CN112028793B - Method for preparing nitrile by bismuth complex catalytic amide dehydration - Google Patents
Method for preparing nitrile by bismuth complex catalytic amide dehydration Download PDFInfo
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- CN112028793B CN112028793B CN202010822370.9A CN202010822370A CN112028793B CN 112028793 B CN112028793 B CN 112028793B CN 202010822370 A CN202010822370 A CN 202010822370A CN 112028793 B CN112028793 B CN 112028793B
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a method for preparing nitrile by catalyzing amide dehydration with a bismuth complex, which comprises the following steps: reacting bismuth salt and a ligand in a solvent at room temperature to obtain a solution containing a bismuth complex; adding amide into the solution containing the bismuth complex, and reacting for 6-18 h at room temperature and normal pressure to realize amide dehydration to generate nitrile, wherein the bismuth complex is used as a catalyst; and separating the obtained reaction liquid to obtain a crude product of the nitrile corresponding to the amide. The method has the advantages of mild reaction conditions, high reaction selectivity, wide substrate applicability, simple post-treatment and energy consumption reduction.
Description
Technical Field
The invention relates to a method for producing nitriles from amides.
Background
Nitriles are important chemical raw materials and synthetic intermediates, widely used in the manufacture of pharmaceuticals, synthetic fibers, and plastics, for example, adiponitrile is a raw material for the preparation of nylon 66. Acrylonitrile is a monomer for producing polyacrylonitrile, and can be copolymerized with other monomers to produce synthetic rubber and engineering plastics. The cyanobenzene is mainly used as an intermediate of high-grade coatings such as benzoguanamine and the like, is also an intermediate for synthesizing pesticides, aliphatic amine and benzoic acid, and can be used as a solvent of nitrile rubber, resin, polymer, coatings and the like. The phenylacetonitrile is used for producing phenylacetic acid, phenethylamine, diphenylacetonitrile, beta-phenethyl alcohol, phenylacetaldehyde, alpha-chloro-phenylacetic acid ethyl ester and the like which are intermediates of medicines and pesticides, and is used for preparing phoxim, phenthol, penicillin, phenobarbital and the like. The o-methylbenzonitrile can be used for synthesizing agricultural bactericides such as kresoxim-methyl, mefenapyr, flutolanil and the like. Cumene carbonitrile may be used to synthesize cumene amine. The o-chlorobenzonitrile is mainly used for synthesizing a dye intermediate 2-cyano-4-nitroaniline, and the o-chlorobenzonitrile is used for synthesizing antimalarial drugs, namely, the nitroquine in the medical industry. Phthalonitrile can be used for synthesizing phthalocyanine pigment and dye, phthalein sulfonamide medicine, xylene diisocyanate plastic, high-heat-resistance polyamide fiber, desulfurization catalyst and the like.
At present, the synthesis method of nitrile mainly comprises the oxidative cyanation of alkane, alkene, alditol and amine substrates, the direct cyanation of alkane, halogenated alkane and alkene substrates by adopting a cyano source as a reaction reagent, and the dehydration cyanation of amide, carboxylic acid (ester) and aldoxime substrates. Among the methods, the method for preparing the corresponding nitrile by amide dehydration has the advantages of low toxicity of reaction reagents, water as a reaction byproduct, high reaction selectivity and the like, and has higher environmental and economic benefits.
The conventional method for preparing nitriles by dehydration of amides employs stoichiometric amounts of an acidic reagent (e.g., P) 4 O 10 、POCl 3 、SOCl 2 、TiCl 4 Etc.) and alkaline agents (e.g., naBH) 4 ) As a dehydrating agent to promote amide dehydration, the methods can generate a large amount of acidic or basic byproducts, corrode equipment and have high environmental protection pressure; on the basis, the scholars develop a series of novel catalysts, including a hydrosilane dehydration system, a high-temperature catalytic system, a palladium catalytic dehydration cyanation system and the like, wherein various transition metals or nitrenes catalytically activate Si-H bonds of hydrosilicide to form electrophilic hydrosilicon species, and reaction intermediates can promote the dehydration of primary amide to form nitrile, but hydrogen and silyl ether are generated along with the reaction process, so that the separation difficulty is increased; the dehydration of amides to nitriles requires higher reaction temperatures in the absence of dehydrating agents: (>160 ℃), campbell et al (Campbell J, mcdouglad G, mcnab H, et al synthesis,2007,20, 3179-3184) report that dehydrating agents 3A silica and tungsten trioxide catalyze the dehydration of amides and oximes under fast vacuum pyrolysis conditions, the reaction does not produce other by-products, but the reaction temperature is higher (above 300 ℃) and only suitable for thermally stable amides. Sueoka et al (Sueoka)S, mitsudome T, mizugaki T, et al. Chem Commun,2010,46, 8243-8245) reports that a material loaded with monomer vanadium oxide on hydrotalcite can be used as a heterogeneous catalyst for amide dehydration, amide is subjected to reflux reaction in mesitylene to dehydrate into nitrile under the catalytic action of 20mol% of load, and the system has high reaction temperature (more than 160 ℃), high energy consumption and increased separation difficulty of nitrile and a solvent.
The amide dehydration reaction in the absence of a dehydrating agent as described above is assumed to be carried out at ordinary room temperature instead, resulting in inefficient reaction.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing nitrile by catalyzing amide dehydration through a bismuth complex under a mild condition.
In order to solve the technical problem, the invention provides a method for preparing nitrile by amide dehydration catalyzed by a bismuth complex, which comprises the following steps:
1) Reacting bismuth salt (trivalent bismuth salt) with ligand in solvent at room temperature (2 +/-0.5) for 2 hours to obtain solution containing bismuth complex;
the bismuth salt: ligand =1 to 5;
2) Adding amide into the solution containing the bismuth complex obtained in the step 1), and reacting for 6-18 h at room temperature and normal pressure to realize dehydration of amide to generate nitrile, wherein the bismuth complex is used as a catalyst;
the amide: bismuth salt =5 to 25 in step 1);
3) And separating the reaction liquid obtained in the step 2) to obtain a crude product of the nitrile corresponding to the amide.
The improvement of the method for preparing the nitrile by catalyzing amide dehydration by the bismuth complex of the invention comprises the following steps:
and 3) carrying out a circulating reaction on the solvent, the catalyst and the unreacted amide obtained in the separation process in the step 3).
As a further improvement of the method for preparing nitrile by catalyzing amide dehydration by the bismuth complex of the invention:
the bismuth salt is at least one of bismuth acetate (preferred), bismuth trifluoride, bismuth trichloride, bismuth tribromide, bismuth nitrate (preferred), bismuth sulfate, bismuth phosphate and bismuth borate;
the ligand is at least one of diethylamine, triethylamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, pyridine, 2 '-bipyridine, 1, 10-phenanthroline, triphenylphosphine, tricyclohexylphosphine and 1,1' -binaphthol.
As a further improvement of the process for preparing nitriles by dehydrating amides catalyzed by bismuth complexes of the invention:
the amide in the step 2) is R- (CONH) 2 ) X R is C 6-20 Aryl radical, C 1-20 Straight or branched alkyl, C 1-20 Straight-chain or branched alkenyl, C 1-20 Straight-chain or branched alkynyl, C 3-20 Cycloalkyl, C 3-20 Alkenyl radical, C 3-20 Azaheterocyclyl group, C 3-20 Oxacyclic group, C 3-20 A thiacyclic group; x is 1 or 2;
the group R may contain at least one (one or more) halogen, hydroxyl, carboxyl, carbonyl, amino, nitro, mercapto, etc.
By way of example, the amide is any of: benzamide, 2-methylbenzamide, 3-methylbenzamide, 2, 3-dimethylbenzamide, 2-nitro-4-carboxybenzamide, 4-tert-butylbenzamide, 4-methoxybenzamide, 2-fluorobenzamide, 2-chlorobenzamide, 2-bromobenzamide, 4-hydroxybenzamide, 3-methoxybenzamide, 4-nitrobenzamide, 2-aminobenzamide, 2-thiophenecarboxamide, terephthalamide, phenylacetamide, naphthalene-1-carboxamide, quinoline-6-carboxamide, 4-pyridinecarboxamide, 2, 5-furandicarboxamide, butyramide, isobutyramide, caproamide, succinamide, adipamide, dodecanamide, octadecanamide, cyclohexanecarboxamide.
As a further improvement of the method for preparing nitrile by catalyzing amide dehydration by the bismuth complex of the invention:
the solvent in the step 1) is at least one of methanol, ethanol, ethylene glycol, isopropanol, tetrahydrofuran, acetonitrile, ethyl acetate, cyclohexane, dichloromethane, 1, 2-dichloroethane and toluene.
As a further improvement of the process for preparing nitriles by the bismuth complex catalyzed amide dehydration of the present invention, the separation in step 3) is: the reaction liquid obtained in the step 2) is rectified under reduced pressure, and distillate is respectively a crude product of a solvent, water and nitrile; the bottom liquid contains catalyst and unreacted amide.
The crude nitrile product can be further purified by conventional rectification to give a pure nitrile product.
In the present invention, 1mol of amide is generally used with 0.5 to 1L of a solvent; the room temperature is 15-35 ℃.
The amide conversion rate of the step 2) of the invention is not less than 95.0%. In the step 3), the reaction solution is separated to obtain nitrile (a crude product of nitrile) with the purity of more than or equal to 95.0%, and then the nitrile with the purity of more than or equal to 99.5% is obtained through further purification.
Compared with the prior art, the invention has the following technical advantages:
(1) The catalyst is simple to prepare, corresponding nitrile is prepared from amide under the catalysis of the bismuth complex, a dehydrating agent is not needed, a byproduct is only water, and the discharge of three wastes is reduced;
(2) The reaction is carried out in a homogeneous catalysis system, and the reaction efficiency is high;
(3) The reaction is carried out under mild conditions, the reaction selectivity is high, the applicability of the substrate is wide, the post-treatment is simple, and the energy consumption is reduced.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
Example 1-1, a method for preparing benzonitrile by catalyzing high-efficiency dehydration of benzamide with a bismuth complex, sequentially comprises the following steps:
(1) Dissolving 3mol of triethylamine in 10L of methanol in a reaction container to obtain a methanol solution containing triethylamine;
dissolving 1mol of bismuth acetate in the methanol solution containing triethylamine, and stirring for 2 hours at room temperature to obtain a solution containing a bismuth complex; bismuth complexes as catalysts;
(2) Adding 15mol of benzamide into the reactor, and stirring and reacting for 12 hours at normal pressure and room temperature; to obtain a reacted material (reaction solution).
(3) GC analysis is carried out on the reacted material obtained in the step (2), the conversion rate of the raw material (benzamide) is 98.8%, and the selectivity is 99.8%;
separating the reacted materials according to the following conditions: rectification under reduced pressure (2.0-5.0 kPa) is carried out, the distillate sequentially obtains methanol, water and crude benzonitrile (fraction at the temperature of about 80-100 ℃), and the bottom liquid is a mixture of a catalyst, unreacted benzamide and the like. The purity of the crude benzonitrile was 95.0%.
And further purifying the crude cyanobenzene product by conventional rectification to obtain the cyanobenzene product. The purity of the benzonitrile product is more than 99.5 percent, and the yield is 96.5 percent. The yield of benzonitrile is calculated by the formula:
wherein, Y-product yield;
M 1 -actual yield of benzonitrile;
M 2 theoretical yield of benzonitrile.
Examples 1-2, recycling of the catalyst:
the first cycle is applied mechanically: benzamide and methanol were additionally added to the bottom liquid separated after the reaction of example 1 and methanol until the total amount of benzamide added and benzamide contained in the bottom liquid was 15mol and the total amount of methanol was 10L (i.e., the same amount as in example 1-1), and the rest was identical to example 1-1. When the reaction time is 12 hours, the conversion rate of the benzamide is 98.6 percent, the reaction selectivity is 99.8 percent, the product yield is 96.3 percent, and the product purity is 99.0 percent.
Description of the drawings: generally, the content of benzamide in the kettle bottom liquid needs to be detected in advance.
The above cycle is repeated, and by the eighth time, the conversion rate of the benzamide is 95.2%, the reaction selectivity is 99.0%, the product yield is 92.0%, and the product purity is 98.0%. At the moment, more impurities exist in the reaction system, the product purity is reduced, and the product is not recycled.
Examples 2 to 5, the molar ratio of the ligand to bismuth acetate in the catalyst was changed, and the amount of bismuth acetate was kept constant; the other operations were identical to those of example 1-1, giving examples 2 to 5, the process parameters and the reaction results are shown in Table 1.
TABLE 1
| Examples | Molar ratio of ligand to bismuth acetate | Conversion of starting Material (%) | Reaction selectivity (%) | Product yield (%) |
| 2 | 1:1 | 95.1 | 99.8 | 92.5 |
| 3 | 2:1 | 97.8 | 99.8 | 95.2 |
| 4 | 4:1 | 99.3 | 99.8 | 97.0 |
| 5 | 5:1 | 99.5 | 99.8 | 97.1 |
Examples 6 to 12 were prepared by changing the kind of bismuth salt, keeping the amount of bismuth salt at 1mol, and performing the same procedure as in example 1-1 to obtain examples 6 to 12, wherein the process parameters and the reaction results are shown in Table 2.
TABLE 2
| Examples | Bismuth salt species | Conversion of starting Material (%) | Reaction selectivity (%) | Product yield (%) |
| 6 | Bismuth sulfate | 96.5 | 99.8 | 94.8 |
| 7 | Bismuth trifluoride | 97.1 | 99.8 | 95.0 |
| 8 | Bismuth trichloride | 97.5 | 99.8 | 95.3 |
| 9 | Bismuth tribromide | 97.2 | 99.8 | 95.8 |
| 10 | Bismuth nitrate | 98.3 | 99.8 | 96.1 |
| 11 | Bismuth phosphate | 97.8 | 99.8 | 95.2 |
| 12 | Boric acid bismuth | 98.6 | 99.8 | 96.3 |
Examples 13 to 22 were prepared by changing the type of ligand and maintaining the amount of ligand at 3mol, and performing the same procedure as in example 1-1 to obtain examples 13 to 22, with the process parameters and reaction results shown in Table 3.
TABLE 3
| Examples | Ligand species | Conversion of starting Material (%) | Reaction selectivity (%) | Product yield (%) |
| 13 | Diethylamine | 98.5 | 99.8 | 95.8 |
| 14 | Ethylene diamine | 98.1 | 99.8 | 95.4 |
| 15 | Diethanolamine (DEA) | 98.8 | 99.8 | 96.3 |
| 16 | Triethanolamine | 99.2 | 99.8 | 96.8 |
| 17 | Pyridine compound | 98.3 | 99.8 | 95.1 |
| 18 | 2,2' -bipyridine | 98.8 | 99.8 | 96.2 |
| 19 | 1, 10-phenanthroline | 98.6 | 99.8 | 96.1 |
| 20 | Triphenylphosphine | 98.9 | 99.8 | 96.5 |
| 21 | Tricyclohexylphosphine | 98.2 | 99.8 | 95.7 |
| 22 | 1,1' -binaphthol | 98.5 | 99.8 | 96.0 |
Examples 23 to 50 were prepared by changing the kind of amide, keeping the amount of the amide constant, and keeping the amount of the amide at 15mol, and the other operations were the same as in example 1-1, to obtain examples 23 to 50, and the process parameters and the reaction results are shown in Table 4.
TABLE 4
Examples 51-54 were prepared by varying the molar ratio of amide to bismuth acetate, maintaining the amount of bismuth acetate at 1mol, otherwise operating identically to example 1-1, to give examples 51-54, with the process parameters and reaction results shown in Table 5.
TABLE 5
| Examples | Molar ratio of amide to bismuth acetate | Conversion ratio of raw Material (%) | Reaction selectivity (%) | Product yield (%) |
| 51 | 5:1 | 99.1 | 99.8 | 97.0 |
| 52 | 10:1 | 99.0 | 99.8 | 96.8 |
| 53 | 20:1 | 97.5 | 99.8 | 95.0 |
| 54 | 25:1 | 95.5 | 99.8 | 93.1 |
Examples 55 to 63, the solvent type was changed and the volume was kept constant; the other operations were identical to those of example 1-1, giving examples 55 to 63, the process parameters and the reaction results are shown in Table 6.
TABLE 6
| Examples | Kind of solvent | Conversion of starting Material (%) | Reaction Selectivity (%) | Product yield (%) |
| 55 | Ethanol | 98.5 | 99.8 | 95.8 |
| 56 | Ethylene glycol | 98.7 | 99.8 | 96.2 |
| 57 | Isopropanol (I-propanol) | 98.4 | 99.8 | 95.7 |
| 58 | Tetrahydrofuran (THF) | 98.5 | 99.8 | 95.9 |
| 59 | Acetonitrile (ACN) | 97.8 | 99.8 | 95.0 |
| 60 | Cyclohexane | 95.5 | 99.8 | 92.7 |
| 61 | Methylene dichloride | 97.8 | 99.8 | 95.3 |
| 62 | 1, 2-dichloroethane | 96.4 | 99.8 | 93.8 |
| 63 | Toluene | 98.2 | 99.8 | 95.0 |
Examples 64 to 69, changing the reaction time in step 2), the same procedure as in example 1-1 was repeated to obtain examples 64 to 69, and the process parameters and the reaction results are shown in Table 7.
TABLE 7
Comparative example 1, only bismuth acetate was added to the reaction system without addition of a ligand;
namely, specifically: (1) Adding 1mol of bismuth acetate and 10L of methanol into a reaction container; then immediately carrying out the subsequent steps;
the subsequent steps were the same as in example 1-1.
The conversion of benzamide was only 35.5% and the yield of benzonitrile was only 31.8%.
Comparative example 2, stirring at room temperature for 2h without step (1),
namely, specifically: (1) Adding 3mol of triethylamine, 1mol of bismuth acetate and 10L of methanol into a reaction container; then immediately carrying out the subsequent steps;
the subsequent steps were the same as in example 1-1.
The conversion of benzamide was only 75.2% and the yield of benzonitrile was only 70.5%.
Finally, it is also noted that the above-mentioned list is only a few specific embodiments of the present invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by the person skilled in the art from the present disclosure are to be considered within the scope of the present invention.
Claims (4)
1. The method for preparing nitrile by dehydrating amide under room temperature under the catalysis of the bismuth complex is characterized by comprising the following steps:
1) Reacting bismuth salt and ligand in solvent at room temperature for 2 +/-0.5 hours to obtain solution containing bismuth complex;
the bismuth salt: the molar ratio of the ligand =1 to 5;
the bismuth salt is at least one of bismuth acetate, bismuth trifluoride, bismuth trichloride, bismuth tribromide, bismuth nitrate, bismuth sulfate, bismuth phosphate and bismuth borate;
the ligand is at least one of diethylamine, triethylamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, pyridine, 2 '-bipyridine, 1, 10-phenanthroline, triphenylphosphine, tricyclohexylphosphine and 1,1' -binaphthol;
2) Adding amide into the solution containing the bismuth complex obtained in the step 1), and reacting at room temperature of 15 to 35 ℃ and normal pressure for 6 to 18h so as to realize amide dehydration to generate nitrile, wherein the bismuth complex is used as a catalyst;
the amide: bismuth salt =5 to 25 in step 1);
amide is R- (CONH) 2 ) X R is C 6-20 Aryl radical, C 1-20 Straight or branched alkyl, C 1-20 Straight-chain or branched alkenyl, C 1-20 Straight-chain or branched alkynyl, C 3-20 Cycloalkyl, C 3-20 Alkenyl radical, C 3-20 Azaheterocyclyl group, C 3-20 Oxacyclic group, C 3-20 A thiacyclic group; x is 1 or 2;
the group R contains at least one of halogen, hydroxyl, carboxyl, carbonyl, amino, nitro and sulfydryl;
3) And separating the reaction liquid obtained in the step 2) to obtain a crude product of the nitrile corresponding to the amide.
2. The method for preparing nitrile by dehydrating amide at room temperature under the catalysis of bismuth complex according to claim 1, wherein:
and 3) carrying out a circulating reaction on the solvent, the catalyst and the unreacted amide obtained in the separation process in the step 3).
3. The bismuth complex catalyzed amide room temperature dehydration process to produce nitrile according to claim 1 or 2 wherein:
the solvent in the step 1) is at least one of methanol, ethanol, ethylene glycol, isopropanol, tetrahydrofuran, acetonitrile, ethyl acetate, cyclohexane, dichloromethane, 1, 2-dichloroethane and toluene.
4. The process for preparing nitriles by dehydration of amides at room temperature catalyzed by bismuth complexes according to claim 1 or 2, characterized in that the separation in step 3) is: the reaction liquid obtained in the step 2) is rectified under reduced pressure, and distillate is respectively a crude product of a solvent, water and nitrile; the bottom liquid contains catalyst and unreacted amide.
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| CN112028726A (en) * | 2020-08-18 | 2020-12-04 | 浙江大学衢州研究院 | Method for continuously preparing nitrile from amide |
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