[go: up one dir, main page]

CN105849080A - Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates - Google Patents

Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates Download PDF

Info

Publication number
CN105849080A
CN105849080A CN201480071558.7A CN201480071558A CN105849080A CN 105849080 A CN105849080 A CN 105849080A CN 201480071558 A CN201480071558 A CN 201480071558A CN 105849080 A CN105849080 A CN 105849080A
Authority
CN
China
Prior art keywords
ether
alcohol compounds
diatomic alcohol
carbonate
glycol
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
Application number
CN201480071558.7A
Other languages
Chinese (zh)
Inventor
肯尼斯·斯滕斯鲁德
帕德麦什·温基塔苏布拉马尼亚姆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Archer Daniels Midland Co
Original Assignee
Archer Daniels Midland Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from PCT/US2014/068809 external-priority patent/WO2015094716A1/en
Application filed by Archer Daniels Midland Co filed Critical Archer Daniels Midland Co
Publication of CN105849080A publication Critical patent/CN105849080A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • C07C43/16—Vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/16—Acetic acid esters of dihydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

A method of preparing a glycol mono-ether or mono-acetate, or carbonate involving either one of two pathways from alkylene glycols, HMF or its reduction derivative products (i.e., FDM, bHMTHFs), is provided. In particular, according to one pathway, the alkylene glycol, HMF or FDM, bHMTHFs are reacted with a dialkyl carbonate in the presence of a deprotonating agent, in substantial absence of an extrinsic catalyst, to produce an ether, and subsequently reacting the ether with an acid base. According to the other pathway, alkylene glycols are reacted with an acetate donor in the presence of an acid, base, to generate an alkylene mono-acetate, and etherified with a carbonate in the presence of a deprotonating agent.

Description

It is directly synthesized bio-based alkyl and furan glycol ether, acetas, ether-acetas and carbonic ester
Benefit of priority
This application claims the U.S. Provisional Application No. submitted to for 20th in December in 2013 61/918,795,2014 12 The PCT/US 2014/68809 of the moon 5 submission and the U.S. Provisional Application No. of December in 2014 submission on the 18th The benefit of priority of 62/093683, respective content is incorporated herein by reference.
Invention field
The present invention relates to a kind of method for making biologically-derived glycol be converted into useful product.Specifically, this Bright relate to a kind of simple and green method synthesizing multiple compounds from aklylene glycol or furan dihydroxylic alcohols.
Background technology
Having ether and alcohol functional group in same a part, glycol ethers is organic solvent one of general class.These Molecule combines the best dissolving power feature of alcohol and ether, and this allows well may be used in wide scope organic chemicals and oil Combination and dissolving power, and the dissolubility in water.Glycol ethers also has higher boiling point.Due to these reasons, Glycol ethers in (i) surface coatings industry as in the active solvent, (ii) brake fluid industry of resin as solvent, (iii) in petroleum industry as in the anti-freezing agent in various petroleum based fuels, (iv) auto industry as antifreezing agent and V () is outstanding for the specialty products of general merchandise.
Typically, glycol ethers is assigned or " e-series " or " p-series " glycol ethers, depends on that they are corresponding Ground is still made up of propylene of ethylene.Typically, e-series glycol ethers be found in medicine, sunscreen cream, cosmetics, In ink, dyestuff and water paint, and p-series glycol ethers be used for degreasing agent, cleaning agent, aerosol paint with And in binding agent.E-series glycol ethers is higher on molecular weight, and can serve as standing further chemical reaction Intermediate.P-series glycol ethers is typically High performance industrial solvent.
The preparation of the glycol ethers conventional generation relating to a kind of alkylene oxide.For example, it is possible to make oxirane (EO) Or expoxy propane (PO) reacts with the alcohol in e-series and p-series accordingly.Glycol ethers molecule can be at them In containing one or more EO or PO molecules.The typical alcohol used include methanol, ethanol, propanol, butanol, Amylalcohol and hexanol.This reaction can produce the glycol ethers with different chain length, depend on reaction mol ratio and Temperature used in this reaction and pressure.The mol ratio of relatively mild condition and this relatively low alkylene oxide and alcohol will produce Single alkylidene amino acetyl group ether, and use more alkylene oxide and higher temperature and pressure to produce two alkylene glycol ethers With three alkylene glycol ethers.These products are purified by distillation.Then glycol ethers can be made anti-with acetic acid further Answer (esterification) to produce corresponding acetate product.Accordingly, there exist and there is the multiple whole race product that may combine.(total Henry Chinn et al. is see, e.g., on body, " market survey is reported: glycol ethers (Marketing Research Report: Glycol Ethers), " chemical economics handbook (Chemical Economics Handbook), 663.5000A 633.5005Q (in November, 2010), SRI consulting firm (SRI Consulting).)
Alternately, this alkylene oxide can be by this alkylidene and the epoxidation of hypochlorous hydration base catalysis subsequently or logical The Direct Epoxidation crossing this alkylidene and tert-butyl hydroperoxide synthesizes.
In other method, glycol ethers can be existed at acidic catalyst or base catalyst with alkylene oxide by alcohol Under reaction produce.Such as, U.S. Patent number 6,124,506 describe the another kind of method of glycol ethers synthesis, the party Method relates to making alkylene oxide react on a catalyst with alcohol, and this catalyst includes a kind of layered double-hydroxide (LDH) Clay (wherein its layer structure is complete) and there is the anion of interlayer, at least some in these aniones It is anionic metal or (gathering) polyoxometalate anion.In a similar fashion, U.S. Patent number 8,748,635 B2 describes a kind of for using solid phase zeolite catalyst by the method for alkanisation anhydrosugar alcohol preparation dehydration sugar ether.
Aklylene glycol can be produced by multiple method.Such as, in a kind of approach, make glucose stand hydrogenation and make With with hydrogenesis to produce propylene glycol (PG) or ethylene glycol (EG).In another kind of approach, make glucose fermentation To produce ethanol and CO2.Then make ethanol conversion become oxirane with a kind of silver catalyst, then make this oxirane With CO2Be reacted to form ring-type carbonic acid ethylidene ester, when reacting with a kind of alcohol this carbonic acid ethylidene ester create right The dialkyl carbonate answered.In the dehydration/reduction step manufacturing epoxide, it is desirable to an additional reaction step Suddenly.These methods are directed to multiple step, and these steps add complexity and the cost producing desired product.
Commercial manufacturers wishes a kind of simpler, single step etherification method.But, for the currently available side of synthesis Method can not make directly from the aklylene glycol (such as ethylene glycol (EG) and propylene glycol (PG)) derived from bio-based source Manufacture ether.First some preceding or middle steps must occur.At present, do not have can optionally make bio-based Become to the direct non-oxidation of aklylene glycol the known method of corresponding monoether.Therefore it provides it is a kind of for direct ether Change not only aklylene glycol but also ring-type (furan) dihydroxylic alcohols will be to be subject to as a kind of new method of the approach of parent material The progress welcome.
Summary of the invention
Present disclosure relates to a kind of method for preparing monoether from diatomic alcohol compounds, and the method comprises or the first approach Or the second approach.In this first approach, make this diatomic alcohol compounds in uniform temperature in the presence of bronsted acid Descend and persistently be enough to be formed a kind of R of this diatomic alcohol compounds1The time contact R of monoesters1Organic acid, then makes this The R of diatomic alcohol compounds1Monoesters at a certain temperature and persistently be enough to form this list in the presence of deprotonation agent The time contact one of ester ether has formula R2(CO3)R2R2Alkyl diester.In this second approach, make this dihydroxylic alcohols Compound at a certain temperature and persistently be enough to form the one of this diatomic alcohol compounds in the presence of deprotonation agent The time contact planting monoesters has formula R2(CO3)R2R2Alkyl diester, then makes the monoesters of this diatomic alcohol compounds exist At a certain temperature and persistently be enough to be formed a kind of R of time contact of this monoesters ether in the presence of bronsted acid1Have Machine acid.This R1And R2It is or identical or different alkyl, cycloalkyl or aryl moieties.
The other feature and advantage of the inventive method will be disclosed in described further below in.It it should be understood that above-mentioned general introduction And described further below and example the most only represents the present invention, and aim to provide for understand as claimed this The summary of invention.
Brief Description Of Drawings
Fig. 1 is a general schematic, the figure shows from a kind of alkylene dihydric alcohol preparation etherificate or acetylation two Two kinds of route of synthesis in unit's alcohol.
Fig. 2 is the schematic diagram of the reaction of an embodiment according to the inventive method, the figure shows propylene glycol and the third two Alcohol-acetas is alkyl etherified.
Fig. 3 is the schematic diagram of the reaction of another embodiment according to the inventive method, the figure shows FDM and FDM acetas is alkyl etherified.
Fig. 4 is the schematic diagram of the reaction of an alternate embodiment according to the inventive method, the figure shows bHMTHF Alkyl etherified with bHMTHF acetas.
Fig. 5 is the schematic diagram of the reaction of another embodiment according to the inventive method, the figure shows aklylene glycol The synthesis of carbonic ester.
Fig. 6 is the schematic diagram of the reaction of another embodiment according to the inventive method, and this figure discloses FDM carbonic acid The synthesis of ester.
Fig. 7 is the schematic diagram of the reaction of another embodiment according to the inventive method, the figure shows bHMTHF The synthesis of carbonic ester.
Detailed description of the invention
The explanation of part I.-
A.
Synthetic method of the present invention provide a kind of for directly from alkyl or furan dihydroxylic alcohols without making from renewable, raw The parent material of thing sill or dehydration or the most originally prepared ether and/or simple, the cleaning of acetas and succinct Method.Compared to the often complicated of conventional ether synthesis and exacting terms, the inventive method relates to making alkyl diol And it is being substantially absent from outside any other in the presence of deprotonation agent with the solution of dialkyl carbonate reagent To react under catalyst.As used in this, this term " is substantially absent from " and refers to a kind of situation, Qi Zhongyi Kind of allocatalysis agent or to a great extent or be completely absent, or with less than the trace of catalytic effect or trace Exist.In other words, there is no allocatalysis agent, or with the amount relative to the dialkyl carbonate reagent in reaction Less than 5%, 3% or 1% w/w level exist.
The method can be used for from reproducible alkylidene, alkyl or furan dihydroxylic alcohols to manufacture monoether, monoesters and Alkoxy ester and without or oxidation to form oxide or dehydration and reduction to form epoxide.The reality of dihydroxylic alcohols Example is glycol such as ethylene glycol (EG), propylene glycol (PG) and 2,3-butanediol (BDO).Alternately, these Reactant materials can be ethylene glycol acetate, Propylene glycol monoacetate or its mixture.This furan dihydroxylic alcohols is anti- Answer thing can be HMF reduction analog (furan-2 ,-5-dimethanol (FDM) and/or 2,5-be double-methylol-four Hydrogen furan (bHMTHF)).Alternately, when HMF is reactant, can ether under the conditions of the reaction according to the invention Change or acetylation HMF self.
Generally in accordance with the inventive method, the method synthesis glycol monoethers mediated according to a kind of alkali.According to an embodiment, Mode simple using one, direct uses alkyl carbonate as a kind of alkylating agent and/or acid catalyzed Fischer acetyl Change and directly prepare monoacetate or ether-acetas or glycol, list-or two carbonic esters from aklylene glycol precursor.Separately In one embodiment, the method also allows for optionally preparing ether, acetas, ether-acetic acid from furan dihydroxylic alcohols Polyisocyanate polyaddition body, monocarbonate and two carbonic esters.According to some embodiment, this monoether is be produced from this reaction favourable And main product.
Fig. 1 represents of the two kinds of alternative route for preparing a kind of glycol monoethers or monoacetate according to the present invention Individual schematic diagram.Two kinds of approach will make it possible to generation or ether or acetate product.In this first approach, make to appoint A kind of solution of aklylene glycol and a kind of two carbonate reagent in the presence of deprotonation agent, be substantially absent from React under allocatalysis agent to produce a kind of ether, and use a kind of acid catalyst, base catalyst or enzyme catalyst subsequently This ether of acetylation.According to this second approach, this aklylene glycol is made to urge at acid catalyst, alkali with a kind of acetas donor React in the presence of agent or enzyme catalyst to produce a kind of alkylidene monoacetate, and then going with a kind of carbonic ester It is etherified in the presence of protonating agent or alkali.In a step subsequently, make ether products or this second way of this first approach The acetate product in footpath contains C with a kind of3The carbonate reaction of chain or longer, pi-allyl, phenyl or benzyl is to produce Raw a kind of monocarbonate or two carbonic esters or both.
Therefore, when starting according to a kind of aklylene glycol of this first approach, a kind of ether will be produced in the first step. Alternately, the first step in another kind of second approach will manufacture a kind of acetas.Specifically, according to this One approach, makes this aklylene glycol contact one in the presence of deprotonation agent under being substantially absent from allocatalysis agent Plant dialkyl carbonate reagent to produce ether.Subsequently, with as shown any one acid (such as acetic acid) or alternately With alkali (such as any alkoxide base (methoxide)) or this ether products of enzyme catalyst acetylation.According to this second approach, make (alternately alkali or enzyme are urged at mineral acid for aklylene glycol and a kind of acetas donor (such as free acid, anhydride, ether) Agent) in the presence of carry out reacting producing a kind of alkylidene monoacetate, then with a kind of carbonic ester in deprotonation agent Or in the presence of alkali, it is etherified this alkylidene monoacetate.In later step, make this intermediate ether or acetate product corresponding Ground acetylation or be etherified into a kind of end product.
This dialkyl carbonate reagent can have a kind of R-group having 1 to 20 carbon atom.When this R-group is When one methyl, ethyl, propyl group, the product of this reaction is typically a kind of ether.When this R-group is a C4-C20 During group, create a kind of carbonic acid mono alkyl ester.This bigger or huger R-part is tended to promote a kind of carbonic acid The formation of mono alkyl ester.For pi-allyl, phenyl or benzyl moiety or there is C when this etherifying agent contains one4Or more During the R-group of big chain, this product is intended to carbonic acid mono alkyl ester or dialkyl carbonate or both mixture.
In other embodiments, the inventive method makes alkyl or furan dihydroxylic alcohols or ethyl glycol acetate and alkyl carbonate exist In the presence of weak base (such as pKa=8-11), direct reaction is to produce corresponding monoether or diether compounds, if these Carbonic ester has the alkyl R-group less than or equal to about 3 carbon.
This reaction is by a kind of deprotonation agent or proton accepter (such as bronsted alkali) auxiliary.Multiple proton accepter Can include, such as, at least one in following item: calcium carbonate, potassium carbonate or sodium carbonate, amine, ammonia etc..Nothing Machine carbonate, specifically, illustrates the low solubility in reactor media, and this makes these carbonic esters at downstream part Reason is easier to separate from end product.
These approach can be squeezed, i.e. this glycol first can be made monoacylated, and then manner described above is carried out Etherificate.This etherificate occurs under not having allocatalysis agent, but only by disposing a kind of bronsted alkali to promote this alkyl Change.This bronsted alkali has the pKa of at least 4, and this contributes to-OH the deprotonation of this polyhydric alcohol.
The amount of the dialkyl carbonate reagent in this reaction can be in every aklylene glycol molecule at least 1 (1) Amount to about 3 (3) stoichiometric equivalents.In order to prepare a kind of monoether, the amount of dialkyl carbonate reagent is with often Hydroxyl (OH) group about 2 (2) stoichiometric equivalents of this alkyl diol exists.
In certain embodiments, this carbonate reagent can be one of following functional group: single propyl group, monobutyl, list penta Base, single hexyl, monobenzyl, single phenyl, monoallyl, dipropyl, dibutyl, diamyl, dihexyl, dibenzyl Base, diphenyl, diallyl.Produced ether or carbonate products cross reference to related application can be accordingly or: monoalky lether or two Alkyl ether, or carbonic acid mono alkyl ester, carbonic acid monoallyl ester, Single-aryl ester carbonate, or dialkyl carbonate, Carbonic acid diallyl ester or diaryl carbonate.
In yet another aspect, present disclosure relates to ether, acetas and the alkyl carbonate according to preceding method synthesis.Always On body, the monoether of this alkylen glycol compound is at least one in following item: the monoether of ethylene glycol (EG), third The monoether of glycol (PG) or the monoether of 2,3-butanediol (BDO).The monoacetate of this alkylen glycol compound It is at least one in following item: ethylene glycol, Propylene glycol monoacetate or 2,3-butanediol (BDO).
Generally, during the acetas of this alkylen glycol compound is following item at least one: ethylene glycol accordingly (EG), propylene glycol (PG), 2,3-butanediol (BDO), ethylene glycol mono-ether or propylene glycol monoether, 2,3-fourth two Alcohol.
Generally, this carbonic acid mono alkyl ester or dialkyl carbonate product can contain following alkyl, pi-allyl or aryl At least one in group: monobutyl, single amyl group, single hexyl, monobenzyl, single phenyl, monoallyl, dibutyl, Diamyl, dihexyl, dibenzyl, diphenyl, diallyl or from C3-C20The monoalkyl of carbon atom or dialkyl group Group.
B.
Fig. 2 illustrates the synthesis of an embodiment according to the inventive method.As shown in this embodiment, This propylene glycol and a kind of two carbonic esters are made under heating and to react to produce third in the presence of nucleophile (such as potassium carbonate) Glycol alkyl ether.
These ethers can be by being processed further manufacturing propylene glycol alkyl ether acetic acid ester with a kind of acetyl alcohol and acid treatment. Similarly, the alkylated reaction described in figures 3 and 4 show accordingly use furan dihydroxylic alcohols, FDM with And the alternate embodiment of bHMTHF.In figure 3, FDM and dialkyl carbonate is made to react to produce FDM alkane Base ether, makes this FDM alkyl ether change into FDM alkylether acetates subsequently.In the diagram, two kinds of bHMTHF are made Isomer by reacting change into three kinds of bHMTHF alkyl ether isomers with ethanol and a kind of acid catalyst, and with After after carrying out acid treatment with acetic acid, change into 3 kinds of bHMTHF alkylether acetates isomers.
An advantage of the present invention is that they can provide for directly (particularly biological from a kind of aklylene glycol Derivative aklylene glycol) prepare simple, the cleaning of ether and succinct method.As used herein, term is " biological Derive " or " bio-based " refer to be produced from renewable biological source (such as plant, cellulose or agricultural biomass Or their derivant) hydrocarbon molecules, compared to so-called fossil base or petroleum base Hydrocarbon.Should Clean method can aid in simplification downstream separation and purge process.
According to an embodiment, when being etherified in pure dialkyl carbonate, it is to observe that dialkyl ether is similar to thing The only product arrived.When carrying out with the dialkyl carbonate (that is, the alkylating agent of stoichiometric amount) of about monovalent During this etherificate, only produce monoether product, although with relatively low productivity (e.g. ,≤10%).Great majority these propylene glycol or Ethylene glycol still unreacted.But, the optimization of condition can be with Further aim productivity.The product of the improvement of target monoalky lether Rate, it is, for example possible to use the dialkyl carbonate of about 2 or 3 equivalents and revise other response parameters (as lower Temperature or longer response time) realize.
According to a kind of controlled reaction carried out at relatively mild temperature and ambient pressure, this method provide one For being etherified the eco-friendly mode of these glycol.This reaction is typically the temperature between about 70 DEG C and 150 DEG C Under carry out.Typically, this reaction is the temperature in the range of about 70 DEG C or 80 DEG C to about 130 DEG C or 140 DEG C Under.More typically, this reaction temperature be in the range of about 80 DEG C or 90 DEG C to about 110 DEG C or 120 DEG C ( In great majority reaction, this temperature is at about 125 DEG C.The reaction condition of these gentlenesses contributes to controlling and minimizing pair Product Compound or other potential isomers and the formation of impurity.
If the etherification reaction of the present invention is in higher temperature, at such as from about 130 DEG C to about 150 DEG C the most about 24 hours Or the prolongation response time of 40 hours operates, then can produce notable with relatively high selectivity and purity level This ether products of productivity.
C.
1. aklylene glycol etherificate
Can adaptive conventional synthesis process as described in this to manufacture multiple common glycol ethers.Such as, table 1 is listed The glycol ethers that some are common, industry is useful is together with their abbreviation and chemical name.
Table 1
Common first names Abbreviation Chemical name
Glycol monoethyl ether EGME 2-methyl cellosolve
Ethylene glycol monomethyl ether acetate EGMEA 2-methoxyethyl acetate
Ethylene glycol monoethyl ether EGEE Cellosolvo
Ethylene glycol monoethylether acetate EGEEA 2-ethoxyethyl acetate
Ethylene glycol ether EGPE 2-allyloxyethanol
Ethylene glycol monobutyl ether EGBE Butoxy ethanol
Glycol dimethyl ether EGDME 1,2-dimethoxy-ethane
Ethylene glycol diethyl ether EGDEE 1,2-diethoxyethane
Diethylene glycol DEG
Diethylene glycol monomethyl ether DEGME 2-(2-methoxy ethoxy)
Ethanol diethylene glycol monoethyl ether DEGEE 2-(2-ethoxy ethoxy) ethanol
Diethylene glycol monobutyl ether DEGBE 2-(2-Butoxyethoxy) ethanol
Diethylene glycol dimethyl ether DEGDME Double (2-methoxy ethyl) ether
TRIGLYME TEGDME
Propylene glycol monomethyl ether PGME 1-methoxy-2-propanol
Propylene glycol methyl ether acetate PGMEA
Dipropylene glycol DPG
Dipropylene glycol monomethyl ether DPGME
2. furan etherificate
The present invention reacts and can also be used together with furan compound.Fig. 3 shows that the synthesis according to an embodiment is anti- The schematic diagram answered, wherein makes FDM and dialkyl carbonate be reacted to form a kind of FDM monoalky lether.Subsequently, Make this ether acetylation to produce corresponding FDM alkylether acetates.Fig. 4 depicts by bHMTHF (THF-binary Alcohol) a kind of similar two-step reaction, wherein make bHMTHF change into THF alkyl ether and the then second of correspondence It is acylated into THF alkylether acetates.
Generally, this furan dihydroxylic alcohols is at least one in following item: FDM, bHMTHF diastereomer (diestereomer), respectively；FDM monoacetate, bHMTHF monoacetate diastereomer, respectively Ground.This ether products has at least one in following alkyl group: monoalkyl, single ethyl, monoallyl.
3. alkyl carbonate is formed
In yet another aspect, present invention reaction can adapt to manufacture organic carbonate, and these organic carbonates are class tools There is the reaction platform of multiple effectiveness, especially in ester exchange, alkylation or arylation.
Fig. 5-7 represents three kinds of single general reactions for preparing carbonic ester according to different embodiments, when this carbonic acid two The R-group of Arrcostab reagent is C3Or when bigger, pi-allyl, benzyl or aryl.In Figure 5, propylene glycol is made Change into the dialkyl carbonate (diaklokycarbonate) of a kind of correspondence.In figure 6, FDM is made to change into one Plant furan carbonic ester, and in the figure 7, make bHMTHF change into isomeric THF carbonic ester.
Part II. example
Following instance synthesizes the further illustrating and as its other party of present disclosure of ether as from propylene glycol and ethylene glycol Face provides.The change of parameter and condition (e.g., temperature, time and reagent concentration, and concrete initial species and urging Agent and the change of amount thereof) can affect and extend the whole practice of the present invention.
A. diol monoacetate
Following instance illustrates the reaction for synthesizing propanediol monoacetate.Ethyl glycol acetate constitutes in application as used Material useful in the solvent, precursor of additive, binding agent, plasticizer, lubricant and surfactant.
Example 1: synthesizing propanediol monoacetate
To one equipped with the 500mL round-bottomed flask of Dean-Stark (dean stark) device loads 100g's A kind of macroporous polymer catalyst (business being used for using in high temperature heterogeneous catalysis of propylene glycol, the acetic acid of 75g and 5g Amberlyst it is referred to as in industryTM70, from Dow Chemical (Dow Chemical, Inc)).This reaction is mixed Thing is heated to 120 DEG C and removes water from this reactant mixture.Residue mainly comprises Propylene glycol monoacetate.
Example 2: synthesizing propanediol monoacetate
To one equipped with the 500mL round-bottomed flask of Dean-Stark device loads the propylene glycol of 100g, 115g Ethyl acetate and 0.5g Feldalat NM.This reactant mixture is heated to 90 DEG C and removes from this reactant mixture Ethanol.Residue mainly comprises Propylene glycol monoacetate.
Example 3: synthesizing propanediol monoacetate
Load in the autoclave engineering reactor (autoclave engineer reactor) of a 1L 200g propylene glycol, The acetic acid of 150mL and 2 dense H2SO4.Assemble this reactor body and this reactor be heated to 130 DEG C persistently 3 hours.Make this reactor cooled.Product is mainly made up of Propylene glycol monoacetate.
B. straight-chain alkyl-sub-glycol monoethers
Example 1: the PG in methanol is methyl etherified (1:1PG/DMC)
Experiment: load the propylene glycol (PG, 65.7mmol) of 5g, 5.53mL in a 100mL kieldahl flask Dimethyl carbonate (65.7mmol), the potassium carbonate of 18.2g and the methanol of 40mL.This mixture equipped with One Friedrichs condenser and reflux (about 80 DEG C) overnight.After such time, this uneven mixing is made Compound is cooled to room temperature, filters excess potassium carbonate, and stores filtrate.The sample making this filtrate stands quantitatively to divide Analysis, its result shows that the PG of about 10% changes into monomethyl ether A and the B of correspondence the most on a 50-50 basis.The most do not describe PG dimethyl ether does not the most describe other products.
Example 2: the PG in methanol is methyl etherified (1:2PG/DMC)
Experiment: be similar to the reaction described in example 1, produces more substantial methyl ether in another kind reacts, its Middle propylene glycol is in 1:2 with the ratio of dimethyl carbonate.The third of 5g is loaded in a 100mL kieldahl flask Glycol (PG, 65.7mmol), the dimethyl carbonate (131.4mmol) of 11.06mL, the potassium carbonate of 18.2g, And the methanol of 40mL.This mixture is equipped with a Freidrichs condenser and refluxes (about 80 DEG C) overnight. After such time, make this uneven mixture be cooled to room temperature, filter excess potassium carbonate, and store filtrate. Analyzed a sample of this filtrate quantitatively by GC/MS, its result shows that the PG of about 40% turns the most on a 50-50 basis The monomethyl ether (18%A and 18%B) that chemical conversion is corresponding, the most about 4% is converted into dimethyl ether.
Example 3:PG is methyl etherified, pure
Experiment: load 1g in a single neck 100mL kieldahl flask equipped with the magnetic stirring bar of PTFE coating Propylene glycol (PG, 13.1mmol), the potassium carbonate (52.6mmol) of 7.27g and the carbonic acid diformazan of 50mL Ester.It is installed on this kieldahl flask and then by this mixture be heated to by a water-cooled Friedrichs condenser 90 DEG C overnight.After such time, remove, filter and analyze an aliquot by GC/MS, this Disclose all of PG and be converted to dimethyl ether analog, without the evidence of monomethyl ether product.
Example 4: the EG in methanol is methyl etherified
Experiment: load the ethylene glycol (EG, 16.1mmol) of 1g, 1.35mL in a 100mL kieldahl flask Dimethyl carbonate (16.1mmol), the potassium carbonate (52.6mmol) of 11.13g and the methanol of 40mL.Should Mixture is equipped with a Freidrichs condenser and refluxes (about 80 DEG C) overnight.After such time, make This uneven mixture is cooled to room temperature, filters excess potassium carbonate, and stores filtrate.Quantitative by GC/MS A sample of this filtrate is analyzed on ground, and its result shows that the EG of about 15% changes into the monomethyl of correspondence the most on a 50-50 basis Ether A and B.The most do not observe that EG dimethyl ether does not the most observe other products.
Example 5:EG is methyl etherified, pure
Experiment: load 1g in a single neck 100mL kieldahl flask equipped with the magnetic stirring bar of PTFE coating Ethylene glycol (EG, 16.1mmol), the potassium carbonate (52.6mmol) of 11.13g and the carbonic acid two of 50mL Methyl ester.It is installed on this kieldahl flask and then by this mixture be heated to by a water-cooled Friedrichs condenser 90 DEG C overnight.After such time, remove, filter and analyze an aliquot by GC/MS, this Disclose all EG and be converted to dimethyl ether analog, without the sign of monomethyl ether product.
Example 6: the EG in methanol is methyl etherified (1:1EG/DMC)
Experiment: load the ethylene glycol (EG, 16.1mmol) of 1g, 1.35mL in a 100mL kieldahl flask Dimethyl carbonate (16.1mmol), the potassium carbonate (52.6mmol) of 11.13g and the methanol of 40mL.Should Mixture is equipped with a Freidrichs condenser and refluxes (about 80 DEG C) overnight.After such time, make This uneven mixture is cooled to room temperature, filters excess potassium carbonate, and stores filtrate.Quantitative by GC/MS A sample of this filtrate is analyzed on ground, and its result shows that the EG of about 15% changes into the monomethyl of correspondence the most on a 50-50 basis Ether A and B.The most do not observe that EG dimethyl ether does not the most observe other products.
C. straight-chain alkyl-sub-glycol carbonate
Example 7: synthesis diphenyl propane-1,2-diyl two carbonic ester, PG diphenyl carbonate C
Experiment: load the third of 1g in a 25mL round-bottomed flask equipped with oval PTFE magnetic stirring bar Glycol A (13.1mmol), the diphenyl carbonate B (25.2mmol) of 5.65g and the potassium carbonate of 3.65g (25.2mmol).Stirring while and at argon shield under, the mixture that this is uneven is heated to 100 DEG C Overnight.After such time, with this mixture of 20mL dchloromethane, filter to remove Excess solid, and And be analyzed by TLC (2% methanol in ethyl acetate, UV-Vis and potassium permanganate irradiate), this shows All propylene glycol have been consumed and have been furthermore shown that only one point.This mother solution aliquot is removed, Use CDCl3It is diluted, and is analyzed by NMR.1H NMR(CDCl3, 400MHz) and δ (ppm) 7.29-7.27 (m, 4H), 7.17-7.15 (m, 4H), 7.13-7.11,4.70-4.69 (m, 1H), 4.10-4.08 (m, 1H), 4.01-3.99 (m, 1H), 1.47 (s, 3H)；13C NMR(CDCl3, 125MHz) and δ (ppm) 158.54、157.51、153.38、151.15、129.78、126.16、121.32、116.14、114.65、74.05、 73.02、16.55。
D. furan dihydroxylic alcohols (FDM and bHMTHF) ether
Example 1. synthesizes double (methoxy) the furan C of (5-(methoxy) furan-2-base) methanol B, 2,5-.
Experiment: load 100 in a 10mL mono-neck kieldahl flask equipped with the magnetic stirring bar of PTFE coating The A (FDM, 0.780mmol) of mg, the potassium carbonate (3.902mmol) of 539mg and the carbonic acid of 5mL Dimethyl ester (413mmol).One reflux condenser is assembled on this flask, and while stirring, should Uneven mixture is heated to 90 DEG C and continues 8 hours.After such time, by filtering removal residual carbonic acid Potassium, and make this filtrate under reduced pressure concentrate.Produced pale yellow oil is made to be dissolved in the dichloromethane of minimum In and load in prefabricated silicagel column, wherein use the flash chromatography of ethyl acetate to provide following two groups of fraction: A) Including C as those of a kind of translucent grease, Rf=0.72, it is weighed as 26mg after concentration.This material Elementary analysis disclose following result: for C8H12O3Desired, C, 61.52；H, 7.74.The C found, 61.43；H, 7.85.B) represent that B is as those of a kind of wax-like buff white solid, Rf=0.54, claim after concentration It is heavily 21mg.The elementary analysis of this material discloses following result: for C7H10O3Desired, C, 59.15； H, 7.09.The C found, 59.28；H, 7.07.
Example 2: synthesis ((2S, 5R)-5-(methoxy) oxolane-2-base) methanol, ((2S, 5S)-5-(methoxy methyl Base) oxolane-2-base) methanol, ((2R, 5R)-5-(methoxy) oxolane-2-base) methanol B；(2R,5S)-2,5- Double (methoxy) oxolane, (2S, 5S)-2, double (methoxy) oxolane of 5-, C
Experiment: load 250 in a single neck 25mL round-bottomed flask equipped with the magnetic stirring bar of PTFE coating The A (9:1 cis/trans, 1.89mmol) of g, the potassium carbonate (7.57mmol) of 1.05g and 15mL carbon Dimethyl phthalate.One reflux condenser is assembled on this flask, and while stirring, by this uneven mixing Compound is heated to 90 DEG C and continues 12 hours.After such time, make light yellow residue under reduced pressure concentrate, carry For a kind of loose, transparent grease.Then this grease is made to be dissolved in the dichloromethane of minimum and load In one prefabricated silicagel column, the flash chromatography of ethyl acetate eluent is wherein used to provide following two groups of fraction: A) Constitute C those, (Rf=0.67, after concentration a kind of loose, the colourless grease of 68mg) disclose with Lower elementary analysis result: for C8H16O3Desired, C, 59.98；H, 10.07.Find: C, 59.87； H, 10.01.B) those of B, (Rf=0.46, the after concentration a kind of loose colourless grease of 94mg) are included Disclose following elementary analysis result: for C7H14O3Desired, C, 57.51；H, 9.65.The C found, 57.70, H 9.53.
E. furan dihydroxylic alcohols carbonic ester
Double (methylene) dipropyl of example 1. (5-(methylol) furan-2-base) methyl propyl carbonate B, furan-2,5-diyl Double (carbonic ester) C.
Experiment: load 100mg in a single neck 5mL round-bottomed flask equipped with the magnetic stirring bar of PTFE coating A (0.780mmol), 1.21mL carbonic acid dipropyl (DPC, 7.80mmol) and 543 μ L DIEA (3.12mmol).This neck clogs and in play under argon shield with a rubber sheet gasket being attached to Ar inlet Under strong stirring, this mixture is heated to 120 DEG C overnight.After such time, excess DPC is removed under a high vacuum And DIEA, and this mixture is dissolved in the dichloromethane of 1mL and loads in a prefabricated silicagel column, Hexane/ethyl acetate eluent gradient flash chromatography method is wherein used to provide fraction, especially for C (Rf1= 0.72), it is weighed as 22mg as a kind of semisolid tacky, translucent after concentration.1H NMR analysis (400MHz, CDCl3) disclose signals below δ (ppm): 6.23 (d, J=8.2Hz, 1H), 6.15 (d, J=8.2Hz, 1H), 5.21 (s, 2H), 5.10 (t, J=6.8Hz, 1H), 4.24 (d, J=6.2Hz, 2H), 4.10 (t, J=7.4Hz, 2H), 1.59 (m, 2H), 1.10 (t, J=7.0Hz, 3H).Additionally, separation eluent fraction Especially for B (Rf=0.54), it is provided that the loose colourless grease of 28mg after concentration a kind.This mixing Thing1H NMR analyze disclose signals below δ (ppm): 6.25 (s, 2H), 5.20 (s, 2H), 4.22 (d, J=6.2Hz, 2H), 1.61 (m, 2H), 1.03 (t, J=6.8Hz, 3H).
Example 2: synthesis ((2R, 5S)-5-(methylol) oxolane-2-base) methyl propyl carbonate, ((2S, 5S)-5-(hydroxyl Methyl) oxolane-2-base) methyl propyl carbonate, ((2R, 5R)-5-(methylol) oxolane-2-base) methyl-propyl carbon Acid esters B；Dipropyl (((2R, 5S)-oxolane-2,5-diyl) double (methylene)) double (carbonic esters), dipropyl (((2S, 5S)- Oxolane-2,5-diyl) double (methylene)) double (carbonic ester) C.
Experiment: load 100mg in a single neck 5mL round-bottomed flask equipped with the magnetic stirring bar of PTFE coating A (0.751mmol), 1.17mL carbonic acid dipropyl (DPC, 7.51mmol) and 522 μ L DIEA (3.00mmol).This neck clogs and in play under argon shield with a rubber sheet gasket being attached to Ar inlet Under strong stirring, this mixture is heated to 120 DEG C overnight.After such time, excess DPC is removed under a high vacuum And DIEA, and this is tacky, yellow oil is dissolved in the dichloromethane of minimum, and load one pre- In the silicagel column of system.Use ethyl acetate to provide two groups of fraction: A as the flash chromatography of eluent) a kind of colourless, Loose grease, Rf=0.70, after concentration be weighed as 18mg, this grease is carried out point by elementary analysis Analysis: for C14H24O7Desired, C, 55.25；H, 7.95.The C 55.12, H 7.84 found.B) a kind of Colourless, loose grease, Rf=0.52, it is weighed as 26mg after concentration: for C10H18O5Desired, C, 55.03；H, 8.31.The C 55.16, H 8.24 found.
The most generally and by means of example describe in detail the present invention.It should be appreciated by those skilled in the art that this Invention is not necessarily limited to the embodiment of specific disclosure, but without departing from such as by following claims or its equivalent (bag Including and be currently known or other equivalent components untapped, they can use within the scope of the invention) defined May be made that modifications and variations in the case of the scope of the present invention.Therefore, unless change additionally departs from the scope of the present invention, Otherwise these changes should be interpreted to be incorporated herein.

Claims (15)

1., for a method of preparing monoether from diatomic alcohol compounds, the method includes or the first approach or the Two approach, wherein:
In this first approach, make this diatomic alcohol compounds and R1Organic acid in the presence of bronsted acid at a constant temperature Degree is lower and persistently be enough to be formed a kind of R of this diatomic alcohol compounds1The time of monoesters contacts, then make this two The R of unit's alcoholic compound1Monoesters and one have formula R2(CO3)R2R2Alkyl diester is in the presence of deprotonation agent The time that at a certain temperature and persistently be enough to be formed monoesters ether contacts；Or
In this second approach, make this diatomic alcohol compounds and there is formula R2(CO3)R2R2Alkyl diester is in deprotonation The time that at a certain temperature and persistently be enough to be formed a kind of monoesters of this diatomic alcohol compounds in the presence of agent enters Row contact, then makes the monoesters of this diatomic alcohol compounds and a kind of R1Organic acid in the presence of bronsted acid one The time that under fixed temperature and persistently be enough to be formed this monoesters ether contacts；
Wherein R1And R2It is identical or different alkyl, cycloalkyl or aryl moieties.
Method the most according to claim 1, wherein this diatomic alcohol compounds is that at least one choosing is the most following The member of the group of item composition: ethylene glycol (EG), propylene glycol (PG) and 2,3 butanediols (BDO).
Method the most according to claim 1, wherein this diatomic alcohol compounds is that at least one choosing is the most following The member of the group of item composition: furyl dimethyl carbinol (FDM) and tetrahydrofurandimethanol (THF dihydroxylic alcohols).
Method the most according to claim 1, wherein said R1Organic acid is acetic acid and described monoesters is one Plant ether acetic acid ester compounds.
Method the most according to claim 1, wherein R1And R2It is identical or different C2To C8Alkyl portion Point.
Method the most according to claim 10, wherein said single and/or two carbonic esters have a kind of C3-C8's R-group.
Method the most according to claim 1, wherein said deprotonation agent is a kind of bronsted alkali.
Method the most according to claim 1, wherein said deprotonation agent selects free the following composition Group: potassium carbonate, sodium carbonate, calcium carbonate and amine.
Method the most according to claim 1, wherein for contact with this bronsted acid and with this deprotonation Agent contact described temperature be between about 70 DEG C and 150 DEG C at a temperature of.
Method the most according to claim 1, wherein for contact with this bronsted acid and with this deprotonation The described temperature of agent contact is between about 80 DEG C and 130 DEG C.
11. methods according to claim 1, wherein for contact with this bronsted acid and with this deprotonation Agent contact described temperature be between about 90 DEG C to about 120 DEG C at a temperature of.
12. methods according to claim 1, wherein said deprotonation agent is a kind of with every diatomic alcohol compounds The inorganic carbonate that the amount of at least 1 (1) to about 3 (3) stoichiometric equivalents exists.
13. 1 kinds are used for the method manufacturing the alkyl carbonate of diatomic alcohol compounds, and the method includes: make this dihydroxylic alcohols Compound and one have formula R2(CO3)R2Alkyl diester in the presence of deprotonation agent the most also And persistently be enough to be formed the R of this diatomic alcohol compounds2The time of alkyl carbonate contacts.
14. methods as claimed in claim 13, wherein this diatomic alcohol compounds is that at least one choosing is the most following The member of the group of item composition: ethylene glycol (EG), propylene glycol (PG) and 2,3 butanediols (BDO).
15. methods according to claim 13, wherein this diatomic alcohol compounds is below at least one choosing freely The member of the group of every composition: furyl dimethyl carbinol (FDM) and tetrahydrofurandimethanol (THF dihydroxylic alcohols).
CN201480071558.7A 2013-12-20 2014-12-19 Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates Pending CN105849080A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US201361918795P 2013-12-20 2013-12-20
US61/918,795 2013-12-20
PCT/US2014/068809 WO2015094716A1 (en) 2013-12-20 2014-12-05 Synthesis of isohexide ethers and carbonates
USPCT/US2014/068809 2014-12-05
US201462093683P 2014-12-18 2014-12-18
US62/093,683 2014-12-18
PCT/US2014/071512 WO2015095710A1 (en) 2013-12-20 2014-12-19 Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates

Publications (1)

Publication Number Publication Date
CN105849080A true CN105849080A (en) 2016-08-10

Family

ID=53403742

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480071558.7A Pending CN105849080A (en) 2013-12-20 2014-12-19 Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates

Country Status (9)

Country Link
EP (1) EP3083548A4 (en)
JP (1) JP2017507899A (en)
KR (1) KR20160099646A (en)
CN (1) CN105849080A (en)
AU (1) AU2014369062A1 (en)
BR (1) BR112016014267A2 (en)
CA (1) CA2934512A1 (en)
MX (1) MX2016008061A (en)
WO (1) WO2015095710A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111349492A (en) * 2020-02-28 2020-06-30 浙江糖能科技有限公司 Application of 2, 5-tetrahydrofuran dimethyl alcohol fatty acid diester in diesel additive
CN114072374A (en) * 2019-09-04 2022-02-18 伊士曼化工公司 Aromatic enol ethers
CN114144397A (en) * 2019-09-04 2022-03-04 伊士曼化工公司 Aromatic enol ethers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH12019500292B1 (en) 2016-08-16 2023-07-05 Ppg Ind Ohio Inc Polymerizable composition for optical articles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880942A (en) * 1987-07-22 1989-11-14 Mitsui Petrochemical Industries, Ltd. Preparation of cyclic carbonates
JPH09227435A (en) * 1996-02-26 1997-09-02 Mitsui Toatsu Chem Inc Production of (poly)ethylene glycol diether
CN102365286A (en) * 2009-10-01 2012-02-29 罗盖特公司 Method for preparing a dialkyl carbonate of dianhydrohexitol

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2963489A (en) * 1953-07-30 1960-12-06 American Cyanamid Co 3, 4-furandimethanol and derivatives
US4012424A (en) * 1975-08-07 1977-03-15 Chem Systems Inc. Cracking of mixtures containing hydroxyesters
US4170596A (en) * 1976-10-05 1979-10-09 Kowa Company, Ltd. Novel monoesters of cis-cyclopentenediol, process for preparation thereof, and process for preparation of lactones from the monoesters
US4192949A (en) * 1977-06-28 1980-03-11 Basf Aktiengesellschaft Preparation of aralkyl phenyl ethers and alkyl phenyl ethers
KR100593529B1 (en) * 2004-03-31 2006-06-28 주식회사 엘지생활건강 Process for preparing ester type bleach activator compound
US8604244B2 (en) * 2010-07-02 2013-12-10 Reviva Pharmaceuticals, Inc. Compositions, synthesis, and methods of using cycloalkylmethylamine derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880942A (en) * 1987-07-22 1989-11-14 Mitsui Petrochemical Industries, Ltd. Preparation of cyclic carbonates
JPH09227435A (en) * 1996-02-26 1997-09-02 Mitsui Toatsu Chem Inc Production of (poly)ethylene glycol diether
CN102365286A (en) * 2009-10-01 2012-02-29 罗盖特公司 Method for preparing a dialkyl carbonate of dianhydrohexitol

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PIETRO TUNDO, ET AL.,: "Green Synthesis of Dimethyl Isosorbide", 《CHEMSUSCHEM》 *
刘小成等: "2-醋酸异山梨醇酯的合成研究", 《化学与生物工程》 *
朱驯: "乙二醇单乙醚醋酸酯的合成工艺改进研究", 《应用化工》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114072374A (en) * 2019-09-04 2022-02-18 伊士曼化工公司 Aromatic enol ethers
CN114144397A (en) * 2019-09-04 2022-03-04 伊士曼化工公司 Aromatic enol ethers
CN114072374B (en) * 2019-09-04 2024-03-08 伊士曼化工公司 Aromatic enol ethers
CN111349492A (en) * 2020-02-28 2020-06-30 浙江糖能科技有限公司 Application of 2, 5-tetrahydrofuran dimethyl alcohol fatty acid diester in diesel additive

Also Published As

Publication number Publication date
MX2016008061A (en) 2017-02-27
WO2015095710A1 (en) 2015-06-25
JP2017507899A (en) 2017-03-23
EP3083548A4 (en) 2017-08-30
KR20160099646A (en) 2016-08-22
AU2014369062A1 (en) 2016-06-30
BR112016014267A2 (en) 2017-08-08
EP3083548A1 (en) 2016-10-26
CA2934512A1 (en) 2015-06-25

Similar Documents

Publication Publication Date Title
Teng et al. A review on the performance of glycerol carbonate production via catalytic transesterification: Effects of influencing parameters
RU2594159C2 (en) Method of separating ethylene glycol and 1,2-butanediol
US10221116B2 (en) Process for the separation of monoethylene glycol and 1,2-butanediol
Du et al. Magnesium-catalyzed synthesis of organic carbonate from 1, 2-diol/alcohol and carbon dioxide
CN105849080A (en) Direct synthesis of bio-based alkyl & furanic diol ethers, acetates, ether-acetates, and carbonates
WO2010074256A1 (en) Process for producing dialkyl carbonate
CN103153463A (en) Method for recovery and recycle of ruthenium homogeneous catalysts
GB2567032B (en) Purification process for ethylene glycol via sequential distillation
US9890131B2 (en) Direct synthesis of bio-based alkyl and furanic diol ethers, acetates, ether-acetates, and carbonates
CN101918347A (en) Production of propylene glycol monoalkyl ether
CN102753516A (en) Method for producing diaryl carbonate
CN103080069B (en) Reactive recovery methylcarbonate from methylcarbonate/carbinol mixture
Terazzi et al. Synthesis of Cyclic Carbonates Catalyzed by CaI2–Et3N and Studies on Their Biocatalytic Kinetic Resolution
US20120330069A1 (en) Production of hydroxy ether hydrocarbons by liquid phase hydrogenolysis of cyclic acetals or cyclic ketals
CN100372830C (en) A kind of method of synthesizing tributyl citrate with catalysis of carbon base sulfonic acid
JP2017525659A (en) Composition of monoalkyl ether of monoanhydro-hexitol, process for its production and use thereof
CN107108645A (en) The CO of bio-based dihydric alcohol2The etherificate of mediation
Giomi et al. A convenient method for producing mono-and dichlorohydrins from glycerol
US20140378712A1 (en) Alkanolysis process
US20220098138A1 (en) Co-feeding ethylene with allyl alcohol in hydroformylation to make 1,4-butanediol and n-propanol
CN104277027A (en) Preparation method of (R)-propylene carbonate
KR102016016B1 (en) anufacturing Method of High Purity 1,2-Octanediol
US8492597B2 (en) Production of propylene glycol from glycerine
CN102015617A (en) Process for preparing alkanediol and dialkyl carbonate
KR102640902B1 (en) Method of preparing, separating, and purifying tetrahydrofuran-2,5-diester using tetrahydrofuran-2,5-dicarboxylic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160810

WD01 Invention patent application deemed withdrawn after publication