CN114804988B - Method for synthesizing brominated organic compound through chemical selectivity controllable oxygen oxidation bromination - Google Patents

Method for synthesizing brominated organic compound through chemical selectivity controllable oxygen oxidation bromination Download PDF

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CN114804988B
CN114804988B CN202210391760.4A CN202210391760A CN114804988B CN 114804988 B CN114804988 B CN 114804988B CN 202210391760 A CN202210391760 A CN 202210391760A CN 114804988 B CN114804988 B CN 114804988B
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CN114804988A (en
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王剑
曾俊延
徐建泓
黄岩毅
虞思思
李军
周倩
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Hangzhou Medical College
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07—ORGANIC CHEMISTRY
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
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    • 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
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    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract

The invention discloses a method for synthesizing a brominated organic compound by oxidizing and brominating oxygen with controllable chemical selectivity, which comprises the following steps: the method comprises the steps of taking bromide anions as a bromine source, taking N-alkylpyridine nitrate ionic liquid shown in a formula (X) as a catalyst, taking molecular oxygen as an oxidant, taking a compound shown in a structure shown in a formula (I), a formula (II) or a formula (III) as a reaction substrate, and carrying out reaction on aromatic hydrogen and/or benzyl hydrogen in the reaction substrate under an acidic conditionAnd/or aromatic carbonyl alpha-H is subjected to monobromination, dibromo or polybromination to prepare the brominated organic compound. The method can be used for converting hydrocarbon bonds at aromatic sites, benzyl sites and aromatic carbonyl alpha-sites into carbon-bromine bonds, has the characteristics of wide substrate applicability, controllable chemical selectivity (namely single-bromine/dibromo/polybrominated), high atom utilization rate, high efficiency, economy and environmental protection, and avoids the use of heavy metal catalysts.

Description

Method for synthesizing brominated organic compound through chemical selectivity controllable oxygen oxidation bromination
Field of the art
The invention relates to a method for synthesizing a brominated organic compound by oxidizing and brominating with oxygen.
(II) background art
Brominated organic compounds are important pharmaceutical and pesticide intermediates. For example, α -bromoacetophenone is an important intermediate of the nonsteroidal anti-inflammatory aryl propionic acid drug; alpha-bromo-o-chloroacetophenone is an important intermediate for synthesizing beta-adrenergic receptor agonist chloropropanalin; the p-bromotoluene is a main raw material for synthesizing pesticide bromoacarb, and the p-bromoanisole is an intermediate for synthesizing gynecological drug chlorovinyl estrel. In addition to mono-brominated compounds, poly-brominated compounds have also important uses, for example, methyl 3, 5-dibromo-2-aminobenzoate is an important intermediate for the expectorant drugs ambroxol and bromhexine; 2-bromo-4, 5-dimethoxy bromobenzyl is a key intermediate of the spasmolytic pityriasis of gastrointestinal tract. With the continuous expansion of the application fields of brominated organic compounds, people pay more attention to the research on the synthesis method of the brominated organic compounds.
Conventionally, in the preparation of organic bromides, bromine is generally required to be used as a bromine source, and a target product is generated, and meanwhile, a byproduct hydrogen bromide with a molar quantity is generated, so that the utilization rate of bromine atoms is only 50%, and the waste of bromine is caused. At the same time, bromine bromination has poor chemical selectivity, and a large amount of organic solvent is often consumed, and a polybrominated product is difficult to obtain selectively. Therefore, improving the atomic utilization of bromine, the chemical selectivity of the reaction, and the environmental friendliness are problems that need to be solved by bromination reactions.
One of the more green monobromination methods is the oxidative bromination method, i.e., the conversion of the reacting bromide anions into "bromide cations" that are directly available for reaction with the substrate by the oxidizing agent. Among the oxidants, the oxygen is most green and cheap, and the oxygen is directly converted into water after oxidizing bromide anions, so that the pollution to the environment is small. At present, some technologies have been explored to perform oxygen oxidation, for example, CN101857518B and CN 102503751B disclose a synthetic method of bromoarene with cupric nitrate as a catalyst and molecular oxygen as an oxidant, and the method uses heavy metal copper salt as a catalyst, which is easy to pollute the environment, has narrow substrate applicability, and is limited to aromatic bromination of phenols and alpha-bromination of acetophenone; CN101857518B discloses an aromatic oxygen oxidation bromination reaction using hydrobromic acid as brominating agent and 2-picoline nitrate as catalyst, the method avoids the use of transition metal elements, but the catalyst has low activity, severe reaction conditions, easy generation of byproducts, and difficult large-scale application. In addition, the above methods are limited by the catalyst activity, and can only synthesize monobrominated products, but cannot further realize polybromination after monobromination (passivating the benzene ring).
The oxygen oxidation bromination technology has fundamental improvement in atom economy compared with the traditional bromine bromination, but the use of heavy metals in the reaction, the realization of chemical selectivity (monobromination/polybromination controllable), the limitation of substrates in the reaction (only limited to the bromination of electron-rich aromatic C-H or ketone alpha-C-H bonds) and the like still restrict the wide application of the technology. Therefore, it is important to find a more green, efficient and versatile oxidative bromination process.
(III) summary of the invention
The invention aims to provide a green synthesis method for directly synthesizing a brominated organic compound from aromatic hydrocarbon derivatives, which can be used for converting hydrocarbon bonds at aromatic sites, benzyl sites and carbonyl alpha sites into carbon-bromine bonds. The method has the characteristics of wide substrate applicability, controllable chemical selectivity, high atom utilization rate, high efficiency, economy and environmental protection, and avoids the use of heavy metal catalysts.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of a brominated organic compound comprises the following steps: the method comprises the steps of taking bromide anions as a bromine source, taking N-alkylpyridine nitrate ionic liquid shown in a formula (X) as a catalyst, taking molecular oxygen as an oxidant, taking a compound shown in a formula (I), a formula (II) or a formula (III) as a reaction substrate, and carrying out monobromination, dibromo or polybromination on aromatic hydrogen and/or benzyl hydrogen and/or aromatic carbonyl alpha-H in the reaction substrate under an acidic condition to prepare a brominated organic compound;
in the formula (X), R' represents a C1-C15 hydrocarbon group or a C5-C12 aryl group;
in formula (I): when the main ring is a benzene ring, n=1 to 6, and the substituent R represents 0 to 5 identical or different substituents; when the main ring is a naphthalene ring, n=1 to 8, and the substituent R represents 0 to 7 identical or different substituents; each substituent is independently selected from the group consisting of hydroxy, amino, C1-C8 alkoxy, mono-C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C12 alkyl, C5-C12 aryl, C5-C12 aryloxy, C1-C8 alkoxycarbonyl, C1-C8 acylamino, halogen, nitro, cyano, carboxy, C1-C8 acyl, or C1-C8 alkoxycarbonyl; and, when at least one of the substituents R is selected from the group consisting of C1-C8 acylamino, nitro, cyano, carboxyl, C1-C8 acyl or C1-C8 acyloxy, then at least one of the substituents R is also selected from the group consisting of a strong electron donating group which is a C1-C8 alkoxy, C5-C12 aryloxy or hydroxy group;
in the formula (II), the substituent R 1 Represents 1 to 5 identical or different substituents, each substituent being independently selected from the group consisting of C1-C8-acyloxy, C1-C8-acylamino, halogen, nitro, cyano or carboxyl; m=1-3, r 2 Represents 0 to 2 identical or different substituents, each substituent being independently selected from the group consisting of C5-C12 aryl, amino, C1-C8 alkoxy, mono-C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C12 alkyl, C1-C8 acyloxy, C1-C8 acylamino, halogen, nitro, cyano, carboxyl, C1-C8 acyl or C1-C8 alkoxyformyl;
in the formula (III), the substituent R 3 Selected from a C5-C12 aryl or a substituted C5-C12 aryl, said substituted C5-C12 aryl having at least one substituent on the aromatic ring, said substituent being selected from alkyl, C1-C8 acyloxy, C1-C8 acylamino, halogen, nitro, cyano, carboxyl or C1-C8 acyl; t=1-3, r 4 Represents 0 to 2 identical or different substituents, each substituent being independently selected from the group consisting of C5-C12 aryl, amino, C1-C8 alkoxy, mono-C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C12 alkyl, C1-C8 acyloxy, C1-C8 acylamino, halogen, nitro, cyano, carboxyl, C1-C8 acyl or C1-C8 alkoxyformyl.
In the invention, the C5-C12 aryl is preferably a common aromatic ring such as phenyl, pyrrolyl, thienyl, naphthyl, pyridyl and the like. The halogen is preferably chlorine, bromine or iodine.
When the compound (I) is taken as a reaction substrate, and the main ring in the compound (I) is free of substituent groups, or contains substituent groups which are electron donating groups and are free of C1-C12 alkyl groups (namely, substituent groups are selected from hydroxyl groups, amino groups, C1-C8 alkoxy groups, mono-C1-C8 hydrocarbylamino groups, di-C1-C8 hydrocarbylamino groups, C5-C12 aryl groups, C5-C12 aryloxy groups and C1-C8 alkoxy formyl groups), or at least one of substituent groups R is selected from C1-C8 acylamino groups, halogen, nitro groups, cyano groups, carboxyl groups, C1-C8 acyl groups or C1-C8 acyloxy groups and at least one substituent group is selected from strong electron donating groups, the mono-bromo, dibromo or polybromide of the compound (I) all occurs on aromatic hydrogen, especially para-position and meta-position aromatic hydrogen; when the substituent of the compound (I) contains a C1-C12 alkyl group, the monobromination of the compound (I) occurs on the aromatic hydrogen, and the dibromo or polybromination occurs on the benzylic hydrogen, whether or not other electron donating groups are also contained.
The invention takes the compound (II) as a reaction substrate, and the monobromination, dibromo or polybromination of the compound (II) all occur on benzyl hydrogen, namely one or two or three of m H are replaced by bromine.
The invention takes the compound (III) as a reaction substrate, and the monobromination, dibromo or polybromination of the compound (III) all occur on carbonyl alpha-H, namely one or two or three of t H are replaced by bromine.
Preferably, in the compound (I), each substituent is independently selected from C1-C8 alkoxy, hydroxy, C1-C12 alkyl or C5-C12 aryloxy.
Preferably, in the compound (II), R 2 Represents 0 to 2 identical or different substituents, each substituent being independently selected from C1-C12-alkyl or C5-C12-aryl.
Preferably, in the compound (III), t=1 to 3, r 4 Represents 0 to 2 identical or different substituents, each substituent being independently selected from C5-C12-aryl, C1-C12-alkyl or halogen.
The reaction temperature of the bromination reaction of the present invention is preferably from room temperature to 120 ℃.
The molecular oxygen used in the bromination reaction of the present invention is preferably added in the form of oxygen and/or air, i.e., in the form of oxygen or air or a mixture of oxygen and air. It is further preferable that the oxygen and/or air used in the present invention have a pressure of 0.1MPa to 3.0MPa, and preferably normal pressure (0.1 MPa), and this can be achieved by continuously introducing air and/or oxygen into the reactor or by sealing the reactor after the reactor is connected to an oxygen balloon.
The bromine source used in the bromination reaction is an acid or a salt of a bromine anion, preferably at least one of hydrobromic acid, sodium bromide and potassium bromide.
The reaction system of the invention needs to be added with acid to form an 'acidic condition', and can be various common inorganic acids and organic acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, acetic acid, nitric acid and the like, preferably hydrobromic acid, acetic acid or hydrochloric acid. The amount of acid used need only be such that the number of moles of hydrogen ions provided is greater than the number of moles of substrate.
The molar ratio of the ionic liquid catalyst to the substrate used in the invention can be set according to the requirements of bromination reaction (namely monobromination, dibromo or polybromination), and is generally 0.01-2.0. For monobromination, it is preferred that the molar ratio of the two is 0.05 to 0.1; for dibromo, the molar ratio of the two is preferably 0.08-0.3; for polybromination, the molar ratio of the two is preferably 0.1 to 1.8.
The invention can control the chemical selectivity of the reaction by changing the feeding ratio of the reaction substrate and the bromine source: for monobromination reactions, br - And a molar ratio of the reaction substrate of 0.8 to 1.5, usually preferably 1 to 1.05, in order to optimize the conversion of the starting material, the selectivity of the product; for dibromo, br - And the molar ratio of the reaction substrate is 2.0 to 3.0, preferably 2.05 to 2.3; for polybromination reactions, br - And the molar ratio of the substrate is n-1.5n, preferably 1.05n-1.3n, wherein n represents the number of carbon-bromine bonds formed and is equal to or greater than 3. For dibromo or polybromination reactions, the bromine source may be added in one portion or in separate portions.
The synthesis method specifically recommended by the invention is carried out according to the following steps: adding a reaction substrate, an ionic liquid catalyst, a bromine source (added at one time or step by step) and acid into a reaction container, introducing air and/or oxygen after the addition is finished to reach a certain pressure, reacting at a certain temperature, and performing conventional post-treatment after the full reaction to obtain the corresponding brominated organic compound.
The bromination reaction can be monitored by Gas Chromatography (GC), thin Layer Chromatography (TLC), liquid Chromatography (LC) and the like to determine the reaction end point.
Compared with the prior art, the invention is characterized in that:
(1) The synthesis method of the invention can realize the bromination of H on the aromatic ring containing electron withdrawing groups, thus realizing the chemical selectivity control (monobromination/dibromination/polybromination) of the substrate under the condition of oxygen and oxygen bromination by simply controlling the amount of the bromide ions and the catalyst, and selectively obtaining dibromo and tribrominated products which are rarely obtained in the oxygen bromination reaction.
(2) The synthesis method can realize bromination of aromatic alpha-H and benzyl H, can realize chemical selectivity control (monobromination/dibromination/polybromination) of a substrate under the condition of oxygen and oxygen bromination by simply controlling the amount of the added bromide ions and catalyst, and can selectively obtain monobrominated, dibromo and polybrominated products.
(3) The ionic liquid is used for catalyzing oxygen oxidation bromination, so that the use of a common heavy metal catalyst in the reaction is avoided, and the catalyst can be recycled without adding additional reagents.
(4) Compared with the existing oxygen oxidation bromination system, the invention has certain advantages of required temperature, reaction time and product yield.
(IV) the specific embodiment:
in order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The synthesis of the ionic liquid catalyst used in the embodiment of the invention is carried out according to the reference document [ ACS Omega 2019,4,5,9400-9406], namely, N-alkylpyridine nitrate ionic liquid is obtained by using nitrate in silver nitrate to replace bromide anions (bromide ions and silver ions form silver bromide precipitates) after generating N-alkylpyridine onium bromide by equimolar pyridine and bromoalkane.
The concentration of the aqueous hydrochloric acid and hydrobromic acid used in the examples are mass fractions.
Example 1:
the synthesis method comprises the following steps:
in an open system (air communication), 2.16g (20 mmol) anisole, 0.86g (3 mmol) N-dodecylpyridine nitrate ionic liquid, 2.16g (21 mmol) sodium bromide, 15mL water, 10mL10% dilute hydrochloric acid were added to a single-necked flask with an air communication condenser. After mixing, stirring was carried out at room temperature for 3 hours, and the completion of the reaction was detected by TLC. The reaction was stopped, 300mL of water and 300mL of ethyl acetate were added to the reaction solution, and the aqueous layer was extracted three times with 300mL of ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate, and ethyl acetate was removed under reduced pressure to give 3.69g of 4-bromoanisole as a product, yield: 99%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ7.38(dt,J＝9.2,2.4Hz,2H),6.78(dt,J＝9.2,2.4Hz,2H),3.78(s,3H).
13 C NMR(101MHz,Chloroform-d)δ158.9,132.4,115.9,113.0,55.6.
example 2:
the synthesis method comprises the following steps:
27g (250 mmol) anisole, 9.91g (50 mmol) N-butylpyridine nitrate ionic liquid, 59.5ml 48% hydrobromic acid aqueous solution (containing 525mmol HBr) were added into a three-neck flask connected with a water-receiving condenser, an oxygen balloon was connected, and the system was sealed. The reaction was carried out at 60℃under normal pressure with the oil bath temperature controlled, after about two hours, 29.0mL of 48% aqueous hydrobromic acid (containing 260mmol of HBr) was slowly added dropwise thereto, the reaction was continued at 60℃for 5.5 hours, TLC follow-up detection was carried out, the reaction of the raw materials was completed, the reaction was stopped, 300mL of water and 300mL of ethyl acetate were added to the reaction solution, and the aqueous layer was extracted three times with 300mL of ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate, and ethyl acetate was removed under reduced pressure to give 63.11g of 2, 4-dibromoanisole as a product, yield: 95%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ7.68(d,J＝2.4Hz,1H),7.40(dd,J＝8.8,2.4Hz,1H),6.79(d,J＝8.4Hz,1H),3.89(s,3H).
13 C NMR(100MHz,Chloroform-d)δ155.2,135.5,131.3,113.1,112.9,112.6,56.4.
example 3:
the synthesis method comprises the following steps:
into a three-necked flask connected to a water-receiving condenser were charged 0.32g (3 mmol) of anisole, 0.59g (3 mmol) of N-butylpyridine nitrate ionic liquid and 1.2mL of 48% aqueous hydrobromic acid (containing 10.5mmol of HBr). Oil bath reaction is carried out at 90 ℃ for 20 hours, the conversion of dibromo products is stopped by GC, and the products are eluted by pure petroleum ether through a silica gel column to obtain 0.90g of 2,4, 5-tribromoanisole product, the yield is: 87%.
Product nuclear magnetism:
1H NMR(400MHz,Chloroform-d)δ7.65(s,2H),3.87(s,3H).
13C NMR(100MHz,Chloroform-d)δ153.9,137.1,119.5,117.6,60.8.
example 4:
the synthesis method comprises the following steps:
to a three-necked flask connected to a water-receiving condenser, 12.8g (100 mmol) of naphthalene, 11.31 g (110 mmol) of sodium bromide, 50ml of water, 50ml of acetic acid and 1.98g (10 mmol) of N-butylpyridine nitrate ion liquid were charged under an open system. The three-necked flask was connected to an air condenser, air was continuously introduced, the reaction temperature was controlled to be 40℃and stirred for 2 hours, and after the substrate was substantially completely converted by GC detection, the reaction was stopped. The reaction solution was separated with ethyl acetate and distilled water, the aqueous layer was extracted with ethyl acetate three times, the organic layers were combined, and the solvent was distilled off under reduced pressure to obtain 19.43 g of 1-bromonaphthalene as a product, with a yield of 94%.
Product nuclear magnetic identification data:
1 H NMR(500MHz,Chloroform-d)δ8.29(d,J＝8.5Hz,1H),7.87(d,J＝8.5Hz,1H),7.84-7.81(m,2H),7.65-7.62(m,1H),7.58-7.55(m,1H),7.35(t,J＝8.0Hz,1H)
13 C NMR(125MHz,Chloroform-d)δ134.6,132.1,129.9,128.3,128.0,127.4,127.1,126.7,126.2,122.9
example 5:
the synthesis method comprises the following steps:
to a three-necked flask connected to a water-receiving condenser were added 2.96g (20 mmol) of phenylbutanone, 1.19g (6 mmol) of N-butylpyridine nitrate ionic liquid, and thereto were added 2.98g (25 mmol) of potassium bromide, 30ml of water, 20 ml of acetic acid at one time at 60℃in an oil bath. After the addition, the three-neck flask is connected with an air condensing tube, oxygen is continuously introduced, the reaction is carried out for 8 hours at the normal pressure and the temperature of 80 ℃, and TLC tracking detection is carried out until the reaction of the raw materials is complete. Stop reaction, use petroleum ether-ethyl acetate = 150:1 (v: v) as eluent, separating by silica gel column chromatography to obtain 4.21g of product alpha-bromophenylbutanone, yield: 93%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ8.01(d,J＝7.2Hz,2H),7.58(tt,J＝7.6,1.6Hz,1H),7.46(t,J＝7.6Hz,2H),5.08(dd,J＝8.0Hz,6.0Hz,1H),2.29-2.08(m,2H),1.08(t,J＝7.2Hz,3H).
13 c NMR (100 MHz, chlorine-d). Delta. 193.3,134.5,133.7,128.9,128.8,49.1,27.0,12.2 example 6:
synthesis method
To a single-necked flask communicating with a water-receiving condenser was added 4.95g (30 mmol) of 2-nitroacetophenone, and 4.4mL of 40% aq hydrobromic acid aqueous solution (containing 31mmol HBr) and 0.34g (1.5 mmol) of N-heptyl pyridine nitrate ion liquid were added at a time. After the addition, an oxygen balloon is connected, the reaction is carried out for 5 hours at the normal pressure and 50 ℃, and TLC tracking detection is carried out until the reaction of the raw materials is complete. Stop the reaction, use petroleum ether-ethyl acetate=50: 1 (v: v) as eluent, and separating by silica gel column chromatography to obtain 6.24g of 2-bromo-1- (2-nitrophenyl) ethanone as a product, yield: 85%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ8.22(d,J＝8.0Hz,1H),7.80(t,J＝7.2Hz,1H),7.69(t,J＝8.0Hz,1H),7.51(d,J＝7.2Hz,1H),4.31(s,2H).
13 c NMR (100 MHz, chlorine-d). Delta. 194.3,145.4,134.9,134.8,131.3,129.1,124.5,33.9 example 7:
the synthesis method comprises the following steps:
into a three-necked flask connected with a water-receiving condenser was charged 4.95g (30 mmol) of 2-nitroacetophenone, 3.96mL of 48% aqueous hydrobromic acid (35 mmol HBr), and 0.48g (3 mmol) of N-heptyl pyridine nitrate ion liquid. The three-necked flask after addition was connected to an air condenser, continuously introduced with oxygen, reacted at normal pressure at 50℃for 5 hours, followed by TLC until the reaction of the starting materials was complete, then 3.4ml of 48% aq hydrobromic acid (30 mmol HBr) was added, reacted at 60℃for 5 hours, and the reaction was stopped by TLC until the monobrominated substituent was complete, and petroleum ether-ethyl acetate=60: 1 (v: v) as eluent, and separating by silica gel column chromatography to obtain 7.85g of 2, 2-dibromo-1- (2-nitrophenyl) ethanone as a product, yield: 81%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ8.27(d,J＝8.0Hz,1H),7.84(t,J＝7.6Hz,1H)7.74(t,J＝8.0Hz,1H)7.69(d,J＝7.2Hz,1H),6.31(s,1H).
13 c NMR (100 MHz, chlorine-d). Delta. 188.8,145.2,135.0,132.3,131.8,131.1,124.6,42.2 example 8:
the synthesis method comprises the following steps:
to a three-necked flask connected to a water-receiving condenser was added 4.90g (30 mmol) of 2-nitroacetophenone, followed by a first addition of 7.9ml of 48% aqueous hydrobromic acid (containing 70mmol of HBr) and 0.72g (3 mmol) of N-heptylpyridine nitrate ion liquid. The three-necked flask after the addition was connected to an air condenser, continuously introduced with oxygen, reacted at normal pressure and 60℃for 11 hours, followed by TLC until the reaction of the raw materials was completed, then 3.4mL of 48% aqueous hydrobromic acid (30 mmol of HBr was added, 100mmol of HBr was added together), reacted at normal pressure and 60℃for 5 hours, and the reaction was stopped by TLC until the reaction of the monobrominated substituent was completed, and petroleum ether-ethyl acetate=70: 1 (v: v) as eluent, and separating by silica gel column chromatography to obtain 6.12g of 2, 2-tribromo-1- (2-nitrophenyl) ethanone as a product, yield: 51%.
Product nuclear magnetic identification data:
1 H NMR(500MHz,Chloroform-d)δ8.34(d,J＝9.0Hz,1H),7.88-7.83(m,2H),7.79-7.75(m,1H)
13 C NMR(125MHz,Chloroform-d)δ187.2,134.9,131.5,130.9,129.4,124.4,40.2
example 9:
the synthesis method comprises the following steps:
9.41g (100-mmol) of phenol and 15.0mL of 40% aq hydrobromic acid (containing 105mmol of HBr) and 3.96g (20 mmol) of N-butylpyridine nitrate ionic liquid are added into a single-neck flask which is communicated with a water receiving condenser pipe, the condenser pipe is connected with a water cooling pipe, an oxygen balloon is connected, and the reaction is carried out for 2 hours under the oil bath at normal pressure and 80 ℃. GC was performed to trace the reaction of the starting materials to completion, the organic layer was retained by ethyl acetate-water extraction, and water washing was performed three times, and ethyl acetate was distilled off under reduced pressure to give 17.13g of 4-bromophenol as a product, yield: 99%.
Product nuclear magnetic identification data:
1 H NMR(600MHz,Chloroform-d)δ＝7.37-7.35(d,J＝1.2Hz,2H),6.76-6.74(d,J＝1.2Hz,2H),4.84(br,1H).
13 C NMR(600MHz,Chloroform-d)δ＝154.6,132.5,117.2,113.0.
example 10:
the synthesis method comprises the following steps: to a three-necked flask connected with an air condenser, 8.51g (50 mmol) of diphenyl ether was added, and 6.2mL of 48% aq hydrobromic acid (containing 55mmol of HBr) and 0.99g (5 mmol) of N-butylpyridine nitrate ion liquid were added at one time, followed by stirring at a low temperature of 20℃under normal pressure for 5 hours by turning on an oxygen balloon. TLC tracking is carried out until the reaction of the raw materials is complete, the reaction is stopped, pure petroleum ether is used as an eluent, and the product of 11.83g of 4-bromodiphenyl ether (4-bromodiphenyl ether) is obtained through silica gel column chromatography separation, and the yield is: 95%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ7.40-7.36(m,2H),7.33-7.28(m,2H),7.11-7.07(m,1H),7.00-6.96(m,2H),6.87-6.82(m,2H)
13 C NMR(100MHz,Chloroform-d)δ156.7,156.5,132.7,129.9,123.7,120.4,119.0,115.6.
example 11:
the synthesis method comprises the following steps: in an open system, 8.51g (50 mmol) of diphenyl ether was added to a single-necked flask connected to a water-receiving condenser, and 11.32g (110 mmol) of sodium bromide, 80.0ml of water, 30.0ml of 10% strength diluted hydrochloric acid and 0.99g (5 mmol) of N-butylpyridine nitrate ion liquid were added at one time, and heated and stirred for 5 hours under an oil bath at normal pressure and 60 ℃. TLC tracking is carried out until the reaction of the raw materials is complete, the reaction is stopped, water and ethyl acetate are added, the solution is separated, the organic layer is washed three times by water, and then the solvent is removed under reduced pressure, so that 15.09g of the product 4,4' -diphenyl ether is obtained, and the yield is: 92%.
Product nuclear magnetic identification data:
1 H NMR(500MHz,Chloroform-d)δ＝7.46(dt,J＝10.0,3.0Hz,4H),6.89(dt,J＝10.0,3.0Hz,4H).
13 C NMR(125MHz,Chloroform-d)δ＝156.0,132.8,120.6,116.2.
example 12:
the synthesis method comprises the following steps:
in an open system, 9.95g (50 mmol) of o-bromoacetophenone and 1.49g (7.5 mmol) of N-butylpyridine nitrate ionic liquid were added to a three-necked flask connected with a water-receiving condenser, the three-necked flask was connected with an air condenser, air was continuously introduced into the three-necked flask at 60℃in an oil bath, and 4.5mL of 48% aqueous hydrogen bromide (containing 40 mmoles of HBr) was added dropwise. After 6 hours of reaction at 60 ℃ and normal pressure, the raw materials are not reduced any more by TLC detection, and the product, namely 10.39g of 2-bromo-1- (2-bromophenyl) ethanone, is obtained by eluting with pure petroleum ether through a silica gel column, and the yield is 75%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ7.64(dd,J＝6.4,1.2Hz,H),7.48(dd,J＝6.0,1.6Hz,H),7.42(td,J＝6.0,1.2Hz,H),7.36(td,J＝6Hz,1.6Hz,H),4.50(s,2H).
13 C NMR(100MHz,Chloroform-d)δ193.9,140.9,134.6,132.6,129.7,127.6,119.8,34.9.
example 13:
the synthesis method comprises the following steps:
in an open system, 1.99g (10 mmol) of o-bromoacetophenone and 0.40g (2 mmol) of N-butylpyridine nitrate ionic liquid were added into a three-necked flask connected with a water-receiving condenser, 2.7ml of 48% aqueous hydrogen bromide (containing 24 mmole of HBr) was added at one time, a condenser was inserted, and oxygen was continuously introduced at 80℃in an oil bath. After 6 hours of reaction at normal pressure and 80 ℃, the raw materials are not reduced any more by TLC detection, and 3.38g of 2, 2-dibromo-1- (2-bromophenyl) ethanone is obtained by eluting with pure petroleum ether through a silica gel column, and the yield is 95%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ7.65(dd J＝7.8,1.2Hz,H),7.57(dd,J＝7.8,2.2Hz,1H),7.46-7.38(m,2H),6.75(s,1H).
13 c NMR (100 MHz, chlorine-d). Delta. 189.4,136.4,133.5,132.9,130.8,127.7,119.1,41.8 example 14:
the synthesis method comprises the following steps:
in an open system, 3.78g (25 mmol) of p-nitroethylbenzene and 1.49g (7.5 mmol) of N-butylpyridinium nitrate ionic liquid are added into a three-necked flask connected with a water-receiving condenser, the three-necked flask is connected with an air condenser, oxygen is continuously introduced into the three-necked flask at the temperature of 60 ℃ in an oil bath, and 0.71ml of 48% hydrobromic acid aqueous solution (6.3 mmol HBr) is added to react under stirring at normal pressure. After 5 hours, 0.89ml of 48% aqueous hydrobromic acid (containing 7.9mmol of HBr) was added thereto and the reaction was stirred, and after 5 hours, 0.4ml of 48% aqueous hydrobromic acid (3.1 mmol of HBr) was added thereto and the reaction was stirred. Thereafter, 0.2mL of 48% aqueous hydrobromic acid (1.8 mmol each time, total 25.0mmol HBr added from the beginning) was added every 3 hours (four times), and the reaction was continued after the addition, and the total reaction time was 40 hours, and it was detected by TLC that there was substantially no starting material. The reaction was stopped and purified by column on silica gel with petroleum ether-ethyl acetate=80: 1 to give 3.44g of 1- (bromomethyl) -4-nitrobenzene in 60% yield.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d)δ8.28(d,J＝8.8Hz,2H),7.76(d,J＝8.8Hz,2H),6.25(q,J＝6.8Hz,1H),1.61(d,J＝6.8Hz,3H).
13 C NMR(100MHz,Chloroform-d)δ148.9,145.2,127.0,123.3,81.6,20.1.
example 15:
the synthesis method comprises the following steps:
in an open system, 2.68g (20 mmol) of N-butylbenzene and 0.40g (2 mmol) of N-butylpyridinium nitrate ionic liquid were charged into a three-necked flask connected to a water-receiving condenser, the three-necked flask was connected to an air condenser, oxygen was continuously introduced at 40℃into an oil bath, and then 3.6ml of 40% aqueous hydrobromic acid (containing 25mmol of HBr) was added. After 10 hours of reaction, the mixture of 1-bromo, 2-butylbenzene and 1-bromo, 4-butylbenzene (molar ratio 1 to 2.6, as identified by nuclear magnetism) was obtained in total 4.04g by eluting with pure petroleum ether through a silica gel column, with a total yield of 93%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,Chloroform-d,o-bromo-butylbenzene:p-bromo-butylbenzene)＝1:2.6δ7.52-7.50(m,1H),7.37(dt,J＝8.8,2.4Hz,5.2H),7.24-7.19(m,2H),7.05-7.03(m,6.2H),2.72(t,J＝7.6Hz,2H),2.55(t,J＝7.6Hz,5.2H),1.63-1.52(m,7.2H),1.40-1.30(m,7.2H),0.97-0.85(m,10.8H).
13 C NMR(100MHz,Chloroform-d)δ142.1,141.8,132.8,131.3,130.3,130.2,127.3,127.3,124.5,119.3,35.9,35.1,33.5,32.1,22.5,22.3,14.0,14.0.
example 16:
the synthesis method comprises the following steps:
in an open system, 2.68g (20 mmol) of N-butylbenzene and 0.79g (4 mmol) of N-butylpyridinium nitrate ionic liquid are added into a three-necked flask which is communicated with a water-receiving condenser, the three-necked flask is connected with an air condenser, oxygen is continuously introduced into the three-necked flask at the temperature of 80 ℃ in an oil bath, 4.5ml of 48% hydrobromic acid aqueous solution (containing 40mmol of HBr) is added for reaction for 12 hours, and the mixture is eluted by pure petroleum ether through a silica gel column to obtain 4.04g of 1-bromo-4- (1-bromobutyl) benzene with the yield of 51%.
Product nuclear magnetic identification data:
1 H NMR(400MHz,CDCl 3 )δ7.46(dt,J＝8.4,2.4Hz,2H),7.26(dt,J＝8.4,2.4Hz,2H),4.90(t,J＝7.6Hz,1H),2.28-2.19(m,1H),2.11-2.02(m,1H),1.53-1.27(m,2H),0.93(t,J＝7.2Hz,3H)
13 C NMR(100MHz,CDCl 3 )δ141.4,131.8,129.0,122.1,54.1,41.9,21.4,13.3.
example 17:
the synthesis method comprises the following steps:
to a three-necked flask connected with a water-receiving condenser, 4.95g (30 mmol) of 4-nitroacetophenone was added, 4.0mL of 48% aq hydrobromic acid (containing 35mmol of HBr) was added at one time, 1.59g (8 mmol) of N-butylpyridine nitrate ionic liquid was put on an oxygen balloon, the reaction was carried out under an oil bath at normal pressure and 40 ℃ for 12 hours, TLC tracking detection was carried out until the reaction of the raw materials was completed, the reaction was stopped, 100mL of water and 100mL of ethyl acetate were added, the liquid was separated, the solvent was removed under reduced pressure from the organic layer, and then 6.98g of 2-bromo-1- (4-nitrophenyl) ethanone was obtained by recrystallisation of ethyl acetate and petroleum ether (v: v=1:3), yield: 95%.
And (3) mechanically applying an ionic liquid:
in the post-synthesis treatment, the water layer obtained after the separation was directly subjected to water removal under reduced pressure to obtain 3.62g (recovery rate: 97%) of recovered ionic liquid. Then, 4.95g (30 mmol) of 4-nitroacetophenone, 3.1mL of 48% hydrobromic acid aqueous solution (35 mmol HBr) and N-butylpyridine nitrate ionic liquid recovered in the previous step, an oxygen balloon were added into a three-necked flask, and the reaction was carried out in an oil bath at 40 ℃ until the conversion of the raw material was complete (TLC detection), and the above-mentioned process of product separation, catalyst recovery and synthesis was repeated. This operation was repeated three times, and the recovery rates of the ionic liquid were 97%,94%,95% and the yields of the obtained products were 91%,90%,86%, respectively, when 16, 18, 26 hours were required.
And (3) product nuclear magnetism identification:
1 H NMR(500MHz,Chloroform-d)δ8.36(dt,J＝9.0,2.3Hz,2H),8.18(dt,J＝9.0,2.3Hz,2H),4.47(s,2H).
13 C NMR(125MHz,Chloroform-d)δ189.9,150.8,138.4,130.1,124.1,30.0.
example 18:
the synthesis method comprises the following steps:
3.93g (25 mmol) bromobenzene, 9.91g (50 mmol) N-butylpyridinium nitrate ionic liquid, 4.2mL48% hydrobromic acid aqueous solution (containing 37.5 mmole HBr) are put into a three-necked flask connected with a water-receiving condenser, the condenser is connected with water, a sealing system is arranged, an oxygen balloon is connected, and the oil bath is heated to reflux and kept. After 34 hours of reaction, GC detects that the raw materials are not converted, the reaction is stopped, and the product 1, 4-dibromobenzene 3.01g is obtained after the reaction is eluted by pure normal hexane through a silica gel column, and the yield is 51%.
And (3) product nuclear magnetism identification:
1 H NMR(400MHz,Chloroform-d)δ7.34(s,4H).
13 C NMR(100MHz,Chloroform-d)δ133.2,121.1.
example 19:
the synthesis method comprises the following steps:
27.23g (160 mmol) of diphenyl ether, 6.34g (32 mmol) of N-butylpyridine nitrate ionic liquid and 99.6mL of 48% hydrobromic acid aqueous solution (containing 880 mmoles of HBr) are added into a three-necked flask communicated with a water receiving condenser tube, oxygen is supplied through an oxygen balloon, a system is closed after a condenser tube (water cooling) is inserted, the reaction is carried out for 35 hours at 95 ℃, the tribromo is not converted into tetrabromo any more through HPLC detection, the ethyl acetate-water extraction is carried out, an ethyl acetate layer is reserved, a spin-dry solvent is adopted, 30mL of ethyl acetate is added for dissolution, 200mL of methanol is added for precipitation of a product, and after filtration, 72.9g of 2,2', 4' -tetrabromobiphenyl ether is obtained, and the yield: 94%.
Product nuclear magnetism:
1H NMR(400MHz,Chloroform-d)δ7.81(d,J＝2.4Hz,1H),7.40(dd,J＝8.4,2.4Hz,1H),6.74(d,J＝8.8Hz,1H).
13C NMR(100MHz,Chloroform-d)δ152.3,136.3,131.8,120.6,117.2,115.2.

Claims (12)

1. the synthesis method of the brominated organic compound is characterized by comprising the following steps: the method comprises the steps of taking bromide anions as a bromine source, taking N-alkylpyridine nitrate ionic liquid shown in a formula (X) as a catalyst, taking molecular oxygen as an oxidant, taking a compound shown in a formula (I), a formula (II) or a formula (III) as a reaction substrate, and carrying out monobromination, dibromo or polybromination on aromatic hydrogen and/or benzyl hydrogen and/or aromatic carbonyl alpha-H in the reaction substrate under an acidic condition to prepare a brominated organic compound;
in the formula (X), R' represents a C1-C15 hydrocarbon group;
in formula (I): when the main ring is a benzene ring, n=1 to 6, and the substituent R represents 0 to 5 identical or different substituents; when the main ring is a naphthalene ring, n=1 to 8, and the substituent R represents 0 to 7 identical or different substituents; each substituent is independently selected from hydroxy, C1-C8 alkoxy, C1-C12 alkyl, C5-C12 aryloxy, or halogen;
in the formula (II), the substituent R 1 Represents 1 to 5 identical or different substituents, each substituent being independently selected from halogen, nitro or cyano; m=1-3, r 2 Represents 0 to 2 identical or different substituents, each substituent being independently selected from C1-C12-alkyl groups;
in the formula (III), the substituent R 3 Selected from a C5-C12 aryl or a substituted C5-C12 aryl, said substituted C5-C12 aryl having at least one substituent on the aromatic ring, said substituent being selected from halogen, nitro or cyano; t=1-3, r 4 Represents 0 to 2 identical or different substituents, each substituent being independently selected from C1-C12 alkyl or halogen;
the C5-C12 aryl is phenyl or naphthyl.
2. The synthesis method according to claim 1, wherein: the halogen is chlorine, bromine or iodine.
3. The synthesis method according to claim 1 or 2, characterized in that: the reaction temperature of the bromination reaction is between room temperature and 120 ℃.
4. The synthesis method according to claim 1 or 2, characterized in that: molecular oxygen used in the bromination reaction is added in the form of oxygen or air or a mixture of oxygen and air, and the pressure of the oxygen or air or the mixture of oxygen and air is 0.1MPa-3.0MPa.
5. The synthesis method according to claim 1 or 2, characterized in that: the bromine source used in the bromination reaction is an acid or salt of a bromide anion.
6. The synthesis method according to claim 5, wherein: the bromine source used in the bromination reaction is at least one of hydrobromic acid, sodium bromide and potassium bromide.
7. The synthesis method according to claim 1 or 2, characterized in that: the reaction system is formed into an acidic condition by adding an acid selected from sulfuric acid, hydrochloric acid, hydrobromic acid, acetic acid or nitric acid.
8. The synthesis method according to claim 1 or 2, characterized in that: the molar ratio of the N-alkylpyridine nitrate ionic liquid to the reaction substrate is 0.01-2.0.
9. The method of synthesis according to claim 8, wherein: for monobromination, the molar ratio of the N-alkylpyridine nitrate ionic liquid to the reaction substrate is 0.05-0.1; for dibromo, the molar ratio of the two is 0.08-0.3; for polybromination, the molar ratio of the two is 0.1-1.8.
10. The synthesis method according to claim 1 or 2, characterized in that: control of Br in the monobromination reaction - And the molar ratio of the reaction substrate is 0.8-1.5; control of Br in dibromoreactions - And the molar ratio of the reaction substrate is 2.0-3.0; in the polybromination reaction, br - And the molar ratio of the substrate is n-1.5n, wherein n represents the number of carbon-bromine bonds formed and n is more than or equal to 3.
11. The method of synthesis according to claim 10, wherein: control of Br in the monobromination reaction - And the molar ratio of the reaction substrate is 1-1.05; control of Br in dibromoreactions - And the molar ratio of the reaction substrate is 2.05-2.3; in the polybromination reaction, br - And the molar ratio of the substrate is 1.05n-1.3n, wherein n represents the number of carbon-bromine bonds formed and n is more than or equal to 3.
12. The synthesis method according to claim 1 or 2, characterized in that: the synthesis method comprises the following steps: adding a reaction substrate, N-alkylpyridine nitrate ionic liquid, a bromine source and acid into a reaction container, introducing air and/or oxygen to reach a certain pressure after the addition, reacting at a certain temperature, and performing aftertreatment after the full reaction to obtain a corresponding brominated organic compound; the bromine source is added in one step or in multiple steps.
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