CN103387543B - A kind of synthetic method of tetrahydropyrazolonederivative derivative - Google Patents
A kind of synthetic method of tetrahydropyrazolonederivative derivative Download PDFInfo
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Abstract
A kind of synthetic method of tetrahydropyrazolonederivative derivative, the structural formula of described tetrahydropyrazolonederivative derivative is as shown in the formula (4a) in reaction equation 1, described synthetic method is with the aromatic aldehyde shown in the structural formula (1a) in such as reaction equation 1, shown in formula (2a) 5, hydrazinobenzene hydrochloride salt shown in 5-dimedone and formula (3a) is substrate, with the ionic liquid shown in formula (b) for catalyzer, take ethanol as reaction solvent, microwave reaction 15 ~ 25 minutes at 70 ~ 80 DEG C, after reaction terminates, steam solvent, solids washed with water filters, namely described tetrahydropyrazolonederivative derivative is obtained through ethyl alcohol recrystallization after filtration cakes torrefaction.The method reaction conditions is gentle, and easy and simple to handle, the reaction times is short, and ionic liquid can be recycled, and building-up process is environmentally friendly, productive rate and purity high.Reaction equation is as follows.
Description
(1) technical field
The present invention relates to a kind of synthetic method of tetrahydropyrazolonederivative derivative.
(2) background technology
Tetrahydro-pyrazole ketone is a compound with extensive physiology and pharmacologically active.Compound containing pyrazoles and pyrazolone structure has weeding, anti-infective, anticancer and tuberculosis effect.Tetrahydro-pyrazole ketone structure has the similar structures of heat shock protein inhibitors (HSP-90) and anti-breast cancer cell-proliferation activity as structural formula 1.Meanwhile, tetrahydro-pyrazole also has tubercule bacillus inhibitor similar structures unit (MTB) as structural formula 2.Thus the synthesis of tetrahydropyrazolonederivative derivative has become a focus of research.The synthetic method wherein reported only has Rao V.K. with trifluoroacetic acid ytterbium for catalyzer has synthesized tetrahydropyrazolonederivative derivative (Bioorg.Med.Chem.Lett.2012 at imidazole ion liquid at 100 DEG C, 22:410-414), the feature of its reaction uses rare metal to be catalyzer, carry out in ionic liquid and heating, reaction times is longer, catalyzer is not only expensive, and is difficult to recycle, and can bring pollution to a certain degree to environment.Not only toxicity is comparatively large, price for its aryl hydrazine raw material used simultaneously, and not easily preserves.Therefore, invention tetrahydropyrazolonederivative derivative synthetic method that is simple and high-efficiency environment friendly seems particularly important.
(3) summary of the invention
For solving expensive catalyst in existing preparation tetrahydropyrazolonederivative derivative technology, being difficult to the unfavorable factors such as recovery and long reaction time, advocate simultaneously one more green, synthesize theory efficiently, the object of the invention is to disclose one with disulfonic acid type ionic liquid for catalyzer, in the synthetic method that ethanol is reaction solvent, the tetrahydropyrazolonederivative derivative under microwave place is entered.The method reaction conditions is gentle, and easy and simple to handle, the reaction times is short, and ionic liquid can be recycled, and building-up process is environmentally friendly, productive rate and purity high.
For reaching the object of invention, the technical solution used in the present invention is as follows:
A kind of synthetic method of tetrahydropyrazolonederivative derivative, the structural formula of described tetrahydropyrazolonederivative derivative is as shown in the formula (4a) in reaction equation 1, described synthetic method is with the aromatic aldehyde shown in the structural formula (1a) in such as reaction equation 1, shown in formula (2a) 5, aryl hydrazine hydrochloride shown in 5-dimedone and formula (3a) is substrate, with the ionic liquid shown in formula (b) for catalyzer, take ethanol as reaction solvent, microwave reaction 15 ~ 25 minutes at 70 ~ 80 DEG C, after reaction terminates, steam solvent, solids washed with water filters, namely described tetrahydropyrazolonederivative derivative is obtained through ethyl alcohol recrystallization after filtration cakes torrefaction.
Reaction equation is as follows:
R in structure above
1for hydrogen, methyl, chlorine; R
2for hydrogen, chlorine, nitro.
The amount of substance of aromatic aldehyde of the present invention, 5,5-dimedones and aryl hydrazine hydrochloride is than being 1:1:1, and described ionic liquid and aromatic aldehyde amount of substance are than being (0.002 ~ 0.008): 1.
The microwave reaction time of the present invention is 15 ~ 25 minutes.
Microwave reaction temperature of the present invention is 70 ~ 80 DEG C, and microwave input power is 400W.
After reaction of the present invention terminates, distillation removing ethanol, obtains solid product and washes with water, can direct reuse after water-soluble ionic liquid distillation dewaters.
Reaction of the present invention is reaction solvent with ethanol, tetrahydrobiopterin synthesis e derivatives under microwave assisted, and its principal character is embodied in following aspect:
1) aryl hydrazine hydrochloride replaces the phenylhydrazine raw material of bibliographical information, and not only price has certain advantage, and aryl hydrazine hydrochloride toxicity is low, is convenient to store and transport;
2) with disulfonic acid type ionic liquid for catalyzer, avoid using rare metal catalyzer, not only reduce environmental pollution, but also can reuse;
3) microwave assisted reaction, the reaction times is short, easy and simple to handle, yield and product purity high.
To sum up, the synthetic method of a kind of tetrahydropyrazolonederivative derivative of the present invention is a kind of green synthesis method, is suitable for suitability for industrialized production.
(4) specific implementation method
Below in conjunction with specific embodiment, the present invention is further described, but protection scope of the present invention is not limited in this.
Embodiment 1
By phenyl aldehyde (25mmol), 5,5-dimedone (25mmol), hydrazinobenzene hydrochloride salt (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 85%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.50 (s, 1H), 7.38 – 7.31 (m, 6H), 7.18 – 7.25 (m, 2H), 6.94 (d, J=8.0Hz, 1H), 2.82 (s, 2H), 2.43 (s, 2H), 1.17 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 28.47,34.85,53.73,105.01,116.21,124.19,127.67,129.85,130.21,130.27,132.09,133.13,138.38,143.46,156.96,193.38.
Embodiment 2:
By p-tolyl aldehyde (25mmol), 5,5-dimedone (25mmol), hydrazinobenzene hydrochloride salt (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 87%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.44 – 7.35 (m, 3H), 7.35-7.28 (m, 2H), 7.17 (d, J=8.0Hz, 2H), 6.90 (d, J=4.0Hz, 2H), 2.85 (s, 2H), 2.41 (s, 2H), 2.23 (s, 3H), 1.20 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 19.75,28.44,34.87,37.13,53.70,123.49,126.01,126.25,128.71,130.97,131.68,134.69,135.70,136.48,137.68,156.73,193.55.
Embodiment 3:
By 4-chloro-benzaldehyde (25mmol), 5,5-dimedone (25mmol), hydrazinobenzene hydrochloride salt (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 88%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.50-7.43 (m, 2H), 7.38 – 7.31 (m, 4H), 7.18 – 7.25 (m, 2H), 6.93 (d, J=8.0Hz, 1H), 2.81 (s, 2H), 2.43 (s, 2H), 1.18 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 28.46,34.86,53.63,105.05,116.22,125.19,127.67,129.87,130.21,130.27,132.09,133.13,138.38,144.46,156.97,193.38.
Embodiment 4:
Will to 3,4-dichlorobenzaldehyde (25mmol), 5,5-dimedone (25mmol), hydrazinobenzene hydrochloride salt (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, joins in this reaction vessel successively, is placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 75 DEG C, reaction terminates rear distillation removing ethanol, and remaining solid 20mL water washing, filters, filter cake ethyl alcohol recrystallization obtains product, yield 87%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.50 (s, 1H), 7.38 – 7.31 (m, 6H), 7.18 – 7.25 (m, 2H), 6.94 (d, J=8.0Hz, 1H), 2.82 (s, 2H), 2.43 (s, 2H), 1.17 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 28.47,34.85,53.73,105.01,116.21,124.19,127.67,129.85,130.21,130.27,132.09,133.13,138.38,143.46,156.96,193.38.
Embodiment 5:
By phenyl aldehyde (25mmol), 5,5-dimedone (25mmol), p-nitrophenyl hydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 75 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 85%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.50 (s, 1H), 7.38 – 7.31 (m, 6H), 7.18 – 7.25 (m, 2H), 6.94 (d, J=8.0Hz, 1H), 2.82 (s, 2H), 2.43 (s, 2H), 1.17 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 28.47,34.85,53.73,105.01,116.21,124.19,127.67,129.85,130.21,130.27,132.09,133.13,138.38,143.46,156.96,193.38.
Embodiment 6:
By 4-chloro-benzaldehyde (25mmol), 5,5-dimedone (25mmol), p-nitrophenyl hydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 75 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 90%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=8.22 (d, J=2.51Hz, 3H), 7.55 – 7.53 (d, J=2.48Hz, 3H), 7.33 (s, 1H), 6.95 (d, J=8.0Hz, 1H), 2.84 (s, 2H), 2.45 (s, 2H), 1.17 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 28.44,34.94,37.07,53.62,116.92,123.55,124.18,127.23,130.78,131.44,133.00,134.18,137.78,140.70,148.26,157.29,193.46.
Embodiment 7:
By 3,4-dichlorobenzaldehyde (25mmol), 5,5-dimedone (25mmol), p-nitrophenyl hydrazine hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, joins in this reaction vessel successively, is placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, and remaining solid 20mL water washing, filters, filter cake ethyl alcohol recrystallization obtains product, yield 92%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=8.24 (d, J=2.51Hz, 2H, C
3-Ar-H), 7.56 – 7.54 (d, J=2.48Hz, 3H), 7.32 (s, 1H), 6.91 (d, J=8.0Hz, 1H), 2.84 (s, 2H), 2.45 (s, 2H), 1.18 (s, 6H);
13cNMR (100MHz, CDCl
3): δ 28.43,34.95,37.04,53.62,116.90,123.55,124.18,127.21,130.77,131.44,133.00,134.08,137.68,140.69,148.25,157.27,193.49.
Embodiment 8:
By 3,4-dichlorobenzaldehyde (25mmol), 5,5-dimedone (25mmol), p-hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, joins in this reaction vessel successively, is placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, and remaining solid 20mL water washing, filters, filter cake ethyl alcohol recrystallization obtains product, yield 91%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.45 – 7.34 (m, 3H), 7.36 (d, J=3.0Hz, 1H), 7.17 (d, J=8.0Hz, 2H), 6.91 (d, J=4.0Hz, 1H), 2.86 (s, 2H), 2.42 (s, 2H), 1.21 (s, 6H);
13c NMR (100MHz, CDCl
3): δ 19.76,28.45,34.87,37.13,53.70,123.49,126.05,126.25,128.72,130.97,131.68,134.70,135.71,136.48,137.68,156.75,193.56.
Embodiment 9:
By 3,4-dichlorobenzaldehyde (25mmol), 5,5-dimedone (25mmol), 3-chlorophenylhydxazine hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, joins in this reaction vessel successively, is placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, and remaining solid 20mL water washing, filters, filter cake ethyl alcohol recrystallization obtains product, yield 88%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.53 (d, J=4.0Hz, 1H), 7.33 (d, J=8.0Hz, 1H), 6.97 – 6.94 (m, 4H), 6.85 (d, J=4.0Hz, 1H), 3.77 (s, 3H), 2.81 (s, 2H), 2.42 (s, 2H), 1.17 (s, 6H, C (CH
3)
2);
13c NMR (100MHz, CDCl
3): δ 28.47,34.84,37.17,53.77,55.39,115.71,115.80,116.29,122.49,124.10,126.97,128.86,129.49,130.36,132.04,138.44,143.22,156.92,159.30,193.33.
Embodiment 10:
By chloro-for 3-4-tolyl aldehyde (25mmol), 5,5-dimedone (25mmol), p-hydrochloride (25mmol), ionic liquid (0.125mmol), dehydrated alcohol 10mL, join in this reaction vessel successively, be placed in by reaction vessel in microwave reactor, microwave reaction 20 minutes (ultrasonic power input 400W) at 80 DEG C, reaction terminates rear distillation removing ethanol, remaining solid 20mL water washing, filter, filter cake ethyl alcohol recrystallization obtains product, yield 85%.
Characterization data:
1h NMR (400MHz, DMSO-d
6): δ=7.44 – 7.35 (m, 3H), 7.35 (d, J=3.0Hz, 1H), 7.17 (d, J=8.0Hz, 2H), 6.90 (d, J=4.0Hz, 1H), 2.85 (s, 2H), 2.41 (s, 2H), 2.23 (s, 3H), 1.20 (s, 6H, C (CH
3)
2);
13c NMR (100MHz, CDCl
3): δ 19.75,28.44,34.87,37.13,53.70,123.49,126.01,126.25,128.71,130.97,131.68,134.69,135.70,136.48,137.68,156.73,193.55.
Embodiment 11: recycling of ionic liquid
For embodiment 1, after reaction terminates, reacting liquid filtering, filter residue 20mL water washing is filtered, and solid ethyl alcohol recrystallization obtains product, directly uses as the catalyst recirculation of lower secondary response after the filtrate distillation containing ionic liquid dewaters, react according to embodiment 1 step, reaction system circulate 4 times time, reaction yield still more than 80%, acquired results following table:
| Cycle index | Product yield (%) |
| 1 | 83 |
| 2 | 82 |
| 3 | 82 |
| 4 | 81 |
Claims (3)
1. the synthetic method of a tetrahydropyrazolonederivative derivative, the structural formula of described tetrahydropyrazolonederivative derivative is as shown in the formula (4a) in reaction equation 1, described synthetic method is with the aromatic aldehyde shown in the structural formula (1a) in such as reaction equation 1, shown in formula (2a) 5, aryl hydrazine hydrochloride shown in 5-dimedone and formula (3a) is substrate, its amount of substance is than being 1:1:1, with the ionic liquid shown in formula (b) for catalyzer, itself and substrate aromatic aldehyde amount of substance are than being (0.002 ~ 0.008): 1, take ethanol as reaction solvent, microwave reaction 15 ~ 25 minutes at 70 ~ 80 DEG C, after reaction terminates, steam solvent, solids washed with water filters, namely described tetrahydropyrazolonederivative derivative is obtained through ethyl alcohol recrystallization after filtration cakes torrefaction,
Reaction equation is as follows:
R in structure above
1for hydrogen, methyl, chlorine; R
2for hydrogen, chlorine, nitro.
2. the synthetic method of tetrahydropyrazolonederivative derivative as claimed in claim 1, it is characterized in that microwave reaction temperature is 70 ~ 80 DEG C, microwave input power is 400W.
3. the synthetic method of tetrahydropyrazolonederivative derivative as claimed in claim 1, after it is characterized in that reaction terminates, distillation removing ethanol, obtains solid product and washes with water, can direct reuse after water-soluble ionic liquid distillation dewaters.
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| CN101508675A (en) * | 2009-03-26 | 2009-08-19 | 浙江工业大学 | Novel disulfonic acid type alkyl imidazole ionic liquid, preparation and uses thereof |
| CN102351773A (en) * | 2011-08-11 | 2012-02-15 | 台州学院 | Synthesis method of indole type compounds |
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| WO2003070236A2 (en) * | 2002-02-19 | 2003-08-28 | Pharmacia Italia S.P.A. | Tricyclic pyrazole derivatives, process for their preparation and their use as antitumor agents |
| CN101508675A (en) * | 2009-03-26 | 2009-08-19 | 浙江工业大学 | Novel disulfonic acid type alkyl imidazole ionic liquid, preparation and uses thereof |
| CN102351773A (en) * | 2011-08-11 | 2012-02-15 | 台州学院 | Synthesis method of indole type compounds |
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