CN102040526A - Preparation method of N,N-diallyl aniline - Google Patents
Preparation method of N,N-diallyl aniline Download PDFInfo
- Publication number
- CN102040526A CN102040526A CN2010105626140A CN201010562614A CN102040526A CN 102040526 A CN102040526 A CN 102040526A CN 2010105626140 A CN2010105626140 A CN 2010105626140A CN 201010562614 A CN201010562614 A CN 201010562614A CN 102040526 A CN102040526 A CN 102040526A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- mol ratio
- aniline
- reaction solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CJIPLMHXHKPZGM-UHFFFAOYSA-N n,n-bis(prop-2-enyl)aniline Chemical compound C=CCN(CC=C)C1=CC=CC=C1 CJIPLMHXHKPZGM-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 allyl halide Chemical class 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 238000004440 column chromatography Methods 0.000 claims abstract description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 235000015320 potassium carbonate Nutrition 0.000 claims description 17
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 9
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 8
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 6
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 4
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 4
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 4
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种N，N-二烯丙基苯胺的制备方法，该方法包括以下步骤：(1)依次将烯丙基卤化物、胺类化合物、碱放入反应溶剂中，在20～70℃下进行反应，反应完全后得反应液；(2)将所述反应液进行萃取后得萃取液；(3)将所述萃取液经干燥、浓缩、柱层析分离后即得N，N-二烯丙基苯胺。本发明条件温和，反应时间短，后处理简单，收率高，而且此方法不需要贵金属作为催化剂，是一项符合对环境友好的绿色合成技术，可以实现规模生产，具有较好的工业应用前景。The present invention relates to a kind of preparation method of N, N-diallyl aniline, and this method comprises the following steps: (1) allyl halide, amine compound, alkali are put into reaction solvent successively, in 20～70 The reaction is carried out at ℃, and the reaction liquid is obtained after the reaction is complete; (2) the extract is obtained after the reaction liquid is extracted; (3) the extract is dried, concentrated, and separated by column chromatography to obtain N, N - Diallylaniline. The invention has mild conditions, short reaction time, simple post-treatment, high yield, and the method does not require precious metals as catalysts, is an environmentally friendly green synthesis technology, can realize large-scale production, and has good industrial application prospects .
Description
Technical field
The present invention relates to the N in the Synthetic Organic Chemistry field, N-diallyl aniline relates in particular to a kind of N, the preparation method of N-diallyl aniline.
Background technology
N, N-diallyl aniline as the important organic synthesis intermediate of a class, is the intermediate of medicine, agrochemicals industry, manufacturing dyestuff and the plastics of preciousness.
Traditional N, the preparation of N-diallyl aniline be in solution with mineral acid as catalyzer and halohydrocarbon or methyl-sulfate as alkylating reagent and amine reaction.Adopting the aniline attack halohydrocarbon that electrophilic group is arranged at present is the best approach of synthetic N-alkyl substituted benzene amine, but its productive rate and selectivity are not significantly improved.This major cause is that the alkylating while of carrying out amine also carrying out its competing reaction, such as generating secondary amine, tertiary amine and quaternary ammonium salt.
Research about this type of reaction early has report, but many limitation are all arranged.The beginning people do not adopt catalyzer, but, the nucleophilicity of part aromatic amine is lower, with the very long reaction times do not participate in substantially yet the reaction or productive rate very low, adopt the sterically hindered big of bulky amine, reaction effect is also bad, and the boiling point of part amine is low, the waste of will volatilizing before reacting again is many, does not make full use of raw material.Overcome these shortcomings so people begin to add catalyzer, the complicated catalyzer of the employing that has must synthesize and just can obtain, such as Pd (OCOCF
3)
2-PPh
3, Mo
3S
4Pd (η
3-allyl) grade slightly improves productive rate but cumbersome, and people adopted simple catalyzer to react afterwards.Synthetic N-alkyl substituted benzene amine great majority adopt precious metal as catalyzer both at home and abroad recently, as Pd, and Pt, Ru.Because having high efficiency, specificity and stereoselectivity under the catalysis of this precious metal, the allylation of amine is widely used in the organic synthesis; Simultaneously this precious metal can be formed allyl metal complex by the nucleophilic reagent attack, generates N-alkyl substituted benzene amine thereby react with amine.But this metal catalyst costs an arm and a leg.
Present green Synthetic Organic Chemistry, and development environment close friend's methodology of organic synthesis more and more cause people's attention, are just becoming an important research content of modern chemistry.The present invention studied in green medium and the catalyst-free condition under synthetic N, the method for N-diallyl substituted aniline.
Summary of the invention
Technical problem to be solved by this invention provides a kind of cost cheapness, efficient, synthetic N fast and under the catalyst-free condition, the preparation method of N-diallyl aniline.
For addressing the above problem, a kind of N of the present invention, the preparation method of N-diallyl aniline may further comprise the steps:
(1) successively allyl halide, aminated compounds, alkali are put into reaction solvent, under 20～70 ℃, react, get reaction solution after reacting completely; The mol ratio of wherein said aminated compounds and described allyl halide is 1: 2～1: 3.6, and the mol ratio of described aminated compounds and described alkali is 1: 3～1: 6, and the mol ratio of described aminated compounds and described reaction solvent is 1: 102～1: 333;
(2) after described reaction solution is extracted extraction liquid;
(3) with described extraction liquid drying, concentrate, promptly get N, N-diallyl aniline after the column chromatography for separation.
Allyl halide in the described step (1) is any one in chlorallylene, the allyl bromide 98.
The structural formula of the aminated compounds in the described step (1) is: R
1NH
2, R wherein
1Be aryl.
Alkali in the described step (1) is any one in salt of wormwood, sodium bicarbonate, the triethylamine.
Reaction solvent in the described step (1) is one or both the mixture in dehydrated alcohol, the water.
Extraction solvent in the described step (2) is unsaturated carbonate hydrogen ammonium solution and ethyl acetate; Described unsaturated carbonate hydrogen ammonium solution and ethyl acetate respectively with described reaction solvent equivalent.
The present invention compared with prior art has the following advantages:
1, because the present invention does not adopt catalyzer, therefore, make the operation step oversimplify, thereby will foreshorten in the reaction times in 5 hours, realized efficiently, purpose fast.
2, because temperature of reaction of the present invention is lower, so the reaction conditions gentleness.
3, because the present invention adopts alkali to promote down synthetic N, N-diallyl aniline, therefore, not only method is simple, and the efficient height, and product yield is up to 99%.
4, because raw material of the present invention is easy to get, do not need any catalyzer, therefore reduced production cost.
5, the present invention is one and meets environment amenable green synthesis techniques, can realize scale production, has better industrial application prospects.
Embodiment
1 one kinds of N of embodiment, the preparation method of N-diallyl aniline may further comprise the steps:
(1)------(volume ratio of dehydrated alcohol and water is 2ml to aniline, alkali---salt of wormwood is put into reaction solvent---dehydrated alcohol/water: 1ml), react 2h under 70 ℃ for allyl bromide 98, aminated compounds successively with allyl halide.Entire reaction course is followed the tracks of with thin layer chromatography, promptly every sampling in 5 minutes, on silica-gel plate, splash into reaction solution point sample, stock liquid aniline point sample respectively with kapillary, two point samples are on the same straight line, silica-gel plate are put into to fill the exhibition bottle that volume ratio is the mixed solution of 10: 1 sherwood oil and ethyl acetate then.After limp is finished, silica-gel plate is placed under the ultraviolet lamp or in the iodine flask observes again, if the point that does not flush with stock liquid aniline in the reaction solution shows then to react completely that this moment must reaction solution.
The mol ratio of aniline and allyl bromide 98 is 1: 3, and the mol ratio of aniline and salt of wormwood is 1: 4, and the mol ratio of aniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
(2) the RE-52AA type Rotary Evaporators that adopts Shanghai inferior Rong Shenghua company limited to produce earlier removes solvent under reduced pressure at 40 ℃, in reaction solution, add again with the saturated sodium bicarbonate solution of reaction solvent amount equivalent and with reaction solvent amount equivalent ethyl acetate, organic phase is told in extraction; Water ethyl acetate extraction three times then merge to organic phase, get extraction liquid.
(3) anhydrous magnesium sulfate added make its drying in the extraction liquid, after filtering filtrate; The RE-52AA type Rotary Evaporators that adopts Shanghai inferior Rong Shenghua company limited to produce then removes solvent under reduced pressure at 40 ℃, gets concentrated solution; The silica gel that adds 2～3 times of concentrated solution quality in concentrated solution is mixed sample again, to mix sample and put into chromatography column, the mixed solution that adds volume ratio and be 80: 1 sherwood oil and ethyl acetate carries out wash-out to be separated, collect elutriant at last, elutriant is put into Rotary Evaporators, promptly get N, N-diallyl aniline at 40 ℃ after concentrating.N, N-diallyl aniline productive rate is 86%.
2 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, and aminated compounds is a m-nitraniline, and alkali is salt of wormwood, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 2ml to dehydrated alcohol/water: 1ml).
Wherein the mol ratio of m-nitraniline and allyl bromide 98 is 1: 3, and the mol ratio of m-nitraniline and salt of wormwood is 1: 4, and the mol ratio of m-nitraniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
Temperature of reaction is 70 ℃, and the reaction times is 5h, and productive rate is 80%.
3 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is a chlorallylene, and aminated compounds is a P-nethoxyaniline, and alkali is salt of wormwood, and reaction solvent is a water.
Wherein the mol ratio of P-nethoxyaniline and chlorallylene is 1: 2.5, and the mol ratio of P-nethoxyaniline and salt of wormwood is 1: 6, and the mol ratio of P-nethoxyaniline and reaction solvent water is 1: 333.
Temperature of reaction is 40 ℃, and the reaction times is 6h, and productive rate is 86%.
4 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is a chlorallylene, and aminated compounds is a para-bromoaniline, and alkali is sodium bicarbonate, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 2ml to dehydrated alcohol/water: 1ml).
Wherein the mol ratio of para-bromoaniline and chlorallylene is 1: 3.6, and the mol ratio of para-bromoaniline and sodium bicarbonate is 1: 6, and the mol ratio of para-bromoaniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
Temperature of reaction is 40 ℃, and the reaction times is 5.5h, and productive rate is 65%.
5 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, and aminated compounds is a m-chloro aniline, and alkali is salt of wormwood, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 2ml to dehydrated alcohol/water: 1ml).
Wherein the mol ratio of m-chloro aniline and allyl bromide 98 is 1: 2.5, and the mol ratio of m-chloro aniline and salt of wormwood is 1: 6, and the mol ratio of m-chloro aniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
Temperature of reaction is 70 ℃, and the reaction times is 9h, and productive rate is 68%.
6 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is a chlorallylene, and aminated compounds is to monomethylaniline, and alkali is triethylamine, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 1ml to dehydrated alcohol/water: 2ml).
Wherein the mol ratio to monomethylaniline and chlorallylene is 1: 2, is 1: 5 to the mol ratio of monomethylaniline and triethylamine, is 1: 34 to the mol ratio of monomethylaniline and reaction solvent dehydrated alcohol, with the mol ratio of water be 1: 222.
Temperature of reaction is 40 ℃, and the reaction times is 7h, and productive rate is 45%.
7 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, and aminated compounds is a p-Chlorobenzoic acid amide, and alkali is salt of wormwood, and reaction solvent is a dehydrated alcohol.
Wherein the mol ratio of p-Chlorobenzoic acid amide and allyl bromide 98 is 1: 2.5, and the mol ratio of p-Chlorobenzoic acid amide and salt of wormwood is 1: 3, and the mol ratio of p-Chlorobenzoic acid amide and reaction solvent dehydrated alcohol is 1: 102.
Temperature of reaction is 20 ℃, and the reaction times is 9h, and productive rate is 66%.
8 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, aminated compounds be between monomethylaniline, alkali is salt of wormwood, reaction solvent is that (volume ratio of dehydrated alcohol and water is 2ml to dehydrated alcohol/water: 1ml).
The mol ratio of monomethylaniline and allyl bromide 98 is 1: 2.8 in the middle of it, and the mol ratio of a monomethylaniline and salt of wormwood is 1: 4, and the mol ratio of a monomethylaniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
Temperature of reaction is 65 ℃, and the reaction times is 5h, and productive rate is 79%.
9 one kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, and aminated compounds is an o-toluidine, and alkali is salt of wormwood, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 1ml to dehydrated alcohol/water: 2ml).
Wherein the mol ratio of o-toluidine and allyl bromide 98 is 1: 2.8, and the mol ratio of o-toluidine and salt of wormwood is 1: 4, and the mol ratio of o-toluidine and reaction solvent dehydrated alcohol is 1: 34, with the mol ratio of water be 1: 222.
Temperature of reaction is 55 ℃, and the reaction times is 5.5h, and productive rate is 59%.
10 1 kinds of N of embodiment, the preparation method of N-diallyl aniline is with embodiment 1.
Wherein allyl halide is an allyl bromide 98, and aminated compounds is a P-nethoxyaniline, and alkali is salt of wormwood, and reaction solvent is that (volume ratio of dehydrated alcohol and water is 2ml to dehydrated alcohol/water: 1ml).
Wherein the mol ratio of P-nethoxyaniline and allyl bromide 98 is 1: 3, and the mol ratio of P-nethoxyaniline and salt of wormwood is 1: 4, and the mol ratio of P-nethoxyaniline and reaction solvent dehydrated alcohol is 1: 68, with the mol ratio of water be 1: 111.
Temperature of reaction is 70 ℃, and the reaction times is 1.5h, and productive rate is 99%.
Each raw material in the foregoing description 1～10 is analytical pure.
Claims (6)
1. N, the preparation method of N-diallyl aniline may further comprise the steps:
(1) successively allyl halide, aminated compounds, alkali are put into reaction solvent, under 20～70 ℃, react, get reaction solution after reacting completely; The mol ratio of wherein said aminated compounds and described allyl halide is 1: 2～1: 3.6, and the mol ratio of described aminated compounds and described alkali is 1: 3～1: 6, and the mol ratio of described aminated compounds and described reaction solvent is 1: 102～1: 333;
(2) after described reaction solution is extracted extraction liquid;
(3) with described extraction liquid drying, concentrate, promptly get N, N-diallyl aniline after the column chromatography for separation.
2. a kind of N as claimed in claim 1, the preparation method of N-diallyl aniline is characterized in that: the allyl halide in the described step (1) is any one in chlorallylene, the allyl bromide 98.
3. a kind of N as claimed in claim 1, the preparation method of N-diallyl aniline is characterized in that: the structural formula of the aminated compounds in the described step (1) is: R
1NH
2, R wherein
1Be aryl.
4. a kind of N as claimed in claim 1, the preparation method of N-allyl group aniline is characterized in that: the alkali in the described step (1) is any one in salt of wormwood, sodium bicarbonate, the triethylamine.
5. a kind of N as claimed in claim 1, the preparation method of N-diallyl aniline is characterized in that: the reaction solvent in the described step (1) is one or both the mixture in dehydrated alcohol, the water.
6. a kind of N as claimed in claim 1, the preparation method of N-diallyl aniline is characterized in that: the extraction solvent in the described step (2) is unsaturated carbonate hydrogen ammonium solution and ethyl acetate; Described unsaturated carbonate hydrogen ammonium solution and ethyl acetate respectively with described reaction solvent equivalent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105626140A CN102040526A (en) | 2010-11-26 | 2010-11-26 | Preparation method of N,N-diallyl aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105626140A CN102040526A (en) | 2010-11-26 | 2010-11-26 | Preparation method of N,N-diallyl aniline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102040526A true CN102040526A (en) | 2011-05-04 |
Family
ID=43907107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105626140A Pending CN102040526A (en) | 2010-11-26 | 2010-11-26 | Preparation method of N,N-diallyl aniline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102040526A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603538A (en) * | 2012-03-12 | 2012-07-25 | 西北师范大学 | Method for preparing N, 2-allyl anilines |
| CN102718664A (en) * | 2012-06-08 | 2012-10-10 | 甘肃省化工研究院 | Preparation method of N-allyl aniline compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701560A (en) * | 1985-05-22 | 1987-10-20 | Rhone-Poulenc Specialties Chimiques | Process for the preparation of N-2-alkenyl-m-trifluoromethylanilines |
| US4956496A (en) * | 1987-12-23 | 1990-09-11 | Rhone-Poulenc Chimie | Process for allylation of perhaloalkyl-, perhaloalkoxy- and perhaloalkylthioanilines in the presence of a catalyst |
| US5210305A (en) * | 1988-07-29 | 1993-05-11 | Rhone-Poulenc Chimie | Process for preparing n-alkylanilines and n-allylanilines |
| CN101633627A (en) * | 2009-07-14 | 2010-01-27 | 浙江闰土股份有限公司 | A kind of method of producing 3-(N, N-diallyl) amino-4-methoxyacetanilide |
-
2010
- 2010-11-26 CN CN2010105626140A patent/CN102040526A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701560A (en) * | 1985-05-22 | 1987-10-20 | Rhone-Poulenc Specialties Chimiques | Process for the preparation of N-2-alkenyl-m-trifluoromethylanilines |
| US4956496A (en) * | 1987-12-23 | 1990-09-11 | Rhone-Poulenc Chimie | Process for allylation of perhaloalkyl-, perhaloalkoxy- and perhaloalkylthioanilines in the presence of a catalyst |
| US5210305A (en) * | 1988-07-29 | 1993-05-11 | Rhone-Poulenc Chimie | Process for preparing n-alkylanilines and n-allylanilines |
| CN101633627A (en) * | 2009-07-14 | 2010-01-27 | 浙江闰土股份有限公司 | A kind of method of producing 3-(N, N-diallyl) amino-4-methoxyacetanilide |
Non-Patent Citations (2)
| Title |
|---|
| 张英菊等: "2-甲氧基-5-乙酰氨基-N,N-二烯丙基苯胺的合成研究", 《染料工业》, vol. 36, no. 02, 15 April 1999 (1999-04-15) * |
| 李耀华等: "3-(N,N-二烯丙基)氨基-4-甲氧基乙酰苯胺合成研究", 《湖北民族学院学报(自然科学版)》, no. 04, 30 December 2005 (2005-12-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603538A (en) * | 2012-03-12 | 2012-07-25 | 西北师范大学 | Method for preparing N, 2-allyl anilines |
| CN102603538B (en) * | 2012-03-12 | 2014-10-15 | 西北师范大学 | Method for preparing N, 2-allyl anilines |
| CN102718664A (en) * | 2012-06-08 | 2012-10-10 | 甘肃省化工研究院 | Preparation method of N-allyl aniline compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106694046B (en) | A kind of preparation method of modified zeolite-like imidazole framework material and its application in carbon dioxide hydrogenation reaction | |
| CN104447443B (en) | A kind of Apremilast and the preparation method of intermediate thereof | |
| CN104478790A (en) | Preparation method of S-type apremilast | |
| CN104263797B (en) | The preparation of the tetrahydro naphthylamines of R 1 | |
| CN104263796A (en) | Preparation method of R-1-aminotetralin | |
| CN104045669A (en) | Separation method suitable for chemical synthesis of salidroside for industrial production | |
| CN101851159B (en) | Method for synthetizing alcohol ester acetate by single step of ethyl acetate and alcohol ester exchange | |
| CN102259025A (en) | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof | |
| CN109096126B (en) | Deuterium labeled D9Synthesis method of clenbuterol hydrochloride | |
| CN102040526A (en) | Preparation method of N,N-diallyl aniline | |
| CN103086845A (en) | Method for preparing L-menthol | |
| CN106542984A (en) | A kind of preparation method of 2 methyl of perfluor, 3 pentanone | |
| CN102040527A (en) | Preparation method of N,N-benzyl diphenylamine | |
| CN103553943A (en) | A method for preparing p-aminophenol by hydrogenation of nitrobenzene | |
| CN105399793A (en) | Cholanic acid preparation method | |
| CN104311404A (en) | Method for producing cinnamyl aldehyde | |
| CN113929575B (en) | Preparation method of (1R, 2S) -methyl dihydrojasmonate | |
| CN103980270A (en) | Method for preparing (R)-3-quinuclidinol | |
| CN104262169B (en) | The preparation of R-2-tetrahydro naphthylamine | |
| CN103435477A (en) | Novel method for synthesizing para-ethoxybenzoic acid | |
| CN103360217B (en) | Preparation method for S-(-)-1,1-diphenyl-1,2-propylene glycol | |
| CN111943805A (en) | Preparation method of (R) -3-chloro-1, 2-propanediol | |
| CN103980095B (en) | A kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol | |
| CN103664826A (en) | Preparation method for aminonaphthol compound | |
| CN104610064A (en) | One-pot method using carbonate as a catalyst for the preparation of dimethyl carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110504 |