CN105152884B - Preparation method of 4-methoxycyclohexanon - Google Patents
Preparation method of 4-methoxycyclohexanon Download PDFInfo
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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Abstract
The invention discloses a preparation method of 4-methoxycyclohexanon. According to the preparation method, hydrogen peroxide is taken as an oxidizing agent, a molecular sieve supported phosphotungstic acid is taken as a catalyst, a 4-methoxycyclohexanon reaction solution is obtained through continuous catalytic oxidation by a tubular reactor, and a target object 4-methoxycyclohexanon with a reaction formula shown in the specification is obtained through solvent extraction and desolvation. According to the preparation method, hydrogen peroxide is taken as the oxidizing agent, the cost of raw materials is low, the raw materials are environment-friendly, no three wastes are generated, and the problems of high cost of other raw materials, high COD (chemical oxygen demand) of wastewater, high salt content of the wastewater, heavy metal chromium pollution and the like are solved. With the adoption of a continuous catalytic oxidation process, the condition that generated targets stay in a reaction system for a long time and have a polymerization reaction is effectively avoided, and danger of potential explosion caused by the fact that hydrogen peroxide accumulates, is not stable at the high temperature and easily decomposes to produce a large amount of oxygen is avoided. A supported phosphotungstic acidmolecular sieve is adopted for catalysis, the reaction yield is greatly improved, the aftertreatment is simple, filtration and separation are not required, and lossless and repeated use of the catalyst is realized.
Description
Technical field
The present invention relates to a kind of preparation method of 4- methoxycyclohexyls ketone, especially continuous catalysis oxidation preparation 4- methoxyl groups
The method of cyclohexanone.
Background technology
4- methoxycyclohexyl ketone is important fine-chemical intermediate, can be used to synthesize Multiple Pesticides and medicine, 4- methoxies
Pentylcyclohexanone chemical structural formula is as follows：
It is mainly used in synthesizing key intermediate (WO2012122747A1) the cis-4- methoxyl groups of spiral shell worm ethyl ester in terms of agricultural chemicals
Cyclohexyl -1- methyl carbamates.
The synthetic method of document report can be summarized as five kinds：
1) document (Medicinal Chemistry (1989), 32 (2), 351-357) report is with hydroquinones as initial former
Material, hydrogenated, methylate, aoxidize three-step reaction preparation, this oxidant sodium bromate used by method document is expensive, and processes generation
A large amount of brine wastes, next methylation reaction step need to carry out in strong basicity system, cause raw material and product to occur poly-
Reaction is closed, yield is substantially reduced.
2) document (WO2007107565) is reported with Isosorbide-5-Nitrae-cyclohexanedione monoethylene acetal as initiation material, hydrogenated to go back
It is former, methylate, hydrolyze three-step reaction and prepare, this method raw material Isosorbide-5-Nitrae-cyclohexanedione monoethylene acetal is without large-scale production, raw material
It is not easy to obtain, secondly methylation reaction needs to carry out in strong basicity system, and post processing produces substantial amounts of brine waste, hydrolyzes repeatedly
The ethylene glycol that step is produced is miscible in waste water, it is difficult to reclaim, waste water COD is higher, not disposable.
3) document (Journal of Chemical Industry and Engineering .2007,12 (58)：3041-3045) report with cyclohexyl methyl ether as initiation material, with
Supported metalloporphyrin is catalyzed, and air oxidation first prepares 4- methoxycyclohexanols, is further continued for being oxidizing to 4- methoxycyclohexyl ketone.This method
Catalyst structure is complicated, and bimetallic porphyrin and monometallic porphyrin are urged by the supported metalloporphyrin for either physically or chemically being formed
The more difficult acquisition of agent, synthetic method are not mature enough.
4) document (CN1137513A) is reported with 4- metoxyphenols as raw material, with palladium carbon catalytic one-stage Hydrogenation for 4- first
Epoxide cyclohexanone, a large amount of 4- methoxycyclohexanols of this method by-product need rectification and purification, ultimate yield only 76% or so.
5) document (Tetrahedron Letters.1994,35 (39), 7151-7154；American Chemical
Society (1957), 79,6295-6299) with 4- metoxyphenols as initiation material, Jing palladium carbons hydrogenating reduction prepares 4- to report
Methoxycyclohexanol, it is oxidized again prepare object, the method hydrogenating reduction yield be more than 99%, technical maturity reliability is mainly asked
Topic is present in oxidation step.The problem that oxidation step is primarily present：Document report has N- first for the oxidant of the reaction at present
Base methylmorpholine-N-oxide, Sha Ruite (Sarrett) reagent PCC, sodium bromate and potassium bichromate.1. document
(US20040186127, WO2003057696) is reported with N-methylmorpholine-N- oxides as oxidant, with four n-propyl mistakes
Ruthenium (VII) acid ammonium is catalyst preparation 4- methoxycyclohexyl ketone, and report yield is 90%, but there is cost of raw material height, by-product
The problems such as N-methylmorpholine recovery complex process.2. document (WO2010057121, WO 2008028860, Medicinal
Chemistry (1989), 32 (2), 351-357) report using Sha Ruite (Sarrett) reagent PCC as oxidant prepare 4-
Methoxycyclohexyl ketone, report yield is 85%, is primarily present cost of raw material height, waste water COD height, heavy metal chromium pollution etc. and asks
Topic.3. document (Tetrahedron Letters (1994), 35 (39), 7151-7154) is reported using sodium bromate as oxidation
Agent, with ammonium ceric nitrate as catalyst preparation 4- methoxycyclohexyl ketone, report yield is 74%, be primarily present the cost of raw material it is high,
The problems such as post processing produces a large amount of brine wastes.4. document (American Chemical Society (1957), 79,6295-
6299) report using potassium bichromate as oxidant, using sulfuric acid as catalyst preparation 4- methoxycyclohexyl ketone, report yield is
50%, it is primarily present and post-processes the problems such as producing a large amount of brine wastes and heavy metal chromium pollution.
Reaction equation is as follows：
Above-mentioned report synthesizes the method for 4- methoxycyclohexyl ketone, and universal yield is not high, between 50～90%.Analysis is former
Because being：This kind of reaction is typically carried out in acid system or alkaline system, and needs certain reaction temperature, such anti-
The object 4- methoxycyclohexyl ketone generated in answering system is unable to stable existence, polymerization can occur instead as the reaction time extends
Should, cause yield to decline.Secondly, the above-mentioned four kinds of oxidants selected in fifth method are not optimal choosing, are summed up
Cost of material is high, waste water COD is high, waste water salt content is big there are problems that and.
The content of the invention
The preparation method of the 4- methoxycyclohexyl ketone that the present invention is provided, is with 4- methoxycyclohexanols as raw material, with peroxide
Change hydrogen be oxidant, with molecular sieve carried type phosphotungstic acid as catalyst, using tubular reactor continuous catalysis oxidation obtain 4- first
Epoxide cyclohexanone reactant liquor, then Jing solvent extractions, precipitation obtain object 4- methoxycyclohexyl ketone, reaction equation is：
4- methoxycyclohexanols of the present invention refer to the 4- methoxycyclohexanol water that mass percentage concentration is 30～50%
Solution；The hydrogen peroxide refers to the hydrogen peroxide that mass percentage concentration is 30～50%；The molecular sieve is 5A molecular sieves；4-
The molar feed ratio of methoxycyclohexanol hydrogen peroxide is 1 1.05～1.5；The charging rate of 4- methoxycyclohexyl alcohol solutions
For 5～15g/min；The rate of addition of hydrogen peroxide is to be defined while dripping with 4- methoxycyclohexanols；The extractant
For toluene or dichloroethanes, ethyl acetate, methyl tertiary butyl ether；70～90 DEG C of tubular reactor reaction temperature.
Concrete operation step：Concrete operations are to be disposed vertically the glass pipe type reactor of internal diameter 2cm, length 60cm, pipe
Tubular reactor is heated to 70～90 DEG C by interior filling 100～150g load phosphotungstic acid molecular sieve catalysts, then respectively by 4- first
Epoxide cyclohexanol and hydrogen peroxide are added from tubular reactor upper end and are reacted in tubular reactor, obtain 4- methoxy basic rings
Flow out from tubular reactor lower end after the condensed device cooling of hexanone reactant liquor, after collecting reactant liquor, Jing solvent extractions, precipitation are obtained
Product 4- methoxycyclohexyl ketone.Gas chromatogram fixative measures 4- methoxycyclohexyl ketone content more than 98.5%, and yield is more than
98%.
The preparation method of load phosphotungstic acid molecular sieve catalyst of the present invention, being will in the reactor with reflux
5A molecular sieves are added after solvent absolute ethyl alcohol, phosphotungstic acid stirring and dissolving, and molecular sieve is 11, Zhi Houjia with the mass ratio of phosphotungstic acid
Hot back flow reaction 2h.Reaction is finished, be cooled to room temperature, suction filtration, infrared lamp drying obtain load phosphotungstic acid molecular sieve crude product.Will be thick
Product are placed in 200 DEG C of Muffle kiln roasting 4h, obtain load phosphotungstic acid molecular sieve catalyst finished product.
The present invention adopt hydrogen peroxide for oxidant, low raw-material cost, environmental protection, three wastes generation, it is to avoid its
Its cost of material is high, waste water COD is high, waste water salt content is big and there are problems that.And due to the company of taking
Continuous catalytic oxidation technique, the object long-time that effectively prevent generation stay in reaction system and polymerisation occur, it is to avoid
Hydrogen peroxide tires out the danger decomposed and produce that substantial amounts of oxygen may occur to explode unstable under collection, high temperature, easy.Using load phosphorus
Wolframic acid molecular sieve catalytic, substantially increases the yield of reaction, and post processing is simple, need not be separated by filtration, realize the nothing of catalyst
Damage and time is used.
Specific implementation method
Embodiment 1：The preparation of load phosphotungstic acid molecular sieve
1000ml absolute ethyl alcohols, 200g phosphotungstic acids are added in the reactor with reflux, is added after stirring and dissolving
200g 5A molecular sieves, heating reflux reaction 2h.Reaction is finished, and is cooled to room temperature, suction filtration, is dried and obtain load phosphotungstic acid molecule
Crude product is placed in 200 DEG C of Muffle kiln roasting 4h, obtains load phosphotungstic acid molecular sieve finished product by sieve crude product.
Embodiment 2：The synthesis of 4- methoxycyclohexyl ketone
The load phosphotungstic acid molecular sieve 100g prepared in weighing embodiment 1, is loaded into internal diameter for 20mm, length 60cm
Tubetype glass reactor in, reactor is disposed vertically and fixation, voltage is adjusted by tubular reactor using heating tape
Internal temperature control is stand-by at 70 DEG C or so.
Weigh 866.6g 4- methoxycyclohexyl alcohol solutions (2mol, 30%) and 238g hydrogen peroxide (2.1mol, 30%)
Prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing peroxidating
Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 1.4g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 2.9h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained is extracted using 350 × 2ml toluene
Take, merge oil reservoir precipitation and obtain 255.2g 4- methoxycyclohexyl ketone, product content 98.6% (GC, internal standard method), yield
98.3%.
Embodiment 3：The synthesis of 4- methoxycyclohexyl ketone
The load phosphotungstic acid molecular sieve 150g prepared in weighing embodiment 1, is loaded into internal diameter for 20mm, length 60cm
Tubetype glass reactor in, reactor is disposed vertically and fixation, voltage is adjusted by tubular reactor using heating tape
Internal temperature control is stand-by at 70 DEG C or so.
(2mol, 50%) with 204g hydrogen peroxide (3mol, 50%) standard to weigh 520.0g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 5.8g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 35min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml, bis- chloroethenes
Alkane extraction, merging oil reservoir precipitation obtain 255.7g 4- methoxycyclohexyl ketone, product content 98.9% (GC, internal standard method), yield
98.8%.
Embodiment 4：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
Weigh 866.6g 4- methoxycyclohexyl alcohol solutions (2mol, 30%) and 238g hydrogen peroxide (2.1mol, 30%)
Prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing peroxidating
Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 1.4g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 2.9h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml acetic acid second
Ester extraction, merging oil reservoir precipitation obtain 256.0g 4- methoxycyclohexyl ketone, product content 98.5% (GC, internal standard method), yield
98.5%.
Embodiment 5：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
(2mol, 50%) with 204g hydrogen peroxide (3mol, 50%) standard to weigh 520.0g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 5.8g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 35min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml tert-butyl groups
Methyl ether extraction, merging oil reservoir precipitation obtain 256.8g 4- methoxycyclohexyl ketone, and product content 98.7% (GC, internal standard method) is received
Rate 99.0%.
Embodiment 6：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
(2mol, 30%) with 204g hydrogen peroxide (3mol, 50%) standard to weigh 866.6g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 3.5g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 58min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained is extracted using 350 × 2ml toluene
Take, merge oil reservoir precipitation and obtain 257.0g 4- methoxycyclohexyl ketone, product content 98.7% (GC, internal standard method), yield
99.1%.
Embodiment 7：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 70 DEG C or so by tubular reactor internal temperature control.
Weigh 520.0g 4- methoxycyclohexyl alcohol solutions (2mol, 50%) and 238g hydrogen peroxide (2.1mol, 30%)
Prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing peroxidating
Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 2.3g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 1.7h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml, bis- chloroethenes
Alkane extraction, merging oil reservoir precipitation obtain 255.2g 4- methoxycyclohexyl ketone, product content 98.6% (GC, internal standard method), yield
98.3%.
Embodiment 8：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
(2mol, 50%) with 340g hydrogen peroxide (3mol, 30%) standard to weigh 520.0g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 9.7g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 35min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml acetic acid second
Ester extraction, merging oil reservoir precipitation obtain 255.5g 4- methoxycyclohexyl ketone, product content 99.0% (GC, internal standard method), yield
98.8%.
Embodiment 9：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 70 DEG C or so by tubular reactor internal temperature control.
Weigh 866.6g 4- methoxycyclohexyl alcohol solutions (2mol, 30%) and 142.8g hydrogen peroxide (2.1mol,
50%) prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing
Oxidation Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 0.8g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 2.9h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml tert-butyl groups
Methyl ether extraction, merging oil reservoir precipitation obtain 255.2g 4- methoxycyclohexyl ketone, and product content 98.7% (GC, internal standard method) is received
Rate 98.4%.
Embodiment 10：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 70 DEG C or so by tubular reactor internal temperature control.
(2mol, 30%) with 340g hydrogen peroxide (3mol, 30%) standard to weigh 866.6g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 2g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 2.9h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained is extracted using 350 × 2ml toluene
Take, merge oil reservoir precipitation and obtain 256.0g 4- methoxycyclohexyl ketone, product content 98.9% (GC, internal standard method), yield
98.9%.
Embodiment 11：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
Weigh 520.0g 4- methoxycyclohexyl alcohol solutions (2mol, 50%) and 142.8g hydrogen peroxide (2.1mol,
50%) prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing
Hydrogen peroxide can be dripped off simultaneously, should adjust charging rate for 0.8g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 35min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml, bis- chloroethenes
Alkane extraction, merging oil reservoir precipitation obtain 255.5g 4- methoxycyclohexyl ketone, product content 98.6% (GC, internal standard method), yield
98.4%.
Embodiment 12：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 70 DEG C or so by tubular reactor internal temperature control.
Weigh 866.6g 4- methoxycyclohexyl alcohol solutions (2mol, 30%) and 238g hydrogen peroxide (2.1mol, 30%)
Prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing peroxidating
Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 4.1g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 58min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml acetic acid second
Ester extraction, merging oil reservoir precipitation obtain 255.0g 4- methoxycyclohexyl ketone, product content 98.7% (GC, internal standard method), yield
98.3%.
Embodiment 13：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
(2mol, 50%) with 204g hydrogen peroxide (3mol, 50%) standard to weigh 520.0g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 2g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 1.7h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained just likes skill using 350 × 2ml
Art butyl ether is extracted, merging oil reservoir precipitation obtains 255.0g 4- methoxycyclohexyl ketone, product content 99.1% (GC, internal standard method),
Yield 98.7%.
Embodiment 14：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 3 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 70 DEG C or so by tubular reactor internal temperature control.
Weigh 866.6g 4- methoxycyclohexyl alcohol solutions (2mol, 30%) and 238g hydrogen peroxide (2.1mol, 30%)
Prepare to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 5g/min, by being calculated as ensureing peroxidating
Hydrogen Energy is dripped off simultaneously, should adjust charging rate for 1.4g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 2.9h is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained is extracted using 350 × 2ml toluene
Take, merge oil reservoir precipitation and obtain 255.2g 4- methoxycyclohexyl ketone, product content 98.8% (GC, internal standard method), yield
98.5%.
Embodiment 15：The synthesis of 4- methoxycyclohexyl ketone
The tubetype glass reactor loaded in embodiment 2 is disposed vertically and fixation, electricity is adjusted using heating tape
Pressure is stand-by at 90 DEG C or so by tubular reactor internal temperature control.
(2mol, 50%) with 204g hydrogen peroxide (3mol, 50%) standard to weigh 520.0g 4- methoxycyclohexyl alcohol solutions
Standby to feed simultaneously, the charging rate for adjusting 4- methoxycyclohexyl alcohol solutions is 15g/min, by being calculated as ensureing hydrogen peroxide
Can drip off simultaneously, charging rate should be adjusted for 5.8g/min.
Start to be added dropwise, reacted by fixed bed after raw material mixing, then 4- methoxy basic rings are obtained after the cooling of condensed device
The reaction of the aqueous solution of hexanone, about 35min is complete.The 4- methoxycyclohexyl ketone aqueous solution that collection is obtained uses 350 × 2ml, bis- chloroethenes
Alkane extraction, merging oil reservoir precipitation obtain 256.3g 4- methoxycyclohexyl ketone, product content 98.9% (GC, internal standard method), yield
99.0%.
Claims (3)
1. a kind of preparation method of 4- methoxycyclohexyls ketone, it is characterised in that be with 4- methoxycyclohexanols as raw material, with peroxide
Change hydrogen be oxidant, with molecular sieve carried type phosphotungstic acid as catalyst, using tubular reactor continuous catalysis oxidation obtain 4- first
Epoxide cyclohexanone reactant liquor, then Jing solvent extractions, precipitation obtain object 4- methoxycyclohexyl ketone, reaction equation is：
70～90 DEG C of tubular reactor reaction temperature.
2. a kind of preparation method of 4- methoxycyclohexyls ketone according to claim 1, it is characterised in that the 4- methoxies basic ring
Hexanol refers to the 4- methoxycyclohexyl alcohol solutions that mass percentage concentration is 30～50%；The hydrogen peroxide refers to quality percentage
Concentration is 30～50% hydrogen peroxide；4- methoxycyclohexanols: the molar feed ratio of hydrogen peroxide is 1: 1.05～1.5；4-
The charging rate of methoxycyclohexyl alcohol solution is 5～15g/min；The rate of addition of hydrogen peroxide is and 4- methoxycyclohexanols
Drip simultaneously and be defined；The extractant is toluene or dichloroethanes, ethyl acetate, methyl tertiary butyl ether.
3. a kind of preparation method of 4- methoxycyclohexyls ketone according to claim 1, it is characterised in that load phosphotungstic acid molecule
The preparation of sieve catalyst is in the reactor with reflux will to add 5A after solvent absolute ethyl alcohol, phosphotungstic acid stirring and dissolving
Molecular sieve, phosphotungstic acid are 1: 1 with molecular sieve quality ratio, and reflux time is 2h, dry, be placed in 200 DEG C of horses after cooling, suction filtration
Not kiln roasting 4h is obtained.
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