CN111072446A - Preparation method of alkyl cyclohexyl bromobenzene - Google Patents

Preparation method of alkyl cyclohexyl bromobenzene Download PDF

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Publication number
CN111072446A
CN111072446A CN201911412858.8A CN201911412858A CN111072446A CN 111072446 A CN111072446 A CN 111072446A CN 201911412858 A CN201911412858 A CN 201911412858A CN 111072446 A CN111072446 A CN 111072446A
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temperature
preparing
alkylcyclohexylbenzene
bromine
bromobenzene
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李勇
李成学
王建
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Yantai Kunyi Lcd Material Co ltd
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Yantai Kunyi Lcd Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of alkyl cyclohexyl bromobenzene, which comprises the following steps: one of alkyl cyclohexyl benzene, alkyl dicyclohexyl benzene and biphenyl is used as a raw material, bromine is used as a bromine source for a synthesis reaction, an oxidant is used as a catalyst, a synthesis product is washed to be neutral by water to obtain a crude organic phase, then a solvent is added into the crude organic phase, the temperature is raised to a boiling state and flows back, and finally the temperature is reduced and filtered to obtain the product.

Description

Preparation method of alkyl cyclohexyl bromobenzene
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method of alkyl cyclohexyl bromobenzene.
Background
In recent years, with the rapid development of liquid crystal display technology, the demand for liquid crystal display materials is expanding, and alkyl cyclohexyl bromobenzene is an important liquid crystal intermediate.
In the prior art, a conventional method for producing alkyl cyclohexyl bromobenzene is shown in figure 1, and alkyl cyclohexyl bromobenzene is synthesized by mainly using alkyl cyclohexyl benzene and bromine as raw materials and iron powder as a catalyst.
The method has the advantages of large bromine consumption, high cost, low yield of 40-60 percent,
therefore, the prior art is subject to further improvement and development.
Disclosure of Invention
In order to solve the problems, a preparation method of alkyl cyclohexyl bromobenzene is provided.
The invention provides the following technical scheme:
a preparation method of alkyl cyclohexyl bromobenzene comprises the following steps: one of alkyl cyclohexyl benzene, alkyl dicyclohexyl benzene and biphenyl is used as a raw material, bromine is used as a bromine source for a synthesis reaction, a synthetic product is washed to be neutral to obtain a crude organic phase, then a solvent is added into the crude organic phase, the temperature is raised to a boiling state and the mixture flows back, and finally the temperature is reduced and the product is obtained after filtration.
Preferably, during the synthesis reaction, the molar ratio of the raw material to bromine is 1: 0.5-1: 0.6.
preferably, the catalyst is H2O2NaClO, NaBrO and HNO3In the above step, the molar addition amount of the catalyst was 0.5 times the amount of the raw material.
Preferably, the reaction temperature is controlled between 0 and 20 ℃ and the reaction time is controlled between 4 and 6 hours during the synthesis reaction.
Preferably, the solvent is any one of methanol, ethanol and acetone, and the weight of the added solvent is 2 times of that of the crude organic phase.
Preferably, the temperature is raised to boiling state and the mixture is refluxed for 1 h.
Preferably, the temperature is reduced to 0 ℃ or lower after refluxing, and then filtration is performed.
Has the advantages that:
the preparation method of the alkyl cyclohexyl bromobenzene can effectively reduce the consumption of bromine and the cost, simultaneously improves the yield to more than 80 percent, does not generate hydrogen bromide waste gas and iron mud solid waste in the production process, and is popularized and used.
Drawings
FIG. 1 is a diagram of the chemical reaction equation for the preparation of alkylcyclohexylbenzene of the prior art;
FIG. 2 is a diagram of the chemical reaction scheme for the preparation of alkylcyclohexylbenzene in accordance with the present invention;
FIG. 3 is a diagram of the chemical reaction scheme for the preparation of ethylcyclohexylbromobenzene in specific example 1 of the present invention;
FIG. 4 is a diagram of the chemical reaction scheme for the preparation of propylcyclohexylbromobenzene in specific example 2 of the present invention;
FIG. 5 is a diagram of the chemical reaction scheme for the preparation of pentylcyclohexylbromobenzene in specific example 3 of the present invention.
Wherein R is C1~C9Linear alkyl group of (1).
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description of the technical solutions of the present invention with reference to the accompanying drawings of the present invention is made clearly and completely, and other similar embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments in the present application shall fall within the protection scope of the present application. In addition, directional terms such as "upper", "lower", "left", "right", etc. in the following embodiments are directions with reference to the drawings only, and thus, the directional terms are used for illustrating the present invention and not for limiting the present invention.
The following are specific examples of the present invention:
specific example 1: preparation of ethylcyclohexylbromobenzene (see FIG. 3 for a specific reaction equation)
Putting 188g of ethyl cyclohexylbenzene and 17g of hydrogen peroxide into a 500ml three-neck flask, stirring and cooling to below 20 ℃, adding 80g of bromine into a constant-pressure dropping funnel, keeping the temperature, slowly dropping, keeping the temperature for 2 hours after dropping, keeping the temperature for 2 hours, and sampling and detecting the bromine to be qualified (the ethyl cyclohexylbenzene is less than 2%, the heat is not qualified, keeping the temperature continuously, and sampling and detecting the bromine once every 1 hour);
adding H into the bottle2O, standing and layering after stirring, and repeating until the pH value is 7;
adding absolute ethyl alcohol with the mass being 2 times of that of the organic phase in the bottle, stirring and heating to boil, keeping boiling and refluxing for 1 hour, cooling to 0 ℃, performing suction filtration, and repeating once again.
Adding the filter cake into a flask, heating until the white solid begins to melt, stirring until the white solid is completely melted, heating, vacuumizing, and drying to obtain 218.4g of colorless liquid product (HPLC GC is 99.3%)
Theoretical yield: 268g of ethylcyclohexylbromobenzene
The yield was 218.4/268%
Specific example 2: preparation of propylcyclohexyl bromobenzene (see FIG. 4 for a specific reaction equation)
Putting 202g of ethyl cyclohexylbenzene and 37.2g of sodium hypochlorite into a 500ml three-neck flask, stirring and cooling to 20 ℃, adding 80g of bromine into a constant-pressure dropping funnel, slowly dropping the bromine at a constant temperature, keeping the temperature for 2 hours after dropping is finished, and keeping the temperature for 2 hours until the sampling detection is qualified (the content of propyl cyclohexylbenzene is less than 2 percent, the temperature is not qualified, keeping the temperature continuously, and sampling and detecting once every 1 hour);
adding H into the bottle2O, standing and layering after stirring, and repeating until the pH value is 7;
adding absolute ethyl alcohol with the mass 2 times of that of the organic phase in the bottle, stirring and heating to boil, keeping boiling and refluxing for 1h, cooling to 0 ℃, performing suction filtration, and repeating once again.
Adding the filter cake into a flask, heating until the white solid begins to melt, stirring until the white solid is completely melted, heating, vacuumizing, and drying to obtain 231.3g (HPLC GC ═ 99.6%)
Theoretical yield: 282g of propylcyclohexyl bromobenzene
The yield was 231.3/282 ═ 100%: 82.0%
Specific example 3: preparation of Pentylcyclohexylbromobenzene (see FIG. 5 for a specific reaction equation)
Putting 230g of pentylcyclohexylbenzene and 59.5g of sodium hypobromite into a 500ml three-neck flask, stirring and cooling to 20 ℃, adding 80g of bromine into a constant-pressure dropping funnel, slowly dropping the bromine at a constant temperature, keeping the temperature for 2 hours after dropping, keeping the temperature for 2 hours, and keeping the temperature for qualified sampling detection (the pentylcyclohexylbenzene is less than 2 percent, the temperature is not qualified, keeping the temperature continuously, and sampling and detecting once every 1 hour);
adding H into the bottle2O, standing and layering after stirring, and repeating until the pH value is 7;
adding absolute ethyl alcohol with the mass 2 times of that of the organic phase in the bottle, stirring and heating to boil, keeping boiling and refluxing for 1h, cooling to 0 ℃, performing suction filtration, and repeating once again.
Adding the filter cake into a flask, heating until the white solid begins to melt, stirring until the white solid is completely melted, heating, vacuumizing, and drying to obtain 259.4g (99.2% GC for HPLC)
Theoretical yield: 310g of propylcyclohexylbromobenzene
The yield is 259.4/310 × 100% ═ 83.7%
The quality and yield of the product synthesized according to the above examples 1-3 are shown in table 1:
table 1: the process of the invention can synthesize the product with high quality and yield
Example numbering Product appearance Yield of HPLC content
Example 1 Colourless liquid 81.5% 99.3%
Example 2 White solid 82% 99.6%
Example 3 White solid 83.7% 99.2%
The present invention has been described in detail, and it should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Claims (9)

1. A preparation method of alkyl cyclohexyl bromobenzene is characterized by comprising the following steps: one of alkyl cyclohexyl benzene, alkyl dicyclohexyl benzene and biphenyl is used as a raw material, bromine is used as a bromine source for synthesis reaction, an oxidant is used as a catalyst, a synthetic product is washed to be neutral by water to obtain a crude organic phase, then a solvent is added into the crude organic phase, the temperature is raised to a boiling state and the mixture flows back, and finally the temperature is lowered and the product is obtained after filtration.
2. The method for preparing alkylcyclohexyl bromobenzene as claimed in claim 1, wherein during the synthesis reaction, the molar ratio of raw material to bromine is 1: 0.5-1: 0.6.
3. the method for preparing alkylcyclohexylbenzene according to claim 1, wherein the catalyst is H2O2NaClO, NaBrO and HNO3One kind of (1).
4. The method for preparing alkylcyclohexylbenzene according to claim 3, wherein the molar addition amount of the catalyst is 0.5 times the molar amount of the starting material.
5. The method for preparing alkylcyclohexylbenzene according to claim 1, wherein the reaction temperature is controlled at 0-20 ℃ and the reaction time is controlled at 4-6 hours during the synthesis reaction.
6. The method for preparing alkylcyclohexylbenzene according to claim 1, wherein the solvent is any one of methanol, ethanol and acetone.
7. The method for preparing alkylcyclohexylbenzene according to claim 1, wherein the weight of the added solvent is 2 times of that of the crude organic phase.
8. The method for preparing alkylcyclohexylbenzene according to claim 1, wherein the temperature is raised to boiling and the reflux is carried out for 1 hour.
9. The method for preparing alkylcyclohexyl bromobenzene as claimed in claim 1, wherein the temperature is reduced to below 0 ℃ after refluxing for filtration.
CN201911412858.8A 2019-12-31 2019-12-31 Preparation method of alkyl cyclohexyl bromobenzene Pending CN111072446A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5654493A (en) * 1995-08-26 1997-08-05 Hoechst Aktiengesellschaft Process for preparing 4-bromophenyl alkyl ethers
US20050137431A1 (en) * 2003-12-15 2005-06-23 Bedekar Ashutosh V. Process for eco-friendly synthesis of bromobenzene
CN102603497A (en) * 2012-03-06 2012-07-25 蚌埠中实化学技术有限公司 1-alkoxy-4-[4-(4-alkyl cyclohexyl) phenyl]-2, 3-difluorobenzene and synthetic method thereof
CN103483153A (en) * 2013-08-30 2014-01-01 烟台海川化学制品有限公司 Preparation method of trans-4,4'-(1-bromophenyl)-cyclohexanol
CN103525429A (en) * 2013-08-30 2014-01-22 晶美晟光电材料(南京)有限公司 Liquid crystal compound and preparation method thereof as well as liquid crystal mixture containing liquid crystal compound and application of liquid crystal mixture

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5654493A (en) * 1995-08-26 1997-08-05 Hoechst Aktiengesellschaft Process for preparing 4-bromophenyl alkyl ethers
US20050137431A1 (en) * 2003-12-15 2005-06-23 Bedekar Ashutosh V. Process for eco-friendly synthesis of bromobenzene
CN102603497A (en) * 2012-03-06 2012-07-25 蚌埠中实化学技术有限公司 1-alkoxy-4-[4-(4-alkyl cyclohexyl) phenyl]-2, 3-difluorobenzene and synthetic method thereof
CN103483153A (en) * 2013-08-30 2014-01-01 烟台海川化学制品有限公司 Preparation method of trans-4,4'-(1-bromophenyl)-cyclohexanol
CN103525429A (en) * 2013-08-30 2014-01-22 晶美晟光电材料(南京)有限公司 Liquid crystal compound and preparation method thereof as well as liquid crystal mixture containing liquid crystal compound and application of liquid crystal mixture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
唐培堃等: "《精细有机合成化学及工艺学》", 30 November 1993, 天津大学出版社 *

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