CN112759531B - Novel imine compound and preparation method thereof - Google Patents

Novel imine compound and preparation method thereof Download PDF

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CN112759531B
CN112759531B CN201911002665.5A CN201911002665A CN112759531B CN 112759531 B CN112759531 B CN 112759531B CN 201911002665 A CN201911002665 A CN 201911002665A CN 112759531 B CN112759531 B CN 112759531B
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acid
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pentyl
butyl
benzylidene
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CN112759531A (en
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王军
马吉星
高明智
刘海涛
马晶
蔡晓霞
刘文蕊
何世雄
胡建军
李昌秀
许景琦
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/18—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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  • Health & Medical Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a novel imine compound and a preparation method thereof. The imine compound has a structure shown in a formula I, can be used as an internal electron donor compound of an olefin polymerization catalyst, has good hydrogen regulation sensitivity, and has wide molecular weight distribution.

Description

Novel imine compound and preparation method thereof
Technical Field
The invention relates to a novel imine ester compound and a preparation method thereof.
Background
With the development of electron donor compounds in catalysts, polyolefin catalysts are continually updated and polypropylene technology is improved for traditional Ziegler-Natta catalysts. The development of the catalyst proceeds from first/second generation TiCl 3 Alkyl aluminum system to third generation magnesium chloride as carrier TiCl 4 TiCl with monoester or aromatic dibasic acid ester as inner electron donor and silane as outer electron donor is added as active center 4 ·ED·MgCl 2 /AlR 3 The ED system, the catalytic olefin polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved. In the prior art, catalyst systems for propylene polymerization are based on magnesium, titanium, halogen and electron donors, wherein the electron donor compound is one of the essential components of the catalyst component. A variety of electron donor compounds have been disclosed, such as mono-or polycarboxylic acid esters, anhydrides, ketones, mono-or polyether, alcohols, amines, and the like, and derivatives thereof, with aromatic dicarboxylic acid esters (such as di-n-butyl phthalate or di-isobutyl phthalate, and the like, see US 4784983) being more commonly used.
Recently, various novel nitrogen atom-containing internal electron donor compounds have appeared, such as maleimide internal electron donor compounds (CN 102268109) and hydrazide internal electron donor compounds (CN 103539874 and CN 103694385), diamide internal electron donor compounds (US 2017/024067), diamine internal electron donor compounds (CN 1087918), imine internal electron donor compounds (CN 105085733 and CN 105085746), amino ester compounds (CN 101104589, CN101125896 and CN 101172965) and amide internal electron donor compounds (US 2012322962), but the resulting catalyst effect is not remarkable.
There remains a need in the art to develop new structural types of internal electron donors to meet the needs of producing different polymers.
Disclosure of Invention
The inventor synthesizes a novel imine structure organic compound through research, and discovers that the imine structure organic compound can be used as an internal electron donor compound of an olefin polymerization catalyst, the hydrogen regulation sensitivity of the catalyst is good, and the molecular weight distribution of the obtained polymer is wide.
In a first aspect, the invention provides an imine compound, the structure of which is shown as a formula I,
in the formula I, R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclic groups of (2), halogen atoms, hydroxy groups and C with or without substituents 1 -C 30 Alkoxy, and R 1 And R is 2 Are not hydrogen at the same time; or R is 1 And R is 2 Linking into a ring;
r is selected from C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclic groups, halogen atoms, hydroxy groups, C with or without substituents 1 -C 30 Alkoxy and amino with or without substituents;
a is C with or without substituents 1 -C 30 Hydrocarbylene, heteroatom or combinations thereof, preferably C with or without substituents 1 -C 30 Alkylene, C with or without substituents 6 -C 30 Arylene, C with or without substituents 4 -C 30 Heteroarylene, or a combination thereof.
The second aspect of the invention also provides a preparation method of the imine compound shown in the formula I, which comprises the following steps:
contacting a compound of formula IIA with RCOX or (RCO) 2 O reacts to generate imine compounds shown in the formula I,
In formula IIA, R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclic groups of (2), halogen atoms, hydroxy groups and C with or without substituents 1 -C 30 Alkoxy, and R 1 And R is 2 Are not hydrogen at the same time; or R is 1 And R is 2 The links are linked into a ring and,
RCOX OR (RCO) 2 In O, R is selected from C containing or not containing substituent 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, containing or beingC without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclyl, halogen atom, hydroxy, C with or without substituents 1 -C 30 Alkoxy and amino with or without substituents,
in RCOX, X is selected from halogen, preferably from chlorine, bromine and iodine.
The third aspect of the invention also provides a preparation method of the imine compound shown in the formula I, which comprises the steps of reacting the compound shown in the formula IIB with the compound shown in the formula IIIB to generate the imine compound shown in the formula I,
in the formula IIB, A is C with or without substituent 1 -C 30 Hydrocarbylene, heteroatom or combinations thereof, preferably C with or without substituents 1 -C 30 Alkylene, C with or without substituents 6 -C 30 Arylene, C with or without substituents 4 -C 30 Heteroarylene or combination thereof, R is selected from C containing or not containing substituent 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclyl, halogen atom, hydroxy, C with or without substituents 1 -C 30 Alkoxy and amino with or without substituents;
in formula IIIB, R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aromatic of (C)C of radicals, with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclic groups of (2), halogen atoms, hydroxy groups and C with or without substituents 1 -C 30 Alkoxy, and R 1 And R is 2 Are not hydrogen at the same time; or R is 1 And R is 2 Linked into a ring.
In a fourth aspect, the present invention also provides the use of an imine compound as described above in olefin polymerization, in particular as an internal electron donor component for an olefin polymerization catalyst.
Detailed Description
In a first aspect, the present invention provides an imine ester compound represented by formula I.
In the formula I, R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclic groups of (2), halogen atoms, hydroxy groups and C with or without substituents 1 -C 30 Alkoxy, and R 1 And R is 2 Are not hydrogen at the same time; or R is 1 And R is 2 Linking into a ring;
r is selected from C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 30 Aryl, C with or without substituents 6 -C 30 Heteroaryl, C with or without substituents 4 -C 30 Heterocyclyl, halogen atom, hydroxy, with or without substituentsC of (2) 1 -C 30 Alkoxy and amino with or without substituents;
a is C with or without substituents 1 -C 30 Hydrocarbylene, heteroatom or combinations thereof, preferably C with or without substituents 1 -C 30 Alkylene, C with or without substituents 6 -C 30 Arylene, C with or without substituents 4 -C 30 Heteroarylene, or a combination thereof.
In the context of the present application, the term "substituent" refers to substituents common in the art, which may be selected from halogen, hydroxy, amino, C 6 -C 20 Aryl (including but not limited to phenyl, naphthyl, etc.), C 7 -C 20 Aralkyl (e.g., benzyl, phenethyl, etc.), C 7 -C 20 Alkylaryl (C) 1 -C 6 Alkyl-substituted phenyl), C 1 -C 10 Alkyl (including C 1 -C 6 Alkyl groups such as methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, etc.), C 1 -C 10 Alkoxy (including C 1 -C 6 Alkoxy groups such as methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, etc.), and the like. In the context of the present application, halogen refers to fluorine, chlorine, bromine or iodine. In the context of this application, the term "alkyl" includes straight chain alkyl, branched alkyl, and cycloalkyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
According to some embodiments of the invention, the substituents are selected from halogen, hydroxy, amino, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl, C 7 -C 20 Alkylaryl, C 1 -C 10 Alkyl and C 1 -C 20 Alkoxy, preferably selected from halogen, hydroxy, amino, phenyl, naphthyl, benzyl, phenethyl, C 1 -C 6 Phenyl substituted by alkyl, C 1 -C 10 Alkyl and C 1 -C 20 Alkoxy groups, more preferably selected fromFluorine, chlorine, bromine, iodine, hydroxyl, amino, phenyl, naphthyl, benzyl, phenethyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, isopentoxy, and n-hexoxy.
According to some embodiments of the invention, R 1 And R is 2 Each independently selected from hydrogen, C with or without substituents 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 2 -C 30 Alkynyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 4 -C 20 Heterocyclyl, halogen atom, hydroxy and C with or without substituents 1 -C 20 An alkoxy group.
According to some embodiments of the invention, R 1 And R is 2 Each independently selected from hydrogen, C with or without substituents 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 6 -C 15 Aryl, C with or without substituents 4 -C 50 Heterocyclyl, halogen atom, hydroxy and C with or without substituents 1 -C 10 An alkoxy group.
According to some embodiments, R 1 And R is 2 Each independently selected from hydrogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 6 -C 15 Aryl groups. According to some embodiments, R 1 And R is 2 Is C with or without substituents 1 -C 10 Straight chain alkyl, C with or without substituents 3 -C 10 Branched alkyl, C with or without substituents 3 -C 10 Cycloalkyl or substituted phenyl or unsubstituted phenyl. Preferably, the substituents are selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, halogen, hydroxy and amino.
According to some embodiments, R 1 And R is 2 Each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, benzyl, phenyl, halophenyl, naphthyl, biphenyl, or a heterocyclic compound-containing group, and the like; the heterocyclic compound-containing group is preferably a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, or a quinoline-containing group.
In some embodiments, R 1 Is hydrogen, R 2 Is C 1 -C 10 Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, etc.), phenyl, C 1 -C 6 Alkyl-substituted phenyl, hydroxy-substituted phenyl, halogen-substituted phenyl or C 1 -C 6 At least two substituted phenyl groups selected from alkyl, halogen and hydroxy.
According to some embodiments, R is selected from C with or without substituents 1 -C 10 Alkyl and C with or without substituents 6 -C 15 Aryl groups. According to some embodiments, R is C with or without substituents 1 -C 10 Straight chain alkyl, C with or without substituents 3 -C 10 Branched alkyl, C with or without substituents 3 -C 10 Cycloalkyl or phenyl with or without substituents, preferably selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, halogen, hydroxy and amino.
According to some embodiments of the invention, A is C with or without substituents 1 -C 20 Alkylene, C 6 -C 20 Arylene group, C 4 -C 20 Heteroarylene, or a combination thereof.
According to some embodiments of the invention, A is C with or without substituents 1 -C 10 Alkylene, C 6 -C 10 Arylene group, C 4 -C 10 Heteroarylene, or a combination thereof.
According to some embodiments of the invention, A is C with or without substituents 1 -C 8 An alkylene group. According to some embodiments, A is unsubstituted C 1 -C 8 Alkylene (e.g. methylene, ethylene, propylene, butylene, pentylene, hexylene) or C 1 -C 6 Alkyl or C 1 -C 6 Alkoxy substituted C 1 -C 8 An alkylene group.
According to some embodiments of the invention, A is- (CR) I R II ) n -, wherein R is I 、R II May be the same or different and is selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 2 -C 30 Alkenyl, C with or without substituents 3 -C 30 Alicyclic hydrocarbon of (C) and C with or without substituent 6 -C 30 An aryl group; n=1-6; or said R I And R is II Linked into a ring.
According to some embodiments, a is- (CR I R II ) n -, wherein R is I 、R II Identical or different, selected from hydrogen, C with or without substituents 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 3 -C 10 Alicyclic hydrocarbon of (C) and C with or without substituent 6 -C 20 An aryl group; n=1, 2, 3, 4, 5 or 6.
According to some embodiments, a is- (CR I R II ) n -, wherein R is I 、R II Identical or different, selected from hydrogen, C with or without substituents 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 3 -C 10 Cycloalkanes and C with or without substituents 6 -C 10 An aryl group; n=1, 2, 3, 4, 5 or 6.
According to some embodiments, a is- (CR I R II ) n -, wherein R is I 、R II Identical or different, selected from hydrogen, C with or without substituents 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, with or without substitutionC of radicals 3 -C 10 Cycloalkanes and C with or without substituents 6 -C 10 An aryl group; n=1, 2, 3, 4, 5 or 6.
According to some embodiments, a is- (CR I R II ) n -, wherein R is I 、R II Identical or different, selected from hydrogen, C with or without substituents 1 -C 8 Alkyl, C with or without substituents 2 -C 8 Alkenyl, C with or without substituents 3 -C 8 Cycloalkanes and C with or without substituents 6 -C 10 An aryl group; n=1, 2, 3, 4, 5 or 6.
According to some embodiments of the invention, a is a heteroatom selected from nitrogen, phosphorus and silicon atoms.
The imine compound shown in the formula I can be selected from but not limited to the following compounds:
2-xylylenediamine ethyl benzoate, 2- (2-methyl) xylylenediamine ethyl benzoate, 2- (3-methyl) xylylenediamine ethyl benzoate, 2- (4-methyl) xylylenediamine ethyl benzoate, 2- (2-ethyl) xylylenediamine ethyl benzoate, 2- (3-ethyl) xylylenediamine ethyl benzoate, 2- (4-ethyl) xylylenediamine ethyl benzoate, 2- (2-propyl) xylylenediamine ethyl benzoate, 2- (3-propyl) xylylenediamine ethyl benzoate, 2- (2-butyl) xylylenediamine ethyl benzoate, 2- (3-butyl) xylylenediamine ethyl benzoate, 2- (4-butyl) xylylenediamine ethyl benzoate, 2- (3-methoxy) xylylenediamine ethyl benzoate, 2- (4-methoxy) xylylenediamine ethyl benzoate, 2- (2-methoxy) xylylenediamine ethyl benzoate, 2- (3-ethoxy) benzylidene ethyl benzoate, 2- (2-ethoxy) benzylidene ethyl benzoate 2- (2-hydroxy) xylylenediamine ethyl benzoate, 2- (3-hydroxy) xylylenediamine ethyl benzoate, 2- (4-hydroxy) xylylenediamine ethyl benzoate, 2- (2, 4-dimethyl) xylylenediamine ethyl benzoate, 2- (2, 4, 6-trimethyl) xylylenediamine ethyl benzoate, 2- (3, 5-di-tert-butyl) xylylenediamine ethyl benzoate, 2- (2-hydroxy-3-tert-butyl) xylylenediamine ethyl benzoate, and the like 2- (2-hydroxy-5-tert-butyl) benzylidene amino ethyl benzoate, 2-benzylidene amino propyl benzoate, 2- (2-methyl) benzylidene amino propyl benzoate, 2- (3-methyl) benzylidene amino propyl benzoate, 2- (4-methyl) benzylidene amino propyl benzoate, 2- (2-ethyl) benzylidene amino propyl benzoate, 2- (3-ethyl) benzylidene amino propyl benzoate, 2- (4-ethyl) benzylidene amino propyl benzoate, 2- (2-propyl) benzylidene amino propyl benzoate, and, 2- (3-propyl) benzaminopropyl benzoate, 2- (4-propyl) benzaminopropyl benzoate, 2- (2-butyl) benzaminopropyl benzoate, 2- (3-butyl) benzaminopropyl benzoate, 2- (4-butyl) benzaminopropyl benzoate, 2- (3-methoxy) benzaminopropyl benzoate, 2- (4-methoxy) benzaminopropyl benzoate, 2- (3-ethoxy) benzaminopropyl benzoate, 2- (4-ethoxy) benzaminopropyl benzoate, 2- (2-hydroxy) benzaminopropyl benzoate, 2- (3-hydroxy) benzaminopropyl benzoate, 2- (4-hydroxy) benzaminopropyl benzoate, 2- (2, 4-dimethyl) benzaminopropyl benzoate, 2- (2, 4-trimethyl) benzaminopropyl benzoate, 2- (2, 4, 6-trimethyl) benzaminopropyl benzoate, 2- (3-di-tert-butyl) benzaminopropyl benzoate, 2- (3-hydroxy) benzaminopropyl benzoate, 2- (3-tert-butyl) benzoate, 2-di-t-butyl) benzaminopropyl benzoate, 2- (3-hydroxy) benzoate, 5-di-butyl) benzaminopropyl benzoate 2- (2-hydroxy-5-tert-butyl) benzaminopropyl benzoate, 3- (2-methyl) benzaminopropyl benzoate, 3- (3-methyl) benzaminopropyl benzoate, 3- (4-methyl) benzaminopropyl benzoate, 3- (2-ethyl) benzaminopropyl benzoate, 3- (3-ethyl) benzaminopropyl benzoate, 3- (4-ethyl) benzaminopropyl benzoate, 3- (2-propyl) benzaminopropyl benzoate, 3- (3-propyl) benzaminopropyl benzoate, 3- (4-propyl) benzaminopropyl benzoate, 3- (2-butyl) benzaminopropyl benzoate, 3- (3-butyl) benzaminopropyl benzoate, 3- (4-butyl) benzaminopropyl benzoate, 3- (3-methoxy) propyl benzoate, 3- (3-ethoxy) propyl benzoate, 3- (3-methoxy) propyl benzoate and 3- (3-ethoxy) propyl benzoate 3- (2-ethoxy) benzaminopropyl benzoate, 3- (2-hydroxy) benzaminopropyl benzoate, 3- (3-hydroxy) benzaminopropyl benzoate, 3- (4-hydroxy) benzaminopropyl benzoate, 3- (2, 4-dimethyl) benzaminopropyl benzoate, 3- (2, 4, 6-trimethyl) benzaminopropyl benzoate, 3- (3, 5-di-t-butyl) benzaminopropyl benzoate, 3- (2-hydroxy-3-t-butyl) benzaminopropyl benzoate, 3- (2-hydroxy-5-t-butyl) benzaminopropyl benzoate, 4-methylbenzoic acid (3-benzaminopropyl benzoate), 4-methylbenzyl [3- (2-methyl) benzaminopropyl benzoate ], 4-methylbenzyl [3- (3-methyl) benzaminopropyl benzoate ], 3- (3-methyl) benzaminopropyl benzoate, 3- (3-methyl) benzyl ] 3- (3-methyl) benzaminopropyl benzoate, 3- (3-methyl) benzyl) propyl benzoate, 4-methyl (3-methyl) benzaminopropyl benzoate, 3- (3-methyl) benzyl) propyl benzoate 4-methylbenzoic acid [3- (4-ethyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-propyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-propyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (4-propyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (4-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-methoxy) benzaminopropyl ester ], 4-methylbenzoic acid [3- (4-methoxy) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-methoxy) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-ethoxy) benzaminopropyl ester ], 4-methylbenzoic acid [3- (4-ethoxy) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-methyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (3-methyl) 2, 4-methyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-methyl) propyl ester ], 4-methylbenzenepropyl ester ] 2-4-methyl-4-benzaminopropyl ester 4-methylbenzoic acid [3- (3, 5-di-tert-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-hydroxy-3-tert-butyl) benzaminopropyl ester ], 4-methylbenzoic acid [3- (2-hydroxy-5-tert-butyl) benzaminopropyl ester ], 4-propylbenzoic acid (3-benzaminopropyl ester), 4-propylbenzoic acid [3- (2-methyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-methyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (4-methyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (2-ethyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-ethyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (4-ethyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-methyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-propyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-ethyl) benzaminopropyl ester ] benzyl ] and 4-propylbenzoic acid [3- (3-ethyl) methyl ] propyl ester 4-propylbenzoic acid [3- (2-butyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-butyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (4-butyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-methoxy) benzaminopropyl ester ], 4-propylbenzoic acid [3- (4-methoxy) benzaminopropyl ester ], 4-propylbenzoic acid [3- (2-methoxy) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3-ethoxy) benzaminopropyl ester ], 4-propylbenzoic acid [3- (4-ethoxy) benzaminopropyl ester ], 4-propylbenzoic acid [3- (2, 4-dimethyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (2, 4, 6-trimethyl) benzaminopropyl ester ], 4-propylbenzoic acid [3- (3, 5-di-tert-butylbenzaminopropyl ester ], 3-di-tert-butylbenzaminopropyl ester, 3-hydroxy-3-propylbenzoate, 3-tert-butylbenzaminopropyl ester 4-propylbenzoic acid [3- (2-hydroxy-5-tert-butyl) benzylidene aminopropyl ester ], benzoic acid (3-benzylidene butyl ester), benzoic acid [3- (2-methyl) benzylidene butyl ester ], benzoic acid [3- (3-methyl) benzylidene butyl ester ], benzoic acid [3- (4-methyl) benzylidene butyl ester ], benzoic acid [3- (2-ethyl) benzylidene butyl ester ], benzoic acid [3- (3-ethyl) benzylidene butyl ester ], benzoic acid [3- (4-ethyl) benzylidene butyl ester ], benzoic acid [3- (2-propyl) benzylidene butyl ester ], benzoic acid [3- (3-propyl) benzylidene butyl ester ], benzoic acid [3- (4-propyl) benzylidene butyl ester ], benzoic acid [3- (2-butyl) benzylidene butyl ester ], benzoic acid [3- (3-butyl) benzylidene butyl ], benzoic acid [3- (4-butyl) benzylidene butyl ], benzoic acid [3- (3-methoxy) benzylidene butyl ], benzoic acid [3- (3-butyl) benzylidene butyl ] benzoic acid [3- (4-methoxy) benzylidene butyl ] benzoic acid [3- (3-methoxybutyl) benzylidene butyl ] benzoic acid ] 3- (3-methoxybutyl) benzylidene ] benzyl ] 3- (3-methoxybutyl) benzylidene butyl) benzoate) 3- (4-ethoxy) benzylidene butyl benzoate, 3- (2-hydroxy) benzylidene butyl benzoate, 3- (3-hydroxy) benzylidene butyl benzoate, 3- (4-hydroxy) benzylidene butyl benzoate, 3- (2, 4-dimethyl) benzylidene butyl benzoate, 3- (2, 4, 6-trimethyl) benzylidene butyl benzoate, 3- (3, 5-di-tert-butyl) benzylidene butyl benzoate, 3- (2-hydroxy-3, 5-di-tert-butyl) benzylidene butyl benzoate, and 3- (2-hydroxy-3-tert-butyl) benzylidene butyl benzoate, 3- (2-hydroxy-5-tert-butyl) benzylidene butyl benzoate, 3- (2-methyl) benzylidene amyl benzoate, 3- (3-methyl) benzylidene amyl benzoate, 3- (4-methyl) benzylidene amyl benzoate, 3- (2-ethyl) benzylidene amyl benzoate, 3- (3-ethyl) benzylidene amyl benzoate, 3- (4-ethyl) benzylidene aminopentanyl benzoate, 3- (2-propyl) benzylidene aminopentanyl benzoate, 3- (3-propyl) benzylidene aminopentanyl benzoate, 3- (4-propyl) benzylidene aminopentanyl benzoate, 3- (2-butyl) benzylidene aminopentanyl benzoate, 3- (3-butyl) benzylidene aminopentanyl benzoate, 3- (4-butyl) benzylidene aminopentanyl benzoate, 3- (3-methoxy) methyleneaminopentanyl benzoate, 3- (3-methoxy) methyleneamyl benzoate, 3- (4-methoxy) benzylidene amyl benzoate 3- (2-methoxy) benzaminopentyl benzoate, 3- (3-ethoxy) benzaminopentyl benzoate, 3- (4-ethoxy) benzaminopentyl benzoate, 3- (2-hydroxy) benzaminopentyl benzoate, 3- (3-hydroxy) benzaminopentyl benzoate, 3- (4-hydroxy) benzaminopentyl benzoate, 3- (2, 4-dimethyl) benzaminopentyl benzoate, 3- (2, 4, 6-trimethyl) benzaminopentyl benzoate, 3- (3, 5-di-tert-butyl) benzamidyl amyl benzoate, 3- (2-hydroxy-3-tert-butyl) benzamidyl amyl benzoate, 3- (2-hydroxy-5-tert-butyl) benzamidyl amyl benzoate, and,
Benzoic acid (4-xylylenediamine-2-pentyl ester), benzoic acid [4- (2-methyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-methyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (4-methyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-ethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-ethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (4-ethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-propyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-propyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (4-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-ethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-methoxy) benzylidene-2-pentyl ester ], benzoic acid [4- (3-methoxy) benzyl ] 4-2-pentyl ester ], benzoic acid [4- (3-methoxy) benzyl ] 2-pentyl ester Benzoic acid [4- (4-ethoxy) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-hydroxy) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3-hydroxy) xylylenediamine-2-pentyl ester ], benzoic acid [4- (4-hydroxy) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2, 4-dimethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2, 4, 6-trimethyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (3, 5-di-tert-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-hydroxy-3-tert-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-hydroxy-5-tert-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-hydroxy-2-benzyl-5-tert-butyl) xylylenediamine-2-pentyl ester ], benzoic acid [4- (2-hydroxy-benzyl-2-pentyl ester ], benzyl-62-pentyl ester), and benzyl (4-methylamino-2-pentyl ester) Benzoic acid (4-hexyleneamino-2-pentyl ester), benzoic acid (4-heptylmethyleneamino-2-pentyl ester), benzoic acid (4-octyleneamino-2-pentyl ester), benzoic acid (4-cyclohexyleneamino-2-pentyl ester), benzoic acid (4-cyclopentyleneamino-2-pentyl ester), benzoic acid [4- (2-cyclohexenyl) methyleneamino-2-pentyl ester ], 4-propylbenzoic acid (4-Ding Yajia amino-2-pentyl ester), 4-propylbenzoic acid (4-hexyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-pentylmethyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-hexyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-heptyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-octyleneamino-2-pentyl ester), 4-methylbenzoic acid (4-hexyleneamino-2-pentyl ester), 4-ethylbenzoic acid (4-heptyleneamino-2-heptyl ester), 4-ethylenebenzoic acid (4-heptyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-octyleneamino-2-pentyl ester), 4-butylbenzoic acid (4-hexylenemethylamino-2-pentyl ester), 4-butylbenzoic acid (4-pentylmethyleneamino-2-pentyl ester), 4-propylbenzoic acid (4-cyclohexylenemethylamino-2-pentyl ester), 4-propylbenzoic acid (4-cyclopentylmethyleneamino-2-pentyl ester), 4-propylbenzoic acid [4- (2-cyclohexenyl) methyleneamino-2-pentyl ester ], 4-methylbenzoic acid (4-benzyleneamino-2-pentyl ester), 4-methylbenzoic acid [4- (2-methyl) benzyleneamino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methyl) benzyleneamino-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methyl) benzyleneamino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-ethyl) benzyleneamino-2-pentyl ester ], 4-methylbenzoic acid [4- (3-ethyl) benzylenemethylamino-2-pentyl ester ], 4-methylbenzoic acid [4- (2-methyl) benzyleneamino-2-pentyl ester ] (4-methyl) benzyleneamino-2-pentyl ester), 4-methylbenzoic acid [4- (3-propyl) xylylenediamine-2-pentyl ester ], 4-methylbenzoic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ], 4-methylbenzoic acid [4- (3-butyl) xylylenediamine-2-pentyl ester ], 4-methylbenzoic acid [4- (4-butyl) xylylenediamine-2-pentyl ester ], 4-methylbenzoic acid [4- (3-methoxy) xylylenediamine-2-pentyl ester ], 4-methylbenzoic acid [4- (4-methoxy) xylylenediamine-2-pentyl ester ]: 4-methylbenzoic acid [4- (3-ethoxy) benzylidene-2-pentyl ] 4-methylbenzoic acid [4- (4-ethoxy) benzylidene-2-pentyl ] 4-methylbenzoic acid [4- (2-hydroxy) benzylidene-2-pentyl ] 4-methylbenzoic acid [4- (3-hydroxy) benzylidene-2-pentyl ] 4-methylbenzoic acid [4- (4-hydroxy) benzylidene-2-pentyl ] 4-methylbenzyl-2-pentyl), 4-methylbenzoic acid [4- (2, 4-dimethyl) benzylidene-2-pentyl ester ], 4-methylbenzoic acid [4- (2, 4, 6-trimethyl) benzylidene-2-pentyl ester ], 4-methylbenzoic acid [4- (3, 5-di-tert-butyl) benzylidene-2-pentyl ester ], 4-methylbenzoic acid [4- (2-hydroxy-3-tert-butyl) benzylidene-2-pentyl ester ], 4-methylbenzoic acid [4- (2-hydroxy-5-tert-butyl) benzylidene-2-pentyl ester ], 4-ethylbenzoic acid (4-benzylidene-2-pentyl ester), 4-ethylbenzoic acid [4- (2-methyl) benzylidene-2-pentyl ester ], 4-ethylbenzylidene-2-pentyl ester ], 4- (4-ethylbenzyl-2-methyl) benzylidene-2-pentyl ester ], 4-benzylidene-2-pentyl ester, 4-ethylbenzyl-2-methyl-2-pentyl ester 4-ethylbenzoic acid [4- (4-ethyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (2-propyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (3-propyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (2-butyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (3-butyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (4-butyl) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (3-methoxy) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (4-methoxy) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (3-ethoxy) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (4-ethoxy) benzylidene-2-pentyl ] 4-ethylbenzoic acid [4- (2-ethoxy) benzylidene-2-pentyl ] 4-ethylbenzyl ] 4- (2-ethoxy) benzylidene-2-pentyl) benzyl ] 4-ethylbenzoate 4-ethylbenzoic acid [4- (3-hydroxy) xylylenediamine-2-pentyl ester ], 4-ethylbenzoic acid [4- (4-hydroxy) xylylenediamine-2-pentyl ester ], 4-ethylbenzoic acid [4- (2, 4-dimethyl) xylylenediamine-2-pentyl ester ], 4-ethylbenzoic acid [4- (2, 4, 6-trimethyl) xylylenediamine-2-pentyl ester ], 4-ethylbenzoic acid [4- (3, 5-di-t-butyl) xylylenediamine-2-pentyl ester ], 4-ethylbenzoic acid [4- (2-hydroxy-3, 5-di-t-butyl) xylylenediamine-2-pentyl ester ]: 4-ethylbenzoic acid [4- (2-hydroxy-3-tert-butyl) benzylidene-2-pentyl ester ], 4-ethylbenzoic acid [4- (2-hydroxy-5-tert-butyl) benzylidene-2-pentyl ester ], 4-propylbenzoic acid (4-benzylidene-2-pentyl ester), 4-propylbenzoic acid [4- (2-methyl) benzylidene-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methyl) benzylidene-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methyl) benzylidene-2-pentyl ester ] 4-propylbenzoic acid [4- (2-ethyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (4-ethyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (2-propyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (3-propyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ]: 4-propylbenzoic acid [4- (3-butyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (4-butyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (3-methoxy) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (4-methoxy) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (3-ethoxy) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (4-ethoxy) xylylenediamine-2-pentyl ester ] 4-propylbenzoic acid [4- (2-ethoxy) xylylenediamine-2-pentyl ], 4-propylbenzoic acid [4- (2-hydroxy) xylylenediamine-2-pentyl ], 4-propylbenzoic acid [4- (3-hydroxy) xylylenediamine-2-pentyl ], 4-propylbenzoic acid [4- (4-hydroxy) xylylenediamine-2-pentyl ], 4-propylbenzoic acid [4- (2, 4-dimethyl) xylylenediamine-2-pentyl ], 4-propylbenzoic acid [4- (2, 4, 6-trimethyl) xylylenediamine-2-pentyl ], a mixture of two or more solvents 4-propylbenzoic acid [4- (3, 5-di-tert-butyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (2-hydroxy-3-tert-butyl) xylylenediamine-2-pentyl ester ], 4-propylbenzoic acid [4- (2-hydroxy-5-tert-butyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid (4-xylylenediamine-2-pentyl ester), 4-butylbenzoic acid [4- (2-methyl) xylylenediamine-2-pentyl ester ], and, 4-butylbenzoic acid [4- (3-methyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (4-methyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (2-ethyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (3-ethyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (4-ethyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (2-propyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (3-propyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (3-butyl) xylylenediamine-2-pentyl ester ], 4-butylbenzoic acid [4- (4-butyl) xylylenediamine-2-pentyl ester ], 4-butylbenzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (3-methoxy) benzylidene-2-pentyl ester ] (4-methoxy) benzylidene-2-pentyl ester ] 4-butylbenzoic acid [3- (3-ethoxy) benzylidene-aminopentanyl ester ], 4-butylbenzoic acid [4- (4-ethoxy) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (2-hydroxy) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (3-hydroxy) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (4-hydroxy) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (2, 4-dimethyl) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (2, 4, 6-trimethyl) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (3, 5-di-tert-butyl) benzylidene-2-pentyl ester ], 4-butylbenzoic acid [4- (2-hydroxy-3, 5-di-tert-butyl) benzylidene-2-pentyl ester ], 4-butylbenzylidene-2-pentyl ester ], 4-tert-butylbenzylidene-2-pentyl ester, 4-butylbenzoic acid [4- (2, 4-dimethyl) benzylidene-2-pentyl ester ] (4-tert-butylbenzyl) 2-butyl) 2-pentyl ester 4-methoxybenzoic acid (4-benzylidene-2-pentyl) ester), 4-methoxybenzoic acid [4- (2-methyl) benzylidene-2-pentyl) ester, 4-methoxybenzoic acid [4- (3-methyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (4-methyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (2-ethyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (3-ethyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (4-ethyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (2-propyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (3-propyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (2-butyl) benzylidene-2-pentyl) ester ], 4-methoxybenzoic acid [4- (3-butyl) benzylidene-2-pentyl) benzyl ] 4- (2-methoxybenzyl) 4-pentyl) benzoate 4-methoxybenzoic acid [4- (3-methoxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [4- (4-methoxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [3- (3-ethoxy) benzylidene-amino pentyl ester ], 4-methoxybenzoic acid [4- (4-ethoxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [4- (2-hydroxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [4- (3-hydroxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [4- (4-hydroxy) benzylidene-2-pentyl ester ], 4-methoxybenzoic acid [4- (2, 4-dimethyl) benzylidene-2-pentyl ester ], 4-ethoxybenzoic acid [4- (2, 4, 6-trimethyl) benzylidene-2-pentyl ester ], 4-ethoxybenzoic acid [4- (3-hydroxy) benzylidene-2-pentyl ester ], 4- (3-hydroxy) benzylidene-2-pentyl ester ] (4-tert-butyl) benzyl) 2-methyl) benzoate 4-ethoxybenzoic acid [4- (2-hydroxy-3-tert-butyl) xylylenediamine-2-pentyl ester ], 4-ethoxybenzoic acid [4- (2-hydroxy-5-tert-butyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-methyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (3-methyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (4-methyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-ethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (3-ethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (4-ethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-propyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (3-propyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-ethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (3-butyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-butyl) xylylenediamine-2-pentyl ester ] ] acetate [4- (4-ethyl) xylylenediamine-2-pentyl ester ] ] [4- (3-methoxy) xylylenediamine-2-pentyl acetate ], acetic acid [4- (4-methoxy) xylylenediamine-2-pentyl acetate ], acetic acid [4- (3-ethoxy) xylylenediamine-2-pentyl ester ], acetic acid [4- (4-ethoxy) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-hydroxy) xylylenediamine-2-pentyl ester ], acetic acid [4- (3-hydroxy) xylylenediamine-2-pentyl ester ], acetic acid [4- (4-hydroxy) xylylenediamine-2-pentyl ester ], acetic acid [4- (2, 4-dimethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2, 4, 6-trimethyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (3, 5-di-tert-butyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-hydroxy-3, 5-di-tert-butyl) xylylenediamine-2-pentyl ester ], acetic acid [4- (2-hydroxy) benzyl ] 2-pentyl ester ], acetic acid [4- (2, 4-dimethyl) xylylenediamine-2-pentyl ester ] (2-hydroxy) benzyl) acetate, 5-tert-butyl) benzyl ] acetate (4-xylylenediamine-2-pentyl) propionate, [4- (2-methyl) xylylenediamine-2-pentyl) propionate, [4- (3-methyl) xylylenediamine-2-pentyl) propionate, [4- (4-methyl) xylylenediamine-2-pentyl) propionate, [4- (2-ethyl) xylylenediamine-2-pentyl) propionate, [4- (3-ethyl) xylylenediamine-2-pentyl) propionate, [4- (4-ethyl) xylylenediamine-2-pentyl) propionate, [4- (2-propyl) xylylenediamine-2-pentyl ] propionate, [4- (3-propyl) xylylenediamine-2-pentyl) propionate, [4- (2-butyl) xylylenediamine-2-pentyl) propionate, [4- (3-butyl) xylylenediamine-2-pentyl) propionate, [4- (4-butyl) xylylenediamine-2-pentyl) propionate, [4- (3-methoxy) xylylenediamine-2-pentyl) propionate, 4- (4-methoxy) xylylenediamine-2-pentyl) propionate, and [4- (2-propyl) xylylenediamine-2-pentyl ] propionate [4- (4-ethoxy) xylylenediamine-2-pentyl propionate ], [4- (2-hydroxy) xylylenediamine-2-pentyl propionate ], [4- (3-hydroxy) xylylenediamine-2-pentyl propionate ], [4- (4-hydroxy) xylylenediamine-2-pentyl propionate ], [4- (2, 4-dimethyl) xylylenediamine-2-pentyl propionate ], and [4- (2, 4, 6-trimethyl) xylylenediamine-2-pentyl propionate ]: [4- (3, 5-di-tert-butyl) xylylenediamine-2-pentyl propionate ], [4- (2-hydroxy-3, 5-di-tert-butyl) xylylenediamine-2-pentyl propionate ], propionic acid [4- (2-hydroxy-3-tert-butyl) xylylenediamine-2-pentyl propionate ], propionic acid [4- (2-hydroxy-5-tert-butyl) xylylenediamine-2-pentyl propionate ], butyric acid (4-xylylenediamine-2-pentyl), butyric acid [4- (2-methyl) xylylenediamine-2-pentyl), butyric acid [4- (3-methyl) xylylenediamine-2-pentyl ], butyric acid [ methyl ] 2-pentyl, [4- (4-methyl) xylylenediamine-2-pentyl butyrate ], [4- (2-ethyl) xylylenediamine-2-pentyl butyrate ], [4- (3-ethyl) xylylenediamine-2-pentyl butyrate ], [4- (4-ethyl) xylylenediamine-2-pentyl butyrate ], [4- (2-propyl) xylylenediamine-2-pentyl butyrate ], [4- (3-propyl) xylylenediamine-2-pentyl butyrate ], [4- (2-butyl) xylylenediamine-2-pentyl butyrate ], [4- (3-butyl) xylylenediamine-2-pentyl butyrate ], [4- (4-butyl) xylylenediamine-2-pentyl butyrate ], [4- (3-methoxy) xylylenediamine-2-pentyl butyrate ], [4- (4-methoxy) xylylenediamine-2-pentyl butyrate ], [4- (3-ethoxy) xylylenediamine-2-pentyl butyrate ], [4- (4-ethoxy) xylylenediamine-2-pentyl butyrate ], 4- (4-ethoxy) xylylenediamine-2-pentyl) butyrate, and [4- (2-hydroxy ] benzylidene-2-pentyl) butyrate [4- (3-hydroxy) xylylene-2-pentyl butyrate ], [4- (4-hydroxy) xylylene-2-pentyl butyrate ], [4- (2, 4-dimethyl) xylylene-2-pentyl butyrate ], butyric acid [4- (2, 4, 6-trimethyl) xylylene-2-pentyl ester ], butyric acid [4- (3, 5-di-tert-butyl) xylylene-2-pentyl ester ], butyric acid [4- (2-hydroxy-3-tert-butyl) xylylene-2-pentyl ester ], butyric acid [4- (2-hydroxy-5-tert-butyl) xylylene-2-pentyl ester ], valeric acid (4-benzylene-2-pentyl ester), valeric acid [4- (2-methyl) benzylene-2-pentyl ester ], valeric acid [4- (3-methyl) benzylene-2-pentyl ester ], valeric acid [4- (2-hydroxy-3-tert-butyl) benzylene-2-pentyl ester ], valeric acid [4- (2-methyl) benzylene-2-pentyl ester ], valeric acid [4- (2-ethyl ] benzylene-2-pentyl ester ] (2-benzyl) 2-pentyl ester) Pentanoic acid [4- (4-ethyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (2-propyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (3-propyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (2-butyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (3-butyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (4-butyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (3-methoxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (4-methoxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (3-ethoxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (4-ethoxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (2-hydroxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (3-hydroxy) benzylidene-2-pentyl ester ], pentanoic acid [4- (4-hydroxy) benzylidene-2-pentyl ester ] 2-pentyl ester, pentanoic acid [4- (2, 4, 6-trimethyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (3, 5-di-tert-butyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (2-hydroxy-3-tert-butyl) benzylidene-2-pentyl ester ], pentanoic acid [4- (2-hydroxy-5-tert-butyl) benzylidene-2-pentyl ester ], benzoic acid (3-methyl-4-benzylidene-2-pentyl ester), benzoic acid [ 3-methyl-4- (2-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-ethyl) benzylidene-2-pentyl ester ], benzyl acid [ 3-methyl-4-methyl-2-pentyl ester ] [ 3-methyl-4-methyl ] benzylidene-2-pentyl ester ] Benzoic acid [ 3-methyl-4- (2-propyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-propyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-butyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-butyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2-hydroxy) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3-hydroxy) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (4-hydroxy) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 4-dimethyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (2, 4, 6-trimethyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-methyl-4- (3, 5-di-tert-butyl) benzylidene-2-pentyl ester ] (3-methyl-4- (2, 4-dimethyl) benzylidene-2-pentyl ester), 3-methyl-4- (2-hydroxy-3-tert-butyl) benzylidene-2-pentyl benzoate, 3-methyl-4- (2-hydroxy-5-tert-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-methyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (3-methyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (4-methyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-ethyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (3-ethyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (4-ethyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-propyl) benzylidene-2-pentyl benzoate, 3-ethyl-2-pentyl benzoate, 3-ethyl-4- (2-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (3-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (4-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-hydroxy) benzylidene-2-pentyl benzoate, 3-ethyl-4- (3-hydroxy) benzylidene-2-pentyl benzoate, 3-ethyl-4- (4-hydroxy) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2, 4-dimethyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2, 4, 6-trimethyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (3, 5-di-tert-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-hydroxy) benzylidene-2-pentyl benzoate, 3-tert-butyl) benzylidene-2-pentyl benzoate, 3-ethyl-4- (2-hydroxy) benzylidene-2-pentyl benzoate, benzoic acid [ 3-ethyl-4- (2-hydroxy-5-tert-butyl) benzylidene-2-pentyl ester ], benzoic acid (3-propyl-4-benzylidene-2-pentyl ester), benzoic acid [ 3-propyl-4- (2-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (3-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (4-methyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (2-ethyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (3-ethyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (4-ethyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (2-propyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-4- (3-propyl) benzylidene-2-pentyl ester ], benzoic acid [ 3-propyl-2-propyl ] benzyl-2-pentyl ester ] (2-butyl) benzyl ] methyl-2-pentyl ester 3-propyl-4- (3-butyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (4-butyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (2-hydroxy) benzylidene-2-pentyl benzoate, 3-propyl-4- (3-hydroxy) benzylidene-2-pentyl benzoate, 3-propyl-4- (4-hydroxy) benzylidene-2-pentyl benzoate, 3-propyl-4- (2, 4-dimethyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (2, 4, 6-trimethyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (3, 5-di-tert-butyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (2-hydroxy-3, 5-di-tert-butyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (3-hydroxy) benzylidene-2-pentyl benzoate, 3-propyl-4- (3-tert-butyl) benzylidene-2-pentyl benzoate, 3-propyl-4- (2-hydroxy) benzyl) benzoate, etc., and 3-propyl-4- (2-butyl) benzyl) benzoate Benzoic acid (5-benzamido-3-heptyl), benzoic acid [5- (2-methyl) benzamido-3-heptyl, benzoic acid [5- (3-methyl) benzamido-3-heptyl ], benzoic acid [5- (4-methyl) benzamido-3-heptyl ], benzoic acid [5- (2-ethyl) benzamido-3-heptyl ], benzoic acid [5- (3-ethyl) benzamido-3-heptyl ], benzoic acid [5- (4-ethyl) benzamido-3-heptyl ], benzoic acid [5- (2-propyl) benzamido-3-heptyl ], benzoic acid [5- (3-propyl) benzamido-3-heptyl ], benzoic acid [5- (2-butyl) benzamido-3-heptyl ], benzoic acid [5- (3-butyl) benzamido-3-heptyl ], benzoic acid [5- (4-butyl) benzamido-3-heptyl ], benzoic acid [5- (3-methoxy) benzamido-3-heptyl ], benzoic acid [5- (3-butyl) benzamido-heptyl) benzyl ] and benzoic acid [5- (2-butyl) benzamido-heptyl) Benzoic acid [5- (2-hydroxy) benzamido-3-heptyl ] benzoate [5- (3-hydroxy) benzamido-3-heptyl ] benzoate [5- (4-hydroxy) benzamido-3-heptyl ] benzoate [5- (2, 4-dimethyl) benzamido-3-heptyl ] benzoate [5- (2, 4, 6-trimethyl) benzamido-3-heptyl ] benzoate [5- (3, 5-di-tert-butyl) benzamido-3-heptyl ] benzoate [5- (2-hydroxy-3, 5-di-tert-butyl) benzamido-3-heptyl ] benzoate benzoic acid [5- (2-hydroxy-3-tert-butyl) benzamido-3-heptyl ester ], benzoic acid [5- (2-hydroxy-5-tert-butyl) benzamido-3-heptyl ester ], benzoic acid (4-methyl-5-benzamido-3-heptyl ester) benzoic acid [ 4-methyl-5- (2-methyl) benzamido-3-heptyl ] benzoate [ 4-methyl-5- (3-methyl) benzamido-3-heptyl ] benzoate ] benzoic acid [ 4-methyl-5- (4-methyl) benzamido-3-heptyl ] benzoate salt Benzoic acid [ 4-methyl-5- (2-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (3-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (4-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (2-propyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (3-propyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (2-butyl) benzamido-3-heptyl ]; benzoic acid [ 4-methyl-5- (3-butyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (4-butyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (3-methoxy) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (4-ethoxy) benzamido-3-heptyl ] Benzoic acid [ 4-methyl-5- (2-hydroxy) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (3-hydroxy) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (4-hydroxy) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (2, 4-dimethyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (2, 4, 6-trimethyl) benzamido-3-heptyl ], benzoic acid [ 4-methyl-5- (3, 5-di-tert-butyl) benzamido-3-heptyl ]; benzoic acid [ 4-methyl-5- (2-hydroxy-3, 5-di-tert-butyl) benzamido-3-heptyl ester ], benzoic acid [ 4-methyl-5- (2-hydroxy-3-tert-butyl) benzamido-3-heptyl ester ], benzoic acid [ 4-methyl-5- (2-hydroxy-5-tert-butyl) benzamido-3-heptyl ester ], benzoic acid (4-ethyl-5-benzamido-3-heptyl ester), benzoic acid [ 4-ethyl-5- (2-methyl) benzamido-3-heptyl ester ] Benzoic acid [ 4-ethyl-5- (3-methyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (4-methyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (2-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (3-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (4-ethyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (2-propyl) benzamido-3-heptyl ]; benzoic acid [ 4-ethyl-5- (3-propyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (2-butyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (3-butyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (4-butyl) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (3-methoxy) benzamido-3-heptyl ] Benzoic acid [ 4-ethyl-5- (4-methoxy) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (4-ethoxy) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (2-hydroxy) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (3-hydroxy) benzamido-3-heptyl ], benzoic acid [ 4-ethyl-5- (4-hydroxy) benzamido-3-heptyl ]; benzoic acid [ 4-ethyl-5- (2, 4-dimethyl) benzamido-3-heptyl ester ], benzoic acid [ 4-ethyl-5- (2, 4, 6-trimethyl) benzamido-3-heptyl ester ], benzoic acid [ 4-ethyl-5- (3, 5-di-tert-butyl) benzamido-3-heptyl ester ], benzoic acid [ 4-ethyl-5- (2-hydroxy-3-tert-butyl) benzamido-3-heptyl ester ] Benzoic acid [ 4-ethyl-5- (2-hydroxy-5-tert-butyl) benzamido-3-heptanoate ] and the like.
The second aspect of the invention also provides a preparation method of the imine compound shown in the formula I, which comprises the following steps:
contacting a compound of formula IIA with RCOX or (RCO) 2 O reacts to produce imine compounds shown in formula I, the reaction formula can be shown as follows
Wherein R in formula IIA 1 、R 2 And A is as defined for formula I, RCOX or (RCO) 2 R in O is defined as formula I, X is selected from halogen, preferably from chlorine, bromineAnd iodine.
According to an embodiment of the invention, the compound of formula IIA is combined with RCOX or (RCO) 2 The O reaction is carried out in the presence of an acid or a base. The acid is selected from inorganic or organic acids, preferably from hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid; the base is selected from inorganic or organic bases, preferably from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, diethylamine, ethylenediamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazobicyclo [5,4,0]Undec-7-ene), DBN (1, 5-diazabicyclon-5-ene), pyrazole, and the like.
According to an embodiment of the invention, the compound of formula IIA is combined with RCOX or (RCO) 2 The O reaction is carried out in a solvent. The solvent may be ether, hydrocarbon, etc., specifically diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether, diglycidyl ether, etc.
According to some embodiments of the invention, the compound of formula IIA is combined with RCOX or (RCO) 2 The O reaction is carried out in the presence of an organic base, preferably triethylamine, and an ethereal solvent, preferably tetrahydrofuran.
The third aspect of the present invention also provides another preparation method of an imine compound represented by formula I, which includes reacting a compound represented by formula IIB with a compound represented by formula IIIB to form an imine compound represented by formula I, where the reaction formula is as follows:
wherein A and R in formula IIB are as defined for formula I, R in formula IIIB 1 And R is 2 Is defined as in formula I.
According to an embodiment of the present invention, the reaction of the compound of formula IIB with the compound of formula IIIB is carried out in the presence of an acid or a base. The acid is selected from inorganic or organic acids, preferably from hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid; the base is selected from inorganic or organic bases, preferably selected from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium t-butoxide, trimethylamine, triethylamine, diethylamine, ethylenediamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazobicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclon-5-ene), pyrazole, and the like.
According to an embodiment of the present invention, the reaction of the compound of formula IIB with the compound of formula IIIB is carried out in a solvent. The solvent may be ether, hydrocarbon, alcohol, etc., specifically diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether, diglycidyl ether, isopropanol, etc.
The fourth aspect of the present invention also provides the use of an imine compound as described above in olefin polymerization, in particular as an internal electron donor component of an olefin polymerization catalyst.
The invention has the following characteristics:
1. the compound used in the invention and the application of the compound in preparation of olefin polymerization catalysts and olefin polymerization reactions are not reported in the literature.
2. The novel internal electron donor compound can be used for obtaining a catalyst with excellent comprehensive performance, and the catalyst has good hydrogen regulation sensitivity when being used for propylene polymerization reaction, and the obtained polypropylene resin has wide molecular weight distribution.
The testing method comprises the following steps:
1. polymer Melt Index (MI): according to GB/T3682-2000;
2. Propylene polymer Isotacticity Index (II): measurement was performed by heptane extraction: 2g of dried polymer sample is put in an extractor and is extracted by boiling heptane for 6 hours, and the ratio of the weight (g) of the polymer obtained by drying the residue to constant weight to 2 (g) is isotacticity;
3. polymer molecular weight distribution MWD (mwd=mw/Mn): PL-GPC220 was used, with trichlorobenzene as a solvent, at 150℃C (standard: polystyrene, flow rate: 1.0mL/min, column: 3x Plgel 10um MlxED-B300X 7.5 nm).
4. Activity calculation: catalyst activity= (mass of polyolefin produced)/(mass of catalyst solid component) g/g.
Examples
The following examples are given to illustrate the invention without limiting it.
Synthesis of (one) Compounds
EXAMPLE 1 Synthesis of the Compound benzoic acid (3-dimethylaminopropyl ester)
Method 1: in a 250 ml three-necked flask, 3.26 g of 3- (xylylenediamine) propanol, 120 ml of THF and 2.15 ml of triethylamine were introduced after purging with nitrogen, and 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring and reacting for 4 hours, heating and refluxing for reacting for 8 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 2.47 g of the product (yield 40%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.13-8.10(1H,m,＝CH),7.97-7.94(2H,m,ArH),7.63-7.61(2H,m,ArH),7.46-7.44(1H,m,ArH),7.36-7.34(2H,m,ArH),7.30-7.28(3H,m,ArH),4.25-4.23(2H,t,OCH 2 ),3.55-3.53(2H,m,＝NCH 2 ),2.12-2.10(2H,t,CH 2 )。
Method 2: in a 250 ml three-necked flask, 3.58 g of (3-amino) propyl benzoate, 120 ml of isopropyl alcohol and 0.15 ml of glacial acetic acid were added after purging with nitrogen, and 2.12 g of benzaldehyde was added dropwise at room temperature and stirred well. After stirring and reacting for 4 hours, the temperature is raised for reacting for 24 hours. Concentrating under reduced pressure, and concentrating with diethyl ether/petroleum etherThe (1:50) mixed solution was recrystallized to give pale yellow crystals, which were dried in vacuo to give 2.47 g of a product (yield 40%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.13-8.11(1H,m,＝CH),7.97-7.95(2H,m,ArH),7.63-7.61(2H,m,ArH),7.46-7.44(1H,m,ArH),7.36-7.34(2H,m,ArH),7.30-7.28(3H,m,ArH),4.25-4.23(2H,t,OCH 2 ),3.55-3.53(2H,m,＝NCH 2 ),2.12-2.10(2H,t,CH 2 )。
EXAMPLE 2 Synthesis of the Compound benzoic acid [4- (3, 5-di-tert-butylbenzylidene-amino) -2-pentyl ] ester
In a 250 ml three-necked flask, 3.03 g of 4- (3, 5-di-tert-butylbenzylidene) -2-pentanol, 120 ml of THF and 1.10 ml of triethylamine were added after nitrogen purging, and 1.40 g of benzoyl chloride was added dropwise at room temperature and stirred uniformly. After stirring and reacting for 4 hours, heating and refluxing for reacting for 10 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 2.10 g of the product (yield: 51%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.23-8.22(1H,m,＝CH),7.99-7.98(2H,m,ArH),7.46-7.44(3H,m,ArH),7.36-7.34(3H,m,ArH),4.20-4.18(1H,t,OCH),3.35-3.32(1H,t,NCH),2.04-2.03(2H,m,CH 2 ),1.41-1.39(3H,d,CH 3 ),1.35-1.32(18H,m,CH 3 ),1.28-1.26(3H,d,CH 3 )。
EXAMPLE 3 Synthesis of the Compound benzoic acid [4- (2-hydroxybenzoimino) -2-pentyl ] ester
In a 250 ml three-necked flask, after nitrogen purging, 4.14 g of 4- (2-hydroxybenzeneimino) -2-pentanol, 150 ml of THF and 2.15 ml of triethylamine were added, 2.80 g of benzoyl chloride was added dropwise at room temperature and stirred well. Stirring and reacting for 6 hours, and then heating and refluxing and reacting for 8 hours. Concentrating under reduced pressure, and weighing with diethyl ether/petroleum ether (1:50) mixture Crystallization gave pale yellow crystals which were dried under vacuum to give 2.36 g of product (yield 38%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.30-8.29(1H,m,＝CH),7.98-7.97(2H,m,ArH),7.46-7.44(2H,m,ArH),7.38-7.37(2H,m,ArH),7.13-7.12(1H,m,ArH),6.86-6.85(1H,m,ArH),6.75-6.74(1H,m,ArH),5.37-5.33(1H,m,OH),4.15-4.14(1H,t,OCH),3.36-3.33(1H,t,NCH),2.04-2.03(2H,m,CH 2 ),1.44-1.43(3H,d,CH 3 ),1.27-1.26(3H,d,CH 3 )。
EXAMPLE 4 Synthesis of the Compound 4-propylbenzoic acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylimino) -2-pentyl ] ester
In a 250 ml three-necked flask, after nitrogen purge, 3.19 g of 4- (3, 5-di-tert-butyl-2-hydroxybenzeneimino) -2-pentanol (100 ml of THF and 1.10 ml of triethylamine) were added dropwise at room temperature, 1.82 g of 4-propylbenzoyl chloride was added dropwise, stirred well, stirred for 6 hours, then heated and refluxed for 10 hours, concentrated under reduced pressure and recrystallized from a mixed solution of diethyl ether/petroleum ether (1:50) to give pale yellow crystals, and dried under vacuum to give 1.95 g of the product (yield 42%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.27-8.26(1H,m,＝CH),7.95-7.94(2H,m,ArH),7.27-7.26(1H,m,ArH),7.23-7.21(2H,m,ArH),7.09-7.08(1H,m,ArH),5.34-5.31(1H,m,OH),4.13-4.12(1H,t,OCH),3.33-3.30(1H,t,NCH),2.55-2.53(2H,t,CH 2 ),2.03-2.02(2H,m,CH 2 ),1.67-1.65(2H,m,CH 2 ),1.43-1.42(3H,d,CH 3 ),1.35-1.32(18H,m,CH 3 ),1.27-1.26(3H,d,CH 3 ),0.98-0.96(3H,t,CH 3 )。
EXAMPLE 5 Synthesis of the Compound caproic acid [4- (3, 5-di-tert-butyl-2-hydroxyphenylmethylamino) -2-pentyl ester ]
6.38 g of 4- (3, 5-) -are introduced after nitrogen purging in a 250 ml three-necked flaskDi-tert-butyl-2-hydroxy-benzylidene-amino) -2-pentanol (F319), 150 ml THF and 2.15 ml triethylamine (F101), 2.68 g hexanoyl chloride (F134) were added dropwise at room temperature and stirred well. After stirring and reacting for 6 hours, heating and refluxing for 16 hours. After concentration under reduced pressure, separation by column chromatography gave 2.67 g (yield 32%) of a pale yellow viscous liquid. 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.24-8.23(1H,m,＝CH),7.29-7.28(1H,m,ArH),7.17-7.15(1H,m,ArH),5.31-5.28(1H,m,OH),4.15-4.13(1H,t,OCH),3.34-3.31(1H,t,NCH),2.25-2.24(2H,t,CH 2 ),1.86-1.85(2H,m,CH 2 ),1.68-1.66(2H,m,CH 2 ),1.43-1.42(3H,d,CH 3 ),1.35-1.32(18H,m,CH 3 ),1.30-1.28(4H,m,CH 2 ),1.27-1.26(3H,d,CH 3 ),0.98-0.96(3H,t,CH 3 )。
EXAMPLE 6 Synthesis of the Compound benzoic acid [ 3-methyl-4- (3, 5-di-tert-butyl-2-hydroxyphenylmethylamino) -2-pentyl ester ]
In a 250 ml three-necked flask, 3.33 g of 3-methyl-4- (3, 5-di-tert-butyl-2-hydroxybenzeneimino) -2-pentanol, 100 ml of THF and 1.10 ml of triethylamine were added after nitrogen purging, 1.40 g of benzoyl chloride was added dropwise at room temperature and stirred well. After stirring and reacting for 6 hours, heating and refluxing for reacting for 12 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 1.70 g of the product (yield 39%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.28-8.27(1H,m,＝CH),7.99-7.98(2H,m,ArH),7.47-7.46(1H,m,ArH),7.35-7.34(2H,m,ArH),7.29-7.28(1H,m,ArH),7.19-7.18(1H,m,ArH),5.32-5.29(1H,m,OH),4.12-4.10(1H,t,OCH),3.30-3.27(1H,t,NCH),2.13-2.12(1H,m,CH 2 ),1.43-1.42(3H,d,CH 3 ),1.35-1.32(18H,m,CH 3 ),1.27-1.26(3H,d,CH 3 ),1.06-1.04(3H,t,CH 3 )。
EXAMPLE 7 Synthesis of the Compound 4-propylbenzoic acid [4- (3-tert-butyl-2-hydroxyphenylmethylamino) -2-pentyl ester ]
In a 250 ml three-necked flask, 5.26 g of 4- (3-di-tert-butyl-2-hydroxybenzeneimino) -2-pentanol, 150 ml of THF and 2.15 ml of triethylamine were added after nitrogen purging, 3.64 g of 4-propylbenzoyl chloride was added dropwise at room temperature and stirred well. Stirring and reacting for 6 hours, and then heating and refluxing and reacting for 10 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 3.68 g of the product (yield 45%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.28-8.27(1H,m,＝CH),7.96-7.94(2H,m,ArH),7.26-7.25(1H,m,ArH),7.23-7.21(2H,m,ArH),7.12-7.10(1H,m,ArH),6.75-6.74(1H,m,ArH),5.34-5.31(1H,m,OH),4.13-4.12(1H,t,OCH),3.34-3.31(1H,t,NCH),2.55-2.53(2H,t,CH 2 ),2.03-2.02(2H,m,CH 2 ),1.66-1.65(2H,m,CH 2 ),1.43-1.42(3H,d,CH 3 ),1.35-1.32(9H,m,CH 3 ),1.28-1.27(3H,d,CH 3 ),0.97-0.96(3H,t,CH 3 )。
EXAMPLE 8 Synthesis of the Compound 4-propylbenzoic acid (4-pentylmethyleneamino-2-pentyl ester)
In a 250 ml three-necked flask, 3.70 g of 4- (pentylmethyleneamino) -2-pentanol, 150 ml of THF and 2.15 ml of triethylamine were introduced after purging with nitrogen, 3.64 g of 4-propylbenzoyl chloride was added dropwise at room temperature and stirred well. Stirring and reacting for 6 hours, and then heating and refluxing and reacting for 10 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 2.38 g of the product (yield 36%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):7.96-7.94(2H,m,ArH),7.53-7.52(1H,m,＝CH),7.24-7.22(2H,m,ArH),4.15-4.13(1H,t,OCH),2.55-2.53(2H,t,CH 2 ),1.84-1.83(1H,t,NCH),1.73-1.71(2H,m,CH 2 ),1.66-1.65(2H,m,CH 2 ),1.43-1.42(3H,d,CH 3 ),1.33-1.30(4H,m,CH 3 ),1.28-1.25(4H,m,CH 2 ),1.08-1.06(3H,d,CH 3 ),0.97-0.96(6H,m,CH 3 )。
EXAMPLE 9 Synthesis of the Compound benzoic acid [4- (3, 5-di-tert-butyl-2-hydroxybenzeneimino) butyl ]
In a 250 ml three-necked flask, 6.10 g of 4- (3, 5-di-tert-butyl-2-hydroxybenzeneimino) butanol, 150 ml of THF and 2.15 ml of triethylamine were introduced after purging with nitrogen, 2.80 g of benzoyl chloride was added dropwise at room temperature, and after stirring for 4 hours, the reaction was continued at elevated temperature and reflux for 12 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 3.19 g of the product (yield: 39%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):8.26-8.25(1H,m,＝CH),7.98-7.97(2H,m,ArH),7.47-7.46(1H,m,ArH),7.37-7.35(2H,m,ArH),7.29-7.28(1H,m,ArH),7.19-7.18(1H,m,ArH),5.32-5.29(1H,m,OH),4.24-4.23(2H,t,OCH 2 ),3.53-3.50(2H,t,NCH 2 ),1.77-1.75(2H,m,CH 2 ),1.65-1.63(2H,m,CH 2 ),1.35-1.32(18H,m,CH 3 )。
EXAMPLE 10 Synthesis of benzoic acid (4-cyclohexylidenamino-2-pentyl ester)
In a 250 ml three-necked flask, 3.94 g of 4-cyclohexylenemethylamino-2-pentanol, 120 ml of THF and 2.15 ml of triethylamine were introduced after nitrogen purging, 2.80 g of benzoyl chloride was added dropwise at room temperature, and the mixture was stirred for 2 hours and then heated to reflux for 12 hours. After concentration under reduced pressure, recrystallization from a mixed solution of diethyl ether/petroleum ether (1:50) gave pale yellow crystals, which were dried under vacuum to give 2.24 g of the product (yield: 37%). 1 H-NMR(δ,ppm,TMS,CDCl 3 ):7.97-7.95(2H,m,ArH),7.52-7.50(1H,m,＝CH),7.46-7.44(1H,m,ArH),7.37-7.35(2H,m,ArH),4.15-4.12(1H,m,OCH),3.30-3.28(1H,t,NCH),1.73-1.71(2H,m,CH 2 ),1.64-1.62(2H,m,CH 2 )1.54-1.52(6H,m,CH 2 ),1.44-1.42(1H,m,CH),1.38-1.35(3H,m,CH 3 ),1.32-1.30(2H,m,CH 2 ),0.97-0.96(3H,d,CH 3 )。
The preparation of the solid component in the catalyst and examples of propylene polymerization are as follows:
example 11
(1) Preparation of catalyst solid component
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate were added in this order, and the temperature was raised to 50℃with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, cooled to below-25 ℃, tiCl is added dropwise within 1 hour 4 56mL, slowly heating to 80 ℃, gradually precipitating a solid, adding 6mmol of the structural compound benzoic acid (3-benzamidopropyl ester), and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to give a solid. 60mL of toluene and TiCl are then added 4 40mL was warmed to 110℃for 2h, the same procedure was repeated, and washed 3 times with 70mL of toluene at 110℃for 10min each, followed by 60mL of hexane and 2 times. And (5) drying in vacuum to obtain the solid catalyst component.
(2) Propylene polymerization
The stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mL, methylcyclohexyldimethoxy silane (CHMMS) 5mL, al/Si (mol) =25, 10mg of the solid component prepared in the above example and 1.2NL of hydrogen were added, 2.5L of liquid propylene was introduced, the temperature was raised to 70℃and maintained for 1 hour, the temperature was lowered, the pressure was released, and the PP resin was obtained by discharging, and the results are shown in Table 1.
Example 12
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with benzoic acid [4- (3, 5-di-tert-butylbenzylidene) -2-pentyl ].
Example 13
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with benzoic acid [4- (2-hydroxybenzoimino) -2-pentyl ester ].
Example 14
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with 4-propylbenzoic acid [4- (3, 5-di-tert-butyl-2-hydroxybenzylidene) -2-pentyl ester ].
Example 15
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with hexanoic acid [4- (3, 5-di-tert-butyl-2-hydroxybenzylidene) -2-pentyl ester ].
Example 16
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with benzoic acid [ 3-methyl-4- (3, 5-di-tert-butyl-2-hydroxy-benzylidene) -2-pentyl ester ].
Example 17
As in example 11, only the compound benzoic acid (3-benzylidene aminopropyl ester) was replaced with 4-propylbenzoic acid [4- (3-tert-butyl-2-hydroxybenzylidene) -2-pentyl ester ].
Example 18
As in example 11, only the compound benzoic acid (3-dimethylaminopropyl ester) was replaced with 4-propylbenzoic acid (4-pentylmethyleneamino-2-pentyl ester).
Example 19
As in example 11, only the compound benzoic acid (3-benzylidene amino propyl ester) was replaced with benzoic acid [4- (3, 5-di-tert-butyl-2-hydroxy-benzylidene amino) butyl ].
Example 20
As in example 11, only the compound benzoic acid (3-dimethylaminopropyl ester) was replaced with benzoic acid ((4-cyclohexylmethylamino-2-pentyl) ester.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (19)

1. The application of the imine compound in olefin polymerization is characterized in that the structure of the imine compound is shown as a formula I:
In the formula I, R 1 And R is 2 Identical or different, each independently selected from hydrogen, C with or without substituents 1 -C 30 Alkyl, C with or without substituents 6 -C 30 And R is an aryl group of 1 And R is 2 Are not hydrogen at the same time;
r is selected from C with or without substituents 1 -C 30 Alkyl, C with or without substituents 6 -C 30 An aryl group;
a is C with or without substituents 1 -C 30 Hydrocarbylene radicals;
the substituents are selected from hydroxy and C 1 -C 10 An alkyl group;
the alkyl is selected from the group consisting of straight chain alkyl, branched alkyl, and cycloalkyl.
2. The use according to claim 1, wherein the substituents are selected from one or more of hydroxy, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl.
3. Use according to claim 1 or 2, characterized in that R 1 And R is 2 Each independently selected from hydrogen, C with or without substituents 1 -C 20 Alkyl, C with or without substituents 6 -C 20 Aryl groups.
4. Use according to claim 3, characterized in that R 1 And R is 2 Each independently selected from hydrogen, C with or without substituents 1 -C 10 Alkyl and C with or without substituents 6 -C 15 Aryl groups.
5. The use according to claim 4, wherein R 1 And R is 2 Each independently C with or without substituents 1 -C 10 Straight chain alkyl, C with or without substituents 3 -C 10 Branched alkyl, C with or without substituents 3 -C 10 Cycloalkyl or phenyl with or without substituents.
6. The use according to claim 1 or 2, wherein R is selected from C with or without substituents 1 -C 10 Alkyl and C with or without substituents 6 -C 15 Aryl groups.
7. The use according to claim 6, wherein R is C with or without substituents 1 -C 10 Straight chain alkyl, C with or without substituents 3 -C 10 Branched alkyl, C with or without substituents 3 -C 10 Cycloalkyl or phenyl with or without substituents.
8. Use according to claim 1 or 2, whichCharacterized in that A is C with or without substituents 1 -C 20 An alkylene group.
9. The use according to claim 8, wherein A is C with or without substituents 1 -C 10 An alkylene group.
10. The use according to claim 9, wherein a is C with or without substituents 1 -C 8 An alkylene group.
11. The use according to claim 10, wherein a is C 1 -C 8 Alkylene, C 1 -C 6 Alkyl substituted C 1 -C 8 An alkylene group.
12. Use according to claim 11, wherein a is methylene, ethylene, propylene, butylene, pentylene or hexylene.
13. The use according to claim 1, wherein the preparation method of the imine compound comprises:
contacting a compound of formula IIA with RCOX or (RCO) 2 O reacts to generate imine compounds shown in the formula I,
wherein R in formula IIA 1 、R 2 And A is as defined for formula I, RCOX or (RCO) 2 R in O is defined as formula I, X is selected from halogen.
14. Use according to claim 13, wherein X is selected from chlorine, bromine and iodine.
15. The use according to claim 1, wherein the preparation method of the imine compound comprises the steps of reacting a compound shown in a formula IIB with a compound shown in a formula IIIB to generate an imine compound shown in a formula I,
wherein A and R in formula IIB are as defined for formula I, R in formula IIIB 1 And R is 2 Is defined as in formula I.
16. Use according to any one of claims 13 to 15, wherein the reaction is carried out in the presence of an acid or base, the acid being selected from inorganic or organic acids; the base is selected from inorganic or organic bases.
17. Use according to claim 16, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, benzenesulfonic acid, p-toluenesulfonic acid and oxalic acid;
And/or the base is selected from sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, trimethylamine, triethylamine, diethylamine, ethylenediamine, pyridine, picoline, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazobicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclon-5-ene) and pyrazole.
18. Use according to any one of claims 13 to 15, wherein the reaction is carried out in a solvent selected from ethers and hydrocarbons.
19. Use according to any one of claims 13 to 15, wherein the reaction is carried out in a solvent selected from diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, ethylene oxide, propylene oxide, butylene oxide, methyl glycidyl ether and diglycidyl ether.
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