DE1028567B - Process for the preparation of bicyclo- (2, 2, 1) -aethynyl- (2) -heptanol- (2) - Google Patents
Process for the preparation of bicyclo- (2, 2, 1) -aethynyl- (2) -heptanol- (2)Info
- Publication number
- DE1028567B DE1028567B DEK31445A DEK0031445A DE1028567B DE 1028567 B DE1028567 B DE 1028567B DE K31445 A DEK31445 A DE K31445A DE K0031445 A DEK0031445 A DE K0031445A DE 1028567 B DE1028567 B DE 1028567B
- Authority
- DE
- Germany
- Prior art keywords
- ether
- acetylene
- mol
- bicyclo
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- KPMKEVXVVHNIEY-RITPCOANSA-N norcamphor Chemical compound C1C[C@@H]2C(=O)C[C@H]1C2 KPMKEVXVVHNIEY-RITPCOANSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical group OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- XZFDKWMYCUEKSS-UHFFFAOYSA-N 6,6-Dimethylbicyclo[3.1.1]heptan-2-one Chemical compound C1C2C(C)(C)C1CCC2=O XZFDKWMYCUEKSS-UHFFFAOYSA-N 0.000 description 2
- LHXDLQBQYFFVNW-UHFFFAOYSA-N Fenchone Chemical compound C1CC2(C)C(=O)C(C)(C)C1C2 LHXDLQBQYFFVNW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000000476 acetylides Chemical class 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- -1 hydrocarbon radicals Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- LHXDLQBQYFFVNW-XCBNKYQSSA-N (+)-Fenchone Natural products C1C[C@]2(C)C(=O)C(C)(C)[C@H]1C2 LHXDLQBQYFFVNW-XCBNKYQSSA-N 0.000 description 1
- MQPHVIPKLRXGDJ-PRJMDXOYSA-N (-)-Pinocamphone Chemical compound C1C(=O)[C@H](C)[C@H]2C(C)(C)[C@@H]1C2 MQPHVIPKLRXGDJ-PRJMDXOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N 3,3,5-trimethylcyclohexan-1-one Chemical compound CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CIHXIRAAMAUYLZ-UHFFFAOYSA-N [K+].[K+].[C-]#[C-] Chemical compound [K+].[K+].[C-]#[C-] CIHXIRAAMAUYLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930006735 fenchone Natural products 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- MQPHVIPKLRXGDJ-RNJXMRFFSA-N isopinocamphone Natural products C1C(=O)[C@@H](C)[C@H]2C(C)(C)[C@@H]1C2 MQPHVIPKLRXGDJ-RNJXMRFFSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- KPMKEVXVVHNIEY-UHFFFAOYSA-N norcamphor Chemical compound C1CC2C(=O)CC1C2 KPMKEVXVVHNIEY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GCRTVIUGJCJVDD-UHFFFAOYSA-N tetrahydrocarvone Natural products CC(C)C1CCC(C)C(=O)C1 GCRTVIUGJCJVDD-UHFFFAOYSA-N 0.000 description 1
- GCRTVIUGJCJVDD-IUCAKERBSA-N trans-Dihydrocarvone Chemical compound CC(C)[C@H]1CC[C@H](C)C(=O)C1 GCRTVIUGJCJVDD-IUCAKERBSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C35/23—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 with hydroxy on a condensed ring system having two rings
- C07C35/28—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 with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms
- C07C35/29—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 with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms being a (2.2.1) system
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Bicyclo- (2i2,1) -äthinyl- (2) -heptanol- (2) Gegenstand der Erfindung ist die Herstellung des neuen Bicyclo- (2,2,1) 1 (2) 4-ieptanol- (2). Process for the preparation of bicyclo- (2i2,1) -äthinyl- (2) -heptanol- (2) The invention relates to the production of the new bicyclo- (2,2,1) 1 (2) 4-ieptanol- (2).
Die Herstellung von a-Alkinolen durch Umsetzung von Carbonylverbindungen mit einem Alkaliacetylid nach dem Reaktionsschema wobei Me ein Alkalimetall und R1 und R2 Kohlenwasserstoftreste bedeuten, ist an sich bekannt.The preparation of a-alkynols by reacting carbonyl compounds with an alkali acetylide according to the reaction scheme where Me is an alkali metal and R1 and R2 are hydrocarbon radicals, is known per se.
So werden tertiäre Äthinylcarbinole z. B. dadurch erhalten, daß man eine Lösung des Ketons in Dimethylacetal zu einer Suspension vonNaftiumacetyhd in flüssigem Ammoniak hinzugibt und Acetylengas mehrere Stunden durch die Reaktionsmischung hindurchleitet (Journal Am. Chem. Soc., Bd. 77, 1955, 5. 487dz, 4875). So tertiary ethynyl carbinols z. B. obtained by a solution of the ketone in dimethyl acetal to a suspension of naftium acetyhd in liquid ammonia is added and acetylene gas is passed through the reaction mixture for several hours (Journal Am. Chem. Soc., Vol. 77, 1955, pp. 487dz, 4875).
In analoger Vi'eise werden tertiäre Äthinylcarbinole, z. B. 1-Äthinylcyclohexanol-(1), dadurch erhalten, daß man trockenes Acetylen in flüssiges Ammoniak einleitet, dem Natrium zugefügt ist, die Reaktionsmischung mit Cyclohexanon versetzt und darauf die Zwischenverbindung mit Eis zersetzt (Belgische Patentschrift 505421). In an analogous way, tertiary ethynyl carbinols, e.g. B. 1-Ethynylcyclohexanol- (1), obtained by introducing dry acetylene into liquid ammonia, the Sodium is added, the reaction mixture is mixed with cyclohexanone and then the intermediate compound decomposes with ice (Belgian patent 505421).
Bei diesem Verfahren entsteht jedoch außer dem gewünschten a-Alkinol stets auch eine gewisse Menge des entsprechenden Acetylenglykols: Dabei ist die Ausbeute an a-Äthinylcarbinol sowohl von den gewählten Versuchsbedingungen als auch von der Konstitution der Ausgangs-Carbonylverbindung abhängig. So erhält man aus monocyclischen hydroaromatischen Ketonen, wie Cyclohexanon, 3-Methyl-5,5-dimethylcyclohexanon, Tetrahydrocarvon, die entsprechenden a-Äthinylcarbinole in Ausbeuten von 60 bis 90 °/0 der Theorie. Demgegenüber werden die a-Äthinyl carbinole von bicyclischen hydroaromatischen Ketonen wie Campher, Fenchon, Pinocamphon oder Nopinon nur mit 10 bis 30°1O der Theorie gebildet. Es war daher zu erwarten, daß auch beim Norcampher die Äthinylierung nur mit schlechten Ausbeuten erfolgen würde. tberraschenderweise wurde nun aber gefunden, daß man aus Norcampher durch Einwirkung von Acetylen, insbesondere von Alkaliacetyliden Bicyclo-(2,2,1 )-äthinyl-(2) -heptanol- (2), (2-Äthinylnorborneol- (2)), in Ausbeuten bis zü 90°/o erhält.In this process, however, in addition to the desired a-alkynol, a certain amount of the corresponding acetylene glycol is always produced: The yield of α-ethynyl carbinol depends on both the experimental conditions chosen and the constitution of the starting carbonyl compound. Thus, from monocyclic hydroaromatic ketones, such as cyclohexanone, 3-methyl-5,5-dimethylcyclohexanone, tetrahydrocarvone, the corresponding α-ethynyl carbinols are obtained in yields of 60 to 90% of theory. In contrast, the a-ethynyl carbinols of bicyclic hydroaromatic ketones such as camphor, fenchone, pinocamphone or nopinone are only formed at 10 to 30 ° 10 of theory. It was therefore to be expected that ethynylation would only take place with poor yields in the case of norcamphor. Surprisingly, however, it has now been found that, by the action of acetylene, in particular alkali acetylides, bicyclo- (2,2,1) -ethinyl- (2) -heptanol- (2), (2-ethynylnorborneol- (2)), in yields of up to 90%.
Die Umsetzung wird zweckmäßig so ausgeführt, daß man ein Alkaliacetylid in flüssigem Ammoniak auf Norcampher bei niedrigen Temperaturen, wie 400 C, einwirken läßt. An Stelle von flüssigem Ammoniak können auch andere Lösungsmittel, z. B. tertiärer Amylalkohol, verwendet werden. Die Umsetzung kann auch mit Acetylengas unter Druck durchgeführt werden. An Stelle von Alkaliacetyliden können auch Schwermetallacetylide verwendet werden. The reaction is expediently carried out in such a way that an alkali acetylide is used act in liquid ammonia on norcamphor at low temperatures, such as 400 C. leaves. Instead of liquid ammonia, other solvents, e.g. B. tertiary Amyl alcohol can be used. The implementation can also be carried out with acetylene gas under pressure be performed. Instead of alkali acetylides, heavy metal acetylides can also be used be used.
2-Äthinylnorborneol-(2) ist selbst hypnotisch und sedativ schwach wirksam, es bildet aber ein wichtiges Zwischenprodukt beim Aufbau von Arzneimitteln. 2-Ethynylnorborneol- (2) is itself hypnotic and sedative weak effective, but it is an important intermediate in the development of drugs.
Beispiel 1 In 11 flüssiges Ammoniak werden unter gleichzeitigem Einleiten von trockenem Acetylen 24 g Natrium (1,04 Mol) innerhalb von 40 Minuten unter Rühren eingetragen. Das Gemisch wird bis zum Verschwinden der blauen Farbe mit Acetylen behandelt und darauf bei etwa --40°C eine Lösung von 110 g Norcampher (1 Mol) in 300 ccm trokkenem Diäthyläther (oder Diisopropyläther) langsam zugefügt und das Gemisch etwa 3 Stunden gerührt. Nun verdünnt man mit 200 ccm Äther, entfernt das Kälte bad, läßt das Ammoniak abdampfen und nimmt den Rückstand mit 500 ccm Eiswasser auf. Nach dem Ansäuern mit 50°lOiger Schwefelsäure wird die Ätherschicht abgetrennt, die wäßrige Phase mehrmals mit Äther extrahiert und die vereinigten Extrakte nach dem Waschen mit verdünnter Natronlauge und mit gesättigter Kochsalzlösung über Natriumsulfat getrocknet. Der nach dem Verdampfen des Lösungsmittels verbleibende hellgelbe Sirup (130 bis 135 g) enthält 120 bis 122 g mit Silbernitrat titrierbares 2-Äthinylnorborneol-(2) (= 88 bis 90% der Theorie), das im Kühlschrank zu einer kristallinen Masse erstarrt. Zur Reinigung wird das rohe 2-Äthinylnorborneol-(2) im Vakuum destilliert. Die Hauptfraktion bildet eine farblose, dicke Flüssigkeit vom Kp. 760 = 195 bis 196°C, Kp.5 68°C, die zu farblosen Kristallen vom F. = 45 bis 46°C erstarrt. Example 1 In 11 liquid ammonia are introduced with simultaneous introduction of dry acetylene 24 g of sodium (1.04 mol) within 40 minutes with stirring registered. The mixture is mixed with acetylene until the blue color disappears treated and then a solution of 110 g norcamphor (1 mol) in 300 cc of dry diethyl ether (or diisopropyl ether) slowly added and that Mixture stirred for about 3 hours. Now you dilute with 200 ccm of ether, remove that Cold bath, allow the ammonia to evaporate and take the residue with 500 cc of ice water on. After acidification with 50 ° 10 sulfuric acid, the ether layer becomes separated, the aqueous phase extracted several times with ether and the combined extracts after washing with dilute sodium hydroxide solution and with saturated sodium chloride solution over sodium sulfate dried. The light yellow syrup that remains after the solvent has evaporated (130 to 135 g) contains 120 to 122 g of 2-ethynylnorborneol- (2) that can be titrated with silver nitrate (= 88 to 90% of theory), which solidifies to a crystalline mass in the refrigerator. For purification, the crude 2-ethynylnorborneol- (2) is distilled in vacuo. The main faction forms a colorless, thick liquid with a b.p. 760 = 195 to 196 ° C, b.p. 5 68 ° C, which solidifies to colorless crystals with a temperature of 45 to 46 ° C.
Analyse für C9H12O: Berechnet . .. C = 79a41 O/o, H = 8n82 °/o; gefunden . . C = 79,50 °/0, H = 8,90 °/o.Analysis for C9H12O: Calculated. .. C = 79a41 o / o, H = 8n82 ° / o; found . . C = 79.50 ° / o, H = 8.90 ° / o.
Die Substanz ist flüchtig, wenig löslich in Wasser, gut löslich in organischen Lösungsmitteln. Sie liefert mit ammoniakalischer Silbernitratlösung eine kristallisierte Silberverbindung (AgC9HllO), welche auch zur Reinigung des Äthinylnorborneols herangezogen werden kann. The substance is volatile, sparingly soluble in water, well soluble in organic solvents. It delivers with ammoniacal silver nitrate solution a crystallized silver compound (AgC9HllO), which is also used to purify the Ethynylnorborneols can be used.
Durch Umsetzung des Silbersalzes mit wäßriger A mmoniumrhodanidlösung wird das 2-Äthinylnorborneol-(2) durch Extraktion mit Äther rein gewonnen. By reacting the silver salt with aqueous ammonium rhodanide solution the 2-ethynylnorborneol- (2) is obtained pure by extraction with ether.
Beispiel 2 Eine Lösung von 40 g Kalium (1,02 Mol) in 600 ccm tertiärem Amylalkohol wird mit 400 ccm trockenem Diäthyläther versetzt, in welchen bei -150C 35 g Acetylen (1,34 Mol) eingeleitet worden waren, und tropft innerhalb von 2 Stunden eine Lösung von 110 g Norcampher (1 Mol), in 300 ccm trockenem Diäthyläther zu. Example 2 A solution of 40 g of potassium (1.02 mol) in 600 cc of tertiary Amyl alcohol is mixed with 400 ccm of dry diethyl ether, in which at -150C 35 g of acetylene (1.34 mol) had been passed in and added dropwise over the course of 2 hours a solution of 110 g of norcamphor (1 mol) in 300 cc of dry diethyl ether.
Das Reaktionsgemisch wird 14 Stunden bei5°C gerührt, über Nacht im Eisschrank stehengelassen und mit 800 ccm Eiswasser zersetzt. Nack dem Ansäuren mit 50 °/Oiger Schwefelsäure trennt man die Amylalkohol-Äther-Phase ab, extrahiert die wäßrige Phase mehrmals mit Äther, wäscht die vereinigten Extrakte (einschließlich der Amylalkohol-Äther-Phase) mit verdünnter Natronlauge und gesättigter Kochsalzlösung und trocknet sie über Natriumsulfat. Der nach dem Abdestillieren des Lösungsmittels verbleibende gelbe Sirup (125 bis 130 g) enthält etwa 100 g titrierbares 2-Äthinylnorborneol-(2) (= 74°/0 der Theorie).The reaction mixture is stirred for 14 hours at 5 ° C, overnight in Left in the refrigerator and decomposed with 800 cc of ice water. Naked the acid the amyl alcohol-ether phase is separated off with 50% sulfuric acid and extracted the aqueous phase several times with ether, washes the combined extracts (including the amyl alcohol-ether phase) with dilute sodium hydroxide solution and saturated saline solution and dry them over sodium sulfate. The one after the solvent has been distilled off remaining yellow syrup (125 to 130 g) contains about 100 g titratable 2-ethynylnorborneol- (2) (= 74% of theory).
Beispiel 3 In eine Suspension von Kaliumacetylid, hergestellt durch Einleiten von 35 g Acetylen (1,34 Mol) in eine Suspension von 250 g gepulvertem Ätzkali in 1,5 1 trockenem Diäthyläther oder Diisopropyläther bei5° C, tropft man innerhalb von 3 Stunden eine Lösung von 110 g Norcampher (1 Mol) in 200 ccm trockenem Äther bei -50C, rührt das Gemisch unter zeitweisem Einleiten von Acetylen 5 Stunden bei5°C und läßt den entstehenden gelblich gefärbten dicken Brei über Nacht im Eisschrank stehen. Das Reaktionsgemisch wird durch Eintragen in 800 g Eiswasser zersetzt, die Ätherphase abgetrennt und die wäßrige Phase mehrmals mit Äther extrahiert. Die vereinigten Extrakte werden mit gesättigter Kochsalzlösung gewaschen, über Natriumsulfat getrocknet und das Lösungsmittel verdampft. Der Rückstand liefert bei der Fraktionierung im Vakuum etwa 110 g 2-Äthinylnorborneol-(2) (81°/o der Theorie) vom Kp.5 = 68 bis 690 C. Es erstarrt beim Abkühlen zu einer kristallinen Masse. Aus dem Destillationsrückstand gewinnt man durch Umiösen aus Alkohol etwa 8,0 g (= 6¢5°/o der Theorie) Bis- (2-hydroxynorbornyl-2)-acetylen in weißen Blättchen vom F. = 187 bis 1880 C. Example 3 In a suspension of potassium acetylide, prepared by Introducing 35 g of acetylene (1.34 mol) into a suspension of 250 g of powdered Caustic potash in 1.5 l of dry diethyl ether or diisopropyl ether at 5 ° C is added dropwise within 3 hours a solution of 110 g of Norcampher (1 mol) in 200 ccm of dry Ether at -50C, the mixture is stirred for 5 hours with occasional introduction of acetylene at 5 ° C and leaves the resulting yellowish colored thick pulp in the refrigerator overnight stand. The reaction mixture is decomposed by pouring it into 800 g of ice water Ether phase separated and the aqueous phase extracted several times with ether. The United Extracts are washed with saturated sodium chloride solution and dried over sodium sulfate and the solvent evaporates. The residue gives in the fractionation in Vacuum about 110 g of 2-ethynylnorborneol- (2) (81% of theory) from bp 5 = 68 to 690 C. It solidifies to a crystalline mass on cooling. From the distillation residue about 8.0 g (= 6 [5% of theory) of bis (2-hydroxynorbornyl-2) acetylene are obtained by dissolving from alcohol in white leaves from F. = 187 to 1880 C.
Führt man die Reaktion bei geringem Überdruck (2 bis 7 atü; mit N2 verdünntes Acetylen) durch, so läßt sich die Reaktionszeit entsprechend abkürzen. If the reaction is carried out at a slight overpressure (2 to 7 atmospheres; with N2 dilute acetylene), the reaction time can be shortened accordingly.
Beispiel 4 In eine Suspension von 50 g Natriumamid (1,28 Mol) in 800 ccm trockenem Äther (oder Diisopropyläther), in welchem bei -80C 35 g Acetylen (1,34 Mol) eingeleitet worden waren, tropft man in 3 Stunden eine Lösung von 110 g Norcampher (1 Mol) in 200 ccm trockenem Äther bei -8°C, rührt das Gemisch unter zeitweisem Einleiten von Acetylen 5 Stunden bei 50C und läßt das gelbbraun gefärbte Reaktionsgemisch über Nacht im Eisschrank stehen. Nach dem Zersetzen mit 800 g Eiswasser und Ansäuern mit 50°/Oiger Schwefelsäure wird die Ätherphase abgetrennt und die wäßrige Phase mehrmals mit Äther extrahiert. Die vereinigten Extrakte werden mit 4°/Oiger Natronlauge und darauf mit gesättigter Kochsalzlösung gewaschen, über Natriumsulfat getrocknet, das Lösungs mittel verdampft, und man erhält bei der Fraktionierung im Vakuum 115 bis 120 g reines 2-Äthinylnorborneol-(2) in einer Ausbeute von 85 bis 89°lo der Theorie. Example 4 In a suspension of 50 g of sodium amide (1.28 mol) in 800 cc of dry ether (or diisopropyl ether) in which 35 g of acetylene at -80C (1.34 mol) had been introduced, a solution of 110 is added dropwise over 3 hours g of norcamphor (1 mol) in 200 ccm of dry ether at -8 ° C, stir the mixture in occasional introduction of acetylene for 5 hours at 50C and leaves the yellow-brown colored Stand the reaction mixture in the refrigerator overnight. After decomposition with 800 g of ice water and acidification with 50% sulfuric acid, the ether phase is separated and the aqueous phase extracted several times with ether. The combined extracts are with 4% sodium hydroxide solution and then washed with saturated sodium chloride solution over sodium sulfate dried, the solvent evaporated medium, and one obtains in the fractionation 115 to 120 g of pure 2-ethynylnorborneol- (2) in a yield of 85 in vacuo up to 89 ° lo of theory.
Beispiel 5 In eine Suspension von 50 g Natriumamid (1,28 Mol) in 500 cm Dimethylformamid werden bei - 10°C 39 g Acetylen (1,5 Mol) eingeleitet und in 2 Stunden eine Lösung von 110 g Norcampher (1 Mol) in 150 cm Di methylformamid eingetropft. Man rührt das Gemisch 3 Stunden bei -100C, zersetzt es mit 800 g Eiswasser', säuert es mit 50°/Oiger Schwefelsäure an und extrahiert das 2-Äthinylnorborneol-(2) mit Äther. Bei der Aufarbeitung der vereinigten Ätherextrakte gemäß Beispiel 4 werden 118 bis 124 g reines 2-Äthinylnorborneol-(2) = 87 bis 91 °/0 der Theorie erhalten. pATENTANSI'RUCII Verfahren zur Herstellung von Bicyclo-(2,2,1)-äthinyl- (2) -heptanol- (2), dadurch gekennzeichnet, daß man auf Norcampher Acetylen oder Metallacetylidé in Gegenwart von flüssigem Ammoniak oder anderen Lösungsmitteln bei niederen Temperaturen in bekannter Weise einwirken läßt. Example 5 In a suspension of 50 g of sodium amide (1.28 mol) in 500 cm of dimethylformamide are introduced and 39 g of acetylene (1.5 mol) at -10 ° C a solution of 110 g of norcamphor (1 mol) in 150 cm of dimethylformamide in 2 hours dripped in. The mixture is stirred for 3 hours at -100C, it is decomposed with 800 g of ice water ', acidify it with 50% sulfuric acid and extract the 2-ethynylnorborneol- (2) with ether. When working up the combined ether extracts according to Example 4 118 to 124 g of pure 2-ethynylnorborneol- (2) = 87 to 91% of theory were obtained. PATENTANSI'RUCII Process for the production of bicyclo- (2,2,1) -äthinyl- (2) -heptanol- (2), characterized in that one uses acetylene or metal acetylidé on norcamphor in the presence of liquid ammonia or other solvents at low temperatures can act in a known manner.
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