Patent GB-824944-A (GB)
Title: Reactions of organomagnesium chloride reagents
IPC: C07B49/00
Filed: 1956-05-04
Abstract: An organomagnesium chloride complex of formula R(MgCl)xnQ, wherein R is a substituted or unsubstituted aryl radical, a substituted or unsubstituted heterocyclic radical exhibiting aromatic or pseudo-aromatic characteristics which includes in its ring an oxygen, sulphur or tertiary nitrogen atom and which is bound to magnesium through a carbon atom of the ring, R containing no functional group reactive under the conditions for forming the complex, Q is a cyclic ether as defined, x is an integer and n is an indeterminate whole number of the order of 1 to 3, is reacted with a compound of an element M as defined below containing at least one halogen atom attached thereto, the remaining valencies being satisfied by hydrocarbon radicals.  M is defined as beryllium, zinc, cadmium, mercury, aluminium, lead, germanium, arsenic, antimony, bismuth and chromium.  When R is a substituted or unsubstituted aryl radical and x is 1, M is aluminium, bismuth, antimony, arsenic, lead, germanium, zinc, cadmium, mercury or beryllium; when R is a substituted or unsubstituted vinylic radical and x is 1, M is bismuth, germanium, lead, zinc, cadmium, mercury or beryllium.  Compound Q is a substituted or unsubstituted cyclic ether having 5 to 6 atoms in the ring, of which one is oxygen, the other ring atoms being carbon with the exception that a substituted nitrogen atom may replace the 4-carbon 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 any substituents, said ether containing no substituent which reacts with the organomagnesium chloride complex or with other components or products of the reaction mixture.  A list of specified R radicals is included.  The reaction may be expressed:- <FORM:0824944/IV (b)/1> where M, R and n are as above, X is halogen, R is a hydrocarbon radical, m is the valency of M, y is 0 or an integer less than m, a is 1, 2, 3 or 4 and (y + a) has a value of 1 to 4.  The preparation of the following compounds is described: (1) divinyl zinc; (2) di-p-chlorophenyl zinc; (3) bis-(2-pyridyl)-zinc; (4) di-o-tolyl cadmium; (5) bis-(4-methyl-1-penten-2-yl)-cadmium; (6) di-5-chlorothienyl cadmium; (7) diphenylmercury; (8) di-p-anisyl-mercury; (9) bis - (2-buten-2-yl)-mercury (10) bis-(2-benzothiazolyl)-mercury; (11) di-m-tolylberyllium; (12) bis-biphenylylberryllium; (13) di-(1-buten-1-yl) - beryllium; (14) bis - 2 - quinolylberyllium; (15) tris-(p-tolyl)-aluminium; (16) tris-(8-quinolyl)-aluminium; (17) tris-(2-propen-2-yl)-aluminium; (18) tetravinyl lead; (19) tetraphenyl lead; (20) tetra-p-tolyl lead; (21) tetradimethylaminophenyl lead; (22) tetra-2-thienyl lead; (23) tetra-2-propen-2-yl lead; (24-53 inclusive) compounds R1nRaPbC1(4-a-n), wherein R1 is ethyl or phenyl and R is vinylphenyl or thienyl; (54) triphenyl stibine; (55) triphenyl arsine; (56) tris-2-thienylarsine; (57, tris-1-buten-1-yl arsine; (59) tris-2-thienyl-stibine; (60) tris-1-buten-1-yl-stibine; (61) triphenyl - bismuthine; (62) tris - 2 - thienyl-bismuthine; (63) tris-1-buten-1-yl bismuthine and (64) pentaphenylchromium chloride. The preparation of compounds of formula VinA1X(3-n), wherein Vi is a vinylic radical, X is halogen and n is 1, 2 or 3 is disclaimed. Specifications 776,993, 777,158 and 779,100 are referred to.