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United States Patent (19) (11) Patent Number: 5,037,977 Tan Et Al

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United States Patent (19) (11) Patent Number: 5,037,977 Tan Et Al United States Patent (19) (11) Patent Number: 5,037,977 Tan et al. (45) Date of Patent: Aug. 6, 1991 54 METHOD FOR PRODUCTION OF DIMERIC 4,778,885 10/1988 Vukovic et al..................... 540/478 ALKALOIDS FOREIGN PATENT DOCUMENTS 75 Inventors: Hiroaki Tan; Naoya Sakamoto; 3801450 8/1988 Fed. Rep. of Germany ...... 540/478 Eiichiro Hata; Takeshi Ishitoku; 2544319 10/1984 France ................................ 540/478 Noriaki Kihara, all of Yamaguchi, Japan Primary Examiner-Diana Rivers Attorney, Agent, or Firm-Nixon & Vanderhye 73) Assignee: Mitsui Petrochemical Industries Ltd., Tokyo, Japan (57) ABSTRACT (21) Appl. No.: 390,903 This invention concerns a method for the production of dimeric alkaloids, characterized by reacting of catha 22 Filed: Aug. 8, 1989 ranthine with vindoline in the presence of Fe3+ and (1) (30) Foreign Application Priority Data removing or inactivating the Fe3+ and allowing the Aug. 11, 1988 JP Japan ................................ 63-1988.97 reaction product to react with a reducing agent or (2) Aug. 11, 1988 JP Japan ................................ 63-198898 allowing presence of oxygen and a dicarboxylic acid or a derivative thereof in the reaction system and allowing I51) Int. Cl............................................. C07D 51.9/04 the reaction product to react with a hydride source. (52) U.S. Cl. ....................................... 540/478; 546/51 In accordance with this invention, such dimeric alkaloid 58) Field of Search......................................... 540/478 as vinblastine, leurosidin, and 3',4'-anhydrovinblastine (56) References Cited which are useful as antineoplastic drugs can be pro U.S. PATENT DOCUMENTS duced in high yields. 4,279,817 7/1981 Kutney ................................ 540/478 4,737,586 4/1988 Potier et al. ........................ 540/478 4 Claims, No Drawings 5,037,977 1. 2 yield of vinblastine which has found actual utility as a METHOD FOR PRODUCTION OF DIMERC cancer depressant is greatly improved in the latter case ALKALOIDS (2). DETAILED DESCRIPTION OF THE BACKGROUND OF THE INVENTION 5 INVENTION 1. Field of the Invention This invention relates to an improved method for This invention embraces the following methods as producing in high yields such dimeric alkaloids as vin aspects thereof. blastine leurosidene, and 3',4'-anhydrovinblastine (1) A method for the production of a dimeric alka which are useful as antineoplastic drugs. 10 loid, characterized by a procedure which comprises More specifically, this invention relates to a method causing reaction of catharanthine with vindoline in the for the production of a dimeric alkaloid, characterized presence of Fe3+ and then (1) removing or inactivating by a procedure which comprises causing reaction of the Fei and allowing a reducing agent to react on the catharanthine with vindoline in the presence of Fe3+, reaction product or (2) allowing presence of oxygen then (1) removing or inactivating the Fe3+ and allow 15 and a dicarboxylic acid or a derivative thereof in the ing a reducing agent to react on the resultant compound reaction system and then causing the reaction product or (2) allowing the presence of oxygen and a dicarbox to react with a hydride source. ylic acid or a derivative thereof in the reaction system (2) A method for the production of 3',4'-anhydrovin and then causing the resultant compound to react with blastine, characterized by a procedure which comprises a hydride source. 20 causing reaction of catharanthine with vindoline in the 2. Description of the Prior Art presence of Fe3+ and then removing or inactivating the Such dimeric alkaloids as vinblastine and 3',4'-anhy Fe3+ and subsequently reducing the reaction product. drovinblastine have been known in the art as con (3) A method for the production of 3',4'-anhydrovin pounds possessing an antineoplastic activity (U.S. Pat. blastine set forth in (2) above, characterized by effecting No. 4,029,663). As means of obtaining these com 25 the inactivation of the Fe3+ by the addition of an iron pounds, methods which consist in extracting the com ligand. pounds from a plant of genus Catharanthus, having the (4) A method for the production of a dimeric alka scientific name of Catharanthus roseous (alias Vinca rosea), and methods which resort to chemical synthesis loid, characterized by a procedure which comprises using catharanthine and vindoline derived from the 30 causing reaction of catharanthine with vindoline in the plant as starting materials have been known to the art. presence of Fe3+, then allowing presence of oxygen The methods by extraction, however, entail difficul and a dicarboxylic acid or a derivative thereof in the ties in separation and purification of the dimeric alka reaction system, and causing the reaction product to loids because the plant has a very small dimeric alka react with a hydride source. loids content and also because a number of analogous 35 (5) A method for the production of a dimeric alkaloid compounds are additionally present in the plant. set forth in (4) above, characterized by the fact that the Among the methods resorting to chemical synthesis, dicarboxylic acid is oxalic acid, malonic acid, or a 2 the method which comprises oxidizing catharanthine position substituted malonic acid and the dimeric alka with a peracid, acylating the resultant N-oxide, causing loid is a compound selected from the group consisting reaction of the acylated product with vindoline and of vinblastine, leurosidine, and 3',4'-anhydrovinblastine. reducing the reaction product with NaBH4 (U.S. Pat. In the working of this invention, the reaction of cath No. 4,144,237) has been known to the art. aranthine with vindoline in the presence of Fe3+ can be The synthesis mentioned above, however, attains carried out as conventionally practiced. Generally this isolation of 3',4'-anhydrovinblastine only in a low yield reaction brings about desirable results when it is carried of 41% and simultaneously gives rise to 10% of isomers 45 out in an atmosphere of nitrogen or under a current of as a by-product. Thus, this method entails difficulties in nitrogen. separation and purification of the dimeric alkaloids. Now, the method which comprises the steps of re moving or inactivating Fe3+ after the coupling reaction SUMMARY OF THE INVENTION and causing reaction of the product of coupling reaction The inventors, mindful of commercialized produc 50 with a reducing agent will be described in detail below. tion of the dimeric alkaloids, have found a special inter The removal of Fe3t is attained by adding a basic est in the method which comprises effecting coupling of compound to the reaction mixture after completion of catharanthine with vindoline in the presence of Fe3+ the coupling reaction thereby inducing precipitation of and then causing the product of coupling to react with Fe3+ and removing the precipitate from the reaction a reducing agent or a hydride source. They have tried 55 system by such a conventional solid-liquid separation the reaction of the product of coupling with various technique as filtration or centrifugal separation. The reducing agents or hydride sources, to find that this basic compound to be used herein may be any of the method is not particularly effective in improving the basic compounds which are capable of inducing the yield of the dimeric alkaloids. The inventors have continued a study with a view to 60 precipitation of Fe3+ without impeding the reaction. improving the yield of the dimeric alkaloids, to acquire The basic compounds which may be mentioned include an unexpected and useful novel knowledge that by (1) metal hydroxides such as sodium hydroxide, potassium removing or inactivating the Fe3+ or (2) allowing the hydroxide, calcium hydroxide, and barium hydroxide; presence of oxygen and a dicarboxylic acid or a deriva carbonates such as potassium carbonate, sodium car tive thereof in the reaction system after the coupling 65 bonate and ammonium carbonate; bicarbonates such as reaction and prior to the addition of the reducing agent sodium bicarbonate and potassium bicarbonate; amines or the hydride source, the yield of 3',4'-anhydrovinblas such as urea, methylamine, ethylamine, dimethylamine, tine is notably improved in the former case (1) or the and trimethylamine; hydroxides of quarternary ammo 3 5,037,977 4. nium such as tetraethyl ammonium hydroxide and aque After the inactivation of Fe3+ is carried out as de ous ammonia. scribed above, a reducing agent is added to the reaction The term "inactivation of Fe3+" refers to any treat system to give the compound aimed at. ment which is capable of eliminating or blocking the When the precipitate of Fe3+ is produced by the adverse effects or impeditive actions of Fe3+ otherwise treatment of inactivation, the treatment mentioned manifested in the subsequent steps. above may be performed on the reaction liquid such as The treatment for the inactivation of Fe3+, therefore, the filtrate which remains after the removal of the pre extensively embraces treatments capable of inhibiting cipitate. The precipitate which is removed from the the coordination of iron to useful components in the reaction system is washed with an organic solvent. The subsequent steps and actions capable of inhibiting the O washings are combined with the reaction liquid such as oxidation by iron. For example, a method which com the filtrate or the supernatant, concentrated under a prises adding an iron ligand to the reaction system after vacuum to expel the organic solvent, admixed with completion of the coupling reaction thereby inactivat water, and then reduced with a reducing agent such as ing the Fe3+ for the purpose of precluding the adverse NaBH4. Otherwise, the mixture of the washings with effects or impeditive actions of Fe3+, a method which 15 the reaction liquid, without being concentrated under a effects inactivation by reducing the Fe3+ to metallic vacuum, may be adjusted to a pH value of less than 6, iron or to Fe2+, and a method which comprises produc subjected to solid-liquid separation, with the water ing different species of ligand by the action of different layer reduced by the addition of a reducing agent such species of ligands and causing the resultant complexes as NaBH4.
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