CN106565553A - Synthetic method of alkynyl sulfone derivative - Google Patents

Synthetic method of alkynyl sulfone derivative Download PDF

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CN106565553A
CN106565553A CN201610861769.1A CN201610861769A CN106565553A CN 106565553 A CN106565553 A CN 106565553A CN 201610861769 A CN201610861769 A CN 201610861769A CN 106565553 A CN106565553 A CN 106565553A
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synthetic method
acid
reaction
alkynyl
organic
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CN106565553B (en
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唐晓冬
戴晨舒
朱秋华
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Southern Medical University
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Southern Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides

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Abstract

The invention provides a synthetic method of an alkynyl sulfone derivative. The method is characterized in that alkynyl sulfone derivative is obtained through a reaction of alkynyl bromide and organic sodium sulfinate in the presence of an organic solvent and a strong acid used as a catalyst; and the organic solvent is one or more of toluene, chloroform, 1,2-dichloroethane, 1,4-dioxane and tetrahydrofuran. The method has the advantages of no use of complex reaction substrates or strong oxidants, simple and easily available reaction raw materials, safety and simplicity in reaction operation, environmentally-friendly reaction process, good substrate applicability, good function group tolerance, and high separation yield under preferable conditions and the alkynyl sulfone derivative synthesized through the method widely exists in natural products and medicine molecules, and also can be used as a very effective alkynylation reagent.

Description

A kind of synthetic method of alkynyl sulfone derivative
Technical field
The invention belongs to technical field of organic synthesis, is specifically designed a kind of new synthetic method of alkynyl sulfone derivative.
Background technology
Sulfone compound has quite varied biological medicine activity, is the weight of many bioactive molecules and natural product Want construction unit.Alkynyl sulfone is the important component part of sulfone compound, and its construction unit not only has biological activity, while alkynes Base sulfone or very important organic synthesiss of a class, are widely used in alkynylation reaction as alkynyl source.Just because of alkynes The importance of base sulfone compound, people are also studying always its synthetic method.(C.Kuhakarn,et al.J.Org.Chem.2016,81,2744–2752；X.Huang,et al.Tetrahedron Lett.2002,43,1059– 1061；N.Singh,et al.Org.Lett.2015,17,2656-2659；W.J.Moran,et Al.Org.Biomol.Chem.2014,12,4156-4162) now it has been reported that synthetic method mainly have：1st, high price iodine examination Agent and the coupling reaction of sulfuryl reagent；2nd, the oxidation of alkynyl sulfide；3rd, the oxidative coupling of end alkynes or acetylenic acid and sulfuryl reagent； 4th, elimination reaction of iodo thiazolinyl sulfone etc..But these methods all exist be not easy to obtain reaction raw materials, harsh reaction condition, Strong oxidizer such as uses at the defect.
Alkynes bromine is important organic synthesiss of a class, with prepare it is simple, react various the features such as.In recent years, based on alkynes The sense dough reaction of bromine is received significant attention.(J.K.Cha,et al.Org.Lett.2015,17,3854-3856； Y.Zhang,et al.J.Org.Chem.2009,74,4630–4633；M.Miura,et al.2009,11,4156-4159； H.Jiang,et al.Chem.Commun.2015,51,5894–5897).Simultaneously sulfinic acid sodium is used as a kind of comparatively gentle sulfone Base reagent, had also obtained vigorous growth with regard to its synthesis application in the last few years.(G.Manolikakes,et al.Org.Lett.2013,15,188-191；R.Prabhu,et al.J.Org.Chem.2014,79,8110-8117； S.B.Mhaske,et al.Org.Lett.2014,16,3836-3839；N.Taniguchi,J.Org.Chem.2015,80, 1764-1770).But there is no the report with regard to obtaining alkynyl sulfone using alkynes bromine and sulfinic acid sodium direct reaction so far, particularly Under conditions of redox-neutral.
The content of the invention
It is an object of the invention to overcome existing alkynyl sulfone synthesising method reacting condition harshness, need to use strong oxidizer Deng not enough, there is provided a kind of synthetic method of new alkynyl sulfone.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of synthetic method of alkynyl sulfone derivative, comprises the steps：
With alkynes bromine, organic sulfinic acid sodium as raw material, in the presence of strong acid as catalyst and organic solvent, reacted, obtained To the alkynyl sulfone derivative；
The organic solvent is any one in toluene, 1,2- dichloroethanes, chloroform, 1,4- dioxane, tetrahydrofuran Plant or several
Inventor has found, is raw material under the catalysis of strong acid with alkynes bromine, organic sulfinic acid sodium, and sulfone glycosylation reaction can occur, One-step synthesis alkynyl sulfone derivative.Organic solvent has significantly impact on the reaction, in some solvents, such as DMF, DMSO Under, generate without target product.
Preferably, the alkynes bromine is the alkynes bromine that aryl replaces；Preferably, the aryl is on phenyl or 2 and/or 4 Phenyl with substituent group, the substituent group is electron-donating group or electron withdraw group；Preferably, the substituent group be alkyl or Halogen；The alkyl is the alkyl of C1～4.
Preferably, organic sulfinic acid sodium is the sulfinic acid sodium that aryl replaces；Preferably, the aryl is phenyl or 2 Position and/or the phenyl of the substituted base of 4 upper bands, the substituent group is electron-donating group or electron withdraw group；Preferably, it is described to take Dai Jiwei alkyl or halogen；The alkyl is the alkyl of C1～4.
The reaction of the present invention can be carried out at a temperature of between room temperature and not higher than organic solvent boiling point, and yield has Fluctuated.Preferably, the temperature of the reaction is 25～80 DEG C.In this temperature range, higher yield is obtained in that.
Preferably, the alkynes bromine and the mol ratio of organic sulfinic acid sodium are 1:(1～3).
Preferably, H in the strong acid+It is 1 with the mol ratio of alkynes bromine:1.
Preferably, the strong acid is to appoint in hydrochloric acid, sulphuric acid, nitric acid, trifluoromethayl sulfonic acid, p-methyl benzenesulfonic acid or trifluoroacetic acid Anticipate one or more.The species of strong acid has an impact to the yield for reacting, it is preferable that the strong acid is hydrochloric acid.Preferably, the salt The concentration of acid is 1～8M, more preferably 1M.
Preferably, also including purification procedures after the completion of reaction, described isolating and purifying is toward reaction system, to add carbon Sour hydrogen sodium solution is simultaneously extracted with ethyl acetate, is collected organic faciess and is removed wherein moisture content and organic solvent successively, obtains thick Product, crude product is further separated by column chromatography.
Preferably, the column chromatography for separation adopts petroleum ether with ethyl acetate volume ratio for (5～20)：1 mixed solvent As eluent.
Preferably, the eluent is petroleum ether and ethyl acetate volume ratio is 10：1 mixed solution.
Compared with prior art, the present invention has advantages below and beneficial effect：
The invention provides a kind of synthetic method of new alkynyl sulfone derivative, this method avoid complex reaction substrate with And the use of strong oxidizer, reaction raw materials are simple and easy to get, and operation is safe and simple, course of reaction environmental friendliness, and substrate is suitable for Property it is good, functional group's tolerance is good, under the preferred conditions, separate yield it is higher；By the alkynyl sulphones of present invention synthesis In being not only widely present in natural product and drug molecule, and it is also used as a kind of very effective alkynyl reagent.
Specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment, but embodiment does not do any type of to the present invention Limit.Unless stated otherwise, reagent, the method and apparatus that the present invention is adopted is for the art conventional reagent, method and apparatus.
In 25 milliliters of reaction tubes, add 0.3mmol phenylacetylene bromines, 0.75mmol SPTS, in the condition of table 1 Under reacted, be cooled to room temperature, add sodium bicarbonate aqueous solution to be simultaneously extracted with ethyl acetate three times, magnesium sulfate is dried, decompression Revolving removes solvent, then by column chromatographic isolation and purification, obtains product, and it is 10 that column chromatography eluent used is volume ratio:1 Petroleum ether:Ethyl acetate mixed solvent.
Table 1
In example 1 below～16, product is prepared via a method which：
In 25 milliliters of reaction tubes, 0.3mmol alkynes bromines, 0.75mmol sulfinic acid sodium, the millis of 0.3mmol hydrochloric acid 1M and 3 are added The toluene for rising, stirring reaction stops heating and stirs after 12 hours under the conditions of 60 DEG C, is cooled to room temperature, adds sodium bicarbonate Aqueous solution is simultaneously extracted with ethyl acetate three times, and magnesium sulfate is dried, and vacuum rotary steam removes solvent, then by column chromatographic isolation and purification, Target product is obtained, it is 10 that column chromatography eluent used is volume ratio:1 petroleum ether:Ethyl acetate mixed solvent.Specifically adopt Alkynes bromine and sulfinic acid sodium are as shown in table 2：
Table 2
The characterize data of the compound of embodiment 1～16 is as follows：
Embodiment 1：1H NMR(400MHz,CDCl3) δ 7.96 (d, J=8.3Hz, 2H), 7.51 (d, J=7.1Hz, 2H), 7.46–7.44(m,1H),7.40-7.34(m,4H),2.46(s,3H).13C NMR(100MHz,CDCl3)δ145.3,138.9, 132.7,131.4,130.0,128.6,127.4,118.0,92.9,85.6,21.7。
Embodiment 2：1H NMR(400MHz,CDCl3) δ 7.95 (d, J=7.9Hz, 2H), 7.39 (t, J=8.7Hz, 4H), 7.16 (d, J=7.7Hz, 2H), 2.46 (s, 3H), 2.37 (s, 3H).13C NMR(100MHz,CDCl3)δ145.2,142.3, 139.1,132.7,129.9,129.4,127.4,114.9,93.7,85.2,21.8,21.7。
Embodiment 3：1H NMR(400MHz,CDCl3) δ 7.95 (d, J=8.0Hz, 2H), 7.43 (d, J=7.9Hz, 2H), 7.38 (d, J=8.0Hz, 2H), 7.19 (d, J=7.9Hz, 2H), 2.66 (q, J=7.6Hz, 2H), 2.46 (s, 3H), 1.20 (t, J=7.6Hz, 3H).13C NMR(100MHz,CDCl3)δ148.5,145.4,139.2,132.8,130.0,128.3, 127.4,115.1,93.7,85.3,29.0,21.7,15.0。
Embodiment 4：1H NMR(400MHz,CDCl3) δ 7.94 (d, J=8.2Hz, 2H), 7.53-7.50 (m, 2H), 7.39 (d, J=8.1Hz, 2H), 7.06 (t, J=8.4Hz, 2H), 2.46 (s, 3H).13C NMR(100MHz,CDCl3)δ164.3(d,J =254Hz), 145.5,138.8,135.0 (d, J=9Hz), 130.0,127.5,116.3 (d, J=22Hz), 114.1 (d, J= 4Hz),91.8,85.5,21.7。
Embodiment 5：1H NMR(400MHz,CDCl3) δ 7.95 (d, J=8.3Hz, 2H), 7.44 (d, J=8.4Hz, 2H), (7.39 d, J=8.1Hz, 2H), 7.34 (d, J=8.8Hz, 2H), 2.47 (s, 3H).13C NMR(100MHz,CDCl3)δ 145.5,138.7,138.0,133.9,130.0,129.1,127.5,116.4,91.5,86.4,21.7。
Embodiment 6：1H NMR(400MHz,CDCl3) δ 7.94 (d, J=8.1Hz, 2H), 7.51 (d, J=8.2Hz, 2H), 7.38 (t, J=9.3Hz, 4H), 2.47 (s, 3H).13C NMR(100MHz,CDCl3)δ145.6,138.7,133.9,132.1, 130.0,127.5,126.4,116.9,91.5,86.6,21.7。
Embodiment 7：1H NMR(400MHz,CDCl3) δ 7.96 (d, J=8.3Hz, 2H), 7.51-7.43 (m, 2H), 7.39 (d, J=8.3Hz, 2H), 7.17-7.07 (m, 2H), 2.46 (s, 3H).13C NMR(100MHz,CDCl3) δ 163.4 (d, J= 256Hz), 145.5,138.7,134.1,133.5 (d, J=8Hz), 130.0,127.5,124.3 (d, J=3Hz), 116.0 (d, ), J=20Hz 107.1 (d, J=15Hz), 90.0,86.6,21.7.
Embodiment 8：1H NMR(400MHz,CDCl3) δ 7.99 (d, J=8.0Hz, 2H), 7.55 (d, J=7.7Hz, 1H), 7.45–7.39(m,4H),7.30–7.27(m,1H),2.49(s,3H).13C NMR(100MHz,CDCl3)δ145.5,138.8, 137.5,134.3,132.4,130.0,129.7,127.5,126.7,118.5,89.8,89.4,21.7。
Embodiment 9：1H NMR(400MHz,CDCl3) δ 8.08 (d, J=8.8Hz, 2H), 7.71-7.67 (m, 1H), 7.62- 7.58 (m, 2H), 7.54-7.45 (m, 3H), 7.36 (t, J=7.6Hz, 2H).13C NMR(100MHz,CDCl3)δ141.8, 134.1,132.7,131.6,129.3,128.7,127.3,117.8,93.5,85.3。
Embodiment 10：1H NMR(400MHz,CDCl3) δ 7.99 (d, J=8.5Hz, 2H), 7.60 (d, J=8.5Hz, 2H), 7.53 (d, J=7.1Hz, 2H), 7.47 (t, J=7.7Hz, 1H), 7.37 (t, J=7.6Hz, 2H), 1.36 (s, 9H).13C NMR (100MHz,CDCl3)δ158.3,138.8,132.7,131.4,128.6,127.3,126.4,118.0,92.9,85.6, 35.4,31.0。
Embodiment 11：1H NMR(400MHz,CDCl3)δ8.15–8.06(m,2H),7.56–7.47(m,3H),7.42– 7.36(m,2H),7.32–7.27(m,2H).13C NMR(100MHz,CDCl3) δ 166.0 (d, J=250Hz), 137.9 (d, J= 3Hz), 132.7,131.7,130.4 (d, J=9Hz), 128.7,117.7,116.7 (d, J=23Hz), 93.7,85.2.
Embodiment 12：1H NMR(400MHz,CDCl3) δ 8.02 (d, J=8.6Hz, 2H), 7.57 (d, J=8.6Hz, 2H), 7.53 (d, J=7.3Hz, 2H), 7.48 (d, J=7.5Hz, 1H), 7.38 (t, J=7.5Hz, 2H).13C NMR(100MHz, CDCl3)δ141.0,140.3,132.8,131.7,129.7,128.9,128.7,117.6,94.0,85.0。
Embodiment 13：1H NMR(400MHz,CDCl3) δ 7.94 (d, J=8.8Hz, 2H), 7.74 (d, J=8.8Hz, 2H), 7.54–7.47(m,3H),7.40–7.36(m,2H).13C NMR(100MHz,CDCl3)δ140.8,132.8,132.7,131.7, 129.6,128.9,128.7,117.6,94.0,85.0。
Embodiment 14：1H NMR(400MHz,CDCl3) δ 7.88 (s, 2H), 7.53 (d, J=7.8Hz, 2H), 7.50-7.44 (m, 3H), 7.37 (t, J=7.5Hz, 2H), 2.47 (s, 3H).13C NMR(100MHz,CDCl3)δ141.7,139.7,135.0, 132.8,131.5,129.2,128.7,127.7,124.6,118.0,93.2,85.5,21.3。
Embodiment 15：1H NMR(400MHz,CDCl3) δ 8.21 (d, J=7.9Hz, 1H), 7.60-7.57 (m, 4H), 7.52-7.48 (m, 2H), 7.39 (t, J=7.6Hz, 2H).13C NMR(100MHz,CDCl3)δ138.9,135.0,133.4, 133.0,132.2,131.7,130.2,128.7,127.3,117.8,93.4,84.2。
Embodiment 16：1H NMR(400MHz,CDCl3)δ8.27–8.24(m,1H),7.82–7.80(m,1H),7.62– 7.46 (m, 5H), 7.40 (t, J=7.7Hz, 2H), 7.26 (s, 1H).13C NMR(100MHz,CDCl3)δ140.4,135.7, 134.9,133.0,131.7,130.5,128.7,127.9,121.4,117.9,93.4,83.9。

Claims (9)

1. a kind of synthetic method of alkynyl sulfone derivative, it is characterised in that comprise the steps：
With alkynes bromine, organic sulfinic acid sodium as raw material, in the presence of strong acid as catalyst and organic solvent, reacted, obtained institute State alkynyl sulfone derivative；
The organic solvent be toluene, chloroform, 1,2- dichloroethanes, 1,4- dioxane or tetrahydrofuran in any one or It is several.
2. synthetic method according to claim 1, it is characterised in that the alkynes bromine is the alkynes bromine that aryl replaces.
3. synthetic method according to claim 1, it is characterised in that organic sulfinic acid sodium is the sub- sulphur that aryl replaces Sour sodium.
4. synthetic method according to claim 1, it is characterised in that the temperature of the reaction is 25 ~ 80 DEG C.
5. synthetic method according to claim 1, it is characterised in that the alkynes bromine is with the mol ratio of organic sulfinic acid sodium 1:（1~3）.
6. synthetic method according to claim 1, it is characterised in that H in the strong acid+It is 1 with the mol ratio of alkynes halogen:1.
7. synthetic method according to claim 1, it is characterised in that the strong acid is hydrochloric acid, sulphuric acid, nitric acid, fluoroform In alkyl sulfonic acid, p-methyl benzenesulfonic acid or trifluoroacetic acid any one or a few.
8. synthetic method according to claim 1, it is characterised in that also including purification procedures after the completion of reaction, institute State that to isolate and purify be toward reaction system, to add sodium bicarbonate solution simultaneously to be extracted with ethyl acetate, collect organic faciess and according to Secondary removing wherein moisture content and organic solvent, obtain crude product, and crude product is further separated by column chromatography.
9. synthetic method according to claim 8, it is characterised in that the column chromatography for separation is using petroleum ether and acetic acid second Ester volume ratio is（5~20）：1 mixed solvent is used as eluent.
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Cited By (1)

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CN115385831A (en) * 2022-08-31 2022-11-25 浙江工业大学 Method for preparing alkyne sulfone compound by oxidation of selenium-containing catalytic system

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CN115385831B (en) * 2022-08-31 2023-11-10 浙江工业大学 Method for preparing alkyne sulfone compound by oxidation of selenium-containing catalytic system

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