CN106883130B - A method of preparing halogenated biphenyl amine - Google Patents
A method of preparing halogenated biphenyl amine Download PDFInfo
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- CN106883130B CN106883130B CN201710176786.6A CN201710176786A CN106883130B CN 106883130 B CN106883130 B CN 106883130B CN 201710176786 A CN201710176786 A CN 201710176786A CN 106883130 B CN106883130 B CN 106883130B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
The present invention relates to fine chemistry industry preparation fields, more particularly to a kind of method of the halogenated biphenyl amine of preparation formula (I), it is catalyst especially with Raney's nickel, inorganic halides are the method for the halogenated biphenyl amine of co-catalyst preparation formula (I), the halogenated biphenyl amine for the formula (I) that this method is prepared has content height, the low feature of dehalogenation impurity.
Description
Technical field
The present invention relates to fine chemistry industry preparation fields, and in particular to a method of halogenated biphenyl amine is prepared, is especially adopted
The method for preparing halogenated biphenyl amine with Raney's nickel and co-catalyst.
Technical background
Currently the technology of halogenated biphenyl amine is prepared to be mainly the following, 1, metal add hydrochloric acid reduction method, this method disadvantage
To generate a large amount of metal solid waste, processing cost is high；2, hydroboron reduction method, this method disadvantage are at high cost, solid waste amount
Greatly；3, hydrazine hydrate reduction method, this method is at high cost, and hydrazine toxicity is big；4, sodium sulfide reducing method, it is big that this method generates waste liquid amount；5,
Catalytic hydrogenation, this method is the disadvantage is that using active metal catalyst and hydrogen, and safety is it may be noted that still only used catalytic amount
Catalyst, while by-product is water, for the clean method of green, so being relatively good restoring method.
Traditional catalyst is containing metal platinum, palladium and Ni-based catalyst in catalytic hydrogenation, and wherein nickel-base catalyst is more
To be cheap, especially Raney's nickel, catalytic activity is moderate, but during hydro-reduction halonitro biphenyl, unavoidably
Ground brings dehalogenation impurity, and dehalogenation impurity content is higher, and dehalogenation impurity in last handling process with product separating difficulty
Greatly, it therefore needs to select co-catalyst and catalyst complex appropriate, to improve the selectivity of hydro-reduction.
Summary of the invention
The present invention provides a kind of new methods that halogenated biphenyl amine is prepared using catalytic hydrogenation, especially with difference
In the common metal platinum, palladium and Ni-based catalyst of the prior art, but using Raney's nickel and co-catalyst catalytic hydrogenation come
The method for preparing halogenated biphenyl amine, this method have selectivity high, can increase substantially the content of halogenated biphenyl amine in product, have
Effect reduces the effect of the content of impurity dehalogenation aminobenzidine.
To achieve the purpose of the present invention, the invention provides the following technical scheme:
A method of preparing halogenated biphenyl amine, which is characterized in that the reaction equation is as follows:
Formula (II) formula (I)
Wherein X is halogen；
Reaction step are as follows:
Step 1: the compound of formula (II) is dissolved in water-miscible organic solvent and is thrown in hydriding reactor, wherein solvent and formula
(II) weight ratio of compound is 2:1-12:1, and the solvent water content is 0-20%, and the solvent is methanol or ethyl alcohol；
Step 2: catalyst Raney's nickel and the iodide solution as co-catalyst are thrown in hydriding reactor at 30-40 DEG C
Interior, the compound amount based on formula (II) is 100 parts by weight, and the Raney's nickel dosage is 0.1-20 parts by weight, wherein co-catalysis
Agent dosage and the weight ratio of Raney's nickel are 1:120-3:1, and heat temperature raising leads to hydrogen when temperature rises to 50-130 DEG C of reaction temperature
Gas starts hydrogenation reaction, and reaction pressure 0.1-5.0MPa keeps the temperature 1-6 hours when pressure is no longer changed in hydriding reactor,
Total reaction time including soaking time is 4-24h；Sampling at this time control in GC, without formula (II) in testing result
Compound, while the content of dehalogenation benzidine is lower than 0.6%, that is, stops reaction；
Step 3: being cooled to 30-35 DEG C, halogenated biphenyl amine of the invention is made in blowing, filtering, precipitation and distillage.
Preferably, the formula (I) compound is 4 '-chloro- 2- aminobphenyls；
Preferably, the iodide are potassium iodide, sodium iodide or cuprous iodide；
Preferably, the weight ratio of solvent and formula (II) compound is 7:1；
The compound amount for being preferably based on formula (II) is 100 parts by weight, and the Raney's nickel dosage is 1.0-3.0 weight
Part, most preferably 2.0 parts by weight, wherein co-catalyst dosage and the weight ratio of Raney's nickel are 1:5-1:20, most preferably 1:10；
Preferably, reaction temperature is 75-90 DEG C, more preferably 80-88 DEG C, most preferably 85 DEG C；
Preferably, reaction pressure is 0.8-1.2 MPa, most preferably 1 MPa.
Unless otherwise indicated, " % " in present specification is weight percentage
About mechanism: the present invention uses Raney's nickel for catalyst, low in cost；Further, co-catalyst is iodide,
It can play the fine generation that must inhibit dehalogenation impurity, while present invention employs suitable catalyst amount, co-catalysts
With the ratio of catalyst, temperature, the pressure of reaction, influence of the above-mentioned factor to reaction effect be also fairly obvious.
About effect:
1, the obtained high-purity halogenated biphenyl amine of the present invention, content are higher than 99.0%.
2, method of the invention is in industrial application value height, such as above-mentioned 4 '-chloro- 2- aminobphenyl is synthesis Boscalid
Important intermediate, 4 '-chloro- 2- aminobphenyls of high-purity can be made by the application method, so further be made pyridine acyl
Bacterium amine.
Specific embodiment
Combined with specific embodiments below and comparative example the present invention will be further described, however, the present invention is not limited thereto.
Embodiment 1:
Potassium iodide prepares 4 '-chloro- 2- aminobphenyls as co-catalyst
The 4 '-chloro- 2 nitro biphenyls that the content of 40g is 99.7% are molten into after liquid and put into the aqueous second for being 5% of 280g
It in alcohol, is heated to being completely dissolved, and while hot puts into the solution in 500mL hydriding reactor, when stirring is cooled to 35 DEG C, by 0.12g
Potassium iodide and 1.2g Raney's nickel are successively put into hydriding reactor, close hydriding reactor, and nitrogen is replaced 3 times, started to warm up, when temperature rises to
At 75 DEG C, logical hydrogen valve is opened, leading to pressure in hydrogen to hydriding reactor is 1.0MPa, closes logical hydrogen valve, is filled with after hydrogen in hydriding reactor
Gradually temperature is increased to 83 ~ 87 DEG C, and in control reaction in entire hydrogenation process between 83 ~ 87 DEG C, and whenever in hydriding reactor
When pressure reduction is to 0.85MPa, opening logical hydrogen valve and mending pressure in hydrogen to kettle is 1.0MPa, until under pressure no longer occurs in kettle
Drop continues to keep the temperature 1.5h at this time, and sampling carries out GC detection, the results showed that remaining without the chloro- 2 nitro biphenyl of raw material 4 '-, 4 '-is chloro-
2- aminobphenyl area normalization is that the area normalization of 99.4%, 2- aminobphenyl is 0.41%,.Reaction solution is filtered at this time, filtrate
Precipitation, then distill under negative pressure, the chloro- 2- aminobphenyl of product 4 '-is obtained, HPLC quantitative levels are 99.2% at this time, dechlorination biphenyl
Amine content is 0.48%, reaction yield 97.9%.
Embodiment 2: except co-catalyst be sodium iodide in addition to, remaining with embodiment 1, the result shows that, in GC control without raw material 4 '-
Chloro- 2 nitro biphenyl is remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are that the area normalization of 99.3%, 2- aminobphenyl is
0.42%,.Reaction solution is filtered at this time, filtrate precipitation, then distillation obtains the chloro- 2- aminobphenyl of product 4 '-, HPLC under negative pressure
Quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.54%, reaction yield 97.3%.
Embodiment 3: except co-catalyst be cuprous iodide in addition to, remaining with embodiment 1, the result shows that, in GC control without raw material
4 '-chloro- 2 nitro biphenyls are remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are that the area normalization of 99.4%, 2- aminobphenyl is
0.39%,.Reaction solution is filtered at this time, filtrate precipitation, then distilled under a high vacuum, obtains the chloro- 2- aminobphenyl of product 4 '-,
HPLC quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.51%, reaction yield 97.8%；
Embodiment 4: except catalyst amount is 0.8g, co-catalyst dosage is outside 0.08g, remaining is the same as embodiment 1, result
Show that control is remaining without the chloro- 2 nitro biphenyl of raw material 4 '-in GC, 4 '-chloro- 2- aminobphenyl area normalizations are in products obtained therefrom
The area normalization of 99.1%, 2- aminobphenyl is 0.43%,.Reaction solution is filtered at this time, filtrate precipitation, then steamed under a high vacuum
It evaporates, obtains the chloro- 2- aminobphenyl of product 4 '-, HPLC quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.55%, and reaction is received
Rate is 97.3%；
Embodiment 5: except catalyst amount is 1.2g, co-catalyst dosage is outside 0.08g, remaining is the same as embodiment 1, result
Show that control is remaining without the chloro- 2 nitro biphenyl of raw material 4 '-in GC, 4 '-chloro- 2- aminobphenyl area normalizations are in products obtained therefrom
The area normalization of 99.1%, 2- aminobphenyl is 0.46%,.Reaction solution is filtered at this time, filtrate precipitation, then steamed under a high vacuum
It evaporates, obtains the chloro- 2- aminobphenyl of product 4 '-, HPLC quantitative levels are 99.0%, and dechlorination biphenyl amine content is 0.58%, and reaction is received
Rate is 97.4%；
Embodiment 6: except reaction temperature is 79-83 DEG C outer, remaining with embodiment 1, the result shows that, control in GC without raw material
4 '-chloro- 2 nitro biphenyls are remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are the face of 99.1%, 2- aminobphenyl in products obtained therefrom
Product normalizing is 0.47%,.Reaction solution is filtered at this time, filtrate precipitation, then distilled under a high vacuum, obtains the chloro- 2- ammonia of product 4 '-
Base biphenyl, HPLC quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.59%, reaction yield 97.6%；
Embodiment 7: except reaction pressure be 1.35 ~ 1.5MPa in addition to, remaining with embodiment 1, the result shows that, in GC control without original
The chloro- 2 nitro biphenyl of material 4 '-is remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are 99.2%, 2- aminobphenyl in products obtained therefrom
Area normalization is 0.46%,.Reaction solution is filtered at this time, filtrate precipitation, then distilled under a high vacuum, obtains the chloro- 2- of product 4 '-
Aminobphenyl, HPLC quantitative levels are 99.2%, and dechlorination biphenyl amine content is 0.58%, reaction yield 97.9%；
Comparative example 1: in addition to not adding co-catalyst, remaining with embodiment 1, the result shows that, no raw material 4 '-chloro-
2 nitro biphenyl is remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are that the area normalization of 95.6%, 2- aminobphenyl is 3.9%,.This
When reaction solution is filtered, filtrate precipitation, then distill under a high vacuum obtains the chloro- 2- aminobphenyl of product 4 '-, HPLC quantitatively contains
Amount is 94.3%, and dechlorination biphenyl amine content is 5.2%, reaction yield 92.2%.Co-catalyst is not added in comparative example explanation,
Finally make dehalogenation benzidine impurity obviously higher.
Comparative example 2: except catalyst amount is 8.2g, co-catalyst dosage is outside 0.82g, remaining with embodiment 1,
The result shows that control is remaining without the chloro- 2 nitro biphenyl of raw material 4 '-in GC, 4 '-chloro- 2- aminobphenyl area normalizations in products obtained therefrom
Area normalization for 97.6%, 2- aminobphenyl is 1.91%.Reaction solution is filtered at this time, filtrate precipitation, then steamed under a high vacuum
It evaporates, obtains the chloro- 2- aminobphenyl of product 4 '-, HPLC quantitative levels are 97.1%, and dechlorination biphenyl amine content is 2.41%, and reaction is received
Rate is 95.5%；The comparative example illustrates that catalyst amount is excessively high, causes reactivity excessively high, finally makes dehalogenation benzidine
Impurity is obviously higher.
Comparative example 3: except reaction temperature be 35 ~ 39 DEG C, remaining with embodiment 1, the result shows that, reaction for 24 hours when GC
The chloro- 2 nitro biphenyl of middle control raw material 4 '-has a residue, area normalization 15.21%, 4 '-chloro- 2- aminobphenyl faces in products obtained therefrom
Product normalizing is that the area normalization of 84.47%, 2- aminobphenyl is 0.31%, and reaction is not finished at this time, the chloro- 2- ammonia of products obtained therefrom 4 '-
Base biphenyl, HPLC quantitative levels are 81.3%, and dechlorination biphenyl amine content is 0.40%, reaction yield 80.0%；The comparative example
Illustrate that reaction temperature is too low, cause reactivity too low, reaction is finally made to need overlong time, interior raw material can not convert for 24 hours
Completely.
Comparative example 4: except reaction temperature be 165 ~ 170 DEG C, remaining with embodiment 1, the result shows that, result table
Bright, no 4 '-chloro- 2 nitro biphenyl of raw material is remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are the face of 98.1%, 2- aminobphenyl
Product normalizing is 1.1%,.Reaction solution is filtered at this time, filtrate precipitation, then distilled under a high vacuum, obtains the chloro- 2- amino of product 4 '-
Biphenyl, HPLC quantitative levels are 97.2%, and dechlorination biphenyl amine content is 1.4%, reaction yield 94.9%.；The comparative example is said
Bright reaction temperature is excessively high, causes reactivity excessively high, finally makes dehalogenation benzidine impurity content higher while miscellaneous with other
Matter generates.
Comparative example 5: except reaction pressure be 6.0 ~ 6.15MPa, remaining with embodiment 1, the result shows that, no raw material
4 '-chloro- 2 nitro biphenyls are remaining, and 4 '-chloro- 2- aminobphenyl area normalizations are that the area normalization of 98.6%, 2- aminobphenyl is
0.8%,.Reaction solution is filtered at this time, filtrate precipitation, then distilled under a high vacuum, obtains the chloro- 2- aminobphenyl of product 4 '-,
HPLC quantitative levels are 98.6%, and dechlorination biphenyl amine content is 1.1%, reaction yield 96.2%.；Comparative example explanation is anti-
Hypertonia is answered, causes reactivity excessively high, finally makes dehalogenation benzidine impurity content higher.
Comparative example 6: except reaction pressure be 0.07 ~ 0.09MPa, remaining with embodiment 1, the result shows that, reaction for 24 hours
When GC in the control chloro- 2 nitro biphenyl of raw material 4 '-have a residue, area normalization 45.30%, 4 '-chloro- 2- amino connection in products obtained therefrom
Benzene area normalization is that the area normalization of 54.41%, 2- aminobphenyl is 0.10%, and reaction is not finished at this time, and products obtained therefrom 4 '-is chloro-
2- aminobphenyl, HPLC quantitative levels are 41.3%, and dechlorination biphenyl amine content is 0.13%, reaction yield 39.7%；The comparison is real
It applies example and illustrates that reaction pressure is too low, cause reactivity too low, reaction is finally made to need overlong time, interior raw material can not for 24 hours
Conversion is complete.
Comparative example 7: except reaction dissolvent is aqueous be 40% in addition to, remaining with embodiment 1, the result shows that, reaction for 24 hours when
The chloro- 2 nitro biphenyl of raw material 4 '-is controlled in GC a residue, area normalization 87.30%, 4 '-chloro- 2- aminobphenyls in products obtained therefrom
Area normalization is that the area normalization of 12.01%, 2- aminobphenyl is 0.40%, and reaction is not finished at this time, the chloro- 2- of products obtained therefrom 4 '-
Aminobphenyl, HPLC quantitative levels are 85.3%, and dechlorination biphenyl amine content is 0.54%, reaction yield 83.2%；The comparison is implemented
Example shows the excessively high progress for being unfavorable for reaction of moisture content.
A kind of method preparing halogenated biphenyl amine of the invention is described by specific example, this field skill
Art personnel can use for reference the content of present invention, and the links such as appropriate feed change, process conditions realize corresponding other purposes, related
Change all without departing from the contents of the present invention, all similar substitutions and modifications are aobvious and easy to those skilled in the art
See, is considered as being included within the scope of the present invention.
Claims (9)
1. a kind of method for preparing halogenated biphenyl amine, which is characterized in that the reaction equation is as follows:
Formula (II) formula (I)
Wherein X is halogen；
Reaction step are as follows:
Step 1: the compound of formula (II) is dissolved in water-miscible organic solvent and is thrown in hydriding reactor, wherein solvent and formula (II)
The weight ratio of compound is 2:1-12:1, and the solvent water content is 0-20 weight %, and the solvent is methanol or ethyl alcohol；
Step 2: at 30-40 DEG C, by catalyst Raney's nickel and the potassium iodide as co-catalyst, sodium iodide or cuprous iodide
Solution is thrown in hydriding reactor, and the compound amount based on formula (II) is 100 parts by weight, and the Raney's nickel dosage is 0.1-20 weight
Part, wherein co-catalyst dosage and the weight ratio of Raney's nickel are 1:120-3:1, heat temperature raising, when temperature rises to 50-130 DEG C instead
When answering temperature, logical hydrogen starts hydrogenation reaction, reaction pressure 0.1-5.0MPa, when pressure is no longer changed in hydriding reactor
When, 1-6 hours are kept the temperature, total reaction time including soaking time is 4-24h；Sampling at this time control in GC, detects
As a result the compound without formula (II) in, while the content of dehalogenation benzidine is lower than 0.6 weight %, that is, stops reaction；
Step 3: being cooled to 30-35 DEG C, the halogenated biphenyl amine is made in blowing, filtering, precipitation and distillage.
2. the method according to claim 1, wherein the formula (I) compound is 4 '-chloro- 2- aminobphenyls.
3. the method according to claim 1, wherein the weight ratio of the solvent and formula (II) compound is 7:1.
4. the method according to claim 1, wherein the compound amount based on formula (II) is 100 parts by weight, institute
Stating Raney's nickel dosage is 1.0-3.0 parts by weight.
5. according to the method described in claim 4, it is characterized in that, the Raney's nickel dosage is 2.0 parts by weight.
6. the method according to claim 1, wherein co-catalyst dosage and the weight ratio of Raney's nickel are 1:5-1:
20。
7. according to the method described in claim 6, it is characterized in that, co-catalyst dosage and the weight ratio of Raney's nickel are 1:10.
8. the method according to claim 1, wherein the reaction temperature is 75-90 DEG C.
9. the method according to claim 1, wherein reaction pressure is 0.8-1.2 MPa.
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