CN105936625A - Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide - Google Patents
Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide Download PDFInfo
- Publication number
- CN105936625A CN105936625A CN201610265760.4A CN201610265760A CN105936625A CN 105936625 A CN105936625 A CN 105936625A CN 201610265760 A CN201610265760 A CN 201610265760A CN 105936625 A CN105936625 A CN 105936625A
- Authority
- CN
- China
- Prior art keywords
- chloro
- benzoylamide
- nitro
- amino
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 3-amino-5-chloro-N,3-dimethyl benzamide, and belongs to the organic chemical synthesis technical field. The synthesis method comprises the steps: 3-nitro-4-chlorobenzoic acid is used as a raw material, N,N'-diisopropyl carbodiimide is used as a condensing agent, 1-hydroxybenzotriazole is used as a condensation activator, firstly, 3-nitro-4-chlorobenzoic acid and N,N'-diisopropyl carbodiimide are subjected to an addition reaction, an addition product is not stable and is converted to a corresponding ester under the action of 1-hydroxybenzotriazole, then the corresponding ester is subjected to a reaction with 3-chloro-2-methylaniline to obtain 3-nitro-4-chloro-N-(3-chloro-2-methylphenyl)benzamide, next the 3-nitro-4-chloro-N-(3-chloro-2-methylphenyl)benzamide is reduced into 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide under the action of zinc and sodium hydroxide. The synthesis method has the advantages of simple operation, less steps, and short production cycle, and the synthesis yield is increased significantly and is increased to 95% or more.
Description
Technical field
The invention discloses the synthetic method of a kind of 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, belong to technical field of organic synthesis.
Background technology
Pigment is different from dyestuff and is that general dyestuff can be dissolved in water or solvent, and pigment is the most water insoluble.Dyestuff is mainly used in the dyeing of textile, but this differentiation is the most fully aware of, because some dyestuff is also possible to water insoluble, and pigment also has the pigment printing for textile and original liquid coloring.The chemical constitution of organic pigment has similarity with organic dyestuff, is therefore typically considered to a branch of dyestuff.Pigment chemically forms to classify, and can be divided into inorganic dyestuff and the big class of organic-fuel two, can be divided into again natural pigment and synthetic dyestuff with regard to its source.Natural pigment has Cinnabaris, laterite, Realgar, peacock green, ground calcium carbonate, wollastonite, Pulvis Talci, mica powder, Kaolin etc. with mineral for source, has the alkermes from animal, natural pearl white etc. with biology for source and from the Resina garciniae of plant, alizarin red, indigo-blue etc..Synthetic dyestuff passes through synthetic, such as inorganic pigments such as titanium white, Griffith's zinc white., lead chromate yellow, barba hispanica, iron oxide red, Plumbum preparatium, and the organic pigment such as red, azophosphine, phthalocyanine blue, quinacridone.
At present external use and the domestic intermediate not have to produce is a lot, although or production but because production scale and the reason such as technology path, technical merit cause production cost too high, or poor quality.C.I. pigment yellow 93 is excellent to the light fastness after the coloring of PVC, for polrvinyl chloride, polyolefinic dope dyeing it can also be used to paint, the coloring of printing-ink.The chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide is as the important intermediate of C.I. pigment yellow 93 organic pigment such as grade, domestic the fewest to its research, only a kind of production method is i.e. with 3-nitro-4-chlorobenzoic acid as raw material, generation 3-nitro-4-chlorobenzoyl chloride is reacted with dimethyl sulfoxide, then 3-nitro-4-chlorobenzoyl chloride reacts the generation 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide again with 3-chloro-2-methyl aniline, finally obtains the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide at catalytic hydrogenation.This art production process operation complexity, production cycle length, yield is relatively low, and therefore, one is simple to operate, and the synthetic method of the 3-chloro-N-of amino-4-(the 3-chloro-2-methyl phenyl) Benzoylamide that yield is high has very important significance.
Summary of the invention
nullThe technical problem that present invention mainly solves: for operation complexity in the current 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide building-up process、Production cycle is long、Total yield of products is low，The highest problem of only 86%，Provide the synthetic method of a kind of 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide，The present invention is with 3-nitro-4-chlorobenzoic acid as raw material，N，N'-DIC is condensing agent、I-hydroxybenzotriazole is condensation activator，First 3-nitro-4-chlorobenzoic acid and N，N'-DIC generation additive reaction，Addition compound product is unstable，Corresponding ester it is converted under the effect of I-hydroxybenzotriazole，Then pass through to react with 3-chloro-2-methyl aniline again to obtain the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide，By zinc and sodium hydroxide effect, the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide is reduced into the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide the most again，The present invention is the most simple to operate、Step is few、With short production cycle，And synthesis yield has obtained significant raising，Bring up to more than 95%.
In order to achieve the above object, the synthetic route of the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide of the present invention is:
The building-up process of the 3-chloro-N-of amino-4-(the 3-chloro-2-methyl phenyl) Benzoylamide that the present invention relates to comprises the following steps:
(1) to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 10～14g3-nitro-4-chlorobenzoic acids, 100～150mL dichloromethane, 40～50mL N, N'-DIC, 5～10mL1-hydroxybenzotriazole, under room temperature, stirring reaction 2～3h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；
(2) the most while stirring 40～50mL3-chloro-2-methyl anilines are added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 3～5h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains the solution containing the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide；
(3) in above-mentioned solution, 1～2g zinc metal sheet, 40～50mL0.1mol/LNaOH it are sequentially added into, it is 70～80 DEG C that oil bath controls solution temperature, then stirring insulation reaction 2～3h, reaction end obtains the mixed liquor containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide；
(4) above-mentioned mixed liquor is filtered, obtain filtrate, 200～300mL deionized waters are added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain the solution containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. the chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide.
The chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide is light gray solid, is slightly soluble in water, is dissolved in most of organic solvent such as dichloromethane, benzene.
The invention has the beneficial effects as follows:
(1) present invention utilizes N, N'-DIC is that condensing agent, I-hydroxybenzotriazole are for being condensed activator, 3-nitro-4-chlorobenzoic acid is made to be converted into ester, react the generation 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide the most again with 3-chloro-2-methyl aniline, simplifies operating procedure；
(2) present invention is the most simple to operate, with short production cycle, and synthesis yield has obtained significant raising, has brought up to 95%.
Detailed description of the invention
First to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 10～14g3-nitro-4-chlorobenzoic acids, 100～150mL dichloromethane, 40～50mL N, N'-DIC, 5～10mL1-hydroxybenzotriazole, under room temperature, stirring reaction 2～3h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；The most while stirring 40～50mL3-chloro-2-methyl anilines are added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 3～5h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains the solution containing the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide；1～2g zinc metal sheet, 40～50mL0.1mol/LNaOH it is sequentially added in above-mentioned solution, it is 70～80 DEG C that oil bath controls solution temperature, then stirring insulation reaction 2～3h, reaction end obtains the mixed liquor containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide；Above-mentioned mixed liquor is filtered, obtain filtrate, 200～300mL deionized waters are added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain the solution containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. the chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide.
Example 1
First to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 10g3-nitro-4-chlorobenzoic acid, 100mL dichloromethane, 40mL N, N'-DIC, 5mL1-hydroxybenzotriazole, under room temperature, stirring reaction 2h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；The most while stirring 40mL3-chloro-2-methyl aniline is added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 3h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains the solution containing the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide；Being sequentially added into 1g zinc metal sheet, 40mL0.1mol/LNaOH in above-mentioned solution, it is 70 DEG C that oil bath controls solution temperature, then stirring insulation reaction 2h, and reaction end obtains the mixed liquor containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide；Above-mentioned mixed liquor is filtered, obtain filtrate, 200mL deionized water is added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain the solution containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. the chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide.
The present invention utilizes N, N'-DIC is that condensing agent, I-hydroxybenzotriazole are for being condensed activator, 3-nitro-4-chlorobenzoic acid is made to be converted into ester, react the generation 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide the most again with 3-chloro-2-methyl aniline, simplifies operating procedure；The present invention is the most simple to operate, with short production cycle, and synthesis yield has obtained significant raising, has brought up to 96%.
Example 2
First to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 12g3-nitro-4-chlorobenzoic acid, 125mL dichloromethane, 45mL N, N'-DIC, 8mL1-hydroxybenzotriazole, under room temperature, stirring reaction 2.5h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；The most while stirring 45mL3-chloro-2-methyl aniline is added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 4h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains the solution containing the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide；1.5g zinc metal sheet, 45mL0.1mol/LNaOH it is sequentially added in above-mentioned solution, it is 75 DEG C that oil bath controls solution temperature, then stirring insulation reaction 2.5h, reaction end obtains the mixed liquor containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide；Above-mentioned mixed liquor is filtered, obtain filtrate, 250mL deionized water is added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain the solution containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. the chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide.
The present invention utilizes N, N'-DIC is that condensing agent, I-hydroxybenzotriazole are for being condensed activator, 3-nitro-4-chlorobenzoic acid is made to be converted into ester, react the generation 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide the most again with 3-chloro-2-methyl aniline, simplifies operating procedure；The present invention is the most simple to operate, with short production cycle, and synthesis yield has obtained significant raising, has brought up to 96.5%.
Example 3
First to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 14g3-nitro-4-chlorobenzoic acid, 150mL dichloromethane, 50mL N, N'-DIC, 10mL1-hydroxybenzotriazole, under room temperature, stirring reaction 3h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；The most while stirring 50mL3-chloro-2-methyl aniline is added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 3h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains the solution containing the 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide；Being sequentially added into 2g zinc metal sheet, 50mL0.1mol/LNaOH in above-mentioned solution, it is 80 DEG C that oil bath controls solution temperature, then stirring insulation reaction 3h, and reaction end obtains the mixed liquor containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide；Above-mentioned mixed liquor is filtered, obtain filtrate, 300mL deionized water is added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain the solution containing the 3-chloro-N-of amino-4-(3-chloro-2-methyl phenyl) Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. the chloro-N-of 3-amino-4-(3-chloro-2-methyl phenyl) Benzoylamide.
The present invention utilizes N, N'-DIC is that condensing agent, I-hydroxybenzotriazole are for being condensed activator, 3-nitro-4-chlorobenzoic acid is made to be converted into ester, react the generation 3-chloro-N-of nitro-4-(3-chloro-2-methyl phenyl) Benzoylamide the most again with 3-chloro-2-methyl aniline, simplifies operating procedure；The present invention is the most simple to operate, with short production cycle, and synthesis yield has obtained significant raising, has brought up to 97.2%.
Claims (1)
1. a 3-amino-4-chloro-N-(3-chloro-2-methyl phenyl) synthetic method of Benzoylamide, it is characterised in that concrete synthesis step is:
(1) to equipped with the 500mL there-necked flask of thermometer and reflux is sequentially added into 10～14g3-nitro-4-chlorobenzoic acids, 100～150mL dichloromethane, 40～50mL N, N'-DIC, 5～10 mL1-hydroxybenzotriazoles, under room temperature, stirring reaction 2～3h, obtains the solution of 3-nitro-4-chloro-phenyl formic acid-1-benzotriazole ester；
(2) the most while stirring 40～50mL3-chloro-2-methyl anilines are added drop-wise in above-mentioned solution with 10mL/min, insulation reaction 3～5h, thin layer chromatography follows the tracks of reaction, and reaction terminates, and obtains containing 3-nitro-4-chloro-N-(3-chloro-2-methyl phenyl) solution of Benzoylamide；
(3) in above-mentioned solution, 1～2g zinc metal sheet, 40～50mL0.1mol/LNaOH it are sequentially added into, it is 70～80 DEG C that oil bath controls solution temperature, then stirring insulation reaction 2～3h, reaction end obtains containing 3-amino-4-chloro-N-(3-chloro-2-methyl phenyl) mixed liquor of Benzoylamide；
(4) above-mentioned mixed liquor is filtered, obtain filtrate, 200～300mL deionized waters are added in filtrate, separatory is carried out with 1000mL pear shape separatory funnel, the organic facies separated is used by volume for petroleum ether: the mixed liquor of ethyl acetate=1:10 crosses chromatographic column as solvent, obtain containing 3-amino-4-chloro-N-(3-chloro-2-methyl phenyl) solution of Benzoylamide, then solution is carried out decompression distillation, obtain light gray solid, i.e. 3-amino-4-chloro-N-(3-chloro-2-methyl phenyl) Benzoylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265760.4A CN105936625A (en) | 2016-04-26 | 2016-04-26 | Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265760.4A CN105936625A (en) | 2016-04-26 | 2016-04-26 | Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105936625A true CN105936625A (en) | 2016-09-14 |
Family
ID=57151492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610265760.4A Withdrawn CN105936625A (en) | 2016-04-26 | 2016-04-26 | Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105936625A (en) |
-
2016
- 2016-04-26 CN CN201610265760.4A patent/CN105936625A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104610071B (en) | A kind of chlorine direct chlorination and hydrogen peroxide oxidation chlorination are prepared the method for 2,6-Dichloro-4-nitroaniline simultaneously | |
| US11773073B2 (en) | Method for synthesizing myricetin | |
| CN110283586B (en) | Near-infrared fluorescent dye and preparation method thereof | |
| CN104130194B (en) | A kind of synthetic method of 5-Amino-2-benzimidazolinone | |
| CN106242990B (en) | Preparation method of 2-amino-4-acetamino anisole | |
| CN101671285B (en) | Preparation method of dibenzenesulfonimide | |
| CN107892654B (en) | Isolongifolane-based fluorescent acid-base indicator and synthetic method and application thereof | |
| CN108101800B (en) | A kind of synthetic method of ortho-aminobenzoic acid | |
| CN102875463A (en) | Synthesis method for high-quality and low-cost bispyrithione | |
| CN105936625A (en) | Synthesis method of 3-amino-4-chloro-N-(3-chloro-2-methylphenyl)benzamide | |
| CN105669357B (en) | A kind of green preparation process of 1,4- diiodo-benzenes | |
| CN102603547B (en) | New synthesis process of 1-amino-2-acetylanthraquinone and derivatives thereof | |
| CN105601523B (en) | A kind of method for synthesizing the chloroaniline of 2,5 dimethoxy 4 | |
| CN102924961B (en) | Preparation method for disperse red | |
| CN106905177A (en) | A kind of preparation method of the biphenyl propionic acid ethyl ester derivative hydrochloride of 2 amino 3 | |
| CN101659650A (en) | Method of preparing piperonal in one kettle way | |
| CN105198697A (en) | Synthetic method for 2-bromofluorene derivatives | |
| EA200801257A1 (en) | METHOD OF OBTAINING IRON OXIDE PIGMENTS | |
| CN109134357A (en) | The method of the efficient high selectivity 2- amino -5- chloropyridine of one-step method | |
| CN105315127B (en) | A kind of preparation method of 4 tert-butyl group bromobenzyl | |
| CN105085286B (en) | A kind of method for synthesizing 1 amino anthraquinones | |
| CN114262285B (en) | Method for preparing 4-aminotoluene-3-sulfonic acid from sulfur trioxide | |
| US1028006A (en) | Manufacture and production of fast ortho-oxy-azo dyestuffs. | |
| CN108238948A (en) | A kind of method that no catalyst oxygen oxidation o-nitroethylbenzene prepares α-o-nitrophenylethanol | |
| US960182A (en) | Gray anthraquinone dye. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20160914 |