- Tetra-alkyl-2,2,5,5-cyclohexanone-4-ol-1 and sulphonylated derivatives thereof
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STR1 New tetra-alkyl-2,2,5,5 cyclohexanone-4-ol-1 and their sulfonated derivatives of the general formula (I), wherein R and R', which may be the same or different, represent an alkyl radical (1-5 atoms of carbon) and R' represents a hydrogen atom or a radical SO--R'" wherein R'" represents an alkyl radical (1-5 atoms of carbon) or an aryl radical (6-14 atoms of carbon), their preparation intermediaries and process, as well as their application to the synthesis of cyclopropanic lactones having the cis structure.
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- A Short, Efficient, Highly Selective Synthesis of (1R,3S)-cis-Chrysanthemic Acid through the Microbiological Reduction of 2,2,5,5-Tetramethyl-1,4-cyclohexanedione
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A highly selective synthesis of (1R,3S)-cis-chrysanthemic acid (1a), a key intermediate in the industrial prepariation of major unnatural pyrethrinoid-type insecticides is reported. 2,2,5,5-Tetramethyl-1,4-cyclohexanedi
- d'Angelo, Jean,Revial, Gilbert,Azerad, Robert,Buisson, Didier
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- STEREOSELECTIVE SYNTHESIS OF (1R,3S)-CIS-CHRYSANTHEMIC ACID THROUGH MICROBIOLOGICAL REDUCTION OF 2,2,5,5-TETRAMETHYL 1,4-CYCLOHEXANEDIONE.
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An efficient, highly stereoselective synthesis of (1R,3S)-cis-chrysanthemic acid 6 is described.The crucial step of this synthesis was the microbiological reduction of dione 1 into (S)-ketol 2.
- Buisson, Didier,Azerad, Robert,Revial, Gilbert,d'Angelo, Jean
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p. 6005 - 6006
(2007/10/02)
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- Studies of Chrysanthemic Acid Derivatives: Catalyses Reactions of 3-(2-Hydroxymethyl-3,3-dimethylcyclopropyl)-2-methylpropanol and Formation of a Novel Eight-membered Cyclic Sulphite
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Acid catalysed reaction of the cyclopropanediol (3) derived from cis-chrysanthemic acid cis-(1) afforded, depending on the reaction conditions, 3-vinyl-2,2,5,5-tetramethyltetrahydrofuran (4) and 4,4,7,7-tetramethyl-3-oxabicycloheptane (5).On treatment with thionyl chloride-pyridine complex there was obtained in addition the eight-membered cyclic sulphite, 6,6,9,9-tetramethyl-3,5-dioxa-4-thiabicyclononane 4-oxide (6).X-Ray analysis confirms a boat-chair conformation with the S=O group trans to the cyclopropane ring in an equatorial situation.Thermal reaction of (6) gave either (4) or a mixture of (5), cis-chrysanthemol (7), and cis-isochrysanthemol (8).
- Crammer, Bernard,Goldschmidt, Zeev,Ikan, Raphael,Cohen, Shmuel
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p. 887 - 891
(2007/10/02)
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- Electrooxidative Cleavage of Carbon-Carbon Bonds. 2. Double Cleavage of α,β-Epoxyalkanones and Enantiospecific Syntheses of Chiral Methyl trans- and cis-Chrysanthemates from (+)- and (-)-Carvones
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The stereospecific synthesis of chiral methyl trans- and cis-chrysanthemates (1 and 26) from (+)- and (-)-carvones (7a,b) is described.Methyl (3R)- and (3S)-3-(1-chloro-1-methylethyl)-5-oxohexanoates (3) and methyl (3S)- and (3R)-3-(1-chloro-1-methylethyl
- Torii, Sigeru,Inokuchi, Tsutomu,Oi, Ryu
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p. 1944 - 1951
(2007/10/02)
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- Synthesis of Methyl (+)-cis-Chrysanthemate and (+)-cis-Homochrysanthemate from (+)-3-Carene
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Synthesis of (+)-dihydrochrysanthemolactone (III) and methyl (+)-cis-homochrysanthemate (IV) has been achieved via a common intermediate, viz. 2,2-dimethyl-3-(2-hydroxy-2-methylpropyl)-cis-cyclopropane-1-acetaldehyde (V), prepared from (+)-3-carene.The dimethyl acetal (VII), obtainable from V, on reacting with CH3MgI, affords the alcohol (VII) from which the aldehyde (XI) is regenerated and subjected to self-aldol condensation.Oxidation of aldol gives a mixture of acids (XI) and (XIV), the methyl esters of which on LAM reduction affords a mixture of diols (VI) and (XV).Oxidation of diols yields a mixture of lactone (III) and the acid (XIV).Oxidation of IX followed by esterification affords XIV, which on dehydration yields IV and the double bond isomer (XIII).Transesterification of IV with 3-phenoxybenzyl alcohol gives the ester (XVI).Oxidation of VI by KMnO4 yields hydroxy acid (XI), from which methyl chrysanthemate (I) has been obtained.
- Naik, R. H.,Kulkarni, G. H.
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p. 859 - 863
(2007/10/02)
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- Addition of Organomagnesium Halides to C = C Bonds, XVI. - A Synthetic Route to Chrysanthemic Acid
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Addition of 1-isobutenylmagnesium bromide (4) to 3,3-dimethylcyclopropene leads to the formation of a 1:1 product as well as considerable amounts of 1:2, 1:3, and higher molecular adducts.Further reaction with carbon dioxide gives, after hydrolysis, a mixture of cis-chrysanthemic acid (6; 39percent) and the higher molecular acids 1 and 2.
- Lehmkuhl, Herbert,Mehler, Klaus
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p. 2244 - 2246
(2007/10/02)
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- STEREOSPECIFIC CYCLOPROPENIC SYNTHESIS OF CIS-CHRYSANTHEMIC METHYL ESTER. 2. THE BY-PASSING DIAZOALKANE WAY (1).
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A stereospecific synthesis of cis-chrysanthemate by catalytic hydrogenation of a cyclopropene is described.The required precursor, a 3H-pyrazole, is obtained here via a novel dianion reaction and MnO2 dehydrogenation of a Δ2-pyrazoline, instead of the more cumbersome diazoaddition method.
- Franck-Neumann, M.,Miesch, M.
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p. 1409 - 1412
(2007/10/02)
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- Synthesis of Methyl 1R(+)-cis-Chrysanthemate and Methyl 1S(+)-cis-2,2-Dimethyl-3-(2-phenylprop-1-enyl)cyclopropane-1-carboxylate from (+)-Car-3-ene
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Synthesis of (+)-dihydrochrysanthemolactone (III), methyl 1R(+)-cis-chrysanthemate (II) and methyl 1S(+)-cis-2,2-dimethyl-3-(2-phenylprop-1-enyl)cyclopropane-1-carboxylate (XIII) has been achieved from a common intermediate 2,2-dimethyl-3-(2-methyl-2-hydroxypropyl)-cis-1-acetonylcyclopropane (IV), which is obtainable from (+)-car-3-ene by a known procedure.
- Bhat, N. G.,Mane, B. M.,Kulkarni, G. H.,Mitra, R. B.
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p. 204 - 206
(2007/10/02)
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- Stereospecific Conversion of (+)-Car-3-ene into (+)-Dihydrochrysanthemolactone and Methyl (+)-cis-Chrysanthemate
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Methyl (+)-cis-chrysanthemate (II, R = CH3) and (+)-dihydrochrysanthemolactone (III) have been synthesised from (+)-car-3-ene (I) via the keto-carboxylic acid (XII).
- Mane, B. M.,Gore, K. G.,Kulkarni, G. H.
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p. 605 - 607
(2007/10/02)
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