Photochemical nitration by tetranitromethane .33. Adduct formation in the photochemical reactions of 1,2,4,5- and 1,2,3,5-tetramethylbenzene
Butts, CP; Eberson, L; Fulton, KL; Hartshorn, MP; Robinson, WT; Timmermanvaughan, DJ
| HERO ID | 1949399 |
|---|---|
| In Press | No |
| Year | 1996 |
| Title | Photochemical nitration by tetranitromethane .33. Adduct formation in the photochemical reactions of 1,2,4,5- and 1,2,3,5-tetramethylbenzene |
| Authors | Butts, CP; Eberson, L; Fulton, KL; Hartshorn, MP; Robinson, WT; Timmermanvaughan, DJ |
| Journal | Acta Chemica Scandinavica |
| Volume | 50 |
| Issue | 11 |
| Page Numbers | 991-1008 |
| Abstract | The photolysis of the charge-transfer complex of tetranitromethane and 1,2,4,5-tetramethylbenzene in dichloromethane or acetonitrile gives the epimeric 1,3,4,6-tetramethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 8 and 9, in addition to products of nuclear nitration 12 and side-chain modification 10, 11, and 13-18. Similar reactions of 1,2,3,5-tetramethylbenzene gave trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethylcyclohexa-1,4-diene 30 and two isomeric 'double' adducts 31 and 32, in addition to products of nuclear nitration 27 and side-chain modification 26, 28 and 29. The eliminative rearrangements of adducts 8 and 30 to give re-aromatized products in acetonitrile or [H-2(3)]acetonitrile and in [H-2]chloroform are reported. The photolysis of the charge-transfer complexes of tetranitromethane with either 1,2,4,5-tetramethylbenzene or 1,2,3,5-tetramethylbenzene in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) gives a marked increase in the yields of ring-nitration products 12 or 27, respectively, reactions presumed to proceed via a nitrosation-oxidation sequence. Reaction of 1,2,4,5-tetramethylbenzene with excess nitrogen dioxide in HFP also results in extensive ring nitration to give 12 and 2,3,5,6-tetramethyl-1,4-dinitrobenzene (25); the latter compound is seen as arising via the 2,3,5,6-tetramethyl- 1,4-dinitrosobenzene (34). Similar reaction of 1,2,3,5-tetramethylbenzene gives ring-nitration product 27 as the major product. X-Ray crystal structures are reported for 2,4,6-trimethyl-1-(2',2',2'-trinitroethyl)benzene (26) and trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-diene (30). (C) Acta Chemica Scandinavica 1996. |
| Doi | 10.3891/acta.chem.scand.50-0991 |
| Wosid | WOS:A1996VP25200006 |
| Is Certified Translation | No |
| Dupe Override | No |
| Comments | Scopus URL: https://www.scopus.com/inward/record.uri?eid=2-s2.0-0347846615&doi=10.3891%2facta.chem.scand.50-0991&partnerID=40&md5=6d62f8d3a6733002bb18ed4a0fa2fe4e |
| Is Public | Yes |
| Language Text | English |