CN108358748B - Preparation method of alkane bromide - Google Patents
Preparation method of alkane bromide Download PDFInfo
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- CN108358748B CN108358748B CN201810266510.1A CN201810266510A CN108358748B CN 108358748 B CN108358748 B CN 108358748B CN 201810266510 A CN201810266510 A CN 201810266510A CN 108358748 B CN108358748 B CN 108358748B
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Abstract
The invention relates to a preparation method of alkane bromide, which comprises the steps of adding alkane, bromine-containing compound or elemental bromine, catalyst and acid into a solvent, adding the solvent into a light-transmitting reaction container under the atmosphere of air or oxygen, sealing, stirring and reacting under the conditions of normal pressure and illumination, and obtaining the alkane bromide through analysis of nuclear magnetic yield, extraction, drying, filtration, reduced pressure distillation and column layer separation. Compared with the prior art, the method has the advantages that cheap and safe bromine salt is used as a bromine source, air is used as an oxidant, and a nitrogen-containing reagent is used as a catalyst, so that the reaction can be carried out under the conditions of normal temperature and normal pressure, the method is energy-saving and economical, the operation is convenient and safe, and the method is environment-friendly.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of alkane bromide.
Background
The alkane bromide is an important organic chemical, and is mainly used as an intermediate to be applied to the synthesis of various organic materials, medicines and daily necessities. Preparation of alkane bromides typically employs radical bromination of alkanes, where the bromine source is predominantly elemental bromine or a higher bromine reagent (e.g., NBS). Elemental bromine (Br)2) The bromine utilization of (2) is usually not more than 50%, because an equal amount of HBr byproduct is generated, and the bromide is a toxic substance, has large pollution in the production process, is inconvenient to store, transport and use and is very dangerous. Bromine reagents are not only complex to synthesize themselves, but also have poor atom economy. In addition, people also try to use bromine anions combined with an oxidant as a bromine source, so that the utilization rate of bromine is improved, and the operation is relatively convenient. The oxidant is PhI ═ O, m-chloroperoxybenzoic acid (MCPBA), NaIO4，H2O2And the like.
H2O2Is the greenest oxidizing agent in the reactions reported so far, since its by-product is only water. In 2000, Pombeiro et al reported Ca [ V (HIDA)2](HIDA) basic form of 2,2A- (hydroxyimino) diacetic acid) as catalyst, KBr as bromine source, H2O2Is used as an oxidizing agent, and is subjected to cyclohexane bromination reaction at room temperature under an acidic system. But its yield is only 10% and the bromine utilization is also very low [ Reis, p.m.; silva, j.a.l.; da Silva, j.j.r.f.; pombeiro, A.J.L.chem.Commun.2000, 1845-1846]。
2008A patent [ CN 101306968A, 2008.6.30; li, Y.; ju, j.; jia, j.; sheng, w.; han, L.; gao, J.Chin.J.chem.2010,28,2428-2432]Diatomaceous earth as catalyst, HBr as bromine source, H2O2The reaction was carried out under heating at 80 ℃ and irradiation with a 60W incandescent lamp. The yield is improved by more than that of the prior art and can reach 80 percent.
But the oxidant for this reaction is H2O2It is prepared in advance, is easy to be decomposed by visible light and is not easy to be stored. The most desirable oxidants are oxygen and air, and alkane bromination reactions using them as oxidants have not been reported so far.
A patent in 2006 [ CN 100462343C, 2006.12.28; wan, s.; wang, s.r.; lu, W.J.org.chem.2006,71,4349-4352 discloses a preparation method of brominated aromatic hydrocarbon. The method uses a nitrogen-containing reagent as a catalyst, and can generate the aromatic bromide under the conditions that a bromine negative ion compound is used as a bromine source and air is used as an oxidant. However, this method is not effective for the bromination reaction of alkanes.
A prior art disclosed in 2017 reports that chlorination of alkane can be realized at room temperature under common illumination conditions by using sodium chloride as a chlorine source and adding an oxidant. [ Zhao, m.; lu, W.org.Lett.2017,19,4560-
However, the addition of the previously prepared oxidant Oxone is still required in this prior art, and the most ideal air cannot be used as the oxidant. And the bromination reaction is less reactive than the chlorination reaction and is less easy to proceed than the chlorination reaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of alkane bromide by using air or oxygen as an oxidant and a bromine anion compound as a bromine source under the condition of illumination. The method has the advantages of high bromine 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 bromide of alkane includes such steps as adding alkane, bromine compound or elementary bromine, catalyst and acid to solvent, adding the solvent to transparent reactor in air or oxygen atmosphere, sealing, stirring while reacting under ordinary pressure and light, and adding CDCl to the mixture after reaction3And internal standard, drying and sampling1H NMR analysis to give nuclear magnetic yield using CH2Cl2Extracting, 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 bromoalkane product.
The reaction can be represented by the following overall reaction equation:
the chemical structure of the alkane is shown as (I), and R-H is sp-containing3All 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;
the bromine-containing compound is a compound containing bromine anions and comprises hydrogen bromide and bromine metal salt, or quaternary ammonium salt containing the bromine anions, or resin and silica gel loaded with the bromine anions;
the catalyst is a nitrogen-containing catalyst and comprises nitric acid, nitrous acid, nitrate and nitrite, and nitrogen oxides comprise NO and NO2A quaternary ammonium salt containing nitrate or nitrite, or a resin or other supporting material carrying nitrate, nitrite or nitrogen oxideFeeding;
the acid includes all protonic acids or Lewis acids, including sulfuric acid, hydrochloric acid or CF3CO2H, and additional materials that can produce such acids in the reaction.
The molar weight of the alkane is 50 to 100 times of that of the bromine-containing compound or the elemental bromine; the molar weight of the nitrogen-containing reagent catalyst is 0.1 to 300 percent of that of bromine-containing compound or elemental bromine; the molar amount of the acid is 100 to 500 percent of the bromine-containing compound or the elemental bromine.
The solvent is an acidic solvent or a neutral solvent.
The acidic solvent is CF3CH2OH, the neutral solvent is CH2Cl2Or CHCl3. 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 at-5 to 50 degrees celsius, wherein relatively electron-rich alkanes (e.g., cyclohexane) can be carried out at room temperature, and the reaction can be accelerated by appropriately raising the temperature relative to electron-poor alkanes (e.g., nitropropane). The reaction time is controlled to be 2-48 hours until the orange red of the bromine basically fades.
The prepared alkane bromide is sp of alkane3Monobrominated of C-H bonds.
Compared with the prior art, the invention has the following advantages:
(1) the bromine salt (such as KBr) which is convenient to store and transport is used as the source of bromine, so that the use of bromine is avoided, a large amount of harmful gas is not generated, the utilization rate of bromine is high, and the bromine is economic and environment-friendly;
(2) the air is used as the final oxidant, so that the cost is greatly reduced, and the method is suitable for being popularized to industrialization;
(3) using nitrogen-containing reagents (e.g. NaNO)2) As a catalyst, the catalyst has low price, easy acquisition, low toxicity and convenient treatment;
(4) 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;
(5) 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
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CF at room temperature3CH2OH (0.2mL), cyclohexane (cyclohexane) (105.2mg, 1.25mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction tube is stirred for 13 hours under the irradiation of a 4W LED with the distance of about 10cm until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave bromocyclohexane (bromocyclohexane) in a yield of 71% based on KBr, with 5% based on KBr of 1, 2-dibromocyclohexane. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction temperature as room temperature and the solvent as CF3CH2OH, the raw material is unsubstituted cyclic alkane, catalyzingThe agent is NaNO2The material amount is 10% of bromine source, the acid is concentrated hydrochloric acid, and the reaction is carried out under the irradiation of an LED.
Example 2
A35 mL glass reaction tube was charged with a magnetic stirrer, NaBr (25.7mg, 0.25mmol), cyclohexane (cyclohexane) (105.2mg, 1.25mmol), 40% NaNO at room temperature2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (63. mu.L, 0.75mmol) were quickly closed and sealed. The reaction tube is stirred for 12 hours under the irradiation of 23W CFL with the distance of about 10cm until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave bromocyclohexane (bromocyclohexane) in a yield of 61% based on KBr, with 12% based on KBr of 1, 2-dibromocyclohexane. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction without solvent, with NaBr as the bromine source, under CFL irradiation.
Example 3
A25 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), cyclohexane (cyclohexane) (105.2mg, 1.25mmol), 40% NaNO at room temperature2Aqueous (6.4mg, 0.038mmol) and 37% aqueous HCl (63. mu.L, 0.75mmol) were quickly closed and sealed. The reaction tube was stirred for 8.5 hours under the irradiation of a 23W CFL at a distance of about 10cm until the color of bromine in the reaction tube substantially faded to terminate the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave bromocyclohexane (bromocyclohexane) in a yield of 70% based on KBr, with 4% (based on KBr) of 1,2-dibromocyclohexane (1,2-dibromocyclohexane) being formed. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates a reaction with 15% catalyst and 3 equivalents acid based on KBr.
Example 4
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CF at room temperature3CH2OH (0.2mL), cyclopentane (104.3mg, 1.5mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction tube was stirred for 9 hours under the irradiation of a CFL of 23W at a distance of about 10cm until the color of bromine in the reaction tube substantially faded to terminate the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1Analysis by H NMR gave bromocyclopentane (bromocylopentane) in 69% yield based on KBr. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction of an alkane having a C5 alkane.
Example 5
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), cyclooctane (112.2mg, 1.0mmol), and 40% NaNO at room temperature2Aqueous (4.3mg, 0.025mmol), trifluoroacetic acid (21. mu.L, 0.25mmol) and 37% aqueous HCl (63. mu.L, 0.75mmol) were quickly closed with a suitable cap and sealed. The reaction tube was stirred under the irradiation of 23W CFL at a distance of about 10cm for 6 hours until the color of bromine in the reaction tube substantially faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying,sampling is carried out1H NMR analysis gave bromocyclooctane (bromocyclooctane) in 80% yield based on KBr. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction of an alkane having a C8 alkane.
Example 6
Air in a 25mL Schleck tube glass reaction tube (containing a stirrer) was replaced with oxygen at room temperature2Under the atmosphere, KBr (29.8mg, 0.25mmol) and CHCl were added3(0.2mL), adamantane (adamantane) (34.1mg, 0.25mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction tube is stirred for 24 hours under the irradiation of 23W CFL with the distance of about 10cm until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave a yield of 67% monobromoadamantane based on KBr, 47% of which was 1-bromoadamantane (1-bromoadamantane) and 20% was 2-bromoadamantane (2-bromoadamantane). Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction atmosphere as O2The alkane is C10 alkane, and the solvent is CHCl3The reaction of (1).
Example 7
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CHCl3(0.18mL), pivalonitrile (62.3mg, 0.75mmol), 40% NaNO2Aqueous solution (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a complementary cap and sealed. The reaction was carried out at 40 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 24 hours until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave 3-bromo-2, 2-dimethylpropionitrile (3-bromo-2,2-dimethyl propanitrile) in a yield of 73% based on KBr.
This example illustrates the reaction of a branched alkane having a cyano group at a temperature of 40 ℃ under heating.
Example 8
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CHCl3(0.18mL), pivalic acid (76.6mg, 0.75mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction was carried out at 40 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 24 hours until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1By H NMR analysis, 3-bromo-2, 2-dimethylpropionic acid (3-bromo-2,2-dimethylpropanoic acid) was obtained in a yield of 73% based on KBr.
This example illustrates the reaction of an alkane which is a branched alkane having a carboxyl group.
Example 9
Air in a 25mL Schleck tube glass reaction tube (containing a stirrer) was replaced with oxygen and oxygen was added2Under the atmosphere, KBr (29.8mg, 0.25mmol) and CHCl were added3(0.18mL), 2-methyl-2-nitropropane (98.0mg, 0.95mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction was carried out at 40 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 25 hours until the color of bromine in the reaction tube is basically faded to finish the reaction. The bottle cap was opened and 2mL of the solution was added to the reaction mixture CDCl3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave a yield of 67% of 1-bromo-2-methyl-2-nitropropane (1-bromo-2-methyl-2-nitropropane) based on KBr. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction of an alkane which is a branched alkane with a nitro group.
Example 10
Air in a 25mL Schleck tube glass reaction tube (containing a stirrer) was replaced with oxygen and oxygen was added2Under the atmosphere, KBr (29.8mg, 0.25mmol) and CH were added2Cl2(0.18mL), nitropropane (66.8mg, 0.75mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction was carried out at 40 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 15 hours until the color of bromine in the reaction tube is basically faded to finish the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave a yield of 83% of monobrominated product based on KBr, of which 49% of 1-bromo-3-nitropropane (1-bromo-3-nitropropane) and 34% of 2-bromo-1-nitropropane (2-bromo-1-nitropropane). Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction of an alkane which is a linear alkane with a nitro group.
Example 11
Air in a 25mL Schleck tube glass reaction tube (containing a stirrer) was replaced with oxygen and oxygen was added2Under the atmosphere, KBr (29.8mg, 0.25mmol) and CH were added2Cl2(0.18mL), nitroethane (93.8mg, 1.25mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction was carried out at 50 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 36 hours until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave a yield of 15% 1-bromo-2-nitroethane (1-bromo-2-nitroethane) based on KBr.
This example illustrates the alkane as C2 and the solvent as CH2Cl2The reaction temperature is 50 ℃ under heating condition.
Example 12
Air in a 25mL Schleck tube glass reaction tube (containing a stirrer) was replaced with oxygen and oxygen was added2Under the atmosphere, KBr (29.8mg, 0.25mmol) and CHCl were added3(0.18mL), propionic acid (propanoic acid) (63.0mg, 0.85mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction was carried out at 40 ℃ under 23W CFL irradiation at a distance of about 10 cm. Stirring for 18 hours until the color of bromine in the reaction tube is basically faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1By H NMR analysis, a yield of bromopropionic acid based on KBr of 92% was obtained, of which 68% was 3-bromopropionic acid (3-bromopropionic acid) and 24% was 2-bromopropionic acid (2-bromopropionic acid).
This example illustrates the reaction of a carboxy-substituted linear alkane.
Example 13
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CF at room temperature3CH2OH (0.2mL), n-hexane (107.7mg, 1.25mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42 μ L,0.5mmol), quickly covering a matched cover, and sealing. The reaction tube was stirred under the irradiation of 23W CFL at a distance of about 10cm for 16 hours until the color of bromine in the reaction tube substantially faded to end the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis gave a KBr-based yield of 47% for n-bromohexane, 2-bromohexane (2-bromohexane) 27% and 3-bromohexane (3-bromohexane) 20%.
This example illustrates the reaction of a linear alkane wherein the alkane is unsubstituted.
Example 14
A35 mL glass reaction tube was charged with a magnetic stirrer, KBr (29.8mg, 0.25mmol), CHCl at room temperature3(0.18mL), 1-methyl-4-nitrobenzene (34.3mg, 0.25mmol), 40% NaNO2Aqueous (4.3mg, 0.025mmol) and 37% aqueous HCl (42. mu.L, 0.5mmol) were quickly closed with a suitable cap and sealed. The reaction tube was stirred for 17 hours under the irradiation of a CFL of 23W at a distance of about 10cm until the color of bromine in the reaction tube substantially faded to terminate the reaction. The bottle cap was opened and 2mL of CDCl was added to the reaction mixture3And internal standard CH2Br2Adding 0.5g of anhydrous sodium sulfate, drying, sampling and carrying out1H NMR analysis showed that the benzyl bromide product, 1-bromomethyl-4-nitrobenzene (1- (bromomethyl) -4-nitrobenzene), was obtained in 67% yield. Using CH for the reaction solution2Cl2Extracting, separating out an organic phase, adding anhydrous sodium sulfate, drying, filtering to remove inorganic salts, and distilling the filtrate under reduced pressure to remove most of the solvent to obtain a crude product; the crude product can be separated by column chromatography to obtain the product.
This example illustrates the reaction of an alkane that is an aryl substituted C1 alkane.
Example 15
A process for preparing the brominated substance of alkane includes such steps as mixing alkane with hydrogen bromide, nitric acid catalyst and sulfuric acid, and adding the mixture of sp3C4 straight-chain alkane with C-H bond, the molar weight of the alkane is 50 percent of that of the hydrogen bromide, the molar weight of the nitric acid catalyst is 0.1 percent of that of the hydrogen bromide, and sulfuric acidThe molar weight of the hydrogen bromide is 100 percent, the hydrogen bromide is added into a light-transmitting reaction container under the air atmosphere, the container is sealed, the stirring reaction is carried out under the conditions of normal pressure and natural illumination, the reaction temperature is controlled at minus 5 ℃, the reaction is carried out for 48 hours, and after the reaction is finished, the mixed reaction is added with CDCl3And internal standard, drying and sampling1H NMR analysis to give nuclear magnetic yield using CH2Cl2Extracting, 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 bromoalkane product.
Example 16
A process for preparing the brominated substance of alkane includes such steps as adding alkane, elementary bromine, quaternary ammonium salt catalyst containing nitrate radical and hydrochloric acid to acidic solvent CF3CH2In OH, the alkane employed is sp-containing3C-H bond C6 cycloalkane, the molar weight of alkane is 10 times of that of simple substance bromine, the molar weight of nitrate radical-containing quaternary ammonium salt catalyst is 150% of that of simple substance bromine, the molar weight of hydrochloric acid is 200% of that of simple substance bromine, the mixture is added into a light-transmitting reaction container under the atmosphere of oxygen, the container is sealed, the mixture is stirred and reacts under the conditions of normal pressure and direct fluorescent lamp illumination with the power of more than 4W, the reaction temperature is controlled at 10 ℃, the reaction time is 24 hours, and after the reaction is finished, the mixed reaction is added into CDCl3And internal standard, drying and sampling1H NMR analysis to give nuclear magnetic yield using CH2Cl2Extracting, 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 bromoalkane product.
Example 17
A process for preparing the bromide of alkane includes such steps as providing alkane, quaternary ammonium salt containing bromide negative ion, nitrite catalyst, CF3CO2H is added into a neutral solvent to be CH2Cl2In (1), the alkane used is an alkane containing sp3C-H bond, C30 branched-chain alkane with nitro substituent, the molar weight of the alkane is 100 times that of the quaternary ammonium salt containing the bromine negative ion, the molar weight of the nitrite is 300 percent of the quaternary ammonium salt containing the bromine negative ion, and CF3CO2The molar weight of H is 500 percent of that of the quaternary ammonium salt containing the bromine negative ions, and a light-transmitting reaction vessel is added under the oxygen atmosphereSealing, stirring under normal pressure and ultraviolet lamp illumination with power of 4W or more, reacting at 50 deg.C for 2 hr, and adding CDCl into the mixed reaction3And internal standard, drying and sampling1H NMR analysis to give nuclear magnetic yield using CH2Cl2Extracting, 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 bromoalkane product.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. A preparation method of alkane bromide is characterized in that alkane, bromine-containing compound, 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 for reaction under the conditions of normal pressure and illumination, and then the alkane bromide is obtained through analysis of nuclear magnetic yield, extraction, drying, filtration, reduced pressure distillation and column layer separation;
the alkane contains sp3All alkanes of C1 to C30 of C-H bond;
the bromine-containing compound is a brominated metal salt;
the catalyst is nitrite;
the acid is a protonic acid.
2. The method for preparing the alkane bromide according to claim 1, wherein the molar amount of the alkane is 50 to 100 times that of the bromine-containing compound; the molar weight of the catalyst is 0.1 to 300 percent of that of the bromine-containing compound; the molar amount of the acid is 100 to 500 percent of the bromine-containing compound.
3. The method according to claim 1, wherein the reaction is carried out without adding a solvent.
4. 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 more than 4W.
5. The method for preparing alkane bromide according to claim 1, wherein the reaction temperature is controlled to be-5 to 50 ℃.
6. The method for preparing alkane bromide according to claim 1, wherein the reaction time is controlled to be 2-48 hours.
7. The method according to claim 1, wherein the alkane bromide is sp of alkane3Monobrominated of C-H bonds.
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