CN105899497B - Novel bis- (hydroxyphenyl) benzoxazoles compounds - Google Patents

Novel bis- (hydroxyphenyl) benzoxazoles compounds Download PDF

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CN105899497B
CN105899497B CN201480064306.1A CN201480064306A CN105899497B CN 105899497 B CN105899497 B CN 105899497B CN 201480064306 A CN201480064306 A CN 201480064306A CN 105899497 B CN105899497 B CN 105899497B
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hydroxyphenyl
bis
carbon atom
benzoxazoles
compounds according
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CN105899497A (en
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西原匡彦
芦田仁
芦田一仁
水野卓巳
伊藤贵敏
三原正稔
岩井利之
中井猛夫
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Osaka Institute of industrial technology of local independent administrative legal person
Honshu Chemical Industry Co Ltd
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Osaka Institute Of Industrial Technology Of Local Independent Administrative Legal Person
Honshu Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/42—Oxazoles
    • A61K31/423—Oxazoles condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic

Abstract

The issue of the present invention is to provide a kind of novel bis- (hydroxyphenyl) benzoxazoles compounds, its resin raw material as epoxy resin or polybenzoxazoles resin etc., or medicine, pesticide, dyestuff and electronic material or their intermediate, raw material and it is useful.As the solution of the above subject, to provide by the following general formula (1) represented by bis- (hydroxyphenyl) benzoxazoles compounds.(in formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；R2Indicate hydrogen atom, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；The cycloalkylidene of A expression carbon atom number 5~10；N indicates 0 or 1~4 integer.)

Description

Novel bis- (hydroxyphenyl) benzoxazoles compounds
Technical field
The present invention relates to novel bis- (hydroxyphenyl) benzoxazoles compounds.Specifically, to be related to as epoxy resin Deng resin raw material, or medicine, pesticide, dyestuff and electronic material or their intermediate, raw material and useful bis- (oxybenzenes Base) benzoxazoles compound.
Background technique
Bis- (hydroxyphenyl) benzoxazoles compounds as epoxy resin etc. resin raw material in use, due to its stretch it is strong Degree, bending strength, impact strength, heat resistance, excellent electrical characteristic, therefore as raw material by expectation.
As such bis- (hydroxyphenyl) benzoxazoles classes, conventionally, there is known 2,2 '-two (4- hydroxyphenyl) -6,6 '-bis- benzene And (the patent such as oxazole or bis- [2- (4- the hydroxyphenyl) -5- benzoxazolyl] hexafluoropropane of 2,2- with 2,2- hexafluoro propylidene Document 1, patent document 2).
Here, 2,2 '-two (4- hydroxyphenyl) -6,6 '-bis- benzoxazoles have high-melting-point, in addition, dissolution in a solvent Property it is low, therefore industrially implement when there are problems in workability or operability, in addition, with 2,2- hexafluoro propylidene 2, Bis- [2- (4- hydroxyphenyl) -5- benzoxazolyl] the hexafluoropropane heat resistances of 2- are insufficient.
Therefore, workability or operability are good, and heat resistance also excellent bis- (oxybenzenes with novel chemical structure Base) benzoxazoles compound exploitation by tight demand.
Existing technical literature
Patent document
Patent document No. 5270432 bulletins of 1 U.S. Patent No.
2 Japanese Unexamined Patent Publication 2007-262204 bulletin of patent document
Summary of the invention
The issue of the present invention is to provide the resin raw material as epoxy resin or polybenzoxazoles resin etc., or medicine, Pesticide, dyestuff and electronic material or their intermediate, raw material and useful novel bis- (hydroxyphenyl) benzoxazoles chemical combination Object.
The present inventors further investigate the problem of above-mentioned bis- (hydroxyphenyl) benzoxazoles compounds, as a result send out Now by using cycloalkylidene as the center framework of bis- (hydroxyphenyl) benzoxazoles compounds, can get solvent solubility, heat-resisting Excellent novel bis- (hydroxyphenyl) the benzoxazoles compounds of the balance of property, thereby completing the present invention.
According to the present invention, it is possible to provide bis- (hydroxyphenyl) benzoxazoles compounds represented by by the following general formula (1).
General formula (1)
(in formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；R2Table Show hydrogen atom, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；A indicates carbon atom number 5 ~10 cycloalkylidene；N indicates 0 or 1~4 integer.)
Bis- (hydroxyphenyl) benzoxazoles compounds of the invention are to have cycloalkylidene skeleton in center framework, due in this way Center framework there is alicyclic structure, therefore fusing point is lower and solvent solubility is also good.
In addition, using bis- (hydroxyphenyl) benzoxazoles compounds of the invention as the resin of raw material, it can be expected that with bis- with 2,2- [2- (4- hydroxyphenyl) -5- benzoxazolyl] hexafluoropropane is that the resin of raw material is compared, and heat resistance is also more excellent.
Specific embodiment
Hereinafter, explaining bis- (hydroxyphenyl) benzoxazoles compounds of the invention in detail.
In bis- (hydroxyphenyl) benzoxazoles compounds represented by (1) of the invention by above-mentioned general formula, in formula, by R1、R2 Shown in carbon atom number 1~8 alkyl be straight-chain, branched or cricoid alkyl, preferably the alkyl of carbon atom number 1~4 or The naphthenic base of carbon atom number 5~8, the straight-chain of more preferable carbon atom number 1~4 or the alkyl of branched.
As such alkyl, specifically, can for example enumerate methyl, ethyl, isopropyl, tert-butyl, isobutyl group, hexamethylene Base, cyclopenta etc..
It, can be through halogen atom, alkoxy, phenyl etc. in the range of not interfering effect of the invention for such alkyl Replace, but preferably without substituted alkyl.
In addition, the alkoxy of carbon atom number 1~8 is straight-chain, branched or cricoid alkoxy in formula, preferably carbon is former The alkoxy of subnumber 1~4 or the cycloalkyloxy of carbon atom number 5~8, the straight-chain of more preferable carbon atom number 1~4 or branched Alkoxy.As such alkoxy, specifically, can for example enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy, just Butoxy, cyclopentyloxy, cyclohexyloxy etc..It, can be through in the range of not interfering effect of the invention for such alkoxy Halogen atom, alkoxy, phenyl etc. replace, but preferably without substituted alkoxy.
In formula, as by R1、R2Shown in phenyl, the preferably phenyl of unsubstituted.However, not interfered for phenyl In the range of effect of the invention, can also alkoxy, the halogen atom etc. of alkyl, methoxyl group through methyl etc. etc. replace.
In formula, as by R1、R2Shown in halogen atom, specifically, it is former to enumerate fluorine atom, chlorine atom, bromine atom, iodine Son.
In above-mentioned substituent R1、R2In, preferably R1For alkyl or phenyl, more preferable R1For alkyl；It is preferred that R2For alkyl, phenyl Or hydrogen atom, more preferable R2For hydrogen atom.
In addition, the substituent R of hydroxyphenyl1Substitution number n be indicate 0 or 1~4 integer, preferably 0,1 or 2, more preferably 0 or 1, particularly preferred 0.R1The position of substitution preferably with respect to hydroxyl be ortho position or contraposition, the position of substitution of hydroxyl relative to When the bonding position of benzoxazoles skeleton is contraposition, R1The position of substitution preferably with respect to hydroxyl be ortho position.
The position of substitution of the hydroxyl of hydroxyphenyl, the position preferably with respect to the bonding of benzoxazoles skeleton are contraposition, meta position, spy It You Xuanwei not align.
In above-mentioned general formula (1), in formula, A indicates that carbon atom number is 5~10 cycloalkylidene.
As such cycloalkylidene, specifically, can for example enumerate amyl- 1, the 1- diyl of ring, hexamethylene -1,1- diyl, ring Hept- 1,1- diyl, 3,3,5- 3-methyl cyclohexanol -1,1- diyl etc..
From the viewpoint of heat resistance, more preferable 3,3,5- 3-methyl cyclohexanol -1,1- diyls.
In turn, for such cycloalkanes skeleton, can replace through alkyl, preferably methyl, it is preferred that number is replaced to be 1~3.
As such bis- (hydroxyphenyl) benzoxazoles compounds of the invention, specifically, it is bis- for example to enumerate 1,1- [2- (4- hydroxyphenyl) -5- benzoxazolyl] -3,3,5- trimethyl-cyclohexanes,
1,1- bis- [2- (3,5- di-t-butyl -4- hydroxyphenyl) -5- benzoxazolyls] -3,3,5- trimethyl-cyclohexanes,
Bis- [2- (3- tert-butyl -4- the hydroxyphenyl) -5- benzoxazolyls] -3 of 1-, 3,5- trimethyl-cyclohexanes,
1,1- bis- [2- (4- hydroxyphenyl) -5- benzoxazolyl] hexamethylenes,
1,1- bis- [2- (3- tert-butyl -4- hydroxyphenyl) -5- benzoxazolyl] hexamethylenes,
1,1- bis- [2- (4- hydroxyphenyl) -5- benzoxazolyl] pentamethylene,
1,1- bis- [2- (4- hydroxyphenyl) -5- benzoxazolyl] cycloheptane,
1,1- bis- [2- (3- methyl -4- hydroxyphenyl) -5- benzoxazolyls] -3,3,5- trimethyl-cyclohexanes,
1,1- bis- [2- (4- hydroxyphenyl) -7- methyl -5- benzoxazolyls] -3,3,5- trimethyl-cyclohexanes,
1,1- bis- [2- (3- methyl -4- hydroxyphenyl) -5- benzoxazolyl] hexamethylenes,
1,1- bis- [2- (3- methyl -4- hydroxyphenyl) -5- benzoxazolyl] pentamethylene,
1,1- bis- [2- (3- phenyl -4- hydroxyphenyl) -5- benzoxazolyl] hexamethylenes etc..
Such as above-mentioned bis- (hydroxyphenyl) benzoxazoles compounds of the invention, manufacturing method are unrestricted.Such as The following method etc. can be enumerated.
(method 1)
It can enumerate, by double aminobenzenes of the following general formula (3) of bis- (hydroxyphenyl) benzoxazoles compounds of corresponding target Phenol (bisaminophenol) class and hydroxybenzoic acid class in organic solvent, carry out condensation reaction as raw material under heating Method (Japanese Unexamined Patent Publication 2007-262204 bulletin etc.).For the manufacturing method, elaboration for example will be in double amino phenols 1,1- bis- (3- amino -4- hydroxyphenyls) -3, the 4-HBA phenyl ester in 3,5- trimethyl-cyclohexanes, hydroxybenzoic acid class are made The case where for raw material.Its reaction equation for example by following formula represented by.
Reaction equation (1)
Hydroxyl as hydroxybenzoic acid class used in above-mentioned reaction, such as represented by can enumerating by the following general formula (2) Phenylamino benzoic acid esters.
General formula (2)
(in formula, R1And the R in n and general formula (1)1And n is identical)
In addition, in above-mentioned reaction, as the material molar ratio of double amino phenols and phenyl hydroxybenzoate class, generally For, relative to 1 mole of double amino phenols, phenyl hydroxybenzoate class is generally 2~5 moles of range, and preferably 2~3 rub Your range.It is preferable to use reaction dissolvents, such as N- alkylamide solvent, the biphenyl that can enumerate n-methyl-2-pyrrolidone etc. Deng aromatic hydrocarbon or their mixed solvent.The usage amount of solvent is in general, relative to double 1 parts by weight of amino phenols For the range of 1~20 parts by weight.In addition, the range that reaction temperature is 150~250 DEG C, reaction pressure is normal pressure, decompression, pressurization It is any, but for ease of remove by-product water or phenol, can also be depressurized.
Reaction is, such as reaction vessel is added in raw material, reaction dissolvent together, with inert gas replacement, then, is warming up to 150~180 DEG C or so of reaction temperature and stirring make decompression in system evaporate the water or phenol of by-product on one side, make on one side It is reacted.Then, further 200~250 DEG C or so will be warming up in system, to complete dehydration closed-loop reaction.Reaction terminates Afterwards, using well known purification process, the crude object and purified of object can be obtained by obtained reaction product.
For example, by obtained reaction solution is cooling or add water, make the solid or the crystallization that are precipitated or filter out reprecipitation, then It is cleaned with water, methanol, it is dry, so that object can be obtained.
In the above method, represented by double amino phenols are by the following general formula (3).
General formula (3)
(in formula, R2, R in A and general formula (1)2, A it is identical)
Therefore, as such double amino phenols, bis- (hydroxyphenyl) benzoxazoles compounds of the invention are corresponded to, specifically For, such as bis- (3- amino -5- methyl -4- hydroxyphenyl) rings of bis- (3- amino -4- hydroxyphenyl) hexamethylenes of 1,1-, 1,1- can be enumerated Bis- (the 3- amino -4- hydroxyphenyls) -3 of hexane, 1,1-, bis- (3- amino -4- hydroxyphenyl) rings penta of 3,5- trimethyl-cyclohexanes, 1,1- Bis- (3- amino -4- hydroxyphenyl) cycloheptane of alkane, 1,1- etc..
Such double amino phenols are for example shown in reaction equation (2), can by by corresponding bisphenol compound in nitric acid In the presence of nitrified, and make the nitro of obtained bis- (nitrophenol) compounds such as palladium carbon or nickel etc. plus hydrogen urge The well known reduction reaction (the Japanese Unexamined Patent Publication 2003-12611 bulletin, Japanese Unexamined Patent Publication that react etc. with hydrogen are carried out in the presence of agent 2003-81925 bulletin etc.) and obtain.
Reaction equation (2)
(in formula, R2, R in A and general formula (1)2, A it is identical)
(method 2)
As the other methods of bis- (hydroxyphenyl) benzoxazoles compounds of the invention are obtained, can enumerate to correspond to target Bis- (hydroxyphenyl) benzoxazoles compounds by represented by the following general formula (4) double nitrophenyl phenolics with by the following general formula (5) institute The methylbenzene phenols of expression is as raw material, and in organic solvent, preferably heating progress dehydrating condensation is anti-in the presence of a catalyst The method answered.
It illustrates for example, as bis- (nitrophenol) classes, with 1,1- bis- (3- nitro -4- hydroxyphenyls) -3,3,5- front three basic rings Hexane, as methylbenzene phenols, the case where with 2,6- di-t-butyl-p-methyl phenol as raw material.It is reacted by for example following Reaction equation (3) is represented.
Reaction equation (3)
In the above method, represented by double nitrophenyl phenolics are by the following general formula (4).
General formula (4)
(in formula, R2, R in A and general formula (1)2, A it is identical)
Therefore, as such double nitrophenyl phenolics, bis- (hydroxyphenyl) benzoxazoles compounds of the invention are corresponded to, specifically For, bis- (3- nitro -5- methyl -4- hydroxyphenyl) hexamethylenes of bis- (3- nitro -4- hydroxyphenyl) hexamethylenes of 1,1-, 1,1- can be enumerated Bis- (the 3- nitro -4- hydroxyphenyls) -3 of alkane, 1,1-, bis- (3- nitro -4- hydroxyphenyl) pentamethylene of 3,5- trimethyl-cyclohexanes, 1,1-, 1,1- bis- (3- nitro -4- hydroxyphenyl) cycloheptane etc..
Such double nitrophenyl phenolics, such as can be by the way that double nitrophenyl phenolics represented by aforementioned formula (4) will be corresponded to Bisphenols represented by the following general formula (6), for example actually without existing for other acid under the conditions of, existed with 50~80% nitric acid 5 DEG C of temperature below nitrify etc. (WO01/81293 bulletin, Japanese Unexamined Patent Publication 11-106365 public affairs in a known manner Report etc.) it is nitrified and is obtained.
General formula (6)
(in formula, R2, R in A and general formula (2)2, A it is identical)
Represented by the methylbenzene phenols of raw material is by the following general formula (5) in the above method.
General formula (5)
(in formula, R1, R in n and general formula (1)1, n it is identical)
Therefore, as such methylbenzene phenols, corresponding bis- (hydroxyphenyl) benzoxazoles compounds of the invention, specifically and Speech, such as 2,6- di-tert-butyl-4-methy phenol, 2,4- dimethyl -6- tert-butyl phenol, 2- tert-butyl -4- methyl can be enumerated Phenol, 2,4,6- pseudocuminols, 2- methoxyl group -4- methylphenol etc..
When above-mentioned reaction, the molar ratio of the raw material of double nitrophenyl phenolics and methylbenzene phenols, it is however generally that, relative to double nitre 1 mole of base phenol, methylbenzene phenols is generally 2~10 moles of range, preferably 3~5 moles of range.
Catalyst can also not use, but in order to improve yield, it is preferable to use.It is excellent as catalyst when using catalyst It is selected as iron (iron powder), sulphur or vulcanized sodium or their mixture, the amount of catalyst is double nitrophenols relative to raw material 1 mole of class, generally 0.01~3 mole of range, when being iron, preferably 0.1~0.3 mole of range, when being sulphur, preferably For 1.5~2.5 moles of range, more preferable 2 moles.
It is preferable to use reaction dissolvents, such as the virtue of halogenated aromatic compounds, biphenyl that can enumerate adjacent dichlorotoleune etc. etc. Fragrant race's hydrocarbon solvent, the alkyl naphthalenes of 2,6- dimethylnaphthalenes, 2,6- diisobutyl naphthalene etc., the amide of n-methyl-2-pyrrolidone etc. Solvent, the polyalkylene glycol ethers class or their mixture of tetraethyleneglycol dimethyl ether, dibutyl ethylene glycol ether etc..Solvent makes Dosage relative to double 1 parts by weight of nitrophenyl phenolic, the preferably range of 1~50 parts by weight, more preferably 10~40 parts by weight Range.
Reaction temperature is preferably 160~200 DEG C of range, more preferably 170~190 DEG C of range.Reaction pressure is normal Pressure is pressurizeed, any, the boiling point of reaction dissolvent under normal pressure situation etc. lower than reaction temperature, in order to mention in decompression High-temperature can pressurize to adjust.
Reaction is, such as double nitrophenyl phenolics of specified amount, methylbenzene phenols, catalyst and instead are added in the reaction vessel Solvent is answered, is warming up to defined reaction temperature while stirring under nitrogen flowing, and maintaining to be reacted at this temperature.
After reaction, by obtained reaction mixture, according to general method, by suitably using catalyst point From method well known to the evaporating separation, crystallization filtering is precipitated etc. of, low boiling point component, bis- (hydroxyphenyl) the benzos evils of object can be obtained The semifinished product of azole, further according to needs, as long as again crystallization filtering is precipitated, the methods of post separation is purified, can be obtained To high-purity product.
For example, the crystallization is filtered out when crystallization is precipitated, i.e., by cooling down reaction solution directly cooling or addition lean solvent Crude or high-purity object can be obtained.Alternatively, after reaction, by being concentrated under reduced pressure reaction dissolvent etc., by gained Residue is purified with column chromatography etc., so that high-purity product can be obtained.
(method 3)
As another method of bis- (hydroxyphenyl) benzoxazoles compounds of the invention is obtained, method can be listed below: It obtains in above-mentioned general formula (1), n is 1 or more, and substituent R1At least one be the tertiary alkyl of tert-butyl etc., and/or replace Base R2For bis- (hydroxyphenyl) benzoxazoles compounds as intermediate of the tertiary alkyl of tert-butyl etc., from obtained conduct Bis- (hydroxyphenyl) benzoxazoles of mesosome replaced through tertiary alkyl pass through debutylize etc. under the presence and heating of acid catalyst Well known method (Japanese Unexamined Patent Publication 2-169530 bulletin, Japanese Unexamined Patent Publication 8-143494 bulletin etc.), sloughs tert-butyl etc. Tertiary alkyl, be replaced to hydrogen atom to obtain target bis- (hydroxyphenyl) benzoxazoles method.
It describes for example using bis- (the 3- nitro -4- hydroxyphenyls) -3 of 1, the 1- as bis- (nitrophenol) classes, 3,5- trimethyls Hexamethylene, the 2,6-di-tert-butyl p-methylphenol as methylbenzene phenols is as raw material, from the reaction institute according to the above method 2 Bis- [2- (3,5- di-t-butyl -4- the hydroxyphenyl) -5- benzoxazolyls] -3 of obtained 1, the 1- as intermediate, 3,5- trimethyls Hexamethylene sloughs tert-butyl to obtain bis- [2- (4- the hydroxyphenyl) -5- benzoxazolyls] -3 of 1,1- of target, 3,5- front threes The case where butylcyclohexane.
Its react for example by following reaction equations (4) represented by.
Reaction equation (4)
In the reaction of above-mentioned debutylizeization, as acid catalyst, preferably p-methyl benzenesulfonic acid, p-toluenesulfonic anhydride etc. is high boiling The acid of point, as the amount of catalyst, relative to bis- (hydroxyphenyl) benzoxazoles compounds, the range of preferably 1~50 mole %, The range of more preferable 10~30 moles of %.When reaction, solvent is generally used, phenol, toluene can be enumerated as preferred solvent The phenols such as phenol.The amount of solvent is not particularly limited, but generally relative to bis- 1 parts by weight of (hydroxyphenyl) benzoxazoles compound, Preferably 10~500 parts by weight or so.Reaction temperature is generally 200~250 DEG C or so of range.
Reaction is, such as tert-butyl substitution-bis- (hydroxyphenyl) benzoxazoles chemical combination of specified amount are added in the reaction vessel Object, catalyst and reaction dissolvent are warming up to defined reaction temperature while stirring under nitrogen atmosphere, and are maintaining the temperature Under reacted.
After reaction, for obtaining object from reaction mixture, it can be used and purifying well known to crystallization, concentration etc. is precipitated Method.Such as by adding solvent or water to reaction solution, or concentration or a combination thereof crystallize, by the object of precipitation Crystallization filter out.Before implementing aforesaid operations to reaction solution, can by be rinsed with water after the solvent that is separated from water is added come Remove water-soluble impurity.In addition, being removed by the neutralisation treatment of alkaline aqueous solution or by being rinsed with water etc. from reaction solution Catalyst, or after carrying out by concentration the removing processing of low boilers etc., can also be chromatographed and be purified by column.
Embodiment
(Production Example)
The synthesis of bis- (3- nitro -4- the hydroxyphenyl) -3,3,5- trimethyl-cyclohexanes of 1,1-
By bis- (4- the hydroxyphenyl) -3,3,5- trimethyl-cyclohexane 9.32g (0.030mol) of 1,1-, methylene chloride 50ml, with It is cooling after the three-necked flask of 100ml is added with magnetite for stirring, with while maintaining reaction temperature is at 0~5 DEG C 3 hours and drips 70% nitric acid 6.10g (0.067mol).In turn, reaction 3 hours is carried out while maintaining the temperature.After reaction, mistake Reaction solution is filtered, 1% sodium bicarbonate aqueous solution is implanted sequentially in the crystallization filtered out, distilled water sufficiently cleans.After drying, obtain Bis- (3- nitro -4- the hydroxyphenyl) -3,3,5- trimethyl-cyclohexane 6.0g of the 1,1- of purity 99.9% (high performance liquid chromatography).
(embodiment 1)
The conjunction of bis- [2- (3,5- di-t-butyl -4- hydroxyphenyl) -5- the benzoxazolyl] -3,3,5- trimethyl-cyclohexanes of 1,1- At
By 1,1- bis- (3- nitro -4- hydroxyphenyl) -3,3,5- trimethyl-cyclohexane 600.5mg (1.50mmol), 2,6- bis- T-butyl-p-methylphenol 1322.3mg (6.00mmol), sulphur powder 96.2mg (3.00mmol) and iron powder 16.8mg (0.30mmol), after the test tube of 100ml is added with o-dichlorohenzene 8ml, at normal temperature, argon gas will be replaced as in test tube.
Then, it is warming up to 180 DEG C while stirring, carries out reaction 48 hours while making it flow back in the temperature. After reaction, low boilers are evaporated under reduced pressure, concentrated residue is purified with silica gel column chromatography, obtain the bis- [2- (3,5- of 1,1- Di-t-butyl -4- hydroxyphenyl) -5- benzoxazolyl] -3,3,5- trimethyl-cyclohexane 571.5mg.Relative to bis- (the 3- nitre of 1,1- Base -4- hydroxyphenyl) -3,3,5- trimethyl-cyclohexane yield be 50%.
Molecular weight (HRMS/MALDI-TOF): 769.4964 (M+H)+
1H NMR qualification result (300MHz, solvent: CDCl3, internal standard: tetramethylsilane)
[table 1]
(embodiment 2)
The synthesis of bis- [2- (4- hydroxyphenyl) -5- the benzoxazolyl] -3,3,5- trimethyl-cyclohexanes of 1,1-
By bis- [2- (3,5- di-t-butyl -4- the hydroxyphenyl) -5- benzoxazolyls] -3,3 of 1,1- synthesized by embodiment 1, 5- trimethyl-cyclohexane 154.2mg (0.20mmol), phenol 2.91g and p-toluenesulfonic anhydride 8.4mg (4.9 × 10-2Mmol) add Enter the pressure-resistant test tube of 10ml and seal, be warming up to 210 DEG C while stirring in microwave reaction device, is carried out in the temperature Reaction 4 hours.
It further heats up to after 230 DEG C, carries out reaction 3 hours, then heat to 250 DEG C, and carry out reaction 5 hours.
It is cooled to room temperature after reaction, obtained liquid after reaction is added to the water, it is water-soluble that alkalinity is further added Liquid is neutralized to pH6 or so, removes water layer.Obtained oil reservoir is purified with silica gel column chromatography, obtains bis- [2- (the 4- oxybenzenes of 1,1- Base) -5- benzoxazolyl] -3,3,5- trimethyl-cyclohexane 42.0mg.Relative to the bis- [2- (3,5- di-t-butyl -4- hydroxyls of 1,1- Phenyl) -5- benzoxazolyl] -3,3,5- trimethyl-cyclohexane yield be 39%.
344 DEG C of fusing point (differential scanning calorimetry)
Molecular weight (HRMS/MALDI-TOF): 545.2461 (M+H)+
1H NMR qualification result (300MHz, solvent: THF-d8, internal standard: tetramethylsilane)
[table 2]
(comparative example)
Make 2,2 '-two (4- hydroxyphenyl) -5 synthesized in method identical with embodiment, 5 '-bis- benzoxazoles (comparative example Compound) with the obtained compound of embodiment 2 be dissolved in methanol, toluene, methyl iso-butyl ketone (MIBK) at room temperature respectively (MIBK), saturated solution is made.The supernatant of saturated solution is extracted, concentration is measured with high performance liquid chromatography.Respective measurement knot Fruit is shown in following tables.It should be noted that the fusing point of comparative example compound is 410 DEG C (differential scanning calorimetry).
It is well understood by above-mentioned result, benzoxazoles compound of the invention is in methanol, toluene, MIBK each solvent Dissolubility is very excellent compared with the compound of comparative example.

Claims (71)

1. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that represented by by the following general formula (1),
In formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；R2Indicate that hydrogen is former Son, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；A indicates carbon atom number 5~10 Cycloalkylidene；N indicates 0 or 1~4 integer.
2. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R1For carbon atom number 1~8 Straight-chain, branched or cricoid alkyl, straight-chain, branched or the cricoid alkoxy of carbon atom number 1~8, phenyl or Halogen atom.
3. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R1For carbon atom number 1~4 Alkyl, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, the cycloalkyloxy of carbon atom number 5~8, phenyl Or halogen atom.
4. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R1For carbon atom number 1~4 Straight-chain or the alkyl of branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen atom of branched.
5. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R1For methyl, ethyl, different Propyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, ring Amoxy, cyclohexyloxy, phenyl or halogen atom.
6. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R2For hydrogen atom, carbon atom Straight-chain, branched or the cricoid alkyl of number 1~8, straight-chain, branched or the cricoid alkoxy of carbon atom number 1~8, Phenyl or halogen atom.
7. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R2For hydrogen atom, carbon atom The alkyl of number 1~4, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, carbon atom number 5~8 cycloalkanes oxygen Base, phenyl or halogen atom.
8. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R2For hydrogen atom, carbon atom Alkoxy, phenyl or the halogen of the alkyl of the straight-chain of number 1~4 or branched, the straight-chain of carbon atom number 1~4 or branched are former Son.
9. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that R2For hydrogen atom, methyl, Ethyl, isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth Oxygroup, cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
10. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that A is amyl- 1, the 1- bis- of ring Base, hexamethylene -1,1- diyl or cycloheptyl -1,1- diyl.
11. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that n 0,1 or 2.
12. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
13. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
14. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 1, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to position be bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be opposite In hydroxyl be ortho position.
15. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that represented by by the following general formula (1),
In formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom, R2Indicate that hydrogen is former Son, the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom, A indicate former through methyl substituted carbon The cycloalkylidene of subnumber 5~10, n indicate 0 or 1~4 integer.
16. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R1For carbon atom number 1~ 8 straight-chain, branched or cricoid alkyl, the straight-chain of carbon atom number 1~8, branched or cricoid alkoxy, phenyl or Halogen atom.
17. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R1For carbon atom number 1~ 4 alkyl, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, the cycloalkyloxy of carbon atom number 5~8, phenyl Or halogen atom.
18. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R1For carbon atom number 1~ The alkyl of 4 straight-chain or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen atom of branched.
19. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R1For methyl, ethyl, Isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
20. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R2For hydrogen atom, carbon original Straight-chain, branched or the cricoid alkyl of subnumber 1~8, the straight-chain of carbon atom number 1~8, branched or cricoid alcoxyl Base, phenyl or halogen atom.
21. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of subnumber 1~4, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, carbon atom number 5~8 cycloalkanes oxygen Base, phenyl or halogen atom.
22. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of the straight-chain of subnumber 1~4 or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen of branched Atom.
23. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that R2For hydrogen atom, first Base, ethyl, isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, just Butoxy, cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
24. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that A is through 1~3 first The cycloalkylidene for the carbon atom number 5~10 that base replaces.
25. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that A 3,3,5- front three Basic ring hex- 1,1- diyl.
26. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that general formula (1) institute The compound of expression is bis- [2- (4- the hydroxyphenyl) -5- benzoxazolyls] -3 of 1,1-, 3,5- trimethyl-cyclohexanes.
27. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that general formula (1) institute The compound of expression is bis- [2- (3,5- di-t-butyl -4- the hydroxyphenyl) -5- benzoxazolyls] -3 of 1,1-, 3,5- 3-methyl cyclohexanols Alkane.
28. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that n 0,1 or 2.
29. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
30. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
31. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 15, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be phase It is ortho position for hydroxyl.
32. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that it is indicated by the following general formula (1),
In formula, R1Indicate former by the alkyl for the carbon atom number 1~8 that halogen atom or phenyl replace, the carbon replaced by halogen atom or phenyl Alkoxy, phenyl or the halogen atom of subnumber 1~8；R2Indicate hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~8 Alkoxy, phenyl or halogen atom, A indicate that the cycloalkylidene of carbon atom number 5~10, n indicate 0 or 1~4 integer.
33. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that R2For hydrogen atom, carbon original Straight-chain, branched or the cricoid alkyl of subnumber 1~8, straight-chain, branched or the cricoid alcoxyl of carbon atom number 1~8 Base, phenyl or halogen atom.
34. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of subnumber 1~4, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, carbon atom number 5~8 cycloalkanes oxygen Base, phenyl or halogen atom.
35. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of the straight-chain of subnumber 1~4 or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen of branched Atom.
36. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that R2For hydrogen atom, first Base, ethyl, isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, just Butoxy, cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
37. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that n 0,1 or 2.
38. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
39. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
40. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 32, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be phase It is ortho position for hydroxyl.
41. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that it is indicated by the following general formula (1),
In formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；R2Indicate that hydrogen is former Son, by the alkyl for the carbon atom number 1~8 that halogen atom or phenyl replace, the carbon atom number 1~8 that is replaced by halogen atom or phenyl Alkoxy, phenyl or halogen atom；A indicates that the cycloalkylidene of carbon atom number 5~10, n indicate 0 or 1~4 integer.
42. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that R1For carbon atom number 1~ 8 straight-chain, branched or cricoid alkyl, straight-chain, branched or the cricoid alkoxy of carbon atom number 1~8, phenyl or Halogen atom.
43. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that R1For carbon atom number 1~ 4 alkyl, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, the cycloalkyloxy of carbon atom number 5~8, phenyl Or halogen atom.
44. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that R1For carbon atom number 1~ The alkyl of 4 straight-chain or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen atom of branched.
45. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that R1For methyl, ethyl, Isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
46. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that n 0,1 or 2.
47. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
48. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
49. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 41, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be phase It is ortho position for hydroxyl.
50. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that it is indicated by the following general formula (1),
In formula, R1Indicate former by the alkyl for the carbon atom number 1~8 that halogen atom or phenyl replace, the carbon replaced by halogen atom or phenyl Alkoxy, phenyl or the halogen atom of subnumber 1~8；R2Indicate hydrogen atom, the alkyl of carbon atom number 1~8, carbon atom number 1~8 Alkoxy, phenyl or halogen atom；A indicate the cycloalkylidene through methyl substituted carbon atom number 5~10, n indicate 0 or 1~4 it is whole Number.
51. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that R2For hydrogen atom, carbon original Straight-chain, branched or the cricoid alkyl of subnumber 1~8, straight-chain, branched or the cricoid alcoxyl of carbon atom number 1~8 Base, phenyl or halogen atom.
52. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of subnumber 1~4, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, carbon atom number 5~8 cycloalkanes oxygen Base, phenyl or halogen atom.
53. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that R2It is former for hydrogen atom, carbon The alkyl of the straight-chain of subnumber 1~4 or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen of branched Atom.
54. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that R2For hydrogen atom, first Base, ethyl, isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, just Butoxy, cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
55. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that A is through 1~3 first The cycloalkylidene for the carbon atom number 5~10 that base replaces.
56. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that A 3,3,5- front three Basic ring hex- 1,1- diyl.
57. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that n 0,1 or 2.
58. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
59. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
60. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 50, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be phase It is ortho position for hydroxyl.
61. a kind of bis- (hydroxyphenyl) benzoxazoles compounds, which is characterized in that it is indicated by the following general formula (1),
In formula, R1Indicate the alkyl of carbon atom number 1~8, the alkoxy of carbon atom number 1~8, phenyl or halogen atom；R2Indicate that hydrogen is former Son, by the alkyl for the carbon atom number 1~8 that halogen atom or phenyl replace, the carbon atom number 1~8 that is replaced by halogen atom or phenyl Alkoxy, phenyl or halogen atom；A indicate the cycloalkylidene through methyl substituted carbon atom number 5~10, n indicate 0 or 1~4 it is whole Number.
62. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that R1For carbon atom number 1~ 8 straight-chain, branched or cricoid alkyl, straight-chain, branched or the cricoid alkoxy of carbon atom number 1~8, phenyl or Halogen atom.
63. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that R1For carbon atom number 1~ 4 alkyl, the naphthenic base of carbon atom number 5~8, the alkoxy of carbon atom number 1~4, the cycloalkyloxy of carbon atom number 5~8, phenyl Or halogen atom.
64. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that R1For carbon atom number 1~ The alkyl of 4 straight-chain or branched, the straight-chain of carbon atom number 1~4 or alkoxy, phenyl or the halogen atom of branched.
65. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that R1For methyl, ethyl, Isopropyl, tert-butyl, isobutyl group, cyclohexyl, cyclopenta, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Cyclopentyloxy, cyclohexyloxy, phenyl or halogen atom.
66. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that A is through 1~3 first The cycloalkylidene for the carbon atom number 5~10 that base replaces.
67. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that A 3,3,5- front three Basic ring hex- 1,1- diyl.
68. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that n 0,1 or 2.
69. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition or meta position that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton,.
70. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that the hydroxyl of hydroxyphenyl The position of substitution is is contraposition relative to the position being bonded with benzoxazoles skeleton, and n is 0.
71. bis- (hydroxyphenyl) benzoxazoles compounds according to claim 61, which is characterized in that the hydroxyl of hydroxyphenyl It is contraposition that the position of substitution, which is relative to the position being bonded with benzoxazoles skeleton, and when n is 1 or 2, R1The position of substitution be phase It is ortho position for hydroxyl.
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