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United States Patent (19) (11) 3,867,453 Mukaiyama Et Al

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United States Patent (19) (11) 3,867,453 Mukaiyama Et Al United States Patent (19) (11) 3,867,453 Mukaiyama et al. (45) Feb. 18, 1975 54 PRODUCTION OF KETONE BY REACTION 260/476 R, 471 C, 586 R, 584 A, 593 R, 570 OF ESTER OR THOL ESTER WITH AB, 570 R, 594, 577,578 GRIGNARD REAGENT 75) Inventors: Teruaki Mukaiyama; Masashi (56) References Cited Araki, both of Tokyo; Hisashi OTHER PUBLICATIONS Takei, Yokohama, all of Japan Kharasch et al., Grignard Reactions of Nonmetallic (73) Assignee: Sumitomo Chemical Company, Substances, Pages 561-562 (1954). Limited, Osaka, Japan Primary Examiner-Daniel D. Horwitz 22 Filed: Mar. 11, 1974 Attorney, Agent, or Firm-Stevens, Davis, Miller & (21) Appl. No.: 449,760 Mosher 57 ABSTRACT 52 U.S. Cl........ 260/570 AB, 260/570 R, 260/577, 260/578, 260/584 A, 260/586 R, 260/590, Ketones are produced by the reaction of an ester or a 260/591, 260/592, 260/593 R, 260/594, thiol ester with a Grignard reagent, optionally in an 260/327 M, 260/470 R, 260/471 C inert solvent at a temperature of preferably from -78 51 Int. Cl........................ C07c87/48, CO7c87/36 to --60C. 58) Field of Search....... 260/590, 591, 592, 327 M, 5 Claims, No Drawings 3,867,453 1 2 PRODUCTION OF KETONE BY REACTION OF commercial scale production since it has many disad ESTER OR THIOL ESTER WITH GRIGNARD vantages such as the yield of the ketone being not so REAGENT high, the reactivity of the organic cadmium compound being so low as to by-produce almost no tertiary alco This invention relates to a process for producing ke 5 hol, stable cadmium compound having to be employed, tones by the reaction of an ester or a thiol ester with a and the like. Grignard reagent. It is an object of the present invention to provide a It has been generally known that the reaction of process for producing ketones in high yield without by Grignard reagents with carboxylic acid derivatives pro producing tertiary alcohols. It is another object of the duces not only ketones but also tertiary alcohols. In O present invention to provide a process for producing order to increase the yields of ketones while suppress ketones using a special ester or thiol ester as one of the ing those of tertiary alcohols, there have been proposed starting materials. Further objects and advantages of some processes for producing ketones by reacting car this invention will be apparent to one skilled in the art boxylic acid derivatives with Grignard reagents. For ex from the accompanying disclosure and discussion. ample, in the reaction of a halogenated acyl compound The present invention provides a process for produc with a Grignard reagent, the yield of the ketone in ing a ketone which comprises reacting a compound of creased to some extent when the halogenated acyl the formula, compound was used in excess, but this process is not suitable for practical production (D. A. Shirley, Org. O Reactions, 8, 28 (1954)). In the reaction of a N 20 N acylimidazole used instead of a halogenated acyl com Ril - - Y - c1 (I) pound with a Grignard reagent, in which the reaction was carried out at a temperature of from 50°C to Na? room temperature for 5 to 8 hours, the yield of the ke tone varied from 5 to 94 percent. Thus this process is wherein R is alkyl having 1-10 carbon atoms, cycloal not suitable for commercial scale production (H. A. kyl having 3-8 carbon atoms, alkenyl having 2-0 car Staab and E. Jost, Ann. 655, 90(1962)). Although bon atoms, alkynyl having 2-10 carbon atoms, phenyl, many other processes such as using an acid amide com phenylalkyl having 7-10 carbon atoms and phenylalke pound and a Grignard reagent, an acid anhydride and nyl having 7-10 carbon atoms which may have at least a Grignard reagent, etc., are proposed, the yields of the one substituent such as alkyl having 1-4 carbon atoms, ketones are not suitable for commercial scale produc alkoxy having 1-4 carbon atoms, oxo, amino, substi tion. Recently, it is reported that the reaction of a 8 tuted amino, halogen and so on, or a radical in which acyloxyquinoline with a Grignard reagent gives ketones two or more of the above-mentioned radicals are (T. Sakan and Y. Mori, Chen. Lett., 793 (1972)). The bonded through -0-; R is a hydrocarbon residue reaction time required in said reaction is about 2.5 35 which can be heterocyclic rings together with the C and hours and the yields are 64 percent for acetophenone, N atoms and which may contain one or more hetero 61 percent for propiophenone, 82 percent for benzo atoms and particularly heterocyclic rings containing R' phenone, etc. But in this process, it should be noted are preferably five-menbered rings or six-membered that the yields of ketones are not so high and further rings which may have at least one substituent such as that 9 percent of triphenylcarbinol is by-produced in 40 lower alkyl; and Y is oxygen or sulfur, with a Grignard the case of the production of benzophenone. reagent of the formula, As mentioned above, in the process for producing ke tones by the reaction of a carboxylic acid derivative R* - Mg - X with a Grignard reagent, it is important to decrease the (II) by-production of tertiary alcohols which are obtained 45 by the undesired reaction of the ketones produced with wherein R is alkyl having 1-0 carbon atoms, cycloal the Grignard reagents and to increase the yields of the kyl having 3-8 carbon atoms, alkenyl having 2-10 car desired ketones. These problems have not been solved bon atoms, or phenyl which may have at least one sub before the present application. stituent such as alkyl having 1-4 carbon atoms, alkoxy It has also been proposed to produce ketones by the 50 having 1-4 carbon atoms, halogen and so on; and X is reaction of a halogenated acyl compound with an or chlorine, bromine or iodine, bromine being preferable. ganic cadmium compound which is used instead of a Specific examples of the heterocyclic radicals in the Grignard reagent, but this process is not suitable for formula (I) are as follows: C CO. O. O. in O. ?h 3,867,453 CH 3 The following compounds are some specific examples ample, 2-pyridylthiol-4-oxovalerateethylene of the compounds of the formula (): dithioacetal, is used as a starting material, the corre 2-pyridyl acetate, 2-pyridyl propionate, 2-pyridyl ben sponding diketone can be obtained by hydrolyzing the zoate; 2-pyridiyl-3-phenyl propionate, 3-pyridyl cinna ethylene dithioacetal moiety in the product obtained by mate, bis(2-pyridyl) adipate, 2-pyridyl (5-ethoxycar the process of the present invention (K. Narasaka et. al., bonyl) valerate), 2-pyridyl-6-oxoheptanoate, Bull. Chem. Soc. Japan 45, 3724 (1972)). The resulting 2-pyridyl-4-oxovalerate ethylene dithioacetal, 2 diketone is a very important compound in chemical in oxazolyl benzoate, 2-oxabenzoxazolyl benzoate, 2 dustries. For example, 1,4-diketone, which can be ob thiazolyl benzoate, 2-benzothiazolyl benzoate, 2-(N- tained as mentioned above, is a very important inter methylimidazolyl) benzoate, 2-(N- 25 mediate for synthesizing cyclopentenones or furanes. methylbenzoimidazolyl) benzoate, 2-pyridylthiol ace Thus the process of the present invention is very impor tate, 2-pyridylthiol propionate, 2-pyridylthiol benzoate, tant and can widely be used in chemical industries. 2-pyridylthiol-3-phenyl propionate, 2-pyridylthiol cin According to the process of the present invention, namate, bis(2-pyridylthiol) adipate, 2-pyridylthiol (5- ketones can be obtained in high yield without the by ethoxycarbonyl) valerate), 2-pyridylthiol-6- production of tertiary alcohols. In addition, the reac oxoheptanoate, 2-pyridylthiol-4-oxovalerate ethylene tion of the present invention can be applied to the com dithioacetal, 2-oxazolylthiol benzoate, 2-oxabenzolyl mercial production of variously complicated ketones. benzoate, 2-thiazolylthiol benzoate, 2-benzothiazolyl Further, the reaction time is significatly short and the thiol benzoate, 2-(N-methylimidazolylthiol) benzoate, high reaction rate can be attained at lower tempera 2-(N-methylbenzoimidazolylthiol) benzoate, etc. 35 ture. As the Grignard reagent, the following compounds The invention is illustrated more particularly by way are some specific examples: of the following examples but, as will be more appar butylmagnesium bromide, hexylmagnesium bromide, ent, is not limited to the details thereof. hexenylmagnesium bromide, cyclohexylmagnesium In the following examples, the products are identified bromide, phenylmagnesium bromide, etc. 40 by means of infrared, NMR and elementary analyses, The reaction can be carried out at lower tempera and the reactions are carried out under an atomosphere tures, preferably from -78°C to +60°C. of argon before the completion of the addition of Inert solvents such as diethyl ether, dibutyl ether, di Grignard reagent. The yields are calculated based on methoxyethane tetrahydrofuran, dioxane, tetrahydro the ester or thiol ester used. pyrans, benzene, toluene, xylene, chlorobenzenes and 45 the like which do not react with the Grignard reagent EXAMPLE can be used, if necessary. Particularly, tetrahydrofuran is most preferable. To a solution of 0.99g of 2-pyridyl benzoate in 10 The Grignard reagent can be used in equimolar to or cc of tetrahydrofuran, 1 cc of tetrahydrofuran contain in excess of the compound of the formula (I). 50 ing an equimolar amount of phenylmagnesium bromide According to the process of this invention, the reac was added dropwise at 0°C with stirring. The reaction tion can be completed in very short time. For example, solution remained transparent. After the completion of when the reaction is carried out at 0°C, it can be com the dropwise addition, about 0.2 cc of water was added pleted immediately after the completion of the addition to the reaction solution to precipitate white magnesium of a Grignard reagent.
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