CH520091A - Perfume intermediate - 14-methyl-bicyclo-(10,3,0)-pentadecene (1,12)- 13 prepn from bicyclo (10,3,0)-pentadecene (1,12)-one-(13) - Google Patents
Perfume intermediate - 14-methyl-bicyclo-(10,3,0)-pentadecene (1,12)- 13 prepn from bicyclo (10,3,0)-pentadecene (1,12)-one-(13)Info
- Publication number
- CH520091A CH520091A CH1401071A CH1401071A CH520091A CH 520091 A CH520091 A CH 520091A CH 1401071 A CH1401071 A CH 1401071A CH 1401071 A CH1401071 A CH 1401071A CH 520091 A CH520091 A CH 520091A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- bicyclo
- pentadecene
- methyl
- prepn
- Prior art date
Links
- 239000002304 perfume Substances 0.000 title abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 125000002619 bicyclic group Chemical group 0.000 claims abstract description 4
- 150000002576 ketones Chemical class 0.000 claims abstract description 4
- 230000000911 decarboxylating effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000012022 methylating agents Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 abstract description 3
- 230000001035 methylating effect Effects 0.000 abstract 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 abstract 1
- PJLHTVIBELQURV-UHFFFAOYSA-N pentadecene Natural products CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Bicyclic unsatd. ketone of formula (I): useful as starting material for muskone perfume is prepd. by (a) reacting bicyclo (10, 3, 0) pentadecene- 1(12) -one-(13) with a lower dialkyl carbonate; (b) methylating in an alkaline medium and (c) saponifying prod. under decarboxylating conditions.
Description
Verfahren zur Herstellung eines bicyclischen ungesättigten Ketons
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines neuen bicyclischen ungesättigten Ketons der Formel
EMI1.1
welches als Ausgangsstoff für die Synthese des bekannten Riechstoffes Muskon wertvoll ist.
Das Verfahren gemäss der Erfindung ist dadurch gekennzeichnet, dass man Bicyclo[10. 3. O]pentadecen-[1(12)]-on-(133 zunächst mit einem niederen Dialkylcarbonat, z. B. Dimethyl- oder Diäthylcarbonat, und anschliessend mit einem Methylierungsmittel, z. B. Methyljodid oder Schwefelsäuredimethylester, in alkalischem Medium umsetzt und das erhaltene Reaktionsprodukt unter decarboxylierend wirkenden Bedingungen verseift.
Das folgende Reaktionsschema veranschaulicht das oben definierte Verfahren.
EMI1.2
<tb>
<SEP> CH2 <SEP> C <SEP> C=O <SEP> CH2C <SEP> C=O
<tb> <SEP> Dialkyl- <SEP> 1
<tb> (cm2)8 <SEP> CH2 <SEP> ' <SEP> (CH2)8 <SEP> CH-COOAlk
<tb> <SEP> carbonat <SEP> l
<tb> <SEP> CH2-C <SEP> CH2 <SEP> CH2 <SEP> C <SEP> CH2
<tb> <SEP> Methylierungs- <SEP> l <SEP> mittel
<tb> <SEP> CH2 <SEP> C <SEP> C=O <SEP> CH2-C <SEP> C=O
<tb> <SEP> I <SEP> l <SEP> ALkali, <SEP> l <SEP> I <SEP> CH3
<tb> (CH2)s <SEP> I <SEP> CHCH3 <SEP> ( <SEP> (CH2)8
<tb> <SEP> H2O, <SEP> -CO2 <SEP> l <SEP> ICOOAlk
<tb> <SEP> CH2-C <SEP> CH2 <SEP> CH2-C <SEP> CH2
<tb>
Die folgenden Beispiele zeigen, wie das oben definierte Verfahren durchgeführt werden kann. Temperaturen sind in Celsiusgraden angegeben.
Beispiel 1
220,3 g (1 Mol) Bicyclo[10 .3. 0]pentadecen- [1(12)]-on-(13) werden in 240 g (2,03 Mol) Kohlensäurediäthylester aufgelöst und unter Rühren bei 50 bis 550 während 2 Stunden in eine Mischung von 720 g (6,01 Mol) Kohlensäurediäthylester und 108 g Natriummethylat (2 Mol) getropft. Bei einem Druck von etwa 80 mm Hg destilliert man langsam zunächst das entstehende Methanol und danach den überschüssigen Kohlensäurediäthylester ab. Anschliessend wird das zähflüssige Reaktionsprodukt mit Toluol verdünnt und bei Zimmertemperatur mit 142 g (1 Mol) Methyljodid drei Tage lang bei Raumtemperatur gerührt. Das vom Lösungsmittel befreite rohe Reaktionsprodukt wird mit 10 % Der Natronlauge verseift und angesäuert. Die organische Phase wird in Toluol aufgenommen.
Nach dem Abdampfen des Lösungsmittels reinigt man das rohe Reaktionsprodukt durch eine Vakuumdestillation.
Ausbeute: 80 g reines 14-Methyl-bicyclo[10. 3. Ojpentadecen-[1(12)J on-(13).
Konstanten: Sdp. 110-1120/0,03 mm Hg; n2r)0 = 1,5118; d24= 0,9910.
Beispiel 2
Zu 3600 g (30 Mol) von auf 550 erhitztes Di äthylcarbonat gibt man portionenweise 540 g (10 Mol) Natriummethylat zu. In das erhaltene Gemisch wird dann bei einem Druck von etwa 80 mm innerhalb von etwa 4 4i/2 Stunden unter Rühren eine Lösung von 1112 g (5 Mol) Bicyclo[10.3.0]pentadecen-[1(12)]-on-(13) zugegeben. Das Reaktionsgemisch wird während 2 Stunden bei 550 unter Destillationsbedingungen erhitzt. Der Destillationsrückstand wird auf etwa 250 abgekühlt und durch Eintragen in eine Mischung von 8 Liter Wasser und 1 Liter Eisessig und Rühren des Gemisches während 15 Minuten zersetzt. Die organische Phase wird abdekantiert, dreimal mit Wasser gewaschen und durch Destillation unter vermindertem Druck vom Di äthylcarbonat befreit. Man erhält 1426 g rohes 14-Äthoxycarbonyl-bicyclo[10 .3.
Ojcyclopenta- decen-[1(12)]-on-(13), das nach Umkristallisation aus Petroläther bei 53 bis 540 schmilzt. Man gewinnt überdies 2700 g Diäthylcarbonat zurück.
Einem Gemisch von 1169,6 g rohem 14-Äthoxycarbonyl-bicyclo[10. 3. 0]cyclopenta- decen-[1 (12)]-on-(13), 1200 ml Methanol und 756,8 g (6 Mol) Dimethylsulfat gibt man bei 30 bis 350 innerhalb von 3 Stunden unter Rühren eine Lösung von 324 g Natriummethylat in 1600 ml Methanol zu. Das Reaktionsgemisch wird während 4 Stunden unter Rückfluss bei 600 erhitzt und dann bei 600 innerhalb einer halben Stunde mit einer Mischung von 1200 ml 30 %iger Natronlauge und 1200 ml Wasser in 4 Portionen versetzt. Das Reaktionsgemisch wird während 4 Stunden bei 600 C gerührt. Das Methanol wird unter vermindertem Druck abdestilliert, worauf der Rückstand bei 500 mit Wasser verdünnt und mit 1800 ml 25%iger Schwefelsäure angesäuert wird. Das Reaktionsgemisch wird mit Toluol extrahiert.
Der Extrakt wird mit Wasser neutral gewaschen, über Natriumsulfat getrocknet und unter vermindertem Druck destilliert, um das Lösungsmittel zu entfernen. Man erhält 946 g Rohprodukt. Durch fraktionierte Destillation des letzteren erhält man 830 g (88,2%, bezogen auf den Ausgangsstoff) von bei 140 bis 1550/0,3 mm Hg überdestillierendem 1 4-Methyl-bicydo[10. 3. 0]pentadecen-[ 1(1 2)J- on-(13).
Process for the preparation of a bicyclic unsaturated ketone
The present invention relates to a process for the preparation of a new bicyclic unsaturated ketone of the formula
EMI1.1
which is valuable as a starting material for the synthesis of the well-known fragrance muscon.
The method according to the invention is characterized in that bicyclo [10. 3. O] pentadecen- [1 (12)] - one- (133 is reacted first with a lower dialkyl carbonate, e.g. dimethyl or diethyl carbonate, and then with a methylating agent, e.g. methyl iodide or sulfuric acid dimethyl ester, in an alkaline medium and the reaction product obtained is saponified under decarboxylating conditions.
The following reaction scheme illustrates the process defined above.
EMI1.2
<tb>
<SEP> CH2 <SEP> C <SEP> C = O <SEP> CH2C <SEP> C = O
<tb> <SEP> Dialkyl- <SEP> 1
<tb> (cm2) 8 <SEP> CH2 <SEP> '<SEP> (CH2) 8 <SEP> CH-COOAlk
<tb> <SEP> carbonate <SEP> l
<tb> <SEP> CH2-C <SEP> CH2 <SEP> CH2 <SEP> C <SEP> CH2
<tb> <SEP> methylation <SEP> l <SEP> medium
<tb> <SEP> CH2 <SEP> C <SEP> C = O <SEP> CH2-C <SEP> C = O
<tb> <SEP> I <SEP> l <SEP> ALkali, <SEP> l <SEP> I <SEP> CH3
<tb> (CH2) s <SEP> I <SEP> CHCH3 <SEP> (<SEP> (CH2) 8
<tb> <SEP> H2O, <SEP> -CO2 <SEP> l <SEP> ICOOAlk
<tb> <SEP> CH2-C <SEP> CH2 <SEP> CH2-C <SEP> CH2
<tb>
The following examples show how the method defined above can be carried out. Temperatures are given in degrees Celsius.
example 1
220.3 g (1 mole) bicyclo [10.3. 0] pentadecen- [1 (12)] - on- (13) are dissolved in 240 g (2.03 mol) of carbonic acid diethyl ester and, with stirring at 50 to 550 for 2 hours, in a mixture of 720 g (6.01 mol) Carbonic acid diethyl ester and 108 g of sodium methylate (2 mol) were added dropwise. At a pressure of about 80 mm Hg, first the methanol formed is slowly distilled off and then the excess diethyl carbonate. The viscous reaction product is then diluted with toluene and stirred at room temperature with 142 g (1 mol) of methyl iodide for three days at room temperature. The crude reaction product freed from the solvent is saponified with 10% sodium hydroxide solution and acidified. The organic phase is taken up in toluene.
After the solvent has been evaporated off, the crude reaction product is purified by vacuum distillation.
Yield: 80 g of pure 14-methyl-bicyclo [10. 3. Ojpentadecen- [1 (12) J on- (13).
Constants: bp 110-1120 / 0.03 mm Hg; n2r) 0 = 1.5118; d24 = 0.9910.
Example 2
540 g (10 mol) of sodium methylate are added in portions to 3600 g (30 mol) of diethyl carbonate heated to 550. A solution of 1112 g (5 mol) of bicyclo [10.3.0] pentadecen- [1 (12)] - on () is then added to the mixture obtained at a pressure of about 80 mm within about 4 4 1/2 hours with stirring. 13) added. The reaction mixture is heated at 550 for 2 hours under distillation conditions. The distillation residue is cooled to about 250 and decomposed by adding it to a mixture of 8 liters of water and 1 liter of glacial acetic acid and stirring the mixture for 15 minutes. The organic phase is decanted off, washed three times with water and freed from diethyl carbonate by distillation under reduced pressure. 1426 g of crude 14-ethoxycarbonyl-bicyclo [10 .3.
Ojcyclopentadecen- [1 (12)] - one- (13), which melts at 53 to 540 after recrystallization from petroleum ether. In addition, 2700 g of diethyl carbonate are recovered.
A mixture of 1169.6 g of crude 14-ethoxycarbonyl-bicyclo [10. 3. 0] cyclopentadecen- [1 (12)] - one (13), 1200 ml of methanol and 756.8 g (6 mol) of dimethyl sulfate are added to a solution of 324 at 30 to 350 within 3 hours with stirring g of sodium methylate in 1600 ml of methanol. The reaction mixture is heated under reflux at 600 for 4 hours and then treated at 600 within half an hour with a mixture of 1200 ml of 30% strength sodium hydroxide solution and 1200 ml of water in 4 portions. The reaction mixture is stirred at 600 ° C. for 4 hours. The methanol is distilled off under reduced pressure, whereupon the residue is diluted at 500 with water and acidified with 1800 ml of 25% strength sulfuric acid. The reaction mixture is extracted with toluene.
The extract is washed neutral with water, dried over sodium sulfate and distilled under reduced pressure in order to remove the solvent. 946 g of crude product are obtained. Fractional distillation of the latter gives 830 g (88.2%, based on the starting material) of 14-methyl-bicydo distilling over at 140 to 1550 / 0.3 mm Hg [10. 3. 0] pentadec- [1 (1 2) J-on- (13).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1401071A CH520091A (en) | 1966-12-08 | 1966-12-08 | Perfume intermediate - 14-methyl-bicyclo-(10,3,0)-pentadecene (1,12)- 13 prepn from bicyclo (10,3,0)-pentadecene (1,12)-one-(13) |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1401071A CH520091A (en) | 1966-12-08 | 1966-12-08 | Perfume intermediate - 14-methyl-bicyclo-(10,3,0)-pentadecene (1,12)- 13 prepn from bicyclo (10,3,0)-pentadecene (1,12)-one-(13) |
| CH288971A CH519456A (en) | 1966-12-08 | 1966-12-08 | Perfume intermediates - bicyclic unsatd ketones derived from cyclododecanone, for cyclopentadecanone prodn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH520091A true CH520091A (en) | 1972-03-15 |
Family
ID=4243873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1401071A CH520091A (en) | 1966-12-08 | 1966-12-08 | Perfume intermediate - 14-methyl-bicyclo-(10,3,0)-pentadecene (1,12)- 13 prepn from bicyclo (10,3,0)-pentadecene (1,12)-one-(13) |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH520091A (en) |
-
1966
- 1966-12-08 CH CH1401071A patent/CH520091A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |