Radiation‐Chemical Synthesis of Phosphonium and Arsonium Salts

Abstract

Structure (2) follows from the N M R spectrum[71, which shows a singlet for the methyl group at T = 9.04 (3 H ) and two unsymmetrical triplets (A2B2 spectrum) for the methylenc groups at T = 8. 70, 8.63, and 8.51 (4 H. at C-2 and C-6), and a t T = 7. 94, 7.84, and 7.73 (4 H , ally1 protons at C-3 and C-5). In CC14 solution the singlet signal for the hydroxymethyl group is at T = 6.68 (3 H), but in dimethyl sulfoxide there arc two signals with relative areas 1:2 (OH;CH2). The signal for the vinyl protons occurs at T = 5.42 (2 H). Infrared spectrum: 880, 1640880, , 1770, 1035, 3360 (broad association band), 3630 (primary OH), and 1365 cm-1 (CH3). Thc infrared spectrum of the alcohol (2) is identical with that of a sample prepared by reducing l-n~ethyl-4-metitylenccyclohexanc-I-carboxylic acid [21 with LiAlH4.A violent explosion occurred during a n attempt t o free N F J from small amounts (less than 2 vol-x) of N2F2 and N 2 0 by adsorption o n active charcoal at low temperatures. Active charcoal grains (600 g, previously dried a t 120°C; manufactured by Messrs. Riedel, Seelze) were placed iii a 2-liter steel pressure flask. T h e vessel was cooled to ~ 100 "C and evacuated for a considerable time. About 25 g of NF3 was introduced during about 10 min and t!ien the gas flow was interrupted at a pressure of 1.5 kg,'cni2 in the adsorption vessel. A short time thereafter a n explosion fractured the metal vessel and ejected glowing active charcoal. Starting materials Chlorobenzene Triphenylphosphine Broniobenzene Triphenylphosphine Iodohenzene Triphenylphosphine 1 -Chloro-4-iodobenzene Triphenylphospine 1,4-Dibromobenzene Triphenylphosphine 1,4-Dichlorobenzene Triphenylphosphine p-Bromotoluene Triphenylphosphine Mole-% 76 24 73.5 26.5 91.7 8.3 74.8 25.2 79.7 20.3 71.5 28.5 64 36According t o RnfLll, carbon does not react with NF3 even at red heat. Gould and Smith [*, 31 found that NF3 reacts with petroleuai: c-.kcin a fluidized bed at 400 -500 "C to eivc N~F J ,The reac:i:in CF4, and C'1F6. NF3-i-3 C I _ CF4-t 2 Nz(:I) was observed only above 500 "C. W e have heated active charcoal grains in a nickel tube and treated them with N F 3 (93.2 vol-0,: NF3; 2.22 % N2; 0.42 0; 02, 1.9 P: N20; 1.31 % N2F2) at atmospheric pressure. U p t o 10OoC n o reaction could be observed. At 150 "C the charcoal reacted with incandescence. N2 and CF4 were the sole products found. N2F4 could not be detected. The r c x t i o n (a) is o that leading to N2F4, CF4, W e assume that the reaction leading to cxplosioii was initiated by the heat of adsorption, which could not be removed sufficiently rapidly. Experiments with 30 g of active charcoal grains, carried out without thermal insulation, resulted in temperature increases of 40 t o 70 "C when gaseous NF3 was led at atmospheric pressure into a vessel containing charcoal and previously evacuated to 1-2 mni. When impure NF3 is passed through active charcoal a t -80 'C, N2F2 and N20 arc completely retained, but at +20 "C only N20 is adsorbed. Wtririug: Spcciol prcvxrvtiuirs (ire i.eq!iired if NF3 i...