CN104030929B - The synthetic method of N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine - Google Patents
The synthetic method of N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine Download PDFInfo
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Abstract
N, N-diethyl-3,7-dimethyl-(Z)-2, the synthetic method of 6-octadiene-1-amine, it relates to technical field of chemistry and chemical engineering, with isoprene for raw material and diethylamine, butyl lithium, it is obtained by reacting formula product N through potassium salt catalyst, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine；Its synthesis technique is simple, easy to operate, and yield is high, and Suitable commercial produces.
Description
Technical field:
The present invention relates to technical field of chemistry and chemical engineering, be specifically related to a kind of N, N-diethyl-3, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine.
Background technology:
N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine, popular name N, N-diethyl-neryl amine (is called for short: NDEA), wherein the isomer of NDEA is N, N-diethyl-3,7-dimethyl-(E)-2,6-octadiene-1-amine.They are raw material and the intermediate of important spices and essence, it is synthesize acyclic and cyclic monoterpenes spice, important source material such as citral, citronellal, nerol, MENTHOL and linalool etc., simultaneously also can as the precursor of some chiral drugs, through asymmetry catalysis synthesis, there is optically active medicine, such as methoprene, vitamin A and E etc..Along with growing to essence and flavoring agent demand of people, the spice of natural extract cannot meet again the supply in market, and research and development NDEA chemically composite perfume becomes more and more important.
At present, the synthetic method of NDEA has: 1) neryl chlorine reacts with diethylamine, but cost is high, and post processing is inconvenient, is not suitable for industrialized production；2) with isoprene and diethylamine for raw material, in lithium or n-BuLi catalytic reaction, yield is 77%, however it is necessary that use benzene or other organic solvent, and environment compatibility is poor.
In the exploitation using second method, also there is the report of some early stages, but yield is not ideal, big all in 55% (fine-chemical intermediate 42 volume 2 phase, 2012, Yang Yang etc.) to 88% (OrganicSynthesesColl.Vol.8.183-190,1993), the yield mentioned in two sections of patents (US2002/0004620 and US4186148) of the U.S. is also relatively low, and the highest is 85%.
Summary of the invention:
It is an object of the invention to provide a kind of N, N-diethyl-3, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, its synthesis technique is simple, easy to operate, and yield is high, and Suitable commercial produces.
In order to solve the problem existing for background technology, the present invention adopts the following technical scheme that with isoprene for raw material and diethylamine, butyl lithium, is obtained by reacting formula product N, N-diethyl-3 through potassium salt catalyst, 7-dimethyl-(Z)-2,6-octadiene-1-amine.
Described potassium salt catalyst selected from potassium carbonate, potassium hydroxide, potassium isopropoxide or potassium tert-butoxide can the mixture of one or more described catalyst, it is preferable that potassium carbonate.
Described isoprene, diethylamine, butyl lithium, potassium salt catalyst mol ratio be 2-8:1:0.01-1:0.01-0.05, it is preferable that 6-7:1:0.2-0.3:0.02-0.03.
Described reaction condition carries out under inert gas shielding, it is preferable that nitrogen.
Described reaction temperature is at 60-100 DEG C, and 70-75 DEG C is optimal reaction temperature.
Described reaction pressure is at 1-3 kilogram, and 2-2.5 kilogram is optimum response pressure.
The described response time at 6-20 hour, it is further recommended that 8-10 hour.
There is advantages that content is more than 95%, yield is more than 93%, and technique is simple, easy to operate, production suitable for industrialized.
Detailed description of the invention:
Contribute to understanding the present invention by following example, but be not limited to present disclosure.
Embodiment 1:
Isoprene (70mL, 0.70mol, 7.0eq.), Et is added in the vexed tank of 100mL2NH (7.3g, 0.10mol, 1.0eq.), potassium carbonate (0.35g, 2.5mmol), it is cooled with an ice bath to 0oC.Slowly dripping n-BuLi (9.6mL, 24mmol, 2.5M) under nitrogen protection, in keeping, temperature is less than 15oC, seals after dripping.Continuing stirring 15 minutes in ice bath, be then to slowly warm up to 75oC, stir 6 hours, pressure is about 2 kilograms.After completion of the reaction, remove oil bath, drip 0.3mL water wherein after the cooling of question response liquid, stir 2 minutes, it is spin-dried for low-boiling point material, using oil pump rectification under vacuum, obtain colourless oil liquid, GC detects N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine content 95%, yield 93%.
Embodiment 2:
Isoprene (50mL, 0.50mol, 5.0eq.), Et is added in the vexed tank of 100mL2NH (7.3g, 0.10mol, 1.0eq.), potassium carbonate (0.35g, 2.5mmol), it is cooled with an ice bath to 0oC.Slowly dripping n-BuLi (9.6mL, 24mmol, 2.5M) under nitrogen protection, in keeping, temperature is less than 5oC, after completion of the reaction, seals after dripping.Stirring 15 minutes in ice bath, be then to slowly warm up to 95oC, stir 16 hours, pressure is about 2.5 kilograms.After completion of the reaction, remove oil bath, drip 0.3mL water wherein after the cooling of question response liquid, stir 2 minutes, it is spin-dried for low-boiling point material, using oil pump rectification under vacuum, obtain colourless oil liquid, GC detects N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine content 88%, yield 33%.
Embodiment 3:
Isoprene (50mL, 0.50mol, 5.0eq.), Et is added in the vexed tank of 100mL2NH (7.3g, 0.10mol, 1.0eq.), potassium carbonate (0.35g, 2.5mmol), it is cooled with an ice bath to 0oC.Slowly dripping n-BuLi (9.6mL, 24mmol, 2.5M) under nitrogen protection, in keeping, temperature is less than 15oC, seals after dripping.Continuing stirring 15 minutes in ice bath, be then to slowly warm up to 75oC, stir 16 hours, pressure is about 2 kilograms.After completion of the reaction, remove oil bath, drip 0.3mL water wherein after the cooling of question response liquid, stir 2 minutes, it is spin-dried for low-boiling point material, using oil pump rectification under vacuum, obtain colourless oil liquid, GC detects N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine content 76%, yield 69%.
Embodiment 4:
Isoprene (50mL, 0.50mol, 5.0eq.), Et is added in the vexed tank of 100mL2NH (7.3g, 0.10mol, 1.0eq.), potassium carbonate (0.35g, 2.5mmol), it is cooled with an ice bath to 15oC.Slowly dripping n-BuLi (9.6mL, 24mmol, 2.5M) under nitrogen protection, in keeping, temperature is less than 15oC, seals after dripping.Ice bath stirs 15 minutes, is then to slowly warm up to 60oC, stirs 16 hours.Pressure is about 1.8 kilograms.After completion of the reaction, remove oil bath, drip 0.3mL water wherein after the cooling of question response liquid, stir 2 minutes, it is spin-dried for low-boiling point material, using oil pump rectification under vacuum, obtain colourless oil liquid, GC detects N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine content 88%, yield 73%.
Embodiment 5:
Isoprene (80mL, 0.80mol, 8.0eq.), Et is added in the vexed tank of 100mL2NH (10mL, 0.10mol, 1.0eq.), potassium carbonate (0.35g, 2.5mmol), it is cooled with an ice bath to 15oC.Slowly dripping n-BuLi (9.6mL, 24mmol, 2.5M) under nitrogen protection, in keeping, temperature is less than 15oC, seals after dripping.Stirring 15 minutes in ice bath, be then to slowly warm up to 75oC, stir 16 hours, pressure is about 1.8 kilograms.After completion of the reaction, remove oil bath, drip 0.3mL water wherein after the cooling of question response liquid, stir 2 minutes, it is spin-dried for low-boiling point material, using oil pump rectification under vacuum, obtain colourless oil liquid, GC detects N, N-diethyl-3,7-dimethyl-(Z)-2,6-octadiene-1-amine content 85%, yield 76%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (7)
1.N, N-diethyl-3, 7-dimethyl-(Z)-2, the synthetic method of 6-octadiene-1-amine, it is characterized in that with isoprene for raw material and diethylamine, butyl lithium, it is obtained by reacting formula product N through potassium salt catalyst, N-diethyl-3, 7-dimethyl-(Z)-2, 6-octadiene-1-amine, when adding butyl lithium, first reaction system is carried out ice bath, it is cooled to 0 DEG C, then butyl lithium is slowly dripped, in keeping, temperature is less than 15 DEG C, described potassium salt catalyst is selected from potassium carbonate, potassium hydroxide, the mixture of a kind of or above-mentioned catalyst in potassium isopropoxide or potassium tert-butoxide.
2. N, N-diethyl-3 according to claim 1, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that described potassium salt catalyst is potassium carbonate.
3. N according to claim 1, N-diethyl-3, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that described isoprene, diethylamine, butyl lithium, potassium salt catalyst mol ratio be 2-8:1:0.01-1:0.01-0.05.
4. N, N-diethyl-3 according to claim 1, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that: described reaction condition carries out under inert gas shielding.
5. N, N-diethyl-3 according to claim 1, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that described reaction temperature is at 60-100 DEG C.
6. N, N-diethyl-3 according to claim 1, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that described reaction pressure is at 1-3 kilogram.
7. N, N-diethyl-3 according to claim 1, the synthetic method of 7-dimethyl-(Z)-2,6-octadiene-1-amine, it is characterised in that the described response time was at 6-20 hour.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107219A (en) * | 1976-05-14 | 1978-08-15 | Nissan Chemical Industries Ltd. | Process for producing chain terpene alcohol |
| US4266087A (en) * | 1978-11-13 | 1981-05-05 | Givaudan Corporation | Process for preparing a myrcenol, cis-ocimenol mixture substantially free of trans-ocimenol |
| EP1142859A2 (en) * | 2000-04-07 | 2001-10-10 | Takasago International Corporation | Process for producing optically active 3,7-dimethyl-6-octenol and process for producing intermediate therefor |
| CN102850227A (en) * | 2012-09-19 | 2013-01-02 | 常州胜杰化工有限公司 | Prochiral allyl amine compound and synthetic method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107219A (en) * | 1976-05-14 | 1978-08-15 | Nissan Chemical Industries Ltd. | Process for producing chain terpene alcohol |
| US4266087A (en) * | 1978-11-13 | 1981-05-05 | Givaudan Corporation | Process for preparing a myrcenol, cis-ocimenol mixture substantially free of trans-ocimenol |
| EP1142859A2 (en) * | 2000-04-07 | 2001-10-10 | Takasago International Corporation | Process for producing optically active 3,7-dimethyl-6-octenol and process for producing intermediate therefor |
| CN102850227A (en) * | 2012-09-19 | 2013-01-02 | 常州胜杰化工有限公司 | Prochiral allyl amine compound and synthetic method thereof |
Non-Patent Citations (3)
| Title |
|---|
| N，N-二乙基-3，7-二甲基-(Z)-2，6-辛二烯-1-胺的合成研究;杨阳等;《精细化工中间体》;20120430;第42卷(第2期);第42页实验部分 * |
| TELOMERIZATION OF ISOPRENE WITH DIALKYLAMINE: N,N-DIETHYLNERYLAMINE;Kunihiko Takabe等;《Organic Syntheses》;19931231;第8卷;第190页 * |
| 以叔戊氧基钾为调节剂的丁二烯和异戊二烯共聚合;张春庆等;《合成橡胶工业》;20110415;第27卷(第6期);第385页 * |
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