Chemie polyfunktioneller moleküle: XCI. Tritertiäre arsine und IHRE verwendung als bausteine zur synthese von arsenhaltigen cryptanden (bzw. spheranden)

Abstract

[HN(CH 2CH 2Cl) 2CH 2CH(CH 3)Cl]Cl (V). [HN{CH 2CH(CH 3)Cl} 3]Cl (VII) and the 1,3,5-trithiacyclohexane derivative (CHS) 3(CH 2CH 2Cl) 3 (IX) react with NaAs(C 6H 5) 2 in liquid ammonia to give N[CH 2CH 2As(C 6H 5) 2] 2CH 2CH(CH 3)As(C 6H 5) 2 (VI). N[CH 2CH(CH 3)As(C 6H 5) 2] 3 (VIII) and (CHS) 3[CH 2CH 2As(C 6H 5) 2] 3 (X). Treatment of VI with HI results, under elimination of benzene, almost quantitatively in the formation of [HN(CH 2CH 2AsI 2) 2CH 2CH(CH 2)AsI 2]I (XI), which is recrystallized from THF as [HN(CH 2CH 2AsI 2) 2CH 2CH(CH 3)AsI 2]I · THF (1/1) (XIa). All attempts to obtain homogeneous products by reaction of VIII or X with HI, such as [HN{CH 2CH(CH 3)AsI 2} 3]I and (CHS) 3(CH 2CH 2AsI 2) 3, failed. With H 2O/NH 3 or H 2S/N(C 2H 5) 3 XIa forms the cryptands [N(CH 2CH 2) 2CH 2CH(CH 3)] 8(As 4O 4) 6 (XII) or [N(CH 2CH 2) 2CH 2CH(CH 3)] 8(As 4S 4) 6 (XIII), which also can be considered as spherands. All the new compounds are characterized, as far as possible, by their IR, Raman, 1H NMR and mass spectra.