CN101838225A - Sulfonylation methods of amine and derivative thereof - Google Patents
Sulfonylation methods of amine and derivative thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic chemistry, in particular to the sulfonylation methods of an amine and a derivative thereof. The invention is realized through the following method: PEG is adopted as the reaction medium and the reaction catalyst, the amine and the derivative thereof and various sulfonyl chloride are added into a reactor to react under 20 to 80DEG C; and after the reaction, the materials are cooled to room temperature, a reaction system is extracted by anhydrous ether, an ether layer is dried by anhydrous sodium sulfate, filtered, depressed and concentrated to obtain corresponding sulfonamide products. The invention is characterized by simple process, cheap and easily available catalyst, environment-friendliness, easy industrial production and the like.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to the Sulphonylation method of a kind of amine and derivative thereof.
Background technology
Sulphonamide is the crucial compound of a class in pharmacy field, because it has good pharmacologically active, extensively uses as antitumor, anti-inflammatory, antiviral.In addition, sulfamide compound can also be used as thermo-responsive recording materials, sensitizing agent, development etc.Why sulphonamide is one of the blocking group of the derivative of the most stable amine and amine, because it is easy to be introduced into, and can reduce the alkalescence of nitrogen-atoms.The acid amides that obtains all is a crystal in most cases, has very strong chromophoric group, and is all very stable to a lot of reaction conditionss such as alkaline hydrolysis and catalytic reduction.Traditional synthetic method generally all is in the presence of alkali (as sodium bicarbonate, pyridine, triethylamine and sodium hydride etc.), in organic solvent (as CH
2Cl
2With DMF etc.) in add SULPHURYL CHLORIDE and amine, reaction generates sulphonamide [(a) Coeffard V.; Thobie-Gautier C.; Beaudet I.; LeGrognec E.; Quintard J.P.Eur.J.Org.Chem.2008,383-91; (b) HolmesT.J.; Lawton R.G.J.Org.Chem.1983,48,3146-3150; (c) Scully F.E.; Bowdring K.J.Org.Chem.1981,46,5077-5081; (d) Pandya R.; MurashimaT.; Tedeschi L.; Barrett A.G.M.J.Org.Chem.2003,68,8274-8276; (e) Su B, Landini S, Davis D.D.Brueggemeier R.W.J.Med.Chem.2007,50,1635-1644; (f) Natarajan A; Guo Y.H; Harbinski F.; Fan Y.H.; Chen H.; Luus L.; Diercks J.J.Med.Chem.2004,47,4979-4982; (g) Gavernet L.; Barrios I.A.; Sella Cravero M.Bioorganic ﹠amp; Medicinal Chemistry.2007,15,5604-614; (h) Purushottamachar P.; Khandelwal A.; Vasaitis T.S.; Bruno R.D.; Gediya L.K.; Njar VCO.Bioorganic ﹠amp; Medicinal Chemistry, 2008,16,3519-3529].
These methods need improve temperature usually, particularly for the substrate of the lower phenyl amines of reactive behavior, and [the Hiroya K. that also needs the very long reaction times that has; Matsumoto S.; Sakamoto T.Org.Lett.2004,6,2953-2956].For primary amine, then there is the side reaction of two sulfonylations, and separates relatively difficulty.In this case, the hydrolysis of SULPHURYL CHLORIDE is main competing reaction, the reduction that this just needs the excessive SULPHURYL CHLORIDE of adding and causes productive rate.
Yet traditional synthetic method generally need be carried out in organic solvent, or adding alkali comes catalyzed reaction.This often needs equipment to have higher anti-corrosion capability for large-scale industrial production, and considers from the angle of environmental protection, is not very good.Therefore, seek the approach that can under mild conditions, effectively synthesize sulphonamide and just become the target that the organic chemist pursues all the time.
Nearly rice, water is subjected to paying attention to widely because of inexpensive, safety and environmental friendliness.Deng Xiaohu has reported under the room temperature and has passed through Na
2CO
3Regulate pH value of aqueous solution and the method for synthetic sulphonamide.This method obtains higher yield [Deng X.H. by simple acidifying and filtering method purifying; Mani N.S.GreenChemistry 2006,8,835-38].
Employing beta-cyclodextrins such as Sridhar R. are catalyzer, are substrate at aqueous phase with various amine and amino acid, have synthesized the product of single sulfonylation, and reaction has good universality [Sridhar R.; Srinivas B.; Pavan Kumar V.; Narender M.; Rama Rao K.Adv.Synth.Cata.2007,349,1873-1876].
R
1＝Ts?or?Ms
Equally, microwave radiation promotes organic synthesis down also to become the focus of chemist's concern in recent years, it have the reaction times short, productive rate is high, simple operation and other advantages.Sharma and Wang Yulu reported respectively and do not added any other alkali, generates the method for sulphonamide in SULPHURYL CHLORIDE of following short period of microwave radiation and amine reaction.[(a) Sharma A, K.; Das S.K.Synth.Commun.2004,34,3807-819; (b) Wang Yulu, Zhao Na, Wang Jinye, Ma Huiqiang, He'nan Normal University's journal (natural science edition) .2005,33,77-79].
In addition, research such as Ahmad R.Massah has also been reported the synthetic method of the synthetic N-aryl benzsulfamide of solid-state grinding, is reflected at and carries out under the room temperature solvent-free condition, and the product separation and purification is easy, and can obtain good yield [Massah A.R.; Azadi D.; Aliyan H.; Momeni A.R.; Naghash H.J.; Kazemi F.Monatsh Chem 2008,139,233-40].
Although microwave, solid-state grinding and water react have its advantage separately, microwave is difficult to be applied to large-scale industrial production at present, and polishing also only is suitable for some active solid reaction.Though water react comparison environmental protection still needs to add catalyzer such as alkali or beta-cyclodextrin, does not reach real environmental protection.
Summary of the invention
The objective of the invention is toxic for catalysts and solvent in the sulfonylation of the derivative that solves amine and amine, the also generation side reaction and the aftertreatment that have are loaded down with trivial details; can not be applied to shortcomings such as industrial production; we provide a kind of simple, effectively, catalysts is cheap, be easy to get and the Sulphonylation method of the derivative of environment amenable amine and amine, for use in suitability for industrialized production.Specifically realize by following technical scheme:
The mol ratio (optimum proportion is 1: 1.2) of amine and SULPHURYL CHLORIDE 1: 0.2～5 is added in the reaction flask, add a certain amount of PEG simultaneously, under 20～80 ℃, finish reaction as reaction medium and catalysts.TLC detects, and reaction is cooled to room temperature after finishing, and reaction system extracts with anhydrous diethyl ether, and ether layer filters behind anhydrous sodium sulfate drying, and concentrating under reduced pressure obtains desired product.Wherein, PEG comprises: from PEG-200 to PEG-600; The derivative of amine and amine comprises: the aromatic amine of various replacements, aliphatic amide, aminosugar or derivatives thereof; SULPHURYL CHLORIDE comprises: benzene sulfonyl chloride, Tosyl chloride, to nitre benzene sulfonyl chloride and methylsulfonyl chloride etc.The ratio of the amount of substance of PEG, reactant can be any than (optimum proportion adds 2mL PEG for the 1mmol reactant), and temperature of reaction is 20 ℃～80 ℃.Its reaction equation is:
(R
2SO
2-=PhSO
2-, Ts-, Ns-, Ms-etc.; R
1=Ph, p-CH
3Ph, p-BrPh, PhCH
2Deng)
What be worth to indicate is, makes reaction medium with PEG, need not to add alkali such as anhydrous sodium bicarbonate or triethylamine and comes catalyzed reaction.
Embodiment
In order further to understand summary of the invention, characteristics and effect of the present invention, exemplify following example now:
Embodiment 1: aniline and the Tosyl chloride mol ratio by 1: 1.2 is added in the reaction flask, and [optimum proportion is that the 1mmol reactant adds 2mL PEG as reaction medium and catalysts to add a certain amount of PEG-200 or PEG-400 or PEG-600.Such as: aniline 1mmol, Tosyl chloride 1.2mmol, PEG-4002mL (roughly the same following)] reaction at room temperature, finished in 5 minutes.After reaction finished, reactant extracted with anhydrous diethyl ether, and ether layer is behind anhydrous sodium sulfate drying, and concentrating under reduced pressure obtains thick product.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 93% (PEG-200), 95% (PEG-400), 85% (PEG-600), m.p.:101～102 ℃.
PEG after it reclaims can be repeatedly used, and productive rate there is no obvious reduction (roughly the same following).
Embodiment 2: with aniline 1mmol, Tosyl chloride 1.2mmol adds in the 25mL flask, adds PEG-4001mL, 1.5mL, 2.0mL and 2.5mL simultaneously respectively as reaction medium and catalysts, at room temperature reacts 5 minutes.After reaction finished, reactant extracted with anhydrous diethyl ether, and ether layer is behind anhydrous sodium sulfate drying, and concentrating under reduced pressure obtains thick product.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 86% (1: 1), 91% (1: 1.5), 95% (1: 2), 92% (1: 2.5).(optimum proportion adds 2mL PEG for the 1mmol reactant)
Embodiment 3: with aniline and Tosyl chloride respectively by the mol ratio of 1: 0.2,1: 0.5,1: 2 and 1: 5, PEG-4002mL adds in the 25mL flask, at room temperature reacted 5 minutes, reacted 4 minutes down at 40 ℃, reacted 3 minutes down at 60 ℃, reaction was cooled to room temperature (reaction of heating) in 2 minutes then under 80 ℃.After reaction finished, reactant extracted with anhydrous diethyl ether, and ether layer is behind anhydrous sodium sulfate drying, and concentrating under reduced pressure obtains thick product.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 95% (r.t.), 90% (40 ℃), 92% (60 ℃), 92% (80 ℃).
Embodiment 4: with aniline 1mmol, and benzene sulfonyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 5 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white crystals 1).Productive rate: 90%; M.p.:109～110 ℃.
Embodiment 5: with aniline 1mmol, and p-nitrophenyl SULPHURYL CHLORIDE 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 50 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain little yellow solid 1).Productive rate: 77%; M.p.:169～170 ℃.
Embodiment 6: with benzylamine 1mmol, and p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 7 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 90%; M.p.:112～113 ℃.
Embodiment 7: will be to monomethylaniline 1mmol, and p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 6 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 89%; M.p.:114～115 ℃.
Embodiment 8: with para-bromoaniline 1mmol, p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL add in the 25mL flask, and room temperature reaction 5 minutes, after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain pale yellow thick liquid 1).Productive rate: 88%.
Embodiment 9: with n-Butyl Amine 99 1mmol, and p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 4 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain colourless liquid 1).Productive rate: 90%.
Embodiment 10: morpholine 1mmol, and p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 4 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 98%, m.p.:147～148 ℃.
Embodiment 11: phenylalanine ethyl ester 1mmol, and Tosyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 10 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 66%, m.p.:73～74 ℃.
Embodiment 12: aniline 1mmol, and Methanesulfonyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 10 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain weak yellow liquid 1).Productive rate: 84%.
Embodiment 13: para-fluoroaniline 1mmol, and Methanesulfonyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 10 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain filbert crystallization 1).Productive rate: 92%, m.p.:101～102 ℃.
Embodiment 14: meta-aminotoluene 1mmol, and Methanesulfonyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 12 minutes, and after reaction finished, reactant extracted with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=4: obtain white, needle-shaped crystals 1).Productive rate: 89%, m.p.:88～89 ℃.
Embodiment 15: with 6-amido-6-deoxidation-1,2:3,4-O-diisopropylidene-D-galactopyranose 1mmol, Methanesulfonyl chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 25 minutes, after reaction finishes, reactant extracts with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=2: obtain white, needle-shaped crystals 1).Productive rate: 90%, m.p.:164～166 ℃.
Embodiment 16: with 6-amido-6-deoxidation-1,2:3,4-O-diisopropylidene-D-galactopyranose 1mmol, p-methyl benzene sulfonic chloride 1.2mmol, PEG-4002.0mL adds in the 25mL flask, at room temperature reacts 20 minutes, after reaction finishes, reactant extracts with anhydrous diethyl ether, obtains thick product behind the concentrating under reduced pressure.Crude product is handled (V through column chromatography
Sherwood oil: V
Ethyl acetate=2: obtain white, needle-shaped crystals 1).Productive rate: 89%, m.p.:73～74 ℃.
Top embodiment can make the present invention of those skilled in the art complete understanding, but does not limit the present invention in any way.
Claims (5)
1. the Sulphonylation method of amine and derivative thereof; it is characterized in that: with PEG is reaction medium and catalysts; amine and derivative thereof and various SULPHURYL CHLORIDE are added in the reactor by 1: 0.2～5 mol ratio; 20～80 ℃ of reactions down, reaction is cooled to room temperature after finishing; reaction system extracts with anhydrous diethyl ether; ether layer filters behind anhydrous sodium sulfate drying, and concentrating under reduced pressure obtains corresponding sulphonamide product.
2. the Sulphonylation method of a kind of amine according to claim 1 and derivative thereof is characterized in that: PEG is: from PEG-200 to PEG-600; Amine with and derivative be: the aromatic amine of various replacements, aliphatic amide, aminosugar or their derivative; SULPHURYL CHLORIDE is: benzene sulfonyl chloride, Tosyl chloride, to nitre benzene sulfonyl chloride and methylsulfonyl chloride.
3. the Sulphonylation method of a kind of amine according to claim 1 and derivative thereof is characterized in that: the mol ratio of amine and derivative thereof and various SULPHURYL CHLORIDE is 1: 1.2.
4. the Sulphonylation method of a kind of amine according to claim 1 and derivative thereof is characterized in that: PEG is any ratio with the ratio of the amount of substance of reactant, and optimum proportion adds 2mL PEG for the 1mmol reactant.
5. the Sulphonylation method of a kind of amine according to claim 1 and derivative thereof, it is characterized in that: reaction equation is as follows:
Wherein: R
2SO
2-=PhSO
2-, Ts-, Ns-, Ms-; R
1=Ph, p-CH
3Ph, p-BrPh, PhCH
2
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| BRPI0111255B1 (en) * | 2000-06-05 | 2015-08-18 | Fmc Corp | Process for the preparation of a sulfonamide |
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| CN109096152A (en) * | 2018-07-31 | 2018-12-28 | 乐平市赛复乐医药化工有限公司 | The preparation method of one inter-species Methanesulfomide base aniline |
| CN109096152B (en) * | 2018-07-31 | 2021-01-08 | 乐平市赛复乐医药化工有限公司 | Preparation method of m-methanesulfonamido aniline |
| CN109020924A (en) * | 2018-10-24 | 2018-12-18 | 湖南农业大学 | Method for synthesizing benzene sulfonamide compound from benzene sulfonyl chloride compound and secondary amine through metal-free catalysis |
| CN109020924B (en) * | 2018-10-24 | 2022-05-13 | 湖南农业大学 | Method for synthesizing benzene sulfonamide compound from benzene sulfonyl chloride compound and secondary amine through metal-free catalysis |
| CN109298092A (en) * | 2018-11-01 | 2019-02-01 | 常州合全药业有限公司 | Detect the HPLC method of sulfonyloxy methyl chlorinity in industrial wastes |
| CN109298092B (en) * | 2018-11-01 | 2021-07-20 | 常州合全药业有限公司 | HPLC method for detecting content of methylsulfonyl chloride in industrial waste liquid |
| CN109456231A (en) * | 2018-12-13 | 2019-03-12 | 临海市奥特休闲用品股份有限公司 | A kind of preparation method of 2- nitro-chlorobenzene -4- sulfonamide |
| CN111548291A (en) * | 2020-05-27 | 2020-08-18 | 山东阳谷华泰化工股份有限公司 | Environment-friendly synthetic method of scorch retarder N-phenyl-N-trichloromethylthio benzenesulfonamide |
| CN111548291B (en) * | 2020-05-27 | 2022-06-21 | 山东阳谷华泰化工股份有限公司 | Environment-friendly synthetic method of scorch retarder N-phenyl-N-trichloromethylthio benzenesulfonamide |
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