CN103833538A - Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method - Google Patents
Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method Download PDFInfo
- Publication number
- CN103833538A CN103833538A CN201410068148.9A CN201410068148A CN103833538A CN 103833538 A CN103833538 A CN 103833538A CN 201410068148 A CN201410068148 A CN 201410068148A CN 103833538 A CN103833538 A CN 103833538A
- Authority
- CN
- China
- Prior art keywords
- benzophenone
- tetraalkyl
- raw material
- prepares
- kettle way
- 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
Classifications
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- 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
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3,3',4,4'-tetraalkyl benzophenone by a one-pot method and belongs to the field of chemical synthesis. The method comprises the steps of mixing o-dialkylphenyl, which serves as a raw material, and Lewis acid and concentrated sulfuric acid, which serve as catalysts, so as to form a mixed liquid, dropwise adding carbon tetrachloride into the mixed liquid, and carrying out heat preservation for 0.5-5 hours at the temperature of 0-30 DEG C after the dropwise adding is completed. Compared with the prior art, the method disclosed by the invention has the advantages that a two-step synthesis method is simplified into the one-pot method, so that the process is simplified, the operation is simpler and more convenient, the product can be obtained by one-step aftertreatment only, and the productivity is increased. Furthermore, the method has low requirements on temperature, the whole process does not need heating or cooling, no special requirements on equipment exist, and the operation is safe, simple and convenient.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of one kettle way and prepare 3,3 ', 4, the method for 4 '-tetraalkyl benzophenone.
Background technology
3,3 ', 4,4 '-tetraalkyl benzophenone is a kind of important industrial chemicals, is used for preparing matrix resin and the high temperature resistant polyester of advanced composite material, has wide market outlook at home and abroad.Domestic preparation 3,3 ', 4,4 '-tetraalkyl benzophenone adjacent dialkyl benzene and organic aldehydes of adopting are prepared by the method reoxidizing after nitration mixture catalyzing and condensing more.
First adjacent dialkyl benzene and carbonyl compound (formaldehyde, any in acetone) are mixed, add afterwards mixed acid catalyst reaction, prepare 3,3 ', 4,4 '-tetraalkyl diphenyl alkane.3,3 ', 4,4 '-tetraalkyl diphenyl alkane is used nitric acid oxidation again, generates 3,3 ', 4,4 '-tetraalkyl benzophenone.But this synthetic method reactions steps is loaded down with trivial details, and long reaction time and yield are low.
Summary of the invention
The object of the invention is provides a kind of one kettle way to prepare 3 for above-mentioned technical problem, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone.
Object of the present invention can be achieved through the following technical solutions:
A kind of one kettle way prepares 3,3 ', 4, the method of 4 '-tetraalkyl benzophenone, the method is take adjacent dialkyl benzene as raw material, take Lewis acid and the vitriol oil as catalyzer, to after described raw material and catalyst mix, form mixed solution, in described mixed solution, dripping tetracol phenixin, after dropwising, is to be incubated 0.5～5h under the condition of 0～30 ℃ in temperature.
Described raw material and lewis acidic mol ratio are 1:0.5～2; The mass ratio of the vitriol oil and raw material is 1:10～15; The mol ratio of raw material and tetracol phenixin is 1:0.5～4.Preferably, described raw material and lewis acidic mol ratio are 1:0.5～1; The mass ratio of the vitriol oil and raw material is 1:10～14; The mol ratio of raw material and tetracol phenixin is 1:1～2.2.
Described adjacent dialkyl benzene is o-Xylol, adjacent diethylbenzene or adjacent diisopropylbenzene(DIPB) (diisopropylbenzene(DIPB)).
Described Lewis acid is the vitriol without crystal water, nitrate or the halogenide of zinc, aluminium, zirconium, iron, tin, titanium.Preferably, described Lewis acid is aluminum chloride, iron(ic) chloride, zinc chloride, tin chloride or titanium chloride.
In technical solution of the present invention, preferably under being the condition of 0～30 ℃, temperature is incubated 0.5～2h.
Beneficial effect of the present invention:
1. with respect to prior art, two-step synthetic method is reduced to one kettle way by technical solution of the present invention, simplified technique, operates easylier, only needs a step aftertreatment can obtain product, improved production capacity.
2. the solvent adopting in technical solution of the present invention is tetracol phenixin, and this solvent phase is for formaldehyde, and acetaldehyde, is more convenient to transportation and stores, reinforced also convenient, and can recovery.
3. the solvent tetracol phenixin using in the present invention is also as reactant, and reaction has directly generated target product after aftertreatment, and having avoided needs to adopt oxygenant (as rare nitric acid) oxidation to prepare the process of target product in traditional technology.
4. this reaction does not have high requirements to temperature, and whole process does not need heating or cooling, and equipment is not had to particular requirement, simple and safe operation yet.
5. this reaction process is very short, drip and only need insulation to get final product aftertreatment in 0.5～2 hour, and transformation efficiency can reach 99%.
6. owing to simplifying technique and last handling process, present method productive rate also increases.
On the whole, with respect to former method, the method cost that the present invention narrates is lower, operate easier, be more applicable to large-scale industrial production.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this:
Embodiment 1
O-Xylol 106g, aluminum chloride 90g and vitriol oil 10g are added in reaction flask.250g tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 0.5 hour under 0-5 ℃ of condition in temperature, and HPLC detects o-Xylol and disappears, and gets final product termination reaction.Wash away unnecessary aluminum chloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 241g.Residue oily matter 500g ethyl alcohol recrystallization, can obtain 3,3 ', 4,4 '-tetramethyl-benzophenone 200g, and productive rate is 84.0%, purity 98.5%.
Embodiment 2
O-Xylol 106g, iron trichloride 130g and vitriol oil 10g are added in reaction flask.154g tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 0.8 hour under 5-10 ℃ of condition in temperature, and HPLC detects o-Xylol and disappears, and gets final product termination reaction.Wash away unnecessary iron trichloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 233g.Residue oily matter 500g ethyl alcohol recrystallization, can obtain 3,3 ', 4,4 '-tetramethyl-benzophenone 209g, and productive rate is 87.8%, purity 98.4%.
Embodiment 3
Adjacent diethylbenzene 134g, zinc chloride 136g and vitriol oil 10g are added in reaction flask.321g tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.5 hours under 0-5 ℃ of condition in temperature, and HPLC detects adjacent diethylbenzene and disappears, and gets final product termination reaction.Wash away unnecessary zinc chloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 296g.Residue oily matter 600g recrystallizing methanol, can obtain 3,3 ', 4,4 '-tetraethyl-benzophenone 244g, and productive rate is 83.0%, purity 98.1%.
Embodiment 4
O-Xylol 1.06kg, zinc chloride 1.36kg and vitriol oil 0.1kg are added in reaction flask.3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.8 hours under the condition of 5-10 ℃ in temperature, and HPLC detects o-Xylol and disappears, and gets final product termination reaction.Wash away unnecessary zinc chloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 2.37kg.Residue oily matter 5kg ethyl alcohol recrystallization, can obtain 3,3 ', 4,4 '-tetramethyl-benzophenone 1.99kg, and productive rate is 83.9%, purity 99.0%.
Embodiment 5
Adjacent diethylbenzene 1.34kg, aluminum chloride 0.90kg and vitriol oil 0.1kg are added in reaction flask.3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.2 hours under 25-30 ℃ of condition in temperature, and HPLC detects adjacent diethylbenzene and disappears, and gets final product termination reaction.Wash away unnecessary aluminum chloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 3.0g.Residue oily matter 6kg recrystallizing methanol, can obtain 3,3 ', 4,4 '-tetraethyl-benzophenone 2.62g, and productive rate is 89.1%, purity 98.6%.
Embodiment 6
Adjacent diethylbenzene 1.34kg, Tai-Ace S 150 1.95kg and vitriol oil 0.1kg are added in reaction flask.3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.2 hours under 20-25 ℃ of condition in temperature, and HPLC detects adjacent diethylbenzene and disappears, and gets final product termination reaction.Wash away unnecessary Tai-Ace S 150 and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 3.2g.Residue oily matter 6kg recrystallizing methanol, can obtain 3,3 ', 4,4 '-tetraethyl-benzophenone 2.43g, and productive rate is 82.6%, purity 98.4%.
Embodiment 7
O-Xylol 1.06kg, tin tetrachloride 2.0kg and vitriol oil 0.1kg are added in reaction flask.3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.8 hours under 15-20 ℃ of condition in temperature, and HPLC detects o-Xylol and disappears, and gets final product termination reaction.Wash away unnecessary tin tetrachloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 2.50kg.Residue oily matter 5kg ethyl alcohol recrystallization, can obtain 3,3 ', 4,4 '-tetramethyl-benzophenone 2.02kg, and productive rate is 84.0%, purity 98.1%
Embodiment 8
O-Xylol 1.06kg, titanium tetrachloride 1.45kg and vitriol oil 0.1kg are added in reaction flask, 3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.8 hours under 15-20 ℃ of condition in temperature, HPLC detects o-Xylol and disappears, and gets final product termination reaction.Wash away unnecessary titanium tetrachloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 2.30kg.Residue oily matter 5kg ethyl alcohol recrystallization, can obtain 3,3 ', 4,4 '-tetramethyl-benzophenone 1.98kg, and productive rate is 83.2%, purity 98.4%
Embodiment 9
Adjacent diisopropylbenzene(DIPB) (diisopropylbenzene(DIPB)) 1.62kg, iron trichloride 1.30kg and vitriol oil 0.1kg are added in reaction flask.3kg tetracol phenixin is added drop-wise in reaction flask, after dropwising, is to be incubated 1.2 hours under 25-30 ℃ of condition in temperature, and HPLC detects adjacent diisopropylbenzene(DIPB) and disappears, and gets final product termination reaction.Wash away unnecessary iron trichloride and the vitriol oil with clear water, until pH=4～5, reclaim under reduced pressure residue tetracol phenixin, obtains oily matter 3.2g.Residue oily matter 6kg recrystallizing methanol, can obtain 3,3 ', 4,4 '-tetraethyl-benzophenone 2.45g, and productive rate is 82.7%, purity 98.0%.
Claims (7)
1. one kettle way prepares 3,3 ', 4, the method of 4 '-tetraalkyl benzophenone, is characterized in that: the method is take adjacent dialkyl benzene as raw material, take Lewis acid and the vitriol oil as catalyzer, to after described raw material and catalyst mix, form mixed solution, in described mixed solution, dripping tetracol phenixin, after dropwising, is to be incubated 0.5～5h under the condition of 0～30 ℃ in temperature.
2. one kettle way according to claim 1 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: described raw material and lewis acidic mol ratio are 1:0.5～2; The mass ratio of the vitriol oil and raw material is 1:10～15; The mol ratio of raw material and tetracol phenixin is 1:0.5～4.
3. one kettle way according to claim 2 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: described raw material and lewis acidic mol ratio are 1:0.5～1; The mass ratio of the vitriol oil and raw material is 1:10～14; The mol ratio of raw material and tetracol phenixin is 1:1～2.2.
4. one kettle way according to claim 1 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: described adjacent dialkyl benzene is o-Xylol, adjacent diethylbenzene or adjacent diisopropylbenzene(DIPB).
5. one kettle way according to claim 1 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: described Lewis acid is the vitriol without crystal water, nitrate or the halogenide of zinc, aluminium, zirconium, iron, tin, titanium.
6. one kettle way according to claim 5 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: described Lewis acid is aluminum chloride, iron(ic) chloride, zinc chloride, tin chloride or titanium chloride.
7. one kettle way according to claim 1 prepares 3, and 3 ', 4, the method for 4 '-tetraalkyl benzophenone, is characterized in that: be to be incubated 0.5～2h under the condition of 0～30 ℃ in temperature.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410068148.9A CN103833538A (en) | 2014-02-27 | 2014-02-27 | Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method |
| CN201410837560.2A CN104557501B (en) | 2014-02-27 | 2014-12-29 | One kettle way prepares the method for 3,3 ', 4,4 '-tetraalkyl benzophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410068148.9A CN103833538A (en) | 2014-02-27 | 2014-02-27 | Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103833538A true CN103833538A (en) | 2014-06-04 |
Family
ID=50797480
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410068148.9A Pending CN103833538A (en) | 2014-02-27 | 2014-02-27 | Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method |
| CN201410837560.2A Active CN104557501B (en) | 2014-02-27 | 2014-12-29 | One kettle way prepares the method for 3,3 ', 4,4 '-tetraalkyl benzophenone |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410837560.2A Active CN104557501B (en) | 2014-02-27 | 2014-12-29 | One kettle way prepares the method for 3,3 ', 4,4 '-tetraalkyl benzophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103833538A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409156B (en) * | 2020-11-30 | 2022-04-08 | 山东华夏神舟新材料有限公司 | Preparation method of tetraalkyl benzophenone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6471835A (en) * | 1987-09-11 | 1989-03-16 | Chemipro Kasei Kaisha Ltd | Production of benzophenones containing hydroxyl group at 4-position |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910006903B1 (en) * | 1989-10-20 | 1991-09-10 | 주식회사 코오롱 | The product process of 2,2'-dihydroxy-4,4'-dialkoxybenzophenone derivatives |
-
2014
- 2014-02-27 CN CN201410068148.9A patent/CN103833538A/en active Pending
- 2014-12-29 CN CN201410837560.2A patent/CN104557501B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6471835A (en) * | 1987-09-11 | 1989-03-16 | Chemipro Kasei Kaisha Ltd | Production of benzophenones containing hydroxyl group at 4-position |
Non-Patent Citations (1)
| Title |
|---|
| 张宗浩: "3,3,′4,4′-四甲基二苯甲酮的合成研究", 《化学推进剂与高分子材料》, no. 01 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557501B (en) | 2016-07-06 |
| CN104557501A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107803220B (en) | Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane | |
| EP3366666B1 (en) | Preparation method for aryl-substituted p-phenylenediamine substance | |
| AU2018253450B2 (en) | Method for preparing azoxystrobin intermediates | |
| CN103012074B (en) | Prepare the method for aromatic methyl ether compound | |
| CN103833538A (en) | Method for preparing 3,3',4,4'-tetraalkyl benzophenone by one-pot method | |
| CN104262109B (en) | A kind of synthetic method of resorcinol | |
| CN105384616A (en) | Synthetic method for methoxyacetone | |
| CN103172480A (en) | Method for preparing iodo aromatic hydrocarbon | |
| CN112679346A (en) | Method for catalytically synthesizing p-tert-butyl methyl benzoate based on eutectic solvent | |
| CN103012121A (en) | Method for synthesizing biphenyl 4,4'-dicarboxylic acid from p-chlorotoluene | |
| TW201226379A (en) | Method of producing 2-(cyclohex-1'-enyl) cyclohexanone | |
| CN109574935B (en) | Process for preparing 3, 4-dimethylpyrazole and its phosphate | |
| CN113861084B (en) | Process for preparing 4,4' -dichlorodiphenyl sulfone by one-pot method | |
| CN105198710A (en) | Method for synthesizing 3-(tert-butyl)phenol | |
| CN102659088A (en) | Water-phase synthesis method of sodium azide | |
| CN103086969B (en) | Synthesis method of iminostilbene carbonyl chloride | |
| CN103524336A (en) | Preparation method of 2-(4-pentyloxybenzoyl) benzoic acid with high secondary-tertiary ratio | |
| CN108046999B (en) | Method for preparing antioxidant 1790 intermediate by solvent-free method | |
| CN111072455A (en) | Method for continuously preparing pentafluorophenol by microreactor | |
| CN105130845A (en) | Method of inhibiting degradation of zero-valent nickel in synthesis of adiponitrile through butadiene method | |
| CN102659624A (en) | Method for preparing cyanophenyl compound | |
| CN107721832A (en) | A kind of preparation method of the fluorobenzene ether of 4 chlorine 3 | |
| CN105198756A (en) | Method for synthesizing diphenylamine | |
| CN103553954B (en) | A kind of dyestuff intermediate 3-acetylaminohydroxyphenylarsonic acid N, the production method of N-dimethoxycarbonyl ethyl aniline | |
| CN114797988B (en) | Synthesis of composite catalyst and method for preparing beta-isophorone |
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 |
Application publication date: 20140604 |