Hydantoine, thiohydantoine, glykocyamidine-XXXIII. Durch Lewis-säuren ausgelöste reduktive umlagerungen vom retrobenzilsäure-typ-VIII reaktionen einiger 5,5-diarylthiohydantoin-derivate mit bortrifluorid-ätheraten, bortrifluorid-ätherat/ bortrifluorid-gemischen und galliumbromid

J. Fetter, J. Nyitrai, K. Lempert

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Abstract

5,5-Diaryldithiohydantoins of type 1b, when refluxed with BF3 dimethyl etherate or mixtures of the former reagent with BF3 in toluene or chlorobenzene, are selectively methylated at the S(2) atom, and/or suffer rearrangement of the retrobenzilic acid type under simultaneous extrusion of the thioxo sulfur atom from position 4 to yield imidazole derivatives of type 6. The latter type of reaction was previously brought about by aluminium chloride. Derivatives already methylated at the S(2) atom are only rearranged, as are also the derivatives of 5,5-diphenyl-4-thiohydantoin (1a, R′{A figure is presented} R″ {A figure is presented} H) if a reaction with the latter occurs at all. Derivatives of 5,5-diphenyl-2-thiohydantoin, on the other hand, are only S-methylated by boron trifluoride dimethyl etherate without being rearranged. The selective methylating properties of the BF3 dimethyl etherate reagent may be applied for the smooth preparation of several hitherto difficulty accessible (di)thiohydantoin derivatives. Gallium tribromide proved to be a catalyst comparable with aluminium trichloride for effecting rearrangements of 5,5-diaryl-4-thio- and -dithiohydantoin derivatives, its milder properties being in some cases favourable. In the cases where the migratory aptitudes of phenyl and p-chlorophenyl groups could be compared, the migratory aptitude of the former was always the greater.

Original languageGerman
Pages (from-to)5933-5941
Number of pages9
JournalTetrahedron
Volume27
Issue number23
DOIs
Publication statusPublished - 1971

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

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title = "Hydantoine, thiohydantoine, glykocyamidine-XXXIII. Durch Lewis-s{\"a}uren ausgel{\"o}ste reduktive umlagerungen vom retrobenzils{\"a}ure-typ-VIII reaktionen einiger 5,5-diarylthiohydantoin-derivate mit bortrifluorid-{\"a}theraten, bortrifluorid-{\"a}therat/ bortrifluorid-gemischen und galliumbromid",
abstract = "5,5-Diaryldithiohydantoins of type 1b, when refluxed with BF3 dimethyl etherate or mixtures of the former reagent with BF3 in toluene or chlorobenzene, are selectively methylated at the S(2) atom, and/or suffer rearrangement of the retrobenzilic acid type under simultaneous extrusion of the thioxo sulfur atom from position 4 to yield imidazole derivatives of type 6. The latter type of reaction was previously brought about by aluminium chloride. Derivatives already methylated at the S(2) atom are only rearranged, as are also the derivatives of 5,5-diphenyl-4-thiohydantoin (1a, R′{A figure is presented} R″ {A figure is presented} H) if a reaction with the latter occurs at all. Derivatives of 5,5-diphenyl-2-thiohydantoin, on the other hand, are only S-methylated by boron trifluoride dimethyl etherate without being rearranged. The selective methylating properties of the BF3 dimethyl etherate reagent may be applied for the smooth preparation of several hitherto difficulty accessible (di)thiohydantoin derivatives. Gallium tribromide proved to be a catalyst comparable with aluminium trichloride for effecting rearrangements of 5,5-diaryl-4-thio- and -dithiohydantoin derivatives, its milder properties being in some cases favourable. In the cases where the migratory aptitudes of phenyl and p-chlorophenyl groups could be compared, the migratory aptitude of the former was always the greater.",
author = "J. Fetter and J. Nyitrai and K. Lempert",
year = "1971",
doi = "10.1016/S0040-4020(01)91757-0",
language = "German",
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pages = "5933--5941",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
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TY - JOUR

T1 - Hydantoine, thiohydantoine, glykocyamidine-XXXIII. Durch Lewis-säuren ausgelöste reduktive umlagerungen vom retrobenzilsäure-typ-VIII reaktionen einiger 5,5-diarylthiohydantoin-derivate mit bortrifluorid-ätheraten, bortrifluorid-ätherat/ bortrifluorid-gemischen und galliumbromid

AU - Fetter, J.

AU - Nyitrai, J.

AU - Lempert, K.

PY - 1971

Y1 - 1971

N2 - 5,5-Diaryldithiohydantoins of type 1b, when refluxed with BF3 dimethyl etherate or mixtures of the former reagent with BF3 in toluene or chlorobenzene, are selectively methylated at the S(2) atom, and/or suffer rearrangement of the retrobenzilic acid type under simultaneous extrusion of the thioxo sulfur atom from position 4 to yield imidazole derivatives of type 6. The latter type of reaction was previously brought about by aluminium chloride. Derivatives already methylated at the S(2) atom are only rearranged, as are also the derivatives of 5,5-diphenyl-4-thiohydantoin (1a, R′{A figure is presented} R″ {A figure is presented} H) if a reaction with the latter occurs at all. Derivatives of 5,5-diphenyl-2-thiohydantoin, on the other hand, are only S-methylated by boron trifluoride dimethyl etherate without being rearranged. The selective methylating properties of the BF3 dimethyl etherate reagent may be applied for the smooth preparation of several hitherto difficulty accessible (di)thiohydantoin derivatives. Gallium tribromide proved to be a catalyst comparable with aluminium trichloride for effecting rearrangements of 5,5-diaryl-4-thio- and -dithiohydantoin derivatives, its milder properties being in some cases favourable. In the cases where the migratory aptitudes of phenyl and p-chlorophenyl groups could be compared, the migratory aptitude of the former was always the greater.

AB - 5,5-Diaryldithiohydantoins of type 1b, when refluxed with BF3 dimethyl etherate or mixtures of the former reagent with BF3 in toluene or chlorobenzene, are selectively methylated at the S(2) atom, and/or suffer rearrangement of the retrobenzilic acid type under simultaneous extrusion of the thioxo sulfur atom from position 4 to yield imidazole derivatives of type 6. The latter type of reaction was previously brought about by aluminium chloride. Derivatives already methylated at the S(2) atom are only rearranged, as are also the derivatives of 5,5-diphenyl-4-thiohydantoin (1a, R′{A figure is presented} R″ {A figure is presented} H) if a reaction with the latter occurs at all. Derivatives of 5,5-diphenyl-2-thiohydantoin, on the other hand, are only S-methylated by boron trifluoride dimethyl etherate without being rearranged. The selective methylating properties of the BF3 dimethyl etherate reagent may be applied for the smooth preparation of several hitherto difficulty accessible (di)thiohydantoin derivatives. Gallium tribromide proved to be a catalyst comparable with aluminium trichloride for effecting rearrangements of 5,5-diaryl-4-thio- and -dithiohydantoin derivatives, its milder properties being in some cases favourable. In the cases where the migratory aptitudes of phenyl and p-chlorophenyl groups could be compared, the migratory aptitude of the former was always the greater.

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U2 - 10.1016/S0040-4020(01)91757-0

DO - 10.1016/S0040-4020(01)91757-0

M3 - Article

VL - 27

SP - 5933

EP - 5941

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 23

ER -