CN101165043A - Solid acid green nitration method for diphenyl ether derivative - Google Patents
Solid acid green nitration method for diphenyl ether derivative Download PDFInfo
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- CN101165043A CN101165043A CNA2006101506213A CN200610150621A CN101165043A CN 101165043 A CN101165043 A CN 101165043A CN A2006101506213 A CNA2006101506213 A CN A2006101506213A CN 200610150621 A CN200610150621 A CN 200610150621A CN 101165043 A CN101165043 A CN 101165043A
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Abstract
The present invention relates to green solid acid nitrating process of diphenyl ether derivative with deactivating group. Inside organic solvent and in the presence of solid acid catalyst, diphenyl ether derivative and nitric acid produce nitration reaction at -30 deg.c to 70 deg.c for 2-14 hr. The solid super strong acid is carried on montmorillonite, molecular sieve, silica, alumina or the mixture of two of the said matters. The nitric acid is concentrated nitric acid or fuming nitric acid; and the organic solvent is dichloromethane, dichloroethane or tetrachloroethylene. Compared with traditional nitrating process with mixed acid, the process of the present invention features use of supported super strong solid acid, no waste acid produced, and reuseable carrier.
Description
Technical field under in the of one
The present invention relates to the solid acid nitrifying method of a class organic compound, particularly can be used as weedicide or the nitrifying method of the diphenyl ether compound that in weedicide is synthetic, uses as intermediate.The green solid acid nitrifying method that specifically has the substituent diphenyl ether derivative of passivation, this solid acid agent is to be the super acids of carrier with materials such as polynite, molecular sieve, silicon oxide, aluminum oxide, and acidic substance comprise mineral acid, inorganic acid anhydrides, organic acid, organic acid anhydride etc.
Two technical backgrounds
The nitration reaction of aromatics is the crucial chemical reaction of a class, and wherein the nitrated of diphenyl ether compound has important effect in fields such as agricultural chemicals are synthetic.In a lot of documents, reported that the nitration reaction by diphenyl ether compound prepares weedicide efficiently.At patent EP0022610, US4,031,131, propose among EP0003416 and the EP0274194 structure as shown in the formula the preparation method of compound, all relate to the nitration reaction of phenyl ether, used nitrating agent is nitric acid or nitrate and vitriolic mixture, and the usage quantity of the common vitriol oil is 2-5 a times of nitric acid.
Wherein X and Y can be H, F, Cl, Br, CF
3, CN, NO
2Deng group.
The a lot of shortcomings of the nitrated existence of nitric acid/sulfuric acid that diphenyl ether derivative is traditional are violent as heat release in the reaction process; Produce a large amount of strong acid waste liquids; Shortcomings such as last handling process complexity.The solid acid nitrifying method has lot of advantages, at first, this nitrifying method improves reaction yield, used carrier can reuse after treatment always, in addition, do not use fluid sulphuric acid and diacetyl oxide in this method, so produce spent acid hardly, greatly simplified last handling process, and spent acid is to the pollution of environment.
Three summary of the invention
The problem to be solved in the present invention is in the preparation diphenyl ether herbicide, the green nitration method of diphenyl ether derivative.
The invention provides a kind of new nitrifying method of aromatic oxide compounds, especially the nitrifying method of diphenyl ether derivative.This method is carried out nitrated as the solid acid agent to diphenyl ether compound with carrier loaded mineral acid or organic acid and acid anhydrides.Described solid acid agent is to use the acid soak carrier, removes water then under reduced pressure, again the finely powdered solid matter of vacuum-drying gained.
Specifically, in organic solvent, above-mentioned solid acid is the agent of nitration reaction solid acid, is nitrating agent with nitric acid, and diphenyl ether compound is carried out nitration reaction.Described organic solvent is the halohydrocarbon of low-carbon (LC), is recommended as methylene dichloride and zellon.Described solid acid carrier is materials such as polynite, molecular sieve, silicon oxide, aluminum oxide, is recommended as silicon oxide and aluminum oxide.Described nitric acid is recommended as the nitric acid of 50-100% concentration.
In nitration reaction, the consumption of used solid acid is recommended as 1～5 times of used nitric acid amount, and further recommending consumption is 1.2～2.5 times.Range of reaction temperature is recommended as-20～70 ℃, further is recommended as-10～20 ℃.Reaction times is recommended as 0.5-8 hour, further is recommended as 2-3 hour.
Table 1 has provided the nitration reaction yield under the differential responses condition, and reaction formula one is the nitration reaction equation.
Reaction formula one
Table 1 reaction conditions is to the influence of solid acid nitration reaction
In experiment, in order to compare with the present invention, our reference has carried out the traditional liquid vitriol oil/nitric acid mixed acid nitrification, has listed nitration reaction condition and reaction yield in the table 2, simultaneously in order to guarantee that reaction carries out having added diacetyl oxide in reaction.
From the data of table 1 and table 2 as can be seen, nitration reaction yield with solid acid is slightly higher than the yield of the nitration reaction of using fluid sulphuric acid, the highest yield is 74.3%, with the highest yield of the nitration reaction of fluid sulphuric acid be 72.9%. with in the nitration reaction of solid acid, low temperature and be that solvent is to reacting favourable with the zellon.
The table 2 liquid vitriol oil/nitric acid mixed acid nitrification yield
This method can use the nitric acid of low concentration as nitrating agent, relatively with nitrosonitric acid and other nitrating agents comparatively economy and safety in production.The most important thing is, in the place near the steps nitration reaction, do not use fluid sulphuric acid and diacetyl oxide,, greatly simplified last handling process, and spent acid is a kind of economy and green nitrifying method to the pollution of environment so produce spent acid hardly.
Four inventive embodiments
Describe the present invention below in conjunction with embodiment:
Embodiment 1:
3-(3-trifluoromethyl-4-chlorine) phenoxy benzoic acid 10g, solid acid 13g drops into there-necked flask, adds methylene dichloride 50ml, 15～20 ℃ of cooling bath temperature controls.Slowly drip 65～68% concentrated nitric acid 8.5ml.Be heated to 30 ℃, isothermal reaction 2h.Suction filtration is used the 40ml washed with dichloromethane, merging filtrate.Filtrate is used 100ml water normal temperature washed twice.Add water 80m1 distillation except that desolvating cooling, suction filtration, the dry nitration product 9.2g that gets, 136～142 ℃ of melting ranges, the content 76.2% of HPLC analysis 3-(3-trifluoromethyl-4-chlorine) phenoxy group-6-nitrobenzoic acid.
Embodiment 2:
3-(3-trifluoromethyl-4-chlorine) phenoxy benzoic acid 10g, solid acid 13g drops into there-necked flask, adds methylene dichloride 50ml, 15～20 ℃ of cooling bath temperature controls.Slowly drip nitrosonitric acid 5.5ml.Be heated to 30 ℃, isothermal reaction 2h.Suction filtration is used the 40ml washed with dichloromethane, merging filtrate.Filtrate is with in the 100ml water normal temperature washing twice.Add water 80ml distillation except that desolvating cooling, suction filtration, the dry nitration product 7.8g that gets, 138～144 ℃ of melting ranges, the content 81.1% of HPLC analysis 3-(3-trifluoromethyl-4-chlorine) phenoxy group-6-nitrobenzoic acid.
Embodiment 3:
3-(3-trifluoromethyl-4-chlorine) phenoxy benzoic acid 10g, solid acid 13g drops into there-necked flask, adds methylene dichloride 40ml, 15～20 ℃ of cooling bath temperature controls.Slowly drip nitrosonitric acid 3.5ml.20 ℃ of reactions of constant temperature 2h.Suction filtration is used the 40ml washed with dichloromethane, merging filtrate.Filtrate is used 100ml water normal temperature washed twice.Add water 80ml distillation except that desolvating cooling, suction filtration, the dry nitration product 10g that gets, 132～138 ℃ of melting ranges, the content 74.6% of HPLC analysis 3-(3-trifluoromethyl-4-chlorine) phenoxy group-6-nitrobenzoic acid.
Claims (7)
1. the green solid of diphenyl ether derivative acid nitrifying method in organic solvent, is an acid reagent with the solid acid, carries out nitrated with nitric acid.
2. diphenyl ether derivative described in claim 1, it is characterized in that on one of them phenyl ring with substituting group be halogen and three methyl halides, have carboxyl or ester group on another phenyl ring.
3. solid acid is a kind of solid acid of loading type described in claim 1, and carrier is the mixture of polynite, molecular sieve, silicon oxide, aluminum oxide or above-mentioned two kinds of materials, and acidic substance comprise mineral acid, inorganic acid anhydrides, organic acid, organic acid anhydride etc.
4. described in claim 1, it is characterized in that used nitric acid is concentrated nitric acid or nitrosonitric acid.
5. solid acid described in claim 2, the weight ratio that it is characterized in that used acidic substance and carrier is 0.05-1: 1.
6. the nitrifying method described in claim 1 is characterized in that used organic solvent is a halohydrocarbon, and temperature of reaction is-30 ℃～70 ℃.
7. the nitrifying method described in claim 1 is characterized in that the reaction mass mol ratio is a diphenyl ether derivative: nitric acid: solid acid agent=1: 0.5-1.5: 0.5-2.5.
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| CNA2006101506213A CN101165043A (en) | 2006-10-19 | 2006-10-19 | Solid acid green nitration method for diphenyl ether derivative |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304052A (en) * | 2011-07-28 | 2012-01-04 | 浙江大学 | Method for preparing 5-bromo-2-hydroxy-3-nitroacetophenone |
| CN102557956A (en) * | 2010-12-20 | 2012-07-11 | 江苏亚邦染料股份有限公司 | Production process of high-purity 1-nitroanthraquinone |
| CN105622495A (en) * | 2016-03-23 | 2016-06-01 | 叶芳 | 4-chloro-3-nitropyridine and preparation method thereof |
| US20160185711A1 (en) * | 2014-12-24 | 2016-06-30 | Zhejiang Rongyao Biotech CO., LTD. | Process and Device for Recycling Waste Acid Produced in Process of Producing Zoalene |
| CN112876367A (en) * | 2021-01-20 | 2021-06-01 | 泰兴中科艾德膜材料科技有限公司 | Preparation method of diaminodiphenyl ether |
| CN113504262A (en) * | 2021-04-16 | 2021-10-15 | 甘肃省化工研究院有限责任公司 | O-methoxyacetanilide nitration thermal safety risk assessment method |
-
2006
- 2006-10-19 CN CNA2006101506213A patent/CN101165043A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557956A (en) * | 2010-12-20 | 2012-07-11 | 江苏亚邦染料股份有限公司 | Production process of high-purity 1-nitroanthraquinone |
| CN102304052A (en) * | 2011-07-28 | 2012-01-04 | 浙江大学 | Method for preparing 5-bromo-2-hydroxy-3-nitroacetophenone |
| US20160185711A1 (en) * | 2014-12-24 | 2016-06-30 | Zhejiang Rongyao Biotech CO., LTD. | Process and Device for Recycling Waste Acid Produced in Process of Producing Zoalene |
| US9527801B2 (en) * | 2014-12-24 | 2016-12-27 | Zhejiang Rongyao Biotech CO., LTD. | Process and device for recycling waste acid produced in process of producing zoalene |
| CN105622495A (en) * | 2016-03-23 | 2016-06-01 | 叶芳 | 4-chloro-3-nitropyridine and preparation method thereof |
| CN112876367A (en) * | 2021-01-20 | 2021-06-01 | 泰兴中科艾德膜材料科技有限公司 | Preparation method of diaminodiphenyl ether |
| CN112876367B (en) * | 2021-01-20 | 2022-08-05 | 泰兴中科艾德膜材料科技有限公司 | Preparation method of diaminodiphenyl ether |
| CN113504262A (en) * | 2021-04-16 | 2021-10-15 | 甘肃省化工研究院有限责任公司 | O-methoxyacetanilide nitration thermal safety risk assessment method |
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Open date: 20080423 |