made of laminate film. The battery element 10 is fitted with a positive electrode lead 21 and a negative electrode lead 22. The positive electrode lead 21 and the negative electrode lead 22 are led out in opposite directions from the inside to the outside of the outer casing 30.

[0158] As shown in Figure 1, the battery element 10 is made up of a stack of a positive electrode 11, a separator 13, and a negative electrode 12. The positive electrode 11 has a positive electrode composite layer 11B formed on both main surfaces of the positive electrode current collector 11A. The negative electrode 12 has a negative electrode composite layer 12B formed on both main surfaces of the negative electrode current collector 12A. The positive electrode composite layer 11B formed on one main surface of the positive electrode current collector 11A of the positive electrode 11 and the negative electrode composite layer 12B formed on one main surface of the negative electrode current collector 12A of the negative electrode 12 adjacent to the positive electrode 11 face each other via the separator 13.

[0159] The non-aqueous electrolyte of this disclosure is injected into the exterior casing 30 of the lithium secondary battery precursor 1. The non-aqueous electrolyte of this disclosure permeates the positive electrode composite layer 11B, the separator 13, and the negative electrode composite layer 12B. In the lithium secondary battery precursor 1, a single cell layer 14 is formed by the adjacent positive electrode composite layer 11B, the separator 13, and the negative electrode composite layer 12B. The positive electrode and negative electrode may be formed with their respective active material layers on one side of their respective current collectors.

[0160] In this embodiment, the lithium secondary battery precursor 1 is of the stacked type, but the disclosure is not limited thereto, and for example, it may be of the wound type. The wound type is formed by stacking a positive electrode, a separator, a negative electrode, and a separator in that order and winding them in layers. The wound type includes cylindrical or rectangular shapes.

[0161] In this embodiment, as shown in Figure 1, the direction in which each of the positive lead and the negative lead protrudes from the inside to the outside of the casing 30 is opposite to the direction of the casing 30, but the disclosure is not limited thereto. For example, the way in which each of the positive lead and the negative lead protrudes from the inside to the outside of the casing 30 is the same direction with respect to the casing 30.

[0162] An example of a lithium secondary battery according to the embodiments of the present disclosure described below is a lithium secondary battery in which an SEI film is formed on the respective surfaces of the positive electrode composite layer 11B and the negative electrode composite layer 12B of the lithium secondary battery precursor 1 by charging and discharging the lithium secondary battery precursor 1.

[0163] Another example of a lithium secondary battery precursor in this disclosure is a coin cell. Figure 2 is a schematic perspective view showing an example of a coin cell battery, which is another example of a lithium secondary battery precursor of the present disclosure. In the coin-type battery shown in Figure 2, a disc-shaped negative electrode 42, a separator 45 injected with a non-aqueous electrolyte, a disc-shaped positive electrode 41, and, if necessary, spacer plates 47 and 48 made of stainless steel or aluminum are stacked in this order and housed between the positive electrode can 43 (hereinafter also referred to as the "battery can") and the sealing plate 44 (hereinafter also referred to as the "battery can lid"). The positive electrode can 43 and the sealing plate 44 are crimped and sealed via a gasket 46. In this example, the non-aqueous electrolyte of this disclosure is used as the non-aqueous electrolyte injected into the separator 45.

[0164] [Lithium-ion secondary battery] Next, a lithium secondary battery according to an embodiment of this disclosure will be described.

[0165] The lithium secondary battery according to this embodiment comprises a case, a positive electrode, a negative electrode, a separator, and an electrolyte. The positive electrode, negative electrode, separator, and electrolyte are housed in the case. The positive electrode is a positive electrode capable of intercalating and releasing lithium ions. The negative electrode is a negative electrode capable of intercalating and releasing lithium ions. The electrolyte is a non-aqueous electrolyte of this disclosure. The negative electrode includes a negative electrode SEI film. The positive electrode includes a positive electrode SEI.

[0166] The lithium secondary battery according to this embodiment differs from the lithium secondary battery precursor according to this embodiment mainly in two respects: the negative electrode includes a negative electrode SEI film (point 1), and the positive electrode includes a positive electrode SEI film (point 2). In other words, the lithium secondary battery according to this embodiment is the same as the lithium secondary battery precursor according to this embodiment, except for points 1 and 2. Therefore, the description of the components other than points 1 and 2 for the lithium secondary battery of this embodiment will be omitted below.

[0167] Regarding the first point, "the negative electrode includes a negative electrode SEI film" means that when the negative electrode comprises a negative electrode current collector and a negative electrode composite layer, it includes a first negative electrode form and a second negative electrode form. The first negative electrode form refers to a form in which a negative electrode SEI film is formed on at least a portion of the surface of the negative electrode composite layer. The second negative electrode form refers to a form in which a negative electrode SEI film is formed on the surface of the negative electrode active material, which is a constituent material of the negative electrode composite layer.

[0168] Regarding the second point, "the positive electrode includes a positive electrode SEI film" means that when the positive electrode comprises a positive electrode current collector and a positive electrode composite layer, it includes a first positive electrode form and a second positive electrode form. 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 composite layer. The second positive electrode form refers to a form in which a positive electrode SEI film is formed on the surface of the positive electrode active material, which is a constituent material of the positive electrode composite layer.

[0169] The SEI membrane includes, for example, at least one selected from the group consisting of a decomposition product of lithium (N-carbonyl) sulfonamide compound (I), a reaction product of lithium (N-carbonyl) sulfonamide compound (I) and an electrolyte, and a decomposition product of said reaction product.

[0170] The components of the negative electrode SEI film and the positive electrode SEI film may be the same or different. The thickness of the negative electrode SEI film and the thickness of the positive electrode SEI film may be the same or different.

[0171] The lithium secondary battery of this disclosure is obtained by charging and discharging the lithium secondary battery precursor of this disclosure. In other words, the lithium secondary battery of this disclosure is obtained by subjecting it to an aging process described later.

[0172] [Method for producing lithium (N-carbonyl) sulfonamide compounds] Next, a method for producing the lithium (N-carbonyl) sulfonamide compound of this disclosure will be described.

[0173] A method for producing a lithium (N-carbonyl) sulfonamide compound comprises a first step and a second step, which will be described later. The first and second steps are performed in this order. This yields the lithium (N-carbonyl) sulfonamide compound of the present disclosure.

[0174] <First step> In the first step, the sulfonamide compound is reacted with a carboxylic acid chloride or carboxylic acid anhydride in a solvent, the resulting salt is removed, and the (N-carbonyl)sulfonamide compound is obtained by column chromatography.

[0175] Each of the sulfonamide compounds, carboxylic acid chlorides, and carboxylic acid anhydrides is appropriately selected depending on the type of (N-carbonyl) sulfonamide compound being produced. Examples of sulfonamide compounds include trifluoromethanesulfonamide, methanesulfonamide, phenoxymethylsulfonamide, ethyl sulfamate, and 2,2,2-trifluoroethylsulfamate. Examples of carboxylic acid chlorides include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, phenyl chloroformate, and acetyl chloride. Examples of carboxylic acid anhydrides 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. Examples of solvents include non-aqueous solvents. Examples of non-aqueous solvents 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 orthoxylene, metaxylene, or paraxylene.

[0176] The reaction in the first step can be carried out under either atmospheric pressure or reduced pressure. The reaction in the first step is preferably carried out under an inert atmosphere to prevent contamination by components that inhibit the formation of the (N-carbonyl)sulfonamide compound (e.g., water). Examples of components that inhibit the formation of the (N-carbonyl)sulfonamide compound include water. Examples of inert atmospheres include a nitrogen atmosphere and an argon atmosphere. The reaction temperature in the first step is preferably -20°C to 60°C, more preferably 0°C to 40°C, and even more preferably 10°C to 30°C. When the reaction temperature is 60°C or lower, the decomposition of the sulfonamide raw material and the carboxylic acid chloride or carboxylic acid anhydride reactant is suppressed, and the rate of (N-carbonyl)sulfonamide compound formation tends to improve. From the viewpoint of ensuring the reaction proceeds efficiently, the reaction time in the first step is preferably 30 minutes to 12 hours, and more preferably 1 hour to 6 hours.

[0177] <Second process> In the second step, the (N-carbonyl)sulfonamide compound is reacted with the lithium salt compound in a solvent. This yields the lithium (N-carbonyl)sulfonamide compound.

[0178] Examples of lithium salt compounds include lithium bis(trimethylsilyl)amide, lithium chloride, lithium carbonate, lithium hydroxide, lithium methoxide, lithium ethoxide, and lithium t-butoxide. Among these, lithium bis(trimethylsilyl)amide, lithium chloride, lithium carbonate, or lithium hydroxide are preferred lithium salt compounds, with lithium bis(trimethylsilyl)amide being more preferred.

[0179] The above reaction in the second step can be carried out under either atmospheric pressure or reduced pressure. second The reaction in the process is preferably carried out under an inert atmosphere to prevent contamination with components (e.g., water) that inhibit the formation of lithium (N-carbonyl) sulfonamide compounds. Examples of components that inhibit the formation of lithium (N-carbonyl) sulfonamide compounds include water. Examples of inert atmospheres include a nitrogen atmosphere and an argon atmosphere. 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. The reaction time in the second step is preferably 30 minutes to 12 hours, and more preferably 1 hour to 6 hours, from the viewpoint of ensuring the reaction proceeds efficiently.

[0180] The method for separating the lithium (N-carbonyl) sulfonamide compound from the product is not particularly limited and can be appropriately adjusted depending on the state of the product obtained. If only the lithium (N-carbonyl) sulfonamide compound is obtained, the lithium (N-carbonyl) sulfonamide compound can be separated without any special treatment. If the product is a slurry in which the lithium (N-carbonyl) sulfonamide compound is dispersed in a solvent, the lithium (N-carbonyl) sulfonamide compound can be separated from the slurry by separating the solvent and drying it. If the product is a solution in which the lithium (N-carbonyl) sulfonamide compound is dissolved in a solvent, the lithium (N-carbonyl) sulfonamide compound can be separated from the solution by distillation, such as by heating and concentration. If the product is a solution in which the lithium (N-carbonyl) sulfonamide compound is dissolved in a solvent, the lithium (N-carbonyl) sulfonamide compound can be precipitated by adding a solvent in which the lithium (N-carbonyl) sulfonamide compound does not dissolve to the solution, and then the solvent is separated from the solution and dried to isolate the lithium (N-carbonyl) sulfonamide compound.

[0181] The lithium (N-carbonyl) sulfonamide compound extracted from the product may be subjected to drying treatment. The drying treatment is not particularly limited and includes, for example, static drying in a shelf dryer, fluidized bed drying in a conical dryer, drying using equipment such as a hot plate or oven, and supplying hot air or warm air with a dryer or similar device.

[0182] The pressure used to dry the lithium (N-carbonyl) sulfonamide compound extracted from the product may be either atmospheric pressure or reduced pressure. The drying temperature for the lithium (N-carbonyl) sulfonamide compound extracted 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 results in excellent drying efficiency. A drying temperature of 100°C or lower suppresses the decomposition of the generated lithium (N-carbonyl) sulfonamide compound, making it easier to stably extract the lithium (N-carbonyl) sulfonamide compound.

[0183] The lithium (N-carbonyl) sulfonamide compound extracted from the product may be used as is, or it may be used after being dispersed or dissolved in a solvent, for example, or mixed with other substances.

[0184] [Method for producing lithium (N-carbonyl) sulfonamide compound (I)] Next, a method for producing the lithium (N-carbonyl) sulfonamide compound (I) of this disclosure will be described.

[0185] The method for producing the lithium (N-carbonyl) sulfonamide compound (I) of the present disclosure is as follows: 1 and L 2 The method is carried out in the same manner as described above for producing lithium (N-carbonyl) sulfonamide compound (I), except that sulfonamide compounds, carboxylic acid chlorides, and carboxylic acid anhydrides may be selected so that each of the bonds may be a single bond. This yields lithium (N-carbonyl) sulfonamide compound (I).

[0186] [Method for producing non-aqueous electrolyte] Next, a method for producing the non-aqueous electrolyte according to this disclosure will be described.

[0187] The method for producing a non-aqueous electrolyte according to this disclosure includes a synthesis step, a dissolution step, and a mixing step. The dissolution step and the mixing step are performed in this order. The synthesis step may be performed before the mixing step.

[0188] In the synthesis process, lithium (N-carbonyl) sulfonamide compound (I) is synthesized. The synthesis process can be carried out in the same manner as the method for producing lithium (N-carbonyl) sulfonamide compound (I) described above.

[0189] In the dissolution step, the electrolyte is dissolved in a non-aqueous solvent to obtain a solution. It is preferable that the electrical conductivity of the resulting non-aqueous electrolyte is reduced compared to the electrical conductivity of the solution before the addition of lithium (N-carbonyl) sulfonamide compound (I).

[0190] In the mixing step, lithium (N-carbonyl) sulfonamide compound (I) and, if necessary, other additives are added to the solution and mixed. This yields a non-aqueous electrolyte. The non-aqueous electrolyte obtained by the method for producing a non-aqueous electrolyte according to this embodiment exhibits a more effective effect in reducing DC resistance in lithium secondary batteries.

[0191] The method for producing a non-aqueous electrolyte described herein includes, but is not limited to, a synthesis step, a dissolution step, and a mixing step.

[0192] [Method for manufacturing lithium secondary battery precursors] Next, the method for producing the lithium secondary battery precursor of this disclosure will be described.

[0193] The present disclosure's method for producing a lithium secondary battery precursor includes a first preparation step, a second preparation step, a third preparation step, a containment step, and an injection step. The containment step and the injection step are performed in this order. Each of the first preparation step, the second preparation step, and the third preparation step is performed before the containment step.

[0194] In the first preparation step, the positive electrode is prepared. Methods for preparing the positive electrode include, for example, applying a positive electrode mixture slurry to the surface of the positive electrode current collector and drying it. The positive electrode mixture slurry contains a positive electrode active material and a binder. Organic solvents are preferred as the solvent in the cathode composite slurry. Examples of organic solvents include N-methyl-2-pyrrolidone (NMP). The method for coating the cathode composite slurry is not particularly limited and includes, for example, slot die coating, slide coating, curtain coating, and gravure coating. The method for drying the cathode composite slurry is not particularly limited and includes drying with warm air, hot air, or low-humidity air; vacuum drying; and drying by infrared (e.g., far-infrared) irradiation. The drying time is not particularly limited and is preferably between 1 minute and 30 minutes. The drying temperature is not particularly limited and is preferably between 40°C and 80°C. It is preferable that the dried product, after being coated with a positive electrode composite slurry onto the positive electrode current collector and dried, be subjected to pressure treatment. This reduces the porosity of the positive electrode active material layer. Examples of methods for pressure treatment include mold presses and roll presses.

[0195] In the second preparation step, the negative electrode is prepared. One method for preparing the negative electrode is to apply a negative electrode slurry to the surface of the negative electrode current collector and allow it to dry. The negative electrode slurry contains a negative electrode active material and a binder. Examples of solvents included in the negative electrode mixture slurry include water and liquid media that are compatible with water. Including a liquid media that is compatible with water in the solvent of the negative electrode mixture slurry can improve the coating properties on the negative electrode current collector. Examples of liquid media that are compatible with water include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphate amides, sulfoxides, carboxylic acid esters, phosphate esters, ethers, and nitriles. The methods for applying, drying, and pressurizing the negative electrode mixture slurry are the same as those exemplified for applying, drying, and pressurizing the positive electrode mixture slurry.

[0196] In the third preparation step, a non-aqueous electrolyte is prepared. The method for preparing the non-aqueous electrolyte is the same as the method described in the non-aqueous electrolyte manufacturing method above.

[0197] In the housing process, the positive electrode, negative electrode, and separator are housed in the case. For example, in the housing process, a battery element is created using a positive electrode, a negative electrode, and a separator. Next, the positive electrode current collector and the positive electrode lead are electrically connected, and the negative electrode current collector and the negative electrode lead are electrically connected. Then, the battery element is housed in a case and fixed in place. The method for electrically connecting the positive electrode current collector and the positive electrode lead is not particularly limited and includes, for example, 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 includes, for example, ultrasonic welding and resistance welding.

[0198] Hereinafter, the state in which the positive electrode, negative electrode, and separator are housed in the case will be referred to as the "assembly."

[0199] In the injection process, the non-aqueous electrolyte of this disclosure is injected into the interior of the assembly. This allows the non-aqueous electrolyte to permeate the positive electrode composite layer, the separator, and the negative electrode composite layer. As a result, a lithium secondary battery precursor is obtained.

[0200] [Method of manufacturing lithium secondary batteries] Next, a method for manufacturing the lithium secondary battery of this disclosure will be described.

[0201] The method for manufacturing a lithium secondary battery according to this disclosure includes a fourth preparation step and an aging step. The fourth preparation step and the aging step are performed in this order.

[0202] In the fourth preparation step, the lithium secondary battery precursor is prepared. The method for preparing the lithium secondary battery precursor is the same as the method described in the section on the manufacturing method of the lithium secondary battery precursor.

[0203] In the aging process, the lithium secondary battery precursor is subjected to an aging treatment. This forms the negative electrode SEI film and the positive electrode SEI film. In other words, a lithium secondary battery is obtained. The aging process involves charging and discharging the lithium secondary battery precursor in an environment between 25°C and 70°C. More specifically, the aging process includes a first charging phase, a first holding phase, a second charging phase, a second holding phase, and a charge-discharge phase. In the first charging phase, the lithium secondary battery precursor is charged in an environment between 25°C and 70°C. In the first holding phase, the lithium secondary battery precursor after the first charging phase is held in an environment between 25°C and 70°C. In the second charging phase, the lithium secondary battery precursor after the first holding phase is charged in an environment between 25°C and 70°C. In the second holding phase, the lithium secondary battery precursor after the second charging phase is held in an environment between 25°C and 70°C. In the charge-discharge phase, the lithium secondary battery precursor after the second holding phase is subjected to one or more combinations of charging and discharging in an environment between 25°C and 70°C.

[0204] The lithium secondary battery obtained by the lithium secondary battery manufacturing method of this disclosure exhibits a more effective suppression of the increase in DC resistance and decrease in discharge capacity even when stored in a high-temperature environment. [Examples]

[0205] The embodiments relating to this disclosure will be described in detail below with reference to the examples. However, this disclosure is not limited in any way to the descriptions of these examples.

[0206] [Synthesis of lithium (N-carbonyl) sulfonamide compound (I)] The synthetic compounds (I-1) to (I-48), represented by the following formula (I), were synthesized as follows. In formula (I) of each of the synthetic compounds (I-1) to (I-48), R 1 , R 2 , L 1 , and L 2This is shown in Tables 1 and 2.

[0207] [ka]

[0208] [Table 1]

[0209] [Table 2]

[0210] [Table 3]

[0211] [Synthesis Example 1] Lithium butoxycarbonyltosylamide [synthetic compound (I-5)], represented by the following structural formula, was synthesized as described below.

[0212] [ka]

[0213] <Step 1: Synthesis of Butoxycarbonyltosylamide> A 200 mL four-necked flask connected to a nitrogen-purged Liebig condenser was charged with p-toluenesulfonyl isocyanate (3.94 g, 20 mmol), dibutyltin dilaurine (0.126 g, 0.2 mmol), and dichloromethane (100 mL) as a solvent. The flask was kept at room temperature, and n-butanol (1.78 g, 24 mmol) was added. The mixture was stirred at reflux temperature (40°C). After 4 hours, the reaction was stopped and the flask was cooled to room temperature. Subsequently, the resulting reaction product was washed. Specifically, 100 mL of distilled water and 10 mL of ethyl acetate were added to the reaction mixture, and the mixture was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. The hexane / ethyl acetate solvent consists of hexane and ethyl acetate. This yielded the first white solid, butoxycarbonyltosylamide (5.27 g, 19.42 mmol, 97% yield). First white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0214] <Step 2: Synthesis of lithium butoxycarbonyltosylamide (I-5)> In a nitrogen-purged 200 mL four-necked flask, butoxycarbonyltosylamide (3.11 g, 11.46 mmol) and tetrahydrofuran (50 mL) as solvent were placed, and the flask was maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M, 1.3 mol / dm³) was added. 3 After adding ), and tetrahydrofuran solution (8.8 mL, 11.46 mmol) over 5 minutes, the mixture was allowed to return to room temperature and stirred for 6 hours, at which point 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 removed by distillation under reduced pressure. This yielded a second white solid, lithium butoxycarbonyltosylamide (2.17 g, 7.83 mmol, 68% yield). Second white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-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)

[0215] As described above, based on the results of Synthesis Example 1, lithium butoxytosylamide [synthetic compound (I-5)] was obtained by the following reaction scheme.

[0216] [ka]

[0217] [Synthesis Example 2] Lithium methoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-10)], represented by the following structural formula, was synthesized as described below.

[0218] [ka]

[0219] <Step 1: Synthesis of Methoxycarbonyltrifluoromethylsulfonamide> In a nitrogen-purged 200 mL four-necked flask, 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 charged. The flask was kept at 0°C, and methyl chloroformate (7.62 g, 81 mmol) was added over 5 minutes. The mixture was then allowed to return to room temperature and stirred for 6 hours. The resulting reaction solution was then filtered to remove the hydrochloride salt, and the solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and the solution was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded a third white solid, methoxycarbonyltrifluoromethylsulfonamide (3.12 g, 33.6 mmol, yield 44.8%). Third white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.51(s,3H), 10.00(br,2H)

[0220] <Step 2: Synthesis of Lithium Methoxycarbonyl Trifluoromethylsulfonamide (I-10)> In a nitrogen-purged 200 mL four-necked flask, methoxycarbonyltrifluoromethylsulfonamide (1.90 g, 9.17 mmol) and diethyl ether (50 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.1 mL, 9.17 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (50 mL) was added at room temperature, and a fourth white solid precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained fourth white solid was removed by distillation under reduced pressure. This results in the fourth white solid, lithium methoxycarbonyltrifluoromethylsulfone. An amide (0.99 g, 4.65 mmol, 51% yield) was obtained. Fourth white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.40(s,3H)

[0221] As described above, based on the results of Synthesis Example 2, lithium methoxycarbonyltrifluoromethylsulfonamide [synthetic compound (I-10)] was obtained by the following reaction scheme.

[0222] [ka]

[0223] [Synthesis Example 3] Lithium methoxycarbonyl tosylamide [synthetic compound (I-1)], represented by the following structural formula, was synthesized as described below.

[0224] [ka]

[0225] <Step 1: Synthesis of Methoxycarbonyltosylamide> The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that n-butanol was replaced with methanol (1.28 g, 40 mmol) in the first step. This yielded the fifth white solid, methoxycarbonyl tosylamide (4.33 g, 18.89 mmol, 94% yield). Fifth white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0226] <Step 2: Synthesis of Lithium Methoxycarbonyl Tosylamide (I-1)> Synthesis Example 1 (Synthesis Compound I - The reaction was carried out in the same manner as in the second step of 5), using methoxycarbonyl tosylamide (1.52 g, 6.63 mmol), tetrahydrofuran (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.1 mL, 6.63 mmol). This yielded lithium methoxycarbonyl tosylamide, a sixth white solid (0.99 g, 4.20 mmol, 63% yield). The sixth white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0227] [Synthesis Example 4] Lithium ethoxycarbonyltosylamide [synthetic compound (I-2)], represented by the following structural formula, was synthesized as described below.

[0228] [ka]

[0229] <Step 1: Synthesis of Ethoxycarbonyltosylamide> The synthesis was carried out in the same manner as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that n-butanol was replaced with ethanol (1.84 g, 40 mmol) in the first step. This yielded the seventh white solid, ethoxycarbonyltosylamide (4.47 g, 18.37 mmol, 92% yield). The seventh white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0230] <Step 2: Synthesis of Lithium Ethoxycarbonyltosylamide (I-2)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using ethoxycarbonyltosylamide (3.24 g, 13.32 mmol), tetrahydrofuran (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (10.2 mL, 13.32 mmol). This yielded lithium ethoxycarbonyl tosylamide (1.14 g, 4.56 mmol, yield 34%), which is a white solid. Eighth white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0231] [Synthesis Example 5] Lithium propoxycarbonyltosylamide [synthetic compound (I-3)], represented by the following structural formula, was synthesized as described below.

[0232] [ka]

[0233] <Step 1: Synthesis of propylcarbonyltosylamide> Synthesis Example 1 (I-5) was synthesized using the same method as the first step of Synthesis Example 1, except that in the first step, p-toluenesulfonyl isocyanate (4.75 g, 24.09 mmol) was used and n-butanol was replaced with n-propanol (1.74 g, 28.9 mmol). This yielded the ninth white solid, propylcarbonyl tosylamide (5.70 g, 22.15 mmol, 92% yield). Ninth white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0234] <Step 2: Synthesis of lithium propoxycarbonyltosylamide (I-3)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using propylcarbonyltosylamide (5.70 g, 22.15 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (17.0 mL, 22.15 mmol). This yielded lithium propoxycarbonyltosylamide, a white solid (3.66 g, 13.90 mmol, 63% yield). The 10th white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0235] [Synthesis Example 6] Lithium isopropoxycarbonyltosylamide [synthetic compound (I-4)], represented by the following structural formula, was synthesized as described below.

[0236] [ka]

[0237] <Step 1: Synthesis of Isopropylcarbonyltosylamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that n-butanol was replaced with isopropanol (2.40 g, 40 mmol) in the first step. This yielded the 11th white solid, isopropylcarbonyltosylamide (4.55 g, 17.68 mmol, yield 88%). The 11th white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0238] <Step 2: Synthesis of lithium isopropoxycarbonyltosylamide (I-4)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using isopropoxycarbonyltosylamide (5.55 g, 21.57 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (16.6 mL, 21.57 mmol). This yielded the twelfth white solid, lithium isopropoxycarbonyl tosylamide (5.46 g, 20.74 mmol, 96% yield). The 12th white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-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)

[0239] [Synthesis Example 7] Lithium-t-butoxycarbonyltosylamide [synthetic compound (I-6)], represented by the following structural formula, was synthesized as described below.

[0240] [ka]

[0241] <Step 1: Synthesis of t-butylcarbonyltosylamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that n-butanol was replaced with t-butylbutyl alcohol (1.78 g, 24 mmol) in the first step. This yielded the 13th white solid, t-butylcarbonyltosylamide (4.53 g, 16.70 mmol, yield 83%). The 13th white solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0242] <Second step: Synthesis of lithium-t-butoxycarbonyltosylamide (I-6)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using t-butylcarbonyltosylamide (2.06 g, 7.59 mmol), tetrahydrofuran (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.8 mL, 7.59 mmol). This yielded lithium-t-butoxycarbonyltosylamide (2.0 g, 7.21 mmol, 95% yield), a white solid of type 14. 14 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0243] [Synthesis Example 8] Lithium-2,2,2-trifluoroethoxycarbonyltosylamide [synthetic compound (I-7)], represented by the following structural formula, was synthesized as described below.

[0244] [ka]

[0245] <Step 1: Synthesis of 2,2,2-trifluoroethoxycarbonyltosylamide> The compound was synthesized using the same method as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that p-toluenesulfonyl isocyanate (4.73 g, 24.0 mmol) was used in the first step, and n-butanol was replaced with 2,2,2-trifluoroethanol (2.40 g, 24.0 mmol). This yielded the 15th white solid, 2,2,2-trifluoroethoxycarbonyltosylamide (5.12 g, 17.22 mmol, 72% yield). 15th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0246] <Second step: Synthesis of lithium-(2,2,2-trifluoroethoxy)tosylamide (I-7)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using 2,2,2-trifluoroethoxycarbonyltosylamide (5.80 g, 19.51 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (15.0 mL, 19.51 mmol). This yielded the 16th white solid, lithium-(2,2,2-trifluoroethoxy)carbonyltosylamide (4.98 g, 16.43 mmol, yield 84%). 16 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0247] [Synthesis Example 9] Lithium phenoxycarbonyltosylamide [synthetic compound (I-8)], represented by the following structural formula, was synthesized as described below.

[0248] [ka]

[0249] <Step 1: Synthesis of phenoxycarbonyltosylamide> The synthesis was carried out in the same manner as the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that in the first step, p-toluenesulfonyl isocyanate (8.32 g, 42.2 mmol) was used and n-butanol was replaced with phenol (4.40 g, 46.7 mmol). This yielded the 17th white solid, phenoxycarbonyltosylamide (10.33 g, 35.50 mmol, yield 84%). 17 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0250] <Step 2: Synthesis of Lithium Phenoxycarbonyltosylamide (I-8)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using phenoxycarbonyltosylamide (2.70 g, 9.27 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.1 mL, 9.27 mmol). This yielded the 18th white solid, lithium phenoxycarbonyl tosylamide (2.0 g, 6.80 mmol, yield 73%). 18 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0251] [Synthesis Example 10] Lithium 2-methoxyethylcarbonyltosylamide [synthetic compound (I-9)], represented by the following structural formula, was synthesized as described below.

[0252] [ka]

[0253] <Step 1: Synthesis of 2-methoxyethylcarbonyltosylamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 1 (Synthetic Compound (I-5)), except that p-toluenesulfonyl isocyanate (4.14 g, 21.0 mmol) was used in the first step, and n-butanol was replaced with 2-methoxyethanol (1.60 g, 21.0 mmol). This yielded the 19th white solid, 2-methoxyethylcarbonyltosylamide (5.63 g, 20.60 mmol, 98% yield). 19 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-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)

[0254] <Second step: Synthesis of lithium 2-methoxyethylcarbonyltosylamide (I-9)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using 2-methoxyethylcarbonyltosylamide (5.63 g, 20.60 mmol), tetrahydrofuran (100 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (15.8 mL, 20.60 mmol). This yielded the 20th white solid, lithium 2-methoxyethylcarbonyl tosylamide (5.45 g, 19.52 mmol, 95% yield). 20th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0255] [Synthesis Example 11] Lithium ethoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-11)], represented by the following structural formula, was synthesized as described below.

[0256] [ka]

[0257] <Step 1: Synthesis of Ethoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that methyl chloroformate was replaced with ethyl chloroformate (8.56 g, 79 mmol) in the first step. This yielded the 21st white solid, ethoxycarbonyltrifluoromethylsulfonamide (3.12 g, 33.6 mmol, 45% yield). 21st White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-NMR: δ1.28(t,J=4.2Hz,3H), 4.32(q,J=4.3Hz,2H), 12.04(br,2H)

[0258] <Step 2: Synthesis of Lithium Ethoxycarbonyl Trifluoromethylsulfonamide (I-11)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using ethoxycarbonyltrifluoromethylsulfonamide (2.01 g, 9.04 mmol), diethyl ether (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.0 mL, 9.04 mmol). This yielded the 22nd white solid, lithium ethoxycarbonyltrifluoromethylsulfonamide (1.43 g, 6.30 mmol, 70% yield). 22nd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.10(t,J=7.0Hz,3H), 3.83(q,J=7.0Hz,2H)

[0259] [Synthesis Example 12] Lithium propoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-12)], represented by the following structural formula, was synthesized as described below.

[0260] [ka]

[0261] <Step 1: Synthesis of propoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with propyl chloroformate (7.07 g, 57.7 mmol). This yielded the 23rd white solid, propoxycarbonyltrifluoromethylsulfonamide (6.40 g, 27.2 mmol, 94% yield). 23rd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ0.87(t,J=7.3Hz,3H), 1.30-1.55(m,2H), 3.86(t,J=6.3Hz,2H)

[0262] <Second step: Lithium propoxycarbonyltrifluoromethylsulfonamide (I-12)> Synthesis of > The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using propoxycarbonyltrifluoromethylsulfonamide (3.28 g, 13.95 mmol), diethyl ether (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (10.7 mL, 13.95 mmol). This yielded lithium propoxycarbonyltrifluoromethylsulfonamide (2.13 g, 8.83 mmol, 63% yield), a white solid (No. 24). 24th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ0.85(t,J=7.3Hz,3H), 1.35-1.60(m,2H), 3.75(t,J=6.6Hz,2H)

[0263] [Synthesis Example 13] Lithium isopropoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-13)], represented by the following structural formula, was synthesized as described below.

[0264] [ka]

[0265] <Step 1: Synthesis of Isopropoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with isopropyl chloroformate (7.07 g, 57.7 mmol). This yielded the 25th white solid, isopropoxycarbonyltrifluoromethylsulfonamide (5.56 g, 23.6 mmol, yield 82%). 25th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.14(d,J=4.3Hz,3H), 1.16(d,J=4.3Hz,3H), 4.60-4.80(m,1H)

[0266] <Step 2: Synthesis of lithium isopropoxycarbonyltrifluoromethylsulfonamide (I-13)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using isopropoxycarbonyltrifluoromethylsulfonamide (3.38 g, 14.37 mmol), diethyl ether (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (11.0 mL, 14.37 mmol). This yielded lithium isopropoxycarbonyltrifluoromethylsulfonamide (2.55 g, 10.58 mmol, 74% yield), a white solid. 26th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 1H-NMR: δ1.10 (d, J=6.2Hz, 6H)

[0267] [Synthesis Example 14] Lithium butoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-14)], represented by the following structural formula, was synthesized as described below.

[0268] [ka]

[0269] <Step 1: Synthesis of Butoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with butyl chloroformate (9.16 g, 67.1 mmol). This yielded the 27th white solid, butoxycarbonyltrifluoromethylsulfonamide (7.32 g, 29.4 mmol, yield 88%). 27th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0270] <Step 2: Synthesis of lithium butoxycarbonyltrifluoromethylsulfonamide (I-14)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using butoxycarbonyltrifluoromethylsulfonamide (2.50 g, 10.03 mmol), diethyl ether (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.7 mL, 10.03 mmol). This yielded lithium butoxycarbonyltrifluoromethylsulfonamide (2.21 g, 8.66 mmol, yield 86%), a white solid. 28th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ0.87(t,J=7.2Hz,3H), 1.15-1.55(m,4H), 3.79(t,J=6.6Hz,2H)

[0271] [Synthesis Example 15] Lithium phenoxycarbonyltrifluoromethylsulfonamide [synthetic compound (I-15)], represented by the following structural formula, was synthesized as described below.

[0272] [ka]

[0273] <Step 1: Synthesis of phenoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with phenyl chloroformate (3.15 g, 20.1 mmol). This yielded the 29th white solid, phenoxycarbonyltrifluoromethylsulfonamide (1.83 g, 6.8 mmol, yield 34%). 29th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.70-6.85(m,3H), 7.16(t,J=7.8Hz, 2H), 9.33(br, 1H)

[0274] <Step 2: Synthesis of Lithium Phenoxycarbonyl Trifluoromethylsulfonamide (I-15)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using phenoxycarbonyltrifluoromethylsulfonamide (1.73 g, 6.43 mmol), diethyl ether (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (4.9 mL, 6.43 mmol). This yielded the 30th white solid, lithium phenoxycarbonyltrifluoromethylsulfonamide (0.78 g, 2.83 mmol, yield 44%). 30th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ5.98(t,J=6.9Hz,1H), 6.23(d,J=7.6Hz,2H), 6.76(t,J=7.4Hz,2H)

[0275] [Synthesis Example 16] Lithium methoxycarbonylmethylsulfonamide [synthetic compound (I-16)], represented by the following structural formula, was synthesized as described below.

[0276] [ka]

[0277] <Step 1: Synthesis of Methoxycarbonylmethylsulfonamide> The compound (I-10) was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, methyl chloroformate (19.87 g, 210 mmol), triethylamine (21.28 g, 210 mmol), 4-dimethylaminopyridine (2.57 g, 21 mmol), and tetrahydrofuran (200 mL) were used as the solvent, and trifluoromethanesulfonamide was replaced with methanesulfonamide (10 g, 105 mmol). This yielded the 31st white solid, methoxycarbonylmethylsulfonamide (0.65 g, 4.24 mmol, yield 4%). 31st White Solid 1 The measurement results obtained by 1H-NMR (CD3OD-d4) are shown below. 1 H-NMR: δ3.24(s,3H), 3.77(s,3H)

[0278] <Step 2: Synthesis of Lithium Methoxycarbonylmethylsulfonamide (I-16)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using methoxycarbonylmethylsulfonamide (0.50 g, 3.25 mmol), tetrahydrofuran (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.5 mL, 3.25 mmol). This yielded lithium methoxycarbonylmethylsulfonamide (0.31 g, 1.96 mmol, 60% yield), a white solid. 32 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ2.61(s,3H), 3.27(s,3H)

[0279] [Synthesis Example 17] Lithium-t-butoxycarbonylmethylsulfonamide [Synthetic Compound (I-17)], represented by the following structural formula, was synthesized as described below.

[0280] [ka]

[0281] (First step: Synthesis of t-butoxycarbonylmethylsulfonamide) The compound was synthesized in the same manner as in the first step of Synthesis Example 16 (Synthetic Compound (I-16)), except that 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) were used as the solvent, and methyl chloroformate was replaced with di-t-butyl dioxide (9.18 g, 42.1 mmol). This yielded the 33rd white solid, t-butoxycarbonylmethylsulfonamide (5.22 g, 26.7 mmol, yield 64%). 33 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.44(s,9H), 3.20(s,3H)

[0282] <Step 2: Synthesis of lithium-t-butoxycarbonylmethylsulfonamide (I-17)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using t-butoxycarbonylmethylsulfonamide (5.0 g, 25.6 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (19.7 mL, 25.6 mmol). This yielded lithium-t-butoxycarbonyltrifluoromethylsulfonamide (4.91 g, 24.5 mmol, 95% yield), a white solid. 34th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.30(s,9H), 2.64(s,3H)

[0283] [Synthesis Example 18] Lithium phenoxycarbonylmethylsulfonamide [synthetic compound (I-18)], represented by the following structural formula, was synthesized as described below.

[0284] [ka]

[0285] <Step 1: Synthesis of phenoxycarbonylmethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that 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) were used as the solvent, and methyl chloroformate was replaced with phenyl chloroformate (5.93 g, 37.8 mmol). This yielded the 35th white solid, phenoxycarbonylmethylsulfonamide (3.25 g, 15.1 mmol, 48% yield). 35th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.31(s,3H), 7.22(d,J=8.4Hz,2H), 7.25-7.50(m,3H)

[0286] <Step 2: Synthesis of Lithium Phenoxycarbonylmethylsulfonamide (I-18)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using phenoxycarbonylmethylsulfonamide (2.11 g, 9.8 mmol), tetrahydrofuran (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.5 mL, 9.8 mmol). This yielded lithium phenoxycarbonylmethylsulfonamide (1.96 g, 8.9 mmol, 90% yield), a white solid (No. 36). 36th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0287] [Synthesis Example 19] Lithium acetylethoxysulfonamide [synthetic compound (I-19)], represented by the following structural formula, was synthesized as described below.

[0288] [ka]

[0289] <Step 1: Synthesis of Acetylethoxysulfonamide> Acetylethoxysulfonamide ethyl was synthesized following the example of the patent document (International Publication No. 2017 / 156179). In a 200 mL four-necked flask purged with nitrogen, chlorosulfonyl isocyanate (7.08 g, 50 mmol) and dichloromethane (100 mL) as solvent were added and kept at 0°C. Acetic acid (3.0 g, 50 mmol) was added, and the mixture was allowed to return to room temperature and stirred for 6 hours. After the reaction was complete, the solvent was concentrated and removed to obtain a white solid. A first reaction solution was prepared by adding tetrahydrofuran (50 mL) to this four-necked flask and kept at 0°C. 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 the second reaction solution. This second reaction solution was added to the four-necked flask containing the first reaction solution over 10 minutes at 0°C, then allowed to return to room temperature and stirred for 6 hours. After that, the resulting reaction solution was filtered to remove the hydrochloride salt, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and the solution was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded the 37th white solid, acetylethoxysulfonamide (2.87 g, 17.2 mmol, 56% yield). 37th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0290] <Step 2: Synthesis of Lithium Acetylethoxysulfonamide (I-19)> Acetylethoxysulfonamide (1.74 g, 10.4 mmol) and tetrahydrofuran (30 mL) as solvent were placed in a nitrogen-purged 200 mL four-necked flask and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (8.0 mL, 10.4 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (30 mL) was added, and solid No. 38 (white) precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid No. 38 (white) was removed by distillation under reduced pressure. This yielded lithium acetylethoxysulfonamide (0.22 g, 1.27 mmol, yield 12%) as the 38th white solid. 38th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.13(t,J=7.2Hz,3H), 1.71(s,3H), 3.86(q,J=7.3Hz,2H)

[0291] [Synthesis Example 20] Lithium ethoxysulfonyl-2,2,2-trifluoroacetylamide [synthetic compound (I-20)], represented by the following structural formula, was synthesized as described below.

[0292] [ka]

[0293] <Step 1: Synthesis of ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide> Following the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, pp. 677-680), ethyl sulfamate (6.45 g, 51.5 mmol, 62% yield) was synthesized. In a nitrogen-purged 200 mL four-necked flask, 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 charged. The flask was kept at 0°C, and anhydrous trifluoroacetic acid (4.13 g, 19.7 mmol) was added over 10 minutes. The mixture was then allowed to return to room temperature and stirred for 6 hours. The resulting reaction solution was then filtered to remove the hydrochloride salt, and the solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and the solution was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded the 39th white solid, ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (1.22 g, 5.52 mmol, yield 34%). 39th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-NMR: δ1.18(t,J=4.5Hz,3H), 3.98(q,J=7.0Hz,2H), 8.38(br,1H)

[0294] <Step 2: Synthesis of lithium ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (I-20)> In a nitrogen-purged 200 mL four-necked flask, ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (1.0 g, 4.5 mmol) and tetrahydrofuran (20 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.5 mL, 4.5 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (20 mL) was added, causing a white solid to precipitate from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent was removed by distillation under reduced pressure. This yielded the 40th white solid lithium ethoxysulfonyl-(2,2,2-trifluoroacetyl)amide (0.12 g, 0.53 mmol, yield 12%). 40th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.08(dt,J=7.0Hz,1.1Hz,H), 3.68(dq,J=7.0Hz,1.1Hz,2H)

[0295] [Synthesis Example 21] Lithium propionyl-(2,2,2-trifluoroethoxy)sulfonamide [synthetic compound (I-21)], represented by the following structural formula, was synthesized as described below.

[0296] [ka]

[0297] <Step 1: Synthesis of propionyl-(2,2,2-trifluoroethoxy)sulfonamide> Following the example of the patent document (International Publication No. 2017 / 156179), propionyl-(2,2,2-trifluoroethoxy)sulfonamide was synthesized. In a 200 mL four-necked flask purged with nitrogen, chlorosulfonyl isocyanate (14.15 g, 100 mmol) and dichloromethane (100 mL) as a solvent were added and kept at 0°C. Propionic acid (7.41 g, 100 mmol) was added, and the mixture was allowed to return to room temperature and stirred for 6 hours. After the reaction was complete, the solvent was concentrated and removed to obtain a white solid. A third reaction solution was prepared by adding tetrahydrofuran (100 mL) to this four-necked flask and kept at 0°C. 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 the fourth reaction solution. This fourth reaction solution was added to a four-necked flask containing the third reaction solution over 10 minutes at 0°C, then allowed to return to room temperature and stirred for 6 hours. After that, the resulting reaction solution was filtered to remove the hydrochloride salt, and the resulting solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and the solution was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded the 41st white solid, propionyl-(2,2,2-trifluoroethoxy)sulfonamide (11.63 g, 49.5 mmol, 50% yield). 41st White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.00(t,J=7.4Hz,3H), 2.32(q,J=7.8Hz,2H), 4.93(q,J=8.6Hz,2H)

[0298] <Step 2: Synthesis of lithium propionyl-(2,2,2-trifluoroethoxy)sulfonamide (I-21)> In a nitrogen-purged 200 mL four-necked flask, propionyl-(2,2,2-trifluoroethoxy)sulfonamide (1.75 g, 7.4 mmol) and tetrahydrofuran (30 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.7 mL, 7.4 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Subsequently, n-hexane (30 mL) was added, and a 42nd white solid precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained 42nd white solid was removed by distillation under reduced pressure. This yielded the 42nd white solid lithium propionyl-(2,2,2-trifluoroethoxy)sulfonamide (0.79 g, 3.28 mmol, yield 44%). 42nd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ0.91(t,J=7.6Hz,3H), 1.98(q,J=7.6Hz,2H), 4.44(q,J=6.5Hz,2H)

[0299] [Synthesis Example 22] Lithium benzoyl-(2,2,2-trifluoroethoxy)sulfonamide [synthetic compound (I-22)], represented by the following structural formula, was synthesized as described below.

[0300] [ka]

[0301] <Step 1: Synthesis of benzoyl-(2,2,2-trifluoroethoxy)sulfonamide> Following the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, pp. 677-680), 2,2,2-trifluoroethylsulfamate (12.4 g, 69.2 mmol, yield 69%) was synthesized. In a nitrogen-purged 200 mL four-necked flask, 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 charged. 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 allowed to return to room temperature and stirred for 6 hours. The resulting reaction solution was then filtered to remove the hydrochloride salt, and the solution was washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the filtrate, and the mixture was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded the 43rd white solid, benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (3.22 g, 11.37 mmol, yield 81%). 43rd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0302] <Step 2: Synthesis of lithium benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (I-22)> In a nitrogen-purged 200 mL four-necked flask, benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (2.06 g, 7.3 mmol) and tetrahydrofuran (20 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.6 mL, 7.3 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (20 mL) was added, and solid 44 was precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid 44 was removed by distillation under reduced pressure. This yielded lithium benzoyl-(2,2,2-trifluoroethoxy)sulfonamide (1.13 g, 3.9 mmol, yield 54%), a white solid. 44th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0303] [Synthesis Example 23] Lithium benzoylethoxysulfonamide [synthetic compound (I-23)], represented by the following structural formula, was synthesized as described below.

[0304] [ka]

[0305] <Step 1: Synthesis of Benzoylethoxysulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 20 (Synthetic Compound (I-20)), except that in the first step, ethyl sulfamate (2.02 g, 16.1 mmol), 4-dimethylaminopyridine (0.39 g, 3.2 mmol), and tetrahydrofuran (30 mL) were used as the solvent, and trifluoroacetic anhydride was replaced with benzoyl chloride (2.72 g, 19.4 mmol) and pyridine with triethylamine (3.27 g, 32.3 mmol). This yielded benzoylethoxysulfonamide (1.95 g, 16.14 mmol, 53% yield), a white solid. 45th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0306] <Step 2: Synthesis of lithium benzoylethoxysulfonamide (I-23)> In a nitrogen-purged 200 mL four-necked flask, benzoylethoxysulfonamide (1.74 g, 7.6 mmol) and tetrahydrofuran (20 mL) as solvent were placed and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.8 mL, 7.6 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (20 mL) was added, and solid 46 was precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid 46 was removed by distillation under reduced pressure. This yielded lithium benzoylethoxysulfonamide (1.29 g, 5.5 mmol, 72% yield), a white solid. 46th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-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)

[0307] [Synthesis Example 24] Lithium acetylphenoxysulfonamide [synthetic compound (I-24)], represented by the following structural formula, was synthesized as described below.

[0308] [ka]

[0309] <First step: Synthesis of phenyl sulfamate> Following the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, pp. 677-680), sulfamoyl chloride was synthesized. The fifth reaction solution was prepared by charging a 200 mL four-necked flask, which had been purged with nitrogen, with sulfamoyl chloride (32.1 g, 278 mmol) and tetrahydrofuran (300 mL) as the solvent, and the solution was kept at 0°C. 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 the sixth reaction solution. This sixth reaction solution was added to the four-necked flask containing the fifth reaction solution over 30 minutes at 0°C, then allowed to return to room temperature and stirred for 6 hours. After that, the resulting reaction solution was filtered to remove the 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 the mixture was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded phenylsulfamate (18.5 g, 107 mmol, 38% yield) as a white solid. 47th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.41(t,J=7.0Hz,3H), 4.29(q,J=7.3Hz,2H), 4.91(br,2H)

[0310] The reaction equation for the first step of synthesis example 24 is as follows:

[0311] [ka]

[0312] (Second step: Synthesis of acetylphenoxysulfonamide) The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that pyridine (4.99 g, 63.1 mmol), 4-dimethylaminopyridine (0.77 g, 6.3 mmol), and tetrahydrofuran (30 mL) were used as the solvent, and methanesulfonamide was replaced with phenylsulfamate (2.68 g, 15.5 mmol) and methyl chloroformate with acetyl chloride (1.46 g, 18.6 mmol) in the first step. This yielded a black solid acetylphenoxysulfonamide (2.11 g, 9.8 mmol, 63% yield). Black solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ2.05(s,3H), 7.27(t,J=8.6Hz,2H), 7.35-7.60(m,3H), 12.44(br,1H)

[0313] <Third step: Synthesis of lithium acetylphenoxysulfonamide (I-24)> Acetylphenoxysulfonamide (2.11 g, 9.8 mmol) and tetrahydrofuran (20 mL) as solvent were placed in a nitrogen-purged 200 mL four-necked flask and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.5 mL, 9.8 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Subsequently, n-hexane (20 mL) was added, and solid no. 48 precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid no. 48 was removed by distillation under reduced pressure. This yielded the 48th white solid lithium acetylphenoxysulfonamide (1.83 g, 8.27 mmol, yield 84%). 48th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.72(s, 3H), 7.05-7.20(m, 3H), 7.30(t,J=5.1Hz, 2H)

[0314] [Synthesis Example 25] Lithium benzoylphenoxysulfonamide [synthetic compound (I-25)], represented by the following structural formula, was synthesized as described below.

[0315] [ka]

[0316] <First step: Synthesis of phenyl sulfamate> Phenyl sulfamate was obtained by the same method as in the first step of Synthesis Example 24 (Synthetic Compound (I-24)).

[0317] <Step 2: Synthesis of Benzoylphenoxysulfonamide> White solid No. 49 was synthesized in the same manner as in the second step of Synthesis Example 24 (Synthetic Compound (I-24)), using phenyl sulfamate (4.10 g, 23.7 mmol), 4-dimethylaminopyridine (0.58 g, 5.8 mmol), and tetrahydrofuran (50 mL) as the solvent, except that acetyl chloride was replaced with benzoyl chloride (3.99 g, 28.4 mmol) and pyridine was replaced with triethylamine (4.79 g, 47.3 mmol). This yielded the 49th white solid, benzoylphenoxysulfonamide (4.93 g, 17.8 mmol, 75% yield). 49th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ7.29(d,J=8.4Hz,2H), 7.30-7.70(m,6H), 7.89(d,J=7.3Hz,2H)

[0318] <Third step: Synthesis of lithium benzoylphenoxysulfonamide (I-25)> In a nitrogen-purged 200 mL four-necked flask, benzoylphenoxysulfonamide (3.12 g, 11.25 mmol) and tetrahydrofuran (30 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (8.7 mL, 11.25 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (30 mL) was added, and solid no. 50 precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid no. 50 was removed by distillation under reduced pressure. This yielded the 50th white solid lithium benzoylphenoxysulfonamide (2.04 g, 7.20 mmol, yield 64%). 50th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ7.05-7.45(m,8H), 7.90(d,J=7.6Hz,2H)

[0319] [Synthesis Example 26] Lithium ethoxycarbonylethoxysulfonamide [Synthetic compound (I-26)], represented by the following structural formula, was synthesized as described below.

[0320] [ka]

[0321] <Step 1: Synthesis of Ethoxycarbonylethoxysulfonamide> A 500 mL four-necked flask connected to a nitrogen-purged Liebig condenser was charged with chlorosulfonyl isocyanate (4.00 g, 28.3 mmol) and dichloromethane (100 mL) as a solvent. The flask was kept at room temperature, and ethanol (3.26 g, 70.8 mmol) and triethylamine (2.86 g, 28.3 mmol) were added. The reaction was stirred at reflux temperature. After 4 hours, the reaction was stopped and the mixture was cooled to room temperature. The resulting reaction product was then washed. Specifically, 100 mL of distilled water and 100 mL of ethyl acetate were added to the reaction mixture, and the mixture was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded the 51st white solid, ethoxycarbonylethoxysulfonamide (5.27 g, 11.3 mmol, 40% yield). The 1H-NMR (CDCl3) measurement results for the 51st white solid are shown below. 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)

[0322] The reaction equation for the first step of synthesis example 26 is as follows:

[0323] [ka]

[0324] <Step 2: Synthesis of Lithium Ethoxycarbonyl Ethoxysulfonamide (I-26)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using ethoxycarbonylethoxysulfonamide (1.02 g, 5.17 mmol), tetrahydrofuran (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.50 mL, 4.55 mmol). This yielded lithium ethoxycarbonylethoxysulfonamide (258 mg, 1.29 mmol, yield 25%), a white solid. 52 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0325] [Synthesis Example 27] Lithium ethoxycarbonyl-2,2,2-trifluoroethoxysulfonamide [Synthetic Compound (I-27)], represented by the following structural formula, was synthesized as described below.

[0326] [ka]

[0327] <Step 1: Synthesis of ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide> Following the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, pp. 677-680), 2,2,2-trifluoroethylsulfamate (12.4 g, 69.2 mmol, yield 69%) was synthesized. In the first step of Synthesis Example 22 (Synthetic Compound (I-22)), 2,2,2-trifluoroethylsulfamate (2.55 g, 14.2 mmol), 4-dimethylaminopyridine (0.35 g, 2.85 mmol), and tetrahydrofuran (30 mL) were used as the solvent. The only differences were that benzoyl chloride was replaced with ethyl chloroformate (3.09 g, 28.5 mmol) and triethylamine was replaced with pyridine (2.25 g, 28.5 mmol). In this same manner as the first step of Synthesis Example 22, the 53rd white solid was synthesized. This yielded the 53rd white solid, ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (2.28 g, 9.08 mmol, yield 64%). 53 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.22(t,J=7.0Hz,3H), 4.17(q,J=6.8Hz,2H), 4.93(q,J=8.4Hz,2H)

[0328] <Step 2: Synthesis of Lithium Ethoxycarbonyl-(2,2,2-Trifluoroethoxy)sulfonamide (I-27)> In a nitrogen-purged 200 mL four-necked flask, ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (2.0 g, 7.96 mmol) and tetrahydrofuran (30 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) and tetrahydrofuran solution (6.1 mL, 7.96 mmol) were added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Subsequently, n-hexane (30 mL) was added, and solid no. 54 precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid no. 54 was removed by distillation under reduced pressure. This yielded the 54th white solid lithium ethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.95 g, 7.58 mmol, 95% yield). 54th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.08(t,J=4.5Hz,3H), 3.81(q,J=6.8Hz,2H), 4.40(q,J=9.2Hz,2H)

[0329] [Synthesis Example 28] Lithium-(2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide [Synthetic Compound (I-28)], represented by the following structural formula, was synthesized as described below.

[0330] [ka]

[0331] <Step 1: Synthesis of 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide> 2,2,2-trifluoroethanol (5.73 g, 57.3 mmol) and chlorobenzene (13 mL) as solvent were charged into a 100 mL four-necked flask connected to a nitrogen-purged Liebig condenser. The flask was kept at room temperature, and chlorosulfonyl isocyanate (4.05 g, 28.6 mmol) was added. The reaction was stirred at reflux temperature. After 12 hours, the reaction was stopped and the flask was 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. This yielded 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (7.34 g, 24.1 mmol, yield 84%), a first colorless, transparent oil. First colorless transparent oil 1 The measurement results by 1H-NMR (CDCl3) are shown below. 1 H-NMR: δ4.59(d,J=8.1Hz,2H), 4.73(d,J=7.6Hz,2H), 8.28(br,1H)

[0332] <Step 2: Synthesis of lithium-(2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide (I-28)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using 2,2,2-trifluoroethoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.50 g, 4.92 mmol), tetrahydrofuran (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.75 mL, 4.88 mmol). This yielded lithium-(2,2,2-trifluoroethoxy)carbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.51 g, 4.85 mmol, 99% yield), a white solid. 55 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ4.43(q,J=9.5Hz,2H), 4.44(q,J=9.0Hz,2H)

[0333] [Synthesis Example 29] Lithium benzoyl-(2,2,2-trifluoroethoxy)sulfonamide [synthetic compound (I-29)], represented by the following structural formula, was synthesized as described below.

[0334] [ka]

[0335] <Step 1: Synthesis of phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide> Following the non-patent literature (Journal of the Chemical Society. Perkin Transactions I, 1982, pp. 677-680), 2,2,2-trifluoroethylsulfamate (12.4 g, 69.2 mmol, yield 69%) was synthesized. In the first step of Synthesis Example 27 (Synthetic Compound (I-27)), 2,2,2-trifluoroethylsulfamate (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) were used as the solvent, and ethyl chloroformate was replaced with phenyl chloroformate (3.35 g, 21.4 mmol) to synthesize White Solid No. 56 using the same method as the first step of Synthesis Example 27. This yielded the 56th white solid, phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.97 g, 6.58 mmol, yield 37%). 56 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0336] <Step 2: Synthesis of Lithium Phenoxycarbonyl-(2,2,2-Trifluoroethoxy)sulfonamide (I-29)> In a nitrogen-purged 200 mL four-necked flask, phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.97 g, 6.58 mmol) and tetrahydrofuran (30 mL) as solvent were charged and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.1 mL, 6.58 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Then, n-hexane (30 mL) was added, and solid No. 57 (white solid) precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained solid No. 57 (white solid) was removed by distillation under reduced pressure. This yielded the 57th white solid, lithium phenoxycarbonyl-(2,2,2-trifluoroethoxy)sulfonamide (1.71 g, 5.60 mmol, yield 85%). 57 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0337] [Synthesis Example 30] Lithium ethoxycarbonyl-p-tolyloxysulfonamide [synthetic compound (I-30)], represented by the following structural formula, was synthesized as described below.

[0338] [ka]

[0339] <Step 1: Synthesis of p-tolyloxycarbonylchlorosulfonamide> Based on non-patent literature (Picard, JA et al., J. Med. Chem., 1996, 39, 1243.), p-tolyloxycarbonylchlorosulfonamide was synthesized. In a 100 mL four-necked flask connected to a nitrogen-purged Liebig condenser, p-cresol (7.04 g, 65.1 mmol) and chlorobenzene (20 mL) as a solvent were charged and kept at room temperature. Chlorosulfonyl isocyanate (9.21 g, 65.1 mmol) was added, and the mixture was stirred at room temperature for 1 hour, after which white solid No. 58 precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained white solid No. 58 was removed by distillation under reduced pressure. This yielded p-tolyloxycarbonylchlorosulfonamide (14.6 g, 58.5 mmol, 90% yield), a white solid. 58th White Solid 1 The measurement results by 1H-NMR (CDCl3) are shown below. 1 H-NMR: δ2.37(s, 3H), 7.09(d, J=8.5Hz, 2H), 7.22(d, J=8.5Hz, 2H)

[0340] <Step 2: Synthesis of Ethoxycarbonyl-p-Tolyloxysulfonamide> Ethoxycarbonyl-p-tolyloxysulfonamide was synthesized based on non-patent literature (Picard, JA et al., J. Med. Chem., 1996, 39, 1243). A 100 mL four-necked flask connected to a nitrogen-purged Liebig condenser was charged with tolyloxycarbonylchlorosulfonamide (5.00 g, 20.0 mmol) and chlorobenzene (30 mL) as a solvent, and the mixture was stirred at reflux temperature for 12 hours. After cooling to room temperature, ethanol (1.85 g, 40.2 mmol) was added, and the mixture was stirred at room temperature. The reaction was stopped after 2 hours, and the resulting reaction product was washed. Specifically, 30 mL of distilled water and 30 mL of ethyl acetate were added to the reaction mixture, and the product was extracted and washed using a separatory funnel. The above water washing was repeated twice, and magnesium sulfate was added to the resulting organic layer, which was then dried and concentrated under reduced pressure. The obtained crude product was separated and purified by flash column chromatography using a hexane / ethyl acetate solvent. This yielded a second colorless, transparent oil, ethoxycarbonyl-p-tolyloxysulfonamide (4.03 g, 15.5 mmol, 78% yield). Second colorless transparent oil 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0341] <Third step: Synthesis of lithium ethoxycarbonyl-p-tolyloxysulfonamide (I-30)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using ethoxycarbonyl-p-tolyloxysulfonamide (2.54 g, 9.80 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.30 mL, 9.49 mmol). This yielded the 59th white solid lithium ethoxycarbonyl-p-tolyloxysulfonamide (1.11 g, 4.19 mmol, yield 43%). 59 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0342] As described above, based on the results of Synthesis Example 30, lithium ethoxycarbonyl-p-tolyloxysulfonamide [synthetic compound (I-30)] was obtained by the following reaction scheme.

[0343] [ka]

[0344] [Synthesis Example 31] Lithium-p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide [synthetic compound (I-31)], represented by the following structural formula, was synthesized as described below.

[0345] [ka]

[0346] <Step 1: Synthesis of p-tolyloxycarbonylchlorosulfonamide> p-Tolyloxycarbonylchlorosulfonamide was synthesized using the same method as in the first step of Synthesis Example 30 (Synthetic Compound (I-30)).

[0347] <Step 2: Synthesis of p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide> The reaction was carried out in the same manner as in the second step of Synthesis Example 30 (Synthetic Compound (I-30)), using p-tolyloxycarbonylchlorosulfonamide (1.50 g, 6.01 mmol), chlorobenzene (10 mL) as the solvent, and 2,2,2-trifluoroethanol (0.60 g, 6.00 mmol). This yielded a third colorless, transparent oil, p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (1.01 g, 3.22 mmol, yield 54%). Third colorless transparent oil 1 The measurement results by 1H-NMR (CDCl3) are shown below. 1 H-NMR: δ2.37(s,3H), 4.62(q,J=8.1Hz,2H), 7.20(m,4H)

[0348] <Third step: Synthesis of lithium-p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (I-31)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic Compound (I-5)), using p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonylamide (1.01 g, 3.22 mmol), tetrahydrofuran (15 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.30 mL, 2.99 mmol). This yielded lithium-p-tolyloxysulfonyl-(2,2,2-trifluoroethoxy)carbonilamide (350 mg, 1.10 mmol, yield 34%), a white solid. 60th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0349] [Synthesis Example 32] Lithium-p-tolyloxycarbonyl-p-tolyloxysulfonamide [Synthetic Compound (I-32)], represented by the following structural formula, was synthesized as described below.

[0350] [ka]

[0351] <Step 1: Synthesis of p-tolyloxycarbonyl-p-tolyloxysulfonamide> The fourth colorless transparent oil was synthesized in the same manner as in the first step of Synthesis Example 28 (Synthetic Compound (I-28)), except that trifluoroethanol was replaced with p-cresol (6.20 g, 57.3 mmol) in the first step. This yielded a fourth colorless, transparent oil, p-tolyloxycarbonyl-p-tolyloxysulfonamide (9.10 g, 28.3 mmol, 99% yield). The fourth colorless and transparent oil 1 The measurement results by 1H-NMR (CDCl3) are shown below. 1 H-NMR: δ2.37(s,3H), 2.38(s,3H), 7.05(d,J=6.8Hz,2H), 7.21(m,6H)

[0352] <Step 2: Synthesis of lithium-p-tolyloxycarbonyl-p-tolyloxysulfonamide (I-32)> The reaction was carried out in the same manner as in the second step of Synthesis Example 1 (Synthetic 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). This yielded lithium-p-tolyloxycarbonyl-p-tolyloxysulfonamide (798 mg, 2.42 mmol, yield 65%), a white solid. 61st White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ2.27(s,3H), 2.28(s,3H), 6.82(d,J=8.6Hz,2H), 7.10(m,6H)

[0353] [Synthesis Example 33] Lithium-4-methylphenoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-33)], represented by the following structural formula, was synthesized as described below.

[0354] [ka]

[0355] <Step 1: Synthesis of 4-methylphenoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with 4-methylphenyl chloroformate (2.52 g, 14.8 mmol). This yielded the fifth colorless, transparent oil, 4-methylphenoxycarbonyltrifluoromethylsulfonamide (1.02 g, 3.6 mmol, yield 27%). Fifth colorless transparent oil 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.61-6.66(m,2H), 6.92-6.97(m,2H), 9.06(br, 1H)

[0356] <Step 2: Synthesis of Lithium-4-methylphenoxycarbonyltrifluoromethylsulfonamide (I-33)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using 4-methylphenoxycarbonyltrifluoromethylsulfonamide (1.02 g, 3.60 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.8 mL, 3.60 mmol). This yielded the 62nd white solid, lithium-4-methylphenoxycarbonyltrifluoromethylsulfonamide (0.76 g, 2.63 mmol, yield 73%). 62 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.18-6.34(m,2H), 6.58-6.66(m,2H)

[0357] [Synthesis Example 34] Lithium-4-methoxyphenoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-34)], represented by the following structural formula, was synthesized as described below.

[0358] [ka]

[0359] <Step 1: Synthesis of 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with 4-methoxyphenyl chloroformate (2.40 g, 12.9 mmol). This yielded the 63rd white solid, 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (1.55 g, 5.2 mmol, yield 48%). 63 White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.65(s,3H), 6.55-6.78(m,4H), 8.86(br, 1H)

[0360] <Step 2: Synthesis of Lithium-4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (I-34)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using 4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (0.95 g, 3.16 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.4 mL, 3.16 mmol). This yielded the 64th white solid lithium-4-methoxyphenoxycarbonyltrifluoromethylsulfonamide (0.79 g, 2.58 mmol, yield 82%). 64th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.55(s,3H), 6.13-6.28(m,2H), 6.43-6.52(m,2H)

[0361] [Synthesis Example 35] Lithium-4-chlorophenoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-35)], represented by the following structural formula, was synthesized as described below.

[0362] [ka]

[0363] <Step 1: Synthesis of 4-chlorophenoxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with 4-chlorophenyl chloroformate (3.07 g, 16.1 mmol). This yielded the sixth colorless, transparent oil, 4-chlorophenoxycarbonyltrifluoromethylsulfonamide (1.54 g, 5.1 mmol, yield 38%). The sixth colorless and transparent oil 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.74-6.79(m,2H), 7.17-7.22(m,2H)

[0364] <Step 2: Synthesis of Lithium-4-Chlorophenoxycarbonyltrifluoromethylsulfonamide (I-35)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using 4-chlorophenoxycarbonyltrifluoromethylsulfonamide (1.54 g, 5.07 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.9 mL, 5.07 mmol). This yielded lithium-4-chlorophenoxycarbonyltrifluoromethylsulfonamide (0.65 g, 2.10 mmol, yield 41%), which is a yellow solid. 65th Yellow Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.40-6.46(m,2H), 6.84-6.90(m,2H)

[0365] [Synthesis Example 36] Lithium-4-fluorophenoxycarbonyltrifluoromethylsulfonamide [Synthetic Compound (I-36)], represented by the following structural formula, was synthesized as described below.

[0366] [ka]

[0367] <Step 1: Synthesis of 4-fluorophenoxycarbonyltrifluoromethylsulfonamide> The compound (I-10) was synthesized using the same method as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with 4-fluorophenyl chloroformate (2.50 g, 14.3 mmol). did. This yielded the seventh colorless, transparent oil, 4-fluorophenoxycarbonyltrifluoromethylsulfonamide (2.02 g, 7.0 mmol, yield 54%). The seventh colorless transparent oil 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.71-6.76(m,2H), 6.94-7.01(m,2H), 9.34(br, 1H)

[0368] <Step 2: Synthesis of lithium-4-fluorophenoxycarbonyltrifluoromethylsulfonamide (I-36)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using 4-fluorophenoxycarbonyltrifluoromethylsulfonamide (2.02 g, 7.03 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (5.4 mL, 7.03 mmol). This yielded the 66th white solid, lithium-4-fluorophenoxycarbonyltrifluoromethylsulfonamide (0.91 g, 3.10 mmol, yield 44%). 66th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ6.21-6.31(m,2H), 6.58-6.68(m,2H)

[0369] [Synthesis Example 37] Lithium allyloxycarbonyltrifluoromethylsulfonamide [Synthetic compound (I-37)], represented by the following structural formula, was synthesized as described below.

[0370] [ka]

[0371] <Step 1: Synthesis of allyloxycarbonyltrifluoromethylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with allyl chloroformate (2.43 g, 20.1 mmol). This yielded the 67th white solid, allyloxycarbonyltrifluoromethylsulfonamide (2.46 g, 10.6 mmol, yield 63%). 67th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0372] <Step 2: Synthesis of Lithium Allyloxycarbonyl Trifluoromethylsulfonamide (I-37)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using allyloxycarbonyltrifluoromethylsulfonamide (2.20 g, 9.44 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.3 mL, 9.44 mmol). This yielded the 68th white solid, lithium allyloxycarbonyltrifluoromethylsulfonamide (1.58 g, 6.63 mmol, 70% yield). 68th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ4.25-4.40(m,2H), 5.00-5.30(m,2H), 5.85-5.96(m,1H)

[0373] [Synthesis Example 38] Lithium butoxycarbonyl-4-fluorophenylsulfonamide [Synthetic Compound (I-38)], represented by the following structural formula, was synthesized as described below.

[0374] [ka]

[0375] <Step 1: Synthesis of Butoxycarbonyl-4-Fluorophenylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 14 (Synthetic Compound (I-14)), except that in the first step, butyl chloroformate (2.34 g, 17.1 mmol), 4-dimethylaminopyridine (0.41 g, 3.4 mmol), and tetrahydrofuran (30 mL) were used as the solvent, and trifluoromethanesulfonamide was replaced with 4-fluorobenzenesulfonamide (2.50 g, 14.3 mmol) and pyridine was replaced with triethylamine (2.89 g, 28.5 mmol). This yielded the 69th white solid, butoxycarbonyl-4-fluorophenylsulfonamide (1.13 g, 4.1 mmol, yield 29%). 69th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0376] <Step 2: Synthesis of lithium butoxycarbonyl-4-fluorophenylsulfonamide (I-38)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using butoxycarbonyl-4-fluorophenylsulfonamide (1.01 g, 3.67 mmol), diethyl ether (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (2.8 mL, 3.67 mmol). This yielded the 70th white solid lithium butoxycarbonyl-4-fluorophenylsulfonamide (0.77 g, 2.72 mmol, yield 74%). 70th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-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)

[0377] [Synthesis Example 39] Lithium methoxycarbonyl-4-trifluoromethylphenylsulfonamide [synthetic compound (I-39)], represented by the following structural formula, was synthesized as described below.

[0378] [ka]

[0379] <Step 1: Synthesis of Methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide> The compound (I-10) was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, methyl chloroformate (2.64 g, 28.0 mmol), 4-dimethylaminopyridine (0.61 g, 5.0 mmol), and tetrahydrofuran (100 mL) were used as the solvent, and trifluoromethanesulfonamide was replaced with 4-(trifluoromethyl)benzenesulfonamide (5.24 g, 23.3 mmol) and pyridine was replaced with triethylamine (2.82 g, 28.0 mmol). This yielded the 71st white solid, methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (5.30 g, 18.7 mmol, yield 80%). 71st White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ3.65(s,3H), 8.04(d,J=9.1Hz,2H), 8.18(d,J=9.1Hz,2H)

[0380] <Step 2: Synthesis of Lithium Methoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide (I-39)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.80 g, 6.36 mmol), tetrahydrofuran (30 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (4.64 mL, 6.03 mmol). This yielded the 72nd white solid, lithium methoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (0.44 g, 1.52 mmol, yield 24%). 72nd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ2.31(s,3H), 7.65(d,J=8.9Hz,2H), 7.70(d,J=8.9Hz,2H)

[0381] [Synthesis Example 40] Lithium methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide [synthetic compound (I-40)], represented by the following structural formula, was synthesized as described below.

[0382] [ka]

[0383] <Step 1: Synthesis of Methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 2 (Synthetic Compound (I-10)), except that in the first step, methyl chloroformate (1.18 g, 12.5 mmol), 4-dimethylaminopyridine (0.13 g, 1.0 mmol), and tetrahydrofuran (50 mL) were used as the solvent, and trifluoromethanesulfonamide was replaced with 4-(trifluoromethoxy)benzenesulfonamide (2.50 g, 10.4 mmol) and pyridine was replaced with triethylamine (1.26 g, 12.5 mmol). This yielded the 73rd white solid, methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.10 g, 10.4 mmol, 100% yield). 73rd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0384] <Step 2: Synthesis of Lithium Methoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide (I-40)> The reaction was carried out in the same manner as in the second step of Synthesis Example 2 (Synthetic Compound (I-10)), using methoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.10 g, 10.4 mmol), tetrahydrofuran (40 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (7.57 mL, 9.84 mmol). This results in lithium methylcarbonyl 4-(trifluoromethoxy)phenyl, the 74th white solid. Sulfone An amide (0.40 g, 1.31 mmol, 13% yield) was obtained. 74th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ2.36(s,3H), 7.42(d,J=9.0Hz,2H), 7.74(d,J=9.0Hz,2H)

[0385] [Synthesis Example 41] Lithium phenoxycarbonylethoxysulfonamide [synthetic compound (I-41)], represented by the following structural formula, was synthesized as described below.

[0386] [ka]

[0387] <Step 1: Synthesis of phenoxycarbonylethoxysulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 20 (Synthetic Compound (I-20)), except that in the first step, ethyl sulfamate (1.80 g, 14.4 mmol), 4-dimethylaminopyridine (0.39 g, 3.2 mmol), and tetrahydrofuran (30 mL) were used as the solvent, and trifluoroacetic anhydride was replaced with phenyl chloroformate (2.70 g, 17.3 mmol) and pyridine was replaced with triethylamine (2.91 g, 28.8 mmol). This yielded the 75th white solid, phenoxycarbonylethoxysulfonamide (2.19 g, 8.93 mmol, 62% yield). 75th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.43(t,J=7.2Hz,3H), 4.52(q,J=7.2Hz,2H), 7.12-7.46(m,5H)

[0388] <Step 2: Synthesis of Lithium Phenoxycarbonylethoxysulfonamide (I-41)> Phenoxycarbonylethoxysulfonamide (2.19 g, 8.9 mmol) and tetrahydrofuran (20 mL) as solvent were placed in a nitrogen-purged 200 mL four-necked flask and maintained at -20°C. Lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (6.9 mL, 8.9 mmol) was added over 5 minutes, and the mixture was allowed to return to room temperature and stirred for 3 hours. Subsequently, n-hexane (20 mL) was added, and white solid No. 76 precipitated from the reaction solution. The reaction solution was filtered under reduced pressure, and the residual solvent of the obtained white solid No. 76 was removed by distillation under reduced pressure. This yielded lithium phenoxycarbonylethoxysulfonamide (2.11 g, 8.4 mmol, 94% yield), a white solid, as shown in the 76th product. 76th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0389] [Synthesis Example 42] Lithium fluorosulfonyl methoxycarbonylamide [synthetic compound (I-42)], represented by the following structural formula, was synthesized as described below.

[0390] [ka]

[0391] <Step 1: Synthesis of fluorosulfonylmethoxycarbonylamide> A 100 mL four-necked flask connected to a nitrogen-purged Liebig condenser 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. Then, potassium difluoride (5.85 g, 74.9 mmol) was added, and the mixture was stirred further. After 2 hours, the reaction was stopped. Subsequently, the resulting reaction product was washed. Specifically, 50 mL of distilled water was added to the reaction mixture, followed by 50 mL of hexane / ethyl acetate, and the mixture was extracted and washed using a separatory funnel. The above water washing was repeated twice, and all organic phases were washed together with saturated saline solution (20 mL). Magnesium sulfate was added to the obtained organic phases, and after drying, the mixture was concentrated under reduced pressure. This yielded the crude product fluorosulfonylmethoxycarbonylamide (9.63 g).

[0392] <Step 2: Synthesis of lithium fluorosulfonyl methoxycarbonylamide> Crude product fluorosulfonylmethoxycarbonylamide (4.50 g) and methanol (25 mL) as solvent were placed in a nitrogen-purged 100 mL four-necked flask. Lithium carbonate (2.33 g, 31.5 mmol) was added, and the mixture was stirred for 1 hour. The reaction solution was concentrated under reduced pressure, and ethyl acetate (20 mL) was added to form a suspension. The suspension was filtered through Celite, and the filtrate was concentrated under reduced pressure. Dichloromethane (20 mL) was added, and the mixture was stirred at room temperature for 1 hour, resulting in the precipitation of solid No. 77, a white solid. The solution was filtered under reduced pressure, and the residual solvent of the obtained solid No. 77 was removed by distillation under reduced pressure. This yielded lithium fluorosulfonylmethoxycarbonylamide (3.30 g, 20.2 mmol, 2-step yield 70%), the white solid No. 77. Below is the 77th white solid. 1 The measurement results obtained using 1H-NMR (DMSO-d6) are shown. 1 H-NMR: δ3.41(s,3H)

[0393] As described above, based on the results of Synthesis Example 42, lithium fluorosulfonyl methoxycarbonylamide [synthetic compound (I-42)] was obtained by the following reaction scheme.

[0394] [ka]

[0395] [Synthesis Example 43] Lithium fluorosulfonylethoxycarbonylamide [synthetic compound (I-43)], represented by the following structural formula, was synthesized as described below.

[0396] [ka]

[0397] <Step 1: Synthesis of fluorosulfonylethoxycarbonylamide> The compound was synthesized in the same manner as in Synthesis Example 42 (Synthesis Compound (I-42)), except that in the first step, chlorosulfonyl isocyanate (8.45 g, 59.7 mmol), potassium difluoride (5.09 g, 65.2 mmol), and acetonitrile (25 mL) were used as the solvent, and methanol was replaced with ethanol (2.50 g, 54.3 mmol). This yielded the crude product fluorosulfonylethoxycarbonylamide (9.29 g).

[0398] <Step 2: Synthesis of lithium fluorosulfonylethoxycarbonylamide> The reaction was carried out in the same manner as in the second step of Synthesis Example 42 (Synthetic Compound (I-42)), using crude product fluorosulfonylethoxycarbonylamide (4.50 g), lithium carbonate (2.14 g, 29.0 mmol), and methanol (25 mL) as the solvent. This yielded the 78th white solid lithium fluorosulfonylethoxycarbonylamide (2.29 g, 12.9 mmol, 2-step yield 49%). 78th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ1.10(t,J=6.8Hz,3H), 3.84(q,J=6.8Hz,2H)

[0399] [Synthesis Example 44] Lithium fluorosulfonylpropoxycarbonylamide [Synthetic compound (I-44)], represented by the following structural formula, was synthesized as described below.

[0400] [ka]

[0401] <Step 1: Synthesis of fluorosulfonylpropoxycarbonylamide> The compound was synthesized in the same manner as in Synthesis Example 42 (Synthesis Compound (I-42)), except that in the first step, chlorosulfonyl isocyanate (7.77 g, 54.9 mmol), potassium difluoride (4.68 g, 59.9 mmol), and acetonitrile (25 mL) were used as the solvent, and methanol was replaced with n-propanol (3.00 g, 49.9 mmol). This yielded the crude product fluorosulfonylpropoxycarbonylamide (9.24 g).

[0402] <Step 2: Synthesis of lithium fluorosulfonylpropoxycarbonylamide> The reaction was carried out 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 the solvent, in the same manner as in the second step of Synthesis Example 42 (Synthetic Compound (I-42)). This yielded the 79th white solid lithium fluorosulfonylpropoxycarbonylamide (1.76 g, 9.21 mmol, 2-step yield 43%). 79th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ0.88(t, J=7.6Hz,3H), 1.46-1.55(m,2H), 3.76(t,J=6.8Hz,2H)

[0403] [Synthesis Example 45] Lithium fluorosulfonyl butoxycarbonylamide [synthetic compound (I-45)], represented by the following structural formula, was synthesized as described below.

[0404] [ka]

[0405] <Step 1: Synthesis of fluorosulfonylbutoxycarbonylamide> The compound was synthesized in the same manner as in Synthesis Example 42 (Synthesis Compound (I-42)), except that in the first step, chlorosulfonyl isocyanate (5.11 g, 36.1 mmol), potassium difluoride (3.08 g, 39.4 mmol), and acetonitrile (15 mL) were used as the solvent, and methanol was replaced with n-butanol (2.43 g, 32.8 mmol). This yielded the crude product fluorosulfonyl butoxycarbonylamide (6.53 g).

[0406] <Step 2: Synthesis of lithium fluorosulfonyl butoxycarbonylamide> The reaction was carried out in the same manner as in the second step of Synthesis Example 42 (Synthetic Compound (I-42)), using crude product fluorosulfonyl butoxycarbonylamide (3.39 g), lithium carbonate (1.38 g, 18.7 mmol), and methanol (15 mL) as the solvent. This yielded the 80th white solid lithium fluorosulfonyl butoxycarbonylamide (2.50 g, 12.2 mmol, 2-step yield 72%). 80th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-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)

[0407] [Synthesis Example 46] Lithium fluorosulfonyl benzyloxycarbonylamide [Synthetic compound (I-46)], represented by the following structural formula, was synthesized as described below.

[0408] [ka]

[0409] <Step 1: Synthesis of fluorosulfonylbenzyloxycarbonylamide> The compound was synthesized in the same manner as in Synthesis Example 42 (Synthesis Compound (I-42)), except that in the first step, chlorosulfonyl isocyanate (3.97 g, 28.1 mmol), potassium difluoride (2.34 g, 30.0 mmol), and acetonitrile (15 mL) were used as the solvent, and methanol was replaced with benzyl alcohol (2.70 g, 25.0 mmol). This yielded the crude product fluorosulfonylbenzyloxycarbonylamide (5.82 g).

[0410] <Step 2: Synthesis of lithium fluorosulfonylbenzyloxycarbonylamide> The reaction was carried out in the same manner as in the second step of Synthesis Example 42 (Synthetic Compound (I-42)), using crude product fluorosulfonylbenzyloxycarbonylamide (3.52 g), lithium carbonate (2.03 g, 27.5 mmol), and methanol (15 mL) as the solvent. . This yielded the 81st white solid, lithium fluorosulfonyl benzyloxycarbonilamide (2.67 g, 11.2 mmol, 2-step yield 74%). 81st White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1 H-NMR: δ4.91(s,2H), 7.25-7.37(m,5H)

[0411] [Synthesis Example 47] Lithium butoxycarbonyl-4-trifluoromethylphenylsulfonamide [Synthetic compound (I-47)], represented by the following structural formula, was synthesized as described below.

[0412] [ka]

[0413] <Step 1: Synthesis of Butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 39 (Synthesis Compound (I-39)), except that in the first step, 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) were used as the solvent, and methyl chloroformate was replaced with butyl chloroformate (1.46 g, 10.7 mmol). This yielded the 82nd white solid, butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.80 g, 5.53 mmol, yield 52%). 82nd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0414] <Step 2: Synthesis of Lithium Butoxycarbonyl-4-(Trifluoromethyl)phenylsulfonamide (I-47)> The reaction was carried out in the same manner as in the second step of Synthesis Example 39 (Synthetic Compound (I-39)), using butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.64 g, 5.03 mmol), tetrahydrofuran (20 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (3.87 mL, 5.03 mmol). This yielded the 83rd white solid, lithium butoxycarbonyl-4-(trifluoromethyl)phenylsulfonamide (1.22 g, 3.68 mmol, yield 73%). 83rd White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 1H-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)

[0415] [Synthesis Example 48] Lithium butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide [Synthetic Compound (I-48)], represented by the following structural formula, was synthesized as described below.

[0416] [ka]

[0417] <Step 1: Synthesis of Butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide> The compound was synthesized in the same manner as in the first step of Synthesis Example 47 (Synthetic Compound (I-47)), except that in the first step, 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) were used as the solvent, and 4-(trifluoromethyl)benzenesulfonamide was replaced with 4-(trifluoromethoxy)benzenesulfonamide (2.80 g, 11.6 mmol). This yielded the 84th white solid, butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.06 g, 8.97 mmol, yield 77%). 84th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0418] <Step 2: Synthesis of Lithium Butoxycarbonyl-4-(Trifluoromethoxy)phenylsulfonamide (I-40)> The reaction was carried out in the same manner as in the second step of Synthesis Example 47 (Synthetic Compound (I-47)), using butoxycarbonyl-4-(trifluoromethoxy)phenylsulfonamide (3.06 g, 8.97 mmol), tetrahydrofuran (50 mL) as the solvent, and lithium bis(trimethylsilyl)amide (1.3 M) tetrahydrofuran solution (6.90 mL, 8.97 mmol). This results in the 85th white solid, lithium butylcarbonyl 4-(trifluoromethoxy)phenyl Sulfone An amide (2.66 g, 7.66 mmol, 85% yield) was obtained. 85th White Solid 1 The measurement results by 1H-NMR (DMSO-d6) are shown below. 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)

[0419] [Example 1] A non-aqueous electrolyte was obtained as described below.

[0420] <Preparation of non-aqueous electrolyte> Ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) were mixed in a volume ratio of EC:DMC:EMC = 30:35:35. This yielded a mixed solvent as a non-aqueous solvent. LiPF6, used as the electrolyte, was dissolved in the resulting mixed solvent so that its concentration in the final non-aqueous electrolyte was 1 mole / liter, thereby obtaining the electrolyte solution.

[0421] Hereafter, the obtained electrolyte will be referred to as the "basic electrolyte."

[0422] As an additive, lithium butoxycarbonyltosylamide (I-5), represented by the following formula (I-5) and synthesized in Synthesis Example 1, was added to the basic electrolyte solution such that its content relative to the total volume of the final non-aqueous electrolyte solution was as shown in Table 4 (mass %). This yielded a non-aqueous electrolyte solution.

[0423] [ka]

[0424] A coin-type battery (hereinafter also simply referred to as "battery") was fabricated as a precursor for lithium secondary batteries in the following manner.

[0425] <Fabrication of the positive electrode> Li(Ni) is used as the positive electrode active material. 0.5 Co 0.2 Mn 0.3 A mixture was obtained by adding 94% by mass of O2, carbon black (3% by mass) as a conductive additive, and polyvinylidene fluoride (PVdF) (3% by mass) as a binder. The obtained mixture was dispersed in N-methylpyrrolidone solvent to obtain a cathode composite slurry. A 20 μm thick aluminum foil was prepared as the positive electrode current collector. The obtained positive electrode slurry was applied to aluminum foil, dried, and then rolled in a press to obtain a sheet-like positive electrode. The positive electrode consists of a positive electrode current collector and a positive electrode active material layer.

[0426] <Fabrication of the negative electrode> A negative electrode slurry was obtained by mixing graphite (96% by mass) as the negative electrode active material, carbon black (1% by mass) as a conductive additive, carboxymethylcellulose sodium dispersed in pure water as a thickener (1% by mass in solid content), and styrene-butadiene rubber (SBR) dispersed in pure water as a binder (2% by mass in solid content). A 10 μm thick copper foil was prepared as the negative electrode current collector. The obtained slurry was applied to copper foil, dried, and then rolled in a press to obtain a sheet-like negative electrode. The negative electrode consists of a negative electrode current collector and a negative electrode active material layer.

[0427] The non-aqueous electrolyte obtained from the production of the non-aqueous electrolyte described above was prepared.

[0428] A porous polyethylene film was prepared as a separator.

[0429] <Manufacturing a coin-type battery> The negative electrode was punched out in a disc shape with a diameter of 14 mm, the positive electrode in a disc shape with a diameter of 13 mm, and the separator in a disc shape with a diameter of 17 mm. This resulted in coin-shaped negative electrodes, coin-shaped positive electrodes, and coin-shaped separators. The obtained coin-shaped negative electrode, coin-shaped separator, and coin-shaped positive electrode were stacked in this order inside a stainless steel battery case (size: 2032). Next, 20 μL of non-aqueous electrolyte was poured into the battery case, immersing the separator, positive electrode, and negative electrode in the non-aqueous electrolyte. Next, an aluminum plate (1.2 mm thick, 16 mm in diameter) and a spring were placed on the positive electrode, and the battery was sealed by crimping the battery can lid via a polypropylene gasket. Based on the above, a coin-shaped lithium secondary battery precursor having the configuration shown in Figure 2 was obtained. The size of the lithium secondary battery precursor was 20 mm in diameter and 3.2 mm in height.

[0430] [Comparative Example 1, Comparative Example 2, Examples 2 to 49] In the preparation of the non-aqueous electrolyte described above, a lithium secondary battery precursor was obtained in the same manner as in Example 1, except that the additives listed in Table 4 were added so that their content relative to the total amount of the final non-aqueous electrolyte was as shown in Table 4 (mass %).

[0431] In Comparative Example 2, lithium trifluoromethylcarbonyltrifluoromethylsulfonamide (C-1), represented by the following formula (C-1), was used.

[0432] [ka]

[0433] [Evaluation Test] The obtained lithium secondary battery precursor was subjected to the following aging treatment to obtain the first battery. The obtained first battery was subjected to the following initial charge-discharge treatment to obtain the second battery. The obtained second battery was subjected to the following DC resistance evaluation treatment to obtain the third battery. The obtained third battery was subjected to a high-temperature storage treatment to obtain the fourth battery. The obtained fourth battery was subjected to the following late charge-discharge treatment to obtain the fifth battery. Using the obtained batteries 1 through 5, the capacity after high-temperature storage, resistance after high-temperature storage, and resistance increase rate were measured according to the measurement method described below. These measurement results are shown in Table 4.

[0434] <Aging process> The lithium secondary battery precursor was subjected to the following aging treatment to obtain the first battery.

[0435] The battery precursor was charged at a temperature range of 25-70°C with a cutoff voltage of 1.5V-3.5V, and then allowed to rest for 5-50 hours. Next, the battery precursor was charged at a temperature range of 25-70°C with a cutoff voltage of 3.5V-4.2V and held for 5-50 hours. Then, the battery precursor was charged to 4.2V at a temperature range of 25-70°C and then discharged to 2.5V.

[0436] <Initial charge / discharge process> The first battery was subjected to the following initial charge-discharge treatment to obtain the second battery.

[0437] The first battery was kept in a 25°C environment for 12 hours. Next, the first battery was charged at a charge rate of 0.2C to 4.2V (SOC (State of Charge) 100%) using constant current constant voltage (0.2C-CCCV), then rested for 30 minutes, and then discharged at a discharge rate of 0.2C to 2.5V using constant current constant voltage (0.2C-CC). This was repeated three times to stabilize the battery. After that, the battery was charged at a charge rate of 0.2C to 4.2V using constant current constant voltage constant voltage (0.5C-CCCV), then rested for 30 minutes, and then discharged at a discharge rate of 1C to 2.5V using constant current constant voltage constant voltage (1C-CC). This resulted in the acquisition of the second battery.

[0438] <Processing for DC resistance evaluation> The second battery was subjected to the following DC resistance evaluation process to obtain the third battery.

[0439] The DC resistance evaluation process was performed in a temperature environment of 25°C. The second battery was discharged at a discharge rate of 0.2C to 2.5V using CC discharge, and then charged at a charge rate of 0.2C using CCCV charging to 3.7V. "CCCV charging" means charging with constant current and constant voltage.

[0440] Next, the second battery was subjected to a CC10s discharge at a discharge rate of 0.2C and a CC10s charge at a charge rate of 0.2C. "CC10s discharge" means discharging at a constant current for 10 seconds. "CC10s charge" means charging at a constant current for 10 seconds.

[0441] Next, the second battery was subjected to a CC10s discharge at a discharge rate of 0.5C and a CC25s charge at a charge rate of 0.2C. Then, the second battery was subjected to a CC10s discharge at a discharge rate of 1C and a CC50s charge at a charge rate of 0.2C. Finally, the second battery was subjected to a CC10s discharge at a discharge rate of 2C and a CC100s charge at a charge rate of 0.2C. This resulted in the third battery.

[0442] <High-temperature preservation treatment> The third cell was subjected to the following high-temperature storage treatment to obtain the fourth cell.

[0443] The third battery was charged to 4.2V at a constant current charge rate of 0.2C in a temperature environment of 25°C. Then, the charged battery was left standing in a 60°C atmosphere for 14 days. This resulted in the production of the fourth battery.

[0444] <Late-stage charge / discharge treatment> The fourth battery was subjected to the following late-stage charge-discharge treatment to obtain the fifth battery.

[0445] The fourth battery was allowed to cool in a 25°C environment, then underwent a first discharge, followed by a first charge and a second discharge. The first discharge indicates constant current discharge (1C-CC) to 2.5V at a discharge rate of 1C. The first charge indicates constant current constant voltage charge (0.2C-CCCV) to 4.2V at a charge rate of 0.2C. The second discharge indicates constant current discharge (1C-CC) to 2.5V at a discharge rate of 1C. This resulted in the acquisition of the fifth battery.

[0446] <Method for measuring volume after high-temperature storage> As shown in the following formula (X1), the relative value of the discharge capacity of the fourth battery in each embodiment to the discharge capacity of the fourth battery in Comparative Example 1 was defined as "Capacity after high-temperature storage [%]". The capacity after high-temperature storage represents the capacity obtained when the second discharge was performed in the later charge-discharge treatment described above.

[0447] Capacity after high-temperature storage [relative value; %] = (Discharge capacity of the 4th battery [mAh / g] / Discharge capacity of the 4th battery in Comparative Example 1 [mAh / g]) × 100 … (X1)

[0448] <Method for measuring resistance after high-temperature storage> As shown in the following formula (X2), the relative value of the DC resistance of the fifth battery to the DC current internal resistance (DCIR) of the fifth battery in Comparative Example 1 was defined as "resistance after high-temperature storage [%]".

[0449] Resistance after high-temperature storage [relative value; %] = (DC resistance of the 5th cell [Ω] / DC resistance of the 5th cell in Comparative Example 1 [Ω]) × 100 ... (x 2)

[0450] The DC resistance was measured using the following method. The fifth cell was subjected to the same DC resistance evaluation process as described above. The DC resistance (Ω) of the fifth cell was determined based on the voltage drop (=voltage before discharge - voltage 10 seconds after discharge) and the current value (i.e., the current value corresponding to the discharge rates of 0.2C to 1C) for each discharge rate from 0.2C to 1C during a "CC10s discharge".

[0451] <Method for measuring resistance increase rate> As shown in the following formula (X3), the relative value of the resistance increase rate to the resistance increase rate of Comparative Example 1 was defined as "resistance increase rate [%]".

[0452] Resistance increase rate [relative value; %] = (resistance increase rate / resistance increase rate of Comparative Example 1) × 100 ... (x 3)

[0453] In equation (X3), the resistance increase rate is obtained by dividing the DC resistance (Ω) of the fourth cell by the DC resistance (Ω) of the second cell. The DC resistance (Ω) of the fourth cell and the DC resistance (Ω) of the second cell are determined in the same way as the method for measuring the DC resistance (Ω) of the fifth cell in the method for measuring resistance after high-temperature storage described above.

[0454] The above relative values ​​of the DC resistance of the fifth battery after the high-temperature storage test correspond to the percentage increase in DC resistance due to storage (hereinafter also simply referred to as the "resistance increase rate"). Here, the increase rate is expressed as follows: 100% indicates neither an increase nor a decrease, over 100% indicates an increase, and less than 100% indicates a decrease.

[0455] The reason we focused on the resistance increase rate is that, while a low resistance value itself is an important performance characteristic of batteries, reducing the resistance increase rate caused by degradation during storage is also an extremely important performance characteristic.

[0456] [Table 4]

[0457] In Table 4, "-" means that the corresponding component is not contained. "Content of each additive" indicates the content (mass%) of the additive relative to the total amount of non-aqueous electrolyte for lithium secondary batteries. "(I)" indicates lithium (N-carbonyl) sulfonamide compound (I). "(II)" indicates lithium fluorophosphate compound (II). "(C-1)" indicates lithium trifluoromethylcarbonyltrifluoromethylsulfonamide (C-1). "(III)" indicates cyclic dicarbonyl compound (III). "(IV)" indicates cyclic sulfur-containing ester compound (IV). "(I-1)" indicates lithium methoxycarbonyl tosylamide (I-1). "(I-2)" indicates lithium ethoxycarbonyl tosylamide (I-2). "(I-4)" indicates lithium isopropoxycarbonyl tosylamide (I-4). "(I-5)" represents lithium butoxycarbonyl tosylamide (I-5). "(I-10)" represents lithium methoxycarbonyltrifluoromethylsulfonamide (I-10). "(I-11)" represents lithium ethoxycarbonyltrifluoromethylsulfonamide (I-11). "(I-12)" represents lithium propoxycarbonyltrifluoromethylsulfonamide (I-12). "(I-13)" represents lithium isopropoxycarbonyltrifluoromethylsulfonamide (I-13). "(I-14)" represents lithium butoxycarbonyltrifluoromethylsulfonamide (I-14). "(I-16)" represents lithium methoxycarbonylmethylsulfonamide (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-methoxyphenoxycarbonyltrifluoromethylsulfonamide (I-34)."(I-37)" represents lithium allyloxycarbonyltrifluoromethylsulfonamide (I-37). "(I-39)" represents lithium methoxycarbonyl-4-trifluoromethylphenylsulfonamide (I-39). "(I-42)" represents lithium fluorosulfonyl methoxycarbonylamide (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)" indicates lithium bisoxalate borate (III-1). "(IV-1)" indicates a cyclic sulfur-containing ester compound (IV-1).

[0458] The non-aqueous electrolytes of Examples 1 to 49 contained lithium (N-carbonyl) sulfonamide compound (I). As a result, the lithium secondary batteries of Examples 1 to 49 maintained a capacity of 100% or more, a resistance of 100% or less, and a resistance increase rate of 100% or less after high-temperature storage. In other words, it was found that the lithium secondary batteries of Examples 1 to 49 can suppress the increase in DC resistance and the decrease in discharge capacity even when stored in a high-temperature environment. On the other hand, the non-aqueous electrolyte of Comparative Example 2 contained lithium trifluoromethylcarbonyltrifluoromethylsulfonamide (C-1) and did not contain lithium (N-carbonyl)sulfonamide compound (I). As a result, the lithium secondary battery of Comparative Example 2 had a capacity of 100% after high-temperature storage, a resistance of 106% after high-temperature storage, and a resistance increase rate of 102%. In other words, it was found that the lithium secondary battery of Comparative Example 2 could not suppress the increase in DC resistance and the decrease in discharge capacity when stored in a high-temperature environment.

[0459] The disclosures of Japanese Patent Application No. 2021-044154, filed on 17 March 2021, and Japanese Patent Application No. 2021-143890, filed on 3 September 2021, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A lithium (N-carbonyl) sulfonamide compound represented by the following formula (I). 【Chemistry 1】 [In formula (I), R １ and R ２ Each of these 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), or 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). L １ and L ２ Each of these represents a single bond or -O-. However, L １ and L ２ Except when each of them is a single bond.

2. An additive for lithium secondary batteries comprising a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I). 【Chemistry 2】 [In formula (I), R1, R2, L1, and L2 are either the first combination or the second combination. In the first combination described above, R １ This 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, except for a trifluoromethyl group), or an aryl group (at least one hydrogen atom of the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms). R ２ This 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, except for a trifluoromethyl group), or an aryl group (at least one hydrogen atom of the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms). L １ and L ２ each represents a single bond or -O-. However, when each of L １ and L ２ is a single bond, and when each of R １ and R ２ is an alkyl group having 1 to 10 carbon atoms in which all hydrogen atoms are substituted with halogen atoms, these cases are excluded. In the second combination described above, R1 represents a p-methylphenyl group, R2 represents a methoxyethyl group, L1 represents a single bond, and L2 represents -O-.

3. An additive for lithium secondary batteries comprising a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I). 【Transformation 3】 In formula (I), R １ represents a halogen atom or a trifluoromethyl group. R ２ This 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 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). L １ and L ２ Each of these represents a single bond or -O-. However, R １ is a halogen atom, and L １ Except when -O-.

4. A non-aqueous electrolyte for lithium secondary batteries comprising an electrolyte, a non-aqueous solvent, and a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I), The non-aqueous electrolyte for lithium secondary batteries has a non-aqueous solvent content of 60% to 99% by mass relative to the total amount of the non-aqueous electrolyte for lithium secondary batteries. 【Chemistry 4】 [In formula (I), R1, R2, L1, and L2 are either the first combination or the second combination. In the first combination described above, R １ This 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, except for a trifluoromethyl group), or an aryl group (at least one hydrogen atom of the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms). R ２ This 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, except for a trifluoromethyl group), or an aryl group (at least one hydrogen atom of the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms). L １ and L ２ Each of these represents a single bond or -O-. However, L １ and L ２ When each of them is a single bond, and R １ and R ２ Except in the case where each of them is a C1-C10 alkyl group in which all hydrogen atoms are replaced by halogen atoms. In the second combination described above, R1 represents a p-methylphenyl group, R2 represents a methoxyethyl group, L1 represents a single bond, and L2 represents -O-.

5. A non-aqueous electrolyte for lithium secondary batteries comprising an electrolyte, a non-aqueous solvent, and a lithium (N-carbonyl) sulfonamide compound (I) represented by the following formula (I), The non-aqueous electrolyte for lithium secondary batteries has a non-aqueous solvent content of 60% to 99% by mass relative to the total amount of the non-aqueous electrolyte for lithium secondary batteries. 【Transformation 5】 In formula (I), R １ represents a halogen atom or a trifluoromethyl group. R ２ This 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 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). L １ and L ２ Each of these represents a single bond or -O-. However, R １ is a halogen atom, and L １ Except when -O-.

6. The electrolyte is lithium hexafluoride phosphate (LiPF). ６ ), lithium tetrafluoroborate (LiBF ４ ), lithium hexafluoride arsenate (LiAsF ６ ), lithium tantalate hexafluoride (LiTaF ６ ), lithium trifluoromethanesulfonate (LiCF ３ SO ３ ), lithium bis(trifluoromethanesulfonyl)imide (Li(CF ３ SO ２ ) ２ N), and lithium bis(pentafluoroethanesulfonyl)imide (Li(C) ２ F ５ SO ２ ) ２ The non-aqueous electrolyte for lithium secondary batteries according to claim 4 or claim 5, which is at least one selected from the group consisting of N).

7. The lithium (N-carbonyl) sulfonamide compound (I) is R1, R2, L1, and L2 are the first combination, The aforementioned R １ This represents the aryl group, Said L １ This represents a single bond, The aforementioned R ２ This represents the alkyl group or the aryl group, Said L ２ A non-aqueous electrolyte for a lithium secondary battery according to claim 4, wherein represents -O-.

8. The lithium (N-carbonyl) sulfonamide compound (I) is R1, R2, L1, and L2 are the first combination, The aforementioned R １ However, representing the alkyl group, Said L １ However, it represents a single bond, The aforementioned R ２ However, representing the alkyl group or the aryl group, Said L ２ However, the non-aqueous electrolyte for lithium secondary batteries according to claim 4, which represents -O-.

9. The lithium (N-carbonyl) sulfonamide compound (I) is The aforementioned R １ However, it represents a fluorine atom, Said L １ However, it represents a single bond, The aforementioned R ２ However, the alkyl group, the alkenyl group, the aryl group, or the aralkyl group represents the alkyl group, Said L ２ However, the non-aqueous electrolyte for lithium secondary batteries according to claim 5, which represents -O-.

10. A non-aqueous electrolyte for a lithium secondary battery according to any one of claims 4 to 9, comprising compound (II), which is at least one compound selected from the group consisting of lithium monofluorophosphate and lithium difluorophosphate.

11. A non-aqueous electrolyte for a lithium secondary battery according to any one of claims 4 to 10, comprising compound (III) represented by the following formula (III). 【Transformation 6】 [In formula (III), M is an alkali metal, Y is a transition element, a group 13, group 14, or group 15 element of the periodic table. b is an integer between 1 and 3. m is an integer between 1 and 4. n is an integer from 0 to 8. q is either 0 or 1, R ３ This 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 substituents or heteroatoms in their structure, and when q is 1 and m is 2 to 4, there are m R ３ They may be joined together.) R ４ This includes halogen atoms, C1-C10 alkyl groups, C1-C10 halogenated alkyl groups, C6-C20 aryl groups, or C6-C20 halogenated aryl groups (these groups may contain substituents or heteroatoms in their structure, and when n is 2-8, there are n R ４ These may each be joined together to form a ring. Q １ , and Q ２ These are, independently, either an oxygen atom or a carbon atom.

12. A non-aqueous electrolyte for a lithium secondary battery according to any one of claims 4 to 11, comprising compound (IV) represented by the following formula (IV). 【Transformation 7】 [In formula (IV), R ５ This 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 This 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 This 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 This 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 any one of claims 4 to 12, wherein the content of the lithium (N-carbonyl) sulfonamide compound (I) is 0.01% by mass or more and 5% by mass or less with respect to the total amount of the non-aqueous electrolyte for lithium secondary batteries.

14. The case and, The case contains a positive electrode, a negative electrode, a separator, and an electrolyte, Equipped with, The positive electrode is a positive electrode capable of intercalating and releasing lithium ions. The aforementioned negative electrode is a negative electrode capable of intercalating and releasing lithium ions. A lithium secondary battery precursor wherein the electrolyte is a non-aqueous electrolyte for lithium secondary batteries according to any one of claims 4 to 13.

15. The lithium secondary battery precursor according to claim 14, wherein the positive electrode contains a lithium-containing composite oxide represented by the following formula (C1) as the positive electrode active material. LiNi ａ Co ｂ Mn ｃ O ２ … Formula (C1) [In formula (C1), a, b, and c are each independently greater than 0 and less than 1, and the sum of a, b, and c is 0.99 or greater and 1.00 or less.]

16. A step of preparing a lithium secondary battery precursor according to claim 14 or claim 15, The process involves charging and discharging the lithium secondary battery precursor. A method for manufacturing lithium secondary batteries, including [the specified component].

17. A lithium secondary battery obtained by charging and discharging a lithium secondary battery precursor according to claim 14 or claim 15.

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