CN102659624A - Method for preparing cyanophenyl compound - Google Patents
Method for preparing cyanophenyl compound Download PDFInfo
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- CN102659624A CN102659624A CN2012101175076A CN201210117507A CN102659624A CN 102659624 A CN102659624 A CN 102659624A CN 2012101175076 A CN2012101175076 A CN 2012101175076A CN 201210117507 A CN201210117507 A CN 201210117507A CN 102659624 A CN102659624 A CN 102659624A
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Abstract
The invention relates to a method for preparing a cyanophenyl compound, which comprises the following steps: adding an alkoxy benzene compound, iodine, catalyst copper nitrate, cyanide and an acetonitrile solvent into a reaction vessel in sequence, wherein the weigh ratio of the alkoxy benzene compound to the cyanide, the catalyst copper nitrate and the iodine is 1:(0.1-5):(0.8-1.2):(0.4-0.5), then sealing the reaction container, agitating and reacting for 5-45 hours at a temperature of 150-200 DEG C, cooling to a room temperature after reaction and purifying a reacted mixture through a column chromatography to obtain the cyanophenyl compound. The preparation method has the beneficial effects that the relatively-cheap the alkoxy benzene compound is taken as a raw material, acid and high-pressure gas are not used, the production cost is remarkably reduced, and as low-boiling point solvent acetonitrile is used, a product is easy to separate and purify.
Description
Technical field
The present invention relates to the chemical intermediate preparation method, be specifically related to a kind of method for preparing compound of benzene nitriles.
Background technology
The cyanobenzene compounds is the important chemical midbody, and the method for synthetic cyanobenzene compounds has multiple, divides by starting raw material and mainly contains five kinds:
(1) with the benzamide compound be raw material (Indian J. Chem. Sect. B, 2003,42,3148-3151), under the effect of dehydrated reagent, produce the cyanobenzene compounds through dehydrating step, reaction formula is following:
(2) be raw material (J. Am. Chem. Soc., 2011,133,10999 – 11005) with the halogeno-benzene compounds, through producing the cyanobenzene compounds with one step of reaction of prussiate, reaction formula is following:
(3) with the phenyl aldehyde compounds be raw material (Synth. Commun., 2004,34,2025-2030), produce the cyanobenzene compounds through aldoxime dehydration, reaction formula is following:
(4) be raw material (Sasaki Y, Utsumi T, Morii A with the toluene compounds; Et al. Manufacture of Carbocyclic or Heterocyclic Nitriles by Vapor phase Ammoxidation [P]; GerOffen, DE 19746883,1988); Produce the cyanobenzene compounds through oxidation proceses of ammonia, reaction formula is following:
(5) during we carry out the research of this patent content, chemist reported with the benzene-like compounds be raw material (
J. Am. Chem. Soc.2012,
134, method 2528-2531).This method is used two equivalent iodate ammonia, two normal cupric nitrates and two normal Glacial acetic acid min. 99.5, and with high boiling N, dinethylformamide under the oxygen effect, carries out cyaniding to phenyl ring as solvent, produces the cyanobenzene compounds.Reaction formula is following:
In above-mentioned five kinds of methods, the benzene feedstock compounds of the 5th kind of method use is comparatively cheap, has bigger industrial application potentiality.Yet the usage quantity of cupric nitrate is bigger in this method; And the use of two equivalent Glacial acetic acid min. 99.5 and oxygen requires high to production unit; High boiling solvent N in addition, the use of dinethylformamide brings bigger difficulty to product separation, and these factors all can cause its industrial cost higher.
Summary of the invention
The objective of the invention is deficiency for solving the problems of the technologies described above; A kind of method for preparing compound of benzene nitriles is provided, and title product is easily separated, requires lower to production unit; And the consumption of catalyzer and auxiliary agent is less, can obviously reduce the production cost of compound of benzene nitriles.
The present invention is the deficiency that solves the problems of the technologies described above; The technical scheme that is adopted is: a kind of method for preparing compound of benzene nitriles adds the alkoxy benzene compounds, iodine, catalyzer cupric nitrate, prussiate and acetonitrile solvent successively in reaction vessel; The amount of substance that alkoxy benzene compounds, prussiate, catalyzer cupric nitrate and iodine add is than being 1:0.1～5:0.8～1.2:0.4～0.5; Sealed reaction vessel then, stirring reaction 5～45h under 150～200 ℃ of conditions, the reaction postcooling is to room temperature; Through column chromatography post reaction mixture is purified, obtain compound of benzene nitriles;
The chemical formula of said alkoxy benzene compounds is following:
Said prussiate is the Tripotassium iron hexacyanide, hydrated iron Potssium Cyanide, hydration yellow prussiate of potash, the Trisodium hexacyanoferrate, hydrated iron sodium cyanide, calcium ferricyanide, iron magnesium cyanide, sodium cyanide or Potssium Cyanide.
The amount of substance that said alkoxy benzene compounds, prussiate, catalyzer cupric nitrate and iodine add is than being 1:0.5:0.8:0.5.
Said being reflected at carried out 35h under 180 ℃.
The acetonitrile solvent add-on is: every 1mmol alkoxy benzene compounds adds 0.2～5mL acetonitrile solvent.
The invention has the beneficial effects as follows:
(1) is raw material with relatively cheap alkoxy benzene compounds, do not use acid and high pressure gas, obviously reduced production cost.
(2) use the low boiling point solvent acetonitrile, the product separate easily is purified.
(3) product purity is high, technology is simple.
Description of drawings:
Fig. 1 is the product 4-phenetole formonitrile HCN of embodiment 1
1H-NMR figure.
Fig. 2 is the product 4-phenetole formonitrile HCN of embodiment 1
13C-NMR figure.
Fig. 3 is the product 4-benzyloxy cyanobenzene of embodiment 2
1H-NMR figure.
Fig. 4 is the product 4-benzyloxy cyanobenzene of embodiment 2
13C-NMR figure.
Fig. 5 is product 4-(the 4-fluorine benzyloxy) cyanobenzene of embodiment 3
1H-NMR figure.
Fig. 6 is product 4-(the 4-fluorine benzyloxy) cyanobenzene of embodiment 3
13C-NMR figure.
Fig. 7 is product 4-(the 2-methyl benzyloxy) cyanobenzene of embodiment 4
1H-NMR figure.
Fig. 8 is product 4-(the 2-methyl benzyloxy) cyanobenzene of embodiment 4
13C-NMR figure.
Fig. 9 is product 2-methyl-4-benzyloxy cyanobenzene of embodiment 5
1H-NMR figure.
Figure 10 is product 2-methyl-4-benzyloxy cyanobenzene of embodiment 5
13C-NMR figure.
Figure 11 is the product 2 of embodiment 6,4-benzyloxy cyanobenzene
1H-NMR figure.
Figure 12 is the product 2 of embodiment 6,4-benzyloxy cyanobenzene
13C-NMR figure.
Figure 13 is product 2-chloro-4-(4-fluorine benzyloxy)-cyanobenzene of embodiment 7
13C-NMR figure.
Figure 14 is product 2-chloro-4-(4-fluorine benzyloxy)-cyanobenzene of embodiment 7
1H-NMR figure.
Figure 15 is the product 4-oxyethyl group-3 of embodiment 8,5-dimethyl benzene formonitrile HCN
13C-NMR figure.
Figure 16 is the product 4-oxyethyl group-3 of embodiment 8,5-dimethyl benzene formonitrile HCN
13C-NMR figure.
Figure 17 is the product 2,3 of embodiment 9,4-trimethoxy-benzonitrile product
1H-NMR figure.
Figure 18 is the product 2,3 of embodiment 9,4-trimethoxy-benzonitrile product
13C-NMR figure.
Embodiment:
Below be specific embodiment of the present invention, but protection scope of the present invention is not limited thereto:
In reaction tubes, add 0.5mmol phenetole, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 4-phenetole formonitrile HCN product, productive rate is 73%.Use
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 2
In reaction tubes, add 0.5mmol benzyloxy benzene, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2.5mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 4-benzyloxy cyanobenzene product, productive rate is 69%.Use
1H-NMR with
13C-NMR confirms the structure of product.
In reaction tubes, add 0.5mmol 4-luorobenzyl phenyl ether, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 1mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 4-(4-fluorine benzyloxy) cyanobenzene product, productive rate is 70%, uses
1H-NMR with
13C-NMR confirms the structure of product.
In reaction tubes, add 0.5mmol 2-methyl-benzyl phenyl ether, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 4-(2-methyl benzyloxy) cyanobenzene product, productive rate is 68%, uses
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 5
In reaction tubes, add 0.5mmol 3-benzyloxy toluene, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 2-methyl-4-benzyloxy cyanobenzene product, productive rate is 71%, uses
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 6
In reaction tubes, add 0.5mmol 1 successively, 3-dibenzyloxy benzene, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 2,4-benzyloxy cyanobenzene product, productive rate is 36%, uses
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 7
In reaction tubes, add 0.5mmol 3-(4-fluorine benzyloxy)-chlorobenzene, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile successively.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 2-chloro-4-(4-fluorine benzyloxy)-cyanobenzene product, productive rate is 20%, uses
1H-NMR with
13C-NMR confirms the structure of product.
In reaction tubes, add 0.5mmol 2-oxyethyl group-1 successively, 3-YLENE, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 4-oxyethyl group-3,5-dimethyl benzene formonitrile HCN product, productive rate is 23%, uses
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 9
In reaction tubes, add 0.5mmol 1,2 successively, 3-trimethoxy-benzene, 0.25mmol iodine, 0.4mmol cupric nitrate, the 0.25mmol Tripotassium iron hexacyanide and 2mL acetonitrile.Behind the sealed reaction tube, reaction tubes is inserted in the oil bath pan that is preheating to 180 ℃, stirred 35 hours at 180 ℃ of lower magnetic forces.After question response finished, cooling reaction system was to room temperature.Through column chromatography post reaction mixture is purified, obtain 2,3,4-trimethoxy-benzonitrile product product, productive rate is 71%, uses
1H-NMR with
13C-NMR confirms the structure of product.
Embodiment 10-17
The Tripotassium iron hexacyanide among the embodiment 1 is substituted with the hydration Tripotassium iron hexacyanide, hydration yellow prussiate of potash, the Trisodium hexacyanoferrate, hydrated iron sodium cyanide, calcium ferricyanide, iron magnesium cyanide, sodium cyanide and Potssium Cyanide respectively, and other conditions are with embodiment 1.The productive rate of 4-phenetole formonitrile HCN is respectively 73% (embodiment 10), 7% (embodiment 11), 58% (embodiment 12), 61% (embodiment 13), 43% (embodiment 14), 36% (embodiment 15), 21% (embodiment 16), 32% (embodiment 17).
Embodiment 18-21
Temperature of reaction among the embodiment 1 is become 150 ℃, 160 ℃, 170 ℃ and 200 ℃ respectively, and other conditions are with embodiment 1.The productive rate of 4-phenetole formonitrile HCN is respectively 7% (embodiment 18), 28% (embodiment 19), 61% (embodiment 20), 72% (embodiment 21).
Embodiment 22-28
With the reaction times among the embodiment 1 become 5 hours respectively, 10 hours, 20 hours, 25 hours, 30 hours, 40 hours and 45 hours, other conditions are with embodiment 1.The productive rate of 4-phenetole formonitrile HCN is respectively 12% (embodiment 22), 43% (embodiment 23), 57% (embodiment 24), 61% (embodiment 25), 68% (embodiment 26), 73% (embodiment 27), 70% (embodiment 28).
Embodiment 29-33
The amount of substance ratio of the phenetole among the embodiment 1, the Tripotassium iron hexacyanide, cupric nitrate, iodine is become 1:0.1:1:0.5 respectively; 1:5:0.8:0.5,1:0.3:1:0.4,1:0.4:1.2:0.5; 1:0.5:1:0.5 other conditions are with embodiment 1.The productive rate of 4-phenetole formonitrile HCN is respectively 11% (embodiment 29), 22% (embodiment 30), 45% (embodiment 31), 55% (embodiment 32), 63% (embodiment 33).
Claims (5)
1. method for preparing compound of benzene nitriles; It is characterized in that: in reaction vessel, add the alkoxy benzene compounds successively; Iodine, catalyzer cupric nitrate, prussiate and acetonitrile solvent, the amount of substance ratio that said alkoxy benzene compounds, prussiate, catalyzer cupric nitrate and iodine add is: 1:0.1～5:0.8～1.2:0.4～0.5, sealed reaction vessel then; Stirring reaction 5～45h under 150～200 ℃ of conditions; The reaction postcooling is purified to post reaction mixture through column chromatography to room temperature, obtains compound of benzene nitriles;
The chemical formula of said alkoxy benzene compounds is following:
2. a kind of method for preparing compound of benzene nitriles as claimed in claim 1 is characterized in that: said prussiate is the Tripotassium iron hexacyanide, hydrated iron Potssium Cyanide, hydration yellow prussiate of potash, the Trisodium hexacyanoferrate, hydrated iron sodium cyanide, calcium ferricyanide, iron magnesium cyanide, sodium cyanide or Potssium Cyanide.
3. a kind of method for preparing compound of benzene nitriles as claimed in claim 1 is characterized in that: the amount of substance that said alkoxy benzene compounds, prussiate, catalyzer cupric nitrate and iodine add is than being 1:0.5:0.8:0.5.
4. a kind of method for preparing compound of benzene nitriles as claimed in claim 1 is characterized in that: said being reflected at carried out 35h under 180 ℃.
5. a kind of method for preparing compound of benzene nitriles as claimed in claim 1, it is characterized in that: the acetonitrile solvent add-on is: every 1mmol alkoxy benzene compounds adds 0.2～5mL acetonitrile solvent.
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| CN2012101175076A CN102659624A (en) | 2012-04-20 | 2012-04-20 | Method for preparing cyanophenyl compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017558A (en) * | 2018-01-18 | 2018-05-11 | 河南省洛阳水文水资源勘测局 | A kind of preparation method of anise nitrile |
| CN113735738A (en) * | 2021-09-30 | 2021-12-03 | 刘嫚嫚 | Method for preparing anisyl nitrile |
-
2012
- 2012-04-20 CN CN2012101175076A patent/CN102659624A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| ALEXANDER等: "Rational Catalysis Design on the Basis of Mechanistic Understanding: Highly Efficient Pd-Catalyzed Cyanation of Aryl Bromides with NaCN in Recyclable Solvents", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| JINHO等: "Copper-Mediated Sequential Cyanation of Aryl C−B and Arene C−H Bonds Using Ammonium Iodide and DMF", 《JACS》 * |
| JINHO等: "Copper-Mediated Sequential Cyanation of Aryl C−B and Arene C−H Bonds Using Ammonium Iodide and DMF", 《JACS》, 24 January 2012 (2012-01-24), pages 2528 - 2531 * |
| MOWRY等: "The Preparation of Nitriles", 《CHEM REV》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017558A (en) * | 2018-01-18 | 2018-05-11 | 河南省洛阳水文水资源勘测局 | A kind of preparation method of anise nitrile |
| CN108017558B (en) * | 2018-01-18 | 2020-06-05 | 河南省洛阳水文水资源勘测局 | Preparation method of anisyl nitrile |
| CN113735738A (en) * | 2021-09-30 | 2021-12-03 | 刘嫚嫚 | Method for preparing anisyl nitrile |
| CN113735738B (en) * | 2021-09-30 | 2024-02-09 | 刘嫚嫚 | Method for preparing anisic nitrile |
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Application publication date: 20120912 |