- RESISTANCE OF ACRYLONITRILE AND OF ITS HYDROFORMYLATION PRODUCTS TO THERMAL AND CATALYTIC ACTION.
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The study of the resistance of acrylonitrile and its hydroformylation products to thermal and catalytic action showed that at 120 degree and 30 MPa pressure in presence of cobalt carbonyls acrylonitrile does not undergo polymerization in presence of an inhibitor (hydroquinone); beta -cyanopropionaldehyde and its dimethyl acetal are stable when the process is conducted in methanol, but in nonpolar solvents (benzene) beta -cyanopropionaldehyde polymerizes. The use of methanol during storage and oxidative treatment of the products of acrylonitrile hydroformylation stabilizes beta -cyanopropionaldehyde.
- Del'nik,Kagna,Katsnel'son,Leenson
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p. 1248 - 1251
(2007/10/02)
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- FORMATION OF THE ACETAL OF beta -CYANOPROPIONALDEHYDE IN THE PRESENCE OF COBALT CARBONYLS.
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As a result of a study of the acetalization of beta -cyanopropionaldehyde with methyl alcohol at various molar ratios in the presence of cobalt carbonyls and under typical conditions for the hydroformylation of acrylonitrile, the equilibrium constants of the acetalization reaction have been determined. It has been shown that to obtain predominant conversion of beta -cyanopropionaldehyde into the diacetal during the hydroformylation, the initial acrylonitrile concentration should be 10-20 wt. %. A retarding effect by acrylonitrile on the acetalization of beta -cyanoproprionaldehyde, under the conditions of the hydroformylation reaction, has been detected.
- Katsnel'son,Del'nik,Kagna,Leenson
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p. 2514 - 2517
(2007/10/02)
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- LIGAND EFFECTS IN THE HYDROFORMYLATION OF ACRYLONITRILE BY COBALT CARBONYL
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The hydroformylation of acrylonitrile (VCN) using Co2(CO)8/L (L = HN(CH2CN)2, , Me2N(CH2)2NMeH, PPh3, and PCy3) has been examined in methanol solvent.Four reaction pathways are observed which are dependent on L.With no L or with L = HN(CH2CN)2, the reaction produces the desired acetal (MeO)2CHCH2CH2CN.For the more basic amines the reactin produces ca. 50percent yields of hydrodimerization products NCCHMe(CH2)2CN/NC(CH2)4CN in a 10/1 ratio and an ca. 30percent yield of the hydrogenation product CH3CH2CN.These reactions are shown to be metal catalyzed.The main reactionfor Co2(CO)8/PR3 catalyzed systems appears to be a classical Michael addition reaction of the solvent, methanol, with acrylonitrile to give MeOCH2CH2CN.Evidence is given to show that this reaction is catalyzed by phosphine which has dissociated under reaction conditions and not by a ligated cobalt complex.
- Dubois, R. A.,Garrou, P. E.
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