CN102432588B - Method for synthesizing karanal - Google Patents
Method for synthesizing karanal Download PDFInfo
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- CN102432588B CN102432588B CN 201110380843 CN201110380843A CN102432588B CN 102432588 B CN102432588 B CN 102432588B CN 201110380843 CN201110380843 CN 201110380843 CN 201110380843 A CN201110380843 A CN 201110380843A CN 102432588 B CN102432588 B CN 102432588B
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Abstract
The invention discloses a method for synthesizing karanal, relating to the synthesis of organic compounds. The method comprises the following steps of: with 2-diethyl methylmalonate as a raw material, carrying out alkylation reaction on 2-butyl bromide and the 2-diethyl methylmalonate to synthesize 2-methyl-2-sec-butyl-diethyl malonate as an intermediate (I); with the obtained 2-methyl-2-sec-butyl-diethyl malonate as a raw material, carrying out reduction reaction on the 2-methyl-2-sec-butyl-diethyl malonate through metal sodium and absolute ethanol to synthesize 2-methyl-2-sec-butyl-1,3 propanediol as an intermediate (II); with the obtained 2-methyl-2-sec-butyl-1,3 propanediol as a raw material, carrying out condensation reaction on 3, 5-dimethyl-4-cycolhexene formaldehyde and the 2-methyl-2-sec-butyl-1,3 propanediol to obtain the karanal product. According to the invention, a complete karanal synthesis route is designed, so that the yield of the karanal product is increased; and the synthesis route provided by the invention is reasonable in design, the raw materials are acquired widely and easily, the synthesis reaction is simple and easy to perform, the cost is lower and the industrial production is easy to realize.
Description
Technical field
The present invention relates to the synthetic method of a kind of synthetic method of organic compound, particularly a kind of karanal.
Background technology
Karanal is a kind of synthetic flavour, does not find its structure at occurring in nature, and it has the strong and gorgeous banksia rose and amber aroma, and fragrance is very lasting.Karanal is mainly used in the daily chemical essence formula, it can be used as functional amber aroma and applies to head perfume to bottom note, because of the persistence of spices in its formula strong, therefore can not excessively use, this kind amber aroma is until bottom note can be brought into play conclusive effect, consumption is generally 10% or 1% diluent, has good fabric lasting effect.Still do not see at home at present the related documents report about the synthetic method of karanal, external English lotus Quest company produce karanal with ligustral and accordingly glycol make (European patent EP 0276998) through acetalation, but this patent does not relate to the design of the complete synthetic route of karanal, and because raw materials used ligustral is mixture, the productive rate that obtains at last karanal is very low, so still can not instruct the suitability for industrialized production of karanal.
Karanal (karanal) chemical name is: 2-(2,4-dimethyl-3-cyclohexyl)-5-methyl-5-(1-methyl-propyl)-1,3-dioxy oxane, molecular formula: C
17H
30O
2, molecular weight is 266.42, outward appearance is colourless liquid, relative density (20 ℃ of g/ml) is 0.960-0.966, refractive index (20 ℃) 1.478-1.484, flash-point〉and 100 ℃, structural formula is as follows:
Summary of the invention
In view of the blank of the complete synthetic method of karanal in present prior art, and the lower problem of gained productive rate, the present invention designs a scientific and reasonable karanal synthetic route.
The present invention is for achieving the above object, and the technical scheme that adopts is: a kind of complete synthetic method of karanal is provided, and concrete synthetic route is divided into three steps:
(1), synthesizing of intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute dehydrated alcohol of 25mL-80mL, add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, after stirring and refluxing 30min-50min, add 2.49g-4.95g 2-n-butyl bromide, at the temperature of 80-90 ℃, back flow reaction 4h-5h, after reaction finishes, reaction mixture is cooled to room temperature, boil off etoh solvent, add volume of mixture 1-3 water dilution doubly, again with diluting rear liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid, extraction liquid is used respectively distilled water, the saturated NaCl aqueous solution is washed 2 times, the dry moisture of removing, filter out impurities after NaCl, ether in filtrate is steamed remove, namely obtain 2-methyl-2-sec-butyl-diethyl malonate,
(2), intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol synthetic: the fritter that the 0.23g-0.46g sodium Metal 99.5 is cut into 2-3mm divides and joins in 2.30g-4.60g 2-methyl-2-sec-butyl-diethyl malonate under stirring for 3 times, drip the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after sodium Metal 99.5 adds, add again the 3-16mL dehydrated alcohol, heating keeps reacting 4-5h under reflux state, after reaction finishes, mixture is heated under 76-80 ℃ boil off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly, with the organic layer in liquid volume 1-3 ethyl acetate extraction diluent doubly after dilution, with 5% dilute hydrochloric acid and saturated NaCl, extraction liquid is washed three times respectively again, the dry moisture of removing, NaCl filters out impurities, steam except after the ethyl acetate in filtrate, obtain 2-methyl-2-sec-butyl-1, 3 propylene glycol,
(3), synthesizing of product karanal: with 13.80g 3, 5-dimethyl-4-cyclohexene formaldehyde and 17.52g-18.25g 2-methyl-2-sec-butyl-1, 3 propylene glycol under agitation join in 40ml dimethylbenzene successively, then add the 0.2-0.3g sal enixum under stirring, heating in water bath backflow 1h-2h, after having reacted, be cooled to room temperature, add 2-3g anhydrous sodium sulphate hermetically drying 12h, filter out impurities, remove the dimethylbenzene in filtrate under reduced pressure, obtain crude product, under nitrogen protection, crude product is carried out underpressure distillation, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get the final product karanal.
Beneficial effect: the present invention adopts the backstepping method to design the route of a complete synthetic karanal, has wherein synthesized intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol, for final synthetic product karanal provides required raw material.The present invention is in the step of synthetic final product karanal, and on the basis of existing technology, operation conditions optimization makes the karanal productive rate that obtains also improve a lot than the document record, the synthetic foundation that provides of these industrialization for karanal.Synthetic route of the present invention is reasonable in design, raw materials used wide material sources, is easy to get, and building-up reactions is simple, and cost is lower, is convenient to realize suitability for industrialized production.
Description of drawings
Fig. 1 is synthetic route schematic diagram of the present invention.
Embodiment
A kind of complete synthetic method of karanal is provided, and concrete synthetic route is divided into three steps:
(1), synthesizing of intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute dehydrated alcohol of 25mL-80mL, add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, after stirring and refluxing 30min-50min, add 2.49g-4.95g 2-n-butyl bromide, at the temperature of 80-90 ℃, back flow reaction 4h-5h, after reaction finishes, reaction mixture is cooled to room temperature, boil off etoh solvent, add volume of mixture 1-3 water dilution doubly, again with diluting rear liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid, extraction liquid is used respectively distilled water, the saturated NaCl aqueous solution is washed 2 times, the dry moisture of removing, filter out impurities after NaCl, ether in filtrate is steamed remove, namely obtain 2-methyl-2-sec-butyl-diethyl malonate,
(2), intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol synthetic: the fritter that the 0.23g-0.46g sodium Metal 99.5 is cut into 2-3mm divides and joins in 2.30g-4.60g 2-methyl-2-sec-butyl-diethyl malonate under stirring for 3 times, drip the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after sodium Metal 99.5 adds, add again the 3-16mL dehydrated alcohol, heating keeps reacting 4-5h under reflux state, after reaction finishes, mixture is heated under 76-80 ℃ boil off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly, with the organic layer in liquid volume 1-3 ethyl acetate extraction diluent doubly after dilution, with 5% dilute hydrochloric acid and saturated NaCl, extraction liquid is washed three times respectively again, the dry moisture of removing, NaCl filters out impurities, steam except after the ethyl acetate in filtrate, obtain 2-methyl-2-sec-butyl-1, 3 propylene glycol,
(3), synthesizing of product karanal: with 13.80g 3, 5-dimethyl-4-cyclohexene formaldehyde and 17.52g-18.25g 2-methyl-2-sec-butyl-1, 3 propylene glycol under agitation join in 40ml dimethylbenzene successively, then add the 0.2-0.3g sal enixum under stirring, heating in water bath backflow 1h-2h, after having reacted, be cooled to room temperature, add 2-3g anhydrous sodium sulphate hermetically drying 12h, filter out impurities, remove the dimethylbenzene in filtrate under reduced pressure, obtain crude product, under nitrogen protection, crude product is carried out underpressure distillation, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get the final product karanal.
Embodiment 1:
(1), intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate is synthetic:
Taking the 0.33g sodium Metal 99.5 slowly puts in the 50mL three-necked bottle that the absolute dehydrated alcohol of 25mL is housed (room temperature).After the sodium total overall reaction, slowly splash into 2.11g 2-methyl-malonic ester, stirring and refluxing 30min with constant pressure funnel, slowly drip again 2.49g 2-n-butyl bromide, at the temperature of 80 ℃, back flow reaction 4h, in reaction process, with GC and TLC following response process;
Reaction is cooled to room temperature with reaction mixture after finishing, and boils off etoh solvent, add the water dilution of equal-volume mixture, with the extracted with diethyl ether of liquid after equal-volume dilution 3 times, after combining extraction liquid, wash extraction liquid 2 times with distilled water, the saturated NaCl aqueous solution respectively again, the dry moisture of removing in extraction liquid, remove by filter impurity NaCl, and steam except ether, namely obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate, be colourless liquid 2.00g, productive rate is 72%;
(2), intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol is synthetic:
Taking 2.30g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL, take the 0.23g sodium Metal 99.5, the fritter that is cut into 2mm divides 3 times and adds in ester, slowly drip again the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after adding for the third time the absolute dehydrated alcohol of 5mL, then add the 3mL dehydrated alcohol, heating keeps reacting 4h under reflux state, in reaction process, with GC and TLC following response process;
After reaction finishes, mixture is heated under 76 ℃ boil off low-boiling-point substance, add the water dilution of equal-volume mixture, with the ethyl acetate extraction organic layer of liquid after the equal-volume dilution, after washing extraction liquid three times with 5% dilute hydrochloric acid and saturated NaCl respectively again, the dry moisture of removing in extraction liquid removes by filter impurity NaCl, after boiling off ethyl acetate, obtain intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol are yellow liquid 1.50g, and productive rate is 65%;
(3), the product karanal is synthetic:
measuring 40ml dimethylbenzene joins in 250ml three neck round-bottomed flasks, take 13.80g 3, 5-dimethyl-4-cyclohexene formaldehyde and 17.52g intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol stir successively and join in dimethylbenzene, then add the 0.2g sal enixum under stirring, heating in water bath backflow 1h, after having reacted, be cooled to room temperature, add 2g anhydrous sodium sulphate hermetically drying 12h, remove by filter anhydrous sodium sulphate, dimethylbenzene in the pressure reducing and steaming filtrate, obtain crude product, crude product underpressure distillation under nitrogen protection, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get final product karanal sterling 20.7g, be colourless liquid, productive rate is 78%.
Embodiment 2:
(1), intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate is synthetic:
Taking the 0.50g sodium Metal 99.5 slowly puts in the 80mL three-necked bottle that the absolute dehydrated alcohol of 50mL is housed (room temperature).After the sodium total overall reaction, slowly splash into 3.10g 2-methyl-malonic ester with constant pressure funnel, stirring and refluxing 40min, more slowly drip 3.83g 2-n-butyl bromide, under 85 ℃, back flow reaction 4.5h is in reaction process, with GC and TLC following response process;
After reaction finishes, reaction mixture is cooled to room temperature, boils off etoh solvent, add the water dilution of 2 times of volume of mixture, again with the extracted with diethyl ether of 2 times of liquid volumes after dilution 3 times, combining extraction liquid is washed 2 times with distilled water, the saturated NaCl aqueous solution respectively, and the dry moisture of removing removes by filter impurity NaCl, and steam except the ether in filtrate, namely obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate, be colourless liquid 3.02g, productive rate is 73%;
(2), intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol is synthetic:
Taking 3.50g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL, take the 0.35g sodium Metal 99.5, the fritter that is cut into 3mm divides under 3 stirrings and adds in ester, slowly drip again the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after adding for the third time the absolute dehydrated alcohol of 5mL, then add the 8mL dehydrated alcohol, heating keeps reacting 4.5h under reflux state, in reaction process, with GC and TLC following response process;
After reaction finishes, mixture is heated under 78 ℃ boil off low-boiling-point substance, add the water dilution of 2 times of volume of mixture, with the ethyl acetate extraction organic layer of 2 times of liquid volumes after dilution, after washing extraction liquid three times with 5% dilute hydrochloric acid and saturated NaCl respectively again, the dry moisture of removing removes by filter impurity NaCl, after boiling off ethyl acetate, obtain intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol are yellow liquid 2.10g, and productive rate is 62%;
(3), the product karanal is synthetic:
measuring 40ml dimethylbenzene joins in 250ml three neck round-bottomed flasks, take 13.80g 3, 5-dimethyl-4-cyclohexene formaldehyde and 17.86g intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol stir down successively and join in dimethylbenzene, then add the 0.25g sal enixum under stirring, heating in water bath backflow 1.5h, after having reacted, be cooled to room temperature, add 2.5g anhydrous sodium sulphate hermetically drying 12h, remove by filter anhydrous sodium sulphate, dimethylbenzene in the pressure reducing and steaming filtrate, obtain crude product, crude product underpressure distillation under nitrogen protection, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get final product karanal sterling 21.0g, be colourless liquid, productive rate is 79%.
Embodiment 3:
(1), intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate is synthetic:
Taking the 0.66g sodium Metal 99.5 slowly puts in the 120mL three-necked bottle that the absolute dehydrated alcohol of 80mL is housed (room temperature).After the sodium total overall reaction, slowly splash into 4.17g 2-methyl-malonic ester with constant pressure funnel, stirring and refluxing 50min, more slowly drip 4.95g 2-n-butyl bromide, under 90 ℃, back flow reaction 5h is in reaction process, with GC and TLC following response process;
After reaction finishes, reaction mixture is cooled to room temperature, boils off etoh solvent, add the water dilution of 3 times of volume of mixture, then with the dilution extracted with diethyl ether 3 times of 3 times of liquid volumes afterwards, combining extraction liquid is washed 2 times with distilled water, the saturated NaCl aqueous solution respectively, the dry moisture of removing, filter out impurities after NaCl, steam except the ether in filtrate, namely obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate, be colourless liquid 4.15g, productive rate is 75%;
(2), intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol is synthetic:
Taking 4.60g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL, take the 0.46g sodium Metal 99.5, being cut into the 3mm fritter divides 3 times to add in ester, slowly drip again the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after adding for the third time the absolute dehydrated alcohol of 5mL, then add the 16mL dehydrated alcohol, heating keeps reacting 5h under reflux state, in reaction process, with GC and TLC following response process;
After reaction finishes, mixture is heated under 80 ℃ boil off low-boiling-point substance, add the water dilution of 3 times of volume of mixture, with the ethyl acetate extraction organic layer of 3 times of liquid volumes after dilution, after washing extraction liquid three times with 5% dilute hydrochloric acid and saturated NaCl respectively again, the dry moisture of removing is after the NaCl that filters out impurities, after boiling off the ethyl acetate in filtrate, obtain intermediate (II) 2-methyl-2-sec-butyl-1,3 propylene glycol are yellow liquid 2.80g, and productive rate is 61%;
(3), the product karanal is synthetic:
measuring 40ml dimethylbenzene joins in 250ml three neck round-bottomed flasks, take 13.80g 3, 5-dimethyl-4-cyclohexene formaldehyde and 18.25g intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol stir down successively and join in dimethylbenzene, then add the 0.3g sal enixum under stirring, heating in water bath backflow 2h, after having reacted, be cooled to room temperature, add 3.0g anhydrous sodium sulphate hermetically drying 12h, remove by filter anhydrous sodium sulphate, dimethylbenzene in the pressure reducing and steaming filtrate, obtain crude product, crude product underpressure distillation under nitrogen protection, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get final product karanal sterling 21.5g, be colourless liquid, productive rate is 81%.
Claims (1)
1. the synthetic method of a karanal, it is characterized in that: synthesis step is:
(1), synthesizing of intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute dehydrated alcohol of 25mL-80mL, add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, after stirring and refluxing 30min-50min, add 2.49g-4.95g 2-n-butyl bromide, at the temperature of 80-90 ℃, back flow reaction 4h-5h, after reaction finishes, reaction mixture is cooled to room temperature, boil off etoh solvent, add volume of mixture 1-3 water dilution doubly, again with diluting rear liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid, extraction liquid is used respectively distilled water, the saturated NaCl aqueous solution is washed 2 times, the dry moisture of removing, after filtering out impurities, ether in filtrate is steamed remove, namely obtain 2-methyl-2-sec-butyl-diethyl malonate,
(2), intermediate (II) 2-methyl-2-sec-butyl-1, 3 propylene glycol synthetic: the fritter that the 0.23g-0.46g sodium Metal 99.5 is cut into 2-3mm divides and joins in 2.30g-4.60g 2-methyl-2-sec-butyl-diethyl malonate under stirring for 3 times, drip the absolute dehydrated alcohol of 5mL after adding sodium Metal 99.5 at every turn, after sodium Metal 99.5 adds, add again the 3-16mL dehydrated alcohol, heating keeps reacting 4-5h under reflux state, after reaction finishes, mixture is heated under 76-80 ℃ boil off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly, with the organic layer in liquid volume 1-3 ethyl acetate extraction diluent doubly after dilution, with 5% dilute hydrochloric acid and saturated NaCl, extraction liquid is washed three times respectively again, the dry moisture of removing, filter out impurities, steam except after the ethyl acetate in filtrate, obtain 2-methyl-2-sec-butyl-1, 3 propylene glycol,
(3), synthesizing of product karanal: with 13.80g 3, 5-dimethyl-4-tetrahydrobenzene formaldehyde and 17.52g-18.25g 2-methyl-2-sec-butyl-1, 3 propylene glycol under agitation join in 40ml dimethylbenzene successively, then add the 0.2-0.3g sal enixum under stirring, heating in water bath backflow 1h-2h, after having reacted, be cooled to room temperature, add 2-3g anhydrous sodium sulphate hermetically drying 12h, filter out impurities, steam except the dimethylbenzene in filtrate, obtain crude product, under nitrogen protection, crude product is carried out underpressure distillation, pressure is-1200Pa, cut under collecting 118-119 ℃, namely get the final product karanal.
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| CN105259281B (en) * | 2015-07-22 | 2018-08-10 | 谱尼测试科技(天津)有限公司 | The assay method of karanal content in a kind of plastic toy material |
| CN105911199B (en) * | 2016-06-23 | 2019-10-15 | 丁立平 | The detection method of karanal in a kind of articles for washing |
| CN115670960A (en) * | 2022-11-03 | 2023-02-03 | 福建卫辰生物技术有限公司 | Mosquito-repelling spray liquid |
| CN116813446A (en) * | 2023-06-26 | 2023-09-29 | 天津玉健生物工程有限公司 | Method for reducing and removing sulfone from sulfonyl compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0276998A2 (en) * | 1987-01-29 | 1988-08-03 | Unilever Plc | Perfumery materials |
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| EP0276998A2 (en) * | 1987-01-29 | 1988-08-03 | Unilever Plc | Perfumery materials |
Non-Patent Citations (4)
| Title |
|---|
| 吴秀芹.香料吐纳麝香和卡拉花醛的合成研究.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 》.2011,(第09期),B018-22第43-49页. |
| 汪朝阳.缩羰化合物香料合成研究进展.《化工时刊》.2000,(第8期),6-8. |
| 缩羰化合物香料合成研究进展;汪朝阳;《化工时刊》;20001231(第8期);6-8 * |
| 香料吐纳麝香和卡拉花醛的合成研究;吴秀芹;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 》;20110915(第09期);B018-22第43-49页 * |
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