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Syntheses and 1 H‐, 13 C‐ and 15 N‐NMR Spectra of Ethynyl Isocyanide, H−C≡C−N≡C, D−C≡C−N≡C and Prop‐1‐ynyl Isocyanide, H 3 CC≡C−N≡C, D 3 CC≡C−N≡C: High Resolution Infrared Spectrum of Prop‐1‐ynyl Isocyanide
Author(s) -
Bürger Hans,
Lentz Dieter,
Meisner Britta,
Nickelt Natascha,
Preugschat Dagmar,
Senzlober Michael
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20000915)6:18<3377::aid-chem3377>3.0.co;2-1
Subject(s) - triple bond , isocyanide , chemistry , medicinal chemistry , stereochemistry , double bond , organic chemistry
Ethynyl isocyanide, H−C≡C−N≡C ( 1 a ), deuteroethynyl isocyanide, D−C≡C−N≡C ( 1 b ), prop‐1‐ynyl isocyanide, H 3 CC≡C−N≡C ( 1 c ), and trideuteroprop‐1‐ynyl isocyanide, D 3 CC≡C−N≡C ( 1 d ) are synthesized by flash vacuum pyrolysis of suitable organometallic precursor molecules (CO) 5 Cr(CN−CCl=CClH) ( 5 a ), (CO) 5 Cr(CN−CCl=CClD) ( 5 b ), (CO) 5 Cr(CN−CCl=CCl−CH 3 ) ( 5 c ) and (CO) 5 Cr(CN−CCl=CCl−CD 3 ) ( 5 d ), respectively. Compounds 5 a–d are formed in two steps by radical alkylation of tetraethylammonium pentacarbonyl(cyano)chromate, NEt 4 [Cr(CO) 5 (CN)] ( 2 ) by 1,1,2,2,‐tetrachloroethane ( 3 a ), 1,1,2,2‐tetrachloro‐1,2‐dideuteroethane ( 3 b ), 1,1,2,2,‐tetrachloropropane ( 3 c ), and 1,1,2,2‐tetrachloro‐1,3,3,3‐tetradeuteropropane ( 3 d ) yielding [(CO) 5 Cr(CN−CCl 2 −CCl 2 −H)] ( 4 a ), [(CO) 5 Cr(CN−CCl 2 −CCl 2 D)] ( 4 b ), [(CO) 5 Cr(CN−CCl 2 −CCl 2 −CH 3 )] ( 4 c ), and [(CO) 5 Cr(CN−CCl 2 −CCl 2 −CD 3 )] ( 4 d ). Dehalogenation of 4 a–d using zinc in diethylether/acetic acid gives 5 a–d , respectively. A multinuclear NMR study revealed the 1 H‐, 13 C‐ and 15 N‐NMR data of 1 a and 1 c . Molecular spectroscopic data of 1 c were determined by high resolution infrared spectroscopy. The by‐products of the pyrolysis are the E and Z isomers of the halogenated ethenyl isocyanides H(Cl)CCCl−NC ( 6 a ) and H 3 C(Cl)CCCl−NC ( 6 c ) which have been characterized by IR, MS and NMR spectroscopy.