CN116606227A - Synthetic method of CLT acid - Google Patents
Synthetic method of CLT acid Download PDFInfo
- Publication number
- CN116606227A CN116606227A CN202310605680.9A CN202310605680A CN116606227A CN 116606227 A CN116606227 A CN 116606227A CN 202310605680 A CN202310605680 A CN 202310605680A CN 116606227 A CN116606227 A CN 116606227A
- Authority
- CN
- China
- Prior art keywords
- reaction
- reaction liquid
- dichlorobenzene
- chlorination
- 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- Withdrawn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
- 239000002253 acid Substances 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 61
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 238000005694 sulfonylation reaction Methods 0.000 claims abstract description 35
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 18
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000005917 acylation reaction Methods 0.000 claims abstract description 6
- 230000017105 transposition Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- GUEWKNDIKSGBBF-UHFFFAOYSA-N S(O)(O)(=O)=O.ClC1=C(C=CC=C1)Cl Chemical compound S(O)(O)(=O)=O.ClC1=C(C=CC=C1)Cl GUEWKNDIKSGBBF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 230000005945 translocation Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- HIHCTGNZNHSZPP-UHFFFAOYSA-N 4-chloro-3-methylaniline Chemical compound CC1=CC(N)=CC=C1Cl HIHCTGNZNHSZPP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/34—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfuric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of synthesis, and particularly relates to a synthesis method of CLT acid, which comprises the following steps: step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution; step 2, chlorination reaction: uniformly stirring the acylation reaction liquid and ferric chloride, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid; step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating and reacting for 5-8 hours, and stopping heating to obtain a sulfonation reaction liquid; and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid. The invention solves the defects of the existing CLT acid process, realizes the synthesis of the CLT acid by using a one-pot method, does not need intermediate transfer treatment, greatly reduces the generation of three wastes, and has good environmental protection.
Description
Technical Field
The invention belongs to the field of synthesis, and particularly relates to a synthesis method of CLT acid.
Background
CLT acid, chemical name 2-amino-5-chloro-4-methylbenzene, abbreviated as C acid, white powder, insoluble in water. Is an important intermediate of red organic pigment. CLT acid is one of the organic intermediates that consume over ten thousand tons worldwide per year. In the CLT acid production process, main pollutants are wastewater, waste gas and waste residues, due to pollution problems, developed countries in the world shut down part of production equipment or limit the output to reduce pollution, and also enterprises in China are forced to stop production due to pollution problems, so that the three wastes treatment problem is related to the fate of CLT acid industry in China along with the increasing importance of the China on environmental protection. At the same time, the low process yield of CLT acid itself becomes one of the key problems of great pollution and limited application of the material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing CLT acid, which solves the defects of the prior CLT acid process, realizes the synthesis of the CLT acid by using a one-pot method, does not need intermediate transfer treatment, greatly reduces the generation of three wastes and has good environmental protection.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method for synthesizing CLT acid, comprising the steps of:
step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution;
step 2, chlorination reaction: stirring the acylation reaction liquid and ferric chloride uniformly, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid
Step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating and reacting for 5-8 hours, and stopping heating to obtain a sulfonation reaction liquid;
and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid.
The sulfonylation reaction in the step 1 includes: a1, adding sulfuric acid into o-dichlorobenzene, and uniformly stirring to obtain sulfuric acid-o-dichlorobenzene mixed solution; the mass concentration of the sulfuric acid in the o-dichlorobenzene is 10-20%, the stirring speed of uniform stirring is 300-500r/min, a2, the m-toluidine is put into a reaction kettle and nitrogen is used for blowing to form a nitrogen protection system, and the nitrogen blowing speed is 5-10mL/min; and a3, slowly dripping sulfuric acid-o-dichlorobenzene mixed solution into a reaction kettle for reaction, heating for reaction for 1-3h to obtain sulfonylation reaction solution, wherein the molar quantity of sulfuric acid in the mixed solution is 50-55% of that of m-toluidine, and the temperature of the heating reaction is 80-85 ℃.
The chlorination reaction in the step 2 comprises the following steps: b1, adding ferric chloride into a sulfonylation reaction solution, uniformly stirring, wherein the adding amount of the ferric chloride is 0.1-0.5% of the mass of the sulfonylation reaction solution, the stirring speed of uniform stirring is 100-200r/min, b2, introducing chlorine into the reaction solution for constant temperature reaction for 2-4h under the condition of avoiding light, filtering to obtain the chlorination reaction solution, the introducing speed of the chlorine is 2-4mL/min, the introducing amount of the chlorine is 110-120% of the m-toluidine molar amount, and the temperature is 4-10 ℃; the method effectively controls the formation of a polychlorinated system by using low-temperature conditions, and simultaneously, ferric chloride is used as a catalyst to form a chlorination reaction.
The reaction step of the translocation sulfonation in the step 3 comprises the following steps: and c1, adding a chlorination reaction liquid into o-dichlorobenzene to obtain a diluted chlorination solution, wherein the volume ratio of the chlorination reaction liquid to the o-dichlorobenzene is 1:0.6-0.9, c2, carrying out constant-temperature reaction on the diluted chlorination solution for 7-10 hours, stopping heating, and obtaining a sulfonation reaction liquid, and the constant-temperature reaction temperature is 170-180 ℃. The step utilizes the solvent characteristic of the o-dichlorobenzene to realize the integral dissolution expansion effect, improves the dispersity of the chlorination reactant in the o-dichlorobenzene and reduces the aggregation of reaction products.
The step of post-processing in the step 4 comprises the following steps: d1, adding sodium hydroxide and water into a sulfonation reaction solution, and uniformly stirring to form turbid liquid, wherein the sodium hydroxide and the water form sodium hydroxide solution with the pH of 10-12, and the molar quantity of the sodium hydroxide is 110-120% of that of m-toluidine; d2, standing the turbid liquid for 2-3 hours to form layering, so as to obtain a water phase and an organic phase, wherein the standing temperature is 20-30 ℃; and d3, adding hydrochloric acid into the water phase to form an acidic solution, filtering to obtain a CLT acid product, wherein the pH value of the acidic solution is 6.5, d4, and recovering o-dichlorobenzene by carrying out reduced pressure distillation on the organic phase.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the defects of the existing CLT acid process, realizes the synthesis of the CLT acid by using a one-pot method, does not need intermediate transfer treatment, greatly reduces the generation of three wastes, and has good environmental protection.
2. According to the invention, o-dichlorobenzene is used as a solvent, so that m-toluidine is dissolved, chlorination and sulfonation are realized under a dissolution system, the use of the solvent is reduced, and the solvent is recycled in post-treatment.
3. The method takes ferric chloride as a catalyst, and adopts a slow-feeding mode to carry out the reaction, so that a gradient reaction system is achieved, the chlorination reaction is effectively promoted, and the chlorine reaction rate is improved.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1
A method for synthesizing CLT acid, comprising the steps of:
step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution;
step 2, chlorination reaction: stirring the acylation reaction liquid and ferric chloride uniformly, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid
Step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating for reaction for 5 hours, and stopping heating to obtain a sulfonation reaction liquid;
and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid.
The sulfonylation reaction in the step 1 includes: a1, adding sulfuric acid into o-dichlorobenzene, and uniformly stirring to obtain sulfuric acid-o-dichlorobenzene mixed solution; the mass concentration of the sulfuric acid in the o-dichlorobenzene is 10%, the stirring speed of uniform stirring is 300r/min, a2, m-toluidine is put into a reaction kettle, nitrogen is used for blowing to form a nitrogen protection system, and the speed of nitrogen blowing is 5mL/min; and a3, slowly dripping sulfuric acid-o-dichlorobenzene mixed solution into a reaction kettle for reaction, heating for reaction for 1h to obtain sulfonylation reaction solution, wherein the molar quantity of sulfuric acid in the mixed solution is 50% of that of m-toluidine, and the temperature of the heating reaction is 80 ℃.
The chlorination reaction in the step 2 comprises the following steps: and b1, adding ferric chloride into the sulfonylation reaction liquid, stirring uniformly, wherein the adding amount of the ferric chloride is 0.1% of the mass of the sulfonylation reaction liquid, the stirring speed of the uniform stirring is 100r/min, b2, introducing chlorine into the sulfonylation reaction liquid for 2 hours under the condition of avoiding light, filtering to obtain the chlorination reaction liquid, the introducing speed of the chlorine is 2mL/min, the introducing amount of the chlorine is 110% of the molar amount of m-toluidine, and the temperature is 4 ℃.
The reaction step of the translocation sulfonation in the step 3 comprises the following steps: and c1, adding a chlorination reaction liquid into o-dichlorobenzene to obtain a chlorination diluted solution, wherein the volume ratio of the chlorination reaction liquid to the o-dichlorobenzene is 1:0.6, c2, carrying out constant-temperature reaction on the chlorination diluted solution for 7 hours, stopping heating, and obtaining a sulfonation reaction liquid, and the constant-temperature reaction temperature is 170 ℃.
The step of post-processing in the step 4 comprises the following steps: d1, adding sodium hydroxide and water into a sulfonation reaction solution, and uniformly stirring to form a turbid solution, wherein the sodium hydroxide and the water form a sodium hydroxide solution with the pH of 10, and the molar quantity of the sodium hydroxide is 110% of that of m-toluidine; d2, standing the turbid liquid for 2-3 hours to form layering, so as to obtain a water phase and an organic phase, wherein the standing temperature is 20 ℃; and d3, adding hydrochloric acid into the water phase to form an acidic solution, filtering to obtain a CLT acid product, wherein the pH value of the acidic solution is 6.5, d4, and recovering o-dichlorobenzene by carrying out reduced pressure distillation on the organic phase.
The CLT acid prepared in this example was a white powder with a total molar yield of 71.4% calculated as m-toluidine.
Example 2
A method for synthesizing CLT acid, comprising the steps of:
step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution;
step 2, chlorination reaction: stirring the acylation reaction liquid and ferric chloride uniformly, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid
Step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating for reaction for 8 hours, and stopping heating to obtain a sulfonation reaction liquid;
and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid.
The sulfonylation reaction in the step 1 includes: a1, adding sulfuric acid into o-dichlorobenzene, and uniformly stirring to obtain sulfuric acid-o-dichlorobenzene mixed solution; the mass concentration of the sulfuric acid in the o-dichlorobenzene is 20%, the stirring speed of uniform stirring is 500r/min, a2, m-toluidine is put into a reaction kettle, nitrogen is used for blowing to form a nitrogen protection system, and the speed of nitrogen blowing is 10mL/min; and a3, slowly dropwise adding the sulfuric acid-o-dichlorobenzene mixed solution into a reaction kettle for reaction, heating for reaction for 3 hours to obtain a sulfonylation reaction solution, wherein the molar quantity of sulfuric acid in the mixed solution is 55% of that of m-toluidine, and the temperature of the heating reaction is 85 ℃.
The chlorination reaction in the step 2 comprises the following steps: and b1, adding ferric chloride into the sulfonylation reaction liquid, stirring uniformly, wherein the adding amount of the ferric chloride is 0.5% of the mass of the sulfonylation reaction liquid, the stirring speed of the uniform stirring is 200r/min, b2, introducing chlorine into the sulfonylation reaction liquid for reaction for 4 hours at constant temperature under the condition of avoiding light, filtering to obtain the chlorination reaction liquid, the introducing speed of the chlorine is 4mL/min, the introducing amount of the chlorine is 120% of the m-toluidine molar amount, and the temperature is 10 ℃.
The reaction step of the translocation sulfonation in the step 3 comprises the following steps: and c1, adding a chlorination reaction liquid into o-dichlorobenzene to obtain a chlorination diluted solution, wherein the volume ratio of the chlorination reaction liquid to the o-dichlorobenzene is 1:0.9, c2, carrying out constant temperature reaction on the chlorination diluted solution for 7-10h, stopping heating to obtain a sulfonation reaction liquid, and the constant temperature reaction amount is 180 ℃.
The step of post-processing in the step 4 comprises the following steps: d1, adding sodium hydroxide and water into a sulfonation reaction solution, and uniformly stirring to form a turbid solution, wherein the sodium hydroxide and the water form a sodium hydroxide solution with the pH of 12, and the molar quantity of the sodium hydroxide is 120% of that of m-toluidine; d2, standing the turbid liquid for 2-3 hours to form layering, so as to obtain a water phase and an organic phase, wherein the standing temperature is 30 ℃; and d3, adding hydrochloric acid into the water phase to form an acidic solution, filtering to obtain a CLT acid product, wherein the pH value of the acidic solution is 6.5, d4, and recovering o-dichlorobenzene by carrying out reduced pressure distillation on the organic phase.
The CLT acid prepared in this example was a white powder with a total molar yield of 72.9% calculated as m-toluidine.
Example 3
A method for synthesizing CLT acid, comprising the steps of:
step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution;
step 2, chlorination reaction: stirring the acylation reaction liquid and ferric chloride uniformly, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid
Step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating for reaction for 7 hours, and stopping heating to obtain a sulfonation reaction liquid;
and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid.
The sulfonylation reaction in the step 1 includes: a1, adding sulfuric acid into o-dichlorobenzene, and uniformly stirring to obtain sulfuric acid-o-dichlorobenzene mixed solution; the mass concentration of the sulfuric acid in the o-dichlorobenzene is 15%, the stirring speed of uniform stirring is 400r/min, a2, m-toluidine is put into a reaction kettle, nitrogen is used for blowing to form a nitrogen protection system, and the speed of nitrogen blowing is 8mL/min; and a3, slowly dropwise adding the sulfuric acid-o-dichlorobenzene mixed solution into a reaction kettle for reaction, heating for 2 hours to obtain a sulfonylation reaction solution, wherein the molar quantity of sulfuric acid in the mixed solution is 53% of that of m-toluidine, and the temperature of the heating reaction is 83 ℃.
The chlorination reaction in the step 2 comprises the following steps: and b1, adding ferric chloride into the sulfonylation reaction liquid, stirring uniformly, wherein the adding amount of the ferric chloride is 0.3% of the mass of the sulfonylation reaction liquid, the stirring speed of the uniform stirring is 150r/min, b2, introducing chlorine into the sulfonylation reaction liquid for 3 hours under the condition of avoiding light, filtering to obtain the chlorination reaction liquid, the introducing speed of the chlorine is 3mL/min, the introducing amount of the chlorine is 115% of the molar amount of m-toluidine, and the temperature is 8 ℃.
The reaction step of the translocation sulfonation in the step 3 comprises the following steps: and c1, adding a chlorination reaction liquid into o-dichlorobenzene to obtain a chlorination diluted solution, wherein the volume ratio of the chlorination reaction liquid to the o-dichlorobenzene is 1:0.8, c2, carrying out constant-temperature reaction on the chlorination diluted solution for 9 hours, stopping heating to obtain a sulfonation reaction liquid, and the constant-temperature reaction temperature is 175 ℃.
The step of post-processing in the step 4 comprises the following steps: d1, adding sodium hydroxide and water into a sulfonation reaction solution, and uniformly stirring to form a turbid solution, wherein the sodium hydroxide and the water form a sodium hydroxide solution with the pH of 11, and the molar quantity of the sodium hydroxide is 115% of that of m-toluidine; d2, standing the turbid liquid for 3 hours to form layering, so as to obtain a water phase and an organic phase, wherein the standing temperature is 25 ℃; and d3, adding hydrochloric acid into the water phase to form an acidic solution, filtering to obtain a CLT acid product, wherein the pH value of the acidic solution is 6.5, d4, and recovering o-dichlorobenzene by carrying out reduced pressure distillation on the organic phase.
The CLT acid prepared in this example was a white powder with a total molar yield of 72.1% calculated as m-toluidine.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (5)
1. A method for synthesizing CLT acid, which is characterized in that: the method comprises the following steps:
step 1, sulfonylation reaction: reacting m-toluidine with sulfuric acid to form a sulfonylation reaction solution;
step 2, chlorination reaction: stirring the acylation reaction liquid and ferric chloride uniformly, slowly introducing chlorine to react, and filtering after the reaction is finished to obtain a chlorination reaction liquid
Step 3, transposition sulfonation: adding o-dichlorobenzene into the chlorination reaction liquid, heating and reacting for 5-8 hours, and stopping heating to obtain a sulfonation reaction liquid;
and step 4, post-treating the sulfonation reaction liquid to obtain the finished CLT acid.
2. The method for synthesizing CLT acid according to claim 1, wherein: the sulfonylation reaction in the step 1 includes: a1, adding sulfuric acid into o-dichlorobenzene, and uniformly stirring to obtain sulfuric acid-o-dichlorobenzene mixed solution; the mass concentration of the sulfuric acid in the o-dichlorobenzene is 10-20%, the stirring speed of uniform stirring is 300-500r/min, a2, the m-toluidine is put into a reaction kettle and nitrogen is used for blowing to form a nitrogen protection system, and the nitrogen blowing speed is 5-10mL/min; and a3, slowly dripping sulfuric acid-o-dichlorobenzene mixed solution into a reaction kettle for reaction, heating for reaction for 1-3h to obtain sulfonylation reaction solution, wherein the molar quantity of sulfuric acid in the mixed solution is 50-55% of that of m-toluidine, and the temperature of the heating reaction is 80-85 ℃.
3. The method for synthesizing CLT acid according to claim 1, wherein: the chlorination reaction in the step 2 comprises the following steps: b1, adding ferric chloride into the sulfonylation reaction liquid, stirring uniformly, wherein the adding amount of the ferric chloride is 0.1-0.5% of the mass of the sulfonylation reaction liquid, the stirring speed of the uniform stirring is 100-200r/min, b2, introducing chlorine into the reaction liquid for reacting for 2-4 hours at constant temperature under the condition of avoiding light, filtering to obtain the chlorination reaction liquid, the introducing speed of the chlorine is 2-4mL/min, the introducing amount of the chlorine is 110-120% of the m-toluidine molar amount, and the temperature is 4-10 ℃.
4. The method for synthesizing CLT acid according to claim 1, wherein: the reaction step of the translocation sulfonation in the step 3 comprises the following steps: and c1, adding a chlorination reaction liquid into o-dichlorobenzene to obtain a diluted chlorination solution, wherein the volume ratio of the chlorination reaction liquid to the o-dichlorobenzene is 1:0.6-0.9, c2, carrying out constant-temperature reaction on the diluted chlorination solution for 7-10 hours, stopping heating, and obtaining a sulfonation reaction liquid, and the constant-temperature reaction temperature is 170-180 ℃.
5. The method for synthesizing CLT acid according to claim 1, wherein: the step of post-processing in the step 4 comprises the following steps: d1, adding sodium hydroxide and water into a sulfonation reaction solution, and uniformly stirring to form turbid liquid, wherein the sodium hydroxide and the water form sodium hydroxide solution with the pH of 10-12, and the molar quantity of the sodium hydroxide is 110-120% of that of m-toluidine; d2, standing the turbid liquid for 2-3 hours to form layering, so as to obtain a water phase and an organic phase, wherein the standing temperature is 20-30 ℃; and d3, adding hydrochloric acid into the water phase to form an acidic solution, filtering to obtain a CLT acid product, wherein the pH value of the acidic solution is 6.5, d4, and recovering o-dichlorobenzene by carrying out reduced pressure distillation on the organic phase.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310605680.9A CN116606227A (en) | 2023-05-26 | 2023-05-26 | Synthetic method of CLT acid |
| CN202311760848.XA CN117924121A (en) | 2023-05-26 | 2023-12-20 | Synthetic method of CLT acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310605680.9A CN116606227A (en) | 2023-05-26 | 2023-05-26 | Synthetic method of CLT acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116606227A true CN116606227A (en) | 2023-08-18 |
Family
ID=87674363
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310605680.9A Withdrawn CN116606227A (en) | 2023-05-26 | 2023-05-26 | Synthetic method of CLT acid |
| CN202311760848.XA Pending CN117924121A (en) | 2023-05-26 | 2023-12-20 | Synthetic method of CLT acid |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311760848.XA Pending CN117924121A (en) | 2023-05-26 | 2023-12-20 | Synthetic method of CLT acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN116606227A (en) |
-
2023
- 2023-05-26 CN CN202310605680.9A patent/CN116606227A/en not_active Withdrawn
- 2023-12-20 CN CN202311760848.XA patent/CN117924121A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN117924121A (en) | 2024-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111217764B (en) | Method for preparing 6-nitro-1, 2, 4-acid oxygen | |
| CN104230724A (en) | Preparation method of diethylene monoisopropanolamine | |
| CN103087550A (en) | Permanent violet product synthesis and production process | |
| CN101177418B (en) | Method for synthesizing thiazine ketone | |
| WO2021114893A1 (en) | Method for preparing 5-acetyl acetylaminobenzimidazolone | |
| CN101372466B (en) | 2-naphthalenesulfonic acid, sodium naphthalene sulfonate and preparation thereof | |
| CN110872259A (en) | Method for continuously producing 5-acetoacetylaminobenzimidazolone | |
| CN116606227A (en) | Synthetic method of CLT acid | |
| CN111018757A (en) | Method for synthesizing 3-mercaptopropionic acid by using acidic waste gas | |
| CN101092380B (en) | Method for preparing 1,2,4 acid through synthesis in homogeneous phase between water and alcohol solvent | |
| CN114539103B (en) | Synthesis method of 2-difluoroethoxy-6-trifluoromethylbenzenesulfonyl chloride | |
| CN115850018A (en) | Synthesis method of 1,2, 4-trifluorobenzene | |
| CN113292489B (en) | Preparation method of dichlorodialkyl nicotinonitrile | |
| CN107445959A (en) | A kind of preparation method of the ketone of 2 azabicyclos [2.2.1] 5 alkene in heptan 3 | |
| CN108689821B (en) | Method for regenerating chloranil by oxidizing hydrogen peroxide | |
| CN106478422A (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN108658751B (en) | Preparation method of trifluoroacetic acid | |
| CN112898225A (en) | Synthesis method of 1, 2-benzisothiazolin-3-ketone | |
| CN108911944A (en) | The preparation method of 2,4 dichloro fluorobenzene | |
| CN114380748B (en) | Synthesis method of 2, 3-dimethyl-6 amino-2H-indazole hydrochloride | |
| CN109485610B (en) | Method for synthesizing 2-chloro-4-phenylquinazoline by one-pot method | |
| CN108715580A (en) | A kind of industrialized preparing process of 2- nitryl-4-thiamphenicol benzoic acids | |
| CN111004250B (en) | Synthetic method of 1, 4-epoxy-2, 3-dicyano-1, 2,3, 4-tetrahydronaphthalene | |
| CN108752246A (en) | A kind of industrialization production method of efficient 2- nitryl-4-thiamphenicol benzoic acids | |
| CN114920622B (en) | Technological method for preparing pentafluorobromide benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20230818 |
|
| WW01 | Invention patent application withdrawn after publication |