CN105294474A - Method for preparing menthane diacetyl amide from p-menthadiene - Google Patents
Method for preparing menthane diacetyl amide from p-menthadiene Download PDFInfo
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Abstract
The invention discloses a method for preparing menthane diacetyl amide from p-menthadiene. The method includes using p-menthadiene as a raw material, reacting p-menthadiene with acetonitrile catalyzed by strong protonic acid aqueous solution to prepare the product, performing neutralization reaction of reaction solution and inorganic strong base aqueous solution to be neutral solution after the full reaction, adding non-water-soluble organic solvent to perform extraction, collecting the precipitation product of standing organic layer, and filtering and washing the precipitation to deposition the solid menthane diacetyl amide. The menthane diacetyl amide has high product yield and purity. Compared with the original preparation method, the method uses p-menthadiene which is cheap and easily available as raw material, has a simple technology route, can greatly reduce the production cost of the menthane diacetyl amide and down-stream product, has a simple operation, and has low toxicity.
Description
Technical field:
The present invention relates to a kind of processing method of producing alkane diethylamide in the Meng, especially relate to a kind of by the Meng diene and acetonitrile single step reaction method produce the Meng alkane diethylamide processing method.
Background technology
Acid amides C – N key is the important feature primitive of the bioactive molecules such as peptide and protein in organism, therefore, many compounds with amide group all have excellent desinsection, antibacterial, weeding, Antiphytoviral and antitumor isoreactivity, are widely used in the field such as medicine, agricultural chemicals.In addition, many amidess are also important organic synthesis intermediates, are often used to synthesis heteroatoms or heterogeneous ring compound, have very important using value in industries such as chemical industry, spices, dyestuff and light textiles.
Since the sixties in last century people's Late Cambrian amides systemic fungicide such as Schmeling, the tens of kinds of medicines with amide structure develop listing in succession, but most compound in use there will be unavoidable toxicity, cause various environment and health problem.With the natural product of nontoxic or low toxicity for raw material, by carrying out the corresponding amide derivatives of modification preparation to reactive site wherein, can increase the biocompatibility of respective compound, reduce the harm to environment and human and livestock health, be the emphasis direction of present stage new drug development.
Turps is the monoterpenes natural essential oil of domestic high yield, from its can derivative synthesis various structures close to the fine chemicals of natural product.Because most turpentine derivatives is very low or almost do not have toxicity to the toxicity of people and animals, increasing turps derived product is used to pesticide synergistic agent, expelling parasite or attractive activity agent, weedicide, antibiotic bactericide etc.As one of turps derivative compound that a class is important, in recent years, synthesis and the application of terpene amides are subject to extensive concern, and pesticide synergistic, weeding, antibacterial, antitumor etc. in be used widely.
The Meng, alkane diethylamide was a kind of monocyclic terpene diamide turpentine derivatives, the physics and chemistry special due to it and structural performance, and the Meng, alkane diethylamide had huge application prospect at medicine, pesticide field.In current existing research, preparation alkane diamines in the Meng mainly contains two kinds of approach: (1) Koval ' skaya (ZhurnalOrganicheskoiKhimii, 1991,27 (4): 757-762) in isopinocampheol Ritter reacts, etc. find that there is a small amount of Meng alkane diethylamide generate, owing to being only one of lower by product of this reaction content, preparation alkane diethylamide efficiency in the Meng is lower in this way, and purifying process is loaded down with trivial details; (2) Koval ' skaya (KhimiyaPrirodnykhSoedinenii; 1989; 5:649-655) etc. and Zhong Xing etc. (CN201110103300.9 (2012)) with 1; 8-alkane in Meng glycol (i.e. terpinum) and acetonitrile are raw material; Ritter reaction is carried out respectively in sulfuric acid or its acetic acid mixed solution; obtain alkane diethylamide in the Meng; but raw material 1; the cost of 8-alkane in Meng glycol (i.e. terpinum) is higher, is unfavorable for carrying out large-scale production and application.And explicitly point out in this section of document, under these processing condition, alkane diethylamide in the Meng can not be generated to diolefinic compounds in the Meng (as limonene) with acetonitrile reaction.If can with to the Meng diene for raw material, realized the preparation of alkane diethylamide in the Meng by alkene acidylate, will effectively reduce its production cost, there is higher prospects for commercial application.
Summary of the invention
In order to solve the shortcomings such as the efficiency that the existing Meng, alkane diethylamide technology of preparing existed is low, cost is high, purifying process is loaded down with trivial details; the invention provides a kind of method by preparing alkane diethylamide in the Meng to diene in the Meng; with cheap and easy to get to the Meng diene and hypotoxic acetonitrile carry out isomery acylation reaction for raw material; simplify production process route; reduce alkane diethylamide and the production cost of derived product thereof in the Meng, decrease the harm of surrounding environment.
Technical scheme of the present invention is: a kind of method by preparing alkane diethylamide in the Meng to diene in the Meng, using diene in the Meng is raw material, under the catalysis of strong protonic acid, carry out amideization reaction with acetonitrile prepare product, inorganic base aqueous solution neutralization reaction liquid is used after abundant reaction, add water-insoluble organic solvent extraction, collect and leave standstill organic layer precipitation product, filtration, washing precipitation obtain alkane diethylamide solid in the Meng.
Strong protonic acid used is a kind of or several arbitrarily aqueous solution in sulfuric acid, phosphoric acid, tosic acid, trifluoromethanesulfonic acid, and add-on is to the Meng 1.0 ~ 3.0 times of diene molar weight.
The add-on of acetonitrile is to the Meng 1.5 ~ 4.0 times of diene molar weight.
Reaction is carried out at 0 DEG C ~ 100 DEG C temperature.
Preferred reaction is carried out at 40 DEG C ~ 80 DEG C temperature.
Reaction times is 1 ~ 12h.
Neutralizing inorganic base aqueous solution used is a kind of or several arbitrarily aqueous solution in potassium hydroxide, sodium hydroxide, ammoniacal liquor.
Extracting water-insoluble organic solvent used is a kind of or several arbitrarily mixture in ether, ester, straight-chain paraffin or naphthenic hydrocarbon.
To diene in the Meng be 1,3-to the Meng diene, Isosorbide-5-Nitrae (5)-to the Meng diene, Isosorbide-5-Nitrae (8)-to the Meng diene, 1,8-to one or more the mixture in Meng diene.
Extract any one that water-insoluble organic solvent used is preferably in ethyl acetate, sherwood oil, normal hexane or hexanaphthene.
Beneficial effect
1. Technology of the present invention can abandon the defects such as existing preparation alkane in Meng diethylamide process efficiency is low, purifying process is loaded down with trivial details, is applicable to multiple batches of, production in enormous quantities.
2. the present invention with cheap and easy to get to the Meng diene for raw material, prepare alkane diethylamide in the Meng by single step reaction, greatly reduce alkane diethylamide and the production cost of derived product thereof in the Meng.
Accompanying drawing explanation
Fig. 1 is alkane diethylamide infrared spectrogram (cm in the Meng
-1: 3314, ν
n-H; 2916, ν
c-H; 1642, ν
c=O).
Fig. 2 is alkane diethylamide mass spectrum (m/z:255.05, M+H in the Meng
+).
Fig. 3 is alkane diethylamide hydrogen nuclear magnetic resonance spectrogram in the Meng (δ: 6.90 ~ 7.40, NH).
Specific embodiments
A kind of processing method of synthesizing alkane diethylamide in the Meng, using diene in the Meng is raw material, under the catalysis of strong protonic acid, carry out Ritter amidate action with acetonitrile prepare product, use inorganic base aqueous solution neutralization reaction liquid to neutral after abundant reaction, add water-insoluble organic solvent extraction, collect and leave standstill organic layer precipitation product, filtration, washing precipitation obtain alkane diethylamide solid in the Meng.Reaction formula is as follows:
Specifically comprise the following steps:
The first step: amideization is reacted: 17.1g (about 0.126mol) is added in 250mL reactor to the one in Meng diene and acetonitrile, mechanical stirring mixes to solution, slowly the strong protonic acid aqueous solution is instilled under ice-water bath condition, dropwise and be slowly warming up to certain temperature, insulation reaction 1h ~ 12h afterwards.Wherein strong protonic acid solution is by a kind of or two kinds and the above water solubles of sulfuric acid, phosphoric acid, tosic acid, trifluoromethanesulfonic acid, mass concentration scope is 20% ~ 80%, add-on is to the Meng 1.0 ~ 3.0 times of diene molar weight, the add-on of acetonitrile is to the Meng 1.5 ~ 4.0 times of diene molar weight, reaction can be carried out at 0 DEG C ~ 100 DEG C temperature, and preferably 40 DEG C ~ 80 DEG C is optimal reaction temperature scope.
1 to diene in the Meng, 3-is to diene in the Meng (α-terpinene), 1,4 (5)-to diene in the Meng (γ-terpinene), 1,4 (8)-to diene in the Meng (terpinolene), 1,8-to one or more the mixture (kautschin or terpinolene) among diene in the Meng (limonene).
Second step: after amideization reaction terminates, reaction solution inorganic strong alkali is neutralized to neutrality, add water-insoluble organic solvent extraction, collect and leave standstill organic layer, get 1% collection liquid, add 0.0536g naphthalene, after fully dissolving with ethanol, detect alkane diethylamide content in the Meng by GC, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain alkane diethylamide solid in the Meng.Wherein during neutralization reaction, the inorganic strong alkali aqueous solution used is a kind of or several arbitrarily mixture of potassium hydroxide, aqueous sodium hydroxide solution, ammoniacal liquor.Extracting water-insoluble organic solvent used is a kind of of ether, ester, straight-chain paraffin or naphthenic hydrocarbon or mixtures several arbitrarily.Be more preferably any one of ethyl acetate, sherwood oil, normal hexane or hexanaphthene.
Raw material to the Meng diene, reaction solution, thick product, finished product etc. all use capillary gas chromatography to carry out reaction tracking and analytical study, internal standard substance: naphthalene.
The instrument that the GC used in the present invention analyzes and condition: Shimadzu 2014AF type gas chromatograph.RTX-5 quartz capillary gas chromatographic column (Φ 0.25mm × 30m × 0.25 μm), temperature programming 70 DEG C → 130 DEG C → 270 DEG C, two sections of temperature rise rates are respectively: 3 DEG C/min and 10 DEG C/min, sampler temperature 260 DEG C, fid detector temperature 260 DEG C, carrier gas is N
2.
Embodiment 1
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 41.3% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 2
Added in 250mL reactor with 15.5g acetonitrile (0.378mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 27.9% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 3
Added in 250mL reactor with 7.8g acetonitrile (0.189mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 28.5% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 4
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 135.7g20% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 6.6% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 5
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 33.9g80% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 16.7% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 6
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 20.6g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.126mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 23.5% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 7
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 61.7g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.378mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 5h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 32.1% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 8
By 17.1g α-terpinene (to diene GC content 93.5% in the Meng, 0.126mol) add in 250mL reactor with 12.4g acetonitrile (0.303mol), mechanical stirring mixes to solution, under ice-water bath condition, slowly instillation contains the tosic acid saturated aqueous solution of 0.277mol tosic acid, dropwise and be slowly warming up to 55 DEG C afterwards, insulation reaction 5h, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 23.1% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, filter, washing precipitation obtains 1, 8-alkane in Meng diethylamide.
Embodiment 9
By 17.1g kautschin (to diene GC content 93.5% in the Meng, 0.126mol) add in 250mL reactor with 12.4g acetonitrile (0.303mol), mechanical stirring mixes to solution, under ice-water bath condition, slowly instillation contains the 60% trifluoromethanesulfonic acid aqueous solution of 0.277mol trifluoromethanesulfonic acid, dropwise and be slowly warming up to 55 DEG C afterwards, insulation reaction 5h, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 24.7% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, filter, washing precipitation obtains 1, 8-alkane in Meng diethylamide.
Embodiment 10
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g γ-terpinene (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 35 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 32.9% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 11
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 85 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 35.6% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 12
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 3h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 25.0% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 13
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g terpinolene (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution potassium hydroxide aqueous solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 40.8% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 14
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add petroleum ether extraction, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 38.9% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 15
17.1g limonene (GC content 97.8%, 0.126mol) and 12.4g acetonitrile (0.303mol) are added in 250mL reactor, mechanical stirring mixes to solution, slowly instills the H of 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 61.1% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 16
17.1g terpinolene (GC content 97.8%, 0.126mol) and 12.4g acetonitrile (0.303mol) are added in 250mL reactor, mechanical stirring mixes to solution, slowly instills the H of 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 55 DEG C, insulation reaction 6h afterwards, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, add extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 49.2% after fully dissolving with ethanol, other filtrate leaving standstill separates out solid product, and filtration, washing precipitation obtain 1,8-alkane in Meng diethylamide.
Embodiment 17
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 0 DEG C afterwards, insulation reaction 6h, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, adds extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 2.3% after fully dissolving with ethanol.
Embodiment 18
Added in 250mL reactor with 12.4g acetonitrile (0.303mol) by 17.1g kautschin (to diene GC content 93.5%, 0.126mol in the Meng), mechanical stirring mixes to solution, the H of slow instillation 45.3g60% under ice-water bath condition
2sO
4the aqueous solution is (containing H
2sO
40.277mol), dropwise and be slowly warming up to 100 DEG C afterwards, insulation reaction 6h, after reaction terminates, reaction solution aqueous sodium hydroxide solution is neutralized to neutrality, adds extraction into ethyl acetate, collected organic layer, get 1% collection liquid and add 0.0536g naphthalene, by GC detection alkane diethylamide productive rate in the Meng 3.7% after fully dissolving with ethanol.
Claims (10)
1. one kind by the method being prepared by diene in the Meng to alkane diethylamide in the Meng, it is characterized in that, using diene in the Meng is raw material, under the catalysis of strong protonic acid, carry out amideization reaction with acetonitrile prepare product, inorganic base aqueous solution neutralization reaction liquid is used after abundant reaction, add water-insoluble organic solvent extraction, collect and leave standstill organic layer precipitation product, filtration, washing precipitation obtain alkane diethylamide solid in the Meng.
2. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, it is characterized in that, strong protonic acid used is a kind of or several arbitrarily aqueous solution in sulfuric acid, phosphoric acid, tosic acid, trifluoromethanesulfonic acid, and add-on is to the Meng 1.0 ~ 3.0 times of diene molar weight.
3. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1 and 2, is characterized in that, the add-on of acetonitrile is to the Meng 1.5 ~ 4.0 times of diene molar weight.
4. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, reacts and carries out at 0 DEG C ~ 100 DEG C temperature.
5. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, reacts and carries out at 40 DEG C ~ 80 DEG C temperature.
6. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, the reaction times is 1 ~ 12h.
7. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, neutralizing inorganic base aqueous solution used is a kind of or several arbitrarily aqueous solution in potassium hydroxide, sodium hydroxide, ammoniacal liquor.
8. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, extracting water-insoluble organic solvent used is a kind of or several arbitrarily mixture in ether, ester, straight-chain paraffin or naphthenic hydrocarbon.
9. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, it is characterized in that, 1 to diene in the Meng, 3-to the Meng diene, 1,4 (5)-to the Meng diene, 1,4 (8)-to the Meng diene, 1,8-to one or more the mixture in Meng diene.
10. the method by preparing alkane diethylamide in the Meng to diene in the Meng according to claim 1, is characterized in that, extracting water-insoluble organic solvent used is any one in ethyl acetate, sherwood oil, normal hexane or hexanaphthene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777571A (en) * | 2016-04-08 | 2016-07-20 | 中国林业科学研究院林产化学工业研究所 | N-acetyl-3-foxlene-1-amine and preparation method thereof |
| CN105968037A (en) * | 2016-06-21 | 2016-09-28 | 中国林业科学研究院林产化学工业研究所 | N-acyl-1,2-cyclo-nitrogen-p-menthane, as well as preparation method and herbicidal activity application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777571A (en) * | 2016-04-08 | 2016-07-20 | 中国林业科学研究院林产化学工业研究所 | N-acetyl-3-foxlene-1-amine and preparation method thereof |
| CN105777571B (en) * | 2016-04-08 | 2018-06-19 | 中国林业科学研究院林产化学工业研究所 | N- acetyl group -3- Foxlene -1- amine and preparation method thereof |
| CN105968037A (en) * | 2016-06-21 | 2016-09-28 | 中国林业科学研究院林产化学工业研究所 | N-acyl-1,2-cyclo-nitrogen-p-menthane, as well as preparation method and herbicidal activity application thereof |
| CN106083604A (en) * | 2016-06-21 | 2016-11-09 | 中国林业科学研究院林产化学工业研究所 | A kind of by unsaturated Oleum Terebinthinae monoterpene prepare 1,8 pairs the Meng alkane diamidogen method |
| CN105968037B (en) * | 2016-06-21 | 2018-04-03 | 中国林业科学研究院林产化学工业研究所 | The ring nitrogen of N acyl groups 1,2 is to Meng's alkane and preparation method thereof and activity of weeding application |
| CN106083604B (en) * | 2016-06-21 | 2019-03-19 | 中国林业科学研究院林产化学工业研究所 | A method of by unsaturated turpentine oil monoterpene preparation 1,8- to Meng's alkane diamines |
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