CN114874099A - Preparation method of alkane chloride - Google Patents

Preparation method of alkane chloride Download PDF

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CN114874099A
CN114874099A CN202210162171.9A CN202210162171A CN114874099A CN 114874099 A CN114874099 A CN 114874099A CN 202210162171 A CN202210162171 A CN 202210162171A CN 114874099 A CN114874099 A CN 114874099A
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chlorine
alkane
acid
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陆文军
徐赉
赵梦迪
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Shanghai Jiaotong University
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    • 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
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/158—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide 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
    • 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
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

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Abstract

The invention relates to a preparation method of alkane chloride, which uses air or oxygen as an oxidant, uses a chlorine-containing compound as the alkane chloride, adds the chlorine-containing compound represented by sodium chloride, a substituent source, alkane, a catalyst or an oxidant and acid into a solvent, adds the solvent into a light-transmitting reaction vessel under the atmosphere of air or oxygen, seals the reaction vessel, stirs the reaction vessel under the conditions of normal pressure and illumination, and obtains the alkane chloride or an ester through analyzing nuclear magnetic yield, extracting, drying and filtering. Compared with the prior art, the invention utilizes cheap and safe chlorine-containing compounds represented by sodium chloride as a chlorine source or a catalyst, can react under the conditions of air normal temperature and normal pressure and containing water, and has the advantages of energy saving, economy, convenient and safe operation and environmental friendliness.

Description

Preparation method of alkane chloride
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of alkane chloride.
Background
The alkane substitute is an important organic chemical, wherein alkane chloride and ester substitute alkane are mainly used as solvents of organic materials and medicines, and bromoalkane is mainly used as an intermediate to be applied to synthesis of various organic materials, medicines and daily necessities. The common alkane is activated to prepare alkane chloride, usually the radical reaction of alkane is adopted, and the reaction is mainly the chlorination reaction with high efficiency, wherein the chlorine source is mainly chlorine gas or chlorine reagent with high valence state (such as NCS). Chlorine (Cl) 2 ) The utilization of chlorine is usually not more than 50 percent, because the equivalent HCl byproduct is generated by the reaction, and chlorine is a highly toxic gas, so the production process has large pollution, and is inconvenient to store, transport and use and very dangerous. The chlorine reagent is not only complex in synthesis, but also poor in atom economy. In addition, in order to improve the utilization rate of chlorine and make the operation more convenient, people also try to use chlorine anions combined with an oxidant as a chlorine source, but the chlorine ions are oxidized to chlorine gas with the standard electrode potential as high as 1.358 volts, and the reactions discovered before are generally more severe in reaction conditions and poor in product selectivity. Wherein the oxidant is high-valence metal ion, sodium hypochlorite, H 2 O 2 Oxone, and the like.
H 2 O 2 Is the greenest oxidizing agent in the reactions reported so far, since its by-product is only water. In 2008, Srinivas et al reported the use of mesoporous molecular sieve SBA-15, hydrochloric acid as the chlorine source, H 2 O 2 Is used as oxidant and is reacted at room temperature in acid system. The reaction chlorine source and the oxidant both need to be excessively added, and the dosage of the molecular sieve is also larger [ Srinivas, D.; saikia, L.Catal.Surv.Asia 2008,12,114]。
Figure BDA0003515261110000011
A part of the prior art disclosed in 2017 reports that chlorination of alkane can be realized at room temperature under the condition of common illumination by using sodium chloride as a chlorine source and adding an oxidant. [ Zhao, m.; lu, W.org.Lett.2017,19, 4560-
Figure BDA0003515261110000021
The conversion of chlorine atoms in this technique is extremely high, but it still requires the addition of the previously prepared oxidant Oxone, and the use of the most ideal air as oxidant cannot be used. The most desirable oxidants are oxygen and air, and alkane chlorination reactions using them as oxidants have not been reported so far.
This laboratory has disclosed a preparation method for bromo alkane in patent CN 108358748B, said method uses sodium nitrite reagent as catalyst, can produce alkane bromide under the condition that bromine anion compound is used as bromine source, air is used as oxidizing agent, said condition uses air as oxidizing agent to implement bromination substitution to alkane and substituted alkane, but said patent is mainly directed at preparation of bromo alkane product, can't obtain chloro product through said method, the invention further improves on the basis of this patent method, have realized the preparation of chloro product. Compared with other chlorination methods, the method has the advantages of direct means, short path, excellent atom economy, mild reaction conditions, simple and convenient operation and environmental friendliness.
Disclosure of Invention
The present invention aims at overcoming the demerits of available technology, and provides one kind of alkane chloride preparing process with air or oxygen as oxidant and chlorine anion compound as chlorine source. The method has the advantages of high chlorine utilization rate, mild reaction conditions, simple and convenient operation and environmental friendliness.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing the chloralkane includes such steps as adding the chloralkane, chlorine-contained compound, catalyst and acid to solvent, adding the solvent to transparent reaction container in air or oxygen atmosphere, sealing, stirring while reacting under ordinary pressure and light, and adding CDCl to the mixture after reaction 3 And internal standard, drying and sampling 1 H NMR analysis to give nuclear magnetic yield using CH 2 Cl 2 Extracting, drying with anhydrous sodium sulfate, filtering, distilling the filtrate under reduced pressure to obtain crude product, and separating the crude product by column chromatography to obtain pure alkane chloride product.
The reaction can be represented by the following overall reaction equation:
Figure BDA0003515261110000022
the chemical structure of the alkane is shown as (I), and R-H is sp-containing 3 All alkanes of C1 to C30 of C-H bonds, including straight, branched or cyclic alkanes, or alkanes bearing one or more substituents, including nitro, carboxyl or aryl groups; such as nitropropane.
The chlorine-containing compound is a compound containing chlorine anions and comprises hydrogen chloride and chlorine-containing metal salt, or quaternary ammonium salt containing the chlorine anions or resin and silica gel loaded with the chlorine anions;
the catalyst is a nitrogen-containing catalyst and comprises nitric acid, nitrous acid, nitrate and nitrite, and nitrogen oxides comprise NO and NO 2 Quaternary ammonium salts containing nitrate or nitrite, or resins and other supporting materials loaded with nitrate, nitrite or nitrogen oxide;
the acids include all protic acids.
The molar weight of the alkane is 50 to 100 times of that of the chlorine-containing compound; the mol weight of the nitrogen-containing reagent catalyst is 0.1 to 300 percent of that of the chlorine-containing compound; the molar amount of the acid is 100 to 500 percent of the chlorine-containing compound or chlorine.
The solvent is an acidic solvent or a neutral solvent.
The acidic solvent is CF 3 CH 2 OH or organic acid, and the neutral solvent is CH 3 NO 2 ，Ph NO 2 ，MeCN，CH 2 Cl 2 Or CHCl 3 . The reaction may also be carried out without addition of a solvent.
The illumination condition is natural light or an external light source, the reaction can be accelerated and the continuity of the reaction can be ensured by properly adding the light source, and the external light source can adopt an incandescent lamp, a straight fluorescent lamp, a compact fluorescent lamp, an LED lamp or an ultraviolet lamp, and the power is more than 4W.
The reaction temperature is controlled to be-5 to 50 ℃, and the reaction time is controlled to be 2 to 48 hours.
The obtained alkane chloride is sp of alkane 3 Monochloride and partial dichloride of C-H bonds.
Compared with the prior art, the invention has the following advantages:
(1) chlorinated alkanes which require more drastic or toxic and harmful production conditions are obtained in a more selective manner in a milder manner.
(2) The synthetic route is short, and the raw materials are simple and cheap.
(3) Chlorine salt (such as NaCl) which is convenient to store and transport can be used as a chlorine source, so that the use of common chlorine is avoided, a large amount of harmful gas cannot be generated, the utilization rate of chlorine atoms is high, and the chlorine-free chlorine storage tank is economic and environment-friendly;
(4) air is used as the final oxidant, so that the cost is greatly reduced, and the method is suitable for being popularized to industrialization;
(5) using nitrogen-containing reagents (e.g. NaNO) 2 ) As catalyst, compared with the commonly used metal catalyst, the price is extremely lowEasy to obtain, low in toxicity and convenient to treat;
(6) the light source used in the reaction is visible light (such as natural light), and a special light source (such as ultraviolet light) is not needed;
(7) the reaction can be carried out under the conditions of normal temperature and normal pressure, the reaction reagent does not need to be dehydrated in advance, a reaction system does not need to be protected by water in the reaction process, and the energy-saving and economic effects are achieved. In a word, the reaction raw materials are cheap and easy to obtain, the operation is convenient and safe, and the method is environment-friendly.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Figure BDA0003515261110000041
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates a reaction at room temperature with nitromethane as the solvent, nitropropane, air and sodium chloride as the starting materials, nitrite as the catalyst, methane in an amount of 10% of the input, methanesulfonic acid as the acid, and a 23 watt LED energy-saving lamp as the light source.
Example 2
Figure BDA0003515261110000042
And adding magnetons into the sealed tube, sequentially adding sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitromethane (0.1L) and hydrochloric acid (0.5mmol,4eq), sealing the tube, using a 23 watt LED lamp at a distance of 3 cm from the tube, and stirring and illuminating. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 HNMR was examined and the yield was calculated.
This example illustrates the reaction of a chlorine source with an acid which is hydrochloric acid.
Example 3
Figure BDA0003515261110000051
The tube was sealed and magnetons were added, followed by sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), dichloromethane (0.1L), hydrochloric acid (0.5mmol,4eq) in that order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 HNMR was examined and the yield was calculated.
This example illustrates the reaction of a chlorine source with an acid such as hydrochloric acid and a solvent such as methylene chloride.
Example 4
Figure BDA0003515261110000052
A magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), nitrobenzene (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 s, precipitating for 10 min, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is nitrobenzene.
Example 5
Figure BDA0003515261110000053
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), acetonitrile (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is acetonitrile.
Example 6
Figure BDA0003515261110000061
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), acetic acid (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in sequence, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is acetic acid.
Example 7
Figure BDA0003515261110000062
Adding magneton into the sealed tube, and sequentially adding sodium chloride (0.5mmol,4eq) and sodium chlorideSodium nitrate (0.0125mmol,0.1eq), nitropropane (0.125mmol,1eq), trifluoroacetic acid (0.1L), methanesulfonic acid (0.5mmol,4eq), sealing the tube, using a 23 watt LED lamp 3 cm from the tube, stirring and illuminating. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the solvent is trifluoroacetic acid.
Example 8
Figure BDA0003515261110000063
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitroethane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is nitroethane.
Example 9
Figure BDA0003515261110000071
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), methyl propionate (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is methyl propionate.
Example 10
Figure BDA0003515261110000072
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), propionic acid (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used at a distance of 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is propionic acid.
Example 11
Figure BDA0003515261110000081
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), alanine amine (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is finished with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is alanine amine.
Example 12
Figure BDA0003515261110000082
Adding magneton, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), dimethyl alanine amine (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) in sequence, sealing the tubeThen, a 23 watt LED lamp is used to be 3 cm away from the tube, and the stirring illumination is carried out. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is dimethyl ammonium propionate.
Example 13
Figure BDA0003515261110000083
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), nitrotert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is nitrotert-butane.
Example 14
Figure BDA0003515261110000091
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), cyano-tert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is cyano-tert-butane.
Example 15
Figure BDA0003515261110000092
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), chlorotert-butane (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is tert-butyl chloride.
Example 16
Figure BDA0003515261110000093
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), pivalic acid (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR check and calculate yield.
This example illustrates the reaction when the starting material is pivalic acid.
Example 17
Figure BDA0003515261110000101
The magneton was added to the tube, sodium chloride (0.5mmol,4eq), sodium nitrite (0.0125mmol,0.1eq), ammonium pivalate (0.125mmol,1eq), nitromethane (0.1L), methanesulfonic acid (0.5mmol,4eq) were added in order, and after the tube was sealed, a 23 watt LED lamp was used 3 cm from the tube, and the tube was stirred and illuminated. The reaction is terminated with CDCl 3 1mL of the diluted solution was added with 0.5g of anhydrous sodium sulfate and a quantitative internal standard CH 2 Br 2 Stirring for 30 seconds, precipitating for 10 minutes, and collecting about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates the reaction when the starting material is amine pivalate.
Example 18
Figure BDA0003515261110000102
Premixed methane with oxygen as 2:1 gas. Sodium nitrite (0.023mmol) is added into a Schlenk tube, vacuum pumping is carried out, 35mL of mixed gas is added into the Schlenk tube after ventilation, 37 percent hydrochloric acid (1.91mmol) and trifluoroacetic acid (0.7mL) are sequentially added, then a screw is screwed, and a 23-watt white LED lamp is used for illumination and stirring at a distance of 1 cm from the reactor. After the reaction was complete, 10mL of CDCl was added 3 After sufficiently shaking, adding quantitative internal standard nitromethane, stirring for 30 seconds, adding 0.5g of anhydrous sodium sulfate, precipitating for 10 minutes, and taking about 500L of supernatant 1 H NMR detected and calculated yield.
This example illustrates a reaction in which the reaction temperature is room temperature, the solvent is trifluoroacetic acid, the raw materials are methane, oxygen and hydrochloric acid, the catalyst is nitrite, the charge amount is 0.2% of methane, and the acid is hydrochloric acid.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of alkane chloride is characterized in that a chlorine-containing compound, alkane, a catalyst and acid are added into a solvent, the solvent is added into a light-transmitting reaction container under the atmosphere of air or oxygen, the container is sealed and stirred to react under the conditions of normal pressure and illumination, and then the alkane chloride is obtained through analysis of nuclear magnetic yield, extraction, drying, filtration, reduced pressure distillation and column layer separation;
wherein the chlorine-containing compound is a compound containing chlorine anions and comprises hydrogen chloride and chlorine-containing metal salt, or quaternary ammonium salt containing the chlorine anions, or resin and silica gel loaded with the chlorine anions.
2. The method of claim 1, wherein the alkane is sp-containing 3 C-H bonded C1 to C30 alkanes.
3. The method of claim 1, wherein the molar amount of the alkane is 25 to 100 times that of the chlorine-containing compound; the molar amount of the acid is 50 to 200 percent of that of the chlorine-containing compound.
4. The method of claim 1, wherein the catalyst is a nitrogen-containing catalyst comprising nitric acid, nitrous acid, nitrate, nitrite, nitrogen oxides comprising NO, NO 2 A quaternary ammonium salt containing nitrate or nitrite, or a resin carrying nitrate, nitrite or nitrogen oxide, and other carrying materials.
5. The method of claim 1, wherein the acid is a protic acid.
6. The method according to claim 1, wherein the lighting condition is natural light or an external light source, and the external light source is an incandescent lamp, a straight fluorescent lamp, a compact fluorescent lamp, an LED lamp or an ultraviolet lamp, and the power is 4W or more.
7. The method for producing an alkane chloride as claimed in claim 1, wherein the reaction temperature is controlled to-5 to 50 ℃.
8. The method for producing an alkane chloride as claimed in claim 1, wherein the reaction time is controlled to 2 to 72 hours.
9. The method of claim 1, wherein the solvent is an acidic solvent or a neutral solvent, and the acidic solvent is CF 3 CH 2 OH or organic acid, and the neutral solvent is CH 3 NO 2 ，PhNO 2 ，MeCN，CH 2 Cl 2 Or CHCl 3 。
10. The method of claim 1, wherein the substituted alkane is sp of alkane 3 A C-H bond.
CN202210162171.9A 2022-02-22 2022-02-22 Preparation method of alkane chloride Pending CN114874099A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
GB1254248A (en) * 1969-07-03 1971-11-17 Gulf Research Development Co A process for preparing chlorinated and brominated aromatic compounds
CN108358748A (en) * 2018-03-28 2018-08-03 上海交通大学 A kind of preparation method of alkane bromo-derivative

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1254248A (en) * 1969-07-03 1971-11-17 Gulf Research Development Co A process for preparing chlorinated and brominated aromatic compounds
CN108358748A (en) * 2018-03-28 2018-08-03 上海交通大学 A kind of preparation method of alkane bromo-derivative

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Title
MENGDI ZHAO AND WENJUN LU: "Visible Light-Induced Oxidative Chlorination of Alkyl sp3 C−H Bonds with NaCl/Oxone at Room Temperature" *
赵梦迪: "可见光驱动的烷烃sp3C-H键氧化氯代和溴代反应" *

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Application publication date: 20220809