Aromatic Fluorine Compounds. I. Preparation of p-Fluoraniline by Catalytic Reduction of Nitrobenzene in Hydrogen Fluoride¹

Catalytic hydrogenation of organic compounds in liquid hydrogen fluoride

“…Pt02 (5.2) 25 °C, 2 h, 16 psi H2 60 Cyclohexane (89) Cyclohexylbenzene (11) Toluene (3) 108-88-3 Pt02 (0.3) 25 °C, 2 h, 16 psi H2 43 Methylcyclohexane (100) p-Xylene (3) 106-42-3 Pt02 (0. trans-1,3-Dimethylcyclohexane (6) czs-1,4-Dimethylcyclohexane (5) m-Xylene (3) 108-38-3 Pt02 (0. Methylcyclopentane ( 15) Acetophenone (4) 98-86-2 Pt02 (0.…”

“…Methylcyclopentane ( 15) Acetophenone (4) 98-86-2 Pt02 (0. 4-Chloroaniline (57) 1 Quinoline (3) 91-22-5 Pt02 (0.3) 25 °C, 1.5 h, 16 psi H2 83 4,5,6,7-Tetrahydroquinoline (90) 1,2,3,4-Tetrahydroquinoline (10) Quinoline (3) Pt02 (0.3) 25 °C, 17 h, 16 psi H2 100 4,5,6,7-Tetrahydroquinoline (50) Decahydroquinoline (50) Isoquinoline (12.9) 119-65-3 Pt02 (0.6) 25 °C, 18 h, 5000 psi H2 66 4,5,6,7-Tetrahydroisoquinoline Benzonitrile (3.0) 100-47-0 Pt02 (0.3) 25 °C, 5 h, 16 psi H2 100 Benzaldehyde (76) Benzamide (3) PhCH=NCH2Ph ( 14) PhCH=NCH2C6Hul (6) p-Xylene (3.0) Pt02 (0.3) 25 °C, 2 h, 16 psi H2 100 czs-1,4-Dimethylcyclohexane (67) 5 mL HF, 25 mL ether trans-1,4-Dimethylcyclohexane Pyridine (14) 110-86-1 0 (pyridine)…”

“…The reduction of nitrobenzenes to p-fluoroanilines in HF has been described. 3 More recently, several reports on hydrogenations in HF-super acid systems have appeared.4™7 In this paper, the noble metal catalyzed hydrogenation of several organic functional groups in anhydrous HF is described. Most noteworthy are the observations that certain aliphatic carboxylic acids are reduced over Pt02 in HF and that aliphatic ketones are reduced to hydrocarbons in HF under extremely mild conditions.…”

Synthesis of cyclopropylmethanol derivatives bearing electronegative substituents

“…These were combined and the product was crystallized by the addition of ether-hexane yielding 0.74 g (44%) of 4, mp 54-58°. A portion was recrystallized from ether-hexane for analysis: mp 57-58°; ir (CCL) 3450 (broad, did not change on dilution, H bonded OH), 3050 (aryl H), 1675 cm-1 (0=0); nmr (CCU) 0.96 (2 H, m, cyclopropyl trans to benzoyl), 1.09 (2 H, m, cvclopropyl cis to benzoyl), 3.02 (1 H, broad s, OH), 3.67 (2 H, s, CH20-), 7.2-7.S (5 H, m, typical benzoyl); mass spectrum (70 ev) m/e (rel intensity) 176 (9), 175 (31), 158 (12), 105 (100), 77 (70), 51 (24).…”

Hydrogenation and Dehydrogenation of Organic Compounds

“…Phenylhydroxylamine is produced over Pt/C at 25°C and 3 atm (gauge) H2 in methanol containing 1% dimethyl sulfoxide (DMSO) (Rylander et al, 1972); phenylhydroxylamine is also produced on Pt/C at higher temperatures and a different solvent concentration (see Equation 7.37). If HF is used instead of H2S04, the product is fluorinated aniline (Fidler et al, 1961). Production of 4-aminophenol is observed on Pt/C in sulfuric acid, containing about 1% DMSO at 25°C and 1-3 atm (gauge) of H2 (Rylander et af., 1973);…”