CN103396435A - 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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CN103396435A
CN103396435A CN2013103058832A CN201310305883A CN103396435A CN 103396435 A CN103396435 A CN 103396435A CN 2013103058832 A CN2013103058832 A CN 2013103058832A CN 201310305883 A CN201310305883 A CN 201310305883A CN 103396435 A CN103396435 A CN 103396435A
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title complex
dibutyl tin
schiff alkali
aromatic aldehyde
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CN103396435B (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, R1 is -OCH3, -Cl or -H, R2 is -H, -Cl or -Br, and R3 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 alkali title complex and preparation method and application
Technical field
The present invention relates to serial dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex, and preparation method thereof, and should the application of series title complex in preparing antitumor drug.
Background technology
Schiff alkali is the compound that a class has pharmacology and physiologically active, because it is take nitrogen-atoms and Sauerstoffatom as ligating atom, comparatively approaching with coenocorrelation, it is the focus that people study always, 3 of series, 5-diiodo-salicylic aldehyde Schiff alkali and the application in preparing antiseptic-germicide thereof are disclosed as Chinese patent CN101302172.
Organotin is the organometallics that a class contains the Sn-C key, has the compound than high biological activity, in sterilization, cancer therapy drug preparation, has wide practical use.Already studied and showed, radicals R and playing an important role with the structure of the part of the tin atom coordination antitumour activity to compound in organotin, as, the antitumour activity of cyclohexyl, normal-butyl and phenyltin compound is stronger, and ethyl takes second place, and methyl is almost without anticancer activity.Before experiment showed, biological activity ratio's coordination of Schiff bases part after forming title complex, obviously strengthen, its title complex has biological and pharmacoligical activities widely.Therefore, Schiff bases part is combined with organotin, becomes a research direction of people's interest.
A kind of dibutyl tin dichloride Schiff alkali coordination compound and the application in preparation treatment cancer of the stomach, nasopharyngeal carcinoma, people's liver cancer or leukemic medicine thereof are disclosed as Chinese patent CN101475583.
Chinese patent CN102718794A discloses a kind of pair of acylhydrazone class Schiff alkali tin diphenyl (IV) title complex and the application in preparation treatment adenocarcinoma of lung, colorectal carcinoma, leukemia cell's medicine thereof.
Chinese patent CN101434616 discloses a kind of organotin Schiff alkali 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 and application in preparing Hepatoma therapy, adenocarcinoma of lung, mammary cancer, prostate cancer, colorectal carcinoma or the leukemic medicine of children's grain morning thereof of acylhydrazone class Schiff aar ligand.
based on the dibutyl tin compounds, be to the experiment proved that the material with antitumour activity, the present invention selects dibutyl tin dichloride or Dibutyltin oxide compound, respectively with o-vanillin, 3, the 5-dichloro-salicylaldehyde, aromatic aldehyde and the o-aminophenols such as 5-bromosalicylaldehyde, the Schiff alkali of the arylamine condensations such as 4-nitro o-aminophenol is part, reaction under certain condition, synthetic having obtained human cervical carcinoma cell (Hela), human breast cancer cell (MCF7), human liver cancer cell (HepG2), human colon cancer cell (Colo205), the stronger title complex of inhibition activity of human lung carcinoma cell (NCI-H460), for the exploitation cancer therapy drug provides new way.
Summary of the invention
One of purpose of the present invention is to provide serial dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex.
Two of the object of the invention is to provide the preparation method of above-mentioned serial dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex.
Three of the object of the invention is to provide the application of above-mentioned serial dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex in medicine.
In order to realize the foregoing invention purpose, the technical solution adopted in the present invention is:
Dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex is the title complex of following structural formula (I):
Figure BDA00003541261700021
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, work as R 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 3In crystal, have the independent molecule of two similar, the center tin of each molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
In a preferred embodiment of the invention, work as R 1For-OCH 3, R 2For-H, R 3For-NO 2The time, 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 3In crystal, have the independent molecule of two similar, the center tin of each molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
In a preferred embodiment of the invention, work as R 1For-Cl, R 2For-Cl, R 3For-NO 2The time, 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 3The center tin of molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
In a preferred embodiment of the invention, work as R 1For-H, R 2For-Br, R 3For-NO 2The time, 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 3The center tin of molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
The preparation method of above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex, it is in reaction vessel, to add successively in order aromatic aldehyde contracting arylamine Schiff alkali, Dibutyltin oxide or dibutyl tin dichloride, sodium methylate and solvent anhydrous methanol, under stirring and refluxing, reacts 8～12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain crystal, be dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex.
Wherein aromatic aldehyde contracting arylamine Schiff alkali, 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 alkali and Dibutyltin oxide or dibutyl tin dichloride is 1:1～1:1.05, the mass ratio of catalyzer sodium methylate and reactant aromatic aldehyde contracting arylamine Schiff alkali 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.
The applicant has carried out anti tumor activity in vitro to above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex and has confirmed research, confirm that this dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex has anti-tumor biological, the purposes that is to say above-mentioned dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex is the application in preparing antitumor drug, is exactly specifically the application in preparing 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 alkali title complex of the present invention has antitumour activity preferably, can it for raw material, prepare anti-cervical cancer, anti-breast cancer, anti-liver cancer, inhibitor against colon carcinoma cells, anti-lung-cancer medicament.With the platinum-containing anticancer drug that generally uses at present, compare, dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex of the present invention has the characteristics such as antitumour activity is high, cost is low, the preparation method is simple, for the exploitation cancer therapy drug provides new way.
The accompanying drawing explanation
Fig. 1 is dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex (I-1) crystal molecule structure iron
Fig. 2 is dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex (I-2) crystal molecule structure iron
Fig. 3 is dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex (I-3) crystal molecule structure iron
Fig. 4 is dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex (I-4) crystal molecule structure iron
Embodiment
By following examples, further describe the present invention, but should notice that scope of the present invention is not subjected to any restriction of these embodiment.
Embodiment 1:
The preparation of dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively in order o-vanillin contracting o-aminophenol Schiff alkali 0.122g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the sorrel crystal, be dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title complex (I-1).Productive rate: 72%, fusing point: 138～140 ℃.
Ultimate analysis (the C of dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title 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 °<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 contracting o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively in order o-vanillin contracting o-aminophenol Schiff alkali 0.487g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the sorrel crystal, be dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title complex (I-1).Productive rate: 75%, fusing point: 138～140 ℃.
Dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title 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 °<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 contracting o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively in order o-vanillin contracting o-aminophenol Schiff alkali 0.243g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the sorrel crystal, be dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title complex (I-1).Productive rate: 74%, fusing point: 138～140 ℃.
Dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title 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 °<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 contracting o-aminophenol Schiff alkali title complex (I-1):
In round-bottomed flask, add successively in order o-vanillin contracting o-aminophenol Schiff alkali 0.365g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the sorrel crystal, be dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title complex (I-1).Productive rate: 79%, fusing point: 138～140 ℃.
Dibutyl tin o-vanillin contracting o-aminophenol Schiff alkali title 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 °<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 contracting 4-nitro o-aminophenol Schiff alkali title complex (2):
In round-bottomed flask, add successively in order o-vanillin contracting 4-nitro o-aminophenol Schiff alkali 0.144g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 71%, fusing point: 172～173 ℃.
Dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 contracting 4-nitro o-aminophenol Schiff alkali title complex (2):
In round-bottomed flask, add successively in order o-vanillin contracting 4-nitro o-aminophenol Schiff alkali 0.577g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0054g (0.1mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title complex of the present invention (2).Productive rate: 74%, fusing point: 172～173 ℃.
Dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order o-vanillin contracting 4-nitro o-aminophenol Schiff alkali 0.288g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 71%, fusing point: 172～173 ℃.
Dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2):
In round-bottomed flask, add successively in order o-vanillin contracting 4-nitro o-aminophenol Schiff alkali 0.432g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title complex (I-2).Productive rate: 72%, fusing point: 172～173 ℃.
Dibutyl tin o-vanillin contracting 4-nitro o-aminophenol Schiff alkali title 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 °<θ<25 °, crystalline size: 0.17 * 0.15 * 0.12mm, R=0.0404, wR=0.1071.
Embodiment 9:
Dibutyl tin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 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, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3).Productive rate: 78%, fusing point: 129～131 ℃.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<θ<27.6 °, crystalline size: 0.25 * 0.23 * 0.21mm, R=0.0339, wR=0.0948.
Embodiment 10:
Dibutyl tin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 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, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3).Productive rate: 74%, fusing point: 129～131 ℃.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<θ<27.6 °, crystalline size: 0.25 * 0.23 * 0.21mm, R=0.0339, wR=0.0948.
Embodiment 11:
Dibutyl tin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 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, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3).Productive rate: 73%, fusing point: 129～131 ℃.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<θ<27.6 °, crystalline size: 0.25 * 0.23 * 0.21mm, R=0.0339, wR=0.0948.
Embodiment 12:
Dibutyl tin 3, the preparation of 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3):
In round-bottomed flask, add successively 3 in order, 5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 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, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain orange red crystal, be dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-3).Productive rate: 78%, fusing point: 129～131 ℃.
Dibutyl tin 3,5-dichloro-salicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 alkali title complex (I-4): add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.169g (0.5mmol), Dibutyltin oxide 0.125g (0.5mmol), sodium methylate 0.0001g (0.002mmol) and 15mL anhydrous methanol in round-bottomed flask, stirring heating backflow 8h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 79%, fusing point: 120～123 ℃.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 alkali title complex (I-4):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.674g (2.0mmol), Dibutyltin oxide 0.518g (2.08mmol), sodium methylate 0.0043g (0.08mmol) and 95mL anhydrous methanol, stirring heating backflow 11h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 74%, fusing point: 120～123 ℃.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 alkali title complex (I-4):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.337g (1.0mmol), dibutyl tin dichloride 0.310g (1.02mmol), sodium methylate 0.111g (2.05mmol) and 56mL anhydrous methanol, stirring heating backflow 10h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 73%, fusing point: 120～123 ℃.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 alkali title complex (I-4):
In round-bottomed flask, add successively in order 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali 0.506g (1.5mmol), dibutyl tin dichloride 0.479g (1.575mmol), sodium methylate 0.164g (3.03mmol) and 63mL anhydrous methanol, stirring heating backflow 12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain the orange crystal, be dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title complex (I-4).Productive rate: 78%, fusing point: 120～123 ℃.
Dibutyl tin 5-bromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff alkali title 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 °<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 alkali title complex of the present invention (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4), its Anticancer Activity in vitro is measured and is realized by the MTT experimental technique.
The MTT analytical method:
With viable cell metabolite reductive agent 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide be the basis.Succinodehydrogenase in the 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, the optical density(OD) with microplate reader mensuration characteristic wavelength, can reflect viable cell quantity indirectly.
Adopt mtt assay to measure dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex (I-1) or title complex (I-2) or title complex (I-3) or title complex (I-4) the inhibition activity to 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 are taken from U.S.'s tissue culture storehouse (ATCC).With the RPMI1640 that contains 10% foetal calf serum (GIBICO company) substratum, at 5% (volume fraction) CO 2, carry out vitro culture in 37 ° of C saturated humidity incubators.
Test process: will test liquid (0.1nM-10uM) and join respectively in each hole according to the concentration gradient of concentration, each concentration is established 6 parallel holes.Experiment is divided into drug test group (the test medicine that adds respectively different concns), control group (only add nutrient solution and cell, do not add the test medicine) and blank group (only add nutrient solution, do not add cell and test medicine).Orifice plate after dosing is placed in to 37 ℃, 5%CO 2In incubator, cultivate 72h.The activity of control drug is measured according to the method for specimen.In having cultivated the orifice plate after 72h, every hole adds MTT40uL (being made into 4mg/mL with the D-Hanks damping fluid).After 37 ℃ of placement 4h, remove supernatant liquor.Every hole adds 150uLDMSO, and vibration 5min, make the Formazan dissolving crystallized.Finally, utilize automatic microplate reader at 570nm wavelength place, to detect the optical density(OD) in each hole.
Data processing: data processing is used GraphPadPrismversion5.0 program, title complex IC 50By the nonlinear regression model (NLRM) that has S shape dose response in program, carrying out match obtains.
With the 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, measured its IC 50Value, result is as shown in table 1, conclusion is: as can be known by data in table, with dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex of the present invention (I-1) 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 alkali title 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
? The 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 (16)

1. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex, is characterized in that, is the title complex of following structural formula (I):
Figure FDA00003541261600011
Wherein: Bu represents normal-butyl,
R 1For-OCH 3,-Cl or-H, R 2For-H ,-Cl or-Br, R 3For-H or-NO 2.
2. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R 1For-OCH 3, R 2For-H, R 3During for-H, form title complex (I-1).
3. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 2, is characterized in that, described title complex (I-1) is crystalline structure.
4. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 3, is characterized in that, 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 3In crystal, have the independent molecule of two similar, the center tin of each molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
5. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R 1For-OCH 3, R 2For-H, R 3For-NO 2The time, form title complex (I-2).
6. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 5, is characterized in that, described title complex (I-2) is crystalline structure.
7. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 6, is characterized in that, 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 3In crystal, have the independent molecule of two similar, the center tin of each molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
8. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R 1For-Cl, R 2For-Cl, R 3For-NO 2The time, form title complex (I-3).
9. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 8, is characterized in that, described title complex (I-3) is crystalline structure.
10. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 9, is characterized in that, described title complex (I-3) is triclinic(crystalline)system, spacer
Figure FDA00003541261600021
, 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 3The center tin of molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
11. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 1, is characterized in that, works as R 1For-H, R 2For-Br, R 3For-NO 2The time, form title complex (I-4).
12. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 11 is characterized in that described title complex (I-4) is crystalline structure.
13. dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex as claimed in claim 12 is characterized in that 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 3The center tin of molecule and ligating atom form pentacoordinate distortion trigonal bipyramid configuration.
14. the preparation method of the described dibutyl tin aromatic aldehyde of claim 1 to 13 any one claim contracting arylamine Schiff alkali title complex, it is characterized in that adding successively in order aromatic aldehyde contracting arylamine Schiff alkali, Dibutyltin oxide or dibutyl tin dichloride, sodium methylate and solvent anhydrous methanol in reaction vessel, under stirring and refluxing, react 8～12h; Cooling, filter; Under 25～45 ℃ of conditions, control the solvent evaporates crystallization, obtain crystal, be dibutyl tin aromatic aldehyde contracting arylamine Schiff alkali title complex;
Wherein aromatic aldehyde contracting arylamine Schiff alkali, 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 alkali and Dibutyltin oxide or dibutyl tin dichloride is 1:1～1:1.05, the mass ratio of catalyzer sodium methylate and reactant aromatic aldehyde contracting arylamine Schiff alkali 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.
15. the application of the described dibutyl tin aromatic aldehyde of claim 1 to 13 any one claim contracting arylamine Schiff alkali title complex in preparation treatment cancer drug.
16. application as claimed in claim 15, is characterized in that, described cancer is cervical cancer, mammary cancer, liver cancer, colorectal carcinoma or lung cancer.
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CN103819358A (en) * 2014-02-19 2014-05-28 桂林理工大学 2-hydroxy-3-(2-hydroxy-3-methoxyl phenylene methanamine) acetophenone and synthesis method
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CN105777796A (en) * 2016-04-11 2016-07-20 衡阳师范学院 3,5-dibromosalicylaldehyde contraction 4-nitro-o-aminophenol Schiff alkali diphenyl tin complex and preparing method and application thereof
CN105777795A (en) * 2016-04-11 2016-07-20 衡阳师范学院 5-chlorosalicylaldehyde contraction 4-nitro-o-aminophenol Schiff alkali diphenyl tin complex and preparing method and application thereof

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CN103819358A (en) * 2014-02-19 2014-05-28 桂林理工大学 2-hydroxy-3-(2-hydroxy-3-methoxyl phenylene methanamine) acetophenone and synthesis method
CN105198937A (en) * 2015-10-10 2015-12-30 衡阳师范学院 Cobalt complex containing 3,5-dichlorosalicylidene 4-nitro-o-aminophenol Schiff alkali and pyridine as well as preparation method and application of cobalt complex
CN105218593A (en) * 2015-10-10 2016-01-06 衡阳师范学院 One contains cobalt complex of 3,5-Dibromosalicylaldehyde contracting 4-nitro o-aminophenol Schiff and pyridine and its preparation method and application
CN105218593B (en) * 2015-10-10 2017-11-28 衡阳师范学院 A kind of cobalt complex of contracted containing 3,5 Dibromosalicylaldehydes 4 nitro o-aminophenol Schiffs and pyridine and its preparation method and application
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