CN100422137C - Nitrobenzene derivative containing phenoxy and its preparation method - Google Patents
Nitrobenzene derivative containing phenoxy and its preparation method Download PDFInfo
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- CN100422137C CN100422137C CNB2006101249163A CN200610124916A CN100422137C CN 100422137 C CN100422137 C CN 100422137C CN B2006101249163 A CNB2006101249163 A CN B2006101249163A CN 200610124916 A CN200610124916 A CN 200610124916A CN 100422137 C CN100422137 C CN 100422137C
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- phenoxy group
- chloro
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- nitrobenzene derivative
- reaction
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Abstract
The present invention relates to a nitrobenzene derivative containing phenoxy group and its preparation method. Said invention also provides its chemical structure formula. The invented product is an important organic chemical intermediate product, it can be used for making moth-proofing finish of cotton-wool fabrics, also can be used for synthesizing new-type diazotized photosensitive material, and also can be used as raw material for synthesizing other fine chemical products.
Description
Technical field
The present invention relates to a kind of organic compound and preparation method thereof, is a kind of nitrobenzene derivative that contains phenoxy group and preparation method thereof specifically.
Background technology
Oil of mirbane is a kind of important chemical material, can prepare the intermediate of various fine chemistry industries by it, therefore has purposes widely.At present the patent report of relevant oil of mirbane and preparation method thereof has a lot, and for example the patent No. is that 02143481.6 patent of invention discloses a kind of chemical synthesis process of 5-chloro-2-N-methyl-p-nitroaniline, but does not but have document to put down in writing for the oil of mirbane that contains phenoxy group.And the oil of mirbane that contains phenoxy group is the extremely important nitrobenzene derivative of a class, and along with the develop rapidly of chemical industry, they are widely used in the new chemical materials field.Therefore, a kind of nitrobenzene derivative that contains phenoxy group of invention and preparation method thereof will play very big pushing effect for the new chemical materials of exploitation.
Description
Purpose of the present invention is exactly the deficiency that exists at prior art, and a kind of nitrobenzene derivative that contains phenoxy group and preparation method thereof is provided.
General structure of the present invention is as follows:
Wherein: X
1, X
2Identical or different, and all represent Cl or F.
Preferred X
1, X
2Be Cl.
Preparation method (A) is as follows: add sodium hydroxide, organic solvent in reactor, start stirring, add the 4-chlorophenol, reflux 4-6 hour, lower the temperature 50-65 ℃ then, add the 2.5-dichloronitrobenzene, be warming up to 100 ℃-150 ℃ and react, with reaction product separate, washing is to neutral and be prepared into.Organic solvent is methyl alcohol, ethanol or acetone.
On the basis of this invention, another general structure of the present invention is as follows:
Wherein: R
1, R
2Identical or different, and all represent H or C
1-C
4Alkyl, X
1, X
4Identical or different, and all represent Cl or F.
Preferred R
1, R
2Identical, and all represent C
1Or C
2Alkyl, X
1, X
2Be Cl.Further specifically be preferably 5-chloro-2-(4 '-chloro phenoxy group)-N, N-Diethyl Aniline or 5-chloro-2-(4 '-chlorophenoxy)-N, accelerine.
Further general structure is as follows again in the present invention:
Wherein: R
1, R
2Identical or different, and all represent H or C
1-C
4Alkyl, X
1, X
2Identical or different, and all represent Cl or F.
Preferred R
1, R
2Identical, and all represent C
2Alkyl, X
1, X
2Be Cl.
The preparation method may further comprise the steps:
A. in reactor, start and stir adding organic solvent and water, stir the compound that adds preparation method (A) preparation down, be warming up to 80-100 ℃, slowly add reductive agent, reacted 4-6 hour, cool off, filter, be washed till neutrality, it is product that the gained solid product obtains aniline with acetone recrystallization;
B. above-mentioned intermediate product, monobromethane, water, yellow soda ash, dodecyl triethyamino benzyl ammonia chloride (TEBA) are added autoclave pressure, 50-100 ℃ of reaction 10-20 hour; Reduce to room temperature, filtration, washing, divide oil-yielding stratum, getting dark oil liquid is N, and N aniline is product;
C. in reactor, add dense H
2SO
4, ice bath reduces to below 10 ℃, slowly adds prepared dark oil liquid, stirs, controlled temperature is lower than 5 ℃ then, drips nitration mixture and carries out nitration reaction, drips the back and continues reaction 6-10 hour; Reaction solution iced analyse, filter and make thing of the present invention.
Reductive agent among the described step a is preferably zinc powder.
Described nitration mixture is by dense H
2SO
4, dense HNO
2And H
2O is formulated.
With 5-chloro-2-(4 '-chloro phenoxy group)-N, N dimethylamine base-4-oil of mirbane is example, and the chemical equation of each step of the present invention is as follows:
1. the preparation of 5-chloro-2-(4 '-chloro phenoxy group) oil of mirbane
2. the preparation of 5-chlorine 2-(4 '-chloro phenoxy group)-aniline
3.5-chloro-2-(4 '-chlorophenoxy)-N, the preparation of N dimethylamine base-4-oil of mirbane
The present invention's series is a kind of important organic chemical industry's intermediate product, and it can be used for the anti-maggot arrangement of cotton wool fabric, also can be used for the synthesizing new diazo photographic material, can also be as the synthesis material of other fine chemical product, and its purposes is very extensive.
Embodiment 1
1, the preparation of 5-chloro-2-(4 '-chloro phenoxy group) oil of mirbane (I)
Having electronic stirring, thermometer is in the four-hole vial of prolong, add sodium hydroxide 16g, solvent 60ml starts stirring, add 4-chlorophenol 25.7g (0.1mol), add and refluxed 4 hours, be cooled to 60 ℃ then, add 36.5g 2.5-dichloronitrobenzene, be warming up to 130 ℃, reaction 8hr, pour into while hot then in the 500ml frozen water, stir 10min, suction filtration, be washed till neutrality, get the 40g yellow solid.mp：70～72℃
2, the preparation of 5-chloro-2-(4 '-chlorophenoxy)-aniline (II)
Having electronic stirring, thermometer is in the four-hole vial of prolong, start stirring, add 70ml solvent and water 70ml, stir adding 40g 5-chloro-2-(4 '-chloro phenoxy group) oil of mirbane down, be warming up to 80 ℃, add reductive agent zinc powder 40g, (slowly adding in batches).
Finish, reacted 4 hours down in 80 ℃.Solid is separated out in cooling.Filter, be washed till neutrality, the solid acetone recrystallization gets 35g 5-chloro-2-(4 '-chlorophenoxy)-aniline.
3,5-chloro-2-(4 '-chloro phenoxy group)-N, the preparation of N-Diethyl Aniline (III)
With 5-chloro-2-(4 '-chloro phenoxy group)-aniline 30g, monobromethane 60ml, water 60ml, yellow soda ash 30g, TEBA0.5g adds autoclave pressure, 100 ℃ were reacted 20 hours, reduced to room temperature, filtered, divide oil-yielding stratum, washed several times with water gets dark oil liquid 30g 5-chloro-2-(4 '-chloro phenoxy group)-N, N-two basic aniline
4,5-chloro-2-(4 '-chloro phenoxy group)-N, the preparation of N dimethylamine base-4-oil of mirbane (IV)
Having electronic stirring, thermometer in the ware mouth vial of prolong, adds dense H
2SO
4100ml, ice bath reduce to 9 ℃, slowly add III14g, stir 10min, drip nitration mixture (15ml H2O forms for the dense H2SO4 of 30ml, the dense HNO3 of 30ml).2 ℃ of controlled temperature finish, reaction 6hn.Reaction solution ice is folded in the 1500ml frozen water, and agitation and filtration gets 70g5-chloro-2-(4 '-chloro phenoxy group)-N, N dimethylamine base-4-oil of mirbane.
Embodiment 2
With 5-chloro-2-(4 '-chlorophenoxy)-aniline (II) 47.5g, 50% monobromethane methanol solution 100ml (W/W), Na
2CO
332g, TEBA0.5g adds autoclave pressure, reaction 24hr under 50～100 ℃, cooling adds water stratification, gets brown oily liquids 48.5g5-chloro-2-(4 '-chloro phenoxy group)-N, accelerine after the oil reservoir washing.
To electronic stirring be housed, the four-hole bottle that temperature is taken into account dropping funnel adds 140ml, H
2SO
4Reduce to 10 ℃ and add 26.8g, stir 15min, keep and drip nitration mixture (ratio is the same) below 10 ℃, controlled temperature≤12 ℃ drip off and stir 6hr, and ice is analysed in the 1000ml water, agitation and filtration gets 5-chloro-2-(4 '-chloro phenoxy group)-N, N dimethylamine base-4-oil of mirbane 28.8g.
Embodiment 3
With 5-chloro-2-(4 '-chlorophenoxy)-aniline 24g, n-propyl bromide 30g, ethanol 50ml, water 100ml, Na
2CO
332g places autoclave pressure, intensification 70-100 ℃ of reaction 24hr, and cooling adds water 400ml, divides oil-yielding stratum, and washed several times with water obtains 28g brown liquid 5-chloro-2-(4 '-chloro phenoxy group)-N, N-dipropyl aniline.
Stirring will arranged, and thermowell adds dense H in the four-hole bottle of dropping funnel
2SO
4200ml, be cooled to 20 ℃, add 5-chloro-2-(4 '-chloro phenoxy group)-N, N-dipropyl aniline 31.2g is cooled to 10 ℃ of whats and drips nitration mixture for 10～12 ℃, finish and stir 3hr, ice is analysed in the 1500ml frozen water, filters, and is washed till neutrality, get 33g 5-chloro-2-(4 '-chloro phenoxy group)-N, N-dipropyl amido-4-oil of mirbane.
Claims (3)
1. nitrobenzene derivative that contains phenoxy group, its general structure is as follows:
Wherein: R
1, R
2Identical or different, and all represent H or C
1-C
4Alkyl, X
1, X
2Identical or different, and all represent Cl or F.
2. a kind of nitrobenzene derivative that contains phenoxy group according to claim 1, wherein: R
1, R
2Identical, and all represent C
1-C
2Alkyl, X
1, X
2Be Cl.
3. a kind of preparation method who contains the nitrobenzene derivative of phenoxy group of claim 2, it may further comprise the steps:
A. in reactor, start and stir adding organic solvent and water, stir adding down
Be warming up to 80-100 ℃, slowly add reductive agent, reacted 4-6 hour down in 80 degree, cool off, filter, be washed till neutrality, it is product that the gained solid product obtains aniline with acetone recrystallization;
B. above-mentioned intermediate product, monobromethane, water, yellow soda ash, dodecyl triethyamino benzyl ammonia chloride are added autoclave pressure, 50-100 ℃ of reaction 10-20 hour; Reduce to room temperature, filtration, washing, divide oil-yielding stratum, getting dark oil liquid is N, and N aniline is product;
C. in reactor, add dense H
2SO
1, ice bath reduces to below 10 ℃, slowly adds prepared dark oil liquid, stirs, controlled temperature is lower than 10 ℃ then, drips nitration mixture and carries out nitration reaction, drips the back and continues reaction 6-10 hour; Reaction solution iced analyse, filter and make thing of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101249163A CN100422137C (en) | 2006-11-02 | 2006-11-02 | Nitrobenzene derivative containing phenoxy and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101249163A CN100422137C (en) | 2006-11-02 | 2006-11-02 | Nitrobenzene derivative containing phenoxy and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1948265A CN1948265A (en) | 2007-04-18 |
| CN100422137C true CN100422137C (en) | 2008-10-01 |
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|---|---|---|---|
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| CN111777520B (en) * | 2020-07-22 | 2023-04-07 | 苏州爱玛特生物科技有限公司 | Synthesis method of multi-substituted dimethylamino phenyl acetic acid compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678311A (en) * | 2002-06-27 | 2005-10-05 | 诺沃挪第克公司 | Aryl carbonyl derivatives as therapeutic agents |
-
2006
- 2006-11-02 CN CNB2006101249163A patent/CN100422137C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1678311A (en) * | 2002-06-27 | 2005-10-05 | 诺沃挪第克公司 | Aryl carbonyl derivatives as therapeutic agents |
Non-Patent Citations (4)
| Title |
|---|
| 《氯代羟基二苯醚合成工艺的改进》. 马梦林等.四川大学学报（自然科学版），第41卷第1期. 2004 |
| 《氯代羟基二苯醚合成工艺的改进》. 马梦林等.四川大学学报（自然科学版），第41卷第1期. 2004 * |
| On the Antimiercrobial Activity and Syntheses of SalicylanilideDerivatives. Y Hamada etc.Yakugaku Zasshi,Vol.101 No.7. 1981 |
| On the Antimiercrobial Activity and Syntheses of SalicylanilideDerivatives. Y Hamada etc.Yakugaku Zasshi,Vol.101 No.7. 1981 * |
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|---|---|
| CN1948265A (en) | 2007-04-18 |
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