JPS6377834A - Production of methyl ketones - Google Patents

Abstract

PURPOSE:To obtain methyl ketones, by reacting a compound having terminal acetylene bond with a proton donative compound in the presence of an aryl telluric acid anhydride, thereby selectively adding water exclusively to the acetylene bond. CONSTITUTION:A methyl ketone is produced by reacting a compound having terminal acetylene bond (e.g. mono-, di- or polyacetylene) with a compound capable of supplying proton (e.g. water, weak acid, organic acid, etc.) in the presence of a compound of formula (Ar is aryl which may have substituent group such as alkyl, alkoxy, amino, halogen, etc.) in a solvent such as acetic acid at 50-150 deg.C. The compound of formula can be synthesized from an aro matic hydrocarbon of formula ArH and a halide of Te<4+> and is converted to a diaryl ditelluride in the course of the reaction. The ditelluride can be recovered and reused in the form of the compound of formula. The compound of formula is non-toxic and easily handled.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a corresponding methyl ketone from a compound having a terminal acetylene compound.

[Conventional technology]

The addition reaction of water to acetylene is used as a method for synthesizing acetaldehyde, and various catalysts have been proposed for use in this reaction. The main known methods include methods using Lewis acids or Hg(U) salts such as mercuric sulfate.

On the other hand, as an example of oxidizing an unsaturated compound using an aryl phosphoric anhydride, there is a reported example of diacetoxylating an olefin in the presence of sulfuric acid as shown below.
0Ac OAc [The 13th Symposium on Organic Sulfur and Phosphorus Compounds, sponsored by the Chemical Society of Japan (1985 17J
'), collection of lecture abstracts p, 57. [Sonoda et al.] =, (for acetylene compounds) has not yet been seen.

[Problem that the invention seeks to solve]

Acid catalysts have low reactivity and are not practical.

In addition, the method using )Ig(II) salt has many practical handling problems due to the high toxicity of Hg(IT).
In addition, the selectivity of the reaction is low, and it is difficult to distinguish between terminal acetylene bonds and internal acetylene bonds when adding water.

[Means for solving problems]

When adding water to a compound having a terminal acetylene bond, the present inventors unexpectedly discovered that by adding water to a compound having a terminal acetylene bond, by adding an arylthyl phosphoric acid anhydride, the terminal acetylene bond was The present invention was completed by discovering that the corresponding methyl ketone can be obtained by selectively adding water only to the bond.

The present invention relates to a compound capable of supplying protons in the presence of an aryl phosphoric acid anhydride represented by the following general formula and the acetylene bond in the production of methyl ketones by adding water to a compound having a terminal acetylene bond. A method for producing methyl ketones, the method comprising reacting them with a compound.

The gist is:

The method of the invention can be applied to many acetylene compounds having terminal acetylene bonds in monoacetylene, diacetylene 1 or polyacetylene.

Also thiols, thioamides, thioesters.

It can also be applied to acetylene compounds having various substituents other than groups that are particularly easily oxidized such as phosphine and phosphite, and water can be selectively added to the terminal acetylene bonds.

Although the method of the present invention allows water to be added to a compound having a terminal acetylene bond as shown in the following formula fat or [bl, the corresponding methyl ketone can be obtained. When applied to a compound that retains its internal acetylene bond,
It has the characteristic that water can be selectively added only to the terminal acetylene bond to obtain the corresponding methyl ketone.

-1 → CL C-(RJ, 1-CCH3(CI R'-CmiC-(R2), 1-CCH:+(in the formula,
R' is a hydrogen atom, a saturated or unsaturated aliphatic compound, an alicyclic compound, or a hydroaromatic compound.

Alternatively, monovalent atomic groups of various hydrocarbons belonging to aromatic compounds, etc., R2 is a divalent hydrocarbon group having 1 or more carbon atoms, n is O or 1, and R3 is a saturated or unsaturated aliphatic group. The aryl phosphoric acid used in the present invention is represented by the following general formula. Ru.

Ar- represents an aryl group (2+), in which the aryl group is phenyl, 8, unsubstituted such as naphthyl, anthryl, phenanthryl, these substituted products with various substituents, or polyesters with multiple substituents. A substituted aryl phosphoric acid anhydride can be used.As a substituent for the aryl group, an alkyl group having 1 to 8 carbon atoms or an alkoxyl group can be used.

Examples include substituted or unsubstituted phenoxy groups, substituted or unsubstituted amino groups, benzyl groups, and halogen atoms. Preferably, heminterlic acid has an electron-donating group such as a methoxy group, an ethoxy group, a butoxy group, or a convex phenoxy group as the 71 iD group of the aryl group. anhydride or nuclentil phosphate anhydride.

The ratio of the aryl phosphoric acid anhydride to the acetylene compound is preferably in the range of 1 to 20 mol%, preferably 5.
The range is from 15 mol% to 15 mol%, more preferably from 8 to 12 mol%. If it is less than 1 mol%, the reaction time will be long and it is not practical, and even if it is used in excess of 20 mol%, the effect will not increase. ＼5 I can't laugh.

Compounds capable of supplying protons used in the method of the present invention include, in addition to water, inorganic weak acids such as carbonic acid, NH-containing acids such as carbonic acids, organic sulfonic acids, and organic phosphonic acids.
The compounds that can supply these protons are the end of the starting acetylene compound (1 mole per acetylene bond)! As mentioned above, preferably use an amount of 2 moles or more.

As the carboxylic acid, aliphatic or aromatic monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids are used. Preferably, straight-chain aliphatic saturated monocarboxylic acids having 2 to 9 carbon atoms, which are liquid at room temperature, and more preferably 2 to 3 carbon atoms, are used, which have good miscibility with water.

In the method of the present invention, it is preferable to use a reaction solvent during the reaction. As the reaction solvent, it is necessary to avoid those that inhibit the reaction, but it is preferable to use a solvent that dissolves the reaction mixture well and has relatively high polarity.

Specific examples of solvents used include carboxylic acids and their anhydrides such as acetic acid and propionic acid, alcohols such as tutanol, ethanol, propatool, and butanol;
\3N-dimethylformamide.

Amides such as N,N-dimethylacetamide, nitriles such as acetonitrile and isobutyronitrile, ethylene glycol dimethyl ether, tetrahydrofuran,
Examples include ethers such as dioxane and cellosolve, carbonate ester +1, δ-butyrolactone, methylene chloride, sulfolane, trimethylsulfoxide, pyridine, and morpholine.

Acetic acid has the function of a reaction solvent and can supply protons, and if 1 mol or more of acetic acid is used per terminal acetylene bond of the raw acetylene compound, water can be added to the acetylene compound without supplying water. This is particularly preferred since it allows the addition reaction to proceed.

It is practically advantageous for the reaction temperature to be at least room temperature, preferably in the range of 50 to 150°C. Moreover, when using a raw material and/or a solvent with a low boiling point, it can also be carried out under pressure. The reaction atmosphere may be atmospheric pressure, but may also be carried out in a nitrogen atmosphere.

After the reaction, the product may be separated and purified by distillation, recrystallization, etc. in accordance with conventional methods.

Arylthyl phosphoric acid anhydride can be synthesized from various aromatic hydrocarbons (denoted as ArH) and halogenated Te'' as shown in 2fi+.

Furthermore, arylthylphosphoric anhydride changes into diaryldityllide during the reaction process, and can be recovered after the reaction. An aryl phosphoric acid anhydride can be easily obtained from the recovered diaryl dityllide as shown in formula (2) and can be reused.

The actual amount of aryl phosphoric acid anhydride consumed is only the operational loss, and costs can be reduced by replenishing the amount corresponding to this.

Furthermore, if an oxidizing agent such as Cu(H), Fe(r!J) or quinones is co-present during use, continuous VC use becomes possible by regenerating the arylthyl phosphoric anhydride within the system.

The applicability of this technology is extremely high, and it can be used for various purposes such as chemical modification of side chains of steroid compounds, synthesis of intermediates for vitamin A synthesis, synthesis of 181 of prostaglandin compounds, and synthesis of natural polyyne compounds. It can be used for various purposes such as application to the reaction of

[Effects of the Invention] The effects obtained by the present invention are: 1) Water can be selectively added only to the terminal acetylene viscosity of an acetylene compound.

2) Arylthyl phosphoric acid anhydride has a mild action, so it can be applied to acetylene compounds with various substituents, and it can be used to add water to only the terminal acetylene bond in terms of aUR without changing the substituents. can be added.

3) Arylthyl phosphoric acid anhydride exhibits the effect of significantly accelerating the reaction even when added in a small amount, so it may be sufficient to use just one portion of the dynamo.

4) Arylthyl phosphate anhydride is easy to handle because it does not have toxicity like Hg(II).

〔Example〕

Hereinafter, the uninvention will be specifically explained using reference examples, working examples, and comparative examples.

(Reference example) Synthesis of aryl phosphoric acid anhydride; l) ρ-
Synthesis of methoxybenzenethyl phosphoric anhydride; (i) p-
Synthesis of methoxyphenyltellurium trichloride; 12 g (0,0445 mol) of tellurium tetrachloride and 14.4 g (0,133 mol) of anisole were added to anhydrous chloroform 75- and heated under reflux for 2 hours while avoiding moisture. did.

The reaction mixture once dissolved during the course of the reaction, and as the reaction progressed further, a yellow solid precipitated.

After the reaction was completed, the mixture was allowed to cool at room temperature for 1 hour, and the precipitate was filtered off, washed with a small amount of chloroform, and then dried under reduced pressure.
12.8 g of yellow foliate crystals with a melting point of 190-192°C were obtained. (Yield: 88%).

Proton NMR and IR analysis identified the product as the title p-methoxyphenyltellurium trichloride.

(ii) Synthesis of P-methoxybenzenethyl phosphoric anhydride; Add 5 g of the compound obtained in (i) above to 10% aqueous sodium carbonate solution, stir at room temperature for 30 minutes, and then neutralize with 20% acetic acid aqueous solution. did. - At night, the precipitated crystals were filtered off and dried at 60°C under reduced pressure.

The yield was quantitative. (Melting point = 205-210°C).

2) According to the above method, various aryl phosphoric acid anhydrides shown in Table 1 were synthesized.

Example-1゜Synthesis of acetophenone from phenylacetylene; 0.153 g (1.5 mmol) of phenylacetylene and ρ-
Methoxybenzenethyl phosphoric anhydride 0.08g (0,1
5 mmol) was added to acetic acid 41R1, heated with stirring, and reacted under reflux for 20 hours.

After the reaction, acetic acid was distilled off under reduced pressure, and then ether 10-
The ether solution obtained by adding
% aqueous solution and dried over anhydrous magnesium sulfate.

Next, ether was distilled off from the ether solution under reduced pressure, and the residue was preliminarily purified by silica gel column chromatography using a benzene-hexane (2:l) mixture as a solvent, followed by gel permeation (G) column chromatography using chloroform as a solvent.
PC) Chromatograph (Japan Analysis Industry Co., Ltd., manufactured by Kiki, LC-0
9 type, JAIGEL-1) 1 and 2] column), the reaction product was purified by Sumitomo AM to obtain 161 g of acetophenone O. (Yield: 89%).

Examples 2 to 6 According to Example 1, reactions were carried out using various aryl phosphoric anhydrides instead of ρ-methoxyhensentelluric acid. The results are shown in Table 1.

Examples-7 to 11. and Comparative Examples-1 to 3゜Example-1
Table 2 shows the results of attempts to react various acetylene compounds using p-methoxybenzenethyl phosphoric acid according to the above.

As shown in each example, water is added to the terminal acetylene bond of an acetylene compound to yield the corresponding methyl ketone. Further, in the case of an acetylene compound having an internal acetylene bond, water is selectively added only to the terminal acetylene bond while retaining the internal acetylene bond to obtain the corresponding methyl ketone.

On the other hand, as shown in the comparative example, in the case of an acetylene compound having only internal acetylene bonds and no terminal acetylene bonds in the molecule, no water addition reaction occurred, and the raw acetylene compound was recovered as it was.

Table 1 Reaction conditions; Solvent: Acetic acid, 720 ml under reflux
time.

Table 2 Reaction conditions: Solvent: Acetic acid, 720 hours under reflux.

Patent Applicant Nitto Chemical Industry Co., Ltd. Subsidiary Amendment (Spontaneous) August 25, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of $ 1986 Patent Application No. 218059 2, Invention Name Process for producing methyl ketones 3 Relationship with the case of the person making the amendment Patent applicant 5-1-5 Marunouchi, Chiyoda-ku, Tokyo 100 4 Number of inventions increased by the amendment 6 Contents of the amendment (1) Regarding q in the description of the invention in the description, q is amended as follows.

1) On page 13, 3rd column to 2nd line from the bottom, "p-methoxybenzenethyl phosphoric acid" is corrected to "7p-methoxybenzenethyl phosphoric anhydride".

2) Page 14, lines 2 to 3, "p-methoxyhensentellurin fjJ J" is corrected to "p-methoxybenzenethyl phosphoric anhydride."

that's all

Claims (1)

[Scope of Claims] 1) A compound capable of supplying protons in the presence of an arylthylphosphoric anhydride represented by the following general formula when producing methyl ketones by adding water to a compound having a terminal acetylene bond. A method for producing methyl ketones, the method comprising reacting the acetylene compound with the acetylene compound. General formula: (In the formula, Ar- represents an aryl group, and is selected from those having no substituent or having a substituent.) 2) The aryl group is an alkyl group having 1 to 8 carbon atoms. , an alkoxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phenoxy group, a benzyl group, and a halogen atom. Manufacturing method described in section.