- A juvenile hormone analogs of the preparation method
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The invention relates to the field of insecticides, and particularly relates to a preparation method of a juvenile hormone analogue (which comprises S-methoprene and S-hydroprene). The preparation method of the juvenile hormone analogues comprises the following steps of: A. adding (2E, 4E)-11-R-3,7,11-trimethyl-2,4-dodecadienoic acid (R is hydrogen or methoxyl) serving as raw material, an organic alkali catalyst and an organic solvent to a reaction vessel, and starting stirring; B. dropwise adding an organic solvent (the same as the organic solvent in the step A) solution of pyrocarbonate; C. after the addition is completed, reacting at 0-30 DEG C for 0-3 hours; D. adding water to stop reaction, and splitting phases of reaction liquid to obtain an organic phase; E. carrying out reduced pressure concentration and distillation to obtain a product, wherein the steps can also be carried out under the condition that the addition sequences of the pyrocarbonate and an organic strongly-alkaline catalyst are exchanged. The preparation method disclosed by the invention has the advantages of mild reaction condition, high product purity, high yield, environment-friendly and safe route and good industrial prospect.
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Paragraph 0031; 0070-0071
(2017/05/10)
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- Combined Biochemical and Electrochemical Approach to Chiral C10-Components for Juvenoid Synthesis, and Preparation of (2E,4E,7S)Stereoisomers of Metoprene and Hydroprene
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Enantioselective acylation of (RS)-3,7-dimethyl-7-methoxyoctan-1-ol and (RS)-3,7-dimethyl-octan-1-ol with vinyl acetate in the presence of lipase from yeast Candida cylindracea was performed to conversion of 40-50%, and subsequent hydrolysis of the products afforded (S)-(-)-enantiomers of these alcohols with ee of 98-100%. The oxydation of these products by bromine generated by electrolysis in a membraneless device in the system "aqueous NaBr (+NaHCO3)/CH2Cl2" in the presence of 4-substituted 2,2,6,6-tetramethyl-1-oxopiperidinium salts furnished the corresponding (S)-(-)-alkanals. The condensation of the latter with the esters of 3-alkoxycarbonyl-2-methylprop-2-enylphosphonic acids in a heterophase system solid KOH-benzene-tetraoctylammonium bromide yielded samples of metoprene and hydroprene of high configurational purity.
- Gamalevich,Zhdankina,Kryshtal',Nikishin,Ogibin,Serebryakov
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p. 467 - 474
(2007/10/03)
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- Synthesis of S-(+)-methoprene
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An optically active juvenile hormone analogue, S-(+)-methoprene (1), is synthesized in six steps from technical grade S-(+)-3,7-dimethyl-1,6-octadiene (''(+)-dihydromyrcene'', e.e. ca. 50percent) by a novel procedure which begins with selective hydroalumination-oxidation to give S-(-)-citronellol.This alcohol is oxidized to give S-(-)-citronellal which on reaction with allylmagnesium chloride affords 6S,10-dimethyl-1,9-undecadien-4R/S-ol (5).Smidt-Moiseev oxygenation of 5 followed by dehydration leads to 6S,10-dimethyl-3E,9-undecadien-2-one.The latter on treatment with isopropoxyethynylmagnesium bromide is transformed into isopropyl 3,7S,11-trimethyl-2E/Z,4E,10-dodecatrienoate which upon Brown solvomercuration-reduction in MeOH gives 1 in 14percent overall yield.
- Odinokov, V. N.,Ishmuratov, G. Yu.,Kharisov, R. Ya.,Serebryakov, E. P.,Tolstikov, G. A.
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- TERPENES IN ORGANIC SYNTHESIS. 13. SYNTHESIS OF S-(+)-METHOPRENE FROM (+)-&β-CITRONELLENE
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S-(+)-Methoprene (I) was synthesized from (+)-β-citronellene (III) with an optical purity of about 50percent.The optical purity of the key intermediate, S-(-)-7-methoxy-3,7-dimethyl-1-octanol (IV), can be increased by fractional crystallization of the optical active acid phthalate salt (VI) followed by hydrolytic crystallization of the alcohol (IV).The yield of (I) at the final synthetic stage can be increased by use of interphase catalysis.S-(+)-Methoprene has a higher morphogenetic activity than the racemic form.
- Serebryakov, E. P.,Zhdankina, G. M.,Kryshtal', G. V.,Mavrov, M. V.,Khao, Nguen Kong
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p. 739 - 743
(2007/10/02)
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