CN101759715A - 5-chloro-salicyloyl hydrazine tributyltin chloride coordination compound as well as preparation method and application thereof - Google Patents
5-chloro-salicyloyl hydrazine tributyltin chloride coordination compound as well as preparation method and application thereof Download PDFInfo
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- CN101759715A CN101759715A CN201010011443A CN201010011443A CN101759715A CN 101759715 A CN101759715 A CN 101759715A CN 201010011443 A CN201010011443 A CN 201010011443A CN 201010011443 A CN201010011443 A CN 201010011443A CN 101759715 A CN101759715 A CN 101759715A
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- tributyltin chloride
- coordination compound
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Abstract
The invention discloses a 5-chloro-salicyloyl hydrazine tributyltin chloride coordination compound which has a structural formula as follows. A preparation method comprises the following steps of: sequentially adding 1.5-2.0 mmol of N-1, 8-naphthyl diacyl-5-chloro-salicyloyl hydrazine, 3.0-4.0 mmol of sodium methoxide and 50 mL of absolute methanol, stirring for 0.5 hour; then adding 2.0-3.0 mmol of tributyltin chloride, stirring for 6-8 hours at normal temperature; filtering, rotationally evaporating filter liquor to obtain a white solid; and then recrystallizing by using methylene dichloride-absolute methanol to obtain a light yellow crystal, i.e. an organotin coordination compound which has higher anticancer activity and can be used as a raw material for preparing drugs treating liver cancer and cervical cancer. Compared with the traditional commonly-used platinum anticancer drug, the organotin coordination compound has the advantages of higher anticancer activity, good lipid solubility, low cost, simple preparation method, and the like.
Description
Technical field
The present invention relates to a kind of 5-chlorine water poplar hydrazides tributyltin chloride coordination compound and preparation method thereof, and the application of this compound in the preparation cancer therapy drug.
Background technology
Organometallics (Organotin Compound) is meant the compound that contains one or more metal-carbon keys (M-C key).Organo-tin compound gets more and more people's extensive concerning because of its widespread use at aspects such as synthetic, catalysis, visit dirt, medicine, PVC stablizers.The eighties in 20th century, in the process to the research of metal cancer therapy drug and screening, some organo-tin compounds of discovery such as Crowe A.J. have the anti-tumor activity higher than cis-platinum, send out the new page of opening thereby opened organic chemistry.Many traditional characterization methods such as infrared optocoupler, nuclear magnetic resonance spectrum, mass spectrum etc. are in the successful utilization of organo-tin compound, for its research provides important guarantee, and the development and application of x-ray diffraction technique more it provides intuitively and accurately structural information.
Hydrazide compound has certain pharmacology and physiological activity, because itself have strong coordination ability, various coordination mode, is people's research object in recent years again always.Hydrazides class part is to be ligating atom with nitrogen-atoms and Sauerstoffatom, comparatively approaching with coenocorrelation, people are to the structure and the existing a large amount of report of character of hydrazides and transition metal complex thereof, result of study shows, hydrazides class part is obviously strengthened before the biological activity ratio's coordination that forms title complex, and its title complex has biology and pharmaceutical activity widely.
Summary of the invention
At above-mentioned prior art, the invention provides a kind of 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, and the preparation method and the application of this compound are provided.
The present invention is achieved by the following technical solutions:
A kind of 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, structural formula is as follows:
A kind of preparation method of 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, step is: add 1.5～2.0mmol N-1 in the round-bottomed flask of 100ml cleaning successively, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, the sodium methylate of 3.0～4.0mmol and the anhydrous methanol of 50mL, stir 0.5～2h, the tributyltin chloride that adds 2.0～3.0mmol again, stirring at normal temperature 6～8h; Filter, the filtrate rotary evaporation gets white solid, uses methylene dichloride-dehydrated alcohol recrystallization then, and wherein methylene dichloride and dehydrated alcohol volume ratio are 1: 1, get pale yellow crystals, are organotin complex, productive rate 65～70%.
Organotin complex of the present invention is through Infrared spectroscopy and nuclear magnetic resonance spectroscopy, and the result is as follows:
IR(KBr，cm
-1)：υ＝1648(C＝N)，1590(C＝N-N＝C)，778(Sn-O)，735(Ar-Cl)654(Sn-C).
1H?NMR(400MHz，DMSO，ppm，25℃)δ＝11.12(1H，Me-OH)，8.11-8.27(1H，ArH)，7.75-7.79(6H，NpH)，7.26-7.29(2H，ArH)，1.61-1.69(12H，-CH
2-CH
2-Me)，1.31-1.50(6H，Sn-CH
2-)，0.83-0.87(3H，-CH
3).
13C?NMR(100MHz，DMSO，ppm，25℃)δ＝161.96，160.02，134.47，133.06，131.77，131.70，131.51，128.15，127.01，126.92，123.76，122.50，121.87，120.59，77.29，76.985，76.665，27.66，27.06，26.74，17.20，13.48.
119Sn?NMR(400MHz，DMSO，ppm，25℃)δ＝-516.93.
Crystallographic data: crystallographic system belongs to oblique system, and spacer is C2/c, and unit cell parameters is:
Z=8, D=1.383 Mgm
-3, μ=0.895mm
-1, F (000)=2824,2.10 °＜θ＜25.01 °, the crystalline size size is 0.49 * 0.39 * 0.35mm, independent point diffraction is 16541, R
1=0.0343, wR
2=0.0788.
The application of described 5-chlorine water poplar hydrazides tributyltin chloride coordination compound in the medicine of preparation treatment people liver cancer, cervical cancer.
5-chlorine water poplar hydrazides tributyltin chloride coordination thing molecular formula of the present invention is C
32H
40ClN
2O
5Sn, molecular weight is 686.83, has higher anti-cancer activity, can its medicine for feedstock production treatment liver cancer, cervical cancer.Compare with the platinum-containing anticancer drug that generally uses at present, organotin complex of the present invention has higher, fat-soluble good, the characteristics such as cost is low, the preparation method is simple of antitumour activity, for the exploitation cancer therapy drug provides new way.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and experimental example:
Embodiment 1: preparation 5-chlorine water poplar hydrazides tributyltin chloride coordination compound
In the round-bottomed flask of 100mL cleaning, add 1.5mmol N-1,8-naphthalene diacyl-5-chlorine water poplar hydrazides, 3.0mmol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 2.0mmol tributyltin chloride subsequently, stirring at normal temperature 6h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, productive rate 65.2%.
Product is through Infrared spectroscopy and nuclear magnetic resonance spectroscopy, and the result is as follows:
IR(KBr，cm
-1)：υ＝1648(C＝N)，1590(C＝N-N＝C)，778(Sn-O)，735(Ar-Cl)654(Sn-C).
1H?NMR(400MHz，DMSO，ppm，25℃)δ＝11.12(1H，Me-OH)，8.11-8.27(1H，ArH)，7.75-7.79(6H，NpH)，7.26-7.29(2H，ArH)，1.61-1.69(12H，-CH
2-CH
2-Me)，1.31-1.50(6H，Sn-CH
2-)，0.83-0.87(3H，-CH
3).
13C?NMR(100MHz，DMSO，ppm，25℃)δ＝161.96，160.02，134.47，133.06，131.77，131.70，131.51，128.15，127.01，126.92，123.76，122.50，121.87，120.59，77.29，76.985，76.665，27.66，27.06，26.74，17.20，13.48.
119Sn?NMR(400MHz，DMSO，ppm，25℃)δ＝-516.93.
Crystallographic data: crystallographic system belongs to oblique system, and spacer is C2/c, and unit cell parameters is:
Z=8, D=1.383 Mgm
-3, μ=0.895mm
-1, F (000)=2824,2.10 °＜θ＜25.01 °, the crystalline size size is 0.49 * 0.39 * 0.35mm, independent point diffraction is 16541, R
1=0.0343, wR
2=0.0788.
Embodiment 2: preparation tributyltin chloride hydrazides coordination compound
Add 1.5mmol N-1 in the round-bottomed flask of 100mL, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, 3.0mmol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 3.0mmol tributyltin chloride subsequently, stirring at normal temperature 6h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, productive rate 67.3%.
Embodiment 3: preparation tributyltin chloride hydrazides coordination compound
Add 2.0mmol N-1 in the round-bottomed flask of 100mL, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, 3mmol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 2.5mmol tributyltin chloride subsequently, stirring at normal temperature 8h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, productive rate 69.5%.
Embodiment 4: preparation tributyltin chloride hydrazides coordination compound
Add 2.0mmol N-1 in the round-bottomed flask of 100mL, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, 3.0mmol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 3.0mmol tributyltin chloride subsequently, stirring at normal temperature 7h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, productive rate 66.1%.
Embodiment 5: preparation tributyltin chloride hydrazides coordination compound
Add 2.0mmol N-1 in the round-bottomed flask of 100mL, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, 4mol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 3.0mmol tributyltin chloride subsequently, and normal temperature stirs 8h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be tributyltin chloride hydrazides coordination compound, productive rate 67.4%.
Embodiment 6: preparation tributyltin chloride hydrazides coordination compound
Add 2.0mmol N-1 in the round-bottomed flask of 100mL, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, 4.0mol sodium methylate and 50mL anhydrous methanol stir 0.5h, add the 2.5mmol tributyltin chloride subsequently, stirring at normal temperature 7h.Filter, the filtrate rotary evaporation, white solid, use then methylene dichloride-dehydrated alcohol (V: V=1: 1) recrystallization, light yellow bulk crystals, be tributyltin chloride hydrazides coordination compound, productive rate 68.7%.
Experimental example: 5-chlorine water poplar hydrazides tributyltin chloride coordination compound of the present invention, when measuring, its external antitumour activity realizes that by MTT experiment forwarding method its principle is:
The MTT analytical method: (4,5-dimethylthiazil-2-yl)-2,5-diphenyl terrazolium bromide is the basis with metabolism reduction 3-.Be present in the relevant desaturase of NADP in the viable cell plastosome, yellow MTT can be reduced into insoluble hepatic Formazan, this enzyme of dead cell thing, MTT is not reduced, behind DMSO dissolving Formazan, available microplate reader is measured the optical density(OD) of characteristic wavelength, carries out relevant data and handles, and reaches a conclusion.
With the MTT analytical method people's liver cancer Bel-7402 cell strain, human cervical carcinoma Hela cell's strain are analyzed, measured its IC
50Value, the result is as shown in table 1, and conclusion is: by data in the table as can be known, and cancer therapy drug of the present invention, higher to people's liver cancer, human cervical carcinoma's antitumour activity, can be used as the candidate compound of cancer therapy drug.
Table 1 tributyltin chloride hydrazides coordination compound cancer therapy drug external activity test data
| People's liver cancer | Cervical cancer | |
| Sample IC 50(μg/mL) | 1.203 | ?0.727 |
| Cis-platinum IC50 (μ g/mL) | 1.23 [1] | ?4.998 [2] |
| Method | MTT | ?MTT |
| Cell strain | Bel-7402 | ?Hela |
List of references: [1] Li Yu, Liu Jie, Cui Zeshi etc., Chinese Medical Sciences University's journal 2004,33 (5): 392-3944.
[2] Pang Rongqing, Wang Li, the Journal of Clinical Oncologies such as Chen Jian 2003,8 (5): 332-334.
Claims (3)
1. 5-chlorine water poplar hydrazides tributyltin chloride coordination compound, it is characterized in that: structural formula is as follows:
2. the preparation method of the described 5-chlorine water of claim 1 poplar hydrazides tributyltin chloride coordination compound, it is characterized in that: step is: add 1.5～2.0mmol N-1 in round-bottomed flask successively, 8-naphthalene diacyl-5-chlorine water poplar hydrazides, the sodium methylate of 3.0～4.0mmol and the anhydrous methanol of 50mL, stir 0.5～2h, the tributyltin chloride that adds 2.0～3.0mmol again, stirring at normal temperature 6～8h; Filter, the filtrate rotary evaporation gets white solid, uses methylene dichloride-dehydrated alcohol recrystallization then, and wherein methylene dichloride and dehydrated alcohol volume ratio are 1: 1, get pale yellow crystals, are organotin complex.
3. the application of the described 5-chlorine water of claim 1 poplar hydrazides tributyltin chloride coordination compound in the medicine of preparation treatment people liver cancer, cervical cancer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757662A (en) * | 2012-07-03 | 2012-10-31 | 大连理工大学 | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof |
| CN102775449A (en) * | 2012-08-20 | 2012-11-14 | 聊城大学 | 1, 7-meta dicarbadecaborane carboxylic acid triphenyl stannic chloride compound as well as preparation method and application of compound |
-
2010
- 2010-01-14 CN CN201010011443A patent/CN101759715A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757662A (en) * | 2012-07-03 | 2012-10-31 | 大连理工大学 | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof |
| CN102757662B (en) * | 2012-07-03 | 2013-11-06 | 大连理工大学 | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof |
| CN102775449A (en) * | 2012-08-20 | 2012-11-14 | 聊城大学 | 1, 7-meta dicarbadecaborane carboxylic acid triphenyl stannic chloride compound as well as preparation method and application of compound |
| CN102775449B (en) * | 2012-08-20 | 2014-10-08 | 聊城大学 | 1, 7-meta dicarbadecaborane carboxylic acid triphenyl stannic chloride compound as well as preparation method and application of compound |
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Open date: 20100630 |