DE1294959B - Process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) - Google Patents
Process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2)Info
- Publication number
- DE1294959B DE1294959B DEF50952A DEF0050952A DE1294959B DE 1294959 B DE1294959 B DE 1294959B DE F50952 A DEF50952 A DE F50952A DE F0050952 A DEF0050952 A DE F0050952A DE 1294959 B DE1294959 B DE 1294959B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- bis
- methyl
- butene
- cyclohexyl
- 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 claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- YXXQTQYRRHHWFL-UHFFFAOYSA-N diiodophosphanyl(diiodo)phosphane Chemical compound IP(I)P(I)I YXXQTQYRRHHWFL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000006027 Birch reduction reaction Methods 0.000 claims description 3
- 150000007530 organic bases Chemical group 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003139 primary aliphatic amines Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic alcohols Chemical class 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical class CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- C07C49/647—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring
- C07C49/653—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Aus Liebigs Annalen der Chemie, Bd. 694, 1966, S. 19 bis 30 sowie S. 31 bis 37, ist es bereits bekannt, das 2, 3-Bis-(1'-methyl-4'-oxo-cyclohexyl)-buten-(2) auf verschiedenen Wegen in jeweils mehrstufigen Reaktionen herzustellen. From Liebigs Annalen der Chemie, Vol. 694, 1966, pp. 19 to 30 and P. 31 to 37, it is already known that the 2,3-bis (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) to be produced in different ways in each case in multi-stage reactions.
Es wurde nun gefunden, daß die Herstellung dieser Verbindung vereinfacht und mit wesentlich günstigeren Ausbeuten durchgeführt werden kann. It has now been found that the production of this connection is simplified and can be carried out with significantly more favorable yields.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von 2,3-Bis-(1'-methyl-4'-oxo-cyclohexyl)-buten-(2) der Formel 1 das dadurch gekennzeichnet ist, daß man eine Verbindung der allgemeinen Formel II in der X eine offene oder ringförmige Ketalgruppierung bedeutet, mit in Schwefelkohlenstoff gelöstem Diphosphortetrajodid in Gegenwart von tertiären organischen Basen behandelt, die erhaltene Verbindung der allgemeinen Formel III in der X die vorstehende Bedeutung besitzt, in einer Birch-Reaktion mit Alkalimetallen in flüssigem Ammoniak oder primären aliphatischen Aminen umsetzt und anschließend die erhaltene Verbindung der allgemeinen Formel IV in der X die vorstehende Bedeutung besitzt, in üblicher Weise sauer hydrolysiert.The invention therefore relates to a process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) of the formula 1 which is characterized in that a compound of the general formula II in which X denotes an open or ring-shaped ketal group, treated with diphosphorus tetraiodide dissolved in carbon disulfide in the presence of tertiary organic bases, the resulting compound of the general formula III in which X has the above meaning, in a Birch reaction with alkali metals in liquid ammonia or primary aliphatic amines and then the compound of the general formula IV in which X has the above meaning, hydrolyzed under acidic conditions in the usual manner.
Das als Ausgangsstoff verwendete Diol der allgemeinen Formel II, in der R die Athylenketalgruppe bedeutet, ist aus Liebigs Annalen der Chemie, Bd. 659, 1966, S. 31 bis 37, bekannt. Als Ketalgruppierung X kommen ketalisierte Oxogruppen in Frage, wobei die Alkoholkomponente der Ketale aus 1- oder 2wertigen Alkoholen besteht. So werden vorzugsweise ringförmige Ketale aus Äthylenglykol gebildet; es können jedoch auch Propylenglykol oder beispielsweise Neopentylglykol verwendet werden. Die Gruppierung X kann auch ein offenes Ketal sein, welches aus niederen aliphatischen Alkoholen, wie Methanol oder Äthanol, gebildet wird. Die Herstellung dieser Ketale erfolgt in üblicher, z. B. in Liebigs Annalen der Chemie, Bd. 684, 1965, S. 32, beschriebener Weise bei Verwendung der entsprechenden Alkohole. The diol of the general formula II used as starting material, in R the ethylene ketal group means, is from Liebig's Annals of Chemistry, Vol. 659, 1966, pp. 31 to 37. Ketalized oxo groups are used as the ketal grouping X in question, the alcohol component of the ketals being from monohydric or dihydric alcohols consists. For example, ring-shaped ketals are preferably formed from ethylene glycol; it however, propylene glycol or, for example, neopentyl glycol can also be used will. The grouping X can also be an open ketal, which consists of lower aliphatic alcohols such as methanol or ethanol is formed. The production this ketals takes place in the usual, z. B. in Liebig's Annalen der Chemie, vol. 684, 1965, p. 32, as described when using the corresponding alcohols.
Die Umsetzung des Diols der allgemeinen Formel II zum Dien der allgemeinen Formel III gelingt überraschenderweise mit Diphosphortetrajodid, welches aus Jod und gelbem Phosphor in absolutem Schwefelkohlenstoff hergestellt wird. Hierbei ist es nicht erforderlich, das feste P2J4 vor der Umsetzung aus der CS-Lösung zu isolieren. Die Wasserabspaltung wird vorteilhaft in tertiären organischen Basen, vorzugsweise Pyridin, aber auch in Picolinen, Collidinen, Chinolin, Isochinolin sowie Trialkylaminen, z. B. Triäthylamin, und tertiären Alkylarylaminen, wie Dimethylanilin, ausgeführt. Im allgemeinen wird das Reaktionsgemisch mehrere Tage stehengelassen, nach dem Abdestillieren der Hauptmenge des Schwefelkohlenstoffes das überschüssige Diphosphortetrajodid zersetzt und anschließend die wäßrige alkalische Lösung mit einem organischen Lösungsmittel, z. B. Essigsäureäthylester, extrahiert. The implementation of the diol of the general formula II to the diene of the general Formula III works surprisingly with diphosphorus tetraiodide, which is made from iodine and yellow phosphorus in absolute carbon disulfide. Here is it is not necessary to isolate the solid P2J4 from the CS solution before the reaction. The elimination of water is advantageous in tertiary organic bases, preferably Pyridine, but also in picolines, collidines, quinoline, isoquinoline and trialkylamines, z. B. triethylamine, and tertiary alkylarylamines, such as dimethylaniline, performed. In general, the reaction mixture is left to stand for several days after distilling off the main amount of carbon disulfide is the excess diphosphorus tetraiodide decomposed and then the aqueous alkaline solution with an organic solvent, z. B. ethyl acetate extracted.
Aus der organischen Phase wird das Dien der allgemeinen Formel 111 mit hohen Ausbeuten erhalten.The diene of the general formula III is obtained from the organic phase obtained with high yields.
Aus dem Dien der allgemeinen Formel 111 wird in einer anschließenden Birch-Reaktion, d. h. durch Einwirkung von Alkalimetall in flüssigem Ammoniak oder primären Aminen, das Butenderivat der allgemeinen Formel IV hergestellt. Als Alkalimetalle werden vorteilhaft Natrium oder Lithium verwendet. The diene of the general formula III becomes in a subsequent Birch reaction, d. H. by the action of alkali metal in liquid ammonia or primary amines, the butene derivative of the general formula IV. As alkali metals Sodium or lithium are advantageously used.
Man arbeitet entweder in flüssigem Ammoniak, kann jedoch aus wasserfreie niedere aliphatische Amine, wie Methylamin, Äthylamin oder Propylamin, verwenden. Nach mehrstündigem Rühren des Reaktionsgemisches wird das überschüssige Alkalimetall zersetzt, Ammoniak bzw. Amin verdunstet bzw. abdestilliert und das Reaktionsprodukt, beispielsweise durch Aufnahme in Äther und Ausschütteln der Ätherlösung, in üblicher Weise aufgearbeitet. Die Ausbeute ist auch bei dieser Reaktionsstufe hoch.One works either in liquid ammonia, but can from anhydrous Use lower aliphatic amines such as methylamine, ethylamine or propylamine. After stirring the reaction mixture for several hours, the excess alkali metal becomes decomposed, ammonia or amine evaporates or distilled off and the reaction product, for example, by being absorbed in ether and shaking out the ethereal solution, in the usual way Way worked up. The yield is also high at this stage of the reaction.
Aus dem Diketal der allgemeinen Formel IV werden schließlich noch die Ketalgruppen in üblicher Weise, d. h. durch saure Hydrolyse, abgespalten. The diketal of the general formula IV finally becomes the ketal groups in the usual way, d. H. by acid hydrolysis.
In Liebigs Annalen der Chemie, Bd. 694, 1966, S. 32, wird erwähnt, daß die Uberführung des Biscarbinols der allgemeinen Formel 11 (dort mit »8« bezeichnet) in das Dien der allgemeinen Formel III (dort mit »6« bezeichnet) nicht gelungen ist. Daß diese Wasserabspaltungsreaktion mittels Diphosphortetrajodid gelingt, ist außerordentlich überraschend, da einerseits Diphosphortetrajodid bisher nicht als wasserabspaltendes Mittel bekannt ist und andererseits nicht zu erwarten war, daß die Wasserabspaltung im gewünschten Sinne verlaufen würde. Die Dehydratisierung gelingt z. B. nicht im gewünschten Sinne mit den üblicherweise verwendeten wasserabspaltenden Mitteln, wie Thionylchlorid, Lewissäuren, Mineralsäuren oder Essigsäureanhydrid. In Liebigs Annalen der Chemie, Vol. 694, 1966, p. 32, it is mentioned that the conversion of biscarbinol to the general formula 11 (there denoted by "8") in the diene of the general formula III (denoted by "6" there) did not succeed is. That this dehydration reaction succeeds by means of diphosphorus tetraiodide extremely surprising, since on the one hand diphosphorus tetraiodide has not yet been considered dehydrating agent is known and on the other hand it was not to be expected that the elimination of water would proceed in the desired sense. The dehydration z. B. not in the desired sense with the dehydrating agents commonly used Means, such as thionyl chloride, Lewis acids, mineral acids or acetic anhydride.
Das neuartige Verfahren gemäß der Erfindung zur Herstellung von 2,3-Bis-(1'-methyl-4'-oxo-cyclohexyl)-buten-(2) ist nicht nur überraschend, sondern auch besonders vorteilhaft und den bisher bekannten Verfahren deutlich überlegen. Dies bezieht sich einmal auf Einsparung verschiedener Reaktionsstufen, andererseits auf die erhaltenen hohen Ausbeuten. The novel process according to the invention for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) is not only surprising, but also particularly advantageous and the previously known Process clearly superior. This refers to the saving of various Reaction stages, on the other hand, on the high yields obtained.
Das Verfahrensprodukt ist ein wertvolles Zwischenprodukt und kann zur Herstellung von Arzneimitteln verwendet werden. The process product is a valuable intermediate product and can used in the manufacture of medicines.
Beispiel a) Aus 125 g Jod und 29,5 g gelbem Phosphor wird in 1,5 1 absolutem CS eine P2J4-Lösung hergestellt. Man filtriert die Lösung und tropft unter Rühren innerhalb einer Stunde eine Lösung von 50 g 2,3 -Bis-( 1 -methyl-4'-äthylendioxy-cyclohexyl)-butan-2,3-diol (II); (X = Äthylendioxy) in 800 ml absolutem Pyridin zu. Nach Stägigem Stehen bei Raumtemperatur wird im Vakuum die Hauptmenge des CS2 abdestilliert und das überschüssige P2J4 mit 2 n-Natronlauge zersetzt. Nach Zugabe von 11 Essigsäureäthylester trennt man die organische Phase ab und wäscht mit 2 n-Natriumthiosulfatlösung und NaC1-Lösung nach. Example a) From 125 g of iodine and 29.5 g of yellow phosphorus, 1.5 1 absolute CS, a P2J4 solution was prepared. The solution is filtered and added dropwise with stirring, a solution of 50 g of 2,3-bis (1-methyl-4'-ethylenedioxy-cyclohexyl) butane-2,3-diol within one hour (II); (X = ethylenedioxy) in 800 ml of absolute pyridine. After standing for a day At room temperature, most of the CS2 and the excess is distilled off in vacuo P2J4 decomposed with 2N sodium hydroxide solution. After addition of 11 ethyl acetate separates the organic phase is washed off and washed with 2N sodium thiosulphate solution and NaCl solution after.
Nach Filtration über Aluminiumoxyd II nach B r o c k m a n n mit Benzol erhält man 37 g 2,3-Bis-(I'-methyl-4'-äthylendioxy-cyclohexyl)-butadien-(1, 1,3) (III); (X = Athylendioxy) als kristallisierendes Ul (86,50in). After filtration over aluminum oxide II according to B r o c k m a n n with Benzene gives 37 g of 2,3-bis- (I'-methyl-4'-ethylenedioxy-cyclohexyl) -butadiene- (1, 1.3) (III); (X = ethylenedioxy) as crystallizing UI (86.50in).
Kristallisation aus Petroläther: 1. Fraktion: 32,5 g (700/n); Schmelzpunkt = 101 bis 102"C.Crystallization from petroleum ether: 1st fraction: 32.5 g (700 / n); Melting point = 101 to 102 "C.
2. Fraktion: 1,3 g. b) Zu 1,5 1 kondensiertem, flüssigem Ammoniak werden 20 g Lithium in kleinen Stücken gegeben. 2nd fraction: 1.3 g. b) To 1.5 l of condensed liquid ammonia 20 g of lithium are given in small pieces.
Nach 10 Minuten langem Rühren tropft man eine Lösung von 59 g des nach a) erhaltenen Diens in 600 ml absolutem Äther zu und rührt das Gemisch weitere 5 Stunden.After stirring for 10 minutes, a solution of 59 g of des according to a) the diene obtained in 600 ml of absolute ether and the mixture is stirred further 5 hours.
Das überschüssige Lithium wird vorsichtig mit Methanol zersetzt. Nach Zugabe von 500 ml Äther läßt man das Ammoniak über Nacht abdunsten. Nach üblicher Aufarbeitung erhält man 55 g kristallisierendes Rohprodukt an Diketal IV der allgemeinen Formel (X = Äthylendioxy). The excess lithium is carefully decomposed with methanol. After adding 500 ml of ether, the ammonia is allowed to evaporate overnight. According to the usual Working up gives 55 g of crystallizing crude product of diketal IV of the general Formula (X = ethylenedioxy).
Kristallisation aus Äther: 1. Fraktion: 39 g weiße Kristalle; Schmelzpunkt = 157 bis 159"C (660/).Crystallization from ether: 1st fraction: 39 g of white crystals; Melting point = 157 to 159 "C (660 /).
2. Fraktion: 5,4 g. 2nd fraction: 5.4 g.
3. Fraktion: 4,8 g. c) 7 g des nach b) erhaltenen Monoolefins in 180 ml Aceton werden mit 25 ml 50/oiger HaSO.I 5 Minuten unter Rückfluß gekocht. Nach dem Versetzen mit NaHCO:1-Lösung wird wie üblich aufgearbeitet. Nach Umkristallisieren aus Petroläther erhält man 4,4 g (830/) 2,3-Bis-[l'-methyl-4'-oxocyclohexyl)-buten-(2) vom Schmelzpunkt 139 bis 141"C. 3rd fraction: 4.8 g. c) 7 g of the monoolefin obtained in b) in 180 ml of acetone are refluxed with 25 ml of 50% HaSO.I for 5 minutes. After the addition of NaHCO: 1 solution, it is worked up as usual. After recrystallization from petroleum ether one receives 4.4 g (830 /) 2,3-bis- [l'-methyl-4'-oxocyclohexyl) -butene- (2) from melting point 139 to 141 "C.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF50952A DE1294959B (en) | 1966-12-15 | 1966-12-15 | Process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF50952A DE1294959B (en) | 1966-12-15 | 1966-12-15 | Process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1294959B true DE1294959B (en) | 1969-05-14 |
Family
ID=7104208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF50952A Pending DE1294959B (en) | 1966-12-15 | 1966-12-15 | Process for the preparation of 2,3-bis- (1'-methyl-4'-oxo-cyclohexyl) -butene- (2) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1294959B (en) |
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1966
- 1966-12-15 DE DEF50952A patent/DE1294959B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
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