WO2018011386A1 - Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione - Google Patents
Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione Download PDFInfo
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- WO2018011386A1 WO2018011386A1 PCT/EP2017/067811 EP2017067811W WO2018011386A1 WO 2018011386 A1 WO2018011386 A1 WO 2018011386A1 EP 2017067811 W EP2017067811 W EP 2017067811W WO 2018011386 A1 WO2018011386 A1 WO 2018011386A1
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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
- C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
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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
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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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
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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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
Definitions
- the present invention relates to a method for preparing 14-methyl-16-oxabicyclo- [10.3.1 ]pentadecenes in a two-step synthesis from 3-methyl-1 ,5-cyclopentadecanedione as starting material. STATE OF THE ART
- Saturated macrocyclic ketones having 14- to 18-membered rings e.g. muscone (3-methylcyclopentadecanone), have interesting properties as fragrances or flavors.
- 3-methyl-cyclopentadec-4-en-1 -one and 3-methyl-cyclopentadec-5-en-1 -one are two unsaturated homologues of muscone that are also valuable musk-like aroma chemicals. Both double bond isomers and the mixtures thereof are also denoted as "muscenone" (DH-muscone).
- Formula (A) depicts muscenone without consideration of possible position and configuration isomers:
- the crude cyclopentadecan-5-ol-1 -one (C) is subjected to a reaction with benzenesulfonic acid in toluene to obtain a mixture of 3-methyl-cyclopentadec-4-en-1 -one and 3-methyl-cyclopentadec-5-en-1 -one (A)
- the present invention relates to a process for preparing at least one compound of the general formula (I)
- reaction product comprising a mixture of the compounds of the general formulae (Ilia) and (1Mb)
- a specific embodiment is a method in which the NaBhU is employed in an amount of 0.1 to 0.5 mole equivalents, based on the amount of the compound of the general formula (II). If the application quantity of the NaBhU is in the mentioned range, the reaction mixture obtained in step a) has an advantageous content, i.e. a high amount of the compounds (Ilia) and (lllb) and a low amount of 3-methyl-cyclopentadecan-1 ,5-diol. DESCRIPTION OF THE INVENTION
- the process of the invention avoids the use of hydrogen which affords complex and expensive technology.
- step a) It is possible to control the reaction in step a) to obtain a high selectivity with regard to the mixture of compounds (Ilia) and (lllb). This is possible by choosing an appropriate amount of NaBhU and/or by choosing an appropriate reaction temperature and/or by terminating the reaction before complete conversion of the diketone (II). An over-reduction can be essentially avoided so that the amount of the undesirable 3-methyl-cyclopentadecane-1 ,5-diol (IV) can be kept remarkably low.
- the main components of the reaction mixture obtained in step a) are the two partially oxidized products (Ilia) and (lllb) and the diketone starting material (II). It has been found that (II) is inert under the condition of reaction step b) and can be easily separated off from the muscenone product (I) and can be recycled to the first reaction step a).
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- muscle refers to all possible position and configuration isomers in pure form and any mixture thereof.
- the term “muscenone” and the formula (I) refers to
- the isomers of 3-methylcyclopentadec-5-en-1 -one are: (-)-(3R,5Z)-3-methylcyclopentadec-5-en-1 -one, (+)-(3S,5Z)-3-methylcyclopentadec-5-en-1 -one, (-)-(3R,5E)-3-methylcyclopentadec-5-en-1 -one and
- (+)-(3S,5E)-3-methylcyclopentadec-5-en-1 -one (+)-(3S,5E)-3-methylcyclopentadec-5-en-1 -one.
- All muscenone compositions are valuable aroma chemicals and can in particular be used to confer, improve, enhance or modify the odor properties of a perfuming composition or a perfumed article. Due to the actual composition the olfactoric properties may vary e.g. from a strong and pure smell of musk to more woody notes.
- Step a) The synthesis of 3-methyl-1 ,5-cyclopentadecanedione (II) that is employed as starting materials in step a) of the process according to the invention can be performed in analogy to the methods for the synthesis of 1 ,5-cyclopentadecanedione described in CH 519454 and CH 513791. In principle, 14-methyl-bicyclo[10.3.0]pentadec-1 (12)-en (V)
- oxidation agent e.g. KMn0 4 , 0 3 , H 2 0 2 and Pb 3 0 4 .
- reaction step a) the NaBH 4 is employed in an amount of 0.07 to 0.7 mole
- the NaBH 4 is added to the compound of the general formula (II).
- the compound of the general formula (II) is preferably employed as a solution in a solvent. Suitable solvents are mentioned in the following.
- the NaBH 4 can be added to the compound of the general formula (II) in form of a solid or a solution in a solvent.
- the solvent used for dissolving the compound of the general formula (II) and the solvent of the NaBH 4 are the same.
- the reaction in step a) is effected in the presence of a solvent, selected from alcohols, ethers, water and mixtures thereof.
- a solvent selected from alcohols, ethers, water and mixtures thereof.
- the solvent is selected from Ci-C 4 -alkanols, Ci-C 4 -alkylene glycols, mono- and di-(Ci-C 4 -alkyl) ethers of Ci-C 4 -alkylene glycols, polyalkylene glycols, polyalkylene glycol mono- and di-(Ci-C 4 -alkyl) ethers, water and mixtures thereof.
- the solvent is particularly preferably selected from among methanol, ethanol, ethylene glycol, ethylene glycol dimethyl ether, mixtures thereof and mixtures of the aforementioned solvents with water.
- methanol or ethanol is used as solvent.
- the reaction in step a) is effected in the presence of an added acid.
- Suitable acids are selected from acids having a pK a value in the range of from 1 to 7, preferably of from 2 to 6.
- the pK a value for dissociation of the first proton (pK a i) is preferably in the range of from 1 to 7, preferably of from 2 to 6.
- Suitable acids are also weakly acidic cation exchanger.
- a specially preferred acid is benzoic acid.
- the reaction in step a) is effected without the addition of an acid.
- the reaction in step a) is effected at a temperature in the range of from -10 to 25°C, more preferably from -5 to 15°C, in particular from 0 to 10°C.
- the reaction in step b) comprises a first period, wherein the NaBFU is added at a first temperature and a second period after the addition of NaBFU is completed at a second temperature.
- the first temperature is in a range of from -10 to 25°C, more preferably from 0 to 20°C.
- the second temperature is in a range of from 0 to 50°C, more preferably from 10 to 35°C. In particular, the first temperature is always lower than the second temperature.
- the reaction in step a) is effected at a pressure within a range from
- reaction in step a) can be carried out in a batch, semi-batch or continuous process.
- the content of at least one of the components (II), (Ilia), (1Mb) or (IV) in the reaction zone or in a discharge from the reaction zone can be determined by suitable analytical measures.
- samples can be taken from the reaction zone at regular intervals and the content of at least one of the components (II), (Ilia), (1Mb) or (IV) detected.
- this measurement can also be carried out by means of an on-line measurement device in the discharge from the reaction zone.
- the content of at least one of the components (II), (Ilia), (1Mb) or (IV) can be determined, for example, by gas chromatography (GC), infrared spectroscopy, UV spectroscopy or chemiluminescence analysis.
- the quantitative analysis is performed by gas chromatography.
- Quantitative GC analysis is a standard method known to a person skilled in the art. In principle, in GC chromatography (as generally in column chromatography) the area of a peak is usually proportional to the number of moles of the corresponding compound. In a mixture of more than one analyte the area of each peak corresponds to the mole fraction of a particular compound in the mixture. The use of an internal standard serves to compensate errors and get a high analytical precision. Precise estimation of the peak areas and calculation of the corresponding mole fractions can be performed with the electronic integration unit of the chromatograph.
- the conversion with regard to starting component (II) in % at a reaction time t is defined as: initial amount of (II)— amount of (II) at t
- step a) the conversion with regard to compound (II) is in a range of from 10 to 80%, preferably of from 20 to 75%.
- the reaction can be terminated, e.g. by adding a substance that deactivates the NaBhU. Suitable substances that deactivate NaBhU are mentioned in the following.
- the total amount of components (Ilia) and (lllb) in the reaction product obtained in step a) is preferably at least 20 mol%, more preferably at least 30 mol%, in particular at least 40 mol%, based on the total amount of components (II), (Ilia), (lllb) and (IV) in the reaction product.
- the amount of 3-methyl-cyclopentadecan-1 ,5-diol (IV) in the reaction product obtained in step a) is preferably not more than 20 mol%, more preferably not more than
- the reaction product obtained in step a) can be subjected to a work-up prior to its use in reaction step b).
- the reaction product obtained in step a) is subjected to at least one after-treatment step, selected from deactivation of unreacted NaBhU, removal of at least one component selected from solvent, acid employed for the reaction and/or the deactivation of unreacted NaBhU, salts obtained in the deactivation of unreacted NaBhU.
- Unreacted NaBhU can be deactivated by addition of an acid. Suitable acids are e.g. HCI, H2SO4, HNOs, H3PO4, etc. If the unreacted NaBhU shall be deactivated this is performed preferably prior to any purification step.
- reaction products formed in the deactivation of NaBhU can be at least partly removed in the following purification.
- reaction product obtained in step a) can be subjected to a purification by extraction.
- a solvent mixture is employed that comprises two at least partly immiscible solvents that form two liquid phases.
- water and organic solvents that are already present in the reaction product of step a) are not removed prior to the extraction.
- one at least partly water immiscible organic solvent is added to the reaction product obtained in step a).
- Suitable at least partly water immiscible organic solvents are halogenated
- step a) If the reaction product obtained in step a) does not already contain a sufficient amount of water and/or an essentially water-miscible solvent, then additional water and/or an essentially water-miscible solvents are added to the reaction product obtained in step a). The two liquid phases are brought into intimate contact, separated, the water phase is separated off and the organic phase containing components (Ilia) and (1Mb) and optionally (II) and/or (IV) is collected.
- water immiscible organic solvents are dichloromethane chloroform, acetyl acetate, diethyl ether, etc.
- the extraction may be repeated once or several times.
- the combined organic phases may be subjected to at least one washing step. Suitable washing media are e.g. water or brine. From the optionally washed organic phase the organic solvent can be removed, preferably by evaporation. Step b)
- step b) of the method according to the invention the reaction product obtained in step a) is treated with an acid to yield at least one compound of the general formula (I).
- any acid can be used for the reaction in step b), i.e. any substance having Bronstedt or Lewis acidity.
- suitable catalysts are protic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid and
- p-toluenesulfonic acid acidic molecular elemental compounds, such as aluminum chloride, boron trifluoride, zinc chloride, oxidic acidic solids, such as zeolites, silicates, aluminates, aluminosilicates, clays and acidic ion exchangers.
- acidic molecular elemental compounds such as aluminum chloride, boron trifluoride, zinc chloride, oxidic acidic solids, such as zeolites, silicates, aluminates, aluminosilicates, clays and acidic ion exchangers.
- the acid employed in reaction step b) comprises or consists of phosphoric acid.
- the reaction in step b) is effected in the presence of a solvent having a boiling point at 1013.25 hPa of at least 85°C.
- the reaction in step b) is effected at a pressure within a range from
- reaction in step b) is effected in the presence of a solvent selected from hydrocarbons and hydrocarbon mixtures, in particular selected from toluene, xylene, heavy naphtha, petroleum ether, decalin and mixtures thereof.
- a solvent selected from hydrocarbons and hydrocarbon mixtures, in particular selected from toluene, xylene, heavy naphtha, petroleum ether, decalin and mixtures thereof.
- a preferred solvent is toluene.
- reaction product obtained in step b) can be subjected to a work-up prior to the use as aroma chemical.
- the reaction product obtained in step b) is subjected to a separation to obtain at least one fraction (F-l) enriched in the compound of the general formula (I) and a fraction (F-ll) enriched in the unreacted compound of the formula (II).
- the reaction product obtained in step b) is preferably subjected to a distillative separation.
- Suitable apparatuses for distillative separation comprise distillation columns, such as tray columns which may be equipped with bubble-caps, sieve plates, sieve trays, structured packings, random packings, valves, side draws, etc., evaporators, such as thin film evaporators, falling film evaporators, forced circulation evaporators, Sambay evaporators, etc., and combinations thereof.
- the reaction product obtained in step b) is preferably subjected in step e) to a distillative separation in at least one distillation column which is provided with separating internals.
- a fraction (F-l) enriched in the compound of the general formula (I) is preferably isolated from the reaction product obtained in step b) which fraction has a content of 3-methyl-cyclopentadecane-1 ,5-diol (IV) of at most 2% by weight, particularly preferably at most 1 % by weight, particularly preferably at most 0.1 % by weight.
- a fraction (F-l) enriched in the compound of the general formula (I) is preferably isolated from the reaction product obtained in step b) which fraction has a content of the compound (I) of at least 90% by weight, particularly preferably at least 95% by weight, particularly preferably at least 99% by weight.
- fraction (F-ll) enriched in the compound of the formula (II) is preferably recycled to the reaction in step a).
- compositions obtainable by the method according to the invention are particularly suitable as fragrances or for providing a fragrance.
- compositions according to the invention for use as fragrances can be diluted, as desired, with at least one customary solvent in this area of application.
- suitable solvents are: ethanol, dipropylene glycol or ethers thereof, phthalates, propylene glycols, or carbonates of diols, preferably ethanol.
- Water is also suitable as solvent for diluting the fragrance compositions according to the invention and can advantageously be used together with suitable emulsifiers.
- the fragrances on the basis of the compounds (I) obtainable by the method according to the invention have high stability and durability.
- the compounds of the formula (I) obtainable by the method according to the invention either in pure form or mixtures thereof are characterized by a pleasant odor of musk.
- fragrances obtained by the method according to the invention are suitable for incorporation in cosmetic compositions and also utility and consumer goods or agents, such as are described in more detail below, in which the fragrance may be
- an organoleptically effective amount is to be understood as meaning particularly an amount which suffices, when used as intended, to bring about a scent impression for the user or consumer.
- Suitable cosmetic compositions are all customary cosmetic compositions.
- the compositions in question are preferably perfume, Eau de Toilette, deodorants, soap, shower gel, bathing gel, creams, lotions, sunscreen, compositions for cleansing and care of hair, such as shampoo, conditioner, hair gel, hair setting compositions in the form of liquids or foams and other cleansing or care compositions for the hair, compositions for decorative application on the human body, such as cosmetic sticks, for example lipsticks, lip care sticks, concealing sticks (concealers), blushers, eye shadow pencils, lip liner pencils, eyeliner pencils, eyebrow pencils, correction pencils, sunscreen sticks, antiacne sticks and comparable products, and also nail varnishes and other products for nail care.
- cosmetic sticks for example lipsticks, lip care sticks, concealing sticks (concealers), blushers, eye shadow pencils, lip liner pencils, eyeliner pencils, eyebrow pencils, correction pencils, sunscreen sticks, antiacne sticks and comparable products, and also nail varnishes and other products for nail
- fragrances obtained by the method according to the invention are specifically suitable for use in perfumes, e.g. as Eau de Toilette, shower gels, bathing gels and body deodorants.
- consumer or utility goods are also suitable for aromatizing consumer or utility goods into which they are incorporated or onto which they are applied and to which they thereby impart a pleasant fresh green accent.
- consumer or utility goods are: room air deodorants (air care), cleaning compositions or care compositions for textiles
- GC-Column DB-WAX (30 m (Length), 0.32 mm (ID), 0.25 ⁇ (Film));
- Injector at 230°C, detector at 280°C and flow 1.5 ml.
- Temperature program 80°C to 250°C in 3°C/min, 250°C for 15 min.
- the conversion is defined as the difference of the area% value of the diketone (II) and 100%.
- the selectivity is defined as area% ⁇ Ilia) + ⁇ Illb)
- the diketone (II) and the EtOH are mixed at room temperature.
- the NaBH 4 is added at 0°C in portions.
- the reaction mixture is stirred at 0°C for 6 h.
- a sample is taken every hour and further analyzed by GC (see table 4).
- the diketone (II) and the EtOH are mixed at room temperature.
- the NaBH 4 is added at 5°C in portions.
- the reaction mixture is stirred at room temperature for 3 h. After 3 h a sample is taken and analyzed by GC (see table 8).
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES17739975T ES2954272T3 (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione |
EP17739975.5A EP3484844B1 (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione |
CN201780043144.7A CN109476577A (en) | 2016-07-15 | 2017-07-14 | By 3- methyl-1,5- cyclopentadecane diketone prepares 14- methyl-1 6- oxabicyclo [10.3.1] ten pentaene |
JP2019501598A JP7039551B2 (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-Methyl-16-oxabicyclo [10.3.1] pentadecene from 3-methyl-1,5-cyclopentadecanedione |
BR112018077067-1A BR112018077067B1 (en) | 2016-07-15 | 2017-07-14 | Process to make a compound |
MX2019000664A MX2019000664A (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione. |
US16/317,279 US10800724B2 (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP16179692 | 2016-07-15 | ||
EP16179692.5 | 2016-07-15 |
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WO2018011386A1 true WO2018011386A1 (en) | 2018-01-18 |
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PCT/EP2017/067811 WO2018011386A1 (en) | 2016-07-15 | 2017-07-14 | Preparation of 14-methyl-16-oxabicyclo[10.3.1]pentadecenes from 3-methyl-1,5-cyclopentadecanedione |
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US (1) | US10800724B2 (en) |
EP (1) | EP3484844B1 (en) |
JP (1) | JP7039551B2 (en) |
CN (1) | CN109476577A (en) |
BR (1) | BR112018077067B1 (en) |
ES (1) | ES2954272T3 (en) |
MX (1) | MX2019000664A (en) |
WO (1) | WO2018011386A1 (en) |
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US10259822B2 (en) * | 2015-11-23 | 2019-04-16 | Basf Se | Method for the preparation of compounds having a 16-oxabicyclo[10.3.1]pentadecene scaffold and the subsequent products thereof |
WO2020066898A1 (en) | 2018-09-28 | 2020-04-02 | 花王株式会社 | Method for producing cyclic enol ether compound |
WO2020150454A1 (en) | 2019-01-17 | 2020-07-23 | International Flavors & Fragrances Inc. | Synthesis of 14-methyl-16-oxabicyclo[10.3.1]hexadec-12-ene |
JPWO2020189661A1 (en) * | 2019-03-18 | 2020-09-24 | ||
JPWO2020189670A1 (en) * | 2019-03-18 | 2020-09-24 | ||
WO2020212264A1 (en) * | 2019-04-15 | 2020-10-22 | Firmenich Sa | Process for preparing bicyclic enolether |
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WO2022017389A1 (en) * | 2020-07-21 | 2022-01-27 | Givaudan Sa | Method for the production of musk fragrance ingredient |
US11993628B2 (en) | 2016-07-11 | 2024-05-28 | Sage Therapeutics, Inc. | C7, C12, and C16 substituted neuroactive steroids and their methods of use |
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JP2023151195A (en) * | 2022-03-31 | 2023-10-16 | 花王株式会社 | Method for producing cyclic diketone compound |
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Also Published As
Publication number | Publication date |
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EP3484844A1 (en) | 2019-05-22 |
US20190300467A1 (en) | 2019-10-03 |
BR112018077067A2 (en) | 2019-04-02 |
CN109476577A (en) | 2019-03-15 |
JP7039551B2 (en) | 2022-03-22 |
US10800724B2 (en) | 2020-10-13 |
JP2019521141A (en) | 2019-07-25 |
ES2954272T3 (en) | 2023-11-21 |
BR112018077067B1 (en) | 2022-05-31 |
MX2019000664A (en) | 2019-05-20 |
EP3484844B1 (en) | 2023-06-14 |
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