CN102432588A - Method for synthesizing karanal - Google Patents
Method for synthesizing karanal Download PDFInfo
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- CN102432588A CN102432588A CN2011103808435A CN201110380843A CN102432588A CN 102432588 A CN102432588 A CN 102432588A CN 2011103808435 A CN2011103808435 A CN 2011103808435A CN 201110380843 A CN201110380843 A CN 201110380843A CN 102432588 A CN102432588 A CN 102432588A
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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 a kind of compound method of organic cpds, particularly a kind of compound method of OK a karaoke club flower aldehyde.
Background technology
OK a karaoke club flower aldehyde is a kind of synthetic flavour, does not find the existence of its structure at occurring in nature, and it has the strong and gorgeous banksia rose and amber aroma, and fragrance is very lasting.OK a karaoke club flower aldehyde is mainly used in the daily chemical essence prescription; It can be used as functional amber aroma and applies to head perfume to bottom note; Because of the persistence of spices in its prescription is strong, so can not excessively use, this kind amber aroma can both be brought into play conclusive effect until bottom note; Consumption is generally 10% or 1% diluent, has good fabric lasting effect.Compound method about OK a karaoke club flower aldehyde is not still seen relevant bibliographical information at present at home; External English lotus Quest company produces OK a karaoke club flower aldehyde and makes (European patent EP 0276998) with ligustral and corresponding diol through acetalation; But this patent does not relate to the design of the complete synthetic route of OK a karaoke club flower aldehyde; And because raw materials used ligustral is a mixture, the productive rate that obtains OK a karaoke club flower aldehyde at last is very low, so still can not instruct the suitability for industrialized production of OK a karaoke club flower aldehyde.
OK a karaoke club flower aldehyde (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, and outward appearance is a colourless liquid, and specific density (20 ℃ of g/ml) is 0.960-0.966, refractive index (20 ℃) 1.478-1.484, Shan Dian>100 ℃, structural formula is following:
Summary of the invention
In view of the blank of the complete compound method of OK a karaoke club flower aldehyde in the present prior art, and the lower problem of gained productive rate, the present invention designs a scientific and reasonable OK a karaoke club flower aldehyde synthetic route.
The present invention is for achieving the above object, and the technical scheme that is adopted is: a kind of complete compound method of OK a karaoke club flower aldehyde is provided, and concrete synthetic route is divided into three steps:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute absolute ethyl alcohol of 25mL-80mL, treat to add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, behind the stirring and refluxing 30min-50min; Add 2.49g-4.95g 2-NBB, under 80-90 ℃ temperature, back flow reaction 4h-5h; Reaction is cooled to room temperature with reaction mixture after finishing, and boils off etoh solvent; Add volume of mixture 1-3 water dilution doubly, again with diluting back liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid; Extraction liquid is washed 2 times with zero(ppm) water, the saturated NaCl aqueous solution respectively, and the dry moisture of removing is behind the NaCl that filters out impurities; The steaming of ether in the filtrate is removed, promptly obtain 2-methyl-2-sec.-butyl-ethyl malonate;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is 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-ethyl malonate under stirring for 3 times, adds the absolute absolute ethyl alcohol of Dropwise 5 mL behind the sodium Metal 99.5 at every turn; After sodium Metal 99.5 adds, add the 3-16mL absolute ethyl alcohol again, heating keeps reflux state reaction 4-5h down; After reaction finishes, mixture heating under 76-80 ℃ is boiled off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly; With the organic layer in the dilution back liquid volume 1-3 ethyl acetate extraction diluent doubly, it is inferior with 5% Hydrogen chloride and saturated NaCl extraction liquid to be given a baby a bath on the third day after its birth respectively again, the dry moisture of removing; NaCl filters out impurities; After steaming the ETHYLE ACETATE that removes in the filtrate, obtain 2-methyl-2-sec.-butyl-1,3 Ucar 35;
(3), product OK a karaoke club flower aldehyde is synthetic: with 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 17.52g-18.25g 2-methyl-2-sec.-butyl-1,3 Ucar 35 under agitation joins in the 40ml YLENE successively, stirs then to add the 0.2-0.3g sal enixum down; Heating in water bath backflow 1h-2h after having reacted, is cooled to room temperature; Add 2-3g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h, filter out impurities, remove the YLENE in the filtrate under reduced pressure; Obtain crude product, under the nitrogen protection, crude product is carried out underpressure distillation; Pressure is-1200Pa, and the cut under collecting 118-119 ℃ promptly gets final product OK a karaoke club flower aldehyde.
Beneficial effect: the present invention adopts the backstepping method to design the route of a complete Synthesis Card garland aldehyde, has wherein synthesized midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35, for final synthetic product OK a karaoke club flower aldehyde provides required raw material.The present invention is in the step of synthetic final product OK a karaoke club flower aldehyde, and on the basis of existing technology, operation conditions optimization makes the OK a karaoke club flower aldehyde productive rate that obtains also improve a lot than the document record, the synthetic foundation that provides of these industriallization for OK a karaoke club flower aldehyde.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 a synthetic route synoptic diagram of the present invention.
Embodiment
A kind of complete compound method of OK a karaoke club flower aldehyde is provided, and concrete synthetic route is divided into three steps:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute absolute ethyl alcohol of 25mL-80mL, treat to add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, behind the stirring and refluxing 30min-50min; Add 2.49g-4.95g 2-NBB, under 80-90 ℃ temperature, back flow reaction 4h-5h; Reaction is cooled to room temperature with reaction mixture after finishing, and boils off etoh solvent; Add volume of mixture 1-3 water dilution doubly, again with diluting back liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid; Extraction liquid is washed 2 times with zero(ppm) water, the saturated NaCl aqueous solution respectively, and the dry moisture of removing is behind the NaCl that filters out impurities; The steaming of ether in the filtrate is removed, promptly obtain 2-methyl-2-sec.-butyl-ethyl malonate;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is 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-ethyl malonate under stirring for 3 times, adds the absolute absolute ethyl alcohol of Dropwise 5 mL behind the sodium Metal 99.5 at every turn; After sodium Metal 99.5 adds, add the 3-16mL absolute ethyl alcohol again, heating keeps reflux state reaction 4-5h down; After reaction finishes, mixture heating under 76-80 ℃ is boiled off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly; With the organic layer in the dilution back liquid volume 1-3 ethyl acetate extraction diluent doubly, it is inferior with 5% Hydrogen chloride and saturated NaCl extraction liquid to be given a baby a bath on the third day after its birth respectively again, the dry moisture of removing; NaCl filters out impurities; After steaming the ETHYLE ACETATE that removes in the filtrate, obtain 2-methyl-2-sec.-butyl-1,3 Ucar 35;
(3), product OK a karaoke club flower aldehyde is synthetic: with 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 17.52g-18.25g 2-methyl-2-sec.-butyl-1,3 Ucar 35 under agitation joins in the 40ml YLENE successively, stirs then to add the 0.2-0.3g sal enixum down; Heating in water bath backflow 1h-2h after having reacted, is cooled to room temperature; Add 2-3g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h, filter out impurities, remove the YLENE in the filtrate under reduced pressure; Obtain crude product, under the nitrogen protection, crude product is carried out underpressure distillation; Pressure is-1200Pa, and the cut under collecting 118-119 ℃ promptly gets final product OK a karaoke club flower aldehyde.
Embodiment 1:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic:
Taking by weighing the 0.33g sodium Metal 99.5 slowly puts in the 50mL three-necked bottle that the absolute absolute ethyl alcohol of 25mL is housed (room temperature).After treating the sodium total overall reaction, slowly splash into 2.11g 2-methyl-malonic ester, stirring and refluxing 30min with constant pressure funnel; Slowly drip 2.49g 2-NBB again, under 80 ℃ temperature, back flow reaction 4h; In the reaction process, with GC and TLC following response process;
Reaction is cooled to room temperature with reactant mixture after finishing, and boils off etoh solvent; Add the water dilution of equal-volume mixture; With the extracted with diethyl ether of equal-volume dilution back liquid 3 times, behind the combining extraction liquid, wash extract 2 times with distilled water, the saturated NaCl aqueous solution respectively again; The dry moisture of removing in the extract; Remove by filter impurity NaCl, and steam and remove ether, promptly obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate; Be colourless liquid 2.00g, productive rate is 72%;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is synthetic:
Taking by weighing 2.30g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL; Take by weighing the 0.23g sodium metal; The fritter that is cut into 2mm divides and adds for 3 times in the ester; The slow more absolute absolute ethyl alcohol of Dropwise 5 mL behind each adding sodium metal; After adding the absolute absolute ethyl alcohol of 5mL for the third time, add the 3mL absolute ethyl alcohol again, heating keeps reflux state reaction 4h down; In the course of reaction, with GC and TLC following response process;
After reaction finishes; Mixture heating under 76 ℃ is boiled off low-boiling-point substance, add the water dilution of equal-volume mixture, with the ethyl acetate extraction organic layer of equal-volume dilution back liquid; After washing extract three times with 5% watery hydrochloric acid and saturated NaCl respectively again; The dry moisture of removing in the extract removes by filter impurity NaCl, boil off ethyl acetate after; Obtain intermediate (II) 2-methyl-2-sec-butyl-1; 3 propane diols are yellow liquid 1.50g, and productive rate is 65%;
(3), product OK a karaoke club flower aldehyde is synthetic:
Measure 40ml YLENE and join in the 250ml three neck round-bottomed flasks, take by weighing 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 17.52g midbody (II) 2-methyl-2-sec.-butyl-1; 3 Ucar 35 stir successively and join in the YLENE, stir then to add 0.2g sal enixum, heating in water bath backflow 1h down; After having reacted, be cooled to room temperature, add 2g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h; Remove by filter the YLENE in SODIUM SULPHATE ANHYDROUS 99PCT, the pressure reducing and steaming filtrate, obtain crude product, crude product underpressure distillation under nitrogen protection; Pressure is-1200Pa, and the cut under collecting 118-119 ℃ promptly gets the pure article 20.7g of final product OK a karaoke club flower aldehyde; Be colourless liquid, productive rate is 78%.
Embodiment 2:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic:
Taking by weighing the 0.50g sodium Metal 99.5 slowly puts in the 80mL three-necked bottle that the absolute absolute ethyl alcohol of 50mL is housed (room temperature).After treating the sodium total overall reaction, slowly splash into 3.10g 2-methyl-malonic ester with constant pressure funnel, stirring and refluxing 40min slowly drips 3.83g 2-NBB again, and under 85 ℃, back flow reaction 4.5h is in the reaction process, with GC and TLC following response process;
After reaction finishes; Reactant 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 dilution back liquid volumes 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 that the ether in the filter liquor; Promptly obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate, be colourless liquid 3.02g, productive rate is 73%;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is synthetic:
Taking by weighing 3.50g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL; Take by weighing the 0.35g sodium metal; The fritter that is cut into 3mm divides to stir for 3 times down and adds in the ester; The slow more absolute absolute ethyl alcohol of Dropwise 5 mL behind each adding sodium metal; After adding the absolute absolute ethyl alcohol of 5mL for the third time, add the 8mL absolute ethyl alcohol again, heating keeps reflux state reaction 4.5h down; In the course of reaction, with GC and TLC following response process;
After reaction finishes; Mixture heating under 78 ℃ is boiled 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 the dilution; After washing extract three times with 5% watery hydrochloric acid and saturated NaCl respectively again; The dry moisture of removing removes by filter impurity NaCl, boil off ethyl acetate after; Obtain intermediate (II) 2-methyl-2-sec-butyl-1; 3 propane diols are yellow liquid 2.10g, and productive rate is 62%;
(3), product OK a karaoke club flower aldehyde is synthetic:
Measure 40ml YLENE and join in the 250ml three neck round-bottomed flasks, take by weighing 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 17.86g midbody (II) 2-methyl-2-sec.-butyl-1; 3 Ucar 35 stir down successively and join in the YLENE, stir then to add 0.25g sal enixum, heating in water bath backflow 1.5h down; After having reacted, be cooled to room temperature, add 2.5g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h; Remove by filter the YLENE in SODIUM SULPHATE ANHYDROUS 99PCT, the pressure reducing and steaming filtrate, obtain crude product, crude product underpressure distillation under nitrogen protection; Pressure is-1200Pa, and the cut under collecting 118-119 ℃ promptly gets the pure article 21.0g of final product OK a karaoke club flower aldehyde; Be colourless liquid, productive rate is 79%.
Embodiment 3:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic:
Taking by weighing the 0.66g sodium Metal 99.5 slowly puts in the 120mL three-necked bottle that the absolute absolute ethyl alcohol of 80mL is housed (room temperature).After treating the sodium total overall reaction, slowly splash into 4.17g 2-methyl-malonic ester with constant pressure funnel, stirring and refluxing 50min slowly drips 4.95g 2-NBB again, and under 90 ℃, back flow reaction 5h is in the reaction process, with GC and TLC following response process;
After reaction finishes; Reactant mixture is cooled to room temperature, boils off etoh solvent; Add the water dilution of 3 times of volume of mixture, with the extracted with diethyl ether of 3 times of dilution back liquid volumes 3 times, combining extraction liquid is washed 2 times with distilled water, the saturated NaCl aqueous solution respectively again; The dry moisture of removing; Filter out impurities behind the NaCl, steam the ether that removes in the filter liquor, promptly obtain intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate; Be colourless liquid 4.15g, productive rate is 75%;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is synthetic:
Taking by weighing 4.60g intermediate (I) 2-methyl-2-sec-butyl-diethyl malonate joins in two mouthfuls of flasks of 50mL; Take by weighing the 0.46g sodium metal; Being cut into the 3mm fritter divides and adds for 3 times in the ester; The slow more absolute absolute ethyl alcohol of Dropwise 5 mL behind each adding sodium metal; After adding the absolute absolute ethyl alcohol of 5mL for the third time, add the 16mL absolute ethyl alcohol again, heating keeps reflux state reaction 5h down; In the course of reaction, with GC and TLC following response process;
After reaction finishes; Mixture heating under 80 ℃ is boiled 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 the dilution; After washing extract three times with 5% watery hydrochloric acid and saturated NaCl respectively again; The dry moisture of removing, behind the NaCl that filters out impurities, boil off the ethyl acetate in the filter liquor after; Obtain intermediate (II) 2-methyl-2-sec-butyl-1; 3 propane diols are yellow liquid 2.80g, and productive rate is 61%;
(3), product OK a karaoke club flower aldehyde is synthetic:
Measure 40ml YLENE and join in the 250ml three neck round-bottomed flasks, take by weighing 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 18.25g midbody (II) 2-methyl-2-sec.-butyl-1; 3 Ucar 35 stir down successively and join in the YLENE, stir then to add 0.3g sal enixum, heating in water bath backflow 2h down; After having reacted, be cooled to room temperature, add 3.0g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h; Remove by filter SODIUM SULPHATE ANHYDROUS 99PCT, the YLENE in the pressure reducing and steaming filtrate obtains crude product; Crude product underpressure distillation under nitrogen protection, pressure be-1200Pa, the cut under collecting 118-119 ℃; Promptly get the pure article 21.5g of final product OK a karaoke club flower aldehyde, be colourless liquid, productive rate is 81%.
Claims (1)
1. the compound method of OK a karaoke club flower aldehyde, it is characterized in that: synthesis step is:
(1), midbody (I) 2-methyl-2-sec.-butyl-ethyl malonate is synthetic: the 0.33g-0.66g sodium Metal 99.5 is joined in the absolute absolute ethyl alcohol of 25mL-80mL, treat to add 2.11g-4.17g 2-methyl-malonic ester after the sodium Metal 99.5 complete reaction, behind the stirring and refluxing 30min-50min; Add 2.49g-4.95g 2-NBB, under 80-90 ℃ temperature, back flow reaction 4h-5h; Reaction is cooled to room temperature with reaction mixture after finishing, and boils off etoh solvent; Add volume of mixture 1-3 water dilution doubly, again with diluting back liquid volume 1-3 extracted with diethyl ether doubly 3 times, combining extraction liquid; Extraction liquid is washed 2 times with zero(ppm) water, the saturated NaCl aqueous solution respectively, and the dry moisture of removing is after filtering out impurities; The steaming of ether in the filtrate is removed, promptly obtain 2-methyl-2-sec.-butyl-ethyl malonate;
(2), midbody (II) 2-methyl-2-sec.-butyl-1,3 Ucar 35 is 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-ethyl malonate under stirring for 3 times, adds the absolute absolute ethyl alcohol of Dropwise 5 mL behind the sodium Metal 99.5 at every turn; After sodium Metal 99.5 adds, add the 3-16mL absolute ethyl alcohol again, heating keeps reflux state reaction 4-5h down; After reaction finishes, mixture heating under 76-80 ℃ is boiled off low-boiling-point substance, add volume of mixture 1-3 water dilution doubly; With the organic layer in the dilution back liquid volume 1-3 ethyl acetate extraction diluent doubly, it is inferior with 5% Hydrogen chloride and saturated NaCl extraction liquid to be given a baby a bath on the third day after its birth respectively again, the dry moisture of removing; Filter out impurities; After steaming the ETHYLE ACETATE that removes in the filtrate, obtain 2-methyl-2-sec.-butyl-1,3 Ucar 35;
(3), product OK a karaoke club flower aldehyde is synthetic: with 13.80g 3,5-dimethyl--4-cyclohexene formaldehyde and 17.52g-18.25g 2-methyl-2-sec.-butyl-1,3 Ucar 35 under agitation joins in the 40ml YLENE successively, stirs then to add the 0.2-0.3g sal enixum down; Heating in water bath backflow 1h-2h after having reacted, is cooled to room temperature; Add 2-3g SODIUM SULPHATE ANHYDROUS 99PCT hermetically drying 12h, filter out impurities, steam the YLENE that removes in the filtrate; Obtain crude product, under the nitrogen protection, crude product is carried out underpressure distillation; Pressure is-1200Pa, and the cut under collecting 118-119 ℃ promptly gets final product OK a karaoke club flower aldehyde.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259281A (en) * | 2015-07-22 | 2016-01-20 | 谱尼测试科技(天津)有限公司 | Method for determination of karanal content of plastic toy material |
| CN105911199A (en) * | 2016-06-23 | 2016-08-31 | 福清出入境检验检疫局综合技术服务中心 | Method for detecting karanal in washing product |
| 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 |
-
2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0276998A2 (en) * | 1987-01-29 | 1988-08-03 | Unilever Plc | Perfumery materials |
Non-Patent Citations (3)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 》 20110915 吴秀芹 香料吐纳麝香和卡拉花醛的合成研究 B018-22第43-49页 1 , 第09期 * |
| 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 》 * |
| 汪朝阳: "缩羰化合物香料合成研究进展", 《化工时刊》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259281A (en) * | 2015-07-22 | 2016-01-20 | 谱尼测试科技(天津)有限公司 | Method for determination of karanal content of plastic toy material |
| 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 |
| CN105911199A (en) * | 2016-06-23 | 2016-08-31 | 福清出入境检验检疫局综合技术服务中心 | Method for detecting karanal in washing product |
| 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 |
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