JPWO2018066371A1 - Method for producing E-olefin compound - Google Patents

Abstract

An object of this invention is to provide the manufacturing method of an E-olefin compound which can be applied by using a wide range of Z-olefin compounds as a substrate. A sulfur compound and a radical initiator are allowed to act on an olefin derivative having an olefin structure representing one or more Z forms in the molecule, and at least one of the olefin structures representing the Z form is isomerized to an olefin structure representing the E form. A process for producing isomers.

Description

  The present invention relates to a method for producing an E-olefin compound useful as a production intermediate and a raw material for chemical products such as pharmaceuticals, agricultural chemicals, and liquid crystal materials.

  E-olefin compounds are useful compounds because they often exhibit excellent properties in the fields of pharmaceuticals, agricultural chemicals, and liquid crystal materials. In particular, in liquid crystal materials, E-olefin compounds are known to exhibit higher clearing points, relatively lower viscosities, and larger elastic constants than the corresponding saturated compounds, and are extremely important compounds. Generally, an E-olefin compound is obtained by subjecting a composition containing an E-olefin compound and a corresponding Z-olefin compound to an isomerization reaction using an arylsulfinic acid as a catalyst, to determine the ratio of the E-olefin compound in the composition. It is manufactured through a process of increasing (Non-Patent Documents 1 and 2). In addition, since arylsulfinic acid is known to be unstable, it is generally purchased and stored as the corresponding arylsulfinate and reacted with an acid such as hydrochloric acid in the reaction system when used. , Fresh arylsulfinic acid is produced and used. At this time, a process of mixing a composition containing an E-olefin compound and a corresponding Z-olefin compound, a sulfinate, an acid and a solvent at room temperature and then heating to a predetermined reaction temperature is generally used. (Patent Literature 1, Non-Patent Literature 1 and Non-Patent Literature 2).

Special table 2012-528798 gazette

H. Nozaki, Y. Nishikawa, M. Kawanishi, R. Noyori, Tetrahedron, 23,2173 (1967) T. W. Gibson, P. Strassburger, J. Org. Chem., 41, 791 (1976)

  By the way, under the conditions of acidity and high temperature in the conventional isomerization reaction, if a compound having a functional group that is weak against an acid, such as an ester group or 2-tetrahydropyranyl group, is used as a substrate, hydrolysis occurs. It is difficult to obtain a compound with good yield. For this reason, applicable substrates are limited under the conditions of conventional isomerization reactions.

  Then, an object of this invention is to provide the manufacturing method of an E-olefin compound which can apply a wide Z-olefin compound as a substrate.

  As a result of intensive studies, the present inventors have made a sulfur compound and a radical initiator act on an olefin derivative having an olefin structure representing one or two or more Z isomers in the molecule, thereby at least one of the olefin structures representing the Z isomer. By isomerizing the olefin into an olefin structure representing the E isomer, it was found that a Z-olefin structure could be isomerized to an E olefin structure without using an acid, and the present invention was completed. It was.

  Although the reason why the Z-olefin structure can be isomerized to the E-olefin structure by such a production method is not necessarily clear, the present inventors generate sulfur radicals by reacting a sulfur compound and a radical initiator. It is thought that isomerization is promoted by the action of radicals on the olefin, and isomers having a thermodynamically stable E-olefin structure are mainly obtained.

  In the present invention, an S—S bond-containing compound is allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule under heating, and at least one of the olefin structures representing the Z isomer is converted. It may be a method for producing an isomer by isomerization to an olefin structure representing E form. Also by this manufacturing method, since a sulfur radical can be generated, the Z-olefin structure can be isomerized to an E-olefin structure in the same manner as when a sulfur compound and a radical initiator are allowed to act.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of an E-olefin compound which can apply a wide Z-olefin compound as a substrate can be provided.

  In the present invention, a sulfur compound and a radical initiator are allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule, and at least one of the olefin structures representing the Z isomer represents an E isomer. This is a method for producing an isomer by isomerization to an olefin structure. In the present specification, an olefin derivative having an olefin structure representing one or more Z isomers in a molecule is also referred to as “Z-olefin derivative”, and at least of the olefin structure representing the Z isomer in the Z-olefin derivative. An olefin derivative substituted with an olefin structure, one of which represents an E form, is also referred to as an “E-olefin derivative”, and a composition containing both of these derivatives is also referred to as an “E / Z-olefin composition”. The above isomers correspond to E-olefin derivatives.

  The olefin derivative only needs to have an E-form and a Z-form stereoisomer, and both carbon atoms in the carbon-carbon double bond of the olefin each have one or two substituents, Tri-substituted olefins or tetra-substituted olefins can be used. Among them, disubstituted olefins in which both carbon atoms in the carbon-carbon double bond of the olefin each have one substituent, that is, olefin derivatives having “—CH═CH—” in the structure are preferable. In the present invention, a Z-olefin derivative may be used alone as a raw material, or an E / Z-olefin composition may be used as a raw material. In the E / Z-olefin composition, the content of the Z-olefin derivative is preferably 10% by mass or more, preferably 20% by mass or more, preferably 30% by mass or more, and 40% by mass. % Or more, preferably 50% by weight or more, preferably 60% by weight or more, preferably 70% by weight or more, preferably 80% by weight or more, 90% by weight % Or more is preferable. Usually, when an olefin derivative is produced, an E / Z-olefin composition in which an E-olefin derivative and a Z-olefin derivative are mixed can be obtained, which can be used as a raw material.

  The isomerized product (E-olefin derivative) produced in the present invention is usually obtained as an E / Z-olefin composition. When both the raw material and the product are E / Z-olefin compositions, the ratio of the E-olefin derivative in the composition is improved, that is, at least one of the olefin structures representing the Z form in the Z-olefin derivative. It is assumed that an isomer is produced when a part is converted to an olefin structure representing E form.

The olefin derivative may be, for example, an alkyl group (one or two or more CH ₂ groups in the alkyl group may be —O—, —CH═CH—, —CO—, —OCO so that the oxygen atom is not directly adjacent to the olefin derivative. -, -COO- or -C≡C-, and one or two or more hydrogen atoms in the alkyl group may be optionally substituted with a halogen atom). compounds having a basic, an acyclic structure or xylene group (the one present in the group -CH 2 cycloheteroalkyl _- or nonadjacent two or more -CH 2 _- is -O- or -S ), A phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, Hydrogen atoms present therein may be replaced by fluorine atoms), A tylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═, and a hydrogen atom present in this group is replaced by a fluorine atom) It is preferably a compound having a cyclic structure based on a carbon skeleton. In the olefin derivative, one “—CH═CH—” may be contained, or two or more “—CH═CH—” may be contained.

  When the olefin derivative has two or more “—CH═CH—”, all “—CH═CH—” represents an olefin derivative, and some “—CH═CH—” represents E Olefin derivatives in which the remaining “—CH═CH—” represents the Z form, and all “—CH═CH—” represents the Z form, and each “—CH═CH— There exist a plurality of isomers in which "" represents E form or Z form. In the present invention, the Z-olefin derivative is a compound in which one or more “—CH═CH—” in the olefin derivative represents a Z form, and “—CH═CH—” all represents a Z form. Even if it is a compound, the compound containing "-CH = CH-" showing one or two or more E bodies may be sufficient. Further, the E-olefin derivative is a compound in which at least one “—CH═CH—” in the olefin derivative represents an E isomer, and “—CH═CH—” all represents a E isomer, Although it may be a compound containing “—CH═CH—” representing one or more Z isomers, it is preferable that all “—CH═CH—” represent E isomers. In addition, the E-olefin derivative which is an isomer has at least one “—CH═CH—” representing the E isomer more than the Z-olefin derivative used as a raw material of the isomer.

  The Z-olefin derivative having one or more cyclic structures in the structure is represented by the general formula (1)

［式中、Ｒ^１及びＲ^２は各々独立してフッ素原子、塩素原子、臭素原子、ヨウ素原子、ヒドロキシル基、シアノ基、カルボキシ基、メタンスルホニルオキシ基、ｐ−トルエンスルホニルオキシ基又はトリフルオロメタンスルホニルオキシ基、炭素原子数１から１５のアルキル基（当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−に置き換えられてもよく、アルキル基中の１又は２以上の水素原子はフッ素原子で置換されていてもよい。）又は−Ｓ^１−Ｒ^３を表し、
Ｓ^１は炭素原子数１〜４のアルキレン基であり、
Ｒ^３は塩素原子、臭素原子、ヨウ素原子、ヒドロキシル基、シアノ基、カルボキシ基、メタンスルホニルオキシ基、ｐ−トルエンスルホニルオキシ基又はトリフルオロメタンスルホニルオキシ基を表し、
Ａ^１及びＡ^２は各々独立して
（ａ）１，４−シクロへキシレン基（この基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−又は−Ｓ−に置き換えられてもよい。）
（ｂ）１，４−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよく、この基中に存在する水素原子はフッ素原子に置換されてもよい。）
（ｃ）ナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基又はデカヒドロナフタレン−２，６−ジイル基（ナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよく、ナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基中に存在する水素原子はフッ素原子に置換されてもよい。）
からなる群より選ばれる基であり、
Ｚ^１及びＺ^２は各々独立して単結合又は炭素原子数１〜１０の直鎖状のアルキレン基を表し、該アルキレン基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−に置き換えられてもよく、Ｚ^１及びＺ^２中に存在する水素原子はフッ素原子に置換されてもよく、
ｍ^１及びｎ^１は各々独立して０から５の整数を表すが、ｍ^１＋ｎ^１は１から５を表し、
Ｙ^１は

[Wherein, R ¹ and R ² are each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, carboxy group, methanesulfonyloxy group, p-toluenesulfonyloxy group, or trifluoromethanesulfonyl. An oxy group, an alkyl group having 1 to 15 carbon atoms (one —CH ₂ — present in the alkyl group or two or more non-adjacent —CH ₂ — are each independently —O—, — S—, —COO—, —OCO—, —CO—, —CH═CH— or —C≡C— may be substituted, and one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms. even though it may.) or an ^-S 1 -R ^3,
S ¹ is an alkylene group having 1 to 4 carbon atoms,
R ³ represents a chlorine atom, bromine atom, iodine atom, hydroxyl group, cyano group, carboxy group, methanesulfonyloxy group, p-toluenesulfonyloxy group or trifluoromethanesulfonyloxy group,
A ¹ and A ² are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — is — (It may be replaced by O- or -S-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N = and present in this group) The hydrogen atom to be substituted may be substituted with a fluorine atom.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═; (The hydrogen atom present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be substituted with a fluorine atom.)
A group selected from the group consisting of:
Z ¹ and Z ² each independently represent a single bond or a linear alkylene group having 1 to 10 carbon atoms, one —CH ₂ — present in the alkylene group or _two not adjacent to each other The above -CH ₂ -may be independently replaced by -O-, -S-, -COO-, -OCO-, -CO-, -CH = CH- or -C≡C-, Hydrogen atoms present in ¹ and Z ² may be substituted with fluorine atoms,
m ¹ and n ¹ each independently represents an integer from 0 to 5, while m ¹ + n ¹ represents 1 to 5,
Y ¹ is

（式中の黒点はＡ^１、Ａ^２、Ｚ^１、Ｚ^２、Ｒ^１及びＲ^２中のＹ^１と直接結合する原子を表す。）
を表し、
Ａ^１及びＡ^２が複数存在する場合は、それらは同一であっても異なっていてもよく、Ｚ^１及びＺ^２が複数存在する場合は、それらは同一であっても異なっていてもよい。］
で表される化合物であることが好ましい。

(The black spot in the formula represents an atom directly bonded to Y ¹ in A ¹ , A ² , Z ¹ , Z ² , R ¹ and R ^2. )
Represents
When a plurality of A ¹ and A ² are present, they may be the same or different, and when a plurality of Z ¹ and Z ² are present, they may be the same or different. ]
It is preferable that it is a compound represented by these.

The E-olefin derivative corresponding to the Z-olefin derivative represented by the general formula (1) (hereinafter also referred to as “E-form of the compound represented by the general formula (1)”) is represented by the following formula (1): Y ¹ of

（式中の黒点はＡ^１、Ａ^２、Ｚ^１、Ｚ^２、Ｒ^１及びＲ^２中のＹ^１と直接結合する原子を表す。）
を表すものである。

(The black spot in the formula represents an atom directly bonded to Y ¹ in A ¹ , A ² , Z ¹ , Z ² , R ¹ and R ^2. )
Is expressed.

  The E form of the compound represented by the general formula (1) is useful as, for example, a compound used as a liquid crystal composition for a liquid crystal display element and an intermediate for synthesizing the compound. The liquid crystal composition preferably has a low viscosity from the viewpoint of improving the response speed, and each component preferably has high miscibility with other components in order to maintain the nematic layer in a wide temperature range. . The type of liquid crystal composition can be selected according to the display method of the liquid crystal panel. For example, when the liquid crystal panel is a VA (Vertical Alignment) method or a PSA (Polymer-Sustained Alignment) method, a liquid crystal composition having a negative dielectric anisotropy (Δε) value is used, and IPS (In- In the case of a plane-switching method, a liquid crystal composition having a positive or negative value of Δε is used.

In the general formula (1), A ¹ and A ² are each independently a trans-1,4-cyclohexylene group or an unsubstituted naphthalene-2,6-diyl group in order to reduce the viscosity of the liquid crystal composition. Or an unsubstituted 1,4-phenylene group. In order to increase the miscibility with other liquid crystal components, a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group is preferable. It is preferable that

In the case of producing a compound with a positive Δε using the E form of the compound represented by the general formula (1), A ¹ and A ² are each independently for increasing Δε.

が好ましく、

Is preferred,

が更に好ましい。

Is more preferable.

When a compound having a negative Δε is produced using the E form of the compound represented by the general formula (1), A ¹ and A ² each independently preferably have the following structure.

  In order to improve long-term reliability when a liquid crystal display element is formed, the liquid crystal composition preferably does not contain a nitrogen atom.

In general formula (1), R ¹ and R ² are each an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 1 to 1 carbon atoms in order to reduce the viscosity of the liquid crystal composition. It is preferably a 12 alkoxy group or an alkenyloxy group having 2 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, Particularly preferred is an alkyl group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms. Moreover, it is preferable that it is linear. At least one of R ¹ and R ² is preferably a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group, a hydroxyl group, a trifluoromethoxy group, or a carboxy group.

When producing a compound in which Δε is positive, either R ¹ or R ² is preferably a fluorine atom, a cyano group, a trifluoromethyl group or a trifluoromethoxy group in order to increase Δε. In order to reduce this, it is preferably a fluorine atom.

In the general formula (1), Z ¹ and Z ² are each independently —CH ₂ O— or —OCH ₂ for decreasing the viscosity of the liquid crystal composition and increasing the miscibility with other liquid crystal components. —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF═CF—, —C≡C— or a single bond are preferred, and —CF ₂ O—, —OCF ₂ — , —CH ₂ CH ₂ — or a single bond is more preferable, a single bond is particularly preferable, and a single bond or —CF ₂ O— is preferable in order to exhibit a large Δε. Z ¹ and Z ² directly bonded to Y ¹ preferably represent a linear alkylene group having 1 to 10 carbon atoms or a single bond, and a linear alkylene group having 1 to 4 carbon atoms or a single bond. Preferably it represents a bond.

  The compound represented by the general formula (1) is composed of a compound represented by the following general formula (1a), general formula (1b), general formula (1c), general formula (1d), or general formula (1e). A compound selected from the group is preferred.

［式中、Ａ^１ａ２及びＺ^１ａ２は前記一般式（１）における、Ａ^２及びＺ^２と同じ意味を表し、
Ｒ^１ａ１は炭素原子数１から１５のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｒ^１ａ２は炭素原子数１から８のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｗ^１ａ１は単結合又は炭素原子数１から４の直鎖状のアルキレン基を表し、該アルキレン基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、又は−Ｃ≡Ｃ−に置き換えられてもよく、Ｗ^１ａ１中に存在する水素原子はフッ素原子に置換されてもよく、
Ｙ^１ａ２は単結合又は−ＣＨ＝ＣＨ−を表し、
ｎ^１ａ１は１から５の整数を表す。］

[ ^Wherein , A ^1a2 and Z ^1a2 represent the same meaning as A ² and Z ² in the general formula (1),
R ^1a1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — present in the alkyl group are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R ^1a2 represents an alkyl group having 1 to 8 carbon atoms, and one —CH ₂ — present in the alkyl group or two or more non-adjacent —CH ₂ — are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W ^1a1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group _- or nonadjacent two or more -CH 2 _- is Each may be independently replaced with -O-, -S-, -COO-, -OCO-, -CO-, or -C≡C-, and the hydrogen atom present in W ^1a1 is replaced with a fluorine atom. May be,
Y ^1a2 represents a single bond or —CH═CH—,
n ^1a1 represents an integer of 1 to 5. ]

［式中、Ａ^１ｂ１、Ａ^１ｂ２、Ｚ^１ｂ１及びＺ^１ｂ２は前記一般式（１）における、Ａ^１、Ａ^２、Ｚ^１及びＺ^２と同じ意味を表し、
Ｒ^１ｂ１及びＲ^１ｂ２は各々独立して炭素原子数１から８のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｗ^１ｂ１及びＷ^１ｂ２は各々独立して単結合又は炭素原子数１から４の直鎖状のアルキレン基を表し、該アルキレン基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、又は−Ｃ≡Ｃ−に置き換えられてもよく、Ｗ^１ｂ１及びＷ^１ｂ２中に存在する水素原子はフッ素原子に置換されてもよく、
Ｙ^１ｂ２及びＹ^１ｂ３は各々独立して単結合又は−ＣＨ＝ＣＨ−を表し、
ｍ^１ｂ１及びｎ^１ｂ１は各々独立して０から５の整数を表すが、ｍ^１ｂ１＋ｎ^１ｂ１は１から５を表す。］

^{Wherein, A 1b1, A 1b2, Z} 1b1 and ^{Z 1b2} is the formula in ^{(1), A 1, A} 2, represents the same meaning as ^{Z 1} and ^{Z 2,}
R ^1b1 and ^{R 1b2} are each independently an alkyl group having 1 to 8 carbon atoms, said alkyl group being present on one -CH ₂ - or nonadjacent two or more -CH ₂ - is Each independently may be replaced by —CH═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO—;
W ^1b1 and W ^1b2 represent each independently a single bond or a linear alkylene group having a carbon number of 1 to 4, one -CH 2 present in the alkylene group _- two of or nonadjacent more -CH ₂ - are each independently -O -, - S -, - COO -, - OCO -, - CO-, or -C≡C- may be replaced ^{by, W 1b1} and ^W in ^1b2 A hydrogen atom present in may be substituted with a fluorine atom,
Y ^1b2 and Y ^1b3 each independently represent a single bond or —CH═CH—,
m ^1b1 and n ^1b1 each independently represent an integer of 0 to 5, while m ^1b1 + n ^1b1 represents 1 to 5. ]

［式中、Ａ^１ｃ２及びＺ^１ｃ２は前記一般式（１）におけるＡ^２及びＺ^２と同じ意味を表し、
Ａ^１ｃ３は

[Wherein, A ^1c2 and Z ^1c2 represent the same meaning as A ² and Z ² in the general formula (1),
A ^1c3

から選ばれる基を表し、
Ｒ^１ｃ１は炭素原子数１から１５のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｒ^１ｃ２はフッ素原子、トリフルオロメトキシ基又はシアノ基を表し、
ｎ^１ｃ１は１から５の整数を表す。］

Represents a group selected from
R ^1c1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — present in the alkyl group are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R ^1c2 represents a fluorine atom, a trifluoromethoxy group or a cyano group,
n ^1c1 represents an integer of 1 to 5. ]

［式中、Ａ^１ｄ２及びＡ^１ｄ３は一般式（１）におけるＡ^２と同じ意味を表し、Ｚ^１ｄ２、Ｚ^１ｄ３及びＺ^１ｄ４は一般式（１）におけるＺ^２と同じ意味を表し、
Ｒ^１ｄ１は炭素原子数１から１５のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｒ^１ｄ２は炭素原子数１から８のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｗ^１ｄ１は単結合又は炭素原子数１から４の直鎖状のアルキレン基を表し、該アルキレン基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、又は−Ｃ≡Ｃ−に置き換えられてもよく、Ｗ^１ｄ１中に存在する水素原子はフッ素原子に置換されてもよく、
Ｙ^１ｄ２は単結合又は−ＣＨ＝ＣＨ−を表し、
ｎ^１ｄ１及びｎ^１ｄ２は各々独立して０から４の整数を表す。］

^{Wherein, A 1d2} and ^{A 1d3} has the same meaning as ^{A 2} in the general formula ^(1), Z ^{1d2, Z 1d3} and ^{Z 1d4} has the same meaning as ^{Z 2} in the general formula (1),
R ^1d1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — present in the alkyl group are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R ^1d2 represents an alkyl group having 1 to 8 carbon atoms, and one —CH ₂ — or two or more non-adjacent —CH ₂ — present in the alkyl group are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
W ^1d1 represents a linear alkylene group having 4 to single bond or a carbon atoms, one -CH 2 present in the alkylene group _- or nonadjacent two or more -CH 2 _- is Each independently may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, or —C≡C—, and the hydrogen atom present in W ^1d1 is replaced with a fluorine atom. May be,
Y ^1d2 represents a single bond or —CH═CH—,
n ^1d1 and n ^1d2 each independently represent an integer of 0 to 4. ]

［式中、Ａ^１ｅ２及びＺ^１ｅ２は前記一般式（１）における、Ａ^２及びＺ^２と同じ意味を表し、
Ｒ^１ｅ１は炭素原子数１から１５のアルキル基を表し、当該アルキル基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は各々独立して、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−又は−ＣＯ−に置き換えられてもよく、
Ｒ^１ｅ２はヒドロキシル基、ヒドロキシメチル基、ブロモメチル基、クロロメチル基、メタンスルホニルオキシメチル基、トルエンスルホニルオキシメチル基、塩素原子、臭素原子、ヨウ素原子、トリフルオロメタンスルホニルオキシ基又は

[ ^Wherein , A ^1e2 and Z ^1e2 represent the same meaning as A ² and Z ² in the general formula (1),
R ^1e1 represents an alkyl group having 1 to 15 carbon atoms, and one —CH ₂ — present in the alkyl group or two or more non-adjacent —CH ₂ — are each independently —CH _2. ═CH—, —C≡C—, —O—, —S—, —COO—, —OCO— or —CO— may be substituted,
R ^1e2 is a hydroxyl group, hydroxymethyl group, bromomethyl group, chloromethyl group, methanesulfonyloxymethyl group, toluenesulfonyloxymethyl group, chlorine atom, bromine atom, iodine atom, trifluoromethanesulfonyloxy group or

（式中の黒点はＡ^１ｅ２中のＲ^１ｅ２と直接結合する炭素原子を表し、Ｒ^１ｅ３は炭素原子数１から５のアルキル基又は水素原子を表す。）を表し、
ｎ^１ｅ１は１から４の整数を表す。］

(Black dot in the formula represents a carbon atom bonded directly with ^{R 1e2} in ^{A 1e2, R 1e3} represents. Alkyl group or a hydrogen atom having 1 to 5 carbon atoms) represent,
n ^1e1 represents an integer of 1 to 4. ]

  Specific examples of preferred compounds are shown below, but the present invention is not limited thereto.

  In general formula (1a), each compound represented by the following general formula (1a-1)-general formula (1a-23) is preferable.

（式中、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２は前記一般式（１ａ）における、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２と同じ意味を表す。）

( ^Wherein , R ^1a1 , Z ^1a2 and R ^1a2 represent the same meaning as R ^1a1 , Z ^1a2 and R ^1a2 in the general formula (1a)).

［式中、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２は前記一般式（１ａ）における、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２と同じ意味を表す。］

[ ^Wherein , R ^1a1 , Z ^1a2 and R ^1a2 represent the same meaning as R ^1a1 , Z ^1a2 and R ^1a2 in the general formula (1a). ]

［式中、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２は前記一般式（１ａ）における、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２と同じ意味を表す。］

[ ^Wherein , R ^1a1 , Z ^1a2 and R ^1a2 represent the same meaning as R ^1a1 , Z ^1a2 and R ^1a2 in the general formula (1a). ]

［式中、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２は前記一般式（１ａ）における、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２と同じ意味を表す。］

[ ^Wherein , R ^1a1 , Z ^1a2 and R ^1a2 represent the same meaning as R ^1a1 , Z ^1a2 and R ^1a2 in the general formula (1a). ]

［式中、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２は前記一般式（１ａ）における、Ｒ^１ａ１、Ｚ^１ａ２及びＲ^１ａ２と同じ意味を表す。］

[ ^Wherein , R ^1a1 , Z ^1a2 and R ^1a2 represent the same meaning as R ^1a1 , Z ^1a2 and R ^1a2 in the general formula (1a). ]

  In general formula (1b), each compound represented by the following general formula (1b-1)-general formula (1b-10) is preferable.

［式中、Ｒ^１ｂ１及びＲ^１ｂ２は前記一般式（１ｂ）における、Ｒ^１ｂ１及びＲ^１ｂ２と同じ意味を表す。］

^{Wherein, R 1b1} and ^{R 1b2} is the formula in ^(1b), the same meanings as ^{R 1b1} and ^{R 1b2.} ]

［式中、Ｒ^１ｂ１及びＲ^１ｂ２は前記一般式（１ｂ）における、Ｒ^１ｂ１及びＲ^１ｂ２と同じ意味を表す。］

^{Wherein, R 1b1} and ^{R 1b2} is the formula in ^(1b), the same meanings as ^{R 1b1} and ^{R 1b2.} ]

  In general formula (1c), each compound represented by the following general formula (1c-1)-general formula (1c-65) is preferable.

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２Ｚ^１ｃ１及びＡ^１ｃ３と同じ意味を表す。］

^{Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is in the general formula ^(1c), the same meanings as R ^1c1, R ^{1c2 Z 1c1} and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２、Ｚ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{[Wherein, R 1c1, R 1c2, Z} 1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^1c1, R ^{1c2, Z} 1c2 and ^{A 1c3.} ]

［式中、Ｒ^１ｃ１、Ｒ^１ｃ２及びＡ^１ｃ３は前記一般式（１ｃ）における、Ｒ^１ｃ１、Ｒ^１ｃ２及びＡ^１ｃ３と同じ意味を表す。］

^{Wherein, R 1c1,} R ^1c2 and ^{A 1c3} is the formula in ^(1c), the same meanings as R ^{1c1, R 1c2} and ^{A 1c3.} ]

  In general formula (1d), each compound represented with the following general formula (1d-1)-general formula (1d-35) is preferable.

［式中、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２は前記一般式（１ｄ）における、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２と同じ意味を表す。］

[Wherein, R ^1d1 , R ^1d2 and Z ^1d2 represent the same meaning as R ^1d1 , R ^1d2 and Z ^1d2 in the general formula (1d). ]

［式中、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２は前記一般式（１ｄ）における、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２と同じ意味を表す。］

[Wherein, R ^1d1 , R ^1d2 and Z ^1d2 represent the same meaning as R ^1d1 , R ^1d2 and Z ^1d2 in the general formula (1d). ]

［式中、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２は前記一般式（１ｄ）における、Ｒ^１ｄ１、Ｒ^１ｄ２及びＺ^１ｄ２と同じ意味を表す。］

[Wherein, R ^1d1 , R ^1d2 and Z ^1d2 represent the same meaning as R ^1d1 , R ^1d2 and Z ^1d2 in the general formula (1d). ]

  In general formula (1e), each compound represented by the following general formula (1e-1)-general formula (1e-13) is preferable.

［式中、Ｒ^１ｅ１、Ｒ^１ｅ２及びＺ^１ｅ２は前記一般式（１ｅ）における、Ｒ^１ｅ１、Ｒ^１ｅ２及びＺ^１ｅ２と同じ意味を表す。］

[ ^Wherein , R ^1e1 , R ^1e2 and Z ^1e2 represent the same meaning as R ^1e1 , R ^1e2 and Z ^1e2 in the general formula (1e). ]

The sulfur compound is not particularly limited as long as it is a compound containing one or more sulfur atoms, but is preferably an organic sulfur compound from the viewpoint of easily generating sulfur radicals and excellent reaction promotion effect, and represented by the following general formula (A) It is more preferable that it is a compound chosen from the compound group represented by-(H). Further, from the same point, the sulfur compound is preferably an SS bond-containing compound, and from the group of compounds represented by the following general formulas (A), (C), (D), (E) and (F) It is more preferable that it is a compound selected, and it is still more preferable that it is a compound selected from the compound group represented by the following general formula (A), (D), and (F). The S—S bond-containing compound may be a compound having one S—S bond or a compound having two or more S—S bonds. Further, the two S atoms in the S—S bond are each independently an unoxidized S atom, ie, —S—, but an oxidized S atom, ie, —S (═O) — or —S ( ═O) ₂ —.

［式中、Ｒ^ａ及びＲ^ｂは各々独立して置換又は無置換のフェニル基、置換又は無置換の炭素原子数１から８のアルキル基、置換又は無置換の炭素原子数２から８のアルケニル基及び水素原子から選ばれる基を表す。］
Ｒ^ａ及び／又はＲ^ｂがフェニル基である場合、該フェニル基は、無置換であるか、又は直鎖状又は分岐状の炭素原子数１から８のアルキル基、直鎖状又は分岐状の炭素原子数１から８のアルコキシ基、直鎖状又は分岐状の炭素原子数２から８のアルケニル基、塩素原子、アミノ基あるいはヒドロキシ基等で置換されていることが好ましい。

[Wherein, R ^a and R ^b are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. Represents a group selected from a group and a hydrogen atom. ]
When R ^a and / or R ^b is a phenyl group, the phenyl group is unsubstituted or a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched group. It is preferably substituted with an alkoxy group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a chlorine atom, an amino group, or a hydroxy group.

When R ^a and / or R ^b are an alkyl group or an alkenyl group, the alkyl group or alkenyl group may be linear or branched. In addition, when R ^a and / or R ^b is an alkyl group or an alkenyl group, the alkyl group or alkenyl group may be unsubstituted or substituted with a chlorine atom, an amino group, a hydroxy group, or the like. preferable.

  Specific examples of these sulfur compounds include diphenyl disulfide, phenyl sulfide, benzenethiol, (phenylsulfonyl) phenyl sulfide, diphenyl disulfone, diphenyl sulfoxide, diphenyl sulfone, di-p-tolyl disulfide, and 2,2′-diaminodiphenyl disulfide. 4,4'-diaminodiphenyl disulfide, 4,4'-dihydroxydiphenyl disulfide, 3,3'-dihydroxydiphenyl disulfide, bis (p-methoxyphenyl) disulfide, 4,4'-dichlorodiphenyl disulfide, 4,4 ' -Difluorodiphenyl disulfide, bis (4-carboxyphenyl) disulfide, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, diary Disulfide, and the like. Among these, diphenyl disulfide, (phenylsulfonyl) phenyl sulfide or diphenyl disulfone is preferable, and diphenyl disulfide is more preferable.

  The addition amount of the sulfur compound used for the isomerization reaction can be, for example, 0.1 to 10 mol% with respect to the total amount of the olefin derivative as the raw material. The lower limit of the amount of sulfur compound added is preferably 0.2 mol% or more, 0.5 mol% or more, 1% or more, or 2% or more with respect to the total amount of the olefin derivative as a raw material. Moreover, it is preferable that the upper limit of the addition amount of a sulfur compound is 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less with respect to the total amount of the olefin derivative which is a raw material.

  A conventionally well-known thing can be used as a radical initiator. Specific examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4). -Dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis- (cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (2-methylpropio) Natto), 2,2′-azobis (N-butyl-2-methylpropionamide), 4,4′-azobis (4-cyanopentanoic acid) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypi Valate, 1,1′-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, t-hexylpe Organic peroxides such as oxy-2-ethylhexanoate, from the viewpoint of excellent reaction acceleration effect, azo compounds are preferred. A radical initiator having an appropriate half-life temperature can be appropriately selected according to the reaction temperature of the isomerization reaction, the type of the substrate, and the like.

  The addition amount of the radical initiator used for the isomerization reaction can be, for example, 0.1 to 10 mol% with respect to the total amount of the olefin derivative as the raw material. The lower limit of the addition amount of the radical initiator is preferably 0.2 mol% or more, 0.5 mol% or more, 1% or more, or 2% or more with respect to the total amount of the olefin derivative as a raw material. Moreover, it is preferable that the upper limit of the addition amount of a radical initiator is 8 mol% or less, 7 mol% or less, 6 mol% or less, or 5 mol% or less with respect to the olefin derivative whole quantity which is a raw material.

  In the method of the present invention, the temperature at which the sulfur compound and the radical initiator are allowed to act can be, for example, 20 ° C to 120 ° C. From the viewpoint of suppressing the assumed side reaction, the temperature is preferably 20 ° C to 90 ° C, and more preferably 20 ° C to 70 ° C.

  The method of the present invention is preferably carried out in the presence of a solvent in order to control the reaction. Examples of the solvent to be used include aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbon solvents such as hexane, heptane and cyclohexane, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and 1,1. Chlorinated solvents such as 1,2,2-tetrachloroethane, ether solvents such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether and t-butyl methyl ether, and alcoholic solvents such as methanol and ethanol can be suitably used. , Toluene, THF, and methanol are particularly preferable. These solvents may be mixed and used as necessary.

  Although the method of the present invention can be carried out in air, it is preferably carried out in an inert atmosphere such as nitrogen from the viewpoint of improving reactivity and suppressing side reactions.

  In the method of the present invention, an SS bond-containing compound is allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule under heating, so that at least the olefin structure representing the Z isomer is present. A method for producing an isomer may be used in which one isomerizes to an olefin structure representing E form. In this method, the reaction can be carried out under the same conditions as in the above method except that the isomerization under heating is an essential requirement without using a radical initiator. The heating temperature can be, for example, 50 ° C to 120 ° C.

  By the method of the present invention, the mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative (E-form / Z-form) is 75/25 or more, that is, the inclusion of the E-olefin derivative in the E / Z-olefin composition The amount can be increased to 75% by mass or more. The mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative is preferably higher, (E isomer / Z isomer) = 80/20 or more is preferable, and 85/15 or more is more preferable. . The mass ratio of the E-olefin derivative to the mass of the Z-olefin derivative (E-form / Z-form) can be quantified by gas chromatography.

  In order to remove the Z-olefin derivative remaining in the E / Z-olefin composition after the isomerization reaction and obtain the target E-olefin derivative, the E / Z-olefin composition may be further purified. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. When using a purification agent, silica gel, alumina, activated carbon, activated clay, celite, zeolite, mesoporous silica, carbon nanotube, carbon nanohorn, Bincho charcoal, charcoal, graphene, ion exchange resin, acid clay, silicon dioxide, diatomaceous earth, Examples include perlite, cellulose, organic polymer, and porous gel. When such purification is repeated, there is a problem that the isolated yield of the E-olefin derivative is lowered. Since the mass ratio can be further increased, the number of purifications can be reduced, and the yield of the E-olefin derivative can be improved.

  Hereinafter, although an example is given and the present invention is explained still in full detail, the present invention is not limited by these.

The gas chromatography analysis was performed under the following conditions.
Sample preparation: 1% by mass acetone solution column introduction amount: 1 μL
Equipment: GC2010 (Shimadzu Corporation)
Column: J & WDB-17MS (30m × 0.25μm × 0.25mm)
Carrier gas: Nitrogen column pressure: (226 kPa), column flow rate: 3.19 mL / min, average speed: 58.8 cm / sec
Split ratio: 50: 1
Injection temperature: 300 ° C, detector temperature: (FID) 320 ° C
Column temperature setting: 100 ° C (1 min) → 10 ° C / min → 300 ° C (14 min)

(Example 1)

式（１）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝５／９５）、ジフェニルジスルフィド（３１ｍｇ）及びメタノール（７．５ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温４７℃に加熱した。内温４７℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（３５ｍｇ）を加えた後、２４時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ体／Ｚ体＝８５／１５であった。この反応溶液にトルエン（１０ｍＬ）及び、水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（２）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ体／Ｚ体＝８５／１５）を得た。

E / Z olefin composition of formula (1) (3 g, E isomer / Z isomer = 5/95), diphenyl disulfide (31 mg) and methanol (7.5 mL) were mixed at room temperature in a reaction vessel substituted with nitrogen. Then, the internal temperature was heated to 47 ° C. 2,2-Azobis (2,4-dimethylvaleronitrile) (35 mg) was added at an internal temperature of 47 ° C., and the mixture was stirred for 24 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 85/15. Toluene (10 mL) and water (10 mL) were added to the reaction solution, and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (2) (quantitative yield, E isomer / Z isomer = 85/15).

(Example 2)

（式（３）及び（４）における「ＴＨＰ」は、２−テトラヒドロピラニル基を示す。）
式（３）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝１０／９０）、ジフェニルジスルフィド（２２ｍｇ）及びＴＨＦ（１０ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温５１℃に加熱した。内温５１℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（２５ｍｇ）を加えた後、１０時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ体／Ｚ体＝８３／１７であった。この反応溶液にトルエン（１０ｍＬ）及び、水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（４）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ体／Ｚ体＝８３／１７）を得た。

(“THP” in formulas (3) and (4) represents a 2-tetrahydropyranyl group.)
After mixing the E / Z olefin composition of formula (3) (3 g, E isomer / Z isomer = 10/90), diphenyl disulfide (22 mg) and THF (10 mL) at room temperature in a reaction vessel substituted with nitrogen. The internal temperature was heated to 51 ° C. 2,2-azobis (2,4-dimethylvaleronitrile) (25 mg) was added at an internal temperature of 51 ° C., followed by stirring for 10 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 83/17. Toluene (10 mL) and water (10 mL) were added to the reaction solution, and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (4) (quantitative yield, E isomer / Z isomer = 83/17).

Example 3

式（５）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝４／９６）、（フェニルスルホニル）フェニルスルフィド（９９ｍｇ）及びトルエン（１０ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温８５℃に加熱した。内温８５℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（９８ｍｇ）を加えた後、５時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ体／Ｚ体＝８５／１５であった。この反応溶液に水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（６）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ体／Ｚ体＝８５／１５）を得た。

Reaction vessel in which E / Z olefin composition of formula (5) (3 g, E isomer / Z isomer = 4/96), (phenylsulfonyl) phenyl sulfide (99 mg) and toluene (10 mL) were replaced with nitrogen at room temperature. And then heated to an internal temperature of 85 ° C. 2,2-azobis (2,4-dimethylvaleronitrile) (98 mg) was added at an internal temperature of 85 ° C., and the mixture was stirred for 5 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 85/15. Water (10 mL) was added to the reaction solution, liquid separation was performed, and the organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (6) (quantitative yield, E isomer / Z isomer = 85/15).

(Example 4)

式（７）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝５／９５）、ジフェニルジスルフィド（３５ｍｇ）及びメタノール（７．５ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温４８℃に加熱した。内温４８℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（４０ｍｇ）を加えた後、３０時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ体／Ｚ体＝８４／１６であった。この反応溶液にトルエン（１０ｍＬ）及び、水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（８）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ体／Ｚ体＝８４／１６）を得た。

E / Z olefin composition of formula (7) (3 g, E isomer / Z isomer = 5/95), diphenyl disulfide (35 mg) and methanol (7.5 mL) were mixed at room temperature in a reaction vessel substituted with nitrogen. Then, the internal temperature was heated to 48 ° C. 2,2-Azobis (2,4-dimethylvaleronitrile) (40 mg) was added at an internal temperature of 48 ° C., and the mixture was stirred for 30 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 84/16. Toluene (10 mL) and water (10 mL) were added to the reaction solution, and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (8) (quantitative yield, E isomer / Z isomer = 84/16).

(Example 5)

式（９）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝５／９５）、ジフェニルジスルフィド（３６ｍｇ）及びトルエン（７．５ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温５１℃に加熱した。内温５１℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（３６ｍｇ）を加えた後、２０時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ体／Ｚ体＝８５／１５であった。この反応溶液に水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（１０）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ体／Ｚ体＝８５／１５）を得た。

E / Z olefin composition of formula (9) (3 g, E isomer / Z isomer = 5/95), diphenyl disulfide (36 mg) and toluene (7.5 mL) were mixed at room temperature in a reaction vessel substituted with nitrogen. Then, the internal temperature was heated to 51 ° C. 2,2-Azobis (2,4-dimethylvaleronitrile) (36 mg) was added at an internal temperature of 51 ° C., followed by stirring for 20 hours. When the reaction liquid was analyzed by gas chromatography, it was E-form / Z-form = 85/15. Water (10 mL) was added to the reaction solution, liquid separation was performed, and the organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (10) (quantitative yield, E isomer / Z isomer = 85/15).

(Example 6)

式（１１）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ，Ｅ体／Ｅ，Ｚ体／Ｚ，Ｚ体＝８／４０／５２））、ジフェニルジスルフィド（２４ｍｇ）及びＴＨＦ（１５ｍＬ）を室温にて、窒素で置換した反応容器で混合した後、内温５１℃に加熱した。内温５１℃にて２，２−アゾビス（２，４−ジメチルバレロニトリル）（２８ｍｇ）を加えた後、２０時間攪拌した。反応液をガスクロマトグラフィーにて分析したところ、Ｅ，Ｅ体／Ｅ，Ｚ体／Ｚ，Ｚ体＝７７／２２／１であった。この反応溶液にトルエン（１０ｍＬ）及び水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（１２）のＥ／Ｚオレフィン組成物（収率定量的、Ｅ，Ｅ体／Ｅ，Ｚ体／Ｚ，Ｚ体＝７７／２２／１）を得た。

E / Z olefin composition of formula (11) (3 g, E, E isomer / E, Z isomer / Z, Z isomer = 8/40/52)), diphenyl disulfide (24 mg) and THF (15 mL) at room temperature. After mixing in a reaction vessel substituted with nitrogen, the mixture was heated to an internal temperature of 51 ° C. 2,2-Azobis (2,4-dimethylvaleronitrile) (28 mg) was added at an internal temperature of 51 ° C., followed by stirring for 20 hours. When the reaction liquid was analyzed by gas chromatography, it was E, E isomer / E, Z isomer / Z, Z isomer = 77/22/1. Toluene (10 mL) and water (10 mL) were added to the reaction solution, and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. Sodium sulfate is filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (12) (quantitative yield, E, E isomer / E, Z isomer / Z, Z isomer). = 77/22/1).

(Comparative Example 1)

式（１）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝５／９５）、ベンゼンスルフィン酸ナトリウム（２７９ｍｇ）、トルエン（７．５ｍＬ）を室温にて混合した後、内温９５℃に加熱した。内温９５℃にて１０質量％塩酸（７．５ｍＬ）をゆっくりと加え、更に５時間撹拌した。反応液をガスクロマトグラフィーにて分析したところ、目的物である式（２）のＥ／Ｚオレフィン組成物は、Ｅ体／Ｚ体＝７９／２１であった。また、副生成物として式（１３）の化合物が１３％生成していた。この反応溶液にＴＨＦ（１０ｍＬ）及び、水（１０ｍＬ）を加え、分液し、有機層を水（１０ｍＬ）、飽和食塩水（１０ｍＬ）の順に洗浄し、無水硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムをろ別した後、シリカゲルカラムクロマトグラフィーにて精製することで、式（２）のＥ／Ｚオレフィン組成物（収率７８％、Ｅ体／Ｚ体＝７９／２１）を得た。

An E / Z olefin composition of the formula (1) (3 g, E-form / Z-form = 5/95), sodium benzenesulfinate (279 mg) and toluene (7.5 mL) were mixed at room temperature, and the internal temperature was 95. Heated to ° C. 10% by mass hydrochloric acid (7.5 mL) was slowly added at an internal temperature of 95 ° C., and the mixture was further stirred for 5 hours. When the reaction liquid was analyzed by gas chromatography, the E / Z olefin composition of the formula (2), which was the target product, was E-form / Z-form = 79/21. Further, 13% of the compound of formula (13) was produced as a by-product. To this reaction solution were added THF (10 mL) and water (10 mL), and the phases were separated. The organic layer was washed with water (10 mL) and saturated brine (10 mL) in this order, and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and purified by silica gel column chromatography to obtain an E / Z olefin composition of formula (2) (yield 78%, E isomer / Z isomer = 79/21).

(Comparative Example 2)

式（３）のＥ／Ｚオレフィン組成物（３ｇ、Ｅ体／Ｚ体＝１０／９０）、ベンゼンスルフィン酸ナトリウム（１９０ｍｇ）及びＴＨＦ（７．５ｍＬ）を室温にて混合した後、内温６６℃に加熱した。内温６６℃にて濃塩酸（０．５ｍＬ）をゆっくりと加え、更に３時間撹拌した。反応液をガスクロマトグラフィーにて分析したところ、目的物である式（４）の化合物は得られず、メインピークとして、式（１４）のＥ／Ｚオレフィン組成物が得られた。

An E / Z olefin composition of the formula (3) (3 g, E isomer / Z isomer = 10/90), sodium benzenesulfinate (190 mg) and THF (7.5 mL) were mixed at room temperature, and then the internal temperature 66 Heated to ° C. Concentrated hydrochloric acid (0.5 mL) was slowly added at an internal temperature of 66 ° C., and the mixture was further stirred for 3 hours. When the reaction solution was analyzed by gas chromatography, the target compound of formula (4) was not obtained, and an E / Z olefin composition of formula (14) was obtained as the main peak.

  As is clear from the above results, the olefin isomerization reaction can be performed using the conditions of the present invention even for substrates that could not be applied under conventional acidic and high temperature isomerization reaction conditions. An E-olefin derivative is obtained.

Claims (6)

  A sulfur compound and a radical initiator are allowed to act on an olefin derivative having an olefin structure representing one or more Z forms in the molecule, and at least one of the olefin structures representing the Z form is converted to an olefin structure representing an E form. A method for producing an isomer by isomerization.   The manufacturing method of Claim 1 whose temperature which makes a sulfur compound and a radical initiator act is 20 to 120 degreeC.   The production method according to claim 1 or 2, wherein the radical initiator is an azo compound. The sulfur compound is represented by the general formula (A) to the general formula (H):

[Wherein, R ^a and R ^b are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. Represents a group selected from a group and a hydrogen atom. ]
The manufacturing method as described in any one of Claims 1-3 which is 1 type, or 2 or more types of compounds chosen from the compound group represented by these.   The manufacturing method as described in any one of Claims 1-3 whose sulfur compound is a SS bond containing compound.   An S—S bond-containing compound is allowed to act on an olefin derivative having an olefin structure representing one or more Z isomers in the molecule under heating, and at least one of the olefin structures representing the Z isomer represents an E isomer. A process for producing an isomer, wherein the olefin is isomerized.