NO128496B - - Google Patents
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- Publication number
- NO128496B NO128496B NO03986/69A NO398669A NO128496B NO 128496 B NO128496 B NO 128496B NO 03986/69 A NO03986/69 A NO 03986/69A NO 398669 A NO398669 A NO 398669A NO 128496 B NO128496 B NO 128496B
- Authority
- NO
- Norway
- Prior art keywords
- acid
- pyridyl
- amino
- sulfuric acid
- phosphorus pentoxide
- Prior art date
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 6
- -1 ketone acetals Chemical class 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- BNBQQYFXBLBYJK-UHFFFAOYSA-N 2-pyridin-2-yl-1,3-oxazole Chemical class C1=COC(C=2N=CC=CC=2)=N1 BNBQQYFXBLBYJK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229940075930 picrate Drugs 0.000 claims description 3
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229940072033 potash Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HJKLEAOXCZIMPI-UHFFFAOYSA-N 2,2-diethoxyethanamine Chemical compound CCOC(CN)OCC HJKLEAOXCZIMPI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006418 Brown reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-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
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- AHISYUZBWDSPQL-UHFFFAOYSA-N 6-methylpyridine-2-carbaldehyde Chemical compound CC1=CC=CC(C=O)=N1 AHISYUZBWDSPQL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 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
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- 150000001241 acetals Chemical class 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MBKFVEJIATUGNM-UHFFFAOYSA-N cyanomethyl pyridine-2-carboxylate Chemical compound N#CCOC(=O)C1=CC=CC=N1 MBKFVEJIATUGNM-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- MLZIGAYUWZORHX-UHFFFAOYSA-N n-(2,2-diethoxyethyl)pyridine-2-carboxamide Chemical compound CCOC(OCC)CNC(=O)C1=CC=CC=N1 MLZIGAYUWZORHX-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QJZUKDFHGGYHMC-UHFFFAOYSA-N pyridine-3-carbaldehyde Chemical compound O=CC1=CC=CN=C1 QJZUKDFHGGYHMC-UHFFFAOYSA-N 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D27/00—Woven pile fabrics
- D03D27/02—Woven pile fabrics wherein the pile is formed by warp or weft
- D03D27/06—Warp pile fabrics
- D03D27/08—Terry fabrics
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D49/00—Details or constructional features not specially adapted for looms of a particular type
- D03D49/04—Control of the tension in warp or cloth
- D03D49/06—Warp let-off mechanisms
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Looms (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
Fremgangsmåte til fremstilling av terapeutisk aktive 2-pyridyl-oksazoler. Process for the preparation of therapeutically active 2-pyridyl-oxazoles.
Gjenstanden for oppfinnelsen er fremstilling av 2-pyridyl-oksazoler og deres The object of the invention is the preparation of 2-pyridyl-oxazoles and theirs
salter. De nye oksazoler kan i de to heterocykliske ringer som substituenter ha lavere salts. The new oxazoles can have lower substituents in the two heterocyclic rings
alkylrester, særlig metyl. Oksazolresten kan alkyl residues, especially methyl. The oxazole residue can
være forbundet med pyridinkjernen i dens be associated with the pyridine nucleus in its
stillinger 2, 3 eller 4. positions 2, 3 or 4.
De nye forbindelser har verdifulle far-makologiske egenskaper, således er de'The new compounds have valuable pharmacological properties, thus they are
analgetisk virksomme. De kan anvendes analgesically active. They can be used
som legemiddel, fremfor alt som analge-tika. Særlig verdifull er 2-pyridyl-(2')-ok-sazol med formelen as a medicine, above all as an analgesic. Particularly valuable is 2-pyridyl-(2')-ox-sazole with the formula
samt dens salter. as well as its salts.
2-pyridyl-oksazolene fremstilles etter The 2-pyridyl-oxazoles are prepared by
i og for seg kjente fremgangsmåter til methods known per se
fremstilling av 2-substituerte oksazoler. preparation of 2-substituted oxazoles.
Fortrinsvis går man frem således at man Preferably, one proceeds in such a way that one
kondenserer a- (N- [pyridyl- metyliden ] - condenses a-(N-[pyridyl-methylidene]-
amino)-aldehyd- eller -ketonacetaler under oksyderende betingelser intramolekylært. Som oksyderende kondensasjonsmid-del tar man hensiktsmessig fosforpentoksyd i konsentrert svovelsyre. amino)-aldehyde or ketone acetals under oxidizing conditions intramolecularly. Phosphorus pentoxide in concentrated sulfuric acid is used as an oxidizing condensation agent.
En annen fremgangsmåte består deri at Another method consists in that
man intramolekylært kondenserer a-(pyri-doyl-amino)-aldehyder eller -ketoner, som one intramolecularly condenses α-(pyridoyl-amino)-aldehydes or ketones, which
i a-stilling til karbonylgruppen og ved in the a-position to the carbonyl group and at
amin-nitrogenet har hver et hydrogen-. atom, slik som f. eks. pyridoyl-aminometyl-ketoner, eller deres funksjonelle deriva-ter, fortrinnsvis i nærvær av kondensa-sjonsmidler, slik som svovelsyre eller, fos-forpentaklorid. the amine nitrogen each has a hydrogen-. atom, such as e.g. pyridoyl-aminomethyl ketones, or their functional derivatives, preferably in the presence of condensing agents, such as sulfuric acid or phosphorus pentachloride.
De nevnte reaksjoner utføres på i og for seg kjent måte, fortrinsvis ved forhøyet temperatur i nærvær eller fravær av for-tynningsmidler og/eller kondensasjonsmid-ler, i åpent eller lukket kar. The aforementioned reactions are carried out in a manner known per se, preferably at an elevated temperature in the presence or absence of diluents and/or condensation agents, in an open or closed vessel.
Alt etter arbeidsmåten får man de nye forbindelser i form av de frie baser eller som salter. Av de siste kan basene frigjøres på vanlig måte, f. eks. ved behandling med alkalier. Av de frie baser kan man som vanlig fremstille saltene, f. eks. ved om-setning med de tilsvarende syrer, slik som f. eks. saltene av halogenvannstoff-syre, svovelsyre, fosforsyre, salpetersyre, perklorsyre, alifatiske, aromatiske eller heterocykliske karbon- eller sulfonsyrer, slik som maursyre, eddiksyre, propionsyre, ok-salsyre, ravsyre, glykolsyre, melkesyre, ep-lesyre, vinsyre, sitronsyre, ascorbinsyre, ok-symaleinsyre, dioksymaleinsyre, pyrodrue-syre, fenyleddiksyre, benzoesyre, p-amino-benzoesyre, antranilsyre, p-oksybenzoesyre, salicylsyre, p-aminosalicylsyre, metansul-fonsyre, etansulfonsyre, oksyetansulfon-syre, etylensulfonsyre, toluolsulfonsyre, naftalinsulfonsyre. Depending on the working method, the new compounds are obtained in the form of free bases or as salts. Of the latter, the bases can be released in the usual way, e.g. by treatment with alkalis. From the free bases the salts can be prepared as usual, e.g. by reaction with the corresponding acids, such as e.g. the salts of hydrohalic acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid, aliphatic, aromatic or heterocyclic carbonic or sulfonic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, oxymaleic acid, dioxymaleic acid, pyruvic acid, phenylacetic acid, benzoic acid, p-aminobenzoic acid, anthranilic acid, p-oxybenzoic acid, salicylic acid, p-aminosalicylic acid, methanesulfonic acid, ethanesulfonic acid, oxyethanesulfonic acid, ethylenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid.
Utgangsstoffene er kjent eller kan fremstilles etter i og for seg kjente fremgangsmåter. Fortrinsvis anvender man slike som fører til de til å begynne med beskrevne 2-pyridyl-oksazoler. The starting materials are known or can be prepared according to methods known per se. Those which lead to the initially described 2-pyridyl-oxazoles are preferably used.
Oppfinnelsen beskrives nærmere i de følgende eksempler. Temperaturene er an-gitt i Celsius-grader. The invention is described in more detail in the following examples. The temperatures are given in degrees Celsius.
Eksempel 1: Example 1:
10 g N-[pyridyl-(2)-metyliden]-amino- acetaldehyd-dietylacetal lar man dryppe langsomt under omrøring ved 0° C til 42 cm<3> konsentrert svovelsyre. Blandingen farges mørkegul. Under god avkjøling inn-føres deretter langsomt 17 g fosforpentoksyd. Den dannede blanding opphetes i 20 minutter til 120° C. Deretter lar man av-kjøle og heller den mørke reaksjonsblan-ding på ca. 500 g is. Etter nøytralisasjon med konsentrert vandig ammoniakk under avkjøling behandles flere ganger varmt med aktivt kull, og det brunlige filtrat un-derkastes dampdestillasjion. Det erholdte destillat (ca. 3 liter) inndampes i vakuum til ca. 500 cm<3>, mettes med pottaske og ekstraheres natten over med eter i Kutscher-Steudel-apparat. Den brunlige olje som blir tilbake ved inndampning av den tørkede eteriske fase destilleres i høyvakuum. Ved 70—75° C/0,1 mm går det over en fargeløs olje, som er ren 2-pyridyl-(2')-oksazol med formelen 10 g of N-[pyridyl-(2)-methylidene]-amino- acetaldehyde-diethyl acetal is allowed to drip slowly with stirring at 0° C to 42 cm<3> concentrated sulfuric acid. The mixture is colored dark yellow. During good cooling, 17 g of phosphorus pentoxide are then introduced slowly. The resulting mixture is heated for 20 minutes to 120° C. It is then allowed to cool and the dark reaction mixture is poured into approx. 500 g of ice. After neutralization with concentrated aqueous ammonia while cooling, it is treated several times hot with activated charcoal, and the brownish filtrate is subjected to steam distillation. The resulting distillate (approx. 3 litres) is evaporated in a vacuum to approx. 500 cm<3>, saturated with pot ash and extracted overnight with ether in a Kutscher-Steudel apparatus. The brownish oil that remains after evaporation of the dried ethereal phase is distilled under high vacuum. At 70-75° C/0.1 mm, a colorless oil passes over, which is pure 2-pyridyl-(2')-oxazole with the formula
Forbindelsen danner et monopikrat, som etter flere gangers krystallisasjon fra etanol smelter ved 165—167° C. The compound forms a monopicrate, which after several times of crystallization from ethanol melts at 165-167°C.
Det dietylacetal som ble anvendt som utgangsstoff kan fåes som følger: 29,5 g friskt destillert bromacetalde-hyd-dietylacetyl (kokepunkt 80—81° C/12 The diethyl acetal that was used as starting material can be obtained as follows: 29.5 g of freshly distilled bromoacetaldehyd-diethylacetyl (boiling point 80-81° C/12
mm) tilsettes ca. 150 cm<3> flytende ammoniakk og opphetes 6 timer ved 110° C/80 mm) is added approx. 150 cm<3> of liquid ammonia and heated for 6 hours at 110° C/80
atm. i rysteautoklav. Etter avkjøling, åp-ning og fordampning av ammoniakken, opptar man med mettet pottaske-oppløs-ning, og ekstraherer natten over med eter i Kutscher-Steudel-apparat. Den eteriske fase tørkes med natriumsulfat og fraksjo-neres over en liten Vigreux-kolonne. Man få således amimo-acetaldehyd-dietylacetal (kokepunkt 54—57° C/12 mm). Det gir med alkoholisk pikrinsyre et pikrat med smelte-punkt 140—142° C. atm. in a shaking autoclave. After cooling, opening and evaporation of the ammonia, take up with saturated pot ash solution, and extract overnight with ether in a Kutscher-Steudel apparatus. The ethereal phase is dried with sodium sulphate and fractionated over a small Vigreux column. Amimo-acetaldehyde-diethyl acetal is thus obtained (boiling point 54-57° C/12 mm). It gives with alcoholic picric acid a picrate with a melting point of 140-142° C.
10 g av dette acetal oppvarmes i destil-lasjonskolben med 8 g friskt destillert py-ridin-2-aldehyd med kokepunkt 62—63°C/ 13 mm i 30 minutter på oljebad til 110° C, og det frigjorte vann avdestilleres. Deretter fjernes det siste vannspor ved 100° C/ 12 mm, og resten destilleres i høyvakuum. Man får således N-[pyridyl-(2) -metyliden] -amino-acetaldehyd-dietylacetal i 10 g of this acetal are heated in the distillation flask with 8 g of freshly distilled pyridine-2-aldehyde with boiling point 62-63°C/ 13 mm for 30 minutes in an oil bath to 110° C, and the freed water is distilled off. The last trace of water is then removed at 100° C/ 12 mm, and the remainder is distilled in a high vacuum. One thus obtains N-[pyridyl-(2)-methylidene]-amino-acetaldehyde-diethyl acetal i
form av en gulaktig olje med kokepunkt 109—114° C/0,5 mm. in the form of a yellowish oil with a boiling point of 109-114° C/0.5 mm.
Eksempel 2. Example 2.
15 g N-[6-metyl-pyridyl-(2)-metyliden] -amino-acetaldehyd-dietylacetal set-tes dråpevis ved -^5—0° C under omrøring til 86 cm<3> konsentrert svovelsyre. Denne blanding drypper man eventuelt under omrøring ved -^5—0° C, til 36 g fosforpentoksyd og 10 cm<3> konsentrert svovelsyre, og oppvarmer 1 time under omrøring ved 130° C. Etter avkjøling heller man det mørkebrune reaksjonsprodukt på is, gjør alkalisk med konsentrert ammoniakk og destillerer med vanndamp. Destillatet (ca. 2 liter) ansyrer man med konsentrert saltsyre, hvorved oppløsningen ikke skal oppvarmes for sterkt, inndamper i vakuum, metter med pottaske og ekstraherer i en Kutscher-Steudel-apparatur med eter. Eteroppløsningen tørkes og inndampes. Resten destilleres i kulerør ved 60° C/0,1 mm Hg. Det således erholdte 2-[6'-metyl-pyridyl-(2')]-oksazol med formelen 15 g of N-[6-methyl-pyridyl-(2)-methylidene]-amino-acetaldehyde-diethyl acetal was added dropwise at -^5-0° C with stirring to 86 cm<3> of concentrated sulfuric acid. This mixture is optionally added dropwise with stirring at -^5-0° C, to 36 g of phosphorus pentoxide and 10 cm<3> of concentrated sulfuric acid, and heated for 1 hour with stirring at 130° C. After cooling, the dark brown reaction product is poured onto ice, make alkaline with concentrated ammonia and distil with steam. The distillate (approx. 2 litres) is acidified with concentrated hydrochloric acid, whereby the solution should not be heated too strongly, evaporated in a vacuum, saturated with pot ash and extracted in a Kutscher-Steudel apparatus with ether. The ether solution is dried and evaporated. The residue is distilled in a bubble tube at 60° C/0.1 mm Hg. The thus obtained 2-[6'-methyl-pyridyl-(2')]-oxazole with the formula
smelter, omkrystallisert fra eter-petrol-eter ved 55—57° C. Det er oppløselig i eter, alkohol og vann. melts, recrystallized from ether-petroleum-ether at 55—57° C. It is soluble in ether, alcohol and water.
Utgangsstoff et fås som følger: Starting material is obtained as follows:
10,2 g (0,1 mol) 6-metyl-pyridin-2-aldehyd opphetes med tilbakeløpskjøler med 11,2 g (0,11 mol) amino-acetaldehyd-dietylacetal i 2 timer til 120—130° C. Det mørkebrune reaksjonsprodukt destilleres ved 95—96° C/0,04 mm Hg. Gjentatt destil-lasjon ved 60—63° C/0,05 mm Hg i kulerør gir N-[6-metyl-pyridyl-(2)-metyliden]-amino-acetaldehyd-dietylacetal som en nesten fargeløs olje. 10.2 g (0.1 mol) of 6-methyl-pyridine-2-aldehyde is heated with a reflux condenser with 11.2 g (0.11 mol) of amino-acetaldehyde-diethyl acetal for 2 hours at 120-130° C. The dark brown reaction product is distilled at 95-96° C/0.04 mm Hg. Repeated distillation at 60-63°C/0.05 mm Hg in bubble tubes gives N-[6-methyl-pyridyl-(2)-methylidene]-amino-acetaldehyde-diethyl acetal as an almost colorless oil.
Eksempel 3. Example 3.
5 g amino-acetaldehyd-dietylacetal oppvarmes med 4 g isonikotinaldehyd i 1 time til 150° C. Det dannede vann avdestilleres derved kontinuerlig i vakuum. Man får 8,5 g nesten fargeløs azometinbase. 5 g av dette lar man dryppe ved -^10° C til 20 cm<3> konsentrert svovelsyre. Blandingen 5 g of amino-acetaldehyde-diethyl acetal are heated with 4 g of isonicotinaldehyde for 1 hour to 150° C. The water formed is thereby continuously distilled off in a vacuum. You get 8.5 g of almost colorless azomethine base. 5 g of this is allowed to drip at -^10° C to 20 cm<3> of concentrated sulfuric acid. The mixture
tilsettes deretter under god avkjøling en oppløsning av 8 g fosforpentoksyd i litt svovelsyre og oppvarmes deretter langsomt sluttelig til 150° C. Etter 1 time lar man avkjøle, tilsetter is og nøytraliserer med konsentrert ammoniakk. Den svakt alka-liske oppløsning vanndampdestilleres. Destillatet av 3 liter innstiller man med kon- a solution of 8 g of phosphorus pentoxide in a little sulfuric acid is then added under good cooling and then slowly heated finally to 150° C. After 1 hour it is allowed to cool, ice is added and neutralized with concentrated ammonia. The slightly alkaline solution is steam distilled. The distillate of 3 liters is adjusted with con-
sentrert saltsyre på pH 3—4, inndamper i vakuum til ca. 200 cm<3>, metter med pottaske og ekstraherer 24 timer kontinuerlig med eter. Resten (1 g) av den tørre eter-fase krystalliserer man ved avrivning. Etter omkrystallisasjonen fra isopropyleter smelter det erholdte 2-pyridyl-(4')-oksa-zol med formelen: concentrated hydrochloric acid at pH 3-4, evaporate in vacuum to approx. 200 cm<3>, saturate with pot ash and extract continuously for 24 hours with ether. The rest (1 g) of the dry ether phase is crystallized by stripping. After the recrystallization from isopropyl ether, the obtained 2-pyridyl-(4')-oxazole melts with the formula:
ved 154—155° C. at 154-155° C.
Ved nøyaktig analog fremgangsmåte får man ved anvendelse av nikotinaldehyd i 43 pst.-ig utbytte den isomere 2-pyridyl-(3')-oksazol med formelen: By an exactly analogous method, by using nicotinaldehyde in 43%, the isomeric 2-pyridyl-(3')-oxazole is obtained with the formula:
Eksempel 4: 5 g pikolinsyre-cyanmetylester blandes med 1,9 g amino-acetaldehyd-dietylacetal og 1 cm<3> trietylamin under avkjøling. Re-aksjonen, som straks setter i gang, gjøres fullstendig ved 1 times digerering på vann-bad. Den brunlige blanding opptas i 2-nor-mal saltsyre, avfarges med kull, mettes med pottaske og ekstraheres med kloroform. Resten fra den organiske ekstrakt (2 g) går fargeløst over ved ca. 100° C/0,01 mm (kuler ør). Example 4: 5 g of picolinic acid cyanomethyl ester are mixed with 1.9 g of amino-acetaldehyde-diethyl acetal and 1 cm<3> of triethylamine while cooling. The reaction, which immediately starts, is completed by 1 hour of digestion in a water bath. The brownish mixture is taken up in 2-nor mal hydrochloric acid, decolorized with charcoal, saturated with pot ash and extracted with chloroform. The residue from the organic extract (2 g) passes colorless at approx. 100° C/0.01 mm (bulbs).
Det således erholdte pikolinoylamino-acetaldehyd-dietylacetal omsettes nøyaktig ifølge den forskrift som er gitt i eksempel The picolinoylamino-acetaldehyde-diethyl acetal thus obtained is reacted exactly according to the regulation given in example
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83471669A | 1969-06-19 | 1969-06-19 |
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| Publication Number | Publication Date |
|---|---|
| NO128496B true NO128496B (en) | 1973-11-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| NO03986/69A NO128496B (en) | 1969-06-19 | 1969-10-07 |
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| US (1) | US3570547A (en) |
| JP (1) | JPS4948575B1 (en) |
| AT (1) | AT289675B (en) |
| BE (1) | BE752203A (en) |
| CH (1) | CH502458A (en) |
| DE (1) | DE1953470A1 (en) |
| FR (1) | FR2052254A5 (en) |
| GB (1) | GB1281600A (en) |
| NL (1) | NL6918269A (en) |
| NO (1) | NO128496B (en) |
| SE (1) | SE350286B (en) |
| ZA (1) | ZA697054B (en) |
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| JPS5819778B2 (en) * | 1976-07-05 | 1983-04-20 | 株式会社岩間織機製作所 | loom winding device |
| JPS5819779B2 (en) * | 1976-07-05 | 1983-04-20 | 株式会社岩間織機製作所 | loom winding device |
| US10344407B2 (en) * | 2016-10-18 | 2019-07-09 | Wowwee Group Ltd. | Interactive loom |
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| US1737688A (en) * | 1929-12-03 | Setts | ||
| US3130756A (en) * | 1961-01-05 | 1964-04-28 | Fieldcrest Mills Inc | Terry motion for looms |
| US3351096A (en) * | 1967-03-20 | 1967-11-07 | Cannon Mills Co | Terry loom with fell shifting means |
-
1969
- 1969-06-19 US US834716A patent/US3570547A/en not_active Expired - Lifetime
- 1969-10-07 ZA ZA697054A patent/ZA697054B/en unknown
- 1969-10-07 NO NO03986/69A patent/NO128496B/no unknown
- 1969-10-22 CH CH1583769A patent/CH502458A/en not_active IP Right Cessation
- 1969-10-22 AT AT995369A patent/AT289675B/en active
- 1969-10-23 GB GB52071/69A patent/GB1281600A/en not_active Expired
- 1969-10-23 DE DE19691953470 patent/DE1953470A1/en active Pending
- 1969-10-27 SE SE14665/69A patent/SE350286B/xx unknown
- 1969-11-20 FR FR6940020A patent/FR2052254A5/fr not_active Expired
- 1969-12-04 NL NL6918269A patent/NL6918269A/xx unknown
-
1970
- 1970-04-15 JP JP45031662A patent/JPS4948575B1/ja active Pending
- 1970-06-18 BE BE752203D patent/BE752203A/en unknown
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| Publication number | Publication date |
|---|---|
| ZA697054B (en) | 1971-05-27 |
| SE350286B (en) | 1972-10-23 |
| DE1953470A1 (en) | 1970-12-23 |
| NL6918269A (en) | 1970-12-22 |
| US3570547A (en) | 1971-03-16 |
| JPS4948575B1 (en) | 1974-12-21 |
| BE752203A (en) | 1970-12-18 |
| CH502458A (en) | 1971-01-31 |
| FR2052254A5 (en) | 1971-04-09 |
| GB1281600A (en) | 1972-07-12 |
| AT289675B (en) | 1971-05-10 |
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