CN109534976A - A kind of preparation method of Alpha-hydroxy ketone intermediate - Google Patents
A kind of preparation method of Alpha-hydroxy ketone intermediate Download PDFInfo
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- CN109534976A CN109534976A CN201811580448.XA CN201811580448A CN109534976A CN 109534976 A CN109534976 A CN 109534976A CN 201811580448 A CN201811580448 A CN 201811580448A CN 109534976 A CN109534976 A CN 109534976A
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- hydroxy ketone
- ketone intermediate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to compounds process for production thereof domain variabilities to disclose a kind of preparation method of Alpha-hydroxy ketone intermediate, it solves the problems, such as in related art using environment and safe operation risk brought by aluminum trichloride (anhydrous) and other lewis acid catalysts, specifically the present invention relates to without using aluminum trichloride (anhydrous) and other lewis acid catalysts, the method for preparing Alpha-hydroxy ketone intermediate, it is few that this method generates the three wastes；It directlys adopt hexafluoroisopropanol and makees solvent, and solvent can be recycled and recycle；Reaction efficiency is higher, and yield is higher with purity, operates more easy thus whole more environmentally protective；Room temperature reaction, mild condition in terms of the emission reduction that lowers consumption, there is positive important meaning without consuming many heats, energy consumption.
Description
Technical field
The invention belongs to compounds process for production thereof field, it is related to needing key to be used during synthesizing Alpha-hydroxy ketone
The preparation method of Alpha-hydroxy ketone intermediate, the preparation method of specifically a kind of Alpha-hydroxy ketone intermediate.
Background technique
Photocuring technology is a kind of efficient, energy-saving and environmental protection green material process for treating surface, is known as towards 21 worlds
The new technology of green industry.Wherein, Alpha-hydroxy ketone is the chief component of ultraviolet photocureable material, is widely used in
The various fields such as electronics, optical fiber, printing, packaging, adhesive, coating and composite material.Its representative products has 1173,184,651
With 2959 etc., the features such as these products are with efficiency of initiation height, the high and low smell of solubility, low pollution, stability are good, color inhibition, and
It is used widely in ultraviolet photocureable material.
Under normal conditions, catalyst is done using aluminum trichloride (anhydrous), after reaction, system becomes homogeneously, needing to anti-
It answers and cryosel acid solution is added in liquid to wash, decompose arone-aluminum chloride complex, further purification obtains product.In reality
Make lewis acid catalyst with anhydrous aluminum chloride in the production process of border, there are some problems: 1) reaction needs the catalyst measured,
And a large amount of heat is released in reaction, to equipment requirement harshness；2) after reacting, reaction solution needs complicated post-processing in homogeneously；3) after
A large amount of acid is excluded in treatment process, alkali, causes environmental pollution；4) production equipment is caused to corrode；5) for overactive
Aromatic ring and high activity raw material, the selectivity of reaction be not high.Therefore environmentally safe catalyst is found, develops more environmentally friendly technique
Route and production technology have realistic meaning.
Industrially producing alpha-hydroxyl ketone, most techniques have all used anhydrous AlCl at present3Although it is a kind of work
Property very high acylation catalyst, but have that catalyst amount is big, and the three wastes are more in actual production, recoverable etc. does not lack
Point, especially for the aromatic ring that some comparisons are active, using AlCl3Catalyst is made, often selectivity is not high, and the three wastes are especially more,
So as to cause the waste of raw material and resource.The present invention relates to any Louis's acid as catalyst is not used, to embody environment friend
Good meaning.
Other louis catalysts, cut both ways, TiCl4、SnCl4、BF3Diethyl ether solution price, and using dangerous；
Anhydrous FeCl3Catalytic efficiency is relatively low etc..
Summary of the invention
The present invention is in order to solve to use aluminum trichloride (anhydrous) and other lewis acid catalyst institute bands in related art
The problem of environment and safe operation risk for coming, a kind of preparation method of Alpha-hydroxy ketone intermediate is provided, avoids reacting
Largely contain aluminic acid or other salt waste water brought by post-processing, simplifies process, technological operation is simple, meets green scale
The requirement that metaplasia produces.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of Alpha-hydroxy ketone intermediate, the structural formula of the Alpha-hydroxy ketone intermediate as shown in formula I,
Formula I
Wherein: Ar is selected to be replaced by C1-C12 alkyl, C1-C4 alkoxy, alkylthio group, halogen, cyano, 2- hydroxyl-oxethyl
Phenyl ring or naphthalene nucleus；
R1、R2It is independently selected from C1-C7 alkyl or by R1And R2Connect into the naphthenic base of C3-C8；
The preparation method comprises the following steps:
1) Ar is mixed with the acyl chlorides for drafting combination；
2) it is reacted in the presence of hexafluoroisopropanol, reaction process stirring is abundant.
Method of the present invention does reaction dissolvent using hexafluoroisopropanol, which can be recycled and recycle,
Compare environmentally friendly.
Preferably, the ratio between amount of substance of Ar and acyl chlorides is (2.2-3) in step 1): 1.
Preferably, reaction temperature of the present invention is selected from 0-40 DEG C.It is further preferred that reaction temperature of the present invention is selected from 25 DEG C.
The present invention can react at room temperature, and reaction condition is realized well, therefore the present invention is a kind of mild preparation method.
Invention further provides α-hydroxyls that a kind of preparation method of Alpha-hydroxy ketone intermediate is prepared
Base ketone intermediate is synthesizing the application in alpha-alcohol ketone photoinitiator, wherein the specific structure of alpha-alcohol ketone photoinitiator
Formula is structure shown in formula II:
Formula II
Wherein, the preferred phenyl of Ar, substituted-phenyl, Ar is most preferably by phenyl, p-methylphenyl, to ethylphenyl, 2- '-hydroxyethoxy
The phenyl ring that base replaces；R1And R2It is respectively and independently selected from methyl, ethyl or by R1And R2Connect into cyclohexyl or cyclopenta.
The Alpha-hydroxy ketone intermediate of structure shown in formula I can obtain the Alpha-hydroxy ketone light of II structure of formula by 'alpha '-hydroxylation
Initiator, and alpha-alcohol ketone photoinitiator is preferably 2- hydroxy-2-methyl -1- phenyl -1- acetone (UV1173), 1- hydroxyl
Cyclohexyl phenyl ketone (UV184), 2- hydroxyl-1-(4-(2- hydroxy ethoxy) phenyl)-2- methyl-1-acetone (UV2959).
The beneficial effects of the present invention are:
1) any Louis's acid as catalyst is not needed, the generation three wastes are few, more environmentally friendly；
2) it directlys adopt hexafluoroisopropanol and makees solvent, and solvent can be recycled and recycle；
3) reaction efficiency is higher, and yield is higher with purity, operates more easy thus whole more environmentally protective；
4) it reacts at room temperature, mild condition, without consuming many heats, energy consumption, in terms of the emission reduction that lowers consumption, has positive great
Meaning.
Specific embodiment
The stream of the preparation method of Alpha-hydroxy ketone intermediate of the present invention is further illustrated combined with specific embodiments below
Journey.
Embodiment 1: the synthesis of cyclohexyl phenyl ketone.
In the dry three-necked flask of 500ml, 73.30g cyclohexyl formyl chloride (0.50mol) is added to 117g benzene
(1.50mol) and 150g hexafluoroisopropanol (0.893mol) stirs 6h, GC or TLC detection reaction at 0 DEG C and steams after completion of the reaction
Recycling design is evaporated, is further distilled, cools down and obtains white solid cyclohexyl phenyl ketone 83.14g, yield 88.34%,
GC96.53%。1HNMR(400MHz,CDCl3):δ7.93(d,2H),7.56-7.49(m,H),7.49-7.42(m,2H),3.30-
3.21(m,1H),1.93-1.79(m,4H),1.79-1.69(m,1H),1.57-1.21(m,5H)。
The cyclohexyl phenyl ketone passes through 'alpha '-hydroxylation energy synthesis of hydroxy cyclohexyl phenyl ketone (UV184).
The synthesis of embodiment 2:2- methyl-1-phenyl-1- acetone.
In the dry three-necked flask of 500ml, 53.26g isobutyryl chloride (0.50mol) is added to 85.80g benzene
(1.10mol) and 150g hexafluoroisopropanol (0.893mol) stirs 6h, GC or TLC detection reaction at 25 DEG C, after completion of the reaction,
It is distilled to recover solvent, further distills, obtains light yellow liquid, 2- methyl-1-phenyl-1- acetone 61.01g, yield 82.37%,
GC98.12%。1HNMR(400MHz,CDCl3):δ7.95(d,2H),7.55(t,H),7.46(t,2H),3.60-3.57(m,1H),
1.23(d,6H)。
The 2- methyl-1-phenyl-1- acetone can synthesize 2- hydroxy-2-methyl-1- phenyl-1- acetone by 'alpha '-hydroxylation
(UV1173).
The synthesis of embodiment 3:4- (2- hydroxy ethoxy) phenyl-2- methyl-1-acetone.
In the dry three-necked flask of 500ml, isobutyryl chloride 63.93g(0.60mol) is added to 207g 2- hydroxy ethoxy
Benzene (1.50mol) and 150g hexafluoroisopropanol (0.893mol) stir 6h, GC or TLC detection reaction, end of reaction at 40 DEG C
Afterwards, it is distilled to recover solvent, is further distilled, cooling obtains white solid, 4- (2- hydroxy ethoxy) phenyl-2- methyl-1-acetone
71.60g, yield 80.55%, GC97.58%.1HNMR(400MHz,CDCl3):δ7.85(d,2H),7.82(d,2H),3.76-
3.72(m,4H),3.61-3.58(m,1H),1.21(d,6H)。
4- (2- hydroxy ethoxy) phenyl-2- methyl-1-acetone can synthesize 2- hydroxyl-1-(4-(2- by 'alpha '-hydroxylation
Hydroxy ethoxy) phenyl)-2- methyl-1-acetone (UV2959).
The synthesis technology of above-mentioned intermediate, without cumbersome reaction treatment, process is simple and easy, environmentally friendly, does not have
Pollution, process flow is easy to implement, more meets the theory of green synthetic chemistry and production.
The foregoing is merely preferred embodiments of the invention, are not intended to limit the invention, all in principle of the invention
Within any modification, equivalent replacement, improvement and so on, should all include again within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of Alpha-hydroxy ketone intermediate, which is characterized in that the structural formula of the Alpha-hydroxy ketone intermediate
As shown in formula I:
Formula I
Wherein: Ar is selected to be replaced by C1-C12 alkyl, C1-C4 alkoxy, alkylthio group, halogen, cyano, 2- hydroxyl-oxethyl
Phenyl ring or naphthalene nucleus；
R1、R2It is independently selected from C1-C7 alkyl or by R1And R2Connect into the naphthenic base of C3-C8；
The preparation method comprises the following steps:
1) Ar is mixed with the acyl chlorides for drafting combination；
2) it is reacted in the presence of hexafluoroisopropanol, reaction process stirring is abundant.
2. a kind of preparation method of Alpha-hydroxy ketone intermediate according to claim 1, it is characterised in that: Ar in step 1)
It is (2.2-3) with the ratio between the amount of substance of acyl chlorides: 1.
3. a kind of preparation method of Alpha-hydroxy ketone intermediate according to claim 2, it is characterised in that: reaction temperature choosing
From 0-40 DEG C.
4. a kind of preparation method of Alpha-hydroxy ketone intermediate according to claim 3, it is characterised in that: reaction temperature choosing
From 25 DEG C.
5. the Alpha-hydroxy ketone that a kind of preparation method of any Alpha-hydroxy ketone intermediate of claim 1-4 is prepared
Application of the intermediate in synthesis alpha-alcohol ketone photoinitiator.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304033A (en) * | 2011-07-18 | 2012-01-04 | 连云港升南化学有限公司 | Process for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
| CN103613492A (en) * | 2013-12-10 | 2014-03-05 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
-
2018
- 2018-12-24 CN CN201811580448.XA patent/CN109534976A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304033A (en) * | 2011-07-18 | 2012-01-04 | 连云港升南化学有限公司 | Process for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
| CN103613492A (en) * | 2013-12-10 | 2014-03-05 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
Non-Patent Citations (3)
| Title |
|---|
| MOTIWALA HASHIM F.等: "Intramolecular Friedel-Crafts Acylation Reaction Promoted by 1,1,1,3,3,3-Hexafluoro-2-propanol", 《ORGANIC LETTERS》 * |
| TANG REN-JIN等: "Friedel–Crafts alkylation reaction with fluorinated alcohols as hydrogen-bond donors and solvents", 《RSC ADVANCES》 * |
| VEKARIYA RAKESH H.等: "Hexafluoro-2-propanol-Promoted Intermolecular Friedel-Crafts Acylation Reaction", 《ORGANIC LETTERS》 * |
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Application publication date: 20190329 |