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Limited Quantity | USD 15-60 |
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CAS No. : | 16529-56-9 | MDL No. : | MFCD00042634 |
Formula : | C5H7N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | WBAXCOMEMKANRN-UHFFFAOYSA-N |
M.W : | 81.12 | Pubchem ID : | 27909 |
Synonyms : |
|
Num. heavy atoms : | 6 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.4 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 25.42 |
TPSA : | 23.79 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.87 cm/s |
Log Po/w (iLOGP) : | 1.51 |
Log Po/w (XLOGP3) : | 1.3 |
Log Po/w (WLOGP) : | 1.33 |
Log Po/w (MLOGP) : | 0.9 |
Log Po/w (SILICOS-IT) : | 0.8 |
Consensus Log Po/w : | 1.17 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.1 |
Solubility : | 6.5 mg/ml ; 0.0802 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.4 |
Solubility : | 3.23 mg/ml ; 0.0398 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -0.73 |
Solubility : | 15.1 mg/ml ; 0.186 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.63 |
Signal Word: | Danger | Class: | 3,6.1 |
Precautionary Statements: | P501-P261-P270-P240-P210-P233-P243-P241-P242-P271-P264-P280-P370+P378-P361+P364-P303+P361+P353-P301+P310+P330-P304+P340+P311-P403+P233-P403+P235-P405 | UN#: | 3273 |
Hazard Statements: | H301+H311+H331-H225 | Packing Group: | Ⅱ |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicobalt octacarbonyl; benzene at 130℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dicobalt octacarbonyl; benzene at 130℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(i) LDA, (ii) /BRN= 969135/; Multistep reaction; | ||
With lithium diisopropyl amide 1.) THF, -78 deg C, 30 min; 2.) -78 deg C to RT; Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine at 120℃; for 10h; Yield given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With lithium diisopropyl amide 1.) THF, -78 deg C, 30 min; 2.) -78 deg C to RT; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With phosphorus pentoxide im Vakuum; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
zunaechst auf 60-70,dann auf 95-100; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
zunaechst auf 60-70,dann auf 95-100; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
zunaechst auf 60-70,dann auf 95-100; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
zunaechst auf 60-70,dann auf 95-100; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With aluminum oxide at 85℃; for 18h; | |
at 120℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100 % Chromat. | With potassium phosphate buffer; Escherichia coli SS1001 cells In water at 35℃; for 1h; | |
With water at 35℃; for 1h; Enzymatic reaction; potassium phosphate buffer; | 18 EXAMPLE; 18 Hydrolysis of 2-Methyl-3-Butenitrile to 2-Methyl-3-Butenoic acid by E. coli SS1001 Cells A 5.0 mL suspension of 0.500 g (wet cell paste) E. COLI SS1001 cells (ATCC PTA-1177) in 50 mM potassium phosphate buffer (pH 7.0) was added to a mixture of 4.91 mL of 50 mM potassium phosphate buffer (PH 7.0) and 81.8 mg of 2-methyl-3-butenenitrile (101 mM final concentration), and the resulting suspension stirred at 35 C. Samples (0.100 mL) were mixed with 0.900 mL of 60 mM N-ethylacetamide (HPLC external standard) in 1: 1 ACETONITRILE : methanol, the resulting mixture was mixed, centrifuged, and the supernatant analyzed by HPLC for 2-METHYL- 3-butenenitrile and 2-methyl-3-butenoic acid. After 1 H, the conversion of 2-methyl-3-butenenitrile was 100 %, and 2-methyl-3-butenoic acid was the only product produced over the course of the reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With aluminium trichloride; 4,5-(bis-{di[3,5-di-tert-butyl)phenyl]phosphonito}-9,9-dimethyl-9H-xanthene In toluene at 90℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4,5-(bis-{di[3,5-di-tert-butyl)phenyl]phosphonito}-9,9-dimethyl-9H-xanthene In toluene at 90℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In acetonitrile at 80℃; for 17h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 110 - 130℃; for 14 - 48.2h; | 1; 2; 3; 4 Example 1The reaction was carried out in a 100 mL autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds. The reactor was operated liquid full, which resulted in a working volume of 118 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 130 psia (896 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (100 torr; 13.3 kPa) to separate the reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.5 wt %), 1.6 wt % Phosphite A, and 1.2 wt % Phosphite A oxides, 3PN (82 wt %), 2PN (0.9 wt %), 4PN (1.2 wt %), 2M3BN (1.4 wt %), 2-methyl-2-butenenitriles (2M2BN, 0.7 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (3.5 wt %), and ADN (2.4 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00046:0.963:1.0 and the total flow rates were such that the residence time in the reactor was about 3.4 hours. Flows were maintained for 24 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both high-pressure liquid chromatography (HPLC) for catalyst and by gas chromatography (GC) for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 92.9% of the BD and 96.5% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, and 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%. Example 2The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and removal of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 110° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00055:0.946:1.0 and the total flow rates were such that the residence time in the reactor was about 7.3 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 91.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.1% Example 3The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00025:0.948:1.0 and the total flow rates were such that the residence time in the reactor was about 8.2 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 10.3 wt % of the reaction mixture. 90.9% of the BD and 95.9% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.5%: Example 4The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 130° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00035:0.925:1.0 and the total flow rates were such that the residence time in the reactor was about 2.0 hours. Flows were maintained for 12 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 12.4 wt % of the reaction mixture. 89.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 110 - 130℃; for 14 - 48.2h; | 1; 2; 3; 4 Example 1 The reaction was carried out in a 100 mL autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds. The reactor was operated liquid full, which resulted in a working volume of 118 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 130 psia (896 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (100 torr; 13.3 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.5 wt %) ,1.6 wt % Phosphite A, and 1.2 wt % Phosphite A oxides, 3PN (82 wt %), 2PN (0.9 wt %), 4PN (1.2 wt %), 2M3BN (1.4 wt %), 2-methyl-2-butenenitriles (2M2BN, 0.7 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (3.5 wt %), and ADN (2.4 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00046:0.963:1.0 and the total flow rates were such that the residence time in the reactor was about 3.4 hours. Flows were maintained for 24 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both high-pressure liquid chromatography (HPLC) for catalyst and by gas chromatography (GC) for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 92.9% of the BD and 96.5% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%.Example 2 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and removal of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 110° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00055:0.946:1.0 and the total flow rates were such that the residence time in the reactor was about 7.3 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 91.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.1%.Example 3 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00025:0.948:1.0 and the total flow rates were such that the residence time in the reactor was about 8.2 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 10.3 wt % of the reaction mixture. 90.9% of the BD and 96.9% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.5%.Example 4 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 130° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst precursor composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %) , 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00035:0.925:1.0 and the total flow rates were such that the residence time in the reactor was about 2.0 hours. Flows were maintained for 12 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 12.4 wt % of the reaction mixture. 89.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%. | |
at 110 - 130℃; for 12 - 40h; | 1; 2; 3; 4 Example 1 The reaction was carried out in a 100 mL autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds. The reactor was operated liquid full, which resulted in a working volume of 118 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 130 psia (896 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (100 torr; 13.3 kPa) to separate reaction products from the catalyst.A catalyst composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.5 wt%), 1.6 wt% Phosphite A, and 1.2 wt% Phosphite A oxides, 3PN (82 wt %), 2PN (0.9 wt %), 4PN (1.2 wt %), 2M3BN (1.4 wt %), 2-methyl-2-butenenitriles (2M2BN, 0.7 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (3.5 wt %), and ADN (2.4 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00046:0.963:1.0 and the total flow rates were such that the residence time in the reactor was about 3.4 hours. Flows were maintained for 24 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both high-pressure liquid chromatography (HPLC) for catalyst and by gas chromatography (GC) for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 92.9% of the BD and 96.5% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%.Example 2 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and removal of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 110° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %), 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00055:0.946:1.0 and the total flow rates were such that the residence time in the reactor was about 7.3 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 6.6 wt % of the reaction mixture. 91.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.1%.Example 3 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 120° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %), 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00025:0.948:1.0 and the total flow rates were such that the residence time in the reactor was about 8.2 hours. Flows were maintained for 40 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 10.3 wt % of the reaction mixture. 90.9% of the BD and 96.9% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.5%.Example 4 The reaction was carried out in a 1 liter autoclave fitted with a magnetically driven stirrer and dip legs for the addition of feeds and extraction of product. The product removal dip leg was adjusted to provide a working volume of 750 mL. The reaction temperature was maintained at 130° C. by means of a combination of electrical heating on the outside and passing coolant through an internal coil. Pressure in the reactor was controlled by a manual back-pressure regulator at 100 psia (689 kPa). The exit tube continuously fed a flash-distillation column, which operated under reduced pressure (300 torr; 40 kPa) to separate reaction products from the catalyst.A catalyst composition solution comprised of (Phosphite A)Ni(crotyl)CN (2.8 wt %), 2.1 wt % Phosphite A, and 1.4 wt % Phosphite A oxides, 3PN (83 wt %), 2PN (6.1 wt %), 4PN (0.8 wt %), 2M3BN (1.4 wt %), 2M2BN (0.9 wt %), dimethylsuccinonitrile (1.0 wt %), MGN (0.2 wt %), and ADN (1.7 wt %), was fed continuously and concurrently with BD and HCN to the autoclave such that the molar ratio of Ni:HCN:BD fed was about 0.00035:0.925:1.0 and the total flow rates were such that the residence time in the reactor was about 2.0 hours. Flows were maintained for 12 hours in order to approach a steady state condition. Samples were periodically drawn from the line exiting the reactor and analyzed by both HPLC for catalyst and by GC for nitrile products and byproducts. The 2M3BN was analyzed at 12.4 wt % of the reaction mixture. 89.1% of the BD and 96.3% of the HCN fed to the autoclave was converted into useful products comprised of 2PN, 3PN, 4PN, and 2M3BN. Of the total moles of BD converted, the selectivity to these useful products was 96.7%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 87.7% 2: 1.3% | at 90℃; | |
1: 34.9% 2: 68.8% | In propyl cyanide; propiononitrile at 80℃; for 1 - 3h; | |
1: 31% 2: 59.1% | for 1 - 3h; |
1: 21.7% 2: 59.6% | for 1 - 3h; | |
1: 33.5% 2: 56.9% | for 1 - 3h; | |
1: 18.4% 2: 55.1% | for 1 - 3h; | |
1: 28.8% 2: 51.9% | for 1 - 3h; | |
1: 7.6% 2: 49.9% | for 1 - 3h; | |
1: 7.9% 2: 25.8% | for 1 - 3h; | |
1: 7.4% 2: 23.5% | for 1 - 3h; | |
1: 8.3% 2: 22.4% | for 1 - 3h; | |
1: 11.1% 2: 20.7% | for 1 - 3h; | |
1: 6% 2: 14% | for 1 - 3h; | |
1: 2.5% 2: 8.8% | for 1 - 3h; | |
With (Ra)-3-Me-binaphthalenyl-2,2'-[(o-1,3-dioxanyl-C6H4O)2-P-O]2 In toluene for 4h; | ||
With 4-tert-Butylcatechol; water at 105℃; for 0.666667h; | ||
at 105℃; for 0.75h; | ||
In tetrahydrofuran at 90℃; for 1.83333h; | ||
In tetrahydrofuran at 90℃; for 2.25h; | ||
With 4-tert-Butylcatechol at 105℃; for 0.666667h; | ||
at 105℃; | ||
In tetrahydrofuran at 90 - 115℃; for 2.66667h; | ||
In tetrahydrofuran at 90℃; for 1.86667h; | ||
In tetrahydrofuran at 25 - 115℃; for 3h; | ||
In tetrahydrofuran at 90 - 115℃; for 4.33333h; | ||
In tetrahydrofuran at 90 - 115℃; for 3.25h; | ||
In tetrahydrofuran at 90 - 115℃; for 4.41667h; | ||
In tetrahydrofuran at 90 - 115℃; for 4.75h; | ||
In tetrahydrofuran at 90 - 115℃; for 4.26667h; | ||
In tetrahydrofuran at 90 - 115℃; for 4.35h; | ||
In tetrahydrofuran at 25 - 115℃; for 2.66667h; | ||
In tetrahydrofuran at 25 - 115℃; for 3.25h; | ||
17 Example 17ZnCl2 is at least partially separated from the nickel complex of Examples 1 to 12 then the nickel complex of Ligand A contacts BD and HC≡N in a reaction zone. A catalyst forms to produce 3PN, 2M3BN, or a combination thereof. The same nickel complexes also react with 2M3BN to produce 3PN.Nickel complexes of Ligand B of Example 16 contact HC≡N and BD in a reaction zone. A catalyst forms to produce 3PN, 2M3BN, or a combination thereof. The same nickel complexes also react with 2M3BN to produce 3PN.In the presence of a Lewis acid promoter, like ZnCl2, the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC≡N and 3PN in a reaction zone. A catalyst forms converting greater than 90% of the 3PN to dinitriles comprising ADN, MGN, and ESN, with an ADN distribution of 95-96%. The ADN distribution equals 100%*wt % ADN/(wt % ADN+wt % MGN+wt % ESN), as determined by gas chromatography (GC).In the presence of a Lewis acid promoter, like ZnCl2, the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC≡N and 2PN in a reaction zone. A catalyst forms converting a portion of the 2PN to 3PN, 4PN, and ADN.In the presence of a Lewis acid promoter, like ZnCl2, triphenylboron, or compounds of the chemical formula [Ni(C4H7C≡N)6][(C6H5)3BC≡NB(C6H5)3]2 as disclosed in U.S. Pat. No. 4,749,801, the nickel complexes of Example 16 contact HC≡N and 3PN in a reaction zone. A catalyst forms converting 3PN to dinitriles comprising ADN, MGN, and ESN, wherein ADN is the major dinitrile product. | ||
With zero-nickel catalyst; phosphorus-containing ligand | Example 1 To includeMethyl-3-butenenitrile 3-pentenenitrile was added with calcium hydroxide,The molar ratio of calcium hydroxide to nitrile was 1: 5, the reaction pressure was 0. IMpa, the reaction temperature was 140 ° C, and the reaction was kept for 8 hours. After the reaction,Filter recovery calcium hydroxide cycle applied,The content of 2-methyl-2-butenenitrile in the filtrate was 96%And 2-methyl-2-butenenitrile with a content of more than 99% is separated by distillation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.7% | In propiononitrile at 125℃; for 0 - 3h; | |
1.4% | for 0 - 3h; | |
1.2% | for 0 - 3h; |
1% | for 0 - 3h; | |
With (Ra)-[1,1']-binaphthalenyl-2,2'-bis[(o-iPr-C6H4)2-phosphite] In toluene at 100℃; | ||
at 130℃; for 2h; | 19; 20; 21; 22; 23; 24; 25 Examples 19-25 50 mmol of 2-methyl-3-butenenitrile (2M3BN) were in each case reacted with catalyst solution C1-6 from Examples 13-18 (0.2 mmol of Ni) at 130° C. for 2 hours. To avoid decomposition processes caused by air and moisture, the reactions were carried out in a closed system. Conversion and selectivity were determined by GC after the reaction was complete. For comparison, the procedure was repeated using a solution of the Ni(m-/p-tolyl phosphite) complex (m/p-tolyl phosphite:Ni=18:1, 0.7% by weight of Ni(0), preparation of the solution of the complex analogous to C1-6 from m/p-tolyl phosphite and nickel powder in the presence of 3-pentenenitrile) under identical conditions (50 mmol of 2M3BN, 0.2 mmol of Ni, 130° C., 2 h) (Example 25). | |
at 130℃; | In einen Rührkessel wurden 97 G DES KATALYSATORS NI-TETRAKIS- (M/P-TOLYL-)- (O-ISOPROPYL- phenyl) phosphit vorgelegt. Zu diesem Katalysator wurden bei 130 OC Reaktortempera- tur kontinuierlich 80 g/h flüssiges 2-METHYL-3-BUTENNITRIL ZUGEFAHREN. MITTELS EINER VAKU- umpumpe wurde ein Druck von 750-800 mbar eingestellt. Durch einen Thermostaten mit einer T = 143 °C wurde genügend Energie zugeführt, um 80 g/h eines Nitrilgemi- sches bestehend aus 2-METHYL-3-BUTENNITRIL (No.2M3BN") UND 3-PENTENNITRIL (No.3PN") (ZU- SAMMENSETZUNG üBER DIE ZEIT SIEHE GRAPHIK 1) GASFöRMIG ABZUFüHREN. DER REAKTORIN- halt betrug konstant 225 ml. Das Nitrilgemisch wurde anschließend bei Normaldruck in 2-Methyl-3-butennitril (Kopf) und 3-PENTENNITRIL (Sumpf) AUFGETRENNT. Die Gemischzusammensetzung ist in Graphik 1 aufgeführt. | |
at 115℃; for 3h; | ||
at 25 - 115℃; for 4h; | ||
17 Example 17ZnCl2 is at least partially separated from the nickel complex of Examples 1 to 12 then the nickel complex of Ligand A contacts BD and HC≡N in a reaction zone. A catalyst forms to produce 3PN, 2M3BN, or a combination thereof. The same nickel complexes also react with 2M3BN to produce 3PN.Nickel complexes of Ligand B of Example 16 contact HC≡N and BD in a reaction zone. A catalyst forms to produce 3PN, 2M3BN, or a combination thereof. The same nickel complexes also react with 2M3BN to produce 3PN.In the presence of a Lewis acid promoter, like ZnCl2, the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC≡N and 3PN in a reaction zone. A catalyst forms converting greater than 90% of the 3PN to dinitriles comprising ADN, MGN, and ESN, with an ADN distribution of 95-96%. The ADN distribution equals 100%*wt % ADN/(wt % ADN+wt % MGN+wt % ESN), as determined by gas chromatography (GC).In the presence of a Lewis acid promoter, like ZnCl2, the soluble nickel complexes of Ligand A from bottle reactors of Examples 1 to 12 contact HC≡N and 2PN in a reaction zone. A catalyst forms converting a portion of the 2PN to 3PN, 4PN, and ADN.In the presence of a Lewis acid promoter, like ZnCl2, triphenylboron, or compounds of the chemical formula [Ni(C4H7C≡N)6][(C6H5)3BC≡NB(C6H5)3]2 as disclosed in U.S. Pat. No. 4,749,801, the nickel complexes of Example 16 contact HC≡N and 3PN in a reaction zone. A catalyst forms converting 3PN to dinitriles comprising ADN, MGN, and ESN, wherein ADN is the major dinitrile product. | ||
With aluminum (III) chloride; tri(O-methylphenyl)phosphite at 100℃; for 8h; | 1.1 2-Methyl-3-butenenitrile,Tri-o-tolyl phosphite,Zero - valent nickel catalyst and aluminum trichloride at 50: 10: 1: 1Of the molar ratio is added to the isomerization reactor,Control reaction pressure of 0. IMpa, reaction temperature of 100 ° C,Insulation reaction 8 hours,To give isomerization solution; analysis of isomerization solution of 3-pentenenitrile, 2-methyl-3-butenenitrile,The molar ratio of tri-o-tolyl phosphite, zero-valent nickel catalyst and aluminum trichloride was 48: 2: 10: 1: 1; | |
With aluminum (III) chloride; tri(O-methylphenyl)phosphite; triethylamine at 100℃; for 12h; | 1 2-methyl-3-butenenitrile, tri-o-tolyl phosphite, zero-valent nickel catalyst, aluminum trichloride and triethylamine were treated with 30:5: 1: 1: 0.5 molar ratio is added to the isomerization reactor, the reaction pressure is controlled to 0. 1Mpa, the reaction temperature is 100 ° C, the insulationThe reaction was carried out for 12 hours. After completion of the reaction, the product 3-pentenenitrile (3PN) and the unreacted complete 2-methyl-3-butenenitrile(2M3BN). The degradation rate of phosphorus-containing ligand was 1.2% and the conversion of 2M3BN was 95% by high performance liquid chromatography (HPLC)3PN selectivity is 95%. | |
With nickel tris(biphenol)diphosphite complex in 3-pentenitrile at 100℃; for 5h; | 10 Isomerization of 2-methyl-3-butenenitrile General procedure: A portion of nickel catalyst containing solution from Example 1-, 0.50 g, was filtered from the remaining nickel metal and was combined with 5.00 g of 2-methyl-3-butenenitrile. The solution was heated to 100° C. for 5 hours and then cooled to room temperature within 5 minutes and analyzed for conversion of 2-methyl-3-butenenitrile by GC. The resulting 2-methyl-3-butenenitrile conversion after 5 hours is listed in the table 3. Same procedure was used with nickel catalyst containing solutions from examples 2-9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,8-diphenylphosphinotriptycene In 1,4-dioxane at 90℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With 1,8-diphenylphosphinotriptycene In 1,4-dioxane at 90℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.6% | With 1,8-diphenylphosphinotriptycene In 1,4-dioxane at 90℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 98 percent / activity I basic alumina / 18 h / 85 °C 2: 13.2 g / Escherichia coli SS1001 cells immobilized in alginate beads / H2O / 22 h / 35 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 98 percent / activity I basic alumina / 18 h / 85 °C 2: Escherichia coli SS1001 cells immobilized in alginate beads / H2O / 22 h / 35 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 98 percent / activity I basic alumina / 18 h / 85 °C 2: Escherichia coli SS1001 cells immobilized in alginate beads / H2O / 22 h / 35 °C 3: 27 percent Chromat. / Comamonas testosteroni 5-MGAM-4D; potassium phosphate buffer / H2O / 0.25 h / 25 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With C26H23P at 100℃; for 1h; | 1 EXAMPLES 1 and 2; Isomerization of 2M3BN to 3PN Procedure: [0124] 20 mg (0.073 mmol, M=275 g/mol, 1.0 eq) of Ni (cod)2 and 5.0 eq of PNP or PNA ligand are charged to a reactor equipped with a stirrer and placed under an argon atmosphere. Approximately 1 ml (810 mg, d=0.81, M=81.12 g/mol) of degassed 2M3BN is added. The mixture is stirred and maintained at a temperature of 100° C. in a closed system for 1 hour. The reaction medium is cooled to ambient temperature (approximately 20° C.). The concentrations of the various constituents of the reaction medium are determined by analysis by GC (gas chromatography). [0125] The results obtained and calculated from these analyses are collated in Table I below: [TABLE-US-00001] TABLE I Molar DC YD YD Ex. Ligand balance (2M3BN) (3 + 4PN) (2M2BN) 1 PNP 97% 87% 89% 6% 2 PNA 97% 48% 84% 8% | |
With (1S,4R)-4,5-Dimethyl-3,6-diphenyl-1-phospha-bicyclo[2.2.1]hepta-2,5-diene-2-carbaldehyde at 100℃; for 1h; | 2 EXAMPLES 1 and 2; Isomerization of 2M3BN to 3PN Procedure: [0124] 20 mg (0.073 mmol, M=275 g/mol, 1.0 eq) of Ni (cod)2 and 5.0 eq of PNP or PNA ligand are charged to a reactor equipped with a stirrer and placed under an argon atmosphere. Approximately 1 ml (810 mg, d=0.81, M=81.12 g/mol) of degassed 2M3BN is added. The mixture is stirred and maintained at a temperature of 100° C. in a closed system for 1 hour. The reaction medium is cooled to ambient temperature (approximately 20° C.). The concentrations of the various constituents of the reaction medium are determined by analysis by GC (gas chromatography). [0125] The results obtained and calculated from these analyses are collated in Table I below: [TABLE-US-00001] TABLE I Molar DC YD YD Ex. Ligand balance (2M3BN) (3 + 4PN) (2M2BN) 1 PNP 97% 87% 89% 6% 2 PNA 97% 48% 84% 8% | |
at 25 - 115℃; for 1.41667h; |
at 25 - 115℃; for 1.41667h; | ||
at 25 - 115℃; for 1.41667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-pentenenitrile; 2-methyl-2-butene nitrile; 2-METHYL-3-BUTENENITRILE; 3-pentenenitrile With 1-butyl-3-methylimidazolium trifluoromethanesulfonimide at 20℃; for 0.166667h; Stage #2: In n-heptane at 100℃; for 3h; | 1 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. | |
With 1-butyl-2,3-dimethylimidazolium bis-(trifluoromethanesulfonyl)amide at 100℃; for 3h; | 4 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. Tests were carried out without using a nonpolar solvent, such as heptane, in order to obtain a single-phase system. The procedure used is identical to that described above, with the exception of the absence of nonpolar solvent. The results obtained are listed in Table III below: | |
With 1-butyl-3-methylimidazolium trifluoromethanesulfonimide at 100℃; for 3h; | 6 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. Tests were carried out without using a nonpolar solvent, such as heptane, in order to obtain a single-phase system. The procedure used is identical to that described above, with the exception of the absence of nonpolar solvent. The results obtained are listed in Table III below: |
With 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate at 100℃; for 3h; | 5 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. Tests were carried out without using a nonpolar solvent, such as heptane, in order to obtain a single-phase system. The procedure used is identical to that described above, with the exception of the absence of nonpolar solvent. The results obtained are listed in Table III below: | |
Stage #1: 2-pentenenitrile; 2-methyl-2-butene nitrile; 2-METHYL-3-BUTENENITRILE; 3-pentenenitrile With 1-butyl-2,3-dimethylimidazolium bis-(trifluoromethanesulfonyl)amide at 20℃; for 0.166667h; Stage #2: In n-heptane at 100℃; for 3h; | 3 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. | |
Stage #1: 2-pentenenitrile; 2-methyl-2-butene nitrile; 2-METHYL-3-BUTENENITRILE; 3-pentenenitrile With 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate at 20℃; for 0.166667h; Stage #2: In n-heptane at 100℃; for 3h; | 2 Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. | |
Stage #1: 2-pentenenitrile; 2-methyl-2-butene nitrile; 2-METHYL-3-BUTENENITRILE; 3-pentenenitrile With sodium triphenylphosphate at 20℃; for 0.166667h; Stage #2: In n-heptane at 100℃; for 3h; | A Isomerization of 2-METHYL-3-BUTENENITRILE (2M3BN) to Linear Pentenenitriles The tests were carried out according to the following procedure and in a “Radleys” parallel reactor which makes possible simultaneous stirring and simultaneous reflux of 12 glass tubes known as Schlenk tubes. [0110] The following are introduced successively and under argon into a glass tube: [0111] 10 mg (0.036 mmol, 1 equivalent) of Ni(COD)2-66 mg (0.18 mmol, 5 equivalents) of TPPMSNa [0112] 1.5 g of ionic liquid [0113] 400 mg (4.93 mmol, 137 equivalents) of 2M3BN. [0114] The solution is stirred at ambient temperature for 10 minutes and then 1.2 ml of heptane are added in order to obtain a two-phase reaction medium. [0115] The tube is closed, then stirred and heated at 100° C. for 3 hours with head cooling. At the end of the reaction, the tubes are cooled in liquid nitrogen. A known amount of butylbenzene (approximately 40 mg, to act as chromatography internal standard) is added to the two-phase reaction medium, which is diluted and homogenized by the addition of 10 ml of THF. The solution obtained is filtered through a short silica column and injected in gas chromatography (GC). [0116] In the tests carried out according to the above procedure, the starting materials comprise 2M3BN and other products. The molar formulation of these products is given in Table I below (the main components are shown). [TABLE-US-00001] The results obtained with various salts are collated in Table II below. By way of comparison, a test was carried out with a catalyst based on nickel and on a ligand, triphenylphosphine, in a single-phase medium. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With I basic alumina at 85℃; for 18h; | 5 EXAMPLE 5; Isomerization 2-Methyl-3-Butenenitrile to a Mixture of (E)-and (Z)-2-Methyl-2-Butenenitrile A mixture of 50 g of 2-methyl-3-butenenitrile and 5 g of activity I basic alumina was heated with stirring at 85 C. After 18 h, the conversion of 2-methyl-3-butenenitrile to a mixture of (E)-AND (Z)-2- methyl-2-butenenitriles was 100 %. The mixture was cooled to ambient temperature and filtered to yield 49.1 g (98 % isolated yield) of a mixture of (E)-2-METHYL-2-BUTENENITRILE (72 mole %) and (Z)-2-METHYL-2-butenenitrile (28 mole %). | |
With Ni[P[(O-o-tolyl)]3]4; zinc(II) chloride at 100℃; Glovebox; Inert atmosphere; | General procedure: The isomerization reactions were performed in a glove box as follows(also called common conditions): 1 mmol NiL4 catalyst, 5 mmol ZnCl2, 1mmol ligand, and 10 mL cumene were added to a three-necked flask andwere thoroughly mixed. The reaction system was kept at 100°C for 30min, then 2M3BN (72.8 % 2M3BN or 90 % 2M3BN, see Supplementarymaterial) was added to the above system. Samplings (0.1 mL) were takenout every hour, which were centrifuged and analyzed using GC. To testthe effect of 2M2BN and 2PN on the activity of the NiL4 catalyst, acertain amount of 2M2BN or 2PN was added to 90 % 2M3BN to obtain2M3BN with different contents of 2M2BN or 2PN. Herein, to get themixed nitriles containing 20 % 2M2BN, 0.65 mL 2M2BN is added to 3.23mL 90 % 2M3BN. Similarly, 0.80 mL 2PN is added to 3.26 mL 90 %2M3BN to provide the mixed nitriles containing 20 % 2PN. (see Supplementarymaterial) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene at 145℃; for 1 - 17.3h; Gas phase; | 6 An empty 0.25-inch (0.64 cm) diameter, 15-inch (37.5 cm) long stainless steel tubular reactor was placed in a nitrogen-filled glove box. A plug of glass wool was placed in the bottom end of the reactor, followed by the amount and type of Ni(0) catalyst shown in Table 1. A thermocouple was inserted into the top of the reactor. Both ends of the reactor were sealed with metal fittings, and the reactor was removed from the glove box and connected to stainless steel reactor feed lines purged with nitrogen. The feed streams of nitrogen, butadiene (BD), HCN and toluene solvent were preheated to 145°C to ensure complete vaporization. The reactor was heated in a split tube furnace to the temperatures shown in Table 1. Gaseous effluent from the reactor passed through a heated sampling valve which permitted periodic on-line gas chromatographic analyses of products. Feed solutions of weighed amounts of butadiene in toluene also contained weighed amounts of acetonitrile which served as an internal gas chromatograph (GC) standard. GC analyses were done on a 30 m DB-23 capillary columnn of a 0.32 mm internal diameter, supplied by J&W Scientific, Folsom, California. The stationary phase was cyanopropyl (50%) methylpolysiloxane. Table 1 shows the specific reaction conditions and summarizes the results. | |
In toluene at 145℃; for 2 - 64h; Gas phase; | 8 An empty 0.25-inch (0.64 cm) diameter, 15-inch (37.5 cm) long stainless steel tubular reactor was placed in a nitrogen-filled glove box. A plug of glass wool was placed in the bottom end of the reactor, followed by the amount and type of Ni(0) catalyst shown in Table 1. A thermocouple was inserted into the top of the reactor. Both ends of the reactor were sealed with metal fittings, and the reactor was removed from the glove box and connected to stainless steel reactor feed lines purged with nitrogen. The feed streams of nitrogen, butadiene (BD), HCN and toluene solvent were preheated to 145°C to ensure complete vaporization. The reactor was heated in a split tube furnace to the temperatures shown in Table 1. Gaseous effluent from the reactor passed through a heated sampling valve which permitted periodic on-line gas chromatographic analyses of products. Feed solutions of weighed amounts of butadiene in toluene also contained weighed amounts of acetonitrile which served as an internal gas chromatograph (GC) standard. GC analyses were done on a 30 m DB-23 capillary columnn of a 0.32 mm internal diameter, supplied by J&W Scientific, Folsom, California. The stationary phase was cyanopropyl (50%) methylpolysiloxane. Table 1 shows the specific reaction conditions and summarizes the results. | |
In toluene at 145℃; for 1 - 56h; Gas phase; | 7 An empty 0.25-inch (0.64 cm) diameter, 15-inch (37.5 cm) long stainless steel tubular reactor was placed in a nitrogen-filled glove box. A plug of glass wool was placed in the bottom end of the reactor, followed by the amount and type of Ni(0) catalyst shown in Table 1. A thermocouple was inserted into the top of the reactor. Both ends of the reactor were sealed with metal fittings, and the reactor was removed from the glove box and connected to stainless steel reactor feed lines purged with nitrogen. The feed streams of nitrogen, butadiene (BD), HCN and toluene solvent were preheated to 145°C to ensure complete vaporization. The reactor was heated in a split tube furnace to the temperatures shown in Table 1. Gaseous effluent from the reactor passed through a heated sampling valve which permitted periodic on-line gas chromatographic analyses of products. Feed solutions of weighed amounts of butadiene in toluene also contained weighed amounts of acetonitrile which served as an internal gas chromatograph (GC) standard. GC analyses were done on a 30 m DB-23 capillary columnn of a 0.32 mm internal diameter, supplied by J&W Scientific, Folsom, California. The stationary phase was cyanopropyl (50%) methylpolysiloxane. Table 1 shows the specific reaction conditions and summarizes the results. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene at 100℃; for 3h; | 22 Examples 22-25; Butadiene Hydrocyanation; [0046] 1,3-Butadiene Solution (BD): 1.56 g of BD were dissolved in 2g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0047] HCN Solution: 0.93 g of liquid HCN was weighed into 1.9 g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0048] Catalyst Solution: For a typical multidentate phosphonite ligand 13 mmol of the bidentate ligand and 10 mmol of Ni(COD)2 were combined in toluene to generate 3 g of catalyst solution. [0049] In the examples as shown in Table IV, the butadiene hydrocyanation processes were carried out as described below. [0050] To a reaction vessel were added 0.1 ml of the catalyst solution. To this was added 0.18 g of the butadiene solution followed by 0.14g of the HCN solution. The vessel was sealed and placed in a reactor set at 100[deg.] C. Samples were removed after three hours. [0051] Table IV lists the productive conversion of butadiene to 2M3BN, c,t-3PN, 4PN (total PN) and the ratio of 3PN/2M3BN, which was analyzed by GC method. | |
In toluene at 100℃; for 3h; | 23 Examples 22-25; Butadiene Hydrocyanation; [0046] 1,3-Butadiene Solution (BD): 1.56 g of BD were dissolved in 2g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0047] HCN Solution: 0.93 g of liquid HCN was weighed into 1.9 g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0048] Catalyst Solution: For a typical multidentate phosphonite ligand 13 mmol of the bidentate ligand and 10 mmol of Ni(COD)2 were combined in toluene to generate 3 g of catalyst solution. [0049] In the examples as shown in Table IV, the butadiene hydrocyanation processes were carried out as described below. [0050] To a reaction vessel were added 0.1 ml of the catalyst solution. To this was added 0.18 g of the butadiene solution followed by 0.14g of the HCN solution. The vessel was sealed and placed in a reactor set at 100[deg.] C. Samples were removed after three hours. [0051] Table IV lists the productive conversion of butadiene to 2M3BN, c,t-3PN, 4PN (total PN) and the ratio of 3PN/2M3BN, which was analyzed by GC method. | |
In toluene at 100℃; for 3h; | 24 Examples 22-25; Butadiene Hydrocyanation; [0046] 1,3-Butadiene Solution (BD): 1.56 g of BD were dissolved in 2g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0047] HCN Solution: 0.93 g of liquid HCN was weighed into 1.9 g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0048] Catalyst Solution: For a typical multidentate phosphonite ligand 13 mmol of the bidentate ligand and 10 mmol of Ni(COD)2 were combined in toluene to generate 3 g of catalyst solution. [0049] In the examples as shown in Table IV, the butadiene hydrocyanation processes were carried out as described below. [0050] To a reaction vessel were added 0.1 ml of the catalyst solution. To this was added 0.18 g of the butadiene solution followed by 0.14g of the HCN solution. The vessel was sealed and placed in a reactor set at 100[deg.] C. Samples were removed after three hours. [0051] Table IV lists the productive conversion of butadiene to 2M3BN, c,t-3PN, 4PN (total PN) and the ratio of 3PN/2M3BN, which was analyzed by GC method. |
In toluene at 100℃; for 3h; | 25 Examples 22-25; Butadiene Hydrocyanation; [0046] 1,3-Butadiene Solution (BD): 1.56 g of BD were dissolved in 2g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0047] HCN Solution: 0.93 g of liquid HCN was weighed into 1.9 g of toluene. The resulting solution was stored in a sealed vessel at -35[deg.] C. until used. [0048] Catalyst Solution: For a typical multidentate phosphonite ligand 13 mmol of the bidentate ligand and 10 mmol of Ni(COD)2 were combined in toluene to generate 3 g of catalyst solution. [0049] In the examples as shown in Table IV, the butadiene hydrocyanation processes were carried out as described below. [0050] To a reaction vessel were added 0.1 ml of the catalyst solution. To this was added 0.18 g of the butadiene solution followed by 0.14g of the HCN solution. The vessel was sealed and placed in a reactor set at 100[deg.] C. Samples were removed after three hours. [0051] Table IV lists the productive conversion of butadiene to 2M3BN, c,t-3PN, 4PN (total PN) and the ratio of 3PN/2M3BN, which was analyzed by GC method. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene at 100℃; for 4 - 8h; | 26 Examples 26-27; Isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile; [0052] For a typical multidentate phosphonite ligand of the invention 0.008g of Ni(COD)2 was mixed with 0.032 mmol of the ligand and dissolved in 0.8g of toluene. To this was added 0.56 g of 2M3BN. The reactor was closed and heated to 100[deg.] C. The reactions were analyzed after 4 hours and 8 hours reaction time. The reaction mixture was analyzed using standard GC methods. The ratio of 2M3BN to 3PN is listed in Table V. | |
In toluene at 100℃; for 4 - 8h; | 28 Examples 26-27; Isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile; [0052] For a typical multidentate phosphonite ligand of the invention 0.008g of Ni(COD)2 was mixed with 0.032 mmol of the ligand and dissolved in 0.8g of toluene. To this was added 0.56 g of 2M3BN. The reactor was closed and heated to 100[deg.] C. The reactions were analyzed after 4 hours and 8 hours reaction time. The reaction mixture was analyzed using standard GC methods. The ratio of 2M3BN to 3PN is listed in Table V. | |
In toluene at 100℃; for 4 - 8h; | 27 Examples 26-27; Isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile; [0052] For a typical multidentate phosphonite ligand of the invention 0.008g of Ni(COD)2 was mixed with 0.032 mmol of the ligand and dissolved in 0.8g of toluene. To this was added 0.56 g of 2M3BN. The reactor was closed and heated to 100[deg.] C. The reactions were analyzed after 4 hours and 8 hours reaction time. The reaction mixture was analyzed using standard GC methods. The ratio of 2M3BN to 3PN is listed in Table V. |
With 1,8-bis(diisopropylphosphino)triptycene; bis(1,5-cyclooctadiene)nickel (0) In 1,4-dioxane at 60℃; for 4h; | ||
93.5 %Chromat. | With bis(1,5-cyclooctadiene)nickel(0); 1,8-bis(diphenylphosphino)-10-n-octyltriptycene In diethylene glycol diethyl ether; toluene at 100℃; for 1.5h; Inert atmosphere; optical yield given as %de; chemoselective reaction; | |
6.7 g | With C66H84Ni; triphenylphosphine In neat (no solvent) for 3h; Schlenk technique; Inert atmosphere; Heating; | |
67 %Spectr. | With Ni(<SUP>4-tBu</SUP>stb)3; triphenylphosphine at 100℃; for 3h; Schlenk technique; | (£)-Pent-3-enenitrile (45 This compound was prepared following a literature procedure but replacing Ni(COD)2 by complex 6. A Schlenk tube was charged with Ni(4 tBustb)3 (1.04 g, 1.11 mmol, 0.9 mol%) and PPh3 (2.91 g, 11.1 mmol, 9 mol%). 2-methylbut-3- enenitrile (12.5 ml, 10.0 g, 123.3 mmol, 1 equiv.) was added and the reaction was heated to 100 °C for 3 h. After allowing the reaction to cool to room temperature, the solution was opened to air and transferred to a round-bottom flask with non-dry toluene. A distillation was attempted, but failed due to the close boiling points of the product and three if it's isomers. All fractions were combined with the residue of the distillation and CH2Br2 (8.65 ml_, 21.43 g, 123.3 mmol, 1 equiv.) was added as internal standard. The yield was determined by NMR: 67% (6.70g, 82.6 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In hexane | 3 EXAMPLE 3 EXAMPLE 3 Production of ethyl 2-chloro-2-methyl-3-butenoate from 2-methyl-3-butenenitrile via 2-chloro-2-methyl-3-butenenitrile (without isolating and purifying the intermediate--1st "through process" variant) 49.0 g (0.5 mol) of 2-methyl-3-butenenitrile (purity about 83%) in 250 ml of n-hexane are placed in a 1.5 l sulphonation flask equipped with a mechanical stirrer and a thermometer and the mixture is cooled (ice bath) to about 5° C. Thereto there are added in one portion while stirring 400 g (0.7 mol, 1.4 eq.) of fresh 13% Javelle water, which has been pre-cooled to about 5° C., followed by 2.8 g (26 mmol, about 5 mol %) of tetramethyl-ammonium chloride. Then, the mixture is stirred at about +5° C. (ice bath) for about 16 hours and at room temperature for one and a half hours. Thereafter, the hexane phase is separated and the flask is rinsed with 50 ml of n-hexane, which at the same time is used to extract the aqueous phase again. The combined organic phase is now washed with 50 ml of water. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4 EXAMPLE 4 EXAMPLE 4 Production of ethyl 2-chloro-2-methyl-3-butenoate from 2-methyl-3-butenenitrile via 2-chloro-2-methyl-3-butenenitrile (without isolating and purifying the intermediate--2nd "through process" variant) This variant is carried out as the 1st variant above, except that cyclohexane is used in place of n-hexane as the solvent and extraction agent. With the analogous reaction of 49.0 g (0.5 mol) of 2-methyl-3-butenenitrile (purity about 83%) there are obtained at the end of the reaction sequence 63.0 g (75.3% based on 2-methyl-3-butenenitrile) of ethyl 2-chloro-2-methyl-3-butenoate as a colourless liquid which is as dear as water (b.p.: 55°-60° C./15 mbar; with a purity according to GC of 97.1%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17.8% | With hydrogen isocyanide; copper(I) bromide | 7 EXAMPLE 7 EXAMPLE 7 In an experiment conducted similarly to that in Example 4 except that the reactants were 0.8 g. of anhydrous cuprous bromide, 1 ml. of thiophen, 6.5 g. of butadiene and 5 ml. of hydrogen cyanide, and heating was continued for 17 hours at 100°C the conversion of butadiene to mononitriles was 48%, and 3-pentenenitrile was obtained in a yield of 82.2% and 2-methyl-3-butene-nitrile in a yield of 17.8% calculated on the butadiene converted. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3 EXAMPLE 3 About 7.5% of the butadiene was converted to 2-methyl-3-butenenitrile in each experiment. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 3-pentenenitrile In not given mixt. of 2-methyl-3-butenenitrile and 3-pentenenitrile (1/1) was reactedwith Ni complex in presence of Zn dust at 20°C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In tetrahydrofuran byproducts: H2; (Ar); std. Schlenk technique; ligand was added to stirred soln. of Ni complex in THF; stirred at room temp. overnight; solvent removed (vac.); dried for 3 h; | |
In tetrahydrofuran-d8 byproducts: H2; (Ar); std. Schlenk technique; ligand was added to stirred soln. of Ni complex in THF-d8; stirred at room temp. overnight; solvent removed (vac.); dried for 3 h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | In not given 30 min; solvent was evapd.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In tetrahydrofuran byproducts: H2; (Ar); std. Schlenk technique; ligand was added to stirred soln. of Ni complex in THF; solvent removed (vac.); dried for 3 h; | |
In tetrahydrofuran-d8 byproducts: H2; (Ar); std. Schlenk technique; ligand was added to stirred soln. of Ni complex in THF-d8; NMR monitoring; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran-d8 byproducts: H2; (N2); a soln. of Ni complex treated with 2-methyl-3-butenenitrile at -20°C, reacted for 1 d; not isolated, detected by NMR; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 6.1% 2: 4% 3: 4.9% 4: 2.6% | With C14H32P2*2H(1-)*2Ni(1+) In decane at 100℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonia; zinc at 120℃; | 5 Example 5 Example 5 demonstrates the integrated, continuous process of the invention operating at steady state. This Example uses a catalyst composition wherein the multidentate P-containing ligand is the bidentate P-containing ligand referred to as “Phosphite A.” Phosphite A is prepared as described in the section above and is obtained as a ligand mixture comprising Phosphite A and the monodentate phosphites having the following structures: A portion of the catalyst composition is obtained as follows. Phosphite A, anhydrous NiCl2, zinc powder, and 3-pentenenitrile are contacted according to the method disclosed in U.S. Pat. No. 6,893,996, which is incorporated herein by reference, to prepare a fresh catalyst composition. The fresh catalyst composition is treated with ammonia, as disclosed in U.S. Pat. No. 3,766,241 which is incorporated herein by reference, and filtered. The treated fresh catalyst composition, in addition to the catalyst composition of the third stream (see below), is used in the hydrocyanation of 1,3-butadiene (BD).After undergoing distillation to remove 4-tert-butylcatechol and 4-vinyl-1-cyclohexene and drying to remove water, BD containing about 0.30 wt % butene is contacted in a continuous manner with HCN in a 1.02:1 BD:HCN molar ratio in the presence of a catalyst composition comprising Phosphite A and a zero-valent nickel [about 300 ppm zero-valent nickel, Ni(0)] in a 2:1 Phosphite A:Ni molar ratio in a reaction zone consisting of a stainless steel, draft-tube, back-mixed reactor with a holdup time of about 3 hours. The reaction zone is maintained at 120° C. to achieve about 96% conversion of BD and to produce a reaction mixture containing about 2.6 wt % BD, about 3.3 wt % butene, about 0.01 wt % HCN, about 1.9 wt % (Z)-2M2BN, about 6.3 wt % 2M3BN, and about 76.1 wt % total of 3PN and 4PN.The reaction mixture is introduced into the bottom of a distillation column having one theoretical stage of packing above the feed location and continuously distilled. The column head pressure is about 5.8 psia (about 0.4 bar) and the column bottom temperature is 120° C. The first stream obtained is a vapor stream withdrawn from the top of the partial condenser and contains about 40.5 wt % BD, about 45.9 wt % butene, about 2.2 wt % 2M3BN, and about 8.3 wt % total of 3PN and 4PN. The second stream obtained is withdrawn from the reflux back to the column and contains about 8.5 wt % 2M3BN, about 2.1 wt % (Z)-2M2BN, about 79.2 wt % total of 3PN and 4PN, about 1.8 wt % BD, and about 2.4 wt % butene. The column base is heated by circulating the bottoms material through an external steam-heated exchanger. The third stream is obtained by withdrawing a portion from the circulating bottoms material and contains about 2.6 wt % 2M3BN, about 52.4 wt % total 3PN and 4PN, about 10 wt % Phosphite A, and about 0.3 wt % Ni(0).The second stream is introduced into a distillation column such that about 15 theoretical stages are above and about 45 theoretical stages are below the feed location and continuously distilled. The column head pressure is about 16.4 psia (about 1.1 bar) and the column head temperature is 120° C. The fourth stream obtained is a vapor stream withdrawn from the top of the partial condenser and contains about 40.6 wt % BD, about 49.3 wt % butene, about 5.3 wt % 2M3BN, and about 0.2 wt % total of 3PN and 4PN. The fifth stream obtained is withdrawn from the reflux back to the column and contains about 51.7 wt % 2M3BN, about 12.7 wt % (Z)-2M2BN, about 5.2 wt % BD, about 8.0 wt % butene, and about 5.0 wt % total 3PN and 4PN. The sixth stream obtained is withdrawn from the base of the column and contains about 96.1 wt % total 3PN and 4PN and about 0.1 wt % 2M3BN.The fifth stream is introduced near the base of a distillation column having 40 theoretical stages and continuously distilled. The column head pressure is about 15.5 psia (about 1.07 bar) and the column head temperature is 108° C. The seventh stream obtained is a vapor stream withdrawn from the top of the partial condenser and contains about 34.4 wt % BD, about 50.8 wt % butene, and about 3.6 wt % 2M3BN. The eighth stream obtained is withdrawn from the reflux back to the column and contains about 20.6 wt % (Z)-2M2BN, about 29.5 wt % 2M3BN, about 33.5 wt % 4-vinyl-1-cyclohexene, about 4.6 wt % BD, and about 9.4 wt % butene. The ninth stream obtained is withdrawn from the base of the column and contains about 62.9 wt % 2M3BN, about 13.4 wt % (Z)-2M2BN, and about 6.5 wt % total 3PN and 4PN.The fourth and seventh streams are combined and introduced into a condenser at -12° C. and 1.05 bar. The vapor stream exiting the condenser contains about 40.8 wt % BD and about 47.4 wt % butene. A portion of this stream is withdrawn and purged from the 3PN manufacturing process while the remainder is returned to the reaction zone. In this way at least a portion of the butene in the fourth and seventh streams is purged, and at least a portion of the 1,3-butadiene in the fourth and seventh streams is returned to the reaction zone.The first stream and the ninth stream are introduced into a scrubber maintained at -7° C. The liquid stream obtained, containing about 5.6 wt % BD, about 6.4 wt % butene, and about 54.7 wt % 2M3BN, is returned to the reaction zone.At least a portion of the sixth stream is hydrocyanated to produce a dinitrile product comprising adiponitrile.At least a portion of the third stream is returned to the reaction zone to be used in the hydrocyanation of BD.At least a portion of the third stream is introduced into a liquid-liquid extraction process to recover at least a portion of the catalyst composition and at least a portion is returned to the reaction zone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(acetonitrile)copper(I) perchlorate; lithium tert-butoxide; (R,R)-1,2-bis(2,5-diphenylphospholanyl)ethane In tetrahydrofuran at 0℃; for 40h; Inert atmosphere; optical yield given as %ee; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(1,5-cyclooctadiene)nickel(0); tris(para-trifluoromethyl)phenyl phosphine In acetonitrile at 80℃; for 17h; Inert atmosphere; optical yield given as %de; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 85.6 %Chromat. 2: 8.2 %Chromat. | With bis(1,5-cyclooctadiene)nickel(0); 1,8-bis(diphenylphosphino)-10-n-octyltriptycene In diethylene glycol diethyl ether; toluene at 120℃; for 1.5h; Inert atmosphere; optical yield given as %de; chemoselective reaction; | |
With Ni[P[(O-o-tolyl)]3]4; zinc(II) chloride at 100℃; Glovebox; Inert atmosphere; | General procedure: The isomerization reactions were performed in a glove box as follows(also called common conditions): 1 mmol NiL4 catalyst, 5 mmol ZnCl2, 1mmol ligand, and 10 mL cumene were added to a three-necked flask andwere thoroughly mixed. The reaction system was kept at 100°C for 30min, then 2M3BN (72.8 % 2M3BN or 90 % 2M3BN, see Supplementarymaterial) was added to the above system. Samplings (0.1 mL) were takenout every hour, which were centrifuged and analyzed using GC. To testthe effect of 2M2BN and 2PN on the activity of the NiL4 catalyst, acertain amount of 2M2BN or 2PN was added to 90 % 2M3BN to obtain2M3BN with different contents of 2M2BN or 2PN. Herein, to get themixed nitriles containing 20 % 2M2BN, 0.65 mL 2M2BN is added to 3.23mL 90 % 2M3BN. Similarly, 0.80 mL 2PN is added to 3.26 mL 90 %2M3BN to provide the mixed nitriles containing 20 % 2PN. (see Supplementarymaterial) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 125℃; Gas phase; | 1 Example 1 - Shared Catalyst Recovery System and Bidentate Ligand in Reaction Zones Zi, Z2 and Z3.[000311] This Example 1 describes operation of a two-step process for thehydrocyanation of 1 ,3-butadiene to make adiponitrile using a single, shared catalyst purification system for each of the first reaction zone for hydrocyanating 1 ,3-butadiene, (Zi), the second reaction zone for isomerizing mixed pentenenitriles to enrich the mixture in 3-pentenenitrile (Z2) and the third reaction zone for hydrocyanating 3- pentenenitrile to adiponitrile (Z3). These Examples use the term "catalyst loop" to include the identified reaction zone (Z-i, Z2 or Z3) along with its associated catalyst handling equipment that may include process equipment for separating, purifying and recycling the catalyst, as well as adding fresh make-up catalyst.[000312] 1 ,3-butadiene and hydrogen cyanide are charged to a first reaction zone (Zi), as shown in Fig. 1 , where the mixture is contacted in the presence of a first catalyst comprising zero-valent Ni and a phosphite-containing ligand, collectively a catalyst system, to produce a reaction product substantially comprising 3-pentenenitrile (3PN) and 2-methyl-3-butenenitrile (2M3BN). In this Example 1 , the catalyst systemcomprises a bidentate phosphite ligand of Formula III as disclosed herein.[000313] As shown in Fig. 1 , 1 ,3-butadiene reactant is fed into the first reaction zone (Z-i) through line 100, hydrogen cyanide reactant is fed into the first reaction zone (Zi) through line 120, and catalyst is fed into the first reaction zone (Z-i) through line 140. A reaction product stream is taken from the first reaction zone (Zi) through line 122. The reaction product stream in line 122 comprises products, byproducts, unreacted reactants and catalyst, which flows through the first reaction zone (Zi). The reaction product stream 122 is introduced into a separation section 125, to obtain, inter alia, a concentrated catalyst stream 140 and product stream 200 comprising 2-methyl-3- butenenitrile (2M3BN). The separation section 125 comprises one or more distillation columns as shown in Fig. 4. Unreacted hydrogen cyanide and 1 ,3-butadiene may also be separated from reaction products and catalyst in separation section 125, although HCN is usually reacted to extinction during normal unit operation. Unreacted 1 ,3- butadiene is recycled to the first reaction zone (Zi) through lines not shown in Fig. 1. A stream comprising 3-pentenenitrile (3PN) is also withdrawn from separation section 125 through a line not shown in Fig. 1. At least a portion of the catalyst separated from reaction products in separation section 125 is recycled to the first reaction zone (Zi) through line 140.[000314] Subsequent to the reaction in the first reaction zone (Zi), the substantial isomerization of 2M3BN in a second reaction zone (Z2) is conducted in the presence of an isomerization catalyst to produce reaction product comprising substantially 3PN. In this Example 1 , the isomerization catalyst is the same catalyst composition introduced into the first reaction zone (Zi).[000315] As shown in Fig. 1 , a feed comprising 2M3BN is introduced into the second reaction zone (Z2) through line 200. Catalyst is introduced into the second reaction zone (Z2) through line 240. The effluent stream 222 from the second reaction zone (Z2) comprises catalyst and 3PN product. This effluent stream 222 passes into separation section 225 to obtain, inter alia, a 3PN product stream 300 and a concentrated catalyst stream 240. Separation section 225 comprises as series of distillation columns as shown in Fig. 5.[000316] Catalyst recycle systems are shown in Fig. 1 for supplying catalyst to the first reaction zone (Zi), the second reaction zone (Z2) and the third reaction zone (Z3). In this Example, the catalyst recycle systems are different from those shown in Fig. 1. In particular, all three reaction zones in this Example 1 share a single catalyst purification and regeneration system.[000317] In the catalyst recycle system for supplying catalyst to the first reaction zone (Zi), a portion of the concentrated catalyst stream in line 140 is diverted into catalyst purge stream 126. This catalyst purge stream 126 is mixed with stream 226 and charged, along with stream 400, to extraction zone 370. The regenerated catalyst stream 340 then returns to Zi and Z2 as streams 140 and 240, respectively. [000318] In this Example 1 , the first reaction zone (Zi) and second reaction zone (Z2) are not provided with dedicated, isolated catalyst recovery systems. They share the catalyst recovery system as described above for the third reaction zone (Z3). Catalyst purge streams from the first reaction zone (Zi) and the second reaction zone (Z2) are combined and charged to extraction zone 370 as shown in Fig. 1.[000319] In this Example 1 , Lewis acid from the third reaction zone (Z3) carries over to reaction zones Zi and Z2 with recycled catalyst into the shared liquid-liquid extraction zone 370 and the catalyst purification and recovery steps.Example 1 Operating Paramters and Results[000320] Nickel dosage is maintained at about 500 ppm weight (based on total feed) in the first reaction zone (Zi). Ligand dosage is controlled at around 3:1 molar ratio of bidentate ligand:nickel.[000321] Catalyst loss is observed when the bottoms (process side of the reboiler) operating temperature in the butadiene column (the first distillation column after the first reaction zone) exceeds about 125°C. While not to limit the scope of the invention by a recitation of theory, it is believed that the loss of the bidentate ligand component of the catalyst is due to thermal degradation. To maintain ligand inventory, the butadiene column bottoms (the first column after the first reaction zone) is controlled at at 125°C. Initially, this results in an unacceptably high level of unreacted butadiene in the pentenenitrile-enriched bottoms product. In an attempt to solve this problem, the butadiene column is upgraded for vacuum operation, and refrigeration equipment is installed for condensing the overheads. Additional monitoring equipment is installed to detect oxygen intrusion from the atmosphere and mitigate the risk of uncontrolled 1 ,3- butadiene polymerization in the presence of oxygen.[000322] The process is carried out under continuous operating conditions, and the residual Lewis acid concentration in the catalyst increases. The physical state of the Lewis acid in the catalyst does not appear to be critical, and may be present in the catalyst in solution or by entrainment. The presence of the Lewis acid appears to correlate with increased conversion of ,3-butadiene to MGN in the first reaction zone (Z^. This initial conversion of 1 ,3-butadiene to MGN results in loss of ADN yield.; [000352] Fig. 4 is a schematic representation of an example of a distillation train, which may be used as separation section 125, shown in Fig. 1. Stream 122 comprising 3PN, 2M3BN, at least one catalyst, and BD is transferred into an apparatus 810 for distillation. In this apparatus, stream 122 is distilled to obtain a BD-enriched stream 812 and a BD-depleted stream 813 comprising 3PN, 2M3BN, and at least one catalyst. The BD-enriched stream 812 may be recycled the first reaction zone (Z-i ).[000353] The BD-depleted stream 813, which comprises 3PN, 2M3BN, and at least one catalyst is then transferred to another apparatus 820 for further distillation. In this apparatus, stream 813 is distilled to obtain a top product stream 824 enriched in BD, a stream 825, comprising 3PN and 2M3BN, and a bottom product stream 140 enriched in at least one catalyst. Stream 824 enriched in BD may also be recycled to the first reaction zone (Z-i ). If excess dinitriles are present in, for example, apparatus 810 or 820, the catalyst may be less thermally stable, causing nickel to plate out on high- temperature surfaces such as exchanger tubes and reboiler walls. Alternatively, this may trigger precipitation of nickel solids, for example, in the column bottoms. The presence of excess dinitriles may also limit the maximum operating temperature and require closer process control, especially temperature control.[000354] Stream 825, comprising 3PN and 2M3BN, is transferred at least in part to another distillation apparatus 830. In this apparatus, the distillation of stream 825 is distilled to obtain 2M3BN-enriched stream 200 and 2M3BN-depleted stream 838 comprising 3PN. Stream 200 may be obtained at the top region of the distillation apparatus, while the stream 838 may be obtained at the bottom region of the distillation apparatus.[000355] Fig. 4 illustrates one distillation system for distilling the effluent from the first reaction zone (Zi). However, it will be understood that it is within the skill in the art to design and operate other distillation systems to achieve the same or essentially the same results. For example, depending upon the thermal stability of catalyst, it may be possible to combine distillation apparatus 810 and distillation apparatus 820 into a single distillation apparatus, where a BN-enriched stream is withdraw as a top draw, a PN-enriched stream is withdrawn as a side draw, and a catalyst-enriched stream is withdrawn as a bottom draw. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Heating; Gas phase; | 2 This Example 2 illustrates segregated catalyst recovery systems. In particular, this Example 2 illustrates a process using three separate catalyst recovery systems where each of reaction zones Zi, Z2 and Z3 contain catalyst comprising nickel and a bidentate phosphite-containing ligand having the structure of Formula III, above.[000324] In this Example 2, as shown in Fig. 1 , 1 ,3-butadiene reactant is fed into the first reaction zone (Z-i) through line 100, hydrogen cyanide reactant is fed into the first reaction zone (Z-i) through line 120, and catalyst is fed into the first reaction zone (Zi) through line 140. A reaction product stream is taken from the first reaction zone (Zi) through line 122. The reaction product stream in line 122 comprises products, byproducts, unreacted reactants and catalyst, which flows through the first reaction zone (Zi). The reaction product stream 122 is introduced into a separation section 125, to obtain, inter alia, a concentrated catalyst stream 140 and product stream 200comprising 2-methyl-3-butenenitrile (2M3BN). The separation section 125 may comprise one or more distillation columns. An example of separation section 125 is shown in Fig. 4. Unreacted hydrogen cyanide and 1 ,3-butadiene may also be separated from reaction products and catalyst in separation section 125. Unreacted 1 ,3-butadiene may be recycled to the first reaction zone (Zi) through lines not shown in Fig. 1. A stream comprising 3-pentenenitrile (3PN) may also be withdrawn from separation section 125 through a line not shown in Fig. 1. At least a portion of the catalyst separated from reaction products in separation section 125 may be recycled to the first reaction zone (Zi) through line 140.[000325] Subsequent to the reaction in the first reaction zone (Zi), the substantial isomerization of 2M3BN in a second reaction zone (Z2) is conducted in the presence of an isomerization catalyst to produce a reaction product comprising substantially 3PN. The isomerization catalyst is also referred to herein as the second catalyst. The isomerization catalyst may be the same as the catalyst introduced into the first reaction zone (Zi). Optionally, the isomerization catalyst may be different from the catalyst introduced into the first reaction zone (Zi).[000326] As shown in Fig. 1 , a feed comprising 2M3BN is introduced into the second reaction zone (Z2) through line 200. Catalyst is introduced into the second reaction zone (Z2) through line 240. The effluent stream 222 from the second reaction zone (Z2) comprises catalyst and 3PN product. This effluent stream 222 passes into separation section 225 to obtain, inter alia, a 3PN product stream 300 and a concentrated catalyst stream 240. Separation section 225 may comprise one or more distillation apparatus. Fig. 5 shows an example of such a separation section 225.[000327] Catalyst recycle systems are shown in Fig. 1 for supplying catalyst to the first reaction zone (Zi) and the second reaction zone (Z2). These catalyst recycle systems comprise further systems for purifying at least a portion of the catalyst prior to recycle.[000328] In the catalyst recycle system for supplying catalyst to the first reaction zone (Z^, a portion of the concentrated catalyst stream in line 140 is diverted into catalyst purge stream 126.[000329] Catalyst in purge stream 126 is in the form of a solution including impurities, such as reaction byproducts and catalyst degradation byproducts. Catalyst in purge stream 126 is fed to liquid/liquid extraction zone 150 to at least partially purify or regenerate the catalyst. The catalyst is purified or regenerated in that at least some byproducts are removed from the catalyst solution.[000330] A non-polar solvent, such as an alkane, is fed into the liquid/liquid extraction zone 150 through line 130. A polar solvent, which is immiscible with the non-polar solvent, is also fed into the liquid/liquid extraction zone 150 through line 500. In extraction zone 150, there is formed a non-polar phase comprising non-polar solvent and catalyst and a polar phase (e.g., a raffinate) comprising polar solvent and, for example, reaction byproducts and catalyst degradation products. The non-polar phase is taken from extraction zone 150 via line 134 to distillation apparatus 155. The polar phase is taken from extraction zone 150 via line 510 to separation section 1000.[000331] An example of separation section 1000 is described in greater detail in Fig. 2. Separation section 1000 may include, collectively, a series of columns (K-i , K2, K3 and K4) which provide for the removal of certain reaction byproducts and certain catalyst degradation products from the polar solvent. The column bottom of K4 provides polar solvent, which is returned to extraction zone 150, via line 500.[000332] Non-polar solvent is distillatively recovered in distillation apparatus 155 and returned to extraction zone 150, via line 130. Extraction zone 150, line 134, distillation apparatus 155 and line 130, collectively, form a recovery loop for recycling non-polar solvent into extraction zone 150. Extraction zone 150, line 510, separation section 1000 and line 500, collectively, form a recovery loop for recycling polar solvent into extraction zone 150. Additional non-polar solvent and polar solvent may be introduced into extraction zone 150 by lines not shown in Fig. 1. This additional solvent may be added for start up and for make-up of solvent lost during the course of the liquid/liquid extraction step.[000333] Column bottoms from distillation column 155 include partially purified catalyst. This catalyst is partially purified or regenerated in the sense that at least some of the catalyst degradation products and/or reaction byproducts have been separated from the solution containing the catalyst. This partially purified catalyst may be taken from distillation column 155 through line 156 and introduced at any point for recycle into the first reaction zone (Zi). In Fig. 1 , partially purified catalyst may be taken from distillation column 155 through line 156 and transferred into line 146 for introduction into catalyst recycle line 140 for recycle into the first reaction zone (Zi). Fig. 1 shows theintroduction of stream 146 downstream of the take-off stream 126, but this stream may, optionally, be introduced upsteam of the take-off stream 126. Stream 146 may also, optionally, be added to any catalyst-containing stream associated with the first reaction zone (Zi).[000334] The partially purified stream of first catalyst, which is subsequently returned to the first reaction zone (Zi) may be provided with additional zero-valent Ni and/or additional phosphorus-containing ligand. In Fig. 1 , additional zero-valent Ni and/or additional phosphorus-containing ligand may be provided via line 145. Also as shown in Fig. 1 , partially purified stream of first catalyst, which is subsequently fed to the first reaction zone (Z-i), may be provided with additional zero-valent Ni and/or phosphorus- containing ligand via line 145. However, it will be understood, that make-up catalyst may be added via different routes, not shown in Fig. 1. For example, make-up catalyst stream 145 may be charged to other sections of the first reaction zone catalyst loop or, for example, directly to the first reaction zone (Zi).[000335] In this Example 2, the second reaction zone (Z2) is provided with a second catalyst recovery system for supplying catalyst to the second reaction zone (Z2). In this second catalyst recycle system, a portion of the concentrated catalyst stream in line 240 is diverted into catalyst purge stream 226. This catalyst purge stream 226 is fed into liquid/liquid extraction zone 250. A non-polar solvent, such as an alkane, is fed into the liquid/liquid extraction zone 250 through line 230. A polar solvent, which is immiscible with the non-polar solvent, is also fed into the liquid/liquid extraction zone 250 through line 700. Dinitriies from sources not shown in Fig. 1 may be added to extraction zone 250, as needed to accomplish desired phase separation and extraction. For example, a portion of the refined dinitrile product stream from the third reaction zone (Z3) may be used. For example, a side stream (not shown) may be taken from line 500 and introduced into extraction zone 250. In extraction zone 250, there is formed a non- polar phase comprising non-polar solvent and catalyst and a polar phase (e.g., a raffinate) comprising, for example, polar solvent, reaction byproducts and certain catalyst degradation products. The non-polar phase is taken from extraction zone 250 via line 234 to distillation apparatus 255. The polar phase is taken from extraction zone 250 via line 710 to separation section 2000. Separation section 2000 is described in greater detail in Fig. 2.[000336] Separation section 2000 includes, collectively, a series of columns (K-i, K2, K3 and K ) which provide for the separation of certain reaction by-products and catalyst degradation products. The column bottom of K4 provides polar solvent, which is returned to extraction zone 250, via line 700. Additional polar solvent, in the form of adiponitrile, as needed for phase separation, may be provided from adiponitrile produced in the third reaction zone (Z3) through lines not shown in Fig. 1.[000337] Non-polar solvent is distillatively recovered in distillation apparatus 255 and returned to extraction zone 250, via line 230. Extraction zone 250, line 234, distillation column 255 and line 230, collectively, form a recovery loop for recycling non-polar solvent into extraction zone 250. Extraction zone 250, line 710, separation section 2000 and line 700, collectively, form a recovery loop for recycling polar solvent into extraction zone 250.[000338] Column bottoms from distillation column 255 include partially purified catalyst. This catalyst is partially purified or regenerated in the sense that at least some of the catalyst degradation products and/or reaction byproducts have been separated from the solution containing the catalyst. This partially purified catalyst may be taken from distillation apparatus 255 through line 248 for introduction into catalyst recycle line 240 for recycle into the second reaction zone (Z2). Any partially purified stream of catalyst, which is subsequently fed to the second reaction zone (Z2), may be provided with additional zero-valent Ni and/or phosphorus-containing ligand, for example, via line 245. Although not shown in Fig. 1 , line 245 may optionally be fed directly into line 246 or line 248 instead of line 240. Other ways of introducing make-up catalyst are known in the art and may be used.; [000356] Fig. 5 is a schematic representation of an example of a distillation train, which may be used as separation section 225, shown in Fig. 1. The isomerization reaction effluent in stream 222 obtained in the second reaction zone is distilled to recover catalyst and products. Stream 222 is introduced into distillation apparatus 940. A pentenenitrile-enriched stream 942, comprising 3PN, 2M3BN, and (Z)-2M2BN, may be obtained from the distillation apparatus 940. Stream 942 may also comprise other pentenenitriles, selected from 4PN, (E)-2M2BN, or a combination thereof, and optionally dimerized BD compounds having the empirical formula CsHi2, such as VCH and ethylidene cyclohexene isomers. A pentenenitrile-depleted stream 240, enriched in at least one catalyst, may be obtained as the bottom product.[000357] Stream 942 may be distilled to purge at least a portion of the lower-boiling (Z)-2M2BN isomer from the 3PN and 2M3BN reaction product mixture. [000358] Stream 942, comprising 3PN, 2M3BN, and (Z)-2M2BN, is distilled in distillation apparatus 950. Stream 954 is obtained as an overhead product that is enriched in (Z)-2M2BN. Stream 955, comprising 3PN and 2M3BN, is obtained as a bottom product and is depleted in (Z)-2M2BN. "Enriched" and "depleted" in (Z)-2M2BN are relative to its concentration in stream 942.[000359] Stream 954 may also comprise other pentenenitriles, selected from the group comprising 2M3BN, (E)-2M2BN, and optionally dimerized BD compounds having the empirical formula CsHi2, such as VCH and ethylidene cyclohexene isomers. Stream 955 may also comprise other pentenenitriles, selected from the group comprising 4PN, 2PN, and (E)-2M2BN.[000360] The distillation is optionally operated in such a manner to cause dimerized BD compounds to be enriched in stream 954 and depleted in stream 955, both relative to the concentration of dimerized BD compounds in stream 942. Optionally, dimerized BD compounds are enriched in stream 954 through an azeotrope of said compounds with 2M3BN. As a result of the operations described above, stream 954 comprises greater than 1% by weight, for example greater than 5% by weight, for example greater than 10% by weight of 2M3BN, relative to the total mass of stream 954.[000361] Stream 955, comprising 3PN and 2M3BN, may be transferred at least in part to distillation apparatus 960. In this apparatus, the distillation of stream 955 occurs to obtain 2M3BN-enriched stream 967 and a 2M3BN-depleted stream 300 comprising 3PN. Stream 967 may be obtained at the top region of the distillation apparatus, while the stream 300 may be obtained at the bottom region of the distillation apparatus.[000362] Fig. 5 illustrates one distillation system for distilling the effluent from the second reaction zone (Z2). However, it will be understood that it is within the skill in the art to design and operate other distillation systems to achieve the same or essentially the same results. For example, a distillation step to remove low boilers may be inserted into the system, as described above. It is also possible to share equipment used for distilling the effluent from the first reaction zone. For example, a stream comprising 3PN and 2M3BN obtained by distilling the effluent from the second reaction zone (Z2) may be passed to a distillation apparatus, such as distillation apparatus 830, used in the distillation of the effluent form the from the first reaction zone (Zi), to obtain a 3PN- enriched stream and a 2M3BN-enriched stream. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tetrahydrofuran / 50 °C / Inert atmosphere 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / water; N,N-dimethyl-formamide / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: tetrahydrofuran / 50 °C / Inert atmosphere 2.1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / water; N,N-dimethyl-formamide / Inert atmosphere 3.1: triisopropylsilyl chloride; lithium hexamethyldisilazane / tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide / -78 °C / Inert atmosphere 3.2: Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran at 50℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: triisopropylsilyl chloride With n-butyllithium; diisopropylamine In tetrahydrofuran at -78℃; for 0.133333h; Inert atmosphere; Stage #2: 2-METHYL-3-BUTENENITRILE In tetrahydrofuran at -78℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -55 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 °C / Inert atmosphere 2.2: 2 h / -78 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -55 °C / Inert atmosphere 3.1: pyridine / tetrahydrofuran / 2.25 h / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -72 °C / Inert atmosphere 3.1: pyridine / tetrahydrofuran / 2.25 h / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -72 °C / Inert atmosphere 3.1: pyridine / tetrahydrofuran / 2.25 h / 0 - 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -55 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -55 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -72 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium; diisopropylamine / tetrahydrofuran / 0.13 h / -78 °C / Inert atmosphere 1.2: 4 h / -78 °C / Inert atmosphere 2.1: Denmark's dimeric catalyst; tetrachlorosilane; N-ethyl-N,N-diisopropylamine / dichloromethane / 0.08 h / -78 - -72 °C / Inert atmosphere 2.2: 24 h / -72 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20 % de | With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | With alumina at 100℃; for 4h; Inert atmosphere; | 5 Example 5 Example 5 [00035] Example 1 was repeated, except that 2M3BN was the olefin evaluated.; Example 1 [00031] To a 50 mL jacketed glass laboratory extractor (reactor), equipped with a magnetic stir bar, digital stir plate, and maintained at 100 °C and 760 mmHg, was charged 3 grams of aluminum oxide catalyst (Cataox SCFa-140, product of Sasol) having an Na20 content of 5.5 ppm. The reactor was purged with flowing nitrogen for 30 minutes. Then 8 mL of refined c2PN was added to the reactor. To the reactor 0.3 mL of adiponitrile (ADN) was added for use as an internal standard. The reactor was then agitated at 700 rpm, and flow of HCN (10 % in valeronitrile) to the reactor at 0.5 mL per hour was initiated. After 4 hours, the reactor was allowed to cool to room temperature, and any residual HCN was removed from the reactor with flowing nitrogen. Samples were obtained from the reactor, and product analysis was conducted by gas chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis(1,5-cyclooctadiene)nickel (0); 1,4-di(diphenylphosphino)-butane In toluene at 100℃; Schlenk technique; Inert atmosphere; | Isomerization of 2M3BN using Ni(COD)2 and diphosphineligands. General procedure: Toluene (2 mL) was added to a Schlenk tube containingNi(COD)2 (0.020 mmol, 1 equiv.) and the diphosphine ligands(dppm, dppe, dppp, dppb, dpppe or dpph, 0.026 mmol, 1.3 equiv.).The solution was stirred for 20 min at ambient temperature and then heated at 100 °C. 2M3BN (200 mL, 100 equiv.) was added usingan Eppendorf pipette, followed by 50 mL of n-decane as an internalstandard. Samples were taken at set times for GC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With N,N,N,N,-tetramethylethylenediamine; copper dichloride at 10 - 90℃; for 50h; Cooling with ice; | 4 In a 500 mL three-necked round bottom flask equipped with a reflux condenser were successively added 8.31 g (0.062 mol) of cupric chloride,17.15 g (0.148 mol) of tetramethylethylenediamine,194.4 g (2.4 mol) of 2-methyl-3-butenenitrile,Then three bottles into the ice water bath,Weigh 230g (2.0mol) methyldichlorosilane,Drops into the flask,Drip finished in 2h,When the system temperature drops <10 ,Then heated to 90 ° C for 48h.After the reaction was cooled to room temperature,And then to the appropriate temperature to cyanogen-containing chlorosilane distilled off by distillation under reduced pressure,The yield of product was 92% with a purity of 99.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nickel tris(biphenol)diphosphite complex with zinc chloride in trans-2-pentenenitrile at 100℃; | 10 Isomerization of 2-methyl-3-butenenitrile General procedure: A portion of nickel catalyst containing solution from Example 1-, 0.50 g, was filtered from the remaining nickel metal and was combined with 5.00 g of 2-methyl-3-butenenitrile. The solution was heated to 100° C. for 5 hours and then cooled to room temperature within 5 minutes and analyzed for conversion of 2-methyl-3-butenenitrile by GC. The resulting 2-methyl-3-butenenitrile conversion after 5 hours is listed in the table 3. Same procedure was used with nickel catalyst containing solutions from examples 2-9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nickel tris(biphenol)diphosphite complex in cis-2-pentenitrile at 100℃; for 5h; | 10 Isomerization of 2-methyl-3-butenenitrile General procedure: A portion of nickel catalyst containing solution from Example 1-, 0.50 g, was filtered from the remaining nickel metal and was combined with 5.00 g of 2-methyl-3-butenenitrile. The solution was heated to 100° C. for 5 hours and then cooled to room temperature within 5 minutes and analyzed for conversion of 2-methyl-3-butenenitrile by GC. The resulting 2-methyl-3-butenenitrile conversion after 5 hours is listed in the table 3. Same procedure was used with nickel catalyst containing solutions from examples 2-9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triphenyl phosphite; cobalt; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; magnesium chloride at 100℃; for 20h; Inert atmosphere; | 8 Example 8 A mixed nitrile consisting of 2-methyl-3-butenenitrile and 2-pentenenitrile in a volume ratio of 9:1, cobalt, triphenyl phosphite, 1,1'-binaphthyl-2,2'-bis(3,5-dimethylphenyl)phosphine, magnesium chloride, and 2-methylfuran is added to the isomerization reactor at a molar ratio of 30:1:50:10:5:50, the reaction pressure is controlled to be 0.3 Mpa, and the reaction temperature is 100 ° C. During the reaction, nitrogen protection, mechanical agitation,The reaction time is 20 hours, after the reaction is over, unreacted 2-pentenenitrile by distillation under reduced pressure, 2-methyl-3-butenenitrile and the product 3-pentenenitrile were separated. The specific process of vacuum distillation is: tower top temperature 65 ° C, tower kettle temperature 135 ° C, The pressure is 15KPa. It is detected and analyzed by a well-known gas chromatography method. The result was: the conversion of 2-methyl-3-butenenitrile was 85%. The selectivity to 3-pentenenitrile was 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Ni[P[(O-o-tolyl)]3]4; zinc(II) chloride at 100℃; Glovebox; Inert atmosphere; | General procedure: The isomerization reactions were performed in a glove box as follows(also called common conditions): 1 mmol NiL4 catalyst, 5 mmol ZnCl2, 1mmol ligand, and 10 mL cumene were added to a three-necked flask andwere thoroughly mixed. The reaction system was kept at 100°C for 30min, then 2M3BN (72.8 % 2M3BN or 90 % 2M3BN, see Supplementarymaterial) was added to the above system. Samplings (0.1 mL) were takenout every hour, which were centrifuged and analyzed using GC. To testthe effect of 2M2BN and 2PN on the activity of the NiL4 catalyst, acertain amount of 2M2BN or 2PN was added to 90 % 2M3BN to obtain2M3BN with different contents of 2M2BN or 2PN. Herein, to get themixed nitriles containing 20 % 2M2BN, 0.65 mL 2M2BN is added to 3.23mL 90 % 2M3BN. Similarly, 0.80 mL 2PN is added to 3.26 mL 90 %2M3BN to provide the mixed nitriles containing 20 % 2PN. (see Supplementarymaterial) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex; neodecanoic acid In toluene at 100℃; for 1h; Cooling with ice; | 1-10 In this Comparative Example 1, 2M3BN and methyldimethoxy silane were hydrosilylated under the following conditions. Reaction mixtures were prepared with 1.17 mL of methyldimethoxysilane, 1.19 mL of 2M3BN (a 25 % molar excess with respect to the methyldimethoxy silane), and 35 μL of neodecanoic acid in glass tube reactors, each of dimensions 19.7 cm (7.75”) in length and 1.9 cm (”) in diameter. Each tube reactor was chilled on dry ice, and then a solution of Karstedt’s catalyst dissolved in toluene such that the resulting catalyst solution contained 1 weight % platinum was added targeting varying Pt concentrations in the reaction mixture in different tube reactors, as summarized below in Table 2. The cyanide impurity concentration in the 2M3BN was measured to be 45 ppm, which translated to a molar concentration of 140.4 mol cyanide impurity per 106 mol 2M3BN. Hydrosilylation reactions were completed using different amounts of Pt catalyst (1 wt% Pt solution was made using toluene solvent to dilute Karstedt’s catalyst, then varying amounts of 1 wt% Pt solution were added) at 100°C with a reaction time of 1 hour. The effluent was analyzed by GC, and conversion of the limiting reagent is shown in Table 2. This comparative example showed that conversion was significantly hindered as Pt concentration was reduced. |
Tags: 16529-56-9 synthesis path| 16529-56-9 SDS| 16529-56-9 COA| 16529-56-9 purity| 16529-56-9 application| 16529-56-9 NMR| 16529-56-9 COA| 16529-56-9 structure
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H311 | Toxic in contact with skin |
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H371 | May cause damage to organs |
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Code | Phrase |
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H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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