SU1574598A1 - Method of obtaining 4-dialkylamino-2-alkyl(or phenyl)naphtho /2,3h/quinolin-7,12-diones - Google Patents

Abstract

The invention relates to heterocyclic compounds, in particular, a method for producing a novel 4-diethylamino (or piperidino) 2-phenyl (or tert-butyl) naphtho [2,3-H] quinoline-7,12-dione, derivatives of which can be used in medicine. The goal is to create a new way of synthesizing new compounds. The process is carried out by cyclization of the corresponding 1-amino-2- (1-dialkylamino-2-acyl vinyl) -anthraquinones in the presence of phosphorus oxychloride in dioxane at 60 - 80 ° C, followed by treatment of the reaction mixture with an aqueous alkali solution. Yield,%, mp. ° C

gross formula: a) 65,6

169-170

C ₂₇ H ₂₂ N ₂ O ₂

b) 53,8

162-163

C ₂₆ HN ₂ O ₂ .

Description

The invention relates to a new method for producing new derivatives of naphtho [2,3 ~ h} quinoline ~ 7,1 2-dione, namely 4-diapipamino-2-alkyl (or phenyl) naphtho [2, 3-h ^ quinoline-7. , 12-dio (I)

NR _Z R ₃ new general formula

of natural compounds, in particular, a method for producing a new 4-diethylamino (or piperidino) 2-phenyl (or tert-butyl) naphtho (.2, 3-b] quinoline-7,12-dione, derivatives of which can be used in medicine. a new method for the synthesis of new compounds The process is carried out by cyclization of the corresponding 1-amino-2- (1-dialkylamino-2-acylvinyl) anthraquinones in the presence of phosphorus oxychloride in dioxane at 60-80 ° C followed by treatment of the reaction mixture with an aqueous alkali solution. %: mp. C; gross formula: a) 65.6; 169-170; C ^ H ^ D ^ O *; b) 53.8; 162-163; · from

C N it And _r 01.

"R ₇ and R ₃ form, together with nitrogen, a radical that can be used as dyes, chelating agents or biologically active compounds"

The purpose of the invention is a new method for producing new 4-dialkip-amino-2alkyl (or phenyl) naphthoC2, 3-h ^ quinoline

7,12-dione, which can be used as dyes, chelating agents or bioactive compounds.

The invention is illustrated by the following examples.

£> and 1574598

2) R, = -C (SND>

"on the.

Example 1. Obtaining 4-diethyl 'amino-2-phenylnaphtho. [2,3 ^_ b] quinoline-.

7,12-dione.

- 1574598 • 4

- Amino-2-benzoyl-tinilantraquinone.

0.74 g of 1-amino-2-ethynylanthraquinone, 0.62 g of benzoyl chloride, 0.40 g of Et ₃ N and 10 mg of Pd (PPh ₃ ) ₂ Cl ₂ in ¹ ₅ 40 ml of absolute benzene are stirred under argon at 70 ° C

1.5 hours (TLC control: silufop, .CHC1 ₃ ). At the end, the mixture is diluted with 900 mp benzene, the precipitate is filtered off jq

Et ₃ N> HCl and remove the solvent in vacuo. The residue is crystallized in 50 mp ether. 1.00 g (95.2%) are obtained.

1 — amino — 2 — benzoylethinylanthraquinone; dark cherry crystals, mp> 5

I248.5-249.5 ° C (from toluene).

Found,%: C 78.57; H 3.79; N, 4.11.

S _1E N ₁₃ GSO _E

Calculated,%: C 78.63; H 3.73;

N, 3.99.

IR Spectrum (CHC1 ₃ , Vcm ' ¹ ): 1640, 1670 (C = 0), 2190 (C = C), 3330, 3485 (Hili).

1-amino-2- (2'-benzoyl-1'-diethylaminovinip) anthraquinone. 25

0.42 g of 1-amino-2-benzoylethinylanthraquinone and .20 ml Et ₂ NH in 120 mp CHC _{1 3 are} stirred at reflux for 3 hours, the solvent and excess Et ^ NH are distilled off, the residue is chromatographed on silica gel jq in CHClg, 1-amino 2- (2'-benzoyl1'-diethylaminovinyl) anthraquinone 0.44 g (86.8%); red crystals, decomp. > 90 ⁶ C (from benzene-hexane)

Found,%: C 76.34; H 5.84; N 6.56., _ S ₁₇ and _p n _d 0 ₃ .

Calculated,%: C 76.39; H 5.70; N 6.60 ,.

PMR spectrum (CDCli, $, ppm,):

1.05 ears. , 1.50 ears. (CH ₃ ) 3.10 ears, ₄₀

3.55 ug. (CH _z). 6.11 (N ^g ). 7.25 7.45 m (H ³ , ZN Ph), 7.7-7.8 m (H ⁴ ', ⁶ ' ⁷ ),

7.80 - 7.85 m (2H Ph), 8.2 - 8.3 m (n ™).

IR spectrum of 1CHO ± _E , V, cm 1640, 1670 (С = 0), 2335, 3480 (NH ₂ ).

4-Diethylamino ~ 2-phenylnaphthoC2,3-h] quinoline-7,1 2-dione.

0.43 g of 1-amino-2- (2'-benzoyl-1 ^{g of} diethylaminovinyl) anthraquinone and 0.31 g of P0Cl ₃ in 24 mp absolute dioxane are heated at 80 ° C for 100 min, cooling gives 0.27 g (65.6 %) 4-diethylamino-2-phenylnaphtho [2,3-h] quinoline-7,12 dione; orange-red crystals, so pl. 169-170 ° C (from ethanol).

Found,%: C 79.59; H, 5.30; N 6.98.,, ^ 17

Calculated,%: C 79.78; H 5.46;

N 6.89. ’,

NMR (CDClj,, ppm,): 1.21 m (CH _e) 3.44 to _(CH?), 7.45 ⁽³ H), 7.5-7.6 m (SH, Ph ), 7.75-7.85 m (H ⁹ - ' ⁰ ), 8.2-8.5 m (n ⁵ ' ⁶ '*', 2H Ph). IR spectrum (СНС.Т ₃ , V, cm * ⁴ ): 1670 (С = 0).

EXAMPLE 2. Preparation of 4-piperidino-2.-tert-butylnaphtho (2,3-b] quinoline-

7,12-dione,

1-amino-2-pivaloylethinylanthane Aquinone.

Similarly, 1-amino-2 ~ benzoylethinylanthraquinone is obtained from 0.49 g of 1amino-2-ethynylanthraquinone and 0.50 g of pivaloyl chloride. Yield 0.57 g (85.5%), dark cherry crystals, mp 188.5-189.5 ° С (from toluene).

Found,%: C 75.94; H 5.19; N 4.24; C 77 P0 ₃ .

Calculated,%: C 76.13; H 5.17; N, 4.23.

PMR spectrum (CDC1 ₃ , tf, ppm):

1.30 CH ₃ , 7.59 d, 7.73 d (H V), 7.75-

7.80 m (H ⁶ ' ⁷ ), 8.20-8.35 m (H ⁵ - ⁹ ).

IR spectrum (СНС1 ₃ , V, cm ¹ ): 1660, pl. 1640 (C = 0), 2190 (C = C), 3330, 3485 (NH ₂ ).

1-amino-2- (4 ’, 4 '-dimethyl-3'oxo1' -piperidinopent-1 '-enip) anthraquinone,

0.60 g of 1-amino-2-beerpoylethinylanthraquinone in 10 mp piperidine is stirred at 20 ° C for 25 minutes, diluted. 50 ml of CHC1 ₅ and the solvent and excess piperidine are removed in vacuo. After recrystallization from 15 ml of a mixture of benzene and hexane (1: 1), 1-amino2- (4 ¹ , 4 '-dimethyl-3'-oxo-G-piperidinopent- 1 '-enyl) anthraquinone 0.59 g (78.3%), bright red crystals, mp. 202-203 ° C (from benzene-hexane).

Found,%: C 74.78; H 6.50;

N 6.72, θϊ 3 ’

Calculated,%: C 74.97; H 6.78;

N, 6.73.

PMR spectrum. (CDC1 ₃ , <G, ppm):

1.10 (СН ₃ ), 1.62 m (у0, 2 * -НУ | 3.2 m (</ - СН ₂ ), 5.70 (Н ^g ), 7.6-7.8 m,

8.15-8.30 m (H ³ · ⁹ ).

ute, poured while stirring in

100 mp 10% aqueous KOH and extracted with CHClj, the chloroform solution was washed with water, dried with calcined MgSO ^ and the solvent was removed in vacuo. After recrystallization of the residue from 200 mp benzene with hexane (1: 3)

5 · - 1574598

IR spectrum I (CHC1 ₃ ), cm- '): 1635,

1670 (C = 0), 3335, 3480 (NH ^). _v

4-1b-teridino-2-tert-butylnaphtho / [2,3b] quinoline-7,12-dione.

0.33 g of 1-amino-2- (4 ', 4'-dimethyl-3 ~ oxo-1'-piperidinopent-1 ^f- phenyl) anthraquinone and 0.23 g of POI j in 25 mp dioxane are stirred at 80 ° C. 35 min, poured into 120 ml of 5% aqueous KOH and then processed as described in example 1. The crude product (0.24 g) was recrystallized from an 8 mp mixture of benzene and hexane (1: 3). Yield of 4-piperidino-2-tert-butylphto [2,3-b] quinoline-7,1 2-dione 0.17 g (53.8%), orange-yellow crystals, mp 162-163 ° С (from ethanol).

Found,%: C 78.21; H, 6.62; N, 7.61.

Calculated,%: C 78.36; H 6.58; N, 7.63.

¹ H-NMR spectrum (CDCl ^, J ¹ , ppm): 1.53 (CH ₃ ), 1.80 m (/ 3, y —CH ₂ ), 3.17 m (rf-CHj 7.08 ( H ³ ), 7.7-7.8 m (H ^9.10 ), 8.20-8.35 m (H ^{f, i} ' ^M ).

Thus, a new method has been developed for the preparation of new 4-dialkylamino-2 ~ alkyl (or phenyl) naphtho [2, 3-h] quinolin-7, 12-diones, which can be widely used in the national economy.

Claims (2)

Claim The method of obtaining 4-di alkyl amino-2apkyl (or phenyl) naphtho [2,3-IZHINOLIN- 7,12-dione General Formula R- ^and e C ₂ H 5 ·; 2) R ₁ - -C (CH ₃ ) /; R ₂ and Rj form, together with an azo nitrogen, a radical characterized in that, 1-amino-2- (1 '-dialkylamino-2'-acyl vinyl) -anthraquinone of the general formula O C = CH — C — R I ' 1? R ₂ R ₃ where R, R ^ and R ₃ have the indicated meanings, are cyclized in the presence of 35 phosphorus oxychloride in dioxane at 60-80 ° C followed by treatment of the reaction mixture with an aqueous solution of alkali.