NO117866B - - Google Patents
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- NO117866B NO117866B NO163322A NO16332266A NO117866B NO 117866 B NO117866 B NO 117866B NO 163322 A NO163322 A NO 163322A NO 16332266 A NO16332266 A NO 16332266A NO 117866 B NO117866 B NO 117866B
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- Norway
- Prior art keywords
- acid
- react
- ester
- allowed
- monocarboxylic acid
- Prior art date
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- -1 aniline magnesium halide Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000003931 anilides Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- INWLQCZOYSRPNW-UHFFFAOYSA-N mepivacaine Chemical compound CN1CCCCC1C(=O)NC1=C(C)C=CC=C1C INWLQCZOYSRPNW-UHFFFAOYSA-N 0.000 claims description 3
- VUHKTERBGMWQAY-UHFFFAOYSA-N N-(2-ethylphenyl)-1-propan-2-ylpiperidine-3-carboxamide Chemical compound C(C)C1=C(NC(C2CN(CCC2)C(C)C)=O)C=CC=C1 VUHKTERBGMWQAY-UHFFFAOYSA-N 0.000 claims description 2
- BOYAEDAIOHNLKU-UHFFFAOYSA-L [Br-].[Mg+2].ClC1=C(N)C(=CC=C1)C.[Br-] Chemical compound [Br-].[Mg+2].ClC1=C(N)C(=CC=C1)C.[Br-] BOYAEDAIOHNLKU-UHFFFAOYSA-L 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- ZICBNHLULHJETL-UHFFFAOYSA-N ethyl 1-methylpiperidine-2-carboxylate Chemical compound CCOC(=O)C1CCCCN1C ZICBNHLULHJETL-UHFFFAOYSA-N 0.000 claims description 2
- MCRPKBUFXAKDKI-UHFFFAOYSA-N ethyl pyridine-4-carboxylate Chemical compound CCOC(=O)C1=CC=NC=C1 MCRPKBUFXAKDKI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- ONXRNTKLIOTLCJ-UHFFFAOYSA-L magnesium 2,6-dimethylaniline dibromide Chemical compound [Br-].[Mg+2].CC1=C(N)C(=CC=C1)C.[Br-] ONXRNTKLIOTLCJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- XIWBSOUNZWSFKU-UHFFFAOYSA-N ethyl piperidine-3-carboxylate Chemical compound CCOC(=O)C1CCCNC1 XIWBSOUNZWSFKU-UHFFFAOYSA-N 0.000 claims 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 claims 1
- TWTWFMUQSOFTRN-UHFFFAOYSA-M CC[Mg]Br Chemical compound CC[Mg]Br TWTWFMUQSOFTRN-UHFFFAOYSA-M 0.000 claims 1
- HDHAIRSXHRAPHN-UHFFFAOYSA-L [Br-].[Mg+2].NC1=CC=CC=C1.[Br-] Chemical compound [Br-].[Mg+2].NC1=CC=CC=C1.[Br-] HDHAIRSXHRAPHN-UHFFFAOYSA-L 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- FCTZHFATVFONMW-UHFFFAOYSA-N n-phenylpyridine-4-carboxamide Chemical compound C=1C=NC=CC=1C(=O)NC1=CC=CC=C1 FCTZHFATVFONMW-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Natural products OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- XQMUEFDDYYIRPT-UHFFFAOYSA-L [Br-].[Mg+2].C(C)C1=C(N)C=CC=C1.[Br-] Chemical compound [Br-].[Mg+2].C(C)C1=C(N)C=CC=C1.[Br-] XQMUEFDDYYIRPT-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WFNLHDJJZSJARK-UHFFFAOYSA-N 2-chloro-6-methylaniline Chemical compound CC1=CC=CC(Cl)=C1N WFNLHDJJZSJARK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 229960005015 local anesthetics Drugs 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DNZSDACGXYHMOL-UHFFFAOYSA-N n-(2-ethylphenyl)piperidine-3-carboxamide Chemical compound CCC1=CC=CC=C1NC(=O)C1CNCCC1 DNZSDACGXYHMOL-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/86—Vessels; Containers; Vacuum locks
- H01J29/867—Means associated with the outside of the vessel for shielding, e.g. magnetic shields
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/86—Vessels; Containers; Vacuum locks
- H01J29/87—Arrangements for preventing or limiting effects of implosion of vessels or containers
Landscapes
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
- Hydrogenated Pyridines (AREA)
- Image-Pickup Tubes, Image-Amplification Tubes, And Storage Tubes (AREA)
Description
Fremgangsmåte til fremstilling av anestetisk virkende amider av N-alkylpiperidin-monokarbonsyre og N-alkylpyrrolidin-«-monokarbonsyre. Process for the production of anesthetically effective amides of N-alkylpiperidine-monocarboxylic acid and N-alkylpyrrolidine-«-monocarboxylic acid.
Foreliggende oppfinnelse angår en The present invention relates to a
fremgangsmåte til fremstilling av amider method for the production of amides
av N-alkylpiperidin-monokarbonsyre og of N-alkylpiperidine monocarboxylic acid and
av N-alkylpyrrolidin-a-monokarbonsyre, of N-alkylpyrrolidine-α-monocarboxylic acid,
hvilke amider har de generelle formler: which amides have the general formulas:
I disse formler betegner R, en alkylgruppe med mindre enn 10 kullstoffato-mer, R2 en lavere alkylgruppe eller et kloratom, R,, et hydrogenatom, en hydroksyl-gruppe, en lavere alkylgruppe eller en alkoksygruppe og R4 et hydrogenatom, et In these formulas R denotes an alkyl group with less than 10 carbon atoms, R 2 denotes a lower alkyl group or a chlorine atom, R 1 denotes a hydrogen atom, a hydroxyl group, a lower alkyl group or an alkoxy group and R 4 a hydrogen atom, a
kloratom, en lavere alkylgruppe eller en chlorine atom, a lower alkyl group or a
alkoksygruppe. Alternativt kan R2, R3 og alkoxy group. Alternatively, R2, R3 and
R4 alle være hydrogen i en og samme forbindelse. Karbonsyreamidgruppen kan R4 can all be hydrogen in one and the same compound. The carboxylic acid amide group can
være tilknyttet piperidinringen i alfa-, be attached to the piperidine ring in alpha-,
beta- eller gammastillingen. the beta or gamma position.
Disse amider har vist seg å være meget These amides have been shown to be very
gode lokalanestetika med giftighet som er meget liten i forhold til forbindelsenes aktivitet. good local anesthetics with toxicity that is very small compared to the activity of the compounds.
De karakteristiske hovedtrekk ved fremgangsmåten ifølge oppfinnelsen er at man lar et anilinmagnesiumhalogenid med den generelle formel: The main characteristic features of the method according to the invention are that one leaves an aniline magnesium halide with the general formula:
i hvilken X betegner halogen og R2, R3 og R4 har de ovenfor angitte betydninger, reagere med en pyridin-monokarbonsyreester eller med en piperidin-monokarbonsyreester eller en pyrrol-a-monokarbonsyreester eller en pyrrolidin-a-monokarbonsyre-ester, hvilke estere kan være hydrerte eller ikke hydrerte, alkylerte eller ikke alkylerte ved nitrogenatomet i den heterocykliske ring, hvorpå man hydro-lyser er det erholdte reaksjonsprodukt med en syre og i tilfelle hvor utgangsmaterialet er en pyridin-monokarbonsyreester eller en pyrrbl-a-monokarbonsyreester underkaster den heterocykliske ring en hydrering med derpå følgende alkylering av nitrogenet i den heterocykliske ring, f. eks. med et dialkylsulfat eller alkylhalogenid. Hydreringen kan utføres med metallisk natrium eller fortrinsvis med vanlige hyd-reringskatalysatorer. in which X denotes halogen and R 2 , R 3 and R 4 have the meanings given above, react with a pyridine monocarboxylic acid ester or with a piperidine monocarboxylic acid ester or a pyrrole α-monocarboxylic acid ester or a pyrrolidine α-monocarboxylic acid ester, which esters can be hydrogenated or not hydrogenated, alkylated or not alkylated at the nitrogen atom of the heterocyclic ring, after which the reaction product obtained is hydrolysed with an acid and in the case where the starting material is a pyridine monocarboxylic acid ester or a pyrrbl-α-monocarboxylic acid ester the heterocyclic ring is subjected to a hydrogenation with subsequent alkylation of the nitrogen in the heterocyclic ring, e.g. with a dialkyl sulfate or alkyl halide. The hydrogenation can be carried out with metallic sodium or preferably with ordinary hydrogenation catalysts.
I det følgende beskrives som eksemp- In the following, it is described as an example
ler noen utførelsesformer for oppfinnelsen. shows some embodiments of the invention.
Eksempel 1: Example 1:
Etylmagnesiumbromid fremstilles på Ethylmagnesium bromide is produced on
vanlig måte ved å la 185 vektsdeler etyl- usual way by allowing 185 parts by weight of ethyl
bromid i 100 deler vannfri eter reagere med 37 deler magnesium-dreiespon. Under kraftig omrøring tilsettes det derpå 121 bromide in 100 parts of anhydrous ether react with 37 parts of magnesium turnings. With vigorous stirring, 121 is then added
deler 2,6-dimetylanilin med en hastighet som er avhengig av gassutviklingens vold- splits 2,6-dimethylaniline at a rate that depends on the violence of gas evolution
somhet. Når gassutviklingen er opphørt, sameness. When gas development has ceased,
tilsettes suspensjonen av 2,6-dimetylanilin-magnesiumbromid 85 deler N-metyl-pipekolinsyre-etylester. Blandingen opp- is added to the suspension of 2,6-dimethylaniline-magnesium bromide 85 parts of N-methyl-pipecolic acid ethyl ester. The mixture up-
varmes under tilbakeløpskjøling y2 time under stadig omrøring, hvorpå den ned- is heated under reflux cooling for 2 hours with constant stirring, after which the
kjøles. Fortynnet saltsyre tilsettes forsik- cooled. Diluted hydrochloric acid is added to ensure
tig for å oppløse og hydrolysere de dan- to dissolve and hydrolyze the resulting
nende maghesiumforbindelser. pH-verdien innstilles på 5.5, den vandige fase fraskil- nende magnesium compounds. The pH value is set to 5.5, the aqueous phase separates
les og ekstraheres med ytterligere meng- read and extracted with additional amounts of
der eter for å fjerne overskuddet av dime- there ether to remove the excess of dime-
tylanilin. Etter tilsetning av et overskudd av ammoniakk til oppløsningen utvinnes reaksj onsproduktet, N-metylpipekolin-syre-2,6-dimetylanilid, ved ekstraksjon med isoamylalkohol. Isoamylalkoholopp- tylaniline. After adding an excess of ammonia to the solution, the reaction product, N-methylpipecolic acid-2,6-dimethylanilide, is recovered by extraction with isoamyl alcohol. isoamyl alcohol
løsningen inndampes til tørrhet, residuet oppløses i fortynnet saltsyre, behandles med trekull og felles påny med NaOH. the solution is evaporated to dryness, the residue is dissolved in dilute hydrochloric acid, treated with charcoal and combined again with NaOH.
Herved fåes N-metyl-pipekolinsyre-2,6-dimetylanilid i krystallinsk form. This gives N-methyl-pipecolic acid-2,6-dimethylanilide in crystalline form.
Eksempel 2: Example 2:
På en måte tilsvarende den i eksempel In a way similar to the one in the example
1 beskrevne fremstilles det 2-etylanilin-magnesiumbromid av 121 vektsdeler 2- 1 described, 2-ethylaniline-magnesium bromide is prepared from 121 parts by weight 2-
etylanilin, og man lar 2-etylanilinmagne-siumbromidet reagere med 78 deler ni-pekotinsyre-etylester. Etter anvendelse av den i eksempel 1 beskrevne fremgangs- ethylaniline, and the 2-ethylaniline magnesium bromide is allowed to react with 78 parts of ni-pecotic acid ethyl ester. After applying the procedure described in example 1,
måte får man nipekotinsyre-2-etylanilid. method one obtains nipecotic acid-2-ethylanilide.
10 deler av dette anilid oppløses i 16 deler isopropylalkohol og 5,3 deler isopropylbro- 10 parts of this anilide are dissolved in 16 parts of isopropyl alcohol and 5.3 parts of isopropyl bro-
mld, - og det tilsettes 5 deler kaliumkarbo- mld, - and 5 parts of potassium carbo- are added
nat. Blandingen oppvarmes under tilbake- night The mixture is heated under reflux
løpskjøling i 12 timer under omrøring, filt- continuous cooling for 12 hours while stirring, felt-
reres og inndampes til tørrhet. Man opp- stirred and evaporated to dryness. One up-
løser residuet i fortynnet saltsyre og feller påny med alkali, hvorved man får N-iso-propylnipekotinsyre-2-etylanilid i form av den frie base. dissolves the residue in dilute hydrochloric acid and precipitates again with alkali, whereby N-iso-propylnipecotic acid-2-ethylanilide is obtained in the form of the free base.
Eksempel 3: Example 3:
På en måte tilsvarende den i eksem- In a way similar to that in ex-
pel 1 beskrevne fremstilles anilinmagne- pel 1 described are prepared aniline magne-
siumbromid av 93 deler anilin, og man lar sium bromide of 93 parts of aniline, and one lets
aniiinmagnesiumbromidet reagere med 75 the amine magnesium bromide reacts with 75
deler isonikotinsyre-etylester. Den herved dannede magnesiumforbindelse oppløses og hydrolyseres i fortynnet saltsyre, hvorpå oppløsningenes pH-verdi innstilles på om- shares isonicotinic acid ethyl ester. The magnesium compound thus formed is dissolved and hydrolysed in dilute hydrochloric acid, after which the solutions' pH value is adjusted to about
kring 7 og eteren fraskilles. Den tilbake- around 7 and the ether is separated. The back-
blivende vandige oppløsning ekstraheres 2 ganger med isoamylalkohol, og oppløs- remaining aqueous solution is extracted twice with isoamyl alcohol, and dissolve
ningen sammen med eteroppløsningen inndampes til tørrhet. Residuet underkas- The extract together with the ether solution is evaporated to dryness. The residue subject to
tes vanndampdestillasjon inntil det er be- water vapor distillation is carried out until it is be-
fridd fra anilin. Det tilbakeblivende iso-nikotinsyreanilid oppløses i fortynnet salt- freed from aniline. The remaining iso-nicotinic acid anilide is dissolved in dilute salt
syre, behandles med trekull, felles påny med alkali, hvorpå bunnfallet frafiltreres og tørres. 99 deler av isonikotinsyreanili- acid, treated with charcoal, precipitated again with alkali, after which the precipitate is filtered off and dried. 99 parts of isonicotinic acid anili-
det oppløses i 240 deler alkohol og 60 deler iseddik. Oppløsningen tilsettes 2,5 deler platinaoksyd, og anilidet hydreres ved et trykk på 2—5 atmosfærer og en tempera- it dissolves in 240 parts alcohol and 60 parts glacial acetic acid. 2.5 parts of platinum oxide are added to the solution, and the anilide is hydrated at a pressure of 2-5 atmospheres and a temperature
tur på 50—80° C. Når det ikke lenger ab- temperature of 50-80° C. When it no longer ab-
sorberes hydrogen, frafiltreres katalysa- hydrogen is sorbed, the catalysis is filtered off
toren. Filtratet tilsettes 40 deler NaOH tower. 40 parts of NaOH are added to the filtrate
oppløst i vann til en 40—50 pst.'s oppløs- dissolved in water to a 40-50 percent solvent
ning, samt 250 deler eter. Etter nedkjøling frafiltreres det utfelte natriumacetat, og filtratet inndampes til krystallisasjon eller til tørrhet. 10 deler av residuet fra inn-dampningen (eller det krystallinske pro- ning, as well as 250 parts of ether. After cooling, the precipitated sodium acetate is filtered off, and the filtrate is evaporated to crystallization or to dryness. 10 parts of the residue from the evaporation (or the crystalline pro-
dukt) oppløses i 16 deler metanol. Oppløs- duct) is dissolved in 16 parts methanol. dissolve-
ningen tilsettes 5 deler kaliumkarbonat og 5,2 deler dimetylsulfat. Den oppvarmes der- 5 parts of potassium carbonate and 5.2 parts of dimethylsulphate are added to the mixture. It is heated there-
på i 6 timer under tilbakeløpskjøling og omrøring hvorpå oppløsningen filtreres og inndampes til tørrhet. Residuet oppløses i fortynnet saltsyre, behandles med trekull og felles påny med alkali. På denne måte får man krystallinsk N-metylisonipekotin- for 6 hours under reflux and stirring, after which the solution is filtered and evaporated to dryness. The residue is dissolved in dilute hydrochloric acid, treated with charcoal and combined again with alkali. In this way, crystalline N-methylisonipecotin is obtained
syreanilid. acid anilide.
Eksempel 4: Example 4:
På en måte tilsvarende den i eksem- In a way similar to that in ex-
pel 1 beskrevne fremstilles 2-klor-6-metyl-anilin-magnesiumbromid av 141,5 deler 2-klor-6-metylanilin. Man lar derpå sist- pel 1 described, 2-chloro-6-methyl-aniline-magnesium bromide is prepared from 141.5 parts of 2-chloro-6-methylaniline. One then lets last-
nevnte forbindelse reagere med 100 deler N-normalt-butyl-pyrrolidin-a-karbonsyre- said compound react with 100 parts of N-normal-butyl-pyrrolidine-α-carboxylic acid-
ester. Ved å bruke den i eksempel 1 be- ester. Using it in Example 1 be-
skrevne fremgangsmåte får man N-nor-malt-butyl-pyrrolidin-a-karbonsyre-2-klor-6-metylanilid. written procedure gives N-nor-malt-butyl-pyrrolidine-α-carboxylic acid-2-chloro-6-methylanilide.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL6507304A NL6507304A (en) | 1965-06-09 | 1965-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO117866B true NO117866B (en) | 1969-10-06 |
Family
ID=19793333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO163322A NO117866B (en) | 1965-06-09 | 1966-06-06 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3422220A (en) |
| AT (1) | AT259643B (en) |
| BE (1) | BE682209A (en) |
| CH (1) | CH446433A (en) |
| DE (1) | DE1462832A1 (en) |
| DK (1) | DK117724B (en) |
| ES (1) | ES327638A1 (en) |
| GB (1) | GB1146078A (en) |
| NL (1) | NL6507304A (en) |
| NO (1) | NO117866B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1175444A (en) * | 1967-03-03 | 1969-12-23 | Thorn Aei Radio Valves & Tubes | Improvements in Implosion-Resistant Cathode Ray Tubes |
| US3541251A (en) * | 1967-09-19 | 1970-11-17 | Standard Elektrik Lorenz Ag | Implosion-protecting frame for television picture tubes and process for its installation |
| US3614519A (en) * | 1967-12-18 | 1971-10-19 | Zenith Radio Corp | Cathode-ray tube magnetic shield |
| JPS597731Y2 (en) * | 1979-06-07 | 1984-03-09 | ソニー株式会社 | cathode ray tube equipment |
| JPS5743347A (en) * | 1980-08-26 | 1982-03-11 | Mitsubishi Electric Corp | Cathode ray tube |
| GB2105956B (en) * | 1981-08-04 | 1985-02-06 | Tokyo Shibaura Electric Co | Cathode ray tube device |
| JPS5851683A (en) * | 1981-09-22 | 1983-03-26 | Mitsubishi Electric Corp | Cathode-ray tube device |
| US4551765A (en) * | 1981-10-26 | 1985-11-05 | Allied Corporation | Cathode ray tube vibration isolator |
| US4556821A (en) * | 1984-03-15 | 1985-12-03 | Rca Corporation | Color image display system having an improved external magnetic shield |
| KR900001701B1 (en) * | 1985-03-20 | 1990-03-19 | 미쯔비시 뎅기 가부시끼가이샤 | Color crt |
| US4943755A (en) * | 1985-05-20 | 1990-07-24 | Mitsubishi Denki Kabushiki Kaisha | Magnetic shielding with constant-current coils for CRT |
| IT1243083B (en) * | 1990-09-28 | 1994-05-23 | Videocolor Spa | CATHODE-RAY TUBE EQUIPPED WITH AN ANTI-IMPLOSION BAND |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE627679A (en) * | 1962-01-29 | |||
| NL291096A (en) * | 1963-04-03 | |||
| US3369074A (en) * | 1965-04-02 | 1968-02-13 | Warwick Electronics Inc | Television tube shield and mounting structure |
-
1965
- 1965-06-09 NL NL6507304A patent/NL6507304A/xx unknown
-
1966
- 1966-05-10 US US549036A patent/US3422220A/en not_active Expired - Lifetime
- 1966-06-04 DE DE19661462832 patent/DE1462832A1/en active Pending
- 1966-06-06 NO NO163322A patent/NO117866B/no unknown
- 1966-06-06 AT AT534766A patent/AT259643B/en active
- 1966-06-06 GB GB25016/66A patent/GB1146078A/en not_active Expired
- 1966-06-06 CH CH813866A patent/CH446433A/en unknown
- 1966-06-06 DK DK290066AA patent/DK117724B/en unknown
- 1966-06-07 ES ES0327638A patent/ES327638A1/en not_active Expired
- 1966-06-07 BE BE682209D patent/BE682209A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US3422220A (en) | 1969-01-14 |
| DE1462832A1 (en) | 1968-12-05 |
| NL6507304A (en) | 1966-12-12 |
| ES327638A1 (en) | 1967-08-16 |
| CH446433A (en) | 1967-11-15 |
| GB1146078A (en) | 1969-03-19 |
| BE682209A (en) | 1966-12-07 |
| DK117724B (en) | 1970-05-25 |
| AT259643B (en) | 1968-01-25 |
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