CN103087107B - Single catechol molybdenum match and preparation method thereof and its application - Google Patents

Single catechol molybdenum match and preparation method thereof and its application Download PDF

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CN103087107B
CN103087107B CN201110344946.6A CN201110344946A CN103087107B CN 103087107 B CN103087107 B CN 103087107B CN 201110344946 A CN201110344946 A CN 201110344946A CN 103087107 B CN103087107 B CN 103087107B
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molybdenum
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鲁晓明
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Capital Normal University
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Abstract

The invention provides a class list catechol molybdenum match, its molecular chemical formula is: { [MoO 3(C 6h 4o 2) (NHRNH 2)] (NH 2rNH 2) n, wherein, R is the straight or branched alkylidene group of 1-6 carbon atom, and it is connected with two amino and forms NH 2rNH 2represent organic amine compound, n be 1 or be greater than 1 integer.The present invention also provides its preparation method, and raw material is easy to get, and cost is low, product is separated out with crystalline form, and purity is large, and productive rate is high, and have good water-soluble and fat-soluble, and confirm that such title complex can be used as anticancer and antitumor drug or chief component by experiment.

Description

Single catechol molybdenum match and preparation method thereof and its application
Technical field
The present invention relates to single catechol molybdenum match and preparation method thereof, also relate to the application of these compounds in the medicine of the generation and growth of preparing prevention and prohibition cancer and tumour.
Background technology
Molybdenum is the micro-bioelement required for organism, and scarce molybdenum can cause cancer and tumor incidence to raise.Document announcement is in the district occurred frequently of the cancers such as esophagus cancer, digestive tract cancer, cancer of the stomach, liver cancer, the rectum cancer, lung cancer, mammary cancer, and in resident's serum, urine sample and hair, the content of molybdenum is starkly lower than Di Fa district.After scarce molybdenum animal and intact animal accept the nitroso compound of doses simultaneously, lack the incidence of the NIH mice knurl of molybdenum animal significantly higher than intact animal.
Within 1991, rise, the research that the anticancer antineoplastic vascular starting four thio ammonium molybdate becomes, at present, use four thio ammonium molybdate to take new vessel as target spot to tumour to treat that to enter the second phase clinical, and reach good anticancer antitumor, extend effect (Quintin, the CelinaG.Kleer in patient's life-span, etal.Cancerresearch2002,62:4854).But four thio ammonium molybdate is very unstable, extremely responsive to light, water and oxygen.Therefore need to be placed in the environment of anhydrous drying, lucifuge, anaerobic, be generally kept in the argon gas of inertia.In 8 weeks, the four thio ammonium molybdate be placed in capsule can only retain the drug effect of 90%.Therefore seek high-efficiency low-toxicity, be better than or be specific to incumbent clinical medicine and to have the new type anticancer antitumor drug of certain stability imperative.
Patent of invention (the 1. Lu Xiaoming that early stage, existing two portions of cancer therapy drugs about molybdenum match were applied, " molybdenum, tungsten and molybdenum tungsten ligand polymer and method for making thereof and its in preparation prevention and the application in treatment cancer and tumour medicine " Chinese invention patent, 200410096494.4; 2. Lu Xiaoming, " the octahedra molybdenum tungsten complex of chirality; their synthetic method and the purposes in cancer therapy drug ", Chinese invention patent, 01110359.0), in flow of research, applicant has found the compound structure uniqueness that more front two parts of patents are reported and has presented the molybdenum match of better anticancer drug effect.
Summary of the invention
Given this, the object of the present invention is to provide a class molybdenum match, namely single catechol molybdenum match and method for making thereof are preparing the application in anticancer, antitumor medicament with it.
For achieving the above object, the present invention adopts following technical scheme:
The invention provides a class list catechol molybdenum match, its molecular chemical formula is:
{[MoO 3(C 6H 4O 2)(NHRNH 2)](NH 2RNH 2)} n
Wherein, R is the straight or branched alkylidene group of 1-6 carbon atom, and it is connected with two amino and forms NH 2rNH 2represent organic amine compound, n be 1 or be greater than 1 integer.
Wherein said organic amine compound is the diamine compounds such as quadrol, 1,2 propylene diamine, 1,3 propylene diamine.
The present invention also provides the preparation method of described single catechol molybdenum match, is in the mixed phase of aqueous phase, organic phase or aqueous phase and organic phase, and the reaction of molybdenum salt, pyrocatechol and organic amine is formed title complex of the present invention.
Concrete, the synthetic method of title complex of the present invention comprises:
1. under normal temperature, pyrocatechol is placed in solvent and is positioned on magnetic stirrer, add organic amine to pH value 10-11;
2.0.5-1.5h after add molybdenum salt continue stir 8-20h;
3. reacted solution is filtered, then the mother liquor of clarification is placed in container, leave standstill after slowly adding the organic solvents such as the ether of arbitrary volume ratio or sherwood oil;
4. crystallize out in container after liang week.
Wherein, aqueous phase is water solvent; Organic phase is organic solvent as the alcohols such as methyl alcohol, ethanol, Virahol, acetonitrile, acetone etc.; Mixed phase is the mixture of aqueous phase and organic phase; Molybdenum salt is the inorganic salt of monokaryon molybdenum or inorganic salt hydrate, the inorganic salt of multinuclear molybdenum or organic salt; Organic amine is the diamine compounds such as quadrol, 1,2-propylene diamine, 1,3-propylene diamine.
Preferably, described molybdenum salt is ammonium molybdate, Sodium orthomolybdate, potassium molybdate, calcium molybdate, molybdic oxide, moly-sulfide, ammonium molybdate, ammonium thiomolybdate, positive tetrabutyl ammonium octamolybdate, the positive tetrabutyl six ammonium molybdate, positive tetrabutyl Ammonium Heptamolybdate, two ammonium molybdate, hexacarbonylmolybdenum or six molybdenum chlorides or their hydrate.
Described solvent is selected from the mixed organic solvents of one or more arbitrary proportions in organic solvent (such as methyl alcohol, ethanol, acetonitrile, acetone), or inorganic solvent (such as water), or the mixed solvent of organic and inorganic arbitrary proportion.Preferably, described solvent is the mixed solvent of ethanol and acetonitrile arbitrary proportion.Preferably, the weight of substrate is 0.2-0.6g: 10-30ml with the ratio of the volume of solvent.
Title complex of the present invention confirms by experiment, and can be used as anticancer and antitumor drug or chief component, therefore the present invention also provides the application in the medicine of the application of described title complex in the medicine of the generation and growth of preparing prevention and prohibition cancer and tumour.
Beneficial effect of the present invention is as follows: front two parts of existing patents of the applicant that compares, and the part of title complex of the present invention is defined as catechol and organic amine, and is only have the monokaryon molybdenum match that a catechol is part.The synthesis of title complex medicine of the present invention, raw material is easy to get, and cost is low, and product is separated out with crystalline form, and purity is large, and productive rate is high; The title complex of the present invention of gained in its natural state can stable existence; The title complex of the present invention of gained has good water-soluble and fat-soluble; The title complex of the present invention of gained has presented excellent restraining effect to A-549 (lung cancer), Bel-7402 (liver cancer), HCT (adenocarcinoma of colon), HL-60 (leukemia), BGC-823 (cancer of the stomach), KB (nasopharyngeal carcinoma).
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of title complex 1 of the present invention.
Fig. 2 A is the molecular structure of title complex 1 of the present invention.
Fig. 2 B, Fig. 2 C and Fig. 2 D are respectively the accumulation graph of title complex 1 of the present invention along a (B), b (C) and c (D) axle.
Fig. 3 is the infrared spectrum of title complex 2 of the present invention.
Fig. 4 A is the molecular structure of title complex 2 of the present invention.
Fig. 4 B and Fig. 4 C is respectively title complex 2 of the present invention along b (B), the accumulation graph of c (C) axle.
Embodiment
Embodiment is intended to set forth the present invention further below, but should it is clear that, the present invention is not limited to the scope described in detail below.
Embodiment 1
0.35g pyrocatechol is put into the 50ml round-bottomed flask filling 15ml dehydrated alcohol, be placed on magnetic stirrer and stir, and slowly to instill 1,3-propylene diamine to pH be 10 ~ 11.Appropriate (NH is slowly added after 1h 4) 2mo 2o 72H 2o (0.2g is dissolved in 20ml acetonitrile) continues to stir 8h to 20h.Filter, clear liquid is placed in long test tube, slowly adds ether to filtrate two times of At The Heights along test tube wall, sealing and standing, after about two weeks, separate out yellow bulk crystals.
Elemental analysis value (%) is (being theoretical value in bracket): C:36.52 (36.48); H:6.26 (6.67); N:13.83 (13.61); Mo:23.48 (23.31).The infrared analysis of title complex 1 shows, in IR (KBr compressing tablet) spectrum, at 4000 ~ 400cm -1measure in scope, as shown in Figure 1.At 873.27cm -1and near 962.94cm-1, there is stronger peak, show the stretching vibration of cis Mo=O; 1099.98cm -1for the stretching vibration absorption peak of Mo-N.Other peak, 804.34cm -1and 740.63cm -1then significantly be classified as the C-H flexural vibration on phenyl ring, show the benzene that there is ortho position replacement in system, 1478.52cm -1and 1580.31cm -1the peak of neighbouring two high strength is attributed to C=C stretching vibration Absorption Characteristics peak on phenyl ring.1274.97cm -1for the stretching vibration absorption peak of C-O on phenyl ring, 1253.05cm -1be C-N vibration absorption peak in 1,3-propylene diamine, and at 3348.73cm -1it is the absorption of vibrations characteristic peak of N-H on 1,3-propylene diamine.
The crystallographic parameter of title complex 1:
Main bond angle and bond distance's data list in table 1, and the crystalline structure of title complex and the structure cell accumulation graph of title complex are shown in Fig. 2 A, 2B, 2C and 2D.
Part bond distance (nm) bond angle (°) of table 1 title complex 1
Show the crystal analysis of title complex, in each structural unit, center Mo atom is octahedral coordination of distortion.Two [MoO are had in complex structure unit 3(C 6h 4o 2) (HNC 3h 6nH 2)] 2-negatively charged ion, two protonated 1,3-propylene diamine and a free ether molecule.With Mo (VI) O of hexa-coordinate described on document 6unlike, center Mo atom with the octahedral structure of distortion only with the coordination of a bidentate ligand pyrocatechol, simultaneously with the nitrogen-atoms coordination of 1, a 3-propylene diamine molecule one end.Wherein the bond distance of molybdenum and nitrogen-atoms is 2.375 (1) nm.The bond distance of molybdenum and end group oxygen is within the scope of 1.722 (8)-1.770 (7) nm, two other Mo-O key Mo (1)-O (1) [2.116 (8) nm], the bond distance of Mo (1)-O (2) [2.118 (8) nm] is slightly long.
Pyrocatechol and 1,3-propylene diamine and central metal coordination are the accurate octahedra geometric configuration of chirality.There is [the MoO of Chiral properties (Λ or Δ) 3(C 6h 4o 2) (HNC 3h 6nH 2)] 2-negatively charged ion and 1,3-propylene diamine molecule passes through O ... HN (2.733nm, 162.7 °), O ... HN (2.720nm, 163.34 °), O ... HN (2.773nm, 171.69 °) hydrogen bond action is arranged in one dimension chirality chain along b direction of principal axis, the different one group of chirality chain of configuration passes through O ... HN (2.806nm, 176.24 °), O ... HN (3.044nm, 163.26 °) hydrogen bond couples together, and intercouples into the meso bilayer chain that thickness is 15.355nm.It is free ether molecule between two adjacent meso bilayer unit.These are combined in lattice as repeating unit composition multiple layers structure.
Embodiment 2
0.35g pyrocatechol is put into the 50ml round-bottomed flask filling 15ml dehydrated alcohol, be placed on magnetic stirrer and stir, and slowly instillation quadrol is 10 ~ 11 to pH.Appropriate (NH is slowly added after 1h 4) 2mo 2o 72H 2o (0.2g is dissolved in 20ml acetonitrile) continues to stir 8h to 20h.Filter, clear liquid is placed in long test tube, slowly adds ether to filtrate two times of At The Heights along test tube wall, sealing and standing, after about two weeks, separate out yellow bulk crystals.
Elemental analysis value (%) is (being theoretical value in bracket): C:31.48 (31.42); H:5.26 (5.27); N:12.26 (12.21); Mo:27.92 (27.87).The infrared analysis of title complex 2 shows, in IR (KBr compressing tablet) spectrum, at 4000 ~ 400cm -1measure in scope, as shown in Figure 3.At 873.48cm -1the peak that neighbouring appearance is stronger, shows the stretching vibration of cis Mo=O; 1100.31cm -1for the stretching vibration absorption peak of Mo-N.Other peak, 804.52cm -1and 749.21cm -1then significantly be classified as the C-H flexural vibration on phenyl ring, show the benzene that there is ortho position replacement in system, 1478.09cm -1and 1620.31cm -1the peak of neighbouring two high strength is attributed to C=C stretching vibration Absorption Characteristics peak on phenyl ring.1274.97cm -1for the stretching vibration absorption peak of C-O on phenyl ring, 1253.40cm -1for C-N vibration absorption peak in quadrol, and at 3430.76cm -1for the absorption of vibrations characteristic peak of N-H on quadrol.The position at these peaks is very identical with the structure parsed.
The crystallographic parameter of title complex 2:
Main bond angle and bond distance's data list in table 2, and crystalline structure and the structure cell accumulation graph of title complex are shown in Fig. 4 A, 4B and 4C.
Part bond distance (nm) bond angle (°) of table 2 title complex 2
Show the crystal analysis of title complex, center Mo atom is octahedral coordination structure equally.[MoO is had in title complex 3(C 6h 4o 2) (NHC 2h 4nH 2)] 2-negatively charged ion and a protonated quadrol molecule.The same with the negatively charged ion of title complex 1, center Mo atom equally with the octahedral structure of distortion not only with two oxygen coordinations on a bidentate ligand pyrocatechol, simultaneously with the nitrogen-atoms coordination of a quadrol molecule one end.Wherein Mo-N key bond distance is 2.446 (1) nm, the bond distance of molybdenum and end group oxygen is within the scope of 1.756 (8)-1.775 (7) nm, two other Mo-O key Mo (1)-O (1) [2.126 (8) nm], the bond distance of Mo (1)-O (2) [2.054 (2) nm] is slightly long.
Pyrocatechol and quadrol and central metal coordination are the accurate octahedra geometric configuration of chirality.There is [the MoO of Chiral properties (Λ or Δ) 3(C 6h 4o 2) (HNC 2h 4nH 2)] 2-negatively charged ion and quadrol molecule pass through O ... HN (2.789nm, 168.8 °), O ... HN (2.740nm, 162.36 °), O ... HN (2.885nm, 174.05 °), O ... HN (2.819nm, 162.76 °) hydrogen bond action is arranged in one dimension chirality chain along C direction of principal axis, the different one group of chirality chain of configuration passes through O ... HN (2.806nm, 176.24 °), O ... HN (3.044nm, 163.26 °) hydrogen bond couples together, and intercouples into meso bilayer chain.These are combined in lattice as repeating unit composition multiple layers structure.
The in-vitro screening of the anticancer drug effect of experimental example 1 title complex of the present invention 1:
The cell experiment of title complex 1
Select the attached tumor cells of logarithmic phase: A-549 (lung cancer), Bel-7402 (liver cancer), HCT (adenocarcinoma of colon), HL-60 (leukemia), BGC-823 (cancer of the stomach), KB (nasopharyngeal carcinoma) are with after trysinization, the cell suspension of 5000/mL is made into the RPM11640 nutrient solution of 10% calf serum, be seeded in 96 well culture plates, 100 μ L are inoculated in every hole, 37 DEG C, 5%CO 2cultivate 24h.
Experimental group: add embodiment 1 gained sample solution 10 μ L (namely use physiological saline solution embodiment 1 gained complex crystal 1, concentration is 5 μ g/mL), every hole final volume is 200 μ L, supplies with RPMI-1640.37 DEG C, 5%CO 2cultivate 3d.
Supernatant liquor is abandoned after cultivating 3d, every hole adds the serum-free medium of the freshly prepared 0.5mg/mLMTT of 100 μ L (tetrazolium bromide), 37 DEG C are continued to cultivate 4h, carefully abandon supernatant, and add 200 μ LDMSO dissolving MTTformazon precipitations, with the mixing of miniature ultrasonic vibrator, microplate reader measures the optical density value at wavelength 544nm place.According to following formulae discovery growth of tumour cell inhibiting rate: growth of tumour cell inhibiting rate (%)=(OD contrast-OD experiment)/(OD contrast-OD blank) × 100%
Result shows, embodiment 1 gained title complex 1 pair of kinds of tumor cells all has good growth-inhibiting effect, is respectively:
Be 75.25%, IC to A-549 (lung cancer) inhibitory rate of cell growth 50=0.55;
Be 68.12%, IC to Bel-7402 (liver cancer) inhibitory rate of cell growth 50=0.43;
Be 63.60%, IC to HCT (adenocarcinoma of colon) inhibitory rate of cell growth 50=0.59;
Be 68.12% to HL-60 (leukemia) inhibitory rate of cell growth;
Be 65.61% to BGC-823 (cancer of the stomach) inhibitory rate of cell growth;
Be 58.80% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth;
Conclusion: this illustrates, title complex 1 of the present invention can for the preparation of the medicine of prevention and therapy cancer.
The in-vitro screening of the anticancer drug effect of experimental example 2 title complex of the present invention 2
The cell experiment of title complex 2
Select the attached tumor cells of logarithmic phase: A-549 (lung cancer), Bel-7402 (liver cancer), HCT (adenocarcinoma of colon), HL-60 (leukemia), BGC-823 (cancer of the stomach), KB (nasopharyngeal carcinoma) are with after trysinization, the cell suspension of 5000/mL is made into the RPM11640 nutrient solution of 10% calf serum, be seeded in 96 well culture plates, 100 μ L are inoculated in every hole, 37 DEG C, 5%CO 2cultivate 24h.
Experimental group: add embodiment 2 gained sample solution 10 μ L (namely use physiological saline solution embodiment 1 gained complex crystal 2, concentration is 5 μ g/mL), every hole final volume is 200 μ L, supplies with RPMI-1640.37 DEG C, 5%CO 2cultivate 3d.
Supernatant liquor is abandoned after cultivating 3d, every hole adds the serum-free medium of the freshly prepared 0.5mg/mLMTT of 100 μ L (tetrazolium bromide), 37 DEG C are continued to cultivate 4h, carefully abandon supernatant, and add 200 μ LDMSO dissolving MTTformazon precipitations, with the mixing of miniature ultrasonic vibrator, microplate reader measures the optical density value at wavelength 544nm place.According to following formulae discovery growth of tumour cell inhibiting rate:
Growth of tumour cell inhibiting rate (%)=(OD contrast-OD experiment)/(OD contrast-OD blank) × 100%
Result shows, embodiment 1 gained title complex 2 pairs of kinds of tumor cells all have good growth-inhibiting effect, are respectively:
Be 71.15%, IC to A-549 (lung cancer) inhibitory rate of cell growth 50=0.55;
Be 68.34%, IC to Bel-7402 (liver cancer) inhibitory rate of cell growth 50=0.53;
Be 63.60%, IC to HCT (adenocarcinoma of colon) inhibitory rate of cell growth 50=0.59;
Be 68.12% to HL-60 (leukemia) inhibitory rate of cell growth;
Be 65.61% to BGC-823 (cancer of the stomach) inhibitory rate of cell growth;
Be 58.70% to KB (nasopharyngeal carcinoma) inhibitory rate of cell growth;
Conclusion: this illustrates, title complex 2 of the present invention can for the preparation of the medicine of prevention and therapy cancer.

Claims (9)

1. single catechol molybdenum match, its molecular chemical formula is:
{[MoO 3(C 6H 4O 2)(NH 2RNH 2)](NH 3RNH 3)} n
Wherein, R is the straight or branched alkylidene group of 1-6 carbon atom, NH 2rNH 2for organic amine compound, n be 1 or be greater than 1 integer.
2. title complex according to claim 1, wherein said organic amine compound is quadrol, 1,2-propylene diamine or 1,3-propylene diamine.
3. prepare the method for single catechol molybdenum match described in claim 1 or 2 for one kind, be with in the solvent of the mixed phase of aqueous phase, organic phase or aqueous phase and organic phase, molybdenum salt or molybdic oxide or hexacarbonylmolybdenum and pyrocatechol and organic amine reacted and forms described title complex; Specifically comprise the steps:
A) under normal temperature, pyrocatechol is placed in solvent and is positioned on magnetic stirrer, add organic amine to pH value 10-11;
B) add molybdenum salt or molybdic oxide or hexacarbonylmolybdenum after 0.5-1.5h to continue to stir 8-20h;
C) reacted solution is filtered, then the mother liquor of clarification is placed in container, leave standstill after slowly adding ether or sherwood oil;
D) crystallize out in two weeks rear containers.
4. method according to claim 3, wherein, aqueous phase is water solvent; Organic phase is organic solvent, and described organic solvent is alcohols, acetonitrile or acetone; Mixed phase is the mixture of aqueous phase and organic phase.
5. method according to claim 4, wherein, described alcohols is methyl alcohol, ethanol or Virahol.
6. method according to claim 3, wherein, described molybdenum salt is the inorganic salt of monokaryon molybdenum or inorganic salt hydrate, the inorganic salt of multinuclear molybdenum or organic salt.
7. method according to claim 3, wherein, described molybdenum salt is ammonium molybdate, Sodium orthomolybdate, potassium molybdate, calcium molybdate, moly-sulfide, ammonium thiomolybdate, positive tetrabutyl ammonium octamolybdate, the positive tetrabutyl six ammonium molybdate, positive tetrabutyl Ammonium Heptamolybdate, two ammonium molybdate or six molybdenum chlorides or their hydrate.
8. method according to claim 3, wherein, organic amine is quadrol, 1,2-propylene diamine, 1,3-propylene diamine.
9. the application of title complex described in claim 1 or 2 in the medicine of the generation and growth of preparing prevention and prohibition tumour.
CN201110344946.6A 2011-11-04 2011-11-04 Single catechol molybdenum match and preparation method thereof and its application Expired - Fee Related CN103087107B (en)

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Publication number Priority date Publication date Assignee Title
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CN1786008A (en) * 2005-11-30 2006-06-14 首都师范大学 Preparation method of low dimension molybdenum match crystal
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Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
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CN1786008A (en) * 2005-11-30 2006-06-14 首都师范大学 Preparation method of low dimension molybdenum match crystal
US20110159116A1 (en) * 2009-12-28 2011-06-30 Colorado State University Research Foundation Biocompatible materials for medical devices

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以邻苯二酚为配体的含钼配合物及其纳米结构的合成、表征及抗癌活性研究;王挺;《首都师范大学硕士学位论文》;20090215;第46、66-67页 *

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