Societe Nationale Des Poudres Et Explosifs

Research, Incorporated

Mcneil Ab

Roy A Olofson

Jean-Pierre G Senet

Marc D Piteau

Jonathan T Martz

Thierry A Malfroot

Guy C Cagnon

Joseph P Pepe

Mark P Bowman

Cynthia Anne Maryanoff

John E Mills

Ann P Lawson

Patrick Wolf

James D Rodgers

Heather L Rayle

Vu A Dang

Gary P Wooden

David A Cherry

Process for obtaining aryl esters by O-dealkylation of an alkyl aryl ether with an acyl halide in the presence of a catalyst chosen from hexaalkylguanidinium salts and tetraalkylphosphonium salts. The alkyl aryl ether corresponds preferentially to the formula Ar(OR).sub.n in which R denotes an alkyl group, in particular a methyl group, n is an integer from 1 to 6 and Ar represents a C.sub.6 to C.sub.14 aromatic radical, a coumarinyl group or a group of a number of phenyl radicals. This process allows also the obtention of aromatic polyester.

Process for obtaining aryl esters by O-dealkylation and applications

Vinyl chloroformates are described of formula ##STR1## in which: R.sub.1 .dbd.R.sub.2 .dbd.Cl, Br or a saturated 1-4 carbon atom alkyl or together they form a cycloaliphatic ring of 4-8 carbon atoms;

Vinyl chloroformates and preparation

A method for the synthesis of the 2-propanone (I) is described starting from alkoxide (II) through the lactone (IV). ##STR1## Excellent control of the location of the substitution on the phenyl ring is achieved and the reaction proceeds in high yield.

Process for producing 1-(5-substituted-2-ethynylphenyl)-2-propanones

Novel 2,2-dihalovinyl haloformates are described of general formula: ##STR1## in which: X is a chlorine or bromine atom;

2,2-dihalovinyl haloformates and process of preparation

A process for the preparation of vinyl carbamates of formula I ##STR1## is described which comprises heating an .alpha.-halogeno-carbamate of formula II ##STR2## in which X is a halogen atom at a temperature between 70.degree. and 250.degree. C. for a period of time between several minutes up to several hours. R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are the same or different. The process is applicable to a great variety of products in which R.sub.1, R.sub.2, R.sub.3, and R.sub.4 have different meanings. The process permits to prepare in a simple and economical fashion, vinyl carbamates, which have industrial value and novel vinyl carbamates.

Process for the preparation of vinyl carbamates

A process for the preparation of fluoroformates of formula: ##STR1## in which R.sup.1 is a substituted or unsubstituted, saturated or unsaturated aliphatic, cycloaliphatic or polycyclic radical, or substituted or unsubstituted araliphatic radical or an aromatic radical, which consists of reacting a carbonate of formula: ##STR2## in which R.sup.1 has the same meaning as hereinabove and R.sup.2 is hydrogen, alkyl of 1-12 carbon atoms, cycloalkyl of 5-12 carbon atoms, saturated or unsaturated, unsubstituted or substituted by one or more halogen atoms or R.sup.2 is aryl, unsubstituted or substituted by one or more halogen atoms, with an alkali or alkaline earth fluoride, ammonium fluoride or a quaternary ammonium fluoride, of formula FNR.sup.3 R.sup.4 R.sup.5 R.sup.6, wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6 are the same or different and are hydrogen, alkyl or aralkyl of 1-12 carbon atoms or a fluoride which is KHF.sub.2, NH.sub.4 HF.sub.2 or KSO.sub.2 F. The fluoride is activated by a complexing agent for the cation which is a cryptate, a cyclic or linear polyether or by means of a polar aprotic compound. The carbonate is split to give a reaction mixture containing an aldehyde and the fluoroformate which is removed from the reaction mixture.

Process for the preparation of fluoroformates

Process for the synthesis of .alpha.-chlorinated chloroformates, and new .alpha.-chlorinated chloroformates. The invention relates to a new process for the manufacture of .alpha.-chlorinated chloroformates and, to new .alpha.-chlorinated chloroformates as new industrial products. The process according to the invention consists of a synthesis, by catalytic phosgenation, of .alpha.-chlorinated chloroformates of the formula: ##STR1## in which: R represents a substituted or unsubstituted hydrocarbon radical and m represents an integer superior or equal to one, this synthesis consisting in reacting phosgene with the aldehyde R--CHO).sub.m, in the presence of a catalyst which is an organic or inorganic substance which is capable in a medium containing an aldehyde of the formula R--CHO).sub.m, phosgene and, possibly, a solvent, of generating a pair of ions one of which is an halogenide anion and the other is a cation which is sufficiently separated from said halogenide anion so as to give to the latter a nucleophilic power enabling it to react with the function(s) aldehyde of the molecule R--CHO).sub.m.

Process for the synthesis of .alpha.-chlorinated chloroformates

Process for the synthesis of .alpha.-chlorinated chloroformates, and new .alpha.-chlorinated chloroformates. The invention relates to a new process for the manufacture of .alpha.-chlorinated chloroformates and, to new .alpha.-chlorinated chloroformates as new industrial products.

Process for the synthesis of alpha-chlorinated chloroformates

There is provided a novel and high yield procedure for transforming acid salts of 14-alkanoyloxymorphinans and derivatives thereof into the corresponding N-alkyl-14-hydroxymorphinans wherein the alkyl moiety on the nitrogen contains the same number of carbon atoms as that previously in the 14-alkanoyl moiety. In the process of the present invention, the acid is neutralized to the free base, the alkanoyl moiety at the 14-oxy then spontaneously shifts to the nitrogen and is subsequently reduced to the corresponding alkyl moiety. O-dealkylation at C-3, where an alkoxy group is originally present, is carried out in the usual manner. There is also provided a readily produced and readily disassociated adduct of the corresponding 14-hydroxy-N-alkanoyl morphinan-6-alkylene ketal with benzene, tetrahydrofuran, and the like.

N-alkyl-14-hydroxymorphinans and derivatives

There is provided a novel, high yield, method of dealkylating N-alkylated 14-hydroxymorphinans and derivatives thereof including, inter alia, oxymorphone and oycodone. There are thus provided, inter alia, more efficient routes for the formation of naloxone, naltrexone, and nalbuphine. In the principal step of the process, the dealkylation using certain oxycarbonyl halides (or haloformates) is carried out on the N-alkyl-14-acyloxy-morphinan which it is desired to dealkylate.

Growing community of inventors

State College, PA, United States of America

Roy A Olofson