CN105777799A - 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone dibenzyl tin complex as well as preparation method and application thereof - Google Patents
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone dibenzyl tin complex as well as preparation method and application thereof Download PDFInfo
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
Abstract
The invention discloses a 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone dibenzyl tin complex of which the structural formula (I) is shown in the description. In the formula, Ph is phenyl, and R is benzyl. The invention further discloses a preparation method of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone dibenzyl tin complex and application thereof to preparation of anti-cancer drugs.
Description
Technical field
The present invention relates to a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound and preparation method thereof, with
And this 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound application in preparing cancer therapy drug.
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.1972, Brown found Ph first3SnOOCCH3Growth to mice cancerous cell has
There is inhibitory action.1980, the research of the chemists such as Crowe showed, many organo-tin compounds have anti tumor activity in vitro.
1989, more than 2,000 kinds of organo-tin compounds were entered by American National anticancer research institute (National Cancer Institute)
Having gone antitumor activity screening, result shows that some organo-tin compounds have inhibitory action to P388 Lymphocytic leukemia.
2002, the activity of organotin carboxylate's ester compounds was being done comprehensive summing up by Gielen et al., thought many organic after research
Tin compound has preferable Anticancer Activity in vitro really.
Research shows, the organic group that organotin atom connects and the part participating in coordination decide organo-tin compound
Biological activity, select some itself have good biological activity organic ligand with in organotin tin atom coordination cause
The great interest of people.Acylhydrazone is by a class Schiff alkali cpd of hydrazide kind compound modification, it
Be condensed by aldehydes or ketones and hydrazides and form, there is good biological activity, stronger coordination ability and various coordination mode, and
And have a wide range of applications at aspects such as medicine, pesticide, material and analytical reagents.In recent years, the most many research worker pair
It compares in terms of biological activity and in depth studies, and research finds that acylhydrazone has anticancer, sterilization, antiinflammatory etc.
Various active.Therefore, acylhydrazone class Schiff aar ligand is combined with organotin, it is intended to obtain the new chemical combination that biological activity is higher
Thing, becomes the research direction that people are interested.
Chinese patent CN 102718794A disclose a kind of double acylhydrazone class Schiff alkali stannous phenide coordination compound and
Prepare the application in the medicine of Antilung gland cancer, colon cancer, leukaemia.
Chinese patent CN 101851251A disclose a kind of acylhydrazone class Schiff aar ligand dibutyl tin coordination compound and
Its application in preparation treatment hepatocarcinoma, adenocarcinoma of lung, breast carcinoma, carcinoma of prostate, colon cancer or the youngest leukemic medicine of grain.
Document (Journal of Organometallic Chemistry, 2014,75:83-91) is reported, organotin
Acylhydrazone class Schiff alkali coordination compound is to human colon cancer cell (HCT-116), human lung adenocarcinoma cell (A549), human umblilical vein endothelial
Cell (HUVEC) has relatively strong biological activity, and is 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
The inhibitory action of the cancerous cell such as cell (A549), human colon cancer cell (HCT-8), people in loop (hl-60).
Document (Bioorganic & Medicinal Chemistry Letters, 2015,25:4461-4463)
Report, multiple acylhydrazone class Schiff aar ligand is to human liver cancer cell (HuH-7) and the anticancer work of human lung adenocarcinoma cell (A549)
Property.
It is the material that the experiment proved that and there is active anticancer based on acylhydrazone class Schiff alkali organotin complex, the present invention
Selecting benzoyl hydrazine, Sodium.beta.-phenylpyruvate to react under certain condition with TriphenylphosphineoxComplex, synthesis has obtained human colon carcinoma
Cell (Colo205), human liver cancer cell (HepG2), breast cancer cell (MCF7), cervical cancer cell (Hela) and people's pulmonary carcinoma are thin
Born of the same parents (NCI-H460) have the coordination compound of certain inhibitory activity, provide new approach for exploitation cancer therapy drug.
Summary of the invention
The first object of the present invention there is provided a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
The second object of the present invention is to provide above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound and prepares
Method.
The third object of the present invention is to provide above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound in system
Application in standby cancer therapy drug.
As a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound of a first aspect of the present invention, for
The coordination compound of structure formula (I)
(I)
Wherein Ph is phenyl, and R is benzyl.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin the coordination compound of the present invention is through elementary analysis, infrared spectrum, core
Magnetic resonance spectrum and X-ray single crystal diffraction structural analysis, result is as follows:
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H 4.99,
N 4.59。
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin the coordination compound of the present invention is crystal structure, and its crystal is three
Oblique system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=1.26730 (5) nm, α=
78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3, Dc=1.474 Mg m-3, m
(MoKα)= 0.963 mm-1, F (000)=624.
Being structurally characterized in that of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound of the present invention: stannum in molecule
Atom is seven coordination distortion pentagonal bipyramid configurations.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin the coordination compound of the present invention has certain thermally-stabilised scope,
Can stable existence below 103 DEG C.
System as a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound of a second aspect of the present invention
Preparation Method, add in the reaction vessel having nitrogen to protect TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.beta.-phenylpyruvate and solvent without
Water methanol, reacts 5 ~ 24 h, cooling under conditions of temperature is 45 ~ 65 DEG C, filters, and controls solvent under conditions of 20 ~ 35 DEG C
Volatilization crystallization, obtains colourless transparent crystal, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
In a preferred embodiment of the invention, described TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.beta.-phenylpyruvate three
The amount of material 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 of dibenzyl dichloride
Stannum adds 15 ~ and 35 milliliters.
A kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound as a third aspect of the present invention is being made
Application in standby cancer therapy drug.
Applicant has carried out extracorporeal anti-tumor and has lived above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound
Property determine research, it is thus identified that 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound has certain Anti-cancer biologic and lives
Property, say, that the purposes of above-mentioned coordination compound is the application in preparing cancer therapy drug, is exactly to prepare anti-human knot specifically
Application in intestinal cancer, people's hepatocarcinoma, human breast carcinoma, human cervical carcinoma, people's lung-cancer medicament.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin the coordination compound of the present invention is to human colon cancer cell, people's hepatocarcinoma
Cell, human breast cancer cell, human cervical carcinoma cell, human lung carcinoma cell etc. demonstrate good active anticancer, the 2-of the present invention
The features such as carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound active anticancer height, low cost, preparation method are simple, for
Develop new cancer therapy drug and provide new way.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
Fig. 2 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound1H NMR spectra.
Fig. 3 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound13C NMR spectra.
Fig. 4 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound119Sn NMR spectra.
Fig. 5 is the crystal structure figure of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
Fig. 6 is the TG-DTG curve of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
Detailed description of the invention
Further describe the present invention by following example, but it should be noted that the scope of the present invention is not implemented by these
Any restriction of example.
Embodiment 1:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.136g is added in the 100mL there-necked flask having nitrogen to protect
(1.0mmol) benzoyl hydrazine, 0.205g (1.1mmol) Sodium.beta.-phenylpyruvate and 25mL solvent absolute methanol, be 45 ~ 65 in temperature
8 h are reacted under conditions of DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain colourless transparent crystal,
It is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 74.4%.Fusing point: 103 ~ 105 DEG C (dec).
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Embodiment 2:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.136g is added in the 100mL there-necked flask having nitrogen to protect
(1.0mmol) benzoyl hydrazine, 0.195g (1.05mmol) Sodium.beta.-phenylpyruvate and 35mL solvent absolute methanol, be 45 ~ 65 in temperature
5 h are reacted under conditions of DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain colourless transparent crystal,
It is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 77.0%.Fusing point: 103 ~ 105 DEG C (dec).
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Embodiment 3:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.142g is added in the 100mL there-necked flask having nitrogen to protect
(1.05mmol) benzoyl hydrazine, 0.214g (1.15mmol) Sodium.beta.-phenylpyruvate and 30mL solvent absolute methanol, temperature be 45 ~
15 h are reacted under conditions of 65 DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain water white transparency brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 78.2%.Fusing point: 103 ~ 105 DEG C
(dec)。
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Embodiment 4:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
1.860g (5.0mmol) TriphenylphosphineoxComplex, 0.694g is added in the 250mL there-necked flask having nitrogen to protect
(5.1mmol) benzoyl hydrazine, 1.004g (5.4mmol) Sodium.beta.-phenylpyruvate and 100mL solvent absolute methanol, be 45 ~ 65 in temperature
20 h are reacted under conditions of DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain water white transparency brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 73.9%.Fusing point: 103 ~ 105 DEG C
(dec)。
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Embodiment 5:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
1.860g (5.0mmol) TriphenylphosphineoxComplex, 0.707g is added in the 250mL there-necked flask having nitrogen to protect
(5.2mmol) benzoyl hydrazine, 1.042g (5.6mmol) Sodium.beta.-phenylpyruvate and 150mL solvent absolute methanol, be 45 ~ 65 in temperature
22 h are reacted under conditions of DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain water white transparency brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 73.2%.Fusing point: 103 ~ 105 DEG C
(dec)。
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Embodiment 6:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound:
3.720g (10.0mmol) TriphenylphosphineoxComplex, 1.387g is added in the 250mL there-necked flask having nitrogen to protect
(10.2mmol) benzoyl hydrazine, 1.972g (10.6mmol) Sodium.beta.-phenylpyruvate and 150mL solvent absolute methanol, temperature be 45 ~
24 h are reacted under conditions of 65 DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain water white transparency brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.Productivity: 71.7%.Fusing point: 103 ~ 105 DEG C
(dec)。
Elementary analysis (C62H60N4O8Sn2): value of calculation: C 60.71, H 4.93, N 4.57；Measured value: C 60.74, H
4.99, N 4.59.
FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440。
1H NMR (400 MHz, DMSO-d6) δ(ppm): 7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41
(m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J = 6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m,
4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s, 2H,), 2.88-2.81 (m, 4H)。
13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04, 151.85, 138.30,
135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76, 127.68, 127.10,
125.59, 123.79, 48.38, 37.04, 31.33。
119Sn NMR (187 MHz, DMSO-d6) δ(ppm): -453.90。
Crystallographic data: anorthic system, space group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=
1.26730 (5) nm, α=78.19 °, β=71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3,
Dc= 1.474 Mg·m-3, m (MoK α)=0.963 mm-1, F (000)=624.
Test example:
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin the coordination compound of the present invention, it is to pass through that its Anticancer Activity in vitro measures
MTT experiment method realizes.
MTT analytic process:
With metabolism reduction 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide it is
Basis.Succinate dehydrogenase in living cells mitochondrion 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 is without 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 by microplate reader, can indirectly reflect living cells quantity.
Mtt assay is used to measure the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound pair of embodiment 1 preparation
Human colon cancer cell (Colo205), human liver cancer cell (HepG2), human breast cancer cell (MCF7), human cervical carcinoma cell
And the inhibitory activity of human lung carcinoma cell (NCI-H460) (Hela).
Cell strain and cultivating system: Colo205, HepG2, MCF7, Hela and NCI-H460 cell strain takes from American. tissue
Incubator (ATCC).RPMI 1640(GIBICO company with containing 10% hyclone) culture medium, in 5%(volume fraction) CO2、
In vitro culture is carried out in 37 DEG C of saturated humidity incubators.
Test process: test medicinal liquid (0.1ng/mL ~ 10ug/mL) is added separately to each according to the Concentraton gradient of concentration
Kong Zhong, each 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 adding culture fluid and cell, be not added with testing medicine) and blank group (only add cultivation medicine, be not added with cell and test medicine).After dosing
Orifice plate is placed in 37 DEG C, 5%CO2Incubator is cultivated 72h.The activity of control drug measures according to the method for test sample.Cultivating
In orifice plate after 72h, every hole adds MTT 40uL(D-Hanks buffer and is made into 4mg/mL).After placing 4h at 37 DEG C, remove
The supernatant.Every hole adds 150uL DMSO, and vibrate 5min, makes Formazan crystallization dissolve.Finally, automatic microplate reader is utilized to exist
The optical density in each hole is detected at 570nm wavelength.
Data process: data process and use Graph Pad Prism version 5.0 program, coordination compound IC50Pass through journey
The nonlinear regression model (NLRM) in sequence with S-shaped dose response is fitted obtaining.
With MTT analytic process to human colon cancer cell (Colo205), human liver cancer cell (HepG2), human breast cancer cell
(MCF7), human cervical carcinoma cell (Hela) and human lung carcinoma cell (NCI-H460) cell strain be analyzed, measure its IC50Value,
Result is as shown in table 1, and conclusion is: from data in table, with the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone dibenzyl of the present invention
Stannum coordination compound is used as cancer therapy drug, to human colon cancer cell (Colo205), human liver cancer cell (HepG2), human breast cancer cell
(MCF7), human cervical carcinoma cell (Hela) and human lung carcinoma cell (NCI-H460) there is certain drug effect, can be as anticarcinogen
The candidate compound of thing.
Table 1 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound cancer therapy drug external activity test data.
People is tied by 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound prepared by remaining embodiment with mtt assay
Colon-cancer cell (Colo205), human liver cancer cell (HepG2), human breast cancer cell (MCF7), human cervical carcinoma cell (Hela) and
The same test example of active anticancer method of testing of human lung carcinoma cell (NCI-H460), test result is essentially identical with table 1.
Claims (9)
1. a 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound, for the coordination compound of following structure formula (I):
(I)
Wherein Ph is phenyl, and R is benzyl.
2. as claimed in claim 1 containing a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound, it is infrared
Spectroscopic data: FT-IR (KBr, ν/cm-1): 3080, 3059, 3024, 2930, 1630, 1614, 1597, 1391,
1338, 696, 590, 555, 455, 440；Its nuclear-magnetism modal data:1H NMR (400 MHz, DMSO-d6) δ(ppm):
7.87 (d, J = 7.1 Hz, 2H), 7.51-7.41 (m, 3H), 7.21-7.13 (m, 3H), 6.96 (d, J =
6.8 Hz, 2H), 6.78 (s, 6H), 6.69(m, 4H), 4.04 (s, 1H), 3.47 (s, 3H), 3.17 (s,
2H,), 2.88-2.81 (m, 4H)；13C NMR (100 MHz, DMSO-d6) δ(ppm): 172.75, 164.04,
151.85, 138.30, 135.97, 134.47, 130.72, 128.86, 127.90, 127.80, 127.76,
127.68, 127.10, 125.59, 123.79, 48.38, 37.04, 31.33；119Sn NMR (187 MHz, DMSO-
d6) δ(ppm): -453.90。
3. 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound as claimed in claim 1, wherein, described 2-
Carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound is crystal structure, and its crystallographic data is as follows: anorthic system, empty
Between group P-1, a=0.95601 (4) nm, b=1.22653 (5) nm, c=1.26730 (5) nm, α=78.19 °, β=
71.78 °, γ=86.0410 (10) °, Z=2, V=1.38155 (10) nm3, Dc=1.474 Mg m-3, m (MoK α)=
0.963 mm-1, F (000)=624；In molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations.
4. described in claim 1,2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound has certain thermally-stabilised model
Enclose, can stable existence below 103 DEG C.
5. the preparation method of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound described in claim 1, its feature
It is in the reaction vessel having nitrogen to protect, to add TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.beta.-phenylpyruvate and solvent without water beetle
Alcohol, reacts 5 ~ 24 h, cooling under conditions of temperature is 45 ~ 65 DEG C, filters, and controls solvent volatilization under conditions of 20 ~ 35 DEG C
Crystallization, obtains colourless transparent crystal, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound.
6. the method for preparation as claimed in claim 5, it is characterised in that described TriphenylphosphineoxComplex, benzoyl hydrazine, phenylpropyl alcohol
The amount of the material of keto acid sodium three is than for 1:(1 ~ 1.05): (1.05 ~ 1.15).
7. the method for preparation as claimed in claim 5, it is characterised in that described solvent absolute methanol consumption is every mM two
Benzyl stannum dichloride adds 15 ~ and 35 milliliters.
8. 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone Dibenzyltin coordination compound described in claim 1 is in preparing cancer therapy drug
Application.
9. the application described in claim 8, wherein said cancerous cell is that human colon cancer cell, human liver cancer cell, human breast carcinoma are thin
Born of the same parents, human cervical carcinoma cell, human lung carcinoma cell.
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