Patent GB-885037-A (GB)
Title: Improvements in and relating to the production of acrylic acid esters
IPC: C07C51/14
Filed: 1959-03-25
Abstract: Complex combinations of a nickel halide and organophosphorus acid compounds containing a pentavalent phosphorus atom having a thiono radical and a thiolo radical attached thereto or a nickel salt thereof and which are used in the production of acrylic acid esters from acetylene, carbon monoxide, and an alcohol (see Group IV(b)) may be obtained by mixing a nickel halide, e.g. the bromide, chloride, fluoride or iodide, with the organophosphorus compound, and if desired either component before admixture may be added to the alcohol used in the acrylic ester synthesis.  The organophosphorus compounds or nickel salt thereof have the general formula: <FORM:0885037/III/1> wherein the X's represent R, R1, RZ or R1Z wherein R and R1 are substituted or unsubstituted alkyl or aryl radicals or trihydrocarbyl silanyl radicals, Z is an oxygen atom or an amido group (-NH- or -NR111- where R111 is an alkyl radical containing up to 22 carbon atoms or an aryl radical which may be substituted, or when taken together RZ and R1Z represent a cyclic dioxa nucleus which may be substituted on the carbon atoms, R11 is a hydrogen atom or a nickel atom and n is 1 when R11 is hydrogen or 2 when R11 is nickel.  It is preferred to use equivalent amounts of the each component in forming the catalyst.  Specified catalysts include a complex combination of nickel bromide and O, O1-dicresyldithiophosphoric (or its nickel salt) to which is added mercuric chloride in butyl bromide. Specification 885,038 is referred to.ALSO:Organo compounds containing phosphorus, sulphur and silicon, of the formula <FORM:0885037/IV (a)/1> wherein the X's represent R, R1, RZ or R1Z wherein R and R1 are trihydrocarbylsilanyl radicals and Z is an oxygen atom or an amide radical (-NH- or -NR111-where R111 is an alkyl radical containing up to 22 carbon atoms or an aryl radical which may be substituted) and R11 is H or nickel, are complexed with nickel halides and used as catalysts in the production of acrylic acid esters (see Group IV(b)).  For example, the nickel halide is admixed with O, O1-di[triethyl (or triphenyl) silanyl]dithiophosphoric acid. Specification 885,038 is referred to.ALSO:Acrylic acid esters are obtained by reacting acetylene with carbon monoxide and an alcohol at elevated temperature and under increased pressure in the presence as catalyst of a complex combination of a nickel halide and either an organic sulphur-phosphorus-containing acid compound containing a pentavalent phosphorus atom having a thiono radical and a thiolo radical attached thereto or a nickel salt thereof or in the presence as catalyst of the nickel salt of the phosphorus compound alone.  The catalyst complex may be prepared by admixing a nickel halide, e.g. the chloride, bromide, fluoride or iodide with the organic phosphorus compound or with the nickel salt thereof. Suitable organic phosphorus compounds are those having the formulae (RZ)(R1Z)P(S)SH, (R)(R1Z)P(S)SH and (R)(R1)P(S)SH, respectively wherein R and R1 are unsubstituted or substituted alkyl or aryl radicals or a trihydrocarbyl-silanyl radical, e.g. triethylsilanyl or triphenylsilanyl, and Z is an oxygen atom or an amido radical (-NH- or -NR111) wherein R111 is an alkyl radical containing up to 22 carbon atoms or a substituted or unsubstituted aryl radical) or when taken together RZ and R1Z can represent a cyclic dioxa nucleus which may be substituted and wherein the two oxygen atoms (Z) are connected to the phosphorus atom of the radical >P(S)SH and wherein the carbon atoms of the dioxa nucleus have their other valencies satisfied by hydrogen atoms or other radicals.  Several organophosphorus compounds are specified including some containing chlorine atoms, nitro groups and substituted amido groups, respectively.  Specified alcohols are ethanol, n-butanol, pentanol, 2-ethylhexanol, dodecanol, 3-ethyl 2-pentanol, and ethylene glycol monomethyl ether. Suitable reaction temperatures are from about 90 DEG C. to 250 DEG C. and reaction pressures should preferably exceed 100 p.s.i.g.  It is preferred to employ equimolar amounts of the nickel halide and the organo-phosphorus compound.  The reaction may be carried out batch-wise or in a continuous manner and the acetylene and carbon monooxide can be added separately or as a mixture of gases. Examples are given for the production of ethyl acrylate using various catalysts of the defined type.  In two of the examples the catalyst comprises a complex combination of nickel bromide and O,O1-dicresyldithiophosphoric acid for its nickel salt to which mercuric chloride in butyl bromide has been added. p  Specification 885,038 is referred to.