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Processes for Producing Alpha-Cyanohydrin Esters and Alpha-Hydroxy Acids

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Processes for Producing Alpha-Cyanohydrin Esters and Alpha-Hydroxy Acids Patentamt Europaisches |||| ||| 1 1|| ||| ||| || || ||| ||| || ||| || || || (19) J European Patent Office Office europeen des brevets (11) EP 0 926 1 34 A2 (12) EUROPEAN PATENT APPLICATION (43) Date of publication:ation: (51) Int. CI.6: C07C 253/08 30.06.1999 Bulletin 1999/26 (21) Application number: 98123461.0 (22) Dateof filing: 11.12.1998 (84) Designated Contracting States: (72) Inventors: AT BE CH CY DE DK ES Fl FR GB GR IE IT LI LU • Ishii, Yasutaka MC NL PT SE Takatsuki.shi, Osaka 569-1 1 1 2 (JP) Designated Extension States: • Nakano, Tatsuya AL LT LV MK RO SI Himeji-shi, Hyogo 670-0094 (JP) (30) Priority: 22.12.1997 JP 35339597 (74) Representative: Grunecker, Kinkeldey, (71) Applicant: Stockmair & Schwanhausser Daicel Chemical Industries, Ltd. Anwaltssozietat Osaka 590-8501 (JP) Maximilianstrasse 58 80538 Munchen (DE) (54) Processes for producing alpha-cyanohydrin esters and alpha-hydroxy acids (57) The present invention relates to a process for the preparation of compounds of formula (4) wherein a carbonyl compound of the formula (3) is reacted in the presence of a cyanogenation agent with an enol ester of the formula (1) or with an oxime ester of the formula (2): s CO 1 ^s r1— c-o-c-cC. (2) O CN O 7 F K , R7—C-R8 (3) R C— O-C— R (4) wherein R1 through R8 have meanings given in the application. The compound of formula (4) can be hydrolysed to obtain the corresponding compound of formula (5): fl7— C-OH (5) CM < CO CO CM <7> O Q_ LU Printed by Xerox (UK) Business Services 2.16.7/3.6 EP 0 926 134 A2 Description FIELD OF THE INVENTION 5 [0001] The present invention relates to processes for producing an a-cyanohydrin ester and an a-hydroxy acid, or salts thereof using an enol ester compound or an oxime ester compound, a carbonyl compound and a cyanogenation agent. BACKGROUND OF THE INVENTION 10 [0002] a-hydroxy acids are very useful compounds as precise fine chemicals such as medicines and agricultural chemicals, or intermediates thereof. [0003] As a process for producing a-hydroxy acids, there has been known a process which comprises reacting a car- bonyl compound such as an aldehyde with a cyanogenation agent such as hydrogen cyanide to produce the corre- 15 sponding a-cyanohydrin compound, then hydrolyzing the obtained a-cyanohydrin compound. In this process, however, since the cyanogenation reaction is reversible, it is generally difficult to obtain the corresponding a-cyanohydrin com- pound (particularly, an a-cyanohydrin compound derived from an aldehyde) in high yield. Moreover, since the obtained a-cyanohydrin compound tends to decompose into the carbonyl compound and hydrogen cyanide by the hydrolysis, it is difficult to produce an a-hydroxy acid in high yield. 20 SUMMARY OF THE INVENTION [0004] It is, therefore, an object of the present invention to provide a process for producing a highly stable a-cyano- hydrin ester useful as a precursor of an a-hydroxy acid in high yield. 25 [0005] It is another object of the present invention to provide a process for producing an a-hydroxy acid or a salt thereof in high yield. [0006] A further object of the present invention is to provide a process for producing an a-hydroxy acid which is gen- eral-purpose and of broader applicability, or a salt thereof. [0007] The inventors of the present invention did intensive investigation, and found that the reaction of an enol ester 30 compound or an oxime ester compound with a carbonyl compound and a cyanogenation agent in the presence of a metal catalyst provides the corresponding a-cyanohydrin ester in high yield and that the corresponding a-hydroxy acid or a salt thereof can be efficiently derived from the a-cyanohydrin ester by hydrolysis. The present invention was accomplished based on the above findings. [0008] That is to say, the present invention provides a process for producing an a-cyanohydrin ester derivative, which 35 comprises, in the presence of a metal catalyst, reacting an enol ester compound shown by the formula (1): R1-c-o-c=cC*4 0) 45 wherein R1 represents a non-reactive atom or a non-reactive organic group; R2, R3, and R4 are the same or differ- ent from each other and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R2, R3, and R4, together with 1 or 2 adjacent carbon atoms, may bond together to form a ring or an oxime ester compound shown by the formula (2): R1-C-0-N=CC* (2) R wherein R5 and R6 are the same or different from each other and each represents a non-reactive atom or a non- reactive organic group; R5 and R6, together with the adjacent carbon atom, may bond together to form a ring; and 2 EP 0 926 134 A2 R1 has the same meaning as defined above with a carbonyl compound shown by the formula (3): 0 7 II R— C-R8 (3) 10 wherein R' and R are the same or different from each other and each represents a non-reactive atom or a non- reactive organic group; and R7 and R8, together with the adjacent carbon atom, may bond together to form a ring and a cyanogenation agent to form an a-cyanohydrin ester shown by the formula (4): 15 CN O R-C-O-C-R1 (4) R8 wherein R1, R', and R have the same meanings as defined above. [0009] As the metal catalyst, for example, transition metal compounds may be used. R1 includes, e.g., hydrogen atom, 25 Ci_i0alkyl groups, C2_ioalkenyl groups, C3_i0cycloalkyl groups and C6_i0aryl groups. R2 to R4 each represents, e.g., a hydrogen atom or a Ci_3alkyl group. R5 and R6 include C^^alkyl groups, C3.10cycloalkyl groups and C6.10aryl groups, etc. R5 and R6, together with the adjacent carbon atom, may bond together to form, e.g., an about 3 to 20-membered cycloalkane ring. As the cyanogenation agent, there may be exemplified hydrogen cyanide, metal cyanides, cyanohy- drin compounds, and acyl cyanides. 30 [001 0] Further, the present invention provides a process for producing an a-hydroxy acid shown by the formula (5) : C02H R7-C-OH {5) 35 I a 40 wherein R7 and R8 have the same meanings as defined above or a salt thereof which comprises hydrolysing an a-cyanohydrin ester produced according to the above process and shown by the formula (4). 45 DETAILED DESCRIPTION OF THE INVENTION [Metal catalyst] so [001 1 ] The metal catalyst includes simple substances and compounds of various metal elements, and may be used singly or as a combination thereof. As the metal elements, there may be exemplified the group 2A elements of the Peri- odic Table of Elements (e.g., magnesium Mg, calcium Ca, strontium Sr, barium Ba), transition metal elements, and the group 3B elements of the Periodic Table of Elements (e.g., boron B, aluminum Al). In the present specification, boron B is also included as a metal element. 55 [001 2] As the transition metal elements, there may be exemplified the group 3A elements [rare earth metal elements (e.g., scandium Sc, yttrium Y, lanthanoid elements (lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, pro- methium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu), actinoid elements (e.g., actinium Ac)], the group 4A elements (e.g., titanium Ti, zirco- 3 EP 0 926 134 A2 nium Zr, hafnium Hf), the group 5A elements (e.g., vanadium V, niobium Nb, tantalum Ta), the group 6A elements (e..g, chromium Cr, molybdenum Mo, tungsten W), the group 7A elements (e.g., manganese Mn, technetium Tc, rhenium Re), the group 8 elements (e.g., iron Fe, ruthenium Ru, osmium Os, cobalt Co, rhodium Rh, iridium Ir, nickel Ni, palla- dium Pd, platinum Pt), the group 1B elements (e.g., copper Cu, silver Ag, gold Au), and the group 2B elements (e.g., 5 zinc Zn, cadmium Cd) of the Periodic Table of Elements. [0013] Preferred elements as a component of the metal catalyst include transition metal elements (e.g., rare earth metal elements such as lanthanoid elements, the group 3A elements such as actinoid elements, the group 4A ele- ments, the group 5A elements, the group 6A elements, the group 7A elements, the group 8 elements, the group 1 B ele- ments, the group 2B elements) and the group 3B elements of the Periodic Table of Elements. 10 [0014] Compounds comprising a metal element include hydroxides, metal oxides (e.g., double oxides or oxygen acids, or salts thereof), organic acid salts, inorganic acid salts, halides, coordination compounds (complex) containing any of the metal elements mentioned above, and polyacids (e.g., heteropolyacids and isopolyacids), or salts thereof. As for the metal compounds, the valence of their elements is not particularly restricted, and may be about 2 to 6. [0015] As the hydroxides, there maybe exemplified Sm(OH)2, Sm(OH)3, Mn(OH)2, MnO(OH), Fe(OH)2, Fe(OH)3, and 15 other corresponding metal hydroxides. As the metal oxides, there may be exemplified Sm02, Sm03, Ti02, Zr02, V203, V205, CrO, Cr203, Mo03, MnO, Mn304, Mn203, Mn02, Mn207, FeO, Fe203, Fe304, Ru02, Ru04, CoO, Co02, Co203, Rh02, Rh203, Cu203, and other corresponding metal oxides. As the double oxides or oxygen acids, or salts thereof, there may be exemplified MnAI204, MnTi03, LaMn03, K2Mn205, CaO • xMnO2(x=0.5, 1, 2, 3, 5), manganates [e.g., manganates (V) such as Na3Mn04, and Ba3[Mn04]2; manganates (VI) such as K2Mn04, Na2Mn04, and BaMn04; and 20 permanganates such as KMn04, NaMn04, LiMn04, NH4Mn04, CsMn04, AgMn04, Ca(Mn04)2, Zn(Mn04)2, Ba(Mn04)2, Mg(Mn04)2, and Cd(Mn04)2; molybdic acid; tungstic acid; and other corresponding metal double oxides or oxygen acids, or salts thereof.
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