CN110407742A - A method of preparing the bromo- 4- methylsulfonyl pyridine of 3- - Google Patents
A method of preparing the bromo- 4- methylsulfonyl pyridine of 3- Download PDFInfo
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- CN110407742A CN110407742A CN201910594226.1A CN201910594226A CN110407742A CN 110407742 A CN110407742 A CN 110407742A CN 201910594226 A CN201910594226 A CN 201910594226A CN 110407742 A CN110407742 A CN 110407742A
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- pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
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- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention relates to technical field of fine, disclose a kind of method for preparing the bromo- 4- methylsulfonyl pyridine of 3-.Specific steps: with 3,4- dibromo pyridine and methyl sulfinic acid sodium for raw material, iodate Asia ketone is catalyst, and L-PROLINE is additive, reacts 24 hours for 100 degrees Celsius in dimethyl sulfoxide, the bromo- 4- methylsulfonyl pyridine of target product 3- can be obtained.The method is easy to operate, and using 3,4- dibromo pyridine and methyl sulfinic acid sodium as reaction raw materials, a step is efficiently synthesized target product, has potential industrial value, is worthy of popularization.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of method for preparing the bromo- 4- methylsulfonyl pyridine of 3-.
Background technique
The bromo- 4- methylsulfonyl pyridine of 3- is a kind of important organic compound, it is widely present in all kinds of natural products and medicine
In object, while such compound is also important the intermediate of organic synthesis.Therefore, how directly, be efficiently synthesized the bromo- 4- of 3-
Methylsulfonyl pyridine has caused the highest attention of chemist.
Currently, the reported bromo- 4- methylsulfonyl pyridine synthetic method of 3- (PCT Int.Appl.2016180537) is mainly logical
Cross the synthesis of two steps: firstly, by 3,4- dibromo pyridine 4- methyl mercapto -3- bromopyridine corresponding with sodium methyl mercaptide reaction generation；Secondly,
Recycle metachloroperbenzoic acid that the oxidation of 4- methyl mercapto -3- bromopyridine is generated the corresponding bromo- 4- methylsulfonyl pyridine of 3-.This method
Existing defect: the yield of the bromo- 4- methylsulfonyl pyridine of first, target product 3- is lower, the receipts that document report to second step is reacted
Rate only has 41%；Second, which constructs target product by two-step reaction, cumbersome, not simple.
Therefore, exploring and developing efficient, the novel bromo- 4- methylsulfonyl pyridine of 3- is one of vital task of chemist.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of efficient, novel bromo- 4- methylsulfonyl pyrroles of 3-
Pyridine method.
The bromo- 4- methylsulfonyl pyridine Step of synthesis 3- according to the present invention is as follows: by 3,4- dibromo pyridine, methyl sulfinic acid
Sodium, iodate Asia ketone, L-PROLINE sequentially add in the pressure pipe containing reaction dissolvent dimethyl sulfoxide, and 100 degrees Celsius with vigorous stir
It mixes 24 hours, after reaction, successively carries out reaction solution concentration and column chromatography for separation, can be obtained the bromo- 4- first of target product 3-
Sulphonyl pyridine.
The reaction dissolvent of system is dimethyl sulfoxide in the present invention.
The concentration of reaction system is 1.25 mol/Ls in the present invention.
3,4- dibromo pyridine in invention, methyl sulfinic acid sodium, iodate Asia ketone, L-PROLINE used in molar ratio be 1:1.2:
0.1:0.2.
Heretofore described reaction temperature is 100 degrees Celsius.
The heretofore described reaction time is 24 hours.
Specific embodiment
The following examples will be helpful to illustrate the present invention, but not limit to its range.
Specific embodiment:
It is sequentially added in the pressure pipe of 50mL dimethyl sulfoxide (4.0mL), 3,4- dibromo pyridines (5mmol, 1.185g),
Methyl sulfinic acid sodium (6mmol, 0.613g), iodate Asia ketone (0.5mmol, 0.095g), L-PROLINE (1.0mmol, 0.115g),
Anti- temperature control is vigorously stirred reaction 24 hours at 100 degrees Celsius.After reaction, it is cooled to room temperature, successively carries out anti-
Liquid concentration and column chromatography for separation are answered, can be obtained the bromo- 4- methylsulfonyl pyridine of target product 3- (1.06g, 90%).
It is as follows to react the equation being related to:
The nuclear magnetic data of the bromo- 4- methylsulfonyl pyridine of target product 3-, mass spectrometric data are as follows:
1H NMR(300MHz,CDCl3) δ 8.90 (s, 1H), 8.75 (d, J=5.0Hz, 1H), 7.95 (d, J=4.8Hz,
1H),3.23(s,3H).
13C NMR(75MHz,CDCl3)δ154.59,149.92,147.00,123.58,117.65,42.03.
Ms (EI): m/z=234.95,236.95 [M+].
The foregoing describe optional embodiments of the invention, to instruct how those skilled in the art implement and reproduce this hair
It is bright.In order to instruct the present invention program, some routine techniques aspects are simplified and saved.Those skilled in the art answer
The understanding is originated from the modification of this respect, within the scope of the present invention.
Claims (5)
1. a kind of method for preparing the bromo- 4- methylsulfonyl pyridine of 3-, it is characterised in that: by 3,4- dibromo pyridine, methyl sulfinic acid sodium,
Iodate Asia ketone, L-PROLINE sequentially add in the pressure pipe containing reaction dissolvent dimethyl sulfoxide, heat and are vigorously stirred, reaction
After, it is cooled to room temperature and successively carries out reaction solution concentration and column chromatography for separation, can be obtained the bromo- 4- methylsulfonyl of target product 3-
Pyridine, wherein the used in molar ratio of 3,4- dibromo pyridines, methyl sulfinic acid sodium, iodate Asia ketone, L-PROLINE is 1:1.2:0.1:
0.2。
2. the method according to claim 1, wherein the decompression steaming that the method also includes carrying out after reaction
It evaporates, column chromatography for separation and collection target product.
3. the method as described in claim 1, it is characterised in that: reaction temperature is at 100 degrees Celsius.
4. the method as described in claim 1, it is characterised in that: the reaction time is 24 hours.
5. the method as described in claim 1, it is characterised in that: the concentration of reaction system is 1.25 mol/Ls.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910594226.1A CN110407742B (en) | 2019-07-03 | 2019-07-03 | Method for preparing 3-bromo-4-methylsulfonylpyridine |
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| CN201910594226.1A CN110407742B (en) | 2019-07-03 | 2019-07-03 | Method for preparing 3-bromo-4-methylsulfonylpyridine |
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| CN110407742A true CN110407742A (en) | 2019-11-05 |
| CN110407742B CN110407742B (en) | 2022-06-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260050A (en) * | 2022-08-04 | 2022-11-01 | 常州大学 | Method for preparing 3-bromo-N-arylpropionamide by participation of NBS |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651408A (en) * | 2004-11-26 | 2005-08-10 | 中国科学院上海有机化学研究所 | Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate |
| CN107686471A (en) * | 2017-09-28 | 2018-02-13 | 四川青木制药有限公司 | A kind of Fei Luokao former times and its synthetic method of intermediate |
| US20180118718A1 (en) * | 2015-05-13 | 2018-05-03 | Selvita S.A. | Substituted Quinoxaline Derivatives |
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2019
- 2019-07-03 CN CN201910594226.1A patent/CN110407742B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651408A (en) * | 2004-11-26 | 2005-08-10 | 中国科学院上海有机化学研究所 | Amino acid accelerated CuI catalyzed aryl halide and coupling reaction of alkyl sulfonate |
| US20180118718A1 (en) * | 2015-05-13 | 2018-05-03 | Selvita S.A. | Substituted Quinoxaline Derivatives |
| CN107686471A (en) * | 2017-09-28 | 2018-02-13 | 四川青木制药有限公司 | A kind of Fei Luokao former times and its synthetic method of intermediate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260050A (en) * | 2022-08-04 | 2022-11-01 | 常州大学 | Method for preparing 3-bromo-N-arylpropionamide by participation of NBS |
| CN115260050B (en) * | 2022-08-04 | 2023-08-22 | 常州大学 | Method for preparing 3-bromo-N-aryl propionamide by using NBS |
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