CN110590671B - Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone - Google Patents

Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone Download PDF

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CN110590671B
CN110590671B CN201910828333.6A CN201910828333A CN110590671B CN 110590671 B CN110590671 B CN 110590671B CN 201910828333 A CN201910828333 A CN 201910828333A CN 110590671 B CN110590671 B CN 110590671B
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杨廷海
林陈兰
罗世鹏
王欣
陈艳飞
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Nantong Volant-Chem Corp
Jiangsu University of Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4,4' -diamino diphenyl sulfone. The structural formula of the copper complex catalyst is as follows:
Figure DDA0003747716130000011
the preparation method comprises the following steps: dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an ethanol aqueous solution, adding a copper chloride aqueous solution, uniformly mixing to obtain a mixed solution, standing at 5 ℃ for reaction for 2-4 days to obtain blue crystals, and thus obtaining the copper complex catalyst. The invention also provides application of the copper complex catalyst in catalytic synthesis of 4,4' -diaminodiphenyl sulfone. The copper complex catalyst disclosed by the invention is simple in synthesis step, the copper salt is cheap and easy to obtain, the catalyst is less in dosage and higher in yield in the application of catalytic synthesis of 4,4' -diamino diphenyl sulfone, the yield of two-step continuous preparation is 84-92%, and the catalyst is safe, pollution-free and environment-friendly.

Description

Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4,4' -diamino diphenyl sulfone.
Background
4,4' -diamino diphenyl sulfone also called dapsone (abbreviated as DDS), it has many excellent chemical properties, it is a chemical industrial product with multiple use, can be used for synthesizing the curing agent in the epoxy resin adhesive, can also be regarded as the synthetic monomer of the high polymer material, used for synthesizing high temperature resistant high polymer material and chromatogram stationary liquid such as polysulfone amide resin, etc.; in addition, it can be used as antibiotic medicine for treating bacterial infection of human or animal, such as Jatropha curcas, etc.
Therefore, the demand of 4,4' -diaminodiphenyl sulfone is also increasing on the market, and there are currently reported various synthetic methods for DDS, such as: 1) Dichlorodiphenyl sulfone or dibromodiphenyl sulfone is used as a raw material, and the halogen ammonolysis reaction is carried out to prepare (chemical product handbook, rubber additive, zhanglian edition, P310; CN201310060592.1; 2) Preparing 4,4 '-diacetyl amino diphenyl sulfoxide from acetanilide and other starting raw materials by Friedel-crafts reaction, oxidizing the sulfoxide by hydrogen peroxide or chromium salt to obtain 4,4' -diacetyl amino diphenyl sulfone, and finally hydrolyzing to obtain a target product (Macromolecules (Washington, DC, united States), 2015,48 (6), 1748-1758; acta Ciencia Indica, chemistry,2009,35 (1), 11-18; j.am.chem.soc.,1939,61,2763-27655; yakugaku Zasshi,1940,60,22-4, extracts 1-3; ) (ii) a 3) 4,4 '-dinitro diphenyl sulfone or 4,4' -diazido diphenyl sulfone is first prepared, and then the nitro or azido group is converted into an amino group (CN 201410734026.9; phosphorous, sulfur and Silicon and the Related Elements,2004,179 (9), 1813-1817; ranliao Yu Ranse,2005,42 (3), 43-46).
The preparation method has the defects of high cost, complex steps, low safety, easy environmental pollution and the like: the method 1) needs ammonia water which is a chemical reagent which is not friendly to the environment, is easy to explode and not easy to store, and needs to react at high temperature and high pressure, so that the method has high requirements on equipment and high environmental protection cost; method 3) functional groups of nitro or azide are converted into amino, the azide is easy to explode and not easy to industrialize, reducing agents such as lithium aluminum hydride and the like are needed for reducing the nitro, the post-treatment is complex, and the cost is high; the raw materials of the method 2) are cheap and easy to obtain, but hydrogen peroxide or heavy metal chromium salt is used during oxidation, the hydrogen peroxide is also easy to explode, and the heavy metal chromium salt is a heavy metal reagent with very heavy environmental pollution.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to solve the defects of complex preparation steps and easy pollution to the environment in the prior art, the invention aims to provide a copper complex catalyst, a preparation method thereof and application thereof in catalytic synthesis of 4,4' -diamino diphenyl sulfone. The invention utilizes the copper complex catalyst to carry out catalytic oxidation reaction under mild conditions to obtain the copper complex catalyst
Figure GDA0003747716120000021
Is oxidized to obtain
Figure GDA0003747716120000022
Finally, hydrolyzing to obtain the target product 4,4' -diamino diphenyl sulfone.
The specific technical scheme is as follows:
a copper complex catalyst having the formula:
Figure GDA0003747716120000031
further, the copper complex catalyst is monoclinic system, P21/c space group, unit cell parameters are as follows:
Figure GDA0003747716120000032
α＝90°，β＝98.476(3)°，γ＝90°。
another object of the present invention is to provide a method for preparing the copper complex catalyst, comprising the steps of:
dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an ethanol aqueous solution, adding an aqueous solution of copper chloride, uniformly mixing to obtain a mixed solution, standing at 5 ℃ for 2-4 days to react to obtain blue crystals, filtering, and drying to obtain the copper complex catalyst.
Preferably, after the 5-hydroxy-3-pyrazolecarboxylic acid is dissolved in an aqueous ethanol solution, the concentration of the 5-hydroxy-3-pyrazolecarboxylic acid is (0.05-0.5) mol/L.
Preferably, the volume ratio of the ethanol to the water in the ethanol aqueous solution is (1-3) to 1; the concentration of the copper chloride in the aqueous solution of the copper chloride is (0.2-2.0) mol/L.
Preferably, the molar ratio of the 5-hydroxy-3-pyrazolecarboxylic acid to the copper chloride in the mixed solution is (2-6): 1.
The invention further aims to provide the application of the copper complex catalyst in the catalytic synthesis of 4,4' -diaminodiphenyl sulfone.
Further, in order to
Figure GDA0003747716120000041
The 4,4' -diamino diphenyl sulfone is obtained by catalytic oxidation and hydrolysis reaction under the condition of the copper complex catalyst.
The chemical reaction equation is as follows:
Figure GDA0003747716120000042
the catalytic oxidation and hydrolysis reaction steps are as follows:
catalytic oxidation: will be provided with
Figure GDA0003747716120000043
(Compound 1) is dissolved in an alcoholic solvent, and then a copper complex catalyst (designated as CuL) is added 2 -Cat.), and continuously introducing oxygen, and carrying out catalytic oxidation reaction at the temperature of 50-100 ℃. Stirring for 12-48 hours, and filtering and separating CuL after the reaction is finished 2 Concentrating the filtrate under reduced pressure to remove the solvent to obtain an intermediate
Figure GDA0003747716120000044
(Compound 2), this intermediate was used directly in the next hydrolysis reaction without purification.
The alcohol solvent is preferably one or more of ethanol, isopropanol and tert-butanol;
Figure GDA0003747716120000051
(compound 1) the concentration of the solution after dissolving in the alcohol solvent is 0.1-5 mol/L; the copper complex catalyst (CuL) 2 -Cat.) is
Figure GDA0003747716120000052
(Compound 1) to 3%.
And (3) hydrolysis reaction: subjecting the above intermediate to reaction
Figure GDA0003747716120000053
(compound 2) is suspended in hydrochloric acid solution with the concentration of 1.0-6.0mol/L, then the temperature is raised to 40-100 ℃, the mixture is stirred for 4-48 hours at the reaction temperature until the hydrolysis is completed, then the mixture is cooled to room temperature, the pH value is adjusted to 10-14 by using sodium hydroxide solution with the mass fraction of 5-20 wt%, a large amount of solid is generated, the solid is filtered and washed, and the crude solid product is recrystallized to obtain a pure product of 4,4' -diaminodiphenyl sulfone (compound 3);
the above-mentioned
Figure GDA0003747716120000054
The concentration of the (compound 2) in the hydrochloric acid solution is preferably 0.1 to 10mol/L; the solvent used for recrystallization is preferably acetone.
The invention has the beneficial effects that:
(1) The copper complex catalyst of the invention is metal ion Cu 2+ The coordination compound is used as the center of the coordination compound, and is coordinated with two nitrogen atoms and two oxygen atoms in two 5-hydroxy-3-pyrazole carboxylic acids and two oxygen atoms in two water molecules, compared with an inorganic metal catalyst, the coordination compound can improve the utilization rate of metal, the dosage of the catalyst is small, the catalytic effect is good, and the coordination compound has higher yield in the application of catalytic synthesis of 4,4' -diamino diphenyl sulfone, wherein the yield of two-step continuous preparation is 84-92%.
(2) The copper complex catalyst disclosed by the invention is simple in synthesis step, the copper salt is cheap and easy to obtain, and the catalyst is less in dosage, safe and pollution-free, environment-friendly and has better popularization and application values and industrialization potentials in the application of catalytic synthesis of 4,4' -diamino diphenyl sulfone.
Drawings
FIG. 1 is a crystal structure diagram (hydrogen atom is omitted in the drawing) of a copper complex catalyst prepared by the present invention;
FIG. 2 is a PXRD pattern of a copper complex catalyst prepared in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples, but the present invention is not limited thereto.
Example 1: preparation of copper complex catalysts
Weighing CuCl 2 ·2H 2 O (20mmol, 3.40g) was dissolved in 100mL of distilled water to obtain CuCl 2 An aqueous solution; 5-hydroxy-3-pyrazolecarboxylic acid (100mmol, 1.28g) was dissolved in a mixed solution of 200mL of ethanol and 100mL of distilled water to prepare a ligand solution. Adding CuCl 2 Adding the water solution into the ligand solution, mixing to obtain transparent sky blue solution, standing at 5 deg.C for 3 days to precipitate blue cluster crystal, filtering, and drying to obtain copper complex catalyst (CuL) 2 -cat.) the product mass was 3.74 g, yield was 53%. The product was characterized by infrared, with the results: IR (KBr, cm) -1 )：3527(m)，3419(m)，2892(w)，1552(s)，1452(s)，1411(m)，1346(m)，1213(m)，1031(w)，904(w)，842(m)，765(m)，597(w)，480(w)。
The copper complex catalyst of the resulting product has the chemical formula [ Cu (H) 2 pzc) 2 (H 2 O) 2 ]In the formula H 3 pzc is 5-hydroxy-3-pyrazolecarboxylic acid; the structural formula is as follows:
Figure GDA0003747716120000071
example 2: preparation of copper complex catalyst
Weighing CuCl 2 ·2H 2 O (50mmol, 8.50g) was dissolved in 100mL of distilled water to give CuCl 2 An aqueous solution; 5-hydroxy-3-pyrazolesCarboxylic acid (200mmol, 2.56g) was dissolved in a mixed solution of 300mL of ethanol and 100mL of distilled water to prepare a ligand solution. Adding CuCl 2 Adding the aqueous solution into the ligand solution, mixing uniformly to obtain a transparent sky blue solution, standing at the temperature of 5 ℃ for 4 days, and separating out 11.8 g of blue cluster crystal, wherein the yield is 67%. The product was characterized by infrared, and the results were: IR (KBr, cm) -1 )：3528(m)，3419(m)，2891(w)，1550(s)，1451(s)，1415(m)，1342(m)，1213(m)，1034(w)，906(w)，843(m)，767(m)，591(w)，483(w)。
The infrared test results showed that the product prepared in this example was the same as the product of example 1, and was a copper complex catalyst [ Cu (H) 2 pzc) 2 (H 2 O) 2 ]。
FIG. 1 shows a copper complex catalyst [ Cu (H) prepared in example 1 2 pzc) 2 (H 2 O) 2 ]The crystal structure of (2) (hydrogen atom is omitted in the figure), it can be seen that the central metal Cu1 of the complex catalyst is in { N } 2 O 4 In the octahedral coordination environment with two H 2 Nitrogen atoms (N1, N1A), two H atoms on pyrazole ring of pzc ligand 2 The carboxyl group of the pzc ligand is coordinated with oxygen atoms O1 and O1A and two coordinated water molecules O4 and O4A.
FIG. 2 shows a copper complex catalyst [ Cu (H) prepared in example 1 2 pzc) 2 (H 2 O) 2 ](denoted as CuL 2 Cat.) as seen by the same simulated diffraction peak positions.
Table 1 shows the copper complex catalyst [ Cu (H) prepared in example 1 2 pzc) 2 (H 2 O) 2 ]Crystallographic data of (a):
TABLE 1
Figure GDA0003747716120000081
Figure GDA0003747716120000091
TABLE 2 is as followsCopper complex catalyst prepared in example 1 [ Cu (H) 2 pzc) 2 (H 2 O) 2 ]Crystal bond length of
Figure GDA0003747716120000092
Data:
TABLE 2
Cu1-N1 1.953(3) Cu1-O1A 1.977(3)
Cu1-N1A 1.953(3) Cu1-O4 2.561(24)
Cu1-O1 1.977(3) Cu1-O4A 2.561(24)
Table 3 shows the copper complex catalyst [ Cu (H) ] prepared in example 1 2 pzc) 2 (H 2 O) 2 ]Crystal bond angle (°) data:
TABLE 3
N1-Cu1-N1A 180.0 O4-Cu1–N1A 90.36(12)
N1-Cu1-O1 81.86(11) O4-Cu1–O1A 89.09(11)
N1-Cu1-O1A 98.14(12) O4A-Cu1–N1A 89.64(12)
N1-Cu1-O4 89.64(12) O4A-Cu1–O1A 90.91(11)
N1-Cu1–O4A 90.36(12) O1A-Cu1–N1A 81.86(11)
O1-Cu1–O1A 180.0 O1-Cu1–O4A 89.09(11)
O1-Cu1–N1A 98.14(12) O4-Cu1–O4A 180.0
O1-Cu1–O4 90.91(11)
It can be seen that the bond lengths of both Cu1-N1 and Cu1-N1A are
Figure GDA0003747716120000093
The bond lengths of Cu1-O1 and Cu1-O1A are all
Figure GDA0003747716120000094
The bond lengths of Cu1-O4 and Cu1-O4A are all
Figure GDA0003747716120000095
Bond angle N1-Cu1-N1A O1-Cu1-O1A and O4-Cu1-O4A are all 180 degrees.
Copper complex catalyst [ Cu (H) 2 pzc) 2 (H 2 O) 2 ]Examples 3 to 4 apply in the catalytic synthesis of 4,4' -diaminodiphenyl sulfone:
example 3: synthesis of 4,4' -diaminodiphenyl sulfone
Catalytic oxidation: in a 1000 ml three-necked flask, mixing
Figure GDA0003747716120000101
(Compound 1, 31.6 g, 100 mmol) was dissolved in 500 mL of isopropanol, and then copper complex catalyst (CuL) was added 2 -Cat.) (0.374 g, 1.0 mmol) as a catalyst, and oxygen was continuously introduced under stirring to conduct catalytic oxidation at 75 ℃. Stirring for 24 hr, cooling to room temperature, and filtering to separate CuL 2 Concentrating the filtrate under reduced pressure to remove isopropanol solvent, and vacuum drying to obtain white solid
Figure GDA0003747716120000102
(Compound 2), all solids were used directly in the next hydrolysis reaction.
And (3) hydrolysis reaction: suspending the solid in 200ml of hydrochloric acid solution with the concentration of 3.0mol/L, heating the reaction solution to reflux to 50 ℃, stirring for 4 hours, cooling to room temperature after complete hydrolysis, adjusting the pH of the solution to 14 by using 10 mass percent of sodium hydroxide solution, precipitating a large amount of solid, filtering and washing the product to obtain a crude product of 4,4' -diaminodiphenyl sulfone, recrystallizing the crude product of 4,4' -diaminodiphenyl sulfone by using acetone to obtain 20.8 g of white solid, namely a pure product of 4,4' -diaminodiphenyl sulfone (compound 3), wherein the yield of the two-step continuous process is 84%.
Identification data: melting point: 175 to 177 ℃; and (3) infrared characterization results: IR (KBr, cm) -1 ): 3480, 3300, 3275, 1630, 1570, 1275, 1214, 1135. Nuclear magnetic results: NMR 1 H(DMSO-d 6 )δ＝7.44(d,J＝8.4Hz,4H),6.58(d,J＝8.4Hz,4H),5.97(br s,4H)ppm；NMR 13 C(DMSO-d 6 )δ＝153.4,129.3,128.8,113.5.
Example 4: synthesis of 4,4' -diaminodiphenyl sulfone
Catalytic oxidation: in a 5L three-necked flask with mechanical stirring, the mixture is stirred
Figure GDA0003747716120000111
(Compound 1, 158 g, 500 mmol) was dissolved in 2000 mL of isopropanol and copper complex catalyst (CuL) was added 2 -Cat.) (2.8 g, 7.5 mmol) as catalyst, and under the condition of stirring, continuously introducing oxygen, and carrying out catalytic oxidation reaction at 80 ℃. Stirring for 24 hr, cooling to room temperature, and filtering to separate CuL 2 -Cat, vacuum concentrating the filtrate to remove isopropanol solvent, and vacuum drying to obtain white solid
Figure GDA0003747716120000112
(Compound 2), all solids were used directly in the next hydrolysis reaction.
And (3) hydrolysis reaction: suspending the solid obtained by the reaction in 1000 ml of hydrochloric acid solution with the concentration of 2.0mol/L, heating the reaction solution to reflux to 100 ℃, stirring for 6 hours, cooling to room temperature after complete hydrolysis, adjusting the pH of the solution to 12 by using 10 mass percent of sodium hydroxide solution, precipitating a large amount of solid, filtering and washing the product to obtain a crude product of 4,4' -diaminodiphenyl sulfone, recrystallizing the crude product of 4,4' -diaminodiphenyl sulfone by using acetone to obtain 114 g of white solid, namely a pure product of 4,4' -diaminodiphenyl sulfone (compound 3), wherein the yield of the two-step continuous process is 92%.
Identification data: melting point: 176 to 178 ℃; and (3) infrared characterization results: IR (KBr, cm) -1 ): 3481, 3301, 3274, 1632, 1570, 1276, 1213, 1135. Nuclear magnetic results: NMR 1 H(DMSO-d 6 )δ＝7.45(d,J＝8.4Hz,4H),6.58(d,J＝8.4Hz,4H),5.96(br s,4H)ppm；NMR 13 C(DMSO-d 6 )δ＝153.4,129.3,128.8,113.5.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.

Claims (6)

1. A copper complex catalyst, characterized in that the copper complex catalyst has the following structural formula:
Figure FDA0003834559700000011
the copper complex catalyst is a monoclinic system, P21/c space group, and unit cell parameters are as follows:
Figure FDA0003834559700000012
α＝90°，β＝98.476(3)°，γ＝90°。
2. a method for preparing the copper complex catalyst according to claim 1, comprising the steps of:
dissolving 5-hydroxy-3-pyrazolecarboxylic acid in an ethanol aqueous solution, adding a copper chloride aqueous solution, uniformly mixing to obtain a mixed solution, standing at 5 ℃ for reaction for 2-4 days to obtain blue crystals, filtering, and drying to obtain the copper complex catalyst.
3. The method for producing a copper complex catalyst according to claim 2, characterized in that: after the 5-hydroxy-3-pyrazolecarboxylic acid is dissolved in an ethanol aqueous solution, the concentration of the 5-hydroxy-3-pyrazolecarboxylic acid is (0.05-0.5) mol/L.
4. The method for producing a copper complex catalyst according to claim 2, characterized in that: the volume ratio of ethanol to water in the ethanol water solution is (1-3) to 1; the concentration of the copper chloride in the aqueous solution of the copper chloride is (0.2-2.0) mol/L.
5. The method for producing a copper complex catalyst according to claim 2, characterized in that: the molar ratio of the 5-hydroxy-3-pyrazolecarboxylic acid to the copper chloride in the mixed solution is (2-6): 1.
6. Use of a copper complex catalyst according to claim 1 for the catalytic synthesis of 4,4' -diaminodiphenyl sulfone, characterized in that: to be provided with
Figure FDA0003834559700000021
As raw material, under the condition of a copper complex catalyst, wherein the copper complex catalyst is marked as CuL 2 -Cat, which is subjected to catalytic oxidation and hydrolysis reaction to obtain 4,4' -diaminodiphenyl sulfone, and the chemical reaction equation is as follows:
Figure FDA0003834559700000022
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