JPS6054297B2 - Method for producing carboxylic acid dodecenyl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing unsaturated carboxylic acid esters useful as intermediates for pheromones, fragrances, or organic compounds, and in particular, a method for producing unsaturated carboxylic acid esters useful as pheromones (including synthetic attractants). It is about the method.

It is well known that animals, especially insects, of which there are said to be over a million species, communicate with each other by emitting substances that attract the same species, and sometimes different species. Substances that are produced within the insect's body and excreted from the body and have a very strong attracting effect, although in small amounts, are called pheromone (attractant). Pheromones are classified into sex pheromones, aggregation pheromones, class pheromones, etc., but sex pheromones are especially well known for their properties. Such fueromones and substances with similar effects obtained by synthesis (herein referred to as synthetic attractants) are used as pest control means, especially harmless or non-polluting pest control means. It is attracting attention as a product that can be used for such purposes. The type of pheromone and synthetic attractant differs depending on the type of insect, but most of them are usually straight-chain unsaturated types that have one double bond and contain a hydroxyl group, aldehyde group, or ester group. It is an oxygen-containing compound, especially a linear unsaturated type oxygen-containing compound containing an ester group.

Examples of such linear unsaturated pheromone and synthetic attractants are shown in Table 11. Conventionally, the chemical synthesis of such pheromones and synthesis attractants has involved extremely complex synthetic methods [for example, one chemical area
(19th year of Tin), pages 640-649]. The present inventors have conducted various studies to produce unsaturated carboxylic acid esters that can be used as pheromones, synthetic attractants, etc. in a relatively simple manner and with good yield, and as a result, they have arrived at the present invention. It's ivy. That is, the present invention is directed to the general formula (where R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is a halogen atom, and m is an integer of 5 to 7).

) and a terminally halogenated olefin represented by the general formula (
In the formula, R4 is a straight chain alkyl group having 2 to 4 carbon atoms, and R5 is hydrogen or a straight chain alkyl group having 2 to 4 carbon atoms.

) and R4 of the olefin.
and the carbon number of at least one of R5 is (91m) (wherein, m is m in the above general formula of the terminally halogenated olefin used in combination.

), and (4) a halogen-containing metal compound of a metal selected from tungsten, molybdenum, and rhenium (including mixtures of the halogen-containing metal compounds), and (B) the periodic rule. A halogenated terminal olefin having 12 carbon atoms is produced by carrying out a disproportionation reaction using a catalyst consisting of a reducing metal compound selected from hydrides, alkylated compounds, and alkyl halides of metals from Groups 1 to 2 in Tables. , and then the halogenated olefin obtained by the reaction is treated with a metal salt of carboxylic acid. The disproportionation reaction of olefins using a catalyst consisting of a tungsten, molybdenum or rhenium compound and an organic compound of Groups 1 to 1 of the Peripheral Table or a hydride of the same metal is known as a metathesis reaction.

In principle, this reaction is an equilibrium reaction, and the main reaction appears to be in which the olefins are cleaved at the double bond and then rearranged according to a statistical proportion. It is something.

Furthermore, it has already been described in British Patent No. 1,283,348 that a halogen-substituted olefin can be produced by applying such a reaction to a halogen-substituted olefin alone or a mixture thereof with an unsubstituted olefin or other halogen-substituted olefin. There is.

That is, the same specification describes that a mixture of p-chlorostyrene and pentene-2 or a mixture of 5-bromopentene-1 and pentene-2 is subjected to a disproportionation reaction using the above catalyst. However, it was completely unknown that unsaturated rubonic acid esters, which are useful as various pheromones and synthesis attractants, can be easily synthesized by using halogenated olefins obtained using such metathesis reactions. The present invention has succeeded in advantageously producing rubonic acid dodecenyl ester, which is useful as a pheromone and a synthetic attractant, by utilizing such a metathesis reaction. Generally, compounds that are effective as pheromones or synthetic attractants are used alone for that purpose, but even compounds that have little or no effect when used alone can have a significant effect when mixed in appropriate proportions. is known to exhibit. From this point of view as well, the present invention, which applies a metathesis reaction capable of simultaneously synthesizing several types of compounds to the production of pheromone or a synthesis attractant, must be called revolutionary. As the starting material olefins in the present invention, a mixture of two or more halogenated olefins may be used depending on the position of the unsaturated bond in the carboxylic acid dodecenyl ester to be synthesized, or at least one halogenated olefin may be used. A mixture of halogenated olefins and at least one olefin may also be used.

The halogen of the halogenated olefin may be chlorine, bromine, or iodine. The terminally oxidized olefin used as the starting material of the present invention has the general formula (wherein,
R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms, x is a halogen atom, and m is an integer of 5 to 7.

) is a terminally halogenated olefin.

Specific examples include 7-octenyl-1-chloride,
Examples include 8-nonenyl-1-chloride, 9-decenyl-1-chloride, 9-octadecenyl-1-chloride, and 9-eicosenyl-1-chloride. In addition, the olefin used together with such a halogenated olefin has the general formula (wherein R4 is a straight-chain alkyl group having 2 to 4 carbon atoms, R
5 is hydrogen or a straight chain alkyl group having 2 to 4 carbon atoms.

).

Specific examples thereof include 1-butene, 1-hexene, 3-hexene, 3-octene, and 5-decene. The halogenated olefin and olefin used as starting materials are at least one of R4 and R5 (of course, both may be used).

) is selected and combined so that the number of carbon atoms in the olefin is (9-m) (where m is m in the above general formula of the terminally halogenated olefin used in combination), and a metathesis reaction is performed. By doing so, a terminally halogenated olefin having 12 carbon atoms, which is an intermediate product in the production method of the present invention, can be easily obtained. For example, as is obvious from the reaction formula below, various halogenated olefins used as intermediate products of the present invention can be easily obtained (R3, R4, and R5 are as described above).

). Specific examples of such halogenated olefins as intermediate products of the present invention include 19-dodecenyl-1-chloride, 28-dodecenyl-1-chloride, 37-dodecenyl-1-chloride, 46-dodecenyl-1-chloride, carbon dioxide useful as a raw material for the synthesis of such pheromone, etc. The number 12 terminally halogenated olefins were difficult to synthesize in the past, but can be synthesized efficiently in the present invention.

The fact that it is not easy to synthesize such a halogenated olefin by such a method is evidenced by the fact that the above compounds 1 and 2 are new compounds that have not been described in any literature. Catalyst component (4) constituting the catalyst used in the present invention
Examples of halogen-containing metal compounds of metals selected from tungsten, molybdenum, and rhenium include WCl6, WCl4, WOCl4, WBr6, MOC
l5, ReCl4, WCl4(Py)2, MO(NO)
2C12(Py)2, etc. (Py in the above formula represents pyridine.

). In addition, as the reducing metal compound selected from hydrides, alkyl compounds, and alkyl halides of metals from Groups 1 to 2 of the periodic table, which are the catalyst component (B), for example, n
-butyl lithium, lithium aluminum hydride, n-
Propylmagnesium bromide, n-butylmagnesium iodide, triethylaluminum, diene. Examples include chillaluminum chloride, ethylaluminum dichloride, and tetraethyltin. Catalyst component (
The proportion of 4) and (B) is usually in the range of 0.1 to 6, preferably 1.0 to 8.0 in molar ratio. COL ethanol, ace. Electron-donating compounds such as tylacetone, trialkylphosphine, and trialkylamine can be added, and by adding these, the catalyst activity and selectivity can be improved. The catalyst of the present invention is sensitive to oxygen and water, and the presence of these will reduce the catalytic activity/performance. Therefore, the raw materials, catalyst components, solvents, reaction equipment, etc. used in the present invention should be thoroughly dehydrated and
It is preferable that the catalyst be dried and that preparation of the catalyst and reaction operations be carried out in an inert gas stream (for example, a nitrogen stream). A suitable solvent can be used in the preparation of the catalyst and the metathesis reaction in the present invention.

Such solvents include, for example, inert hydrocarbons and halogenated hydrocarbons such as benzene, n-hexane, cyclohexane, toluene, chlorobenzene, and the like. In addition, the temperature for catalyst preparation and metathesis reaction is -50 to 160°C, preferably -30 to 800°C.
is appropriate. In the metathesis reaction of the present invention, as can be seen from the above reaction formula, various compounds are simultaneously produced as by-products in addition to the desired halogenated olefin.
For example, in Example 6 below, as shown in the following formula, the target compound C2H5-CH=CH-C8Hl6Cl
In addition, various compounds are produced as by-products. Since the compounds produced by such side reactions can be used as raw materials for the reaction after separation, such side reactions do not pose much of a disadvantage. The desired halogenated olefin is separated from the metathesis reaction product in the present invention (however, this separation is not essential).

), the halogenated olefin can be converted to dodecenyl acetate by reacting it with a metal carboxylate, such as silver acetate. The carboxylic acid dodecenyl ester obtained by the production method of the present invention can be used as a pheromone or a synthetic attractant, and can also be used as a raw material for fragrances, polymer compounds, and as a starting material for the synthesis of other complex organic compounds. . Next, examples will be given and explained.

Example 1 6 l mmol of WCl is added to a 200 ml three-necked flask that has been thoroughly dried and purged with nitrogen, and then 50 ml of cyclohexane that has been dehydrated and purged with nitrogen is added and dissolved.

Next, 1 mmol of ethanol, 50 mmol of 9-octadecenyl-1-chloride (purity 73%), and 50 mmol of 5-decene are added in this order, and finally 4 mmol of ethylaluminum dichloride is added, and the mixture is reacted with vigorous stirring at room temperature. Each of the above operations is performed in a nitrogen stream. A small amount of methanol is added to the first powder to stop the reaction, and after separating the methanol layer containing the waste catalyst, NaHCO
After neutralizing with 3 aqueous solution and adding a small amount of ether, the organic layer was separated by washing with water several times, dried with Na2sO4, and analyzed by gas chromatography. As a result, 2.84y of 9-tetradecenyl-1-chloride was produced. I understood.

From this reaction solution, 9-tetradecenyl-1 was obtained by distillation under reduced pressure.
-After separating the fraction containing chloride, it was dissolved in a mixed solvent of acetic acid and dimethyl sulfoxide (1°1) using silver acetate.
The product was acetylated by heating at 0°C for 1CJI1f, and the product was purified by column chromatography using silica gel.
2.2y of tetradecenyl-1-acetate was isolated.

It was confirmed that this product was 9-tetradecenyl acetate based on elemental analysis, mass spectrometry, and analysis of products obtained by ozonolysis. Furthermore, cis-9-tetradecenyl-1-acetate was separated from this 9-tetradecenyl-1-acetate (a mixture of cis and trans) by thin layer chromatography using silver nitrate-silica gel.

This cis-form is effective as a pheromone for armyworms, white moths, teal moths, apple moths, etc. Example 2 A reaction was carried out under the same conditions as in Example 1, except that the solvent was changed to methylcyclohexane, the reaction temperature was changed to -20°C, and the reaction time was changed to 1 hour. Ruacete day. 2f was obtained.

The cis isomer content of 9-tetradecenyl acetate is 96
As a result of comparing the IR absorbance of C-1 with that of commercially available pure trans-9-tetradecenyl acetate, it was concluded that it was 80% or more.

Examples 3 to 5 Same method as Example 1, but omitting the addition of ethanol and using Table 2 instead of ethylaluminum dichloride.
When the reaction was carried out using the catalyst component (B) described in Table 2, 9-tetradecenyl-1-chloride was obtained in the yield shown in Table 2.

9-tetradecenyl-1-acetate could also be produced from this 9-tetradecenyl-1-chloride in the same manner as in Example 1.

Example 6 The reaction was carried out under the same conditions as in Example 1 except that 5-decene was changed to 3-hexene. As a result, 9-
2.31y of dodecenyl-1-chloride was obtained.

This was acetylated in the same manner as in Example 1 to obtain 2.0 g of 9-dodecenyl-1-acetate. Example 7 WC was placed in a 200 mL three-neck flask that had been purged with nitrogen.
Add 13 liters of millimole, then add 20 liters of dehydrated chlorobenzene.
ml was added, and while stirring, dry NO gas was introduced at normal pressure, and the mixture was treated at room temperature for 1 hour.

Thereafter, the NO gas in the flask is completely removed under reduced pressure using a vacuum pump. Next, chlorobenzene was added to dilute the total volume to 50ml, and then 3 mmol of pyridine, 50 mmol of 9-octadecenyl-1-chloride, 50 mmol of 1-hexene, and 10 mmol of ethylaluminum dichloride were added.
Millimoles were also added and reacted at 50°C for 1 hour. Gas chromatographic analysis of the reaction products revealed that 9-tetradecenyl-1-chloride 1.3y1 and ω-decenyl-1-
It was found that 1.04y of chloride was contained. When 0.50y of the latter was treated with silver acetate, 0.51g of ω-decenyl acetate was obtained, and when treated with ammoniacal silver oxide, 0.40y of ω-decenyl alcohol was obtained.

And, ω-decenyl alcohol can be used as a fragrance having a rose-like odor. Examples 8-14 In place of WCl3, pyridine, and ethylaluminum dichloride in Example 7, MOCl5 was used, respectively.
, tri-n-butylphosphine, and methylaluminum sesquichloride were used in the same molar amounts as in Example 7, and in place of 9-octadecenyl-1-chloride and 1-hexene in Example 7, the compounds listed in Table 3 below were used, respectively. The reaction was carried out according to Example 7, except that 25 mmol each of halogenated olefin (1) and olefin (■) were used and the reaction was carried out at room temperature for 2 hours.
Each halogenated olefin (intermediate product) shown in Table 3 was obtained.

Next, the intermediate product 5-decenyl-1-chloride of Example 8 was heated with silver isopentanoate in a mixed solvent of isopentanoic acid and dimethyl sulfoxide to obtain 5-decenyl-1-isopentenoate.

In addition, the halogenated olefins as intermediate products obtained in Examples 9, 10, 11, 12, 13, and 14 were treated in the same manner as in Example 1, and the halogenated olefins as shown in Table 13 were obtained. A saturated carboxylic acid ester was obtained.

Each of these esters is effective as a pheromone and attractant as shown in Table 1. Furthermore, among the intermediate olefins listed in Table 3, the products of Examples 8, 11, 12, 13 and 14 are new compounds, among which 5-decenyl-1-chloride and 7-hexadecenyl-1-chloride was identified as follows.

That is, the intermediate product of Example 8, 5-decenyl-1-
The composition of chloride has a parent peak with mass number 174 by gas chromatography-mass spectrometry, and 41,
Because it has peaks at 5, 69, 97, and 111,
It was confirmed that it was a linear ClOHl9Cl with no branching. Furthermore, as a result of analysis of ozone decomposition products using the same method, n-pentylaldehyde was mainly detected, indicating that the double bond is located at the 5th position from the end of the methyl group, that is, CH3-(CH2)3 -CH=CH-(CH
2) It was confirmed that it was 3-CH2Cl (5-decenyl-1-chloride). In addition, the structure of the intermediate product 7-hexadecenyl-1-chloride of Example 11 was determined by the same analysis method as in Example 9, with parent peak 258 and 41
, 55, 69N8, 97, 111 and 125, and since n-nonylaldehyde is mainly produced by ozone decomposition,
=CH-(CH2)5-CH2Cl (7-hexadecenyl-1-chloride).

Claims (1)

[Claims] 1 General formula R^3-CH=CH-(CH_2)_m-CH_2X(
In the formula, R^3 is hydrogen or an alkyl group having 1 to 10 carbon atoms, X is a halogen atom, and m is an integer of 5 to 7. ) and a terminally halogenated olefin represented by the general formula R
^4-CH=CH-R^5 (wherein, R^4 is a straight-chain alkyl group having 2 to 4 carbon atoms, R^
5 is hydrogen or a straight chain alkyl group having 2 to 4 carbon atoms. ) and R^ of the olefin.
The number of carbon atoms in at least one of 4 and R^5 is (9-m)
(In the formula, m is m in the above general formula of the terminally halogenated olefin to be used in combination.) a halogen-containing metal compound (including a mixture of the halogen-containing metal compounds); and (B) a reducing metal compound selected from hydrides, alkylates, and alkyl halides of metals from groups I to IV of the periodic table. A carboxylic acid characterized by carrying out a disproportionation reaction using a catalyst to produce a terminal halogenated olefin having 12 carbon atoms, and then treating the halogenated olefin obtained by the reaction with a metal salt of a carboxylic acid. Method for producing acid dodecenyl ester.