CN104496850A - Method for synthesizing p-methylphenylacetonitrile - Google Patents
Method for synthesizing p-methylphenylacetonitrile Download PDFInfo
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- CN104496850A CN104496850A CN201410773545.6A CN201410773545A CN104496850A CN 104496850 A CN104496850 A CN 104496850A CN 201410773545 A CN201410773545 A CN 201410773545A CN 104496850 A CN104496850 A CN 104496850A
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- phase
- methylbenzeneacetonitrile
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- oil phase
- transfer catalyst
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- 238000000034 method Methods 0.000 title abstract description 6
- RNHKXHKUKJXLAU-UHFFFAOYSA-N 2-(4-methylphenyl)acetonitrile Chemical compound CC1=CC=C(CC#N)C=C1 RNHKXHKUKJXLAU-UHFFFAOYSA-N 0.000 title abstract 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005070 sampling Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- WMGVPDQNPUQRND-UHFFFAOYSA-N (2-methylphenyl)acetonitrile Chemical compound CC1=CC=CC=C1CC#N WMGVPDQNPUQRND-UHFFFAOYSA-N 0.000 claims description 35
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 13
- 238000010189 synthetic method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000013517 stratification Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 208000012839 conversion disease Diseases 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000002825 nitriles Chemical group 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LZBOHNCMCCSTJX-UHFFFAOYSA-N 1-(chloromethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CCl)=C1 LZBOHNCMCCSTJX-UHFFFAOYSA-N 0.000 description 1
- VDAACASZHZYJJX-UHFFFAOYSA-N 2-[4-(aminomethyl)phenyl]acetonitrile Chemical compound NCC1=CC=C(CC#N)C=C1 VDAACASZHZYJJX-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 stratification Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing p-methylphenylacetonitrile. The method comprises the following steps: (1) adding p-methylbenzyl chloride and water into a cyaniding reactor, pouring weighted sodium cyanide, stirring and dissolving, further adding a phase transfer catalyst, slowly heating to 50-70 DEG C, keeping the temperature at 50-70 DEG C and reacting, sampling and analyzing and when the content of p-methylbenzyl chloride is less than or equal to 1% or after p-methylbenzyl chloride is completely reacted, stopping the reaction; standing and layering an oil phase and a water phase and separating the water phase containing sodium chloride and a small amount of sodium cyanide, wherein the retained oil phase part is a cyanide liquid; and (2) adding a 0-5wt% Na2CO3 aqueous liquid, stirring, washing the cyanide liquid oil phase, standing and layering, discharging the water phase and retaining the oil phase part to obtain p-methylphenylacetonitrile; and if a product having better appearance and quality is needed, rectifying p-methylphenylacetonitrile. The method has the advantages of simplicity in operation, shorter process route, small emission of three wastes, relatively less environmental pollution, no need of additional use of organic solvents during the reaction process, mild reaction conditions, high purity of the product and the like.
Description
Technical field
The present invention relates to the synthetic method of a kind of fine chemical product to methylbenzeneacetonitrile.
Background technology
To methylbenzeneacetonitrile, have another name called 2-(4-aminomethyl phenyl) acetonitrile, structural formula is as follows:
A kind of important organic synthesis intermediate, for the preparation of the intermediate etc. of spices, dyestuff, medicine and agricultural chemicals.Its synthetic method is reported there are no open source literature.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of simple to operate, synthetic method to methylbenzeneacetonitrile that environmental pollution is relatively less.
The technical scheme solved the problems of the technologies described above is: a kind of synthetic method to methylbenzeneacetonitrile, comprises the following steps:
(1) add methyl benzyl chloride and water in cyanogenation still, pour load weighted sodium cyanide into, stirring and dissolving, continue to add phase-transfer catalyst, described phase-transfer catalyst is Tetrabutyl amonium bromide or tetrabutylammonium chloride; Add by 1:1.01 ~ 1.1 mol ratio methyl benzyl chloride and sodium cyanide, the add-on of phase-transfer catalyst is to methyl benzyl chloride weight 3 ~ 10 ‰, and the add-on of water is 60 ~ 90% of sodium cyanide weight; Slowly be heated to 50 ~ 70 DEG C, remain on 50 ~ 70 DEG C of reactions, sampling analysis, to stopped reaction after methyl benzyl chloride≤1% or complete reaction; Stratification oil phase and aqueous phase, separate aqueous phase, and the oil phase part of reservation is divided into cyanating solution.
(2) 0 ~ 5wt% Na is added
2cO
3the aqueous solution, agitator treating cyanating solution oil phase, stratification, discharges aqueous phase, retains oil phase part and divides and obtain methylbenzeneacetonitrile.
Further technical scheme of the present invention is: step (2) obtains putting into rectifying tower reactor again to methylbenzeneacetonitrile and carries out rectifying, collects 95 ~ 130 DEG C, the cut under-98 ~-101KPa condition, obtains purity >=99% pair methylbenzeneacetonitrile.
0 ~ 5wt% Na in step (2)
2cO
3the add-on of the aqueous solution is 30 ~ 80% of cyanating solution volume.
In step (1), phase-transfer catalyst adds at twice under the constant prerequisite of total amount, adds the phase-transfer catalyst of gross weight 45 ~ 55%, when reaction conversion ratio is 45 ~ 55%, then add remaining phase transfer catalyst when reacting and just starting.
A kind of synthetic method to methylbenzeneacetonitrile of the present invention, with to methyl benzyl chloride for raw material, obtain methylbenzeneacetonitrile through cyanogenation, reaction formula is as follows:
A kind of synthetic method to methylbenzeneacetonitrile of the present invention has following beneficial effect:
1), simple to operate.
2), operational path is shorter, and three waste discharge is few.
3), do not need in reaction process in addition with an organic solvent, thus do not need the operation of solvent recuperation.
4), reaction conditions is gentle, and safety is secure, is easy to realize industrialization.
5), reaction belongs to single reaction, and thoroughly, do not have solvent again, product purity is high in reaction.The unreacted a small amount of impurity that methyl benzyl chloride and raw material are brought methyl benzyl chloride to methylbenzeneacetonitrile and trace is only had in final organic phase.
6), there is no side reaction, can ensure that consumption is low, product purity can be made again high; Production cost is relatively low.
Below, in conjunction with the accompanying drawings and embodiments the technical characteristic of a kind of synthetic method to methylbenzeneacetonitrile of the present invention is described further.
Accompanying drawing explanation
Fig. 1: production equipment of the present invention.
In figure: 1-to methyl benzyl chloride feeding tube, 2-water feeding tube, 3-cyanogenation still, 4-sodium cyanide, catalyst charging hole, 5, other materials add entrance, 6-is to methylbenzeneacetonitrile rectifying tower reactor, 7-is to methyl benzyl chloride receiver, and 8-is to methylbenzeneacetonitrile receiver, and 81-connects vacuum pipe.
Embodiment
Embodiment 1: to the preparation method of methylbenzeneacetonitrile, comprise the following steps:
1, add in cyanogenation still 3 methyl benzyl chloride 273kg, water 80L, pour load weighted sodium cyanide 100kg into, stirring and dissolving, continue to add Tetrabutyl amonium bromide 0.6kg; Slowly be heated to 55 ~ 65 DEG C, remain on 50 ~ 65 DEG C of reactions, when reaction conversion ratio about 50%, add Tetrabutyl amonium bromide 0.5kg, continue reaction, sampling analysis, stopped reaction after to methyl benzyl chloride≤1% or complete reaction; Stratification oil phase and aqueous phase, separate the aqueous phase of sodium chloride-containing and a small amount of sodium cyanide, and collect reuse or process, the oil phase part of reservation is divided into cyanating solution;
2, add clear water 120kg, agitator treating cyanating solution oil phase, stratification, discharge aqueous phase, collect, part reuse, discharges after partially disposed, retains oil phase part and divides and obtain first product to methylbenzeneacetonitrile.
3, rectifying: first product puts into rectifying tower reactor 6 to methylbenzeneacetonitrile, collects 90 ~ 100 DEG C, and the cut under-95 ~-98Kpa condition obtains, to methyl benzyl chloride (wherein containing methylbenzeneacetonitrile), being back to cyanogenation; When containing methyl benzyl chloride≤0.3% in tower reactor, being switched to methylbenzeneacetonitrile receiver 8, collecting 95 ~ 130 DEG C, the cut under-98 ~-101KPa condition, obtain purity >=99% pair methylbenzeneacetonitrile.The a small amount of raffinate of tower reactor collects raffinate storage tank.
Embodiment 2: a kind of synthetic method to methylbenzeneacetonitrile, comprises the following steps:
1, add methyl benzyl chloride 250ml(methyl benzyl chloride content >=98% in the glass four-hole bottle of 500ml) and water 65g, pour load weighted sodium cyanide 96g into, stirring and dissolving, continue to add phase-transfer catalyst Tetrabutyl amonium bromide 1.3g; Slowly be heated to 55 ~ 65 DEG C, remain on 55 ~ 65 DEG C of reactions, if reaction is too violent, difficult control of temperature, can reduce mixing speed; Sampling analysis, to stopped reaction after methyl benzyl chloride≤1% or complete reaction; Stratification oil phase and aqueous phase, separate the aqueous phase of sodium chloride-containing and a small amount of sodium cyanide, collection and treatment, and the oil phase part of reservation is divided into cyanating solution;
2,1 ~ 5wt% Na is added
2cO
3the aqueous solution, agitator treating cyanating solution oil phase, stratification, discharges aqueous phase; Add clear water 80g again, agitator treating cyanating solution oil phase, stratification, aqueous phase collection and treatment.Retain oil phase part to divide and obtain methylbenzeneacetonitrile.Sampling analysis, to methylbenzeneacetonitrile >=97%.
Embodiment 1, with after clear water washing, then carries out rectifying, obtain to the purity of methylbenzeneacetonitrile than embodiment 2 without rectifying obtain high to the purity of methylbenzeneacetonitrile.Embodiment 1 through rectifying obtain limpid to methylbenzeneacetonitrile outward appearance, can be used as production marketing, it is poor to methylbenzeneacetonitrile visual appearance that embodiment 2 obtains, and can be used as intermediate product, be used as other reaction raw material.
In embodiment 2, add Na
2cO
3the object of the aqueous solution considers from secure context, guarantee system meta-alkalescence.
Claims (4)
1. to a synthetic method for methylbenzeneacetonitrile, it is characterized in that: comprise the following steps:
(1) add methyl benzyl chloride and water in cyanogenation still, pour load weighted sodium cyanide into, stirring and dissolving, continue to add phase-transfer catalyst, described phase-transfer catalyst is Tetrabutyl amonium bromide or tetrabutylammonium chloride; Add by 1:1.01 ~ 1.1 mol ratio methyl benzyl chloride and sodium cyanide, the add-on of phase-transfer catalyst is to methyl benzyl chloride weight 3 ~ 10 ‰, and the add-on of water is 60 ~ 90% of sodium cyanide weight; Slowly be heated to 50 ~ 70 DEG C, remain on 50 ~ 70 DEG C of reactions, sampling analysis, to stopped reaction after methyl benzyl chloride≤1% or complete reaction; Stratification oil phase and aqueous phase, separate aqueous phase, and the oil phase part of reservation is divided into cyanating solution;
(2) 0 ~ 5wt% Na is added
2cO
3the aqueous solution, agitator treating cyanating solution oil phase, stratification, discharges aqueous phase, retains oil phase part and divides and obtain methylbenzeneacetonitrile.
2. the synthetic method to methylbenzeneacetonitrile according to claim 1, it is characterized in that: step (2) obtains putting into rectifying tower reactor again to methylbenzeneacetonitrile and carries out rectifying, collect 95 ~ 130 DEG C, the cut under-98 ~-101KPa condition, obtain purity >=99% pair methylbenzeneacetonitrile.
3. the synthetic method to methylbenzeneacetonitrile according to claim 1 and 2, is characterized in that: 0 ~ 5wt% Na in step (2)
2cO
3the add-on of the aqueous solution is 30 ~ 80% of cyanating solution volume.
4. the synthetic method to methylbenzeneacetonitrile according to claim 1 and 2, it is characterized in that: in step (1), phase-transfer catalyst adds at twice under the constant prerequisite of total amount, the phase-transfer catalyst of gross weight 45 ~ 55% is added when reacting and just starting, when reaction conversion ratio is 45 ~ 55%, then add remaining phase transfer catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410773545.6A CN104496850A (en) | 2014-12-15 | 2014-12-15 | Method for synthesizing p-methylphenylacetonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410773545.6A CN104496850A (en) | 2014-12-15 | 2014-12-15 | Method for synthesizing p-methylphenylacetonitrile |
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|---|---|
| CN104496850A true CN104496850A (en) | 2015-04-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536599A (en) * | 1978-08-22 | 1985-08-20 | Sumitomo Chemical Company, Limited | Synthesis of amine derivatives |
| WO2003070666A2 (en) * | 2002-02-15 | 2003-08-28 | Value Recovery, Inc. | Process for making organic products from non-product streams using phase transfer catalysis |
| CN101456826A (en) * | 2008-11-24 | 2009-06-17 | 张家港市华盛化学有限公司 | Method for preparing 2-chloro-4-fluorobenzene nitrile |
| CN102381918A (en) * | 2011-08-31 | 2012-03-21 | 河南科技大学 | Method for synthesizing benzyl cyanide compound by using benzyl chloride compound |
| CN104402698A (en) * | 2014-10-29 | 2015-03-11 | 柳州丰康泰科技有限公司 | 2-(4-methylphenyl)propionic acid syntehsis method |
-
2014
- 2014-12-15 CN CN201410773545.6A patent/CN104496850A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536599A (en) * | 1978-08-22 | 1985-08-20 | Sumitomo Chemical Company, Limited | Synthesis of amine derivatives |
| WO2003070666A2 (en) * | 2002-02-15 | 2003-08-28 | Value Recovery, Inc. | Process for making organic products from non-product streams using phase transfer catalysis |
| CN101456826A (en) * | 2008-11-24 | 2009-06-17 | 张家港市华盛化学有限公司 | Method for preparing 2-chloro-4-fluorobenzene nitrile |
| CN102381918A (en) * | 2011-08-31 | 2012-03-21 | 河南科技大学 | Method for synthesizing benzyl cyanide compound by using benzyl chloride compound |
| CN104402698A (en) * | 2014-10-29 | 2015-03-11 | 柳州丰康泰科技有限公司 | 2-(4-methylphenyl)propionic acid syntehsis method |
Non-Patent Citations (2)
| Title |
|---|
| B.TAMAMI，S.GHASEMI: "Nucleophilic Substitution Reactions Using Polyacrylamide-Based Phase Transfer Catalyst in Organic and Aqueous Media", 《J.IRAN.CHEM.SOC.》, vol. 5, 31 October 2008 (2008-10-31), XP036299632, DOI: doi:10.1007/BF03246485 * |
| STEVEN L.REGEN: "Triphase Catalysis.Applications to Organic Synthesis", 《J.ORG.CHEM.》, vol. 42, no. 5, 31 December 1977 (1977-12-31), pages 875 - 879 * |
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