CN104829506B - The industrialized preparing process of high-purity 2-nitryl-4-thiamphenicol benzoic acid - Google Patents
The industrialized preparing process of high-purity 2-nitryl-4-thiamphenicol benzoic acid Download PDFInfo
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- CN104829506B CN104829506B CN201510165545.2A CN201510165545A CN104829506B CN 104829506 B CN104829506 B CN 104829506B CN 201510165545 A CN201510165545 A CN 201510165545A CN 104829506 B CN104829506 B CN 104829506B
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Abstract
The industrialized preparing process of a kind of high-purity 2 nitro 4 thiamphenicol benzoic acids, comprises the following steps: a, neighbour's nitro MSM toluene nitric acid oxidation is generated crude product；B, addition alkaline matter are neutralized；C, reduce with reducing agent；D, centrifugal filtration isolated mother solution；E, acid out；F, centrifugal filtration obtain solid product 2 nitro 4 thiamphenicol benzoic acid wet product after separating；G, it is final qualified products after drying.This production method can realize large-scale industrial production.
Description
Technical field
The present invention relates to the production technology of 2-nitryl-4-thiamphenicol benzoic acid, a kind of high-purity 2-nitryl-4-thiamphenicol benzoic acid
Industrialized preparing process.
Background technology
2-nitryl-4-thiamphenicol benzoic acid is a kind of important intermediate in adjacent, p-methyl benzene sulfonic chloride and derived product thereof.
Adjacent, p-methyl benzene sulfonic chloride and derived product thereof include paratoluensulfonyl chloride, adjacency pair toluene sulfochloride, para toluene sulfonamide,
Orthotoluene sulfonamide, adjacency pair toluenesulfonamide, to methylsulfonyltoluene, N-ethyl adjacency pair toluenesulfonamide, tolysulfonyl
Isocyanates, adjacent nitro are to methylsulfonyltoluene, 2-nitryl-4-thiamphenicol benzoic acid etc..China produces these series of products and initiates
In generation nineteen fifty, produce orthotoluene sulfonamide for acesulpham k.Fast along with industries such as world's chemical industry, medicine, pesticide
Speed development, these series of products have been widely used in medicine, pesticide, plastics, dyestuff, coating, spice, auxiliary agent, change
The industries such as work surfactant, disinfectant, reagent, cosmetics and resin, become very important fine chemical product.
The most in recent years, along with continually developing of new medical product and Pesticidal products, para-position series of products were in medicine and agriculture
The application of medicine industry gets more and more, and presents the situation of quickly rise.
At present, 2-nitryl-4-thiamphenicol benzoic acid is mainly used in synthetic pesticide mesotrione, but in crude product 2-nitro-4-first
Sulfuryl benzoic acid has a kind of organic impurities, a kind of toxicity can be generated further after follow-up synthesizing methyl sulphur oxadiazon great
Organic impurities 1-cyano group-6-(mesyl)-7-nitro-9H-ton-9-ketone, so the essence of 2-nitryl-4-thiamphenicol benzoic acid
System purifies the most crucial and necessary, has no the report of the industrialized process for refining and purifying of 2-nitryl-4-thiamphenicol benzoic acid at present
Lead.
Summary of the invention
It is contemplated that propose the industrialized preparing process of a kind of high-purity 2-nitryl-4-thiamphenicol benzoic acid, can realize extensive
Industrialized production.
The industrialized preparing process of this high-purity 2-nitryl-4-thiamphenicol benzoic acid comprises the following steps:
A, generation crude product: by neighbour's nitro MSM toluene nitric acid oxidation, generate 2-nitryl-4-thiamphenicol benzoic acid crude product；
B, neutralization: 2-nitryl-4-thiamphenicol benzoic acid crude product and water are put into and neutralizes in still, add alkaline matter and carry out
Neutralizing, wherein the additional proportion of 2-nitryl-4-thiamphenicol benzoic acid crude product, water and alkaline matter is in mass ratio: 2-nitro
-4-thiamphenicol benzoic acid crude product: water: alkaline matter=1: (1～10): (0.25～3), neutralizes the PH at the end of reaction
Value controls 8～12；
C, reduction: in b step gained material, add the reducing agent of quality is material gross mass 0.01%～10%, enter
Row reduction reaction；
D, mother solution separate: c walks gained material and sends into the first centrifuge filtration separation, obtain mother solution；
E, acid out: walked by d in mother liquid obtained feeding acid out still, adding quality is 1%～the 30% of mother solution gross mass
Acid, carries out acid out, and at the end of acid out, pH value controls 0.1～1；
F, finished product separate: e walking gained material and sends into the second centrifuge, centrifugal filtration obtains solid product 2-after separating
Nitryl-4-thiamphenicol benzoic acid wet product；
G, be dried: by 2-nitryl-4-thiamphenicol benzoic acid wet product feeding drying machine be final qualified products after drying.
The industrialized preparing process of this high-purity 2-nitryl-4-thiamphenicol benzoic acid, by neighbour's nitro MSM toluene and nitric acid oxidation
Synthesis thick product is neutralized, reduction, centrifugation, acid out, again centrifugation, after drying, obtain highly purified 2-
Nitryl-4-thiamphenicol benzoic acid.This product purification method is that inorganic method purifies, and does not use organic solvent, compares more conventional
Organic solvent method of purification, the proportion of goods damageds are low, do not have solvent consumption, low cost, convenient separation, easily operate.This is raw
Product method can realize large-scale industrial production.
Accompanying drawing explanation
Accompanying drawing is the process chart of the industrialized purification production method of this high-purity 2-nitryl-4-thiamphenicol benzoic acid.
Detailed description of the invention
As it can be seen, the industrialized preparing process of this high-purity 2-nitryl-4-thiamphenicol benzoic acid comprises the following steps:
A, generation crude product: by neighbour's nitro MSM toluene nitric acid oxidation, generate the 2-nitro that mass content is 50～99%
-4-thiamphenicol benzoic acid crude product；
B, neutralization: 2-nitryl-4-thiamphenicol benzoic acid crude product and water are put into and neutralizes in still, add alkaline matter and carry out
Neutralizing, wherein the additional proportion of 2-nitryl-4-thiamphenicol benzoic acid crude product, water and alkaline matter is in mass ratio: 2-nitro
-4-thiamphenicol benzoic acid crude product: water: alkaline matter=1: (1～10): (0.25～3), neutralizes pH value at the end of reaction
Control 8～12；
C, reduction: in b step gained material, add the reducing agent of quality is material gross mass 0.01%～10%, enter
Row reduction reaction；
D, mother solution separate: c walks gained material and sends into the first centrifuge filtration separation, obtain mother solution；After filtration
Solid be 2-nitryl-4-thiamphenicol benzoic acid synthesis material 2-nitro-4-methylsulfonyltoluene, can be with reuse after washing.
E, acid out: walked by d in mother liquid obtained feeding acid out still, adding quality is 1%～the 30% of mother solution gross mass
Acid, carries out acid out, and at the end of acid out, pH value controls 0.1～1；
F, finished product separate: e walking gained material and sends into the second centrifuge, centrifugal filtration obtains solid product 2-after separating
Nitryl-4-thiamphenicol benzoic acid wet product；
G, be dried: by 2-nitryl-4-thiamphenicol benzoic acid wet product feeding drying machine be final qualified products after drying；
In the industrialized preparing process of this high-purity 2-nitryl-4-thiamphenicol benzoic acid, the alkaline matter in b step can be hydrogen
One in sodium oxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, sodium bicarbonate, sodium carbonate, adds in c step
Reducing agent can be the one in ferrous salt, nitrite, (burnt) sulphite, thiosulfate etc., adds in e step
Acid can be the one in hydrochloric acid, sulphuric acid, nitric acid.
Embodiment is described below, and each embodiment device therefor is all: neutralize still 10000L；Acid out still 10000L；The first,
Second centrifuge PGZ-1600, drying machine: vacuum rake dryer.
Embodiment 1
1, deliver to the 2-nitryl-4-thiamphenicol benzoic acid crude product 1056 kilograms of content 50% neutralize still, add water 1056 liters,
Stirring is lower puts into the sodium hydrate aqueous solution 528 kilograms that concentration is 15%, and surveying pH value is 10.
2, add 264 kilograms of sodium nitrite to stir 30 minutes.
3, send into the first centrifuge to filter.
4, after filtering, gained liquid delivers to acid out still, adds 850 kilograms of the nitric acid that concentration is 10%, adds stirring 30 points
Clock, surveying pH value is 1.
5, then material is sent into the second centrifuge separating and filtering, obtain 2-nitro 4-thiamphenicol benzoic acid wet product 565 public
Jin.
6, send into drying machine to be dried, obtain dry product 492 kilograms.2-nitro 4-thiamphenicol benzoic acid content is 99.3%, refined
Yield 93.2%.
Embodiment 2
1, by the 2-nitryl-4-thiamphenicol benzoic acid crude product 776 kilograms of content 75.3%, deliver to neutralize in still, add water 2500
Rising, the lower concentration that puts into of stirring is 6% potassium hydroxide aqueous solution 2328 kilograms, and survey pH value is 8.
2, add 56 kilograms of sodium sulfite, stir 45 minutes.
3, it is then fed into the first centrifuge to filter.
4, after filtering, gained liquid delivers to acid out still, adds 800 kilograms of the sulphuric acid that concentration is 28%, adds stirring 30 points
Clock, surveying pH value is 0.5.
Then 5, material sent into the second centrifuge filter, obtain 2-nitryl-4-thiamphenicol benzoic acid wet product 641 kilograms,
6, send into drying machine to be dried, obtain dry product 548 kilograms, 2-nitryl-4-thiamphenicol benzoic acid 99.1%, refined yield 93.8%.
Embodiment 3
1, by content 99%2-nitryl-4-thiamphenicol benzoic acid crude product 505 kilograms, deliver to neutralize in still, add water 5050 liters,
Stirring is lower puts into sodium carbonate solid 96 kilograms, stirs 30 minutes, and surveying pH value is 7, adds sodium carbonate solid 32 public
Jin, stirs 30 minutes, and surveying pH value is 9.
2, add 0.56 kilogram of sodium thiosulfate, stir 45 minutes.
3, it is then fed into the first centrifuge to filter.
4, filter gained liquid and deliver to acid out still, add the hydrochloric acid 570 kilograms that concentration is 10%, add stirring 30 minutes,
PH value 1.
5, the second centrifuge filtration sent into by material, obtains 2-nitro 4-thiamphenicol benzoic acid wet product 540 kilograms after filtration.
6, send into drying machine to be dried, obtain dry product 471 kilograms, 2-nitro 4-thiamphenicol benzoic acid content 99.5%, refined receipts
Rate 94.3%.
Claims (1)
1. an industrialized preparing process for 2-nitryl-4-thiamphenicol benzoic acid, is characterized in that comprising the following steps:
A, generation crude product: by neighbour's nitro MSM toluene nitric acid oxidation, generate 2-nitryl-4-thiamphenicol benzoic acid crude product；
B, neutralization: 2-nitryl-4-thiamphenicol benzoic acid crude product and water are put into and neutralizes in still, add alkaline matter to be neutralized, wherein the additional proportion of 2-nitryl-4-thiamphenicol benzoic acid crude product, water and alkaline matter is 2-nitryl-4-thiamphenicol benzoic acid crude product in mass ratio: water: alkaline matter=1: (1～10): (0.25～3), and at the end of neutralizing reaction, pH value controls 8～12；
C, reduction: in b step gained material, add the reducing agent of quality is material gross mass 0.001%～10%, carry out reduction reaction；
D, mother solution separate: c walks gained material and sends into the first centrifuge filtration separation, obtain mother solution；
E, acid out: walked by d in mother liquid obtained feeding acid out still, add the acid of quality is mother solution gross mass 1%～30%, carry out acid out, and at the end of acid out, pH value controls 0.1～1；
F, finished product separate: e walking gained material and sends into the second centrifuge, centrifugal filtration obtains solid product 2-nitryl-4-thiamphenicol benzoic acid wet product after separating；
G, be dried: by 2-nitryl-4-thiamphenicol benzoic acid wet product feeding drying machine be final qualified products after drying；Wherein, the described alkaline matter in b step is the one in sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, sodium bicarbonate, sodium carbonate, the reducing agent added in described c step is the one in ferrous salt, nitrite, sulphite, thiosulfate, and the acid added in described e step is the one in hydrochloric acid, sulphuric acid, nitric acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250525C (en) * | 2001-03-26 | 2006-04-12 | 辛甄塔有限公司 | Purification of 2-nitro-4-methylsulphonylbenzoic acid |
| CN101503383A (en) * | 2009-03-16 | 2009-08-12 | 嘉兴学院 | Preparation of o-nitro p-methylsulfonylbenzoic acid |
| CN104262215A (en) * | 2014-09-22 | 2015-01-07 | 锦州凯创化工科技有限公司 | Preparation method of 2-nitro-4-methyl sulfone benzoic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250525C (en) * | 2001-03-26 | 2006-04-12 | 辛甄塔有限公司 | Purification of 2-nitro-4-methylsulphonylbenzoic acid |
| CN101503383A (en) * | 2009-03-16 | 2009-08-12 | 嘉兴学院 | Preparation of o-nitro p-methylsulfonylbenzoic acid |
| CN104262215A (en) * | 2014-09-22 | 2015-01-07 | 锦州凯创化工科技有限公司 | Preparation method of 2-nitro-4-methyl sulfone benzoic acid |
Non-Patent Citations (1)
| Title |
|---|
| 气- 液氧化制备2- 硝基-4- 甲砜基苯甲酸工艺的研究;刘虎等;《安徽化工》;20130831;第39卷(第4期);第48-50页 * |
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Effective date of registration: 20191230 Address after: 314201 room 318, building 1, west of Washan Road, south of Zhongshan Road, Ganggang District, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Jiafu New Material Technology Co., Ltd Address before: No. 2288 Jiaxing City, Zhejiang province 314201 Jiaxing port Zhapu Economic Development Zone of Binhai Road Patentee before: Zhejiang Jiahua Energy Chemical Co., Ltd. |
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