Patent GB-721196-A (GB)
Title: Improvements in alkylene polyamine derivatives
Filed: 1950-12-02
Abstract: The invention comprises compounds of formula <FORM:0721196/IV (b)/1> where n is 2 or 3, m is zero or an integer, D is -CH2COOH, -CH2CH2COOH or an alkali metal or ammonium salt thereof, A is an alkyl group of at least 7 carbon atoms or a cycloalkyl group of 6 carbon atoms, either group having one or two hydrogen atoms replaced by -COOR, -COOM, -OR or -OR1OR, where R is alkyl or hydrogen, M is an alkali metal or ammonium radicle and R1 is an alkylene group, each of the replacing groups being spaced from the N atoms by at least two carbon atoms of the hydrocarbon group carrying them.  They may be made by reacting one mol. of a polyamine, e.g. ethylene or trimethylene diamines or diethylene triamine, with two mols. of a chloro derivative of the substituent desired in the A positions, the imino hydrogens then being substituted by means of chloracetic acid or by an alkali metal cyanide with a formaldehyde-yielding substance under alkaline conditions, c.f. U.S.A. Specification 2,407,645.  Also one mol. of alpha, beta-dichloro ethylene may be reacted with two mols. of an amine of the substituent desired in the A positions with subsequent treatment as above or esters of acrylic type unsaturated acids may be reacted with the diamine either before or after hydro-halogenation, the remaining hydrogen atoms attached to the nitrogen atoms being substituted as before. Alkylene polyamine derivatives in which A is a substituted cycloalkyl group of 6 carbon atoms are obtained from condensation products of a Diels-Alder reaction.  A preferred compound is <FORM:0721196/IV (b)/2> where D is as above defined and R is H or alkyl.  They may be made by condensing maleic anhydride with butadiene, the esterified dicarboxylic acid product being condensed with a polyamine as described for the acrylic type esters.  Ester products may be saponified to yield alkali metal or ammonium salts and the latter acidified to yield the free acids. Preferred compounds are derivatives of ethylene diamine in which A is a long-chain acid such as undecylenic acid.  The preparation of the dimethyl ester of ethylene diamine N,N1-di-(sodium acetate)-N,N1-di-(9-ethyl nonylic acid) is described, the appropriate undecylenic acid being converted to its methyl ester, treated with hydrogen bromide and the resultant bromide reacted with ethylene diamine, the product thus obtained being treated with sodium chloracetate to yield the desired salt.  This ester is saponified with sodium hydroxide and the free acid liberated with sulphuric acid.  Other isomers of undecylenic acid may be used in which case A may be <FORM:0721196/IV (b)/3> where x is an integer of 1-8.  By reacting omega-undecylenic acid methyl ester with hypochlorous acid and the product with ethylene diamine and sodium chloracetate a compound <FORM:0721196/IV (b)/4> is obtained on hydrolysis with alkali.  Similarly a product is described as obtainable by reacting the hydrochloric acid derivative of methyl undecylenic acid ester with diethylene triamine and the resultant derivative with sodium chloropropionate.  The products are wetting agents and detergents being compatible with soap and sequestering calcium ions.ALSO:Compounds of formula <FORM:0721196/III/1> where n is 2 or 3, m is O or an integer, D is CH2COOH, CH2CH2COOH or an alkali metal or ammonium salt thereof, A is an alkyl group of at least 7 carbon atoms or a cycloalkyl group of 6 carbon atoms, either group having one or two hydrogen atoms replaced by COOR, COOM, OR or OR1OR where R is alkyl or hydrogen, M is an alkali metal or ammonium radicle and R1 is an alkylene group, each of the replacing groups being spaced from the N atoms by at least two carbon atoms of the hydrocarbon group carrying them, are said to be compatible with soap and to form washing compounds when added thereto in amounts of e.g. 1 to 5 per cent by weight.  Preferred compounds are derivatives of ethylene diamine in which A is a long chain acid such as undecylenic acid, e.g. N, N1-di-(sodium acetate), N. N1-di(9-ethyl nonylic acid), and the free acid obtained after saponification thereof.  Other compounds described are <FORM:0721196/III/2> and the product obtainable by reacting the hydrochloric acid derivative of methyl undecylenic acid ester with diethylene triamine and the resultant derivative with sodium chloropropionate.  A preferred cycloalkyl compound is <FORM:0721196/III/3> where D is as above and R is H or alkyl.  The preparation of the compounds is described in Group IV (b)