DE1668156C - Process for the production of a mixture of 3 ice dimethylamine 4 phenyl 4 ice carbathoxy Delta to the power of 1 cyclohexene and 3 trans Dimethylamine 4 phenyl 4 trans carbathoxy Delta to the power of 1 cyclohexene - Google Patents
Process for the production of a mixture of 3 ice dimethylamine 4 phenyl 4 ice carbathoxy Delta to the power of 1 cyclohexene and 3 trans Dimethylamine 4 phenyl 4 trans carbathoxy Delta to the power of 1 cyclohexeneInfo
- Publication number
- DE1668156C DE1668156C DE1668156C DE 1668156 C DE1668156 C DE 1668156C DE 1668156 C DE1668156 C DE 1668156C
- Authority
- DE
- Germany
- Prior art keywords
- trans
- phenyl
- cyclohexene
- dimethylamine
- carbathoxy
- 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
- 239000000203 mixture Substances 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N Cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims 3
- ZCHIILIKSYVXQM-UHFFFAOYSA-N 4-phenyl-4$l^{5}-phosphabicyclo[3.2.0]hept-2-ene 4-oxide Chemical compound C1=CC2CCC2P1(=O)C1=CC=CC=C1 ZCHIILIKSYVXQM-UHFFFAOYSA-N 0.000 title 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 title 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N Crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- -1 Dimethylamine-propionic acid ethyl ester Chemical compound 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ONPJWQSDZCGSQM-UHFFFAOYSA-N 2-phenylprop-2-enoic acid Chemical class OC(=O)C(=C)C1=CC=CC=C1 ONPJWQSDZCGSQM-UHFFFAOYSA-N 0.000 description 1
- VPCDQGACGWYTMC-UHFFFAOYSA-N Nitrosyl chloride Chemical compound ClN=O VPCDQGACGWYTMC-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N Phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BUNYBPVXEKRSGY-UHFFFAOYSA-N buta-1,3-dien-1-amine Chemical class NC=CC=C BUNYBPVXEKRSGY-UHFFFAOYSA-N 0.000 description 1
- 150000001935 cyclohexenes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Description
I 668I 668
In tleni Patent 1 518 959 wird ein Verfahren zur Herstellung von basisch substituierten Cyclohexenen durch Umsetzung von Aminobutadienen-(1,3) mit Atropasäureestern beschrieben, durch das auch das 3-Dimethylamino-4-phenyl-4-carbäthoxy- l'-cyclohexen hergestellt werden kann. Diese Verbindung fällt dabei a,ls ein Gemisch der entsprechenden 3-cis-4-cis- und der entsprechenden 3-trans-4-trans-Verbindung an, welches zur Gewinnung des allein gewünschten trans-Isomeren entsprechend aufgearbeitet wird.In tleni patent 1 518 959 a method for Preparation of basic substituted cyclohexenes by reacting aminobutadienes (1,3) with Atropic acid esters described, through which the 3-dimethylamino-4-phenyl-4-carbäthoxy- l'-cyclohexene can be produced. This compound precipitates a, ls a mixture of the corresponding 3-cis-4-cis- and the corresponding 3-trans-4-trans compound, which is used to obtain the only desired trans isomers is worked up accordingly.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines Gemisches aus 3-cis-Dimethylamino-4 - phenyl - 4 - eis - carbäthoxy -. I'- cyclohexen und - trans - Dimethylamine - 4 - phenyf - 3 - trans- carbäthoxy- l'-cyclohexen. Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, daß man a-Phenyl-/f-dimethylamino-propionsäureäthylester mit Crotonaldehyd bei 90 bis 14O0C einige Stunden in Gegenwart von 0,5 bis 1 Äquivalent Diäthylcarbonat kondensiert.The invention relates to a process for the preparation of a mixture of 3-cis-dimethylamino-4-phenyl-4-cis-carbethoxy. I'- cyclohexene and - trans - dimethylamine - 4 - phenyf - 3 - trans- carbäthoxy- l'-cyclohexene. The inventive method is characterized in that a-phenyl / f-dimethylamino-ethyl propionate condensed with crotonaldehyde at 90 to 14O 0 C for several hours in the presence of 0.5 to 1 equivalent of diethyl carbonate.
Bevorzugt ist ein sechsstündiges Erhitzen auf 1200C.Preference is given to heating to 120 ° C. for six hours.
Das anfallende Produkt kann dann zur Gewinnung der allein interessierenden 3-trans-4-trans-Verbindung ίο gemäß dem Verfahren des Patents 1 518 959 in seine Komponenten aufgetrennt werden.The resulting product can then be used to obtain the only 3-trans-4-trans compound of interest ίο be separated into its components according to the method of patent 1,518,959.
Die verfahrensmäßige Reaktionsfolge könnte dem hier aufgezeichneten Formelschema entsprechend ablaufen :The procedural reaction sequence could proceed according to the formula scheme recorded here :
N(CHj)1
2 C6H5
H COOC2H5 N (CHj) 1
2 C 6 H 5
H COOC 2 H 5
N(CH3J2 N (CH 3 J 2
QH5 QH 5
^COOC2H5 Hl°^ COOC 2 H 5 Hl °
N(CH3J2
C6H5 N (CH 3 J 2
C 6 H 5
N(CH3 N (CH 3
COOC2H5 COOC 2 H 5
1,2-Addition1,2 addition
COOC2H5 COOC 2 H 5
cis/trans-Isomerecis / trans isomers
221.3 g(l Mol)a-Phenyl-fi-dimethylamino-propionsäureäthylester, 105,1 g (1,5 Mol) Crotonaldehyd und 118,1 g(l Mol) Diäthylcarbonat werden unter Rühren 6 Stunden auf 1200C erhitzt. Das Gemisch wird noch warm in 1 I 2 n-HCI eingetragen, durch Extraktion mit Benzol oder Äthylacetat von Neutralprodukten befreit und die wäßrige Phase alkalisch gemacht. Das abgeschiedene öl wird nach dem Trocknen im Feinvakuum destilliert. Das Isomcrengemisch geht bei 0.01 Torr/95 bis 100° C über. Es wird in verdünnter HCl gelöst und kann dann weiter über die Zink-Chloridkomplexverbindung in seine Komponenten aufgeteilt werden. Ausbeute 134 g (49% der Theorie).221.3 g (l mol) of a-phenyl-fi-dimethylamino-ethyl propionate, 105.1 g (1.5 mol) of crotonaldehyde and 118.1 g (l mol) of diethyl carbonate are heated with stirring for 6 hours at 120 0 C. The mixture is introduced into 1 l of 2N HCl while still warm, freed from neutral products by extraction with benzene or ethyl acetate, and the aqueous phase is made alkaline. After drying, the separated oil is distilled in a fine vacuum. The isomer mixture goes over at 0.01 Torr / 95 to 100 ° C. It is dissolved in dilute HCl and can then be further divided into its components via the zinc chloride complex compound. Yield 134 g (49% of theory).
Man erhält 3 - trans- Dimethylamino-4- phenyl-4-trans-carbäthoxyl'-cyclohexen vom Siedepunkt 0.01 Torr/96 bis 97 C, Hydrochlorid (aus Dioxan) Fp. If9 C.3-trans-dimethylamino-4-phenyl-4-trans-carbethoxyl'-cyclohexene is obtained with a boiling point of 0.01 Torr / 96 to 97 C, hydrochloride (from dioxane) Mp. If9 C.
Analyse für C17H24ClNO2 (Molekulargewicht 309,85): Berechnet:Analysis for C 17 H 24 ClNO 2 (molecular weight 309.85): Calculated:
C 65,89, H 7,81, Cl 11,45, N 4,52%;
gefunden:
C 65,60, H 7,62, Cl 11,35, N 4,70%.C 65.89, H 7.81, Cl 11.45, N 4.52%;
found:
C 65.60, H 7.62, Cl 11.35, N 4.70%.
Claims (1)
Family
ID=
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