CN101565388B - Preparation method of 2-aryl propionitrile compounds - Google Patents
Preparation method of 2-aryl propionitrile compounds Download PDFInfo
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- CN101565388B CN101565388B CN2009100523728A CN200910052372A CN101565388B CN 101565388 B CN101565388 B CN 101565388B CN 2009100523728 A CN2009100523728 A CN 2009100523728A CN 200910052372 A CN200910052372 A CN 200910052372A CN 101565388 B CN101565388 B CN 101565388B
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Abstract
The invention discloses a preparation method of 2-aryl propionitrile compounds, which belongs to the technical field of chemical preparation. The preparation method of 2-aryl propionitrile compounds comprises the steps of: dissolving substituted phenylacetonitrile in methyl carbonate and adding a catalytic amount of ionic liquid to react for 1 to 15 hours at a temperature ranging from 25 to 180 DEG C to prepare 2-aryl propionitrile compounds. The preparation method of 2-aryl propionitrile compounds has the advantages that the green catalyst, namely the ionic liquid, is used instead of the traditional catalyst which has poor catalytic activity and is difficult to recycle; the reaction conditions are mild and the yield and selectivity are very high; in addition, the green reagent, namely themethyl carbonate, is used for avoiding the use of toxic and hazardous reagents, therefore, the preparation method is safe and convenient in operation.
Description
Technical field
The present invention relates to the chemical preparation technical field, specifically a kind of preparation method of 2-aryl propionitrile compounds.
Background technology
The 2-aryl propionitrile compounds is important organic raw material and Chemicals; This compounds can hydrolysis can generate carboxylic acid, and reduction can generate amine, can also derive many other functional groups; Be not only the preparation anodyne (like ketoprofen; Naproxen, important intermediate Ibuprofen), and be the presoma of dyestuff preparation.So this compounds has purposes very widely in industry, agricultural and medicine and other fields.The methylated method of benzyl cyanide compound is a lot, from present bibliographical information, roughly can be divided into two kinds of methods; The one, the methylation method of traditional benzyl cyanide compound, methylating reagent are (chemical reagent, 201-202 such as halomethane and methyl-sulfate; 228, (2003)), two are to use the methylating reagent such as methylcarbonate (the Applied Catalysis of nontoxic green; A:general, 344-353,292 (2005)), aldehyde, methyl alcohol (Chemistry-A European Journal; 8228-8239; 12 (2006)) or trimethoxy-methane (Journal of Organic Chemistry, 9540-9544,63 (1998)) as methylating reagent.
More than all have very big shortcoming in two kinds of methods.Though first kind of compound method reacted carry out very fast, and reaction conditions is gentle, and the methylating reagent that this method is used is halomethane or methyl-sulfate, and this compounds is deleterious, and volatility is very strong, and environment and people have all been caused very big injury; The catalyzer of using in the reaction is highly basic sodium hydroxide or weak mineral alkali salt of wormwood; Alkali corrosion property is very big to equipment damage very by force, and inconvenient operation, recycles difficulty; And also there is the problem of recycling difficulty in weak base, and this method product selectivity is also very poor.Second method research many, especially methylcarbonate is more deep relatively as the research of methylating reagent.People such as Tanaka use metal Ru class catalysis aldehyde and the nitrile that contains active methylene radical to react as 130-230 ℃ in temperature of reaction; Experimental result is more satisfactory; Weak point has been to use expensive metal Ru class catalyzer; Catalyzer is prone to inactivation in aqueous system, and temperature of reaction compare higher, troublesome poeration.Tundo etc. have done detailed research to the methylation reaction of methylcarbonate and nitrile.Be reflected under solution-air phase-transfer catalysis (GC-PTC) condition and carry out, catalyzer is the salt of wormwood bed that is coated with polyoxyethylene glycol, and in the reaction of methylcarbonate and benzyl cyanide, the transformation efficiency of benzyl cyanide is up to 98%, and the dimethyl-product only accounts for 1%.The methylation reaction of benzyl cyanide compound and methylcarbonate also can carry out in autoclave, and monomethylation product productive rate can reach more than 80%, with NH when making catalyzer with alkaline carbonate
2The selectivity of product 2-phenyl propionitrile was more than 90% when-Na-Al-MCM-41 made catalyzer.The methylation reaction of benzyl cyanide and methylcarbonate also can carry out in gas phase, and as solid base catalyst, gas-phase reaction has been avoided this complicated process of separating catalyst in the liquid phase reaction with the molecular sieve of alkalimetal ion exchange.Fu etc. find that the NaY zeolite activity is better, and under optimized reaction conditions, the productive rate of product 2-phenyl propionitrile can reach 72%.
From analyzing; Second method uses methylcarbonate to carry out benzyl cyanide compound fine poisonous and hazardous methylating reagent problem of using that solved when methylating as methylating reagent; But there is very big shortcoming in the existing catalyst system; As when obtaining the ideal selectivity, then must use precious metal as catalyzer; If when adopting heterogeneous catalyst such as NaY zeolite, be more convenient though reaction finishes to separate, the productive rate of 2-phenyl propionitrile is relatively very low; Use equally like salt of wormwood as catalyzer, can obtain very highly selective, but temperature of reaction is very high.Because all there is deficiency in above-mentioned catalyst system, new catalystsystem awaits research.
Summary of the invention
The object of the present invention is to provide the preparation method of the 2-aryl propionitrile compounds that a kind of preparation technology is simple, environmental effect is good.
In order to overcome deficiency of the prior art, the present invention uses ionic liquid to be catalyzer, with nontoxic green methylating reagent methylcarbonate and benzyl cyanide compound prepared in reaction 2-aryl propionitrile compounds.Benzyl cyanide compound provided by the invention can use general formula (I) to represent:
Simultaneously in (I):
R
1For: itrile group;
R
2For: hydrogen, halogen, C
1-C
10Alkyl, C
1-C
6Alkenyl, methoxyl group, nitro, carboxaldehyde radicals, the methyl-formiate base, amido, phenyl contains the substituting group phenyl ,-N (C
1-C
10Alkyl)
2,-(CH
2)
nCOOH, wherein n is 1～10 integer, comprises 1 and 10.
Comparatively preferred compound is in the general formula (I) among the present invention:
R
1Select itrile group.
R
2Select C
1-C
10Alkyl, phenyl, and contain substituent phenyl.
The alkyl of indication comprises the straight or branched alkyl in the general formula (I).Halogen comprises fluorine, chlorine, bromine, iodine.Alkenyl is meant the straight or branched form, the group of 1 to 6 carbon-carbon double bond, for example, propenyl, allyl group etc.
2-aryl propionitrile compounds provided by the invention, be that the method for preparation of compound of general formula (I) expression is following:
Above-mentioned reaction formula formula of (II) is benzyl cyanide and benzyl cyanide compound, and is on sale on market, and DMC is a methylcarbonate, and IL is an ionic liquid.
Specific operation process is: in autoclave, add benzyl cyanide or benzyl cyanide compound and methylcarbonate (DMC); The ionic liquid that adds catalytic amount is that reaction made the 2-aryl propionitrile compounds in 1-15 hour between the room temperature to 180 ℃ in temperature of reaction; Preferred temperature is 90 ℃ to 180 ℃, and preferred temperature is 120-180 ℃; Ionic liquid for example can be selected from [Bmim] OAc (1-butyl-3-Methylimidazole acetate), [Bmim] Cl (1-butyl-3-Methylimidazole villaumite), [Bmim] Br (1-butyl-3-Methylimidazole bromine salt), [Pmim] I (1-propyl group-3-Methylimidazole salt compounded of iodine) and [Bmim] BF
4In (1-butyl-3-methyl imidazolium tetrafluoroborate) any one; It is 1%～100% that catalytic amount refers to the molar percentage that catalyst consumption accounts for raw material, and preferable range is 1%～50%, and most preferred range is 2%～15%; The mol ratio of raw material and methylcarbonate (DMC) is 1: 1～100, and preferable range is 1: 1～50.
Following last handling process is a general process, and reaction mixture is cooled to room temperature, adds entry and organic solvent, carries out separatory, and water merges organic phase with SX twice then, and rotary evaporation removes and desolvates, and obtains product.Solvent can be selected from a kind of in anhydrous diethyl ether, methylene dichloride, trichloromethane, ETHYLE ACETATE and the toluene.
The present invention has compared different ionic liquid and has carried out methylated influence to using methylcarbonate as methylating reagent and benzyl cyanide compound.Reaction formula is following, and reaction result is listed in table 1.
The ionic liquid-catalyzed performance that table 1 is different
| Ionic liquid (IL) a | Transformation efficiency (%) | Selectivity (%) | Yield (%) | By product (%) |
| - | - | - | - | - |
| [Bmim]OAc | 98 | 100 | 98 | no |
| [Bmim]Cl | 96 | 100 | 96 | no |
| [Bmim]Br | 76 | 92 | 70 | 1 |
| [Pmim]I | 59 | 100 | 59 | no |
| [Bmim]BF 4 | 100 | 60 | 60 | 40 |
Reaction conditions is 130 ℃, and reaction times 10h, DMC are solvent, and catalyst consumption is the mole number 10% of indoles consumption.
The result finds that under identical reaction conditions, if do not add any catalyzer, this reaction is not carried out, and is that productive rate is all more than 60% behind the catalyzer and add ionic liquid, and the selectivity of discovery methylate is also all more than 60%.The catalytic effect of finding alkali ionic liquid [Bmim] OAc is best.
Therefore, non diffusible ion liquid [Bmim] OAc is a catalyzer, has studied different temperature of reaction is carried out methylation reaction to methylcarbonate and benzyl cyanide compound influence.Reaction formula is following:
The influence of table 2 differing temps
| Temperature of reaction (℃) a | Transformation efficiency (%) | Selectivity (%) | Yield (%) |
| 90 | Traces | -- | Traces |
| 110 | 30 | 92 | 28 |
| 120 | 75 | 100 | 75 |
| 130 | 98 | 100 | 98 |
| 150 | 99 | 100 | 99 |
Reaction conditions is a catalyzer with [Bmim] OAc all, and reaction times 10h, DMC are solvent, and catalyst consumption is the mole number 10% of benzyl cyanide consumption.
The result finds that the productive rate of reaction when temperature of reaction is 130 ℃ just reaches the highest.
Our stagnant catalyst is [Bmim] OAc, and temperature of reaction is 130 ℃, has investigated catalyst levels and DMC and benzyl cyanide has been carried out the influence of methylation reaction.
The influence of table 3 catalyst levels
| Catalyst levels (mmol) | Selectivity (%) | Yield (%) a |
| 0.02 | 100 | 82 |
| 0.04 | 100 | 91 |
| 0.06 | 100 | 94 |
| 0.1 | 100 | 96 |
Reaction conditions all [Bmim] OAc is a catalyzer, and reaction times 10h, DMC are solvent, and temperature of reaction is 130 ℃.
The result find catalyst levels what to not influence of product selectivity, be 10% o'clock of benzyl cyanide mole dosage at catalyst levels, the yield of product obtains being to the maximum 96%.
From the result of table 1, table 2 and table 3, it is catalyzer that optimum reaction conditions should be ionic liquid [Bmim] OAc, and catalyst levels is 10% of a substrate mole dosage, and temperature of reaction is 130 ℃, and methylcarbonate is made solvent and methylating reagent.
Methylcarbonate is a kind of important organic synthesis intermediate, contains functional groups such as carbonyl, methyl and methoxyl group in the molecular structure, thus can be widely used in carbonylation, methylate, organic synthesis such as methoxycarbonylization.Have aborning safe in utilization, nontoxic, convenient, pollute less, characteristics such as transportation easily.Because DMC is nontoxic, the phosgene of alternative severe toxicity, methyl-chloroformate, methyl-sulfate etc. use as methylating agent or carbonylation agent, improve the security of production operation, reduce environmental pollution.As solvent, the alternative fluorine of methylcarbonate Lyons, trichloroethane, trieline, benzene, YLENE etc. are used for paint, cleaning solvent etc.As gasoline dope, methylcarbonate can improve its octane value and oxygen level, and then improves its anti-knocking property.In addition, methylcarbonate also can be made the additive of sanitising agent, tensio-active agent and softening agent.Because purposes is very extensive, methylcarbonate is described as " the new foundation stone " of current organic synthesis.
In addition, also used ionic liquid to be catalyzer among the present invention.Ionic liquid has the characteristics of following several respects: the temperature range that 1. is in a liquid state is big, can reach 300 ℃, and water is 100 ℃; Amine is 40 ℃; Help kinetic control, and since ion liquid fusing point near room temperature, the generation of side reactions such as lower fusing point can be avoided decomposing, disproportionation; 2. soluble end is wide, many inorganic, organic, the organo-metallic of solubilized, macromolecular material, and solubleness is relatively large; 3. there is not significant vapour pressure, not volatile, reduce the problem of environmental pollution that produces because of volatilization, can be used for the high vacuum system; 4. stable, nonflammable, can conduct heat, can flow; 5. they and some organic solvents do not dissolve each other, and a non-water, two-phase system that polarity is adjustable can be provided, and the non-polar phase that dissolves altogether that the hydrophobic ionic liquid can be used as a water uses; 6. they show Flanklin acid with super acids acidity, and acid-basicity is adjustable, its zwitterion can the phase co-conversion, thereby realizes required acid-basicity.
In sum, advantage of the present invention has been to use " green reagent " methylcarbonate, avoids the use of high toxicity and corrosive reagent, and safety is convenient to operation, and productive rate is high, does not produce spent acid; Use ionic liquid to be catalyzer in addition, not only consumption is few, and safety, and catalyzer also can recycle and reuse.
Embodiment
The following example can be used to further specify the present invention, but does not mean that restriction the present invention.
Embodiment 1
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer; Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃; In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature, add the deionized water of 10mL; Use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product; Merge the ether phase; Remove ether with water pump, obtain colourless liquid 2-phenyl propionitrile (0.257g, 98%).
Embodiment 2
In the 40mL autoclave, add respectively to the methylbenzene acetonitrile (0.262g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase; And reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump; Obtain colourless liquid 2-(to methyl) phenyl propionitrile (0.244g, 84%).
Embodiment 3
In the 40mL autoclave, add respectively to the ethylbenzene acetonitrile (0.290g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase; And reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump; Obtain colourless liquid 2-(to ethyl) phenyl propionitrile (0.256g, 82%).
Embodiment 4
In the 40mL autoclave, add respectively to the ethylbenzene acetonitrile (0.356g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase; And reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump; Obtain colourless liquid 2-(to normal-butyl) phenyl propionitrile (0.318g, 85%).
Embodiment 5
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 110 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.074g, 28%).
Embodiment 6
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 120 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.197g, 75%).
Embodiment 7
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (39.6mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 150 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.259g, 99%).
Embodiment 8
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] Cl (34.9mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.252g, 96%).
Embodiment 9
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] Br (43.8mg, 0.2mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.183g, 70%).
Embodiment 10
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (7.9mg, 0.04mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.215g, 82%).
Embodiment 11
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (15.8mg, 0.08mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.238g, 91%).
Embodiment 12
In the 40mL autoclave, add respectively benzyl cyanide (0.234g, 2mmol), [Bmim] OAc (23.6mg, 0.12mmol), methylcarbonate (10mL) and stirrer.Be placed on the reaction kettle that sample mixture is housed and be heated to the reaction kettle internal temperature in the oil bath that is equipped with stirring, thermopair and reach 130 ℃.In this temperature, stirring reaction 10h under this catalyzer.When reaction finishes, make the reaction kettle cool to room temperature.Add the deionized water of 10mL, use the anhydrous diethyl ether of 3 * 10mL to extract then, ionic liquid is soluble in the aqueous phase, and reactant is dissolved in ether mutually with product, merges the ether phase, removes ether with water pump, obtains colourless liquid 2-phenyl propionitrile (0.246g, 94%).
Claims (1)
1. the preparation method of a 2-aryl propionitrile compounds is characterized in that the general formula of this compounds is:
Simultaneously in (I):
R
1For: itrile group;
R
2For: hydrogen or C
1-C
10Alkyl; Its preparation method was that benzyl cyanide or benzyl cyanide compound are dissolved in the methylcarbonate, adds the ionic liquid of catalytic amount, 25～180 ℃ of stirring reactions 1～15 hour; Reaction finishes to be cooled to room temperature, adds entry and solvent, carries out separatory; Water is with twice of SX then; Merge organic phase, rotary evaporation removes and desolvates, and makes the 2-aryl propionitrile compounds; Wherein, ionic liquid is: any one in 1-butyl-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole villaumite, 1-butyl-3-Methylimidazole bromine salt, 1-propyl group-3-Methylimidazole salt compounded of iodine and the 1-butyl-3-methyl imidazolium tetrafluoroborate; It is 1%～100% that catalytic amount refers to the molar percentage that catalyst consumption accounts for benzyl cyanide or benzyl cyanide compound; Solvent is: anhydrous diethyl ether, methylene dichloride, trichloromethane, ETHYLE ACETATE or toluene; The mol ratio of benzyl cyanide or benzyl cyanide compound and methylcarbonate is 1: 1～100.
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