DE1470379C - 11 (1 methyl 4 piperidyhden) morphan thridin its acid salts and manufacturing process - Google Patents
11 (1 methyl 4 piperidyhden) morphan thridin its acid salts and manufacturing processInfo
- Publication number
- DE1470379C DE1470379C DE1470379C DE 1470379 C DE1470379 C DE 1470379C DE 1470379 C DE1470379 C DE 1470379C
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- piperidylidene
- compound
- thridin
- piperidyhden
- 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
- 239000002253 acid Substances 0.000 title claims description 9
- 150000003839 salts Chemical class 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title 1
- ZPAPCUKKKOSLPZ-UHFFFAOYSA-N morphan Chemical compound C1CNC2CCCC1C2 ZPAPCUKKKOSLPZ-UHFFFAOYSA-N 0.000 title 1
- -1 1-methyl-4-piperidylidene Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000012024 dehydrating agents Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 238000006798 ring closing metathesis reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 1
- MYGXGCCFTPKWIH-UHFFFAOYSA-N 4-chloro-1-methylpiperidine Chemical compound CN1CCC(Cl)CC1 MYGXGCCFTPKWIH-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003474 anti-emetic effect Effects 0.000 description 1
- 230000000794 anti-serotonin Effects 0.000 description 1
- 239000002111 antiemetic agent Substances 0.000 description 1
- 239000003420 antiserotonin agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000812 cholinergic antagonist Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001558 histaminolytic effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000000506 psychotropic effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002048 spasmolytic effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Description
Die Erfindung betrifft 1 l-(l-Methyl-4-piperidyliden)-morphanthridin mit der Formel IThe invention relates to 11- (1-methyl-4-piperidylidene) -morphanthridine with the formula I.
CH=NvCH = Nv
dessen Säureadditionssalze und Herstellungsverfahren.its acid addition salts and manufacturing process.
Diese Verbindungen .weisen eine überlegene ■ histaminolytisctie und ferner eine psychotrope, antiemetische, spasmolytische sowie eine Antiserotoninwirkung auf.These compounds have a superior histaminolytic effect and also a psychotropic, antiemetic, spasmolytic and an antiserotonin effect on.
Sie werden dadurch hergestellt, daß entwederThey are made by either
a) die Verbindung der Formel IIa) the compound of formula II
Stoffperoxid, Jod, Chromsäure, Kaliumpermanganat, Eisen(III)-cnlorid, nitrose Gase oder Luft, bei gegebenenfalls erhöhten Temperaturen, besonders zwischen 60 und 1200C, zweckmäßig in einem organischen Lösungsmittel oder in Wasser bzw. in einer verdünnten Mineralsäure, behandelt und gegebenenfalls die nach a) oder b) erhaltene Verbindung mit .Säuren in Salze übergeführt wird.'Substance peroxide, iodine, chromic acid, potassium permanganate, iron (III) chloride, nitrous gases or air, at optionally elevated temperatures, especially between 60 and 120 0 C, expediently in an organic solvent or in water or in a dilute mineral acid, treated and if appropriate, the compound obtained according to a) or b) is converted into salts with "acids."
Die Arbeitsweise a) wird vorzugsweise mit PoIyphosphorsäure oder Phosphortrichlorid zwischen 80 und 1600C durchgeführt.The procedure a) is preferably carried out with phosphorus trichloride or PoIyphosphorsäure between 80 and 160 0 C.
Zur Herstellung der Säuresalze kommen physiologisch verträgliche anorganische oder organische Säuren, wie Salz-, Schwefel-, Phosphor-, Zitronen-, Malein-, Fumar- und Weinsäure in Betracht.Physiologically compatible inorganic or organic compounds are used for the preparation of the acid salts Acids, such as hydrochloric, sulfuric, phosphoric, citric, maleic, fumaric and tartaric acid, are suitable.
Die für die Arbeitsweise b) erforderliche Ausgangsverbindung der Formel HI wird im belgischen Patent 652938 (s. C. A.,· 64, 19475 h [1966]) beschrieben.The starting compound of the formula HI required for procedure b) is described in the Belgian patent 652938 (see C.A., 64, 19475h [1966]).
Die nachstehenden Beispiele dienen zur näheren Erläuterung der Erfindung.The following examples serve to explain the invention in more detail.
mit einem wasserabspaltenden Mittel, wie Phosphorpentoxid, Phosphorhalogenide, Polyphosphorsäure,
Polyphosphorsäureester, Aluminiumchlorid oder wasserfreies Zinkchlorid, bei erhöhten Temperaturen,
gegebenenfalls in Gegenwart eines inerten Lösungsmittels, beispielsweise Toluol oder Xylol, oder
b) die Verbindung der Formel IIIwith a dehydrating agent, such as phosphorus pentoxide, phosphorus halides, polyphosphoric acid, polyphosphoric acid ester, aluminum chloride or anhydrous zinc chloride, at elevated temperatures, optionally in the presence of an inert solvent, for example toluene or xylene, or
b) the compound of formula III
mit einem Oxydationsmittel, wie Chinon, Wasserll-(l-Methyl-4-piperidyliden)-morphanthridin with an oxidizing agent such as quinone, water-III- (1-methyl-4-piperidylidene) -morphanthridine
Zu einer Lösung von 49,2 g 2-Aminobenzophenon in 300 ml absolutem Tetrahydrofuran tropft man unter Rühren eine aus 22,6 g Magnesiumspänen und 113 g 4-Chlor-l-methylpiperidin in 375 ml Tetrahydrofuran hergestellte Grignardverbindung zu und erhitzt 3 Stunden unter Rückfluß. Der nach anschließendem Einengen verbleibende Rückstand wird mit Eis und Ammoniumchlorid behandelt und das langsam kristallisierende Produkt abgesaugt, getrocknet und aus Essigester umkristallisiert. Man erhält 47,8 g2-Amino-a-hydroxy-a-(l-methyl-4-piperidyl)-diphenylmethan vom Schmelzpunkt 145 bis 1470C.A Grignard compound prepared from 22.6 g of magnesium turnings and 113 g of 4-chloro-1-methylpiperidine in 375 ml of tetrahydrofuran is added dropwise with stirring to a solution of 49.2 g of 2-aminobenzophenone in 300 ml of absolute tetrahydrofuran, and the mixture is refluxed for 3 hours . The residue remaining after subsequent concentration is treated with ice and ammonium chloride and the slowly crystallizing product is filtered off with suction, dried and recrystallized from ethyl acetate. This gives 47.8 g 2-amino-a-hydroxy-a- (l-methyl-4-piperidyl) diphenylmethane of melting point 145 to 147 0 C.
55 g dieser Verbindung werden in 305 ml 80%iger Schwefelsäure eingetragen, 5 Minuten auf 95 bis 1000C erhitzt, nach Abkühlung auf Eis gegossen und mit Ammoniak alkalisch gestellt. Das als öl abgeschiedene 2-Amino-a-(l -methyl-4-piperidyliden)-diphenyl-methan wird ausgeäthert, über Natriumsulfat getrocknet und nach Einengen fraktioniert.55 g of this compound are introduced into 305 ml of 80% strength sulfuric acid, heated to 95 to 100 ° C. for 5 minutes, after cooling poured onto ice and made alkaline with ammonia. The 2-amino-a- (1-methyl-4-piperidylidene) -diphenyl-methane which has separated out as an oil is extracted with ether, dried over sodium sulfate and, after concentration, fractionated.
Ausbeute: 40,0 g, Kp.?,o9mm : 171 bis 1740C.Yield: 40.0 g, bp ? , o9 mm : 171 to 174 0 C.
20 g der Aminoverbindung werden mit 25 ml Ameisensäure, 100 ml Toluol 4 Stunden am Wasserabscheider erhitzt. Nach Abkühlung.gießt man auf Eis, macht mit Ammoniak alkalisch, äthert aus, trocknet die Ätherlösung über Natriumsulfat, engt ein und kristallisiert den Rückstand aus Benzol20 g of the amino compound are mixed with 25 ml of formic acid and 100 ml of toluene on a water separator for 4 hours heated. After cooling, it is poured onto ice, made alkaline with ammonia, etherified, dry the ethereal solution over sodium sulfate, concentrate and crystallize the residue from benzene
III unter Zusatz von Petroläther um. Man erhält 11,5 gIII with the addition of petroleum ether. 11.5 g are obtained
2-Formylamino-a-(l-methyl-4-piperidyliden)-diphenylmethan vom Schmelzpunkt 122 bis 124° C.2-Formylamino-a- (1-methyl-4-piperidylidene) -diphenylmethane from melting point 122 to 124 ° C.
11,3g 2 - Formylamino - α - (1 - methyl - 4 - piperidyliden)-diphenylmethan werden in 50 g Polyphosphorsäure 45 Minuten auf 150 bis 160° C erhitzt. Nach dem Erkalten wird die Reaktionsmischung auf Eis gegeben, mit Ammoniak alkalisch gestellt und aus-11.3g 2 - formylamino - α - (1 - methyl - 4 - piperidylidene) diphenylmethane are heated in 50 g of polyphosphoric acid to 150 to 160 ° C for 45 minutes. To When it cools, the reaction mixture is poured onto ice, made alkaline with ammonia and
geäthert. Die Ätherlösung wird getrocknet, eingeengt und der Rückstand durch Chromatographie gereinigt. Man erhält 2,0 g ll-(l-Methyl-4-piperidyliden)-morphanthridin vom Schmelzpunkt LOl bis 103c C.etherified. The ether solution is dried and concentrated, and the residue is purified by chromatography. This gives 2.0 g of ll- (l-methyl-4-piperidylidene) -morphanthridin from the melting point to 103 c LOl C.
11 -(I -Methyl-4-piperidyliden)-morphanthridin11 - (I -methyl-4-piperidylidene) -morphanthridine
288 mg 5,6-Dihydro-ll-(l-methyl-4-piperidyliden)-morphanthridin werden in 15 ml Toluol mit 245 mg Chloranil 3 Stunden gekocht. Die Reaktionslösung wird nach Abkühlen filtriert und mit Salzsäure extrahiert. Aus der salzsauren Lösung wird mit Ammoniak die Base in Freiheit gesetzt und in Äther aufgenommen, Nach dem Trocknen über Natriumsulfat und Einengen der Atherlösung erhält man 150 mg 11-(1-Methyl-4-piperidyliden)-morphanthridin vom Schmelzpunkt 103°C.288 mg of 5,6-dihydro-II- (1-methyl-4-piperidylidene) -morphanthridine are boiled in 15 ml of toluene with 245 mg of chloranil for 3 hours. The reaction solution is filtered after cooling and extracted with hydrochloric acid. The hydrochloric acid solution becomes with ammonia the base set free and taken up in ether, After drying over sodium sulfate and concentrating the ether solution, 150 mg of 11- (1-methyl-4-piperidylidene) -morphanthridine are obtained with a melting point of 103 ° C.
Die gleiche Verbindung wird auch erhalten, wenn man 288mg 5,6-Dihydro-ll-(l-methyl-4-piperidyliden)-morphanthridin in 30 ml verdünnter Salzsäure löst und unter Erhitzen auf 1000C 8 Stunden lang Luft durchleitet. .The same compound is also obtained when 288mg of 5,6-dihydro-ll- (l-methyl-4-piperidylidene) -morphanthridin dissolved in 30 ml diluted hydrochloric acid and 8 hours by passing air under heating to 100 0 C. .
Ausbeute: 170 mg, Schmp.: 100 bis 1020C.Yield: 170 mg, m.p .: 100 to 102 0 C.
Claims (3)
b)- die Verbindung der Formel IIIwith a dehydrating agent at elevated temperatures, optionally in the presence of an inert solvent, or
b) - the compound of formula III
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1695753B2 (en) | Process for the preparation of 6,6-disubstituted 2,2-dimethyl-4-oxopiperidines | |
| DE1720019C3 (en) | 1 -Benzyl-2-aminoacetyl-pyrrole derivatives, their salts and process for their preparation | |
| DE1470379C (en) | 11 (1 methyl 4 piperidyhden) morphan thridin its acid salts and manufacturing process | |
| DE1470379B1 (en) | 11- (1-Methyl-4-piperidylidene) -morphanthridine, its acid salts and production process | |
| DE2431409C2 (en) | Process for the preparation of 1-aminoanthraquinone | |
| DD207914A5 (en) | PROCESS FOR THE PREPARATION OF DERIVATIVES OF VINYL PHOSPHONES OR VINYLPYROPHOSPHONIC ACIDS | |
| DE1921842A1 (en) | Process for the preparation of cycloaliphatic halides | |
| DE1267684B (en) | Method of making iron | |
| DE2009780C2 (en) | N, o-Dilithium derivative of 2-phenyl-2-imidazoline, a process for the production thereof and a process for the production of imidazo [2, l-a] isoindoles | |
| DE2410310A1 (en) | PROCESS FOR THE PREPARATION OF 1-AMINOANTHRAQUINONE | |
| DE1920081C (en) | Process for the preparation of 4 5 Benztropon 2 7 dicarboxylic acid esters | |
| DE2521895A1 (en) | Alpha-Amino-2-adamantylacetic acid prepn - from 2-adamantylacetic acid via alpha-bromo-2-adamantylacetic acid | |
| DE906936C (en) | Process for the preparation of acid amides by rearrangement of ketoximes | |
| DE2321332C2 (en) | Process for the preparation of 2-nitro-5-chlorobenzenesulfonic acid chloride or of 2-nitro-5-chlorobenzenesulfonic acid | |
| DE1593315B1 (en) | 9-isopropylidene-9,10-dihydroanthracene-10-carboxylic acid-ß-diaethylamino-ethyl ester, their salts and process for their preparation | |
| DE544886C (en) | Process for the preparation of substitution products of aromatic hydrocarbons | |
| DE947370C (en) | Process for the preparation of 4-thionylamino-2-oxy-benzoyl chloride | |
| AT375372B (en) | METHOD FOR PRODUCING NEW 15-BROMO-1,2DIDEHYDRO-3-HYDROXYASPIDOSPERMIDINE-3-CARBONS [UR - METHYLESTER DERIVATIVES | |
| AT325600B (en) | PROCESS FOR THE PRODUCTION OF ARYLALKYLPYRRYLAMINO ETHANOLS AND THEIR SALT | |
| AT238174B (en) | Process for the preparation of N- (2,3-dimethylphenyl) anthranilic acid and its salts | |
| DE1793463C3 (en) | ||
| DE1205063B (en) | Process for the production of nitrosylsulphuric acid | |
| CH435253A (en) | Process for the continuous production of tetrahydrophthalic anhydride | |
| DE1033671B (en) | Process for the production of diazomethane | |
| DE1196649B (en) | Process for the preparation of 1-oximino-2-chlorocyclododecadiene-5, 9 |