WO2005014565A2 - Cis-3,5-bisubstitue-dihydro-furan-2-ones ainsi que preparation et utilisation de ceux-ci - Google Patents

Cis-3,5-bisubstitue-dihydro-furan-2-ones ainsi que preparation et utilisation de ceux-ci Download PDF

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WO2005014565A2
WO2005014565A2 PCT/US2004/025668 US2004025668W WO2005014565A2 WO 2005014565 A2 WO2005014565 A2 WO 2005014565A2 US 2004025668 W US2004025668 W US 2004025668W WO 2005014565 A2 WO2005014565 A2 WO 2005014565A2
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formula
compound
product
furan
methyl
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PCT/US2004/025668
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WO2005014565A3 (fr
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Paul Joseph Fagan
Charles J. Brandenburg
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E.I. Dupont De Nemours And Company
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    • 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
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms

Definitions

  • the present invention relates to the novel preparation of pure cis- 3,5-disubstituted-dihydro-furan-2-ones and also relates to novel compositions of matter, those being the chemically pure and enantiomerically pure e/s-isomers of 3,5-disubstituted-dihydro-furan-2- ones and the use of said compositions as flavors or fragrances.
  • Enantiomerically pure cis-(3R,5S)-3,5- dimethyl-dihydro-furan-2-one has been prepared by reaction of (S)- propylene oxide with the anion of the diester of malonic acid producing (5S -methyl-butyrolactone, which was followed by formylation of the 3- position, reduction to the (S5)-3-(hydroxymethyl)- 5-methyl-dihydro-furan- 2-one, dehydration to the (S5)-3-methylene-5-methyl-dihydro-furan-2-one, and hydrogenation over 10% palladium on carbon to yield pure cis- (3fi,5S)-3,5-dimethyl-dihydro-furan-2-one (White, J.
  • compositions c/s-(3S,5S)-3-methyl-5-phenyl- dihydro-furan-2-one has been prepared in enantiomerically pure form from an expensive organometallic iron reagent (Davies, S. G.; Polywka, R.; Warner, P. Tetrahedron, Vol. 46, pp 4847-4856 (1990)).
  • organometallic iron reagent Dioxides, S. G.; Polywka, R.; Warner, P. Tetrahedron, Vol. 46, pp 4847-4856 (1990).
  • These former compositions are the only enantiomerically pure c/s-3- (dihydrocarbylmethano)-5-(hydrocarbyl)-dihydro-furan-2-ones described in the art.
  • the present invention provides for new enantiomerically pure compositions c/s-(3S,5S)-3-(dihydrocarbylmethano)-5-(hydrocarbyl)- dihydro-furan-2-ones, c/ ' s-(3R,5r?) ⁇ 3-(dihydrocarbylmethano)-5- (hydrocarbyl)-dihydro-furan-2-ones, cis-(3S,5R)-3- (dihydrocarbylmethano)-5-(hydrocarbyl)-dihydro-furan-2-ones, and cis- (3R,5S)-3-(dihydrocarbylmethano)-5-(hydrocarbyl)-dihydro-furan-2-ones.
  • R-i, and the group at position 3 of the lactone ring have a cis orientation with respect to each other;
  • R 1 is selected from linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl or substituted hydrocarbyl radicals;
  • R 2 and R 3 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl or substituted hydrocarbyl radicals.
  • the novel process is described by the sequence of steps in Scheme 1 , and comprises the steps of: (a) contacting a lactone of formula II with an oxalic acid diester in the presence of a base and a solvent to form an intermediate mixture comprising a compound of formula III and isolating the compound of formula III from the intermediate mixture; (b) treating the isolated compound of formula III with an aldehyde or a ketone and isolating a compound of formula IV from the product mixture; and (c) hydrogenating the compound of formula IV in the presence of a catalyst and optionally a solvent and isolating a pure compound of formula I; wherein, R is a hydrocarbyl or substituted hydrocarbyl group, X + is a cation, and wherein the pure compound is defined as greater than 95 percent pure by gas chromatographic analysis.
  • the product of the process, formula I is a racemic mixture of the optical isomers.
  • the present invention relates to novel compositions of matter represented by formula 1 wherein Ri, and the group at position 3 of the lactone ring (containing R 2 and R 3 ) have a cis orientation with respect to each other; Ri comprises a group selected from the groups consisting of linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups; R 2) and R 3 are independently selected from the groups consisting of hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups excluding compounds wherein R 2 and R 3 are both H, when Ri is methyl or phenyl; and said composition contains a molar ratio of cis:trans stereoisomers greater than 49:1 ; and said compositions have greater than 95 percent enantiomeric purity, being the (3S,5S), (3R,5R), (3S,5R), or (3R,5S) optically pure isomers.
  • novel compositions of the present invention may be prepared to greater than 95 percent purity by gas chromatographic (GC) analysis.
  • the present invention relates to an additional process to produce the optically pure, (3S,5S), (3R,5R), (3S,5R), or (3R,5S), cis isomer of compounds of formula I, comprising the same steps as the previously described process, with the exception that the starting compound Formula II is either the pure (R) or (S) stereoisomer.
  • the present invention relates to methods to improve, enhance, or modify the flavor or fragrance of a product formulation; methods to improve or modify the rheology of an oil, hydrocarbon, petroleum product; methods of formulating a cosmetic product; and methods of formulating a liquid detergent or cleaning product.
  • Figure 1 Structure of c/s-3-octyl-5-methyl-dihydro-furan-2-one as determined by X-ray crystallography analysis.
  • R-i, and the group at position 3 of the lactone ring have a cis orientation with respect to each other;
  • Ri comprises a group selected from the groups consisting of linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups;
  • R 2 , and R 3 are independently selected from the groups consisting of hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups; and said composition contains a molar ratio of cis:trans stereoisomers greater than 49:1.
  • the novel process is described by the sequence of steps in Scheme 1 , and comprises the steps of: (a) contacting a lactone of formula II with an oxalic acid diester in the presence of a base and a solvent to form an intermediate mixture comprising a compound of formula III and isolating the compound of formula III from the intermediate mixture; (b) treating the isolated compound of formula III with an aldehyde or ketone, to form a second intermediate mixture comprising a compound of formula IV and isolating the compound of formula IV from the second intermediate mixture; and (c) hydrogenating the compound of formula IV in the presence of a catalyst and optionally a solvent to form a product mixture comprising a compound of formula I and isolating a pure compound of formula I from the product mixture;
  • R is a hydrocarbyl or substituted hydrocarbyl group
  • X + is a cation.
  • the product of the process, formula I is a racemic mixture of the optical isomers.
  • pure compound of formula I is meant that the purity of the isolated compound is at least about 95 percent as determined by gas chromatographic analysis.
  • compositions of matter comprising compounds represented by formula 1 wherein, R-i and the group at position 3 of the lactone ring (containing R 2 and R 3 ) have a cis orientation with respect to each other; Ri is selected from linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl or substituted hydrocarbyl radicals; R 2 and R 3 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals excluding compounds wherein R 2 and R 3 are both H, when Ri is methyl or phenyl; said composition contains a molar ratio of the cis to trans stereoisomers of greater than 49:1 ; and said composition is greater than 95 percent enantiomerically pure, being the (3S,5S), (3R,5R), (3S,5R), or (3R,5S) optically pure isomer.
  • hydrocarbyl group is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
  • substituted hydrocarbyl herein is meant a hydrocarbyl group, which contains one or more substituent groups, which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are heteroaromatic rings.
  • composition of matter comprising the compounds represented by formula I may be prepared to possess an overall purity of greater than 95 percent as determined by gas chromatographic analysis.
  • the percent purity is calculated from the chromatogram as an area percent of the main component peak relative to the summed area for all peaks in the chromatogram.
  • composition of formula I wherein, R-i, and the group at position 3 of the lactone ring (containing R 2 and R 3 ) have a cis orientation with respect to each other;
  • Ri is selected from linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals;
  • R 2 and R 3 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals excluding compounds wherein R 2 and R 3 are both H, when Ri is methyl or phenyl; and in addition, wherein said composition of formula I comprises greater than 96 percent optically purity, being the (3S,5S), (3R,5R), (3S,5R), or (3R,5S) optically pure isomers.
  • the process is described by the sequence of steps in Scheme 2, wherein the starting gamma-methyl-gamma-butyrolactone (Formula II) is greater than 96% enantiomeric excess the (R) or (S) stereoisomer.
  • the novel process yields a single stereoisomer with the cis orientation of R-i and the group at position 3 of the lactone ring (containing R 2 and R 3 ) rather than a mixture of two possible stereoisomers, and further affords a route to the optically pure isomer, being the (3S,5S), (3R,5R), (3S,5R), or (3R,5S) optically pure isomers that are not known.
  • the process for preparing the enantiomerically pure composition of formula I comprises the steps: (a) contacting an optically pure stereoisomer of a lactone of formula II with an oxalic acid diester in the presence of a base and a solvent to form an intermediate mixture comprising an optically pure compound of formula III and isolating the optically pure compound of formula III from the intermediate mixture; (b) treating the isolated optically pure compound of formula III with an aldehyde or ketone, to form a second intermediate mixture and isolating an optically pure compound of formula IV from the second intermediate mixture; and (c) hydrogenating the optically pure compound of formula IV in the presence of a catalyst and optionally a solvent to form a product mixture and isolating an enantiomerically pure compound of formula I from the product mixture.
  • Lactones of formula II from Scheme 1 are commercially available from Aldrich, St. Louis, MO.
  • Lactones of formula II from Scheme 2 which are the pure (R) or (S) isomer may be prepared from a malonic acid diester by reaction with a base at elevated temperature to form the malonic acid diester enolate salt; and then reacting the salt with either an (R) or (S) epoxide to form the lactone.
  • the details of the preparation are given in Hedenstroem, Erik; Hoegberg, Hans-Erik; Wassgren, Ann-Britt; Bergstroem, Gunnar; Loefqvist, Jan; Tetrahedron; 48; 1992; pp. 3139-3146.
  • the two processes of the present invention may be run under the same conditions, the detailed conditions are provided below, while the starting compound is different; one starting compound being a racemic mixture and the other starting compound being a pure (R) or (S) stereoisomer.
  • the first step of the processes is conducted at a temperature of at least about 25°C and a pressure less than or equal to 2000 psi, preferably about 75°C and about atmospheric pressure.
  • the reaction may optionally run at higher temperatures, at about 100°C to about 120°C under higher pressures of about 700 psi.
  • the reaction may optionally employ an organic solvent and use a phase transfer catalyst.
  • the first step of the process can employ any number of solvents or combinations thereof; these include but are not limited to methanol, ethanol and isopropanol.
  • the R group of the oxalic acid diester of the first step in the processes may be a hydrocarbyl or substituted hydrocarbyl group, preferably, a methyl or ethyl group.
  • the base of the first step of the processes may be selected from the group consisting of metal alkoxides, metal oxides, hydroxides, carbonates and phosphates.
  • the metal alkoxides, oxides, hydroxides, carbonates and phosphates employed herein may be used as solutions, powders, granules, or other particulate forms, or may be supported on an essentially inert support as is common in the art of catalysis.
  • Representative bases include but are not limited to sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium n-butoxide, potassium carbonate, cesium carbonate, sodium carbonate, barium carbonate, sodium hydrogen carbonate, magnesium oxide, barium oxide, barium hydroxide, lanthanum oxide, potassium hydroxide, cadmium oxide, rubidium oxide, lithium hydroxide, strontium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, potassium phosphate and mixtures thereof.
  • the second step of the processes of the present invention is conducted at a temperature of at least about 0°C and a pressure less than or equal to 2000 psi, preferably about 10°C and about atmospheric pressure.
  • the second step of the processes can employ any number of solvents or combinations thereof, these include but are not limited to water, toluene, xylenes, hexanes, ethyl acetate, chlorobenzene, 1 ,2- dichlorobenzene, acetonitrile, methylene chloride, acetone, methyl ethyl ketone, dimethylacetamide, chloroform, chlorobutane, and benzene.
  • solvents or combinations thereof include but are not limited to water, toluene, xylenes, hexanes, ethyl acetate, chlorobenzene, 1 ,2- dichlorobenzene, acetonitrile, methylene chloride, acetone, methyl ethyl ketone, dimethylacetamide, chloroform, chlorobutane, and benzene.
  • the aldehyde or ketone of the second step of the novel processes may be represented by the formula R 2 COR 3 , wherein R 2 and R 3 are independently selected from hydrogen and linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl or substituted hydrocarbyl radicals.
  • the hydrocarbyl or substituted hydrocarbyl groups of R 2 and/or R 3 may contain from one to 30 carbon atoms.
  • the third step of the processes, hydrogenation may be conducted at a temperature of at least about 20°C up to about 200°C and a pressure less than or equal to 2000 psi, preferably about atmospheric pressure.
  • the contact time for the hydrogenation step may be from about 15 minutes to about 12 hours.
  • the hydrogenation catalyst of the third step of the processes can include one or more metals selected from Group 8 elements from the Periodic Table of Elements, more preferably, the group consisting of iridium, nickel, palladium, platinum, rhenium, rhodium and ruthenium.
  • the metal catalyst can optionally be supported on a catalyst support. The metal can be deposited on the support using any method known in the art.
  • the catalyst has about 1 % to about 10% by weight of metal present on the support.
  • the catalyst support can be any solid, inert substance including, but not limited to, metal oxides such as silica, alumina, and titania, and carbons.
  • the catalyst support can be in the form of powder, granules, pellets, or the like.
  • the metal catalyst can also be a homogenous hydrogenation catalyst that dissolves in a solution or the substance to be hydrogenated.
  • the homogeneous catalyst may consist of a combination of ligands and metal ions; in the case of charged species; counter ions may also be present. Isolation of the intermediate compounds or products of the present inventive processes may be accomplished by techniques common to the art.
  • the isolation techniques include but are not limited to filtration, distillation (including vacuum distillation and steam distillation), melt crystallization, solvent extraction, and sublimation.
  • filtration the desired product or intermediate may be the filtrate or the solid.
  • Vacuum distillation is the preferred method of distillation, as it decreases the amount of by-products.
  • the present invention further relates to methods to improve, enhance, or modify the flavor or fragrance of a product formulation comprising adding an effective amount of the compositions of the present invention to the product formulation.
  • the compositions of the present invention may be useful in both fine and functional perfumery.
  • compositions are of use as a perfuming ingredient include but are not limited to perfumes and colognes, soaps, shower and bath gels, shampoos and other hair-care products, body or air deodorants, detergents or fabric softeners or other household products.
  • the compositions of the present invention may be useful for the flavor industry.
  • the compositions can be used to flavor various articles including, but not limited to, foodstuffs, beverages, chewing gums, toothpaste or pharmaceutical preparations.
  • the present invention further relates to methods for modifying the rheology of an oil, hydrocarbon, petroleum or petroleum product, comprising adding an effective amount of the lactone compositions of the present invention to the oil, hydrocarbon, petroleum or petroleum product.
  • the present invention further relates to methods of formulating a cosmetic product comprising adding an effective amount of the lactone compositions of the present invention to the cosmetic product.
  • the present invention further relates to methods of formulating a liquid detergent or cleaning product comprising adding an effective amount of the lactone compositions of the present invention to the liquid detergent or cleaning product.
  • a 100 mL flask was charged with 2.00 g of 3-hexylidene-5-methyl-dihydro-furan-2-one (mixture of E and Z stereoisomers), 0.210 g of 10% palladium on carbon catalyst (Aldrich Chemical Company), 40 mL of denatured ethanol, and 10 mL of methanol.
  • the flask was attached to a high vacuum line via an adapter, and the apparatus was degassed. An atmosphere of dihydrogen gas was admitted to the flask, and gas uptake was monitored using a mercury manometer connected to the vacuum line. After 12 hours, the hydrogen gas and solvents were removed in vacuo.
  • the solution containing the product was filtered from the catalyst, and solvents were removed in vacuo yielding crude product that by GC analysis indicated a >99% conversion and >97% yield to the desired product.
  • Table 4 Comparison of selected inter-proton distances in cis- and trans - 3-hexyl-5-methyl-dihydro-furan-2-one with distances derived from cross- relaxation rates from NOE NMR experiments. Units are in Angstroms (10 " 8 cm). The NOE distances are based on a calculated D1 - D2 distance of 1.79 A.
  • the compound c/s-3-heptyl-5-methyl-dihydro-furan-2-one was prepared by the procedure of Example 11 using 1.9 g of (E,Z)-3- heptylidene-5-methyl-dihydro-furan-2-one (prepared by the procedure of Example 6).
  • the crude product was isolated by sublimation yielding crude product that by GC analysis indicated a >99% conversion and >97% yield to the desired product. After sublimation, 0.399 g of a colorless solid was obtained (21 % yield; some loss of crude product was observed owing to incomplete transfer of material from vessel to vessel).
  • GC purity 99.7%.
  • the compound c/ ' s-3-octyl-5-methyl-dihydro-furan-2-one was prepared by the procedure of Example 11 using 2.0 g of (E,Z)-3- octylidene-5-methyl-dihydro-furan-2-one (prepared by the procedure of Example 7).
  • the crude product was obtained with 99% conversion and in .97% yield.
  • the product was isolated by sublimation yielding 1.55 g of a colorless solid (77% yield; some loss of crude product was observed owing to incomplete transfer of material from vessel to vessel)..
  • GC purity 99%.
  • Figure 1 describes the structure of c/s-3-octyl-5-methyl-dihydro- furan-2-one as determined by X-ray crystallography analysis. Structure demonstrates the cis orientation of the octyl and methyl groups on the lactone ring. The asymmetric unit contains one molecule as shown with thermal ellipsoids drawn to the 50% probability level.
  • EXAMPLE 20 Preparation of c/s-3-cyclohexylmethyl-5-methyl-dihvdro-furan-2-one
  • a 100 mL round bottomed flask equipped with a Teflon ® -coated magnetic stirring bar was charged with 1.041 g of (E,Z)-3-cyclohexylmethylidene-5-methyl-dihydro-furan-2-one (prepared as in Example 19), 0.105 g of 10% palladium on carbon catalyst (Aldrich Chemical Company), 20.0 mL of denatured ethanol, and 5 ml of methanol. This was placed on a high vacuum line and degassed.
  • the (5S)-3-methyloxalyl-5-methyl- dihydro-2-furanone sodium salt is prepared from this compound according to Procedure 1 using (5S)-5-methyl-dihydro-furan-2-one in place of gamma-methyl-gamma-butyrolactone.
  • the (5S)-c/s-3-hexylidene-5- methyI-dihydro-furan-2-one is prepared from this salt according to the procedure of Example 5 using this salt in place of methyloxalyl-gamma- methyl-ga ma-butyrolactone sodium salt .
  • the compound (5f?)-5-methyl-dihydro-furan-2-one is prepared by the procedure reported in the literature using (R)-propylene oxide: Hedenstroem, Erik; Hoegberg, Hans-Erik; Wassgren, Ann-Britt; Bergstroem, Gunnar; Loefqvist, Jan; Tetrahedron; 48; 1992; pp. 3139- 3146.
  • the (5R)-3-methyloxalyl-5-methyl- // 7y ro-2-ft/rano/?e sodium salt is prepared from this compound according to Procedure 1 using (5R)-5- methyl-dihydro-furan-2-one in place of gamma-methyl-gamma- butyrolactone.
  • the (5R -c/s-3-hexylidene-5-methyl-dihydro-furan-2-one is prepared from this salt according to the procedure of Example 5 using this salt in place of methyloxalyl-gamma-methyl-gamma-butyrolactone sodium salt .

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Abstract

L'invention concerne un procédé amélioré de préparation de cis-3-dihydrocarbylméthano-5-hydrocarbyldihydro-furan-2-ones. L'invention concerne également de nouvelles compositions comprenant des cis-3-dihydrocarbylméthano-5-hydrocarbyldihydro-furan-2-ones purs au niveau énantiomérique, étant les isomères purs au niveau optique (3S,5S), (3R,5R), (3S,5R), ou (3R,5S), ainsi qu'un nouveau procédé plus économique de préparation de ces isomères purs au niveau optique.
PCT/US2004/025668 2003-08-07 2004-08-06 Cis-3,5-bisubstitue-dihydro-furan-2-ones ainsi que preparation et utilisation de ceux-ci WO2005014565A2 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299345A (zh) * 2018-02-09 2018-07-20 东北制药集团股份有限公司 一种α-乙酰-γ-丁内酯的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4980342A (en) * 1989-02-24 1990-12-25 Henkel Corporation Process for the preparation of α-alkyl lactones
US20020143195A1 (en) * 2000-12-22 2002-10-03 Puts Rutger D. Process for the preparation of a-methylenelactones and a-substituted hydrocarbylidene lactones

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4980342A (en) * 1989-02-24 1990-12-25 Henkel Corporation Process for the preparation of α-alkyl lactones
US20020143195A1 (en) * 2000-12-22 2002-10-03 Puts Rutger D. Process for the preparation of a-methylenelactones and a-substituted hydrocarbylidene lactones

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
BARRETT A G M ET AL: "Total synthesis of (+)-milbemycin beta3" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 51, no. 25, 12 December 1986 (1986-12-12), pages 4840-4856, XP002273308 ISSN: 0022-3263 *
CLARK STILL W ET AL: "Remote Asymmetric Induction. A Stereoselective Approach to Acyclic Diols via Cyclic Hydroboration" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 102, 1980, pages 7385-7387, XP002182870 ISSN: 0002-7863 *
DATABASE CROSSFIRE BEILSTEIN BEILSTEIN INSTITUT ZUR FOERDERUNG DER WISSENSCHAFTEN, FRANKFURT AM MAIN, DE; Reaction ID 3818487 1988, XP002316016 & LEHMANN J ET AL: ARCH. PHARMAZIE, vol. 320, no. 1, 1987, pages 22-29, WEINHEIM, GERMANY *
GIERASCH T M ET AL: "Extensively Stereodiversified Scaffolds for use in Diversity-Oriented Library Synthesis" ORGANIC LETTERS, ACS, WASHINGTON, DC, US, vol. 5, no. 5, 2 May 2003 (2003-05-02), pages 621-624, XP002316011 ISSN: 1523-7060 *
ISHIHARA M ET AL: "The Absolute Configuration of Marmelo Lactones" AGRIC. BIOL. CHEM., vol. 47, no. 9, 1983, pages 2121-2122, XP009043342 *
KEMPF D J: "Dipeptide Analogues: Versatile Synthesis of the Hydroxyethyene Isostere" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 51, no. 21, 1986, pages 3921-3926, XP002316013 ISSN: 0022-3263 *
MCWILLIAMS J C ET AL: "Tandem Asymmetric Transformations" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 118, 1996, pages 11970-11971, XP002316014 ISSN: 0002-7863 *
NAKAMURA E ET AL: "Trichlorotitanium and Alkoxytitanium Homoenolates. Preparation, Characterization, and Utilization for Organic Synthesis" JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 108, 1986, pages 3745-3755, XP002316015 ISSN: 0002-7863 *
REISSIG H U ET AL: "Ester Groups as Effective Ligands in Chelate-Controlled Additions of Cuprates and Grignard Reagents to Chiral beta-Formyl Esters" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 58, 1993, pages 6280-6285, XP002316012 ISSN: 0022-3263 *
SUNG H K ET AL: "An asymmetric synthesis of a key intermediate to 1beta-methylcarbapenem antibiotics" TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 36, no. 37, 11 September 1995 (1995-09-11), pages 6713-6716, XP004027323 ISSN: 0040-4039 *
URABE H ET AL: "Reagent-controlled Stereoselection in Radical Addition to alpha-Methylenebutyrolactones" JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, CHEMICAL SOCIETY. LETCHWORTH, GB, 1995, pages 1043-1044, XP009043357 ISSN: 0022-4936 *

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CN108299345A (zh) * 2018-02-09 2018-07-20 东北制药集团股份有限公司 一种α-乙酰-γ-丁内酯的制备方法

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