CN103553860B - Method for synthesizing sulfamide compounds - Google Patents
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- CN103553860B CN103553860B CN201310536289.4A CN201310536289A CN103553860B CN 103553860 B CN103553860 B CN 103553860B CN 201310536289 A CN201310536289 A CN 201310536289A CN 103553860 B CN103553860 B CN 103553860B
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Abstract
The invention relates to a method for preparing sulfamide compounds. The method comprises the following steps: reacting a nitryl compound with sulfinic acid or salt thereof in the presence of a composite catalytic system of copper catalyst/organic borate; adding quaternary ammonium salt promoter to promote the reaction, so that the reaction time is remarkably shortened, and the sulfamide compounds can be prepared with high yield. The method has the remarkable advantages of high reaction yield, strong universality and the like, is low in reaction temperature and short in time, and has excellent industrial prospect and industrial enlargement value.
Description
Technical field
The present invention relates to the preparation method of pharmaceutical synthesis field sulfamide compound, relate more specifically to a kind of method of-sulfinate and nitro-compound Reactive Synthesis sulfamide compound under copper catalyst/organic boric acid ester composite catalyst system effect.
Background technology
Sulfamide compound, as the very important pharmaceutical intermediate of one, has now been widely used in the field such as biological medicine, organic synthesis, and sulfonamide structure is also prevalent among pharmaceutical preparation.According to statistics in 2011, before world rankings 100 medicine in have the applied medicine of 10% need containing the minor structure of sulphonamide nearly.Therefore, sulphonamide has become one of important construction unit of medicine and bioactive compounds.Traditional sulphonamide synthetic method adopts acyl chlorides and amine to react the synthesis realizing sulphonamide, but adopts SULPHURYL CHLORIDE often to cause raw material to be difficult to the shortcoming of preserving, response stimulus is strong as raw material, makes the method leave hidden danger in amplificationization is produced.In addition, usually adopt the electrophilic aromatic substitution reaction of (1) chlorsulfonic acid and the oxidation chlorination of (2) organosulfur compound in the synthesis of precursor SULPHURYL CHLORIDE, these reactions relate to harsh reaction conditions and poisonous reaction reagent etc. and limit its application.As can be seen here, develop a kind of high yield, the synthetic method of sulfamide compound that universality is strong be vast organic chemistry, a urgent difficult problem that pharmaceutical synthesis researchist faces.
About the synthetic method of sulfamide compound or technique have many relevant reports in prior art, such as:
Tang Xiaodong etc. (" Copper-catalyzed sulfonamides formation from sodium sulfinates and amines ", Chem.Commun, 2013,49,6102-6104) disclose a kind of synthetic method of sulphonamide.Described method with-sulfinate and amine be raw material, with oxygen or methyl-sulphoxide for oxygenant, under the effect of copper catalyst, prepare corresponding sulfonamide compounds through oxidative coupling reaction.
J.Robb DeBergh etc. (" Synthesis of Aryl Sulfonamides via Palladium-Catalyzed Chlorosulfonylation of Arylboronic Acids ", J.Am.Chem.Soc., 2013,135,10638-10641) disclose a kind of preparation method of sulphonamide.Described method be aryl boric acid occur under palladium catalyst effect chlorosulfonylation reaction prepare sulfonyl chloride intermediate; and then generate corresponding sulphonamide to amine reaction in－situ; this reaction conditions is gentle, raw material is easy to get, but needs to use expensive palladium chtalyst reagent, is difficult to industrialization.
J.S.Yadav etc. (" Iodine-catalyzed ontermolecular hydroamination of vinylarenes ", Tetrahedron letters, 2009,50,5351-5353) disclose a kind of synthetic method of sulphonamide, it adopts iodine to be solvent as catalyzer, toluene, makes benzsulfamide and vinylbenzene react 2.5 hours at 110 DEG C, can obtain the yield of 90%, but this temperature of reaction is high, alkene is easy to polymerization and causes by product to increase.
The preparation method that application discloses a kind of sulphonamide of CN102675163A.It passes through-sulfinic acid or-sulfinate and nitro-compound under atmosphere of inert gases, take copper compound as the preparation that catalyzer achieves sulphonamide.But the method has specificity for the combination of catalyst/solvent, even if adopt identical copper compound catalyzer, and due to the difference of solvent all can the huge deviation of inducing reaction property, cause product yield difference huge, even cannot carry out, above-mentioned reason makes the method narrow application range, universality poor, is difficult to industrial applications.
Organoboron reagent is usually in the middle of the reaction of catalytic preparation of amide, such as: boric acid and aryl boric acid the reaction of directly catalysis carboxylic acid and amine can carry out synthesizing amide [see H.Charville, D.Jackson, G.Hodges and A.Whiting, Chem.Commun., 2010,46,1813 – 182].But these usually react long reaction time, condition is harsh.In addition, yet there are no organoboron reagent in prior art to react for catalysis-sulfinate and nitro-compound and prepare the relevant report of sulphonamide.
The many defects existed for prior art and the specificity feature of organic catalytic reaction, the present invention is intended to searching one, and cost is low, yield is high, be suitable for the novel processing step of the sulfamide compound of suitability for industrialized production, to meet the demand of vast medical synthetic work person, and realize Economic concept that is green, environmental protection.
Summary of the invention
For many defects of above-mentioned existence, the present inventor, after having paid a large amount of creative works, develops a kind of novel processing step of sulfamide compound through further investigation.Surprisingly, the present invention adopts composite catalyst system (copper catalyst/organoboron reagent composite catalyst system, "/" wherein represents " with " relation), and carry out suitable and reasonably processing parameter select and achieve beyond thought technique effect.The method of the invention has the plurality of advantages such as reaction yield is high, cost is low, universality is good, has good industrialization prospect.
Specifically, the invention provides the preparation method of sulfamide compound shown in a kind of formula (I),
Described method comprises: under the composite catalyst system effect of copper catalyst/organic boric acid ester, and formula (II) compound and formula (III) compound react in organic solvent,
Wherein, R
1, R
2be selected from independently of one another with substituting group or unsubstituted C
1-C
6alkyl, with substituting group or unsubstituted C
1-C
6alkoxyl group, with substituting group or unsubstituted C
5-C
12aryl or with substituting group or unsubstituted C
4-C
12heteroaryl; Described C
5-C
12aryl or C
4-C
12heteroaryl is phenyl, naphthyl, pyridyl, pyrryl, thienyl or furyl; Described substituting group is halogen, C
1-C
6alkyl, C
1-C
6alkoxyl group; Described substituting group is preferably halogen, methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl, methoxy or ethoxy;
M is H, NH
4 +or metallic cation; Be preferably H, NH
4 +, alkali metal cation or alkaline earth metal cation; Be more preferably H, NH
4+, Li
+, Na
+, K
+, Ru
+or Cs
+.
In described method of the present invention, halogen atom refers to fluorine, chlorine, bromine or iodine atom.
In described method of the present invention, C
1-C
6alkyl refers to the alkyl with 1-6 carbon atom, and it can be straight or branched, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl etc. in non-limiting manner.
In described method of the present invention, C
1-C
6alkoxyl group then refers to " C defined above
1-C
6alkyl " be connected with O atom after group.
In described method of the present invention, organic solvent when formula (II) and (III) react is not particularly limited, can be in organic synthesis field any Conventional solvents used, such as can be benzene in non-limiting manner, toluene, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetonitrile, methyl-phenoxide, dioxane, ethylene dichloride, methylene dichloride, trichloromethane, tetracol phenixin, normal hexane, tetrahydrofuran (THF) (THF), ether, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, amylalcohol, one or more in hexanol etc., be preferably toluene, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), acetonitrile, methyl-phenoxide, dioxane, tetrahydrofuran (THF), trichloromethane.
In described method of the present invention, described formula (II) is 1-2.5:1 with the mol ratio of formula (III) compound, this scope includes any sub-range scope wherein, as 1.1-2.4:1,1.2-2.3:1,1.3-2.2:1,1.4-2.1:1,1.5-2.0:1,1.6-1.9:1, also include any concrete point value wherein, exemplarily such as can be 1.1:1,1.2:1,1.4:1,1.6:1,1.8:1,2:1,2.2:1,2.4:1 or 2.5:1.
In described method of the present invention, described copper catalyst is elemental copper or copper compound, is preferably Cu, CuCl
2, CuCl, CuBr
2, CuBr, CuI
2, CuI, CuCO
3, Cu (OTf)
2, CuOAc or Cu (OAc)
2in any one.
In described method of the present invention, described organic boric acid ester is trimethyl borate, triethyl borate, triethanolamine borate, B (OCH
2cF
3)
3in any one.
In described method of the present invention, the mole dosage of described copper catalyst is the 0.5-5% of both integral molar quantities of (II) and (III), this scope includes any sub-range scope wherein, as 1-4%, 2-3%, also include any concrete point value wherein, exemplarily such as can be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% of both integral molar quantities of (II) and (III).
In described method of the present invention, the mol ratio of described copper catalyst and organic boric acid ester is 1:1-2, such as, can be 1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:2.0.
Preferably, react and carry out under atmosphere of inert gases, described rare gas element is any one in nitrogen, argon gas.
More preferably, except the above-mentioned copper catalyst of use and organic boric acid ester, also in reaction system, promotor can be added further, described promotor is quaternary ammonium salt, can be any one in benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride in non-limiting manner.When adding promotor, unexpectedly further shorten the reaction times.Wherein in mass, promotor can be 1-3:1 with the ratio of copper catalyst, as 1:1,1.5:1,2:1,2.5:1 or 3:1, and preferred 2-1:1.
In described method of the present invention, reaction times, there is no particular limitation, such as by liquid chromatographic detection object product or raw material residual percentage and determine the suitable reaction times, it typically is 1-18 hour, is such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours or 18 hours in non-limiting manner.
In described method of the present invention, temperature of reaction is 60-120 DEG C, such as can be 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C in non-limiting manner.
Reaction terminates, and after obtaining crude product, conventional means can be adopted to purify, such as, reaction system can be cooled to room temperature, cross that silica gel chromatographic column is separated, evaporation removing eluting solvent, vacuum-drying and obtain desired sulfonyl amine product
The present invention is by using the composite catalyst system of copper catalyst/organic boric acid ester, and preferably add promotor further, and effectively make formula II and III compound react, thus high yield prepare sulfamide compound, and have reaction temperature and, the plurality of advantages such as universality is good, there is good prospects for commercial application and marketable value.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
Embodiment 1
60ml N-Methyl pyrrolidone, 8mmol oil of mirbane is added successively in 100ml flask, and 10mmol is to methyl sodium benzene sulphinate, the 0.09mmol cuprous chloride of two kinds of reaction raw materials integral molar quantities 5% and the trimethyl borate of 0.09mmol is incorporated as under heated and stirred, in 80 DEG C, stirring reaction 10h under nitrogen atmosphere, be cooled to room temperature after completion of the reaction, cross silica gel chromatographic column separation, evaporate removing eluting solvent, vacuum-drying obtains desired sulfonyl amine product, and yield is 95%.
1H-NMR(CDCl
3,300MHz)δ：2.41(s,3H)，4.12(s,1H)，6.70(d,2H)，6.91(t,1H)，7.18(d,2H)，7.42(d,2H)，7.81(d,2H)。
MS m/z：247.09(M+1,100)。
Embodiment 2
50ml N-Methyl pyrrolidone, 10mmol is added successively to methoxy nitrobenzene in 100ml flask, and 12mmol is to methyl sodium benzene sulphinate, 0.66mmol cuprous chloride and the 0.99mmol triethyl borate of two kinds of reaction raw materials integral molar quantities 3% is incorporated as under heated and stirred, in 100 DEG C, stirring reaction 10h under nitrogen atmosphere, be cooled to room temperature after completion of the reaction, cross silica gel chromatographic column separation, evaporate removing eluting solvent, vacuum-drying obtains desired sulfonyl amine product, and yield is 92%.
1H-NMR(CDCl
3,300MHz)δ：2.40(s,3H)，3.79(s,3H)，4.09(s,1H)，6.68(d,2H)，6.97(d,2H)，7.39(d,2H)，7.76(d,2H)。
MS m/z：277.10(M+1,100)。
Embodiment 3
75ml N-Methyl pyrrolidone, 12mmol is added successively to methoxy nitrobenzene in 100ml flask, and 24mmol is to chlorobenzene sulfinic acid sodium, 1.44mmol cuprous chloride and the 2.88mmol triethanolamine borate of two kinds of reaction raw materials integral molar quantities 4% is incorporated as under heated and stirred, in 120 DEG C, stirring reaction 15h under nitrogen atmosphere, be cooled to room temperature after completion of the reaction, cross silica gel chromatographic column separation, evaporate removing eluting solvent, vacuum-drying obtains desired sulfonyl amine product, and yield is 91%.
1H-NMR(CDCl
3,300MHz)δ：3.81(s,3H)，4.05(s,1H)，6.70(d,2H)，7.02(d,2H)，7.59(d,2H)，7.78(d,2H)。
MS m/z：297.06(M+1,100)。
Embodiment 4
In 100ml flask, once add 55ml N-Methyl pyrrolidone, 6mmol4-nitropyridine, and 9mmol is to methyl sodium benzene sulphinate, under heated and stirred, is incorporated as 0.3mmol cuprous chloride and the 0.6mmol B (OCH of two kinds of reaction raw materials integral molar quantities 2%
2cF
3)
3, in 110 DEG C, stirring reaction 12h under nitrogen atmosphere, be cooled to room temperature after completion of the reaction, cross that silica gel chromatographic column is separated, evaporation removing eluting solvent, vacuum-drying obtains desired sulfonyl amine product, and yield is 93%.
1H-NMR(CDCl
3,300MHz)δ：2.38(s,3H)，4.06(s,1H)，7.04(d,2H)，7.43(d,2H)，7.80(d,2H)，8.51(d,2H)。
MS m/z：248.11(M+1,100)。
Embodiment 5
65ml N-Methyl pyrrolidone is once added in 100ml flask, 8mmol oil of mirbane, and 12mmol methyl-sulfinic acid sodium, 0.2mmol cuprous chloride and the 0.2mmol trimethyl borate of two kinds of reaction raw materials integral molar quantities 1% is incorporated as under heated and stirred, in 90 DEG C, stirring reaction 16h under nitrogen atmosphere, be cooled to room temperature after completion of the reaction, cross silica gel chromatographic column separation, evaporate removing eluting solvent, vacuum-drying obtains desired sulfonyl amine product, and yield is 94%.
1H-NMR(CDCl
3,300MHz)δ：2.97(s,3H)，4.07(s,1H)，6.71(d,2H)，6.85(t,1H)，7.23(d,2H)。
MS m/z：171.08(M+1,100)。
Embodiment 6-13
Carried out embodiment 6-13 with the same way of embodiment 1 respectively, difference part is to adopt different reaction solvents.Concrete outcome sees the following form 1.
Table 1. adopts the product yield under different solvents
Embodiment 14-23
Carried out embodiment 14-23 with the same way of embodiment 1 respectively, difference part is to adopt different catalyst system, and concrete outcome sees the following form 2.
Table 2. adopts the product yield under different copper catalysts
Embodiment 24-29
Carried out embodiment 24-29 with the same way of embodiment 1 respectively, difference part is also in reaction system, to add different promotors, and wherein the mass ratio of promotor and copper catalyst and cuprous chloride is as follows respectively:
Embodiment 24 is 1:1; Embodiment 25 is 2:1; Embodiment 26 is 3:1; Embodiment 27 is 1.5:1; Embodiment 28 is 2.5:1; Embodiment 29 is 3:1.
Adopt gas-chromatography-liquid chromatography coupling assaying reaction yield, concrete outcome sees the following form 3.
Table 3. adopts the product yield under different promotor
As can be seen here:
Copper catalyst/organic boric acid ester catalyst system is applied to nitro-compound and-sulfinate reacts the reaction type preparing sulphonamide, draws following result through large quantity research:
1, from above-described embodiment 1-5, adopt copper catalyst, and when adding various different organic boric acid ester, reaction all obtains high yield (>91%), confirms the excellent catalytic performance of copper catalyst/organic boric acid ester system.
2, can be found out by above-mentioned table 1, adopt cuprous chloride/this reaction of trimethyl borate catalysis, react under differential responses solvent and all can carry out, and achieve suitable high yield, and yield reaches as high as 93%;
3, can be found out by above-mentioned table 2, when adopting different copper catalysts, product yield is all kept, and confirms that sulphonamide is prepared in the catalysis of various copper compound or the high yield of the equal energy of simple substance under the cooperation of organic boric acid ester.
4, can be found out by above-mentioned table 3, when adding various quaternary ammonium salt promotor in reaction system, not only increase yield, and obviously shorten the reaction times, the reaction times shortens half at most.
Therefore, method of the present invention compared with prior art, by the use of copper catalyst/organic boric acid ester catalyst system, not only makes reaction yield high, and makes various copper catalyst, reaction solvent all can be practical, thus expands the scope of application of reaction; In addition, significantly reducing time of reaction by introducing quaternary ammonium salt promotor, achieving beyond thought technique effect, for the amplification of sulfamide compound or suitability for industrialized production, there is very strong industrial prospect and economic benefit.Although organic catalytic reaction has certain not predictability, but the present inventor investigated the preparation method of a kind of high yield, sulfamide compound that universality is strong through a large amount of creative works, and create obvious positively effect, there is investigation and application significantly and be worth.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (4)
1. a preparation method for sulfamide compound shown in formula (I),
Described method comprises: under the composite catalyst system effect of copper catalyst/organic boric acid ester, and formula (II) compound and formula (III) compound react in organic solvent,
Wherein, R
1be selected from unsubstituted C
1-C
6alkyl or with substituent phenyl, R2 is selected from substituting group or unsubstituted phenyl or unsubstituted pyridyl; Described substituting group is halogen, C
1-C
6alkyl, C
1-C
6alkoxyl group;
M is Na
+;
Described organic solvent is the one in toluene, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dimethyl formamide, acetonitrile, methyl-phenoxide, dioxane, trichloromethane, tetrahydrofuran (THF);
Described copper catalyst is Cu, CuCl
2, CuCl, CuBr
2, CuBr, CuI
2, CuI, CuCO
3, Cu (OTf)
2, CuOAc or Cu (OAc)
2in any one;
Described organic boric acid ester is trimethyl borate, triethyl borate, triethanolamine borate, B (OCH
2cF
3)
3in any one.
2. the preparation method of sulfamide compound shown in a kind of formula (I) according to claim 1, is characterized in that: formula (II) is 1-2.5:1 with the mol ratio of formula (III) compound.
3. the preparation method of sulfamide compound shown in a kind of formula (I) according to claim 1 or 2, is characterized in that: the mole dosage of described copper catalyst be (II) and the 0.5-5% of integral molar quantities both (III); The mol ratio of described copper catalyst and organic boric acid ester is 1:1-2.
4. the preparation method of sulfamide compound shown in a kind of formula (I) according to claim 1 or 2, it is characterized in that: except the above-mentioned copper catalyst of use and boric acid ester, also in reaction system, add promotor further, described promotor is any one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride; Wherein in mass, promotor is 1-3:1 with the ratio of copper catalyst.
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| CN104628606A (en) * | 2015-02-06 | 2015-05-20 | 王桦 | Preparation method of sulfohydrazide compound |
| CN108440345B (en) * | 2018-04-08 | 2020-11-24 | 西北师范大学 | Preparation method of sulfonamide compound |
| CN110372463B (en) * | 2019-07-12 | 2020-06-30 | 浙江大学 | Method for synthesizing sulfonamide compound by coupling of nitroaromatic and boric acid compound |
| CN111170905B (en) * | 2019-12-28 | 2022-04-29 | 台州学院 | Synthetic method of sulfonamide compound |
| CN114057616B (en) * | 2021-11-12 | 2023-04-25 | 温州大学 | Method for synthesizing N-substituted benzene sulfonamide compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3934972A (en) * | 1973-04-25 | 1976-01-27 | Imperial Chemical Industries Limited | Dyeing process |
| CN1159444A (en) * | 1995-11-14 | 1997-09-17 | 赫彻斯特股份公司 | Sulfuryl amino substituted benzoyl guanidine, preparation process and applications as medicine or diagnostic agent and the medicine containing same |
| CN1432003A (en) * | 2000-06-05 | 2003-07-23 | Fmc有限公司 | Process to prepare sulfonamides |
| CN102675163A (en) * | 2012-05-23 | 2012-09-19 | 湘潭大学 | Preparation method of sulfonamide |
-
2013
- 2013-11-03 CN CN201310536289.4A patent/CN103553860B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3934972A (en) * | 1973-04-25 | 1976-01-27 | Imperial Chemical Industries Limited | Dyeing process |
| CN1159444A (en) * | 1995-11-14 | 1997-09-17 | 赫彻斯特股份公司 | Sulfuryl amino substituted benzoyl guanidine, preparation process and applications as medicine or diagnostic agent and the medicine containing same |
| CN1432003A (en) * | 2000-06-05 | 2003-07-23 | Fmc有限公司 | Process to prepare sulfonamides |
| CN102675163A (en) * | 2012-05-23 | 2012-09-19 | 湘潭大学 | Preparation method of sulfonamide |
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