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CAS No. : | 51806-23-6 |
Formula : | C15H24O5 |
M.W : | 284.35 |
SMILES Code : | O=C(OC)C(C1C(CCCCC)C(CC1)=O)C(OC)=O |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | at 180℃; for 4 h; Inert atmosphere | Under nitrogen protection, the addition intermediate prepared in Example 5 (85.3 g, 0.3 mol) was added to a solution with a constant pressure drop In a three-necked flask with a bucket, a thermometer, and a condenser, the oil bath was heated to 180 °C, and a mixture of deionized water and methanol (90 mL, 1/1) was slowly added dropwise with rapid stirring. The addition was completed within 4 hours. One hour after the reaction, the reaction was stopped by cooling to room temperature. Crude vacuum distillation, collecting 140-141 °C (2-3mmHg) distillate, to obtain 57.7g of methyl dihydrojasmonate, yield 85percent, purity 98percent. |
283.48 g | at 215℃; for 4 h; | To a reaction apparatus equipped with a distillation distillation pipe, 283.48 g of dimethyl 2- (3-oxo-2-pentylcyclopentyl) malonate obtained in Example 1 was added, heated to 215 ° C.,Water was added dropwise. A dropwise addition reaction was carried out at 215 ° C. for 4 hours while distilling out generated carbon dioxide and methanol.After completion of the reaction, 203.27 g of crude product was obtained.Methyl (3-oxo-2-pentylcyclopentyl) acetate (148.71 g) obtained by fractionating the crude product was purified by reverse-It has fruity and jasmine-like fragrance,It was also excellent as a perfume material. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.7% | at 180 - 215℃; for 4 - 16 h; | A 1 L four-neck flask equipped with a stirrer, a supply unit, a thermometer and a rectifier was charged with 600 g of raw material containing 545 g (1.92 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180°C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to 6 g/h from the start of the supply to the 2nd hour, to 3 g/h from the 2nd hour to the 8th hour and to 1.2 g/h after the 8th hour with measuring the content of water in the reaction solution by a Karl Fischer's coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) such that the content of water was limited to 0.4percent by weight or less. Then, the reaction was completed for 16 hours from the start of the supply of water. The maximum water concentration in the reaction solution was 0.21percent by weight. During the reaction, the difference (X-Y) between the integrating molar number X (excluding distilled water content) of the water to be supplied and the molar number Y of the water reacted with dimethyl 2-pentyl-3-oxo-cyclopentylmalonate was 14.8percent at a maximum based on the molar number of the charged dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. It was found that the reaction product contained 423 g (1.87 mol, yield: 97.3percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 10.8 g (0.051 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid.; Comparative Example 1 The same 1 L four-neck flask that was used in Example 1 was charged with 600 g of raw material containing 557 g (1.96 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180°C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to a constant rate (6 g/h) . Then, the reaction was completed for 9 hours from the start of the supply of water. During the supply of water, the content of water in the reaction solution was measured by a Karl Fischer's coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) and as a result, the maximum water concentration in the reaction solution was 0.44percent by weight. It was found that the reaction product contained 402 g (1.78 mol, yield: 90.7percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 33.5 g (0.158 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid.; Example 2 The same 1 L four-neck flask that was used in Example 1 was charged with 600 g of raw material containing 550 g (1.94 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 215°C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to 18 g/h from the start of the supply to the 1st hour, to 12 g/h from the 1st hour to the 2nd hour, to 6 g/h from the 2nd hour to the 3rd hour and to 3 g/h after the 3rd hour with measuring the content of water in the reaction solution by a Karl Fischer' s coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) such that the content of water was limited to 0.4percent by weight or less. Then, the reaction was completed for 4 hours from the start of the supply of water. The maximum water concentration in the reaction solution was 0.14percent by weight. During the reaction, the difference (X-Y) between the integrating molar number X (excluding distilled water content) of the water to be supplied and the molar number Y of the water reacted with dimethyl 2-pentyl-3-oxo-cyclopentylmalonate was 10.3percent at a maximum based on the molar number of the supplied dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. It was found that the reaction product contained 420 g (1.86 mol, yield: 96.0percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 5.8 g (0.027 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.5% | at 180 - 215℃; for 3.75 - 15 h; | A reactor shown in Fig. 1 which was provided with a reaction vessel 1 constituted of a 1 L four-neck flask equipped with a stirrer 2, a supply unit 3, a thermometer 4 and a Packed column 5 and a cooling tube (condenser) 6 and a receiver 7 installed downstream of the Packed column 5 was used to run a reaction. The reaction vessel 1 was charged with 600 g of raw material containing 556 g (1.96 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 215°C with stirring under normal pressure. Then, water was supplied from the supply unit 3 at a rate of 12 g/h. Among the vapor generated during the reaction, components containing methyl 2-pentyl-3-oxo-cyclopentylacetate, dimethyl 2-pentyl-3-oxo-cyclopentylmalonate and 2-pentyl-2-cyclopentenone and water were condensed in the Packed column 5 and returned continuously to the reaction vessel 1. Methanol was distilled out of the system, condensed in the condenser 6 and recovered in the receiver 7. Then, the reaction was completed for 3.75 hours from the start of the supply of water. It was found that the reaction product contained 413 g (1.83 mol, yield: 93.5percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 69.8 g (2.18 mol) of methanol could be recovered from the fractions condensed outside of the system.; Example 4 A reactor shown in Fig. 2 which was provided with a reaction vessel 10 constituted of a 2L four-neck flask equipped with a stirrer 2, a supply unit 3 and a thermometer 4, a cooler provided with two cooling tubes (condensers) 8 and 9 arranged in series and a thermometer 14 arranged between the two cooling tubes and a receiver 7 was used to run a reaction. The reaction vessel 10 was charged with 1111 g of raw material containing 1068 g (3.76 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180°C with stirring under normal pressure. Then, the supply of water from supply unit 3 was started. During the supply of water, the supply rate of water was adjusted to 11.6 g/h from the start of the supply to the 2nd hour, to 5.6 g/h from the 2nd hour to the 8th hour and to 2.3 g/h after the 8th hour. Among the vapor generated during the reaction, components containing methyl 2-pentyl-3-oxo-cyclopentylacetate, dimethyl 2-pentyl-3-oxo-cyclopentylmalonate and 2-pentyl-2-cyclopentenone and water were condensed in the first cooling tube 8 with controlling the supply rate of cooling water such that the vapor temperature was 65°C at the outlet of the cooling tube 8 and returned continuously to the reaction vessel 10, and methanol was condensed in the second cooling tube 9 with supplying a 0°C cooling medium and recovered in the receiver 7. Then, the reaction was completed for 15 hours from the start of the supply of water. The reaction product contained 811 g (3.59 mol, yield: 95.5percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 132.6 g (4.14 mol) of methanol could be recovered from the fraction condensed outside of the system.; Example 5 A reactor shown in Fig. 3 which was provided with a reaction vessel 13 constituted of a 3L four-neck flask equipped with a stirrer 2, a supply unit 3, a thermometer 4 and a rectifier 11 with 15-stages, a cooling tube (condenser) 12 and a receiver 7 which were installed downstream of the rectifier 11 provided with a thermometer 15 was used to run a reaction. The reaction vessel 13 was charged with 1933 g of raw material containing 1840 g (6.48 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180°C with stirring under normal pressure. Then, the supply of water from supply unit 3 was started. During the supply of water, the supply rate of water was adjusted to 19 g/h from the start of the supply to the 2nd hour, to 9.5 g/h from the 2nd hour to the 8th hour and to 3.8 g/h after the 8th hour. Among the vapor generated during the reaction, components containing methyl 2-pentyl-3-oxo-cyclopentylacetate, dimethyl 2-pentyl-3-oxo-cyclopentylmalonate and 2-pentyl-2-cyclopentenone and water were refluxed continuously to the reaction vessel 13 at a reflux ratio of 5, while maintaining the top temperature of the rectifier at 65°C. Methanol was condensed in the condenser 12 outside of the system and recovered in the receiver 7. Then, the reaction was completed for 14 hours from the start of the supply of water. The reaction product contained 1414 g (6.26 mol, yield: 96.6percent) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 177.2 g (5.54 mol) of methanol could be recovered from the fraction condensed outside of the system. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.7 - 97.3% | With water; at 180 - 215℃; for 4 - 16h;Product distribution / selectivity; | A 1 L four-neck flask equipped with a stirrer, a supply unit, a thermometer and a rectifier was charged with 600 g of raw material containing 545 g (1.92 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to 6 g/h from the start of the supply to the 2nd hour, to 3 g/h from the 2nd hour to the 8th hour and to 1.2 g/h after the 8th hour with measuring the content of water in the reaction solution by a Karl Fischer's coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) such that the content of water was limited to 0.4% by weight or less. Then, the reaction was completed for 16 hours from the start of the supply of water. The maximum water concentration in the reaction solution was 0.21% by weight. During the reaction, the difference (X-Y) between the integrating molar number X (excluding distilled water content) of the water to be supplied and the molar number Y of the water reacted with dimethyl 2-pentyl-3-oxo-cyclopentylmalonate was 14.8% at a maximum based on the molar number of the charged dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. It was found that the reaction product contained 423 g (1.87 mol, yield: 97.3%) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 10.8 g (0.051 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid.; Comparative Example 1 The same 1 L four-neck flask that was used in Example 1 was charged with 600 g of raw material containing 557 g (1.96 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 180C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to a constant rate (6 g/h) . Then, the reaction was completed for 9 hours from the start of the supply of water. During the supply of water, the content of water in the reaction solution was measured by a Karl Fischer's coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) and as a result, the maximum water concentration in the reaction solution was 0.44% by weight. It was found that the reaction product contained 402 g (1.78 mol, yield: 90.7%) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 33.5 g (0.158 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid.; Example 2 The same 1 L four-neck flask that was used in Example 1 was charged with 600 g of raw material containing 550 g (1.94 mol) of dimethyl 2-pentyl-3-oxo-cyclopentylmalonate produced in the same manner as in Production Example 1 and the raw material was heated to 215C with stirring under normal pressure. Then, the supply of water to the bottom of the reactor was started. During the supply of water, the supply rate of water was adjusted to 18 g/h from the start of the supply to the 1st hour, to 12 g/h from the 1st hour to the 2nd hour, to 6 g/h from the 2nd hour to the 3rd hour and to 3 g/h after the 3rd hour with measuring the content of water in the reaction solution by a Karl Fischer' s coulometric titration (instrument: Trace-water measuring device AQ-7, manufactured by HIRANUMA SANGYO Co. , Ltd.) such that the content of water was limited to 0.4% by weight or less. Then, the reaction was completed for 4 hours from the start of the supply of water. The maximum water concentration in the reaction solution was 0.14% by weight. During the reaction, the difference (X-Y) between the integrating molar number X (excluding distilled water content) of the water to be supplied and the molar number Y of the water reacted with dimethyl 2-pentyl-3-oxo-cyclopentylmalonate was 10.3% at a maximum based on the molar number of the supplied dimethyl 2-pentyl-3-oxo-cyclopentylmalonate. It was found that the reaction product contained 420 g (1.86 mol, yield: 96.0%) of methyl 2-pentyl-3-oxo-cyclopentylacetate and 5.8 g (0.027 mol) of 2-pentyl-3-oxo-cyclopentylacetic acid. |
Tags: 51806-23-6 synthesis path| 51806-23-6 SDS| 51806-23-6 COA| 51806-23-6 purity| 51806-23-6 application| 51806-23-6 NMR| 51806-23-6 COA| 51806-23-6 structure
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H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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