CN111269272A - Complex for synthesizing dye intermediate and preparation method thereof - Google Patents
Complex for synthesizing dye intermediate and preparation method thereof Download PDFInfo
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- CN111269272A CN111269272A CN202010130223.5A CN202010130223A CN111269272A CN 111269272 A CN111269272 A CN 111269272A CN 202010130223 A CN202010130223 A CN 202010130223A CN 111269272 A CN111269272 A CN 111269272A
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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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
Abstract
The invention discloses a complex for synthesizing a dye intermediate and a preparation method thereof; the complex is mainly applied to a Heck reaction to prepare a dye intermediate; the conventional Heck reaction is generally carried out in PdCl2Or Pd (OAc)2The method is carried out under the action of an equal-phase catalyst, but the palladium catalyst has poor thermal stability in the reaction process, and palladium ions are easy to be reduced to generate palladium black to inactivate the catalyst; the occurrence of the palladium catalyst of the organic phosphorus ligand greatly improves the service life and the efficiency of the catalyst, and the organic phosphorus ligand is generally sensitive to air, complicated to operate, relatively high in toxicity, not friendly to the environment and expensive; the N ^ N bidentate ligand is a ligand with smaller toxicity, and the N ^ N bidentate ligand palladium complex can also be highThe pyridine-imine palladium complex is actively catalyzed in the Heck reaction, so that the pyridine-imine palladium complex prepared by the invention is applied to the Heck reaction.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a complex for synthesizing a dye intermediate and a preparation method thereof.
Background
Heck coupling has become an important method for reacting olefin derivatives with halogenated aromatic hydrocarbons since the early 70 s of the last century. Mizoroki and Heck discovered the Heck reaction in 1971 and 1972, respectively, and opened up the research field of Heck coupling reaction, this classical Heck organic reaction refers to the C-C coupling reaction in which a metal catalyst catalyzes the reaction of a halogenated aromatic hydrocarbon, benzoyl chloride or aryl diazonium salt, etc. with an olefin to produce a substituted olefin under basic conditions. The reaction has wide substrate applicability, can efficiently synthesize C-C bonds in one step, has high regioselectivity and stereoselectivity of products, and plays an important role in organic synthesis. The Heck reaction is widely applied to the field of organic synthesis of medicines, pesticides, luminescent materials, high polymers and the like, is a research hotspot of catalytic chemistry and organic synthesis, and provides an effective synthesis means for a plurality of natural products, bioactive substances, fine chemicals and intermediates thereof.
The conventional Heck reaction is generally carried out in PdCl2Or Pd (OAc)2The catalyst is carried out under the action of an isohomogeneous catalyst, but the catalyst is easily reduced by palladium ions to generate palladium black in the reaction process, so that the catalyst is deactivated and the application performance of the catalyst is reduced. To improve catalyst life and efficiency, scientists have developed palladium complex catalyst systems in which palladium catalysts containing organophosphorus ligands have been extensively studied, however, the organophosphorus ligands have the disadvantage of being relatively sensitive and toxic. As a nitrogen-containing ligand with smaller toxicity, the N ^ N bidentate palladium complex can also catalyze the Heck reaction with high activity, and provides a new breakthrough for the research on the Heck reaction catalyzed by the palladium complex. In the Heck coupling reaction, the activity of the Pd catalyst is greatly affected by the ligand. Recently, organophosphorus ligands have been developed for the purpose of studying novel Pd complexes. However, to overcome the disadvantages of organophosphorus ligands such as reactivity, toxicity and instability, sp3N-bidentate Pd complexes have been developed and such complexes have good catalytic activity.
Disclosure of Invention
The invention aims to provide a pyridine-imine palladium complex.
Another object of the present invention is to provide a method for preparing the above pyridine-imine palladium complex.
The invention further aims to provide the application of the pyridine-imine palladium complex in the Heck reaction.
The above purpose of the invention is realized by the following technical scheme:
a pyridine-imine palladium complex, the structural formula of which is shown as the following formula (i):
the pyridine-imine palladium complex obtained by the invention has low toxicity when being applied to a Heck reaction for preparing a series of dye intermediates. The conventional Heck reaction is generally carried out in PdCl2Or Pd (OAc)2The method is carried out under the action of a homogeneous catalyst, but the palladium catalyst has poor thermal stability in the reaction process, and palladium ions are easy to reduce to generate palladium black to inactivate the catalyst. The presence of palladium catalysts with organophosphorous ligands greatly improves catalyst life and efficiency, and organophosphorous ligands are generally sensitive to air, cumbersome to operate, highly toxic and environmentally unfriendly, and expensive. Therefore, the pyridine-imine palladium complex prepared by the invention is applied to Heck reaction.
A preparation method of a pyridine-imine palladium complex comprises the following steps:
carrying out substitution reaction on 4-chloroaniline and benzhydrol in a molar ratio of 1:2 to generate 2, 6-di (benzhydryl) -4-chloroaniline (II);
2, 6-bis (benzhydryl) -4-chloroaniline (II) and pyridine-2-formaldehyde are catalyzed by p-toluenesulfonic acid to generate pyridine-imine ligand (III) in a molar ratio of 1: 1;
pyridine-imine ligands (III) with PdCl at room temperature2Reacting at a molar ratio of 1:1 to obtain the pyridine-imine palladium complex (I).
The synthesis reaction formula is as follows:
the invention also provides application of the pyridine-imine palladium complex as a catalyst in a Heck reaction.
The Heck reaction can be seen in the following reaction equation:
the pyridine-imine palladium complex is used as a Heck reaction catalyst for 12-24 h. The reaction temperature is 110 ℃enAt 150 ℃. The reaction solvent is DMA, DMF or Toluene. The base used in the reaction is Na2CO3，K2CO3Or NaOAc to obtain stilbene dye intermediate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the prepared pyridine-imine palladium complex with high thermal stability is not easy to inactivate when being applied to Heck reaction.
(2) The prepared pyridine-imine palladium complex has low toxicity and is environment-friendly.
Drawings
FIG. 1 is a single crystal structural diagram of a pyridine-imine palladium complex prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The structural formula of the pyridine-imine palladium complex in each example is as follows:
the pyridine-imine palladium complex is prepared by the following reaction formula:
the invention provides the application of the pyridine-imine palladium complex as a catalyst in a Heck reaction, wherein the Heck reaction can be seen in the following reaction equation:
the method for calculating the conversion rate of all substrates is used for calculating through gas chromatography tests, and the conversion rate of bromobenzene is obtained through checking the integral area of peaks and then calculating.
Example 1
This example provides 2, 6-bis (benzhydryl) -4-chloroaniline, which was synthesized as follows.
Synthesis of 2, 6-bis (benzhydryl) -4-chloroaniline: adding 4-chloroaniline (2.30g, 23.5mmol) and benzhydrol (8.65g, 47mmol) into a 150mL bottle at room temperature, heating and refluxing, heating to 70 ℃, and dissolving ZnCl with concentrated HCl2(3g, 23.5mmol), after melting of 4-chloroaniline and benzhydryl, ZnCl was added dropwise2The HCl solution was mixed and heated to 160 ℃ for 4 h. After the reaction is stopped, the reaction mixture is cooled to room temperature and CH is added2Cl2Dissolving the solid, extracting, retaining organic phase, adding Na2CO3Removing HCl, filtering, retaining filtrate, adding silica gel into the filtrate to adsorb impurities, filtering, rotary-steaming the filtrate to obtain solid powder, washing with ethyl acetate, and drying in vacuum drying oven to obtain white powder with yield of 82.0%.1H-NMR(400MHz,CDCl3),δ(ppm):7.28-7.12(m,20H,Ph),6.68(s,2H,Ar-H),5.48(s,2H,CH),5.20(s,2H,NH2).13C-NMR(100MHz,CDCl3),δ(ppm):154.10,142.97,138.67,132.07,128.88,127.59,126.76,114.04,55.07.
Example 2
This example provides a pyridine-imine ligand, which was synthesized as follows.
Synthesis of pyridine-imine ligand: pyridine 2-formaldehyde (0.535g, 5.0mmol), 2, 6-bis (benzhydryl) -4-chloroaniline (2.75g, 5.0mmol) and a proper amount of p-toluenesulfonic acid are added into 80mL of toluene, the mixture is heated and refluxed for 8h at 130 ℃, and a crude product obtained after solvent is dried in a spinning mode is recrystallized by ethanol to obtain yellow crystals, wherein the yield is 84.7%.1H-NMR(400MHz,CDCl3),δ(ppm):8.62(d,1H,Py),8.07(d,1H,Py),7.75(t,1H,Py),7.34(t,1H,Py),7.30-7.06(m,12H,Ph),7.01(t,8H,Ph),6.92(s,2H,Ar-H),6.47(s,2H,CH),5.32(s,2H,CH),1.80(s,3H,CH3).13C-NMR(100MHz,CDCl3),δ(ppm):168.81,161.33,151.78,148.52,143.95,143.17,137.89,137.16,130.05,127.89,126.50,123.26,115.18,51.15,16.47.
Example 3
This example provides a pyridine-imine palladium complex, which is synthesized as follows.
Synthesis of pyridine-imine palladium complex: the pyridine-imine ligand (0.548g, 1.0mmol) and PdCl were accurately weighed2(0.177g, 1.0mmol) was added to a 50mL round-bottom flask, 10mL of methanol was slowly added, and the mixture was heated to reflux overnight. After the reaction is finished, filtering while the reaction is hot to obtain a solid, dissolving the solid in 5mL of dichloromethane, performing dry-method column chromatography by using 200-mesh silica gel powder with 300 meshes by using dichloromethane as a mobile phase, decompressing the filtrate to remove the solvent, recrystallizing the obtained solid by using dichloromethane/ethanol (5mL/15mL), filtering, and drying in a vacuum drying oven to obtain light yellow powder with the yield of 82.1%.1H-NMR(400MHz,CDCl3),δ(ppm):9.12(d,1H,Py),7.72(t,1H,Py),7.60(t,1H,Py),7.27-7.04(m,20H,Ph),6.68(s,2H,Ar-H),6.35(d,1H,Py),5.87(s,2H,CH),2.18(s,3H,CH3),1.02(s,3H,Pd-CH3).13C-NMR(100MHz,CDCl3),δ(ppm):172.12,151.07,149.92,143.68,142.04,140.94,137.04,136.35,135.53,130.42,129.73,128.15,126.63,125.35,52.62,21.84,17.33.
Example 4
The prepared pyridine-imine palladium complex is used for catalyzing Heck reaction under different reaction conditions.
Firstly, 4 mu mol (3.8mg) of pyridine-imine palladium complex is dissolved in 5mL of reaction solvent to prepare the solution with the concentration of 8 multiplied by 10- 4And (3) a pyridine-imine palladium complex solution in mol/L. Taking a dry 50mL Schlenk tube, putting a clean dry magnetic stirrer, sequentially adding 2.0mmol (210 mu L,313mg) of bromobenzene, 2.4mmol (280 mu L,254mg) of styrene, 2.2mmol of alkali and 4mL of reaction solvent into the Schlenk tube under the protection of nitrogen, finally taking 50 mu L of solution out of the prepared pyridine-imine palladium complex solution by using a clean injector (the range is 50 mu L), injecting the solution into the Schlenk tube, sealing, placing the reaction solution into methyl silicone oil, stirring at 150 ℃ until the reaction time is stopped, taking 25 mu L of solution out of the reaction solution by using the clean injector (the range is 50 mu L), diluting the taken reaction solution by using the reaction solvent by 3-4 timesAnd then, injecting 1-2 mu L of diluent into the gas chromatography, checking the integral area, and then calculating to obtain the conversion rate of bromobenzene. Meanwhile, the reaction solution was cooled to room temperature, and after cooling to room temperature, the reaction solution was extracted three times with ethyl acetate (3 × 40m L) and deionized water (50mL), the organic phase was taken, then washed three times with saturated saline, and then dried over anhydrous magnesium sulfate to remove a small amount of water remaining in the organic phase, the magnesium sulfate was removed by filtration, and the organic phase was concentrated by rotary evaporation, and then separated by silica gel column chromatography, the solvent was removed by rotary evaporation, and dried in a vacuum oven for 24 hours to obtain a pure white flaky solid (1, 2-stilbene).1H NMR(400MHz,CDCl3),δ(ppm)7.52(d,4H,Ph),7.36(t,4H,Ph),7.26(t,2H,Ph),6.91(s,2H,CH)；13C-NMR(100MHz,CDCl3),δ(ppm):137.25,129.65,128.57,128.46,127.52.
TABLE 1 results of pyridine-imine palladium complexes catalyzed Heck reaction
| Serial number | Alkali | Solvent(s) | Temperature of | Time of day | Conversion rate |
| 1 | Na2CO3 | DMA | 130 | 12 | trance |
| 2 | Na2CO3 | DMA | 150 | 12 | 90 |
| 3 | Na2CO3 | DMA | 150 | 24 | 92 |
| 4 | NaOAc | DMA | 150 | 12 | 78 |
| 5 | KCO3 | DMA | 150 | 12 | 44 |
| 6 | Na2CO3 | DMF | 150 | 12 | 62 |
| 7 | Na2CO3 | Toluene | 110 | 12 | 34 |
From the data in the table 1, we can see that the pyridine-imine palladium complex prepared by the invention can efficiently catalyze Heck to prepare a dye intermediate 1, 2-stilbene; the conventional Heck reaction is generally carried out in PdCl2Or Pd (OAc)2Under the action of homogeneous catalyst, but in the course of reaction PdCl2Or Pd (OAc)2The catalyst has poor thermal stability, palladium ions are easy to be reduced to generate palladium black to deactivate the catalyst, the existence of the palladium catalyst of an organophosphorus ligand greatly improves the service life and efficiency of the catalyst, and the organophosphorus ligand is generally sensitive to air, complicated to operate, high in toxicity and not friendly to environment and high in price (see A.F. Littke, G.C.Fu, J.Am.chem.Soc.123(2001) 6989. 7000. and R.B.Bedford, chem.Comm. (2003)1787 1796.).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A pyridine-imine palladium complex, wherein the pyridine-imine palladium complex has a structure represented by formula (I):
2. the process for preparing a pyridine-imine palladium complex (I) according to claim 1, characterized by comprising the steps of:
(1) carrying out substitution reaction on 4-chloroaniline and benzhydrol to generate 2, 6-di (benzhydryl) -4-chloroaniline, wherein the structural formula is shown as (II);
(2) generating a pyridine-imine ligand by the 2, 6-bis (benzhydryl) -4-chloroaniline (II) prepared in the step (1) and pyridine-2-formaldehyde under the catalysis of p-toluenesulfonic acid, wherein the structural formula is shown as (III);
(3) the pyridine-imine ligand (III) and PdCl prepared by the step (2)2Reacting to obtain the pyridine-imine palladium complex (I) with the structure shown in the formula I.
3. Use of the pyridine-imine palladium complex (I) according to claim 1 as a catalyst in Heck reactions.
4. The pyridine-imine palladium complex according to claim 3, when applied to Heck reaction, the reaction time is 12 h-24 h, the reaction temperature is 110-150 ℃, the reaction solvent is DMA, DMF or Toluene, and the alkali used in the reaction is Na2CO3，K2CO3Or NaOAc.
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| CN112774731A (en) * | 2021-01-22 | 2021-05-11 | 邹育英 | Para-methoxy substituted palladium catalyst and application thereof in Heck reaction |
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| CN112774731A (en) * | 2021-01-22 | 2021-05-11 | 邹育英 | Para-methoxy substituted palladium catalyst and application thereof in Heck reaction |
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