Syntheses and cis-trans isomerization of light-sensitive benzenediazo sulfides

Abstract

The solvent was removed under reduced pressure to give a residue which was treated with water to give 0.2 g of a product which melted at 219°on recrystallization from 2-propanol and was identical with lb described above by mixture melting point, spectral comparison, and tic behavior.iV-Thioformyl derivative 4e was obtained in 71% yield by refluxing 4b with thiophosgene in toluene: mp 236°on recrystallization from methylene chloride-ether; ir 3250, 1660, and 1610 cm-1.

Catalytically Active Azoaldolase. Preparation on Solid Support

“…The trans isomer of the model compound p-carboxybenzeneazo derivative of N-acetyl-cysteine has a molar absorption coefficient (see Fig. 6) of 15700 M-' x cm-' at 329 nm (unpublished results) in agreement with the values reported for similar benzenediazoalkyl-sulfides [20]. Assuming that the molar absorption coefficient is retained by the chromophores in the protein, a total of 8 sulfhydryl groups have been modified in the coupling reaction per molecule of tetrameric enzyme.…”

Ion−Radical Complexes and SRN1-like Reactions in the Gas-Phase. A Negative-Ion Mass Spectrometric Investigation of Arylazo Sulfides

“…Arylazo sulfides [( E )- 1a ,4c ( E )- 1b ,4c ( E )- 1c ,4d ( Z )- 1c ,4c ( E )- and ( Z )- 1d , ( Z )- 1e , ( Z )- 1f ,4d ( Z )- 1g , 4e ], aryl phenyl sulfides ( 2a ,4b 2b 4a ), and aryl tert -butyl sulfides ( 2c ,4c 2e ) were analytically pure samples prepared as reported. tert -Butyl 4-nitrophenyl sulfide ( 2d ) was an authentic sample from our laboratory, isolated in the reactions on the corresponding arylazo sulfide ( Z )- 1d with nucleophiles: 4g mp 37.1−38.0 °C (petroleum ether); 1 H NMR (CDCl 3 , 80 MHz) δ 1.35 (9H, s), 7.66 and 8.16 (2H each, AA‘BB‘, J 8.6 Hz).…”

Ligand Abstraction in the Reaction of Aryldiazonium Ions with some Iron Complexes Containing Coordinated Cysteine, Maleonitriledithiol, or Triarylphosphine

“…The sulfonic acid 8g is insoluble in dilute acid but soluble in water and most polar organic solvents. S-(Arenediazo) derivatives from thiols have not been notable for thermal stability and few examples of stable, well-characterized compounds exist (27)(28)(29). Interest in these compounds has centered around their photochemical cis-trans isomerism and utility in photographic applications (29,30).…”