CN107602415A - A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles - Google Patents

A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles Download PDF

Info

Publication number
CN107602415A
CN107602415A CN201710887154.0A CN201710887154A CN107602415A CN 107602415 A CN107602415 A CN 107602415A CN 201710887154 A CN201710887154 A CN 201710887154A CN 107602415 A CN107602415 A CN 107602415A
Authority
CN
China
Prior art keywords
aromatic
iii
nitrite
porphyrin
nitrile
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
Application number
CN201710887154.0A
Other languages
Chinese (zh)
Inventor
刘强
何维
郭欣
郭灿城
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
Original Assignee
YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD filed Critical YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
Priority to CN201710887154.0A priority Critical patent/CN107602415A/en
Publication of CN107602415A publication Critical patent/CN107602415A/en
Pending legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles, this method is in air atmosphere and in organic carboxyl acid solution system, and fragrant vinyl compound or heteroaromatic vinyl compound are catalyzed reaction generation aromatic nitrile compounds or heteroaromatic nitrile compounds in next step with nitrite in Fe (III) porphyrin；The advantages of this method is：1) reaction condition is gentle, simple to operate easily-controllable, and yield is higher；2) using efficient Fe (III) porphyrin catalyst, unused poisonous CN carbanionic reagents, the pollution to environment is reduced；3) raw material, nitrogen source, acid reagent etc. are cheap is easy to get, and significantly lowers production cost, can promote the use of industrial production.

Description

Method for synthesizing aromatic nitrile by catalyzing nitrite to oxidize aromatic olefin in one pot by Fe (III) porphyrin
Technical Field
The invention relates to a synthetic method of aromatic nitrile, in particular to a method for synthesizing aromatic nitrile by catalyzing nitrite oxidation aromatic olefin with Fe (III) porphyrin in one pot; belongs to the technical field of pharmaceutical intermediates and organic chemical synthesis.
Background
Aryl olefins are unsaturated aromatic compounds containing carbon-carbon double bonds, which are mainly obtained from petroleum raw materials, such as styrene which is typically obtained from petrochemical ethylbenzene catalytic dehydrogenation or co-oxidation methods, which are well-established and industrially produced processes, so that styrene is a cheap raw material. The aromatic nitrile compounds are very important intermediates for synthesizing pesticides, aliphatic amine or benzoic acid, and can be used as solvents of nitrile rubber, resin, polymers, coatings and the like. In addition, benzonitrile is a basic structural unit of many natural products, bioactive molecules and drug molecules, and has very wide application in psychopharmaceuticals. Therefore, the conversion of low-cost aryl olefins into aryl nitriles is of great economic interest.
At present, the method for synthesizing aryl nitrile compounds from aryl olefin is a hot spot of research of chemists. As early as 1950, William i.denton started with aryl olefins at 524-. By using MoO3-A1203As a catalyst, an aromatic nitrile was produced by introducing ammonia gas into the reaction system. In 1962, when Y.L.Chow studied the light addition reaction of styrene with N-nitrosopiperidine, the resulting product was tosylated in triethylamine to afford benzonitrile. The 2013 JIAONING topic group is prepared by reacting TMSN with TEMPO catalyst3Is a nitrogen source, O2Olefins are converted to cyano-and carbonyl-containing compounds by breaking the carbon-carbon double bond for the source of oxygen. Cracking double bonds of olefin under the catalysis of iodobenzene diacetate, and reacting with nitrogen source NH4HCO3Acting to generate nitrile compounds. Chinese patent (CN102329248A) discloses a method for synthesizing benzonitrile, which takes styrene oxide and ammonia gas as raw materials, adopts oxides of Fe, Ni, Co, Zn, Cr or Cu and the like as catalysts, and obtains the benzonitrile by ammoniation under the action of the catalysts. Although great progress has been made in the research on the synthesis of nitrile compounds from olefins, the research is only limited by theoretical research, but the reaction conditions and operation are difficult to control in the industrial practical process.
Disclosure of Invention
Aiming at the defects of harsh reaction conditions, low yield and the like of the existing method for synthesizing aryl nitrile compounds from aryl olefin compounds, the invention aims to provide a method for synthesizing aromatic nitrile by one-step reaction of aryl ethylene and nitrite under mild reaction conditions at high yield.
In order to achieve the technical purpose, the invention provides a method for synthesizing aromatic nitrile in one pot by oxidizing aromatic olefin with nitrite under the catalysis of Fe (III) porphyrin.
In a preferred embodiment, the aromatic vinyl compound has a structure represented by formula 1 or formula 2:
the aromatic heterocyclic alkene compound has a structure shown in a formula 3:
the aromatic nitrile compound has a structure of formula 4 or formula 5:
the aromatic heterocyclic nitrile compound has a structure of formula 6:
wherein,
R1、R2、R3、R4and R5Independently selected from hydrogen, alkyl, alkoxy, halogen, haloalkyl, alkanoyloxy or nitro;
x is O, S or N.
In a more preferred embodiment, the aromatic vinyl compound is styrene, p-methylstyrene, m-methylstyrene, 2, 5-dimethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-chloromethylstyrene, p-tert-butylstyrene, p-acetoxystyrene, p-nitrostyrene, 2,4, 6-trimethylstyrene or naphthylene.
In a more preferred embodiment, the heteroaromatic vinyl compound is thiopheneethene.
In a more preferred embodiment, the aromatic nitrile compound is benzonitrile, p-methylbenzonitrile, m-methylbenzonitrile, 2, 5-dimethylbenzonitrile, p-methoxybenzonitrile, p-ethoxybenzonitrile, p-chlorobenzonitrile, m-chlorobenzonitrile, o-chlorobenzonitrile, p-bromobenzonitrile, m-bromobenzonitrile, o-bromobenzonitrile, p-chloromethylbenzonitrile, p-tert-butylbenzonitrile, p-acetoxybenzonitrile, p-nitrobenzonitrile, 2,4, 6-trimethylbenzonitrile, or naphthonitrile.
In a more preferred embodiment, the aromatic heterocyclic nitrile compound is thiophenecarbonitrile.
Preferably, the Fe (iii) porphyrin has a structure of formula 7 or a structure of formula 8:
wherein,
R6、R7and R8Independently selected from hydrogen, hydroxy, nitro, trifluoromethyl, halogen, alkyl, alkoxy, cyano, amino, pyridyl,Carboxyl, sulfonic acid group, glycosyl, cyclodextrin group or calixarene group;
m and M1Is Fe (III) ion;
x is hydroxide ion, nitrate ion, trifluoromethyl sulfonate ion, perhalogenate ion, halogen ion, acetate ion, cyanate ion, carbonyl ligand, acetylacetone ligand or pyridine ligand.
In a preferred embodiment, the reaction conditions are as follows: the pH value of the organic carboxylic acid solution system is 3.0-4.5, the reaction temperature is 55-75 ℃, the reaction time is 4-8 h, and the concentration of Fe (III) porphyrin in the organic carboxylic acid solution system is 1-100 ppm.
In a more preferable scheme, the organic carboxylic acid in the organic carboxylic acid solution system is at least one of formic acid, glacial acetic acid and propionic acid.
In a more preferred embodiment, the solvent in the organic carboxylic acid solution system is acetonitrile.
In a preferable scheme, the molar ratio of the aromatic alkene compound or the aromatic heterocyclic alkene compound to the nitrite is 1: 2-1: 6.
In a preferred embodiment, the nitrite is at least one of sodium nitrite, potassium nitrite and silver nitrite.
The specific method for synthesizing the aromatic nitrile by catalyzing the aromatic olefin by the metalloporphyrin comprises the following steps: mixing Fe (III) porphyrin (the concentration of a catalyst is 1-100 ppm), a nitrite, an aromatic olefin compound (the molar ratio of the nitrite to the aromatic olefin compound is 2-6: 1), an organic carboxylic acid and an organic solvent (the pH value is 3.0-4.5), placing the mixture in a reaction tube, reacting for 4-8 hours at the temperature of 50-80 ℃ in an air atmosphere, cooling to room temperature after the reaction is finished, carrying out reduced pressure distillation and concentration, and purifying by column chromatography to obtain a series of aromatic nitrile compounds;
the specific reaction equation is as follows:
in the method, the eluent adopted by column chromatography is a mixed solvent of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is (20-100): 1.
the reaction principle of aryl alkene compounds and nitrite is as follows: nitrite reacts to generate NO and NO under the weak acidic condition2The mixed gas reacts with aromatic olefin to generate an intermediate α -nitro acetophenone oxime, and the intermediate is converted into a benzonitrile compound after a period of reaction.
Compared with the prior art, the technical scheme of the invention has the following advantages and effects:
1) the reaction condition is mild, and the reaction can be carried out under the air atmosphere and the low-temperature condition.
2) The reaction is simple and the operation is easy to control.
3) The reaction yield is high, the yield reaches 60-96% according to different substituent groups, and various derivatives with different groups can be prepared.
4) Fe (III) porphyrin catalyst is used as a catalyst and nitrite is used as a nitrogen source, so that toxic CN negative ion reagent is avoided, and the pollution to the environment is reduced.
5) The aryl ethylene, nitrite and the like are used as raw materials, the price is low, the raw materials are easy to obtain, the production cost is obviously reduced, and the method can be popularized and applied to industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of benzonitrile prepared in example 1;
FIG. 2 is a nuclear magnetic carbon spectrum of benzonitrile prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of p-tolunitrile prepared in example 2;
FIG. 4 is a nuclear magnetic carbon spectrum of p-tolunitrile prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be performed with reference to conventional techniques for process parameters not specifically mentioned.
The substrate starting materials, solvents and the like mentioned in the following examples were all commercial products (analytical reagents) on the market and were not further purified.
The product is separated by chromatography, column silica gel (300-400 mesh).
1H NMR (400MHz/500MHz), 13C NMR (100MHz), in CDCl3As solvent, TMS was used as internal standard.
Multiplicity is defined as follows: s (singlet); d (doublet); t (triplet); q (quartet) and m (multiplet). Coupling constant J (Hertz).
Example 1
Synthesis of benzonitrile
Adding 0.4 mmol of styrene, 2 mmol of sodium nitrite, 1 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The benzonitrile structure is shown in the following formula:
the compound was a colorless liquid with a yield of 84%, and its nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.60(dd,J＝12.0,7.6Hz,3H),7.45(t,J＝7.8Hz,2H)；13CNMR(101MHz,CDCl3)δ132.82,132.05,129.16,118.82,112.28.
example 2
Synthesis of p-methylbenzonitrile
Adding 0.4 mmol of p-methylstyrene, 2 mmol of sodium nitrite, 0.5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and performing column chromatography separation and purification to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-methyl benzonitrile is shown as the following formula:
the compound was a colorless liquid with a yield of 87.26%, and had the following nuclear magnetic data:
1H NMR(400MHz,CDCl3)δ7.54(d,J＝8.1Hz,2H),7.26(d,J＝2.1Hz,2H),2.42(s,3H)；13C NMR(101MHz,CDCl3)δ143.71,132.06,129.85,119.18,109.33,21.85.
example 3
Synthesis of m-methyl benzonitrile
Adding 0.4 mmol of m-methylstyrene, 2 mmol of sodium nitrite, 2 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the m-methyl benzonitrile is shown as the following formula:
the compound was a colorless liquid with a yield of 71.23%, and had the following nuclear magnetic data:
1H NMR(400MHz,CDCl3)δ7.45(d,J＝4.7Hz,2H),7.41(d,J＝7.7Hz,1H),7.35(t,J＝5.9Hz,1H),2.39(s,3H)；13C NMR(101MHz,CDCl3)δ139.23,133.64,132.50,129.28,128.99,119.03,112.28,21.14.
example 4
Synthesis of 2, 5-dimethylbenzonitrile
Adding 0.4 mmol of 2, 5-dimethyl styrene, 2 mmol of sodium nitrite, 3 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the 2, 5-dimethyl benzonitrile is shown as the following formula:
the compound was a white solid with a yield of 75.75%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.39(s,1H),7.26(d,J＝2.7Hz,1H),7.18(d,J＝7.9Hz,1H),2.49(s,3H),2.33(s,3H)；13C NMR(101MHz,CDCl3)δ138.85,136.06,133.56,132.71,130.11,118.35,112.53,20.62,19.93.
example 5
Synthesis of p-methoxybenzonitrile
Adding 0.4 mmol of p-methoxystyrene, 2 mmol of sodium nitrite, 1 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-methoxybenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 86.39%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.59(d,J＝8.8Hz,2H),6.95(d,J＝8.8Hz,2H),3.86(s,3H)；13C NMR(101MHz,CDCl3)δ162.86,134.00,119.23,114.76,103.99,55.55.
example 6
Synthesis of p-ethoxybenzonitrile
Adding 0.4 mmol of p-ethoxystyrene, 2 mmol of sodium nitrite, 2 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-ethoxybenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 85.86%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.8Hz,2H),6.93(d,J＝8.8Hz,2H),4.08(q,J＝6.9Hz,2H),1.44(t,J＝7.0Hz,3H)；13C NMR(101MHz,CDCl3)δ162.27,133.98,119.32,115.16,103.70,63.94,14.57.
example 7
Synthesis of p-chlorobenzonitrile
Adding 0.4 mmol of p-chlorostyrene, 2 mmol of sodium nitrite, 4 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-chlorobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 82.91%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.61(d,J＝8.5Hz,2H),7.47(d,J＝8.5Hz,2H)；13C NMR(101MHz,CDCl3)δ139.57,133.40,129.71,117.98,110.80.
example 8
Synthesis of m-chlorobenzonitrile
Adding 0.4 mmol of m-chlorostyrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The m-chlorobenzonitrile structure is shown as the following formula:
the compound was a white solid with a yield of 60.18%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.65(s,1H),7.60(d,J＝8.1Hz,1H),7.56(d,J＝7.8Hz,1H),7.47–7.40(m,1H).；13C NMR(101MHz,CDCl3)δ135.28,133.26,131.96,130.50,130.31,117.46,114.00.
example 9
Synthesis of o-chlorobenzonitrile
Adding 0.4 mmol of o-chlorostyrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the o-chlorobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 50.65% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.68(d,J＝7.4Hz,1H),7.59–7.56(m,1H),7.53(d,J＝1.4Hz,1H),7.40–7.37(m,1H)；13C NMR(101MHz,CDCl3)δ136.91,134.04,133.87,130.07,127.16,115.97,113.45.
example 10
Synthesis of p-bromobenzonitrile
Adding 0.4 mmol of p-bromostyrene, 2 mmol of sodium nitrite, 4 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-bromobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 92.22% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.64(d,J＝8.4Hz,2H),7.53(d,J＝8.5Hz,2H)；13C NMR(101MHz,CDCl3)δ133.42,132.66,128.03,118.07,111.25.
example 11
Synthesis of m-bromobenzonitrile
Adding 0.4 mmol of m-bromostyrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the m-bromobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 84.26%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.73(s,1H),7.68(d,J＝8.2Hz,1H),7.53(d,J＝7.7Hz,1H),7.29(t,J＝7.9Hz,1H)；13C NMR(101MHz,CDCl3)δ136.14,134.78,130.73,130.63,122.93,117.30,114.23.
example 12
Synthesis of o-bromobenzonitrile
Adding 0.4 mmol of o-bromostyrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the o-bromobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 78.49%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ7.62(ddd,J＝15.9,9.3,4.2Hz,2H),7.42–7.35(m,2H)；13C NMR(101MHz,CDCl3)δ134.34,133.91,133.22,127.65,125.35,118.78,117.15.
example 13
Synthesis of 2-cyanonaphthalene
Adding 0.4 mmol of 2-vinylnaphthalene, 2 mmol of sodium nitrite, 3 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The 2-cyanonaphthalene structure is shown as the following formula:
the compound was a white solid with a yield of 81.3% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ8.20(s,1H),7.88(t,J＝8.4Hz,3H),7.64–7.56(m,3H)；13C NMR(101MHz,CDCl3)δ134.66,134.17,132.25,129.21,129.07,128.43,128.07,127.68,126.35,119.28,109.38.
example 14
Synthesis of p-chloromethyl benzonitrile
Adding 0.4 mmol of p-chloromethyl styrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-chloromethyl benzonitrile is shown as the following formula:
the compound was a white solid with a yield of 96.2% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.66(d,J＝8.2Hz,2H),7.51(d,J＝8.2Hz,2H),4.61(s,2H)；13C NMR(101MHz,CDCl3)δ142.43,132.55,129.17,118.41,112.26,44.93.
example 15
Synthesis of p-tert-butylbenzonitrile
Adding 0.4 mmol of p-tert-butylstyrene, 2 mmol of sodium nitrite, 1 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-tert-butyl benzonitrile is shown as the following formula:
the compound was a white solid with a yield of 89.2% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.59(d,J＝8.4Hz,2H),7.48(d,J＝8.4Hz,2H),1.33(s,9H)；13C NMR(101MHz,CDCl3)δ156.66,131.98,126.18,119.18,109.32,35.28,30.96.
example 16
Synthesis of p-nitrobenzonitrile
Adding 0.4 mmol of p-nitrostyrene, 2 mmol of sodium nitrite, 5 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-nitrobenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 80.67%, and the nuclear magnetic data was as follows:
1H NMR(400MHz,CDCl3)δ8.37(d,J＝8.7Hz,2H),7.90(d,J＝8.7Hz,2H)；13C NMR(101MHz,CDCl3)δ150.06,133.50,124.30,118.35,116.80.
example 17
Synthesis of 2,4, 6-trimethylbenzonitrile
Adding 0.4 mmol of 2,4, 6-trimethylstyrene, 2 mmol of sodium nitrite, 2 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and separating and purifying through column chromatography to obtain a target product, wherein eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the 2,4, 6-trimethylbenzonitrile is shown as the following formula:
the compound was a white solid with a yield of 82.5% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ6.93(s,2H),2.48(s,6H),2.32(s,3H)；13C NMR(101MHz,CDCl3)δ142.81,141.98,128.20,117.65,110.32,21.58,20.63.
example 18
Synthesis of p-acetoxybenzonitrile
Adding 0.4 mmol of p-acetoxystyrene, 2 mmol of sodium nitrite, 3 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product through a rotary evaporator, and performing column chromatography separation and purification to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the p-acetoxy cyanobenzene is shown as the following formula:
the compound was a white solid with a yield of 88.9% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.69(d,J＝8.6Hz,2H),7.24(d,J＝8.6Hz,2H),2.33(s,3H)；13C NMR(101MHz,CDCl3)δ168.51,153.91,133.68,122.75,118.24,109.76,21.11.
example 19
Synthesis of 2-cyanothiophenes
Adding 0.4 mmol of 2-vinyl thiophene, 2 mmol of sodium nitrite, 2 mg of metal iron (III) porphyrin and 4.5 ml of acetonitrile solvent into a reaction test tube, heating and stirring at 70 ℃ in the air atmosphere, dropwise adding 0.5 ml of formic acid within the first 0.5 hour, reacting for 4 hours, stopping heating and stirring, cooling to room temperature, obtaining a crude product by a rotary evaporator, and separating and purifying by column chromatography to obtain a target product, wherein the eluent of the column chromatography is a mixed solvent of petroleum ether and ethyl acetate. The structure of the 2-cyanothiophene is shown as the following formula:
the compound was a yellow solid with a yield of 76.34% and the nuclear magnetic data were as follows:
1H NMR(400MHz,CDCl3)δ7.64(d,J＝3.7Hz,1H),7.61(d,J＝5.1Hz,1H),7.15–7.12(m,1H)；13C NMR(101MHz,CDCl3)δ137.41,132.56,127.65,114.22,109.97.
control experimental group:
in the following examples, styrene is used as a raw material, sodium nitrite is used as a nitrogen source, and benzonitrile is synthesized; the optimization of the experimental conditions is further explained. Experimental procedure with reference to example 1, the specific experimental conditions are as follows:
yields were determined by GC (using an internal standard of p-dichlorobenzene).
As can be seen from the above table, the amount of sodium nitrite is preferably about 5 times equivalent to the substrate styrene, and the relative increase or decrease of the amount of sodium nitrite results in the decrease of the benzonitrile yield.
The reaction proceeds in an acidic medium, but it is preferable to use a weak organic acid, and as can be seen from the table, the yield of benzoic acid is significantly improved by using a weak acidic organic carboxylic acid.
From the solvent of choice, solvents other than acetonitrile are not ideal.
At a temperature of 50 ℃ the reaction proceeds smoothly, and when the temperature rises to 70 ℃ the yield is already appreciable.

Claims (8)

1. A method for synthesizing aromatic nitrile by catalyzing nitrite oxidation aromatic olefin with Fe (III) porphyrin in one pot is characterized in that: in the air atmosphere and in an organic carboxylic acid solution system, aromatic vinyl compounds or aromatic heterocyclic vinyl compounds and nitrite react in one step under the catalysis of Fe (III) porphyrin to generate aromatic nitrile compounds or aromatic heterocyclic nitrile compounds.
2. The method for synthesizing aromatic nitrile in one pot by catalyzing nitrite oxidation aromatic olefin by Fe (III) porphyrin according to claim 1, wherein:
the aromatic vinyl compound has a structure shown in a formula 1 or a formula 2:
the aromatic heterocyclic alkene compound has a structure shown in a formula 3:
the aromatic nitrile compound has a structure of formula 4 or formula 5:
the aromatic heterocyclic nitrile compound has a structure of formula 6:
wherein,
R1、R2、R3、R4and R5Independently selected from hydrogen, alkyl, alkoxy, halogen, haloalkyl, alkanoyloxy or nitro;
x is O, S or N.
3. The method for synthesizing aromatic nitrile in one pot by catalyzing nitrite oxidation aromatic olefin by Fe (III) porphyrin according to claim 2, wherein:
the aromatic vinyl compound is styrene, p-methylstyrene, m-methylstyrene, 2, 5-dimethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-chloromethylstyrene, p-tert-butylstyrene, p-acetoxystyrene, p-nitrostyrene, 2,4, 6-trimethylstyrene or naphthalene;
the aromatic heterocyclic alkene compound is thiophene ethylene;
the aromatic nitrile compound is benzonitrile, p-methylbenzonitrile, m-methylbenzonitrile, 2, 5-dimethylbenzonitrile, p-methoxybenzonitrile, p-ethoxybenzonitrile, p-chlorobenzonitrile, m-chlorobenzonitrile, o-chlorobenzonitrile, p-bromobenzonitrile, m-bromobenzonitrile, o-bromobenzonitrile, p-chloromethylbenzonitrile, p-tert-butylbenzonitrile, p-acetoxybenzonitrile, p-nitrobenzonitrile, 2,4, 6-trimethylbenzonitrile or naphthonitrile;
the aromatic heterocyclic nitrile compound is thiophene formonitrile.
4. The method for synthesizing aromatic nitrile in one pot by catalyzing nitrite oxidation aromatic olefin by Fe (III) porphyrin according to claim 1, wherein:
the Fe (III) porphyrin has a structure of formula 7 or a structure of formula 8:
wherein,
R6、R7and R8Independently selecting hydrogen, hydroxyl, nitro, trifluoromethyl, halogen, alkyl, alkoxy, cyano, amino, pyridyl, carboxyl, sulfonic group, glycosyl, cyclodextrin group or calixarene group;
m and M1Is Fe (III) ion;
x is hydroxide ion, nitrate ion, trifluoromethyl sulfonate ion, perhalogenate ion, halogen ion, acetate ion, cyanate ion, carbonyl ligand, acetylacetone ligand or pyridine ligand.
5. The method for synthesizing aromatic nitrile by catalyzing nitrite oxidation aromatic olefin in one pot by Fe (III) porphyrin according to any one of claims 1 to 4, wherein: the reaction conditions are as follows: the pH value of the organic carboxylic acid solution system is 3.0-4.5, the reaction temperature is 55-75 ℃, the reaction time is 4-8 h, and the concentration of Fe (III) porphyrin in the organic carboxylic acid solution system is 1-100 ppm.
6. The method for synthesizing aromatic nitrile in one pot by catalyzing nitrite oxidation aromatic olefin by Fe (III) porphyrin according to claim 5, wherein: in the organic carboxylic acid solution system, the organic carboxylic acid is at least one of formic acid, glacial acetic acid and propionic acid, and the solvent is acetonitrile.
7. The method for synthesizing aromatic nitrile by catalyzing nitrite oxidation aromatic olefin in one pot by Fe (III) porphyrin according to any one of claims 1 to 4, wherein: the molar ratio of the aromatic alkene compound or the aromatic heterocyclic alkene compound to the nitrite is 1: 2-1: 6.
8. The method for synthesizing aromatic nitrile in one pot by catalyzing nitrite oxidation aromatic olefin by Fe (III) porphyrin according to claim 7, wherein: the nitrite is at least one of sodium nitrite, potassium nitrite and silver nitrite.
CN201710887154.0A 2017-09-25 2017-09-25 A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles Pending CN107602415A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710887154.0A CN107602415A (en) 2017-09-25 2017-09-25 A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710887154.0A CN107602415A (en) 2017-09-25 2017-09-25 A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles

Publications (1)

Publication Number Publication Date
CN107602415A true CN107602415A (en) 2018-01-19

Family

ID=61057912

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710887154.0A Pending CN107602415A (en) 2017-09-25 2017-09-25 A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles

Country Status (1)

Country Link
CN (1) CN107602415A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111499541A (en) * 2019-10-31 2020-08-07 沅江华龙催化科技有限公司 Method for synthesizing (E) -1-styrylcyclohexane-1-nitrile compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS523001B2 (en) * 1972-12-07 1977-01-25

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS523001B2 (en) * 1972-12-07 1977-01-25

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
QIANG LIU ETAL: "Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant", 《TETRAHEDRON LETTERS》 *
方宝: "亚硝酸钠作为氮源与氧化剂的芳香烯烃制备芳香腈的研究", 《湖南大学硕士论文》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111499541A (en) * 2019-10-31 2020-08-07 沅江华龙催化科技有限公司 Method for synthesizing (E) -1-styrylcyclohexane-1-nitrile compound
CN111499541B (en) * 2019-10-31 2023-01-31 新疆普禾粟新型环保材料有限公司 Method for synthesizing (E) -1-styrylcyclohexane-1-nitrile compound

Similar Documents

Publication Publication Date Title
Zhang et al. A metal-free catalytic system for the oxidation of benzylic methylenes and primary amines under solvent-free conditions
CN104024201B (en) Use the manufacture method of the farnesal of vanudium complex
CN106902880A (en) Application of the mercaptopyrimidine univalent copper complex of 4,6 dimethyl 2 in catalysis ketone or aldehyde hydrogen transfer reaction prepare alcohol
CN107573259A (en) A kind of method of catalysis of metalloporphyrin aromatic olefin synthesis aromatic nitriles
Lee et al. Chiral bipyridine–copper (I) complex-catalyzed enantioselective allylic oxidation of cyclic alkenes
CN110003011B (en) Preparation method of nitroolefin derivative by taking nitrate as nitro source
Shevchenko et al. Direct asymmetric α-hydroxylation of cyclic α-branched ketones through enol catalysis
CN113788765B (en) Preparation method of alpha, beta-unsaturated amide
CN105566021A (en) Preparation method of alpha, beta-unsaturated carboxylic acid compounds
CN107602415A (en) A kind of method of Fe (III) porphyrin catalysis nitrite-oxidizing aromatic olefin One-step Synthesis aromatic nitriles
Yamashita et al. Catalytic Asymmetric Mannich‐Type Reactions Using a Novel Chiral Iron Complex
CN114213201B (en) Method for obtaining MBH reaction product by catalysis of microchannel reactor
Yu et al. Metal-Free: A Novel and Efficient Aerobic Oxidation of Primary Amines to Oximes Using N, N′, N ″-Trihydroxyisocyanuric Acid and Acetaldoxime as Catalysts in Water
CN107032939B (en) Synthetic method of alpha, beta-unsaturated nitroolefin derivative
Ma et al. Cu (OAc) 2/malononitrile/water: a simple reaction system for synthesis of aromatic nitriles from aldoximes
Yang et al. CaCl2-or MgCl2-catalyzed allylic oxidations of ionone-like dienes
CN109824501B (en) Aryl iodine compound containing carboxydifluoro methylene at ortho position and preparation method thereof
CN107118196B (en) The preparation method of different coumarin derivative
CN109134538B (en) Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof
Lanari et al. Copper (II) Triflate–Sodium Dodecyl Sulfate Catalyzed Preparation of 1, 2-Diphenyl-2, 3-dihydro-4-pyridones in Aqueous Acidic Medium
Paul et al. Silica supported ferric nitrate nonahydrate: selective oxidation of benzoins under mild conditions
Cai et al. Promotion Mechanism of H2O for Stereoselectivity in Pd (II)-catalyzed C―H Arylation of Diarylphosphinamides with Arylboronic Acids
CN115093346B (en) Method for preparing nitrile compound from different substituted cycloalkanone in one step
CN107629049B (en) Synthesis method of pyridine [2,1-a ] isoindole compound
CN109456180A (en) A kind of β of no metal catalytic, the synthetic method of compound in β-dichloro

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180119

WD01 Invention patent application deemed withdrawn after publication