HYDROCYANATION OF ACTIVATED OLEFINS

Abstract: Nitriles are prepared by contacting an activated olefin, with gaseous hydrogen cyanide in the presence of a catalyst containing an element selected from the group consisting of Group IA and IIA. In this way for example high yields of cyanoesters may be obtained by contacting alpha, beta-­ unsaturated alkyl acrylates, such as methyl acrylate with gaseous hydrogen cyanide in the presence of a catalyst containing an alkali metal.

Description: HYDROCYANATION OF ACTIVATED OLEFINS This invention relates to a novel process for the catalytic addition of gaseous hydrogen cyanide to activated olefins. There are several known methods for hydrocyanating unactivated olefins in the vapor phase. Teter, U.S. Patent 2,385,741, describes the addition of hydrogen cyanide to unactivated olefins in the presence of a finelydivided metallic cobalt catalyst. Darvis, U.S. Patents 3,278,575 and 3,278,576,discloses that finely-divided metallic nickel or palladium can also be employed to catalyze the addition of hydrogen cyanide to unactivated olefins. The highest yield of organic nitriles obtained by any of these processes is 42. Furthermore, it is also known in the prior art, i.e. Cordar U.S. Patent 2,904,581, that organic nitriles can be prepared from activated olefins. Activated olefins are hydrocarbons which contain an activating group in close proximity to an olefinic carbon atom. Preferably, this activating group is adjacent to an olefinic carbon. Yields as high as 805S have been obtained by this process. Unfortunately, this is a liquid phase process and both hydrogen cyanide and the activated olefin tend to polymerize at the disclosed reaction conditions. Also, it is very difficult to separate the homogeneous catalyst from the reaction product. The inventive process results in much higher yields of organic nitriles than the prior art vapor phase processes. Furthermore, these higher yields are accomplished at substantially lower temperatures. Finally, since the process of the invention is conducted in the vapor phase the hydrogen cyanide and activated olefin polymerization problem is eliminated. It has now been found that nitriles can be produced by contacting an activated olefin with gaseous hydrogen cyanide in the presence of a catalyst containing at least one element selected from the group consisting of Group IA and IIA of the Periodic Table. In a particular embodiment of the invention alpha, beta-unsaturated alkyl acrylates are contacted with gaseous hydrogen cyanide in the presence of a catalyst containing an alkali metal to produce high yields of cyanoesters. According to the present invention, nitriles are produced by the catalytic addition of hydrogen cyanide to activate olefins. The overall reaction taking place in this process is represented by the following equation: EMI2.1 wherein R1, R2, R3 and X are defined below. Nitriles are well known organic chemicals having a wide variety of uses as solvents and the like. They are also important intermediates for the preparation of a broad spectrum of organic chemicals as described, for example, in the text "The Chemistry of Organic Cyanogen Compounds" by V. Migridichian, American Chemical Society Monograph No. 105, Reinhold Publishing Company (New York, 1947). Reactants The preferred activated olefins which can be employed in this invention are compounds of the general formula: EMI3.1 wherein R1, R1 and R3 are each independently selected from the group consisting of: (1) hydrogen; (2) C14 alkyl; (3) aromatic hydrocarbon radical; (4) alicyclic hydrocarbon radical; (5) aralkyl hydrocarbon radical; EMI3.2 wherein R4 is hydrogen or a C14 alkyl and n is O to 4; and EMI3.3 wherein R5 is hydrogen or a C1-4 alkyl and s is 0 to 4; and wherein X is selected from the group consisting of: EMI3.4 wherein R6 is hydrogen or a C1-12 alkyl and t is O to 2; (2) -(CH2)u-CN, wherein u is O or 1; and EMI3.5 afherein R7 is hydrogen or a C 1-12 radical and v is O to 2. Examples of these activated olefin include acrolein, methacrolein, acrylonitrile, methacrylonitrile, methyl acrylate and ethyl acrylate. Preferably, R1, R2 and R3 are each independently selected from: (1) hydrogen; (2) C14 alkyl; and X is selected from the group consisting of EMI4.1 wherein R6 is H or C14 alkyl; (2) -CN; EMI4.2 wherein R7 is H or C14 alkyl. More preferably, the olefinically unsaturated compounds comprise compounds wherein R1, R2 and R3 are each independently selected from hydrogen and methyl and wherein X is EMI4.3 and EMI4.4 The activated olefin is contacted with gaseous hydrogen cyanide to produce the cyanoester. The ratio - of the olefin to hydrogen cyanide is not critical. The instant reaction will proceed with either excess olefin or excess hydrogen cyanide. However, the use of excess activated olefin is preferred, since this minimizes the loss of HCN. Accordingly, it is preferred to employ a molar ratio of activated olefin to HCN of greater than one and preferably between one to ten, in particular from one to two. If desired, a carrier gas which is inert to the reactants, products and catalysts can be included in the reaction system. Thus, gases such as nitrogen, the noble gases, lower alkanes, carbon monoxide, carbon dioxide, ammonia and minor amounts of hydrogen sulfide can be added to the reaction system. Process Conditions In carrying out the inventive process, the activated olefin and hydrogen cyanide in the vapor phase are contacted with a catalyst as described below. This process is preferably conducted on a continuous basis but it can also be accomplished in a batch mode. Either fixed and fluid catalyst beds can be used. The reaction temperature is normally maintained between 400C and 3500C, preferably 1500C to 3000 C. The reaction pressure is normally maintained at O to 7 kg/cm2 (100 psi), preferably 0.7 kg/cmê to 2;8 kg/cmê (10 to 40 psi). When the process is carried out in the continuous basis, the contact time is normally ten seconds to ten minutes, preferably 10 seconds to 5 minutes. When the reaction is carried out in a batch mode, reactants and catalysts are contacted with one another for a period of 10 minutes to 6 hours, preferably 1 hour to 4 hours. A reaction time of less than 10 minutes or more than 6 hours can be used if desired, although better results will be obtained if the reaction time is maintained within this range. Catalyst The heterogeneous catalyst employed in this process comprises at least one element selected from the group consisting of Group IA and IIA of the Periodic Table or a mixture of elements from each Periodic Table. Preferred catalysts comprise at least one of K, Li, Cs, Ca, Ba and Mg. Especially preferred catalysts contain at least one of K, Li and Cs. This catalyst can be promoted with a wide variety of metals selected from groups VIB, VIIB, VIII and IB. Preferred promoters include Ru, Cr, Mn, Cu, Ni and Ti. The catalyst used according to the present invention is primarily a compound of a metal capable of withstanding the temperatures employed. These various metal compounds include oxides, hydroxides, and various salts, e.g. ferrocyanides, phophates, carbonates, silicates, aluminates, cyanides and salts of organic acids such as the acetates, formates and butyrates. Preferred catalysts contain oxygen or oxygen-containing anions. The free metals may also be used. Compounds which are somewhat basic in nature or which at least in part react with hydrogen cyanide to form metal cyanides have been found to be particularly good. The catalyst can be prepared by methods well known in the art. For example, these catalysts can be produced by evaporating a solution of a soluble compound on an inert carrier, or mixing an aqueous slurry of an insoluble compound or of the free metal with an inert carrier, filtering, pressing, drying and calcining the filter cake, and finally grinding the filter cake to the desired particle size. The inert carriers which may be used with this catalyst include aluminates, silicates, titanates and phosphates and mixtures thereof. Preferred carriers are aluminates and silicates. Basic compounds such as quartz, diatomaceous earth, various clays and pumice may also be used. Recovery The reaction product obtained upon completion of this reaction are partially in the gas phase. This reaction product can be subjected to suitable known separation techniques to obtain the desired end product. For example, the product can be condensed to a liquid. The liquid product can then be filtered to remove catalyst therefrom and then separated into component parts by the use of solvent extraction and distillation. SPECIFIC EMBODIMENTS In order to more clearly illustrate the present invention, the following working examples are presented. In these examples, the following definition is used: Yield = Moles of Nitrile Product Formed Moles of HCN Fed Example 1 A catalyst comprising 7.6% LiOAc on a low surface area alumina was prepared as follows. First, 4.11 grams of LiOAc were dissolved in 20 grams of water. Next, 50 grams of a low surface area alumina, i.e. alumina with a surface area of less than 5 square meters per gram, were stirred into the lithium solution . This mixture was dried for 15 hours at 1250C and calcined for 16 hours at 350 C 40 cc. of the above catalyst were packed into a reactor. A furnace heated the reactor while nitrogen flowed over the catalyst bed. When the reaction temperature reached 2500C, the gas was changed to a mixture of 79 to 10% HCN in nitrogen, and the system was allowed to equilibrate for 15 minutes. Methyl acrylate was then pumped in at a rate of 10 cc. per hour. The output of the reactor was passed to a pair of dry ice cooled glass condensors, and the product was collected. The product was warmed to room temperature, weighed and analyzed. The results are shown in Table 1. Example 2 A catalyst comprising 11.2 weight percent KNO3 on a low surface area alumina was prepared as follows. First, 6.31 grams of KNO3 were dissolved in 20 grams of water. Next, 50 grams of a low surface area alumina, i.e. alumina with a surface area of less than 5 square meters per gram, were mixed with the aqueous potassium solution. This mixture was dried for 15 hours at 1250C and calcined for 5 hours at 2600C and 15 hours at 5380C. The catalyst prepared above was placed into the experimental apparatus described in Example 1. The results are shown in Table I. Examples 3, 4 and 5 Other catalysts containing Group IA or Group IIA elements were prepared by the techniques described in Example 2. These catalysts were also placed in the experimental apparatus described in Example 1 and the results are shown in Table I. Example 6 A catalyst comprising MgA1204 was prepared as follows. First, 85.47 grams of Mg(No3)2-6H20 were dissolved in water. Next, 33.99 grams of A1203 powder were slurried in water. These two aqueous solutions were mixed together and evaporated to the consistency of toothpaste. The mixture was then dried for 15 hours at 1250C and calcined 5 hours at 2600C (5000F) and 20 hours at 5380C (1,0000F). This catalyst was placed in the experimental apparatus described in Example 1 and the results are shown in Table I. Examples 7 and 8 Catalysts containing potassium were prepared by the technique described in Example 6. These catalysts were also placed in the experimental apparatus described in Example 1 and the results are shown in Table I. Example 9 A catalyst comprising 23.78 weight percent of En(CN)6 on a low surface area alumina was prepared as follows. First, 15.6 grams EMn(CN)6 were dissolved in 20 grams of water. 50 grams of a low surface area alumina were mixed with this aqueous solution. The mixture was then dried for 15 hours at 1250C and calcined for 3 hours at 3500C. This catalyst was placed in the experimental apparatus described in Example 1 and the results are shown in Table I. Example 10, 11 and 12 Other catalysts containing potassium were prepared and placed in the experimental apparatus described in Example 1. The results are shown in Table I. TABLE I Various Catalysts Useful for the Hydrocyanation of Methyl Acrylate Methyl Acrylate Feed Rate: 10 cc/hr HCN Feed Rate: 50 cc/min (7% to 10% HCN, 90% to 93% N2) Temperature: 2500 C. Pressure: Atmospheric Example Catalyst Yield (%) 1 7.60 LiOAc on LSAA 80.4 2 11.20% KN03 on LSAA 98.4 3 19.57% CsN03 on LSAA 71.5 4 22.76% Ca(N03)2 on HSAA 60.9 5 24.60% Ba(N03)2 on LSAA 64.7 6 MgAl2O4 43.3 7 K2Si205 73.2 8 S2A1204 53.8 9 23.78% EMn(CN)6 on LSAA 58.1 10 10.81% S2CrO4 on HSAA 90.6 11 12.72% K4Ru(CN)6 on HSAA 25.5 12 8.92% K2HP04 on LSAA 75.6 LSAA = Low Surface Area Alumina (approximately 5 sq. m/gm.) 2HSAA = High Surface Area Alumina (approximately 100 sq. m/gm.) Examples 13 to 18 A catalyst comprising CaA1204 was prepared as follows. First, 78.72 grams of Ca(N03)2.4E20 were dissolved in water. Also 33.99 grams of A1203 powder were slurried in water. These two aqueous solutions were mixed together and evaporated to the consistency of toothpaste. This mixture was then dried for 15 hours at 1250C and calcined for 5 hours at 2600C (5000F) and 20 hours at 5380C (1,0000F). The catalyst was then placed in the experimental apparatus described in Example 1 except that the process conditions were adjusted as shown in Table II. The results of these experiments are shown in Table II. Examples 19 to 22 Other catalysts were also tested under various process conditions. These results are shown in Table II. TABLE II Various Process Conditions for the Hydrocyanation of Methyl Acrylate (MA) HCN Feed: 7% to 10% HCN, 90% to 93% N Pressure: 1 atmosphere 2 Methyl Acrylate Flow Rate Example Catalyst Temp.( C) (cc/Hr) 13 CaA1204 175 10 14 " 200 10 15 " 225 10 16 " 250 10 17 " 275 10 18 " 200 10 19 7.60% LiOAc on LSAA 250 10 20 " 250 10 21 11.20% KNO on LSAA 250 10 3 22 11 250 2.1 HCN Flow Rate Example (cc/Min) Yield (%) 13 50 15.2 14 50 27.1 15 50 46.7 16 50 74.8 17 50 54.6 18 100 13.5 19 50 88.8 20 25 81.6 21 50 79.5 22 50 49.2 Examples 27 to 25 The catalyst and experimental apparartus shown in Example 2 were used in these examples. Three different activated olefins were tested and each of them yielded some nitrile. The results are shown in table III. TABLE III Hydrocyanation of Other Activated Olefins HCN Feed Rate: 50 cc/min (7% to 10% HCN in nitrogen) Olefin Feed Rate: 10 ml/hr Catalyst: 11.20% KNO on HSAA Temperature: 1500C Pressure: Atmospheric Example Activated Olefin Yield (%) of Nitrile 23 Acrylic Acid Approximately 1 24 Acrolein Approximately 1 25 Acrylonitrile Approximately 1

Claims: CLAIMS: .1. A process for producing nitriles comprising contacting an activated olefin with gaseous hydrogen cyanide in the presence of a catalyst containing at least one element selected from the group consisting of Groups IA and IIA of the Periodic Table. 2. A process as claimed in claim 1 characterised in that the activated olefin is represented by the following formula: EMI14.1 wherein R1, R2 and R3 are each independently selected from: (1) hydrogen; (2) C1¯4 alkyl; (3) aromatic hydrocarbon radical; (4) alicyclic hydrocarbon radical; (5) aralkyl hydrocarbon radical; EMI14.2 wherein R4 is either H or a alkyl and n is O to 4; and EMI14.3 wherein R5 is either H or a C14 alkyl and s is O to 4; and wherein X is selected from the group consisting of: EMI14.4 wherein R6 is either H or a C1-12 alkyl and t is O to 2; (2) -(CH2)U-CN, wherein u is O to 2; and EMI14.5 wherein R7 is either H or a C1-12 alkyl and v is O to 2. 3. A process as claimed in claim 2 characterised in that R1, R2 and R3 independently represent 0 -C-OR4, wherein R4 is either H or a C14 alkyl group. 4. A process as claimed in claim 2 characterised in that R1, R2 and R7 independently represent H or C14 alkyl. 5. A process as claimed in claim 4 characterised in that R1, R2 and R3 independently represent H or CH3. 6. A process as claimed in any of claims 2 to 5 characterised in that X is selected from the following: EMI15.1 wherein R6 is either H or a C14 alkyl; (2) -CN; or EMI15.2 wherein R7 is either H or a C1 alkyl 7. A process as claimed in claim 6 characterised in that X is EMI15.3 8. A process as claimed in any of claims 1 to 7 characterised in that the molar ratio of activated olefin to hydrogen cyanide is between 1:1 and 2:1. 9. A process as claimed in any of claims 1 to 8 characterised in that the catalyst is heterogeneous. 10. A process as claimed in any of claims 1 to 9 characterised in that the reaction is carried out at a temperature between 1500C and 3000 C. 11. A process as claimed in any of claims 1 to 10 characterised in that the reaction is carried out at a pressure of from 0.7 kg/cm2 (10 psi) and 2.8 kg/cm2 (40 psi). 12. A process as claimed in any of claims 1 to 11 characterised in that the catalyst comprises a mixture of Group IA and Group IIA elements, 13. A process as claimed in any of claims 1 to 12 characterised in that the catalyst comprises at least one of the following metals: Li, Na, K, Rb, Cs, Mg, Ca, Sn and Ba. 14. A process as claimed in any of claims 1 to 13 characterised in that the catalyst is supported on an inert carrier. 15. A process as claimed in claim 14 characterised in that the carrier is alumina, silica or alumina silicate. 16. A process as claimed in any of claims 1 to 15 characterised in that a cyanoester is produced. 17. A process for producing a cyanoester comprising contacting an alpha, beta-unsaturated alkyl acrylate with gaseous hydrogen cyanide in the presence of a catalyst containing an alkali metal component.

Inventors: GRAHAM, ANNE MARIE, PESA, FREDERICK ANTHONY
Applicants: THE STANDARD OIL COMPANY
Application year: 1980
Main classification: C07C120
IPC codes: B01J23