CN117945946A - Method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation - Google Patents
Method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation Download PDFInfo
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- CN117945946A CN117945946A CN202311805941.8A CN202311805941A CN117945946A CN 117945946 A CN117945946 A CN 117945946A CN 202311805941 A CN202311805941 A CN 202311805941A CN 117945946 A CN117945946 A CN 117945946A
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- China
- Prior art keywords
- hydroxylamine
- chlorophenyl
- catalytic hydrogenation
- synthesizing
- nitrochlorobenzene
- Prior art date
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- JBGGHWCSFZVUFV-UHFFFAOYSA-N n-(2-chlorophenyl)hydroxylamine Chemical compound ONC1=CC=CC=C1Cl JBGGHWCSFZVUFV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000002390 rotary evaporation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical class C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation, which relates to the technical field of synthesis of o-chlorophenyl hydroxylamine. The synthesis comprises the following steps: weighing raw materials of ortho-nitrochlorobenzene, sodium hydroxide, tetrahydrofuran solvent and nickel catalyst according to a certain proportion; adding reaction raw materials, a solvent and a catalyst into an autoclave respectively; introducing hydrogen into the autoclave for exhausting, pressurizing by 10 kg, heating to 30-35 ℃, and carrying out heat preservation reaction; and cooling and recovering to obtain the o-chlorophenyl hydroxylamine. The invention has the advantages that: the o-chlorophenyl hydroxylamine is synthesized by catalytic hydrogenation of o-nitrochlorobenzene, when the aryl group of the N-aryl hydroxylamine contains chlorine, the reaction has excellent chemical selectivity, the o-chlorophenyl hydroxylamine is synthesized with high selectivity, the impurity in the product is less, the yield of the o-chlorophenyl hydroxylamine is improved, and the synthesis method is environment-friendly and has lower cost.
Description
Technical Field
The invention relates to the technical field of synthesis of o-chlorophenyl hydroxylamine, in particular to a method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation.
Background
N-arylhydroxylamine is a multifunctional organic molecule used as an intermediate for synthesizing industrially valuable fine chemicals, bioactive drugs and polymerization inhibitors. In the reported synthesis of N-aryl hydroxylamine, the nitroaromatics can be selectively reduced from stoichiometric Fe or Zn, also with sodium borohydride or hydrazine hydrate, or by catalytic hydrogenation with heterogeneous metal catalysts (with Pt, ni, pd, rh, ir, ag, au). Metal reduction is severely contaminated and unsuitable for industrialization, while the development of heterogeneous metal catalytic systems has been of great interest because of their stability, their reusability and their ease of separation, and hydrogenation is an environmentally friendly and economical route.
However, since the reduction products of nitroaromatics are complex and diverse products consisting of nitrosamines, aromatic amines, hydroxylamines, hydrazines, pyrimidinylbenzenes and azobenzenes, the preparation of N-arylhydroxylamines with high selectivity has been a challenge. The o-chlorophenyl hydroxylamine belongs to one of N-aryl hydroxylamine, so that the synthesis of the o-chlorophenyl hydroxylamine has the problems, and the yield of the o-chlorophenyl hydroxylamine prepared by the prior art is lower. In the process of producing o-chloroaniline, a method for synthesizing o-chlorophenyl hydroxylamine by directly hydrogenating o-nitrochlorobenzene is found, the route is green and environment-friendly, the cost is low, the preparation has high selectivity, and the yield of the o-chlorophenyl hydroxylamine is improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation, which can solve the problems that the preparation of the o-chlorophenyl hydroxylamine in the prior art does not have high selectivity and has lower yield.
In order to solve the technical problems, the technical scheme of the invention is as follows: the method comprises the following steps:
s1, weighing raw materials of ortho-nitrochlorobenzene, sodium hydroxide and solvent tetrahydrofuran and catalyst nickel according to a proportion;
s2, respectively adding the reaction raw materials, the solvent and the catalyst into an autoclave;
S3, introducing hydrogen into the autoclave for exhausting, pressurizing by 10 kg, heating to 30-35 ℃, and carrying out heat preservation reaction;
s4, cooling and recycling to obtain the o-chlorophenyl hydroxylamine.
Further, in the step S1, the mass ratio of the o-nitrochlorobenzene to the sodium hydroxide to the nickel is: 100:1:1-10.
Further, in the step S3, the incubation time is 5 hours.
Further, in the step S4, the temperature is cooled to room temperature.
Further, in the step S4, after cooling, exhausting, and spin-evaporating to recover the solvent to obtain the o-chlorophenyl hydroxylamine product.
The invention has the advantages that: the o-chlorophenyl hydroxylamine is synthesized by catalytic hydrogenation of o-nitrochlorobenzene, when the aryl group of the N-aryl hydroxylamine contains chlorine, the reaction has excellent chemical selectivity, the synthesis of the o-chlorophenyl hydroxylamine has high selectivity, the impurity in the product is less, the yield of the o-chlorophenyl hydroxylamine is improved, and the synthesis method is environment-friendly and has lower cost.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. The following examples will provide those skilled in the art with a more complete understanding of the present invention and are not intended to limit the invention to the embodiments described.
The specific implementation mode adopts the following technical scheme: the method comprises the following steps:
s1, weighing raw materials of ortho-nitrochlorobenzene, sodium hydroxide, tetrahydrofuran solvent and nickel catalyst according to a proportion, wherein the mass ratio of the ortho-nitrochlorobenzene to the sodium hydroxide to the nickel is as follows: 100:1:1-10.
S2, adding the reaction raw materials, the solvent and the catalyst into the autoclave respectively.
S3, after introducing hydrogen into the autoclave for exhausting, pressurizing by 10 kg, heating to 30-35 ℃, and keeping the temperature for 5 hours, wherein the reaction process is as follows:
。
s4, cooling to room temperature, exhausting, and rotationally evaporating to recover the solvent to obtain the o-chlorophenyl hydroxylamine product.
Example 1:
100g of o-nitrochlorobenzene, 500ml of tetrahydrofuran, 1g of sodium hydroxide and 3 g of catalyst nickel are weighed, the materials are respectively added into an autoclave, 10 kg of pressure is applied after hydrogen is introduced into the autoclave for exhausting, the temperature is heated to 35 ℃, the reaction is carried out for 5 hours, the temperature is cooled to room temperature, the exhaust is carried out, the solvent is recovered by rotary evaporation, and the product o-chlorophenyl hydroxylamine is obtained with the yield of 82%.
Example 2:
100 g of o-nitrochlorobenzene, 500ml of tetrahydrofuran, 1g of sodium hydroxide and 1g of catalyst nickel are weighed, the materials are respectively added into an autoclave, 10 kg of pressure is applied after hydrogen is introduced into the autoclave for exhausting, the temperature is heated to 35 ℃, the reaction is carried out for 5 hours, the room temperature is cooled, the exhaust is carried out, the solvent is recovered by rotary evaporation, and the o-chlorophenyl hydroxylamine product is obtained with the yield of 78%.
Example 3:
100g of o-nitrochlorobenzene, 500ml of tetrahydrofuran, 1g of sodium hydroxide and 10g of catalyst nickel are weighed, the materials are respectively added into an autoclave, 10 kg of pressure is applied after hydrogen is introduced into the autoclave for exhausting, the temperature is heated to 35 ℃, the reaction is carried out for 5 hours, the room temperature is cooled, the exhaust is carried out, the solvent is recovered by rotary evaporation, and the o-chlorophenyl hydroxylamine product is obtained with the yield of 80 percent.
Comparative example:
48.2 g of o-nitrochlorobenzene, 360 g of ethanol, 360 g of 1, 2-dichloroethane, 8g of nickel and 2g of tetrabutylammonium bromide are weighed, 46.9 g of hydrazine hydrate is added dropwise at 15 ℃, the dripping is finished, the temperature is kept for 4 hours, the filtration and the rotary evaporation are carried out to recover the solvent, and the o-chlorophenyl hydroxylamine product is obtained, and the yield is 75%.
As can be seen from the above examples 1-3 and comparative examples, according to the synthesis method of the present invention, the synthesis of o-chlorophenyl hydroxylamine by catalytic hydrogenation of o-nitrochlorobenzene has excellent chemical selectivity, the product has few impurities, the yield of o-chlorophenyl hydroxylamine of examples 1-3 is significantly improved compared with the comparative examples, the synthesis method is environment-friendly and has low cost, and example 1 is the best example.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The method for synthesizing the o-chlorophenyl hydroxylamine by catalytic hydrogenation is characterized by comprising the following steps of: the method comprises the following steps:
s1, weighing raw materials of ortho-nitrochlorobenzene, sodium hydroxide and solvent tetrahydrofuran and catalyst nickel according to a proportion;
s2, respectively adding the reaction raw materials, the solvent and the catalyst into an autoclave;
S3, introducing hydrogen into the autoclave for exhausting, pressurizing by 10 kg, heating to 30-35 ℃, and carrying out heat preservation reaction;
s4, cooling and recycling to obtain the o-chlorophenyl hydroxylamine.
2. The method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation according to claim 1, wherein: in the step S1, the mass ratio of the o-nitrochlorobenzene to the sodium hydroxide to the nickel is: 100:1:1-10.
3. The method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation according to claim 1, wherein: in the step S3, the reaction time is kept at 5 hours.
4. The method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation according to claim 1, wherein: in the step S4, the mixture is cooled to room temperature.
5. The method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation according to claim 1, wherein: in the step S4, after cooling, exhausting, and rotationally steaming to recover the solvent to obtain the o-chlorophenyl hydroxylamine product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311805941.8A CN117945946A (en) | 2023-12-26 | 2023-12-26 | Method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311805941.8A CN117945946A (en) | 2023-12-26 | 2023-12-26 | Method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117945946A true CN117945946A (en) | 2024-04-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311805941.8A Pending CN117945946A (en) | 2023-12-26 | 2023-12-26 | Method for synthesizing o-chlorophenyl hydroxylamine by catalytic hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117945946A (en) |
-
2023
- 2023-12-26 CN CN202311805941.8A patent/CN117945946A/en active Pending
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