DE2529603A1 - PROCESS FOR THE PRODUCTION OF NORPATCHOULENOL - Google Patents
PROCESS FOR THE PRODUCTION OF NORPATCHOULENOLInfo
- Publication number
- DE2529603A1 DE2529603A1 DE19752529603 DE2529603A DE2529603A1 DE 2529603 A1 DE2529603 A1 DE 2529603A1 DE 19752529603 DE19752529603 DE 19752529603 DE 2529603 A DE2529603 A DE 2529603A DE 2529603 A1 DE2529603 A1 DE 2529603A1
- Authority
- DE
- Germany
- Prior art keywords
- ppm
- acid
- norpatchoulenol
- formula
- solution
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 11
- OSQSDJNIURJARY-CDGCEXEKSA-N 41429-52-1 Chemical compound C1=CC[C@@]2(O)C(C)(C)[C@@H]3C[C@H]1[C@@]2(C)CC3 OSQSDJNIURJARY-CDGCEXEKSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- GGHMUJBZYLPWFD-CUZKYEQNSA-N patchouli alcohol Chemical compound C1C[C@]2(C)[C@@]3(O)CC[C@H](C)[C@@H]2C[C@@H]1C3(C)C GGHMUJBZYLPWFD-CUZKYEQNSA-N 0.000 claims description 7
- GGHMUJBZYLPWFD-UHFFFAOYSA-N rac-patchouli alcohol Natural products C1CC2(C)C3(O)CCC(C)C2CC1C3(C)C GGHMUJBZYLPWFD-UHFFFAOYSA-N 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000911 decarboxylating effect Effects 0.000 claims 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000283973 Oryctolagus cuniculus Species 0.000 description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 241000282472 Canis lupus familiaris Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 241000700159 Rattus Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- ACKFDYCQCBEDNU-UHFFFAOYSA-J lead(2+);tetraacetate Chemical compound [Pb+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ACKFDYCQCBEDNU-UHFFFAOYSA-J 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001738 pogostemon cablin oil Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000237369 Helix pomatia Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229940105631 nembutal Drugs 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- WEXRUCMBJFQVBZ-UHFFFAOYSA-N pentobarbital Chemical compound CCCC(C)C1(CC)C(=O)NC(=O)NC1=O WEXRUCMBJFQVBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/02—Saturated compounds containing hydroxy or O-metal groups
- C07C62/06—Saturated compounds containing hydroxy or O-metal groups polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
Description
PATENTANWALT DR. FRANZ LEDERERPATENT ADVOCATE DR. FRANZ LEDERER
6600/266600/26
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Norpatchoulenol, dem die FormelThe present invention relates to a process for the preparation of norpatchoulenol which has the formula
zukommt.comes to.
Norpatchoulenol ist eine bekannte Verbindung, die beispielsweise in der französischen Patentpublikation Nummer 2 151 522 beschrieben ist. Norpatchoulenol ist eine sehr wichtige Riechstoffkomponente von Patchouli-Oel, in welchem es in sehr viel geringern Eonzen-Norpatchoulenol is a well-known compound, for example in the French patent publication Number 2 151 522 is described. Norpatchoulenol is a very important fragrance component of patchouli oil, in which there is much less concentration of
Hl/18.6.1975St. / 18.6.1975
609808/1011609808/1011
trationen vorkommt, als Patchoulol. Letzteres ist, obwohl die Hauptkomponente von Patchouli-Oel darstellend, praktisch geruchlos. Das Verhältnis der "beiden Alkohole ist ungefähr 1:100.trations occurs as patchoulol. The latter is practical, although it is the main component of patchouli oil odorless. The ratio of the "two alcohols" is approximately 1: 100.
Das erfindungsgemässe Verfahren zur Herstellung von Norpatchoulenol (Formel I) ist dadurch gekennzeichnet, dass man die Säure der FormelThe inventive method for the production of Norpatchoulenol (formula I) is characterized in that one has the acid of the formula
1111
OOHOOH
oxidativ decarboxyliert.oxidatively decarboxylated.
Die oxidative. Decarboxylierung kann "beispielsweise mit Bleitetraacetat durchgeführt werden, wobei inerte organische oder polare koordinierende Lösungsmittel verwendet werden können, wie z.B. Benzol, Chlorbenzol, Chloroform, Dimethylformamid, Tetrahydrofuran, Acetonitril, Dioxan, Dimethylsulfoxid oder Pyridin. Die Reaktionsgeschwindigkeit hängt vom Lösungsmittel und von der Temperatur ab. Im allgemeinen wird man bestrebt sein, bei möglichst tiefen Temperaturen zu arbeiten, da damit Nebenreaktionen vermieden werden können. Die Temperatur kann aber im übrigen zwischen Raumtemperatur oder sogar darunter und der Rückflusstemperatur des Reaktionsgemisches liegen.The oxidative. Decarboxylation can be carried out, for example, with lead tetraacetate, with inert organic or polar coordinating solvents can be used, such as benzene, chlorobenzene, chloroform, Dimethylformamide, tetrahydrofuran, acetonitrile, dioxane, dimethyl sulfoxide or pyridine. The speed of response depends on the solvent and the temperature. In general one will strive for as deep as possible Temperatures to work, since side reactions can be avoided. The temperature can, however, between Room temperature or even below and the reflux temperature of the reaction mixture.
Vorzugsweise verwendet man für die erfindungsgemässe Reaktion Kupfer(II)acetat als Katalysator. Die Reaktion wird auch durch Basen, wie z.B. Pyridin, sowie durch Salze wie Lithiumacetat, katalysiert.Preference is given to using copper (II) acetate as catalyst for the reaction according to the invention. The reaction is also catalyzed by bases such as pyridine and salts such as lithium acetate.
609808/1011609808/1011
Die Säure der Formel II kann durch Oxidation der 4-Methy!gruppe von Patclioulol (Formel III)The acid of the formula II can be obtained by oxidation of the 4-methyl group of Patclioulol (formula III)
111111
erhalten werden. Diese Oxidation kann auf rein chemischem Wege oder nach einem "biologischen Verfahren vorgenommen werden. Ein besonders interessantes biologisches Oxidationsverfahren besteht darin, Patchoulol Kaninchen, Hunden oder Ratten oral zu verabreichen, wodurch das Patchoulol praktisch quantitativ zu einem G-emisch der Säure II und dem G-lykol der Formelcan be obtained. This oxidation can be carried out purely chemically or according to a "biological process" will. A particularly interesting biological oxidation process is patchoulol rabbits, dogs Or to administer rats orally, whereby the patchoulol practically quantitatively to a mixture of the acid II and the G-lycol of the formula
IVIV
CH OHCH OH
metabolisiert wird.is metabolized.
Each einem andern Verfahren zur Herstellung der Säure II verwendet man den Hydroxy-aldehydIn each other process for the preparation of the acid II one uses the hydroxy-aldehyde
CHOCHO
der seinerseits durch Oxidation aus dem Glykol IV erhalten werden kann, beispielsweise mittels Chromsäure in Pyridin.which in turn can be obtained from the glycol IV by oxidation, for example by means of chromic acid in pyridine.
6 09808/10116 09808/1011
Die Oxidation des Hydroxyaldehyde V zur Säure II kann z.B. mit feuchtem Silberoxid (in situ hergestellt aus Silbernitrat und Ammoniumhydroxid) durchgeführt werden.The oxidation of the hydroxyaldehyde V to the acid II can be carried out, for example, with moist silver oxide (prepared in situ from Silver nitrate and ammonium hydroxide).
Eine geringe Menge des Hydroxy-aldehyds der Formel V wird auch bei der oben erwähnten biologischen Oxidation von Patchoulol in Kaninchen, Hunden oder Ratten gebildet.A small amount of the hydroxy-aldehyde of the formula V is also used in the above-mentioned biological oxidation of Patchoulol is formed in rabbits, dogs, or rats.
Die Verbindungen der Formeln II, IV und V welche sich in der FormelThe compounds of the formulas II, IV and V which are in the formula
VlVl
worin R eine HOOC-, HOCH2- oder OHC-Gruppe bedeutet zusammenfassen lassen, sind neu und bilden ebenfalls Gegenstand der vorliegenden Erfindung.in which R denotes a HOOC, HOCH 2 or OHC group, are new and also form the subject of the present invention.
609808/1011609808/1011
Zu einer Lösung von 500 mg der Säure II, 200 mg Kupfer(II)-acetat und 1 ml Pyridin in 50 ml Benzol gi"bt man 800 mg Bleitetraacetat und erhitzt dann das Gemisch 30 Minuten zum Rückfluss. Nach dem Abkühlen fügt man 1,2-Propandiol zu und extrahiert mit Aethyläther. Die Verdampfung des Lösungsmittels ergibt ein OeI, das an SiOp ehromat ographiert wird. Man erhält so 300 mg eines Produktes, das auf Grund der dünnschichtchromatographischen, IE- und NMR-Analyse mit natürlichem Norpatchoulenol identisch ist.To a solution of 500 mg of acid II, 200 mg of copper (II) acetate and 1 ml of pyridine in 50 ml of benzene 800 mg of lead tetraacetate are added and the mixture is then refluxed for 30 minutes. After cooling 1,2-propanediol is added and the mixture is extracted with ethyl ether. Evaporation of the solvent gives an oil which is ographed on SiOp ehromat. You get 300 mg of a product that, due to the thin-layer chromatographic, IE and NMR analysis with natural norpatchoulenol is identical.
Die Säure II kann wie folgt erhalten werden:The acid II can be obtained as follows:
36 Stunden vor der Verabreichung von Patchoulol werden Kaninchen in Metabolismus-Käfige verbracht und dort 24 Stunden nüchtern gehalten. Dann erhält jedes Kaninchen (Albino, ca. 3 kg) 1 g Patchoulol (oder 1,5 bzw. 2 g je nach dem Versuch) als Suspension in 20 ml einer 1^-igen Carboxymethylcellulose-Lösung, anschliessend 25 ml Wasser. Die Verabreichung erfolgt am mit Nembutal (30 mg/kg) anästhesierten Tier. Nachher kann das Tier nach Belieben V/asser und Nahrung aufnehmen. Der Urin wird alle 24 Stunden gesammelt.36 hours before patchoulol administration rabbits are placed in metabolism cages and fasted there for 24 hours. Then each rabbit receives (Albino, approx. 3 kg) 1 g patchoulol (or 1.5 or 2 g depending on the experiment) as a suspension in 20 ml of a 1 ^ -igen Carboxymethyl cellulose solution, then 25 ml of water. The administration is carried out on the animal anesthetized with Nembutal (30 mg / kg). Afterwards the animal can eat and drink at will Ingesting food. The urine is collected every 24 hours.
Der während 26 Stunden gesammelte urin wird mit lOfo-lgev Salzsäure auf ein pH von 4,5 angesäuert. Dann fügt man 6 ml (ß-D-Glucuronid)-glucuronidase (Sue d'Helix Pomatia de I1Industrie Biologique Francaise) zu, lässt 24 Stunden bei 370C stehen und säuert dann auf pH = 1 an. Nach Sättigung mit NaCl wird die Lösung mit Aethylather extrahiert.The urine collected over the course of 26 hours is acidified to a pH of 4.5 with 10fo-lgev hydrochloric acid. Then 6 ml (β-D-glucuronide) -glucuronidase (Sue d'Helix Pomatia de I 1 Industrie Biologique Francaise) are added, left to stand at 37 ° C. for 24 hours and then acidified to pH = 1. After saturation with NaCl, the solution is extracted with ethyl ether.
609608/1011609608/1011
= δ τ-..= δ τ- ..
25796032579603
Hach Verdampfen des Aethers erhält man ein -viskoses OeI, das sofort an SiOp chromatographiert wird. Man erhält so 20 bis AOfo Säure II und 10 "bis 30fo Glykol IV mit Aethyläther (50$) und Petroläther (50$£) als Eluiermittel.After evaporation of the ether, a -viscous oil is obtained, which is immediately chromatographed on SiOp. This gives 20 to AOfo acid II and 10 "to 30% glycol IV with ethyl ether ($ 50) and petroleum ether ($ 50) as eluants.
Säure II:Acid II:
I.E.-^c=0 1700 cm"1 HMB: CH--C- 0,9 ppm (s, 3H) und 1,1 ppm (s, 6H)IE- ^ c = 0 1700 cm " 1 HMB: CH - C- 0.9 ppm (s, 3H) and 1.1 ppm (s, 6H)
I.E.^0n = 3600 und 3500 cm"1 . VC=Q 1725 cm"1 HMR: CH--C- 0,9 ppm (s, 3H), 1,10 ppm (s,IE ^ 0n = 3600 and 3500 cm " 1. V C = Q 1725 cm" 1 HMR: CH - C- 0.9 ppm (s, 3H), 1.10 ppm (s,
und 1,13 ppm (s, 3H), CSLo-c- 3,65 ppm (s, 3H)and 1.13 ppm (s, 3H), CSLo-c- 3.65 ppm (s, 3H)
O Glykol IV: O glycol IV:
F = 104-1050C [oCß]^01? = -120° I.R.Vrvrr = 3620 und 3450 cm"1 F = 104-105 0 C [oCß] ^ 01 ? = -120 ° IRVrvrr = 3620 and 3450 cm " 1
UJlUJl
HMHi OEL-G- 0,85 ppm (s, 3H) und 1,1 ppm (s, 6H) -C-CH9 3,45 ppm (d, J=7,5 Hz, 2H) H OHHMHi OEL-G- 0.85 ppm (s, 3H) and 1.1 ppm (s, 6H) -C-CH 9 3.45 ppm (d, J = 7.5 Hz, 2H) H OH
I.E. V Qg = 3600 und 3500 cm"1, Vc=0 1725 cm"1 HMR; ΟΗ,-y- 0,85 ppm (s, 3H) und 1,1 ppm (s, 6H) CH5-C-O- 2,05 ppm (s, 3H), -C-CH2-O-C-IE V Qg = 3600 and 3500 cm " 1 , V c = 0 1725 cm" 1 HMR; ΟΗ, -y- 0.85 ppm (s, 3H) and 1.1 ppm (s, 6H) CH 5 -CO- 2.05 ppm (s, 3H), -C-CH 2 -OC-
0 HO0 HO
3,90 ppm (d, J = 7,5 Hz, 2H).3.90 ppm (d, J = 7.5 Hz, 2H).
— 1 — - 1 -
3 g Chromsäureanhydrid/Pyridin-Komplex werden in 50 ml Methylenchlorid, enthaltend 6 Tropfen Pyridin, gelöst. Man fügt dann die lösung von 460 mg des Glykols IV in 10 ml Methylenchlorid zu und rührt 4 Stunden bei Raumtemperatur. Das Reaktionsgemiseh wird filtriert und der Niederschlag mit 50 ml Methylenchlorid gewaschen. Die vereinigten Filtrate werden gewaschen;4 mal mit je 10 ml einer 5^-igen wässerigen Sodalösung, 3 mal mit je 10 ml einer 10?&-igen Salzsäurelösung, 2 mal mit je 10 ml einer gesättigten wässerigen Natriumbicarbonatlösung und schliesslich 2 mal mit je 10 ml Wasser. Die organische Lösung wird über Natriumsulfat getrocknet, dann filtriert. Nach Destillation des Lösungsmittels erhält man 465 mg des Aldehyds V, der sich durch Chromatographie an einer SiOp-Kolonne reinigen lässt. Der gereinigte Aldehyd V kann durch folgende Daten charakterisiert werden:3 g of chromic anhydride / pyridine complex are dissolved in 50 ml of methylene chloride containing 6 drops of pyridine. The solution of 460 mg of glycol IV in 10 ml of methylene chloride is then added and the mixture is stirred for 4 hours at room temperature. The reaction mixture is filtered and the precipitate is washed with 50 ml of methylene chloride. The combined filtrates are washed; 4 times with 10 ml each of a 5 ^ aqueous Soda solution, 3 times with 10 ml each of a 10% hydrochloric acid solution, 2 times with 10 ml each of a saturated aqueous sodium bicarbonate solution and finally 2 times with 10 ml each Water. The organic solution is dried over sodium sulfate, then filtered. After distillation of the solvent 465 mg of aldehyde V are obtained, which is determined by chromatography can be cleaned on a SiOp column. The cleaned one Aldehyde V can be characterized by the following data:
[aD]0HC!13 = -40° ; IR: S>0H bei 3500 cm"1, ν ö==0 bei 1715 cnf1; MMR: GH--0- Singlett (3 H) bei 0,89 ppm; CEU-C- 2 vereinigte Singlette (6H) bei 1,08 ppm; -C- CHO Singlett (IH) bei 9,64 ppm,[a D ] 0HC! 1 3 = -40 °; IR: S> 0H at 3500 cm " 1 , ν ö == 0 at 1715 cnf 1 ; MMR : GH - 0 singlet (3 H) at 0.89 ppm; CEU-C- 2 united singlets (6H) at 1.08 ppm; -C- CHO singlet (IH) at 9.64 ppm,
Zu einer Lösung von 440 mg Silbernitrat in 1 ml Wasser gibt man unter Rühren eine Lösung von 200 mg Natriumhydroxid in 1 ml Wasser, dann die Lösung von I46 mg des Aldehyds Y in 0,5 ml Pentan. Man rührt 30 Minuten bei Raumtemperatur und erwärmt dann während 2 Stunden. Nach dem Abkühlen filtriert man und wäscht den Niederschlag mit 10 ml warmem Wasser. Die vereinigten Eiltrate werden 2 mal mit je 5 ml Aethylather von 220B angesäuert. Man fügt Natriumchlorid bis zur Sättigung der Lösung zu und extrahiert 3 mal mit je 10 ml Aethyläther.To a solution of 440 mg of silver nitrate in 1 ml of water, a solution of 200 mg of sodium hydroxide in 1 ml of water is added with stirring, then the solution of 146 mg of aldehyde Y in 0.5 ml of pentane. The mixture is stirred for 30 minutes at room temperature and then heated for 2 hours. After cooling, it is filtered and the precipitate is washed with 10 ml of warm water. The combined Eiltrate are acidified twice with 5 ml of ethyl ether of 22 0 B twice. Sodium chloride is added until the solution is saturated and it is extracted 3 times with 10 ml of ethyl ether each time.
25796032579603
Die vereinigten Aetherphasen werden mit gesättigter ITatriumchloridlösung gewaschen und dann über Natriumsulfat getrocknet. Fach Filtration wird das Lösungsmittel abdestilliert, Man erhält 110 mg der Säure II mit folgenden charakteristischen physiko-chemiechen Konstanten:The combined ether phases are washed with saturated sodium chloride solution and then over sodium sulfate dried. Subject filtration, the solvent is distilled off. 110 mg of acid II are obtained with the following characteristics physico-chemical constants:
[O0] 01101J = -87°; IR: Vco "bei 1700 cnT1,^ bei 3180 und 2600 cm"1, V0H bei 3480 cm"1; FMR: CH3-C- Singlett (3H) bei[O 0 ] 01101 J = -87 °; IR: V co "at 1700 cnT 1 , ^ at 3180 and 2600 cm" 1 , V 0H at 3480 cm "1; FMR: CH 3 -C- singlet (3H) at
0,88 ppm; CH3-C- Singlett (3H) bei 1,08 ppm; CH3-C- Singlett (3H) bei 1,11 ppm.0.88 ppm; CH 3 -C singlet (3H) at 1.08 ppm; CH 3 -C singlet (3H) at 1.11 ppm.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1067674A CH589018A5 (en) | 1974-08-02 | 1974-08-02 | Norpatchoulenol mfr. by oxidative decarboxylation of corresp. acid - obtd. by e.g. oxidn. of patchoulol |
| CH460275 | 1975-04-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2529603A1 true DE2529603A1 (en) | 1976-02-19 |
Family
ID=25695870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19752529603 Withdrawn DE2529603A1 (en) | 1974-08-02 | 1975-07-02 | PROCESS FOR THE PRODUCTION OF NORPATCHOULENOL |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5143750A (en) |
| DE (1) | DE2529603A1 (en) |
| FR (1) | FR2280625A1 (en) |
| GB (1) | GB1457719A (en) |
| NL (1) | NL7508836A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008663A1 (en) * | 1978-08-10 | 1980-03-19 | L. Givaudan & Cie Société Anonyme | Methanonaphthalene, as well as a process for its preparation and its use for the preparation of norpatchoulenol |
-
1975
- 1975-07-02 DE DE19752529603 patent/DE2529603A1/en not_active Withdrawn
- 1975-07-24 FR FR7523128A patent/FR2280625A1/en active Granted
- 1975-07-24 NL NL7508836A patent/NL7508836A/en not_active Application Discontinuation
- 1975-07-30 JP JP9299775A patent/JPS5143750A/en active Pending
- 1975-08-01 GB GB3225875A patent/GB1457719A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008663A1 (en) * | 1978-08-10 | 1980-03-19 | L. Givaudan & Cie Société Anonyme | Methanonaphthalene, as well as a process for its preparation and its use for the preparation of norpatchoulenol |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1457719A (en) | 1976-12-08 |
| FR2280625B1 (en) | 1980-05-16 |
| JPS5143750A (en) | 1976-04-14 |
| NL7508836A (en) | 1976-02-04 |
| FR2280625A1 (en) | 1976-02-27 |
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