A method for the rapid phase-transfer hydrolysis of benzyl chloride to prepare (substituted) benzyl alcohol / aldehyde

Abstract

This invention discloses a method for the rapid phase-transfer hydrolysis of benzyl chloride to prepare (substituted) benzyl alcohol / aldehyde, comprising: uniformly dispersing a solid porous material and an ionic liquid in water; performing a hydrolysis reaction using benzyl chloride and water as raw materials; and allowing the reaction solution to stand and separate into an organic phase and an aqueous phase after the reaction, wherein the organic phase is the (substituted) benzyl alcohol / aldehyde. This invention involves uniformly dispersing a solid porous material and an ionic liquid in water, and performing a rapid hydrolysis reaction using benzyl chloride and water as raw materials. Quaternary phosphine or quaternary ammonium cations carry hydroxide ions and porous materials from the aqueous phase into the organic phase through electrostatically assisted hydrogen bonding, van der Waals forces, and other weak interactions. The inherent cavity of the solid porous material provides abundant mass transfer channels for the reaction in the organic phase, and the acid sites within the cavity catalyze the hydrolysis reaction, resulting in a reaction rate at least twice that of traditional phase transfer methods at the same conversion rate.

Description

Technical Field

[0001] This invention belongs to the field of process intensification, and specifically relates to a method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride. Background Technology

[0002] Benzyl chloride hydrolysis is the most commonly used method in industry for the preparation of (substituted) benzyl alcohol and (substituted) benzaldehyde. Patent CN104926611A proposes a new process for the alkali-free continuous hydrolysis of benzyl chloride to prepare benzyl alcohol. The introduced phase transfer catalyst solves the mass transfer problem, ensuring timely material transfer and avoiding the aggravation of side reactions. Patent CN1626493A reports a method for preparing benzaldehyde and substituted benzaldehyde using a cyclic phase transfer catalytic hydrolysis method. The phase transfer catalyst and hydrolysis process water are recycled, and the entire hydrolysis process produces no wastewater, waste gas, or waste residue, making it a clean production process. Patent CN102491887A discloses a method integrating the acid hydrolysis and hydrolysis reactions of benzyl dichloroide to produce benzaldehyde and acyl chloride. This method integrates the acid hydrolysis and hydrolysis reactions of benzyl dichloroide, allowing unreacted benzyl dichloroide to be completely eliminated through hydrolysis. This method saves equipment investment, reduces separation energy consumption, and improves product yield. Desikan et al. (Chemical Engineering Science. 2000, 55, 6119-6127) compared the catalytic activity of soluble phase-transfer catalysts and polymer-supported phase-transfer catalysts in the reaction of benzyl chloride with an aqueous sodium acetate solution. Due to the limitations imposed by external and intraparticle mass transfer on the three-phase catalyst, the reaction activity was lower, and the reaction rate was limited, with the activity being 50% lower than that of the corresponding soluble catalyst. Therefore, although current phase-transfer catalytic systems used for this type of reaction have improved the reaction rate to some extent, the reaction time remains very long, reaching up to 20 hours and requiring at least 3 hours. Summary of the Invention

[0003] To address the slow catalytic hydrolysis rate of benzyl chloride in existing methods, this invention provides a method for the rapid phase-transfer hydrolysis of benzyl chloride to prepare (substituted) benzyl alcohol / aldehyde. A solid porous material and an ionic liquid are uniformly dispersed in water, where the inherent cavities enhance mass transfer, resulting in a reaction rate at least twice that of conventional phase-transfer methods at the same conversion rate.

[0004] This invention provides the following technical solution:

[0005] A method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase-transfer hydrolysis of benzyl chloride includes: uniformly dispersing a solid porous material and an ionic liquid in water; performing a rapid hydrolysis reaction using benzyl chloride and water as raw materials; after the reaction, allowing the reaction solution to stand and separate into an organic phase and an aqueous phase, the organic phase being the (substituted) benzyl alcohol / aldehyde; wherein the solid porous material is a molecular cage or a metal-organic framework; and the ionic liquid is a quaternary phosphine salt ionic liquid or a quaternary ammonium salt ionic liquid. During the reaction, the quaternary phosphine or quaternary ammonium cations carry hydroxide ions and the solid porous material from the aqueous phase into the organic phase through electrostatically assisted hydrogen bonding, van der Waals forces, and other weak interactions. The inherent cavity of the solid porous material provides abundant mass transfer channels for the reaction in the organic phase, and the acid sites within the cavity catalyze the hydrolysis reaction; after the reaction, the quaternary phosphine or quaternary ammonium cations carry the porous material and chloride ions back to the aqueous phase, leaving only (substituted) benzyl alcohol or (substituted) benzaldehyde in the organic phase.

[0006] The molecular cage is one of the following: copper-based or vanadium-based small rhombic truncated half-cube, copper-based large rhombic truncated half-cube, substituted or unsubstituted zirconium-based tetrahedron, zirconium-based cube, substituted or unsubstituted vanadium-based regular octahedron, vanadium-based truncated triangular prism, vanadium-based truncated tetraangular prism, vanadium-based or copper-based octahedron, vanadium-based rhombic dodecahedron, substituted or unsubstituted vanadium-based tetrahedron, substituted or unsubstituted vanadium-based truncated tetrahedron, vanadium-based cubic octahedron, vanadium-based octahedron, vanadium-based icosahedron, vanadium-based icosahedron, substituted or unsubstituted vanadium-based cyclic vanadium-oxygen cluster-based coordination cage, etc.

[0007] The copper-based small rhombohedral half-cube is MOP-18; the vanadium-based small rhombohedral half-cube is Nanoball-1; the copper-based large rhombohedral half-cube is MOP-1; the substituted or unsubstituted zirconium-based tetrahedrons are ZrT-1, ZrT-3, ZrT-1-NH2, TCPB-1; the zirconium-based cube is HCCF-1; the substituted or unsubstituted vanadium-based regular octahedrons are VMOP-1, VMOP-2, VMOP-3, VMOP-26; the vanadium-based truncated triangular prism is VMOP-4; the vanadium-based truncated tetraangular prism is VMOP-5; the copper-based octahedrons are MOP-28, Cu-MOP; the vanadium-based octahedrons are VMOP-6, VMOP-7, V-MOP-19, VMOP-21, VMOP-31; the vanadium-based rhombus... The dodecahedron is VMOP-8; the substituted or unsubstituted vanadium-based tetrahedra are VMOP-11, VMOP-12, VMOP-13, VMOP-14, and VMOP-15; the substituted or unsubstituted vanadium-based truncated tetrahedra are VMOP-16, VMOP-17, VMOP-α, and VMOP-β; the vanadium-based cubic octahedron is VMOP-18, VMOP-19, and VMOP-20; the vanadium-based octadecahedron is VMOP-22, VMOP-27, and VMOP-28; the vanadium-based tetradecahedron is VMOP-23; the vanadium-based pentahedron is VMOP-24; the vanadium-based icosahedron is VMOP-25; and the substituted or unsubstituted vanadium-based cyclic vanadium-oxygen cluster coordination cages are HD-H, HD-Br, HD-OCH3, and HD-OH.

[0008] The metal-organic framework is one of UiO-66, UiO-66-NH2, UiO-67, NU-1000, PCN-222, MIL-100-Cr, MIL-101-Cr, MIL-100-Fe, ZIF-8, ZIF-11, ZIF-67, MOF-74, MIL-53-Al, MIL-53-Fe, MIL-53-Ga, MIL-53-NH2, MOF-303, MOF-333, MOF-801, MIL-177-LT, etc.

[0009] The quaternary phosphine salt ionic liquid is one of tributyl(tetradecyl)phosphine chloride, methyltributylphosphine iodide, ethyltributylphosphine bromide, tetrabutylphosphine bromide, and hexyltributylphosphine bromide.

[0010] The quaternary ammonium salt ionic liquid is one of benzyltriethylammonium chloride, tributylhexylammonium bromide, benzyltriethylammonium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium bromide.

[0011] The benzyl chloride is one of benzyl chloride, o-chlorobenzyl chloride, m-chlorobenzyl chloride, p-chlorobenzyl chloride, o-nitrobenzyl chloride, p-nitrobenzyl chloride, p-aminobenzyl chloride, o-fluorobenzyl chloride, p-fluorobenzyl chloride, p-bromobenzyl chloride, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, benzylene dichloro, o-chlorobenzylene dichloro, 3-chlorodichloromethylbenzene, p-chlorophenyldichloromethane, 2-(dichloromethyl)phenol, 2-fluorobenzylmethyl chloride, 3-fluorodichloromethylbenzene, 4-(dichloromethyl)phenol, 1-(dichloromethyl)-4-toluene, 4-fluorobenzylmethyl chloride, and 4-cyanodichlorobenzyl.

[0012] Corresponding to the benzyl chloride, the (substituted) benzyl alcohol / aldehyde is benzyl alcohol, o-chlorobenzyl alcohol, m-chlorobenzyl alcohol, p-chlorobenzyl alcohol, o-nitrobenzyl alcohol, p-nitrobenzyl alcohol, p-aminobenzyl alcohol, o-fluorobenzyl alcohol, p-fluorobenzyl alcohol, p-bromobenzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, 2-hydroxybenzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, p-hydroxybenzaldehyde, p-methylbenzaldehyde, 4-fluorobenzaldehyde, 4-cyanobenzaldehyde.

[0013] The weight ratio of water to benzyl chloride is 2:1 to 5:1.

[0014] The amount of the solid porous material added is 0.1 to 10 wt% of the weight of benzyl chloride.

[0015] The amount of the ionic liquid added is 0.5 to 20 wt% of the weight of benzyl chloride.

[0016] The hydrolysis reaction is carried out at a temperature of 90–105°C for 1–3 hours, and the reaction rate is at least twice that of conventional phase transfer at the same conversion rate.

[0017] The beneficial effects of this invention are reflected in:

[0018] This invention involves uniformly dispersing solid porous materials and ionic liquids in water, and using benzyl chloride and water as raw materials for a rapid hydrolysis reaction. Quaternary phosphine or quaternary ammonium cations carry hydroxide ions and porous materials from the aqueous phase into the organic phase through weak interactions such as electrostatically assisted hydrogen bonding and van der Waals forces. The inherent cavities of the solid porous material provide abundant mass transfer channels for the reaction in the organic phase. Acid sites within the cavities catalyze the hydrolysis reaction, and the reaction rate is at least twice that of traditional phase transfer at the same conversion rate. Detailed Implementation

[0019] The technical solution of the present invention will be further described below with reference to the embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally carried out in accordance with the means known to those skilled in the art.

[0020] Example 1

[0021] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 0.05 g MOP-18, 0.25 g tributyl(tetradecyl)phosphine chloride, 50 g benzyl chloride, and 100 g water were added, respectively. The mixture was reacted at 90 °C for 1 h until the benzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 33.8 g, and the organic phase was analyzed by gas chromatography. The mass percentage of benzyl alcohol was calculated to be 99.8%, and the reaction rate was 0.093 mol / (L·min).

[0022] Example 2

[0023] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 5 g Nanoball-1, 10 g methyltributylphosphine iodide, 50 g o-chlorobenzyl chloride, and 250 g water were added. The reaction was carried out at 105 °C for 3 h until the o-chlorobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.7 g and was analyzed by gas chromatography. The mass percentage of o-chlorobenzyl alcohol was calculated to be 99.4%, and the reaction rate was 0.031 mol / (L·min).

[0024] Example 3

[0025] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 0.5 g ZrT-1-NH2, 1 g ethyltributylphosphine bromide, 50 g m-chlorobenzyl chloride, and 120 g water were added. The mixture was reacted at 95 °C for 1.5 h until the m-chlorobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.5 g and was analyzed by gas chromatography. The mass percentage of m-chlorobenzyl alcohol was calculated to be 99.1%, and the reaction rate was 0.062 mol / (L·min).

[0026] Example 4

[0027] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 1.5 g of NU-1000, 3 g of tetrabutylphosphine bromide, 50 g of p-chlorobenzyl chloride, and 120 g of water were added. The mixture was reacted at 95 °C for 1.5 h until the p-chlorobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.6 g and was analyzed by gas chromatography. The mass percentage of p-chlorobenzyl alcohol was calculated to be 99.3%, and the reaction rate was 0.065 mol / (L·min).

[0028] Example 5

[0029] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 2.5 g of UiO-66, 4 g of hexyltributylphosphine bromide, 50 g of benzyl dichloroethylene, and 140 g of water were added. The reaction was carried out at 100 °C for 2 h until the benzyl dichloroethylene was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.2 g and was analyzed by gas chromatography. The benzaldehyde content was calculated to be 99.1% by mass, and the reaction rate was 0.047 mol / (L·min).

[0030] Example 6

[0031] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 3 g of MIL-53-Fe, 2.5 g of benzyltriethylammonium chloride, 50 g of o-benzyl chloride, and 160 g of water were added. The reaction was carried out at 93 °C for 2 h until the o-benzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 33.2 g. The organic phase was analyzed by gas chromatography, and the mass percentage of o-chlorobenzaldehyde was calculated to be 99.5%, with a reaction rate of 0.049 mol / (L·min).

[0032] Example 7

[0033] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 4 g of MIL-101-Cr, 6 g of tributylhexylammonium bromide, 50 g of 3-chlorodichloromethylbenzene, and 180 g of water were added. The reaction was carried out at 98 °C for 2.5 h until the 3-chlorodichloromethylbenzene was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 31.8 g. The organic phase was analyzed by gas chromatography, and the mass percentage of m-chlorobenzaldehyde was calculated to be 99.1%, with a reaction rate of 0.037 mol / (L·min).

[0034] Example 8

[0035] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 3.7 g of MIL-100-Fe, 4.5 g of benzyltriethylammonium bromide, 50 g of p-chlorophenyl dichloromethane, and 200 g of water were added. The reaction was carried out at 96 °C for 1.5 h until the p-chlorophenyl dichloromethane was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 33.3 g and was analyzed by gas chromatography. The mass percentage of p-chlorobenzaldehyde was calculated to be 99.6%, and the reaction rate was 0.068 mol / (L·min).

[0036] Example 9

[0037] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 4.5 g of MIL-53-Al, 6.8 g of tetrabutylammonium chloride, 50 g of p-chlorophenyl dichloromethane, and 250 g of water were added. The reaction was carried out at 99 °C for 2.5 h until the p-chlorophenyl dichloromethane was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.9 g and was analyzed by gas chromatography. The mass percentage of p-chlorobenzaldehyde was calculated to be 99.4%, and the reaction rate was 0.045 mol / (L·min).

[0038] Example 10

[0039] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 2.8 g of VMOP-28, 8.2 g of tetrabutylammonium bromide, 50 g of 4-cyanobenzyl chloride, and 250 g of water were added. The mixture was reacted at 97 °C for 3 h until the 4-cyanobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.5 g and was analyzed by gas chromatography. The mass percentage of 4-cyanobenzyl was calculated to be 99.1%, and the reaction rate was 0.035 mol / (L·min).

[0040] Example 11

[0041] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 3 g of HD-H, 4.6 g of tetrabutylammonium bromide, 50 g of o-nitrobenzyl chloride, and 250 g of water were added. The reaction was carried out at 95 °C for 2 h until the o-nitrobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.7 g and was analyzed by gas chromatography. The mass percentage of o-nitrobenzyl alcohol was calculated to be 99.5%, and the reaction rate was 0.05 mol / (L·min).

[0042] Example 12

[0043] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 4.5 g of HD-Br, 5.2 g of tetrabutylphosphine bromide, 50 g of p-bromobenzyl chloride, and 250 g of water were added. The reaction was carried out at 97 °C for 1 h until the p-bromobenzyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.9 g and was analyzed by gas chromatography. The mass percentage of p-bromobenzyl alcohol was calculated to be 99.7%, and the reaction rate was 0.087 mol / (L·min).

[0044] Example 13

[0045] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 1.2 g of HD-OCH3, 7.8 g of hexyltributylphosphine bromide, 50 g of 2-fluorobenzylmethyl chloride, and 250 g of water were added. The reaction was carried out at 99 °C for 2.5 h until the 2-fluorobenzylmethyl chloride was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.8 g and was analyzed by gas chromatography. The mass percentage of 2-fluorobenzaldehyde was calculated to be 99.5%, and the reaction rate was 0.046 mol / (L·min).

[0046] Example 14

[0047] In a 500 mL flat-bottomed three-necked reactor equipped with a magnetic stirrer, 3.6 g of HD-OH, 8 g of benzyltriethylammonium chloride, 50 g of 1-(dichloromethyl)-4-toluene, and 250 g of water were added. The reaction was carried out at 105 °C for 3 h until the 1-(dichloromethyl)-4-toluene was completely reacted. The reaction solution was allowed to stand and separate into organic and aqueous phases. The organic phase weighed 32.4 g and was analyzed by gas chromatography. The mass percentage of p-methylbenzaldehyde was calculated to be 99.3%, and the reaction rate was 0.038 mol / (L·min).

[0048] Comparative Example 1

[0049] Compared to Example 1, the only difference is that MOP-18 was not added to the reaction system. Benzyl chloride required 6 hours to react completely, and the organic phase weighed 33.2 g. Gas chromatography analysis of the organic phase showed that the benzyl alcohol content was 99.2% by mass, and the reaction rate was 0.016 mol / (L·min).

[0050] Comparative Example 2

[0051] Compared to Example 8, the only difference is that MIL-100-Fe was not added to the reaction system. The reaction of p-chlorophenyl dichloromethane required 8 hours to complete. The organic phase weighed 33.1 g. Gas chromatography analysis of the organic phase revealed a p-chlorobenzaldehyde content of 99.3% and a reaction rate of 0.012 mol / (L·min).

Claims

1. A process for the fast phase transfer hydrolysis of benzyl chloride to produce (substituted) benzyl alcohol / aldehyde, characterized by: include: A solid porous material and an ionic liquid are uniformly dispersed in water, and a hydrolysis reaction is carried out using benzyl chloride and water as raw materials. After the reaction, the reaction solution is allowed to stand and separate into an organic phase and an aqueous phase, the organic phase being (substituted) benzyl alcohol / aldehyde. The solid porous material is either a molecular cage or a metal-organic framework. The molecular cage is a copper-based or vanadium-based small rhombic truncated half-cube, a copper-based large rhombic truncated half-cube, a substituted or unsubstituted zirconium-based tetrahedron, a zirconium-based cube, a substituted or unsubstituted vanadium-based regular octahedron, a vanadium-based truncated triangular prism, a vanadium-based truncated tetrahedron, a vanadium-based octahedron, a vanadium-based rhombic dodecahedron, a substituted or unsubstituted vanadium-based tetrahedron, a substituted or unsubstituted vanadium-based truncated tetrahedron, a vanadium-based octahedron, a vanadium-based tetradecahedron, a vanadium-based pentahedron, or a vanadium-based dihedron. The invention comprises one of the following: a decahedron, a substituted or unsubstituted vanadium-based cyclic vanadium-oxygen cluster coordination cage; the copper-based small rhombic truncated half-cube is MOP-18; the vanadium-based small rhombic truncated half-cube is Nanoball-1; the copper-based large rhombic truncated half-cube is MOP-1; the substituted or unsubstituted zirconium-based tetrahedron is ZrT-1, ZrT-3, ZrT-1-NH2, TCPB-1; the zirconium-based cube is HCCF-1; the substituted or unsubstituted vanadium-based regular octahedron is VMOP-1, VMOP-2, VMOP-3, VMOP-26; the vanadium-based truncated triangular prism is VMOP-4; the vanadium-based truncated tetraangular prism is VMOP-5; and the vanadium-based octahedron is VMOP-6. VMOP-7, V-MOP-19, VMOP-21, VMOP-31; the vanadium-based rhombic dodecahedron is VMOP-8; the substituted or unsubstituted vanadium-based tetrahedron is VMOP-11, VMOP-12, VMOP-13, VMOP-14, VMOP-15; the substituted or unsubstituted vanadium-based truncated tetrahedron is VMOP-16, VMOP-17, VMOP-α, VMOP-β; the vanadium-based octadecahedron is VMOP-22, VMOP-27, VMOP-28; the vanadium-based tetradecahedron is VMOP-23; the vanadium-based pentahedron is VMOP-24; the vanadium-based icosahedron is VMOP-25; the substituted... The unsubstituted vanadium-based cyclic vanadium oxide cluster coordination cage may be HD-H, HD-Br, HD-OCH3, or HD-OH; the metal-organic framework may be one of UiO-66, UiO-66-NH2, UiO-67, NU-1000, PCN-222, MIL-100-Cr, MIL-101-Cr, MIL-100-Fe, ZIF-8, ZIF-11, ZIF-67, MIL-53-Al, MIL-53-Fe, MIL-53-Ga, MIL-53-NH2, MOF-303, MOF-333, MOF-801, or MIL-177-LT; and the ionic liquid may be a quaternary phosphine salt ionic liquid or a quaternary ammonium salt ionic liquid.

2. A process for the rapid phase transfer hydrolysis of benzyl chloride to produce (substituted) benzyl alcohol / aldehyde as claimed in claim 1, wherein: The quaternary phosphine salt ionic liquid is one of tributyl(tetradecyl)phosphine chloride, methyltributylphosphine iodide, ethyltributylphosphine bromide, tetrabutylphosphine bromide, and hexyltributylphosphine bromide.

3. A process for the rapid phase transfer hydrolysis of benzyl chloride to produce (substituted) benzyl alcohol / aldehyde as claimed in claim 1, wherein: The quaternary ammonium salt ionic liquid is one of benzyltriethylammonium chloride, tributylhexylammonium bromide, benzyltriethylammonium bromide, tetrabutylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium bromide.

4. The method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride according to claim 1, characterized in that: The benzyl chloride is one of benzyl chloride, o-chlorobenzyl chloride, m-chlorobenzyl chloride, p-chlorobenzyl chloride, o-nitrobenzyl chloride, p-nitrobenzyl chloride, p-aminobenzyl chloride, o-fluorobenzyl chloride, p-fluorobenzyl chloride, p-bromobenzyl chloride, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, benzylene dichloro, o-chlorobenzylene dichloro, 3-chlorodichloromethylbenzene, p-chlorophenyldichloromethane, 2-(dichloromethyl)phenol, 2-fluorobenzylmethyl chloride, 3-fluorodichloromethylbenzene, 4-(dichloromethyl)phenol, 1-(dichloromethyl)-4-toluene, 4-fluorobenzylmethyl chloride, and 4-cyanodichlorobenzyl.

5. The method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride according to claim 1, characterized in that: The weight ratio of water to benzyl chloride is 2:1 to 5:

1.

6. The method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride according to claim 1, characterized in that: The amount of the solid porous material added is 0.1 to 10 wt% of the weight of benzyl chloride.

7. The method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride according to claim 1, characterized in that: The amount of the ionic liquid added is 0.5 to 20 wt% of the weight of benzyl chloride.

8. The method for preparing (substituted) benzyl alcohol / aldehyde by rapid phase transfer hydrolysis of benzyl chloride according to claim 1, characterized in that: The hydrolysis reaction is carried out at a temperature of 90–105 °C for 1–3 h.