DE1618797A1 - Process for the catalytic hydrocyanation of unsaturated organic compounds - Google Patents

Description

E. I. DU PONT DE HEHOURS AND COMPANY 10th and Market Streets, Wilmington / Delawar · 19898, V, St. A,

Process for the catalytic hydrocyanation of unsaturated

organic compounds

It is known that the addition of hydrogen cyanide to double bonds, which are adjacent to an activating group, such as a nitrile or carboxy group, for example easy to proceed. On the other hand, the addition of hydrogen cyanide to non-activated double bonds takes place if Difficult at all, usually requiring the use of high pressures and temperatures. An improvement this procedure consists in that nickeloarbonyl with or without the addition of a tertiary aryl phosphine or arsine is used * However, there is a disadvantage to this method indicates that using non-conjugated olefinic starting materials a relatively high percentage of undesirable poly / animal products is formed, and also in all cases Successful expansions can be achieved «In addition, this process is

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ren for the production of adiponitrile from the fentenenitriles not satisfactory.

In the German patents and. ... ...

(Patent applications D 40 818 and D 40 857) are improvements this process described, which consists in the fact that a large number of catalysts from zero-valued nickel compounds optionally used together with a promoter consisting of tetraalkylammonium or an alkali borohydride.

The present invention contemplates the use of certain promoters to activate the nickel catalyst. The promoter is generally a compound containing a zinc, cadmium, beryllium, aluminum, gallium, indium, silver, Titanium, zirconium, hafnium, germanium, tin, vanadium, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, Palladium * thorium, erbium, iron or cobalt catalyst or mixtures of these catalysts. Preferably the compound should be at least partially soluble in the system be. In addition, the connection should preferably not have a slope to carry out an oxidation, as this is generally the case at least a partial loss of the ileal catalyst Consequence.

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The anionic part of the compound is preferably a fluoride, Chloride, bromide or iodide, an anion of a lower fatty acid with 2 to 7 carbon atoms «

HPO ₅ ² -, H ₂ PO ₂ ", CP ₅ COO-, OSO ₂ C ₇ P ₁₅ -

O".

or SO ^ or the like, but organometallic compounds are also possible (for example (CgH ₅ ), AlgCl ₅ and CgH The promoter serves to improve the number of possible cycles and in certain cases to increase the yield and reaction rate becomes particularly clear in the hydrocyanation of 5- or 4-pentenenitrile to adiponitrile. The amount of promoter used can generally vary from promoter to catalyst within a molar ratio of about 1:16 to 50 μl. The promoter can be used by various methods. At the beginning of the reaction, at least a certain amount of the promoter can be added to the reaction mixture, further additives can be added at any point during the reaction *

The catalysts are generally zero-valent nickel compounds * that are free of carbon monoxide · You can be educated or are made in situ and consist of nickel compounds, which have ligands, for example alkyl or aryl

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(where any of the radicals mentioned have up to 18 carbon atoms contains) -phosphine, -areine, -stibine, -phosphite, -arsenite, -stibites and mixtures of such ligands.

A preferred group of these nickel compounds has the general structure

^A 3

where A ,, A ^, A, and A ^ are neutral ligands that are the same or can be different and correspond to the formula F (XYZ), where X and Y are R or OR and Z has the formula OR and the three substituents R, which can be the same or different, represent an alkyl or aryl group having up to 18 carbon atoms, with aryl being preferred. Particularly preferred substituents R are

f \ and fi

where X is Cl, OCH. or CH, * If necessary, the Substituents R, if possible, be linked to one another. The preferred neutral ligands of this group are the ary! phosphites, such as triphenyl phosphite, TrI- (nH-p-chlorophenyl) phosphite, Trl (tt + p-taethoxyphenyl) phosphite and

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Tri (m-KP-eresyl) phosphite and mixtures of these phosphites. Under many of the reaction conditions there was a lack of harmony the substituents A ,, A ", A- or Ah are evaporated from the nickel.

The ligands suitable for the formation of the catalyst can be defined quite broadly as those atoms or molecules which are able to act as <F- 7Γ- bonded partners in one or more coordination mouths. A description of a smaller ligand can be found in " Advances Inorganic Chemistry "by F. Albert Cotton and G. Wilkinson * Intersoienoe Publishers, in particular on pages 602 to 606 (1962).

Satisfactory methods of making these nickel compounds are ia of the French patent 1 297 934, in "Chem. Soo. Journal" (London), pp. 1378-1389 (1960) and in "JACS", 81, 4200 to 4209, (1959).

In many cases it is advantageous if there is an excess of certain neutral ligands with respect to the nickel coraplex. The preferred ligands are the aryl phosphites in which the aryl groups contain up to 18 carbon atoms. In general, the excess ligand is in an at least two-fold olefinic carbon black, based on the

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dene nickel. The only limitation on the excess of ligand is practical because the ligand can even be used as a solvent. In general, however, very little benefit is obtained when using an excess of more than 500 moles of the ligand relative to 1 mole of nickel. The preferred triaryl phosphites which can be used as excess ligand are tri-phenyl phosphite, tri (si + p-insthoxyphenyl) -phosph.it υτΑ tri- (n + p-ureeayl) -phosphite and also?

The use of an excess of ligand can be used in the by controlling the product distribution and thus reducing the amount of by-products formed as well as lengthening it serve the life of the catalyst. The used excess Ligand can be the same as the ligand attached to the nickel in the nickel compound fed to the reactor or differ from this.

There are several methods of making the nickel compounds in situ. For example, nickel carbonyl and a neutral ligand as defined above (with the exception of carbon monoxide) added to the reaction mixture; will. in the general will in at least eirieai part of the original Nickel carbonyls every four moles of CO under the reaction conditions

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by another ligand, such as tri-phenyl phosphite, replaced. A second method is to use the neutral ligand (as defined above), a nickel (II) compound such as a nickel halide, for example NiClp, Ni (CN) ₂ or bis (aoetylacetonato) nickel (II), and add one hydride ion source. Suitable sources of H "ions are compounds of the formula M ¹ CBH ^] _x , M * [AlH ^] _χ » H ^ and Κ'Η _χ , where M 'is an alkali metal or alkaline earth metal and X is a number, which A third method is carried out in such a way that dieyclopentadleny / nickel is added to the reaction mixture with a neutral ligand such as M (OR), where H is As, P or Sb and R is aryl In any case, the catalyst is formed under the hydrocyanation reaction conditions specified below, there is no need to adhere to any other special temperatures or pressures *

The present invention provides a process for the preparation of nitriles or dinitriles from non-conjugated olefins In high yield under mild conditions, with only minimal polymers being formed and the use of the Catalyst limited to a minimum.

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The method according to the invention is generally unsaturated organic compounds containing 2 to 20 carbon atoms and at least one non-conjugated aliphatic can be used Have carbon-carbon double bond. the 3-pentenenitriles and 4-pentenenitriles are particularly preferred. Suitable unsaturated compounds are olefins and olefins which are substituted with groups which do not constitute the catalyst attack * e.g. cyano groups. To those unsaturated Compounds are mono-olefins, which are 2 to 3 20 Contain carbon atoms, e.g. ethylene, propylene * Butene-1, pentene-2, hexene-2 or the like. (non-conjugated diolefins, such as allene) and substituted compounds such as 3-pentenenitrile and 4-pentenenitrile.

The most significant advantage of the method according to the invention over the previously known method is that the catalyst life in the production of dinitriles, such as for example adiponitriles from either 3-pentenenitrile or 4-pentenenitrile, is extended «The total number of cycles (Molar ratio of product to catalyst) that can be achieved often depends on the impurities in the system. Yet a uniform improvement is achieved through the use of the promoter. Will implementation under optimal conditions carried out, then the number of achievable cycles

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be over 200. Improved yields and reaction rates are also achieved by using the promoter achieved »

In general, the catalysts of the invention cause the isomerization of j3-pentenenitrile to 4-pentenenitrile. The catalysts are therefore particularly suitable for the synthanes of adiponitrile and substituted adiponitrile. This property of enabling isomerization can be expressed in simple terms: -. » Example be exploited in that pure 3 is ^"p contacted sntennitril with the catalyst in the presence of 1 mole KLSQj, per mole of nickel * whereupon ⁰ G is heated for one hour at 32O and analyzing anschliesend 4-Pentsnnitril, for example by gas chromatography using a 2 m long copper tube with a diameter of 6.35 vm (l / 4 ^w), with 20 # (2-oyanoäthoxypropan) (based on weight) Tris. ₇ welohes to fireclay bricks having a size of 0.17 His 0.25 Bun.. (60-80 mesh, USStandard SiebgröSe) is deposited, is filled, the adsorbent is heated to 100 ^p C and the evaporator at 150 ⁰ C held, wherein a Heliurastrcra of 75 ml / minute is maintained WSErmeleitfShigkeitsdetektor a can be used The relative elution time of 4-pentenenitrile is approximately 30 minutes. The formation of 4-pentenenitrile can be seen as an indication that the catalyst

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catalyzes the isomerization of ^ -Pantenniltril ~ u 4-Pentonnicril. Preferably at least $ 0.5 4-Pen'v3nnitrii are formed. The catalysts prepared in situ can then be regarded as corresponding to this test if the Niokel connection, provided that it is used together with at least one Stoichiometric equivalent amount of the Ligsuidsn is added. Provides the preconfigured Nlokel complexes as required.

The hydrocyanation reaction can be carried out by that a reactor is loaded with all starting materials or even more preferably with the catalyst or catalyst components, the unsaturated organic compound, the promoter and, if a solvent is used, charged with this whereupon the hydrogen gas over the surface passed through the reaction mixture or through the reaction mixture is pearled. Another method is to put the catalyst, promoter, hydrogen cyanide and, if one, in the reactor Solvent is used to submit this and the unsaturated Add compound slowly to the reaction mixture. The molar ratio of the unsaturated compound to the catalyst generally varies from about 10: 1 to 2000: 1. at A process carried out continuously can do a lot larger katalyaatonsengs, for example with a ratio of unsaturated compound to catalyst of 1: 5, in the

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Reactor are introduced.

Preferably, a reaction medium is used, for example by stirring or shaking. The cyanated product can be obtained by customary methods, for example by distillation. The reaction can either be batchwise or continuously be performed.

The hydrocyanation reaction can be carried out with or without the use of a Solvent are carried out. The solvent should be liquid and opposite at the reaction temperature and pressure inert to the unsaturated compound and the catalyst. In general, such solvents are hydrocarbons, such as benzene or xylene, or nitriles, such as acetonitrile or benzonitrile, are used. In many In some cases, the ligand can serve as a solvent.

Certain ether the reaction mixture may be added, many of which are ^v ether solvent. This ether act to that improved yield and generally higher cycles are ersielt, particularly in the production of adiponitrile from 3-pentenenitrile or 4-pentenenitrile "This influence is ia generally at temperatures of about 20 to 75 ^e C is the largest. About 75 % by volume of ether can, based on the

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entire reaction mixture, can be used. These ethers can be acyclic or acyclic and contain 1 to 5 Kthei bonds between lower alkylene radicals or arene radicals. Acyclic ethers are terminated with lower alkyl groups. Of these ethers, dioxan, trioxane, CH ₅ -O-CIi ₂ CHg-O-CH ₃ , CKL-0-CHgCHg-O-CHgCHg-O-CH-j, o ~ dimethoxybenzene, tetrahydrofuran or the like. mentioned.

Which is preferably adhered to the exact temperature *, depends to some extent on the particular catalyst-used 'of each set of the unsaturated compound and ¹ desired speed. In general Taraperaturen can be adhered to 200 ⁰ C of -25, temperatures are preferably from 0 to 150 ⁰ C.

Usually atmospheric pressure is used to carry out the present Invention satisfactory, but higher pressures up to about 100 atmospheres can optionally be used will.

The following examples illustrate the invention without restricting it. Unless otherwise stated, all percentages relate to the weight.

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example 1

A 50 ml three-necked round bottom flask, which is provided with a reflux condenser, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an oil bath ^{kept at a temperature of 115 °} C. and flushed with dry, deoxygenated nitrogen. The flask is filled with 0.350 g (0.0018 mol) of ZnHPO ₃ and then with 0.650 g (0.0005 mol) of Ni [P (OC ₆ H ₅ ) ^] ₄ , 16 g (0.2 mol) of 3-pentenenitrile and 3 * 1 g (0.01 mol) of P (OCgH ₅ ), charged. A stream of dry, deoxygenated nitrogen gas is then bubbled through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The hydrogen cyanide is renewed if necessary. The nitrogen gas flow is set to 10 ml of nitrogen per minute in order to set a feed amount of gaseous hydrogen cyanide which is equivalent to approximately 0.5 ml (measured at ^{0 ° C.) of liquid hydrogen cyanide per hour.} The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture. It is then passed over the surface of the reaction mixture in the flask. The reaction is ended after 6 1/2 'hours.

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Analysis by gas chromatography shows that 64.5 $ des 5-pentenenitrile have been converted into dinitriles, with from the converted 3-pentenenitrile $ 73.2 from adiponitrile and 26.8 $ consist of 1,3-dicyanobutane and 1,2-dioyanobutane. The number of cycles (molar ratio of the dioyanobutanes produced to the catalyst fed in) is 242.

Example 2

A 50 ml three-necked round bottom flask fitted with a reflux condenser, which is connected to a dry ice trap, an inlet and a magnetic stirrer is provided in a a temperature of 115 ° C held oil bath used and with purged with dry, deoxygenated nitrogen. The flask is filled with 0.219 g (0.001 mol) of Zn (CH, C00) .2H 0 and another

y ti. C.

closing with 0.650 g (0.0005 mol) Ni [P (OC ₆ H ₅ ),] ^ 20 g (0.25 mol)> pentenenitrile and 3.1 g (0.01 mol) P (OC ₆ H ₅ ) , loaded. Then a. Stream of dry, deoxygenated nitrogen gas is bubbled through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The nitrogen gas flow is used to set a feed amount of gaseous hydrogen cyanide, which is equivalent to approximately 1.0 ml (measured at 0 ^° C.) of liquid hydrogen cyanide per hour, to 20 ml

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Set nitrogen per minute. The gas mixture obtained is then passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction mixture in the flask. The reaction is ended after three hours.

Analysis by gas chromatography sseigt "that the crude product l6 _f 2% adiponitrile ($ 79 based on the converted 3--Pentennitr.il) and k _t h%, ^ -. Containing Diejanobutan" The number of cycles is 92.

Example 3

A 50 Kl three-necked round bottom flask Tnit case a Rüekflußkühler which * with a dry ice is ^ / * erbunden a Sinlaß and a magnetic stirrer is provided * is used in a heated on a Temperacur of about 94 ⁰ C oil bath. The cults will r.iii; dry, deoxygenated nitrogen, flushed, 0.251 g (0.001 mol) of Zn [H ₃ PO ₂ I ₂ ^ H ₅₃ O and then 0.650 g (0.001 mol) of Ni [P (OCgH ₁ -),] ^, 20 g (0.25 mol) of 3-penonitrile and 3..I g (0.01 mol) of P (OC ₆ H ₅ ) are added. The temperature of the oil bath is gradually increased from 94 ⁰ C to 119 ^a G for a period of 11 l / 4 hours. In this way, the temperature of the reaction mixture becomes close to 110 ° C for most of the heating period

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held. A stream of dry, deoxygenated nitrogen gas is bubbled through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The hydrogen cyanide is renewed if necessary. The nitrogen gas stream is äuqivalent for setting a Beschickungsraenge of gaseous hydrogen cyanide, which is about 0.5 ml (measured at 0 ⁰ C) of liquid hydrogen cyanide per hour * set at 10 ml per minute of nitrogen. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of poisoning and then flushed over the surface of the reaction mixture in the flask. The reaction is ended after 11 1/4 hours.

Analysis by gas chromatography shows that 4l # des 3-pentenenitrile have been converted to dinitriles, with of the dinitriles obtained, $ 75 * 1, from adiponitriles $ 21.3 consist of 1,3-dicyanobutane and 2.7 $ of 1,2-dicyanobutane. The number of cycles is 183.

Example 4

A 50 ml three-necked round bottom flask fitted with a reflux condenser, which is connected to a dry ice trap, an inlet

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ff

and a magnetic stirrer is provided, is inserted into a bath maintained at a temperature of 8O ⁰ C oil bath and purged with dry, deoxygenated nitrogen. The flask is filled with 0.10 g (0.00044 mol) of zinc bromide and then with 0.325 g (0.00025 mol) of Ni [P (OC ₆ H ₅ ^] ₄ , 20 g (0.25 mol)> pentenenitrile and 3 .1 g (0.01 mol) of P (OC ₆ H ₅ J ^. A stream of dry, deoxygenated nitrogen gas is passed through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath The nitrogen gas flow is adjusted to set a feed amount of gaseous hydrogen cyanide which is equivalent to approximately 0.4 ml (measured at 0 ^° C.) of a liquid hydrogen cyanide per hour. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove »Removal of traces of moisture and then rinsed over the surface of the reaction mixture in the flask. The reaction is complete after 7 hours.

Analysis by gas chromatography shows that 25 $ des 3-pentenenitrile have been converted into dinitriles, with the converted 3-pentenenitrile at $ 82 from adiponitrile, 15 / consists of 1,3-dicyanobutane and 2 ^ 4 $ of 1,2-dicyanobutane. The number of cycles is 250.

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Example 5

A 50 ml three-necked round bottom flask provided with a reflux condenser, which is connected to a Trookeneisfalle, an inlet and a magnetic stirrer, in a at a temperature of 90 - used 5 ⁰ C held oil bath and treated with dry, deoxygenated nitrogen flushed. The flask is filled with 0.437 g (0.0015 mol) of Zn (GP ₃ COO) ₂ and then with 3.4 ml (0.01 mol) of P (OC ₆ H ₅ ) ,, 39.1 ml (0.4 mol ) 3-pentenenitrile and 1.40 g (0.001 mol) Ni [P (OC ₆ H ₅ ) 34th charged. A stream of trooken, deoxygenated nitrogen gas is bubbled through a liquid hydrogen cyanide contained in a 20 ml flask contained in an ice bath. The hydrogen cyanide is renewed if necessary. The nitrogen gas flow is adjusted to 28 ml nitrogen per minute. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction mixture in the flask. The reaction is complete after IT hours and 52 minutes.

Analysis by means of gas chromatography shows that 47.3 % of the 3-pentenenitrile has been converted into dinitriles, the dinitriles produced being 80.5 $ from adiponitrile, 15.8 $ from 1,3-dicyanotoutane and 3 * 7 $ Compose 1,2-dicyanobutane. The number of cycles is 189.

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Example 6

A 50 ml three-necked round-bottomed flask, which is provided with a reflux condenser, which is provided with an oxner dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 90 °} C. and flushed with dry, deoxygenated nitrogen. The flask is filled with 0.300 g (0.0008 MoX) cadmium iodide and then with 0.650 g (0.0005 mol) Ni [P (OC ₆ H ₅ ) -J ^, 20 g (0.25 mol) 3-penteimitrile and 3.1 g (0.01 mole) P (OCgH ₅ ) - charged. A stream of dry, of Sauerstoj? F befreitein nitrogen gas is 10 ml of a liquid Cyanwasserctoffs, which is contained in a 20 ml flask is cooled in an Eisb & cL, bubbled. Represents nitrogen gas stream is such eingestelltdaß a feed amount of gaseous hydrogen cyanide obtained is which is about 0.5 ml (measured at 0 ^e C) a liquid Cysnw & sserstoffs "corresponds per hour. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then rinsed over the surface of the reaction mixture in the flask and stopped the reaction for 6 1/2 hours.

Analysis by gas chromatography shows that 29 »6 # des 3-pentenenitrile have been converted to dinitriles, see

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the converted 3-pentenenitrile at $ 84.3 from Adiponitrll, Ij5.4 # from 1,3-Dieyanobutane and $ 2.2 from 1,2-Dlcyanobutane together " puts. The number of cycles is 148.

Example 7

A 50 ml three-necked round-bottomed flask, which is provided with a RüokflußkUhler, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 90 °} C. and flushed with dry, deoxygenated nitrogen . The flask is charged with 0.110 g (0,00OJ mole) of cadmium iodide and subsequently with 0.325 g (0.00025 mol) NICP (OC ₆ H ₅ J ₃ J _4, 25.0 g (0.31 mol) of 3-pentenenitrile and 3.1 g (0.01 mol) of P (OCgH -) - are charged A stream of dry, deoxygenated nitrogen gas is passed through 10 ml of a liquid hydrogen cyanide contained in a 20 ml flask which is in a Ice bath is cooled, bubbled. The hydrogen cyanide is renewed if necessary. The nitrogen gas flow is adjusted to 5 ml of nitrogen per minute. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then over the surface of the reaction mixture rinsed in the flask. The reaction is ended after 10 hours.

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Analysis by gas chromatography shows that 1?, 8 # des 3-pentenenitrile have been converted into dinitriles, with See the converted 3-pentonitrile from $ 88.5 from adiponitrile and $ 11.6 composed of 1,3-dicyanobufcan and 1,2-dleyanobutane. The number of cycles is 200.

Example 8

A 50 ml twist-neck round-bottom flask, which is provided with a reflux condenser, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 90 °} C. and flushed with dry, deoxygenated nitrogen. The flask is charged with 0.15 g (0.0005 mol) zinc iodide and then with 0 * 325 g (0.00025 mol) of Ni [P (OC ₆ H _{5)] 4,} 20 g (0.25 mol) 3 -Pentenenitrile and 3.1 g (0.01 mol) P (OCgH ₅ ), rinsed. A stream of dry, deoxygenated nitrogen gas is bubbled through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The nitrogen gas stream is equivalent to the setting of a Beschiokungsmenge of gaseous hydrogen cyanide to about 0.5 ml (screened eat at 0 ⁰ C) of liquid hydrogen cyanide per hour, adjusted to 10 ml per minute of nitrogen. The hydrogen cyanide is renewed if necessary. The obtained öaaraie chung

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is used by a bed of phosphorus pentoxide to remove Traces of moisture passed and then washed over the surface of the reaction mixture in the flask. After 12 hours the reaction is terminated.

Analysis by Qaschromatography shows that 44.5 # des 3-pentenenitrile have been converted into dinitriles, with the converted 3-pentenenitrile was $ 83 * 5 from adiponitrile 14.2 # from 1,3-dicyanobutanes and 2.3 $ from 1,2-dicyanobutane composed. The number of cycles is 435.

Example 9

A 50 ml three-necked round bottom flask, an inlet and a magnetic stirrer 1st provided with a reflux condenser, which is connected to a dry ice trap is placed in a bath maintained at a temperature of 80 ⁰ G oil bath and purged with dry, deoxygenated nitrogen. The piston is 0.28? g (ο, ΟΟΙ mol) ZnSO ₁ ..7H ₀ O and then with 0.650 g (0.0005 mol) Ni [P (OC ₆ H ₅ ) -J ₄ , 20.0 g (0.25 mol) 3- Pentenenitrile and 3.1 g (0.01 mole) P (OC ₆ H ₅ ). A stream of dry, deoxygenated nitrogen gas is bubbled through 10 ml of liquid hydrogen cyanide contained in a 20 ml flask which is cooled in a bis-bath. The nitrogen gas flow is used to set a loading

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sehickungsmenge which is approximately 0, _f 5 ml (measured at 0 ⁰ C) equivalent of gaseous hydrogen cyanide Cyanwasserstoffj of liquid per hour, adjusted to 10 rnl of nitrogen per minute. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction mixture in the flask. The reaction is ended after 6 hours.

Analysis by gas chromatography shows that 22% of the 3-pentenenitrile have been converted into dinitrile * 79.0 % of the converted 3-pentenenitrile being made up of adiponitrile, 20.8% from 1,3-dioyanobutane and 0.2% from 1, 2-dicyanobutane composed. The number of cycles is 110.

Example 10

A mixture of 20 g of 3-pentenenitrile, 11 g of triphenyl phosphite, 0.5 g anhydrous zinc chloride and 4.5 g tetrakis (triphenylphosphite) nickel (0) is placed in a 100 ml twist neck flask, the provided with a gas inlet tube above the liquid level, a gas outlet through a reflux condenser and a thermometer is initiated. The system is flushed with nitrogen and the mixture is heated to 120 ° C. A stream of nitrogen gas is passed through the liquid hydrogen cyanide,

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whereupon the oas mixture obtained is stirred over the surface of the hot catalytic converters! Total will be 9 ml of liquid hydrogen cyanide added over a period of 30 minutes «

Analysis by means of Oaschromatography shows that the liquid crude product 57.5JS adiponitrile, 14.2 # l, 3 ~ dioyanobutane and 1.8 # Contains 1,2-dioyanobutane.

Example 11

A mixture of 20 g of 3-pentenenitrile, 11 g of tryphenyl phosphite, 0.8 g of zinc bromide and 4.5 g of tetrakis (triphenyl phosphite) niokel (0) is placed in a 100 ral glass flask. The system is purged with nitrogen, is heated whereupon the Reaktionsmlsohung to 120 ⁰ C. Hydrogen cyanide gas is then flushed over the surface of the stirred reaction mixture by means of a nitrogen carrier gas. A total of 18 ml of liquid hydrogen cyanide are added over a period of 4 ^ minutes. Analysis by means of Oaschromatography shows that the sample contains 64.2 # adiponitrile, 15 «8 ^ 1,3-dicyanobutane and 2.0 # 1,2-dioyanobutane.

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Example 12

A mixture of 20 g of 2-ientenenitrile, 11 g of iriphenylphosphite, 0.65 e of cadmium chloride and 4.5 g of tetrakls (triphenylphosphite) nickel (O) is placed in a 100 BSI oil bottle. The system is purged riding nitrogen and heated to Igo ⁰ C. Hydrogen cyanide gas is then flushed over the surface of the stirred reaction mixture by means of a nitrogen carrier gas. A total of 9 Mi of a liquid hydrogen cyanide are added over a period of one hour »

Analysis by gas chromatography shows that the crude product 8.1Ji adiponitrile, 2.5 # l, 3-Bic * mnobütah and 0.9 #!, Ä butane contains *

example

A mixture of 20 g of 3-pentenenitrile> 2.0 gg ₅ ^ and 0.22 g of zinc chloride is placed in a 100 ml three-necked glass flask which is provided with a gas inlet tube above the liquid level, a gas outlet through a reflux condenser and a thermometer « the system is purged with nitrogen, and the mixture is heated to 120 ⁰ C · A stream of Stick · hydrogen gas is bubbled through the liquid hydrogen cyanide, is rinsed after which the obtained Oasmischung on the surface of the stirred hot mixture. A total of 9 ml of the

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liquid hydrogen cyanide during a span of one Hour added.

Analysis by means of oaso chromatography shows that the liquid crude product contains 35 * ² ^ adiponitrile 11, 3 # 1,3-dcyanobutane and 1,5 # 1,2-dioyanobutane.

Example 14

A 50 ml twist-neck round-bottom flask fitted with a reflux condenser, an inlet and a magnetic stirrer, is connected to a reflux condenser, is placed in an oil bath kept at a temperature of 40 to 41 ° C. and is filled with dry nitrogen which has been deoxygenated rinsed »The flask is rinsed with 0.0511 g (3.75 x 10" * mol) ZnCl ₂ , 14.6 ml (0.15 mol) 3-pentenenitrile, 14.6 ml dioxane (freshly dried on acidic aluminum oxide), 0.8l ml (3 χ 1O ~ ³ mol)

and 0.440 g (3 χ 10 "* moles) of NIt (P-CH ₅ C ₆ H ₄ O) ₃ P] ₄

Stream of dry, deoxygenated nitrogen gas is replaced by 8.8 ml of a liquid hydrogen cyanide «weloher In contained in a 20 ml flask which is chilled in an ice bath is pearled. The oasis solution obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture passed and then flushed over the surface of the reaction mixture in the flask. After 16 hours and 35 minutes

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ff

the reaction is ended. During this period, 7.7 ml of the liquid hydrogen cyanide are introduced into the reactor.

Analysis by Oaschromatography shows that 60.8 $ des 3-pentenenitrile have been converted, the converted 3-pentenenitrile at 84.5 # from adiponitrile, 11.8 # from 1,3-Dicyanobutane, 1 * 01 $ from 1,2-Dieyanobutane and 2.27 # from composed of cis- and trans-2-pentenenitrile »The number of cycles is 288.

Example 15

A 50 ml three-necked round bottom flask connected to a RückfluSkühler which with a dry ice trap, an inlet and a magnetic stirrer is provided, is inserted into a bath maintained at a temperature of 8l to 92 ⁹ C oil bath and treated with dry, deoxygenated nitrogen flushed. The flask is filled with 0.0950 g (7 × 10 "* mol) ZnCl ₃ , 27.4 ml (0.28 mol) 3-pentenenitrile and 0.506 g (7 × 10 ** mol) Ni [P (OC ₂ H ₅ ), 3 ^. A stream of dry, deoxygenated nitrogen gas is fed at a rate of 16 ml per minute through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath.

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pearled. The gas mixture obtained is then made into a bed Phoaphorpentoxyd passed to remove traces of moisture and then rinsed over the surface of the reaction mixture in the flask. By hydrogen cyanide in that Piston is replaced if necessary * After two hours and 22 minutes the reaction is over *

Analysis by oasis chromatography shows that 11.7 $ des 3-pentenenitrile have been converted, the converted 3-pentenenitrile being $ 51.5 from adiponitrile, # 13.4 from 1,3-dicyanobutane and>, 2 # composed of 1,2-dioyanobutane. The number of cycles is 52.2.

Example 16

A 50 ml three-necked round bottom flask lußkühler with a Rüokf, which is connected to a dry ice trap, an inlet and a magnetic stirrer 1st provided, is inserted into a bath maintained at a temperature of 60 to 65 ^e C oil bath and freed with dry, oxygen Purged with nitrogen. The flask is filled with 0.049 g (>, 60 χ 10 "* mol) ZnCl ₂ , 29.2" 1 (0.3 mol) 3-pentenenitrile, 0.98 ml (3 χ 10 ⁵ mol) (P-GH ₃ OC ₆ H ₄ O) ₅ P and 0.498 g of OX 10 ** mol) NlCp-CH ₃ OC ₆ H ₄ O) ₃ P] _4. A stream of dry, deoxygenated nitrogen gas is replaced by a liquid hydrogen cyanide which

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contained in a 20 ml flask which is placed in an ice bath is cooled, pearled. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction solution in the flask. After 19 hours and The reaction is ended in 35 minutes. During this period, 4.5 ml of the liquid hydrogen cyanide are added to the reactor initiated.

Analysis by gas chromatography shows that 26.4 pounds of des 3-pentenenitrile have been converted into dinitriles, the 3-pentenenitrile converted in this way consisting of 80.9 $ from adiponitrile, 17.1% from 1,3-dicyanobutane and 2.11 from 1,2-dicyanobutane. The number of cycles is 264.

Example 17

A 50 ml three-necked round bottom flask 1st connected to a reflux condenser which is connected to a dry ice trap, an inlet and a magnetic stirrer is provided, is inserted into a at a temperature of 57-60 ⁰ C held oil bath and treated with dry, deoxygenated nitrogen * The flask is flushed with 0.049 g (3.60 χ 10 "^ moles) ZnCl ₂ , 24.3 g (0.3 moles) 3-pentenenitrile, 0.93 g (3 x 10" ⁵ moles) P (OC ₆ H ₅ ), and 0.420 g (3 χ 10 mol) Ni [P (OCgH ₅ ) -] 4 charged. A stream of dry

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Deoxygenated nitrogen gas is bubbled through 10 ml of a liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath * The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then over the surface of the reaction mixture in the flask. The reaction is ended after 5 hours and 5 minutes. During this period, be introduced into the reactor 7.0 ml of liquid hydrogen cyanide AEEA s.

Analysis by gas chromatography shows that 25 * 1% of the 5-pentenenitrile has been converted into dinitrile, the 3-pentenenitrile converted in this way being 77.3 $ from adiponitrile, 17 * 3 $ from 1,3-dicyanobutane and to 2.5 # composed of 1,2-dicyanobutane »In addition, 2.03 $ cis and trans-2-pentenenitrile are formed. The number of cycles is 249.

Example l8

A 50 ml three-necked round bottom flask, an inlet and a magnetic stirrer is provided with a reflux condenser, which is connected to a Trocksneisfalle is used in a bath maintained at a temperature of 115 ⁰ C oil bath and purged with dry, deoxygenated nitrogen. The piston

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is with 0.352 g (0.0019 mol) Zn [HPO ₃ I ₂ , 20 g (0> 2 * 7 Mel) 3-Pentenenitrll, 3A S (0> 01 mol) P (OC ₆ H ₅ J ^ and 0.925 g (0.0005 mol) Ni £ P (QCgH ^ Cl),] ψ. A stream of dry, deoxygenated nitrogen gas is passed in an amount of 15 ml per minute through a liquid hydrogen cyanide in a 20 ml flask, which is cooled in an ice bath, bubbled * The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction mixture in the flask.After three hours and 50 minutes, the reaction is terminated.

Analysis by Oaschromatography shows that 17 # des 3-pentenenitrile have been converted into dinitriles, the converted j5-pentenenitrile consists of $ 70.6 adlponitrile. The number of cycles is 77.

Example 19

A 50 ml three-necked round-bottomed flask, which is connected to a reflux condenser, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 50 °} C. and flushed with dry, deoxygenated nitrogen Piston is with

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0.220 g (Ο, ΟΟΟβ mol) CdJ ₂ , 25.0 g (0.308 mol) 3-pentenenitrile, 1.62 g (0.004 mol) P (OC ₆ H ₄ OCH ₅ ) ^ and 0.720 g (0.0004 mol) Ni [P (OCgHuOCH -,) - »3h charged. A stream of dry, deoxygenated nitrogen gas is bubbled at a rate of 5 nil per minute through a liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then flushed over the surface of the reaction mixture in the flask. The reaction is terminated after about 6 hours.

Analysis by gas chromatography shows that 51 * 7 $ des 3-pentenenitrile have been converted into dinitriles, with the 3-pentenenitrile converted in this way turns out to be $ 83 13 "7" adiponitriles from 1,3-dicyanobutane and 2.9 # from 1,2-dicyanobutane composed «The number of cycles is 376.

Example 20

A 50 ml three-necked round bottom flask, which is provided with a reflux condenser, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an oil bath kept ^{at a temperature of 81 + 3 ° C and with}

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purged with dry, deoxygenated nitrogen. The flask is filled with 0.254 g (2.6 χ ΙΟ " ¹ * mol) of Zn (OSOgC ₇ P ₁₅ ) ₂ and then with 29.2 ml (0.3 mol) of 3-pentenenitrile, 0.785 ml (3 X 10 *" ⁵ mol) P (OC ₆ H ₅ ) ₃ and 0.420 g (3 X 10 " ⁴ mol) Ni [P (OCgH ₁ -KJ ^ are charged. A stream of dry, deoxygenated nitrogen gas is passed through a liquid hydrogen cyanide which is dissolved in A 20 ml flask, which is cooled in an ice bath, is bubbled. The hydrogen cyanide is renewed if necessary. The nitrogen gas flow is adjusted to 15 ml of nitrogen per minute. The oas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of liquid and then rinsed over the surface of the reaction mixture in the flask »After 6 hours and 40 minutes the reaction is ended *

Analysis by gas chromatography shows that Y, Z% of the 3-pentenenitrile has been converted into dinitriles, the dinitriles produced being 73 * 7 ^ from adiponitriles 20.7% from 1,3-dicyanobutane and 5 * 7 # Compose 1,2-dioyanobutane. The number of cycles is 172.

Example 21 ^, ^ "

Example 20 is repeated, essentially the same

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Conditions are maintained as in Example 20, except that the Zn (OSO ₂ C ₇ P _{15) 2} is replaced by 0.275 g <2.72 x 10 ~ ⁴ mol) Cd (OSO ₂ CJP.-). ₂ This results in a 0.9% conversion of 3-pentenenitrile into dinitrile, with the dinitriles produced being 79.3% from adiponitrile, 16.9% from 1,3-dicyanobutane and 3.8% from 1,2 - Compose dicyanobutane * The number of cycles is II5.

Examples 22-25

Examples 22-25 show the effect of using a large molar excess of ZnCl ₂ compared to the Niokel catalyst. With the exception of the amount of ZnClg, these examples are carried out under identical conditions.

In each case, a 50 ml three-necked round-bottom flask, which is provided with a RUokflusskühler, which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath maintained at a temperature of 80 to 85 0} C and with dry oxygen purged with liberated nitrogen. The flask is filled with the zinc chloride, 14.6 ml (0.15 mol) of 3-pentenenitrile, 7.3 ml of dioxane (freshly dried on neutral aluminum acid), 7.3 ml of tri-p-oresylphosphate and 0.110 g (7.5 χ 10 * ^ Moles) of tetralds (tris-p-cresylphosphite) niokel (0) charged. A stream

SAD ORIGINAL

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Or

of dry, oxygen VCN "liberated nitrogen Uird durcth a liquid hydrogen cyanide _f the holding in a 20 ml flask · enc" vilrö 1st, which is cooled with an ice bath, bubbled ge ~. The Gasnsisehung obtained is zav through a bed of Phospliorpentoxyd removal of Traces of moisture passed and then flushed over the surface of the reaction solution in the calving. "The cyanide peat in the 20 ml flask is renewed if necessary. The reaction is ended? when the absorption of cyanogen aerate ceases.

The following table shows «that more moles of 3-pentenenitrile in Dinitriles are converted per mole of nickel when the amount of zinc chloride present is increased. Analysis of the products shows> that the yield to aediponitrile is not worth mentioning Dimensions changes.

Table I.

Molar ratio of ZnCl «to the molar ratio of the dinitriles produced

Niokelcatalyst to the Niokelkatalysator

2.5 359

5.0. H66 10.0 594

20.0 676

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Example 2o

A 50 ml Dreihalsrundkolban, d.er with a reflux condenser, which is connected to a dry ice trap, an inlet UNAE a Magnetrtihrer is provided is uni used in a bath maintained at a temperature of 125 ⁰ C oil bath with dry, deoxygenated nitrogen purged «Bsi ⁵ flask is made with 0.82 ml of a 1 molar solution of (CpHc) ₀ AlGl in n-hexadecane [8.2 χ 10" * mol (CgH ₅ ) ^ AlCl], 0.82 ml of a 1 molar solution CgHeAlCIg in cyclohsxane (8.2 χ 10 "mol

CgH ₅ AlCl ₂ ) and then with 3.46 ml (1.31 χ ΙΟ " ² mol) P (OC ₆ H ₅ ), 20.3 g (0.25 mol) 3-pentenenitrile and 2.29 g ( 1.64 χ 10 "- ⁵ moles) of Ni [P (OCgH _5)] ^ charged. A stream of dry, deoxygenated nitrogen gas is bubbled through 4.0 ml of a liquid cyano aqueous solution contained in a 20 ml container which is cooled in an ice bath. A further 5.5 b> 1 hydrogen cyanide are then added 90 minutes after the start and a further 3.5 ml when the reaction is started today, as will be explained in more detail below. The nitrogen gas flow is set in order to set a feed amount of hydrogen cyanide of approximately 2 ml (measured at 0 ^° C.) of a liquid hydrogen cyanide β per hour. The oas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and then

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3 *

Rinsed over the surface of the reaction mixture in the flask. The reaction is ended after one hour and 50 minutes. After 15 hours and 25 minutes, the bath is again brought to 126 ° C heated, followed by an additional two hours and 25 minutes continued and then ended.

The analysis by means of gas chromatography shows that 49.6 $ of 3-pentenenitrile have been converted into dinitriles, the dinitriles produced being 62.6 $ from adiponitrile, 28.9 $ from 1,3-dicyanobutane and 8.6 $ composed of 1,2-dicyanobutane. The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst introduced) is 75.7 «

Example 27

A 50 ml, three-necked round bottom flask fitted with a reflux condenser connected to a dry ice trap, an inlet and a magnetic stirrer is placed in an oil bath kept at a temperature of 129 + 1 ° C and flushed with dry, deoxygenated nitrogen . The flask is filled with 0.219 g (1 * 64 × 10 ** ^ mol) AlCl, and then with 4.06 g (1.31 × 10 " ² mol) P (OC ₆ H ₅ ) ,, 20.3 g ( 0.25 mol) 3-pentenenitrile and 2.29 g (1.64 χ 10 " ³ mol) Ni [P (OC ₆ H ₅ ) ^ I ₄ charged. A stream of dry, deoxygenated nitrogen gas is passed through 4 , 8 ml of a liquid hydrogen cyanide ^,

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QS

contained in a 20 ml container, which is cooled in an ice bath, pearled. After about an hour, another 6.5 ml of hydrogen cyanide is added to the container. The nitrogen gas stream is at JO to. "55 ml of nitrogen per minute for a total of hydrogen cyanide feed setting of 6.8 ml (measured at ⁰ ° C) set a liquid hydrogen cyanide. The gas mixture is passed through a bed of Phos pentoxide to remove Peuchtlgkeltsspuren passed and across the surface of Reaktionsmiß chung rinsed in the flask. After 6 I / 2 hours, the reaction is terminated.

Analysis by means of Oaschromatography shows that 31.5% of the 3-pentenenitrile has been converted into dinitrile, the dinitrile produced being 65.6% from adiponitrile, 29.4% from 1,3-dicyanobutane and 4.9% Compose 1,2-dicyanobutane. The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst introduced) is 48.1.

Example 28

A 50 ml three-necked round bottom flask, which is provided with a reflux condenser which is connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath heated to 155 °} C. and flushed with dry, deoxygenated nitrogen. The flask is filled with 0.82 ml of a 1 molar solution of (C ₃ H ₅ ) _{g of} AlCl in n-hexadecane [8.2 10 mol

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(C ₀ H, -) _O A1C1], 0 _s B2 ml of a 1 molar solution of C ₂ H ₅ AlCl ₂ in cyclohexane (8.2 10 "* 'mol C ₂ H ₁ -AlClp), 4.06 g (1.31 χ ΙΟ " ² mol) P (OCgH ₅ ) ,, 20.3 g (0 _s 25 mol) 3-pentenenitrile and 0.28. g (1.64 10 "- ⁵ mol) Ni (CO) ₂ ^ are charged in the order mentioned. The oil bath is cooled to 152 to 3 ° C. over a period of 63 minutes, while carbon dioxide is not evacuated from the reaction . a stream of dry, deoxygenated nitrogen gas is by 15 * 2 ml of liquid hydrogen cyanide * contained in a 20 ml-container, which is cooled in an Bisbad, bubbled. the nitrogen gas stream wire · sur setting of a hydrogen cyanide-Gesamtbeschicfcung of 9 * 5 RiI (measured at ⁰ ° C.) of a liquid hydrogen cyanide ε adjusted to 35 nil nitrogen per minute. The gas mlseroing obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture and flushed over the surface of the reaction mixture in the flask. The reaction is ended in 4 hours and 7 minutes.

The analysis of Kittel's Craschromatography shows that 3β.5 # of 3-pentene-nitrile3 have been converted into dinitrile, the dinitriles produced being 44 * 1 $ from adiponitrile 37 * 4 $ from 1,3-dieyanobutane and 18.5 ^ s-us 1 ₉ compose 2-dicyanobutane. The look! the cycles (molar ratio of the dicyanobutanes produced

1 098 47/18 A3

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on the train © catalyst) is 55 * 6 «

Example 29

UNAE is provided a 50 ml three-necked round bottom flask, * which is connected to a · dry ice trap with a Rückflußkübler.., An inlet and an Magnetrülirer _"Ä i ^\? Ird in a bath maintained at a temperature of. 1C? ° C oil bath used purged with dry ^ 'ion deoxygenated nitrogen. Dar piston lüifc 0 £ i9 g (1.64 x 1 (T ^ mol) AlCl- and then χ with 4.06 g (1.3 to 1 10 ^"2 moles ) P (OCgHj.) ^, 20.3 g (0.25 MoX) 3 ~ Fentennifcril and K ₅ 29 S (1 * 64 χ 10 ~ ³ mol) Ni [P (OC ₆ Hp) ₃ J ₁₁₁ charged of dry, deoxygenated? Stickstoffg & s viird by liquid C3? anwas3erstoff ₅ "is included container, which is cooled in an Bisbad? ge" which, in a 20 ml bubbled. the nitrogen gas stream WI5? d for adjusting a hydrogen cyanide "Bsschiokungsinenge of about 3 ^ l (eaten at ⁰ ° C.) of a liquid hydrogen cyanide per hour adjusted to 38 to 44 ml. The gas mixture obtained is removed through a bed of phosphorus pentoside tion of traces of moisture and then flushed over the surface of the reaction mixture in the flask. 15 minutes after the start, the temperature of the oil bath is reduced to 90 Ms 93 ⁰ C. The reaction is ended 2 hours and 10 minutes after the start of the supply of hydrogen cyanide »

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Analysis by Sasehromatographie shows that 8l $ ₅ 6 have been the 5 'Pentermitrils converted to dinitriles, wherein the generated dinitriles to 4j5,7 # of Adiponitrile 4l, l% of l, 3 ° X3icyanofoutan and 15S2 # 1, The number of cycles (molar ratio of the Dicyanobutaae produced to the catalyst introduced) is 125 ·

Example j50

Bin 50 ml Brelhalsrundkolben which is connected with a reflux condenser, "Tssleher with a Trooteeneisfalle, an inlet and a magnetic stirrer is provided, is inserted into a bath maintained at a temperature of 8O ⁰ C oil bath and rinsed liberated with dry ^ of oxygen, nitrogen. The flask is filled with 0.450 g (O ₅ OOl mol) GaI, and then with 0.650 g (.0.0005 mol) Hi [P (OCgEL) ₃ ] ^, 20.0 g (0.24? Mol)> pentenenitrll and 3 * 1 g (O ₅ Ol mol) P (OCgH ₅ ), charged. A stream of dry, deoxygenated nitrogen gas is bubbled through 10 ml of a liquid hydrogen cyanide * contained in a 20 ml container which is cooled in a bath. The nitrogen gas flow is increased to 10 ml per minute of nitrogen (screened eat at 0 ⁰ C) set a liquid hydrogen cyanide per hour of hydrogen cyanide for adjusting a feed rate of about 0.5 ml. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture

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passed and then over the surface of the reaction mixture Rinsed in the flask. After 6 1/2 hours the reaction will completed.

The analysis by means of gas chromatography shows that the dinitriles produced are composed of ^] ¥}% adiponitrile 35 * 3 $ from 1,3-dicyanobutane and 20.9 $ from 1,2-dicyanobutane. The number of cycles (molar ratio of the produced dicyanobutanes to the catalyst introduced) is 84.

Example Jl

A 50 ral three-necked round bottom flask provided with a reflux condenser, which 1st connected to a dry ice trap, an inlet and a magnetic stirrer is used in a bath maintained at a temperature of 64 + 2 ⁰ C oil bath and purged with nitrogen. The flask is filled with 0.06 g of InCX ₅ and then with 25 ml of 3-pentennyltril> 0.7 ml

P (0 - / "" V-CH ₃ ), and 0.4 g Ni [P (0- / ~ \ - CR ₃₅ ) ^] ₂₁ charged.

A stream of nitrogen gas is passed through 8.8 nil of a liquid Hydrogen cyanide contained in a 20 ml flask, which chilled in an ice bath, pearled. The nitrogen gas stream is adjusted to 4 ml of nitrogen per minute. The gas solution obtained is over the surface of the reaction mixture in the

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SAD ORIGf

A »4! 98 R '■■ -"' ■ "■ ^: ■■■■". '". '.

«V:. ;: ■■■■: ■■ -..-

Flask flushed. Naeia J5 hours and 51 minutes will be the reaction

Analysis by means of gas chromatography shows that the reaction mixture 4.0 | T adiponitrile 1 * 1 $ 1 * j5-Dic # anobutane and 0.3 $ 1.2 "- '0iG; f £! .nobui-an contains"

Example 52 - "". . - ■ "_'■;

A .30 i-iil-D-rci-neck round-bottom flask with a overflow cooler, which is connected to a ice trap. an inlet with a thermometer and a magnetic stirrer. ”is placed in a at a temperature of 130 +. 2 ⁰ C held "oil-baö used os.d gasptllt with nitrogen * The flask" is ■ with O., l3 till (I # 64 m 10 '™ · ^ mol) t liquidrr titanium tetrachloride and moreover with 4.06 g' (1.32 x iO " ² mol) P (OC ₆ H ₅ ) ^ 20.3 S (0.23 IiOl) 3-pentenenitrile and 2 ^ 29 g Cl, 64 χ! 0" ^ mol) Mi [P (00 ^ H ₅ ) _] i> viewed .. A stream of nitrogen gas becomes liquid through οί.ίΆβ.ϊΐ}. Hydrogen cyanide .. which is contained in a 20 ml flask "wholly cooled in an ice bath," is "directed" The Stiökshoff gas flow "is reduced to 38% nitrogen per minute to set a total hydrogen cyanide" charge of 9 ral ■ (measured at 0 ⁰ G) of a liquid hydrogen gyanide. The gas mixture obtained is rinsed over the surface of the reaction unit in a flask after 5 hours and 131 minutes

- ^ - T09847 / 18A3

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the reaction is ended.

Analysis by gas chromatography shows that 15 * 8 $ des 5 »pentenenitrile has been converted into dinitrile, whereby the 3-pentenenitrile converted in this way to 78, Oji Adiponitriles $ 6.7 from 1,3-dicyanobutane and $ 5.3 from 1,2-dicyanobutane composed «The number of cycles (molar ratio of Bieyanobutanes generated to the catalyst supplied) 24.3. '

Example 53

A 50 mI "Draihalsrundkolben, which is provided with a reflux condenser, which is connected to a Tröckeneisfalle, an inlet, a thermometer and a magnetic stirrer is used in a bath maintained at a temperature of 65 + 2 ⁰ C oil bath and purged with nitrogen. The flask is filled with 0.21 g (4.5 χ ΙΟ ** mol) of Zr (C ^ H ₇ O ₂ ) Jj ₁ and then with -0.81 ml of P- (O-JJf-CH -) -,

29 * 2 ml (0.30543.MoI) 3-? Eatennitrli and 0.440 g (3 χ 1θ " ^ψ mol) Ki- [P (O-ii-CH, Ul ^) are charged A 20 ml flask is held, which is cooled in an ice bath, bubbled * The nitrogen gas flow is used to adjust a total _{hydrogen cyanide feed from I 5} 2 ecm- · (measured at O ⁰ C) liquid hydrogen cyanide to 7 com nitrogen adjusted per minute. The Qas mixture obtained

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is over the surface of the reaction mixture in the flask rinsed »The reaction is ended after 4 hours and 41 minutes.

The analysis by means of gas chromatography shows that 3 3-pentenenitriles have been converted into dinitriles, wöbe ·! the 3-pent.enenitrile converted in this way to $ 2.6 from adiponitrile 31 * 2 $ from 1,3-dicyanobutane and 16 ₉ 2% . The composition of 1,2-dicyanobutane is 32.9. The number of cycles (molar ratio of the dicyanobutanes produced to ... the.

Example 34 -

, A 50 ml three-necked round-bottomed flask. Equipped with a Hückflußkühler, which is connected to a dry ice trap, an inlet, a thermometer and a magnetic EUhrer is lind used in a bath maintained at a temperature of ^ 3 + 2 ^e C oil bath with nitrogen flushed. The flask is filled with 0.905 ml of a 0.497mL solution (4.5 .'ίο ** mol) of titanium trichloride in 1-pentenenitrile and then with 388 g of 3-pentenenitrile 14.6 ml of CH ₅ OCH ₂ CH ₂ OCH ₅ , , 0.902 g of P (Ow0u.GH ₃ ), and 0.440 g of Ni [P (0-0-CI ^ KJjJ). A stream of nitrogen gas is passed through liquid hydrogen cyanide, which contains 20 ml of "Koiben , which" in an ice bath is cooled, pearled »The ätiöfcötöf <* -

AD 4198 R

gas stream is to a Gesaratcyanwasserstoff feed setting I ₄ I ml (measured at 0 ⁰ C) s adjusted to 3.5 ml per minute of nitrogen liquid hydrogen cyanide. The oil quench obtained is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 12 hours and 5 minutes.

The analysis by means of gas chromatography shows that 12.4 # of 3-pentenenitrile has been converted into dinitrile, with the 3-pentenenitrile converted in this way being converted to 8 # from adiponitrile 7 * 8 # from 1,3-dicyanobutane and 1 , 4 # composed of 1 _s 2-dicyanobutene · The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst fed) is 62.3.

Example 35

A 50 ml three-necked round bottom flask provided with a reflux condenser, which is connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer is used in a bath maintained at a temperature of 62 ⁰ C oil bath and "flushed it nitrogen. The flask is filled with 12.2 ml of 3-pentenenitrile and then with 2.42 ml of a 0.497in solution of titanium chloride in 3-pentenenitrile, 0.81 _{ml of P (O - ^ - CH 5} ), 14.6 ml of CH ₅ OCHgCHgOQH ₅ and 0.390 g NiCPiOCgHg) -] ^ beeohickt, Ein Stiele- -

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Substance stream gas is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an electrolytic bath. Dar Stiokstoffgasstrom becomes a Gesamtcyanwasserstoff feed setting of 3.9 »1 (measured at 0 ⁰ C) liquid hydrogen cyanide in 4 ml nitrogen per minute regulated. The gas mixture obtained is flushed over the surface of the reaction chamber in the flask. The reaction is ended after 20 hours and 20 minutes. .

Analysis by gas chromatography shows that 16 % of 3-pentenenitrile have been converted into dinitriles, the product obtained by converting> -pentonitrile to 89.71% from adiponitrile 8.8% from 1.3 -Dicyanobutane and 1.6% composed of l, 2 ~ dicyanobutane. The number of cycles (MoI ratio of the dioyanobutanes produced to the catalyst fed in) is 82.2 * The conversion of j3 * -pentenenitrile into compounds other than dinitriles or 4-pentenenitrile is 0.6% based on the J-pentenenitrile fed in.

Example 36

A 50 ml three-necked round-bottom flask fitted with a cooler which is connected to a trooke ice trap, an inlet, equipped with a thermometer and a magnetic stirrer, in

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at a temperature of 6l + 1 ° C held oil bath used and flushed with nitrogen. The flask is filled with 0.069 g (4.5 x ΙΟ ** mol) of titanium trichloride and then with 14.6 ml (0.15 mol) of 3-pentenenitrile, 0.785 ml (3 π 10 " ⁵ mol) of P (Oa ₆ IL) -, 0.390 g

(3.0 χ IQ "* 'MoX) Ni [P (OC ₆ H ₅ U] ₂ ^ and 14.6 ml C ₆ H ₄ Cl _{3 are} charged. A nitrogen gas stream is replaced by liquid hydrogen cyanide, which is in a 20 ml -Flask is contained, which is cooled in an ice bath * bubbled. The nitrogen gas flow is regulated to adjust a total hydrogen cyanide charge of approximately 5 ml (kept at 0 ° C) liquid hydrogen cyanide to 5 ml nitrogen per minute The surface of the reaction mixture in the flask is rinsed and the reaction is terminated after 19 hours and 35 minutes.

The analysis by gas chromatography shows that the 98.7 $ 3 * pentenenitrile have been converted to dinitriles, wherein the product thus produced from the 3-pentenenitrile jsu 84.1 $ from Adiponitrile 12 _Ä $ 8 ~ la3 from dicyanobutane and $ 3.1 composed of 1,2-dicyanobutane. The Anaahl the rent up (Molver * · ratio of DIC produced: yanobutane to the stated catalyst) is 140. © manifestly yield loss to 2-pentenenitriles and S-methyl-2-butennitrilen of less than \ $ _ä based on the 3-pentenenitrile fed in, observed.

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Example ^37;

A 50 ml three-necked round bottom flask fitted with a reflux cooler connected to a dry ice trap, an inlet, a thermometer and; provided with a magnetic stirrer, is immersed in an oil bath maintained at a temperature of 65 + 3 * 0 and flushed with nitrogen. The flask is filled with 0.29 g (9 χ 10 mol) of hafnium tetrachloride and then with 29 * 2 ml (0.298 mol) of 3-pentenenitrile, 1.62 ml (β χ PCO - ^ - CH,) ^ and 0.880 g (6 10 "^ mol) Ni [P (O - ^ - CH ₅ U] ^ charged. A stream of nitrogen gas is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The Nitrogen gas flow is adjusted to 7 com nitrogen per minute in order to create an oil charge of 8.4 com (measured at ^{0 0} O) L. The resulting gas quench is flushed over the surface of the reaction mixture in the flask The reaction is ended for 22 hours.

Analysis by gas chromatography shows that 4.9 $ des 3-Pentenenltrils have been converted into dinitriles, whereby the 3-pentenenitrile converted in this way to 81.6% Adlponitrile ,! 15.7 ^ from 1,3-dicyanobutane and 2,7 ^ 1,2-dioyanobutane composes. The number of cycles (molar ratio of the generated Dicyanobutane to the catalyst fed in) is 23.8. Ea he

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an obvious conversion follows an amount of $ 0.9 as shown by an analysis of the nitriles.

Example 38

A 50 ml three-necked round bottom flask, which is provided with a RÜokf fl ux condenser, which is connected to a dry ice trap * an inlet, a thermometer "and a magnetic stirrer", is placed in an ^{oil bath kept at a temperature of about 45 °} C. and flushed with nitrogen. The flask is filled with 0.105 g (4.5 χ 10 mol) of zinc tetra-chloride and then with 29.2 ml (0.298 mol) of 3-pentenenitrile, 0.8 ml of P (O - ^ - CH _{5 I 3} and 0.440 g (3 X 10 "* mol) NifPiO-if-CH,) -] ^. A nitrogen gas stream is bubbled through liquid hydrogen cyanide contained in a 50 ml flask which is cooled in a bis-bath. The nitrogen gas stream is used to adjust a Total hydrogen cyanide charge of 1 ml (measured at ⁰ ° C.) of liquid hydrogen cyanide is adjusted to approximately 4 ml of nitrogen per minute. The gas mixture obtained is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 4 hours and 5 minutes.

Analysis by means of Oaschromatography shows that the in Dinitrile converted 3-pentenenitrile to 81.5 # from adiponitrile

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17 * 3 # composed of 1,5-dicyanobutane and 1.2% of 1,2-dicyanobutane. The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst fed in) is 26.5. The apparent loss of 3-pentenenitrile to 2-pentenenitriles, based on the 3-pentenenitrile fed, is less than

Example 39

A 50 ml three-necked round bottom flask fitted with a reflux condenser connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer is placed in an oil bath maintained at a temperature near 65 ° C. and flushed with nitrogen. The flask is filled with 12.2 ml of 3-pentenenitrile and then with 2.42 ml of a 0.497 ml solution of titanium trichloride in 3-pentenenitrile (1 * 2 χ IG "'mol), so that a total of 14.6 ml of 3-pentenenitrile are added , 0.8 l ml of P (<H? -CH «) y. 0.390 g (3 χ ΙΟ" ⁴ mol) Ni [P (O-Ji-CH-) ₅ ] ^ and 14.6 ml of dioxane charged. A nitrogen gas stream is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The nitrogen gas flow is adjusted to set a total ^{hydrogen cyanide charge of 1.2 ml (measured at 0} ° C.) of liquid hydrogen cyanide to 4 ml of nitrogen per minute. The gas mixture obtained is passed over the surface of the reaction mixture in the flask.

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washes. The reaction is ended after 6 hours and 15 minutes.

The analysis by gas chromatography shows that 21 2 $ 3-pentenenitrile are converted to dinitriles * with the thus converted J-pentenenitrile check to 91.150 from Adiponitrile 7.50 0 from 1,3-Dioyanobutan and $ 1.35 from Composed of 1,2-dleyanobutane. The number of cycles (molar ratio of the dioyanobutanes produced to the catalyst fed) is 105. An apparent conversion to other nitriles as high as 1.60 is found when analyzing the nitriles.

Example 40

A 50 ml three-necked round bottom flask provided with a reflux condenser, which falls with a dry ice is connected to an inlet, a thermometer and a Magnetrtihrer is used in a bath maintained at a temperature of 86 + I ⁰ C oil bath and purged with nitrogen. The flask is filled with 0.058 g (4.5 x 10 " ⁴ mol) of TiCl ₀ , (a mixture of TiCl ₀ and TiCl, in such a ratio that the apparent valence of the titanium is 2.3) and then with 14.6 ml (0.15 mol) 3-pentenenitrile, 0.785 «1 (3 X 10" ⁵ mol) P (OC ₆ H ₅ ) J and 0.420 g (3 χ 10 Ni [P (OCgH ₁ -).,] ^ charged A stream of nitrogen gas is passed through the liquid hydrogen cyanide, which is contained in a 20 ml flask

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is «which is cooled in an Elsbad, pearled. The nitrogen gas flow is adjusted to set a total ^{hydrogen cyanide charge of 8 ml (measured at 0} ° C.) of liquid hydrogen cyanide to 12 ra3 nitrogen per minute and after 4 hours and 15 minutes to 4 ml nitrogen per minute. The gas mixture obtained is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 20 hours and 35 minutes. "'*

Analysis by gas chromatography shows "that 32.6 % of the 3-pentenenitrile has been converted into dinitrile", with the 3-pentenenitrile converted in this way to 82.7 $ from adiponitrile 13.3 $ from 1,3-dioyanobutane and 4 * 0 $ consists of 1 »2-dicyanobutane« The number of cycles (molar ratio of the dioyanohutanes produced to the catalyst supplied) is lf> 9 <There is one! obvious conversion to other nitriles «like

emerges from an analysis of the nitriles at a height Of 3

The 50 ml head-neck round-bottom flask has a reflux condenser connected to a dry _{oath trap for} an inlet, a thermometer and a magnet

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SV

placed in an oil bath maintained at a temperature of approximately 86 ° C and purged with nitrogen. The flask is charged with 0.108 g (7 χ 10 mol) of titanium trichloride and then charged with 27.4 ml (0.28 mol) of 3-Fentennitril and 0.506 g (7 x 1O ~ ⁴ mol) of Ni [P (OCgHc) *] ^ . A stream of nitrogen gas is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The nitrogen gas flow is adjusted to set a total hydrogen cyanide loading of 1.9 ml (measured at 0 ° C.) of liquid hydrogen cyanide to 12 ml nitrogen per minute. The gas rise obtained is flushed over the surface of the heat dissipation in the flask. The reaction is ended after 2 hours and 55 minutes.

Analysis by gas chromatography shows that 6.6 # des 3-Pöntennitrils have been converted into dinitriles, whereby the 3-pentenenitrll converted in this way to 84.6 # Adiponitrile 10.9 $ from 1,3-Dlcyanobutane and 4.6 # from 1,2-Dieyano " butane is composed «The number of cycles (molar ratio of Dlcyanobutane generated to the supplied catalyst) is 26.4. As can be seen from an analysis of the nitriles, an obvious conversion to other nitriles, in one Height of

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Example 42

A 50 ηα three-necked round bottom flask * with a reflux condenser, which is connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer is provided, in a bath maintained at a temperature of 44 + 2 ⁰ C oil bath is used, and purged with nitrogen. The flask is filled with 0.092 g (6 10 mol) of titanium trichloride and then with 1.20 g (3 χ 10 " ⁵ MoX) P (O-0-O-OH-) _5i 29 * 2 ml (0.3 mol) 3-pentenenitrile and 0.498 g (3 χ ΙΟ " ⁴ mol) NiCP (O - ^ - O-CH ₅ ) -1 ^ chilled in an ice bath, pearled. The nitrogen gas flow is adjusted to adjust a total hydrogen cyanide charge of approximately 5 * 2 ml (measured at cinnamon temperature) of liquid hydrogen cyanide to 18 ml nitrogen per minute. The reaction ends after 4 hours and 15 minutes «

Analysis by gas chromatography shows that 9,156 des 3-pentenenitrile has been converted into dinitrile, whereby the 3-pentenenitrile converted in this way to 88.7 ^ Adiponitriles $ 8.8 from 1,3-dicyanobutane and $ 2.5 from 1,2-cyanobutane composed. The number of cycles (molar ratio of

pioyanobutanes generated to the added catalyst) 93 * 2. The loss to 2-pentenenitrile is negligible.

Example 43

A 50 ml three-necked round bottom flask, an inlet, a thermometer and a Magnetrtihrer is provided with a reflux condenser, which is connected to a dry ice trap "is used in a bath maintained at a temperature of 47 + 2 ⁰ C oil bath and purged with nitrogen. The flask is filled with 4.8 ml of a 0.497m solution of titanium trichloride in 3-pentenenitrile (2.4 10 "mol) and then with 9.8 ml of 3-pentenenitrile, 14.6 ml of dioxane * 1.62 ml (6 χ 10 * 3 mol) P (O- ^ CH,) - and 0.880 g (6 χ 10 "* mol) Ni [P (O-O-CH,) _] ^ charged * A nitrogen gas stream is fed through liquid hydrogen cyanide contained in a 20 ral flask cooled in an ice bath. The nitrogen gas stream is adjusted to set an Oesarotoyanasestoff-Beschlokung from 6.8 ml (measured at ⁰ ° C.) of liquid hydrogen cyanide to 4 ml of nitrogen per minute. The gas mixture obtained is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 20 hours and 55 minutes.

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Analysis by Qaschromatography shows that 38.0 # des j-PeMeffltrits ^ l ^

that in dileW ^ way ^ umiilian ^ »S ^

Adlponitrile, $ 6.7 from 1,3-dicyanobutane and 1,2 # from 1,2-dioyanobutane composed. The number of cycles (Moiverhlltnl% siiNsi ' Dlcyanobutanen generated to the listed catalyst) is 93.2. - · - ...

Example 44 ", *;

Bin 50 ml "three-necked round bottom flask," the 'rather with a dry ice trap connected to an inlet, an' with a Rüokfluflkühler, WEL thermometer and a magnetic stirrer is provided, is inserted into a bath maintained at a temperature of 40 + I ⁰ C oil bath, and with Purged with nitrogen. The flask is filled with 0.05 g (4.5 χ 10 * WoI) TiCl ₀ - and then with 14.6 ml (0.15 mol) 3-pentene nitrll, 14.6 ml dioxane, 0.81 ml PCo-0-OH ^) ^ and 0.440 g (5 χ 10 ^eJi mol) N: LiP (O - ^ - CRj,] ^ charged , which is cooled in an egg toad, bubbled "The nitrogen gas flow is set to adjust a total cyan" hydrogen charge of 5 * 7 ml (measured at 0 ⁹ C) liquid cyanide to 3 "5 ml nitrogen per minute. The resulting" Qasmlechung is over the surface of the Re & ktionamisohung in

rinsed the flask ·. After 21 hours and 3 minutes.

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the implementation is terminated.

Analysis by means of gas chromatography shows that 15.0% of the 3-pentenenitrile has been converted into dinitrile, the 3-pentenenitrile converted in this way to 90.5 # from adiponitrile 8.4 # from 1,3-dioyanobutane and 1 , 3 # composed of 1,2-dicyanobutane. The number of cycles (molar ratio of the generated Dloyanobutane to the added catalyst) is 75 * 5.

Example 45

A 50 ml three-necked round bottom flask, which is provided with a RUokf lußkUhler, which is connected to a Trooke ice trap, an inlet, a thermometer and a magnetic stirrer, is placed in an oil bath, whereby the contents of the flask are kept at a temperature of 40 ° C. The flask is purged with nitrogen. The flask is then filled with 2.42 ml of a 0.497m solution of titanium trichloride (1.2 χ ΙΟ ** mol) in 3-pentenenitrile and then with 19 * 5. ml of 3-pentenenitrile, 7 * 3 ml of dioxane, 0 * 81 ml of P (O-O-CH -) - and 0.440 g of Ni [P (0-0-CH ₃ ), J _{4 were} charged. A stream of nitrogen gas is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The stick-

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a hydrogen gas feed Qesantayanwasserstoff * of 2.8 ml (measured at 0 ⁰ C) liquid hydrogen cyanide to 3> 5 "1 per minute of nitrogen is set to set. The oas mixture obtained is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 21 hours and 23 minutes

Analysis by gas chromatography shows that 29 * 8J & des 3-pentenenitrile has been converted into dinitrile, whereby the 3-pentenenitrile converted in this way to 89.7 # Adiponitrile 8.45 ß composed of 1,3-dicyanobutane and 2.0 $ from 1,2-dicyanobutane. The number of cycles (molar ratio of the cyanobutanes produced to the catalyst fed in) is 225 As can be seen from an analysis of the nitriles, there is an obvious conversion to other nitriles, and that at an altitude from l, 0j6.

Example 46

A 50 ml three-necked round bottom flask fitted with a reflux condenser connected to a dry ice trap, an inlet, a A thermometer and a magnetic tap is placed in an oil bath, the contents of the flask being kept at 40 ° C. The flask is then purged with nitrogen. The piston we with

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2.42 ml of a 0.497m solution of titanium trichloride in 5-pentenenitrile and then with 12.2 ml of 3-phenylene, 14.6 ml of 1,2-dimethoxybenzene, 0.81 ml of P (O - ^ - CHj) ₅ and 0.440 g Ni [P (0-0-CH. ^ ^ * "- sends a stream of nitrogen gas through liquid hydrogen cyanide contained in a 50 ml flask which is cooled in an ice bath. the nitrogen is for a Qesamteyanwasseratoff feed setting of 4.7 ml (measured at 0 ⁰ C) liquid hydrogen cyanide to 3.5 ml nitrogen per minute regulated gas stream. the Oasmischung obtained is flushed over the surface of Reactions mi schurig in the piston " The reaction is ended after 26 hours and 20 minutes.

Analysis by gas chromatography shows that 56.5J ^ des 3-pentenenitrile have been converted into dinitriles, the 3-pentenenitrile converted in this way at £ 87.4 from adlponyltrile, $ 10.3 from 1,3-dieyanobutane and # 2.3 from 1,2-diyanobutane consists «The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst supplied) is 277 * As from an analysis of the nitriles shows an obvious one Conversion to other nitriles at a rate of 0.3 #.

Example 47

A 50 ml three-necked round bottom flask fitted with a reflux condenser connected to a trooke ice trap, an inlet and

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a magnetic stirrer «is immersed in an oil bath maintained at a temperature of 120 to 152 ⁰ C and flushed with dry, deoxygenated nitrogen. The flask is filled with 0.312 g (1.64 10 " ⁵ mol) SnClg, 4.06 g (l _# 21 χ IQ" * ² mol) P (OC ₆ H ₅ ) ₅ and 30.3 g (0 * 25 Mol) 2- * pentenenitrile and then charged with 2.29 g (1.64 χ 10 -2 mol) Ni [P (OC ₆ H ₅ ) ₃ 1 ₄ . A stream of dry, deoxygenated nitrogen gas is bubbled through 5.2 ml of hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath. The hydrogen cyanide is renewed if necessary. The nitrogen gas flow is regulated to 25 ml nitrogen gas per minute. The resulting gas mixture is flushed over the surface of the reaction mixture in the flask. The reaction is terminated after 18 hours and 45 minutes. * The total amount of hydrogen cyanide which has been added to the reaction is 8.5 ml.

Analysis by Gasohromatographle shows DAFL 20 of the reaction medium at the completion of reaction consist of adiponitrile. Of the 3-pentewitrile which has been converted into diitrile, 80j consists of adiponitrile. The number of cycles (molar ratio of the dicyanobutanes produced to the catalyst fed in) is 45. ■ "!:

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it

Example 48

A 50 ml three-necked round bottom flask "with a reflux condenser, is weloher connected to a dry ice trap, an inlet and a magnetic stirrer 1st provided, in a used at a temperature of 32-43 ⁰ C held oil bath and treated with dry» deoxygenated nitrogen purged . The flask is filled with 0.0855 6 SnCl ₂ , 12.01 g 3-pentenenitrile, 14.6 ml dioxane, 0.81 ml P (OC ₆ H ₅ ) ₅ and then with 0.440 g Ni [P (OC ₆ H ₅ U] _4. A stream of dry, deoxygenated nitrogen gas is bubbled through 8.9 ml of hydrogen cyanide contained in a 20 ml flask which is cooled in an ice bath The reaction mixture was rinsed in the flask, and after 5 hours and 41 minutes, the reaction was terminated, and the total amount of hydrogen cyanide added to the reaction medium was 3.3 ml.

Analysis by means of gas chromatography shows that 11.456 of the 3-pentenenitrile have been converted into dinitriles, with the dinitriles produced converting to 81.4 # from adiponitrile, 14.2 $ from 1,3-dicyanobutane and 3.2 $ from 1,2- Compose Dlcyanobutane. The number of cycles is 55 # 9 *

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Example 49

A 50 ml three-necked round bottom flask, an inlet and a magnetic stirrer is provided with a reflux condenser, which 1st connected to a dry ice trap is immersed in a at a temperature of 80-83 ⁰ C held oil bath and purged with dry, deoxygenated nitrogen . The flask is filled with 0.071 g (4.5 x 10 "* mol) SnP ₂ , 29.2 ml (0.3 mol) 3-pentenenitrll, 0.785 ml (3 χ 10 ~ ⁵ mol) P (OC ₆ H ₅ ) , and then charged with 0.420 g (3 x 10 "* mol) Ni [P (OC ₆ H ₅ ^] _4. One stream

from dry, deoxygenated nitrogen gas is through 6.6 ml of a liquid hydrogen cyanide in a 20 ml flask is contained, which is cooled in an ice bath, pearled. The nitrogen gas flow is increased to 4 ml nitrogen per minute regulated. The reaction is ended after 4 hours and 58 minutes. The total amount of hydrogen cyanide involved in the reaction has been supplied is 1.6 ml.

Analysis by means of Oaschromatography shows that 6 # of the 3-pentene nitrile have been converted into dinitriles, the produced dinitriles at 69.3 # from adiponitrile, 22.1 # from 1,3-dicyanobutane and $ 8.5 from 1,2-dicyanobutane. the Number of cycles is 59.

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In each of Examples 50 to 65, the same reaction conditions are maintained "with the exception" that no promoter is used. In this way, no detectable amounts of dinitriles can be determined.

Example 50

A 50 ml three-necked glass flask is fitted with a gas inlet tube "which is positioned so that the gas can be flushed over the surface of the contents of the flask." The flask is also fitted with a thermometer and a gas outlet line through a water-cooled reflux condenser. The flask is heated by means of an oil bath. Before adding the reagents, the whole system is purged well with purified nitrogen. Hydrogen cyanide is tortured by bubbling purified nitrogen through the liquid until the volume is reduced to half, whereupon the residue is distilled. The reaction flask is charged with 25 ml of 3-pentenenitrile, 0.032 g of VC1, 0.7 ml of tri-p-cresyl phosphite and 0.4 g of tetrakis-tri-p-cresyl phosphite nickel (0). The flask is placed in an oil bath, through which a temperature of 57 to 64 ° C is maintained. Hydrogen cyanide gas is then flushed over the surface of the catalyst mixture in a nitrogen carrier gas. The nitrogen flow rate is adjusted so that approximately

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is

0.2 ml of the liquid hydrogen cyanide are added per hour « After 6.5 hours of operation, the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. Analysis shows that the sample had $ 1.21 adiponitrile .22 pounds contains l, j3- »dicyanobutane and 0.2 $ 1,2-dicyanobutane.

Example 51

Following the procedure described in Example 50, 25 ml of> -pentenenitrile, 0.053 g of FeC-L **, 0.88 g of tri-p-cresyl phosphite and 0.4 g of tetrakis (tri-p-cresyl phosphite) nickel (05) are placed in the reaction flask To maintain a temperature of 58 to 62 ^° C., the flask is placed in an oil bath, whereupon hydrogen cyanide gas flows over the surface of the catalyst mixture

• ■ S

a nitrogen carrier gas is purged · The Sticksfcoff flow rate; is adjusted in such a way that approximately 0.2 ml of the liquid hydrogen cyanide are supplied per hour. After 5 hours of operation, the reaction is stopped. After standing at 25 ⁰ C under nitrogen over a period of 2 days wirdJ the mixture to 57 to 6O ⁰ C heated "which again is carried out an addition of hydrogen cyanide * A total of 0.2 ml of liquid hydrogen cyanide is supplied over a period of one hour. The addition is then stopped, whereupon the crude liquid is analyzed by means of cte-chromatography.

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Analysis shows that the sample contained 10.29 # adiponitrile 2 Contains 1,3-dicyanobutane and $ 0.55 1,2-dicyanobutane.

Example 52

Following the procedure described in Example 50, 25 ml of 3-pentenenitrile, 0.034 g of iron (II) chloride, 0.88 g of tri-p-cresyl phosphite and 0.4 g of tetrakis-Ctri-p-cresylphosphite (nickello) are introduced into the reaction flask. To maintain a temperature of 57 to 59 ^° C., the flask is placed in an oil bath, whereupon hydrogen cyanide gas in a nitrogen carrier gas is flushed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted so that approximately 0.2 ml of the liquid hydrogen cyanide is added per hour. After 4 hours of operation, the reaction is stopped. After 17 stttndigem standing at 25 ⁰ C under nitrogen the mixture is heated at 58 to 59 ° C, where again occurs a hydrogen cyanide addition. A total of 0.1 ml of liquid hydrogen cyanide is added over a period of one hour. The addition is then stopped, whereupon the crude liquid is analyzed by gas chromatography. Analysis shows that the sample contains 6.8 liters of adiponitrile, 1.6 liters of 1,3-dicyanobutane and 0.25 liters of 1,2-dicyanobutane.

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ft

Example 53

Following the procedure described in Example 50, 25 ml of 3-pentenenitrile, 0.034 g of MnClg, 0.88 g of tri-p-cresyl phosphite and 0.4 g of tetrakis (tri-p-cresyl phosphite) nickel (0) are introduced into the reaction flask. The piston is provided Äufrechterhaltung a temperature 57-61 ⁰ C in an oil bath, to which hydrogen _cyanide; is flushed over the surface of the catalyst mixture in a nitrogen carrier gas. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After about 4.5 hours, the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. The analysis shows that the sample contains 2.01 % adiponitrile, 0.5% adiponitrile, 0.5% Si 1,3-dicyanobutane and 0.25% 1,2-dicyanobutane Contains

example

After the working catfish described in Example 50, 25 ml 3-pentenenitrile, 0.043 g ChromilllJ -chloridi 0.7 ml tri-p-cresyl phosphite and 0.4 ml tetrakis (tri-p-cresylphosphite) nickel (0) added to the reaction flask. The flask is used to keep up a temperature of 5? placed in an oil bath up to 59 ° G, whereupon hydrogen cyanide gas in a nitrogen carrier gas over the Surface of the catalyst mixture is rinsed. The nitrogen

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The flow rate is adjusted so that approximately 0.2 ml liquid hydrogen cyanide per hour are supplied. To

The reaction is stopped for 4 hours, whereupon the crude liquid is analyzed by gas chromatography. Analysis shows that the sample was $ 2.66 adiponitrile, $ 0.35 1,3-dicyanobutane and 0.07 # 1,2-dicyanobutane.

Example 55

According to the method described in Example 50, 20.66 g 3-pentenenitrile, 0.035 g cobalt (II) chloride, 0.7 ml tri-p-cresyl phosphite and add 0.4 g of tetrakis (tri-p-cresylphosphite) nickel (0) to the reaction flask. The piston is used to maintain placed in an oil bath at a temperature of 59 to 60 ° C, whereupon Hydrogen cyanide gas iri a nitrogen carrier gas over the surface the catalyst mixture is rinsed. The nitrogen flow rate is adjusted so that approximately 0.2 ml of liquid hydrogen cyanide are added per hour. To

The reaction is stopped for 5 hours, after which the crude liquid product is analyzed by means of gas chromatography. Analysis shows that the sample contains 12.47 % adiponitrile, 2.90% 1,3-dicyanobutane and 0.6L # 1,2-dicyanobutane.

Example 56

After the working catfish described in Example 50, 20.93 g

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3-pentenenitrile, 0.065 g zirconium (IV) »chloride, 0.7 ml tri-p-cresyl phosphite and 0.4 g of tetrakis (tri-p-oresylphosphite) nickel (0) introduced into the reaction flask. Piston is used to maintain placed in an oil bath at a temperature of 58 to 59 ° C, whereupon hydrogen cyanide gas in a nitrogen carrier gas over the Surface of the catalyst mixture is passed. The nitrogen flow rate is adjusted in such a way that approximately 0.2 ml of liquid hydrogen cyanide are fed in per hour The reaction is stopped for 1 hours, whereupon the crude liquid is analyzed by means of oase chromatography. The analysis shows the sample $ 0.9 adiponitrile $ 0.21 1,3-dieyanobutane and 0.06 # 1,2-dicyanobutane.

Example 57

According to the procedure described in Example 50, 25 ml of 3-pentenenitrile, 0.04l g of scandium (III) chloride, 0.7 ml of tri-pcresylphosphite and 0.4 g of tetrakis (tri-p-cresylphosphite) nickel (G) introduced into the reaction flask. The flask is placed to maintain a temperature of 59 ⁰ C in an oil bath, to which hydrogen cyanide gas is purged in a nitrogen carrier gas over the surface of Kittalysatormischung. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen hydrogen per hour. After 3.5 hours, the reaction is stopped, whereupon the crude liquid

. 69 -

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is analyzed using gas chromatography. The analysis shows4 that the sample 1,3Jf adiponitrile 0,23 # 1,3-dicyanobutane and $ 0.22 contains 1,2-dicyanobutane.

Example 58

According to the procedure described in Example 50, 25 ml of 3-pentenenitr ⁴ .l, 0.051 g of tin (II) chloride, 0.7 ml of Trl-p-cresylphosphite and 0.4 g of tetrakis (tri «p-cresylphosphite) are added. "Nickel (0) introduced into the reaction flask" The flask is placed in an oil bath to maintain a temperature of 58 to 59 ° C, whereupon hydrogen oyanide gas in a nitrogen carrier gas is passed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After 5 hours the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. The analysis shows that the sample contains 12.27 $ adiponitrile, 2.9 ^ 1,3-dicyanobutane and 0.63 $ 1,2-dicyanobutane .

Example 59

According to the procedure described in Example 50, 25 ml 3-pentenenitrile, 0.048 g palladium (II) chloride, 0.7 ml tri-pcresyl phosphite and 0.4 g of tetrakis (tri-p-cresylphGsphit) -nickel (0)

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introduced into the reaction flask. The flask is set oil bath to maintain a temperature of 58-60 ⁰ C in, whereupon hydrogen cyanide is passed into a Stickstoffträgergae over the surface of the catalyst mixture. The nitrogen flow rate is adjusted so that approximately 0.2 ml of liquid hydrogen cyanide3 is supplied per hour. After 3.5 hours the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. Analysis shows that the sample contains 0.30 # adiponitrile, 0.04 # 1,25-dieyanobutane and 0.12 # 1,2-dicyanobutane.

Example 60

According to the procedure described in Example 50, 25 ml of 3-pentenenitrile, 0.055 g of bis-acetonitrile dichlorochromium (II} _5, 0.7 ml of tri-p-cresyl phosphite and 0.4 g of tetrakis (tri-p-cresyl phosphite) nickel (O) introduced in the reaction flask. the flask is placed an oil bath to maintain a temperature of 56-65 ⁰ C in, whereupon hydrogen cyanide is conducted in a nitrogen carrier gas over the surface of the catalyst mixture. the nitrogen flow rate is adjusted so that approximately 0.2 ml liquid hydrogen cyanide per hour are fed in. After 3 hours, the reaction is stopped, whereupon the crude liquid is analyzed by means of oaschromatography. The analysis shows that the sample is 12-17 $ adiponitrile

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1,3-Di cyano butane and 0.48 % 1,2-Dicyanobutan contains.

Example 6l

After the working catfish described in Example 50, 25 ml of 3-pentenenitrile, 0.10 g of thorium (17) chloride, 0.7 ml of tri-poresylphosphite and 0.4 g of tetrakis (trl-p-cresylphosphite) -nicke1 (0) introduced into the reaction flask. The piston is used to Aufrechterhai tung a temperature from 59 to 6O ⁰ C in an oil bath set, whereupon hydrogen cyanide gas in a nitrogen carrier gas * is passed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After half an hour and 40 minutes, the reaction is stopped, whereupon the crude liquid is analyzed by means of oaschromatography. The analysis shows that the sample contains 0.77 # adiponitrile 0.01j6 1,3-dicyanobutane and 0.01 # 1,2-dicyanobutane.

Example 62

According to the procedure described in Example 50, 25 ml. 3-pentenenitrile, 0.047 β gallium (III) chloride, 0.7 »1 tri-pcreeyl phosphite and 0.4 g tetraki8 (tri-p-oresyl phosphite) nickel (0) introduced into the reaction flask. The flask is placed in an oil bath

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to maintain a temperature of 58 to 60 ° C «whereupon hydrogen cyanide gas in a nitrogen carrier gas is flushed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After 5 hours the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. The analysis shows that the sample contains 3.73% adiponitrile 3 * 00 # 1, J-dioyanobutane and 2, VJ & 1,2-dicyanobutane.

Example 63

After the Arbeitsswelse described in Example 50, 25 ml of 3-pentenenitrile, 0.079 g of rhenium (III) chloride, 0.7 ml of tri-pcresylphosphite and 0.4 g of tetrakis (trl-p-oresylphosphite) -nlckel (0) are in the Reaction flask inserted. To maintain a temperature of 55 to 65 ⁰ O, the flask is placed in an oil bath, whereupon hydrogen cyanide gas in a nitrogen carrier gas is flushed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After h hours, the reaction is stopped, whereupon the crude liquid by means of; Gas chromatography is analyzed. The analysis shows that sample C contains, 82 # adiponitrile, 0.19 # 1,3-dicyanobutane and 0.11 μl of 1,2-di-cyano butan.

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Example 64

After the working catfish described in Example 50, 25 ml of 3-pentenenitrile, 0.1 g of tris (tetrahydrofuran) trichlorochrome (III), 0.7 ml of tri-p-cresyl phosphite and 0.4 g of tetrakis (tri-p-cresyl phosphite) - nickel (0) is introduced into the reaction flask. The flask is set to maintain a temperature of 41-42 ⁰ C in an oil bath, to which hydrogen cyanide is passed into a Stlckstoffträgergas over the surface of the catalyst mixture. The nitrogen flow rate is adjusted so that approximately 0.2 ml of liquid hydrogen cyanide3 is supplied per hour. After 5.5 hours the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. Analysis shows the sample contains $ 11.63 adiponitrile, 1.5 # 1,3-dioyanobutane, and 0.14 # 1,2-dicyanobutane.

Example 65

After the work catfish described in Example 50, 15.1 g 2-pentenenitrile, 5 # 0 g tetrahydrofuran, 0.4 g tris (tetrahydrofuran) trichlorochromiumClII), 1.4 ml of tri-p-cresyl phosphite and 0.8 g Tetrakis (tri-p-cresylphosphite) nickel (0) into the reaction flask introduced. The flask is placed in an oil bath to maintain a temperature of 41 to 43 ° C, whereupon hydrogen cyanide

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gas In a nitrogen carrier gas over the surface of the Catalyst mixture is flushed. The nitrogen flow rate is adjusted so that approximately 0.2 ml of liquid Hydrogen cyanide are fed per hour. After 46 hours the reaction is stopped «whereupon the crude liquid is analyzed by gas chromatography · The analysis shows that the sample 6O, 8l # adiponitrile 5.51 # 1,3-dieyanobutane and Contains 1,2-dicyanobutane.

Example 66

According to the procedure described in Example 31, 25 ml 3-pentenenitrile, 0.4 g tetrakis (tri-p-cresylphosphite) nickel (0), 0.05 g tungsten (V) chloride and 0.7 ml tri-p-oresyl phosphite in introduced the reaction flask. The piston is used to maintain placed in an oil bath at a temperature of 57 to 59 ° C, whereupon hydrogen cyanide gas in a nitrogen carrier gas over the Surface of the catalyst mixture is rinsed. The nitrogen flow rate is adjusted so that approximately 0.2 ml of liquid hydrogen cyanide s are supplied per hour. To The reaction is stopped for about 5 hours, after which the crude liquid is analyzed by gas chromatography. The analysis shows that the sample 1.22 # adiponitrile 0.29 # 1,3-dicyanobutane and 0.14 ^ 1,2-dicyanobutane.

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Example 67

Following the procedure described in Example 31, 25 ml of 3-pentenenitrile, 0.4 g of tetrakis-tri-p-eresylphosphite) nickel (0) and 0.036 g of aluminum (III) chloride are introduced into the reaction flask. The flask is placed in an oil bath to maintain a temperature of 57 ⁹ C, whereupon hydrogen cyanide gas in a nitrogen carrier gas is flushed over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to deliver approximately 0.2 ml of liquid hydrogen cyanide per hour. After about 20.5 hours, the reaction is stopped and the crude liquid is analyzed by gas chromatography. Analysis shows that the sample contains 6.48 # adiponitrile, 7.67 ^ 1,3-dicyanobutane, and 2,4256 1,2-dicyanobutane.

Example 68

Following the procedure described in Example j51, 25 ml of 3-pentenenitrile, 0.4 g of TetrakisCtri-p-cresylphosphite nickel (0) and 0.051 g of tin (II) chloride are introduced into the reaction flask. The flask is placed an oil bath to maintain a temperature of 56-57 ⁰ C in a, to which hydrogen cyanide gas is purged in a nitrogen carrier gas over the surface of the catalyst mixture. The nitrogen flow rate becomes such

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set so that approximately 0.2 ml of liquid hydrogen cyanide are fed per hour. After about 20 hours the reaction is stopped, whereupon the crude liquid is analyzed by means of oaehromatography. The analysis shows that the sample contains 9.68 % adiponitrile 3, 16.6% 1,5-dicyanobutane and 0.66% 1,2-dioyano-butane contains,

Example 69

According to the working cycle described in example j51, 25 dl 3-pentenenitrile, 0.4 g tetrakis (tri-p-cresylphosphite) nickel (0), 0.078 g germanium (IV) iodide and 0.7 ml tri-p-cresyl phosphite introduced into the reaction flask. The flask is placed in an oil bath to maintain a temperature of 59 to 61 ° C. whereupon hydrogen cyanide gas in a nitrogen carrier gas over the Surface of the catalyst mixture is passed. The stick material FlieSgeschwindigkelt is set so that approximately 0.2 ml of liquid hydrogen cyanide ^ are fed per hour. After about 3.5 hours, the reaction is stopped, whereupon the crude liquid is analyzed by gas chromatography. The analysis shows that the sample contains 0.44 $ adiponitrile 0, Contains 1,3-dicyanobutane and a trace of 1,2-dicyanobutane.

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Example 70

According to the working mode described in Example 31, 25 ml of 3-pentenenitrile, 0.4 g of tetrakis (tri-p-oresylphosphite) nickel (0) and 0.0j} 4 g of manganese chloride are introduced into the reaction flask. The flask is placed to maintain a temperature of 6l to 65 ⁰ C in an oil bath, is passed whereupon hydrogen cyanide gas in a nitrogen carrier gas over the surface of the catalyst mixture. The nitrogen flow rate is adjusted to add approximately 0.2 ml of liquid hydrogen cyanide per hour. After about 20.5 hours, the reaction is stopped and the crude liquid is analyzed by means of oaschromatography. Analysis shows the sample contains $ 15.28 adiponitrile, $ 5.57 1,3-dicyanobutane, and $ 0.97 1,2-dicyanobutane.

Example 71

A 50 ml three-necked round-bottomed flask fitted with a reflux condenser connected to a dry ice trap, an inlet and a magnetic stirrer is placed in an ^{oil bath maintained at 80 °} C. and flushed with dry, deoxygenated nitrogen . The flask is filled with 0.10 g (0.00051 mol) AgBB '^ and then with IjO g (0.000768 mol) Ni [P (OC ₆ H ₅ ) J ₁ ^ 20 g (0.247 mol) 3-pentenenitrile and 1.91 g (0.00616 moles) of P (OCgH ₅ ) - charged. A stream

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from nitrogen gas, which has been de-oxygenated, is replaced by 10 ml of a liquid hydrogen cyanide in a 20 ml container is included, which is cooled in an ice bath, pearled. The nitrogen gas flow is increased to 15 ml nitrogen per Minute set. The gas mixture obtained is passed through a bed of phosphorus pentoxide to remove traces of moisture passed and then over the surface of the reaction mixture rinsed in the flask. After 2 hours and 18 minutes the Reaction ended. Gas chromatographic analysis shows that the reaction mixture is 4.82 $ adiponitrile, 1.54 $ 1,3-dicyanobutane and 0.24 # 1,2-dioysnobutane. The number of cycles is 18.8.

Example 72

A 50 ml three-necked round bottom flask, which is provided with a reflux condenser connected to a dry ice trap, an inlet and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 82 to 86 °} C. and flushed with dry, deoxygenated nitrogen . The flask is filled with 0.170 g (4.5 x 10 ~ * mol) ErCl ₅ VOH ₂ O, 29.2 ml (0.3 mol) 3-pentenenitrile, 0.78 ml (3 χ 10 " ⁵ mol) P ( OC ₆ H ₅ ), and then charged with 0.420 g (3 χ 10 "* mol) Ni [P (OC ₆ H ₅ J ₅ I ₁ ^. A stream of dry, deoxygenated nitrogen gas is passed through

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8.4 ml of hydrogen cyanide contained in a 20 ml flask Is "which is cooled in an ice bath" pearled. The received Gas mixture is flushed over the surface of the reaction mixture in the flask. After 2 hours and 43 minutes, the. Reaction ended. The total amount of hydrogen cyanide charged to the reaction medium is 1.8 ml.

Gas chromatographic analysis shows that Τϊ% of the dinitriles produced consist of adiponitrile. The number of cycles is 5 to 7

Example 73

A 50 ml three-necked flask equipped with a reflux condenser connected to a dry ice trap, an inlet and a magnetic stirrer is placed in an oil bath kept at a temperature of 75 to 77 ° C and flushed with dry, deoxygenated nitrogen . The flask is filled with two spatula tips (approximately 0.1 to 0.2 g) BeCl ₀ * 39.1 ml (0.4 mol) 3-pentenenitrile, 3 * 4 ml (1.1 χ 10 ~ ² mol) P ( QC ₆ H ₅ ) ^ and then charged with 1.40 g (1.1 χ 10 -2 mol) Nl [P (OCgH ₅ ) -] ^. (The BeCl ₂ was assessed rather than weighed due to its extreme toxicity. The relevant surface of the spatula used was approximately 1 mm wide and 5 mm long).

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A stream of dry, deoxygenated nitrogen gas is replaced by 10.5 ml of hydrogen cyanide in a 20 ml flask is contained, which is cooled in an ice bath, pearled. The oas mixture obtained is spread over the surface of the reaction mixture rinsed in the flask.

After 50 minutes the flask contains approximately 3% adiponitrile which corresponds to a 79 # yield of adiponitrile and 15 cycles. The total amount of hydrogen cyanide which is added to the reaction medium is 1.5 ml.

Example 74

A 50 ml three-necked round bottom flask old lußkühler a Fdbk, which is connected to a Trookeneisfalle, an inlet and a magnet is provided stirrer, is placed in a bath maintained at a temperature of 80 ⁰ C oil bath and purged with dry, deoxygenated Stiokstoff . The flask is filled with 0.65 g (5 X to '** mol) NitPCQCgHg) ^, 0.2 g MoCl ₂ , 20 g (0.248 mol) 3-pentehnitrile and 3 * 0 g (0.01 mol) P ( OC ₆ H ₅ ) ₅ charged. A stream of dry, deoxygenated nitrogen gas is bubbled in an amount of 15 ml per minute through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in an Elsjbad

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is rinsed over the surface of the reaction solution in the flask. The reaction is carried out until the catalyst appears to be consumed. At this point the gas chromatographic analysis that the reaction mixture $ 3.26 Adiponyltrile, 0.79 £ 1,3-Dloyanobutane and 0,] j6 # 1,2-Dicyano butane contains. The number of cycles is 19 «

Example 75

In a 50 ml Olas reactor equipped with a stirrer 19 * 35 g of a solution containing the following ingredients was introduced:

0.47 g (0.32 mmol)

0.10 g (0.73 mmol)

1.35 g (3.83 mmol) P (O-X Q

19.12 g (236.0 mmol) of 4-pentenenitrile, 21.04 g total

The reactor is protected by an atmosphere of dry nitrogen gas ,, is heated and the solution of 8O ⁰ C * An aliquot of solution output is analyzed for Mono "and Dinitri! Products. A gaseous charge of hydrogen cyanide is slowly passed over the reaction surface over a period of 296 minutes in an amount of 1.0 ml per hour, with after

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Vk

10, 15, 25, 35, 45 and 296 minutes all quotations removed for analysis will. The weight of the final reaction mixture is 10.70 g. The weight of the aliquots removed is 8.48 g.

The analytical values for at time 0 and after 296 minutes samples taken are as follows:

Analysis * weight %

Minutes t = 0 t = 296 - 44.92 0.84 M * «ar 10.09 0.4? <0.12 - <0.10 0.58 19.95 85.85 1.55 4.10

Connection

Adiponitrile

1,2-dicyanobufcan

1,3-dicyanobufcan

cis-2-pentenenitrile

c i s-2-methyl "2" butenenitrile Valeronitrile

trans-2-pentenenitrile

fcrans-3-pentenenitrile

4-pentenenitrile

Gls-3-pentenniferil

The catalyst efficiency is 174 cycles after 296 minutes, based on the product that remains in the reactor.

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The value of 174 cycles does not include Dinitri! Products and unconverted ones active catalyst «which has been removed with the aliquots for the analyzes.

Example 76

There are the following starting materials in one equipped with a stirrer 50 ml flask given by controlling the temperature the liquid> which circulates in a jacket surrounding the reactor »is kept at 60 ° C. The piston «which is completed with respect to the atmosphere purged with dry nitrogen gas. Then during the reaction a continuous, slow stream of nitrogen gas (3 mmol per Minute) passed through the reactor. The exhaust gas from the reactor is passed through a dry ice trap and then through a liquid seal made of paraffin oil is discharged into the atmosphere.

5.0 g of catalyst solution that

0.82 g (0.56 mmol tetrakieltri (p-oresyl)

phosphite] nickel (0) contains 4.18 g of toluene solvent 0.12 g (0.88 mmol) of ZnCl ₂
2.00 g (5.7 mmol) of TrI (p-oresyl) phosphite 19 »3 g (238 mmol) of 2-methyl-3-butenenitrile.

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In an amount of 2 mmol per minute during a tent » span of ITE minutes Cy watering off steam into the steam room released into the reactor The experiment will be terminated if the hydrocyanation reaction is still actively progressing *

The product withdrawn from the reactor weighs 30.3 g and is analyzed for mono * and dinitrile by means of gas chromatography. It is found that there are 0.15 % adiponitrile 6> 2 _S 9% 1,3-di-eyanobutane, 3 "9 * $ 2-methyl" 2-butenenitrile and 2.02% 2-methyl-3-butenenitrile contains. The catalyst efficiency for the product from 1,3-pioyanobutane is 320 cycles.

Example 77

The following starting materials are placed in a 50 ral flask equipped with a stirrer, which is kept ^{at 40 ° C. by controlling the temperature of the liquid that circulates through a jacket surrounding the reactor.} The flask, which is closed to the atmosphere, is initially flushed with dry nitrogen gas, after which a continuous stream of nitrogen is maintained through the reactor during the reaction at a rate of 1 mmol per minute. The exhaust gas from the reactor is passed through a Trookeneia trap and then through a liquid seal made of paraffin oil to the atmosphere

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St.

submittedϊ

8.6l g of catalyst solution that

1 # 42 g (0.97 «mol) TetrakisCtri (p-cresyl) -

phosphorous] nickel (O) contains Τ * 19 β toluene solvent. 0.19 g (1 * 0 mmol) SnCl ₂

5.60 g (15 * 9 mmol) of tri (p-oresyl) phosphite.

Both hydrogen cyanide and 4-pentenenitrile are continuously fed to the reactor during the reaction period. Of the Hydrogen cyanide stream is started a few minutes before the 4-pentenenitrile to ensure that there is an excess of hydrogen cyanide in the reactor. In an amount of 0.75 mmol per minute hydrogen cyanide vapor is in the vapor space in the Reactor set free, while liquid 4-pentenenitrile in an amount of 0.50 mmol per minute in the reaction mixture is introduced. After 4-pentennyltrile has been fed in for 26Ό minutes, the Versuoh, while the Hydrooyanierungsreaktion nooh actively progresses, ended.

9 small samples are taken at Zwisohenintervallen from the reaction mixture and by means of gas chromatography on mono- and Dinitrile examined. The total weight of the samples is approximately 0.9 g. The end product obtained from the reactor

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weighs 26.1 g and has the following composition, as is evident from an analysis by means of Oaschromatography; Adiponitrile 36,956, 1,2-dicyanobutane O, II &: 1,3-dicyanobutane 6, O6 #, tear-3-pentenenitrile 0.80 #, 4-pentenenitrile 0.09 # and cis -3-pentenenitrile 0.86 #. The total dinitrile catalyst efficiency based on the initial nickel loading is 105 cycles.

Example 78

A 100 ml three neck round bottom flask fitted with a reflux condenser connected to a dry ice trap, inlet, thermometer and magnetic stirrer is placed in an oil bath and purged with nitrogen. The flask is filled with 5.15 g (0.015 mol) P (OC ₆ H ₅ ) y 52.0 g (0.500 mol) styrene, 6.50 g (0.005 mol) Ni [P (OC ₆ H ₅ ),] ^ , 0.68 g (0.005 mol) of zinc chloride and 50 ml of methyl cyanide. The contents of the flask are kept at a temperature of 86.5 to 88 ^° C. during the reaction. A nitrogen gas stream is bubbled through liquid hydrogen cyanide contained in a flask cooled in a water bath at ambient temperature. The resulting gas mixture is flushed over the surface of the reaction mixture in the flask. The reaction is ended after one hour and 3 minutes. The total amount of hydrogen cyanide introduced into the reaction

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is about 5 * 5 ml.

Analysis by gas chromatography shows that 3.5 $ des added styrene

to

₂ CH ₂ CN

have been converted.

Example 79

A 100 ml three-necked round bottom flask, which is provided with a reflux condenser connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer, is placed in an ^{oil bath kept at a temperature of 104 °} C. and flushed with nitrogen. The flask is filled with 1.03 g (0.003 mol) P (OC ₆ H ₅ ), 8.22 g (0.100 mol) cyclohexene, 1.30 g (0.001 mol) Ni [P (OC ₆ H ₅ ) I ₄ , 0.70 g (0.005 mol) of zinc chloride and 10 ml of methyloyanide charged. A stream of nitrogen gas is passed through 24.7 ml of liquid hydrogen cyanide contained in a flask which is placed in a water bath at ambient temperature,

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door is cooled * in an amount of approximately 90 pearls per Minute (4 ml HCN / hour) bubbled * After one hour and 24 minutes, the hydrogen cyanide flow is stopped for 48 minutes and then recorded again for another 13 minutes »

The distillation gives 8.11 g of cyclohexyloyanide. this means a 74 # yield »based on the supplied Cyοlohexen.

Example 80

A 100 ml three-necked round bottom flask fitted with a RüokflufikUhler, which is connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer is provided « placed in an oil bath and purged with nitrogen. The piston becomes with 27.93 g (0.300 mol)

I CH ₂ - CH - CN

3 # 90 g (0.003 mole) NiCP (OC ₆ H ₅ J ₅ J ₄ , 0.816 g (0.006 mole) zinc «.

Charge chloride and 30 ml of methyl cyanide. The contents of the flask is kept at 93 to 97 ° C during * the reaction · A stick · Substance gas flow is replaced by liquid hydrogen cyanide, which in a flask which is cooled in a water bath at ambient temperature, pearled. The received oasis hunger

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is over the surface of the reaction mixture in the flask flushed. The reaction is ended after one hour and 9 minutes. The total amount of hydrogen cyanide in the reactor is supplied »is approximately 13 ml.

The distillation gives 21.75 g of a fraction which boils at 90 to 95 ° C. and is a compound of the formula

which to JOJi in the cis and au 60% in the trans configuration «is identified. This corresponds to a yield of 60Ji based on the olefin starting material.

Example 8l

A 100 ml three-necked round-bottomed flask fitted with a reef condenser connected to a dry ice trap, "a BInIaB, a thermometer and a magnetic stirrer" is placed in an oil bath and flushed with nitrogen. The flask is filled with 8.42 g (0.100 mol) hexene-1, 0.65 g (0.005 mol) Ni [P (OC ₆ H ₅ ), I ₄ , 0.38 g (0.002 mol) tin (II) - Chloride and 10 ml Methyloyänld charged. The contents of the flask are kept at a temperature of 57 to 66 ° C. during the reaction. A

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Nitrogen gas flow is in an amount of approximately ISO beads per minute (approx. 5 ml HCN / hour) by liquid hydrogen cyanide, contained in a flask cooled in a water bath at ambient temperature. After one hour and 26 minutes, the reaction is ended »

Distillation of the reaction mixture yields 4.60 g of a fraction which boils at 54 to -59 ° C./8 mm Hg. When this fraction is separated by vapor phase chromatography and collected, two main components are obtained. The first component consists of 2k% of the fraction and is identified as 2 «cyanohexane, while the second component consists of 74% of the fraction and is identified as 1-cyanohexane.

Example 82

A 100 ml three neck round bottom flask fitted with a reflux condenser attached to a dry ice trap, inlet, thermometer and magnetic stirrer is placed in an oil bath and purged with nitrogen. The flask is filled with 6.81 g (0.100 mol) of cyclopentene, 1.30 g (O ₀ OOl mol) of Ni [P (OC ₆ H ₅ ) ^] ₄ , 0.760 g (0.004 mol) of ZIm (II) chloride and 20 ml of methyl cyanide charged. The contents of the flask are kept at a temperature of 47.5 to 58 ^° C. during the reaction

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The nitrogen gas stream is in the amount of approximately 120 beads per minute by liquid hydrogen cyanide contained in a flask placed in a water bath at ambient temperature is cooled, pearled. The preserved Oasmisohung is over the surface of the reaction mixture in the flask flushed. When the reaction mixture is distilled, a yield of 20%, based on the cyclopentene fed in, is obtained Cyclopentyloyanide.

Example 8?

A 100 ml three-necked round bottom flask fitted with a reflux condenser connected to a dry ice trap, an invitation, a thermometer and a magnetic stirrer is placed in an oil bath and flushed with nitrogen. The flask is filled with 12.12 g (0.100 mol) octene-1, 1.30 g (0.001 mol) Ni [P (OC ₆ H ₅ ) _{I 4} , 0.760 g (0.004 mol) tin (II) chloride and 10 ml of methyloyanide charged. The contents of the flask are kept at a temperature of 79 to 82 ^° C. during the reaction. A stream of nitrogen gas is bubbled through liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature. The resulting oas mixture is flushed over the surface of the reaction mixture in the flask. The reaction is ended after 41 minutes.

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Pie total amount of hydrogen cyanide, which in the reactor is about 2.4 ml.

Working up the mixture results in a length of 40 pounds Yield of nonanenitriles, which are $ 71 from 1-nonanenitrile and to consist of 2-nonanenitrile.

Example 84

A 100 ml three-necked round bottom flask, which is provided with a reflux condenser connected to a dry ice trap, an inlet, a thermometer and a magnetic stirrer, is ^{immersed in an oil bath kept at a temperature of 77 °} C. and flushed with nitrogen. 1.30 g (0.001 mol) of Ni [P (OC ₆ H ₅ ) J ₂₁ , 0.760 g (0.004 mol) of tin (II) chloride and 15 ml of methyl cyanide are charged into a flask.

Pann is ethylene gas in the flask in an amount of 550 ecm initiated per minute during implementation. A stream of nitrogen gas is passed through 29 ml of liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature. The oasis solution obtained is rinsed over the surface of the reaction mixture The original temperature of the contents of the flask is 64 ° C.

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After a reaction time of 53 minutes, this temperature reaches 72 ^° C. After 2 hours and 43 minutes, the supply of hydrogen cyanide is interrupted after 10 ml of hydrogen cyanide have been introduced into the flask in the oil bath. After a further 15 minutes, the supply of hydrogen cyanide is immediately resumed. The temperature rises by I ⁰ C, whereupon the reaction is ended. The reaction mixture is distilled. In this case fall to 20.63 g of a fraction boiling at 40 to 98 ⁰ and C is determined by means of NMR spectrum as Fropionitril (6.70 g). This means one. Number of cycles of 125 *

Example 85

A 100 ml three-necked round bottom flask provided with a reflux condenser, which is connected to a dry ice trap, an Invitation, a thermometer and a magnetic stirrer is used in a bath maintained at a temperature of 92 ⁰ C oil bath and purged with nitrogen. The flask is loaded with 9.46 g (0.100 mol)

CH ₂

'' CH-CH-

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1, JO g (0.001 mol) Ni [P (OC ₆ Xi ₅ U] ₂ ^, 0.7c · g (0.004 mol) tin (II) chloride and 10 ml of methylcyaiiia / baschiclrt. A nitrogen gas stream is replaced by liquid hydrogen cyanide contained in a flask is where cooled in a water bath at ambient temperature, g "pearls. the egg-keeping gas mixture is flushed over the surface of Reaktionsraischung * the temperature of the reaction mixture at the start 72 ⁰ C. after 58 minutes, the Temperature rose to 88 ° C. After a further 57 minutes, the temperature fell to 72 ° C., whereupon the reaction was ended. A total of 7 * 5 ml of hydrogen cyanide were introduced into the reactor.

The analysis shows a 77% yield

based on the olefin starting material.

Example 86

A 100 ml three-necked round bottom flask fitted with a RUok-fl ow condenser, which is connected to a dry ice trap, is provided with an inlet and a magnetic stirrer, is placed in an oil bath and flushed with nitrogen. The flask is charged at 8.42 g

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(0.100 mol) a-methylpentene-O, 1 * 30 g (0.001 mol) N ₆₅₅ 0.76 g (0.004 mol) tin (II) chloride and 10 ml methyl cyanide. The contents of the flask are kept ^{at 51 to 58 ° C. during the reaction.} A stream of nitrogen gas is bubbled at about 120 beads per minute through liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature. The resulting gas mixture is flushed over the surface of the reaction mixture contained in the flask. The total amount of hydrogen cyanide which is fed to the reaction mixture is 5.5 ml · After one hour and 37 minutes, the reaction is terminated.

During the distillation, a nitrile fraction is obtained, the one Yield of 27Ji based on the S-methylpentene-3 starting material is equivalent to. When separating by means of vapor phase chromatography and collection of this nitrile fraction falls in 14 # yield 2-cyano-4-methylpentane and in 85 # yield l-cyano-4-methylpentane.

Example 87

A 100 ml three-necked round bottom flask fitted with a RUokfluJ3kUhler which is connected to a Trook ice trap , an inlet,

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a thermometer and a magnetic stirrer is placed in an oil bath. The flask is filled with 8.42 g (0.100 mol) 2-methylpentene-l, 1.30 g (0.001 mol) Ni [P (OC ₅ H ₅ ^] ₄ , 0.76 g (0.004 mol) tin (II) Chloride and 10 ml of methyl cyanide are charged The contents of the flask are kept at a temperature of 52 to 58 ° C. during the reaction After 18 minutes, the supply of hydrogen cyanide into the flask is 2.4 ml. At this point, the supply of hydrogen cyanide is stopped, while the reaction is ended after a further 6 minutes.

The distillation gives 9% (based on the 2-methylpentene-1) methylcyanopentanes, which are 53 * 1 $ from 1-cyano-2-methylpentane, 36.4 # from 1-cyano-4-roethylpentane and 6, 7 $ composed of an isomer believed to be 2-cyano-4-methylpentane.

example

A 100 ml three-necked round bottom flask fitted with a reflux condenser, which is connected to a trooke ice trap, an inlet, a thermometer and a magnetic stirrer is provided

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JO

Inserted in an oil bath. The flask is filled with 8.42 g (0.100 mol) of a mixture of cis- and trans-hexene-2, 1.30 g (0.001 mol) NiCP (OC ₆ H ₅ J ₅ ] ^, 0.76 g (0.004 mol ) Tin dichloride and 10 ml of methyloyanide are charged. The contents of the flask are kept during the reaction at 56 to 60 ° C. A nitrogen gas stream is bubbled through 26.4 ml of liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature The resulting gas mixture is rinsed over the surface of the reaction mixture in the flask. After 33 minutes, the supply of hydrogen cyanide is 3.5 ml into the flask in the oil bath. After a further 11 minutes, the reaction is terminated.

Analysis shows the presence of $ 36 (based on the Hexen-2) cyanohexanes supplied, which are composed of 75 $ from 1-cyanohexane and 23 $ from 2-cyanohexane.

Example 89

A 100 ml three-necked round bottom flask fitted with a Rüokflufiktihler, which is connected to a dry ice trap, an inlet, a thermometer and a magnet stir it is provided placed in an oil bath and purged with nitrogen. The flask is filled with 6.71 g (0.100 mol) of 1-cyanopropene-2, 1.30 g (0.001 mol)

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NiCP (OC ₆ H ₅ ) ^] ₄ , 0.76 g (0.004 mol) of tin dichloride and 10 ml of methyl cyanide were charged. The contents of the flask are kept ^{at 84 to 94 ° C. during the reaction.} A stream of nitrogen gas is bubbled through 16 ml of liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature. The resulting oasis solution is rinsed over the surface of the reaction mixture in the flask. After 27 minutes, the supply of hydrogen cyanide to the flask in the oil bath is 4.5 ml. After a further 8 minutes, the reaction is terminated.

Analysis shows a 70 # conversion of the 1-cyanopropene-2 into a mixture of 57 $ olutaronitrile and 41 # methylsuccinonitrile.

Example 90

A 100 ml three-necked round bottom flask fitted with a refluflcooler connected to a Trooke ice trap, an inlet, a thermometer and a magnetic stirrer is placed in an oil bath maintained at a temperature of 100 ° C and flushed with nitrogen. The flask is filled with 10.71 g (0.100 mol) of 1-cyanooyclohexene O >> 1.30 g (0.001 mol) Ni [P (OC ₆ H ₅ ) ₅ ) ₄ , 0.70 g (0.005 mol) zinc chloride and 10 ml methyl

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AD% 198 R

eyanid loaded. A stream of nitrogen gas is bubbled through liquid hydrogen cyanide contained in a flask which is cooled in a water bath at ambient temperature. The resulting gas mixture is flushed over the surface of the reaction mixture in the flask. The flask content is on at startup, a temperature of 86 ⁰ C, the temperature rises to 77 minutes 98 ⁰ C and falls after a further 22 minutes 9O ⁰ C. At this point the reaction is terminated. The total amount of hydrogen cyanide added to the reaction mixture is 6 ml.

The analysis shows a yield of 80 # (based on the supplied l-Dicyanocyclohexen- ^) on dinitriles, which to $ 53 from trans-l ^ -Dicyanocyelohexane and $ 45 from unknown Composed of dinitriles.

Example 91

A 50 ml three-necked round bottom flask equipped with a V-flow condenser, which is connected to a Trooke ice trap, an inlet, and a magnetic stirrer, is placed in an oil bath and flushed with dry, deoxygenated nitrogen. The flask is filled with 0.097 g (4.5 x 10 "* mol) NbOCl ₃ ,

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29.2 ml (0.3 mol) 3- * entenenitrile, 0.785 ml (3 x ΙΟ * ⁵ mol)

and 0.420 g (3 x 10 * ⁴ moles) of NitPCOC3Hg) ^ dissolved.

The contents of the flask are kept at a temperature of 78 to 83 ^° C. during the reaction. A stream of dry, deoxygenated nitrogen is bubbled through liquid hydrogen cyanide contained in a 20 ml flask which is cooled in a water bath at ambient temperature. The gas mixture obtained is flushed over the surface of the reaction mixture. The reaction is ended after one hour and 23 minutes.

Analysis by gas chromatography shows that the crude Reaction mixture contains 1.2 $ adlponitrile.

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Claims (2)

AD 4198 R June 23, 1967 JOi Claims 1 · A method for the catalytic Hydrooyanierung of an unsaturated organic compound which has at least one non-conjugated ethylenic carbon-carbon double bond and contains 2 to 20 carbon atoms, characterized in that the unsaturated compound with hydrogen cyanide in the presence of a zero-valent nickel-phosphorus, arsenic - Or -antimony complex at a temperature between -25 to 20Q ⁰ C in the presence of a zinc, cadmium, beryllium, aluminum, gallium, indium, silver, titanium, zirconium, hafnium, germanium -, tin, vandadin, niobium, scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, erbium, iron or cobalt compounds, which are in a molar ratio of 1:16 to 5051 »based on the nickel complex, is present. 2. Chemical compounds «as described above. - 102 - 109847/1843 BATH ORIGINAL