Fluoroacetate acetamide

Alkyl cations thus formed may recombine with the nucleophile (Eq. 10) giving tri-fluoroacetates or acetamides under anodic oxidation conditions in CF3COOH or CH3CN, respectively. For example, electrooxidation of cyclohexane (7) in CH2C12/ CF3COOH yielded 84 % cyclohexyl trifluoroacetate (15) [23] oxidation of adamantane (9) gave acetamide (16) cleanly (Scheme 4) [24]. 

A three-necked flask with an efficient stirrer and a heated Vigreux column (30 cm) connected to a reflux head with a variable take off and a condenser was charged with a mixture of ethyl chloroacetate (300 g, 2.44 mol), KF (200 g, 3.44 mol) and acetamide (100 g). The mixture was heated with stirring and after 3 min refluxing began the temperature at the head of the column was 117 "C. The reaction was maintained at that temperature (2 h) while the crude product was distilled until the temperature gradually fell to 7(TC. The crude distillate (216 g) was redistilled to give 1 yield 137 g (53%) bp 117 — 118 C. iVote Fluoroacetic acid and its derivatives are extremely toxic and all relevant precautions should be taken. 

Many cellulose derivatives form lyotropic liquid crystals in suitable solvents and several thermotropic cellulose derivatives have been reported (1-3) Cellulosic liquid crystalline systems reported prior to early 1982 have been tabulated (1). Since then, some new substituted cellulosic derivatives which form thermotropic cholesteric phases have been prepared (4), and much effort has been devoted to investigating the previously-reported systems. Anisotropic solutions of cellulose acetate and triacetate in tri-fluoroacetic acid have attracted the attention of several groups. Chiroptical properties (5,6), refractive index (7), phase boundaries (8), nuclear magnetic resonance spectra (9,10) and differential scanning calorimetry (11,12) have been reported for this system. However, trifluoroacetic acid causes degradation of cellulosic polymers this calls into question some of the physical measurements on these mesophases, because time is required for the mesophase solutions to achieve their equilibrium order. Mixtures of trifluoroacetic acid with chlorinated solvents have been employed to minimize this problem (13), and anisotropic solutions of cellulose acetate and triacetate in other solvents have been examined (14,15). The mesophase formed by (hydroxypropyl)cellulose (HPC) in water (16) is stable and easy to handle, and has thus attracted further attention (10,11,17-19), as has the thermotropic mesophase of HPC (20). Detailed studies of mesophase formation and chain rigidity for HPC in dimethyl acetamide (21) and for the benzoic acid ester of HPC in acetone and benzene (22) have been published. Anisotropic solutions of methylol cellulose in dimethyl sulfoxide (23) and of cellulose in dimethyl acetamide/ LiCl (24) were reported. Cellulose tricarbanilate in methyl ethyl ketone forms a liquid crystalline solution (25) with optical properties which are quite distinct from those of previously reported cholesteric cellulosic mesophases (26). 

Giller, S., 1956. The influence of acetamide on citrate accumulation after fluoroacetate poisoning. Biochem. J. 63,182-1187. 

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