Amines and amides are N,N-cyclodialkylated by reaction with an unstrained cyclic ether in the presence of a b-subgroup metal oxide alkylation catalyst, preferably a group IV-b metal oxide such as titanium dioxide.
|
1. The process of converting an N,N-dialkylatable amino or amido group into an N,N-cyclodialkylated amino or amido group which comprises reacting a compound containing at least one N,N-dialkylatable amino or amido group with an unstrained cyclic ether co-reactive therewith in the presence of a viable b-subgroup metal oxide alkylation catalyst other than a group i-b metal oxide so that at least one such N,N-dialkylatable amino or amido group is transformed into an N,N-cyclodialkylated amino or amido group, respectively., such that when said group being transformed in an amino group, said cyclic ether has a furan ring system, a dihydrofuran ring system, a pyran ring system or a dihydropyran ring system.
2. A process of
at least four carbon atoms in the ring. 3. A process of claim 1 wherein said compound has at least one N,N-dialkylatable primary amino group in the molecule. 4. A process of claim 1 wherein the reaction is conducted in the vapor phase by contacting a vapor phase mixture of the reactants with a bed of the catalyst. 5. A process of claim 1 wherein the reaction is conducted in the liquid phase in the presence of the catalyst. 6. A process of claim 1 wherein the reaction is conducted at a temperature of at least about 200°C but below that at which the catalyst becomes inactive. 7. A process of claim 1 wherein the catalyst is composed predominantly or entirely of one or more oxides of one or more group IV-b metals. 8. A process of claim 7 wherein the catalyst is composed predominantly or entirely of titanium dioxide. 9. The process of converting an N,N-dialkylatable amino group into an N,N-cyclodialkylated amino group which comprises reacting a compound containing at least one N,N-dialkylatable amino group with an unstrained cyclic ether co-reactive therewith in the presence of a viable b-subgroup metal oxide alkylation catalyst other than a group i-b metal oxide at a temperature of at least about 200°C but below that at which the catalyst becomes inactive, so that at least one such N,N-dialkylatable amino group is transformed into an N,N-cyclodialkylated amino group., said cyclic ether having a furan ring system, a dihydrofuran ring system, a pyran ring system or a dihydropyran ring system. 10. A process of
system or a dihydropyran ring system. 11. A process of claim 9 wherein said compound has at least one N,N-dialkylatable primary amino group in the molecule. 12. A process of claim 11 wherein said compound is a primary aromatic amine. 13. A process of claim 12 wherein the amine is a mononuclear primary aromatic amine having one or two amino groups on one or two aromatic rings. 14. A process of claim 11 wherein said compound is a primary aliphatic amine. 15. A process of claim 14 wherein said amine is a monoalkyl amine. 16. A process of claim 9 wherein the catalyst is composed predominantly or entirely of a dioxide of one or more group IV-b metals. 17. A process of claim 16 wherein the ether is furan, a dihydrofuran, tetrahydrofuran, a mono- or polyalkyl substituted tetrahydrofuran, furfuryl alcohol, a dihydrofurfuryl alcohol, tetrahydrofurfuryl alcohol, an alkoxytetrahydrofuran, a hydroxytetrahydrofuran, furaldehyde, furfurylamine,or dihydropyran, or tetrahydropyran.. 18. A process of claim 17 wherein said compound is a primary aromatic amine or a primary aliphatic amine. 19. A process for the production of imidazolidones which comprises heating a compound containing at least one N,N-dialkylatable primary amino group with an oxazolidone in the presence of a viable catalyst consisting essentially of a dioxide of at least one group IV-b metal so that N,N-cyclodialkylation of the amino group takes place. 20. A process of claim 19 wherein said compound is a primary aromatic or aliphatic amine, said oxazolidone is 2-oxazolidone and said catalyst consists essentially of titanium dioxide. 21. A process for the production of N,N-cyclodialkylated amines which comprises reacting N,N-cyclodialkylatable primary or secondary aliphatic amine or N,N-cyclodialkylatable primary or secondary aromatic amine with an unstrained cyclic ether co-reactive therewith in the presence of a viable b-subgroup metal oxide catalyst other than a group i-b metal oxide at a temperature of at least about 200°C, but below that at which the catalyst becomes inactive, so that N,N-cyclodialkylated amine is produced. 2. A process of claim 21 wherein the amine used in the reaction is a primary alkyl amine or a primary aromatic amine, wherein the ether has but a single ring composed of a furan ring system, a dihydrofuran ring system, a tetrahydrofuran ring system, or a dihydropyran ring system and wherein the catalyst is composed predominantly or entirely of titanium dioxide or zirconium dioxide. 23. A process of claim 22 wherein the reaction is conducted in the vapor phase by contact a vapor phase mixture of the reactants with a bed of the catalyst. |
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Ti-X-L2873-23-10. Ti-X-649-84-1. It was of the anatase crystallographic form and had a surface area of 153 m2 /g.
Catalyst No. 40--ZrO2 ; Harshaw Zr-0304. It had a surface area of 46.1 m2 /g.
Catalyst No. 44--ZnO; Harshaw Zn 0701.
Catalyst No. 45--Ti2 O3 ; Cerac, Inc. T-1157. It had a surface area of 0.2 m2 /g.
Catalyst No. 56--TiO; Cerac, Inc. T-1154. It had a surface area of less than 0.1 m2 /g.
The other catalyst referred to in Table I was synthesized as reported in Example 1.
PAC Preparation of Catalyst No. 24--TiO2Titanium isopropoxide (155.15 g) was dissolved in 200 mL of isopropanol and heated to 60°C with stirring. Distilled water (42.5 mL) was added dropwise maintaining the temperature below 70°C to precipitate titania. Excess isopropanol was evaporated off under a dry nitrogen stream at 50°-60°C to give a thick paste. The paste was extruded through a 50 cc plastic syringe and air-dried overnight. The extrusions were oven-dried at 110°C for 2 hours and then calcined at 450°C overnight to give 41.7 g of finished catalyst.
| TABLE I |
| __________________________________________________________________________ |
| Alkylations Using Individual B-Subgroup Metal Oxide Catalysts |
| __________________________________________________________________________ |
| Run Number 1 2 3 4 5 6 7 8 9 10 11 |
| __________________________________________________________________________ |
| Catalyst TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| Catalyst Number |
| 21 21 22 22 36 36 36 36 24 24 24 |
| Temperature, °C. |
| 250 300 250 300 300 325 350 375 300 350 400 |
| Aniline Conversion, % |
| 54 87 69 95 59 70 71 64 38 88 68 |
| Ether Conversion, % |
| 18 45 19 61 22 35 54 72 9 60 99 |
| Product Distribution, wt. percent |
| N--et aniline |
| 64.4 |
| 38.2 |
| 51.9 |
| 16.7 |
| 63.7 |
| 52.8 |
| 51.5 |
| 51.5 |
| 82.7 |
| 50.0 |
| 22.0 |
| o-et aniline 2.6 2.0 0.9 1.4 0.7 2.3 4.9 9.8 4.1 3.5 21.1 |
| p-et aniline 4.5 1.9 3.5 3.4 0.9 1.3 1.6 2.3 4.5 1.3 9.2 |
| N,N--di-et aniline |
| 11.8 |
| 18.7 |
| 12.9 |
| 6.9 17.8 |
| 17.9 |
| 13.1 |
| 7.8 5.2 20.3 |
| 1.8 |
| 2,6-di-et aniline |
| 2.9 2.2 3.2 6.1 2.4 2.8 3.9 7.4 -- 2.6 13.8 |
| Other ring di-et anilines |
| 7.1 17.1 |
| 12.9 |
| 22.8 |
| 8.8 13.5 |
| 15.3 |
| 11.9 |
| -- 14.2 |
| 11.8 |
| Ring tri-et anilines |
| 3.3 12.4 |
| 12.2 |
| 30.4 |
| 4.0 6.1 5.1 3.4 -- 4.9 5.3 |
| Others 3.3 7.6 2.5 12.3 |
| 1.6 3.2 4.5 5.9 3.5 3.2 15.0 |
| N--alkylation, % |
| 76.2 |
| 56.9 |
| 64.8 |
| 23.6 |
| 81.5 |
| 70.7 |
| 64.6 |
| 59.3 |
| 87.9 |
| 70.3 |
| 23.8 |
| Ring alkylation, % |
| 10.0 |
| 6.1 7.6 10.9 |
| 4.0 6.4 10.5 |
| 19.5 |
| 8.6 7.4 44.1 |
| Di-, tri-, & others, % |
| 13.7 |
| 37.1 |
| 27.6 |
| 65.5 |
| 14.4 |
| 22.8 |
| 24.8 |
| 21.2 |
| 3.5 22.3 |
| 32.1 |
| Ratio of o-et to p-et |
| 0.6 1.1 0.3 0.4 0.8 1.8 3.1 4.3 0.9 2.7 2.3 |
| Gaseous products, mL/hr |
| 5 55 0 75 20 70 200 400 25 205 600 |
| __________________________________________________________________________ |
| Run Number 12 13 14 15 16 17 18 19 20 21 |
| __________________________________________________________________________ |
| Catalyst ZrO2 |
| ZrO2 |
| ZrO2 |
| ZrO2 |
| ZnO ZnO ZnO ZnO Ti2 O3 |
| Ti2 O3 |
| Catalyst Number 40 40 40 40 44 44 44 44 45 45 |
| Temperature, °C. |
| 300 325 350 375 325 350 375 400 300 325 |
| Aniline Conversion, % |
| 94 94 77 44 37 35 40 30 10 15 |
| Ether Conversion, % |
| 58 89 99.5 |
| 99.9 |
| 17 38 67 94 -- 1 |
| Product Distribution, wt. percent |
| N--et aniline 69.1 |
| 63.4 |
| 79.5 |
| 90.5 |
| 86.4 |
| 79.8 |
| 68.5 |
| 52.7 |
| 97.9 |
| 96.3 |
| o-et aniline -- 0.2 0.7 1.8 -- -- 3.9 1.1 -- -- |
| p-et aniline -- 0.2 0.4 0.7 -- 0.4 0.4 0.1 -- -- |
| N,N--di-et aniline |
| 30.4 |
| 31.1 |
| 15.3 |
| 5.7 2.1 2.2 2.5 2.1 2.1 3.1 |
| 2,6-di-et aniline |
| -- -- -- -- -- 4.0 4.0 5.5 -- -- |
| Other ring di-et anilines |
| -- -- -- -- -- 2.0 2.7 8.2 -- -- |
| Ring tri-et anilines |
| -- -- -- -- -- -- 1.2 6.8 -- -- |
| Others 0.5 5.2 4.1 1.4 11.5 |
| 11.6 |
| 16.6 |
| 23.5 |
| -- 0.6 |
| N--alkylation, % 99.5 |
| 94.5 |
| 94.8 |
| 96.2 |
| 88.5 |
| 82.0 |
| 71.0 |
| 54.8 |
| 100.0 |
| 99.4 |
| Ring alkylation, % |
| -- 0.4 1.2 2.5 -- 4.4 8.3 6.7 -- -- |
| Di-, tri-, & others, % |
| 0.5 5.2 4.1 1.4 11.5 |
| 13.6 |
| 20.5 |
| 38.5 |
| -- 0.6 |
| Ratio of o-et to p-et |
| -- 1.0 1.8 2.6 -- -- 9.8 11.0 |
| -- -- |
| Gaseous products, mL/hr |
| 320 800 1370 |
| 1570 |
| 160 340 820 1560 |
| 10 20 |
| __________________________________________________________________________ |
| Run Number 22 23 24 25 26 27 28 29 30 31* 32 |
| __________________________________________________________________________ |
| Catalyst Ti2 O3 |
| Ti2 O3 |
| TiO TiO TiO TiO TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| Catalyst Number |
| 45 45 56 56 56 56 22 22 22 22 22 |
| Temperature, C. |
| 350 375 300 350 375 400 325 350 375 375 400 |
| Aniline Conversion, % |
| 23 30 7 20 29 30 95 91 86 71 65 |
| Ether Conversion, % |
| 1.4 9 1 5 10 18 77 93 98 76 96 |
| Product Distribution, wt. percent |
| N--et aniline |
| 92.5 |
| 87.0 |
| 98.8 |
| 96.8 |
| 95.3 |
| 87.8 |
| 11.5 |
| 5.1 3.3 26.5 |
| 12.0 |
| o-et aniline -- 0.6 -- -- -- 1.1 2.4 6.1 12.0 |
| 12.2 |
| 22.9 |
| p-et-aniline -- -- -- -- -- -- 4.1 6.2 8.8 7.8 10.6 |
| N,N--di-et aniline |
| 6.0 6.3 1.2 3.2 3.6 3.1 3.1 0.6 0.3 2.5 0.6 |
| 2,6 di-et aniline |
| -- -- -- -- -- 3.4 11.7 |
| 20.4 |
| 25.7 |
| 12.1 |
| 21.5 |
| Other ring di-et anilines |
| -- -- -- -- -- 3.6 17.1 |
| 7.9 4.4 13.8 |
| 5.6 |
| Ring tri-et anilines |
| -- -- -- -- -- -- 32.4 |
| 30.3 |
| 17.8 |
| 9.3 7.7 |
| Others 1.6 6.1 -- -- 1.1 0.8 17.7 |
| 23.6 |
| 27.8 |
| 15.8 |
| 19.0 |
| N--alkylation, % |
| 98.5 |
| 93.3 |
| 100 100 98.9 |
| 90.9 |
| 14.6 |
| 5.7 3.6 29.0 |
| 12.6 |
| Ring alkylation, % |
| -- 0.6 -- -- -- 1.1 18.2 |
| 32.7 |
| 46.5 |
| 32.1 |
| 55.0 |
| Di, tri-, & others, % |
| 1.6 6.1 -- -- 1.1 7.8 67.2 |
| 61.8 |
| 50.0 |
| 38.9 |
| 32.3 |
| Ratio of o-et to p-et |
| -- -- -- -- -- -- 0.6 1.0 1.4 1.6 2.2 |
| Gaseous products, mL/hr |
| 50 50 0 15 30 70 225 315 410 670 730 |
| __________________________________________________________________________ |
| *The LHSV was 0.4 per hour |
In another group of runs the vapor phase alkylation of aniline with diethyl ether was performed in the same manner using various catalysts composed of two different metal oxides, one or both of which was a B-subgroup metal oxide. One of these mixed metal oxide catalysts was obtained from a commercial source. The others were prepared by me.
The commercial catalyst, Catalyst No. 50, was a mixed ZrO2 -TiO2 catalyst from Cerac, Inc., Z-1079. It had a surface area of less than 0.1 m2 /g.
Examples 2 through 8 describe the procedures used by me in synthesizing the mixed metal oxide catalysts.
PAC Preparation of Catalyst No. 19--TiO2 -5% MoO3155.25 Grams of titanium isopropoxide was dissolved in 200 mL of isopropanol and the solution was heated to 60°C with stirring. Distilled water (42.5 mL) was added dropwise while maintaining the temperature below 70°C to precipitate titania. Then 6.15 mL of a 10% aqueous solution of (NH4)2 MoO4 was added and excess solvent evaporated off under a dry nitrogen stream at 60°C The damp precipitate was moistened with distilled water to give a thick paste. This was extruded through a 50 cc plastic syringe. The extrusions were air-dried, then oven-dried for three hours at 110°C, and then calcined overnight at 450°C to give 43.5 g of finished catalyst.
PAC Preparation of Catalyst No. 25--TiO2 -10% MoO3A solution made from 155.25 g of titanium isopropoxide and 200 mL of isopropanol was heated to 60°C with stirring. Distilled water (42.5 mL) was added dropwise while maintaining the temperature below 70°C to precipitate titania. Then 12.3 mL of a 10% aqueous solution of (NH4)2 MoO4 was added with stirring and excess solvent evaporated off under a dry nitrogen stream at 50°-60°C to give a thick paste. This was extruded through a 50 cc plastic syringe. The extrusions were air-dried for two hours, then oven-dried overnight at 100°C, and then calcined for eight hours at 450°C to give 43.8 g of finished catalyst.
PAC Preparation of Catalyst No. 26--TiO2 -5% WO3A solution of 77.63 g of titanium isopropoxide in 100 mL of isopropanol was heated to 60°C with stirring. Distilled water (21.3 mL) was added dropwise while maintaining the temperature below 70°C to precipitate titania. Then 12.35 g of a 10% aqueous solution of (NH4)6 H2 W12 O40.xH2 O was added with stirring. Excess solvent was evaporated off under a dry nitrogen stream at 50°-60°C to give a nearly dry powder. To this was added water to give a thick paste which was extruded through a 50 cc plastic syringe. The extrusions were air-dried for four hours, then oven-dried for three hours at 100°C, and then calcined at 450°C overnight to give 22.7 g of finished catalyst.
PAC Preparation of Catalyst No. 27--TiO2 -5% Fe2 O3A solution of 77.63 g of titanium isopropoxide in 100 mL of isopropanol was heated to 60°C with stirring. Distilled water (21.3 mL) was added dropwise while maintaining the temperature below 70°C to precipitate titania. To this slurry was added 53.16 g of a 10% aqueous solution of Fe(NO3)3.9H2 O with stirring. Excess isopropanol and water were evaporated off by means of a dry nitrogen stream at 50°-60°C to give a thick paste. Extrusions of the paste through a 50 cc plastic syringe were air-dried overnight, oven dried at 100°C for four hours, and then calcined at 450° C. for four hours. This yielded 22.8 g of finished catalyst.
PAC Preparation of Catalyst No. 32--TiO2 -10% Fe2 O3The procedure of Example 5 was repeated in the same fashion except that 106.32 g of the 10% aqeuous solution of Fe(NO3)3.9H2 O was added to the titania slurry. During the stripping at 50°-60° C., the solids began to granulate and turn dark brown before all of the isopropanol has been removed. This experiment yielded 22.3 g of a dense, black finished catalyst.
PAC Preparation of Catalyst No. 35--TiO2 -20% Fe2 O3A solution of 77.63 g of titanium isopropoxide in 100 mL of isopropanol was heated to 60°C with stirring. Distilled water (21.3 mL) was added dropwise while maintaining the temperature below 70°C to precipitate titania. To this slurry was added 100 g of a 21.26 wt % aqueous solution of Fe(NO3)3.9H2 O with stirring. Excess isopropanol and water were evaporated off by means of a dry nitrogen stream at 40°-50°C to give a thin paste. Further evaporation of water was conducted at low heat with a hot plate to give a thick paste. The paste was oven-dried at 100°C overnight. The resulting large particles were crushed to less than 2 mm, then calcined at 450°C for six hours to give 26.0 g of finished catalyst.
PAC Preparation of Catalyst No. 38--TiO2 -10% Fe2 O3The procedure of Example 5 was repeated in the same manner except that 10.63 g of Fe(NO3)3.9H2 O in 50 mL of water was used. After removing the excess solvent the thick paste of the catalyst was poured onto a flat surface and air-dried, then oven-dried at 100°C overnight. Calcining at 450°C for six hours gave 23.4 g of finished catalyst.
| TABLE II |
| __________________________________________________________________________ |
| Alkylations Using Two Metal Oxides One or Both Being a B-Subgroup Metal |
| Oxide Catalyst |
| __________________________________________________________________________ |
| Run Number |
| 33 34 35 36 37 38 39 40 |
| __________________________________________________________________________ |
| Catalyst TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| 5% MoO3 |
| 5% MoO3 |
| 5% MoO3 |
| 10% MoO3 |
| 10% MoO3 |
| 10% MoO3 |
| 10% MoO3 |
| 5% WO3 |
| Catalyst Number |
| 19 19 19 25 25 25 25 26 |
| Temperature, °C. |
| 325 350 375 300 325 350 375 325 |
| Aniline 82 64 65 65 60 59 34 91 |
| Conversion, % |
| Ether 54 63 92 55 49 57 55 64 |
| Conversion, % |
| Product Distribution, wt. percent |
| N--et aniline |
| 52.0 51.9 23.5 62.6 63.7 54.5 46.6 45.3 |
| o-et aniline |
| 6.4 10.5 20.2 5.8 7.7 12.1 12.8 3.7 |
| p-et aniline |
| 2.0 3.3 7.4 2.6 3.1 4.7 5.2 2.2 |
| N,N--di-et aniline |
| 11.0 6.3 2.1 9.4 6.9 3.7 1.4 18.2 |
| 2,6-di-et aniline |
| 3.5 4.3 11.5 3.1 2.9 3.6 3.7 1.9 |
| Other ring di-et |
| 14.0 10.9 10.6 10.1 9.0 10.7 9.0 17.9 |
| anilines |
| Ring tri-et anilines |
| 3.7 2.6 4.0 1.8 1.2 1.7 2.4 6.7 |
| Others 7.4 10.2 20.8 4.5 5.5 9.0 19.0 4.2 |
| N--alkylation, % |
| 63.0 58.2 25.6 72.0 70.6 58.2 48.0 63.5 |
| Ring alkylation, % |
| 11.9 18.1 39.1 11.5 13.7 20.4 21.7 7.8 |
| Di-, tri-, & others, % |
| 25.1 23.7 35.4 16.4 15.7 21.4 30.4 28.8 |
| Ratio of o-et |
| 3.2 3.2 2.7 2.2 2.5 2.6 2.5 1.7 |
| to p-et |
| Gaseous products, |
| 160 195 550 0 0 200 370 220 |
| mL/hr |
| __________________________________________________________________________ |
| Run Number |
| 41 42 43 44** 45 46 47 48 |
| __________________________________________________________________________ |
| Catalyst TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| 5% WO3 |
| 5% Fe2 O3 |
| 5% Fe2 O3 |
| 5% Fe2 O3 |
| 10% Fe2 O3 |
| 10% Fe2 O3 |
| 10% Fe2 O3 |
| 20% Fe2 |
| O3 |
| Catalyst Number |
| 26 27 27 27 32 32 32 35 |
| Temperature, °C. |
| 350 350 375 375 300 350 375 350 |
| Aniline 89 87 78 55 13 31 33 14 |
| Conversion, % |
| Ether 89 76 83 78 13 50 69 22 |
| Conversion, % |
| Product Distribution, wt. percent |
| N--et aniline |
| 27.8 40.5 39.8 43.0 87.7 56.2 31.3 39.2 |
| o-et aniline |
| 7.7 7.7 12.0 17.9 6.4 23.4 36.4 46.6 |
| p-et aniline |
| 4.3 2.3 3.1 3.8 -- 5.5 6.2 -- |
| N,N--di-et aniline |
| 7.0 10.6 6.2 3.3 0.6 1.6 1.4 -- |
| 2,6-di-et aniline |
| 9.0 5.4 6.5 6.1 -- 3.6 4.8 2.4 |
| Other ring di-et |
| 20.3 19.7 14.1 10.5 -- 6.1 5.2 3.3 |
| anilines |
| Ring tri-et anilines |
| 12.5 5.4 3.5 1.7 -- -- 3.7 2.4 |
| Others 11.3 8.4 14.9 13.8 5.3 3.7 10.9 6.0 |
| N--alkylation, % |
| 34.8 51.1 46.0 46.3 88.3 57.8 32.7 39.2 |
| Ring alkylation, % |
| 21.0 15.4 21.6 27.8 6.4 32.5 47.4 49.0 |
| Di-, tri-, & others, % |
| 44.1 33.5 32.5 26.0 5.3 9.8 19.8 11.7 |
| Ratio of o-et |
| 1.8 3.4 3.9 4.7 -- 4.3 5.9 -- |
| to p-et |
| Gaseous products, |
| 475 295 415 460 15 450 690 190 |
| mL/hr |
| __________________________________________________________________________ |
| Run Number |
| 49 50 51 52 53 54 55 56 57 |
| __________________________________________________________________________ |
| Catalyst TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| TiO2 -- |
| ZrO2 -- |
| ZrO2 -- |
| ZrO2 -- |
| ZrO2 -- |
| 20% Fe2 O3 |
| 10% Fe2 O3 |
| 10% Fe2 O3 |
| 10% Fe2 O3 |
| 10% Fe2 O' |
| TiO2 |
| TiO2 |
| TiO2 |
| TiO2 |
| Catalyst Number |
| 35 38 38 38 38 50 50 50 50 |
| Temperature, °C. |
| 375 300 350 375 400 300 350 375 400 |
| Aniline 18 30 66 57 41 1 15 14 11 |
| Conversion, % |
| Ether 50 10 65 78 90 5 18 13 15 |
| Conversion, % |
| Product Distribution, wt. percent |
| N--aniline |
| 20.6 87.3 57.1 46.8 33.4 100 95.9 88.7 81.2 |
| o-et aniline |
| 56.8 1.5 9.1 16.1 25.6 -- -- -- 0.7 |
| p-et aniline |
| 1.0 0.2 1.6 3.2 6.0 -- -- -- -- |
| N,N--di-et aniline |
| -- 5.5 7.8 3.0 1.0 -- 2.8 1.8 1.0 |
| 2,6 di-et aniline |
| 3.9 1.3 4.7 5.5 4.2 -- -- -- -- |
| Other ring di-et |
| 4.9 2.3 11.5 9.6 8.9 -- -- -- -- |
| anilines |
| Ring tri-et anilines |
| 3.2 0.1 2.3 2.9 4.4 -- -- -- -- |
| Others 9.5 1.8 5.8 12.9 16.5 -- 1.3 9.4 17.1 |
| N--alkylation, % |
| 20.6 92.8 64.9 49.8 34.4 100 98.7 90.5 82.2 |
| Ring alkylation, % |
| 61.7 3.0 15.4 24.8 35.8 -- -- -- 0.7 |
| Di-, tri-, & others, % |
| 17.6 4.2 19.6 25.4 29.8 -- 1.3 9.4 17.1 |
| Ratio of o-et |
| 56.8 7.5 6.1 5.0 4.3 -- -- -- -- |
| to p-et |
| Gaseous products, |
| 410 40 350 620 990 30 110 110 160 |
| mL/hr |
| __________________________________________________________________________ |
| **Water was included in the reactant feed so that the molar ratio of |
| H2 O aniline:ether was 5:1:2.5. |
In another series of alkylations various different ether alkylating agents were used in reactions with aniline. In these experiments the following ethers were employed: tetrahydrofuran (THF), dibutyl ether (bu2 O), tetrahydropyran (THP), and 1,4-dioxane (dioxane). The results of these experiments are set forth in Table III.
| TABLE III |
| ______________________________________ |
| Alkylations Using Other Ether Akylating Agents |
| Run Number 58 59 60 61 62 63 |
| ______________________________________ |
| Alkylating Agent |
| THF Bu2 O |
| Bu2 O |
| THF THP Diox- |
| ane |
| Catalyst Number |
| 19 19 19 22 22 22 |
| Temperature, °C. |
| 350 350 400 250 300 300 |
| Etheraniline mole |
| 3:1 1:1 1:1 3:1 3:1 2:1 |
| ratio |
| Aniline Conversion, |
| 91 36 30 98 74 32 |
| Ether Conversion, % |
| 83 66 96 43 46 24 |
| Product Distribution, wt. percent |
| N--ET aniline 19.0 |
| o-et aniline 5.6 |
| p-et aniline 16.1 |
| N,N--di-et aniline -- |
| 2,6-di-et aniline 3.9 |
| Other di-et anilines 11.9 |
| Ring bu anilines 25.7 |
| N--bu aniline |
| 1.7 24.8 20.6 |
| 1-phenyl pyrrole |
| 5.0 |
| 1-phenyl pyrrolidine |
| 65.0 96.8 17.8 |
| 1-phenyl piperidine 97.9 |
| Others 28.3 75.2 53.7 3.2 2.1 25.6 |
| N--alkylation, % 19.0 |
| Ring alkyation, % 25.6 |
| Di-, tri- & others, 55.3 |
| % |
| Ratio of o-et to p-et 0.3 |
| Gaseous products, 100 |
| mL/hr |
| ______________________________________ |
Table IV summarizes the results of additional runs in which N-ethylaniline was alkylated with diethyl ether (Runs 64-68) and 2,6-diethylaniline was alkylated with dimethyl ether (Runs 69-70) using several different catalysts based on titanium dioxide. In Runs 64-68, the reactants were fed in a ratio of 2 moles of the ether per mole of the aniline reactant. In Runs 69 and 70 this ratio was 2.5 to 1.
| TABLE IV |
| ______________________________________ |
| Alkylations of Substituted Anilines |
| Run Number 64 65 66 67 68 69 70 |
| ______________________________________ |
| Catalyst Number |
| 24 24 19 19 32 21 21 |
| Temperature, °C. |
| 350 400 350 400 375 250 300 |
| Amine 30 51 63 88 39 43 86 |
| Conversion % |
| Ether 54 93 71 98 40 |
| Conversion, % |
| Product Distribution, wt. percent |
| Aniline 5.1 19.8 25.6 48.4 33.0 |
| N--et aniline |
| 69.5 48.6 |
| 37.5 12.5 60.6 |
| 48.5 |
| o-et aniline |
| 1.7 5.9 4.4 11.7 1.6 |
| p-et aniline |
| 0.9 3.1 1.7 6.4 0.2 |
| N,N--di-et aniline |
| 12.4 4.9 6.1 0.9 1.2 |
| 2,6-di-et aniline |
| 0.8 2.2 1.7 3.1 0.4 |
| Other di-et |
| 6.3 8.3 6.7 4.1 1.0 |
| anilines |
| 4-me-2,6-di-et 2 |
| aniline |
| N--me-2,6-di-et 42 13 |
| aniline |
| N,N--di-me-2,6- 58 26 |
| di-et aniline |
| N,4-di-me-2,6-di-et 15 |
| aniline |
| N,N,4-tri-me-2,6- 44 |
| di-et aniline |
| Others 3.3 7.2 16.3 12.9 1.9 |
| N--alkylation, % |
| 12.4 4.9 6.1 0.9 1.2 100 39 |
| Ring alkylation, |
| 3.4 11.2 7.8 21.2 2.2 61 |
| Di-, tri- & others, |
| 9.2 15.5 23.0 17.0 3.0 |
| % |
| Ratio of o-et |
| 1.9 1.9 2.6 1.8 8.0 -- 120 |
| to p-et |
| Gaseous products, |
| 200 140 360 710 330 |
| mL/hr |
| ______________________________________ |
In contrast to the results reported above, extensive amounts of decomposition of the alkylating agent were encountered when using an alcohol as the alkylating agent and an iron oxide-germanium oxide catalyst in accordance with the prior art. See in this connection U.S. Pat. No. 4,351,958. In particular, when ethanol and aniline were reacted in the above manner at 350 C over a catalyst composed of 96.1 weight percent Fe2 O3 and 3.9 weight percent GeO2, non-condensable gases were evolved at the rate of 1800 mL/hr. In fact, no ethanol passed through the reaction zone--the ethanol which did not react with the aniline was completely destroyed.
As noted above, the inclusion of water in the feed to the catalyst can be helpful insofar as the regiochemical aspects of the process are concerned. For example a comparison of Runs 43 and 44 in Table II shows that the presence of water resulted in an increase in the ratio of o-ethylaniline to p-ethylaniline from 3.9 to 4.7. When water is employed, it will normally be used in amounts no higher than about 10 moles per mole of ether used, preferably in amounts falling in the range of about 0.1 to about 5 moles per mole of ether used.
An extensive series of N,N-cyclodialkylation reactions of this invention was carried out using Catalyst No. 22, and the tubular reactor and vapor phase reaction procedure described above. The reaction conditions used and results obtained are summarized in Table V. All conversions shown in Table V are based on the amines/amide except as otherwise indicated.
| TABLE V |
| __________________________________________________________________________ |
| Gem Cyclodialkylation of Amines and Amides |
| Run Molar |
| Temp |
| Conver- |
| Product |
| No. Reactants Ratio* |
| °C. |
| sion, % |
| Yield, % |
| Products(s) |
| __________________________________________________________________________ |
| 71 Tetrahydrofuran & Aniline |
| 3:1 300 98 92 1-Phenylpyrrolidine |
| 72 Tetrahydrofuran & Aniline |
| 3:1 250 98 97 1-Phenylpyrrolidine |
| 73 Tetrahydropyran & Aniline |
| 3:1 300 74 98 1-Phenylpiperidine |
| 74 Furan & Aniline 3:1 250 70 99 1-Phenylpyrrole |
| 75 Tetrahydrofuran & Methylamine |
| 1:1 300 42** 100 1-Methylpyrrolidine |
| 76 Tetrahydrofuran & n-Butylamine |
| 2:1 300 14 41 1-Butylpyrrolidine |
| 77 2,5-Dihydrofuran & Methylamine |
| 2:3 250 15** 43 1-Methylpyrrolidine |
| 78 2,3-Dihydrofuran |
| 1:1 275 26** 64 1-Methylpyrrolidine |
| 2,5-Dihydrofuran & Methylamine |
| 8 1-Methylpyrrolidine |
| 79 Dihyrdopyran |
| 3:1 250 31 43 1-Phenylpiperidine |
| Dihydrofuran & Aniline |
| 80 2,5-Dimethyltetrahydrofuran & Aniline |
| 3:1 250 70 88 1-Phenyl-2,5-dimethylpyrroli |
| dine |
| 81 Tetrahydrofuran & 2,6-Diethylaniline |
| 3:1 250 69 96 1-(2,6-Diethylphenyl)pyrroli |
| dine |
| 82 Tetrahydrofuran & N--methylaniline |
| 3:1 305 95 65 1-Phenylpyrrolidine |
| 83 Gamma-Butyrolactone & Aniline |
| 3:1 200 93 97 1-Phenyl-2-pyrrolidone |
| 84 Furfuryl alcohol & Aniline |
| 3:1 225 57 10 1-Phenyl-2-hydroxymethylpyrr |
| ole |
| 55 1-Phenyl-2-methylpyrrole |
| 85 Tetrahydrofurfuryl alcohol & Aniline |
| 3:1 300 37 58 1-Phenylpiperidine |
| 86 2-Methoxytetrahydrofuran & Aniline |
| 2:1 225 45 70 1-Phenylpyrrolidine |
| 87 Furfuryl amine & Aniline |
| 2:1 325 8 15 1-Phenyl-2-methylpyrrole |
| 5 1-Phenyl-2-methylpyrrolidine |
| 6 1-Phenylpyrrole |
| 88 2-Furaldehyde & Aniline |
| 2:1 350 20 5 1-Phenylpyrrole |
| 4 1-Phenyl-2-methylpyrrole |
| 89 Tetrahydrofuran & Acetamide |
| 2:1 200 76 45 1-Acetylpyrrolidine |
| 90 Tetrahydrofuran & o-Anisidine |
| 2:1 275 30 9 1-(2-Methoxyphenyl)pyrrolidi |
| ne |
| 26 1-(2-Hydroxyphenyl)pyrrolidi |
| ne |
| 91 Tetrahydrofuran & Anthranilonitrile |
| 2:1 250 6 43 1-(2-Cyanophenyl)pyrrolidine |
| . |
| 57 1-Phenylpyrrolidine |
| 92 Tetrahydrofuran & o-Chloroaniline |
| 2:1 250 5 59 1-(2-Chlorophenyl)pyrrolidin |
| e |
| 35 1-Phenylpyrrolidine |
| 93 3-Hydroxytetrahydrofuran & Methylamine |
| *** 275 12** 61 1-Methylpyrrol |
| 38 1-Methylpyrrolidine |
| 94 Tetrahydrofuran & Methylenebis Aniline |
| 6:1 300 100 44 1-Phenylpyrrolidine |
| 27 1-(p-Tolyl)pyrrolidine |
| __________________________________________________________________________ |
| *Cyclic ether:Amine/Amide |
| **Based on the cyclic ether |
| ***Not known |
It will be noted that in Run 85, a ring expansion occurred during the course of the N,N-cyclodialkylation reaction. See in this connection, J. Chem. Soc., Section B, 1970, 1525-27, which reports that reaction of ammonia with tetrahydrofuryl alcohol over a palladium/alumina catalyst at 300°C gave 1,2,3,4-tetrahydropyridine.
Example 9 illustrates the use of a liquid phase batch type operation in the practice of this invention. Additionally, it shows the applicability of the N,N-cyclodialkylation reaction to an unstrained cyclic ether having a heterocyclic nitrogen atom in the ring.
PAC Bynthesis Synthesis of N-PhenylimidazolidoneAniline (15.40 g; 0.165 mole) and 2-oxazolidone (9.60 g; 0.110 mole) were refluxed for 6.5 hours with 1.00 g (0.0125 mole) of titanium dioxide (Harshaw Ti 0720 which had been calcined at 300°C for 4 hours). The reaction mass was cooled to 0°C and the crystals which had formed were filtered off. The crystals were recrystallized from ethanol to give N-phenylimidazolidone in 47% yield. The conversion based on 2-oxazolidone was 99%.
Liquid phase or vapor phase procedures similar to those described in the above examples may be used in connection with other suitably reactive cyclic ethers containing one or more hetero atoms other than oxygen.
The conditions used in the process of this invention are susceptible to considerable variation. For example, while my process is usually conducted with an excess of the ether reactant relative to the aromatic amine reactant, a stoichiometric deficiency of the ether may be used, especially when seeking to maximize monoalkylation and minimize polyalkylation. Likewise, the ratio used will be influenced to some extent by the composition of the amine (i.e., whether it is a monoamine or a polyamine), the composition of the ether (i.e., whether it is a monoether or a polyether), and the extent and type of alkylation (i.e., nuclear alkylation and/or N-alkylation) desired. In most cases, the reaction mixture will contain about 0.5 to about 5 molar equivalents of the ether per molar equivalent of the amine. In the case of reactions between monoethers and monoamines, the molar ratio of ether to amine is preferably in the range of about 1:1 to about 3:1.
It is possible to vary certain aspects and other features of the above described invention without departing from the lawful scope or true spirit thereof.
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| Mar 19 1987 | HARGIS, DUANE C | Ethyl Corporation | ASSIGNMENT OF ASSIGNORS INTEREST | 005000 | /0212 | |
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