Preparation method and application of tert-butyl aryl ether

Abstract

The invention discloses a preparation method and application of tert-butyl aryl ether, and belongs to the technical field of organic compound preparation. The present invention comprises the steps of reacting an aryl halide with an alkali metal alkoxide solid in an organic solvent under the catalysis of a catalyst to produce a tert-butyl aryl ether; aryl of the aryl halide is provided with or not provided with a substituent group; the catalyst is a phase transfer catalyst or a combination of a phase transfer catalyst and a halide. In the reaction for preparing the tert-butyl aryl ether through the reaction of the aryl halide and the alkali metal alkoxide solid in the organic solvent, the phase transfer catalyst is adopted to replace a metal catalyst in the prior art, and compared with the prior art, the method has the advantages of lower reaction cost, shorter reaction time, higher yield and higher purity.

Description

[0001] This application is a divisional application of the invention patent application with the application date of November 20, 2024, application number 2024116637899, and invention name “A preparation method and application of tert-butyl aromatic ether”. Technical Field

[0002] The present invention relates to the technical field of organic compound preparation, and in particular to a preparation method of tert-butyl aryl ether and application thereof. Background Art

[0003] Aryl ethers are a special motif commonly found in pharmaceuticals, agrochemicals, and natural products. Aryl ethers are also one of the most valuable synthetic intermediates, undergoing a variety of transformations in CC and CN bonding reactions. Tert-butoxybenzaldehyde has an aromatic flavor and is an important component of perfumes and fragrances, widely used in the flavor and fragrance industry. As a pharmaceutical intermediate, p-tert-butoxybenzaldehyde plays an important role in drug synthesis. It can be used as a starting material or key intermediate in the synthesis of certain drugs and converted into pharmacologically active drug molecules through a series of chemical reactions. Tert-butyl aryl ether is also an important intermediate in organic synthesis and can be further reacted to produce tert-butoxystyrene, which can be used as the main component of photoresist resins and has important applications in the semiconductor industry.

[0004] Makoto Watanabe et al.'s 1999 paper, "Palladium / P(t-Bu)3-catalyzedsynthesis of aryl t-butyl ethers and application to the first synthesis of 4-chlorobenzofuran," discloses the production of tert-butyl aryl ether products from an aryl halide starting material and a sodium tert-butoxide starting material catalyzed by a palladium catalyst, wherein xylene is used as a solvent and the reaction temperature is 120°C. The results show that using p-chlorobenzaldehyde as the aryl halide starting material and reacting in the presence of 1 mol% Pd(OAc)2 catalyst, the product yield is 60%, wherein the purity of p-tert-butylbenzaldehyde is 95%.

[0005] Chinese invention patent application CN116082127A discloses a method for preparing 4-tert-butoxystyrene. The first step, S1, involves the preparation of tert-butyl aryl ether. Specifically, bromobenzene and potassium or sodium tert-butoxide (an organic base) are reacted in DMSO, DMF, or DMAC (a first reaction solvent) at 110-120°C for 10-13 hours under the catalysis of cuprous iodide (a copper catalyst) to produce phenyl tert-butyl ether. In Example 1 of this application, the GC content of phenyl tert-butyl ether was 99.44%, with a yield of 75%. In Example 2, the GC content was 99.37%, with a yield of 77%.

[0006] The above two technical solutions for preparing tert-butyl aryl ether have defects that are not conducive to industrial large-scale preparation, including: the need for the use of metal catalysts, long reaction times, low yields, low purity, etc. Summary of the Invention

[0007] The present invention aims to address the above-mentioned problems existing in the prior art and to provide a method for preparing tert-butyl aryl ether and its application. The present invention utilizes a phase transfer catalyst (PTC) instead of the metal catalyst used in the prior art in the reaction of an aryl halide with an alkali metal alkoxide solid in an organic solvent to prepare the tert-butyl aryl ether. Compared to the prior art, the present invention achieves lower reaction costs, shorter reaction times, higher yields, and higher purity.

[0008] In order to achieve the above object, the technical solution of the present invention is as follows:

[0009] In a first aspect, the present invention provides a method for preparing tert-butyl aryl ether, comprising reacting an aryl halide with an alkali metal alkoxide solid in an organic solvent in the presence of a catalyst to produce the tert-butyl aryl ether, wherein the aryl halide has an aryl group (e.g., a phenyl group) with or without a substituent (e.g., an aldehyde group). The catalyst comprises at least a phase transfer catalyst, and specifically, the catalyst can be a phase transfer catalyst or a combination of a phase transfer catalyst and a halide.

[0010] In some embodiments, the phase transfer catalyst is a halogen-containing phase transfer catalyst.

[0011] In some embodiments, the halogen-containing phase transfer catalyst is a halogen-containing quaternary ammonium salt.

[0012] In some embodiments, the quaternary ammonium salt containing halogen is selected from one or any combination of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

[0013] In some embodiments, the phase transfer catalyst is a halogen-free phase transfer catalyst.

[0014] In some embodiments, the halogen-free phase transfer catalyst is selected from one of polyethers (e.g., polyethylene glycol, polyethylene glycol dialkyl ether), cyclic crown ethers (e.g., 18-crown-6, 15-crown-5, cyclodextrin), halogen-free quaternary ammonium salts (e.g., tetrabutylammonium hydrogen sulfate), tertiary amines (e.g., pyridine, tributylamine), quaternary ammonium bases, and quaternary phosphonium salts.

[0015] In some embodiments, the phase transfer catalyst is used in combination with a halide selected from potassium iodide, sodium iodide, potassium bromide, and sodium bromide as a catalyst. When the phase transfer catalyst and the halide are used as a catalyst, the amount of the phase transfer catalyst used is 0.5-2.0 mol% based on the molar amount of the aryl halide, and the amount of the halide used is 1-5% by weight of the aryl halide.

[0016] In some embodiments, the aryl halide is any one of aryl chloride, aryl bromide, and aryl iodide.

[0017] In some embodiments, the aryl halide is a halobenzaldehyde, such as chlorobenzaldehyde (eg, p-chlorobenzaldehyde), bromobenzaldehyde, or iodobenzaldehyde.

[0018] In some embodiments, the aryl chloride is chlorobenzene or p-chlorobenzaldehyde.

[0019] In some embodiments, the alkali metal alkoxide is any one of lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide.

[0020] In some embodiments, the tert-butyl aryl ether is tert-butylphenyl ether or tert-butoxybenzaldehyde.

[0021] In some embodiments, the tert-butoxybenzaldehyde is any one of o-tert-butoxybenzaldehyde, m-tert-butoxybenzaldehyde, or p-tert-butoxybenzaldehyde.

[0022] In some embodiments, the organic solvent is any one of DMF, DMSO or DMAC.

[0023] In some embodiments, when a phase transfer catalyst is selected as the catalyst, the amount of the phase transfer catalyst is 0.5-2.0 mol% based on the molar amount of the aryl halide, or a range between any two of the aforementioned values may be selected, for example, 0.5-1.0 mol%, 1.0-2.0 mol%, or 1.5-2.0 mol%. In a specific embodiment, the amount of the phase transfer catalyst can be selected to be 0.5 mol%, 1.0 mol%, 1.5 mol%, or 2.0 mol% based on the molar amount of the aryl halide. For illustrative purposes only, an amount of 1.5 mol% of the phase transfer catalyst based on the molar amount of the aryl halide means that when the amount of the aryl halide is 1 mol, the amount of the phase transfer catalyst is 0.015 mol.

[0024] In some embodiments, the reaction temperature is 125-150° C., and the reaction time is 4-6 hours.

[0025] In some embodiments, the molar ratio of the aryl halide to the alkali metal alkoxide is 1:1.5-1:1.75, and a range between any two of the aforementioned values can also be selected, for example, 1:1.55-1:1.6, 1:1.65-1:1.75; in a specific embodiment, the usage ratio of the aryl halide to the alkali metal alkoxide can be selected as 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75.

[0026] In some embodiments, when the phase transfer catalyst is combined with the halide as a catalyst, the amount of the phase transfer catalyst used is 0.5-2.0 mol% based on the molar amount of the aryl halide, and the range between any two of the aforementioned values can also be selected, for example, 0.5-1.0 mol%, 1.0-2.0 mol%, 1.5-2.0 mol%; in a specific embodiment, 0.5 mol%, 1.0 mol%, 1.5 mol% or 2.0 mol% can be selected; and the amount of the halide used is 1-5 wt% based on the weight of the aryl halide, and the range between any two of the aforementioned values can also be selected, for example, 1-3 wt%, 1-4 wt%, 2-4 wt%, 3-4 wt%; in a specific embodiment, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% can be selected. For illustrative purposes only, the amount of the halide used being 3 wt % based on the weight of the aryl halide means that when the amount of the aryl halide used is 10 g, the amount of the halide used is 0.3 g.

[0027] In a second aspect, the present invention further provides an application of the tert-butyl aryl ether prepared by the above-mentioned preparation method, wherein the tert-butyl aryl ether is reacted with a Wittig reagent to prepare tert-butoxystyrene. Specifically, the tert-butoxybenzaldehyde (e.g., p-tert-butoxybenzaldehyde) is reacted with a Wittig reagent (ylide reagent / Wittig reagent) to produce tert-butoxystyrene (e.g., p-tert-butoxystyrene).

[0028] In some embodiments, the Wittig reagent is methylenetriphenylphosphine.

[0029] The reaction principle of the present invention is as follows:

[0030] Phase transfer catalysts help reactants transfer from one phase to another phase where a reaction can occur, accelerating or enabling reactions between substances in two mutually incompatible solvents (liquid-liquid or solid-liquid). During a reaction, the catalyst transfers a reacting entity from one phase to the other, allowing it to interact with the substrate and react. The present invention has discovered that the use of a phase transfer catalyst improves the reaction efficiency of an aryl halide, typically soluble in an organic solvent, with an alkali metal alkoxide solid, typically poorly soluble in an organic solvent, in the presence of only an organic phase, compared to the prior art. This is likely because the alkali metal alkoxide solid is difficult to homogeneously disperse in the organic phase, while the phase transfer catalyst promotes better contact and reaction between the alkali metal alkoxide solid itself, as a solid phase, and the aryl halide homogeneously dispersed in the organic phase, thereby improving reaction efficiency.

[0031] The beneficial effects of the present invention are as follows:

[0032] Verified by the present invention, tetrabutylammonium bromide, polyethylene glycol and 18-crown ether-6 as phase-transfer catalyst representatives have achieved a higher reaction yield than metal catalysts (for example Pd and Cu metal catalysts) in the preparation of tert-butyl aryl ether, and catalyst cost is significantly reduced. In phase-transfer catalysts, halogen-containing phase-transfer catalysts, for example halogen-containing quaternary ammonium salts, are particularly advantageous for the preparation of tert-butyl aryl ether. In addition, providing a halogen halide (for example, potassium iodide, sodium iodide, potassium bromide, sodium bromide) with a halogen-containing phase-transfer catalyst or a halogen-free phase-transfer catalyst combination as a composite catalyst is also particularly advantageous for the preparation of tert-butyl aryl ether. Through testing, the halogen halide potassium iodide and the halogen-containing phase-transfer catalyst tetrabutylammonium iodide are combined as a composite catalyst, and the target product yield can reach 96.4%.

[0033] The present invention develops a high-yield reaction process by adjusting a series of reaction factors such as the amount of catalyst used (feeding amount), reaction temperature range, reaction time, molar ratio of raw material feeding amount, composition of composite catalyst, etc. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the embodiments.

[0035] Examples 1-3

[0036] The raw materials involved in this embodiment are p-chlorobenzaldehyde and sodium tert-butoxide, the proportions are shown in Table 1, the catalyst used is shown in Table 2, and the organic solvent is dimethylformamide (DMF). The reaction formula is as follows:

[0037]

[0038] Reaction steps: At room temperature (25°C) and normal pressure, 10.0 g of p-chlorobenzaldehyde (technically pure) (CHO-C6H4-Cl) and tetrabutylammonium bromide (TBAB) as shown in Table 1 below were placed in a 250 mL three-necked flask, 45 g of DMF (technically pure) was added as a solvent, and the mixture was stirred and dissolved. Under the same conditions, the tetrabutylammonium bromide was replaced with the catalysts shown in Table 2 (all commercially available) to carry out the reaction. The amount of the catalyst tetrabutylammonium bromide was 1 mol% of the p-chlorobenzaldehyde amount, and the amount of the other catalysts was equimolar to the amount of the tetrabutylammonium bromide to facilitate comparison of the catalyst effects. Subsequently, a total amount of sodium tert-butoxide ((CH3)3-C-ONa) solid (technically pure) 1.6 times the molar amount of the p-chlorobenzaldehyde raw material was added to the three-necked flask in three batches (each batch of equal weight). The reactants were stirred at 100-200 rpm during the feeding process. The reaction system temperature was monitored and maintained at no more than 40°C. After the feeding was completed and the temperature stabilized, the reaction system was slowly heated to a reflux temperature of 130°C. The reflux reaction was timed to proceed for 5 hours starting from the time the reflux temperature was reached. During the reaction, the reaction progress was tracked by spot plate and LC detection of product generation and raw material consumption. After the reflux reaction is completed, 0.1 mol / L dilute sulfuric acid (industrial pure) is slowly added dropwise to the three-necked flask until the pH value of the reaction system reaches the range of 2-3; then ethyl acetate is used as an extractant to extract the product in the reaction system, and the extract is washed 4 times with pure water. Finally, the obtained washed product is concentrated by rotary evaporation at 40°C to obtain a crude product of 4-tert-butoxybenzaldehyde (CHO-C6H4-OC-(CH3)3, molecular weight 178.23), which is then purified by distillation to obtain a pure product with a purity higher than 99%. The yield (in g) is weighed and the yield (%) is calculated as shown in Table 2 below.

[0039] Table 1

[0040] Molecular weight (g / mol) Weight (g) mole (mol) Equivalent (equiv.) p-Chlorobenzaldehyde 140.57 10.0 0.071 1 Tetrabutylammonium bromide 322.37 0.23 0.00071 0.01 Sodium tert-butoxide 96.10 10.9 0.1136 1.6

[0041] Table 2

[0042]

[0043]

[0044] Note: Table 2 sets different non-phase transfer catalysts to form Comparative Example 1 and Comparative Example 2 under the same reaction conditions; wherein Comparative Example 1: according to the prior art 1 (Makoto Watanabe et al.), 3 times the molar amount of Pd(OAc)2 of P(t-Bu)3 is added; Comparative Example 2: according to the metal catalyst of the prior art 2 CN116082127A, cuprous iodide is selected as the catalyst.

[0045] This example investigates the effects of using a phase transfer catalyst and a non-phase transfer catalyst on the yield of the preparation reaction of 4-tert-butoxybenzaldehyde (target product).

[0046] As shown in the results in Table 2, the three phase transfer catalysts of Examples 1-3 all achieved higher yields of the target product than the two non-phase transfer catalysts in the prior art (Comparative Examples 1-2). Without being limited by theory, this may be because the phase transfer catalyst catalyzes and promotes the reaction between the sodium tert-butoxide solid and the p-chlorobenzaldehyde in the DMF organic phase.

[0047] Of the three phase transfer catalysts in Examples 1-3, tetrabutylammonium bromide (a halogen-containing phase transfer catalyst) achieved the highest yield of the target product, exceeding that of the halogen-free phase transfer catalysts polyethylene glycol and 18-crown ether-6. Without being bound by theory, this may be because the halide ion (bromide ion) in tetrabutylammonium bromide activates the para-chloride in p-chlorobenzaldehyde, thereby promoting the reaction process in which the tert-butoxide ion from sodium tert-butoxide replaces the para-chloride.

[0048] Examples 4-5

[0049] Based on Example 1, this example further investigated the effect of using equimolar amounts of different quaternary ammonium salt phase transfer catalysts on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Aside from the catalyst type, all other reaction conditions were the same as in Example 1. The results are shown in Table 3.

[0050] Table 3

[0051] catalyst Yield (g) Yield (%) Example 1 Tetrabutylammonium bromide 10.2 80.6 Example 4 Tetrabutylammonium iodide 10.4 82.2 Example 5 Tetrabutylammonium chloride 9.8 77.4

[0052] As shown in the results of Table 3, tetrabutylammonium iodide achieved a higher yield of the target product than tetrabutylammonium bromide, while the target product yield achieved by tetrabutylammonium chloride was lower than that of tetrabutylammonium bromide and tetrabutylammonium iodide, but still higher than that of the two non-quaternary ammonium salt phase transfer catalysts (polyethylene glycol and 18-crown ether-6) in Table 2. Without being limited by theory, this may be because the iodide ion in tetrabutylammonium iodide is more active than the bromide ion in tetrabutylammonium bromide, further activating the para-chlorine in p-chlorobenzaldehyde, thereby further promoting the reaction process of the tert-butoxide ion from sodium tert-butoxide replacing the para-chlorine.

[0053] Examples 6-8

[0054] Based on Example 4, this example further investigated the effect of using different molar amounts of tetrabutylammonium iodide on the yield of the p-tert-butoxybenzaldehyde preparation reaction. Aside from the catalyst dosage, all other reaction conditions were the same as in Example 4. The results are shown in Table 4.

[0055] Table 4

[0056] Phase transfer catalyst dosage (mol%) Yield (g) Yield (%) Example 6 0.5 10.0 79.0 Example 4 1.0 10.4 82.2 Example 7 1.5 10.7 84.6 Example 8 2.0 10.7 84.6

[0057] As shown in the results in Table 4, when the catalyst feed amount decreased from 1 mol% to 0.5 mol%, the yield decreased, and when it increased from 1 mol% to 1.5 mol%, the yield increased. When it was further increased to 2.0%, the yield did not increase further, proving that the more the catalyst feed amount, the more it promoted the reaction, but it reached a plateau at 1.5 mol%.

[0058] Examples 9-13

[0059] Based on Example 7, this example further investigated the effect of using different reflux temperatures as the reaction temperature on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the reflux temperature, all other reaction conditions were the same as in Example 7. The results are shown in Table 5.

[0060] Table 5

[0061] Reflux temperature (℃) Yield (g) Yield (%) Example 9 120 9.7 76.7 Example 10 125 10.5 83.0 Example 7 130 10.7 84.6 Example 11 135 10.9 86.1 Example 12 140 10.6 83.8 Example 13 150 10.2 80.6

[0062] As shown in Table 5, a relatively high yield is maintained within the temperature range of 125-150°C, while the yield decreases outside this range. Without being bound by theory, this may be because relatively low reflux temperatures may lead to incomplete reaction and reduced yield, while relatively high reflux temperatures may destroy the aldehyde group of the p-chlorobenzaldehyde starting material, resulting in an increase in reaction impurities and a reduced yield.

[0063] Examples 14-16

[0064] Based on Example 11, this example further investigated the effect of different reaction times on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the reaction time, all other reaction conditions were the same as in Example 11. The results are shown in Table 6.

[0065] Table 6

[0066] Reaction time (hours) Yield (g) Yield (%) Example 14 3.0 9.5 75.1 Example 15 4.0 10.8 85.3 Example 11 5.0 10.9 86.1 Example 16 6.0 10.9 86.1

[0067] As shown in the results of Table 6, when the reaction time was shortened from 5 hours to 4 hours, the yield hardly changed, and when the reaction time was extended to 6 hours, the yield also remained basically unchanged, indicating that the reaction had basically reached the reaction endpoint at 4 hours.

[0068] Examples 17-21

[0069] Based on Example 15, this example further investigated the effect of varying the molar ratio of p-chlorobenzaldehyde to sodium tert-butoxide on the yield of the p-tert-butoxybenzaldehyde preparation reaction. Aside from the molar ratio, all other reaction conditions were the same as in Example 15. The results are shown in Table 7.

[0070] Table 7

[0071]

[0072] As shown in the results in Table 7, there is an excess of sodium tert-butoxide between p-chlorobenzaldehyde and sodium tert-butoxide. When the amount of sodium tert-butoxide is increased to 1.65 times the molar amount of p-chlorobenzaldehyde, the yield increase basically reaches a plateau, and further increasing the amount of sodium tert-butoxide does not significantly increase the yield.

[0073] Examples 22-25

[0074] Based on Example 19, this example constructed composite catalysts composed of tetrabutylammonium iodide and various halides and examined their effects on the yield of the p-tert-butoxybenzaldehyde preparation reaction. Specifically, a homogeneous mixture of 1.5 mol% tetrabutylammonium iodide and 2 wt% potassium iodide, sodium iodide, potassium bromide, or potassium chloride, based on the p-chlorobenzaldehyde charge, was added to the reaction system as the composite catalyst. Aside from the catalyst, all other reaction conditions were the same as in Example 19. The results are shown in Table 8.

[0075] Table 8

[0076] Catalyst or composite catalyst Yield (g) Yield (%) Example 19 1.5 mol% tetrabutylammonium iodide 11.2 88.5 Comparative Example 3 2 wt% potassium iodide 3.0 23.7 Example 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Example 23 1.5 mol% tetrabutylammonium iodide + 2 wt% sodium iodide 11.9 94.0 Example 24 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium bromide 11.6 91.7 Example 25 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium chloride 11.2 88.5

[0077] As shown in Table 8, potassium iodide or sodium iodide, which provide iodide ions, and potassium bromide, which provides bromide ions, all further improved the yield of the target product to varying degrees compared to tetrabutylammonium iodide alone. However, potassium chloride, which provides chloride ions, failed to further improve the yield of the target product compared to tetrabutylammonium iodide alone. This indicates that not all types of halides can improve the yield of the target product when combined with tetrabutylammonium iodide to form a composite catalyst.

[0078] Examples 26-29

[0079] Based on Example 22, this example further investigated the effect of varying potassium iodide addition levels on the yield of the p-tert-butyloxybenzaldehyde preparation reaction in a composite catalyst. Aside from the potassium iodide addition level, all other reaction conditions were the same as in Example 22. The results are shown in Table 9.

[0080] Table 9

[0081] Composite catalyst Yield (g) Yield (%) Example 26 1.5 mol% tetrabutylammonium iodide + 1 wt% potassium iodide 11.5 90.9 Example 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Example 27 1.5 mol% tetrabutylammonium iodide + 3 wt% potassium iodide 12.1 95.6 Example 28 1.5 mol% tetrabutylammonium iodide + 4 wt% potassium iodide 12.2 96.4 Example 29 1.5 mol% tetrabutylammonium iodide + 5 wt% potassium iodide 12.2 96.4

[0082] As shown in the results of Table 9, increasing the potassium iodide dosage in the composite catalyst to 4 wt% maximized the yield of the target product, while further increasing it to 5 wt% failed to further improve the yield of the target product.

[0083] Examples 30-31

[0084] This example investigates the effect of a composite catalyst composed of a non-quaternary ammonium salt phase transfer catalyst and potassium iodide on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Aside from the catalyst, all other reaction conditions were the same as in Example 22. The results are shown in Table 10.

[0085] Table 10

[0086] catalyst Yield (g) Yield (%) Example 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Example 30 1.5 mol% polyethylene glycol + 2 wt% potassium iodide 9.8 77.4 Example 31 1.5 mol% 18-crown ether-6 + 2 wt% potassium iodide 10.4 82.2

[0087] As shown in Table 10 results, in non-quaternary ammonium salt phase-transfer catalyst (polyethylene glycol, 18-crown ether-6), adding 2 weight % potassium iodide has also further improved the target product yield equally.Compare with Example 22, the yield of the target product of embodiment 30-31 is relatively low, and it can be seen that quaternary ammonium salt phase-transfer catalyst tetrabutylammonium iodide obviously has better technical effect than non-quaternary ammonium salt phase-transfer catalyst polyethylene glycol, 18-crown ether-6 and halide potassium iodide are combined into composite catalyst after.

[0088] Example 32

[0089] Preparation of further derivatives of tert-butyl aryl ether (p-tert-butoxystyrene):

[0090] The raw materials involved in this example are the pure p-tert-butoxybenzaldehyde product obtained in the previous example and methylenetriphenylphosphine as a Wittig reagent, and the solvent is petroleum ether.

[0091] At room temperature (25°C) and normal pressure, 10g of pure p-tert-butyloxybenzaldehyde was dissolved in 80g of petroleum ether (technically pure), placed in a 250mL three-necked flask, heated to 65°C, and stirred to fully dissolve. Subsequently, a total of 16.25g of methylenetriphenylphosphine (CH2=P-Ph3, molecular weight 276.31) solid was added to the three-necked flask in three batches (each batch of equal weight). The temperature was adjusted to 60°C reflux temperature, and the reflux reaction was timed for 3 hours starting from the time reflux temperature was reached. The reaction progress was tracked by detecting the amount of product by GC.

[0092] After the reaction was completed for 3 hours, the reaction system was concentrated by rotary evaporation at 35°C, and then the concentrated product was extracted with ethyl acetate as an extractant. The extract was then washed 4 times with pure water. Finally, the obtained washed product was concentrated by rotary evaporation at 40°C to obtain a crude product of tert-butoxystyrene (CH2=CH-C6H4-OC-(CH3)3, molecular weight 176.25), which was then purified by distillation to obtain a pure product with a purity higher than 99%. The yield (in g) was weighed to be 8.9 g, and the calculated yield (%) was 90.0%.

[0093] Although the present invention has been disclosed above with reference to preferred embodiments, this is not intended to limit the present invention. Any person skilled in the art may make some modifications and improvements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be based on the definition of the claims.

Claims

1. A method for preparing tert-butyl aryl ether, characterized in that: The method comprises the following steps: reacting aryl halide with alkali metal alcoholate solid in an organic solvent under the catalysis of a catalyst to produce tert-butyl aryl ether; the aryl halide has or does not have a substituent on its aryl group; and the catalyst contains at least a phase transfer catalyst.

2. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The aryl halide is any one of aryl chloride, aryl bromide and aryl iodide; the aryl chloride is chlorobenzene or p-chlorobenzaldehyde.

3. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The alkali metal alkoxide is any one of lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide.

4. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The phase transfer catalyst is a halogen-containing phase transfer catalyst; the halogen-containing phase transfer catalyst is a halogen-containing quaternary ammonium salt; the halogen-containing quaternary ammonium salt is selected from any one or a combination of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride.

5. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The organic solvent is any one of DMF, DMSO and DMAC.

6. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The tert-butyl aryl ether is tert-butylphenyl ether or tert-butoxybenzaldehyde; the tert-butoxybenzaldehyde is any one of o-tert-butoxybenzaldehyde, m-tert-butoxybenzaldehyde and p-tert-butoxybenzaldehyde.

7. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The usage amount of the phase transfer catalyst is 0.5-2.0 mol % based on the molar amount of the aryl halide; the molar ratio of the aryl halide to the alkali metal alkoxide is 1:1.5-1:1.

75.

8. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The catalyst is a phase transfer catalyst or a combination of a phase transfer catalyst and a halide; the halide is selected from any one of potassium iodide, sodium iodide, potassium bromide, and sodium bromide; when the combination of the phase transfer catalyst and the halide is used as a catalyst, the amount of the phase transfer catalyst used is 0.5-2.0 mol% based on the molar amount of the aryl halide, and the amount of the halide used is 1-5% by weight of the aryl halide.

9. The method for preparing tert-butyl aryl ether according to claim 1, wherein: The reaction temperature is 125-150° C., and the reaction time is 4-6 hours.

10. Use of the tert-butyl aryl ether prepared by the preparation method according to any one of claims 1 to 9, characterized in that: The tert-butyl aryl ether is reacted with a Wittig reagent to prepare tert-butoxystyrene.

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