CN106883130A - A kind of method for preparing halogenated biphenyl amine - Google Patents
A kind of method for preparing halogenated biphenyl amine Download PDFInfo
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- CN106883130A CN106883130A CN201710176786.6A CN201710176786A CN106883130A CN 106883130 A CN106883130 A CN 106883130A CN 201710176786 A CN201710176786 A CN 201710176786A CN 106883130 A CN106883130 A CN 106883130A
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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 field, and in particular to a kind of formula（Ⅰ）Halogenated biphenyl amine method, especially with Raney's nickel be catalyst, inorganic halides be co-catalyst formula（Ⅰ）Halogenated biphenyl amine method, the formula that the method is prepared（Ⅰ）Halogenated biphenyl amine have content high, the characteristics of dehalogenation impurity is low.
Description
Technical field
The present invention relates to fine chemistry industry preparation field, and in particular to a kind of method for preparing halogenated biphenyl amine, particularly adopt
The method that halogenated biphenyl amine is prepared with Raney's nickel and co-catalyst.
Technical background
The current technology for preparing halogenated biphenyl amine mainly has following several, 1, metal add hydrochloric acid reducing process, the method shortcoming
To produce substantial amounts of metal solid waste, processing cost is high；2nd, hydroboron reducing process, the method shortcoming is high cost, solid waste amount
Greatly；3rd, hydrazine hydrate reduction method, the method high cost, hydrazine toxicity is big；4th, sodium sulfide reducing method, the method produces waste liquid amount big；5、
Catalytic hydrogenation, the method has the disadvantage to use active metal catalyst and hydrogen, and safety is it may be noted that still only used catalytic amount
Catalyst, while accessory substance be water, be green cleaning method, so being relatively good restoring method.
In catalytic hydrogenation traditional catalyst be containing metal platinum, palladium and Ni-based catalyst, wherein nickel-base catalyst more
For cheap, especially Raney's nickel, catalysis activity is moderate, but during hydro-reduction halonitro biphenyl, unavoidably
Bring dehalogenation impurity, and dehalogenation impurity content is higher, and dehalogenation impurity in last handling process with product separating difficulty
Greatly, thus need the appropriate co-catalyst of selection and catalyst complex and improve the selectivity of hydro-reduction.
The content of the invention
The invention provides a kind of new method that halogenated biphenyl amine is prepared using catalytic hydrogenation, especially with difference
Common metal platinum, palladium and Ni-based catalyst in prior art, but using Raney's nickel and co-catalyst catalytic hydrogenation come
The method for preparing halogenated biphenyl amine, the method has selectivity high, can increase substantially the content of halogenated biphenyl amine in product, has
Effect reduces the effect of the content of impurity dehalogenation aminobenzidine.
To realize the purpose of the present invention, the present invention provides following technical scheme：
A kind of method for preparing halogenated biphenyl amine, it is characterised in that the reaction equation is as follows：
Formula（II）Formula（I）
Wherein X is halogen；
Reactions steps are：
Step one, by formula（Ⅱ）Compound be dissolved in water-miscible organic solvent and throw in hydriding reactor, wherein solvent and formula（Ⅱ）
The weight ratio of compound is 2:1-12:1, the solvent water content is 0-20%, and the solvent is methyl alcohol or ethanol；
Step 2, at 30-40 DEG C, thrown in hydriding reactor using catalyst Raney's nickel and as the iodide solution of co-catalyst,
Based on formula（Ⅱ）Compound amount be 100 weight portions, the Raney's nickel consumption be 0.1-20 weight portions, wherein co-catalyst use
Amount is 1 with the weight ratio of Raney's nickel:120-3:1, heat temperature raising, when temperature rises to 50-130 DEG C of reaction temperature, logical hydrogen is opened
Beginning hydrogenation reaction, reaction pressure is 0.1-5.0MPa, when pressure no longer changes in hydriding reactor, is incubated 1-6 hours, including
Soaking time is 4-24h in interior total reaction time；Now sampling controlled in GC, without formula in testing result（Ⅱ）Chemical combination
Thing, while the content of dehalogenation benzidine is less than 0.6%, that is, stops reaction；
Step 3, it is cooled to 30-35 DEG C, blowing, filtering, precipitation and distillage are obtained halogenated biphenyl amine of the invention.
Preferably, the formula（I）Compound is 4 '-chloro- 2- aminobphenyls；
Preferably, the iodide are KI, sodium iodide or cuprous iodide；
Preferably, solvent and formula（Ⅱ）The weight ratio of compound is 7:1；
It is preferably based on formula（Ⅱ）Compound amount be 100 weight portions, the Raney's nickel consumption be 1.0-3.0 weight portions, most
Preferably 2.0 weight portions, wherein co-catalyst consumption are 1 with the weight ratio of Raney's nickel:5-1:20, most preferably 1:10；
Preferably, reaction temperature is 75-90 DEG C, most preferably more preferably 80-88 DEG C, 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
On mechanism：It is catalyst that the present invention uses Raney's nickel, with low cost；Further, co-catalyst is iodide, and it can
To play the fine generation that must suppress dehalogenation impurity, while present invention employs suitable catalyst amount, co-catalyst with urge
The ratio of agent, the temperature of reaction, pressure, influence of the above-mentioned factor to reaction effect is also fairly obvious.
On effect：
1st, the prepared high-purity halogenated biphenyl amine of the present invention, its content is higher than 99.0%.
2nd, the method for the present invention is high in industrial application value, such as above-mentioned 4 '-chloro- 2- aminobphenyls are synthesis Boscalids
Important intermediate, 4 '-chloro- 2- aminobphenyls of high-purity can be obtained by the application method, and then pyridine acyl is further obtained
Bacterium amine.
Specific embodiment
With reference to specific embodiment and comparative example, the present invention will be further described, but the invention is not restricted to this.
Embodiment 1：
KI prepares 4 '-chloro- 2- aminobphenyls as co-catalyst
The 4 '-chloro- 2 nitro biphenyl that the content of 40g is 99.7% is molten into after liquid put into 280g it is aqueous be 5% ethanol in,
It is heated to being completely dissolved, and while hot puts into 500mL hydriding reactors the solution, stirring is when being cooled to 35 DEG C, by 0.12g KI
Put into hydriding reactor successively with 1.2g Raney's nickels, close hydriding reactor, nitrogen displacement 3 times is started to warm up, when temperature rises to 75 DEG C
When, open and lead to hydrogen valve, it is 1.0MPa to lead to pressure in hydrogen to hydriding reactor, closes logical hydrogen valve, and hydriding reactor is interior gradually after being filled with hydrogen
Temperature is increased to 83 ~ 87 DEG C, and controls to react between 83 ~ 87 DEG C in whole hydrogenation process, and whenever pressure in hydriding reactor
When being reduced to 0.85MPa, it is 1.0MPa to open logical hydrogen valve and mend pressure in hydrogen to kettle, until declining no longer occurs in pressure in kettle,
Now continue to be incubated 1.5h, sampling carries out GC detections, as a result show without raw material 4 '-chloro- 2 nitro biphenyl is remaining, 4 '-chloro- 2- ammonia
Base biphenyl area normalization is 0.41% for the area normalization of 99.4%, 2- aminobphenyls,.Now by reacting liquid filtering, filtrate precipitation,
Distill under negative pressure again, obtain product 4 '-chloro- 2- aminobphenyls, now HPLC quantitative levels are 99.2%, and dechlorination benzidine contains
It is 0.48% to measure, and reaction yield is 97.9%.
Embodiment 2：In addition to co-catalyst is sodium iodide,, with embodiment 1, its result shows for remaining, controlled in GC without raw material 4 '-
Chloro- 2 nitro biphenyl is remaining, and 4 '-chloro- 2- aminobphenyls area normalization is for the area normalization of 99.3%, 2- aminobphenyls
0.42%,.Now by reacting liquid filtering, filtrate precipitation, then distillation obtains product 4 '-chloro- 2- aminobphenyls, HPLC under negative pressure
Quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.54%, and reaction yield is 97.3%.
Embodiment 3：In addition to co-catalyst is cuprous iodide,, with embodiment 1, its result shows, is controlled without raw material in GC for remaining
4 '-chloro- 2 nitro biphenyl is remaining, and 4 '-chloro- 2- aminobphenyls area normalization is for the area normalization of 99.4%, 2- aminobphenyls
0.39%,.Now by reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, product 4 '-chloro- 2- aminobphenyls are obtained,
HPLC quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.51%, and reaction yield is 97.8%；
Embodiment 4：Except catalyst amount be 0.8g, co-catalyst consumption be 0.08g outside, remaining with embodiment 1, its result table
It is bright, controlled in GC without raw material 4 '-chloro- 2 nitro biphenyl is remaining, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls area normalization is
The area normalization of 99.1%, 2- aminobphenyl is 0.43%,.Now by reacting liquid filtering, filtrate precipitation, then steam under a high vacuum
Evaporate, obtain product 4 '-chloro- 2- aminobphenyls, 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 be 1.2g, co-catalyst consumption be 0.08g outside, remaining with embodiment 1, its result table
It is bright, controlled in GC without raw material 4 '-chloro- 2 nitro biphenyl is remaining, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls area normalization is
The area normalization of 99.1%, 2- aminobphenyl is 0.46%,.Now by reacting liquid filtering, filtrate precipitation, then steam under a high vacuum
Evaporate, obtain product 4 '-chloro- 2- aminobphenyls, HPLC quantitative levels are 99.0%, and dechlorination biphenyl amine content is 0.58%, and reaction is received
Rate is 97.4%；
Embodiment 6：In addition to reaction temperature is 79-83 DEG C,, with embodiment 1, its result shows for remaining, controlled in GC without raw material 4 '-chloro-
2 nitro biphenyl is remaining, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls area normalization is the area normalization of 99.1%, 2- aminobphenyls
It is 0.47%,.Now by reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, product 4 '-chloro- 2- aminobphenyls are obtained,
HPLC quantitative levels are 99.1%, and dechlorination biphenyl amine content is 0.59%, and reaction yield is 97.6%；
Embodiment 7：In addition to reaction pressure is 1.35 ~ 1.5MPa,, with embodiment 1, its result shows, is controlled without raw material in GC for remaining
4 '-chloro- 2 nitro biphenyl is remaining, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls area normalization is the face of 99.2%, 2- aminobphenyls
Product normalizing is 0.46%,.Now by reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, obtain product 4 '-chloro- 2- ammonia
Base biphenyl, HPLC quantitative levels are 99.2%, and dechlorination biphenyl amine content is 0.58%, and reaction yield is 97.9%；
Comparative example 1：In addition to without co-catalyst,, with embodiment 1, its result shows for remaining, without raw material 4 '-chloro- 2- nitre
Base biphenyl is remaining, and 4 '-chloro- 2- aminobphenyls area normalization is 3.9% for the area normalization of 95.6%, 2- aminobphenyls,.Now will
Reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, product 4 '-chloro- 2- aminobphenyls are obtained, HPLC quantitative levels are
94.3%, dechlorination biphenyl amine content is 5.2%, and reaction yield is 92.2%.Comparative example explanation is not added with co-catalyst, finally
So that dehalogenation benzidine impurity is substantially higher.
Comparative example 2：Except catalyst amount be 8.2g, co-catalyst consumption be 0.82g outside, remaining with embodiment 1, its
Result shows, controlled in GC without raw material 4 '-chloro- 2 nitro biphenyl is remaining, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls area normalization
The area normalization for being 97.6%, 2- aminobphenyls is 1.91%.Now by reacting liquid filtering, filtrate precipitation, then steam under a high vacuum
Evaporate, obtain product 4 '-chloro- 2- aminobphenyls, HPLC quantitative levels are 97.1%, and dechlorination biphenyl amine content is 2.41%, and reaction is received
Rate is 95.5%；Comparative example explanation catalyst amount is too high, causes reactivity too high, finally causes dehalogenation benzidine
Impurity is substantially higher.
Comparative example 3：Except reaction temperature is 35 ~ 39 DEG C,, with embodiment 1, its result shows for remaining, GC during reaction 24h
Middle control raw material 4 '-chloro- 2 nitro biphenyl has residue, and area normalization is 15.21%, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls face
Product normalizing is 0.31% for the area normalization of 84.47%, 2- aminobphenyls, now reacts and does not terminate, products obtained therefrom 4 '-chloro- 2- ammonia
Base biphenyl, HPLC quantitative levels are 81.3%, and dechlorination biphenyl amine content is 0.40%, and reaction yield is 80.0%；The comparative example
Illustrate that reaction temperature is too low, cause reactivity too low, finally cause that reaction needs overlong time, raw material cannot be converted in 24h
Completely.
Comparative example 4：Except reaction temperature is 165 ~ 170 DEG C,, with embodiment 1, its result shows for remaining, its result table
It is bright, without raw material 4 '-chloro- 2 nitro biphenyl residue, 4 '-chloro- 2- aminobphenyls area normalization is the face of 98.1%, 2- aminobphenyls
Product normalizing is 1.1%,.Now by reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, obtain product 4 '-chloro- 2- amino
Biphenyl, HPLC quantitative levels are 97.2%, and dechlorination biphenyl amine content is 1.4%, and reaction yield is 94.9%.；The comparative example says
Bright reaction temperature is too high, causes reactivity too high, finally causes that dehalogenation benzidine impurity content is higher, while miscellaneous with other
Matter is produced.
Comparative example 5：Except reaction pressure is 6.0 ~ 6.15MPa,, with embodiment 1, its result shows, without raw material for remaining
4 '-chloro- 2 nitro biphenyl is remaining, and 4 '-chloro- 2- aminobphenyls area normalization is for the area normalization of 98.6%, 2- aminobphenyls
0.8%,.Now by reacting liquid filtering, filtrate precipitation, then distill under a high vacuum, product 4 '-chloro- 2- aminobphenyls are obtained,
HPLC quantitative levels are 98.6%, and dechlorination biphenyl amine content is 1.1%, and reaction yield is 96.2%.；Comparative example explanation is anti-
Hypertonia is answered, causes reactivity too high, finally cause that dehalogenation benzidine impurity content is higher.
Comparative example 6：Except reaction pressure is 0.07 ~ 0.09MPa,, with embodiment 1, its result shows for remaining, reacts 24h
When GC in control raw material 4 '-chloro- 2 nitro biphenyl and have residue, area normalization is 45.30%, 4 ' in products obtained therefrom-chloro- 2- amino connection
Benzene area normalization is 0.10% for the area normalization of 54.41%, 2- aminobphenyls, now reacts and does not terminate, products obtained therefrom 4 '-chloro-
2- aminobphenyls, HPLC quantitative levels are 41.3%, and dechlorination biphenyl amine content is 0.13%, and reaction yield is 39.7%；The contrast reality
Apply example explanation reaction pressure too low, cause reactivity too low, finally cause that reaction needs overlong time, raw material cannot in 24h
Conversion is complete.
Comparative example 7：It is that in addition to 40%,, with embodiment 1, its result shows for remaining except reaction dissolvent is aqueous, during reaction 24h
Raw material 4 '-chloro- 2 nitro biphenyl is controlled in GC residue, and area normalization is 87.30%, 4 ' in products obtained therefrom-chloro- 2- aminobphenyls
Area normalization is that the area normalization of 12.01%, 2- aminobphenyls is 0.40%, now reacts and does not terminate, products obtained therefrom 4 '-chloro- 2-
Aminobphenyl, HPLC quantitative levels are 85.3%, and dechlorination biphenyl amine content is 0.54%, and reaction yield is 83.2%；The contrast is implemented
Example shows too high the carrying out for being unfavorable for reaction of moisture.
A kind of method for preparing halogenated biphenyl amine of the invention is described by specific example, this area skill
Art personnel can use for reference the links such as present invention, appropriate feed change, process conditions to realize corresponding other purposes, and it is related
Change all without departing from present disclosure, all similar replacements and change are to those skilled in the art aobvious and easy
See, be considered as being included within the scope of the present invention.
Claims (10)
1. a kind of method for preparing halogenated biphenyl amine, it is characterised in that the reaction equation is as follows：
Formula（II）Formula（I）
Wherein X is halogen；
Reactions steps are：
Step one, by formula（Ⅱ）Compound be dissolved in water-miscible organic solvent and throw in hydriding reactor, wherein solvent and formula（Ⅱ）
The weight ratio of compound is 2:1-12:1, the solvent water content is 0-20%, and the solvent is methyl alcohol or ethanol；
Step 2, at 30-40 DEG C, thrown in hydriding reactor using catalyst Raney's nickel and as the iodide solution of co-catalyst,
Based on formula（Ⅱ）Compound amount be 100 weight portions, the Raney's nickel consumption be 0.1-20 weight portions, wherein co-catalyst use
Amount is 1 with the weight ratio of Raney's nickel:120-3:1, heat temperature raising, when temperature rises to 50-130 DEG C of reaction temperature, logical hydrogen is opened
Beginning hydrogenation reaction, reaction pressure is 0.1-5.0MPa, when pressure no longer changes in hydriding reactor, is incubated 1-6 hours, including
Soaking time is 4-24h in interior total reaction time；Now sampling controlled in GC, without formula in testing result（Ⅱ）Chemical combination
Thing, while the content of dehalogenation benzidine is less than 0.6%, that is, stops reaction；
Step 3, it is cooled to 30-35 DEG C, blowing, filtering, precipitation and distillage are obtained halogenated biphenyl amine of the invention.
2. method according to claim 1, it is characterised in that the formula（I）Compound is 4 '-chloro- 2- aminobphenyls.
3. method according to claim 1, it is characterised in that the iodide are KI, sodium iodide or cuprous iodide.
4. method according to claim 1, it is characterised in that the solvent and formula（Ⅱ）The weight ratio of compound is 7:1.
5. method according to claim 1, it is characterised in that based on formula（Ⅱ）Compound amount be 100 weight portions, institute
Raney's nickel consumption is stated for 1.0-3.0 weight portions.
6. method according to claim 5, it is characterised in that the Raney's nickel consumption is 2.0 weight portions.
7. method according to claim 1, it is characterised in that co-catalyst consumption is 1 with the weight ratio of Raney's nickel:5-1:
20。
8. method according to claim 7, it is characterised in that co-catalyst consumption is 1 with the weight ratio of Raney's nickel:10.
9. method according to claim 1, it is characterised in that the reaction temperature is 75-90 DEG C.
10. method according to claim 1, it is characterised in that reaction pressure is 0.8-1.2 MPa.
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