Formic deuteriated

I.r., n.m.r., and mass spectroscopy showed that the N-H bonded compound was present, rather than its isomers, e.g. F2P(S)-N=Pp20H or HS-F2P=N P0F2. The A -deuteriated analogues, XX P(S)-ND-POF2, were obtained by solvolysis with deuteriated formic acid. 

Treatment of trans,trans-2,6-ociddiene (122) with deuteriated formic acid HCO2D in the presence of deuteriosulphuric acid gave the cyclized formate ester 123. A concerted mechanism (equation 63) was proposed for this reaction73. The stereospecific ring-closure of the 1,4-cyclohexadiene derivative 124 in acetic anhydride/perchloric acid affords the octalin 125, which was isolated as the diacetate 126 (equation 64)74. 

Cervinka and Kriz95 investigated the mechanism of the Luke reduction with the use of deuteriated formic acid. 1-Methylpyridinium iodide afforded a mixture of l-methyl-5-deuterio-3-piperideine (92, R = H) and l-methyl-3,5-dideuteriopiperidine (93, R = H). A mixture containing l,3-dimethyl-3,5-dideuteriopiperidine (93, R = Me) was obtained from 1,3-dimethylpyridinium iodide. 

A sample of the deuteriated polymer (0.531 g) was ozonized as a suspension in CH2CI2, and the product treated with formic acid-hydrogen peroxide as described previously in this section. Cyclization to d2-succinic anhydrides and derivatization to form the d2 N-(o-biphenyl) succinimides were also performed by previously described methods. %-NMR (acetone-d6, 200 MHz, ) resonances at 6 2.62 (s), 2.62 (d, J 4.4 Hz), 2.84 (s), 2.84 (d, J 4.4Hz), 7.48 (m). Measurement of peak areas by triangulation indicated that the d2-N-(o-biphenyl) succinimide produced in the above experiment was 55% meso-isomer and 45% d>l-isomer. 

Other Systems.— The addition of formic, acetic, and chloroacetic acids to quadri-cyclane at 20 °C affords the corresponding esters of exo-2-norbornenol and nortri-cyclenol. Solvent effects and the results obtained using the 0-deuteriated carboxylic acids are interpreted in terms of the six-centre addition mechanism (97) the minor pathway to nortricyclyl products, in the absence of added mineral acid, is the result of leakage from (97) to the norbornenyl cation. ... 

Physical Properties.—In studies of the secondary thioamide. function, the i.r. and, where possible, the Raman spectra of a series of iV-methyl-thioamides XCSNHMe (X = CSNHMe, CSNH2, CONHj, or COjK) and of N- and C-deuteriated products were determined, vibrational analyses were proposed, and the results were compared with data for other JV-methyl-thioamides. The C n.m.r. spectra of a series of tertiary thioamides of formic, acetic, trifluoroacetic, propionic, and... 

Singleton, D.L., G. Paraskevopoulos, R.S. Irwin, G.S. Jolly, and D.J. McKenney (1988), Rate and mechanism of the reaction of hydroxyl radicals with formic and deuteriated formic acids, J. Am. Chem. Soc, 110, 7786-7790. 

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