JPS5830293B2 - Fuhouwano Carbon Sunester Luino Tenkanhou - Google Patents

Description

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

The conventionally known metathesis (disproportionation reaction) of alkenes mainly concerns alkenes without functional groups, and the most effective catalysts are W and Mo compounds, C4H9Li, CH3MgBr.

C2H5AlCl2. Combinations with compounds such as (C2H5)3A1 are known.

However, there are no reports on the application of these catalysts to the metathesis of acyclic alkenes having functional groups such as carbonyl groups, carbalkoxy groups, and nitrile groups.

This may be because the suitable catalyst systems and optimal reaction conditions are generally different for reactions of olefins with functional groups and for reactions of olefins without functional groups, or that the activity of these catalyst systems is low. This seems to be due to

The present inventors have already discovered that a catalyst formed by combining a compound of W, Mo 2 , Re 2 , Ta and a methylaluminum compound is
They discovered that it was effective for the metathesis of non-conjugated, unsaturated carboxylic acid esters and applied for a patent, but at the same time they applied a catalyst and conditions that are said to be effective for the reaction of olefins that do not have functional groups. It was found that satisfactory results could not be obtained with olefins having functional groups.

As a result of further research, the present inventors discovered that W.

Metathesis of a non-conjugated unsaturated carboxylic acid ester proceeds with a combination catalyst of a Mo or Re compound and an organoaluminum compound having 2 or more carbon atoms, and the number of functional groups,
They succeeded in discovering a technology that changes things such as the number of carbon atoms.

The characteristics of the catalyst system of the present invention are that, in addition to showing satisfactory activity for the above reactions, the raw materials are easily available, the catalyst has low toxicity, and post-treatment is easy. .

The latter feature is decisive in practical use compared to the only reported example of a catalyst combining WCl6 and highly toxic (CHa)4Sn in the disproportionation reaction of methyl oleate or methyl linoleate. This can be said to be a great advantage.

In this way, with respect to the reaction of alkenes having functional groups, alkyl aluminum compounds, which have been thought to be weak against functional groups, can be treated with W.

Only with the unique idea of combining Mo and Re compounds and careful observation skills, we were able to develop a completely new technology for converting unsaturated carboxylic acid esters and arrive at the present invention. Ta.

That is, the present invention provides [I] unsaturated carboxylic acid esters having a carbon-carbon unsaturated double bond and not having an unsaturated bond in a conjugate position with the unsaturated carboxylic acid ester, or combining this with [■] a functional group. (A) W2MO
and at least one selected from the group consisting of halides, oxyhalides, alkoxides, and alkoxyhalides of Re and (B) an organoaluminum compound having an alkyl group having 2 or more carbon atoms, (A)/(B
) in a metal ratio in the range of 172.5 to 1/6.

[I] The unsaturated carboxylic acid ester that has a carbon-carbon double bond and does not have an unsaturated bond at a position conjugated with the carbon-carbon double bond used in the present invention is Compounds that do not have atoms other than bonded hydrogen and carbon, such as compounds represented by the general formula % (esters of unsaturated carboxylic acids, carboxylic esters of unsaturated alcohols, and esters of unsaturated carboxylic acids and unsaturated alcohols). ) is preferably used.

In the formula, R1 represents hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkenyl group, but R1 is a group other than the above, such as a hydrocarbon group or a halogenated hydrocarbon group that does not eliminate the reaction activity. It's okay.

Alternatively, it may be X described later. R2 and R3 represent hydrogen or a lower alkyl group, with hydrogen being preferred.

X is a hydrocarbon group substituted with Y described below, and is a group that does not have a conjugated double bond other than a benzene nucleus, specifically,
For example,

Here, R4 mainly represents hydrogen, and one or more of R4 may be the same group as R1 and/or Y.

However, R4 does not need to be all the same.

Here, R5 and R6 represent an alkyl group, a cycloalkyl group, or an aryl group, but may also be a group other than those mentioned above, such as a hydrocarbon group or a halogenated hydrocarbon group, which does not eliminate the reaction activity.

Further, R5 and R6 may contain an ester group.

Specific examples include vinyl ethyl acetate, vinyl isobutyl acetate, vinyl cyclohexyl acetate, vinyl phenyl acetate, ethyl 4-pentenoate, amyl 4-pentenoate, 4-
Benzyl pentenoate, propyl 3-decenoate, methyl 9-decenoate, methyl 10-undecenoate, ethyl 10-undecenoate, methyl 13-tetradecenoate, methyl oleate, ethyl oleate, butyl oleate, methyl isooleate, ethyl cis-6-octadecenoate,
Butyl cis-6-octadecenoate, ethyl elaidate, butyl elaidate, methyl brasidate, ethyl brasidate, methyl erucate, ethyl erucate, methyl linoleate, diethyl 2-allylmalonate, allyl acetate, oleyl acetate, acetic acid Examples include 2-hexenyl, 3-hexenyl acetate, 2-hexenyl butyrate, allyl propionate, and oleyl benzoate.

The unsaturated compound having no functional group (lI) used in the present invention is one having no atoms other than hydrogen and carbon directly bonded to the carbon atom of a carbon-carbon double bond, and having the general formula R7R8C=R9RIG. represented, C=
Examples include chain compounds that do not have an unsaturated bond at the position conjugated with C.

In the formula, R7, R9: hydrogen and lower alkyl group, with hydrogen being preferred.

R8, R10: hydrogen, alkyl group, cycloalkyl group,
Indicates hydrocarbon groups such as aralkyl groups, aryl groups, alkenyl groups that do not eliminate reaction activity, and halogenated hydrocarbon groups.

Specifically, for example, ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 3-hexene, 3-pentene, ■-octene, 2-octene,
4-octene, ■-decene, 5-decene, allylbenzene, P-chlorostyrene, 1,7-octadiene, 1,
9-decadiene, oleyl chloride, 4-methyl-1-
Penten etc. will give you a horse.

A cyclic compound represented by can also be used.

11 R12, R13, R14: Mainly indicates hydrogen, but The back of these 2 or more are alkyl group, cycloalkyl group, Aralkyl group, aryl group group, the reaction activity is lost. alkenyl that does not Hydrocarbon groups such as groups and With halogenated hydrocarbon group There may be.

shows.

Further, in the formula, two or more of R11 and R14 may be different groups.

Examples of the cyclic compound include cyclooctene, cycloheptene, cyclododecene, cyclododecatriene, cyclopentene, cyclobutene, and 1,5-cyclooctadiene.

(However, cyclohexene is excluded.

) Bicycloalkenes such as norbornene and dicyclopentadiene, which are cyclic compounds other than those represented by the above general formula, can also be used.

When using the above-mentioned cyclic compound, it is necessary to use the compound [I] in the present invention in sufficient excess so as not to form a polymer.

The catalyst used in the present invention (W, M of Al components.

and one or two halides, oxyhalides, alkoxides, and alkoxyhalides of Re.
Used as a mixture of more than one species.

Among these, compounds of W and Mo are preferred, and chlorides and alkoxy chlorides of W and Mo having a valence of 4 or more are particularly preferred.

A specific example is WC+6. WBr6+WF6,WI
6rMOCI5, MoBr3, MoC14, MIO
CI3. ReCl3°Re0C13, WOCl4. Mo
0C13,Mo(OC2H,)2C13゜MO(OC2
H3)2C13, MO(OC6H5)2C13-, etc. can be mentioned.

As the catalyst (Bl component, one or more organic aluminum compounds having an alkyl group having 2 or more carbon atoms are used, but usually a compound represented by the general formula RpAIX3-p (p = 1 to 3) , R is an alkyl group having 2 or more carbon atoms, X is halogen, H
Represents % alkoxy.

) is valid. Specifically, (C2R5)3 A'l
, (C2H5')2 A I CI .

(C2H5)1,5AICI, :5. C2H5AlCl
2゜(C2I-(5)2AIH2(isO-C4H9)
3Al.

(iso C4H9)2AICI, (n-C6H
13) 3Al.

(Cs R17)3A l, (C2H5)2A I
OC2H5, (C2H5)2AIF, (C2H5)2
Examples include AIBr.

The quantitative relationship between catalyst (4) component and (B) component is (A)/(B)
) is used in a metal atomic ratio of 1/2.5 to 1/6.

In addition to (4) and (B) both precepts, compounds having a carbonyl group such as ketones, amides, aldehydes, esters, and quinones, carboxylic acids and derivatives thereof, alkyl halides, and /S halogens are added as a third component. halogenated hydrocarbons such as vinyl chloride compounds, alcohols, amines, water, phenols, acetals, ethers, and titanium,
It is often effective to further increase the reaction activity by adding an appropriate amount of a compound having an alkoxy group such as zirconium, potassium, boron, magnesium, aluminum, vanadium, etc.

Also CO2, 02, NO. Treatment with a gas such as C12 is also often effective in increasing reaction activity.

Furthermore, it is also possible to carry out the reaction by supporting the above catalyst system on a carrier usually used for solid catalysts or an organic polymer such as a polymer having a carbonyl group or a hydroxyl group such as polyvinyl acetate or its (partially) saponified product. .

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, an alkyl aluminum compound may be prepared by combining aluminum chloride and alkyl lithium.

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

The solvents used in the present invention include a very wide range of hydrocarbons, halogenated hydrocarbons, and even ethers, esters, and nitriles that are inert to catalysts, that is, polar solvents that could not be used conventionally. It can also be carried out in a solvent.

This is one of the important features of the present invention.

Specific examples include n-hebutane, isooctane,
Examples include hexadecane, benzene, toluene, tecarin, cyclohexane, dichloroethane, hexamethylene dipromide, chlorobenzene, dichlorobenzene, diphenyl ether, ether, tetrahydrofuran, ethyl acetate, methyl stearate, acetonitrile, and the like.

Suitable temperatures for carrying out the method of the invention are -30°C to +30°C.
00°C, but a temperature of -10'C to +200°C is usually preferred.

Further, the reaction is usually carried out at normal pressure, but it can also be carried out under reduced pressure or increased pressure.

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, unless otherwise specified, the yield was calculated based on the peak area of the gas chromatogram.

In other words, in the case of self-metathesis reaction 2AB and AAABB, the yield of AA (or BB) is [amount (mol) calculated from the area of the gas chromatogram of the product (AA) by the internal standard method/AB used as a raw material] amount (mol))
Calculated using X100.

In addition, cross metathesis reaction 2CD+2EF#CE+C
The case of F+DE+DF was also calculated using a similar formula, but in this case, the denominator was CD or EF.

That is, CE (or CF or DE, DF
) is calculated from the area of the gas chromatogram of the product (DE) using the internal standard method (mol)
/Amount of CD or EF used as raw material (mo])
) Calculated using XI 00.

Example 1 15 ml of 1°2-dichloroethane as a solvent and 1.5 ml of methyl oleate were placed in a sealed 50 ml glass reaction vessel (glass ampoule) that was thoroughly dried and purged with nitrogen, and then a WCl6 chlorobenzene solution ( 0,05
Add 2rnl of mo ]/l).

After stirring for about 10 minutes, add 1.5 ml of a chlorobenzene solution (0.2 mol/l) of (C2H5) 2 A lc +.
In addition, the reaction was carried out at a reaction temperature of 30° C. for 20 hours.

As a result, the reaction product is 9-octadecene [■]
and dimethyl 8-hexadecene-1,16-dicarboxylate ([■]: CH30CO(CH2)7CH-CH(CH
2) 7COOCH3) was obtained.

The yield of CI) was about 12%, and the yield of [■] was about 9%.

Example 2 Instead of using (C2H5) two-person ICI in Example 1, a chlorobenzene solution of (C8H17)3AI (0,2
The same experiment was repeated except that 1.5 ml of mol/#) was added.

As a result, the yield of [1] was about 7%, and the yield of (n) was about 4%.
Met.

Example 3 The same experiment as in Example 1 except that instead of using (C2H6) two-person ICI, 1.5 ml of a chlorobenzene solution (0.2 mo 1./l) of (C2H5)1-5 AICh-5 was added. repeated.

As a result, the yield of [■] is about 5%, and the yield of [■] is about 3%.
Met.

Example 4 In Example 1, instead of the chlorobenzene solution of WCl6, a chlorobenzene solution of MoCl3 (0.05 mol
/l) 2ml! A similar experiment was carried out except that the reaction was carried out at 70° C. for 24 hours.

As a result, the yield of [■] was about 6%, and the yield of (II) was about 4%.
%, and the total meta-cis yield was about 20%.

Example 5 In Example 1, instead of the chlorobenzene solution of WCl6, a chlorobenzene solution of Mo0C13 (0.05 mo
l/l) was used and the reaction was incubated at 70'C for 2 ml.
As a result of conducting the same experiment except that it was carried out for 4 hours, [I
], [■] and the total mecthesis yield were about 8%, about 5%, and about 25%, respectively. Chlorobenzene solution of 6 (0,
1 ml of 1 mo I/l) and the reaction was
A similar experiment was conducted except that it was conducted at ℃ for 24 hours.

As a result, the yields of [■] and (II) were approximately 9
% and about 6%, and the total mecthesis yield is about 17
%Met.

Example 7 Oleyl acetate ITL and 3TL of chlorobenzene were placed in a well-dried glass reaction vessel purged with nitrogen, followed by a solution of WCl6 in chlorobenzene (0.05 mol/l).
Add 2ml of.

After stirring for about 10 minutes, 0.3 ml of a toluene solution of (C2H5)2AICI (1.0 mo I/l) was added and the reaction was carried out at 20°C for 200 hours.

As a result, the yield of 0) was about 4%, and the yield of 1,18-diacetoxy-9-octadecene (III) was about 3%.

Example 8 The same experiment as in Example 9 was repeated except that 3 ml of ethyl acetate was used instead of 3 ml of chlorobenzene and the reaction was carried out at a temperature of 50°C.

As a result, the yield of CI) was approximately 6%, and the yield of [■] was approximately 5%.
Met.

Example 9 Instead of using (C2H5)2AICI in Example 9, C2
Chlorobenzene solution of H6AlCl2 (0.5 mol/
The same experiment was repeated except that 0.6 ml of oleyl acetate was used and a mixture of 1 ml of oleyl acetate and 2 TL of 1-hexene was used instead of 1 ml of oleyl acetate.

As a result, the formation of tetradecenyl acetate (IV,l) was confirmed on the gas chromatogram.

The yield of (IV) was about 4%.

The yield was calculated based on the oleyl acetate used.

Example 10 Put 2 ml of vinyl ethyl acetate into a well-dried glass container and purify it with nitrogen.
mo 1/l) and 27711, (C2H5)2A
Chlorobenzene solution of ICI (0.5mol/#
) was added thereto, and the reaction was carried out at a reaction temperature of 132 to 134°C for 200 hours.

As a result, ethyl dihydromuconate ([■]: C2H50
The formation of COCH2CH-CHCH2COOC2H6) was confirmed as σ on the gas chromatogram.

The yield of [v] was about 7%.Example 11 Example 10 (herein, instead of the chlorobenzene solution of WCl6, the chlorobenzene solution of WOCl4 (0,0
Same as above except that 2ml of 5mol/l) was used.
In fact, I conducted an experiment.

As a result, the yield of (V) was about 9%.

Example 12 In Example 10, instead of the WCl6 chlorobenzene solution, a WBr6 chlorobenzene solution (0.05
A similar experiment was conducted except that 2 ml (mol/l) was used.

As a result, the yield of (V) was about 5%.

Example 13 Instead of using WCl6 in Example 1, Mo (C2
H, 0) 2 Cl 3 glue D/L/benzene solution (0,
The same experiment was repeated except that 0.5 ml of 2 mol/A) was used.

As a result, the yield of CI) was 10%, and the yield of 1jT) was 8%.
Met.

Example 14 1 TLl of methyl oleate was placed in a well-dried glass reaction vessel that was purged with nitrogen, and then 4 TLl of a chlorobenzene solution of ReCl3 (0.05 mol/l) was added.
After stirring for 0 minutes, a chlorobenzene solution of C2H5AlCl2 (
Add 0.8 rnl of 1,0mo I/l) to 200G
The reaction was carried out for 40 hours.

As a result, the yield of CI) was approximately 5%, and the yield of (II) was 4%.
Met.

Example 15 After purging a stainless steel autoclave with an internal volume of 300 m1 with nitrogen several times, 26.1 g of methyl oleate was removed.
(88.2 mmol), then add 30 ml of WCl6 chlorobenzene solution (0.05 mo I/l) (
4.1.5 mmol) and a chlorobenzene solution (1 mol/l) of C2H5AlCl2. ．． 5m1 (4,5m
mol) added.

Finally, ethylene was charged from the cylinder to a pressure of 20 kg/ffl.

The reaction temperature was controlled at 60°C and the reaction was carried out for 5 hours.

After the reaction was completed, a small amount of methanol was added to stop the reaction, the contents were taken out, and after being touched, the product was quantified by gas chromatography.

The yields of methyl 9-decenoate and 1-decene were each 18%.

However, the yield was calculated based on the oleic acid used.

By appropriate selection of ethylene pressure, no formation of the self-metathesis products of methyl oleate, 9-octadecene and methyl 8-hexadecene-1,16-dicarboxylate, was observed.

Example 16 A Nituro flask with an internal volume of 50 ml equipped with a cooling tube and a three-way cock was purged with nitrogen several times, and 2 ml of methyl 9-decenoate (synthesized according to Example 15) and 1-
12 ml of hexene was added.

Next, a chlorobenzene solution of WC16 (0.05 mo
1.2 ml of a chlorobenzene solution (0.5 mol/A) of C2H5AIC12 was added.

The reaction was carried out at 60°C for 5 hours.

In order to remove the ethylene produced by the reaction from the system, a three-way cock was attached to the cooling pipe, and the reaction was carried out while nitrogen gas was flowing.

According to gas chromatogram, the product was methyl 9-tetradecenoate and the yield was 11% (calculated based on the methyl 9-decenoate used).

) In addition, a small amount of self-metathesis reaction products 5-decene and dimethyl 8-hexadecene-1,16-dicarboxylate were produced.

Example 17 An experiment similar to Example 1 was conducted except that methyl erucate was used instead of methyl oleate.

As a result, the reaction products were 9-octadecene CI) and 13-
Dimethyl hexacosenioate [■] was obtained, the yield of CI) was 10%, and the yield of [■] was 8%.

Example 18 Instead of using (C2H5) two-person ICI in Example 17, 1.5 ml of a chlorobenzene solution (0.2 mol/l) of (C2H5)t-5AI C11,5 was added, and the reaction temperature was 70°C. Allowed time to react.

As a result, 9-octadecene was obtained in a yield of 18%, and dimethyl 13-hexacosendioate was obtained in a yield of 15%.

Example 19 In Example 15, 31.1 g of methyl erucate (88.2 mmol) was used instead of 26.1 g of methyl oleate.
), C2H5AlCl2 in chlorobenzene solution (1,
(C2H5)1- instead of 0 mol/l) 4.5 ml
5AICI0. , a chlorobenzene solution (1,0-E/
A similar experiment was carried out by adding 4.5 ml (4.5 mmol) of ethylene 60 at a pressure of 9/i.

As a result, the reaction products were 1-decene [I] and methyl 13-tetradecenoate (II), and the yield was calculated based on the charged methyl erucate (CI) 15%.
and (II) 16%.

Example 20 In Example 7, instead of the toluene solution of (C2H5)2A and ICI, a toluene solution of (ls o C4Hg)3A I (1,0 mol/A?) 0.4 m
A similar experiment was conducted except that 1 was used.

As a result, the yield of [1] and CI) was about 6% each.
and about 4%.

Comparative Examples 1-2. Examples 21 to 23 Glass containers (4), (B) that were well dried and replaced with nitrogen
, (C) Add 1 ml each of methyl oleate to (D) and (E), then add 2 ml each of a WCl6 chlorobenzene solution (0.05 mol/A), 5
After stirring for a minute, a chlorobenzene solution (0.5 mol/A) of (C2H5)1-5AIC11a5 was added to each solution.
2 ml (Comparative Example 1), 0, 4 ml (Comparative Example 2),
0.6 ml (Example 21), 0.8 ml (Example 22) and 1.2 ml (Example 23) were added, and the reaction was carried out at a reaction temperature of 50° C. for 400 hours.

Results (A), (B), (C), (D) and (E)
The yields of [I] are approximately 0.1% and 0.4%, respectively.
, 15%, 8% and 5%, the yield of [■] is about 0.05%, respectively.

They were 0.3%, 19%, 8% and 5%.

Claims (1)

[Scope of Claims] 1 [I] Unsaturated carboxylic acid esters having a carbon-carbon unsaturated double bond and not having an unsaturated bond in a conjugate position with the carbon-carbon double bond, or this and (II) a functional (A) W, Mo and R
At least one member selected from the group consisting of halides, oxyhalides, alkoxides, and alkoxyhalides of (e) and (B) an organoaluminum compound having an alkyl group having 2 or more carbon atoms are combined into (A)/(B). A method for converting unsaturated carboxylic acid esters, which comprises bringing them into contact with a catalyst comprising a combination of metals having an atomic ratio of 172.5 to 1/6.