MECHANISTIC ANALYSIS OF THE REACTIONS OF (PENTAFLUOROPHENYL)NITRENE IN ALKANES

被引：53

作者：

YOUNG, MJT ^{[1
]}

PLATZ, MS ^{[1
]}

机构：

[1] OHIO STATE UNIV,DEPT CHEM,COLUMBUS,OH 43210

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1991年 / 56卷 / 22期

关键词：

D O I：

10.1021/jo00022a036

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Photolysis of pentafluorophenyl azide in n-butane, cyclopentane, or 2,3-dimethylbutane releases singlet (pentafluorophenyl)nitrene, which can insert into a CH bond, ring expand to a ketenimine, or undergo intersystem crossing (ISC) to the triplet state of the nitrene. In alkanes at 25-degrees-C ring expansion is the major process, CH insertion is only modest, and ISC is unimportant. At temperatures below -78-degrees-C, ISC is the dominant process. Differential activation parameters are derived and compared with those of phenyl azide.

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页码：6403 / 6406

页数：4

相关论文

共 26 条

[1]

ADMASU A, UNPUB

[2] STUDIES IN AZIDE CHEMISTRY .9. INVESTIGATIONS INVOLVING FLUORINATED AZIDOPYRIMIDINES AND 4-AZIDO-3-CHLORO-2,5,6-TRIFLUOROPYRIDINE [J].

BANKS, RE ;

PRAKASH, A ;

VENAYAK, ND .

JOURNAL OF FLUORINE CHEMISTRY, 1980, 16 (04) :325-338

[3] STUDIES IN AZIDE CHEMISTRY, .5. SYNTHESIS OF 4-AZIDO-2,3,5,6-TETRAFLUORO-, 4-AZIDO-3CHLORO-2,5,6-TRIFLUORO-PYRIDINE, AND 4-AZIDO-3,5-DICHLORO-2,6-DIFLUORO-[PYRIDINE] AND SOME THERMAL REACTIONS OF TETRAFLUORO-COMPOUND [J].

BANKS, RE ;

SPARKES, GR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1972, (23) :2964-2970

[4] STUDIES IN AZIDE CHEMISTRY .6. SOME REACTIONS OF PERFLUOROAZIDOBENZENE AND PERFLUORO-4-AZIDOTOLUENE [J].

BANKS, RE ;

PRAKASH, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1974, (11) :1365-1371

[5] DECISIVE EVIDENCE FOR THE OCCURRENCE OF RING-EXPANSION DURING PYROLYSIS OF AZIDOPENTAFLUOROBENZENE - X-RAY CRYSTALLOGRAPHIC ANALYSIS OF PENTAFLUOROPHENYL-NITRENE DIMER [J].

BANKS, RE ;

VENAYAK, ND ;

HAMOR, TA .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (19) :900-901

[6] SOME COMMENTS ON THE PERFLUORO EFFECT .3. HE(I-ALPHA) PHOTOELECTRON-SPECTRA OF SOME HIGHER AROMATIC PERFLUORO COMPOUNDS [J].

BASTIDE, J ;

HALL, D ;

HEILBRONNER, E ;

MAIER, JP ;

PLEVEY, RG .

JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 1979, 16 (03) :205-208

[7]

Bayley H., 1983, PHOTOGENERATED REAGE

[8] AROMATIC POLYFLUORO-COMPOUNDS .23. POLYFLUORO-AZO-, -AXOXY-, AND -HYDRAZO-BENZENES [J].

BURDON, J ;

MORTON, CJ ;

THOMAS, DF .

JOURNAL OF THE CHEMICAL SOCIETY, 1965, (APR) :2621-&

[9] A DETERMINATION OF THE TRIPLET SINGLET SPLITTING IN PHENYLNITRENE VIA PHOTODETACHMENT SPECTROSCOPY [J].

DRZAIC, PS ;

BRAUMAN, JI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (12) :3443-3446

[10]

ELAND JHD, 1974, PHOTOELECTRON SPECTR