CN109336756B - Hydrogenation dehalogenation method of halogenated aromatic hydrocarbon - Google Patents
Hydrogenation dehalogenation method of halogenated aromatic hydrocarbon Download PDFInfo
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
The invention relates to dehalogenation reaction, in particular to a method for hydrogenating and dehalogenating halogenated aromatic hydrocarbon. The method takes imidazole or imidazole derivatives or analogues as a reducing agent, and halogenated aromatic hydrocarbon is hydrogenated and dehalogenated into aromatic hydrocarbon under the action of illumination and a photosensitizer. The specific operation is as follows: halogenated aromatic hydrocarbon, imidazole or imidazole derivative or analogue, catalyst, photosensitizer and alkaline compound are dissolved in organic solvent, then placed in light source environment under the condition of air to make reaction, finally the product is separated by column chromatography, and its yield can be up to 89%. The invention uses imidazole or imidazole derivative or analogue as a reducing agent for hydrodehalogenation for the first time, and uses a photosensitizer for hydrodehalogenation for the first time. Provides a novel method for hydrodehalogenation of halogenated aromatic hydrocarbon, which is mild and easy to operate.
Description
Technical Field
The invention relates to dehalogenation reaction, in particular to a method for hydrogenating and dehalogenating halogenated aromatic hydrocarbon.
Background
In the halogenated aromatic hydrocarbon, the carbon-halogen bond energy of brominated aromatic hydrocarbon and iodo aromatic hydrocarbon is smaller, and the carbon-halogen bond energy of chlorinated aromatic hydrocarbon and fluoro aromatic hydrocarbon is larger; in addition, brominated aromatic hydrocarbon and iodo aromatic hydrocarbon are easy to prepare and are cheaper, and chlorinated aromatic hydrocarbon and fluorinated aromatic hydrocarbon are generally higher in price, so that the chlorinated aromatic hydrocarbon and the fluorinated aromatic hydrocarbon have good application value after being effectively treated; most of the reported toxic halogenated aromatic hydrocarbons are chlorinated aromatic hydrocarbons, such as hexachloro cyclohexane, dioxin, and the like.
There have been many reports on the hydrogenation of aryl and alkyl halides. The metal catalyst exhibits excellent performance in this respect. However, activation of C-F bonds and C-Cl bonds by transition metal complexes is a major challenge. Hydrofluoric acid is considered to be the best material for defluorination, however, other effective catalysts need to be developed due to the strong corrosiveness of hydrofluoric acid. Researchers have therefore focused on and developed many highly efficient transition metal catalysts, and to date there are many examples of Rh, Zr, Nb, Fe, Ru, Ti and Ni catalysts.
The hydrogenation of the C-Cl bond of the aromatic compound is also usually dominated by transition metals, mainly Ru, Rh, Ni, Pd, Pt, etc. These transition metal catalysts are mostly noble metals and have high toxicity.
On the premise that transition metal catalysis is the mainstream, relatively novel catalytic technologies such as photocatalysis and electrocatalysis have been reported. Compared with the transition metal catalysis, the catalytic technology has the advantages of milder reaction conditions and higher reaction speed. But has the disadvantage of being less applicable than transition metal catalysis.
Palladium on carbon and metallic nickel catalytic hydrogenation are well-known hydrodehalogenation methods, but such methods inevitably use hydrogen and pressure reactors. Moreover, the metal catalysts are difficult to catalyze due to the high bond energy of C-F bonds and C-Cl bonds.
Disclosure of Invention
The invention provides a mild hydrogenation and dehalogenation method of halogenated aromatic hydrocarbon, which is used for carrying out photocatalytic hydrogenation and dehalogenation at room temperature.
The invention provides the following technical scheme:
a process for hydrogenating and dehalogenating the halogenated aromatic hydrocarbon features that the imidazole or its derivative or analog is used as reducer, and under the action of light and photosensitizer, the halogenated aromatic hydrocarbon is hydrogenated and dehalogenated into aromatic hydrocarbon.
Further, the imidazole derivative or analog is 1-vinylimidazole, N-ethylimidazole, 2-bromo-4-nitroimidazole, 1, 2-dimethylimidazole, 4-nitroimidazole, benzimidazole, 1-N-butylimidazole, 4-iodo-1H-imidazole, 1- (4-nitrobenzyl) imidazole, 1- (4-aminobenzyl) imidazole, 2,5, 6-trimethylbenzimidazole, 2- (trifluoromethyl) benzimidazole, 2-hydroxybenzimidazole, 1-tritylimidazole, 2,4, 5-triiodoimidazole, 4, 5-diiodo-1H-imidazole, 1-ethyl-3-methylimidazole iodide, 1-octyl-3-methylimidazole chloride, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole chloride, (2,4, 6-triisopropylphenylsulfonyl) imidazole, 2-mercaptomethylbenzimidazole, 1- (4-formylphenyl) imidazole, 1- (4-nitrophenyl) -1H-imidazole, 1- (4-aminophenyl) imidazole, N-propylimidazole, N-acetylimidazole, 2-chloro-4-nitroimidazole, 2-mercapto-1-methylimidazole, 2-undecylimidazole, 2, 4-dimethylimidazole, 4, 5-diphenylimidazole, 4-azabenzimidazole, 2-methylimidazole, 4-methylimidazole or 4-iodoimidazole.
Further, the photosensitizer is methylene blue, rose bengal, eosin B, eosin Y, or fluorescein.
Further, the specific operation is as follows:
halogenated aromatic hydrocarbon, imidazole or imidazole derivatives or analogues, a catalyst, a photosensitizer and an alkaline compound are dissolved in an organic solvent, then the mixture is placed under a light source to react under the air condition, and finally the product is separated by column chromatography, wherein the catalyst is copper salt, iron salt or aluminum salt. The reaction formula is as follows:
in the formula, X is F, Cl, Br or I, and R is any substituent.
Further, the molar ratio of the halogenated aromatic hydrocarbon, the imidazole or the imidazole derivative or the analog and the basic compound is 1:1: 1.8.
Further, the amount of the catalyst is 12mmol%, and the amount of the photosensitizer is 2 mmol%.
Further, the wavelength of the light source is 254 nm. The irradiation energy at a wavelength of 254nm is strong, and the hydrodehalogenation effect of the halogenated aromatic hydrocarbon is good under the ultraviolet light condition at a wavelength of 254nm, and it is presumed that the hydrodehalogenation reaction of the halogenated aromatic hydrocarbon can also proceed under the irradiation of light at other wavelengths.
Further, the basic compound is lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, magnesium tert-butoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride or calcium hydride.
Further, the organic solvent is any one or two of isopropanol, methanol, ethanol, DMF, DMA, DMSO or acetonitrile.
Compared with the prior art, the invention has the beneficial effects that:
1. in the traditional method, hydrogenation and dehalogenation reaction are mostly carried out under the conditions of high temperature and high pressure, and noble metal catalysts such as nickel, ruthenium, palladium and the like are also used, and the noble metal catalysts have high toxicity. The invention is carried out under the illumination condition, and has the advantages that the light belongs to clean energy and is very environment-friendly. The illumination condition is easy to realize, and the reaction condition is easy to control: the light source is turned on in response to the start, and turned off otherwise. This is not possible with conventional heating methods. Wherein, the reaction yield is higher under the ultraviolet condition with the wavelength of 254nm, mainly because the illumination energy of the wavelength band is stronger, the dehalogenation effect is better.
2. The invention uses imidazole or imidazole derivatives or analogues for the first time as a reducing agent for hydrodehalogenation.
3. In the method, the catalyst is copper salt, iron salt or aluminum salt, and compared with the traditional method, the method has the advantages of wide source range of the copper salt, the iron salt or the aluminum salt, low price, small toxicity, no toxicity and environmental protection.
4. The invention uses the photosensitizer for hydrodehalogenation reaction for the first time. Photosensitizers are organic compounds and are easily degraded. In addition, the photosensitizer can increase the absorption of light energy by reactants and accelerate the reaction. After the photosensitizer is added, the use of metal salt can be reduced or even eliminated.
5. The addition of the basic compound significantly increases the yield.
Drawings
FIG. 1 is a nuclear magnetic diagram of the product obtained in example 2 of the present invention.
FIG. 2 is a nuclear magnetic diagram of the product obtained in example 3 of the present invention.
FIG. 3 is a nuclear magnetic diagram of the product obtained in example 4 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1 hydrodechlorination of o-chlorobenzoic acid
Step 1: 78mg (0.5mmol) of o-chlorobenzoic acid, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of ammonium copper sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli t-butoxide were weighed out in a quartz reaction tube, respectively. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 87%. The product obtained is benzoic acid.
EXAMPLE 22 Hydrodechlorination of chloro-N-phenylbenzamide
Step 1: 116mg (0.5mmol) of 2-chloro-n-phenylbenzamide, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of ammonium copper sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli tert-butoxide were weighed out in a quartz reaction tube, respectively. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 87%. The product obtained is a nitrogen-phenyl benzamide.
EXAMPLE hydrodechlorination of 32-chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of ammonium copper sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli tert-butoxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction is finished, the product is separated by column chromatography, and the yield is 85%. The obtained product is p-methyl benzoic acid.
EXAMPLE 42 hydrodechlorination of chloro-5-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-5-methylbenzoic acid, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of ammonium copper sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli tert-butoxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction, the product was isolated by column chromatography with a yield of 86%. The product obtained is 5-methylbenzoic acid.
EXAMPLE 52 hydrodechlorination of chloro-5-nitrobenzoic acid
Step 1: 101mg (0.5mmol) of 2-chloro-5-nitrobenzoic acid, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of ammonium copper sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli tert-butoxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 89%. The product obtained is 5-nitrobenzoic acid.
EXAMPLE 62 Hydrodechlorination of chlorobenzamide
Step 1: 78mg (0.5mmol) of 2-chlorobenzamide, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of cuprammonium sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli t-butoxide were weighed out in a quartz reaction tube, respectively. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 79%. The product obtained was benzamide.
Example 72 Hydrodechlorination of chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 34mg (0.5mmol) of imidazole, 24mg (12 mmol) of copper ammonium sulfate (hexahydrate), 7mg (2 mmol) of eosin Y, and 72mg (0.9mmol) of lithium t-BuOli-butoxide are weighed out in a quartz reaction tube, respectively. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction, the product was isolated by column chromatography with a yield of 80%. The obtained product is p-methyl benzoic acid.
Example hydrodechlorination of 82-chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 73mg (0.5mmol) of 5, 6-dimethyl-1-hydrobenzimidazole, 24mg (12 mmol) of cuprammonium sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli-t-butoxide were weighed out in a quartz reaction tube, respectively. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 81%. The obtained product is p-methyl benzoic acid.
Example hydrodechlorination of 92-chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 41mg (0.5mmol) of 4-methylimidazole, 24mg (12 mmol) of cuprammonium sulfate (hexahydrate), 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli-butoxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction was completed, the product was isolated by column chromatography with a yield of 81.5%. The obtained product is p-methyl benzoic acid.
EXAMPLE 102 Hydrodechlorination of chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 34mg (0.5mmol) of imidazole, 6mg (12 mmol) of ferrous sulfide, 11mg (2 mmol) of rose bengal, and 72mg (0.9mmol) of lithium t-BuOli t-butoxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction is finished, the product is separated by column chromatography. The yield was 80%. The obtained product is p-methyl benzoic acid.
EXAMPLE 112 hydrodechlorination of chloro-4-methylbenzoic acid
Step 1: 85mg (0.5mmol) of 2-chloro-4-methylbenzoic acid, 34mg (0.5mmol) of imidazole, 6mg (12 mmol) of ferrous sulfide, 11mg (2 mmol) of rose bengal, and 36mg (0.9mmol) of sodium hydroxide were weighed out respectively in a quartz reaction tube. Isopropyl alcohol and DMF, each 1.5ml, were added as solvents.
Step 2: the quartz reaction tube is placed under 254nm ultraviolet light under air condition for full illumination for 72 hours. The reaction formula is as follows:
and step 3: after the reaction, the product was isolated by column chromatography with a yield of 80.5%. The obtained product is p-methyl benzoic acid.
The above examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The range of parameters within which the present invention can be practiced is not limited to those specifically exemplified in the following examples. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Claims (7)
1. A method for hydrogenating and dehalogenating halogenated aromatic hydrocarbon is characterized in that imidazole or imidazole derivatives or analogues are used as a reducing agent, and the halogenated aromatic hydrocarbon is hydrogenated and dehalogenated into aromatic hydrocarbon under the action of illumination and a photosensitizer; the imidazole derivative or analog is 5, 6-dimethyl-1-hydrobenzimidazole or 4-methylimidazole; the photosensitizer is rose bengal or eosin Y.
2. The process according to claim 1, characterized by the fact that it is carried out in the following manner:
halogenated aromatic hydrocarbon, imidazole or imidazole derivatives or analogues, a catalyst, a photosensitizer and an alkaline compound are dissolved in an organic solvent, then the mixture is placed under a light source to react under the air condition, and finally the product is separated by column chromatography, wherein the catalyst is copper salt, iron salt or aluminum salt.
3. The process according to claim 2, wherein the molar ratio of halogenated aromatic hydrocarbon, imidazole or its derivative or analogue to basic compound is 1:1: 1.8.
4. The process according to claim 2, wherein the catalyst is used in an amount of 12mmol% and the photosensitizer is used in an amount of 2 mmol%.
5. The method as claimed in claim 2, wherein the light source has a wavelength of 254 nm.
6. The process of claim 2, wherein the basic compound is lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, magnesium tert-butoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride or calcium hydride.
7. The method of claim 2, wherein the organic solvent is one or two selected from isopropanol, methanol, ethanol, DMF, DMA, DMSO, and acetonitrile.
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