Patent GB-833654-A (GB)
Title: Reactions of organomagnesium chloride reagents
IPC: C07F3/02
Filed: 1956-05-03
Abstract: Substituted alcohols are prepared by reacting with an olefin oxide an organo-magnesium complex R(MgCl)x.nQ and hydrolysing the reaction product, the complex being as defined in, and conditions of reaction as described in Specification 802,517. The complexes are also described in Specifications 776,993, 777,158 and 779,100.  The general reaction is represented <FORM:0833654/IV (b)/1> RR1R11C-COH-R111R1111 + R1R11COH-CRR111R1111.  With x mols. of olefin oxide per mol. of complex, polymeric products are obtained: RR1R11C -CR111R1111(OR1R11C -CR111R1111)x-1OH.  In examples: (1) R is vinyl and ethylene oxide yields b -vinyl ethanol; (2) excess ethylene oxide gives a polymer CH2=CHCH2CH2(OCH2CH2)xOH; (3 propylene oxide gives 2-methyl-3-buten-1-ol; (4) R is phenyl, ethylene oxide giving b -phenyl ethanol; (5) R is thienyl and the product b -2-thienylethanol; (6) 2,3-butylene oxide with the vinyl complex yields 3-vinylbutanol-2; (9) R is phenyl, 7 mols. of ethylene oxide giving phenyl (ethoxy)6 ethanol; (14)-(19) R=p-chlorphenyl and yields with olefin oxides, R substituted alcohols and with 3 mols, ethylene oxide p-chlorophenyl ethoxy-ethoxyethanol; (20)-(25) R is tolyl yielding tolyl substituted alcohols; (26)-(29) R is anisyl or phenetyl; (30) 7 mols. of ethylene oxide with various polychlorphenylphenyl complexes give polychlorphenylethyl mono ethers of hexaethylene glycol; (34) 6 mols. ethylene oxide and polychlor-biphenylyl complexes yield similar monoethers of penta-ethylene glycol; (35) R is a -naphthyl; (36) R is trifluormethylphenyl and vinyl ethylene oxide yields b -vinyl, b -o-trifluormethylphenyl ethanol; (37)-(42) R is dimethyl (or ethyl) aminophenyl and R substituted ethanols or ethyl ethers of hexaethylene glycol are obtained; (43)-(47) R is chlor-tolyl, anisyl or phenetyl; (48) R is ethyltetrachlorphenyl; (49)-(51) R is a -thienyl; (52)-(54) R is 2-pyridyl; (55) R is 2-furyl; (56) R is 5-chlor-2-thienyl; (57)-(58) R is m-fluorphenyl and polyfluorphenyl; (59) -(65) R is benzothiazolyl, benzoxazolyl, quinolyl, and trichlor-pyrimidyl; (66)-(73) R is cyclohexenyl, and various alkenyl yielding unsaturated alcohols; (74)-(75) R is 2-N-methylpyrryl or 4-vinylphenyl.  The products, when phenylethanols or aliphatic vinylic alcohols, are used in perfumes, highly chlorinated alcohols are used as insecticides and fungicides, those containing multiple olefin oxide residues are wetting agents and detergents, those containing amino groups may be converted to quaternary ammonium bromides giving germicidal properties, and vinylic types may be polymerized to yield products used in latex paints.  They may all be converted to esters which may be useful as perfume oils, plasticizers or for polymer formation.ALSO:An organo-magnesium complex R(MgCl)x.nQ, where R is an aryl, vinylic or heterocyclic Q a cyclic ether having 5 or 6 ring atoms of which only one is oxygen, as more fully defined in Specifications 776,993, 777,158, and 779,100, n is 1-3, and x a small integer, is reacted with an olefin oxide and the product hydrolysed to give substituted alcohols.  With a molar excess of olefin oxide, polymers are obtained.  The compound Q is preferably employed as reaction medium.  In Example (2), ethylene oxide in tetrahydrofuran is added to a solution of vinyl magnesium chloride-tetrahydrofuran complex in the same solvent and the product hydrolysed with dilute hydrochloric acid to give a product CH2=CHCH2CH2(OCH2CH2)xOH.