JPS5812274B2 - 1-Hydroxybenzotriazoleluino - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to reducing acyl-substituted nitrobenzenes represented by the general formula (wherein R represents hydrogen or an alkyl group, and X represents a halogen) to obtain A hydroxyalkyl-substituted nitrobenzene represented by R and Production of 1-hydroxybenzotriazoles, which consists of preparing substituted nitrobenzenes and then reacting them with hydrazine to obtain 1-hydroxybenzotriazoles represented by the general formula (wherein R has the same meaning as above) It is about law.

Among the acyl-substituted nitrobenzenes (I) used as raw materials in this invention, 3'-nitro-4'-chlorolaurophenone is a new compound, and it can be prepared by reacting fuming nitric acid with 4'-1-chlorolaurophenone. can be manufactured.

The reaction of this invention begins with acyl-substituted nitrobenzenes (
This is done by reducing I).

Acyl-substituted nitrobenzenes are represented by the above general formula (I), and more specifically, hydrogen or methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, etc. It means a compound having an alkyl group as R and a halogen such as chloro or brome as X.

The reduction methods used here include a method of reducing borohydride with an alkali metal borohydride such as sodium borohydride and potassium borohydride, and a method using an aluminum alkoxide such as aluminum isopropoxide. Can be mentioned.

When an alkali metal borohydride is used, the reaction is carried out in a conventional manner in a solvent that does not adversely affect the reaction, such as water, methanol, ethanol, tetrahydrofuran, dioxane, etc., usually under cooling or at room temperature.

When aluminum alkoxide is used, the reaction is usually carried out in a solvent such as isopropyl alcohol under heating according to a conventional method.

This invention is carried out by subsequently subjecting the hydroxyalkyl-substituted nitrobenzenes (■) thus obtained to a dehydration reaction.

The method used here includes a method using a dehydrating agent such as p-toluenesulfonic acid, phosphorus pentoxide, or acidic potassium sulfate.

This reaction is usually carried out under heating without a solvent.

The alkenyl-substituted nitrobenzenes (I
II) is then treated with hydrazine.

The hydrazine used here is usually a hydrate thereof.

Although this reaction can be carried out without a solvent, it is usually carried out in a solvent, and in addition to ethanol, tetrahydrofuran, etc., any solvent that does not adversely affect this reaction can be used.

This reaction is usually carried out under heating.

Moreover, this reaction can also be carried out in the presence of a base such as potassium carbonate or sodium hydroxide.

The 1-hydroxybenzotriazole (IV) thus obtained is isolated and collected by a conventional method.

The object product ([V) obtained by this invention is a new compound and is useful as an ultraviolet absorber and as a synthetic intermediate for an amidation or esterification condensing agent.

Next, the present invention will be explained with reference to examples.

Example 1 (a) 3-nitro-4-chloroacetophenone l57
150 ml of methanol is added to the solution, and 1.5 g of sodium borohydride is gradually added to this solution at a temperature below 20° C. After stirring at room temperature for 2.5 hours, the reaction solution is concentrated.

After adding water to the residue, it is extracted three times with 150 ml of ether, and the extract is washed with water and dried over sodium sulfate.

The solvent was distilled off from this solution under reduced pressure, and the residue was dissolved in a small amount of benzene. After adding n-hexane and leaving it in a cool place, pale yellow crystals of 1-(3-nitro-
12.5 f of 4-chlorophenyl)ethanol are obtained.

Elemental analysis: C8H8N03Cl Calculated value: C47.65, H 4.0 0, N 6.9
5, CI17.60 Experimental value: C47.56, H3.96, N6.93, CI
17.64 (b) 1-(3-nitro-4-chlorophenyl)ethanol 3 0. 0.6y of monohydrate of luenesulfonic acid is distilled on an oil bath at 150° C. under a reduced pressure of 4 to 5 mmHg in a room gas stream.

Dissolve the distillate in 250 ml of ether and add sodium bicarbonate.
After washing with IJum aqueous solution and water in this order, drying with sodium sulfate.

After distilling off the solvent from this solution, the residue was distilled again to produce 3-nitro-4 with a bpl of 20-122°C/6 Hg.
-23.6 g of chlorostyrene are obtained.

This stuff will crystallize if left alone.

mp31℃0 elemental analysis: C8H6N02Cl calculated value C52.32, H3.29, N7.63, CI
19.33 Experimental value C52.48, H3.12, N7.75, CI
19.35 (/υ 45.7 r of 3-nitro-4-chlorostyrene, 400 ml of 99% ethanol and 5 ml of hydrazine hydrate
Add 07 and heat under reflux in a 100°C oil bath for 48 hours.

After concentrating the reaction solution under reduced pressure, the residue was dissolved in 1.5 liters of water,
Wash 3 times with 200 ml of ether.

The ether layer is extracted with 100 ml of water, combined with the aqueous layer, and adjusted to pH 1 with concentrated hydrochloric acid.

After stirring this for 1 hour, the precipitate was collected by filtration, washed with 300 ml of water, and then dried under reduced pressure using phosphorus pentoxide.

The obtained crystal 36.7F was added to 60 rnl of methanol, and after removing insoluble matter, the slurry was concentrated under reduced pressure to give about 2.
00ml and leave it in a cool place.

When the precipitate was collected, 20.2 f of 1-hydroxy-6-vinyl-1H-penzotriazole was obtained as brown crystals with a temperature of mp 151 to 152°C.

In addition, this mother liquor was concentrated to about 100 d, and when it was cooled and a lot of precipitated crystals were collected, the same target substance 11.7
Get S'.

Total yield 31.9g. Elemental analysis: C8H, N30 Calculated values: C59.62, H4.38, N26.07 Experimental values: C59.65, H4.23, N26.21 Example
2 (Production of raw material compound) 600 ml of fuming nitric acid (specific gravity: 1.50) cooled with ice water
Add 4'-chlorolaurophenone 722 at 0-3℃,
After stirring for 10 minutes, pour the reaction mixture onto 3 kg of ice.

A large amount of the precipitate was collected and recrystallized from 95% ethanol. When the precipitate was collected, 66.0 g of 3'-1 ditro-4'-chlorolaurophenone was obtained as yellow crystals with a mp of 50 to 50.5°C.

In addition, this mother liquor was concentrated and the residue was dissolved in 50ml of 95% ethanol.
When crystallized from 1, the target substance 52 is also obtained.

Total yield 712. Elemental analysis: C, 8H23NO3Cl Calculated values: C63.60, H7.71, N4.12, CI
10.44 Experimental values: C63.83, H7.90, N4.23, Cl
10.39 (a) Add 350 m/m of methanol to the 3'ditro-4'-chlorolaurophenone 342 obtained above, 20
While cooling to below .degree. C., 3.02 liters of sodium chloride pentahydride is added to this solution with stirring, and the mixture is stirred at room temperature for 1.5 hours.

The reaction solution was concentrated under reduced pressure, 300 ml of water was added to the residue, and the mixture was diluted once with 250 rrL of ether and twice with 100 ml of ether.
Extract times.

The extract is washed with water, dried over magnesium sulfate, and then treated with activated carbon.

After the solvent was distilled off from this solution under reduced pressure, the residue was distilled under reduced pressure to obtain bp213-215℃/2HHg1
33.9S' of 1-(3'-bitro-4'-chlorophenyl)dodecanol as a yellow oil is obtained.

Elemental analysis: C, 8H, 8N03Cl Calculated values: C63.23, H8.25, N4.10, CI
10.38 Experimental value: C63.01, H8.32, N4.35, CI
10.39 (portion) 1-(3'-nitro-4'-chlorophenyl)dodecanol 3.8fKp-}Toluenesulfonic acid monohydrate 0.155' is added and distilled under reduced pressure.

bpl85-190℃/2ax Hg fraction 2.7
7 was collected and dissolved in 49 ml of ether, washed in this order with water, sodium bicarbonate aqueous solution, and water, and dried over magnesium sulfate.

After drying, the solvent is distilled off under reduced pressure to obtain 2.7 g of β-decyl-3nitro-4-chlorostyrene as a yellow oil.

Elemental analysis: C, 8H26NO2Cl Calculated values: C66.75, H8.09, N4.32Cl
10.96 Experimental values: C66.65, H8.11, N 4. 3 0
, Cl10.98 (c) β-decyl-3-nitro-4-chlorostyrene 1
5. 100 d of 99% ethanol and 10 g of hydrazine monohydrate are added to OS' and heated under reflux for 2 days.

After cooling the reaction solution, it is concentrated, water is added to the residue, acidified with concentrated hydrochloric acid, and extracted three times with ether 200IrLl.

After washing the extract with water, it is dried with magnesium sulfate.

The solvent is distilled off from this solution under reduced pressure, the residue is dissolved in a small amount of benzene, n-hexane is added, and the mixture is left in a cool place.

When a lot of the precipitate was collected, 1-hydroxy-6-(1-dodecenyl)-1H-benzo}IJ azole 6.77 was obtained as a white powder with an mpl of 15 to 116°C.

Elemental analysis:・C18H27N30

Claims (1)

[Scope of Claims] 1. Acyl-substituted nitrobenzenes represented by the general formula (in the formula, R means hydrogen or an alkyl group, and X means a halogen) are reduced to produce the general formula (in the formula, R and or The hydroxyalkyl-substituted nitrobenzenes represented by the formula (same meaning as above) are obtained, which is then subjected to a dehydration reaction to produce alkenyl-substituted nitrobenzenes represented by the general formula (wherein R and X have the same meanings as above) 1. A method for producing 1-hydroxybenzotriazoles, which comprises preparing 1-hydroxybenzotriazoles and then reacting hydrazine thereto to obtain 1-hydroxybenzotriazoles represented by the general formula (wherein R has the same meaning as above).