CN103396435B - Dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex as well as preparation method and application thereof - Google Patents
Dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex as well as preparation method and application thereof Download PDFInfo
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- CN103396435B CN103396435B CN201310305883.2A CN201310305883A CN103396435B CN 103396435 B CN103396435 B CN 103396435B CN 201310305883 A CN201310305883 A CN 201310305883A CN 103396435 B CN103396435 B CN 103396435B
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- -1 Dibutyl tin aromatic aldehyde Chemical class 0.000 title claims abstract description 140
- 239000002262 Schiff base Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000010668 complexation reaction Methods 0.000 title description 3
- 239000003814 drug Substances 0.000 claims abstract description 19
- 206010009944 Colon cancer Diseases 0.000 claims abstract description 11
- 201000007270 liver cancer Diseases 0.000 claims abstract description 11
- 208000014018 liver neoplasm Diseases 0.000 claims abstract description 11
- 206010006187 Breast cancer Diseases 0.000 claims abstract description 10
- 208000026310 Breast neoplasm Diseases 0.000 claims abstract description 10
- 206010058467 Lung neoplasm malignant Diseases 0.000 claims abstract description 9
- 201000005202 lung cancer Diseases 0.000 claims abstract description 6
- 208000020816 lung neoplasm Diseases 0.000 claims abstract description 6
- 206010008342 Cervix carcinoma Diseases 0.000 claims abstract description 4
- 208000006105 Uterine Cervical Neoplasms Diseases 0.000 claims abstract description 4
- 201000010881 cervical cancer Diseases 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 44
- 239000013078 crystal Substances 0.000 claims description 26
- 125000006850 spacer group Chemical group 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 6
- 208000001333 Colorectal Neoplasms Diseases 0.000 claims description 3
- 201000010989 colorectal carcinoma Diseases 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 206010028980 Neoplasm Diseases 0.000 claims 2
- 201000011510 cancer Diseases 0.000 claims 2
- 230000001225 therapeutic effect Effects 0.000 claims 1
- 229940079593 drug Drugs 0.000 abstract description 8
- 208000029742 colonic neoplasm Diseases 0.000 abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 28
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 18
- 229910020813 Sn-C Inorganic materials 0.000 description 17
- 229910018732 Sn—C Inorganic materials 0.000 description 17
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 229910020923 Sn-O Inorganic materials 0.000 description 16
- 238000002447 crystallographic data Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 230000000259 anti-tumor effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011275 oncology therapy Methods 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 208000019065 cervical carcinoma Diseases 0.000 description 5
- 125000006414 CCl Chemical group ClC* 0.000 description 4
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 4
- 235000005291 Rumex acetosa Nutrition 0.000 description 4
- 240000007001 Rumex acetosella Species 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000003513 sheep sorrel Nutrition 0.000 description 4
- 239000002246 antineoplastic agent Substances 0.000 description 3
- 229940041181 antineoplastic drug Drugs 0.000 description 3
- 201000005296 lung carcinoma 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
- 208000010507 Adenocarcinoma of Lung Diseases 0.000 description 2
- 208000002454 Nasopharyngeal Carcinoma Diseases 0.000 description 2
- 206010061306 Nasopharyngeal cancer Diseases 0.000 description 2
- 208000005718 Stomach Neoplasms Diseases 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 201000008275 breast carcinoma Diseases 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 239000003112 inhibitor 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
- 201000011216 nasopharynx carcinoma Diseases 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 201000000498 stomach carcinoma Diseases 0.000 description 2
- FABVMBDCVAJXMB-UHFFFAOYSA-N 3,5-dichloro-2-hydroxybenzaldehyde Chemical compound OC1=C(Cl)C=C(Cl)C=C1C=O FABVMBDCVAJXMB-UHFFFAOYSA-N 0.000 description 1
- 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
- 190000008236 Carboplatin Chemical compound 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
- 230000001093 anti-cancer Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000003556 assay Methods 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
- 244000309466 calf Species 0.000 description 1
- 229960004562 carboplatin Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 231100000673 dose–response relationship Toxicity 0.000 description 1
- 238000003255 drug test Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 206010073071 hepatocellular carcinoma Diseases 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex which has a structural formula (I) as shown in the specification, wherein Bu represents normal butyl, R<1> is -OCH3, -Cl or -H, R<2> is -H, -Cl or -Br, and R<3> is -H or -NO2. The invention further discloses a preparation method of the dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex and an application of the dibutyl tin aromatic aldehyde condensed arylamine Schiff base complex for preparing medicines for treating cervical cancer, breast cancer, liver cancer, colon cancer or lung cancer.
Description
Technical field
The present invention relates to serial dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex, and preparation method thereof, and this serial title complex is preparing the application in antitumor drug.
Background technology
Schiff is the compound that a class has pharmacology and physiologically active, because it is for ligating atom with nitrogen-atoms and Sauerstoffatom, comparatively close with coenocorrelation, it is the focus that people study always, disclose 3,5-diiodo-salicylic aldehyde Schiff of series as Chinese patent CN101302172 and preparing the application in antiseptic-germicide.
Organotin is the organometallics that a class contains Sn-C key, has the compound compared with high biological activity, has wide practical use in sterilization, cancer therapy drug preparation.Already studied and shown, radicals R and playing an important role with the antitumour activity of structure to compound of the part of tin atom coordination in organotin, e.g., the antitumour activity of cyclohexyl, normal-butyl and phenyltin compound is comparatively strong, and ethyl takes second place, and methyl is almost without antitumour activity.Experiment proves, obviously strengthen before biological activity ratio's coordination of Schiff class part after forming title complex, its title complex has biological and pharmacoligical activities widely.Therefore, Schiff class part is combined with organotin, becomes a research direction of people's interest.
As Chinese patent CN101475583 discloses a kind of dibutyl tin dichloride Schiff coordination compound and the application in preparation treatment cancer of the stomach, nasopharyngeal carcinoma, people's liver cancer or leukemic medicine thereof.
Chinese patent CN102718794A discloses a kind of two acylhydrazone class Schiff tin diphenyl (IV) title complex and the application in the medicine of preparation treatment adenocarcinoma of lung, colorectal carcinoma, leukemia cell thereof.
Chinese patent CN101434616 discloses a kind of organotin Schiff coordination compound and the application in preparation treatment cancer of the stomach, nasopharyngeal carcinoma, people's liver cancer or leukemic medicine thereof.
Chinese patent CN101851251A discloses a kind of dibutyl tin (IV) 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.
The experiment proved that the material with antitumour activity based on dibutyl tin compounds, the present invention selects dibutyl tin dichloride or Dibutyltin oxide compound, respectively with o-vanillin, 3, 5-dichloro-salicylaldehyde, aromatic aldehyde and the o-aminophenols such as 5-bromosalicylaldehyde, the Schiff of the arylamine condensations such as 4-nitro o-aminophenol is part, react under certain condition, synthesis obtains human cervical carcinoma cell (Hela), human breast cancer cell (MCF7), human liver cancer cell (HepG2), human colon cancer cell (Colo205), the title complex that the inhibit activities of human lung carcinoma cell (NCI-H460) is stronger, for exploitation cancer therapy drug provides new way.
Summary of the invention
An object of the present invention is to provide serial dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex.
Two of the object of the invention is the preparation method providing above-mentioned serial dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex.
Three of the object of the invention is to provide the application of above-mentioned serial dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex in medicine.
In order to realize foregoing invention object, the technical solution adopted in the present invention is:
Dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex, the title complex for following structural formula (I):
Wherein: Bu represents normal-butyl,
R
1for-OCH
3,-Cl or-H, R
2for-H ,-Cl or-Br, R
3for-H or-NO
2.
In a preferred embodiment of the invention, R is worked as
1for-OCH
3, R
2for-H, R
3during for-H, form title complex (I-1).
In a preferred embodiment of the invention, described title complex (I-1) is crystalline structure.
In a preferred embodiment of the invention, described title complex (I-1) is oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3; There is the independent molecule of two similar in crystal, the center tin of each molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration.
In a preferred embodiment of the invention, R is worked as
1for-OCH
3, R
2for-H, R
3for-NO
2time, form title complex (I-2).
In a preferred embodiment of the invention, described title complex (I-2) is crystalline structure.
In a preferred embodiment of the invention, described title complex (I-2) is oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3; There is the independent molecule of two similar in crystal, the center tin of each molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration.
In a preferred embodiment of the invention, R is worked as
1for-Cl, R
2for-Cl, R
3for-NO
2time, form title complex (I-3).
In a preferred embodiment of the invention, described title complex (I-3) is crystalline structure.
In a preferred embodiment of the invention, described title complex (I-3) is triclinic(crystalline)system, spacer P1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3; The center tin of molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration.
In a preferred embodiment of the invention, R is worked as
1for-H, R
2for-Br, R
3for-NO
2time, form title complex (I-4).
In a preferred embodiment of the invention, described title complex (I-4) is crystalline structure.
In a preferred embodiment of the invention, described title complex (I-4) is oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3; The center tin of molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration.
The preparation method of above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex, it adds aromatic aldehyde contracting arylamine Schiff base, Dibutyltin oxide or dibutyl tin dichloride, sodium methylate and solvent anhydrous methanol in order successively in reaction vessel, under stirring and refluxing, react 8 ~ 12h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain crystal, be dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex.
Wherein aromatic aldehyde contracting arylamine Schiff base, dibutyl tin dichloride or Dibutyltin oxide are reactant, sodium methylate is catalyzer, anhydrous methanol is reaction solvent, the mass ratio of reactant aromatic aldehyde contracting arylamine Schiff base and Dibutyltin oxide or dibutyl tin dichloride is 1:1 ~ 1:1.05, the mass ratio of catalyst sodium methoxide and reactant aromatic aldehyde contracting arylamine Schiff base is 0.004:1 ~ 2.05:1, and the consumption of solvent anhydrous methanol is that every mmole Dibutyltin oxide or dibutyl tin dichloride add 30 ~ 55 ml methanol.
Applicant has carried out anti tumor activity in vitro to above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex and has confirmed research, confirm that this dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex has anti-tumor biological, that is the purposes of above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex is preparing the application in antitumor drug, is exactly specifically preparing the application in anti-cervical cancer or anti-breast cancer or anti-liver cancer or inhibitor against colon carcinoma cells or anti-lung-cancer medicament.
Dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex of the present invention has good antitumour activity, it can prepare anti-cervical cancer, anti-breast cancer, anti-liver cancer, inhibitor against colon carcinoma cells, anti-lung-cancer medicament for raw material.Compared with the platinum-containing anticancer drug generally used at present, dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex of the present invention has the features such as antitumour activity is high, cost is low, preparation method is simple, for exploitation cancer therapy drug provides new way.
Accompanying drawing explanation
Fig. 1 is dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-1) crystal molecular structure figure
Fig. 2 is dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-2) crystal molecular structure figure
Fig. 3 is dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-3) crystal molecular structure figure
Fig. 4 is dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-4) crystal molecular structure figure
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 dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1):
O-vanillin p-aminobenzoic o-aminophenol Schiff 0.122g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol is added in order successively, stirring heating backflow 8h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain sorrel crystal, be dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1).Productive rate: 72%, fusing point: 138 ~ 140 DEG C.
Ultimate analysis (the C of dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1)
44h
58n
2o
6sn
2): theoretical value: C, 55.72, H, 6.16, N, 2.95; Measured value: C, 55.62, H, 6.15; N, 2.99.
IR(KBr,cm
-1):2954,2920,2853ν(C-H),1603,1585ν(C=N),1245ν(C-O),601ν(Sn-O),523ν(Sn-N),420ν(Sn-C)。
1HNMR(CDCl
3,400MHz),δ(ppm):7.34(d,J=8.0Hz,1H,H-3),7.18(t,J=7.6Hz,1H,H-4),6.88(t,J=8.0Hz,1H,H-5),8.66(s,1H,H-7),6.95(d,J=7.6Hz,1H,H-9),6.69(t,J=6.4Hz,1H,H-10),6.67(t,J=8.4Hz,1H,H-11),6.85(d,J=8.0Hz,1H,H-12),3.86(s,3H,Ar-OCH
3),1.52(t,J=6.8Hz,4H,H-α),1.62(quint,J=6.8Hz,4H,H-β),1.31(sext,J=7.2Hz,4H,H-γ),0.82(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.36(Ar-OCH
3),161.86(C-7),13.47(C-θ),22.28(C-α),26.53(C-γ),26.95(C-β),114.75,115.96,116.19,116.93,117.83,118.54,126.60,130.00,131.80,151.79,159.72,160.63(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3, D
c=1.469Mgm
-3, μ (MoK
α)=1.213mm
-1, F (000)=1936,1.82 ° of < θ < 27.49 °, crystalline size: 0.35 × 0.23 × 0.21mm, R=0.0371, wR=0.1019.
Embodiment 2:
The preparation of dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1):
O-vanillin p-aminobenzoic o-aminophenol Schiff 0.487g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol is added in order successively, stirring heating backflow 11h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain sorrel crystal, be dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1).Productive rate: 75%, fusing point: 138 ~ 140 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1) ultimate analysis (C
44h
58n
2o
6sn
2): theoretical value: C, 55.72, H, 6.16; N, 2.95; Measured value: C, 55.62, H, 6.15, N, 2.99.
IR(KBr,cm
-1):2954,2920,2853ν(C-H),1603,1585ν(C=N),1245ν(C-O),601ν(Sn-O),523ν(Sn-N),420ν(Sn-C)。
1HNMR(CDCl
3,400MHz),δ(ppm):7.34(d,J=8.0Hz,1H,H-3),7.18(t,J=7.6Hz,1H,H-4),6.88(t,J=8.0Hz,1H,H-5),8.66(s,1H,H-7),6.95(d,J=7.6Hz,1H,H-9),6.69(t,J=6.4Hz,1H,H-10),6.67(t,J=8.4Hz,1H,H-11),6.85(d,J=8.0Hz,1H,H-12),3.86(s,3H,Ar-OCH
3),1.52(t,J=6.8Hz,4H,H-α),1.62(quint,J=6.8Hz,4H,H-β),1.31(sext,J=7.2Hz,4H,H-γ),0.82(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.36(Ar-OCH
3),161.86(C-7),13.47(C-θ),22.28(C-α),26.53(C-γ),26.95(C-β),114.75,115.96,116.19,116.93,117.83,118.54,126.60,130.00,131.80,151.79,159.72,160.63(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3, D
c=1.469Mgm
-3, μ (MoK
α)=1.213mm
-1, F (000)=1936,1.82 ° of < θ < 27.49 °, crystalline size: 0.35 × 0.23 × 0.21mm, R=0.0371, wR=0.1019.
Embodiment 3:
The preparation of dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1):
O-vanillin p-aminobenzoic o-aminophenol Schiff 0.243g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol is added in order successively, stirring heating backflow 10h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain sorrel crystal, be dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1).Productive rate: 74%, fusing point: 138 ~ 140 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1) ultimate analysis (C
44h
58n
2o
6sn
2): theoretical value: C, 55.72, H, 6.16, N, 2.95; Measured value: C, 55.62, H, 6.15, N, 2.99.
IR(KBr,cm
-1):2954,2920,2853ν(C-H),1603,1585ν(C=N),1245ν(C-O),601ν(Sn-O),523ν(Sn-N),420ν(Sn-C)。
1HNMR(CDCl
3,400MHz),δ(ppm):7.34(d,J=8.0Hz,1H,H-3),7.18(t,J=7.6Hz,1H,H-4),6.88(t,J=8.0Hz,1H,H-5),8.66(s,1H,H-7),6.95(d,J=7.6Hz,1H,H-9),6.69(t,J=6.4Hz,1H,H-10),6.67(t,J=8.4Hz,1H,H-11),6.85(d,J=8.0Hz,1H,H-12),3.86(s,3H,Ar-OCH
3),1.52(t,J=6.8Hz,4H,H-α),1.62(quint,J=6.8Hz,4H,H-β),1.31(sext,J=7.2Hz,4H,H-γ),0.82(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.36(Ar-OCH
3),161.86(C-7),13.47(C-θ),22.28(C-α),26.53(C-γ),26.95(C-β),114.75,115.96,116.19,116.93,117.83,118.54,126.60,130.00,131.80,151.79,159.72,160.63(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3, D
c=1.469Mgm
-3, μ (MoK
α)=1.213mm
-1, F (000)=1936,1.82 ° of < θ < 27.49 °, crystalline size: 0.35 × 0.23 × 0.21mm, R=0.0371, wR=0.1019.
Embodiment 4:
The preparation of dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1):
O-vanillin p-aminobenzoic o-aminophenol Schiff 0.365g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol is added in order successively, stirring heating backflow 12h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain sorrel crystal, be dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1).Productive rate: 79%, fusing point: 138 ~ 140 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic o-aminophenol Schiff base complex (I-1) ultimate analysis (C
44h
58n
2o
6sn
2): theoretical value: C, 55.72, H, 6.16, N, 2.95; Measured value: C, 55.62; H, 6.15, N, 2.99.
IR(KBr,cm
-1):2954,2920,2853ν(C-H),1603,1585ν(C=N),1245ν(C-O),601ν(Sn-O),523ν(Sn-N),420ν(Sn-C)。
1HNMR(CDCl
3,400MHz),δ(ppm):7.34(d,J=8.0Hz,1H,H-3),7.18(t,J=7.6Hz,1H,H-4),6.88(t,J=8.0Hz,1H,H-5),8.66(s,1H,H-7),6.95(d,J=7.6Hz,1H,H-9),6.69(t,J=6.4Hz,1H,H-10),6.67(t,J=8.4Hz,1H,H-11),6.85(d,J=8.0Hz,1H,H-12),3.86(s,3H,Ar-OCH
3),1.52(t,J=6.8Hz,4H,H-α),1.62(quint,J=6.8Hz,4H,H-β),1.31(sext,J=7.2Hz,4H,H-γ),0.82(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.36(Ar-OCH
3),161.86(C-7),13.47(C-θ),22.28(C-α),26.53(C-γ),26.95(C-β),114.75,115.96,116.19,116.93,117.83,118.54,126.60,130.00,131.80,151.79,159.72,160.63(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3, D
c=1.469Mgm
-3, μ (MoK
α)=1.213mm
-1, F (000)=1936,1.82 ° of < θ < 27.49 °, crystalline size: 0.35 × 0.23 × 0.21mm, R=0.0371, wR=0.1019.
Embodiment 5:
The preparation of dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (2):
O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff 0.144g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol is added in order successively, stirring heating backflow 8h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2).Productive rate: 71%, fusing point: 172 ~ 173 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2) ultimate analysis (C
44h
56n
4o
10sn
2): theoretical value: C, 50.89, H, 5.44, N, 5.40; Measured value: C, 50.97, H, 5.54, N, 5.33.
IR(KBr,cm
-1):2961,2921,2851ν(C-H),1606,1590ν(C=N),1506ν(C-NO
2),1248ν(C-O),669ν(Sn-O),507ν(Sn-N),419ν(Sn-C)。UV-vis(CH
3COCH
3),λ
max(nm):365,458。
1HNMR(CDCl
3,400MHz),δ(ppm):7.00(d,J=7.2Hz,1H,H-3),6.74(t,J=7.6Hz,1H,H-4),6.95(d,J=8.0Hz,1H,H-5),8.77(s,1H,H-7),8.33(d,J=1.6Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=2.0Hz,1H,H-11),6,82(d,J=8.8Hz,1H,H-12),3.87(s,3H,Ar-OCH
3),1.48-1.75(m,8H,H-α,H-β),1.32(sext,J=6.8Hz,4H,H-γ),0.83(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.35(Ar-OCH
3),164.25(C-7),13.46(C-θ),22.85(C-α),26.49(C-γ),26.85(C-β),111.78,116.84,117.48,117.90,125.98,127.10,131.56,137.24,151.85,166.06(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3, D
c=1.465Mgm
-3, μ (MoK
α)=1.118mm
-1, F (000)=2112,1.58 ° of < θ < 25 °, crystalline size: 0.17 × 0.15 × 0.12mm, R=0.0404, wR=0.1071.
Embodiment 6:
The preparation of dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (2):
O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff 0.577g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol is added in order successively, stirring heating backflow 11h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (2) of the present invention.Productive rate: 74%, fusing point: 172 ~ 173 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2) ultimate analysis (C
44h
56n
4o
10sn
2): theoretical value: C, 50.89, H, 5.44, N, 5.40; Measured value: C, 50.97, H, 5.54, N, 5.33.
IR(KBr,cm
-1):2961,2921,2851ν(C-H),1606,1590ν(C=N),1506ν(C-NO
2),1248ν(C-O),669ν(Sn-O),507ν(Sn-N),419ν(Sn-C)。UV-vis(CH
3COCH
3),λ
max(nm):365,458。
1HNMR(CDCl
3,400MHz),δ(ppm):7.00(d,J=7.2Hz,1H,H-3),6.74(t,J=7.6Hz,1H,H-4),6.95(d,J=8.0Hz,1H,H-5),8.77(s,1H,H-7),8.33(d,J=1.6Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=2.0Hz,1H,H-11),6,82(d,J=8.8Hz,1H,H-12),3.87(s,3H,Ar-OCH
3),1.48-1.75(m,8H,H-α,H-β),1.32(sext,J=6.8Hz,4H,H-γ),0.83(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.35(Ar-OCH
3),164.25(C-7),13.46(C-θ),22.85(C-α),26.49(C-γ),26.85(C-β),111.78,116.84,117.48,117.90,125.98,127.10,131.56,137.24,151.85,166.06(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3, D
c=1.465Mgm
-3, μ (MoK
α)=1.118mm
-1, F (000)=2112,1.58 ° of < θ < 25 °, crystalline size: 0.17 × 0.15 × 0.12mm, R=0.0404, wR=0.1071.
Embodiment 7:
The preparation of dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2):
O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff 0.288g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol is added in order successively, stirring heating backflow 10h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2).Productive rate: 71%, fusing point: 172 ~ 173 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2) ultimate analysis (C
44h
56n
4o
10sn
2): theoretical value: C, 50.89, H, 5.44, N, 5.40; Measured value: C, 50.97, H, 5.54, N, 5.33.
IR(KBr,cm
-1):2961,2921,2851ν(C-H),1606,1590ν(C=N),1506ν(C-NO
2),1248ν(C-O),669ν(Sn-O),507ν(Sn-N),419ν(Sn-C)。UV-vis(CH
3COCH
3),λ
max(nm):365,458。
1HNMR(CDCl
3,400MHz),δ(ppm):7.00(d,J=7.2Hz,1H,H-3),6.74(t,J=7.6Hz,1H,H-4),6.95(d,J=8.0Hz,1H,H-5),8.77(s,1H,H-7),8.33(d,J=1.6Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=2.0Hz,1H,H-11),6,82(d,J=8.8Hz,1H,H-12),3.87(s,3H,Ar-OCH
3),1.48-1.75(m,8H,H-α,H-β),1.32(sext,J=6.8Hz,4H,H-γ),0.83(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.35(Ar-OCH
3),164.25(C-7),13.46(C-θ),22.85(C-α),26.49(C-γ),26.85(C-β),111.78,116.84,117.48,117.90,125.98,127.10,131.56,137.24,151.85,166.06(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3, D
c=1.465Mgm
-3, μ (MoK
α)=1.118mm
-1, F (000)=2112,1.58 ° of < θ < 25 °, crystalline size: 0.17 × 0.15 × 0.12mm, R=0.0404, wR=0.1071.
Embodiment 8:
The preparation of dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2):
O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff 0.432g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol is added in order successively, stirring heating backflow 12h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2).Productive rate: 72%, fusing point: 172 ~ 173 DEG C.
Dibutyl tin O-vanillin p-aminobenzoic 4-nitro o-aminophenol Schiff base complex (I-2) ultimate analysis (C
44h
56n
4o
10sn
2): theoretical value: C, 50.89, H, 5.44, N, 5.40; Measured value: C, 50.97; H, 5.54, N, 5.33.
IR(KBr,cm
-1):2961,2921,2851ν(C-H),1606,1590ν(C=N),1506ν(C-NO
2),1248ν(C-O),669ν(Sn-O),507ν(Sn-N),419ν(Sn-C)。UV-vis(CH
3COCH
3),λ
max(nm):365,458。
1HNMR(CDCl
3,400MHz),δ(ppm):7.00(d,J=7.2Hz,1H,H-3),6.74(t,J=7.6Hz,1H,H-4),6.95(d,J=8.0Hz,1H,H-5),8.77(s,1H,H-7),8.33(d,J=1.6Hz,1H,H-9),8.13(dd,J
1=8.8Hz,J
2=2.0Hz,1H,H-11),6,82(d,J=8.8Hz,1H,H-12),3.87(s,3H,Ar-OCH
3),1.48-1.75(m,8H,H-α,H-β),1.32(sext,J=6.8Hz,4H,H-γ),0.83(t,J=7.2Hz,6H,H-θ)。
13CNMR(CDCl
3,100MHz),δ(ppm):56.35(Ar-OCH
3),164.25(C-7),13.46(C-θ),22.85(C-α),26.49(C-γ),26.85(C-β),111.78,116.84,117.48,117.90,125.98,127.10,131.56,137.24,151.85,166.06(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3, D
c=1.465Mgm
-3, μ (MoK
α)=1.118mm
-1, F (000)=2112,1.58 ° of < θ < 25 °, crystalline size: 0.17 × 0.15 × 0.12mm, R=0.0404, wR=0.1071.
Embodiment 9:
The preparation of dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3):
3 are added successively in order in round-bottomed flask, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.164g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3).Productive rate: 78%, fusing point: 129 ~ 131 DEG C.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3) ultimate analysis (C
21h
24cl
2n
2o
4sn): theoretical value: C, 45.20, H, 4.33, N, 5.02; Measured value: C, 45.28, H, 4.23, N, 5.09.
IR(KBr,cm
-1):2955,2919ν(C-H),1603,1580ν(C=N),1494ν(C-NO
2),1158ν(C-O),1075ν(C-Cl),520ν(Sn-O),484ν(Sn-N),423ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.73(d,J=2.4Hz,1H,H-3),7.71(d,J=2.4Hz,1H,H-5),9.27(s,1H,H-7),8.65(d,J=2.4Hz,1H,H-9),8.07(dd,J
1=9.2Hz,J
2=2.4Hz,1H,H-11),6.81(d,J=9.2Hz,1H,H-12),1.35-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.04(C-7),13.17(C-θ),25.43(C-α),26.34(C-γ),26.49(C-β),113.34,117.69,117.80,119.40,125.59,125.78,131.93,133.77,134.41,136.14,161.96,166.48(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer P1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3, D
c=1.609Mgm
-3, μ (MoK
α)=1.371mm
-1, F (000)=560,1.86 ° of < θ < 27.6 °, crystalline size: 0.25 × 0.23 × 0.21mm, R=0.0339, wR=0.0948.
Embodiment 10:
The preparation of dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3):
3 are added successively in order in round-bottomed flask, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.654g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3).Productive rate: 74%, fusing point: 129 ~ 131 DEG C.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3) ultimate analysis (C
21h
24cl
2n
2o
4sn): theoretical value: C, 45.20, H, 4.33, N, 5.02, measured value: C, 45.28, H, 4.23, N, 5.09.
IR(KBr,cm
-1):2955,2919ν(C-H),1603,1580ν(C=N),1494ν(C-NO
2),1158ν(C-O),1075ν(C-Cl),520ν(Sn-O),484ν(Sn-N),423ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.73(d,J=2.4Hz,1H,H-3),7.71(d,J=2.4Hz,1H,H-5),9.27(s,1H,H-7),8.65(d,J=2.4Hz,1H,H-9),8.07(dd,J
1=9.2Hz,J
2=2.4Hz,1H,H-11),6.81(d,J=9.2Hz,1H,H-12),1.35-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.04(C-7),13.17(C-θ),25.43(C-α),26.34(C-γ),26.49(C-β),113.34,117.69,117.80,119.40,125.59,125.78,131.93,133.77,134.41,136.14,161.96,166.48(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer P1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3, D
c=1.609Mgm
-3, μ (MoK
α)=1.371mm
-1, F (000)=560,1.86 ° of < θ < 27.6 °, crystalline size: 0.25 × 0.23 × 0.21mm, R=0.0339, wR=0.0948.
Embodiment 11:
The preparation of dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (3):
3 are added successively in order in round-bottomed flask, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.327g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3).Productive rate: 73%, fusing point: 129 ~ 131 DEG C.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3) ultimate analysis (C
21h
24cl
2n
2o
4sn): theoretical value: C, 45.20, H, 4.33, N, 5.02; Measured value: C, 45.28, H, 4.23, N, 5.09.
IR(KBr,cm
-1):2955,2919ν(C-H),1603,1580ν(C=N),1494ν(C-NO
2),1158ν(C-O),1075ν(C-Cl),520ν(Sn-O),484ν(Sn-N),423ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.73(d,J=2.4Hz,1H,H-3),7.71(d,J=2.4Hz,1H,H-5),9.27(s,1H,H-7),8.65(d,J=2.4Hz,1H,H-9),8.07(dd,J
1=9.2Hz,J
2=2.4Hz,1H,H-11),6.81(d,J=9.2Hz,1H,H-12),1.35-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.04(C-7),13.17(C-θ),25.43(C-α),26.34(C-γ),26.49(C-β),113.34,117.69,117.80,119.40,125.59,125.78,131.93,133.77,134.41,136.14,161.96,166.48(Ar-C)。Crystallographic data: triclinic(crystalline)system, spacer P1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3, D
c=1.609Mgm
-3, μ (MoK
α)=1.371mm
-1, F (000)=560,1.86 ° of < θ < 27.6 °, crystalline size: 0.25 × 0.23 × 0.21mm, R=0.0339, wR=0.0948.
Embodiment 12:
The preparation of dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3):
3 are added successively in order in round-bottomed flask, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.491g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain reddish-orange crystals, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3).Productive rate: 78%, fusing point: 129 ~ 131 DEG C.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-3) ultimate analysis (C
21h
24cl
2n
2o
4sn): theoretical value: C, 45.20, H, 4.33, N, 5.02; Measured value: C, 45.28, H, 4.23, N, 5.09.
IR(KBr,cm
-1):2955,2919ν(C-H),1603,1580ν(C=N),1494ν(C-NO
2),1158ν(C-O),1075ν(C-Cl),520ν(Sn-O),484ν(Sn-N),423ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):7.73(d,J=2.4Hz,1H,H-3),7.71(d,J=2.4Hz,1H,H-5),9.27(s,1H,H-7),8.65(d,J=2.4Hz,1H,H-9),8.07(dd,J
1=9.2Hz,J
2=2.4Hz,1H,H-11),6.81(d,J=9.2Hz,1H,H-12),1.35-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.04(C-7),13.17(C-θ),25.43(C-α),26.34(C-γ),26.49(C-β),113.34,117.69,117.80,119.40,125.59,125.78,131.93,133.77,134.41,136.14,161.96,166.48(Ar-C)。
Crystallographic data: triclinic(crystalline)system, spacer P1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3, D
c=1.609Mgm
-3, μ (MoK
α)=1.371mm
-1, F (000)=560,1.86 ° of < θ < 27.6 °, crystalline size: 0.25 × 0.23 × 0.21mm, R=0.0339, wR=0.0948.
Embodiment 13:
The preparation of dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4): add 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.169g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol in round-bottomed flask in order successively, stirring heating backflow 8h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain orange crystals, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4).Productive rate: 79%, fusing point: 120 ~ 123 DEG C.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4) ultimate analysis (C
21h
25brN
2o
4sn): theoretical value: C, 44.40, H, 4.44, N, 4.93; Measured value: C, 44.45, H, 4.49, N, 4.83.
IR(KBr,cm
-1):3055,2955ν(C-H),1605,1518ν(C=N),1173ν(C-O),517ν(Sn-O),473ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.65(d,J=8.8Hz,1H,H-2),7.49(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.84(d,J=1.8Hz,1H,H-5),9.26(s,1H,H-7),8.64(d,J=1.8Hz,1H,H-9),8.05(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.78(d,J=8.8Hz,1H,H-12),1.36-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.51(C-7),13.17(C-θ),25.13(C-α),25.50(C-γ),26.53(C-β),105.92,113.08,117.51,119.66,123.97,125.39,131.89,135.98,137.74,138.82,166.46,168.01(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3, D
c=1.629Mgm
-3, μ (MoK
α)=2.855mm
-1, F (000)=1128,2.45 ° of < θ < 27.46 °, crystalline size: 0.23 × 0.21 × 0.18mm, R=0.0371, wR=0.0935.
Embodiment 14:
The preparation of dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4):
5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.674g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0043g (0.08mmol) and 95mL anhydrous methanol is added in order successively, stirring heating backflow 11h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain orange crystals, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4).Productive rate: 74%, fusing point: 120 ~ 123 DEG C.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4) ultimate analysis (C
21h
25brN
2o
4sn): theoretical value: C, 44.40, H, 4.44, N, 4.93; Measured value: C, 44.45, H, 4.49, N, 4.83.
IR(KBr,cm
-1):3055,2955ν(C-H),1605,1518ν(C=N),1173ν(C-O),517ν(Sn-O),473ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.65(d,J=8.8Hz,1H,H-2),7.49(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.84(d,J=1.8Hz,1H,H-5),9.26(s,1H,H-7),8.64(d,J=1.8Hz,1H,H-9),8.05(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.78(d,J=8.8Hz,1H,H-12),1.36-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.51(C-7),13.17(C-θ),25.13(C-α),25.50(C-γ),26.53(C-β),105.92,113.08,117.51,119.66,123.97,125.39,131.89,135.98,137.74,138.82,166.46,168.01(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3, D
c=1.629Mgm
-3, μ (MoK
α)=2.855mm
-1, F (000)=1128,2.45 ° of < θ < 27.46 °, crystalline size: 0.23 × 0.21 × 0.18mm, R=0.0371, wR=0.0935.
Embodiment 15:
The preparation of dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4):
5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.337g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol is added in order successively, stirring heating backflow 10h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain orange crystals, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4).Productive rate: 73%, fusing point: 120 ~ 123 DEG C.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4) ultimate analysis (C
21h
25brN
2o
4sn): theoretical value: C, 44.40, H, 4.44, N, 4.93; Measured value: C, 44.45; H, 4.49, N, 4.83.
IR(KBr,cm
-1):3055,2955ν(C-H),1605,1518ν(C=N),1173ν(C-O),517ν(Sn-O),473ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.65(d,J=8.8Hz,1H,H-2),7.49(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.84(d,J=1.8Hz,1H,H-5),9.26(s,1H,H-7),8.64(d,J=1.8Hz,1H,H-9),8.05(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.78(d,J=8.8Hz,1H,H-12),1.36-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.51(C-7),13.17(C-θ),25.13(C-α),25.50(C-γ),26.53(C-β),105.92,113.08,117.51,119.66,123.97,125.39,131.89,135.98,137.74,138.82,166.46,168.01(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3, D
c=1.629Mgm
-3, μ (MoK
α)=2.855mm
-1, F (000)=1128,2.45 ° of < θ < 27.46 °, crystalline size: 0.23 × 0.21 × 0.18mm, R=0.0371, wR=0.0935.
Embodiment 16:
The preparation of dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4):
5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff 0.506g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol is added in order successively, stirring heating backflow 12h in round-bottomed flask; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain orange crystals, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4).Productive rate: 78%, fusing point: 120 ~ 123 DEG C.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff base complex (I-4) ultimate analysis (C
21h
25brN
2o
4sn): theoretical value: C, 44.40, H, 4.44, N, 4.93; Measured value: C, 44.45; H, 4.49, N, 4.83.
IR(KBr,cm
-1):3055,2955ν(C-H),1605,1518ν(C=N),1173ν(C-O),517ν(Sn-O),473ν(Sn-N),419ν(Sn-C)。
1HNMR(DMSO-d
6,400MHz),δ(ppm):6.65(d,J=8.8Hz,1H,H-2),7.49(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-3),7.84(d,J=1.8Hz,1H,H-5),9.26(s,1H,H-7),8.64(d,J=1.8Hz,1H,H-9),8.05(dd,J
1=8.8Hz,J
2=1.8Hz,1H,H-11),6.78(d,J=8.8Hz,1H,H-12),1.36-1.43(m,8H,H-α,H-β),1.19(sext,J=6.8Hz,4H,H-γ),0.73(t,J=7.2Hz,6H,H-θ)。
13CNMR(DMSO-d
6,100MHz),δ(ppm):164.51(C-7),13.17(C-θ),25.13(C-α),25.50(C-γ),26.53(C-β),105.92,113.08,117.51,119.66,123.97,125.39,131.89,135.98,137.74,138.82,166.46,168.01(Ar-C)。
Crystallographic data: oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3, D
c=1.629Mgm
-3, μ (MoK
α)=2.855mm
-1, F (000)=1128,2.45 ° of < θ < 27.46 °, crystalline size: 0.23 × 0.21 × 0.18mm, R=0.0371, wR=0.0935.
Test example: dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-1) of the present invention or title complex (I-2) or title complex (I-3) or title complex (I-4), its Anticancer Activity in vitro is measured and realized by MTT experiment method.
MTT analytical method:
Based on living cells metabolize thing reductive agent 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 dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) to the inhibit activities of human cervical carcinoma cell (Hela), human breast cancer cell (MCF7), human liver cancer cell (HepG2), human colon cancer cell (Colo205), human lung carcinoma cell (NCI-H460).
Cell strain and culture system:
Hela, MCF7, HepG2, Colo205 and NCI-H460 cell strain takes from American. tissue incubator (ATCC).With RPMI1640 (GIBICO company) substratum containing 10% foetal calf serum, at 5% (volume fraction) CO
2, carry out vitro culture in 37 ° of C saturated humidity incubators.
Test process: join in each hole respectively by testing the concentration gradient of liquid (0.1nM-10uM) according to concentration, each concentration establishes 6 parallel holes.Experiment is divided into drug test 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 nutrient solution, 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 (being made into 4mg/mL with D-Hanks damping fluid).After placing 4h at 37 DEG C, remove supernatant liquor.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 cervical carcinoma cell (Hela) cell strain, human breast cancer cell (MCF7) cell strain, human liver cancer cell (HepG2) cell strain, human colon cancer cell (Colo205) cell strain, 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, with dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-1) of the present invention or title complex (I-2) or title complex (I-3) or title complex (I-4) as cancer therapy drug, higher to human cervical carcinoma, human breast carcinoma, people's liver cancer, human colon carcinoma, people's lung cancer activity, can be used as the candidate compound of cancer therapy drug.
Table 1 dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) cancer therapy drug external activity test data
Human cervical carcinoma | Human breast carcinoma | People's liver cancer | Human colon carcinoma | People's lung cancer | |
Cell strain | Hela | MCF7 | HepG2 | Colo205 | NCI-H460 |
Title complex (I-1) IC 50(uM/mL) | 1.646 | 7.368 | 1.502 | 0.3602 | 2.432 |
Title complex (I-2) IC 50(uM/mL) | 2.778 | 6.197 | 0.8222 | 0.696 | 4.349 |
Title complex (I-3) IC 50(uM/mL) | 2.623 | 8.117 | 2.111 | 0.8225 | 4.738 |
Title complex (I-4) IC 50(uM/mL) | 3.128 | 5.694 | 18.75 | 0.5975 | 5.645 |
Carboplatin IC 50(uM/mL) | 22.56 | 34.76 | 25.93 | 3.883 | 21.87 |
Method | MTT | MTT | MTT | MTT | MTT |
Claims (4)
1. dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex, is characterized in that, the title complex for following structural formula (I):
Wherein: Bu represents normal-butyl,
Work as R
1for-OCH
3, R
2for-H, R
3during for-H, form title complex (I-1); Described title complex (I-1) is oblique system, spacer P2
1/ n, a=1.24970 (4) nm, b=1.79750 (6) nm, c=1.93207 (6) nm, α=γ=90 °, β=98.994 (2) °, Z=8, V=4.2867 (2) nm
3; There is the independent molecule of two similar in crystal, the center tin of each molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration;
Work as R
1for-OCH
3, R
2for-H, R
3for-NO
2time, form title complex (I-2); Described title complex (I-2) is oblique system, spacer P2
1/ n, a=1.41051 (5) nm, b=1.80144 (7) nm, c=1.91174 (8) nm, α=γ=90 °, β=104.219 (2) °, Z=8, V=4.7088 (3) nm
3; There is the independent molecule of two similar in crystal, the center tin of each molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration;
Work as R
1for-Cl, R
2for-Cl, R
3for-NO
2time, form title complex (I-3); Described title complex (I-3) is triclinic(crystalline)system, spacer P 1, a=0.99404 (2) nm, b=1.05990 (2) nm, c=1.12964 (2) nm, α=98.4720 (10) °, β=99.9630 (10) °, γ=95.1310 (10) °, Z=2, V=1.15133 (4) nm
3; The center tin of molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration;
Work as R
1for-H, R
2for-Br, R
3for-NO
2time, form title complex (I-4); Described title complex (I-4) is oblique system, spacer P2
1/ c, a=1.71353 (9) nm, b=0.95197 (5) nm, c=1.43022 (7) nm, α=γ=90 °, β=96.7560 (10) °, Z=4, V=2.3168 (2) nm
3; The center tin of molecule and ligating atom form pentacoordinate and to distort trigonal bipyramid configuration.
2. the preparation method of dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex according to claim 1, it is characterized in that adding aromatic aldehyde contracting arylamine Schiff base, Dibutyltin oxide or dibutyl tin dichloride, sodium methylate and solvent anhydrous methanol in order successively in reaction vessel, under stirring and refluxing, react 8 ~ 12h; Cooling, filters; Under 25 ~ 45 DEG C of conditions, control solvent evaporates crystallization, obtain crystal, be dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex;
Wherein aromatic aldehyde contracting arylamine Schiff base, dibutyl tin dichloride or Dibutyltin oxide are reactant, sodium methylate is catalyzer, anhydrous methanol is reaction solvent, the mass ratio of reactant aromatic aldehyde contracting arylamine Schiff base and Dibutyltin oxide or dibutyl tin dichloride is 1:1 ~ 1:1.05, the mass ratio of catalyst sodium methoxide and reactant aromatic aldehyde contracting arylamine Schiff base is 0.004:1 ~ 2.05:1, and the consumption of solvent anhydrous methanol is that every mmole Dibutyltin oxide or dibutyl tin dichloride add 30 ~ 55 ml methanol.
3. dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex according to claim 1 is preparing the application in Therapeutic cancer medicine.
4. apply as claimed in claim 3, it is characterized in that, described cancer is cervical cancer, mammary cancer, liver cancer, colorectal carcinoma or lung cancer.
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