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WO1999059947A1 - Procede de preparation d'ethers et d'esters - Google Patents

Procede de preparation d'ethers et d'esters Download PDF

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Publication number
WO1999059947A1
WO1999059947A1 PCT/AU1999/000364 AU9900364W WO9959947A1 WO 1999059947 A1 WO1999059947 A1 WO 1999059947A1 AU 9900364 W AU9900364 W AU 9900364W WO 9959947 A1 WO9959947 A1 WO 9959947A1
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Prior art keywords
alcohol
halide
ether
produce
mmol
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PCT/AU1999/000364
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English (en)
Inventor
Teresa Cablewski
Laurence John Bagnell
Christopher Roy Strauss
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Priority to AU36941/99A priority Critical patent/AU3694199A/en
Publication of WO1999059947A1 publication Critical patent/WO1999059947A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/36—Esters of dithiocarboxylic acids
    • 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
    • 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
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • This invention relates to a process for preparing ethers and esters (including thioethers, thioesters and dithioesters) from alcohols using organic halide which can be regenerated in situ.
  • ethers usually employs either strongly acidic or basic conditions.
  • the traditional process for the preparation of symmetrical or unsymmetrical ethers is the Williamson synthesis, which involves condensation of a sodium or potassium alkoxide or aryl oxide with an organic halide. This process is still the most commonly used procedure, even though it results in the production of stoichiometric quantities of salt and does not work well with base labile compounds.
  • U.S. Patent 4613682 to Eickholt describes a method for the preparation of aromatic ethers by reacting a phenolic compound with an organic halide. The process is carried out by passing the reactants in the vapour phase over a solid catalyst containing a metal oxide or a metal until the corresponding ether (i.e. the product of reaction of the phenol with the organic halide) is formed. The byproduct hydrogen halide formed may be reacted with a halide acceptor, such as methanol.
  • Methods for esterification of carboxyhc acids have been summarized (Raber, D.J. et al. , J. Org. Chem., 1979, 44, 1149) and reviewed (Haslam, E.
  • esterification can proceed by transfer of the acyl moiety to an alcohol.
  • the additional synthetic step lowers the atom economy, a stoichiometric amount of HC1 or carboxyhc acid respectively is by-produced, and adverse side reactions may occur.
  • the carboxylate ion can be employed as a 20 nucleophile. Even sterically crowded acids can be esterified this way. Examples include reactions of carboxylate salts, either preformed or generated in situ, with suitable alkylating agents such a trialkyloxonium salts, alkyl halides, dialkyl sulfates, alkyl chlorosulfites, alkyl phosphites and diazomethane. Although such reactions may proceed to ambient temperature, they do not appear to have been conducted catalytically.
  • the leaving group of the alkylating 25 agent contributes to the waste produced (including some hazardous salts), in stoichiometric amounts at least.
  • salts account for the bulk of industrial chemical wastes. They can pollute soil and ground water and have been implicated in the formation of acid-dew.
  • the present invention provides a process for the synthesis of ethers or esters comprising reacting an alcohol or carboxyhc acid with an organic halide to produce an ether or ester respectively and a hydrogen halide, wherein further organic halide for the production of ether or ester is generated in situ by reaction of the hydrogen halide with an alcohol.
  • This cyclic process for the formation of ethers and esters from alcohols provides a convenient and environmentally beneficial route to a wide range of commercially useful ethers, esters, lactones, polyethers, polyesters, cyclic ethers and ether and ester compositions, as well as their sulphur containing counterparts.
  • the process reduces the production of environmentally unfriendly hydrogen halides and, in view of the fact that the process can be conducted at or near neutrality, can be employed for reactions involving acid or base labile compounds.
  • the process also produces little waste materials and can be performed without the solid metal oxide or metal catalysts described in US Patent 4,613,682.
  • the reaction may also be conducted in the liquid phase, there being no need to conduct the reaction in the vapour phase as described in the US 4,613,682.
  • R is the residue of an alcohol, thiol, carboxyhc acid, thioacid or dithioacid
  • R' is the residue of an organic halide
  • R" is the residue of an alcohol or thiol
  • X is halide
  • Y is -CO 2 -, -O-, -S-, -C(O)S-, or -C(S)S-
  • Z is -O- or -S-.
  • R is the residue of a carboxyhc acid, thioacid or dithioacid
  • R' is advantageous for R' to be the same as R" as the product of the reaction shown in Equations 1 and 3 would be the same.
  • R'X used to "catalyse" the reaction sequences
  • the amount of RYR' produced would be quite minimal.
  • the nature of the reactants may be selected in such a way that the major contaminating products can be removed, e.g. by distillation, throughout the process.
  • HX would react with the alcohol or thiol, R"ZH, to generate the organic halide, R"X, as per Equation 2.
  • the organic halide can then react with RYH as per Equation 3 to produce the desired product, RYR", and regenerate HX.
  • reaction between the acid and the organic halide can be initiated with the addition of an alkali metal halide salt as shown in Scheme 2 below.
  • R, R" and X are as defined above, and
  • Z, Z' and Z" are independently selected from O and S.
  • esters refers to carboxyhc esters (-C(O)O-), thioester (-C(O)S-) and dithioesters (-C(S)S-).
  • alcohol refers to organic compounds containing one or more hydroxy (OH) or sulphydryl (SH) groups.
  • carboxyhc acid refers to organic acids having one or more carboxyhc (-C(O)OH) groups, thioacid (-C(O)SH) groups or dithioacid (-C(S)SH) groups, and salts or anhydrides thereof.
  • Equation 1 an excess of alcohol (or thiol) (R ⁇ ) and a minor amount of corresponding organic halide (RX) undergo a displacement reaction to afford ether (R 2 O) and hydrogen halide ( ⁇ X), or its ions ⁇ + and X " .
  • hydrogen halide refers to HX and/or its constituent ions.
  • the halide is preferably a good nucleophile (to accommodate Equation 2), a good leaving group (to satisfy Equation 1) and poorly basic to preclude competing elimination reactions.
  • the halides Br “ and I " possess these properties and represent the preferred halides for use in the present process.
  • Other halides, such as Cl " may also be useful, as may other anions having the abovementioned properties.
  • Equation 2 It would be expected on the basis of Equation 2 that removal of water should favourably shift the position of equilibrium and limit the reverse reaction in Equation 3.
  • Equation 1 it has been reported in the literature (N.T. Farinacci and L.P. Hammett, J. Am. Chem. Soc, 1937, 59, 2542; Streitwieser, A. Jr. "Solvolytic Displacement Reactions” (McGraw-Hill: New York, 1962) pp. 34-38) that the rate of solvolytic displacement of alkyl halides by alcohols (see Equation 1) can be significantly accelerated by the addition of small amounts of water. Accordingly, for some reactions conducted in the liquid phase, complete removal of water may be detrimental. Despite these competing mechanisms involving water it is preferable for at least some of the water produced during the etherification to be removed.
  • One method of removing water is via azeotropy with aromatic hydrocarbons, such as toluene or xylenes, although the presence of these aromatic compounds in the reaction medium tends to inhibit nucleophilic substitutions, possibly due to the poor solvating properties of these low- polarity hydrocarbons.
  • Drying agents such as molecular sieves and CaSO 4 , may also be used, although removal of hydrogen halide along with the water can occur which is detrimental to the regeneration of the organic halide.
  • One way of minimising the effects of removal of water on the ability of the hydrogen halide to regenerate the organic halide, is to provide another process for the generation of hydrogen halide.
  • One method of achieving this is via the addition of a hydrogen halide generating compound, such as iodoform, tetrachloromethane or tetrabromoethane. These compounds decompose slowly in the presence of the alcohol to form HI and HBr, which produce the organic halide necessary for the etherification reaction. This procedure can also be used to replenish hydrogen halides lost by co-distillation with water. After completion of the reaction, unspent hydrogen halide generating compound could be recoverable by crystallisation and filtration.
  • Equation 1 It has been found that various factors affect the rate and extent of the reactions shown above in equations 1 and 2. As has been reported by Gelles et al (supra) when the concentration of alcohol is 10 to 50 times larger than the concentration of organic halide, the first order rate constant for Equation 1 can rise substantially. Thus the rate and extent of the reaction in equation 1 can depend on the relative concentrations of RX and ROH as well the concentration of water present.
  • the varying composition of the reaction mixture may have an influence on the nature of the products. Changes in polarity of the medium may result in a switching of the mechanism between S N 2 and S N 1. In the case of the latter mechanism, this may, in some circumstances, result in racemization of the products.
  • the initial organic halide may be generated in situ by the addition of a hydrogen halide, or by the addition of a compound which generates a hydrogen halide.
  • a hydrogen halide or by the addition of a compound which generates a hydrogen halide.
  • acid labile reactants it is preferred to commence the cyclic reaction sequence with an organic halide.
  • the halide is preferably a good leaving group (to satisfy Equation 1) and poorly basic to restrict competing elimination reaction.
  • the halides Br “ and I " possess these properties and represent the preferred halides for use in the esterification reaction.
  • R"OH it is also preferable for R"OH to be converted readily into R"X, e.g. by activation through protonation as an oxonium ion. Under basic conditions the forward reaction of Equation 2 would be inefficient. These requirements for the regeneration of R"X from R'OH make it desirable to have the free carboxyhc acid as the starting material. However free carboxyhc acids are generally poor nucleophiles. Accordingly the use of carboxylate anions as reactants may be preferable in some circumstances. Carboxyhc acids commonly have pKa's of around 4 and accordingly a pH within the range 4 to 7 may provide sufficient dissolution for the constraints associated with Equations 1 and 2 to be met and for the overall reaction to proceed.
  • reductid of an alcohol and “residue of thiol” as used herein refer to organic moieties capable of supporting hydroxyl or sulfhydryl functionalities respectively.
  • residue of an organic halide refers to organic moiety capable of supporting a halide functionality.
  • trace or “trace amount” when used in relation to a reactant, such as an organic halide or alkali metal halide, indicate that the amount added to the reaction is not stoichiometric, but is an amount sufficient to initiate or promote the reaction to the extent that the desired product is obtained.
  • the trace amount could refer to an amount added to the reaction mixture, or to a concentration of the reactant generated in situ.
  • the reactant RYH may be a carboxyhc acid, a thioacid, a dithioacid, an alcohol or a thiol.
  • RYH is a carboxyhc acid or an alcohol.
  • the carboxyhc acid may be any organic compound bearing one or more carboxyhc acid groups, optionally together with one or more non-deleterious substituents.
  • the carboxyhc acid or its corresponding carboxylate, should be capable of reacting with an organic halide to produce an ester.
  • Suitable monoacids include saturated or unsaturated alkanoic or alkenoic acids, such as straight chain or branched, saturated or unsaturated fatty acids, preferably having 1 to 18 carbon atoms, such as acetic acid, propanoic acid, butanoic acid, hexanoic acid, cyclohexanoic acid; and aromatic acids, such as benzoic acid, p-toluic acid.
  • suitable poly acids include malonic acid and terephthalic acid.
  • the carboxyhc acid may be a mixture of two or more carboxyhc acids, such that the final product will be a composition of esters, which could be fractionated if desired.
  • thioacids and dithioacids useful in accordance with the present invention include those which correspond to the carboxyhc acids described above in which one or more of the carboxyhc acid groups are replaced with the thioacid or dithioacid group.
  • the alcohol may be any organic compound bearing one or more hydroxy groups (optionally with one or more non-deleterious substituents) which are capable of reacting with an organic halide to produce an ether.
  • suitable monoalcohols include saturated or unsaturated monoalkanols, such as the products of hydrogenation of straight-chained or branched, saturated or unsaturated fatty acids or derivatives thereof, aliphatic or cyclic alkanols, preferably having 1 to 18 carbon atoms, such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol; and aromatic alcohols, such as phenol and naphthol.
  • Suitable polyols include ethylene glycol, 1 ,2-propylene glycol, 1 ,2-butylene glycol, neopentyl glycol, glycerol, diglycerol, triglycerol, tetraglycerol, trimethylolpropane, di-tri-methylolpropane, pentaerythritol, di-pentaerythritol, and sugar alcohols, such as sorbitan, glucose, fructose and sucrose.
  • the alcohol may also be a mixture of two or more alcohols, such that the final product of the reaction will be a composition of symmetrical and unsymmetrical ethers, which could be fractionated if desired.
  • thiols useful in accordance with the present invention include those which correspond to the alcohols described above in which one or more of the hydroxy groups is replaced with a sulfhydryl group.
  • the organic halides, R'X and R"X may be any organic halides capable of reacting with carboxyhc acids or alcohols (or thio equivalents) to produce esters or ethers respectively.
  • the groups R' and R" may be residues of the alcohols or carboxyhc acids described above.
  • the halide is attached to an aliphatic carbon atom.
  • the group R' corresponds to the group R.
  • the alcohol (or thiol), R"ZH, of Equation 2 may be any of the alcohols or thiols described above in relation to RYH.
  • R R.
  • the alcohol or thiol should be capable of reacting with HX to regenerate organic halide R"X.
  • the organic acid RC(Z')ZH of Equation 6 may be any of the acids described above in relation to RYH.
  • the salt QX represents an alkali metal halide.
  • the alkali metal halide is selected from LiCl, LiBr, Lil, NaCl, NaBr, Nal, CsCl, CsBr, Csl, KC1, Kbr and KI.
  • the reaction is preferably carried out using the alcohol (or thiol) as the solvent, although other solvents may be added if it is necessary to change the polarity of the solvent to achieve the desired product.
  • the reaction may be carried out in a solvent which can dissolve the alcohol and provide the desired polarity characteristics.
  • Suitable solvents include nitromethane, nitroethane, nitropropane, dimethylformamide, dimethylacetamide and acetonitrile.
  • the reaction may be carried out at any suitable temperature and pressure.
  • the temperature and pressure selected for a particular reaction will depend on the nature of the reactants and the solvent used. Generally the reaction will be carried out at a temperature between 40° and 400°C, more preferably between 70°C and 250°C.
  • the reaction will generally be conducted at atmospheric pressure, although in the case of some volatile alcohols or solvents, or in the case of some reactants which require reaction temperatures higher than the vapour pressure of the solvent system, the reaction can be performed in a pressurized vessel.
  • unsymmetrical ethers in the preparation of unsymmetrical ethers according to the method of the invention there will necessarily be some symmetrical product formed by reaction of the alcohol with the organic halide generated by reaction of the hydrogen halide with the alcohol.
  • the unsymmetrical product may be separated from the symmetrical product (if desired) using standard techniques, such as distillation, liquid chromatography, crystallisation and recrystallisation, zone refining or solvent partitioning.
  • the process according to the invention may also be used to prepare useful mixtures of ethers by starting with a mixture of alcohols.
  • These mixtures of ethers may be useful as anti-knock agents for motor fuels, solvents, heat transfer oils, polymers or chromatographic supports.
  • the likely product is a polyether, although if the alcohol has a number of hydroxy groups attached to a central core it is possible to produce dendrimers.
  • diols it is possible to produce polyethers, which may be straight-chain or cyclic. It is also possible to react a diol to produce an intramolecular ring closure, thereby producing a cyclic ether.
  • the process according to the invention may be operated in batch or continuous mode.
  • the alcohol and the organic halide are added to a reaction vessel and, if necessary, the mixture is heated to the desired temperature for an appropriate time to produce the desired ether or ether compositions.
  • the water produced by the process may optionally be removed during the reaction by known methods. As the concentration of water increases during progress of the reaction the hydrogen halide could be removed from the reaction system by dissolution in the water. As mentioned above the reaction rate could be maintained by the progressive addition of organic halide.
  • the alcohol may be added continuously to an excess of organic halide, heated if necessary, the ether and water formed being removed by distillation.
  • the mixed vapours may be fractionated and the ether and the water separately condensed.
  • the ether may be sufficiently insoluble in water for separation to occur after condensation of the product vapours without fractionation.
  • ether product for example to remove traces of RX or HX or to dry the ether. This may be done by standard methods.
  • the temperature is not critical for the operation of the process, the reaction rates will increase in the usual manner as temperature increases.
  • the preferred temperature for the process is in the range of 40° to 400°C.
  • pressure is not a significant factor for the operation of the process, although the increased operating temperature possible by using elevated pressures may be an advantage in some cases.
  • the process according to the invention provides a method for the synthesis of ethers, and esters from alcohols which avoids the use of strong acid (eg. concentrated sulfuric acid) catalysts and dehydrating agents of the Williamson process and the prior art processes, with the attendant cost and effluent disposal problems being also avoided.
  • strong acid eg. concentrated sulfuric acid
  • reaction mixtures also contained the corresponding cyclopropylmethyl halides and when water accumulated in the mixture, acid- catalysed decomposition of the starting material and product occurred.
  • This example indicates that CHI 3 and CBr 4 decompose slowly in the presence of alcohol to form HI and HBr, which then catalyse the etherification in accordance with
  • H 1 nmr confirmed the presence of ether linkages in the polymer (H 1 adjacent to ether linkage, gives chemical shift of 3.40 ppm, H 1 adjacent to hydroxy group, gives chemical shift of 3.62 ppm) with the ratio of hydroxy groups to ether linkages ca. 1:7.5.
  • a pressure vessel was charged with 0.5 g of n-butanol and heated at 200 °C for 2 hours.
  • a reaction mixture comprising 1-butanol (5.0 g, 67.5 mmol), 1-bromobutane (0.961 g, 7.0 mmol) and lithium bromide (0.589 g, 6.8 mmol) was prepared. Two pressure vessels were charged with 0.5 g of the reaction mixture each, then heated for 2 hours at 200 °C.
  • a reaction mixture was prepared consisting of; n-butanol (1.0 g, 13.5 mmol), 1-bromobutane (0.185 g,1.35 mmol), cesium bromide (0.287 g, 1.35 mmol) and water (0.349 g, 19.4 mmol). Two pressure vessels were charged with 0.5 g of the reaction mixture each, then heated to 200°C.
  • a reaction mixture was prepared consisting of; n-butanol (1.0 g, 13.5 mmol), 48% aqueous hydrobromic acid (0.221 g,1.3 mmol) and lithium bromide (0.117 g, 1.35 mmol).
  • Two pressure vessels were charged with 0.5 g of the reaction mixture each, then heated to 200 °C.
  • GC analysis showed conversion of 39% after 1 hour and 47% after 2 hours of alcohol to 1,1 '- oxybisbutane. There was 8% of 1-bromobutane detected after 1 hour and 8% after 2 hours of the process.
  • a reaction mixture was prepared consisting of; 2-butanol (1.0 g, 13.5 mmol) and 2-bromobutane 10 (0.196 g, 1.4 mmol).
  • a pressure vessel was charged with 0.59 g of the reaction mixture and heated to 150°C. After 5 hours, GC analysis showed 8% conversion of alcohol to 2,2'- oxybisbutane with an unchanged level of 2-bromobutane.
  • EIMS [m/z (rel. int.)]; 130(M + , 1), 115(1), 101(9), 83(3), 59(21), 57(39), 45(100).
  • a reaction mixture was prepared consisting of; 2-butanol (1.0 g, 13.5 mmol), 2-bromobutane (0.181 g, 1.3 mmol) and lithium bromide (0.115 g, 1.3 mmol).
  • a pressure vessel was charged with 0.426 g of the reaction mixture and heated to 150°C. After 5 hours, GC analysis showed 20 18%> conversion of alcohol to 2,2 '-oxybisbutane.
  • a reaction mixture was prepared consisting of; 2-butanol (13.5 mmol) and 2-bromobutane (1.35 mmol).
  • a pressure vessel was charged with 0.5 g of the reaction mixture, placed in an oven at 25 130°C. After 24 hours, 21% of 2-butanol was converted to di-2 -butyl ether and 2-bromobutane was present at approximately its starting concentration.
  • a reaction mixture of 2-phenethanol (2.4 g, 20 mmol), (2-bromoethyl)benzene (0.37 g, 2 mmol), lithium bromide (0.17 g, 2 mmol) and 1 drop of water (for dissolving LiBr) was prepared.
  • Pressure vessels were charged with 0.3 g of the reaction mixture and heated at 220 °C for 2, 4, or 24 hours. Conversion of alcohol to di-2-phenyl ethyl ether was estimated at 59, 68, and 89% respectively.
  • a reaction mixture of 2-phenethanol (2.4 g, 20 mmol), lithium bromide (0.17 g, 2 mmol) and 2 drops of water (for dissolving LiBr) was prepared. Pressure vessels were charged with 0.3 g of the reaction mixture then placed in an oven at 220 °C for 2, 4, or 24 hours. Conversion of alcohol to di-2-phenyl ethyl ether was estimated at 6, 12, and 41% respectively and (1%>) of (2-bromoethyl)benzene was formed .
  • a reaction mixture of phenol (1.88g, 20 mmol) and n-butanol (1.48 g, 20 mmol) was prepared. Pressure vessels were charged with 0.3 g of the reaction mixture then heated at 200 °C for 2, 4, or 24 hours. After 24 hours only traces of di-n butyl ether and n- butoxybenzene were observed.
  • a reaction mixture was prepared consisting of; phenol (10 mmol), n-butanol (10 mmol), 1- bromobutane (1 mmol), and water (10 mmol).
  • a pressure vessel was charged with 0.4 g of the reaction mixture and heated at 200 °C. After 1 hour, di-n-butyl ether was formed predominantly. After 20 hours di-n-butyl ether (20%) and butyl phenyl ether (16%) had formed.
  • the EIMS of the latter product at 70eV [m/z (rel. int)]; 150(M + ,18), 135(1), 121(1), 94(100), 79(11), 66(10), 51(7), 41(11).
  • a reaction mixture was prepared consisting of; 2,4,6-trimethylbenzoic acid (0.25 g, 1.5 mmol), 2-propanol (0.45 g, 7.5 mmol) and 2-bromopropane (0.044 g, 0.36 mmol).
  • a 5 pressure tube was loaded with approximately 0.2 g of the reaction mixture and heated at 150°C for 18 hours.
  • GC analysis 14% conversion of the acid to the ester.
  • EIMS [m/z, (rel. int.)]; 206(M + , 18), 147(86), 146(100), 119(30), 91(32), 77(18), 41(23).
  • a reaction mixture was prepared consisting of; 2,4,6-trimethylbenzoic acid (0.2 g, 1.2 mmol), 2-propanol (0.38 g, 3.05 mmol), 2-bromopropane (0.035 g, 0.12 mmol) and lithium bromide (0.042 g, 0.24 mmol).
  • Pressure tubes were each loaded with approximately 0.2 g of the reaction mixture and heated at 150°C for 1 hour and 18 hours.
  • GC analysis respectively 5 showed 10% and 37% conversion of the acid to the ester.
  • a reaction mixture was prepared consisting of; 2,4,6-trimethylbenzoic acid (0.25 g, 1.5 0 mmol), 2-bromopropane (0.92 g, 7.5 mmol) and lithium bromide (0.026 g, 0.3 mmol). Pressure tubes were loaded with approximately 0.2 g of the reaction mixture and heated at 150°C for 4 hours. GC analysis showed 39% conversion of the acid to the ester.
  • Benzoic acid (8.24 g, 68 mmol), n-butanol (5.0 g, 68 mmol) and n-butyl bromide (1.1 g, 8 mmol) were stirred at 120° C butyl alcohol to n-butyl benzoate.
  • EIMS at 70eV [m/z (rel. int.)]; 178(M + , 1), 123(64), 122(17), 106(8), 105(100),79(11), 77(63), 56(23), 51(34), 50(12), 41(17).

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Abstract

L'invention concerne un procédé pour la synthèse d'éthers ou d'esters, consistant à faire réagir un alcool ou un acide carboxylique avec un halogénure organique, de sorte qu'un éther ou un ester soit produit respectivement ainsi qu'un halogénure d'hydrogène. On génère encore de l'halogénure organique in situ pour la production d'éther ou d'ester par la mise en réaction de l'halogénure d'hydrogène avec un alcool.
PCT/AU1999/000364 1998-05-15 1999-05-14 Procede de preparation d'ethers et d'esters Ceased WO1999059947A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006104884A3 (fr) * 2005-03-28 2007-03-29 Shell Oil Co Conversion d'halogenures d'alkyle en alcoxylates d'alcool
US7498372B2 (en) 2005-11-29 2009-03-03 Ferro Corporation Ether-ester plasticizers
US8115039B2 (en) 2005-03-28 2012-02-14 Shell Oil Company Catalytic distillation process for primary haloalkanes

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613682A (en) * 1985-08-19 1986-09-23 The Dow Chemical Company Ether synthesis
JPS62149639A (ja) * 1985-12-24 1987-07-03 Koei Chem Co Ltd ポリオールの部分エーテル類の製造方法
JPS63152341A (ja) * 1986-08-21 1988-06-24 Tokuyama Soda Co Ltd アシルオキシハロゲン化炭化水素の製造方法
JPH0253748A (ja) * 1988-08-12 1990-02-22 Wakayama Pref Gov エーテル類の製造方法
JPH03220172A (ja) * 1990-01-25 1991-09-27 Tokuyama Soda Co Ltd チオカルボン酸エステル化合物及びその製造方法
JPH04342540A (ja) * 1991-05-20 1992-11-30 Daiso Co Ltd エーテル類の製法
US5260475A (en) * 1990-06-22 1993-11-09 Rhone-Poulenc Chimie Esterification of hydroxybenzoic acids
JPH09132563A (ja) * 1995-11-09 1997-05-20 Mitsui Toatsu Chem Inc 含硫（メタ）アクリレート化合物およびその用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4613682A (en) * 1985-08-19 1986-09-23 The Dow Chemical Company Ether synthesis
JPS62149639A (ja) * 1985-12-24 1987-07-03 Koei Chem Co Ltd ポリオールの部分エーテル類の製造方法
JPS63152341A (ja) * 1986-08-21 1988-06-24 Tokuyama Soda Co Ltd アシルオキシハロゲン化炭化水素の製造方法
JPH0253748A (ja) * 1988-08-12 1990-02-22 Wakayama Pref Gov エーテル類の製造方法
JPH03220172A (ja) * 1990-01-25 1991-09-27 Tokuyama Soda Co Ltd チオカルボン酸エステル化合物及びその製造方法
US5260475A (en) * 1990-06-22 1993-11-09 Rhone-Poulenc Chimie Esterification of hydroxybenzoic acids
JPH04342540A (ja) * 1991-05-20 1992-11-30 Daiso Co Ltd エーテル類の製法
JPH09132563A (ja) * 1995-11-09 1997-05-20 Mitsui Toatsu Chem Inc 含硫（メタ）アクリレート化合物およびその用途

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; Class A25, AN 1987-224848 *
DATABASE WPI Derwent World Patents Index; Class A25, AN 1993-014056 *
DATABASE WPI Derwent World Patents Index; Class A41, AN 1990-103176 *
DATABASE WPI Derwent World Patents Index; Class A41, AN 1997-328466 *
DATABASE WPI Derwent World Patents Index; Class B05, AN 1988-216588 *
DATABASE WPI Derwent World Patents Index; Class G06, AN 1991-329216 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006104884A3 (fr) * 2005-03-28 2007-03-29 Shell Oil Co Conversion d'halogenures d'alkyle en alcoxylates d'alcool
US8115039B2 (en) 2005-03-28 2012-02-14 Shell Oil Company Catalytic distillation process for primary haloalkanes
US7498372B2 (en) 2005-11-29 2009-03-03 Ferro Corporation Ether-ester plasticizers

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