CN117886681A - Selective oxidation method for benzyl compound and allyl compound - Google Patents

Selective oxidation method for benzyl compound and allyl compound Download PDF

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CN117886681A
CN117886681A CN202410028290.4A CN202410028290A CN117886681A CN 117886681 A CN117886681 A CN 117886681A CN 202410028290 A CN202410028290 A CN 202410028290A CN 117886681 A CN117886681 A CN 117886681A
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benzyl
reaction
allyl
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许华建
杨新宇
徐俊
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
    • C07J7/0005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21
    • C07J7/001—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group
    • C07J7/0015—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group not substituted in position 17 alfa
    • C07J7/002—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group not substituted in position 17 alfa not substituted in position 16
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a selective oxidation method of benzyl compounds and allyl compounds, which takes benzyl compounds and allyl compounds as raw materials, haloalkane as a catalytic reagent, acetonitrile as a reaction solvent, air as a molecular oxygen source and reacts under the condition of illumination, and benzyl ketone compounds and allyl compounds are generated by selective oxidation. The method has the advantages of high reaction efficiency, mild reaction conditions, convenient operation, economy, green property and the like, and is suitable for large-scale production.

Description

Selective oxidation method for benzyl compound and allyl compound
Technical Field
The invention relates to a selective oxidation method of benzyl compounds and allyl compounds, which enables the benzyl compounds and the allyl compounds to be selectively oxidized into benzyl ketone compounds and allyl ketone compounds by activating molecular oxygen through haloalkane light, and belongs to the field of organic synthesis.
Background
Carbonyl compounds are widely used in various natural products and chemical products, among which benzyl ketone compounds and allyl ketone compounds are the most widely used carbonyl compounds. Has extremely high application value in industrial production, synthesis of drug molecules and reconversion as an intermediate.
The most common method for synthesizing benzyl ketone by benzyl compound is Friedel-Crafts reaction, namely benzene reacts with acetyl chloride, acetic anhydride or acetic acid under the catalysis of stoichiometric anhydrous aluminum trichloride. The synthesis method generates a large amount of toxic organic waste liquid which is difficult to treat and has high cost, and simultaneously has the problems of large catalyst consumption, difficult product separation and the like. In the gas-solid phase catalytic reaction system, the requirements on the catalyst and the reaction device are high, the reaction temperature is high, and a large amount of non-renewable energy sources are required to be consumed. The current industry uses metal complexes to oxidize and prepare at homogeneous phase high temperature, and the yield is lower. Synthesis of allylketones also often requires highly toxic reagents (based on toxic elements such as chromium, selenium) or expensive catalysts (such as palladium, rhodium), which are conflicting with the concept of green chemistry.
In recent years, metal complexes and metal molecular sieves such as Cr and the like are blended with peroxides such as H 2 O 2 Benzyl ketones and TBHP and the like can be prepared by light irradiationAllylketones, which require the consumption of large amounts of peroxides, present a high cost and safety problem.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a selective oxidation method of benzyl compounds and allyl compounds. The method has the advantages of high reaction efficiency, mild reaction conditions, convenient operation, economy, green property and the like, and is suitable for large-scale production.
The invention relates to a selective oxidation method of benzyl compounds and allyl compounds, which is characterized in that benzyl compounds or allyl compounds are used as raw materials, haloalkane is used as a catalytic agent, air is used as a molecular oxygen source, the reaction is carried out under the condition of illumination, and benzyl ketone compounds or allyl ketone compounds are obtained after separation and purification.
Specifically, benzyl compounds or allyl compounds are dissolved in a solvent under the air atmosphere, haloalkane is added as an activating reagent of molecular oxygen, the reaction is carried out under the illumination condition, and after the reaction is finished, benzyl ketone compounds or allyl ketone compounds are obtained through separation and purification.
The structure of the benzyl compound is shown as follows:
the structure of the allyl compound is as follows:
wherein R is 3 、R 4 Is long-chain alkyl, and the total number of carbon atoms is 6-32.
The haloalkane is selected from compounds of the following structure:
the addition amount of the alkyl halide is 5-20eq, calculated by taking a substrate as a reference.
The solvent is selected from acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene, nitromethane or tetrahydrofuran.
The reaction temperature is 25-35 ℃, preferably 30 ℃ and the reaction time is 3-24h.
The illumination wavelength is 365nm-455nm.
The separation and purification are to add saturated sodium bicarbonate water solution into the reaction liquid, then extract the reaction liquid with ethyl acetate for three times, dry the reaction liquid with anhydrous sodium sulfate, remove the solvent by rotary evaporation and then carry out column chromatography separation. The eluent in the column chromatography separation and purification is petroleum ether: ethyl acetate=20:1 to 1:1, v/v.
The reaction route of the invention is schematically shown as follows:
the beneficial effects of the invention are as follows:
1. the synthesis method has the characteristics of green and high efficiency, high yield and wide substrate range.
2. The synthesis method is simple, the synthesis time is short, the reaction can be carried out at normal temperature and normal pressure, the operation is easy, the product selectivity is good, and the yield is high.
3. The synthesis method is suitable for the site-selective oxidation of benzyl and allyl groups in drug molecules.
4. The alkyl halide used for catalysis is redistilled for recycling, and the residue of heavy metal or the post-treatment of toxic reagent waste liquid in the previous reaction are avoided, so that the harm to the environment is reduced, and the reaction cost is reduced.
Detailed Description
To further illustrate the features and advantages of the present invention, the following describes the technical aspects of the present invention in connection with specific embodiments. The following examples are provided to further illustrate the invention and are not intended to limit the invention.
Example 1:
to a 25mL clear Schlenk tube equipped with a magnetic stirrer was added ethyl benzene 1a (0.2 mmol), dibromoethane 1mmol, and 2mL of anhydrous acetonitrile was added under an air atmosphere. After 5h reaction at room temperature with the light wavelength set at 395nm, saturated aqueous sodium bicarbonate ethyl acetate was added to extract 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and then concentrated in vacuo, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=5:1) to give colorless transparent liquid 1b (23 mg, 96%). The nuclear magnetic data of the compound are: 1 H NMR(600MHz,Chloroform-d)δ7.94(d,J＝7.9Hz,2H),7.54(t,J＝7.3Hz,1H),7.44(t,J＝7.7Hz,2H),2.59(s,3H). 13 C NMR(151MHz,Chloroform-d)δ198.11,137.08,133.08,128.54,128.27,126.59.
example 2:
diphenylmethane 2a was used in place of ethylbenzene 1a for a reaction time of 6h, otherwise identical to example 1. The product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=10:1) to give 2b (34.6 mg, 95%) as a white solid. The nuclear magnetic data of the compound are: 1 HNMR(600MHz,Chloroform-d)δ7.81(d,J＝7.3Hz,2H),7.58(t,J＝7.4Hz,1H),7.47(t,J＝7.7Hz,2H).
13 C NMR(151MHz,Chloroform-d)δ196.71,137.57,132.43,130.05,128.28.
example 3:
with 4-nitro-compoundThe reaction time was 24 hours in place of ethylbenzene 1a by phenethyl bromide 3a, and the procedure was as in example 1. The product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=5:1) to give 3b (39.7 mg, 82%) as a pale yellow solid, whose nuclear magnetic data were: 1 H NMR(600MHz,Chloroform-d)δ8.34(d,J＝8.9Hz,2H),8.15(d,J＝9.0Hz,2H),4.46(s,2H). 13 C NMR(151MHz,Chloroform-d)δ190.03,150.83,138.49,130.22,124.18,30.26.
example 4:
phenylbutyric acid 4a was used in place of ethylbenzene 1a for a reaction time of 24h, otherwise identical to example 1. The product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=1:1) to give 4b (26.4 mg, 74%) as a white solid, which had nuclear magnetic data of: 1 HNMR(600MHz,Chloroform-d)δ7.98(dd,J＝8.4,1.3Hz,2H),7.57(t,J＝7.4Hz,1H),7.47(t,J＝7.7Hz,2H),3.31(t,J＝6.6Hz,2H),2.81(t,J＝6.6Hz,2H). 13 C NMR(151MHz,Chloroform-d)δ
197.97,179.04,136.48,133.46,128.77,128.17,33.28,28.18.
example 5:
4-phenylbutyronitrile 5a was used instead of ethylbenzene 1a, and the reaction time was 12h, otherwise identical to example 1. The product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=10:1) to give clear oily liquid 5b (28.1 mg, 89%) as a nuclear magnetic data of the compound: 1 H NMR(600MHz,Chloroform-d)δ7.94(d,J＝7.2Hz,2H),7.61(t,J＝7.4Hz,1H),7.49(t,J＝7.8Hz,2H),3.38-3.36(m,2H),2.76(t,J＝7.2Hz,2H). 13 C NMR(151MHz,Chloroform-d)δ195.45,135.67,133.97,128.95,128.09,119.34,34.33,11.87.
example 6:
Boc-D-homophenylalanine 6a was used in place of ethylbenzene 1a for 24h with the procedure of example 1. The product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=2:1) to give a clear oily liquid 6b (49.7 mg, 81%), the nuclear magnetic data of which were: 1 H NMR(600MHz,Chloroform-d)δ7.94(d,J＝7.3Hz,2H),7.58(t,J＝7.4Hz,1H),7.47(t,J＝7.8Hz,2H),5.62(d,J＝8.5Hz,1H),4.69(dt,J＝8.3,3.9Hz,2H),3.74(s,3H),3.72(d,J＝4.0Hz,1H),3.53(dd,J＝18.1,4.0Hz,1H),1.43(s,9H). 13 C NMR(151MHz,Chloroform-d)δ197.78,172.02,155.56,136.01,133.70,128.71,128.13,80.00,52.64,49.53,40.94,28.29.
example 7:
to a 25mL clear Schlenk tube equipped with a magnetic stirrer was added raw material progesterone 7a (0.2 mmol), dibromoethane 2mmol, and 2mL anhydrous acetonitrile was added under an air atmosphere. After 3.5h reaction at room temperature with the light wavelength set to 395nm, saturated aqueous sodium bicarbonate ethyl acetate was added to extract 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and then concentrated in vacuo, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=2:1) to give 7b (41.9 mg, 49%) as a pale yellow solid. The nuclear magnetic data of the compound are: 1 H NMR(400MHz,Chloroform-d)δ6.16(s,1H),2.68(dd,J＝16.0,4.0Hz,2H),2.58-2.46(m,2H),2.14(s,2H),2.08-2.00(m,1H),1.92(dd,J＝12.3,4.1Hz,3H),1.77-1.69(m,5H),1.50(d,J＝8.3Hz,3H),1.41(d,J＝7.9Hz,1H),1.27(dd,J＝17.2,11.0Hz,2H),1.15(s,5H),0.66(s,4H). 13 C NMR(101MHz,Chloroform-d)δ209.04,201.81,199.48,160.61,125.78,63.21,56.58,50.77,46.59,43.97,39.77,38.21,35.59,34.08,34.02,31.60.
example 8:
to a 25mL clear Schlenk tube equipped with a magnetic stirrer was added cyclohexene 8a (0.2 mmol), dichloroethane 2mmol, and 2mL of anhydrous acetonitrile under an air atmosphere. After 12h reaction at room temperature with the light wavelength set at 395nm, saturated aqueous sodium bicarbonate ethyl acetate was added to extract 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and then concentrated in vacuo, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=5:1) to give colorless liquid 8b (16.3 mg, 85%). The nuclear magnetic data of the compound are: 1 H NMR(400MHz,Chloroform-d)δ6.95-6.90(m,1H),5.94-5.91(m,1H),2.36-2.33(m,2H),2.29-2.26(m,2H),1.96-1.91(m,2H).13C NMR(101MHz,Chloroform-d)δ199.7,150.7,129.8,38.0,25.6,22.7
example 9:
to a 25mL clear Schlenk tube equipped with a magnetic stirrer was added raw material cholesterol 9a (0.2 mmol), dibromoethane 2mmol, and 2mL of anhydrous acetone was added under an air atmosphere. After 5h reaction at room temperature with the light wavelength set to 395nm, saturated aqueous sodium bicarbonate ethyl acetate was added to extract 3 times, the organic phases were combined, dried over anhydrous sodium sulfate, and then concentrated in vacuo, and the product was purified by silica gel column chromatography (petroleum ether: ethyl acetate=2:1) to give 9b (49.6 mg, 62%) as a white solid. The nuclear magnetic data of the compound are: 1H NMR (400 MHz, chloroform-d) delta 5.69 (s, 1H), 3.69-3.64 (m, 1H), 2.53-2.49 (m, 1H), 2.43-2.37 (m, 2H), 2.27-2.21 (m, 1H), 2.05-1.86 (m, 5H), 1.67-1.48 (m, 8H), 1.34-1.07 (m, 13H), 0.93-0.85 (m, 8H), 0.68 (s, 3H); 13C NMR (101 MHz, chloride-d). Delta. 202.5,165.3,126.2,70.6,54.8,53.5,50.0,49.9,45.5,43.2,39.6,38.7,38.4,36.4,36.3,35.8,31.2,28.6,28.1,26.4,23.9,22.9,22.6,21.3,18.9,17.4,12.1.
Example 10:
reference standard for reaction conditions with compound 1 a:
conditions (conditions) Reaction parameters Yield of 2a (%)
1 Standard conditions (air, normal temperature 25 ℃, 395nm wavelength.) 96
2 Reaction under nitrogen 0
3 Reaction under dark conditions 0
4 Replaced by 365nm/455nm light sources 56/23
5 Reaction under pure oxygen condition 82
6 Reaction at 0 DEG C 0
7 Reaction at 30 DEG C 96
8 Reaction at 50 DEG C 90
9 Reaction at 70 DEG C 83
10 Solvent exchange to acetone/dichloromethane/tetrahydrofuran 89/0/76

Claims (9)

1. A process for the selective oxidation of benzyl and allyl compounds characterized by:
using benzyl compound or allyl compound as raw material, using haloalkane as catalytic agent, using air as molecular oxygen source, making reaction under the condition of illumination, and selectively oxidizing to obtain benzyl ketone compound or allyl ketone compound;
the structure of the benzyl compound is shown as follows:
the structure of the allyl compound is as follows:
wherein R is 3 、R 4 Is long-chain alkyl, and the total number of carbon atoms is 6-32.
2. The method according to claim 1, characterized in that:
dissolving a benzyl compound or an allyl compound in a solvent under an air atmosphere, adding haloalkane as an activating reagent of molecular oxygen, reacting under the condition of illumination, and separating and purifying after the reaction is finished to obtain the benzyl ketone compound or the allyl ketone compound.
3. The method according to claim 1, characterized in that:
the alkyl halide is selected from 1,2 dibromoethane, dibromomethane or 1,2 dichloroethane, and the addition amount is 5-20 equivalents.
4. The method according to claim 2, characterized in that:
the illumination wavelength is 365nm-455nm.
5. The method according to claim 2, characterized in that:
the solvent is selected from acetonitrile, acetone, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene, nitromethane or tetrahydrofuran.
6. The method according to claim 2, characterized in that:
the reaction temperature is 25-35 ℃ and the reaction time is 3-24h.
7. The method according to claim 2, characterized in that:
the reaction temperature is normal temperature.
8. The method according to claim 2, characterized in that:
the separation and purification are to add saturated sodium bicarbonate water solution into the reaction liquid, then extract the reaction liquid with ethyl acetate, dry the reaction liquid with anhydrous sodium sulfate, remove the solvent by rotary evaporation and then carry out column chromatography separation.
9. The method according to claim 8, wherein:
the eluent used in the column chromatography separation and purification is petroleum ether: ethyl acetate=20:1 to 1:1, v/v.
CN202410028290.4A 2024-01-09 2024-01-09 Selective oxidation method for benzyl compound and allyl compound Pending CN117886681A (en)

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