N-[3-(Dimethylamino)propyl]methacrylamide

Liquid

In the process of Example 1, to a 500 ml flask, equipped with a thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged xylene 20 g, methyl methacrylate (MMA, Aldrich) 62.7 g and phenothiazine (PTZ) 0.31 g. The mixture was heated toward to reflux with a very slow dry air purge. When the batch temperature reached 70° C., dibutyltin oxide (BuIn the process of Example 1, to a 500 ml flask, equipped with a thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged xylene 20 g, methyl methacrylate (MMA, Aldrich) 62.7 g and phenothiazine (PTZ) 0.31 g. The mixture was heated toward to reflux with a very slow dry air purge. When the batch temperature reached 70° C., dibutyltin oxide (BuIn the process of Example 1, to a 500 ml flask, equipped with a thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged xylene 20 g, methyl methacrylate (MMA, Aldrich) 62.7 g and phenothiazine (PTZ) 0.31 g. The mixture was heated toward to reflux with a very slow dry air purge. When the batch temperature reached 70° C., dibutyltin oxide (BuIn the process of Example 1, to a 500 ml flask, equipped with a thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged xylene 20 g, methyl methacrylate (MMA, Aldrich) 62.7 g and phenothiazine (PTZ) 0.31 g. The mixture was heated toward to reflux with a very slow dry air purge. When the batch temperature reached 70° C., dibutyltin oxide (BuIn the process of Example 6, to a 500 ml flask, equipped with thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged methyl methacrylate (Aldrich) 206.7 g and phenothiazine 0.3 g. The mixture was heated toward to reflux with a very slow dry air purge. When batch temperature reached 70° C., dibutyltin oxide (Eurecat 9555 from Crompton) 5.01 g was added. Heating continued. When the batch began to boil at 101° C., dimethylethanolamine (DMEA from BASF) 11.8 g was added quickly. Distillate started to come out after 15 minutes and the batch became free from insoluble catalyst and clear. Then, 35.3 g DMEA was added over 45 minutes and the batch temperature was allowed to rise. Distillate was collected. After finishing DMEA, Tyzor TPT 0.35 g was added, the batch was held at reflux at 103-107° C. for one hour then DMAPA 53.34 g was added over 90 minutes. Continue to collect distillate at 60-65° C. and to allow the reaction temperature to rise. After the addition, the batch was held at 120-150° C. for three hours. The batch temperature rose gradually. A total 57 grams of methanol/methacrylate azeotrope was collected. The remaining methyl methacrylate was distilled under vacuum until the batch temperature decreased to 130° C. at -17.5 inch Hg. A total 63.5 g of the distillate was collected, which would be recycled. HPLC analysis showed 185 gram residual contained 45.4percent DMAPMA, 41.9percent dimethylaminoethyl methacrylate (DMAEMA) and 1.6percent methacrylic acid. This accounted for 95percent yield for DMAPMA from DMAPA and 94percent for DMAEMA from DMEA (Ex No.6).; The process of was run according to that described above for the process of Example 6.; EXAMPLE 12DMAPMA distillate from the above reactions, containing water-insoluble organotin catalysts and 1300 ppm methacrylic acid (MMA) 170.0 g was mixed with 25percent NaOH 2 g and phenothiazine 0.05 g. The mixture was subjected to vacuum distillation. The distillate was collected at 91-93° C. and -30.3 inch Hg to yield 105 g pure DMAPMA (91percent yield) containing no water-insoluble and non-detectable MAA (<10 ppm) by HPLC analysis.In the process of Example 6, to a 500 ml flask, equipped with thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged methyl methacrylate (Aldrich) 206.7 g and phenothiazine 0.3 g. The mixture was heated toward to reflux with a very slow dry air purge. When batch temperature reached 70° C., dibutyltin oxide (Eurecat 9555 from Crompton) 5.01 g was added. Heating continued. When the batch began to boil at 101° C., dimethylethanolamine (DMEA from BASF) 11.8 g was added quickly. Distillate started to come out after 15 minutes and the batch became free from insoluble catalyst and clear. Then, 35.3 g DMEA was added over 45 minutes and the batch temperature was allowed to rise. Distillate was collected. After finishing DMEA, Tyzor TPT 0.35 g was added, the batch was held at reflux at 103-107° C. for one hour then DMAPA 53.34 g was added over 90 minutes. Continue to collect distillate at 60-65° C. and to allow the reaction temperature to rise. After the addition, the batch was held at 120-150° C. for three hours. The batch temperature rose gradually. A total 57 grams of methanol/methacrylate azeotrope was collected. The remaining methyl methacrylate was distilled under vacuum until the batch temperature decreased to 130° C. at -17.5 inch Hg. A total 63.5 g of the distillate was collected, which would be recycled. HPLC analysis showed 185 gram residual contained 45.4percent DMAPMA, 41.9percent dimethylaminoethyl methacrylate (DMAEMA) and 1.6percent methacrylic acid. This accounted for 95percent yield for DMAPMA from DMAPA and 94percent for DMAEMA from DMEA (Ex No.6).; The process of Example 10 was run according to that described above for the process of Example 7, except that small amount of hexane was used to remove any residual amount of water from the system. A lightly better yield was observed.; EXAMPLE 12DMAPMA distillate from the above reactions, containing water-insoluble organotin catalysts and 1300 ppm methacrylic acid (MMA) 170.0 g was mixed with 25percent NaOH 2 g and phenothiazine 0.05 g. The mixture was subjected to vacuum distillation. The distillate was collected at 91-93° C. and -30.3 inch Hg to yield 105 g pure DMAPMA (91percent yield) containing no water-insoluble and non-detectable MAA (<10 ppm) by HPLC analysis.In the process of Example 6, to a 500 ml flask, equipped with thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged methyl methacrylate (Aldrich) 206.7 g and phenothiazine 0.3 g. The mixture was heated toward to reflux with a very slow dry air purge. When batch temperature reached 70° C., dibutyltin oxide (Eurecat 9555 from Crompton) 5.01 g was added. Heating continued. When the batch began to boil at 101° C., dimethylethanolamine (DMEA from BASF) 11.8 g was added quickly. Distillate started to come out after 15 minutes and the batch became free from insoluble catalyst and clear. Then, 35.3 g DMEA was added over 45 minutes and the batch temperature was allowed to rise. Distillate was collected. After finishing DMEA, Tyzor TPT 0.35 g was added, the batch was held at reflux at 103-107° C. for one hour then DMAPA 53.34 g was added over 90 minutes. Continue to collect distillate at 60-65° C. and to allow the reaction temperature to rise. After the addition, the batch was held at 120-150° C. for three hours. The batch temperature rose gradually. A total 57 grams of methanol/methacrylate azeotrope was collected. The remaining methyl methacrylate was distilled under vacuum until the batch temperature decreased to 130° C. at -17.5 inch Hg. A total 63.5 g of the distillate was collected, which would be recycled. HPLC analysis showed 185 gram residual contained 45.4percent DMAPMA, 41.9percent dimethylaminoethyl methacrylate (DMAEMA) and 1.6percent methacrylic acid. This accounted for 95percent yield for DMAPMA from DMAPA and 94percent for DMAEMA from DMEA (Ex No.6).; The process of Example 8 was run according to that described above for the process of Example 6, except that dioctyltin oxide (Eurecat DOTO, Crompton) was used as the transesterification catalyst.; EXAMPLE 12DMAPMA distillate from the above reactions, containing water-insoluble organotin catalysts and 1300 ppm methacrylic acid (MMA) 170.0 g was mixed with 25percent NaOH 2 g and phenothiazine 0.05 g. The mixture was subjected to vacuum distillation. The distillate was collected at 91-93° C. and -30.3 inch Hg to yield 105 g pure DMAPMA (91percent yield) containing no water-insoluble and non-detectable MAA (<10 ppm) by HPLC analysis.In the process of Example 6, to a 500 ml flask, equipped with thermometer, gas inlet, addition port, magnetic stirrer and distillation column of 5-plates topped with a distillation head connecting to a condenser, were charged methyl methacrylate (Aldrich) 206.7 g and phenothiazine 0.3 g. The mixture was heated toward to reflux with a very slow dry air purge. When batch temperature reached 70° C., dibutyltin oxide (Eurecat 9555 from Crompton) 5.01 g was added. Heating continued. When the batch began to boil at 101° C., dimethylethanolamine (DMEA from BASF) 11.8 g was added quickly. Distillate started to come out after 15 minutes and the batch became free from insoluble catalyst and clear. Then, 35.3 g DMEA was added over 45 minutes and the batch temperature was allowed to rise. Distillate was collected. After finishing DMEA, Tyzor TPT 0.35 g was added, the batch was held at reflux at 103-107° C. for one hour then DMAPA 53.34 g was added over 90 minutes. Continue to collect distillate at 60-65° C. and to allow the reaction temperature to rise. After the addition, the batch was held at 120-150° C. for three hours. The batch temperature rose gradually. A total 57 grams of methanol/methacrylate azeotrope was collected. The remaining methyl methacrylate was distilled under vacuum until the batch temperature decreased to 130° C. at -17.5 inch Hg. A total 63.5 g of the distillate was collected, which would be recycled. HPLC analysis showed 185 gram residual contained 45.4percent DMAPMA, 41.9percent dimethylaminoethyl methacrylate (DMAEMA) and 1.6percent methacrylic acid. This accounted for 95percent yield for DMAPMA from DMAPA and 94percent for DMAEMA from DMEA (Ex No.6).; The process of Example 7 was run according to that described above for the process of Example 6, except that dibutyltin oxide from Aldrich was used as the transesterification catalyst.; The process of was run according to that described above for the process of Example 7, except that part of the MMA was recycled from previous reactions.; EXAMPLE 12DMAPMA distillate from the above reactions, containing water-insoluble organotin catalysts and 1300 ppm methacrylic acid (MMA) 170.0 g was mixed with 25percent NaOH 2 g and phenothiazine 0.05 g. The mixture was subjected to vacuum distillation. The distillate was collected at 91-93° C. and -30.3 inch Hg to yield 105 g pure DMAPMA (91percent yield) containing no water-insoluble and non-detectable MAA (<10 ppm) by HPLC analysis.

Intermediates

500,000 - 1,000,000 lb

Molecular Weight:170.25
XLogP3:0.9
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:5
Exact Mass:170.141913202
Monoisotopic Mass:170.141913202
Topological Polar Surface Area:32.3
Heavy Atom Count:12
Complexity:164
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes