CN105646276A

CN105646276A - Preparation method of o-methyl phenyl hydroxylamine

Info

Publication number: CN105646276A
Application number: CN201610125347.8A
Authority: CN
Inventors: 王红伟; 刘敏; 杨红兵; 戴顺坤; 黄会真; 杨继华
Original assignee: Anhui Guoxing Biochemistry Co Ltd
Current assignee: Anhui Guoxing Biochemistry Co Ltd
Priority date: 2016-03-04
Filing date: 2016-03-04
Publication date: 2016-06-08

Abstract

The invention discloses a preparation method of o-methyl phenyl hydroxylamine. The preparation method includes: using ortho nitrotoluene as a raw material, hydrazine hydrate as reductant, a ZSM-5 molecular sieve loaded with metal Ni as a catalyst to synthesize o-methyl phenyl hydroxylamine. Reaction yield can reach 95.0%, and byproducts are lower than 0.1%. The ZSM-5 molecular sieve treated with Fe3+ is adopted, Ni is loaded, the catalyst is an environment-friendly catalyst which is short in reaction period, high in product quality and high in yield, discharge of three wastes is reduced, requirements of environment-friendly chemical process is met, and the preparation method has good industrial application value.

Description

A kind of o-methyl-phenyl-azanol preparation method

Technical field

The invention belongs to compou nd synthesis technical field, particularly relate to a kind of o-methyl-phenyl-azanol preparation method.

Background technology

Pyraclostrobin Pyraclostrobin has another name called pyraclostrobin, is that BASF Aktiengesellschaft is in a kind of methoxy acrylic acid methyl ester. class wide-spectrum bactericide having pyrrazole structure concurrently of discovery in 1993. In current document, the synthetic route about pyraclostrobin of report is through being reduced into o-methyl-phenyl-azanol with ortho-methylnitrobenzene for raw material, the route raw material reacted with methylchloroformate and dimethyl sulfate again is easy to get, being prone to industrialized production, therefore the preparation of o-methyl-phenyl-azanol becomes crucial. ASHUTOSHH etc. (Processforthepreparationofahydroxylamine [p] .US:5166435) make catalyst with noble metals such as Pt, by the o-methyl-phenyl-azanol that ortho-methylnitrobenzene catalytic hydrogenation obtains, existence is following ties a problem: the 1) expensive catalyst that the present invention uses, and easy in inactivation is difficult to regeneration cycle use; 2) the hydrogenation reduction process of nitrobenzene compounds is extremely complex, and product, except o-methyl-phenyl-azanol, also has many by-products, causes product content and yield low, and product purity is poor; 3) waste water and dregs that the inventive method produces is serious, considerably increases the three-protection design cost of enterprise.

Summary of the invention

In order to overcome the defect of prior art, it is an object of the invention to provide a kind of efficiently, economic, green, safety and meet the preparation method of pyraclostrobin intermediate o-methyl-phenyl-azanol of industrialization production requirements, with ortho-methylnitrobenzene for raw material, hydrazine hydrate is as reducing agent, and the ZSM-5 molecular sieve of carried metal Ni synthesizes o-methyl-phenyl-azanol as catalyst.

It is an object of the invention to be realized by techniques below scheme: a kind of o-methyl-phenyl-azanol preparation method, concrete preparation process is:

(1) ion exchange: take a certain amount of FeCl respectively₃And ZSM-5 molecular sieve, then add water, be warmed up to 60 DEG C, stir 4h, obtain 1%��5% (wt%) Fe³⁺ZSM-5, name A;

(2) infusion process: adopt infusion process by W metal load A molecular sieve after the treatment, then 120 DEG C of drying, obtain containing 1%��3% (wt%) Ni²⁺ZSM-5, called after Ni/A, standby;

(3) ortho-methylnitrobenzene, solvent and catalyst are joined in four-hole boiling flask, then heat to 30��35 DEG C, start to drip hydrazine hydrate, time for adding controls at 1��1.5h, controls dropping temperature at 30��40 DEG C, after completion of dropwise addition, stirring reaction 2h at 30��40 DEG C, controlling in sampling, after middle control is qualified, reaction terminates;Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product.

Optimize further, described FeCl₃: the mass ratio of ZSM-5 molecular sieve is 1��5:34.5.

Optimize further, described ortho-methylnitrobenzene: solvent: catalyst: the mass ratio of hydrazine hydrate is 1:3��5:0.05��0.075:0.5��1.0.

Optimizing further, described solvent is the one in dichloroethanes, ethanol and oxolane.

Compared with prior art, provide the benefit that:

1) present invention process is simple to operate, less costly, adopts the yield of o-methyl-phenyl-azanol of this kind of technique synthesis up to more than 95.0%, and by-products content is lower than 0.1%;

2) Ni of carried metal NiZSM-5 molecular sieve²⁺Not in the channel, but the CHARGE DISTRIBUTION near ZSM-5 active center can be directly affected, thus affecting the catalytic performance of ZSM-5, Ni²⁺It is located parallel in " Z " the font passage in [100] direction, deviates ten-ring center, change the active porosity of " Z " font access portal, simultaneously Ni²⁺The reactant itself being likely to and enter molecular sieve channels contacts, and participates in catalytic action;

3) temperature of the method controls at 30-35 DEG C, and this temperature conditions is gentleer, it is easy to controlling, energy consumption is relatively low, and o-methyl-phenyl-azanol is more easy to generation in addition, and is not easily excessively reduced into other by-products.

Detailed description of the invention

Below by example, the present invention is described, but the present invention is not limited to these embodiments.

Embodiment 1

A kind of o-methyl-phenyl-azanol preparation method, concrete preparation process is:

(1) ion exchange: take the FeCl of 3g respectively₃With 34.5gZSM-5 molecular sieve, then add water, be warming up to 60 DEG C, stir 4h, obtain 3%Fe³⁺ZSM-5, name A;

(2) infusion process: adopt infusion process by W metal load A molecular sieve after the treatment, then 120 DEG C of drying, obtain containing 3% (wt%) Ni²⁺ZSM-5, called after Ni/A, standby;

(3) 100g ortho-methylnitrobenzene, 300g dichloroethanes and 7.5g catalyst are joined in the four-hole boiling flask of 1000ml, then 35 DEG C it are warmed up to, start to drip 100g hydrazine hydrate, time for adding controls at 1.5h, controls dropping temperature at 40 DEG C, after completion of dropwise addition, stirring reaction 2h at 40 DEG C, controlling in sampling, after middle control is qualified, reaction terminates; Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product. The product yield of the inventive method reaches 97.0%, and main byproducts content is 0.06%.

Embodiment 2

(1) ion exchange: take 5gFeCl respectively₃With 34.5gZSM-5 molecular sieve, then add water, be warming up to 60 DEG C, stir 4h, obtain 5% (wt%) Fe³⁺ZSM-5, name A;

(2) infusion process: adopt infusion process by W metal load A molecular sieve after the treatment, then 120 DEG C of drying, obtain containing 2% (wt%) Ni²⁺ZSM-5, called after Ni/A, standby.

(3) 100g ortho-methylnitrobenzene, 300g dichloroethanes and 7g catalyst are joined in the four-hole boiling flask of 1000ml, then 30 DEG C it are warmed up to, start to drip 100g hydrazine hydrate, time for adding controls at 1h, controls dropping temperature at 35 DEG C, after completion of dropwise addition, stirring reaction 2h at 35 DEG C, controlling in sampling, after middle control is qualified, reaction terminates; Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product.The product yield of the inventive method reaches 96.0%, Main By product 0.05%.

Embodiment 3

(1) ion exchange:: take 5gFeCl respectively₃With 34.5gZSM-5 molecular sieve, then add water, be warming up to 60 DEG C, stir 4h, obtain 5% (wt%) Fe³⁺ZSM-5, name A;

(2) infusion process: adopt infusion process by W metal load A molecular sieve after the treatment, then 120 DEG C of drying, obtain containing 2.5% (wt%) Ni²⁺ZSM-5, called after Ni/A, standby;

(3) 100g ortho-methylnitrobenzene, 300g dichloroethanes and 7g catalyst are joined in the four-hole boiling flask of 1000ml, then 35 DEG C it are warmed up to, start to drip 60g hydrazine hydrate, time for adding controls at 1.5h, controls dropping temperature at 40 DEG C, after completion of dropwise addition, stirring reaction 2h at 40 DEG C, controlling in sampling, after middle control is qualified, reaction terminates. Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product. The product yield of the inventive method reaches more than 95.0%, Main By product 0.09%.

Embodiment 4

(1) ion exchange: take 2gFeCl respectively₃With 34.5gZSM-5 molecular sieve, then add water, be warming up to 60 DEG C, stir 4h, obtain 2% (wt%)) Fe³⁺ZSM-5, name A;

(3) 100g ortho-methylnitrobenzene, 300g dichloroethanes and 6g catalyst are joined in the four-hole boiling flask of 1000ml, then 33 DEG C it are warmed up to, start to drip 60g hydrazine hydrate, time for adding controls at 1.2h, controls dropping temperature at 37 DEG C, after completion of dropwise addition, stirring reaction 2h at 37 DEG C, controlling in sampling, after middle control is qualified, reaction terminates; Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product. The product yield of the inventive method reaches 96.8%, Main By product 0.03%.

Claims

1. an o-methyl-phenyl-azanol preparation method, it is characterised in that concrete preparation process is:

(1) ion exchange: take a certain amount of FeCl respectively₃And ZSM-5 molecular sieve, then add water, be warmed up to 60 DEG C, stir 4h, obtain 1%��5%Fe³⁺ZSM-5, name A;

(2) infusion process: adopt infusion process by W metal load A molecular sieve after the treatment, then 120 DEG C of drying, obtain containing 1%��3%Ni²⁺ZSM-5, called after Ni/A;

(3) ortho-methylnitrobenzene, solvent and catalyst are joined in four-hole boiling flask, then heat to 30��35 DEG C, start to drip hydrazine hydrate, time for adding controls at 1��1.5h, controls dropping temperature at 30��40 DEG C, after completion of dropwise addition, stirring reaction 2h at 30��40 DEG C, controlling in sampling, after middle control is qualified, reaction terminates; Filtered while hot, filter cake absolute ethanol washing, concentrating under reduced pressure, then add water precipitation solid, and filtration drying obtains product.

2. o-methyl-phenyl-azanol preparation method according to claim 1, it is characterised in that described FeCl₃: the mass ratio of ZSM-5 molecular sieve is 1��5:34.5.

3. o-methyl-phenyl-azanol preparation method according to claim 1, it is characterised in that described ortho-methylnitrobenzene: solvent: catalyst: the mass ratio of hydrazine hydrate is 1:3��5:0.05��0.075:0.5��1.0.

4. o-methyl-phenyl-azanol preparation method according to claim 1, it is characterised in that described solvent is the one in dichloroethanes, ethanol and oxolane.