CN1768032A - Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone - Google Patents
Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone Download PDFInfo
- Publication number
- CN1768032A CN1768032A CN 200480009129 CN200480009129A CN1768032A CN 1768032 A CN1768032 A CN 1768032A CN 200480009129 CN200480009129 CN 200480009129 CN 200480009129 A CN200480009129 A CN 200480009129A CN 1768032 A CN1768032 A CN 1768032A
- Authority
- CN
- China
- Prior art keywords
- diallyl
- making
- dihydroxy diphenylsulphone
- reaction
- rearrangement reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention is characterized by subjecting 4,4'-diallyloxydiphenyl sulfone to a rearrangement reaction under microwave irradiation, preferably in molten state, to produce objective 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone efficiently in a short time, in high yield and in high purity. Further preferably, by carrying out said reaction in substantially oxygen-free atmosphere in the presence of at least one compound selected from a group consisting of an antioxidant, an organic basic compound and a chelate compound, the above-described object can be attained in more preferable manner.
Description
Technical field
The present invention relates to developer or the useful material 3 of polymeric additive, 3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone as the hotness recording materials.
Background technology
3,3 '-diallyl-4,4 '-dihydroxy diphenylsulphone is as the developer of hotness recording materials or the useful material of polymeric additive, once proposed 4,4 '-two allyloxy sulfobenzides carry out claisen (Cleisen) rearrangement reaction and make 3,3 '-diallyl-4, the method for 4 '-dihydroxy diphenylsulphone.For example, with 4,4 '-two allyloxy sulfobenzides are in the trichlorobenzene solvent, and in 216 to 219 ℃ were reacted 10 hours down, make mp139 to 144 ℃ material (patent documentation 1) with 93.3% yield.In addition, institute's alkalinity is scaled 4 below the 50ppm with sodium hydroxide, 4 '-two allyloxy sulfobenzides are in paraffin solvent, and in 205 to 210 ℃ were reacted 7 hours, and the HPLC ratio of components (purity) behind the purifying is 96.2% (spy opens 2002-30064) or 97.1% (spy opens 2002-30065).These methods all exist must carry out under the high temperature more than 200 ℃ for a long time, for example the shortcoming of reaction in 7 to 10 hours.In addition, with the molar ratio computing with respect to the raw material that drops into, yield is about 70% low yield.
Therefore seek more effective (reaction times is short, high yield), and the few high purity 3 of the by product of sneaking into, 3 '-diallyl-4, the exploitation of the method for making of 4 '-dihydroxy diphenylsulphone.
Summary of the invention
The present inventor studies for solving aforesaid problem, found that, 4,4 '-two allyloxy sulfobenzides carry out rearrangement reaction under microwave irradiation, thus can with before needed 7 hours to 10 hours be reflected at approximate number minute to about 30 minutes short period of time, make 3 with high yield, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone.
In addition, the present inventor further studies, found that, for suppressing side reaction, be preferable in the environment that anaerobic exists in fact, in being selected from by antioxidant, at least a kind of compound in the group that organo-alkali compound and sequestrant are formed exists down, more preferably at least a kind of compound in being selected from the group of being made up of organo-alkali compound and/or sequestrant exists down, carries out the rearrangement reaction of 4,4 '-two allyloxy sulfobenzides, especially the rearrangement reaction under microwave irradiation, can significantly shorten the reaction times thus, simultaneously with high yield, the mode that by product is few obtains purpose product 3,3 '-diallyl-4,4 '-dihydroxy diphenylsulphone.
That is, the present invention relates to
1.3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone is characterized in that, with 4,4 '-two allyloxy sulfobenzides carry out rearrangement reaction under microwave irradiation.
As the 1st described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out under molten state.
As the 2nd described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out under 230 to 300 ℃.
As the 1st or 2 described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxyl thionyl benzene is wherein carried out in the rearrangement reaction environment that substantially anaerobic exists.
As the 1st described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of alkaline matter.
As the 1st described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of antioxidant.
As the 6th described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein antioxidant is an xitix.
As the 1st described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of sequestrant.
As the 8th described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein sequestrant is ethylenediamine tetraacetic acid (EDTA) or the condensed ring class sequestrant that comprises the nitrogen atom aromatic nucleus.
As the 9th described 3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein condensed ring class sequestrant is a phenanthroline.
11.3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone is characterized in that, under microwave irradiation, 230 to 300 ℃, and alkaline matter or sequestrant in the presence of, carry out the rearrangement reaction of 4,4 '-two allyloxy sulfobenzides.
Preferred forms
The present invention is by with 4, and 4 '-two allyloxy sulfobenzides carry out rearrangement reaction under microwave irradiation implements.
As 4 of raw material of the present invention, 4 '-two allyloxy sulfobenzides are by with 4,4 '-dihydroxy diphenylsulphone and allyl chloride or allyl group bromination thing exist following the reaction to make (spy opens clear 60-169456) in alkali such as alkali metal hydroxide, alkaline earth metal hydroxidess in organic solvent.At raw material 4; contained alkali in 4 '-two allyloxy sulfobenzides when carrying out rearrangement reaction of the present invention, may promote 3; 3 '-diallyl-4, the generation of 2 '-dihydroxy diphenylsulphone or 5-(3-allyl group-4-hydroxyl) benzenesulfonyl-1-oxa--by products such as 2-methyl indan.Because of these by products are difficult for removing, when therefore being used as the developer of hotness recording materials, become the reason of quality reductions such as background fog, so preferred use 4, contained alkali number is 4,4 '-two following allyloxy sulfobenzides of 100ppm in 4 '-two allyloxy sulfobenzides.
Among the present invention, be to suppress side reaction or polyreaction, preferably will be reflected under the atmosphere of rare gas elementes such as nitrogen, argon gas and carry out under the state of anaerobic in fact.
The combination of sequestrant and antioxidant is preferably 1, the combination of 10-phenanthroline class or EDTA and xitix.
Be used in microwave of the present invention and be generally hertzian wave, can use wherein any with 300MHz to 30GHz frequency.Industrial microwave irradiation machine uses 2450MHz or 918MHz, so use it to get final product usually.Irradiation time can be according to the wattage of charging capacity, microwave applicator etc. and different, therefore cannot treat different things as the same, but be generally 1 to 60 minute under 100 to 10kW after reaching temperature of reaction.The angle of calm reaction easy to control etc. preferably finished reaction at about 5 to about 30 minutes.By electromagnetic interrupted (switch) irradiation etc., temperature of reaction is controlled at 150 to 350 ℃, preferred 230 to 300 ℃, more preferably in 240 to 290 ℃ the scope.Being used in microwave irradiation experimental installation of the present invention is for example made, is sold by Milestone company, CEM company, microelectronics (share) company etc.
Among the present invention, rearrangement reaction can be carried out under the arbitrary condition in the presence of solvent-free or the solvent.When using solvent, the preferred high boiling solvent of inertia.For example, can use N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO) isopolarity solvent, chlorobenzene classes such as orthodichlorobenzene, trichlorobenzene, high boiling aliphatic hydrocarbon etc.When using solvent, usually with raw material 4,4 '-two allyloxy sulfobenzides are dissolved or dispersed in the solvent and use.At this moment, temperature of reaction is generally about 190 to about 220 ℃.In addition, also can use a small amount of solvent of raw material wetness degree, below 1 of several branches of 4,4 '-two allyloxy sulfobenzides for example, for example below 1/3rd, preferred below 1/4th, more preferably below 1/5th.
Use solvent-free or when making a small amount of solvent of raw material wetness degree, preferably in advance raw material made molten state, and under this state irradiating microwaves, carry out rearrangement reaction.Thus, the generation of by product can be suppressed to low-levelly, can further shorten the reaction times.For raw material is made molten state in advance, can adopt irradiating microwaves on raw material, become molten state, or use other method, for example the heater heats of passing through electricradiator or use thermal medium in the past becomes molten state.
In the present invention, slave unit feed intake efficient well and the angle that need not reclaim solvent consider, preferably under solvent-free, carry out rearrangement reaction.
Among the present invention, be to suppress side reaction or polyreaction, will be reflected in the environment of rare gas elementes such as nitrogen, argon gas and carry out under existing in anaerobic in fact.In addition, for suppressing by product, preferably will be reflected under the existence that is selected from least a compound in the group of forming by antioxidant, organo-alkali compound and sequestrant and carry out.In addition, a kind of preferred form is for carrying out under at least a coexistence in (1) antioxidant and (2) organo-alkali compound or sequestrant.
As antioxidant can exemplify as, xitix, vitamin-E, methoxyl group quinhydrones, butylhydroquinone etc., more preferably xitix.In addition, only otherwise influence effect of the present invention, also can use its salt.
The addition of antioxidant is promptly enough below the 1 quality % (being quality % below unless otherwise specified) of 4,4 '-two allyloxy sulfobenzides, is generally about 0.01% to about 0.5%.
Organo-alkali compound can exemplify as, N, accelerine, N, N such as N-Diethyl Aniline, dimethyl aminopyridine, nitrogenous ring compounds such as N-two low alkyl group aromatic amines, vulkacit H, rubane, quinoline, isoquinoline 99.9, toluquinoline, quinoxaline etc.In addition, as low alkyl group, preferred carbon number 1 to 6, preferred 1 to 3 alkyl.Aromatic nucleus in the aromatic amine can be enumerated 5 to 6 Yuans rings, the aromatic nucleus of preferred 6 Yuans rings.As nitrogenous ring compound, preferred carbon number is about 5 to about 15, more preferably from about 6 to about 12 nitrogenous ring compound (doing the nitrogen-atoms number is 1 to 4, and it is following to account for half of whole atoms of forming ring).In these, excellent N, N-two low alkyl group aromatic amines.
The sequestrant of Shi Yonging for example can be enumerated the heterocycle sequestrant of nitrogen atom or aliphatics polyamino polyacetic acid etc. in the present invention.The heterocycle of nitrogen atom for example can be enumerated pyridine ring, condensed pyridine ring etc.The heterocycle sequestrant of nitrogen atom for example can enumerate contain that 1 to 3, preferred 2 these pyridine rings or condensed pyridine ring and carbon number are 8 to 18, preferred carbon number is 9 to 12 aromatic heterocyclic compounds, this compound can have the substituting group of hydroxyl, phenyl etc.For example can enumerate, 1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline, 2,9-dimethyl-1,1 of 10-phenanthroline etc., 10-phenanthroline class, oxine (oxine), 2,2 '-diquinolyl, 2,2 '-dipyridyl, 2,2 ', 2 "-terpyridyl, 1,8-naphthyridines class etc.As aliphatics polyamino polyacetic acid, can enumerate at carbon number and be 2 to 5, contain 2 to 3, preferred 2 amino in preferred 2 to 3 the aliphatic hydrocarbon, and hydrogen that should amino is fully by the compound of acetic acid substituted, for example, and ethylenediamine tetraacetic acid (EDTA) (EDTA), trimethylenedinitrilo-tertraacetic acid (PDT) etc.The heterocycle sequestrant of preferred nitrogen atom for example can enumerate 1,10-phenanthroline class, most preferably 1,10-phenanthroline.As aliphatics polyamino polyacetic acid, preferred EDTA.The addition of sequestrant is promptly abundant below the 1 quality % (being quality % below unless otherwise specified) of 4,4 '-two allyloxy sulfobenzides, is about 0.01% to about 0.5% usually.
As the combination of sequestrant and antioxidant, sequestrant, preferred 1,10-phenanthroline class or EDTA and be preferred as the combination of the xitix of antioxidant.
The addition of these side reaction inhibitors is promptly enough below the 1 quality % (being quality % below unless otherwise specified) of 4,4 '-two allyloxy sulfobenzides, is generally about 0.01% to about 0.5%.
Reaction can following three kinds of modes be carried out: with 4, the batch-type of irradiating microwaves then in the disposable adding reactor of 4 '-two allyloxy sulfobenzides, in the reactor of irradiating microwaves continuously or be divided into aliquot and supply with 4, the semi-batch of 4 '-two allyloxy sulfobenzides, in the reactor of irradiating microwaves, supply with 4,4 '-two allyloxy sulfobenzides continuously and discharge the flow type of resultant continuously.
Resultant of reaction usable highly effective liquid chromatography is confirmed.After reaction finishes, 3,3 '-two allyloxys-4 in the resultant of reaction of gained, the content of 4 '-dihydroxy diphenylsulphone is more than 85%, to be preferably more than 90%.The gained resultant is by well-established law, carry out acid out after for example being dissolved in alkaline aqueous solution, or the heating for dissolving postcooling separated out crystallization in organic solvent, separates by filtration, or makes up both method purifying such as (acid outs and recrystallize from organic solvent).The purifying 3 that so makes, 3 '-diallyl-4, the purity of 4 '-dihydroxy diphenylsulphone is generally (area % in the high performance liquid chromatography: following identical) more than 97%, and yield is (the mole % that is equivalent to add-on: following identical) more than 80%.
Embodiment
Describe the present invention in detail by embodiment, but be not to limit the present invention with these embodiment.
Embodiment 1
In quartz flask with temperature sensor, magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g and N, accelerine 0.01g carries out the nitrogen displacement.Microwave with 2450MHz under the condition that nitrogen flows into shines with 100W, after 160 ℃ of following fusions, by the switch that shines temperature of reaction is remained on 280 ℃ of reactions 5 minutes.The efficient liquid phase chromatographic analysis value of gained resultant of reaction (the area % of high performance liquid chromatography: following identical) shows 3; 3 '-diallyl-4; 4 '-dihydroxy diphenylsulphone (below; abbreviate two as and reset body) 89.5%; 3-allyl group-4-hydroxyl-4 '-allyloxy sulfobenzide (below; abbreviate substance row body as) 1.4%; 5-(3-allyl group-4-hydroxyl) phenyl sulfonyl-1-oxa--2-methyl indan (below; abbreviate the indane body as) 1.1%; 3-allyl group-4,4 '-dihydroxy diphenylsulphone (below, abbreviate monoene propyl group body as) 1.5%; isomer 0.8%, dimer 1.8%.
After this resultant of reaction dissolves with 10 weight % aqueous sodium hydroxide solutions, add the processing of decolouring of a small amount of activated carbon heated and stirred, behind the filtering gac, in filtrate, add the hydrochloric acid neutralization, separate out crystallization, it is 96% to 98% purifying 3 that yield that can 80% to 90% (quality %: following identical) obtains purity, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone.
Embodiment 2
In quartz flask with temperature sensor, magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g and N, accelerine 0.01g carries out nitrogen replacement.Under the condition that nitrogen flows into, the microwave of 2450MHz is shone with 100W, after 160 ℃ of following fusions, the switch by irradiation remains on 255 ℃ of reactions 20 minutes with temperature of reaction.In the efficient liquid phase chromatographic analysis value of gained resultant of reaction, two rearrangement bodies are 91.1%, substance row body 1.6%, and the indane body is 1.0%, monoene propyl group body is 1.1%, isomer 0.6%, dimer 1.4%.
With this resultant of reaction method purifying with embodiment 1 record, it is 96% to 98% purifying 3 that yield that can 80% to 90% (quality %: following identical) obtains purity, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone.
Embodiment 3
In quartz flask with temperature sensor, magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g, carry out the nitrogen displacement.Microwave with 2450MHz under the condition that nitrogen flows into shines with 100W, after 160 ℃ of following fusions, by the switch that shines temperature of reaction is remained on 280 ℃ of reactions 5 minutes.The efficient liquid phase chromatographic analysis value of gained resultant of reaction shows that two rearrangement bodies are 87.4%, substance row body 1.9%, and the indane body is 1.7%, monoene propyl group body is 2.6%, isomer 1.7%, dimer 1.9%.This resultant of reaction is by the method purifying of embodiment 1 record, and it is 96% to 98% purifying 3 that yield that can 80% to 90% (quality %: following identical) obtains purity, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone.
Embodiment 4
In quartz flask with temperature sensor and magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g and 1,10-phenanthroline 10mg carries out the nitrogen displacement.Under the condition that nitrogen flows into, the microwave of 2450MHz is shone with 100W, after 160 ℃ of following fusions, the switch by irradiation remains on 280 ℃ of reactions 5 minutes with temperature of reaction.Two rearrangement bodies are 90.5% in the efficient liquid phase chromatographic analysis value of gained resultant of reaction, substance row body 1.5%, and the indane body is 1.5%, monoene propyl group body is 1.5%, not clear composition 0.8%, dimer 1.6%.This resultant of reaction is with after the 10 weight % aqueous sodium hydroxide solutions dissolvings, adds the processing of decolouring of a small amount of activated carbon heated and stirred.Filtration of active charcoal adds the neutralization of 20% sulfuric acid in filtrate then, separates out crystallization.Purifying 3,3 '-diallyl-4,4 '-dihydroxy diphenylsulphone are 8.45g (yield 84.5%).The liquid chromatography analysis shows that two rearrangement body burdens are 97.0%.
Embodiment 5
In quartz flask with temperature sensor and magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g, 1,10-phenanthroline 5mg and xitix 5mg carry out the nitrogen displacement.By the electricradiator heating, after 160 ℃ of fusions, the microwave that shines 2450MHz with 100W is warming up to 260 ℃ under nitrogen inflow condition, by the switch that shines temperature of reaction is remained on 260 ℃ of reactions 16 minutes.The efficient liquid phase chromatographic analysis value of gained resultant of reaction is as follows, and two rearrangement bodies are 93.6%, substance row body 1.3%, and the indane body is 1.2%, monoene propyl group body is 0.3%, not clear composition 0.6%, dimer 1.2%.This resultant of reaction obtains 3 of purifying, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone 8.70g (yield 87.0%) with the method purifying identical with embodiment 1.The efficient liquid phase chromatographic analysis value shows that two rearrangement bodies are 97.5%.
Embodiment 7
In quartz flask with temperature sensor and magnetic stirring apparatus, add 4,4 '-two allyloxy sulfobenzide 10.00g, EDTA5mg and xitix 5mg, carry out the nitrogen displacement.Microwave with 2450MHz under the condition that nitrogen flows into shines with 100W, is warming up to 260 ℃, by the switch that shines temperature of reaction is remained on 260 ℃ of reactions 16 minutes.The efficient liquid phase chromatographic analysis value of gained resultant of reaction is as follows, and two rearrangement bodies are 91.8%, substance row body 1.1%, and the indane body is 1.2%, monoene propyl group body is 0.4%, not clear composition 0.8%, dimer 1.9%.This resultant of reaction obtains 3 of purifying, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone 8.50g (yield 85.0%) with the method purifying identical with embodiment 1.The efficient liquid phase chromatographic analysis value shows that two rearrangement bodies are 97.2%.
Embodiment 8
In having the 100ml quartz flask of temperature sensor and magnetic stirring apparatus, add trichlorobenzene 20g, 4,4 '-two allyloxy sulfobenzide 10.00g, o-phenanthroline 10mg and xitix 10mg, carry out the nitrogen displacement.Following in the condition that nitrogen flows into, by the oil bath heating, reacted 7 hours down at 210 ℃.The efficient liquid phase chromatographic analysis value of gained resultant of reaction is as follows, and two rearrangement bodies are 95.3%, substance row body 2.2%, and the indane body is 0.7%, monoene propyl group body is 0.1%, not clear composition 0.1%, dimer 0.5%.The trichlorobenzene solution of resultant of reaction extracts with 10 weight % aqueous sodium hydroxide solutions under heating.In extraction liquid, add a small amount of activated carbon and stir the processing of decolouring, behind the filtering activated carbon, in filtrate, add the neutralization of 20% sulfuric acid, separate out crystallization.Obtain 3 of purifying, 3 '-diallyl-4,4 '-dihydroxy diphenylsulphone 8.80g (yield 88.0%).The efficient liquid phase chromatographic analysis value shows that two rearrangement bodies are 97.0%.
Industrial applicibility
4,4 '-two allyloxy diphenyl sulphone (DPS)s change 3 into, 3 '-diallyl-4,4 '-dihydroxydiphenylsulisomer Rearrangement reaction minute got final product to about 30 minutes by be kept to approximate number in 7 to 10 hours that needed in the past Finish, not only can suppress in addition accessory substance and generate, and make object with high yield, moreover can In solvent-free, react, therefore economically highly beneficial.
Claims (11)
1.3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone is characterized in that, with 4,4 '-two allyloxy sulfobenzides carry out rearrangement reaction under microwave irradiation.
2. as claimed in claim 13,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out under molten state.
3. as claimed in claim 23,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out under 230 to 300 ℃.
4. as claimed in claim 1 or 23,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone is wherein carried out in the rearrangement reaction environment that substantially anaerobic exists.
5. as claimed in claim 13,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of alkaline matter.
6. as claimed in claim 13,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of antioxidant.
7. as claimed in claim 63,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of as the xitix of antioxidant.
8. as claimed in claim 13,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein rearrangement reaction is carried out in the presence of sequestrant.
9. as claimed in claim 83,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein sequestrant is ethylenediamine tetraacetic acid (EDTA) or the condensed ring sequestrant that comprises the nitrogen atom aromatic nucleus.
10. as claimed in claim 93,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone, wherein the condensed ring sequestrant is a phenanthroline.
11.3,3 '-diallyl-4, the method for making of 4 '-dihydroxy diphenylsulphone is characterized in that, under microwave irradiation, temperature be 230 to 300 ℃, and alkaline matter or sequestrant in the presence of carry out the rearrangement reaction of 4,4 '-two allyloxy sulfobenzides.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP100352/2003 | 2003-04-03 | ||
| JP2003100352A JP4248915B2 (en) | 2003-04-03 | 2003-04-03 | Process for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone |
| JP306348/2003 | 2003-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1768032A true CN1768032A (en) | 2006-05-03 |
Family
ID=33524446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480009129 Pending CN1768032A (en) | 2003-04-03 | 2004-03-31 | Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4248915B2 (en) |
| CN (1) | CN1768032A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880717A (en) * | 2014-03-21 | 2014-06-25 | 江苏傲伦达科技实业股份有限公司 | Preparation method of bis(3-allyl-4-hydroxy phenyl) sulfone and derivative thereof |
| CN106397283A (en) * | 2016-08-31 | 2017-02-15 | 金华盛纸业（苏州工业园区）有限公司 | Preparation method of temperature-sensitive developer 4,4'-sulfonylbis[2-(2-propenyl)]phenol |
| CN107406377A (en) * | 2015-04-27 | 2017-11-28 | 日华化学株式会社 | Pi-allyl substitutes the manufacture method of bisphenol compound |
| CN115784951A (en) * | 2022-12-23 | 2023-03-14 | 潍坊大有生物化工有限公司 | Preparation method of heat-sensitive color developing agent 4,4' -sulfonyl bis [2- (2-propenyl) ] phenol |
-
2003
- 2003-04-03 JP JP2003100352A patent/JP4248915B2/en not_active Expired - Fee Related
-
2004
- 2004-03-31 CN CN 200480009129 patent/CN1768032A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880717A (en) * | 2014-03-21 | 2014-06-25 | 江苏傲伦达科技实业股份有限公司 | Preparation method of bis(3-allyl-4-hydroxy phenyl) sulfone and derivative thereof |
| CN103880717B (en) * | 2014-03-21 | 2015-11-04 | 江苏傲伦达科技实业股份有限公司 | The preparation method of two (3-allyl group-4-hydroxy phenyl) sulfones and derivative thereof |
| CN107406377A (en) * | 2015-04-27 | 2017-11-28 | 日华化学株式会社 | Pi-allyl substitutes the manufacture method of bisphenol compound |
| CN107406377B (en) * | 2015-04-27 | 2019-07-09 | 日华化学株式会社 | The manufacturing method of allyl substitution bisphenol compound |
| CN106397283A (en) * | 2016-08-31 | 2017-02-15 | 金华盛纸业（苏州工业园区）有限公司 | Preparation method of temperature-sensitive developer 4,4'-sulfonylbis[2-(2-propenyl)]phenol |
| CN115784951A (en) * | 2022-12-23 | 2023-03-14 | 潍坊大有生物化工有限公司 | Preparation method of heat-sensitive color developing agent 4,4' -sulfonyl bis [2- (2-propenyl) ] phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4248915B2 (en) | 2009-04-02 |
| JP2004345955A (en) | 2004-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1950373A (en) | Processes of preparing glycolurils and cucurbiturils using microwave | |
| KR100525977B1 (en) | Method for producing 3,4-alkylenedioxythiophenes and 3,4-dialkoxythiophenes | |
| CN104262071A (en) | Photocatalysis synthesis method of biphenyl compounds | |
| Chu et al. | Synthesis of di (hetero) aryl sulfides by defluorinative sulfenylation of polyfluoroalkyl ketones with sodium sulfinates or arylsulfonyl chlorides | |
| KR20040022232A (en) | Process for preparation of 5-methyl-1-phenyl-2(1h)-pyridinone | |
| CN1768032A (en) | Method for producing 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone | |
| JP2011219737A (en) | Diepoxy compound, composition containing the compound, and cured product obtained by curing the composition | |
| CN1680374A (en) | Novel synthesis and crystallization of piperazine ring-containing compounds | |
| Velasco et al. | NIS/HFIP‐Mediated Synthesis of Indene‐Based β‐Iodoalkenyl Sulfides from Propargylic Sulfides | |
| CN109928902B (en) | Method for synthesizing heat-sensitive color developing agent 4,4' -sulfonyl bis [2- (2-propenyl) ] phenol | |
| CN115160312B (en) | Viridigdine key intermediate and preparation method thereof | |
| US20060217574A1 (en) | Method for producing 3,3 diallyl-4,4 dihydroxydiphenylsulfone | |
| JP2000336133A (en) | New oxetanesulfonic ester, oxetane-derived novolak resin using the same and its production | |
| CN113620811B (en) | Halogenation method of aromatic compound | |
| CN111574427B (en) | Synthesis method of 2-indole-3-oxoindoline compound | |
| JP6856471B2 (en) | A method for producing a lactone compound and a method for producing biotin using the lactone compound. | |
| CN114292415A (en) | One-step simple synthesis method and application of aminated lignin | |
| CN113943979A (en) | Method for preparing On-DNA thioether compound from On-DNA aryl halide | |
| WO2009111162A1 (en) | Process for the preparation of 3-hydroxymorphinan derivatives | |
| CN102302949A (en) | Novel photocatalytic sensitizer and preparation method thereof | |
| CN111253367B (en) | Sulfurizing method of nitrogen-containing heterocycle substituted pyrrole derivative | |
| CN115724794A (en) | Preparation method of 2-aminoquinoline derivative | |
| KR102482479B1 (en) | Catalyst and method for preparation the same | |
| CN109796372B (en) | Method for preparing polysubstituted alkenyl amidine | |
| EP0334188A2 (en) | Process for producing aromatic nitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |