A 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 invention comprises the following steps: reacting an aryl halide with an alkali metal alkoxide 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 the aryl group; the catalyst is a phase transfer catalyst or a combination of a phase transfer catalyst and a halide. In the reaction of preparing tert-butyl aryl ether by reacting an aryl halide with an alkali metal alkoxide solid in an organic solvent, the phase transfer catalyst is used instead of the metal catalyst in the prior art, and compared with the prior art, the method has lower reaction cost, shorter reaction time, higher yield and higher purity.

Description

Technical Field

[0001] The 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

[0002] 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, with a variety of transformations in CC and CN bonding reactions. Tert-butoxybenzaldehyde has an aromatic flavor and is an important ingredient in perfumes and fragrances, and is widely used in the flavor and fragrance industry. As a pharmaceutical intermediate, p-tert-butoxybenzaldehyde plays an important role in the synthesis of drugs. It can be used as a starting material or key intermediate for 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, which 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.

[0003] Makoto Watanabe et al.'s 1999 paper "Palladium / P(t-Bu) 3 "-catalyzed synthesis of aryl t-butyl ethers and application to the first synthesis of 4-chlorobenzofuran" discloses the production of tert-butyl aryl ether products from aryl halide raw materials and sodium tert-butoxide raw materials by palladium catalyst catalysis, wherein xylene is used as solvent and the reaction temperature is 120°C; the results show that using p-chlorobenzaldehyde as aryl halide raw material, in the presence of 1 mol% Pd(OAc) 2 The reaction was carried out under the presence of a catalyst, and the product yield was 60%, wherein the purity of p-tert-butylbenzaldehyde was 95%.

[0004] Chinese invention patent application CN116082127A discloses a method for preparing 4-tert-butoxystyrene, wherein the first step S1 is the preparation of tert-butyl aryl ether, specifically using bromobenzene and potassium tert-butoxide or sodium tert-butoxide (organic base) in DMSO or DMF or DMAC solvent (first reaction solvent) under the catalysis of cuprous iodide (copper catalyst) at 110-120°C for 10-13h to produce phenyl tert-butyl ether. In Example 1 of the application, the GC detection content of phenyl tert-butyl ether is 99.44%, and the yield is 75%; in Example 2, the GC detection content is 99.37%, and the yield is 77%.

[0005] 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 to use a metal catalyst, long reaction time, low yield, low purity, etc. Summary of the invention

[0006] The purpose of the present invention is to solve the above problems existing in the prior art and provide a method for preparing tert-butyl aryl ether and its application. In the reaction of preparing tert-butyl aryl ether by reacting aryl halide with alkali metal alkoxide solid in an organic solvent, a phase transfer catalyst (PTC) is used to replace the metal catalyst in the prior art, which has lower reaction cost, shorter reaction time, higher yield and higher purity compared with the prior art.

[0007] In order to achieve the above object, the technical solution of the present invention is as follows:

[0008] 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 under the catalysis of a catalyst to produce the tert-butyl aryl ether, wherein the aryl group (e.g., phenyl) of the aryl halide has (e.g., aldehyde group) or no substituent. The catalyst contains 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.

[0009] In some embodiments, the phase transfer catalyst is a halogen-containing phase transfer catalyst.

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

[0011] 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.

[0012] In some embodiments, the phase transfer catalyst is a halogen-free phase transfer catalyst.

[0013] In some embodiments, the halogen-free phase transfer catalyst is selected from one of polyethers (e.g., polyethylene glycol, polyethylene glycol dialkyl ethers), cyclic crown ethers (e.g., 18-crown ether-6, 15-crown ether-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.

[0014] In some embodiments, the phase transfer catalyst is used in combination with a halide selected from any one of 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% of the weight of the aryl halide.

[0015] In some embodiments, the aryl halide is any one of aryl chloride, aryl bromide, and aryl iodide.

[0016] In some embodiments, the aryl halide is a halobenzaldehyde, such as chlorobenzaldehyde (eg, p-chlorobenzaldehyde), bromobenzaldehyde, or iodobenzaldehyde.

[0017] In some embodiments, the aryl chloride is chlorobenzene or p-chlorobenzaldehyde.

[0018] In some embodiments, the alkali metal alkoxide is any one of lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide.

[0019] In some embodiments, the tert-butyl aryl ether is tert-butylphenyl ether or tert-butoxybenzaldehyde.

[0020] In some embodiments, the tert-butoxybenzaldehyde is any one of o-tert-butoxybenzaldehyde, m-tert-butoxybenzaldehyde, or p-tert-butoxybenzaldehyde.

[0021] In some embodiments, the organic solvent is any one of DMF, DMSO or DMAC.

[0022] 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, and the range between any two of the above values ​​can also be selected, such as 0.5-1.0 mol%, 1.0-2.0 mol%, 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 exemplary purposes only, the amount of the phase transfer catalyst used is 1.5 mol% based on the molar amount of the aryl halide, which means that when the amount of the aryl halide used is 1 mol, the amount of the phase transfer catalyst used is 0.015 mol.

[0023] In some embodiments, the reaction temperature is 125-150° C., and the reaction time is 4-6 hours.

[0024] In some embodiments, the molar ratio of the aryl halide to the alkali metal alkoxide is 1:1.5-1:1.75, and the 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.

[0025] 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, such as 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, such as 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.

[0026] In a second aspect, the present invention also provides an application of the tert-butyl aryl ether prepared by the above 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).

[0027] In some embodiments, the Wittig reagent is methylenetriphenylphosphine.

[0028] The reaction principle of the present invention is as follows:

[0029] Phase transfer catalysts can help reactants transfer from one phase to another phase where reactions can occur, and can accelerate or enable substances in two mutually incompatible solvents (liquid-liquid two-phase system or solid-liquid two-phase system) to react. During the reaction, the catalyst transfers an entity that actually participates in the reaction from one phase to another phase so that it meets the substrate and reacts. The present invention finds that the use of phase transfer catalysts improves the reaction efficiency of aryl halides that are usually soluble in organic solvents and alkali metal alkoxide solids that are usually insoluble in organic solvents in the presence of only an organic phase compared to the prior art. This may be because alkali metal alkoxide solids are difficult to be homogeneously dispersed in the organic phase, and the phase transfer catalyst promotes better contact and reaction between the alkali metal alkoxide solids themselves as a solid phase and the aryl halides that are homogeneously dispersed in the organic phase, thereby improving the reaction efficiency.

[0030] The beneficial effects of the present invention are as follows:

[0031] 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 (such as 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, such as halogen-containing quaternary ammonium salts, are particularly advantageous for the preparation of tert-butyl aryl ether. In addition, providing a halogenated halide (such as potassium iodide, sodium iodide, potassium bromide, sodium bromide) in combination with a halogen-containing phase-transfer catalyst or a halogen-free phase-transfer catalyst as a composite catalyst is also particularly advantageous for the preparation of tert-butyl aryl ether. After testing, the halogenated 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%.

[0032] The present invention develops a high-yield reaction process by adjusting a series of reaction elements 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

[0033] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments.

[0034] Examples 1-3

[0035] 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:

[0036]

[0037] Reaction steps: At room temperature (25°C) and normal pressure, 10.0 g of p-chlorobenzaldehyde (industrial pure) (CHO-C 6 H 4 -Cl) and tetrabutylammonium bromide are placed in a 250mL three-necked flask, and 45g DMF (industrial pure) is added as solvent, and stirring is dissolved. Under the same conditions, tetrabutylammonium bromide is replaced by catalyst shown in Table 2 (all commercially available) to react, and the charging amount of catalyst tetrabutylammonium bromide is 1mol% of the charging amount of p-chlorobenzaldehyde, and the charging amount of other catalysts is an equimolar amount of tetrabutylammonium bromide with the charging amount, so as to compare the catalyst effect. Subsequently, sodium tert-butoxide ((CH 4 ) 2 ) 2 ) 3 ) 4 ) 5 ) 6 ) 1 ) 2 ) 2 ) 4 ) 3 ) 4 ) 5 ) 6 ) 2 ) 2 ) 4 ) 2 ) 4 ) 3 ) 4 ) 6 ) 2 ) 4 ) 2 ) 4 ) 4 ) 6 ) 2 ) 4 ... 3 ) 3 -C-ONa) solid (industrial pure), the reactant is stirred at 100-200rpm during the feeding process, and the temperature of the reaction system is monitored and maintained at no more than 40°C. After the feeding is completed and the temperature is stable, the reaction system is slowly heated to the reflux temperature of 130°C, and the reflux reaction is timed for 5 hours from the time the reflux temperature is reached. During the reaction, the reaction progress is tracked by detecting the formation of the product and the consumption of the raw materials through the spot plate and LC. After the reflux reaction is completed, 0.1 mol / L dilute sulfuric acid (industrial pure) is slowly added to the three-necked flask until the pH value of the reaction system reaches 2-3; then ethyl acetate is used as an extractant to extract the product in the reaction system, and then the extract is washed with pure water 4 times, and finally the obtained washed product is concentrated by rotary evaporation at 40°C to obtain 4-tert-butyloxybenzaldehyde (CHO-C 6 H 4 -OC-(CH 3 ) 3 , molecular weight 178.23) crude product, and then distilled and purified to obtain a pure product with a purity higher than 99%. The yield (in g) was weighed and the yield (%) was calculated as shown in Table 2 below.

[0038] Table 1

[0039] 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

[0040] Table 2

[0041] catalyst Yield (g) Yield (%) Example 1 Tetrabutylammonium bromide (phase transfer catalyst) 10.2 80.6 Example 2 Polyethylene glycol (molecular weight 800; PEG-800) (phase transfer catalyst) 9.1 71.9 Example 3 <![CDATA[18-Crown-6 (C 12 H 24 O 6 )(Phase transfer catalyst)]]> 9.4 74.2 Comparative Example 1 <![CDATA[Pd(OAc) 2 (non-phase transfer catalyst)]]> 8.5 67.2 Comparative Example 2 Cuprous iodide (non-phase transfer catalyst) 5.5 43.5

[0042] Note: Table 2 sets different non-phase transfer catalysts to form Comparative Example 1 and Comparative Example 2 under the same reaction conditions; Comparative Example 1: According to the prior art 1 (Makoto Watanabe et al.), Pd(OAc) is also added 2 3 times the molar amount of P(t-Bu) 3; Comparative Example 2: According to the metal catalyst of the prior art CN116082127A, cuprous iodide was selected as the catalyst.

[0043] 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 p-tert-butoxybenzaldehyde (target product).

[0044] As shown in the results of Table 2, the three phase transfer catalysts of Examples 1-3 all obtained higher target product yields than the two non-phase transfer catalysts (Comparative Examples 1-2) in the prior art. 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.

[0045] Among 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, which was higher than the halogen-free phase transfer catalysts polyethylene glycol and 18-crown ether-6. Without being limited by theory, this may be because the halogen ions (bromide ions) in tetrabutylammonium bromide activated the para-chlorine in p-chlorobenzaldehyde, thereby promoting the reaction process in which the tert-butoxide ions from sodium tert-butoxide replaced the para-chlorine.

[0046] Embodiment 4-5

[0047] On the basis of Example 1, this example further investigates the effect of using equimolar amounts of different quaternary ammonium salt phase transfer catalysts on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the catalyst type, other reaction conditions are the same as in Example 1. The results are shown in Table 3.

[0048] Table 3

[0049] 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

[0050] As shown in the results of Table 3, tetrabutylammonium iodide achieves a higher yield of the target product than tetrabutylammonium bromide, while the yield of the target product achieved by tetrabutylammonium chloride is lower than that of tetrabutylammonium bromide and tetrabutylammonium iodide, but still higher than the two non-quaternary ammonium salt phase transfer catalysts (polyethylene glycol, 18-crown ether-6) in Table 2. Without being limited by theory, this may be because the activity of the iodide ion in tetrabutylammonium iodide is higher than that of the bromide ion in tetrabutylammonium bromide, which further activates 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.

[0051] Embodiment 6-8

[0052] Based on Example 4, this example further investigates the effect of using different molar amounts of tetrabutylammonium iodide on the yield of the preparation reaction of p-tert-butoxybenzaldehyde. Except for the catalyst dosage, other reaction conditions are the same as those in Example 4. The results are shown in Table 4.

[0053] Table 4

[0054] 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

[0055] As shown in the results of 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, and when it 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%.

[0056] Examples 9-13

[0057] Based on Example 7, this example further investigates the effect of using different reflux temperatures as reaction temperatures on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the reflux temperature, other reaction conditions are the same as those in Example 7. The results are shown in Table 5.

[0058] Table 5

[0059] 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 Embodiment 11 135 10.9 86.1 Example 12 140 10.6 83.8 Embodiment 13 150 10.2 80.6

[0060] As shown in the results of Table 5, a relatively high yield is retained within the range of 125-150°C, and the yield decreases outside this range. Without being limited by theory, this may be because a relatively low reflux temperature may lead to incomplete reaction and reduced yield, while a relatively high reflux temperature may cause the aldehyde group of the p-chlorobenzaldehyde raw material to be destroyed, resulting in an increase in reaction impurities, thereby reducing the yield.

[0061] Examples 14-16

[0062] Based on Example 11, this example further investigates the effect of different reaction times on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the reaction time, other reaction conditions are the same as those in Example 11. The results are shown in Table 6.

[0063] Table 6

[0064] Response time (hours) Yield (g) Yield (%) Embodiment 14 3.0 9.5 75.1 Embodiment 15 4.0 10.8 85.3 Embodiment 11 5.0 10.9 86.1 Example 16 6.0 10.9 86.1

[0065] 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 it was extended to 6 hours, the yield also basically did not change, indicating that the reaction had basically reached the reaction endpoint at 4 hours.

[0066] Examples 17-21

[0067] On the basis of Example 15, this example further investigates the effect of different molar ratios of p-chlorobenzaldehyde and sodium tert-butoxide on the yield of p-tert-butoxybenzaldehyde preparation reaction. Except for the molar ratio of raw material feed, other reaction conditions are the same as those in Example 15. The results are shown in Table 7.

[0068] Table 7

[0069]

[0070] As shown in the results of Table 7, there is an excess amount of sodium tert-butoxide between p-chlorobenzaldehyde and sodium tert-butoxide. When the amount of sodium tert-butoxide increases 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.

[0071] Examples 22-25

[0072] On the basis of Example 19, this example constructs a composite catalyst of tetrabutylammonium iodide and different halides, and investigates the effect of the composite catalyst on the yield of the preparation reaction of tert-butoxybenzaldehyde. Specifically, 1.5 mol% tetrabutylammonium iodide of the p-chlorobenzaldehyde feed amount and 2 wt% of potassium iodide or sodium iodide or potassium bromide or potassium chloride of the p-chlorobenzaldehyde feed amount are mixed into a homogeneous mixture as a composite catalyst added to the reaction system. Except for the catalyst, other reaction conditions are the same as in Example 19. The results are shown in Table 8.

[0073] Table 8

[0074] Catalyst or composite catalyst Yield (g) Yield (%) Embodiment 19 1.5 mol% Tetrabutylammonium iodide 11.2 88.5 Comparative Example 3 2 wt% potassium iodide 3.0 23.7 Embodiment 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Embodiment 23 1.5 mol% tetrabutylammonium iodide + 2 wt% sodium iodide 11.9 94.0 Embodiment 24 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium bromide 11.6 91.7 Embodiment 25 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium chloride 11.2 88.5

[0075] As shown in the results of Table 8, potassium iodide or sodium iodide providing iodide ions and potassium bromide providing bromide ions further improved the yield of the target product to varying degrees relative to tetrabutylammonium iodide alone, but potassium chloride providing chloride ions failed to further improve the yield of the target product relative to tetrabutylammonium iodide alone. It can be seen that not all types of halides can improve the yield of the target product after forming a composite catalyst with tetrabutylammonium iodide.

[0076] Examples 26-29

[0077] Based on Example 22, this example further investigates the effect of different potassium iodide addition amounts on the yield of the preparation reaction of p-tert-butyloxybenzaldehyde in the composite catalyst. Except for the potassium iodide addition amount, the other reaction conditions are the same as those in Example 22. The results are shown in Table 9.

[0078] Table 9

[0079] Composite catalyst Yield (g) Yield (%) Embodiment 26 1.5 mol% tetrabutylammonium iodide + 1 wt% potassium iodide 11.5 90.9 Embodiment 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Embodiment 27 1.5 mol% tetrabutylammonium iodide + 3 wt% potassium iodide 12.1 95.6 Embodiment 28 1.5 mol% tetrabutylammonium iodide + 4 wt% potassium iodide 12.2 96.4 Embodiment 29 1.5 mol% tetrabutylammonium iodide + 5 wt% potassium iodide 12.2 96.4

[0080] 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.

[0081] Examples 30-31

[0082] This example investigates the effect of constructing a composite catalyst of a non-quaternary ammonium salt phase transfer catalyst and potassium iodide on the yield of the p-tert-butyloxybenzaldehyde preparation reaction. Except for the different catalysts, the other reaction conditions are the same as in Example 22. The results are shown in Table 10.

[0083] Table 10

[0084] catalyst Yield (g) Yield (%) Embodiment 22 1.5 mol% tetrabutylammonium iodide + 2 wt% potassium iodide 11.9 94.0 Embodiment 30 1.5 mol% polyethylene glycol + 2 wt% potassium iodide 9.8 77.4 Embodiment 31 1.5 mol% 18-crown ether-6 + 2 wt% potassium iodide 10.4 82.2

[0085] As shown in the results of Table 10, adding 2 wt % potassium iodide in non-quaternary ammonium salt phase transfer catalyst (polyethylene glycol, 18-crown ether-6) also further improves the target product yield. Compared with Example 22, the yield of the target product of Examples 30-31 is relatively low, and it can be seen that the quaternary ammonium salt phase transfer catalyst tetrabutylammonium iodide has a better technical effect than the non-quaternary ammonium salt phase transfer catalyst polyethylene glycol, 18-crown ether-6 and the halide potassium iodide combined into a composite catalyst.

[0086] Embodiment 32

[0087] Preparation of further derivatives of tert-butyl aryl ether (p-tert-butoxystyrene):

[0088] The raw materials involved in this example are the pure p-tert-butoxybenzaldehyde product obtained in the above examples and methylenetriphenylphosphine as a Wittig reagent, and the solvent is petroleum ether.

[0089] At room temperature (25°C) and normal pressure, 10g of pure p-tert-butyloxybenzaldehyde was dissolved in 80g of petroleum ether (industrial pure), placed in a 250mL three-necked flask, heated to 65°C, and stirred to fully dissolve. Then, a total of 16.25g of methylenetriphenylphosphine (CH 2 =P-Ph 3 The temperature was adjusted to reflux temperature of 60°C, and the reflux reaction was timed to 3 hours from the time the reflux temperature was reached. The reaction progress was tracked by detecting the amount of the product by GC.

[0090] After the reaction was completed for 3 h, the reaction system was concentrated by rotary evaporation at 35 ° C, and then ethyl acetate was used as an extractant to extract the concentrated product, and then the extract was washed with pure water for 4 times. Finally, the obtained washed product was concentrated by rotary evaporation at 40 ° C to obtain tert-butyloxystyrene (CH 2 =CH-C 6 H 4 -OC-(CH 3 ) 3 , molecular weight 176.25) crude product, and then distilled and purified 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%.

[0091] Although the present invention has been disclosed as above with preferred embodiments, it 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 p-chlorobenzaldehyde with solid sodium tert-butoxide in an organic solvent under the catalysis of a catalyst to produce p-tert-butoxybenzaldehyde; the catalyst at least contains a phase transfer catalyst; the phase transfer catalyst is a phase transfer catalyst containing halogen; the phase transfer catalyst containing halogen is a quaternary ammonium salt containing halogen; the quaternary ammonium salt containing halogen is selected from any one or a combination of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride; the reaction temperature is 125-150°C, and the reaction time is 4-6 hours.

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

3. The method for preparing tert-butyl aryl ether according to claim 1, characterized in that: The usage amount of the phase transfer catalyst is 0.5-2.0 mol% based on the molar amount of the p-chlorobenzaldehyde; the molar ratio of the p-chlorobenzaldehyde to the sodium tert-butoxide is 1:1.5-1:1.

75.

4. The method for preparing tert-butyl aryl ether according to claim 1, characterized in that: The catalyst is a combination of the 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 p-chlorobenzaldehyde, and the amount of the halide used is 1-5% of the weight of the p-chlorobenzaldehyde.

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