JPH0316986B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to indazolone derivatives and methods for producing the same. That is, the present invention is based on the general formula The present invention provides an indazolone derivative represented by:

The compound of the present invention has pale yellow to greenish-yellow crystals that turn purple upon air oxidation in a solvent. They discovered that the color changes quickly from pale yellow to purple, making it useful as an oxygen detection substance.
In addition, the purple substance obtained by oxidation of this compound has the general formula This compound is a substance useful as a purple pigment.

The invention also relates to the general formula (In the formula, R is a lower alkyl group) is condensed with phenylhydrazine to form a compound with the general formula The present invention provides a method for producing an indazolone derivative represented by:

The condensation reaction of the method of the present invention proceeds easily by heating the starting materials, succinyl succinate and phenylhydrazine, in an organic solvent under an acid catalyst. The ratio of starting materials during the reaction is usually 2 moles or more, preferably 2 moles or more of phenylhydrazines per 1 mole of succinyl succinate.
It is 2.1 to 3 moles. The solvent is not particularly limited as long as it is an organic solvent inert to the reaction, but benzene, toluene, xylene, chlorobenzene, acetic acid, and the like are preferred. The amount of the solvent to be used is not particularly limited, but it is usually about 3 to about 100 times, preferably about 5 to about 20 times the weight of the succinyl succinate.

As the acid catalyst used in this reaction, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, etc. are generally used. When an organic acid such as acetic acid is used as a reaction solvent, or when a hydrochloride or sulfate of phenylhydrazines is used, it is not necessary to further add an acid catalyst. The amount of acid catalyst used is usually about 0.01 mole based on the succinyl succinate.

The reaction temperature is usually about 50°C to about 200°C, preferably about 70°C to about 150°C. The reaction time is usually about 30 minutes to 5 hours.

The present invention will be explained in more detail below with reference to Examples.

Example 1 1 with thermometer, cooler and stirrer
- 25.6 parts of succinyl succinic acid diethyl ester, 32.4 parts of phenylhydrazine in a four-necked flask,
300 parts of toluene and 0.5 part of 36% hydrochloric acid were added, and the mixture was heated under reflux for 4 hours while introducing nitrogen gas.
The reactant initially became a homogeneous solution, but as the reaction progressed, white crystals precipitated. After cooling the reaction mixture, the product was isolated by filtration, washed with acetone, and air-dried. 1H, 5H-4,8-dihydro-2,6-diphenylbenzo[2,1-
d: 15 parts of 4,5-d']diindazole-3,7-dione were obtained.

Elemental analysis value _: C69.3, _H4.7 , N16.7% Calculated value _{as C20H16N4O2} C69.77, H4.65,
N16.28% IR (KBr, cm ^-1 ): 3450 (NH), 2890 (CH ₂ ),
3050 (phenyl group H), 1640 (C=O), 1600, 1490
(Phenyl group), 1300 (C-N), 745, 690 (-substituted benzene out-of-plane bending vibration) ¹ H-NMR (DMSO-d ₆ solvent δ): 1.58 (-CH ₂
-), 7.8 to 8.1 (phenyl group H) Usage Example 1 2 mg of the compound of the present invention obtained in Example 1 was dissolved in 50 ml of N-methyl-2-pyrrolidone in a nitrogen gas atmosphere. 20 ml of the solution was placed in a 10 mm diameter test tube equipped with a gas introduction tube, and nitrogen gas containing 5% oxygen gas was passed through the tube at a flow rate of 1/min for 1 minute.
The solution was colored purple, and the absorbance at 570 nm on a spectrophotometer increased by 0.2 compared to before the gas was introduced. This compound has been found to be useful as a substance that can visually detect oxygen gas through this change in hue.

Use Example 2 5 parts of the compound of the invention obtained in Example 1 and 5 parts of chloranil were heated under reflux for 1 hour in 100 parts of glacial acetic acid. After the reaction was completed, the reaction solution was cooled to room temperature and 100 parts of water was added to produce a purple solid. This solid was collected, thoroughly washed with water and methanol, and then dried under reduced pressure. Yield 5 parts. The product was identified by elemental analysis, IR spectrum, UV spectrum, and NMR spectrum as 1H, 5H−2.6
-diphenylbenzo[2,1-d:4.5-d']diindazole-3,7-dione.

Elemental analysis value _: C69.9, H3.8, N17.1% Calculated value _{as C20H14N4O2 C70.18} , H4.09,
N16.37% IR (KBr, cm ^-1 ): 3400 (NH), 3050 (phenyl group H), 1700 (C=O), 1600, 1490 (phenyl group),
¹ H-NMR (DMSO-d ₆ solvent δ): 7.8 to 8.2 (phenyl group H) 0.02 parts of this compound was dissolved in 100 parts of DOP, 200 parts of polyvinyl chloride was added, and the mixture was kneaded with a roll at 150°C.

A transparent PVC sheet with a clear blue color was obtained and had excellent heat resistance and weather resistance.

In addition to polyvinyl chloride, this compound was also suitable for coloring thermoplastic resins such as polyethylene, ethylene/vinyl acetate copolymer, polypropylene, and polystyrene.

Claims (1)

[Claims] 1. General formula An indazolone derivative represented by 2 General formula A general formula characterized by condensing a succinyl succinate ester represented by (wherein R is a lower alkyl group) with phenylhydrazine A method for producing an indazolone derivative represented by