SU658124A1 - Method of obtaining alkyl-a-naphthols - Google Patents

Description

one

The invention relates to chemical technology, specifically to a new method for producing alkyl-oh-naphtols.

Alkyl-cC-naphthols are a raw material for the production of pesticides, for example, naphthylurethane insecticide.

A known method for producing alkyl naphthols from naphthalene hydrocarbons, mainly dimethyl naphthalenes or oil refining fractions containing them, is that the hydrocarbons are subjected to sulfonation at 25-40 in the organic solvent followed by alkaline melting of the resulting sulfonic acids. The yield of alkyl naphthols is 76-80% of theoretical ll. . .

However, this method has several disadvantages. Dp of insecticide production is most valuable for alkyl-oh-naphthols. However, when sulfating alkalkaftschschinov form-25 with approximately equal amounts of alkyl-OB- and alkyl- | 1-naphtadine sulfonic acids. The alkaline melting of such a mixture of sulfonic acids leads to a mixture of alkyl (xgnaftoles and alkyl-p) -; aphtolov. Pos "

the latter are ballast because they give inactive urethanes.

The alkyl fractions containing alkyl naphthalenes also contain alkyl benzenes. According to the existing technology, the alkyl benzenes are converted to alkyl benzene sulfonic acids and then to the hydroxyphenols. Since alkylphenols form undesirable impurities, it is necessary either to separate the alkyl benzenes from the oil fraction, or to separate the alkylphenols from the finished product. These separations are additional stages and greatly complicate the process.

The aim of the invention is to improve the quality and increase the yield of alkyl-oC-naphthols, simplify the technology and expand the raw material base.

This goal is achieved by nitration of alkylnaphthalene containing fractions, reduction of the obtained nitro compounds to amines and hydrolysis of the latter under the reaction conditions of Bucherer, i.e. boiling with a sodium bisulfite hydroalcoholic solution

Distinctive features of the process are the nitration of the alkylnaphthalene-containing fraction of oil refining with a nitrating mixture, usually at 55-60 ° C or with nitric acid at eS-lO.C, the recovery of the cC-nitrokine-naphthalene, preferably with iron powder in the presence of hydrochloric acid at EO-CG or with hydrogen. catalyst containing platinum at room temperature and atmospheric pressure. The resulting nitro compounds containing o (nitroalkylnaphthalene) are hydrolyzed under the conditions of the Bucherer reaction. At the same time, the naphthylamines hydrolyze into aminonaphols much more easily than the longer phenols. The selection of the conditions can be carried out in such a way that the aniline derivatives remain practically unchanged. Due to the difference in properties, the amino impurity can be easily separated from naphthols, for example, by washing with an aqueous solution of the acid. The proposed method allows, in a manner IMT, to expand the raw material base and to use it for the production of alkyl naphthols, petroleum fractions containing significant impurities, alkyl benzenes. When THM does not require a lot of laborious separation of alkyl benzenes. Separated alkylanilines could be used in industry. Nitration of alkyl naphthalene-containing fractions is carried out with nitrous mixture or concentrated nitric acid at 65- 70 ° C. Under such conditions, alkylnaphthalenes form alkyl-sb-nitronaphthalenes. The resulting nitro-medianes, without their isolation from the nitroproduct, are usually reduced by metal (for example, iron) in the presence of tvii acid, or hydrogen in the presence of a catalyst (e.g., platinum). The resulting amines are separated from the reaction mixture by extraction with dilute mineral acid, and after decomposition of the salts with an amine base, they are obtained in pure form. Hydrolysis of amines, which are a mixture of alkylanilines and alkyl-C-naphthylamines, is carried out by boiling with an aqueous-alcoholic solution of sodium bisulfite for 20-30 hours. In this case, only alkyl-c is hydrolyzed (g-naphthylamine The resulting mixture of acid and alkyl -Chunaftol is separated to obtain pure components. The yield of alkyl-cC-naphthols is 85-87% based on alkyl naphthalenes. The method is illustrated by examples of the preparation of alkyl-oC-naphthols. Example: 1. Using as a raw material a fraction containing dimethylnaphtali The dimethylnaphthalene-containing fraction (bp 250-270 ° C) from catalytic gas oil cracking (b.p.HF-ZBO C) distillation. The dimethyl-aphthaline-containing gas fraction of catalytic cracking before and after nitration, has the following indicators. Refractive index, 4970 1.4465 Density, g / cm 0.8765 0.7975 Group composition, wt.%: Paraffin-naphthenic hydrocarbons64, 6 96.0 monocyclic aromatic hydrocarbons 20.8 3.0 bicyclic aromatic hydrocarbons 14.6 1 , 0 In a glass nitrator, 1000 g of an isolated fraction containing 146 g (mol) of bicyclic is placed. 680 g of the nitrating mixture of the composition, wt.%: nitric acid 22.3, sulfuric acid 66.7, water 11.0, are poured in over the course of 1 hour with 55-bOS and vigorous stirring. After the addition is complete, the reaction mass is kept at this temperature for an additional 1 hour, and then cooled and the acid layer is separated. The organic layer is washed with an aqueous solution of sodium bicarbonate and then with water. The obtained nitroproduct is placed in a reduction vessel, 380 g (6.97 mol) of iron powder, activated with hydrochloric acid, dried and dried through a No. 025 sieve, are added, and 23 ml of concentrated solution is poured dropwise with vigorous stirring. hydrochloric acid, maintaining the temperature of 90-100 ° C. After the addition of the acid is completed, the mixture is stirred at this temperature for another 2 hours, then neutralized with soda, the precipitate of iron oxides is filtered and washed with petroleum ether, the washing liquid is added to the main filtrate . The resulting solution was extracted with 50 ml of diluted (1: 1) by volume) hydrochloric acid. The extract is treated with a solution of 120 g of sodium hydroxide in 200 ml of water and the separated aromatic amines, in the form of a dark oily layer, is separated and used further without further purification. After separation of the amines, the hydrocarbon layer is washed with water and dried with anhydrous calcium chloride. After the distillation of petroleum ether, the residue is analyzed (see Table 1). The resulting mixture of aromatic amines is mixed with 2.5 kg of a 38% aqueous solution of sodium bisulfite, 600 ml of water and 300 ml of ethyl alcohol and boiled with vigorous stirring for 24 After cooling, the mixture is extracted with benzene and the aqueous solution is treated with 50% aqueous sodium hydroxide solution to pH 9. The mixture is boiled for 1 h, then cooled and acidified diluted. (1: 1 by volume) with hydrochloric acid to pH 2. Extracted alkyl naphthols are extracted with benzene, the extract is washed with water and dried by aeotropic distillation of water with benzene, benzene is removed and 138 g of alkyl naphthols are obtained as brown oil {85% yield from theoretical). Alkylnaphthol obtained from the dimethylnaphthalene containing fraction has the following characteristics: Boiling point 175-195 C / 10 mm Content of hydro-hg strong groups 9.9 weight%% Average molecular weight 172 Content alkyl alkyl numbers, wt.% 100.0 including: dimethylnaphthols 97.0 alkylnaptols of unidentified structure 3.0 The benzene extract of the reaction mixture for the hydrolysis of aromatic amines is washed with water and dried by azeotric distillation of water with benzene; benzyl is removed and 175 g of alkylanes are obtained as a dark oil. Alkilanines obtained from dimethyl naphthal containing fractions have the following characteristics: Boiling point 185-210 C / 10 Hg Amino group content, 9.5 wt.% Average molecular weight 169 Amino content; IR: -; wt,% by weight 100.0 including: alkylanilines 71.2 alkylaminotetralins19, 2 shchlaminoindanes4, b dimethylnaphthlamines5, 0 Thus, from dimethylnaphthal containing the gas oil catalytic cracking fraction under the described conditions, dimethyl-sb-naphtols are produced at a rate of 13.8% for taken fraction (sludge yield 85% of bicyclic aromatic hydrocarbons, contained in this fraction); at the same time, alkylanilines are obtained from output 17.5 (to the taken fraction or 76% of monocyclic aromatic hydrocarbons. Example 2. A nitrator is loaded with 1000 g of dimethlnaphthalene containing fractions and with eS-JO C and intensive stirring for 1 h they are poured 300 g of 60% Pn-nitric acid. The reaction mass is extracted at this temperature for 3 hours, then treated as described in Example 1 and dried with anhydrous calcium chloride. The nitroproduct obtained is placed in a reduction vessel fixed on a rocking chair and added there 10 g of catalyst ( platinum oxide) and reduced with hydrogen at atmospheric pressure until absorption is stopped.The catalyst is filtered off and the filtrate is extracted with hydrochloric acid as described in example 1. Hydrolysis of the separated amines in the presence of sodium bisulfite is carried out as described in example 1; g of alkyl naphthols and 185 g of alkylanilines, the properties of which are identical to those given. Thus, the yield of alkyl-o-gnaftoles under these conditions is 14% per fraction (87%), and the yield of alkylanilines is 18.5% (80%). Example 3. Use as raw material alkylnaphthalene fraction. As this fraction, gas oil is used for catalytic cracking (so kip. 230-360s), characterized by the following indicators :, Refractive index, П SP 1,4998 Density, g / cm 50,9105 Bromine number 6.5 Group composition, weight. %: paraffin-naphthenic hydrocarbons45.0 aromatic hydrocarbons55, 0 including: alkylbenzenes19.8 alkylteralins and alkylindanes5.3 alkylnaphthalenes 21.0 alkyl diphenyls2.0 alkylfluorenes3.5 alkylphenanthrenes and alkylanthracene1.9 unidentified 1.5 Nitration 1000g g gram % nitric acid and the processing of the reaction mixture l out as described in Example 2. The washed and dried nitric products is reduced with hydrogen in the presence of platinum oxide, as described in the same example. Hydrolysis of the isolated aromatic amines and separation of the reaction mass give 213 g of alkyl naphthols and 274 g of alkylanilines. the product has the following characteristics: boiling point, 55-235 ° C / 10 mm Hg. Hydroxyphenyl content, 9.3 wt.% Average molecular weight183

The content of phenolic compounds, wt.% 100,0

including:

alkylnaphols 89.0

tricyclic phenols (antrola, phenatrol) 7.0

unidentified 4.0

In this way, alkyl-gA-naphthols are obtained from catalytic cracking gas oil under the conditions described here with a yield of 21.3% for the taken gas oil (86%) containing 3-4% isomeric alkyl naphtholes; together with this, alkylanilines are obtained with a yield of 27.4% on the taken oil (78%).

Claims (5)

1. The method of producing alkyl-oC-naphthols from alkylnaphthalene-containing oil refining fractions differs in that, in order to improve the quality and increase the yield of the target products, simplify the technology and expand the raw material base, the initial fraction of oil refining is negated, resulting in The nitroproductive product containing ot-nitroalkylnaphthalene is reduced to amines, and the latter are hydro / shtered by boiling in an aqueous-alcoholic medium in the presence of sodium bisulfite. 2, Method POP.1, characterized in that, the nitration is carried out with a nitrating mixture at Z3-BS C. 3, Method POP.1, characterized in that the nitration is carried out with nitric acid at 65-70 s. 4. A method according to claim 1, characterized in that the reduction is carried out with iron powder in the presence of hydrochloric acid at 90-100 ° C. 5. Method according to Claim 1, characterized in that the reduction is carried out with hydrogen in the presence of platinum at room temperature and atmospheric pressure. Sources of information taken into account in the examination 1. USSR author's certificate 189423, cl. C 07 C 125/06, 1967.