Halogenated cyclohexylbenzene compound and preparation method thereof

Abstract

The invention discloses a halogenated cyclohexylbenzene compound and a preparation method thereof, and relates to the field of organic chemistry, and the halogenated cyclohexylbenzene compound is obtained by using dihalogenated benzene and cyclohexyl metal halide as raw materials and stirring and reacting under the action of a catalyst. The synthetic route of the halogenated cyclohexylbenzene compound is novel, the yield is high, byproducts are few, environmental pollution is small, a new view angle and method are provided for preparation of the halogenated cyclohexylbenzene compound, and the halogenated cyclohexylbenzene compound is worthy of popularization.

Description

Technical Field

[0001] The invention relates to the field of organic chemistry, in particular to organic photoelectric materials, and in particular to a halogenated cyclohexylbenzene compound and a preparation method thereof. Background Art

[0002] Halogenated cyclohexylbenzene compounds are important organic chemical raw materials, widely used in synthetic materials, medicine, pesticides and other fields. In the field of organic optoelectronics, halogenated cyclohexylbenzene compounds are important intermediates that can be used to construct a variety of functional molecular structures.

[0003] In the prior art, chlorocyclohexylbenzene can be synthesized mainly by the alkylation reaction of benzene and cyclohexene (referring to paper Organic Letters, 2011, vol.13, #19, p.4977-4979), and the dependence of this process on catalyst is strong, and the product generated is difficult to separate in addition. In addition, the patent of application publication number CN116283725A discloses the method for synthesizing bromocyclohexylbenzene with o-bromophenyl boric acid and bromocyclohexane as raw materials, and the target product yield of the method is low, and o-bromophenyl boric acid itself can also be coupled. Although there is also a variety of synthetic methods reported, these methods still have the problems of high cost, strict reaction conditions, low yield and selectivity, many by-products, environmental pollution, etc.

[0004] The present invention aims to provide a halogenated cyclohexylbenzene compound and a preparation method thereof. The halogenated cyclohexylbenzene compound is obtained by reacting dihalogenated benzene and cyclohexyl metal halide as raw materials under the action of a catalyst, and by optimizing the reaction conditions, the yield and purity of the halogenated cyclohexylbenzene compound are significantly improved, while the production cost and environmental pollution are reduced. The present invention can not only promote the industrial production of the synthesis of the halogenated cyclohexylbenzene compound, but also provide a new perspective and method for research in related fields. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a halogenated cyclohexylbenzene compound and a preparation method thereof.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A halogenated cyclohexylbenzene compound, the preparation method of which comprises the following steps:

[0008] (1) adding dihalobenzene to solvent A and stirring, then adding inorganic salt, heating to 100-110° C., and stirring for 3-3.5 hours to obtain a mixed solution;

[0009] (2) Under an inert gas atmosphere, the mixed solution was cooled to 1-10°C, and then solvent B was added and stirred for 10-15 minutes, followed by dropwise addition of cyclohexyl metal halide, the temperature was controlled not to exceed 10°C during the addition, and stirring was continued for 1-1.5 hours after the addition was completed, and then a catalyst was added, and the temperature was raised to 85-90°C and stirred for reaction for 12-14 hours to obtain a reaction solution;

[0010] (3) adding ice water to the reaction solution and stirring, adjusting the pH to 4-6 with aqueous hydrochloric acid, and then extracting, concentrating and distilling to obtain a halogenated cyclohexylbenzene compound;

[0011] The synthetic route of the compound containing halogenated cyclohexylbenzene is as follows:

[0012]

[0013] Wherein: X and Y are selected from chlorine, bromine, iodine, and fluorine;

[0014] M is selected from magnesium, zinc, aluminum, and manganese;

[0015] Z is selected from chlorine, bromine, iodine, and fluorine;

[0016] Furthermore, the Y may be in the ortho, meta or para position relative to X, X and Y may be the same or different; Z and X may be the same or different; and Z and Y may be the same or different.

[0017] Furthermore, X is preferably chlorine or bromine; Y is preferably chlorine or bromine; M is preferably magnesium, zinc or aluminum; and Z is preferably chlorine, bromine or iodine.

[0018] Furthermore, the solvent A in (1) is selected from one of toluene, xylene, n-hexane, sec-butyl acetate, and EnaoslvFS130;

[0019] Furthermore, the solvent B in (2) is selected from one of N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, and propylene carbonate; the catalyst can be selected from one of acetylacetonate nickel, 1,2-bis(diphenylphosphine)ethane nickel chloride, nickel chloride dimethoxyethane, 1,3-bis(diphenylphosphine propane) nickel dichloride, and 1,3-bis(diphenylphosphine propane) palladium dichloride;

[0020] Furthermore, the mass fraction of the hydrochloric acid aqueous solution in (3) is 5-7%;

[0021] Furthermore, the molar ratio of the dihalobenzene to the cyclohexyl metal halide is 1:(1.0-3.0); the molar ratio of the dihalobenzene to the inorganic salt is 1:(1.2-2.4); the molar ratio of the dihalobenzene to the catalyst is 1:(0.01-0.05); the cyclohexyl metal halide is prepared by adding the cyclohexyl metal halide to anhydrous tetrahydrofuran, stirring and mixing to prepare a solution with a concentration of 0.5-2 mol / L, and then adding it for use.

[0022] Beneficial effects of the invention: The invention provides a halogenated cyclohexylbenzene compound and a preparation method thereof, wherein the halogenated cyclohexylbenzene compound is obtained by stirring a reaction with dihalogenated benzene and a cyclohexyl metal halide as raw materials under the action of a catalyst. The halogenated cyclohexylbenzene compound has a novel synthesis route, high yield, few by-products, and little environmental pollution, and provides a new perspective and method for the preparation of halogenated cyclohexylbenzene compounds, which is worthy of promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of 1-chloro-2-cyclohexylbenzene prepared in Example 3. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027]

[0028] (1) Add 19.145 g (100 mmol) of o-bromochlorobenzene and 200 mL of toluene to a dry 500 mL three-necked flask, stir for 5 min, then add 16.35 g (120 mmol) of anhydrous zinc chloride, raise the temperature to 100° C. and keep it in a slightly boiling state, stir for 3 h, and obtain a mixed solution;

[0029] (2) Under a nitrogen atmosphere, the mixture was cooled to 4°C, 100 mL of anhydrous tetrahydrofuran was added and stirred for 10 min, and then 48.0 mL of a tetrahydrofuran solution of cyclohexylmagnesium bromide was added dropwise, and the temperature was controlled at 6°C during the addition. After the addition was completed, stirring was continued for 1 h, and then 0.26 g (1 mmol) of nickel acetylacetonate was added, and the temperature was raised to 85°C and stirred for 12 h to obtain a reaction solution; the tetrahydrofuran solution of cyclohexylmagnesium bromide was prepared by adding 95 mmol of cyclohexylmagnesium bromide to 47.5 mL of anhydrous tetrahydrofuran and stirring and mixing, and the concentration was 2 mol / L;

[0030] (3) After adding 200 mL of ice water to the reaction solution and stirring, the pH was adjusted to 6 with a 5% hydrochloric acid aqueous solution, and the reaction mixture was allowed to stand for stratification. The organic phase was extracted, concentrated, and distilled, and the fraction at 80-85° C. was collected to obtain 16.26 g of 1-bromo-2-cyclohexylbenzene with a purity of 98% and a yield of 68%;

[0031] Example 2

[0032]

[0033] (1) Add 23.591 g (100 mmol) of o-dibromobenzene and 200 mL of toluene to a dry 500 mL three-necked flask, stir for 7 min, then add 16.35 g (120 mmol) of anhydrous zinc chloride, raise the temperature to 105° C. and keep it in a slightly boiling state, stir for 3.2 h, and obtain a mixed solution;

[0034] (2) Under a nitrogen atmosphere, the mixture was cooled to 6°C, 100 mL of anhydrous tetrahydrofuran was added and stirred for 12 min, and then 48.5 mL of a tetrahydrofuran solution of cyclohexylmagnesium bromide was added dropwise, and the temperature was controlled to be 8°C during the addition. After the addition was completed, stirring was continued for 1.2 h, and then 0.26 g (1 mmol) of nickel acetylacetonate was added, and the temperature was raised to 85°C and stirred for reaction for 12 h to obtain a reaction solution; the tetrahydrofuran solution of cyclohexylmagnesium bromide was prepared by adding 95 mmol of cyclohexylmagnesium bromide to 47.5 mL of anhydrous tetrahydrofuran and stirring and mixing, and the concentration was 2 mol / L;

[0035] (3) After adding 200 mL of ice water to the reaction solution and stirring, the pH value was adjusted to 5 with a 6% hydrochloric acid aqueous solution, and the mixture was allowed to stand for stratification. The organic phase was extracted, concentrated, and distilled, and the fraction at 80-85° C. was collected to obtain 14.82 g of 1-bromo-2-cyclohexylbenzene with a purity of 97% and a yield of 62%;

[0036] Example 3

[0037]

[0038] (1) Add 14.71 g (100 mmol) of o-dichlorobenzene and 200 mL of toluene to a dry 500 mL three-necked flask, stir for 6 min, then add 16.35 g (120 mmol) of anhydrous zinc chloride, raise the temperature to 110° C. and keep it in a slightly boiling state, stir for 3.3 h, and obtain a mixed solution;

[0039] (2) Under a nitrogen atmosphere, the mixture was cooled to 8°C, 100 mL of anhydrous tetrahydrofuran was added and stirred for 14 min, and then 64.5 mL of a tetrahydrofuran solution of cyclohexylmagnesium bromide was added dropwise, and the temperature was controlled at 5°C during the addition. After the addition was completed, stirring was continued for 1.4 h, and then 0.26 g (1 mmol) of nickel acetylacetonate was added, and the temperature was raised to 88°C and stirred for 13 h to obtain a reaction solution; the tetrahydrofuran solution of cyclohexylmagnesium bromide was prepared by adding 95 mmol of cyclohexylmagnesium bromide to 64.0 mL of anhydrous tetrahydrofuran and stirring and mixing, and the concentration was 1.5 mol / L;

[0040] (3) After adding 200 mL of ice water to the reaction solution and stirring, the pH was adjusted to 4 with a 7% hydrochloric acid aqueous solution, and the reaction mixture was allowed to stand for stratification. The organic phase was extracted, concentrated, and distilled, and the fraction at 80-85° C. was collected to obtain 13.4 g of 1-chloro-2-cyclohexylbenzene with a purity of 98.77% and a yield of 69%;

[0041] Example 4

[0042]

[0043] (1) Add 14.71 g (100 mmol) of o-dichlorobenzene and 200 mL of toluene to a dry 500 mL three-necked flask, stir for 6 min, then add 16.35 g (120 mmol) of anhydrous zinc chloride, raise the temperature to 105° C. and keep it in a slightly boiling state, stir for 3.2 h, and obtain a mixed solution;

[0044] (2) Under a nitrogen atmosphere, the mixed solution was cooled to 8°C, 100 mL of anhydrous tetrahydrofuran was added and stirred for 12 min, and then 64.5 mL of a tetrahydrofuran solution of cyclohexylmagnesium chloride was added dropwise, and the temperature was controlled to be 4°C during the addition. After the addition was completed, stirring was continued for 1.3 h, and then 0.26 g (1 mmol) of nickel acetylacetonate was added. The temperature was raised to 90°C and stirred for 14 h to obtain a reaction solution; the tetrahydrofuran solution of cyclohexylmagnesium chloride was prepared by adding 95 mmol of cyclohexylmagnesium chloride to 64.0 mL of anhydrous tetrahydrofuran and stirring and mixing, and the concentration was 1.5 mol / L;

[0045] (3) After adding 200 mL of ice water to the reaction solution and stirring, the pH value was adjusted to 5 with a 6% hydrochloric acid aqueous solution, and the reaction mixture was allowed to stand for stratification. The organic phase was extracted, concentrated, and distilled, and the fraction at 80-85° C. was collected to obtain 8.6 g of 1-chloro-2-cyclohexylbenzene with a purity of 95% and a yield of 45%;

[0046] Example 5

[0047] Compared with Example 1, toluene was replaced with Enaoslv FS130 (supplier: Shanghai Ruiyi Environmental Protection Technology Co., Ltd.), and the rest was exactly the same as Example 1, to obtain 15.54 g of 1-bromo-2-cyclohexylbenzene with a purity of 98% and a yield of 65%;

[0048] Example 6

[0049] Compared with Example 1, anhydrous zinc chloride was replaced with ferric chloride, and the rest was the same as Example 1, to obtain 15.54 g of 1-bromo-2-cyclohexylbenzene with a purity of 98% and a yield of 65%;

[0050] Example 7

[0051] Compared with Example 5, anhydrous zinc chloride was replaced with ferric chloride, and the rest was the same as Example 5, to obtain 15.54 g of 1-bromo-2-cyclohexylbenzene with a purity of 98% and a yield of 65%;

[0052] Example 8

[0053] Compared with Example 2, tetrahydrofuran was replaced with propylene carbonate, and the rest was the same as Example 2, to obtain 11.71 g of 1-bromo-2-cyclohexylbenzene with a purity of 96% and a yield of 49%;

[0054] Example 9

[0055] Compared with Example 1, o-bromochlorobenzene was replaced with m-bromochlorobenzene, and the rest was the same as Example 1, to obtain 15.21 g of 1-bromo-2-cyclohexylbenzene with a purity of 98% and a yield of 63.6%;

[0056] Example 10

[0057] Compared with Example 1, o-bromochlorobenzene was replaced with p-bromofluorobenzene, and the rest was the same as Example 1, to obtain 17.1 g of 1-bromo-2-cyclohexylbenzene with a purity of 97% and a yield of 71.5%.

[0058] The applicant declares that the present invention illustrates a halogenated cyclohexylbenzene compound of the present invention through the above-mentioned embodiment, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a halogenated cyclohexylbenzene compound, characterized in that: The steps include: (1) adding dihalobenzene to solvent A and stirring, then adding an inorganic salt, heating and stirring to obtain a mixed solution; (2) Under an inert gas atmosphere, the mixed solution is cooled, solvent B is added and stirred, and then cyclohexyl metal halide is added dropwise, and the temperature is controlled not to exceed 10° C. during the addition. After the addition is completed, stirring is continued and a catalyst is added. After the temperature is raised, stirring is performed to obtain a reaction solution; (3) After adding ice water to the reaction solution and stirring, the pH is adjusted to acidic with aqueous hydrochloric acid, followed by extraction, concentration and distillation to obtain a halogenated cyclohexylbenzene compound.

2. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: The synthetic route of the halogenated cyclohexylbenzene compound is as follows: Wherein, X and Y are selected from one of chlorine, bromine, iodine and fluorine; M is selected from one of magnesium, zinc, aluminum and manganese; and Z is selected from one of chlorine, bromine, iodine and fluorine.

3. The method for preparing a halogenated cyclohexylbenzene compound according to claim 2, characterized in that: The Y may be located at the ortho, meta or para position relative to X; X and Y may be the same or different; Z and X may be the same or different; and Z and Y may be the same or different.

4. The method for preparing a halogenated cyclohexylbenzene compound according to claim 2, characterized in that: The X is selected from chlorine or bromine; Y is selected from chlorine or bromine; M is selected from magnesium, zinc or aluminum; and Z is selected from chlorine, bromine or iodine.

5. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: In (1), solvent A is selected from toluene, xylene, n-hexane, sec-butyl acetate, and Enaoslv FS130; in (3), the mass fraction of the hydrochloric acid solution is 5-7%, and the adjusted pH range is 4-6.

6. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: In the above (2), the solvent B is selected from one of N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide and propylene carbonate.

7. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: In the above (2), the catalyst is selected from nickel acetylacetonate, 1,2-bis(diphenylphosphine)ethane nickel chloride, nickel dimethoxyethane chloride, 1,3-bis(diphenylphosphine propane) nickel dichloride, and 1,3-bis(diphenylphosphine propane) palladium dichloride.

8. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: The molar ratio of the dihalobenzene to the cyclohexyl metal halide is 1:(1.0-3.0); the molar ratio of the dihalobenzene to the inorganic salt is 1:(1.2-2.4); and the molar ratio of the dihalobenzene to the catalyst is 1:(0.01-0.05).

9. The method for preparing a halogenated cyclohexylbenzene compound according to claim 1, characterized in that: The cyclohexyl metal halide is prepared by adding the cyclohexyl metal halide into anhydrous tetrahydrofuran, stirring and mixing to prepare a solution with a concentration of 0.5-2 mol / L, and then adding the solution for use.

10. A halogenated cyclohexylbenzene compound prepared by the method for preparing a halogenated cyclohexylbenzene compound according to any one of claims 1 to 9.

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