CN113248367B - Method for realizing continuous production of acyl chloride compound by catalysis of immobilized organic base - Google Patents
Method for realizing continuous production of acyl chloride compound by catalysis of immobilized organic base Download PDFInfo
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- CN113248367B CN113248367B CN202110550537.5A CN202110550537A CN113248367B CN 113248367 B CN113248367 B CN 113248367B CN 202110550537 A CN202110550537 A CN 202110550537A CN 113248367 B CN113248367 B CN 113248367B
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- 150000007530 organic bases Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000001263 acyl chlorides Chemical class 0.000 title claims abstract description 29
- 238000010924 continuous production Methods 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 45
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 14
- GEKPNPPFAYJZRD-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl chloride Chemical compound ClC(=O)CC(C)CC(C)(C)C GEKPNPPFAYJZRD-UHFFFAOYSA-N 0.000 claims abstract description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 125000002252 acyl group Chemical group 0.000 claims abstract description 10
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 9
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims abstract description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001361 adipic acid Substances 0.000 claims abstract description 7
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 7
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 6
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 50
- 239000012295 chemical reaction liquid Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000007818 Grignard reagent Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 150000004795 grignard reagents Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- JUIKUQOUMZUFQT-UHFFFAOYSA-N 2-bromoacetamide Chemical compound NC(=O)CBr JUIKUQOUMZUFQT-UHFFFAOYSA-N 0.000 claims description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical group BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- YOQRXZIMSKLRCY-UHFFFAOYSA-N 5-bromonicotinamide Chemical compound NC(=O)C1=CN=CC(Br)=C1 YOQRXZIMSKLRCY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 8
- -1 nicotinamide organic base Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229960003966 nicotinamide Drugs 0.000 abstract description 3
- 239000011570 nicotinamide Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 235000005152 nicotinamide Nutrition 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 abstract 1
- 125000002843 carboxylic acid group Chemical group 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000005815 base catalysis Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PFDVZMRMKCSCBG-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)acetamide Chemical compound CCO[Si](OCC)(OCC)CCCNC(C)=O PFDVZMRMKCSCBG-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- NVXNQZXMEWSWRX-UHFFFAOYSA-N BrC1=NC=CC=C1.O1CCCC1 Chemical compound BrC1=NC=CC=C1.O1CCCC1 NVXNQZXMEWSWRX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- JOPQCTQPHGGFQZ-UHFFFAOYSA-N [SiH4].C(C)(=O)N Chemical compound [SiH4].C(C)(=O)N JOPQCTQPHGGFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- VSRVYCZMSNZEPA-UHFFFAOYSA-N pyridine silane Chemical compound [SiH4].C1=CC=NC=C1 VSRVYCZMSNZEPA-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- UYYPZPBYSNXKTE-UHFFFAOYSA-N triethoxy(3-pyridin-3-ylpropyl)silane Chemical compound C(C)O[Si](CCCC=1C=NC=CC=1)(OCC)OCC UYYPZPBYSNXKTE-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for realizing continuous production of acyl chloride compounds by catalysis of immobilized organic base, belonging to the technical field of organic chemical industry, wherein a glass microchannel reactor is treated by amino, pyridine, acetamide and nicotinamide organic base silane coupling agents, and an immobilized organic base catalyst is used; 3,5, 5-trimethylhexanoic acid, adipic acid, trimethylacetic acid, benzoic acid and terephthalic acid are taken as raw materials, and acyl chlorination reaction is carried out through a fixed bed microchannel to generate corresponding 3,5, 5-trimethylhexanoyl chloride, adipoyl chloride, trimethylacetyl chloride, benzoyl chloride and terephthaloyl chloride; the solvent is one or more of toluene, dichloromethane, dichloroethane, cyclohexane and tetrahydrofuran; the material molar ratio is the number of carboxylic acid groups: the solid phosgene is 3: 1-1.5; the reaction temperature is 30-150 ℃, the total material feeding speed is 5-40 mL/min, and the reaction time is 2-16 min. The method for producing 3,5, 5-trimethyl hexanoyl chloride, benzoyl chloride and adipoyl chloride realizes the reutilization of the catalyst, has high product purity and safe production process, and reduces the environmental pollution.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a method for realizing continuous production of acyl chloride compounds by catalysis of immobilized organic base.
Background
Most of compounds containing acyl chloride groups in molecules are medicines or medical intermediates or basic raw materials for synthesizing medicines. The chlorination reaction of carboxylic acid compounds has important significance in actual production, and the ester compounds are produced by using acyl chloride to replace corresponding carboxylic acid and alcohol, so that the production cost can be reduced, the product quality can be improved, and the environmental pollution can be reduced.
Acyl chloride is used as a reactant and is matched with other raw materials for reaction, and various chemical intermediates or products with novel structures and excellent performance can be synthesized by modifying various substituent groups and utilizing the splicing principle of an active structure and carrying out high-molecular polymerization, so that the acyl chloride has increasingly wide application in the aspects of medicines, pesticides, resource environments and the like.
Currently, the most important method for obtaining acyl chloride is to synthesize acyl chloride by using carboxylic acid and acylating agent. The phosphorus trichloride method is convenient for preparing low-boiling-point acyl chloride by using carboxylic acid and an acyl chlorination reagent; the phosphorus pentachloride method is convenient for preparing acyl chloride with high boiling point, has narrow application range and less application in laboratories and industries; the industrial production of the thionyl chloride method and the phosgene method is earlier, but the problems of environmental protection, operation and the like exist, and an ideal substitute is urgently needed to be found.
In addition, because organic base is often added in a small amount in a reaction system as a catalyst, the organic base in the product acyl chloride is often not subjected to separation post-treatment, which brings impurities to the acyl chloride system, and thus affects the purity of the product.
Disclosure of Invention
The technical problem is as follows: the invention provides a method for realizing continuous production of acyl chloride compounds by catalysis of immobilized organic base, which realizes the reutilization of catalyst and solves the problems of low purity caused by difficult recovery of catalyst and separation of organic base in the product acyl chloride.
The technical scheme is as follows: in order to achieve the purpose, the method for realizing the continuous production of the acyl chloride compound by the catalysis of the immobilized organic base comprises the following steps:
1) introducing a tetrahydrofuran solution of KH-550 (amino functional group silane) containing organic base catalyst groups/synthesized organic base silane coupling agent into a microchannel reactor at 140-150 ℃, introducing nitrogen into the microchannel after the channel is filled with the solution, evacuating the solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with the organic base catalyst groups on the inner wall of the channel;
2) dissolving organic acid in a solvent to obtain a reaction solution a;
3) dissolving solid phosgene in a solvent to obtain a reaction solution b; the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: the solid phosgene is 3: 1-3: 1.5;
4) respectively introducing the reaction liquid a obtained in the step 2) and the reaction liquid b obtained in the step 3) into a microchannel reactor through a feed pump to obtain a mixed liquid c;
5) rectifying the mixed liquid c obtained in the step 4) to obtain the acyl chloride compound.
Further, in the step 1), the synthetic organic base silane coupling agent is obtained by the following steps:
immersing magnesium powder in tetrahydrofuran, and slowly dripping magnesium powder according to the molar ratio of 1: 1 in tetrahydrofuran solution of an organic base; wherein the organic base is selected from bromopyridine, bromoacetamide, 5-bromonicotinamide; the reaction produces a grignard reagent, the grignard reagent produced is reacted with a compound in a molar ratio of 1: 3-chloropropyltriethoxysilane of 1 to obtain the synthetic organic alkali silane coupling agent.
Further, in the step 2), the organic acid is any one of 3,5, 5-trimethylhexanoic acid, adipic acid, trimethylacetic acid, benzoic acid and terephthalic acid; in the step 6), the mixed solution c is rectified to obtain 3,5, 5-trimethyl hexanoyl chloride, adipoyl chloride, trimethyl acetyl chloride, benzoyl chloride and terephthaloyl chloride.
Further, in the step 3), the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: and the solid phosgene is 3: 1.2-3: 1.4.
Further, in the step 1), the feeding speed of the micro-channel reactor is 1-5 mL/min, and after the channel is filled with the solution, the feeding is closed and kept for 5-10 min.
Further, in the step 4), the feeding rate of the feeding pump is controlled to be 5-40 mL/min, and the mixture stays in the microchannel reactor for 4-8 min at the reaction temperature of 40-90 ℃ to perform acyl chlorination reaction, so as to obtain a mixed solution c.
Further, in the step 2) and the step 3), the solvent is one or more of toluene, dichloromethane, dichloroethane, cyclohexane and tetrahydrofuran.
Further, in the step 1), when KH-550 is adopted, the structure of the organic base silane coupling agent is as follows:
when a synthetic organobase silane coupling agent is employed, the synthetic organobase silane coupling agent has the following structure:
From left to right are: a pyridine group, an acetamide group, a nicotinamide group.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the organic base catalyst is immobilized on the wall of the microchannel by using the silane coupling agent to form the catalytic fixed bed, so that the utilization rate of the catalyst is greatly improved, and the problems of difficult catalyst recovery and low product purity are solved;
2. the operation is simple, the mass transfer and heat transfer of the reaction are greatly improved by using the microchannel reactor, the energy utilization rate is improved, the yield is improved, the continuous production is realized by the continuous flow reaction, the product quality control is good, and the repeatability is good;
3. the invention has high safety, and the closed reaction in the microchannel reactor effectively prevents the safety problems of leakage of a small amount of possible phosgene or corrosive products and the like, and ensures the safety of the production process;
4. the solid phosgene used as the acyl chlorination reagent has good acyl chlorination effect, and generates carbon dioxide and hydrogen chloride gas through acyl chlorination reaction, so that compared with the traditional acyl chlorination reagent, the acyl chlorination reagent does not generate polluting acidic gas and heavy polluting wastewater; the invention has safe production process, no harmful gas and greatly reduced environmental pollution.
Drawings
FIG. 1 is a schematic cross-sectional view of an organic base catalyzed fixed bed microchannel treated with a pyridine silane coupling agent;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 3,5, 5-trimethylhexanoyl chloride.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
A method for realizing continuous production of acyl chloride compounds by catalysis of immobilized organic base comprises the following steps:
1) introducing a tetrahydrofuran solution of a KH-550/synthesized organic base silane coupling agent into a microchannel reactor at 140-150 ℃, introducing nitrogen into a microchannel after the microchannel is filled with the solution, emptying the solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an organic base catalyst on the inner wall of the channel;
2) dissolving organic acid in a solvent to obtain a reaction solution a;
3) dissolving solid phosgene in a solvent to obtain a reaction solution b; the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: the solid phosgene is 3: 1-3: 1.5;
4) respectively introducing the reaction liquid a obtained in the step 2) and the reaction liquid b obtained in the step 3) into a microchannel reactor through a feed pump to obtain a mixed liquid c;
5) rectifying the mixed liquid c obtained in the step 4) to obtain the acyl chloride compound.
In the step 1), the synthesized organic alkali silane coupling agent is obtained through the following steps:
immersing magnesium powder in tetrahydrofuran, and slowly dripping magnesium powder according to the molar ratio of 1: 1 in tetrahydrofuran solution of an organic base; wherein the organic base is selected from bromopyridine, bromoacetamide, 5-bromonicotinamide; reacting to form a grignard reagent, the formed grignard reagent being present in a molar ratio of 1: 3-chloropropyltriethoxysilane of 1 to obtain the synthetic organic alkali silane coupling agent.
In the step 2), the organic acid is any one of 3,5, 5-trimethylhexanoic acid, adipic acid, trimethylacetic acid, benzoic acid and terephthalic acid; and 6), rectifying the mixed solution c to obtain 3,5, 5-trimethyl hexanoyl chloride, adipoyl chloride, trimethyl acetyl chloride, benzoyl chloride and terephthaloyl chloride.
In the step 3), the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: and the solid phosgene is 3: 1.2-3: 1.4.
In the step 1), the feeding speed of the microchannel reactor is 1-5 mL/min, and after the channel is filled with the solution, the feeding is closed and kept for 5-10 min.
In the step 4), the feeding speed of the feeding pump is controlled to be 5-40 mL/min, and the mixture stays in the microchannel reactor for 4-8 min at the reaction temperature of 40-90 ℃ to carry out acyl chlorination reaction, so that a mixed solution c is obtained.
In the step 2) and the step 3), the solvent is one or more of toluene, dichloromethane, dichloroethane, cyclohexane and tetrahydrofuran.
In step 1), when KH-550 is used, the structure of the organic base silane coupling agent is as follows:
when a synthetic organobase silane coupling agent is employed, the synthetic organobase silane coupling agent has the following structure:
From left to right are: a pyridine group, an acetamide group, a nicotinamide group.
Example 1
The invention relates to a method for synthesizing 3,5, 5-trimethyl hexanoyl chloride by using immobilized organic base catalysis, which comprises the following steps:
1) preparing 10g of KH-550 silane coupling agent into 100mL of tetrahydrofuran solution;
2) introducing the KH-550 solution into a microchannel reactor at 140 ℃ at a feeding speed of 1mL/min, after the channel is filled with the solution, closing the feeding and keeping for 5min, introducing nitrogen into the microchannel, emptying the coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an amino catalyst on the inner wall of the channel;
3) dissolving 61.3g of 3,5, 5-trimethylhexanoic acid in a solvent of tetrahydrofuran to obtain a reaction solution a;
4) dissolving 50.0g of solid phosgene in tetrahydrofuran solvent, wherein the molar ratio of 3,5, 5-trimethylhexanoic acid to the solid phosgene is 3:1.3, so as to obtain reaction liquid b;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 10mL/min, and staying for 8min in the microchannel reactor at a reaction temperature of 55 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain the 3,5, 5-trimethyl hexanoyl chloride.
The product yield of the 3,5, 5-trimethyl hexanoyl chloride prepared by the method is 98.12% and the purity reaches 99.8%.
Example 2
The invention relates to a method for synthesizing 3,5, 5-trimethyl hexanoyl chloride by using immobilized organic base catalysis, which comprises the following steps:
1) preparing 10g of KH-550 silane coupling agent into 100mL of tetrahydrofuran solution;
2) introducing the KH-550 solution into a microchannel reactor at 140 ℃ at a feeding speed of 5mL/min, after the channel is filled with the solution, closing the feeding and keeping for 10min, introducing nitrogen into the microchannel, emptying the coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an amino catalyst on the inner wall of the channel;
3) dissolving 95.9g of 3,5, 5-trimethylhexanoic acid in a composite solvent of dichloromethane and toluene to obtain a reaction solution a;
4) dissolving 60.0g of solid phosgene in a composite solvent of dichloromethane and toluene to obtain a reaction solution b, wherein the molar ratio of 3,5, 5-trimethylhexanoic acid to the solid phosgene is 3: 1;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 5mL/min, and staying in the microchannel reactor for 16min at a reaction temperature of 30 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain the 3,5, 5-trimethyl hexanoyl chloride.
The product yield of the 3,5, 5-trimethyl hexanoyl chloride prepared by the method is 90.63 percent and the purity reaches 99.5 percent.
Example 3
The invention relates to a method for synthesizing trimethylacetyl chloride by using immobilized organic base catalysis, which comprises the following steps:
1) 2.4g of magnesium powder is immersed in 25mL of tetrahydrofuran, and 50mL of 0.5mol/L bromopyridine tetrahydrofuran solution is slowly dropped to react to generate the Grignard reagent. Slowly dripping 50 mL0.5mol/L3-chloropropyltriethoxysilane in an ice bath to react to obtain an aminosilane coupling agent;
2) introducing a 3-pyridylpropyltriethoxysilane solution into a microchannel reactor at 150 ℃ at a feeding speed of 1mL/min, closing feeding and keeping for 5min after a channel is filled with the solution, introducing nitrogen into the microchannel, emptying a coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an amino catalyst on the inner wall of the channel;
3) dissolving 30.9g of trimethylacetic acid in a solvent of cyclohexane to obtain a reaction solution a;
4) dissolving 60.0g of solid phosgene in cyclohexane solvent, wherein the molar ratio of trimethyl acetic acid to the solid phosgene is 3:1.5, and obtaining reaction liquid b;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 10mL/min, and staying for 8min in the microchannel reactor at a reaction temperature of 90 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain the trimethylacetyl chloride.
The yield of the benzoyl chloride prepared by the method is 92.62 percent and the purity reaches 99.1 percent.
Example 4
The invention discloses a method for synthesizing adipoyl chloride by using immobilized organic base catalysis, which comprises the following steps:
1) 2.4g of magnesium powder is immersed in 25mL of tetrahydrofuran, and 50mL of 0.5mol/L bromoacetamide tetrahydrofuran solution is slowly dropped to react to generate the Grignard reagent. Slowly dripping 50 mL0.5mol/L3-chloropropyltriethoxysilane in an ice bath to react to obtain an acetamide silane coupling agent;
2) introducing a 3-acetamidopropyltriethoxysilane solution into a microchannel reactor at 150 ℃ at a feeding speed of 1mL/min, after the channel is filled with the solution, closing the feeding and keeping for 5min, introducing nitrogen into the microchannel, emptying the coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an acetamide catalyst on the inner wall of the channel;
3) dissolving 74.0g of adipic acid in tetrahydrofuran solvent to obtain reaction liquid a;
4) 60.0g of phosgene in solid form was dissolved in tetrahydrofuran solvent, and the molar ratio of adipic acid to phosgene in question was the number of carboxyl groups, since adipic acid has two carboxyl groups: obtaining reaction liquid b by using solid phosgene as 3: 1.5;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 40mL/min, and staying in the microchannel reactor for 2min at a reaction temperature of 150 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain adipoyl chloride.
The product yield of adipoyl chloride prepared by the method is 85.59 percent and the purity reaches 98.9 percent.
Example 5
The invention relates to a method for synthesizing benzoyl chloride by using immobilized organic base catalysis, which comprises the following steps:
1) 2.4g of magnesium powder is immersed in 25mL of tetrahydrofuran, and 50mL of 0.5mol/L bromoacetamide tetrahydrofuran solution is slowly dropped to react to generate the Grignard reagent. Slowly dripping 50 mL0.5mol/L3-chloropropyltriethoxysilane in an ice bath to react to obtain a nicotinamide silane coupling agent;
2) introducing a 3-acetamidopropyltriethoxysilane solution into a microchannel reactor at 150 ℃ at a feeding speed of 1mL/min, after the channel is filled with the solution, closing the feeding and keeping for 5min, introducing nitrogen into the microchannel, emptying the coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an acetamide catalyst on the inner wall of the channel;
3) dissolving 61.7g of benzoic acid in a solvent of toluene to obtain a reaction solution a;
4) dissolving 60.0g of solid phosgene in a solvent toluene, wherein the molar ratio of benzoic acid to the solid phosgene is 3:1.2, so as to obtain a reaction liquid b;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 20mL/min, and staying for 4min in the microchannel reactor at a reaction temperature of 90 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain the benzoyl chloride.
The yield of the benzoyl chloride prepared by the method is 89.85% and the purity reaches 98.7%.
Example 6
The invention relates to a method for synthesizing terephthaloyl chloride by using immobilized organic base as a catalyst, which comprises the following steps:
1) 2.4g of magnesium powder is immersed in 25mL of tetrahydrofuran, and 50mL of 0.5 mol/L3-bromonicotinamide tetrahydrofuran solution is slowly dropped to react to generate the Grignard reagent. Slowly dripping 50 mL0.5mol/L3-chloropropyltriethoxysilane in an ice bath to react to obtain a nicotinamide silane coupling agent;
2) introducing a 3-nicotinamide propyltriethoxysilane solution into a microchannel reactor at a feeding speed of 1mL/min at 150 ℃, closing feeding and keeping for 5min after a channel is filled with the solution, introducing nitrogen into the microchannel, emptying a coupling agent solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with a nicotinamide catalyst on the inner wall of the channel;
3) dissolving 76.3g of terephthalic acid in a composite solvent of solvents of toluene, cyclohexane and dichloroethane to obtain a reaction liquid a;
4) 60.0g of solid phosgene is dissolved in a composite solvent of solvents toluene, cyclohexane and dichloroethane, and because terephthalic acid has two carboxyl groups, the molar ratio of the terephthalic acid to the solid phosgene is the number of the carboxyl groups: obtaining reaction liquid b by using solid phosgene as 3: 1;
5) respectively introducing the reaction liquid a obtained in the step 3) and the reaction liquid b obtained in the step 4) into a microchannel reactor through a feeding pump at a feeding rate of 40mL/min, and staying for 2min in the microchannel reactor at a reaction temperature of 110 ℃ to obtain a mixed liquid c;
6) rectifying the mixed solution c obtained in the step 5) to obtain the terephthaloyl chloride.
The product yield of the terephthaloyl chloride prepared by the above method is 85.34% and the purity is 99.8%.
Claims (7)
1. A method for realizing continuous production of acyl chloride compounds by catalysis of immobilized organic base is characterized by comprising the following steps:
1) introducing an organic alkali silane coupling agent of KH-550 or a synthesized tetrahydrofuran solution of the organic alkali silane coupling agent into a microchannel reactor at 140-150 ℃, introducing nitrogen into the microchannel after the channel is filled with the solution, emptying the solution, and naturally cooling to normal temperature to obtain a catalytic fixed bed microchannel with an organic alkali catalyst group on the inner wall of the channel;
2) dissolving organic acid in a solvent to obtain a reaction solution a;
3) dissolving solid phosgene in a solvent to obtain a reaction solution b; the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: the solid phosgene is =3: 1-3: 1.5;
4) respectively introducing the reaction liquid a obtained in the step 2) and the reaction liquid b obtained in the step 3) into a microchannel reactor through a feed pump to obtain a mixed liquid c;
5) rectifying the mixed liquid c obtained in the step 4) to obtain an acyl chloride compound;
in the step 1), when KH-550 is adopted, the structure of the organic alkali silane coupling agent is as follows:
when a synthetic organobase silane coupling agent is employed, the synthetic organobase silane coupling agent has the following structure:
2. The method for realizing the continuous production of the acyl chloride compound catalyzed by the organic base supported on the carrier according to claim 1, wherein in the step 1), the synthetic organic base silane coupling agent is obtained by the following steps:
immersing magnesium powder in tetrahydrofuran, and slowly dripping magnesium powder according to the molar ratio of 1: 1 in tetrahydrofuran solution of an organic base; wherein the organic base is selected from bromopyridine, bromoacetamide, 5-bromonicotinamide; the reaction produces a grignard reagent, the grignard reagent produced is reacted with a compound in a molar ratio of 1: 3-chloropropyltriethoxysilane of 1 to obtain the synthetic organic alkali silane coupling agent.
3. The method for continuous production of acyl chloride compound catalyzed by organic base supported on the carrier of claim 1, wherein in the step 2), the organic acid is any one of 3,5, 5-trimethylhexanoic acid, adipic acid, trimethylacetic acid, benzoic acid and terephthalic acid; in the step 5), the mixed solution c is rectified to obtain 3,5, 5-trimethyl hexanoyl chloride, adipoyl chloride, trimethyl acetyl chloride, benzoyl chloride and terephthaloyl chloride.
4. The method for realizing the continuous production of the acyl chloride compound under the catalysis of the immobilized organic base according to claim 1, wherein in the step 3), the molar ratio of the organic acid to the solid phosgene is the number of carboxyl groups: and solid phosgene =3: 1.2-3: 1.4.
5. The method for realizing the continuous production of the acyl chloride compound under the catalysis of the immobilized organic base according to claim 1, wherein in the step 1), the feeding speed of the microchannel reactor is 1-5 mL/min, and after the channels are filled with the solution, the feeding is stopped and kept for 5-10 min.
6. The method for realizing the continuous production of the acyl chloride compound under the catalysis of the immobilized organic base according to claim 1, wherein in the step 4), the feeding rate of the feeding pump is controlled to be 5-40 mL/min, and the acyl chloride compound stays in the microchannel reactor for 4-8 min at the reaction temperature of 40-90 ℃ to perform the acyl chlorination reaction, so as to obtain the mixed solution c.
7. The method for realizing the continuous production of the acyl chloride compound under the catalysis of the immobilized organic base according to claim 1, wherein in the step 2) and the step 3), the solvent is one or more of toluene, dichloromethane, dichloroethane, cyclohexane and tetrahydrofuran.
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