CN102659658A - Method for synthesis of highly functionalized pyrrole compound - Google Patents
Method for synthesis of highly functionalized pyrrole compound Download PDFInfo
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- CN102659658A CN102659658A CN201210095298XA CN201210095298A CN102659658A CN 102659658 A CN102659658 A CN 102659658A CN 201210095298X A CN201210095298X A CN 201210095298XA CN 201210095298 A CN201210095298 A CN 201210095298A CN 102659658 A CN102659658 A CN 102659658A
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Abstract
The invention belongs to the technical field of organic synthetic chemistry and especially relates to a method for synthesis of a highly functionalized pyrrole compound. The highly functionalized pyrrole compound is obtained by two reaction processes. The method for synthesis of the highly functionalized pyrrole compound comprises that functionalized ketene dithioacetal and alkynol as raw materials are synthesized into a dialkylthio-substituted enyne compound and the dialkylthio-substituted enyne compound and primary amine are prepared into the highly functionalized pyrrole compound. The method for synthesis of the highly functionalized pyrrole compound has simple processes, adopts easily available raw materials and reagents, realizes simultaneous introduction of multiple substituent groups and easy separation purification of products, and is suitable for synthesis of various highly-functionalized pyrrole compounds.
Description
Technical field
The invention belongs to the Synthetic Organic Chemistry technical field, be specifically related to a kind of azoles and compound method thereof of highly functionalization.
Background technology
The pyrroles is one type of important heterogeneous ring compound; Be not only the key structure unit of many biologically active native products, medicine and organic conductive material etc.; But also be multiduty organic synthesis, so the compound method of development pyrrole ring be always one of important subject of Synthetic Organic Chemistry (
Comprehensive Heterocyclic Chemistry III 2008,
3, pp 45-268.;
Nat. Prod. Rep.,
2006,
23, 517-531.;
ARKIVOC 2007,
10, 121-141.).Up to the present the method that has developed comprises: Knorr is synthetic, Hantzsch reaction, Paal-Knorr condensation reaction, reductive coupling reaction, azepine Wittig reaction, polycomponent coupling method and other multistep operant response etc.[4C+1N] type ring-closure reaction of substituted alkynes alkene of 1,1-bialkyl sulphide and primary amine is the method for the azoles of an easy synthetic highly functionalization; From functionalized dithio keteal and alkynol is that the synthetic substituted alkynes ene compound of 1,1-bialkyl sulphide of raw material is sub as organic synthesis, is further prepared the azoles of highly functionalization again by substituted alkynes alkene of 1,1-bialkyl sulphide and primary amine generation cascade reaction.This reaction meets Atom economy, can efficiently, simply synthesize the pyrroles's type compound with highly functionalization.
In recent years; The organic chemical reactions of functionalized dithio keteal becomes one of important directions of current organic chemistry research; The chemical reaction of multiple functionalized dithio keteal is in the news; Such as (Chem. J. Chinese Universities such as halo decarboxylic reaction, carbon-to-carbon linked reaction, carbon-heteroatoms linked reaction, multi-component reactions
2010,
4, 727-730; Synlett
2011,
8, 1073-1080; ).Rapid deterioration along with global ecological environment; How to realize that Sustainable development has become the significant problem of face of mankind, with decontamination from the source, save resource be the Green Chemistry research of the core strong means that become the increasingly serious ecological environment problem of solution (
Energy Environ. Sci. 2009,
2, 1038-1049.).The substituted alkynes alkene of 1,1-bialkyl sulphide has environmental friendliness, advantage such as cheap, and these advantages make it be particularly suitable for the midbody of producing as chemical industry.Up to the present, bibliographical information is not also seen in the reaction of the azoles of the synthetic highly functionalization of substituted alkynes alkene of 1,1-bialkyl sulphide and primary amine.
Summary of the invention
The purpose of this invention is to provide a kind of azoles method for preparing highly functionalization with substituted alkynes alkene of 1,1-bialkyl sulphide and primary amine reaction.
The present invention has developed the ring-closure reaction of substituted alkynes alkene of a kind of 1,1-bialkyl sulphide and primary amine, and its reaction equation is following:
Comprise the substituted alkynes alkene of a kind of 1,1-bialkyl sulphide
1With primary amine R
3-NH
2Be heated to 100 ℃ and in non-aqueous solvent, react the azoles that obtains highly functionalization
2, wherein, R
1Be aryl, heteroaryl, R
2Be aryl, R
3Be alkyl, R
'Be alkyl, amino.
The preparation method of the azoles of highly functionalization of the present invention comprises synthetic, the annulation of the substituted alkynes alkene of 1,1-bialkyl sulphide etc.
Detailed process can be represented as follows:
(1)From functionalized dithio keteal and alkynol is the synthetic substituted alkynes ene compound of 1,1-bialkyl sulphide of raw material
1
Its consumption is: the mol ratio of functionalized dithio keteal and propynol and trivalent iron salt is 1:1.1:0.3.Solvent is a polar solvent, for example
N, N-N (DMF), 1,4-dioxane, ethanol, acetonitrile.
(2)In certain reaction temperature and solvent, by the substituted alkynes alkene of 1,1-bialkyl sulphide
1Prepare the azoles of highly functionalization with primary amine
2
With respect to the substituted alkynes alkene of 1,1-bialkyl sulphide
1, the amount of primary amine is
12.5 times of consumption.Temperature of reaction is 80-120 ° of C, is the best with 100 ° of C.Solvent can be selected toluene, 1, and 4-dioxane, methyl alcohol, DMSO 99.8MIN. are best with high boiling point, nonpolar DMSO 99.8MIN..
The present invention has simple to operate; Raw material and reagent are easy to get, mild condition, reaction system environmental protection; The product easy separation and easy purification; Be applicable to the azoles of synthetic various highly functionalizations, be specially adapted to large-scale industrial production, can make highly purified azoles efficiently, with high yield.
Description of drawings
Fig. 1 is a reaction expression of the present invention;
Fig. 2 is pyrroles 2a's
1The nuclear magnetic resonance spectrum of H-NMR;
Fig. 3 is pyrroles 2a's
13The nuclear magnetic resonance spectrum of C-NMR;
Fig. 4 is pyrroles 2d's
1The nuclear magnetic resonance spectrum of H-NMR;
Fig. 5 is pyrroles 2d's
13The nuclear magnetic resonance spectrum of C-NMR.
Embodiment
Following embodiment will help to explain the present invention, but not limit to its scope.
Embodiment 1
1) the substituted alkynes alkene of 1,1-bialkyl sulphide
1aPreparation
In the 25 mL round-bottomed flasks that have magnetic stirring apparatus, add acetonitrile (CH
3CN) (4 mL), α-ethanoyl dithio keteal (0.320g, 2.0 mmol) and 1,3-phenylbenzene propynol (0.499g, 12 mmol), under 20 ° of C of room temperature, whipped state, TLC detects substrate and disappears, and reaction finishes.In reaction solution impouring saturated sodium-chloride water solution (10 mL),, merge organic phase with methylene dichloride (3 * 10 mL) extraction; Calcium Chloride Powder Anhydrous is dry, filter; Organic solvent is removed in underpressure distillation then, obtains solid mixture, and (elutriant is V through silica gel column chromatography
Sherwood oil: V
ETHYLE ACETATE=10: 3) obtain white solid 0.61g, the structure of product turns out to be the substituted alkynes alkene of 1,1-bialkyl sulphide through NMR, MS
1a, yield is 88%.
2) pyrrole derivative
2aPreparation
In the 25 mL round-bottomed flasks that have magnetic stirring apparatus, add DMSO 99.8MIN. (2 mL), the substituted alkynes alkene of 1,1-bialkyl sulphide
1a(0.35g, 1.0 mmol) and benzylamine (0.30ml, 2.5 mmol) after stirring, put it into and continue in 100 ° of C oil baths to stir.TLC detects substrate and disappears, and reaction finishes.With (10 mL) in the reaction solution impouring saturated sodium-chloride water solution; Extract with methylene dichloride (3 * 10 mL); Merge organic phase; Water (3 * 10 mL) backwash organic phase then, dry through Calcium Chloride Powder Anhydrous, filter, step such as underpressure distillation obtains the heavy-gravity solid, (elutriant is V to pass through silica gel column chromatography at last
Sherwood oil: V
ETHYLE ACETATE=10: 2) obtain white solid 0.42g, turn out to be pyrrole derivative through NMR, MS
2a, the substituted alkynes alkene of its yield 1,1-bialkyl sulphide
1aFor the basis is 87%.
The spectrum elucidation data
2a:
1 H?NMR?(500?MHz,?CDCl
3)?δ?2.57?(s,?3H),?3.78?(s,?2H),?4.62?(d,?
J?=?4.5?Hz,?2H),?4.84?(s,?2H),?6.73?(d,?
J?=?7.5?Hz,?2H),?6.83?(s,?1H),?6.87?(d,?
J?=?7.0?Hz,?2H),?6.96?(d,?
J?=?7.0?Hz,?2H),?7.15-7.25?(m,?6H),?7.25-7.31?(m,?8H);?
13 C?NMR?(CDCl
3,?125?MHz)?δ?11.82,?30.20,?47.24,?50.40,?120.33,?122.54,?125.58,?126.30,?126.74,?127.17,?127.30,?127.58,?127.77,?128.08,?128.56,128.57,?128.57,?128.81,?129.95,?133.51,?134.97,?136.16,?136.99,?139.11,?193.18;?
HRMS?(ESI)?m/z?calculated?for?C
33H
31N
2S?[M+1]
+?:?487.2208?found:?487.2155.
Embodiment 2
Use
1bReplace in the instance 1
1a, temperature is 80 ℃, and other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2b:
1 H-NMR?(500?MHz,?CDCl
3)?δ?2.56?(s,?3H),?3.80?(s,?2H),?4.69?(d,?
J?=?4.5?Hz,?2H),?4.85?(s,?2H),?6.85?(d,?
J?=?7.5?Hz,?2H),?6.91-6.99?(m,?6H),?7.153-7.30?(m,?12H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.99,?30.38,?47.36,?50.50,?111.96,?122.92,?125.58,?126.14,?126.38,?127.38,?127.45,?127.64,?127.67,?127.90,?128.29,?128.57,?128.62,?128.85,?129.22,?133.81,?136.02,?136.24,?136.67,?138.67,?192.56;
?HRMS?(ESI)?m/z?calculated?for?C
31H
29N
2S?
2[M+1]
+?:?493.1772?found:?493.1672.
Embodiment 3
Use
1cReplace in the instance 1
1a, temperature is 120 ℃, and other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2c:
1 H-NMR?(500?MHz,?CDCl
3)?δ?2.73?(s,?3H),?3.90?(s,?2H),?4.77?(d,?
J?=?4.5?Hz,?2H),?5.00?(s,?2H),?6.88?(d,?
J?=?7.0?Hz,?2H),?7.01-7.05?(m,?7H),?7.31?(d,?
J?=?7.5?Hz,?2H),?7.42-7.47?(m,?8H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.84,?29.49,?47.28,?50.43,?115.27,?115.44,?120.41,?122.67,?125.56,?126.88,?127.04,?127.41,?127.65,?128.11,?128.63,?128.88,?128.91,?129.17,?129.23,?129.95,?133.56,?134.69,?134.71,?134.90,?136.16,?136.87,?160.48,?162.43,?193.16;
?HRMS?(ESI)?m/z?calculated?for?C
33H
30FN
2S?[M+1]
+?:?505.2114?found:?505.2079.
Embodiment 4
Use
1dReplace in the instance 1
1a, toluene is solvent, and other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2d:
1 H-NMR?(500?MHz,?CDCl
3)?δ?3.67?(s,?2H),?4.65?(d,?
J?=?4.5?Hz,?2H),?4.73?(s,?2H),?6.28?(s,?2H),?6.78?(s,?1H),?6.88?(t,?
J?=?8.0?Hz,?2H),?6.98-7.01?(m,?4H),?7.12-7.20?(m,?7H),?7.21-7.33?(m,?4H);?
13 C?-NMR?(CDCl
3,?125?MHz)?δ?29.77,?46.02,?48.73,?102.32,?117.98,?122.30,?125.94,?126.39,?127.24,?128.43,?128.43,?128.59,?129.06,?130.70,?135.00,?135.82,?136.77,?139.01,?147.37,?186.91;?
HRMS?(ESI)?m/z?calculated?for?C
32H
28N
3S?[M-1]
+?:?486.2004?found:?486.2005.
Embodiment 5
Replace the benzylamine in the instance 1 with furylamine, 1, the 4-dioxane is a solvent, and other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2e:
1 H-NMR?(500?MHz,?CDCl
3)?δ?2.68?(s,?3H),?4.00?(s,?2H),?4.66,?(d,?
J?=?3.5?Hz,?2H),?4.74?(s,?2H),?5.87?(s,?1H),?6.02?(s,?1H),?6.18?(s,?1H),?6.27?(s,?1H),?6.82?(s,?1H),?7.03?(d,?
J?=?7.0?Hz,?2H),?7.16-7.32?(m,?12H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.91,?30.10,?40.87,?42.51,?107.80,?107.86,?110.22,?110.35,?120.31,?122.26,?126.34,?126.69,?126.93,?127.79,?127.87,?128.62,?128.64,?133.72,?134.44,?139.12,?142.10,?142.47,?149.34,?149.88,?193.02;
?HRMS?(ESI)?m/z?calculated?for?C
29H
27N
2O
2S?[M+1]
+?:?467.1793?found:?467.1742.
Embodiment 6
Replace the benzylamine in the instance 1 with ethamine, other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2f:
1 H-NMR?(500?MHz,?CDCl
3)?δ?0.74?(t,?
J?=?7.0?Hz,?3H),?1.04?(t,?
J?=?7.5?Hz,?3H),?2.64?(s,?3H),?3.46-3.51?(m,?2H),?3.69?(q,?
J?=?7.0,?7.5?Hz,?2H),?3.93?(s,?2H),?6.50?(s,?1H),?7.05?(d,?
J?=?7.5?Hz,?2H),?7.18?(t,?
J?=?7.5?Hz,?1H),?7.24-7.34?(m,?7H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.72,?12.57,?15.46,?30.15,?38.88,?40.21,?119.80,?122.38,?126.29,?126.66,?127.88,?128.55,?128.62,?129.92,?132.59,?135.08,?139.59,?192.80;
?HRMS?(ESI)?m/z?calculated?for?C
23H
27N
2S?[M+1]
+?:?363.1895?found:?363.1793.
Embodiment 7
Replace the benzylamine in the instance 1 with thanomin, other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2g:
1 H-NMR?(500?MHz,?CDCl
3)?δ?1.15?(s,?1H),?1.88?(s,?1H),?2.60?(s,?3H),?3.43?(q,?2H),?3.62?(t,?
J?=?6.0?Hz,?2H),?3.70?(q,?2H),?3.81?(t,?
J?=?6.0?Hz,?2H),?3.99?(s,?2H),?7.04?(d,?
J?=?7.5?Hz,?3H),?7.19?(d,?
J?=?7.5?Hz,?1H),?7.27?(t,?
J?=?7.0?Hz,?3H),?7.31-7.37?(m,?4H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.95,?30.24,?46.06,?47.26,?60.55,?61.51,?119.98,?123.12,?126.38,?126.68,?127.22,?127.82,?128.57,?128.65,?129.83,?132.76,?135.18,?139.34,?194.22;
?HRMS?(ESI)?m/z?calculated?for?C
23H
27N
2O
2S?[M+1]
+?:?395.1793?found:?395.1794.
Embodiment 8
Replace the benzylamine in the instance 1 with allyl amine, other conditions are with instance 1, and experimental result is seen table 1.
The spectrum elucidation data
2h:
1 H-NMR?(500?MHz,?CDCl
3)?δ?2.59?(s,?3H),?3.90?(s,?2H),?4.10?(s,?t,?
J?=?5.0Hz,?2H),?4.24?(d,?
J?=?2.0?Hz,?2H),?4.82?(t,?
J?=?16.0?Hz,?2H),?4.93?(d,?
J?=?10.0?Hz,?1H),?5.10?(d,?
J?=?10.5?Hz,?1H),?5.38-5.45?(m,?1H),?5.64-5.72?(m,?1H),?6.62?(s,?1H),?7.03?(d,?
J?=?7.5?Hz,?2H),?7.18?(t,?
J?=?7.0?Hz,?1H),?7.25?(t,?
J?=?7.0?Hz,?3H),?7.29-7.34?(m,?4H);?
13 C-NMR?(CDCl
3,?125?MHz)?δ?11.67,?30.09,?46.28,?48.00,?116.47,?117.74,?119.91,?122.32,?126.29,?126.72,?127.80,?128.56,?128.66,?129.85,?131.92,?132.79,?133.47,?134.84,?139.28,?193.13;?
HRMS?(ESI)?m/z?calculated?for?C
25H
27N
2S?[M+1]
+?:?387.1895?found:?387.1785.
Table 1
| Embodiment | The substituted alkynes alkene of 1,1-bialkyl sulphide 1 | The pyrroles of highly functionalization 2 |
| 1 |  |  |
| 2 | (87%) |  |
| 3 |  |  |
| 4 |  |  |
| 5 |  |  |
| 6 |  |  |
| 7 |  |  |
| 8 |  |  |
Claims (3)
1. the compound method of the azoles of a highly functionalization is characterized in that reaction equation is following:
Wherein, R
1Be aryl, heteroaryl, R
2Be aryl, R
3Be alkyl, R
'Be alkyl, amino,
Concrete steps are following:
From functionalized dithio keteal and alkynol is the synthetic substituted alkynes ene compound of 1,1-bialkyl sulphide of raw material
1:
Its consumption is: the mol ratio of functionalized dithio keteal and propynol and trivalent iron salt is 1:1.1:0.3, and solvent is a polar solvent;
In certain reaction temperature and solvent, by the substituted alkynes alkene of 1,1-bialkyl sulphide
1Prepare the azoles of highly functionalization with primary amine
2:
With respect to the substituted alkynes alkene of 1,1-bialkyl sulphide
1, the amount of primary amine is
12.5 times of consumption, temperature of reaction is 80-120 ° of C, solvent is a toluene, 1,4-dioxane, methyl alcohol, DMSO 99.8MIN..
2. press the compound method of the azoles of the described a kind of highly functionalization of claim, it is characterized in that the solvent in (1)
For
N, N-N (DMF), 1,4-dioxane, ethanol, acetonitrile, the temperature of reaction in (2) is 100 ° of C.
3. press the azoles of the highly functionalization of the described compound method preparation of claim.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145600A (en) * | 2013-03-06 | 2013-06-12 | 东北师范大学 | Synthesis method of silver-catalyzed polysubstitued pyrrole compounds |
| CN104860864A (en) * | 2015-06-04 | 2015-08-26 | 广西师范大学 | New synthetizing method of 2-carbonyl-5-alkynyl pyrrole compound |
| CN105061286A (en) * | 2015-09-08 | 2015-11-18 | 张涛 | Synthesis method of alkynyl substituted pyrrole compounds |
| CN105152828A (en) * | 2015-08-18 | 2015-12-16 | 杨雪峰 | Synthetic method of acetylenic ketone compound |
-
2012
- 2012-04-01 CN CN201210095298XA patent/CN102659658A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145600A (en) * | 2013-03-06 | 2013-06-12 | 东北师范大学 | Synthesis method of silver-catalyzed polysubstitued pyrrole compounds |
| CN104860864A (en) * | 2015-06-04 | 2015-08-26 | 广西师范大学 | New synthetizing method of 2-carbonyl-5-alkynyl pyrrole compound |
| CN105152828A (en) * | 2015-08-18 | 2015-12-16 | 杨雪峰 | Synthetic method of acetylenic ketone compound |
| CN105061286A (en) * | 2015-09-08 | 2015-11-18 | 张涛 | Synthesis method of alkynyl substituted pyrrole compounds |
| CN105061286B (en) * | 2015-09-08 | 2017-11-24 | 上海蓝木化工有限公司 | A kind of synthetic method of alkynyl substituted azoles |
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Application publication date: 20120912 |