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 PDF

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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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dibutyl tin
schiff base
aromatic aldehyde
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CN103396435A (en
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蒋伍玖
邝代治
冯泳兰
张复兴
庾江喜
李俊华
王剑秋
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Hengyang Normal University
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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

Dibutyl tin aromatic aldehyde contracting arylamine Schiff base complex and preparation method and application
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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