CN101054394A - Nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative and preparation method and application thereof - Google Patents
Nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative and preparation method and application thereof Download PDFInfo
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- CN101054394A CN101054394A CN 200710039467 CN200710039467A CN101054394A CN 101054394 A CN101054394 A CN 101054394A CN 200710039467 CN200710039467 CN 200710039467 CN 200710039467 A CN200710039467 A CN 200710039467A CN 101054394 A CN101054394 A CN 101054394A
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- tetrabutylamine
- aromatic imine
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Abstract
The present invention discloses a nitro aryl imine hexamolybdic acid tetrabutyl ammonium derivative for suppressing leucocythemia K562 cell line proliferation activity. The nitro may be o-nitro, m- nitro, p-nitro, and R denotes the methyl, methoxy, ethyl etc.
Description
Technical field
The present invention relates to nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative and preparation method thereof and its application on inhibition leukemia K 562 cell line proliferation activity.
Background technology
The polyacid nano-cluster is a kind of pure substance nanoparticle, can assemble and chemically modified it easily, thereby regulate and control its structure and properties effectively.
According to the literature, six molybdate nano-clusters have anti-tumor activity.In order to seek the novel medicine with anti-tumor activity, the present invention selects six molybdate nano-clusters as research object, and design synthesizes a series of nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivatives.Wish to seek a kind of nano level lead compound of novel hybrid with anti-tumor activity.
Summary of the invention
The objective of the invention is for a kind of active nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative of the leukemia K 562 cell line proliferation of inhibition that has is provided.
Another object of the present invention is for the preparation method of this derivative is provided.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of have suppress the active nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative of leukemia K 562 cell line proliferation, with general formula (I) expression:
In the formula:
R＝H，2-CH
3，3-CH
3，2-OCH
3，2-C
2H
5，2，6-CH
3(2)
The position of nitro can be ortho position, a position or contraposition.
Mtt assay (four tell the salt colorimetry) by zooblast-Molecular Biology Lab's standard is measured, and a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative has the leukemia K 562 of inhibition cell line proliferation activity; Can determine the structure of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative by the X-single crystal diffraction.
A nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative of the present invention includes:
The 2-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
The 3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
The 4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methyl-3-nitro aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methyl-5-nitro aromatic imine generation six aluminic acid TBuAs
3-methyl-2-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
3-methyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
3-methyl-5-nitro aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methoxyl group-3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methoxyl group-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-methoxyl group-5-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-ethyl-3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-ethyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2-ethyl-5-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2,6-dimethyl-3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
2,6-dimethyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine
Nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative with general formula (I) expression can prepare with the following method:
Is raw material with eight molybdic acids and general formula for the substituted aniline hydrochloride of (II), in the presence of dewatering agent dicyclohexyl carbodiimide (DCC), refluxes in acetonitrile solution 7～9 hours, obtains the compound that general formula (I) is represented.
R＝H，2-CH
3，3-CH
3，2-OCH
3，2-C
2H
5，2，6-CH
3(2)
The used dewatering agent of this step is dicyclohexyl carbodiimide (DCC).
Used formula (II) compound and the mol ratio of eight molybdic acids and DCC are 1: 1: 2～1: 2: 3 in this step, and preferred proportion is 1: 1.5: 2.5.
The preparation method of substituted aniline hydrochloride is that substituted aniline and ethanol mix, heating for dissolving, add again concentrated hydrochloric acid to the pH value of solution to acidity, cooling has a large amount of precipitations to separate out, i.e. the compound of general formula (II) expression.
Reaction is what to carry out under the reflux temperature of acetonitrile solvent in this step, and the reaction times is 7～9 hours, and the preferred time is 8 hours.Desolventizing after reaction is finished filters, washing, recrystallization.
Target compound of the present invention (I) adopts the X-single crystal diffraction to determine its structure.
Description of drawings
Fig. 1 is the single crystal structure figure of embodiment of the invention l;
Fig. 2 is the single crystal structure figure of the embodiment of the invention 2;
Fig. 3 is the single crystal structure figure of the embodiment of the invention 3;
Embodiment
Further specify technical characterstic of the present invention below in conjunction with embodiment:
Embodiments of the invention are selected for use following derivative to carry out emphasis as representative and are set forth:
2-methyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine (Ia)
2-methyl-5-nitro aromatic imine generation six aluminic acid TBuAs (Ib)
3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine (Ic)
Embodiment 1: preparation 2-methyl-4-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine (Ia)
With (Bu
4N)
4[α-Mo
8O
26] (1.0mmol), DCC (2.5mmol) and 2-methyl-4-N-methyl-p-nitroaniline hydrochloride (1.5mmol) is mixed in anhydrous acetonitrile (15ml), refluxes and stirs 8 hours, has a large amount of white precipitates to generate and dark red solution.Stopped reaction is cooled to room temperature, removes by filter white precipitate, places dark red filtrate, treats that acetonitrile slowly volatilizees to finish, and obtains the red solid of colloidal.Obtain afterwards orange crystal twice with acetone and alcoholic acid mixing solutions (30ml, 1: 1.5) recrystallization.Productive rate: 60%
Ultimate analysis: measured value (%) C, 31.24; H, 5.21; N, 3.74.
Calculated value (%) C, 31.26; H, 5.25; N, 3.74.
IR (the KBr compressing tablet, cm-1): 2962,2868,1597,1573,1516,1483,1381,1319,1147,976,957,882,790.
1H NMR(δ，ppm，CD
3CN)：0.98(t，24H，-CH
3，[Bu
4N]
+)，1.38(m，16H，-CH
2-，[Bu
4N]
+)，1.65(m，16H，-CH
2-，[Bu
4N]
+)，3.14(m，16H，-CH
2-，[Bu
4N]
+)，2.68(s，3H，Ar-CH
3)，7.30-8.15(m，3H，ArH).
Single crystal structure figure as shown in Figure 1.
The single crystal structure data:
Empirical formula C39 H78 Mo6 N4 O20
Formula weight 1498.69
Temperature 297(2)K
Wavelength 0.71073
Crystal system Monoclinic
Space group P2
1/c
Unit cell dimensions a＝16.6532(9)
b＝16.7588(9)
c＝20.2461(11)
α＝90°
β＝91.0320(10)°
γ＝90°
Volume5649.5(5)
3
Density(calculated)1.762Mg/m
3
Absorption coefficient 1.361mm
-1
F(000)3008
Crystal size 0.20×0.20×0.10mm
3
Theta range for data collection 1.58 to 26.00°.
Index ranges -20＜＝h＜＝20，-20＜＝k＜＝20，-24＜＝l＜＝24
Reflections collected 57534
Independent reflections 11097[R(int)＝0.0287]
Completeness to theta＝26.00 99.9％
Absorption correction None
Max.and min.transmission 0.8759 and 0.7725
Refinement method Full-matrix least-squares on F
2
Data/restraints/parameters 11097/67/688
Goodness-of-fit on F
2 1.110
Final R indices[I＞2sigma(I)]R1＝0.0671，wR2＝0.2057
R indices(all data)R1＝0.0881，wR2＝0.2251
Largest diff.peak and hole 2.267 and-0.658e.
-3
Embodiment 2: preparation 2-methyl-5-nitro aromatic imine substituted hexamolybdic acid tetrabutylamine (Ib)
With (Bu
4N)
4[α-Mo
8O
26] (1.0mmol), DCC (2.5mmol) and 2-methyl-5-nitro anilinechloride (1.5mmol) are mixed in anhydrous acetonitrile (15ml), reflux and stir 8 hours, have a large amount of white precipitates to generate and dark red solution.Stopped reaction is cooled to room temperature, removes by filter white precipitate, places dark red filtrate, treats that acetonitrile slowly volatilizees to finish, and obtains the red solid of colloidal.Obtain afterwards orange crystal twice with acetone and alcoholic acid mixing solutions (30ml, 1: 1.5) recrystallization.Productive rate: 56%
Ultimate analysis: measured value (%) C, 31.24; H, 5.21; N, 3.74.
Calculated value (%) C, 31.26; H, 5.25; N, 3.74.
IR (the KBr compressing tablet, cm-1): 2958,2872,1491,1466,1373,1334,1225,1140,976,956,882,796.
1H NMR(δ，ppm，CD
3CN)：1.02(t，24H，-CH
3，[Bu
4N]
+)，1.43(m，16H，-CH
2-，[Bu
4N]
+)，1.69(m，16H，-CH
2-，[Bu
4N]
+)，3.18(m，16H，-CH
2-，[Bu
4N]
+)，2.73(s，3H，Ar-CH
3)，7.50-7.93(m，3H，ArH)
Single crystal structure figure as shown in Figure 2.
The single crystal structure data:
Empirical formula C39 H78 Mo6 N4 O20
Formula weight 1498.69
Temperature 297(2)K
Wavelength 0.71073
Crystal system Monoclinic
Space group P2
1/c
Unit cell dimensions a＝12.4519(7)
b＝19.5005(11)
c＝23.6287(14)
α＝90°
β＝92.0620(10)°
γ＝90°
Volume5733.8(6)
3
Density(calculated)1.736Mg/m
3
Absorption coefficient 1.341mm
-1
F(000)3008
Crystal size 0.30×0.30×0.20mm
3
θrange for data collection 1.35-27.00°.
Index ranges -15＜＝h＜＝15，-24＜＝k＜＝24，-30＜＝l＜＝29
Reflections collected 47475
Independent reflections 12490[R(int)＝0.0241]
Completeness to theta＝27.00 99.8％
Absorption correction None
Max.and min.transmission 0.7752 and 0.6891
Refinement method Full-matrix least-squares on F
2
Data/restraints/parameters 12490/44/659
Goodness-of-fit on F
2 1.036
Final R indices[I＞2sigma(I)]R1＝0.0392，wR2＝0.1022
R indices(all data)R1＝0.0548，wR2＝0.1129
Largest diff.peak and hole 0.728 and-0.493e.
-3
Embodiment 3: preparation 3-nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine (Ic)
With (Bu
4N)
4[α-Mo
8O
26] (1.0mmol), DCC (2.5mmol) and 3-N-methyl-p-nitroaniline hydrochloride (1.5mmol) are mixed in anhydrous acetonitrile (15ml), reflux and stir 8 hours, have a large amount of white precipitates to generate and dark red solution.Stopped reaction is cooled to room temperature, removes by filter white precipitate, places dark red filtrate, treats that acetonitrile slowly volatilizees to finish, and obtains the red solid of colloidal.Obtain afterwards orange crystal twice with acetone and alcoholic acid mixing solutions (30ml, 1: 1.5) recrystallization.Productive rate: 58%
Ultimate analysis: measured value (%) C, 30.73; H, 5.12; N, 3.78.
Calculated value (%) C, 31.26; H, 5.25; N, 3.74.
IR (the KBr compressing tablet, cm-1): 2962,2868,1597,1573,1516,1483,1381,1319,1147,976,957,882,790.
1H NMR(δ，ppm，CD
3CN)：1.02(t，24H，-CH
3，[Bu
4N]
+)，1.42(m，16H，-CH
2-，[Bu
4N]
+)，1.69(m，16H，-CH
2-，[Bu
4N]
+)，3.20(m，16H，-CH
2-，[Bu
4N]
+)，7.60-8.06(m，3H，ArH)
Single crystal structure figure is as shown in Figure 3:
The single crystal structure data:
Identification code 061114
Empirical formula C38 H76 Mo6 N4 O20
Formula weight 1484.67
Temperature 297(2)K
Wavelength 0.71073
Crystal system monoclinic
Space group P2
1/c
Unit cell dimensions a＝16.8273(17)
b＝17.3291(17)
c＝19.685(2)
α＝90°.
β＝91.057(2)°.
γ＝90°.
Volume5739.1(10)
3
Density(calculated)1.718Mg/m
3
Absorption coefficient 1.339mm
-1
F(000)2976
Crystal size 0.20×0.10×0.10mm
3
Theta range for data collection 1.21 to 25.00°.
Index ranges -20＜＝h＜＝20，-20＜＝k＜＝20，-23＜＝l＜＝23
Reflections collected 39217
Independent reflections 10101[R(int)＝0.0640]
Completeness to theta＝25.00° 100.0％
Max.and min.transmission 0.8777 and 0.7755
Refinement method Full-matrix least-squares on F
2
Data/restraints/parameters 10101/566/613
Goodness-of-fit on F
2 1.194
Final R indices[I＞2sigma(I)]R1＝0.0790，wR2＝0.1384
R indices(all data)R1＝0.1363，wR2＝0.1565
Largest diff.peak and hole 0.589 and-0.609e.
-3
Suppress leukemia K 562 cell line proliferation determination of activity experiment
Adopt the mtt assay (four tell the salt colorimetry) of Shanghai Normal University's zooblast-Molecular Biology Lab's standard to measure, adopt 5-Fu as the positive control data.
Test materials and content:
Examination material: human leukemia K562 cell
Experimental technique: mtt assay
Experimental temperature: 37 ℃
Experimental period: 2007.03.05-2007.03.12
Part of compounds suppresses leukemia K 562 cell line proliferation active testing data and sees Table 1.
Table 1. part of compounds suppresses leukemia K 562 cell line proliferation active testing data
| Compound | Concentration (μ g/ml) | |||||
| Inhibiting rate (%) | ||||||
| 10 -2 | 10 -1 | 1.0 | 10.0 | 10 2 | 50.0 | |
| 1 | 31.0977 | 38.1929 | 41.1192 | 53.3399 | 50.7831 | 51.9195 |
| 2 | 44.5456 | 43.1031 | 44.8492 | 50.6666 | 54.2730 | 52.2694 |
| 3 | 33.7405 | 25.6792 | 22.7082 | 40.2097 | 60.4445 | 49.2029 |
| 5-Fu | - | - | - | 26.6941 | - | 50.6966 |
By above data as can be seen: a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative has the leukemia K 562 of inhibition cell line proliferation activity.
Claims (9)
1, a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative, represent with general formula (I):
In the formula:
R＝H，2-CH
3，3-CH
3，2-OCH
3，2-C
2H
5，2，6-CH
3(2)
The position of nitro is ortho position, a position or contraposition.
2, the preparation method of the nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative in the claim 1 is as follows:
Is raw material with eight molybdic acids and general formula for the substituted aniline hydrochloride of (II), in the presence of dewatering agent, refluxes in acetonitrile solution 7～9 hours, obtains the compound that general formula (I) is represented:
R＝H，2-CH
3，3-CH
3，2-OCH
3，2-C
2H
5，2，6-CH
3(2)
3, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 2 is characterized in that: described dewatering agent is a dicyclohexyl carbodiimide.
4, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 2 is characterized in that: the mol ratio of compound, eight molybdic acids and three kinds of materials of DCC that formula (II) is represented is 1: 1: 2～1: 2: 3.
5, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 4 is characterized in that: the mol ratio of compound, eight molybdic acids and three kinds of materials of DCC that formula (II) is represented is 1: 1.5: 2.5.
6, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 2, it is characterized in that: the preparation method of described substituted aniline hydrochloride is: substituted aniline and ethanol mix, heating for dissolving, add again concentrated hydrochloric acid to the pH value of solution to acidity, cooling, there are a large amount of precipitations to separate out, i.e. the compound of general formula (II) expression.
7, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 2 is characterized in that: entire reaction is to carry out under the reflux temperature of acetonitrile solvent, and the reaction times is 7～9 hours.
8, the preparation method of a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 7 is characterized in that: entire reaction is to carry out under the reflux temperature of acetonitrile solvent, and the reaction times is 8 hours.
9, a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative according to claim 1 is characterized in that: a nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative has the leukemia K 562 of inhibition cell line proliferation activity.
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|---|---|---|---|
| CNB2007100394677A CN100558736C (en) | 2007-04-13 | 2007-04-13 | One nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative and its production and application |
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|---|---|---|---|
| CNB2007100394677A CN100558736C (en) | 2007-04-13 | 2007-04-13 | One nitryl aromatic imine substituted hexamolybdic acid tetrabutylamine derivative and its production and application |
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| Publication Number | Publication Date |
|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157706B (en) * | 2007-11-13 | 2010-06-09 | 上海师范大学 | Precursor compound with herbicide activity |
| CN104211733A (en) * | 2014-08-12 | 2014-12-17 | 清华大学 | Preparation method and application of phenylaethylenum diazene hexamolybdate tetrabutyl ammonium and derivative thereof |
-
2007
- 2007-04-13 CN CNB2007100394677A patent/CN100558736C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157706B (en) * | 2007-11-13 | 2010-06-09 | 上海师范大学 | Precursor compound with herbicide activity |
| CN104211733A (en) * | 2014-08-12 | 2014-12-17 | 清华大学 | Preparation method and application of phenylaethylenum diazene hexamolybdate tetrabutyl ammonium and derivative thereof |
| CN104211733B (en) * | 2014-08-12 | 2016-08-24 | 清华大学 | Benzene ethylene diazene six molybdic acid TBuA and the preparation method of derivative thereof and application |
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|---|---|
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