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Macrocyclic Siloxanes with Two Exocyclic trans ‐Silanol and Two Exocyclic trans ‐Amino Functions − Stereoselective Syntheses and Structures
Author(s) -
Tacke Reinhold,
Burschka Christian,
Heermann Joachim,
Richter Ingo,
Wagner Brigitte,
Willeke Reiner
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200109)2001:9<2211::aid-ejic2211>3.0.co;2-k
Subject(s) - silanol , chemistry , ring (chemistry) , stereoselectivity , silane , solid state , silicate , stereochemistry , molar ratio , medicinal chemistry , organic chemistry , catalysis
A simple preparative method for the stereoselective synthesis of ten‐ and twelve‐membered cyclosiloxanes with two exocyclic trans ‐silanol and two exocyclic trans ‐amino functions has been developed. Thus, treatment of trimethoxy(morpholinomethyl)silane ( 5 ) with two molar equivalents of HOPh 2 Si−SiPh 2 OH and HOPh 2 Si−O−SiPh 2 OH, respectively, yielded trans ‐1,6‐bis(2‐hydroxy‐1,1,2,2‐tetraphenyldisilan‐1‐yloxy)‐1,6‐bis(morpholinomethyl)‐3,3,4,4,8,8,9,9‐octaphenyl‐2,5,7,10‐tetraoxa‐1,3,4,6,8,9‐hexasilacyclodecane ( 6 , 10‐membered ring) and trans ‐2,8‐bis(3‐hydroxy‐1,1,3,3‐tetraphenyldisiloxan‐1‐yloxy)‐2,8‐bis(morpholinomethyl)‐4,4,6, 6,10,10,12,12‐octaphenylcyclohexasiloxane ( 7 , 12‐membered ring). In contrast, treatment of 5 with two molar equivalents of HOPh 2 C−CPh 2 OH afforded (morpholiniomethyl)bis[tetraphenylethane‐1,2‐diolato(2−)]silicate ( 3 ), a zwitterionic spirocyclic λ 5 Si ‐silicate. Compounds 3 , 6· EtOAc, and 7· PhMe were characterized by elemental analyses (C, H N), solid‐state 29 Si VACP/MAS NMR studies, solution NMR experiments ( 1 H, 13 C, 29 Si; CDCl 3 ), and crystal structure analyses.