Patent GB-756271-A (GB)
Title: New quaternary salts and the production thereof
Inventor: MARTIN HENRY
IPC: C07D211/62
Filed: 1954-07-29
Abstract: The invention comprises quaternary salts of the general formula <FORM:0756271/IV(a)/1> wherein Am is an amido group which may be mono- or di-substituted by alkyl radicals, R is either (a) an alkyl radical, the chain of which may be interrupted by an oxygen atom, an -NH-, >N-alkyl, -CONH-, <FORM:0756271/IV(a)/2> or -COO- group, or (b) an aralkyl or aryl radical, the total number of carbon atoms in R and any alkyl substituent to Am being at least 4, and X is a halogen atom, an alkoxysulphonyloxy or an alkylsulphonyloxy group; and their production, when R is other than aryl, by quaternization of the corresponding free isonicotinamide with a compound RX.  The invention also includes the production of quaternary salts of the above general formula wherein R can be aryl by reaction of the corresponding free isonicotinamide with a strongly negative compound, such compounds being specified in "Journal fur praktische Chemie," Vol. 83, page 325 (1911) and "Das Pyridin und Seine Derivate," by Maier-Bode & Altpeter, 1934, page 22, and analogues of these compounds in which the halogen atoms are replaced by a different halogen atom or by an alkylsulphonyloxy or an alkoxysulphonyloxy group, to form an addition compound which is then reacted with a base R.NH2 to form the desired quaternary salt.  The first of the above methods can be performed in the presence of solvents such as aromatic hydrocarbons, esters or alcohols or in absence of solvents and in the presence of an excess of the ester component.  If the anion in the product is a halogen ion this may then be exchanged for another anion.  Examples of strongly negative components used in the second of the above methods are 2,4-dinitro- and 2,4,6-trinitro-halogen benzenes, brom-cyanogen and chlor-cyanogen.  In examples: (1) isonicotinamide and n-hexyl bromide heated in xylene yield N1-brom-N1-hexyl-isonicotinamide; (2) to (13) the corresponding n-octyl, n-decyl, n-dodecyl, n-hexadecyl, n-butyl, n-amyl, n-iso-amyl, n-tetradecyl, n-octadecyl, n-heptyl, n-nonyl and n-undecyl compounds are similarly prepared; (14) N1-chlor-N1-(carbo-n-hexyloxy)-methyl-isonicotinamide is prepared from chloracetic acid n-hexyl ester and isonicotinamide in dioxan; (15) to (18) compounds in which X is Cl and R is -CH2COOC10H21(n), -CH2COOC12H25(n), -CH2CONHC12H25(n) and -CH2COOC16H33(n) are prepared similarly; (19) to (22) N1-chloro-N1-methyl-N2-n-dodecyl -, N1 - methylsulphonato - N1 - methyl-N2 - n - dodecyl -, N1 - chloro - N1 - benzyl-N2 - n - dodecyl - and N1 - iodo - N1 - ethyl-N2-dimethyl-isonicotinamides are prepared from the appropriate isonicotinamides by reaction with respectively, methyl chloride, methyl-sulphonic acid methyl ester, benzyl chloride and ethyl iodide; reference is also made to the use of b -butoxy-ethyl bromide and b -ethoxy butyl chloride and also to other sulphonic acid esters; (23) isonicotinamide and 2,4-dinitrochloro benzene are heated to form an addition product which is isolated and heated with aniline in ethanol to give N1-chloro-N1-phenyl-isonicotinamide.