POLYTHIOLS AS CIS/TRANS ISOMERIZATION CATALYSTS FOR UNSATURATED COMPOUNDS

Technical Field

The invention relates to unsaturated compound cis/trans-isomerization.

Background of the invention

Unsaturated compound having a carbon-carbon double bond. These compounds are in a cis or trans configuration. In particular, the functional group containing C=O of unsaturated compounds in the technically very important and having different properties, depending on the corresponding compound exists in what kind of double bond isomers (cis or trans). These compounds to the field of flavors, and vitamin the field of pharmaceutical composition (in particular vitamin K1 and tocopherol) synthesis of particular importance. Isomer in the smell in their hand and to the asymmetric addition to the carbon-carbon double bond different in particular of conduct.

Known carbon-carbon double bond can be isomerized. If for example DE   25   57   837 in, known transition metal derivatives and sulfur compounds (such as sulfide or disulfide or single thiol (monomercaptan) surfactant capable of isomerization.

US   4,028,385 discloses transition metal catalyst and an organic sulfur compound (such as sulfide or disulfide or single thiol (monomercaptan)) for isomerization farnesyl acetate and farnesyl acetate and rectification the corresponding three-dimensional heterogeneous mixture.

However, have been observed: in the prior art relates to the of organic sulfur compounds of the following unsaturated compound is not very effective, the unsaturated compound is selected from the group consisting of unsaturated ketone, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group.

Content of the invention

Therefore, the problem to be solved by the invention is:to provide the following compounds are very effective isomerization method and isomerization catalyst, said compound is selected from the group consisting of unsaturated ketone, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group.

Unexpectedly, it has been found that: according to Claim 1, 8 and 10 and the method according to claim 16 the composition can solve the problem. It has been found that: poly thiol is especially suitable for the isomerization of the above-mentioned compounds. They are very effectively make these compounds of the carbon-carbon double bond isomerization. Because the method of the present invention, substantially all the undesired isomer into a desired isomer become possible. This is not only in pure isomer circumstances is possible, and under the condition of the mixture is also possible.

Other aspects of the invention are the subject of other independent claim. Particularly preferred is subordinate to the embodiment of the subject of the claim.

Invention details

In the 1st aspect, the invention relates to unsaturated compounds of cis/trans-isomerization A method, said compound selected from unsaturated ketone A, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group, the method comprises the following steps:

A) provide unsaturated compound A cis-or trans-isomer;

B) to step a) unsaturated compound A in the cis or trans isomer by adding polymercaptans;

C) heating polymercaptans and unsaturated compound A cis or trans isomer mixture to between 20 the said unsaturated compounds and [...] A a temperature between the boiling point of, in particular between 50 the said unsaturated compounds and [...] A a temperature between the boiling point of;

So as to produce the unsaturated compounds of A a mixture of cis/trans-isomer.

In the substituent, fragment in the context of or groups (moieties), the terminology in this document, "independently" said: the same designated substituent, fragment or group can be in the same molecule with different meaning in at the same time.

As used in this document, "poly (poly)" LED to the name of substance means is of the form of each molecule comprises two or more corresponding functional group of the substance.

"C_x-y-alkyl" group is comprises x y carbon atoms of the alkyl group, i.e., for example, C_1-3-alkyl group comprises 1-3 carbon atoms of the alkyl group. Alkyl groups can be linear or branched. For example, -CH (CH₃)-CH₂-CH₃ is considered C₄-alkyl group.

"C_x-y-alkylene" group is comprises x y carbon atoms of the alkylene group, i.e., for example, C₂-C₆ alkylene group is comprises 2-6 carbon atoms of the alkyl group. Alkylene group may be a linear or branched. For example, -CH (CH₃)-CH₂-group is considered C₃-alkylene group.

"Aromatic polymercaptans" has 2 or more with an aromatic hydrocarbon directly combined with SH group of the poly thiol.

In this document " phenolic alcohol " expressed in: directly combined with the aromatic group of the hydroxyl group of the alcohol.

The terms used in this document, "solid center" the atom is provided with a the following group, these groups of any two groups in the exchange rise to stereoisomers. Stereo isomer are has the same atomic and bonding the molecular formula of (a) the order of the isomeric molecule, but their atoms of the three-dimensional orientation different from the space.

The configuration of the stereo center are defined as R or S. In determining the absolute configuration of the stereochemistry R/S-concepts and rules are known to those skilled in the art.

In the present document, if the hydrogen addition to the carbon-carbon double bond to form of the centre three-dimensional carbon , the carbon-carbon double bond is defined as "prochiral".

Cis/trans-isomer at the double bond of the configuration isomers with different orientations. In the present document, the term "cis" and "Z" equivalent use, or vice versa; the term "trans" and "E" equivalent use, or vice versa. Therefore, for example, the term "cis/trans-isomerization catalyst" is equivalent to the "E/Z isomerization catalyst" terminology.

The term "cis/trans-isomerization catalyst" is that the cis-isomer (Z-isomer) isomerization of the cis/trans isomer mixture (E/Z isomer mixture) or the trans-isomer (isomer E) isomerization of the cis/trans isomer mixture (E/Z isomer mixture) of the catalyst.

Terminology "E/Z", and "cis/trans" "R/S" E and Z respectively of said mixture, a mixture of cis and trans mixture of and R and S.

Terminology "isomerization" (or isomerization isomerize) in the entire document should be understood as limited to cis/trans-isomerization.

"Cis/trans ratio of balance" is used as a method of the present invention makes the isomerization of trans-isomers accept states the syn-form sustained or extended period of time (i.e., until the time is no longer observed that the cis/trans ratio of the further changes) to obtain the results of a specific cis and trans isomers to the ratio. Each pair of cis/trans-isomers have different balance cis/trans ratio.

"Non-equilibrium cis/trans ratio" is different from a "cis/trans ratio of balance" of any cis/trans isomer ratio.

"Unsaturated" compound, unsaturated ketone, ketal, aldehyde, aldehyde, carboxylic acid, unsaturated carboxylic acid ester or unsaturated carboxylic acid amide is defined as: ethylenically unsaturated (i.e., in its chemical structure having at least one carbon-carbon double bond), and preferably has at least one prochiral carbon-carbon double bond ketone, aldehyde, ketal, aldehyde, aldehyde, carboxylic acid, unsaturated carboxylic acid ester or unsaturated carboxylic acid amide.

In the present document, if the existing in certain types with a symbol mark or group mark, then in one concrete -like to the group in the context of the definition or symbols comprising said of the same marks is also applicable to the other type.

In the present document, any single dashed line represents following , substituent through said keying with the remainder of the molecule.

In the present document, bold marking for example A or I_Ibp or I_hbp in this document is only used for improvement in readability and used for identification.

A unsaturated compound

Unsaturated compound selected from unsaturated ketone A, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group, in its chemical structure having at least one carbon-carbon double bond and preferably has at least one prochiral carbon-carbon double bond.

It can have more than 1 a prochiral carbon-carbon double bond and/or 1 or a plurality of non-prochiral carbon-carbon double bond.

Preferably, unsaturated compounds formula A (I-0A) or (I-0B) or (I-0C) or (I-0D) or (I-0E) or (I-0F)

Wherein R 'representative linear or cycloaliphatic hydrocarbyl group, optionally comprising additional carbon-carbon double bond of the; Q' represents a group selected from the following group of the group in the group consisting of

Wherein R⁰ representative C₁-C₄-alkyl group, represents in particular methyl group;

Q¹ and Q² representative C₁-C₁₀ alkyl group or a halogenated C₁-C₁₀ alkyl group; C₁-C₄-alkyl group or together form a C₂-C₆ alkylene group or C₆-C₈link Asia alkyl group;

R " representative C₁-C₄-alkyl group, represents in particular methyl or ethyl group; and

R "' representative or H C₁-C₄-alkyl group, represents in particular methyl or ethyl group;

And wherein the wavy line represents a carbon-carbon bond, with the adjacent carbon-carbon double bond is connected to the or the carbon-carbon double bond is in the Z or in the-configuration E-configuration;

The Chinese (I-0B) or (I-0D) or (I-0F) with dashed-line The double bond of carbon-carbon bond represents a single or double carbon-carbon bond.

In one embodiment, type (I-0A) or (I-0C) R with the following formula of the group ''

And preferably to methyl ketone or its ketal, α-Ionone preferably, β-Ionone, Ionone γ; different α-Ionone, different β-Ionone, γ heteroploid-Ionone; n-methyl Ionone α, β, or n-methyl Ionone n-methyl Ionone γ; or its ketal.

Preferably, unsaturated compounds is not saturated and underburnt lime A unsaturated ketal or unsaturated aldehyde or unsaturated acetal.

In a preferred embodiment, the unsaturated compound is unsaturated ketone A or its ketal or unsaturated aldehyde or its acetal and γ relative to the carbonyl group, δ position having a carbon-carbon double bond.

In another preferred embodiment, the unsaturated compound is unsaturated ketone A or its ketal or unsaturated aldehyde or its acetal and with respect to the carbonyl group of the α, β position having a carbon-carbon double bond.

In still another preferred embodiment, the unsaturated compound is unsaturated ketone A or its ketal or unsaturated aldehyde or its acetal and with respect to the carbonyl group of the α, β position and having a carbon-carbon double bond γ relative to the carbonyl group, δ position having a carbon-carbon double bond.

Strongly preferably, A unsaturated compound of formula (I) or (II)

Representative wherein Q or H CH₃, m and p representative independently of each other 0 to 3 the conditions of spin-off value: the sum of the m and p is 0 to 3;

Wherein the wavy line represents a carbon-carbon bond, with the adjacent carbon-carbon double bond is connected to the or the carbon-carbon double bond is in the Z or in the-configuration E-configuration, wherein s1 and s2 represented by the formula of (I) and (II) in the sub-structure may be in any order;

The Chinese (I) and (II) having a dashed-line The double bond of carbon-carbon bond represents a single or double carbon-carbon bond;

And wherein Representative three-dimensional center.

P the sum of the m and is preferably 0 to 2, especially 0 or 1.

Therefore, formula (I) or (II) and underburnt lime unsaturated unsaturated aldehyde can be a single material or when the Mark wave key is connected with the three-dimensional center or with different orientations at the double bond of the different three-dimensional of the mixture of isomers. However, preferably, type (I) or (II) unsaturated unsaturated the aldehyde is and underburnt lime in the solid center has a particular configuration and a separate material. Preferably, the configuration of the stereo center is R configuration. If p ≥ 2, is preferably, for Mark all the different stereo center is in the same configuration, in other words: all R configuration S configuration or all, preferably all is in the R configuration.

Particularly preferred unsaturated unsaturated the aldehyde has the type and underburnt lime (II). Most preferably, the unsaturated unsaturated the aldehyde elects and underburnt lime in the free 3, 7-dimethyl-octa -2, 6-di- olefine aldehyde , 3, 7-dimethyl-octa-2- olefine aldehyde , 6, 10-dimethyl -3, 5, 9-triene-2-one, 6, 10-dimethyl -5, 9-dien-2-one, 6, 10-dimethyl-5-ene-2-one, 6, 10-dimethyl-3-ene-2-one, 6, 10-dimethyl -3, 5-dien-2-one, (R)-6, 10-dimethyl-3-ene-2-one, 6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-one, 6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one, 6, 10, 14-trimethyl fifteen carbon-5-ene-2-one and (R)-6, 10, 14-trimethyl fifteen carbon-5-ene-2-one and all of them may be of the group consisting of-isomer E/Z.

Most preferably, the unsaturated unsaturated the aldehyde is the alkone and underburnt lime.

Furthermore, preferably, the unsaturated compound is unsaturated A and underburnt lime in the ketal or acetal of unsaturated aldehyde, particularly of formula (I) or (II) acetal or ketal.

Technical personnel in the field by ketone known per se to form a ketal or by aldehyde form the acetal.

Ketal of unsaturated ketone can be preferably formed by the above-mentioned unsaturated alkone and mellow form. Acetal of unsaturated aldehyde can be by the above-mentioned unsaturated aldehyde and mellow form.

Techniques known to those skilled in this field: synthesis of acetal or ketal alternative pathway. In principle, for example in Pério Tetrahedron   Letters   1997, 38 (45), 7867-7870 or in the Howard J.Org.Chem. 1960 and Lorette, 25,521-525 disclosed in, through the original ester can also be used for treatment of a ketone or an aldehyde compound or through the transform shrinks (transketalization) reaction to form a ketal or acetal, all the contents of the two has been incorporated in this text by reference.

Preferably, by the above-mentioned unsaturated unsaturated aldehyde and mellow and underburnt lime to form a ketal or acetal.

In principle, for the ketal or acetal any mellowmellow may is formed, that is, : comprising alcohol produced may be 1 or a plurality of hydroxyl groups. Is mellow mayphenolic alcohol or fatty alcohol or the fat link race is mellow. However, preferably, one hydroxy group with mellow (ol=)or two hydroxyl groups (= glycol).

If mellow with a hydroxy group, then mellow preferably has 1 to 12 carbon atoms of the alcohol. Specifically, with a hydroxyl group are as follows from the group consisting of free elects mellowly : methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, pentane-1-ol, 3-methyl-butane-1-ol, 2-methyl butane-1-ol, 2, 2- dimethyl third -1-ol, pentane-3-ol, pentane-2-ol, 3-methyl butane-2-ol, 2-methylbut-1-ol, hexane-1-ol, hexane-2-ol, hexane-3-ol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 2, 2-dimethyl-1-butanol, 2, 3-dimethyl-1-butanol, 3, 3-dimethyl-1-butanol, 3, 3-dimethyl-2-butanol, 2-ethyl-1-butanol, and heptanol, octanol and halogenated C₁-C₈-all structural isomer of alkyl alcohols, in particular 2, 2, 2-trifluorethanol. Particularly suitable is a primary or secondary alcohol. Preferably, the primary alcohol is used as a hydroxyl group of the alcohol. Specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol or 2, 2, 2-trifluoro ethyl alcohol, preferably methanol, ethanol, 1-propanol, 1-butanol or 2, 2, 2-trifluoro-ethanol is used as a has a hydroxyl group of the alcohol.

In another embodiment, mellow is glycol. Preferably, diols selected from the group consisting of the following: ethane -1, 2-diol, propane -1, 2-diol, propane -1, 3-diol, butane -1, 4-diol, butane -1, 3-diol, butane -1, 2-diol, butane -2, 3-diol, 2-methyl propane -1, 2-diol, 2-methyl propane -1, 3-diol, 2, 2-dimethyl-propane -1, 3-diol, 1, 2-dimethyl-propane -1, 3-diol, 3-methyl pentane -2, 4-diol and 2-(hydroxymethyl) cyclohexanol, benzene -1, 2-glycol and cyclohexane -1, 2-diol. Two cyclohexane -1, 2-diol is preferably in stereo isomer same type (syn-)-cyclohexane -1, 2-diol (= cis-cyclohexane -1, 2-diol).

In one embodiment, 2 hydroxy group and 2 with adjacent carbon atoms, these glycol is a vicinal diol. Vicinal diol in the ketal or acetal form a 5 membered ring.

Particularly suitable is the following O-glycol, its is selected from the group consisting of ethane -1, 2-diol, propane -1, 2-diol, butane -1, 2-diol, butane -2, 3-diol, 2-methyl propane -1, 2-diol, benzene -1, 2-diol and same type -cyclohexane -1, the group consisting of 2-diol, especially ethane -1, 2-diol.

Other particularly suitable is the following diol, wherein the hydroxy group is 3 carbon atoms are separated, the ketal or acetal form very stable 6 membered ring. This type of the special appropriate diol is propane -1, 3-diol, butane -1, 3-diol, 2-methyl propane -1, 3-diol, 2-methyl butane -1, 3-diol, 2, 2-dimethyl-propane -1, 3-diol, 1, 2-dimethyl-propane -1, 3-diol, 3-methyl pentane -2, 4-diol and 2-(hydroxymethyl) ring hexanol.

Preferably, primary alcohol is used as the diol.

Known technical personnel in the field for acetal or ketal forming reaction conditions and stoichiometric. In particular, the acid acetal or ketal is formed under the influence of.

Preferred unsaturated ketone is preferably the ketal or acetal of unsaturated aldehyde of the formula (XI) or (XII)

In formula (XI) and (XII) with the group and symbol before in this document has the formula (I) and (II) limit the meaning of the same.

Q¹ and Q² representative separately or together C₁-C₁₀ alkyl group or a halogenated C₁-C₁₀ alkyl group;

Or together form a C₂-C₆ alkylene group or C₆-C₈link Asia alkyl group.

Especially, Q¹ and Q² representative

Linear C₁-C₁₀ alkyl group or fluorinated linear C₁-C₁₀ alkyl group, preferably linear C₁-C₄ alkyl group or-CH₂ CF₃ group

The group or the following formula

wherein Q³, Q⁴, Q⁵ and Q⁶ independently represent a hydrogen atom or a methyl or ethyl group.

optimal, type (XI) either the (XII) ketal or the acetal are (E) - 2- (4,8- dimethyl ninth stem - 3,7- two alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, the (E)-2,6- dimethyl - 10,10- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 2,6- two alkene, (E) - 2- (4,8- dimethyl ninth stem - 3- alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, the (E)-6,10- dimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 5- alkene, the (E)-2,5,5- trimethyl - 2- (4,8,12- trimethyl 13 carbon - 3- alkene - 1- base) - 1,3- two wicked alkane, the (R, E)-2,5,5- trimethyl- 2- (4,8,12- trimethyl 13 carbon - 3- alkene - 1- base) - 1,3- two wicked alkane, (E)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5- alkene, (R, E)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5- alkene, (Z) - 2- (4,8- dimethyl ninth stem - 3,7- two alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, (Z)-2,6- dimethyl - 10,10- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 2,6- two alkene, (Z) - 2- (4,8- dimethyl ninth stem - 3- alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, (Z)-6,10- dimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 5- alkene, (Z)-2,5,5- trimethyl - 2- (4,8,12- trimethyl 13 - 3- alkene - 1- base) - 1,3- two wicked alkane, (R, Z)-2,5,5- trimethyl - 2- (4,8,12- trimethyl 13 carbon - 3- alkene - 1- base) - 1,3- two wicked alkane, 2,5,5- trimethyl - 2-((3E,7E) - 4,8,12- trimethyl 13 carbon - 3,7,11- three alkene - 1- base) - 1,3- two wicked alkane, (6E,10E)-2,6,10- trimethyl - 14,14- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 2,6,10- three alkene, 2,5,5- trimethyl - 2-((3E,7E) - 4,8,12- trimethyl 13 carbon - 3,7- two alkene - 1- base) - 1,3- two wicked alkane, (5E,9E)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5,9- two alkene, 2,5,5- trimethyl - 2-((3Z,7E) - 4,8,12- trimethyl 13 carbon - 3,7,11- three alkene - 1- base) - 1,3- two wicked alkane, 2,5,5- trimethyl - 2-((3E,7Z) - 4,8,12- trimethyl 13 carbon - 3,7,11- three alkene - 1- base) - 1,3- two wicked alkane, 2,5,5- trimethyl - 2-((3Z,7Z) - 4,8,12- trimethyl 13 carbon - 3,7,11- three alkene - 1- base) - 1,3- two wicked alkane, (6Z,10E)-2,6,10- trimethyl - 14,14- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 2,6,10- three alkene, (6E,10Z)-2,6,10- trimethyl - 14,14- pair(2,2,2- three fluorine ethoxy group) 15 carbon - 2,6,10- three alkene, (6Z,10Z)-2,6,10- trimethyl - 14,14- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 2,6,10- three alkene, 2,5,5- trimethyl - 2-((3Z,7E) - 4,8,12- trimethyl 13 carbon - 3,7- two alkene - 1- base) - 1,3- two wicked alkane, 2,5,5- trimethyl - 2-((3E,7Z) - 4,8,12- trimethyl 13 carbon - 3,7- two alkene - 1- base) - 1,3- two wicked alkane, 2,5,5- trimethyl - 2-((3Z,7Z) - 4,8,12- trimethyl 13 carbon - 3,7- two alkene - 1- base) - 1,3- two wicked alkane, (5Z,9E)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5,9- two alkene, (5E,9Z)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5,9- two alkene, (5Z,9Z)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5,9- two alkene, (E) - 2- (2,6- dimethyl age - 1- alkene - 1- base) - 5,5- dimethyl - 1,3- two wicked alkane, (E)-3,7- dimethyl - 1,1- pair (2,2,2- three fluorine ethoxy group) Xin - 2- alkene, (E)-3,7- dimethyl - 1,1- pair (2,2,2- three fluorine ethoxy group) Xin - 2,6- two alkene, (Z) - 2- (2,6- dimethyl age - 1- alkene - 1- base) - 5,5- dimethyl - 1,3- two wicked alkane, (Z)-3,7- dimethyl- 1,1- pair (2,2,2- three fluorine ethoxy group) Xin - 2- alkene, (Z)-3,7- dimethyl - 1,1- pair (2,2,2- three fluorine ethoxy group) Xin - 2,6- two alkene, 2,6- dimethyl - 8,8- pair (2,2,2- three fluorine ethoxy group) Xin - 2- alkene, (R)-2,6- dimethyl - 8,8- pair (2,2,2- three fluorine ethoxy group) Xin - 2- alkene, 2-((1Z,3E) - 4,8- dimethyl ninth stem - 1,3,7- three alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, 2-((1E,3Z) - 4,8- dimethyl ninth stem - 1,3,7- three alkene - 1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, 2-((1Z,3Z) - 4,8- dimethyl ninth stem - 1,3,7- three alkene -1- base) - 2,5,5- trimethyl - 1,3- two wicked alkane, (6Z,8E)-2,6- dimethyl - 10,10- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 2,6,8- three alkene, (6E,8Z)-2,6- dimethyl - 10,10- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 2,6,8- three alkene, (6Z,8Z)-2,6- dimethyl - 10,10- pair (2,2,2- three fluorine ethoxy group) 11 carbon - 2,6,8- three alkene, (Z)-2,5- dimethyl - 2- (4,8,12- trimethyl 13 carbon - 3- alkene - 1- base) - 1,3- two wicked alkane, (R, Z)-2,5- dimethyl - 2- (4,8,12- trimethyl 13 carbon - 3- alkene - 1- base) - 1,3- two wicked alkane, (Z)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5- alkene and (R, Z)-6,10,14- trimethyl - 2,2- pair (2,2,2- three fluorine ethoxy group) 15 carbon - 5- alkene.

In step a) in, A provide unsaturated compounds of cis-or trans-isomer.

In one embodiment, the compound A only a single stereoisomers. Said compound A single stereoisomers can be stereoisomers of the stereospecific synthetic or the result of the separation process.

In another embodiment, the unsaturated compound A cis or trans isomer of non-balance as a cis/trans ratio of the cis and trans of the mixture of isomers is provided. Typically, the non-balance cis/trans ratio is greater than 70/30, preferably more than 80/20, more preferably greater than 90/10 or less than 30/70, is preferably less than 20/80, more preferably less than 10/90.

Polymercaptans

In step b) in, to step a) unsaturated compound A in the cis or trans isomer by adding polymercaptans;

Polymercaptans is to make the carbon-carbon double bond isomerization of cis/trans-isomerization catalyst.

It is worth noting that, we have observed that the: with only 1 mercapto group of a thiol (i.e., single thiol) can not be used as the unsaturated compound A of cis/trans-isomerization catalyst, or compared with the poly thiol, only show a very low efficiency.

Particularly suitable polymercaptans is aromatic poly mercaptane or type (X) poly thiol

Wherein n1 from 1 to 4 of the integer, in particular 2,

M1 from 2 to 8 of the integer, in particular 3 or 4, preferably 4;

The molecular weight of the representative A 28g/mol to 400g/mol between, preferably 90g/mol to 150g/mol aliphatic between m1 monovalent hydrocarbyl.

1st group of preferred poly thiol is aromatic polymercaptans. SH group in aromatic on hydrocarbon directly combined. Aromatic hydrocarbons may have one or several aromatic ring. The aromatic rings can be formed or can be spacer condensed ring system (for example, the alkylene group or the functional group) are separated. SH group can be incorporated directly in the same or different on the aromatic ring on the aromatic ring.

Particularly preferred aromatic polymercaptans is 4, the 4 [...] -dithiopurine biphenyltetrazole (4, the 4 [...] -dimercaptobiphenyl) or 4, 4 the thiol generation of benzoin[...] -sulfur (4, the 4 [...] -thiodibenzenethiol).

Another group of preferred polymercaptans formula (X) poly thiol.

These substance is polyol A (OH)_m1 and provided with a terminal sulfhydryl group of the carboxylic acid SH-(CH₂)_n1-COOH ester. A molecular weight of 62 and 538 the preferred polyol between A (OH)_m1 is trimethylolpropane, three hydroxymethyl ethane, three hydroxy methylmethane, three propylene glycol, 1, 2-propylene glycol, 1, the isomer 4-butanediol, 1, 5-pentanediol of the isomer, 1, 6-hexane diol isomers, dipropylene glycol, 1, 4-cyclohexyldimethanol and its isomer, 1, 4-bis (2-hydroxy-ethoxy) cyclohexane, ten methylene glycol, norbornene glycol, 1, 4-benzene ethanol, 2, 4-dimethyl-2-vinyl-hexane -1, 3-diol, 2-butene -1, 4-diol, ethoxylated trimethylolpropane, three methylol hexane, 1, 2, 4-butanetriol, pentaerythritol, dipentaerythritol (=2, 2 the [...] -(oxygen double (methylene)) double (2-(hydroxymethyl)-propane -1, 3-diol)), di (trimethylolpropane) (=2, 2 the [...] -(oxygen (methylene)) double (2-ethyl-propane -1, 3-diol)), two (three hydroxymethyl ethane) (=2, 2 the [...] -(oxygen double (methylene)) double (2-methyl-propane -1, 3-diol)), ethylene glycol, diethylene glycol, dipropylene glycol.

The technicians of this field know: preparing the above ester can be by different methods, are not limited to, polyols having terminal mercapto group with the above-mentioned reaction of the carboxylic acid.

Polymercaptans pentaerythritol tetra (mercapto acetate), trimethylolpropane (mercapto acetate) propane three , dithiopurine acetic acid ethylene glycol ester, pentaerythritol tetra-(3-mercapto propionate), trimethylolpropane propane three -(3-mercapto propionate) (=2-ethyl-2-( ((3-mercapto propionyl) oxy) methyl) propane -1, 3-di-dihydrogenmethylenebisphosphonate (3-mercapto propionate)) and ethylene glycol-(3-mercapto propionate) has been found to be highly preferred of the formula (X) is the poly and mercaptane all the above-mentioned poly thiol preferred poly thiol.

Formula (X) a poly thiol as a cis/trans-isomerization catalyst is very favourable, because poly thiol generally has a very low vapor pressure (i.e., high boiling point), thus allowing them to the lower temperature (for example, distillation of low-boiling isomer) is used. Furthermore, each molecular weight poly thiol bearing the thiol functional group of the high density, this is very advantageous, because only few catalyst needs to be added.

Using poly thiol as a cis/trans-isomerization catalyst is very advantageous, because they allow very rapid isomerization.

A relative to the amount of the unsaturated compound, is added to the unsaturated compound A in the cis or trans isomer of poly thiol amount is preferably in the 1 and 20 between weight %, particularly in a 3 and 5 between weight %.

In view of the molar ratio, preferably, polymercaptans and unsaturated compound in A mole ratios of 1/100 and 20/100 between, particularly in a 1/100 and 4/100 between.

The polymercaptans adding the unsaturated compound is not the mode A key, can be carried out according to the need. Can be in the step c) is added before or during poly thiol.

Isomerization

In step c) in, the polymercaptans and unsaturated compound A cis or trans isomer mixture is heated to between 20 the A [...] and unsaturated compounds between the boiling point of the temperature, in particular between 50 the A [...] and unsaturated compound a temperature between the boiling point of. In the present document, "unsaturated compounds the boiling point of the A" is defined as formed by said method the minimum boiling of the boiling point of the cis or trans isomer.

The polymercaptans and under the action of the temperature, of the unsaturated compound A cis and/or trans-isomer isomerization. Formed by isomerizing the ratio of cis and trans isomers (converge) gradually to balance at any time, for example, balance cis/trans ratio. The balance cis/trans ratio is the specific value, its for each kind of unsaturated compound A is different.

Have been observed: isomerization rate strongly depends on the polymercaptans and polymercaptans single thiol much faster. Furthermore, the is already observed: compared with a single thiol, polymercaptans lead to unsaturated compounds under the A the temperature of the less the degradation.

Has also been observed that: the polar solvent is added to promote effect isomerization, the polarity solvent such as amide, pyrrolidone, sulfone, sulfoxide, ionic liquid, especially N, N-dimethyl formamide (DMF) or N-methyl-2-pyrrolidone (NMP), sulfolane, dimethyl sulfoxide (DMSO) and 1-butyl-3-methyl imidazolium bromide.

Therefore, preferably, the presence of the polar solvent of cis/trans-isomerization method, in particular, the polarity solvent is selected from the group consisting of ionic liquid, in particular 1-butyl-3-methylimidazolium bromide; N, N-dimethyl formamide (DMF); N-methyl-2-pyrrolidone (NMP); and sulfolane the group consisting of dimethyl sulfoxide (DMSO).

More preferably, the presence of the polar solvent of cis/trans-isomerization method, in particular, the polarity solvent is selected from the group consisting of ionic liquid, in particular 1-butyl-3-methylimidazolium bromide; N, N-dimethyl formamide (DMF); N-methyl-2-pyrrolidone (NMP) and the group consisting of dimethyl sulfoxide (DMSO).

Unsaturated compounds of A isomerization of cis-or trans-isomer is very of concern, because a very isomer are often interesting isomer. Most cis and trans isomers with different nature. For example, compared with the cis-isomer, trans-isomer of the core of the interesting nature (such as smell or in particular in the chemical reaction of the reactive) obviously different. Under the condition of the citral, geranial trans-isomer (= (E)-3, 7-dimethyl-octa -2, 6- two olefine aldehydes) has strong lemon odor, the cis-isomer Neral (= (Z)-3, 7-dimethyl-octa -2, 6- two olefine aldehydes) is not too strong lemon odor but more sweet. On the other hand, if the unsaturated compounds with A prochiral carbon-carbon double bond, the prochiral carbon-carbon double bond can lead to the specific three-dimensional heterogeneous configuration the formation of the chiral compound. For example, the asymmetric hydrogenation of unsaturated compounds to A S R or the formation of the configuration of the stereo center.

Isomerization to provide the at least a portion of the undesired isomer into a desired isomer (isomer of interest=)the only possible. In the best possible manner by isomerization and separating method, even can realize: in undesired isomer or desired and undesired cis/trans isomer mixture, substantially all of the undesired isomer can be converted to the desired isomer. To later in this document, the method may more detail.

The cis/trans-isomerization method A unsaturated compound to the unsaturated compound A a mixture of cis/trans-isomer.

In the mixture can be separated from the desired isomer. Because the cis and trans isomers having a different boiling point, therefore, the most popular is a distillation process for the separation of. In order to minimize thermal degradation of the isomer, recommendations and under reduced pressure by way of the distillation column for distillation. However, the boiling point is very similar to the very often, in spite of this, through the use of specific distillation technology and equipment, can be separated or at least the enrichment of the desired isomer.

Because the most low boiling isomers of the isomer is not always of interest, as described below, in principle, need two interesting different method.

If the low boiling isomer is the isomer of interest, in another aspect, the invention relates to the unsaturated compounds of A mixture of cis and trans isomers of producing unsaturated compound A respectively the specific cis-isomer to the trans-isomer and the specific method, the unsaturated compound selected from unsaturated ketone A, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group, the method comprises the following steps

I) A provide unsaturated compounds of cis-isomer and trans of the mixture of isomers, wherein the cis-isomer of the weight of the W_cisand transform isomer weight of W_trans;

Ii) into poly thiol

Iii) the mixture is heated to a temperature T_iso1, the temperature is isomer I_lbp the boiling point, the isomer I_lbp has steps i) cis/trans isomer mixture of the minimum boiling point;

Iv) distilled to produce isomers I_lbp and collect isomer I_lbp;

V) in step ii) added in the presence of the poly thiol, a cis/trans-isomerization than isomer I_lbp higher the boiling point of the isomer I_hbp;

Wherein v in steps) later, then repeat steps iii), iv) and v)

And wherein if the collection of isomer I_lbp the unsaturated compound is cis-isomer of A, collect the isomer I_lbp weight higher than W_cis;

Or

If the collected isomer I_lbp A the unsaturated compounds is the trans-isomer, collect the isomer I_lbp weight higher than W_trans;

Wherein the weight W_cis and weight W_trans are respectively 0 g to 10 tons, incidental conditions are W_cis and W_trans greater than the ratio of 70/30 or less than 30/70, incidental conditions are W_cis and W_trans the two do not are 0 g.

In this method, in step i) A provide unsaturated compounds in the cis-isomer and trans of the mixture of isomers, wherein the cis-isomer of the weight of the W_cisand transform isomer weight of W_trans. Because the weight of the cis-isomer W_cis or trans isomer weight W_trans to 0 g to 10 tons, incidental conditions are W_cis and W_trans the two do not are 0 g, in the context of the "mixture" is also suitable for single stereoisomers, and true not only be used in a mixture of the stereoisomers.

In the preferred embodiment, weight W_cis and weight W_trans both is not 0 g, therefore in step i) in providing a mixture of, unsaturated compounds of cis and trans isomers A both actual presence.

In this method, isomer of interest (i.e., the desired isomer) is isomer I_lbp, the isomer I_lbp i is provided with steps) to provide the cis/trans isomer mixture of isomers of the minimum boiling point.

In step iv) in, separating and collecting by distillation the isomer I_lbp.

In order to optimize the purity, by the use of specific distillation technology to carry out distillation, so as to ensure that by the other isomer as little as possible of the impurities. In particular, have also realized the: part only collect in distillation of the desired isomer (i.e., the most pure fraction), and the residue in the distillation flask.

In order to optimize the yield of the desired isomer, in step v) in, the poly thiol (in step ii) adding) the presence, it has specific isomer I_lbp higher the boiling point of the isomer I_hbp is cis/trans-isomerization.

Even if in the preferred cases, in step iv) in, only partially isomer I_lbp is distilled and collecting, distillation residues still include isomers I_lbp. In this case, in step v) to the distillation residue in cis/trans-isomerization carried out.

The presence of the poly thiol, continuous or batch-isomerization isomer I_hbp and/or distillation remaining residue. Due to the desired product by the removal, distillation remaining residue rich in undesired isomer achieve the non--balance cis/trans ratio, so according to the principle of forces Xia Telie adjusting system and through the use of cis/trans-isomerization catalyst polymercaptans to promote the conversion of isomer not expected (i.e., isomerization) to the desired isomer explorations in order to achieve balance of cis/trans ratio. V the steps) later, then repeat steps iii), iv) and v), the increase of the yield is guaranteed. The desired isomer isomer I_lbp heavily dependent on total yield of the number of repetition and/or the separation efficiency by distillation.

This method results in the undesired isomer net (net) into a desired isomer, in other words, this means that: when the in step a) initially provided A of the unsaturated compounds in the mixture of cis and trans-isomer, cis-isomers with weight W_cisand transform isomer with weight W_trans time,

-If the collection of isomer I_lbp the unsaturated compound is cis-isomer of A, collect the isomer I_lbp weight higher than W_cis;

Or

-If the collection of isomer I_lbp A the unsaturated compounds is the trans-isomer, collect the isomer I_lbp weight higher than W_trans.

As mentioned above, in principle, substantially all of the undesired isomer can be converted to the desired isomer.

Therefore, preferably, the collected isomer I_lbp isomer weight higher than W_cis and W_trans sum total of 80 weight %, preferably higher than W_cis and W_trans sum total of 90 weight %.

If a higher boiling point is of the stereoisomers isomers of interest, in another aspect, the invention relates to the unsaturated compounds of A mixture of cis and trans isomers of producing unsaturated compound A respectively the specific cis-isomer to the trans-isomer and the specific method, the unsaturated compound selected from unsaturated ketone A, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group, the method comprises the following steps

A) provide unsaturated compound A of cis-isomer and trans of the mixture of isomers, wherein the cis-isomer of the weight of the W_cisand transform isomer weight of W_trans;

B) adding poly thiol

C) the mixture is heated to a temperature T_isol, the temperature is isomer I_lbp the boiling point, the isomer I_lbp has steps a) cis/trans isomer mixture of the minimum boiling point;

D) distilling isomer I_lbp

E) from step d) separating a residue of the specific isomer I_hbp, the isomer I_hbp than isomer I_lbp higher boiling point, and collecting said isomer I_hbp;

F) in step b) is added in the presence of mercaptan, cis/trans-isomerization isomer I_lbp and step e) the remainder (if step e) if that exists after residue);

Wherein in the step f) after, then repeat steps c), d), e) and f)

And wherein if the collection of isomer I_hbp the unsaturated compound is cis-isomer of A, collect the isomer I_hbp weight higher than W_cis;

Or

If the collected isomer I_hbp A the unsaturated compounds is the trans-isomer, collect the isomer I_hbp weight higher than W_trans;

Wherein the weight W_cis and weight W_trans are respectively 0 g to 10 tons, incidental conditions are W_cis and W_trans greater than the ratio of 70/30 or less than 30/70, incidental conditions are W_cis and W_trans the two do not are 0 g.

In the method, in the step a) unsaturated compound A provided in cis-isomer and trans of the mixture of isomers, wherein the cis-isomer of the weight of the W_cisand transform isomer weight of W_anti-type. Because the weight of the cis-isomer W_cis or trans isomer weight W_trans to 0 g to 10 tons, incidental conditions are W_cis and W_trans the two do not are 0 g, in the context of the "mixture" is also suitable for single stereoisomers, and true not only be used in a mixture of the stereoisomers.

In the preferred embodiment, weight W_cis and weight W_trans both is not 0 g, therefore in step a) in the mixture provided in, unsaturated compounds of cis and trans isomers A both actual presence.

In this method, isomer of interest (i.e., the desired isomer) is isomer I_hbp, the isomer I_hbp than isomer I_lbp higher boiling point, the isomer I_lbp is provided with steps a) providing the cis/trans isomer mixture of isomers of the minimum boiling point.

In step d) in, the low boiling point of the distilled from isomer I_lbp.

From step d) in the distillation residue separating specific isomer I_hbp and in step e) to collect in, the isomer I_hbp than isomer I_lbp higher boiling point,

Preferably through the specific distillation technology to carry out specific isomer I_hbp separation, for example, the use of side of the rectification column in the out point (  point   take-off side) and, finally, to a further rectification to the side out of the material point to collect, for example, EP   2   269   998   A2 (the special map 1 and 3) in the technical and apparatus have been disclosed, all of its content has been incorporated in this text by reference.

In order to optimize isomer I_hbp purity, by the use of specific distillation technology to performing step d) and e) the distillation, so as to ensure that the other isomer as little as possible of the impurities. In particular, also realizes: distillate only collect a portion of the desired isomer I_hbp (in other words, the most pure fraction), and the other fraction and the remaining in the distilling flask residue in the bottle, and in the step d) is in the minimum boiling point of the distilled from isomer I_lbp merger.

In step f) in, in step b) is added in the presence of mercaptan, isomerization isomer I_lbp and step e) the remainder (if step e) if that exists after the residue).

Even if in the preferred cases, in step e) in, only partially isomer I_hbp is distilled and collecting, distillation residues still include isomers I_hbp.

The presence of the poly thiol, continuous or batch-isomerization isomer I_lbp and/or the step e) residues. Due to the desired product by the removal, distillation remaining residue rich in undesired isomer achieve the non--balance cis/trans ratio, so according to the principle of forces Xia Telie adjusting system and through the use of cis/trans-isomerization catalyst polymercaptans to promote the conversion of isomer not expected (i.e., isomerization) to the desired isomer explorations in order to achieve balance of the cis/trans ratio. Through in step f) after, then repeat steps c), d), e) and f), the increase of the yield is guaranteed. The desired isomer isomer I_hbp heavily dependent on total yield of the number of repetition and/or the separation efficiency by distillation.

This method results in the undesired isomer net (net) into a desired isomer, in other words, this means that: when the step a) initially provided in A of the saturated compound in the mixture of cis and trans-isomer, cis-isomers with weight W_cisand transform isomer with weight W_trans time,

-If the collection of isomer I_hbp the unsaturated compound is cis-isomer of A, collect the isomer I_hbp weight higher than W_cis;

Or

-If the collection of isomer I_hbp A the unsaturated compounds is the trans-isomer, collect the isomer I_hbp weight higher than W_trans;

As mentioned above, in principle, substantially all of the undesired isomer can be converted to the desired isomer.

Therefore, preferably, the collected isomer I_hbp isomer weight higher than W_cis and W_trans sum total of 80 weight %, preferably higher than W_cis and W_trans sum total of 90 weight %.

Discussed in the preceding paragraphs are A producing unsaturated compound and the specific cis-isomer of trans-isomer in two kinds of methods, A relative to the amount of the unsaturated compound, preferably, polymercaptans in the amount 1 and 20 between % by weight, in particular 3 and 5 between weight %.

Furthermore, preferably, polymercaptans and unsaturated compound in the molar ratio of A 1/100 and 20/100 between, particularly in a 1/100 and 4/100 between.

Has also been observed that: the polar solvent is added to promote effect isomerization, the polarity solvent such as amide, pyrrolidone, sulfone, sulfoxide, ionic liquid, especially N, N-dimethyl formamide (DMF) or N-methyl-2-pyrrolidone (NMP), sulfolane, dimethyl sulfoxide (DMSO) and 1-butyl-3-methyl imidazolium bromide.

Therefore, preferably, the presence of the polar solvent of cis/trans-isomerization method, in particular, the polarity solvent is selected from the group consisting of ionic liquid (in particular 1-butyl-3-methyl imidazolium bromide), N, N-dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), sulfolane and the group consisting of dimethyl sulfoxide (DMSO).

More preferably, the presence of the polar solvent of cis/trans-isomerization method, in particular, the polarity solvent is selected from the group consisting of ionic liquid (in particular 1-butyl-3-methyl imidazolium bromide), N, N-dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP) and the group consisting of dimethyl sulfoxide (DMSO).

Furthermore, preferably, as described in detail in the foregoing, in cis/trans-isomerization method, polymercaptans formula (X).

In another aspect, the invention relates to compositions, the composition comprises

-Polymercaptans, and

-Formula (I) or (II) A the unsaturated compounds.

In the present document, have been discussed in detail before the poly thiol of formula (I) or (II) unsaturated compound A and their ratio and their preferred embodiment.

Preferably, the composition also comprises at least one kind of polar solvent, in particular, said at least one polar solvent is selected from the group consisting of ionic liquid (in particular 1-butyl-3-methyl imidazolium bromide), N, N-dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), sulfolane and the group consisting of dimethyl sulfoxide (DMSO).

Preferably, the composition also comprises at least one kind of polar solvent, in particular, said at least one polar solvent is selected from the group consisting of ionic liquid (in particular 1-butyl-3-methyl imidazolium bromide), N, N-dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP) and the group consisting of dimethyl sulfoxide (DMSO).

In another aspect, the invention relates to a ketal or acetal, the ketal or acetal is selected from the group consisting of 2-(4, 8- dimethyl ninth stem -3, 7-diene-1-yl)-2, 5, 5-trimethyl -1, 3-dioxane, 2, 6-dimethyl -10, 10-bis (2, 2, 2-trifluoroethoxy)-2, 6-diene, 2-(4, 8- dimethyl ninth stem -3-ene-1-yl)-2, 5, 5-trimethyl -1, 3-dioxane, 6, 10-dimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy)-5-ene, 2, 5, 5-trimethyl-2-(4, 8, 12-trimethyl thirteen carbon-3-ene-1-yl)-1, 3-dioxane, (R)-2, 5, 5-trimethyl-2-(4, 8, 12-trimethyl thirteen carbon-3-ene-1-yl)-1, 3-dioxane, 6, 10, 14-trimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy) fifteen carbon-5-ene, (R)-6, 10, 14-trimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy) fifteen carbon-5-ene, 2, 5, 5-trimethyl-2-(4, 8, 12-trimethyl thirteen carbon -3, 7, 11-trien-1-yl)-1, 3-dioxane, 2, 6, 10-trimethyl -14, 14-bis-(2, 2, 2-trifluoroethoxy) fifteen carbon -2, 6, 10-triene, 2, 5, 5-trimethyl-2-(4, 8, 12-trimethyl thirteen carbon -3, 7-diene-1-yl)-1, 3-dioxane, 6, 10, 14-trimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy) fifteen carbon -5, 9-diene, 2-(2, 6-dimethylheptyl-1-en-1-yl)-5, 5-dimethyl -1, 3-dioxane, 3, 7-dimethyl -1, 1-bis (2, 2, 2-trifluoroethoxy) Oct-2-ene, 3, 7-dimethyl -1, 1-bis (2, 2, 2-trifluoroethoxy) octa -2, 6-diene, 2, 8-dimethyl -6, 8-bis (2, 2, 2-trifluoroethoxy) Oct-2-ene, (R)-2, 8-dimethyl -6, 8-bis (2, 2, 2-trifluoroethoxy) Oct-2-ene, 2-(4, 8- dimethyl ninth stem -1, 3, 7-triene-1-yl)-2, 5, 5-trimethyl -1, 3-dioxane, 2, 6-dimethyl -10, 10-bis (2, 2, 2-trifluoroethoxy)-2, 6, 8-triene, 2, 5-dimethyl-2-(4, 8, 12-trimethyl thirteen carbon-3-ene-1-yl)-1, 3-dioxane, (R)-2, 5-dimethyl-2-(4, 8, 12-trimethyl thirteen carbon-3-ene-1-yl)-1, 3-dioxane, 6, 10, 14-trimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy) fifteen carbon-5-ene and (R)-6, 10, 14-trimethyl -2, 2-bis (2, 2, 2-trifluoroethoxy) fifteen carbon-5-ene and all of them may be of the group of the isomer composition E/Z.

These ketal and acetal is particularly suitable according to the method of the present invention is the isomerization.

Finally, in another aspect, the present invention relates to a poly thiol as a unsaturated compounds of cis/trans-isomerization A the use of the catalyst, the unsaturated compound selected from unsaturated ketone A, unsaturated ketal, unsaturated aldehyde, unsaturated acetals, unsaturated carboxylic acid, unsaturated carboxylic acid ester and unsaturated carboxylic acid amide group. In the present document, the have been discussed in detail before use.

Embodiment

Through the following experiment to further explain the invention.

In the 1st series of experiments, separation by distillation has been 6, 10-dimethyl -5, 9-dien-2-one isomer. E-isomer has been separated to 99.5% of the (E)-6, 10-dimethyl -5, 9-dien-2-one (measured by GC) content, Z-isomer in the concentrated fraction is separated, with the same 75.4% of the (Z)-6, 10-dimethyl -5, 9-dien-2-one and the content of 24.1% of the (E)-6, 10-dimethyl -5, 9-dien-2-one content (total 99.5% of the isomer, measured by GC).

E or Z isomer to the adding amount is 5 weight % (the concentration of is opposite in the alkone) table 1 catalyst. Then the mixture stirred in argon and heated to the 140 [...] , isomerization in this condition. After a certain reaction time, GC and E through regular measuring the amount of Z isomer.

Table 1 Figure 1 are respectively used for isomerization in (E)-and (Z)-6, 10-dimethyl -5, 9-dien-2-one of the catalyst.

Figure 1a) display these isomerization the results of the experiment. X-axis represents heating time, that is, in 140 the isomerization of time under [...] ; y-axis represents sample and the measuring of the stereoisomers in the percentage of E-isomer (E / (E+Z)). For example E / (E+Z) value is 80% E/Z ratio is representative of the 80 [...] 20. Figure 1a) display: all the catalyst are both induced isomerization, in other words: in the case of-isomer E, curve decline with time; in the case of Z-isomer, curve rise with time. Figure 1a) also display: poly thiol (examples 1 and 2 (solid-line)) in single thiol (examples reference 1 to reference 6 (dashed-line)) isomerization of much faster. Figure 1a) also display: 6, 10-dimethyl -5, 9-dien-2-one of the cis/trans ratio of balance/60-65% E between (E+Z).

Figure 1b) display the stability behaviour. X-axis once again, on behalf of the heating time, that is, in 140 the isomerization of time under [...] ; y-shaft to be representative of isomerization of the purity of the isomer ("P", to % meter) and measured by GC. Deviate from 100% expressed: has formed one or more by-product. Figure 1b) display: poly thiol with a single thiol is significantly more good stability behaviour.

In the 2nd series of experiments, separation by distillation has been 6, 10-dimethyl-5-ene-2-one isomer. E-isomer has been separated 95.5% of the (E)-6, 10-dimethyl-5-ene-2-one (measured by GC) content, Z-isomer in the concentrated fraction is separated, with the same 72.0% of the (Z)-6, 10-dimethyl-5-ene-2-one and the content of 27.2% of the (E)-6, 10-dimethyl-5-ene-2-one content (total 99.2% of the isomer, measured by GC).

To E-isomers or Z-isomer of the respectively added in different concentrations (1 weight %, 3 weight % and 3 weight %)of 4, 4 the thiol generation of benzoin[...] -sulfur (3). Then the mixture stirred in argon and heating to 140 the isomerization mixture and [...]. After heating for a certain period, and determine the GC E through regular the amount of Z isomer.

Figure 2a) shows the experimental result of the isomerization. X-axis represents heating time, that is, in 140 the isomerization of time under [...] ; y-axis represents sample and the measuring of the stereoisomers in the percentage of E-isomer (E / (E+Z)). For example E / (E+Z) value is 80% E/Z ratio is representative of the 80 [...] 20. Figure 2a) shows the poly thiol the effect of different concentration: 1% ("3 (1%)"), 3% ("3 (3%)") and 5% ("3 (5%)"). Isomerization rate depends on the concentration of use. Furthermore, Figure 2a) display: 6, 10-dimethyl-5-ene-2-one balance cis/trans ratio is about 65% E / (E+Z).

In the 3rd series of experiments, separation by distillation has been 6, 10-dimethyl-5-ene-2-one isomer. E-isomer has been separated 95.3% of the (E)-6, 10-dimethyl-5-ene-2-one (measured by GC) content, Z-isomer in the concentrated fraction is separated, with the same 75.8% of the (Z)-6, 10-dimethyl-5-ene-2-one and the content of 23.4% of the (E)-6, 10-dimethyl-5-ene-2-one content (total 99.2% of the isomer, measured by GC).

As shown in table 2 is shown in, or Z isomer to E by adding different amounts of poly thiol. Then the mixture stirred in argon and heated to the 140 [...] , isomerization in this condition. After a certain reaction time, GC and E through regular measuring the amount of Z isomer.

Table 2 Figure 3 are respectively used for isomerization in (E)-and (Z)-6, 10-dimethyl-5-ene-2-one of the catalyst.

is opposite in the alkone * the concentration of the

Figure 3a) shows the results of these isomerization experiments. X-axis represents heating time, that is, in 140 the isomerization of time under [...] ; y-axis represents sample and the measuring of the stereoisomers in the percentage of E-isomer (E / (E+Z)). For example E / (E+Z) value is 80% E/Z ratio is representative of the 80 [...] 20. Figure 3a) display: 6, 10-dimethyl-5-ene-2-one of the cis/trans ratio of balance/60-70% E between (E+Z).

In the 4th series of experiments, separation by distillation has been 6, 10, 14-trimethyl fifteen carbon-5-ene-2-one isomer. E-isomer has been separated to 96.3% of the (E)-6, 10, 14-trimethyl fifteen carbon-5-ene-2-one (measured by GC) content, (Z)-6, 10, 14-trimethyl fifteen carbon-5-ene-2-one has been separated the 0.1 [...] 89.3 E/Z ratio of (the purity is 89.4%, measured by GC).

E or Z isomer to adding 5% of the weight of pentaerythritol tetra (3-mercapto propionate) subsequently joined table 3 is shown in the solvent. Then the mixture stirred in argon and heating to 90 the [...] , isomerization in this condition. After a certain reaction time, GC and E through regular measuring the amount of Z isomer.

Table 3 Figure 4 in, polar solvent to the pentaerythritol tetra (3-mercapto propionate) is used for (E)-and (Z)-6, 10, 14-trimethyl fifteen carbon-5-ene-2-one of the impact of the isomerization efficiency.

is opposite in the alkone * the concentration of the

Figure 4a)-c) display these isomerization the results of the experiment. X-axis represents heating time, that is, in 90 the isomerization of time under [...] ; y-axis represents sample and the measuring of the stereoisomers in the percentage of E-isomer (E / (E+Z)). For example E / (E+Z) value is 80% E/Z ratio is representative of the 80 [...] 20. Figure 4a) DMF display the promotion effects the isomerization rate. Figure 4b) display the ionic liquid 1-butyl-3-methyl imidazolium bromide to the promoting effect isomerization rate. Figure 4c) display the promotion of the DMSO effect isomerization rate.

Figure 4a)-c) show that : (E, Z)-6, 10, 14-trimethyl fifteen carbon-5-ene-2-one balance cis/trans ratio is about 60-63% E / (E+Z).

In the 5th series of experiments, separation by distillation has been 6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-one isomer. ZZ-isomer has been separated 88.6% of (5Z, 9Z)-6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-ketone content, 0% of the (5E, 9E)-6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-one and the content of 4.0% of the (5E, 9Z)-and (5Z, 9E)-6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-one and the content (total 92.6% of the 6, 10, 14-trimethyl fifteen carbon -5, 9, 13-triene-2-one, is measured by GC).

Adding to the above-mentioned sample 5% of the weight of pentaerythritol tetra (3-mercapto propionate). Then the mixture stirred in argon and heated to 105 the [...] , isomerization in this condition. After a certain reaction time, the GC on a regular basis to determine the amount of various kinds of isomers.

Figure 5a)-c) display these isomerization the results of the experiment. X-axis represents heating time, that is, in 105 the isomerization of time under [...] ; Figure 5a) of the representative y-shaft in the weight ratio of ZZ/(ZZ+EZ+ZE+EE). Figure 5b) of the representative y-shaft in the weight ratio of (EZ+ZE)/(ZZ+EZ+ZE+EE). Figure 5c) of the representative y-shaft in the weight ratio of EE/(ZZ+EZ+ZE+EE). Figure 5a)-c) display: all isomers is isomerization, thereby providing: about 40% ZZ / (ZZ+EZ+ZE+EE), about 46% (EZ+ZE)/(ZZ+EZ+ZE+EE) and about 14% EE / (ZZ+EZ+ZE+EE) ratio of the stereoisomers.

In the 6th series of experiments, separation by distillation has been 6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one isomer. EZ-and ZE-of the mixture of isomers has been separated is 93.3% of the (5E, 9Z)-and (5Z, 9E)-6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one and the content, 3.0% of the (5E, 9E)-6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one content, 1.0% of (5Z, 9Z)-6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one content (total 97.3% of the 6, 10, 14-trimethyl fifteen carbon -5, 9-dien-2-one, is measured by GC).

Adding to the above-mentioned sample 5% of the weight of pentaerythritol tetra (3-mercapto propionate). Then the mixture stirred in argon and heating to 90 the [...] , isomerization in this condition. After a certain reaction time, the GC on a regular basis to determine the amount of various kinds of isomers.

Figure 6a)-c) display these isomerization the results of the experiment. X-axis represents heating time, that is, in 90 the isomerization of time under [...] ; Figure 6a) of the representative y-shaft in the weight ratio of ZZ/(ZZ+EZ+ZE+EE). Figure 6b) the representative y-shaft in the weight ratio of (EZ+ZE)/(ZZ+EZ+ZE+EE). Figure 6c) of the representative y-shaft in the weight ratio of EE/(ZZ+EZ+ZE+EE). Figure 6a)-c) display: all isomers is isomerization, and the balance is close to about 15% ZZ / (ZZ+EZ+ZE+EE), about 54% (EZ+ZE)/(ZZ+EZ+ZE+EE) and about 31% EE / (ZZ+EZ+ZE+EE).