JPS6044295B2 - Olefin hydrogen cyanide addition treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for catalytically adding hydrogen cyanide to olefins.

U.S. Patent 357 to Drinkard et al.
No. 956, No. 3,655,723 and No. 3,775,461 describe a process for the hydrocyanation treatment of olefins using a cobalt compound having a cobalt valence of 0.25 to 1.75 as a catalyst.

In this catalyst, the valence of cobalt is −1 [(C, H
. O). P]. Produced by treating common cobalt compounds such as CoH with oxidizing agents such as FeCl or CoCl2, or by treating cobalt compounds in which cobalt is a complex salt with a valence of +2 or +3 with a reducing agent. . According to the present invention, an olefinically unsaturated compound having 2 to 20 carbon atoms, hydrogen cyanide, 0.0002 to 0.5 mol per mol of olefin (in the formula (a) each Y is the same or different) phenyl or phenyl substituted with lower alkyl, (
b) Each L may be the same or different, and the formula R1
(CN) (in the formula, R1 is lower alkyl),
(c) x is an integer from 0 to 2, and (d) each R is hydrogen, and the molar ratio of the promoter to cobalt compound is from 1:16 to 20.
A non-oxidizing Lewis acid promoter in an amount of: 1:1 is mixed at a temperature of -25 to 200° C. in the absence of an oxidizing agent for the cobalt compound. be done.

The method of the invention consists of mixing (1) an olefin, (2) hydrogen cyanide, (3) a monocomplexed cobalt compound, and (4) a non-oxidizing Lewis acid promoter.

The term "mixed" as used herein is used to limit the ingredients that are added and is intended to optionally include premixed ingredients.

When operating according to the invention using a monocomplexed cobalt compound in which the cobalt has a valence of -1 and a non-oxidizing Lewis acid promoter, the Drinkard
) et al. U.S. Pat.
There is no need to add an oxidizing agent as taught by No. 3,775,461. In other words, the reaction of the present invention is carried out in the absence of an oxidizing agent for the cobalt compound. The olefins to be hydrocyanated according to the present invention include olefinically unsaturated compounds/substances having 2 to 20 carbon atoms, i.e., hydrocarbons having one or two aliphatic carbon-carbon double bonds, and cyano, formyl, etc. , lower alkoxycarbonyl, lower alkylcarbonyl, and arylcarbonyl having 1 to 4 substituents at least one carbon atom away from the carbon-carbon double bond. Examples of suitable olefins are ethylene, propylene, butene-1, butene-2, isobutene, pentene-2
, hexene-2, decene-1, dodecene-2, octadecene-1, eicosene-2, butadiene-1●3, hexadiene-1/4, styrene, 3-pentenenitrile,
These include 4-pentenenitrile, 2-methyl-3-butenenitrile, 10-undecenal, methyl 10-undecenoate, 3-methyl-1-hexen-5-one, and the like. Preferred olefins are 3-pentenenitrile and 4-pentenenitrile. (1) The hydrogen cyanide addition method is carried out in the presence of hydrogen cyanide.

The amount of hydrogen cyanide used can vary within a wide range. This is because its amount does not affect the course of the reaction. In a continuous process, hydrogen cyanide is fed at such a rate that it is consumed at the same rate as it is fed.
On the other hand, a large excess of hydrogen cyanide can also be used. The hydrogen cyanide addition reaction of the present invention has the formula [(YO)3P]4-. , COHLO or [(YO)
3P〕3C0CC6R40P(0Y)2〕Here, each YN
Xl Each L and each R are as defined above.

The method is carried out using a monocomplexed cobalt compound.

Examples of typical cobalt compounds are tetrakis(triphenylphosphite)cobalt hydride, 2-(diphenoxyphosphinoxy)phenyltris(triphenylphosphite)cobalt and acetonitriletris(triphenylphosphite)cobalt hydride. It's a monster. The amount of cobalt compounds present is approximately 0.00% per mole of olefin.
It can be varied within the range of 0,002 to 0.5 mol.

Preferably the cobalt compound is about 0 per mole of olefin.
．． present in an amount of 0.01 to 0.1 mol. This cobalt compound can be produced in various ways.

The cobalt compound can be prepared by reducing a cobalt salt with a suitable reducing agent such as zinc powder or sodium borohydride in the presence of a triarylphosphite. For example, [(C6H5O)3P]4C0H can be prepared by reducing anhydrous cobalt chloride with an excess of zinc powder in a solution of triphenyl phosphite in acetonyl or 3-pentenenitrile.

Similarly, cobalt nitrate hydrate can be reduced with sodium borohydride in the presence of triarylphosphite. Phosphinoxyphenyl cobalt compounds are prepared by reacting π-cyclooctenyl-π-cycloocter 1,5-dienecobalt CO(C8Hl3) (C8Hl2) with a suitable triphenylphosphite at room temperature.

The cobaltonitrile compound is prepared by preparing π-cyclooctenyl-π-cycloocta1 in the presence of a stoichiometric amount of at least one triphenylphosphite and an excess of at least one organic nitrile in a liquid solution. - Can be produced by reducing 5-diene cobalt with hydrogen. Usually organic nitriles are used as reaction solvents. There is no need to isolate the cobalt compound before use. An example of a triphenyl phosphite suitable for use in these reactions is phenyl;04
-m- and p-tolyl; o-, m- and p-ethylphenyl; p-n-propylphenyl; m- and p-
Isopropylphenyl; 2●4-diisopropylphenyl; m- and p-tert-butylphenyl;
and triphenyl phosphite containing a mixture of these groups.

Many of the phosphites used in the preparation of these complexes are commercially available materials.

These can be prepared by reacting a suitable phenol with PCl3 in the presence of triethylamine. Phosphite production is done by KOsOlapOffOrganOphOs
phOn]SCOmpOunds. sJ. Wiley&
SOns,sN. Y. ,N. Y. (1950). Nitriles of the formula (CN) in which R1 is lower alkyl can be used to produce cobaltonitrile compounds.

Acetonitrile is a typical example. The process of the invention is carried out using a non-oxidizing Lewis acid promoter (cocatalyst).

Suitable accelerators include triarylborons as well as metals,
For example, beryllium, zinc, cadmium, aluminum, gallium, indium, scandium, titanium, zirconium, hafium, vanadium, niobium, chromium,
Includes molybdenum, tungsten, manganese, iron, copper, germanium, tin, lead, and rare earth cations. Preferred promoters are triarylborons as well as metals in the cationic form: beryllium (■), zinc (■), cadmium (■), aluminum (■), gallium (■), indium (■), scandium (■) , titanium (■),
Zirconium (■), Hafnium (■), Vanadium (
■), Niobium (■), Chromium (■), Molybdenum (■)
, tungsten (■), manganese (■), iron (■), copper (■), germanium (■), tin (■), and lead (
■). Examples of typical r 2 promoters of this type are salts of the metals mentioned above, where the anions are fluorine, chlorine, bromine, iodine, cyanide and acetic acid ions. Particularly preferred accelerators are triphenylboron, SnCl. , Sn
Br2, ZnCl. , ZnBr2, FeCl2, FeB
r2, FeI2, ,A]Cl3 and AlBr3. The Lewis acid promoter can be used in an amount where the molar ratio of promoter to cobalt compound is about 1:16 to 20:1. Preferably, the amount of Lewis acid used is a molar ratio of promoter to cobalt compound of about 1:5 to 10:1. The reaction mixture also contains up to 95% by weight of the formula (YO), based on the total reaction mixture.
) Additional phosphite ligands of 3P can be included beyond those present in the cobalt compound.

Preferably, this ligand is the same as the ligand in the cobalt complex. The reaction time of the present invention is not critical.
When the reactants are combined, at least some amount of the hydrogen cyanide addition product is almost immediately formed. To obtain optimum yields in batch operations, it is preferred to continue the reaction for several minutes to about two servings or longer after the last reaction component is added. Pressure is not critical in the reactions of this invention.

Pressures higher than atmospheric pressure and thus lower pressures can be employed. It is preferable to carry out the operation at the autogenous pressure that occurs when the reaction is carried out in a closed system. There is no need to add diluent or reaction medium in this method.

For example, when the addition of a diluent is desired to promote miscibility of the reaction components, the diluent must be inert to the reaction components and the product. Examples of suitable diluents are:
liquid hydrocarbons such as hexane, benzene, and toluene; ethers such as diethyl ether and tetrahydrofuran; saturated aliphatic and aromatic nitriles,
For example, acetonitrile, benzonitrile, etc.
The process of the invention is particularly suitable for the production of adiponilyle by hydrocyanation of 3-pentenenitrile, 4-pentenenitrile, or mixtures thereof.

In a most preferred embodiment, 3-pentenenitrile is
Mix with hydrogen cyanide, tetrakis(triphenylphosphite) cobalt hydride, triphenylphosphite and chloride or bromide of zinc, iron or aluminum for hydrocyanation treatment. The nitrile products of this invention are widely useful, as is well known to those skilled in the art.

The resulting nitriles can also be reduced to amines of known utility. The preferred product, adiponitrile, can be hydrogenated to hexamethylene diamine or hydrolyzed to adipic acid, and these products are valuable intermediates in the production of nylon. The following examples illustrate the preparation of cobalt complexes and their use in the hydrocyanation of various olefins.

The present invention is not limited to these examples. All percentages are by weight. All temperatures are in degrees Celsius unless otherwise noted. Cobalt Complex Examples A and B illustrate the preparation of cobalt complexes.

These complexes were prepared using appropriate techniques that protect the reaction mixture and product from contact with air. A nitrogen-filled glovebox was used in these examples. Example A Preparation of [(C6FI5O)3P]4C0H Into a Sanro glass flask equipped with a nitrogen gas inlet, a water-cooled reflux condenser and a mechanical stirrer was added 14.5 V (0.05 mol) of cobalt nitrate hexahydrate and 400 ml of cobalt nitrate hexahydrate. I added 3 tritrils of cesetoni.

This salt was dissolved and 75y (0.25 mol) of triphenylphosphite was added. Keep solution at room temperature, 3.0
y (0.082 mol) of sodium borohydride was added in small portions over about 2 hours. A yellow precipitate formed.
The precipitate was collected, washed with methanol, dried, and redissolved in 200 ml of methylene chloride from the filter to remove inorganic salts. A solution of cobalt tetrakis(triphenylphosphite) hydride in methylene chloride was concentrated under reduced pressure to 75 ml and then 300 ml of pentane was added. A yellow solid product was collected, washed with pentane and dried. This structure was confirmed by 1H nuclear magnetic resonance (NMR) spectroscopy. Example B [(C6H5O)3P]3C0C6H40P(0C6H
5) 2 starting materials π-cyclooctenyl-π-cyclooctet-15-dienecobalt CO(C8Hl3) (
C8Hl.

), 0tsuka and ROssi, ノJOnrNC
hm. SOc. , 1968A, page 12630. 13y triphenylphosphite (a) in 20ml of benzene. 042
mol) of 3.6y(:riCO(C8Hl.

) (C8Hl3) (a). 013 mol) was added. The resulting solution was left at room temperature overnight. The benzene was evaporated under reduced pressure and the residue was triturated with hexane. The hexane was evaporated and the crude solid product was collected and washed with hexane. Recrystallization from acetone gave a 7.0y pale yellow solid, melting point about 190-195 (decomposed). Analysis C72H
59 Ol.

Calculated value for P4CO: Cl66.57:Hl4.5
8; COl4.54 Actual value: Cl66.38; Hl4.
83; COl 4.59lH and 31P nmr spectra show three normally coordinated triphenylphosphite units bonded to the cobalt atom and in the usual way via the phosphorus atom and to one ortho position of the triphenylphosphite phenyl ring. This is consistent with a structure having one triphenylphosphite unit bonded to a cobalt atom by a cobalt-to-carbon bond.

The bond to cobalt then replaces one of the bonds to the hydrogen in the ortho position of the triphenylphosphite ligand. It is thought that this cobalt compound has this structure.

This coupling method is based on G. W. ParshallAccOu
ntsOfChemicalResearch. ．． V.O.
l. 3, 139 (1970). Example C))〈○×-℃) Production of 3P (3C0HCH3CN 40
7.5y triotolyl phosphite (a) in m1 acetonitrile. 2. Prepare a solution of 0.02 mol).
0y (0.00725 mol) of CO(C8Hl.

) (C8Hl3) was dissolved in this solution. 50pSig
(3.5kg/d gauge) 4. After stirring for a while, the pressure was released and the solution was cooled to -35°C.

The yellow solid was collected, washed with acetonitrile, and dried (
7.8y). Recrystallization of a 1.0y sample from benzene-acetonitrile yields a 0.87y yellow solid, melting point (
(evacuated capillary) 140-145 (decomposition) were obtained.

Analysis Example D for C65H67O9P3NCO Preparation of [(C6H5O)3P]3C0HCH3CN 8m
1.34y triphenylphosphite (a) in acetonitrile of t. 0043 mol) in 2 ml of tetrahydrofuran at 0.40 V(7)CO(C8Hl
2) Combined with a solution of (C8Hl3) in a pressure bottle.

The bottle was evacuated and filled with 50 pSig (3.5k9/d gauge) hydrogen. Within 4 minutes at room temperature, most of the initial red color disappeared and a yellow solid formed. After the bottle was stirred at 0°C under a hydrogen pressure of 50 psjg (3.5 kg/Clt gauge), the hydrogen was released. The solid was collected, washed with acetonitrile, and dried to yield 1.1 q of yellow powder; melting point (evacuated capillary) approximately 145°C (
decomposition), 220M of C6D6-tetramethylsilane solution
HznIT1r: quartet (J53), region above 22.1 ppm tetramethylsilane. 36 in benzene solution
．． 43M pressure 31P-Nmlr; 1 broad peak 144
ppm is the area below external 85% H3PO4. infrared(
Mineral oil) is 2280c! The nitrile placed at n-1 is shown. Analysis L3COHCH3CN. ．． C56H49NO9
This yield for P3CO could be satisfactorily recrystallized from benzene solution by adding acetonitrile. Hydrocyanation of Olefins The following examples were carried out using the cobalt complexes prepared in Examples AD.

Examples 1-9 Hydrocyanation of 3-pentenenitrile Hydrogen cyanide (HCN) was carefully fractionally distilled to remove impurities and stabilizers and then mixed with distilled 3-pentenenitrile (3PN) under a nitrogen atmosphere. hand? A solution was prepared.

The resulting solution was stored in glass pins with rubber septum caps at approximately 5 oz. 2m1 sealed with rubber bulkhead
The hydrogen cyanide addition reaction was carried out in an ampoule.

In each ampoule, in a nitrogen-filled glove box, add catalyst A [(C6H5O)3P]4C0H1, the promoter shown in Table 1, the phosphite ligand shown in Table 1, and 3PN.
I put it in. A sample of the HCN/3PN solution was added via syringe and the ampoule was heated as shown in Table 1. Additional HCN
/3PN solution was added as shown in Table 1 and the mixture was heated again.

The product was then taken out with a syringe and analyzed by gas chromatography with the addition of an internal standard. 60/80
Mesh Gas-Chromium (Gas-ChrOm)Q3
3.18 filled with % ECNSS-M? A x3.05 m column was used.

[Applied Science Lab Ora
tOry. sIn. ”), Pennsylvania. Bucking from the State COlle?]. Computer analysis of the output from the flame ionization detector converted the area to weight percent at the appropriate retention time. More than one amount of HCN/ When the 3PN solution and times were as shown in Table I, the HCN/3PN solution was added at the beginning of each time period and the analysis was performed at the end of the last period.

Triphenylboron, a white crystalline solid, was used as purchased. Zinc salt and tin salt are 10% before use.
Vacuum drying was performed at 0°. Zinc, tin and boron compounds were usually dissolved in the 3PN before addition of other ingredients. The details and the results obtained are shown in Table I. Examples 10-12 Catalyst B [(C,H,O).

P]3C0C6H. 0P (0C6H5). The operations of Examples 1 to ε9 were repeated except that ε9 was used as the cobalt complex. Details and data are shown in Table ■. Examples 13-2
3 These examples are based on catalyst A [(C.

H, O)3P]. Examples 1 to 9 using accelerators such as COH
It was carried out according to the procedure. The ferrous bromide and ferrous iodide used in these examples were nominally anhydrous commercial samples. 80/100 mesh gas-chrome Q
3.18-×1.83 packed with 5% ECNSS-M
wL, (Applied Science Laboratories) was used for gas chromatography analysis.

A thermal conductivity detector was used. Table 1 shows the peak heights (Tnm) at appropriate retention times for 2-methylglutaronitrile (MGN) and adiponitrile (ADN). Using these conditions, a 1% solution of ADN or MGN will give a peak height equal to about 25-5'. Details and data are shown in Table ■. The peak at the retention time of ethylsuccinonitrile is not listed in the table, but is generally about 10 times the peak height of MGN.
Present in ~50%. Example 24 0.13q of catalyst B [(C6H5O)3P]3C0C6
H40P(0C6H5)2, 0.5m103[)Nl2
3m9 ZrlBr2, 100Pe (C6H5O)3
Examples 13-23 were repeated using P1 and 50Pe(7)HCN/3PN solutions.

The reaction time was 17 hours for 100 runs. The peak height was 1gTf0f11 for MGN and 16gTf0f11 for ADN. Example 25 Hydrocyanation of 4-pentenenitrile 0.13 g of catalyst B [(C6H5O)3P]3C0C6H40P(0
C6H5)2, 0.50 ml of 4-pentenenitrile (
4PN), 10 mg Zncl2, 60Pe (C6H
5O)3P and about 11M(7)H in acetonitrile
Examples 13-23 were repeated using 50 μ' of CN solution.

Reaction time was approximately 17 hours with heating from an 800°C oil bath. The peak height is 61TWL1 and A for MGN.
957077 for DN! It was hot. Example 26-2
8 Cobalt catalyst shown, 0.20 mt of 4PN1 about 10 m
9 ZnCl.

, 0.25 mt of the indicated ligand and 35 μe of an approximately 11 M (7) HCN solution in CH3CN.
-23 operations were repeated. This mixture was warmed in an 800 °C oil bath overnight. Details are shown in Table ■. Example 29 0.13y of [(C6H5O),P]4C0H160P
e's (C6Fl5O)3P10.5mt's 4PN1 approx. 1
Examples 13-2 using 0 nLt(7)ZnCl2 and about 11M(7)HCN5Opl in acetonitrile
The operation in step 3 was repeated.

This mixture was warmed in 100 oil for 2 hours. Vapor phase chromatography analysis showed a peak at 72= for MGN and a peak at 155 Tnm for ADN. Examples 30-31 Hydrocyanation of butadiene Using a glove box filled with nitrogen, 0.1
0y of cobalt compound and 0.015g of ZnCl.

and 5 ml of a solution containing tetrahydrofuran in an approximately 20 ml glass pressure bottle. Then about 7 moles, or about 35
0 m9 of butadiene was condensed in. To this mixture of 00 and 50Pe(7) HCN/tetrahydrofuran solution (
Approximately 8 M) was added via syringe. Then this bottle is 75
) in an oil bath overnight. Cool the bottle to room temperature and
If pressure was present, it was released. Terephthalic acid end-linked polyethylene ether glycol [molecular weight 200
0014% J8O/100 mesh Chromasorb (
3.18 of ChrOmasOrb)W]? ×6.10m
．． The remaining liquid was analyzed by gas chromatography in the same manner as in Examples 1 to 9, except that the column was used.

Chromasorb W is a product of JOhns-ManviIIeCOrp. The results of vapor phase chromatography analysis of the residual liquid are summarized in Table 3. In some cases not shown in Table 1, small amounts of 2-methyl-2-butenenitrile and 2-methyl-3-butenenitrile were produced. Example 32 1-hexene hydrogen cyanide addition using a glove box filled with nitrogen to 0.209
of [(C6ll5O)3P]4C0H125mg of Zn
cl2, 0.50 ml of (C6ll5O)3P and 0
．． 50 mL of 1-hexene was placed in a small serum ampoule.

The sealed ampoule was then placed in a fumeh hood.
11M in 50μ' acetonitrile
(7) Added with a hypodermic syringe of HCN solution. (HCN was available purified; acetonitrile was a nominally anhydrous commercial material). The ampoule was then heated in a 120° oil bath for 17 hours. Samples were collected and subjected to gas chromatography and mass spectrometry analysis. Vapor phase chromatography and mass spectrometry showed the presence of C7 nitrile. Example 33 Addition of hydrogen cyanide to styrene 0.13y [(C6H5O)3P]4C0H,. 0.
50ml of (C6H5O)3P1 about 10mg of ZnCl
.

and 0.25 mt tert-butylpyrocatechol stabilized styrene mixture was prepared. 50 Pe of an approximately 11 M (7) HCN solution in CH3CN was added and the mixture was warmed in an 801 oil bath overnight. Its presence was shown by vapor phase chromatography analysis. This material was also observed when the same mixture was heated in a 1000 °C oil bath overnight.
Example 34 Continuous addition of HCN 0.65y [(C6H5O)3P]4C0HN0.3
0WL1, (C6H5O)3P12.50m1 (7)
A mixture of 3PN and 65 mg ZnCl2 was placed in a small flask fitted with a rubber septum to keep the air out.

The flask was transferred from the nitrogen-filled glove box to a fume hood where it was heated in an 80°C oil bath. This mixture was stirred with a magnetic stirrer. A solution of about 100% HCN in 3PN was added continuously via syringe at a rate of about 5 μ'/hour.

When this product was analyzed as in Examples 13-23, M
13077L peak and AD in time relative to GN
300 in time for N. The peak of garlic was shown. The summary of the present invention is as follows.

Olefinically unsaturated compound having 2 to 20 carbon atoms, hydrogen cyanide, 0.0002 to 0.5 mol per mol of olefin of the formula [(YO)3P]4-XCOHLO or (in the formula (a) each Y is the same) (b) each L may be the same or different and has the formula R(CN) ( (C) x is an integer from O to 2, and (d) each R is hydrogen.

a monocomplexed cobalt compound, and the molar ratio of the promoter to the cobalt compound is from 1:16 to 20.
A method for the hydrocyanation treatment of unsaturated compounds, characterized in that an amount of a non-oxidizing Lewis acid promoter of 1:1 is mixed at -25 DEG to 200 DEG C. in the absence of an oxidizing agent for the cobalt compound.

Non-oxidizing Lewis acid promoters include triarylboron as well as the cationic forms of beryllium (■), zinc (■), cadmium (■), aluminum (■), gallium (■), indium (■), and scandium (■). ), titanium (■),
Zirconium (■), Hafnium (■), Vanadium (
■), Niobium (■), Chromium (■), Molybdenum (■)
, tungsten (■), manganese (■), iron (■), copper (1), germanium (■), tin (■) and lead (■
) The above method 1 is selected from the group consisting of:

The above method 2, wherein the 3-olefinically unsaturated compound is 3-pentenenitrile or 4-pentenenitrile.

4. The method of 3 above, wherein the mixture contains 0.01 to 0.1 mole of cobalt compound per mole of olefin.

5 Lewis acid promoter has a molar ratio of promoter to cobalt compound of 1
: 5 to 10:1.

6. The method of claim 5, wherein the mixture contains an additional phosphite ligand of the formula in excess of the ligand present in the cobalt compound in an amount of up to 95% by weight based on the total reaction mixture.

l The non-oxidizing Lewis acid promoter is triphenylboron, Sn
cl2, SrlBr2, Zncl2, ZrlBr2, F
eCl.

, FeBr2, FeI2, AlCl3 and AlBr3
The above 6 methods are selected from the group consisting of. 7. The method of 7 above, wherein the cobalt compound is of the formula.

] The method of 8 above, wherein the cobalt compound is tetrakis(triphenylphosphite)cobalt hydride.

10. The method of 9 above, wherein the additional phosphite ligand is triphenylphosphite.

1. The method according to 10 above, wherein the Lewis acid promoter is a chloride or bromide of zinc, iron or aluminum.

Claims (1)

[Scope of Claims] 1. Olefinically unsaturated compound having 2 to 20 carbon atoms, hydrogen cyanide, 0.0002 to 0.5 per mole of olefin.
Mole formula [(YO)_3P]_4_-_xCoHL_x
or [(YO)_3P]_3Co[C_6R_4OP
(OY)_2] (wherein (a) each Y may be the same or different and is phenyl or phenyl substituted with a lower alkyl group, and (b) each L is the same and may be different, and is a ligand of the formula R^1(CN) (wherein R^1 is lower alkyl), and (c) x is 0
and (d) each R is hydrogen) and the molar ratio of the promoter to the cobalt compound is from 1:16 to 20.
A method for the hydrocyanation treatment of unsaturated compounds, characterized in that an amount of a non-oxidizing Lewis acid promoter of 1:1 is mixed at -25 to 200°C in the absence of an oxide to a cobalt compound.