Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles
AssigneeE. I. Du Pont de Nemours and Company
InventorsThomas Foo, James Michael Garner, Wilson Tam
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Abstract
Improved liquid phase process useful in the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitrites and to the liquid phase process of isomerization of the nitriles to, among other things, 3- and/or 4-monoalkene linear nitrites. The improvement involves conducting the process in the presence of zero-valent nickel and a multidentate phosphite ligand.
Claims26
An improved process for the liquid phase hydrocyanation of diolefinic compounds and subsequent isomerization of the resulting nonconjugated 2-alkyl-3-monoalkenenitriles comprising reacting an acyclic aliphatic diolefinic compound with a source of HCN;
- the improvement comprising conducting the hydrocyanation and subsequent isomerization in the presence of a catalyst precursor composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VII, VIII, IX and X, as set forth below:
- ##STR51## wherein each R.sup.1 is independently a H, halogen, primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.2 and R.sup.2' are independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- when R.sup.2' is not hydrogen, R.sup.2' cannot be ortho to the oxygen;
- each R.sup.5' is independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.9 is independently H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- and
- each X is independently O or CH(R.sup.4'), wherein R.sup.4' is H, aryl, or a C.sub.1 to C.sub.12 alkyl.
An improved process for the liquid phase hydrocyanation of acyclic aliphatic diolefinic compounds comprising reacting an acyclic aliphatic diolefinic compound with a source of HCN;
- the improvement comprising conducting the hydrocyanation reaction in the presence of a catalyst precursor composition comprising a zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VIII, IX and X, as set forth below:
- ##STR52## wherein each R.sup.1 is independently a H, halogen, primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.2 and R.sup.2' are independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- when R.sup.2' is not hydrogen, R.sup.2' cannot be ortho to the oxygen;
- each R.sup.5' is independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.9 is independently H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- and
- each X is independently O or CH(R4'), wherein R.sup.4' is H, aryl, or a C.sub.1 to C.sub.12 alkyl.
An improved process for the isomerization of a nonconjugated 2-alkyl-3-monoalkenenitrile, the improvement comprising carrying out the isomerization in the presence of a catalyst precursor composition comprising a zero-valent nickel and at least one multidentate phosphite ligand selected from the group consisting of compounds represented by Formulas I, II, III, IV, V, VI, VII, VIII, IX and X, as set forth below:
- ##STR53## wherein each R.sup.1 is independently a H, halogen, primary, secondary, or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.2 and R.sup.2' are independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- when R.sup.2' is not hydrogen, R.sup.2' cannot be ortho to the oxygen;
- each R.sup.5' is independently a H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- each R.sup.9 is independently H, halogen, primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms, OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl, or CO.sub.2 R.sup.3' wherein R.sup.3' is a C.sub.1 to C.sub.12 alkyl, or aryl;
- and
- each X is independently O or CH(R4'), wherein R.sup.4' is H, aryl, or a C.sub.1 to C.sub.12 alkyl.
Dependencies are inferred from the claim text.