CN106554283B - A kind of preparation method of 2,4- dinitrobenzenes oxyethanol - Google Patents
A kind of preparation method of 2,4- dinitrobenzenes oxyethanol Download PDFInfo
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- CN106554283B CN106554283B CN201610953822.0A CN201610953822A CN106554283B CN 106554283 B CN106554283 B CN 106554283B CN 201610953822 A CN201610953822 A CN 201610953822A CN 106554283 B CN106554283 B CN 106554283B
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- dinitrobenzene
- oxyethanol
- ethylene oxide
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- 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
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Abstract
The present invention relates to a kind of preparation methods of 2,4 dinitrobenzene oxyethanols, include the following steps：(1) condensation reaction：It with 2,4 dinitrofluorobenzene for raw material, is hydrolyzed in certain density alkaline aqueous solution, then carries out with ethylene oxide being condensed to yield condensation reaction solution；(2) it extracts：Reaction solution is added dropwise in certain organic solvent, is layered, 2,4 dinitrobenzene oxyethanol crude products are obtained after concentrating decrease temperature crystalline；(3) it purifies：2,4 dinitrobenzene oxyethanol crude products handle to obtain 2,4 dinitrobenzene oxyethanol highly finished product by recrystallization.The present invention reduces environmental pollution while improving product quality quality, so that production is cleaned, environmental protection, product is made to be more suitable for producing in enormous quantities.
Description
Technical field
The present invention relates to a kind of preparation methods of chemical intermediate, more particularly, to 2, the 4- 2,4-dinitrophenoxies of Gao Pin a kind of
The preparation method of ethyl alcohol.
Background technology
2,4- dinitrobenzene oxyethanols are a kind of important chemical industry, medicine intermediate for producing amino benzenes compounds, can
For multiple fields such as dyestuff, hair dye, medicine, pesticide materials.
Preparation method report about 2,4- dinitrobenzene oxyethanols is less, and Chinese patent CN 105367426A are disclosed
The synthetic method of one kind 2,4- dinitrophenoxy ethyl alcohol, using 2,4-dinitrochlorobenzene, ethylene glycol, highly basic class as reaction
Object, deionized water synthesize 2,4- dinitrophenoxies ethyl alcohol, that is, first step by 2,4- dinitros as dispersant, using two-step method
Chlorobenzene heating melts and is uniformly mixed to form approximate homogeneous system with ethylene glycol；Second step is that highly basic is added dropwise into reaction system
Solution is reacted, and deionized water is then added, and system is made further to disperse, and completes synthetic reaction.It uses ethylene glycol potassium
Synthetic method synthesizes object using a large amount of ethylene glycol as solvent.Verification to above scheme simultaneously optimizes, and finds to use
Method described in the patent can generate a large amount of byproducts in last handling process, seriously polluted, be not easy industrialized production.
For green and low cost synthesis 2,4- dinitrobenzene oxyethanols, the present invention provide a kind of system by repeatedly trial
The green synthesis method of standby 2,4- dinitrobenzene oxyethanols.
Invention content
In order to overcome the shortcomings of the prior art, the present invention provides 2, the 4- dinitros of a kind of new green and low cost
The preparation method of base Phenoxyethanol.
The preparation method of one kind 2,4- dinitrobenzene oxyethanols, includes the following steps：
(1) condensation reaction：Using 2,4-dinitrochlorobenzene as raw material, hydrolyzed in certain density alkaline aqueous solution, then with
Ethylene oxide carries out being condensed to yield condensation reaction solution；
(2) it extracts：Reaction solution is added dropwise in certain organic solvent, is layered, 2,4- dinitros are obtained after concentrating decrease temperature crystalline
Base Phenoxyethanol crude product；
(3) it purifies：2,4- dinitrobenzenes oxyethanol crude product handles to obtain 2,4- dinitrobenzenes oxyethanol essence by recrystallization
Product.
Preferably, in step (1), alkaline aqueous solution is sodium hydrate aqueous solution, wet chemical, potassium hydroxide water
One kind in solution.3. the preparation method of 2,4- dinitrobenzenes oxyethanol according to claim 2, it is characterised in that：Institute
It is 5~15% to state alkaline aqueous solution mass concentration.
Preferably, in step (2), the organic solvent of extraction is toluene, tetrahydrofuran, methyl tertiary butyl ether(MTBE), acetic acid
One kind in ethyl ester, methanol, ethyl alcohol.
Preferably, in step (3), recrystallization is methanol-water solution with solvent.
Preferably, setting-up point is 80~100 DEG C.
Preferably, in step (1), the time that ethylene oxide is passed through is 3.5~5.5h.
Preferably, in step (1), the molar ratio of alkali and 2,4-dinitrochlorobenzene is 1~3：1.
Preferably, in step (1), the molar ratio of ethylene oxide and 2,4-dinitrochlorobenzene is 0.08~0.15：1.
Preferably, the preparation method of 2, the 4- dinitrobenzene oxyethanols, includes the following steps：
(1) condensation reaction：In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4- dinitros are sequentially added
Chlorobenzene 202g, potassium hydroxide 123.2g are in 1200ml water, and stirring is warming up to 90 DEG C of heat preservation 1.0h, and heat preservation is finished slowly leads into system
Enter ethylene oxide 49.0g, it is 4.5h to lead to the ethylene oxide time, after leading to epoxy, insulation reaction 0.5h；
(2) it extracts：It is cooled to room temperature to be extracted with solvent toluene, stratification, organic phase obtains 2,4- bis- after being concentrated under reduced pressure
Nitro Phenoxyethanol crude product；
(3) it purifies：2,4- dinitrobenzene oxyethanol crude products, which are added to 1100ml methanol-waters, to be recrystallized, and obtains 2,4-
Dinitrobenzene oxyethanol highly finished product.
The present invention reduces environmental pollution while improving product quality quality, so that production is cleaned, environmental protection, makes
Product is more suitable for producing in enormous quantities.
Specific implementation mode
The present invention is further explained in the light of specific embodiments, but invention which is intended to be protected is not limited to
This.
Embodiment 1
Synthetic route of the present invention is as follows：
In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene 202g is sequentially added
(1.0mol), sodium hydroxide 88.0g (2.2mol) are warming up to 90 DEG C of heat preservation 1.0h in the stirring of 1200ml water, and heat preservation is finished into system
It is slowly introducing ethylene oxide 49.0g (0.12mol), it is 4.5h to lead to the ethylene oxide time, after leading to epoxy, insulation reaction
0.5h is cooled to room temperature and is extracted with solvent toluene, stratification, and organic phase obtains 2,4- dinitrobenzene oxyethanols after being concentrated under reduced pressure
Crude product 208g is added into 1100ml methanol-waters and is recrystallized, and obtains 2,4- dinitrobenzene oxyethanol highly finished product 193g,
Yield 84.6%, purity 99.1%.
Embodiment 2
In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene 202g is sequentially added
(1.0mol), potassium carbonate 165.6g (1.2mol) are warming up to 90 DEG C of heat preservation 1.0h in the stirring of 1200ml water, and heat preservation is finished into system
It is slowly introducing ethylene oxide 49.0g (0.12mol), leads to ethylene oxide time 4.5h, after leading to epoxy, insulation reaction 0.5h,
It is cooled to room temperature to be extracted with solvent toluene, stratification, organic phase obtains 2,4- dinitrobenzene oxyethanol crude products after being concentrated under reduced pressure
215g is added into 1100ml methanol-waters and is recrystallized, and obtains 2,4- dinitrobenzene oxyethanol highly finished product 200g, yield
87.7%, purity 99.15%.
Embodiment 3
In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene 202g is sequentially added
(1.0mol), potassium hydroxide 123.2g (2.2mol) are warming up to 90 DEG C of heat preservation 1.0h in the stirring of 1200ml water, and heat preservation is finished to system
In be slowly introducing ethylene oxide 49.0g (0.12mol), lead to ethylene oxide time 4.5h, lead to epoxy after, insulation reaction
0.5h is cooled to room temperature and is extracted with solvent toluene, stratification, and organic phase obtains 2,4- dinitrobenzene oxyethanols after being concentrated under reduced pressure
Crude product 228g is added into 1100ml methanol-waters and is recrystallized, and obtains 2,4- dinitrobenzene oxyethanol highly finished product 218g,
Yield 95.6%, purity 99.35%.
Embodiment 4
In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene 202g is sequentially added
(1.0mol), potassium hydroxide 123.2g (2.2mol) are warming up to 90 DEG C of heat preservation 1.0h in the stirring of 1200ml water, and heat preservation is finished to system
In be slowly introducing ethylene oxide 49.0g (0.12mol), lead to ethylene oxide time 4.5h, lead to epoxy after, insulation reaction
0.5h is cooled to room temperature and is extracted with solvents tetrahydrofurane, stratification, and organic phase obtains 2,4- 2,4-dinitrophenoxies after being concentrated under reduced pressure
Ethyl alcohol crude product 223g, is added into 1100ml methanol-waters and is recrystallized, and obtains 2,4- dinitrobenzene oxyethanol highly finished product
210g, yield 92.1%, purity 99.21%.
Embodiment 5
In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene 202g is sequentially added
(1.0mol), potassium hydroxide 123.2g (2.2mol) are warming up to 90 DEG C of heat preservation 1.0h in the stirring of 1200ml water, and heat preservation is finished to system
In be slowly introducing ethylene oxide 49.0g (0.12mol), lead to ethylene oxide time 4.5h, lead to epoxy after, insulation reaction
0.5h is cooled to room temperature and is extracted with solvent methyl t-butyl ether, stratification, and 2,4- dinitros are obtained after organic solvent is concentrated under reduced pressure
Base Phenoxyethanol crude product 213g, is added into 1100ml methanol-waters and is recrystallized, and obtains 2,4- dinitrobenzenes oxyethanol essence
Product 200g, yield 87.7%, purity 92.1%.
Embodiment 6-8
Use ethyl acetate, methanol, ethyl alcohol to be extracted as extractant respectively, obtain yield be respectively 88.52%,
86.3% and 86.4%.
The selection of catalyst alkali and the implementation of solvent are found according to the present invention, makees catalyst with potassium hydroxide and uses toluene
As extractant best results.
Claims (1)
1. one kind 2, the preparation method of 4- dinitrobenzene oxyethanols, it is characterised in that include the following steps：
（1）Condensation reaction：In the 2000ml four-hole boiling flasks equipped with thermometer, blender, 2,4-dinitrochlorobenzene is sequentially added
202g, potassium hydroxide 123.2g are in 1200ml water, and stirring is warming up to 90 DEG C of heat preservation 1.0h, and heat preservation, which is finished, is slowly introducing ring into system
Oxidative ethane 49.0g, it is 4.5h to lead to the ethylene oxide time, after leading to epoxy, insulation reaction 0.5h；
（2）Extraction：It is cooled to room temperature to be extracted with solvent toluene, stratification, organic phase obtains 2,4- dinitros after being concentrated under reduced pressure
Phenoxyethanol crude product 228g；
（3）Purifying：2,4- dinitrobenzene oxyethanol crude products, which are added to 1100ml methanol-waters, to be recrystallized, and 2,4- dinitros are obtained
Base Phenoxyethanol highly finished product 218g, yield 95.6%, purity 99.35%.
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| CN201610953822.0A CN106554283B (en) | 2016-11-03 | 2016-11-03 | A kind of preparation method of 2,4- dinitrobenzenes oxyethanol |
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| CN201610953822.0A CN106554283B (en) | 2016-11-03 | 2016-11-03 | A kind of preparation method of 2,4- dinitrobenzenes oxyethanol |
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| CN105801440B (en) * | 2014-12-30 | 2017-11-21 | 江苏安诺其化工有限公司 | A kind of preparation method of the nitrophenol of 2 amino 4 |
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Address after: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Patentee after: Zhejiang DINGLONG Technology Co.,Ltd. Patentee after: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. Address before: 311228 Linjiang Industrial Park, Xiaoshan District, Zhejiang, Hangzhou Patentee before: ZHEJIANG DINGLONG TECHNOLOGY Co.,Ltd. Patentee before: JIANGSU DINGLONG TECHNOLOGY Co.,Ltd. |
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