Patent GB-820083-A (GB)
Title: Reactions of organomagnesium chloride reagents
IPC: C07D213/55
Filed: 1956-05-03
Abstract: Substituted carboxylic acids or salts or esters thereof are prepared by reacting with an a -halocarboxylic acid or a derivative thereof formed at the acid radical, an organo-magnesium chloride complex of formula R(MgCl)x.nQ, where R is a substituted or unsubstituted aryl group, vinylic radical or heterocyclic radical exhibiting aromatic or pseudoaromatic characteristics which includes in its heterocyclic ring an oxygen, sulphur or tertiary nitrogen atom and which is bound to magnesium through a carbon of an aromatic or pseudoaromatic ring, and R contains no functional group which is reactive under the conditions for the formation of the complex, n is 1-3, x is 1 or 2, and Q a substituted or unsubstituted cyclic ether having 5 or 6 atoms in the ring of which one is oxygen, the others being carbon with the exception that a substituted nitrogen may replace the carbon in the 4-position when the ring has 6 atoms, the ring containing not more than one double bond and at least one carbon adjacent to the oxygen being free of substituents, said ether containing no substituent which is reactive with organomagnesium chlorides or any other components or products of the process. Such complexes are described in Specifications 776,993, 777,158 and 779,100.  Reaction may be effected in compound Q or an inert hydrocarbon.  R may be defined as <FORM:0820083/IV (a)/1> where the Rs represent H, F, Cl, alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy or dialkylamino. Alternatively, where x = 1, R may be a vinyl group <FORM:0820083/IV (a)/2> or, when x = 2, a group <FORM:0820083/IV (a)/3> the Rs being H or substituted or unsubstituted aliphatic or aromatic hydrocarbon groups, while R1 may be cyclized with R11 or R111 and R111 may be chlorine. Preferably an ester or salt of the a -halo acid is used. The general reaction may be represented: RMgCl.nQ + R1R11XC.CO2R111 --> RR1R11CCO2R111 where R1 and R11 are H or organic radicals, X is halogen, and R111 an organic group or a metal, usually an alkali metal.  With a bifunctional MgCl complex, the reaction is: R(MgCl)2.nQ + R1R11XCCO2R111 --> R(R1R11CCO2R111)2 In the following examples, Q is tetrahydrofuran and x is 1 unless otherwise stated: (1) the vinyl complex with ethyl bromacetate yields ethyl 3-butenoate; (2) with ethyl a -chlordiethylacetate yields a -vinyl-a ,a -diethylacetate; (3) with ethyl a  - chlor - a  - phenylacetate, ethyl a  - vinyl - a -phenylacetate; (4) the phenyl complex with ethyl bromacetate gives ethyl phenylacetate; (6) with sodium chloracetate followed by acid hydrolysis gives phenylacetic acid; (8) with sodium a -bromstearate, a -phenylstearic acid; (9) with sodium dichloracetate, diphenylacetic acid; (10), (11) the p-chlorphenyl complex with sodium mono- or di-chloracetate yields monoor di-(p-chlorphenyl) acetic acid; (12)-(14) o-, m- and p-tolyl complexes yield similarly tolylacetates; (15) the p-anisyl complex and ethyl chloracetate give 2-ethyl p-anisylacetate; (16) the p-phenetyl complex and a -bromstearate give a -p-phenetylstearic acid; (17)-(20) the di-penta-chlorphenyl complexes similarly give di-penta-chlorphenyl-substituted acids and esters; (21) the 2-m-xylyl complex is used in producing ethyl 2-m-xylylacetate; (22) the biphenyl complex is used similarly; (23) the trichlorbiphenyl complex with ethyl chloracetate gives ethyl trichlorbiphenylacetate; (24) the nonachlorbiphenyl complex and sodium a -bromstearate give a -monochlorbiphenylstearic acid; (25) o-trifluormethylphenyl complex and a -2-chlor-a -phenylacetate give ethyl a -o-trifluormethyl - phenyl - a  - phenylacetate; (26)-(29) p-dimethyl (or ethyl) aminophenyl complexes are used to produce p-dimethyl (or ethyl) aminophenylacetates and a -p-diethylaminophenylstearic acid; (30) chlortolyl complex and sodium chloracetate give chlortolylacetic acid; (31) chloranisyl complex is used in producing ethyl a  - chloranisyl - a  - phenylacetate; (32) chlorphenetyl complex is used for bis chlorphenetylacetic acid; (33) ethyltetrachlorphenyl complex for ethyltetrachlorphenylacetic acid; (34)-(38) thienyl complex is used in preparing a -thienylacetic acid and ethyl ester, ethyl a -thienyl, a ,a  - diethylacetate, a ,a  - thienylstearic acid, and a ,a -thienyldiphenylacetic acid; (39)-(41) a -pyridyl, a -furyl, and 5-chlorthienyl complexes with ethyl chloracetate yield ethyl a -pyridyl-, a -furyl-, and 5-chlorthienyl-acetates; (42) m-fluorphenyl complex yields m-fluorphenyl - acetate; (44)-(48) 2 - benzothiazolyl, 2 - benzoxazolyl, 2 - methyl - 5 - benzothiazolyl, 2-, 6- or 8-quinolyl, and 8-quinolinyl complexes are used in producing corresponding substituted acetic or stearic acids or acetates; (49)-(58) 1-cyclohexen-1-yl, and various propenyl, butenyl, and methylpentenyl complexes are used in preparing the corresponding substituted fatty acids and esters; (59) the N-methyl-2-pyrryl complex yields the corresponding substituted ethyl acetate; (60)-(62) p-vinylphenyl complex is used in preparing substituted acetates and propionates.  The products, acids and esters, are of use as perfumes, plasticizers and solvents; vinyl compounds for polymerization with other olefinic compounds to give resins; dialkylamino and tertiary nitrogen-containing compounds for quaternization to give detergents and germicides; highly chlorinated phenyl and biphenylyl compounds for fireproofing and bactericides; naphthylacetic acids and esters for agricultural purposes.