NO140007B - ANALOGICAL PROCEDURE FOR THE PREPARATION OF THERAPEUTICALLY ACTIVE INDOLCARBOXYLIC ACIDS - Google Patents
ANALOGICAL PROCEDURE FOR THE PREPARATION OF THERAPEUTICALLY ACTIVE INDOLCARBOXYLIC ACIDS Download PDFInfo
- Publication number
- NO140007B NO140007B NO307/73A NO30773A NO140007B NO 140007 B NO140007 B NO 140007B NO 307/73 A NO307/73 A NO 307/73A NO 30773 A NO30773 A NO 30773A NO 140007 B NO140007 B NO 140007B
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- Prior art keywords
- ketene
- indolcarboxylic
- acids
- preparation
- polymer
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- 238000000034 method Methods 0.000 title claims description 12
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical class C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 26
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006640 acetylation reaction Methods 0.000 claims description 8
- 230000021736 acetylation Effects 0.000 claims description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 235000019256 formaldehyde Nutrition 0.000 description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P3/00—Drugs for disorders of the metabolism
- A61P3/08—Drugs for disorders of the metabolism for glucose homeostasis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/42—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/60—Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Diabetes (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Hematology (AREA)
- Obesity (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Endocrinology (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Indole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Fremgangsmåte ved acetylering av formaldehydpolymere. Procedure for acetylation of formaldehyde polymers.
Den foreliggende oppfinnelse angår en fremgangsmåte ved acetylering av høypo-lymere av formaldehyd. The present invention relates to a method for the acetylation of high polymers of formaldehyde.
Som kjent har acetylering av formaldehydpolymere det formål å nedsette disse polymeres termiske spaltning ved de høye temperaturer som må anvendes når disse polymere skal benyttes i de kjente forme-metoder ved innsprøytning, ekstrudering osv., som vanlig anvendes ved bearbeidelse av termoplastiske materialer. As is known, acetylation of formaldehyde polymers has the purpose of reducing the thermal decomposition of these polymers at the high temperatures that must be used when these polymers are to be used in the known molding methods by injection, extrusion, etc., which are commonly used when processing thermoplastic materials.
Hittil er denne acetylering blitt utført So far this acetylation has been carried out
ved behandling i varm tilstand med eddik - syreanhydrid, i nærvær av en katalysator, som etterpå må fjernes fra den polymere. Denne fremgangsmåte krever anvendelse av store mengder eddiksyreanhydrid, for det ene for å oppnå en tilstrekkelig fukt-ning av det polymere pulver, hvis tilsyne-latende volumvekt er liten, og for det an-net for å begrense sluttkonsentrasjonen av eddiksyre, som dannes i løpet av reaksjonen og som, hvis den forefinnes i betydelig mengde, bidrar til spaltning av den polymere, mens behandlingen foregår. Før ed-diksyreanhydridet føres tilbake igjen i pro-sessen må det renses, særlig for å nedsette dets innhold av eddiksyre. by treatment in a hot state with acetic acid - anhydride, in the presence of a catalyst, which must then be removed from the polymer. This method requires the use of large amounts of acetic anhydride, on the one hand to achieve sufficient wetting of the polymeric powder, whose apparent volume weight is small, and on the other hand to limit the final concentration of acetic acid, which is formed during of the reaction and which, if present in a significant amount, contributes to the splitting of the polymer while the treatment takes place. Before the acetic anhydride is fed back into the process, it must be purified, in particular to reduce its content of acetic acid.
Hvis man fortynner eddiksyreanhydri-det tilstrekkelig med et passende fortyn-ningsmiddel, kan det anvendes mindre mengder eddiksyreanhydrid, men i så til-felle blir resultatene mindre gode, og det inntrer forskjellige gjenvinningsvanskelig-heter, som i høy grad kompliserer fremgangsmåten. If the acetic anhydride is sufficiently diluted with a suitable diluent, smaller quantities of acetic anhydride can be used, but in this case the results are less good, and various recovery difficulties arise, which greatly complicate the process.
Fremgangsmåten i henhold til opp- The procedure according to up-
finnelsen unngår disse ulemper og har den fordel å være meget enkel, effektiv og øko-nomisk. Den består i hovedsaken deri at acetyleringen av høypolymere av formaldehyd skjer ved innvirkning av gassformet keten (CH2 = C = O) ved forholdsvis høy temperatur. the invention avoids these disadvantages and has the advantage of being very simple, efficient and economical. It essentially consists in the fact that the acetylation of high polymers of formaldehyde takes place by the influence of gaseous ketene (CH2 = C = O) at a relatively high temperature.
Oppfinnerne har funnet at til tross for formaldehydpolymeres forholdsvis lette spaltbarhet ved varme, kan det ved bruk av temperaturer på 100—200° C, spesielt 140 —160° C, oppnås en effektiv acetylering av polymere ved hjelp av keten uten at det inntrer noen nevneverdig spaltning av dette eller dets produkter. The inventors have found that, despite the relatively easy heat splitting of formaldehyde polymers, by using temperatures of 100-200° C, especially 140-160° C, an effective acetylation of polymers can be achieved by means of the ketene without any significant cleavage of this or its products.
Dette kan forklares derved at over en viss temperatur tiltar acetyleringsreaksjo-nens hastighet meget sterkere enn den termiske spaltning av ikke acetylerte polymere. This can be explained by the fact that above a certain temperature the speed of the acetylation reaction increases much more strongly than the thermal decomposition of non-acetylated polymers.
Keten kan lett fås på billig måte, f. eks. av aceton eller eddiksyreanhydrid som ut-gangsmateriale. Keten can be easily obtained cheaply, e.g. of acetone or acetic anhydride as starting material.
På grunn av ketenets store reaktivitet i reaksjonen kan denne utføres uten tilste-deværelse av noen som helst katalysator. Due to the great reactivity of the ketene in the reaction, this can be carried out without the presence of any catalyst.
De høypolymere formaldehyder som man ønsker å acetylere bør fortrinnsvis be-finne seg i passende findelt tilstand, f. eks. i form av pulverkorn hvis størrelse ligger mellom 50 og 100 mikron (som akkurat er den kornstørrelse som fås ved de kjente polymerisasjonsmetoder for formaldehyd) eller endog, forefinnes oppløst i et oppløs-ningsmiddel. The high-polymer formaldehydes that one wishes to acetylate should preferably be in a suitably finely divided state, e.g. in the form of powder grains whose size is between 50 and 100 microns (which is exactly the grain size obtained by the known polymerization methods for formaldehyde) or even, found dissolved in a solvent.
Man kan også la ketenet innvirke på pulverformede polymere som er dispergert i et inert miljø, f. eks. i et alifatisk eller aromatisk, eventuelt klorert hydrokarbon, idet det gassformige keten bobles gjennom suspensjonen. One can also allow the ketene to act on powdered polymers that are dispersed in an inert environment, e.g. in an aliphatic or aromatic, optionally chlorinated hydrocarbon, the gaseous ketene being bubbled through the suspension.
For å unngå enhver oksydasjon av den-polymere i varm tilstand og for å oppnå en intim berøring mellom ketenet og poly-merpulveret, kan det være fordelaktig at man på forhånd fjerner luft, som måtte være innesluttet i pulveret, f. eks. ved at reaktoren som inneholder den polymere settes under vakuum, før ketenet innføres. For å begrense den termiske spaltning av den polymere kan fremgangsmåten med fordel utføres før reaktoren er blitt opp-hetet til den temperatur ved hvilken man ellers ønsker å tilføre ketenet, som på forhånd er blitt oppvarmet til den samme temperatur. In order to avoid any oxidation of the polymer in a hot state and to achieve an intimate contact between the ketene and the polymer powder, it may be advantageous to remove air in advance, which may be trapped in the powder, e.g. in that the reactor containing the polymer is placed under vacuum before the ketene is introduced. In order to limit the thermal decomposition of the polymer, the method can advantageously be carried out before the reactor has been heated to the temperature at which one would otherwise like to add the ketene, which has been heated to the same temperature in advance.
Som reaktor kan det anvendes et hvil-ket som helst lukket rom, som kan opphe-tes og som eventuelt er utstyrt med en røreinnretning som gir en passende om-røring av pulveret, eller suspensjonen eller, oppløsningen av den polymere. For å holde de pulverformede polymere i stadig omrø-ring, kan man spesielt benytte fluidise-ringsteknikken. As a reactor, any closed space can be used, which can be heated and which is optionally equipped with a stirring device which provides a suitable stirring of the powder, or the suspension or the solution of the polymer. In order to keep the powdered polymers in constant agitation, the fluidization technique can especially be used.
Da den struktur som de formaldehydpolymere generelt har tilsvarer strukturen hos polyoksymetylenglykoler, vil ketenet reagere med okshydrylgruppene, som rep-resenterer en meget liten prosentmengde av makromolekylet. Under disse forhold er den mengde keten som behøves for en gitt vektmengde polymerpulver forholdsvis meget liten. Det er derfor tilstrekkelig at det til reaktoren stadig tilføres tilstrekkelig meget keten til å erstatte dettes forbruk i reaksjonsrommet. As the structure of the formaldehyde polymers generally corresponds to the structure of polyoxymethylene glycols, the ketene will react with the oxyhydryl groups, which represent a very small percentage of the macromolecule. Under these conditions, the amount of ketene required for a given amount of polymer powder by weight is relatively very small. It is therefore sufficient that a sufficient amount of ketene is continuously supplied to the reactor to replace its consumption in the reaction space.
De nedenstående eksempler belyser oppfinnelsen. The following examples illustrate the invention.
Eksempel 1. Example 1.
Det anvendes et pulver av høypoly-mert formaldehyd, som har følgende egenskaper : — Den prosentmengde av produktet som ei oppløselig i en vandig oppløsning som inneholder 1 mol natriumsulfitt pr. li-ter, ved omrøring i 1 time ved 20° C, ut-gjør 8,1, — pulveret er blitt oppvarmet i 7 dager i en ovn i hvilken lufttrykket er vanlig og temperaturen er 110° C, hvorved pulveret har tapt 16 pst. av sin vekt, — den absolutte viskositet er som definerl av Cragg (J. Col. Sei 1, 261—269, 1946) A powder of highly polymerized formaldehyde is used, which has the following properties: — The percentage of the product which is not soluble in an aqueous solution containing 1 mol of sodium sulphite per litres, when stirred for 1 hour at 20° C, amounts to 8.1, — the powder has been heated for 7 days in an oven in which the air pressure is normal and the temperature is 110° C, whereby the powder has lost 16 percent .of its weight, — the absolute viscosity is as definerl by Cragg (J. Col. Sei 1, 261—269, 1946)
og målt ved konsentrasjon 0,5 pst. ved 60° C i paraklorfenol som inneholder 2 vektprosent alfapinen har verdien 2,2, den termiske spaltningshurtighet ved 222° C, etter de første 10 minutters for-løp, er 5,7, uttrykt som vekttap i- prosent pr. minutt av den resterende polymere. and measured at a concentration of 0.5 percent at 60° C. in parachlorophenol containing 2 percent by weight alphapinene has the value 2.2, the rate of thermal decomposition at 222° C., after the first 10 minutes, is 5.7, expressed as weight loss in percent per minute of the remaining polymer.
Som reaktor anvendes det en sylind-risk, vertikal glassbeholder, på hvis midt-parti det er fastsveiset en sirkulær, hori-sontal plate av sintret glass. Ved sitt nedre parti har denne beholder en rørstuss, som er utstyrt med en kran og er forbundet med en kilde for gassformig keten, og ved sitt øvre parti har tre rørstusser, av hvilke den As a reactor, a cylindrical, vertical glass container is used, on the middle part of which a circular, horizontal plate of sintered glass is welded. At its lower part, this container has a pipe connection, which is equipped with a tap and is connected to a source of gaseous ketene, and at its upper part has three pipe connections, of which the
ene er så stor og er utstyrt med en løs-bar propp for innføring av pulveret, mens one is so large and is equipped with a removable plug for introducing the powder, while
de to- andre rørstusser er via ventiler forbundet med atmosfæren, resp. med en va-.kuumpumpe. the other two pipe ends are connected to the atmosphere via valves, resp. with a vacuum pump.
På den sintrede glassplate fordeles det jevnt 5 g polymer av ovennevnte art, rom-met evakueres, det tilføres keten som er fått ved pyrolyse av aceton, som først slip-pes ut igjen gjennom utløpsrøret til atmosfæren etter at det ønskede trykk er blitt etablert. Apparatet dyppes deretter i et oljebad som holdes på 140° C i 4 timer, og i hele denne tid ledes det igjennom en langsom strøm av keten, som er blitt forhånds-oppvarmet ved å føres gjennom en foran apparatet anbragt slange, som er neddyk-ket i det samme oljebad. On the sintered glass plate, 5 g of polymer of the above-mentioned type is evenly distributed, the room is evacuated, the ketene obtained by pyrolysis of acetone is added, which is only released again through the outlet pipe to the atmosphere after the desired pressure has been established. The apparatus is then immersed in an oil bath which is kept at 140° C for 4 hours, and during this whole time it is led through a slow stream of ketene, which has been pre-heated by being passed through a hose placed in front of the apparatus, which is immersed ket in the same oil bath.
Etter behandlingen tas pulveret ut av apparatet, vaskes med aceton og tørkes i vakuum. Det har da følgende egenskaper: After treatment, the powder is removed from the apparatus, washed with acetone and dried in a vacuum. It then has the following properties:
Oppløselighet i vandig natriumsulfitt 0 % Tap i ovnen ved. opphetning ved Solubility in aqueous sodium sulphite 0% Loss in the furnace at. heating by
Videre finner man at i løpet av behandlingen har pulveret bare lidt et vekttap på 5- pst. Furthermore, it is found that during the treatment the powder has only suffered a weight loss of 5 per cent.
Eksempel 2. Example 2.
Man anbringer 5 g av ovennevnte høy-polymer i en ballong, som er forsynt med en rører som sette i langsom bevegelse og 5 g of the above-mentioned high-polymer is placed in a balloon, which is equipped with a stirrer that sets in slow motion and
som passerer meget nær ved ballongens i vegger, slik at pulveret røres om og. gnis godt. Videre går man frem nøyaktig som i eksempel 1, hva angår tilføring av vakuum og omrøring i kulden, men ballon-t gen dyppes dereter i et oljebad som hol-i des på 150° C, og gjennomledningen av which passes very close to the walls of the balloon, so that the powder is stirred around and. rub well. You then proceed exactly as in example 1, with regard to the addition of vacuum and stirring in the cold, but the balloon is then dipped in an oil bath held at 150° C, and the passage of
Produktets egenskaper etter behandlingen og vasking med aceton var som føl-ger: Oppløselighet i vandig natriumsulfitt 0 % Tap ved opphetningen ved 110° C 6% Viskositeten, lite forandret Termisk spaltnings- hastighet 0,85 % pr. min. The product's properties after treatment and washing with acetone were as follows: Solubility in aqueous sodium sulphite 0% Loss on heating at 110° C 6% Viscosity, little changed Thermal decomposition speed 0.85% per my.
Vekttapet under behandlingen er ca. 6%. keten fortsettes i 2 timer ved denne temperatur. The weight loss during the treatment is approx. 6%. the chain is continued for 2 hours at this temperature.
Etter behandlingen og vasking med aceton har produktet følgende egenskaper: Oppløselighet i vandig natriumsulfitt 0% Tap ved opphetningen ved 110° C 0,4 % Iboende viskositet uforandret Hastighet av termisk After the treatment and washing with acetone, the product has the following properties: Solubility in aqueous sodium sulphite 0% Loss on heating at 110° C 0.4% Inherent viscosity unchanged Rate of thermal
spaltning 0,48 % pr. min. cleavage 0.48% per my.
Vekttapet under behandlingen er under 3 %. The weight loss during the treatment is less than 3%.
Ved pressing ved 200° C og et trykk på 150 kg/cm^ fremstilles det en 0,12 mm tykk film av det behandlede produkt. Denne film kan brettes 20 ganger langs en og samme linje uten å gå istykker. By pressing at 200° C and a pressure of 150 kg/cm^, a 0.12 mm thick film is produced from the treated product. This film can be folded 20 times along one and the same line without breaking.
Eksempel 3. Example 3.
Den samme polymere som i eks. 1 be-handles på samme måte og i det samme ap-parat, med den forskjell at tilførselsstrøm-men av keten opprettholdes i 1 time ved 160° C. The same polymer as in ex. 1 is treated in the same way and in the same apparatus, with the difference that the supply flow of the chain is maintained for 1 hour at 160° C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722203542 DE2203542A1 (en) | 1972-01-26 | 1972-01-26 | BLOOD SUGAR-LOWERING INDOLCARBONIC ACID DERIVATIVES AND PROCESS FOR THEIR PRODUCTION |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO140007B true NO140007B (en) | 1979-03-12 |
| NO140007C NO140007C (en) | 1979-06-20 |
Family
ID=5834053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO307/73A NO140007C (en) | 1972-01-26 | 1973-01-25 | ANALOGICAL PROCEDURE FOR THE PREPARATION OF THERAPEUTICALLY ACTIVE INDOLCARBOXYLIC ACIDS |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS5930703B2 (en) |
| AR (2) | AR194640A1 (en) |
| AT (3) | AT320634B (en) |
| AU (1) | AU465326B2 (en) |
| BE (1) | BE794483A (en) |
| CA (1) | CA983511A (en) |
| CH (2) | CH587816A5 (en) |
| CS (2) | CS164222B2 (en) |
| DD (1) | DD103642A5 (en) |
| DE (1) | DE2203542A1 (en) |
| DK (1) | DK134517C (en) |
| EG (1) | EG10793A (en) |
| ES (1) | ES410934A1 (en) |
| FI (1) | FI55829C (en) |
| FR (1) | FR2169181B1 (en) |
| GB (2) | GB1369578A (en) |
| HU (1) | HU164871B (en) |
| IL (1) | IL41350A (en) |
| NL (1) | NL154420B (en) |
| NO (1) | NO140007C (en) |
| PL (2) | PL92384B1 (en) |
| SE (1) | SE388196B (en) |
| SU (2) | SU509219A3 (en) |
| YU (2) | YU17473A (en) |
| ZA (1) | ZA73545B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5579169A (en) * | 1978-12-12 | 1980-06-14 | Seiko Epson Corp | Ink jet type recorder |
| JPS5945108U (en) * | 1982-09-20 | 1984-03-26 | トヨタ自動車株式会社 | Suspension arm of Utsusha bone type suspension |
| US4510157A (en) * | 1982-12-27 | 1985-04-09 | Ayerst, Mckenna & Harrison, Inc. | 6,7,8,9-Tetrahydro-1H-benz(g)indol-8-amine derivatives |
| US4470990A (en) * | 1983-03-14 | 1984-09-11 | Ayerst, Mckenna & Harrison Inc. | 6,7,8,9-Tetrahydronaphtho(1,2-B)furan-8-amine derivatives and their use as dopamine receptor stimulants |
| FR2768146B1 (en) | 1997-09-05 | 2000-05-05 | Oreal | NOVEL COMPOUNDS FROM THE INDOLE-CARBOXYLIC FAMILY AND THEIR USE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3332846A (en) * | 1965-03-02 | 1967-07-25 | American Cyanamid Co | Method of inducing hypoglycemia with a substituted indole |
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0
- BE BE794483D patent/BE794483A/en not_active IP Right Cessation
-
1972
- 1972-01-26 DE DE19722203542 patent/DE2203542A1/en active Granted
-
1973
- 1973-01-21 IL IL41350A patent/IL41350A/en unknown
- 1973-01-22 CH CH1530476A patent/CH587816A5/xx not_active IP Right Cessation
- 1973-01-22 GB GB616774A patent/GB1369578A/en not_active Expired
- 1973-01-22 GB GB318573A patent/GB1369577A/en not_active Expired
- 1973-01-22 YU YU00174/73A patent/YU17473A/en unknown
- 1973-01-22 CH CH85973A patent/CH586677A5/xx not_active IP Right Cessation
- 1973-01-22 DD DD168375A patent/DD103642A5/xx unknown
- 1973-01-22 EG EG23/73A patent/EG10793A/en active
- 1973-01-22 NL NL737300871A patent/NL154420B/en not_active IP Right Cessation
- 1973-01-22 AR AR246234A patent/AR194640A1/en active
- 1973-01-23 AU AU51374/73A patent/AU465326B2/en not_active Expired
- 1973-01-23 FI FI177/73A patent/FI55829C/en active
- 1973-01-24 CS CS8086*A patent/CS164222B2/cs unknown
- 1973-01-24 CS CS537A patent/CS164221B2/cs unknown
- 1973-01-24 ES ES410934A patent/ES410934A1/en not_active Expired
- 1973-01-24 FR FR7302419A patent/FR2169181B1/fr not_active Expired
- 1973-01-24 CA CA161,918A patent/CA983511A/en not_active Expired
- 1973-01-25 ZA ZA730545A patent/ZA73545B/en unknown
- 1973-01-25 NO NO307/73A patent/NO140007C/en unknown
- 1973-01-25 PL PL1973182916A patent/PL92384B1/pl unknown
- 1973-01-25 PL PL1973160407A patent/PL89093B1/pl unknown
- 1973-01-25 AT AT64073A patent/AT320634B/en not_active IP Right Cessation
- 1973-01-25 AT AT62074*7A patent/AT327885B/en active
- 1973-01-25 DK DK42173A patent/DK134517C/en active
- 1973-01-25 SE SE7301029A patent/SE388196B/en unknown
- 1973-01-25 AT AT62074*A patent/ATA62074A/en unknown
- 1973-01-25 HU HUBO1411A patent/HU164871B/hu unknown
- 1973-01-26 JP JP48010925A patent/JPS5930703B2/en not_active Expired
- 1973-01-26 SU SU1886348A patent/SU509219A3/en active
- 1973-07-12 AR AR249042A patent/AR195134A1/en active
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1974
- 1974-08-30 SU SU2056253A patent/SU530642A3/en active
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1979
- 1979-07-23 YU YU01795/79A patent/YU179579A/en unknown
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