CN102093431A - Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster - Google Patents
Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster Download PDFInfo
- Publication number
- CN102093431A CN102093431A CN2011100258908A CN201110025890A CN102093431A CN 102093431 A CN102093431 A CN 102093431A CN 2011100258908 A CN2011100258908 A CN 2011100258908A CN 201110025890 A CN201110025890 A CN 201110025890A CN 102093431 A CN102093431 A CN 102093431A
- Authority
- CN
- China
- Prior art keywords
- title complex
- cluster
- preparation
- ferrocene
- organotin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CXOZQHPXKPDQGT-LURJTMIESA-N C[C@H]1C=CCC1 Chemical compound C[C@H]1C=CCC1 CXOZQHPXKPDQGT-LURJTMIESA-N 0.000 description 1
- VBGYITIDBRSEJV-UHFFFAOYSA-N OC(C[n]1nc(C(F)(F)F)cc1C1CCCC1)=O Chemical compound OC(C[n]1nc(C(F)(F)F)cc1C1CCCC1)=O VBGYITIDBRSEJV-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention provides an organotin-oxygen cluster containing ferrocene pyrazole. The cluster is characterized in that the complexes with the following chemical formulas are prepared from a ligand 3-trifluoromethyl-5-ferrocene pyrazole acetic acid (LCOOH) and monobutyltin oxide, dibutyltin oxide and triphenyltin hydroxide respectively: [BuSnO(OOCL)]6, [Ph4Sn2O(OCH3)(OOCL)]2 and [Bu4Sn2O(OOCL)2]2. The cluster has inhibiting effects on human lung cancer cells (A549), hepatoma cells (HepG2) and mouse melanoma (B16-F10) and the inhibiting effects are obviously superior to the inhibiting effects of the control drugs 5-fluorouracil and cisplatin, so the cluster can be applied to preparing the anti-tumor drugs.
Description
One, technical field
The present invention relates to a class and have the anti-tumor activity a metal-organic complex, exactly is organotin oxygen duster compound and the application in the preparation antitumor drug thereof that a class contains the ferrocene pyrazolyl.
Two, background technology
Since nineteen sixty-five U.S. Rosenbe chanced on cis-platinum and has antitumour activity, the medical of metal complexes had caused people's extensive concern, had opened up the frontier of metal complexes cancer therapy drug research.Platinum compound is being obtained some effects aspect some cancer of treatment really, but severe side effect also shows, and this replaces with regard to impelling us to seek some new medicines.Along with people to the pharmacological action of metal complexes understanding further deeply, new efficient, low toxicity, the metallic compound with antitumour activity constantly are synthesized out.Brown found Ph first in 1972
3SnO
2CCH
3Had since the growth effect that suppresses mouse tumor, people are more and more to synthetic, the molecular structure and the bioactivity research of organotin, and obtained a lot of significative results.The anticancer test center of the U.S. (NCI) has screened more than 2000 kind of organo-tin compound till 1989, wherein much is organotin oxygen duster compound.What research was more now mainly is the compound of trialkylated tin and dialkyl tin.Since the lower molecular weight organo-tin compound can grievous injury the immunity system of animal body, so the small molecular weight organo-tin compound is unsuitable for and makes carcinostatic agent.The Sherman suggestion replaces small molecular weight alkyl tin with low toxicity or nontoxic chain alkyl, cycloalkyl, aryl organo-tin compound with antitumour activity, and its anticancer effect may be better.The carboxylic acid compound of many dibutyl tins, tributyl tin and triphenyltin has shown anticancer efficiently work.Many antitumour activitys are measured and are shown, radicals R in the organotin is the principal element of the antitumour activity of the whole title complex of decision, the title complex antitumour activity of cyclohexyl, normal-butyl and phenyl is the strongest, ethyl takes second place, the most weak nearly unavailable of methyl, but the structure of part plays an important role equally to the antitumour activity and the anticancer spectrum of title complex.Title complex under physiological condition by slow hydrolytic process, final formation active intermediate and the effect of cancer cells dna molecular, and then hinder duplicating of DNA and bring into play antitumour activity, organic ligand R promotes that title complex enters the transmembrane movement of cancer cells, and influences the final activity of title complex therefrom.
The applicant has carried out following literature search to the application's theme:
1, http://www.google.com net result for retrieval: (2010/12/28)
2, CNKI result for retrieval:
In full-ferrocene pyrazoles organotin oxygen duster compound do not have pertinent literature.
In full-anti-tumor activity ferrocene pyrazoles organotin oxygen duster compound do not have pertinent literature.
Three, summary of the invention
The object of the present invention is to provide a class to have the organotin oxygen duster compound of anti-tumor activity, technical problem to be solved is the anti-tumor activity of selecting part and confirming this organotin duster compound.
The present invention selects the 3-trifluoromethyl-5-ferrocene pyrazolyl acetic acid of biologically active as part, respectively with Mono-n-butyltin, Dibutyltin oxide and the synthetic organotin oxygen duster compound that contains the ferrocene pyrazolyl of fentin hydroxide assembling.And it is carried out antitumor activity screening.
3-trifluoromethyl-5-ferrocene pyrazolyl acetic acid has following chemical formula:
Be convenient statement in the following description, note is done: LCOOH.
One of ferrocene pyrazolyl organotin oxygen duster compound that the present invention is alleged is the title complex that following chemical formula is arranged by ligand L COOH and Mono-n-butyltin preparation:
L:R ' in the formula: n-Bu,
For convenient statement, be designated as: [BuSnO (OOCL)] in the following description
6
Two of the ferrocene pyrazolyl organotin oxygen duster compound that the present invention is alleged is the title complexs that following chemical formula is arranged by ligand L COOH and Dibutyltin oxide preparation:
L:R ' in the formula: n-Bu
For convenient statement, be designated as: [Bu in the following description
4Sn
2O (OOCL)
2]
2
Three of the ferrocene pyrazolyl organotin oxygen duster compound that the present invention is alleged is the title complexs that following chemical formula is arranged by ligand L COOH and fentin hydroxide preparation:
L:R in the formula:
For convenient statement, be designated as: [Ph in the following description
4Sn
2O (OCH
3) (OOCL)]
2
The applicant has carried out anti tumor activity in vitro research to above-mentioned three kinds of title complexs, confirm that the three all has anti-tumor bioactivity, the purposes that is to say above-mentioned three kinds of title complexs is exactly the application in the preparation antitumor drug, specifically is exactly the application in the anti-lung cancer of preparation or anti-liver cancer or melanoma medicine.
The present invention has following characteristics:
1, the present invention has chosen 3-trifluoromethyl-5-ferrocene pyrazolyl acetic acid as part, not only provide advantageous conditions for the assembling metal title complex, and it is low to have introduced toxicity, the organic group that biological activity is good, thus reach the biological activity (seeing Table 1) that improves title complex.
2, the raw material of the present invention's employing cheaply is easy to get, and cost is low.And toxicity is low, environmental friendliness.
Four, description of drawings
Fig. 1 is title complex [BuSnO (OOCL)]
6Crystalline structure figure.
Fig. 2 is title complex [Bu
4Sn
2O (OOCL)
2]
2Crystalline structure figure.
Fig. 3 is title complex [Ph
4Sn
2O (OCH
3) (OOCL)]
2Crystalline structure figure.
Five, embodiment
Further describe the present invention by following examples, but should notice that scope of the present invention is not subjected to any restriction of these embodiment.
One, part [3-trifluoromethyl-5-ferrocene pyrazolyl acetic acid (LCOOH)] is synthetic:
(6.40g 0.02mol) is dissolved in the acetonitrile, and (3.36g 0.03mol) joins in the above-mentioned solution, behind 60 ℃ of heating 2h, with BrCH to take by weighing t-BuOK again to take by weighing 5-ferrocenyl-3-trifluoromethyl pyrazol S
2COOC
2H
5(6.68g 0.04mol) dropwise splashes in the flask, drips off afterreaction and carries out 4～5h, and TLC detects principal reaction to be finished substantially.Decompression steams acetonitrile, adds the water temperature rising reflux and makes the product hydrolysis, finishes reaction behind the 1.5h, takes out mixture, drips the pH of rare HCl (1M) regulator solution under the ice bath to slightly acidic (pH=5～6) in said mixture.Extract repeatedly with ethyl acetate, keep ethyl acetate layer, use anhydrous MgSO
4Dried overnight is filtered.Steam ethyl acetate, get yellow oil, pass through column chromatography for separation.Obtain pure product 3.40g, productive rate 45%, MS:(EI, 70eV): MS:(EI): M/z=378.02[M
+] .Anal.Calc for C
15H
13O
2N
2F
3Fe:C 47.70, H3.39, and N 7.38%; Found:C 47.62, and H 3.44, N 7.41%.
1H NMR (400MHz, CDCl
3): δ=4.293 (s, 5H), 4.490 (s, 4H), 5.086 (s, 2H), 6.512 (s, 1H)
Two, organotin oxygen duster compound is synthetic
1, [Ph
4Sn
2O (OCH
3) (OOCL)]
2Synthetic
Take by weighing Ph
3SnOH (0.1472,0.4mmol) and LCOOH (0.1512g, 0.4mmol) in the 50mL round-bottomed flask, add 25mL benzene, remove the less water that generates in the dereaction with water-and-oil separator, underpressure distillation is removed benzene and is got yellow solid behind the backflow 12h, with methylene dichloride: methyl alcohol=2: 1 (v/v) dissolving, filter, change in the 50mL fine taper bottle and leave standstill, have yellow crystals to separate out after the week.Anal.Calcd.for?C
82H
70N
4O
8F
6Fe
2Sn
4：C?50.77，H?3.64，N?2.89；Found：C?50.57，H?3.655，N?2.902(％).
119Sn?NMR(CDCl
3)：δ＝-88.243ppm.
2, [BuSnO (OOCL)]
6Synthetic
Take by weighing n-BuSnO (OH) (0.0836g, 0.4mmol) and LCOOH (0.1512,0.4mmol) in the 50mL round-bottomed flask, add 25mL benzene, remove the less water that generates in the dereaction with water-and-oil separator, underpressure distillation is removed benzene and is got yellow oil behind the backflow 12h, uses the acetonitrile dissolution filter, change in the 50mL fine taper bottle and leave standstill, separate out yellow bulk crystals after three days.Anal.Calcd?forC
120H
124N
12O
18F
18Fe
6Sn
6：C?42.25，H?3.66，N?4.93；Found：C?42.18，H?3.723，N?4.648(％).
119Sn?NMR(CDCl3)：δ＝-478.1ppm.
3, [Bu
4Sn
2O (OOCL)
2]
2Synthetic
Take by weighing n-Bu
2SnO (0.0996g, 0.4mmol) and LCOOH (0.1512,0.4mmol) in the 50mL round-bottomed flask, add 25mL benzene, remove the less water that generates in the dereaction with water-and-oil separator, underpressure distillation is removed benzene and is got yellow oil behind the backflow 12h, filters with dissolve with methanol, change in the 50mL fine taper bottle and leave standstill, separate out yellow bulk crystals after the week.Anal.Calcd.forC
96H
120N
8O
10F
12Fe
4Sn
4：C?46.64；H?4.89；N?4.53；Found：C?46.48，H?4.810；N?4.312(％).
119Sn?NMR(CDCl
3)：δ＝-200.568，-204.243ppm.
Three, the anti tumor activity in vitro of ferrocene pyrazolyl organotin oxygen duster compound research
Adopt MTT[3-(4,5)-two methyl-2-thiazole-(2,5)-and phenyl bromination tetrazole indigo plant] method measures analog derivative to human lung carcinoma cell (A549), the minimum inhibitory concentration of human liver cancer cell (HepG2) and murine melanoma (B16-F10) (minimalinhibitory concentration, MIC).
(1) preparation of nutrient solution (every liter): 1. suspension cell: RPMI-1640 cultivates one bag in powder (10.4g), new-born calf serum 100mL, penicillin solution (200,000 U/mL) 0.5ml, Streptomycin sulphate solution (200,000 U/mL) 0.5mL, after adding the tri-distilled water dissolving, the NaHCO with 5.6%
3The solution adjust pH is settled to 1000mL at last to 7.2-7.4.Filtration sterilization.2. attached cell: the same, add NaHCO again
32.00g, HEPES 2.38g.
(2) preparation of D-Hanks damping fluid (every liter): NaCl 8.00g, KCl 0.40g, Na
2HPO
412H
2O 0.06g, KH
2PO
40.06g, NaHCO
30.35g.Autoclaving.
(3) preparation of trypsin solution: utilizing the D-Hanks damping fluid to be made into concentration is 0.5% trypsin solution.Filtration sterilization.
(4) preparation of experiment soup: specimen is made into storing solution with a spot of tri-distilled water dissolving, general 10 times of preparation storing solutions by the experiment maximum concentration.According to the compound dissolution difference, available tri-distilled water directly dissolves, or with a small amount of DMSO hydrotropy, adds the tri-distilled water dissolving again.The concentration of DMSO in nutrient solution is unsuitable excessive, and the final concentration of DMSO generally is no more than 0.05%-0.1% in the every porocyte suspension after the dosing.Storing solution is stored in-20 ℃ of refrigerators standby.
(5) cultivation of human lung carcinoma cell (A549): be the adherent growth cell, routine is incubated in the RPMI-1640 nutrient solution (containing 10% calf serum, 100U/mL Streptomycin sulphate), puts 37 ℃, 5%CO
2Cultivate in the incubator, went down to posterity once every 3-4 days.Discard original fluid when going down to posterity earlier, again with the washing of D-Hanks damping fluid; Use 0.5% tryptic digestion about 30 seconds then, add a small amount of fresh medium and stop digestion; Piping and druming makes attached cell split away off from the culturing bottle wall; Pipette in right amount to the fresh culture bottle, the restock fresh medium is to original volume (nutrient solution volume be about culturing bottle capacity 1/10).
(6) cultivation of human liver cancer cell (HepG2): be the suspension growth cell, routine is incubated in the RPMI-1640 nutrient solution (containing 10% calf serum, 100U/mL Streptomycin sulphate), places 37 ℃, 5%CO
2Cultivate in the incubator, went down to posterity once every 3-4 days.When going down to posterity nutrient solution in the former bottle is transferred in the centrifuge tube, the centrifugal 5min of 1000rpm discards original fluid, add the equivalent fresh medium, piping and druming evenly pipettes in right amount to the fresh culture bottle, and the restock fresh medium is to original volume (nutrient solution volume be about culturing bottle capacity 1/10).
(7) cultivation of murine melanoma (B16-F10): identical with the cultural method of human liver cancer cell (HepG2).
(8) cell is hatched: 3 kinds of tumour cells in the vegetative period of taking the logarithm, the accent concentration of cell suspension is 1-1.5 * 10
5Individual mL
-1Every hole adds cell suspension 100 μ L in 96 well culture plates, puts 37 ℃, 5%CO
2Cultivate 24h in the incubator.After cultivating 24h, add soup by design respectively.
(9) dosing: will test soup and join respectively in each hole according to the concentration gradient of ultimate density, each concentration is established 6 parallel holes.Experiment is divided into drug test group (the test medicine that adds different concns respectively), control group (only add nutrient solution and cell, do not add the test medicine) and blank group (only add nutrient solution, do not add cell and test medicine).96 orifice plates after the dosing are placed 37 ℃, 5%CO
2Cultivate 48h in the incubator.The activity of positive control medicine (5-fluorouracil, cis-platinum) is measured according to the method for specimen.
(10) mensuration of survivaling cell: in having cultivated 96 orifice plates behind the 48h, every hole adds MTT 40 μ L (being made into 4mg/mL with the D-Hanks damping fluid).Behind 37 ℃ of placement 4h, remove supernatant liquor.Every hole adds 150 μ LDMSO, and vibration 5min makes formazan crystallization dissolving.At last, utilize automatic microplate reader to detect the optical density(OD) (OD value) in each hole at 570nm wavelength place.
The calculating of inhibiting rate: the inhibiting rate of cell growth calculates according to following formula:
Growth inhibition ratio=(1-survival rate) * 100%=[1-(OD
Experiment-O
Blank)/(OD
Contrast-OD
Blank)] * 100% (OD
ExperimentThe average optical of expression testing drug group, OD
ContrastThe average optical of expression control group, OD
BlankThe average optical of expression control group).
Half-inhibition concentration (IC
50) be defined as the drug level when the survival of 50% tumour cell.According to the optical density(OD) of measuring (OD value), make the typical curve of inhibitory rate of cell growth, on typical curve, try to achieve its corresponding drug level.The IC that records
50Be shown in Table 1
The listed part of table 1 the present invention contains the inhibition IC of ferrocene pyrazolyl organotin carboxylicesters to tumour cell
50Value (μ g/mL)
This shows that these three kinds of title complexs obviously are better than contrasting medicine 5-fluorouracil and cis-platinum to the restraining effect of A549, HepG2 and B16-F10, be expected in the preparation antitumor drug, use.
Claims (9)
1. organotin oxygen duster compound that contains the ferrocene pyrazolyl is characterized in that: by the title complex that following chemical formula is arranged of ligand L COOH and Mono-n-butyltin preparation:
L:R ' in the formula: n-Bu.
2. the purposes of title complex as claimed in claim 1 is characterized in that: the application of this title complex in the preparation antitumor drug.
3. the purposes of title complex according to claim 2 is characterized in that: the application of this title complex in the anti-lung cancer of preparation or anti-liver cancer or melanoma medicine.
4. organotin oxygen duster compound that contains the ferrocene pyrazolyl is characterized in that: by the title complex that following chemical formula is arranged of ligand L COOH and Dibutyltin oxide preparation:
L:R ' in the formula: n-Bu.
5. the purposes of title complex as claimed in claim 4 is characterized in that: the application of this title complex in the preparation antitumor drug.
6. the purposes of title complex according to claim 5 is characterized in that: the application of this title complex in the anti-lung cancer of preparation or anti-liver cancer or melanoma medicine.
7. organotin oxygen duster compound that contains the ferrocene pyrazolyl is characterized in that: by the title complex that following chemical formula is arranged of ligand L COOH and fentin hydroxide preparation:
L:R in the formula:
8. the purposes of title complex as claimed in claim 7 is characterized in that: the application of this title complex in the preparation antitumor drug.
9. the purposes of title complex according to claim 8 is characterized in that: the application of this title complex in the anti-lung cancer of preparation or anti-liver cancer or melanoma medicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110025890 CN102093431B (en) | 2011-01-24 | 2011-01-24 | Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110025890 CN102093431B (en) | 2011-01-24 | 2011-01-24 | Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102093431A true CN102093431A (en) | 2011-06-15 |
| CN102093431B CN102093431B (en) | 2013-06-12 |
Family
ID=44126718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110025890 Expired - Fee Related CN102093431B (en) | 2011-01-24 | 2011-01-24 | Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102093431B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391314A (en) * | 2011-11-29 | 2012-03-28 | 聊城大学 | 2,6-dipicolinic acid-(ferrocene monoformic acid)triphenyltin complex, its preparation method and its application |
| CN102424693A (en) * | 2011-10-10 | 2012-04-25 | 聊城大学 | Tetra-2,6-dipicolinic acid-di-(ferrocenedicarboxylic acid)triphenyl tin complex, and its preparation method and application |
| CN103113420A (en) * | 2013-02-04 | 2013-05-22 | 衡阳师范学院 | Ferrocenyl containing dibutyl tin-oxo cluster as well as preparation method and application thereof |
| CN104031092A (en) * | 2014-05-26 | 2014-09-10 | 上海应用技术学院 | Ferrocene benzotriazole derivatives as well as preparation method and application of ferrocene benzotriazoles derivatives |
| RU2533823C1 (en) * | 2013-07-05 | 2014-11-20 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | 1-(1,1,1,3,3,3-hexafluoro-2-ferrocenylprop-2-yl)-imidazole, possessing antitumour activity and methods of obtaining thereof (versions) |
| CN106588973A (en) * | 2016-12-12 | 2017-04-26 | 吉林医药学院 | Hexanuclear drum-shaped organotin carboxylate complex of p-methylphenyl tin, and preparation method and application thereof |
| RU2714891C1 (en) * | 2019-10-15 | 2020-02-20 | Общество С Ограниченной Ответственностью "Научно-Исследовательская Фирма "Ультрасан" (Ооо Ниф "Ультрасан") | Ferrocenylalkyl derivatives of dipyrazolylselenides as biologically active compounds and methods for production thereof (versions) |
| CN113402567A (en) * | 2021-06-15 | 2021-09-17 | 宁德师范学院 | Two-dimensional layered germanium vanadium oxygen cluster compound and synthesis method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2156965A1 (en) * | 1994-09-09 | 1996-03-10 | Marcel Gielen | Aromatic fluorine-containing organotin compounds and anti-tumour compositions |
-
2011
- 2011-01-24 CN CN 201110025890 patent/CN102093431B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2156965A1 (en) * | 1994-09-09 | 1996-03-10 | Marcel Gielen | Aromatic fluorine-containing organotin compounds and anti-tumour compositions |
Non-Patent Citations (2)
| Title |
|---|
| 卢文贯，等: "二正丁基锡邻二茂铁基苯甲酸酯配合物的合成、表征及其体外抗肿瘤活性", 《化学研究与应用》, vol. 13, no. 4, 31 August 2001 (2001-08-31), pages 372 - 375 * |
| 陈绍文，等: "具有抗肿瘤活性有机锡化合物的研究进展", 《聊城大学学报（自然科学版）》, vol. 19, no. 3, 30 September 2006 (2006-09-30), pages 50 - 53 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424693A (en) * | 2011-10-10 | 2012-04-25 | 聊城大学 | Tetra-2,6-dipicolinic acid-di-(ferrocenedicarboxylic acid)triphenyl tin complex, and its preparation method and application |
| CN102424693B (en) * | 2011-10-10 | 2014-02-12 | 聊城大学 | Tetra-2,6-dipicolinic acid-di-(ferrocenedicarboxylic acid)triphenyl tin complex, and its preparation method and application |
| CN102391314A (en) * | 2011-11-29 | 2012-03-28 | 聊城大学 | 2,6-dipicolinic acid-(ferrocene monoformic acid)triphenyltin complex, its preparation method and its application |
| CN102391314B (en) * | 2011-11-29 | 2013-09-11 | 聊城大学 | 2,6-dipicolinic acid-(ferrocene monoformic acid)triphenyltin complex, preparation method and application thereof |
| CN103113420A (en) * | 2013-02-04 | 2013-05-22 | 衡阳师范学院 | Ferrocenyl containing dibutyl tin-oxo cluster as well as preparation method and application thereof |
| CN103113420B (en) * | 2013-02-04 | 2015-12-23 | 衡阳师范学院 | A kind of dibutyl tin oxygen duster compound containing ferrocenyl and preparation method and application |
| RU2533823C1 (en) * | 2013-07-05 | 2014-11-20 | Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) | 1-(1,1,1,3,3,3-hexafluoro-2-ferrocenylprop-2-yl)-imidazole, possessing antitumour activity and methods of obtaining thereof (versions) |
| CN104031092A (en) * | 2014-05-26 | 2014-09-10 | 上海应用技术学院 | Ferrocene benzotriazole derivatives as well as preparation method and application of ferrocene benzotriazoles derivatives |
| CN106588973A (en) * | 2016-12-12 | 2017-04-26 | 吉林医药学院 | Hexanuclear drum-shaped organotin carboxylate complex of p-methylphenyl tin, and preparation method and application thereof |
| CN106588973B (en) * | 2016-12-12 | 2019-02-22 | 吉林医药学院 | A kind of six core drum type organotin carboxylate complexs of p-methylphenyl tin and its preparation method and application |
| RU2714891C1 (en) * | 2019-10-15 | 2020-02-20 | Общество С Ограниченной Ответственностью "Научно-Исследовательская Фирма "Ультрасан" (Ооо Ниф "Ультрасан") | Ferrocenylalkyl derivatives of dipyrazolylselenides as biologically active compounds and methods for production thereof (versions) |
| CN113402567A (en) * | 2021-06-15 | 2021-09-17 | 宁德师范学院 | Two-dimensional layered germanium vanadium oxygen cluster compound and synthesis method and application thereof |
| CN113402567B (en) * | 2021-06-15 | 2023-06-09 | 宁德师范学院 | Two-dimensional layered germanium vanadium oxide cluster compound and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102093431B (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093431B (en) | Organotin-oxygen cluster containing ferrocene pyrazole and application of cluster | |
| CN101003470B (en) | Analog of mono carbonyl structure of curcumin, and usage | |
| CN103113420B (en) | A kind of dibutyl tin oxygen duster compound containing ferrocenyl and preparation method and application | |
| CN103554170A (en) | Aryl organic acid ester-containing tricyclohexyltin compounds, and preparation methods and application thereof | |
| CN103420990B (en) | 7-oxygen, sulphur or azepine substituted cumarin and derivative thereof and purposes | |
| CN103396435B (en) | Dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex as well as preparation method and application thereof | |
| CN103509046B (en) | Two [three (2-methyl-2-phenyl propyl) tin] dicarboxylic esters and preparation method and application | |
| CN103087115A (en) | Ferrocenyl-containing tributyltin benzoate coordination polymer, and preparation method and application thereof | |
| CN102627597A (en) | Indole-3-carboxaldehyde isobutyryl hydrazone derivatives and preparation method thereof | |
| CN102627685A (en) | Nitric oxide-donating glutathione compound, preparation method and medical purpose thereof | |
| CN102250150A (en) | Organic hydridized tetra-core platinum complex and preparation method thereof as well as application technology field of complex in antitumor medicament preparation | |
| CN104558094A (en) | Sapogenin derivative, preparation method of derivative and application thereof in preparation of antitumor drugs | |
| CN101747353A (en) | N'-(3-nitrobenzoyl)-N-salicylyl hydrazne copper complex as well as preparation method and application thereof | |
| CN102101874B (en) | Di(cyclopentadienyl)iron pyrazol copper and silver complexes and use thereof | |
| CN103483373B (en) | Tributyl tin organic acid acetic and preparation method and application | |
| CN102381951A (en) | Cyclohexanone-contained mono-carbonyl analogues of curcumin and usage thereof | |
| CN105061441A (en) | Coumarin pyrazole compounds containing nitrogen heterocycles such as piperazine and the like, preparation of coumarin pyrazole compounds and application of coumarin pyrazole compounds in tumor cell inhibition | |
| CN110698512B (en) | Tin complex with 2-acetylpyridine thiosemicarbazone as ligand and synthesis method thereof | |
| CN108164490B (en) | Genistein derivatives, their preparation and use | |
| CN112876414A (en) | Polyamine-modified naphthalimide conjugate, and preparation method and application thereof | |
| CN103450252B (en) | Dibutyltin alpha-naphthylacetate having tin-containing oxygen heterocyclic structure and preparation method and application thereof | |
| CN113735915B (en) | Heteronuclear metal iridium-rhenium complex and preparation method and application thereof | |
| CN103319431B (en) | 2-mercaptoacetophenone-containing 1, 3, 4-oxadiazole derivative, its preparation method and antitumor activity | |
| CN111704631B (en) | Preparation method and application of bis [ tri (2-methyl-2-phenyl) propyltin ] pamoate complex | |
| CN113929669B (en) | Novel hesperetin pyrimidine hydrazone derivative as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130612 Termination date: 20170124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |