CN109369407A - The preparation method of o-nitrobenzyl bromide - Google Patents
The preparation method of o-nitrobenzyl bromide Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of o-nitrobenzyl bromide, which is, using NaClO/HBr as bromating agent, o-nitrobenzyl bromide to be made by bromination reaction under the initiation using azodiisobutyronitrile as initiator using ortho-methylnitrobenzene as raw material.Preparation method of the invention, o-nitrobenzyl bromide is prepared by bromating agent of NaClO/HBr, raw material is easy to get, is low in cost, and simple process, easy to operate, reaction condition is mild, reaction selectivity is higher, reaction yield > 72% (in terms of ortho-methylnitrobenzene), the content > 97% of o-nitrobenzyl bromide in solid product after purification process is suitble to industrialization promotion.
Description
Technical field
The present invention relates to a kind of preparation methods of o-nitrobenzyl bromide.
Background technique
O-nitrobenzyl bromide is an important intermediate of pesticide pyraclostrobin, and chemical formula is as follows:
The preparation method of o-nitrobenzyl bromide, mainly using ortho-methylnitrobenzene as raw material, with Br2、H2O2/HBr、KBrO3/
HBr, NBS etc. are bromating agent, prepare o-nitrobenzyl bromide under the radical initiators such as illumination or azodiisobutyronitrile.But these
Method there are yields relatively low, expensive raw material price, the cost is relatively high.Such as: anti-through bromination using ortho-methylnitrobenzene as starting material
O-nitrobenzyl bromide should be obtained, yield is 58%~62% (in terms of ortho-methylnitrobenzene), and synthetic method is as follows:
Therefore, obtain that a kind of raw material is easy to get, is low in cost, simple process, easy to operate, reaction condition is mild, reaction choosing
The preparation method of high, high income the o-nitrobenzyl bromide of selecting property has a very important significance.
Summary of the invention
It is easy to get the technical problem to be solved by the present invention is to overcoming the deficiencies of the prior art and provide a kind of raw material, is at low cost
Honest and clean, simple process, easy to operate, reaction condition is mild, reaction selectivity is high, the preparation side of the o-nitrobenzyl bromide of high income
Method.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of preparation method of o-nitrobenzyl bromide, the preparation method are using ortho-methylnitrobenzene as raw material, with NaClO/
HBr is bromating agent, and o-nitrobenzyl bromide is made by bromination reaction under the initiation using azodiisobutyronitrile as initiator,
Chemical equation is as follows:
Above-mentioned preparation method, it is preferred that the following steps are included:
S1, solvent is divided into two parts, respectively the first solvent and the second solvent；Azodiisobutyronitrile is divided into two parts, point
It Wei not the first initiator and the second initiator；Ortho-methylnitrobenzene, hydrobromic acid solution, the first initiator, the first solvent are mixed, obtained
To the first mixed solution；Second solvent is mixed with the second initiator, obtains the second mixed solution；
S2, the first mixed solution obtained in step S1 is heated；
S3, the second mixed solution obtained in step S1 and liquor natrii hypochloritis are added drop-wise to simultaneously it is heated in step S2
Bromination reaction is carried out in the first mixed solution afterwards；
S4, continue bromination reaction after solution in step S3 drips, obtain o-nitrobenzyl bromide.
Above-mentioned preparation method, it is preferred that the molar ratio of hydrobromic acid is 1 in the ortho-methylnitrobenzene and hydrobromic acid solution:
0.7~1.5；The molar ratio of the ortho-methylnitrobenzene and azodiisobutyronitrile is 1: 0.03~0.1；First initiator and
The mass ratio of two initiators is 0.5g: 2g~3g；The mass ratio of the ortho-methylnitrobenzene and solvent is 1: 3.0~8.0；Described
The mass ratio of one solvent and the second solvent is 136g~177g: 70g；The ortho-methylnitrobenzene and hypochlorous acid in liquor natrii hypochloritis
The molar ratio of sodium is 1: 0.7~1.4.
Above-mentioned preparation method, it is preferred that the molar ratio of hydrobromic acid is 1 in the ortho-methylnitrobenzene and hydrobromic acid solution:
1.0~1.3；The molar ratio of the ortho-methylnitrobenzene and azodiisobutyronitrile is 1: 0.05~0.07；The ortho-methylnitrobenzene with
The mass ratio of solvent is 1: 5.0~6.0；The molar ratio of the ortho-methylnitrobenzene and sodium hypochlorite in liquor natrii hypochloritis is 1:
0.9~1.2.
Above-mentioned preparation method, it is preferred that the mass concentration of the liquor natrii hypochloritis is 10%~13%；The hydrogen bromine
The mass concentration of acid solution is 40%~48%.
Above-mentioned preparation method, it is preferred that the solvent is one of dichloroethanes, carbon tetrachloride or chlorobenzene.
Above-mentioned preparation method, it is preferred that in the step S2, the heating is that the first mixed solution is heated to 75 DEG C
~85 DEG C.
Above-mentioned preparation method, it is preferred that in the step S3, the time for adding of second mixed solution is 2h；Institute
The time for adding for stating liquor natrii hypochloritis is 2.5h；The temperature that reaction system is controlled during the dropwise addition is 75 DEG C~85 DEG C.
Above-mentioned preparation method, it is preferred that in the step S4, the time of the bromination reaction is 2.5h.
Above-mentioned preparation method, it is preferred that further comprising the steps of after the completion of the bromination reaction in the step S4:
At 40 DEG C by bromination reaction after organic phase in obtained reaction mixture separate；Use mass concentration for 10% sulfurous
Acid sodium aqueous solution washs isolated organic phase.
Compared with prior art, the invention has the following advantages that
The present invention provides a kind of preparation methods of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, with NaClO/HBr
For bromating agent, reacted to obtain o-nitrobenzyl bromide under the initiation of azodiisobutyronitrile.Preparation method of the present invention, with
NaClO/HBr is bromating agent, and raw material is easy to get, is low in cost, and simple process, easy to operate, reaction condition are mild, selecting response
Higher, the reaction yield > 72% (in terms of ortho-methylnitrobenzene) of property, o-nitrobenzyl bromide contains in the solid product after purification process
> 97% is measured, industrialization promotion is suitble to.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection model not thereby limiting the invention
It encloses.
Unless otherwise instructed, agents useful for same of the present invention is commercially available, and instrument equipment of the present invention is that conventional instrument is set
Standby, operating method of the present invention is conventional practices.
Embodiment 1
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
206g dichloroethanes is divided into two parts, respectively the first solvent 136g, the second solvent 70g；2.5g azo two is different
Butyronitrile (AIBN) is divided into two parts, respectively the first initiator 0.5g, the second initiator 2.0g.
41.2g (0.30mol) ortho-methylnitrobenzene, 136g dichloroethanes (the first solvent), 54.6g hydrobromic acid solution (are somebody's turn to do
The mass concentration of hydrobromic acid is 40% in solution, i.e., contains 0.27mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile
(the first initiator) is uniformly mixed, and obtains the first mixed solution.
2.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g dichloroethanes (the second solvent), second is mixed
Close solution.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 75 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 137.3g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
13.0%, i.e., contain 0.24mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 75 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 253.2g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 18.5% in the organic phase, and reaction yield is 72.3% (with adjacent nitro first
Benzene meter).The organic phase can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrazoles oxygroup first
Base] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
Embodiment 2
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
247g dichloroethanes is divided into two parts, respectively the first solvent 177g, the second solvent 70g；3.5g azo two is different
Butyronitrile (AIBN) is divided into two parts, respectively the first initiator 0.5g, the second initiator 3.0g.
41.2g (0.30mol) ortho-methylnitrobenzene, 177g dichloroethanes (the first solvent), 50.6g hydrobromic acid solution (are somebody's turn to do
The mass concentration of hydrobromic acid is 48% in solution, i.e., contains 0.30mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile
(the first initiator) is uniformly mixed, and obtains the first mixed solution.
3.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g dichloroethanes (the second solvent), obtains
Two mixed solutions.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 78 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 200.9g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
10.0%, i.e., contain 0.27mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 78 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 294.2g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 16.0% in the organic phase, and reaction yield is 72.6% (with adjacent nitro first
Benzene meter).The organic phase can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrazoles oxygroup first
Base] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
Embodiment 3
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
230g carbon tetrachloride is divided into two parts, respectively the first solvent 160g, the second solvent 70g；2.5g azo two is different
Butyronitrile (AIBN) is divided into two parts, respectively the first initiator 0.5g, the second initiator 2.0g.
41.2g (0.30mol) ortho-methylnitrobenzene, 160g carbon tetrachloride (the first solvent), 66.7g hydrobromic acid solution (are somebody's turn to do
The mass concentration of hydrobromic acid is 40% in solution, i.e., contains 0.33mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile
(the first initiator) is uniformly mixed, and obtains the first mixed solution.
2.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g carbon tetrachloride (the second solvent), obtains
Two mixed solutions.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 75 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 223.2g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
10.0%, i.e., contain 0.30mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 75 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 277.2g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 17.1% in the organic phase, and reaction yield is 73.1% (with adjacent nitro first
Benzene meter).The organic phase can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrazoles oxygroup first
Base] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
Embodiment 4
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
230g dichloroethanes is divided into two parts, respectively the first solvent 160g, the second solvent 70g；2.5g azo two is different
Butyronitrile (AIBN) is divided into two parts, respectively the first initiator 0.5g, the second initiator 2.0g.
41.2g (0.30mol) ortho-methylnitrobenzene, 160g dichloroethanes (the first solvent), 72.8g hydrobromic acid solution (are somebody's turn to do
The mass concentration of hydrobromic acid is 40% in solution, i.e., contains 0.36mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile
(the first initiator) is uniformly mixed, and obtains the first mixed solution.
2.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g dichloroethanes (the second solvent), obtains
Two mixed solutions.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 78 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 245.5g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
10.0%, i.e., contain 0.33mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 78 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 276.4g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 17.3% in the organic phase, and reaction yield is 73.8% (with adjacent nitro first
Benzene meter).O-nitrobenzyl bromide solution can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrrole
Azoles oxygroup methyl] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
Embodiment 5
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
230g chlorobenzene is divided into two parts, respectively the first solvent 160g, the second solvent 70g；By 3.5g azodiisobutyronitrile
(AIBN) it is divided into two parts, respectively the first initiator 0.5g, the second initiator 3.0g.
By 41.2g (0.30mol) ortho-methylnitrobenzene, 160g chlorobenzene (the first solvent), 72.8g hydrobromic acid solution (solution
The mass concentration of middle hydrobromic acid is 40%, i.e., contains 0.36mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile (first
Initiator) it is uniformly mixed, obtain the first mixed solution.
3.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g chlorobenzene (the second solvent), it is mixed to obtain second
Close solution.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 75 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 188.9g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
13.0%, i.e., contain 0.33mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 75 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 277.9g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 17.1% in the organic phase, and reaction yield is 73.3% (with adjacent nitro first
Benzene meter).O-nitrobenzyl bromide solution can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrrole
Azoles oxygroup methyl] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
Embodiment 6
A kind of preparation method of o-nitrobenzyl bromide, using ortho-methylnitrobenzene as raw material, using NaClO/HBr as bromating agent,
O-nitrobenzyl bromide is made by bromination reaction under using azodiisobutyronitrile as the initiation of initiator, comprising the following steps:
(1) the first mixed solution and the second mixed solution are prepared:
230g chlorobenzene is divided into two parts, respectively the first solvent 160g, the second solvent 70g；By 3.5g azodiisobutyronitrile
(AIBN) it is divided into two parts, respectively the first initiator 0.5g, the second initiator 3.0g.
By 41.2g (0.30mol) ortho-methylnitrobenzene, 160g chlorobenzene (the first solvent), 78.9g (hydrobromic acid in the solution
Mass concentration is 40%, i.e., contains 0.39mol hydrobromic acid in the solution) and 0.5g azodiisobutyronitrile (the first initiator) mixing
Uniformly, the first mixed solution is obtained.
3.0g azodiisobutyronitrile (the second initiator) is uniformly mixed with 70g chlorobenzene (the second solvent), it is mixed to obtain second
Close solution.
(2) in the 500mL four-hole bottle equipped with mechanical stirring, thermometer, reflux condensing tube and dropping funel, step is added
(1) the first mixed solution made from is heated to 85 DEG C under stirring condition, and keeps the temperature, then drips simultaneously into four-hole bottle
Adding the second mixed solution made from step (1) and 267.8g liquor natrii hypochloritis, (mass concentration of sodium hypochlorite is in the solution
10.0%, i.e., contain 0.36mol sodium hypochlorite in the solution) bromination reaction is carried out, wherein the time for adding of the second mixed solution
It is 2 hours, the time for adding of liquor natrii hypochloritis is 2.5 hours, after being added dropwise to complete, and continues to be stirred to react 2.5 at 85 DEG C small
When, reaction terminates, and obtains reaction mixture.
(3) organic phase in reaction mixture that step (2) obtains is separated at 40 DEG C, gained organic phase 30g
The sodium sulfite aqueous solution that mass concentration is 10% washs, and layering obtains 276.2g organic phase and (as contains o-nitrobenzyl bromide
Organic solution), the content of o-nitrobenzyl bromide is 17.5% in the organic phase, and reaction yield is 74.6% (with adjacent nitro first
Benzene meter).O-nitrobenzyl bromide solution can be directly used for pyraclostrobin next step intermediate 2- [(N-4- rubigan) -3- pyrrole
Azoles oxygroup methyl] nitrobenzene synthesis；Or petroleum ether is added to obtain solid o-nitrobenzyl bromide, content > 97% after precipitation.
The shadow of different material amount ratio, different solvents type and differential responses temperature to reaction yield in Examples 1 to 6
It rings, as shown in table 1 below:
Reaction yield data in 1 embodiment of the present invention 1~6 of table under different condition
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of o-nitrobenzyl bromide, which is characterized in that the preparation method be using ortho-methylnitrobenzene as raw material,
Using NaClO/HBr as bromating agent, adjacent nitre is made by bromination reaction under the initiation using azodiisobutyronitrile as initiator
Base benzyl bromide, chemical equation are as follows:
2. preparation method according to claim 1, which is characterized in that the preparation method comprises the following steps:
S1, solvent is divided into two parts, respectively the first solvent and the second solvent；Azodiisobutyronitrile is divided into two parts, respectively
First initiator and the second initiator；Ortho-methylnitrobenzene, hydrobromic acid solution, the first initiator, the first solvent are mixed, obtain the
One mixed solution；Second solvent is mixed with the second initiator, obtains the second mixed solution；
S2, the first mixed solution obtained in step S1 is heated；
S3, the second mixed solution obtained in step S1 and liquor natrii hypochloritis are added drop-wise to simultaneously it is heated in step S2 after the
Bromination reaction is carried out in one mixed solution；
S4, continue bromination reaction after solution in step S3 drips, obtain o-nitrobenzyl bromide.
3. preparation method according to claim 2, which is characterized in that hydrogen bromine in the ortho-methylnitrobenzene and hydrobromic acid solution
The molar ratio of acid is 1: 0.7~1.5；The molar ratio of the ortho-methylnitrobenzene and azodiisobutyronitrile is 1: 0.03~0.1；It is described
The mass ratio of first initiator and the second initiator is 0.5g: 2g~3g；The mass ratio of the ortho-methylnitrobenzene and solvent is 1:
3.0~8.0；The mass ratio of first solvent and the second solvent is 136g~177g: 70g；The ortho-methylnitrobenzene and time chlorine
The molar ratio of sodium hypochlorite is 1: 0.7~1.4 in acid sodium solution.
4. preparation method according to claim 3, which is characterized in that hydrogen bromine in the ortho-methylnitrobenzene and hydrobromic acid solution
The molar ratio of acid is 1: 1.0~1.3；The molar ratio of the ortho-methylnitrobenzene and azodiisobutyronitrile is 1: 0.05~0.07；Institute
The mass ratio for stating ortho-methylnitrobenzene and solvent is 1: 5.0~6.0；The ortho-methylnitrobenzene and sodium hypochlorite in liquor natrii hypochloritis
Molar ratio be 1: 0.9~1.2.
5. the preparation method according to claim 4, which is characterized in that the mass concentration of the liquor natrii hypochloritis is 10%
~13%；The mass concentration of the hydrobromic acid solution is 40%~48%.
6. the preparation method according to any one of claim 2~5, which is characterized in that the solvent is dichloroethanes, four
One of chlorination carbon or chlorobenzene.
7. the preparation method according to any one of claim 2~5, which is characterized in that in the step S2, the heating
It is that the first mixed solution is heated to 75 DEG C~85 DEG C.
8. the preparation method according to any one of claim 2~5, which is characterized in that in the step S3, described second
The time for adding of mixed solution is 2h；The time for adding of the liquor natrii hypochloritis is 2.5h；It is controlled during the dropwise addition anti-
The temperature for answering system is 75 DEG C~85 DEG C.
9. the preparation method according to any one of claim 2~5, which is characterized in that in the step S4, the bromination
The time of reaction is 2.5h.
10. the preparation method according to any one of claim 2~5, which is characterized in that in the step S4, the bromine
Change further comprising the steps of after the reaction was completed: at 40 DEG C by bromination reaction after organic phase in obtained reaction mixture isolate
Come；Mass concentration is used to wash for 10% sodium sulfite aqueous solution to isolated organic phase.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999747A (en) * | 2019-04-23 | 2019-07-12 | 浙江工业大学 | A kind of device and preparation method thereof of serialization preparation adjacent nitro benzyl bromine |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
| CN114773204A (en) * | 2022-05-24 | 2022-07-22 | 浙江禾本科技股份有限公司 | Method for continuously preparing benzyl bromide derivative |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999747A (en) * | 2019-04-23 | 2019-07-12 | 浙江工业大学 | A kind of device and preparation method thereof of serialization preparation adjacent nitro benzyl bromine |
| CN114369029A (en) * | 2022-01-05 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of o-nitrobenzyl bromide |
| CN114773204A (en) * | 2022-05-24 | 2022-07-22 | 浙江禾本科技股份有限公司 | Method for continuously preparing benzyl bromide derivative |
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