Patent GB-806710-A (GB)
Title: Reactions of organomagnesium chloride complexes
IPC: C07F3/02
Filed: 1956-06-01
Abstract: A divinyldiketone ViCOCH2COVi (Vi=vinyl radical) polymerizes to form a resin having metal chelating properties.ALSO:Organo-magnesium chloride complexes of the formula R(MgCl)x.nQ, where R is an aryl, vinylic or heterocyclic group, x is 1 or 2, n from 1-3, and Q a heterocyclic ether having 5 or 6 atoms in the ring, of which only one is oxygen and the others carbon except that a substituted nitrogen may replace carbon in the 4-position of a 6-atom ring, the ring containing not more than one double bond and at least one carbon adjacent the oxygen being free of substituents, are reacted with a mono-ester, a polyester, an acyl halide, a nitrile, a cyanogen halide or an orthoester, and the products hydrolysed to give substituted alcohols, ketones, aldehydes, acetals, nitriles or esters.  Where the reactant is an unsaturated ester or nitrile, e.g. an acrylic ester or nitrile, the product may be another ester or nitrile. The complexes are prepared as in Specifications 776,993, 777,158, 779,100 and 792,537, and the reactions effected as in Specification 802,517. Alcohol products may be dehydrated to mono- or poly-olefins.  Thus where R is a chlorphenyl radical and the reactant a mono-ester, the product may be, e.g., <FORM:0806710/IV (b)/1> on dehydration. Similarly where R is heterocyclic the products may be <FORM:0806710/IV (b)/2> Among numerous examples wherein the compound Q is generally tetrahydrofuran but in a few cases is tetrahydropyran or its 2-methoxy or 2-ethoxy derivative, dihydropyran or tetrahydrofurfuryl ethyl ether, the following are typical: (1) R is vinyl and ethyl malonate yields 3,5 - divinyl - 3,5 - dihydroxypentadiene-1,6; (3) ethyl phthalate gives o-phenylene bis(divinyl carbinol); (4), (5) methyl formate gives acrolein or 1,4-pentadiene-3-ol; (7) butyl laurate gives 3-undecyl-1,4-pentadien-3-ol; (9), (10) diethyl oxalate yields ethyl 2-hydroxy-2-vinyl - 3 - butenoate or 3,4 - divinyl - 3,4 - divinyl - 3,4 - dihydroxy - 1,5 - hexadiene; (12) dibutyl succinate gives 3,6 - divinyl - 3,6 - dihydroxy - 1,7 - octadiene which is dehydrated by refluxing with acetic acid+iodine to 3,6-divinyl - 1,3,5,7 - octatetraene; (15), (16) diethyl sebacate yields ethyl 10,10-divinyl-10-hydroxycaprate, dehydrated to 10,10-divinyl-9-decenoate, or 3,12-divinyl-3,12-dihydroxy-1,13-tetradecadiene, dehydrated to 3,12-divinyl - 1,3,11,13 - tetradecatetraene; (18), (19) diethyl terephthalate gives ethyl p-(divinyl-hydroxymethyl) benzoate or p-phenylene bis(divinylcarbinol); (21) methyl anisate gives divinyl (p - methoxyphenyl) carbinol; (22) methyl furoate gives divinyl (a -furyl) carbinol; (23) methyl nicotinate gives divinyl (3-pyridyl) carbinol; (24) butyl 2,4-dichlorphenoxyacetate gives divinyl (2,4-dichlorphenoxymethyl) carbinol; (27) methyl acrylate gives methyl-4-pentenoate; (28), (29) acetyl chloride yields 3-methyl - 1,4 - pentadiene - 3 - ol, dehydrated to 2 - vinyl - 1,3 - butadiene, or methyl vinyl ketone; (35), (36) oxalyl chloride gives methylenepyruvyl chloride or diacrylyl; (37), (38) the acid chloride of monoethyl succinate gives ethyl b -acrylylpropionate or 3,6-dihydroxy-1,7-octadiene; (42), (43) a -furoyl chloride gives vinyl a -furyl ketone or divinyl (a -furyl) carbinol; (44) acetonitrile yields methyl vinyl ketone; (47) acrylonitrile gives b -vinyl propionitrile; (48), (49) fumaronitrile gives 2-vinyl succinonitrile or b -vinyl-b -acrylyl propionitrile; (50), (51) R is phenyl and methyl formate gives benzaldehyde or benzhydrol; (58) methyl levulinate gives 1,1,4-triphenyl-1,4-dihydroxypentane dehydrating to 1,1,4-triphenyl-1,3-pentadiene; (59) methyl acrylate gives methyl b -phenyl propionate; (66), (67) R is p-chlorophenyl and methyl formate yields p-chlorbenzaldehyde or di-(p-chlorphenyl) carbinol; (68) diethyl oxalate gives di-(p-chlorphenyl) hydroxyacetate; (69) dibutyl succinate yields 1,1,4,4 - tetra - (p - chlorphenyl) - 1,4 - dihydroxybutane; (72) oxalyl chloride gives di-p-chlorbenzoyl; (73) butyronitrile gives p-chlorphenyl propyl ketone; (74) R is o-tolyl, methyl formate giving o-tolualdehyde; (80) R is p-tolyl, and furoyl chloride gives p-tolyl a -furyl ketone; (81) R is anisyl, methyl formate giving anisaldehyde; (82) R is phenetyl and ethyl acetate gives di-(phenetyl) methyl carbinol; (84) methyl levulinate yields 1,1,4-tri-(phenetyl)-1,4-dihydroxypentane giving on dehydration 1,1,4-tri-(phenetyl)-1,3-pentadiene; (85) R is anisyl and furoyl chloride gives dianisyl (a -furyl) carbinol yielding 5,5-dianisyl levulinic acid on boiling with acid; (86) R is 3,4-dichlorphenyl, ethyl acetate giving di(3,4-dichlorphenyl) methyl carbinol; (88) dibutyl succinate gives 1,1,4,4-tetra-(3,4-dichlorphenyl)-1,4-dihydroxybutane dehydrated to the corresponding 1,3-butadiene; (98) the corresponding 1,2,4,5-tetrachlorphenyl compounds are formed when R is tetrachlorphenyl; (103) similarly where R is 2,3,4,5,6-pentachlorphenyl; (106) 2-m-xylyl magnesium chloride complex and methyl formate give 2,6-dimethylbenzaldehyde; (112) R is biphenylyl and butyl laurate gives 1,1-di-(biphenylyl)-1-dodecanol; (117) acrylonitrile gives b -biphenylylpropionitrile; (118), (119) R is tri- (or nona-) chlorbiphenylyl, methyl levulinate giving methyl 4-tri- (or nona-) chlorbiphenylyl - 4 - hydroxyvalerate giving the 3-pentenoate on dehydration; (120)-(122) R is naphthyl, reaction as in (4) or (29) yielding naphthaldehyde, dinaphthyl methyl carbinol or naphthyl methyl ketone; (125) R is trifluormethylphenyl (TFM), ethyl acetate giving di-(TFM) methyl carbinol which dehydrates to a ,a  - di - (TFM) ethylene; (126)-(132) ethyl di-(TFM) hydroxyacetate, butyl 4,4-di-(TFM)-4 - hydroxybutyrate, 1,1,6,6 - tetra - (TFM) - 1,6 - dihydroxyhexane, di - (TFM) phenyl carbinol, di - (TFM) a  - furyl carbinol giving on ring opening 5,5-di-(TFM) levulinic acid, methyl 4-(TFM)-4-hydroxyvalerate, and (TFM)-phenyl ketone are prepared as in earlier examples; (133)-(154) R is p-dimethyl (or ethyl) aminophenyl (DMA or DEA) and in analogous manner are prepared DMA-benzaldehyde, di-(DEA)-carbinol, di - (DMA) - 1 - dodecanol, ethyl di-(DEA) hydroxyacetate, tetra-(DMA) ethylene glycol, di-(DMA)-anisyl carbinol, di-(DMA)-(2,4 - dichlorphenoxymethyl) carbinol, DMA-methyl ketone, di-(p-dimethylaminobenzoyl) ethyl b  - (p - dimethylaminobenzoyl) propionate, and like compounds; (165)-(174) R is chloranisyl and analogous reactions are effected; (175)-(184) R is chlorphenetyl; (185) R is ethyltetrachlorphenyl; (186)-(202) R is thienyl; (203)-(219) R is pyridyl; (220)-(236) R is furyl; (237)-(253) R is 5-chlor-2-thienyl; (254)-(265) R is mono-, di-, tri- or pentafluorphenyl; (266) R is 2-benzothiazolyl; (267) 2-benzoxazolyl; (268) 2-methyl-5-benzothiazolyl; (269)-(271) quinolyl; (272) 6-chlor-2-methoxy-9-acridyl; (273)-(275) various chlorpyrimidyl; (276)-(289) various cyclohexenyl, and (chlor) alkenyl; (290) 1,3-butadien-2-yl; (293) N-methyl pyrryl; (292)-(294) 4-vinylphenyl; (296), (297), (302) R is p-chlorphenyl and ethyl perfluorbutyrate (caprate or acetate) yields bis-p-chlorphenyl perfluorpropyl (nonyl or methyl) carbinol.  Products containing unsaturated, e.g. vinyl, groups may be polymerized.  Some have fungicidal properties.  Some tertiary alcohols, especially the chlorine and fluorine derivatives, have insecticidal properties.