Patent GB-829243-A (GB)
Title: Preparation of organomagnesium chlorides
IPC: C07F3/02
Filed: 1957-09-18
Abstract: Organomagnesium chlorides are prepared by reacting a substituted or unsubstituted heterocyclic chloride exhibiting aromatic or pseudoaromatic characteristics or a substituted or unsubstituted vinylic chloride with activated magnesium in the presence of an ethylene polyether of formula RdO(CH2CH2O)xRe, wherein x is an integer from 1 to 8, Rd and Re are the same or different and are substituted or unsubstituted hydrocarbon radicals, said heterocyclic chloride containing at least one chlorine atom bonded directly to a carbon atom constituting part of the aromatic or pseudoaromatic heterocyclic system and said vinylic chloride containing at least one chlorine atom bonded directly to a carbon atom which carries an ethylenically-unsaturated double bond, the permissible substituents in the heterocyclic and vinylic chlorides and in Rd and Re being groups which are not reactive with the reactants or reaction products under the conditions of reaction. Preferably Rd and Re are C1-5 aliphatic hydrocarbon groups, phenyl groups, substituted phenyl groups having not more than 5 atoms in each substituting group and not more than 3 substituting groups or aralkyl groups in which the aryl portion is phenyl and having not more than 4 carbon atoms in the alkyl portion.  Specified ethylene polyethers include diethylene glycol diethyl and dimethyl ethers, ethylene glycol dimethyl ether, tri- and tetra-ethylene glycol dimethyl ethers. The Specification includes lists of specified vinylic and heterocyclic compounds.  The process is carried out by activating the magnesium by adding to it a small amount of an alkyl or aryl halide (e.g. ethyl bromide, butyl bromide, isopropyl chloride, allyl chloride, ethyl chloride, allyl bromide, bromobenzene, benzyl chloride or methyl iodine) and a small amount of an alkyl ether, an ethylene polyether or a cyclic polymethylene oxide ether (an iodine crystal may also be added, if desired) and then adding to the activated magnesium the vinylic or heterocyclic chloride dissolved in the ethylene polyether.  The products may be used with or without isolation in a manner analogous to the classic Grignard synthesis, e.g. the preparation of divinyl carbinol from vinyl magnesium chloride in an ethylene polyether solution and ethyl formate.  The preparation of the following is described in the examples: (1) vinyl magnesium chloride; (2) 2-thienyl magnesium chloride; (4) acrylic acid from vinyl magnesium chloride and CO2; (7) 5-chlorothienyl magnesium chloride; (8) a -pyridyl magnesium chloride; (9) 2 - N - methyl - pyrrylmagnesium chloride; (10) 2 -, 6 -, and 8 - quinolyl-magnesium chlorides; (11) 2-benzothiazoyl-magnesium chloride; (12) 2-chloropyrimidyl magnesium chloride; (13) 2-acridyl magnesium chloride; (14) 2-benzoxazoyl magnesium chloride; (15) b -tolylvinyl magnesium chloride; (16) b -naphthylvinyl magnesium chloride; (17) b -phenylmethylvinyl magnesium chloride; (18) b ,b -didecylvinyl magnesium chloride; (19) a -phenyl-b ,b -diethylvinyl magnesium chloride; (20) 2-propenyl magnesium chloride; (21) 4-methyl - 2 - penten-2-yl magnesium chloride; (22) 1-cyclohexen-1-yl magnesium chloride; (23) b -chloro-b -methyl magnesium chloride; (25) a -pyridyl-dithiocarboxylic acid from a -pyridyl magnesium chloride and CS2; (26) phenyl vinyl carbinol from vinyl magnesium chloride and benzaldehyde; (27) 1-(a -thienyl)-l-cyclohexanol from 2-thienyl magnesium chloride and cyclohexanone; (28) 3,6-divinyl-3,6-dihydroxy-octadiene-1,7 from vinyl magnesium chloride and ethyl succinate; (29) ethyl 10,10-divinyl-10-hydroxycaprate from vinyl magnesium chloride and diethyl sebacate; (30) di-(2-thienoyl)-glyoxal from 2-thienyl magnesium chloride and oxalyl chloride; (31) pyridine-2-aldehyde from 2-pyridyl magnesium chloride and dimethyl formamide; (32) 5-chloro-2-thienyl methyl ketone from 5-chloro-2-thienyl magnesium chloride and acetonitrile; (33) ethyl di-(2-buten-2-yl)-hydroxyacetate from 2-buten-2-yl magnesium chloride and diethyl oxalate; (34) b -(2-propen-2-yl)-ethanol from 2-propen-2-yl magnesium chloride and ethylene oxide; (35) b -2-N-methylpyrryl ethanol from 2-N-methylpyrryl magnesium chloride and ethylene oxide; (36) 1,4-pentadiene from vinyl magnesium chloride and allyl chloride; (37) 2-butylthiophene from 2-thienyl magnesium chloride and dibutyl sulphate; (38) 2-(g -chloro-propyl)-furan from 2-furyl magnesium chloride and g -chloro-propyl-p-toluene sulphonate; (39) di-(1-cyclohexenyl methyl)-ether from 1-cyclohexenyl magnesium chloride and chloromethyl ether; (40) ethyl 3-butenoate from vinyl magnesium chloride and ethyl bromoacetate; (41) ethyl-a -furyl acetate from a -furyl magnesium chloride and ethyl chloroacetate; (42) acetaldehyde from vinyl magnesium chloride and CO2-free air; (43) vinyl sulphinic acid from vinyl magnesium chloride and SO2; (44) a -thienyl sulphinic acid from a -thienyl magnesium chloride and SO2; (45) tetravinyl tin from vinyl magnesium chloride and tin tetrachloride; (45a) tetravinyl-germanium from vinyl magnesium chloride and germanium tetrachloride; (45b) trivinylphenyl tin from vinyl magnesium chloride and phenyl tin trichloride; (46) thienyl vinyl tin dichloride and vinyl dithienyl tin chloride from thienyl magnesium chloride and vinyl tin trichloride; (49) trivinyl borane from vinyl magnesium chloride and boron trichloride; (50) trivinyl aluminium from vinyl magnesium chloride and aluminium trichloride; (51) divinyl mercury from vinyl magnesium chloride p  and mercury dichloride; (52) trivinyl antimony from vinyl magnesium chloride and antimony trichloride; and (53) trivinyl arsine from vinyl magnesium chloride and arsenic trichloride.ALSO:Organo magnesium chlorides prepared by reacting activated magnesium with a substituted or unsubstituted heterocyclic chloride (as defined in the Specification) or a substituted or unsubstituted vinylic chloride in the presence of an ethylene polyether of formula RdO(CH2CH2O)xRe wherein x is an integer from 1 to 8 and Rd and Re are the same or different and are substituted or unsubstituted hydrocarbon radicals are used in the preparation of organo silicon compounds. In examples (47) tetravinyl silane is prepared by reacting vinyl magnesium chloride in diethylene glycol diethyl ether with silicon tetrachloride, and (48) trivinyl phenyl silane is prepared by reacting vinyl magnesium chloride in diethylene glycol dimethyl ether with phenyl silicon trichloride.