CN106366113A - 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex and its preparation method and use - Google Patents

2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex and its preparation method and use Download PDF

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CN106366113A
CN106366113A CN201610691923.5A CN201610691923A CN106366113A CN 106366113 A CN106366113 A CN 106366113A CN 201610691923 A CN201610691923 A CN 201610691923A CN 106366113 A CN106366113 A CN 106366113A
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propionic acid
dichloro benzyl
stannum
coordination compound
toluyl hydrazone
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CN201610691923.5A
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Chinese (zh)
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谭宇星
蒋伍玖
庾江喜
朱小明
邝代治
张复兴
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衡阳师范学院
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/22Tin compounds
    • C07F7/2284Compounds with one or more Sn-N linkages

Abstract

The invention discloses a 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex. The 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex has a structure shown in the structural formula (I). In the structural formula (I), R represents 2, 4-dichlorobenzyl. The invention also discloses a preparation method of the 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex and a use of the 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex in preparation of an anticancer drug.

Description

A kind of 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound And its preparation method and application

Technical field

The present invention relates to a kind of 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound and its system Preparation Method, and this 2- carbonyl propionic acid prepared in cancer therapy drug to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound Application.

Background technology

Organotin is the metallo-organic compound that a class contains sn-c key.Researcher just noticed before very early The Anticancer Activity in vitro of organo-tin compound.The research of organotin (iv) antitumor activity of compound can trace back to nineteen twenty-nine. 1967, kanisawa etc. thought that stannic chloride is invalid to the primary tumor of mice and rat.But in 1972, brown found, By food or drug administration by injection, triphenyltin acetate ph3snoocch3The tumour growth of mice can be suppressed, and triphenyltin chloride Then can not.Between 1972 ~ 1977 years, the substantial amounts of organo-tin compound of Dutch scholar's research, but find no screening valency further The compound of value.They continue deeper into research, finally found that the tin compound of two organic group coordinations, such as tin-oxide (r2Sno), stannum hydroxide [ snr2(oh) x ] etc. have anti-tumor activity, and find out that they all contain or hydrolyze and can produce stannum oxygen Key.1980, crowe etc. was found that some organo-tin compounds have preferable active anticancer again, from this, resisted with regard to organotin The research of cancer activity becomes another extremely active focus after cisplatin.1989, American National anticancer research institute (national cancer institute) has carried out antitumor activity screening, result table to more than 2,000 kinds of organo-tin compounds Some organo-tin compounds bright have inhibitory action to p388 Lymphocytic leukemia.2002, gielen et al. was to organic The activity of stannum carboxylate compound has done comprehensive summing up, thinks that many organo-tin compounds have really preferably external after research Active anticancer.

Research shows, the organic group that organic tin atom connects and the part participating in being coordinated decide organo-tin compound Biological activity, select some to have the tin atom in organic ligand and the organotin of good biological activity in itself and be coordinated and cause The great interest of people.Acylhydrazone is by a class schiff alkali cpd of hydrazide kind compound modification, they Formed by aldehydes or ketones and hydrazides condensation, there is in molecule the of bonding similar with peptide bond, there is good biological activity, stronger joining Capability and various coordination mode, and have a wide range of applications at aspects such as medicine, pesticide, material and analytical reagents.Closely Nian Lai, both at home and abroad many research worker it is compared in terms of biological activity and in depth studies, research finds acylhydrazone class Compound has the various active such as anticancer, sterilization, antiinflammatory.Therefore, acylhydrazone class schiff aar ligand is combined with organotin it is intended to Obtain the higher noval chemical compound of biological activity, become people's research direction interested.

Chinese patent cn 102718794a discloses a kind of pair of acylhydrazone class schiff alkali stannous phenide coordination compound and its in system Application in standby Antilung gland cancer, colon cancer, the medicine of leukaemia.

Chinese patent cn 101851251a disclose a kind of dibutyl tin coordination compound of acylhydrazone class schiff aar ligand and its Application in preparation treatment hepatocarcinoma, adenocarcinoma of lung, breast carcinoma, carcinoma of prostate, colon cancer or early children's leukemic medicine of grain.

Document (journal of organometallic chemistry, 2014,75:83-91) is reported, organotin Acylhydrazone class schiff alkali coordination compound is thin to human colon cancer cell (hct-116), human lung adenocarcinoma cell (a549), human umblilical vein endothelial Born of the same parents (huvec) have compared with strong biological activity, and are better than carboplatin.

Document (journal of organometallic chemistry, 2013,724:23-31) is reported, series has Machine stannum acylhydrazone class schiff alkali coordination compound, organo-tin compound and acylhydrazone class schiff aar ligand are respectively to human lung adenocarcinoma cell (a549), the inhibitory action of the cancerous cell such as human colon cancer cell (hct-8), people in loop (hl-60).

Document (bioorganic & medicinal chemistry letters, 2015,25:4461- 4463) Report, the active anticancer to human liver cancer cell (huh-7) and human lung adenocarcinoma cell (a549) for multiple acylhydrazone class schiff aar ligands.

Document (journal of organometallic chemistry, 2016,804:48-58) is reported, two hydrocarbon Base stannum acylhydrazone class schiff alkali coordination compound is to human lung adenocarcinoma cell (a549), human cervical carcinoma cell (hela), human breast cancer cell (mcf-7) inhibitory action of cancerous cell such as.

It is to the experiment proved that the material with active anticancer based on acylhydrazone class schiff alkali organotin complex, the present invention selects Select and toluyl hydrazine, Sodium Pyruvate and two (2,4- dichloro benzyl) stannum dichloride are reacted under certain condition, synthesis obtains To human lung carcinoma cell (h460), human liver cancer cell (hepg2) and human breast cancer cell (mcf7), there is certain inhibitory activity Coordination compound, provides new approach for exploitation cancer therapy drug.

Content of the invention

The first object of the present invention there is provided a kind of 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) Stannum coordination compound.

The second object of the present invention is to provide above-mentioned 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum Coordination compound preparation method.

The third object of the present invention is to provide above-mentioned 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum Application in preparing cancer therapy drug for the coordination compound.

As a first aspect of the present invention a kind of 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum Coordination compound, is the coordination compound of structural formula (i)

(i)

Wherein r is 2,4- dichloro benzyl.

The 2- carbonyl propionic acid of the present invention is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound through elementary analysiss, red External spectrum, nuclear magnetic resoance spectrum and x- ray single crystal diffraction structural analyses, result is as follows:

Elementary analysiss (c52h48cl8n4o8sn2): value of calculation: c 45.32, h 3.51, n 4.07;Measured value: c 45.38, h 3.51, n 4.04.

ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414.

1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h).

13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77.

119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.

The 2- carbonyl propionic acid of the present invention is crystal structure to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, its Crystal is monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, b=1.14311 (3) nm, c=1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc=1.634 mg m-3, m (mok α)=1.329 mm-1, f (000)=1376.

The 2- carbonyl propionic acid of the present invention is structurally characterized in that to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound: In molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations.

The 2- carbonyl propionic acid of the present invention has certain heat to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound Stability range, can stable existence below 116 DEG C.

As a second aspect of the present invention a kind of 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum The preparation method of coordination compound, adds two (2,4- dichloro benzyl) stannum dichloride, to methyl in the reaction vessel having nitrogen protection Benzoyl hydrazine, Sodium Pyruvate and solvent absolute methanol, react 5 ~ 24 h, cooling under conditions of temperature is 45 ~ 65 DEG C, filter, Control solvent volatilization crystallization under conditions of 20 ~ 35 DEG C, obtain yellow transparent crystal, as 2- carbonyl propionic acid is to toluyl hydrazone Two (2,4- dichloro benzyl) stannum coordination compound.

The 2- carbonyl propionic acid of the present invention to the preparation characteristic of toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound is: From the relatively easy raw material being easy to get, without the separation of intermediate, directly obtain baroque molecule, i.e. one kettle way;This The reaction of sample economically and environmentally close friend on advantageously.

In a preferred embodiment of the invention, described two (2,4- dichloro benzyl) stannum dichloride, to toluyl Hydrazine, the amount of the material of Sodium Pyruvate three are than for 1:(1 ~ 1.05): (1.05 ~ 1.15).

In a preferred embodiment of the invention, described solvent absolute methanol consumption is every mM two (2,4- dichloros Benzyl) stannum dichloride adds 15 ~ and 35 milliliters.

As a third aspect of the present invention a kind of 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum Application in preparing cancer therapy drug for the coordination compound.

Applicant has carried out body to above-mentioned 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound Outer active anticancer determines research it is thus identified that 2- carbonyl propionic acid has to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound Certain anticancer bioactive is that is to say, that the purposes of above-mentioned coordination compound is the application in preparing cancer therapy drug, specifically It is exactly the application in preparing anti-human pulmonary carcinoma, human liver cancer and human breast carcinoma medicine.

The 2- carbonyl propionic acid of the present invention to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound to human lung carcinoma cell, Human liver cancer cell and human breast cancer cell show good active anticancer, and the 2- carbonyl propionic acid of the present invention is to toluyl hydrazone The features such as two (2,4- dichloro benzyl) stannum coordination compound active anticancer height, low cost, preparation method are simple, for developing new anticarcinogen Thing provides new way.

Brief description

Fig. 1 is the ir spectrogram to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid.

Fig. 2 is 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound1H nmr spectrogram.

Fig. 3 is 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound13C nmr spectrogram.

Fig. 4 is 2- carbonyl propionic acid to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound119Sn nmr spectrogram.

Fig. 5 is the crystal structure figure to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid.

Fig. 6 is the tg-dtg curve to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid.

Specific embodiment

By detailed description below, the present invention is described in further detail.

Embodiment 1:

The preparation to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid:

0.510g (1.0mmol) two (2,4- dichloro benzyl) dichloride is added in the 100ml there-necked flask having nitrogen protection Stannum, 0.150g (1.0mmol) to toluyl hydrazine, 0.121g (1.1mmol) Sodium Pyruvate and 15ml solvent absolute methanol, React 8 h under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, control solvent volatilization crystallization under conditions of 20 ~ 35 DEG C, obtain Yellow transparent crystal, as 2- carbonyl propionic acid are to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound.Yield: 68.3%. Fusing point: 116 ~ 118 DEG C (dec).

Elementary analysiss (c52h48cl8n4o8sn2): value of calculation: c 45.32, h 3.51, n 4.07;Measured value: c 45.38, h 3.51, n 4.04.

ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414.

1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h).

13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77.

119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.

Crystallographic data: monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, b=1.14311 (3) nm, C=1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc= 1.634 mg·m-3, m (mok α)=1.329 mm-1, f (000)=1376.

Embodiment 2:

The preparation to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid:

0.510g (1.0mmol) two (2,4- dichloro benzyl) dichloride is added in the 100ml there-necked flask having nitrogen protection Stannum, 0.150g (1.0mmol) are to toluyl hydrazine, 0.115g (1.05mmol) Sodium Pyruvate and 35ml solvent no water beetle Alcohol, reacts 5 h under conditions of temperature is 45 ~ 65 DEG C, and cooling is filtered, and controls solvent volatilization knot under conditions of 20 ~ 35 DEG C Crystalline substance, obtains yellow transparent crystal, as 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound.Yield: 72.5%.Fusing point: 116 ~ 118 DEG C (dec).

Elementary analysiss (c52h48cl8n4o8sn2): value of calculation: c 45.32, h 3.51, n 4.07;Measured value: c 45.38, h 3.51, n 4.04.

ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414.

1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h).

13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77.

119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.

Crystallographic data: monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, b=1.14311 (3) nm, C=1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc= 1.634 mg·m-3, m (mok α)=1.329 mm-1, f (000)=1376.

Embodiment 3:

The preparation to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid:

0.510g (1.0mmol) two (2,4- dichloro benzyl) dichloride is added in the 100ml there-necked flask having nitrogen protection Stannum, 0.158g (1.05mmol) are to toluyl hydrazine, 0.126g (1.15mmol) Sodium Pyruvate and 25ml solvent no water beetle Alcohol, reacts 24 h under conditions of temperature is 45 ~ 65 DEG C, and cooling is filtered, and controls solvent volatilization knot under conditions of 20 ~ 35 DEG C Crystalline substance, obtains yellow transparent crystal, as 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound.Yield: 71.1%.Fusing point: 116 ~ 118 DEG C (dec).

Elementary analysiss (c52h48cl8n4o8sn2): value of calculation: c 45.32, h 3.51, n 4.07;Measured value: c 45.38, h 3.51, n 4.04.

ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414.

1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h).

13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77.

119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.

Crystallographic data: monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, b=1.14311 (3) nm, C=1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc= 1.634 mg·m-3, m (mok α)=1.329 mm-1, f (000)=1376.

Embodiment 4:

The preparation to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid:

5.100g (10.0mmol) two (2,4- dichloro benzyl) dichloride is added in the 500ml there-necked flask having nitrogen protection Stannum, 1.545g (10.3mmol) are to toluyl hydrazine, 1.210g (11.0mmol) Sodium Pyruvate and 200ml solvent no water beetle Alcohol, reacts 22 h under conditions of temperature is 45 ~ 65 DEG C, and cooling is filtered, and controls solvent volatilization knot under conditions of 20 ~ 35 DEG C Crystalline substance, obtains yellow transparent crystal, as 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound.Yield: 68.7%.Fusing point: 116 ~ 118 DEG C (dec).

Elementary analysiss (c52h48cl8n4o8sn2): value of calculation: c 45.32, h 3.51, n 4.07;Measured value: c 45.38, h 3.51, n 4.04.

ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414.

1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h).

13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77.

119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.

Crystallographic data: monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, b=1.14311 (3) nm, C=1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc= 1.634 mg·m-3, m (mok α)=1.329 mm-1, f (000)=1376.

Test example:

The 2- carbonyl propionic acid of the present invention is surveyed to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, its Anticancer Activity in vitro Surely realized by mtt experimental technique.

Mtt analytic process:

With metabolism reduction 3- (4,5-dimethylthiazol-2-yl) -2,5-diphenyltetrazolium bromide it is Basis.Succinate dehydrogenase in living cells mitochondria can make exogenous mtt be reduced to water-insoluble bluish violet crystallization first a ceremonial jade-ladle, used in libation (formazan) and be deposited in cell, and dead cell no this function.Dimethyl sulfoxide (dmso) can dissolve the first a ceremonial jade-ladle, used in libation in cell, Measure the optical density of characteristic wavelength with microplate reader, can indirectly reflect living cells quantity.

The 2- carbonyl propionic acid of embodiment 1 preparation is measured to toluyl hydrazone two (2,4- dichloro benzyl) using mtt method The inhibitory activity to human lung carcinoma cell (h460), human liver cancer cell (hepg2) and human breast cancer cell (mcf7) for the stannum coordination compound.

Cell strain and cultivating system: h460, hepg2 and mcf7 cell strain takes from American. tissue incubator (atcc).With containing Rpmi 1640 (gibico company) culture medium of 10% hyclone, in 5% (volume fraction) co2, 37 DEG C of saturated humidity incubators Inside carry out In vitro culture.

Test process: test medicinal liquid (1nm ~ 10 μm) is added separately in each hole according to the Concentraton gradient of concentration, often Individual concentration sets 6 parallel holes.Experiment is divided into drug study group (being separately added into the test medicine of variable concentrations), matched group (only to add training Nutrient solution and cell, are not added with testing medicine) and blank group (only adding culture medicine, be not added with cell and test medicine).Orifice plate after dosing is put In 37 DEG C, 5%co272h is cultivated in incubator.The activity of control drug measures according to the method for test sample.Cultivating 72h In orifice plate afterwards, every hole adds mtt 40 μ l (being made into 4mg/ml with d-hanks buffer).After placing 4h at 37 DEG C, remove upper strata Clear liquid.Every hole adds 150 μ l dmso, vibrates 5min, makes formazan crystallize dissolving.Finally, using automatic microplate reader in 570nm The optical density in each hole is detected at wavelength.

Data processing: data processing uses graph pad prism version 7.0 program, coordination compound ic50By journey The nonlinear regression model (NLRM) in sequence with s shape dose response is fitted obtaining.

Thin to human lung carcinoma cell (h460), human liver cancer cell (hepg2) and human breast cancer cell (mcf7) with mtt analytic process Born of the same parents' strain is analyzed, and measures its ic50Value, as shown in table 1, conclusion is result: from data in table, with the 2- carbonyl of the present invention Propanoic acid is used as cancer therapy drug to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, to human lung carcinoma cell (h460), people Hepatoma carcinoma cell (hepg2) and human breast cancer cell (mcf7) have certain drug effect, can be used as the candidate compound of cancer therapy drug.

Table 1 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound cancer therapy drug external activity Test data.

Human lung cancer Human liver cancer Human breast carcinoma Cell strain h460 hepg2 mcf7 ic50(μm) 1.64±0.07 0.70±0.15 0.87±0.22

The 2- carbonyl propionic acid of remaining embodiment preparation is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound with mtt The active anticancer method of testing to human lung carcinoma cell (h460), human liver cancer cell (hepg2) and human breast cancer cell (mcf7) for the method Same test example, test result is essentially identical with table 1.

These are only the preferred embodiments of the present invention and test example, be not limited to the present invention it is clear that the skill of this area Art personnel can carry out various changes, modification without departing from the spirit and scope of the present invention to the present invention.If to the present invention's These modifications and modification belong within the scope of the claims in the present invention and its equivalent technologies, belong to the protection model of the present invention Enclose.

Claims (9)

1. a kind of 2- carbonyl propionic acid is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, for following structural formula (i) Coordination compound:
(i)
Wherein r is 2,4- dichloro benzyl.
2. containing a kind of 2- carbonyl propionic acid, toluyl hydrazone two (2,4- dichloro benzyl) stannum is joined as claimed in claim 1 Compound, its ir data: ft-ir (kbr, ν/cm-1): 3089, 3059, 2918, 1616, 1581, 1471, 1392, 1317, 1201, 1176, 1026, 842, 815, 746, 727, 626, 594, 538, 453, 414;Its Nuclear-magnetism modal data:1h nmr (500 mhz, cdcl3, δ/ppm): 7.80 (d,j=8.1 hz, 2h), 7.26 (s, 2h), 7.22 (d,j=8.1 hz, 2h), 7.04 (m, 4h), 3.49 (s, 3h), 3.17 (d,j=12.0 hz, 2h), 3.10 (d,j=12.0 hz, 2h), 2.49 (s, 3h), 2.43 (s, 3h), 1.02 (s, 1h);13c nmr (126 mhz, cdcl3, δ/ppm): 174.77, 163.69, 155.10, 143.49, 133.49, 133.34, 132.85, 132.28, 130.81, 129.07, 128.88, 128.46, 127.43, 50.92, 27.62, 21.79, 13.77;119sn nmr (187 mhz, cdcl3, δ/ppm): -243.58.
3. 2- carbonyl propionic acid as claimed in claim 1 is to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, its In, described 2- carbonyl propionic acid is crystal structure to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound, its crystallography Data is as follows: monoclinic system, space group p2 (1)/n, a=1.39157 (3) nm, and b=1.14311 (3) nm, c= 1.80656 (5) nm, α=γ=90 °, β=103.0000 (10) °, z=2, v=2.80007 (12) nm3, dc= 1.634 mg·m-3, m (mok α)=1.329 mm-1, f (000)=1376;In molecule, tin atom is seven coordination distortion five JIAOSHUANG Cone configuration.
4. 2- carbonyl propionic acid described in claim 1 toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound is had certain Thermally-stabilised scope, can stable existence below 116 DEG C.
5. the preparation to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound for the 2- carbonyl propionic acid described in claim 1 Method, is characterized in that adding two (2,4- dichloro benzyl) stannum dichloride in the reaction vessel having nitrogen protection, to methylbenzene first Hydrazides, Sodium Pyruvate and solvent absolute methanol, react 5 ~ 24 h, cooling under conditions of temperature is 45 ~ 65 DEG C, filter, 20 ~ Control solvent volatilization crystallization under conditions of 35 DEG C, obtain yellow transparent crystal, as 2- carbonyl propionic acid to toluyl hydrazone two (2, 4- dichloro benzyl) stannum coordination compound.
6. the method for preparation as claimed in claim 5 is it is characterised in that described two (2,4- dichloro benzyl) stannum dichloride, right Toluyl hydrazine, the amount of the material of Sodium Pyruvate three are than for 1:(1 ~ 1.05): (1.05 ~ 1.15).
7. the method for preparation as claimed in claim 5 is it is characterised in that described solvent absolute methanol consumption is every mM two (2,4- dichloro benzyl) stannum dichloride adds 15 ~ and 35 milliliters.
8. 2- carbonyl propionic acid described in claim 1 is preparing anticancer to toluyl hydrazone two (2,4- dichloro benzyl) stannum coordination compound Application in medicine.
9. the application described in claim 8, wherein said cancerous cell is human lung carcinoma cell, human liver cancer cell, human breast cancer cell.
CN201610691923.5A 2016-08-20 2016-08-20 2-oxo-propionic acid p-toluyl hydrazone di-2, 4-dichlorobenzyltin complex and its preparation method and use CN106366113A (en)

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