DE1807087A1 - Olefin hydrocyanation - Google Patents

Abstract

2-20C cpds. having >=1 -C=C- bonds sepd. by >=1 -C-C- bond are hydrocyanated by contacting the cpd. with HCN at -25 to 200 degrees C in presence of a catalyst of formula (Z3P)3 CoX (where Z = R or OR, R = is not >18C alkyl or hydrocarbyl aryl, and X = hal or CN.The nitrile prods are inters. e.g. for polyamides, and are added. in high yield under mild conditions, with minimal formation of polymer

Description

Process for the addition of hydrogen cyanide to olefins It is known that the addition of hydrogen cyanide to double bonds, an activating one Group, such as a nitrile or an acyloxy group, are adjacent, is easy to do. In contrast, hydrogen cyanide is added to non-activated ones Double bonds only with difficulty, if they happen at all, and typically requires high pressures of about 70 kg / cm2 (1000 psi) or greater and high temperatures between 200 and 400 ° C.

US Pat. No. 2,666,748 describes a procedure in which cobalt carbonyl with or without the addition of a tertiary arylphosphine @ or -arsins is used. These methods have the disadvantage that a relative high percentage of undesirable polymeric products is obtained, provided monoolefinic starting materials. can be used.

In addition, this process does not work satisfactorily the production of adiponitrile from 3- or 4-pentenenitrile.

The selective formation of 4-pentenenitrile from 3-pentenenitrile without the Formation of the thermodynamically more stable 2-pentenenitrile is not yet known become.

The present invention provides a method or step irk a process by which nitriles or dinitriles are obtained from olefins in high yields can be prepared under mild conditions with minimal polymer formation.

The inventive method is generally based on unsaturated Compounds with 2 to 20 carbon atoms applicable, the at least one aliphatic Have carbon / carbon double bond. Butadiene, 3-pentenenitrile, 4-pentenenitrile and 2-methyl-3-butenenitrile are particularly preferred to suitable unsaturated ones Compounds are monoolefins as well as monoolefins to be counted those substituted with groups are that do not attack the catalyst, such as the cyano, aldehyde, ester and Keto group.

These unsaturated compounds include diolefins such as butadiene, Monoolefins with 2 to 20 carbon atoms, such as ethylene, propylene, butene-1, pentene-2 or hexene-2 and substituted compounds such as styrene, 3-pentenenitrile and 4-pentenenitrile The process is particularly advantageous in the production of 2-methyl-glutaronitrile from 2-methyl-3-butenenitrile.

In a preferred procedure of the present invention, in which adiponitrile is formed from 3-pentenenitriles or 2-methyl-3-butenenitrile implementation takes place in several stages. In the first stage, the Isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile takes place. At the next step finds the isconerization of 3-pentenenitrile in 4-pentenenitrile instead of under this, the last stage follows, in which hydrogen cyanide is added to 4-pentenenitrile to form adiponitrile. With this frenzy can the 3-pentenenitrile and 2-methyl-3-butenenitrile by Hydrooyanisrung of Butadiene can be obtained.

The isoneration stage is catalyzed by cobelt or rhodium compounds with a value of less than +2, in general with an effective value in the system from 0.25 to 1.75 and the cobalt or rhodium compounds mentioned below for catalyzing the hydrocyanation stage.

The catalysts for the hydrocyanation stage are cobalt or. Rhodium compounds, of which it is believed that at least a portion of the cobalt or rhodium is one Has a value of +1. Such catalysts can easily be made from usual cobalt or rhodium compounds, in which the cobalt or rhodium is a Has valence of -1, w @@ HCO [P (C6H5) 3] 4 or HCo [POC6H5) 3] 4; or valence 0 has, such as CO2 (CO) 6 [POC6H5) 3] 2; or the valence 2, such as CoCl2 or the valence 3, like RhCl3, by adding such a compound with a sufficient amount of a Oxidizing or reducing agents treated to the average or effective Bringing the valence of cobalt or rhodium @@ below +2, in general only in the range from +0.25 to +1.75 and preferably in the range from +0.75 to +1.25. The cobalt or rhodium can be introduced into the catalyst system in many forms, including coordination compounds of cobalt or rhodium or salts of cobalt or rhodium. Suitable coordination compounds can the low valence cobalt or rhodium along with a sigma / pi binding ligand contain. The connection will then oxidized by common methods, for example with iron (III) chloride with the formation of a general-purpose catalyst Formula L3MX, in which M is Co or Rh, X is an anion and L is a neutral ligand. All atoms or molecules that act as sign @ / pi-bound partners in one or more Coordination bonds can function as ligands L are useful. A description such ligands can be found in the book "Advanced Inorganic Chemistry" by F. Albert Cotton and G.

Wilkinson, published by Interscience Publishers, a division by John Wiley & Sons, 1962, Library of Congress Catalog Card No. 62-14818, particularly on pages 602-606. Preferred ligands used have the formula Z3M ', where Z and M' have the meanings given above.

In those cases in which the carbon or rhodium are added to the system as Salx be supplied or as a +2 or +3 valent complex it is in general required to use a reducing agent. Approved reducing agents therefor zind metals that are sufficiently electronegative to convert cobaite into Co + 1 or rhodium reduce in Rh + 1 su. In a preferred mode of operation of the present invention the cobalt or rhodium salt is reduced with a metal, which at the same time acts as an accelerator for the catalyst. Such accelerators are described below described. Suitable cobalt and rhodium salts are generally the salts of Mineral acids, lower fatty acids, organic sulfonic acids, acetonylacetonate, of fluoroboric acid and with salioylaldehyde. Of these, the Halegenide and here especially the chlorides, bromides and iodides are preferred because of their easy accessibility and their ease of use.

In a preferred mode of operation of the invention, a phosphite is used used to increase the activity of the catalyst and to increase the ixomere distribution control of the product.

This is of particular importance in the manufacture of adiponitrile from 3-pentene @litrile or 4-pentenenitrile, where a catalyst system such as such from cobalt chloride and iron, results in a product made almost entirely of methylglutaronitrile exists, while the same catalyst system, when combined with a phosphite, such as triphenyl phosphite, is used, can give a product in which 80% or more of the dinitriles produced from adiponitrile, which is normally the product you want is. The preferred phosphites have the formula P (OR) 3, wherein R is an alkyl or aryl radical with up to 18 carbon atoms. In general the phosphite is in a molar ratio of phosphite to cobalt or rhodium of 0.5: 1 to 12: 1 and preferably 2.5: 1 to 4.5: 1 used.

A preferred class of catalysts likely has the structure [(Z) 3M '] 3MX, where Z is OR or R, where R is an alkyl or aryl group up to 18 carbon atoms, M 'cobalt or rhodium and X a halogen or CN means.

These catalysts can be used by any of several different procedures getting produced; for example, the catalysts of the formula (Z3M ') 3 RhX, wherein Z, M 'and X are as defined above, easily obtained by a rhodium halide with an excess of a compound of the formula Z3P slightly elevated temperatures, such as about 100 ° C. If you use the cobalt catalysts, so the catalyst can also be made in situ by mixing the two components in a reaction vessel, preferably in practically equimolar amounts. The HCo (Z3M ') 4 starting material can be prepared according to the procedure described in Example 55 below. The catalyst compounds are preferably obtained by partial reduction of a cobalt halide with a metal such as zinc or iron in the presence of a compound of the formula Z3M ', wherein Z and M 'have the meaning given above have made.

The hydrocyanation or isomerization reaction can with or chne Solvent to be carried out. The solvent should be at the reaction temperature be liquid and towards the unsaturated compound and the catalyst itself behave inert. In general, such solvents are hydrocarbons, such as Benzene, xylene, or nitriles, such as acetonitrile, benzonitrile or adiponitrile.

the exact temperature used depends to some extent on the catalyst used in each case, the unsaturated compound used in each case and the desired speed of implementation. In general, temperatures from -25 to 200 ° C, with the range from 0 to 150 ° C as well for the isomerization as is preferred for the Hydrocyanierun.

Both the isomerization reaction and the hydrocyanation reaction can be done by placing all of the reactants in a conversion vessel. In the case of hydrocyanation, it is preferred that a reaction vessel with the catalyst or catalyst components, the unsaturated compound and the garade to be used Solvent is charged and the hydrogen cyanide gas over the surface of the The reaction mixture is passed or bubbled through the reaction vessel. If a gaseous, unsaturated, organic compound is used, can the hydrogen cyanide and the unsaturated organic compound optionally together are introduced into the reaction medium. The molar ratio of unsaturated Compound to catalyst generally varies from about 10; 1 to 2000: 1 at discontinuous operation. When working continuously, for example when using a fixed bed catalyst, a much higher proportion of catalyst, for example a ratio of unsaturated compound to Catalyst such as 1: 2 can be used.

If desired, hardly any accelerator can be used in the catalyst to activate for the hydrocyanation reaction.

The accelerator is generally a Lewis acid such as a cationic one Form of a metal, such as zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, Titanium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium, sioandium, chromium, Molybdenum, tungsten, manganese, rhonium, palladium, thorium, copper, lead or iron, Other designated accelerators are salts of the aforementioned metals, including Aluminum chloride, zinc chloride, cad @ dumiodide, titanium trichloride, titanium tetrachloride, Zinc acetate, ethyl aluminum dichloride, chromium (III) chloride, tin chloride and zinc iodide. The Beschleundgar brings about an improvement in the katalysaborffekt @@@@ it and in some Cases, such as the hydrocyanation of 3- or 4-pentene @ itril to adiponitrile, can he cause a varied yield. The preferred accelerators are Katienese Forwen of zinc, cadmium, aluminum, indium, zircon, tin, wangan, caloium, copper, Bled and iron. These metals can be added to the catalyst system in the form of a salmon be supplied if a previously reduced catalyst is used, or in the form of the Metailes, which in the case of a non-reduced catalyst at the same time serves to reduce the catalyst rather than the activity of the catalyst to increase. Suitable anions are the halides, in particular the chlorides, promides and iodides, and the lower fats. Preferably the Beschl @@@ ger at the conversion of the metal and the unreduced or incompletely reduced Catalyst precursor formed. In general, the accelerator is in one molar ratio @@ of cobalt or rhodium to accelerator from 16: 1 to 1:16 used. The pressure applied is not critical @@ d can range from 0.1 to 10 or more atmospheres varii @@@@. However, it is important to use the partial pressure, the HOW in the reaction @@@@@@ below 1 atmosphere.

If desired, an excess of pi-bonded ligands, such as an aryl phosphite, are added to the reaction mixture. De The reaction gene is preferably agitated, such as by stirring or shaking.

The cyanated products can by customary methods, such as by Crystallization of the product obtained from a solution or by distillation will.

The nitriles formed in accordance with the present invention are chemical Intermediates. Aliponitrile is, for example, an intermediate product, as is the case with the Manufacture of hexamethylene adipamide, a commercial polyamide that 1st signed for the production of fibers, films or pressed articles.

Other mitrils can be converted into the corresponding acids and amines which represent common commercial products.

EXAMPLE 1 to 51 A 50 ml glass three-necked round bottom flask is equipped with a water-cooled reflux condenser with a dry ice trap is connected, a gas inlet above the liquid level and a magnetic stirrer, immersed in an oil bath, which is given in Table I under temperature Temperature asked. The calving is purged with nitrogen gas and with the in table I filled specified compounds. In the examples 1 to 3 and 5 to 50 are 20 g of 3-pentenenitrile submitted to the @@@@@. In Examples 4 and 51 in the flask submitted 20 g of 2-methyl-5-butenenitrile. A stream of nitrogen is going through liquid hydrogen cyanide, which is in a 20 ml glass flask, cooled with an ice bath, located, separated.

The gas mixture obtained is above the surface of the reaction mixture blown into the flask. The nitrogen flow is adjusted so that the amount of supplied HCN (measured as a liquid at 0 ° C) which is supplied to the flask corresponding to the amount given in Table I. The amounts of ADN (adiponitrile), MON (2-methylglutaronitrile), ÄSN (ethylsucoinonitrile) and 4-PN (4-pentenenitrile), as indicated in Table I for the product refer to the percentage of the particular nitrile in the crude reaction mixture, as determined by gas chromatography Analysis have been determined. In Examples 2, 3, 49 and 50, the "+" indicates that the substance specified under reduction @@ ittel is actually an activator and not a Is reducing agent. In Example 37, Co (QAc) 2 means cobalt acetate. In the examples 9 and 10, the "+" indicates that an oxidizing agent instead of a reducing agent was used. In Example 13, 2.5 ml of the phosphite ligand is added to the flask. In Examples 25 and 47, Co (Acac) 2 means cobalt acetonylacetonate. In the examples 26 and 46, Co (Sal) 2 means a cobalt salicyladehyde complex. In the examples 27 and 48, Co (hyqn) 2 means a cobalt-8-hydroxyquinoline complex. For example 50 becomes the HCl fed to the flask in the form of 1 ml of concentrated hydrochloric acid fed. In Example 51, the product is 7.56 g of 3-pentenenitrile instead of that in 4-pentenenitrile given in the table.

Table I At- Catalyst Reducing Ligand HCN-To- Tem- Time Product sp. Connection amount medium +) connection amount lead- pe- hrs. AND MON ÄSN no. Connection (g) connection amount (g) speed. ra-%%% dung (g) ml / h tur ° C LIC B r Ch 8cu. E8 ' 13 U \ II \ CX OOO w4 Cl CA 1 CcC12 0.13 Zn 0.03 P <O3) 3 10 0.05 80 co 0.84 0.17 2 o "0.92 + Cl2 0.14 1? 10 0> 1 120 22 0.27 Ilr n r o 10 0.03 NO «0.92 O o, a8 4 00012 0.65 HCo6 6.5 P (006R5> 3 3.1 0.2 80 F U.5 * * G 00012 1.30 æ o 0.2 80 24 4> 23 1.80 0.56 os cOc12 0.63 1 6.5 0.2 80 50 15.06 4.54 0.91 o UCU CUCINnO 8 0012 1.5 6.5 Q ° 000Q 9 HcoOC66,5 Pe013 +) o, 6 CV o OOW » rJ r3 10 n 6.5 Hs013 +) 1.3 er n 0 ,? 11 00012 1.3 Pe 0.28 P (006H5) 3 6.2 16 42.79 4.36 1s66 12 CO012 Pe 0.28 P (o-) 3 14 1 1 21 20.14 3.7.4 0.47 O X Pooh 9 *% umu FW n X q Q oo M> wa aP owoo t4 S stt r oo ca oo WW XNN sb «r ~ t o. t V e $ g m * In X, F oo ffi. o see below Table I (continued) By- Catalyst Reducing Ligand HCN-To-Tem- Time Product sp. Connection amount medium +) connection amount lead- pe- hrs. AND MON ÄSN no. ra-%%% dung (g) ml / h tur ° C O'rt In. jh O cu EI \ OE (r- cr, CV O r oo 'o CP "r3 (5 0 8 $ o 04 a P9IßX8 $ ilC% o 8iui oc:; i. (ao; $ 0 rJ VI rD Br! 13 cDcL2 1.3 Pe o, 2B fl09)> 0.1 2 21 »0.36 14 COCl2 g P (oc> 6.9 n t4sfl I 0.64 15 2 to 1.0 to 6.2 8 16 ooc 1 1.0 1 100 '19 0 0.17 0 1? 1 0.1 1 12.4 t 22 15.69 .6> 0.79, 9 coc1 p 19 cn «'1. 22 0.61 0.96 * not specified i "0.3 t 6.2, 1 - 3.41 1, 0.40 ear 22 OO 1 cr 1 1 1 1 22 12.96 4.90.5o X 4X c 0.3 t Ir L .1 24 1, -1.0 fw kk 2, -at, 6 O o, aS- 1 rl IX) M oaoo ca o sa ooeo t S oh 8 k S n BB to BUBBSBRSJ eeeeesasa X 14 æ ItE o 4 y Table I (continued) By- Catalyst Reducing Ligand HCN-To-Tem- Time Product sp. Connection amount medium +) connection amount lead- pe- hrs. AND MON ÄSN no. ra-%%% dung (g) ml / h tur ° C 26 Co (Sal) 2 3.0 Fe 0.28 P (OC6H5) 3 0.1 80 22 0 1.14 0.20 27 Co (hy @ n) 2 3.5 Fe 0.28 "" 80 5 0.15 0.25 0 28 CoCl2 1.3 Fe 0.28 "6.2" 140 21 14.91 8.23 0.86 29 CoCl2 "Nb 0.43" 12.4 "100 21 0, 17 0.17 0 30 CoCl2 "In 1.1""""19 13.99 4.36 1.23 31 CoCl2" Hf 1.0 """" 19 0.56 0.18 0 32 CoCl2 "Ce 0 , 7 """" 22 1.78 0.48 0.15 33 CoCl2 "Zr 0.4""""21 16.82 3.79 0.75 34 CoCl2" Ti 0.4 """" 22 0 , 29 0.22 0 35 CoCl2 "CaH 0.8""""" 19.39 4.93 0.82 36 CoCl2 "V 0.5""""" 0.22 0.20 0 37 Co (OAo ) 2 1.2 Fe 0.28 """""0.17 0.38 0 38 CoCl2 1.3 Bi 1.0""""""" 0.21 1.19 0 39 Co (BF4) 2 2.3 Fe 0.28 """""0 0.19 0 Table I (continued) At- Catalyst Reducing Ligand HCN-To- Temp- Time Product sp. Connection - Amount medium +) Compound Amount forgs.- pe- Hours ADN MGN ÄSN no. Dung (g) compound amount (g) speed ra-%%% dung (g) ml / h temperature ° C 40 CoF2 1.0 Fe 0.28 P (OC6H5) 3 12 , 4 0.1 100 22 0 0.18 0 41 CoCl2 1.3 B10H14 0.1 """""20 1.0 0.59 0 42 CoCl2 1.3 NaBH4 0.1 """" 20 0.47 1.16 0 43 CoCl2 1.3 P (C4H9) 3 1.0 """" 21 0.46 1.14 0 44 CoCl2 1.3 Cr (CO) 6 0.8 """" 21 0.2 0.55 0 45 Co (CN) 2 1.1 CaH 0.4 "" 22 0.149 0.18 6.44 46 Co (Sal) 2 3.0 Zn 0.33 """0 3.43 0.32 47 Co (Acao) 2 2.6 Zn 0.33""" 0.21 4.33 0.46 48 Co (Hyqn) 2 3.5 Zn 0.33 """0 0.45 0.11 Table I (continued) For Catalyst Reduction Ligand HCN-To-Tem- Time Product sp. Connection quantity medium +) connection quantity lead. - pera- Std. 4-PN (%) No. (g) connection amount (g) speed. tur dung (g) ml / h ° C sD 1l \ 49 oo4P (0 <>c3)> 74 1.47 znc12 0.14 '0 100 20 1> 5 8 o6H5) 3P73Hncl 0.92 HCl +) 6.5 0.2 120 8 9 51 00C12 0.65 'iiooP (oc6 6.5 0 1 22 7.56 ru ooo I »u uo o £ W NUZ rl-> AO% s 0% ws no W. ft OS EXAMPLE 52 A 400 ml stainless steel printer is cooled with dry ice. Nitrogen is passed through the tube and then 6.5 g of HCo [P (OC6H5) 3] 4, 0.65 g of Cocl2, 87 ml of liquid butadiene and 35 ml of liquid hydrogen cyanide are added. The tube is closed, briefly evacuated and heated to 100 ° C. for 8 hours. After this time the pipe is cooled to 25 ° C, ventilated and the liquid is recovered.

Gas chromatographic analysis indicates that the liquid sample Contains 3-pentenenitrile and 2-methyl-3-butenenitrile.

EXAMPLE 53 A 50-ml, 3-neck, glass, round-bottom flask that comes with a water-cooled reflux condenser, connected to a dry ice trap, sinem Gas inlet above the liquid level and a magnetic stirrer fitted is immersed in an oil bath kept at 120 ° C. The flask is filled with nitrogen gas rinsed and then 6.5 g of HCo [P (OC6H5) 3] 4, 0.65 g of Cocl2 and 20 g of 2-methyl-3-but @ itril admit it. The mixture is heated to 120 ° C for 22 hours. After this time has elapsed gas chromatographic analysis indicates that the liquid sample contains 7.56% 3-pentenenitrile contains.

The tetrakis (triphenylphosphite) cobalt hydride used in the above example is produced according to the script of Example 54.

EXAMPLE 54 In a glass three-neck flask with a nitrogen gas inlet, a water cooled reflux condenser and one If a mechanical stirrer is fitted, 29.0 g (0.10 mol) of cobalt nitrate hexahydrate are added and submitted 400 ml of acetonitrile.

The salt is brought into solution in a steam bath and added to it 150 g (0.50 mol) of triphenyl phosphite were added. The color changes from blue to dark purple. The solution is cooled to room temperature and 5.0 g (0.136 Moles) of sodium borohydride are added in small portions over a period of about 4 hours. The color of the reaction mixture slowly changes from blue to brown to yellow, while at the same time a yellow precipitate forms. The precipitation will collected, washed with methanol and removed from the filter with 200 ml of benzene brought back into solution by inorganic salts. The tetraicis (triphenylphosphite) cobalt hydride is precipitated with 1.5 l of methanol, filtered and washed in vacuo. It melts at 146 to 148 ° C. When recrystallizing from benzene / methanol (9/1) increases the melting point at 157 to 159 ° C. The yield is 71 g (54.5%).

Example 55 A 5-ml, three-necked, round-bottomed glass flask equipped with a water-cooled reflux condenser attached to a dry ice trap. a gas inlet above the liquid level and a magnetic stirrer, is immersed in an oil bath operated at 80 ° C. The flask is flushed with nitrogen gas and 1.3 g CoCl2, 6.2 g P (OC6H5) 3, O, 28 g iron powder and 20 ml < submitted. A stream of nitrogen is bubbled through liquid hydrogen cyanide in a flask cooled with an ice bath. The gas mixture obtained is passed above the surface of the reaction mixture in the flask. The nitrogen gas flow is regulated so that about 0.1 ml / hour. Hydrogen cyanide (measured as a liquid at 0 ° C) is added to the reaction flask.

The reaction is terminated after 24 hours. The gas chromatographic analysis and the infrared analysis show that a hydrocyanation of the carbon / carbon double bond of the has taken place.

Example 56 A 50 ml glass three-necked round bottom flask equipped with a water-cooled reflux condenser connected to a trooke ice trap, a gas inlet above the liquid level and a magnetic stirrer is immersed in an oil bath operated at 80 ° C. The flask is flushed with nitrogen gas and 1.3 g of CoCl2, 6.2 g of P (OC6H5) 3, 0.28 g of iron powder, 10 ml of CH3CN and 10 ml are added submitted. A stream of nitrogen gas is sparged through liquid hydrogen cyanide contained in a flask cooled in an ice bath. The resulting gas mixture is passed over the surface of the reaction mixture in the flask. The nitrogen gas flow is regulated so that about 0.1 ml / hour. Hydrogen cyanide (measured as a liquid at 0 ° C), fed to the reaction flask.

The reaction is terminated after 23 hours. Gas chromatographic analysis and infrared analysis indicate that the hydrocyanation of the carbon / carbon double bond of the has taken place.

Example 57 Example 56 is repeated with the exception that 10 ml @instead of that used in Example 56 can be used and the reaction is stopped after 21 hours. Again, the gas chromatographic analysis and the infrared analysis indicate that the hydrocyanation of the carbon-carbon double bond has found des.

EXAMPLE 58 A 50 ml, three-necked, round-bottomed, glass flask fitted with a water-cooled reflux condenser connected to a trooke ice trap is, a gas inlet above the liquid addition and a magnetic stirrer immersed in an oil bath operated at 80 ° C.

The flask is flushed with nitrogen gas and 1.3 g of CoCl2, 6.2 g of P (OC6H5) 3, 25 ml of allyloyanide and 0.28 g of iron powder are provided. You let one Nitrogen gas flow through liquid hydrogen cyanide in a flask, which is cooled by an ice bath, bubble through it. The gas mixture obtained is passed over the surface of the reaction mixture in the flask. Dar nitrogen gas flow is set so that about 0.1 ml / hour. Hydrogen cyanide (measured as a liquid at 0 ° C) are fed to the reaction flask. After 21 hours the reaction will canceled.

Gas chromatographic analysis indicates that the raw reaction mixture Contains 22.8% glutaxonitrile.

EXAMPLE 59 A 50-ml, three-necked, round-bottomed glass flask fitted with a water-cooled reflux condenser connected to a dry ice trap 1st, a gas inlet above the liquid level and a magnetic stirrer immersed in an oil bed operated at 80 ° C. The flask is purged with nitrogen gas and 1.3 g CoCl2, 6.2 g P (CO6H5) 3, 0.28 g ice powder are added and submitted 25 ml of 2-methyl-3-butenenitrile. A stream of nitrogen is passed through Liquid hydrogen gyanide, which is in a flask, which is passed through an ice bath is cooled, parallel through. The gas mixture obtained is over the surface the reaction mixture passed into the flask. The nitrogen gas flow is regulated that about 01 ml / hour Hydrogen cyanide (measured as a liquid at 0 ° C) into the reaction flask are fed. The reaction is terminated after 21 hours.

Gas chromatographic analysis indicates the crude reaction mixture Contains 0.09% adipenitrile, 23.2% 2-methyl-glutaronitrile and 0% ethylsnocinonitrile.

EXAMPLE 60 A 50 ml, three-necked, round-bottomed glass flask fitted with a water-cooled reflux cooler connected to a dry ice trap 1st, a gas inlet above the liquid anivesus and a magnetic stirrer immersed in an oil bath driven at 120 ° C. The flask is filled with nitrogen gas rinsed and there are 1.3 g of CoCl2, 12.4 g of P (OC6H5) 3, 0.08 g of aluminum powder and 25 ml of 2-methyl-3-butenenitrile (containing 8.32% 3-pentenenitrile) were initially introduced. The mixture is heated to 130 ° C for 9 hours. After this time has elapsed, the gas chromatographic Analysis indicates that the liquid sample contains 17.3% 3-pentenenitrile.

EXAMPLE 61 The same formulation as in example 60 with the exception of That 0.33 g of zinc powder is used instead of aluminum powder is carried out. After completing the implementation shows gas chromatographic analysis indicates that the concentration of 5-pantenenitrile @uf has increased by 16.1%.

EXAMPLE 62 A similar implementation as in example 60 is carried out carried out using 1.3 g CoCl2, 9.3 g P (CO6H5) 3, 0.33 g zinc powder and 25 ml of 2-methyl-3-butenenitrile. The mixture is heated to 130 ° C. for 9 hours. After this time has elapsed, the gas chromatographic analysis shows that the Has increased concentration of 3-pentenenitrile to 17.3%.

Claims (4)

P a t e n t a n s p r ü c h e 1. Behavior for the production of organic cyano compounds, thereby gekermzeich that one is the double bond of an unsaturated organic compound with an elefinic carbon / carbon double bond and 2 to 20 carbon atoms hydrocyandert, by the compound mentioned with hydrogen cyanide in the presence of a catalyst, said catalyst being a compound of the formula (Z3M ') 3MX, in which Z is R or OR, R is an alkyl or aryl group of up to 18 carbon atoms, and M 'represents P, As or Sb and N Co or Rh and X is halogen or CN. 2. Process for the preparation of an organic cyano compound by Hydrocyanation of the double bond in an unsaturated organic compound with olefinic carbon-carbon double bond and 2 to 20 carbon atoms de-cooled, characterized in that the entire unsaturated organic compound, hydrogen cyanide, and a compound of a metal M, wherein M signifies cobalt or rhodium, and an oxidizing or reducing agent in one Amount that is sufficient to bring the effective valence of M to 0.25 to 1.75, feeds. 3. Process for isomerizing 3-pentenenitrile in 4-pentenenitrile, characterized in that one reaction gas vessel is 3-peutenenitrile and a compound of a metal M, in which N is cobalt or rhodium, and an oxidation or Reducing agent in an amount sufficient to achieve the effective Bring valence of M to 0.25 to 1.75, adds. 4. Procedure for isomerizing 2-methyl-3-butenenitrile in 3-pentenenitrile, characterized in that 2-methyl-3-butenenitrile and a reaction vessel a compound of a metal M, in which M is cobalt or rhodium, and an oxidation or reducing agents in an amount sufficient to achieve the effective valency to bring from M to 0.25 to 1.75, supplies.