CN105175457A - Pyridine oxadiazole complex capable of catalyzing DHPMs (Dihydropyrimidinones) - Google Patents
Pyridine oxadiazole complex capable of catalyzing DHPMs (Dihydropyrimidinones) Download PDFInfo
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- CN105175457A CN105175457A CN201510644052.7A CN201510644052A CN105175457A CN 105175457 A CN105175457 A CN 105175457A CN 201510644052 A CN201510644052 A CN 201510644052A CN 105175457 A CN105175457 A CN 105175457A
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- synthesis
- alkyl
- dihydropyrimidinones
- title complex
- oxadiazole
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a pyridine oxadiazole complex capable of catalyzing DHPMs (Dihydropyrimidinones) and provides a method for synthesizing a complex containing p-toluenesulfonic acid and pyridine oxadiazole. According to the invention, a crystal structure of the complex is determined by the aid of single crystal X-rays; further, catalytic activity of the complex on DHPMs is further researched; a series of DHPMs are synthesized with the method which is simple and easy to operate, and the catalytic yield can be up to 98%.
Description
Technical field
The invention belongs to inorganic chemistry, organic chemistry and medicinal chemistry art, relate to the synthesis of title complex and catalyze and synthesize the experimental technique of dihydropyrimidinones.
Background technology
In 1891, the synthetic method of people's Late Cambrian dihydropyrimidinones (Dihydropyrimidinones, DHPMs) also presented development trend in the ascendant.This is because research in recent years shows, DHPMs has the using value of important biology and pharmacology and medical science aspect, and such as they can be used as field (P.B.Thorat, the N.A.Waghmode such as calcium antagonist, sterilization, antiviral, depressor, N.N.Karade
tetrahedronLett. 2014,
55, 5718-5721; Y.Qiu, H.Sun, Z.Ma, W.Xia,
j.Mol.Catal.A:Chem. 2014,
392, 76-82; G.B.D.Rao, B.Anjaneyulu, M.P.Kaushik,
rSCAdv. 2014,
4, 43321-43325.).The routine synthesis of DHPMs compound usually adopts traditional Biginelli reaction, under concentrated hydrochloric acid catalysis, utilize methyl aceto acetate, all kinds of aromatic aldehyde and urea condensation realize (P.Biginelli,
chem.Ber., 1891,
24, 1317-2962).But the method long reaction time, complicated operation, productive rate are low.In order to improve productive rate and Reaction time shorten, the synthetic method of this compounds is obtaining great development recently in decades.Such as with Lewis Acids and Bases, organic bases solid state reaction, comprise the liquid phase reaction of ionic liquid or the condition of microwave reaction under catalyze and synthesize serial DHPMs compound.Although these new technologies improve the deficiency of traditional B iginelli reaction to a certain extent, but still have that temperature of reaction is high, long reaction time, expensive catalyst or to shortcomings such as environment are unfriendly.Therefore the realization of the method for a green syt is found efficiently to prepare still extremely urgent to DHPMs compound.
Recently, the design of title complex and synthesis cause the concern of chemist and material scholar gradually.This be due to complex-bound organic ligand and inorganic metal common, structure-rich, unique.It not only has inorganic and organic property concurrently, and can show the new property that colourful topological framework and mineral compound and organic compound all do not have.Therefore this material optical, electrical, magnetic, catalysis, fractionation by adsorption, information store and have in the field such as biological activity and study widely (Q.L.Zhu, Q.Xu,
chem.Soc.Rev. 2014,
43, 5468-5512; S.Sanda, S.Parshamoni, S.Biswas, S.Konar,
chem.Commun. (Camb.) 2015,
51, 6576-6579; J.Liu, W.Xia, W.j.Mu, P.z.Li, Y.l.Zhao, R.q.Zou,
j.Mater.Chem.A 2015,
3, 5275-5279.).Design and synthesis has ad hoc structure and expects that the title complex of character is the important content of coordination chemistry research always.Due to its nature and function of structures shape of title complex, people by the regulation and control to organic ligand or the aspect such as construction unit and the coordination between they and metal ion, the many new complexes with excellent structure and high-performance of design and synthesis.Recently, people achieve good research to the research of title complex in catalytic performance.There is bibliographical information transition metal ion (as Co
2+, Fe
3+, Ni
2+and Cu
2+) and sulphonic acids part be all once used to catalyzing organic synthesis (M.Sutradhar, M.F.C.GuedesdaSilva, A.J.L.Pombeiro,
catal.Commun. 2014,
57, 103-106; N.B.Li, J.Y.Wang, X.H.Zhang, R.H.Qiu, X.Wang, J.Y.Chen, S.F.Yin, X.H.Xu,
daltonTrans. 2014,
43, 11696-11708; F.Ke, L.G.Qiu, J.Zhu,
nanoscale 2014,
6, 1596-1601; M.Nasr-Esfahani, I.Mohammadpoor-Baltork, A.R.Khosropour, M.Moghadam, V.Mirkhani, S.Tangestaninejad,
j.Mol.Catal.A:Chem. 2013,
379, 243-254).Therefore the present invention considers both advantage above simultaneously, adopts tosic acid and cobalt ion and organoligand coordination to form the title complex with catalytic activity.Through experimental studies have found that above-mentioned composition catalyst achieves prepared by the efficient catalytic of DHPMs compounds.This has important directive significance to synthesizing dihydro pyrimidinones in future.
Summary of the invention
The invention provides the synthetic method that a kind of synthesis has a metal-organic complex of high-efficiency catalytic activity, and be used for efficient catalytic synthesizing dihydro pyrimidines.Invention achieves the green synthesis method of the consumption of minimizing catalyzer, Reaction time shorten, simplification experimental implementation.
For achieving the above object, by tosic acid, sodium hydroxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and
bPO(2,5-two (pyridin-4-yl)-1,3,4-oxadiazole) is water-soluble with in the mixing solutions of methyl alcohol, wherein
bPOstructural formula as Fig. 1.
Then transferred to by solution in reactor and heat 120 degree after 5 hours, the title complex that precipitation obtains red crystals is filtered in cooling
1.By products obtained therefrom
1determine that its molecular structure is as Fig. 2 through Advances in crystal X-ray diffraction analysis.
Finally by product
1grinding is as catalyzer, and what adopt one kettle way catalysis series phenyl aldehyde, methyl aceto acetate and urea is obtained by reacting Dihydropyrimidines.Wherein catalytic result is as Fig. 3.
Concrete synthesis step of the present invention is as follows.
Embodiment one, product
1synthesis
By the tosic acid (0.2mmol) of 0.035g, 0.008g sodium hydroxide (0.2mmol), 0.045g
bPO(0.2mmol) and in the mixing solutions of 0.029g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (0.1mmol) water-soluble (2mL) and methyl alcohol (3mL).Reaction mixture is transferred in reactor heat 120 degree be slowly down to room temperature, filtration with 5 degree speed hourly after 5 hours, leave standstill, the target product of precipitation redness
1and determine its crystalline structure figure.
Embodiment two, catalyze and synthesize the method for dihydropyrimidinones
The product 1 getting 0.02mmol joins as catalyzer in the mixture of 1mmol phenyl aldehyde, 2mmol methyl aceto acetate and 1.5mmol urea, 80 degrees Celsius oil bath pan in heating 2 hours, obtain colorless product, finally purify with water and methyl alcohol lotion and obtain target product.Finally select different aldehyde at identical conditions catalysis obtain series dihydropyrimidinonesand and derivative.
Embodiment
Be described in detail embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The invention provides the synthetic method that a kind of synthesis has a metal-organic complex of high-efficiency catalytic activity, and be used for efficient catalytic synthesizing dihydro pyrimidone and derivative thereof.Invention achieves the green synthesis method of the consumption of minimizing catalyzer, Reaction time shorten, simplification experimental implementation.
For achieving the above object, concrete synthesis step of the present invention is as follows.
Embodiment one, product
1synthesis
By the tosic acid (0.2mmol) of 0.035g, 0.008g sodium hydroxide (0.2mmol), 0.045g
bPO(0.2mmol) and in the mixing solutions of 0.029g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (0.1mmol) water-soluble (2mL) and methyl alcohol (3mL).Reaction mixture is transferred in reactor heat 120 degree be slowly down to room temperature, filtration with 5 degree speed hourly after 5 hours, leave standstill, the target product of precipitation redness
1and determine its crystalline structure figure.Wherein
bPOstructural formula as Fig. 1; Products obtained therefrom
1determine that its molecular structure is as Fig. 2 through Advances in crystal X-ray diffraction analysis.
Embodiment two, catalyze and synthesize the method for dihydropyrimidinones
The product 1 getting 0.02mmol joins as catalyzer in the mixture of 1mmol phenyl aldehyde, 2mmol methyl aceto acetate and 1.5mmol urea, 80 degrees Celsius oil bath pan in heating 2 hours, obtain colorless product, finally purify with water and methyl alcohol lotion and obtain target product.Finally select different aldehyde at identical conditions catalysis obtain series dihydropyrimidinonesand and derivative.Wherein catalytic result is as Fig. 3.
Accompanying drawing explanation
Fig. 1, compound
bPOthe molecular formula of (2,5-two (pyridin-4-yl)-1,3,4-oxadiazole).
Fig. 2, product
1crystalline structure figure.
Fig. 3, product
1catalytic result figure.
Claims (5)
1. contain the synthesis of title complex and the synthetic method for efficient catalytic synthesizing dihydro pyrimidinones thereof of tosic acid and oxadiazole, it is characterized in that synthesis step is:
(1) embodiment one, title complex
1synthesis, by a certain proportion of tosic acid, sodium hydroxide,
bPO(2,5-two (pyridin-4-yl)-1,3,4-oxadiazole) and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in a certain amount of water and organic solvent; Reaction mixture is transferred in reactor to have heated and be slowly down to room temperature, filtration afterwards, leave standstill, separate out red target product
1and determine its crystalline structure figure;
(2) embodiment two, catalyze and synthesize the method for dihydropyrimidinones, its preparation process is with target product
1for catalyzer, get appropriate product
1after catalyzer reaction formula for some time that catalysis is following at moderate temperatures, obtain target product, finally purify with water and organic solvent lotion and obtain pure product;
(3) reaction formula is:
；
In formula: R
1be selected from H, halogen, nitro, cyano group, trifluoromethyl, C
1~ C
9alkyl or C
1~ C
9alkoxyl group; R2 is C
1-10the unsubstituted C of alkyl, OR
3-8cycloalkyl or single-, two-or the three-C that replaces
3-8cycloalkyl, the substituting group wherein in cycloalkyl independently be selected from hydroxyl, C
1-8alkyl, halo C
1-8alkyl, alkane C
1-8the C of alkoxyl group or halo
1-8alkoxyl group; R
3, R
4and R
5each is independently selected from hydrogen, halogen, halo C
1-10alkyl, the aryl not replacing or replace or the C not replacing or replace
1-10alkyl, the substituting group wherein on alkyl is selected from C
1-7alkoxyl group, halo C
1-7alkoxyl group or aryl; R
6and R
7each is independently selected from hydrogen or C
1-10alkyl.
2. the title complex according to claims 1
1synthesis, it is characterized in that used tosic acid, sodium hydroxide,
bPO(2,5-two (pyridin-4-yl)-1,3,4-oxadiazole) and the ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are 0.1 ~ 3.5:0.1 ~ 3.5:0.1 ~ 3.5:0.1 ~ 3.5.
3. the title complex according to claims 1
1synthesis and catalyze and synthesize the method for dihydropyrimidinones, it is characterized in that selected temperature range is from room temperature to 200 degrees Celsius.
4. the title complex according to claims 1
1synthesis and catalyze and synthesize the method for dihydropyrimidinones, it is characterized in that required reaction time range was from 0.4 hour to 168 hours.
5. the title complex according to claims 1
1synthesis and catalyze and synthesize the method for dihydropyrimidinones, it is characterized in that selected organic solvent to be carbon atom quantity be the single methanol of 1-10, two alcohol, triol, tetrol or polyhydroxy-alcohol, acetone, ethyl acetate, dimethyl sulfoxide (DMSO), DMF, methylene dichloride, trichloromethane, tetracol phenixin, Nitromethane 99Min., tetrahydrofuran (THF), N-Methyl pyrrolidone, sherwood oil, benzene, the single solvent of toluene or mixed solvent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830934A (en) * | 2009-03-12 | 2010-09-15 | 北京化工大学 | Synthesis and structure of cobaltic biligand coordination polymer |
| BR102012021717A2 (en) * | 2012-08-29 | 2014-08-26 | Univ Brasilia Fudacao | IONALLY MARKED METAL CATALYZERS FOR MULTI-COMPONENT REACTIONS, THEIR PROCESS FOR OBTAINING AND APPLYING THEM TO OBTAIN BIOACTIVE SUBSTANCES |
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2015
- 2015-10-09 CN CN201510644052.7A patent/CN105175457A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830934A (en) * | 2009-03-12 | 2010-09-15 | 北京化工大学 | Synthesis and structure of cobaltic biligand coordination polymer |
| BR102012021717A2 (en) * | 2012-08-29 | 2014-08-26 | Univ Brasilia Fudacao | IONALLY MARKED METAL CATALYZERS FOR MULTI-COMPONENT REACTIONS, THEIR PROCESS FOR OBTAINING AND APPLYING THEM TO OBTAIN BIOACTIVE SUBSTANCES |
Non-Patent Citations (1)
| Title |
|---|
| MASOUD NASR-ESFAHANI ET AL.: "Efficient And Green Catalytic Synthesis Of Dihydropyrimidinone (Thione) Derivatives Using Cobalt Nitrate In Solvent-Free Conditions Using Cobalt Nitrate In Solvent-Free Conditions", 《J.CHIL.CHEM.SOC.》 * |
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Application publication date: 20151223 |