CN111057095A - Tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex and preparation method and application thereof - Google Patents
Tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex and preparation method and application thereof Download PDFInfo
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- LIEBYXBJTRFHAJ-UHFFFAOYSA-M tricyclohexylstannyl 5-chloro-2-oxo-1H-pyridine-3-carboxylate Chemical compound C1CCC(CC1)[Sn](C2CCCCC2)(C3CCCCC3)OC(=O)C4=CC(=CNC4=O)Cl LIEBYXBJTRFHAJ-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010668 complexation reaction Methods 0.000 title description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical compound C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 claims description 15
- XBHXNMLFJZTSAS-UHFFFAOYSA-N 5-chloro-2-oxo-1h-pyridine-3-carboxylic acid Chemical compound OC(=O)C1=CC(Cl)=CNC1=O XBHXNMLFJZTSAS-UHFFFAOYSA-N 0.000 claims description 12
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- 239000003814 drug Substances 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002447 crystallographic data Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 230000001093 anti-cancer Effects 0.000 claims description 7
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- 229940041181 antineoplastic drug Drugs 0.000 abstract description 11
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl tin Chemical compound 0.000 description 6
- 230000004071 biological effect Effects 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 4
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 4
- 239000003560 cancer drug Substances 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 150000003606 tin compounds Chemical class 0.000 description 2
- OAVCWZUKQIEFGG-UHFFFAOYSA-O 2-(5-methyl-2H-tetrazol-1-ium-1-yl)-1,3-thiazole Chemical compound CC1=NN=N[NH+]1C1=NC=CS1 OAVCWZUKQIEFGG-UHFFFAOYSA-O 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical compound C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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Abstract
The invention discloses a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex as well as a preparation method and application thereof, wherein the complex is represented by the following structural formula (I):
. The invention also discloses a preparation method of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex and application of the complex in preparation of antitumor drugs.
Description
Technical Field
The invention relates to a tricyclohexyl tin 5-chloro-2-hydroxypyridine-3-formate complex, a preparation method thereof and application of the complex in preparation of antitumor drugs.
Background
Since Brown's first discovery of organotin Carboxylates (CH)3CO2SnPh3) Has the advantages ofSince the bioactivity of mouse tumor, the research on the synthesis, structure and bioactivity of organotin carboxylate complexes has been receiving much attention from scientists. However, the known organotin compounds are generally highly toxic and thus have limited applications. Research has shown that the structure, reactivity and biological activity of organotin compounds are related both to the structure of the hydrocarbon group directly attached to the tin atom and to the nature of the ligand. The optimization of the structure of the organic tin complex through molecular design so as to adjust the balance between the toxicity and the biological activity of the organic tin complex is an important direction of research of people at present. The functional activation of alkyl or ligand can greatly change the coordination mode of tin atom, and further influence the bioactivity of organic tin complex. Research shows that the toxicity of the organic tin compound is related to the relative molecular mass of the organic tin compound, the smaller the relative molecular mass is, the greater the toxicity is, and the larger the relative molecular mass of the large steric hindrance alkyl tin. Therefore, the novel alkyl tin complex with large steric hindrance is synthesized, and the structure and the biological activity of the complex are researched, so that the method has important research significance.
As is well known, nitrogen heterocycles are important and common structural units of medicines, pesticides, functional materials and the like, and most of them are closely related to life systems, so that the research on the structure of organotin derivatives of such ligands can not only provide useful information for the revealed anticancer mechanism, but also provide a possible molecular design scheme for the development of novel drugs. Nitrogen-containing heteroatom carboxylic acid is an important carboxylic acid ligand, and the synthesis of novel nitrogen-containing heterocyclic organic tin carboxylate compounds and the research on the biological activity of the nitrogen-containing heterocyclic organic tin carboxylate compounds are very necessary. For example, Chinese patent CN101402650B discloses the application of a dibutyltin and quinolinecarboxylic acid complex in preparing medicines for treating gastric cancer, nasopharyngeal carcinoma, human liver cancer or leukemia.
Based on that the tricyclohexyl tin hydroxide is a substance which is proved to have good biological activity by experiments, and the cyclohexyl has the characteristics of large steric hindrance, large molecular weight and the like, the tricyclohexyl tin hydroxide is selected to react with a heterocyclic carboxylic acid ligand 5-chloro-2-hydroxypyridine-3-formic acid under certain conditions to synthesize a complex with strong inhibitory activity to A549 (human lung cancer cells), Hela (human cervical cancer cells) and HGC-27 (human gastric cancer cells), and a new way is provided for developing anticancer drugs.
Disclosure of Invention
In view of the problems of the prior art, the first object of the present invention is to provide a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex.
It is a second object of the present invention to provide a process for preparing the above tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex.
The third purpose of the invention is to provide the application of the tricyclohexyl tin 5-chloro-2-hydroxypyridine-3-formate complex in preparing anti-cancer drugs.
A tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex as a first aspect of the present invention is a complex of the following structural formula (I):
(I)。
the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex is subjected to elemental analysis, infrared spectroscopic analysis, nuclear magnetic resonance spectroscopy and X-ray single crystal structure analysis, and the result is as follows:
elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex has a crystal structure, and the crystallographic data of the complex are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11)nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382 Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
the tricyclohexyl tin 5-chlorine-2-hydroxypyridine-3-formic ether complex has the structural characteristics that: the central tin in the molecule forms a triangular bipyramid configuration with the coordinating atoms.
In the second aspect of the invention, the preparation method of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex comprises the steps of sequentially placing tricyclohexyltin hydroxide, 5-chloro-2-hydroxypyridine-3-formic acid and a solvent toluene in a 250 mL round-bottom flask, installing a Dean-Stark water separator, and carrying out heating reflux reaction at 112-120 ℃ for 6-12 h. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex.
In a preferred embodiment of the present invention, the ratio of the amounts of the tricyclohexyltin hydroxide and 5-chloro-2-hydroxypyridine-3-carboxylic acid is 1 (1-1.1).
In a preferred embodiment of the invention, the solvent toluene is added in an amount of 25-35 ml per millimole of tricyclohexyltin hydroxide.
The third aspect of the invention relates to the application of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex in preparing anti-cancer drugs.
The applicant carries out in-vitro antitumor activity confirmation research on the complex, and confirms that the complex has certain antitumor biological activity, namely the application of the complex in preparing antitumor drugs, in particular in preparing anti-human lung cancer drugs, human cervical cancer drugs and human gastric cancer drugs.
The tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex shows good anticancer activity on human lung cancer cells, human cervical cancer cells, human gastric cancer cells and the like, and can be used as a raw material for preparing anti-lung cancer, anti-cervical cancer and anti-gastric cancer medicines. Compared with the platinum anticancer drugs commonly used at present, the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex has the characteristics of high anticancer activity, low cost, simple preparation method and the like, and provides a new way for developing anticancer drugs.
Drawings
FIG. 1 is a crystal molecular structural diagram of a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex.
FIG. 2 is an IR spectrum of a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex.
FIG. 3 is a diagram of a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex1H NMR spectrum.
FIG. 4 is a diagram of a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex13C NMR spectrum.
FIG. 5 is a diagram of a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex119Sn NMR spectrum.
Detailed Description
The present invention is further illustrated in detail by the following examples, but it should be noted that the scope of the present invention is not limited by these examples at all.
Example 1:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
0.3854 g (1 mmol) of tricyclohexyltin hydroxide, 0.1741 g (1 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 25 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is arranged, and the mixture is heated and refluxed at 120 ℃ for 6 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 71%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 2:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
0.3852 g (1.0 mmol) of tricyclohexyltin hydroxide, 0.1915 g (1.1 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 25 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 8 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 72%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 3:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
0.3857 g (1.0 mmol) of tricyclohexyltin hydroxide, 0.1916 g (1.1 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 35 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 8 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 70%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 4:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
0.7705 g (2.0mmol) of tricyclohexyltin hydroxide, 0.3652 g (2.1 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 50 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 8 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 73%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 5:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
0.7703 g (2.0mmol) of tricyclohexyltin hydroxide, 0.3489 g (2.0mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 60 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 12 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 72%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
Crystals thereofAnd (3) learning data: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 6:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
1.1556 g (3.0 mmol) of tricyclohexyltin hydroxide, 0.5229 g (3.0 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 75 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 12 hours. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 74%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
example 7:
preparation of tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex:
1.1557 g (3.0 mmol) of tricyclohexyltin hydroxide, 0.5743 g (3.3 mmol) of 5-chloro-2-hydroxypyridine-3-carboxylic acid and 90 mL of solvent toluene are sequentially added into a 250 mL round-bottom flask, a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 120 ℃ for 6 h. After the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex. Yield: 72%, melting point: 119 ℃ and 122 ℃.
Elemental analysis (C)25H40ClNO4Sn): theoretical value: c, 52.43; h, 7.04; and N, 2.45. Measurement value: c, 52.49; h, 7.08; and N, 2.41.
IR(KBr, v/cm-1): 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s),1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m)。
1HNMR (CDCl3, 500MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s,1H), 3.48 (s, 3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H)。
13CNMR(CDCl3, 125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60,110.82, 50.80, 34.90, 31.04, 28.86, 26.77。
119Sn NMR(CDCl3, 186 MHz), δ(ppm): 50.10。
The crystallographic data are as follows: the crystal belongs to monoclinic system and space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3，Dc=1.382Mg·m-3，μ(MoKa)=1.054mm-1，F(000)= 1184，1.79°＜θ< 25.01 °, crystal size: 0.24X 0.22X 0.20 mm,R=0.0370，wR=0.0954。
test example:
the in vitro anticancer activity of the tricyclohexyl tin 5-chloro-2-hydroxypyridine-3-formate complex is determined by an MTT (methyl thiazolyl tetrazolium) experimental method.
MTT assay:
based on the metabolic reduction of 3- (4, 5-dimethylthiozol-2-yl) -2, 5-diaryltetrazolium bromide. Succinate dehydrogenase in mitochondria of living cells can reduce exogenous MTT to water-insoluble blue-purple crystalline Formazan (Formazan) and deposit in cells, while dead cells do not have this function. Dimethyl sulfoxide (DMSO) can dissolve formazan in cells, and the optical density of characteristic wavelength is measured by enzyme labeling instrument, which can indirectly reflect the number of living cells.
MTT method was used to measure the inhibitory activity of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex prepared in example 1 on human lung cancer cells (A549), human cervical cancer cells (Hela), and human gastric cancer cells (HGC-27).
Cell line and culture System: the A549, Hela and HGC-27 cell lines were obtained from the American tissue culture Bank (ATCC). Using RPMI1640 medium (GIBICO) containing 10% fetal bovine serum at 5% (volume fraction) CO2And culturing in vitro in a 37 ℃ saturated humidity incubator.
The testing process comprises the following steps: test drug solution (0.0625. mu. mol)and/L-0.5 mu mol/L) are added into each hole according to concentration gradient of concentration, and each concentration is provided with 3 parallel holes. The experiment was divided into drug test group (with different concentrations of test drug added), control group (with culture medium and cells only, without test drug added) and blank group (with culture medium only, without cells and test drug added). Placing the medicated hole plate at 37 deg.C and 5% CO2Culturing in an incubator for 24 h. The activity of the control drug was determined as per the method of the test sample. In the well plate after 48 hours of incubation, 20uL of MTT (5 g/L in PBS) was added to each well. After standing at 37 ℃ for 4h, the supernatant was removed. Add 150uL DMSO to each well, shake for 10min to dissolve the Formazan crystals. Finally, the absorbance of each well was measured at a wavelength of 570nm using a BioTek multifunctional microplate reader.
Data processing: data processing Using GraAr Pad Prism version5.0 program, Complex IC50Fitting was done by a non-linear regression model with sigmoidal dose response in the program.
Analyzing human lung cancer cell (A549) cell line, human cervical cancer cell (Hela) cell line and human gastric cancer cell (HGC-27) cell line by MTT analysis method, and determining IC50The results are shown in table 1, with the conclusion that: as can be seen from the data in the table, the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex disclosed by the invention is used as an anticancer drug, has high anticancer activity on human lung cancer, human cervical cancer and human gastric cancer, and can be used as a candidate complex of the anticancer drug.
Table 1 tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex anticancer drug in vitro activity test data.
| Human lung cancer cell | Human cervixCancer cell | Human gastric cancer cell | |
| Cell line | A549 | Hela | HGC-27 |
| IC50μM | 0.4332 | 0.703 | 0.1249 |
The tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complexes prepared in the remaining examples were tested for anticancer activities by MTT method against human lung cancer cells (a 549), human cervical cancer cells (Hela) and human gastric cancer cells (HGC-27) in the same experimental examples, and the test results were substantially the same as those in table 1.
Claims (8)
1. A tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex, which is a complex of the following structural formula (I):
(I)。
2. the complex of claim 1 comprising a tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex having an infrared spectrum of: FT-IR (KBr, v/cm)-1) 3242.34(w), 2920.23(s), 2846.93(s), 1627.92(s), 1570.06(s), 1444.68(s), 1419.61(s), 1386.82(s), 1334.74(w), 1301.95(w),1236.37(m),1209.37(m), 1170.79 (w), 1124.50(w), 1089.78(w), 1039.63(w),1014.56(m), 991.41(m), 914.26(w), 877.61(w), 819.75(m), 725.23(s), 659.66(w),594.08(w), 536.21(w), 487.99(w), 464.84(w), 422.41(m), nuclear magnetic spectrum data thereof:1HNMR(CDCl3, 500 MHz)δ(ppm): 12.24 (s, 1H), 8.29 (s, 1H), 8.14 (s, 1H), 3.48 (s,3H), 2.06-1.94 (m, 9H), 1.74-1.68 (m, 15H), 1.35-1.33 (m, 9H);13CNMR(CDCl3,125MHz)δ(ppm): 171.87, 164.25, 151.73, 139.82, 122.60, 110.82, 50.80, 34.90,31.04, 28.86, 26.77;119Sn NMR (CDCl3，186 MHz), δ(ppm): 50.10。
3. the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex of claim 1, wherein the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex has a crystal structure with the following crystallographic data: monoclinic system, space groupP 2 1 /c，a=0.98532(7) nm，b=2.04085(15) nm，c=1.39537(11) nm，α=90°，β=101°，γ=90°，Z=4，V=2.7522(8) nm3(ii) a The central tin in the molecule and the coordination atom form a triangular bipyramid configuration.
4. The preparation method of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex as described in claim 1, wherein tricyclohexyltin hydroxide, 5-chloro-2-hydroxypyridine-3-carboxylic acid and toluene as solvent are sequentially added into a 250 mL round-bottomed flask, and then a Dean-Stark water separator is installed, and the reaction is heated and refluxed at 112-120 ℃ for 6-12 hours; after the reaction is finished, filtering while the reaction is hot, removing the solvent from the filtrate by using a rotary evaporator to obtain a reddish brown solid, and recrystallizing the reddish brown solid by using methanol to obtain the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-formate complex.
5. The method according to claim 4, wherein the ratio of the amounts of the tricyclohexyltin hydroxide and 5-chloro-2-hydroxypyridine-3-carboxylic acid is 1 (1 to 1.1).
6. The method according to claim 4, wherein the solvent toluene is used in an amount of 25 to 35 ml per mmol of tricyclohexyltin hydroxide.
7. Use of the tricyclohexyltin 5-chloro-2-hydroxypyridine-3-carboxylate complex of claim 1 in the preparation of an anti-cancer medicament.
8. The use of claim 7, wherein the cancer cell is lung cancer, cervical cancer, gastric cancer.
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