Classifications

• • 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups

Definitions

• the invention relates to a new process for the preparation of cyclopentadecanolide.
• Cyclopentadecanolide is a natural musk fragrance.
• Various processes are known for its production, but they have a number of disadvantages, in particular that they only give low yields and that the starting materials are not readily accessible.
• the process has the part that working with peroxides requires special precautionary measures and that the yield of cyclopentadecanolide is only at most 57.9%, based on 13-oxa-bicyclo [10.4.Q] -hexadecen- [1 (12)].
• 15-hydroxy-pentadecanoic acid is cyclized by vacuum distillation of its polyester (J.Am. Chem. Soc. 58, 654 (1936)).
• This process has the disadvantage that the starting materials for the preparation of 15-hydroxy-pentadecanoic acid, such as 9,10,1,6-trihydroxy-hexadecanecarboxylic acid (J.Chem.Soc. 1963, 3505), erucyl alcohol (J.Chem. Soc. 1962, 2348), Undec-10-enoic acid [Tetrahedron 19, 905 (1963); Japanese patent application 68 04 262] are too expensive for an economical process or are not available in sufficient quantities.
• the Russian inventor's certificate 521 274 describes a process in which 13-oxa-bicyclo [10.4.Q] hexadecen- [1 (12)] with butyl nitrite / NaHS0 3 is converted into 12-keto-cyclopentadecanolide and this is converted according to Clemmensen Cyclopentadecanolide is reduced.
• the yield of cyclopentadecanolide in this process is only 36%, as can be seen from the examples.
• the reaction time of 90 hours spent on the Clemmensen reduction is technically unsustainable.
• the invention is therefore based on the object of developing a process which, starting from the easily accessible 13-oxa-bicyclo [10.4.Q] -hexadecen- [1 (12)], gives cyclopentadecanolide in high purity and avoiding complex process steps .
• the resulting 12-oximinocyclopentadecanolide can then be hydrolyzed in a manner known per se, for example with sodium bisulfite, to give 12-ketocyclopentadecanolide, ie a compound of the formula (I) in which X represents the oxygen atom, or with hydrazine hydrate in the corresponding hydrazone , ie a compound of formula (I) in which X represents the -NNH 2 group, are converted.
• the hydrazone can be reduced according to Wolff-Kishner with sodium or a sodium alcoholate, the ketone according to Huang-Minlon with hydrazine in the presence of sodium or potassium hydroxide with simultaneous cleavage of the lactone ring to 15-hydroxypentadecanoic acid.
• the 12-oximino-cyclopentadecanolide is reduced immediately, ie without saponifying it to the ketone, with an excess of hydrazine hydrate in the presence of alkali metal hydroxide with cleavage of the lactone ring to 15-hydroxypentadecanoic acid.
• the reductive cleavage is carried out by heating the mixture of oxime, hydrazine and alkali in a high-boiling organic solvent such as ethylene or diethylene glycol, at temperatures of 150 to 200 ° C.
• the molar ratio of hydrazine: 12-oximinocyclopentadecanolide should be between 1.5 -3: 1.
• Hydrazine is preferably used in the form of 80% hydrazine hydrate.
• Sodium or potassium hydroxide is preferably used as the alkali hydroxide.
• the molar ratio of alkali metal hydroxide: 12-oximinocyclopentadecanolide is advantageously 3-5: 1.
• the 15-hydroxypentadecanoic acid can be cyclized by the customary processes known from the literature for the preparation of lactones from hydroxycarboxylic acids.
• the above-mentioned method by Spanagel and Carothers J.Am.Chem.Soc. 58, 654 (1936)
• a linear polyester is first prepared from 15-hydroxypentadecanoic acid and then in the presence of a depolymerization catalyst , such as magnesium chloride, magnesium oxide, lead dioxide, etc. is depolymerized.
• reflux condenser and Hinh - rer provided 4 1 three-necked flask 1000 ml of diethylene glycol were introduced.
• 280 g (5 mol) of potassium hydroxide, 269 g (1 mol) of 12-oximinocyclopentadecanolide and 187.5 g of 80% hydrazine hydrate were then added in succession with cooling.
• the apparatus was then flushed with nitrogen and the reaction mixture was heated to reflux for 2 hours.
• the excess hydrazine hydrate was then distilled off in a mixture with water.
• the bottom temperature was raised to 185 to 195 0 C. This temperature was maintained until nitrogen evolution ceased (about 9 hours).
• reaction mixture was mixed with one liter of ice water and acidified to pH 2 with hydrochloric acid.
• the precipitated reaction product was extracted with ethyl acetate while hot. When the warm ethyl acetate solution cooled, the product crystallized again. The product is separated and dried.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pyrane Compounds (AREA)

Applications Claiming Priority (2)

Publications (2)

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ID=6013771

Family Applications (1)

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Citations (3)

Family Cites Families (3)

• 1977
  • 1977-07-13 DE DE2731543A patent/DE2731543C3/de not_active Expired
• 1978
  • 1978-06-26 EP EP78100237A patent/EP0000476B1/fr not_active Expired
  • 1978-06-26 DE DE7878100237T patent/DE2861130D1/de not_active Expired
  • 1978-06-30 US US05/921,158 patent/US4187222A/en not_active Expired - Lifetime
  • 1978-07-11 IT IT50241/78A patent/IT1105097B/it active
  • 1978-07-12 JP JP8415678A patent/JPS5419989A/ja active Granted

Patent Citations (3)

Non-Patent Citations (6)

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