CN112010876A - Copper (I) complex based on butanone and methoxy salicylaldehyde amino triazole Schiff base and synthesis method thereof - Google Patents

Copper (I) complex based on butanone and methoxy salicylaldehyde amino triazole Schiff base and synthesis method thereof Download PDF

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CN112010876A
CN112010876A CN202010990650.0A CN202010990650A CN112010876A CN 112010876 A CN112010876 A CN 112010876A CN 202010990650 A CN202010990650 A CN 202010990650A CN 112010876 A CN112010876 A CN 112010876A
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copper
butanone
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CN112010876B (en
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杨育兵
王雅洁
蒋毅民
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Liuzhou Institute of Technology
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Abstract

The invention discloses a copper (I) complex based on butanone and methoxy salicylaldehyde amino triazole Schiff base and a synthesis method thereof, wherein the synthesis method comprises the following steps: (1) weighing 8-12 mg of 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base and 4-6 mg of CuCl into a glass tube with one sealed end, adding 1.0-3.0 mL of butanone, and shaking to fully mix the materials; then the other end of the glass tube is sealed under the vacuum condition; (2) placing the sealed glass tube in an oven at the temperature of 110-130 ℃ for reaction, stopping heating after the reaction is carried out for 60-80 hours, and then cooling to room temperature at the temperature of 10 ℃ per hour to obtain colorless long-strip crystals, namely Cu (HL)2Cl]And (3) obtaining the product. 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-Methylbenzo [ g ]] [1,2,4]Triazolo [1,5-c] [1,3,5]The oxadiazolazine is a novel polycyclic compound, can be used as an intermediate to be applied to the fields of medicines, pesticides and the like, forms a complex with metal ions, has good antibacterial and anticancer activities, and has important potential application.

Description

Copper (I) complex based on butanone and methoxy salicylaldehyde amino triazole Schiff base and synthesis method thereof
Technical Field
The invention relates to a copper complex and an in-situ synthesis method thereof, in particular to a copper (I) complex based on butanone and 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base and a synthesis method thereof.
Background
In-situ synthesis technology appeared in recent years is widely applied to the fields of chemistry, chemical engineering, materials and the like. The in-situ synthesis refers to the in-situ generation of one or more novel compounds in a reaction system through chemical reaction under certain conditions. By in-situ synthesis, compounds which are difficult to obtain by other synthetic methods can be obtained.
At present, although in-situ ligand reaction is reported in a few documents, no report is found on the generation of a copper (I) complex by the reaction of 3-methoxysalicylaldehyde-3-amino-1, 2, 4-triazole Schiff base (the structure is shown in a formula (1)) and solvent butanone to generate 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g ] [1,2,4] triazolo [1,5-c ] [1,3,5] oxadiazoline (abbreviated as HL, the structure is shown in a formula (2)).
The structural formula of the 3-methoxy salicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base is shown as the formula (1):
Figure 327031DEST_PATH_IMAGE001
（1）
the structural formula of the 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g ] [1,2,4] triazolo [1,5-c ] [1,3,5] oxadiazolazine (HL) is shown as the formula (2):
Figure 4132DEST_PATH_IMAGE002
（2）。
disclosure of Invention
To obtain novel 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g ]
The invention discloses a [1,2,4] triazolo [1,5-c ] [1,3,5] oxadiazolazine complex, and discloses a copper (I) complex taking butanone and 3-methoxy salicylaldehyde-3-amino-1, 2, 4-triazole Schiff base as raw materials and an in-situ synthesis method of the copper (I) complex.
The invention relates to a copper (I) complex based on butanone and 3-methoxy salicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base, which has a chemical formula of [ Cu (HL)2Cl]Wherein HL = 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g] [1,2,4]Triazolo [1,5-c][1,3,5]Oxadiazolazine, the crystal of the complex belongs to a monoclinic system, C2/C space group, and the unit cell parameters are as follows:a =20.297(2) Å，b = 7.0045(5)Å ，c =20.9912(18)Å，α= 90.00º，β=91.608(9)º，γ= 90.00º，V = 2983.2 (4) Å3；
the structural formula of the complex is shown as the formula (3):
Figure 349662DEST_PATH_IMAGE003
（3）。
said complex [ Cu (HL)2Cl]The synthetic route of (A) is as follows:
Figure 703283DEST_PATH_IMAGE004
。
said complex [ Cu (HL)2Cl]The in-situ synthesis method comprises the following steps:
(1) weighing 8-12 mg of 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base and 4-6 mg of CuCl into a glass tube with one sealed end, adding 1.0-3.0 mL of butanone, and shaking to fully mix the materials; then the other end of the glass tube is sealed under the vacuum condition;
(2) placing the sealed glass tube in an oven at the temperature of 110-130 ℃ for reaction, stopping heating after the reaction is carried out for 60-80 hours, and then cooling to room temperature at the temperature of 10 ℃ per hour to obtain colorless long-strip crystals, namely Cu (HL)2Cl]And (3) obtaining the product.
From complex [ Cu (HL)2Cl]The synthetic route shows that the addition reaction of the solvent butanone and the 3-methoxy salicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base is carried out, and then a molecule of water H is removed2O, to form 7-methoxy-5, 13-dimethyl3, 11-dihydro-5H-5, 11-methylbenzo [ g ] yl] [1,2,4]Triazolo [1,5-c] [1,3,5]Oxadiazolazine (HL), in turn, coordinates with metallic copper (I).
The 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g ] [1,2,4] triazolo [1,5-c ] [1,3,5] oxadiazoline in the product is a novel polycyclic compound, can be used as an intermediate to be applied to the fields of medicines, pesticides and the like, forms a complex with metal ions, has good antibacterial and anticancer activities, and has important potential application.
The in-situ synthesis of the complex and the method thereof have the advantages of easily available raw materials, low cost, simple process and the like. In addition, the IC of the complex of the invention on partial cell strains is preliminarily determined by an MTT colorimetric method50The results show that the complex has certain antitumor activity.
Drawings
FIG. 1 shows the complex [ Cu (HL) of example 12Cl]Molecular structure of (2) (hydrogen atom is omitted).
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1
Complex [ Cu (HL)2Cl]The in-situ synthesis method comprises the following steps:
(1) respectively weighing 10.9mg (0.05 mmol) of 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base and 5.0 mg (0.05 mmol) of CuCl into a glass tube which is about 19 cm long and 1.0 cm in inner diameter and is sealed at one end, adding 2.0 mL of butanone, and shaking to fully mix the materials; then the other end of the glass tube is sealed under the vacuum condition;
(2) and (3) placing the sealed glass tube in a 120 ℃ oven for reaction, stopping heating after the reaction is carried out for 72 hours, and then cooling to room temperature at 10 ℃ per hour to obtain the colorless strip crystal. I.e., [ Cu (HL)2Cl]The product, yield 45.7%.
Referring to FIG. 1, it can be seen that only one of the smallest units of the complex of example 1 is crystallographically independentThe central copper (I) ion being coordinated with 1 chlorine atom Cl and 1N atom each from two ligands (HL) to form a compound of the formula [ Cu (HL)2Cl]The complex of (1). The minimum structural unit of the complex forms a three-dimensional crystal structure through weak bond interaction.
Example 2
Determination of IC of two complexes of the examples on partial cell lines by means of MTT colorimetry50As shown in Table 1, HL-7702 was a human normal liver cell line, A549 was a human lung cancer cell line, T-24 was a human bladder cancer cell line, and MGC80-3 was a human gastric cancer cell line.
TABLE 1 IC of the copper complexes of the invention on different cell lines50Value (μ M)
Figure 501475DEST_PATH_IMAGE006
The results in Table 1 show that the copper complex of example 1 has a certain antitumor activity.

Claims (3)

1. Copper (I) complex based on butanone and 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base is characterized in that: the copper (I) complex has the chemical formula [ Cu (HL)2Cl]Wherein HL = 7-methoxy-5, 13-dimethyl-3, 11-dihydro-5H-5, 11-methylbenzo [ g] [1,2,4]Triazolo [1,5-c][1,3,5]Oxadiazolazine, the crystal of the complex belongs to a monoclinic system, C2/C space group, and the unit cell parameters are as follows:a =20.297(2) Å，b = 7.0045(5)Å ，c =20.9912(18)Å，
α= 90.00º，β=91.608(9)º，γ= 90.00º，V = 2983.2 (4) Å3；
the structural formula of the complex is as follows:
Figure 751461DEST_PATH_IMAGE001
。
2. according to the claimsThe copper (I) complex according to claim 1, which is characterized by comprising [ Cu (HL) ]2Cl]The synthetic route of (A) is as follows:
Figure 934181DEST_PATH_IMAGE002
。
3. the method of synthesizing a copper (i) complex according to claim 3, wherein the method of synthesizing comprises the steps of:
(1) weighing 8-12 mg of 3-methoxysalicylaldehyde-condensed-3-amino-1, 2, 4-triazole Schiff base and 4-6 mg of CuCl into a glass tube with one sealed end, adding 1.0-3.0 mL of butanone, and shaking to fully mix the materials; then the other end of the glass tube is sealed under the vacuum condition;
(2) placing the sealed glass tube in an oven at the temperature of 110-130 ℃ for reaction, stopping heating after the reaction is carried out for 60-80 hours, and then cooling to room temperature at the temperature of 10 ℃ per hour to obtain colorless long-strip crystals, namely Cu (HL)2Cl]And (3) obtaining the product.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100204467A1 (en) * 2007-07-18 2010-08-12 Cis Bio International Lanthanide (iii) ion complexing compounds, luminescent lanthanide (iii) ion complexes and use thereof as fluorescent labels
CN106397461A (en) * 2016-09-13 2017-02-15 桂林理工大学 Magnetic material salicylaldehyde derivative Schiff base copper complex [Cu4(emdo)4].H2O and synthesis method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100204467A1 (en) * 2007-07-18 2010-08-12 Cis Bio International Lanthanide (iii) ion complexing compounds, luminescent lanthanide (iii) ion complexes and use thereof as fluorescent labels
CN106397461A (en) * 2016-09-13 2017-02-15 桂林理工大学 Magnetic material salicylaldehyde derivative Schiff base copper complex [Cu4(emdo)4].H2O and synthesis method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NIKOLAY YU. GOROBETS等: "Unexpected alternative direction of a Biginelli-like multicomponent reaction with 3-amino-1,2,4-triazole as the urea component", 《TETRAHEDRON LETTERS》 *
高霞等: "1,5-双(苯并三氮唑)戊烷钬配合物的抑菌性研究", 《化学工程与装备》 *

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