Patent GB-853440-A (GB)
Title: Detergent sulphonic acid and sulphate salts of certain amphoteric detergents
IPC: C07D233/18
Filed: 1956-12-03
Abstract: The invention comprises certain water-soluble detergent salts in which the anion is an alkali metal salt of an amino-acid containing five or more carbon atoms and a tertiary or quaternary nitrogen atom, and the cation is an organic sulphate ester or sulphonate having six or more carbon atoms ; the ions are as defined below, but the compounds of Specification 803,119 are excluded.  The salts may have one of the five formulae:  <FORM:0853440/IV(b)/1> where G is the cation (defined below), M is an alkali metal and the other groups are as follows :-R is a C4-C18 hydrocarbon radical ; Rb is an aliphatic or aralkyl hydrocarbon radical of 6-18 carbon atoms, the aliphatic part of the aralkyl group having at least 3 carbon atoms ; Rc is an aliphatic or aralkyl hydrocarbon radical of 4-18 carbon atoms ; Rd is a hydrocarbon group of 1-12 carbon atoms (optionally substituted, if aliphatic by hydroxy, keto or an ether linkage); Re is a C1-C4 aliphatic hydrocarbon radical (optionally substituted by hydroxyl if not C1); R1 is H or a C1-C4 aliphatic hydrocarbon radical (optionally substituted by hydroxy, keto or an ether linkage) ; R2 is as R1 (but nos H) ; R5 is as R2 (but not keto substituted); D it CH2-or-CONHRe- ; Q is R2OH, R2COOM or R2OR2COOM, or is R6 below ; Q1 is H or as for Q ; Y is H, RdCOOM or is R8 below ; Y1 is H or R5 COOM, or is R7 below ; T is RdCOOM or is R8 below ; R6 is as for R2 (but not hydroxy substituted) : R7 is as for R5 ; R8 is as for Rd ; y is 1-5 ; z is 0-5 ; and p is 0 or 1 (but p and z are never both zero).  The anion G may be one of the following : R,CO,NRg-Rh,X, Rf,X, Rf,COORk,X, or Rf,Z,(C2H4O)x,SO3, where R is as before, Rf is a C6-C20 aliphatic or aralkyl hydrocarbon radical ; Rg is H or a C1-C8 aliphatic hydrocarbon radical (optionally substituted by hydroxyl or an ether linkage) ; Rh is as for Ra but may contain a CONH or NHCO linkage ; Rk is as for Rh but must be aliphatic, X is SO3 or OSO3, Z is O or S, and x is 1-5.  The products which are quaternary salts are made by reacting the corresponding quaternary hydroxide or halide with an alkali metal salt of the appropriate sulphonic acid or sulphate ester at 100-140 DEG  F. in the presence of a strong mineral acid to bring the pH down to 7-9.  The mixture is then evaporated to dryness and the desired product extracted with an organic solvent, or the aqueous solution (containing inorganic salts) can be used directly as a wetting agent or detergent.  The products which are salts of tertiary bases are made similarly by using the free base as starting material. Many examples are given, in which the various groups are as follows :-R1 Rb and Rc are undecyl, dodecyl, tridecyl or nonylphenyl ; Rd R2 and R5 are CH2, C2H4, CH2CHOH, C2H4OCH2, C2H4OCH2CHOH, (C2H4O)3 CH2, C6H4 and CH2C6H4 ; Re is C2H4 ; R6 is C2H5 ; R8 is CH3, (C2H4O)1-3 H, C6 H5 and CH2, C6H5 ; R5 is hexyl, nonyl, decyl, undecyl, dodecyl, octylphenyl, nonylphenyl and undecylphenyl ; Rg is methyl ; Rh and Rk are C2H4, C4H8, CH2CHOHCH2, C2H4NHCOCH2, C2H4OC2H4OC2H4 and C6H4. Many other suitable reactants are mentioned, of the types given below.  Starting materials: (a) Amides and cyclic amidines.  A diamine NH2R2NH2 is reacted with and acid RCOOH to produce an amide or a cyclic amidine (depending on the conditions) and this is further treated with Hal-Q, Hal-Q1 or Hal-R2 COOM.  If Q is to contain a terminal hydroxy group it is possible to start with a hydroxydiamine NH2R2NHR2OH.  Specific products obtained are N-lauroylamidoethyl-glycine, N-ethyl-N-lauroylamido-ethyl-glycine and the corresponding N-hydroxyethyl and N-carboxymethoxyethyl compounds ; N-lauroylamidoethyl-imino-bis-acetic acid, N-nonylbenzoylamidoethoxyethyl-imino-bis-acetic acid ; the 1 : 1-disubstituted-2-undecyl-imidazolinium hydroxides where one substituent is carboxymethyl and the other is carboxymethyl, ethyl, hydroxyethyl or carboxymethoxyethyl ; and a cyclic amidine with a larger ring by condensing nonylbenzoic acid with diamino-diethylether and reacting with chloracetic acid.  Other suitable reactants are mentioned.  (b) Amines containing an Rb group are made from RbNH2 by reaction wtith Hal-Y, Hal-T and Hal-Rd-COOM (or acrylonitrile and subsequent hydrolysis) ; and in the case of a hydroxy-substituted product ethylene oxide may be used instead of the chlorhydrin. Specified amines are dodecyl-methyl-amine, dodecyl-di-methyl-amine, dodecyl-di-triglycol-amine (after-reacted at the OH groups with 1 or 2 mols of chloracetic acid), hexyl-benzyl-(b  - carboxy -b hydroxyethyl)-amine, dodecyl-phenyl-(carboxymethoxyethyl)-amine N-(nonylphenyl)-ethanolamine, and dodecyl-(hydroxyethoxyethyl)- (carboxyethyl)-amine.  The last four can be quaternated with chloracetic acid, and other similar betaines are dodecyl-dimethyl, dodecyl-carboxyethyl-carboxyphenyl and dodecyl-carboxyethyl-carboxybenzyl.  Betaines derived from imino-bis acetic acid are nonyl-carboxyethyl, nonyldihydroxypropyl and nonylphenyl-hydroxyethyl.  The preparation of N-dodecylglycine and N-dodecyl-imino-bis-acetic acid is also described.  Other suitable reactants are mentioned, and are disclosed in U.S.A. Specification 2,528,378.  (c) Compounds containing an Rc group.  Various polyamines are obtained by reacting ammonia with ethylene oxide, propylene oxide or epichlorhydrin, and are further alkylated with RcCH2Cl or acylated with RcCOOH. Alternatively butylene diamine can be reacted with butylene dichloride in the presence of caustic soda to give N:N1-di-(aminobutyl)-butylene diamine.  Finally the acid group is introduced with Hal-R5-COOH.  There are made this way (1) N-dodecyl-ethylene-diamines further substituted as follows: N1-carboxymethyl; N-(b -carboxy-b -hydroxyethyl)-N1-carboxymethyl; N1-(b -carboxy-b -hydroxyethyl)-N1-carboxymethyl; N : N1-di-(hydroxyethyl)-N1-carboxymethyl; and N:N1:N1-tri-(carboxymethyl); (2) N1-lauroyl-diethylene triamines further substituted as follows: N3-carboxymethyl, N2:N3-di-(carboxymethyl); N2:N3:N3-tri-(carboxymethyl), N2-hydroxyethyl-N3-carboxymethyl; N2: N3-di (hydroxyethyl)-N3-(carboxymethyl); N2: N3-di-(carboxymethoxyethyl)-N3-carboxymethyl; and N2: N3-di [(b -carboxy-b -hydroxy)-ethoxyethyl]-N3 - carboxymethyl; (3) 1-monylbenzylamino-3-carboxyethylamino-2-propanol; (4) 1-[(nonylbenzyl)-(carboxyethyl)-amino]-3-[di-(carboxyethyl) -amino]-2- propanol.  In addition, epichlorhydrin is reacted with 2 mols of 1:3-diamino-propanol and the product acylated at one end with amylbenzoic acid and reacted at the other end with chloracetic acid. Other suitable reactants are mentioned.  Some of these starting materials are covered by Specification 853,441.