CN109689603A - The manufacturing method of E- olefin(e) compound - Google Patents
The manufacturing method of E- olefin(e) compound Download PDFInfo
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- CN109689603A CN109689603A CN201780053379.4A CN201780053379A CN109689603A CN 109689603 A CN109689603 A CN 109689603A CN 201780053379 A CN201780053379 A CN 201780053379A CN 109689603 A CN109689603 A CN 109689603A
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- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/08—Isomerisation
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- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
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- C07C43/235—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring
- C07C43/247—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring and to a carbon atom of a ring other than a six-membered aromatic ring containing halogen
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
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- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The object of the present invention is to provide the manufacturing methods for the E- olefin(e) compound that can apply extensive Z- olefin(e) compound as matrix.A kind of manufacturing method of isomerization body, the alkene derivatives of its alkene structures for acting on sulphur compound and radical initiator with one or more representative Z body in molecule, make at least one of alkene structures for representing Z body be isomerized to represent the alkene structures of E body.
Description
Technical field
The present invention relates to the manufacture intermediate and substance as chemical products such as medicine, pesticide, liquid crystal materials are useful
The manufacturing method of E- olefin(e) compound.
Background technique
E- olefin(e) compound in medicine, pesticide, liquid crystal material field more shows excellent characteristic, is useful chemical combination
Object.In particular, known in liquid crystal material, E- olefin(e) compound shows high transparency compared with corresponding saturated compounds
Point, lower viscosity and big elastic constant are extremely important compounds.In general, E- olefin(e) compound is via such as
Under process manufacture: composition comprising E- olefin(e) compound and corresponding Z- olefin(e) compound is carried out aryl Asia
Sulphonic acids are used as the isomerization reaction of catalyst, to improve the ratio (non-patent literature of the E- olefin(e) compound in composition
1,2).Furthermore it is known that aryl sulfinic acid is unstable, thus generally with corresponding arylsulfinate come buy, keeping, when use
Make in the reaction system itself and hydrochloric acid etc. acid react, generate fresh aryl sulfinic acid carry out using.At this point, generalling use as follows
Such process: by composition, sulfinate, acid and solvent comprising E- olefin(e) compound and corresponding Z- olefin(e) compound
After mixing at room temperature, it is heated to scheduled reaction temperature (patent document 1, non-patent literature 1 and non-patent literature 2).
[changing 1]
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application Publication 2012-528798 bulletin
Non-patent literature
Non-patent literature 1:H.Nozaki, Y.Nishikawa, M.Kawanishi, R.Noyori, tetrahedron
(Tetrahedron),23,2173(1967)
Non-patent literature 2:T.W.Gibson, P.Strassburger, J.Org.Chem., 41,791 (1976)
Summary of the invention
Subject to be solved by the invention
However, under the conditions of as the acidity in previous isomerization reaction and high temperature, if will have acid nonfast
The compound of functional group such as ester group, 2- THP trtrahydropyranyl etc. is used as matrix, then can hydrolyze, therefore, it is difficult to yields well
Obtain desired isomerized body.Therefore, under conditions of previous isomerization reaction, the matrix that can be applied is limited.
Therefore, the object of the present invention is to provide the E- that can apply extensive Z- olefin(e) compound as matrix
The manufacturing method of olefin(e) compound.
The method used for solving the problem
The inventors of the present invention have made intensive studies, as a result, it has been found that, by the manufacturing method of following isomerization body, even if not
Using acid, Z- alkene structures can be also isomerized to E- alkene structures, so as to complete the present invention, the manufacture of the isomerization body
Method is the alkene for acting on sulphur compound and radical initiator with one or more representative Z body in molecule
At least one of the alkene structures for representing Z body are isomerized to represent the alkene structures of E body by the alkene derivatives of structure.
Manufacturing method in this way, the reasons why Z- alkene structures can be isomerized to E- alkene structures do not know,
But the inventors of the present invention think, sulphur compound and radical initiator react to generate Thiyl Radical, which makees
For alkene, to promote isomerization, the substance based on the isomerization body with thermodynamically stable E- alkene structures is obtained.
In addition, the present invention can be the manufacturing method of following isomerization body: making the compound containing S -- S under heating
For the alkene derivatives of the alkene structures with one or more representative Z body in molecule, the alkene knot of Z body will be represented
At least one of structure is isomerized to represent the alkene structures of E body.Due to manufacturing method in this way, sulphur can be also generated certainly
By base, it is thus possible in the same manner as the case where making sulphur compound and radical initiator is acted on, by Z- alkene structures isomery
Turn to E- alkene structures.
Invention effect
It can be using extensive Z- olefin(e) compound as matrix come applying, E- is Olefination according to the present invention it is possible to provide
Close the manufacturing method of object.
Specific embodiment
The present invention is the representative Z for acting on sulphur compound and radical initiator in molecule with one or more
At least one of the alkene structures for representing Z body are isomerized to represent the alkene of E body by the alkene derivatives of the alkene structures of body
The manufacturing method of the isomerization body of structure.It is explained, in this specification, also will there is one or more in molecule
Representative Z body alkene structures alkene derivatives be known as " Z- alkene derivatives ", also by the representative Z body in Z- alkene derivatives
At least one of alkene structures represented E body alkene structures replace after alkene derivatives be known as that " E- alkene is derivative
Object " also will be known as " E/Z- compositions of olefines " comprising the composition of the two derivative.Above-mentioned isomerization body is equivalent to E- alkene
Derivative.
As long as the carbon-of alkene can be used there are E body and the substance of the stereoisomer of Z body in alkene derivatives
The carbon atom of two sides in carbon double bond respectively has the disubstituted olefin of one or two substituent group, three substituted olefines or four substitutions
Alkene.Wherein, the carbon atom of two sides in the carbon-to-carbon double bond of preferred alkenes respectively has the disubstituted olefin of a substituent group,
With the alkene derivatives of "-CH=CH- " i.e. in structure.In the present invention, Z- alkene derivatives can be used alone as raw material,
E/Z- compositions of olefines can be used as raw material.In E/Z- compositions of olefines, the content of Z- alkene derivatives is for example preferably 10
Quality % or more, preferably 20 mass % or more, preferably 30 mass % or more, preferably 40 mass % or more, preferably 50
Quality % or more, preferably 60 mass % or more, preferably 70 mass % or more, preferably 80 mass % or more, preferably 90
Quality % or more.In general, if manufacture alkene derivatives, can obtain E- alkene derivatives and Z- alkene derivatives are mixed with
E/Z- compositions of olefines, thus raw material can be used as.
Manufactured isomerization body (E- alkene derivatives) is obtained usually as E/Z- compositions of olefines in the present invention.?
In the case that raw material and product both sides are E/Z- compositions of olefines, the ratio of the E- alkene derivatives in composition can be mentioned
Height, i.e., at least part in the alkene structures of the representative Z body in Z- alkene derivatives can be changed into the alkene knot for representing E body
Structure, to manufacture isomerization body.
Alkene derivatives are preferably for example with alkyl (CH more than one or two of the alkyl2Base can be with
The mode of oxygen atom not direct neighbor is replaced by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C-, in the alkyl
One or more hydrogen atom can be arbitrarily substituted with halogen atoms.) etc. chain structure based on carbon skeletons change
It closes object or has and 1-CH in the group (is present in cyclohexylidene2Or non-conterminous 2 or more-CH2It can be with
Replaced by-O- or-S-.), (being present in 1-CH=or non-conterminous 2 or more-CH=in the group can be with for phenylene
Replaced by-N=, the hydrogen atom being present in the group can be replaced by fluorine atoms.), naphthylene (be present in 1 in the group
A-CH=or non-conterminous 2 or more-CH=can be replaced by-N=, and the hydrogen atom being present in the group can be by fluorine
Atom replaces.) etc. cyclic structure based on carbon skeletons compound.In alkene derivatives, "-a CH=can have
CH- ", it is possible to have more than two "-CH=CH- ".
In the case where alkene derivatives have more than two "-CH=CH- ", represented according to whole "-CH=CH- "
The alkene derivatives of E body, a part "-CH=CH- " represent E body and alkene that remaining "-CH=CH- " represents Z body is derivative
Object and "-the CH=CH- " of whole represent the mode of the alkene derivatives of Z body, and there are each "-CH=CH- " to represent E body or Z
A variety of isomers of body.In the present invention, Z- alkene derivatives are one or two of alkene derivatives or more "-CH=
CH- " represents the compound of Z body, the compound of Z body can be all represented for "-CH=CH- ", or include one or two
The compound of "-CH=CH- " of a above representative E body.In addition, E- alkene derivatives are at least one of alkene derivatives
"-CH=CH- " represents the compound of E body, the compound of E body can be all represented for "-CH=CH- ", or include one
The compound of a or more than two "-CH=CH- " for representing Z body, but be preferably the chemical combination that "-CH=CH- " all represents E body
Object.It is explained, the Z- alkene derivatives of the E- alkene derivatives as isomerization body and the raw material as isomerization body
It compares, it is at least to have "-the CH=CH- " for representing E body more.
Z- alkene derivatives in structure with more than one cyclic structure are preferably chemical combination represented by general formula (1)
Object.
[changing 2]
R1-(A1-Z1)m1-Y1-(Z2-A2)n1-R2 (1)
[in formula, R1And R2Each independently represent fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl, cyano, carboxyl,
Methanesulfonyloxy group, tolysulfonyl oxygroup or trifluorometanesulfonyloxy, carbon atom number 1 to 15 alkyl (be present in the alkane
1-CH in base2Or non-conterminous 2 or more-CH2Each independently can by-O- ,-S- ,-COO- ,-OCO- ,-
CO- ,-CH=CH- or-C ≡ C- replace, and 1 or 2 or more hydrogen atom in alkyl can be replaced by fluorine atoms.) or-S1-R3,
S1For the alkylidene of carbon atom number 1~4,
R3Indicate chlorine atom, bromine atom, iodine atom, hydroxyl, cyano, carboxyl, methanesulfonyloxy group, tolysulfonyl oxygroup
Or trifluorometanesulfonyloxy,
A1And A2The group being each independently in the group being made of following group:
(a) 1,4- cyclohexylidene (is present in 1-CH in the group2Or non-conterminous 2 or more-CH2It can be with
Replaced by-O- or-S-.)
(b) 1,4- phenylene (be present in 1-CH=or non-conterminous 2 or more-CH=in the group can by-
N=replaces, and the hydrogen atom being present in the group can be replaced by fluorine atoms.)
(c) naphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl or decahydronaphthalene -2,6- diyl (are present in naphthalene -2,6-
1-CH=or non-conterminous 2 or more-CH=in diyl or 1,2,3,4- naphthane-2,6- diyl can be taken by-N=
In generation, it is present in naphthalene -2,6- diyl or 1, the hydrogen atom in 2,3,4- naphthane -2,6- diyls can be replaced by fluorine atoms.),
Z1And Z2The alkylidene for each independently representing the straight-chain of singly-bound or carbon atom number 1~10, is present in the alkylidene
In 1-CH2Or non-conterminous 2 or more-CH2Each independently can by-O- ,-S- ,-COO- ,-OCO- ,-CO- ,-
CH=CH- or-C ≡ C- replaces, and is present in Z1And Z2In hydrogen atom can be replaced by fluorine atoms,
m1And n1Each independently represent 0 to 5 integer, but m1+n1Indicate 1 to 5,
Y1It indicates:
[changing 3]
(stain in formula indicates A1、A2、Z1、Z2、R1And R2In and Y1The atom bound directly.),
In A1And A2In the case where multiple, they can be the same or different, in Z1And Z2There is a situation where multiple
Under, they can be the same or different.]
E- alkene derivatives corresponding with Z- alkene derivatives represented by general formula (1) are (hereinafter also referred to as " general formula (1)
The E body of represented compound ".) it is Y in general formula (1)1It indicates
[changing 4]
Compound (stain in formula indicates A1、A2、Z1、Z2、R1And R2In and Y1The atom bound directly.).
The E body of compound represented by general formula (1) is as the chemical combination for being used for example as liquid-crystal composition used for liquid crystal display element
Object and intermediate for synthesizing the compound are useful.From the viewpoint of improving response speed, liquid-crystal composition is excellent
Select viscosity low, in addition, in order to maintain nematic phase with wide temperature range, preferably each ingredient has the high miscibility with other compositions.
In addition, the type of liquid-crystal composition can be selected in conjunction with the display mode of liquid crystal display panel.For example, being VA in liquid crystal display panel
(Vertical Alignment, vertically oriented) mode or PSA (Polymer-Sustained Alignment, polymer stabilizing
Orientation) in the case where mode, the liquid-crystal composition being negative using dielectric constant anisotropy (Δ ε) value, for IPS (In-
Plane-Switching, plane conversion) it the use of Δ ε value is positive or negative liquid-crystal composition in the case where mode.
In general formula (1), in order to reduce the viscosity of liquid-crystal composition, A1And A2It is each independently preferably anti-form-1,4- is sub-
Cyclohexyl, non-substituted naphthalene -2,6- diyl or non-substituted Isosorbide-5-Nitrae-phenylene, in order to improve the mixing with other liquid crystal compositions
Property, preferably anti-form-1,4- cyclohexylidene or non-substituted Isosorbide-5-Nitrae-phenylene.
In the case where manufacturing the compound that Δ ε is positive using the E body of compound represented by general formula (1), in order to increase
Big Δ ε, A1And A2It is preferably each independently
[changing 5]
Further preferably
[changing 6]
In the case where manufacturing the compound that Δ ε is negative using the E body of compound represented by general formula (1), A1And A2Respectively
From independently preferably following structures.
[changing 7]
Long-term reliability when liquid crystal display element is made to improve, liquid-crystal composition does not preferably contain nitrogen-atoms.
In general formula (1), in order to reduce the viscosity of liquid-crystal composition, R1And R2Preferably the alkyl of carbon atom number 1~12,
The alkenyloxy group of the alkenyl of carbon atom number 2~12, the alkoxy of carbon atom number 1~12 or carbon atom number 2~12, more preferably carbon are former
The alkyl of subnumber 1~8 or the alkenyl of carbon atom number 2~8, the particularly preferably alkyl of carbon atom number 1~5 or carbon atom number 2~5
Alkenyl.Furthermore it is preferred that being straight-chain.In addition, R1And R2In at least one party be preferably methanesulfonyloxy group, tolysulfonyl
Oxygroup, trifluorometanesulfonyloxy, hydroxyl, trifluoromethoxy, carboxyl.
In the case where manufacturing the compound that Δ ε is positive, in order to increase Δ ε, R1Or R2In either preferably fluorine it is former
Son, cyano, trifluoromethyl or trifluoromethoxy, in order to reduce viscosity, preferably fluorine atom.
In general formula (1), in order to reduce the viscosity of liquid-crystal composition and improve the miscibility with other liquid crystal compositions, Z1
And Z2It is each independently preferably-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2,-CF=CF- ,-C ≡ C- or singly-bound,
Further preferably-CF2O-、-OCF2-、-CH2CH2Or singly-bound, particularly preferably singly-bound, in order to show big Δ ε, preferably
Singly-bound or-CF2O-.With Y1The Z bound directly1And Z2It is preferred that indicate the alkylidene or singly-bound of the straight-chain of carbon atom number 1~10,
It is preferred that indicating the alkylidene or singly-bound of the straight-chain of carbon atom number 1~4.
Compound represented by general formula (1) is preferably selected from by general formula below (1a), general formula (1b), general formula (1c), leads to
Compound in the group of the composition of compound represented by formula (1d) or general formula (1e).
[changing 8]
[in formula, A1a2And Z1a2It indicates and the A in above-mentioned general formula (1)2And Z2Identical meaning,
R1a1Indicate the alkyl of carbon atom number 1 to 15,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1a2Indicate the alkyl of carbon atom number 1 to 8,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
W1a1Indicate the alkylidene of the straight-chain of singly-bound or carbon atom number 1 to 4,1-CH being present in the alkylidene2-
Or non-conterminous 2 or more-CH2It can be replaced each independently by-O- ,-S- ,-COO- ,-OCO- ,-CO- or-C ≡ C-,
It is present in W1a1In hydrogen atom can be replaced by fluorine atoms,
Y1a2Indicate singly-bound or-CH=CH-,
n1a1Indicate 1 to 5 integer.]
[changing 9]
[in formula, A1b1、A1b2、Z1b1And Z1b2It indicates and the A in above-mentioned general formula (1)1、A2、Z1And Z2Identical meaning,
R1b1And R1b2The alkyl for each independently representing carbon atom number 1 to 8,1-CH being present in the alkyl2Or not
2 or more adjacent-CH2It each independently can be by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-
Replace,
W1b1And W1b2The alkylidene for each independently representing the straight-chain of singly-bound or carbon atom number 1 to 4 is present in the alkylene
1-CH in base2Or non-conterminous 2 or more-CH2It each independently can be by-O- ,-S- ,-COO- ,-OCO- ,-CO-
Or-C ≡ C- replaces, and is present in W1b1And W1b2In hydrogen atom can be replaced by fluorine atoms,
Y1b2And Y1b3Singly-bound or-CH=CH- are each independently represented,
m1b1And n1b1Each independently represent 0 to 5 integer, but m1b1+n1b1Indicate 1 to 5.]
[changing 10]
[in formula, A1c2And Z1c2It indicates and the A in above-mentioned general formula (1)2And Z2Identical meaning,
A1c3Indicate the group for being selected from following group,
[changing 11]
R1c1Indicate the alkyl of carbon atom number 1 to 15,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1c2Indicate fluorine atom, trifluoromethoxy or cyano,
n1c1Indicate 1 to 5 integer.]
[changing 12]
[in formula, A1d2And A1d3It indicates and the A in general formula (1)2Identical meaning, Z1d2、Z1d3And Z1d4It indicates and general formula (1)
In Z2Identical meaning,
R1d1Indicate the alkyl of carbon atom number 1 to 15,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1d2Indicate the alkyl of carbon atom number 1 to 8,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
W1d1Indicate the alkylidene of the straight-chain of singly-bound or carbon atom number 1 to 4,1-CH being present in the alkylidene2-
Or non-conterminous 2 or more-CH2It can be taken each independently by-O- ,-S- ,-COO- ,-OCO- ,-CO- or-C ≡ C-
In generation, is present in W1d1In hydrogen atom can be replaced by fluorine atoms,
Y1d2Indicate singly-bound or-CH=CH-,
n1d1And n1d2Each independently represent 0 to 4 integer.]
[changing 13]
[in formula, A1e2And Z1e2It indicates and the A in above-mentioned general formula (1)2And Z2Identical meaning,
R1e1Indicate the alkyl of carbon atom number 1 to 15,1-CH being present in the alkyl2Or non-conterminous 2 or more
- CH2It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1e2Indicate hydroxyl, methylol, bromomethyl, chloromethyl, methanesulfonyloxymethyl, tosyloxymethyl, chlorine
Atom, bromine atom, iodine atom, trifluorometanesulfonyloxy or
[changing 14]
(stain in formula indicates A1e2In and R1e2The carbon atom bound directly, R1e3Indicate the alkyl of carbon atom number 1 to 5
Or hydrogen atom.),
n1e1Indicate 1 to 4 integer.]
By the particular instantiation of preferred compound in hereinafter, but the present invention is not limited thereto.
In general formula (1a), each compound represented by general formula (1a-1)~general formula (1a-23) preferably below.
[changing 15]
(in formula, R1a1、Z1a2And R1a2It indicates and the R in above-mentioned general formula (1a)1a1、Z1a2And R1a2Identical meaning.)
[changing 16]
[in formula, R1a1、Z1a2And R1a2It indicates and the R in above-mentioned general formula (1a)1a1、Z1a2And R1a2Identical meaning.]
[changing 17]
[in formula, R1a1、Z1a2And R1a2It indicates and the R in above-mentioned general formula (1a)1a1、Z1a2And R1a2Identical meaning.]
[changing 18]
[in formula, R1a1、Z1a2And R1a2It indicates and the R in above-mentioned general formula (1a)1a1、Z1a2And R1a2Identical meaning.]
[changing 19]
[in formula, R1a1、Z1a2And R1a2It indicates and the R in above-mentioned general formula (1a)1a1、Z1a2And R1a2Identical meaning.]
In general formula (1b), each compound represented by general formula (1b-1)~general formula (1b-10) preferably below.
[changing 20]
[in formula, R1b1And R1b2It indicates and the R in above-mentioned general formula (1b)1b1And R1b2Identical meaning.]
[changing 21]
[in formula, R1b1And R1b2It indicates and the R in above-mentioned general formula (1b)1b1And R1b2Identical meaning.]
In general formula (1c), each compound represented by general formula (1c-1)~general formula (1c-65) preferably below.
[changing 22]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2Z1c1And A1c3It is identical to contain
Justice.]
[changing 23]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 24]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 25]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 26]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 27]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 28]
[in formula, R1c1、R1c2、Z1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2、Z1c2And A1c3It is identical to contain
Justice.]
[changing 29]
[in formula, R1c1、R1c2And A1c3It indicates and the R in above-mentioned general formula (1c)1c1、R1c2And A1c3Identical meaning.]
In general formula (1d), each compound represented by general formula (1d-1)~general formula (1d-35) preferably below.
[changing 30]
[in formula, R1d1、R1d2And Z1d2It indicates and the R in above-mentioned general formula (1d)1d1、R1d2And Z1d2Identical meaning.]
[changing 31]
[in formula, R1d1、R1d2And Z1d2It indicates and the R in above-mentioned general formula (1d)1d1、R1d2And Z1d2Identical meaning.] [change
32]
[changing 33]
[in formula, R1d1、R1d2And Z1d2It indicates and the R in above-mentioned general formula (1d)1d1、R1d2And Z1d2Identical meaning.]
In general formula (1e), each compound represented by general formula (1e-1)~general formula (1e-13) preferably below.
[changing 34]
[in formula, R1e1、R1e2And Z1e2It indicates and the R in above-mentioned general formula (1e)1e1、R1e2And Z1e2Identical meaning.]
As sulphur compound, be not particularly limited as long as the compound containing more than one sulphur atom, but from be easy
Generate Thiyl Radical and reaction facilitation effect it is excellent from the aspect of, preferably organosulfur compound, more preferably selected from following
Compound in compound group represented by general formula (A)~(H).In addition, sulphur compound preferably contains from the aspect of similarly
The compound of S -- S, the change being more preferably selected from compound group represented by the following general formula (A), (C), (D), (E) and (F)
Close object, the compound being further preferably selected from compound group represented by the following general formula (A), (D) and (F).It is explained
, the compound containing S -- S can be the compound with a S -- S, or with more than two S -- Ss
Compound.In addition, two S atoms in S -- S can be not oxidized S atom, i.e.-S- each independently, or
The S atom of oxidation, i.e.-S (=O)-or-S (=O)2-。
[changing 35]
[in formula, RaAnd RbIt each independently represents selected from substituted or non-substituted phenyl, substituted or non-substituted carbon atom
The alkyl of number 1 to 8, the alkenyl of substituted or non-substituted carbon atom number 2 to 8 and the group in hydrogen atom.]
In RaAnd/or RbIn the case where phenyl, the phenyl is preferably non-substituted, or by the carbon of straight-chain or branched
The carbon atom of the alkoxy of the carbon atom number 1 to 8 of the alkyl of atomicity 1 to 8, straight-chain or branched, straight-chain or branched
Alkenyl, chlorine atom, amino or hydroxyl of number 2 to 8 etc. replace.
In RaAnd/or RbIn the case where alkyl or alkenyl, which can may be branch for straight-chain
Shape.In addition, in RaAnd/or RbIn the case where alkyl or alkenyl, the alkyl or alkenyl is preferably non-substituted, or by chlorine atom,
Amino or hydroxyl etc. replace.
As the concrete example of these sulphur compounds, Diphenyl disulfide ether, aralkyl sulfid, benzenethiol, (phenyl sulphur can be enumerated
Acyl group) aralkyl sulfid, two sulfone of diphenyl, diphenyl sulfoxide, diphenyl sulfone, di-p-tolyl disulfide, 2,2'- diamino hexichol
Base disulfide, 4,4'- diamino-diphenyl disulfide, 4,4'- dihydroxydiphenyl disulfide, 3,3'- dihydroxydiphenyl two
Thioether, bis- (p-methoxyphenyl) disulfides, 4,4'- dichlorophenyl disulfide, 4,4'- difluorodiphenyl base disulfide, bis- (4-
Carboxyl phenyl) disulfide, dimethyl disulfide, diethyl disulphide, dipropyl disulfide, diisopropyl disulfide ether, two allyls
Base disulfide etc..Wherein, preferably two sulfone of Diphenyl disulfide ether, (phenyl sulfonyl) aralkyl sulfid or diphenyl, more preferably
Diphenyl disulfide ether.
The additive amount of sulphur compound used in isomerization reaction is for example total relative to the alkene derivatives as raw material
Amount can be set to 0.1~10 mole of %.The lower limit value of the additive amount of sulphur compound is total relative to the alkene derivatives as raw material
Amount is preferably 0.2 mole of % or more, 0.5 mole of % or more, 1% or more or 2% or more.In addition, the additive amount of sulphur compound
Upper limit value is preferably 8 moles of % or less, 7 moles of % or less, 6 moles of % or less relative to the alkene derivatives total amount as raw material
Or 5 moles of % or less.
As radical initiator, known substance can be used.As its concrete example, it is even that 2,2 '-can be enumerated
Nitrogen bis-isobutyronitrile, 2,2 '-azos are double-and (2,4- methyl pentane nitrile), 2,2 '-azos are double-(4- methoxyl group -2,4- dimethyl-penten
Nitrile), 2,2 '-azos bis- (2- methylbutyronitriles), 1,1 '-azos it is double-(hexamethylene -1- nitrile), bis- (the 2- first of dimethyl 2,2 '-azo
Base propionic ester), 2,2 '-azos bis- (N- butyl -2- methyl propanamides), the azo compounds such as 4,4 '-azos bis- (4- cyanopentanoic acids)
Object；Benzoyl peroxide, lauroyl peroxide, the peroxidating pivalic acid tert-butyl ester, 1,1 '-bis--(tert-butyl hydroperoxide) hexamethylenes,
The organic peroxides such as peroxidating -2 ethyl hexanoic acid tert-pentyl ester, the tertiary own ester of peroxidating -2 ethyl hexanoic acid, but promote effect from reaction
From the aspect of fruit is excellent, preferably azo-compound.It is explained, radical initiator can combine isomerization reaction
Reaction temperature, the type of matrix etc. being suitable for substance that selection has suitable half life temperature.
The additive amount of radical initiator used in isomerization reaction is for example derivative relative to the alkene as raw material
Object total amount can be set to 0.1~10 mole of %.The lower limit value of the additive amount of radical initiator is relative to the alkene as raw material
Derivative total amount is preferably 0.2 mole of % or more, 0.5 mole of % or more, 1% or more or 2% or more.In addition, free radical causes
The upper limit value of the additive amount of agent relative to the alkene derivatives total amount as raw material be preferably 8 moles of % or less, 7 moles of % with
Under, 6 moles of % or less or 5 mole of % or less.
In method of the invention, the temperature for acting on sulphur compound and radical initiator for example can be set to 20 DEG C
~120 DEG C.From the viewpoint of the side reaction for inhibiting anticipation, above-mentioned temperature is preferably 20 DEG C~90 DEG C, more preferably 20 DEG C~
70℃。
In order to control reaction, method of the invention preferably carries out in the presence of solvent.As used solvent, Ke Yihe
The aromatic system solvent such as toluene, benzene, dimethylbenzene is used suitablely；Hexane, heptane, hexamethylene etc. are saturated hydrocarbon system solvent；Dichloro
The chlorine series solvents such as methane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes；Tetrahydrofuran (THF), diethyl
The ether series solvents such as base ether, Di Iso Propyl Ether, t-butyl methyl ether；The alcohol series solvents such as methanol, ethyl alcohol, particularly preferably toluene,
THF, methanol.These solvents can be used in mixed way as needed.
Method of the invention can carry out in air, but from the viewpoint of improving reactivity and inhibiting side reaction,
It is preferred that being carried out under the inert atmospheres such as nitrogen.
It is explained, method of the invention is also possible to the manufacturing method of following isomerization body: making containing S -- S
Compound is acted under heating in molecule, and there is one or more to represent the alkene derivatives of the alkene structures of Z body, will
At least one of the alkene structures for representing Z body are isomerized to represent the alkene structures of E body.In this method, free radical is not used
Initiator, and to carry out isomerization under heating as necessary condition, it in addition to this, can be according to same as above-mentioned method
Condition reacted.Heating temperature can be set to such as 50 DEG C~120 DEG C.
It by means of the present invention, can be by the mass ratio relative to the E- alkene derivatives of the quality of Z- alkene derivatives
Rate (E body/Z body) is improved to 75/25 or more, i.e., improves the content of the E- alkene derivatives in E/Z- compositions of olefines to 75 matter
Measure % or more.The quality ratio of the E- alkene derivatives of quality relative to Z- alkene derivatives is preferably higher, preferably (E
Body/Z body)=80/20 or more, more preferably 85/15 or more.The E- alkene derivatives of quality relative to Z- alkene derivatives
Quality ratio (E body/Z body) can use gas-chromatography to quantify.
In order to remove Z- alkene derivatives remaining in the E/Z- compositions of olefines after isomerization reaction, target E- is obtained
Alkene derivatives can further refine E/Z- compositions of olefines.As refining methd, chromatography, recrystallization, steaming can be enumerated
Evaporate, distil, reprecipitation, absorption, liquid separation processing etc..Using refining agent, as refining agent, can enumerate silica gel,
Aluminium oxide, active carbon, atlapulgite, cerite, zeolite, mesoporous silicon oxide, carbon nanotube, carbon nanohorn, binchotan, wood
It is charcoal, graphene, ion exchange resin, Emathlite, silica, diatomite, perlite, cellulose, organic polymer, porous
Matter gel etc..If repeating such purification, the problems such as decline there are the separation yield of E- alkene derivatives, but according to
It is derivative relative to the E- alkene of the quality of Z- alkene derivatives method of the invention, it is possible to more be improved by isomerization reaction
The quality ratio of object, therefore the number of purification can be reduced, it can be improved the yield of E- alkene derivatives.
Embodiment
Hereinafter, the present invention is described in further detail in citing, but the present invention is not limited thereto.
About gas chromatographic analysis, implement according to condition below.
Sample modulation: 1 mass % acetone soln
Column import volume: 1 μ L
Device: GC2010 (Shimadzu Seisakusho Ltd.)
Column: J&WDB-17MS (the μ m 0.25mm of 30m × 0.25)
Carrier gas: nitrogen
Column pressure: (226kPa), column flow: 3.19mL/ minute, average speed: 58.8cm/ seconds
Split ratio: 50:1
Inlet temperature: 300 DEG C, detector temperature: 320 DEG C of (FID)
Column heating setting: 100 DEG C (1 minute) → 10 DEG C/min → 300 DEG C (14 minutes)
(embodiment 1)
[changing 36]
By E/Z compositions of olefines (3g, E body/body=5/95 Z), Diphenyl disulfide ether (31mg) and the methanol of formula (1)
(7.5mL) after mixing, is heated to 47 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.47 DEG C of additions of temperature inside
After 2,2- azos bis- (2,4- methyl pentane nitrile) (35mg), stir within 24 hours.Reaction solution is divided using gas-chromatography
It analyses, as a result E body/body=85/15 Z.Toluene (10mL) and water (10mL), liquid separation, according to water are added into the reaction solution
The sequential purge organic layer of (10mL), saturated salt solution (10mL) are added anhydrous sodium sulfate and are dried.Sodium sulphate is filtered out
Afterwards, it is refined using silica gel column chromatography, to obtain E/Z compositions of olefines (quantitative yield, E body/body=85/ Z of formula (2)
15)。
(embodiment 2)
[changing 37]
(" THP " in formula (3) and (4) indicates 2- THP trtrahydropyranyl.)
By E/Z compositions of olefines (3g, E body/body=10/90 Z), Diphenyl disulfide ether (22mg) and the THF of formula (3)
(10mL) after mixing, is heated to 51 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.It is added 2 for 51 DEG C of temperature inside,
After 2- azo bis- (2,4- methyl pentane nitrile) (25mg), stir within 10 hours.Reaction solution is analyzed using gas-chromatography,
As a result E body/body=83/17 Z.Be added toluene (10mL) and water (10mL) into the reaction solution, liquid separation, according to water (10mL),
The sequential purge organic layer of saturated salt solution (10mL) is added anhydrous sodium sulfate and is dried.After sodium sulphate is filtered out, silicon is utilized
Rubber column gel column chromatographic refining, to obtain the E/Z compositions of olefines (quantitative yield, E body/body=83/17 Z) of formula (4).
(embodiment 3)
[changing 38]
By the E/Z compositions of olefines (3g, E body/body=4/96 Z) of formula (5), (phenyl sulfonyl) aralkyl sulfid (99mg) and
Toluene (10mL) after mixing, is heated to 85 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.Add for 85 DEG C of temperature inside
After entering 2,2- azo bis- (2,4- methyl pentane nitrile) (98mg), stir within 5 hours.Reaction solution is divided using gas-chromatography
It analyses, as a result E body/body=85/15 Z.Water (10mL) is added into the reaction solution, liquid separation, according to water (10mL), saturated salt solution
The sequential purge organic layer of (10mL) is added anhydrous sodium sulfate and is dried.After sodium sulphate is filtered out, silica gel column chromatography essence is utilized
System, to obtain the E/Z compositions of olefines (quantitative yield, E body/body=85/15 Z) of formula (6).
(embodiment 4)
[changing 39]
By E/Z compositions of olefines (3g, E body/body=5/95 Z), Diphenyl disulfide ether (35mg) and the methanol of formula (7)
(7.5mL) after mixing, is heated to 48 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.48 DEG C of additions of temperature inside
After 2,2- azos bis- (2,4- methyl pentane nitrile) (40mg), stir within 30 hours.Reaction solution is divided using gas-chromatography
It analyses, as a result E body/body=84/16 Z.Toluene (10mL) and water (10mL), liquid separation, according to water are added into the reaction solution
The sequential purge organic layer of (10mL), saturated salt solution (10mL) are added anhydrous sodium sulfate and are dried.Sodium sulphate is filtered out
Afterwards, it is refined using silica gel column chromatography, to obtain E/Z compositions of olefines (quantitative yield, E body/body=84/ Z of formula (8)
16)。
(embodiment 5)
[changing 40]
By E/Z compositions of olefines (3g, E body/body=5/95 Z), Diphenyl disulfide ether (36mg) and the toluene of formula (9)
(7.5mL) after mixing, is heated to 51 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.51 DEG C of additions of temperature inside
After 2,2- azos bis- (2,4- methyl pentane nitrile) (36mg), stir within 20 hours.Reaction solution is divided using gas-chromatography
It analyses, as a result E body/body=85/15 Z.Water (10mL) is added into the reaction solution, liquid separation, according to water (10mL), saturated salt solution
The sequential purge organic layer of (10mL) is added anhydrous sodium sulfate and is dried.After sodium sulphate is filtered out, silica gel column chromatography essence is utilized
System, to obtain the E/Z compositions of olefines (quantitative yield, E body/body=85/15 Z) of formula (10).
(embodiment 6)
[changing 41]
By the E/Z compositions of olefines (3g, E, E body/E, Z body/Z, body=8/40/52 Z) of formula (11)), Diphenyl disulfide ether
(24mg) and THF (15mL) after mixing, are heated to 51 DEG C of interior temperature at room temperature, in the reaction vessel after nitrogen is replaced.Inside
After warm 51 DEG C of addition 2,2- azos bis- (2,4- methyl pentane nitrile) (28mg), stir within 20 hours.Using gas-chromatography to anti-
Liquid is answered to be analyzed, as a result E, E body/E, Z body/Z, body=77/22/1 Z.Toluene (10mL) and water are added into the reaction solution
(10mL), liquid separation are added anhydrous sodium sulfate and carry out according to water (10mL), the sequential purge organic layer of saturated salt solution (10mL)
It is dry.It after sodium sulphate is filtered out, is refined using silica gel column chromatography, to obtain the E/Z compositions of olefines (quantitative yield of formula (12)
, E, E body/E, Z body/Z, body=77/22/1 Z).
(comparative example 1)
[changing 42]
By E/Z compositions of olefines (3g, E body/body=5/95 Z), the benzene sulfinic acid sodium salt (279mg), toluene of formula (1)
After (7.5mL) is mixed at room temperature, it is heated to 95 DEG C of interior temperature.95 DEG C of temperature is slowly added to the hydrochloric acid (7.5mL) of 10 mass % inside,
It stirs within further progress 5 hours.Reaction solution is analyzed using gas-chromatography, as a result the E/Z alkene as the formula of object (2)
Compositions of hydrocarbons is E body/body=79/21 Z.In addition, generating 13% formula (13) compound as by-product.It is molten to the reaction
THF (10mL) is added in liquid and water (10mL), liquid separation, the sequential purge according to water (10mL), saturated salt solution (10mL) are organic
Layer is added anhydrous sodium sulfate and is dried.It after sodium sulphate is filtered out, is refined using silica gel column chromatography, to obtain the E/ of formula (2)
Z compositions of olefines (yield 78%, E body/body=79/21 Z).
(comparative example 2)
[changing 43]
By E/Z compositions of olefines (3g, E body/body=10/90 Z), benzene sulfinic acid sodium salt (190mg) and the THF of formula (3)
After (7.5mL) is mixed at room temperature, it is heated to 66 DEG C of interior temperature.Inside temperature 66 DEG C be slowly added to concentrated hydrochloric acid (0.5mL), further into
It stirs within row 3 hours.Reaction solution is analyzed using gas-chromatography, does not as a result obtain formula (4) compound as object,
As main peak, the E/Z compositions of olefines of formula (14) has been obtained.
It can see from above result, it can not under the conditions of about the isomerization reaction as previous acidity and high temperature
The matrix of application is obtained using height ratio as target if being able to carry out olefin isomerization using condition of the invention
E- alkene derivatives.
Claims (6)
1. a kind of manufacturing method of isomerization body, make sulphur compound and radical initiator act in molecule have one or
The alkene derivatives of more than two alkene structures for representing Z body, at least one of the alkene structures for representing Z body are different
Structure turns to the alkene structures for representing E body.
2. the manufacturing method according to claim 1, the temperature 20 for acting on sulphur compound and radical initiator
DEG C~120 DEG C.
3. manufacturing method according to claim 1 or 2, radical initiator is azo-compound.
4. manufacturing method described in any one of claim 1 to 3, sulphur compound is selected from general formula (A)~general formula (H) institute
One kind or two or more compound in the compound group of expression:
[changing 1]
Ra-S-S-Rb (A)
Ra-S-Rb (B)
In formula, RaAnd RbIt each independently represents selected from substituted or non-substituted phenyl, substituted or non-substituted carbon atom number 1 to 8
Alkyl, substituted or non-substituted carbon atom number 2 to 8 alkenyl and the group in hydrogen atom.
5. manufacturing method described in any one of claim 1 to 3, sulphur compound is the compound containing S -- S.
6. a kind of manufacturing method of isomerization body, acting on the compound containing S -- S under heating has one in molecule
Or the alkene derivatives of more than two alkene structures for representing Z body, by least one of the alkene structures for representing Z body
It is isomerized to represent the alkene structures of E body.
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| JP2016-196604 | 2016-10-04 | ||
| JP2016196604 | 2016-10-04 | ||
| PCT/JP2017/034061 WO2018066371A1 (en) | 2016-10-04 | 2017-09-21 | Process for producing e-olefin compound |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878001A (en) * | 2019-11-29 | 2020-03-13 | 温州大学 | Process for the isomerization of (Z) -olefins to (E) -olefins |
| CN111978142A (en) * | 2020-08-07 | 2020-11-24 | 厦门大学 | Method for isomerizing cis-olefin into trans-olefin |
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| US8137583B2 (en) * | 2008-05-29 | 2012-03-20 | Jnc Corporation | Liquid crystal four-ring compound having fluorine, liquid crystal composition, and liquid crystal display device |
| JP2014019646A (en) * | 2012-07-12 | 2014-02-03 | Jnc Corp | Liquid crystal compound having fluorovinyl group, liquid crystal composition and liquid crystal display element |
| EP2868647B1 (en) * | 2013-10-30 | 2017-07-12 | Shin-Etsu Chemical Co., Ltd. | Method for producing (E)-2-isopropyl-5-methyl-2,4-hexadienyl acetate |
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- 2017-09-21 CN CN201780053379.4A patent/CN109689603A/en not_active Withdrawn
- 2017-09-21 JP JP2018513677A patent/JP6443708B2/en not_active Expired - Fee Related
- 2017-09-21 WO PCT/JP2017/034061 patent/WO2018066371A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110878001A (en) * | 2019-11-29 | 2020-03-13 | 温州大学 | Process for the isomerization of (Z) -olefins to (E) -olefins |
| CN111978142A (en) * | 2020-08-07 | 2020-11-24 | 厦门大学 | Method for isomerizing cis-olefin into trans-olefin |
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| WO2018066371A1 (en) | 2018-04-12 |
| JP6443708B2 (en) | 2018-12-26 |
| JPWO2018066371A1 (en) | 2018-10-04 |
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