Patent GB-823958-A (GB)
Title: Organomagnesium chloride complexes
IPC: C07F3/02
Filed: 1956-05-09
Abstract: The invention comprises organomagnesium chloride complexes of formula R(MgCl.nQ)x, wherein n is an integer from 1 to 3, x is a small whole number, R is an aliphatic (other than vinylic), cycloaliphatic or aralkyl radical, the magnesium being bonded to a saturated carbon atom and Q is a substituted or unsubstituted cyclic ether having 5 or 6 atoms in the ring, the other ring atoms being carbon with the exception that a substituted nitrogen atom may replace the carbon atom in the 4 position when the ring has 6 atoms, the ring containing not more than one double bond and at least one carbon atom in the ring adjacent to the oxygen atom being free of substituents, the said ether containing no substituent reactive to the organo magnesium chloride or to any of the other components or products of the reaction mixture. Compounds within this definition include tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, 2 - ethoxytetrahydropyran, tetrahydrofurfuryl ether, dihydropyran and N-methylmorpholine.  The magnesium is reacted with the organic chloride in the presence of the compound Q which also acts as reaction medium; if necessary the reaction may be initiated by a small amount of ethyl bromide and/or ether and/or an iodine crystal. The complex may be broken by heating with a high boiling solvent such as xylene, cumene or kerosene, the compound Q distilling off until a solid (which contains residual amounts of Q) is obtained.  The complex may be used in synthetic reactions to give alcohols, ketones, aldehydes, acetals, ketals, hydrocarbons, ethers, carboxylic acids (particularly acetic acid), esters, phenols, mercaptans, sulphinic acids, sulphoxides, sulphones, sulphides, disulphides, alkyl hydrogen selenides, alkyl hydrogen tellurides, organometallic compounds, or thio acids.  Examples 1 to 22 inclusive describe the preparation of the tetrahydrofuran complexes of methyl, ethyl, n-propyl, isopropyl, tert.-butyl, isobutyl, sec.-butyl, n-hexyl, n-heptyl, cyclohexyl, n-octyl, n-decyl, n-lauryl, 2-ethylhexyl, n-octadecyl, cyclopentyl, 1 : 4 - cyclohexylene, 2,2 - difluoroethyl, 2,2 - difluoropropyl, benzyl, allyl and b -methallyl magnesium chlorides.  The other examples describe (using the Grignard reagent as its complex with one or other of the specified Q compounds), the preparation of (23) allyldimethyl carbinol from allylmagnesium chloride and acetone; (24) dibutylundecylcarbinol from butyl magnesium chloride and methyl laurate; (25) methallylphenylketone and dimethallylphenyl carbinol from methallyl magnesium chloride and benzoyl chloride; (26) benzyl methyl ketone from benzyl magnesium chloride and acetonitrile; (27) nonylaldehyde diethyl acetal from n-octyl magnesium chloride and ethyl orthoformate; and phenyl acetaldehyde dimethyl acetal from benzyl magnesium chloride and methyl orthoformate; (28) 2-hexadecanone diethyl ketal from n-tetradecylmagnesium chloride and ethyl orthoacetate; (20) 2-cyclohexyl propanol-1 and 1-cyclohexylpropanol-2 from cyclohexylmagnesium chloride and propylene oxide; (30) 2-methyl hept-2,6-diene and 2 -methylhex-2-ene from isopent-2-en-1-yl magnesium chloride and allyl chloride and ethyl bromide respectively; and 1-tridecene from n -decyl magnesium chloride and allyl chloride; (31) n-tridecyl chloride from a -chloropropyl toluene sulphonate and n-decyl magnesium chloride; (32) 3-methyl heptane from sec.-butyl magnesium chloride and butyl sulphate: (33) methyl ethyl (2-ethyl hexyl) methyl ether from 2-ethyl hexyl magnesium chloride and ethyl chloromethyl methyl ether (itself prepared from hydrochloric acid, methanol and propionaldehyde); (34) di-n-nonyl ether from n-heptyl magnesium chloride and b ,b -dichloroethyl ether; di-iso-amyl ether from isopropyl magnesium chloride and b ,b 1-dichloroethyl ether; (35) ethyl pentadecanoate from n-tridecyl magnesium chloride and ethyl bromacetate; (36) benzyl mercaptan from benzyl magnesium chloride and powdered sulphur; (37) decyl hydrogen selenide from decyl magnesium chloride and powdered selenium; (38) n-amyl alcohol and tridecyl alcohol from oxygen and n-amyl magnesium chloride and tridecyl magnesium chloride respectively; (39) isobutyl sulphinic acid from isobutyl magnesium chloride and sulphur dioxide; (40) decyl sulphonyl chloride from n-decyl magnesium chloride and sulphuryl dichloride; (41) dioctyl sulphide from n-octyl magnesium chloride and sulphur monochloride; (42) triethyl aluminium from ethyl magnesium chloride and aluminium trichloride; tributyl tin chloride and tetrabutyl tin from butyl magnesium chloride and stannic chloride; tribenzyl antimony from benzyl magnesium chloride and antimony trichloride; triallyl boron from allylmagnesium chloride and boron trimethoxide; (43) phenyl acetic acid, dibenzyl ketone and tribenzyl carbinol from benzylmagnesium chloride and carbon dioxide; and (44) undecandithioic acid from decyl magnesium chloride and carbon disulphide. Specification 777,158 is referred to.