CN108912067A - A kind of 2,3,5 triphenyltetrazolium chlorid preparation method - Google Patents
A kind of 2,3,5 triphenyltetrazolium chlorid preparation method Download PDFInfo
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- CN108912067A CN108912067A CN201811129202.0A CN201811129202A CN108912067A CN 108912067 A CN108912067 A CN 108912067A CN 201811129202 A CN201811129202 A CN 201811129202A CN 108912067 A CN108912067 A CN 108912067A
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- triphenyltertrazoliumchloride
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- benzaldehyde
- phenylhydrazine
- aniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to the preparation methods of tetraphenylphosphonium chloride tetrazole more particularly to tetraphenylphosphonium chloride tetrazole.The present invention is using benzaldehyde, aniline, phenylhydrazine as base stock, after synthesizing phenylhydrazone with phenylhydrazine first with benzaldehyde, the red colored crystalline body for the diazonium salt synthesis San Ben Ji formazan for recycling aniline to be formed recycles organic catalyst that will be cyclized into 2,3,5- benzyltriphenylphosphonium chloride tetrazoles；The technique is completely avoided using lead tetraacetate as the catalyst to synthesizing the product.The present invention does not use lead tetraacetate compared with traditional handicraft, eliminates influence of the lead to environment, and yield is up to 70% or more, purity >=99% (HPLC).
Description
Technical field
The present invention relates to the preparation methods of tetraphenylphosphonium chloride tetrazole more particularly to tetraphenylphosphonium chloride tetrazole.
Background technique
2,3, 5-Triphenyltertrazoliumchloride is the sensitive reagents of reduced sugar, it can distinguish ethyl alcohol, ketone and simple aldehyde and survey
Determine active titration diborane, five borines and the decaborane of dehydrogenase；It can be also used for the germination percentage of calibrating vegetable seeds, survey
Determine the activity of dehydrogenase, titrates borine, analyze the residual quantity of pesticide；As it can be seen that this is a reagent.
Common technique is《Organic synthesis topical reference book》The synthetic method of page 841：San Ben Ji formazan is dissolved in chloroform,
Lead tetraacetate to red is added under freezing conditions to disappear.Chloroform is steamed, residue is dissolved in water, adds hydrochloric acid, and lead chloride is precipitated.Filtering,
Liquid liquid is quenched with chloroform to be taken three times.It quenches and liquid is taken to heat concentration in water-bath, add diethyl ether and 2,3, 5-Triphenyltertrazoliumchloride is precipitated
It is brilliant --- crystal is filtered, drying is 2,3, 5-Triphenyltertrazoliumchloride product.
The lead tetraacetate that this method uses, lead element in the middle belongs to heavy metal, is harmful to the human body, while also polluting ring
Border.
Summary of the invention
The purpose of the present invention is to solve the above problem of the existing technology, provides a kind of 2,3,5- benzyltriphenylphosphonium chlorides
Tetrazole preparation method.The present invention does not use leaded raw material, reduces environmental pollution and the harm to human body.
The object of the present invention is achieved like this：A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, it is with benzene
Formaldehyde, aniline, phenylhydrazine are base stock, and including following
Step 1 synthesizes phenylhydrazone with phenylhydrazine using benzaldehyde；
Step 2, with the red colored crystalline body for the diazonium salt synthesis San Ben Ji formazan that aniline is formed；
Step 3 will be cyclized into 2,3, 5-Triphenyltertrazoliumchloride using organic catalyst；
Yield is up to 70% or more, purity >=99% (HPLC).
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, in the step one, it is
Phenylhydrazone is synthesized in organic solvent, and the mass ratio of organic solvent and benzaldehyde is 4: 1.
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, which is characterized in that the organic solvent is preferred
For methanol.
Any one described 2,3, 5-Triphenyltertrazoliumchloride preparation method, the water content of the organic solvent are low
In 1%.
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, the content of the benzaldehyde, phenylhydrazine, aniline
It is 99% or more.
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, the benzaldehyde: phenylhydrazine: mole matter of aniline
Amount is than being 1: 1.05: 1.2.
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, the organic catalyst packet in the step 3
Include one or more of morpholino b acid, N-morpholinyl, ring amine ethanesulfonic acid, ring amine propane sulfonic acid.
The present invention is using benzaldehyde, aniline, phenylhydrazine as base stock, by synthesizing phenylhydrazone with phenylhydrazine first with benzaldehyde
Afterwards, the red colored crystalline body for the diazonium salt synthesis San Ben Ji formazan for recycling aniline to be formed, recycles organic catalyst that will be cyclized into
2,3, 5-Triphenyltertrazoliumchloride；The technique is completely avoided using lead tetraacetate as the catalyst to synthesizing the product.This
Invention does not use lead tetraacetate compared with traditional handicraft, eliminates influence of the lead to environment.Yield is up to 70% or more, purity >=99%
(HPLC).The invention enables product qualities to get a promotion, which light yellow is improved to white powder product by common.And
It is easy to industrially realize.
Specific embodiment
A kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, it be using benzaldehyde, aniline, phenylhydrazine as base stock,
And including following
Step 1 synthesizes phenylhydrazone with phenylhydrazine using benzaldehyde；
Step 2, with the red colored crystalline body for the diazonium salt synthesis San Ben Ji formazan that aniline is formed；
Step 3, using organic catalyst, such as morpholino b acid, N-morpholinyl, ring amine ethanesulfonic acid, the third sulphur of ring amine
One or more of acid will be cyclized into 2,3, 5-Triphenyltertrazoliumchloride；
Yield is up to 70% or more, purity >=99% (HPLC).
Embodiment 1
212 grams (2mol) benzaldehyde newly distilled is dissolved in 1250ml methanol, 216 grams of (2mol) benzene are added under stiring
Hydrazine.There is a small amount of heat releases during phenylhydrazine is added, control temperature is no more than 30 DEG C；Obtained product is protected from light sealing and protects
It deposits；
When 200 grams of sodium hydroxides are added in 2L methanol and 200 grams of anhydrous sodium acetates are stirred dissolution, and being cooled to 0 DEG C,
The 150 grams of benzaldehyde-phenylhydrazones and liquid agitation is uniform are added；Separately by 186 grams of aniline (2mol), 500ml concentrated hydrochloric acid, 200ml water
It is made into anilinechloride solution, which is cooled to 0 DEG C, the solution that 250ml water and 140~150 grams of sodium nitrites are made into.
Diazonium salt is slowly added in the solution that second step is made under stiring, control reaction temperature is no more than 5 DEG C, analysis
Red little crystallization out, is stirred to react 2 hours, after finishing material, natural temperature reaction to room temperature, coreaction 24 hours；By the crystal
After centrifugal dehydration, after brilliant intracorporal sodium chloride wash clean, it is ensured that after NaCl is qualified, which is dried to obtain triphen first
It praises, yield is greater than 90%, 165 DEG C of fusing point
By 100 grams of triphen first for being dissolved in 500 grams of methanol, 50 grams of hydrochloric acid solutions are first added and start to be added dropwise after stirring
Catalyst 10 grams of catalyst is added altogether, remaining 50 grams of hydrochloric acid is slowly added dropwise after dripping catalyst；Keep reaction
Temperature is in 20~25 DEG C, and after the solid in reaction system all disappears, i.e. reaction terminates；After distilling out methanol, by the object
Material is put into crystallizing tank, is crystallized under room temperature；After obtained mixed crystal is carried out centrifugal dehydration, recrystallized with water
Once to get arrive 300 grams of product, yield 93.02%, purity 98.2% (HPLC).
Embodiment 2
1060 grams (5mol) benzaldehyde newly distilled is dissolved in 3125ml methanol, 540 grams of (5mol) benzene are added under stiring
Hydrazine.There is a small amount of heat releases during phenylhydrazine is added, control temperature is no more than 30 DEG C；Obtained product is protected from light sealing and protects
It deposits；
When 500 grams of sodium hydroxides are added in 5L methanol and 500 grams of anhydrous sodium acetates are stirred dissolution, and being cooled to 0 DEG C,
The 375 grams of benzaldehyde-phenylhydrazones and liquid agitation is uniform are added；Separately by 465 grams of aniline (5mol), 2500ml concentrated hydrochloric acid, 500ml
Water is made into anilinechloride solution, which is cooled to 0 DEG C, the solution that 625ml water and 350~375 grams of sodium nitrites are made into.
Diazonium salt is slowly added in the solution that second step is made under stiring, control reaction temperature is no more than 5 DEG C, analysis
Red little crystallization out, is stirred to react 2 hours, after finishing material, natural temperature reaction to room temperature, coreaction 24 hours；By the crystal
After centrifugal dehydration, after brilliant intracorporal sodium chloride wash clean, it is ensured that after NaCl is qualified, which is dried to obtain triphen first
It praises, yield is greater than 92%, 165 DEG C of fusing point
By 250 grams of triphen first for being dissolved in 1250 grams of methanol, 125 grams of hydrochloric acid solutions are first added and start to drip after stirring
Add catalyst, 25 grams of catalyst is added altogether, remaining 125 grams of hydrochloric acid is slowly added dropwise after dripping catalyst；Keep anti-
Temperature is answered to be in 20~25 DEG C, after the solid in reaction system all disappears, i.e. reaction terminates；After distilling out methanol, by this
Material is put into crystallizing tank, is crystallized under room temperature；After obtained mixed crystal is carried out centrifugal dehydration, tied again with water
It is brilliant once to get arriving 758 grams of product, yield 94.01%, purity 98.8% (HPLC).
Embodiment 3
42.4 kilograms (400mol) benzaldehyde newly distilled is dissolved in 250L methanol, 43.2 kilograms are added under stiring
(400mol) phenylhydrazine.There is a small amount of heat releases during phenylhydrazine is added, control temperature is no more than 30 DEG C；Obtained product
It is protected from light and is sealed；
40 kilograms of sodium hydroxides are added in 400L methanol and 40 kilograms of anhydrous sodium acetates are stirred dissolution, and are cooled to 0
DEG C when, the 300 kilograms of benzaldehyde-phenylhydrazones and liquid agitation is uniform are added；Separately by 37.2 kilograms of aniline (400mol), 1001 is dense
Hydrochloric acid, 4001 water are made into anilinechloride solution, which are cooled to 0 DEG C, 5001 water are matched with 28~30 kilograms of sodium nitrites
At solution.
Diazonium salt is slowly added in the solution that second step is made under stiring, control reaction temperature is no more than 5 DEG C, analysis
Red little crystallization out, is stirred to react 2 hours, after finishing material, natural temperature reaction to room temperature, coreaction 24 hours；By the crystal
After centrifugal dehydration, after brilliant intracorporal sodium chloride wash clean, it is ensured that after NaCl is qualified, which is dried to obtain triphen first
It praises, yield is greater than 90%, 165 DEG C of fusing point.
By 200 kilograms of triphen first for being dissolved in 1000L methanol, 10 kilograms of hydrochloric acid solutions are first added, after stirring, start
Catalyst is added dropwise, 2 kg catalysts are added altogether, after dripping catalyst, remaining 10 kilograms of hydrochloric acid is slowly added dropwise；It protects
It holds reaction temperature and is in 20~25 DEG C, after the solid in reaction system all disappears, i.e. reaction terminates；After distilling out methanol,
The material is put into crystallizing tank, is crystallized under room temperature；After obtained mixed crystal is carried out centrifugal dehydration, carried out with water
Recrystallization once to get arrive 60.6 kilograms of product, yield 93.95%, purity 98.5% (HPLC).
The product that above-mentioned each embodiment obtains is white powder.
Claims (7)
1. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method, which is characterized in that it is to be with benzaldehyde, aniline, phenylhydrazine
Base stock, and including following
Step 1 synthesizes phenylhydrazone with phenylhydrazine using benzaldehyde；
Step 2, the red colored crystalline body that the diazonium salt synthesis triphenyl first formed with aniline is jumped up；
Step 3 will be cyclized into 2,3, 5-Triphenyltertrazoliumchloride using organic catalyst；
Yield is up to 70% or more, purity >=99%, HPLC.
2. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 1, which is characterized in that described
In step 1, it is to synthesize phenylhydrazone in organic solvent, and the mass ratio of organic solvent and benzaldehyde is 4: 1.
3. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 2, which is characterized in that described to have
Solvent is preferably methanol.
4. any one 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 2 or 3, feature exist
In the water content of the organic solvent is lower than 1%.
5. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 1, which is characterized in that described
Benzaldehyde, phenylhydrazine, aniline content be 99% or more.
6. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 1, which is characterized in that the benzene
Formaldehyde: phenylhydrazine: the molal weight ratio of aniline is 1: 1.05: 1.2.
7. a kind of 2,3, 5-Triphenyltertrazoliumchloride preparation method according to claim 1, which is characterized in that its feature
It is, the organic catalyst in the step 3 includes morpholino b acid, N-morpholinyl, cyclohexylamine ethanesulfonic acid, cyclohexylamine
One or more of propane sulfonic acid.
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| CN201811129202.0A CN108912067A (en) | 2018-09-27 | 2018-09-27 | A kind of 2,3,5 triphenyltetrazolium chlorid preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117791A (en) * | 2019-05-23 | 2019-08-13 | 电子科技大学 | A kind of binding force promotor for holes on high density interconnected printed circuit board brownification liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980216A (en) * | 2014-06-05 | 2014-08-13 | 湖北百诺捷生物科技有限公司 | Synthesis method of chloridized-2,3,5-triphenyl tetrazolium chloride |
-
2018
- 2018-09-27 CN CN201811129202.0A patent/CN108912067A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980216A (en) * | 2014-06-05 | 2014-08-13 | 湖北百诺捷生物科技有限公司 | Synthesis method of chloridized-2,3,5-triphenyl tetrazolium chloride |
Non-Patent Citations (3)
| Title |
|---|
| 冯芳等: "《药物分析》", 31 December 2003 * |
| 沈文广: "《东南大学硕士学位论文》", 31 December 2007 * |
| 邵俊等: "《环境与化学实验基础知识汇编》", 31 December 2016 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117791A (en) * | 2019-05-23 | 2019-08-13 | 电子科技大学 | A kind of binding force promotor for holes on high density interconnected printed circuit board brownification liquid |
| CN110117791B (en) * | 2019-05-23 | 2023-11-10 | 电子科技大学 | Binding force promoter for brown oxide liquid of high-density interconnection printed circuit board |
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