CN109627219A - A kind of production method of 5- amino-6-methyl benzimidazolone - Google Patents
A kind of production method of 5- amino-6-methyl benzimidazolone Download PDFInfo
- Publication number
- CN109627219A CN109627219A CN201811633578.5A CN201811633578A CN109627219A CN 109627219 A CN109627219 A CN 109627219A CN 201811633578 A CN201811633578 A CN 201811633578A CN 109627219 A CN109627219 A CN 109627219A
- Authority
- CN
- China
- Prior art keywords
- amino
- methyl benzimidazolone
- methyl
- production method
- benzimidazolone
- 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- Withdrawn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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of production method of 5- amino-6-methyl benzimidazolone, it is characterised in that in turn include the following steps: step 1 flows back 3,4- diaminotoluene with urea in a solvent, and then condensation reaction obtains 5- methyl benzimidazolone；Step 2 nitrifies 5- methyl benzimidazolone, obtains 5- nitro -6- methyl benzimidazolone；Step 3 restores 5- nitro -6- methyl benzimidazolone to obtain target compound 5- amino-6-methyl benzimidazolone.Present invention condensation temp in step 1 is 120-140 DEG C.The tail gas generated in the reaction process of step 1 is burned towards boiler furnace.The present invention is condensed using 1,2- dimethylbenzene, ethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, mixed xylenes system, and yield is up to 99%, more environmentally-friendly；The ammonia nitrogen in waste water can be greatly decreased；Condensation of the invention, nitrification, reduction yield all compare that other methods are much higher, and comprehensive yield reaches 90%-92%.
Description
Technical field
The invention belongs to compounds process for production thereof technical fields, and in particular to a kind of preparation side of fine-chemical intermediate
Method.
Background technique
5- amino-6-methyl benzimidazolone is the important Pigment Intermediates for synthetic dyestuff orange 64, there is Germany at present
BASF (former Ciba) production, but technology, there is no disclosure, the document that current position can be found is fewer, even if having one
A little files are also all the document of some laboratory tests, not the particular technique introduction of industrialized production.The correlation that can be found
Document has: CN1675185, and the patent describe the synthetic methods of 5- amino-6-methyl benzimidazolone, first carries out in amylalcohol
Cyclization, then reduction is nitrified, product yield is very low；6087480 patent of US is using 5- nitro -6- methyl benzimidazolone
It is restored for raw material, and is not also had in the raw materials market, oneself can only be synthesized, and do not introduce specific synthetic method；
CN101863840A more specifically describes the synthetic method of 5- amino-6-methyl benzimidazolone, but it uses experiment
The method of room, cyclization yield 98.5%；It is nitrified when nitrifying in the process using dust technology, generates a large amount of nitric acid waste water, it is difficult to locate
Reason；Restoring method only uses palladium carbon hydrogenating reduction that could obtain higher yields 91.8%, and makees solvent with DMF, it is necessary to adopt
It is recycled with rectification under vacuum.
Summary of the invention
In view of the deficienciess of the prior art, the present invention provides a kind of producer of 5- amino-6-methyl benzimidazolone
Method.
The present invention is achieved by the following technical solutions:
A kind of production method of 5- amino-6-methyl benzimidazolone, it is characterised in that in turn include the following steps:
Step 1 flows back 3,4- diaminotoluene with urea in a solvent, and then condensation reaction obtains 5- methyl benzo
Imidazolone；
5- methyl benzimidazolone is nitrified in acetate system, chlorobenzene system, dust technology system, is obtained by step 2
To 5- nitro -6- methyl benzimidazolone；
Step 3 restores 5- nitro -6- methyl benzimidazolone to obtain target compound 5- amino -6- methyl benzo miaow
Oxazolone.
Condensing agent used is 1,2- dimethylbenzene, ethylbenzene, 1,3- dimethylbenzene, 1,4- dimethylbenzene, mixing two in the step 1
Toluene, condensation temp are 120-140 DEG C.
With a small amount of moisture contained in water segregator removal raw material after flowing back in the step 1.
The tail gas generated in the step 1 reaction process is burned towards boiler furnace.
Solvent is nitrified in the step 2 using recyclable acetic acid or chlorobenzene, nitrification temperature is 40-80 DEG C.
Reduction mode used in the step 3 is to do catalyst hydrogenation reduction with nickel.
The dicyandiamide solution that the step 3 uses is methanol-water solution, methanol concentration 30-90%.
Compared with prior art, the beneficial effects of the present invention are:
1. being condensed using 1,2- dimethylbenzene, ethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, mixed xylenes system, receive
Rate is up to 99%, and smell is smaller relative to dichloro-benzenes, and remains in product without polystream, more environmentally-friendly；
2. first carrying out turnout reason before condensation reaction, temperature can be increased rapidly, can significantly promote the poly- splitting or integrating of urea
The ratio of solution side reaction, 3,4- diaminotoluenes and urea is 1:1.05-1:1.20, and the ammonia nitrogen in waste water can be greatly decreased；
3. being the ammonia absorbed in tail gas with water in traditional handicraft, the ammonium hydroxide absorbed is difficult because containing organic residue
It carries out using by the fixed gas of ammonia and dimethylbenzene in tail gas towards boiler burning in the present invention, combustion product is nitrogen, two
Carbonoxide, it is very environmentally friendly；
4. being nitrified in acetate system, solvent can be recycled, avoid in previous methods using dust technology nitrification and
The a large amount of nitric acid waste water generated, and then reluctant situation.And the yield nitrified in acetate system can be up to
99%；
5. being restored in methanol system, methanol concentration requirement is very low, is 30%-90%, can reduce cost, reacts
It is easier to, solvent recovery is simple, and product is insoluble in water, it is easy to be precipitated, yield is up to 92%-94%；
6. the yield for being condensed, nitrifying, restoring in the present invention is all compared, other methods are much higher, and comprehensive yield reaches
90%-92%.
Specific embodiment
Specific embodiment is given below, the invention will be further described.
3,4- diaminotoluene 500KG is taken, is added in 3000 liters of reaction kettles, urea 245KG is added, mixed xylenes is added
1500 liters, temperature rising reflux separates the moisture in material with water segregator, and condensation starts to carry out at 120 DEG C, when temperature reaches 138
Reaction terminates after DEG C, keeps exhaust pipe unimpeded in reaction process, and tail gas is led to boiler furnace and is burnt.Reaction terminates
Afterwards, 500 liters are filled the water in reaction kettle with pump, then carry out distillation recovery dimethylbenzene using azeotropic in a kettle, distillation terminates
Moisturizing is stirred afterwards, after filters pressing, obtains the filter cake (give money as a gift 600KG) of 5- methyl benzimidazolone, yield 99%；
Filter cake is added in 6300 liters of reaction kettle, is added 3000 liters of acetic acid, be warming up to 60 DEG C, nitric acid 310KG, drop is added dropwise
It is half an hour between added-time, present invention kettle is passed through cooling water and controls temperature at 60-80 DEG C.After completion of dropwise addition, continue stirring 30
Minute, filtrate, after filtrate is applied several times, recovery of acetic acid are collected in then filters pressing.It collects and obtains after filter cake is washed to neutral
5- nitro -6- methyl benzimidazolone (give money as a gift 775KG), yield 99.05%；
5- nitro -6- methyl benzimidazolone is added in 8000 liters of autoclave pressure, is added 4000 liters of methanol, nickel is added
Catalyst 20KG is replaced 5 times with nitrogen, is warming up to 60-80 DEG C and is then passed to hydrogen, maintains pressure between 1.0-3.0MPA, and 2
Sample detection restores completeness after hour, and after reaction terminates, catalyst is recovered by filtration, and filtrate, which is collected, is distilled to recover methanol, steams
After evaporating, room temperature is cooled the temperature to, product 5- amino-6-methyl benzimidazolone is precipitated in water, filters pressing, after washing and drying
Obtain finished product 612KG, yield 93.5%.
In conclusion only presently preferred embodiments of the present invention, is not used to limit the scope of implementation of the present invention, it is all according to
Equivalent changes and modifications carried out by shape described in scope of the invention as claimed, construction, feature and spirit should be included in this
In the scope of the claims of invention.
Claims (7)
1. a kind of production method of 5- amino-6-methyl benzimidazolone, it is characterised in that in turn include the following steps:
Step 1 flows back 3,4- diaminotoluene with urea in a solvent, and then condensation reaction obtains 5- tolimidazole
Ketone；
5- methyl benzimidazolone is nitrified in acetate system, chlorobenzene system, dust technology system, obtains 5- by step 2
Nitro -6- methyl benzimidazolone；
Step 3 restores 5- nitro -6- methyl benzimidazolone to obtain target compound 5- amino -6- tolimidazole
Ketone.
2. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: institute
Stating condensing agent used in step 1 is 1,2- dimethylbenzene, ethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, mixed xylenes, condensation
Temperature is 120-140 DEG C.
3. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: institute
It states after flowing back in step 1 with a small amount of moisture contained in water segregator removal raw material.
4. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: will
The tail gas generated in the step 1 reaction process is burned towards boiler furnace.
5. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: institute
It states and nitrifies solvent in step 2 using recyclable acetic acid or chlorobenzene, nitrification temperature is 40-80 DEG C.
6. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: institute
Stating reduction mode used in step 3 is to do catalyst hydrogenation reduction with nickel.
7. a kind of production method of 5- amino-6-methyl benzimidazolone according to claim 1, it is characterised in that: institute
The dicyandiamide solution that step 3 uses is stated as methanol-water solution, methanol concentration 30-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811633578.5A CN109627219A (en) | 2018-12-29 | 2018-12-29 | A kind of production method of 5- amino-6-methyl benzimidazolone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811633578.5A CN109627219A (en) | 2018-12-29 | 2018-12-29 | A kind of production method of 5- amino-6-methyl benzimidazolone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109627219A true CN109627219A (en) | 2019-04-16 |
Family
ID=66054456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811633578.5A Withdrawn CN109627219A (en) | 2018-12-29 | 2018-12-29 | A kind of production method of 5- amino-6-methyl benzimidazolone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627219A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256435A (en) * | 2019-07-04 | 2019-09-20 | 绍兴市精益生物化工有限公司 | One-step synthesis method of 1, 3-dimethyl uric acid |
| CN111362879A (en) * | 2020-04-28 | 2020-07-03 | 山东汇海医药化工有限公司 | Method for preparing benzimidazolone in aqueous solvent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288461A (en) * | 1998-01-13 | 2001-03-21 | 西巴特殊化学品控股有限公司 | Process for preparing sparingly soluble aromatic amines |
| CN101863840A (en) * | 2010-06-18 | 2010-10-20 | 淄博圣马化工厂 | Preparation method of 5-amino-6-methyl benzimidazolone |
| CN102924385A (en) * | 2012-10-22 | 2013-02-13 | 江苏康恒化工有限公司 | Method for preparing 5-amino benzimidazolone with high purity by catalytic hydrogenation |
-
2018
- 2018-12-29 CN CN201811633578.5A patent/CN109627219A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288461A (en) * | 1998-01-13 | 2001-03-21 | 西巴特殊化学品控股有限公司 | Process for preparing sparingly soluble aromatic amines |
| CN101863840A (en) * | 2010-06-18 | 2010-10-20 | 淄博圣马化工厂 | Preparation method of 5-amino-6-methyl benzimidazolone |
| CN102924385A (en) * | 2012-10-22 | 2013-02-13 | 江苏康恒化工有限公司 | Method for preparing 5-amino benzimidazolone with high purity by catalytic hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| 姚其正: "《药物合成反应》", 30 September 2012 * |
| 张虹 等: "4-[[1-[(4-氟苯基)甲基]-1 H-2-苯并咪唑基]氨基]-1-哌啶甲酸乙酯的合成", 《中国药物化学杂志》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256435A (en) * | 2019-07-04 | 2019-09-20 | 绍兴市精益生物化工有限公司 | One-step synthesis method of 1, 3-dimethyl uric acid |
| CN111362879A (en) * | 2020-04-28 | 2020-07-03 | 山东汇海医药化工有限公司 | Method for preparing benzimidazolone in aqueous solvent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627219A (en) | A kind of production method of 5- amino-6-methyl benzimidazolone | |
| CN112812020B (en) | Method and device for producing hexamethylene diamine from caprolactam | |
| CN104557357B (en) | The manufacture method of nitrile and its corresponding amine | |
| CN107746380B (en) | Industrial production method of 2-amino-4-acetamino anisole | |
| CN103864624A (en) | Simple method for efficiently preparing secondary amine through alkali catalyzed N-alkylation | |
| CN105924363B (en) | Preparation method of N-methyl-4-methoxyaniline | |
| CN102295605B (en) | Method for preparing benzimidazolone derivative | |
| CN103086895A (en) | Method for preparing aromatic amine from mixed nitrochlorobenzene | |
| CN102408430A (en) | Synthetic process and special equipment for substituted bis [tetraphenylporphinatoiron] | |
| CN101948465A (en) | Method for preparing vitamin B1 intermediate | |
| CN103524308A (en) | Method for preparing halogenated phenol compounds | |
| CN101037393B (en) | Synthetic process for preparing arylamine by reduction of aromatic nitro compound | |
| CN114957090B (en) | Process for the preparation of fused isoindole derivatives | |
| CN102408383B (en) | Method for synthesizing dibenzophenazine by utilizing 2-naphthylamine under the effect of catalyst | |
| CN214422544U (en) | Device for producing hexamethylene diamine from caprolactam | |
| Li et al. | Foldamer‐Derived Preorganized Bi‐and Tri‐zinc Porphyrin Tweezers for a Pentafluorobenzene‐bearing Pyridine Guest: The Binding Pattern Study | |
| CN108299466A (en) | A kind of improved Du Lutewei synthetic methods | |
| CN1869003A (en) | Preparation method of 4-aminobenzoyl-N-(4-aminobenzoyl) amine | |
| CN110105249B (en) | Preparation method of 4,4' -diphenylmethane diisocyanate | |
| CN107673994A (en) | A kind of preparation method of arylmethane class compound | |
| CN103012087B (en) | Green synthetic method of alpha, alpha'-double benzylidene cycloalkanone compound | |
| CN101781288B (en) | Preparation method of Pranlukast intermediate | |
| CN104910142A (en) | Method for preparing vitamin B1 intermediate (pyrimidine) | |
| CN114573496B (en) | Preparation method of 4-chloroindole-3-acetic acid | |
| CN115991707A (en) | Preparation method of indoloquinoxaline compound |
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: 20190416 |
|
| WW01 | Invention patent application withdrawn after publication |