DE1593280B - - Google Patents

Description

A ₁
A ₄ -Ni-A ₂

in which A ₁ , A ₂ , A ₃ and A _{4 are} CNR, acrylonitrile or M (X, Y, Z), where M is phosphorus, arsenic or antimony, X. Y and Z are R, OR, NR ₂ , Cl or F and R stands for an alkyl or aryl group with up to 18 carbon atoms, as a catalyst and converts from Vi6 to 16 mol per mole of the nickel complex of an alkali borohydride or a tetra (lower - alkyl) ammonium borohydride as an accelerator. ■

The addition of hydrogen cyanide to double bonds which are adjacent to an activating group, such as, for example, a nitrile or an acyloxy group, is known to be easy. In contrast, the addition of hydrogen cyanide to non-activated double bonds takes place only with difficulty, if it takes place at all; normally the use of high pressures of about 70 kg / cm ² or more and high temperatures between 200 and 400 ^° C. is required. US Pat. No. 2,571,099 describes an improvement on this method which consists in using nickel carbonyl with or without the addition of a tertiary aryl phosphine or arsine. This process has the disadvantage that a relatively high percentage of undesirable polymeric products is obtained if monoolefinic starting materials are used; in all cases relatively poor yields are obtained. Furthermore, this process for the preparation of adiponitrile from pentenenitriles is unsatisfactory.

The object of the invention is therefore to provide a method by which nitriles or dinitriles from olefins in high yields under mild conditions with minimal polymer formation can be produced.

The invention relates to a process for the preparation of organic nitriles by reacting an organic compound containing at least one ethylenic carbon-carbon double bond with hydrogen cyanide in the presence of a zero-valent nickel complex as a catalyst and an accelerator, which is characterized in that 3- or 4- Pentenenitrile, butadiene, allene or allyl cyanide with hydrogen cyanide at a temperature between -25 and +200 ⁰ C in the presence of a zero-valent nickel complex of the general formula

I.
A ₄ -Ni-A ₂

A ₃

in which A ₁ , A ₂ , A ₃ and A _{4 are} CNR, acrylonitrile or M (X, Y, Z), where M door is phosphorus, arsenic or antimony, X, Y and Z door R, OR, NR ₂ , Cl or F and R door is an alkyl or aryl group with up to 18 carbon atoms, as a catalyst as well

* 2o from V ₁₆ to 16 mol per mol of the nickel complex, an alkali borohydride or a tetra (lower-alkyl) ammonium borohydride as an accelerator.

Nickel compounds which are formed in advance or produced in situ are used as catalysts will. These catalysts include nickel compounds, the phosphines, arsines, stibines, Contain phosphites, arsenites, stibites, acrylonitrile and mixtures of these compounds.

A preferred class of catalysts are nickel complexes with phosphites, arsenites, stibites, substituted acrylonitrile, phosphines, arsines or stibines, which cause the isomerization of 3-pentenenitrile to 4-pentenenitrile. These catalysts are particularly suitable for the synthesis of adiponitrile and substituted adiponitriles. This isomerization property can be obtained in a simple manner by contacting pure 3-pentenenitrile with the catalyst in the presence of 1 mol of H ₂ SO ₄ per mol of nickel, which is followed by heating at 120 ^° C. for 1 hour.

If necessary, if this is possible,

Groups falling under the definition of X, Y and Z may be linked to one another. It is believed that in these nickel complexes at least some of the nickel is in the zero-valent state. In many Cases, it is advantageous to use an excess of the neutral ligand present in relation to the Use nickel complex. This method can be used to determine the isomer distribution control and thus reduce the amount of by-products formed and the catalyst life to extend. As ligands suitable according to the invention, atoms or molecules can be used defined as σ-π-bonded partners in one or more coordinative bonds are able to act. In general, the neutral ones Ligands such as CO and M (X, Y, Z), wherein M, X, Y and Z are those given above Have meaning, preferred. A description of such ligands can be found in »Advances Inorganic Chemistry «by Falbert Cotton and G. W i 1 k i η s ο η (published by Interscience Publishers, a division of John Wijey & Sons), 1962, Library of Congress Catalog Card No. 62-14818, in particular pp. 602 to 606.

Satisfactory processes for the preparation of these catalysts are described in French U.S. Patent 1,297,934. Other

3 4

Methods for the production of these catalysts find 10: 1 to 2000: 1 with a batchwise through-

see J. C h a 11 and F. A. H a r t in »Chem. guided process, with continuous work

Soc. Journal "(London), pp. 1378 to 1389 (1960), as is the case when the catalog

and Lewis S. Meri wether and Marilyn L. Fieη e lysator is used in the form of a fixed bed,

in "JACS", 81, pp. 4200 to 4209 (1950). A much higher amount of catalyst can be used

There are several methods of in-situ fabrication, for example in this case the

position of the catalyst. For example, ratio of unsaturated compound to catalyst

Nickel carbonyl and a neutral ligand as it is 1: 2.

has been defined above, with the exception of Koh- Preferably the reaction medium is agitated,

Lenmonoxide, is added to the reaction mixture, for example by stirring or shaking. The

the. It is preferable to wait before using the cyanated product can according to conventional methods

of the catalyst until the carbon monoxide methods are separated off, for example by distillation

development has stopped. Be a second method.

consists in using the neutral ligand (as previously defined), a nickel (II) compound, or without a solvent; such as a nickel halide. z. B. NiCl ₂ , the solvent should be brought together at the reaction _{temperature Ni (CN) 2} or Ni-bis-acetonylacetonate, and a compound which is liquid under the reaction pressure and which provides hydride ions. The unsaturated compound and the catalyst Suitable compounds that provide Η-ions must be inert. In many cases the ligand can serve as a perforation of the structure M ¹ BH ₄ , M'A1H ₄ , H ₂ and M ¹ H _x , 20 solvents.

where M 'stands for an alkali metal or an alkaline earth metal In general, such solutions are used and χ is a number which corresponds to the valency of the medium hydrocarbons, such as, for example, benzene metal. This second method is suitable or xylene, or nitriles, such as acetogut for the preparation of many catalysts, which nitrile or benzonitrile, is used,
can be used independently. 25 The reaction temperatures are between -25 A third method of in-situ Katalysatorherstel- and +200 ⁰ C, preferably between 0 and 150 ⁰ C. lung, which is suitable when the ligand is atmospheric pressure to carry out the P (OR ) ₃ is the ligand, a nickel-present invention is satisfactory; Pressures of halide, such as NiCl ₂ , and a base, about 0.7 to 10 atmospheres are preferred, such as diethylamine or pyridine, but pressures of 0.5 to 100 atmospheres can also be added. A fourth method is to have spheres applied as appropriate.
Dicyclopentadienylnickel a neutral ligand,. · _T ,
such as M (OR) ₃ , where M As, P or Sb B e ι s ρ 1 e 1 1
and R is aryl to be added in the reaction mixture. A mixture of 20 g of 3-pentenenitrile and 2.2 g. In each case, the catalyst is formed under the conditions described after the triphenyl phosphite in a 100 ml three-necked glass cyanogen flask, which has a deposit above the liquid , whereby neither a special temperature level-ending gas inlet pipe, one through temperatures nor pressures have to be observed. a gas outlet conduit leading to a reflux condenser

Alkali borohydrides or a thermometer are provided as accelerators. Use tetra- (lower-alkyl) ammonium borohydrides. The system is flushed with nitrogen, whereupon sodium borohydride and potassium borohydride, 0.9 ml of liquid nickel tetracarbonyl dropwise, are particularly preferred. The promoter causes one to be given. After the evolution of gas has ended, the yield is improved; in certain cases, such as lung 0.2 g of sodium borohydride is heated worbeispielsweise in Cyanwasserstoffanlagerung of the mixture to 120 ⁰ C are added. Then 3- or 4-pentenenitrile is used to produce adipo-45 a stream of nitrogen gas through liquid cyanitrile, an improved isomer distribution is the hydrogen bubbling and the resulting gas mixture is the result. The amount of borohydride used can be passed over the surface of the stirred hot catalyst by a molar ratio of accelerator to catalyst mixture. A total of 9 ml of liquid will vary from 1:16 to 16: 1. The borohydride can be added to HCN over a period of 40 minutes, for example to the reaction mixture at the beginning of the 5 °. Analysis by gas chromatography or at a time during the reaction shows that 19.4% Adipo reaction will be added to the crude liquid product when the activity of the nitrile, 7.0% 2-methylglutaronitrile and 3.0% ethyl catalyst is in its effectiveness has decreased. contains succinonitrile. The yield of dinitrile is

The addition of hydrogen cyanide can carry through 29.4%, the degree of conversion to dinitrile is

be performed by putting a reactor with all 55 24.1%.

Respondents sent, you can also d - ·, »
preferably proceed so that the reactor with the

Catalyst and the accelerator, the unsaturated A mixture of 20 g of 3-pentenenitrile, 5.0 g of Ni (CO) ₂ compound and the solvent, if such a [P (C ₆ H ₅ ) J] ₂ and 0.2 g of sodium borohydride is used in, is charged, whereupon water-cyanide 60 is placed in a 100 ml glass flask. The system is purged hydrogen gas over the surface of the reaction mixture with nitrogen and heated to 120 ⁰ C. Hydrogen cyanide gas is then passed or bubbled through the reaction mixture by means of a nitrogen carrier. When using a gaseous unsaturated gas passed over the hot reaction mixture, the organic compound can contain the hydrogen cyanide. 6.3 g of HCN are added over a period of time from and the unsaturated organic compound together 65 40 minutes. There is one to be introduced into the reaction medium. The exothermic reaction takes place, so that the reaction molar ratio of unsaturated compound to caustic temperature fluctuates around 3 ° C above the surrounding bath, generally approximately. An analysis using gas chromatography

shows that the crude product is 28.5% adiponitrile, 5.0% 2-methylglutaronitrile and 1.6% ethylsuccinonitrile contains.

The yield of dinitrile is 35.1%. the degree of conversion to dinitrile is 32.4%.

Example 3

A mixture of 20 g of 3-pentenenitrile, 0.9 ml of Ni (CO) ₄ and 0.2 g of sodium borohydride is placed in a 100 ml glass flask. The system is purged with nitrogen and hydrogen cyanide gas is passed over the reaction mixture. The reaction temperature rises by 2 to 32 ° C. and then gradually falls. A total of 6.3 g of HCN are added over a period of one hour. Analysis by gas chromatography shows that the crude liquid product contains 0.2% adiponitrile, 0.5% 2-methylglutaronitrile and 0.3% ethylsuccinonitrile. The yield of dinitrile formed is 1.0%, the degree of conversion to dinitrile is 0.74%.

Example 4

A mixture of 5.0 g Ni (CO) ₂ [As (C ₆ H ₅ ) _{I 2} , 20 g 3-pentenenitrile and 0.2 g sodium borohydride is placed in a 100 ml glass flask, flushed with nitrogen and then on 120 ⁰ C heated. Hydrogen cyanide gas is then passed over the hot reaction mixture. A total of 5 ml of liquid hydrogen cyanide is added over a period of one hour. Gas chromatography analysis of the crude liquid shows that it contains 11.4% adiponitrile and 7.6% 2-methylglutaronitrile.

The yield of dinitrile formed is 19.8%, the degree of conversion to dinitrile is 13.8%.

Example 5

A mixture of 5.0 g Ni [P (OC ₂ H ₅ ) J] ₄ , 0.2 g sodium borohydride and 20 ml m-xylene is placed in a 100 ml glass reaction flask and flushed with nitrogen. The mixture is heated to 12O ⁰ C. Butadiene gas is bubbled through liquid hydrogen cyanide and the gas mixture obtained is passed over the hot catalyst solution. A total of 4 ml of liquid hydrogen cyanide are added. At this point analysis by gas chromatography shows that the crude liquid is 0.1% adiponitrile, 3.3% 2-methylglutaronitrile, 6% 2-methyl-2-butenenitrile. Contains 5% 2-methyl-3-butenenitrile, 14% 3-pentenenitrile and 1% 4-pentenenitrile.

At this point in the process, the flow of butadiene is stopped, whereupon another 12 ml of liquid Hydrogen cyanide can be introduced into the system in the form of a gas (nitrogen carrier). The analysis using Gas chromatography shows that the crude liquid obtained is 1.4% adiponitrile, 7.4% 2-methylglutaronitrile, 9% 2-methyl-2-butenenitrile, 4% 2-methyl-3-butenenitrile, Contains 14% 3-pentenenitrile and 1% 4-pentenenitrile.

The yield of dinitrile formed is 8.8%, the degree of conversion to dinitrile is 21.4%.

Example 6

A mixture of 5.0 g Ni [P (OC ₂ H ₅ ) 3] ₄ , 20 g 3-pentenenitrile and 0.2 g sodium borohydride is placed in a 100 ml glass flask. The system is purged with nitrogen and heated to 120 ⁰ C. Hydrogen cyanide gas is then passed over the surface of the hot reaction mixture using a nitrogen purge gas. A total of 9 ml of liquid hydrogen cyanide is added over a period of one hour. A light yellow solid substance is present during the entire reaction period. Gas chromatography analysis of the crude liquid shows that it contains 23% adiponitrile, 3.6% 2-methylglutaronitrile and 0.9% ethylsuccinonitrile. The yield of dinitrile formed is 27.5%, the degree of conversion to dinitrile is 25.5%.

Example 7

A mixture of 20 g of 3-pentenenitrile, 0.6 g of nickel cyanide, 6.2 g of triphenyl phosphite and 0.2 g of sodium borohydride is placed in a 100 ml glass flask and flushed with nitrogen. The mixture is ^{heated to 120 °} C., whereupon hydrogen cyanide gas is passed over the surface of the hot mixture. A total of 4 ml of liquid hydrogen cyanide are added over a period of 30 minutes. Gas chromatography analysis of the crude liquid shows that it contains 1.6% adipomitrile and 1.3% 2-methylglutaronitrile.

The yield of dinitrile formed is 2.9%, the degree of conversion to dinitrile is 2.8%.

Example 8

A mixture of 13.5 g Ni [P (OC ₆ H ₅ ) ₃ ] ₄ . 60 g of 3-pentenenitrile and 0.2 g of sodium borohydride are placed in a 200 ml glass flask, whereupon the system is flushed with nitrogen. The mixture is ^{heated to 120 °} C., whereupon hydrogen cyanide gas is passed over the hot reaction mixture. The temperature of the mixture rises to 123 ° C while the bath temperature is 122 ° C. A total of 10 ml of HCN are introduced into the system over a period of one hour. At this point the temperature of the reaction mixture is the same as that of the bath. Analysis shows that the crude liquid contains 23% adiponitrile, 5% 2-methylglutaronitrile and 2% ethylsuccinonitrile. About 0.1 g additional sodium borohydride is added to the reaction mixture and the stream of HCN is restarted. The temperature of the mixture rises by 3 ° C above the temperature of the bath. Hydrogen cyanide gas is passed over the mixture so long until the temperature of the reaction mixture, and the bath is 12O ⁰ C. Analysis of the crude liquid shows that it contains 25% adiponitrile, 6.7% 2-methylglutaronitrile and 2% ethylsuccinonitrile.

Another addition of 0.2 g of sodium borohydride, followed by the addition of HCN, has one Temperature rise in the reaction mixture of 7 ° C result. A total of 25 ml of liquid Hydrogen cyanide was passed over the surface of the mixture over a period of 45 minutes. The temperature of the mixture and the bath is 121 ° C. The analysis shows that the liquid is 31% Contains adiponitrile, 8.5% 2-methylglutaronitrile and 3% ethylsuccinonitrile.

The yield of dinitrile formed is 42.5%, the degree of conversion to dinitrile is 38.5%.

Example 9

A mixture of 4.5 g Ni [P (OC ₆ H ₅ ) J] ₄ and 20 g 3-pentenenitrile is placed in a 100 ml glass flask, whereupon the system is flushed with nitrogen. The mixture is ^{heated to 120 0} C, whereupon

Hydrogen cyanide gas is passed over the hot reaction mixture by means of a nitrogen carrier gas. A total of 9 ml of HCN are added over a period of 1.5 hours. Gradually, a light green solid substance forms. Gas chromatographic analysis of the crude liquid shows that it contains 2.9% adiponitrile. About 0.1 g of sodium borohydride are added to the used catalyst system, whereupon the mixture is ^{heated to 120 °} C. again. Hydrogen cyanide gas is then passed over the hot reaction mixture by means of a nitrogen carrier gas. The temperature of the reaction mixture increases during the initial addition of HCN to 5 ⁰ C above the temperature of the oil bath (121 ⁰ C). After the temperature of the mixture has fallen to 121 ° C., a liquid sample is taken and analyzed by means of gas chromatography. Analysis shows that the crude sample contains 24% adiponitrile. Another addition of sodium borohydride, followed by the addition of HCN, increases the adiponitrile concentration in the crude liquid reaction mixture to 27%. The yield of dinitrile formed is 27%, the degree of conversion to dinitrile is 24.5%.

25th

30th

35

20 g of 3-pentenenitrile and 0.2 g of sodium borohydride are placed in a 100 ml glass flask, whereupon the system is flushed well with nitrogen. The mixture is heated to 120 ° C, whereupon hydrogen cyanide gas is passed over the hot reaction mixture by means of a nitrogen carrier gas. After a Introduction time of about 9 minutes, the temperature of the reaction mixture rises to 128 ° C; this The temperature is 8 ° above the temperature of the surrounding bath. Total will be during 6.3 g of HCN were added over a period of 45 minutes. Analysis by gas chromatography shows that the crude liquid product has 20% adiponitrile, 5% 2-methylglutaronitrile and 2.3% ethyl succinonitrile contains.

The yield of dinitrile formed is 27.3%, the degree of conversion to dinitrile is 25.2%.

Example 11

A mixture of 20 g of 3-pentenenitrile, 2.5 g of triphenylantimony and 0.9 ml of liquid nickel tetracarbonyl is placed in a 100 ml glass flask. After completion of the evolution of gas (carbon monoxide) 0.2 g of sodium borohydride and the mixture is heated to 120 ⁰ C are added. A stream of HCN gas is then passed over the surface of the reaction mixture. A total of 6.3 g of HCN are added over a period of 30 minutes. Analysis by gas chromatography

i s ρ i e 1 10 I ^{6 3} Be 5.0 g > —P - A mix of H ₅ QH ₅ , H ₅ Q Ni (CO), P
"I. I.
C ₆

shows that the crude liquid sample had 1.8% adiponitrile, 2.6% 2-methylglutaronitrile and 1.6% ethyl succinonitrile contains.

The yield of dinitrile formed is 6.0%, the degree of conversion to dinitrile is 5.0%.

Example 12

A mixture of 20 g of ^{3-Penteniit; i} 10 g of triphenylphosphine, 3.15 g bis ^(p Acrylnitr and 0.2 g

Sodium borohydride is in a 1 islvslben,

which was flushed well with nitrogen.

The mixture is heated to 120 ⁰ C are obtained ml hydrogen cyanide gas in a nitrogen., _ ^ S is passed over the surface of the reaction mixture. The reaction temperature rises to 129 ° C. and then slowly falls. A total of 6.3 g of HCN are added over a period of 45 minutes. Analysis by gas chromatography shows that the crude liquid sample contains 4.1% adiponitrile and trace amounts of 2-methylglutaronitrile and ethylsuccinonitrile. The yield of dinitrile formed is 4.1%, the degree of conversion to dinitrile is 5.05%.

Example 13

Ni [P (OC ₂ H ₅ ) ₃ ] 4. is in 3-pentenenitrile (which contains 95% trans-3-pentenenitrile and 5% cis-3-pentenenitrile) at room temperature to form a 0.226 molar solution for the nickel complex and 8.78 molar for the 3-pentenenitrile (18.7 or 81.3 percent by weight). The nickel complex and its solution are permanently shielded from the atmosphere by means of a nitrogen blanket. Then an "O" ring syringe with a capacity of 100 ml is filled with this solution and inserted into an injection pump that can be operated at alternating speed for subsequent introduction into the reactor.

Anhydrous liquid hydrogen cyanide (stabilized with H ₂ SO ₄ and SO ₂ ) is placed in a freely movable plastic syringe with a capacity of 50 ml, which is placed in a metal cylinder which is open at both ends and which completely surrounds the syringe cylinder. The cylinder is wound with copper coils through which ice water is circulated to keep the hydrogen cyanide at a temperature of 0 to 5 ° C. This arrangement, which contains the HCN syringe, is installed in an injection pump that can be operated at alternating speed for subsequent delivery to the reactor.

Numerous small glass tubes are each filled with approximately 0.1 g of powdered sodium borohydride. These tubes are fitted with a flask at one end and placed in a dry atmosphere for the subsequent use to add the pipe contents to the reactor at certain time intervals stored during the reaction period.

The reactor is a cylindrical glass kettle, the height of which is twice the diameter; its content is 50 ecm. An overflow is provided at the top. The head of the reactor is with an effective stirrer and four small openings, which are made by means of semi-permeable rubber membranes are locked. The reactor is jacketed to allow the circulation of a heat transfer fluid to enable, which one to 125 ° C

209542/536

10

is provided. The reactants are extracted from the syringes through small stainless steel tubes, which open into the reactor through the semi-permeable rubber membranes. Under the actual process conditions under which vigorous stirring takes place, the liquid volume of the reactor in the quiescent state is 35 ecm. Exhaust gas and liquid product escape through the overflow opening. The liquid product is in one Collecting vessel is collected and periodically removed, the exhaust gas is on its way through to the drain out a kept at a temperature of 0 to 5 ° C condenser. Before starting the implementation will the reactor with pure nitrogen to remove atmospheric oxygen and water vapor flushed. A slight nitrogen purge is maintained during the reaction to allow for possibility the entry of oxygen. The temperature in the reactor is controlled by means of a Thermocouple measured and continuously * with the help of an automatic strip chart recorder recorded.

After thorough flushing with nitrogen, 0.2 g of NaBH _{4 are} added to the reactor at room temperature. 35 ecm of the catalyst solution in 3-pentenenitrile are pumped into the reactor, whereupon stirring is started. The circulation of the heat transfer medium in the jacket is started. After the reactor ^{temperature has reached 105 °} C., the HCN feed pump is started and set in such a way that it feeds 1.32 mmol of HCN per minute.

The moment at which the HCN influx begins is recorded as the no-stop time. 8 minutes after the no-stop time the exotherm and visual observations indicate that the reaction has begun and runs normally. Then the catalyst and 3-pentenenitrile solution are added to the reactor with a Pumped in at a speed of 1 cc / minute. The feed ratios (in moles) are:

HCN / 3-pentenenitrile = 0.15,

3-pentenenitrile / Ni [P (OC ₂ H ₅ ) 3] ₄ = 38.7.

The first liquid product runs out of the overflow 15 minutes after the no-stop time. The reactor is now operated continuously. The NaBH ₄ is added every 20 minutes in 0.1 g portions, starting 30 minutes after the no-stop time. Since the liquid build-up is 35 ecm and the loading speed is 1 ccm / minute, the “space time” or “dwell time” is calculated to be 35 minutes. After 155 minutes, the product concentrations in the reactor are constant, so that it can be assumed that the reactor is now under uniform conditions. These constant conditions are maintained until the point in time of 225 minutes; then the feed ratios are changed to show the operation of the process under different conditions. Table I summarizes the information on the reaction conditions and the product analyzes during the entire experiment. When the reaction has ended, the reactor is emptied and washed with benzene. The benzene used for washing is kept separately; Table III lists the ingredients contained in this benzene.

Table I feed ratio

Time, minutes temperature HCN / 3-PN 3-PN / Cat. ' Adiponitrile Remarks ⁰ C Weight percent 0 to 15 - - - - Start period 20th ■ 121.0 0.15 38.7 0.6 Approach to the 41 121.5 0.15 38.7 2.0 constant state 71 122.0 0.15 38.7 6.4 91 121.0 0.15 38.7 7.2 111 121.5 0.15 38.7 7.0 133 121.5 0.15 38.7 7.8 151 121.5 0.15 38.7 8.6 Procedure implementation 173 121.5. 0.15 38.7 8.6 under constant 193 121.5 0.15 38.7 8.3 conditions 216 121.5 0.15 38.7 8.7 238 122 - 10.6 Procedure implementation 251 122 0.25 38.7 12.8 at higher 270 121.5 0.25 38.7 12.2 PN conversion rate 280 121.5 0.25 38.7 12.7 308 121.5 0.25 - 38.7 11.1 328 121.5 0.25 38.7 10.9 349 121.5 0.25 38.7 11.4 368 121.5 0.25 38.7 12.6 377 121.5 ■ - - 13.9

Table II

Material balance, turnover and yield calculations

Introduced Taken total 311.8 g Catalyst and 302.85 g product 3-PN rehearse 16.5 g HCN 12.6 g during the Attempt 1.8 g NaBH ₄ 330.1 g 315.4 g

IO

95.5% total material balance

The end product contains 3.5 g of solids - im
essentially all Na ₂ Ni (CNV The liquid product 20 is analyzed by GC as follows:

Recyclable PN:

trans-3-pentenenitrile 5138%]

cis-3-pentenenitrile 10.36% > 67.07%

4-pentenenitrile 5.33% J.

cis-3-pentenenitrile 0.70%

trans-2-pentenenitrile 0.88%

Valeronitrile 1.48%

unknown (cis-3-methyl- ■ 4.65%

2-butenenitrile) 0.08%

Ethyl succinonitrile 0.32%

2-methylglutaronitrile 1.19%.

Product:

Adiponitrile ...: 8.11% 8.11%

Other components:
Nickel (titrimetric

Analysis) 1.19% 1.19%

81.02%

The remainder not taken into account is assumed to be ethyl phosphite (or products which incurred during the decomposition of phosphite) and complexed CN "acts

Table III
Yield calculation based on the following pentenenitrile balance

[Charging ^ I withdrawn liquid product. Benzene \ 96.8 g total J ~ difference - \ 311.8 g total; t \ 315.4-3.5 = 312g (96.8 g) +0.74 3-pentenenitrile (311.8 g) (312 g) (0.0241) = 233 g (0.813) = 253 g (0.6174) = 193 g 0.03 moles 3.15 moles 2.38 moles - -0.205 4-pentenenitrile 0 (312 g) (0.0533) = 16.6 g 0.205 moles - -0.056 Valeronitrile 0 (312 g) (0.0148) = 4.62 g 0.056 moles - -0.064 cis-2-PN-trans-2-PN 0 (312 g) not known (0.0166) = 5.18 g 0.064 moles - -0.072 Ethyl succinonitrile and 0 (312 g) 2-methylglutaronitrile (0.0251) = 7.83 g 0.072 moles (96.8 g) -0.237 Adiponitrile 0 (312 g) (0.004) = 0.387 g (0.0811) = 25.3 g 0.003 moles 0.234 moles Mole output PN, not considered for +0.106

_PN . _{Balance sheet =}

PN sales =

3.15

0.535 (100) 3.15

= 17.0%

... .. .., _t 0.237 (100) .._ _{0 /}

Adiponite yield = - = 44.3%

example

0.20 g of sodium borohydride are placed in a flask 65 which is closed by means of a serum stopper,

presented, which is provided with a magnetic stirrer and. The flask is filled with nitrogen. ge

with a reflux condenser, the gas inlet and purge, whereupon a nitrogen flow of about 5 ml / mi

Has nozzle tubes, as well as an injection port, groove is maintained during the reaction.

A slurry of 5.0 g (0.00385 mol) of tetrakis (triphenylphosphite) nickel catalyst in 50 ml of p-xylene is injected into the flask through the injection opening, whereupon the flask is ^{heated to 120 °} C. and kept at this temperature during the reaction will. A gaseous mixture of allene (flow rate about 0.0026 mol / minute) and hydrogen cyanide (flow rate about 0.0019 mol / minute) is passed over the well-stirred solution over a period of 200 minutes while 0.390 mol of hydrogen cyanide is passed into the flask will. The reaction mixture is then cooled and distilled by evaporation at room temperature under a pressure of 0.02 mm, 12.9 g of a residue and 56.1 g of a condensate being obtained, which is composed of butenenitriles and p-xyloI. Part of the condensate is subjected to gas chromatography (tricresyl phosphate column, 70 ° C.); the individual components are collected from the effluent and identified by infrared and NMR spectroscopy. For the quantitative determination of the reaction mixture, part of the condensate, to which 1,2-dichloroethane is added as an internal standard, is subjected to gas chromatography; four butenenitriles and the internal standard are isolated from the effluent stream in a single trap and the contents of that trap are analyzed by NMR spectroscopy. In this way it is found that the butenenitrile yield is 14.02 g (0.209 mol, 54%, based on hydrogen cyanide) and the composition of the butenenitriles is as follows: 81.5% allyl cyanide, 8.8% methacrylonitrile, 6.6% cis -Crotononitrile and 4.8% trans -crotononitrile.

Example 15

0.10 g of sodium borohydride are placed in a flask equipped with a magnetic stirrer, a reflux condenser with gas inlet and outlet tubes and an injection port which is closed with a serum stopper. The flask is purged with nitrogen and a nitrogen flow of about 10 ml / minute is maintained during the reaction. A slurry of 2.0 g (0,00154Mol) of tetrakis (triphenyl phosphite) -Nickelkatalysator in 22.1 g (0.330 mol) of allyl cyanide is injected into the piston through the injection port, is heated and the flask to 120 ⁰ C and at this temperature is held during the reaction. At a flow rate of 0.0027 mol / minute, gaseous hydrogen cyanide is passed over the well-stirred solution for a period of 145 minutes. At the same time, 0.390 moles of hydrogen cyanide are introduced into the flask. The reaction mixture is then cooled and ^{distilled by evaporation at 100 °} C. and 0.01 mm, 2.5 g of a residue and 21.3 g of condensate being obtained. Gas chromatography of part of the condensate is used to determine the presence of two main product components, which are isolated from the effluent and identified as glutaronitrile and methylsuccinonitrile by means of infrared and NMR spectroscopy. The quantitative analysis is carried out by gas chromatography, the integrated areas under the product peaks being compared with the area under the glutaronitrile peak of a standard solution of glutaronitrile in allyl cyanide. In this way it is determined that glutaronitrile and methyl

succinonitrile can be obtained in yields of 9.2 and 2.6%, based on allyl cyanide.

Example 16

The reaction is carried out according to the procedure described in Example 15 with 23.5 g (0.350 mol) of allyl cyanide, 0.390 mol (flow rate about 0.0031 mol / minute) hydrogen cyanide, 2.0 g (0.00154 mol) Tetrakis (triphenyl phosphite) nickel catalyst and 0.10 g sodium borohydride, but at one temperature carried out at 80 ° C. The reaction mixture is processed in the manner described in Example 15 and analyzed. Glutaronitrile and methylsuccinonitrile are produced in yields of 0.9 and 0.5%, based on allyl cyanide, formed.

Example 17

The reaction is according to the procedure described in Example 15 with 22.4 g (0.334 mol) of AlIyI cyanide, 0.390 mol (flow rate about 0.0027 mol / minute) hydrogen cyanide and 0.10 g of sodium borohydride, but with 2.0 g (0.00276 mole) of tetrakis (triethyl phosphite) nickel as a catalyst and at a temperature of 100 ⁰ C. The reaction mixture is processed and analyzed in the manner described in Example 15. Glutaronitrile and methylsuccinonitrile are formed in yields of 17.5 and 6.8%, respectively, based on allyl cyanide.

Example 18

The reaction is carried out exactly as described in Example 17, but in the presence of additional sodium borohydride (0.50 g total). Glutaronitrile and methyl succinonitrile are formed in yields of 2.3 and 8.0%, based on allyl cyanide.

Example 19

The reaction is carried out exactly according to the procedure described in Example 17, although 50 ml of p-xylene are added. Glutaronitrile and methylsuccinonitrile are used in yields of 1.4 and 0.7%, based on allyl cyanide, formed.

Example 20

In a mixture of 6 g of insoluble polymeric nickel complex, which is prepared by a method described below, 0.2 g of NaBH ₄ and 26.6 g of 3-pentenenitrile in a 200 ml reactor equipped with a mechanical stirrer, reflux condenser, gas inlet tube and heating jacket is provided, 6.8 g of HCN are introduced in the form of a gas together with some nitrogen over a period of one hour. Gas chromatographic analysis of the product shows that 3.6% of the 3-pentenenitrile is converted into dinitrile. which consist of 67% adiponitrile, 22% of 2-methylglutaronitrile and 11% of ethylsuccinonitrile.

The polymeric nickel complex is produced in three stages. An insoluble terpolymer is formed by polymerizing a mixture of 10.4 g styrene, 23 g p-iodostyrene, 1.0 g divinylbenzene and 0.3 g benzolyperoxide as a dispersion in 200 ml water and 0.5 g polyvinyl alcohol (Elvanol 52-22) prepared at 6O ⁰ C for a period of 2 hours and 85 ° C over a period of 12 hours. The polymer (30.5 g), which consists of small spheres, is filtered through a sieve with

a clear mesh size of 0.15mm (lOOmesh) isolated. It is washed with methanol before drying. This polymer suspended in 250 ml Benzene, is treated with lithium butyl (60 ml of a 15% solution in hexane) for 16 hours at 25 ° C, whereupon 21.2 g of diphenylphosphine chloride are added and stirring is continued for a further 15 hours is continued for a long time. The polymeric phosphine is by adding 800 ml of methanol and by Filtration isolated. The polymer weighs 33.8 g and contains 3.5% phosphorus. To one part (30 g) this Polymer suspended in 200 ml of tetrahydrofuran, 12.5 g of nickel tetracarbonyl are added at 25 ° C. with stirring added in 25 ml of tetrahydrofuran. After 30 minutes the mixture is under for 1 hour Held at reflux. 1.23 l carbon monoxide are set free. 31.5 g of the nickel containing Polymer are isolated by filtration and dried under a stream of nitrogen. The polymer contains 6.5% nickel and 2.9% phosphorus.

Example 21

Nickel tetrakistrifluorophosphine, Ni (PF ₃ I ₄ , is prepared according to T. K ruck and K. B aur, Chem. Ber., 98, 3070 (1965), by direct reaction of PF ₃ and nickel, with the exception that the metallic nickel is not produced by the thermal decomposition of nickel (II) oxalate, but by the reduction of NiCl ₂ · 6H ₂ O with NaBH _4. 8 g (0.136 mol) of pyrophoric nickel powder are placed in an ampoule and "placed in an 80- is cc autoclave is set under a pressure of 300 atmospheres PF _3, followed by heating to 100 ° C and shaken for 45 hours at this temperature, excess PF _3, at -. 100 ⁰ C stripped and the residue distilled, the boiling point is 60 ° C / 600 mm Hg. The yield is 34 g, ie 61%.

a) 1 g (0.0025 mol) of this Ni (PFj) ₄ and 10 g (0.123 mol) of 3-pentenenitrile are heated to 6O ⁰ C. When heated, PF ₃ escapes, whereby the two-phase system • changes into a single phase. HCN is passed over the surface of the reactants by means of a stream of nitrogen (40 ml / minute). No dinitriles can be found in the product obtained.

_{b) 0.1 g of NaBH 4 are} added to the same reaction as described above under a). After one hour, 0.21% 1,2-dicyanobutane, 0.16% 1,3-dicyanobutane and a trace of adiponitrile are obtained.

The yield of dinitrile formed is 0.37%, the degree of conversion to dinitrile is 0.27%.

Further improvements regarding the conversion of 3-pentenenitrile to dinitrile are made with larger amounts of free phosphite were observed. Table IV shows this effect.

Table IV Example 22

A mixture of 20 g of 3-pentenenitrile, 4.5 g of Ni [P (OCeH ₅ ),] * 2.2 g of P (OC ₆ Hj) ₃ and 0.2 g of NaBH ₄ is placed in a 100 ml glass reaction flask . The system is purged with nitrogen, and the mixture is heated to 120 ⁰ C. Hydrogen cyanide gas is purged over the surface of the hot mixture in a nitrogen carrier gas. A total of 9 ml of liquid hydrogen cyanide is added over a period of 45 minutes. Gas chromatographic analysis shows that the crude product contains 29.6% adiponitrile, 5.8% 2-methylglutaronitrile and 1.6% ethylsuccinonitrile.

The yield of dinitrile formed is 27.0%, the degree of conversion to dinitrile is 26.8%.

at
game 22 Mole excess
Phosphite / mole Ni Adiponitrile % Dinitrile in
2-methyl
glutaronitrile the product
Ethyl succino
nitrile B. 2 29.6 5.8 1.6 C. 4th 33.4 6.5 1.8 D. 6th 37.1 6.9 2.0 E. 10 43.3 7.8 2.4

Table V

Yield to Degree of implementation Example 22 formed dinitrile to dinitrile B. 27.0 26.8 C. 41.7 44.2 D. 46.0 52.1 E. 53.5 88.2

Example 23

A mixture of 20 g of 3-pentenenitrile, 4,5 ^- g Ni [P (OC ₂ H _{5) 3] 4} and 0.05 g of lithium borohydride is placed in a 100 ml GIaskolben. The system is purged with nitrogen and the mixture is heated to 120 ° C. Hydrogen cyanide gas is purged over the surface of the hot mixture in a nitrogen carrier gas. A total of 9 ml of liquid hydrogen cyanide is added over a period of 50 minutes. Gas chromatographic analysis shows that the crude reaction mixture contains 5.4% adiponitrile, 1.1% 2-methylglutaronitrile and 0.3% ethylsuccinonitrile.

The yield of dinitrile formed is 6.8%, the degree of conversion to dinitrile is 6.15%.

Example 24

A mixture of 20 g of 3-pentenenitrile, 4.5 g of Ni [P (OC ₆ H _s ) 3] ₄ and 0.2 g of tetramethylammonium borohydride is placed in a 100 ml glass reaction flask. The system is purged with nitrogen, is heated and then the reaction mixture to 120 ⁰ C. Hydrogen cyanide gas in a nitrogen carrier gas is then purged over the surface of the hot mixture. A total of 9 ml of liquid hydrogen cyanide is added over a period of one hour. Gas chromatographic analysis shows that the crude reaction mixture contains 10% adiponitrile, 2.3% 2-methylglutaronitrile and 0.8% ethylsuccinonitrile.

The yield of dinitrile formed is 13.1%, the degree of conversion to dinitrile is 11.9%. '

209542/530

17th
Example 25

A mixture of 20 g of 4-pentenenitrile, 4.5 g of Ni [P (OC ₆ H ₅ ) J] ₄ and 0.2 g of sodium borohydride is placed in a 100 ml glass flask. The system is purged with nitrogen, is heated and then the reaction mixture to 120 ⁰ C. Hydrogen cyanide gas in a nitrogen carrier gas is then passed over the hot mixture. A total of 9 ml of liquid hydrogen cyanide is added over a period of one hour. Gas chromatographic analysis of the crude reaction mixture shows that the sample contains 24% adiponitrile, 5.9% 2-methylglutaronitrile and 1.2% ethylsuccinonitrile.

The yield of dinitrile formed is 31.1%, the degree of conversion to dinitrile is 24.5%.

Example 26

A mixture of 20 g of 3-pentenenitrile, 4.5 g, ₂₀ Ni [P (OC ₆ H ₅ ) ₃ ] ₄ Wd 0.2 g of potassium borohydride is placed in a 100 ml glass flask. The system is purged with nitrogen, is heated and then the reaction mixture to 120 ⁰ C. Hydrogen cyanide gas in a nitrogen carrier gas is then passed over the surface of the hot mixture. A total of 9 ml of liquid hydrogen cyanide is added over a period of 50 minutes. Gas chromatographic analysis shows that the crude reaction mixture contains 21% adiponitrile, 5.7% 2-methylglutaronitrile and 1.7% ethylsuccinonitrile.

The yield of dinitrile formed is 28.4%, the degree of conversion to dinitrile is 25.8%.

Example 27

35

A mixture of 20 g of 3-pentenenitrile and 3.8 g of phenyldiphenylphosphinite is placed in a 100 ml glass flask. The system is purged with nitrogen and 1 ml of liquid nickel tetracarbonyl is added. There is a violent evolution of gas. After completion of gas evolution 0.2 g of sodium borohydride and the mixture is heated to 120 ⁰ C are added. Hydrogen cyanide gas in a nitrogen carrier gas is then purged over the surface of the hot mixture. A total of 9 ml of liquid hydrogen cyanide is added over a period of 50 minutes. Gas chromatographic analysis shows that the crude reaction mixture contains 33% adiponitrile, 6.4% 2-methylglutaronitrile and 1.7% ethylsuccinonitrile.

The yield of dinitrile formed is 41.1%, the degree of conversion to dinitrile is 36.3%.

Example 28

55

A mixture of 20 g of 3-pentenenitrile and 1.4 g of tributylphosphine is placed in a 100 ml glass flask. The system is purged with nitrogen and 1 ml of liquid nickel tetracarbonyl is added dropwise. The solution is then ^{heated to 50 °} C. and kept at this temperature until the evolution of gas ceases. To the clear solution 0.2 g of sodium borohydride and the mixture is heated to 120 ⁰ C are given. Hydrogen cyanide gas in a nitrogen carrier gas is then purged over the surface of the hot reaction mixture. The temperature of the mixture rises to 122 ° C and then slowly decreases. A total of 9 ml of liquid hydrogen cyanide is added over a period of 40 minutes. Gas chromatographic analysis shows that the crude product contains 0.1% adiponitrile, 0.7% 2-methylglutaronitrile and 0.2% ethylsuccinonitrile.

The yield of dinitrile formed is 1.7%, the degree of conversion to dinitrile is 1.3%.

Example 29

A mixture of 20 g of 3-pentenenitrile, 2 g of bisacetylacetonatonickel (II) and 3.6 g of triphenyl / phosphine is placed in a 100 ml glass flask which has previously been flushed with nitrogen. The mixture is heated to 12O ⁰ C, followed by 0.4 g sodium borohydride are added. A yellow-green reaction mixture is formed. Hydrogen cyanide gas is purged over the surface of the reaction mixture in a nitrogen carrier gas. The temperature of the reaction mixture rises to 128 ° C. and then slowly decreases. A total of 9 ml of liquid hydrogen cyanide is added over a period of 45 minutes. Gas chromatographic analysis shows that the crude liquid product contains 1% adiponitrile, 0.2% 2-methylglutaronitrile and 0.08% ethylsuccinonitrile.

Example 30

A mixture of 20 g of 3-pentenenitrile and 2 g of o-phenylene-bis-dimethylarsine is in a 100-nil three-necked glass flask with a gas inlet tube which ends above the liquid level, a gas outlet which leads through a reflux condenser, and a thermometer is provided, submitted. The system is purged with nitrogen and 1.0 ml of liquid nickel tetracarbonyl is added dropwise. The solution is ^{heated to 50 °} C. and kept at this temperature until the evolution of carbon monoxide gas ceases. At this time, 0.2 g of sodium borohydride and the mixture is heated to 120 ⁰ C are added. A stream of hydrogen cyanide gas is passed over the surface of the reaction mixture using a nitrogen purge gas. A total of 9 ml of liquid hydrogen cyanide is added over a period of one hour. Gas chromatographic analysis shows that the crude product contains 5.2% adiponitrile, 4.6% 2-methylglutaronitrile and 1.7% ethylsuccinonitrile.

Example 31

A mixture of 20 g of 3-pentenenitrile and 3.0 g of (C ₆ H ₅ ) _{I 2} PCl is placed in a 100 ml glass flask. The system is purged well with nitrogen and 1 ml of liquid nickel tetracarbonyl is added dropwise. There is a vigorous evolution of gas. After completion of gas evolution 0.2 g of sodium borohydride and the mixture is heated to 120 ⁰ C are added. Hydrogen cyanide gas in a nitrogen carrier gas is then purged over the surface of the reaction mixture. A total of 9 ml of liquid hydrogen cyanide is added over a period of 20 minutes. Gas chromatographic analysis shows that the crude product contains 0.4% adiponitrile, 0.3% 2-methyl-glutaronitrile and 0.3% ethylsuccinonitrile.

Example 32

A mixture of 2.72 g

OCH,

10.15 g of 3-pentenenitrile and 0.05 g of sodium borohydride are placed in a 50 ml three-necked glass flask equipped with a gas inlet tube which ends above the liquid level, a gas outlet which leads through a reflux condenser, and a thermometer. The system is purged with nitrogen and a stream of HCN gas is passed over the surface of the reaction mixture at a rate of approximately 2 ml / hour together with nitrogen at a rate of 22 ecm / minute. The initial temperature of the supplied gas is 21 ⁰ C and the exhaust gas "o 94 ° C; after 11 minutes, however, the temperature of the supplied gas rises to 117 ° C and that of the exhaust gas to 122 ° C; the gases are kept near these temperatures for the remainder of the experiment. The experiment is stopped after a further 82 minutes. Analysis of the crude liquid shows that there is 20.49% adiponitrile, 3.62% 2-methylglutaronitrile and 0.81% ethylsuccinonitrile.

Example 33

A mixture of 2.81 g

Ni

10.15 g of 3-pentenenitrile and 0.05 g of sodium borohydride is placed in a 50 ml three-necked glass flask which is supplied with a gas inlet pipe which ends above the liquid level, a gas outlet which passes through a Condenser leads, and a thermometer is fitted, submitted. The system runs on nitrogen purged, followed by a stream of HCN gas at a rate of approximately 2 ml / hour with nitrogen at a rate of about 35 cc / minute over the surface of the reaction mixture is directed. The initial temperature of the bath is 138 ° C; this temperature rises Gradually to 135 ° C. during the test, which lasted 275 minutes. After this time, the apparatus is put out of service. It turns out that the crude liquid is 10.5% adiponitrile, 2.59% 2-methylglutaronitrile and 0.90% ethyl succinonitrile contains.

Claims (1)

Claim: Process for the preparation of organic nitriles by reacting an organic compound containing at least one ethylenic carbon-carbon double bond with hydrogen cyanide in the presence of a zero-valent nickel complex as a catalyst and an accelerator, characterized in that 3- or 4-pentenenitrile, butadiene, allene or allyl cyanide are used with hydrogen cyanide at a temperature between -25 and +200 ⁰ C in the presence of a zero-valent nickel complex of the general formula