CN106810539A - A kind of phenyl bridged pyrazolate base benzimidizole derivatives and preparation method thereof - Google Patents
A kind of phenyl bridged pyrazolate base benzimidizole derivatives and preparation method thereof Download PDFInfo
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- CN106810539A CN106810539A CN201510846504.XA CN201510846504A CN106810539A CN 106810539 A CN106810539 A CN 106810539A CN 201510846504 A CN201510846504 A CN 201510846504A CN 106810539 A CN106810539 A CN 106810539A
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
Abstract
The invention discloses a kind of phenyl bridged pyrazolate base benzimidizole derivatives and preparation method thereof.With 3- bromophenyl-hydrazines as raw material, phenyl bridged pyrazolate base benzimidizole derivatives are synthesized by three-step reaction.Such compound can be used to synthesize the ruthenium complex of high catalytic activity as tridentate ligand.The present invention has the advantages that raw material is cheap and easy to get, combined coefficient is high and product is easy to derivatization.
Description
Technical field
The present invention relates to a kind of phenyl bridged pyrazolate base benzimidizole derivatives and preparation method thereof.
With 3- bromophenyl-hydrazines as raw material, phenyl bridged pyrazolate base benzimidazole is synthesized by three-step reaction and has been spread out
It is biological.Such compound can be used to synthesize the ruthenium complex of high catalytic activity as tridentate ligand.
The present invention has the advantages that raw material is cheap and easy to get, combined coefficient is high and product is easy to derivatization.
Technical background
The chelant thing that pincerlike (pincer) part is formed with transition-metal coordination has good stabilization
Property, reactivity and stereoselectivity, be widely used in Coordinative Chemistry, organic synthesis,
The field such as homogeneous catalysis and functional material.
Phenyl bridging pincer ligand can be adjusted by adjusting ligand structure and change central metal
Save its catalysis activity and selectivity., Duan Weiliang groups (W.L.Duan, J.Am. in 2010
Chem.Soc.2010,132,5562.) catalyst head is made using chiral PCP pincerlike palladium compounds
The secondary asymmetric reduction reaction for realizing diaryl phosphin hydrogen and ketenes, be up to 93% yield and
99% stereoselectivity have successfully been obtained a series of chiral phosphine-derivatives.The reaction is embodied as
The design synthesis of chiral phosphine ligand provides an approach for simple and effective.2013,
Nishiyama groups (H.Nishiyama, et al.Angew.Chem.Int.Ed.2013,52,
11011.) chiral double (oxazolines are found) benzene NCN pincer rhodium compounds can be catalyzed end group alkene
The reaction of asymmetric pair of boronation, chiral double boron compounds are converted into chiral 1,2- through boron removal reaction
Diol, derivatives, stereoselectivity is up to 99%.The reaction is optical voidness 1,2- high in high yield
The synthesis of diol, derivatives provides a kind of new method of convenience and high-efficiency., Huang Zheng little in 2014
Group (Z.Huang, et al.Angew.Chem.Int.Ed.2014,53,1390.) reports phenyl bridge
The PCP types pincer complex of iridium of connection shows catalysis very high and lives in dehydrating alkanes reaction
Property, more than 99%, turn over number (TON) value is up to 6000 to conversion ratio in cyclooctane dehydrogenation reaction.
The invention discloses a kind of phenyl bridged pyrazolate base benzimidizole derivatives and its preparation side
Method.With 3- bromophenyl-hydrazines as raw material, phenyl bridged pyrazolate base benzene is synthesized by simple three-step reaction
Benzimidazole derivative.Such compound can be used to synthesize the ruthenium of high catalytic activity as tridentate ligand
Complex.The present invention is with raw material is cheap and easy to get, combined coefficient is high and product is easy to derivatization etc.
Advantage.
Phenyl bridged pyrazolate base benzimidizole derivatives
The content of the invention
Be easy to get it is an object of the invention to provide a kind of raw material, reaction condition is gentle, wide adaptability,
A kind of method of phenyl bridged pyrazolate base benzimidizole derivatives can be efficiently synthesized.
The phenyl bridged pyrazolate base benzimidizole derivatives that the present invention is provided, structural formula such as following formula 1
It is shown：
Wherein R1It is one or two or more kinds in hydrogen, methyl or phenyl；R3It is hydrogen, methyl
Or one or two or more kinds in phenyl；R2It is the one kind in hydrogen or methyl or two kinds.
The preparation method of the phenyl bridged pyrazolate base benzimidizole derivatives, including following step
Suddenly：
(1) with 3- bromophenyl-hydrazines 2 as initiation material, 3- bromophenyl-hydrazines 2 and the initial ring of beta-diketon 3
Change reaction generation 4；
(2) under cryogenic conditions 4 with n-BuLi/N,N-dimethylformamide reaction generation 5；
(3) 5 spread out with the condensation reaction of o-phenylenediamine 6 generation phenyl bridged pyrazolate base benzimidazole
Biological 1；
After reaction terminates, reaction solution is cooled to room temperature, decompression is lower to remove volatile component, Ran Houyong
Column chromatography for separation.Target product is confirmed by nuclear magnetic resoance spectrum.
Reaction equation：
Wherein R1It is one or two or more kinds in hydrogen, methyl or phenyl；R3It is hydrogen, methyl
Or one or two or more kinds in phenyl；R2It is the one kind in hydrogen or methyl or two kinds.
In the step (1), 3- bromophenyl-hydrazines are 0.2 with the mol ratio of beta-diketon:1-4:1；Instead
The solvent answered is more than the one or two kinds of in methyl alcohol, ethanol and n-butanol；Solvent load is
1-5mL/mmol3- bromophenyl-hydrazines；Reaction temperature is 30-120 DEG C；Reaction time is 2-12 hours.
In the step (2), 4 is 0.5 with the mol ratio of n-BuLi:1-2:1；4 and N, N-
The mol ratio of dimethylformamide is 0.5:1-2:1；The solvent of reaction is n-hexane, ether and four
One or two kinds of in hydrogen furans, 4 is every 1mmol4, solvent with the usage ratio of solvent
Consumption is 5-10mL；The low-temp reaction, reaction temperature is -80-50 DEG C；Reaction time is
2-8 hours.
In the step (3), 5 is 0.5 with the mol ratio of o-phenylenediamine 6:1-4:1；Reaction
Solvent is more than the one or two kinds of in toluene, chlorobenzene and nitrobenzene, 5 with the consumption of solvent
Ratio is every 1mmol5, and solvent load is 5-30mL；Reaction temperature is 50-180 DEG C；Instead
It is 2-8 hours between seasonable.
Technical scheme is characterised by：
1. raw material 3- bromophenyl-hydrazines 2, o-phenylenediamine 6 are commercial prod, can directly buy and use.
2. raw material beta-diketon 3 can be used by simply preparing or directly buying.
In a word, the present invention has synthesized phenyl bridging with 3- bromophenyl-hydrazines as raw material by three-step reaction
Pyrazolyl benzimidizole derivatives 1.The ruthenium that such compound can be used to synthesize high catalytic activity is matched somebody with somebody
Compound.The present invention have that raw material is cheap and easy to get, combined coefficient is high and product to be easy to derivatization etc. excellent
Point.
Specific embodiment
Contribute to further understand the present invention by following embodiments, but present disclosure is simultaneously
It is not limited only to this.
Embodiment 1
3- bromophenyl-hydrazines 2 (1.40g, 7.5mmol), levulinic are added in 50mL reaction bulbs
Ketone 3a (1.00g, 10.0mmol) and 10mL ethanol, 65 DEG C of stirring reactions 6 hours.Instead
After should terminating, mixture is cooled to room temperature, decompression is lower to remove volatile component, then uses silicagel column
(eluent is petroleum ether (60-90 DEG C)/ethyl acetate, v/v=30 to chromatography:1), obtain
To yellow liquid product 4a (1.52g, yield 81%).Target product passes through nuclear magnetic resoance spectrum
It is confirmed.
Embodiment 2
With operation with embodiment 1, difference from Example 1 is acetylacetone,2,4-pentanedione to reactions steps
3a consumptions are (0.75g, 7.5mmol).Stop reaction, mesh is obtained through same method post processing
Mark product 4a (1.35g, yield 72%).When illustrating the acetylacetone,2,4-pentanedione 3a using equimolar amounts,
Reaction yield reduction.
Embodiment 3
With operation with embodiment 1, difference from Example 1 is reaction temperature to reactions steps
It is 30 DEG C.Stop reaction, (0.38g is received to obtain target product 4a through same method post processing
Rate 20%).Illustrate to reduce reaction temperature, be unfavorable for that target product is generated.
Embodiment 4
With operation with embodiment 1, difference from Example 1 is the reaction time to reactions steps
It is 1 hour.Stop reaction, through same method post processing obtain target product 4a (0.49g,
Yield 26%).Illustrate to shorten the reaction time, reaction yield reduction.
Embodiment 5
With operation with embodiment 1, difference from Example 1 is reaction system to reactions steps
Middle addition is 1,3- diphenylprop diketone 3b (2.24g, 10.0mmol).Stop reaction, warp
Same method post processing obtains target product 4b (2.25g, yield 80%).Target product passes through
Nuclear magnetic resoance spectrum is confirmed.
Embodiment 6
N2Under atmosphere, at -78 DEG C, to nBuLi's (2.5M in hexanes, 2.2mmol)
The THF solution (10mL) of 4a (502mg, 2.0mmol) is added dropwise in THF (10mL) solution,
Reaction solution continues to be kept for 30 minutes at -78 DEG C after completion of dropping, then to adding N, N- in reaction solution
Dimethylformamide (0.3mL, 4.0mmol), reaction solution warms naturally to room temperature, reaction solution
It is quenched with methyl alcohol (2mL).Reaction solution is poured into saturation NH4In the Cl aqueous solution (20mL), use
Dichloromethane is extracted 3 times for (20mL/ times), collects organic phase, uses anhydrous Na2SO4Dry, mistake
Filter, collects filtrate, and volatile components are removed under decompression, and the crude product for obtaining is by silica gel column layer
Analysis separates (petroleum ether (60-90 DEG C)/ether, v/v=20:1) yellow liquid product 5a, is obtained
(240mg, yield 60%).
Embodiment 7
With operation with embodiment 6, difference from Example 6 is reaction temperature to reactions steps
It is 0 DEG C.Stop reaction, (88mg is received to obtain target product 5a through same method post processing
Rate 22%).Illustrate to rise high reaction temperature, be unfavorable for that target product is generated.
Embodiment 8
With operation with embodiment 6, difference from Example 6 is reactions steps, reactant
That added in system is 1- (3 '-bromophenyl) -3,5- diphenyl -1H- pyrazoles 4b (750mg, 2.0
mmol).Stop reaction, (337mg is received to obtain target product 5b through same method post processing
Rate 52%).Target product is confirmed by nuclear magnetic resoance spectrum.
Embodiment 9
5a (100mg, 0.5mmol), o-phenylenediamine 6 (54 are sequentially added in 50mL reaction bulbs
Mg, 0.5mmol) and 10mL nitrobenzene, 150 DEG C of reaction 2h.After reaction terminates, will be anti-
Liquid is answered to be cooled to room temperature, decompression is lower to remove volatile component, then separates (wash-out with silica gel column chromatography
Liquid is petroleum ether (60-90 DEG C)/ethyl acetate, v/v=3:1) product as light yellow solid 1a, is obtained
(88mg, yield 61%).Target product is confirmed by nuclear magnetic resoance spectrum.
Embodiment 10
With operation with embodiment 9, difference from Example 9 is reaction temperature to reactions steps
It is 80 DEG C.Stop reaction, (32mg is received to obtain target product 1a through same method post processing
Rate 22%).Illustrate to reduce reaction temperature, be unfavorable for that target product is generated.
Embodiment 11
With operation with embodiment 9, difference from Example 9 is o-phenylenediamine to reactions steps
7 consumptions (108mg, 1mmol).Stop reaction, target product is obtained through same method post processing
1a (65mg, yield 45%).Illustrate to increase o-phenylenediamine consumption, be unfavorable for that target product is given birth to
Into.
Embodiment 12
With operation with embodiment 9, difference from Example 9 is the reaction time to reactions steps
It is 6h.Stop reaction, target product 1a (86mg, yield are obtained through same method post processing
60%).Illustrate that the extension reaction time is unhelpful to improving target product yield.
Embodiment 13
With operation with embodiment 9, difference from Example 9 is reactions steps, reactant
That added in system is 5b (162mg, 0.5mmol).Stop reaction, post-processed through same method
Obtain target product 1b (134mg, yield 65%).Target product is obtained by nuclear magnetic resoance spectrum
To confirmation.
Typical compound characterize data
Phenyl bridged pyrazolate base benzimidizole derivatives 1a, light yellow solid.1H NMR(CDCl3,
400MHz, 23 DEG C) δ 8.00 (m, 1H), 7.89 (t, J=1.6Hz, 1H), 7.62 (m, 2H),
7.28(m,4H),6.73(s,1H),6.06(s,1H),2.40(s,3H),2.19(s,3H)；13C{1H}NMR(CDCl3,100MHz,23℃)δ151.2,149.5,140.4,139.5,
131.3,129.8,126.4,125.9,123.0,122.9,120.4,116.8,107.3,13.5,12.1。
C18H16N4HRMS theoretical values ([M+]):288.1375；Measured value:288.1382.
1- (3 '-bromophenyl) -3,5 dimethyl -1H- pyrazoles 4a, yellow liquid.1H NMR(CDCl3,400
MHz, 23 DEG C) δ 7.63 (m, 1H), 7.46 (d, J=7.8Hz, 1H), 7.37 (m, 1H),
7.29 (t, J=8.0Hz, 1H), 5.98 (s, 1H), 2.30 (s, 3H), 2.28 (s, 3H)；13C{1H}
NMR(CDCl3,100MHz,23℃)δ149.6,141.2,139.6,130.25,130.20,
127.7,123.0,122.6,107.6,13.6,12.6。C11H11BrN2HRMS theoretical values
([M+]):250.0106；Measured value:250.0114.
3- (3,5 dimethyl -1H- pyrazolyls) benzaldehyde 5a, yellow liquid.1H NMR(CDCl3,400
MHz, 23 DEG C) δ 9.97 (s, 1H), 7.90 (t, J=1.6Hz, 1H), 7.78 (m, 1H), 7.67
(m, 1H), 7.54 (t, J=7.8Hz, 1H), 5.96 (s, 1H), 2.28 (s, 3H), 2.23 (s, 3
H)；13C{1H}NMR(CDCl3,100MHz,23℃)δ191.3,149.6,140.7,139.5,
137.1,134.2,129.8,127.9,124.8,107.8,13.4,12.5。C12H12N2The HRMS of O
Theoretical value ([M+]):200.0950；Measured value:200.0954.
Claims (5)
1. a kind of phenyl bridged pyrazolate base benzimidizole derivatives, it is characterised in that：Structural formula
As shown in following formula 1：
Wherein R1It is one or two or more kinds in hydrogen, methyl or phenyl；R3It is hydrogen, methyl
Or one or two or more kinds in phenyl；R2It is the one kind in hydrogen or methyl or two kinds.
2. the preparation side of phenyl bridged pyrazolate base benzimidizole derivatives described in a kind of claim 1
Method, it is characterised in that：Comprise the following steps：
(1) with 3- bromophenyl-hydrazines 2 as initiation material, 3- bromophenyl-hydrazines 2 and the initial ring of beta-diketon 3
Change reaction generation 4；
(2) under cryogenic conditions 4 with n-BuLi/N,N-dimethylformamide reaction generation 5；
(3) 5 spread out with the condensation reaction of o-phenylenediamine 6 generation phenyl bridged pyrazolate base benzimidazole
Biological 1；
Reaction equation：
Wherein R1It is one or two or more kinds in hydrogen, methyl or phenyl；R3It is hydrogen, methyl
Or one or two or more kinds in phenyl；R2It is the one kind in hydrogen or methyl or two kinds.
3. preparation method as claimed in claim 2, it is characterised in that：The step (1)
In, 3- bromophenyl-hydrazines are 0.2 with the mol ratio of beta-diketon:1-4:1；The solvent of reaction is methyl alcohol, second
It is more than the one or two kinds of in alcohol and n-butanol；Solvent load is 1-5mL/mmol3- bromobenzenes
Hydrazine；Reaction temperature is 30-120 DEG C；Reaction time is 2-12 hours.
4. preparation method as claimed in claim 2, it is characterised in that：The step (2)
In, 4 is 0.5 with the mol ratio of n-BuLi:1-2:1；4 rub with N,N-dimethylformamide
You are than being 0.5:1-2:1；The solvent of reaction be n-hexane, ether and tetrahydrofuran in one kind or
Two kinds of person, 4 is every 1mmol4 with the usage ratio of solvent, and solvent load is 5-10mL；Institute
Low-temp reaction is stated, reaction temperature is -80-50 DEG C；Reaction time is 2-8 hours.
5. preparation method as claimed in claim 2, it is characterised in that：The step (3)
In, 5 is 0.5 with the mol ratio of o-phenylenediamine 6:1-4:1；The solvent of reaction is toluene, chlorobenzene
More than the one or two kinds of in nitrobenzene, 5 is every 1mmol5 with the usage ratio of solvent,
Solvent load is 5-30mL；Reaction temperature is 50-180 DEG C；Reaction time is 2-8 hours.
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Citations (3)
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|---|---|---|---|---|
| JP2008024698A (en) * | 2006-06-21 | 2008-02-07 | Mitsubishi Chemicals Corp | Organic compound, charge transport material, charge transport material composition and organic electroluminescent device |
| CN103087049A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院大连化学物理研究所 | 2,6-bis[(5,6-dialkyl)-1,2,4-triazinyl-3-yl]-pyridine and preparation method thereof |
| CN104672208A (en) * | 2013-11-27 | 2015-06-03 | 中国科学院大连化学物理研究所 | Synthesis method of (3,5-bistrifluoromethylpyrazolyl)pyridine derivatives |
-
2015
- 2015-11-27 CN CN201510846504.XA patent/CN106810539A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008024698A (en) * | 2006-06-21 | 2008-02-07 | Mitsubishi Chemicals Corp | Organic compound, charge transport material, charge transport material composition and organic electroluminescent device |
| CN103087049A (en) * | 2011-11-03 | 2013-05-08 | 中国科学院大连化学物理研究所 | 2,6-bis[(5,6-dialkyl)-1,2,4-triazinyl-3-yl]-pyridine and preparation method thereof |
| CN104672208A (en) * | 2013-11-27 | 2015-06-03 | 中国科学院大连化学物理研究所 | Synthesis method of (3,5-bistrifluoromethylpyrazolyl)pyridine derivatives |
Non-Patent Citations (2)
| Title |
|---|
| PAULO DANI等: "Hydrogen-Transfer Catalysis with Pincer-Aryl Ruthenium(ii) Complexes", 《ANGEW. CHEM. INT. ED.》 * |
| WANGMING DU等: "Ruthenium(II) Complex Catalysts Bearing a Pyridyl-Based Benzimidazolyl−Benzotriazolyl Ligand for Transfer Hydrogenation of Ketones", 《ORGANOMETALLICS》 * |
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Application publication date: 20170609 |