SU1395644A1 - Method of producing 1,3-di-substituted 2-aminobenzanthrone - Google Patents

Abstract

The invention relates to the field of the aniline dye industry, in particular, to a method for producing new 1,3-disubstituted 2-aminobenzantrone of the general formula H2 R-fTVR where R -, CN, Ph, which can be used to dye synthetic fibers in bulk. The proposed method allows to obtain new 1,3-disubstituted 2-aminobenzantrone from the available technologically available method in high yield (80-90%). The essence of the method is that 1-halogen- or 1-nitroanthraquinone undergoes condensation with more than twice the amount of a compound having a methylene group, activated by at least one cyano group, in an environment of polar amotone organic solvent in the presence of an alkaline agent and, possibly, salts of monovalent copper as a catalyst. 3 hp f-ly. to SA: with a joint venture of: 4 hours

Description

The invention relates to the aniline coating industry, in particular, to a process for the preparation of novel 1,3-disubstituted 2-aminobenzantrone of the general formula

where R -, CN, Ph,

which can be used for

dyeing synthetic fibers in

mass.

The purpose of the invention is the synthesis of new 1,3-disubstituted 2-aminobenzantrone from the available technologically Available method in high yield and using the obtained compounds B | as dyes for synthetic fibers in the mass.

: 2 t Aminobenzantrons of the indicated total f | hermula are obtained by condensation of 1-halo- or 1-nitro-anthraquinone with a compound having a methylene group, tirovirovanny, at least about (diagonal group, in the environment of a polar ahpoTOHHoro organic solvent in the presence of a compound character, possibly in the presence of the | 1toisator.

; Dimethylformamide, for methyl sulfoxide, 1: examethanol, should be used as a solvent. As a basic compound, it is advisable to use an alkali metal hydride or carbonate.

; Monovalent copper compounds should be used as a catalyst.

The essence of the proposed method lies in the fact that the amino group in the BtopoM position of the benzanthrone is formed when the cycle is closed. To obtain the proposed method, 2-aminobenzene of the aforementioned general formula 1, a halogen- or 1-nitroanthraquinone is introduced into the reaction with a minimum of two times the molar excess of the compound with the active methylene group. The reaction of C1PO is carried out in two stages: 1 first — at room temperature until the initial derivative of anthrax H is absent (the second is when heating the reaction mass at 50–100 ° C or extracting it with boiling aqueous solution

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,

0

five

0

50

35 Q

dd

50

55

alkali to form the desired product.

Conducting the condensation process in the presence of a basic compound allows the reactive anion of the compound to be obtained with the active methylene group and to bind the acid that appears during the reaction. These compounds dye the synthetic fibers in bulk in yellow with a red tinge.

The invention is illustrated by the following examples.

Example 1. To a solution of 2.26 g (0.02 mol) of cyano acetic ester and 1.12 g (0.002 mol) of potassium hydroxide in 10 ml of dimethylformamide was added 1.67 g (0.005 M) of 1-iodantraquinone and 1.9 g (0.01 M) monovalent copper iodide. The reaction mass was colored green. The mixture was stirred at 20 ° C until the starting 1-Iodantraquinone disappeared, monitored the reaction with TLC, then the temperature was raised to, stirred for 4 hours, cooled, poured into 200 ml of water, the precipitate was separated, dried, extracted with chloroform, the solvent was removed, 1 was obtained , 5 g (77.5%) 1,3-dicarb-ethoxy-2-aminobenzantrone. Red needles (from aqueous ethanol), t.sh1.117-. IR spectrum, cm-: 1655, 1710, (); 3330-3480 (NH,); L „„, nm (lg): 461 (3.456).

Found,%: C 70.63; 70.86; H 4.72; 5.07; M 389

CjjHigNOj.

Calculated,%: C, 70.94; H 4.92; M 389.

The compound dyes polyamide fiber in a bright yellow color with a reddish tinge, heat-resistant in polymer melt for 90 minutes. Dyes polyester fiber in a bright yellow color with a red tint, heat-resistant in polymer melt 120 min.

Example 2. Analogously to Example 1, a solution of 2.26 g (0.02 mol) of cyanoacetic ether and 1.12 g (0.002 mol) of potassium hydroxide in 10 ml of dimethyl sulfoxide was added to 1.67 g (0.005 M) 1 • iodantraquinone and 1.9 g (0.01 mol) of copper iodide. Received 1,3-dicarb-ethoxy-2-aminobenzonron.

Example C. To a solution of 1 g (0.015 mol) of mapondinitrile and 1.68 g (0.03 mol) of potassium hydroxide in 80 ml of dimethylformamide was added 1 g

(0.003 mol) of 1-iodantraquinone, the reaction mass was colored green. Next, the mass was stirred pr and 20 ° C until the disappearance of 1-iodantraquinone (100 h), controlling the course of the TLC reaction. Piped into 500 ml of water, heated at boiling for 2 hours, cooled, the precipitate was separated, washed with water, 0.8 g (91%) of 1,3-cyan-2-aminobenzantrone was obtained. Red needles (from pentanol), so pl. (vozgn.); IR spectrum, cm: 1660 (), 2210 (CrN), 3250, 3350, 3415 (NHj); A „, im (IgC): 468 (3,571)

485 (3.631).

Found,%: C 77.16; 77.06; H 3.43 3.34; N 13.98; 14.07; M 295.

C HgNjO.

Calculated,%: C 77.28; H 3.07; N 14.25; M 295.

The compound obtained dyes polyester fiber in a bright yellow color with a reddish tinge, heat-resistant in polymer melt 120 minutes.

Example 4. Analogously to example 2, iodantraquinone is added to a solution of 1 g (0.015 mol) of little nodinitrile and 1.68 g (0.03 mol) of potassium hydroxide in 80 ml of dimethylsulfox — 1 g (0.003 mol) of an oxide.

1.3 dicyan-2-aminobenzaphron was obtained.

Example. 5. To a solution of 1 g (0.015 mol) of malonodinitrile and 1 g (0.018 mol) of potassium hydroxide in 25 ml of dimethyl formamide, 0.76 (0.003 mol) of 1-nitroanthraquinone was added, the reaction mass was colored green, the last was stirred for 30 minutes until the disappearance of 1-nitroanthraquinone, controlling the reaction by TLC, the temperature was raised to 50 ° C, stirred for 1 h, diluted with 250 ml of water, heated at boiling for 1 h, cooled, the precipitate was separated, 0.76 g was obtained (86.3% ) 1,3-dicyan-2-aminobenzantron, which is identical in properties to that described in example 3.

Example 6. Analogously to Example 5, to a solution of 1 g (0.015 mol) little nodinitrile and 1 g (0.018 mol) of potassium hydroxide in 25 ml of dimethylformamide was added 0.38 g (0.015 mol) of 1-nitroanthraquinone. Received 1, 3-dicyan-2-aminobenzantron.

Example 7. To a solution of 2.34 g (0.02 mol) of phenylacetonitrile and 1.12 g (0.02 mol) of potassium hydroxide in 5 ml of dimethylformamide and a solution

d

0

0.5 g (0.002 mol) of 1-hlorrantrahonona in 25 ml of dimethylformamide, stirred for 5 min, the reaction mass was painted red, it was heated to 100 C, stirred for 15 min, cooled to 20 C poured into 100 ml of water, neutralized with ammonia solution , the precipitate was separated, gHuchili 0.55 g of 1,3-diphenyl-2-aminobentanrone. IR spectrum, 1650

(); 3275, 3325 (u); L,

nm

(lg): 407 (4.168), 425 (4.162).

The resulting compound dyes polyamide and polyester fibers in

5 bright yellow with a red tint. The proposed method, compared with the known method of producing 2-aminobenzantron by reducing 2-nitrobenzantron, allows obtaining new 0-aminobenzantrone derivatives from available using available technology with a yield of 80-90%, which significantly exceeds the yield of 35% 2-aminobenzantrone , obtained by the reduction of 2-nitro-benzene, while the new derivatives of 2-aminobenzantron stained polyamide and polyester fibers in mass in bright yellow colors with a red tinge. The known 2-aminobenzantron is an intermediate product in the synthesis of vat dyes.

35

Claims (3)

1. A method for producing 1,3-disamide1-2-aminobenzantrone of the general formula where R is COOCjHj, CN, Ph, the fact that 1-halogen- or 1-nitro-anthraquinone is reacted with a compound containing a methylene group activated by a cyano group at a molar ratio of 1: 1-10 in an aprotic polar solvent medium in the presence of potassium hydroxide until no starting anthraquinone derivative is present. by- by the following heating of the reaction mass to 30-OO C or by treating it with boiling water. 2. Method POP.1, characterized in that, for the purpose of abbreviation 51395644 The duration of the process, the mutual yield of the target product, the interaction is carried out in the presence of solidarity, is carried out at a molar ratio of monovalent copper. The derivative of anthraquinone and 3. The method according to claim 1, characterized by the activation of the method and with the fact that, for the purpose of increasing the number of groups, 1: 4-10.