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With iron beim Chlorieren; |
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| 1: 33 % Chromat.
2: 50 % Chromat. |
With sulfuryl dichloride for 2h; Heating; |
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With chlorine In 1,2-dichloro-ethane at 80℃; for 3 - 6h; |
3; 5; 6
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan' s first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 3.39g of the fluorine-containingK-L-type zeolite (from Tosoh) that had been prepared in Example 1 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.08 mol/hr. The water content of the fluorine-containing K-L-type zeolite that had been prepared in Example 1 and calcinated at 400°C for 1 hour was 0.1% by weight. After 3 hours, the orthoxylene conversion was 64%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 9.8.; (Example 5) Chlorination with a catalyst of fluorine-containing L-type zeolite: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 0.17 g of the fluorine-containing K-L-type zeolite (from Tosoh) that had been prepared in Example 2 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the fluorine-containing K-L-type zeolite that had been prepared in Example 2 and calcinated at 400°C for 1 hour was 0.1 % by weight. After 6 hours, the orthoxylene conversion was 97 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.7.; (Example 6) Chlorination with a catalyst of fluorine-containing L-type zeolite: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct. and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 0.17 g of the fluorine-containing K-L-type zeolite (from Tosoh) that had been prepared in Example 2 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 0.05 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the fluorine-containing K-L-type zeolite that had been prepared in Example 2 and calcinated at 400°C for 1 hour was 0.1 % by weight. After 6 hours, the orthoxylene conversion was 98 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.8. |
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With chlorine In 1,2-dichloro-ethane at 80℃; for 4h; |
1; 3; 6
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 3.39 g of a K-L-type zeolite (from Tosoh) that had been calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.08 mol/hr. The water content of the K-L-type zeolite that had been calcinated at 400°C for 1 hour was 0.1 % by weight. After 2 hours, the orthoxylene conversion was 49%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.1. After 4 hours, the orthoxylene conversion was 94%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.5.; (Comparative Example 3) A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16. 96 g of orthoxylene (Sigma Aldrich Japan' s first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 0.17 g of a K-L-type zeolite (from Tosoh) that had been calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the K-L-type zeolite that had been calcinated at 400°C for 1 hour was 0.1% by weight. After 6 hours, the orthoxylene conversion was 91%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 7.5.; (Comparative Example 6) A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 12.74 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 45 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 2.54 g of a K-L-type zeolite (from Tosoh) that had been calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.082 mol/hr. The water content of the K-L-type zeolite that had been calcinated at 400°C for 1 hour was 0.1% by weight. After 1 hour, the orthoxylene conversion was 43 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 9.6. |
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With chlorine at 80 - 100℃; for 4 - 8h; Neat (no solvent); |
2; 5
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 53 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, and 2.5 g of a K-L-type zeolite (from Tosoh) that had been calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.13 mol/hr. The water content of the K-L-type zeolite that had been calcinated at 400°C for 1 hour was 0.1% by weight. After 4 hours, the orthoxylene conversion was 46 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 1.6.; (Comparative Example 5) A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 53 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, and 2.5 g of a K-L-type zeolite (from Tosoh) that had been calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 100°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. After this was heated at 100°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.13 mol/hr. The water content of the K-L-type zeolite that had been calcinated at 400°C for 1 hour was 0.1% by weight. After 8 hours, the orthoxylene conversion was 40%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 1.6. |
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With chlorine In 1,2-dichloro-ethane at 80℃; for 2h; |
15
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 3.39 g of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.08 mol/hr. The water content of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour was 0.1% by weight. After 2 hours, the orthoxylene conversion was 58%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.9. |
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With chlorine at 100℃; Neat (no solvent); |
16
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 53 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, and 2.5 g of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 100°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 100°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.13 mol/hr. The water content of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour was 0.1% by weight. After 8 hours, the orthoxylene conversion was 43%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 1.8. |
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With chlorine at 80℃; for 4h; Neat (no solvent); |
4
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet duct, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 53 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, and 2.5 g of the fluorine-containing K-L-type zeolite (from Tosoh) that had been prepared in Example 1 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.13 mol/hr. The water content of the fluorine-containing K-L-type zeolite that had been prepared in Example 1 and calcinated at 400°C for 1 hour was 0.1% by weight. After 4 hours, the orthoxylene conversion was 42%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 1.8. |
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With chlorine In 1,2-dichloro-ethane at 80℃; for 1 - 7.25h; |
15; 17; 18; 20; 21; 22
A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 3.39 g of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. After this was heated at 80°C, the nitrogen gas was exchanged for chlorine gas and the reaction was started. The chlorine gas flow rate was controlled to be 0.08 mol/hr. The water content of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 13 and calcinated at 400°C for 1 hour was 0.1% by weight. After 2 hours, the orthoxylene conversion was 58%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 8.9.; (Example 17) Chlorination with a catalyst of L-type zeolite having the crystal size of at most 100 nm: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 12.74 g of orthoxylene (Sigma Aldrich Japan' s first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 45 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 2.54 g of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 14 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.082 mol/hr. The water content of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 14 and calcinated at 400°C for 1 hour was 0.1 % by weight. After 1 hour, the orthoxylene conversion was 46 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 10.3.; (Example 18) Chlorination with a catalyst of L-type zeolite having the crystal size of at most 100 nm: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 0.17 g of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 14 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 14 and calcinated at 400°C for 1 hour was 0.1 % by weight. After 6 hours, the orthoxylene conversion was 97 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 10.4.; (Example 20) Chlorination with a catalyst of fluorine-containing L-type zeolite having the crystal size of at most 100 nm: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan' s first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical), and 0.17 g of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 400°C for 1 hour and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 400°C for 1 hour was 0.1% by weight. After 6 hours, the orthoxylene conversion was 98%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 11.7. After 7.25 hours, the orthoxylene conversion was over 100 %, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 20.9. At the point at which the conversion was over 100%, the 4-chloro-orthoxylene selectivity significantly increased.; (Example 21) Chlorination with a catalyst of fluorine-containing L-type zeolite having the crystal size of at most 100 nm: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical) , and 0.17 g of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 165°C for 12 hours and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet tube. After this was heated at 80°C, the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 165°C for 12 hours was 1.3% by weight. After 6 hours, the orthoxylene conversion was 97%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 10.7.; (Example 22) Chlorination with a catalyst of fluorine-containing L-type zeolite having the crystal size of at most 100 nm: A 100-ml four-neck flask was equipped with a reflux condenser, a thermometer, a chlorine inlet tube, and a sampling duct. This was so designed that waste chlorine gas could be exhausted from the top of the reflux condenser and trapped in an aqueous sodium hydroxide solution. Heating it was effected in an oil bath. 16.96 g of orthoxylene (Sigma Aldrich Japan's first class grade chemical) that had been previously dried with Molecular Sieve 4A to have a water content of 20 ppm, and 0.17 g of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 165°C for 12 hours and then cooled in a desiccator were put into the flask, and heated at 80°C with nitrogen gas being introduced thereinto through the chlorine gas inlet duct. Then, this was heated at 130°C for 12 hours to remove water from the zeolite. Next, this was cooled to 80°C, and 60 ml of 1,2-dichloroethane (Sigma Aldrich Japan's first class grade chemical) was added to it, and the nitrogen gas was mixed with chlorine gas and the reaction was started. The gas blend ratio was nitrogen gas/chlorine gas = 4 by volume. The chlorine gas flow rate was controlled to be 0.026 mol/hr. The water content of the fluorine-containing L-type zeolite having the crystal size of at most 100 nm that had been prepared in Example 19 and calcinated at 165°C for 12 hours was 1.3 % by weight. Since the zeolite was heated in xylene at 130°C, the water content thereof during reaction would be lower than 1. 3 % by weight since this was not exposed at all to air after its heating at 130°C. After 6 hours, the orthoxylene conversion was 97%, and the production ratio of 4-chloro-orthoxylene/3-chloro-orthoxylene was 11.4. |
| 1: 62 %Chromat.
2: 3 %Chromat. |
With N-chloro-succinimide In 1,2-dichloro-ethane at 80℃; regiospecific reaction; |
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With chlorine for 3.5h; |
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