JPS588378B2 - Fuhouwa alcohol carbon sane ester Rui no Tenkanhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for converting carboxylic acid esters of unsaturated alcohols.

The conventionally known metathesis (disproportionation reaction) of alkenes mainly concerns alkenes that do not have a polar group, and there have been no reports on the metathesis of carboxylic acid esters of unsaturated alcohols.

The present inventors have conducted a series of studies on the metathesis of alkenes having polar groups, and have conducted repeated experiments on the metathesis reaction of unsaturated alcohols and their derivatives, considering it to be an extremely useful technique.

As a result, it was discovered that the metasense of carboxylic acid esters of unsaturated alcohols or mixtures of these and alkenes can be carried out by using the following catalysts, and based on this knowledge, the present invention was achieved.

That is, the present invention provides [1] carboxylic acid esters of unsaturated alcohols that have a carbon-carbon double bond to which atoms other than carbon or hydrogen are not directly bonded, and do not have an unsaturated bond at a position conjugated with the carbon-carbon double bond; W, or a mixture of at least one compound selected from W,
Mo and Re halides, oxyhalides,
An unsaturated alcohol, characterized in that it is brought into contact with a catalyst comprising a combination of at least one selected from the group consisting of alkoxides and alkoxy halides and (B) an organotin compound having at least one carbon-tin bond. A method for converting carboxylic acid esters is provided.

The carboxylic acid ester of an unsaturated alcohol used in the present invention has a carbon-carbon double bond to which atoms other than carbon or hydrogen are not directly bonded, and does not have an unsaturated bond in a conjugate position with the carbon-carbon double bond. is a compound represented by the general formula R1R2C-CR3X.

In the formula, R1 to R3 are hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkenyl group, but other groups such as hydrocarbon groups and halogenated hydrocarbon groups that do not eliminate the activity of the catalyst It may be,
It may also be a group represented by X below.

Hydrogen is particularly preferred as R2 and R3.

X is a group containing a carbon atom substituted with Y described later and containing no triple bond or conjugated double bond other than a benzene nucleus, and is, for example, a group represented by.

Here, R4 is hydrogen, a hydrocarbon group, or a group similar to R1 to R3.

Furthermore, R4 may be X and/or Y.

Not all R4s need to be the same.

Hydrogen is particularly preferred as R4.

Y is a group represented by -OCOR'', and R5 represents a group similar to R1 to R3 other than hydrogen.

Specific examples include 9-octadecenyl acetate, 9-octadecenyl gropionate, 9-octadecenyl benzoate, 9-octadecenyl isobutyrate, 11-
docosenyl acetate-1, 3-hexenyl acetate,
Allyl acetate, crotyl acetate, 1,4-diacetoxybutene-2,3-putenyl azetate, ■・1
Examples include 8-diacetoxy-9-octadecene, 7-octenyl acetate, and p-acetoxyallylbenzene.

Furthermore, in addition to the above-mentioned compounds, there may also be mentioned a polymer having a non-conjugated carbon-carbon double bond, which is substituted with the above-mentioned polar group (-Y).

Furthermore, it is also possible to carry out the reaction using a mixture of the above-mentioned unsaturated alcohol with at least one alkene having no ester functional group to obtain a cross-reaction product of the two.

[2] As alkenes having no functional group, the general formula R
Examples include chain alkenes represented by 6R7C=CR8R9.

In the formula, R6, R8: hydrogen and a lower alkyl group (preferably hydrogen) R7, R9: hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a hydrocarbon residue such as an alkenyl group that does not eliminate the reaction activity groups and halogenated hydrocarbon residues -Z-: -(CRm0)d- (d≧1) and (cRlo).

-CR” =CR12- (CRmu3)f-(e≧1,
f≧1) R 1 0, R”, R 1 2, R 13: Mainly represents hydrogen, but one or more of these represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group having a reactive activity. Hydrocarbon residues such as alkenyl groups and halogenated hydrocarbon residues that do not disappear may also be used.

shows.

Furthermore, two or more of R 1 0 and Rl3 in the formula may be different groups.

Specifically, the chain alkenes include ethylene, 3-
Examples include hexene, 2-octene, 1-decene, allylbenzene, p-chlorostyrene, 1.9-decadiene, oleyl chloride, 4-methyl-1-pentene, and the like.

Examples of the cyclic alkenes include cyclooctene, cycloheptene, cyclododecene, cyclotriene, cyclopentene, cyclobutene, and 5-cyclooctadiene.

Further, as a compound other than the above general formula, pinchloroalkenes such as norbornene can also be used.

In addition, in addition to the above-mentioned compound [2], as compounds used in the present invention and used for cross-reaction with compound [1],
General formula R” CH=CH (CH2) a COOR15
Examples include unsaturated esters represented by (a≧1).

Here, R14 represents a group similar to R1, and R15 represents an alkyl group, a cycloalkyl group, or an aryl group.

The halides, oxyhalides, alkoxides, and alkoxyhalides of W, Mo, and Re, which are catalyst components used in the present invention, may be used singly or as a mixture of two or more thereof.

Also, mixtures of two or more compounds that produce these compounds through reaction can also be effectively used.

Among these, W and Mo compounds are preferred, and halides and alkoxy halides are particularly preferred.

Specific examples Toshiteha, WCl6, WB r 6, wF6, W
I6, MoC15, MoBrs, MoCl4, MoCl
3, ReCl5, WOCl4, Mo QCl 3, W
(QC6H5) a, MO (OC2H5)
2 C 1 a , Mo (OC2H3 ) 2 C
1 and 3 can be given.

Specific examples of the alkyltin compound having at least one carbon-tin bond as the catalyst (B) component include (CH3)4S
n, (CH3)3SnC1, (CH3)2SnC
l2, (C2Hs)4Sn, (C2H5)3SnC1
, (C2H5)3SnBr, (C2H5)3SnOC
2H5, (C2H5)sSnI, (C2H5) 3
SnOSn (C2H5)3, (C2H5
)2S nC 12(C2H5)SnCl3, (C4
Examples include Ho)4Sn and (CHa)3SnH.

Among these components (B), tetraalkyltin is particularly preferred.

Further, it is also possible to use the above-mentioned catalysts (A) and (B) by supporting them on a carrier normally used for solid catalysts.

Depending on the reaction, it is not necessary to use the above-mentioned compounds themselves as starting materials for both components (A) and (B); for example, a methyltin compound may be produced in the reaction system by combining tin tetrachloride and methylaluminum sesquichloride. It is possible.

The reaction of the present invention is carried out in the presence or absence of a solvent that does not cause loss of activity, but it is preferable to use a suitable solvent as necessary.

The solvents used in the present invention are wide-ranging, and include hydrocarbons, halogenated hydrocarbons, as well as ethers and esters.

That is, one of the features of the present invention is that it can be carried out in a polar solvent that has not been used conventionally.

Specific examples include n-hebutane, isooctane, hexatecane, benzene, toluene, tecarin, cyclohexane, dichloroethane, diphenyl ether, chlorobenzene, hexamethylene cyfuromide, dichlorobenzene,
Ether, tetrahydrofuran, ethyl acetate, methyl stearate, etc. can be mentioned as some of them.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples unless they go beyond the gist of the invention.

In the following examples, yields are calculated based on the peak area of the gas chromatogram unless otherwise specified.

In many cases, an internal standard was used in this calculation to improve analytical accuracy.

Example 1 In a glass ampoule that had been thoroughly dried in advance and was purged with nitrogen, 3 ml of chlorobenzene as a solvent and 1 rr of oleyl acetate synthesized from oleyl alcohol and acetic anhydride.
Insert Ll.

Next, a solution of WCl6 in chlorobenzene (0.05 mo
Add 2 ml of tetramethyltin chlorobenzene solution (0.2 mol/l) and stir well.
The ampoule was sealed and reacted at 70°C for 17 hours.

As a result, a conversion rate of oleyl acetate of about 20% and a yield of l.18-diacetoquine-9-octadecene of about 4% were obtained.

The total metathesis product yield was approximately 15%, including the metasense product that occurs following double bond isomerization.

Example 2 In Example 1, instead of the tetramethyltin chlorobenzene solution, a tetraethyltin chlorobenzene solution (0.
A similar experiment was conducted using 1 ml of 2mol/73).

As a result, a conversion rate of oleyl acetate of about 15% and a yield of 1,18-diacetoxy-9-octadecene of about 3% were obtained.

Example 3 In Example 1, a chlorobenzene solution of trimethyltin chloride (
A similar experiment was conducted using 2 ml of 0.2 mol/g).

As a result, a conversion rate of oleyl acetate of about 10% and a yield of 1.18-diacetoxy-9-octadecene of about 2% were obtained.

Example 4 In Example 1, a chlorobenzene solution of diethyltin dichloride (0.2
An experiment similar to Hokaha was conducted using 5al (mol/l).

As a result, a conversion rate of oleyl acetate of about 5% and a yield of 1,18-diacetoxy-9-octadecene of about 1% were obtained.

Example 5 In Example 1, tetraphenyltin was substituted for tetramethyltin.
．． A similar experiment was conducted except that 877 Lmol was used and the reaction temperature was 100°C.

As a result, a conversion rate of oleyl acetate of about 1% and a yield of 1,18-diacetoxy-9-octadecene of about 0.5% were obtained.

Example 6 10 ml of the solvent chlorobenzene was placed in a 50 ml three-neck round bottom flask with a condenser that had been thoroughly dried in advance.
, Add 3rnl of oleyl acetate, then add 6ml of WC16 chlorobenzene solution (0.05mol/g), stir well with a stirrer, then add 5ml of tetramethyltin chlorobenzene solution (0.2mol/l). .

This is heated while stirring well, and the reaction is carried out while refluxing the chlorobenzene (reaction temperature: about 134°C).

The conversion rate of oleyl acetate was about 30% in a reaction time of about 7 hours, 1
- A yield of about 25% of the total metathesis product containing 18-diacetoxy-9-octadecene was obtained.

Example 7 In Example 6, 1 oleyl isobutyrate was used instead of oleyl acetate.
A similar experiment was conducted except that rnl was used.

As a result, about 10% of the total metathesis product containing 9-octadecene was obtained.

Example 8 An experiment similar to Example 6 was conducted except that allyl acetate 2-sulfur was used instead of oleyl acetate.

As a result, a yield of about 5% of 1,4-diacetoxy-2-butene was obtained.

Example 9 An experiment similar to Example 6 was conducted except that a mixture of 2 rul of 1,4-diacetoxy-2-butene and 2 ml of 1-decene was used instead of oleyl acetate.

As a result, the yield of allyl acetate was about 2%, and the yield of a compound believed to be 2-undecenyl acetate was about 2%.

Example 10 An experiment similar to Example 6 was conducted except that a mixture of 2 ml of oleyl acetate and 2 ml of oleyl chloride was used instead of oleyl acetate.

As a result, various cross-reaction products including 1-acetoxy-18-chloro-9-octadecene were obtained in a yield of about 10%.

Example 11 In Example 1, instead of the chlorobenzene solution of WCl6, a chlorobenzene solution of W(OC6H5)6 (0.
1 mol/l! ) was used, and the reaction temperature was 100° C., but the same experiment was conducted.

As a result, the conversion rate of oleyl acetate was about 10%, and 1.18-
The yield of diacetoxy-9-octadecene was about 3%.

Example 12 In Example 1, a chlorobenzene solution of Mo QCl3 (0.0
5 mol/g) was used, and 3 ml of a chlorobenzene solution of cutatetramethyltin (0.2 mol/g) was used.
A similar experiment was conducted except that 1 was used.

As a result, the conversion rate of oleyl acetate was 12%, and the yield of 1.18-diacetoxy-9-octadecene was about 5%.

Example 13 In Example 1, a chlorobenzene solution of ReC15 (o. 0
Use 4rnl of 5mol/l:) and 2ml of tetramethyltin chlorobenzene solution! The same experiment was conducted except that

As a result, a conversion rate of oleyl acetate of about 5% and a yield of 1,18-diacetoxy-9-octadecene of about 2% were obtained.

Example 14 In Example 8, a chlorobenzene solution of WOCl4 (0.05 mol/
A similar experiment was conducted except that 6rnl of 1) was used.

As a result, a conversion rate of allyl acetate of about 25% and a yield of 1,4-diacetoxy-2-butene of about 7% were obtained.

Example 15 In Example 8, MO (QC 2 H5 ) 2 c i 3 was used instead of the chlorobenzene solution of We l 6.
Chlorobenzene solution (0.1 mol/l
) was used, but the same experiment was conducted.

As a result, a conversion rate of allyl acetate of about 18% and a yield of 1,4-diacetoxy-2-butene of about 6% were obtained.

Example 16 In Example 9, a chlorobenzene solution of MoCl (0.05 mol) was used instead of a chlorobenzene solution of wcl6.
A similar experiment was conducted, except that 6rnl of /73) was used.

As a result, a yield of about 3% of allyl acetate and a yield of about 5% of a compound believed to be 2-undecenyl acetate were obtained.

Example 17 In Example 6, WB r. , chlorobenzene solution (0.05
mol/l) was used, and instead of oleyl acetate, 2IrLl of oleyl acetate and 1.5m of 4-octene were used.
A similar experiment was carried out except that a mixture of 1.

As a result, the yield of 9-r-ridecenyl acetate was about 5%,
A yield of about 3% of 4-tridecene was obtained.

Claims (1)

[Scope of Claims] 1 [1] An unsaturated alcohol having a carbon-carbon double bond to which no atom other than hydrogen or carbon is directly bonded, and having no unsaturated bond at a position conjugated with the carbon-carbon double bond. (A) W,
Mo and Re halides, oxyhalides,
An unsaturated alcohol characterized in that it is brought into contact with a catalyst comprising a combination of at least one member selected from the group consisting of alkoxides and alkokene halides and (B) an organotin compound having at least one carbon monotin bond. A method for converting carboxylic acid esters.