SU812178A3 - Method of preparing derivatives of 1-azaxanthon-3-carboxylic acid of their salts with aliphatic amines - Google Patents

Description

Ij is a cyano-, alkoxycarbonyl radical, in which the alkyl part has 1-6 carbon atoms, carbsnssamide, undergoes K11Slot 4y or alkaline hydrolysis, and at a temperature of 10-15 O.

In the formula It, the estor R2 may be in positions b, 7, 8, or 9 of the aa-axentank ring.

Inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or organic acids, in particular trifluoroacetic acid, are used to maintain acid hydrolysis.

Usually, acid hydrolysis is carried out |

The process is conducted from one hour to 2 days.

Compounds of the general I can be converted into the salts of aliphatic communes in the 1H "manner by heating the starting reagents in a suitable solvent.

The outcome of the combination of the formula formula II can be obtained from compounds of the general formula

Efflj

Sh

where 2 is as defined above, which is translated into compounds of the general formula

Kochoryu is reacted with a compound that is active (methylacetadetate, ethyl acetate), acetylcarboxylic acid (dimethylacetylenedibarboxylate, diethyl acetylenediborboxylate), with hectare of cyano acid and cyanoacid (cyanoacetate hydrochloride), and cytoacrythroxide;

I When using methylene-Sodium, it is preferable to conduct the process in the presence of organic amine, butylamine, benzylamine, 2-me (methyl imidazole, morpholine), which takes from catalytic amounts to 5 mol. eq. per 1 mole of the compound of general formula III.,

It is desirable to conduct the process in an organic solvent, such as aliphatic alcohol, aromatic hydrocarbon, dimethylformamide at the boiling point for 1-24 hours. J In case the compound of general formula III is reacted with acetylene carbonate derivative, it is also desirable the presence of organic. in solvent medium at boiling point.

Leucorium cyanocarboxylic acid halide is used as one of the starting materials for the preparation of compounds of general formula II, then the reactions are carried out in the presence of a substituted formuline or its mixture with an organic solvent.

Process temperature varies

from 20 to, last carried out / for from .30 minutes to 2 days. The amount of cyanocarboxylic acid halide used is 1-10 mol. SQ. on the basis of the starting compound of formula II, the compound of formula II, in which R is an alkoxy group, is obtained by reacting a compound of formula II,

5 where R is a hydroxy group, with diazomethane or haloalkyl, preferably in an organic solvent at a temperature from 0 to organic boiling point.

Compounds of formula iI, where R is hydroxy group, are obtained by reacting compounds of formula II, where RJJ is an amino group, with an alkali metal nitrite in an aqueous solution of inorganic or organic acid.

Below are the prikuryury of obtaining outgoing. compounds.

And pm ime jp 1. A mixture of 2 ml of morpholine, 3 MP of dimethylformamide and 10 ml of water is heated, while stirring for 5 minutes, 1.71 g of fine-grained "valuable 4-hydroxy-744Ng -1 -benzopyran-3-" is added. carbonitrile. The mixture is then heated at this temperature for 1 hour. The resulting precipitate is filtered by filtration, npokOiBeuoT with water, recrystallized from acetic acid and washed with chloroform. Obtain 1.32 g of 0 crystals of 2-g1 "but-4-oxo-4H-1-beisopyran-3-carboxaldehyde, so pl. 252-255 With (with different.).

JMP spectrum (DMSO - d) t 10.19 (1H, s); 9.67 {approx. 1.5 N, broad, ka / s). : 8.11 (1H, d, 3 ″ 2 and 8 Hz), 7.97-7.30 (ЗН, t).

Elemental analysis for QQ. Calculated,%: C 63.49, H 3.73, N 7.41.

Found,%: C 53.59, H 3.44, 0 N 7.45.

The compounds listed in Table 2 are prepared analogously. one.

Table 1

6-Methyl-4-hydroxy-4H-1-benopyran-Z-carbonitrile

6-ETHIL-4-OXI-4N-1-benzopyran-3-carbonitrile

b-Chloro-4-hydroxy-4H-1-benzopyran-3-carbonitrile.

6-Methoxy-4-OXI-1H-1-benzopyran-3-carbonitrile, 8-dimethyl-4-oxo-4H-benzopyran-3-carbonitrile

7-Hydroxy-4-OXO-4N-1-benzopyran-Z-carbonitrile

6-Nitro-4-oxo-4H-1-benzopyran-3-carbonitrile

6-Isopropyl-4-oxo-4N-1-benzopyran-3-carbonitrile

6-n-Butyl-4-oxo-4N-1-benzopyran-3-carbonitrile

8-Methoxy-4-OXO-4N-1-benzopyran-3-carbonitrile

282-284 (with dec.) (Acetic acid)

246-249 (with dec.) (Acetone) 308-310 (with dec.) (Acetic acid)

251-254 (with dec.) (Chloroform)

259-263 (with dec.) (Acetic acid) 297-399 (with dec.) (Acetic acid)

290-293 (with decomp.) (Formic acid)

206-208 (acetic acid)

220-222 (acetic acid) 235-238 (chloroform) 3-Cyanobenzo (f) -chromone b-Dimethylgshino-4-OXO. -1-benzopyran-3-carbon -. . reel 6-tert-Vutyl-4-oxo-4N-1-benzpyran-3-carb: Onitrile

Example 2. A mixture of 2.17 g of amino-6-ethyl-4-oxo-4H-1-benzopyran-3-carboxyldehyde, 4.0 ml of ethyl acetoacetate, 50 ml of ethanol and 5 ml of piperidium nvi revgotz with reverse cooling NIKOM with stirring for 2 hours After cooling, the residue is isolated by filtration and recrystallized from ethanol. According to this procedure, 1.60 g of substance is obtained as yellowish needles, which are 7-ethyl-2-methyl-1-azaxanthone-3-carboxylate, m.p. 149-151С.

IR spectrum (Mujol),: 1715, 1665.

Ethyl 2-methyl-12-Amino-4-oxo-4H-1-ben-ao-axantoi-3zopyran-3-carboxal-carboxylate

guide

Ethyl-7-methoxy2-Amino-6-methoxy-4-2-methyl-1-azak-oxo-4H-1-ben3opirantanone-3-carbo-3-carboxaldehyde

Ethyl-7,9-dimethyl-2-Amio-b, 8-dimethyl-2-methyl-1-azac-4-oxo-4Я-1-benzopyransan-3-carbo 3-carboxaldehyde

ETHIL-7-HLOR-22-Amino-6-chloro-4-6kso-methyl-1-aeksan-4N-1-benzopyran-3-carbton-3-carboxylate

ethyl-7-nitro-22-amino-6-yitro-4-oxo-methyl-1-azaxan-4H-1-benzopyran-3toi-3-carboxylate

-carboxaldehyde

Continued table. one

NMR spectrum (ODCU) - (f: 9.15 {1H, S) 8.08 (1H, S), 7.37-7.75 (2, m): k, kk (2H, q, 3. 7-GC) 2.97 (3H, S); 2.81 (2H, q, 3 7 Hz); 1, lt5 (3N, J 7); 1, 33 (3H, t, 3 7 Hz).

Elemental analysis for

Calculated,%: C 69.44; H 5.50; N 3.50.

Found,%; C 69.58 H 5.44; N 4.28.

In a similar manner, the compounds listed in Table 2 are obtained. 2. Table 2

155-156 (ethanol)

203-205 (ethanol)

xylate

165-166 (ethanol)

xylate

175-176 (ethyl acetate)

212-213 (dimethylformamide) 2-Aminobenzo (f) - 258-260 (with decomp.) Chromone-3-carbox- (foaming, 2-amino-6-dimelg1MI-276-280 (with decomp.) But 4-oxo-4H-1-benzoforof and meta. Zopyran-3-carbox-amino-6-tert-buyl-4-oxo-4 Ht-1-benopyran-3-carboxaldehyde / acetic acid) nol aldehyde 240- 242 (acetic acid) aldehyde

Example 3. A mixture of 2.17 g of amino-6-ethyl-4-oxo-4H-1-6enzo-11iran-3-carboxapydehyde, 4.0 ml of acetylanoacetate, 50 ml of ethanol and 5.0 ml of piperidine are heated under reflux for 30 After cooling, the crystalline precipitate is isolated by filtration and washed with chloroform. According to the method described above, poluchaio 2.07 g of substance in the form of colorless needles, which represents the original connection

Ethyl 2-amino-1-azaxantoi-3-carboxylate

Ethyl 2-amino-7-methoxy-1-azaxantoi-3-carboxylate

Ethyl 2-amino-7,9-dimethyl-1-azaxanthone-3-carboxylate

Ethyl-2-c1MINO-7-methyl-1-azaxanthone-3-carboxylate and Ethyl 2-amino-7-methyl-1-azaxanthone-3-carboxylate 4 Ethyl 2-amino-7-isopropyl-1 gasaxant. He-3- carboxylate

Tyl-2-amino-9-methoxy-1-azaxanthone-3-carbo3-xylate

Etsh1-2-amino-7-n-butyl-1-gaeoxanton-3-carboxylate

Ethyl 2-amino benzo (f) -1-azaxanthone-3-carboxylate

Ethyl 2-a№4INo-8-hydroxy-1-azaxanthone-3-carboxin Ethyl 2-c1 Mino-7-methoxy-1-azaxanthone-3-carboxylate

is 2-amino-7-ethyl-1-aeaxiton-3-carboxylate, t, pl. 279 280s .. Elemental analysis; l C H NgO, Calculated,%: C 65.37; and 5.16, N, 8.97.

Found,%: with 65.24, H 5.08; N8.86.

In a similar manner, the compounds obtained in Table 1 are obtained. 3.. Table3

Melting point, C (solvent for recuring)

- ethanol)

- ethanol)

- ethanol)

299-300

(dimethylformamide)

277-279

(chloroform)

243-244 (ethanol)

300

(methylformamide)

234.5-235 (ethanol)

279-280

(chloroform - ethano

300

(dimethylformamide)

lat

286-288

(chloroform - ethano

Example 4. A mixture of 366 mg of 2-amino-4-ocoo-4H-1-benopyran-3.-Carboxaldehyde, 500 mg of methyl-3-oxopropiolate and 0.6 ml of piperidine in 20 ml of methanol heating with reverse | A1 cooler for 6 hours The reaction mixture is concentrated under reduced pressure and the residue is chromatographed on a column of silica gel. The elution is carried out with chloroform and a portion of the eluate of sabrgiot and recrystalline is extracted from methanol, described yutodike get 52 mg of the substance in the form of yellow crystals, which is a 2 and-propyl-1-aza) xantone-3-carboxylate, m.p. , 105-106 0.

IR (K & g), 1725, 1680.

5SR spectrum (sos) (G: 9.23 (1H, S) 8.35 (1H, dd, 3-8 and 2 Hz); 7.3-. 8.0 OH, t); 3.95 MH, S); 3.32,

UH, t, 7 Hz); 1.6-2.3 (2H, t 1.06 (ЗН, t, 3 «7 ГЦЬ

Eleyer analysis for Ct7 5 0.

Calculated,%: C 68.67; H 5.08; And 4 | 71.

Found,%: C 68.79; H 5.02; N 4.62.

EXAMPLE 5 A mixture of 1.085 g of 2-amIr-b-8Tyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde, 2.0 ml of ethylbay zoyl is shedat, 5 O of ml of ethanol and. 1.0 pipidine is heated under reflux for 6 hours and in a hot condition a small amount of non-soluble substances are filtered off. The filtrate is cooled and the resulting precipitate is removed by filtration and the recrystallization is called ethanol. According to the described 2gAMiio-1 azaksan27f MHHO-4-OKCO-4Hton-3-carboxamide -1-beisopyran-3-carboxaldehyde 2-Amio-7 chloro-12-AftaiHO-6-HLOR-4N-1-benzopyran-3-azaxaiton- 3-carboxamide. -carboxaldehyde

 ° PRI me R 7. Mixture. 217 mg 2-ami; no-6-ethyl-4-oxo-4H-1-beisopyran-3-V 5 -carboxaldehyde, 300 mg of malononyl reel, 5 ml of ethanol and 0.5 mL of piperidine are mixed under heating at reflux for 15 min. and after cooling, the limited but soluble solubles were collected by filtration. and recrystallized from dimethylformamide. According to the procedure described above, psklujut 160 mg. 2-amino-7-ethyl-1-aEaxantoi-3-carboxy-5

| above method get 635 mg of ethyl-7-ethyl-2-phenyl-1-azaxanthone-3-carbooxylate in the form of light yellow needles, so pl. 176-177p. .

IR (Nujol), 1730, 1675.

NMR spectrum (COCIj) cP: 9.12 (IH.S 8.18 (IH.s); 7.30-7.87 (7H.m) -, 4.28 (2H, q, 3-7) ), 2.82 (2H, g, 3 - 7 Hz), 1.03-1.53 (6H, t + t).

Elemental analysis for

Calculated,%: C 73.98 H 5.13; M 3.75.

Found%: C 74.10 H 5.08 / N 3.71 ...

EXAMPLE JP 6, A mixture of 217 mg of 2-a 1INO-6-ethyl-4-oxo-1H-1-benzopyran - 3-carboxald Eguid, 300 mg of cyanoacetg (, 5 ml of ethanol and 6.5 ml of piperidine heated under stirring for 1 h after cooling, the moderately soluble product is collected by filtration and nepecplusalized from a mixture of dimethylformamide - gsheta.P6 using the procedure described above, 180 mg of crystals of 2-a-7-ethyl-1-aaxanthone-3-carboxamide, t.

NMR spectrum () (f: 9.50 (1H, S. 8.2d (lH, d, 3 .2 Hz); 7.88 (1H, ddX} 7.63 (1H, d, 3 - 9 g 2 , 91 (2H, q, 3-7 Hz) (3N, t, 3. 7 At).

Elemental analysis for N HjOa

Calculated,%: C 6-3,59} H 4.63 / M 14.83.

Found,%: C 63.40) H 4.72, M 14, ..

According to a similar procedure, the compounds listed in Table 2 are obtained. four.

T a b l and c a 4

nitrile in the form of colorless needles, so pl. ZEP ..

IR spectrum (NuJoO, cm: 3325, 3125, 2225, 1660.

NMR spectrum (CF-COOO), (f: 9.07 (1H, S); 8.16 (IH.d, 3 2 Hz) 7.8i8 (1H, d ,, d); 7.63 (1H , d, 3 9 Hz) {2.92 (2H, q, J. 7 Hz) -J 1.39 (3N, t, 3. 7 HZ).

Elemental analysis for N N Ol

Calculated,%: C 67.91; H 5.18; M 15.84. 300 (dimethylformamide) 300 (dimethylformalide):

Found,%: C 67.75, H 4.01, N16.00.

Initial compound

2 - Amino-4-oxr-4N-1-benzopyran-Z to Arbox alde guide

2-AMINO-6-HLOR-4-oxo-4N-1-benzopyran-3-carboxaldehyde

2-amino-6-dimethyl-amino-4-oxo-4H-1-benzopyran-3-carboxaldehyde 2-amino-b-isopropyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde

2-amino-6-methyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde Example 8. A mixture of 2.17 g of 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde , 1.788 g of dimethyl acetylenedicarboxylate, 50 ml of methanol and 0.5 ml of tritylamine are stirred at reflux for 3 hours and after cooling, the precipitate is collected by filtration. The resulting precipitate is added to chloroform and, after stirring, the sparingly soluble product is filtered off. The filtrate is concentrated to dryness and dissolved in 50 ml of a mixture of n-hexane-chloroform - acetone (10: 5: 0.5). The solution was passed through a column of silica gel (30 g) and eluted with the same solvent system. The eluate is concentrated and the residue is recrystallized from methanol. According to the procedure described above, 590 mg of dimethyl-7-ethyl-1-azaxanthone-2, 3-dicarboxylate are obtained in the form of colorless needles, t. Pl. 169-170 with IR spectrum (Nujol 1720, 1670. 9.20 (IH.S) -, NMR spectrum (CDCIj) 8.10 (1H, d, 3 Hz); 7.68 (1H. Dd ,. 3 2 and 8 Hz); 7.52 (1H, d, 3

According to a similar procedure, the compounds listed in Table 5 are prepared.

Table 5

Melting point, C

Product (recrystallization solvent)

2-amino-1-azaksan-300 ton-3-carbonitrile

2-AMINO-7-HLOR-1-300 -axaxanton-3-carbonitrile-2-amino-7-dimethyl-300-amino-1-azaxanthone-3-carbonitrile

7-Isopropyl-2-amino-300-3-cyano-1-azaxan-. tone

7-Methyl-2-amino-3-300 - Cyano-1-azaxanthone 8 Hz) -, 4.05 (3H, S); 3.99 (ZN) 2.83 (2I, q.); 1.33 (ZN, t, 3 7 HZ). Elemental analysis for Calculated,%: C 63.34; H 4.43, N 4.10. ,%: C 63.15, H, 30; N i, 01. Example 9. A mixture of 1.83 g of 2-amino-4-oxo-4H-1-benzopyran-3-carboxaldehyde, 1.6 g of dimethyl tetlendicarboxylate, 50 ml of ethanol and 1 drop of triethylmino is stirred under reflux for 2 h. . The resulting reaction mixture was concentrated under reduced pressure and ether was added until a precipitate formed. The crystalline product is collected by filtration, washed with ether and recrystallized from methanol. According to the procedure described above, 2.06 g of dimethyl-1-azaxanthone-2,3-dicarboxylate are obtained in the form of colorless needles, mp. 149-151 0 .. IR spectrum (KBG), cm: 1750, 1730, 1675.

NMR spectrum (CDCI) rf: 9.28 {1H, S) 8.20 (1H, dd, 3 2 and 8 Hz).

Elemental analysis for NCjr.

Calculated,% C 55,34; H 2, EO; N 4.03.

Found,%: C 55.25 / H 2.74; N 3.94.

Example 10. A mixture of 2.17 g of 2-ami of o-6-ethyl-4-oxo-4H-1.-benzopyran-3-carboxaldehyde, 2.5L g of diethylacetylenedicarboxylate, 5O ml of ethanol and 0.5 ml of triethylamine H ire reflux for 2 hours and heat a small amount of the partially soluble product while hot. The filtrate is cooled and the resulting crystal is collected by filtration and nejpe crystallized with ethanol. According to the procedure described above, 3.2 g of diethyl-7-ethyl-1-azaxanthone-2, 3-dicarboxylate are obtained in the form of colorless crystals, t, pl. 112; .

IR (Nujol), cm: 1745, 1718, 1665.

Nuclear Magnetic Resonance Spectrum (CDCU) (J: 9.28 (1H, S). 8SD {1H, S), 7.43-7.83 (2H, m); 4.274, 77 (ktt, q + q) V 2.82 (2H, q, 3 7 Hz); 1.17-1.62 (9H).

Elemental analysis for N0.

Calculated,%: C 65, OZ; H 5.19, N 3.79.

Found,%: C 65.23, H 5.04; N 3.87.

Example 11. A mixture of 217 mg of 2-aMino-6,8-dimethyl-4-oxo-4H-benzopyran-3-carboxaldehyde, 255 mg of diethylene dicarboxylate, 10 ml of ethanol and 0.05 ml of triethylamine are heated under reflux and for 3 hours, after which 150 mg of diethyl acetylenedicarboxylate, 1 ml of ethanol and 2 drops of triethylamine are added. The resulting mixture is heated under reflux for an additional 2 hours. After cooling, the precipitate is collected by filtration and recrystallized twice from ethanol. According to the described procedure, polupigot 260 mg of diethyl-7, .9-dimethyl-1-azaxanthone-2,3-dicarboxylate as yellow crystals, so pl. 156-159 ° C.

IR spectrum {NujoO, 1740,, 1675. NMR spectrum {COCl9) o: 9.22.

(GT1.3), 7.90 (IH.S); 7.45 (1H, S), 4.57 (2H, q, J 7 Hz),., 5 (2H, q,

J. 7 HZ); 2.58 (3H, S,), 2.43 (3N, 5) —1.47 (6H, t, 3 7 HZ).

Example 12. According to the method similar to that described in Example 9, dimethyl-7-chloro-1-azaxan-2,3-2 is obtained from 2-amino-6-chloro-4-oxo-4H-1-benopyran-3-carboxaldehyde. dicarboxylate - slightly yellowish needles (recrystallization solvent ethyl acetate), so pl. 220-223 C.

Elemental analysis for C H / ONO C1,; Calculated,%: C 55.34 / H 2.90, N 4.03.

Found, I ,: C 55.25; H 2.74, N 3.94.

Apply p. 3. A mixture of 5.5 g of 2-amlo-4-oxo-4H-1-benzopyran-3-carboxaldehyde, 5 g of ethyl propiolate, 25 ml of dimethyl chormamide and 0.1 ml of triethylamine is heated under stirring for 1 hour. The resulting reaction mixture concentrated under reduced pressure and the residue is recrystallized from. methanol. According to a similar method of semi-.

3.5 g of ethyl-3.-N- (3-formyl-4-oxy-l-benzopiran-2-yl) aminocrylate as colorless needles, t. pl. 201203 S ...

IR spectrum (KBG), cm: 1700, 1680.

Nuclear Magnetic Resonance Spectrum (CDCl3) cf: .10.47

(1H, S), 8.23 (1H, dd, .0 2 and 8 Hz); 7.68 (1H, d, 3 9 Hz); 7.3-7.8 (3N, t): 5.45 (, 1H, d, 3 9 Hz); 4.38 (2H, d, 3 6 gd): 3, fit (ZI,

t, 3 6 rd).

Elemental analysis for H N0. . Calculated,%: C 62.71 / And 4.56, N 4.88.

Found,%: C 62.47J H 4.40,

N 4.81.

A mixture of 3.5 g of ethyl-3-N- (3-formyl-4-oxo-4n-1-benzopyran-2-yl) aminracrylate, 5 ml of triethylamine and 20 ml of toluene is then heated under reflux for 24 h. The resulting reaction mixture is concentrated under reduced pressure and the residue is recrystallized from methanol. According to the procedure described above, 1.42 g of ethyl-1-azaxanthone-3-carboxylate are obtained in the form of light yellow crystals, mp 139-140 ° C.

IR spectrum (KBG), cm: 1715, 1670, .1615.

NMR spectrum (COCU) d: 9.2-.9.4 2H, t) -, 8.35 (1H, dd, 3 2, and 7 Hz); 7.2-8.0 (ZN.t), 4.50 (2H, q, U 8 Hz), 1.34 (3N, t, 3 8 Hz).

Elemental analysis for H N0.

Calculated,%: C, 66.91; H 4.12; N 5.20.

Found,%: C 66.71; H 4.00; N 5.11.

Example 14. A mixture of 2.23 g

2-hilino-6-chloro-4-oxo-4H-1-benzopyran-3-carboxaldehyde, 5 g of ethylpropionate, 30 ml of dimethylformamide and 0.1 ml of triethylamine are stirred at 90 ° C for 1 hour. After cooling, the mixture is filtered to isolate draft. The precipitate obtained is washed with methanol, whereby 1.6 g of ethyl-3-N- (3-formyl-6-chloro-4-px-4H-1-benzopropyran-2-yl) amino-acrylate are obtained in the form of silver crystals. These crystals are stirred with 15 ml of dimethylformamide and 5 ml of triethylamine with heating at 130-140 ° C. for 2 hours. The resulting reaction mixture is concentrated under reduced pressure and the residue is recrystallized from ethanol. According to the procedure described above, 650 ml of ethyl 7-chloro-1-azaxanthone --- carboxylate are obtained in the form of light yellow needles, so pl. 176-177 C. IR spectrum (KBr): 1725, 1675, NMR spectrum {C D C 13) 9.37 (1H, 3 2 Hz); 9.26 (1H, d, a 2 Hz), 8/30 (1H, d, 3 2 Hz) 7.80 (1R, dd. 3 2 and 8 Hz), J, 60 (1H, d, tJ 8 d); 4, 84 (2H, q, 3 7 Hz) V 1.43 (3N, t, Hz). Elementary analysis for H.N-0 “Calculated,%: C 59.32; H 3.32; 4.61,%: C 59.40; H 3.18; Found, Example 15. According to the procedure ,, as described in Example 9 and 2-amino-6-nitro-4-oxo-4H-1-benzopy-3-carboxaldehyde, these 7-nitro-1-azaxan-3- carboxylate light yellow plates (when recrystallized from dimethylformamide) t. pl. 228-229 ° C. IR spectrum (KBr),: 1720, 1675. Nuclear Magnetic Resonance Spectrum (CFgCOOD) cf: 9.1-9.3 (2H, Br, 5) 5 8.92 (1H, d, TJ 2 Hz

Initial compound

7

Melting point, C (recrystallization solvent)

221-222- (ethanol)

Ethyl 7-methyl-2-hydroxy-1-azaxanthone-3-carboxylate

269-270

Ethyl 7-methoxy-2 (chloroform-ethanol) -oxy-1-az-axanton-3-carboxylate

142-144. (Ethanol)

Ethyl 7-n-butyl-2-ox. And 1-azaxanthone-3-carboxylate

252-254

Ethyl-9-methoxy-2 (dimethylformamide) -oxy-1-az.axanton-3-to arboxylate 0.42 (1H, dd, 3 2 and 9 Hz)} 7.48 (1H, d,: i 9 Hz ); 4.22 (2H, q, 3 7 Hz) 1.10 (3N, t, J 7 Hz). fAoNflOfi Elemental analysis of dd C, d 3.21; %: C 57.33, Suspected, 8.92. Found,%: C 56.96; H 3.09, N 8.76. Example 16. A mixture consisting of 3.17 g of 2-g1-IMO-6-ethyl-4-oxo-4H-1-benopyran-3-carboxaldehyde, / 8 g of diethyl malonate, 15 ml of pyridine, 1 ml of 1,8-diazabicyclo 5.4.0 U ofdecene and 50 ml of ethanol are stirred under heating at reflux for 15 hours. The reaction mixture is concentrated under reduced pressure and the residue is acidified with hydrochloric acid. The precipitate obtained is filtered, washed with water and recrystallized from ethanol. According to this procedure, 1.23 g of ethyl-7-ethyl-2-hydroxy-1-azaxanthone-3-carboxylate are obtained in the form of light yellow needles, mp. 200-204 ° C. IR spectrum (KBG), cm-: 1675, 1610. NMR spectrum (COClS) ": 1.35 {3N, t, E 7 Hz); 1.53 (3N, 3 7 Hz) 7 Hz); 2.87 (2H, q. 3 4.58 (2H, q, a 7 Hz); 7.4-7.8 (2H); 8.23 (1H, q, 3 2 Hz), 9.30 ( 1H, S). By the same procedure, compounds were prepared, as shown in Table 6. Table 6

Example 17. A mixture consisting of 326 mg of 2-amino-6,8-dimethyl-4-oxo-4J-1-benzopyran-3-carboxaldehyde, 7.5 ml of ethanol, 2.0 ml of pyridine, 2.0 ml diethyl malonate and 0.1 MP of 1,8-diazabicyclo 5,4,0 -7-undezene heated under reflux for 4 h, after which the solvent is distilled off. To the residue was added 1 n. Chloris1: hydrofluoric acid solution and sparingly soluble product is collected by filtration and dissolved in chloroform. Chloroform chromatography solution coziness violently and elute with chloroform-acetone-formic acid mixture (9: 1: 0.1). The purified solution is additionally recrystallized with Tle ethanol. Obtain 20 mg of light yellow crystals of ethyl 2-hydroxy-7,9-dimethyl-1-azaxanthone-3-carboxylate, so pl. 251-253 0.

IR (Nujol), cm: 1700, 1675, 1650.

Initial compound

7.-Methyl-3-cyano-1-azaxanthone

Z-Cyano-1-azaksan7-Isopropyl-3-cyano-1-azaxanthone

7-Chloro-3-cyano-1-azaxanthone

7,9-Dimethyl-3-cyano-1-azaxanthone 7 -t-Butyl-3 - cyano-1-azaxanthone

. NMR spectrum (CDCl3) (f; 12.30 (IH.er) 9.22 (1H, S), 7.93 (1H, S), 7, kS (H,) (2ti, q. T) 7 HZ); 2.57 (3H, S); 2. (3H, S); 1, 50 (30N ;; t).

Example 18, 1.82 g of 2-amino-b-ethyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde was dissolved in -fO ml of dimethylformamide, after which 3.5 g of cyanoacetyl chloride was added. The mixture reacts at 6 ° C for 3 hours with constant stirring. Then the solvent was distilled off under reduced pressure and the resulting residue was chromatographed over silica gel. The desired product is separated from chloro. molten slut and recrystallized from acetonitrile. According to the described procedure, 1.03 g of 7-ethyl-3 cyano-1-azaxanthone is obtained, m. Pl. 183185RS

The compounds obtained in Table 7 are obtained in the same way.

1: Table 7

melting point, C (recrystallization solvent)

240-242 (ethanol)

220-226 (ethanol) tone

203-205 (ethanol)

286-288

(dimethylformamide)

254-257 (acetonitrile)

247-249 (acetonitrile) Example 19 1.0 g of ethyl-T-ethyl -2-hydroxy-2-azaxanthone-3.-carboxylate was dissolved in 20 ml of chloroform and the solution obtained in solution. An excess amount of diaeomethoethane, dissolved in ether, is added dropwise over 15 minutes with stirring and at room temperature. The reaction mixture is peremeshivat for 45 minutes at room temperature and then a small amount of acetic acid mixture is added to decompose the excess diazomethane. The solvent is distilled | 1. -the residue is chrome-doped on a strong kagel and eluted with chloroform acetone-formic acid (20: 1: 0). The first fraction is recrystallized from acetone to form 615 ethyl-7 hydroxy-2-methoxy-1-azaxanton-3 carboxylate as colorless needles, T. Pl. 145-14b. Elemental analysis for C y Calculated,%: C 66.05 {H 5.42, N 4.28. Found,%: C 66.12, H 5.23, N 4, 21. IR spectrum (Nujpl), cm g-: 1730, 1670, 1605, 1590, 1310, 1240, 1220. 815, 790. NMR spectrum (COCIi) (G: 9.17 (GN, 8.13 ( 1H, bs), 7.55 (2H, m); AU (2H, q, .3 7 HZ), C, 20 (3H, S) / 2.82 i (2H, q,: J 7 Hz)} 1 , 43 (ЗН, t, 3 "7 HZ); 1, 32 (ЗН, t, Э - 7 HZ. Example 20. To a mixture of 25 ml of phosphorus trichloride and 3 g of n phosphorus chloride was added 974 ml of ethyl-7-ethyl-2-hydroxy-1-azaxanthone-3-carboxylate with stirring for 12 hours and then phosphorus trichloride was distilled off under reduced pressure. To the resulting residue, while cooling with ice, add gradually ethanol with to dissolve the residue, the solvent is then distilled off and the residue is chromatographed on silica gel. The “1st product” was eluted with benzene and recrystallized from isopropyl ester, resulting in 658 mg of atil-7-ethyl-2-chloro-1-azaxan-tone-3-carboxylate as colorless crystals, mp. 160-161 ° C. Elemental analysis for C H HO O C Calculated, C 61.54; H 4.25; N 4.22. Found: C 61.46, H 3.98 / N.4.27. -, IR spectrum (Nujol), cm-: 1720, 1658, 1585, 1265, 1210, ISO. NMR spectrum (COCI - &) (f: I, 30 J3H, t, 3 7 Hz) {, k3 (3H, t, 3 rij); 2.7 (2H, q, J 7 Hz), (2H, q, 3 7 Hz) 1. 7, (IH, d, 3.8 Hz); 7.63 (IH, dd, 3-2 and 8 Hz), 8.03 (1H, 3 2 Hz), 9.06 (1H, S). Example 21: 884 mg of ethyl-7-ethyl: -2-chloro-1-azaxanthone-3-carboxylate were added to 20 ml of chloroform, 3 ml of methylamino-ethanol solution was added to the resulting solution. The mixture was stirred at room temperature for 2 hours and then the solvent was distilled off, water was added and the resulting mixture was collected from the filterworm and recrystallized from dimethylformamide. According to the described procedure, 730 mg of 7-ethyl-2-methyl-1-azino-1-azaxanthone-3-carboxylate are obtained in the form of colorless needles, t. Pl. 205-207 C. Elemental analysis of dl. Calculated,%: C, 66.24; H, 5.56; N 8.58. Found,%: C 66.22; H 5.47V N 8.74. IR spectrum (Nujol), cm-: 3250, 1660, 1610, 1582, 1280, 1240. NMR spectrum (СF3COOp) cf: 1.36 (ZN, t, 3 - 7 Hz); 1.53 (3N, t, J Hz), 2.90 (2H, q, J - 7 Hz), 3.50 (3H, S), 1 |, 60 (2H, q, 3. 7 Hz), 7.60 (1H, a; J - 8 Hz); 7.90 (1H, dd, 3-2 and 8 Hz), 8.20 (1H, d, 3 2 Hz); 9.3: (1H, S). Example 22. A mixture consisting of 2.17 g of 2-amino-6-ethyl-4-oxo-4H-1-benopyran-3-carboxaldehyde, 25 ml of dimethylformamide, 5 g of ethylpropyl and 0.1 ml of triethylamine pere- mix at 1 hour and stand at room temperature. The resulting crystals are collected by filtration and recrystallized from acetone to form 1.65 g of ethyl 3- (6-ethyl-e-formyl-4-hydroxy-4H-1-benzopyra-2-yl) and shnouacrylate in the form of colorless isl, m.p. 201-203 ° C. IR spectrum (KBg), cm-: 3070, 1700 1665, 1635. NMR spectrum (COCl4) f; 13.50 (1H, d, e - 12 Hz); 10.36 (iH, si ;; 8.2. (1H, d, 3 - 2 Hz) 7.17-7.73 (ЗН, t), 5.42 (1H, d, 3 - 9 Hz) t.31 1 (2H, q. 1-7 Hz), 2.75 (2H, q, 3 "7 Hz), 1.35 (3N, t, E - 7 Hz); 1.28 (3N, t, 3 - 7 Hz ). Elemental analysis for C S Calculated,%: C 64.75, H 5.43, N 4.44. On "Dio: C 64.72; H 5.40; N 4.33. In a method similar to that described above , from 2r uiHHo6eH3o f of chromono-3g carvoxaldehyde, ethyl-3-2-formylbenzo f J-chromon-2-Il-aminocoacrylate is obtained, m.p. 228-230GS (with dec.), Recrystallization solvent: chloroform - petrodeyny ether. Example 23. A mixture consisting of 1.58 g of ethyl-3- (6-ethyl-3-formyl-4-oxo-4H-1-benopyran-2-yl) amino-acrylate obtained in Example 22, 15 4L of dimethylphrmamide and 5 ml of triethylmino is heated under reflux at 130 ° C for 2.5 hours. The resulting reaction mixture is concentrated and 50 ml of ethanol is added to the residue. Ethanol solution is cooled. and the precipitated crystals are collected by filtration and recrystallized from ethanol with the formation of 920 mg of ethyl 7-ethyl-2-azaxanthone-3-carboxylate as light yellow needles, so pl. 140-142 C.

IR spectrum (KBG), cm -: 1725, 1670.

NMR spectrum (CDCIa) cJ; 9.27 (2H, m) 8.11 (IH, close to S); -j, k2-7.82 (2H, m); it.SI (2H, q, a 7 Hz); 2.83 (2H, q,: j 8 Hz); 1, and 1.38 (, t, and t).

Elemental analysis for C - (5 4

Calculated,%: C H 5.08, N 4.71.

Found,%: C 68.86; H 4.80 N 4.85.

By the method, similarly described above, from ethyl-3- (3-formylbenzo f

7-Methyl-3-cyano-1-az axanton

7-Ethyl-3-cyano-1-azaxanthone

7-Iso11propyl-3-cyano-1-azaxanthone

7,9-Dimethyl-3-cyano-1-azaxanthone Example 25. To a solution of 0.5 g of 7-isopropyl-2-g1 Mino-3 Cyano-1-azaxone in 80 ml of acetic acid was added 1.0 g of sodium nitrite at. After 1 hour, 3 ml of water was added to the mixture and heating was continued for 1 hour. The solvent was distilled off under reduced pressure, and then water was added to the residue. Gel-chromone-2-yl) amino-acrylate, ethylbenzo f -1-azaxanthone-3-carboxylate, m.p. 186-188 t (recrystallization acetone pacTBO remover).

Example24. 2.2 (g of 2-amino-4-oxo 4H-1-benzopyran-3-carboxaldehyde and then 2.5 g of cyanoacetylene are added to 70 ml of dimethylformamide. The mixture is heated under stirring at 140 ° C for 15 hours,

the solvent is distilled off under reduced pressure. The residue is chromatographed on silica gel and eluted with chloroform, after which it is recrystallized from acetonitrile to form 0.83 g of 3-cyano-1-azaxanthone in

the form of crystals, so pl. 220-226 ° C.

NMR spectrum (OMSO - dj,) cG; J ,, k (4H, t); 9.10 (1H, d,: 2H), 9.30 /

(1H, d, 3 2 Hz).

Elemental analysis for C N N0.,

Calculated,%: C, 70.27; H 2.72; N 12.61.

Found,%: C 70.12, H 2.55, N 12.50.

In a similar manner, the compounds listed in Table 2 are obtained. eight.

Table 8

240-242 (ethyl acetate)

183-185

(acetonitrile)

203-205 (ethanol)

254-257 (acetonitrile) the precipitate is collected by filtration, washed with water and recrystallized from ethanol to form 7-isopropyl-2-hydroxy-3-cyano-1-azaxanthone in the form of yellow crystals, so pl. . Elemental analysis for C (, H) Calculated,%: C 68.56; H 4.32; N 10, OO.

Found,%: C 68.28 / H 4.34, N 9.70.

The following is an example of the preparation of a compound of general formula I.

 933 mg of 7-ethyl-2-methyl-1-azaxanHOH-3-carboxylate are added to a 55% strength solution of sulfuric acid and the mixture is stirred for 1 hour. After cooling, a mixture of water and ice in a mixture of 100 ml is added to the reaction mixture. by filtration and recrystallization from ethylshetat

Ethyl 2-methyl-1-azaxto-3-carboxylate

Ethyl 7-methoxy-2-methyl-1-azaxanthbn-3-carboxylate

Ethyl 2,7,9-trimethyl-az ax anton-3-to arboxylate

Ethyl 7-chloro-2-methyl-1-azaxanthone-3-carboxylate

Ethyl 7-nitro-2-methyl-1-azaxanthone-3-carboxylate

Methyl-2-n-propyl-1-azaxanthone-3-carboxylate

Ethyl 7-ethyl-2-phenyl-1-azaxanthone-3-carboxylate

Example 27. A mixture of 1.56 g of methyl 2-amino-7-methyl-1g-aaxanthone-3-carboxylate, 10 ml of acetic acid and 10 ml of 85% sulfuric acid solution is stirred for 4 hours after / The precipitate obtained is collected by filtration and recrystallized from acetic acid-water. According to the procedure described

acetone in this order. Agree, but this method is obtained from 510 mg of crystals of 7-methyl-2-methyl-1-azaxanthone-3-carboxylic acid, so pl. 243245 0. ;.

Elemental analysis for

Calculated,%: C 67.84, H 4.63; N4.95.

Found,%: C 67.75; H 4.43, N 4.89.

0

Similarly, compounds obtained in Table 1 are obtained. 9.

.Table 9

300 (80% dimethylformamide)

94-296 (dimethylformamide)

300 (acetic acid)

292-294 (ethanol)

300 (dimethylformaClide)

217-218 (ethanol)

268-269 (ethyl acetate)

1.28 g of colorless needles of 2-amino-7-ztil-1-azaxanthone-3-carboxylic acid, so pl. 313-314 C (with decomp.).

Elemental angshiz dl

Calculated,%: C 63.38; And 4.26 N 9.86.

Found,%; C 63.24; H 4.56; . N 9.70.

In a similar manner, the compounds obtained in Table 1 are obtained. ten.

Initial compound

2-Amino-1-azaksanton-3-carboxylic

2-Amino-7-methoxy-1-azaxanthone-3-carbonic acid, 2-gi “1ino-7,9-dimethyl 1-azaxanthone-3-carboxylic acid 2-amino-7-chloro-1-azaxanthone-3-carnic acid 2-Amino-7-methyl-1-azaxanthone-3-carboxylic acid 2-Amino-7-isopropyl-1-azaxanthone-3-carboxylic acid 2-Amino-9-methoxy-1-azaxanthone-3-carboxylic acid 2- Amino-7-n-butyl. -1-azaxanthone-3-carboxylic acid 2-aminobenzo h -1-azaxanthone-3-carboxylic acid 2-AMINO-8-hydroxy-1-azaxanthone-3-carboxylic acid

0. P and meper 28, Mixture 1.0 g Ethyl-1-azaxanthone-3-carboxylate, 8 ml of glacial acetic acid and 8 ml of a 55% solution of sulfuric acid. Stir while heating under reflux at 130 s for 1h After cooling, the precipitate is isolated by filtration, washed with water and recrystallized from a 70% strength solution of dimethylformamide. According to this method, 822 g of 1-azaxanthone-3-carboxylic acid are obtained in the form of colorless needles, so pl. 272p.

Table 10

Melting point, ° C (recrystallization solvent)

330 (dimethylformamide)

acid

337-339 (with decomp.) (Dimethylformamide)

 3 3 O (dimethylformamide) lot

320-322 (with decomp.) (Dimethylformamide)

300

(dimethylformamide)

300 (dimethylformamide)

300 (dimethylformamide)

303.-304

(dimethylformamide)

300

(dimethylformamide)

300 (dimethylformamide)

IR spectrum (KBG), cm -1: 1700, 1670, 1615, 1605.

NMR spectrum (daso -dfe); 9.28 (1H, d, D 2 Hz), 8.97 (1H, d, 3 2 Hz) 5 8.17 (1H, dd, 3 2 and 8 Hz) 7.3-8.0 (G, t).

Elemental analysis for dLO.

Calculated,%: C 64.73; H 2.93; N 5.81. .

Found,%: C 64.51; H 2.77; N 5.63.

Compounds are obtained in a similar manner, the 5 1 given in Table. eleven.

Initial compound

Ethyl 7-chloro-1-azax-ITON-3-carboxylate

Etsh1-7-nitro-1-azaksanton-Z-carboxylate

Ethyl 7-ethyl-1-azaxanthone-3-carboxylate

Ethylbeiso h -l-aaxanton-3-carboxylate

Example 29. A mixture of 341 mg of dimethyl-7-ethyl-1-azaxanthone-2, 3-dicarboxylate, 2 ml of acetic acid and 2 ml of 55% sulfuric acid solution was stirred at JB for 4 h. After cooling, water is added and the precipitate is collected by filtration and heated over a direct fire in a round bottom flask, whereby the precipitate melts and foams. After the foam is deposited, melt, cool, and recrystallize from acetone. According to the described procedure, 125 mg of 7-ethyl-1-azaxanthone-3-carboxylic acid are obtained in the form of colorless needles, i.e. Ш1. 238-239 ° C.

IR spectrum (Nujol), 1600, 1675.

NMR spectrum (DMSO-dt): 9.08 (1H, d, 3 2 Hz): 8.81 (1H, d, 3 4 Hz); 7.80 (1H, 5), 7.69 (1H, dd,: j 2 and 8 Hz); 7, "9 (1H, d, 3 - 8 Hz 2.75 (2H, q, E - 7 HZ); 1, 2lt (GH, t, 3 - 7 Hz). Elemental analysis for H N N0.

Cpxeno,%: C, 66.9; H 4.12, N 5.20.

Found,%: C 66.71, H 3.94; M 5.10.

Example 30 A mixture consisting of 1.5 g of dimethyl-7-chloro-1-azaxanthone-2, 3-dicarb6 xylate, 10 ml of a 55% solution of sulfuric acid and 10 m of glacial acetic acid is stirred at 130 ° C within 6 hours. After cooling, the precipitate is collected by filtration, washed with water and recrystallized from a 70% dimethylformamilide solution. According to the procedure described above, 723 mg is obtained.

Table 11

Melting point, ° С (recTV recrystallization solvent)

300-301

(70% -11th dimethyl-. FormMamid)

300 {70% dimethylformamide)

238-239 (acetone)

300 (dimethylformamide)

7-chloro-1-azaksanton-2,3-dicarboxylic acid in the form of colorless needles, so pl. 266-269 0 (with diff.)

NMR spectrum (DMSO - d6) f; 7.9-8.1

0 (2H, t); 8.20 (1H, d, 3 - 2 Hz), 9.03 (1H, S).

Example 31. A mixture consisting of 170 mg of diethyl-7-ztil-1-azaxanthone-2, 3-dicarboxylate, 1 ml of acetic acid and 1 ml of 55% sulfuric acid (ACIDS, heated at 130 s for 3 h. The resulting residue is collected by filtration and recrystallized from acetic acid. According to this procedure, 30 30 mg of 7-ethyl-1-azaxanthone-2,3-dicarboxylic acid is obtained in the eide of crystals, mp 210-211 C (c .)

IR Spectrum (NUJO), 1728, 1695, 1675.

S

yes P-spectrum (dmso-d,) cf. 8.93 (1H, S), 7.97 (1H, -3. 2 Hz); 7.80 (1H, dd, 3, 2 Hz); 7.62 (1H, d, 3 9 Hz); 2.78 (2H, q, and 7 Hz); 1.27, (3N, t, -3. 7 Hz);

0

Example 32. A mixture consisting of 185 mg of diethyl-7,9-dimethyl-1-azaxanthone-2, 3-dicarboxylate, 1 ml of acetic acid and 1 ml of 55%

5 sulfuric acid solutions are heated for 2 hours and the sparingly soluble product is isolated by filtration. The product obtained is dissolved in an aqueous solution of sodium hydrogencarbonate and filtered from

0 a small amount of a limited soluble product. The acidic acid filtrate and the precipitate is collected by filtration and recrystallized from acetic acid-water. According to

5 j

to the procedure described above, 20 mg of 7,9-dimethyl-1 - azaxanthone-2,3-dicarboxylic acid are obtained in the form of light yellow needles, pl. 175 177С (depolarization temperature)

.-- f

IR-h; spectrum (N and j o 1), cm

: 1725G 1710, 1670.

NMR spectrum (DMSO - dfc) d:

9.17 (1H.S), 7.85 (1H, d, 3 2 Hz) i 7.65 (1H. D, .3 2 HZ); 2.53 (3H, S) 2, ij5 (IH.S). .

Il p and me 3 3 o A mixture consisting of 43,700 mg of ethyl 7-ethyl-2-oxy-1-aeacanthone-3-carboxoxylate, 20 ml of glacial acetic acid and 10 ml of a 55% solution of sulfuric acid, stirred under reflux at 130 s for 5 hours. After cooling the precipitate

. collected by filtration, washed with water and recrystallized from dimethylformamide. According to the above method, obtain 492 mg of 7-ethyl-2-hydroxy-1-azaxanthone-3-carboxylic acid in the form of colorless plates, so pl. 292-29BS .

IR spectrum (KBG), cm: 1740, 1675, 1610.

Initial compound

7-Methyl-2 hydroxy-1-azaxanthone-3-carboxylic

7-Methoxy-2-hydroxy-1d-azaxanthone-3-carbonic acid

9-Methoxy-2-hydroxy-1-azansakgon-3-carboxylic acid

2-Oxy-7,9-dimethyl-1-azansan-3-carboxylic acid

7-n-Butyl-2-hydroxy-1-azaxanthone-3-carboxylic acid

Example 35. A mixture of 500 mg of 9-7-ethyl-2-methoxy 1-azaxanthone-3-carboxylate, 10 ml of acetic acid and 5 ml of a 55% sulfuric acid solution is stirred at 80 ° C for 2 hours, after which

NMR spectrum (,} (f: 1.25 - (3N, t, 3 7 Hz). 2.75 (2H, q, 3-7 Hz); 7.5 (.1H, d, 3 9 Hz) ; 7.70 (1H, dd, 3 9 And 2 Hz); 7.83 (1H, d, 3 2 Hz), 8.7 (1H..5J .-.

. .--.

Example 34. A mixture consisting of 600 mg of ethyl 2-hydroxy-1-azaxan-. ton-3-carboxylate, 10 ml of glacial acetic acid. and 5 ml of 55%

sulfuric acid solution, stirred at reflux for 4 h. After cooling, the precipitate is collected by filtration, dried with water and recrystallized from dimethylformamide. According to the procedure described above, 418 mg of 2-hydroxy-1-azaxanthone-3-carboxylic acid is obtained as white crystals, mp above 300 ° C. IR spectrum (KVg), 1745,

1660, 1620,

NMR spectrum (HMCO-d.) Tf: 7.6-8.1 (3N, t), 8.17 (1H, dd, 3 8 Hz); 8.82 (IH.S). .

In a similar manner, the compounds listed in Table 2 are obtained. 12.

Table 12

Melting point, C (recrystallization solvent)

300

(dimethylformamide)

acid

300 (dime tilformamide)

300 (dimethylformamide)

300

(dimethylformamide)

300-305 (dimethylformamide)

, 20 ml of water. And continue stirring at this temperature for 10 minutes. After cooling, the resulting precipitate is collected by filtration, washed with water, dried and grown in 3 ml of dimethylformamide. TO

3 g of silica gel is added to the resulting solution and it is well rewarded / after which dimechilf rmamide is distilled off. The residue is passed through a 50 l column of silica gel and eluted with chloroform-acetone formic acid solution (9: 1: 0.1), resulting in a yield of 390 mg crystals, cotsuenle are recrystallized from a mixture of dimethylformamide - ethanol with the formation of 358 lita 7-ethyl-2-methoxy-1-azaxanthio-3-carboxylic acid in the form of colorless needles, so pl. ..

Elemental analysis for

Calculated: C 64.21, H 4; 38; N 4.68

Found: C 64.10) H 4.24} N 4.71.

IR spectrum (Hojol), cm-: 1690, 1660, 1600, 1590, 1290, 825, 790..

yes | P-spectrum {flMCO-dt) (fJ 8.70 (tH, 5b 7.80 (1H, m) j 7, M-, 63 (2H, m); V, 05 j (3H, SM 2, 73 | 2H. Q, H. 7 rn) tt, Z3 l3H, t, E - 7 HZ) I

Example 36 In a 3.5 ml 50 ml aqueous solution of sulfuric acid and acetic acid (Isl), 681 mg of ethyl 7-ethid-2-meth "la" io-1-azaxanthone-3-carboxylate are dissolved. The test solution is heated at SOU with IB for 6 hours and then the pH of the solution is adjusted to 5. with 10% strength sodium hydroxide solution. The resulting precipitate is collected

Initial compound

1-Azaksanton-Z-carbo-nitrile

7-Ethyl-1-azaksanton-3-carbonitrile

2-Amino-7-dimethylamino-1-azaxanthone-Z-to rbonitrile

7-tert-Butyl-1-azaxanthone-3-carbonitrile

Example 38. A mixture consisting of 27 mg of 7-ethyl-1-azaxanthone of 3-carboxylic acid, 12 mg of diafiltration, is quenched with water and cross-flow {dstllyzivayuyu- from a mixture of dimethylphmyl-ethanol with the formation of 488 mg of 7-ethyl-2-methylamino 1-azaxanthone-3-carboxylic acid c. form kris5 allov, t. pl. .

Elemental analysis for C.

Number,%: C 64.42; H 4.73; N9.39.

Found,%: C, 64.24; H, 4.50); “W 9,19.

IR spectrum {Nujol), cm: 3270, il690, 1605, 1570, 1300, 1127.

5th spectrum (mfCO-d (,) (f: 1.25 (ЗН, t, 3 - 7.5 ГЦ)} 2.73 (2Н, q, 3 - 7 ГЦ) 3.03 (ЗН, d, : - “HZ),

5 7.2-7.8 (2H,) 7.8v (lH, d, O “, 2 HZ); 8.7v (JH, S).,

Example 37. In a mixture consisting of 10 m of a 50% aqueous solution of serum acid and 10 ml of acetic acid for 2 hours at the time, 0.875 g of 7-isopropyl-3-ciag / o -1-azaxanthone. After completion of the reaction, water is added to the reaction mixture and the resulting precipitate is collected by filtration, washed with water, dried and recrystallized from ethanol. According to the procedure described above, 0.623 g of 7-isopropyl-1-azaxanthone-3-carboic acid is obtained, m.p. 259; 261 C.

Similarly, the compounds are given in Table. 13.

13

Table

Melting point, C (recrystallization solvent)

267-26 &

(ethyl acetate)

238-J239

(dimethylformamide)

258-260 (with dec.) (Acetic acid)

225-228. (ethanol)

nolamine and 10 ml of ethanol; dissolved by heating. The solution obtained is concentrated and after cooling, the crystals collected are collected | ash1. According to the procedure described above, 25 mg of diethanol salt (No. Sna-7-etyl-1-azaxanthone-3-carboxylic acid in the form of colorless crystals, pl. 162-164 C) is obtained. Element1 Analysis for Calculated,% s С 60.96; H, 5.92; N, 7.48. Found: C, 60.70; H, 5.87; M, 7.48. EXAMPLE 39 A mixture of 50 mg of 2-amine, 9-7-getkl-1 Asaxantone-3-carvoxamide, 0.5 ml of 55% sulfuric acid and 0.5 ml of acetic acid are heated at 6 hours. After cooling, 2 ml of water is added to the reaction mixture. The slightly soluble product is filtered off and the water is punched. Dissolve the excess amount of an aqueous solution of dvethano amine and when heated and then non-soluble products the filter is from t The filtrate is acidified with hydrochloric acid, the precipitate is filtered and recrystallized from dimethylformamide and in. In this method, 32 mg of 2-g in 1-7-ethyl-1-azaxan-3-carboxylic acid are obtained. in the form of colorless needles, mp 313-314 C (with decomp.) Claims for obtaining 1-aza santoi-3-carboxylic acid derivatives Formula of where R is hydrogen, C; (- Cg-alkyl, phenyl , carboxy-, hydroxy-, C- | -C4-alkoxy-, amino group which may be unsubstituted or substituted by one al silt, m. O, 1, 2J R — C —Cg-alkyl, C — C alkoxy-j, nitro, Xoxy, carboxy, chlorine, butadienylene.), Which form a benzene ring with any of the adjacent carbon atoms or an amino group, unsubstituted or substituted alkyl alone, or their salts with aliphatic amines, characterized in that. that a compound of the general formula where R is hydrogen, C-Cg-AlKiL, phenyl, alkoxycarbonyl with Cj-C alkyl, hydroxy, alkoxy or amino, unsubstituted or substituted by one C | -C-alkyl, has the meanings indicated above t diano, alkoxycarbonyl radical with C -Cg-alkyl, carboxamide, is subjected to acid or alkaline / gu hydrolysis at a temperature of 50-150 ° С "Priority by signs 18.03.77. The method of obtaining CoM ™ dininsiya formula 1, in which m 1 about - X, i. 12.20.77, Method of obtaining compounds of formula 1, where m O. Sources of information taken into account in the examination 1, Advances in organic chemistry, Ed. And, l. Knun natz, That 3, M., Mir, 1966, p., 190-221.

Claims (1)

The claims hydrogen, CC-C g-alkyl, phenyl, alkoxycarbonyl with · C.-Cg-alkyl, hydroxy, CC-SC alkoxy or amino, unsubstituted or substituted by one Cj-C ₃ -alkyl, have the meanings indicated above - cyano, alkoxycarbonylradi-cal with -C ₆ -alkyl, carboxyamide, is subjected to acid or alkaline hydrolysis at a temperature of 50-150 ° C. m., R 2 ^R 4 A method of obtaining derivatives of 1-azaxantone-3-carboxylic acid of the general formula ··. i <50011 where Rj - hydrogen, C ^ - C ₆ alkyl, fairy ~ Neal, carboxy, hydroxy, C4-C4-alkoxy, amino, · Priority by signs: 03/18/77. A method of obtaining compounds of formula 1, in which t = 12 · 12.20.77. A method of obtaining compounds of formula 1, where m = 0.