A kind of preparation method of 1-chloromethylnaphthalene

Abstract

The invention relates to the technical field of organic synthesis, and specifically discloses a preparation method of 1-chloromethylnaphthalene. The preparation method includes the following steps: uniformly mixing naphthalene, paraformaldehyde, Lewis acid, phase transfer catalyst and a hydrochloric acid solution with a mass concentration of 42% to 43%, heat preservation reaction, standing for liquid separation, and washing the oil phase to obtain 1 - chloromethyl naphthalene crude product; 1- chloromethyl naphthalene crude product is added to an alcohol solvent, the temperature is raised to dissolve clear, cooled for crystallization, filtered, washed, and dried to obtain 1- chloromethyl naphthalene product; wherein, the Lewis acid is ferric chloride A mixture of copper chloride and copper chloride; the phase transfer catalyst is one or both of benzyltrimethylammonium chloride or benzyltriethylammonium chloride. The invention effectively improves the yield and purity of the 1-chloromethyl naphthalene product through a simple process, and effectively shortens the reaction time for preparing the 1-chloromethyl naphthalene, without rectification, and only needs to be crystallized and purified by using an alcohol solvent. , low energy consumption, high operational safety and broad market prospects.

Description

technical field

[0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1-chloromethylnaphthalene. Background technique

[0002] 1-Chloromethylnaphthalene, also known as α-chloromethylnaphthalene, English name 1-chloromethylnaphthalene, melting point 32℃, boiling point 164℃~165℃ (2.67kPa), refractive index 1.6370, density 1.180g / cm 3 , flash point> 110 ℃, soluble in ether, benzene, as a tear irritant. 1-Chloromethylnaphthalene is an important organic synthesis intermediate, which can synthesize α-naphthalene carboxaldehyde, 1-naphthalene carboxaldehyde, 1-naphthaleneacetic acid, 1-naphthoyl chloride, 1-naphthaleneacetonitrile, 1-naphthaleneacetamide, 1-Naphthylmethylamine and other products.

[0003] At present, 1-chloromethylnaphthalene is mainly prepared by chloromethylation of naphthalene, and the prepared product has complex components, usually containing naphthalene, 2-chloromethylnaphthalene and 1,4-dichlo...

Examples

Embodiment 1

[0041] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0042] Step a, 128g (1mol) of naphthalene, 60g (2mol) of paraformaldehyde, FeCl 3 3.25g (0.02mol), CuCl 2 2.69g (0.02mol), 3.42g (0.015mol) of benzyltriethylammonium chloride and 214.7g (2.5mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, and the temperature was raised to 40°C for 3 hours. Set liquid separation, the oil phase is washed twice with 10wt% potassium carbonate solution and water respectively to obtain 1-chloromethylnaphthalene crude product;

[0043] In step b, the crude 1-chloromethylnaphthalene was added to 192 g of absolute ethanol, heated to 26 °C to dissolve, then cooled to -5 °C at a rate of 0.5 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was placed in a vacuum drying oven, and dried at 25 mmHg and 35° C. for 5 h to obtain 171.5 g of 1-chloromethylnaph...

Embodiment 2

[0045] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0046] Step a, 128g (1mol) of naphthalene, 60g (2mol) of paraformaldehyde, FeCl 3 3.25g (0.02mol), CuCl 21.35g (0.01mol), 2.28g (0.01mol) of benzyltriethylammonium chloride and 257.6g (3mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, heated to 45°C and incubated for 3h, cooled and allowed to stand Separation, the oil phase was washed twice with 10wt% potassium carbonate solution and water, respectively, to obtain 1-chloromethylnaphthalene crude product;

[0047] In step b, the crude 1-chloromethylnaphthalene was added to 160 g of absolute ethanol, heated to 27 °C to dissolve, then cooled to -3 °C at a rate of 0.6 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was put into a vacuum drying oven, and dried at 25mmHg and 30°C for 6h to obtain 168.8g of 1-chloromethylnaphthalen...

Embodiment 3

[0049] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0050] Step a, 128g (1mol) of naphthalene, 45g (1.5mol) of paraformaldehyde, FeCl 3 2.44g (0.015mol), CuCl 2 2.03 g (0.015 mol), 1.82 g (0.008 mol) of benzyltriethylammonium chloride and 214.7 g (2.5 mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, and the temperature was raised to 45 °C for 4 hours, then the temperature was cooled, and the mixture was kept quiet. Set liquid separation, the oil phase is washed twice with 10wt% potassium carbonate solution and water respectively to obtain 1-chloromethylnaphthalene crude product;

[0051] In step b, the crude 1-chloromethylnaphthalene was added to 128 g of absolute ethanol, heated to 28 °C for dissolving, then cooled to -5 °C at a rate of 0.8 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was placed in a vacuum drying oven, a...

technical field

[0001] The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1-chloromethylnaphthalene. Background technique

[0002] 1-Chloromethylnaphthalene, also known as α-chloromethylnaphthalene, English name 1-chloromethylnaphthalene, melting point 32℃, boiling point 164℃~165℃ (2.67kPa), refractive index 1.6370, density 1.180g / cm 3 , flash point> 110 ℃, soluble in ether, benzene, as a tear irritant. 1-Chloromethylnaphthalene is an important organic synthesis intermediate, which can synthesize α-naphthalene carboxaldehyde, 1-naphthalene carboxaldehyde, 1-naphthaleneacetic acid, 1-naphthoyl chloride, 1-naphthaleneacetonitrile, 1-naphthaleneacetamide, 1-Naphthylmethylamine and other products.

[0003] At present, 1-chloromethylnaphthalene is mainly prepared by chloromethylation of naphthalene, and the prepared product has complex components, usually containing naphthalene, 2-chloromethylnaphthalene and 1,4-dichlo...

Examples

Embodiment 1

[0041] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0042] Step a, 128g (1mol) of naphthalene, 60g (2mol) of paraformaldehyde, FeCl 3 3.25g (0.02mol), CuCl 2 2.69g (0.02mol), 3.42g (0.015mol) of benzyltriethylammonium chloride and 214.7g (2.5mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, and the temperature was raised to 40°C for 3 hours. Set liquid separation, the oil phase is washed twice with 10wt% potassium carbonate solution and water respectively to obtain 1-chloromethylnaphthalene crude product;

[0043] In step b, the crude 1-chloromethylnaphthalene was added to 192 g of absolute ethanol, heated to 26 °C to dissolve, then cooled to -5 °C at a rate of 0.5 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was placed in a vacuum drying oven, and dried at 25 mmHg and 35° C. for 5 h to obtain 171.5 g of 1-chloromethylnaph...

Embodiment 2

[0045] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0046] Step a, 128g (1mol) of naphthalene, 60g (2mol) of paraformaldehyde, FeCl 3 3.25g (0.02mol), CuCl 21.35g (0.01mol), 2.28g (0.01mol) of benzyltriethylammonium chloride and 257.6g (3mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, heated to 45°C and incubated for 3h, cooled and allowed to stand Separation, the oil phase was washed twice with 10wt% potassium carbonate solution and water, respectively, to obtain 1-chloromethylnaphthalene crude product;

[0047] In step b, the crude 1-chloromethylnaphthalene was added to 160 g of absolute ethanol, heated to 27 °C to dissolve, then cooled to -3 °C at a rate of 0.6 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was put into a vacuum drying oven, and dried at 25mmHg and 30°C for 6h to obtain 168.8g of 1-chloromethylnaphthalen...

Embodiment 3

[0049] The present embodiment provides a preparation method of 1-chloromethylnaphthalene, comprising the following steps:

[0050] Step a, 128g (1mol) of naphthalene, 45g (1.5mol) of paraformaldehyde, FeCl 3 2.44g (0.015mol), CuCl 2 2.03 g (0.015 mol), 1.82 g (0.008 mol) of benzyltriethylammonium chloride and 214.7 g (2.5 mol) of hydrochloric acid solution with a mass concentration of 42.5% were mixed evenly, and the temperature was raised to 45 °C for 4 hours, then the temperature was cooled, and the mixture was kept quiet. Set liquid separation, the oil phase is washed twice with 10wt% potassium carbonate solution and water respectively to obtain 1-chloromethylnaphthalene crude product;

[0051] In step b, the crude 1-chloromethylnaphthalene was added to 128 g of absolute ethanol, heated to 28 °C for dissolving, then cooled to -5 °C at a rate of 0.8 °C / 10min for 2 hours, then filtered and washed with absolute ethanol. , the filter cake was placed in a vacuum drying oven, a...