CN108822107B - Method for dehalogenation and reduction of polyhalogenated perylene diimide aromatic hydrocarbon by nickel catalysis - Google Patents
Method for dehalogenation and reduction of polyhalogenated perylene diimide aromatic hydrocarbon by nickel catalysis Download PDFInfo
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Abstract
The invention discloses a dehalogenation reduction method of nickel-catalyzed halogenated perylene diimide arene, which is to realize dehalogenation reduction of polyhalogenated perylene diimide arene in an organic solvent by a catalytic system containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride in a reactor in inert atmosphere. The synthetic route provided by the invention has the advantages of simplicity, high efficiency, cheap raw materials, good repeatability and the like.
Description
Technical Field
The invention relates to a method for dehalogenation and reduction of polyhalogenated perylene diimide aromatic hydrocarbon by nickel catalysis.
Background
Perylene pigments with perylene diimide as a matrix structure belong to high-grade organic pigments, and the pigments have excellent sun-proof and heat-resistant properties and are applied to industrial and building coatings, such as: automobile coatings, metal surface coatings, building exterior wall coatings and the like. The halogenated perylene diimide serving as an intermediate of the perylene pigment can be converted into perylene diimide derivatives containing different substituent groups, so that the pigment has different color differences, and the colorism of the perylene pigment is enriched.
Although the perylene pigment has excellent performance and wide application range, the halogenated perylene diimide is extremely difficult to be naturally degraded. Since the 80's of the 20 th century, the environmental hazards of large quantities of halogen-containing aromatic hydrocarbons have become more and more serious. People degrade the general chemical (such as polychlorinated biphenyl, polybrominated biphenyl and other polyhalogenated aromatic hydrocarbons) into harmless products as much as possible, and therefore, people are dedicated to dehalogenation of halogen-containing organic matters to eliminate the toxicity of the halogen-containing organic matters. In the last half century, the dehalogenation reduction of multimetallic catalytic systems has provided the primary dehalogenation process. However, the method uses noble metals such as rhodium and palladium, and the noble metals are very limited in resources and expensive, so the method is not adopted by the industry. It is imperative to develop a common and inexpensive metal catalytic dehalogenation reduction process. The nickel-containing or titanium-containing compound has abundant reserves in the crust of the earth, and is cheap and easy to obtain. Therefore, the nickel-titanium system is used as the catalyst for dehalogenation and reduction of polyhalogenated aromatic hydrocarbon, and has good practical significance and industrial prospect.
Disclosure of Invention
The invention aims to overcome the defects existing in the dehalogenation reduction process of the polyhalogenated perylene diimide aromatic hydrocarbon catalyzed by the existing noble metal and develop a low-cost and high-efficiency dehalogenation reduction method.
The invention develops new special application by using a cheap reagent nickel dichloride as a catalyst for dehalogenation reduction.
The invention aims to provide a simple and efficient dehalogenation reduction method for a polyhalogenated perylene diimide system.
The invention is characterized in that a combined catalytic system simultaneously containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride efficiently realizes dehalogenation reduction of polyhalogenated perylene diimide aromatic hydrocarbon in one step in an organic solvent.
The invention relates to a dehalogenation reduction reaction of raw material polyhalogenated perylene diimide under the combined action of nickel dichloride, titanium powder and sodium hydride, and the dehalogenated perylene diimide is efficiently produced in one step with the yield up to 99%. The reaction of the invention has low requirements on raw materials, reagents and conditions, simple operation and easy separation and purification.
The technical scheme of the invention is as follows:
a nickel-catalyzed dehalogenation reduction method for polyhalogenated perylene diimide aromatic hydrocarbon is characterized by comprising the following steps: under inert atmosphere, the halogenated perylene diimide arene realizes dehalogenation reduction of the polyhalogenated perylene diimide arene in an organic solvent under a combined catalytic system simultaneously containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride.
Preferably, the method comprises the steps of: (1) adding polyhalogenated perylene diimide aromatic hydrocarbon, nickel dibromide, titanium powder, sodium hydride and an organic solvent in sequence, and heating for reaction; (2) after the reaction is finished, naturally cooling to room temperature; (3) slowly pouring the reaction mixed solution into saturated ammonium chloride aqueous solution for quenching, fully stirring, extracting with dichloromethane for three times, combining organic phases, washing the organic phases twice with distilled water, washing the organic phases once with saturated salt solution, drying with anhydrous sodium sulfate, and removing the organic solvent through a rotary evaporator under reduced pressure to obtain a concentrated mixture; (4) the concentrated mixture was further purified by silica gel column chromatography to obtain the objective compound.
Further preferably, the nitrogen atom of the imide moiety of the polyhalogenated perylene diimide aromatic hydrocarbon is connected to a hydrogen atom, a straight-chain alkyl group, a branched alkyl group, or an aryl group.
Further preferably, the organic solvent is tetrahydrofuran, pyridine, or a mixed solvent of any of these two solvents.
Further preferably, the organic solvent is a mixed solvent of tetrahydrofuran and pyridine in a volume ratio of 1: 1.
Further preferably, the feeding molar ratio of the raw materials of the polyhalogenated perylene diimide arene, the nickel dichloride, the titanium powder and the sodium hydride is 1:0.1-1:4-10:5-20 in sequence.
Further preferably, the feeding molar ratio of the raw materials of the polyhalogenated perylene diimide arene, the nickel dichloride, the titanium powder and the sodium hydride is 1:0.2:6:10 in sequence.
Further preferably, the reaction temperature of the dehalogenation reduction reaction is 60-110 ℃, and the reaction time is 6-24 hours.
Further preferably, the reaction temperature of the dehalogenation reduction reaction is 100 ℃ and the reaction time is 12 hours.
Further preferably, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
The invention has the advantages that:
1. the method provided by the invention can realize high-efficiency dehalogenation reduction in one step, and the reaction route has the advantages of simplicity, high efficiency and environmental friendliness;
2. the method provided by the invention has low requirements on the used raw materials, reagents and solvents;
3. the method provided by the invention has the advantages of good repeatability and high yield which is up to 99%.
Drawings
FIG. 1 shows the reaction scheme of nickel-catalyzed dehalogenation of different reactants according to the preferred embodiment of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The methods described in the following examples are conventional methods unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Referring to FIG. 1, the dehalogenation reduction process of the preferred embodiment of the present invention is shown in formula I:
the dehalogenated perylene diimide product is shown as a formula II:
example 1 preparation of Compound 2a from Tetrachloroperylene diimide
Under the protection of nitrogen, C was added into a 50m L Schlenk reaction tube4Alkyl tetrachloroperylene diimide substrate (1.0mmol), nickel dichloride (0.2mmol), titanium powder (6.0mmol), sodium hydride (10.0mmol), tetrahydrofuran (10.0m L) and pyridine (10.0m L) were heated to 100 ℃ and reacted for 12 hours, after the reaction was finished, they were naturally cooled to room temperature, the reaction mixture was slowly poured into 100m L saturated ammonium chloride aqueous solution to quench, stirred well for 30 minutes, extracted with 100m L dichloromethane, extracted repeatedly three times, the organic phases were combined, washed twice with distilled water, washed with saturated brine once, dried over anhydrous sodium sulfate, and the dichloromethane solvent was removed by rotary evaporator under reduced pressure to give a concentrated mixture, the product was further purified by silica gel column chromatography, adsorbent: 300 and 400 mesh silica gel, eluent: anhydrous methanol and dichloromethane, and 0.447g of compound 2a was finally obtained as a red solid (yield: 89%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 502.2 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.57(d,8H),4.17(t,4H),1.57–1.62(m,4H),1.17–1.20(m,4H),0.93(t,6H).
example 2 preparation of Compound 2a from Tetrabromoperylene diimide
The preparation method is basically the same as example 1, except that: the corresponding tetrachloroperylene diimide in example 1 was replaced with the corresponding tetrabromophylenediimide to obtain 0.402g of compound 2a as a red solid (yield: 80%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 502.2 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.67(d,8H),4.17(t,4H),1.57–1.62(m,4H),1.17–1.20(m,4H),0.93(t,6H).
example 3 preparation of Compound 2b from Tetrachloroperylene diimide
The preparation method is basically the same as example 1, except that: c in example 14Replacement of alkyl tetrachloroperylene diimides by C6Alkyl tetrachloroperylene diimide, 0.430g of compound 2b as a red solid was obtained (yield: 77%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 558.3 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.68(d,8H),4.17(t,4H),1.57–1.63(m,4H),1.16–1.25(m,8H),0.91(t,6H).
example 4 preparation of Compound 2b from Tetrabromoperylene diimide
The preparation method is basically the same as that of example 3, except that: the corresponding tetrachloroperylene diimide in example 3 was replaced with the corresponding tetrabromo perylene diimide. Compound 2b was obtained as a red solid in an amount of 0.457g (yield: 81%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 558.3 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.68(d,8H),4.17(t,4H),1.57–1.63(m,4H),1.16–1.25(m,8H),0.91(t,6H).
example 5 preparation of Compound 2c from Tetrachloroperylene diimide
The preparation method is basically the same as that of example 3, except that: c in example 36Replacement of alkyl tetrachloroperylene diimides by C8Alkyl tetrachloroperylene diimide, 0.541g of compound 2c as a red solid was obtained (yield: 88%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 614.4 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.67(d,8H),4.18(t,4H),1.74(m,4H),1.15–1.25(m,20H),0.89(t,6H).
example 6 preparation of Compound 2c from Tetrabromoperylene diimide
The preparation method is basically the same as example 5, except that: the corresponding tetrachloroperylene diimide in example 5 was replaced with the corresponding tetrabromo perylene diimide. Compound 2c was obtained as a red solid (0.554 g, yield: 90%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 614.4 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.67(d,8H),4.18(t,4H),1.74(m,4H),1.15–1.25(m,20H),0.89(t,6H).
example 7 preparation of Compound 2d from Tetrachloroperylene diimide
The preparation method is basically the same as example 5, except that: c in example 58Replacement of alkyl tetrachloroperylene diimides by C12Alkyl tetrachloroperylene diimide, 0.676g (yield: 93%) of compound 2d as a red solid was obtained.
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 726.5 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.71(d,8H),4.22(t,4H),1.58–0.88(m,46H).
example 8 preparation of Compound 2d from Tetrabromoperylene diimide
The preparation method is basically the same as example 7, except that: the corresponding tetrachloroperylene diimide in example 7 was replaced with the corresponding tetrabromo perylene diimide. Compound 2d was obtained as a red solid (0.690 g, yield: 95%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 726.5 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.71(d,8H),4.22(t,4H),1.58–0.88(m,46H).
example 9 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation method is basically the same as example 7, except that: c in example 712Replacement of alkyl tetrachloroperylene diimide by 2,6-iPrC6H3Aryl tetrachloroperylene diimide, 0.682g of compound 2e was obtained as a red solid (yield: 96%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 710.4 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.81(d,4H),8.78(d,4H),7.5(t,2H),7.35(d,4H),2.76(septet,4H),1.18(d,24H).
example 10 preparation of Compound 2e from Tetrabromoperylene diimide
The preparation method is basically the same as that of example 9, except that: the corresponding tetrachloroperylene diimide in example 9 was replaced with the corresponding tetrabromo perylene diimide. Compound 2e was obtained as a red solid (0.703 g, yield: 99%).
The structural confirmation data for this product are shown below:
mass Spectrometry MS (MA L DI-TOF) 710.4 (M)+).
Nuclear magnetic hydrogen spectrum:1H NMR(400MHz,CDCl3)(ppm):＝8.81(d,4H),8.78(d,4H),7.5(t,2H),7.35(d,4H),2.76(septet,4H),1.18(d,24H).
example 11 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation was substantially the same as in example 9 except that tetrahydrofuran (10.0m L) and pyridine (10.0m L) in example 9 were replaced with tetrahydrofuran (20.0m L), and 0.369g (yield: 52%) of compound 2e was obtained as a red solid.
Example 12 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation was substantially the same as in example 9 except that tetrahydrofuran (10.0m L) and pyridine (10.0m L) in example 9 were replaced with pyridine (20.0m L), whereby 0.540g (yield: 76%) of Compound 2e was obtained as a red solid.
Example 13 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation method is basically the same as that of example 9, except that: the nickel dichloride (0.2mmol), titanium powder (6.0mmol) and sodium hydride (10.0mmol) in example 9 were replaced with nickel dichloride (0.1mmol), titanium powder (4.0mmol) and sodium hydride (5.0 mmol). Compound 2e was obtained as a red solid in an amount of 0.547g (yield: 77%).
Example 14 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation method is basically the same as that of example 9, except that: the nickel dichloride (0.2mmol), titanium powder (6.0mmol) and sodium hydride (10.0mmol) in example 9 were replaced with nickel dichloride (1.0mmol), titanium powder (10.0mmol) and sodium hydride (20.0 mmol). Compound 2e was obtained as a red solid in an amount of 0.575g (yield: 81%).
Example 15 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation method is basically the same as that of example 9, except that: the heating to 100 ℃ in example 9 was replaced by heating to 40 ℃ for 12 hours, and the reaction was carried out for 6 hours. Compound 2e was obtained as a red solid (0.241 g, yield: 34%).
Example 16 preparation of Compound 2e from Tetrachloroperylene diimide
The preparation method is basically the same as that of example 9, except that: the heating to 100 ℃ in example 9 was replaced by heating to 40 ℃ for 12 hours, and the reaction was carried out for 24 hours. Compound 2e was obtained as a red solid (0.368 g, yield: 52%).
The nitrogen is replaced by inert gas argon as protective gas, and the tetrachloro (or tetrabromo) perylene diimide arene can realize dechlorination (or debromination) reduction in an organic solvent in one step with high efficiency under the combined catalytic system simultaneously containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride. The principle is the same and is not described in detail.
In the atmosphere of nitrogen or argon, the tetrachloro (or tetrabromo) perylene diimide aromatic hydrocarbon is replaced by dichloroperylene (or dibromo) perylene diimide, and under the combined catalytic system simultaneously containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride, the dehalogenation reduction can be efficiently carried out in one step in an organic solvent, and the principle is the same, so that the details are omitted.
The above embodiments are merely to explain the technical solutions of the present invention in detail, and the present invention is not limited to the above embodiments, and it should be understood by those skilled in the art that all modifications and substitutions based on the above principles and spirit of the present invention should be within the protection scope of the present invention.
Claims (8)
1. A method for dehalogenating and reducing polyhalogenated perylene diimide aromatic hydrocarbon by nickel catalysis is characterized in that: under inert atmosphere, under the combined catalytic system simultaneously containing catalytic amount of nickel dichloride, excessive titanium powder and excessive sodium hydride, the polyhalogenated perylene diimide arene is dehalogenated and reduced in an organic solvent;
the dehalogenation reduction method is shown as the following general formula I:
the dehalogenation reduction product is shown as the following general formula II:
the organic solvent is tetrahydrofuran, pyridine or any mixed solvent of the two solvents.
2. The method of claim 1, wherein: the method comprises the following steps: (1) adding polyhalogenated perylene diimide aromatic hydrocarbon, nickel dichloride, titanium powder, sodium hydride and an organic solvent in sequence, and heating for reaction; (2) after the reaction is finished, naturally cooling to room temperature; (3) slowly pouring the reaction mixed solution into saturated ammonium chloride aqueous solution for quenching, fully stirring, extracting with dichloromethane for three times, combining organic phases, washing the organic phases twice with distilled water, washing the organic phases once with saturated salt solution, drying with anhydrous sodium sulfate, and removing the organic solvent through a rotary evaporator under reduced pressure to obtain a concentrated mixture; (4) the concentrated mixture was further purified by silica gel column chromatography to obtain the objective compound.
3. The method according to claim 1 or 2, characterized in that: the organic solvent is a mixed solvent of tetrahydrofuran and pyridine according to the volume ratio of 1: 1.
4. The method according to claim 1 or 2, characterized in that: the raw materials of polyhalogenated perylene diimide aromatic hydrocarbon, nickel dichloride, titanium powder and sodium hydride are sequentially fed in a molar ratio of 1:0.1-1:4-10: 5-20.
5. The method of claim 4, wherein: the raw materials of the polyhalogenated perylene diimide arene, the nickel dichloride, the titanium powder and the sodium hydride are sequentially added in a molar ratio of 1:0.2:6: 10.
6. The method according to claim 1 or 2, characterized in that: the reaction temperature of the dehalogenation reduction reaction is 40-100 ℃, and the reaction time is 6-24 hours.
7. The method of claim 6, wherein: the reaction temperature of the dehalogenation reduction reaction is 100 ℃, and the reaction time is 12 hours.
8. The method according to claim 1 or 2, characterized in that: the inert atmosphere is nitrogen atmosphere or argon atmosphere.
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