Synthesis method of 1-chloromethyl naphthalene and application of catalyst and non-cationic surfactant thereof

Abstract

The invention relates to a synthesis method of 1-chloromethyl naphthalene and application of a catalyst and a non-cationic surfactant thereof. The invention provides the application of the non-cationic surfactant for synthesizing the catalyst of the 1-chloromethyl naphthalene with a quaternary ammonium salt by using methanal or paraformaldehyde, naphthalene and concentrated hydrochloric acid as raw materials. The synthesis method of the 1-chloromethyl naphthalene comprises the following steps of: (a) mixing the methanal or the paraformaldehyde, the naphthalene, the concentrated hydrochloric acid and the catalyst; (b) stirring for reacting for a period of time at reaction temperature and cooling; and (c) separating and purifying to obtain the 1-chloromethyl naphthalene, wherein in the step(a), the catalyst consists of the quaternary ammonium salt and the non-cationic surfactant. The invention provides the catalyst which is used for synthesizing the 1-chloromethyl naphthalene and consists of the quaternary ammonium salt and the non-cationic surfactant, wherein the mass ratio of the quaternary ammonium salt to the non-cationic surfactant is 1:(0.1-0.5). The invention solves the problems of long reaction time and low reaction yield of the traditional synthesis method of the 1-chloromethyl naphthalene.

Description

technical field

[0001] The present invention relates to the new application of non-cationic surfactant; The present invention relates to a kind of synthetic method again, specifically relate to the synthetic method of 1-chloromethyl naphthalene; The present invention also relates to the used catalyst of the synthetic method of 1-chloromethyl naphthalene. Background technique

[0002] 1-Chloromethylnaphthalene, also known as α-chloromethylnaphthalene, English name 1-chloromethylnaphthalene, crystal, melting point 32°C, boiling point 135-136°C (0.798kPa), refractive index 1.6370, density 1.180g / cm 3 , flash point > 110 ° C, soluble in ether and benzene, and is a lacrimal irritant.

[0003] 1-Chloromethylnaphthalene is an important intermediate in organic synthesis, which can be used to synthesize α-naphthaldehyde, 1-naphthoic acid, 1-naphthylacetic acid, 1-naphthoyl chloride, 1-naphthaleneacetonitrile, 1-naphthaleneacetamide, 1-Naphthylmethylamine and other products. [0...

Examples

preparation example Construction

[0042] A kind of synthetic method of 1-chloromethylnaphthalene, the method uses the catalyst that the synthetic 1-chloromethylnaphthalene proposed by the present invention is used, and the method comprises the following steps:

[0043]a), formaldehyde or paraformaldehyde and naphthalene, concentrated hydrochloric acid, catalyzer are mixed, and catalyzer is the catalyzer that the synthetic 1-chloromethylnaphthalene of the present invention proposes, and the mass ratio of catalyzer and naphthalene is 0.01~0.04: 1, naphthalene and The molar ratio of concentrated hydrochloric acid is 1:1.8~3, and the molar ratio of naphthalene to formaldehyde or paraformaldehyde is 1:1.5~2.5; there is no order in adding the two components of the catalyst;

[0044] b), stirring and reacting at the reaction temperature for a period of time, the reaction temperature is 70-90°C, the reaction temperature is preferably 75-80°C, and the reaction period is 3-5 hours;

[0045] c), cooled to room temperatur...

Embodiment 1

[0053] In a 500ml three-necked flask equipped with a thermometer and a condenser tube, add 25.6g (0.20mol) of naphthalene, 11g (converted into formaldehyde 0.37mol) of paraformaldehyde, and 40ml of 36% concentrated hydrochloric acid (0.47mol) respectively. The weight ratio of the catalyst is 1.000:0.03, and the composition of the catalyst is tetraethylammonium bromide:N, N-sodium oleoylmethyl taurate=1:0.5. Stir at 75°C for 5h. After cooling, extract with cyclohexane and use 10% NaHCO 3 The solution was washed, and the cyclohexane was removed by rotary evaporation. Carried out vacuum distillation to obtain 33.86 g of 99.1% 1-chloromethylnaphthalene product. The product yield of 1-chloromethylnaphthalene is 95.7%.

Embodiment 2

[0058] In a 500ml three-neck flask equipped with a thermometer and a condenser tube, add 12.8g (0.10mol) of naphthalene, 6g (converted into formaldehyde 0.20mol) of paraformaldehyde, and 18ml of concentrated hydrochloric acid (0.21mol), according to the weight ratio of naphthalene to catalyst The catalyst is added at a ratio of 1.000:0.04, and the composition of the catalyst is tetraethylammonium chloride: fatty acid diethanolamide=1:0.2. Stir at 80°C for 4h. After cooling, extract with cyclohexane and use 10% NaHCO 3 The solution was washed, and the cyclohexane was removed by rotary evaporation. Carried out vacuum distillation to obtain 16.84 g of 99.3% 1-chloromethylnaphthalene product. The product yield of 1-chloromethylnaphthalene is 95.4%.

technical field

[0001] The present invention relates to the new application of non-cationic surfactant; The present invention relates to a kind of synthetic method again, specifically relate to the synthetic method of 1-chloromethyl naphthalene; The present invention also relates to the used catalyst of the synthetic method of 1-chloromethyl naphthalene. Background technique

[0002] 1-Chloromethylnaphthalene, also known as α-chloromethylnaphthalene, English name 1-chloromethylnaphthalene, crystal, melting point 32°C, boiling point 135-136°C (0.798kPa), refractive index 1.6370, density 1.180g / cm 3 , flash point > 110 ° C, soluble in ether and benzene, and is a lacrimal irritant.

[0003] 1-Chloromethylnaphthalene is an important intermediate in organic synthesis, which can be used to synthesize α-naphthaldehyde, 1-naphthoic acid, 1-naphthylacetic acid, 1-naphthoyl chloride, 1-naphthaleneacetonitrile, 1-naphthaleneacetamide, 1-Naphthylmethylamine and other products. [0...

Examples

preparation example Construction

[0042] A kind of synthetic method of 1-chloromethylnaphthalene, the method uses the catalyst that the synthetic 1-chloromethylnaphthalene proposed by the present invention is used, and the method comprises the following steps:

[0043]a), formaldehyde or paraformaldehyde and naphthalene, concentrated hydrochloric acid, catalyzer are mixed, and catalyzer is the catalyzer that the synthetic 1-chloromethylnaphthalene of the present invention proposes, and the mass ratio of catalyzer and naphthalene is 0.01~0.04: 1, naphthalene and The molar ratio of concentrated hydrochloric acid is 1:1.8~3, and the molar ratio of naphthalene to formaldehyde or paraformaldehyde is 1:1.5~2.5; there is no order in adding the two components of the catalyst;

[0044] b), stirring and reacting at the reaction temperature for a period of time, the reaction temperature is 70-90°C, the reaction temperature is preferably 75-80°C, and the reaction period is 3-5 hours;

[0045] c), cooled to room temperatur...

Embodiment 1

[0053] In a 500ml three-necked flask equipped with a thermometer and a condenser tube, add 25.6g (0.20mol) of naphthalene, 11g (converted into formaldehyde 0.37mol) of paraformaldehyde, and 40ml of 36% concentrated hydrochloric acid (0.47mol) respectively. The weight ratio of the catalyst is 1.000:0.03, and the composition of the catalyst is tetraethylammonium bromide:N, N-sodium oleoylmethyl taurate=1:0.5. Stir at 75°C for 5h. After cooling, extract with cyclohexane and use 10% NaHCO 3 The solution was washed, and the cyclohexane was removed by rotary evaporation. Carried out vacuum distillation to obtain 33.86 g of 99.1% 1-chloromethylnaphthalene product. The product yield of 1-chloromethylnaphthalene is 95.7%.

Embodiment 2

[0058] In a 500ml three-neck flask equipped with a thermometer and a condenser tube, add 12.8g (0.10mol) of naphthalene, 6g (converted into formaldehyde 0.20mol) of paraformaldehyde, and 18ml of concentrated hydrochloric acid (0.21mol), according to the weight ratio of naphthalene to catalyst The catalyst is added at a ratio of 1.000:0.04, and the composition of the catalyst is tetraethylammonium chloride: fatty acid diethanolamide=1:0.2. Stir at 80°C for 4h. After cooling, extract with cyclohexane and use 10% NaHCO 3 The solution was washed, and the cyclohexane was removed by rotary evaporation. Carried out vacuum distillation to obtain 16.84 g of 99.3% 1-chloromethylnaphthalene product. The product yield of 1-chloromethylnaphthalene is 95.4%.