EP0000476B1 - Procédé de préparation de cyclopentadécanolide - Google Patents

Procédé de préparation de cyclopentadécanolide Download PDF

Info

Publication number
EP0000476B1
EP0000476B1 EP78100237A EP78100237A EP0000476B1 EP 0000476 B1 EP0000476 B1 EP 0000476B1 EP 78100237 A EP78100237 A EP 78100237A EP 78100237 A EP78100237 A EP 78100237A EP 0000476 B1 EP0000476 B1 EP 0000476B1
Authority
EP
European Patent Office
Prior art keywords
acid
oxa
lactone
cyclopentadecanolide
give
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100237A
Other languages
German (de)
English (en)
Other versions
EP0000476A1 (fr
Inventor
Kurt Dr. Bauer
Alfred Dr. Körber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Haarmann and Reimer GmbH
Original Assignee
Haarmann and Reimer GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haarmann and Reimer GmbH filed Critical Haarmann and Reimer GmbH
Publication of EP0000476A1 publication Critical patent/EP0000476A1/fr
Application granted granted Critical
Publication of EP0000476B1 publication Critical patent/EP0000476B1/fr
Expired legal-status Critical Current

Links

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.

Landscapes

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

Claims (2)

1. Procédé de préparation de cyclopentadéca- nolide, caractérisé en ce qu'on transforme, de façon connue en soi, le 13-oxa-bicy- clo[10.4.0]-hexadécène-[1(12)] en une lactone de formule générale I:
Figure imgb0004
dans laquelle
X représente un atome d'oxygène, le groupe =NOH ou le groupe =N-NH2,
on réduit cette lactone de formule générale I en acide 15-hydroxydécanoïque avec ouverture du noyau lactone suivant Wolff-Kishner ou Huang-Minlon, puis on soumet cet acide 15-hydroxydécanoïque à une cyclisation en cyclopentadécano- lide de façon connue en soi.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on fait réagir le 13-oxa-bicy- clo[10.4.0]-hexadécène-[1(12)] avec du chlorure de nitrosyle ou un composé azoté formant des ions nitrosyle dans les conditions réactionnelles, pour obtenir le 12-oximinocyclopentadécanolide que l'on transforme, avec de l'hydrate d'hydrazine, suivant Huang-Minlon, en présence d'un hydroxyde alcalin, en acide 15-hydroxypentadé- canoïque, puis on polymérise ce dernier et on dé- polymérise le polyester linéaire formé en présence de catalyseurs de dépolymérisation.
EP78100237A 1977-07-13 1978-06-26 Procédé de préparation de cyclopentadécanolide Expired EP0000476B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2731543A DE2731543C3 (de) 1977-07-13 1977-07-13 Verfahren zur Herstellung von Cyclopentadecanolid
DE2731543 1977-07-13

Publications (2)

Publication Number Publication Date
EP0000476A1 EP0000476A1 (fr) 1979-02-07
EP0000476B1 true EP0000476B1 (fr) 1981-10-07

Family

ID=6013771

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100237A Expired EP0000476B1 (fr) 1977-07-13 1978-06-26 Procédé de préparation de cyclopentadécanolide

Country Status (5)

Country Link
US (1) US4187222A (fr)
EP (1) EP0000476B1 (fr)
JP (1) JPS5419989A (fr)
DE (2) DE2731543C3 (fr)
IT (1) IT1105097B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0626291B2 (ja) * 1985-03-15 1994-04-06 株式会社東芝 利得制御装置
DE4115182A1 (de) * 1991-05-09 1992-11-12 Haarmann & Reimer Gmbh Neue derivate cyclischer lactone, verfahren zu ihrer herstellung und verfahren zur herstellung von 15-pentadecanolid und seinen homologen
DE10041198B4 (de) 2000-08-23 2004-01-15 Symrise Gmbh & Co. Kg Verfahren zur Herstellung makrocyclischer Ester
GB2423986A (en) * 2004-12-24 2006-09-13 Givaudan Sa Fragrance Compound

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2092031A (en) * 1937-09-07 Process of preparing cycijc esters
US3890353A (en) * 1969-05-29 1975-06-17 Firmenich & Cie Process for preparing lactones
JPS5125033B2 (fr) * 1971-08-18 1976-07-28
DE2410859A1 (de) * 1974-03-07 1975-09-18 Haarmann & Reimer Gmbh Macrocyclische ketolactone
SU521274A1 (ru) * 1974-03-29 1976-07-15 Ордена Ленина Институт Элементоорганических Соединений Ан Ссср Способ получени циклопентадеканолида или его метильного производного
DE2511410C2 (de) * 1975-03-15 1983-10-20 Basf Ag, 6700 Ludwigshafen 12-Oxo-15-hydroxy-tetradecancarbonsäurelactone und Verfahren zu ihrer Herstellung

Also Published As

Publication number Publication date
DE2731543A1 (de) 1979-01-18
EP0000476A1 (fr) 1979-02-07
DE2731543C3 (de) 1980-07-31
IT7850241A0 (it) 1978-07-11
IT1105097B (it) 1985-10-28
DE2861130D1 (en) 1981-12-17
JPS5419989A (en) 1979-02-15
DE2731543B2 (de) 1979-11-22
US4187222A (en) 1980-02-05
JPS6121474B2 (fr) 1986-05-27

Similar Documents

Publication Publication Date Title
DE2434208A1 (de) Derivat der 2-azetidinsulfensaeure und verfahren zu seiner herstellung
EP0000476B1 (fr) Procédé de préparation de cyclopentadécanolide
DE2511410C2 (de) 12-Oxo-15-hydroxy-tetradecancarbonsäurelactone und Verfahren zu ihrer Herstellung
EP0001089B1 (fr) Procédé de préparation de 2-tetrahydrofurannones substituées par un radical halogénovinyle; certaines 2-tetrahydrofurannones substituées par un radical halogénovinyle
DE3122995C2 (fr)
DE1145179B (de) Verfahren zur Herstellung von bicyclischen Laktonen
EP0061669B1 (fr) Procédé de préparation de cyclohexane-1,3-diones, ainsi que cyclohexanes-1,3-diones bicycliques
DE3338853C2 (de) Verfahren zur Herstellung von 2-Cyclopentenonen
DE1951294C3 (de) Verfahren zur Herstellung von 3-Hydroxy-2-methyl-y-pyron (Maltol)
EP0119546B1 (fr) Procédé de préparation de composés de la série 4-oxo-damascone ainsi que les parfums de cette série de composés
EP0121838B1 (fr) Procédé pour la préparation de butène-2 diones-1,4 substituées en positions 1 et 4
EP1525176B1 (fr) Procede de production de cetones macrocycliques par condensation de dieckmann en phase gazeuse
DE2150146B2 (de) Verfahren zur Herstellung von Flavon-7-oxyessigsäureäthylester
DE3123177C2 (fr)
DE1271713B (de) Verfahren zur Herstellung von organischen Carbonylverbindungen
DE915938C (de) Verfahren zur Herstellung von Oxoacylaminen der Cyclopentanopolyhydrophenanthrenreihe
EP0398099B1 (fr) Procédé pour la préparation de cyclopentanones
DE1643281C (de) Verfahren zur Herstellung von Zearalan
DE1142595B (de) Verfahren zur Herstellung von 4-(2,6,6-Trimethyl-cyclohexen-(1)-yl)-2-methylbuten-(3)-al-(1)
EP0089585A1 (fr) Procédé de préparation de 2-alkyl-4,4-diacyloxy-2-buténals
DE1287080B (de) Verfahren zur Herstellung von Alkoxyolefinen
DE3006983A1 (de) Verfahren zur herstellung einer brassylsaeurediester-vorstufe und von brassylsaeurediester
EP0089576A2 (fr) 1,1-Diacyloxy-3-alcoyle-4-hydroxy-2-butènes, leur préparation et utilisation
DE1076683B (de) Verfahren zur Herstellung der Ameisensaeureester von 1-Alkinylcycloalkanolen
EP0087097A2 (fr) 2-Alkyl-1,3-diacyloxy-4-hydroxy-1-butènes, leur préparation et leur utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

REF Corresponds to:

Ref document number: 2861130

Country of ref document: DE

Date of ref document: 19811217

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19950515

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950524

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19950613

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950615

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19950627

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19950628

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19960630

Ref country code: BE

Effective date: 19960630

BERE Be: lapsed

Owner name: HAARMANN & REIMER G.M.B.H.

Effective date: 19960630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960626

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT