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Processes for Producing (4E)-5-Chloro-2-Isopropyl-4-Pentenoic Ester and Optically Active Isomer Thereof

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Processes for Producing (4E)-5-Chloro-2-Isopropyl-4-Pentenoic Ester and Optically Active Isomer Thereof Europäisches Patentamt *EP001571138A1* (19) European Patent Office Office européen des brevets (11) EP 1 571 138 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 158(3) EPC (43) Date of publication: (51) Int Cl.7: C07C 67/32, C07C 69/65, 07.09.2005 Bulletin 2005/36 C07B 53/00, C07B 57/00 (21) Application number: 03777366.0 (86) International application number: PCT/JP2003/015694 (22) Date of filing: 09.12.2003 (87) International publication number: WO 2004/052828 (24.06.2004 Gazette 2004/26) (84) Designated Contracting States: • MATSUMURA, Yasushi, AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Asahi Glass Company, Limited HU IE IT LI LU MC NL PT RO SE SI SK TR Ichihara-shi, Chiba 290-8566 (JP) Designated Extension States: • MORIZAWA, Yoshitomi, AL LT LV MK Asahi Glass Company, Limited Yokohama-shi, Kanagawa 221-8755 (JP) (30) Priority: 09.12.2002 JP 2002356651 • KAMINUMA, Toshihiko, 21.05.2003 JP 2003143256 Asahi Glass Company, Limited Yokohama-shi, Kanagawa 221-8755 (JP) (71) Applicant: ASAHI GLASS COMPANY LTD. • AOKI, Yuuichi, Asahi Glass Company, Limited Tokyo 100-8405 (JP) Yokohama-shi, Kanagawa 221-8755 (JP) (72) Inventors: (74) Representative: Müller-Boré & Partner • MORI, Nobuaki, Asahi Glass Company, Limited Patentanwälte Ichihara-shi, Chiba 290-8566 (JP) Grafinger Strasse 2 81671 München (DE) (54) PROCESSES FOR PRODUCING (4E)-5-CHLORO-2-ISOPROPYL-4-PENTENOIC ESTER AND OPTICALLY ACTIVE ISOMER THEREOF (57) The present invention provides processes for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate and an op- tical isomer of the (4E)-5-chloro-2-isopropyl-4-pentenoate, namely a process for producing a (4E)-5-chloro-2-isopropyl- 4-pentenoate represented by the following formula (4), which comprises reacting a compound represented by the following formula (2) in the presence of an aprotic solvent (II) with a base (II) and then with (1E)-1,3-dichloro-1-propene to give a compound represented by the following formula (3), and dealkoxycarbonylating either ester in the compound represented by the following formula (3), and a process for producing a (S)-(4E)-5-chloro-2-isopropyl-4-pentenoate represented by the following formula (5), which comprises optically resolving a (4E)-5-chloro-2-isopropyl-4-pentenoate represented by the formula (4) obtained by the above-mentioned process (wherein R is a lower alkyl group or an aralkyl group). EP 1 571 138 A1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 1 571 138 A1 2 EP 1 571 138 A1 Description TECHNICAL FIELD 5 [0001] The present invention relates to a process for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate useful as an intermediate for an agrochemical or a medicine. The present invention also relates to a process for producing an (S)-(4E)-5-chloro-2-isopropyl-4-pentenoate especially useful as an intermediate for an agrochemical or a medicine. 10 BACKGROUND ART [0002] For synthesis of (4E)-5-chloro-2-isopropyl-4-pentenoates and their analogues, the following processes have been reported. 15 (1) A process for producing a 5-chloro-2-isopropyl-4-pentenoate by reacting methyl isopentanoate with 1,3-dichlo- ro-1-propene in the presence of lithium diisopropylamide (LDA) at an extremely low temperature (-78°C) (USP4492799). (2) The process (1) in which the reaction is carried out at -15°C by using sodium iodide (NaI) for higher reactivity (Examples in WO02/08172 and WO01/09079). 20 (3) A process for synthesizing 5-chloro-2-isopropyl-4-pentenoic acid, which comprises quaternary alkylation of diethyl isopropylmalonate with 1,3-dichloro-1-propene in ethanol as a solvent in the presence of sodium ethoxide (NaOC2H5), hydrolysis of the two ester linkages and monodecarboxylation of the resulting dicarboxylic acid ("Akad. Nauk Armyan, S.S.R. Khim. Nauki", 1960, vol.13 (4), p.259-262, (Russia)). (4) A process for synthesizing various 4-pentenoate derivatives, which comprises quaternary alkylation of a diethyl 25 malonate derivative with a chloropropene derivative in toluene as a solvent in the presence of sodium hydride (NaH) and dealkoxycarbonylation of either ester linkage (USP4492799). For synthesis of optically active (S)-(4E)-5-chloro-2-isopropyl-4-pentenoates and their analogues, the fol- lowing processes have been reported. (5) A process for producing ethyl (S)-(4E)-5-chloro-2-isopropyl-4-pentenoate, which comprises adding porcine 30 liver esterase (Roche Diagnostics, Technical Grade) all at once to the racemic ethyl (4E)-5-chloro-2-isopropyl- 4-pentenoate obtained by the process (2) (WO01/09079). (6) A process for producing (S)-(4E)-5-chloro-2-isopropyl-4-pentenoic acid, which comprises hydrolyzing the ra- cemic ethyl (4E)-5-chloro-2-isopropyl-4-pentenoate obtained by the process (2), treating the resulting racemic (4E)-5-chloro-2-isopropyl-4-pentenoic acid with optically active cinchonidine for diastereomeric salt formation, sep- 35 arating the (S)-diastereomer salt by recrystallization and treating the (S)-diastereomeric salt with an acid (WO01/09079). [0003] The reports of the processes (1), (3) and (4), however, are silent about the E/Z ratio of the double bond in the 5-chloro-2-isopropyl-4-pentenoates. Further, while the process (2) was reported to give the E-isomers of a 5-chloro- 40 2-isopropyl-4-pentenoate in yields of 84% and 76%, reproduction of experiments disclosed therein by the present inventors did not gave the E-isomer in the reported yield, but in a yield of only about 4.2%. Thus, it has been difficult to selectively synthesize the E-isomer of 5-chloro-2-isopropyl-4-pentenoates in high yields without isomerization to the Z-form. [0004] Further, because the use of lithium diisopropylamide (LDA) requires that the reaction temperature must be 45 kept thermostatically at such an extremely low temperature as -78°C, and because LDA is prepared from expensive n-butyllithium (n-BuLi), the process (1) is unsuitable for industrial mass production for economical reasons and in view of operational difficulties and gives the product in such a low yield as 46%. The process (2) has a problem that the product is obtained in a low yield and is difficult to purify because methyl isopentanoate as the starting material under- goes side reactions such as selfcondensation. The process (3) has a problem that esterification of 5-chloro-2-isopropyl- 50 4-pentenoic acid, which is obtainable in a 23% yield, gives a 5-chloro-2-isopropyl-4-pentenoate in a still lower yield. The process (4) is economically and operationally unsuitable for industrial mass production in view of the use of NaH. [0005] The report of the process (5) does not sufficiently disclose the reaction conditions for production of an optically active isomer and keeps it totally unclear how to obtain the desired compound at all. The processes (5) and (6) are unsuitable for industrial mass production because the use of the process (2) for production of the racemate to be 55 resolved lowers the total yield considerably. 3 EP 1 571 138 A1 DISCLOSURE OF THE INVENTION [0006] The present invention has been accomplished to solve the above-mentioned problems and provides a process for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate using inexpensive starting material and reagents. The process 5 of the present invention can selectively produce the E-form in a high yield through simple reactions and is suitable for industrial mass production. The present invention also provides a process for producing an (S)-(4E)-5-chloro-2-iso- propyl-4-pentenoate in a high yield and in a high enantio excess by optical resolution of the resulting (4E)-5-chloro- 2-isopropyl-4-pentenoate. [0007] Namely, the present invention provides the followings. 10 1. A process for producing a (4E)-5-chloro-2-isopropyl-4-pentenoate represented by the following formula (4) (wherein R is a lower alkyl group or an aralkyl group), which comprises reacting a compound represented by the following formula (2) in the presence of an aprotic solvent (II) with a base (II) and then with (1E)-1,3-dichloro- 1-propene to give a compound represented by the following formula (3), and dealkoxycarbonylating either ester 15 in the compound represented by the following formula (3). 20 25 2. The process according to 1, wherein the base (II) is a metal alkoxide represented by the formula M2OR2 (wherein 30 M2 is Na or K, and R2 is a lower alkyl group). 3. The process according to 2, wherein the compound represented by the formula (2) is reacted with the metal alkoxide represented by the formula M2OR2 (wherein M2 and R2 are the same as defined above) as the base (II) in the presence of the aprotic solvent (II), and then an alcohol represented by the formula R2OH produced as a by-product is removed before the reaction with (1E)-1,3-dichloro-1-propene. 35 4. The process according to any one of 1 to 3, wherein the aprotic solvent (II) consists of at least one solvent selected from the group consisting of toluene, xylene, benzene, heptane, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, dimethyl sulfoxide, diethylene glycol dimethyl ether, tetrahydrofuran, t-butyl methyl ether and sulfolane. 5. The process according to any one of 1 to 4, wherein the compound represented by the formula (2) is a compound 40 obtained by reacting a compound represented by the following formula (1) with a base (I) and then with an isopropyl halide in an aprotic solvent (I) (wherein R is the same as defined above). 45 50 6. The process according to 5, wherein the base (I) is a metal alkoxide represented by the formula M1OR1 (wherein M1 is Na or K, and R1 is a lower alkyl group).
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