F Ethyl chloroformate

Disulfuryl dilluoride, 4326 f Ethyl chloroformate, 1164 Ethyl oxalyl chloride, 1456 /V-Ethy l-/V-propylcarbamoyl chloride, 2468... 

Disulfuryl dichloride, 4097 Disulfuryl difluoride, 4320 f Ethyl chloroformate, 1160 Ethyl oxalyl chloride, 1452 /V-Ethyl-iV-propylcarbamoyl chloride, 2462... 

Prepn is by dropwise addn of a cold aq sodium peroxide (1.0 molar) so In to 1.0 mole of vigorously stirred ethyl chloroformate while maintain, ing the temp at 6— 10°. The mixt is stirred for an addnl half hr after all the sodium peroxide has been added. The oily prod is then sepd, washed with distd w and dried using anhyd Naj S04. An 81 % yield is obtd. The frozen ester is sens to the shock from a No 6 elect detong cap, producing a more brisant deton than an equal amt (0.25 lb) of benzoyl peroxide Ref F. Strain et al, JACS 72,1254-63 (1950) CA 46,1984(1950)... 

Mateo Castro R., Domenech Carbo M.T., Peris Martinez V., Gimeno Adelantado J.V., Bosch Reig F., Study of binding media in works of art by gas chromatographic analysis of amino acids and fatty acids derivatized with ethyl chloroformate, Journal of Chromatography A, 1997, 778, 373 381. 

R.M. Castro, M.T. Domenech Carbo, V.P. Martinez, J.V. Gimeno Adelantado, F. Bosch Reig, Study of Binding Media in Works of Art by Gas Chromatographic Analysis of Amino Acids and Fatty Acids Derivatized with Ethyl Chloroformate, J. Chromatography, A, 778, 373 381 (1997). 

Goswami and Sarkar3 claimed to have prepared methyl and ethyl fluoroformates by the action of thallium fluoride on the corresponding chloroformates. These fluoroformates were described as powerful lacrimators. We found that no appreciable reaction took place between potassium fluoride and ethyl chloroformate in boiling carbon tetrachloride or nitrobenzene. Ethyl fluoroformate could, however, be readily produced by the action of potassium fluoride on ethyl chloroformate by using the autoclave technique. It was found not to have the lacrimatory properties claimed for it, and was non-toxic in comparison with M.F.A. This non-toxicity was to be expected, as the fluoroformate contains the COF and not the CH2F- group. 

Hydrophobic, fluorinated hyperbranched grafts were synthesized from an ethyl chloroformate activated hyperbranched 3-PAA/Au graft using the fluorinated alkyl amine H2N(CH2)(CF2)6CF3. Reaction of an activated 3-PAA/Au film with H2N(CH2 ) (CF2 leCFs produced a fluorinated film that almost doubled in thickness. XPS analysis showed 46 atom-% F in the product fluoramidated graft which is 86% of the theoretical atomic concentration for a homogenous... 

Finally, a third way of synthesis is from imipramine (7.1.1), which nndergoes demethylation by snccessive reaction with ethyl chloroformate, giving 5-[3-(Af-carbethoxy-iV-methyl)aniino-propyl]-10,ll-dihydro-5H-dibenz[b,f azepine (7.1.15), the alkaline hydrolysis of which leads to desipramine (7.1.13) [23,24],... 

A procedure for obtaining indole-3-carboxylate ester from the f-pyrrolidino-o-nitrostyrene intermediates in the Leimgruber-Batcho indole synthesis was demonstrated. Although ethyl chloroformate is evidently not reactive enough, phosgene followed by methanolysis effects f) -carbomethoxylation. Reductive cyclization then gives the indole esters. <95SC95>... 

F5 Ethylene dichloride Fg Methylene chloride F 7 Chloroform F8 Ethyl ether F9 Ethyl acetate F o n-butyl alcohol F11 Isopropyl alcohol F 2 Acetone F23 Methyl alcohol... 

On the other hand, for more easily ionizable electrophiles, like ethyl chloroformate or benzoyl chloride, the first reaction stage is ionization with formation of lithium chloride and a carbocation. The latter then reacts with the atom of highest electron density in the ambident anion, namely, with the nitrogen atom. A similar use of aldimines for the synthesis of ot,/f-unsaturated aldehydes was reported by Corey and coworkers and by Nagata and coworkers . 

Aminopyridine-3-ketimines, prepared by addition of Grignard or lithium reagents to nicoti-nonitriles, have been cyclized with phosgene, ethyl chloroformate, or carbonyl diimidazole to give pyrido[2,3-f/lpyrimidin-2( 1 f/)-ones, e.g. 47.73 75... 

Rosseel, M.T. Vermeulen, A.M. Belpaire, F.M. Reversed-phase high-performance liquid chromatographic analysis of atenolol enantiomers in plasma after chiral derivatization with (-l-)-l-(9-flu-orenyl)ethyl chloroformate. J.Chromatogr., 1991, 568, 239—245... 

Mixed malonates. Ethyl chloroformate reacts with the a-anion of f-butyl acetate to give ethyl f-butyl malonate in 70-75% yield. The reaction is a general route to mixed malonates. Ethyl chloroformate can be replaced by other... 

Ethyl chloroformate added dropwise with stirring at -20 to -10° to formyl-alanine and triethylamine in chloroform, and kept 2hrs. at the above temp. -> 5-ethoxycarbonyloxy-4-methyloxazole (startg. m. f. 799). Y 80%. M. Murakami and M. Iwanami, Bull. Chem. Soc. Japan 41, 726 (1968). 

Isopropylidenetriphenylphosphorane in tetrahydrofuran mixed with an equimolar amount of ethyl chloroformate, allowed to stand a few hrs., 3 moles n-propyl-magnesium bromide added, and refluxed ca. 5 hrs. isopropyl -propyl ketone. Y 58%. F. e. s. T. Mukaiyama, R. Yoda, and I. Kuwajima, Tetrah. Let. 1969, 23... 

N-(s-Triazoi-4-yl)phenylacetamidine refluxed 12 hrs. with an equimolar amount of ethyl chloroformate in dry nitromethane or acetonitrile 3-phenyl-l,2,4-triazole. Y 91%. - Other acylating agents sudi as acetic anhydride, carboxylic acids, or HCl may be used in place of ethyl diloroformate. F. e. s. H. G. O. Becker et al., J. pr. 311, 471 (1969) synthesis of 1,3,4-oxadiazoles cf. ibid. 311, 646. 

Ethyl chloroformate added dropwise at 0° during 10 min. to a mixture of A-tert-butylpyridine and a soln. of er -butylmagnesium chloride in tetrahydrofuran, then treated at 0° with water -> l-ethoxycarbonyl-2,4-di-terr-butyl-l,2-dihydro-pyridine. Y 55%, - In the absence of ethyl chloroformate, pyridine derivs. react poorly with Grignard compds. F. e. s. G. Fraenkel, J. W. Cooper, and C. M. Fink, Ang. Ch. 82, 518 (1970). 

An ethereal soln. of -BuLi added to a stirred soln. of /r 5-N-(but-2-enyl)aniline in ether at — 50° under argon, stirred for 20 min at —50° to — 30°, treated with a soln. of 2 eqs. /-BuLi in pentane at — 30°, warmed to 20° over 2-4 h, treated with diethyl carbonate at — 50°, stirred overnight allowing the temp, to rise to 20°, and hydrolysed with water - product. Y 78%. Reaction failed with ethyl chloroformate or CO2. F.e.s. J. Barluenga et al.. Tetrahedron Letters 29, 4859-62 (1988) 3-substitution with various electrophiles s. J. Chem. Soc. Chem. Commun. 1988, 1135-6. 

DL-Phenylalanine heated with tri-n-butyltin oxide in toluene, the water removed azeotropically with most of the toluene, cooled to 0, added with exclusion of moisture to a cold toluene soln. of a mixed anhydride prepared from carbo-benzoxyglycine and ethyl chloroformate (s. Synth. Meth. 7, 447), stirred 0.5 hr. at —5° and 3 hrs. at room temp., water added, stirred 10 min., 1 N NaOH-soln. added, and stirred another 10 min. -> N-carbobenzoxyglycyl-DL-phenylalanine. Y Sl%.—The trialkyltin group can be easily attached, and easily removed by dil. acid or base. No racemization occurred during Ibe prepn. of tri-n-butyltin L-leucinate. F. e. and limitation s. M. Frankel et al., J. Org. Chem. 30, 1596 (1965). 

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