DE931351C - Process for the production of isomeric 6-methyl-ª ‡ -ionons (ª ‡ -ions) by ring closure of 3-methyl pseudoionons - Google Patents
Process for the production of isomeric 6-methyl-ª ‡ -ionons (ª ‡ -ions) by ring closure of 3-methyl pseudoiononsInfo
- Publication number
- DE931351C DE931351C DEP31424A DEP0031424A DE931351C DE 931351 C DE931351 C DE 931351C DE P31424 A DEP31424 A DE P31424A DE P0031424 A DEP0031424 A DE P0031424A DE 931351 C DE931351 C DE 931351C
- Authority
- DE
- Germany
- Prior art keywords
- vol
- methyl
- ring closure
- ionons
- isomeric
- 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
- 238000006798 ring closing metathesis reaction Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 13
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 235000000396 iron Nutrition 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 claims 1
- 238000007363 ring formation reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000007659 semicarbazones Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000015164 Iris germanica var. florentina Nutrition 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000000659 freezing mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 244000023249 iris florentino Species 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von isomeren 6-Methyl-a-jononen (a-Ironen) durch Ringschluß von 3-Methylps eudoj ononen Die Erfindung betrifft die Herstellung eines Gemisches von 6-Methyl-α-jononen (α-Ironen) mit einem hohen Gehalt an einem Stereoisomeren, welches ein 4-Phenylsemicarbazon vom Schmelzpunkt 164,5 bis I650 und ein Dihydroketon liefert (dessen Semicarbazon bei I72,5 bis I730 und dessen 2, -Dinitrophenylhydrazon bei I30 bis 13I° schmilzt). Beim gegenwärtigen Stand der Wissenschaft kann man annehmen, daß dieses Stereoisomere die cis (2,6)-Struktur aufweist (Naves, Helvetica Chimica Acta, Bd.31, 1948, S. 905), während das ein 4-Phenylsemicarbazon vom Schmelzpunkt 174,5 bis 175,50 liefernde Stereoisomere (Naves, Grampoloff, Bachmann, Helvetica Chimica Acta, Bd. 30, I947, S. I609 und 222I) die trans (2,6)-Struktur aufweisen wurde. Das Stereoisomere, dessen -Phenylsemicarbazon bei 164,5 bis I650 (162 bis I630) schmilzt, kommt in der racemischen und aktiven Form in der Irisessenz vor und verleiht dieser überwiegend ihre hohe Bedeutung für die Riechstoffindustrie (Naves, Bachmann, Helvetica Chimica Acta, Bd. 30, 1947, 5. 2222 bis 2243, und Bd. 3I, 1948, S. 894).Process for the preparation of isomeric 6-methyl-a-ions (a-irons) by ring closure of 3-methylps eudoj ononen The invention relates to manufacture a mixture of 6-methyl-α-ions (α-irons) with a high content on a stereoisomer which is a 4-phenylsemicarbazone of melting point 164.5 to I650 and a dihydroketone (its semicarbazone at I72.5 to I730 and its 2, -Dinitrophenylhydrazone melts at 130 to 131 °). At the present According to the state of the art, one can assume that this stereoisomer has the cis (2,6) structure (Naves, Helvetica Chimica Acta, Vol. 31, 1948, p. 905), while a 4-phenylsemicarbazone from melting point 174.5 to 175.50 yielding stereoisomers (Naves, Grampoloff, Bachmann, Helvetica Chimica Acta, Vol. 30, I947, pp. I609 and 222I) the trans (2,6) structure was exhibited. The stereoisomer, its -phenylsemicarbazone at 164.5 to 1650 (162 to 1630) melts, comes in the racemic and active form in the iris essence and gives this predominantly its high importance for the fragrance industry (Naves, Bachmann, Helvetica Chimica Acta, vol. 30, 1947, pp. 2222-2243, and vol. 3I, 1948, p. 894).
Der Ringschluß der Pseudoirone durch Einwirkung von Schwefelsäure oder Phosphorsäure führt bei Anlehnung an die Ringschlußverfahren für Pseudojonone zu Gemischen, in denen das dl-a-Iron überwiegt, dessen -Phenylsemicarbazon bei 174,5 bis I75,50 schmilzt (Naves, Helvetica Chimica Acta, Bd. 3I, I948, S. 900, und die in dieser Abhandlung erwähnten Veröffentlichungen). The ring closure of the pseudoirons by the action of sulfuric acid or phosphoric acid, based on the ring closure process, leads to pseudojonones to mixtures in which the dl-a-iron predominates, its -phenylsemicarbazone at 174.5 until I75,50 melts (Naves, Helvetica Chimica Acta, Vol. 3I, I948, p. 900, and the in publications mentioned in this paper).
Die Erfindung betrifft ein Verfahren zur Herstellung von isomeren 6-Methyl-a-j ononen (a-Ironen) durch Ringschluß von 3-Methylpseudojononen, gekennzeichnet durch die Verwendung von Bortrifluorid in wasserfreiem Medium als Ringschlußmittel für Pseudoirone zur Herstellung von Gemischen, die einenhohenGehalt ana-Ironen und in besondere an dem Stereoisomeren aufweisen, dessen 4-Phenylsemicarbazon bei 164,5 bis I650 schmilzt, und das den für die Riechstoffindustrie wichtigsten Bestandteil der aus dem ätherischen Öl der Iriswurzeln erhaltenen Ketonprodukte bildet. The invention relates to a process for the preparation of isomers 6-methyl-a-ionons (a-irons) characterized by the ring closure of 3-methyl pseudojonones through the use of boron trifluoride in an anhydrous medium as a ring closure agent for pseudoirons for the preparation of mixtures that have a high content of ana-iron and have in particular in the stereoisomer, its 4-phenylsemicarbazone at 164.5 melts to I650, and that is the most important component for the fragrance industry which forms ketone products obtained from the essential oil of orris roots.
Es wurde nun gefunden, daß die Verwendung von Bortrifluqrid als Ringschlußmittel in wasserfreiem Medium ein Irongemisch liefert, das nicht nur einen sehr hohen Gehalt an a-Isomerem, sondern vornehmlich an jenem Isomeren aufweist, dessen 4-Phenylsemicarbazon bei 164,5 bis I650 schmilzt. It has now been found that the use of boron trifluoride as a ring closing agent in an anhydrous medium provides an iron mixture that not only has a very high content of the a-isomer, but primarily of that isomer whose 4-phenylsemicarbazone melts at 164.5 to 1650.
Das vorliegende Verfahren ist im folgenden näher beschrieben, doch ist die Erfindung nicht auf die hier gemachten Angaben beschränkt. Sie erstreckt sich vielmehr unter Berücksichtigung der aufgeführten Beschränkungen auch auf andere Möglichkeiten, wie sie sich aus Veränderungen der Temperatur, der Konzentration der Umsetzungsmittel ergeben. The present method is detailed below, however the invention is not limited to the information given here. She stretches rather, it also applies to others, taking into account the restrictions listed Ways of how they arise from changes in temperature, concentration the conversion funds result.
Beispiel 103 g technisches Pseudoiron, das durch Kondensation von 3-Methylcitral mit Aceton erhalten wurde und folgende Eigenschaften aufweist: D24° = o,goo8; n25= 1,53420; Dispersion nF-nC = o,o2630; Titer (durch Oximierung) = 98,4 0/o und 300 g trockenes Benzol werden mit einem Eis-Salz-Gemisch auf oO abgekühlt. Dieses Gemisch wird innerhalb 45 Minuten mit 38 g Bortrifluorid unter lebhaftem Rühren und Einhaltung einer Temperatur von o bis 50 versetzt. Nach Einbringen von etwa 33 g des Umsetzungsmittels stieg die Temperatur trotz der Kältemischung auf 12 bis I50 an und blieb ioMinuten über 100. Sobald diese Temperatur erreicht und die Zugabe des Bortrifluorids beendet ist, werden unter ständigem Weiterrühren bei einer Temperatur von weniger als 100 560 ccm einer 80/oigen wäßrigen Natronlauge zugegeben. Die Farbe des Gemisches, die bei der Zugabe des Bortrifluorids nach dunkelbraun umgeschlagen ist, wird rasch blaßgelb. Nach beendeter Zugabe des Alkalis wird die Benzolschicht durch Dekantieren abgetrennt und neutral gewaschen. Das Benzol wird abdestilliert und der Rückstand bei vermindertem Druck fraktioniert. Example 103 g of technical pseudoiron obtained by condensation of 3-methylcitral was obtained with acetone and has the following properties: D24 ° = o, goo8; n25 = 1.53420; Dispersion nF-nC = o, o2630; Titer (by oximation) = 98.4 0 / o and 300 g of dry benzene are cooled to oO with an ice-salt mixture. This mixture is stirred with 38 g of boron trifluoride within 45 minutes Stirring and maintaining a temperature of 0 to 50 are added. After introducing about 33 g of the reaction agent, the temperature rose despite the freezing mixture 12 to 150 and stayed 10 minutes over 100. As soon as this temperature was reached and the addition of the boron trifluoride is complete, stirring continuously a temperature of less than 100 560 ccm of 80% aqueous sodium hydroxide solution admitted. The color of the mixture, which was dark brown when the boron trifluoride was added is turned over, quickly turns pale yellow. After the addition of the alkali is complete, the The benzene layer was separated off by decantation and washed neutral. The benzene will distilled off and the residue fractionated under reduced pressure.
Man erhält 85,2 g Iron, d. h. 82,7°/ der Theorie, mit einem Titer von 98,60/0 (Oximierung), das nach der Refraktionsdispersion 92 bis 95 ob a-Iron enthält: D240 = o,g362; n020 = I,50I42; Dispersion nF-nC = o,OI350.85.2 g of iron are obtained, i.e. H. 82.7 ° / of theory, with a titer of 98.60 / 0 (oximation), which after refraction dispersion 92 to 95 ob a-Iron contains: D240 = o, g362; n020 = 1.550I42; Dispersion nF-nC = o, OI350.
Dieses Gemisch wird in der üblichen Weise in das 4-Phenylsemicarbazon ubergeführt. 10 g hiervon lieferten nach fraktionierter Kristallisation aus Alkohol 3,4g 4-Phenylsemicarbazon vom Schmelzpunkt I74,5 bis I75,50 und 8 g 4-Phenylsemicarbazon vom Schmelzpunkt I64,5 bis I650. Aus diesem werden durch Hydrolyse in einer siedenden wäßrigen Phthalsäurelösung 4,4 g dl-a-Iron erhalten, welches dasselbe 4-Phenylsemicarbazon ergibt und abgesehen vom Drehvermögen die gleichen physikalischen Eigenschaften wie das aus absoluter Irisessenz gewonnene a-I.ron zeigt und auch dessen Geruch aufweist. 2 g hiervon ergeben beim Hydrieren mit Raney-Nickel-Katalysator in 30 ccm -Alkohol bei 200 unter Aufnahme von I MolWasserstoff das Dihydro-a-iron, dessen Semicarbazon bei I72,5 bis I730 und dessen 2,4-Dinitrophenylhydrazon bei I30 bis I3IO schmilzt. Keines der hergestellten Produkte zeigte bei der Mischung mit dem entsprechenden Präparat aus a-Iron, das aus absoluter Irisessenz gewonnen wurde, eine Schmelzpunkterniedrigung. This mixture is converted into 4-phenylsemicarbazone in the usual way transferred. 10 g of this yielded after fractional crystallization from alcohol 3.4 g of 4-phenylsemicarbazone with a melting point of 174.5 to 175.50 and 8 g of 4-phenylsemicarbazone from melting point I64.5 to I650. For this are by hydrolysis in a boiling aqueous phthalic acid solution obtained 4.4 g of dl-a-iron, which is the same 4-phenylsemicarbazone gives the same physical properties aside from rotatability as the a-I.ron obtained from absolute iris essence shows and also its smell having. 2 g of this result on hydrogenation with a Raney nickel catalyst in 30 ccm -alcohol at 200 with uptake of 1 mole of hydrogen the dihydro-a-iron, its Semicarbazone from I72.5 to I730 and its 2,4-dinitrophenylhydrazone from I30 to I3IO melts. None of the products produced showed when mixed with the corresponding preparation from a-iron, which was obtained from absolute iris essence, a lowering of the melting point.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH931351X | 1948-05-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE931351C true DE931351C (en) | 1955-08-08 |
Family
ID=4548788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP31424A Expired DE931351C (en) | 1948-05-04 | 1949-01-12 | Process for the production of isomeric 6-methyl-ª ‡ -ionons (ª ‡ -ions) by ring closure of 3-methyl pseudoionons |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE931351C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1109677B (en) * | 1958-08-01 | 1961-06-29 | Hoffmann La Roche | Process for the preparation of unsaturated ketones of the ionone type |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR975343A (en) * | 1948-05-04 | 1951-03-05 | Givaudan & Cie Sa | Process for the preparation of methyl-6, alpha-ionones (alpha-irones) isomers, by the cyclization of methyl-3-pseudo-ionones |
| DE812313C (en) * | 1948-02-05 | 1951-08-27 | Givaudan & Cie Sa | Process for the production of ª ‡ -ionons from pseudo-ionons |
-
1949
- 1949-01-12 DE DEP31424A patent/DE931351C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE812313C (en) * | 1948-02-05 | 1951-08-27 | Givaudan & Cie Sa | Process for the production of ª ‡ -ionons from pseudo-ionons |
| FR975343A (en) * | 1948-05-04 | 1951-03-05 | Givaudan & Cie Sa | Process for the preparation of methyl-6, alpha-ionones (alpha-irones) isomers, by the cyclization of methyl-3-pseudo-ionones |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1109677B (en) * | 1958-08-01 | 1961-06-29 | Hoffmann La Roche | Process for the preparation of unsaturated ketones of the ionone type |
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