CN114516801A - Improved nitrobenzene compound reduction process - Google Patents
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- CN114516801A CN114516801A CN202210241186.4A CN202210241186A CN114516801A CN 114516801 A CN114516801 A CN 114516801A CN 202210241186 A CN202210241186 A CN 202210241186A CN 114516801 A CN114516801 A CN 114516801A
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- improved
- nitrobenzene compound
- reduction process
- hydrazine hydrate
- nitrobenzene
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- -1 nitrobenzene compound Chemical class 0.000 title claims abstract description 47
- 238000011946 reduction process Methods 0.000 title claims description 19
- 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 claims abstract description 43
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 4
- 150000001448 anilines Chemical class 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- OMNWKPZIFZJANV-UHFFFAOYSA-N 1-(4-chlorophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=C(Cl)C=C1 OMNWKPZIFZJANV-UHFFFAOYSA-N 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 31
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000002518 antifoaming agent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229940032296 ferric chloride Drugs 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000005740 Boscalid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 2
- 229940118790 boscalid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- AXLUNJTWKATZOC-UHFFFAOYSA-N hydrazine nitrobenzene hydrate Chemical compound O.NN.[N+](=O)([O-])C1=CC=CC=C1 AXLUNJTWKATZOC-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an improved nitrobenzene compound reduction method, which uses hydrazine hydrate as a reducing agent to reduce nitrobenzene compounds into aniline compounds, and the reaction is carried out under the condition of no solvent, wherein the reaction temperature is more than 95 ℃ and less than 110 ℃.
Description
Technical Field
The present application relates to an improved nitrobenzene compound reduction process.
Background
The method for reducing nitrobenzene into aniline mainly comprises the following five methods: the method comprises the following steps: the metal is reduced by hydrochloric acid, the method has the defects of generating a large amount of metal solid waste and high treatment cost; the method 2 comprises the following steps: the boron hydride reduction method has the defects of high cost and large solid waste; the method 3 comprises the following steps: hydrazine hydrate reduction method, the method is with high costs, hydrazine hydrate toxicity is great; the method 4 comprises the following steps: the sodium sulfide reduction method has large amount of waste liquid generated by the method; the method 5 comprises the following steps: catalytic hydrogenation processes, which have the disadvantage of using active metal catalysts and hydrogen, generally require high temperatures and pressures.
Non-patent document 1 reports the following hydrazine hydrate reduction method: using activated carbon and ferric chloride hexahydrate as catalysts, absolute ethyl alcohol as a solvent, 4' -chloro-2-nitrobiphenyl: the molar ratio of hydrazine hydrate is 1: 2.5.
Non-patent document 1: boscalid Synthesis research (Sun bin, Li Shuxue; loaded in chemical research and application, volume 26, phase 10)
Disclosure of Invention
In the nitrobenzene hydrazine hydrate reduction method disclosed in non-patent document 1, the molar ratio of the nitrobenzene compound to the hydrazine hydrate is as high as 1:2.5, and the hydrazine hydrate is in large excess compared to the stoichiometry of the 1:1.5 molar ratio. Hydrazine hydrate is high in cost and toxicity, subsequent hydrazine salt needs to be concentrated and recycled through rectification or neutralized, operation is complicated, and treatment cost is high, so that the hydrazine hydrate is unfavorable in environmental protection and economy.
The present inventors have studied the reason why hydrazine hydrate as a reducing agent needs to be greatly excessive in the reduction method of non-patent document 1, and found that this method uses ethanol that is miscible with hydrazine hydrate as a solvent, and because the reaction can be carried out only at low temperature due to the low boiling point of ethanol, the reaction must be completed by using a large excess of hydrazine hydrate.
In view of the above problems, the present invention aims to provide an improved method for reducing a nitrobenzene compound hydrazine hydrate, by which the amount of hydrazine hydrate can be greatly reduced.
Specifically, the present invention provides:
(1) an improved nitrobenzene compound reduction process using hydrazine hydrate as a reducing agent to reduce nitrobenzene compounds to aniline compounds is carried out in the absence of solvent at a temperature above 95 ℃ and below 110 ℃, preferably 100 ℃ and 108 ℃.
(2) An improved process for the reduction of a nitrobenzene compound according to (1) above, wherein the molar ratio of nitro groups to hydrazine hydrate in the nitrobenzene compound is 1: (1.5-1.7), preferably about 1 (1.55-1.65).
(3) An improved nitrobenzene compound reduction process according to the above (1) or (2) wherein further a catalyst, preferably activated carbon and ferric chloride, is used.
(4) The improved reduction process for a nitrobenzene compound according to any one of the above (1) to (3), wherein the nitrobenzene compound is a nitrobiphenyl compound.
(5) The improved nitrobenzene compound reduction process according to (4) above wherein the nitrobiphenyl compound is 4' -halo-2-nitrobiphenyl.
(6) The improved nitrobenzene compound reduction process of (5) above wherein the 4 '-halo-2-nitrobiphenyl is 4' -chloro-2-nitrobiphenyl.
(7) The improved nitrobenzene compound reduction process according to any one of (1) to (6) above wherein the reaction is carried out in the further presence of an antifoaming agent.
(8) The improved process for the reduction of a nitrobenzene compound according to (7) above, wherein the defoamer is of the XP series or the OP series, preferably XP70, XP80, OP-10 or a mixture thereof.
(9) The improved nitrobenzene compound reduction process according to (8) above, wherein the amount of the antifoaming agent is 1 to 10% of the total mass of the nitrobenzene compound and the hydrazine hydrate.
Detailed Description
In the present application, "%" means weight percent unless otherwise specified.
In the present application, the term "halogen" includes fluorine, chlorine, bromine and iodine.
As used herein, the term "nitrobenzene compound" includes nitrobenzene itself and nitrobenzene compounds optionally having 1 to 5 substituents on the benzene ring including, but not limited to, halogen, C1-10Alkyl radical, C1-10Alkyloxy, C3-10Cycloalkyl, C3-10Cycloalkyloxy radical, C6-10Aryl, and the like.
Specifically, the substituent may be 1 or 2 or more selected from the following groups: halogen, C1-6Alkyl radical, C1-6Alkyloxy, C3-6Cycloalkyl radical, C3-6Cycloalkyloxy, phenyl, said phenyl being optionally substituted by 1 or 2 or more selected from halogen, C1-6Alkyl radical, C1-6Alkyl oxygenBase, C3-6Cycloalkyl and C3-6A substituent in cycloalkyloxy.
More specifically, the substituent may be a halophenyl group.
In some embodiments, the nitrobenzene compound is 4 '-halo-2-nitrobiphenyl, more specifically 4' -chloro-2-nitrobiphenyl. The compound is an important intermediate for synthesizing pesticide boscalid.
The method takes a nitrobenzene compound as a substrate and uses hydrazine hydrate as a reducing agent to reduce the nitrobenzene compound into an aniline compound, and is characterized in that the reduction reaction is carried out under the condition of no solvent, and the reaction temperature is more than 95 ℃ and less than 110 ℃.
In the method, the reaction speed is accelerated by increasing the reaction temperature, and meanwhile, the nitrobenzene compound is changed into a molten state at the reaction temperature to form a liquid-liquid two-phase reaction system with hydrazine hydrate, so that a solvent is not required. The reaction temperature is determined depending on the specific type of nitrobenzene compound, and is usually set in the range of 95 ℃ or higher and lower than 110 ℃, preferably in the range of 100 to 108 ℃.
In the liquid-liquid two-phase reaction system of the nitrobenzene compound and the hydrazine hydrate, a catalyst is preferably used. The kind and amount of the catalyst are determined according to the specific kind of the substrate nitrobenzene compound. For example, when the substrate is 4' -halo-2-nitrobiphenyl, ferric chloride and activated carbon are generally used as catalysts.
Compared with the low-temperature catalytic reduction method in non-patent document 1, the method of the present invention can greatly reduce the amount of hydrazine hydrate used as a reducing agent by raising the reaction temperature and increasing the reaction speed, and the molar ratio of nitro groups to hydrazine hydrate in the nitrobenzene compound is preferably 1 (1.5-1.7), more preferably about 1 (1.55-1.65). When the molar equivalent of hydrazine hydrate is less than 1.5, the reaction is incomplete; when the reaction efficiency exceeds 1.65, the reaction efficiency improving effect reaches a plateau stage, and environmental burden and cost waste are caused by large excess.
The reducing agent hydrazine hydrate used in the process of the present invention may be either new hydrazine hydrate or industrially recovered hydrazine hydrate.
The hydrazine hydrate is preferably added dropwise.
In order to avoid the problems that the reaction is slow and the dropwise added hydrazine hydrate is likely to locally accumulate, thereby causing unstable reaction and difficult temperature control, the preferable range temperature is set to be 100 ℃ or higher and lower than the boiling point of hydrazine hydrate by 110 ℃, more preferably 100-.
In the method of the present invention, since a solvent-free reaction system is used, and the problem of entrainment of air bubbles may occur in a relatively high reaction temperature range of 95 ℃ to less than 110 ℃, it is preferable to add a suitable amount of a defoaming agent to the reaction system. The antifoam can be added together at the time of dosing.
The classes of antifoaming agents include the XP series, OP series, and the like, and specific examples include, but are not limited to, XP70, XP80, OP-10, and the like, or mixtures thereof. The dosage of the defoaming agent is generally 1 to 10 per thousand of the total mass of the nitrobenzene compound and the hydrazine hydrate.
After the reaction is finished and the temperature is reduced, the nitrobenzene compound is converted from a molten state into a solid state and is difficult to separate from the solid catalyst. Therefore, it is preferable that the target nitrobenzene compound is dissolved by adding a solvent after the completion of the reaction and then separated from the catalyst by filtration. The kind and amount of the solvent may be any solvent that can sufficiently dissolve the target nitrobenzene compound and is immiscible with water, and specific examples include, but are not limited to, toluene, xylene, and the like.
By the method, the hydrazine hydrate content in the water layer in the reaction system after the reaction is finished is less than 1 percent, and the hydrazine hydrate concentration operation is not needed, so the complex hydrazine hydrate post-treatment is simplified.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these specific embodiments, and any modification and variation within the scope of the present invention will fall within the scope of the present invention.
Example 1
791 g of 4' -chloro-2-nitrobiphenyl, 36.4 g of activated carbon, 9.1 g of ferric chloride and 1.5 g of antifoaming agent XP-70 are added into a reaction bottle, the temperature is raised to 100-.
The water phase after separation was checked by gas chromatography, and it was confirmed that the hydrazine hydrate content was less than 1%.
Liquid chromatography conditions:
mobile phase: acetonitrile: water (pH adjusted to 4.0-4.5 with formic acid) 80: 20
A chromatographic column: kromasil-5C 182.5X 4.6mm (or other equivalent chromatographic column)
Column temperature: wavelength at 30 ℃: flow rate at 225 nm: 1.0 ml/min
Gas chromatography conditions:
a chromatographic column: se-54 chromatographic column (or other equivalent chromatographic columns)
Temperature of the column box: holding at 55 deg.C for 1 min; the temperature was increased to 200 ℃ at a rate of 11.5 ℃ per minute for 5 minutes.
Temperature of the gasification chamber: 200 ℃, detector temperature: 200 deg.C
Example 2
56.56 g of 4' -chloro-2-nitrobiphenyl, 2.6 g of activated carbon, 0.65 g of ferric chloride and 0.4 g of antifoaming agent XP-70 are added into a reaction bottle, the temperature is respectively raised to 95-100 ℃, 100-105 ℃ and 105-110 ℃, and 24.36 g of hydrazine hydrate is added in batches. Otherwise, the procedure was as in example 1.
The residual percentages of 1/3/, 2/3 of the total amount of hydrazine hydrate added dropwise, and of 4' -chloro-2-nitrobiphenyl at all times and 1 hour and 2 hours after the addition were as follows, respectively, as monitored by high performance liquid chromatography:
TABLE 1
Note: meaning that after the remaining% of starting material is less than 1% or very close to 1%, the reaction is complete and no longer monitored.
The inventor of the present application has found that if the temperature in the early stage of the reaction is lower than 100 ℃, the reaction is slow, and the temperature control is difficult in the subsequent hydrazine hydrate dropping process, which may be caused by that when the temperature is low, the dropped hydrazine hydrate reacts slowly, resulting in local accumulation, and after reaching a certain degree, the reaction is suddenly accelerated in a certain period of time, resulting in violent heat release.
On the other hand, when the reaction temperature is close to the boiling point of hydrazine hydrate of 110 ℃, part of hydrazine hydrate is volatilized, which is not favorable for the reaction.
Therefore, the reaction temperature is more preferably set to 100 ℃ to 108 ℃.
Claims (9)
1. An improved nitrobenzene compound reduction process using hydrazine hydrate as a reducing agent to reduce nitrobenzene compounds to aniline compounds is carried out in the absence of solvent at a temperature above 95 ℃ and below 110 ℃, preferably 100 ℃ and 108 ℃.
2. An improved nitrobenzene compound reduction process according to claim 1 wherein the molar ratio of nitro groups to hydrazine hydrate in the nitrobenzene compound is 1: (1.5-1.7), preferably about 1 (1.55-1.65).
3. The improved nitrobenzene compound reduction process according to claim 1 or 2 wherein further a catalyst, preferably activated carbon and ferric chloride, is used.
4. An improved nitrobenzene compound reduction process according to any one of claims 1 to 3 wherein the nitrobenzene compound is a nitrobiphenyl compound.
5. The improved nitrobenzene compound reduction process of claim 4 wherein the nitrobiphenyl compound is 4' -halo-2-nitrobiphenyl.
6. An improved nitrobenzene compound reduction process according to claim 5 wherein the 4 '-halo-2-nitrobiphenyl is 4' -chloro-2-nitrobiphenyl.
7. An improved nitrobenzene compound reduction process according to any one of claims 1 to 6 wherein the reaction is carried out in the further presence of a defoamer.
8. The improved nitrobenzene compound reduction process according to claim 7 wherein the defoamer is of the XP series or the OP series, preferably XP70, XP80, OP-10 or mixtures thereof.
9. The improved nitrobenzene compound reduction process of claim 8 wherein the amount of defoamer used is between 1 and 10 per thousand of the total mass of nitrobenzene compound and hydrazine hydrate.
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| CN202210241186.4A CN114516801A (en) | 2022-03-11 | 2022-03-11 | Improved nitrobenzene compound reduction process |
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|---|---|---|---|---|
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
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| CN109894136A (en) * | 2018-10-23 | 2019-06-18 | 兰州大学 | A kind of catalyst and preparation method and purposes |
-
2022
- 2022-03-11 CN CN202210241186.4A patent/CN114516801A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN103274952A (en) * | 2013-05-13 | 2013-09-04 | 泰莱斯（南通）医药化工有限公司 | Method for preparing o-Chloro-p-phenylenediamine |
| CN108558747A (en) * | 2018-03-31 | 2018-09-21 | 山东罗欣药业集团恒欣药业有限公司 | A kind of preparation method of Rui Gefeini |
| CN109894136A (en) * | 2018-10-23 | 2019-06-18 | 兰州大学 | A kind of catalyst and preparation method and purposes |
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| Title |
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