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US 5,821,378 AGranted
Hydrocyanation of diolefins and isomerization of nonconjugated 2-alkyl-3-monoalkenenitriles
AssigneeE. I. Du Pont de Nemours and Company
InventorsThomas Foo, Wilson Tam
Life of this patent
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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 nitrites to 3- and/or 4-monoalkene linear nitriles. The improvement involves conducting the process in the presence of zero-valent nickel and a multidentate phosphite ligand. The invention also provides a novel method of making phosphorochloridite.
Claims41
An improved process for the liquid phase hydrocyanation of diolefinic compounds and subsequent isomerization of the resulting nonconjugated 2-alkyl-3-monoalkenenitriles to 3 and/or 4-monoalkene linear nitriles 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, X, XI, XII, XIII, XIV and XV as set forth below:
- ##STR83## wherein each R.sup.1 is independently a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- each R.sup.5 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- ##STR84## wherein each R.sup.6 and R.sup.7 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- and
- each R.sup.8 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- ##STR85## wherein each R.sup.9 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- and
- each R.sup.10 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- ##STR86## wherein each R.sup.14 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms or Si(R.sup.11).sub.3 where R.sup.11 is independently a branched or straight chain alkyl of up to 12 carbon atoms or phenyl or CO.sub.2 R.sup.3" wherein R.sup.3" is a secondary alkyl of up to 6 carbon atoms;
- ##STR87## wherein R.sup.12 is H or a branched or straight chain alkyl of up to 12 carbon atoms;
- and
- each R.sup.13 is independently a branched or straight chain alkyl of up to 12 carbon atoms;
- ##STR88## wherein in Formulas VI through XV each R.sup.1 is independently, H, halogen, a C.sub.1 to C.sub.12 alkyl, or OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl;
- each R.sup.2 is independently a secondary or tertiary hydrocarbyl of 3 to 12 carbon atoms, or OR.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl or benzyl;
- or a cyclic group of the formula ##STR89## forming a five membered ring attached to the phenyl ring, wherein R.sup.w is H or CH.sub.3 and Z is --O-- or --CH.sub.2 --;
- each R.sup.2' is independently H or a primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms at either the meta or para position to the oxygen;
- or CN, CO.sub.2 R.sup.4" or OR.sup.4" wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl at either the meta or para position to the oxygen of the phenoxy ring;
- each R.sup.5' is independently H or a primary or secondary hydrocarbyl of 1 to 3 carbon atoms;
- for Formulas VI and IX, R.sup.5' is optionally OR.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- for Formulas X and XI, R.sup.5' is optionally CO.sub.2 R.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- and
- each X is independently O or CH(R.sup.4'), wherein R.sup.4' is H, a substituted phenyl, or a C.sub.1 to C.sub.12 alkyl;
- and wherein said reaction is carried out to produce 3 and/or 4-monoalkene linear nitriles.
21 more elements
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 to produce a nonconjugated acyclic nitrile;
- 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, VII, VIII, IX, X, XI, XII, XIII, XIV and XV as set forth below:
- ##STR90## wherein each R.sup.1 is independently a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- each R.sup.5 is independently a branched or straight chain alkyl of up to 12 carbon atoms or OR.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl;
- ##STR91## wherein each R.sup.6 and R.sup.7 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- and
- each R.sup.8 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- ##STR92## wherein each R.sup.9 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- and
- each R.sup.10 is independently a branched or straight chain alkyl of up to 12 carbon atoms or OR.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl;
- ##STR93## wherein each R.sup.14 is independently a branched or straight chain alkyl of up to 12 carbon atoms or Si(R.sup.11).sub.3 where R.sup.11 is independently a branched or straight chain alkyl of up to 12 carbon atoms or phenyl or CO.sub.2 R.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl;
- ##STR94## wherein R.sup.12 is H or a branched or straight chain alkyl of up to 12 carbon atoms;
- and
- each R.sup.13 is independently a branched or straight chain alkyl of up to 12 carbon atoms;
- ##STR95## wherein Formulas VI through XV each R.sup.1 is independently, H, halogen, a C.sub.1 to C.sub.12 alkyl, or OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl;
- each R.sup.2 is independently a secondary or tertiary hydrocarbyl of 3 to 12 carbon atoms, or OR.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl or benzyl;
- or a cyclic group of the formula ##STR96## forming a five membered ring attached to the phenyl ring, wherein R.sup.w is H or CH.sub.3 and Z is --O-- or --CH.sub.2 --;
- each R.sup.2' is independently H or a primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms at either the meta or para position to the oxygen;
- or CN, CO.sub.2 R.sup.4" or OR.sup.4" wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl at either the meta or para position to the oxygen of the phenoxy ring;
- each R.sup.5' is independently H or a primary or secondary or tertiary hydrocarbyl of 1 to 6 carbon atoms in;
- for Formulas VI and IX, R.sup.5' is optionally OR.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- for Formulas X and XI, R.sup.5' is optionally CO.sub.2 R.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- and
- each X is independently O or CH(R.sup.4'), wherein R.sup.4' is H, a substituted phenyl, or a C.sub.1 to C.sub.12 alkyl;
- and wherein said reaction is carried out to produce a nonconjugated acyclic nitrile.
21 more elements
An improved process for the isomerization of a nonconjugated 2-alkyl-3-monoalkenenitrile to 3 and/or 4-momoalkene linear nitriles, 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, X, XI, XII, XIII, XIV and XV as set forth below:
- ##STR97## wherein each R.sup.1 is independently a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- each R.sup.5 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- ##STR98## wherein each R.sup.6 and R.sup.7 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- and
- each R.sup.8 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- ##STR99## wherein each R.sup.9 is independently H or a branched or straight chain alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 alkyl;
- and
- each R.sup.10 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms;
- ##STR100## wherein each R.sup.14 is independently a tertiary substituted hydrocarbon of up to 12 carbon atoms or Si(R.sup.11).sub.3 where R.sup.11 is independently a branched or straight chain alkyl of up to 12 carbon atoms or phenyl or CO.sub.2 R.sup.3" wherein R.sup.3" is a secondary alkyl of up to 6 carbon atoms;
- ##STR101## wherein R.sup.12 is H or a branched or straight chain alkyl of up to 12 carbon atoms;
- and
- each R.sup.13 is independently a branched or straight chain alkyl of up to 12 carbon atoms;
- ##STR102## wherein in Formulas VI through XV each R.sub.1 is independently, H, halogen, a C.sub.1 to C.sub.12 alkyl, or OR.sup.3 wherein R.sup.3 is a C.sub.1 to C.sub.12 alkyl;
- each R.sup.2 is independently a secondary or tertiary hydrocarbyl of 3 to 12 carbon atoms, or OR.sup.4" wherein R.sup.4" is C.sub.1 to C.sub.6 alkyl or benzyl;
- or a cyclic group of the formula ##STR103## forming a five membered ring attached to the phenyl ring, wherein R.sup.w is H or CH.sub.3 and Z is --O-- or --CH.sub.2 --;
- each R.sup.2 is independently H or a primary, secondary or tertiary hydrocarbyl of 1 to 12 carbon atoms at either the meta or para position to the oxygen;
- or CN, CO.sub.2 R.sup.4" or OR.sup.4" wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl at either the meta or para position to the oxygen of the phenoxy ring;
- each R.sup.5' is independently H or a primary or secondary hydrocarbyl of 1 to 3 carbon atoms;
- for Formulas VI and IX, R.sup.5' is optionally OR.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- for Formulas X and XI, R.sup.5' is optionally CO.sub.2 R.sup.4", wherein R.sup.4" is a C.sub.1 to C.sub.6 alkyl;
- and
- each X is independently O or CH(R.sup.4'), wherein R.sup.4' is H, a substituted phenyl, or a C.sub.1 to C.sub.12 alkyl;
- and wherein said isomerization is carried out to produce a 3 and/or 4-monoalkene linear nitriles.
20 more elements
Dependencies are inferred from the claim text.