Patent GB-1066116-A (GB)
Title: Derivatives of bis (hydroxy-4-phenyl) acetic acid
IPC: C07C69/734
Filed: 1965-04-28
Abstract: The invention comprises bis-(4-hydroxy-phenyl)-acetic acid derivatives of the formula <FORM:1066116/C2/1> in which X1, X2, X3 and X4 denote hydrogen chlorine or bromine atoms, D denotes a chlorine atom, a hydroxy, dimethylamino or diethylamino group or a residue -OR1, R1 denoting an aliphatic, alicyclic or aromatic hydrocarbon residue or -OR denoting a residue of the formula <FORM:1066116/C2/2> in which n is 1 or 2, A and B denote a group -CH2COOH1-CH2COOR or -COR, R denoting an aliphatic, alicyclic or aromatic hydrocarbon residue or a residue of the formula <FORM:1066116/C2/3> in which n is 1 or 2.  When at least one of the symbols X1, X2, X3 and X4 denotes chlorine A and B may also denote hydrogen.  The compounds may be prepared by treating bis(4-hydroxyphenyl)-acetic acid or an ester thereof either with chlorine or bromine, to effect nuclear halogenation, or with a halogenated compound capable of reacting with the phenolic hydroxyl groups and, in either event, the products may then be esterified or saponified or converted into salts, acid chlorides or amides. Examples are given in which (1) bis-(4-hydroxyphenyl)-acetic acid is chlorinated, the final product being bis-(3,5-dichloro-4-hydroxyphenyl)-acetic acid, which may then be esterified with methanol (Example 2) to yield a methyl ester which, in turn, may be reacted with ethyl monochloracetate (Example 3) to yield the diethyl and monomethyl ester of the formula <FORM:1066116/C2/4> R denoting ethyl.  This product may be saponified (Example 4). In Example 5, bis-(4-hydroxyphenyl) -acetic acid is esterified with methanol and then reacted with ethyl monochloracetate to yield the ester of the formula <FORM:1066116/C2/5> which may be saponified (Example 6) to yield the corresponding triacid.  Example 7 describes the preparation of a salt of bis-(3,5-dichloro-4-phenyl) -acetic acid with 2-methylimidazole. In Example 8, bis-(3,5-dichloro-4-hydroxyphenyl)-acetic acid is acetylated with acetyl chloride to yield the acid. <FORM:1066116/C2/6> which may then be converted into its acid chloride, by treatment with thionyl chloride, and then into its dimethylamide, by treatment with dimethylamine.  In Example 9, the amide of Example 8 is saponified to yield the amide <FORM:1066116/C2/7> In Example 10, the butyl ester of bis-(4-hydroxyphenyl) -acetic acid is epoxidized with epichlorohydrin to yield the ester <FORM:1066116/C2/8> and in the final example bis-(4-hydroxyphenyl)-acetic acid is esterified with epichlorhydrin to yield the ester <FORM:1066116/C2/9> The products are useful as herbicides, fungicides and bactericides and the products containing epoxy groups are also useful in the manufacture of epoxy resins or acrylic resins (see Divisions A5 and C3).ALSO:As components in the manufacture of epoxy resins or thermosetting acrylic resins, use is made of bis-(4-hydroxyphenyl) acetic acid derivatives of the formula <FORM:1066116/C3/1> in which X1, X2, X3 and X4 denote hydrogen chlorine or bromine atoms, D denotes a residue -OR1, in which R1 represents an aliphatic, alicyclic or aromatic hydrocarbon residue or -OR1 represents a residue of the formula <FORM:1066116/C3/2> in which n is 1 or 2, and A and B denote residues of the formula <FORM:1066116/C3/3> in which n is 1 or 2 (see Division C2).  Example 11 describes the manufacture of an epoxy resin by reacting bis-(4-hydroxyphenyl) acetic acid with the compound of the formula <FORM:1066116/C3/4> Example 10 illustrates the preparation of a styrene-methyl methacrylate-butyl acrylate-acrylamide - acrylic acid - glyoxal tetra-allyl acetal copolymer by solution polymerization in xylene/butanol in the presence of benzoyl peroxide and lauryl mercaptan; the solution is treated with the compound of the last formula above and then pigmented with titanium dioxide.ALSO:As herbicides, fungicides and batericides, use is made of bis(4-hydroxyphenyl)acetic acid derivatives of the formula <FORM:1066116/A5-A6/1> in which X1, X2, X3 and X4 denote hydrogen, chlorine or bromine atoms, D denotes chlorine or a group -OH, -OCH3, -N(CH3)2 or -N(C2H5)2, and A and B denote groups -CH2COOH, -CH2COOR or -COR, the symbol R denoting an aliphatic, alicyclic or aromatic hydrocarbon residue.  When at least one of the symbols X1, X2, X3 and X4 denotes chlorine, A and B may also denote hydrogen (see Division C2).  The products are applied by spraying in an aqueous or oily medium.