CN105399764A - 2-oxo-propionic acid benzoyl hydrazone dibenzyl tin complex as well as preparation method and application thereof - Google Patents
2-oxo-propionic acid benzoyl hydrazone dibenzyl tin complex as well as preparation method and application thereof Download PDFInfo
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- CN105399764A CN105399764A CN201510764232.9A CN201510764232A CN105399764A CN 105399764 A CN105399764 A CN 105399764A CN 201510764232 A CN201510764232 A CN 201510764232A CN 105399764 A CN105399764 A CN 105399764A
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- propionic acid
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- benzoyl hydrazone
- acid benzoyl
- carbonyl propionic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 2-oxo-propionic acid benzoyl hydrazone dibenzyl tin Chemical compound 0.000 title abstract 4
- 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
- RJPFRUMILSYQEI-UHFFFAOYSA-N C(C1=CC=CC=C1)[Sn]CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)NN=C(C(C)=C=O)O Chemical compound C(C1=CC=CC=C1)[Sn]CC1=CC=CC=C1.C(C1=CC=CC=C1)(=O)NN=C(C(C)=C=O)O RJPFRUMILSYQEI-UHFFFAOYSA-N 0.000 claims description 48
- 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
- 229940079593 drug Drugs 0.000 claims description 12
- 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 description 11
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000013078 crystal Substances 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
- 208000029742 colonic neoplasm Diseases 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 201000007270 liver cancer Diseases 0.000 claims description 9
- 208000014018 liver neoplasm Diseases 0.000 claims description 9
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000006850 spacer group Chemical group 0.000 claims description 8
- 208000019065 cervical carcinoma Diseases 0.000 claims description 7
- 238000002447 crystallographic data Methods 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
- 229910052718 tin Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910020923 Sn-O Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 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 49
- 238000012360 testing method Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000259 anti-tumor effect Effects 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000001093 anti-cancer Effects 0.000 description 6
- 230000004071 biological effect Effects 0.000 description 6
- 238000000338 in vitro Methods 0.000 description 5
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 208000001333 Colorectal Neoplasms Diseases 0.000 description 3
- 201000010989 colorectal carcinoma Diseases 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 201000005249 lung adenocarcinoma Diseases 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
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material 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
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000452 restraining effect Effects 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
- 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
- 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
- 238000013459 approach Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 201000008275 breast carcinoma Diseases 0.000 description 1
- 244000309466 calf Species 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013016 damping Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 125000002524 organometallic group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 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
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000007858 starting material 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
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 210000003606 umbilical 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention discloses a 2-oxo-propionic acid benzoyl hydrazone dibenzyl tin complex with a structural formula (I) shown in the specification, wherein Ph is phenyl. The invention also discloses a preparation method of the 2-oxo-propionic acid benzoyl hydrazone dibenzyl tin complex and application of the 2-oxo-propionic acid benzoyl hydrazone dibenzyl tin complex in preparation of anti-cancer drugs.
Description
Technical field
The present invention relates to a kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex and preparation method thereof, and this 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex is preparing the application in cancer therapy drug.
Background technology
Organotin is the organometallics that a class contains Sn-C key.Researcher just noticed the Anticancer Activity in vitro of organo-tin compound before very early.1972, Brown Late Cambrian Ph
3snOOCCH
3inhibited to the growth of mouse cancer cells.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 (NationalCancerInstitute) has carried out antitumor activity screening to more than 2,000 kinds of organo-tin compounds, and result shows that some organo-tin compounds have restraining effect to P388 Lymphocytic leukemia.2002, the people such as Gielen were doing comprehensive summing up to the activity of organotin carboxylate's ester cpds, thought that many organo-tin compounds have good Anticancer Activity in vitro really after research.
Research shows, the part of the organic group that organotin atom connects and participation coordination decides the biological activity of organo-tin compound, selects the tin atom coordination in some organic ligands with good biological activity itself and organotin to cause the great interest of people.Acylhydrazone is by a class Schiff compound of hydrazide kind compound modification, they are formed by aldehydes or ketones and hydrazides condensation, there is good biological activity, stronger coordination ability and various coordination mode, and have a wide range of applications in medicine, agricultural chemicals, material and analytical reagent etc.In recent years, domestic and international many researchists compare it and in depth study in biological activity, and research finds that acylhydrazone has the various active such as anticancer, sterilization, anti-inflammatory.Therefore, acylhydrazone class Schiff part is combined with organotin, attempts to obtain the stronger new compound of biological activity, become the interested research direction of people.
Chinese patent CN102718794A discloses a kind of pair of acylhydrazone class Schiff tin diphenyl title complex and the application in the medicine preparing anti-lung gland cancer, colorectal carcinoma, leukemia cell thereof.
Chinese patent CN101851251A discloses a kind of dibutyl tin title complex of acylhydrazone class Schiff part and is preparing the application in Hepatoma therapy, adenocarcinoma of lung, mammary cancer, prostate cancer, colorectal carcinoma or the leukemic medicine of young grain morning.
Document (JournalofOrganometallicChemistry, 2014,75:83-91) report, organotin acylhydrazone class Schiff base complex has comparatively 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 (JournalofOrganometallicChemistry, 2013,724:23-31) report, serial organotin acylhydrazone class Schiff base complex, organo-tin compound and acylhydrazone class Schiff part are respectively to the restraining effect of the cancer cells such as human lung adenocarcinoma cell (A549), human colon cancer cell (HCT-8), people in loop (hl-60).
Document (Bioorganic & MedicinalChemistryLetters, 2015,25:4461-4463) is reported, multiple acylhydrazone class Schiff part is to the antitumour activity of human liver cancer cell (HuH-7) and human lung adenocarcinoma cell (A549).
The experiment proved that the material with antitumour activity based on acylhydrazone class Schiff organotin complex, the present invention selects benzoyl hydrazine, Sodium.alpha.-ketopropionate and TriphenylphosphineoxComplex to react under certain condition, synthesis obtains title complex 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) to certain inhibit activities, for exploitation cancer therapy drug provides new approach.
Summary of the invention
The first object of the present invention there is provided a kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
The second object of the present invention is to provide above-mentioned 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin complex preparation method.
The third object of the present invention is to provide above-mentioned 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex and is preparing the application in cancer therapy drug.
As a kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of a first aspect of the present invention, it is the title complex of structural formula (I)
(I)
Wherein Ph is phenyl.
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention is through ultimate analysis, infrared spectra, ultraviolet-visible spectrum, nuclear magnetic resonance spectrum and the structural analysis of X-ray single crystal diffraction, and result is as follows:
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention is crystalline structure, its crystal is oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
The constructional feature of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention is: in molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations, forms one dimensional infinite chain structure by Sn-O key bridging.
As the preparation method of a kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of a second aspect of the present invention; TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.alpha.-ketopropionate and solvent anhydrous methanol is added in the reaction vessel having nitrogen protection; be react 5 ~ 24h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; under the condition of 20 ~ 35 DEG C, control solvent evaporates crystallization, obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
In a preferred embodiment of the invention, the amount of substance of described TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.alpha.-ketopropionate three is than being 1:(1 ~ 1.05): (1.05 ~ 1.15).
In a preferred embodiment of the invention, described solvent anhydrous methanol consumption is that every mmole TriphenylphosphineoxComplex adds 15 ~ 35 milliliters.
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin complex preparation method of the present invention is one kettle way, adds direct reaction in reactor together by whole raw material, without the separation of intermediate, directly prepares 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.And the customary preparation methods of this area is for first to prepare part, again part and metallic starting compound are reacted and prepare title complex, 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin complex preparation method of the present invention compares this area customary preparation methods, there is the last handling process saving intermediate steps, save the advantages such as a large amount of human and material resources, financial resources.
A kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex as a third aspect of the present invention is preparing the application in cancer therapy drug.
Applicant has carried out anti tumor activity in vitro to above-mentioned 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex and has determined research, confirm 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex and there is certain anticancer bioactive, that is the purposes of above-mentioned title complex is preparing the application in cancer therapy drug, is exactly the application in the anti-human colorectal carcinoma of preparation, people's liver cancer, human breast carcinoma, human cervical carcinoma, people's lung-cancer medicament specifically.
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention demonstrates good antitumour activity 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 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex antitumour activity of the present invention is high, cost is low, preparation method is simple, provide new way for developing new cancer therapy drug.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
Fig. 2 is the UV-Vis spectrogram of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
Fig. 3 is 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex
1hNMR spectrogram.
Fig. 4 is 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex
13cNMR spectrogram.
Fig. 5 is the crystalline structure figure of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
Fig. 6 is the TG-DTG curve of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
Embodiment
Further describe the present invention by following examples, but scope of the present invention should be noted not by any restriction of these embodiments.
Embodiment 1:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.136g (1.0mmol) benzoyl hydrazine, 0.121g (1.1mmol) Sodium.alpha.-ketopropionate and 25mL solvent anhydrous methanol is added in the 100mL there-necked flask having nitrogen protection; be react 8h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 83.1%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Embodiment 2:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.136g (1.0mmol) benzoyl hydrazine, 0.116g (1.05mmol) Sodium.alpha.-ketopropionate and 35mL solvent anhydrous methanol is added in the 100mL there-necked flask having nitrogen protection; be react 5h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 82.7%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Embodiment 3:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
0.372g (1.0mmol) TriphenylphosphineoxComplex, 0.142g (1.05mmol) benzoyl hydrazine, 0.126g (1.15mmol) Sodium.alpha.-ketopropionate and 30mL solvent anhydrous methanol is added in the 100mL there-necked flask having nitrogen protection; be react 15h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 84.0%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Embodiment 4:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
1.860g (5.0mmol) TriphenylphosphineoxComplex, 0.694g (5.1mmol) benzoyl hydrazine, 0.594g (5.4mmol) Sodium.alpha.-ketopropionate and 100mL solvent anhydrous methanol is added in the 250mL there-necked flask having nitrogen protection; be react 20h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 81.9%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Embodiment 5:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
1.860g (5.0mmol) TriphenylphosphineoxComplex, 0.707g (5.2mmol) benzoyl hydrazine, 0.616g (5.6mmol) Sodium.alpha.-ketopropionate and 150mL solvent anhydrous methanol is added in the 250mL there-necked flask having nitrogen protection; be react 22h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 80.6%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Embodiment 6:
The preparation of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex:
3.720g (10.0mmol) TriphenylphosphineoxComplex, 1.387g (10.2mmol) benzoyl hydrazine, 1.166g (10.6mmol) Sodium.alpha.-ketopropionate and 150mL solvent anhydrous methanol is added in the 250mL there-necked flask having nitrogen protection; be react 24h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; solvent evaporates crystallization is controlled under the condition of 20 ~ 35 DEG C; obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.Productive rate: 78.7%.Fusing point: 120 ~ 122 DEG C (dec).
Ultimate analysis (C
25h
26n
2o
4sn): calculated value: C55.90, H4.88, N5.21; Measured value: C55.84, H4.89, N5.15.
FT-IR(KBr,ν/cm
-1):3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442。
UV-vis(DMF),λmax(nm):328。
1HNMR(400MHz,CDCl
3)δ(ppm):8.05(d,
J=7.6Hz,2H),7.57-7.54(m,1H),7.47-7.44(m,2H),7.11-6.99(m,10H),3.49(d,
J=2.1Hz,3H),3.10(s,4H),2.17(s,3H),0.93(q,
J=3.7Hz,1H)。
13CNMR(100MHz,CDCl
3)δ(ppm):174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90。
Crystallographic data: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088.
Test example:
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention, its Anticancer Activity in vitro is measured and is realized by MTT experiment method.
MTT analytical method:
Based on metabolism reduction 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide.Succinodehydrogenase in viable cell plastosome can make exogenous MTT be reduced to water-insoluble bluish voilet crystallization first a ceremonial jade-ladle, used in libation (Formazan) and be deposited in cell, and dead cell is without this function.First a ceremonial jade-ladle, used in libation in dimethyl sulfoxide (DMSO) (DMSO) energy dissolved cell, measures the optical density(OD) of characteristic wavelength, can indirectly reflect viable cell quantity by microplate reader.
Mtt assay is adopted to measure the 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of embodiment 1 preparation to the inhibit activities of 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 and culture system: Colo205, HepG2, MCF7, Hela and NCI-H460 cell strain takes from American. tissue incubator (ATCC).RPMI1640(GIBICO company with containing 10% foetal calf serum) substratum, in 5%(volume fraction) CO
2, carry out vitro culture in 37 DEG C of saturated humidity incubators.
Test process: join in each hole respectively by testing the concentration gradient of liquid (0.1ng/mL ~ 10ug/mL) according to concentration, each concentration establishes 6 parallel holes.Experiment is divided into drug study group (adding the test medicine of different concns respectively), control group (only add nutrient solution and cell, do not add test medicine) and blank group (only add cultivation medicine, do not add cell and test medicine).Orifice plate after dosing is placed in 37 DEG C, 5%CO
272h is cultivated in incubator.The activity of control drug measures according to the method for test sample.In orifice plate after having cultivated 72h, every hole adds MTT40uL(D-Hanks damping fluid and is made into 4mg/mL).After placing 4h at 37 DEG C, remove supernatant liquid.Every hole adds 150uLDMSO, and vibration 5min, makes Formazan dissolving crystallized.Finally, automatic microplate reader is utilized to detect the optical density(OD) in each hole at 570nm wavelength place.
Data processing: data processing uses GraphPadPrismversion5.0 program, title complex IC
50carry out matching by the nonlinear regression model (NLRM) in program with S shape dose response to obtain.
With MTT analytical method, 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 are analyzed, measure its IC
50value, result is as shown in table 1, conclusion is: from data in table, cancer therapy drug is used as with 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex of the present invention, 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 used as the candidate compound of cancer therapy drug.
Table 12-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex cancer therapy drug external activity test data.
2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex prepared by all the other embodiments is with the same test example of antitumour activity testing method of mtt assay 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 and table 1 are substantially identical.
Claims (10)
1. a 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex, the title complex for following structural formula (I):
(I)
Wherein Ph is phenyl.
2. as claimed in claim 1 containing a kind of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex, its ir data: FT-IR (KBr, ν/cm
-1): 3435,3078,3022,2941,1599,1584,1389,1335,590,552,459,442; Its ultraviolet-visible light modal data: UV-vis (DMF), λ max (nm): 328; Its nuclear-magnetism modal data:
1hNMR (400MHz, CDCl
3) δ (ppm): 8.05 (d,
j=7.6Hz, 2H), 7.57-7.54 (m, 1H), 7.47-7.44 (m, 2H), 7.11-6.99 (m, 10H), 3.49 (d,
j=2.1Hz, 3H), 3.10 (s, 4H), 2.17 (s, 3H), 0.93 (q,
j=3.7Hz, 1H);
13cNMR (100MHz, CDCl
3) δ (ppm): 174.79,160.94,152.91,136.16,132.89,132.07,128.71,124.40,128.19,125.46,109.98,50.84,33.66,12.90.
3. 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex as claimed in claim 1, wherein, described 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex is crystalline structure, and its crystallographic data is as follows: oblique system, spacer P2 (1)/n, a=1.2237 (2) nm, b=0.94388 (15) nm, c=2.0654 (4) nm, α=γ=90 °, β=91.406 (2) °, Z=4, V=2.3850 (7) nm
3, Dc=1.496Mgm
-3, m (MoK α)=1.104mm
-1, F (000)=1088; In molecule, tin atom is seven coordination distortion pentagonal bipyramid configurations, forms one dimensional infinite chain structure by Sn-O key bridging.
4. described in claim 1,2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex has certain thermally-stabilised scope, can stable existence below 120 DEG C.
5. the preparation method of 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex according to claim 1; it is characterized in that in the reaction vessel having nitrogen protection, add TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.alpha.-ketopropionate and solvent anhydrous methanol; be react 5 ~ 24h under the condition of 45 ~ 65 DEG C in temperature; cooling; filter; under the condition of 20 ~ 35 DEG C, control solvent evaporates crystallization, obtain light green transparent crystals, be 2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex.
6. the method for preparation as claimed in claim 5, is characterized in that, the amount of substance of described TriphenylphosphineoxComplex, benzoyl hydrazine, Sodium.alpha.-ketopropionate three is than being 1:(1 ~ 1.05): (1.05 ~ 1.15).
7. the method for preparation as claimed in claim 5, it is characterized in that, described solvent anhydrous methanol consumption is that every mmole TriphenylphosphineoxComplex adds 15 ~ 35 milliliters.
8. the method for preparation as claimed in claim 5, is characterized in that, adopts one kettle way preparation.
9. described in claim 1,2-carbonyl propionic acid benzoyl hydrazone Dibenzyltin title complex is preparing the application in cancer therapy drug.
10. application according to claim 9, wherein said cancer cells 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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| CN105753896A (en) * | 2016-04-11 | 2016-07-13 | 衡阳师范学院 | 2-carbonyl-3-phenylpropionic acid p-hydroxyphenylcarbonylhydrazone dibenzyl tin complex as well as preparation method and application thereof |
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| CN106366120A (en) * | 2016-08-30 | 2017-02-01 | 衡阳师范学院 | 2-carbonyl butyric acid p-metoxybenzene formyl hydrazone diphenyl tin complex and preparation method and application thereof |
| CN106366120B (en) * | 2016-08-30 | 2019-02-19 | 衡阳师范学院 | A kind of ALPHA-ketobutyric acid is to methoxybenzoyl hydrazone stannous phenide complex and its preparation method and application |
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