WO2017170096A1 - Procédé de production d'un nouveau composé dihydroxy - Google Patents

Procédé de production d'un nouveau composé dihydroxy Download PDF

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WO2017170096A1
WO2017170096A1 PCT/JP2017/011627 JP2017011627W WO2017170096A1 WO 2017170096 A1 WO2017170096 A1 WO 2017170096A1 JP 2017011627 W JP2017011627 W JP 2017011627W WO 2017170096 A1 WO2017170096 A1 WO 2017170096A1
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general formula
phenyl
group
reaction
formula
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Japanese (ja)
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隼 溝口
緒旺 路
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Honshu Chemical Industry Co Ltd
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Honshu Chemical Industry Co Ltd
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Priority to JP2018509160A priority Critical patent/JPWO2017170096A1/ja
Priority to CN201780020587.4A priority patent/CN108884039A/zh
Priority to KR1020187029703A priority patent/KR102408697B1/ko
Publication of WO2017170096A1 publication Critical patent/WO2017170096A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a novel dihydroxy compound.
  • bisphenoxy alcohols compounds in which the hydrogen atom of the hydroxy group of bisphenol is substituted with a hydroxyalkyl group
  • thermoplastic synthetic resin raw materials such as polycarbonate resins, thermosetting resin raw materials such as epoxy resins, and antioxidant raw materials.
  • thermosetting resin raw materials such as epoxy resins
  • antioxidant raw materials such as antioxidant raw materials.
  • the performance required for these bisphenoxy alcohols has become increasingly sophisticated.
  • 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine having an N-phenylisoindoline skeleton is known (non-patent document). 1).
  • a method for producing bisphenoxy alcohols a method for producing bisphenol compounds by reacting a bisphenol compound with an alkylene carbonate or an alkylene oxide is known.
  • the product bisphenoxy alcohol further reacts with alkylene carbonates or alkylene oxides to form a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group, resulting in a low reaction selectivity.
  • the resulting compound is colored and has poor thermal stability, so it must be repeatedly purified for use as an optical application, which is industrially disadvantageous. Yes (Non-patent Document 1, Patent Document 1).
  • Patent Document 2 discloses hydrogen chloride gas and cation exchange resins generally used as catalysts in the production of bisphenols by dehydration condensation of phenols and ketones. It is stated that solid acids and the like show no activity.
  • Patent Documents 3 and 4 disclose a method in which fluorenones and phenoxyethanol are reacted in the presence of a sulfuric acid or heteropolyacid catalyst.
  • JP 09-255609 A Japanese Patent Laid-Open No. 2000-191577 Japanese Patent Application Laid-Open No. 07-165657 JP 2007-023016 A International Publication No. 2015/107467
  • the present invention has been made against the background described above, and an object of the present invention is to provide a method for producing a novel dihydroxy compound having an indoline skeleton having high heat resistance and high refractive index.
  • the inventors have conducted a condensation reaction using an N-phenylisatin compound and a phenoxyalcohol compound as starting materials, so that the reactivity is higher than that of a conventional reaction. Further, it was found that the production method is an industrially advantageous method for producing a high-quality dihydroxy compound because the condensation reaction proceeds under milder conditions than the conventional method, The present invention has been completed.
  • a dihydroxy compound represented by the general formula (1) is produced by reacting an N-phenylisatin compound represented by the following general formula (2) with a phenoxy alcohol compound represented by the following general formula (3).
  • Method. wherein R represents an alkylene group having 2 to 6 carbon atoms, R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different. When n is 2, R 2 is the same But it may be different.) (In the formula, R 2 and n are the same as those in the general formula (1).) (In the formula, R, R 1 and m are the same as those in the general formula (1).)
  • the reactivity of the N-phenylisatin compound and the phenoxy alcohol compound is more specific than the reactivity of the conventionally known cardo-structured ketones and the phenoxy alcohol compound. It is a manufacturing method characterized by being high. Further, since the reactivity of the N-phenylisatin compound and the phenoxyalcohol compound is high, the reaction proceeds at a higher yield and / or higher conversion rate than the conventional reaction or the reaction time is longer when compared under the same reaction conditions. Moreover, since the reaction proceeds under mild conditions, it can be an industrially advantageous production method. Furthermore, the production method of the present invention is useful as an industrial production method because a highly pure dihydroxy compound containing almost no impurities can be obtained.
  • the dihydroxy compound of the present invention is represented by the following general formula (1).
  • R represents an alkylene group having 2 to 6 carbon atoms
  • R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
  • m represents an integer of 0 to 3
  • n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different.
  • R 2 is the same But it may be different.
  • each R is independently an alkylene group having 2 to 6 carbon atoms.
  • alkylene group examples include 1,2-ethylenediyl group, 1,2- Examples thereof include a propanediyl group, a 1,3-propanediyl group, a pentamethylene group, and a hexamethylene group, preferably a linear or branched alkylene group having 2 to 4 carbon atoms, particularly preferably.
  • the hydroxyalkoxy group represented by “—O—R—OH” in the general formula (1) will be described.
  • the bonding position of the hydroxy group bonded to the alkylene group R is alkylene bonded directly to the ether group. It is not bonded to the carbon atom constituting the group R (the 1st carbon atom).
  • R is an alkylene group having 3 or more carbon atoms
  • the bonding position of the hydroxy group is preferably the 2- or 3-position of the alkylene group “R”, and more preferably the 2-position.
  • Specific examples include 2-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxy-1-methylethoxy group, 3-hydroxypropoxy group and the like.
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when R 1 is an alkyl group having 1 to 8 carbon atoms, Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • R 1 and R 2 are alkoxy groups having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like.
  • Such an alkoxy group may have, for example, a substituent such as a phenyl group or an alkoxy group, as long as the effects of the present invention are not impaired.
  • Preferred R 1 and R 2 are methyl groups.
  • m is 0, 1, 2, or 3, Preferably it is 0, 1 or 2, Especially preferably, it is 0 or 1.
  • n is 0, 1 or 2, Preferably it is 0 or 1, Especially preferably, it is 0.
  • the “—O—R—OH” group substituted for the phenyl group directly bonded to the 3-position carbon atom of the indoline skeleton and the substitution position of R 1 are first described as “
  • the —O—R—OH ”group is preferably substituted at the 4-position or 2-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, more preferably at the 4-position.
  • R 1 is preferably substituted at the o-position or the p-position with respect to the “—O—R—OH” group, and is a phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton.
  • the “—O—R—OH” group when the “—O—R—OH” group is substituted at the 4-position, it is preferably substituted at the 3-position or the 5-position, and the “—O—R—OH” group is substituted at the 2-position. When it is, it is preferable to substitute at the 3-position or 5-position.
  • the substitution position of R 1 is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, or R 1 is substituted on 3-position and 5-position "-O-R-OH” group is 4-position, it is preferred that R 1 is substituted on the 2- and 5-positions.
  • R 1 is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, R 1 is preferably substituted at the 2-position, 3-position and 5-position.
  • the dihydroxy compound represented by the general formula (1) is preferably a compound represented by the following general formula (4).
  • R 2 and n are the same as those in formula (1), and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • each R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that the total number of carbon atoms of R 4 substituted for each hydroxyethoxy group is 4 or less.
  • preferred examples and specific examples of R 2 and n are the same as those in the general formula (1).
  • R 3 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
  • preferred examples and specific examples thereof are represented by the general formula (1 ) Is the same as when R 1 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
  • R 3 is more preferably a hydrogen atom or a methyl group.
  • At least one of R 3 at the 3-position and the 5-position is preferably a hydrogen atom with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton
  • R 3 at the 2nd and 5th positions is preferably a hydrogen atom with respect to the phenyl carbon atom directly bonded to the 3rd carbon atom of the indoline skeleton.
  • all R 3 are preferably hydrogen atoms.
  • R 4 is an alkyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, and the like.
  • R 4 is particularly preferably a hydrogen atom or a methyl group.
  • dihydroxy compound represented by the general formula (1) of the present invention examples include 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indole-2- on 3,3-bis (4- (2-hydroxy-2-methylethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxy-1-methylethoxy) Phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -1-phenyl-1H-indole-2-one 3,3- Bis (3-ethyl-4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis (4- (2-hydroxyethoxy)
  • one of the raw materials is an N-phenylisatin compound represented by the following general formula (2).
  • R 2 and n are the same as those in the general formula (1).
  • Preferred examples and specific examples of R 2 and n are the same as those in the general formula (1).
  • N-phenylisatin compound represented by the general formula (2) examples include 1-phenyl-1H-indole-2,3-dione 1- (4-methylphenyl)- Examples thereof include 1H-indole-2,3-dione 1- (2-methylphenyl) -1H-indole-2,3-dione 1- (4-methoxyphenyl) -1H-indole-2,3-dione.
  • Another raw material is a phenoxy alcohol compound represented by the following general formula (3).
  • R, R 1 and m are the same as those in the general formula (1).
  • Preferred examples and specific examples relating to R, R 1 and m are also the same as those in the general formula (1).
  • a compound represented by the general formula (6) is preferable.
  • R 3 and R 4 are the same as those in the general formula (4).
  • Preferred examples and specific examples relating to R 3 and R 4 are also the same as those in the general formula (4).
  • Specific examples of the compound represented by the general formula (6) include 2-phenoxyethanol 2-phenoxypropanol 1-phenoxy-2-propanol 2- (2-methylphenoxy) ethanol 2- (2 -Ethylphenoxy) ethanol 2- (2,6-dimethylphenoxy) ethanol 2- (2,5-dimethylphenoxy) ethanol 2- (2,3,6-trimethylphenoxy) ethanol and the like.
  • an N-phenylisatin compound represented by the general formula (2) and a phenoxy alcohol compound represented by the general formula (3) are reacted to give a general formula (1) having an indoline skeleton.
  • the method for producing the dihydroxy compound represented by) will be described in detail.
  • the condensation reaction is carried out by reacting the above N-phenylisatin compound with a phenoxy alcohol compound, usually in the presence of an acid catalyst.
  • an N-phenylisatin compound and a phenoxyalcohol compound are reacted in the presence of an acid catalyst, and the resulting reaction mixture is neutralized with an alkali, and then crystallized and filtered according to a known method to produce primary crystals. An analysis filtrate is obtained.
  • the charged molar ratio of the phenoxy alcohol compound to the N-phenyl isatin compound is not particularly limited as long as it is the theoretical value (2.0) or more, but preferably 3.0 times the molar amount or more. More preferably, it is used in the range of 3.5 to 20 times the molar amount, particularly preferably in the range of 4.0 to 15 times the molar amount.
  • the acid catalyst include hydrochloric acid, hydrogen chloride gas, 60-98% sulfuric acid, 85% phosphoric acid and other inorganic acids, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, etc.
  • Hydrogen chloride gas is preferred.
  • the amount of such an acid catalyst used varies depending on the reaction conditions. For example, in the case of hydrogen chloride gas, after replacing the air in the reaction system with an inert gas such as nitrogen gas, hydrogen chloride gas is blown, the hydrogen chloride gas concentration in the gas phase in the reaction vessel is preferably 75 to 100% by volume, and the hydrogen chloride concentration in the reaction solution is preferably saturated.
  • hydrochloric acid it is used in the range of 5 to 70 parts by weight, preferably in the range of 10 to 40 parts by weight, more preferably in the range of 20 to 30 parts by weight with respect to 100 parts by weight of the phenoxy alcohol compound.
  • sulfuric acid is used as the acid catalyst, there is a concern that the hue of the compound deteriorates because sulfuric acid remains in the target compound, and when using a heteropolyacid as the acid catalyst, the reaction temperature needs to be increased. Therefore, the reaction selectivity is not efficient and is not efficient.
  • a co-catalyst may be used together with the acid catalyst as necessary.
  • the reaction rate can be accelerated by using thiols as a co-catalyst.
  • thiols include alkyl mercaptans and mercaptocarboxylic acids, preferably alkyl mercaptans having 1 to 12 carbon atoms and mercaptocarboxylic acids having 1 to 12 carbon atoms, such as methyl mercaptan.
  • alkali metal salts such as ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, and sodium salts thereof, thioacetic acid, thioglycolic acid, ⁇ -mercaptopropionic acid, and the like. Moreover, these can be used individually or in combination of 2 or more types.
  • the amount of thiols used as a co-catalyst is usually in the range of 0.5 to 20 mol%, preferably in the range of 2 to 10 mol%, relative to the starting N-phenylisatin compound.
  • the reaction solvent As the reaction solvent, the starting N-phenylisatin compound and the phenoxyalcohol compound have a low melting point, and if there is no problem in operability, it is not necessary to use a solvent. It may be used for reasons such as improving the reaction rate.
  • the reaction solvent is not particularly limited as long as it does not distill from the reactor at the reaction temperature and is inert to the reaction.
  • aromatic hydrocarbons such as toluene and xylene, methanol, n-propyl alcohol, isobutyl alcohol, etc.
  • aliphatic alcohols such as hexane, heptane and cyclohexane, carboxylic acid esters such as ethyl acetate and butyl acetate, and mixtures thereof. Of these, aliphatic alcohols are preferably used.
  • a small amount of water may be added as necessary.
  • the acid catalyst is hydrogen chloride gas
  • water is preferable for promoting the absorption of hydrogen chloride gas by the catalyst.
  • the addition amount is preferably in the range of 0.5 to 15.0 parts by weight with respect to 100 parts by weight of the phenoxy alcohol compound.
  • the reaction temperature varies depending on conditions such as the catalyst used, but is preferably in the range of 20 to 70 ° C, more preferably in the range of 30 to 60 ° C.
  • the reaction pressure is usually carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under pressure or reduced pressure so that the reaction temperature falls within the above range. If the reaction is carried out under such conditions, the reaction is usually completed in about 1 to 30 hours.
  • the end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis.
  • the end point of the reaction is preferably the point at which the unreacted N-phenylisatin compound disappears and no increase in the desired product is observed.
  • the reaction yield based on the phenoxy alcohol compound is usually about 75 to 95 mol%.
  • an alkaline solution such as aqueous ammonia or sodium hydroxide solution is added to the resulting reaction mixture to neutralize the acid catalyst, and the reaction containing the dihydroxy compound represented by the general formula (1) of the present invention A finished mixture is obtained.
  • water washing treatment is performed to add water and an insoluble organic solvent to the water and sufficiently stir to separate the oil layer. Do. As the organic solvent used at this time, it is necessary to dissolve the dihydroxy compound of the general formula (1) and to have a low solubility in water.
  • an aromatic hydrocarbon such as toluene or xylene, an aliphatic hydrocarbon such as cyclohexane or n-heptane, an aliphatic ketone such as methyl isobutyl ketone, or an alcohol solvent such as butanol is employed.
  • the organic solvent layer obtained after the neutralization and washing with water is partially removed by distillation, if necessary, and then the organic solvent is heated as it is or once to a uniform solution, cooled or appropriately crystallized.
  • crystals are precipitated by adding a precipitation solvent or a poor solvent and cooling, a crude or high-purity target product can be obtained by filtering the crystals.
  • the target product obtained above can be further purified by recrystallization using a solvent.
  • Organic solvents used at this time include aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and alcohols such as butanol.
  • a solvent is mentioned, These can be used individually or in mixture of 2 or more types. Instead of the above crystallization operation, after completion of the reaction, the reaction solvent and the like are concentrated under reduced pressure, and the residue is purified by column chromatography or the like to obtain a high purity product.
  • the dihydroxy compound represented by the general formula (1) may contain, a 1EO body (monohydroxyalkoxy body) represented by the following general formula (7), the following general formula (8) And a multi-EO body represented by the formula (a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group).
  • the N-phenylisatin compound represented by the general formula (2) is reacted with the phenoxy alcohol compound represented by the general formula (3) to obtain the compound represented by the general formula (1).
  • the above 1EO body is represented by the following general formula (7).
  • R, R 1 , R 2 , m and n are the same as those in the general formula (1).
  • Preferred examples and specific examples relating to R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the above multi-EO body is represented by the following general formula (8).
  • R, R 1 , R 2 , m, and n are the same as those in the general formula (1), and k each independently represents an integer of 1 to 5, provided that k is 1 at the same time.
  • R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the 3EO body which is a compound more likely to be contained in the multi-EO body represented by the general formula (8) is represented by the following general formula (9). (In the formula, R, R 1 , R 2 , m and n are the same as those in the general formula (1).) Preferred examples and specific examples relating to R, R 1 , R 2 , m, and n are the same as those in the general formula (1).
  • the reaction proceeds under mild reaction conditions, and the target dihydroxy compound is obtained in a higher yield and / or higher conversion rate than the conventional reaction. Can be obtained.
  • the dihydroxy compound represented by the general formula (1) obtained by the production method of the present invention does not contain impurities of the multi-EO body represented by the above-mentioned 1EO body and 3EO body and has high purity. Excellent optical properties such as thermal stability and product hue. Since the dihydroxy compound represented by the general formula (1) obtained by the production method of the present invention has high purity, it is expected to have high heat resistance and high refractive index, and particularly excellent effects in polycarbonate for optical materials. There is expected.
  • polycarbonate by using high-molecular weight polycarbonate, it has excellent transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc., optical applications such as optical discs and lenses, and engineering plastics in the automotive field, electrical / electronic field, various types. Use in various fields such as containers can be expected.
  • Polycarbonate oligomers can be used not only as raw materials for producing high molecular weight polycarbonate by various polymerization methods, but also as surface modifiers, flame retardants, ultraviolet absorbers, fluidity modifiers, plasticizers. Also, it can be widely used as additives such as polymer modifiers such as resin alloy solubilizers.
  • the dihydroxy compound of the present invention obtained by the production method of the present invention uses an epoxy resin, an oxetane resin, an acrylic resin, a polyester, a polyarylate, and a polyether ether in addition to the polycarbonate using a terminal hydroxy group.
  • a resin raw material such as ketone, polysulfone, novolak, and resol
  • other photosensitive composition raw material, resist additive, developer, and antioxidant can also be expected.
  • it can be expected to be used as an acrylic monomer or acrylic resin raw material such as diacrylate obtained by reacting the dihydroxy compound of the present invention with acrylic acid or the like, and as an optical hard coating material using them.
  • Refractive index measuring device Refractometer RA-500N manufactured by Kyoto Electronics Industry Co., Ltd. Measuring method: A THF solution (THF refractive index of 1.40) having a concentration of 10, 15, or 30% was adjusted, and the refractive index of the measurement compound was calculated from the refractive index of the solution by extrapolation. 3.
  • Purity measurement device CLASS-LC10 manufactured by Shimadzu Corporation Pump: LC-10ATvp Column oven: CTO-10Avp Detector: SPD-10Avp Column: Shim-pack CLC-ODS 6mm inner diameter, 150mm length Oven temperature: 50 ° C Flow rate: 1.0ml / min Mobile phase: (A) Methanol, (B) 0.2 vol% acetic acid water Gradient condition: (A) Volume% (time from the start of analysis) 60% (0min) ⁇ 60% (20min) ⁇ 100% (40min) ⁇ 100% (50min) Sample injection volume: 20 ⁇ l Detection wavelength: 280nm
  • the obtained oil layer was heated to 160 ° C., the solvent was removed by distillation under a reduced pressure of 1.0 kPa, then cooled, 582.2 g of toluene was added at 110 ° C., and 72.3 g of methanol at 70 ° C. Was added. Thereafter, the mixture was cooled to 30 ° C., and the precipitated crystals were separated by filtration to obtain 61.4 g of crude crystals as white crystals. After adding 226.5 g of 1-butanol to 55.5 g of the obtained crude crystals and dissolving at 110 ° C., 112.7 g of 1-butanol was removed by distillation under normal pressure, then cooled to 30 ° C. and precipitated.
  • Example 2 Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one-2
  • 0.35 g (0.0024 mol) of n-octyl mercaptan was charged, and 20.7 g of methanesulfonic acid was added while maintaining the temperature in the system at 50 to 55 ° C., and then at 50 to 55 ° C.
  • the production method of the present invention is a high-purity dihydroxy containing almost no impurities of the 1EO body represented by the general formula (7) and the 3EO body represented by the general formula (9). It was confirmed that this was a method capable of obtaining a compound, and it became clear that it was useful as an industrial production method.
  • the N-phenylisatin compound represented by the general formula (2) and a phenol compound were reacted with reference to the production method described in JP-T-2010-505011, etc., and then the obtained indoline was obtained.
  • Step 1 Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one (Step 1) Production of 3,3-bis (4-hydroxyphenyl) -1-phenyl-1H-indole-2-one 225.9 g (2.40 mol) of phenol in a four-necked flask equipped with a thermometer, stirrer and condenser. ), 44.6 g (0.20 mol) of 1-phenyl-1H-indole-2,3-dione was charged, and the reaction vessel was purged with nitrogen, and then hydrogen chloride gas was blown at 40 ° C. The hydrogen gas concentration was 95% or more.
  • the production method of the present invention is a production method characterized by being specifically higher than the reactivity with a compound.
  • this reactivity is high, so that the reaction proceeds at a high yield and / or high conversion rate or the reaction time can be shortened as compared with a conventionally known production method, Since the reaction proceeds under mild conditions, it can be an industrially advantageous production method.
  • the production method of the present invention is useful as an industrial production method because a highly pure dihydroxy compound containing almost no impurities can be obtained.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

Le problème à la base de la présente invention concerne un procédé de production d'un nouveau composé dihydroxy qui présente un squelette indoline. Le problème est résolu par un procédé dans lequel un composé dihydroxy représenté par la formule générale (1) est produit par réaction d'un composé de type N-phénylisatine représenté par la formule générale (2) et d'un composé de type phénoxyalcool représenté par la formule générale (3). Formule (1) (Dans la formule, R représente un groupe alkylène en C2-6, R1 et R2 représentent chacun indépendamment un groupe alkyle en C1-8 ou un groupe alcoxy en C1-8, m représente un entier de 0-3 et n représente un nombre entier de 0 à 2; cependant, lorsque m est égal ou supérieur à 2, R1 peut être identique ou différent et, lorsque n est égal à 2, R2 peut être identique ou différent.) Formule (2) (Dans la formule, R2 et n sont les mêmes que dans la formule générale (1).) Formule (3) (Dans la formule, R, R1 et m sont les mêmes que dans la formule générale (1).)
PCT/JP2017/011627 2016-03-28 2017-03-23 Procédé de production d'un nouveau composé dihydroxy Ceased WO2017170096A1 (fr)

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JP2018509160A JPWO2017170096A1 (ja) 2016-03-28 2017-03-23 新規なジヒドロキシ化合物の製造方法
CN201780020587.4A CN108884039A (zh) 2016-03-28 2017-03-23 新颖的二羟基化合物的制造方法
KR1020187029703A KR102408697B1 (ko) 2016-03-28 2017-03-23 신규한 디히드록시 화합물의 제조방법

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CN108884039A (zh) 2018-11-23
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