Alkyl group-containing phosphine compound and production method therefor

Abstract

Provided are a novel alkyl group-containing phosphine compound useful as a ligand, and a method for producing the same. More specifically, a compound represented by formula (1) and a method for producing the same are provided. (In formula (1), A represents an alkyl group represented by a chemical formula selected from formulae (2) and (3). In formula (1), R1 and R2 each independently represent a hydrocarbon group which may be substituted or a pyridyl group which may be substituted. In formula (1), n1 and n2 are each independently an integer of 0-2, and the total of n1 and n2 is 0-2.)

Description

Alkyl-containing phosphine compound and method for producing same REFERENCE TO RELATED APPLICATIONS

[0001] This patent application claims priority based on Japanese Patent Application No. 2024-133401 filed on August 8, 2024, and Japanese Patent Application No. 2025-022878 filed on February 14, 2025, the entire disclosures of which are incorporated herein by reference.

[0002] The present invention relates to a novel alkyl group-containing phosphine compound (hereinafter also referred to as a compound represented by formula (1)), and a method for producing the alkyl group-containing phosphine compound.

[0003] Numerous phosphines have been designed and synthesized and used in various catalytic reactions. Phosphines play a major role in improving activity and controlling chemoselectivity or stereoselectivity. In particular, the structural design of trisubstituted alkylphosphines is important for controlling the activity of homogeneous transition metal catalysts.

[0004] In recent years, it has been reported that trisubstituted phosphines bearing bulky substituents at remote positions exhibit high activity in cross-coupling reactions. For example, the CyTyrranoPhos ligand has bulky substituents at the 3,5-positions of the phenyl group on phosphorus, giving it the steric characteristic of occupying a remote space rather than near the metal (Non-Patent Document 1). This allows for high catalytic reaction efficiency in Suzuki-Miyaura (SM) coupling. On the other hand, Non-Patent Document 2 describes how N-heterocyclic carbene ligands achieve high catalytic activity by imparting flexibility to the bulky substituents of the aryl group linked to the imidazole ring (Non-Patent Document 2). Based on the above findings, introducing flexible and bulky substituents into remote positions in phosphine ligands may be one method for dramatically improving catalytic activity.

[0005] Newman-Stonebraker, SH et al., Science 2021, 374, pp.301-308Altenhoff, G. et al., J. Am. Chem. Soc. 2004, 126, pp.15195-15201

[0006] However, no examples of phosphines having flexible and bulky substituents at remote positions as described above have been known, and there is a demand for such phosphines.

[0007] An object of the present invention is to provide a novel alkyl group-containing phosphine compound useful as a ligand and a method for producing the same.

[0008] As a result of intensive investigations, the present inventors have found that the novel alkyl group-containing phosphine compound of the present invention can be obtained by reacting a compound represented by the following formula (4) with a phosphine compound represented by the following formula (5), and have thus completed the present invention.

[0009] That is, according to the present invention, the following inventions are provided: [1] An alkyl group-containing phosphine compound represented by the following formula (1): (In formula (1), A represents the following formulas (2) and (3): (In formula (2), the wavy line indicates a bond to P.) (In formula (3), the wavy line indicates a bond to P.) In formula (1), R １ , R ２ are each independently an optionally substituted hydrocarbon group or an optionally substituted pyridyl group, and in formula (1), n1 and n2 are each independently an integer of 0 to 2, and the sum of n1 and n2 is 0 to 2. In formula (1), P represents a phosphorus atom. [2] R １ , R ２are each independently a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted alicyclic hydrocarbon group, an optionally substituted phenyl group, and an optionally substituted adamantyl group. [3] An alkyl group-containing phosphine compound represented by the following formula (1): (In formula (1), A represents the following formulas (2) and (3): (In formula (2), the wavy line indicates a bond to P.) (In formula (3), the wavy line indicates a bond to P.) In formula (1), R １ , R ２ are each independently an optionally substituted hydrocarbon group or an optionally substituted pyridyl group, and in formula (1), n1 and n2 are each independently an integer of 0 to 2, and the sum of n1 and n2 is 0 to 2. A method for producing the compound represented by formula (4): (In formula (4), R ３ represents one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.) and a first raw material compound represented by the following formula (5): (In formula (5), R １ , R ２, n1 and n2 have the same meanings as in formula (1). In formula (5), P represents a phosphorus atom. A method for producing an alkyl group-containing phosphine compound, comprising a reaction step of synthesizing an alkyl group-containing phosphine compound represented by formula (1) by reacting a phosphine compound represented by the following formula (4): (In formula (4), R ３ represents one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

[10] A compound represented by the following formula (4): (In formula (4), R ３ represents one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, comprising reacting a compound represented by the following formula (6): and compounds represented by the following formulas (7) to (9): (In formula (7), R ３ is the same as formula (4). (In formula (8), R ３ is the same as formula (4). (In formula (9), R ３is synonymous with formula (4).

[11] A method for producing a compound according to

[10] , wherein in the reaction step, triphenylphosphine is further present when the halogen-containing compound is a compound represented by formula (7), pyridine is further present when the halogen-containing compound is a compound represented by formula (8), and iodine is further present when the halogen-containing compound is a compound represented by formula (9).

[0010] According to the present invention, a novel alkyl group-containing phosphine compound and a method for producing the same can be provided. Such a novel alkyl group-containing phosphine compound is useful as a ligand.

[0011] The compound represented by formula (6) obtained in Example 1 １ 1H-NMR spectrum of the compound represented by formula (6) obtained in Example 1. １３ 1 is a C-NMR spectrum of the compound represented by formula (4-1) obtained in Example 2-1. １ 1H-NMR spectrum of the compound represented by formula (4-1) obtained in Example 2-1. １３ 1 is a C-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 4. １ 1H-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 4. １３ 1 is a C-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 4. ３１ 1 is a P-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 5. １ 1H-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 5. １３ 1 is a C-NMR spectrum of the alkyl group-containing phosphine compound obtained in Example 5. ３１ 1 is a P-NMR spectrum of the alkyl group-containing phosphine compound (TIB-PPh ２ TIB-PPh 24 hours after preparation of the solution containing the compound ２Compounds and their oxides ３１ 1 is a P-NMR spectrum of the alkyl group-containing phosphine compound (TIB-PCy ２ TIB-PCy 24 hours after preparation of the solution containing the compound ２ Compounds and their oxides ３１ P-NMR spectrum.

[0012] [Alkyl Group-Containing Phosphine Compound] The alkyl group-containing phosphine compound of the present invention is represented by the following formula (1): It is expressed as:

[0013] In formula (1), A represents the following formulas (2) and (3): is an alkyl group represented by a chemical formula selected from the group consisting of:

[0014] As used herein, the term "triisobutylene (hereinafter also referred to as TIB) group" refers to an isobutylene trimer structure (having 12 carbon atoms). Specific examples of the TIB group include TIB groups derived from the structures of the following formulas (2-1), (2-2), and (10-1), with the TIB group derived from the structure of formula (2-1) being preferred.

[0015] Examples of the TIB group derived from the structure of the following formula (2-1) (2,2,6,6-tetramethyl-4-methyleneheptane) include the TIB group represented by the following formula (2) and the TIB group represented by the following formula (3), with the TIB group represented by the following formula (2) being preferred. Also, examples of the TIB group derived from the structure of the following formula (2-2) (2,2,4,6,6-pentamethyl-3-heptene) include the TIB group represented by the following formula (3):

[0016] An example of the TIB group derived from the structure of the following formula (10-1) (2,4,4,6,6-pentamethylhept-1-ene) is the TIB group represented by the following formula (10).

[0017] R in formula (1) １ , R ２ are each independently an optionally substituted hydrocarbon group, an alkoxy group, an amide group, or an optionally substituted pyridyl group. １ If there are two R １ may be the same or different, and are preferably the same. ２ If there are two R ２ may be the same or different, and are preferably the same. １ and R ２ The number of carbon atoms in the hydrocarbon group represented by is not particularly limited, but may be 1 to 36, preferably 2 to 30, and more preferably 3 to 10. Examples of the hydrocarbon group include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.

[0018] R １ and R ２ The number of carbon atoms in the alkyl group represented by is not particularly limited, but examples thereof include those having 1 to 20 carbon atoms, preferably 1 to 12, and more preferably 1 to 8. The alkyl group may be either a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, a saturated hydrocarbon group having 8 carbon atoms (for example, a linear octyl group or a branched octyl group), a nonyl group, a decyl group, an undecyl group, a saturated hydrocarbon group having 12 carbon atoms (for example, a linear dodecyl group or a branched dodecyl group), and a TIB (triisobutylene) group, and preferred are a tert-butyl group, a branched octyl group, a branched dodecyl group, and a TIB group.

[0019] R １ and R ２ The alkyl group represented by may be substituted, and the substituents include halogen atoms, -P(TIB) ２groups and alkoxy groups, and preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -P(TIB) ２ a straight or branched chain C group such as a methoxy group or an ethoxy group １－４ It is referred to as an alkoxy group.

[0020] R １ and R ２ The number of carbon atoms in the alicyclic hydrocarbon group represented by is not particularly limited, but examples include 3 to 36 carbon atoms, preferably 5 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms. The alicyclic hydrocarbon group may be either a saturated or unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group may be either a monocyclic or polycyclic group, and examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups, with cyclopentyl and cyclohexyl groups being preferred. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, 2-alkyladamantan-2-yl, 1-(adamantan-1-yl)alkan-1-yl, norbornyl, methylnorbornyl, and isobornyl groups, with adamantyl being preferred.

[0021] R １ and R ２ The alicyclic hydrocarbon group represented by the formula (I) may be substituted, and examples of the substituent include a halogen atom and an alkoxy group, and preferably a linear or branched C C group such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, or an ethoxy group. １－４ It is referred to as an alkoxy group.

[0022] According to a preferred embodiment of the present invention, R １ and R ２ The adamantyl group represented by the formula (I) may be substituted, and examples of the substituent include a halogen atom and an alkoxy group, and preferably a linear or branched C C group such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxy group, or an ethoxy group. １－４ It is referred to as an alkoxy group.

[0023] R １ and R ２ The aromatic hydrocarbon group represented by the formula (I) is not particularly limited in the number of carbon atoms, but may have 3 to 36 carbon atoms, preferably 5 to 30, and more preferably 6 to 20. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and preferably a phenyl group.

[0024] R １ and R ２ The aromatic hydrocarbon group represented by may be substituted, and the substituents include halogen atoms, -P(TIB) ２ , a 2-furyl group, a 2-thienyl group, a cyclopentadienyl group and an alkoxy group, and preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -P(TIB) ２ , a linear or branched chain C such as a methoxy group, an ethoxy group, etc. １－４ It is referred to as an alkoxy group.

[0025] According to a preferred embodiment of the present invention, R １ and R ２ The aromatic hydrocarbon group (preferably a phenyl group) represented by may be substituted, and the substituent may be a straight-chain or branched C １－４ Alkyl group; straight-chain or branched-chain C such as methoxy group (OMe) and tert-butoxy group (O-tert-Bu) １－４ Alkoxy group; dimethylamino group (NMe ２ ), -P(TIB) ２ groups, substituted phenyl groups, and halogen atoms are more preferred. １ and R ２Examples of the optionally substituted phenyl group represented by the formula (I) include tolyl groups such as o-tolyl, m-tolyl, and p-tolyl; xylyl groups such as 2,4-xylyl, 2,5-xylyl, and 3,5-xylyl; tert-butylphenyl groups such as p-tert-butylphenyl; di-tert-butoxyphenyl groups such as 3,5-di-tert-butylphenyl; di-tert-butylpyridylphenyl; methoxyphenyl groups such as p-methoxyphenyl and o-methoxyphenyl; tert-butoxyphenyl groups such as p-tert-butoxyphenyl; pentafluorophenyl; (2,4,6-triisopropylphenyl)phenyl; and o-(TIB) ２ -p-phenyl group, p-(TIB) ２ -P-phenyl group, m-(TIB) ２ (TIB) such as -P-phenyl group ２ A —P-phenyl group is an example.

[0026] R １ and R ２ The pyridyl group represented by the formula (I) may be substituted, and the substituents thereof include a halogen atom, -P(TIB) ２ and an alkoxy group, and preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, -P(TIB) ２ , a linear or branched chain C such as a methoxy group, an ethoxy group, etc. １－４ It is referred to as an alkoxy group.

[0027] In formula (1), n1 and n2 are each independently an integer of 0 to 2, and the sum of n1 and n2 is 0 to 2.

[0028] When A in formula (1) is 2 or more, each A independently represents an alkyl group represented by a chemical formula selected from the above formulas (2) and (3). Here, when there is 2 or more A (specifically, when the sum of n1 and n2 is 0 or 1 and there are 2 or 3 A), A is an alkyl group represented by a chemical formula selected from the following formulas (2) and (3), and each A may be the same or different, and is preferably the same.

[0029] The wavy line in formula (2) indicates a bond to P.

[0030] The wavy line in formula (3) indicates a bond to P.

[0031] In formula (1), A, R １ , R ２ According to a preferred embodiment of the combination of n1 and n2, A is an alkyl group represented by the chemical formula (2) or (3), more preferably an alkyl group represented by the chemical formula (2), n1 is 2, n2 is 0, and R １ are both groups selected from the group consisting of an optionally substituted alkyl group, an optionally substituted phenyl group, and an optionally substituted alicyclic hydrocarbon group (preferably an optionally substituted cyclohexyl group or an optionally substituted adamantyl group), and R ２ In formula (1), A, R １ , R ２ According to another preferred embodiment of the combination of n1 and n2, A is an alkyl group represented by the chemical formula (2) or (3), more preferably an alkyl group represented by the chemical formula (2), n1 is 1, n2 is 0, and R １ represents a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted phenyl group, and an optionally substituted alicyclic hydrocarbon group (preferably an optionally substituted cyclohexyl group or an optionally substituted adamantyl group), and R ２ In formula (1), A, R １ , R ２ According to another preferred embodiment of the combination of n1 and n2, A is an alkyl group represented by the chemical formula (2) or (3), more preferably an alkyl group represented by the chemical formula (2), n1 is 0, n2 is 0, and R １ and R ２ does not exist.

[0032] Preferred embodiments of the alkyl group-containing phosphine compound represented by the above formula (1) include the following compounds: In the following formula, tBu represents a tertiary butyl group, TIB represents a triisobutylene group, and iPr represents an isopropyl group.

[0033] The ligand composed of the alkyl group-containing phosphine compound represented by the above formula (1) has two or more bulky tert-butyl groups at positions distant from the phosphorus atom, and it is believed that the tert-butyl groups can flexibly stabilize the active metal center and improve catalytic activity.

[0034] (Characteristics of the alkyl group-containing phosphine compound represented by the above formula (1)) The stability of the compound represented by the above formula (1) of the present invention can be evaluated by measuring the residual rate (purity) of the compound represented by the above formula (1) after leaving a solution containing the compound represented by the formula (1) in air. Therefore, the above stability is preferably oxidative stability. Such stability may be, for example, that after a solution containing the compound represented by the formula (1) obtained by dissolving the compound represented by the formula (1) in a solvent (e.g., dehydrated toluene) is stored in air at 25°C for 24 hours, the residual rate of the compound represented by the formula (1) in the solution is 60% or more, preferably 70% or more, and more preferably 75%. There is no particular upper limit, but 100% or less is preferred. The residual rate of the compound represented by the above formula (1) is ３１ The residual rate (purity) (%) of the compound represented by formula (1) is calculated as the area percentage of the area of ​​the compound represented by formula (1) relative to the area of ​​all detected peaks.

[0035] Examples of oxides produced when a compound of formula (1) is oxidized include compounds in which an oxygen atom is bonded to the phosphorus atom of the compound of formula (1). When the compound of formula (1) is, for example, a compound of formula (1-1) below, an example of an oxide of the compound of formula (1) is a compound of formula (1-3) below. When the compound of formula (1) is, for example, a compound of formula (1-2) below, an example of an oxide of the compound of formula (1) is a compound of formula (1-4) below.

[0036] It is known that phosphine compounds such as tricyclohexylphosphine are easily oxidized in air, and the compound of the present invention represented by the above formula (1) is advantageous in that it can improve stability in air (preferably, oxidative stability).

[0037] The flash point of the alkyl group-containing phosphine compound of the present invention represented by the above formula (1) is not particularly limited, but from the viewpoint of deregulation of production, storage, and / or import / export, it is, for example, 110°C or higher, preferably 130°C or higher, and more preferably 150°C or higher. The upper limit is not particularly limited, but it can be 300°C or lower. The flash point can be measured in accordance with the ASTM D7094 standard. Such measurement can be easily performed in accordance with the ASTM D7094 standard by using a commercially available automatic flash point tester (e.g., ERAFLASH X, manufactured by eralytics).

[0038] The compound of the present invention represented by the above formula (1) is advantageous in that it has a high flash point.

[0039] [Method for producing alkyl group-containing phosphine compound] The method for producing the alkyl group-containing phosphine compound represented by the formula (1) is not particularly limited, but includes, for example, a reaction step of reacting a compound represented by the formula (4) with a phosphine compound represented by the formula (5) to synthesize the alkyl group-containing phosphine compound represented by the formula (1). The reaction step will be described in detail below.

[0040] (Halogenated triisobutylene compound) The compound represented by the following formula (4): (In formula (4), R ３ represents one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.) A compound represented by the formula (I) is also called a halogenated triisobutylene compound.

[0041] In formula (4), R ３ is preferably a bromine atom or a chlorine atom, and more preferably a bromine atom. ３A halogenated triisobutylene compound (a compound represented by formula (4-1) described below) in which is a bromine atom is 1-bromo-2-(2,2-dimethylpropyl)-4,4-dimethylpentane, which will hereinafter also be referred to as a brominated triisobutylene compound or a TIB-Br compound. A method for producing a halogenated triisobutylene compound will be described later.

[0042] (Phosphine Compound) The phosphine compound used in the present invention is represented by the following formula (5): In formula (5), R １ , R ２ , n1 and n2 have the same meanings as in formula (1), and preferred embodiments are also the same.

[0043] Preferred embodiments of the phosphine compound represented by the above formula (5) include the following compounds.

[0044] The amount of the phosphine compound represented by formula (5) used is not particularly limited as long as it does not impair the effects of the present invention, but is set to an amount such that the reactive group (hydrogen group) contained in the phosphine compound is, for example, 0.1 to 2.0 equivalents, preferably 0.2 to 1.5 equivalents, relative to 1 equivalent of the halogeno group contained in the halogenated triisobutylene compound represented by formula (4). According to another embodiment of the present invention, the amount of the phosphine compound represented by formula (5) used is, for example, 0.1 to 2.0 times the molar amount, preferably 0.2 to 1.5 times the molar amount, relative to 1 mole of the halogenated triisobutylene compound represented by formula (4).

[0045] (Solvent) The solvent used in the reaction step is not particularly limited, but from the viewpoint of maintaining the oxidation resistance of the tri-substituted phosphine compound, which is the target of synthesis, a non-aqueous solvent is preferred. For example, amide solvents such as N,N-dimethylformamide (DMF) and dimethylacetamide; ether solvents such as tetrahydrofuran (THF), cyclopentyl methyl ether (CPME), dioxane, diethyl ether, glyme, and diglyme; halogenated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; aromatic hydrocarbon solvents such as toluene, benzene, o-, m-, and p-xylene and mesitylene; aliphatic hydrocarbon solvents such as pentane, normal hexane, and cyclohexane; fluorine-containing organic solvents such as hexafluorobenzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, α,α,α-trifluoromethylbenzene, and dichloropentafluoropropane can be used. Among these, DMF, THF, and mixtures thereof are preferred from the viewpoint of improving the affinity of the added base.

[0046] The amount of the solvent used is not particularly limited, but may be, for example, 1 to 10,000 parts by mass, and preferably 10 to 4,000 parts by mass, relative to 100 parts by mass of the total of the halogenated triisobutylene compound and the phosphine compound represented by formula (5).

[0047] (Reaction Conditions) The atmosphere in which the halogenated triisobutylene compound and the phosphine compound represented by the above formula (5) are brought into contact with each other is not particularly limited. From the viewpoint of maintaining the oxidation resistance of the tri-substituted phosphine compound, which is the synthesis target, an inert gas atmosphere is preferred, and a nitrogen or argon atmosphere is more preferred.

[0048] The temperature in the reaction step of the halogenated triisobutylene compound and the phosphine compound represented by the formula (5) is not particularly limited, but is, for example, −80 to 120° C., and from the viewpoint of shortening the reaction time, is preferably 0 to 110° C., and more preferably room temperature to 105° C. Here, room temperature is 20 to 30° C.

[0049] The reaction time for the reaction step of the halogenated triisobutylene compound with the phosphine compound represented by the formula (5) is not particularly limited, but is, for example, 0.1 hours or more, and from the viewpoint of shortening the reaction time, is preferably 0.1 hours to 60 hours, more preferably 1 hour to 54 hours, and even more preferably 5 hours to 48 hours.

[0050] According to one embodiment of the present invention, it is preferable to further use a base in the reaction step of the halogenated triisobutylene compound with the phosphine compound represented by the formula (5). The base is not particularly limited, but examples thereof include potassium tert-butoxide (tBuOK), sodium carbonate (Na ２ CO ３ ), potassium carbonate (K ２ CO ３ ), cesium carbonate (Cs ２ CO ３ ) and the like, and from the viewpoint of reactivity and availability, tBuOK, K ２ CO ３ is preferred.

[0051] The amount of the base used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably an amount such that the counter anion in the base (which may be referred to as a counter anion derived from the base) is, for example, 0.5 to 20 equivalents, preferably 1 to 10 equivalents, relative to 1 equivalent of the halogeno group contained in the halogenated triisobutylene compound represented by formula (4). － (tert-butoxide anion), and the base is K ２ CO ３ In the case of CO ３ ２－ According to another embodiment of the present invention, the amount of the base used is, for example, 0.5 to 20 times by mole, and preferably 1 to 10 times by mole, per 1 mole of the halogenated triisobutylene compound represented by formula (4).

[0052] [Method for Purifying Alkyl Group-Containing Phosphine Compound] According to one embodiment of the present invention, the method for producing an alkyl group-containing phosphine compound of the present invention may further include a step of purifying the alkyl group-containing phosphine compound synthesized above. The purification method is not particularly limited, and a conventionally known purification method can be applied. Examples of the purification method include solvent distillation under reduced pressure, filtration (e.g., silica gel filtration), preparative chromatography, vacuum filtration, recrystallization, liquid separation, washing with a solvent, and ultrasonic washing, and preparative chromatography, recrystallization, and solvent distillation under reduced pressure are preferred.

[0053] According to a preferred embodiment of the present invention, when the alkyl group-containing phosphine compound obtained in the reaction step is oily, its purification method is preparative chromatography. The column used in the chromatography is not particularly limited, but a normal phase column is preferred. The conditions for preparative chromatography include, for example, the following: Developing solvent: hexane / CH ２ Cl ２ = 10 / 1 Column: normal phase silica gel (Universal column L size (Yamazen Co., Ltd.)) Instrument: Smart Flash AKROS (Yamazen Co., Ltd.) Temperature: room temperature Detection wavelength: 254 nm

[0054] According to another preferred embodiment of the present invention, when the alkyl group-containing phosphine compound obtained in the above reaction step is in the form of crystals, the purification method is recrystallization.

[0055] [Method for Producing Halogenated Triisobutylene Compound] The method for producing the halogenated triisobutylene compound represented by formula (4) of the present invention is not particularly limited, but may include, for example, a step of synthesizing the halogenated triisobutylene compound represented by formula (4) by reacting a TIB-OH compound represented by formula (6) with a halogen-containing compound represented by a chemical formula selected from the group consisting of formulas (7) to (9). The production method is described in detail below.

[0056] (Compound Represented by Formula (6)) The compound represented by the following formula (6) is 2-(2,2-dimethylpropyl)-4,4-dimethyl-1-pentanol, and hereinafter may also be referred to as a triisobutylene hydroxide compound or a TIB-OH compound. The compound represented by the above formula (6) is not particularly limited, but can be synthesized, for example, in accordance with the method described in International Publication No. 2020 / 017141 (Patent Document 1).

[0057] (Halogen-containing compound) The halogen-containing compound used in the present invention is represented by the following formulas (7) to (9): The compound is represented by a chemical formula selected from the group consisting of:

[0058] R in the above formulas (7), (8), and (9) ３ has the same meaning as formula (4), and preferred embodiments are also the same.

[0059] Preferred embodiments of the halogen-containing compound include the compound represented by the above formula (7) or the compound represented by the above formula (8), and more preferably the compound represented by the above formula (7).

[0060] The amount of the halogen-containing compound used is not particularly limited as long as it does not impair the effects of the present invention, but may be, for example, 0.5 to 2.0 times by mole, and preferably 1.0 to 1.8 times by mole, per mole of the TIB-OH compound.

[0061] (Solvent) The solvent used in the reaction step is not particularly limited, but examples thereof include halogenated solvents such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; aromatic hydrocarbon solvents such as toluene, benzene, o-, m-, and p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; ether solvents such as cyclopentyl methyl ether (hereinafter also referred to as CPME), tetrahydrofuran (hereinafter also referred to as THF), dioxane, diethyl ether, glyme, and diglyme; and fluorinated organic solvents such as hexafluorobenzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, α,α,α-trifluoromethylbenzene, and dichloropentafluoropropane. Among these, from the viewpoints of shortening the reaction time, improving the purification efficiency, and improving the yield, dichloromethane, toluene, CPME, and mixtures thereof are preferred, and dichloromethane is more preferred. As a preferred embodiment of the halogen-containing compound and solvent of the present invention, when the halogen-containing compound is a compound represented by the chemical formula (7), the solvent may be dichloromethane or chloroform, more preferably dichloromethane, and when the halogen-containing compound is a compound represented by the chemical formula (8), the solvent may be toluene or CPME, more preferably toluene.

[0062] The amount of the solvent used is not particularly limited, but may be, for example, 0.01 to 10,000 parts by mass, preferably 0.03 to 6,000 parts by mass, per 100 parts by mass of the TIB-OH compound and the halogen-containing compound combined. According to one embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (7), the amount of the solvent used is preferably 100 to 10,000 parts by mass, more preferably 400 to 6,000 parts by mass, and even more preferably 300 to 1,200 parts by mass or 4,000 to 6,000 parts by mass, per 100 parts by mass of the TIB-OH compound and the halogen-containing compound combined. According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (8), the amount of the solvent used is preferably 0.1 to 200 parts by mass, more preferably 1 to 70 parts by mass, per 100 parts by mass of the TIB-OH compound and the halogen-containing compound combined.

[0063] (Reaction Conditions) The temperature at which the TIB-OH compound and the halogen-containing compound are reacted is not particularly limited, but is, for example, −30° C. or higher, and from the viewpoint of shortening the reaction time, is preferably −30 to 150° C. According to one embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (7), the temperature at which the TIB-OH compound and the halogen-containing compound are reacted is preferably −30 to 100° C., more preferably −20 to 50° C., and even more preferably room temperature or 35 to 50° C. Here, room temperature is 20 to 30° C. According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (8), the temperature at which the TIB-OH compound and the halogen-containing compound are reacted is preferably 80 to 150° C., more preferably 90 to 100° C.

[0064] The time for reacting the TIB-OH compound with the halogen-containing compound is not particularly limited, but is, for example, 0.1 hour or more. From the viewpoint of shortening the reaction time, it is preferably 0.5 hours to 3 days, more preferably 1 hour to 2 days. According to one embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (7), the temperature for reacting the TIB-OH compound with the halogen-containing compound is preferably 0.1 hours to 3 days, more preferably 1 hour to 2 days, and even more preferably 0.5 to 4 hours or 1 day to 2 days. According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (8), the temperature for reacting the TIB-OH compound with the halogen-containing compound is preferably 0.5 hours to 4 hours, more preferably 1 hour to 3 hours.

[0065] According to a preferred embodiment of the present invention, in the method for producing a halogenated triisobutylene compound represented by formula (4) of the present invention, when the halogen-containing compound is a compound represented by formula (7), the solvent used in the reaction step is dichloromethane or chloroform, preferably dichloromethane, and the reaction temperature of the TIB-OH compound and the halogen-containing compound is 35 to 50°C, the reaction time is 0.5 to 4 hours, and the amount of the solvent used is 300 to 1200 parts by mass per 100 parts by mass of the total of the TIB-OH compound and the halogen-containing compound. In particular, when the reaction temperature is within the above range, it is possible to reduce the amount of solvent and shorten the reaction time.

[0066] According to one embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (7), it is preferable to further add triphenylphosphine when reacting the TIB-OH compound with the halogen-containing compound. The amount of triphenylphosphine used is not particularly limited as long as it does not impair the effects of the present invention, but it is, for example, 0.5 to 2.0 times by mole, and preferably 1.0 to 1.8 times by mole, per mole of the TIB-OH compound.

[0067] According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (8), pyridine is preferably further present when reacting the TIB-OH compound with the halogen-containing compound. The amount of pyridine used is not particularly limited as long as it does not impair the effects of the present invention, but may be, for example, 0.5 to 2.0 times by mole, and preferably 1.0 to 1.8 times by mole, per mole of the TIB-OH compound.

[0068] According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (9), it is preferable to further add iodine to the reaction of the TIB-OH compound with the halogen-containing compound. The amount of iodine used is not particularly limited as long as it does not impair the effects of the present invention, but may be, for example, 0.5 to 2.0 times by mole, and preferably 1.0 to 1.8 times by mole, per mole of the TIB-OH compound.

[0069] [Method for Purifying a Halogenated Triisobutylene Compound] According to one embodiment of the present invention, the method for producing a halogenated triisobutylene compound of the present invention may further include a step of purifying the halogenated triisobutylene compound synthesized above. The purification method is not particularly limited, and conventionally known purification methods can be applied. Examples of purification methods include filtration (e.g., silica gel filtration), preparative chromatography, vacuum filtration, recrystallization, liquid separation, solvent distillation, washing with a solvent, and ultrasonic washing, and preferably filtration (e.g., silica gel filtration) or preparative chromatography.

[0070] The column used in the above-mentioned chromatography is not particularly limited, but a normal phase column is preferred. Examples of conditions for preparative chromatography include the following: Developing solvent: a mixed solvent of ethyl acetate / hexane = 10 / 90 (volume %) Column: normal phase silica gel (preferably Universal Column L size (manufactured by Yamazen Co., Ltd.)) Instrument: Smart Flash AKROS (manufactured by Yamazen Co., Ltd.) Temperature: room temperature Detection wavelength: 254 nm

[0071] According to one embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (7), filtration (e.g., silica gel filtration) is preferred as a method for purifying the halogenated triisobutylene compound synthesized above. For example, by distilling off the polar solvent, such as dichloromethane, used in the reaction step after completion of the reaction, and adding a nonpolar solvent, such as hexane, it becomes possible to utilize the difference in solubility between the target halogenated triisobutylene compound and the by-product. By using a nonpolar solvent, by-products that are insoluble in the nonpolar solvent can be removed by silica gel filtration alone, and the target halogenated triisobutylene compound can be isolated.

[0072] According to another embodiment of the present invention, when the halogen-containing compound is a compound represented by formula (8), the halogenated triisobutylene compound synthesized above is preferably purified by preparative chromatography.

[0073] The present invention will be specifically explained below with reference to examples, but the present invention is not limited to these examples.

[0074] The structural analysis of the compound represented by formula (1) obtained by the methods of Examples 4 and 5 below was carried out under the following conditions: １ H-NMR measurement, １３ C-NMR measurement, and ３１ P-NMR measurement was carried out. １ H-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) １ H-NMR measurement conditions: frequency 600.03MHz, CD ２ Cl ２ Solvent / measurement time: about 30 minutes １３ C-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) １３ C-NMR measurement conditions: frequency 150.89 MHz, CD ２ Cl ２ Solvent / measurement time: approx. 60 minutes ３１P-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) ３１ P-NMR measurement conditions: frequency 242.97MHz, CD ２ Cl ２ Solvent / measurement time: about 30 minutes

[0075] The compounds represented by formula (4-1) and (6) obtained by the following method were structurally analyzed under the following conditions: １ H-NMR measurement and １３ C-NMR measurement was carried out. １ H-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) １ H-NMR measurement conditions: frequency 600.03 MHz, CDCl ３ Solvent / measurement time: about 30 minutes １３ C-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) １３ C-NMR measurement conditions: frequency 150.89 MHz, CDCl ３ Solvent / measurement time: Approximately 60 minutes

[0076] The oxidation stability test of the compound represented by formula (1) in Example 6 below was carried out under the following conditions: ３１ P-NMR measurement was carried out. ３１ P-NMR conditions] NMR measurement device: spectrometer AVANCE NEO, magnet Ascend 600 (manufactured by BRUKER JAPAN) ３１ P-NMR measurement conditions: frequency 242.97 MHz, CDCl ３ Solvent / measurement time: about 30 minutes

[0077] Example 1 Production of Compound Represented by Formula (6) (TIB-OH Compound) A compound represented by formula (6) was synthesized with reference to the description of Synthesis Example 1 in WO 2020 / 017141.

[0078] Specifically, the reaction was carried out by the following method. In a reaction vessel under a nitrogen stream, 60 mL of anhydrous THF was added to 10.00 g (59.4 mmol) of a triisobutylene raw material (manufactured by TCI) containing a compound represented by the following formula (11-1) (sometimes abbreviated as "compound (11-1)") and a compound represented by the following formula (11-2) (sometimes abbreviated as "compound (11-2)"), and the mixture was stirred. 9-Borabicyclo[3.3.1]nonane (9-BBN) (89.1 mmol) was added dropwise to the mixture at 0°C under ice cooling, and the mixture was heated to 35°C after 30 minutes (Reaction Scheme I).

[0079] The reaction mixture was cooled again on ice, and 79 mL (238 mmol) of 3M NaOH aq was added dropwise. ２ O ２ The solution (80 mL) was added dropwise and allowed to react overnight (Reaction Scheme II).

[0080] After separating the organic and aqueous layers, the organic layer was added with K ２ CO ３ The water remaining in the organic solvent was separated by adding MgSO. After separating the aqueous layer, the same procedure was repeated two more times. The aqueous layers were combined and extracted three times with ethyl acetate. Finally, the organic layers were combined and extracted with MgSO. ４ The drying agent was filtered off, and the solvent was distilled off under reduced pressure to obtain 18.22 g of a colorless, transparent, oily crude product. Note that the unreacted internal olefin structure was removed during the distillation under reduced pressure.

[0081] The crude product was roughly purified by vacuum distillation (bath temperature: 100°C, top temperature: 45°C, vacuum level: 1.3 kPa), and then purified on a silica gel column (Silicagel: 92.8 g, eluent: Heptane / Ethyl acetate = 7 / 1) to obtain a white solid TIB-OH compound. The yield was 2.74 g (14.7 mmol), 25%.

[0082] <Compound represented by formula (6) (TIB-OH compound) １ H-NMR measurement and １３ C-NMR measurement of the obtained TIB-OH compound １ H-NMR measurement and １３ C-NMR measurement was carried out.１ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in Figure 2. １ H-NMR spectral data and １３ C-NMR spectrum data was obtained. Spectral analysis confirmed that the compound was the compound represented by formula (6). 1 H-NMR(600.03MHz,CDCl3): δ 0.93(s,18H), 1.14-1.39(d,4H), 1.23 (s, 1H), 1.64(m,1H), 3.52(t,2H) 13 C-NMR(150.89MHz,CDCl3): δ 67.9, 47.5, 33.9, 31.2, 30.3

[0083] <Production of Compound Represented by Formula (4-1) (TIB-Br Compound)-1> [Example 2] [Example 2-1] The compound represented by formula (6) (TIB-OH compound) (1.24 g, 6.65 mmol) obtained in Example 1 and 120 mL of dichloromethane were placed in a 100 mL recovery flask and stirred while cooling with ice water. ３ ) (2.61 g, 9.98 mmol) was added and dissolved by stirring. N-bromosuccinimide (NBS) (1.72 g, 9.98 mmol) was added to the resulting solution, and the mixture was stirred at room temperature for 2 days to allow the reaction to proceed (Reaction Formula III). After the reaction, the solvent was distilled off, and the product was extracted with hexane and then purified by filtration using silica gel. After distilling off the solvent, 1.40 g (85%) of the target TIB-Br compound was obtained (Table 1).

[0084]

[0085] The chemical structure of the isolated TIB-Br compound was determined by NMR measurement. １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in Figure 4. １ H-NMR spectral data and １３C-NMR spectrum data was obtained. Spectral analysis confirmed that the compound was the compound represented by formula (4-1). 1 H-NMR(600.03MHz,CDCl3): δ 0.94(s,18H),1.21-1.44(dd,4H),1.85(m,1H),3.47(d,2H) 13 C-NMR(150.89MHz,CDCl3): δ 49.1, 44.1, 33.2, 31.1, 30.2

[0086] [Examples 2-2 to 2-3] In Examples 2-2 and 2-3, TIB-Br compounds were synthesized in the same manner as in Example 2-1, except that the amounts of TIB-OH compound, dichloromethane, triphenylphosphine, and N-bromosuccinimide used were the amounts shown in Table 1. The yields of the TIB-Br compounds obtained in Examples 2-2 and 2-3 are shown in Table 1.

[0087] [Example 2-4] The compound represented by formula (6) (TIB-OH compound) (1.24 g, 6.65 mmol) obtained in Example 1 and 13.3 mL of dichloromethane were placed in a 25 mL Schlenk flask and stirred while cooling with ice water. ３ ) (2.61 g, 9.98 mmol) was added and then stirred to dissolve. N-bromosuccinimide (NBS) (1.72 g, 9.98 mmol) was added to the resulting solution, and the mixture was stirred at 40°C (under solvent reflux) for 3 hours to allow the reaction to proceed (Reaction Formula III). After the reaction, the dichloromethane solvent was distilled off, and hexane was added, followed by filtration and purification using a small amount of silica gel. After the hexane solvent was distilled off, 1.40 g (85%) of the target TIB-Br compound was isolated. The results are shown in Table 2.

[0088]

[0089] The yield (85%) of the TIB-Br compound in Example 2-4 was similar to that in Example 2-1. Meanwhile, the amount of solvent used in Example 2-4 was significantly reduced from that in Example 2-1, and the reaction time in Example 2-4 was also significantly shortened from that in Example 2-1. Therefore, the production method in Example 2-4 can reduce the production cost of the TIB-Br compound. Furthermore, the production cost of the TIB-Br compound can be reduced by avoiding expensive column fractionation as a purification method and employing an inexpensive silica gel filtration method.

[0090] <Production of Compound Represented by Formula (4-1) (TIB-Br Compound)-2> [Example 3] [Example 3-1] A 25 mL Schlenk flask was charged with a TIB-OH compound (a compound represented by formula (6)) (2.79 g, 15 mmol) and 4 mL of CPME as a solvent, and the resulting mixture was cooled to -10°C and stirred. ３ (4.47 g, 16.5 mmol) was added and dissolved with stirring. After stirring at room temperature for 30 minutes, the mixture was heated to 100°C and reacted for 2 hours. After that, the reaction solution was cooled to -10°C, and water was gradually added. After that, the organic layer was recovered by extraction and separation, and the solvent was distilled off to obtain a crude product. Next, the obtained crude product was purified by preparative chromatography (column: normal phase silica gel (Universal Column L size (Yamazen Corporation)), equipment: Smart Flash AKROS (Yamazen Corporation), temperature: room temperature, detection wavelength: 254 nm). As the developing solution for preparative chromatography, a mixed solution of ethyl acetate / hexane was used, and the ethyl acetate concentration was gradually changed to 5% by volume and 10% by volume. As a result, when the ethyl acetate concentration of the chromatographic developing solution (ethyl acetate / hexane) was 10% by volume, the target substance (TIB-Br compound) was isolated (yield: 36%). The chemical structure of the TIB-Br compound isolated in Example 3-1 was assigned by NMR measurement, and it was confirmed to be the same as that of Example 2-1, and to be the compound represented by formula (4-1).

[0091] [Example 3-2] A TIB-Br compound was synthesized in the same manner as in Example 3-1, except that the solvent used in Example 3-2 was changed from CPME to toluene. As a result, the yield was 49%.

[0092] <Compound represented by formula (1) (alkyl-containing phosphine compound; TIB-PPh ２ Production of Compounds

[0093] Example 4: Under an inert gas atmosphere (specifically, N ２ In a glove box under atmospheric pressure, diphenylphosphine (PHPh) was added to a 20 mL Schlenk flask. ２ (a phosphine compound represented by formula (5)) (70 μL, 0.441 mmol, 1.1 eq) and potassium tert-butoxide (tBuOK) (49 mg, 0.441 mmol, 1.1 eq) were added, and DMF (4 mL) solvent was added and stirred at room temperature for 20 minutes. Thereafter, TIB-Br compound (a compound represented by formula (4-1)) (100 mg, 0.401 mmol, 1.0 eq) was added, and the reaction was carried out by stirring at 100°C for 24 hours (Reaction Formula IV). After the reaction, as a post-treatment, the DMF solvent was distilled off and the reaction product was extracted with diethyl ether, and the extract was washed with pure water and saturated saline. After this washing, the diethyl ether layer was recovered and dehydrated and dried, and the solvent was distilled off, resulting in the target TIB-PPh. ２ A compound (compound represented by formula (1-1)) was obtained (61 mg, yield 43%, colorless oil). The results are shown in Table 3.

[0094]

[0095] Isolated TIB-PPh ２ The chemical structure of the compound was determined by NMR measurement. ２ Compound １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in FIG. ３１ The P-NMR spectrum is shown in Figure 7. １ H-NMR spectral data, １３ C-NMR spectral data and３１ P-NMR spectrum data was obtained. Spectral analysis confirmed that the compound was the compound represented by formula (1-1). 1 H-NMR(600.03MHz,CD2Cl2): δ 0.82(s,18H),1.2-1.5(m,4H),2.07(d,2H), 7.30-7.44 (m,10H) 13 C-NMR(150.89MHz,CD2Cl2): δ 139.7, 133.1, 128.3, 128.2, 51.5, 38.5, 31.3, 30.3, 28.2 31 P-NMR(242.97MHz,CD2Cl2): δ -19.5

[0096] <Compound represented by formula (1) (alkyl-containing phosphine compound; TIB-PCy ２ Production of Compounds

[0097] [Example 5] Under an inert gas atmosphere (specifically, N ２ In a glove box under atmospheric pressure, dicyclohexylphosphine (PHCy) was placed in a 20 mL Schlenk flask. ２ (a phosphine compound represented by formula (5)) (0.12 mL, 0.60 mmol, 1.0 eq) and potassium carbonate (K ２ CO ３ ) (0.82 g, 6.0 mmol, 10 eq) was added, and DMF (6 mL) solvent was added and stirred at room temperature for 20 minutes. Thereafter, TIB-Br compound (compound represented by formula (4)) (450 mg, 1.8 mmol, 3.0 eq) was added, and the mixture was stirred at 100°C for 48 hours to react (Reaction Formula V). After the reaction, as a post-treatment, the DMF solvent was distilled off, and the reaction product was extracted with dichloromethane, and the extract was washed with methanol. As a result of distilling off the solvent, the target TIB-PCy ２ A compound (compound represented by formula (1-2)) was obtained (15 mg, yield 7%, colorless crystals). The results are shown in Table 4.

[0098]

[0099] Isolated TIB-PCy ２The chemical structure of the compound was determined by NMR measurement. ２ Compound １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in FIG. ３１ The P-NMR spectrum is shown in Figure 10. １ H-NMR spectral data, １３ C-NMR spectral data and ３１ P-NMR spectrum data was obtained. Spectral analysis confirmed that the compound was the compound represented by formula (1-2). 1 H-NMR(600.03MHz,CD2Cl2): δ 0.8-1.0(m), 1.2-1.6(m), 1.79(m) 13 C-NMR(150.89MHz,CD2Cl2): δ 51.8, 33.6, 32.0, 31.3, 30.6, 30.0, 29.6, 27.4, 26.7 31 P-NMR(242.97MHz,CD2Cl2): δ -10.2

[0100] <Compound represented by formula (1) (alkyl-containing phosphine compound; TIB-PPh ２ Compound, TIB-PCy ２ Example 6: Study on the oxidation stability of TIB-PPh obtained in Example 4 ２ Compound TIB-PCy obtained in Example 5 ２ compound, and tricyclohexylphosphine (Cy ３ The oxidation stability of each compound was measured. 15 mg of each compound was dissolved in 0.6 mL of dehydrated toluene to obtain a solution containing each compound. The resulting solution was left in the air at 25°C and stirred for approximately 8 hours. A small amount of each solution was sampled 0, 3, 6, and 24 hours after the solution preparation, and the NMR solvent CDCl was added. ３ Dissolved in ３１ P-NMR measurement was performed. The results of the residual rate (purity) of the above compound are shown in Table 5. The residual rate (purity) (%) of the above compound was calculated as the area percentage of the area of ​​the above compound relative to the area of ​​all detected peaks. TIB-PPh ２24 hours after preparation of the compound-containing solution ３１ The P-NMR spectrum is shown in Figure 11. In Figure 11, a indicates TIB-PPh ２ Compound derived, b is TIB-PPh ２ Oxide of the compound (compound of formula (1-3)) ３１ P-NMR assigned peaks are shown. ２ 24 hours after preparation of the compound-containing solution ３１ The P-NMR spectrum is shown in Figure 12. In Figure 12, c indicates TIB-PCy ２ Compound origin, d is TIB-PCy ２ Oxide of the compound (compound of formula (1-4)) ３１ P-NMR assigned peaks are shown.

[0101] <Compound represented by formula (1) (alkyl-containing phosphine compound; TIB-PPh ２ Measurement of flash point of TIB-PPh obtained in Example 4 ２ Compound and Cy ３ The flash point of TIB-PPh was measured in accordance with ASTM D7094 using an automatic flash point tester (ERAFLASH X, manufactured by eralytics). The results are shown in Table 6. ２ Compounds: n = 2 results (average value), Cy ３ P indicates the results for n=1.

Claims

1. An alkyl group-containing phosphine compound represented by the following formula (1): (In formula (1), A represents the following formulas (2) and (3): (In formula (2), the wavy line indicates a bond to P.) (In formula (3), the wavy line indicates a bond to P.) In formula (1), R １ , R ２ are each independently an optionally substituted hydrocarbon group or an optionally substituted pyridyl group, and in formula (1), n1 and n2 are each independently an integer of 0 to 2, and the sum of n1 and n2 is 0 to 2.

2. R １ , R ２ are each independently a group selected from the group consisting of an optionally substituted alkyl group, an optionally substituted alicyclic hydrocarbon group, an optionally substituted phenyl group, and an optionally substituted adamantyl group.

3. An alkyl group-containing phosphine compound represented by the following formula (1): (In formula (1), A represents the following formulas (2) and (3): (In formula (2), the wavy line indicates a bond to P.) (In formula (3), the wavy line indicates a bond to P.) In formula (1), R １ , R ２ are each independently an optionally substituted hydrocarbon group or an optionally substituted pyridyl group, and in formula (1), n1 and n2 are each independently an integer of 0 to 2, and the sum of n1 and n2 is 0 to 2. A method for producing the compound represented by formula (4): (In formula (4), R ３ represents one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom. (In formula (5), R １ , R ２ , n1 and n2 are defined as in formula (1).

4. The method according to claim 3, wherein a base is present in the reaction step.

5. The method according to claim 3 or 4, wherein the reaction temperature in the reaction step is -80 to 120°C.

6. The method according to claim 3 or 4, wherein a non-aqueous solvent is further present in the reaction step.

7. The method according to claim 3 or 4, wherein the reaction time of the reaction step is 0.1 to 60 hours.

8. The production method according to claim 3 or 4, wherein the amount of base used in the reaction step is an amount such that the amount of counter anion in the base is 0.5 to 20 equivalents per equivalent of the halogeno group in the compound represented by formula (4).

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