CN103242178A - Synthetic method of 2-chloro-3-phenoxyl-6-nitroaniline - Google Patents
Synthetic method of 2-chloro-3-phenoxyl-6-nitroaniline Download PDFInfo
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Abstract
The invention discloses a synthetic method of 2-chloro-3-phenoxyl-6-nitroaniline. The method comprises the following steps of: (1) under an ammonolysis reaction condition, contacting 2, 3, 4-trichloronitrobenzene with an aminating agent in the presence of an organic solvent; and (2) under an etherification reaction condition, contacting the purified or non-purified products of ammonolysis reaction in the mixture obtained by the step (1) with phenol in the presence of an alkali compound, and performing solid-liquid separation for the mixture obtained by contact to obtain 2-chloro-3-phenoxyl-6-nitroaniline, wherein the alkali compound is potassium carbonate and/or sodium carbonate. According to the method provided by the invention, the yield of the synthesized 2-chloro-3-phenoxyl-6-nitroaniline is high and the purity is good, the method is simplified in industrialized production and operation, and the solvent can be recycled.
Description
Technical field
The present invention relates to the synthetic method of a kind of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
Background technology
2-chloro-3-phenoxy group-the 6-N-methyl-p-nitroaniline is diphenyl ether herbicide, is a kind of proporphyrinogen oxidase inhibitor.Be mainly used in preventing and kill off potato before the seedling gramineous weeds in Sunflower Receptacle and the winter wheat field and broadleaf weeds.Its mechanism of action is: after using, at soil surface deposition one deck medicine film, when gramineous weeds and broadleaf weeds penetrated soil surface, weedicide was respectively by the tender shoots of seedling, and plumular axis and coleoptile absorb.Suck after several days, seedling is with regard to flavescence, and growth retardation is last dead.Compare most of weedicides, 2-chloro-3-phenoxy group-the 6-N-methyl-p-nitroaniline is littler to the dependency of soil humidity.
At present, the method that multiple production 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline is arranged, but when these methods of employing are carried out the actual production of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, when especially carrying out suitability for industrialized production, no matter be to adopt the synthetic method of multistep or the synthetic method of " one kettle way ", purification procedures is many in the middle of all existing, it is many to relate to solvent species, product impurity is many, the solvent recuperation difficulty, thereby not only the low yield of purity is low for the 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline product that causes suitability for industrialized production, and production operation inconvenience, energy consumption is big, the problem that cost is high.
Therefore, when carrying out 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline suitability for industrialized production, need to obtain the more synthetic method of high product purity and yield, and simplify production operation, make solvent be easy to reclaim, to solve above-mentioned suitability for industrialized production operation inconvenience, how not easy to be recycled, the product impurity problem how of solvent species that prior art exists.
Summary of the invention
The objective of the invention is in order to obtain the high synthetic method of product purity and yield, product impurity is many in the solution prior art, and suitability for industrialized production operation inconvenience, solvent species is problem not easy to be recycled how, and the synthetic method of a kind of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline is provided.
To achieve these goals, the invention provides the synthetic method of a kind of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, this method comprises: (1) contacts with aminating agent 2,3,4-trichloronitrobenzene under the ammonolysis reaction condition in the presence of organic solvent; (2) under the etherification reaction condition, make the ammonolysis reaction product purification in step (1) the gained mixture or do not contact in the presence of basic cpd with phenol behind the purifying, and will contact gained mixture solid-liquid separation, obtain 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline; Wherein, described basic cpd is salt of wormwood and/or yellow soda ash.
By the synthetic method of 2-chloro-3-phenoxy group provided by the invention-6-N-methyl-p-nitroaniline, can obtain highly purified 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline product with high yield.In embodiment 1, the yield of synthetic 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline can reach 75%, and product purity is 97.9%.And the method for employing prior art in the Comparative Examples 1, the yield of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline only is 70%, product purity also only is 95.6%.And also need recrystallization purifying, the acidifying of etherification reaction product, the precipitation of ammonolysis reaction product in the Comparative Examples 1 and separate, than the production operation complexity of embodiment 1.In the method provided by the invention, adopting salt of wormwood and/or yellow soda ash is technical measures such as basic cpd and filtering separation etherification reaction product, can solve in the prior art when using highly basic the problem more than the impurity in the product.And such measure can dispense and need ammonolysis reaction product separation steps in the prior art and need Glacial acetic acid acidifying and frozen water precipitation and separate the step that the etherification reaction product just can obtain 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, thereby simplified production technique; And owing to reduced the kind of the organic solvent that uses, when having avoided aftertreatment etherification reaction product simultaneously water is introduced system, thereby can realize the Recovery of Organic Solvent recycling more easily.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
" one kettle way " synthetic method among the present invention refers to need the baroque molecule that obtains through polystep reaction, from be simple and easy to relatively raw material, without the separation of intermediate, and can directly obtain the synthetic method of target product.Etherification reaction among the present invention refers to that the hydroxyl on the phenol is reacted into the reaction of ehter bond with chlorine in the compound of chlorine substituent is arranged.
The invention provides the synthetic method of a kind of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, this method comprises: (1) contacts with aminating agent 2,3,4-trichloronitrobenzene under the ammonolysis reaction condition in the presence of organic solvent; (2) under the etherification reaction condition, make the ammonolysis reaction product purification in step (1) the gained mixture or do not contact in the presence of basic cpd with phenol behind the purifying, and will contact gained mixture solid-liquid separation, obtain 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline; Described basic cpd is salt of wormwood and/or yellow soda ash.
According to the present invention, the amount of the aminating agent that uses in the described ammonolysis reaction is as long as can finish 2,3, the ammonolysis reaction of 4-trichloronitrobenzene, the target product that obtains ammonolysis reaction gets final product, but the yield height of the target product that is replaced by amino for the chlorine that obtains on the phenyl ring 2, under the preferable case, described 2, the mol ratio of the ammonia in 3,4-trichloronitrobenzene and the described aminating agent is 1:3-10, is preferably 1:3-5.
According to the present invention, there is no particular limitation to use described aminating agent, and that uses for this area is conventional can provide ammonia to get final product in the ammonolysis reaction process, and under the preferable case, described aminating agent is ammonia or liquefied ammonia.
According to the present invention, the amount of the organic solvent that uses in the described ammonolysis reaction is as long as can guarantee 2,3,4-trichloronitrobenzene and aminating agent are finished described ammonolysis reaction and are got final product, under the preferable case, and described 2, the weight ratio of 3,4-trichloronitrobenzene and described organic solvent is 1:3-12, is preferably 1:7-10.
According to the present invention, there is no particular limitation for the organic solvent that uses in the described ammonolysis reaction, needing only ammonolysis reaction is inertia, under the preferable case, described organic solvent is acetonitrile, N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and the N-Methyl pyrrolidone (NMP) one or more are preferably dimethyl sulfoxide (DMSO) and/or N-Methyl pyrrolidone.
Among the present invention, described ammonolysis reaction can also carry out under inert atmosphere.Described inert atmosphere can be nitrogen.
According to the present invention, the condition that described ammonolysis reaction carries out can be the conventional reaction conditions that uses in this area, and under the preferable case, described ammonolysis reaction condition comprises: temperature of reaction is 20-100 ℃, and reaction pressure is 1-10bar, and the reaction times is 5-40 hour; Preferred described ammonolysis reaction condition comprises: temperature of reaction is 50-70 ℃, and reaction pressure is 3-5bar, and the reaction times is 20-30 hour.
According to the present invention, require in the described etherification reaction process in the presence of basic cpd, to carry out, in order to reduce the impurity in the reaction product, the quality of control product is selected the not strong described basic cpd of alkalescence, and more preferably described basic cpd is salt of wormwood.
The present invention does not use stronger sodium hydroxide or the potassium hydroxide of alkalescence to remove remaining aminating agent, has avoided the influence of strongly alkaline compound to reaction product yield and purity, and the actually operating of the suitability for industrialized production of being more convenient for is enhanced productivity.
According to the present invention, the amount of the basic cpd that uses in the described etherification reaction, described 2,3 with what feed intake relatively at first according to above-mentioned explanation, the 4-trichloronitrobenzene is mete-wand.Though use above-mentioned basic cpd can reduce impurity in the reaction product, the quality of control product, but in order to guarantee to realize that described etherification reaction can obtain 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline target product with high yield, need an amount of described basic cpd.Under the preferable case, described basic cpd and described 2,3, the mol ratio of 4-trichloronitrobenzene is 1:0.2-1; Preferred described basic cpd and described 2,3, the mol ratio of 4-trichloronitrobenzene is 1:0.4-0.8.
According to the present invention, the amount of the described phenol that uses in the described etherification reaction is as long as can finish 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline that described etherification reaction obtains high yield.Because the present invention adopts " one kettle way " synthetic 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, directly carry out etherification reaction after finishing ammonolysis reaction, therefore in etherification reaction, the employing of the amount of the raw material of Jia Ruing is mete-wand with the raw material that feeds intake at first again, namely the amount of the phenol that in described etherification reaction, adds feed intake relatively at first described 2,3, the 4-trichloronitrobenzene is mete-wand, under the preferable case, and described 2, the weight ratio of 3,4-trichloronitrobenzene and described phenol is 1:0.4-0.8.
Among the present invention, to the aftertreatment of described etherification reaction product, take method unlike the prior art.Prior art adds Glacial acetic acid in the described etherification reaction product and carries out separating of product with water, but causes the organic solvent in the product to be difficult for Separation and Recovery.According to the present invention, after the described etherification reaction, the filter cake of taking filtration treatment to obtain is the etherification reaction product, the filtrate that obtains simultaneously is not owing to use Glacial acetic acid and water, wherein only contain the organic solvent that ammonolysis reaction uses, therefore can carry out the filtrate precipitation easily and realize Recovery of Organic Solvent.Among the present invention, obtain the etherification reaction product by filtering afterwards in step (2), the filtrate precipitation reclaims solvent.The method that organic solvent reclaims can for example can be vacuum distillation method for the method for routine use.The organic solvent that obtains can use in ammonolysis reaction again, is beneficial to suitability for industrialized production and also can reduces production costs.
Among the present invention, the etherificate product filter cake that obtains can also further be made with extra care, for example can be for obtaining purified product with carrying out recrystallization after a small amount of organic solvent drip washing filter cake.The organic solvent that drip washing is used can be for identical with the organic solvent of ammonolysis reaction use.Recrystallization can be the recrystallization method of routine, and the organic solvent that recrystallization uses can be as at least a in methyl alcohol, ethanol, propyl alcohol, Virahol and the butanols, and preferred described organic solvent is methyl alcohol.After recrystallization, carry out drying and obtain yellow solid, further can use magnetic nuclear resonance method to analyze the structure of yellow solid.
According to the present invention, the condition that described etherification reaction carries out can be the conventional reaction conditions that uses in this area, and under the preferable case, described etherification reaction condition comprises: temperature of reaction is 20-120 ℃, and the reaction times is 10-30 hour; Preferred described etherification reaction condition comprises: temperature of reaction is 70-90 ℃, and the reaction times is 15-20 hour.
Below will describe the present invention by embodiment.
In following examples, the hydrogen of product spectrum and carbon spectrum data obtain by carry out the magnetic nuclear resonance method analysis on nuclear magnetic resonance spectrometer (Bruker Avance III500MHz, manufacturer's Brooker,Switzerland company).The high resolution mass spectrum data of product are by Agilent G1969A LC/MSD-TOF-MS(manufacturer Anjelen Sci. ﹠ Tech. Inc) on analyze and obtain.
The yield that preparation method of the present invention obtains 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline calculates according to following formula:
Y=m
2×p
2×M
1×100%/(m
1×p
1×M
2)
Y wherein: product yield
m
1: 2,3,4-trichloronitrobenzene weight
p
1: 2,3,4-trichloronitrobenzene purity
M
1: 2,3,4-trichloronitrobenzene molecular weight
m
2: 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline weight
p
2: 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline purity
M
2: 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline molecular weight
Purity (the p of the 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline product that obtains
2) measure by chromatogram quantitative analysis of the liquid phase method (instrument model Agilent1200LC, manufacturer Anjelen Sci. ﹠ Tech. Inc).
In the raw material that uses in following examples:
2,3,4-trichloronitrobenzene is 99% chemical pure, is the commercially available product of Suzhou Yacoo Chemical Reagent Corporation;
Dimethyl sulfoxide (DMSO) is 99% analytical pure, is the commercially available product of Beijing chemical reagents corporation;
N-Methyl pyrrolidone is 99% analytical pure, is the commercially available product of Beijing chemical reagents corporation.
Embodiment 1
Present embodiment is used for the synthetic method of explanation 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
(1) ammonolysis reaction: with 2,3,4-trichloronitrobenzene 77.0g(0.34mol) and dimethyl sulfoxide (DMSO) 770g add autoclave successively and stir; Heating up under nitrogen atmosphere and being heated to temperature is 50 ℃; Feed ammonia 29.0g(1.7mol), autoclave pressure is 0.3MPa, reacts 26 hours.Autoclave is cooled to 30 ℃, and wherein material is shifted out, and obtains the ammonolysis reaction product;
(2) etherification reaction: with phenol 30.8g(0.32mol) and salt of wormwood 58.8g(0.42mol) add in the ammonolysis reaction product, and be warming up to 70 ℃, reacted 20 hours.Be cooled to 25 ℃, filter and obtain etherification reaction product filter cake; Filter cake is with a small amount of dimethyl sulfoxide (DMSO) drip washing, add after 120g recrystallizing methanol, the drying yellow solid 68.3g; The filtrate precipitation reclaims solvent.
The gained yellow solid is through nucleus magnetic resonance and high resolution mass spectrum methods analyst, and the proton nmr spectra of acquisition, carbon-13 nmr spectra and high resolution mass spectrum data are as follows:
1HNMR (500MHz, d
6-DMSO): δ 8.04-8.06 (d, 1H), 7.46-7.49 (m, 4H), 7.27-7.30 (m, 1H), 7.14-7.16 (m, 2H), 6.16-6.18 (d, 1H);
13CNMR (500MHz, CDCl
3): δ 105.3,109.9, and 120.2,125.4,126.0,128.3,130.2,143.4,154.4,159.0; HRMS calcd for[M+H]
+265.0374, found:265.0397; Determine that the gained yellow solid is 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.9%.Further calculate, product yield is 75%.
Embodiment 2
Present embodiment is used for the synthetic method of explanation 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
(1) ammonolysis reaction: with 2,3,4-trichloronitrobenzene 79.3g(0.35mol) and N-Methyl pyrrolidone (NMP) 555g add autoclave successively and stir; Heating up under nitrogen atmosphere and being heated to temperature is 70 ℃; Feed liquefied ammonia 17.9g(1.05mol), autoclave pressure is 0.5MPa, reacts 20 hours.Autoclave is cooled to 30 ℃, and wherein material is shifted out, and obtains the ammonolysis reaction product.
(2) etherification reaction: with phenol 64.0g(0.67mol) and salt of wormwood 121.0g(0.87mol) add in the ammonolysis reaction product, and be warming up to 90 ℃, reacted 15 hours.Be cooled to 25 ℃, filter and obtain etherification reaction product filter cake; Filter cake is with small amount of N MP drip washing, add after 130g recrystallizing methanol, the drying yellow solid 68.7g; The filtrate precipitation reclaims solvent.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.6%.Further calculate, product yield is 73%.
Embodiment 3
Present embodiment is used for the synthetic method of explanation 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
(1) ammonolysis reaction: with 2,3,4-trichloronitrobenzene 65.7g(0.29mol) and dimethyl sulfoxide (DMSO) 530g add autoclave successively and stir; Heating up under nitrogen atmosphere and being heated to temperature is 50 ℃; Feed ammonia 19.6(1.15mol), autoclave pressure is 0.4MPa, reacts 24 hours.Autoclave is cooled to 30 ℃, and wherein material is migrated out, and obtains the ammonolysis reaction product.
(2) etherification reaction: with phenol 40g(0.42mol) and salt of wormwood 60.0g(0.43mol) add in the ammonolysis reaction product, and be warming up to 90 ℃, reacted 15 hours.Be cooled to 25 ℃, filter and obtain etherification reaction product filter cake; Filter cake is with a small amount of dimethyl sulfoxide (DMSO) drip washing, add after 100g recrystallizing methanol, the drying yellow solid 57.8g; The filtrate precipitation reclaims solvent.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.5%.Further calculate, product yield is 74%.
Embodiment 4
Present embodiment is used for the synthetic method of explanation 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
(1) ammonolysis reaction: with 2,3,4-trichloronitrobenzene 65.7g(0.29mol) and dimethyl sulfoxide (DMSO) 460g add autoclave successively and stir; Heating up under nitrogen atmosphere and being heated to temperature is 100 ℃, feeds ammonia 17g(1.0mol), autoclave pressure is 0.5MPa, reacts 6 hours.Autoclave is cooled to 30 ℃, and wherein material is shifted out, and obtains the ammonolysis reaction product.
(2) etherification reaction: with phenol 32.0g(0.34mol) and salt of wormwood 50.0g(0.36mol) add in the ammonolysis reaction product, and be warming up to 80 ℃, reacted 20 hours.Be cooled to 25 ℃, filter and obtain etherification reaction product filter cake; Filter cake is with a small amount of dimethyl sulfoxide (DMSO) drip washing, add after 110g recrystallizing methanol, the drying yellow solid 54.5g; The filtrate precipitation reclaims solvent.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.3%.Further calculate, product yield is 70%.
Embodiment 5
According to the method for embodiment 1, different is to substitute dimethyl sulfoxide (DMSO) 770g with the dimethyl sulfoxide (DMSO) 770g that reclaims in (1) ammonolysis reaction.Get yellow solid 66.6g at last.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.6%.Further calculate, product yield is 73%.
Comparative Examples 1
This Comparative Examples is used for the method for the synthetic 2-chloro-3-phenoxy group of explanation prior art-6-N-methyl-p-nitroaniline.
(1) ammonolysis reaction: with 2,3,4-trichloronitrobenzene 77.0g(0.34mol) and dimethyl sulfoxide (DMSO) 770g add autoclave successively and stir; Heating up under nitrogen atmosphere and being heated to temperature is 50 ℃; Feed ammonia 29.0g(1.7mol), autoclave pressure is 0.3MPa, reacts 26 hours.Autoclave is cooled to 30 ℃, wherein material is shifted out add in the 34g NaOH solution (40 weight %) to remove ammonia, and the ammonolysis reaction product that obtains carries out recrystallization purifying with methyl iso-butyl ketone (MIBK);
(2) etherification reaction: with phenol 30.8g(0.32mol) and 51g NaOH solution (40 weight %) add in the ammonolysis reaction product, and be warming up to 70 ℃, reacted 20 hours.Be cooled to 25 ℃ and the 7ml Glacial acetic acid added the acidifying of etherification reaction product, add frozen water then and precipitate, separate obtaining pale brown look thick product, and use the Virahol recrystallization, obtain yellow solid 65.3g.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 95.6%.Further calculate, product yield is 70%.
Comparative Examples 2
According to the method for embodiment 1, different is: the ammonolysis reaction product methyl iso-butyl ketone (MIBK) recrystallization purifying that obtains, and replace the ammonolysis reaction product to be used for step (2) etherification reaction the purified product.The yellow solid product that finally obtains is 57.6g.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.6%.Further calculate, product yield is 63%.
Comparative Examples 3
According to the method for embodiment 1, different is: the etherification reaction product separates the employing prior art and substitutes filtering separation, is specially:
Be cooled to 25 ℃ and the 8ml Glacial acetic acid added the acidifying of etherification reaction product, add frozen water then and precipitate, separate obtaining thick product, and use the Virahol recrystallization, obtain yellow solid 66.0g.
The gained yellow solid is defined as 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline through nucleus magnetic resonance and high resolution mass spectrum methods analyst.
The purity that records product 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline by the chromatogram quantitative analysis of the liquid phase method is 97.2%.Further calculate, product yield is 72%.
By the experimental result of above-described embodiment and Comparative Examples as can be seen, the synthetic method of 2-chloro-3-phenoxy group of the present invention-6-N-methyl-p-nitroaniline can obtain highly purified product with high yield, and the prior art operation that building-up process compares ratio 1 is more simplified.
Embodiment 5 uses the organic solvent that reclaims to carry out the synthetic of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline as different from Example 1.From the experimental data result as can be seen, He Cheng 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline product still has very high yield and product purity.Illustrate that method provided by the invention can realize the organic solvent recycling, thereby reduce production costs, be conducive to the suitability for industrialized production of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline.
Comparative Examples 3 is compared with embodiment 1, though used salt of wormwood in etherification reaction, the processing of etherification reaction product also need add Glacial acetic acid with frozen water and separate, and is more complicated, and uses multiple organic solvent, and organic solvent is difficult for the Separation and Recovery utilization.
Claims (10)
1. the synthetic method of 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline, this method comprises:
(1) under the ammonolysis reaction condition, 2,3,4-trichloronitrobenzene is contacted in the presence of organic solvent with aminating agent;
(2) under the etherification reaction condition, make the ammonolysis reaction product purification in step (1) the gained mixture or do not contact in the presence of basic cpd with phenol behind the purifying, and will contact gained mixture solid-liquid separation, obtain 2-chloro-3-phenoxy group-6-N-methyl-p-nitroaniline;
Wherein, described basic cpd is salt of wormwood and/or yellow soda ash.
2. method according to claim 1, wherein, described basic cpd is salt of wormwood.
3. method according to claim 1 and 2, wherein, described basic cpd and described 2,3, the mol ratio of 4-trichloronitrobenzene is 1:0.2-1; Preferred described basic cpd and described 2,3, the mol ratio of 4-trichloronitrobenzene is 1:0.4-0.8.
4. method according to claim 1 and 2, wherein described 2,3, the weight ratio of 4-trichloronitrobenzene and described phenol is 1:0.4-0.8.
5. method according to claim 1 and 2, wherein, described aminating agent is ammonia or liquefied ammonia, described 2,3, the mol ratio of 4-trichloronitrobenzene and described aminating agent is 1:3-10, preferred described 2,3, the mol ratio of 4-trichloronitrobenzene and described aminating agent is 1:3-5.
6. method according to claim 1 and 2, wherein described 2,3, the weight ratio of 4-trichloronitrobenzene and described organic solvent is 1:3-12, and is preferred described 2,3, the weight ratio of 4-trichloronitrobenzene and described organic solvent is 1:7-10.
7. method according to claim 1 and 2, wherein, described organic solvent is acetonitrile, N, one or more in dinethylformamide, dimethyl sulfoxide (DMSO) and the N-Methyl pyrrolidone, and preferred described organic solvent is dimethyl sulfoxide (DMSO) and/or N-Methyl pyrrolidone.
8. method according to claim 1 and 2, wherein, this method comprises that also the liquid that solid-liquid separation is obtained carries out precipitation to reclaim organic solvent wherein.
9. according to any described method among the claim 1-8, wherein, described ammonolysis reaction condition comprises: temperature of reaction is 20-100 ℃, and reaction pressure is 1-10bar, and the reaction times is 5-40 hour; Preferred described ammonolysis reaction condition comprises: temperature of reaction is 50-70 ℃, and reaction pressure is 3-5bar, and the reaction times is 20-30 hour.
10. according to any described method among the claim 1-8, wherein, described etherification reaction condition comprises: temperature of reaction is 20-120 ℃, and the reaction times is 10-30 hour; Preferred described etherification reaction condition comprises: temperature of reaction is 70-90 ℃, and the reaction times is 15-20 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181089A (en) * | 2021-12-20 | 2022-03-15 | 中建安装集团有限公司 | Method for continuously synthesizing p-nitroaniline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364875A (en) * | 1979-09-24 | 1982-12-21 | Celamerck Gmbh & Co. Kg | Process for the preparation of certain diphenyl ethers |
| US4391159A (en) * | 1980-12-03 | 1983-07-05 | Gulf & Western Manufacturing Company | Parking brake actuating device |
| US20040259732A1 (en) * | 2003-04-28 | 2004-12-23 | Monsanto Technology, L.L.C. | Treatment of plants and plant propagation materials with an antioxidant to improve plant health and/or yield |
| US20060276339A1 (en) * | 2002-10-16 | 2006-12-07 | Windsor J B | Methods and compositions for increasing the efficacy of biologically-active ingredients |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4364875A (en) * | 1979-09-24 | 1982-12-21 | Celamerck Gmbh & Co. Kg | Process for the preparation of certain diphenyl ethers |
| US4391159A (en) * | 1980-12-03 | 1983-07-05 | Gulf & Western Manufacturing Company | Parking brake actuating device |
| US20060276339A1 (en) * | 2002-10-16 | 2006-12-07 | Windsor J B | Methods and compositions for increasing the efficacy of biologically-active ingredients |
| US20040259732A1 (en) * | 2003-04-28 | 2004-12-23 | Monsanto Technology, L.L.C. | Treatment of plants and plant propagation materials with an antioxidant to improve plant health and/or yield |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181089A (en) * | 2021-12-20 | 2022-03-15 | 中建安装集团有限公司 | Method for continuously synthesizing p-nitroaniline |
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