Structure of 4635-87-4
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| CAS No. : | 4635-87-4 |
| Formula : | C5H7N |
| M.W : | 81.12 |
| SMILES Code : | C/C=C/CC#N |
| English Name : | Pent-3-enenitrile |
* 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 |
|---|---|---|
| 1: 87.7% 2: 1.3% | at 90℃; | |
| 1: 34.9% 2: 68.8% | In Butyronitrile; 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: 56.67% 2: 28.88% | With nickel-tris(2-ethylphenyl)phosphite; bis(4-methoxyphenyl)amine at 50℃; for 5h; Inert atmosphere; | 1.2; 2-3; 1 (2) One-step hydrocyanide reaction method: nickel-phosphite tris(2-ethylphenyl) ester catalyst (1.5mmol), aromatic amine A1 (0.9mmol) and butadiene (2.0mol) were placed in a stainless steel reactor, replaced with nitrogen, and the reaction system was heated to 50 °C; Then the hydrocyanic acid (1.9mol) was slowly added to the kettle with a pump, and the feeding time lasted for 2h; After the feeding is completed, the reaction is continued at 50°C; As the reaction progressed, samples were acquired from the reactor at different times and analyzed, and the results are shown in Table 2. |
| 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 | |
| With tetradentate phosphite ligand-nickel catalyst A at 60 - 90℃; for 1h; | 1 Preparation of adiponitrile: (i) Primary hydrocyanation of butadiene To the reactor containing 5.0 mmol (calculated as nickel) tetradentate phosphite ligand-nickel catalyst A, add 2.5 mol of butadiene (BD) at a reaction temperature of 60-90 ° C and a reaction pressure of 2.0 MPa. 2.0 mol of HCN was slowly added under the conditions, and the reaction was continued for 1.0 h after the addition was completed. After the reaction was completed, samples were taken to analyze the distribution of the product by GC.As a result of the analysis, >99.9% of the starting HCN was converted to 3-pentenenitrile (3PN) and 2-methyl-3-butenenitrile (2M3BN) with an overall selectivity of 96.5% for 3PN and 2M3BN.Meanwhile, the ratio (3PN/2M3BN) of 3-pentenenitrile (3PN) to 2-methyl-3-butenenitrile (2M3BN) was 72.3/27.7. | |
| With porous polymer-nickel catalyst at 75℃; | 1.3.i (i) Hydrocyanation Reaction of Butadiene Into the reactor charged with porous polymer-nickel catalyst A (the content of Ni was 10 mmol), 20.16 g (0.40 mol) of butadiene (BD) was added, and 8.91 g (0.33 mol) of HCN was added dropwise within 0.5 hours. The mixture was reacted for 1 hour under the conditions of the reaction temperature of 75° C. and the reaction pressure of 1.2 MPa. After the reaction was completed, the product was discharged from the bottom of the reactor. After separating the catalyst by filtration, the sample was taken, and the distribution of the product was analyzed by GC to determine the conversion of starting HCN into 3-pentenenitrile (3PN) and 2-methyl-3-butenenitrile (2M3BN) and the ratio of 3-pentenenitrile (3PN) to 2-methyl-3-butenenitrile (2M3BN) (3PN/2M3BN). The results were shown in Table 2-1. | |
| With porous polymer-nickel catalyst at 75℃; | 1.3.i (i) Hydrocyanation Reaction of Butadiene Into the reactor charged with porous polymer-nickel catalyst A (the content of Ni was 10 mmol), 20.16 g (0.40 mol) of butadiene (BD) was added, and 8.91 g (0.33 mol) of HCN was added dropwise within 0.5 hours. The mixture was reacted for 1 hour under the conditions of the reaction temperature of 75° C. and the reaction pressure of 1.2 MPa. After the reaction was completed, the product was discharged from the bottom of the reactor. After separating the catalyst by filtration, the sample was taken, and the distribution of the product was analyzed by GC to determine the conversion of starting HCN into 3-pentenenitrile (3PN) and 2-methyl-3-butenenitrile (2M3BN) and the ratio of 3-pentenenitrile (3PN) to 2-methyl-3-butenenitrile (2M3BN) (3PN/2M3BN). The results were shown in Table 2-1. | |
| With sodium tetrahydroborate; tris(2-biphenylyl) phosphate; nickel dichloride In toluene at 80℃; Inert atmosphere; Overall yield = 65 percent; | 1 Example 1 Add nickel chloride, tris(2, 2'-biphenol) diphosphite, toluene and sodium borohydride into the reactor at a molar ratio of 1:2:100:10, and pass nitrogen into the reactor. When the reaction pressure reaches 2MPa, stir mechanically for 1 hour at a reaction temperature of 30°C to obtain the catalytic system.At a reaction temperature of 80°C, 1, 3-butadiene and hydrocyanic acid were introduced into the catalytic system with a molar ratio of 120:100, and the mixture was mechanically stirred for 5 hours.It was detected and analyzed by a well-known gas chromatography analysis method. The results were: the yield of 3-pentenenitrile and 2-methyl-3-butenenitrile was 65%, and the selectivity of 3-pentenenitrile was 82%. , the selectivity of 2-methyl-3-butenenitrile is 14%. |

| 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. | |
| With porous polymer-nickel catalyst at 150℃; | 1.3.ii (ii) Isomerization of 2-methyl-3-butenenitrile (2M3BN): 2M3BN was obtained by separating the reaction product of step (i), 64.90 g (0.80 mol) of 2M3BN was added into a reactor charged with porous polymer-nickel catalyst A (the content of Ni was 10 mmol). The mixture was reacted at the reaction temperature of 150° C. and the reaction pressure of 0.6 MPa for 2.5 hours. After the reaction was completed, the product was discharged from the bottom of the reactor. After separating the catalyst by filtration, the sample was taken, and the ratio of the product 3PN to 2M3BN was analyzed by GC (with valeronitrile as the internal standard). The results were shown in Table 2-1. | |
| With porous polymer-nickel catalyst at 150℃; | 1.3.ii (ii) Isomerization of 2-methyl-3-butenenitrile (2M3BN): 2M3BN was obtained by separating the reaction product of step (i), 64.90 g (0.80 mol) of 2M3BN was added into a reactor charged with porous polymer-nickel catalyst A (the content of Ni was 10 mmol). The mixture was reacted at the reaction temperature of 150° C. and the reaction pressure of 0.6 MPa for 2.5 hours. After the reaction was completed, the product was discharged from the bottom of the reactor. After separating the catalyst by filtration, the sample was taken, and the ratio of the product 3PN to 2M3BN was analyzed by GC (with valeronitrile as the internal standard). The results were shown in Table 2-1. | |
| With nickel; tris-(o-tolyl)phosphine; lithium chloride at 90℃; Inert atmosphere; | 2-4 Example 4 Add nickel powder, tri-o-tolyl phosphite, acetonitrile and lithium chloride into the reactor at a molar ratio of 1:20:50:5, and pass argon into the reactor until the reaction pressure is 0.1MPa , at a reaction temperature of 60°C, and mechanically stirred for 0.5 hours to obtain the catalytic system.At a reaction temperature of 90°C, add 2-methyl-3-butenenitrile to the catalytic system with a molar ratio of 50 and stir mechanically for 0.5 hours.It was detected and analyzed by a well-known gas chromatography analysis method. The result is: the conversion rate of 2-methyl-3-butenenitrile is 86%, and the number of molecules of raw material converted per mole of catalyst per hour is 172, 3-pentenenitrile selectivity is 99%. | |
| With nickel; C34H40O6P2; zinc(II) chloride at 90℃; | 4-6; 3 Experimental Example 4. Isomerization of 2-methyl-3-butenenitrile using the nickel complex solution prepared in Experimental Example 1. A portion of the nickel catalyst containing solution from Experimental Example 1, 0.50 g, is filtered and charged to a 5 mL glass serum vial, along with 5.00 g of 2-methyl-3 -butenenitrile. The resulting solution is heated to 90° C, and maintained at that temperature for 2.5 h then cooled to room temperature and then analyzed by gas chromatography (GC) within 5 minutes of the conclusion of the experiment. The conversion of 2M3BN is determined to be 83%, and the selectivity to 3 -pentenenitriles is 97%. | |
| With nickel; C53H42O6P2; zinc(II) chloride at 100℃; | 1; 6-10; 1-2 Experimental Example 1. Synthesis of the nickel complex of Ligand A by dissolving metal process. In a glove-box having a argon atmosphere, nickel metal powder, 0.41 g, Ligand A, 1.00 g, zinc chloride, 0.05 g, and 3 -pentenenitrile, 5.10 g are combined in a 10 mL serum bottle sealed with a polytetrafluoroethylene lined septum. The solution is stirred with a magnetic stirrer at 60°C. for 21 hr to afford solution of the nickel complex of Ligand A in a solution of 3-pentenitrile. The concentration of the nickel complex of Ligand A in solution is measured by high-performance liquid chromatography. A portion of the nickel catalyst containing solution from Experimental Example 1, 0.50 g, is filtered and charged to a 5 mL glass serum vial, along with 5.00 g of 2-methy 1-3 -butenenitrile. The resulting solution is heated to 100° C and maintained at that temperature for 5 hr, then cooled to room temperature before being analyzed by gas chromatography (GC) within 5 minutes of the conclusion of the experiment. The conversion of 2M3BN is determined to be 87%, and the selectivity to 3 -pentenenitriles is 94%. | |
| With nickel; C54H70As2N6 at 90℃; | 5-8 Experimental Example 5. Isomerization of 2-methyl-3-butenenitrile using the nickel complex solution prepared in Experimental Example 1. A portion of the nickel catalyst containing solution from Experimental Example 1, 0.50 g, is filtered and charged to a 5 mL glass serum vial, along with 5.00 g of 2-methyl-3-butenenitrile. The resulting solution is heated to 90 °C, and maintained at that temperature for 2.5 h then cooled to room temperature and is then analyzed by gas chromatography (GC) within 5 minutes of the conclusion of the experiment. The conversion of 2M3BN is determined to be 89%, and the selectivity to 3 -pentenenitriles is 93%. | |
| With nickel; C10H22O6P2Si at 100℃; | 3-4 Experimental Example 3. Isomerization of 2-methyl-3-butenenitrile using the nickel complex solution prepared in Experimental Example 1. A portion of the nickel catalyst containing solution from Experimental Example 1, 0.50 g, is filtered and charged to a 5 mL glass serum vial, along with 5.00 g of 2-methyl-3 -butenenitrile. The resulting solution is heated to 100° C and maintained at that temperature for 5 h, then cooled to room temperature and is then analyzed by gas chromatography (GC) within 5 minutes of the conclusion of the experiment. The conversion of 2M3BN is determined to be 81%, and the selectivity to 3 -pentenenitriles is 91%. | |
| With nickel; C78H94O8P2 at 100℃; | 4-6; 3-4 The procedure of Experimental Example 4 is repeated, but the nickel complex of Ligand C is substituted for that of Ligand A. The conversion of 2M3BN Is determined to be 81.3%, and the selectivity to 3 -pentenenitriles is 90.1%. |

| 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 |
|---|---|---|
| at 100℃; for 1h; | 1 Example 1 In the example, the abbreviations that are used have the meanings that are indicated below. [TABLE-US-00001] cod: 1,5-cyclooctadiene. eq: equivalent. 2M3BN: 2-methyl-3-butenenitrile. 2M2BN: 2-methyl-2-butenenitrile. 3PN: 3-pentene nitrile. 4PN: 4-pentene nitrile. 3 + 4PN: 3PN + 4PN. TT (Y): Rate of transformation of the product to be hydrocyanated Y that corresponds to the ratio of the number of transformed moles of Y to the number of initial moles of Y. RR (X): Actual yield of compound X that corresponds to the ratio of the number of formed moles of X to the number of maximum moles of X. RT (X): Selectivity of compound X that corresponds to the ratio of RR (X) to TT (Y). CPG: Gas phase chromatography. ml: milliliter mol: mole. mmol: millimol. [0085] In the tests below, the products used are: [0086] a composition that comprises 2M3BN and other products. The molar formulation of this composition is given in Table 1 below. [TABLE-US-00002] TABLE 1 Component Abbreviation Mol % 2-Methyl-3-butenenitrile 2M3BN 77.89 trans-2-Methyl-2-butenenitrile T2M2BN 11.81 2-Methylbutyronitrile 2MBN 0.03 cis-2-Pentene nitrile C2PN 5.12 4-Vinylcyclohexene 4VCH 0.08 cis-2-Methyl-2-butenenitrile C2M2BN 0.24 4-Pentene nitrile 4PN 0.04 trans-3-Pentene nitrile T3PN 4.69 trans-2-Pentene nitrile T2PN 0.07 cis-3-Pentene nitrite C3PN 0.05 [0087] ligands defined in Table II below: [TABLE-US-00003] TABLE II [CHEMMOL-00002] Tris(2-furyl)phosphine Ligand A [CHEMMOL-00003] Bis(2-furyl)phenylphosphine Ligand B [CHEMMOL-00004] (2-furyl)diphenylphosphine Ligand C [0088] The tests were carried out according to the following operating procedure: [0089] In a pill machine that is equipped with a magnetized bar and under argon, the following are loaded: 20 mg (0.073 mmol; M 275 g/mol; 1.0 equivalent) of Ni(cod)2 and 5.0 equivalents of ligand A, B or C. About 1 ml (810 mg; d=0.81; M=81.12 g/mol) of degassed and anhydrous 2M3BN is added. The mixture is stirred at 100° C. in a closed system for 1 hour, then cooled at ambient temperature. The concentrations of different products are determined by analysis by GPC of the reaction medium. [0090] The results that are obtained are summarized in Table III below: [TABLE-US-00004] TABLE III Example Ligand TT (2M3BN) RT (3 + 4PN) RT (2M2BN) 1 Ligand A 32% 89% 3% 2 Ligand B 72% 92% 1% 3 Ligand C 81% 91% 5% | |
| at 100℃; for 1h; | 3 Example 3 In the example, the abbreviations that are used have the meanings that are indicated below. [TABLE-US-00001] cod: 1,5-cyclooctadiene. eq: equivalent. 2M3BN: 2-methyl-3-butenenitrile. 2M2BN: 2-methyl-2-butenenitrile. 3PN: 3-pentene nitrile. 4PN: 4-pentene nitrile. 3 + 4PN: 3PN + 4PN. TT (Y): Rate of transformation of the product to be hydrocyanated Y that corresponds to the ratio of the number of transformed moles of Y to the number of initial moles of Y. RR (X): Actual yield of compound X that corresponds to the ratio of the number of formed moles of X to the number of maximum moles of X. RT (X): Selectivity of compound X that corresponds to the ratio of RR (X) to TT (Y). CPG: Gas phase chromatography. ml: milliliter mol: mole. mmol: millimol. [0085] In the tests below, the products used are: [0086] a composition that comprises 2M3BN and other products. The molar formulation of this composition is given in Table 1 below. [TABLE-US-00002] TABLE 1 Component Abbreviation Mol % 2-Methyl-3-butenenitrile 2M3BN 77.89 trans-2-Methyl-2-butenenitrile T2M2BN 11.81 2-Methylbutyronitrile 2MBN 0.03 cis-2-Pentene nitrile C2PN 5.12 4-Vinylcyclohexene 4VCH 0.08 cis-2-Methyl-2-butenenitrile C2M2BN 0.24 4-Pentene nitrile 4PN 0.04 trans-3-Pentene nitrile T3PN 4.69 trans-2-Pentene nitrile T2PN 0.07 cis-3-Pentene nitrite C3PN 0.05 [0087] ligands defined in Table II below: [TABLE-US-00003] TABLE II [CHEMMOL-00002] Tris(2-furyl)phosphine Ligand A [CHEMMOL-00003] Bis(2-furyl)phenylphosphine Ligand B [CHEMMOL-00004] (2-furyl)diphenylphosphine Ligand C [0088] The tests were carried out according to the following operating procedure: [0089] In a pill machine that is equipped with a magnetized bar and under argon, the following are loaded: 20 mg (0.073 mmol; M 275 g/mol; 1.0 equivalent) of Ni(cod)2 and 5.0 equivalents of ligand A, B or C. About 1 ml (810 mg; d=0.81; M=81.12 g/mol) of degassed and anhydrous 2M3BN is added. The mixture is stirred at 100° C. in a closed system for 1 hour, then cooled at ambient temperature. The concentrations of different products are determined by analysis by GPC of the reaction medium. [0090] The results that are obtained are summarized in Table III below: [TABLE-US-00004] TABLE III Example Ligand TT (2M3BN) RT (3 + 4PN) RT (2M2BN) 1 Ligand A 32% 89% 3% 2 Ligand B 72% 92% 1% 3 Ligand C 81% 91% 5% | |
| at 100℃; for 1h; | 2 Example 2 In the example, the abbreviations that are used have the meanings that are indicated below. [TABLE-US-00001] cod: 1,5-cyclooctadiene. eq: equivalent. 2M3BN: 2-methyl-3-butenenitrile. 2M2BN: 2-methyl-2-butenenitrile. 3PN: 3-pentene nitrile. 4PN: 4-pentene nitrile. 3 + 4PN: 3PN + 4PN. TT (Y): Rate of transformation of the product to be hydrocyanated Y that corresponds to the ratio of the number of transformed moles of Y to the number of initial moles of Y. RR (X): Actual yield of compound X that corresponds to the ratio of the number of formed moles of X to the number of maximum moles of X. RT (X): Selectivity of compound X that corresponds to the ratio of RR (X) to TT (Y). CPG: Gas phase chromatography. ml: milliliter mol: mole. mmol: millimol. [0085] In the tests below, the products used are: [0086] a composition that comprises 2M3BN and other products. The molar formulation of this composition is given in Table 1 below. [TABLE-US-00002] TABLE 1 Component Abbreviation Mol % 2-Methyl-3-butenenitrile 2M3BN 77.89 trans-2-Methyl-2-butenenitrile T2M2BN 11.81 2-Methylbutyronitrile 2MBN 0.03 cis-2-Pentene nitrile C2PN 5.12 4-Vinylcyclohexene 4VCH 0.08 cis-2-Methyl-2-butenenitrile C2M2BN 0.24 4-Pentene nitrile 4PN 0.04 trans-3-Pentene nitrile T3PN 4.69 trans-2-Pentene nitrile T2PN 0.07 cis-3-Pentene nitrite C3PN 0.05 [0087] ligands defined in Table II below: [TABLE-US-00003] TABLE II [CHEMMOL-00002] Tris(2-furyl)phosphine Ligand A [CHEMMOL-00003] Bis(2-furyl)phenylphosphine Ligand B [CHEMMOL-00004] (2-furyl)diphenylphosphine Ligand C [0088] The tests were carried out according to the following operating procedure: [0089] In a pill machine that is equipped with a magnetized bar and under argon, the following are loaded: 20 mg (0.073 mmol; M 275 g/mol; 1.0 equivalent) of Ni(cod)2 and 5.0 equivalents of ligand A, B or C. About 1 ml (810 mg; d=0.81; M=81.12 g/mol) of degassed and anhydrous 2M3BN is added. The mixture is stirred at 100° C. in a closed system for 1 hour, then cooled at ambient temperature. The concentrations of different products are determined by analysis by GPC of the reaction medium. [0090] The results that are obtained are summarized in Table III below: [TABLE-US-00004] TABLE III Example Ligand TT (2M3BN) RT (3 + 4PN) RT (2M2BN) 1 Ligand A 32% 89% 3% 2 Ligand B 72% 92% 1% 3 Ligand C 81% 91% 5% |
| 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 |
|---|---|---|
| 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 |
|---|---|---|
| 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 |
|---|---|---|
| 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 triphenyl phosphite; triphenylborane; nickel; 1,2-bis-(diphenylphosphino)ethane In benzene at 130℃; for 6h; Inert atmosphere; | 1-8 Example 2 2-methyl-2-butenenitrile, nickel, triphenyl phosphite, 1,2-bisdiphenylphosphine ethane, triphenylboron, andbenzene at 30:1:5:5:1: The ratio of the number of moles of 50 was added to the isomerization reactor, and thereaction pressure was set to 0.3 MPa, and the reaction temperature was set to 130 °C. During the reaction,nitrogen gas protection, mechanical stirring, reaction time was 6 hours, and after the reaction was completed,unreacted 2-methyl-2-butenenitrile and product 3-pentenenitrile were separated by vacuum distillation. . Theanalysis was carried out by a conventional gas chromatography method, and as a result, the conversion of 2-methyl-2-butenenitrile was 83%, and the selectivity of 3-pentenenitrile was 89.5%. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 1: 47.9 % 2: 8.7 % 3: 31.7 % | Stage #1: methyl (9E)-octadec-9-enoate; 3-pentenenitrile With C6H11N2(1+)*C36H58Cl2N2O3PRu(1+)*F6P(1-)*C2N3(1-) at 80℃; Schlenk technique; Inert atmosphere; Stage #2: With palladium-carbon at 80℃; | 1-6 General procedure: In a 250 mL round-bottomed flask, add 20 g of the above-mentioned metathesis catalyst solution I, and add 200 g of methyl oleate (oleic acid was purchased from Indonesian Harvest Industrial grade high-purity oleic acid, with a total unsaturated acid content of 92%, oleic acid The methyl ester was prepared according to the method of Biomass and Bioenergy, 2010, 34 (1): 134-139), and 50 g of 3PN (prepared according to the method of J. Organometallics 1984, 3, 33). The obtained 3PN was prepared by the chromatographic internal standard method. (Measurement content >98% using toluene as standard). A Schlenk device was used, and the nitrogen in the system was replaced three times. The system was heated to 80°C and reacted for 3 hours. A small amount of 2-butene is discharged with the exhaust gas and absorbed through the air bag. The reaction solution is separated at 40-50°C to avoid any possible precipitation due to solidification of the product. The lower metathesis catalyst solution I was returned to the round bottom flask for application experiments. The upper reaction liquid was introduced into a pressure-resistant reactor for hydrogenation, 5% Pd/C was added, and hydrogenation was performed at 80° C. and a hydrogen pressure of 1 MPa. A mixture of 11-CUA, adiponitrile, n-undecane, etc. was obtained, approximately 250 g. Through gas chromatography, the composition of each component in the system was analyzed using the area normalization method. See Table 1 for specific data. |