Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 m...Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 molar ratio on the conversion of dimethyl ether and the product selectivity were investigated under the same catalyst formulation.Results showed that a maximum conversion of dimethyl ether was obtained when a mixture consisting of 0.3 mol dimethyl ether and 120 ml acetic acid was reacted at 180 ℃ and 3.0 MPa for 10 h at a stirring speed of 600 rpm under a syngas flow with a CO/H2 molar ratio of 2.5,which was catalyzed by a catalyst mixture comprising 0.3 g RhI3,6 g PPh3 and 1.3 g CH3I.The selectivity of ethylidene diacetate increased with temperature,decreased with the CO/H2 molar ratio and exhibited a maximum with pressure.展开更多
The novel fungicidal agents, （E）-5-[1-（2-oxo-l-oxaspiro[4,5]dec/non-3-en-3-yl）ethylidene]-2-aminoimidazolin- 4-one derivatives, were designed and synthesized in moderate to excellent yields in four steps using a-h...The novel fungicidal agents, （E）-5-[1-（2-oxo-l-oxaspiro[4,5]dec/non-3-en-3-yl）ethylidene]-2-aminoimidazolin- 4-one derivatives, were designed and synthesized in moderate to excellent yields in four steps using a-hydroxyketone and diketene as raw materials and characterized by HR-ESI-MS, 1H NMR and X-ray diffraction. The preliminary bioassay showed that some of these compounds, such as 5e, 6a, 6e, and 7h exhibit 87.8%, 91.3%, 89.9% and 87.8% inhibition rates against Sclerotinia scleotiorum, 3b, 3c, 4c and 7h exhibit 96.4%, 92.5%, 90.3% and 76.9% inhibition rates against Phytophthora capsici at the concentration of 50 μg/mL, respectively. These compounds exhibited significant fungicidal activities against S. scleotiorum and P. capsici with EC50 values of 2.56 --11.60 μg/mL, and compounds 6e and 7h exhibited weak inhibition against the spore germination of S. scleoti- orum, while the spore germination ofP. capsici was strongly inhibited by compound 7h solution. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） observation indicated that compound 7h had a significant impact on the structure and function of the hyphal cell wall ofP. capsici mycelium.展开更多
文摘Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 molar ratio on the conversion of dimethyl ether and the product selectivity were investigated under the same catalyst formulation.Results showed that a maximum conversion of dimethyl ether was obtained when a mixture consisting of 0.3 mol dimethyl ether and 120 ml acetic acid was reacted at 180 ℃ and 3.0 MPa for 10 h at a stirring speed of 600 rpm under a syngas flow with a CO/H2 molar ratio of 2.5,which was catalyzed by a catalyst mixture comprising 0.3 g RhI3,6 g PPh3 and 1.3 g CH3I.The selectivity of ethylidene diacetate increased with temperature,decreased with the CO/H2 molar ratio and exhibited a maximum with pressure.
基金This project was co-tbunded by the Ph.D Program of Ministry of Education, China （No. 20130008110003）, and the National Natural Science Foundation of China （No. 21172254）.
文摘The novel fungicidal agents, （E）-5-[1-（2-oxo-l-oxaspiro[4,5]dec/non-3-en-3-yl）ethylidene]-2-aminoimidazolin- 4-one derivatives, were designed and synthesized in moderate to excellent yields in four steps using a-hydroxyketone and diketene as raw materials and characterized by HR-ESI-MS, 1H NMR and X-ray diffraction. The preliminary bioassay showed that some of these compounds, such as 5e, 6a, 6e, and 7h exhibit 87.8%, 91.3%, 89.9% and 87.8% inhibition rates against Sclerotinia scleotiorum, 3b, 3c, 4c and 7h exhibit 96.4%, 92.5%, 90.3% and 76.9% inhibition rates against Phytophthora capsici at the concentration of 50 μg/mL, respectively. These compounds exhibited significant fungicidal activities against S. scleotiorum and P. capsici with EC50 values of 2.56 --11.60 μg/mL, and compounds 6e and 7h exhibited weak inhibition against the spore germination of S. scleoti- orum, while the spore germination ofP. capsici was strongly inhibited by compound 7h solution. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） observation indicated that compound 7h had a significant impact on the structure and function of the hyphal cell wall ofP. capsici mycelium.
