CN109574898A - The method that microchannel oxidizing process prepares aromatic series hyperis compound - Google Patents
The method that microchannel oxidizing process prepares aromatic series hyperis compound Download PDFInfo
- Publication number
- CN109574898A CN109574898A CN201811646861.1A CN201811646861A CN109574898A CN 109574898 A CN109574898 A CN 109574898A CN 201811646861 A CN201811646861 A CN 201811646861A CN 109574898 A CN109574898 A CN 109574898A
- Authority
- CN
- China
- Prior art keywords
- aromatic series
- reaction
- compound
- hyperis
- preparation
- 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
- C07C407/00—Preparation of peroxy compounds
Abstract
The invention discloses a kind of method that microchannel oxidizing process prepares aromatic series hyperis compound, this method processes are as follows: by catalyst, azodiisobutyronitrile azo compound of n-Hydroxyphthalimide class hydroxylamine compound is initiator；It is declined channel reactor using JD-SSIC carborundum plate, is continually fed into oxygen and keeps certain flow rate, reaching reaction pressure range is 0.5 ~ 4.5MPa；Aromatic series isopropyl base class compound, catalyst, initiator are mixed, certain solvent is added, it is flowed into microchannel by preheating by metering pump and oxidation reaction occurs, reaction temperature is 60 ~ 95 DEG C, reaction time is 30 ~ 180min, gas-liquid separation after reaction obtains product aromatic series hyperis compound solution, and product yield is up to 49%.The present invention uses organic phase homogeneous catalytic oxidation system, and uses micro passage reaction, and mass transfer and heat-transfer effect are good, and oxidation time is short, efficiently avoids the explosive of reaction, thus high income, selectivity are good and safety is good.
Description
Technical field
The present invention relates to oxidations to prepare aromatic series hyperis compound, and in particular to a kind of microchannel oxidizing process
The method for preparing aromatic series hyperis compound.
Background technique
Aromatic series hyperis compound is important chemical intermediate, is widely used in medicine, pesticide and rubber
The fields such as glue, they can also prepare phenol compound by hydrolysis.
Currently, the method for domestic synthesis aromatic series hyperis compound mainly uses aromatic series isopropyl base class
Close the oxidizing process of object.Method for oxidation mainly has base catalysis method, metal catalysed processes, catalytic organism method and microchannel Ozonation
Deng.
United States Patent (USP) (US4237319) reports base catalysis method, is catalysis with sodium hydrate aqueous solution in autoclave
Agent, air are oxidant, and 0.65MPa, reacts 31 hours, a diisopropyl benzene is oxidized to a diperoxy hydrogen isopropyl by 106 DEG C
Base benzene, yield 59.4%, the technique are water phase heterogeneous reaction, and big to equipment corrosion, the waste water of generation is more, and reaction exists
Explosion potential.
Ying Fang Hsu et al. (Journal of Molecular Catalysis A:Chemical, 1997,
Metal catalysed processes 120:109-116) are reported, in autoclave, with Cu (OAc)2/ resin is catalyst, and oxygen is oxidation
Agent, 0.0267MPa, react 3 hours, isopropylbenzene is oxidized to hydrogen peroxide cumene, yield 7.1%, the technique by 90 DEG C
Yield is very low, and there are explosion potentials for reaction.
Osamu Fukuda et al. (Advanced Synthesis & Catalysis, 2001,343:809-813)
Catalytic organism method is reported, in autoclave, using n-Hydroxyphthalimide as catalyst, azodiisobutyronitrile is to draw
Agent is sent out, a diisopropyl benzene is oxidized to a diperoxy hydrogen cumene, 75 DEG C, reacts 20 hours, yield 56%, the work
The skill reaction time is long, and there are explosion potentials for reaction.
Chinese patent (CN102382024) reports microchannel Ozonation, in continous way tubular reactor, with smelly
Oxygen is oxidant, and by cumene oxidation at hydrogen peroxide cumene, 0.5MPa, reacts 6min, yield 38.2% should by 60 DEG C
The technological reaction time is short, and reaction safety coefficient is high, but yield is lower, and ozone is more expensive, high production cost.
Summary of the invention
In view of the deficienciess of the prior art, the present invention, which provides a kind of microchannel oxidizing process, prepares aromatic series isopropyl peroxide
Change the method for hydrogen compound.This method uses organic phase homogeneous catalytic oxidation system, and uses board-like micro passage reaction, mass transfer
Good with heat-transfer effect, oxidation time is short, efficiently avoids the explosive of reaction, thus high income, selectivity it is good and
Safety is good.
In the present invention, catalyst is made using n-Hydroxyphthalimide type organic, azodiisobutyronitrile class has
Machine object makees initiator, using organic solvents such as acetonitriles, forms homogeneous organic reaction system, oxygen can be also dissolved in organic under high pressure
Solution, so that reaction comes into full contact with, mass transfer effect is good, and it reduce reaction temperatures, improves yield.
In the present invention, the reaction for preparing aromatic series hyperis compound is strong exothermal reaction, board-like micro- logical
Road reactor has very big specific surface area, and mass transfer and heat-transfer effect are good, in conjunction with above-mentioned homogeneous organic reaction system, oxidation reaction
Time is short, and reaction thermal energy is removed in time, efficiently avoids the explosive of reaction, improves yield, selectivity and reaction
Safety.
The content of present invention is described as follows:
A kind of preparation method of aromatic series hyperis compound, it is characterised in that with n-Hydroxyphthalimide
Class hydroxylamine compound is catalyst, using azodiisobutyronitrile azo compound as initiator；By aromatic series isopropyl base class chemical combination
Object, catalyst, initiator and organic solvent mixing, put into microchannel plate by metering pump after the preheating of gained reaction mixture and answer
Device is constantly passed through certain flow rate oxygen at the same time and reactor is made to reach certain pressure, recycles at a temperature of 60 ~ 95 DEG C anti-
It answers, after reaction gas-liquid separation, obtains aromatic series hyperis compound solution.
A kind of preparation method of aromatic series hyperis compound, it is characterised in that aromatic series isopropyl
The general structure of class compound such as formula (I), (II), (III), (IV) are shown:
R is hydrogen atom or halogen atom.
The preparation method of a kind of aromatic series hyperis compound, it is characterised in that catalyst is N- hydroxyl
Base phthalimide, N- hydroxyl -4- nitrophthalimide or N- hydroxyl -4- chlorophthalimide；Cause
Agent is azodiisobutyronitrile, azobisisoheptonitrile or azo-bis-iso-dimethyl；Organic solvent is acetonitrile, bis- chloroethene of 1,2-
Alkane, ethyl acetate.
A kind of preparation method of aromatic series hyperis compound, it is characterised in that micro passage reaction
Model JD-SSIC carborundum plate decline channel reactor, channel internal diameter is 1.58 ~ 2mm.Reaction raw materials liquid enters microchannel
The flow velocity of reactor is 5 ~ 30mL/min, and reaction time is 30 ~ 180min.
A kind of preparation method of aromatic series hyperis compound, it is characterised in that aromatic series isopropyl
The molar ratio range of class compound, catalyst, initiator are as follows: 1:0.05 ~ 0.25:0.01 ~ 0.1.
The preparation method of a kind of aromatic series hyperis compound, it is characterised in that reaction mixture is pre-
Heat is to 50 ~ 60 DEG C.
The preparation method of a kind of aromatic series hyperis compound, it is characterised in that oxygen enters micro- logical
The flow velocity of road reactor is 0.2 ~ 1mL/min, and pressure limit is 0.5 ~ 4.5MPa in micro passage reaction.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1
In preheater be added m-Diisopropylbenzene 32.4g(200 mmol), n-Hydroxyphthalimide 3.3g(20
Mmol), azodiisobutyronitrile 1g(6 mmol) and 200 mL of acetonitrile, mixed dissolution be preheated to 60 DEG C, obtain reaction raw materials liquid and wait for
With.
The JD-SSIC carborundum plate channel reactor that declines is warming up to 75 DEG C, is passed through oxygen, pressure 2.6Mpa, oxygen
Flow velocity is 0.2mL/min.It is passed through reaction raw materials liquid, flow velocity 30mL/min is separated after the feed liquid after reaction carries out gas-liquid separation
Obtained reaction mixture, which is passed through again in micro passage reaction, carries out circular response, and the one way reaction time is 2min, adds up reaction
Time is 180min.A diperoxy hydrogen isopropyl benzene solution is finally obtained, is analyzed with liquid chromatograph, obtaining yield is
49%, selectivity is 92.1%.
Embodiment 2
N- hydroxyl -4- nitrophthalimide 4.2g(20 mmol) is replaced into n-Hydroxyphthalimide 3.3g(20
Mmol), other reaction conditions and operating process are the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution is obtained, yield is
43.2%, selectivity is 90.2%.
Embodiment 3
N- hydroxyl -4- chlorophthalimide 4.0g(20 mmol) is replaced into n-Hydroxyphthalimide 3.3g(20
Mmol), other reaction conditions and operating process are the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution is obtained, yield is
43.8%, selectivity is 90.6%.
Embodiment 4
Azobisisoheptonitrile 1.5g(6 mmol) is replaced into azodiisobutyronitrile 1g(6 mmol), it other reaction conditions and operated
Journey is the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution, yield 46.1% are obtained, selectivity is 91.4%.
Embodiment 5
By azo-bis-iso-dimethyl 1.4g(6 mmol) replace azodiisobutyronitrile 1g(6 mmol), other reaction conditions and
Operating process is the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution, yield 47.2% are obtained, selectivity is 90.9%.
Embodiment 6
1, the 2- dichloroethanes of 200mL is replaced into 200mL acetonitrile, other reaction conditions and operating process are the same as embodiment 1.It obtains
Between diperoxy hydrogen isopropyl benzene solution, yield 45.3%, selectivity be 91.9%.
Embodiment 7
200mL ethyl acetate is replaced into 200mL acetonitrile, other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy
Change hydrogen isopropyl benzene solution, yield 48.8%, selectivity is 92.1%.
Embodiment 8
Cumene 24.0g(200 mmol) is replaced into m-Diisopropylbenzene 32.5g(200 mmol), other reaction conditions and operation
Process is the same as embodiment 1.Hydrogen peroxide isopropyl benzene solution, yield 46.6% are obtained, selectivity is 91.6%.
Embodiment 9
Adjacent diisopropylbenzene (DIPB) 32.5g(200 mmol) is replaced into m-Diisopropylbenzene 32.5g(200 mmol), other reaction conditions and behaviour
Make process with embodiment 1.Adjacent diperoxy hydrogen isopropyl benzene solution, yield 40.5% are obtained, selectivity is 90.1%.
Embodiment 10
P-Diisopropylbenzene 32.5g(200 mmol) is replaced into m-Diisopropylbenzene 32.5g(200 mmol), other reaction conditions and behaviour
Make process with embodiment 1.It obtains to diperoxy hydrogen isopropyl benzene solution, yield 45.9%, selectivity is 92.3%.
Embodiment 11
75 DEG C are replaced by 60 DEG C of reaction temperature, other reaction conditions and operating process are the same as embodiment 1.It is different to obtain diperoxy hydrogen
Propyl benzole soln, yield 32.2%, selectivity are 93.6%.
Embodiment 12
75 DEG C are replaced by 95 DEG C of reaction temperature, other reaction conditions and operating process are the same as embodiment 1.It is different to obtain diperoxy hydrogen
Propyl benzole soln, yield 22.6%, selectivity are 40.1%.
Embodiment 13
Reaction pressure 0.5MPa is replaced into 2.6MPa, other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy
Hydrogen isopropyl benzene solution, yield 24.4%, selectivity are 91.9%.
Embodiment 14
Reaction pressure 4.5MPa is replaced into 2.6MPa, other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy
Hydrogen isopropyl benzene solution, yield 48.9%, selectivity are 92.3%.
Embodiment 15
Oxygen gas flow rate 1mL/min is replaced into 0.2mL/min, other reaction conditions and operating process are the same as embodiment 1.Two mistake between obtaining
Hydrogen oxide isopropyl benzene solution, yield 49%, selectivity are 92.1%.
Embodiment 16
50 DEG C will be preheated to and replace 60 DEG C, other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy hydrogen isopropyl
Base benzole soln, yield 41.2%, selectivity are 91.9%.
Embodiment 17
N-Hydroxyphthalimide 1.6g(10 mmol) is replaced into n-Hydroxyphthalimide 3.3g(20 mmol),
Other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy hydrogen isopropyl benzene solution, yield 23.1%, selection
Property is 90.2%.
Embodiment 18
N-Hydroxyphthalimide 8.2g(50 mmol) is replaced into n-Hydroxyphthalimide 3.3g(20 mmol),
Other reaction conditions and operating process are the same as embodiment 1.Obtain a diperoxy hydrogen isopropyl benzene solution, yield 48.8%, selection
Property is 91.3%.
Embodiment 19
Azodiisobutyronitrile 0.4g(2 mmol) is replaced into azodiisobutyronitrile 1g(6 mmol), it other reaction conditions and operated
Journey is the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution, yield 40.1% are obtained, selectivity is 89.9%.
Embodiment 20
Azodiisobutyronitrile 3.3g(20 mmol) is replaced into azodiisobutyronitrile 1g(6 mmol), other reaction conditions and operation
Process is the same as embodiment 1.A diperoxy hydrogen isopropyl benzene solution, yield 47.9% are obtained, selectivity is 90.3%.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (7)
1. a kind of preparation method of aromatic series hyperis compound, it is characterised in that sub- with N- hydroxyl phthalyl
Amine hydroxylamine compound is catalyst, using azodiisobutyronitrile azo compound as initiator；By aromatic series isopropyl base class
Object, catalyst, initiator and organic solvent mixing are closed, microchannel plate is put by metering pump after the preheating of gained reaction mixture
Device is answered, be constantly passed through certain flow rate oxygen at the same time and reactor is made to reach certain pressure, is recycled at a temperature of 60 ~ 95 DEG C anti-
It answers, after reaction gas-liquid separation, obtains product aromatic series hyperis compound solution.
2. a kind of preparation method of aromatic series hyperis compound according to claim 1, it is characterised in that
The general structure such as formula (I) of aromatic series isopropyl base class compound, (II), (III), (IV) are shown:
R is hydrogen atom or halogen atom.
3. a kind of preparation method of aromatic series hyperis compound according to claim 1, it is characterised in that
Catalyst is n-Hydroxyphthalimide, N- hydroxyl -4- nitrophthalimide or N- hydroxyl -4- chlore O-phthalic acid
Acid imide；Initiator is azodiisobutyronitrile, azobisisoheptonitrile or azo-bis-iso-dimethyl；Organic solvent be acetonitrile,
1,2- dichloroethanes or ethyl acetate.
4. a kind of preparation method of aromatic series hyperis compound according to claim 1, it is characterised in that
The molar ratio range of aromatic series isopropyl base class compound, catalyst, initiator are as follows: 1:0.05 ~ 0.25:0.01 ~ 0.1.
5. a kind of preparation method of aromatic series hyperis compound according to claim 1, it is characterised in that
Reaction mixture is preheated to 50 ~ 60 DEG C.
6. a kind of preparation method of aromatic series hyperis compound according to claim 5, it is characterised in that
The flow velocity that oxygen enters micro passage reaction is 0.2 ~ 1mL/min, and pressure limit is 0.5 ~ 4.5MPa in micro passage reaction.
7. a kind of preparation method of aromatic series hyperis compound according to claim 1, it is characterised in that
The model JD-SSIC silicon carbide microplate formula channel reactor of micro passage reaction, channel internal diameter are 1.58 ~ 2mm, reaction raw materials
The flow velocity that liquid enters micro passage reaction is 5 ~ 30mL/min, and reaction time is 30 ~ 180min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646861.1A CN109574898A (en) | 2018-12-29 | 2018-12-29 | The method that microchannel oxidizing process prepares aromatic series hyperis compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646861.1A CN109574898A (en) | 2018-12-29 | 2018-12-29 | The method that microchannel oxidizing process prepares aromatic series hyperis compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109574898A true CN109574898A (en) | 2019-04-05 |
Family
ID=65914928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811646861.1A Pending CN109574898A (en) | 2018-12-29 | 2018-12-29 | The method that microchannel oxidizing process prepares aromatic series hyperis compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109574898A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437117A (en) * | 2019-09-10 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of method that cumene oxidation prepares cumene hydroperoxide |
| CN113620853A (en) * | 2021-08-10 | 2021-11-09 | 万华化学集团股份有限公司 | Preparation method of diisopropylbenzene hydroperoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623453A (en) * | 2018-06-22 | 2018-10-09 | 杭州陶瑞生物科技有限公司 | A method of preparing aryl formate compound using microchannel continuous flow reactor |
| CN108752254A (en) * | 2018-05-22 | 2018-11-06 | 上海道箴医药科技有限公司 | 2-[1-（Ethylsulfonyl）- 3- azetidins subunit] acetonitrile preparation method |
| CN108794321A (en) * | 2018-07-16 | 2018-11-13 | 山东冠森高分子材料科技股份有限公司 | The method that aromatic carboxylic-acid compound is synthesized in continuous flow micro passage reaction |
-
2018
- 2018-12-29 CN CN201811646861.1A patent/CN109574898A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752254A (en) * | 2018-05-22 | 2018-11-06 | 上海道箴医药科技有限公司 | 2-[1-（Ethylsulfonyl）- 3- azetidins subunit] acetonitrile preparation method |
| CN108623453A (en) * | 2018-06-22 | 2018-10-09 | 杭州陶瑞生物科技有限公司 | A method of preparing aryl formate compound using microchannel continuous flow reactor |
| CN108794321A (en) * | 2018-07-16 | 2018-11-13 | 山东冠森高分子材料科技股份有限公司 | The method that aromatic carboxylic-acid compound is synthesized in continuous flow micro passage reaction |
Non-Patent Citations (1)
| Title |
|---|
| OSAMU FUKUDA,等: "Preparation of Hydroperoxides by N-Hydroxyphthalimide-Catalyzed Aerobic Oxidation of Alkylbenzenes and Hydroaromatic Compounds and Its Application", 《ADV. SYNTH. CATAL.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437117A (en) * | 2019-09-10 | 2019-11-12 | 万华化学集团股份有限公司 | A kind of method that cumene oxidation prepares cumene hydroperoxide |
| CN110437117B (en) * | 2019-09-10 | 2021-07-23 | 万华化学集团股份有限公司 | Method for preparing cumene hydroperoxide by oxidizing cumene |
| CN113620853A (en) * | 2021-08-10 | 2021-11-09 | 万华化学集团股份有限公司 | Preparation method of diisopropylbenzene hydroperoxide |
| CN113620853B (en) * | 2021-08-10 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of diisopropylbenzene hydroperoxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818533B (en) | Preparation method of m-trifluoromethylphenol | |
| TW201038518A (en) | Process for producing phenol | |
| TW200922915A (en) | Oxidation of hydrocarbons | |
| CN103539762B (en) | Epoxidation of propylene produces the method for propylene oxide | |
| JP2004504273A (en) | Hydrocarbon oxidation method | |
| CN109574898A (en) | The method that microchannel oxidizing process prepares aromatic series hyperis compound | |
| CN109232218B (en) | Method for preparing benzil by oxidizing benzoin in microreactor | |
| CN211725714U (en) | High-throughput micro-reaction equipment for preparing di-tert-butyl peroxide | |
| CN103418434B (en) | Homogeneous phase molybdenum basic ring oxidation catalyst | |
| CN107602358B (en) | Method for preparing methoxy acetone by using micro-reaction device | |
| WO2011015000A1 (en) | Process and device for preparing benzaldehyde and benzyl alcohol by multistage oxidation of toluene | |
| CN108752175A (en) | A kind of continuous preparation method of benzil or derivatives thereof | |
| US7038089B2 (en) | Process for preparation of hydroperoxides | |
| KR20080037723A (en) | Decomposition of cumene hydroperoxide | |
| CN111056934B (en) | Method for preparing alpha-hydroxy ketone photoinitiator in microreactor | |
| CN102516051B (en) | Method for preparing isophorone by acetone liquid condensation with alkali catalyst | |
| Barton et al. | The functionalization of saturated hydrocarbons part XXIX. Application of tert-butyl hydroperoxide and dioxygen using soluble Fe (III) and Cu (II) chelates. | |
| Yube et al. | Efficient oxidation of aromatics with peroxides under severe conditions using a microreaction system | |
| CN109772326A (en) | A kind of catalyst and its preparation method and application synthesizing Fluorenone | |
| CN109369498B (en) | Method for continuously synthesizing 4-bromo-2-p-chlorophenyl-5-trifluoromethylpyrrole-3-nitrile by using microreactor | |
| CN100503541C (en) | Production of anone by cyclohexane liquid-phase oxidation | |
| CN103172508A (en) | Method for preparing 1,4-benzoquinone by directly oxidizing benzene | |
| CN107522638A (en) | Prepare the microreactor and method of o-methyl formate benzene sulfonamide | |
| CN112239450B (en) | Method for synthesizing epsilon-caprolactone | |
| CN112939765A (en) | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190405 |
|
| RJ01 | Rejection of invention patent application after publication |