Hydration of nitriles to amides using cupreous catalysts
.[.Aliphatic nitriles.]. .Iadd.Olefinic nitriles of three to six carbon atoms .Iaddend.are converted to the corresponding amides by contacting the nitrile in the presence of water with a cupreous catalyst containing copper prepared by reducing copper hydroxide or a copper salt.
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Examples 1-11 -- Using Salts Reduced with Hydrogen
A number of copper catalysts were prepared by heating about 20 g. of a copper salt in a 640 cc./min. flow of a gaseous hydrogen stream containing 20 percent hydrogen in nitrogen for four hours. The catalysts were tested for catalytic activity by loading one gram of the catalyst in a glass ampoule and adding 5 cc. of a 7 percent acrylontrile-in-water solution. The ampoule was sealed and heated to the temperature specified for one hour. After the reaction, the ampoule was cooled and the contents were analyzed by vapor phase chromatography. The results of these experiments are shown in Table I. No by-products were observed. The indicated conversions and yields are based on acrylonitrile consumed.
TABLE I
______________________________________
HYDRATION OF ACRYLONITRILE TO ACRYL-
AMIDE USING COPPER CATALYSTS PREPARED BY
REDUCING COPPER SALTS WITH HYDROGEN
Reduc-
Copper tion Hydration, percent
salt temp. 80.degree. C.
130.degree. C.
Example:
reduced .degree.C.
Conv. Yield Conv. Yield
______________________________________
1 Cu(NO.sub.3).sub.2
175 7 0 34 1.1
2 Cu(NO.sub.3).sub.3
275 7 100 59 85
3 Cu.sub.2 CrO.sub.4
275 46 0 36 2.7
4 Cu(Ac).sub.2
275 21 21 48 38
.[.5 CuCl.sub.2
300 38 0 38 0.3
6 CuCl 300 41 0 45 3.6
7 CuBr 300 18 0 17 1.4
8 CuSO.sub.4
300 3 0 4 3.].
9 CuCO.sub.3
175 74 97 (3) (3)
10 CuC.sub.7 O.sub.4
175 16 90 (3) (3)
11 Cu--Cr.sup.3
175 62 95 (3) (3)
______________________________________
(3) No data
2 Carbonate.
Examples 12-16 -- Reduction of Copper Salts with NaBH.sub.4
Various copper salts were treated with 200 cc. of a 0.5 molar solution of NaBH.sub.4 in water for one hour at 25.degree. C. These catalysts were tested as shown in the examples above, and the results are shown in Table II. No by-products were detected in the product.
TABLE II Hydration of Acrylonitrile to Acrylamide using Copper Catalysts Prepared by Reducing Copper Salts with NaBH.sub.4 ______________________________________
Copper Salt Hydration at 100.degree. C. for 1 hr.
Ex. Reduced Conversion Yield
______________________________________
12 Cu(NO.sub.3).sub.2
98.9 90.5
13 Cu(C.sub.2 H.sub.3 O.sub.3).sub.3
100 86.6
14 CuCrO.sub.4 *
9.9 28.6
15 CuC.sub.2 O.sub.4
100 91.6
16 Copper Tartrate
51.6 80.1
______________________________________
*0.25 g. of catalyst employed rather than 1 g.
Example 17 -- Reduction of CuCl.sub.2 with Zn
To prepare a Urushibara-A copper catalyst, zinc was added to an aqueous solution of cupric chloride to precipitate metallic copper. After the evolution of gas had ceased, the product was leached with acetic acid to form the desired catalyst. Using the same procedure as shown in Example 1, 0.51 g. of the catalyst was used to hydrate acrylonitrile to acrylamide at 75.degree. C. for one hour. The conversion of the nitrile was 16 percent with a 55.2 percent yield of the amide. No by-products were observed.
Example 18 -- Reduction of Copper Nitrate with Hydrazine
Copper nitrate was reduced to copper metal by contacting 0.1 mole of Cu(NO.sub.3).sub.2 in 100 cc. of water with 200 cc. of 0.1 molar aqueous hydrazine over a one hour period at 25.degree. C. One gram of the copper catalyst prepared was reacted with 5 cc. of a 7 percent aqueous acrylonitrile solution at 100.degree. C. for one hour. The acrylonitrile was 11.2 percent converted to give a 9.8 percent yield of acrylamide. No by-products were detected.
In the same manner as described above, other copper salts are reduced to obtain desirable copper catalysts. For example, a solution of cupric nitrate is reduced with metallic zinc to give a desirable copper catalyst that is employed in the conversion of acrylonitrile to acrylamide.[.,.]. .Iadd.or .Iaddend.methacrylonitrile to methacrylamide .[.or pentanonitrile to pentanoamide..]..Iadd..
Claims
1. In the process for converting an.[.aliphatic nitrile.]..Iadd.olefinic nitrile of 3 to 6 carbon atoms.Iaddend.to the corresponding amide by reacting the nitrile with water in the presence of a catalyst, the improvement comprising conducting the reaction in the presence of a catalytic amount of copper prepared by reducing copper hydroxide or a copper salt.
2. The process of claim 1 wherein the catalyst is obtained from copper hydroxide or a copper salt having an anion containing nitrogen, sulfur or an organic carboxylic acid.
3. The process of claim 1 wherein the catalyst is obtained from copper nitrate, copper acetate, copper carbonate, copper oxalate, copper sulfide, copper chloride or copper hydroxide.
4. The process of claim 1 wherein the catalyst is obtained from copper nitrate, copper acetate or copper oxalate.
5. The process of claim 1 wherein the catalyst is prepared by a hydrogen reduction.Iadd.of copper nitrate, copper acetate, copper carbonate, copper hydroxide or copper oxalate.Iaddend.at a temperature of about 50.degree. to about 500.degree. C.
6. The process of claim 5 wherein the temperature is about 150.degree. to about 350.degree. C.
7. The process of claim 1 wherein the copper hydroxide or copper salt is reduced with NaBH.sub.4 or hydrazine in the liquid phase.
8. The process of claim 1 wherein the reducing agent is an active metal..[.9. The process of claim 1 wherein the nitrile is an olefinic nitrile of
three to six cabron atoms..]. 10. The process of claim 1 wherein the nitrile is acrylonitrile.
| 3381034 | April 1968 | Greene |
| 3499879 | March 1970 | Kobayashi |
| 3631104 | December 1971 | Habermann et al. |
| 4056565 | November 1, 1977 | Matsuda |
| 753365 | December 1970 | BEX |
| 24696 | June 1970 | CLX |
| 552987 | June 1932 | DE2 |
| 551869 | July 1932 | DE2 |
| 2036126 | February 1971 | DEX |
| 43-22851 | October 1968 | JPX |
| 44-5205 | March 1969 | JPX |
| 45-21295 | July 1970 | JPX |
- Watanabe et al., Bull. Chem. Soc. Japan 40 (1967) pp. 1660-1665. Watanabe Bull. Chem. Soc. Japan 32 (1959) pp. 1280-1282. Watanabe Bull. Chem. Soc. Japan 37 (1964) p. 1327. Watanabe Bull. Chem. Soc. Japan 39 (1966) pp. 8-14.
Type: Grant
Filed: Feb 26, 1981
Date of Patent: Aug 23, 1983
Assignee: The Dow Chemical Co. (Midland, MI)
Inventors: Clarence E. Habermann (Midland, MI), Ben A. Tefertiller (Midland, MI)
Primary Examiner: Arthur P. Demers
Attorney: Charles J. Enright
Application Number: 6/238,395
International Classification: C07C10300;
