Patent GB-820084-A (GB)
Title: Reactions of organomagnesium chloride complexes
IPC: C07C1/32
Filed: 1956-05-04
Abstract: Organo-magnesium chloride complexes 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 carbon of an aromatic or pseudoaromatic ring, R containing no functional group which is reactive under the conditions for formation of the complex, n being 1-3, x 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 except that a substituted nitrogen may replace the carbon in the 4-position when the ring has six 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 organo-magnesium chlorides or any other components or products of the process are described in Specifications 776,993, 777,158 and 779,100. These are reacted with organic halides, sulphonates or sulphates or a or b  haloethers to give hydrocarbons, halogenated hydrocarbons or ethers.  Reaction may be effected in compound Q or inert hydrocarbon as reaction medium preferably between room temperature and the reflux temperature.  R may be defined as <FORM:0820084/IV (a)/1> where the Rs represent H, F, Cl, alkyl, alkenyl, aryl, aralkyl, heterocyclic, alkoxy, aryloxy or dialkylamino.  Alternatively, where x = 1, R may be a vinylic group <FORM:0820084/IV (a)/2> or, where x = 2, a group <FORM:0820084/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.  The general reaction with an organic halide is RMgCl.nQ + R1X --> RR1 + MgClX + nQ with a sulphonate RMgCl.nQ + R1-OSO2-R11 --> RR1 + MgCl.-OSO2-R11 + nQ with a sulphate RMgCl.nQ + R1-OSO2-OR1 --> RR1 + MgCl-OSO2OR1 + NQ and with haloethers RMgClnQ + XCH(R1)OR11 --> RCH(R1)OR11 + nQ RMgCl.nQ + R1CHXCH2OR11 --> R1CH(R)CH2OR11 + nQ With a bifunctional MgCl complex, a typical reaction is R(MgCl)2.nQ + R1X --> R(R1)2 In the following examples, Q is tetrahydrofuran and x is 1 unless specified: (1) the vinyl complex is reacted with 1,2,4-trichlorbenzene to yield 3,4-dichlorstyrene; (2) ethyl bromide similarly gives butene-1; (3) g -chlorpropyl-p-toluene-sulphonate yields 5-chlorpentene-1; (3) allyl chloride gives 1,4-pentadiene; (4) benzyl chloride gives allylbenzene; (6) stearyl chloride gives eicosene-1; (7) vinyl chloride gives 1,3-butadiene; (8) 1,2,4,5-tetrachlorbenzene gives 2,4,5-trichlorstyrene; (9) 1,3,5-trichlorbenzene gives 3,5-dichlorstyrene; (10) 1,4-dichlor-2-brombenzene gives 2,5-dichlorstyrene; (11) dibutyl sulphate gives hexene-1; (12) chlormethyl ether gives diallyl ether; (13) ethyl chlormethyl ether gives ethyl allyl ether; (14)-(15) cyclohexyl (or decyl) chlormethyl ether react similarly; (16) ethylene glycol di(chlormethyl) ether gives ethylene glycol diallylether; (17) ethyl 1-chlorpropyl ether gives ethyl penten-1-yl-3 ether; (18)-(24) various unsaturated ethers are produced similarly; (25) the phenyl complex reacts with ethyl bromide giving ethylbenzene; (26) with g -chlorpropyl p-toluenesulphonate giving g -chlorpropyl benzene; (27)-(29) with appropriate halides giving allyl benzene, diphenylmethane, and stearyl benzene; (30)-(35) with various ethers yielding dibenzyl, n-amyl benzyl, diethylene glycol dibenzyl, decyl 1-phenyl-1-propyl, phenyl b -phenylethyl, and di (b -phenylethyl) ethers; (36)-(42) the p-chlorphenyl complex reacts with various halides, sulphonates, and haloethers giving p-ethylchlorbenzene, p-chlor-(g -chlorpropyl) benzene, chlor-p-allylbenzene, p - chlorphenylphenylmethane, 4 - chlorstyrene, di (p-chlorphenylmethyl) ether, and di[b -(p-chlorphenyl)] ethyl ether; (43)-(54) o- and p-tolyl complexes react in analogous manner; (55)-(66) p-anisyl and phenetyl complexes similarly yield substituted anisoles, phenetoles, and anisyl- or phenetyl-substituted ethers; (67)-(90) di-, tri-, tetra-, and pentachlorphenyl complexes give chlorinated hydrocarbons and chlorphenyl-substituted ethers; (91)-(97) m-2-xylyl complexes give substituted xylenes and sylyl-substituted ethers; (98)-(101) biphenylyl, tri- and nona-chlorbiphenylyl, and naphthyl complexes react similarly; (102)-(105) trifluormethylphenyl complex gives trifluormethylphenyl derivatives; (106)-(117) p-dimethyl (or ethyl) aminophenyl complexes are reacted to give p-dialkylamino-g -chlorpropylbenzene, 1 - dialkylamino - 4 - allyl (and benzyl) benzene, p-dialkylaminostyrene, di (p-dialkylaminophenylmethyl) ether, and cyclohexyl p-dialkylaminophenylmethyl ether; (118) -(126) chlortolyl, chloranisyl, chlorphenetyl, and ethyltetrachlorphenyl complexes give substituted chlortoluenes, chloranisoles, chlorphenetoles, tetrachlorbenzenes and ethers containing these groups as substituents; (127)-(148) 2-thienyl, 2-pyridyl, 2-furyl and 5-chlor-2-thienyl complexes similarly yield substituted thiophenes, pyridines and furans, and thenyl and thienyl-substituted ehters; (149)-(162) m-fluorphenyl, di-, tri-, tetra-, and pentafluorphenyl complexes give substituted fluorbenzenes, including fluorstyrenes, and fluorphenylsubstituted ethers; (163-(165) 2-benzothiazolyl, 2-benzoxazolyl, and 2-methyl-5-benzothithiazolyl complexes react similarly; (166)-(172) 2-, 6-, and 8-quinolyl complexes are employed; (173) 4,5,6-trichlor-2-pyrimidyl complex with allyl chloride gives 2-allyl-4,5,6-trichlorpyrimidine; (174)-(194) cyclohexenyl, 4-methylpenten-1-yl, 1- and 2-propenyl, 1- and 2-butenyl complexes yield corresponding alkenes and dienes, and alkenyl and alkenyl-substituted ethers; (195)-(200) N-methyl-2-pyrryl complexes give substituted N-methylpyrroles, di [(N - methyl - 2 - pyrryl)methyl) ether; and ethyl 1 - (N - methyl - 2 - pyrryl) - 1 - propyl ether; (201)-(210) 4-binylphenyl complexes are reacted to yield substituted styrenes and vinylphenyl-substituted ethers. Olefinic products are of use as polymerization intermediates, others as solvents and plasticizers, detergent intermediates and, in particular, ethers, as perfume ingredients.