Isomerization of 1,3,4,5,6-Pentachlorocyclohexene-1 Isomers in Dimethyl Sulfoxide

Kurihara, Norio; Wakamura, Sadao; Nakamura, Takeshi; Nakajima, Minoru

doi:10.1080/00021369.1974.10861382

Cited by 3 publications

(2 citation statements)

References 3 publications

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“…Crystalline products IV (32 mg, 16%) of mp 78°C, XXII (60 mg, 29%) of mp 66SC and XXIII (35 mg, 17%) of mp 71°C were obtained by n-hexane elution. PMR: o~~~if-tV: 4,90 (triplet, H-3), 4 …”

Section: (123/45)-345-trichloro-i 2-epoxycyclohexane (Xx)mentioning

confidence: 99%

Syntheses and PMR Studies of 1,2,3,4,5-Pentachlorocyclohexane Isomers, Tetrachloromonomethoxycyclohexane Isomers and Related Compounds

Tanaka

Kiso

Yoshida

et al. 1975

Agricultural and Biological Chemistry

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Two diastereomers of 1,2,3,4,5-pentachlorocyclohexane tt and two diastereomers of tetrachloromonomethoxycyclohexane were synthesized stepwise from diastereomers of 3 4 5-. ' , tnchlorocyclohexene, which had been derived from the DL-(36/45)-, DL-(34/56)-and (346/5)-isomers of 3,4,5,6-tetrachlorocyclohexene tt (a-, f3-and y-BTC, respectively) by selective reduction with LiAlH4. The configurations of all the products and intermediary trichlorocyc10hexene isomers were determined by PMR studies.During structure-activity relationship studies on BHC isomers and analogs, compounds having a hydrogen atom in place of a chlorine atom in the structure of ),-BHC (lindane) (I) are required. We here describe the synthesis of two such diastereomers of pentachlorocyclohexane: the 134/25-isomer (lI)tt having an intermediary structure of u-(III) and y-BHC, and the 1245/3-isomer (IV) with that of ()-(V) and y-BHC. We also describe the preparation of two diastereomers (VI and VII) of tetrachloromonomethoxycyclohexane with the configuration 134/25. The configurations of these compounds were determined by synthetic routes, and by PMR spectroscopic analyses. We also report the preparation of three new diastereomers of 3,4,5-trichlorocyclohexene as the key intermediates in the synthetic course to the pentachlorocyclohexanes or tetrachloromonomethoxycyclohexanes starting from three isomers of BTC (VIII, IX t Studies on BHC Isomers and Related Compounds. Part XI.tt The nomenclature and numbering system adopted in this report follow that described in a previous report. lI The following abbreviations are used: BHC= 1,2,3,4,5,6-hexachlorocycIohexane, BTC = 3,4,-5,6-tetrachlorocyclohexene, PMR=proton magnetic resonance spectroscopy, IR=infrared absorption spectroscopy, tIc = thin-layer chromatography. and X). Synthetic methods 1. Three diastereomers of 3,4,5-trichlorocyclohexeneReactions between lithium aluminum hydride and the compound VIII, IX and X (u-, (3-and y-BTC, respectively) gave only the respective 34/5-(XI), 3/45-(XII) and 35/4-isomer (XIII). Although compound X might afford XIII also by an SN2 reaction, the entire results seem to be a proof that the SN2' mechanism prevails. Another possible reaction course (SN2 mechanism) should produce XII, XI and XI from VIII, IX and X, respectively, but we did not find any of these compounds in the products of the reactions (see Fig. 2).The reaction mechanism was studied using lithium aluminum deuteride instead of the hydride. The structures of the deuteriated products were examined by PMR. From the isomer VIII, only XI' and not XI" was obtained (Fig. 2). Compound XI' was shown to have the pseudo-axial deuterium atom at the 6-position. Similarly, IX and X gave XII' and XIII', respectively. Results showed that these deuteriated products were produced by an SN2' attack of lithium aluminum deuteride

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Section: (123/45)-345-trichloro-i 2-epoxycyclohexane (Xx)mentioning

confidence: 99%

Syntheses and PMR Studies of 1,2,3,4,5-Pentachlorocyclohexane Isomers, Tetrachloromonomethoxycyclohexane Isomers and Related Compounds

Tanaka

Kiso

Yoshida

et al. 1975

Agricultural and Biological Chemistry

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“…The infrared spectrum corresponded almost entirely with that published by Kolka et al (1954) for 7-PCCH. As only a single peak was developed on GLC using polar columns, the product was probably the pure 36/45 isomer (Kurihara et al, 1974).…”

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Dehydrochlorination of some organochlorine pesticides in freeze-dried egg and egg fat during storage

Hill¹,

Smart²

1981

J. Agric. Food Chem.

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Synthesis and structure of three isomers of 1,3,4,5-tetrachlorocyclohexene.

Kurihara¹,

Kohsaka²,

Nakajima³

1981

Agricultural and Biological Chemistry

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By controlled reduction of 1,3,4,5,6- (Fig. 1). The entire results seemedto showthat the SN2' mechanism prevailed, although the compound VII might also be produced by an SN2 mechanism from IV. When(36/45)-hexachlorocyclohexene (VIII)1} was reduced by LiAlH4, a known isomer of PCCHE(III) was obtained, which was followed by a further reduction to give the compoundVI. These reactions were also explained by the SN2' mechanism. Structural StudiesCompound V from (36/45)-PCCHE (I).

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Isomerization of 1,3,4,5,6-Pentachlorocyclohexene-1 Isomers in Dimethyl Sulfoxide

Cited by 3 publications

References 3 publications

Syntheses and PMR Studies of 1,2,3,4,5-Pentachlorocyclohexane Isomers, Tetrachloromonomethoxycyclohexane Isomers and Related Compounds

Syntheses and PMR Studies of 1,2,3,4,5-Pentachlorocyclohexane Isomers, Tetrachloromonomethoxycyclohexane Isomers and Related Compounds

Dehydrochlorination of some organochlorine pesticides in freeze-dried egg and egg fat during storage

Synthesis and structure of three isomers of 1,3,4,5-tetrachlorocyclohexene.

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