DE1793079B1 - Process for the preparation of 2- (2'-methyl-1'-propenyl) -4-methyl-tetrahydropyran (rose oxide) - Google Patents
Process for the preparation of 2- (2'-methyl-1'-propenyl) -4-methyl-tetrahydropyran (rose oxide)Info
- Publication number
- DE1793079B1 DE1793079B1 DE19681793079 DE1793079A DE1793079B1 DE 1793079 B1 DE1793079 B1 DE 1793079B1 DE 19681793079 DE19681793079 DE 19681793079 DE 1793079 A DE1793079 A DE 1793079A DE 1793079 B1 DE1793079 B1 DE 1793079B1
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- propenyl
- rose oxide
- tetrahydropyran
- preparation
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title description 10
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 title description 10
- 229930007790 rose oxide Natural products 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- WQNLWKDARWVSKE-UHFFFAOYSA-N 2,6-dimethyloct-2-ene Chemical compound CCC(C)CCC=C(C)C WQNLWKDARWVSKE-UHFFFAOYSA-N 0.000 description 1
- -1 3 - chloro - 2,6 - dimethyl - octene Chemical compound 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrane Compounds (AREA)
Description
:".'ie Erfindung betrifft ein Verfahren zur Herstellung von 2-U'-Methyl-l'-propenyl)-4-methyltetrah v"or-yran (Rosenoxyd), das dadurch gekennzeichnet isi,üaiÄman5-Chior-2,6-dimethyl-octen-(li-ol-(8)bei J6( ii 26UC eier Pyrolyse unterwirft.: "The invention relates to a method of manufacture of 2-U'-methyl-1'-propenyl) -4-methyltetrah v "or-yran (rose oxide), which is characterized by, üaiÄman5-Chior-2,6-dimethyl-octen- (li-ol- (8) bei J6 (ii 26UC eggs subjected to pyrolysis.
λ us aer bntiscnen Patentschrift 1 079 421 sind mehrere verfahren zur Herstellung von Rosenoxyd, ausgehend von 3-Chlor-2,6-dimethyl-1-octen-8-öl, bekannt. Das ais einziges durchgeführte Verfahren berunt auf Behandeln des Ausgangsmaterials mit Säure. Es stellt dies zweifelsohne das einfachste und deshalb auch vorteilhafteste der verschiedenen Verfahren der britischen Patentschrift dar.There are several of these in patent specification 1,079,421 Process for the production of rose oxide, starting from 3-chloro-2,6-dimethyl-1-octene-8-oil, is known. The only process performed is based on treating the starting material with acid. It This is undoubtedly the simplest and therefore also the most advantageous of the various methods of the British patent specification.
Gegenüber diesem Verfahren weist das erfindungsgemäße Verfahren die Vorteile auf, daß es in der Durchführung einfacher ist, sich zur kontinuierlichen Herstellung von Rosenoxyd vorzüglich eignet und ein reineres Produkt liefert.Compared to this method, the method according to the invention has the advantages that it can be carried out is simpler, is eminently suitable for the continuous production of rose oxide and a Delivers purer product.
Bei dem erfindungsgemäßen Verfahren wird ein Gemisch von eis- und trans-Isomeren des Rosenoxyds erhalten, in dem das geruchlich besonders wertvolle cis-Isomere überwiegt. Das erhaltene Pyrolysat kann durch übliche Reinigungsmethoden, z. B. durch Vakuumdestillation und/oder Säulenchromatographie an Silicagel, gereinigt werden.In the process according to the invention, a mixture of cis and trans isomers of rose oxide is used obtained, in which the odor-particularly valuable cis-isomer predominates. The pyrolysate obtained can by common cleaning methods, e.g. B. by vacuum distillation and / or column chromatography Silica gel.
Das als Ausgangsmaterial verwendete 3-Chlor-2,6-dimethyl-octen-(l)-ol-(8) kann nach der britischen Patentschrift 1 079 421 oder durch Chlorierung von 2,6 - Dimethyl - 2 - octen - (1) - öl - (8) mit Chlor in Tetrachlorkohlenstoff hergestellt werden.The 3-chloro-2,6-dimethyl-octen- (l) -ol- (8) used as starting material can according to British Patent 1,079,421 or by chlorination of 2,6 - dimethyl - 2 - octene - (1) - oil - (8) with chlorine in carbon tetrachloride getting produced.
Die folgenden Beispiele erläutern das erfindungsgemäße Verfahren.The following examples explain the process according to the invention.
;-Chlor-2,6-dimethyl-octen-!l)-ol-(8) wird in einen auf 260" C (Wandtemperatur) erhitzten Kolben eingetropft. Gleichzeitig wird durch den Kolben ein btick-Stickstoffstrom von etwa 1 l/Min, geleitet. Die mit dem Stickstoffstrom aus dem Kolben austretenden Pyrolyseprodukte werden kondensiert und das Kondensat an einer mit Siiicagel (0,05 bis 0,2 mm) beschickten Säule Chromatographien, wobei mit einem Ge-.mi^ch von Petrolather (Kp. 40 bis 50 C) Aceton (95:5) eluiert wird. Aus 5.57 g 3-Chlor-2,6-dimethyioctsn-ü )-ol-(8) werden neben 3,73 g nicht umgesetztem Ai; .gangsmaterial 0,98 g eis - trans - 2 - (2' - Methvii -propenyi)-4-methyltetrahydropyran(cis:trans = 2: ii voüi Kp. 10 70 bis 75 C erhalten. ; -Chlor-2,6-dimethyl-octen-! L) -ol- (8) is added dropwise to a flask heated to 260 "C (wall temperature). At the same time, a stream of nitrogen of about 1 l / min. The pyrolysis products emerging from the flask with the nitrogen stream are condensed and the condensate is chromatographed on a column filled with silica gel (0.05 to 0.2 mm), with a mixture of petroleum ether (bp 40 to 50 C) acetone (95: 5) is eluted. From 5.57 g of 3-chloro-2,6-dimethyioctsn-ü) -ol- (8), in addition to 3.73 g of unreacted aluminum starting material, 0.98 g of ice - trans - 2 - (2 '- Methvii -propenyi) -4-methyltetrahydropyran (cis: trans = 2: ii voüi bp 10 70 to 75 ° C obtained.
Das als Ausgangsmaterial verwendete j-Chior-2.6-dimethyl-octen-(l )-oi-(S) ist wie folgt erhalten worden: Eine Lösung von 2 g 2,6-Dimethyl-2-octen-( 1 )-0I-18) in 250 ml Tetrachlorkohlenstoff wird tropfenweise bei 25 C mit einer Lösung von Chlor in Tetrachlorkohlenstoff versetzt, während gleichzeitig ein Stickstoffstrom (4 l/Min.) durch die Reaktionslösung geleitet wird. Die Reaktion wird abgebrochen, sobald mittels der Dünnschichtchromatographie Kein Ausgarjgsmaterial mehr im Reaktionsgemisch nachweisbar ist. Das Lösungsmittel wird dann bei 30° C im Wasserstrahlvakuum abgezogen und der Rückstand an einer Silicagelsäule (0,05 bis 0,2 mm) mit einem Gemisch von Petrolather (Kp. 40 bis 500C) Aceton (95:5) chromatographiert. Man erhält 3-Chlor-2,6-dimethylocten-(l)-ol-(8), das folgende Infrarotabsorptionsbanden aufweist: 908 OC = CH2). 3083 OC = CH2), 1646 (>C = CH2), 3344 (OH), 1060 (OH)cm"1. Die Ausbeute beträgt 97% der Theorie.The j-Chior-2.6-dimethyl-octen- (l) -oi- (S) used as starting material was obtained as follows: A solution of 2 g of 2,6-dimethyl-2-octen- (1) -OI- 18) In 250 ml of carbon tetrachloride, a solution of chlorine in carbon tetrachloride is added dropwise at 25 C, while a stream of nitrogen (4 l / min.) Is passed through the reaction solution at the same time. The reaction is terminated as soon as no more exhausting material can be detected in the reaction mixture by means of thin-layer chromatography. The solvent is then stripped at 30 ° C in a water jet vacuum and (0.05 to 0.2 mm) of the residue on a silica gel with a mixture of petroleum ether acetone: chromatographed (b.p. 40 to 50 0 C.) (95 5). 3-chloro-2,6-dimethylocten- (1) -ol- (8) is obtained, which has the following infrared absorption bands: 908 OC = CH 2 ). 3083 OC = CH 2 ), 1646 (> C = CH 2 ), 3344 (OH), 1060 (OH) cm " 1. The yield is 97% of theory.
20 g 3 - Chlor - 2,6 - dimethyl - octen - (1) - öl - (8) werden gemäß Beispiel 1 pyrolysiert. Das erhaltene kondensierte Pyrolysat wird dann mit 5% (bezogen auf das Ausgangsmaterial) Bortrioxid versetzt und 5 Minuten auf 100 bis 110° C erhitzt, um alkoholische Bestandteile in nicht flüchtige Ester zu überführen. Anschließend wird das Reaktionsgemisch vakuumdestilliert, wobei man beim Kp.10 70 bis 8O0C 4,5 g reines cis-2-(2'-Methyl-Y-propenyl)-4-methyltetrahydropyran erhält.20 g of 3 - chloro - 2,6 - dimethyl - octene - (1) - oil - (8) are pyrolyzed according to Example 1. The condensed pyrolysate obtained is then mixed with 5% (based on the starting material) boron trioxide and heated to 100 to 110 ° C. for 5 minutes in order to convert alcoholic constituents into non-volatile esters. The reaction mixture is vacuum distilled to give in Kp. 10 70 to 8O 0 C 4.5 g of pure cis-2- (2'-methyl -Y- propenyl) -4-methyltetrahydropyran.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1201267A CH484893A (en) | 1967-08-24 | 1967-08-24 | Method for producing a fragrance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1793079B1 true DE1793079B1 (en) | 1972-02-03 |
Family
ID=4379019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681793079 Pending DE1793079B1 (en) | 1967-08-24 | 1968-07-31 | Process for the preparation of 2- (2'-methyl-1'-propenyl) -4-methyl-tetrahydropyran (rose oxide) |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE719879A (en) |
| CH (1) | CH484893A (en) |
| DE (1) | DE1793079B1 (en) |
| ES (1) | ES357510A1 (en) |
| FR (1) | FR1603259A (en) |
| GB (1) | GB1180160A (en) |
| NL (1) | NL138931B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021769A1 (en) * | 1979-06-19 | 1981-01-07 | Sumitomo Chemical Company, Limited | Processes for producing 2,6-dimethyl-3-alkoxy-oct-1-en-8-ol, dehydrocitronellol and 2-(2'-methyl-1'-propenyl)-4-Methyltetrahydropyran |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1079421A (en) * | 1964-06-18 | 1967-08-16 | Boake Roberts & Co Ltd | Chlorinated citronellol and its conversion to rose oxide |
-
1967
- 1967-08-24 CH CH1201267A patent/CH484893A/en not_active IP Right Cessation
-
1968
- 1968-07-31 DE DE19681793079 patent/DE1793079B1/en active Pending
- 1968-08-08 GB GB3787668A patent/GB1180160A/en not_active Expired
- 1968-08-19 NL NL6811790A patent/NL138931B/en unknown
- 1968-08-21 FR FR1603259D patent/FR1603259A/en not_active Expired
- 1968-08-23 ES ES357510A patent/ES357510A1/en not_active Expired
- 1968-08-23 BE BE719879D patent/BE719879A/xx unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1079421A (en) * | 1964-06-18 | 1967-08-16 | Boake Roberts & Co Ltd | Chlorinated citronellol and its conversion to rose oxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0021769A1 (en) * | 1979-06-19 | 1981-01-07 | Sumitomo Chemical Company, Limited | Processes for producing 2,6-dimethyl-3-alkoxy-oct-1-en-8-ol, dehydrocitronellol and 2-(2'-methyl-1'-propenyl)-4-Methyltetrahydropyran |
Also Published As
| Publication number | Publication date |
|---|---|
| CH484893A (en) | 1970-01-31 |
| BE719879A (en) | 1969-02-24 |
| GB1180160A (en) | 1970-02-04 |
| NL6811790A (en) | 1969-02-26 |
| FR1603259A (en) | 1971-03-29 |
| ES357510A1 (en) | 1970-03-16 |
| NL138931B (en) | 1973-05-15 |
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