CN106866432A - A kind of synthesis technique of nitrophenol and its intermediate - Google Patents
A kind of synthesis technique of nitrophenol and its intermediate Download PDFInfo
- Publication number
- CN106866432A CN106866432A CN201710207249.3A CN201710207249A CN106866432A CN 106866432 A CN106866432 A CN 106866432A CN 201710207249 A CN201710207249 A CN 201710207249A CN 106866432 A CN106866432 A CN 106866432A
- Authority
- CN
- China
- Prior art keywords
- compound
- nitrophenol
- organic solvent
- synthetic method
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Abstract
The present invention relates to a kind of nitrophenol and its synthesis technique of intermediate.The invention discloses a kind of synthetic method of the nitrophenol of 2 amino 4.Specific statement process is as follows：The first step, in organic solvent, compound (II) is synthesized by 2 amino-phenols (I) and hydrochloric acid or sulfuric acid reaction, does not reclaim organic solvent, directly carries out next step reaction；Second step, in organic solvent, compound (II) obtains compound (III) by low temperature nitric acid nitrating, and reaction terminates；3rd step, to adding liquid caustic soda in system, Distillation recovery organic solvent, distillation leftover mixes with inorganic acid, separation of solid and liquid obtains compound (IV), mother liquor through distillation and concentration obtain can commercialization byproduct sodium chloride or sodium sulphate, distillation cooling water recovery reaction.It is approximately represented as with chemical equation：
Description
Technical field
The present invention relates to the preparation method of organic compound, more particularly to a kind of nitrophenol and its intermediate synthesis
Technique.
Background technology
2- Amino-4-nitrophenols as a kind of chemical industry synthesis intermediate, be widely used in dyestuff including active black ACE,
Such as production such as blood-pressure drug acebutolol, 2- butyl -6- nitroindolines of neutral black BL/BRL/BGL and medical product.
The method for synthesizing 2- Amino-4-nitrophenols can be divided into electrochemical reducing and the class of chemical reduction method two, wherein, change
Learn reducing process includes general chemical reagent chemical reduction method and metal catalytic hydrogenating reduction method again.Electrochemical reducing is because being produced into
The factors such as this height, electrochemistry facility shortage do not have level capable of being industrialized still.At present, chemical reduction method, especially to 2,4- bis-
2- nitro in nitrophenol structure carries out selective reduction, then synthesizes 2- Amino-4-nitrophenols and is generally studied
With use.【US2464194、US4115652】Disclose with akali sulphide (including sodium persulfide, sodium bisulfide, hydrogen sulfide ammonium etc.)
It is reducing agent reductase 12,2, 4-dinitrophenol is 2- Amino-4-nitrophenols.Although the method can synthesize target compound,
Be exist low material concentration, production process and product with sulfide stink, the reaction time is long, equipment capacity is low, product
Yield is low so that production cost is high, and in order to keep the stablizing relatively, it is necessary to adding chlorine in reaction system of system acid-base value
Change the inorganic matters such as ammonium, limewash, increased the solid waste amount of enterprise's production, although in this way, at the end of reaction, still exist in system
The impurity such as 2- nitros-PAP, 2,4- diaminophenols, azo-compound and tar, have a strong impact on product quality.
【CN105801432、CN105801440】Disclose and catalyst is combined as with Iron(III) chloride hexahydrate/activated carbon, be with hydrazine hydrate
Reducing agent selective reduction 2,4- dinitrophenol is 2- Amino-4-nitrophenols.Sodium sulfide reducing is solved to a certain extent
Pollution in technique is big, the not high deficiency of product quality, but still inevitable 2- nitros-PAP, 2,4- diaminobenzenes
The generation of the impurity such as phenol, azo-compound and tar, meanwhile, hydrazine hydrate is hypertoxic type compound, with severe corrosive, and valency
Lattice are expensive, are unsuitable in field of fine chemical use of large-scale production.
Catalytic hydrogenating reduction nitro generates amino, and the hydrazine hydrate of the sulfide of stench and severe toxicity is not related to, and the three wastes are few,
It is a cleaning procedure praised highly energetically by the Ministry of Science and Technology, Chinese Ministry of Environmental Protection, is widely used in the production of amino-compound.
【CN105566126】A kind of method that liquid phase catalytic hydrogenation prepares 2- Amino-4-nitrophenols is disclosed, with 2,4- dinitro-chlorines
The technical grade 2,4-DNP sodium that benzene hydrolysis is obtained is raw material, and 5%Pd/C is catalyst, in aqueous phase system, through catalysis
Hydrogenation reduction, obtains 2- Amino-4-nitrophenol sodium, and catalyst is recovered by filtration, and filtrate separates out 2- amino -4- after acid adjustment
Nitrophenol, filtering, obtains 2- Amino-4-nitrophenol finished products.Have the advantages that to pollute small, high income, but weak point is
Because technique final step is acid-base neutralization process, inevitably sandwiched in 2- Amino-4-nitrophenol solid precipitation processes
A large amount of salinities, cause 2- Amino-4-nitrophenol active constituent contents to be difficult to meet downstream product production requirement, need to be tied again
The treatment such as crystalline substance is processed 2- Amino-4-nitrophenols.
The present invention discloses the synthesis technique of a kind of nitrophenol and its intermediate, is simply modified by substrate, has
Pollution that effect avoids existing process presence is big, the shortcomings of security is low, occupational health is not up to standard, product quality is not high, have
Serial operation is strong, the disposable advantage for obtaining high-quality product.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided the synthesis work of a kind of nitrophenol and its intermediate
Skill.
A kind of nitrophenol (V) and its synthesis technique of intermediate (IV), comprise the steps of：
1) under the conditions of in organic solvent, acid binding agent is presence or absence of, by 2,4-DNP (I) and chemical combination
Thing (II) synthesizes compound (III) by esterification, wherein compound (II) and 2,4-DNP (I) molal quantity it
Than being 1~1.02:1；
2) compound (III) obtains compound (IV) through catalyst choice catalytic hydrogenating reduction；
3) compound (IV) through hydrolysis, again with hydrochloric acid or sulfuric acid regulation system pH in aqueous slkali through obtaining 2- ammonia
Base -4- nitrophenols (V),
It is expressed as with chemical equation：
Wherein R is the 1-4 alkyl of carbon atom, R1It is Cl-, HO-, R2COO-, R2It is the 1-4 alkyl of carbon atom.
Further, described step 1) in organic solvent used for chloroform, dichloromethane, dichloroethanes or acetone one
Plant or several mixing, organic solvent is 2~3 with the mass ratio of compound (I):1.
Further, described step 1) in acid binding agent used for triethylamine, potassium carbonate, pyridine one or more mix
Close, acid binding agent is 0.5~1.0 with the mol ratio of compound (I):1.
Further, the step 2) organic solvent used be methyl alcohol, the ester of dichloroethanes, 4~7 carbon, it is organic
Solvent is 2~4 with the mass ratio of compound (III):1.
Further, described step 2) in catalyst used for Pd/C, Raney-Ni, Ru/C one or more
Mixing, the quality of catalyst is the 1.0%~0.3% of the quality of compound (I).
Further, described step 3) in alkali used be NaOH, potassium hydroxide one or two mixing.
A kind of midbody compound (III), structural formula is as follows：
Wherein R is the 1-4 alkyl of carbon atom.
A kind of midbody compound (III), structural formula is as follows：
Wherein R is the 1-4 alkyl of carbon atom.
The present invention disclose method and is simply modified by substrate, effectively prevent the pollution of existing process presence greatly,
The shortcomings of security is low, occupational health is not up to standard, product quality is not high, with serial operation it is strong, disposably obtain Gao Pin
The advantage of matter product.
Specific embodiment
The following examples further illustrate some features of the invention, but the present invention applies for the content of protection
Do not limited by following embodiments with scope.
Embodiment 1.
184kg 2,4-DNPs are mixed with 79kg chloroacetic chlorides, 101kg triethylamines, 540kg chloroforms, reaction knot
Beam, obtains 225kg 2,4- dinitro phenylacetates；
225kg 2,4- dinitros phenylacetate are mixed with 450kg methyl alcohol, 0.67kg Pd/C, hydrogen, 2,4- bis- is passed through
The conversion of nitro-acetic acid phenyl ester is complete, obtains the nitro-acetic acid phenyl ester of 181.5kg 2- amino -4；
Mixed with 185.2kg sodium hydroxide solutions by the nitro-acetic acid phenyl ester of 181.5kg 2- amino -4, reaction is completed, and is obtained
To the 2- Amino-4-nitrophenols of 140.6kg purity 99.8%.
Embodiment 2.
184kg 2,4-DNPs are mixed with 123kg isoveryl chloride, 71.9kg potassium carbonate, 368kg acetone, is reacted
Terminate, obtain 266kg 2,4- dinitro isoamyl acid phenenyl esters；
By 266kg 2,4- dinitro isoamyls acid phenenyl ester, 1064kg propyl acetates, 2.66kg Ru/C mixing, reaction is complete,
Obtain the 2- amino -4- nitro isoamyl acid phenenyl esters of 207.9kg purity 98.7%.
Embodiment 3.
Mixed by 184kg 2,4- dinitrophenol and 123kg isoveryl chloride, 71.9kg potassium carbonate, 552kg dichloroethanes
Close, reaction terminates, and obtains 800kg 2,4- dinitro isoamyl acid phenenyl ester dichloroethane solutions；
By 800kg 2,4- dinitro isoamyl acid phenenyl ester dichloroethane solutions mix with 1.06kg Pd/C, stirring until
Reaction is complete, obtains the 2- amino -4- nitro isoamyl acid phenenyl esters of 221kg purity 99.7%.
Embodiment 4.
Mixed with 92.5kg propionyl chlorides, 79kg pyridines, 552kg dichloroethanes by 184kg 2,4-DNPs, instead
Should terminate, obtain 780kg 2,4- dinitro phenyl propionate dichloroethane solutions；
By 780kg 2,4- dinitro phenyl propionate dichloroethane solutions mix with 2.0kg Raney's nickels, and reaction terminates, and obtains
To the 2- amino -4- nitropropionic acid phenyl esters of 201kg purity 99.2%.
Claims (8)
1. a kind of synthetic method of nitrophenol, it is characterised in that comprise the steps of：
1) under the conditions of in organic solvent, acid binding agent is presence or absence of, by 2,4-DNP (I) and compound
(II) compound (III), wherein the ratio between compound (II) and 2,4-DNP (I) molal quantity are synthesized by esterification
It is 1~1.02:1；
2) in organic solvent system, compound (III) obtains compound (IV) through catalyst choice catalytic hydrogenating reduction；
3) compound (IV) through hydrolysis, again with hydrochloric acid or sulfuric acid regulation system pH in aqueous slkali through obtaining 2- amino -4-
Nitrophenol (V),
It is expressed as with chemical equation：
Wherein R is the 1-4 alkyl of carbon atom, R1It is Cl-, HO-, R2COO-, R2It is the 1-4 alkyl of carbon atom.
2. as claimed in claim 1 a kind of synthetic method of nitrophenol, it is characterised in that described step 1) in it is used organic
Solvent is the quality of one or more mixing of chloroform, dichloromethane, dichloroethanes or acetone, organic solvent and compound (I)
The ratio between be 2~3:1.
3. a kind of synthetic method of nitrophenol as claimed in claim 1, it is characterised in that described step 1) in used tie up acid
Agent is one or more mixing of triethylamine, potassium carbonate, pyridine, and acid binding agent is 0.5~1.0 with the mol ratio of compound (I):1.
4. a kind of synthetic method of nitrophenol as claimed in claim 1, it is characterised in that the step 2) it is used organic
Solvent is the ester of methyl alcohol, dichloroethanes, 4~7 carbon, and the organic solvent is 2~4 with the mass ratio of compound (III):1.
5. a kind of synthetic method of nitrophenol as claimed in claim 1, it is characterised in that described step 2) in used urge
Agent is the mixing of one or more of Pd/C, Raney-Ni, Ru/C, and the quality of catalyst is the quality of compound (I)
1.0%~0.3%.
6. as claimed in claim 1 a kind of synthetic method of nitrophenol, it is characterised in that described step 3) in alkali used be
One or two mixing of NaOH, potassium hydroxide.
7. a kind of midbody compound (III), structural formula is as follows：
Wherein R is the 1-4 alkyl of carbon atom.
8. a kind of midbody compound (IV), structural formula is as follows：
Wherein R is the 1-4 alkyl of carbon atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710207249.3A CN106866432A (en) | 2017-03-31 | 2017-03-31 | A kind of synthesis technique of nitrophenol and its intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710207249.3A CN106866432A (en) | 2017-03-31 | 2017-03-31 | A kind of synthesis technique of nitrophenol and its intermediate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106866432A true CN106866432A (en) | 2017-06-20 |
Family
ID=59159711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710207249.3A Pending CN106866432A (en) | 2017-03-31 | 2017-03-31 | A kind of synthesis technique of nitrophenol and its intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866432A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094405A (en) * | 2020-09-23 | 2020-12-18 | 安徽生源化工有限公司 | Synthesis and application method of modified PEG (polyethylene glycol) ball |
| CN113045428A (en) * | 2019-12-26 | 2021-06-29 | 中国农业大学 | Compounds and their use in fat reduction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793107A (en) * | 2005-12-29 | 2006-06-28 | 上海应用技术学院 | Process for preparing and separating purifying amino-4-nitrophenol |
| CN101679375A (en) * | 2007-03-23 | 2010-03-24 | 捷瑞尼股份公司 | 8-oxy-quinoline derivatives as bradykinin b2 receptor modulators |
| WO2015154732A1 (en) * | 2014-04-09 | 2015-10-15 | Agra Group A.S. | Plant stimulators, use thereof and method of plant stimulation |
| CN105566126A (en) * | 2014-11-07 | 2016-05-11 | 沈阳化工研究院有限公司 | Method for preparing 2-amino-4-nitrophenol through liquid catalytic hydrogenation |
-
2017
- 2017-03-31 CN CN201710207249.3A patent/CN106866432A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793107A (en) * | 2005-12-29 | 2006-06-28 | 上海应用技术学院 | Process for preparing and separating purifying amino-4-nitrophenol |
| CN101679375A (en) * | 2007-03-23 | 2010-03-24 | 捷瑞尼股份公司 | 8-oxy-quinoline derivatives as bradykinin b2 receptor modulators |
| WO2015154732A1 (en) * | 2014-04-09 | 2015-10-15 | Agra Group A.S. | Plant stimulators, use thereof and method of plant stimulation |
| CN105566126A (en) * | 2014-11-07 | 2016-05-11 | 沈阳化工研究院有限公司 | Method for preparing 2-amino-4-nitrophenol through liquid catalytic hydrogenation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045428A (en) * | 2019-12-26 | 2021-06-29 | 中国农业大学 | Compounds and their use in fat reduction |
| CN113045428B (en) * | 2019-12-26 | 2022-04-22 | 中国农业大学 | Compounds and their use in fat reduction |
| CN112094405A (en) * | 2020-09-23 | 2020-12-18 | 安徽生源化工有限公司 | Synthesis and application method of modified PEG (polyethylene glycol) ball |
| CN112094405B (en) * | 2020-09-23 | 2023-05-26 | 安徽生源化工有限公司 | Synthesis and application method of modified PEG (polyethylene glycol) ball |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101362710B (en) | Method for preparing aminobenzenesulfonic acid by catalytic hydrogenation | |
| CN105566126A (en) | Method for preparing 2-amino-4-nitrophenol through liquid catalytic hydrogenation | |
| CN113429295B (en) | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor | |
| CN103396306A (en) | Cardanol Gemini polyoxyethylene ether carboxylate and preparation method thereof | |
| CN106866432A (en) | A kind of synthesis technique of nitrophenol and its intermediate | |
| CN106866449A (en) | A kind of method that the acetyl-anisidine of 2 amino 4 is prepared using 2,4 dinitrophenol hydrogenating reduction by-product recoveries | |
| CN107434769B (en) | A kind of 4-aminodiphenylamine production desalination method | |
| CN105727982B (en) | A kind of catalyst of synthesis of low-carbon alcohol and preparation method thereof | |
| CN107619383A (en) | A kind of method for preparing carbasalate calcium micro-crystal powder | |
| CN100439328C (en) | Catalytical hydrogenation process to produce II acid | |
| CN104368340A (en) | Sponge silver catalyst preparation method and application of sponge silver catalyst to oxidation and synthesis of cinnamic acid from cinnamaldehyde | |
| CN103657732B (en) | Preparation method of SO4<2->/TiO2-ZnO mixed crystal solid acid carrier coordination catalyst | |
| CN102875435A (en) | Organic thiosulfuric acid derivative preparation method | |
| CN100551917C (en) | A kind of synthetic method of rubber accelerator DZ | |
| CN103880694A (en) | Preparation method of 2-hydroxy-5-aminobenzoic acid | |
| CN101362705A (en) | 3,5-diaminobenzoic acid preparation method | |
| CN108047032B (en) | By α-ketoglutaric acid to glutaric acid synthetic method | |
| CN104744217A (en) | Hydroquinone synthesis method | |
| CN105017044A (en) | Preparation method of trans-4-aminomethylcyclohexanecarboxylic acid | |
| CN103254095B (en) | Separating and purifying method in iobitridol preparation process | |
| CN101643386A (en) | Preparation method of 2, 6-dichlor fluorbenzene | |
| CN101575301B (en) | Preparation method of 2-amino-5-chlorobenzamide | |
| CN106220842A (en) | The preparation method of poly glycol monomethyl ether propionic ester | |
| CN113979888A (en) | Method for preparing N, N, N-trineovalerylated-1, 3, 5-triaminobenzene | |
| CN108586427B (en) | Preparation method of atorvastatin calcium intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170620 |
|
| RJ01 | Rejection of invention patent application after publication |