CN114349618B - Preparation method and application of chloro intermediate for synthesizing photoinitiator - Google Patents
Preparation method and application of chloro intermediate for synthesizing photoinitiator Download PDFInfo
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- 125000001309 chloro group Chemical group Cl* 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 49
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- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
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- 239000012074 organic phase Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 23
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 19
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 18
- 239000005457 ice water Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 32
- 239000012752 auxiliary agent Substances 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
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- LYGZOGDWCOYSGJ-UHFFFAOYSA-N 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropanoyl)phenoxy]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1OC1=CC=C(C(=O)C(C)(C)O)C=C1 LYGZOGDWCOYSGJ-UHFFFAOYSA-N 0.000 description 5
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a chloro intermediate of a synthetic photoinitiator and application thereof, wherein the preparation method comprises the steps of adding sulfuric acid with the concentration of 30% -85% as an auxiliary agent in a chloro reaction, which can inhibit the occurrence of chloro substitution reaction on a benzene ring, promote the selectivity of alpha-chloro reaction and further promote the yield of products; compared with the traditional chlorination process using acetic acid as a solvent, the method disclosed by the invention has the advantages that the sulfuric acid with the concentration is used as an auxiliary agent, the selectivity of alpha-chlorination reaction is improved, sulfuric acid in a product is conveniently separated after the chlorination reaction is finished, and a sulfuric acid phase obtained by liquid separation can be recycled, so that the material cost is reduced, the liquid separation operation is simple, and the energy consumption is lower.
Description
Technical Field
The invention belongs to the field of preparation of photoinitiators, and relates to a preparation method and application of a chloro intermediate for synthesizing a photoinitiator.
Background
2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy ] -phenyl } -2-methyl-propan-1-one is an α -hydroxyketone photoinitiator; which exhibits excellent performance in printing ink formulations;
the traditional preparation process of 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy ] -phenyl } -2-methyl-propan-1-one takes diphenyl ether as raw material, and sequentially carries out Friedel-crafts reaction, chlorination reaction and alkaline hydrolysis reaction to obtain the product, wherein the chlorination reaction adopts glacial acetic acid as a solvent, and the product is subjected to vacuum desolventizing after the chlorination reaction is finished, acetic acid in the chlorination reaction liquid cannot be completely separated, more residues exist in the process, acetate formed by reaction with alkali liquor in the subsequent alkaline hydrolysis reaction is dissolved in water, recycling is difficult, and the vacuum desolventizing energy consumption and the cost are high;
therefore, the development of a preparation method of the alpha-chloro intermediate with high alpha-chloro selectivity, low cost, low energy consumption and simple operation is still of great significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a chloro intermediate of a synthetic photoinitiator, wherein the preparation method comprises the steps of adding sulfuric acid with the concentration of 30% -85% as an auxiliary agent in a chloro reaction, so that side reactions on benzene rings can be reduced, the occurrence of chloro substitution reaction on the benzene rings can be inhibited, the selectivity of alpha-chloro reaction can be improved, and the product yield can be further improved; compared with the traditional chlorination process using acetic acid as a solvent, the method disclosed by the invention has the advantages that the sulfuric acid with the concentration is used as an auxiliary agent, the selectivity of alpha-chlorination reaction is improved, sulfuric acid in a product is conveniently separated after the chlorination reaction is finished, and a sulfuric acid phase obtained by liquid separation can be recycled, so that the material cost is reduced, the liquid separation operation is simple, and the energy consumption is lower.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a chloro intermediate for synthesizing a photoinitiator, wherein the molecular structure of the chloro intermediate is shown in the following formula a;
the preparation method comprises the following steps: mixing a compound solution of the formula b with sulfuric acid with the concentration of 30% -85% (comprising 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80% and the like in an exemplary manner), and introducing chlorine gas to perform chlorination reaction to obtain a chlorinated intermediate solution; the formula of the compound of formula b is shown below;
2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy ] -phenyl } -2-methyl-propan-1-one is an alpha-hydroxyketone photoinitiator, which is prepared from diphenyl ether as raw material by Friedel-crafts reaction, chlorination reaction and alkaline hydrolysis reaction in sequence; acetic acid is used as a solvent in a large amount in the traditional chlorination reaction process, and is not easy to be removed cleanly after the reaction is finished by vacuum desolventization, and although the residual acetic acid cannot directly influence the subsequent reaction, more alkaline aqueous solution is consumed in the subsequent alkaline hydrolysis reaction, and the acetic acid is converted into acetate to be dissolved in water and is not easy to be recycled; and the energy consumption of vacuum desolventizing is high; in order to solve the technical problems, the invention provides a chlorination process which has high selectivity and high yield of alpha-chlorination reaction, is easy to recycle and reuse auxiliary agents, and is simple to operate, low in cost and low in energy consumption;
in the preparation process of the chloro intermediate, sulfuric acid with the concentration of 30-85% is added as an auxiliary agent, and the occurrence of chloro substitution reaction on a benzene ring can be effectively inhibited, so that the selectivity of alpha-chloro reaction is improved, the yield of a target product is further improved, and the selectivity of the chloro reaction can reach more than 98%;
and the sulfuric acid with the concentration of 30-85% is used as an auxiliary agent, after the chlorination reaction is finished, water can be added, and the mixture is stood to realize layering of a chlorinated intermediate solution and a sulfuric acid phase, so that the sulfuric acid residue in the chlorinated intermediate solution is less, the recycling and the application of the sulfuric acid are conveniently realized, the problem of difficult separation of acetic acid in the traditional process is solved, the energy consumption and the process cost are reduced, and the operation is simpler.
The invention discovers that when the concentration of sulfuric acid is 30% -85%, the alpha-chloro reactivity is optimal, after the reaction is finished, sulfuric acid and chloro intermediate solution are easier to realize two-phase separation by standing and layering, when the concentration of the initial sulfuric acid is 30% -70%, water is not needed to be added before subsequent standing and separating, when the concentration of the initial sulfuric acid is more than 70%, the concentration of the sulfuric acid can be adjusted to be 30% -70% by adding water before standing and separating, and further, the two-phase separation of sulfuric acid and chloro intermediate organic phase is convenient to be realized by standing and separating.
The above-described chlorination equation is shown below:
preferably, the operating temperature at which the solution of compound of formula b is mixed with sulfuric acid having a concentration of 30% to 85% (exemplary including 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.) is-5 ℃ to 5 ℃, for example-4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃, 1 ℃, 2 ℃, 3 ℃ or 4 ℃, etc.
In the invention, the compound solution of the formula b and sulfuric acid are mixed at the temperature, and the mixing process is required to be accompanied by stirring, especially when sulfuric acid with relatively high concentration is used, the temperature is controlled and accompanied by stirring, so that obvious heat release or excessively rapid local heat release can be effectively avoided.
The concentration of sulfuric acid is not too high, and when concentrated sulfuric acid having a concentration of more than 85% is used, the reaction solution becomes black.
Preferably, the chlorination reaction is carried out at a temperature of 25℃to 50℃such as 30℃and 35℃and 40℃or 45℃and the like.
The preferred reaction temperature of the invention is in the above temperature range, when the temperature is more than 50 ℃, the side reaction on the benzene ring can be obviously increased, the side reaction has an increasing trend when the temperature is higher, especially the side reaction is more obvious in the later stage of the reaction, when the temperature is less than 25 ℃, the reaction rate is relatively low, which is not beneficial to improving the efficiency and shortening the production period.
Preferably, the compound of formula b is reacted with H in sulfuric acid 2 SO 4 The mass ratio of (2) is 0.75-1.25:1, such as 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1 or 1.2:1, etc.).
The invention adopts the proportion, which is convenient for improving the selectivity of the alpha-chloro reaction and reducing the generation of byproducts; when the addition amount of sulfuric acid is low, the effect of the auxiliary agent is not obvious, the sulfuric acid phase can not be directly separated after the reaction is finished, a large amount of water is needed to be added for separating liquid, the obtained diluted sulfuric acid can not be reused, the generation of waste acid water can not be effectively reduced, the environmental pressure is high, and when the addition amount of sulfuric acid is too high, more products can be dissolved to cause low yield.
Preferably, the solvent of the compound solution of formula b is selected from any one or a combination of at least two of chlorobenzene, dichloroethane or dichloromethane.
Preferably, the chlorination reaction is carried out in a reaction device connected to a tail gas absorbing device, preferably the absorbent in the tail gas absorbing device is selected from alkali lyes, preferably aqueous sodium hydroxide.
The aqueous solution of sodium hydroxide is used as the absorption liquid, which can absorb HCl generated by the chlorination reaction, thereby avoiding environmental pollution.
Preferably, after the chlorination reaction is finished, water is added into the reaction liquid, and the mixture is mixed and separated to obtain an organic phase and a sulfuric acid phase, and the organic phase is washed with water to obtain a chlorinated intermediate solution.
Preferably, the water is added in an amount such that H in the sulfuric acid phase is obtained from the separation 2 SO 4 The concentration of (2) is 30% to 70%, for example 35%, 40%, 45%, 50%, 55%, 60% or 65%, etc.
In the invention, the addition amount of water is controlled so that H in sulfuric acid phase obtained by separating liquid 2 SO 4 The concentration of the alkali solution is 30-70%, and in the concentration range, on one hand, the sulfuric acid phase and the organic phase are conveniently formed by standing and layering, so that the separation of the sulfuric acid phase and the organic phase is realized, the process operation is simple, the cost is low, the energy consumption is low, and the alkali solution consumption in the subsequent alkaline hydrolysis reaction is low; on the other hand, the sulfuric acid phase is convenient to apply mechanically, and the recycling of the sulfuric acid auxiliary agent is realized.
Preferably, the compound of formula b is prepared by a process comprising the steps of:
(1) Mixing diphenyl ether, an organic solvent and a catalyst, and then dropwise adding isobutyryl chloride to perform Friedel-crafts reaction;
(2) And (3) mixing the reaction solution obtained in the step (1) with a hydrolysis reagent for hydrolysis reaction, separating the solution to obtain an organic phase, and then washing with water to obtain a compound solution of the formula b.
Preferably, the catalyst is selected from anhydrous aluminum trichloride.
In the preparation method of the invention, the reaction equation of the preparation method of the compound of the formula b is shown as follows;
preferably, the temperature of the Friedel-crafts reaction in step (1) is from-5℃to 0℃such as-4 ℃, -3 ℃, -2℃or-1 ℃.
Preferably, the method of mixing the diphenyl ether, the organic solvent and the catalyst in step (1) comprises mixing the diphenyl ether and the organic solvent, followed by adding the catalyst at-5 to 0 ℃ (exemplary including-4 ℃, -3 ℃, -2 ℃ or-1 ℃).
Preferably, the organic solvent in step (1) is selected from any one or a combination of at least two of chlorobenzene, dichloroethane or dichloromethane.
Preferably, the friedel-crafts reaction in step (1) is carried out in a reaction device connected to a tail gas absorbing device, the absorbent of which is selected from water, preferably ice water.
In the Friedel-crafts reaction, the tail gas absorbing device adopts ice water as an absorbent, and absorbs HCl generated by the Friedel-crafts reaction to obtain ice water solution containing HCl, and the ice water solution can be used as a hydrolysis reagent subsequently, so that comprehensive utilization of resources is realized.
Preferably, the hydrolysis reagent in step (2) is selected from ice water solutions comprising HCl.
Preferably, the ice water solution containing HCl is ice water from a tail gas absorber.
The absorbent ice water in the tail gas absorbing device can be used as a hydrolysis reagent for hydrolysis after the Friedel-crafts reaction.
Preferably, the water washing is followed by purification.
Preferably, the method of purification comprises desolventizing and recrystallisation.
Preferably, the solvent for recrystallization is any one or a combination of at least two of methanol, petroleum ether or n-hexane.
In a second aspect, the invention provides a preparation method of a photoinitiator, wherein the structural formula of the photoinitiator is shown as formula c:
the preparation method comprises the following steps:
preparing a chlorinated intermediate solution by a method as described in the first aspect;
and (II) mixing the chlorinated intermediate solution in the step (I) with alkali liquor, and heating to perform alkaline hydrolysis reaction to obtain the photoinitiator.
In the present invention, the alkaline hydrolysis reaction equation of the chlorinated intermediate solution is as follows:
preferably, the lye of step (II) is an aqueous sodium hydroxide solution, preferably at a concentration of 10% -50% (exemplary include 15%, 20%, 25%, 30%, 35%, 40% or 45%, etc.).
Preferably, the alkaline hydrolysis reaction is carried out at a temperature of 50℃to 80℃such as 55℃60℃65℃70℃or 75℃in step (II).
In the present invention, the alkaline hydrolysis reaction is carried out in the above temperature range, and most advantageously, the alkaline hydrolysis reaction rate is slow at a temperature lower than 50℃and it takes 2 times or more to lengthen the time, and the side reaction elimination reaction tends to increase at a temperature higher than 80 ℃.
Preferably, stirring is carried out during the alkaline hydrolysis reaction at the elevated temperature in step (II).
Preferably, the step (II) further comprises cooling, liquid separation, organic phase water washing, desolventizing, recrystallization and drying after the alkaline hydrolysis reaction is finished, so as to obtain the photoinitiator.
Preferably, the solvent for recrystallization is selected from any one or a combination of at least two of methanol, petroleum ether or n-hexane.
As a preferable technical scheme of the invention, the preparation method of the photoinitiator comprises the following steps:
(a) Mixing diphenyl ether and an organic solvent in a reaction device, cooling to-5-0 ℃, adding a catalyst, and then dropwise adding isobutyryl chloride to perform Friedel-crafts reaction, wherein the reaction device is connected with a tail gas absorbing device, and an absorbent of the tail gas absorbing device is selected from ice water;
(b) And (3) mixing the reaction liquid obtained in the step (a) with ice water in a tail gas absorption device, separating the liquid to obtain an organic phase, and then washing the organic phase with water to obtain a compound solution of the formula b.
(c) Mixing the compound solution of the formula b obtained in the step (b) with sulfuric acid with the concentration of 30-85% in a reaction device at the temperature of-5 ℃, wherein the reaction device is connected with a tail gas absorption device, and an absorbent in the tail gas absorption device is selected from sodium hydroxide aqueous solution; the temperature is raised to 25 ℃ to 50 ℃ under the condition of fully stirring in the reaction device, and chlorine is introduced to carry out chlorination reaction;
(d) After the reaction in the step (c) is finished, adding water into the reaction solution, stirring, separating the solution to obtain an organic phase and a sulfuric acid phase, and washing the organic phase by water to obtain a chlorinated intermediate solution; wherein water is added to the reaction solution in such an amount that H in the resulting sulfuric acid phase 2 SO 4 The concentration of (2) is 30% -70%;
(e) Mixing the chlorinated intermediate solution obtained in the step (d) with a sodium hydroxide aqueous solution, heating to 50-80 ℃, carrying out alkaline hydrolysis reaction with stirring, cooling, standing for layering after the reaction is completed, separating liquid, washing an organic phase with water, desolventizing, recrystallizing with methanol, filtering, and drying to obtain the white solid photoinitiator.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method, sulfuric acid with the concentration of 30-85% is adopted as an auxiliary agent for the chlorination reaction, so that the occurrence of the chloro substitution reaction on the benzene ring can be inhibited, the selectivity of the alpha-chloro substitution reaction is improved, and the yield of the product is improved;
(2) Compared with the traditional chlorination process using acetic acid as a solvent, the preparation method disclosed by the invention has the advantages that after the chlorination reaction is finished, sulfuric acid with the concentration of 30% -85% is used as an auxiliary agent, the sulfuric acid and the chlorinated intermediate solution are conveniently separated in a standing and liquid separating mode, the sulfuric acid residue in the chlorinated intermediate solution is less, the consumption of alkali liquor in the subsequent alkaline hydrolysis reaction is less, and compared with the traditional vacuum desolventizing and acetic acid removing mode, the liquid separating mode is simpler to operate and lower in energy consumption;
(3) The sulfuric acid phase obtained by liquid separation in the preparation method can be directly used, and the process cost is low.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present example provides a process for the preparation of 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy ] -phenyl } -2-methyl-propan-1-one, comprising the steps of:
(1) In a reaction device, mixing 221.3g (1.3 mol) of diphenyl ether with 300mL of chlorobenzene, cooling to-5 ℃, connecting the reaction device with a tail gas absorbing device, adding 373.3g (2.8 mol) of anhydrous aluminum chloride into the reaction device, wherein the tail gas absorbing agent is ice water; then, 297.8g (2.8 mol) of isobutyryl chloride is dripped, the reaction is carried out under the condition of heat preservation and stirring, and the reaction is detected to be complete by thin layer chromatography;
(2) Mixing the reaction liquid obtained in the step (1) with ice water in a tail gas absorption device, stirring for 0.5h, standing in a separating funnel to separate two phases, and washing an organic phase with water to obtain a compound solution of the formula b; HPLC detection content > 95%;
(3) In a reaction device, controlling the temperature at 0 ℃, uniformly mixing the compound solution of the formula b obtained in the step (2) with 530g of 75% sulfuric acid, heating to 35 ℃ and fully stirring, introducing 184.6g of chlorine into the reaction device, controlling the introducing speed of the chlorine to be slower at the end of the reaction, detecting that the reaction is complete by thin layer chromatography, opening a vent valve, introducing tail gas into a tail gas absorbing device, and using the tail gas absorbent as sodium hydroxide aqueous solution;
(4) Adding 206mL of water into the reaction solution obtained in the step (3), uniformly stirring, standing for layering, separating the solution, and washing the organic phase with water to obtain a chlorinated intermediate solution with the HPLC purity of 97%; h in the sulfuric acid phase obtained 2 SO 4 Is 54%;
(5) Mixing the chloro intermediate solution obtained in the step (4) with 418g of 30% sodium hydroxide aqueous solution, raising the temperature to 60 ℃, fully stirring and preserving heat for reaction, detecting the reaction to be complete by thin layer chromatography, cooling to room temperature, standing for layering, separating liquid, washing an organic phase with water, distilling chlorobenzene, recrystallizing and purifying with methanol, filtering, and drying to obtain 400.6g (yield 89.9%) of white crystals (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy ] -phenyl } -2-methyl-propan-1-one), wherein the melting point is 98-101 ℃ and the purity is 98.8%.
Nuclear magnetic resonance analysis was performed on the white crystals obtained, and the results were as follows:
1H-NMR(CDCl3,400MH):7.89(d,4H),6.95(d,4H),2.54(s,2H),1.39(s,12H)。
example 2
This example differs from example 1 in that 530g of 75% sulfuric acid was replaced in step (3) by using the 54% sulfuric acid separated in step (4) of example 1, and in that no more water was added in step (4), and other parameters and conditions were exactly the same as in example 1.
The product obtained in step (5) of this example was white crystals with a purity of 98.1% and a yield of 86.3%.
Example 3
This example differs from example 1 in that 530g of 75% sulfuric acid in step (3) was replaced with 610g of 65% sulfuric acid, and in step (4) no water was added, and other parameters and conditions were exactly the same as in example 1.
The product obtained in step (5) of this example was white crystals with a purity of 98.3% and a yield of 88.5%.
Example 4
This example differs from example 1 in that no water is added in step (4), and other parameters and conditions are exactly the same as in example 1.
In this example, the delamination of the reaction liquid after the reaction was not obvious, and a large amount of the product was dissolved in the sulfuric acid phase, so that the post-treatment could not be performed without adding water in the step (4).
Comparative example 1
This comparative example differs from example 1 in that sulfuric acid was not added in step (3), and other parameters and conditions were exactly the same as in example 1. In this example, the purity of the chlorinated intermediate obtained by HPLC detection of the reaction solution after the same reaction time was only 47%.
Comparative example 2
This comparative example differs from example 1 in that 530g of 75% sulfuric acid in step (3) was replaced with 1985g of 20% sulfuric acid, and water was not added in step (4), and other parameters and conditions were exactly the same as in example 1.
The product obtained in this comparative example was white crystals with a purity of 97.8% and a yield of 78.9%.
Comparative example 3
This comparative example differs from example 1 in that the solvent was removed from the solution obtained in step (2), and 530g of 75% sulfuric acid in step (3) was replaced with 330g of acetic acid, while no solvent was added, and other parameters and conditions were exactly the same as in example 1. After the same time of reaction in step (3) and example 1, HPLC was performed to detect that 35% of the compound of formula b remained as the reaction starting material.
Comparative example 4
This comparative example differs from example 1 in that 530g of 75% sulfuric acid in step (3) was replaced with 405g of 98% sulfuric acid, and other parameters and conditions were exactly the same as in example 1.
In the comparative example, when concentrated sulfuric acid was added, the reaction solution was progressively darker as the reaction proceeded, and the reaction solution obtained in step (3) was tested by HPLC to obtain a content of chloro compound of only 75%.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (30)
1. A preparation method of a chloro intermediate of a synthetic photoinitiator is characterized in that the molecular structure of the chloro intermediate is shown in the following formula a;
the preparation method comprises the following steps: mixing the compound solution of the formula b with sulfuric acid with the concentration of 30% -85%, and introducing chlorine gas to perform chlorination reaction to obtain a chlorinated intermediate solution; the formula of the compound of formula b is shown below;
2. the process according to claim 1, wherein the temperature at which the solution of the compound of formula b is mixed with sulfuric acid having a concentration of 30% to 85% is-5 ℃ to 5 ℃.
3. The process according to claim 1, wherein the chlorination reaction is carried out at a temperature of 25℃to 50 ℃.
4. The process according to claim 1, wherein the compound of formula b is reacted with H in sulfuric acid 2 SO 4 The mass ratio of (2) is 0.75-1.25:1.
5. The process according to claim 1, wherein the solvent of the solution of the compound of formula b is selected from any one or a combination of at least two of chlorobenzene, dichloroethane or dichloromethane.
6. The process of claim 1, wherein the chlorination reaction is carried out in a reaction device coupled to an off-gas absorber.
7. The method according to claim 6, wherein the absorbent in the tail gas absorbing device is selected from lye.
8. The method according to claim 7, wherein the alkaline solution is an aqueous sodium hydroxide solution.
9. The preparation method according to claim 1, wherein the preparation method further comprises the steps of adding water into the reaction solution after the chlorination reaction is finished, mixing, separating the solution to obtain an organic phase and a sulfuric acid phase, and washing the organic phase with water to obtain a chlorinated intermediate solution.
10. The process according to claim 9, wherein the water is added in such an amount that H in the sulfuric acid phase obtained from the separation 2 SO 4 The concentration of (2) is 30% -70%.
11. The process according to claim 1, wherein the compound of formula b is prepared by a process comprising the steps of:
(1) Mixing diphenyl ether, an organic solvent and a catalyst, and then dropwise adding isobutyryl chloride to perform Friedel-crafts reaction;
(2) And (3) mixing the reaction solution obtained in the step (1) with a hydrolysis reagent for hydrolysis reaction, separating the solution to obtain an organic phase, and then washing with water to obtain a compound solution of the formula b.
12. The method of preparation according to claim 11, wherein the catalyst is selected from the group consisting of anhydrous aluminum trichloride.
13. The process according to claim 11, wherein the temperature of the friedel-crafts reaction in step (1) is-5 ℃ to 0 ℃.
14. The method of preparing according to claim 11, wherein the method of mixing the diphenyl ether, the organic solvent and the catalyst in step (1) comprises mixing the diphenyl ether and the organic solvent, followed by adding the catalyst at-5 to 0 ℃.
15. The method according to claim 11, wherein the organic solvent in step (1) is selected from one or a combination of at least two of chlorobenzene, dichloroethane or dichloromethane.
16. The process of claim 11 wherein the friedel-crafts reaction in step (1) is carried out in a reaction apparatus connected to a tail gas absorber, the absorber of the tail gas absorber being selected from water.
17. The method of claim 16, wherein the absorbent is ice water.
18. The process according to claim 11, wherein the hydrolysis reagent in step (2) is selected from the group consisting of ice water solutions containing HCl.
19. The method of claim 18, wherein the ice water solution comprising HCl is ice water from a tail gas absorber.
20. The method of claim 11, wherein the washing with water is followed by purification.
21. The method of claim 20, wherein the purification comprises desolventizing and recrystallizing.
22. The method of claim 21, wherein the solvent for recrystallization is any one or a combination of at least two of methanol, petroleum ether, or n-hexane.
23. A preparation method of a photoinitiator is characterized in that the structural formula of the photoinitiator is shown as a formula c:
the preparation method comprises the following steps:
preparing a chlorinated intermediate solution by the process of any one of claims 1-6;
and (II) mixing the chlorinated intermediate solution in the step (I) with alkali liquor, and heating to perform alkaline hydrolysis reaction to obtain the photoinitiator.
24. The process of claim 23, wherein the lye of step (ii) is aqueous sodium hydroxide.
25. The process of claim 24, wherein the lye is an aqueous sodium hydroxide solution having a concentration of 10% to 50%.
26. The process according to claim 23, wherein the alkaline hydrolysis is carried out at a temperature of 50℃to 80℃at a temperature elevated in step (II).
27. The process according to claim 23, wherein the alkaline hydrolysis is carried out at elevated temperature in step (ii) with stirring.
28. The process of claim 23, wherein the step (ii) further comprises cooling, separating liquid, washing the organic phase with water, desolventizing, recrystallizing, and drying to obtain the photoinitiator.
29. The method of claim 28, wherein the solvent for recrystallization is selected from any one or a combination of at least two of methanol, petroleum ether, and n-hexane.
30. The method of preparation according to claim 23, characterized in that the method of preparation comprises the steps of:
(a) Mixing diphenyl ether and an organic solvent in a reaction device, cooling to-5-0 ℃, adding a catalyst, and then dropwise adding isobutyryl chloride to perform Friedel-crafts reaction, wherein the reaction device is connected with a tail gas absorbing device, and an absorbent of the tail gas absorbing device is selected from ice water;
(b) Mixing the reaction liquid obtained in the step (a) with ice water in a tail gas absorption device, separating the liquid to obtain an organic phase, and then washing the organic phase with water to obtain a compound solution of a formula b;
(c) Mixing the compound solution of the formula b obtained in the step (b) with sulfuric acid with the concentration of 30-85% in a reaction device at the temperature of-5 ℃, wherein the reaction device is connected with a tail gas absorption device, and an absorbent in the tail gas absorption device is selected from sodium hydroxide aqueous solution; the temperature is raised to 25 ℃ to 50 ℃ under the condition of fully stirring in the reaction device, and chlorine is introduced to carry out chlorination reaction;
(d) After the reaction in the step (c) is finished, adding water into the reaction solution, stirring, separating the solution to obtain an organic phase and a sulfuric acid phase, and washing the organic phase by water to obtain a chlorinated intermediate solution; wherein water is added to the reaction solution in such an amount that H in the resulting sulfuric acid phase 2 SO 4 The concentration of (2) is 30% -70%;
(e) Mixing the chlorinated intermediate solution obtained in the step (d) with a sodium hydroxide aqueous solution, heating to 50-80 ℃, carrying out alkaline hydrolysis reaction with stirring, cooling, standing for layering after the reaction is completed, separating liquid, washing an organic phase with water, desolventizing, recrystallizing with methanol, filtering, and drying to obtain the white solid photoinitiator.
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| CN103351287A (en) * | 2013-06-27 | 2013-10-16 | 江苏扬农化工集团有限公司 | Method for synthesizing 2-chloropropionaldehyde |
| CN106659162A (en) * | 2014-06-04 | 2017-05-10 | 孟山都技术公司 | 3,6-dichlorosalicylic acid compounds and related synthetic processes |
| CN111138260A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Preparation method of α -hydroxyketone bifunctional photoinitiator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103351287A (en) * | 2013-06-27 | 2013-10-16 | 江苏扬农化工集团有限公司 | Method for synthesizing 2-chloropropionaldehyde |
| CN106659162A (en) * | 2014-06-04 | 2017-05-10 | 孟山都技术公司 | 3,6-dichlorosalicylic acid compounds and related synthetic processes |
| CN111138260A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Preparation method of α -hydroxyketone bifunctional photoinitiator |
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