Chemistry of 1,3-Dioxepins. XVI. The Synthesis, Characterization and Crystallographic Analysis of Some Arylsulphanyl-, Arylsulphinyl-, Arylsulphonyl- and Benzoyl- N-Substituted Derivatives of 1a,2,6,6a-Tetrahydro-1H,4H-[1,3]dioxepino[5,6-b]azirines

摘要

Chemo-selective synthesis and characterization of N-[(4-nitrophenyl)sulphanyl]- 2 and N-[(4-nitrophenyl)sulphinyl]- 3 N-[(4-aminophenyl)sulphonyl]- 5 and N-(4-aminobenzoyl)- 7 derivatives of 1a,2,6,6a-tetrahydro-1H,4H-[1,3]dioxepino[5,6-b]azirines, starting from 1a,2,6,6a-tetrahydro-1H,4H-[1,3]dioxepino[5,6-b]azirine (1), are described. Their solid state conformational behaviour based on Crystallographic analysis shows that: (ⅰ) dioxepinoazirine moiety of 2, 5 and 7 adopts a boat-chair (BC) conformation, while dioxepinoaziridine moiety of 3 adopts a twistboat (TB) conformation; (ⅱ) the substituent on aziridine nitrogen is always in trans and never in cis position in relation to the dioxepane ring; (ⅲ) the orientation of sulphanyl-, sulphinyl-sulphonyl- and carbonyl- moiety in 2, 3, 5 and 7 are defined by torsion angles C1-S1-N1-C7 of 110.7(2)°, 82.6(2)°, 88.80(11)°and C1-C-N1-C7 of 64.9(5)°, respectively; (ⅳ) Phenyl moiety of sulphinyl and sulphonyl derivatives, 3 and 5, is perpendicular to the S-N bond with the torsion angles N1-S1-C1-C2 of 67.9(3)° and -92.54(13)°, respectively, while that of sulphanyl- 2 and carbonyl- 7 derivatives is coplanar to S-N or C-N bonds with the torsion angles N1-S1-C1-C2 and N1-C-C1-C2 of 168.5(2)° and 170.9(4)°, respectively. Obtained data will serve for further investigation of steric and electronic properties of studied compounds aimed at designing antihyperglycaemically more potent analogues.%Opisana je kemo-selektivna sinteza i karakterizacija N-[(4-nitrofenil)sulfenil]- (2) i N-[(4-nitrofenil)sulfmil]-(3) N-[(4-aminofenil)sulfonil]- (5) i N-(4-aminobenzoil)- (7) analoga antihiperglikemičkih N-sulfonil-1a,2,6,6a-tetrahidro-1H,4H-[1,3]dioksepino[5,6-b]azirina, polazeći od 1a,2,6,6a-tetrahidro-1H,4H-[1,3]dioksepino[5,6-b]-azirina (1). Njihovo konformacijsko ponašanje u čvrstom stanju, temeljeno na provedenoj kristalografskoj analizi pokazuje da: (ⅰ) dioksepinoazirinski dio molekule u spojeva 2, 5 and 7 zauzima čamac-stolac (BC), dok u spoju 3 zauzima konformaciju izvijenog čamca (TB); (ⅱ) supstituent na aziridinskom dušiku je uvijek u trans, a nikad u cis položaju u odnosu na dioksepanski prsten; (ⅲ) orijentacija sulfenilne-, sulfinilne-, sulfonilne- i acilne-skupine u spojeva 2, 3, 5 i 7 definirana je torzijskim kutovima C1-S1-N1-C7 od 110.7(2)° i 82.6(2)°, 88.80(11)° odnosno C1-C-N1-C7 od 64.9(5)°; (ⅳ) Fenilna skupina od sulfinil- i sulfonil derivata 3 i 5 je okomita na S-N vezu s torzijskim kutovima N1-S1-C1-C2 od 67.9(3)° i -92.54(13)°, dok je ona u sulfenil- 2 i karbonil- 7 derivata koplanarna sa S-N ili C-N vezom, s torzijskim kutovima N1-S1-C1-C2 i N1-C-C1-C2 od 168.5(2)° odnosno 170.9(4)°. Dobiveni podaci služit će za daljnja istraživanja steričkih i elektronskih svojstava studiranih spojeva, usmjerena dizajnu antihiperglikemički djelotvornijih analoga.