CN105753896A - 2-carbonyl-3-phenylpropionic acid p-hydroxyphenylcarbonylhydrazone dibenzyl tin complex as well as preparation method and application thereof - Google Patents
2-carbonyl-3-phenylpropionic acid p-hydroxyphenylcarbonylhydrazone dibenzyl tin complex as well as preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RHUZYGNZONJZMX-UHFFFAOYSA-N C(C1=CC=CC=C1)[Sn]CC1=CC=CC=C1.OC1=CC=C(C=C1)C(=O)NN=C(C(CC1=CC=CC=C1)=C=O)O Chemical compound C(C1=CC=CC=C1)[Sn]CC1=CC=CC=C1.OC1=CC=C(C=C1)C(=O)NN=C(C(CC1=CC=CC=C1)=C=O)O RHUZYGNZONJZMX-UHFFFAOYSA-N 0.000 title abstract 3
- 238000010668 complexation reaction Methods 0.000 title description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 88
- SVSRQMUJHHQAAX-UHFFFAOYSA-N dibenzyltin Chemical compound C=1C=CC=CC=1C[Sn]CC1=CC=CC=C1 SVSRQMUJHHQAAX-UHFFFAOYSA-N 0.000 claims description 44
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 44
- 150000007857 hydrazones Chemical class 0.000 claims description 44
- 229960003742 phenol Drugs 0.000 claims description 44
- NSZRQCQXHMPQEY-UHFFFAOYSA-N C(=O)=C(C(=O)O)CC1=CC=CC=C1 Chemical compound C(=O)=C(C(=O)O)CC1=CC=CC=C1 NSZRQCQXHMPQEY-UHFFFAOYSA-N 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000003814 drug Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 206010009944 Colon cancer Diseases 0.000 claims description 12
- 208000029742 colonic neoplasm Diseases 0.000 claims description 12
- 229940079593 drug Drugs 0.000 claims description 12
- IZFQZZZGGIUQIW-UHFFFAOYSA-N C(=O)NN.OC1=CC=CC=C1 Chemical compound C(=O)NN.OC1=CC=CC=C1 IZFQZZZGGIUQIW-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 201000007270 liver cancer Diseases 0.000 claims description 10
- 208000014018 liver neoplasm Diseases 0.000 claims description 10
- 238000011275 oncology therapy Methods 0.000 claims description 10
- 206010006187 Breast cancer Diseases 0.000 claims description 9
- 208000026310 Breast neoplasm Diseases 0.000 claims description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 8
- 206010058467 Lung neoplasm malignant Diseases 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 208000019065 cervical carcinoma Diseases 0.000 claims description 7
- 201000005296 lung carcinoma Diseases 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 206010028980 Neoplasm Diseases 0.000 claims description 4
- 201000011510 cancer Diseases 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000005311 nuclear magnetism Effects 0.000 claims 1
- 239000002246 antineoplastic agent Substances 0.000 abstract 1
- 229940041181 antineoplastic drug Drugs 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 47
- 230000001093 anti-cancer Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 238000000338 in vitro Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000000259 anti-tumor effect Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 201000005249 lung adenocarcinoma Diseases 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000004071 biological effect Effects 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
- 125000002524 organometallic group Chemical group 0.000 description 2
- 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 2
- 229910052718 tin Inorganic materials 0.000 description 2
- FTZIQBGFCYJWKA-UHFFFAOYSA-N 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium Chemical compound S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 FTZIQBGFCYJWKA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010008342 Cervix carcinoma Diseases 0.000 description 1
- 208000028018 Lymphocytic leukaemia Diseases 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms 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
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000008275 breast carcinoma Diseases 0.000 description 1
- 239000007853 buffer solution 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
- 150000007942 carboxylates Chemical class 0.000 description 1
- 201000010881 cervical cancer Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 210000002889 endothelial cell Anatomy 0.000 description 1
- -1 ester compounds Chemical class 0.000 description 1
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- 239000001963 growth medium Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 208000003747 lymphoid leukemia Diseases 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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Classifications
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a 2-carbonyl-3-phenylpropionic acid p-hydroxyphenylcarbonylhydrazone dibenzyl tin complex which is a complex shown in the structural formula (I), wherein Ph is phenyl. The invention also discloses a preparation method of the 2-carbonyl-3-phenylpropionic acid p-hydroxyphenylcarbonylhydrazone dibenzyl tin complex and an application in preparation of anti-cancer drugs.
Description
Technical field
The present invention relates to a kind of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex and preparation method thereof, and this 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex application in preparing cancer therapy drug.
Background technology
Organotin is the metallo-organic compound that a class contains Sn-C key.Researcher just noticed the Anticancer Activity in vitro of organo-tin compound before very early.1972, Brown found Ph first3SnOOCCH3Growth to mouse cancer cell is inhibited.1980, the research of the chemists such as Crowe showed, many organo-tin compounds have anti tumor activity in vitro.1989, American National anticancer research institute (National
Cancer Institute) more than 2,000 kinds of organo-tin compounds have been carried out 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 that many organo-tin compounds have preferable Anticancer Activity in vitro really after research.
Research shows, the organic group connected on organotin atom and the part participating in coordination decide the biologically active of organo-tin compound, select some tin atom coordinations having in the organic ligand of good biological activity and organotin itself to cause the great interest of people.Acylhydrazone is by a class of hydrazide kind compound modification
Schiff alkali cpd, they are condensed by aldehydes or ketones and hydrazides and form, have good biologically active, stronger coordination ability and various coordination mode, and have a wide range of applications at aspects such as medicine, agricultural chemicals, material and analytical reagents.In recent years, both at home and abroad it is compared in terms of biologically active and in depth studies by many researchers, and research finds that acylhydrazone has the various active such as anticancer, sterilization, anti-inflammatory.Therefore, by acylhydrazone class Schiff
Aar ligand is combined with organotin, it is intended to obtain the noval chemical compound that biologically active is higher, becomes the research direction that people are interested.
Chinese patent CN 102718794A discloses a kind of double acylhydrazone class
Schiff alkali stannous phenide complex and the application in the medicine preparing Antilung gland cancer, colon cancer, leukaemia thereof.
Chinese patent CN 101851251A discloses a kind of acylhydrazone class
The dibutyl tin complex of Schiff aar ligand and the application in preparation treatment liver cancer, adenocarcinoma of lung, breast cancer, prostate cancer, colon cancer or the youngest leukemic medicine of grain thereof.
Document (Journal of Organometallic Chemistry, 2014,75:83-91) report, organotin acylhydrazone class Schiff alkali complex has relatively strong biological activity to human colon cancer cell (HCT-116), human lung adenocarcinoma cell (A549), Human umbilical vein endothelial cells (HUVEC), and is better than carboplatin.
Document (Journal of Organometallic Chemistry, 2013,724:23-31) is reported, series organotin acylhydrazone class Schiff alkali complex, organo-tin compound and acylhydrazone class
Schiff aar ligand inhibitory action to cancer cells such as human lung adenocarcinoma cell (A549), human colon cancer cell (HCT-8), people in loop (hl-60) respectively.
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 active anticancer of human lung adenocarcinoma cell (A549).
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 selects para hydroxybenzene formylhydrazine, Sodium.beta.-phenylpyruvate to react under certain condition with TriphenylphosphineoxComplex, synthesis has obtained the complex to human colon cancer cell (Colo205), human liver cancer cell (HepG2), breast cancer cell (MCF7), cervical cancer cell (Hela) and human lung carcinoma cell (NCI-H460) with certain inhibitory activity, provides 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 para hydroxybenzene formyl hydrazone Dibenzyltin complex.
The second object of the present invention is to provide above-mentioned 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex preparation method.
The third object of the present invention is to provide the application in preparing cancer therapy drug of the above-mentioned 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.
As a kind of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of a first aspect of the present invention, for the complex of structure formula (I)
(I)
Wherein Ph is phenyl.
2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin the complex of the present invention is through elementary analysis, infrared spectrum and nuclear magnetic resoance spectrum structural analysis, and result is as follows:
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Being structurally characterized in that of the 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of the present invention: in molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations.
2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin the complex of the present invention has certain thermally-stabilised scope, can stable existence below 184 DEG C.
Preparation method as a kind of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of a second aspect of the present invention; TriphenylphosphineoxComplex, para hydroxybenzene formylhydrazine, Sodium.beta.-phenylpyruvate and solvent absolute methanol is added in the reaction vessel having nitrogen to protect; 5 ~ 24 h are reacted under conditions of temperature is 45 ~ 65 DEG C; cooling; filter; solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C; obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.
In a preferred embodiment of the invention, the amount of the material of described TriphenylphosphineoxComplex, para hydroxybenzene formylhydrazine, Sodium.beta.-phenylpyruvate three is than for 1:(1 ~ 1.05): (1.05 ~ 1.15).
In a preferred embodiment of the invention, described solvent absolute methanol consumption be every mM of TriphenylphosphineoxComplex add 15 ~ 35 milliliters.
As the application in preparing cancer therapy drug of a kind of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of a third aspect of the present invention.
Applicant has carried out anti tumor activity in vitro to above-mentioned 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex and has determined research, confirm 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex and there is certain anticancer bioactive, the purposes of the most above-mentioned complex is the application in preparing cancer therapy drug, is exactly the application in preparing anti-human colon cancer, people's liver cancer, human breast carcinoma, human cervical carcinoma, people's lung-cancer medicament specifically.
2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin the complex of the present invention demonstrates good active anticancer to human colon cancer cell, human liver cancer cell, human breast cancer cell, human cervical carcinoma cell, human lung carcinoma cell etc., the features such as the 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex active anticancer height of the present invention, low cost, preparation method are simple, provide new way for developing new cancer therapy drug.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.
Fig. 2 is 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex1H NMR spectra.
Fig. 3 is 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex13C NMR spectra.
Fig. 4 is the TG-DTG curve of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.
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 by any restriction of these embodiments.
Embodiment 1:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
0.372g is added in the 100mL there-necked flask having nitrogen to protect
(1.0mmol) TriphenylphosphineoxComplex, 0.152g (1.0mmol) para hydroxybenzene formylhydrazine, 0.205g (1.1mmol) Sodium.beta.-phenylpyruvate and 25mL solvent absolute methanol, 8 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 86.8%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Embodiment 2:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
0.372g is added in the 100mL there-necked flask having nitrogen to protect
(1.0mmol) TriphenylphosphineoxComplex, 0.152g (1.0mmol) para hydroxybenzene formylhydrazine, 0.195g (1.05mmol) Sodium.beta.-phenylpyruvate and 35mL solvent absolute methanol, 5 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 88.4%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Embodiment 3:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
0.372g is added in the 100mL there-necked flask having nitrogen to protect
(1.0mmol) TriphenylphosphineoxComplex, 0.160g (1.05mmol) para hydroxybenzene formylhydrazine, 0.214g (1.15mmol) Sodium.beta.-phenylpyruvate and 30mL solvent absolute methanol, 15 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 89.9%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Embodiment 4:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
1.860g is added in the 250mL there-necked flask having nitrogen to protect
(5.0mmol) TriphenylphosphineoxComplex, 0.775g (5.1mmol) para hydroxybenzene formylhydrazine, 1.004g (5.4mmol) Sodium.beta.-phenylpyruvate and 100mL solvent absolute methanol, 20 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 85.4%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Embodiment 5:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
1.860g is added in the 250mL there-necked flask having nitrogen to protect
(5.0mmol) TriphenylphosphineoxComplex, 0.790g (5.2mmol) para hydroxybenzene formylhydrazine, 1.042g (5.6mmol) Sodium.beta.-phenylpyruvate and 150mL solvent absolute methanol, 22 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 87.6%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Embodiment 6:
The preparation of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex:
3.720g is added in the 250mL there-necked flask having nitrogen to protect
(10.0mmol) TriphenylphosphineoxComplex, 1.550g (10.2mmol) para hydroxybenzene formylhydrazine, 1.972g (10.6mmol) Sodium.beta.-phenylpyruvate and 150mL solvent absolute methanol, 24 h are reacted under conditions of temperature is 45 ~ 65 DEG C, cooling, filter, solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C, obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.Productivity: 83.3%.Fusing point: 184 ~ 186 DEG C (dec).
Elementary analysis (C31H30N2O5Sn): calculated value: C 59.17, H 4.81, N 4.45；Measured value: C 59.24, H 4.76, N 4.42.
FT-IR
(KBr, ν/cm-1): 3296, 3061, 3026,
2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518, 460。
1H NMR
(400 MHz, DMSO-d 6) δ(ppm):
9.98 (s, 1H), 7.77 (d,J = 7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m,
13H), 4.12 (s, 1H), 3.42 (s, 2H), 3.17(s, 3H), 2.81 (s, 4H)。
13C NMR
(100 MHz, DMSO-d 6) δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
Test example:
2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin the complex of the present invention, its Anticancer Activity in vitro is measured and is realized by MTT experiment method.
MTT analytic approach:
With metabolism reduction 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium
Based on bromide.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 is without this function.Dimethyl sulfoxide (DMSO) (DMSO) can dissolve the first a ceremonial jade-ladle, used in libation in cell, measures the optical density of characteristic wavelength with ELIASA, can indirectly reflect living cells quantity.
Mtt assay is used to measure the 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of embodiment 1 preparation to human colon cancer cell (Colo205), human liver cancer cell (HepG2), human breast cancer cell (MCF7), human cervical carcinoma cell (Hela) and the inhibitory activity of human lung carcinoma cell (NCI-H460).
Cell line and cultivating system: Colo205, HepG2, MCF7, Hela and NCI-H460 cell line takes from American. tissue incubator (ATCC).RPMI 1640(GIBICO company with containing 10% hyclone) culture medium, in 5%(volume fraction) CO2, carry out in vitro culture in 37 DEG C of saturated humidity incubators.
Test process: test liquid (0.1ng/mL ~ 10ug/mL) being added separately in each hole according to the concentration gradient of concentration, each concentration sets 6 parallel holes.Experiment is divided into drug study group (being separately added into the test medicine of variable concentrations), control group (only adding 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 placed in 37 DEG C, 5%CO2Incubator is cultivated 72h.The activity of control drug measures according to the method for test sample.In orifice plate after having cultivated 72h, every hole adds MTT
40uL(D-Hanks buffer solution is made into 4mg/mL).After placing 4h at 37 DEG C, remove supernatant liquor.Every hole adds 150uL DMSO, and vibrate 5min, makes Formazan crystallization dissolve.Finally, automatic ELIASA is utilized to detect the optical density in each hole at 570nm wavelength.
Data process: data process and use Graph Pad Prism version 5.0 program, complex IC50It is fitted obtaining by program has the nonlinear regression model (NLRM) of S-shaped dose response.
With MTT analytic approach, 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 line are analyzed, measure its IC50Value, result is as shown in table 1, conclusion is: from data in table, it is used as cancer therapy drug with the 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex of the present invention, 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) are had certain drug effect, can be as the candidate compound of cancer therapy drug.
Table 1 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex cancer therapy drug external activity test data.
2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex prepared by remaining embodiment is with the mtt assay same test example of active anticancer method of testing 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), and test result is essentially identical with table 1.
Claims (8)
1. a 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex, for the complex of following structure formula (I):
(I)
Wherein Ph is phenyl.
2. as claimed in claim 1 containing a kind of 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex, its ir data: FT-IR
(KBr, ν/cm-1):
3296, 3061, 3026, 2808, 1641, 1589, 1492, 1386, 1168, 759, 696, 648, 592, 518,
460；Its nuclear-magnetism modal data:1H NMR (400 MHz, DMSO-d 6) δ(ppm): 9.98 (s, 1H), 7.77 (d,J =
7.31 Hz, 2H), 7.16 (m, 4H), 6.66-6.92 (m, 13H), 4.12 (s, 1H), 3.42 (s, 2H),
3.17(s, 3H), 2.81 (s, 4H)；13C NMR (100 MHz, DMSO-d 6)
δ(ppm):
172.94, 164.64, 160.34, 150.34, 138.62, 136.40, 129.94, 128.09, 127.97, 127.31,
125.74, 125.21, 123.95, 114.86, 48.62, 31.45。
3. described in claim 1,2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex has certain thermally-stabilised scope, can stable existence below 184 DEG C.
4. the preparation method of the 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex described in claim 1; it is characterized in that adding TriphenylphosphineoxComplex, para hydroxybenzene formylhydrazine, Sodium.beta.-phenylpyruvate and solvent absolute methanol in the reaction vessel having nitrogen to protect; 5 ~ 24 h are reacted under conditions of temperature is 45 ~ 65 DEG C; cooling; filter; solvent volatilization crystallization is controlled under conditions of 20 ~ 35 DEG C; obtain orange colour transparent crystal, be 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex.
5. the method for preparation as claimed in claim 4, it is characterised in that described TriphenylphosphineoxComplex, para hydroxybenzene formylhydrazine, Sodium.beta.-phenylpyruvate three the amount ratio of material for 1:(1 ~ 1.05): (1.05 ~ 1.15).
6. the method for preparation as claimed in claim 4, it is characterised in that described solvent absolute methanol consumption be every mM of TriphenylphosphineoxComplex add 15 ~ 35 milliliters.
7. 2-carbonyl-3-phenylpropionic acid para hydroxybenzene formyl hydrazone Dibenzyltin complex application in preparing cancer therapy drug described in claim 1.
8. the application described in claim 7, wherein said cancer cell is human colon cancer cell, human liver cancer cell, human breast cancer cell, human cervical carcinoma cell, human lung carcinoma cell.
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