NO150553B - INFLATABLE BATH - Google Patents
INFLATABLE BATH Download PDFInfo
- Publication number
- NO150553B NO150553B NO794213A NO794213A NO150553B NO 150553 B NO150553 B NO 150553B NO 794213 A NO794213 A NO 794213A NO 794213 A NO794213 A NO 794213A NO 150553 B NO150553 B NO 150553B
- Authority
- NO
- Norway
- Prior art keywords
- group
- substituted
- general formula
- basic
- lower alkyl
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000002170 ethers Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004036 acetal group Chemical group 0.000 claims description 3
- 150000001241 acetals Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003386 piperidinyl group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical group [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical group CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- -1 dialkylamino alcohols Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000002048 spasmolytic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 208000005392 Spasm Diseases 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XQYZDYMELSJDRZ-UHFFFAOYSA-N papaverine Chemical compound C1=C(OC)C(OC)=CC=C1CC1=NC=CC2=CC(OC)=C(OC)C=C12 XQYZDYMELSJDRZ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OCWGRWAYARCRTQ-UHFFFAOYSA-N 2-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CC(Cl)CN(C)C OCWGRWAYARCRTQ-UHFFFAOYSA-N 0.000 description 1
- RAGSWDIQBBZLLL-UHFFFAOYSA-N 2-chloroethyl(diethyl)azanium;chloride Chemical compound Cl.CCN(CC)CCCl RAGSWDIQBBZLLL-UHFFFAOYSA-N 0.000 description 1
- WQMAANNAZKNUDL-UHFFFAOYSA-N 2-dimethylaminoethyl chloride Chemical compound CN(C)CCCl WQMAANNAZKNUDL-UHFFFAOYSA-N 0.000 description 1
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 1
- 229930008281 A03AD01 - Papaverine Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- YYHIRPUVYUUCTJ-UHFFFAOYSA-N methyl 2-[2-(dimethylamino)ethoxy]benzoate Chemical compound COC(=O)C1=CC=CC=C1OCCN(C)C YYHIRPUVYUUCTJ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UKTPBONTZVCEST-UHFFFAOYSA-N n-[4-[2-(diethylamino)ethoxy]phenyl]benzamide Chemical compound C1=CC(OCCN(CC)CC)=CC=C1NC(=O)C1=CC=CC=C1 UKTPBONTZVCEST-UHFFFAOYSA-N 0.000 description 1
- 229960001789 papaverine Drugs 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 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 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B7/00—Collapsible, foldable, inflatable or like vessels
- B63B7/06—Collapsible, foldable, inflatable or like vessels having parts of non-rigid material
- B63B7/08—Inflatable
- B63B7/082—Inflatable having parts of rigid material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B3/00—Hulls characterised by their structure or component parts
- B63B3/14—Hull parts
- B63B3/38—Keels
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Ocean & Marine Engineering (AREA)
- Toys (AREA)
- Tents Or Canopies (AREA)
- Cosmetics (AREA)
Description
Fremgangsmåte til fremstilling av terapeutisk virksomme basiske etere av substituerte oksy-benzosyrer, så vel som deres salter og kvarternære ammoniumforbindelser. Process for the preparation of therapeutically active basic ethers of substituted oxybenzoic acids, as well as their salts and quaternary ammonium compounds.
Oppfinnelsen vedrører en fremgangs--måte til fremstilling av nye terapeutisk The invention relates to a process for the production of new therapeutics
virksomme, basiske etere av substituerte active, basic ethers of substituted
oksybenzosyrer med den generelle formel I oxybenzoic acids of the general formula I
hvori R, betyr en ikke substituert eller en med halogen, nitro- eller lavere alkylgrupper substituert fenolrest, eller en lavalkyl-fenylrest, hvor alkylgruppen kan være substituert med en hydroksylgruppe, R2 betyr hydrogen, lavere alkyl eller fenyl eller betyr en morfolingruppe, R3 og R4 betyr lavere alkylgrupper eller sammen med nitro-genatomet en piperidingruppe, R5 betyr hydrogen eller halogen og R„ betyr en rett eller forgrenet lavere alkylengruppe, samt deres salter og kvaternære ammoniumforbindelser, og fremgangsmåten er karakterisert ved at et basisk substituert alkylhalogenid eller et salt herav med den generelle formel II hvori R.,, R, og Rn har den ovenfor angitte betydning og Hal betyr et halogen, omsettes eventuelt i nærvær av et basisk kondensa-sjonsmiddel med et oksybenzosyreamid eller med en alkaliforbindelse av dette med den generelle forbindelse III hvori R,, Rn og R- har den ovenfor angitte betydning eller at basisk substituerte alkylhalogenider med den generelle formel II foretres med reaksjonsdyktige oksybenzoylderivater, hvor-etter gruppen in which R, means an unsubstituted or one substituted with halogen, nitro or lower alkyl groups phenol residue, or a lower alkyl phenyl residue, where the alkyl group may be substituted with a hydroxyl group, R 2 means hydrogen, lower alkyl or phenyl or means a morpholine group, R 3 and R4 means lower alkyl groups or together with the nitrogen atom a piperidine group, R5 means hydrogen or halogen and R„ means a straight or branched lower alkylene group, as well as their salts and quaternary ammonium compounds, and the method is characterized in that a basic substituted alkyl halide or a salt thereof with the general formula II in which R,, R, and Rn have the above-mentioned meaning and Hal means a halogen, optionally in the presence of a basic condensing agent is reacted with an oxybenzoic acid amide or with an alkali compound thereof with the general compound III in which R,, Rn and R- have the meaning given above or that basic substituted alkyl halides of the general form el II is etherified with reactive oxybenzoyl derivatives, where-after the group
innføres på i og for seg kjent måte eller når R,, og R4 er lavere alkylgrupper ved at oksy-benzosyreamider med den generelle formel III kondenseres med acetaler av ha- introduced in a manner known per se or when R1 and R4 are lower alkyl groups by oxybenzoic acid amides of the general formula III being condensed with acetals of ha-
logenerte aldehyder, de dannede kondensasj onsprodukter omsettes med di-lavere-alkylformamider i nærvær av maursyre eller aldehydene som er dannet etter foregående forsåpning av acetalgruppene med eller uten oppvarmning hydreres i nærvær av et di-lavere alkylamin. halogenated aldehydes, the condensation products formed are reacted with di-lower alkylformamides in the presence of formic acid or the aldehydes formed after previous saponification of the acetal groups with or without heating are hydrated in the presence of a di-lower alkylamine.
Forbindelsene fremstillet ifølge oppfinnelsen er farmokologisk virksomme og viser ved dyreforsøk in vitro og in vivo overraskende en for denne forbindelsesklasse ikke ventet spasmolytisk, spesielt mot bariumkloridspasme utpreget spasmolytisk virkning, dessuten har et flertall av disse forbindelser ved siden av denne spasmolyttiske virkning også en analgetisk og sedativ virkning. Som eksempel for den farmakologiske virkning av noen av forbindelsene ifølge oppfinnelsen er det i følgende tabell opp-ført den spasmolyttiske virkning overfor bariumkloridspasme in vitro, idet virknin-gen av papaverin som kjent referansestoff ble satt lik 1, samtidig er det anført den minste dødelige dose (DLmi) i mg/kg, dvs. den minste dosis, som dreper en mus etter intravenøs administrering: The compounds produced according to the invention are pharmacologically active and, in animal experiments in vitro and in vivo, surprisingly show a spasmolytic effect not expected for this compound class, especially against barium chloride spasm, a pronounced spasmolytic effect, moreover, a majority of these compounds have, in addition to this spasmolytic effect, also an analgesic and sedative effect effect. As an example of the pharmacological effect of some of the compounds according to the invention, the spasmolytic effect against barium chloride spasm in vitro is listed in the following table, the effect of papaverine as a known reference substance being set equal to 1, at the same time the smallest lethal dose is listed (DLmi) in mg/kg, i.e. the smallest dose, which kills a mouse after intravenous administration:
Fremstillingen av disse nye basiske etere ifølge oppfinnelsen kan gjennomføres etter fremgangsmåter som er kjent for fremstilling av basiske etere. Således kan en forbindelse med den generelle formel The production of these new basic ethers according to the invention can be carried out according to methods which are known for the production of basic ethers. Thus, a compound with the general formula can
resp. deres alkaliforbindelser (fenolater) respectively their alkali compounds (phenolates)
omsettes med reaksjonsdyktige estere, spesielt estere av halogenhydrogensyrer med aminoalkoholer med monoalkylaminoalko-holer eller dialkylaminoalkoholer. De ved anvendelsen av aminoalkoholer og mono-akylaminoalkoholer dannede produkter al-kyleres deretter på vanlig måte, f. eks. med maursyre og med formaldehyd eller med di-metylsulfat. reacted with reactive esters, especially esters of halogenated acids with amino alcohols with monoalkylamino alcohols or dialkylamino alcohols. The products formed by the use of amino alcohols and mono-alkyl amino alcohols are then alkylated in the usual way, e.g. with formic acid and with formaldehyde or with dimethylsulphate.
Man kan imidlertid også kondensere forbindelsen III, resp. deres alkalisalter med acetaler av halogenerte aldehyder og omsette de dannede kondensasjonsproduk-ter med dialkylformamider i nærvær av maursyre eller etter foregående uten av-kjøling eller med avkjøling foretatt forsåpning hydrere acetalgruppen i nærvær av et dialkylamin. However, one can also condense the compound III, resp. their alkali salts with acetals of halogenated aldehydes and react the formed condensation products with dialkylformamides in the presence of formic acid or, after previous saponification without cooling or with cooling, hydrate the acetal group in the presence of a dialkylamine.
Ved omsetning av alkaliforbindelsen av forbindelser III med alkylendihalogenider .og etterfølgende erstatning av hydroksyl-gruppen med sekundære eller tertiære ami-ner eller av III med alkylenklorhydriner med halogen, resp. med tionylklorid og innvirk-ning av dialkylaminene får man likeledes de nye basiske etere ifølge oppfinnelsen med den generelle formel I. By reacting the alkali compound of compounds III with alkylene dihalides and subsequent replacement of the hydroxyl group with secondary or tertiary amines or of III with alkylene chlorohydrins with halogen, resp. with thionyl chloride and the action of the dialkylamines, the new basic ethers according to the invention with the general formula I are also obtained.
Blir ved de forannevnte omsetninger alkaliforbindelser med III erstattet med reaksjonsdyktige oksybenzoylderivater f. eks. med o-oksybenzosyremetylester-kalium, så får man basiske etere av reaksjonsdyktige oksybenzoylderivater, som f. eks. ved tilsetning av anilin og oppvarmning med metallisk natrium kan overføres i de basiske etere ifølge oppfinnelsen med den generelle formel I. In the aforementioned reactions, if alkali compounds with III are replaced with reactive oxybenzoyl derivatives, e.g. with o-oxybenzoic acid methyl ester-potassium, you get basic ethers of reactive oxybenzoyl derivatives, such as e.g. by adding aniline and heating with metallic sodium can be transferred into the basic ethers according to the invention with the general formula I.
Fortrinnsvis omsettes basisk substituerte alkylhalogenider med formel II Preferably, basic substituted alkyl halides of formula II are reacted
idet R3 og R4 har den ovenfor nevnte betydning og Hal betyr et halogen med en forbindelse med den generelle formel wherein R 3 and R 4 have the above-mentioned meaning and Hal means a halogen with a compound of the general formula
idet Rj, R2 og R5 har den ovenfor definerte betydning, eventuelt under anvendelse av et oppløsningsmiddel og ved anvendelse av et alkalisk kondensasj onsmiddel. Denne foretrukne utførelsesform gjelder i samme grad for omsetning av en forbindelse med formel III med et salt av en forbindelse med formel II, idet det likeledes i steden for den beregnede anvendes den dobbelte støkiometriske mengde alkalisk kondensasj onsmiddel resp. for omsetningen av et al-kalisalt av en forbindelse med formel III med et basisk substituert alkylhalogenid. with Rj, R2 and R5 having the meaning defined above, possibly using a solvent and using an alkaline condensation agent. This preferred embodiment applies to the same extent for the reaction of a compound of formula III with a salt of a compound of formula II, as the double stoichiometric amount of alkaline condensing agent or for the reaction of an alkali metal salt of a compound of formula III with a basic substituted alkyl halide.
Det ble overraskende funnet at anvendelsen av et keton, som f. eks. aceton, metyletylketon, gir spesielt høye utbytter og rene sluttprodukter ennskjønt reaksjonen også er gjennomførbar i andre oppløsnings-midler som i lavere alkanoler, aromatiske hydrokarboner. It was surprisingly found that the use of a ketone, such as acetone, methyl ethyl ketone, gives particularly high yields and clean end products, although the reaction is also feasible in other solvents such as in lower alkanols, aromatic hydrocarbons.
Dessuten kan forbindelsen ifølge oppfinnelsen også fremstiles idet man først foretrer reaksjonsryktige oksybenzoylderivater med basisk substituerte alkylhalogenider og deretter overfører de således dannede basiske etere i forbindelsene ifølge oppfinnelsen med formel I. Moreover, the compound according to the invention can also be prepared by first etherifying reactive oxybenzoyl derivatives with basic substituted alkyl halides and then transferring the thus formed basic ethers into the compounds according to the invention with formula I.
Oppfinnelsen skal i det følgende for-klares nærmere ved hjelp av noen ikke be-grensende eksempler. In the following, the invention will be explained in more detail with the help of some non-limiting examples.
Eksempel 1. Example 1.
Man oppvarmer under omrøring blandingen av 28,5 (1/10 mol) o-oksybenzoylefe-drid, 200 ml metyletylketon og 4 g NaOH til kokning, tildrypper 13,56 g dietylaminoetyl-klorid oppløst i 50 ml metyletylketon, og koker etter tildrypningens avslutning videre under tilbakeløp og omrøring i 6 timer. Deretter avkjøler man reaksjonsblan-dingen til værelsestemperatur, fjerner det ved reaksjonen dannede og i oppløsnings-midlet uoppløselige natriumklorid ved fra-sugning eller filtrering, destillerer fra filtratet 200 ml av oppløsningsmidlet og helr ler residuet i 500 ml vann, idet basen først utskiller seg oljeaktig, men imidlertid ut-krystalliserer meget hurtig. Smeltepunkt er While stirring, the mixture of 28.5 (1/10 mol) o-oxybenzoyl ephedride, 200 ml of methyl ethyl ketone and 4 g of NaOH is heated to boiling, 13.56 g of diethylaminoethyl chloride dissolved in 50 ml of methyl ethyl ketone is added drop by drop, and boiled after the addition has finished further under reflux and stirring for 6 hours. The reaction mixture is then cooled to room temperature, the sodium chloride formed during the reaction and which is insoluble in the solvent is removed by suction or filtration, 200 ml of the solvent is distilled from the filtrate and the residue is poured into 500 ml of water, the base first separating as an oil , but however crystallizes out very quickly. Melting point is
lik 115—116° C, utbytte: 31,5 g, dvs. 82 pst. equal to 115-116° C, yield: 31.5 g, i.e. 82 per cent.
Basen er lett oppløselig i eter, metanol, aceton. The base is easily soluble in ether, methanol, acetone.
For fremstilling av hydrokloridet opp-løser man basen i eter og blander denne eteriske oppløsning under omrøring med isopropanol, som er mettet med saltsyre-gass. Klorhydratet av o-dietylaminoetoksy-benzoylefedrid faller da ut i form av fine hvite krystaller, som suges fra vaskes med eter og tørkes. Smeltepunkt = 199—200° C. To prepare the hydrochloride, the base is dissolved in ether and this ethereal solution is mixed while stirring with isopropanol, which is saturated with hydrochloric acid gas. The hydrochloride of o-diethylaminoethoxy-benzoylephedride then precipitates out in the form of fine white crystals, which are sucked off, washed with ether and dried. Melting point = 199-200° C.
Eksempel 2. Example 2.
22,9 g (1/10 mol) o-oksybenzoylmorfo-lid-natrium (fremstilt f. eks. ved blanding av en metanolisk oppløsning av o-oksyben-zoylmorfolid med støkiometriske mengder metanolisk natronlut og inndampes til tørrhet) oppvarmes til kokning og under omrøring med 500 ml metyletylketon. Man tildrypper deretter 13,56 g dietylaminoetyl-klorid oppløst i 50 ml metyletylketon og koker videre i 5 timer under omrøring. Man avkjøler blandingen, f raf Utrerer natrium-kloridet og destillerer fra filtratet 500 ml av oppløsningsmidlet og heller residuet i 100 ml 5 pst.-ig saltsyre. Denne vandige opp- 22.9 g (1/10 mol) o-oxybenzoylmorpholide sodium (prepared, for example, by mixing a methanolic solution of o-oxybenzoylmorpholide with stoichiometric amounts of methanolic caustic soda and evaporating to dryness) is heated to boiling and under stirring with 500 ml of methyl ethyl ketone. 13.56 g of diethylaminoethyl chloride dissolved in 50 ml of methyl ethyl ketone are then added dropwise and the mixture is boiled for 5 hours with stirring. The mixture is cooled, the sodium chloride is filtered off and 500 ml of the solvent is distilled from the filtrate and the residue is poured into 100 ml of 5% hydrochloric acid. This aqueous up-
løsning utrystes tre ganger med eter, derpå oppløser man heri 20 g kokesalt og blander med 20 ml konsentrert natronlut, opptar basen som også er vannoppløselig i eter, tørker den eteriske oppløsning med vannfri soda og blander med HCl-mettet isopropanol. De utfelte hvite krystaller suges fra, vaskes med eter og tørkes. Man får således 25,5 g (75 pst. av det teoretiske) av klorhydratet av o-dietylaminoetoksybenzoyl-morfolid, med smeltepunkt 123° C. solution is shaken three times with ether, then 20 g of common salt are dissolved in it and mixed with 20 ml of concentrated caustic soda, the base which is also water-soluble in ether is taken up, the ethereal solution is dried with anhydrous soda and mixed with HCl-saturated isopropanol. The precipitated white crystals are filtered off, washed with ether and dried. You thus get 25.5 g (75 per cent of the theoretical) of the hydrochloride of o-diethylaminoethoxybenzoyl morpholide, with a melting point of 123° C.
Eksempel 3. Example 3.
Man oppvarmer blandingen av 28,9 g (1/10 mol) o-oksybenzoyl-difenylamid, 200 ml metanol og 4gNaOH til kokning, tildrypper under omrøring 13,56 g dietylamino-etylklorid oppløst i 50 ml metanol og koker deretter i ytterligere 8 timer. Den varme reaksjonsblanding helles i 1000 ml koldt vann, basen som utskiller seg som olje opptas i eter. den eteriske oppløsning tørkes med vannfritt soda. Man fører nu under god omrøring tørr klorhydrogengass inn i den eteriske oppløsning, frasuger de utfelte hvite krystaller, vasker de med eter og tørker. Man får 30,5 g (72 pst.) o-dietyl-aminoetoksy-benzoyldifenylamid-klorhy-drat med smeltepunkt 201° C. The mixture of 28.9 g (1/10 mol) o-oxybenzoyl-diphenylamide, 200 ml of methanol and 4 g of NaOH is heated to boiling, 13.56 g of diethylamino-ethyl chloride dissolved in 50 ml of methanol is added dropwise while stirring and then boiled for a further 8 hours . The hot reaction mixture is poured into 1000 ml of cold water, the base which separates as an oil is taken up in ether. the ethereal solution is dried with anhydrous soda. Dry chlorine hydrogen gas is now introduced into the ethereal solution with good stirring, the precipitated white crystals are sucked off, washed with ether and dried. 30.5 g (72 percent) of o-diethylaminoethoxy-benzoyldiphenylamide chlorohydrate with a melting point of 201° C is obtained.
Eksempel 4. Example 4.
Man koker under tilbakeløp og omrø-ring blandingen av 95 g (1/2 mol) o-oksybenzosyremetylester-kalium, 500 ml benzol, 54 g dimetylaminoetylklorid og noen krystaller kaliumjodid i 48 timer, avkjøler, utryster reaksj onsblandingen flere ganger med fortynnet saltsyre, gjør den vandige fase alkalisk med konsentrert natronlut, opptar basen i eter, tørker den eteriske oppløsning med soda og renser råbasen en-ten ved destillering i vakuum (kokepunkt 180—190° C ved 30 mm Hg, utbytte 46,8 g = 42 pst.) eller ved utfelling som klorhy-drat og omkrystallisering av klorhydratet (smeltepunkt 140° C fra alkohol/eter). The mixture of 95 g (1/2 mol) o-oxybenzoic acid methyl ester potassium, 500 ml of benzene, 54 g of dimethylaminoethyl chloride and some crystals of potassium iodide is boiled under reflux and stirring for 48 hours, cooled, the reaction mixture is shaken several times with dilute hydrochloric acid, make the aqueous phase alkaline with concentrated caustic soda, take up the base in ether, dry the ethereal solution with soda and purify the crude base either by distillation in vacuum (boiling point 180-190° C at 30 mm Hg, yield 46.8 g = 42 percent .) or by precipitation as chlorhydrate and recrystallization of the chlorhydrate (melting point 140° C from alcohol/ether).
38 g (2/10 mol) av den således dannede o-dimetylaminoetoksybenzosyremetylester blandes med 18,6 g anilin, oppvarmes til ca. 120° C og holdes etter tilsetning av 1 g natrium i småstykker ytterligere 30 minutter ved denne temperatur. Ved avkjøling stivner massen. Man oppløser den ved oppvarmning med 100 ml metanol, heller den metanoliske oppløsning langsomt under 38 g (2/10 mol) of the o-dimethylaminoethoxybenzoic acid methyl ester thus formed is mixed with 18.6 g of aniline, heated to approx. 120° C and, after adding 1 g of sodium in small pieces, is kept at this temperature for a further 30 minutes. On cooling, the mass solidifies. It is dissolved by heating with 100 ml of methanol, pouring the methanolic solution slowly under
omrøring i 500 ml 2 pst.-ig saltsyre, utryster tre ganger med eter og blander deretter med konsentrert natronlut til alkalisk reaksj on. Basen faller først oljeaktig ut, men krystalliserer meget hurtig, smeltepunkt 60° C. Overføringen i klorhydratet foregår på allerede beskrevet måte og gir 38 g (60 pst.) o-dimetylaminoetoksy-benzanilid-klorhydrat, med smeltepunkt 228° C. stirring in 500 ml of 2% hydrochloric acid, shaking three times with ether and then mixing with concentrated caustic soda to an alkaline reaction. The base first falls out oily, but crystallizes very quickly, melting point 60° C. The transfer into the chlorhydrate takes place in the manner already described and yields 38 g (60 per cent) of o-dimethylaminoethoxy-benzanilide chlorohydrate, with a melting point 228° C.
Eksempel 5. Example 5.
Oppløsningen av 21,3 g (1/10 mol) o-oksybenzanilid i 200 ml metyletylketon oppvarmer man under omrøring til koking, tilsetter 4 g NaOH og tildrypper oppløsningen av 14,8 g N-piperidinoetylklorid i 50 ml metyletylketon. Man holder i 6 timer under omrøring ved kokning og heller deretter den ennu varme reaksjonsblanding i The solution of 21.3 g (1/10 mol) o-oxybenzanilide in 200 ml of methyl ethyl ketone is heated while stirring to boiling, 4 g of NaOH are added and the solution of 14.8 g of N-piperidinoethyl chloride in 50 ml of methyl ethyl ketone is added dropwise. It is kept for 6 hours while stirring when boiling and then the still warm reaction mixture is poured in
1000 ml koldt vann, hvorpå den ved reaksjonen dannede base først faller ut oljeaktig, men krystalliserer meget hurtig. Man frasuger etter fullstendig avkjøling, vasker bunnfallet godt med vann, oppløser det i eter, utryster den eteriske oppløsning med fortynnet saltsyre og frigjør base fra den vandige oppløsning av klorhydratet med konsentrert natronlut idet den med en gang krystaliserer igjen. Man suger fra vasker man vann og tørker. Utbyttet o-N-piperidinoetoksy-benzanilid: 27,6 g (85 pst.), smeltepunkt 113° C. 1000 ml of cold water, whereupon the base formed by the reaction first precipitates out oily, but crystallizes very quickly. After complete cooling, suction is applied, the precipitate is washed well with water, dissolved in ether, the ethereal solution is shaken with dilute hydrochloric acid and the base is liberated from the aqueous solution of the hydrochloric acid with concentrated caustic soda, as it immediately crystallizes again. You vacuum, wash with water and dry. Yield o-N-piperidinoethoxy-benzanilide: 27.6 g (85%), mp 113°C.
Klorhydratet har et smeltepunkt på 179° C. The hydrochloride has a melting point of 179°C.
Eksempel 6. Example 6.
En blanding av 34,4 g (2/10 mol) di-etylaminoetylklorid, 300 ml metyletylketon, 42,6 g o-oksybenzanilid og 16 g NaOH oppvarmes under omrøring langsomt til kokning og kokes i 4 timer. Den videre opp-arbeidelse foregår på den måte som er an-ført i eksempel 5 idet det må iakttas at basens krystallisering p.g.a. det lave smeltepunkt først foregår etter uthelling av reaksj onsblandingen i vann og fullstendig avkjøling. Man får 53,6 g o-diethylamino-etoksy-benzanilid (86 pst.), med smeltepunkt 44° C. A mixture of 34.4 g (2/10 mol) of diethylaminoethyl chloride, 300 ml of methyl ethyl ketone, 42.6 g of o-oxybenzanilide and 16 g of NaOH is slowly heated to boiling with stirring and boiled for 4 hours. The further processing takes place in the manner stated in example 5, as it must be observed that the crystallization of the base due to the low melting point only occurs after pouring the reaction mixture into water and complete cooling. 53.6 g of o-diethylamino-ethoxy-benzanilide (86 percent) are obtained, with a melting point of 44° C.
Klorhydratet smelter ved 173° C. Anvendes det i steden for det i eksempel 6 anvendte dietylamino-etylklorid-hy-droklorid, dimetylaminoisopropyl-klorid-hydroklorid resp. dimetylaminopropylklo-rid-hydroklorid, så får man dimetylaminoisopropoksy-o-benz-anilid resp. dimetylaminopropoksy-o-benzanilid The hydrochloride melts at 173° C. If it is used instead of the diethylamino ethyl chloride hydrochloride used in example 6, dimethylaminoisopropyl chloride hydrochloride resp. dimethylaminopropyl chloride-hydrochloride, then you get dimethylaminoisopropoxy-o-benz-anilide or dimethylaminopropoxy-o-benzanilide
hvis HC1 salt har et smeltepunkt på 169° C. if HC1 salt has a melting point of 169° C.
Eksempel 7. Example 7.
31,2 g (1/10 mol) av den ifølge eksempel 6 fremstilte base og 25,6 g etyljodid opp-løses i 200 ml metyletylketon og kokes i 8 timer under tilbakeløp. Man avdestillerer deretter ca. 100 ml oppløsningsmiddel heller residuet i et begerglass og blander det med 500 ml tørr eter, idet det ved reaksjonen dannede kvartære salt hurtig utfel-les krystallisert. Man suger fra, vasker med eter og tørker, utbytte 44 g = 94 pst. med smeltepunkt 166° C. 31.2 g (1/10 mol) of the base prepared according to example 6 and 25.6 g of ethyl iodide are dissolved in 200 ml of methyl ethyl ketone and boiled for 8 hours under reflux. It is then distilled approx. 100 ml of solvent pour the residue into a beaker and mix it with 500 ml of dry ether, the quaternary salt formed by the reaction quickly precipitates out crystallized. It is filtered off with suction, washed with ether and dried, yield 44 g = 94% with a melting point of 166° C.
Eksempel 8. Example 8.
Man oppløser 21,3 g (1/10 mol) m-oksybenzanilid i 200 ml dietylketon, oppvarmer til kokning, tilsetter 4 g NaOH og lar under omrøring 13,6 g dietylaminoetylklo-rid oppløst i 50 ml dietylketon, tildryppe. Etter tre timers kokning under tilbakeløp avkjøles det filtreres og fra residuet for-dampes oppløsningsmidlet og utrøres med 500 ml vann. Basen opptas i eter, den eteriske oppløsning tørkes og blandes med saltsurt isopropanol. Man får 28,8 g (82 pst.) m-dietylamino-etoksy-benzanilid-d-hydroklorid, med smeltepunkt 151° C. Dissolve 21.3 g (1/10 mol) of m-oxybenzanilide in 200 ml of diethyl ketone, heat to boiling, add 4 g of NaOH and, while stirring, allow 13.6 g of diethylaminoethyl chloride dissolved in 50 ml of diethyl ketone to drip in. After boiling under reflux for three hours, it is cooled, filtered and the solvent is evaporated from the residue and stirred with 500 ml of water. The base is taken up in ether, the ethereal solution is dried and mixed with hydrochloric isopropanol. 28.8 g (82 percent) of m-diethylamino-ethoxy-benzanilide-d-hydrochloride are obtained, with a melting point of 151° C.
Eksempel 9. Example 9.
På samme måte som i eksempel 8 får man ved anvendelse av p-oksybenzanilid klorhydratet av p-dietylaminoetoksy-benz-anilid i et utbytte på 80 pst., med smeltepunkt 185° C. In the same way as in example 8, by using p-oxybenzanilide, the hydrochloride of p-diethylaminoethoxy-benzanilide is obtained in a yield of 80%, with a melting point of 185°C.
Ytterligere eksempler på forbindelser ifølge oppfinnelsen er: o-dietylaminoetoksybenzoyl-2-metyl-anilid-HCl, smeltepunkt 169° C o-dietylaminoetoksybenzoyl-o-xylidid-HC1, smeltepunkt 159° C o-dietylaminoetoksybenzoyl-2-klor-anilid-HCl, smeltepunkt 120° C o-dietylaminoetoksybenzoyl-3-klor-anilid-HCl, smeltepunkt 105° C o-dietylaminoetoksybenzoyl-4-klor-anilid-HCl, smeltepunkt 162° C o-dietylaminoetoksybenzoyl-2-nitro-anilid-HCl, smeltepunkt 186° C 2-dietylaminoetoksy-5-klor-benz-anilid-HCl, smeltepunkt 141° C. Further examples of compounds according to the invention are: o-diethylaminoethoxybenzoyl-2-methyl-anilide-HCl, melting point 169° C o-diethylaminoethoxybenzoyl-o-xylidide-HCl, melting point 159° C o-diethylaminoethoxybenzoyl-2-chloro-anilide-HCl, melting point 120° C o-diethylaminoethoxybenzoyl-3-chloro-anilide-HCl, melting point 105° C o-diethylaminoethoxybenzoyl-4-chloro-anilide-HCl, melting point 162° C o-diethylaminoethoxybenzoyl-2-nitro-anilide-HCl, melting point 186 ° C 2-diethylaminoethoxy-5-chloro-benz-anilide-HCl, melting point 141° C.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7850205 | 1978-12-29 |
Publications (3)
Publication Number | Publication Date |
---|---|
NO794213L NO794213L (en) | 1980-07-01 |
NO150553B true NO150553B (en) | 1984-07-30 |
NO150553C NO150553C (en) | 1984-11-07 |
Family
ID=10501976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO794213A NO150553C (en) | 1978-12-29 | 1979-12-20 | INFLATABLE BATH |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0013114B1 (en) |
CA (1) | CA1116477A (en) |
DE (1) | DE2965967D1 (en) |
NO (1) | NO150553C (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3409760C1 (en) * | 1984-03-16 | 1985-06-27 | Metzeler Kautschuk GmbH, 8000 München | Self-supporting inflatable boat |
IT1240299B (en) * | 1990-04-13 | 1993-12-07 | Martino Di Montegiordano Anton | RIGID STRUCTURE VESSEL WITH PNEUMATIC FLOATING THROUGH OBLONG, LONGITUDINAL, BELOW AIR CHAMBER BELOW |
US5152243A (en) * | 1991-08-22 | 1992-10-06 | Yung Hsin Plastics Corporation | Structure of inflatable boat |
US8800466B1 (en) | 2010-06-23 | 2014-08-12 | Navatek, Ltd. | Inflatable watercraft with reinforced panels |
CN111836758B (en) * | 2019-02-15 | 2022-09-20 | 太阳有限公司 | Inflatable motor boat |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB576108A (en) * | 1942-12-24 | 1946-03-19 | Elliot Equipment Ltd | Improvements in or relating to inflatable dinghies |
ES332380A1 (en) * | 1965-10-19 | 1967-10-01 | Metzeler Ag | Improvements in the manufacture of supplementary wood, plastic or metal fund for inflatable boats. (Machine-translation by Google Translate, not legally binding) |
FR1482860A (en) * | 1966-01-19 | 1967-06-02 | Pennel & Flipo Ets | Pneumatic boat |
DE1964657A1 (en) * | 1969-12-23 | 1971-07-01 | Metzeler Ag | Inflatable boat |
DE1964656C3 (en) * | 1969-12-23 | 1978-06-08 | Metzeler Ag, 8000 Muenchen | Inflatable boat |
GB1273692A (en) * | 1970-01-16 | 1972-05-10 | Keith William English | Improvements in or relating to boat hulls |
GB1319072A (en) * | 1970-05-22 | 1973-05-31 | Dunlop Holdings Ltd | Inflatable boats |
IT942690B (en) * | 1970-10-22 | 1973-04-02 | Metzeler Ag | PNEUMATIC SLEEVE |
FR2398660A1 (en) * | 1977-07-28 | 1979-02-23 | Zodiac | IMPROVEMENTS FOR PNEUMATIC MOTOR BOATS |
-
1979
- 1979-12-17 DE DE7979302932T patent/DE2965967D1/en not_active Expired
- 1979-12-17 EP EP79302932A patent/EP0013114B1/en not_active Expired
- 1979-12-20 NO NO794213A patent/NO150553C/en unknown
- 1979-12-28 CA CA000342790A patent/CA1116477A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1116477A (en) | 1982-01-19 |
EP0013114B1 (en) | 1983-07-20 |
EP0013114A1 (en) | 1980-07-09 |
DE2965967D1 (en) | 1983-08-25 |
NO150553C (en) | 1984-11-07 |
NO794213L (en) | 1980-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
GB2141716A (en) | Oxazolidines | |
NO153082B (en) | APPARATUS FOR STAPPING A WRINKED RODFORM SHEET | |
NO154554B (en) | PROCEDURE FOR THE MANUFACTURING OF MINERAL BUILDING FIBERS. | |
NO139918B (en) | NEW IONIC IODINE BENZENE DERIVATIVES FOR USE IN X-RAY CONTRAST AGENTS | |
US3974156A (en) | 2-(Substituted anilino) methylmorpholine compounds | |
IE42119B1 (en) | Aralkylamine derivatives | |
NO150553B (en) | INFLATABLE BATH | |
NO137965B (en) | ANALOGICAL PROCEDURES FOR THE PREPARATION OF NEW CYCLIC THERAPEUTIC ACTIVE DIRECTIVE DERIVATIVES AND SALTS OF THESE WITH PHARMACEUTICAL ACCEPTABLE ACIDS | |
US3254120A (en) | N-(tertiaryaminoalkoxy-benzoyl) anilides | |
US4131686A (en) | Novel benzylalcohol derivatives and processes for preparing the same | |
US4663340A (en) | Alpha-adrenoreceptor agonistic 2-[(2-cyclopropyl-5-methyl- or 2-cyclopropyl-5-chlorophenoxy)methyl]-2-imidazolines | |
US3077472A (en) | 3-[4-(aminoalkoxy)-phenyl]-4-(4-oxyphenyl)-alkanes and alkenes | |
JPS5839820B2 (en) | Method for producing serinol and serinol derivatives | |
NO145209B (en) | APPARATUS FOR MAGNETIC EFFECT OF A FLOWING LIQUID | |
NO126914B (en) | ||
US4108994A (en) | 5-thiazole-methane-amines, and their use as antilipolytics | |
CA1041098A (en) | 1-(3-(naphthyl-1-yl-oxy)-propyl)-piperazine derivatives | |
US3209026A (en) | Cyclohexyloxycyclopropylamines | |
US4101579A (en) | Phenethanolamine ethers | |
NO121584B (en) | ||
JPS5822107B2 (en) | α↓-aminomethylene↓-β↓-formylaminopropionitrile and its production method | |
DK142844B (en) | Analogous process for the preparation of substituted N- (2-pyrrolidylmethyl) benzamide derivatives. | |
US4161532A (en) | N-(1'-ethyl-2'-oxo-5'-pyrrolidinylmethyl) benzamide compounds and derivatives, method of preparation and pharmaceutical preparations | |
HU180716B (en) | Process for preparing substituted amino-alkyl-guanidines | |
GB2178035A (en) | Novel benzamides and their preparation and therapeutic application |