SU111045A1 - Method of producing beta-alkoxy- and beta-alkyl mercapto-glutaconic aldehyde salts of ditetrahydroquinolide - Google Patents

Description

SI

CH

where: AO or S;

R: - SNZ: -C, H- „

X is an acid residue. The present invention permits the preparation of o6iueii compounds.

formulas, I, based on 1,5-bis (L-tetrahydroquinolyl) pentadiene-1,4on-3 and 1,5-bis (M-tetrahydroquinolyl) pentadiene-1,4-thion-3 of the general structure (II):

where: A has the same meaning as in formula I, by treating dialkyls with tetrafate in a solution of aromatic hydrocarbons when heated to 100 °, with sufficient yields and high purity. Example 1. Methylsulfate of ditetrahydrohinolida-methoxyglutaconic aldehyde

0.68 g of 1,5-bis (M-tetrahydroquinolyl) pentadiene (1,4), it {3) is dissolved by heating in 4 ml of dry benzene and 0.5 g of dimethyl sulfate in 2 ml of benzene is added to the solution. The liquid is heated for 30 minutes. on the water bath, and soon it becomes orange. Upon cooling and rubbing the walls of the flask with a glass rod, a fine crystalline reddish-brown precipitate is precipitated, which is filtered and sprinkled on the filter with dry benzene and ether.

The output of 0.65 g (69,1%). T. pl. 154 --- 155 °.

Small reddish-brown crystal.

And one and 0.4 g of fi-methoxyglutaconyl a.1.1 dehydrate ditetrahydroquinolide methyl sulfate is dissolved in 4 ml of methanol, the solution is heated to boiling, and an equal volume of 10% potassium iodide is added to it. The precipitated crystalline precipitate is filtered off after cooling and the filter is r-washed with water, methanol and ether.

Yield 0.3 g (73.1). T. pl. 140-141.

Small kirnichno-red prisms with metallic shine (from anhydrous meta-nola). T. nl. 143 -144

11 epXl o rt a t. 1.3 g of methyl sulfate ditertra1ndroquinolide 3-methoxyglutaconic aldehyde is dissolved in 25 ml of anhydrous methanol, 8 ml of a 10% aqueous solution of chlorine-sodium in anhydrous methanol and liquid is added to the solution before kineni.

The precipitated crystalline precipitate is filtered off after cooling and washed on a filter)

a small amount of anhydrous methanol.

Yield 1.1 g (86.7%). T. pl. 190-191 °.

Large dark red prisms with a bluish sheen (from anhydrous methanol). T. pl. 207-208 °. Example 2. Ethyl sulfate ditetrahydrohinolida ji-Egoxyglutaconic aldehyde

0.68 g of 1,5-bis (L-tetrahydroquinolyl) nentadien (1,4) -one (3) is dissolved by heating in 4 ml of dry benzene and 6.62 g of diethyl sulfate is added to the solution in 2 ml of benzo- chz. The liquid is heated for 2 hours. on a boiling water bath, and it gradually acquires an orange color. Upon cooling and rubbing the walls of the flask with a glass rod, a small crystalline orange-red precipitate is released, which is filtered and H1) is washed on the filter with 4 ml of dry benzene and ether.

Yield 0.56 g (56.2%). T. pl. 169 170 °.

Small orange-red crystals.

Iodine and d. 0.60 g of ethyl sulfate ditetrahydroquinolide B-ethoxyglutaconic aldehyde are dissolved in 6 ml of methanol, the solution is heated to kineni, and an equal volume of 10% aqueous solution of potassium iodide is added to it.

The precipitated crystalline precipitate, after cooling, is filtered and washed on the filter with water, methanol and ether.

The output of 0.36 g (60%). T. pl. 153-154.

Small same prism-colored prisms (from anhydrous methanol). T. pl. 155,156 °.

Eper chlorine, 1.5 g of ethyl sulfate, ditet) 1-hydroxychloride J-STO-hydroxy glutaconic aldehyde is dissolved, heated by heating with 10% anhydrous methanol, i) the solution is added with 5 ml of a 10% solution of sodium chloride in anhydrous methanol and the liquid is heated to boiling.

The precipitated crystalline precipitate is filtered off after cooling and washed on the filter.

7.5 ml anhydrous

methanol (in peskolkoe receptions).

The yield of 1.25 g (94.3% of T. pl. 211-.

After two-time crystallization from anhydrous netanol, Krupp orange plates with m.p. 217 218 Example 3. Methyl sulphate of ditetrahydroquinolide S-methyl mercapto-glutaconic aldehyde

0.36 g of 1,5-bis (L-tetra1-idrohi 1olyl) pentadiene (1,4) -thioia (3) is dissolved under heating and 40 ml of dry benzene and in a solution of 0.26 g dimethyl sulfate in 5 l . dry benzene, and the color of the solution from orange immediately turns into red-orange.

The liquid is heated for 30 minutes. na waters sing bath. Upon cooling and rubbing of the walls of the flask with a glass rod, a red crystalline precipitate is released, which is washed out with filter benzene and ether.

Yield 0.4 g (82.3%). i nl 135-136.

Small red crystals.

Perchlorate. 0.8 g of methylsulphate mta diptet) agpdroquino.1nda 3-methylmercaptoglutaconic aldehyde is dissolved at a typical temperature in 8 ml of 1M methanol and added to the solution 8 .If.gr 10% sodium perchloric acid in anhydrous methanol. At the same time, dark oil is immediately released, which will soon be closed off.

The precipitate is filtered off and washed onto (.ihTpe 16 ml of water and 4 ml of ethanol.

Yield 0.72 g (MJ%}. So pl.

Brownish green with metallic sheen (from anhydrous methano.ch). T.p.ch. 204-205.

Subject invention

The method of obtaining salts of 3-alkoxy-1 and 1-tetrahydrokhnpolid: 1 -alkylmer Itoglutac Opaaldehydes, about 1.5 pp (-tetrahydroquinol) pe-gadien (1,4) -one ( 3) p, respectively, 1,5-bis (-tetrahydroxpnol) pentadiene (1,4) -thiop (3) is treated with dpa, .- 1 sulfate. In a solution of aromatic hydrocarbons, such as benzene, at) 1 agrevipip to temperature () s 100 .