JPS6110588A - 1-azaxanthone derivative and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [ring A is substituted by halogen, nitro, alkyl, alkoxyl or butadienylene group (-CH=CH-CH=CH-) forming benzene ring with the two adjacent carbon atoms at the 6-, 7-, 8- and 9-positions; R1 is H, alkyl, phenyl, amino, alkoxycarbonyl or OH; R2 is cyano, alkoxycarbonyl or -CONH2]. EXAMPLE:Ethyl 7-ethyl-2-methyl-1-azaxanthone-3-carboxylate. USE:An antiallergic agent. PREPARATION:A compound expressed by formula II, e.g. 2-amino-6-ethyl-4-oxo- 4H-1-benzopyran-3-carboxaldehyde, is reacted with an active methylene compound, e.g. ethyl acetoacetate, or an acetylenecarboxylic acid derivative.

Description

[Detailed description of the invention] [In the formula, ring A is a halogen atom, nitro, or alkyl.

Butadienylene group (-C
H=CH-CJ-1=CH-J, and R
1 represents hydrogen, alkyl, amino, carboxy, alkoxycarbonyl, or hydroxyl group; R2 represents cyano, alkoxycarbonyl, or 100NH2, respectively; and a method for producing the same.

More specifically, the compound represented by the general formula (+1) is represented by the general formula (n) [wherein A ring is a halogen atom, nitro, or alkyl.

Butadienylene group (-
CH=CH-CH-FCH-)] is produced by reacting an active methylene compound or an acetylene carboxylic acid derivative.

The 1-azaxanthone derivative represented by general formula (1) of the present invention has an antiallergic effect and is useful as a medicine such as an antiallergic agent.

To explain in more detail the substituent on ring A in each of the above formulas, examples of the alkyl group include methyl, ethyl, propyl, and isof-10-pyl.

Examples include linear monobranched alkyl groups having 1 to 6 carbon atoms such as butyl, isobutyl, t-butyl, pentyl, and hexyl groups, and among them, lower alkyl groups having 1 to 3 carbon atoms are practically preferred. Examples of halogen atoms include chlorine, bromine, iodine, and fluorine, and examples of alkoxy groups include methoxy.

Examples include alkoxy groups in which the alkyl moiety has 1 to 4 carbon atoms, such as ethoxy, 10-poquino, and butoxy groups.

One or more substituents on the benzene ring represented by these A rings may be the same or different and may be substituted at any position of the A ring.

Further, the substituent R1 is hydrogen, alkyl, or phenyl.

Indicates amino, alkoxycarbonyl or hydroxyl group,
The alkyl of R1 or R2 and the alkyl moiety of alkoxycarbonyl include straight chain alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-10-methyl, n-hexyl and the like.

The compound of general formula (1) of the present invention can be produced by the following method. That is, it is produced by reacting the compound of general formula (It) with an active methylene compound. The active methylene compounds used in the reaction include methyl acetoacetate, ethyl acetoacetate, methyl cyanacetate,
Examples include ethyl cyanacetate, ananoacetamide, malonitrile, ethyl oxaloacetate, diethyl malonate, dimethyl malonate, and ethyl benzoylacetate 3-oxo-n--)1-ph50ate. The amount of these raw methylene compounds to be used is usually about -1 to 10 times the practical amount per mole of the raw material compound of general formula (U).

In the above reaction, the presence of a base is generally desirable, and the base used is an organic amine, for example, a tertiary amine such as 1,8-diazavinchlo(5,4,0)-7-undecene or triethylamine.

Secondary amines such as piperidine, pyrrolidine, morpholine, diethylamine, Schiff's pyramine, dibutylamine, primary amines such as n-butylamine, benzylamine, aniline, and imidazole.

Examples include heterocyclic bases such as 2-methylimidazole. The amount of these organic bases to be used is usually determined by the general formula (II)
The catalyst amount is about 5 times the mole of the raw material compound.

It is generally preferable to carry out the reaction in an organic solvent, and examples of the solvent include alcohols such as methanol, ethanol, gropanol and butanol, aromatic hydrocarbons such as benzene and toluene, and dimethylformamide. Although there are no particular limitations on other reaction conditions such as reaction temperature and reaction time, it is common to carry out the reaction at room temperature to around the boiling point of the solvent used for about 1 hour to 24 hours.

Moreover, the compound of general formula (T) can be produced by reacting the compound of general formula ([1) with acetylene carboxylic acids. Acetylene carboxylic acids used in the reaction include acetylene dicarboxylic acid dimethyl ester, acetylene dicarboxylic acid diethyl ester,
Examples include methyl 10 piolate and ethyl 10 piolate. When a propiolic acid ester is used, the intermediate aminoacrylate derivative can be isolated, but it is also possible to directly carry out the ring-closing reaction without isolation, leading to the compound of general formula (1). The amount of these acetylene dicarboxylic acid derivatives used is usually determined by the general formula (II)
Practically speaking, the amount is about 1 to 10 times the mole of the raw material compound.

In the above reaction, the presence of a base is generally desirable, and the base used includes organic amines, such as triethylamine, tripropylamine, and truffles.

Examples include tertiary amines such as thylamine, heterocyclic bases such as pyridine, quinoline, imidazole, and 2-methylimidazole, and secondary amines such as piperidine, pyrrolidine, morpholine, diethylamine, dipropylamine, and diptylamine. The amount of these organic bases to be used is usually about a catalytic amount to about 10 times the mole of the raw material compound of general formula (It).

The reaction is generally carried out in an organic solvent,
Examples of this solvent include methanol, ethanol,
Examples include alcohols such as propatool and butanol, aromatic hydrocarbons (benzene, toluene, xylene, etc.), and dimethylformamide. Other reaction conditions such as reaction temperature and reaction time are not particularly limited, but it is common to carry out a time window of about 1 to 24 hours at room temperature and around the boiling point of the solvent used. ) has an antiallergic effect and is useful as a prophylactic or therapeutic agent for allergic diseases such as allergic asthma, allergic skin inflammation, and hay fever.

When the compound of general formula (1) is used, for example, as a prophylactic or therapeutic agent for the above-mentioned allergic diseases, the adult dose is usually about 1 to 500 μ/day in the form of tablets, capsules, powders, solutions, etc. In addition to oral administration, it can be administered in appropriate dosage forms such as injections, atomized inhalants, and ointments.

In addition, general formula (II) which is one of the raw material compounds of the present invention
The compound can be produced by the following method.

That is, the general formula (1
) (In the formula, ring A is produced by reacting a compound having the same meaning as above with water in the presence of a base.As the base used in the reaction, organic amines are used, such as ethylamine, n -) Primary amines such as lopylamine, n-'thylamine, benzylamine, aniline, dimethylamine, diethylamine, dipropylamine, dibutylamine.

Secondary amines such as morpholine, piperidine, and pyrrolidine, and tertiary amines such as toluethylamine.

Examples include heterocyclic bases such as imidazole and 2-methylimidazole, and inorganic bases such as aqueous ammonia, aqueous acetic acid, ammonium carbonate, sodium carbonate, and sodium hydrogen carbonate. These bases can be used in a catalytic amount to a large excess, and are not particularly limited.

The reaction is generally preferably carried out in a water-miscible solvent;
For example, dimethylformamide, dimethyl sulfoxide,
Examples include hexamethylphosphoric acid triamide, organic acids such as formic acid, acetic acid, and 7' propionic acid, and ethers such as tetrahydrofuran and dioxane. There are no particular restrictions on other reaction conditions such as reaction temperature, reaction time, etc.
Generally, the reaction is carried out at about 0°C for several minutes to about 3 hours.

Reference example 2 ml of morpholine, 8 ml of dimethylformamide.

4-oxo-4H-1-benzopyran-3 was prepared by heating a mixture of 1 orui of water to 60°C and powdering it while stirring.
- 1.71.9 of carbonitrile was added over 5 minutes. After heating for 1 hour, the precipitate was collected by filtration, washed with water, recrystallized from acetic acid, and washed with chloroform.
2-Amino-4-oxo-4H-1-benzopyran-3
-Crystals of carboxaldehyde 1.82. f was obtained. Melting point: 252-255°C (decomposition) Nuclear magnetic resonance spectrum) /I/ (DMSO-d6)
δ: 10.19 (IH, s), g, 67 (Ca1.5H
, br, s), 8.11 (IH, dd, J=2, sHz
), 7.97-7.80 (8H.

m) Elemental analysis Calculated value as C1oH7NO8: C, 68,49; H, 178; N, 7.41 Actual value: C, 68,59; H, 8,44iN, 7.45 Similarly, prepare the following compound. Obtained.

Example 1 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-8-carboxaldehyde 2.1'1 g, acetoacetic acid ethyl ester 4.9 ml, 1 polyol 5
0m1. While stirring the mixture of piperidine 5d, 2
The mixture was heated to reflux for an hour. When cooled, the precipitate is filtered and recrystallized from ethanol to obtain ethyl 7-ethyl-2-methyl-1.
Yellow needles of -azaxanthone-3-carboxylate 1.6011 were obtained.

Infrared absorption scale (Nujol) Lyn: 171
5゜Kanming spectrum (CDCIllδ:9.15(1
B, s).

8.09 (LH, S), 7: f37-7.75 (2H,
m).

4.44 (2H, q, J=7Hz), 2.9? (8H,
s).

2.81 (21-I, Q, J = 7H2l, 1.45 (8
H,t.

J=7H2), 1.88 (8H, t, J='1Hz) Elemental analysis C,, ii-Calculated value as H1□No4: C, 69,44; H, 5,50; N, 4.
50 actual value: C, 69, 58: H, 5, 44; N, 4.
EXAMPLE 28 The following compounds were produced in the same manner.

Example 2 2-amino-6-nityl-4-oxo-4H-1-benzopyran-3-carpoxaldehyde2. ITg, cyanacetic acid ethyl ester 4.0 ml, ethanol 59
m1. A mixture of 5.0 ml of piperidine was heated under reflux for 80 minutes, and the precipitated crystals were collected by filtration and washed with chloroform to form colorless needles of ethyl 2-amino-7-ethyl-1-azaxanthone-8-carboxylate. Akira 2.07
g was obtained.

Melting point 279-280℃ Elemental analysis Calculated value as C1□H16N204: C,6
5,87iH, 5,16iN, 8.97 Actual value: C, e
s, 24; H, 5, os; N, s, se and so forth (the following compound was produced by doing the same).

Example 8 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-8-carboxaldehyde 1.0851 ethyl benzoyl acetate 2,0 rnl, ethanol 5
011IZ, piperidine 1. The mixture of QRE was heated under reflux for 6 hours while stirring, and a small amount of insoluble material was removed while the mixture was still warm. After cooling the r liquid, the precipitate was collected and recrystallized from ethanol to obtain ethyl-ethyl-2-phenyl-1-
Azaxanthone-3-carboxylate 685η was obtained as pale yellow needles. Melting point: 176-177°C Infrared absorption spectrum (Nujol) cm”: 1780
, 1675 nuclear magnetic resonance spectrum (CDCI, S δ
:9.12 (1B, S), 8.18 (IH, S), 7.
80-7.87<TH,m), 4.28C2H,q,J
='1H1).

2.82 (2H, Q, J=7Hz), 1.08-1.5
8 (sH, t-1-t) Elemental analysis Cz@Ht9NO4 and L Calculated value: C,?
8.98; H, 5,18iN, 8.75 Actual value: C, ?
4.10; H, 5,08; N, 171 Example 4 2-Amino-6-ethyl-4-okine-4H-1-benzobilane-8-carboxaldehyde 21? A mixture of cyanoacetamide 800'P, ethanol 5 mg, and piperidine 0.6114 was heated to reflux for 1 hour while stirring, and the hardly soluble material was collected by filtration, and dimethylformamide was added.
Recrystallization from acetone yields 2-amino-7-ethyl-1
-Azaxanthone-8-carboxamide crystal 180
TI9 was obtained. Melting point>800°C Nuclear magnetic resonance spectrum (CF, C00D) δ: 9.50
(IH,S), 8.20CIH,d, J=2Hz).

7.88 (tH, dd), 7.68 (IH, d, J=”
1Hz).

2.91 (2H, (1, J=?H2), 1.88 (8H
,t.

J=7H2J Elemental analysis C16H, N, 0. Calculated value: C, 6
8,59; H, 4,68iN, 14.81 actual value: C,
68,40; H, 4,72; N, 14.79 The following compounds were similarly produced.

[I Example 5 While stirring a mixture of 217 q of 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde, 5 oz of malonitrile, 5 ml of ethanol, and 0.5 ml of piperidine, 15 The mixture was heated under reflux for a minute, and the hardly soluble materials were collected by filtration.

Recrystallization from dimethylformamide gives 2-amino-
1.601 Rg of colorless needles of 7-ethyl-1-azaxanthone-8-carbonitrile were obtained.

Melting point>800°C Infrared absorption spectrum (Nujor) cm: 882
5゜8125.2225.1660 Nuclear magnetic resonance spectrum (CF8COOD) δ: 9.07
(IH, s), 8.16 (IH, d, J=2H2), 7
．． 88 (IH, dd), 7.68 (LH, d, J=9H
z).

2.92 (2H, q, J=7Hz), 1.39 (3H,
t.

J=7H2) Elemental analysis Calculated value as C15H1, N80□: C,6
7,91iH, 4,18iN, 15.84 actual value: C,
67,75i1(,4,01iN, 16.00) The following compounds were produced in the same manner.

Example 6 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-8-carboxaldehyde 2.17 g, acetylene dicarboxylic acid dimethyl ester 1.778 F, methano-) Lt 50 ml, triethylamine 0.5
The mixture in step d was heated under reflux for 8 hours with hot stirring, and the cold precipitate was collected by filtration. This was added to C70 form and stirred, the hardly soluble materials were filtered off, the filtrate was concentrated to dryness, and then mixed with n-hexane-chloroform-acetone (10:5:0.5), about 5
The eluate was dissolved in 0.0 ml of alcohol and eluted with the same solvent on a silica gel column (301/2 months). The eluate was concentrated and the residue was recrystallized from methanol to yield dimethyl 7-ethyl-l-azaxanthone-2,8-dicarboxylate. colorless needle crystals of
90η was obtained.

Melting point 169-170℃ Infrared absorption spectrum # (Nujol) crn-'H17
45°1720.1670 Nuclear magnetic resonance spectrum (CDCI, )δ:9.20
(IH.

S), 8.10 (IH, d, J=2H2), 7.68 (
IH.

dd, J=2andgHz), 7.52 (I
H, d, J==8Hz).

4.05 (8H, S), 3.9j (8H, S), 2.8
8 (2H.

Q = J = 7H2) e 1-88 (8H-t-
J = 7Hz,) Elemental analysis Calculated value as Cl8H1,N06: C, 68,84; H, 4,48; N, 4.10
Actual value: C, 63,15; H, 4,80; N, 4.01
Example 7 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde 2.17y, acetylene dicarboxylic acid diethyl ester 2.55J9.
A mixture of 50 mJ of ethanol and 1.5 ml of triethylamine was heated under reflux for 2 hours, the heated crystals were collected by filtration, and recrystallized from ethanol to give diethyl 7-ethyl-1-
8.229 colorless crystals of azaxanthone-2,3-dicarboxylate were obtained. Melting point 112-118℃ Infrared absorption shale (NujoJ)ctn-'
: 1745.

1718.1665 Nuclear magnetic resonance spectrum (CDCI 81δ: 9.28
(IH.

S), 8.18 (IH, S), 7.48-7.88 (2
H, m).

4.27-4.77 (4H, (] + Q), 2.82 (2
)(,q.

J=7. H2), 1.17-1.62 (9H) Elemental analysis C20H19NO6 and t Calculated value: C, 65, 1; H, 5, 19; N, 8.79 Actual value: C, 65, 26;) (, 5,02; N, 8.87
Example 8 2-amino-6,8-dimethyl-4-oxo-4H-1
-Benzopyran-3-carboxaldehyde 21? ”
P, acetylene dicarboxylic acid diethyl ester 255
#v, ethanol 10mA', triethylamine 0.0
5 ml of the mixture was heated to reflux for 3 hours and chilled at 150'f.
Ethanol 1mA! - add 2 drops of triethylamine,
The mixture was further heated under reflux for 2 hours. The cold precipitate was collected by filtration and recrystallized twice from ethanol to obtain yellow crystals of diethyl 7,9-dimethyl-1-azaxanthone-2,8-dicarboxylate. Melting point 156-159
°C infrared absorption spectrum tv (NujoI) cm: 1
740°1725.1675 Nuclear magnetic resonance spectrum (CDCI 8n δ: 9.22 (
IH.

S), 7.90(1)1. S 1.7.45 (IH, S
1,4:57(2H,q,J=7Hz),4.45(
2) (, q.

J=THz), 2.58<8H,s), 2.48C8H
,s).

1.47 (6H,t, J=7Hz) Example 9 2-Amino-6-chloro-4-oxo-4H-1-benzopyran-8-carboxaldehyde 2.281 Acetylene dicarboxylic acid dimethyl ester 4.1. li+, ethanol 50ml 1. The mixture with one drop of triethylamine was heated to reflux for 5 hours with stirring. The result of precipitation on a cold plate was collected and recrystallized from ethyl acetate to obtain 8.28I of dimethyl 7-chloro-1-azaxanthone-2,8-dicarpoquinate as pale yellow needles.

Melting point 220-228°C Elemental analysis C16H,, Calculated value as NO6C1: C,
55,84i) 1,2.90; N, 4.08 actual value: C
, 55, 25; H, 2,74iN, 8.94 Example 10 2-amino-6-chloro-4-oxo-4H-1-benzopyran-8-carboxaldehyde 2.28 g, ethyl propiolate 5,1 dimethyl Formamide 80m
,) ethylamine o, i m/ was heated at 90°C for 1 hour while stirring, and a lot of cold precipitate was collected,
When washed with methanol, ethyl 3-N-(8-formyl-
6-chloro-4-oxo-4H-1-benzopyran-2
1.6 g of crude crystals of -ylnoaminoacrylate were obtained.

Add this to 15 ml of dimethylformamide (1 liter)! 130-140 while stirring with 5 mg of J ethylamine.
'C for 2 hours. The reaction solution was concentrated under reduced pressure, and the residue was recrystallized from ethanol to give ethyl 7-chloro-1-
650 kg of pale yellow needle crystals of azaxanthone-8-carboxylate were obtained.

Melting point: 176-177°C Infrared absorption spectrum ()G3rXt-”: 1725.
1675 nuclear magnetic resonance spectrum (CDCI) δ: 9.
8? (IH.

d, J=2Hz), 9.27 (IH, d, J=2Hz)
.

8JO (IH, d, J=2Hz), 7.80 (IH, d
d.

J=2and8Hz), ? ,60(ti-i,c
t, J=8Hz).

4.84 (2H, q, J=7Hz), 1.4.8 (IH
, 4°J=7Hz) Elemental analysis Calculated value as C16HLl, N04C1: C
, 59,82iH, 8,82; N, 4.61 actual value: C
,59,40;H,1,18;N,4.44 Example 11 2-amino-6-nitro-4-
Oxo-4H-1-benzopyran-8-carboxaldehyde to ethyl 7-nitro-1-azaxanthone-
8-carboxylate was synthesized.

Pale yellow plate crystals (recrystallized from dimethylformamide) Melting point 228-229°C Infrared absorption spectrum)/1z(KBr)fi: 172
0.1675 nuclear magnetic resonance spectrum (CF8CO2D)
δ: 9,1-98 (2H, broads), 8
．． 92 (IH, d, J=2Hz).

8.42 (IH, dd, J=2and9H2)C7,4
8 (IH, d, J = 9Hz), 4.22 (2H, Q, J
=7Hz).

1.10 (8H, t, J=7H2) Elemental analysis C1
Calculated value as 6H1°N206: C, 57, 88; H,
8,21; N, 8.92 actual value: C, 56,96; H,
8,09iN, 8.76 Example 12 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-3-carboxaldehyde 8.1Ti, diethyl malonate 8g, pyridine 15ml, 1.8-diazapink o(s,4.o)-7-undecene 1 ml. A mixture of 50 ml of ethanol was heated to reflux with stirring for 15 hours. The reaction solution was concentrated under reduced pressure, and dilute hydrochloric acid was added to the residue to make it acidic. The precipitate was collected by filtration, washed with water, and then recrystallized from ethanol to give pale yellow needle crystals of 7-ethyl-2-hydroxy-1-azaxanthate 7,-3-carboxylate.
．． Obtained 28J. Melting point: 200-204°C Infrared absorption spectrum (KB'r)m: 1675, 1610 Nuclear magnetic resonance spectrum (CDCl2) δ: 1.85 (8H
.

't, J=7Hz), 1.58(8H,t, J=7H
z).

2.87 (2H,Q, J=7H2), 4.
58 (2H,q.

J = 7Hz), 7.4-7.8 (2H), 8.28 (I
H, Q.

J=2)12), 9.80 (IH,s) Example 18 2-Amino-6,8-dimethyl-4-oxo-4H-1
-benzopyran-8-carboxaldehyde 826q,
x9/-Lua, 5 ml, 2.0 tons, malonic acid diethyl ester 2. A mixture of QWLl and 0,1 ynl of 1,8-diazabicyclo(5,4,0)-7-undecene was heated under reflux for 4 hours. The solvent was distilled off, IN hydrochloric acid was added to the residue, the poorly soluble material was collected by filtration, dissolved in chloroform, and subjected to silica gel chromatography.
Elution and purification with acetone-formic acid (9:1:0.1) and recrystallization from ethanol yielded ethyl 2-hydroxyi/-7.
A pale yellow crystal 20'9 of 9-dimethyl-1-azaxanthone-8-carboxylate was obtained. Melting point 2'51-25
8℃ infrared absorption spectrum (Nujol) cm-1:1
700°1675.1650 Nuclear magnetic resonance spectrum (CDC18) δ: 12.80
(IH.

br J, 9.22 (IH, S), 7.98 (IH, l
.

7.45 (IH, S), 4.55 (2H, q, J=7H
2).

2.57 (8H, s), 2.48 (8H, S), 1.5
0 (8H.

t) The following compounds were produced in the same manner.

Runyl Example 14 2-amino-6-ethyl-4-oxo-4H-1-benzopyran-8-carboxaldehyde 2.17I, dimethylformamide 251. Propiolic acid ethyl ester 51) A mixture of 0.1 ml of ethylamine was heated at 90° C. for 1 hour while stirring, and then allowed to stand at room temperature. The precipitated crystals were collected by filtration and recrystallized from acetone to form ethyl 8-(6-ethyl-8-formyl-4-oxo-4).
1.6i of colorless needle-like crystals of H-1-henzopyran-2]aminoacrylate were obtained. Melting point: 201-208°C Infrared absorption ratio: ) /l/ (KBr)cR: 807
0.

1700.1665.1685 Nuclear magnetic resonance spectrum CCDCl, ) δ: 18.60 (I
H.

d, J=12H2), 1G, 86 (IH, S), 8.0
2 (IH, d, J=2Hz), 7.17~'1
．． 1 B (8H, m).

5.42 (IH, d, J = 9H2), 4.84 (2H,
q.

J=7Hz), 2.75 (2H,q, J=7Hz).

1.85 (8H, t, J=7Hz), 1.28 (8H,
t.

J=yHz) Elemental analysis Calculated value as C17H1□NO5: C, 64,75; H, 5,48; N, 4.44
Actual value: C, 64,72; H, 5,40; N, 4.88
In the same manner, 2-aminobenzo(f)chromone-8-carboxaldehyde and I) ethyl 8-(8-formylbenzo(f)-chromone-2)aminoacrylate was obtained. Melting point: 22 g - 280°C (decomposed) Example 15 Ethyl 8-(6-ethyl-8-formyl-4-okine-4H-1-benzopyran'-2) obtained in Example 14
-aminoacryle-) 1.58J, dimethylformamide 151117. ) ethylamine 5117! The mixture was heated under reflux at 180° C. for 2.5 hours and then concentrated. Approximately 50 ml of ethanol was added to the residue, cooled, and the precipitated crystals were collected by filtration. Recrystallized from ethanol to give ethyl 7-
920 η of pale yellow needles of ethyl-1-azaxanthone-8-carboxylenite were obtained. Melting point 140-142℃ Infrared absorption spectrum (KBr) cra: f725,
1670 nuclear magnetic resonance spectrum ('CDCl,) δ:9
．． 27 (2H.

m), 8.11 (IH, near s), 7.
42-7:82 (2H, m), 4.51 (!H, Q, J
=7Hz), 2.88 (2H, Q, J=8Hz), 1.
48 and 1.88 (8H.

Claims (2)

[Claims] (1), General formula ▲ Numerical formula, chemical formula, table, etc. Butadienylene group forming a ring (-CH=
1-azaxanthone derivatives substituted with CH-CH=CH-), R_1 represents hydrogen, alkyl, phenyl, amino, alkoxycarbonyl or hydroxyl group, and R_2 represents cyano, alkoxycarbonyl or -CONH_2, respectively. . (2), general formula ▲ Numerical formula, chemical formula, table, etc. Butadienylene group forming a ring (-CH=
A general formula characterized by reacting an active methylene compound or an acetylene carboxylic acid derivative with a compound represented by CH-CH=CH-) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ring A has the same meaning as above, R_1 represents hydrogen, alkyl, phenyl, amino, carboxy, alkoxycarbonyl or hydroxyl group, and R_2 represents cyano, alkoxycarbonyl or -CONH_2. Law.