SU498904A3 - The method of obtaining polyhydroxyl esters - Google Patents

Description

(54) METHOD FOR OBTAINING POLYHYDROXYL COMPLEX

The aethers of the known method consist in the fact that 2-methylindole of the general formula where AG, Z and W are above are subjected in the presence of an alkaline agent to reacting with the alkyl halide dioxypropyl ester of the haloalkanoic acid of the general formula Iiiai-A-COoCiio-Cll7CH2 B4 where Hal is a halogen . A, R, -, and y are the indicated values, followed by hydrolysis of the obtained compound in acidic with de and isolation of the target product by known methods. An alcoholate, hydride or amvd of a silk metal is usually used as a silk agent. Oo-Psopropylidene Example; DL-(2-methyl-3-P-chlorobenzoyl-6-chloroindolyl-1) dioxypropyl ester; Qt--propionic acid. 15.0 g of 2-chmethyl-3-P-chloro-isoyl-6-chlorindole and 165 ml of di-methylformamide, and then 2.15 of 60% sodium hydride suspension in a vase are introduced into a three-bulb flask; new oil. At the end of the hydrogen evolution, 15.4 g of CX-bromopropionic acid isopropylidene-glyceryl ester are added dropwise and incubated overnight. The dimethylformamide is distilled under vacuum and 50 g of ice is added. The aqueous suspension is extracted several times with methylene chloride. The chloromethylene salts are combined, washed with water, and dried over magnesium sulfate. Then filtered and distilled in vacuo. The residue is chromatographed on a silica gel column and eluted with an acetic acid (7: 3) benzene ethyl ester mixture. 14 g of an amorphous, homogeneous product is collected chromatographically on a thin layer. As a result of the new purification by treatment with activated carbon, 12.8 g (81% ) amorphous product, soluble in most organic solvents. Found,%: C 6O, 9; H 5.0; N 3,0; C1 14.5. Calculated,%; C, 61.23; H, 3.14; N 2.86; Ci 14.46,. PRI mme R 2. Glycerol esters of jy r, (2 -: e l 3-p-chlorobylIsoll. 6-hlorindoli, - | -1) C (Irogyuaoic acid. Into a flask of moisture from a wake of a flask of O.-. Isopropylidondondi - OO, 7 g of DL hydroxypropyl ester (2 -methyl-3- .-. p-chlorobenzoyl-in-chloroIlpolpol.) were added - OS iijio- pionic acid, and the batch in example 1, 53.5 ml of methoxyethiol and 13.5 g of bo. <RTI ID = 0.0> .-. </ RTI> acid. Mixed at 8 ° C for 4 hours, allowed to cool to the temperature of TeN.roto, and then diluted with 2OO ml of methylene chloride. The solution is washed even) with 200 ml of water, dried, decolorized with activated angle ((.1 diluted, and ne) heated to prepare methylene chloride. 8.4 g of amorphous product are obtained,. TOfjbiii is cleaned on a splitkagel column, and then the chlorofor of ethane (0: 1) is eluted with skgesy. 6.9 g of a homogeneous product are collected chromatographically on a thin layer. Then, a new purification is carried out by revolving the product with activated carbon, dissolving in ethanol, heating with a reverse 1, 1 M condenser, filtering and evaporating the baths to dryness in high vacuum. 6.4-8 g of DL glyceryl ester (2- -methyl-3-p-chlorobenzo 11.g -e-chloro-1-chloryl-1) -a-progpunic acid in the form of amorphous product, slightly colored) are obtained in the yellow color and soluble in alcohols, acetone and chloroform. Found,%: C 58.7; H 4.70; N 3.4; C1 15.5. S2-21 4 N Og. Mol weight 45O, 32. Calculated,%: C 58.68; II 4.7; N 3.11; C1 15.75. Example 3. o, o -1-zopropylide &amp; dioxypropyl ether (2 g methyl-3-p-chlorobenzoyl-6-methoxy-1-cholyl-1) acetic acid, 8.9 g 0, O-isopropylideneglycerol mixed with 129 mg of a 507cd suspension of sodium hydride in mineral oil and 5 g of (2-methyl-.3-p-chloro-benoyl-b-methoxy-incholyl-) acetic acid methyl ester create a vacuum of 5 mm Hg. Art. The reaction mixture is heated for 2 hours at 75 ° C and the excess of O, 0 -isoprotein-lycerol pilide and heated to 80 ° C under vacuum (O, 3 mmHg) is distilled off. The oily residue is converted into a dough in 35 cm3 of isopropyl ether for 1 hour, then it is frozen overnight, filtered under vacuum, the precipitate is washed with ice-cold isopropyl ether and dried in vacuo at a comp. Temperature. This gives 5.885 g of 0 „, 0“ - “isopropylideidioxypropyl efHra (2-Methyl ™ Zgch g, chlorobenzoyl - 6-methoxy indolyl) acetic acid.

For analysis, the compound is purified by recrystallization in isopropanol, and then in ethanol and finally in isopropyl ether. The resulting compound is light yellow needles, soluble in chloro ™ form, ethanol, acetone and benzene, little i soluble in ether, insoluble in water; t, pl. 117 ° C.

Found,%: C 64.4; H 5.5; C1 7.5; N 3,0;

 N Og. Mol weight 471.95.

Calculated,%: C 63.63; H 5.55; C, 7.51; N 2.97,

PRI me R 4. Glyceryl ether

(2 methyl-3-Pg-.chlorobenzoyl 6 methoxy-dO-. Lil-1) -acetic acid.

A mixture of 7.85 g of the ester obtained in Example 3, 8.55 g of boric acid and 38, methoxyethanol is heated for 18 hours at

, then the temperature of the reaction mixture is brought to 15 ° C, poured into water, filter

room

Isopropylidenedioxypropyl ether (2-methyl-. Svetloveorichy- Chloroform .V-toluoJv.6 -methyl hydroxyl). 1) "-. - Acetic acid 3 Isopropyl vendeoxypropyl ester {2g-.methyl k.3 p-methoxybene-eip 6 Methoxyindindyl-1) acetic acid Acid (2-methi1 {3-tt-methoxybenoyl-.6-methoxyisdol-3-methoxybenol-ester). -acc; succinic acid 5. Isopropyl vendedioxypropyl ester (2-methyl-3-y-fluorobenzoyl-b-chloroindolyl -1) "propionic acid 6Glyceryl ether (2methyl - 3 p -fluorobenzoyl 7b-btg-chlorindoles; -) propionic acid 7 Isopropylidevodioxypropyl ester, (ty l-3-1g-fluorobenzoyl 1 - "6-methoxyind ORI l-1) - -yl1-acid 8

ruyu1 in vacuum, wash the precipitate with water until neutral wash water and dry. R-. vacuum. The residue is dissolved in

3 3 cm of isopropanol, heated with reverse

cooler, filter hot, cool, add 10 cm of iso propyl ether with stirring, ice, filter under vacuum, wash the precipitate with ice cold isopropyl ether and dry. Obtain 3.5 g of glyceryl ether (2-mg tilg-p-chlorobenzoyl-6-methoxyindoles / -) - .g, acetic acid.

For analysis, the product is purified by crystallization by stallation in benzene.

The compound obtained is yellow crystals, soluble in acetone and chloroform, slightly soluble in benzene, insoluble in water; m.p. 136 С

Found%; C, 61.1; H 5.1; C1 8.2; N3.3,

  ° 6 ° 431.89, Calculated,%; C, 61.18; H 5.14;

C1 8.21; N 3.24.

Analogously to examples 1-4 receive with a.

Unity, list and indicators of which

are shown in the table.

Condition Solvent Temperature

melting, ° C

11S

methylene

148 Glyceryl ether (2 "methi; 3 ™ 1trifluoromethyl" YellowIsopropanol 1g benzoyl "6" methoxyndoyl or "1)" "acetic acid firm solidly Ethyl. lots, ester ether, hydrochloric acid, chloroform, methanol, acetone, colorless, chloroform, acetone, 96-97 needles, colorless, chloroform, toluene, crystals, ordinary white-orazhozheye cryorganic steels, solvents, colorless colors, alcohols, alcohol, chloroform,

9 Isopropyl ester dioxypropyl ether (2- "methyl- .-" 3 ft ™ TpH4) TopMeTHn6eH3OHJb-.6 "-. MeTOKCHHHaonH b-l AND acetic acid Compound No. 1 is insoluble in water and

Subject invention

The method of obtaining polyhydroxyl complex 1x-esters of the general formula

, (0-AG

Sh1z

Y

A-COO-CHj-CK-Clls

ORi OR2

and 2

hydrogen, halogen, ntrograaGD €

pa, trifluoromethyl, or lower alkoxy, N o N "dialkylamino, alkyne, thioalkyl, or alkylsul ({unyl group;

Ag - aryl or diclohexpl, homo or heterocyclic, unsubstituted or stb ishchenchen1Sh th one or more halogen-mi. lower a) living, trig {) tormethyls, alkoxyl, thioagasilic or alg-. iful fon flax m and gru r pa mi;

 bivalent, linear or branched: lien aliphatic radical n formula

 Ш1

TO

 hydrogen or lower alkyl | R "hydrogen or together form an alkylenY residue of cetal. formulas, 5

/

Cd

Table continuation

Chloroform

-1 / IvG Methylene Chloride Zfir

in water.

: Where R and lower alkyl rad No.icaJbij characterized in that 2 methylindole formulas

CO-AG

where Ab J 2 and V have the above-mentioned values, in the presence of an alkaline agent, react with alkylidene dioxypropyl haloalkanoic acid of the general formula

(oo; ii2-Cii- (H2

oh oh

xtx

B “4

d have

"3"

where ™ is halogen, A,

these values, followed by the hydrolysis of the semi-synthetic compound in an acidic medium and the separation of the target product using known methods. ether; Compound No. 2.9