CN108864099A - A kind of synthetic method of high-purity 6-Furfurylaminopurine - Google Patents
A kind of synthetic method of high-purity 6-Furfurylaminopurine Download PDFInfo
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- CN108864099A CN108864099A CN201811046989.4A CN201811046989A CN108864099A CN 108864099 A CN108864099 A CN 108864099A CN 201811046989 A CN201811046989 A CN 201811046989A CN 108864099 A CN108864099 A CN 108864099A
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- China
- Prior art keywords
- furfurylaminopurine
- purity
- synthetic method
- chloropurine
- dbu
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D473/00—Heterocyclic compounds containing purine ring systems
- C07D473/26—Heterocyclic compounds containing purine ring systems with an oxygen, sulphur, or nitrogen atom directly attached in position 2 or 6, but not in both
- C07D473/32—Nitrogen atom
- C07D473/34—Nitrogen atom attached in position 6, e.g. adenine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic methods of high-purity 6-Furfurylaminopurine.In 11 carbon -7- alkene of 1,8- diazabicylo（DBU）In the presence of, by chaff amine and 6-chloropurine under hexamethyldisilazane counterflow condition, nucleophilic substitution is carried out, 6-Furfurylaminopurine crude product is obtained, be recrystallized to give 6-Furfurylaminopurine, 99.5% or more HPLC purity is single miscellaneous less than 0.1%.Route simple process of the present invention, high income, non-wastewater discharge.
Description
Technical field
The present invention relates to a kind of synthetic methods of high-purity 6-Furfurylaminopurine, belong to technical field of organic synthesis.
Background technique
6-Furfurylaminopurine, white crystals or white crystalline powder, also known as 6-nonylaminopurine, kinetin, are one
The natural plants endogenous hormones of kind purines and first basic element of cell division of mankind's discovery, can be artificial synthesized.Chaff amino
Purine, which has, promotes cell division and tissue differentiation；The differentiation of induced bud releases apical dominance；Protein and chlorophyll is delayed to drop
Solution has the effect of fresh-keeping and health care；Delay absciss layer to be formed, increases the effects of bearing fruit.This agent is mainly used for tissue cultures, with auxin
Cooperation promotes cell division, evoked callus and tissue differentiation.
The synthetic method of 6-Furfurylaminopurine mainly has at present：Adenine is condensed under alkali effect with chaff chlorine；Methyl mercapto is fast
Purine and the condensation of chaff amine；Adenine and the condensation of chaff amine；Acyl purine and furoyl chloride are condensed into furoyl purine, then lithium aluminium hydride reduction again
It obtains；Adenine and furfuryl alcohol condensation etc., however these methods are there are raw material sources are limited or the problems such as yield is low, using 6- chlorine
Purine and chaff amine reaction method are more direct, and since 6 chlorine activity are very high, it is anti-in ethyl alcohol or butanol solvent to have document report
It answers, easily generation chlorine replaces by-product by alcohol, causes single miscellaneous unqualified.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides 6-chloropurines and chaff amine nucleophilic substitution, filter, again
Crystallization obtains high-purity 6-Furfurylaminopurine scheme.
To achieve the goals above, the present invention adopts the following technical scheme that：In the presence of DBU, chaff amine and 6-chloropurine exist
It is reacted in hexamethyldisilazane, obtains 6-Furfurylaminopurine crude product, be recrystallized to give high-purity 6-Furfurylaminopurine, HPLC purity
99.5% or more, it is single miscellaneous less than 0.1%.
Further, in the above-mentioned technical solutions, reaction is preferably mixed using chaff amine with DBU, by 6-chloropurine and pregnancy
Base disilazane is warming up to 110-115 DEG C, starts that chaff amine is added dropwise and DBU mixture mode carries out.
Further, in the above-mentioned technical solutions, the 6-chloropurine and chaff amine molar ratio are 1:1-1.15.
Further, in the above-mentioned technical solutions, the 6-chloropurine and DBU molar ratio are 1：1-1.2.
Further, in the above-mentioned technical solutions, the reaction temperature is at 110-130 DEG C.
Further, in the above-mentioned technical solutions, the recrystallization solvent ethyl alcohol.
Advantageous effect of the invention
The present invention obtains 6-Furfurylaminopurine crude product by 6-chloropurine and chaff amine nucleophilic substitution, and high-purity 6- is obtained after recrystallization
Chaff adenine phosphate, 99.5% or more HPLC purity are single miscellaneous less than 0.1%.Reaction condition is mild, and raw material sources are extensive, purity and receipts
Rate is high.
Specific embodiment
Embodiment 1：
6-chloropurine 100g and hexamethyldisilazane 150g is added to three-necked flask, is warming up to 110 DEG C, be added dropwise chaff amine 65g and
The mixed liquor of DBU125g, drips off, and is heated to reflux 2h, is cooled to 20 DEG C, filters, and it is fast to obtain 6- chaff amino for filter cake ethyl alcohol recrystallization
Purine 156g, white powder, yield 96%, HPLC purity 99.7%, single miscellaneous 0.02%.
Embodiment 2：
6-chloropurine 100g and hexamethyldisilazane 180g is added to three-necked flask, is warming up to 110 DEG C, be added dropwise chaff amine 70g and
The mixed liquor of DBU120g, drips off, and is heated to reflux 2h, cools down, and filters, and filter cake recrystallization obtains 6-Furfurylaminopurine 159g, white
Powder, yield 98%, HPLC purity 99.7%, single miscellaneous 0.02%.
Embodiment 3：
6-chloropurine 200g and hexamethyldisilazane 300g is added to three-necked flask, is warming up to 110 DEG C, be added dropwise chaff amine 106g and
The mixed liquor of DBU208g, drips off, and is heated to reflux 2h, cools down, and filters, and filter cake recrystallization obtains 6-Furfurylaminopurine 309g, white
Powder, yield 95%, HPLC purity 99.5%, single miscellaneous 0.03%.
Claims (6)
1. a kind of synthetic method of high-purity 6-Furfurylaminopurine, it is characterised in that：In the presence of DBU, by chaff amine and 6-chloropurine
It is reacted in hexamethyldisilazane, obtains 6-Furfurylaminopurine crude product, be recrystallized to give high-purity 6-Furfurylaminopurine, HPLC is pure
99.5% or more degree, it is single miscellaneous less than 0.1%.
2. the synthetic method of high-purity 6-Furfurylaminopurine according to claims 1, it is characterised in that：Reaction using chaff amine with
DBU mixing, is warming up to 110-115 DEG C for 6-chloropurine and hexamethyldisilazane, starts that chaff amine and DBU mixture mode is added dropwise
It carries out.
3. according to the synthetic method of the high-purity 6-Furfurylaminopurine of claims 1 or 2, it is characterised in that：6-chloropurine with
The molar ratio of chaff amine is 1：1-1.15.
4. according to the synthetic method of the high-purity 6-Furfurylaminopurine of claims 1 or 2, it is characterised in that：6-chloropurine with
DBU molar ratio is 1：1-1.2.
5. according to the synthetic method of the high-purity 6-Furfurylaminopurine of claims 1 or 2, it is characterised in that：Reaction temperature exists
110-130℃。
6. according to the synthetic method of the high-purity 6-Furfurylaminopurine of claims 1 or 2, it is characterised in that：Recrystallization solvent
Selected from ethyl alcohol.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811046989.4A CN108864099A (en) | 2018-09-08 | 2018-09-08 | A kind of synthetic method of high-purity 6-Furfurylaminopurine |
| PCT/CN2019/102634 WO2020048343A1 (en) | 2018-09-08 | 2019-08-26 | Synthesis method for 6-furfurylaminopurine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811046989.4A CN108864099A (en) | 2018-09-08 | 2018-09-08 | A kind of synthetic method of high-purity 6-Furfurylaminopurine |
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| Publication Number | Publication Date |
|---|---|
| CN108864099A true CN108864099A (en) | 2018-11-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811046989.4A Pending CN108864099A (en) | 2018-09-08 | 2018-09-08 | A kind of synthetic method of high-purity 6-Furfurylaminopurine |
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| CN (1) | CN108864099A (en) |
| WO (1) | WO2020048343A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020048343A1 (en) * | 2018-09-08 | 2020-03-12 | 湖北荆洪生物科技股份有限公司 | Synthesis method for 6-furfurylaminopurine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314910A (en) * | 1998-06-23 | 2001-09-26 | 葛兰素集团有限公司 | Adenosine derivatives |
| CN106632338A (en) * | 2016-12-16 | 2017-05-10 | 温州医科大学 | 9-subsituted-N-(2-chlorobenzyl)purine-6-amine derivative, as well as preparation method and application thereof |
| CN106883233A (en) * | 2017-02-27 | 2017-06-23 | 江苏省农用激素工程技术研究中心有限公司 | The synthetic method of adenine and its derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864099A (en) * | 2018-09-08 | 2018-11-23 | 湖北荆洪生物科技股份有限公司 | A kind of synthetic method of high-purity 6-Furfurylaminopurine |
-
2018
- 2018-09-08 CN CN201811046989.4A patent/CN108864099A/en active Pending
-
2019
- 2019-08-26 WO PCT/CN2019/102634 patent/WO2020048343A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314910A (en) * | 1998-06-23 | 2001-09-26 | 葛兰素集团有限公司 | Adenosine derivatives |
| CN106632338A (en) * | 2016-12-16 | 2017-05-10 | 温州医科大学 | 9-subsituted-N-(2-chlorobenzyl)purine-6-amine derivative, as well as preparation method and application thereof |
| CN106883233A (en) * | 2017-02-27 | 2017-06-23 | 江苏省农用激素工程技术研究中心有限公司 | The synthetic method of adenine and its derivative |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020048343A1 (en) * | 2018-09-08 | 2020-03-12 | 湖北荆洪生物科技股份有限公司 | Synthesis method for 6-furfurylaminopurine |
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| WO2020048343A1 (en) | 2020-03-12 |
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Application publication date: 20181123 |
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