WO2009131966A1 - Methods for preparing aldehydes by self-aldol condensation - Google Patents
Methods for preparing aldehydes by self-aldol condensation Download PDFInfo
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- WO2009131966A1 WO2009131966A1 PCT/US2009/041187 US2009041187W WO2009131966A1 WO 2009131966 A1 WO2009131966 A1 WO 2009131966A1 US 2009041187 W US2009041187 W US 2009041187W WO 2009131966 A1 WO2009131966 A1 WO 2009131966A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
Definitions
- the disclosure relates generally to methods for preparing self-aldol condensation products of ⁇ , ⁇ -unsaturated aldehydes having at least two ⁇ -hydrogens. More specifically, the disclosure describes methods for preparing intermediates useful in the synthesis of flavoring and fragrance compounds from 3-methyl-2-butenal, also known as prenyl aldehyde.
- (2E)-5-methyl-2-(l-methylethenyl)-2,4-hexadienal also known as dehydrolavandulal, (1) is formed, as shown in the following formula:
- (2E,4E)-3,7-dimethyl-2,4,6-octatrienal also known as dehydrocitral, (2) is formed, as shown in the following formula:
- dehydrolavandulal (1) involves the addition of a costly reagent, 2- methyl-3-butyn-2-ol, to prenyl aldehyde under acidic conditions. Subsequent loss of water and rearrangement yields dehydrolavandulal (1), as shown in Scheme 1 (see Fisher et. al., DE 2,212,948).
- the present disclosure provides cost-efficient methods for obtaining dehydrolavandulal (1) from prenyl aldehyde, via amine-catalyzed self-aldol condensation reactions.
- dehydrocitral (2) For previous routes to dehydrocitral (2) see, e.g., Traas, et. al., Tetrahedron Lett., 1977, 2129-2132.
- Another method of preparing dehydrocitral (2) involves the coupling of imine derivatives of prenyl aldehyde with prenyl aldehyde under weakly acidic conditions in the presence of a drying agent to obtain dehydrocitral (2), as shown in Scheme 2.
- the ⁇ -1,4- condensation product 4,6,6-trimethyl-l,3-cyclohexadiene-l-carboxaldehyde (3), was exclusively obtained by reaction of the lithium dienolate of prenyl aldehyde with prenyl aldehyde in tetrahydrofuran at -70 0 C to -20 0 C (Duhamel et al., Tetrahedron Lett., 32:4495 (1991)).
- the present disclosure provides methods for preparing ⁇ -l,2-addition products of prenyl aldehyde, as shown in Scheme 5, by use of a weak acid and a catalytic amount of a primary amine at temperatures of 10 0 C or greater.
- the disclosure also provides methods for preparing ⁇ -l,2-adducts of prenyl aldehyde, as shown in Scheme 4, at mild reaction temperatures of 10 0 C or greater, instead of -78 0 C, by use of a weak acid and a catalytic amount of a secondary or tertiary amine.
- Methods are provided for preparing self-aldol condensation products of 3-methyl-2- butenal.
- the method involves reacting 3-methyl-2-butenal with an amine and a weak acid at a temperature of at least 10 0 C, for example, from about 10 0 C to about 90 0 C.
- the addition product formed is the 1,2-condensation product.
- a primary amine is used, and an ⁇ - 1,2-condensation product of 3- methyl-2-butenal is formed.
- a secondary or tertiary amine is used, and a ⁇ - 1,2-condensation product of 3-methyl-2-butenal is formed.
- the weak acid can be a carboxylic acid, such as propionic acid, nonanoic acid, benzoic acid, and the like.
- the primary amine can be an alkyl amine, such as cyclohexylamine, and also can include alkyl primary amines having tertiary alkyl groups, such as tert-octylamine, tert-butylamine, and the like.
- the secondary amine can be a dialkylamine, such as morpholine, diisobutylamine, and the like.
- the tertiary amine can be a trialkylamine, such as diisopropylethylamine.
- the self-aldol reaction products prepared in accordance with the present disclosure provide intermediates for the synthesis of various compounds useful as flavors and fragrances.
- (2E)-5-methyl-2-(l-methylethenyl)-2,4-hexadienal (1) also known as dehydrolavandulal (1)
- Dehydrolavandulal (1) can be reduced to lavandulol or tetrahydrolavandulol, both of which have the scent of roses and are useful in artificial lavender oils and perfumery.
- (2E,4E)-3,7-dimethyl-2,4,6-octatrienal (2) also known as dehydrocitral (2), can be formed.
- Dehydrocitral (2) is the direct precursor to 2,6,6- trimethyl-l,3-cyclohexadiene-l-carboxaldehyde, also known as safranal.
- Safranal has the aroma of saffron, and is commercially valuable as a flavor and fragrance.
- the disclosed methods avoid the use of highly corrosive acids and bases. All synthetic steps of the disclosed methods involve relatively simple transformations and generate minimal waste. The disclosed methods avoid the use of alkyl halides or organometallic reagents. In addition, aqueous work-up procedures can be minimized or eliminated. DETAILED DESCRIPTION
- the present disclosure is directed to methods for preparing self-aldol addition products (adducts) of prenyl aldehyde.
- the self-aldol addition products can be prepared from a reaction mixture comprising prenyl aldehyde, an amine, and a weak acid.
- ⁇ -l,2-adducts and ⁇ -l,2-adducts of prenyl aldehyde can be formed selectively. It is theorized, but not relied upon herein, that the initially formed self-aldol addition products undergo dehydration in situ to yield the self-aldol condensation products.
- the reaction optionally can be heated to provide a reaction temperature above room temperature. Alternatively, the reaction can be cooled to provide a reaction temperature below room temperature and at least 10 0 C.
- the ⁇ -l,2-adduct can be obtained by the self- aldol reaction of prenyl aldehyde in the presence of a catalytic amount of a primary amine (H 2 NR 1 ) and a catalytic amount of a weak acid (RCO 2 H), wherein R is Ci to Cn alkyl, aryl, or substituted aryl, and R 1 is C 3 to Ci 2 alkyl or C 4 to Ci 2 cycloalkyl (Scheme 6).
- a catalytic amount of a primary amine H 2 NR 1
- RCO 2 H a catalytic amount of a weak acid
- the ⁇ -l,2-adduct can be obtained by the self-aldol reaction of prenyl aldehyde in the presence of a catalytic amount of a secondary amine, HNR R , or tertiary amine, NR R R , and a catalytic amount of a weak acid RCO 2 H, wherein R is C] to Cn alkyl, aryl, or substituted aryl, and R 2 , R 3 , and R 4 are independently selected from Ci to C 6 alkyl, eycloalkyl, aryl, or substituted aryl (Scheme 7).
- the secondary amine also can include cyclic and heterocyclic amines.
- Cyclic amines can include cyclic compounds comprising at least one nitrogen atom and 4 to 15 carbon atoms.
- Heterocyclic amines can include cyclic compounds comprising at least one nitrogen atom, 4 to 15 carbon atoms, and one to three oxygen and/or sulfur atoms.
- the tertiary amine can include, for example, N-substituted cyclic amines and N-substituted heterocyclic amines. Suitable N- substituents include Ci to C 3 alkyl groups.
- the reaction can be carried out at a temperature from about 10 0 C to about 90 0 C.
- the reaction can be heated to provide a reaction temperature above room temperature.
- Suitable reaction temperatures include, but are not limited to, temperatures of about 30 0 C to about 90 0 C, and about 40 0 C to about 70 0 C.
- the reaction also can be carried out at temperatures in excess of 90 0 C.
- the reaction can be carried out using pressure equipment.
- the reaction can be carried out at room temperature, or optionally can be cooled to temperatures below room temperature and at least 10 0 C.
- Suitable reaction temperatures can include about 10 0 C to about 30 0 C, for example, about 15 0 C to about 25 0 C, and about 20 0 C.
- the reaction mixture includes an organic solvent or a mixture of organic solvents.
- concentration of prenyl aldehyde in the solvent is determined by one skilled in the art, but typically is from about 0.5 M to about 2 M.
- organic solvents include, but are not limited to, linear and branched alkanes, such as pentanes, hexanes, heptanes, octanes, nonanes, and decanes; cycloalkanes, such as cyclopentane, cyclohexane, methylcyclohexane, and cycloheptane; aromatic hydrocarbons, such as toluene; ethers, such as diethyl ether, diisopropyl ether, tert-butyl ethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1 ,2-dimethoxyethane (glyme), and diethylene
- solvents also are encompassed by the present disclosure, and use of such mixtures often improves reaction selectivity and reduces formation of by-products.
- Representative solvent mixtures include, but are not limited to, mixtures of heptane and tert-amyl alcohol, mixtures of octane and tert-amyl alcohol, and mixtures of tetrahydrofuran and toluene.
- the reaction mixture includes an optional drying agent.
- drying agents include, but are not limited to, sodium sulfate and molecular sieves.
- the reaction mixture includes a weak acid, such as a weak organic acid or a weak inorganic acid.
- the weak acid is present in the reaction mixture in a catalytic amount.
- a catalytic amount of the weak acid means that the molar concentration of the weak acid is less than the molar concentration of prenyl aldehyde in the reaction mixture.
- the molar concentration of the weak acid can be about 0.5% to about 95% of the molar concentration of prenyl aldehyde, for example, about 1% to about 50%, about 5% to about 30%, or about 10% to about 25%.
- the molar concentration of the weak acid can be slightly greater than the molar concentration of prenyl aldehyde without adversely affecting the process, as shown by Example 2.
- the weak acid generally has a pK a relative to water of about 2 to about 6.
- the weak acid includes a carboxylic acid having a pK a relative to water of about 2 to about 6.
- the carboxylic acid includes an alkanoic acid represented by the formula RCO 2 H, wherein R is preferably Ci to Cn alkyl, more preferably Ci to C 1O alkyl, most preferably Ci to C 6 alkyl.
- Suitable examples of weak alkanoic acids for use in the present disclosure include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), and hexadecanoic acid (palmitic acid).
- the carboxylic acid also includes aromatic carboxylic acids and substituted aromatic carboxylic acids.
- An example of an aromatic carboxylic acid is benzoic acid.
- Suitable aromatic carboxylic acid substituents include halides, Cj to C 3 alkyl groups, Ci to C 3 alkyl ethers, and the like.
- the carboxylic acid includes an alkanedioic acid.
- Suitable examples of weak alkanedioic acids include hexanedioic acid (adipic acid) and tartaric acid.
- Another suitable weak acid is citric acid.
- the weak acid includes a weakly acidic ion- exchange resin. Mixtures of more than one weak acid also can be used.
- the reaction mixture includes an amine, such as a primary amine, secondary amine, or tertiary amine.
- the amine is present in the reaction mixture in a catalytic amount.
- a catalytic amount of the amine means that the molar concentration of the amine is less than the molar concentration of prenyl aldehyde in the reaction mixture.
- the molar concentration of the amine can be about 0.5% to about 95% of the molar concentration of prenyl aldehyde, for example, about 1% to about 50%, about 5% to about 30%, or about 10% to about 25%.
- the amine can be a primary amine represented by the formula H 2 NR 1 , wherein R 1 is preferably C 3 to Ci 2 alkyl or C 4 to Ci 2 cycloalkyl, more preferably C 6 to Cio alkyl or Ce to C 10 cycloalkyl, most preferably C? to C 9 alkyl.
- R can be a secondary alkyl group, a cycloalkyl group, or a tertiary alkyl group.
- Suitable examples of primary amines for use in the present disclosure include, but are not limited to, 2-aminobutane, tert-butylamine, 1- methylbutylamine (also known as 2-aminopentane), 1-ethylpropylamine (also known as 3- aminopentane), 2-aminohexane, 3-aminohexane, cyclohexylamine, tert-octylamine, and mixtures thereof.
- Preferred primary amines include hindered amines or tertiary alkyl amines such as tert- octylamine, tert-butylamine, cyclohexylamine, and the like.
- the amine is a secondary amine or a tertiary amine.
- Suitable secondary amines can be represented by the formula HNR 2 R 3
- suitable tertiary amines can be represented by the formula NR R R , wherein R , R , and R are independently selected from Ci to Cg alkyl, cycloalkyl, aryl, or substituted aryl.
- the secondary amine also can include cyclic and heterocyclic amines. Cyclic amines, for example, can include cyclic compounds comprising at least one nitrogen atom and 4 to 15 carbon atoms.
- Heterocyclic amines can include cyclic compounds comprising at least one nitrogen atom, 4 to 15 carbon atoms, and one to three oxygen and/or sulfur atoms.
- the tertiary amine can include, for example, N-substituted cyclic amines and N-substituted heterocyclic amines. Suitable N-substituents include Ci to C 3 alkyl groups.
- Suitable examples of secondary amines for use in the present disclosure include, but are not limited to, diethylamine, diisobutylamine, morpholine, pyrrolidine, and mixtures thereof.
- Suitable examples of tertiary amines for use in the present disclosure include, but are not limited to, diisopropylethylamine, triethylamine, and mixtures thereof.
- the present disclosure also encompasses methods for preparing self-aldol condensation products of ⁇ , ⁇ -unsaturated aldehydes having at least two ⁇ -hydrogens.
- the self-aldol condensation products can be prepared by reacting an ⁇ , ⁇ -unsaturated aldehyde having at least two ⁇ -hydrogens in the presence of an amine and a weak acid at a temperature of at least 10 0 C.
- Suitable ⁇ , ⁇ -unsaturated aldehydes include, but are not limited to, (E)-2-butenal (crotonaldehyde), trans-2-methyl-2-butenal (tiglic aldehyde), and (E)-2-pentenal.
- dehydrolavandulal can be converted to (2E)-5-methyl-2-(l - methylethenyl)-2,4-hexadien-l-ol (dehydrolavandulol) with sodium borohydride in methanol, and then reduced to tetrahydrolavandulol using sodium hypophosphite hydrate and catalytic palladium on carbon, as shown in Scheme 9.
- tetrahydrolavandulol 2E-5-methyl-2-(l - methylethenyl)-2,4-hexadien-l-ol
- dehydrolavandulal (1) to dehydrolavandulol.
- the selective reduction of an aldehyde to an alcohol in the presence of unsaturated carbon-carbon double bonds can be achieved by catalytic hydro genation, as is shown for the known conversion of citral to geraniol in Scheme 10.
- This reduction of citral to geraniol is analogous to the conversion of dehydrolavandulal (1) to dehydrolavandulol.
- Suitable catalysts useful for this transformation include Fe or Zn salts with Ru compounds (see, e.g., Jpn.
- Lavandulol 5-Methyl-2-(l-methylethenyl)-4-hexen-l-ol
- lavandulol has an herbal rose-like odor and is greatly valued in perfumery for use in artificial lavender oils.
- Lavandulol can be obtained by catalytic hydrogenation of dehydrolavandulol, as shown in Scheme 11. dehydrolavandulol lavandulol
- the irregular terpenoid dehydrolavandulal serves as a direct precursor to the acetate ester of (2E)-5-methyl-2-(l- methylethyl)-2,4-hexadien-l-ol, which was recently shown to be the sex pheromone of the passion vine mealybug, Planococcus minor (see, Millar, J. G., Tetrahedron Lett. 49, 315-317 (2008)).
- the latter insect is a significant pest of more than 250 host plants, including major crops as diverse as corn, soybeans, tomatoes, tree fruits such as oranges and lemons, rice, grapes, peanuts, coffee, cotton, and potatoes.
- dehydrocitral (2) can be converted to 2,6,6- trimethyl-l,3-cyclohexadiene-l-carboxaldehyde (safranal) according to the route in Scheme 13 (see, e.g., Retamar, et. al., Essenze, Derivati Agrumari, 63:407-413 (1993)). Safranal has the aroma of saffron, and is commercially valuable as a flavor and fragrance.
- reagent 10 ⁇ L (0.06 mmol) of tert-octylamine (purchased from Aldrich Chemical Co., Milwaukee, WI), and a TEFLON®-coated spin bar were added to a 25 mL, 1-neck reaction flask fitted with a reflux condenser connected to an apparatus similar to that described by Johnson and Schneider (Org. Synth., 30, 18 (1950)), such that the mixture in the flask is protected from atmospheric conditions throughout the course of the reaction.
- tert-octylamine purchased from Aldrich Chemical Co., Milwaukee, WI
- the N-tert-octyl imine derivative of 3-methyl-2-butenal may be an "intermediate" in the self-aldol reaction process. As reaction time is increased, and the reaction proceeds to a greater percent conversion, the presence of the imine derivative in the reaction product diminishes.
- a primary amine catalyst is essential for the reaction to proceed.
- Example 1 When the procedure of Example 1 was repeated in the absence of tert-octylamine, virtually no polyenals were obtained via self-aldol condensation of 3-methyl-2-butenal, as determined by proton NMR analysis of the crude reaction product.
- Replacement of tert-octylamine with an equivalent catalytic amount of cyclohexylamine (a less hindered primary amine) resulted in formation of self-aldol products of 3-methyl-2-butenal, although the reaction occurred at a slower rate.
- a drying agent e.g., anhydrous Na 2 SO 4
- This mixture subsequently was stirred at room temperature for 19 hours, after which it was diluted with 8 mL of hexane and filtered through a small pad of HYFLO SUPER-CEL® to remove the molecular sieves. 300 mg of anhydrous potassium carbonate was added to the filtrate, which subsequently was stirred at room temperature for 30 minutes to neutralize propionic acid. The product then was isolated by filtering off any solid material through a small pad of HYFLO SUPER-CEL®, followed by removal of the volatile organic solvents by evaporation at reduced pressure.
- the polyenal mixture consisted of dehydrolavandulal (1), dehydrocitral (2), and 4,6,6- trimethyl-l,3-cyclohexadiene-l-carboxaldehyde (3) in a 86:7:7 ratio, respectively. Furthermore, the product mixture contained less of the N-tert-octyl imine derivative of 3-methyl-2-butenal compared to the reaction in Example 1 (approximately 50% of the product compared to 70% of the product in Example 1).
- carboxylic acid catalysts were found to be suitable for performing the self aldol reaction.
- the carboxylic acid catalyst can be insoluble in the reaction mixture.
- Replacement of propionic acid with AMBERLITE® IRC-50 ion exchange resin (weakly acidic resin, 20-50 mesh) in 1:1 (v/v) heptane:tert-amyl alcohol with a catalytic amount of tert- octylamine at 20 0 C also yielded the self-aldol condensation products of 3-methyl-2-butenal.
- Use of AMBERLITE® as compared to propionic acid was found to decrease the rate of reaction. In the absence of propionic acid (or a compound of comparable acidity), the self-aldol condensation of 3-methyl-2-butenal proceeds very slowly or does not appreciably occur.
- This heterogeneous mixture was stirred vigorously at room temperature for 2 hours, after which it was diluted with 20 mL of 3:1 (v/v) hexane:dichloromethane.
- the organic layer then was washed in successive order with 20 mL of 5% (w/v) aqueous NaCl mixed with 2.0 mL of 2M aqueous HCl; 20 mL of 10% (w/v) aqueous NaCl; 15 mL of saturated aqueous sodium bicarbonate; and 15 mL of saturated brine.
- the organic layer then was dried over anhydrous magnesium sulfate and subsequently filtered.
- dehydrolavandulal (1) as the major product (>83% of the polyenal mixture) was unexpected since it was not detected in previous studies of the self-aldol condensation of 3-methyl-2-butenal. For example, see: D. Cahard, et al., Tetrahedron Lett., 39, 7093 (1998).
- dehydrolavandulol (2E)-5-methyl-2-(l-methylethenyl)-2,4-hexadien-l-ol (dehydrolavandulol), accompanied by minor amounts of the alcohols obtained via reduction of the dehydrocitral (2) and 4,6,6-trimethyl-l,3-cyclohexadiene-l-carboxaldehyde (3) present in the starting material.
- dehydrolavandulol was ascertained by proton NMR analysis (recorded in CDCI3 solution at 300 MHz).
- the polyenal mixture consisted of dehydrolavandulal (1), dehydrocitral (2), and 4,6,6- trimethyl-l ⁇ -cyclohexadiene-l-carboxaldehyde (3) in a 10:2:1 ratio, respectively.
- Approximately 45% of the crude product consisted of the N-tert-octyl imine derivative of 3- methyl-2-butenal.
- the ratio of dehydrolavandulal (1) to dehydrocitral (2) was less favorable (approximately 3:1).
- dehydrocitral (2) Although the formation of dehydrocitral (2) relative to dehydrolavandulal (1) increased slightly at higher temperature, the process is still attractive for the manufacture of fragrance chemicals since these two compounds comprised greater than 90% of the product mixture and can be separated by fractional distillation. Exhaustive hydrogenation of dehydrocitral (2) affords 3,7-dimethyloctan-l-ol (tetrahydrogeraniol), which possesses a rose petal-like odor and is often used to perfume household products.
- the mixture was stirred at room temperature for 18 hours, after which the mixture was diluted with 4.0 mL of hexane, and 50 mg of anhydrous potassium carbonate was added to the flask. This mixture subsequently was stirred at room temperature for 60 minutes to neutralize benzoic acid. The product then was isolated by filtering off any solid material through a small pad of HYFLO SUPER-CEL®, followed by removal of the volatile organic solvents by evaporation at reduced pressure.
- the polyenal obtained in this process was a 3:1 mixture of 2E:2Z stereoisomers of dehydrocitral (2), accompanied by minor amounts of "enamine intermediates" involved in this self-aldol process.
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JP2011506384A JP2011518832A (en) | 2008-04-24 | 2009-04-21 | Preparation of aldehydes by self-aldol condensation |
EP09734851A EP2271609A1 (en) | 2008-04-24 | 2009-04-21 | Methods for preparing aldehydes by self-aldol condensation |
CN2009801246665A CN102083781A (en) | 2008-04-24 | 2009-04-21 | Methods for preparing aldehydes by self-aldol condensation |
BRPI0911536A BRPI0911536A2 (en) | 2008-04-24 | 2009-04-21 | methods for the preparation of aldehydes by aldolic self-condensation |
CA2721813A CA2721813A1 (en) | 2008-04-24 | 2009-04-21 | Methods for preparing aldehydes by self-aldol condensation |
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WO2022104287A1 (en) * | 2020-11-16 | 2022-05-19 | Abbey Kirk J | Method for producing alpha-methylene lactones |
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US2230591A (en) * | 1937-02-06 | 1941-02-04 | Gen Aniline & Film Corp | Aliphatic aldehyde condensation products and a process for making them |
DE2212948A1 (en) | 1972-03-17 | 1973-09-20 | Basf Ag | Alpha,beta-unsatd aldehydes branched in alpha - position - by catalysed alkylation of unsatd alcohols |
US4438286A (en) * | 1981-10-16 | 1984-03-20 | Sumitomo Chemical Company, Limited | Substituted esters and alcohols |
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I.A. DYAKONOVA; G.V. CHERKAEV; M.B. ERMAN: "Alkali-catalyzed Self-condensation of 3-Methylbut-2-enal: Formation of Novel Rosoxide Dehydro Analogue", MENDELEEV COMMUNICATIONS, vol. 4, no. 3, 1994, pages 88 - 88, XP002530367 * |
L. DUHAMEL; J.-E. ANCEL: "Polyvinylogation Reagents: 1-Lithio-4-trimethylsiloxy-penta-1,3-diene and 1-Lithio-4-ethoxy-2-methyl-buta-1,3-diene", TETRAHEDRON, vol. 48, no. 42, 1992, pages 9237 - 9250, XP002530368 * |
R. KUHN; CH. GRUNDMANN: "Richard Kuhn und Christoph Grundmann: Synthese von Des-crocetin (Tetradecaheptaen-(1.3.5.7.9.11.13)-dicarbonsäure-(1.14))", CHEMISCHE BERICHTE, vol. 70, 1937, pages 1318 - 1330, XP002530366 * |
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KR20110016898A (en) | 2011-02-18 |
CA2721813A1 (en) | 2009-10-29 |
EP2271609A1 (en) | 2011-01-12 |
US7632973B2 (en) | 2009-12-15 |
US20090270658A1 (en) | 2009-10-29 |
BRPI0911536A2 (en) | 2019-03-12 |
CN102083781A (en) | 2011-06-01 |
JP2011518832A (en) | 2011-06-30 |
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