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United States Patent (19) 11 Patent Number: 4,760,196 Fukumoto Et Al

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United States Patent (19) 11 Patent Number: 4,760,196 Fukumoto Et Al United States Patent (19) 11 Patent Number: 4,760,196 Fukumoto et al. 45 Date of Patent: Jul. 26, 1988 54 METHOD FOR PREPARING AN ALDEHYDE OR ALCOHOL BY REDUCTION OF A OTHER PUBLICATIONS CARBOXYLIC ACD Nystron, “J. Amer. Chem. Soc.'', vol. 69, pp. 2548 (1947). 75 Inventors: Takehiko Fukumoto; Akira Brown et al., "J. Amer. Chem. Soc.", vol. 75, p. 6263 Yamamoto, both of Niigata, Japan (1953). 73 Assignee: Shin-Etsu Chemical Co., Ltd., Tokyo, Pettit et al., “J. Organic Chem.”, vol. 27, p. 2127 (1962). Japan Primary Examiner-Werren B. Lone Attorney, Agent, or Firm-Jules E. Goldberg 21 Appl. No.: 47,612 57 ABSTRACT (22 Filed: May 8, 1987 The inventive method is particularly advantageous for the preparation of an unsaturated alcohol or aldehyde 30 Foreign Application Priority Data by the reduction of a corresponding unsaturated car boxylic acid since the unsaturated double bond in the May 12, 1986 JP Japan ................................ 61-108274 starting acid is not hydrogenated by the reaction of 51) Int. Cl* .............................................. C07C 45/54 reduction. The method comprises first reacting the 52 U.S. C. .................................... 568/484; 568/490; starting acid with an alkyl chloroformate to form an 568/864 intermediate compound by the dehydrochlorination and the intermediate compound is then reduced by 58. Field of Search ............... 568/484, 490, 485, 864, using sodium borohydride as the reducing agent. The 568/886 proportion of the aldehyde to alcohol in the product (56) References Cited mixture can be controlled by modifying the amount of U.S. PATENT DOCUMENTS the reducing agent and/or the reaction time. 4,156,791 5/1979 Childs ................................. 568/864 3 Claims, No Drawings 4,760,196 1. 2 reaction is sometimes accompanied by undesirable side METHOD FOR PRE PARING AN ALDEHYDE OR reactions when the product is not sufficiently stable ALCOHOL BY REDUCTION OF A CARBOXYLC resulting in decrease in the yield of the desired product. ACD The selectivity of the reducing reaction is also not with out problems. In addition, the diglyme used as the sol BACKGROUND OF THE INVENTION vent can be recovered with some difficulties and the The present invention relates to a method for prepar waste material containing aluminum chloride may be ing an aldehyde or alcohol by the reduction of a carbox responsible for very serious environmental pollution ylic acid or, more particularly, to a method for prepar when the waste water is discharged to public waterway ing an aldehyde or alcohol by the reduction of a corre 10 without appropriate treatment of sewage disposal. sponding carboxylic acid using a metal borohydride as Lithium aluminum hydride and sodium borohydride the reducing agent. both belong to a class of typical complex compounds When an aldehyde or an alcohol compound is desired capable of reducing various kinds of organic com to be prepared by the reduction of a corresponding pounds by releasing hydrogen in the form of hydride carboxylic acid, it is a usual practice that the carboxylic 15 ions. The problems in these hydrides as an industrial acid is reduced as a solution in diethyl ether or tetrahy reducing agent are the expensiveness of lithium alumi drofuran using lithium aluminum hydride LiAlH4 as the num hydride having a relatively high reducing power reducing agent. The applicability of this reducing and the relatively low reducing power of the less expen method, however, is limited even by setting aside the sive sodium borohydride necessitating combined use of problem of expensiveness of this reagent to probibit 20 an auxiliary reagent to cause complicacy of the process industrial application of the method. For example, re and low yield of the product. At any rate, each of these duction of an unsaturated carboxylic acid by this hydrides is not suitable as a reducing agent when a method is not always suitable for the preparation of the carboxylic acid should be reduced to the corresponding corresponding unsaturated aldehyde or alcohol since aldehyde and not to the alcohol. the reduction takes place not selectively at the carboxyl 25 group alone but also the unsaturated linkage in the un SUMMARY OF THE INVENTION saturated carboxylic acid is also susceptible to reduc An object of the present invention is therefore to tion. When cinnamic acid is reduced in an ether solution provide a method for the preparation of an aldehyde or by using lithium aluminum hydride as the reducing alcohol by reducing a carboxylic acid using a metal agent, for example, the reaction product is not the de 30 borohydride or, in particular, sodium borohydride as sired cinnamyl alcohol but dihydro-cinnamyl alcohol as the reducing agent. is taught by R.F. Nystron, et al. in Journal of the Amer Another object of the invention is to provide a ican Chemical Society, volume 69, page 2548 (1947). method for preparing an unsaturated aldehyde or alco The unsaturated linkage in the unsaturated carboxylic hol by reducing a corresponding unsaturated carboxylic acid may be protected from reduction by using a reduc 35 ing agent system of lithium aluminum hydride com acid with a metal borohydride as the reducing agent bined with anhydrous aluminum chloride. For example, without affecting the unsaturated linkage in the acid. sorbic acid CH3CH=CH-CH=CH-COOH can be Thus, the method of the present invention for the reduced by this method into hexa-2,4-dienol preparation of an aldehyde of the general formula CH3CH=CH-CH=CH-CH2OH. This method, RCHO or alcohol of the general formula RCH2OH, in however, is not practical due to the extremely low yield which R is a monovalent hydrocarbon group having 1 of the reaction product of, for example, only 20% in the to 20 carbon atoms selected from the class consisting of above mentioned reduction of sorbic acid. Moreover, alkyl, alkenyl, alkynyl and aryl groups, by reducing a the reaction product in the reduction of a carboxylic carboxylic acid comprises the steps of: acid using lithium aluminum hydride is always the cor 45 (a) reacting a carboxylic acid represented by the gen responding alcohol while the corresponding aldehyde eral formula compound, which should have been formed at the inter mediate stage, can hardly be obtained as the final prod R-CO-OH, (I) uCt. in which R has the same meaning as defined above, and Sodium borohydride is less expensive as a reducing 50 agent than lithium aluminum hydride and is used in a chloroformate ester represented by the general for various synthetic reactions. The reducing power of this mula reducing agent is, however, not strong enough to re duce a carboxylic acid into a corresponding aldehyde or CICO-OR, (II) alcohol. The reducing power of sodium borohydride 55 in which R1 is a monovalent hydrocarbon group having can be strengthened by performing the reducing reac 1 to 20 carbon atoms selected from the class consisting tion in diglyme as the solvent by combining sodium of alkyl, alkenyl, alkynyl and aryl groups or, in particu boorhydride with anhydrous aluminum chloride as is lar, alkyl groups, in the presence of an acid acceptor to taught by H. C. Brown et al. in Journal of the American form an intermediate compound represented by the Chemical Society, volume 75, page 6263 (1953) or by 60 general formula combining sodium borohydride with boron trifluoride BF3 as is taught by G. R. Pettit, et al. in Journal of R-CO-O-CO-OR, (III) Organic Chemistry, volume 27, page 2127 (1962). These improved methods for increasing the reducing in which R and Reach have the same meaning as de power of sodium borohydride are still not quite satisfac 65 fined above; and tory due to the use of a Lewis acid such as anhydrous (b) reducing the intermediate compound with an aluminum chloride and boron trifluoride. Namely, the alkali metal borohydride, such as sodium borohydride procedure of the reaction is usually troublesome and the NaBH4 and lithium borohydride LiBH4 or, preferably, 4,760,196 3 4. sodium borohydride, as the reducing agent into the When an aldehyde compound is the desired product, aldehyde of the formula RCHO or alcohol of the for the temperature should preferably be in the range from mula RCH2OH. -50 C. to 0 C. so that the yield of the aldehyde com pound can be increased relative to the alcohol com DETALED DESCRIPTION OF THE pound. The solvent used in this step may be the same PREFERRED EMBODIMENTS one as in the reaction of the starting carboxylic acid and As is described in the above given summary of the the chloroformate ester including dialkyl ethers, e.g. invention, the starting carboxylic acid is reduced by the diethyl ether, cyclic ethers, e.g., tetrahydrofuran, 1,2- metal borohydride not in the form of the free acid but in dimethoxy ethane, i.e. diglyme, and the like. It is not the form of a very specific intermediate compound 10 necessary that the solvent used in the reaction of reduc something like an acid anhydride which is formed by tion is anhydrous and a mixture of water and an organic the dehydrochlorination reaction between the starting solvent can be used without particularly disadvanta carboxylic acid and a chloroformate ester. This method geous effect provided that the reactants are soluble in of reduction is very advantageous because, if not to the medium. Tetrahydrofuran is one of the preferred mention the inexpensiveness of the reducing agent, the 15 organic solvents which can be used in both steps for the reducing reaction can be controlled to give an aldehyde preparation of the intermediate compound and for the compound which is intermediate in the course of the reduction of the same.
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