摘要:

AbstractOxidation of the cis isomer of the λ3‐cyclotriphosphazane [EtNP(OCH2CF3)]3with trimethylamine‐N‐oxide (TMNO) gives the cis isomer of trioxo‐λ5‐cyclotriphosphazane [EtNP(O)(OCH2CF3)]3; the trans isomer of [EtNP(O)(OCH2CF3)]3is obtained by the treatment of a cis and trans mixture of [EtNP(OCH2CF3)]3with aqueous H2O2. The two trioxocyclotriphosphazanes have been characterized by elemental analysis, IR, and NMR (1H,13C,19F, and31P) spectroscopy. The solid state structures of both the isomers have been determined by single crystal X‐ray diffraction. The six‐membered P3N3ring in both the isomers exhibits a twist‐boat conformation; in the cis isomer, the trifluoroethoxy substituents lie on the same side of the ring, whereas, in the trans isomer, two trifluoroethoxy groups are on one side of the ring and the third on the other side of the ring. Crystal data for cis‐[EtNP(O)(OCH2CF3)]3: monoclinic,P21/n,a= 13.593(3),b= 9.721(2),c= 17.539(3) Å, β = 99.49(2)°,V= 2286(1) Å3,Z= 4, and FinalR= 0.047. Crystal data for trans‐[EtNP(O)(OCH2CF3)]3: monoclinic,P21/n,a= 11.685(4),b= 15.115(5),c= 13.233(5) Å, ‐ = 102.21(3)°,V= 2284(

ISSN:1042-7163    

DOI:10.1002/hc.520060114

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY

摘要:

AbstractLithiation of 1‐cyanomethylbenzotriazole (4) with LDA and subsequent reactions with alkyl halides or carbonyl compounds afforded the corresponding 1‐(α‐cyanoalkyl)‐ and 1‐(α‐cyanoalkenyl)‐benzotriazoles. Bromination of4with NBS formed 1‐(bromocyanomethyl)benzotriazole. 1‐Cyanoalkylbenzotriazoles condensed with hydrazine hydrate to give 4‐amino‐3,5‐bis(benzotriazol‐1‐yl)triazoles which underwent deamination with sodium nitrite to yield 3,5‐

ISSN:1042-7163    

DOI:10.1002/hc.520060115

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY

摘要:

Abstractω‐Bromoacetophenone reacts with the sodium salt of ethyl cyanoacetate to afford α‐cyano‐β‐phenyl‐Δαβ‐butenolide. This butenolide undergoes azo coupling with diazotized aromatic amines (ArNH2) to afford the hydrazo derivatives. These hydrazo derivatives (ArPh, 4‐ClC6H4, 4‐MeC6H4, 4‐MeOC6H4) were transformed into the corresponding 3(2H)‐pyridazinone derivatives on stirring in methanol in the presence of potassium hydroxide. These latter compounds were converted into the corresponding 3‐cyano‐2,5‐dihydroxy‐4‐phenyl‐N‐arylpyrrole derivatives on reduction with zinc dust in refluxing acetic acid, presumably via reductive cleavage of the NN bond of the pyridazine fo

ISSN:1042-7163    

DOI:10.1002/hc.520060116

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY

摘要:

AbstractStable benzene‐fused polysulfide compounds, 3,4‐dihydro‐1,2,5‐benzotrithiepins (1a‐c), have been prepared, and the structure of1ahas been determined by X‐ray crystallographic analysis. While the electrophilic oxidation of compounds1with m‐chloroperbenzoic acid gave the corresponding 3,4‐dihydro‐1,2,5‐benzotrithiepin 5‐oxides (2) in moderate yields, the oxidation of1with N‐bromosuccinimide afforded a mixture of 5‐oxides2, unexpected, inseparable 3,4‐dihydro‐1,2,5‐benzotrithiepin 2,2‐dioxides (3), and 3,4‐dihydro‐1,2,5‐benzotrithiepin 1,1‐dioxides (4). Semiempirical PM3 calculations were carried out, and the computed HOMO of1asuggested a significant favoring of electrophilic reactions at the sulfur atom at the 5‐position. The treatment of 5‐oxides2with acetyl bromide or oxalyl dibromide as halogenating reagents gave 2,2‐dioxides3and 1,1‐dioxides4, suggesting that an intramolecular halogen transfer from the 5‐position (sulfide moiety) to the 1‐ and 2‐p

ISSN:1042-7163    

DOI:10.1002/hc.520060117

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY

摘要:

AbstractThe crystal and molecular structures of both neutral and anionic 1‐methyl‐1H‐tetrazole‐5‐thiol, as its potassium(18‐crown‐6) salt, are reported. In the solid state, the molecular thiotetrazole adopts a planar, dimeric arrangement, in which two neighboring molecules are hydrogen bridged. Each monomeric unit exhibits considerable π electron delocalization over the CN2S fragment. The anionic form displays extensive, but not uniform, π electron delocalization within the ring, which also extends to the exocyclic carbon–sulfur bond, the structure being best described as a hybrid. The potassium cation is coordinated to the macrocyclic 18‐crown‐6 ether as expected, but it also interacts with the NCS fragment of the t

ISSN:1042-7163    

DOI:10.1002/hc.520060118

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY

ISSN:1042-7163    

DOI:10.1002/hc.520060103

出版商:VCH Publishers, Inc.    

年代:1995

数据来源: WILEY