CN107074757A

CN107074757A - The manufacture method of trifluoromethyl alkylthio compound

Info

Publication number: CN107074757A
Application number: CN201580060249.4A
Authority: CN
Inventors: 金原明
Original assignee: Kumiai Chemical Industry Co Ltd
Current assignee: Ihara Chemical Industry Co Ltd; Kumiai Chemical Industry Co Ltd
Priority date: 2014-11-12
Filing date: 2015-11-05
Publication date: 2017-08-18
Anticipated expiration: 2035-11-05
Also published as: CN107074757B; WO2016076183A1; IL252029A0; JPWO2016076183A1; JP6236545B2

Abstract

The manufacture method of the trifluoromethyl alkylthio compound represented by formula (1), it is characterized in that, in the presence of the compound and fluorine compounds represented by following formulas (2), addition temperature more than 45 DEG C and thiophosgene is added with the addition time of more than 0.25 hour.In formula (1), R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl etc., R1 represents C₁~C₄Alkyl etc., R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl etc..In formula (2), R is as defined in above-mentioned formula (1), and L represents halogen atom, C₁~C₄Alkylsulfonyloxy etc..

Description

The manufacture method of trifluoromethyl alkylthio compound

Technical field

The low alkyl the present invention relates to the manufacture method of trifluoromethyl alkylthio compound, more particularly to by reactivity Compound is used as the manufacture method of the trifluoromethyl alkylthio compound of raw material.

Background technology

Fluoroalkylsulfanyl is useful substituent in medicine, agricultural chemical compound.For example, having disclosed in patent document 1 Evil biological insect control agent has trifluoroethyl sulfinyl on phenyl ring, has trifluoromethylthio, fluorine in the end of alkyloxy side chain There is important effect in the expression of Pesticidal activity for alkylthio group.

In the autofrettage of the trifluoromethylthio of the alkyloxy side chain end described in patent document 1, first, make as original The halogenated alkyl compound of material reacts with metal thiocyanate salt, the (" manufacture of patent document 1 of synthesis sulfocyanic ester compound Method 11 ").Then, resulting sulfocyanic ester compound is made to be reacted with trifluoromethyl reagent, so that manufacturing purpose thing Trifluoromethyl alkylthio compound (patent document 1 " manufacture method 12 ").

Specifically, as described in the embodiment 11 of patent document 1, synthesized by bromination amyl group compound and potassium rhodanide Sulfocyanic ester compound, then as described in embodiment 12, sends out sulfocyanic ester compound and trifluoromethyl trimethylsilane Raw reaction, manufacturing purpose thing trifluoromethylthio amyl group ether compound.

The raw material of patent document 1 is the low halogenated alkyl compound of reactivity, but is implementing anti-as described in the document During the trifluoromethylthio of the low halogenated alkyl compound of answering property, it is necessary to make first its with metal thiocyanate salt etc. the system of reacting Into sulfur-containing compound, trifluoromethylation is carried out using trifluoromethyl reagent afterwards.But, in such existing method, it is Purpose thing is obtained, it is necessary to multiple processes, thus also has room for improvement in industry manufacture.In addition, trifluoromethylation reacts The middle commercially available trifluoromethyl reagent used is expensive, in terms of the economy for also require that and further reduce cost.

On the other hand, the compound with trifluoromethylthio has very high in medicine, the drug design of pesticide field Serviceability.Therefore, there is the chemical combination of trifluoromethylthio using single step (single step) and using more inexpensive raw material manufacture The exploitation of the method for thing is considered as the key subjects that should be solved, and various methods are had studied so far.

For example, in patent document 2, making benzyl halide compound be reacted with potassium fluoride and thiophosgene, obtaining purpose Thing trifluoromethylthio benzyl compounds.Using this method, the raw material used in trifluoromethylthio is to obtain at low cost Potassium fluoride and thiophosgene, can be by benzyl halide compound through single step reaction manufacturing purpose thing trifluoromethylthio benzvl compounds Thing.In addition, having recorded following methods in the embodiment of patent document 2：Will spray drying potassium fluoride, -4 '-chlorine of 4- bromomethyls two Benzophenone, the mixture of dry acetonitrile are cooled to 0 DEG C in a nitrogen atmosphere, thiophosgene are added wherein small after 0 DEG C of stirring 2 When, stirring in 8 hours is stirred at room temperature afterwards.Additionally describing needs to maintain reaction temperature into appropriate level, so that Thiophosgene will not decompose (page 13) under high temperature again.

But, in the manufacture method that patent document 2 is recorded, thiophosgene is disposably added at low temperature, so Method can only be applied to the high compound of reactivity as benzyl halide compound, to such as acyclic alkyl groups chemical combination Reactivity low halogenated alkyl compound be not appropriate in the case of trifluoromethylthio as thing.In fact, this hair A person of good sense is for the low halogenated alkyl compound of reactivity, and the embodiment 1 for having attempted referenced patent document 2 carries out the system of purpose thing Make, as a result yield it is low (equivalent to this specification " comparative example 13 ").

In patent document 3, halogenated methyl aryl compound is reacted with potassium fluoride and thiophosgene, obtain purpose thing Trifluoromethylthio methyl aryl compound.Recorded anhydrous acetonitrile, potassium fluoride, hydrogen fluoride in the embodiment 1 of patent document 3 Reactive tank is cooled to -15 DEG C by potassium, o-chlorobenzyl chlorine as raw material, adds the sulphur light of Leng KURA thereto using the times of 2 hours Gas.In addition, having been recorded in embodiment 9,16 etc. thiophosgene is added in the time of 60 DEG C of utilizations 2 hours.

But, the high compound of reactivity as halogenated methyl aryl compound is also used only in patent document 3 and makees Also it is entirely the high o-chlorobenzyl chlorine of reactivity in the compound described in embodiment for raw material.On the other hand, in patent document On the low halogenated alkyl compound of reactivity is had no into record as raw material or implied in 3.In addition, in patent document 3, being Raising stirring efficiency, addition is referred to as the granular object of bead (bead), it is necessary to using special reaction in reaction system Device.

In non-patent literature 1, halogenated aryl compound is reacted with potassium fluoride and thiophosgene, obtain purpose thing three Fluorine methyl mercapto aryl compound.Using this method, single step reaction manufacturing purpose thing can be passed through by raw material halogenated aryl compound Trifluoromethylthio aryl compound.

But, the high halogenated aryl compound work of reactivity is also used only in the manufacture method that non-patent literature 1 is recorded For raw material.In addition, in the publication on using the low halogenated alkyl compound of reactivity thio as the trifluoromethyl of raw material The manufacture method of alkyl compound also has no record or implied.

Prior art literature

Patent document

Patent document 1：No. 2013/157229 publication of International Publication No. (0238~0256 section, 0409 section, 0410 section etc.)

Patent document 2：Japanese Unexamined Patent Publication 2000-53638 publications (claim 1,0026 section etc.)

Patent document 3：No. 2011/080752 publication of International Publication No. (claim 1, page 13~25 etc.)

Non-patent literature

Non-patent literature 1：“The preparation of trifluoromethyl aryl sulfides using KF and thiophosgene”(James H.Clark,Stewart J.Tavener)Journal of Fluorine Chemistry,Vol.85,p.169-172(1997)

The content of the invention

Invent problem to be solved

As described above, in the manufacture method described in patent document 2,3 and non-patent literature 1, using potassium fluoride and sulphur Phosgene use in single step reaction, but above-mentioned document reactive high halogenated aryl compound as initiation material, and right Record or imply in the low halogenated alkyl compound of reactivity is had no as the manufacture method of raw material.

It is an object of the invention to provide a kind of manufacture method of trifluoromethyl alkylthio compound, it is without many works Sequence, is industrially preferred without using special reaction unit using the raw material for being capable of low cost acquisition.

The means to solve the problem

Depth has been repeated in manufacture method of the present inventor in view of the foregoing for trifluoromethyl alkylthio compound Enter research, as a result surprisingly, it was found that in the presence of alkyl compound and fluorine compounds, by heating while than certain Certain condition more slowly adds thiophosgene, and purpose thing trifluoromethyl alkylthio compound can be obtained in high yield.Based on this Technological thought completes the present invention.

That is, the present invention solves above-mentioned problem by providing the technical scheme described in the item of following [1]~[15].

[1] manufacture method of the trifluoromethyl alkylthio compound represented by following formulas (1), it is characterised in that In the presence of the compound and fluorine compounds that are represented by following formulas (2), addition temperature more than 45 DEG C and with 0.25 hour Addition time addition thiophosgene above,

Formula (1)：

[changing 1]

(in formula, R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀ Alkenyl, replaced or unsubstituted C by R1₂~C₁₀Alkynyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl carbonyl epoxide, replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryl, Replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryloxy group or by one or two The R2 substitutions of above identical or different or unsubstituted C₆~C₁₀Aryl (C₁~C₄) alkoxy,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl oxycarbonyl Base epoxide, replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryl, by one or two Identical or different R2 substitutions or unsubstituted C more than individual₆~C₁₀Aryloxy group or by the identical of one or more Or different R2 substitutions or unsubstituted C₆~C₁₀Aryl (C₁~C₄) alkoxy,

R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl, C₁~C₄Haloalkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl halide Epoxide, C₁~C₄Halogenated alkylthio or C₁~C₄Alkylsulfinyl.)

Formula (2)：

[changing 2]

(in formula, R as defined in above-mentioned formula (1),

L represents halogen atom, C₁~C₄Alkylsulfonyloxy, C₁~C₄Haloalkylsulfonyloxy or with or without The C of substituent₆~C₁₀Aryl-sulfonyl oxygen.).

[2] manufacture method of the trifluoromethyl alkylthio compound as described in [1], sulphur light is added with following conditions Gas.

The addition time (h) × (addition temperature (DEG C) -45)≤10

[3] manufacture method of the trifluoromethyl alkylthio compound as described in [1] or [2], wherein, relative to 1 mole The compound represented by above-mentioned formula (2), the adding speed of thiophosgene is less than 10 mols/hr.

[4] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[3], wherein, below The condition addition thiophosgene stated.

1≤above-mentioned adding speed (mol/hr) × (above-mentioned)≤400 of addition temperature (DEG C) -45

[5] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[4], wherein, fluorination Compound is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, magnesium fluoride, calcirm-fluoride or theirs is mixed Compound.

[6] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[4], wherein, fluorination Compound is Methanaminium, N,N,N-trimethyl-, fluoride, potassium fluoride, cesium fluoride or their mixture.

[7] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[6], wherein, relatively In 1.0 moles of compounds represented by above-mentioned formula (2), closed using the fluorination of less than more than 3.0 moles 12.0 moles of scopes Thing.

[8] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[6], wherein, relatively In 1.0 moles of compounds represented by above-mentioned formula (2), closed using the fluorination of less than more than 4.0 moles 9.0 moles of scopes Thing.

[9] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[8], wherein, relatively In 1.0 moles of compounds represented by above-mentioned formula (2), the thiophosgene of less than more than 1.0 moles 3.0 moles of scope is used.

[10] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[8], wherein, phase For 1.0 moles of compounds represented by above-mentioned formula (2), the sulphur light of less than more than 1.0 moles 2.0 moles of scope is used Gas.

[11] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[10], wherein, should Method is implementation in less than more than 60 DEG C 100 DEG C of scope in temperature.

[12] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[10], wherein, should Method is implementation in less than more than 70 DEG C 90 DEG C of scope in temperature.

[13] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[12], wherein, In above-mentioned formula (1) and above-mentioned formula (2),

R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀Alkenyl, quilt R1 replaces or unsubstituted C₂~C₁₀Alkynyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkane Base carbonyl epoxide, by one or more identical or different R2 replace or unsubstituted phenyl, by one or two More than identical or different R2 substitutions or unsubstituted phenoxy group or by the identical or different of one or more R2 replaces or unsubstituted benzyloxy,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl oxycarbonyl Base epoxide, by one or more identical or different R2 replace or unsubstituted phenyl, by one or more Identical or different R2 substitutions or unsubstituted phenoxy group or taken by one or more identical or different R2 Generation or unsubstituted benzyloxy,

R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl, C₁~C₄Haloalkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl halide Epoxide, C₁~C₄Halogenated alkylthio or C₁~C₄Alkylsulfinyl,

L is by halogen atom, C₁~C₄Alkylsulfonyloxy, C₁~C₄Haloalkylsulfonyloxy or with or without taking Dai Ji phenylsulfonyloxy is represented.

[14] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[12], wherein, In above-mentioned formula (1) and above-mentioned formula (2),

R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀Alkenyl, quilt R1 replaces or unsubstituted C₂~C₁₀Alkynyl, replaced or unsubstituted by one or more identical or different R2 Phenyl or replaced or unsubstituted benzyloxy by one or more identical or different R2,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl carbonyl epoxide, by one or More than two identical or different R2 substitutions or unsubstituted phenyl, the identical or different R2 by one or more Substitution or is replaced or unsubstituted benzyl unsubstituted phenoxy group by one or more identical or different R2 Epoxide,

R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl, C₁~C₄Halogenated alkylthio or C₁~C₄Haloalkyl sulfenyl Base,

L is represented by halogen atom.

[15] manufacture method of the trifluoromethyl alkylthio compound as any one of [1]~[12], wherein, on State in formula (1) and above-mentioned formula (2),

R represents 4- Acetoxybutyls, 3- ethoxycarbonyl propyls, 4- [2,4- dimethyl -5- (2,2,2- trifluoro second sulphur Base) phenoxy group] butyl, 4- [2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenoxy group] butyl, n-hexyl, just Decyl, phenyl, benzyloxy, 8- nonenyls, 1- hexin bases, 3- methoxy-propyls, 3- [the fluoro- 5- of the chloro- 2- of 4- (2,2,2- trifluoro second Sulfenyl) phenoxy group] propyl group or 3- acetyloxypropyls,

L is represented by bromine atoms or iodine atom.

The effect of invention

In accordance with the invention it is possible to using the low alkyl compound of reactivity as initiation material, to obtain fluoroform in high yield Base alkylthio compound.

Embodiment

1. illustrated for the symbol and term described in this specification.

Halogen atom refers to fluorine atom, chlorine atom, bromine atoms or iodine atom.

C₁~C₃Etc the statement based on the symbol of element and index number represent that first prime number of then described group is Scope represented by index number.For example, representing that carbon number is 1~3 in this case.C₁~C₆Statement represent carbon atom Number is 1~6, C₁~C₁₂Statement represent carbon number be 1~12.

C₁~C₁₀Alkyl represents the straight chain that carbon number is 1~10 or the alkyl of branch-like.It is used as C₁~C₁₀Alkyl, for example Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, 1- methyl fourths can be enumerated Base, 2- methyl butyls, isopentyl, 1- ethyl propyls, 1,1- dimethyl propyls, neopentyl, 1,2- dimethyl propyls, n-hexyl, 1- methyl amyls, 2- methyl amyls, 3- methyl amyls, isohesyl, 1- ethyl-butyls, 2- ethyl-butyls, 3,3- dimethylbutyls, 1,3- dimethylbutyls, 1,1,2- thmethylpropyls, 1,2,2- thmethylpropyls, 1- ethyl -1- methyl-propyls, 1- ethyls -2- Methyl-propyl, n-heptyl, 1- methylhexyls, 2- methylhexyls, 3- methylhexyls, 4- methylhexyls, different heptyl, 1- ethyls penta Base, 2- ethyl pentyl groups, 3- ethyl pentyl groups, 1,1- dimethyl amyl groups, 1,4- dimethyl amyl groups, 1- butyls, 1,1,3- front threes Base butyl, 1,3,3- trimethyl butyls, 2,2,3- trimethyl butyls, 2,3,3- trimethyl butyls, 1,1,2,2- tetramethyls propyl group, N-octyl, 1- methylheptyls, 2- methylheptyls, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, iso-octyl, 1- ethyl hexyls Base, 2- ethylhexyls, 3- ethylhexyls, 4- ethylhexyls, 1,1- dimethylhexanyls, 5,5- dimethylhexanyls, 1,5- dimethyl Hexyl, 1- propylpentyls, 2- propylpentyls, 2,4,4- tri-methyl-amyls, 1- ethyl -1- methyl amyls, n-nonyl, 1- methyl are pungent Base, 2- Methyl Octyls, 3- Methyl Octyls, 4- Methyl Octyls, 5- Methyl Octyls, 6- Methyl Octyls, isononyl, 1- ethylheptyls, 2- ethylheptyls, 3- ethylheptyls, 4- ethylheptyls, 5- ethylheptyls, 1,1- dimethyl heptyl, 1,2- dimethyl heptyl, 2, 6- dimethyl heptyl, 1- propyl group hexyl, 2- propyl group hexyl, 3- propyl group hexyl, 1,1,5- trimethyls, 1,3,5- trimethyls oneself Base, 3,5,5- trimethyls, 1- ethyl -1- methylhexyls, 1- butyl amyl group, positive decyl, 1- Nonyls, 2- methyl nonyls Base, 3- Nonyls, 4- Nonyls, 5- Nonyls, 6- Nonyls, 7- Nonyls, isodecyl, 1- ethyloctanyls, 2- ethyloctanyls, 3- ethyloctanyls, 4- ethyloctanyls, 5- ethyloctanyls, 6- ethyloctanyls, 3,3- dimethyl octyl group, 3,7- bis- Methyl Octyl, 1- propylheptyls, 2- propylheptyls, 3- propylheptyls, 1,1,5- trimethyls heptyl, 2,2,6- trimethyls heptyl, 2,4,6- trimethyl heptyl, 4,6,6- trimethyl heptyl, 1- ethyl -1- methylheptyls, 1- butyl hexyl, 2- butyl hexyls etc., But it is not limited to these.

It is used as preferred C₁~C₁₀Alkyl, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, the tert-butyl group, n-pentyl, 1- methyl butyls, 2- methyl butyls, isopentyl, 1- ethyl propyls, 1,2- dimethyl propyls, just oneself Base, 1- methyl amyls, 2- methyl amyls, 3- methyl amyls, isohesyl, 1- ethyl-butyls, 2- ethyl-butyls, 1,3- dimethyl butyrates Base, 1- Ethyl-2-Methyls propyl group, n-heptyl, 1- methylhexyls, 2- methylhexyls, 3- methylhexyls, 4- methylhexyls, different heptan Base, 1- ethyl pentyl groups, 2- ethyl pentyl groups, 3- ethyl pentyl groups, 1,4- dimethyl amyl groups, 1- butyls, n-octyl, 1- methyl heptan Base, 2- methylheptyls, 3- methylheptyls, 4- methylheptyls, 5- methylheptyls, iso-octyl, 1- ethylhexyls, 2- ethylhexyls, 3- ethylhexyls, 4- ethylhexyls, 1- propylpentyls, 2- propylpentyls, n-nonyl, 1- Methyl Octyls, 2- Methyl Octyls, 3- first Base octyl group, 4- Methyl Octyls, 5- Methyl Octyls, 6- Methyl Octyls, isononyl, 1- ethylheptyls, 2- ethylheptyls, 3- ethyls heptan Base, 4- ethylheptyls, 5- ethylheptyls, 1,2- dimethyl heptyl, 2,6- dimethyl heptyl, 1- propyl group hexyl, 2- propyl group hexyl, 3- propyl group hexyl, 1- butyl amyl group, positive decyl, 1- Nonyls, 2- Nonyls, 3- Nonyls, 4- Nonyls, 5- first Base nonyl, 6- Nonyls, 7- Nonyls, isodecyl, 1- ethyloctanyls, 2- ethyloctanyls, 3- ethyloctanyls, 4- ethyls are pungent Base, 5- ethyloctanyls, 6- ethyloctanyls, 3,7- dimethyl octyl group, 1- propylheptyls, 2- propylheptyls, 3- propylheptyls, 2,4, 6- trimethyls heptyl, 1- butyl hexyl, 2- butyl hexyls.Among them, can more preferably enumerate methyl, ethyl, n-propyl, Normal-butyl, sec-butyl, n-pentyl, 1- methyl butyls, 1- ethyl propyls, 1,1- dimethyl propyls, n-hexyl, 1- methyl amyls, N-heptyl, 1- methylhexyls, n-octyl, 1- methylheptyls, n-nonyl, 1- Methyl Octyls, positive decyl, 1- Nonyls etc..

C₂~C₁₀Alkenyl represents the straight chain that carbon number is 2~10 or the alkenyl of branch-like.It is used as C₂~C₁₀Alkenyl, for example Vinyl, 1- acrylic, 2- acrylic, isopropenyl, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1,3- fourths two can be enumerated Alkenyl, 1- methyl-1-propylenes base, 1- methyl -2- acrylic, 2- methyl-1-propylenes base, 2- methyl -2- acrylic, 1- amylenes Base, 2- pentenyls, 3- pentenyls, 4- pentenyls, 1,3- pentadienyls, 2,4- pentadienyls, 1- methyl isophthalic acids-cyclobutenyl, 1- first Base -2- cyclobutenyls, 1- methyl -3- cyclobutenyls, 2-methyl-1-butene alkenyl, 2- methyl-2-butenes base, 2- methyl -3- cyclobutenyls, 3-methyl-1-butene base, 3- methyl-2-butenes base, 3- methyl -3- cyclobutenyls, 1,1- dimethyl -2- acrylic, 1,2- diformazans Base -2- acrylic, 1,2- dimethyl -1- acrylic, 1- ethyl -2- acrylic, 1- vinyl -2- acrylic, 1- hexenyls, 2- Hexenyl, 3- hexenyls, 4- hexenyls, 5- hexenyls, 1,3- hexadienyls, 1,4- hexadienyls, 1,5- hexadienyls, 2,4- Hexadienyl, 2,5- hexadienyls, 3,5- hexadienyls, 1,3,5- hexatrienes base, 1- methyl-1-pentenes alkenyl, 1- methyl -2- penta Alkenyl, 1- methyl-3-pentenyls, 1- methyl -4- pentenyls, 1- methyl -5- pentenyls, 2- methyl-1-pentenes alkenyl, 2- methyl - 2- pentenyls, 2- methyl-3-pentenyls, 2- methyl -4- pentenyls, 2- methyl -5- pentenyls, 3- methyl-1-pentenes alkenyl, 3- first Base -2- pentenyls, 3- methyl-3-pentenyls, 3- methyl -4- pentenyls, 3- methyl -5- pentenyls, 4-methyl-1-pentene base, 4- methyl -2- pentenyls, 4- methyl-3-pentenyls, 4- methyl -4- pentenyls, 4- methyl -5- pentenyls, 1- ethyl -1- butylene Base, 1- ethyl -2- cyclobutenyls, 1- ethyl -3- cyclobutenyls, 2- ethyl -1- cyclobutenyls, 2- ethyl -2- cyclobutenyls, 2- ethyls -3- Cyclobutenyl, 1,1- dimethyl -2- cyclobutenyls, 1,1- dimethyl -3- cyclobutenyls, 2,2- dimethyl -3- cyclobutenyls, 3,3- diformazans Base -1- cyclobutenyls, 1,2- dimethyl -1- cyclobutenyls, 1,2- dimethyl -2- cyclobutenyls, 1,2- dimethyl -3- cyclobutenyls, 1,3- Dimethyl -1- cyclobutenyls, 1,3- dimethyl -2- cyclobutenyls, 1,3- dimethyl -3- cyclobutenyls, 1,1,2- trimethyl -2- propylene Base, 1- heptenyls, 2- heptenyls, 3- heptenyls, 4- heptenyls, 5- heptenyls, 6- heptenyls, 1,3- heptadiene base, 1,4- heptan Dialkylene, 1,5- heptadiene base, 1,6- heptadiene base, 2,4- heptadiene base, 2,5- heptadiene base, 2,6- heptadiene base, 3,5- Heptadiene base, 3,6- heptadiene base, 1,3,5- heptantrienes base, 1,3,6- heptantrienes base, 2,4,6- heptantrienes base, 1- octenyls, 2- octenyls, 3- octenyls, 4- octenyls, 5- octenyls, 6- octenyls, 7- octenyls, 1,3- octadienyls, 1,4- octadienes Base, 1,5- octadienyls, 1,6- octadienyls, 1,7- octadienyls, 2,4- octadienyls, 2,5- octadienyls, 2,6- pungent two Alkenyl, 2,7- octadienyls, 3,5- octadienyls, 3,6- octadienyls, 3,7- octadienyls, 1,3,5- sarohornenes base, 1,3, 6- sarohornenes base, 1,3,7- sarohornenes base, 2,4,6- sarohornenes base, 2,4,7- sarohornenes base, 1,3,5,7- octatetraenes base, 1- nonyls Alkenyl, 2- nonenyls, 3- nonenyls, 4- nonenyls, 5- nonenyls, 6- nonenyls, 7- nonenyls, 8- nonenyls, 1,3- nonyls two Alkenyl, 1,4- nonadienes base, 1,5- nonadienes base, 1,6- nonadienes base, 1,7- nonadienes base, 1,8- nonadienes base, 2,4- nonyls Dialkylene, 2,5- nonadienes base, 2,6- nonadienes base, 2,7- nonadienes base, 2,8- nonadienes base, 3,5- nonadienes base, 3,6- Nonadiene base, 3,7- nonadienes base, 3,8- nonadienes base, 1,3,5- nonyls trialkenyl, 1,3,6- nonyls trialkenyl, 1,3,7- nonyl triolefins Base, 1,3,8- nonyls trialkenyl, 2,4,6- nonyls trialkenyl, 2,4,7- nonyls trialkenyl, 2,4,8- nonyls trialkenyl, 1,3,5,7- nonyl tetraenes Base, 1,3,5,8- nonyls apos, 2,4,6,8- nonyls apos, 1- decene base, 2- decene base, 3- decene base, 4- decene base, the 5- last of the ten Heavenly stems Alkenyl, 6- decene base, 7- decene base, 8- decene base, 9- decene base, 1,3- decadinene base, 1,4- decadinene base, 1,5- decadinene Base, 1,6- decadinene base, 1,7- decadinene base, 1,8- decadinene base, 1,9- decadinene base, 2,4- decadinene base, the 2,5- last of the ten Heavenly stems two Alkenyl, 2,6- decadinene base, 2,7- decadinene base, 2,8- decadinene base, 2,9- decadinene base, 3,5- decadinene base, the 3,6- last of the ten Heavenly stems Dialkylene, 3,7- decadinene base, 3,8- decadinene base, 3,9- decadinene base, 1,3,5- last of the ten Heavenly stems trialkenyl, 1,3,6- last of the ten Heavenly stems trialkenyl, 1,3,7- last of the ten Heavenly stems trialkenyl, 1,3,8- last of the ten Heavenly stems trialkenyl, 1,3,9- last of the ten Heavenly stems trialkenyl, 2,4,6- last of the ten Heavenly stems trialkenyl, 2,4,7- last of the ten Heavenly stems trialkenyl, 2, 4,8- last of the ten Heavenly stems trialkenyl, 2,4,9- last of the ten Heavenly stems trialkenyl, 1,3,5,7- decatetraenes base, 1,3,5,8- decatetraenes base, 1,3,5,9- decatetraenes Base, 2,4,6,8- decatetraene bases, 2,4,6,9- decatetraene bases, the alkenyl of 1,3,5, the 7-9- last of the ten Heavenly stems five etc., but it is not limited to these.

It is used as preferred C₂~C₁₀Alkenyl, for example, can enumerate vinyl, 1- acrylic, 2- acrylic, isopropenyl, 1- Cyclobutenyl, 2- cyclobutenyls, 3- cyclobutenyls, 1,3- butadienyls, 1- pentenyls, 2- pentenyls, 3- pentenyls, 4- pentenyls, 1, 3- pentadienyls, 2,4- pentadienyls, 1- hexenyls, 2- hexenyls, 3- hexenyls, 4- hexenyls, 5- hexenyls, 1,3- oneself two Alkenyl, 1,4- hexadienyls, 1,5- hexadienyls, 2,4- hexadienyls, 2,5- hexadienyls, 3,5- hexadienyls, 1,3,5- Hexatriene base, 1- heptenyls, 2- heptenyls, 3- heptenyls, 4- heptenyls, 5- heptenyls, 6- heptenyls, 1,3- heptadiene base, 1,4- heptadiene base, 1,5- heptadiene base, 1,6- heptadiene base, 2,4- heptadiene base, 2,5- heptadiene base, 2,6- heptadiene Base, 3,5- heptadiene base, 3,6- heptadiene base, 1,3,5- heptantrienes base, 1,3,6- heptantrienes base, 2,4,6- heptantrienes base, 1- Octenyl, 2- octenyls, 3- octenyls, 4- octenyls, 5- octenyls, 6- octenyls, 7- octenyls, 1,3- octadienyls, 1, 4- octadienyls, 1,5- octadienyls, 1,6- octadienyls, 1,7- octadienyls, 2,4- octadienyls, 2,5- octadienyls, 2,6- octadienyls, 2,7- octadienyls, 3,5- octadienyls, 3,6- octadienyls, 3,7- octadienyls, 1,3,5- sarohornenes Base, 1,3,6- sarohornenes base, 1,3,7- sarohornenes base, 2,4,6- sarohornenes base, 2,4,7- sarohornenes base, 1,3,5,7- octatetraenes Base, 1- nonenyls, 2- nonenyls, 3- nonenyls, 4- nonenyls, 5- nonenyls, 6- nonenyls, 7- nonenyls, 8- nonenyls, 1, 3- nonadienes base, 1,4- nonadienes base, 1,5- nonadienes base, 1,6- nonadienes base, 1,7- nonadienes base, 1,8- nonadienes base, 2,4- nonadienes base, 2,5- nonadienes base, 2,6- nonadienes base, 2,7- nonadienes base, 2,8- nonadienes base, 3,5- nonadienes Base, 3,6- nonadienes base, 3,7- nonadienes base, 3,8- nonadienes base, 1,3,5- nonyls trialkenyl, 1,3,6- nonyls trialkenyl, 1,3, 7- nonyls trialkenyl, 1,3,8- nonyls trialkenyl, 2,4,6- nonyls trialkenyl, 2,4,7- nonyls trialkenyl, 2,4,8- nonyls trialkenyl, 1,3,5, 7- nonyls apos, 1,3,5,8- nonyls apos, 2,4,6,8- nonyls apos, 1- decene base, 2- decene base, 3- decene base, the 4- last of the ten Heavenly stems Alkenyl, 5- decene base, 6- decene base, 7- decene base, 8- decene base, 9- decene base, 1,3- decadinene base, 1,4- decadinene base, 1,5- decadinene base, 1,6- decadinene base, 1,7- decadinene base, 1,8- decadinene base, 1,9- decadinene base, 2,4- decadinene Base, 2,5- decadinene base, 2,6- decadinene base, 2,7- decadinene base, 2,8- decadinene base, 2,9- decadinene base, the 3,5- last of the ten Heavenly stems two Alkenyl, 3,6- decadinene base, 3,7- decadinene base, 3,8- decadinene base, 3,9- decadinene base, 1,3,5- last of the ten Heavenly stems trialkenyl, 1,3, 6- last of the ten Heavenly stems trialkenyl, 1,3,7- last of the ten Heavenly stems trialkenyl, 1,3,8- last of the ten Heavenly stems trialkenyl, 1,3,9- last of the ten Heavenly stems trialkenyl, 2,4,6- last of the ten Heavenly stems trialkenyl, 2,4,7- Last of the ten Heavenly stems trialkenyl, 2,4,8- last of the ten Heavenly stems trialkenyl, 2,4,9- last of the ten Heavenly stems trialkenyl, 1,3,5,7- decatetraenes base, 1,3,5,8- decatetraenes base, 1,3, 5,9- decatetraenes base, 2,4,6,8- decatetraenes base, 2,4,6,9- decatetraenes base, the alkenyl of the 1,3,5,7-9- last of the ten Heavenly stems five.Among them, more Preferred vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1- pentenyls, 2- pentenyls, 3- Pentenyl, 4- pentenyls, 1- hexenyls, 2- hexenyls, 3- hexenyls, 4- hexenyls, 5- hexenyls, 1- heptenyls, 2- heptene Base, 3- heptenyls, 4- heptenyls, 5- heptenyls, 6- heptenyls, 1- octenyls, 2- octenyls, 3- octenyls, 4- octenyls, 5- Octenyl, 6- octenyls, 7- octenyls, 1- nonenyls, 2- nonenyls, 3- nonenyls, 4- nonenyls, 5- nonenyls, 6- nonenes Base, 7- nonenyls, 8- nonenyls, 1- decene base, 2- decene base, 3- decene base, 4- decene base, 5- decene base, 6- decene base, 7- Decene base, 8- decene base, 9- decene bases etc..

C₂~C₁₀Alkynyl represents the straight chain that carbon number is 2~10 or the alkynyl of branch-like.It is used as C₂~C₁₀Alkynyl, for example Acetenyl, 1- propinyls, 2-propynyl, 1- butynyls, 2- butynyls, 3- butynyls, 1,3- diacetylene base, 1- first can be enumerated Base -2-propynyl, 1- pentynyls, valerylene base, 3- pentynyls, 4- pentynyls, 1,3- pentadiines base, 3- methyl isophthalic acids-butynyl, 1- methyl -2- butynyls, 1- methyl -3- butynyls, 2- methyl -3- butynyls, 1- ethyls -2-propynyl, 1,1- dimethyl -2- Propinyl, 1- hexin bases, 2- hexin bases, 3- hexin bases, 4- hexin bases, 5- hexin bases, 1,3- adipic alkynyls, 2,4- hexadiines Oneself three alkynyls, 3- methyl-1-pentenes alkynyl, 4- methyl-1-pentenes alkynyl, 1- methyl-valerylene of base, 3,5- adipic alkynyls, 1,3,5- Base, 4- methyl-valerylene base, 1- methyl -3- pentynyls, 2- methyl -3- pentynyls, 1- methyl -4- pentynyls, 2- methyl -4- Pentynyl, 3- methyl -4- pentynyls, 3,3- dimethyl -1- butynyls, 1,1- dimethyl -2- butynyls, 1- ethyl -2- butine Base, 1,1- dimethyl -3- butynyls, 2,2- dimethyl -3- butynyls, 1,2- dimethyl -3- butynyls, 1- ethyl -3- butine Base, 2- ethyl -3- butynyls, 1- (n-propyl) -2-propynyl, 1- (isopropyl) -2-propynyl, 1- ethyl -1- methyl -2- third Alkynyl, 1- heptynyls, 2- heptynyls, 3- heptynyls, 4- heptynyls, 5- heptynyls, 6- heptynyls, 1,3- heptadiynes base, 1,6- Heptadiyne base, alkynyl in 1,3,5- heptan three, alkynyl in 2,4,6- heptan three, 3- methyl isophthalic acids-hexin base, 4- methyl isophthalic acids-hexin base, 5- first Base -1- hexin bases, 1- methyl -2- hexin bases, 4- methyl -2- hexin bases, 5- methyl -2- hexin bases, 1- methyl -3- hexin bases, 2- methyl -3- hexin bases, 5- methyl -3- hexin bases, 1- methyl -4- hexin bases, 2- methyl -4- hexin bases, 3- methyl -4- hexins Base, 1- methyl -5- hexin bases, 2- methyl -5- hexin bases, 3- methyl -5- hexin bases, 4- methyl -5- hexin bases, 3,3- diformazans Base -1- pentynyls, 4,4- dimethyl -1- pentynyls, 3,4- dimethyl -1- pentynyls, 3- ethyl -1- pentynyls, 1,1- diformazans Base-valerylene base, 4,4- dimethyl-valerylene base, 1,4- dimethyl-valerylene base, 1- ethyls-valerylene base, 1,1- diformazans Base -3- pentynyls, 2,2- dimethyl -3- pentynyls, 1,2- dimethyl -3- pentynyls, 1- ethyl -3- amyl groups, 2- ethyls -3- penta Alkynyl, 1,1- dimethyl -4- pentynyls, 2,2- dimethyl -4- pentynyls, 3,3- dimethyl -4- pentynyls, 1- ethyls -4- penta Alkynyl, 2- ethyl -4- pentynyls, 3- ethyl -4- pentynyls, 1- (n-propyl) -1- methyl -2-propynyl, 1- (isopropyl) -1- Methyl -2-propynyl, 1,1- diethyl -2-propynyl, 1- (normal-butyl) -2-propynyl, 1- octynyls, 2- octynyls, 3- are pungent Alkynyl, 4- octynyls, 5- octynyls, 6- octynyls, 7- octynyls, the pungent diynyls of 1,3-, the pungent diynyls of 1,7-, 1,3,5- pungent three Pungent four alkynyl of alkynyl, 1,3,5,7-, 3- methyl isophthalic acids-heptynyl, 4- methyl isophthalic acids-heptynyl, 5- methyl isophthalic acids-heptynyl, 6- methyl- 1- heptynyls, 1- methyl -2- heptynyls, 4- methyl -2- heptynyls, 5- methyl -2- heptynyls, 6- methyl -2- heptynyls, 1- first Base -3- heptynyls, 2- methyl -3- heptynyls, 5- methyl -3- heptynyls, 6- methyl -3- heptynyls, 1- methyl -4- heptynyls, 2- methyl -4- heptynyls, 3- methyl -4- heptynyls, 6- methyl -4- heptynyls, 1- methyl -5- heptynyls, 2- methyl -5- heptyne Base, 3- methyl -5- heptynyls, 4- methyl -5- heptynyls, 1- methyl -6- heptynyls, 2- methyl -6- heptynyls, 3- methyl -6- Heptynyl, 4- methyl -6- heptynyls, 5- methyl -6- heptynyls, 1- n-heptylacetylenes base, 2- n-heptylacetylenes base, 3- n-heptylacetylenes base, 4- n-heptylacetylenes base, 5- N-heptylacetylene base, 6- n-heptylacetylenes base, 7- n-heptylacetylenes base, 8- n-heptylacetylenes base, 2,4- nonyls diynyl, 3- methyl isophthalic acids-octynyl, 4- methyl isophthalic acids-octyne Base, 5- methyl isophthalic acids-octynyl, 6- methyl isophthalic acids-octynyl, 7- methyl isophthalic acids-octynyl, 1- methyl -2- octynyls, 4- methyl -2- Octynyl, 5- methyl -2- octynyls, 6- methyl -2- octynyls, 7- methyl -2- octynyls, 1- methyl -3- octynyls, 2- first Base -3- octynyls, 5- methyl -3- octynyls, 6- methyl -3- octynyls, 7- methyl -3- octynyls, 1- methyl -4- octynyls, 2- methyl -4- octynyls, 3- methyl -4- octynyls, 6- methyl -4- octynyls, 7- methyl -4- octynyls, 1- methyl -5- octynes Base, 2- methyl -5- octynyls, 3- methyl -5- octynyls, 4- methyl -5- octynyls, 7- methyl -5- octynyls, 1- methyl -6- Octynyl, 2- methyl -6- octynyls, 3- methyl -6- octynyls, 4- methyl -6- octynyls, 5- methyl -6- octynyls, 1- first Base -7- octynyls, 2- methyl -7- octynyls, 3- methyl -7- octynyls, 4- methyl -7- octynyls, 5- methyl -7- octynyls, 6- methyl -7- octynyls, 1- decynyls, 2- decynyls, 3- decynyls, 4- decynyls, 5- decynyls, 6- decynyls, 7- decine Base, 8- decynyls, 9- decynyls, 1,3- last of the ten Heavenly stems diynyl, 1,7- last of the ten Heavenly stems diynyl, 3- methyl isophthalic acids-n-heptylacetylene base, 4- methyl isophthalic acids-n-heptylacetylene Base, 5- methyl isophthalic acids-n-heptylacetylene base, 6- methyl isophthalic acids-n-heptylacetylene base, 7- methyl isophthalic acids-n-heptylacetylene base, 8- methyl isophthalic acids-n-heptylacetylene base, 1- methyl -2- N-heptylacetylene base, 4- methyl -2- n-heptylacetylenes base, 5- methyl -2- n-heptylacetylenes base, 6- methyl -2- n-heptylacetylenes base, 7- methyl -2- n-heptylacetylenes base, 8- first Base -2- n-heptylacetylenes base, 1- methyl -3- n-heptylacetylenes base, 2- methyl -3- n-heptylacetylenes base, 5- methyl -3- n-heptylacetylenes base, 6- methyl -3- n-heptylacetylenes base, 7- methyl -3- n-heptylacetylenes base, 8- methyl -3- n-heptylacetylenes base, 1- methyl -4- n-heptylacetylenes base, 2- methyl -4- n-heptylacetylenes base, 3- methyl -4- n-heptylacetylenes Base, 6- methyl -4- n-heptylacetylenes base, 7- methyl -4- n-heptylacetylenes base, 8- methyl -4- n-heptylacetylenes base, 1- methyl -5- n-heptylacetylenes base, 2- methyl -5- N-heptylacetylene base, 3- methyl -5- n-heptylacetylenes base, 4- methyl -5- n-heptylacetylenes base, 7- methyl -5- n-heptylacetylenes base, 8- methyl -5- n-heptylacetylenes base, 1- first Base -6- n-heptylacetylenes base, 2- methyl -6- n-heptylacetylenes base, 3- methyl -6- n-heptylacetylenes base, 4- methyl -6- n-heptylacetylenes base, 5- methyl -6- n-heptylacetylenes base, 8- methyl -6- n-heptylacetylenes base, 1- methyl -7- n-heptylacetylenes base, 2- methyl -7- n-heptylacetylenes base, 3- methyl -7- n-heptylacetylenes base, 4- methyl -7- n-heptylacetylenes Base, 5- methyl -7- n-heptylacetylenes base, 6- methyl -7- n-heptylacetylenes base, 1- methyl -8- n-heptylacetylenes base, 2- methyl -8- n-heptylacetylenes base, 3- methyl -8- N-heptylacetylene base, 4- methyl -8- n-heptylacetylenes base, 5- methyl -8- n-heptylacetylenes base, 6- methyl -8- n-heptylacetylenes base, 7- methyl -8- n-heptylacetylene bases etc., but simultaneously It is not limited to these.

It is used as preferred C₂~C₁₀Alkynyl, for example, can enumerate acetenyl, 1- propinyls, 2-propynyl, 1- butynyls, 2- Butynyl, 3- butynyls, 1,3- diacetylene base, 1- methyl -2-propynyl, 1- pentynyls, valerylene base, 3- pentynyls, 4- penta Alkynyl, 1,3- pentadiines base, 3- methyl isophthalic acids-butynyl, 1- methyl -2- butynyls, 1- methyl -3- butynyls, 2- methyl -3- fourths Alkynyl, 1- ethyls -2-propynyl, 1,1- dimethyl -2-propynyl, 1- hexin bases, 2- hexin bases, 3- hexin bases, 4- hexin bases, Oneself three alkynyls, 3- methyl-1-pentene alkynes of 5- hexin bases, 1,3- adipic alkynyls, 2,4- adipic alkynyls, 3,5- adipic alkynyls, 1,3,5- Base, 4- methyl-1-pentenes alkynyl, 1- methyl-valerylene base, 4- methyl-valerylene base, 1- methyl -3- pentynyls, 2- methyl -3- Pentynyl, 1- methyl -4- pentynyls, 2- methyl -4- pentynyls, 3- methyl -4- pentynyls, 3,3- dimethyl -1- butynyls, 1, 1- dimethyl -2- butynyls, 1- ethyl -2- butynyls, 1,1- dimethyl -3- butynyls, 2,2- dimethyl -3- butynyls, 1, 2- dimethyl -3- butynyls, 1- ethyl -3- butynyls, 2- ethyl -3- butynyls, 1- (n-propyl) -2-propynyl, 1- (isopropyls Base) -2-propynyl, 1- ethyls -1- methyl -2-propynyl, 1- heptynyls, 2- heptynyls, 3- heptynyls, 4- heptynyls, 5- heptan Alkynyl, 6- heptynyls, 1,3- heptadiynes base, 1,6- heptadiynes base, alkynyl in 1,3,5- heptan three, alkynyl in 2,4,6- heptan three, 1- octynes Base, 2- octynyls, 3- octynyls, 4- octynyls, 5- octynyls, 6- octynyls, 7- octynyls, the pungent diynyls of 1,3-, 1,7- are pungent Pungent three alkynyl of diynyl, 1,3,5-, pungent four alkynyls of 1,3,5,7-, 1- n-heptylacetylenes base, 2- n-heptylacetylenes base, 3- n-heptylacetylenes base, 4- n-heptylacetylenes base, 5- N-heptylacetylene base, 6- n-heptylacetylenes base, 7- n-heptylacetylenes base, 8- n-heptylacetylenes base, 2,4- nonyls diynyl, 1- decynyls, 2- decynyls, 3- decynyls, 4- Decynyl, 5- decynyls, 6- decynyls, 7- decynyls, 8- decynyls, 9- decynyls, 1,3- last of the ten Heavenly stems diynyl, 1,7- last of the ten Heavenly stems diines Base.Among them, acetenyl, 1- propinyls, 2-propynyl, 1- butynyls, 2- butynyls, 3- butine can be more preferably enumerated Base, 1- pentynyls, valerylene base, 3- pentynyls, 4- pentynyls, 1- hexin bases, 2- hexin bases, 3- hexin bases, 4- hexin bases, 5- Hexin base, 1- heptynyls, 2- heptynyls, 3- heptynyls, 4- heptynyls, 5- heptynyls, 6- heptynyls, 1- octynyls, 2- octynes Base, 3- octynyls, 4- octynyls, 5- octynyls, 6- octynyls, 7- octynyls, 1- n-heptylacetylenes base, 2- n-heptylacetylenes base, 3- n-heptylacetylenes base, 4- N-heptylacetylene base, 5- n-heptylacetylenes base, 6- n-heptylacetylenes base, 7- n-heptylacetylenes base, 8- n-heptylacetylenes base, 1- decynyls, 2- decynyls, 3- decynyls, 4- decine Base, 5- decynyls, 6- decynyls, 7- decynyls, 8- decynyls, 9- decynyls etc..

C₁~C₄Alkyl represents the straight chain that carbon number is 1~4 or the alkyl of branch-like.It is used as C₁~C₄Alkyl, for example may be used To enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl group etc..

It is used as preferred C₁~C₄Alkyl, for example, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group Deng.

C₁~C₄Alcoxyl basis representation carbon number is 1~4 straight chain or the alkoxy of branch-like.It is used as C₁~C₄Alkoxy, Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tertiary fourth oxygen can for example be enumerated Base etc..

It is used as preferred C₁~C₄Alkoxy, such as can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy.

C₁~C₄Alkyl-carbonyl represent moieties have the carbon number of above-mentioned implication for 1~4 (alkyl)-C (=O)- Base.It is used as C₁~C₄Alkyl-carbonyl, for example, can enumerate methyl carbonyl (acetyl group), ethylcarbonyl group (propiono), n-propyl carbonyl Base, Isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl group, butylcarbonyl, tert-butyl carbonyl (valeryl) etc..

It is used as preferred C₁~C₄Alkyl-carbonyl, for example, can enumerate methyl carbonyl (acetyl group), ethylcarbonyl group (propionyl Base), n-propyl carbonyl, Isopropylcarbonyl, n-butylcarbonyl, tert-butyl carbonyl (valeryl) etc..

C₁~C₄Alkoxy carbonyl group represents (alkoxy)-C that there is alkoxy portion the carbon number of above-mentioned implication to be 1~4 (=O)-base.It is used as C₁~C₄Alkoxy carbonyl group, for example, can enumerate methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, different Propoxycarbonyl, n-butoxycarbonyl, s-butoxycarbonyl, isobutoxy carbonyl, tert-butoxycarbonyl etc..

It is used as preferred C₁~C₄Alkoxy carbonyl group, for example, can enumerate methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl Base, isopropoxy carbonyl, n-butoxycarbonyl, tert-butoxycarbonyl etc..

C₁~C₄Alkyl-carbonyl oxygen basis representation alkylcarbonyl groups have the (alkyl that the carbon number of above-mentioned implication is 1~4 Carbonyl)-O- bases.It is used as C₁~C₄Alkyl carbonyl epoxide, for example, can enumerate methyl carbonyl epoxide (acetoxyl group), ethylcarbonyl group Epoxide (propiono epoxide), n-propyl carbonyl epoxide, Isopropylcarbonyl epoxide, n-butylcarbonyl epoxide, sec-butylcarbonyl group epoxide, Butylcarbonyl epoxide, tert-butyl carbonyl epoxide (valeryl epoxide) etc..

It is used as preferred C₁~C₄Alkyl carbonyl epoxide, for example, can enumerate methyl carbonyl epoxide (acetoxyl group), ethyl carbonyl Base epoxide (propiono epoxide), n-propyl carbonyl epoxide, Isopropylcarbonyl epoxide, n-butylcarbonyl epoxide, tert-butyl carbonyl oxygen Base (valeryl epoxide) etc..

It is used as C₆~C₁₀Aryl, such as can enumerate phenyl, naphthyl.

It is used as C₆~C₁₀Aryloxy group, such as can enumerate phenoxy group, 1- naphthoxys, 2- naphthoxys.

C₆~C₁₀Aryl (C₁~C₄) alcoxyl basis representation aryl moiety and alkoxy portion have above-mentioned implication by carbon atom The alkoxy that the carbon number for the aryl substitution that number is 6~10 is 1~4.It is used as C₆~C₁₀Aryl (C₁~C₄) alkoxy, for example Benzyloxy, 1- phenyl ethoxies, 2- phenyl ethoxies, 3- phenyl-propoxies, 4- phenylbutoxies etc. can be enumerated, but is not limited In these.

It is used as preferred C₆~C₁₀Aryl (C₁~C₄) alkoxy, such as can enumerate benzyloxy, 2- phenyl ethoxies.

C₁~C₄Haloalkyl represents the straight chain that the carbon number replaced by 1~9 identical or different halogen atom is 1~4 Or the alkyl of branch-like.

It is used as C₁~C₄Haloalkyl, for example, can enumerate methyl fluoride, difluoromethyl, trifluoromethyl, chlorodifluoramethyl-, 2- Fluoro ethyl, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, the fluoro ethyls of 1,1,2,2- tetra-, pentafluoroethyl group, the chloro- 1,1,2,2- tetra- of 2- The chloro- fluoro ethyls of 1,2,2,2- tetra- of fluoro ethyl, 1-, 3- fluoropropyls, 3,3,3- trifluoro propyls, the fluoropropyls of 2,2,3,3- tetra-, 2,2,3, The fluoro- 1- trifluoromethyls ethyl of the fluoropropyls of 3,3- five, 2,2,2- tri-, heptafluoropropyl, the fluoro- 1- trifluoromethyls ethyls of 1,2,2,2- tetra-, The chloro- fluoropropyls of 1,1,2,3,3- five of 2,3- bis-, 4- fluorine butyl, 4,4,4- triRuorobutyls, the fluoro- 1- methyl-propyls of 3,3,3- tri-, 3, The fluoro- 2- methyl-propyls of 3,3- tri-, the chloro- 4,4- difluorobutyl groups of 4-, 2,2,3,3,4,4- hexafluoros butyl, 2,2,3,4,4,4- hexafluoro fourths The fluoro- 1- methyl isophthalic acids-trifluoromethyl ethyl of base, 2,2,2- tri-, the fluoro- 2- trifluoromethylpropyls of 3,3,3- tri-, 2,2,3,3,4,4,4- The fluoro- 2- trifluoromethylpropyls of seven fluorine butyl, 2,3,3,3- tetra-, 1,1,2,2,3,3,4,4- octafluoros butyl, 1,1,2,2,3,3,4, 4,4- nine fluorine butyl, the octafluoro butyl of 4- chloro- 1,1,2,2,3,3,4,4- etc., but it is not limited to these.

It is used as preferred C₁~C₄Haloalkyl, for example, can enumerate methyl fluoride, difluoromethyl, trifluoromethyl, 2- fluorine second Base, the fluoro ethyls of 2,2- bis-, 2,2,2- trifluoroethyls, the fluoro ethyls of 1,1,2,2- tetra-, pentafluoroethyl group, 3- fluoropropyls, 3,3,3- trifluoros Propyl group, the fluoropropyls of 2,2,3,3- tetra-, the fluoropropyls of 2,2,3,3,3- five, the fluoro- 1- trifluoromethyls ethyls of 2,2,2- tri-, heptafluoropropyl, The fluoro- 1- trifluoromethyls ethyls of 1,2,2,2- tetra-, 4- fluorine butyl, 4,4,4- triRuorobutyls, 2,2,3,3,4,4- hexafluoros butyl, 2,2, The fluoro- 1- methyl isophthalic acids-trifluoromethyl ethyls of 2- tri-, the fluoro- 2- trifluoromethylpropyls of 3,3,3- tri-, the fluorine fourths of 2,2,3,3,4,4,4- seven The fluoro- 2- trifluoromethylpropyls of base, 2,3,3,3- tetra-, 1,1,2,2,3,3,4,4- octafluoros butyl, 1,1,2,2,3,3,4,4,4- nine Fluorine butyl etc..

C₁~C₄Haloalkoxy basis representation haloalkyl moiety have above-mentioned implication, by 1~9 identical or different halogen The carbon number of atom substitution is 1~4 straight chain or (alkyl)-O- bases of branch-like.

It is used as C₁~C₄Halogenated alkoxy, for example, can enumerate difluoro-methoxy, chlorine difluoro-methoxy, trifluoromethoxy, 2- Fluorine ethyoxyl, 2,2- difluoroethoxies, 2,2,2- trifluoro ethoxies, five fluorine ethyoxyls, 3- fluorine propoxyl group, the oxygen of 3,3- difluoros third It is base, 3,3,3- trifluoros propoxyl group, 2,2,3,3- tetrafluoros propoxyl group, the fluorine propoxyl group of 2,2,3,3,3- five, seven fluorine propoxyl group, seven fluoro- 2- propoxyl group, 4- fluorine butoxy, 4,4,4- trifluoros butoxy, 2,2,3,3,4,4- hexafluoros butoxy, the fluoro- 2- trifluoros of 3,3,3- tri- Methyl propoxyl group, the fluorine butoxy of 2,2,3,3,4,4,4- seven, the fluoro- 2- trifluoromethyls propoxyl group of 2,3,3,3- tetra-, 1,1,2,2,3, 3,4,4- octafluoro butoxy, nine fluorine butoxy etc., but it is not limited to these.

It is used as preferred C₁~C₄Halogenated alkoxy, for example, can enumerate difluoro-methoxy, trifluoromethoxy, 2,2,2- tri- Fluorine ethyoxyl, five fluorine ethyoxyls, 3,3,3- trifluoros propoxyl group, seven fluorine propoxyl group, seven fluoro- 2- propoxyl group, 4- fluorine butoxy, 4,4, The fluoro- 2- trifluoromethyls propoxyl group of 4- trifluoros butoxy, 3,3,3- tri-, the fluorine butoxy of 2,2,3,3,4,4,4- seven, 1,1,2,2,3, 3,4,4- octafluoros butoxy, nine fluorine butoxy etc..

C₁~C₄Halogenated alkylthio represent haloalkyl moiety have above-mentioned implication, by 1~9 identical or different halogen The carbon number of atom substitution is 1~4 straight chain or (alkyl)-S- bases of branch-like.It is used as C₁~C₄Halogenated alkylthio, for example Fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, 2- fluorine ethylmercapto group, 2,2- difluoros ethylmercapto group, 2,2,2- trifluoro second can be enumerated Sulfenyl, 3- fluorine rosickyite base, 3,3- difluoro rosickyite base, 3,3,3- trifluoropropyls sulfenyl, 4- fluorine butylthio, 4,4- difluoros butylthio, 4, 4,4- trifluoro butylthios etc., but it is not limited to these.

It is used as preferred C₁~C₄Halogenated alkylthio, can for example enumerate fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, 2,2- difluoros ethylmercapto group, 2,2,2- trifluoros ethylmercapto group, 3,3,3- trifluoropropyl sulfenyls etc..

C₁~C₄Alkylsulfinyl represent haloalkyl moiety have above-mentioned implication, by identical or different 1~ The carbon number of 9 halogen atom substitutions is 1~4 straight chain or (alkyl)-SO- bases of branch-like.

It is used as C₁~C₄Alkylsulfinyl, for example, can enumerate methyl fluoride sulfinyl, difluoromethyl sulfenyl The sub- sulphur of base, trifluoromethyl sulphinyl base, 2- fluoro ethyls sulfinyl, 2,2- difluoros ethylsulfinyl, 2,2,2- trifluoroethyls Acyl group, 3- fluoropropyls sulfinyl, 3,3- difluoros propylsulfenyl, 3,3,3- trifluoro propyls sulfinyl, 4- fluorine butyl are sub- Sulfonyl, 4,4- difluorobutyl groups sulfinyl, 4,4,4- triRuorobutyl sulfinyls etc., but it is not limited to these.

It is used as preferred C₁~C₄Alkylsulfinyl, for example, can enumerate methyl fluoride sulfinyl, difluoromethyl sub- Sulfonyl, trifluoromethyl sulphinyl base, 2,2- difluoros ethylsulfinyl, 2,2,2- trifluoroethyls sulfinyl, 3,3,3- tri- Fluoropropyl sulfinyl etc..

C₁~C₄Alkylsulfonyloxy group basis representation moieties have the carbon number of above-mentioned implication for 1~4 (alkyl)- SO2-O- bases.

It is used as C₁~C₄Alkylsulfonyloxy, for example, can enumerate methanesulfonyloxy group, ethanesulfonyl epoxide, n-propane sulphur Acyloxy, normal butane sulfonyloxy etc., but it is not limited to these.

It is used as preferred C₁~C₄Alkylsulfonyloxy, for example, can enumerate methanesulfonyloxy group.

C₁~C₄Haloalkylsulfonyloxy represents the (halogen that the carbon number that haloalkyl moiety is above-mentioned implication is 1~4 Substituted alkyl)-SO2-O- bases.

It is used as C₁~C₄Haloalkylsulfonyloxy, for example, can enumerate trifluorometanesulfonyloxy, 2,2,2- HFC-143as Sulfonyloxy, 3,3,3- trifluoro propanesulfonyloxies, 4,4,4- trifluorobutane sulfonyloxies, nine fluorine butane sulfonyloxies etc., but It is not limited to these.

It is used as preferred C₁~C₄Haloalkylsulfonyloxy, for example, can enumerate trifluorometanesulfonyloxy, nine fluorine butane Sulfonyloxy etc..

C₆~C₁₀Aryl-sulfonyl oxygen basis representation C₆~C₁₀Aryl moiety be above-mentioned implication carbon number be 6~10 (virtue Base)-SO2-O- bases.

It is used as C₆~C₁₀Aryl-sulfonyl oxygen, for example, can enumerate benzenesulfonyl epoxide.

2. the manufacture method of the trifluoromethyl alkylthio compound of the present invention

The present invention is following methods：The alkyl compound that will be represented by formula (2) is as starting compound, by the raw material Compound is mixed with fluorine compounds, and thiophosgene is added in resulting raw mixture, the L bases of starting compound is passed through trifluoro Butylthiomethylization reaction reacts, so as to manufacture trifluoromethyl alkylthio compound.Change to being used in the present invention below Compound, reaction condition etc. are described in detail.

(starting compound)

The raw material used in the present invention is the alkyl compound represented by following formulas (2), and it is not in the prior art The reactive high alkyl compound used, but the low alkyl compound of reactivity.

Formula (2)：

[changing 3]

L represents halogen atom, C₁~C₄Alkylsulfonyloxy, C₁~C₄Haloalkylsulfonyloxy or with or without The C of substituent₆~C₁₀Aryl-sulfonyl oxygen.)

The high alkyl compound of reactivity is such as representing in benzyl position, the α positions of carbonyl carbon, pi-allyl position or propargyl position Alkyl compound with leaving groups such as halogen atom, alkylsulfonyloxy or aryl-sulfonyl oxygens.Have in benzyl position and leave away The starting compound used in the specifically above-mentioned patent document 2 and 3 of the alkyl compound of group, even if in the bar not heated Trifluoromethylthioization reaction is also promptly carried out under part.

Above-mentioned patent document 2 is also applied for the alkyl compound that there is leaving group in pi-allyl position, propargyl position Reaction condition, as a result they promptly reacted in room temperature, to have obtained target compound (reference example described later in high yield 1、2).Thus, in this manual, the alkyl compound for having leaving group in pi-allyl position, propargyl position is also contained in instead In Ying Xinggao alkyl compound group.

The low alkyl compound of reactivity refers to the compound group for not including the high alkyl compound of above-mentioned reactivity.Separately Outside, alkene, alkynes are included even in the side chain and main chain of the low alkyl compound of reactivity sometimes, also refers to formula (2) and broad sense It is upper to be referred to as the low alkyl compound of reactivity.

As the alkyl compound of above-mentioned formula (2), (2- bromoethyls) benzene, benzyl -2- specifically, for example, can be enumerated The bromo- 1- butylene of bromoethyl ether, n-propyl chloride, 1- N-Propyl Bromides, 1- iodopropanes, 1- NBBs, 4-, the iodo- 1- butine of 4-, the bromo- 5- of 1- Methyl amylether, the 5- chloro- 2- of bromine amyl group -4- fluoro- 5- (2,2,2- trifluoros ethylmercapto group) phenyl ether, the chloro- 2- of 5- bromine amyl group -4- are fluoro- 5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether, 5- bromine pentaacetic acids ester, 6- bromocaproic acids ethyl ester, 1- chlorohexanes, 1- bromines oneself Alkane, 1- iodohexanes, 6- bromine hexylacetic acids ester, 6- bromine hexyl -2,4- dimethyl -5- (2,2,2- trifluoros ethylmercapto group) phenyl ether, 6- Bromine hexyl -2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether, 1- heptyl bromides, the bromo- 3- heptene of 1-, 1- are bromo- The bromo- 3- octynes of 3- heptyne, 1- iodo-octanes, methanesulfonic acid monooctyl ester, p-methyl benzenesulfonic acid monooctyl ester, 1-, 1- bromononanes, the bromo- 4- nonenes of 1-, 1- The bromo- 4- decene of iodo- 4- n-heptylacetylenes, 1- bromo-decanes, 10-, the iodo- 4- decine of 10-, 1- bromo-n-11s, the bromo- 5- endecatylenes of 11-, 11- The bromo- 1- endecatylenes of iodo- 5- hendecynes, 11-, 1- bromo-dodecanes etc., but it is not limited to these.

(fluorine compounds)

As the fluorine compounds used in the present invention, for example, it can enumerate tetralkyl ammonium fluorides salt；It is fluorinated alkali metal salt Class；It is fluorinated alkaline-earth metal class；And their mixture.Among them, more preferably tetralkyl ammonium fluorides salt；It is fluorinated alkali metal Salt；And their mixture.

As the concrete example of these fluorine compounds, Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, fluorination can be preferably enumerated Sodium, potassium fluoride, cesium fluoride, magnesium fluoride, any mixture of calcirm-fluoride and their arbitrary proportions, but it is not limited to these.As The concrete example of preferred fluorine compounds, can enumerate Methanaminium, N,N,N-trimethyl-, fluoride, potassium fluoride, cesium fluoride and their arbitrary proportions Any mixture.As the concrete example of further preferred fluorine compounds, potassium fluoride can be enumerated.Shape on the fluorine compounds State, as long as can be reacted, it is possible to be any form, those skilled in the art can properly select.

(potassium fluoride)

On the form of the potassium fluoride used in the present invention, as long as can be reacted, it is possible to be any form, this area Technical staff can properly select.Potassium fluoride can be directly using generally commercially available potassium fluoride, also can be with equal in a solvent The state of even dissolving or partly soluble state are used.In the potassium fluoride, from the dissolving in organic solvent is reacted, divide From the aspect of scattered property, including powder body form and the big potassium fluoride based on spray drying preparation method of specific surface area.

(consumptions of fluorine compounds)

On the consumption of the fluorine compounds in the present invention, as long as can be reacted, so that it may be any amount, people in the art Member can suitably adjust.Suppress and business efficiency in terms of from yield, accessory substance, the consumptions of fluorine compounds can example go out The alkyl compound represented relative to 1.0 moles by formula (2) is more than 3.0 moles of scope, is preferably more than 3.0 moles Less than 15.0 moles of scope, more preferably less than more than 3.0 moles 12.0 moles scope, be more preferably 4.0 moles Scope below 9.0 moles of the above.

(consumption of thiophosgene)

On the consumption of the thiophosgene in the present invention, as long as can be reacted, it is possible to be any amount, people in the art Member can suitably adjust.Suppress and business efficiency in terms of from yield, accessory substance, the consumption of thiophosgene can example go out phase It is less than more than 0.9 mole 5.0 moles of scope, is preferably 1.0 for 1.0 moles of alkyl compound represented by formula (2) Less than 3.0 moles of scope more than mole, more preferably less than more than 1.0 moles 2.0 moles of scope.

(solvent)

Present invention preferably uses solvent implementation.As the solvent used in the present invention, for example, it can enumerate nitrile (such as second Nitrile etc.)；Ethers (such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), dioxane, ethylene glycol Dimethyl ether, diethylene glycol dimethyl ether etc.)；Halogenated hydrocarbon (such as dichloromethane, chloroform, carbon tetrachloride, tetrachloroethanes)；Aromatic series Hydro carbons (such as benzene, chlorobenzene, dichloro-benzenes, nitro benzene,toluene,xylene)；Amide-type (such as N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC), 1-METHYLPYRROLIDONE (NMP) etc.)；Glyoxalidine ketone (such as 1,3- diformazans Base -2- glyoxalidine ketone (DMI) etc.)；Sulfoxide type (such as dimethyl sulfoxide (DMSO) (DMSO))；And their arbitrary proportion is mixed Bonding solvent, but it is not limited to these.As the preferred embodiment of these solvents, acetonitrile can be enumerated.

The acetonitrile used in the present invention is preferably through dehydration, and dewatering can suitably be adjusted by those skilled in the art.

(consumption of solvent)

As long as the consumption on the solvent in the present invention can be reacted, it is possible to be any amount.Solvent in the present invention Consumption can suitably be adjusted by those skilled in the art.Suppress and business efficiency in terms of from yield, accessory substance, make For the consumption of solvent, for example, the compound relative to 1.0 general Formulas (2) is 0.01~50L (liters), preferably 0.1~15L, More preferably 0.1~10L.

(reaction temperature)

The reaction temperature of trifluoro butylthiomethylization reaction in the present invention can suitably be adjusted by those skilled in the art. Suppress and business efficiency in terms of from yield, accessory substance, as reaction temperature, can example go out and usually more than 50 DEG C and be In scope below the boiling point of used solvent, preferably less than more than 50 DEG C 110 DEG C of scope, more preferably more than 60 DEG C Less than 100 DEG C of scope, more preferably less than more than 70 DEG C 90 DEG C of scope.

(reaction time)

It is not particularly limited for the reaction time of the trifluoro butylthiomethylization reaction in the present invention.Reaction in the present invention Time can suitably be adjusted by those skilled in the art.Suppress and business efficiency in terms of from yield, accessory substance, as Reaction time, can example go out usually 0.5 hour~48 hours, be preferably 1 hour~36 hours, more preferably 1 hour~24 The scope of hour.Herein, " reaction time " refer to after the thiophosgene for just having added whole amount untill reaction terminating when Between.Reaction time in the present invention is the addition time phase region with thiophosgene for during consuming the curing of unreacted raw material Not.

(product)

It is the trifluoromethyl alkylthio compound represented by following formulas (1) by product produced by the present invention.

Formula (1)：

[changing 4]

(in formula, R is identical with the definition in above-mentioned formula (2).)

As the trifluoromethyl alkylthio compound of above-mentioned formula (1), specifically, for example, [2- (trifluoros can be enumerated Methyl mercapto) ethyl] benzene, benzyl -2- (trifluoromethylthio) ethylether, 1- trifluoromethylthios propane, 1- trifluoromethylthios butane, 4- Trifluoromethylthio -1- butylene, 4- trifluoromethylthio -1- butine, the 5- fluoro- 5- of the chloro- 2- of trifluoromethylthio amyl group -4- (2,2,2- tri- Fluorine ethylmercapto group) phenyl ether, the 5- chloro- 2- of trifluoromethylthio amyl group -4- fluoro- 5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether, 6- trifluoromethylthios ethyl hexanoate, 5- (trifluoromethylthio) pentaacetic acids ester, 1- methoxyl group -5- trifluoromethylthios pentane, 1- tri- Fluorine methyl mercapto hexane, 6- trifluoromethylthio hexylacetic acids ester, 6- trifluoromethylthio hexyl -2,4- dimethyl -5- (2,2,2- trifluoros Ethylmercapto group) phenyl ether, 6- trifluoromethylthio hexyl -2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether, 1- Trifluoromethylthio heptane, 1- trifluoromethylthio -3- heptene, 1- trifluoromethylthio -3- heptyne, 1- trifluoromethylthios octane, 1- (three Fluorine methyl mercapto) -3- octynes, 1- trifluoromethylthios nonane, 1- trifluoromethylthio -4- nonenes, 1- trifluoromethylthio -4- n-heptylacetylenes, 1- Trifluoromethylthio decane, 10- trifluoromethylthio -4- decene, 10- trifluoromethylthio -4- decine, 1- trifluoromethylthios hendecane, 11- trifluoromethylthio -5- endecatylenes, 11- trifluoromethylthio -5- undecynes alkynes, 11- (trifluoromethylthio) -1- endecatylenes, 1- trifluoromethylthio dodecanes etc., but it is not limited to these.

3. the adding conditional of thiophosgene

It is a feature of the present invention that in the raw mixture of the starting compound comprising formula (2) and fluorine compounds, More than 45 DEG C of addition temperature and add thiophosgene with addition time of more than 0.25 hour.Below to the adding conditional of thiophosgene It is described in detail.

(adding method)

Addition of the thiophosgene into raw mixture can be carried out using known method.It can such as enumerate using a point liquid Funnel, dropping funel, buret, syringe etc. are added drop-wise to method in reaction system etc..A small amount of sulphur is added in the time of cost In the case of phosgene, preferred compositions use syringe and syringe pump.A large amount of sulphur light are added into reactor etc. in the cost time In the case of gas, method for being added drop-wise to using constant displacement pump, drip tank etc. in reaction system etc. can be enumerated.In addition, in addition sulphur During phosgene, in order that reaction is carried out, raw mixture is stirred preferably by agitator etc..

(addition temperature)

As long as the addition temperature of the thiophosgene in the present invention is more than 45 DEG C, it is possible to by those skilled in the art suitably Adjustment.From yield, accessory substance suppress and business efficiency in terms of, as addition temperature, can example go out usually 45 DEG C with In scope below upper and the solvent for used in boiling point, preferably less than more than 50 DEG C 110 DEG C of scope, more preferably 60 Less than 100 DEG C of scope more than DEG C, more preferably less than more than 70 DEG C 90 DEG C of scope.Herein, " addition temperature " refers to The temperature of the reaction system after thiophosgene is just added.If in addition, the, it can be said that sulphur light once added into raw mixture It is a small amount of that the amount of gas is relative, then influence of the temperature of thiophosgene to reaction system is small, thus can also mix raw material when adding The temperature of compound is used as addition temperature.

(addition time)

As long as the addition time of the thiophosgene in the present invention is more than 0.25 hour (i.e. 15 minutes), it is possible to by this area Technical staff suitably adjusts.The aspect particularly improved from yield, can as the lower limit of the addition time in the present invention With example go out preferably more than 0.5 hour, more preferably more than 1.0 hours, be more preferably more than 2.0 hours, it is especially excellent Elect as more than 3.5 hours.In addition, particularly suppressing and business efficiency in terms of from accessory substance, adding in the present invention is used as The upper limit between added-time, can be gone out preferably less than 48 hours, more preferably less than 36 hours, more preferably 24 hours with example Below, it is particularly preferably less than 12 hours.The scope of addition time in the present invention can combine above-mentioned lower and upper limit, Suitably adjusted by those skilled in the art.As addition the time upper and lower bound combination, for example can example go out preferably 0.5 hour~48 hours, more preferably 1.0 hours~36 hours, more preferably 2.0 hours~24 hours, particularly preferably For 3.5 hours~12 hours.But, the present invention is not by any restriction of these combinations.Herein, " addition time " refers to from adding Increase the beginning and (start to add thiophosgene into reaction system) and play untill addition terminates and (whole amount is added in reaction system) Time.

The adding speed of the compound represented as thiophosgene relative to 1 mole by formula (2) is (hereafter as " mole adding Acceleration "), it is often preferred that less than 10 mols/hr.When mole adding speed is less than 10 mols/hr, with raising mesh Material yield tendency.Mole adding speed is preferably less than 5 mols/hr, more preferably less than 2 mols/hr, enter One step is preferably less than 1 mol/hr.In addition, particularly suppressing and business efficiency in terms of from accessory substance, this hair is used as The lower limit of mole adding speed in bright, can example go out preferably more than 0.028 mol/hr, more preferably 0.042 mole/ Hour more than, more preferably more than 0.083 mol/hr.The scope of mole adding speed in the present invention can will be upper The upper and lower bound combination stated, is suitably adjusted by those skilled in the art.It is used as the upper and lower bound of mole adding speed Combination, for example can example go out preferably 0.028 mol/hr~5 mols/hr, more preferably 0.042 mol/hr~2 rub That/hour, more preferably 0.083 mol/hr~1 mol/hr.But, the present invention is not appointed by these combinations What is limited.It should be noted that a mole adding speed is expressed from the next.

Mole adding speed=(whole additions (mol) that the thiophosgene that addition is terminated is played since addition/add Between added-time (h)) molal quantity (mol) of formula (2) that contains in raw mixture before/addition

The addition of thiophosgene is preferably played addition since addition and is terminated with substantially certain speed progress, but is adding Even if it is also what is allowed that adding speed, which slightly changes, between the added-time.As the amplitude of fluctuation for mole adding speed allowed, Relative to mole adding speed be -20%~+20% in the range of, be preferably -10%~+10% in the range of, more preferably - In the range of 5%~+5%.

(combination of addition temperature and addition time)

In the present invention, in order to obtain purpose thing in high yield, in the presence of alkyl compound and fluorine compounds on one side Carrying out heating, slowly addition thiophosgene is important on one side.The present inventor has carried out condition research in detail, as a result specify that, It is preferred that the addition time by addition temperature influenceed.Embodiment and reference example are described in detail below.

In the case that the addition temperature of thiophosgene is 40 DEG C, thiophosgene is added even with the times of 3.5 hours, also can not To obtain purpose thing in high yield.In the case that the addition temperature of thiophosgene is 50 DEG C, sulphur light is being added using the time of 3.5 hours During gas, purpose thing has been obtained with moderate yield.In the case that the addition temperature of thiophosgene is 60 DEG C, utilizing 1 hour Time addition thiophosgene when, purpose thing has been obtained with moderate yield；Thiophosgene is being added using the time of 2 hours When, to have obtained purpose thing in high yield；When adding thiophosgene using the time of 3.5 hours, purpose has been obtained with higher yield Thing.In the case where the addition temperature of thiophosgene is 80 DEG C, when adding thiophosgene using the time of 0.5 hour, with medium journey The yield of degree has obtained purpose thing；When adding thiophosgene using the time of 1 hour, to have obtained purpose thing in high yield.

So as on the combination of addition temperature and addition time, go out in terms of yield, accessory substance suppression and business efficiency Hair, in the case where addition temperature is 45 DEG C~55 DEG C, can example to go out the addition time be usually 3.5 hours~48 hours, preferably For 3.5 hours~36 hours, more preferably 3.5 hours~24 hours.In the case where addition temperature is 55 DEG C~70 DEG C, it can show Example go out the addition time be usually 1.0 hours~48 hours, be preferably 2.0 hours~36 hours, it is more preferably 3.5 hours~24 small When.In the case where addition temperature is 70 DEG C~90 DEG C, can example to go out the addition time be usually 0.5 hour~48 hours, preferably For 1.0 hours~36 hours, more preferably 1.0 hours~24 hours, more preferably 2.0 hours~12 hours.But, this Invention is not by any restriction of these combinations, and the combination of addition temperature and addition time can be appropriate by those skilled in the art Ground is adjusted.

In addition, suppressing and business efficiency in terms of from yield, accessory substance, addition temperature and the group of addition time are used as The condition of conjunction, is preferably set in following scopes.

The addition time (h) × (addition temperature (DEG C) -45)≤10

When above-mentioned " addition time (h) × (addition temperature (DEG C) -45) " is less than 10, there is yield reduction.From purpose Set out in terms of the yield of material, as the value of " addition time (h) × (addition temperature (DEG C) -45) ", preferably more than 15, more Preferably more than 25, it is more preferably more than 50.In addition, particularly suppress and business efficiency in terms of from accessory substance, As the upper limit of " addition time (h) × (addition temperature (DEG C) -45) " in the present invention, can example go out preferably less than 2340, More preferably less than 1320, it is more preferably less than 540.In the present invention " addition time (h) × (addition temperature (DEG C)- 45) scope " can combine above-mentioned upper and lower bound, suitably be adjusted by those skilled in the art.It is used as " the addition time (h) combination of the upper and lower bound of × (addition temperature (DEG C) -45) ", for example can example go out preferably 15~2340, more preferably 25~1320, it is more preferably 50~540.But, the present invention is not by any restriction of these combinations.

In addition, suppressing and business efficiency in terms of from yield, accessory substance, the pass of mole adding speed and addition temperature System is preferably set in following scope.

1≤mole adding speed (mol/hr) × (addition temperature (DEG C) -45)≤400

Above range is preferably less than more than 1.2 300, more preferably less than more than 2 100, more preferably more than 5 50 Below.

According to the present invention, as described above, it is possible under conditions of multiple processes are needed unlike patent document 1 and make It is capable of the raw material of low cost acquisition to obtain the trifluoromethyl alkylthio compound as desired substance with thiophosgene etc., thus It is industrially preferred from the aspect of productivity ratio, cost.Further, since also without using described in patent document 3 The special reaction units such as bead stirring, thus from this viewpoint, industrially could also say that preferred.

Doctor agricultural chemicals (pharmaceuticals and agriculture are used as by the trifluoromethyl alkylthio compound of the manufacture method manufacture of the present invention Medicine) and its intermediate be useful.Specifically, such as also recorded in patent document 1, as insecticide, killed tick agent etc. Noxious organism control agent and its intermediate are useful.

Embodiment

Then embodiment is enumerated the manufacture method of the present invention is specifically described, but the present invention is not by these embodiments Any restriction.

Below in an example, room temperature is usually 10 DEG C~35 DEG C of scope.

In this specification, as long as no special limitation, under the addition use of the thiophosgene of embodiment, comparative example and reference example State equipment.

Dropping feeder；Stream is micro- to react with syringe pump (YSP-101YMC companies manufacture)

Syringe；Glass syringe 10ml Hamilton gastight#1010, tefl o n luer and plunger Seal (HAMILTON systems)

In this specification, the measure of each physical property uses following equipment in embodiment, comparative example and reference example.

¹H NMR spectrums (¹H-NMR)；JEOL JMN-ECS300 or JEOL JMN-Lambda-400 (JEOL's strains Formula commercial firm manufacture), internal standard material：Tetramethylsilane (TMS)

Gas chromatographic analysis (GC analyses)；6850Network GC System (Agilent Technologies systems), inspection Survey method：FID

On GC analysis methods, documents below is may be referred to as needed.

Document (a)：(society) Japanization association compile, " new experimental chemistry by the analytical chemistry II " of seat 9, page 60~86 (1977 Year), publisher's meal spring it is new I, Wan Shan Co., Ltd. is (for example, on the stationary phase liquid that can be used in post, may be referred to Page 66.)

Document (b)：(society) Japanization association compiles, " experimental chemistry by seat 20-1 analytical chemistry " the 5th edition, page 121~129 (2007), publisher village Tian Chengsi youth, Wan Shan Co., Ltd. are (for example, on the specifically used of capillary hollow post separation post Method, may be referred to page 124~125.)

(embodiment 1)

The manufacture of 6- (trifluoromethylthio) hexylacetic acid ester

[changing 5]

Being heated to reflux the lower time using 1 hour by thiophosgene 7.2mL (94mmol) 6- is added drop-wise to using dropping funel (reaction now in bromine hexylacetic acid ester 15.0g (67.2mmol) and potassium fluoride 23.4g (403mmol) acetonitrile 400mL solution Temperature in system is 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, by reactant mixture natural cooling To room temperature, insoluble matter is filtered out.After water is added in filtrate and is extracted using diisopropyl ether, organic layer is utilized into saturated sodium bicarbonate The aqueous solution, saturated aqueous common salt cleaning.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, inorganic matter is filtered out, is depressurized Under solvent is distilled off.Resulting thick product is refined by vacuum distillation (122-124 DEG C of 20hPa, boiling point), obtain for 6- (trifluoromethylthio) hexylacetic acid ester 15.6g (yield 95%) of weak yellow liquid.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.35-1.50(m,4H),1.59-1.73(m,4H),2.05(s,3H), 2.88(t,2H),4.06(t,2H)

By the result of embodiment 1 according to raw material (6- bromine hexylacetic acids ester) molal quantity (" raw material (mmol) " in table), Total addition molal quantity (" thiophosgene (mmol) " in table) of thiophosgene, addition time (" addition time (h) " in table), addition Temperature (" addition temperature (DEG C) " in table), reaction time (" reaction time (h) " in table), thiophosgene are relative to every 1 mole Value (the table of the adding speed (" mole adding speed (mol/h) " in table) of raw material, " addition time × (addition temperature -45) " In " T* (C-45) (h DEG C) "), the value (" V* (C-45) in table of " mole adding speed × (addition temperature -45) " (mol DEG C/h) "), the order of yield (" yield (%) " in table) is summarised in table 1.

(embodiment 2~4)

Change addition temperature, addition time respectively, thiophosgene 0.60mL (7.7mmol) acetonitrile 4.5mL solution is added dropwise Into 6- bromine hexylacetic acid ester 1.2g (5.5mmol), potassium fluoride 1.9g (33mmol) acetonitrile 32mL solution.After stirring 1 hour, A part for reactant mixture is analyzed using GC, the yield of purpose thing is calculated by area percent method.By result It is summarised in similarly to Example 1 in table 1.It should be noted that in the GC analyses of embodiment 2~4, in addition to purpose thing also It detected unreacted starting compound (6- bromine hexylacetic acids ester).

[table 1]

(embodiment 5)

The manufacture of 6- (trifluoromethylthio) ethyl hexanoate

[changing 6]

Thiophosgene 1.2mL (15mmol) acetonitrile 3.8mL solution is added drop-wise in the time for being heated to reflux lower utilization 1 hour In 6- bromocaproic acid ethyl ester 2.4g (11mmol) and potassium fluoride 3.8g (65mmol) acetonitrile 62mL solution (in reaction system now Temperature be 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.To reactant mixture Middle addition water, after being extracted using diisopropyl ether, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.It will divide After the organic layer that liquid is obtained is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression, so as to obtain to be red 6- (trifluoromethylthio) the ethyl hexanoate 2.5g (yield 96%) of brown liquid.Result is summarised in table 2.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：1.26(t,3H),1.41-1.48(m,2H),1.62-1.75(m,4H), 2.31(t,2H),2.88(t,2H),4.13(t,2H)

(embodiment 6)

The preparation method of 6- (trifluoromethylthio) hexyl -2,4- dimethyl -5- (2,2,2- trifluoros ethylmercapto group) phenyl ether

[changing 7]

Thiophosgene 0.27mL (3.5mmol) acetonitrile 2.0mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour To 6- bromine hexyl -2,4- dimethyl -5- (2,2,2- trifluoros ethylmercapto group) phenyl ether 1.0g (2.5mmol) and potassium fluoride 0.87g In the acetonitrile 15mL solution of (15mmol) (temperature in reaction system now is 80 DEG C).Reactant mixture is being heated to reflux After lower stirring 1 hour, reactant mixture is naturally cooled into room temperature.Water is added into reactant mixture, is carried using diisopropyl ether After taking, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.The organic layer that point liquid is obtained utilizes anhydrous sulphur After sour magnesium is dried, filter out and solvent is distilled off under inorganic matter, decompression.Resulting thick product is carried using silica gel column chromatography It is pure, obtain 6- (trifluoromethylthio) hexyl -2,4- dimethyl -5- (2,2,2- trifluoro ethylmercapto group) phenyl ether for colourless liquid 0.87g (yield 83%).Result is summarised in table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.48-1.53(m,4H),1.69-1.85(m,4H),2.17(s,3H), 2.38(s,3H),2.90(t,2H),3.31(q,2H),3.94(t,2H),6.96(s,1H),7.00(s,1H)

(embodiment 7)

The preparation method of 6- (trifluoromethylthio) hexyl -2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether

[changing 8]

Thiophosgene 0.080mL (1.0mmol) acetonitrile 1.0mL solution is dripped in the time for being heated to reflux lower utilization 1 hour It is added to 6- bromine hexyl -2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenyl ether 0.30g (0.72mmol) and fluorination In potassium 0.25g (4.3mmol) acetonitrile 5.0mL solution (temperature in reaction system now is 80 DEG C).By reactant mixture After lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.Water is added into reactant mixture, is extracted using diisopropyl ether Afterwards, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.The organic layer that point liquid is obtained utilizes anhydrous slufuric acid After magnesium is dried, filter out and solvent is distilled off under inorganic matter, decompression.Resulting thick product is purified using silica gel column chromatography, Obtain 6- (trifluoromethylthio) hexyl -2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) benzene for filbert liquid Base ether 0.29g (yield 91%).Result is summarized in table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.49-1.52(m,4H),1.71-1.76(m,2H),1.78-1.85 (m,2H),2.23(s,3H),2.28(s,3H),2.90(t,2H),3.32-3.44(m,2H),4.04(t,2H),7.01(s, 1H),7.37(s,1H)

(embodiment 8)

The manufacture of 1- (trifluoromethylthio) octane

[changing 9]

Thiophosgene 1.2mL (15mmol) acetonitrile 3.8mL solution is added drop-wise in the time for being heated to reflux lower utilization 1 hour (the temperature in reaction system now in 1- iodo-octanes 2.6g (11mmol) and potassium fluoride 3.8g (65mmol) acetonitrile 62mL solution Spend for 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.Add into reactant mixture Enter water, after being extracted using hexane, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Point liquid is obtained After organic layer is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression, so as to obtain as bronzing liquid 1- (trifluoromethylthio) octane 2.2g (yield 95%).Result is summarized in table 2.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：0.89(t,3H),1.27-1.43(m,10H),1.65-1.72(m, 2H),2.87(t,2H)

(embodiment 9)

The manufacture of 1- (trifluoromethylthio) dodecane

[changing 10]

Oar thiophosgene 1.2mL (15mmol) acetonitrile 3.8mL solution is added drop-wise in the time for being heated to reflux lower utilization 1 hour In 1- bromo-dodecanes 2.7g (11mmol) and potassium fluoride 3.8g (65mmol) acetonitrile 62mL solution (in reaction system now Temperature is 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.Into reactant mixture Water is added, after being extracted using hexane, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.Point liquid is obtained Organic layer using anhydrous magnesium sulfate dry after, filter out and solvent be distilled off under inorganic matter, decompression, so as to obtain as bronzing liquid 1- (trifluoromethylthio) the dodecane 2.9g (99%) of body.Result is summarized in table 2.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：0.88(t,3H),1.23-1.43(m,16H),1.64-1.72(m, 2H),2.87(t,2H)

(embodiment 10)

The preparation method of [2- (trifluoromethylthio) ethyl] benzene

[changing 11]

Thiophosgene 1.2mL (15mmol) acetonitrile 3.8mL solution is added drop-wise in the time for being heated to reflux lower utilization 1 hour (reaction system now in (2- bromoethyls) benzene 2.00g (11mmol) and potassium fluoride 3.8g (65mmol) acetonitrile 62mL solution Interior temperature is 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.To reaction mixing Water is added in thing, is extracted using diisopropyl ether.The organic layer that point liquid is obtained utilizes saturated sodium bicarbonate aqueous solution, saturated common salt Water is cleaned, and the organic layer after point liquid is dried using anhydrous magnesium sulfate.Filter out after inorganic matter, solvent is distilled off under decompression, so that Obtain [2- (trifluoromethylthio) ethyl] benzene 2.2g (yield 98%) for brown liquid.Result is summarized in table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：2.97-3.02(m,2H),3.11-3.16(m,2H),7.18-7.35 (m,5H)

(embodiment 11)

The preparation method of benzyl -2- (trifluoromethylthio) ethylether

[changing 12]

Thiophosgene 0.45mL (5.9mmol) acetonitrile 4.5mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour (now anti-into benzyl -2- bromoethyl ether 0.90g (4.2mmol) and potassium fluoride 1.5g (25mmol) acetonitrile 24mL solution It is 80 DEG C to answer the temperature in system).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.To anti- Answer and water is added in mixture, it is after being extracted using diisopropyl ether, organic layer saturated sodium bicarbonate aqueous solution, saturated aqueous common salt is clear Wash.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression.By institute Obtained thick product is purified using silica gel column chromatography, obtains benzyl -2- (trifluoromethylthio) ethylether for colourless liquid 0.80g (yield 81%).Result is summarized in table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：3.10(t,2H),3.72(t,2H),4.56(s,2H),7.29-7.38 (m,5H)

(embodiment 12)

The preparation method of 11- (trifluoromethylthio) -1- endecatylenes

[changing 13]

Thiophosgene 0.59mL (7.7mmol) acetonitrile 4.4mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour (now anti-into the bromo- 1- endecatylenes 1.3g (5.5mmol) of 11- and potassium fluoride 1.9g (33mmol) acetonitrile 32mL solution It is 80 DEG C to answer the temperature in system).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.To anti- Answer and water is added in mixture, it is after being extracted using diisopropyl ether, organic layer saturated sodium bicarbonate aqueous solution, saturated aqueous common salt is clear Wash.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression, so that Obtain 11- (trifluoromethylthio) -1- endecatylenes 1.30g (yield 93%) for brown liquid.It should be noted that due to Pass through¹Included in the product that H-NMR is obtained 15% the bromo- 1- endecatylenes of raw material 11-, thus the yield calculated by purity For 79%, it is summarised in table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.26-1.43(m,12H),1.65-1.72(m,2H),2.01-2.07 (m,2H),2.87(t,2H),4.91-5.02(m,2H),5.76-5.86(m,1H)

(embodiment 13)

The preparation method of 1- (trifluoromethylthio) -3- octynes

[changing 14]

Thiophosgene 0.56mL (7.4mmol) acetonitrile 2.0mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour (the reactant now into the bromo- 3- octynes 1.00g (5.3mmol) of 1- and potassium fluoride 1.8g (32mmol) acetonitrile 30mL solution Temperature in system is 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, room temperature is naturally cooled to.It is mixed to reaction Water is added in compound, after being extracted using diisopropyl ether, organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt. After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression, so as to obtain For 1- (trifluoromethylthio) -3- octynes 1.1g (yield 95%) of brown liquid.It should be noted that due to passing through¹H-NMR Included in obtained product 14% the bromo- 3- octynes of raw material 1-, thus the yield calculated by purity is 82%, is collected In table 2.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：0.91(t,3H),1.38-1.52(m,4H),2.12-2.18(m,2H), 2.53-2.59(m,2H),3.01(t,2H)

(embodiment 14)

The manufacture of 1- methoxyl groups -5- (trifluoromethylthio) pentane

[changing 15]

Thiophosgene 5.9mL (77mmol) acetonitrile 4.0mL solution is dripped in the time utilization for being heated to reflux lower utilization 1 hour Liquid funnel is added drop-wise to the bromo- 5- methyl amylethers 10.0g (55.2mmol) of 1- and potassium fluoride 19.2g (331mmol) acetonitrile 320mL In solution (temperature in reaction system now is 80 DEG C)., will be anti-by reactant mixture after lower stirring is heated to reflux 1 hour Solution is answered to naturally cool to room temperature.Water is added into reactant mixture, after being extracted using diisopropyl ether, by organic layer saturated carbon Sour hydrogen sodium water solution, saturated aqueous common salt cleaning.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter out inorganic Solvent is distilled off under thing, decompression.Resulting thick product is purified by vacuum distillation (89-92 DEG C of 60hPa, boiling point), is obtained To 1- methoxyl groups -5- (trifluoromethylthio) the pentane 9.6g (yield 86%) for yellow liquid.Result is summarized in table 2.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：1.43-1.51(m,2H),1.56-1.64(m,2H),1.68-1.76 (m,2H),2.89(t,2H),3.33(s,3H),3.38(t,2H)

[table 2]

(comparative example 1~12, embodiment 15~17,19,21,23~26)

Change addition temperature, addition time respectively, thiophosgene 0.51mL (6.6mmol) acetonitrile 4.5mL solution is added dropwise Into the bromo- 5- methyl amylethers 1.0g (5.5mmol) of 1-, potassium fluoride 1.4g (23mmol) acetonitrile 32mL solution, it is compared Experiment.A part for reactant mixture is analyzed using GC, the yield of purpose thing is calculated by area percent method.Will As a result it is summarized in table 3.On the addition time of the thiophosgene in table, numerical value " 0 " place represents the sulphur of disposable addition whole amount Phosgene.In addition, numerical value " ∞ " means infinity.It should be noted that comparative example 1~12, embodiment 15~17,19,21, In 23~26 GC analyses, unreacted starting compound (the bromo- 5- methyl amylethers of 1-) is also detected in addition to purpose thing.

(embodiment 18,20,22,27)

Change dropping temperature, time for adding respectively to be added drop-wise to thiophosgene 1.0mL (13.3mmol) acetonitrile 4.0mL solution In the bromo- 5- methyl amylethers 2.0g (11.0mmol) of 1-, potassium fluoride 2.7g (46mmol) acetonitrile 64mL solution, reality is compared Test.A part for reactant mixture is analyzed using GC, the yield of purpose thing is calculated by area percent method.Will knot Fruit is summarized in table 3.It should be noted that in the GC analyses of embodiment 18,20,22,27, also detected in addition to purpose thing Unreacted starting compound (the bromo- 5- methyl amylethers of 1-).

[table 3]

(embodiment 28)

The preparation method of the 5- chloro- 2- of (trifluoromethylthio) amyl group -4- fluoro- 5- (2,2,2- trifluoros ethylmercapto group) phenyl ether

[changing 18]

Thiophosgene 0.26mL (3.4mmol) acetonitrile 2.0mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour To the fluoro- 5- of the 5- chloro- 2- of bromine amyl group -4- (2,2,2- trifluoros ethylmercapto group) phenyl ether 1.0g (2.4mmol) and potassium fluoride 0.85g In the acetonitrile 14mL solution of (15mmol) (temperature in reaction system now is 80 DEG C).Reactant mixture is being heated to reflux After lower stirring 1 hour, room temperature is naturally cooled to.Water is added into reactant mixture, after being extracted using diisopropyl ether, by organic layer Cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter Go out under inorganic matter, decompression and solvent is distilled off, so as to obtain fluoro- for the chloro- 2- of 5- (trifluoromethylthio) amyl group -4- of brown liquid 5- (2,2,2- trifluoros ethylmercapto group) phenyl ether 1.0g (yield 95%).Result is summarized in table 4.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.58-1.66(m,2H),2.92(t,2H),3.41(q,2H),4.03 (t,2H),7.19-7.24(m,2H)

(embodiment 29~31)

Change addition temperature, addition time respectively to be added drop-wise to the μ L (1.2mmol) of thiophosgene 91 acetonitrile 0.50mL solution The 5- chloro- 2- of bromine amyl group -4- fluoro- 5- (2,2,2- trifluoros ethylmercapto group) phenyl ether 0.35g (0.85mmol), potassium fluoride 0.30g In the acetonitrile 5.0mL solution of (5.1mmol).After stirring 1 hour, a part for reactant mixture is analyzed using GC, led to Cross the yield that area percent method calculates purpose thing.Result is summarized in table 4.It should be noted that in embodiment 29~31 GC analysis in, also detected in addition to purpose thing unreacted starting compound (the fluoro- 5- of the 5- chloro- 2- of bromine amyl group -4- (2, 2,2- trifluoros ethylmercapto group) phenyl ether).

(embodiment 32)

The manufacture of 5- (trifluoromethylthio) pentaacetic acid ester

[changing 19]

Thiophosgene 0.6mL (7.7mmol) acetonitrile 4.5mL solution is added dropwise in the time for being heated to reflux lower utilization 1 hour (the reaction now into 5- bromine pentaacetic acid ester 1.2g (5.5mmol) and potassium fluoride 1.9g (33mmol) acetonitrile 32mL solution Temperature in system is 80 DEG C).By reactant mixture after lower stirring is heated to reflux 1 hour, by reactant mixture natural cooling To room temperature, insoluble matter is filtered out.Water is added in filtrate, after being extracted using hexane, by organic layer saturated sodium bicarbonate aqueous solution, Saturated aqueous common salt is cleaned.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, inorganic matter is filtered out, the lower distillation of decompression is removed Solvent is removed, so as to obtain 5- (trifluoromethylthio) pentaacetic acid ester 1.2g (yield 94%) of bronzing liquid.Result is collected In table 4.

¹H-NMR(300MHz,CDCl₃)δ(ppm)：1.43-1.53(m,2H),1.62-1.79(m,4H),2.05(s,3H), 2.89(t,2H),4.07(t,2H)

(embodiment 33~35)

Change addition temperature, addition time respectively, thiophosgene 0.60mL (7.7mmol) acetonitrile 4.5mL solution is added dropwise Into 5- bromine pentaacetic acid ester 1.2g (5.5mmol), potassium fluoride 1.9g (33mmol) acetonitrile 32mL solution.After stirring 1 hour, A part for reactant mixture is analyzed using GC, the yield of purpose thing is calculated by area percent method.By result It is summarized in table 4.It should be noted that in the GC analyses of embodiment 33~35, unreacted is also detected in addition to purpose thing Starting compound (5- bromine pentaacetic acids ester).

[table 4]

(comparative example 13)

The manufacture of 1- methoxyl groups -5- (trifluoromethylthio) pentane

[changing 20]

Thiophosgene 0.51mL (6.6mmol) is added to the bromo- 5- methyl amylethers 1.0g (5.5mmol) of 1- and fluorine at 0 DEG C In the acetonitrile 32mL solution for changing potassium 1.4g (23mmol).By reactant mixture after 0 DEG C is stirred 2 hours, 6 are stirred at room temperature small When.A part for reactant mixture is analyzed using GC, yield is calculated by area percent method, mesh is as a result detected Thing 1- methoxyl groups -5- (trifluoromethylthio) pentane be that the bromo- 5- methyl amylethers of 9%, raw material 1- are 90% (yield 9%).Will As a result it is summarized in table 5.

Japanese Unexamined Patent Publication 2000-53638 has been attempted for the starting compound (the bromo- 5- methyl amylethers of 1-) of embodiment 14 The method of publication (patent document 2), is not as a result almost reacted (comparative example 13).Thus, the manufacturer that patent document 2 is recorded Method can only be applied to the high compound of reactivity as benzyl halide compound, and not be suitable for the low alkylation of reactivity The trifluoromethylthio of compound.

(reference example 1)

The manufacture of 1- phenyl -3- (trifluoromethylthio) propylene

[changing 21]

Thiophosgene 0.51mL (6.6mmol) is added to Chinese cassia tree bromide (the bromo- 1- phenylpropens of 3-) 1.0g at 0 DEG C In (5.5mmol) and potassium fluoride 1.4g (23mmol) acetonitrile 32mL solution.By reactant mixture after 0 DEG C is stirred 2 hours, in It is stirred at room temperature 17 hours.Water is added into reactant mixture, it is after being extracted using hexane, organic layer is molten with saturated sodium bicarbonate water Liquid, saturated aqueous common salt cleaning.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, inorganic matter is filtered out, decompression is lower to steam Solvent is removed in distillation, so as to obtain 1- phenyl -3- (trifluoromethylthio) the propylene 1.2g (yield 100%) for brown liquid.Will knot Fruit is summarized in table 5.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：3.72(d,2H),6.19-6.26(m,1H),6.60(d,1H),7.25- 7.39(m,5H)

(reference example 2)

The manufacture of 1- (trifluoromethylthio) -2- octynes

[changing 22]

Thiophosgene 0.51mL (6.6mmol) is added to the bromo- 2- octynes 1.1g (5.5mmol) of 1- and potassium fluoride at 0 DEG C In 1.4g (23mmol) acetonitrile 32mL solution.By reactant mixture after 0 DEG C is stirred 2 hours, it is stirred at room temperature 17 hours.To Water is added in reactant mixture, it is after being extracted using hexane, organic layer saturated sodium bicarbonate aqueous solution, saturated aqueous common salt is clear Wash.After the organic layer that point liquid is obtained is dried using anhydrous magnesium sulfate, filter out and solvent is distilled off under inorganic matter, decompression, so that Obtain 1- (trifluoromethylthio) -2- octynes 1.2g (yield 100%) for brown liquid.Result is summarized in table 5.

¹H-NMR(400MHz,CDCl₃)δ(ppm)：0.90(t,3H),1.26-1.39(m,4H),1.46-1.54(m,2H), 2.16-2.21(m,2H),3.65(t,2H)

For having the alkyl compound of leaving group to apply the reaction of patent document 2 in pi-allyl position, propargyl position Condition, is as a result reacted rapidly in room temperature, to have obtained target compound (reference example 1,2) in high yield.Thus, in this explanation In book, in pi-allyl position, propargyl position there is the alkyl compound of leaving group to be also contained in the high alkyl compound of reactivity In group.

(reference example 3)

The manufacture of 2- chlorobenzyls-trifluoromethyl thioether (uses the high alkyl compound of reactivity as the manufacturer of raw material Method)

[changing 23]

Thiophosgene 0.60mL (7.7mmol) is added to 1- chloro- 2- (chloromethyl) benzene 0.9g (5.5mmol) and fluorine at 0 DEG C In the acetonitrile 32mL solution for changing potassium 1.9g (33mmol).By reactant mixture after 0 DEG C is stirred 2 hours, stirred in the case where being heated to reflux Mix 1 hour (temperature in reaction system now is 80 DEG C).Water is added into reactant mixture, will after being extracted using hexane Organic layer is cleaned with saturated sodium bicarbonate aqueous solution, saturated aqueous common salt.The organic layer that point liquid is obtained is done using anhydrous magnesium sulfate After dry, filter out and solvent is distilled off under inorganic matter, decompression, so as to obtain 2- chlorobenzyls-trifluoromethyl thioether for brown liquid 1.2g (yield 98%).Further, since passing through¹Included in the product that H-NMR is obtained 13% the chloro- 2- (chloromethanes of raw material 1- Base) benzene, thus the yield calculated by purity is 85%, is summarized in table 5.

[table 5]

Industrial applicibility

According to the present invention, it is possible to provide use the low alkyl compound of reactivity as the trifluoromethyl thio-alkylation of raw material The manufacture method of compound.

According to the present invention, it is possible to provide the manufacture method of trifluoromethyl alkylthio compound, it is used without many processes It is capable of the raw material of low cost acquisition, is industrially preferred without using special reaction unit.

And then, in accordance with the invention it is possible to produce on an industrial scale as doctor's agricultural chemicals and its useful fluoroform of intermediate Base alkylthio compound.

For example, institute in No. 2013/157229 publication of the compound group such as International Publication No. produced in embodiment 6,7 and 28 Disclose with excellent Pesticidal activity, be industrially useful.

For example, 6- (trifluoromethylthio) the hexylacetic acid esters produced in embodiment 1~4 are carrying out deacetylated alcohol being made After compound, can be derivatized to according to the manufacture method 7 disclosed in No. 2013/157229 publication of International Publication No. has with excellent The compound of evil biological insect control activity.

Thus, the present invention has very high industrial utility value.

Claims

1. the manufacture method of the trifluoromethyl alkylthio compound represented by following formulas (1), it is characterised in that by following In the presence of compound and fluorine compounds that formula (2) is represented, addition temperature more than 45 DEG C and with more than 0.25 hour The addition time adds thiophosgene,

Formula (1)：

[changing 1]

In formula (1), R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀Alkene Base, replaced or unsubstituted C by R1₂~C₁₀Alkynyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁ ~C₄Alkyl carbonyl epoxide, replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryl, Replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryloxy group or by one or two The R2 substitutions of above identical or different or unsubstituted C₆~C₁₀Aryl (C₁~C₄) alkoxy,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl-carbonyl oxygen Base, replaced or unsubstituted C by one or more identical or different R2₆~C₁₀Aryl, by one or two with On identical or different R2 substitutions or unsubstituted C₆~C₁₀Aryloxy group or by the identical of one or more or not Same R2 substitutions or unsubstituted C₆~C₁₀Aryl (C₁~C₄) alkoxy,

R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl, C₁~C₄Haloalkyl, C₁~C₄Alkoxy, C₁~C₄Halogenated alkoxy, C₁~C₄Halogenated alkylthio or C₁~C₄Alkylsulfinyl,

Formula (2)：

[changing 2]

In formula (2), R as defined in above-mentioned formula (1),

L represents halogen atom, C₁~C₄Alkylsulfonyloxy, C₁~C₄Haloalkylsulfonyloxy or with or without substitution The C of base₆~C₁₀Aryl-sulfonyl oxygen.

2. the manufacture method of trifluoromethyl alkylthio compound as claimed in claim 1, wherein, added with following conditions Thiophosgene,

Above-mentioned addition time (h) × (above-mentioned)≤10 of addition temperature (DEG C) -45.

3. the manufacture method of trifluoromethyl alkylthio compound as claimed in claim 1, wherein, relative to 1 mole by upper The compound of formula (2) expression is stated, the adding speed of thiophosgene is less than 10 mols/hr.

4. the manufacture method of trifluoromethyl alkylthio compound as claimed in claim 3, wherein, added with following conditions Thiophosgene,

1≤above-mentioned adding speed (mol/hr) × (above-mentioned)≤400 of addition temperature (DEG C) -45.

5. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, fluorination Compound is Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, magnesium fluoride, calcirm-fluoride or theirs is mixed Compound.

6. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, fluorination Compound is Methanaminium, N,N,N-trimethyl-, fluoride, potassium fluoride, cesium fluoride or their mixture.

7. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, relatively In 1.0 moles of compounds represented by above-mentioned formula (2), closed using the fluorination of less than more than 3.0 moles 12.0 moles of scopes Thing.

8. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, relatively In 1.0 moles of compounds represented by above-mentioned formula (2), the thiophosgene of less than more than 1.0 moles 3.0 moles of scope is used.

9. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, the system It is implementation in less than more than 60 DEG C 100 DEG C of scope that method, which is made, in addition temperature.

10. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, upper State in formula (1) and above-mentioned formula (2),

R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀Alkenyl, taken by R1 Generation or unsubstituted C₂~C₁₀Alkynyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl oxycarbonyl Base epoxide, by one or more identical or different R2 replace or unsubstituted phenyl, by one or more Identical or different R2 substitutions or unsubstituted phenoxy group or taken by one or more identical or different R2 Generation or unsubstituted benzyloxy,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkyl-carbonyl, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl-carbonyl oxygen Base, replaced or unsubstituted phenyl, the phase by one or more by one or more identical or different R2 With or different R2 substitutions or unsubstituted phenoxy group or replaced by one or more identical or different R2 or Unsubstituted benzyloxy,

L is by halogen atom, C₁~C₄Alkylsulfonyloxy, C₁~C₄Haloalkylsulfonyloxy or with or without substituent Phenylsulfonyloxy represent.

11. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, upper State in formula (1) and above-mentioned formula (2),

R represents to be replaced by R1 or unsubstituted C₁~C₁₀Alkyl, replaced or unsubstituted C by R1₂~C₁₀Alkenyl, taken by R1 Generation or unsubstituted C₂~C₁₀Alkynyl, replaced or unsubstituted benzene by one or more identical or different R2 Base or replaced or unsubstituted benzyloxy by one or more identical or different R2,

R1 represents C₁~C₄Alkyl, C₁~C₄Alkoxy, C₁~C₄Alkoxy carbonyl group, C₁~C₄Alkyl carbonyl epoxide, by one or two More than identical or different R2 substitutions or unsubstituted phenyl, replaced by one or more identical or different R2 Or unsubstituted phenoxy group or replaced or unsubstituted benzyloxy by one or more identical or different R2 Base,

R2 represents hydrogen atom, halogen atom, C₁~C₄Alkyl, C₁~C₄Halogenated alkylthio or C₁~C₄Alkylsulfinyl,

L is represented by halogen atom.

12. such as manufacture method of trifluoromethyl alkylthio compound according to any one of claims 1 to 4, wherein, upper State in formula (1) and above-mentioned formula (2),

R represents 4- Acetoxybutyls, 3- ethoxycarbonyl propyls, 4- [2,4- dimethyl -5- (2,2,2- trifluoros ethylmercapto group) benzene Epoxide] butyl, 4- [2,4- dimethyl -5- (2,2,2- trifluoroethyls sulfinyl) phenoxy group] butyl, n-hexyl, positive decyl, Phenyl, benzyloxy, 8- nonenyls, 1- hexin bases, 3- methoxy-propyls, 3- [the fluoro- 5- of the chloro- 2- of 4- (2,2,2- trifluoros ethylmercapto group) Phenoxy group] propyl group or 3- acetyloxypropyls,

L is represented by bromine atoms or iodine atom.