CN102020726A - Macromolecule difunctional group alpha-hydroxy-ketone photoinitiator and preparation method thereof - Google Patents
Macromolecule difunctional group alpha-hydroxy-ketone photoinitiator and preparation method thereof Download PDFInfo
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- CN102020726A CN102020726A CN 201010551989 CN201010551989A CN102020726A CN 102020726 A CN102020726 A CN 102020726A CN 201010551989 CN201010551989 CN 201010551989 CN 201010551989 A CN201010551989 A CN 201010551989A CN 102020726 A CN102020726 A CN 102020726A
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Abstract
The invention discloses a macromolecule difunctional group alpha-hydroxy-ketone photoinitiator shown in the following formula and a preparation method thereof. The preparation method comprises: firstly, preparing acyl chloride by hexahydrobenzoic acid; carrying out Friedel-Crafts acylations reaction on the acyl chloride and halogeno benzene in the presence of catalysis by lewis acid; then, in the presence of the catalysis, synthetizing a diketone midbody by ketone and bisphenol; and carrying out alpha-site halogenating and hydrolyzing on the diketone midbody to obtain a target product by. The macromolecule difunctional group alpha-hydroxy-ketone photoinitiator has good compatibility with resin, the volatility of the difunctional group alpha-hydroxy-ketone photoinitiator is greatly improved if compared with corresponding micromolecule photoinitiato, but the photo-initiation activity is not obviously reduced. Most importantly, because of the influence by conjugation, the photoinitiator disclosed by the invention has obvious red shift of absorption wavelength, has higher light absorption efficiency and has good application prospect in the material industries of paint, ink and the like.
Description
Technical field:
The present invention relates to the light trigger field, be specifically related to class macromole bifunctional alpha-alcohol ketone photoinitiator and preparation method thereof.
Background technology:
Photocuring technology is as a kind of " new technology of green industry geared to the 21st century ", have solvent-free, pollution-free, save the energy, multiple advantages such as economize on resources, on base materials such as paper, woodenware, plastics, metal, CD, optical fiber, obtain fine application, show bright development prospect day by day, it in all photocuring technology products ultraviolet ray (UV) curing technology, and light trigger is the important component of UV curing system, is one of the solidification rate of decision system and principal element of state of cure.Hydroxyacetone compounds is that a class is efficient and use light trigger very widely, and its mainstream product has DAROCUR 1173 and IRGACURE 184, and its structure is as follows:
As micromolecular light trigger, that these two products have also inevitably occurred is poor with the consistency of polymkeric substance, shortcomings such as migration and volatilization take place the fragment after the photodissociation easily, serious restriction its application at food and medicine trade.Compare with the small molecules light trigger, macromolecular photoinitiator has strong, the advantages such as environment compatibility good, resin compatible good, functional diversity of low, the anti-transfer ability of volatility, if micromolecular alpha-hydroxyacetone compounds is made macromolecular alpha-hydroxyacetone compounds or polymerisable structure, then the shortcoming of small molecules light trigger will effectively be overcome, and then the Application Areas of hydroxyketone photoinitiator is expanded greatly.Increase molecular weight, do not reduce the efficiency of initiation of unit formula amount simultaneously again, the most simple method is to make the bifunctional molecular structure.At present, the Irgacure 127 of ciba company has obtained market approval, successful commercialization as a kind of bifunctional alcohol ketone photoinitiator.Chinese patent CN101333263A has also reported a kind of alpha-hydroxyacetone compounds of bifunctional, and its structure is as follows:
The alpha-hydroxyacetone compounds of bifunctional has improved to a great extent that the small molecules light trigger easily moves, easily xanthochromia and problem odorous, and every performance is more excellent.
Summary of the invention:
The invention provides alpha-alcohol ketone photoinitiator of a class macromole bifunctional and preparation method thereof.
A class macromole bifunctional alpha-alcohol ketone photoinitiator provided by the invention, general structure is suc as formula shown in the I:
R in the formula (I)
1, R
2Be selected from hydrogen, C respectively alone
1-C
4Alkyl, halogen, C
1-C
4Alkoxyl group, benzyl, C
1-C
4Alkylthio;
Ar is selected from Resorcinol, pyrocatechol, Resorcinol, 2 in the formula (I), two (4-hydroxy phenyl) propane, 1 of 2-, and 4-naphthalenediol, 1,4-dihydroxy benaophenonel are removed two groups behind the hydroxy functional group.
Prepare the concrete grammar of macromole bifunctional alpha-alcohol ketone photoinitiator of the present invention, comprise following step:
(a) heptanaphthenic acid and chlorination reagent effect prepare cyclohexanecarbonyl chloride;
(b) cyclohexanecarbonyl chloride carries out the intermediate of the electrophilic substitution reaction system on the aromatic nucleus to fluorophenyl cyclohexyl ketone with fluorobenzene or replacement fluorobenzene under Lewis acid (Lewis) catalysis.
(c) intermediate is carrying out intermediate that nucleophilic substitution reaction aromatic nucleus on obtain contain dicyclohexyl benzophenone structure with diphenol to fluorophenyl cyclohexyl ketone under the effect of catalyzer.
(d) this diketone intermediate obtains the phenylcyclohexane ketone intermediate of two chloros again with the substitution reaction of chlorine generation α position reactive hydrogen under the effect of catalyzer.
(e) this chloro intermediate obtains the product of bimolecular alpha-alcohol ketone with aqueous sodium hydroxide solution generation hydrolysis reaction under catalyst action.
Reaction equation is as follows:
The used chlorination reagent of the present invention comprises sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, phosgene; Preferred sulfur oxychloride or phosphorus trichloride.
The used lewis acid catalyst of the present invention comprises aluminum chloride, iron trichloride, zinc chloride or alchlor; Preferred aluminum chloride, its proportioning are 1.0-5 times of acyl chlorides.Temperature of reaction is controlled at-20 ℃-80 ℃.
The used Ar of the present invention is selected from Resorcinol, pyrocatechol, Resorcinol, 2, two (4-hydroxy phenyl) propane, 1 of 2-, and 4-naphthalenediol, 1,4-dihydroxy benaophenonel are removed two groups behind the hydroxy functional group, and its structure is respectively:
The used catalyzer of nucleophilic reaction comprises sodium hydroxide, yellow soda ash, salt of wormwood, potassium hydroxide on the aromatic nucleus of the present invention, preferred salt of wormwood.Solvent for use is selected from benzene, toluene, methyl-sulphoxide and is abbreviated as DMSO, N, and dinethylformamide is abbreviated as DMF, and N,N-dimethylacetamide is abbreviated as DMAC, oil of mirbane; Preferred DMF and toluene.Temperature of reaction is 20 ℃-200 ℃.
The substitution reaction catalyst system therefor of α of the present invention position reactive hydrogen is the DMF or the vitriol oil.Solvent is selected from ethylene dichloride, methylene dichloride, chloroform, tetracol phenixin, oil of mirbane, dithiocarbonic anhydride or tetrahydrofuran (THF); Preferred ethylene dichloride.Temperature of reaction is 0 ℃-100 ℃.
Described chloro intermediate hydrolysis reaction catalyst system therefor is tetramethyl ammonium chloride, 4 bromide, tri-n-octyl methyl ammonium chloride, trioctylphosphine methyl brometo de amonio, benzyl triethylammonium chloride, tetraethylammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, octadecyl trimethyl ammonium chloride or octadecyl trimethylammonium bromide.Described solvent comprises benzene, toluene, ethylene dichloride or tetracol phenixin, preferred benzene.Described hydrolysing agent is yellow soda ash, salt of wormwood, potassium hydroxide or the aqueous sodium hydroxide solution of 0.1%-60%, preferred aqueous sodium hydroxide solution, and concentration is 0.1%-60%; Preferred 30% sodium hydroxide solution, temperature of reaction are 20 ℃-100 ℃.
The alpha-alcohol ketone photoinitiator of one class macromole bifunctional of the present invention's preparation has bigger relative molecular mass, good with the consistency of resin, the corresponding small molecules light trigger of volatility significantly decreases, light-initiated activity is suitable with corresponding small molecules light trigger, what is more important is because the influence of conjugation, the obvious red shift of alpha-alcohol ketone initiator absorbing wavelength of this macromole bifunctional, efficiency of light absorption is higher, can replace micromolecular alpha-alcohol ketone photoinitiator to use fully, and raw material is easy to get, synthetic operation is simple, the product yield height.
Description of drawings
Fig. 1 is the IR spectrogram of the bimolecular alpha-alcohol ketone that obtains of embodiment 1.
Embodiment:
The following example describes the present invention in detail, but following example is not limited only to the present invention again.
Embodiment 1:
In being housed, the 500mL there-necked flask of stirring adds 64g (0.5mol) heptanaphthenic acid, start stirring, controlled temperature is slowly to drip 30.3g (0.22mol) phosphorus trichloride under 40 ℃-50 ℃, dripped off in 2 hours, dropwise follow-up continuation of insurance temperature reaction 4 hours, standing demix, branch falls down a layer raffinate and gets cyclohexanecarbonyl chloride 70.9g, yield 96.8%.
Get 72g (0.54mol) aluminum trichloride (anhydrous) and place reaction flask, add 139.4g (1.45mol) fluorobenzene, stir, be cooled to 10 ℃ and slowly drip 70.9g (0.48mol) cyclohexanecarbonyl chloride down, be warming up to 35 ℃ of-40 ℃ of stirring reactions after adding 2 hours, after reaction finishes reaction solution ground slowly poured in 10% the hydrochloric acid soln, vigorous stirring, tell organic phase, washing, after fluorobenzene was reclaimed in distillation, further rectifying obtained intermediate to fluorophenyl cyclohexyl ketone 90.6g (0.44mol), and yield is 91.7%.
To mechanical stirring is housed, prolong, drop into 24.2g (0.22mol) Resorcinol in the there-necked flask of water trap, 90.6g (0.44mol) to fluorophenyl cyclohexyl ketone, the 20g potash solid, 250mLN, the toluene of dinethylformamide (DMF) and 50mL, vacuumize, logical nitrogen, repeated multiple times is slowly intensification of beginning behind the air in draining bottle, stir, reaction down 4 hours refluxes, take the water that reaction generates out of with refluxing toluene, steam solvent earlier after reaction finishes, add benzene and hot water again, the flush away inorganic salt, rectification under vacuum obtained diketone intermediate 71.8g after the organic phase decompression removed solvent, and product yield is 68.4%.
Get 71.8g products therefrom of last step and place reaction flask, add 0.72g N, dinethylformamide (DMF) and 200ml ethylene dichloride, slowly be warmed up to 50 ℃, stir, slowly feed chlorine, sampling detects after raw material reaction finishes and stops logical chlorine, logical nitrogen is caught up with the hydrogen chloride gas of remainder chlorine and generation, removes to obtain two chloro ketone intermediate 78.1g behind the solvent, and product yield is 95.5%.
Get step product 78.1g and place reaction flask, drop into 1g Dodecyl trimethyl ammonium chloride, the sodium hydroxide solution of 156.2g 30%, 150mL benzene, be warming up to 80 ℃ of-100 ℃ of stirring reactions 4 hours, standing demix after reaction finishes, divide the sub-cloud water, after upper organic phase removed solvent, raffinate obtained target product 1 with the sherwood oil recrystallization, 4-two [4-(1 '-hydroxyl-cyclohexyl ketone) phenoxy group] benzene 72.0g, product yield 98.9%.
Embodiment 2
Resorcinol with among the pyrocatechol replacement embodiment one obtains intermediate 1, and 2-two [4-cyclohexyl ketone) phenoxy group] benzene 46.5g, yield is 44.2%.
Embodiment 3
Replace Resorcinol among the embodiment one with Resorcinol, obtain between intermediate 1,3-two [(4-cyclohexyl ketone) phenoxy group] benzene 60.2g, yield is 57.1%.
Embodiment 4
With 2, two (4-hydroxy phenyl) propane of 2-replace the Resorcinol among the embodiment one, obtain intermediate 2,2-two [(4-cyclohexyl ketone) hexichol ether] propane 79.04g, and yield is 75.3%.
Embodiment 5
With 1, the 4-naphthalenediol replaces the Resorcinol among the embodiment one, obtains intermediate 1,4-two [(4-cyclohexyl ketone) phenoxy group] naphthalene 63.2g, and yield is 60.2%.
Embodiment 6
Resorcinol with among 1, the 4 dihydroxy benaophenonel replacement embodiment one obtains intermediate 1,4-two [(4-cyclohexyl ketone) phenoxy group] benzophenone 58.5g, and yield is 55.7%.
Claims (8)
1. a class macromole bifunctional alpha-alcohol ketone photoinitiator is characterized in that, the chemical structure of this light trigger is suc as formula shown in (I):
R in the formula (I)
1, R
2Be selected from hydrogen, C respectively alone
1-C
4Alkyl, halogen, C
1-C
4Alkoxyl group, benzyl, C
1-C
4Alkylthio;
Ar is selected from Resorcinol, pyrocatechol, Resorcinol, 2 in the formula (I), two (4-hydroxy phenyl) propane, 1 of 2-, and 4-naphthalenediol, 1,4-dihydroxy benaophenonel are removed two groups behind the hydroxy functional group.
2. prepare the method for the described macromole bifunctional of claim 1 alpha-alcohol ketone photoinitiator, it is characterized in that, this method may further comprise the steps:
(a) heptanaphthenic acid and chlorination reagent effect prepare cyclohexanecarbonyl chloride;
(b) cyclohexanecarbonyl chloride with fluorobenzene or replace fluorobenzene and carry out electrophilic substitution reaction on the aromatic nucleus, makes intermediate to fluorophenyl cyclohexyl ketone under Lewis acid (Lewis) catalysis.
(c) intermediate is carrying out intermediate that nucleophilic substitution reaction aromatic nucleus on obtain contain dicyclohexyl benzophenone structure with diphenol to fluorophenyl cyclohexyl ketone under the effect of catalyzer.
(d) this diketone intermediate obtains the phenylcyclohexane ketone intermediate of two chloros again with the substitution reaction of chlorine generation α position reactive hydrogen under the effect of catalyzer.
(e) this chloro intermediate obtains the product of bimolecular alpha-alcohol ketone with aqueous sodium hydroxide solution generation hydrolysis reaction under catalyst action;
Concrete reaction equation is as follows:
3. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that, described Friedel-Crafts acylation reaction catalyst system therefor is selected from aluminum chloride, iron trichloride, zinc chloride or alchlor, and its mole proportioning is 1.0-5 a times of acyl chlorides; Preferred aluminum chloride.
4. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that described nucleophilic substitution reaction catalyst system therefor is selected from yellow soda ash, salt of wormwood, potassium hydroxide or sodium hydroxide; Preferred salt of wormwood.
5. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that, described nucleophilic substitution reaction solvent for use is selected from benzene, toluene, 1,2-ethylene dichloride, 1,1-ethylene dichloride, chloroform, tetracol phenixin, methyl-sulphoxide are abbreviated as DMSO, N, dinethylformamide is abbreviated as DMF or N,N-dimethylacetamide is abbreviated as DMAC.
6. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that the halogenating reaction catalyst system therefor of described α position reactive hydrogen is the DMF or the vitriol oil.
7. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that described hydrolysis reaction catalyst system therefor is tetramethyl ammonium chloride, 4 bromide, tri-n-octyl methyl ammonium chloride, trioctylphosphine methyl brometo de amonio, benzyl triethylammonium chloride, tetraethylammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, octadecyl trimethyl ammonium chloride or octadecyl trimethylammonium bromide.
8. according to the preparation method of the described macromole bifunctional of claim 2 alpha-alcohol ketone photoinitiator, it is characterized in that described hydrolysing agent is yellow soda ash, salt of wormwood, potassium hydroxide or the aqueous sodium hydroxide solution of 0.1%-60%, preferred aqueous sodium hydroxide solution.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103064251A (en) * | 2012-12-05 | 2013-04-24 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing bifunctional photoinitiator |
| CN108794660A (en) * | 2017-04-26 | 2018-11-13 | 常州强力先端电子材料有限公司 | Photoinitiator of bifunctionality structure containing sulfone and its preparation method and application |
| CN108911959A (en) * | 2018-07-04 | 2018-11-30 | 大丰鑫源达化工有限公司 | A kind of preparation process of photoinitiator 184 |
| CN109503343A (en) * | 2018-12-28 | 2019-03-22 | 常州久日化学有限公司 | A kind of preparation method of photoinitiator 184 |
| CN109647530A (en) * | 2018-12-24 | 2019-04-19 | 交城县兆晨煤焦有限公司 | With the method for supported catalyst synthesis alpha-alcohol ketone intermediate |
| CN110563589A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-methyl cinnamate photoinitiator, and preparation method and application thereof |
| CN115838327A (en) * | 2022-12-06 | 2023-03-24 | 常州久日化学有限公司 | Alkaline hydrolysis method of photoinitiator 184 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140145A (en) * | 1991-11-12 | 1993-06-08 | Idemitsu Kosan Co Ltd | Cyclic compound, its production and organic electroluminescence element consisting of the same |
| CN1646572A (en) * | 2002-04-19 | 2005-07-27 | 西巴特殊化学品控股有限公司 | Curing of coatings induced by plasma |
| CN101333263A (en) * | 2008-07-30 | 2008-12-31 | 南通新昱化工有限公司 | Macromolecule polyfunctional alpha-alcohol ketone photoinitiator and producing method thereof |
-
2010
- 2010-11-18 CN CN2010105519897A patent/CN102020726B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140145A (en) * | 1991-11-12 | 1993-06-08 | Idemitsu Kosan Co Ltd | Cyclic compound, its production and organic electroluminescence element consisting of the same |
| CN1646572A (en) * | 2002-04-19 | 2005-07-27 | 西巴特殊化学品控股有限公司 | Curing of coatings induced by plasma |
| CN101333263A (en) * | 2008-07-30 | 2008-12-31 | 南通新昱化工有限公司 | Macromolecule polyfunctional alpha-alcohol ketone photoinitiator and producing method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103064251A (en) * | 2012-12-05 | 2013-04-24 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing bifunctional photoinitiator |
| CN108794660A (en) * | 2017-04-26 | 2018-11-13 | 常州强力先端电子材料有限公司 | Photoinitiator of bifunctionality structure containing sulfone and its preparation method and application |
| CN108794660B (en) * | 2017-04-26 | 2020-12-01 | 常州强力先端电子材料有限公司 | Bifunctional photoinitiator containing sulfone structure and preparation method and application thereof |
| CN110563589A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-methyl cinnamate photoinitiator, and preparation method and application thereof |
| CN110563589B (en) * | 2018-06-06 | 2023-02-03 | 湖北固润科技股份有限公司 | Mono-or di-methyl cinnamate photoinitiator, and preparation method and application thereof |
| CN108911959A (en) * | 2018-07-04 | 2018-11-30 | 大丰鑫源达化工有限公司 | A kind of preparation process of photoinitiator 184 |
| CN108911959B (en) * | 2018-07-04 | 2021-12-10 | 大丰鑫源达化工有限公司 | Preparation process of photoinitiator 184 |
| CN109647530A (en) * | 2018-12-24 | 2019-04-19 | 交城县兆晨煤焦有限公司 | With the method for supported catalyst synthesis alpha-alcohol ketone intermediate |
| CN109503343A (en) * | 2018-12-28 | 2019-03-22 | 常州久日化学有限公司 | A kind of preparation method of photoinitiator 184 |
| CN109503343B (en) * | 2018-12-28 | 2022-07-12 | 常州久日化学有限公司 | Preparation method of photoinitiator 184 |
| CN115838327A (en) * | 2022-12-06 | 2023-03-24 | 常州久日化学有限公司 | Alkaline hydrolysis method of photoinitiator 184 |
| CN115838327B (en) * | 2022-12-06 | 2024-05-03 | 湖南久日新材料有限公司 | Alkaline hydrolysis method of photoinitiator 184 |
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