SU301327A1 - METHOD OF OBTAINING p-NITROALOXYMETHYLENE PHENOLS - Google Patents

Description

This invention relates to a process for the production of phenols in the side chain which are nitro-substituted, which can be used as antioxidant additives to oil oils as intermediates for the production of phenol-aldehyde resins.

Using the proposed method, using a known reaction, it is possible to obtain new chemical compounds that, compared with their analogues, possess new properties.

The method consists in that the corresponding isomer of hydroxybenzyl alcohol is reacted with a-pitroolefins at a temperature of 50-75 ° C. B environment of an organic solvent in the presence of a base, such as triethylamine, followed by isolation of the target product by known methods.

In the case of using the o-isomer, the process is carried out in a non-polar solvent.

When using the P-isomer, the process is conducted in ethyl acetate. The yield of the target products reaches 90%.

Example 1. Obtaining o- (2-nitroisoproxymethylene) -phenol.

In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 12.4 g (0.2 mol) of o-hydroxybenzyl alcohol (mp 84.5 ° C), 13.1 g (0.15 mol), -1-propylene This mixture is dissolved in 50 ml of absolute benzene and 1 g (0.01 mol) of dry triethylamine is added dropwise with stirring. There is a slight increase in temperature. Stirring is continued for 30 minutes, after which the temperature is raised to 50 ° C. The mixture is heated at this temperature for 6 hours. At the end of the reaction, a separation was observed: the bottom layer was a viscous, bright red oil. A mixture of 6 ml of 10% hydrochloric acid is neutralized. The layer is separated from the benzene solution, washed with hot water and a 20% aqueous solution of ethanol. The resulting oil is dissolved in ethyl acetate and dried with anhydrous sodium sulfate, then filtered and the ether is distilled off. Then the product is washed twice with carbon tetrachloride and vacuum.

Benzene is distilled off from the benzene solution, and the remaining oil is washed with a 20% aqueous solution of ethanol and carbon tetrachloride. The solvent was removed from the resulting product under vacuum.

As a result of this purification, a bright red, viscous oil was obtained. The product readily dissolves in acetone, dioxane, dimethylformamide, lower alcohols, acetic acid, chloroform, dichloroethane, ethyl acetate, nitrobenzene, and more difficult in benzene; it is difficult - in ethyl ether, carbon tetrachloride, petroleum ether, 50% aqueous solution of ethanol, insoluble in water, n-hexane, nheptane.

After additional purification of the product by reprecipitation from ethyl acetate with petroleum ether, 15.6 g (72.1% of the theoretical) of o- (2-nitroisopropoxymethylene) -phenol were obtained with a batch of kip. 137-138 ° C at 2 mm. Hg Art. 1.5353; df 1,2104, MR found 54.17.

Found,%: C 57.2; H 6.5; N6,5. Mol weight 210.

CioHisNO.

Calculated,%: C, 56.87; H 6.16; N 6.63, Mol. weight 211. MR 53,57.

Example 2. Getting o- (2-nitropropoxymethylene) -phenol.

A mixture of 12.4 g (0.1 mol) of o-hydroxybenzyl alcohol, 13.1 g (0.15 mol) of 2-nitro-1-propylene, 50 ml of dry benzene and 1 g (0.01 mol) of triethylamine is stirred 6 hour at 57 ° C. Without heating, distilled off at 10 mm Hg. Art. triethylamine and benzene, and then unreacted 2-nitro-1-propylene. The resulting bright red, viscous oil is washed with carbon tetrachloride, then with warm water and with a 10% aqueous solution of ethanol (to separate it from hydroxybenzyl alcohol). The remaining product is dissolved in ethyl acetate, dried with anhydrous sodium sulfate, filtered, and reprecipitated twice from ethyl acetate with petroleum ether (to separate the nitroolefin from the residues). The solvent was removed from the obtained oil under vacuum. The result is 17.9 g of oil. The product readily dissolves in acetone, dioxane, dimethylformamide, lower alcohols, acetic acid, chloroform, dichloroethane, ethyl acetate, nitrobenzene; hexane, n-heptane.

The resulting suspension is additionally re-precipitated from hot benzene with petroleum ether, separated and evacuated. Output about (2 - nitropropoxymethylene) - phenol 17.1 g (81.1% of theoretical). This is a bright red, viscous oil, / ig 1,5378; df 1.2113.

MR found 53.7.

Found,%: C 57.1; H 6.4; N 6.4. Mol weight 209.

CioHiaNOi.

Calculated,%: C, 56.87; H6.16; N6.63. Mol weight 211. MR 53,57.

Example 3. Obtaining o- (2-nitro-1-ethylethoxymethylene) -phenol.

The experiment was carried out according to the procedure described in Example 2. To a mixture of 12.4 g (0.1 mol of o-hydroxybenzyl alcohol, 12.1 g (0.12 mol) of 1-nitro-1-butylene, 50 ml of dry benzene was added dropwise 2.1 g (0.015 mol) of tripropylamine under stirring. The process was carried out for 4 hours at 75 ° C and 2 hours at 65 ° C. Tripropylamine, benzene and unreacted 1-nitro-1-butylene were distilled off. dissolved in hot benzene,

filter and produce a double re-treatment of benzene with petroleum ether. The product is then separated, washed with carbon tetrachloride to separate the nitroolefin from the residues) and 20% aqueous solution of ethyl alcohol (to separate from hydroxybenzyl alcohol). The residual matter was dissolved in ethyl acetate, dried with anhydrous sodium sulfate, filtered, and the ether was distilled off. The resulting viscous oil is further purified by reprecipitation of the hot benzene solution with petroleum ether, separated and vacuumized.

The product readily dissolves in acetone, dioxane, dimethylformamide, lower alcohols, acetic acid, chloroform, dichloroethane, ethyl acetate, nitrobenzene, somewhat worse in benzene, more difficult in toluene, carbon tetrachloride, difficult in ethyl ether, 50% aqueous ethanol solution, petroleum ether, insoluble in water, n-hexane, heptane.

The yield of o- (2-nitro-1-ethylethoxymethylene) -phenol is 11.2 g (49.8% of the theoretical). It is a thick, red, yellow colored oil; ng 1.5532; df 1.1778; MR found 60.08.

Found,%: C 58.9; H 6.9; N 6.1. Mol weight 223.

C ,, Hi5N04.

Calculated,%: C 58.62; H 6.66; N 6.22. Mol weight 225. MR 58,19.

Example 4. Obtaining - (2-nitro-1-ethylethoxymethylene) -phenol.

In a three-necked flask equipped with a stirrer, thermometer, reflux condenser, 8.8 g (0.07 mol) / g-hydroxybenzyl alcohol (mp 125.5 ° C), 11.1 g (0.11 mol) are placed Initro-1-butylene. This mixture is dissolved in 25 ml of dry ethyl acetate and with stirring, a solution of 0.7 g (0.007 mol) of dry triethylamine in 5 ml of ethyl acetate is added dropwise. There is a slight increase in temperature. The process is carried out for 6 hours at 60 ° C. Without heating, distilled off at 10 mm Hg. Art. triethylamine and ethyl acetate and then unreacted nitroolefin. The product obtained is dissolved in chloroform, filtered (hydroxybenzyl alcohol is separated), then the solvent is distilled off. When heated, the oil is re-precipitated from benzene with petroleum ether, then washed with carbon tetrachloride and a 20% aqueous solution of ethyl alcohol. The resulting material was dissolved in ethyl acetate, dried with anhydrous sodium sulfate, filtered, and the ether was distilled off.

The product readily dissolves in acetone, dioxane, dimethylformamide, lower alcohols, acetic acid, chloroform, dichloroethane; ethyl acetate, somewhat worse in benzene, more difficult in toluene, ethyl ether, difficult in carbon tetrachloride, insoluble in water, petroleum ether , n-hexane, n-heptane. The output of g- (2-nitro-1-ethylethoxymethylene) -phenol is 5.1 g (32% of the theoretical).

It is a thick, viscous oil of red-yellow color, ngi-1,5305; df 1.1705. MR found 58.9.

Found,%; C, 59.1; H 6.9; N 5.9. Mol weight 223.

C, iHi5N04.

Calculated,%: C 58.62; H 6.66; N 6.22, Mol. weight 225. MR 58,19.

Example 5. Preparation of o- (2-nitro-1-tr of chloromethylethoxymethylene) -phenol.

The mixture was carried out according to the procedure described in Example 2. To a mixture of 6.2 g (0.05 mol) of o-hydroxybenzyl alcohol, 11.3 g (0.06 mol.ol) 1-nitro-3, 3.3- trichloropropene-1.25 ml of dry benzene was added with stirring 1 g (0.01 lgol) of dry triethylamine. The process was carried out for 3 hours at 50 ° C and 3 hours at 55 ° C. Without heating, it was distilled off at 10 mm Hg. triethylamine and benzene, and then unreacted nitroolefin. The resulting viscous oil of red-yellow color is washed with carbon tetrachloride, hot water and 30% aqueous solution of ethyl alcohol, then dissolved in ethyl acetate. they are dried with anhydrous sodium sulfate. The solution is filtered and the product is twice re-precipitated from ethyl acetate with petroleum ether. The solvent is removed from the resulting yellow-red oil under vacuum. The substance is easily dissolved in acetone, dioxane, dimethylformamide, lower alcohols, acetic acid, nitrobenzene , chloroform, ethyl acetate, it is more difficult - in benzene, it is difficult - in tetrachloride carbon, petroleum ether, ethyl ether, 40% aqueous solution of ethyl alcohol, insoluble in water, n-hexane, n-heptane.

The output of the o- (2-nitro-1-trichloromethyl ethoxymethylene) -phenol 14.1 g (89.3% of theoretical); pbo 1.5562; df 1.4421. MR found 69.3.

Found,%: C 38.5 H 3.6; N 4.1; C1 33.4. Mol weight 311.312. С1оН, оЫС1з04.

Calculated,%: C 38.2, H 3.2; N 4.4; C1 33.8. Mol weight 314. MR 68,17.

Subject invention

Claims (3)

1. A method of producing p-nitroalkoxymethylene phenols, characterized in that the corresponding isomer of hydroxybenzyl alcohol is reacted with a-nitroolefins at a temperature of 50-75 ° C in an organic solvent medium in the presence of a base, for example triethylamine, followed by release of the desired product by known methods. 2. A method according to claim 1, characterized in that, in the case of using the o-isomer, the process is carried out in an environment of a non-polar solvent. 3. Method according to paragraphs. 1 and 2, characterized in that, in the case of using the p-isomer, the process is carried out in ethyl acetate.