JPS5859971A - Preparation of 3-hydroxyquinophthalone compound - Google Patents

Abstract

PURPOSE:To obtain titled compound in high purity and yield, by condensing 3- hydroxy-2-methylcinchonic acid with phthalic anhydride, etc. in tetramethylene sulfone as a solvent, and brominating the resultant compound without separation, etc. CONSTITUTION:3-Hydroxycinchonic acid is condensed with phthalic anhydride or trimellitic acid anhydride in tetramethylene sulfone solvent to give 3-hydroxyquinophthalone or a compound of formulaI. The former without separation is then brominated to give 4-bromo-3-hydroxyquinophthalone of formulaII. Alternatively, the compound of formulaI is subjected to the desalting or acid chloride forming reaction to esterify methyl cellosolve or ethyl cellosolve and afford the aimed 3-hydroxyquinophthalone compound of formula III (R is CH3 or C2H5). USE:A dyeing material for fibers and coloring material for resins.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 3-
Method for producing hydroxyquinophthane compounds.

Specifically, 6-hydro-vI+cy-2-methyl cinchoninic acid and phthalic anhydride are subjected to a condensation reaction in the presence of tetramethylene sulfone, and the resulting 6-hydro-p-xyquinophthane is not separated, Subsequently, a bromination reaction is carried out to form a 4-bromo-3-hydroxyquinophtha p/, represented by the formula (bon).
Or S-human pj? 2-Methyl cinchoninic acid and trimellitic anhydride are subjected to a condensation reaction in the presence of tetramethylene sulfone, and the resulting 3-hytoxyquinophthalone trout body represented by formula (m) is separated. Without continuing the formula (■), the carboxyl group of the compound, the methoxyethoxycarbonyl group or the -? 5. Perform esterification to jetoxycarbonyl group. Formula (II), represented by υ (in formula ■, R is methyl or ethyl group)
The present invention relates to a method for producing 6-hydroxyquinophthalone compounds.

In the method of the present invention, the 4-poum-6-7-doxyquinophthalone compound represented by formula (1) or the 3-droxyquinophthalone compound represented by formula (■) is a compound of nylon, polyester, cellulose. Dyeing of various fibers such as acetate, polyolefin, polyurethane, etc., copolymerization of polystyrene (Pg resin), ac-alternative ρ-nidosilstyrene (hcABm resin)% 7crip nitrile-ruze-air styrene copolymer (AB841tl resin → Holly resin) It is a known compound that is extremely useful for coloring olefin resins, polyvinyl chloride resins, polyamide resins, etc.

The following compounds are generally prepared by carrying out a condensation reaction of 3-hydroxy-2-methyl cinchonine (3-hydroxy-2-methyl cinchonine stirrup) and anhydrous phthalic acid.
- Human-oxyquinophthalone is isolated and this material is subjected to bromination reaction to obtain the compound of formula (1), 6-
Hydroxy-2-methylquinosine is also L<is 3-human pl
? A condensation reaction of C2-methyldino: +5-NO and trimellitic anhydride is carried out, the resulting condensation reaction product of the compound of the formula (nl) is unified, and this is esterified with a Senlup compound to obtain the corresponding formula ( Compound II) has been obtained.

A method of producing a single reaction product using 3-human-xy-2-methylquinoline in the condensation reaction is described, for example, in U.S. Patent No. 200
No. 6022 discloses that 5-human-xy-2-methylquinoline and anhydrous quinoline are condensed to prepare 3-L deρoxyquino7rip, but this method is However, when the reaction is completed and discharged into water, the #l molten reactant forms a large lump due to cooling, making stirring difficult. A method of condensing 7-acid and O-sica with a bonic acid anhydride, such as 7-talic anhydride, using various inert solvents such as O-di-fvx-rubenzene, tritalbenzene, and yohyonitrobenzene (U.S. Patent No. 3
No. 023213, #iIJ No. 3023214) have also been proposed, but these methods also cause agglomeration after the completion of the reaction, which makes it difficult to process the condensation reaction and requires the expense of purifying the condensation reaction mass using a new organic solvent. In addition, since it is difficult to further react the condensation reaction product as it is, JP-A-48-56722 discloses a method in which the condensation reaction product is used as a solvent during the synthesis reaction, and after the reaction is completed, the reaction product is treated with a lower Alpool. Although this method can alleviate the difficulty of condensation reactions, it has the disadvantage that the condensation reaction is slow and the yield is low even if the reaction is carried out for a long time.

However, no satisfactory method for producing the condensation reaction product 3-doxyquinophtane and the 3-+-doxyquinophtane derivative represented by the formula (Rin) could be obtained using the known methods. Furthermore, in order to react the bromination reaction of shiquinoftane in a 3-dose compound or to react the compound of formula (1) to the chemical compound of formula (1), an inert solvent is selected and used in each reaction. I), the reaction to a compound of formula (1) was carried out.

The present invention provides an industrially very advantageous method for producing highly pure 3-hydroxyquinophthane and 77-turn metals, which involves the condensation of 3-hydroxyquinophtane and a compound of formula (1). The solvent used in the production of the reaction product is used as is, and the compounds of formula (I) and formula (1) are subsequently produced.

Next, embodiments of the method of the present invention will be explained. As a solvent for the overall reaction, phthalic anhydride or trimellitic anhydride was used in the presence of tetramethylene sulfone in a sol ratio of 0.5 to 3 to 1114 mol of 3-human-xy-2-methylsinzene. Tetramethylene sulfone is 4 to 1 per mole of 3-human-xy-2-methylsine:I nic acid.
0 molar amount is used. Inert solvents such as nitrobenzene, trithalolbenzene, 0-dicoolbenzene, 0-etho-toluene, coolnaphthalene, tetrabylonaphthalene, etc. can also be used together during the condensation reaction or after the total reaction, depending on the necessity of the reaction. be.

In the condensation reaction, starting materials are placed in a reactor equipped with a stirring device, and when condensed at a temperature of 175 to 220°C, 1 to 1
The reaction is completed in 2 hours. A very preferred temperature for the reaction is 200-205°C, and the water produced during the reaction is distilled out of the reaction system through a cooler.

! ! After the completion of the Kura reaction, the obtained reaction solution is cooled to 80 to 150°C, followed by a bromination reaction to obtain the compound of formula (1), or a desalting reaction to obtain the compound of formula (If).
or methyl cellosolve, via acid tarrolidation,
Esterification of methyl cellosolve is carried out.

The bromination reaction is carried out at 80-120°C with a molar ratio of 1, θ-20/
After adding bromine of 3-kF-2-methyl cinchoninic acid to Xu A, it is kept at the same temperature for 1 to 5 hours. After the reaction is complete, methanol or water is added to the reaction mixture, and the precipitated crystals are passed through, washed with water, and dried to obtain highly pure 4-poum 3-.
Human-xyquino 7-turns are obtained in high yield.

In addition, for esterification by desalting reaction, the condensation reaction solution of the compound of the formula (seal) is cooled to 100" to 150°C, and an alkali such as potassium sulfuric acid or soda ash is added to form a carboxylic acid. After conversion to um salt, 1.0-204 l ratio/3
- * F w coconut-2-methyl cinchoninic acid, P-
Silenesulfonic acid methoxyethyl ester &iP
- Add toluenesulfonic acid ethoxyethyl ester,
The mixture is kept warm at 100°C to 150°C for 2 to 10 hours to complete esterification.

In order to perform esterification using acid tallide, the formula (
The condensation reaction solution of the carbon dioxide) compound was cooled to 80-120@
．． Add 0 to 20 phosphor ratio/3-human-xy-2-methylcinchobenzic acid, acid tallide and other agents such as thiophyl chloride and phosphorus oxychloride, and keep warm at 1Iill temperature for 1 to 5 hours to cool the acid. terminating the reaction. At this time, addition of a small amount of dimethylformamide is effective in accelerating the reaction. Methyl cellosolve or methyl cellosolve at a molar ratio of LO to 3.0 is further added to this reaction solution, and the mixture is kept at 100 to 130° C. for 1 to 5 hours to complete the esterification.

In either case, after the esterification reaction is completed, methanol or water is added, and the precipitated crystals are filtered, washed with water, and dried to obtain highly pure quinophthane compounds represented by formula (1) in high yield.

If the alcohol and tetramethylene sulfone are recovered from liquid V after separating the metal compound of formula (1) and formula (1) obtained in this way, the production can be carried out without discharging waste liquid to the outside. water, so there is no problem of water pollution. Formula (I) and formula (II) obtained by the method of the present invention
Since the compound can be obtained in high purity, there is no need for any purification, and when used as a resin coloring material, it can be colored very clearly.

Examples are shown below.

Example 1 3-hydroyac-2-methyl cinchoninic acid 15 was added to the reactor.
1, 22 N of 7-tar acid anhydride, and 45 g of tetramethylene sulfone were added, the temperature was gradually raised to 200° C., and the temperature was maintained at this temperature for 3 hours with stirring. During that time, the water produced during the temperature rise and retention was distilled out of the reaction system from the cooler and separated.

After the condensation reaction was completed, the reaction solution was cooled to 120°C.

Reaction in suspension! Ryohin 113I was added to the mixture under slow AC and kept at the same temperature for 2 hours. 80% methanol water 50-
was added, stirred at 65-70°C, passed through at room temperature, washed with water, and dried to obtain a bright colored powder 2alj (yield: 96%).
2-Methyl cinchoninic acid) was obtained in the dough at jlt3-mP, 22s ~ 230℃, bromine content 2α5% (theoretical bromine content: 2L7%) 0 The metal compound has the following structure. Ta.

δ Example 2 Put 21.1F of anhydrous ψmetic acid and tetotumethylene ^phone 901 into a reactor, and while stirring,
The mixture was heated and dissolved at 200°C. 3-t-toxy-2-methylcincitric acid 2α3I was stirred at 190-200°C for 1 hour, and then stirred at 200°C for 3 hours. The water produced during the valve temperature and heat retention was distilled out of the reaction system from the cooler and separated. After completion of the condensation reaction, trithalolbenzene 651i was added to the reaction solution, cooled to 100°C, dimethylform 74Fo, aj' was added as a catalyst, and thionyl chloride 31. After adding f at 90℃, 3 at 125-130℃
The acid tarridation reaction was carried out by stirring for a period of time. - Add 166g of Chirsenrup and stir at 125℃ for 2 hours,
It was cooled to 80° C. and discharged into 200 g of methanol.

After cooling to 25"○, filtration, washing with methanol 10011, water washing, and drying gave 30.1 N of a reddish-colored powder. (Yield: 76.8% to 3-droxy-2-methylcincitric acid. )0 dye has the following structural formula, and dyes acetate fibers and polyester fibers in bright reddish yellow color IJ1.

After the completion of the condensation reaction in this example, the reaction solution was cooled to 120°C, and the carbonation power was measured! Add 14I, and then add Ep-)methoxydiethyl ester of luenesulfonic acid 2aO to give 12
After reacting at 0° C. for 2 hours, the mixture was cooled to room temperature, added with 80% methanol 200I, filtered, washed with water, and dried to obtain dye 33JF having the same structural formula as above.

Claims (1)

[Claims] 13-Hydroxy-2-methylcinchonine a and m-hydrophthalate are subjected to a condensation reaction in the presence of tetramethylene sulfone, and the resulting 3-hydroxyquinophthal-7 is 2.3-Huto-xy-2-methylcinco Condensation reaction of nic acid and mellitic anhydride is carried out in the presence of tetramethylene sulfone, and the resulting 5-human-xyquinophthalone derivative represented by formula (m)υ is subsequently converted to the formula (m) without separation. (m) A formula (
n) A method for producing 3-hydroxyquinophthane compounds represented by [Formula (n), R is methyl or ethyl group].