SU39769A1 - The method of obtaining 6 methoxy- and 6-ethoxytinaldine - Google Patents

Description

6-methoxyquinaldine and 6-ethoxyquinaldine are the raw materials for synthesizing the most valuable non-paratharaton with other effective action. Some of the applications of both quinaldines are:

1.a) Panchromatic sensitizers belonging to the groups of isocyanine and carbocyanine dyes; b) sensitizers for the infrared part of the spectrum.

2. Desensitizers are substances that have the property of lowering the light intensity of the emulsion so that the development process can be carried out. normal lighting conditions.

3. Preparations for the purpose of chemoterash.

In recent years, it has been established that some derivatives of quinolip bases have a high bacterium and are more effective. The bacteripticity of such enie compounds increases more abundantly in the presence of quin wave m heterocycle of b-methoxy or 6-ethoxy groups.

Both quinaldines are mentioned in the literature (germ. Pat., Ns 167770 1E04; Mills a. Pope, Phot. Journ. 1920, 183; 253; Terutaro Ogata. Proceed, imp. Acad. Tokyo, 3,335; 3,336-

338; Ch. Z. 1927, II, 1961-1962; U. X. Brahmachari a. I. Bliottahayee. Jouni Indian. Clieni. Soc. 1930, 527-530), but the details of their methods are extremely scarce.

W. Braunholtz (Journ. Chem. Soc. (1922), 121, 169-173) first described the method for producing 6-ethoxyquinaldine using the} Dohner-Miller method, i.e., from p-phenetidine, hydrochloric acid and acetaldehyde. The yield of the reaction product boiling at 165 - 180 ° and 14 mm, about 25-30% of theory. To obtain a clean base, the reaction product is wrung out. Wet on a porous clay plate from oily impurities and crystallize from a .1Irope.

There is no description of a method for producing 6-tags-like syngaldipa in the literature.

The P | 1 Institute of Chemical Reagents has been developed.: A creeping method for both hipaldins, consisting in a .. cd. When heated, 6-ethoxy or 6-etoxy-4-chloro; aldine with 100 ,, -. M and idrazine hydrate forms 6-ethoxy or b-methoxy-quinhal-4-hydrazine; hydrazine yield is close to theoretical (95-97, theory). The hydrazine obtained is oxidized by a boiling solution of sodium chromate.

(or dichromate) in the corresponding quinaldnn; the yield of the pure product distilled with water vapor is about 85–90 o the theory.

C1

A. Condensation b-methox-n 6-ethoxy-4-chlorochinaldine with hydrazipgndrate proceeds as follows:

Ci

.0 - NH.Xll. - nowhere R denotes methyl or ethyl rpyiniy.

Example 1. Getting 6-meth () of ksikhinaldil-4-gi phase a. 21 g of 6-me1-oxy-4-chlorochinaldine (m. IZO-101) and 21 g of 100; the hydraznhydrate hydrate boiled slightly (reflux) for 5 hours. By the end of this time, the oily layer, located at the bottom and bottom of the liquid, begins to harden very quickly and solidifies. To the mixture are added 100-150 sylph of water, carefully chop the yellowish; i) nb-methoxyxyhaldyl-4-1ikii, and the lump is sucked off with a liquid. Drazin and Got

the reaction hydrazine in a weak vinegar 0d is dissolved in the slot (,, - nd), added to the actus angle and boiled 1G) -wy for 20 minutes. TO

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the solution is added to a weak zaag ha, | th am.with. The arresting almost colorless crystalline precipitate is; 6-methoxy-hipald. 1-4-hydrazum P a are sucked off, washed with water and dried with ordinary temper 1 pc. 19 g of the crude product (93 ° theory) are obtained with a melting point of 192-19 (v-, After crystallization from (i alcohol), well-formed crystals of pure 1-o hydrazip with temperature melt, -1-2 210-212 (decomposed) are obtained.

Properties It is very difficult to spread in boiling water, from which it is crystallized in the form of long endless needles. Slightly soluble in benzene or toluene. Easily) soluble in boiling 95 ”- reduced. Easily soluble in various acids: hydrochloric, sulfuric, acetic, etc.

The 6th etoxin quinine Dil-4-hydrazine-hydrochloride is a colorless crystalline crystal, easily soluble in hot aqueous alcohol and in water. Melting temperature 275-277 (with decomposition).

PRI. 1 e p 2. Getting 6-ethoxyquina, 1di; 1-4-hydrazine. 22.2 g of 6-ethoxy4-chlorochinaldine (temperature: melt. - | enp 78 - 78.5) and 23 g of 100% hydrazine hydrate boil gently (reverse hopper. 8–9 hours). To Koitsu this time oily layers completely hardens. After cooling, 150 cm of water and further processing, as well as isolation of the reaction product, are added to the reaction mixture, as in the preparation of 6-meth () Ciichialpl-4-hydrazine. According to the data of B.1 ed1 o-yellow crystalline i-KOif) product 21 t, t. S. 98% of theory. The reaction temperature of the reaction; 1 p () of duct 170-173 (with decomposition). For, -1cccii pure product crista /: lksu from 95% - about alcohol. The floor is almost impersonal, hydrated, crystallized and in the form of short needles, with a floating temperature of 177-178.

Properties It is difficult to grow very quickly: in a boiling water; crystal | is dpp1, i1-lami; hard 1) Astvorpm in boiling pepzo, 1e and tsluole. Easily dissolve. In boiling water:, -; alcohol, dilute acids (hydrochloric, acetic, sulfuric).

6-ethoxyquinaldyl-4- hydrazine hydrochloride - colorless needles, easily soluble in water, hotter than alcohol; hard soluble and alcohol. Melting point 292-294 (with decomposition).

Sulfate fine colorless crystalline) powder is very difficult to dissolve in alcohol in cold water. Le | -so soluble in hot water. Temperature float chenp 261 (with times / in the form).

3R ХН ХП, - | - N.bCr.O: 1-LO

gi;: pl.HI; Vrixpoi:,. on three.;

.-: z 3R - H -I 2 HaOH - 2Cr (OIi),: -,

Example 1. Oxidation of 6-methoxyquinaldyl-4-hydrazine to 6-methoxyquinaldine. 60.9 g of 6 methoxyquinaldyl-hydrazine (melting point 210–212 °) are dissolved in 360 cm of 5.5–6 ° C acetic acid. The resulting solution of hydrazine acetate is poured dropwise (from a separating funnel) into a continuously boiling solution of 60 g of sodium bichromate — in 2000 s., Water, to which is added 100 cm — 35 of the 1 st sodium hydroxide solution. The addition of a hydrazine acetate solution is accompanied by a uniform evolution of gas (nitrogen) and the appearance of flocculated, chromium hydroxide. As hydrazine oxidizes, oily droplets of dark-6-methoxy-hexalde appear on the surface of the liquid. At the end of the addition of the hydrazine solution, the mixture of ca. rt is still 10-15 minutes 1, after which a free b-methoxymnaldine is formed and distilled off with steam. In the receiver, perepantnuy pale yellow oil gradually crystallizes, with (more quickly when cooled with ice) into colorless crystal needles CHIST01YO 6 methoxyquinaldine. 44-46.5 g of product are obtained with a melting point of 57.5 -. Leave 85-90 / ,, theory.

Properties Peregpapny with waters n; /; The product is crystallized by vapor in the form of colorless, short crystals, with a melting temperature of 57.5-58. Easy

When stored in air, both hydrazines (free bases) gradually tinge and darken. Solg: hydrazines are stable and can be used for the purification of hydrazines.

B. Oxidation of 6-methoxyquinaldyl-4-hydrazine and 6-ethoxyquinald-4-hydrazine with sodium chromate (I.111 dichromate) in 6-method 1-s-11; ice floes and 6-ethoxy1 and 1; in, leaking. with; e d ui. m m about b 1 s about m;

soluble in organic solution: solids, more tr-dn - in cold ligroin. Easily soluble in dilute acids. Aqueous solutions of 6-methoxy.quinaldine salts intensely fluoresce in a bluish-blue color.

Salts of 6-methoxyquinaldine: picrate- yellow needles, very difficult to dissolve in alcohol. Melting point 218-219 °.

Iodoethyl is greenish-yellow needles, easily soluble in alcohol and in water; insoluble in benzene. Melting point 194--195 (with decomposition).

Chromate is golden yellow crystalline Ily. Melting point 171-172 (with decomposition).

Example 2. Oxidation of 6-ethoxyquinaldyl - 4 - hydrazine to 6-ethoxyquinaldine. 21.7 g of 6-ethoxyquinaldyl-4-hydrazine with a melting point of 177-178 are dissolved in 200 cm-4% -v. vinegar acid acid. The resulting solution of hydrazine acetate is (from a separating funnel it is poured into a batch of 20 t of sodium bichromat in 400-500r, u of water, to which} 35-40 cm of 35L of sodium hydroxide is added). The oxidation reaction of 11pO is the same. as well as I-Mogoxininaldyl-4-hydrazine.

15.8 - 16.8 g of pure 6-ethoxychalimdipa are obtained with a melting point of 70 -7 D. Income 85-90 ,, theory.

Hlorgndrat of pure ocHOBaiiHH melts at 184 - 186 iikrat - irk 191 - 192,: fo.mat - at 144 - 145 (with decomposition) and iodate - at 181 - 182.

Appearance: the physical properties of the II melting constants of full gyu coincide with those for the base described by V. Brauriholtxe.M.

Predemt ii 3 about a bout e and i.

The way to b-methoxy-and () - ethoxychipaldine. characterized in that 6 - methoxy- or () -ethoxy-4-chlorochinaldine is treated with hydrazine to obtain b-methy-ci-1 or tl-ethoxy-4-hydrazine xinaldia jia, which is oxidized further by hrolkggom lib with bichromate in 6-non-toxic-i, - 1and 6-ethoxyquinldin.