CN104529815A - Method for synthesizing 2,4-dinitrobenzene oxygen amine - Google Patents
Method for synthesizing 2,4-dinitrobenzene oxygen amine Download PDFInfo
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- CN104529815A CN104529815A CN201410729653.3A CN201410729653A CN104529815A CN 104529815 A CN104529815 A CN 104529815A CN 201410729653 A CN201410729653 A CN 201410729653A CN 104529815 A CN104529815 A CN 104529815A
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- dinitrophenoxy
- hydroxylammonium salt
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- BBDSZAPYPCSXLJ-UHFFFAOYSA-N CC(NOc(c(N=O)c1)ccc1N=O)=O Chemical compound CC(NOc(c(N=O)c1)ccc1N=O)=O BBDSZAPYPCSXLJ-UHFFFAOYSA-N 0.000 description 1
- VVVQMFIZLFEQKE-UHFFFAOYSA-N CNOc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O Chemical compound CNOc(c([N+]([O-])=O)c1)ccc1[N+]([O-])=O VVVQMFIZLFEQKE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for synthesizing 2,4-dinitrobenzene oxygen amine. The method comprises the following steps: adding hydroxylammonium salt, water and acetic ester into a reaction vessel according to the ratio of n (acetic ester): n (hydroxylammonium salt) being 1.0-2.0:1, dropwise adding 30% alkali metal hydroxide aqueous solution at 15-40 DEG C and continuously reacting for 1 hour according to the ratio of n (alkali metal hydroxide): n (hydroxylammonium salt) being 1.5-3; heating up to 50 DEG C after the reaction, dropwise adding an acetic ester solution of 2,4-dinitrochlorobenzene (at the concentration of 50%) according to the ratio of n (2,4-dinitrochlorobenzene): n (hydroxylammonium salt) being 0.5-1.0, and continuously reacting for 2 hours after dropwise adding; cooling, filtering, beating and washing with alkali lye; adding filter cake into the reaction vessel, adding equimolar hydrochloric acid, heating up and reacting for 1-3 hours, cooling and filtering; and recrystallizing the filter cake with methanol so as to obtain the product. According to the invention, reaction steps are short; raw materials are cheap and easily available; operation is simple; and the method is easy for industrial production.
Description
Technical field
The present invention relates to compou nd synthesis method and technology field, the method for particularly a kind of synthesis.
Background technology
2,4-dinitrophenoxy amine (2,4-2,4-dinitrophenoxy amine, O-(2,4-dinitrophenyl) azanol) is an excellent aminating agent in organic synthesis, can be used for all kinds of amination reaction containing secondary nitrogen and carbanion compound.Carry out amination with 2,4-dinitrophenoxy amine not only easy and simple to handle, and be applicable to there are other in its molecule to compound introducing amino influential when nitrosification or reduction subsequently.
Method at present for the synthesis of 2,4-2,4-dinitrophenoxy amine has:
1) Eidem (J Heterocyel Chem 1967,4,413) describes with after nitrogen-atoms in tertiary fourth oxygen formyl chloride protection azanol, then reacts with DNFB introduce aryl on Sauerstoffatom, finally uses the technique of trifluoroacetic acid hydrolysis.This technique adopts tertiary fourth oxygen formyl chloride and trifluoroacetic acid to make raw material, expensive.
2) Japan Kokai 87-70344 discloses and forms HP with Tetra hydro Phthalic anhydride and azanol, then reacts with DNFB, the then technique of hydrazinolysis or azanol solution.Though this processing step is short, hydrazinolysis or azanol solution troublesome poeration, by product not easily reclaims, and cost is higher.
3) (the Chinese Journal of Pharmaceuticals 1993 such as Xin's great waves, 03,134-135) describe and in the mixed solution of second cyanogen and ethanol, pass into dry hydrogen chloride obtain ethyl acetimidate hydrochloride, react with oxammonium hydrochloride again and generate acethydroximic acid ethyl ester, Sauerstoffatom carries out virtue, then by the technique of perchloric acid hydrolysis.This processing step is longer, complex process and troublesome poeration, is unfavorable for large production.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of raw material cheap and easy to get, step is short, easy and simple to handle, the method for synthesis 2, the 4-2,4-dinitrophenoxy amine of easy suitability for industrialized production.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: first carry out oximation reaction by acetic ester and hydroxylammonium salt and protect N, its reaction formula is shown below:
In formula, R is methyl or ethyl, and HX is hydrochloric acid or sulfuric acid;
Then the product of gained and DNFB react, and its reaction formula is shown below:
And then add hydrochloric acid and be hydrolyzed, its reaction formula is shown below:
Concrete synthesis step is as follows:
(1) in reaction vessel, add hydroxylammonium salt, water and acetic ester, then at 15-40 DEG C of temperature, in reaction vessel, drip alkali metal hydroxide aqueous solution that mass percent is 25-35% and be incubated 1-2 hour; The consumption of water is 0.5-2 times of hydroxylammonium salt weight, and the mol ratio of acetic ester and hydroxylammonium salt is 1.0-2.0:1, and the mol ratio of alkali metal hydroxide and hydroxylammonium salt is 1.5-3.0:1;
(2) insulation is warming up to 40-50 DEG C after terminating, drip 2, the acetate solution (mass percent of DNFB in the acetate solution configured is 40-50%) of 4-dinitrochlorobenzene, dropwises rear 40-50 DEG C of insulation 1-2 hour; In DNFB and step (1), the mol ratio of added hydroxylammonium salt is 0.5-1.0:1;
(3) filter after the material that step (2) is synthesized being down to room temperature, gained filter cake mass percent is 3-5% alkali metal hydroxide aqueous solution making beating washing, filter cake and mass percent are that between 3-5% alkali metal hydroxide aqueous solution, weight ratio is 1:1-2, and then filtration obtains filter cake;
(4) in reaction vessel, add step (3) again filter the filter cake obtained, then add with step (2) in 2, the equimolar mass percent of 4-dinitrochlorobenzene is that (wait mole is 2 to 10-20% hydrochloric acid, the mol ratio of 4-dinitrochlorobenzene and hydrochloric acid), then 50-70 DEG C of reaction 1-3 hour is warming up to, be down to room temperature (according to room temperature environment at that time, general 15-30 degree) after reaction terminates to filter and obtain filtrate;
(5) the filtrate 5-6 times weight obtained by step (4) methyl alcohol carries out reflux to filtrate, cooling realizes recrystallization, the crystallization refiltering acquisition is at 50-60 DEG C, vacuum-drying 3-4 hour under 0.5-0.8MPa, obtain 2,4-2,4-dinitrophenoxy amine product.
In above-mentioned steps (1), the consumption of water is preferably the 0.8-1.5 of hydroxylammonium salt weight doubly, and very few hydroxylammonium salt cannot dissolve completely the generation causing side reaction, too high, causes productivity to decline, and energy consumption increases.
In above-mentioned steps (1), alkali metal hydroxide is sodium hydroxide or potassium hydroxide, is preferably sodium hydroxide, and because both performances are more or less the same, but price differs greatly, and sodium hydroxide can significantly reduce costs.
In above-mentioned steps (1), the mol ratio of alkali metal hydroxide and hydroxylammonium salt is preferably 1.6-2.2:1, crosses low reaction incomplete, too high, easily causes side reaction.
In above-mentioned steps (1), the mol ratio of acetic ester and hydroxylammonium salt is preferably 1.1-1.5:1, crosses low reaction incomplete, too high wastage of material.
In above-mentioned steps (1), temperature of reaction is preferably 20-30 DEG C, crosses low reaction incomplete, too high, easily causes side reaction.
DNFB is preferably 0.6-0.8:1 with the mol ratio of added hydroxylammonium salt in step (1) in above-mentioned steps (2), and too low then raw material consumption increases, and too high alkylation not exclusively, easily produces side reaction.
Reaction times is 1-2 hour in above-mentioned steps (4), crosses hydrolysis at least not exclusively, longly causes side reaction to increase; Temperature of reaction is 50-60 DEG C, and too low then hydrolysis not exclusively, too highly causes side reaction to increase.
Compared with prior art, the invention has the advantages that:
1. the present invention synthesizes in the method for 2,4-2,4-dinitrophenoxy amine expensive raw materials such as not using tertiary fourth oxygen formyl chloride and trifluoroacetic acid, and raw material is cheap and easy to get.
2. the present invention synthesizes in the method for 2,4-2,4-dinitrophenoxy amine, and in hydrolysis reaction, adopt hydrochloric acid hydrolysis, not only raw material is cheap and easy to get, and process is simple.
3. the present invention synthesizes the method for 2,4-2,4-dinitrophenoxy amine and original acethydroximic acid ethyl ester technics comparing, avoids step longer, and complex process and troublesome poeration are unfavorable for the problems such as large production, easy suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
Be equipped with electric stirring, thermometer, prolong 500mL four-hole boiling flask in add 35g water, 35g (0.50mo1) oxammonium hydrochloride, stirred at ambient temperature adds 44.4g (0.60mol) methyl acetate after dissolving again, constant temperature 25 DEG C, start to drip 30% liquid caustic soda 120g (0.90mol), joining day 1h, reacts 1h after having added at 25 DEG C.Then be warmed up to 50 DEG C, drip the methyl acetate solution 121.5g (0.30mol) of the DNFB of 1:1, joining day 2h, reacts 2h after having added at 50 DEG C, is then cooled to 25 DEG C.Filter, the filter cake 5% liquid caustic soda making beating washing of mass ratio 1:1, filters again; Solid drops in the four-hole boiling flask of 500mL, and add 36.6g water, 36.6g (0.30mo1) 31% hydrochloric acid, is warmed up to 60 DEG C, reacts and is cooled to 25 DEG C after 2 hours.Filter, solid 5 times of weight percent methanol backflow recrystallizations, 50 DEG C of vacuum-dryings obtain product 37.1g, yield 61.0%, and liquid content is 98.3%.
Embodiment 2
Water consumption changes 50g into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 37.6g, and yield 62.1%, liquid content is 98.7%.
Embodiment 3
NaOH changes KOH into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 37.4g, and yield 61.7%, liquid content is 98.6%
Embodiment 4
Methyl acetate changes ethyl acetate into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 36.8g, and yield 60.4%, liquid content is 98.1%
Embodiment 5
NaOH consumption changes 0.8mol into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 34.8g, and yield 57.6%, liquid content is 98.8%.
Embodiment 6
Methyl acetate consumption changes 0.75mol into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 37.4g, and yield 61.3%, liquid content is 97.9%.
Embodiment 7
DNFB consumption changes 0.4mol into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 36.2g, and yield 43.7%, liquid content is 96.3%.
Embodiment 8
Hydrolysising reacting temperature is 70 DEG C, and the insulation reaction time is 2h, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 37.7g, and yield 61.9%, liquid content is 98.1%.
Embodiment 9
Oxammonium hydrochloride changes oxammonium sulfate into, the other the same as in Example 1, and result is 2,4-2,4-dinitrophenoxy amine 35.1g, and yield 57.8%, liquid content is 98.3%
, aftertreatment simple from the known preparation process of the present invention of above-mentioned specific embodiment easily and productive rate is high, is easy to hydrolysis and is separated.
Claims (9)
1. the method for synthesis 2, a 4-2,4-dinitrophenoxy amine, is characterized in that: first carry out oximation reaction by acetic ester and hydroxylammonium salt and protect N, its reaction formula is shown below:
In formula, R is methyl or ethyl, and HX is hydrochloric acid or sulfuric acid;
Then react with DNFB, its reaction formula is shown below:
Add hydrochloric acid hydrolysis again, its reaction formula is shown below:
2. the method for synthesis 2,4-2,4-dinitrophenoxy amine according to claim 1, is characterized in that: concrete synthesis step is as follows:
(1) in reaction vessel, add hydroxylammonium salt, water and acetic ester, then at 15-40 DEG C of temperature, in reaction vessel, drip alkali metal hydroxide aqueous solution that mass percent is 25-35% and be incubated 1-2 hour; The consumption of water is 0.5-2 times of hydroxylammonium salt weight, and the mol ratio of acetic ester and hydroxylammonium salt is 1.0-2.0:1, and the mol ratio of alkali metal hydroxide and hydroxylammonium salt is 1.5-3.0:1;
(2) insulation is warming up to 40-50 DEG C after terminating, and drips the acetate solution of DNFB, dropwises rear 40-50 DEG C of insulation 1-2 hour; In DNFB and step (1), the mol ratio of added hydroxylammonium salt is 0.5-1.0:1;
(3) filter after the material that step (2) is synthesized being down to room temperature, gained filter cake mass percent is 3-5% alkali metal hydroxide aqueous solution making beating washing, filter cake and mass percent are that between 3-5% alkali metal hydroxide aqueous solution, weight ratio is 1:1-2, and then filtration obtains filter cake;
(4) in reaction vessel, add step (3) again filter the filter cake obtained, then add with step (2) in 2, the equimolar mass percent of 4-dinitrochlorobenzene is 10-20% hydrochloric acid, then afterwards intensification 50-70 DEG C reaction 1-3 hour, reaction terminate after be down to room temperature filter obtain filtrate;
(5) the filtrate 5-6 times weight obtained by step (4) methyl alcohol carries out reflux to filtrate, cooling realizes recrystallization, refilter crystallization at 50-60 DEG C, vacuum-drying 3-4 hour under 0.5-0.8MPa, obtain 2,4-2,4-dinitrophenoxy amine product.
3. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in described step (1), acetic ester is methyl acetate or ethyl acetate; Alkali metal hydroxide is sodium hydroxide or potassium hydroxide; Hydroxylammonium salt is oxammonium hydrochloride or oxammonium sulfate.
4. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (1), the consumption of water is 0.8-1.5 times of hydroxylammonium salt weight.
5. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (1), the mol ratio of alkali metal hydroxide and hydroxylammonium salt is 1.6-2.2:1.
6. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (1), the mol ratio of acetic ester and hydroxylammonium salt is 1.1-1.5:1.
7. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (1), temperature of reaction is 20-30 DEG C.
8. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (2) in DNFB and step (1) added by the mol ratio of hydroxylammonium salt be 0.6-0.8:1.
9. according to right 2, synthesize the method for 2,4-2,4-dinitrophenoxy amine, it is characterized in that: in step (4), the reaction times is 1-2 hour, and temperature of reaction is 50-60 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019218445A1 (en) * | 2018-05-15 | 2019-11-21 | 中国农业科学院北京畜牧兽医研究所 | Method for synthesizing urease inhibitor acetohydroxamic acid |
| CN113698318A (en) * | 2021-09-14 | 2021-11-26 | 宁波四明化工有限公司 | 2, 4-dinitrophenoxy amine synthesis method and reaction container |
| CN115108891A (en) * | 2022-07-18 | 2022-09-27 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
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| WO2010027114A1 (en) * | 2008-09-05 | 2010-03-11 | Choongwae Pharma Corporation | Use of pyrazole-pyridine derivatives and its salts for treating or reventin osteoporosis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019218445A1 (en) * | 2018-05-15 | 2019-11-21 | 中国农业科学院北京畜牧兽医研究所 | Method for synthesizing urease inhibitor acetohydroxamic acid |
| CN113698318A (en) * | 2021-09-14 | 2021-11-26 | 宁波四明化工有限公司 | 2, 4-dinitrophenoxy amine synthesis method and reaction container |
| CN115108891A (en) * | 2022-07-18 | 2022-09-27 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
| CN115108891B (en) * | 2022-07-18 | 2024-04-23 | 烟台盛华液晶材料有限公司 | Preparation method of 3, 5-difluorophenol |
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Effective date of registration: 20171103 Address after: 315204 No. 801 Beihai Road, Zhenhai crab Town, Ningbo City, Zhejiang province (Ningbo chemical industry zone) Patentee after: Ningbo Siming Chemical Co. Ltd. Address before: 315213 No. 1515 Beihai Road, crab Chemical Industrial District, Zhenhai District, Zhejiang, Ningbo Patentee before: Ningbo Ouxun Chemistry New Material Technology Co., Ltd. |