pent-4-enenitrile

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was equipped with stirrer, reflux condenser, thermometer, and charged with 75 ml of water and 36.8 grams (0.75 mole) sodium cyanide. Stirring was commenced and there was added 8.5 grams of tricapryl(methyl)ammonium chloride (ALIQUAT 336 phase-transfer catalyst) followed by 67.5 grams (0.50 mole) of the bromide product mixture comprising 55.7% cyclopropylmethyl bromide, 37.2% bromocyclobutane, and 7.1% bromobutene. The mixture slowly exothermed to about 50° C. After about 1 hour, heating was commenced so as to maintain the temperature of the mixture at 45° C. After 7 hours, gas chromatographic analysis of the organic phase indicated that cyclopropylmethyl bromide and 4-bromo-1-butene (i.e., bromobutene) were consumed, that cyclobutyl bromide was unchanged, and that cyclopropylacetonitrile and 1-cyano-3-butene were formed. The ratio (area %) of cyclopropylacetonitrile to 1-cyano-3-butene was 88:12. A minute trace (less than 1 area %) of cyanocyclobutane was detected. A flask was equipped with stirrer reflux condenser slowly exothermed to about 50° C heating After 7 hours were consumed

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was equipped with stirrer, reflux condenser, thermometer, and charged with 75 ml of water and 36.8 grams (0.75 mole) sodium cyanide. Stirring was commenced and there was added 8.5 grams of tricapryl(methyl)ammonium chloride (ALIQUAT 336 phase-transfer catalyst) followed by 67.5 grams (0.50 mole) of the bromide product mixture comprising 55.7% cyclopropylmethyl bromide, 37.2% bromocyclobutane, and 7.1% bromobutene. The mixture slowly exothermed to about 50° C. After about 1 hour, heating was commenced so as to maintain the temperature of the mixture at 45° C. After 7 hours, gas chromatographic analysis of the organic phase indicated that cyclopropylmethyl bromide and 4-bromo-1-butene (i.e., bromobutene) were consumed, that cyclobutyl bromide was unchanged, and that cyclopropylacetonitrile and 1-cyano-3-butene were formed. The ratio (area %) of cyclopropylacetonitrile to 1-cyano-3-butene was 88:12. A minute trace (less than 1 area %) of cyanocyclobutane was detected. A flask was equipped with stirrer reflux condenser slowly exothermed to about 50° C heating After 7 hours were consumed

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A flask was equipped with stirrer, reflux condenser, thermometer, and charged with 75 ml of water and 36.8 grams (0.75 mole) sodium cyanide. Stirring was commenced and there was added 8.5 grams of tricapryl(methyl)ammonium chloride (ALIQUAT 336 phase-transfer catalyst) followed by 67.5 grams (0.50 mole) of the bromide product mixture comprising 55.7% cyclopropylmethyl bromide, 37.2% bromocyclobutane, and 7.1% bromobutene. The mixture slowly exothermed to about 50° C. After about 1 hour, heating was commenced so as to maintain the temperature of the mixture at 45° C. After 7 hours, gas chromatographic analysis of the organic phase indicated that cyclopropylmethyl bromide and 4-bromo-1-butene (i.e., bromobutene) were consumed, that cyclobutyl bromide was unchanged, and that cyclopropylacetonitrile and 1-cyano-3-butene were formed. The ratio (area %) of cyclopropylacetonitrile to 1-cyano-3-butene was 88:12. A minute trace (less than 1 area %) of cyanocyclobutane was detected. A flask was equipped with stirrer reflux condenser slowly exothermed to about 50° C heating After 7 hours were consumed

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The process of the present invention is applied to a waste stream from a process which involves the direct addition of two molecules of hydrogen cyanide to a molecule of butadiene thereby producing adiponitrile. The process is conducted in two steps. With reference to the drawing, the first step (reactor 1) involves the addition of one molecule of hydrogen cyanide (stream 2) to dry butadiene (stream 3) in the presence of a catalyst (stream 4) consisting of zero-valent nickel usually in the form of a nickel tetrakis-tritolylphosphite, to produce a mixture of cis- and trans-3-pentenenitrile and 4-pentenenitrile. This reaction mixture is withdrawn from reactor 1 via line 5, treated to remove impurities and then introduced into reactor 6 along with additional HCN (line 7), ligand (line 8) and triarylborane catalyst promoter such as triphenylborane (line 9). In this reaction which can be conducted in one or more steps, 4-pentenenitrile is formed by the in situ isomerization of 3-pentenenitrile. The 4-pentenenitrile is then converted to adiponitrile by the addition of one molecule of HCN. The effluent from the reactor 6 is passed to extractor 13 and there contacted with cyclohexane (line 14). The cyclohexane extractant (line 15) is subsequently directed to further treatment for product recovery. During the hydrocyanation as described as hereinabove a portion of the zero-valent nickel catalyst is oxidized to nickel cyanide which is insoluble in the reaction medium and which forms insoluble complexes with the triarylborane. The tails from the extraction vessel (line 16) contain such complexes which are subsequently separated from the tails (line 16) by centrifuge 17. A typical analysis of this sludge is set forth below in Table I. to produce This reaction mixture is withdrawn from reactor 1 via line 5 treated to remove impurities introduced into reactor 6 along with additional HCN (line 7), ligand (line 8) and triarylborane catalyst promoter such as triphenylborane (line 9) In this reaction which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of Boc-piperidinone (1 g, 5 mmol) and tetrabutylammonium cyanate (2.86 g, 10 mmol) in MeOH (12 mL) was added cyclohexyl isocyanide (0.62 mL, 5 mmol) and pent-4-en-1-amine hydrochloride (732 mg, 6 mmol, prepared from the LAH reduction of 4-cyano-butene) in MeOH (8 mL) dropwise. The reaction mixture was stirred at rt for 1.5 h, diluted with EtOAC, washes with aq NaHCO3, brine, dried over sodium sulfate, concentrated in vacuo and purified by flash chromatography (silica gel, EtOAc) to provide the desired product LRMS (M+1)=419. diluted with EtOAC dried over sodium sulfate concentrated in vacuo purified by flash chromatography (silica gel, EtOAc)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The isomerization of cis-2-pentenenitrile (boiling point 127° C./1013 mbar) gives rise to the target products trans-3-pentenenitrile (boiling point 143° C./1013 mbar) and cis-3-pentenenitrile (boiling point 146° C./1013 mbar), and also small amounts of 4-pentenenitrile (boiling point 146° C./1013 mbar) and trans-2-pentenenitrile (boiling point 144° C./1013 mbar). Trans-3-pentenenitrile, cis-3-pentenenitrile and 4-pentenenitrile can be used, after distillative removal, for the hydrocyanation with hydrogen cyanide to give adiponitrile. cis- and trans-2-pentenenitrile can be recycled into the isomerization stage after distillative removal. after distillative removal

Conditions: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 8.1 parts of 4-pentenonitrile, 1.4 parts of dicobalt octacarbonyl, 2.6 parts of pyridine, 8 parts of methanol and 30 parts of acetone is reacted in the same way as in Example 1. The pressure is brought to 200 bars by forcing in carbon monoxide at room temperature. The autoclave is heated to 160° C, the pressure is raised to 300 bars by forcing in further carbon monoxide, and the autoclave is shaken for two hours under these conditions. Fractional distillation of the material discharged from the autoclave gives 10.6 parts of 5-cyanovaleric acid methyl ester (75.1% of theory); boiling point 122°-124° C/11 mm Hg. is reacted in the same way as in Example 1 the pressure is raised to 300 bars Fractional distillation of the material