CN106279252A - A kind of 2 carbonyl 3 phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compounds and its preparation method and application - Google Patents
A kind of 2 carbonyl 3 phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compounds and its preparation method and application Download PDFInfo
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- CN106279252A CN106279252A CN201610662832.9A CN201610662832A CN106279252A CN 106279252 A CN106279252 A CN 106279252A CN 201610662832 A CN201610662832 A CN 201610662832A CN 106279252 A CN106279252 A CN 106279252A
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- Prior art keywords
- carbonyl
- phenylpropionic acid
- coordination compound
- butyl tin
- benzoyl hydrazone
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- -1 carbonyl 3 phenylpropionic acid benzoyl hydrazone di-n-butyl tin Chemical compound 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003814 drug Substances 0.000 claims abstract description 20
- 229940079593 drug Drugs 0.000 claims abstract description 12
- 238000011275 oncology therapy Methods 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 206010006187 Breast cancer Diseases 0.000 claims description 11
- 208000026310 Breast neoplasm Diseases 0.000 claims description 11
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 10
- 206010058467 Lung neoplasm malignant Diseases 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- MQGYVGKMCRDEAF-UHFFFAOYSA-M sodium;2-oxo-3-phenylpropanoate Chemical compound [Na+].[O-]C(=O)C(=O)CC1=CC=CC=C1 MQGYVGKMCRDEAF-UHFFFAOYSA-M 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 201000005296 lung carcinoma Diseases 0.000 claims description 7
- 238000000902 119Sn nuclear magnetic resonance spectroscopy Methods 0.000 claims description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 201000007270 liver cancer Diseases 0.000 claims description 6
- 208000014018 liver neoplasm Diseases 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002447 crystallographic data Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 241000254173 Coleoptera Species 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000005311 nuclear magnetism Effects 0.000 claims 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 37
- 230000001093 anti-cancer Effects 0.000 description 13
- 238000011160 research Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000004071 biological effect Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 206010009944 Colon cancer Diseases 0.000 description 4
- 208000029742 colonic neoplasm Diseases 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 201000005249 lung adenocarcinoma Diseases 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- 150000004753 Schiff bases Chemical class 0.000 description 3
- 230000000259 anti-tumor effect Effects 0.000 description 3
- 201000008275 breast carcinoma Diseases 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 3
- 241000699670 Mus sp. Species 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- AZKSAVLVSZKNRD-UHFFFAOYSA-M 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide Chemical compound [Br-].S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 AZKSAVLVSZKNRD-UHFFFAOYSA-M 0.000 description 1
- FKMQIAIGLLCJAU-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)NN=C(C(CC1=CC=CC=C1)=C=O)O Chemical compound C(C1=CC=CC=C1)(=O)NN=C(C(CC1=CC=CC=C1)=C=O)O FKMQIAIGLLCJAU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000028018 Lymphocytic leukaemia Diseases 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- 229910020813 Sn-C Inorganic materials 0.000 description 1
- 229910018732 Sn—C Inorganic materials 0.000 description 1
- 102000019259 Succinate Dehydrogenase Human genes 0.000 description 1
- 108010012901 Succinate Dehydrogenase Proteins 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000003560 cancer drug Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- YAYRGNWWLMLWJE-UHFFFAOYSA-L carboplatin Chemical compound O=C1O[Pt](N)(N)OC(=O)C11CCC1 YAYRGNWWLMLWJE-UHFFFAOYSA-L 0.000 description 1
- 229960004562 carboplatin Drugs 0.000 description 1
- 208000019065 cervical carcinoma Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 1
- 229960004316 cisplatin Drugs 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000003511 endothelial effect Effects 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 208000003747 lymphoid leukemia Diseases 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 201000001514 prostate carcinoma Diseases 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000001942 tin-119 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000004614 tumor growth Effects 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a kind of 2 carbonyl 3 phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compounds, for the coordination compound of following structure formula (I), wherein Ph is phenyl, and R is normal-butyl.The invention also discloses the preparation method of this 2 carbonyl 3 phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound and the application in preparing cancer therapy drug.
Description
Technical field
The present invention relates to a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound and preparation method thereof,
And this 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin 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.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 Ph3SnOOCCH3Can suppress the tumor growth of mice, and triphenyltin chloride
Then can not.Between 1972 ~ 1977 years, Holland's substantial amounts of organo-tin compound of scholar's research, but find no further screening valency
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 an anti-tumor activity, and find out that they all contain or hydrolyze and can produce stannum oxygen
Key.1980, Crowe etc. was found that again some organo-tin compounds have preferable active anticancer, from this, resisted about 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
Brighter organo-tin compounds 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 the most external really after research
Active anticancer.
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 compound of hydrazide kind compound modification, they
It is condensed by aldehydes or ketones and hydrazides and forms, molecule has 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, it is compared in terms of biological activity by the most many research worker in depth studies, and research finds acylhydrazone class
Compound has the various active such as anticancer, sterilization, antiinflammatory.Therefore, acylhydrazone class Schiff part is combined with organotin, it is intended to
Obtain the noval chemical compound that biological activity is higher, become the research direction that people are interested.
Chinese patent CN 102718794A discloses a kind of double acylhydrazone class Schiff stannous phenide coordination compound and in system
Standby Antilung gland cancer, colon cancer, leukaemia medicine in application.
Chinese patent CN 101851251A disclose a kind of acylhydrazone class Schiff part di-n-butyl 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 base complex 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 relatively 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 base complex, organo-tin compound and acylhydrazone class Schiff part 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, multiple acylhydrazone class Schiff part is to human liver cancer cell (HuH-7) and the active anticancer of human lung adenocarcinoma cell (A549).
Document (Journal of Organometallic Chemistry, 2016,804:48-58) is reported, two hydrocarbon
Base stannum acylhydrazone class Schiff base complex 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.
Being the material that the experiment proved that and have active anticancer based on acylhydrazone class Schiff organotin complex, the present invention selects
Select benzoyl hydrazine, Sodium.beta.-phenylpyruvate reacts under certain condition with Dibutyltin oxide, and synthesis has obtained human lung carcinoma cell
(H460), human liver cancer cell (HepG2) and human breast cancer cell (MCF7) there is the coordination compound of certain inhibitory activity, anti-for exploitation
Cancer drug provides new approach.
Summary of the invention
The first object of the present invention there is provided a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin and coordinates
Thing.
The second object of the present invention is to provide above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound system
Preparation Method.
The third object of the present invention is to provide above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound and exists
Prepare the application in cancer therapy drug.
As a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound of a first aspect of the present invention,
Coordination compound for structure formula (I)
(I)
Wherein Ph is phenyl, and R is normal-butyl.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin the coordination compound of the present invention through elementary analysis, infrared spectrum,
Nuclear magnetic resoance spectrum and X-ray single crystal diffraction structural analysis, result is as follows:
Elementary analysis (C50H68N4O8Sn2): value of calculation: C 55.07, H 6.29, N 5.14；Measured value: C 55.14, H 6.24,
N 5.19。
FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616, 1589,
1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551, 491,
457。
1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H), 7.49~7.60 (m,
5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d, 3H), 1.59~1.62
(m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q, 1H), 0.78 (t, J
=7.3 Hz, 6H)。
13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19, 155.66, 135.04,
132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07, 26.60, 26.34,
21.57, 13.40。
119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin the coordination compound of the present invention is crystal structure, and its crystal is
Monoclinic system, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11) nm, c=1.09850 (5)
Nm, α=γ=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419 Mg m-3, m (MoK α)=
1.032 mm-1, F (000)=1120.
Being structurally characterized in that of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound of the present invention: in molecule
Tin atom is seven coordination distortion pentagonal bipyramid configurations.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin the coordination compound of the present invention has certain thermally-stabilised model
Enclose, can stable existence below 91 DEG C.
A kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound as a second aspect of the present invention
Preparation method, add in the reaction vessel having nitrogen to protect Dibutyltin oxide, 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 yellow transparent crystal, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.
The preparation characteristic of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound of the present invention is: from relatively
Raw material simple and easy to get sets out, and without the separation of intermediate, directly obtains baroque molecule, i.e. one kettle way；Such instead
Should economically and environmentally on close friend advantageously.
In a preferred embodiment of the invention, described Dibutyltin oxide, benzoyl hydrazine, Sodium.beta.-phenylpyruvate three
The amount of material is 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 Dibutyltin oxide
Add 15 ~ 35 milliliters.
A kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound as a third aspect of the present invention exists
Prepare the application in cancer therapy drug.
Applicant has carried out external anticancer work to above-mentioned 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound
Property determines research, it is thus identified that 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound has certain Anti-cancer biologic
Activity, say, that the purposes of above-mentioned coordination compound is the application in preparing cancer therapy drug, be exactly specifically prepare anti-human
Application in pulmonary carcinoma, people's hepatocarcinoma and human breast carcinoma medicine.
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin the coordination compound of the present invention is to human lung carcinoma cell, people's hepatocarcinoma
Cell and human breast cancer cell demonstrate good active anticancer, and the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone two of the present invention is just
The features such as butyl tin coordination compound active anticancer height, low cost, preparation method are simple, provide new way for developing new cancer therapy drug
Footpath.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.
Fig. 2 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound1H NMR spectra.
Fig. 3 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound13C NMR spectra.
Fig. 4 is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound119Sn NMR spectra.
Fig. 5 is the crystal structure figure of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.
Fig. 6 is the TG-DTG curve of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.
Detailed description of the invention
By detailed description below, the present invention is described in further detail.
Embodiment 1:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound:
0.248g (1.0mmol) Dibutyltin oxide, 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 15mL 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 yellow transparent crystal,
It is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.Productivity: 77.6%.Fusing point: 91 ~ 93 DEG C (dec).
Elementary analysis (C50H68N4O8Sn2): value of calculation: C 55.07, H 6.29, N 5.14；Measured value: C 55.14, H
6.24, N 5.19.
FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616, 1589,
1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551, 491,
457。
1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H), 7.49~7.60 (m,
5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d, 3H), 1.59~1.62
(m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q, 1H), 0.78 (t, J
=7.3 Hz, 6H)。
13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19, 155.66, 135.04,
132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07, 26.60, 26.34,
21.57, 13.40。
119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
Crystallographic data: monoclinic system, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11)
Nm, c=1.09850 (5) nm, α=γ=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419
Mg·m-3, m (MoK α)=1.032 mm-1, F (000)=1120.
Embodiment 2:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound:
0.248g (1.0mmol) Dibutyltin oxide, 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 yellow transparent crystal,
It is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.Productivity: 78.5%.Fusing point: 91 ~ 93 DEG C (dec).
Elementary analysis (C50H68N4O8Sn2): value of calculation: C 55.07, H 6.29, N 5.14；Measured value: C 55.14, H
6.24, N 5.19.
FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616, 1589,
1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551, 491,
457。
1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H), 7.49~7.60 (m,
5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d, 3H), 1.59~1.62
(m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q, 1H), 0.78 (t, J
=7.3 Hz, 6H)。
13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19, 155.66, 135.04,
132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07, 26.60, 26.34,
21.57, 13.40。
119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
Crystallographic data: monoclinic system, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11)
Nm, c=1.09850 (5) nm, α=γ=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419
Mg·m-3, m (MoK α)=1.032 mm-1, F (000)=1120.
Embodiment 3:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound:
0.248g (1.0mmol) Dibutyltin oxide, 0.143g is added in the 100mL there-necked flask having nitrogen to protect
(1.05mmol) benzoyl hydrazine, 0.214g (1.15mmol) Sodium.beta.-phenylpyruvate and 25mL 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 yellow transparent brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.Productivity: 76.0%.Fusing point: 91 ~ 93 DEG C
(dec)。
Elementary analysis (C50H68N4O8Sn2): value of calculation: C 55.07, H 6.29, N 5.14；Measured value: C 55.14, H
6.24, N 5.19.
FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616, 1589,
1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551, 491,
457。
1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H), 7.49~7.60 (m,
5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d, 3H), 1.59~1.62
(m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q, 1H), 0.78 (t, J
=7.3 Hz, 6H)。
13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19, 155.66, 135.04,
132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07, 26.60, 26.34,
21.57, 13.40。
119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
Crystallographic data: monoclinic system, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11)
Nm, c=1.09850 (5) nm, α=γ=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419
Mg·m-3, m (MoK α)=1.032 mm-1, F (000)=1120.
Embodiment 4:
The preparation of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound:
2.480g (10.0mmol) Dibutyltin oxide, 1.400g is added in the 500mL there-necked flask having nitrogen to protect
(10.3mmol) benzoyl hydrazine, 2.046g (11.0mmol) Sodium.beta.-phenylpyruvate and 200mL solvent absolute methanol, temperature be 45 ~
22 h are reacted under conditions of 65 DEG C, cooling, filter, under conditions of 20 ~ 35 DEG C, control solvent volatilization crystallization, obtain yellow transparent brilliant
Body, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.Productivity: 75.3%.Fusing point: 91 ~ 93 DEG C
(dec)。
Elementary analysis (C50H68N4O8Sn2): value of calculation: C 55.07, H 6.29, N 5.14；Measured value: C 55.14, H
6.24, N 5.19.
FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616, 1589,
1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551, 491,
457。
1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H), 7.49~7.60 (m,
5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d, 3H), 1.59~1.62
(m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q, 1H), 0.78 (t, J
=7.3 Hz, 6H)。
13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19, 155.66, 135.04,
132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07, 26.60, 26.34,
21.57, 13.40。
119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
Crystallographic data: monoclinic system, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11)
Nm, c=1.09850 (5) nm, α=γ=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419
Mg·m-3, m (MoK α)=1.032 mm-1, F (000)=1120.
Test example:
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin the coordination compound of the present invention, it is logical that its Anticancer Activity in vitro measures
Cross what MTT experiment method realized.
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 di-n-butyl tin coordination compound of embodiment 1 preparation
To human lung carcinoma cell (H460), human liver cancer cell (HepG2) and the inhibitory activity of human breast cancer cell (MCF7).
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, at 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, be not added with testing medicine) and blank group (only adding cultivation medicine, be not added with cell and test medicine).Orifice plate after dosing is put
In 37 DEG C, 5%CO2Incubator is cultivated 72h.The activity of control drug measures according to the method for test sample.Cultivating 72h
After orifice plate in, 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, and vibrate 5min, makes Formazan crystallization dissolve.Finally, utilize automatic microplate reader at 570nm
The optical density in each hole is detected at wavelength.
Data process: data process and use Graph Pad Prism version 7.0 program, coordination compound IC50Pass through journey
The nonlinear regression model (NLRM) in sequence with S-shaped 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, result is as shown in table 1, and conclusion is: from data in table, with the 2-carbonyl of the present invention
Base-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound is used as cancer therapy drug, thin to human lung carcinoma cell (H460), people's hepatocarcinoma
Born of the same parents (HepG2) and human breast cancer cell (MCF7) have certain drug effect, can be as the candidate compound of cancer therapy drug.
Table 1 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound cancer therapy drug external activity test number
According to.
| People's pulmonary carcinoma | People's hepatocarcinoma | Human breast carcinoma | |
| Cell strain | H460 | HepG2 | MCF7 |
| IC50(μM) | 0.84±0.08 | 0.45±0.15 | 0.53±0.15 |
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound prepared by remaining embodiment with mtt assay to people
The active anticancer method of testing of lung carcinoma cell (H460), human liver cancer cell (HepG2) and human breast cancer cell (MCF7) is with 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 change, modification without departing from the spirit and scope of the present invention to the present invention.If to the present invention's
These amendments and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, belong to the protection model of the present invention
Enclose.
Claims (9)
1. a 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound, for the coordination compound of following structure formula (I):
(I)
Wherein Ph is phenyl, and R is normal-butyl.
2. as claimed in claim 1 containing a kind of 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound, it is red
External spectrum data: FT-IR (KBr, ν/cm-1): 3446, 3084, 3028, 2956, 2924, 2856, 1616,
1589, 1579, 1492, 1388, 1344, 1172, 1074, 860, 754, 711, 698, 630, 586, 551,
491, 457；Its nuclear-magnetism modal data:1H NMR (500 MHz, CDCl3, δ/ppm): 8.26 (d, J =7.5 Hz, 2H),
7.49~7.60 (m, 5H), 7.26~7.29 (m, 2H), 7.21 (m, 1H), 4.45 (s, 2H), 3.50 (d,
3H), 1.59~1.62 (m, 4H), 1.46~1.52 (m, 4H), 1.20~1.28 (m, 4H), 1.07~1.10 (q,
1H), 0.78 (t, J=7.3 Hz, 6H)；13C NMR (125 MHz, CDCl3, δ/ppm): 175.06, 164.19,
155.66, 135.04, 132.56, 129.88, 128.72, 128.67, 128.43, 127.03, 50.89, 33.07,
26.60, 26.34, 21.57, 13.40；119Sn NMR (187 MHz, CDCl3, δ/ppm): -158.08。
3. 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound as claimed in claim 1, wherein, described
2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound is crystal structure, and its crystallographic data is as follows: monoclinic crystal
System, space group P2 (1)/c, a=1.14677 (6) nm, b=2.04929 (11) nm, c=1.09850 (5) nm, α=γ
=90 °, β=98.536 (5) °, Z=2, V=2.5529 (2) nm3, Dc=1.419 Mg m-3, m (MoK α)=1.032 mm-1, F
(000) = 1120；In molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations.
4. 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound described in claim 1 has certain thermally-stabilised
Scope, can stable existence below 91 DEG C.
5. the preparation method of the 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound described in claim 1, it is special
Levy is to add Dibutyltin oxide, benzoyl hydrazine, Sodium.beta.-phenylpyruvate and solvent in the reaction vessel having nitrogen to protect 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 yellow transparent crystal, is 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin coordination compound.
6. the method for preparation as claimed in claim 5, it is characterised in that described Dibutyltin oxide, benzoyl hydrazine, propiophenone
The amount of the material of acid sodium three ratio is 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
Butyl stannum oxide adds 15 ~ and 35 milliliters.
8. 2-carbonyl-3-phenylpropionic acid benzoyl hydrazone di-n-butyl tin 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 human lung carcinoma cell, human liver cancer cell, human breast cancer cell.
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| CN105198921A (en) * | 2015-11-11 | 2015-12-30 | 衡阳师范学院 | 2-carbonyl-2-phenylacetic acid salicyloyl hydrazone dibutyltin complex as well as preparation method and application of 2-carbonyl-2-phenylacetic acid salicyloyl hydrazone dibutyltin complex |
| CN105541898A (en) * | 2015-11-11 | 2016-05-04 | 衡阳师范学院 | Benzoylhydrazone bis(p-methylbenzyl) tin 2-carbonyl-3-phenylpropionate complex, and preparation method and application thereof |
| CN105693762A (en) * | 2016-04-23 | 2016-06-22 | 衡阳师范学院 | 2-carbonyl-2-phenylacetic acid benzoylhydrazone di-n-butyltin tin complex and preparation method and application thereof |
| CN105777798A (en) * | 2016-04-23 | 2016-07-20 | 衡阳师范学院 | 2-carbonyl-2-phenylacetic acid para hydroxybenzene formyl hydrazone dibutyl tin complex as well as preparation method and application thereof |
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| CN105541898A (en) * | 2015-11-11 | 2016-05-04 | 衡阳师范学院 | Benzoylhydrazone bis(p-methylbenzyl) tin 2-carbonyl-3-phenylpropionate complex, and preparation method and application thereof |
| CN105693762A (en) * | 2016-04-23 | 2016-06-22 | 衡阳师范学院 | 2-carbonyl-2-phenylacetic acid benzoylhydrazone di-n-butyltin tin complex and preparation method and application thereof |
| CN105777798A (en) * | 2016-04-23 | 2016-07-20 | 衡阳师范学院 | 2-carbonyl-2-phenylacetic acid para hydroxybenzene formyl hydrazone dibutyl tin complex as well as preparation method and application thereof |
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