CN107915659B - Synthetic method of 3, 4-dichlorobenzonitrile - Google Patents
Synthetic method of 3, 4-dichlorobenzonitrile Download PDFInfo
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- CN107915659B CN107915659B CN201711116630.5A CN201711116630A CN107915659B CN 107915659 B CN107915659 B CN 107915659B CN 201711116630 A CN201711116630 A CN 201711116630A CN 107915659 B CN107915659 B CN 107915659B
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- dichlorobromobenzene
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- KUWBYWUSERRVQP-UHFFFAOYSA-N 3,4-dichlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1Cl KUWBYWUSERRVQP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- CFPZDVAZISWERM-UHFFFAOYSA-N 4-bromo-1,2-dichlorobenzene Chemical compound ClC1=CC=C(Br)C=C1Cl CFPZDVAZISWERM-UHFFFAOYSA-N 0.000 claims abstract description 29
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005893 bromination reaction Methods 0.000 claims abstract description 10
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000031709 bromination Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims description 5
- 229930182821 L-proline Natural products 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229960002429 proline Drugs 0.000 claims description 4
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000012043 crude product Substances 0.000 description 8
- WYUIWKFIFOJVKW-UHFFFAOYSA-N 1,2-dichloro-4-methylbenzene Chemical compound CC1=CC=C(Cl)C(Cl)=C1 WYUIWKFIFOJVKW-UHFFFAOYSA-N 0.000 description 6
- HVKCZUVMQPUWSX-UHFFFAOYSA-N 1-bromo-2,3-dichlorobenzene Chemical compound ClC1=CC=CC(Br)=C1Cl HVKCZUVMQPUWSX-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BTBFCBQZFMQBNT-UHFFFAOYSA-N 3,4-difluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1F BTBFCBQZFMQBNT-UHFFFAOYSA-N 0.000 description 2
- 239000005502 Cyhalofop-butyl Substances 0.000 description 2
- TYIYMOAHACZAMQ-CQSZACIVSA-N Cyhalofop-butyl Chemical group C1=CC(O[C@H](C)C(=O)OCCCC)=CC=C1OC1=CC=C(C#N)C=C1F TYIYMOAHACZAMQ-CQSZACIVSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZWUSBSHBFFPRNE-UHFFFAOYSA-N 3,4-dichlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1Cl ZWUSBSHBFFPRNE-UHFFFAOYSA-N 0.000 description 1
- VPHHJAOJUJHJKD-UHFFFAOYSA-N 3,4-dichlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1 VPHHJAOJUJHJKD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- -1 and preferably Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 3, 4-dichlorobenzonitrile, which comprises the following steps: (1) 1, 2-dichlorobenzene is taken as a raw material, a catalyst A is added, bromine is dropwise added after the temperature is raised, the reaction is carried out under the condition of heat preservation after the dropwise addition is finished, and 3, 4-dichlorobromobenzene is obtained through post-treatment; (2) mixing cuprous cyanide, a catalyst B and a solvent, heating, dropwise adding 3, 4-dichlorobromobenzene diluent, keeping the temperature for reaction after dropwise adding, and performing post-treatment to obtain the 3, 4-dichlorobenzonitrile. The method adopts 1, 2-dichlorobenzene as a raw material, obtains the 3, 4-dichlorobenzonitrile through two-step reactions of bromination and cyanidation, has the molar yield of more than 85 percent and the purity of more than or equal to 98 percent, has low raw material cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of preparation of pesticides and medical intermediates, and particularly relates to a synthetic method of 3, 4-dichlorobenzonitrile.
Background
The 3, 4-difluorobenzonitrile is an important intermediate for preparing the herbicide cyhalofop-butyl, the herbicide has high efficiency, low toxicity and low residue, is very safe to rice crops, has excellent selectivity and can prevent and kill gramineous weeds. 3, 4-dichlorobenzonitrile is a raw material for synthesizing 3, 4-difluorobenzonitrile, so that the 3, 4-dichlorobenzonitrile has a greater application value in the field of pesticides, and the synthesis method thereof is more and more concerned by people.
Specifically, there are many synthetic methods for 3, 4-dichlorobenzonitrile, which can be classified into the following ones according to the starting materials:
(1) the method for synthesizing 3, 4-dichlorobenzonitrile by using 3, 4-dichlorotoluene as a raw material and performing ammoxidation under the action of a catalyst is adopted by most of China. However, since 3, 4-dichlorotoluene is a by-product in the production of 2, 4-dichlorotoluene, the supply of 3, 4-dichlorotoluene is limited to the production of 2, 4-dichlorotoluene after the demand for the main product 2, 4-dichlorotoluene has been relaxed.
(2) 3, 4-dichlorobenzonitrile is synthesized by using 3, 4-dichlorobenzoic acid as a starting material through thionyl chloride chlorination, re-amidation and dehydration by using thionyl chloride. The method has the advantages of expensive initial raw materials, more production process steps and discharge of a large amount of sulfur dioxide and hydrogen chloride gas.
(3) The method uses 3, 4-dichlorobenzaldehyde as a starting material, generates oxime with hydroxylamine hydrochloride, and then generates 3, 4-dichlorobenzonitrile by dehydration, but the starting material is very difficult to obtain and expensive.
Due to the rapid development of cyhalofop-butyl, the market gap of 3, 4-dichlorobenzonitrile is more than 1000 tons/year, and a new method capable of realizing industrial production is imperative to find. The synthesis processes have various characteristics, but have certain disadvantages, and the most important problem is that the raw material supply has a larger problem, so a novel method for synthesizing 3, 4-dichlorobenzonitrile is developed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing 3, 4-dichlorobenzonitrile, which has the advantages of short synthetic route, easily available raw materials, high yield, low cost and less pollution.
The technical scheme adopted by the invention is as follows:
a synthetic method of 3, 4-dichlorobenzonitrile comprises the following steps:
(1) bromination of
1, 2-dichlorobenzene is taken as a raw material, a catalyst A is added, bromine is dropwise added after the temperature is raised, the reaction is carried out under the condition of heat preservation after the dropwise addition is finished, and 3, 4-dichlorobromobenzene is obtained through post-treatment;
(2) cyanidation of
Mixing cuprous cyanide, a catalyst B and a solvent, heating, dropwise adding 3, 4-dichlorobromobenzene diluent, keeping the temperature for reaction after dropwise adding, and performing post-treatment to obtain the 3, 4-dichlorobenzonitrile.
The method adopts 1, 2-dichlorobenzene as a raw material, obtains the 3, 4-dichlorobenzonitrile through two-step reactions of bromination and cyanidation, has the molar yield of more than 85 percent and the purity of more than or equal to 98 percent, has low raw material cost, and is suitable for industrial production.
The synthetic route of the invention is as follows:
in the step (1), the catalyst A is iron powder or ferric trichloride, and the adding amount of the catalyst A is 1-15% of the mass of 1, 2-dichlorobenzene; the specific catalyst is selected, so that the bromination reaction rate can be accelerated, the generation of byproducts can be obviously controlled, and the content of isomers is reduced.
The adding molar ratio of the 1, 2-dichlorobenzene to the bromine is 1.0-1.3: 1, heating to 30-75 ℃ before dropwise adding;
preferably, step (1) is carried out under conditions protected from light, which favour higher yields;
preferably, the dropping speed of the bromine is 0.2-0.3 mL/min, the dropping speed of the bromine is preferably slow, and the accumulation of the bromine caused by too fast dropping of the bromine is prevented, so that dibrominated or even polybrominated substitution byproducts are generated;
in the step (1), the reaction temperature is 30-75 ℃, and the reaction time is 1-4 h; if the reaction temperature is too low, the reaction speed is slow, the reaction temperature is too high, the content of byproducts is increased, preferably, the reaction temperature is 45-60 ℃, and the reaction time is 1.5-3 hours;
in the step (1), the post-treatment comprises adding sodium sulfite solution and dichloromethane for extraction and washing.
In the step (2), the catalyst B is L-proline or hydrated 1, 10-phenanthroline, and the dosage of the catalyst B is 5 per mill-2% of the mass of 3, 4-dichlorobromobenzene;
the solvent is N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) or dimethyl sulfoxide (DMSO), and preferably, the solvent is DMF.
In the step (2), the adding molar ratio of 3, 4-dichlorobromobenzene to cuprous cyanide is 1: 1.0-1.3;
in the step (2), the reaction temperature is 100-150 ℃, and the reaction time is 2-4 h; if the reaction temperature is too low, the reaction speed is slow, impurities are increased obviously after the reaction temperature is higher than 130 ℃, the conversion rate and the yield are low, and preferably, the reaction temperature is 110-130 ℃.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a new synthesis method of 3, 4-dichlorobenzonitrile, which has the advantages of short reaction steps, cheap and easily available raw materials, mild and controllable reaction conditions and great industrial application prospect.
Detailed Description
Example 1
(1) Bromination of
Mixing 26.2g of 1, 2-dichlorobenzene and 2.75g of iron powder, heating to 45 ℃, slowly dripping 26g of bromine at the speed of 0.2mL/min, keeping the temperature for reaction for 2h after dripping is finished, adding a sodium sulfite solution and dichloromethane for extraction and washing after the reaction is finished, desolventizing to obtain 41.6g of a crude product, wherein the crude product contains 5.5% of 1, 2-dichlorobenzene, 2.1% of isomer 2, 3-dichlorobromobenzene, and 0.6% of high-boiling (mainly dibromo or polybrominated products, the same as the latter), rectifying, collecting fractions at 100-110 ℃ under-0.09-minus 0.1MPa for recycling, collecting fractions at 160-165 ℃ under-0.09-minus 0.1MPa for fine products, and obtaining 33.2g of 3, 4-dichlorobromobenzene, the purity of 3, 4-dichlorobromobenzene is 98.5%, and the molar yield is 90.3%.
(2) Cyanidation of
5.4g of cuprous cyanide, 0.1g L-proline and 25g of DMF are mixed and heated to 128 ℃,3, 4-dichlorobromobenzene diluent (a mixed solution of 11.3g of 3, 4-dichlorobromobenzene and 10g of DMF) is added dropwise, the reaction is kept warm for 3 hours after the dropwise addition is finished, and after the reaction is finished and water washing is carried out for layering, 8.3g of a product is obtained, the purity of 3, 4-dichlorobenzonitrile is 98.2%, and the molar yield is 96.5%.
Example 2
(1) Bromination of
Mixing 26.2g of 1, 2-dichlorobenzene and 2.75g of iron powder, heating to 75 ℃, slowly dripping 26g of bromine at the speed of 0.25mL/min, keeping the temperature for reaction for 2 hours after dripping is finished, adding a sodium sulfite solution and dichloromethane for extraction and washing after the reaction is finished, and desolventizing to obtain 41.3g of a crude product, wherein the crude product contains 4.8% of 1, 2-dichlorobenzene, 2.0% of isomer 2, 3-dichlorobromobenzene and 5.2% of high boiling point, rectifying, collecting fractions at 100-110 ℃ under the pressure of-0.09 MPa to-0.1 MPa for recycling, collecting fractions at 160-165 ℃ under the pressure of-0.09 MPa to-0.1 MPa for obtaining 31.5g of a refined product of 3, 4-dichlorobromobenzene, the purity of 3, 4-dichlorobromobenzene is 98.3%, and the molar yield is 85.7%.
(2) Cyanidation of
5.4g of cuprous cyanide, 0.1g L-proline and 25g of DMF are mixed and heated to 150 ℃,3, 4-dichlorobromobenzene diluent (a mixed solution of 11.3g of 3, 4-dichlorobromobenzene and 10g of DMF) is added dropwise, the reaction is kept warm for 3 hours after the dropwise addition is finished, and after the reaction is finished and the reaction is layered by washing, 9.7g of a product is obtained, wherein a plurality of high impurity peaks appear, the purity of 3, 4-dichlorobenzonitrile is 37.89%, and the molar yield (pure) is 42.5%.
Example 3
(1) Bromination of
Mixing 26.2g of o-dichlorobenzene and 0.59g of ferric trichloride, heating to 45 ℃, slowly dripping 26g of bromine at the speed of 0.3mL/min, keeping the temperature for reaction for 2h after dripping is finished, adding a sodium sulfite solution and dichloromethane for extraction and washing after the reaction is finished, and desolventizing to obtain 41.1g of a crude product, wherein the crude product contains 5.0% of 1, 2-dichlorobenzene, 1.0% of isomer 2, 3-dichlorobromobenzene and 2.6% of high boiling point, rectifying, collecting fractions at 100-110 ℃ under the pressure of-0.09 to-0.1 MPa for recycling, collecting fractions at 160-165 ℃ under the pressure of-0.09 to-0.1 MPa for recycling, and obtaining 33.1g of a refined 3, 4-dichlorobromobenzene, the purity of 3, 4-dichlorobromobenzene is 98.5%, and the molar yield is 90.0%.
(2) Cyanidation of
Mixing and heating 5.4g of cuprous cyanide, 0.1g of hydrated 1, 10-phenanthroline and 25g of DMF to 128 ℃, dropwise adding 3, 4-dichlorobromobenzene diluent (a mixed solution of 11.3g of 3, 4-dichlorobromobenzene and 10g of DMF), keeping the temperature for reacting for 3 hours after dropwise adding, and obtaining 8.1g of a product after the reaction is finished and layering by washing, wherein the purity of 3, 4-dichlorobenzonitrile is 98.0%, and the molar yield is 94.2%.
Example 4
(1) Bromination of
Mixing 26.2g of o-dichlorobenzene and 0.59g of ferric trichloride, heating to 75 ℃, slowly dripping 26g of bromine at the speed of 0.2mL/min, keeping the temperature for reaction for 2h after dripping is finished, adding a sodium sulfite solution and dichloromethane for extraction and washing after the reaction is finished, and desolventizing to obtain 40.9g of a crude product, wherein the crude product contains 4.5% of 1, 2-dichlorobenzene, 1.2% of isomer 2, 3-dichlorobromobenzene and 5.6% of high boiling point, rectifying, collecting fractions at 100-110 ℃ under-0.09-0.1 MPa for recycling, collecting fractions at 160-165 ℃ under-0.09-0.1 MPa for use, and obtaining 31.8g of a refined product of 3, 4-dichlorobromobenzene, the purity of which is 98.0%, and the molar yield of which is 86.5%.
(2) Cyanidation of
Mixing and heating 5.4g of cuprous cyanide, 0.1g of hydrated 1, 10-phenanthroline and 25g of DMF to 150 ℃, dropwise adding 3, 4-dichlorobromobenzene diluent (a mixed solution of 11.3g of 3, 4-dichlorobromobenzene and 10g of DMF), keeping the temperature for reaction for 3 hours after dropwise adding is finished, washing and layering after the reaction is finished to obtain 8.5g of a product, wherein the purity of 3, 4-dichlorobenzonitrile is 82.6%, and the molar yield (depurative) is 81.6%.
Comparative example 1
(1) Bromination of
26.2g of 1, 2-dichlorobenzene and the mixture are put into a reaction bottle, heated to 45 ℃, 26g of bromine is slowly dripped at the speed of 0.25mL/min, after the dripping is finished, the reaction is kept for 5 hours, the reaction liquid is sampled by a middle control mode, the conversion rate of the 3, 4-dichlorobromobenzene is 75 percent, and the reaction is slow.
(2) Cyanidation of
5.4g of cuprous cyanide and 25g of DMF are mixed and heated to 128 ℃,3, 4-dichlorobromobenzene diluent (a mixed solution of 11.3g of 3, 4-dichlorobromobenzene and 10g of DMF) is added dropwise, the reaction is kept warm for 6 hours after the dropwise addition is finished, and after the reaction is finished and water washing is carried out for layering, 6.8g of a product is obtained, the purity of 3, 4-dichlorobenzonitrile is 98.3%, and the molar yield is 79.1%.
Comparative example 2
Compared with the example 1, the difference is only that in the step (1), the dropping speed of bromine is 1.5mL/min, the bromine is accumulated due to the excessively high dropping speed of the bromine, the temperature is increased excessively, the content of the by-product is high, the dropping is finished, the reaction is kept for 2 hours, the reaction liquid is subjected to controlled sampling, the conversion rate of the 3, 4-dichlorobromobenzene is 68 percent, the isomer 2, 3-dichlorobromobenzene is 9 percent, and the high boiling point is 18 percent.
Claims (1)
1. The method for synthesizing 3, 4-dichlorobenzonitrile is characterized by comprising the following steps of:
(1) bromination of
1, 2-dichlorobenzene is taken as a raw material, a catalyst A is added, bromine is dropwise added after the temperature is raised, the reaction is carried out under the condition of heat preservation after the dropwise addition is finished, and 3, 4-dichlorobromobenzene is obtained through post-treatment;
(2) cyanidation of
Mixing cuprous cyanide, a catalyst B and a solvent, heating, dropwise adding 3, 4-dichlorobromobenzene diluent, carrying out heat preservation reaction after dropwise adding is finished, and carrying out post-treatment to obtain 3, 4-dichlorobenzonitrile;
in the step (1), the catalyst A is ferric trichloride, and the adding amount of the catalyst A is 1-15% of the mass of 1, 2-dichlorobenzene; the dropping speed of the bromine is 0.2-0.3 mL/min;
in the step (1), the adding molar ratio of the 1, 2-dichlorobenzene to the bromine is 1.0-1.3: 1, heating to 30-75 ℃ before dropwise adding;
in the step (1), the reaction temperature is 45-75 ℃, and the reaction time is 1.5-3 h;
in the step (2), the catalyst B is L-proline or hydrated 1, 10-phenanthroline, and the dosage of the catalyst B is 5 per mill-2% of the mass of 3, 4-dichlorobromobenzene;
in the step (2), the adding molar ratio of the 3, 4-dichlorobromobenzene to the cuprous cyanide is 1: 1.0-1.3; the reaction temperature is 110-130 ℃, and the reaction time is 2-4 h.
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| CN102875276A (en) * | 2012-10-24 | 2013-01-16 | 大连理工大学 | A method for preparing cyanoarenes by aryl bromides |
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| CN102875276A (en) * | 2012-10-24 | 2013-01-16 | 大连理工大学 | A method for preparing cyanoarenes by aryl bromides |
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