CN105233870A - Pyridine ethylene coordination polymers capable of catalyzing dihydropyrimidinones synthesis - Google Patents
Pyridine ethylene coordination polymers capable of catalyzing dihydropyrimidinones synthesis Download PDFInfo
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- CN105233870A CN105233870A CN201510614456.1A CN201510614456A CN105233870A CN 105233870 A CN105233870 A CN 105233870A CN 201510614456 A CN201510614456 A CN 201510614456A CN 105233870 A CN105233870 A CN 105233870A
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- synthesis
- alkyl
- dihydropyrimidinones
- alkoxyl
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Abstract
The invention provides a synthesis method of metal coordination polymers (MCPs) containing pyridine ethylene and p-aminobenzene sulfonic acid. The crystal structure of the metal coordination polymers is determined via single crystal X-ray diffraction. Catalytic activity of the metal coordination polymers on dihydropyrimidinones is studied. Catalyzed synthesis of dihydropyrimidinones is realized via a method which is simple and convenient in operation; and catalytic yield can be as high as 97%.
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 be between metal ion and organic ligand by the polymer that coordinate bond is formed, there is network structure that is highly regular and infinite expanding.It not only has the property of organic molecule and inorganic metal concurrently, and has occurred the new property that inorganic compound and organic compound do not have.Therefore it all many-sides such as magnetic, drug delivery, fluorescence, superconduction, adsorption of metal ions, nonlinear optics, catalysis all have a good application prospect (M.Ranocchiari, J.A.v.Bokhoven,
phys.Chem.Chem.Phys. 2011,
13, 6388-6396; H.R.Fu, Y.Kang, J.Zhang,
inorg.Chem. 2014,
53, 4209-4214; C.x.Ding, X.Rui, C.Wang, Y.s.Xie,
crystEngComm 2014,
16, 1010-1019; B) D.K.Singha, P.Mahata,
inorg.Chem. 2015,
54, 6373-6379).In these research fields, the catalytic activity of metal coordinating polymer causes the great interest of researchers, this be due to existing bibliographical information it can as the experiment of catalyst various organic reactions, such as suzuki reaction, alkylated reaction, coupling reaction, than (Corma, A., Garcia such as Ji Neili reactions, H., Xamena, F.X.L.
chem.Rev.,
2010, 110,4606-4655; Song, F.J., Wang, C., Falkowski, J.M., Ma, L.Q., Lin, W.B.,
j.Am.Chem.Soc.,
2010, 132,15390-15398.).Therefore constantly explore and design, environmental friendliness gentle at reaction condition and simple to operate to join the new catalyst of polymer based on metal in the ascendant.
Consider that dihydropyrimidinones has higher biologically active, it has very large using value in biological and pharmacology and medical science, and such as they can as pharmacologically active (K.S.Atwal such as the calcium ion channel blocker of antihypertensive, antibacterial, antiviral, anti-inflammatory and α 1a-antagonisms, 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.).Therefore people are caused to the synthesis of this compounds and study interest widely.Although along with the development of modern technologies and deepening continuously of research, the synthetic technology that the synthetic method of dihydropyrimidinones is more traditional is improved greatly (P.Biginelli,
chem.Ber., 1891,
24, 1317-2962; Cheng, C., Jing, H., RSCAdv.,
2014, 4,34325-34331; Yu, J.; Shi, F., Gong, L.Z., Acc.Chem.Res.,
2011, 44,1156-1171; Shi, X.L.; Yang, H.; Tao, M.; Zhang, W., RSCAdv.,
2013, 3,3939-3945).But still also come with some shortcomings, such as need the longer reaction time, higher reaction temperature, expensive catalyst and to the shortcoming such as environment is unfriendly, therefore reasonably design the catalyst with higher catalytic activity extremely urgent.
Therefore the present invention openly uses sulfanilic acid and pyridine ethene assemble the catalyst of formation under certain conditions as connector and metal ion and achieve it and synthesize the efficient catalytic of 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 catalyst, Reaction time shorten, simplification experimental implementation.
For achieving the above object, by sulfanilic acid, NaOH, cobalt nitrate and
dPE(1,2-bis-(pyridin-4-yl) ethene) is water-soluble with in the mixed solution of methyl alcohol, wherein
dPEstructural formula as Fig. 1.
Then transferred to by solution in reactor and heat 120 degree after 5 hours, the coordination polymer 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 catalyst, and what adopt one kettle way catalysis series benzaldehyde, ethyl acetoacetate 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 sulfanilic acid (0.2mmol) of 0.035g, 0.008g NaOH (0.2mmol), 0.036g
dPE(0.2mmol) and in the mixed solution of 0.029g cobalt nitrate (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 crystal structure figure.
Embodiment two, catalyze and synthesize the method for dihydropyrimidinones
The product 1 getting 0.02mmol joins as catalyst in the mixture of 1mmol benzaldehyde, 2mmol ethyl acetoacetate 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 dihydropyrimidinones.
Accompanying drawing explanation
Fig. 1, compound
dPEthe molecular formula of (1,2-bis-(pyridin-4-yl) ethene).
Fig. 2, product
1crystal structure figure.
Fig. 3, product
1catalytic result figure.
Detailed description of the invention
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 catalyst, 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 sulfanilic acid (0.2mmol) of 0.035g, 0.008g NaOH (0.2mmol), 0.036g
dPE(0.2mmol) and in the mixed solution of 0.029g cobalt nitrate (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 crystal structure figure.Wherein
dPEstructural 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 catalyst in the mixture of 1mmol benzaldehyde, 2mmol ethyl acetoacetate 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 dihydropyrimidinones.Wherein catalytic result is as Fig. 3.
Claims (5)
1. contain the synthesis of metal coordinating polymer and the synthetic method for efficient catalytic synthesizing dihydro pyrimidinones thereof of sulfanilic acid and pyridine ethene, it is characterized in that synthesis step is:
(1) embodiment one, complex
1synthesis
By a certain proportion of sulfanilic acid, NaOH,
dPE(1,2-bis-(pyridin-4-yl) ethene) and cobalt nitrate 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 crystal structure figure;
(2) embodiment two, catalyze and synthesize the method for dihydropyrimidinones
Its preparation process is with target product
1for catalyst, get appropriate product
1after catalyst reaction equation a period of time that catalysis is following at moderate temperatures, obtain target product, finally purify with water and organic solvent lotion and obtain pure product;
Reaction equation is:
；
In formula: R
1be selected from H, halogen, nitro, cyano group, trifluoromethyl, C
1~ C
9alkyl or C
1~ C
9alkoxyl; 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 or halo
1-8alkoxyl; 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, halo C
1-7alkoxyl or aryl; R
6and R
7each is independently selected from hydrogen or C
1-10alkyl.
2. the complex according to claims 1
1synthesis, it is characterized in that used sulfanilic acid, NaOH,
dPEthe ratio of (1,2-bis-(pyridin-4-yl) ethene) and cobalt nitrate is 0.1 ~ 3.5:0.1 ~ 3.5:0.1 ~ 3.5:0.1 ~ 3.5.
3. the 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 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 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, carrene, chloroform, carbon tetrachloride, nitromethane, oxolane, 1-METHYLPYRROLIDONE, benzinum, benzene, the single solvent of toluene or mixed solvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820127A (en) * | 2016-04-12 | 2016-08-03 | 齐鲁工业大学 | Cobalt sulfanilate with function of catalytically synthesizing dihydropyrimidinone compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021687A1 (en) * | 1995-12-14 | 1997-06-19 | Merck & Co., Inc. | Process for making dihydropyrimidinones |
| CN101781258A (en) * | 2009-10-23 | 2010-07-21 | 赣南师范学院 | Dihydro pyrimidone sulfoacid as well as salt compound and preparation method thereof |
| CN103113308A (en) * | 2013-01-25 | 2013-05-22 | 浙江大学 | Method for preparing dihydropyrimidinone derivative |
-
2015
- 2015-09-24 CN CN201510614456.1A patent/CN105233870A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021687A1 (en) * | 1995-12-14 | 1997-06-19 | Merck & Co., Inc. | Process for making dihydropyrimidinones |
| CN101781258A (en) * | 2009-10-23 | 2010-07-21 | 赣南师范学院 | Dihydro pyrimidone sulfoacid as well as salt compound and preparation method thereof |
| CN103113308A (en) * | 2013-01-25 | 2013-05-22 | 浙江大学 | Method for preparing dihydropyrimidinone derivative |
Non-Patent Citations (2)
| Title |
|---|
| JIN-HUA WANG,ET AL: "A series of phenyl sulfonate metal coordination polymers as catalysts for one-pot Biginelli reactions under solvent-free conditions", 《DALTON TRANSACTIONS》 * |
| ZHONG-XIANG DU,ET AL: "catena-Poly[[[diaquacobalt(II)]-μ-(E)-1,2-bis(4-pyridyl)ethylene-k2N:N’]bis(4-aminobenzenesulfonate)hexahydrate]", 《ACTA CRYSTALLOGRAPHICA SECTION E》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820127A (en) * | 2016-04-12 | 2016-08-03 | 齐鲁工业大学 | Cobalt sulfanilate with function of catalytically synthesizing dihydropyrimidinone compound |
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