JPH02138251A - Cyclohexadiene derivatives - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I (R<1> is lower alkyl; R2 and R3 are H, lower alkyl or mutually bond to form -(CH2)4- or-CH=CH-CH:CH-; a is aromatic five- or six-membered heterocycle containing 1-3 heteroatom selected from N, O and S, pyrazine-N-oxide ring, etc.). EXAMPLE:2,6-Di-tert-butyl-4-pyrazinyllmino-2,5-cyclohexadien-1-one. USE:An intermediate for synthesis of a p-aminophenol derivative having anti- inflammatory action and lipoxygenase inhibition. PREPARATION:A quinone derivative of formula II and an aromatic heterocyclic amine derivative of formula H2N-a are condensed at 100-200 deg.C to obtain the objective compound of formula I.

Description

[Detailed description of the invention] Industrial applications The present invention relates to cyclohexadiene derivatives.

Disclosure of the Invention The cyclohexadiene derivative of the present invention is represented by the following general formula.

R2R3 [In the formula, R1 represents a lower alkyl group. R2 represents a hydrogen atom or a lower alkyl group, R3 represents a hydrogen atom or a lower alkyl group, or R2 and R3 are combined to form a group -(C
112) 4- or the group -CII=CH-CII=
Indicates CII-. α is an aromatic hetero 5- or 6-membered ring group containing 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms, pyrazine-N-oxide ring group, pyridazine-N-oxide ring group, or pyrimidine -N represents an oxide ring group, and these aromatic heterocyclic groups have 1 to 3 substituents selected from a lower alkyl group, a halogen atom, a phenyl group, a lower alkoxycarbonyl group, an amino group, and a lower alkoxy group. You may do so. However, the above-mentioned aromatic hetero 5- or 6-membered ring groups include a thiazole ring group, an isothiazole ring group, a pyridine ring group, and 1. 3. It must not be a 5-triazine ring group. ] The compound of the present invention represented by the above general formula (1) is a novel compound not yet described in literature, and has the following general formula (2)% formula % [wherein R1, R2, R3 and α are the same as above. ] This compound is useful as a synthetic intermediate for the p-aminophenol derivative represented by the following formula.

The p-aminophenol derivatives of general formula (2) above can be used to treat acute inflammation or chronic inflammatory diseases such as arthritis and rheumatism by reducing inflammation, and by inhibiting the production of lipoxygenase metabolites, such as asthma. It is a known compound useful in the treatment of diseases such as bronchitis, bronchitis, and dry disease (Japanese Patent Application Laid-Open No. 64-25756).

In this specification, each layer shown below has the following meaning.

Examples of the lower alkyl group include straight or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1eN-butyl, pentyl, and hexyl.

Examples of lower alkoxy groups include straight or branched alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, 5ec-butoxy, jett-butoxy, pentyloxy, and hexyloxy groups. I can give an example.

Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms.

Examples of lower alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,
Examples include alkoxycarbonyl groups in which the alkoxy moiety has 1 to 6 carbon atoms, such as Ierl-butoxycarbonyl, pentyloxycarbonyl, and hexyloxycarbonyl groups.

Examples of the hetero 5- or 6-membered ring group containing 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms represented by α include a pyrrole ring group, a furan ring group, a thiophene ring group,
Examples include a pyrazole ring group, an imidazole ring group, an isoxazole ring group, an oxazole ring group, a triazole ring group, a thiadiazole ring group, an oxadiazole ring group, a triazine ring group, a pyrazine ring group, a pyrimidine ring group, and a pyridazine ring group.

Representative examples of the aromatic hetero 5- or 6-membered ring group containing 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms include 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl,
-pyrrolyl, 2-furyl, 3-furyl, 2-thienyl,
3-thienyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3
-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxasilyl, 4-oxasilyl, 5-oxasilyl, 1. 2. 3-1 lyazol-1-yl,
1. 2. :3-) riazol-4-yl, 1. 2
．． 3-triazol-5-yl, 1.2.4-triazol-1-yl, 1,2゜4-triazol-3-yl, 1.2.44lyazol-5-yl, 1.2.3-yl
Thiadiazol-4-yl, 1. ．． 2.3-thiadiazol-5yl, 1. 2. 4-thiadiazole-3-
yl, L, 2,4-thiadiazol-5-yl, 1,3
゜4-thiadiazol-2-yl, l, 2.3-oxadiazol-4-yl, 1.2.3-oxadiazol-5-yl, 1,2.4-oxadiazol-3-yl , 1,2.4-oxadiazol-5-yl, 1.3.
4-oxadiazol-2-yl, 1,2.44-riazin-3-yl, 1.2.4-triazin-5-yl, 1.
2. 4-triazin-6-yl, 1. ．． 2.3-1 riazin-4-yl, 1,2.3-1 riazin-5-yl, pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl,
Examples include 5-pyrimidinyl, 3-pyridazinyl, and 4-pyridazinyl groups.

Also, pyrazine-N-oxide ring group, pyridazine-N-
Representative examples of the oxide ring group or pyrimidine-N-oxide ring group include pyrazine-1-oxide-2-yl, pyrazine-1-oxide-3yl, pyrimidin-1-oxide-2-yl, and pyrimidine-1-yl. oxide-4-yl,
Pyrimidine 1-oxide-5-yl, pyrimidine-1-
Examples include oxide-6-yl, pyridazin-1-oxide-3-yl, pyridazin-1-oxide-4-yl, pyridazin-1-oxide-5-yl, and pyridazin-1-oxide-6-yl groups.

The cyclohexadiene derivative of the present invention can be produced by various methods. A specific example thereof is shown in the reaction scheme below.

Reaction Scheme-1> [In the formula, R1, R2, R3 and α are the same as above. ] According to the method shown in Reaction Scheme-1 above, the compound (1) of the present invention can be produced by a condensation reaction between the quinone derivative (3) and the aromatic heterocyclic amine derivative (4).

In the above, among the quinone derivatives (3) used as raw material compounds, alkylbenzoquinones are known or are described, for example, in Chemical Pharmaceutical Bulletin [Chem, Pha+m flu34, 121
(+986)],
The method of D., Liolla et al. CJ
, Org, Chem,, 48. 2932
(1983)). Alkylnaphthoquinones are also known or described, for example, in the Journal of the American Chemical Society CJ, Am, Chem, Soc, 70.
3165 (1948)) according to the method of L. F. Fieser (1948).

Moreover, the aromatic heterocyclic amine derivative (4), which is the other raw material compound, is a known compound.

For example, The Chemistry of Heterocyclic Compounders [G, B, Ba+lin T
heChemisDy of l1elerocycle
ic Compounds, Volume 41.

1nlerscience, New York,
1982, Chapter 8], same document (T, Nakagom
e: R, N, Ca5llc ed., vol. 28, 1973.

Chapter 6], same document (D, J, B "own, 16
Volume, 1962.

Chapter 9, J. Brown, Volume 16 (Su
pplement I) 1970, Chapter 9] etc.

The condensation reaction shown in the above reaction scheme-1 is described by Neeriker and H, Kessler (A, Reilker and IfK).
Tetrahedron [Te1rahe]
The reaction can be carried out by heating the quinone derivative (3) and the aromatic heterocyclic amine derivative (4) to about 100 to 200°C and reacting them according to the method described in Dron23, 3723 (+976)].

Further, the above condensation reaction is carried out with the quinone derivative (3) in the presence of a halide Lewis acid such as aluminum chloride, ferric chloride, titanium tetrachloride, tin chloride, zinc chloride, etc.
An aromatic heterocyclic amine derivative (4) that also serves as a deoxidizing agent,
It can also be carried out by reacting in an inert organic solvent. Examples of the inert organic solvent used in the reaction include halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,2-trichloroethane, and chloroform;
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and reaction temperature conditions range from room temperature to about 120°C.
can be adopted. An inert organic base such as pyridine or l-ethylamine may also be added to the reaction system as a deoxidizing agent. The ratio of the quinone derivative (3) and the aromatic heterocyclic amine conductor (4) to be used is not particularly limited, but is usually about 1 to 10 times the molar amount of the former to the latter, preferably about 1 to 3 times the molar amount of the latter. It is preferable to use a molar amount.

Incidentally, reactions using titanium tetrachloride are described in, for example, the Journal of Organic Chemistry [jOtg, Ch.
em,, 32. 3246 (1967): H as described in I.

It can be carried out according to the method of Weinga+Ien et al.

In addition, the above reaction can be carried out using a Lewis acid other than the above, such as boron trifluoride/ethyl ether, tetrahydrofuran,
It can also be carried out by reacting both starting compounds in a suitable solvent such as dioxane at a temperature of room temperature to about 100°C. This reaction was described by J. Figueras (J.
ras) et al. CJ, Org.

Chem, , 36. 3497 (1971))
known as.

Furthermore, among the compounds of general formula (1) of the present invention, compounds in which α is a pyrazine-N-oxide ring group, a pyridazine-N-oxide ring group, or a pyrimidine-N-oxide ring group can also be produced by the following method. can do.

<Reaction Scheme-2> [In the formula, R1, R2 and R3 are the same as above. α represents a pyrazine ring group, a pyridazine ring group, or a pyrimidine ring group, and α
2 represents a pyrazine-N-oxide ring group, a pyridazine-N-oxide ring group, or a pyrimidine-N-oxide ring group,
The heterocyclic group represented by α1 and α2 may have 1 to 3 groups selected from a lower alkyl group, a halogen atom, a phenyl group, a lower alkoxycarbonyl group, and a lower alkoxy group as substituents. . ] According to the method shown in the above reaction scheme-2, compound (5)
The compound (1a) of the present invention can be obtained by the oxidation reaction.

Production of compound (1a) from compound (5) (oxidation reaction)
For example, in an inert organic solvent such as dichloromethane, chloroform, acetic acid, etc., using an organic peracid such as 3-chloroperbenzoic acid or peracetic acid in an amount of about 1 to 5 times the molar amount of compound (5), This can be advantageously carried out at a temperature of about 50'C for about 5 to 30 hours. The compound (5) used as a raw material in this reaction can be prepared, for example, by the condensation reaction of the quinone derivative (3) shown in the reaction scheme-1 and the aromatic heterocyclic amine derivative (4) using an appropriate raw material compound. It can be manufactured in a similar manner.

The p-aminophenol derivative of general formula (2) obtained from the compound (1) of the present invention can be obtained without or after isolating the compound (1) of the present invention obtained as described above from the reaction system. can be synthesized by subsequently subjecting it to a reduction reaction as shown in Reaction Scheme 3 below.

Reaction Scheme 3> [In the formula, R1, R2, R3 and α are the same as above. The reduction reaction of the compound (1) of the present invention can be carried out in accordance with a conventional method, for example, by transferring the compound (1) of the present invention into TeI-rahydrofuran and adding an aqueous solution of sodium hydrosulfide in an amount of 2 to 50 times the molar amount. Can be implemented. Depending on the type of substituent α of the compound (1) of the present invention, the above reduction reaction can be carried out, for example, by using zinc powder in acetic acid, or by using palladium-carbon or platinum dioxide in a solvent such as ethyl acetate, alcohol, or tetrahydrofuran. It can also be carried out by a method of catalytic hydrogenation using as a catalyst, a method of using sodium borohydride in a mixture of tetrahydrofuran and water, and the like.

The compound (1) of the present invention obtained by the reactions shown in the above reaction schemes can be easily isolated and purified by conventional separation means. Examples of the separation means include solvent extraction, recrystallization, and column chromatography.

Hereinafter, in order to explain the present invention in more detail, production examples of raw material compounds for producing the compounds of the present invention will be listed as reference examples, and then production examples of the compounds of the present invention will be listed as examples.

Reference Example 1 Production of 2-1erl-butyl-6-isopropyl-1,4benzoquinone 160 g of sodium dichromate dihydrate was dissolved in a mixture of 97% sulfuric acid LOOyl and water 230 rA', - It was added dropwise to a solution of 45.0 g of tell-butyl-6-iprobylphenol in 35011 diethyl ether at 5 to 10° C. over 2.5 hours while stirring. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed with saturated aqueous sodium bicarbonate and then with saturated brine, dried over magnesium sulfate, and concentrated. The obtained crude product was purified by silica gel column chromatography (diethyl ether:hexane-1,:10) to obtain the target compound L.
2. '1 g was obtained as a pale yellow oil.

II-NMR (CDC(13): δ1.12
(d, J=6.8Hz, 6TI) 1, 29 (s,
911), 3. 09 (d 5eplet.

J=6,811z, 1, l11z, 111) 6.45
(dd, J=2.6Hz, 1.1llz.

1ll) 6.53 (d, J=2.61Tz, IH) Reference Example 2 Production process 1 of 2-1crt-butyl-5,6,7,8-tetrahydro-1,4-naphthoquinone 2-1erl-butyl -1,4-benzoquinone 120g
was suspended in acetic acid 3707/, and added with butadiene 52 under water cooling.
g, and the flask was stoppered and left at room temperature for 48 hours. Thereafter, 9 g of sodium acetate was added to the reaction mixture, heated under reflux for 30 minutes, and concentrated. The residue was dissolved in dichloromethane, washed with water, and then dried over magnesium sulfate. The crude product obtained by concentration was washed with hexane, and 2-1ef
75 g of +-butyl-5,8-dihydro-1,4-naphthohydroquinone was obtained as a pale red solid.

Melting point 122-124 ° C I (-NMR (CDCA'3): δ 1, 39 (s, 911), 3. 23 (
d, J-1, 511x, 4l-1), 4
．． 35 (broad, 211)5, 90 (b
road s, 211)6, 64 (s,
III) Step 2 50 g of 2-1erl-butyl-5,8-dihydro-1,4 naphthohydroquinone was suspended in 30011 ethyl acetate, 300 mg of platinum dioxide was added, and hydrogen gas was passed into the flask and stirred at room temperature. After 5.11 liters of hydrogen gas had been consumed, the reaction mixture was filtered through Celite and the furnace liquid was concentrated. The obtained crude product was washed with hexane, and 2-1
erl-butyl 5, 6. 7. 39 g of 8-tetrahydro-1,4-naphthohydroquinone was obtained as a pale red solid.

Melting point 134-135°C 1C11-N (CDC13): δ 1,. 38 (s, 9H), 1.70-1.90 (
+++, 411), 2. 50-2. 70
(m.

41T), 4. 40 (broad s, 2
11), 6, 63 (s, 1.11) Step 3 22 g of 2-1erl-butyl-5,6,7,8-tetrahydro-1,4-naphthohydroquinone was dissolved in 1007A of acetic acid.
10 g of nitric acid was slowly added while stirring at room temperature. The reaction mixture was stirred at room temperature for 20 minutes, poured into fresh water, and extracted with dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, and concentrated to obtain 21 g of the target compound as a pale yellow solid.

Melting point 50-52°C II-NMR (CDC/3): δ1, 27
(s, 91(), 1.60-1., 80
(m, 4l-1), 2. 30-2. 50
(m.

41-D, 6. 51 (s, III)
Example 1 2.6-di-1erl-butyl-4-pyrazinylimino-2,5-cyclohexadien-1-one [Compound 1]
Production (Method I) 47 g of 2.6-di-1ft-butyl-1,4-benzoquinone and 20 g of aminopyrazine were added to 30 M of tetrahydrofuran and dissolved by heating. To this was added a yellow suspension prepared in advance by adding titanium tetrachloride 1211 dropwise to a solution of pyridine 35111 in 200 y/dichloroethane under water cooling and stirring, and the mixture was heated under reflux for 1 hour. Furthermore, a mixed suspension of pyridine 70yA', titanium tetrachloride 2411 and dichloroethane 200z/ was added to the reaction mixture, and after heating under reflux for 2 hours, a mixed suspension of pyridine 1.77L and titanium tetrachloride 611 and dichloroethane 1007A' was added. 3
Heating and refluxing for 0 minutes was repeated. The reaction mixture was then cooled to room temperature and filtered through Celite. The crude product obtained by washing the insoluble matter with ethyl acetate and concentrating the furnace solution was
Purified by silica gel column chromatography (eluent; diethyl ether:hexane-1:10 → 1:1),
Washed with cold hexane.

In this way, 1158 g of 2,6-di-1ert-butyl-4-pyrazinylimino-2,5-cyclohexadiene-1 compound was obtained as a yellow solid.

(Method ■) Pyridine 97.1yI was dissolved in dichloroethane 944d, titanium tetrachloride 32.9z/ was added thereto, and the mixture was heated under reflux for 15 minutes. Then 2,6-di-1erlbutyl-
132.2 g of 1,4-benzoquinone and 57.1 g of aminopyrazine were added, and the mixture was heated under reflux for 42 hours. After the reaction mixture was cooled to room temperature, it was filtered through Celite, and insoluble materials were washed with dichloromethane. The crude product obtained by concentrating the solution was purified by silica gel column chromatography (diethyl ether:hexane-3N) to obtain compound 1.
82.8g was obtained.

(Method ■) Dissolve 1.62 yl of pyridine in 6011 dichloroethane, add 1 ml of aluminum chloride, and 0.0 ml of powder. 89 g was added and heated under reflux for 15 minutes. Then 2.6 g tert-
2.20 g of butyl-1,4-benzoquinone and 0.95 g of aminopyrazine were added, and the mixture was heated under reflux for 17.5 hours.

After the reaction mixture was cooled to room temperature, it was filtered through Celite (21+), and insoluble materials were washed with dichloromethane. The crude product obtained by concentrating the liquid was purified by silica gel column chromatography (diethyl ether:hexane-3,7) to obtain 11.73 g of compound.

(Method ■) 11.02 g of 2.6-ferl-butyl-1,4-benzoquinone and 4.76 g of aminopyrazine were heated at 150° C. for 6 hours with stirring. After cooling the reaction mixture to room temperature, it was purified by silica gel column chromatography (diethyl ether:hexane-1=4) to obtain compound 13.
．． 95g was obtained.

Table 1 shows the physical properties (melting point and IIN MR value) of the obtained Compound 1.

Examples 2 to 29 Production of Compounds 2 to 29 In the same manner as Method I, Method ■, Method ■, or Method ■ of Example 1, 2
．． 6-dimethyl-1,4-benzoquinone, 2,6-diisopropyl-1,4-benzoquinone, 2-1erl-butyl-6-isopropyl-1,4-benzoquinone, 2,
6-di1e “1-butyl-1゜4-benzoquinone, 2
．． 5-di-1ert-butyl 1,4-benzoquinone, 2
, 3,6-trimethyl-1,4-benzoquinone, 2-methyl-5,6゜7.8-tetrahydro-1,4-naphthoquinone, 2-erl-butyl-5,6,7,8-tetrahydro Target compounds (Compounds 2 to 29) were produced from each of 1,4-naphthoquinone and 2-methyl to 1°4-naphthoquinone and an aminodiazine derivative.

The structure and physical properties of each compound obtained are shown in Table 1 below.

Table 1 Example 30 Preparation of 2.6-di-1ert-butyl-4-(3-pyrazolylimino)-2,5-cyclohexadien-1-one [Compound 30] 2.6-di-1ert-butyl -1,4-benzoquinone 5.3g, 3-aminopyrazole 2.1g and acetic acid 16
The drops were heated at 110°C for 15 minutes with stirring. After cooling the reaction mixture to room temperature, silica gel column chromatography (diethyl ether:chloroform-1:20
) to give 2゜6-di-1ef-butyl-4-(
5.5 g of 3-pyrazolylimino)-2,5-cyclohexadien-1-one [Compound 3] was obtained as a pale red solid.

Physical properties of the obtained compound 30 (melting point and “■IN M R
values) are shown in Table 2.

Examples 31 and 32 Preparation of Compound 31 and Compound 32 In the same manner as in Example 30, 2,6-diisopropyl-1
, 4-benzoquinone and 2-1erl-butyl-6-isopropyl-1,4-benzoquinone were reacted with 3-aminopyrazole to produce the target compounds (compound 31 and compound 32).

The structure and physical properties of each compound obtained are shown in Table 2.

Example 33 2.3.6-Dolimethyl-4-(3-pyrazolylimino)-2,5-cyclohexadien-1one [Compound 33
] Production of 1.62 zl of pyridine was dissolved in 6011 ml of dichloroethane, and 0.5 zl of titanium tetrachloride was dissolved in this. Add M and heat to reflux for 15 minutes, then 2. 3. 5-1 methyl-1,4
- 1.50 g of benzoquinone and 0.0 g of 3-aminopyrazole.
83 g was added and heated under reflux for 2 hours. After the reaction mixture was cooled to room temperature, it was filtered through Celite, and insoluble matter was washed with chloroform. The crude product obtained by concentrating the m solution was purified by silica gel column chromatography (diethyl ether:hexane-1:1) to give 2.3°6-dolimethyl-4-(3-pyrazolylimino)-2,5 -Cyclohexadien-1-one [Compound 3330.52g
was obtained as a yellow solid.

The structure and physical properties of the obtained compound 33 are shown in Table 2.

Examples 34 to 5G Preparation of Compounds 34 to 56 In the same manner as in Example 33, 2,6-jetl-butyl-1,4-benzoquinone and an appropriate aromatic heterocyclic amine derivative were reacted to produce the desired compound. Compounds (Compound 34 to Compound 56) were produced.

The structure and physical properties of each compound obtained are shown in Table 2 below.

Example 57 Preparation of 2-N-(3,5-dierl-butyl-4-oxo-2,5-cyclohexadienylidene)aminopyrazine-4-oxide [Compound 57] 1.62y of pyridine was dissolved in 6011 of dichloroethane! 0.55 zl of titanium tetrachloride was added thereto, and the mixture was heated under reflux for 15 minutes. Then 2,6-di-1erlbutyl-
2.20 g of 1,4-benzoquinone and 2-aminopyrazine-4-oxide], 11. g was added thereto, and the mixture was heated under reflux for 2 hours. After cooling the reaction mixture to room temperature, it was filtered through Celite,
Insoluble matter was washed with dichloromethane. The crude product obtained by concentrating the liquid was subjected to silica gel column chromatography (
Eluate: diethyl ether:hexane-2=3) to obtain 570.65 g of the compound as a yellow solid.

Melting point = 152-153°C TI-NMR (CDC123): δ1.23
(s, 9H), 1.32 (s, 9TI) 6.82
(d, J=2.6IIz, 1.11)6.
98 (d, J=2.611z, ITD7.93
-7.95 (m, 211), 8.32 (dd, J
=3.51Tz,l',511z,III) Example 58 1-N-(3,5-di1ft-butyl-4-oxo-2,5-cyclohexadienylidene)aminopyrazine-4-oxide [Compound 58 2. Production of 6-sheet tcrt-butyl-4-pyrazinylimino-2,5-cyclohexadien-1-one [Compound 1]
30. Og and 70% 3-chloroperbenzoic acid25. Og
was dissolved in 1000y/dichloromethane and diluted with 15% at room temperature.
Stir for hours. The reaction mixture was poured into 5% aqueous sodium bicarbonate, the organic layer was separated, and the aqueous layer was further extracted with dichloromethane. The organic layers were combined, washed with 5% aqueous sodium bicarbonate and then with water, dried over magnesium sulfate, and concentrated. The obtained crude product was purified by silica gel column chromatography (eluent: diethyl ether:hexane-1:1 → diethyl ether → ethyl acetate) to obtain 2-N-(3,5-
Di1erl-butyl-4-oxo-2,5-cyclohexadienylidene)aminopyrazine-4-oxide (compound 57)9. Along with 0 g, 581.8 g of the compound was obtained. The physical properties of the compound 58 are as follows.

Melting point = 165-167°C II-NMR (CDC13): δ 1, 23 (btoads, 9)-1),
1. 33 (broad s, 9I-1), 6
．． 54 (broad s, III), 7.
16 (broad s, ILI), 8.
1.4(broad s, 11(), 8.2
4 (dd, J = 4.1l-1z, 0.711z
, III), 8.29 (d, J=4.1Hz,
III) (and above)

Claims (1)

[Claims] [1] General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 represents a lower alkyl group. R^2 represents a hydrogen atom or a lower alkyl group, R^3 represents a hydrogen atom or a lower alkyl group, or R^2 and R^3 are combined to form a group -(CH_2)_4- or a group -CH= Indicates CH-CH=CH-. α is an aromatic hetero 5- or 6-membered ring group containing 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms, pyrazine-N-oxide ring group, pyridazine-N-oxide ring group, or pyrimidine -N-oxide ring group, and aromatic heterocyclic groups such as these have 1 to 3 substituents selected from lower alkyl groups, halogen atoms, phenyl groups, lower alkoxycarbonyl groups, amino groups, and lower alkoxy groups. It may have. However, the aromatic hetero 5- or 6-membered ring group must not be a thiazole ring group, an isothiazole ring group, a pyridine ring group, or a 1,3,5-triazine ring group. ] A cyclohexadiene derivative represented by