CN105131046A - Synthetic method based on catalyst for catalysis of dihydropyrimidine ketone compounds - Google Patents
Synthetic method based on catalyst for catalysis of dihydropyrimidine ketone compounds Download PDFInfo
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- CN105131046A CN105131046A CN201510561992.XA CN201510561992A CN105131046A CN 105131046 A CN105131046 A CN 105131046A CN 201510561992 A CN201510561992 A CN 201510561992A CN 105131046 A CN105131046 A CN 105131046A
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- synthesis
- alkyl
- dihydropyrimidinones
- title complex
- alkoxyl group
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Abstract
The invention provides an experimental method for synthesis of metal-complex polymers (MCPs) containing sulfanilic acid. The crystal structure of the metal-complex polymers (MCPs) is determined through monocrystal X-rays. The catalytic activity of the metal-complex polymers to dihydropyrimidine ketone compounds is researched further. Catalyzed synthesis of series dihydropyrimidine ketone compounds is carried out through a simple method which is easy to operate, and the catalysis yield can be as high as 98%.
Description
Technical field
The invention belongs to inorganic chemistry, organic chemistry and medicinal chemistry art, relate to the synthesis of metal coordinating polymer and catalyze and synthesize the experimental technique of dihydropyrimidinones.
Background technology
Metal coordinating polymer not only has various topological framework, and in gas absorption and storage, fluorescence, adsorption of metal ions, drug delivery and catalysis etc., there is potential using value (D.Y.Ma, Z.Li, J.X.Xiao, R.Deng, P.F.Lin, R.Q.Chen, Y.Q.Liang, H.F.Guo, B.Liu, J.Q.Liu
inorg.Chem. 2015,
54, 6719-6726; H.G.a.A.Corma, andF.X.Llabre ' siXamena,
chem.Rev. 2010,
110, 4606-4655).The research in this field has at present become the hot research content of the subject such as inorganic chemistry and materials chemistry.Research shows that the selection of organic ligand has a great impact the structure of target ligand polymer and performance.Therefore, in this article, we select Sulphanilic Acid and 4,4'-dipyridyl to be assembled into coordination polymer material under certain conditions as linker and metal ion.And have bibliographical information to contain sulfonic compound usually used as Protic Acid Catalyzed synthesis of organic substance.Transition metal ion is (as Co simultaneously
2+, Fe
3+, Ni
2+and Cu
2+) be all once used to catalyzing organic synthesis (E.M.Usai, M.F.Sini, D.Meloni, V.Solinas, A.Salis,
microporousMesoporousMater. 2013,
179, 54-62; S.Srivastava, M.S.Dagur, R.Gupta,
eur.J.Inorg.Chem. 2014,
2014, 4966-4974).Therefore the present invention considers both advantage above simultaneously, and we select Sulphanilic Acid and 4,4'-dipyridyl to assemble under certain conditions as linker and metal ion and form MCPs.
Consider that dihydropyrimidinones has higher biological activity, it has very large using value in biology and pharmacology and medical science, and often can as the important intermediate of organic synthesis, such as they can be used as the pharmacologically active (K.S.Atwal such as the calcium ion channel blocker of antihypertensive drug, antibacterial, antiviral, anti-inflammatory and α 1a-antagonism, G.C.Rovnyak, S.D.Kimball, D.M.Floyd, S.Moreland, B.N.Swanson, J.Z.Gougoutas, J.Schwartz, K.M.Smillie, M.F.Malley
j.Med.Chem. 1990,
33, 2629 – 2635.).Although the solid state reaction of utilization, the liquid phase reaction comprising ionic liquid, metal and Lewis acid base catalysis and utilize the method for other catalyst to obtain good progress, but still also come with some shortcomings, such as need the longer reaction times, expensive reagent, stronger Lewis Acids and Bases and use harmful organic solvent sometimes.Therefore the present invention openly uses above-mentioned MCPs catalyzer to achieve efficient preparation to dihydropyrimidinones.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 the metal organic coordination polymer 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 Phenylsulfonic acid, sodium hydroxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and
bPY(4,4'-dipyridyl) is water-soluble with in the mixing solutions of methyl alcohol, wherein
bPYstructural formula as Fig. 1.
Then transferred to by solution in reactor and heat 120 degree after 5 hours, the ligand polymer that precipitation obtains red crystals is filtered in cooling
1.By products obtained therefrom
1its molecular structure is determined, 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 Sulphanilic Acid (0.2mmol) of 0.035g, 0.008g sodium hydroxide (0.2mmol), 0.031g
bPY(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, 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 the metal organic coordination polymer 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, by Phenylsulfonic acid, sodium hydroxide, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and
bPY(4,4'-dipyridyl) is water-soluble with in the mixing solutions of methyl alcohol, wherein
bPYstructural formula as Fig. 1.
Then transferred to by solution in reactor and heat 120 degree after 5 hours, the ligand polymer that precipitation obtains red crystals is filtered in cooling
1.By products obtained therefrom
1its molecular structure is determined, 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 Sulphanilic Acid (0.2mmol) of 0.035g, 0.008g sodium hydroxide (0.2mmol), 0.031g
bPY(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, 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.
Accompanying drawing explanation
Fig. 1, compound
bPYmolecular formula.
Fig. 2, product
1crystalline structure figure.
Fig. 3, product
1catalytic result figure.
Claims (5)
1., containing the synthesis of metal coordinating polymer and the synthetic method for efficient catalytic synthesizing dihydro pyrimidinones thereof of Sulphanilic Acid, it is characterized in that synthesis step is:
1) embodiment one, title complex
1synthesis, by a certain proportion of Phenylsulfonic acid, sodium hydroxide,
bPY(4,4'-dipyridyl) and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in a certain amount of water and organic solvent, are then transferred in reactor by reaction mixture to have heated and are 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;
Catalyzed 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 Sulphanilic Acid, sodium hydroxide,
bPYthe ratio of (4,4'-dipyridyl) and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239288A (en) * | 2018-01-15 | 2018-07-03 | 齐鲁工业大学 | One kind is based on sulphonic acids metallic silver coordination polymer and preparation method thereof |
Citations (1)
| 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 |
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Patent Citations (1)
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| MASOUD NASR-ESFAHANI等: "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.》 * |
| MIN WANG等: "Synthesis and characterization of transition metal methanesulfonates and their catalytic behavior in Biginelli reactions", 《TRANSITION METAL CHEMISTRY》 * |
| YONGHUI WANG等: "Novel Hydrogen-Bonded Three-Dimensional Networks Encapsulating One-Dimensional Covalent Chains: [M(4,4’-bipy)(H2O)4](4-abs)2·nH2O(4,4’-bipy=4,4’-Bipyridine; 4-abs=4-Aminobenzenesulfonate)(M=Co,n=1; M=Mn,n=2)", 《INORG. CHEM.》 * |
| YUNFENG QIU等: "Efficient, stable, and reusable Lewis acid–surfactant-combinedcatalyst: One-pot Biginelli and solvent-free esterification reactions", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 向诗银等: "3,4-二氢嘧啶-2-酮衍生物合成研究进展", 《精细石油化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239288A (en) * | 2018-01-15 | 2018-07-03 | 齐鲁工业大学 | One kind is based on sulphonic acids metallic silver coordination polymer and preparation method thereof |
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