CN104093710A - Method for producing epoxy-carboxylic acid esters - Google Patents
Method for producing epoxy-carboxylic acid esters Download PDFInfo
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- CN104093710A CN104093710A CN201380007204.1A CN201380007204A CN104093710A CN 104093710 A CN104093710 A CN 104093710A CN 201380007204 A CN201380007204 A CN 201380007204A CN 104093710 A CN104093710 A CN 104093710A
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- epoxide
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- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 150000002118 epoxides Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000002195 soluble material Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229940039748 oxalate Drugs 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 206010037544 Purging Diseases 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a method for producing epoxides of formula (I), wherein R is an organic group with 1-10 C atoms, and compounds of formula (II) and an oxidation agent are subjected to reactions. The method is characterized in that the production takes place continuously in a tube reactor.
Description
Describe
The present invention relates to a kind of method of preparing the epoxide with formula I,
Wherein R is the organic group with 1-10 carbon atom,
Wherein make to have compound and the oxidant reaction of formula II,
Wherein said preparation is to carry out continuously in tubular reactor.
Epoxide is significant in industrial application widely, especially also as raw material for other chemosynthesis.
The epoxide with formula I is for example the raw material for the preparation of carbonic ether, for example, referring to not yet disclosed patent application PCT/EP2011/058945 and PCT/EP2011/069626.
So need very cheaply and effectively to prepare the synthetic method of epoxide.
Albrecht Berkessel etc., in Tetrahedron Letters40 (1999), have described in 7965-7968 by methyl acrylate and be oxidized to prepare the epoxide with formula I with hydrogen peroxide under the existence of manganese complex and oxalate.Information about continuous production is not provided.
Dirk E.de Vos etc., also in Tetrahedron Letters39 (1998), have described the epoxidation reaction that uses manganese complex and oxalate to use hydrogen peroxide for alkene as catalyzer or promotor in 3221-3224.
In US 5 329 024 and EP-A 2 354 131, mention the continuation method of alkene epoxidation.But EP-A 2 354 131 does not relate to the epoxidation of acrylate.US 5 329 024 has mentioned except other alkene, and acrylate can be used as for epoxidised raw material; As can, for the reactor of continuous production, having mentioned and can select tubular reactor or stirred vessel.
The object of this invention is to provide a kind of simple and effective method of preparing epoxide from acrylate; Described epoxide should especially obtain with very high productive rate and selectivity.
Therefore, found the method that beginning is described herein.
Raw material
There is the epoxide of formula I
To prepare from the compound with formula II by the inventive method,
Wherein the radicals R in two structural formulas is identical.
R is the organic group with 1-10 carbon atom.Except carbon and hydrogen atom, organic group also can contain heteroatoms, for example oxygen and nitrogen.Oxygen and nitrogen can especially exist as the composition of hydroxyl, ether group, amino or nitro.
Preferably not containing any heteroatomic R, so preferably alkyl of R.Alkyl can be the alkyl of aromatics or aliphatic series.
In a preferred embodiment, R is C1-C10 alkyl.Alkyl can be also straight chain or branching.R is particularly preferably C1-C4 alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or the tertiary butyl.
R is very particularly preferably methyl.
The starting compound with formula II is vinylformic acid C1-C10 alkyl ester or vinylformic acid C1-C4 alkyl ester in the situation that of above-mentioned preferred embodiment, is very particularly preferably methyl acrylate.
Formula I compound and oxidant reaction.Possible oxygenant is conventional oxygenant, for example superoxide or peracid.Preferred oxygenant is hydrogen peroxide (H
2o
2).Hydrogen peroxide preferably uses with the form of the aqueous solution.The concentration of hydrogen peroxide in water preferably 10-70 % by weight, especially 20-60 % by weight, based on solution meter (being the gross weight of hydrogen peroxide and water).
Oxygenant, preferred hydrogen peroxide preferably use with molar excess, thereby formula I starting compound are as far as possible fully reacted; The consumption of oxygenant can be for example 1.1-2 equivalent, especially 1.2-1.7 equivalent, the formula II starting compound meter based on 1 equivalent.
This reaction is preferably carried out under the existence of the manganese complex as catalyzer.
Possible manganese complex is if Albrecht Berkessel etc. is in Tetrahedron Letters40 (1999), in 7965-7968 and Dirk E.de Vos etc. in Tetrahedron Letters39 (1998), those described in 3221-3224.
Preferably use manganese-nitrogen complex, preferred wherein manganese is with those manganese-nitrogen complexes of its corresponding oxidation state and three nitrogen-atoms coordinations.
For the initial compounds of manganese-nitrogen complex, be applicable to form manganese salt and the nitrogen compound of title complex, be preferably added in reaction mixture.Then, catalytic effect starts by forming on the spot manganese-nitrogen complex.The final catalysis of manganese-nitrogen complex the decomposition of hydrogen peroxide, to become V from III relevant with the cationic, oxidized state of manganese for this.
The especially salt of bivalent manganese, for example MnSO of possible manganese salt
4.
Also the nitrogen compound that is extremely suitable for forming title complex is for example Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane (referred to as TMTACN).
The preferred consumption in each case of manganese-nitrogen complex or manganese salt and nitrogen compound is 0.005-0.2 mole, and particularly preferably 0.01-0.1 mole, is very particularly preferably 0.02-0.08 mole, according to the formula II starting compound meter of every 100 moles.
Except catalyzer, can also preferably use promotor.Especially reductive agent of suitable promotor, for example xitix, squaric acid, oxalic acid, or oxalate, for example sodium oxalate.Preferably oxalic acid or oxalate.Particularly preferably oxalic acid/oxalate system; It is as buffer reagent.
The consumption of promotor can be for example 0.1-20 mole, especially 0.5-10 mole, and particularly preferably 1-5 mole, according to the formula II starting compound meter of every 100 moles.
Carry out the inventive method
According to the present invention, the preparation of formula II epoxide is to carry out continuously in tubular reactor.
In continuous production, raw material is added in tubular reactor continuously, and the product mixtures of formation is taken out continuously.
Above-mentioned raw materials can separate and add individually; But any above-mentioned raw materials also can mix and add in tubular reactor as mixture.
In a preferred embodiment, previously prepared two kinds of mixtures:
-the aqueous solution that contains water-soluble material, preferably contains hydrogen peroxide and oxalic acid/oxalate; With
-organic solution, it contains formula II compound and can be dissolved in initial compounds wherein; This preferably manganese-nitrogen complex solution or for this initial compounds at the solution of formula II acrylic type compound.
In preferred embodiments, these two kinds of mixtures are taken out continuously and added in tubular reactor via suitable pump system from two material containers.
Reaction in tubular reactor is heat release, and starts immediately.Tubular reactor carries out cooling, thus this reaction preferably at the temperature of 0-40 DEG C, in tubular reactor, carry out, especially 0-30 DEG C.This reaction can be carried out under normal atmosphere, subatmospheric pressure or superatmospheric pressure.It is favourable having a shade below the rare gas element of atmospheric pressure, especially nitrogen, thereby helps reaction medium distribute, mix and carry in the mode that does not contain foam in tubular reactor.Gauge pressure can be for example 1-10 bar.
For the object of the invention, term " tubular reactor " represents whole reactor unit; It can comprise single pipe or multiple parallel connected pipe.These pipes preferably have only little interior diameter, so also referred to as kapillary.
Tubular reactor preferably comprises one or more parallel connected kapillaries, reaction mixture flows through from these kapillaries, wherein kapillary can have the interior diameter that is less than 5 millimeters, is especially less than 3 millimeters, is especially less than 2 millimeters or be less than the interior diameter of 1 millimeter.Interior diameter capillaceous is generally at least 0.1 millimeter.
Interior diameter capillaceous is very particularly preferably 0.1-5 millimeter, and especially 0.2-4 millimeter is very particularly preferably 0.5-3 millimeter.
Here, interior diameter capillaceous is the maximum diameter along cross section; The in the situation that of circle capillaceous or semi-circular cross-section, interior diameter is the twice of radius.
Preferably at least 5 meters of length capillaceous, especially at least 10 meters.Most suitable tubular reactor has for example kapillary of the one or more 10-150 of having rice length, especially 20-130 rice, is 30-100 rice in particularly preferred embodiments.
In a preferred embodiment, tubular reactor comprises at least two parallel connected kapillaries, and for example 2-5 two parallel connected kapillaries, especially comprise two parallel connected kapillaries.
Preferably 5-200 minute of the residence time of reaction mixture in tubular reactor or kapillary is particularly preferably 10-100 minute, especially preferably 20-80 minute.
According to the type of raw material and consumption, after by tubular reactor, obtain the reaction product of single-phase or two-phase.If the formula I epoxide obtaining can be water-soluble, obtain the water that contains epoxide.If the epoxide obtaining can not be water-soluble or be obtained those water-soluble more epoxide of specific energy, except water, also obtain the phase substantially being formed by epoxide.
Organic phase (epoxide) can be separated in a simple manner; The epoxide obtaining can be by known method from aqueous phase separation out, for example extraction.
Finally, also can purify to the epoxide obtaining, the epoxide of for example separating as organic phase and by the combined amount of extracting and separating epoxide out.
The inventive method is the simple and efficient continuation method of preparing epoxide from acrylate; Epoxide can obtain with high yield and selectivity by the inventive method.
Embodiment
Preparation epoxy group(ing) methyl propionate (MEP)
MEP is corresponding to formula I compound that wherein R is methyl.
TMTACN is Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane.
This preparation method is according to hereinafter described carrying out continuously.
In the time that experiment starts, in material container, add the solution (material container V1) of methyl acrylate/TMTACN/ acetic acid Mn (II) and add H
2o
2the solution (material container V2) of/sodium oxalate/oxalic acid, and carry and avoid in pump head, to occur bubbling in order to improve, with 5 bar nitrogen purgings.To expect that stream 1 (methyl acrylate/TMTACN/ acetic acid Mn (II)) and material stream 2 (hydrogen peroxide+sodium oxalate+oxalic acid) add (via the weight control detecting) in reactor by Kontron or Bischoffs pump.
Reactor comprises two parallel semicircle microchannels, and described passage has the radius of 1.2mm and the cumulative volume of 200ml.These material streams directly mixed before reactor, carry, and unzip in discharge container via pressure-regulator (20 bar) via reactor.For fear of rear reaction, excessive hydrogen peroxide decomposes by saturated sodium bisulfite solution in discharge container.
The reaction of methyl acrylate and hydrogen peroxide is to use different H
2o
2initial concentration carries out.
The essential characteristic of experiment operation and gained epoxide is as follows for shown in embodiment 1-3:
The H of embodiment 1:20% concentration
2o
2the aqueous solution
Shown mol% is the acrylate meter based on used.
Space-time yield (STY): 244g/ liter (l)/hour (h)
The consumption of TMTACN is the TMTACN/kg reaction product (MEP) of 1.0g
The H of embodiment 2:30% concentration
2o
2the aqueous solution
The TMTACN/kg MEP of STY:320g/l/h-1.1g
The H of embodiment 3:50% concentration
2o
2the aqueous solution
The TMTACN/kg MEP of STY:370g/l/h – 2.9g
The aftertreatment of embodiment 1-3
MEP solubleness in water at 20 DEG C is 43g/10g water.The density of MEP is 1.16g/ml, higher than approximately 40% productive rate (at the H of 50% concentration
2o
2situation under), reaction discharging by two phase composites, i.e. the phase being formed by MEP of the water on upper strata and lower floor.
For aftertreatment, isolate lower floor's phase, and extraction is dissolved in the MEP of upper strata in mutually.Under reduced pressure remove desolventizing, and distill out thick MEP product, this carries out under 24-28 DEG C (10 millibars).
The master data of embodiment is listed in following table.
Claims (12)
1. prepare a method for the epoxide with formula I,
Wherein R is the organic group with 1-10 carbon atom,
Wherein make to have compound and the oxidant reaction of formula II,
Wherein said preparation is to carry out continuously in tubular reactor.
2. according to the process of claim 1 wherein that the R in formula I and II is C1-C10 alkyl.
3. according to the method for claim 1 or 2, wherein oxygenant is hydrogen peroxide.
4. according to the method for any one in claim 1-3, wherein reaction is to carry out under the existence of the manganese complex as catalyzer.
5. according to the method for claim 4, wherein reaction is carried out in addition under the existence of oxalic acid or oxalate.
6. according to the method for any one in claim 1-5, wherein tubular reactor comprises one or more parallel connected kapillaries, and reaction mixture flows through from these kapillaries, and wherein kapillary has the interior diameter that is less than 5 millimeters.
7. according to the method for any one in claim 1-6, wherein kapillary has the length of at least 10 meters.
8. according to the method for any one in claim 1-7, wherein tubular reactor comprises at least two parallel connected kapillaries.
9. according to the method for any one in claim 1-8, wherein the residence time of reaction medium in kapillary is 5-200 minute.
10. according to the method for any one in claim 1-9, wherein react at the temperature of 0-30 DEG C and carry out.
11. according to the method for any one in claim 1-10, wherein the aqueous solution that contains water-soluble material and the organic solution that contains formula II compound and dissolve in initial compounds wherein is separately added to tubular reactor individually.
12. according to the method for claim 11, wherein organic solution be manganese-nitrogen complex or for the initial compounds of this title complex the solution at formula II compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12153206 | 2012-01-31 | ||
| EP12153206.3 | 2012-01-31 | ||
| PCT/EP2013/051034 WO2013113578A1 (en) | 2012-01-31 | 2013-01-21 | Method for producing epoxy-carboxylic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104093710A true CN104093710A (en) | 2014-10-08 |
Family
ID=47603691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380007204.1A Pending CN104093710A (en) | 2012-01-31 | 2013-01-21 | Method for producing epoxy-carboxylic acid esters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2809663A1 (en) |
| JP (1) | JP2015529628A (en) |
| KR (1) | KR20140117386A (en) |
| CN (1) | CN104093710A (en) |
| WO (1) | WO2013113578A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX356142B (en) | 2012-06-13 | 2018-05-16 | Basf Se | Method for producing macrocyclic ketones. |
| EP3059229A1 (en) | 2015-02-17 | 2016-08-24 | Evonik Degussa GmbH | Method for the epoxidation of an olefin with hydrogen peroxide |
| US10087158B2 (en) * | 2015-02-17 | 2018-10-02 | Evonik Degussa Gmbh | Method for the epoxidation of an olefin with hydrogen peroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516738A (en) * | 1993-03-30 | 1996-05-14 | National Starch And Chemical Investment Holding Corporation | Epoxidation of olefins via certain manganese complexes |
| US20030055293A1 (en) * | 2000-04-27 | 2003-03-20 | Hanns Wurziger | Method for epoxidizing olefins |
| CN102822156A (en) * | 2010-02-02 | 2012-12-12 | 迈图专业化学股份有限公司 | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1489074A1 (en) * | 2003-06-18 | 2004-12-22 | Degussa AG | Process for the epoxidation of propene |
| EP2354131A1 (en) | 2010-02-02 | 2011-08-10 | Momentive Specialty Chemicals Research Belgium | Process for the manufacture of a 1,2-epoxide and a device for carrying out said process |
-
2013
- 2013-01-21 KR KR1020147018629A patent/KR20140117386A/en not_active Withdrawn
- 2013-01-21 WO PCT/EP2013/051034 patent/WO2013113578A1/en active Application Filing
- 2013-01-21 JP JP2014555144A patent/JP2015529628A/en active Pending
- 2013-01-21 EP EP13701049.2A patent/EP2809663A1/en not_active Withdrawn
- 2013-01-21 CN CN201380007204.1A patent/CN104093710A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5516738A (en) * | 1993-03-30 | 1996-05-14 | National Starch And Chemical Investment Holding Corporation | Epoxidation of olefins via certain manganese complexes |
| US20030055293A1 (en) * | 2000-04-27 | 2003-03-20 | Hanns Wurziger | Method for epoxidizing olefins |
| CN102822156A (en) * | 2010-02-02 | 2012-12-12 | 迈图专业化学股份有限公司 | Manufacture of an epoxyethyl carboxylate or glycidyl carboxylate |
Non-Patent Citations (1)
| Title |
|---|
| DIRK E. DE VOS ET AL.: "Epoxidation of Terminal of Electron-deficient Olefins with H2O2, catalyzed by Mn-trimethyltriazacyclonane Complexes in the Presence of an Oxalate Buffer", 《TETRAHEDRON LETTERS》, vol. 39, 23 June 1998 (1998-06-23) * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015529628A (en) | 2015-10-08 |
| KR20140117386A (en) | 2014-10-07 |
| EP2809663A1 (en) | 2014-12-10 |
| WO2013113578A1 (en) | 2013-08-08 |
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