CN106866562A - The synthetic method of BTA - Google Patents
The synthetic method of BTA Download PDFInfo
- Publication number
- CN106866562A CN106866562A CN201710255152.XA CN201710255152A CN106866562A CN 106866562 A CN106866562 A CN 106866562A CN 201710255152 A CN201710255152 A CN 201710255152A CN 106866562 A CN106866562 A CN 106866562A
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- CN
- China
- Prior art keywords
- bta
- hydrazine hydrate
- added
- nitrochlorobenzene
- synthetic method
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- 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.)
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- 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
Abstract
The invention discloses the synthetic method of BTA, comprise the following steps：Add o-nitrochlorobenzene to synthesize 1 hydroxybenzotriazole with hydrazine hydrate in tetrahydrofuran as solvent, restore 1 hydroxybenzotriazole and prepare BTA.The preparation principle of BTA and the preparation principle of existing method are identical in the present invention, and the present invention improves the yield of BTA by changing the extracting process in the preparation of reaction temperature, reaction time, the selection of solvent and BTA.
Description
Technical field
The present invention relates to a kind of synthetic method of medicine intermediate, and in particular to the synthetic method of BTA.
Background technology
BTA (BTA) is a kind of important fine chemical product.It widely used, is mainly used as copper and copper is closed
The corrosion inhibiter of gold, take a picture antifoggant, metal antirusting agent and organic synthesis intermediate；It is also widely used for coating additive, lubrication
Oil additive, synthetic dyestuffs intermediate, the preservative of synthetic detergent, anti-coagulants, Polymer material stabilizer, plant growth are adjusted
Section agent, anti-blushing agent, vapour phase inhibitor and UV absorbers and analytical reagent etc..
Numerous studies work was done in domestic and international synthesis of many researchers to BTA.Up to the present, the synthesis reported
Route has diaminobenzidine, benzimidazolone method, adjacent nitro phenylhydrazine method, o-nitrochlorobenzene method；But, existing synthetic method is received
Rate is low.
The content of the invention
The technical problems to be solved by the invention are that the method yield of conventional synthesis BTA is low, it is therefore intended that provided
The synthetic method of BTA, solves the problems, such as that the method yield of conventional synthesis BTA is low.
The present invention is achieved through the following technical solutions：
The synthetic method of BTA, comprises the following steps：
S1, in a kettle., with tetrahydrofuran as solvent, adds a certain amount of o-nitrochlorobenzene, chlorine near 3.5 times moles
The hydrazine hydrate of the 85% of nitrobenzene, 20%NaOH solution, the 20%NaOH are added after the 3-5h that flowed back after being warming up to 80-110 DEG C
The amount of the material of solution is 2 times of the amount of the material of o-nitrochlorobenzene；
Reacted reaction solution reclaims hydrazine hydrate with alcohol-water-hydrazine azeotropic distillation in S2, step S1, using a liter high-temperature
Mode reclaim dimethyl sulfoxide；
Add a certain amount of water complete to residue in Liquid Residue after S3, in step s 2 recovery hydrazine hydrate, dimethyl sulfoxide
Concentrated hydrochloric acid is added after CL, now there are a large amount of white crystals to separate out, filtering is drained and with cryosel water washing 2-3 time, and acquisition is in vain
Color crystal I-hydroxybenzotriazole；
S4, by I-hydroxybenzotriazole and 2-3 times of reduced iron powder relative to I-hydroxybenzotriazole mole and relative
In 1-10 times of water of I-hydroxybenzotriazole quality is added to reactor, after being warming up to 85 DEG C be incubated 1 hour, be added dropwise relative to
10% hydrochloric acid solution of 1-2 times of I-hydroxybenzotriazole molal quantity, the time for adding of 10% hydrochloric acid solution is small less than 1
When, the insulation reaction that flowed back after completion of dropping 1-3 hours filters unnecessary iron powder while hot, adds appropriate NaOH solution to adjust in filtrate
The pH to 3-4 of filtrate, adds NaCl in filtrate, form 10%NaCl solution, in -5 DEG C or so crystallisation by cooling, filtering, and uses ice
Water washing, 60 DEG C of vacuum drying, obtains product BTA.The preparation principle of BTA and existing method in the present invention
Preparation principle is identical, and the present invention is by changing the extraction in the preparation of reaction temperature, reaction time, the selection of solvent and BTA
Method is taken to improve the yield of BTA.
Reaction temperature in the step S1 is 85 DEG C.Synthesis I-hydroxybenzotriazole when, temperature to react influence compared with
Greatly, after test of many times, 85 DEG C is the optimum temperature of reaction.
Return time is 4h in the step S1.It is solvent to use tetrahydrofuran, and the reaction time is 4 hours optimal.
In the step S1 when o-nitrochlorobenzene is added with hydrazine hydrate in reactor, according to o-nitrochlorobenzene and hydration
The ratio between amount of material of hydrazine is 1:3.5 ratio is added at twice, is warming up to after adding o-nitrochlorobenzene and hydrazine hydrate for the first time
Flowed back after 80-110 DEG C after 3-5h, somewhat cooled down, add second addition o-nitrochlorobenzene and hydrazine hydrate before 20%NaOH solution.
Adding o-nitrochlorobenzene and hydrazine hydrate, yield at twice can stablize 96% or so.
Molecular sieve is added when being flowed back after being warming up to 80-110 DEG C after the first time addition o-nitrochlorobenzene and hydrazine hydrate.Point
Son sieve can accelerate reaction rate, improve yield.
The present invention compared with prior art, has the following advantages and advantages：
1st, the synthetic method of BTA of the present invention selects tetrahydrofuran for solvent can be by the yield of BTA
Stablize 96% or so, than the high income of the BTA in existing method；
2nd, the synthetic method of BTA of the present invention is carried by changing existing extracting process by the way of saltouing
Production efficiency high simultaneously reduces production cost；
3rd, the synthetic method method of BTA of the present invention is simple, and the optimal reaction temperature of this method is 85 DEG C or so,
Reaction temperature is not high, safe operation.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
The synthetic method of BTA of the present invention, comprises the following steps：
S1, in a kettle., with tetrahydrofuran as solvent, adds a certain amount of o-nitrochlorobenzene, chlorine near 3.5 times moles
The hydrazine hydrate of the 85% of nitrobenzene, 20%NaOH solution, the 20%NaOH are added after the 3-5h that flowed back after being warming up to 80-110 DEG C
The amount of the material of solution is 2 times of the amount of the material of o-nitrochlorobenzene；
Reacted reaction solution reclaims hydrazine hydrate with alcohol-water-hydrazine azeotropic distillation in S2, step S1, using a liter high-temperature
Mode reclaim dimethyl sulfoxide；
Add a certain amount of water complete to residue in Liquid Residue after S3, in step s 2 recovery hydrazine hydrate, dimethyl sulfoxide
Concentrated hydrochloric acid is added after CL, now there are a large amount of white crystals to separate out, filtering is drained and with cryosel water washing 2-3 time, and acquisition is in vain
Color crystal I-hydroxybenzotriazole；
S4, by I-hydroxybenzotriazole and 2-3 times of reduced iron powder relative to I-hydroxybenzotriazole mole and relative
In 1-10 times of water of I-hydroxybenzotriazole quality is added to reactor, after being warming up to 85 DEG C be incubated 1 hour, be added dropwise relative to
10% hydrochloric acid solution of 1-2 times of I-hydroxybenzotriazole molal quantity, the time for adding of 10% hydrochloric acid solution is small less than 1
When, the insulation reaction that flowed back after completion of dropping 1-3 hours filters unnecessary iron powder while hot, adds appropriate NaOH solution to adjust in filtrate
The pH to 3-4 of filtrate, adds NaCl in filtrate, form 10%NaCl solution, in -5 DEG C or so crystallisation by cooling, filtering, and uses ice
Water washing, 60 DEG C of vacuum drying, obtains product BTA.The preparation principle of BTA and existing method in the present invention
Preparation principle is identical, and the present invention is by changing the extraction in the preparation of reaction temperature, reaction time, the selection of solvent and BTA
Method is taken to improve the yield of BTA.
Reaction temperature in the step S1 is 85 DEG C.Synthesis I-hydroxybenzotriazole when, temperature to react influence compared with
Greatly, after test of many times, 85 DEG C is the optimum temperature of reaction.
Return time is 4h in the step S1.It is solvent to use tetrahydrofuran, and the reaction time is 4 hours optimal.
In the step S1 when o-nitrochlorobenzene is added with hydrazine hydrate in reactor, according to o-nitrochlorobenzene and hydration
The ratio between amount of material of hydrazine is 1:3.5 ratio is added at twice, is warming up to after adding o-nitrochlorobenzene and hydrazine hydrate for the first time
Flowed back after 80-110 DEG C after 3-5h, somewhat cooled down, add second addition o-nitrochlorobenzene and hydrazine hydrate before 20%NaOH solution.
Adding o-nitrochlorobenzene and hydrazine hydrate, yield at twice can stablize 96%.
Molecular sieve is added when being flowed back after being warming up to 80-110 DEG C after the first time addition o-nitrochlorobenzene and hydrazine hydrate.Point
Son sieve can accelerate reaction rate, improve yield.
Above-described specific embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that and the foregoing is only specific embodiment of the invention, be not intended to limit the present invention
Protection domain, all any modification, equivalent substitution and improvements within the spirit and principles in the present invention, done etc. all should include
Within protection scope of the present invention.
Claims (5)
1. the synthetic method of BTA, it is characterised in that comprise the following steps：
S1, in a kettle., with tetrahydrofuran as solvent, adds a certain amount of o-nitrochlorobenzene, chlorine nitro near 3.5 times moles
The hydrazine hydrate of the 85% of benzene, 20%NaOH solution, the 20%NaOH solution are added after the 3-5h that flowed back after being warming up to 80-110 DEG C
The amount of material be 2 times of amount of the material of o-nitrochlorobenzene；
Reacted reaction solution reclaims hydrazine hydrate with alcohol-water-hydrazine azeotropic distillation in S2, step S1, using the side of liter high-temperature
Formula reclaims dimethyl sulfoxide；
Add a certain amount of water completely molten to residue in Liquid Residue after S3, in step s 2 recovery hydrazine hydrate, dimethyl sulfoxide
Concentrated hydrochloric acid is added after solution, now there are a large amount of white crystals to separate out, filtering is drained and with cryosel water washing 2-3 time, obtains white crystalline substance
Body I-hydroxybenzotriazole；
S4, by I-hydroxybenzotriazole and 2-3 times of reduced iron powder relative to I-hydroxybenzotriazole mole and relative to 1-
The water of 1-10 times of hydroxybenzotriazole quality is added in reactor, and 1 hour is incubated after being warming up to 85 DEG C, is added dropwise relative to 1- hydroxyls
10% hydrochloric acid solution of 1-2 times of base BTA molal quantity, the time for adding of 10% hydrochloric acid solution is less than 1 hour, drop
Add and flowed back after finishing insulation reaction 1-3 hours, unnecessary iron powder is filtered while hot, appropriate NaOH solution regulation filtrate is added in filtrate
PH to 3-4, adds NaCl in filtrate, form 10%NaCl solution, in -5 DEG C or so crystallisation by cooling, filtering, and is washed with frozen water,
60 DEG C of vacuum drying, obtain product BTA.
2. the synthetic method of BTA according to claim 1, it is characterised in that the reaction temperature in the step S1
Spend is 85 DEG C.
3. the synthetic method of BTA according to claim 2, it is characterised in that return time in the step S1
It is 4h.
4. the synthetic method of BTA according to claim 1, it is characterised in that to reaction in the step S1
It is 1 according to the ratio between the amount of material of o-nitrochlorobenzene and hydrazine hydrate when adding o-nitrochlorobenzene and hydrazine hydrate in kettle:3.5 ratio
Value is added at twice, somewhat cold after the 3-5h that flowed back after being warming up to 80-110 DEG C after first time addition o-nitrochlorobenzene and hydrazine hydrate
But, second addition o-nitrochlorobenzene and hydrazine hydrate before 20%NaOH solution are added.
5. the synthetic method of BTA according to claim 4, it is characterised in that the first time adds adjacent nitro
Molecular sieve is added when being flowed back after being warming up to 80-110 DEG C after chlorobenzene and hydrazine hydrate.
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| CN201710255152.XA CN106866562A (en) | 2017-04-19 | 2017-04-19 | The synthetic method of BTA |
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| CN201710255152.XA CN106866562A (en) | 2017-04-19 | 2017-04-19 | The synthetic method of BTA |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942502A (en) * | 2019-04-12 | 2019-06-28 | 天津科技大学 | A kind of preparation method of needle-shaped benzotriazole crystal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875483A (en) * | 2012-10-26 | 2013-01-16 | 陈守文 | Synthesis technique of benzotriazole |
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- 2017-04-19 CN CN201710255152.XA patent/CN106866562A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875483A (en) * | 2012-10-26 | 2013-01-16 | 陈守文 | Synthesis technique of benzotriazole |
Non-Patent Citations (1)
| Title |
|---|
| 郑清: "苯并三氮唑合成的改进", 《辽宁化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942502A (en) * | 2019-04-12 | 2019-06-28 | 天津科技大学 | A kind of preparation method of needle-shaped benzotriazole crystal |
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