CN107892646A - The manufacture method of isomerization body - Google Patents
The manufacture method of isomerization body Download PDFInfo
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- CN107892646A CN107892646A CN201710875111.0A CN201710875111A CN107892646A CN 107892646 A CN107892646 A CN 107892646A CN 201710875111 A CN201710875111 A CN 201710875111A CN 107892646 A CN107892646 A CN 107892646A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/09—Geometrical isomers
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Abstract
It is an object of the invention to provide a kind of manufacture method of E olefin(e) compounds, can obtain target E olefin(e) compounds compared with conventional method with height ratio.A kind of manufacture method of isomerization body, make alkene derivatives isomerization in the case where solvent be present of the alkene structures with one or more performance Z bodies in molecule, isomerization body is obtained so as to show at least one alkene structures for being isomerizated into performance E bodies of the alkene structures of Z bodies, in this method, the isomerization body is set optionally to separate out while carrying out isomerization.
Description
Technical field
The present invention relates to the manufacture intermediate as synthetics such as medicine, agricultural chemicals, liquid crystal materials and raw material thing are useful
E- olefin(e) compounds manufacture method.
Background technology
E- olefin(e) compounds majority medicine, agricultural chemicals, liquid crystal material field in show excellent characteristic, be useful change
Compound.Particularly for liquid crystal material, it is known that E- olefin(e) compounds show high limpid compared with corresponding saturated compounds
Point, relatively low viscosity and big elastic constant, it is extremely important compound.In general, E- olefin(e) compounds are by as follows
Process manufactures, i.e.,：By for the composition comprising E- olefin(e) compounds and corresponding Z- olefin(e) compounds, carrying out having used virtue
Isomerization reaction of the base sulfinic acid class as catalyst, make ratio rise (the non-patent text of the E- olefin(e) compounds in composition
Offer 1,2).Additionally, it is known that aryl sulfinic acid is unstable, therefore is typically bought, keeping in the form of corresponding arylsulfinate,
Used during use in reaction system with the acid reaction such as hydrochloric acid after generating new aryl sulfinic acid.Now, it is usually used to include
Composition, sulfinate, acid and the solvent of E- olefin(e) compounds and corresponding Z- olefin(e) compounds are heated to after mixed at room temperature
The process (patent document 1, non-patent literature 1 and non-patent literature 2) of predetermined reaction temperature.
[changing 1]
In addition, in patent document 2, it is proposed that make by using aryl sulfinic acid class as the isomerization reaction of catalyst and
The ratio of E- olefin(e) compounds in the obtained composition comprising E- olefin(e) compounds and corresponding Z- olefin(e) compounds is higher
Method.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application Publication 2012-528798 publications
Patent document 2：Japanese Unexamined Patent Publication 2016-121076 publications
Non-patent literature
Non-patent literature 1：H.Nozaki, Y.Nishikawa, M.Kawanishi, R.Noyori, Tetrahedron (four
Face body), 23,2173 (1967)
Non-patent literature 2：T.W.Gibson,P.Strassburger,J.Org.Chem.,41,791(1976)
The content of the invention
The invention problem to be solved
In addition, as also referred in patent document 2, in order to obtain pure E- olefin(e) compounds, it is necessary to above-mentioned
After isomerization reaction, many purification operations are repeated in order to remove the Z- olefin(e) compounds of remaining.Therefore, yield rate is disliked
Change, and then cost uprises., it is necessary to be refined to high particularly in the case of using E- olefin(e) compounds as liquid crystal material
Purity, therefore E- olefin(e) compounds are preferably obtained with higher ratio in the stage of isomerization reaction.
Then, can be with conventional method it is an object of the invention to provide a kind of manufacture method of E- olefin(e) compounds
Target E- olefin(e) compounds are obtained compared to height ratio.
The method for solving problem
The present inventor etc. has made intensive studies, and as a result finds, passes through the manufacture method of following isomerization body, Neng Gouyu
Conventional method is compared obtains desired isomerized body, i.e. E- olefin(e) compounds with height ratio, and the manufacture method is：Make in molecule
Alkene derivatives isomerization in the case where solvent be present of alkene structures with one or more performance Z bodies, from
And show at least one alkene structures for being isomerizated into performance E bodies of the alkene structures of Z bodies and obtain isomerization body, this method
In, isomerization body is optionally separated out while carrying out isomerization, so as to complete the present invention.
The reasons why can obtaining desired isomerized body compared with conventional method with height ratio by the manufacture method, may not
It is clear, but the present inventor etc. thinks, if making isomerization body optionally separate out, under the concentration of the isomerization body in solution
Drop, therefore balanced deflection, more alkene derivatives are converted into thermodynamically stable isomerization body.
Invention effect
According to the present invention, it is possible to provide a kind of manufacture method of E- olefin(e) compounds, can be compared with conventional method with height
Ratio obtains target E- olefin(e) compounds.
Brief description of the drawings
Fig. 1 is represented on Examples 1 and 2, and the warp of the ratio of E- alkene derivatives is determined by gas chromatographic analysis
The figure of Shi Bianhua result.
Embodiment
The present invention is a kind of manufacture method of isomerization body, makes have one or more performance Z bodies in molecule
The alkene derivatives of alkene structures isomerization in the case where solvent be present, so as to show at least one of the alkene structures of Z bodies
It is isomerizated into the alkene structures of performance E bodies and obtains isomerization body, in this method, while makes isomerization body optionally separate out one
Side carries out isomerization.It should be noted that in this specification, will there is the alkene of one or more performance Z bodies in molecule
The alkene derivatives of hydrocarbon structure are also referred to as " Z- alkene derivatives ", will show the alkene structures of Z bodies extremely in Z- alkene derivatives
Alkene derivatives after few one alkene structures by performance E bodies substitute are also referred to as " E- alkene derivatives ", will include both
The composition of derivative is also referred to as " E/Z- compositions of olefines ".Above-mentioned isomerization body is equivalent to E- alkene derivatives.
The isomerization method of Z- alkene derivatives is not particularly limited, and can be applicable known method, but from can
React in a mild condition, the aspect that E- alkene derivatives separate out is set out, preferably by making sulphur compound and free radical
The method that initiator is had an effect makes Z- alkene derivatives isomerization.
Alkene derivatives are simply by the presence of E bodies and the stereoisomer of Z bodies, in the carbon-to-carbon double bond that can use alkene
Two carbon atoms respectively have one or two substituent disubstituted olefin, three substituted olefines or four substituted olefines.Wherein,
Two carbon atoms in the carbon-to-carbon double bond of preferred alkenes have the disubstituted olefin of a substituent respectively, i.e., have in structure
The alkene derivatives of "-CH=CH- ".In the present invention, Z- alkene derivatives can be used separately as raw material, can also be by E/
Z- compositions of olefines uses as raw material.In E/Z- compositions of olefines, the content of Z- alkene derivatives is preferably such as 10 matter
More than % is measured, preferably more than 20 mass %, preferably more than 30 mass %, preferably more than 40 mass %, preferably 50 matter
More than % is measured, preferably more than 60 mass %, preferably more than 70 mass %, preferably more than 80 mass %, preferably 90 matter
Measure more than %.Generally, when manufacturing alkene derivatives, it can obtain the E/Z- that E- alkene derivatives and Z- alkene derivatives are mixed
Compositions of olefines, therefore can be used as raw material.
The isomerization body (E- alkene derivatives) manufactured in the present invention obtains usually as E/Z- compositions of olefines.In raw material
In the case of being E/Z- compositions of olefines with both products, because the ratio of the E- alkene derivatives in composition is carried
At least a portion that the alkene structures of Z bodies are showed in height, i.e. Z- alkene derivatives is converted into the alkene structures of performance E bodies, from
And isomerization body is manufactured.
Alkene derivatives are preferably for example with alkyl (one or more the CH in the alkyl2Base can be with
The mode that oxygen atom does not abut directly against is substituted by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C-, in the alkyl
One or more hydrogen atom arbitrarily can be substituted by halogen atom.) etc. carbon skeleton be basic chain structure chemical combination
Thing, or with a cyclohexylidene (- CH present in the group2- or not adjacent more than two-CH2- can be by-O-
Or-S- substitutions.), (- CH=present in the group or not adjacent more than two-CH=can be by-N=for phenylene
Substitute, hydrogen atom present in the group can be replaced by fluorine atoms.), naphthylene (- CH=present in the group or
Adjacent more than two-CH=can not substituted by-N=, and hydrogen atom present in the group can be replaced by fluorine atoms.)
Deng the compound that carbon skeleton is basic cyclic structure.In alkene derivatives, there can be one "-CH=CH- ", can also have
Have more than two "-CH=CH- ".
In the case that alkene derivatives have more than two "-CH=CH- ", exist as whole "-CH=CH- " performances
The alkene derivatives of E bodies, a part "-CH=CH- " performance E bodies and the alkene derivatives of remaining "-CH=CH- " performance Z bodies,
With the alkene derivatives of "-CH=CH- " performance Z bodies of whole are such, each "-CH=CH- " performance E bodies or Z bodies it is a variety of
Isomers.In the present invention, Z- alkene derivatives are that one or more "-CH=CH- " in alkene derivatives shows Z bodies
Compound, can be "-CH=CH- " all performance Z bodies compounds, or include one or more performance
The compound of "-CH=CH- " of E bodies.In addition, E- alkene derivatives are at least one "-CH=CH- " table in alkene derivatives
The compound of existing E bodies, can be the compound that "-CH=CH- " all shows E bodies, or comprising one or more
Performance Z bodies "-CH=CH- " compound, but be preferably "-CH=CH- " all performance E bodies compounds.Need to illustrate
, the E- alkene derivatives as isomerization body are compared with as the Z- alkene derivatives of isomerization body raw material, more with extremely
"-the CH=CH- " of few performance E bodies.
Suitable for the alkene derivatives of the manufacture method of the present invention, from easily making E- alkene derivatives optionally separate out
From the viewpoint of, the fusing point of E- alkene derivatives is preferably higher than the fusing point of Z- alkene derivatives more than 10 DEG C, preferably high 15 DEG C with
On, it is more preferably high more than 20 DEG C, it is further preferably high more than 30 DEG C, it is particularly preferably high more than 40 DEG C, it is most preferably high more than 50 DEG C.
The fusing point of commonly known E- alkene derivatives is higher than the fusing point of Z- alkene derivatives, but according to the experience of the present inventor etc., fusing point
The more big deliquescent difference of difference it is also bigger.It can thus be assumed that when the difference of fusing point is big, E- alkene is easily only made in reaction system
Separate out derivatives selectively.
It should be noted that the E- alkene derivatives (purity represented by formula (2) in embodiment：99.9%) fusing point is
175 DEG C, the E/Z- compositions of olefines (purity represented by formula (1) in embodiment：99.5%, " E bodies：18.7%th, Z bodies：
80.8% ") fusing point is 106 DEG C.Although pure Z- alkene derivatives can not manufacture, fusing point can not be determined, its fusing point should
When the fusing point than above-mentioned E/Z- compositions of olefines is low.It should be noted that fusing point can be determined by method as shown below.
＜ devices ＞
Petrographic microscope
·METTLER TOLEDO FP82HT Hot Stage
·METTLER TOLEDO FP90Central Processor
＜ utensils ＞
Slide
Cover glass
＜ samples adjust ＞
Collection about 10mg samples are placed in slide, covered.
＜ determines ＞
Programming rate (1.0 DEG C/min)
To same sample twice from nematic phase become the temperature measuring of isotropic phase, be averaged value as molten
Point (temperature for becoming isotropic phase from nematic phase).
The method of the present invention can be suitably adapted to require extreme high purity, as liquid crystal group used for liquid crystal display element
The compound and the manufacture of the intermediate for synthesizing the compound that compound uses.Such compound generally by recrystallize into
Go refined etc., thus will also realize that, the crystallinity of E- alkene derivatives is high.Therefore, can relatively easily be analysed in reaction system
Go out.
The Z- alkene derivatives with more than one cyclic structure are preferably the chemical combination represented by formula (1) in structure
Thing.
[changing 2]
R1-(A1-Z1)m1-Y1-(Z2-A2)n1-R2 (1)
[in formula, R1And R2Independently of one another represent fluorine atom, chlorine atom, bromine atoms, iodine atom, hydroxyl, cyano group, carboxyl,
Methanesulfonyloxy group, tolysulfonyl epoxide or trifluorometanesulfonyloxy, the alkyl of carbon number 1 to 15 (are deposited in the alkyl
- a CH2- or not adjacent more than two-CH2- independently of one another can by-O- ,-S- ,-COO- ,-OCO- ,-
CO- ,-CH=CH- or-C ≡ C- substitute, and one or more the hydrogen atom in alkyl can be replaced by fluorine atoms.) or-
S1-R3, S1For the alkylidene of carbon number 1~4, R3Represent chlorine atom, bromine atoms, iodine atom, hydroxyl, cyano group, carboxyl, methane
Sulfonyloxy, tolysulfonyl epoxide or trifluorometanesulfonyloxy,
A1And A2The group being each independently in the group being made up of (a), (b), (c),
(a) a 1,4- cyclohexylidenes (- CH present in the group2- or not adjacent more than two-CH2- can be with
Substituted by-O- or-S-.)
(b) 1,4- phenylenes (- CH=present in the group or not adjacent more than two-CH=can by-
N=substitutes, and hydrogen atom present in the group can be replaced by fluorine atoms.)
(c) naphthalene -2,6- diyls, 1,2,3,4-tetralin -2,6- diyls or decahydronaphthalenes -2,6- diyls (naphthalene -2,6- two
- CH=present in base or 1,2,3,4-tetralin -2,6- diyls or not adjacent more than two-CH=can be with
Substituted by-N=, hydrogen atom present in naphthalene -2,6- diyl or 1,2,3,4-tetrahydro-naphthalene -2,6- diyl can be taken by fluorine atom
Generation.)
Z1And Z2The alkylidene of the straight-chain of singly-bound or carbon number 1~10 is represented independently of one another, is existed in the alkylidene
- a CH2- or not adjacent more than two-CH2- independently of one another can by-O- ,-S- ,-COO- ,-OCO- ,-CO- ,-
CH=CH- or-C ≡ C- substitute, Z1And Z2Present in hydrogen atom can be replaced by fluorine atoms,
m1And n10 to 5 integer, m are represented independently of one another1+n11 to 5 is represented,
Y1Represent：
[changing 3]
(stain in formula represents A1、A2、Z1、Z2、R1And R2In and Y1Directly in conjunction with atom.),
A1And A2When having multiple, they can be the same or different, Z1And Z2When having multiple, they can be with identical
Can also be different.]
E- alkene derivatives (hereinafter also referred to " formula (1) institute corresponding with the Z- alkene derivatives represented by formula (1)
The E bodies of the compound of expression ".) be formula (1) in Y1Represent the compound of following structure.
[changing 4]
(stain in formula represents A1、A2、Z1、Z2、R1And R2In and Y1Directly in conjunction with atom.)
The E bodies of compound represented by formula (1) are as used in liquid-crystal composition for example used for liquid crystal display element
Compound and the intermediate for synthesizing the compound are useful.From the viewpoint of response speed is improved, liquid-crystal composition
Preferred viscosities are low, in addition to maintaining nematic phase over a wide temperature range, preferably each composition has the height with other compositions
Combination.In addition, the species of liquid-crystal composition can be selected according to the display mode of liquid crystal panel.For example, liquid crystal panel
For VA (vertical orientated (Vertical Alignment)) modes or PSA, (polymer stabilizing is orientated (Polymer-Sustained
Alignment the use of the value of dielectric constant anisotropy (Δ ε) is negative liquid-crystal composition)) in the case of mode, liquid crystal surface
In the case that plate is IPS (plane conversion (In-Plane-Switching)) mode, the value using Δ ε is positive or negative liquid crystal group
Compound.
In formula (1), in order to reduce the viscosity of liquid-crystal composition, A1And A2Independently of one another be preferably anti-form-1,4- Asias ring
Hexyl, unsubstituted naphthalene -2,6- diyl or unsubstituted Isosorbide-5-Nitrae-phenylene, in order to improve the Combination with other liquid crystal compositions,
Preferably anti-form-1,4- cyclohexylidenes or unsubstituted 1,4- phenylenes.
In the case of being positive compound using the E bodies manufacture Δ ε of the compound represented by formula (1), in order that Δ ε
Greatly, A1And A2It is preferred independently of one another
[changing 5]
Further preferably
[changing 6]
In the case of being negative compound using the E bodies manufacture Δ ε of the compound represented by formula (1), A1And A2Each solely
On the spot preferably following structure.
[changing 7]
Long-term reliability when liquid crystal display cells are made in order to improve, liquid-crystal composition preferably not nitrogen atom.
In formula (1), in order to reduce the viscosity of liquid-crystal composition, R1And R2The preferably alkyl of carbon number 1~12, carbon
The alkenyloxy group of the alkenyl of atomicity 2~12, the alkoxy of carbon number 1~12 or carbon number 2~12, more preferably carbon atom
The alkyl of number 1~8 or the alkenyl of carbon number 2~8, the particularly preferably alkyl of carbon number 1~5 or carbon number 2~5
Alkenyl.Additionally, it is preferred that it is straight-chain.In addition, R1And R2At least one party be preferably methanesulfonyloxy group, tolysulfonyl epoxide,
Trifluorometanesulfonyloxy, hydroxyl, trifluoromethoxy, carboxyl.
In the case of Δ ε is manufactured as positive compound, in order that Δ ε is big, preferably R1Or R2In either one for fluorine atom,
Cyano group, trifluoromethyl or trifluoromethoxy, in order to reduce viscosity, preferably fluorine atom.
In formula (1), in order to reduce the viscosity of liquid-crystal composition and improve the Combination with other liquid crystal compositions, Z1With
Z2It is preferably-CH independently of one another2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2- ,-CF=CF- ,-C ≡ C- or singly-bound, enter
One step is preferably-CF2O-、-OCF2-、-CH2CH2- or singly-bound, particularly preferably singly-bound, it is preferably single to show big Δ ε
Key or-CF2O-.With Y1Directly in conjunction with Z1And Z2It is preferred that the alkylidene or singly-bound of the straight-chain of carbon number 1~10 are represented, it is excellent
Choosing represents the alkylidene or singly-bound of the straight-chain of carbon number 1~4.
From the viewpoint of E- alkene derivatives is easier precipitation, the R in formula (1)1、R2、A1、A2、Z1、Z2、m1And n1
Preferably following combination：
R1And R2Fluorine atom, the alkyl of carbon number 1~12, the alkenyl of carbon number 2~12, carbon are represented independently of one another
The alkoxy of atomicity 1~12 or the alkenyloxy group of carbon number 2~12,
A1And A2The group being each independently in the group being made up of (a), (b),
(a) a 1,4- cyclohexylidenes (- CH present in the group2- or not adjacent more than two-CH2- can be with
Substituted by-O- or-S-.)
(b) 1,4- phenylenes (- CH=present in the group or not adjacent more than two-CH=can by-
N=substitutes, and hydrogen atom present in the group can be replaced by fluorine atoms.)
Z1And Z2It is each independently-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2- ,-CF=CF- ,-C ≡ C- or
Singly-bound,
m1And n10 to 4 integer, m are represented independently of one another1+n1For 1 to 4；
More preferably following combination：
R1And R2Fluorine atom, the alkyl of carbon number 1~8 or the alkoxy of carbon number 1~8 are represented independently of one another,
A1For the group in the group being made up of (a), (b),
(a) 1,4- cyclohexylidenes
(b) (hydrogen atom present in the group can be replaced by fluorine atoms 1,4- phenylenes.)
Z1For-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2- or singly-bound,
A2And Z2Being not present, i.e. n1 represents 0,
m1For 1 to 4 integer；
More preferably following combination：
R1And R2Fluorine atom, the alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 are represented independently of one another,
A1For the group in the group being made up of (a), (b),
(a) 1,4- cyclohexylidenes
(b) (hydrogen atom present in the group can be replaced by fluorine atoms 1,4- phenylenes.)
Z1For-CH2O-、-OCH2-、-CH2CH2- or singly-bound,
A2And Z2Being not present, i.e. n1 represents 0,
m1For 1 to 3 integer.
Compound represented by formula (1) is preferably selected from by following formula (1a), formula (1b), formula (1c), logical
Compound group represented by formula (1d) or formula (1e) into group in compound.
[changing 8]
[in formula, A1a2And Z1a2Represent and the A in aforementioned formula (1)2And Z2Identical implication,
R1a1The alkyl of carbon number 1 to 15 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1a2The alkyl of carbon number 1 to 8 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
W1a1Represent the alkylidene of the straight-chain of singly-bound or carbon number 1 to 4 ,-a CH present in the alkylidene2- or
Not adjacent more than two-CH2- can be substituted independently of one another by-O- ,-S- ,-COO- ,-OCO- ,-CO- or-C ≡ C-,
W1a1Present in hydrogen atom can be replaced by fluorine atoms,
Y1a2Singly-bound or-CH=CH- are represented,
n1a1Represent 1 to 5 integer.]
[changing 9]
[in formula, A1b1、A1b2、Z1b1And Z1b2Represent and the A in aforementioned formula (1)1、A2、Z1And Z2Identical implication,
R1b1And R1b2The alkyl of carbon number 1 to 8 ,-a CH present in the alkyl are represented independently of one another2- or not
Adjacent more than two-CH2- independently of one another can by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-
CO- substitutes,
W1b1And W1b2The alkylidene of the straight-chain of singly-bound or carbon number 1 to 4 is represented independently of one another, is deposited in the alkylidene
- a CH2- or not adjacent more than two-CH2- independently of one another can be by-O- ,-S- ,-COO- ,-OCO- ,-CO-
Or-C ≡ C- substitutions, W1b1And W1b2Present in hydrogen atom can be replaced by fluorine atoms,
Y1b2And Y1b3Singly-bound or-CH=CH- are represented independently of one another,
m1b1And n1b10 to 5 integer, m are represented independently of one another1b1+n1b1Represent 1 to 5.]
[changing 10]
[in formula, A1c2And Z1c2Represent and the A in aforementioned formula (1)2And Z2Identical implication,
A1c3Expression is selected from
[changing 11]
Group,
R1c1The alkyl of carbon number 1 to 15 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1c2Fluorine atom, trifluoromethoxy or cyano group are represented,
n1c1Represent 1 to 5 integer.]
[changing 12]
[in formula, A1d2And A1d3Represent and the A in formula (1)2Identical implication, Z1d2、Z1d3And Z1d4Represent and formula (1)
In Z2Identical implication,
R1d1The alkyl of carbon number 1 to 15 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1d2The alkyl of carbon number 1 to 8 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
W1d1Represent the alkylidene of the straight-chain of singly-bound or carbon number 1 to 4 ,-a CH present in the alkylidene2- or
Not adjacent more than two-CH2- can be substituted independently of one another by-O- ,-S- ,-COO- ,-OCO- ,-CO- or-C ≡ C-,
W1d1Present in hydrogen atom can be replaced by fluorine atoms,
Y1d2Singly-bound or-CH=CH- are represented,
n1d1And n1d20 to 4 integer is represented independently of one another.]
[changing 13]
[in formula, A1e2And Z1e2Represent and the A in aforementioned formula (1)2And Z2Identical implication,
R1e1The alkyl of carbon number 1 to 15 is represented ,-a CH present in the alkyl2- or not adjacent two or more
- CH2- can be substituted independently of one another by-CH=CH- ,-C ≡ C- ,-O- ,-S- ,-COO- ,-OCO- or-CO-,
R1e2Represent hydroxyl, hydroxymethyl, bromomethyl, chloromethyl, methanesulfonyloxymethyl, tosyloxymethyl,
Chlorine atom, bromine atoms, iodine atom, trifluorometanesulfonyloxy or
[changing 14]
(stain in formula represents A1e2In and R1e2Directly in conjunction with carbon atom, R1e3Represent the alkyl of carbon number 1 to 5
Or hydrogen atom.)
n1e1Represent 1 to 4 integer.]
The concrete example of preferable compound described below, but the invention is not restricted to this.
In formula (1a), each compound represented by preferably following formula (1a-1)~formula (1a-23).
[changing 15]
(in formula, R1a1、Z1a2And R1a2Represent and the R in aforementioned formula (1a)1a1、Z1a2And R1a2Identical implication.)
[changing 16]
[in formula, R1a1、Z1a2And R1a2Represent and the R in aforementioned formula (1a)1a1、Z1a2And R1a2Identical implication.]
[changing 17]
[in formula, R1a1、Z1a2And R1a2Represent and the R in aforementioned formula (1a)1a1、Z1a2And R1a2Identical implication.]
[changing 18]
[in formula, R1a1、Z1a2And R1a2Represent and the R in aforementioned formula (1a)1a1、Z1a2And R1a2Identical implication.]
[changing 19]
[in formula, R1a1、Z1a2And R1a2Represent and the R in aforementioned formula (1a)1a1、Z1a2And R1a2Identical implication.]
In formula (1b), each compound represented by preferably following formula (1b-1)~formula (1b-10).
[changing 20]
[in formula, R1b1And R1b2Represent and the R in aforementioned formula (1b)1b1And R1b2Identical implication.]
[changing 21]
[in formula, R1b1And R1b2Represent and the R in aforementioned formula (1b)1b1And R1b2Identical implication.]
In formula (1c), each compound represented by preferably following formula (1c-1)~formula (1c-65).
[changing 22]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c1And A1c3Identical contains
Justice.]
[changing 23]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 24]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 25]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 26]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 27]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 28]
[in formula, R1c1、R1c2、Z1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2、Z1c2And A1c3Identical contains
Justice.]
[changing 29]
[in formula, R1c1、R1c2And A1c3Represent and the R in aforementioned formula (1c)1c1、R1c2And A1c3Identical implication.]
In formula (1d), each compound represented by preferably following formula (1d-1)~formula (1d-35).
[changing 30]
[in formula, R1d1、R1d2And Z1d2Represent and the R in aforementioned formula (1d)1d1、R1d2And Z1d2Identical implication.]
[changing 31]
[in formula, R1d1、R1d2And Z1d2Represent and the R in aforementioned formula (1d)1d1、R1d2And Z1d2Identical implication.]
[changing 32]
[changing 33]
[in formula, R1d1、R1d2And Z1d2Represent and the R in aforementioned formula (1d)1d1、R1d2And Z1d2Identical implication.]
In formula (1e), each compound represented by preferably following formula (1e-1)~formula (1e-13).
[changing 34]
[in formula, R1e1、R1e2And Z1e2Represent and the R in aforementioned formula (1e)1e1、R1e2And Z1e2Identical implication.]
As sulphur compound, as long as the compound comprising more than one sulphur atom is just not particularly limited, but from easy
Produce Thiyl Radical and react the excellent aspect of facilitation effect and set out, preferably organosulfur compound, more preferably selected from following
The compound of compound group represented by formula (A)~(H).In addition, from same aspect, sulphur compound is preferably to contain S-
The compound of S keys, the more preferably compound selected from the compound group represented by following formulas (A), (C), (D), (E) and (F),
Compound more preferably selected from the compound group represented by following formulas (A), (D) and (F).It should be noted that contain
The compound of S -- S can be the compound with S -- S or the compound with two or more S -- S.Separately
Outside, two S atoms in S -- S can be separately not oxidized S atom, i.e.-S-, or after being oxidized
S atom, i.e.-S (=O)-or-S (=O)2-。
[changing 35]
Ra-S-S-Rb (A)
Ra-S-Rb (B)
[in formula, RaAnd RbRepresent independently of one another selected from substituted or unsubstituted phenyl, substituted or unsubstituted carbon atom
The group of the alkyl of number 1 to 8, the alkenyl of substituted or unsubstituted carbon number 2 to 8 and hydrogen atom.]
RaAnd/or RbIn the case of for phenyl, preferably the phenyl is unsubstituted, or the carbon atom by straight-chain or branched
The carbon number 2 of the alkoxy of the carbon number 1 to 8 of the alkyl of number 1 to 8, straight-chain or branched, straight-chain or branched to
8 alkenyl, chlorine atom, amino or hydroxyl etc. substitute.
RaAnd/or RbIn the case of alkyl or alkenyl, the alkyl or alkenyl can be that straight-chain can also be branched.
In addition, RaAnd/or RbIn the case of for alkyl or alkenyl, the preferably alkyl or alkenyl to be unsubstituted, or by chlorine atom, amino or
Hydroxyl etc. substitutes.
As the concrete example of these sulphur compounds, Diphenyl disulfide ether, aralkyl sulfid, benzenethiol, (phenyl sulphur can be enumerated
Acyl) aralkyl sulfid, the sulfone of diphenyl two, diphenyl sulfoxide, diphenyl sulfone, di-p-tolyl disulfide, 2,2'- diamino-diphenyls
Disulfide, 4,4'- diamino-diphenyls disulfide, 4,4'- dihydroxydiphenyls disulfide, the sulphur of 3,3'- dihydroxydiphenyls two
Ether, double (p-methoxyphenyl) disulfides, 4,4'- dichlorophenyls disulfide, 4,4'- difluorodiphenyl bases disulfide, double (4- carboxylics
Base phenyl) disulfide, dimethyl disulfide, diethyl disulphide, dipropyl disulfide, diisopropyl disulfide ether, diallyl
Disulfide etc..In these, preferably Diphenyl disulfide ether, (phenylSulphon) aralkyl sulfid or the sulfone of diphenyl two, more preferably diphenyl
Disulfide.
Addition for the sulphur compound of isomerization reaction for example can relative to the alkene derivatives total amount as raw material
To be set to 0.1~10 mole of %.The lower limit of the addition of sulphur compound is excellent relative to the alkene derivatives total amount as raw material
Elect 0.2 mole of more than %, 0.5 mole of more than %, more than 1% or more than 2% as.In addition, the upper limit of the addition of sulphur compound
Value is preferably 8 moles of below %, 7 moles of below %, 6 moles of below % or 5 relative to the alkene derivatives total amount as raw material
Mole below %.
As radical initiator, known material can be used.As its concrete example, 2 can be enumerated, 2 '-azo
Bis-isobutyronitrile, 2,2 '-azo be double-and (2,4- methyl pentane nitriles), 2,2 '-azo be double-(4- methoxyl group -2,4- methyl pentane nitriles),
Double (the 2- methyl of 2,2 '-azo double (2- methylbutyronitriles), 1,1 '-azo pair-(hexamethylene -1- formonitrile HCNs), dimethyl 2,2 '-azo
Propionic ester), 2,2 '-azo double (N- butyl -2- methyl propanamides), the azo-compound such as 4,4 '-azo double (4- cyanopentanoic acids)；
Benzoyl peroxide, lauroyl peroxide, tert-Butyl peroxypivalate, 1,1 '-bis--(tert-butyl hydroperoxide) hexamethylene, uncle
The organic peroxides such as amyl peroxy -2 ethyl hexanoic acid ester, tertiary hexyl peroxidating -2 ethyl hexanoic acid ester, promote effect from reaction
The excellent aspect of fruit is set out, preferably azo-compound.It should be noted that radical initiator can be according to isomerization reaction
Reaction temperature, species of matrix etc., suitable material of the selection with appropriate half life temperature.
Addition for the radical initiator of isomerization reaction is total for example relative to the alkene derivatives as raw material
Amount can be set to 0.1~10 mole of %.The lower limit of the addition of radical initiator is relative to the alkene derivative as raw material
Thing total amount is preferably 0.2 mole of more than %, 0.5 mole of more than %, more than 1% or more than 2%.In addition, radical initiator
The higher limit of addition is preferably that 8 moles of below %, 7 moles of below %, 6 are rubbed relative to the alkene derivatives total amount as raw material
You are below % or 5 mole of below %.
As long as the reaction temperature in the method for the present invention can be such that E- alkene derivatives optionally separate out and be less than E-
The temperature of the fusing point of alkene derivatives just without special problem, can be set to such as 20 DEG C~120 DEG C.From easily making E- alkene spread out
From the viewpoint of biology separates out, said temperature is preferably 20 DEG C~90 DEG C, more preferably 20 DEG C~70 DEG C, more preferably 30
DEG C~50 DEG C.
The solvent used in method as the present invention, such as can suitably use the aromatic series such as toluene, benzene, dimethylbenzene
Series solvent；The saturation hydrocarbon system solvent such as hexane, heptane, hexamethylene；Dichloromethane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,
The chlorine series solvent such as 1,2,2- tetrachloroethanes；The ether systems such as tetrahydrofuran (THF), Anaesthetie Ether, Di Iso Propyl Ether, t-butyl methyl ether
Solvent；The alcohol series solvents such as methanol, ethanol, particularly preferred toluene, THF, methanol.These solvents can be used in mixed way as needed.
Solvent can suitably select according to the species of matrix.For example, in the case of using the low matrix of polarity, preferably select
Polar solvent (such as alcohol series solvent, ether series solvent etc.), in the case of using the high matrix of polarity, preferably selects non-polar solven
(such as fragrant family solvent, saturation hydrocarbon system etc.).In addition, it is also preferred that refined using being suitable to recrystallize target E- alkene derivatives
Solvent.
Amount for the solvent of isomerization reaction is not particularly limited, for example, relative to the mass of E/Z- compositions of olefines 100
Part, 100~1000 mass parts can be set to.
From the viewpoint of improving reactivity and suppressing side reaction, method of the invention is preferably under the inert atmospheres such as nitrogen
Carry out, preferably avoid being mixed into other gases as far as possible.For example, the concentration of the oxygen in atmosphere is preferably less than 10%, more preferably 7%
Hereinafter, more preferably less than 3%.
By method of the invention, it is possible to making ratio of the quality of E- alkene derivatives relative to the quality of Z- alkene derivatives
Rate (E bodies/Z bodies) is improved to more than 90/10, i.e. the content of the E- alkene derivatives in E/Z- compositions of olefines is improved to 90
More than quality %.The quality of E- alkene derivatives is preferably higher relative to the ratio of the quality of Z- alkene derivatives, is preferably (E
Body/Z bodies)=more than 93/7, more preferably more than 97/3.The quality of E- alkene derivatives relative to Z- alkene derivatives quality
Ratio (E bodies/Z bodies) can be quantified by gas-chromatography.
In order to which Z- alkene derivatives remaining in the E/Z- compositions of olefines after isomerization reaction are removed, target E- is obtained
Alkene derivatives, E/Z- compositions of olefines can further be refined.As process for purification, chromatogram, recrystallization, steaming can be enumerated
Evaporate, distil, reprecipitation, absorption, liquid separation processing etc..In the case of using refining agent, as refining agent, silica gel, oxidation can be enumerated
Aluminium, activated carbon, atlapulgite, cerite, zeolite, mesoporous silicon oxide, CNT, carbon nanohorn, binchotan, charcoal, stone
Black alkene, ion exchange resin, Emathlite, silica, diatomite, pearlite, cellulose, organic polymer, Porous coagulate
Glue etc..If refined as being repeated, the isolated yield that E- alkene derivatives be present reduces the problem of such, but according to
The method of the present invention, the quality of E- alkene derivatives can be more improved relative to Z- alkene derivatives by isomerization reaction
The ratio of quality, therefore refined number can be reduced, it is possible to increase the yield of E- alkene derivatives.
Embodiment
Hereinafter, the present invention is described in further detail in citing, but the invention is not restricted to this.
On gas chromatographic analysis, implement under the following conditions.
Sample is modulated：1 mass % acetone solns
Chromatographic column import volume：1μL
Device：GC2010 (Shimadzu Seisakusho Ltd.)
Chromatographic column：J&WDB-17MS(30m×0.25μm×0.25mm)
Carrier gas：Nitrogen
Chromatogram column pressure：(226kPa), chromatogram column flow：3.19mL/min, average speed：58.8cm/sec
Split ratio：50:1
Implantation temperature：300 DEG C, detector temperature：(FID)320℃
Chromatographic column heating setting：100℃(1min)→10℃/min→300℃(14min)
(embodiment 1)
[changing 36]
By E/Z compositions of olefines (50g, E body/Z body=4/96), Diphenyl disulfide ether (347mg) and the ethanol of formula (1)
After (125mL) will be mixed in the reaction vessel after being replaced with nitrogen at room temperature, interior 47 DEG C of temperature is heated to.47 DEG C of additions of temperature inside
After 2,2- azos double (2,4- methyl pentane nitrile) (395mg), in oxygen concentration, stirring 12 is small under the blanket of nitrogen of (about 1%) below 3%
When.It should be noted that in the way of reaction, the generation of precipitate is confirmed.Reaction solution is analyzed by gas-chromatography,
As a result E bodies/Z body=97/3.After reaction solution is cooled into 10 DEG C, 50mL methanol is added.Then, precipitate is filtered out, made
Surface clean (above hanging け to clean) is carried out with methanol (50mL).The precipitate of gained is set to be dissolved in the mixed solvent of toluene and hexane
Afterwards, add water (150mL) and carry out liquid separation, clean organic layer using water (150mL), saturated aqueous common salt (150mL) successively, add nothing
Aqueous sodium persulfate is dried.After filtering out sodium sulphate, refined by silica gel column chromatography, so as to obtain the E/Z alkene groups of formula (2)
Compound (39.7g, E body/Z body=99/1).
(embodiment 2)
[changing 37]
By E/Z compositions of olefines (45g, E body/Z body=4/96), Diphenyl disulfide ether (312mg) and the ethanol of formula (1)
After (113mL) is mixed in the reaction vessel after being replaced with nitrogen at room temperature, interior 47 DEG C of temperature is heated to.47 DEG C of temperature adds 2 inside,
After 2- azos double (2,4- methyl pentane nitrile) (356mg), stirred 20 hours under the blanket of nitrogen of (about 5%) below 7% in oxygen concentration.
It should be noted that in the way of reaction, the generation of precipitate is confirmed.Reaction solution is analyzed by gas-chromatography, tied
Fruit E bodies/Z body=95/5.Toluene (135mL) and water (135mL), liquid separation, successively using water are added into the reaction solution
(135mL), saturated aqueous common salt (135mL) clean organic layer, add anhydrous sodium sulfate and are dried.After filtering out sodium sulphate, pass through
Silica gel column chromatography is refined, so as to obtain the E/Z compositions of olefines of formula (2) (37.9g, E body/Z body=95/5).
It should be noted that on Examples 1 and 2, the ratio of E- alkene derivatives is determined by gas chromatographic analysis
Rheological parameters' change with time.It the results are shown in Fig. 1.As shown in Figure 1, by further reducing the oxygen concentration in reaction system, for shortening
Reaction time, increase E- alkene derivatives are effective.
(comparative example 1)
[changing 38]
By E/Z compositions of olefines (3g, E body/Z body=4/96), benzene sulfinic acid sodium salt (190mg) and the toluene of formula (1)
(7.5mL) is heated to interior 95 DEG C of temperature after mixed at room temperature.95 DEG C of temperature is slowly added to acetic acid (1.5mL) inside, at 95 DEG C further
Stirring 3 hours.It should be noted that in the way of reaction, the generation unconfirmed to precipitate.After being cooled to room temperature, water is added
(7.5mL) carries out liquid separation, successively using water (7.5mL), saturated aqueous sodium carbonate (7.5mL) and saturated aqueous common salt (7.5mL)
Organic layer is cleaned, anhydrous sodium sulfate is added and is dried.After filtering out sodium sulphate, concentration, refined by silica gel column chromatography, from
And obtain the E/Z compositions of olefines (2.9g, E body/Z body=83/17) of formula (2).
,, can be with the case of the isomerization method for being applicable the present invention compared with conventional method from result above
More height ratio obtains target E- alkene derivatives.
Claims (7)
1. a kind of manufacture method of isomerization body, make the alkene structures with one or more performance Z bodies in molecule
Alkene derivatives isomerization in the case where solvent be present, so as at least one isomerization of the alkene structures of the performance Z bodies
Isomerization body is obtained into the alkene structures of performance E bodies, in this method, the isomerization body is optionally separated out while entering
Row isomerization.
2. the manufacture method of isomerization body according to claim 1, by the way that sulphur compound and radical initiator occurs
Act on and carry out isomerization.
3. the manufacture method of isomerization body according to claim 2, the sulphur compound is the compound containing S -- S.
4. the manufacture method of isomerization body according to claim 2, the sulphur compound is selected from formula (A)~formula
(H) one or more kinds of compounds of the compound group represented by,
Ra-S-S-Rb (A)
Ra-S-Rb (B)
In formula, RaAnd RbRepresent independently of one another selected from substituted or unsubstituted phenyl, substituted or unsubstituted carbon number 1 to 8
Alkyl, the alkenyl of substituted or unsubstituted carbon number 2 to 8 and the group of hydrogen atom.
5. the manufacture method of the isomerization body according to any one of claim 2~4, radical initiator are azo compounds
Thing.
6. according to the manufacture method of isomerization body according to any one of claims 1 to 5, there are one or two in the molecule
The alkene derivatives of the alkene structures of performance Z bodies more than individual are formula (1),
R1-(A1-Z1)m1-Y1-(Z2-A2)n1-R2 (1)
In formula, R1And R2Fluorine atom, chlorine atom, bromine atoms, iodine atom, hydroxyl, cyano group, carboxyl, methane sulphur are represented independently of one another
The alkyl or-S of acyloxy, tolysulfonyl epoxide or trifluorometanesulfonyloxy, carbon number 1 to 151-R3, deposit in the alkyl
- a CH2- or not adjacent more than two-CH2- independently of one another can by-O- ,-S- ,-COO- ,-OCO- ,-
CO- ,-CH=CH- or-C ≡ C- substitute, and one or more the hydrogen atom in alkyl can be replaced by fluorine atoms,
S1For the alkylidene of carbon number 1~4,
R3Represent chlorine atom, bromine atoms, iodine atom, hydroxyl, cyano group, carboxyl, methanesulfonyloxy group, tolysulfonyl epoxide or three
Fluoromethane sulfonyloxy,
A1And A2The group being each independently in the group being made up of (a), (b), (c),
(a) Isosorbide-5-Nitrae-cyclohexylidene ,-a CH present in the group2- or not adjacent more than two-CH2- can be by-O-
Or-S- substitutions；
(b) Isosorbide-5-Nitrae-phenylene ,-a CH=present in the group or not adjacent more than two-CH=can be by-N=
Substitute, hydrogen atom present in the group can be replaced by fluorine atoms；
(c) naphthalene -2,6- diyl, 1,2,3,4-tetrahydro-naphthalene -2,6- diyl or decahydronaphthalenes -2,6- diyl, naphthalene -2,6- diyl or
- CH=present in 1,2,3,4-tetralin -2,6- diyls or not adjacent more than two-CH=can be by-N=
Substituting, hydrogen atom present in naphthalene -2,6- diyl or 1,2,3,4-tetrahydro-naphthalene -2,6- diyl can be replaced by fluorine atoms,
Z1And Z2The alkylidene of the straight-chain of singly-bound or carbon number 1~10 is represented independently of one another, one present in the alkylidene
Individual-CH2- or not adjacent more than two-CH2- independently of one another can be by-O- ,-S- ,-COO- ,-OCO- ,-CO- ,-CH=
CH- or-C ≡ C- substitute, Z1And Z2Present in hydrogen atom can be replaced by fluorine atoms,
m1And n10 to 5 integer, m are represented independently of one another1+n11 to 5 is represented,
Y1Represent：
Stain in formula represents A1、A2、Z1、Z2、R1And R2In and Y1Directly in conjunction with atom；
A1And A2When having multiple, they can be the same or different, Z1And Z2When having multiple, they can with it is identical can also
It is different.
7. according to the manufacture method of isomerization body according to any one of claims 1 to 6, the fusing point of the isomerization body and institute
State in molecule with one or more performance Z bodies alkene structures alkene derivatives fusing point compare high 10 DEG C with
On.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS459369Y1 (en) * | 1968-08-19 | 1970-05-02 | ||
| US4338170A (en) * | 1979-06-14 | 1982-07-06 | Nissan Chemical Industries, Ltd. | Isomerization of β-γ-unsaturated alcohol or its ester |
| JPH10273471A (en) * | 1997-03-28 | 1998-10-13 | Mitsubishi Chem Corp | Production of furamic acid |
| CN102046570A (en) * | 2008-05-29 | 2011-05-04 | 智索株式会社 | Liquid crystalline tetracyclic compound having fluorine atom, liquid crystal composition and liquid crystal display element |
| JP2012017263A (en) * | 2010-07-06 | 2012-01-26 | Shin-Etsu Chemical Co Ltd | Method of producing e,e-aliphatic conjugated diene compound by radical isomerization in the presence of urea |
| US20140021406A1 (en) * | 2012-07-12 | 2014-01-23 | Jnc Petrochemical Corporation | Liquid crystal compound having fluorovinyl group, liquid crystal composition and liquid crystal display device |
| CN105732334A (en) * | 2014-12-24 | 2016-07-06 | Dic株式会社 | Method for manufacturing olefinic derivative composition |
-
2016
- 2016-10-04 JP JP2016196603A patent/JP6805698B2/en active Active
-
2017
- 2017-09-25 CN CN201710875111.0A patent/CN107892646A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS459369Y1 (en) * | 1968-08-19 | 1970-05-02 | ||
| US4338170A (en) * | 1979-06-14 | 1982-07-06 | Nissan Chemical Industries, Ltd. | Isomerization of β-γ-unsaturated alcohol or its ester |
| JPH10273471A (en) * | 1997-03-28 | 1998-10-13 | Mitsubishi Chem Corp | Production of furamic acid |
| CN102046570A (en) * | 2008-05-29 | 2011-05-04 | 智索株式会社 | Liquid crystalline tetracyclic compound having fluorine atom, liquid crystal composition and liquid crystal display element |
| JP2012017263A (en) * | 2010-07-06 | 2012-01-26 | Shin-Etsu Chemical Co Ltd | Method of producing e,e-aliphatic conjugated diene compound by radical isomerization in the presence of urea |
| US20140021406A1 (en) * | 2012-07-12 | 2014-01-23 | Jnc Petrochemical Corporation | Liquid crystal compound having fluorovinyl group, liquid crystal composition and liquid crystal display device |
| CN105732334A (en) * | 2014-12-24 | 2016-07-06 | Dic株式会社 | Method for manufacturing olefinic derivative composition |
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| JP6805698B2 (en) | 2020-12-23 |
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