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 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 easily accessible.
• 15-hydroxypentadecanoic acid is cyclized by vacuum distillation of its polyester [J. At the. Chem. Soc. 58, 654 (1936)].
• This process has the disadvantage that the starting materials for the preparation of 15-hydroxy-pentadecanoic acid, such as 9,10,16-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 [10.4.0] hexadecen- [1 (12)] with butyl nitrite / NaHS0 3 is converted into the 12-keto-cyclopentadecanolide and this is followed Clemmensen is reduced to cyclopentadecanolide.
• 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 [10.4.0] hexadecene [1 (12)], gives cyclopentadecanolide in high purity and avoiding complex process steps .
• the process according to the invention although it opens the macrocycle, yields much better yields than the known processes, which likewise use 13-oxa-bicyclo [10.4.0] hexadecen- [1 (12)] go out and in which the macrocycle is maintained in all reaction steps.
• cyclopentadecanolide of high purity is obtained in yields of 75 to 85% of theory, based on 13-oxa-bicyclo [10.4.0] hexadecene [1 (12)], with process steps which can be carried out without any technical effort.
• 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 immediately, ie without saponifying to the ketone, reduced with an excess of hydrazine hydrate in the presence of alkali hydroxide with cleavage of the lactone ring to 15-hydroxypentadecanoic acid.
• the reducing cleavage is carried out by heating the mixture of oxime, hydrazine and alkali hydroxide in a higher-boiling organic solvent, such as ethylene or diethylene glycol, to temperatures of 150 to 200 ° C.
• the hydrazine: 12-oximinocyclopentadecanolide molar ratio 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. At the. Chem. Soc. 58, 654 (1936)], in which a linear polyester is first prepared from 15-hydroxypentadecanoic acid, which is then depolymerized in the presence of a depolymerization catalyst such as magnesium chloride, magnesium oxide, lead dioxide, etc.
• 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.
• Example 4 50 g of 12-keto-cyclopentadecanolide (prepared according to Example 4) were treated with 36.6 g of 80% hydrazine hydrate and 54.7 g of potassium hydroxide in 150 ml of diethylene glycol among those in Example 3 implemented reaction conditions.

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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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• 1977
  • 1977-07-13 DE DE2731543A patent/DE2731543C3/de not_active Expired
• 1978
  • 1978-06-26 DE DE7878100237T patent/DE2861130D1/de not_active Expired
  • 1978-06-26 EP EP78100237A patent/EP0000476B1/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

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