Synthesis of analogs of juvenile hormone on the basis of the telomerization reaction of piperylene with sulfones
In continuing the work on the study of the telomerization of 1,3-dienes with sulfones containing an active H atom, and also with the aim of synthesizing analogs of juvenile hormone (JH) based on the telomers obtained, they studied the catalytic telomerization of 1,3-pentadiene (piperylene) with ..beta..-substituted sulfonates. It was established that trans-piperlyene participates in the telomerization reaction with sulfones in the presence of the catalytic system PdCl/sub 2/(Ph/sub 3/P)/sub 2/-PhONa. Methyl 2-phenylsulfonyl-3,7-dimethyl-4(E), 9-decadienecarboxylate (II) is formed in a yield of 65% by the reaction of methyl phenylsulfonylacetate (I) with piperylene in the course of 20 h at 85/sup 0/C. The presence of absorption bands at 920 (CH/sub 2/=C) and 980 cm/sup -1/ (E-CH=CH) in the IR spectrum of compound (II) and the presence of a group of multiplet signals at delta 4.8-5.3 ppm in the PMR spectrum, corresponding to five protons of double bonds, indicate the addition of two molecules of piperylene to the molecule of the sulfone (I). The oxidation with oxygen on a Pd/Cu-catalyst proceeds smoothly to the methyl ketone (III); this clearly confirms the presence of the terminal C=C bond in the telomer (II). In the PMR spectrum of (II), notice is taken of the group of signals in the region of 3.30-3.53 ppm corresponding to three methoxy protons. There are three pairs of doublets (J = 7 Hz) in the region of 0.1-1.3 ppm which correspond to the methyl group. The complexity of the PMR spectrum is probably explained by the fact that the reaction leads to the formation of a complex mixture of diastereoisomers. As was to be expected, methyl 3,7-dimethyl-4,9-decadienoate (IV) is formed as the sole product with a yield of 70% in the desulfonation of the telomer (II) using Na/Hg in methanol according to the method of (5); the structure of (IV) was established with the aid of /sup 13/C NMR spectroscopy.
- Research Organization:
- Institute of Chemistry, Ufa, USSR
- OSTI ID:
- 6226529
- Journal Information:
- Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States), Journal Name: Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States) Vol. 35:4; ISSN BACCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
550200 -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
BIOLOGICAL EFFECTS
CARBON 13
CARBON ISOTOPES
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COPPER COMPOUNDS
DIENES
ELECTRON SPIN RESONANCE
EVEN-ODD NUCLEI
HORMONES
HYDROCARBONS
HYPERFINE STRUCTURE
INFRARED SPECTRA
ISOMERS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
METABOLIC ACTIVATION
MOLECULAR STRUCTURE
MULTIPLETS
NMR SPECTRA
NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PALLADIUM COMPOUNDS
PENTADIENES
POLYENES
POLYMERIZATION
RESONANCE
SPECTRA
STABLE ISOTOPES
SULFONES
SYNTHESIS
TELOMERIZATION
TRANSITION ELEMENT COMPOUNDS