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Facile Syntheses of New Cavitands with Mixed Substituents
Author(s) -
Flauaus Manuela,
Herzing Michael,
Köllhofer Axel,
Laly Myriam,
Plenio Herbert
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200103)2001:6<1061::aid-ejoc1061>3.0.co;2-1
Subject(s) - chemistry , yield (engineering) , thiourea , cavitand , stoichiometry , medicinal chemistry , hydrazine (antidepressant) , hydrolysis , hydrate , organic chemistry , polymer chemistry , chromatography , supramolecular chemistry , molecule , materials science , metallurgy
The (CH 2 Br) 4 cavitand 1 and its reactions with NaOAc in varying stoichiometric ratios have been used to prepare a series of five different (CH 2 OAc) 4− n (CH 2 Br) n cavitands ( n = 0−3) 2 − 6 with mixed substituents, which can be separated by column chromatography (combined yield >95%) and are thus available in multi‐gram quantities. The substitution reaction is statistical and the yields of individual acetates are controlled by the amount of NaOAc relative to 1 . Careful hydrolysis of cavitands 2 − 6 with LiOH in THF‐water results in the formation of the (CH 2 OH) 4− n (CH 2 Br) n cavitands ( n = 0−3) 7 − 11 in yields of between 70−85%, Treatment of 2 − 6 with thiourea and NaOH affords the respective (CH 2 SH) 4− n (CH 2 OH) n cavitands ( n = 0−3) 12 − 16 in yields of around 90%. Reactions of 2 − 6 with K‐Phthalimide generate the respective (CH 2 Pht.) 4− n (CH 2 OAc) n cavitands ( n = 0−3) 17 − 21 , which can be cleaved with hydrazine hydrate resulting in the (CH 2 NH 2 ) 4− n (CH 2 OH) n cavitands ( n = 0−3) 22 − 26 in an overall yield of 60−70%.