Urethanes phenyl

Phenyl- and a-naphthyl-urethanes (Phenyl- and a-naphthyl-carbamates). Both phenyl isocyanate and a-naphthyl isocyanate react with alcohols to yield phenyl-urethanes and a-naphthyl-urethanes respectively ... 

Alcohol B.P. M.P. 3 6>Dlnltro-benzoate p-NItro- benzoate Phenyl- urethane... 

Alcohol B.P. Benzoate />-Nltro- benzoate 3 S-Dinltro- benzoate Phenyl- urethane a-Naphtbyl- urethane Other Derivatives... 

Isobutyl chloroformate [543-27-1] M 136.6, b 123-127 /atm, 128.8 /atm, d 1.053, n 1.4070. It can be dried over CaCl2 and fractionated at atm press while keeping moisture out. Its purity can be checked by conversion to the phenyl urethane derivative with PhNCO [Saunders et al. J Am Chem Soc 73 3796 7957.] IR v 1780cm [Thompson and Jameson Spectrochim Acta 13 236 7959 Rose Justus Liebigs Ann Chem 205 227 1880]. 

This alcohol, of the formula (CH3)2CH. CHjOH, is found in the free state in the distillation water of the oil of Eucalyptus Amygdalina. It boils at 108 5°, and has a specific gravity 0 8003. It yields a phenyl-urethane melting at 80°. 

Isoamyl alcohol, (CH3)2. CH. CHjCHjOH, has been found in the free state in various eucalyptus oils, and also in geranium, lavender, and peppermint oils. It boils at 131° and jdelds a phenyl-urethane, melting at 53°. 

Preparation of the urethane, CgHj. NH. COOC,gH,7. A mixture of 2 or 3 grams of the alcohol is mixed with rather more than the theoretical amount of phenyl-isocyanate, and allowed to stand in a stoppered flask for a week. It is then mixed with water, and a current of steam passed through the mixture, in order to remove the unaltered linalol. The crystalline mass which remains is collected, dried on a porous plate, and extracted with ether, which dissolves the phenyl-urethane. The ethereal solution is aflowed to evaporate spontaneously when crystals of the urethane separate, which melt at 65°. 

It yields a phenyl-urethane, melting at 45". On oxidation it yields an aldehyde having an odour of lemons, which yields a semicarhazone, melting at 135°. 

It appeared that the impure alcohol isolated from balsam of Peru was, in fact, identical with nerolidol. When allowed to stand for three to four weeks with phenyl-isocyanate both alcohols yielded a phenyl-urethane, melting at 37" to 38°. A mixture of the two bodies suffered no depression in melting-point. The alcohols have the formula 15 260-The alcohol from balsam of Peru is therefore mixed with a small quantity -of an alcohol of higher specific gravity, the nature of which is still undetermined. Traces of benzyl alcohol were found in it, but not in sufficient quantity to account for the differences observed. Oxidation experiments did not throw any light on the question. It may therefore be safely assumed that the peruviol of Thoms consisted in the main of nerolidol, but contaminated with a substance of the same boiling-point to such an extent that its combustion figures pointed to the formula CjjH. jO instead of... 

It yields a diphenyl-urethane, which melts at 99° to 100°, and is very useful for identification purposes. The phenyl-urethane, melting at 80° is less useful for this purpose, since its melting-point is almost identical with those of benzyl and nonyl alcohols. It combines with phthalic acid to form a phthalic acid ester, melting at 188° to 189°. 

It can be characterised by its phenyl-urethane, melting at 47° to 48°, or by oxidising its acetic acid solution by means of chromic acid, when it yields hydrocinnamic acid, melting at 49°. 

Cinnamic alcohol forms a phenyl-urethane, melting at 90° to 91°, and a diphenyl-urethane, melting at 97° to 98°. On oxidation it yields cinnamic acid, melting at 133°, and by more thorough oxidation, benzoic acid, melting at 120°. 

It yields a well-defined phenyl-urethane, melting at 113°. It requires considerable care to obtain this compound, which should be prepared as follows terpineol mixed with the theoretical amount of phenyl-isocyanate is left for four days at the ordinary room temperature. Crystals separate which are diphenyl urea,, and are removed by treating the product with anhydrous ether, in which the diphenyl urea is insoluble. If the liquid be very carefully and slowly evaporated fine needles of terpinyl-phenyl urethane separate. This compound has the formula C Hj. NH. COOCjqHj-. The correspnanding naphthyl-urethane melts at 147° to 148°. 

It yields the following crystalline derivatives, which are suitable for its identification nitrosochloride melting at 103°, nitrol-piperidine melting at 108°, nitrol-anilide melting at 110°, and phenyl-urethane melting at 85°. 

Figure 4. Contact angle 6 of cellophane and PVA films as a function of phenyl-urethanation time (---) cellophane (----) PVA (O, ,) receding ( .If) ad-...

Mononitrodi phenyl urethane, Cj5H 4N2Q,, mw 286.28 N 9.79%, Only crae isomer is found in Beil... 

Dlnltro-benzoate p-Nitro- benzcate Phenyl- urethane a-Naph- thyl- urethane Hydrogen 3-nitro- phthalate Other Derivatives... 

To avoid the risk associated with extrusion thru dies, the proplnt was at first made in flaked form. The gelatinizer finally adopted was benzyl-phenyl-urethane (Ref 30)... 

Nitro- benzoate °C Phenyl- urethan °C 1- Hydrogen Naphthyl- 3-nitro-urethan phthalate °C °C O-Alkyl Other saccharin derivatives °C °C ... 

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