CN102887841A - Preparation method of compound dansyl chloride - Google Patents
Preparation method of compound dansyl chloride Download PDFInfo
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- CN102887841A CN102887841A CN2012104316502A CN201210431650A CN102887841A CN 102887841 A CN102887841 A CN 102887841A CN 2012104316502 A CN2012104316502 A CN 2012104316502A CN 201210431650 A CN201210431650 A CN 201210431650A CN 102887841 A CN102887841 A CN 102887841A
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- dansyl chloride
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- dansyl
- sulfonic acid
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- 0 CC1[C@](C)CCCC=CCC1C*S(Cl)(=O)=O Chemical compound CC1[C@](C)CCCC=CCC1C*S(Cl)(=O)=O 0.000 description 1
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Abstract
The invention provides a synthesis and purification method of dansyl chloride. The method comprises the following steps of: (1) preparation of dansyl acid; and (2) preparation of dansyl chloride: putting dansyl acid into a dry 500mL single-opening bottle, adding phosphorus oxychloride, connecting the single-opening bottle with a condensation pipe and a drying pipe, controlling the temperature of oil bath at 90 DEG C for reaction overnight, stopping the reaction, cooling to room temperature and performing a quenching reaction with ice water, extracting with 3*500mL dichloromethane, drying the extract liquid with anhydrous sodium sulfate and performing spin drying to obtain orange solid, and recrystallizing n-hexane to obtain a pure product of dansyl chloride. The invention provides a brand new synthesis and purification method of dansyl chloride; the yield of the final product exceeds 70%, and the yield of the intermediate product exceeds 40%; the production method is scientific and reasonable; and elaborate theoretical and practical guide is provided for the subsequent expanded production.
Description
Technical field
The invention belongs to the compound preparation field, especially a kind of preparation method of compound dansyl chloride.
Background technology
At present, because Bioexperiment makes new breakthroughs, make us in the process for the treatment of and the searching cause of disease, means are mistake more, the result is more accurate, so for treating various diseases the property pharmaceutical requirements is also increased gradually, therefore, various compounds with new function are in a large amount of being developed, and the whole world all has the new compound of the various difficult and complicated cases of opposing in searching, so in the process of these new compound exploitations, can produce the compound of numerous new textures and new configuration, and then searching is useful in these numerous new compounds, and the molecule for the treatment of use is arranged, and therefore developing new compound is one and important process.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of compound dansyl chloride is provided, synthetic also this compound of purifying of the present invention makes its purity arrive certain requirement, can further test or application it.
The present invention realizes that the technical scheme of purpose is as follows:
A kind of preparation method of dansyl chloride, step is as follows:
⑴ the preparation of red sulfonic acid
Take by weighing sodium bicarbonate and be dissolved in 500mL water, be added in the 2L there-necked flask, then slowly add 1-Naphthylamine-5-sulfonic, stir 30min, drip methyl-sulfate, keep low-temp reaction 5h, then be warming up to 60～70 ℃, keep spending the night, transfer to acidity with concentrated hydrochloric acid, have a large amount of solids to separate out, filter, filter cake boils to solid entirely molten with dilute hydrochloric acid, twice in recrystallization, filter to get tabular crystal, drying gets the red sulfonic acid of compound;
⑵ the preparation of dansyl chloride
Take by weighing red sulfonic acid and put into dry 500mL single port bottle, add phosphorus oxychloride, single port bottle graft prolong and drying tube, the control oil bath temperature spends the night 90 ℃ of reactions, stopped reaction, the frozen water cancellation is reacted after being cooled to room temperature, and extraction is with 3 * 500mL methylene dichloride, the extraction liquid anhydrous sodium sulfate drying, be spin-dried for, get the safran solid, the normal hexane recrystallization gets the dansyl chloride sterling.
And described sodium bicarbonate: 1-Naphthylamine-5-sulfonic: the mol ratio of methyl-sulfate is: 4:1:2.
And described red sulfonic acid: the mass ratio of phosphorus oxychloride is: 3:10-30.
Advantage of the present invention and beneficial effect are:
1, the invention provides a kind of synthetic and purification process of dansyl chloride, its final product productive rate be 70% or more and the productive rate of intermediate product also more than 40%, production method science, rationally is for follow-up expanding production provides detailed theory and practice guidance.
2, the invention provides synthesis condition, the raw material of each step in the dansyl chloride building-up process, and the nuclear-magnetism figure of synthetic after product, for the analysis and identification of intermediate product in the building-up process provides detailed support.
Description of drawings
Fig. 1 is the nuclear-magnetism figure of the red sulfonic acid of the present invention,
1HNMR:(300MHz, DMSO);
Fig. 2 is the nuclear-magnetism figure of dansyl chloride of the present invention,
1HNMR:(300MHz, CDCl
3).
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further specified, following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The preparation method's of the compounds of this invention dansyl chloride route is as follows:
Raw material is as follows, is commercially available.
1-Naphthylamine-5-sulfonic
Methyl-sulfate
Phosphorus oxychloride is heavily steamed
Quadrol
Sodium bicarbonate
Triethylamine
Piperazine anhydrous
Triethylamine.
The preparation method of dansyl chloride, step is as follows:
⑴ the preparation of red sulfonic acid
Take by weighing sodium bicarbonate (2mol) and be dissolved in 500mL water, be added in the 2L there-necked flask, then slowly add 1-Naphthylamine-5-sulfonic (0.5mol), stir 30min, drip the 1.0mol methyl-sulfate, keep low-temp reaction 5h.Then be warming up to 60～70 ℃, keep spending the night, transfer to acidity with concentrated hydrochloric acid, have a large amount of solids to separate out.Filter, filter cake boils to solid entirely molten with 0.1M dilute hydrochloric acid, and recrystallization twice filters to get tabular crystal, drying.Get altogether 62g of the red sulfonic acid of compound, yield 49.3%.
⑵ the preparation of dansyl chloride
Take by weighing the red sulfonic acid of 30g and put into dry 500mL single port bottle, add the 200mL phosphorus oxychloride, single port bottle graft prolong and drying tube, the control oil bath temperature spends the night 90 ℃ of reactions.Stopped reaction is cooled to frozen water cancellation reaction after the room temperature, and extraction is with 3 * 500mL methylene dichloride.The extraction liquid anhydrous sodium sulfate drying is spin-dried for, and gets the safran solid.Crude product is 24.2g altogether, yield approximately 75%.The normal hexane recrystallization gets sterling.
Claims (3)
1. the preparation method of a dansyl chloride, it is characterized in that: step is as follows:
⑴ the preparation of red sulfonic acid
Take by weighing sodium bicarbonate and be dissolved in 500mL water, be added in the 2L there-necked flask, then slowly add 1-Naphthylamine-5-sulfonic, stir 30min, drip methyl-sulfate, keep low-temp reaction 5h, then be warming up to 60～70 ℃, keep spending the night, transfer to acidity with concentrated hydrochloric acid, have a large amount of solids to separate out, filter, filter cake boils to solid entirely molten with dilute hydrochloric acid, twice in recrystallization, filter to get tabular crystal, drying gets the red sulfonic acid of compound;
⑵ the preparation of dansyl chloride
Take by weighing red sulfonic acid and put into dry 500mL single port bottle, add phosphorus oxychloride, single port bottle graft prolong and drying tube, the control oil bath temperature spends the night 90 ℃ of reactions, stopped reaction, the frozen water cancellation is reacted after being cooled to room temperature, and extraction is with 3 * 500mL methylene dichloride, the extraction liquid anhydrous sodium sulfate drying, be spin-dried for, get the safran solid, the normal hexane recrystallization gets the dansyl chloride sterling.
2. the preparation method of dansyl chloride according to claim 1, it is characterized in that: described sodium bicarbonate: 1-Naphthylamine-5-sulfonic: the mol ratio of methyl-sulfate is: 4:1:2.
3. the preparation method of dansyl chloride according to claim 1, it is characterized in that: described red sulfonic acid: the mass ratio of phosphorus oxychloride is: 3:10-30.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945285A (en) * | 2015-05-26 | 2015-09-30 | 无锡贝塔医药科技有限公司 | Synthesis method of isotope labeled dansyl chloride-13C2 |
| CN110372542A (en) * | 2019-07-01 | 2019-10-25 | 大连理工大学 | One group of isotope labelling dansyl Cl and its synthetic method |
| CN111349028A (en) * | 2020-03-11 | 2020-06-30 | 苏州根岸生物科技有限责任公司 | Synthesis method of dansyl chloride for preparing fluorescent probe |
| CN112010782A (en) * | 2019-05-31 | 2020-12-01 | 中国医学科学院药物研究所 | 3-deuterated dansyl chloride and preparation method and application thereof |
| CN112010790A (en) * | 2019-05-31 | 2020-12-01 | 中国医学科学院药物研究所 | Preparation method of 6-deuterated dansyl chloride |
| CN115430407A (en) * | 2022-09-16 | 2022-12-06 | 华北电力大学（保定） | Preparation method of fluorescence response type water phase adsorbent, product and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945285A (en) * | 2015-05-26 | 2015-09-30 | 无锡贝塔医药科技有限公司 | Synthesis method of isotope labeled dansyl chloride-13C2 |
| CN112010782A (en) * | 2019-05-31 | 2020-12-01 | 中国医学科学院药物研究所 | 3-deuterated dansyl chloride and preparation method and application thereof |
| CN112010790A (en) * | 2019-05-31 | 2020-12-01 | 中国医学科学院药物研究所 | Preparation method of 6-deuterated dansyl chloride |
| CN112010782B (en) * | 2019-05-31 | 2023-01-06 | 中国医学科学院药物研究所 | 3-deuterated dansyl chloride and preparation method and application thereof |
| CN110372542A (en) * | 2019-07-01 | 2019-10-25 | 大连理工大学 | One group of isotope labelling dansyl Cl and its synthetic method |
| CN111349028A (en) * | 2020-03-11 | 2020-06-30 | 苏州根岸生物科技有限责任公司 | Synthesis method of dansyl chloride for preparing fluorescent probe |
| CN111349028B (en) * | 2020-03-11 | 2022-02-11 | 苏州根岸生物科技有限责任公司 | Synthesis method of dansyl chloride for preparing fluorescent probe |
| CN115430407A (en) * | 2022-09-16 | 2022-12-06 | 华北电力大学（保定） | Preparation method of fluorescence response type water phase adsorbent, product and application thereof |
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Application publication date: 20130123 |