DE1793710C3 - Cis and trans epoxyocimes, processes for their production and their use - Google Patents
Cis and trans epoxyocimes, processes for their production and their useInfo
- Publication number
- DE1793710C3 DE1793710C3 DE19681793710 DE1793710A DE1793710C3 DE 1793710 C3 DE1793710 C3 DE 1793710C3 DE 19681793710 DE19681793710 DE 19681793710 DE 1793710 A DE1793710 A DE 1793710A DE 1793710 C3 DE1793710 C3 DE 1793710C3
- Authority
- DE
- Germany
- Prior art keywords
- trans
- cis
- ocimen
- epoxyocimes
- peracid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- IHPKGUQCSIINRJ-CSKARUKUSA-N (E)-β-ocimene Chemical compound CC(C)=CC\C=C(/C)C=C IHPKGUQCSIINRJ-CSKARUKUSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 4
- 239000002304 perfume Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M buffer Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- 238000006735 epoxidation reaction Methods 0.000 claims 2
- 150000002118 epoxides Chemical class 0.000 claims 2
- WUIFRGYQELQKDN-NTMALXAHSA-N (E)-Ocimene Natural products CC(C)CC\C=C(\C)C=C WUIFRGYQELQKDN-NTMALXAHSA-N 0.000 claims 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- STABAPSYCQFWOK-UHFFFAOYSA-N 4-chlorobenzenecarboperoxoic acid Chemical compound OOC(=O)C1=CC=C(Cl)C=C1 STABAPSYCQFWOK-UHFFFAOYSA-N 0.000 claims 1
- 240000002319 Citrus sinensis Species 0.000 claims 1
- 235000005976 Citrus sinensis Nutrition 0.000 claims 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 claims 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N Peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M Potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M Sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 230000002708 enhancing Effects 0.000 claims 1
- 150000007823 ocimene derivatives Chemical class 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 230000001105 regulatory Effects 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229940095064 tartrate Drugs 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N triclene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- 235000010701 Lavanda vera Nutrition 0.000 description 3
- 240000002809 Lavandula angustifolia Species 0.000 description 3
- 235000003515 Lavandula officinalis Nutrition 0.000 description 3
- 239000001102 lavandula vera Substances 0.000 description 3
- 235000018219 lavender Nutrition 0.000 description 3
- JOZKFWLRHCDGJA-LLVKDONJSA-N Citronellyl acetate Natural products CC(=O)OCC[C@H](C)CCC=C(C)C JOZKFWLRHCDGJA-LLVKDONJSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N Coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N Nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N Phenethyl alcohol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WXCMHFPAUCOJIG-UHFFFAOYSA-N 4'-tert-Butyl-2',6'-dimethyl-3',5'-dinitroacetophenone Chemical compound CC(=O)C1=C(C)C([N+]([O-])=O)=C(C(C)(C)C)C([N+]([O-])=O)=C1C WXCMHFPAUCOJIG-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 240000002268 Citrus limon Species 0.000 description 1
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 1
- FLKPEMZONWLCSK-UHFFFAOYSA-N Diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 1
- HFJRKMMYBMWEAD-UHFFFAOYSA-N Dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 240000009136 Monarda didyma Species 0.000 description 1
- SUAUILGSCPYJCS-UHFFFAOYSA-N Musk ambrette Chemical compound COC1=C([N+]([O-])=O)C(C)=C([N+]([O-])=O)C=C1C(C)(C)C SUAUILGSCPYJCS-UHFFFAOYSA-N 0.000 description 1
- 229940067107 Phenylethyl Alcohol Drugs 0.000 description 1
- 235000016976 Quercus macrolepis Nutrition 0.000 description 1
- 244000305267 Quercus macrolepis Species 0.000 description 1
- 240000003136 Rosmarinus officinalis Species 0.000 description 1
- 235000002912 Salvia officinalis Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N methylphenylketone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000002020 sage Nutrition 0.000 description 1
- 239000001296 salvia officinalis l. Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Description
EpoxydringesEpoxy rings
trans-Ocimentrans-ocimen
trans-Epoxyocimentrans-epoxyocimes
sek.-Ocimenolsec-ocimenol
CHOCHO
1. CH3-CH2-CH = NR1. CH 3 -CH 2 -CH = NR
Z Hydrolyse/H + Z hydrolysis / H +
OROR
CHOCHO
«-Sinensal«-Sinensal
Die folgenden Beispiele, in welchen die Temperaturen in Celsiusgraden angegeben sind, zeigen, wie die Erfindung ausgeführt werden kann.The following examples, in which the temperatures are given in degrees Celsius, show how the Invention can be carried out.
Beispiel I
Herstellung von trans-EpoxyccimenExample I.
Manufacture of trans-epoxyccimes
Eine Lösung von 204 g trans-Ocimen und 150 g Natriumacetat in 750 ml Methylenchlorid wurde während 1 Stunde bei Raumtemperatur gerührt und dann innerhalb etwa 15 Minuten auf 0° abgekühlt. Anschließend wurde eine Lösung von 3 g Natriumacetat in 315 g 42%iger Peressigsäure tropfenweise mit einer solchen Geschwindigkeit eingetragen, daß die Temperatur des Reaktionsgemisches auf 20—25° stieg. Durch Aufrecherhalten einer geeigneten Zugabegeschwindigkeit, jedoch ohne Entfernung der Kühlvorrichtung, wurde die Temperatur konstant gehalten, bis die Zugabe der Peressigsäure beendet war. Unter diesen Bedingungen dauerte die Zugabe der Peressigsäure etwa 1 Stunde. Das Reaktionsgemisch wurde während weiterer 4 Stunden bei Raumtemperatur gerührt, worauf das feste Nebenprodukt abfiltriert und mit Methylenchlorid gewaschen wurde. Die vereinigten Methylenchloridlösungen wurden in Eiswasser gegossen, worauf das Gemisch kräftig geschüttelt und die organische Schicht abgetrennt wurde. Die letztere wurde mit Portionen von 125 ml der folgenden Lösungsmittel gewaschen: Wasser (einmal) gesättigte Natriumbicarbonatlösung (zweimal) und Wasser (einmal). Nach dem Trocknen und Einengen wurde der Rückstand destilliert. Man erhielt 205 g trans-Epoxyocimen (90% Ausbeute), Kp. = 45—47°/ 0,1 Torr, df = 0,9082; ng1 = 1,4802.A solution of 204 g of trans-Ocimen and 150 g of sodium acetate in 750 ml of methylene chloride was stirred for 1 hour at room temperature and then cooled to 0 ° over about 15 minutes. A solution of 3 g of sodium acetate in 315 g of 42% strength peracetic acid was then added dropwise at such a rate that the temperature of the reaction mixture rose to 20-25 °. By maintaining a suitable rate of addition, but without removing the cooling device, the temperature was held constant until the addition of the peracetic acid was complete. Under these conditions, the addition of the peracetic acid took about 1 hour. The reaction mixture was stirred for a further 4 hours at room temperature, after which the solid by-product was filtered off and washed with methylene chloride. The combined methylene chloride solutions were poured into ice water, the mixture was shaken vigorously and the organic layer was separated. The latter was washed with 125 ml portions of the following solvents: water (once), saturated sodium bicarbonate solution (twice) and water (once). After drying and concentration, the residue was distilled. 205 g of trans-epoxyocimen were obtained (90% yield), b.p. = 45-47 ° / 0.1 Torr, df = 0.9082; ng 1 = 1.4802.
Beispiel 2
Herstellung von cis-OcimenepoxydExample 2
Manufacture of cis-Ocimenepoxide
cis-Ocimen wurde in der im Beispiel 1 für trans-Ocimen beschriebenen Weise epoxydiert. Das cis-Ocimenepoxyd wies die folgenden Konstanten auf: df = 0,8996;«ϊ" = 1,4721. Die Ausbeute betrug etwa 90%.cis-Ocimen was epoxidized in the manner described in Example 1 for trans-Ocimen. The cis-Ocimenepoxide had the following constants: df = 0.8996; «ϊ" = 1.4721. The yield was about 90%.
Eine Parfümkomposition mit Lavendelgeruch wurde durch Mischen der folgenden Komponenten hergestellt: A perfume composition with a scent of lavender was prepared by mixing the following components:
1 In Phthalsäure-diäthylcster.1 In phthalic acid diethyl ester.
985985
Durch Zugabe von 15 Gewichtsteilen Irans-Epoxyoeimen zu dieser Riechstoffkomposition wurde deren Kopfnote wesentlich verstärkt und verbessert.By adding 15 parts by weight of Irans epoxy oils The top note of this fragrance composition has been significantly strengthened and improved.
Claims (4)
L cis-EpoxyocimenPatent claims:
L cis-epoxyocimen
Die für die Epoxydierung verwendete Persäure kann beispielsweise Peressigsäure, Perbenzoesäure; Monochlorperbenzoesäure oder Perphthalsäure sein. Als Lösungsmittel sind chlorierte Kohlenwasserstoffe, beispielsweise Chloroform, Methylenchlorid, Trichloräthylen oder Dichloräthan, verwendbar. Vorteilhaft ist die Verwendung von Peressigsäure in Methylenchlorid. Als Puffersubstanzen eignen sich beispielsweise organische Alkalisalze, wie Natrium- oder Kalium-formiat, -acetat, -propionat, -butyrat, -oxalat, -citrat oder -tartrat. Vorteilhafterweise wird Natriumacetat verwendet.The new compounds are prepared by epoxidizing the non-conjugated double bond of ocimen in a manner known per se using a peracid in a buffered medium.
The peracid used for the epoxidation can, for example, peracetic acid, perbenzoic acid; Be monochloroperbenzoic acid or perphthalic acid. Chlorinated hydrocarbons, for example chloroform, methylene chloride, trichlorethylene or dichloroethane, can be used as solvents. The use of peracetic acid in methylene chloride is advantageous. Organic alkali salts such as sodium or potassium formate, acetate, propionate, butyrate, oxalate, citrate or tartrate are suitable as buffer substances. Sodium acetate is advantageously used.
Die Monoepoxyde von cis-Ocimen und trans-Ocimen sind Riechstoffe, die interessante Geruchseigenschaften besitzen. Sie eignen sich besonders für die Verstärkung der Kopfnote von Parfümkompositionen und werden zweckmäßigerweise in Mengen von etwa 0,5 bis 3%, bezogen auf das Gesamtgewicht einer Parfümkomposition, verwendet. Diese Zahlen sind jedoch nicht als Grenzwerte aufzufassen, da die genannten Epoxyde je nach den gewünschten Geruchseffekten auch in höheren Mengen verwendet werden können.The selective epoxidation of the nichiconjugated double bond of the ocimene while avoiding attack on the other double bonds is a critical operation and must be carried out under carefully regulated conditions if good yields of the desired epoxide are to be achieved. It was z. B. found that the control of the reaction temperature by the usual methods is inadequate. The cooling capacity of the temperature control device (cooling apparatus) should be such that after the start of the addition of the epoxidizing agent at a certain rate, the temperature rises rapidly to a certain level and remains practically constant until the addition of the epoxidizing agent is complete. To achieve optimal yields it is advisable, for example, to cool the reaction vessel to about 0 ° C. and to add the epoxidizing agent drop by drop at such a rate that the temperature first rises to 20-25 ° C. and then remains practically constant at this level without the cooling device must be put out of operation.
The monoepoxides of cis-Ocimen and trans-Ocimen are fragrances that have interesting olfactory properties. They are particularly suitable for enhancing the top note of perfume compositions and are expediently used in amounts of about 0.5 to 3%, based on the total weight of a perfume composition. However, these figures are not to be taken as limit values, since the epoxides mentioned can also be used in larger quantities, depending on the desired odor effects.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH852967A CH478077A (en) | 1967-06-15 | 1967-06-15 | Preparation process for B-sinensal |
| CH1756867A CH488642A (en) | 1967-06-15 | 1967-12-14 | A-sinensal preparation process |
| CH1756867 | 1967-12-14 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1793710A1 DE1793710A1 (en) | 1972-10-19 |
| DE1793710B2 DE1793710B2 (en) | 1977-05-26 |
| DE1793710C3 true DE1793710C3 (en) | 1978-01-05 |
Family
ID=
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