EP0000476B1 - Verfahren zur Herstellung von Cyclopentadecanolid - Google Patents
Verfahren zur Herstellung von Cyclopentadecanolid Download PDFInfo
- 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
Links
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- -1 nitrosyl ions Chemical class 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 238000006856 Wolf-Kishner-Huang Minlon reduction reaction Methods 0.000 claims description 3
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000004157 Nitrosyl chloride Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 2
- VPCDQGACGWYTMC-UHFFFAOYSA-N nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019392 nitrosyl chloride Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- BZUNJUAMQZRJIP-UHFFFAOYSA-N 15-hydroxypentadecanoic acid Chemical compound OCCCCCCCCCCCCCCC(O)=O BZUNJUAMQZRJIP-UHFFFAOYSA-N 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 150000007857 hydrazones Chemical class 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- SYZADARSZXMEIX-UHFFFAOYSA-N 3,4,6,7,8,9,10,11,12,13,14,14a-dodecahydro-2h-cyclododeca[b]pyran Chemical compound C1CCCCCCCCC=C2CCCOC21 SYZADARSZXMEIX-UHFFFAOYSA-N 0.000 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CFOQKXQWGLAKSK-KTKRTIGZSA-N (13Z)-docosen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCO CFOQKXQWGLAKSK-KTKRTIGZSA-N 0.000 description 1
- VTTPSKGLNAUJMQ-UHFFFAOYSA-N 10,11,17-trihydroxyheptadecanoic acid Chemical compound OCCCCCCC(O)C(O)CCCCCCCCC(O)=O VTTPSKGLNAUJMQ-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- CFOQKXQWGLAKSK-UHFFFAOYSA-N 13-docosen-1-ol Natural products CCCCCCCCC=CCCCCCCCCCCCCO CFOQKXQWGLAKSK-UHFFFAOYSA-N 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- 238000006214 Clemmensen reduction reaction Methods 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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)
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 (de) | 1979-02-07 |
| EP0000476B1 true EP0000476B1 (de) | 1981-10-07 |
Family
ID=6013771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100237A Expired EP0000476B1 (de) | 1977-07-13 | 1978-06-26 | Verfahren zur Herstellung von Cyclopentadecanolid |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4187222A (enrdf_load_stackoverflow) |
| EP (1) | EP0000476B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS5419989A (enrdf_load_stackoverflow) |
| DE (2) | DE2731543C3 (enrdf_load_stackoverflow) |
| IT (1) | IT1105097B (enrdf_load_stackoverflow) |
Families Citing this family (4)
| 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)
| 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 (enrdf_load_stackoverflow) * | 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 |
-
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
Also Published As
| Publication number | Publication date |
|---|---|
| IT7850241A0 (it) | 1978-07-11 |
| DE2861130D1 (en) | 1981-12-17 |
| DE2731543A1 (de) | 1979-01-18 |
| DE2731543B2 (de) | 1979-11-22 |
| JPS5419989A (en) | 1979-02-15 |
| JPS6121474B2 (enrdf_load_stackoverflow) | 1986-05-27 |
| US4187222A (en) | 1980-02-05 |
| EP0000476A1 (de) | 1979-02-07 |
| DE2731543C3 (de) | 1980-07-31 |
| IT1105097B (it) | 1985-10-28 |
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