CN110143924A - A kind of preparation method of substituted aromatic hydroxylamine compound - Google Patents
A kind of preparation method of substituted aromatic hydroxylamine compound Download PDFInfo
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- CN110143924A CN110143924A CN201910500992.7A CN201910500992A CN110143924A CN 110143924 A CN110143924 A CN 110143924A CN 201910500992 A CN201910500992 A CN 201910500992A CN 110143924 A CN110143924 A CN 110143924A
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Abstract
The present invention relates to a kind of preparation methods of substituted aromatic hydroxylamine compound, be by nitrobenzene compound substituted shown in formula (II) in the presence of solvent, under the active metal catalyst effect containing molybdenum, aromatic hydroxylamine compound substituted shown in formula (I) is obtained with hydrogen or hydrazine reaction.Method of the invention not only has satisfactory highly selective, but also is avoided in synthesis process using the additive for being difficult to remove, and has that at low cost, equipment investment is few, reaction condition is mild, production easy to clean.
Description
The application be the applying date be on November 06th, 2014, application No. is 2014106214979, it is entitled " a kind of
The divisional application of the patent application of the preparation method of substituted aromatic hydroxylamine compound ".
Technical field
The present invention relates to a kind of preparation methods of compound, and in particular to a kind of preparation method of aromatic hydroxylamine compound.
Background technique
N- [2- [[1- (4- chlorphenyl) pyrazole-3-yl] oxygen methyl] phenyl] azanol is to be used to prepare fungicide pyrazoles ether bacterium
The key intermediate of ester.Pyraclostrobin is BASF Aktiengesellschaft in a kind of methoxy with pyrrazole structure of discovery in 1993
Base esters of acrylic acid wide-spectrum bactericide is registered and is listed, had been used in 100 various crops at present for 2001.2009, sale
Volume reaches 7.35 hundred million dollars, is only second to Fluoxastrobin, becomes world's second largest fungicide.
Aromatic hydroxylamine is a kind of important organic synthesis intermediate, is widely used in the conjunction of pesticide, medicine, fine chemistry industry
At such great application prospect of compound.In reduction process, intermediate aromatic hydroxylamine is quickly converted to aromatic nitro compound
Corresponding amine, control reaction is very difficult, therefore, prepares aromatic hydroxylamine compound in organic synthesis or challenge
Problem.
Aromatic hydroxylamine generally using corresponding aromatic nitro compound as raw material restore prepare, the method for reduction have it is several,
Wherein, had the shortcomings that using the method that metallic zinc restores on an industrial scale in the presence of very big waste material, using transition metal such as platinum or
Palladium is the heterogeneous reduction of catalyst, to obtain enough selectivity, such reaction must in additive such as sulfur-containing compound or
It being carried out in the presence of organic base, such additives poison the catalyst or make its inactivation, and along with various disadvantages, this
Transition-metal catalyst needed for outer is fairly expensive.
Summary of the invention
The purpose of the present invention is to provide preparation fragrance hydroxyls that is a kind of easy to implement and being suitable for industrialization large-scale production
On the one hand the method for amine compounds, this method have satisfactory highly selective, while cost is relatively low, is especially just catalyzed
For agent.
For this purpose, the present invention provide it is a kind of with high yield and specificity method, for convert preparation with
Substituted aromatic hydroxylamine compound shown in following formula (I).
The method of the present invention is avoided that using the additive for being difficult to remove, at low cost, equipment investment is few, reaction condition temperature
The advantages that with production easy to clean.
Above-mentioned purpose can be realized by the method being described below in detail.
The present invention, which provides, a kind of makes the formula (II) class nitrobenzene compound and hydrogen or hydrazine in the activity gold containing molybdenum
The method of the aromatic hydroxylamine compound of preparation formula (I) class is reacted in the presence of metal catalyst.
The reaction in the presence of solvent, makes nitrobenzene compound shown in formula (II) containing molybdenum using hydrogen or hydrazine
It reacts and carries out in the presence of active metal catalyst.
In active metal catalyst containing molybdenum used in the method for the present invention, the mass percent of molybdenum is greater than or equal to 1%
And less than 100%.
In addition to molybdenum, the active metal catalyst may include other one or more active metals, as iron, aluminium, copper,
Any one in zinc, chromium or nickel or two or more mixtures, these active metals account for the total matter of the active metal catalyst
At most the 99% of amount.
The catalyst uses preferably in the form of fine particle.Used catalyst usually has 10-600 μm in the present invention, excellent
Select 20-200 μm of average particle size (weight average).
Preactivated turn for being more advantageous to the reaction is carried out to for the active metal catalyst in the method for the present invention
The raising of rate and selectivity, the described activation can be usually used by the buck processing with 0.5% come simple realization
0.5% sodium hydroxide or potassium hydroxide 0-50 DEG C at a temperature of mixed processing and realize, the activation can be at once
To be applied to carry out before method of the invention, it is long-term after can also directly mixing the active metal catalyst with buck
Storage is to maintain catalytic activity.
In the method for the present invention, the active metal catalyst usage amount containing molybdenum is substrate nitro benzene shown in formula (II)
The 0.1~10% of compound quality, preferably 0.5~5%, more preferably 0.8~2%.
In the method for the present invention, the reaction should carry out in the presence of solvent, and suitable solvent has tetrahydrofuran, toluene, first
The mixing of one or more of base tertbutyl ether, glycol dimethyl ether, dichloroethanes, methylene chloride, ethyl alcohol, isopropanol etc.
Object.
In the method for the present invention, the preferred mass concentration in entire reaction mixture of nitrobenzene compound shown in formula (II)
It is 5~50%, more preferably 10~20%；The mass ratio of the solvent and nitrobenzene compound shown in formula (II) is 1:0.5-
20。
Present invention reaction usually requires temperature control, usually carries out in the closed or open reaction vessel with stirring,
Reaction temperature is -20~100 DEG C, preferably 0~80 DEG C, more preferably 10~50 DEG C.
In the method for the present invention, hydrazine is interpreted as hydrazine reaction object, is colourless liquid, and per molecule hydrazine includes about 1 molecular water
Hydrazine hydrate (N2H4H2O) or solution, especially aqueous solution, preferably water content are the solution of 20-70 weight %, it is preferable to use water
Hydrazine is closed, the preferably molar ratio of hydrazine and nitrobenzene compound is 1.1-5.5:1.
In the preferred embodiments of the invention, Hydrogen Vapor Pressure is maintained at 0.01~1MPa, more preferably 0.02~0.5MPa.
Compared with prior art, the beneficial effects of the present invention are: method of the invention not only has satisfactory Gao Xuan
Selecting property, and avoided in synthesis process using the additive for being difficult to remove, at low cost, equipment investment is few, reaction condition
Mildly, production easy to clean.In the method for the present invention, the catalyst is not poisoned in hydrogenation process or is not poisoned significantly, and
More batches of similar reaction process can be carried out continuously, i.e. the catalyst can be recycled.It is of the invention for post-processing
Preferred embodiment is to stand reaction mixture, so that catalyst precipitates from reaction mixture, and then is separated with product,
It can also such as be filtered by conventional method in that art if needing, remove catalyst.
Raw materials used nitrobenzene compound (II) can pass through methodology of organic synthesis system known in the art in the method for the present invention
It is standby to obtain.Formula (I) compound obtained through the invention can further react to obtain with acylating reagent formula (III) compound, then with
Alkylating reagent reacts the formula that obtains (IV) compound in the presence of a base:
These same conversions are well known in the art, and can synthesize to obtain according to open source literature method and condition.
Specific embodiment
The present invention will be further illustrated by the following example, but not limited by the following example.
Embodiment 1
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g methyl tertiary butyl ether(MTBE)
In, the active molybdenum catalyst of 0.045g is added into system, is successively replaced 3 times with nitrogen, hydrogen after closed, is then charged with hydrogen
Gas reacts at 25 DEG C, keeps system pressure 0.1MPa, continues stir about 1~10 hour at a temperature of this, in reaction process
Sampling is analyzed by HPLC, and raw material converts completely, and selectivity of product is greater than 95.8%, and product Compound is identified by 1H-NMR.
Embodiment 2
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g methyl tertiary butyl ether(MTBE)
In, into system, (catalyst uses 30 DEG C of sodium hydroxide solution of 0.5% to impregnate to the active molybdenum catalyst of addition 0.045g in advance
For 24 hours r), it is successively replaced 3 times with nitrogen, hydrogen after closed, is then charged with hydrogen, reacts at 25 DEG C, keep system pressure
0.1MPa continues stir about 1~10 hour at a temperature of this, and sampling passes through HPLC analysis, feed stock conversion in reaction process
98.9%, selectivity of product is greater than 98.0%, and product Compound is identified by 1H-NMR.
Embodiment 3
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g tetrahydrofuran,
The active molybdenum catalyst of 0.045g is added into system, is successively replaced 3 times with nitrogen, hydrogen after closed, is then charged with hydrogen,
It reacts at 25 DEG C, keeps system pressure 0.5MPa, continue stir about 1~10 hour at a temperature of this, sampled in reaction process
It is analyzed by HPLC, feed stock conversion is higher than 99.0%, and selectivity of product is greater than 97.8%, and product Compound is reflected by 1H-NMR
Not.
Embodiment 4
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g tetrahydrofuran,
Into system, (catalyst uses 30 DEG C of sodium hydroxide solution of 0.5% to impregnate to the active molybdenum catalyst of addition 0.045g in advance
For 24 hours r), it is successively replaced 3 times with nitrogen, hydrogen after closed, is then charged with hydrogen, reacts at 25 DEG C, keep system pressure
0.1MPa continues stir about 1~10 hour at a temperature of this, and sampling is higher than by HPLC analysis, feed stock conversion in reaction process
99.2%, selectivity of product is greater than 99.2%, and product Compound is identified by 1H-NMR.
Embodiment 5
By 4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene be dissolved in 20g tetrahydrofuran and
In the mixed solution of 10g toluene, the active molybdenum catalyst of 0.045g and 0.5% sodium hydroxide solution are added into system
0.01g is successively replaced 3 times with nitrogen, hydrogen after closed, is then charged with hydrogen, reacts at 35 DEG C, keep system pressure
0.1MPa continues stir about 1~10 hour at a temperature of this, and sampling is higher than by HPLC analysis, feed stock conversion in reaction process
99.2%, selectivity of product is greater than 99.1%, and product Compound is identified by 1H-NMR.
Embodiment 6
By 4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene be dissolved in 20g tetrahydrofuran and
In the mixed solution of 10g toluene, the active molybdenum catalyst of 0.042g is added into system, successively with nitrogen, hydrogen displacement 3 after closing
It is secondary, it is then charged with hydrogen, is reacted at 10 DEG C, system pressure 0.5MPa is kept, continuation stir about 1~10 is small at a temperature of this
When, sampling is analyzed by HPLC in reaction process, and feed stock conversion is up to 100%, and selectivity of product is greater than 96.9%, product chemical combination
Object is identified by 1H-NMR.
Embodiment 7
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g ethyl alcohol, Xiang Ti
The active molybdenum catalyst of 0.085g is added in system, is successively replaced 3 times with nitrogen, hydrogen after closed, hydrogen is then charged with, at 15 DEG C
Under react, keep system pressure 0.1MPa, continue stir about 1~10 hour at a temperature of this, sample and pass through in reaction process
HPLC analysis, feed stock conversion is up to 99.5%, and selectivity of product is greater than 95.1%, and product Compound is identified by 1H-NMR.
Embodiment 8
4.5g 2- [1- (4- chlorphenyl) pyrazoles -3 '-oxygroup methyl] -1- nitrobenzene is dissolved in 30g methyl tertiary butyl ether(MTBE)
In, the active molybdenum catalyst of 0.045g is added into system, 5.4g50% hydrazine hydrate is added after closed, occurs at 25 DEG C anti-
It answers, system pressure is kept to be less than 0.1MPa, continues stir about 1~10 hour at a temperature of this, sampled in reaction process and pass through HPLC
Analysis, up to 99%, selectivity of product 98.1%, product Compound is identified feed stock conversion by 1H-NMR.
Claims (10)
1. a kind of preparation method of substituted aromatic hydroxylamine compound, it is characterised in that: substituted nitrobenzene shown in formula (II)
Compound in the presence of solvent, under the active metal catalyst effect containing molybdenum, is reacted to obtain with hydrogen and is taken shown in formula (I)
The aromatic hydroxylamine compound in generation
2. preparation method described in accordance with the claim 1, it is characterised in that: in the active metal catalyst containing molybdenum,
The mass percent of molybdenum is greater than or equal to 1% and less than 100%, and surplus is other metals.
3. preparation method according to claim 2, it is characterised in that: other described metals appointing in aluminium, copper, chromium
The mixture for one or more of anticipating.
4. preparation method described in accordance with the claim 1, it is characterised in that: the active metal catalyst uses 0.1 in advance~
At a temperature of mixed processing of 0.5% sodium hydroxide or potassium hydroxide at 0-50 DEG C.
5. preparation method described in accordance with the claim 1, it is characterised in that: the active metal catalyst usage amount containing molybdenum
Be the 0.1~10% of nitrobenzene compound quality substituted shown in formula (II), preferably 0.5~5%, more preferably 0.8~
2%.
6. preparation method described in accordance with the claim 1, it is characterised in that: the solvent is selected from tetrahydrofuran, toluene, methyl
The mixture of one or more of tertbutyl ether, glycol dimethyl ether, dichloroethanes, methylene chloride, ethyl alcohol or isopropanol.
7. preparation method described in accordance with the claim 1, it is characterised in that: substituted nitrobenzene compound shown in formula (II) exists
Mass concentration in entire reaction mixture is 5~50%, more preferably 10~20%；Shown in the solvent and formula (II)
The mass ratio of nitrobenzene compound is 1:0.5-20.
8. preparation method described in accordance with the claim 1, it is characterised in that: the reaction -20~100 DEG C at a temperature of into
Row, preferably 0~80 DEG C at a temperature of carry out, more preferably 10~50 DEG C at a temperature of carry out.
9. preparation method described in accordance with the claim 1, it is characterised in that: the hydrogen in reaction pressure is maintained at 0.01~
1MPa, more preferably 0.02~0.5MPa.
10. preparation method described in accordance with the claim 1, it is characterised in that: hydrazine and nitrobenzene compound in the reaction
Molar ratio is 1.1-5.5:1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153960A (en) * | 2010-09-21 | 2013-06-12 | 巴斯夫欧洲公司 | Process for preparing substituted N-phenylhydroxylamines |
| CN103415508A (en) * | 2011-03-09 | 2013-11-27 | 巴斯夫欧洲公司 | Process for preparing substituted n-phenylhydroxylamines |
| CN103588599A (en) * | 2013-11-13 | 2014-02-19 | 大连九信生物化工科技有限公司 | Method for preparing hydroxylamine through nitro-reduction |
| CN104059021A (en) * | 2013-03-18 | 2014-09-24 | 华中师范大学 | Preparation method of N-hydroxyaniline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10147580A (en) * | 1996-09-17 | 1998-06-02 | Mitsui Chem Inc | Production of tetrahydrofuran derivative |
| CN101357894B (en) * | 2008-08-07 | 2011-05-11 | 大连理工大学 | Method for selectively reducing preparation of arylhydroxylamine from aromatic nitro compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153960A (en) * | 2010-09-21 | 2013-06-12 | 巴斯夫欧洲公司 | Process for preparing substituted N-phenylhydroxylamines |
| CN103415508A (en) * | 2011-03-09 | 2013-11-27 | 巴斯夫欧洲公司 | Process for preparing substituted n-phenylhydroxylamines |
| CN104059021A (en) * | 2013-03-18 | 2014-09-24 | 华中师范大学 | Preparation method of N-hydroxyaniline |
| CN103588599A (en) * | 2013-11-13 | 2014-02-19 | 大连九信生物化工科技有限公司 | Method for preparing hydroxylamine through nitro-reduction |
Non-Patent Citations (1)
| Title |
|---|
| 刘迎新: ""镍基催化剂上间-二硝基苯催化加氢反应性能及其反应动力学的研究"", 《天津大学博士学位论文》 * |
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