CH314558A - Process for the preparation of a basic ketone - Google Patents
Process for the preparation of a basic ketoneInfo
- Publication number
- CH314558A CH314558A CH314558DA CH314558A CH 314558 A CH314558 A CH 314558A CH 314558D A CH314558D A CH 314558DA CH 314558 A CH314558 A CH 314558A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- phenyl
- pyridyl
- dimethylamino
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 150000002576 ketones Chemical class 0.000 title description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- -1 amino-4-phenyl-4-pyridyl Chemical group 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- RXQNHIDQIJXKTK-UHFFFAOYSA-N azane;pentanoic acid Chemical compound [NH4+].CCCCC([O-])=O RXQNHIDQIJXKTK-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 6
- ZMLUHYJUTIZTOJ-UHFFFAOYSA-N 2-dimethylamino-2-methyl-1-chloro-ethane Natural products ClCC(C)N(C)C ZMLUHYJUTIZTOJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FLAKGKCBSLMHQU-UHFFFAOYSA-N CC[Mg] Chemical compound CC[Mg] FLAKGKCBSLMHQU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940126601 medicinal product Drugs 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung eines basischen Ketons Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von 2-Dimethyl- amino-4-phenyl-4-py ridyl -(2') -heptanon-(5) , welches dadurch gekennzeichnet ist, dass man einen u-Phenyl-a-pyridyl-(2)-y-dimethyl-amino- valeriaiisäureester mit einem Äthylmagnesium- lialogenid umsetzt.
Bei der Herstellung der Ausgangsverbin dung aus Phenylpyridyl-(2)-essigsäureäthyl- ester und 2-Dimethylaminopropylchlorid in Gel-enwar t von Natriumamid fällt ein Iso- merengemisch an, welches neben der Aus gangsverbindung den isomeren a-Phenyl-a- pyridy l- (2) - l-methyl-y-dimethylamino -butter- säureester enthält.
Bei Durchführung des Ver fahrens gemäss der Erfindung mit diesem Produkt wird neben dem 2-Dimethyl-amino-4- phenyl-4-pyridyl-(2')-heptanon-(5) das isomere 7 -Dimethylamino-2-methyl-3-phenyl-3-pyridyl- (2')-liexanon-(4) ,erhalten.
Bei Herstellung der Maleinate in Essigsäureäthylester als Lö sungsmittel erfolgt die Trennung des isomeren Basengemisches, und es kristallisiert lediglich das Maleinat des 2-Dimethylamino-4-phenyl-4- pyridyl-(2')-heptanon-(5) aus. Das Salz findet als Arzneimittel Verwendung, ist in Wasser löslieh und weist einen Schmelzpunkt von 147 bis 148 auf.
Beispiel 51 Gewichtsteile Phenyl-pyridyl-(2)-essig- säutreäthylester werden mit 9,1 Gewichtsteilen Natriumamid und 27 Gewichtsteilen 2-Di- methylamino-propylchlorid in 200 Gewichts teilen Toluol umgesetzt und zwei Stunden unter R,ückfluss gekocht.
Bei der Aufarbeitung wird in guter Aus beute ein Gemisch von a-Phenyl-a-pyridyl-(2)- y-dimethyl-aminovaleriansäure-äthylester und a-Plienyl-a-pyrid'yl- (2) -ss- methyl - y - dimethyl- amino-buttersäureester mit dem Kpo,8 160 bis 163 erhalten.
29,5 Gewichtsteile dieses Gemisches wer den in 150 Gewichtsteilen Benzol gelöst und zu einer Grignardlösung getropft, welche aus 6 Gewichtsteilen Magnesiumspänen, 27,5 Ge wichtsteilen Äthylbromid und 100 Gewichts teilen Äther bereitet war. Es wird zwei Stun den auf 60 .erwärmt und in üblicher Weise aufgearbeitet.
Das Isomerengemigeh der beiden entstan denen Ketone, das 2-Dimethyl-amino-4-phenyl- 4-pyridyl-(2')-heptanon-(5) und das 1-Di- methylamino-2-methyl-3-phenyl-3-pyridyl- (2') - hexanon-(4) wird bei der Destillation als viskoses rotes Öl vom Kpo,8164-166 erhalten.
Bei Herstellung der Maleinate in Essig ester scheidet sich aus dem Isomerengemisch nur das Maleinat des 2-Dimethylamino-4- phenyl-4-pyrid'yl-(2')-heptaton-(5) nach län gerem Stehen aus, das aus Essigester öfter umkristallisiert den Schmelzpunkt 147-148 zeigt. Die Base hat die Formel:
EMI0002.0001
Process for the preparation of a basic ketone The present invention is a process for the preparation of 2-dimethylamino-4-phenyl-4-pyridyl- (2 ') -heptanone- (5), which is characterized in that one u-Phenyl-a-pyridyl- (2) -y-dimethylamino-valeriaiic acid ester is reacted with an ethylmagnesium lialogenide.
In the preparation of the starting compound from phenylpyridyl- (2) -acetic acid ethyl ester and 2-dimethylaminopropyl chloride in gel-enwar t of sodium amide, an isomer mixture is produced which, in addition to the starting compound, contains the isomeric a-phenyl-a-pyridy l- (2) - l-methyl-y-dimethylamino butyric acid ester.
When carrying out the process according to the invention with this product, in addition to the 2-dimethyl-amino-4-phenyl-4-pyridyl- (2 ') - heptanone- (5), the isomeric 7-dimethylamino-2-methyl-3- phenyl-3-pyridyl- (2 ') -liexanone- (4).
When producing the maleate in ethyl acetate as a solvent, the isomeric base mixture is separated, and only the maleate of 2-dimethylamino-4-phenyl-4-pyridyl- (2 ') - heptanone- (5) crystallizes out. The salt is used as a medicinal product, is soluble in water and has a melting point of 147 to 148.
EXAMPLE 51 parts by weight of phenylpyridyl (2) acetic acid ethyl ester are reacted with 9.1 parts by weight of sodium amide and 27 parts by weight of 2-dimethylaminopropyl chloride in 200 parts by weight of toluene and refluxed for two hours.
When working up, a mixture of a-phenyl-a-pyridyl- (2) -y-dimethyl-aminovaleric acid-ethyl ester and a-plienyl-a-pyrid'yl- (2) -ss-methyl-y - Dimethyl amino butyric acid ester with the Kpo, 8 160 to 163 obtained.
29.5 parts by weight of this mixture who dissolved in 150 parts by weight of benzene and added dropwise to a Grignard solution, which was prepared from 6 parts by weight of magnesium turnings, 27.5 parts by weight of ethyl bromide and 100 parts by weight of ether. It is warmed to 60 for two hours and worked up in the usual way.
The mixture of isomers of the two ketones, 2-dimethylamino-4-phenyl-4-pyridyl- (2 ') -heptanone- (5) and 1-dimethylamino-2-methyl-3-phenyl-3, were produced -pyridyl- (2 ') -hexanone- (4) is obtained on distillation as a viscous red oil from Kpo, 8164-166.
When the maleate is produced in ethyl acetate, only the maleate of 2-dimethylamino-4-phenyl-4-pyrid'yl- (2 ') - heptaton- (5) separates from the isomer mixture after standing for a long time, and that of ethyl acetate more often recrystallized shows the melting point 147-148. The base has the formula:
EMI0002.0001
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE314558X | 1951-02-08 | ||
| CH305886T | 1952-01-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH314558A true CH314558A (en) | 1956-06-15 |
Family
ID=25735016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH314558D CH314558A (en) | 1951-02-08 | 1952-01-24 | Process for the preparation of a basic ketone |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH314558A (en) |
-
1952
- 1952-01-24 CH CH314558D patent/CH314558A/en unknown
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