Direct polynitroaliphatic alcohol addition to alkenes. 1. Synthesis of new 2-fluoro-2,2-dinitroethyl acetals and ethers

Aliphatic nitro alcohols. Synthesis, chemical transformations and applications

“…108 Adduct 266 was obtained by reaction of 107 with 2-methylpent-1-ene at 20 8C in the presence of HgSO 4 or Hg 2 SO 4 (yields 74% and 58%, respectively). 178 The reaction of the nitro alcohol 107 with buta-1,3-diene affords a mixture of 1,2-addition product 267 and 1,4-addition product 268 in a ratio of 77 : 23, their total yield being 53%. 178 Two products 269 and 270 resulting from radical C-and O-addition (yields 28% and 70%, respectively) have been synthesised by the reaction of hexan-1-ol with 1-nitroprop-1-ene in the presence of tert-butyl peroxide.…”

“…178 The reaction of the nitro alcohol 107 with buta-1,3-diene affords a mixture of 1,2-addition product 267 and 1,4-addition product 268 in a ratio of 77 : 23, their total yield being 53%. 178 Two products 269 and 270 resulting from radical C-and O-addition (yields 28% and 70%, respectively) have been synthesised by the reaction of hexan-1-ol with 1-nitroprop-1-ene in the presence of tert-butyl peroxide. 179 1,1,1-Trinitroethanol adds to the C=N bond in perfluoroguanidine at ambient temperature to give compound 271.…”

“…183 Polycondensation of formaldehyde with the diol HOCH 2 C(-NO 2 ) 2 CH 2 CH 2 C(NO 2 ) 2 CH 2 OH in the presence of sulfuric acid affords poly(nitroformal). 185 Nitro alcohols add to acyclic 178,186 or cyclic 108,142,178 vinyl ethers 275 in the presence of catalysts to give acetals 276 (see Table 14).…”

“…The addition of nitro alcohols 277 to 2,3-dihydropyran in THF and HMPT in the presence of butyllithium at a temperature between 790 8C and 740 8C leads to the compounds 209. 154 The nitro alcohol 107 adds to ethoxyacetylene in CH 2 Cl 2 at 20 8C in the presence of HgSO 4 187 or Hg(OAc) 2 178 or in the presence of HgO in CF 3 COOH 92 giving rise to 2 : 1 adduct 278 (yields 100%, 95%, or 70%, respectively). When this reaction is carried out in the presence of Hg(OAc) 2 in CH 2 Cl 2 and hexane at 20 8C, the 1 : 1 adduct 279 is produced in 73% yield in addition to the adduct 278 (yield 27%).…”

“…When this reaction is carried out in the presence of Hg(OAc) 2 in CH 2 Cl 2 and hexane at 20 8C, the 1 : 1 adduct 279 is produced in 73% yield in addition to the adduct 278 (yield 27%). 178 Two compounds, 1 : 1 adduct 280 and 2 : 1 adduct 281, were obtained by refluxing the nitro alcohol 107 and divinyl ether in CH 2 Cl 2 in the presence of HgSO 4 or Hg 2 SO 4 . It was found that the ratio of 280 to 281 depends appreciably on the 107 : ether ratio.…”