NO146358B - ANALOGY PROCEDURE FOR THE PREPARATION OF NEW THERAPEUTICALLY ACTIVE PROSTAGLANDINES - Google Patents
ANALOGY PROCEDURE FOR THE PREPARATION OF NEW THERAPEUTICALLY ACTIVE PROSTAGLANDINES Download PDFInfo
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- NO146358B NO146358B NO753051A NO753051A NO146358B NO 146358 B NO146358 B NO 146358B NO 753051 A NO753051 A NO 753051A NO 753051 A NO753051 A NO 753051A NO 146358 B NO146358 B NO 146358B
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- polyoxymethylenes
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- prostaglandines
- therapeutically active
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 25
- -1 polyoxymethylenes Polymers 0.000 claims description 22
- 229920006324 polyoxymethylene Polymers 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000003381 stabilizer Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 229940094443 oxytocics prostaglandins Drugs 0.000 abstract 1
- 150000003180 prostaglandins Chemical class 0.000 abstract 1
- 229930185605 Bisphenol Natural products 0.000 description 12
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical class OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000581 salicylamide Drugs 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C405/00—Compounds containing a five-membered ring having two side-chains in ortho position to each other, and having oxygen atoms directly attached to the ring in ortho position to one of the side-chains, one side-chain containing, not directly attached to the ring, a carbon atom having three bonds to hetero atoms with at the most one bond to halogen, and the other side-chain having oxygen atoms attached in gamma-position to the ring, e.g. prostaglandins ; Analogues or derivatives thereof
- C07C405/0008—Analogues having the carboxyl group in the side-chains replaced by other functional groups
- C07C405/0016—Analogues having the carboxyl group in the side-chains replaced by other functional groups containing only hydroxy, etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Furan Compounds (AREA)
Abstract
Analogifremgangsmåte ved fremstilling av nye terapeutisk aktive prostaglandiner.Analogous process for the preparation of new therapeutically active prostaglandins.
Description
Fremgangsmåte til stabilisering av høymolekylære polyacetaler. Process for stabilizing high molecular weight polyacetals.
Oppfinnelsen vedrører stabilisering av The invention relates to stabilization of
polyacetaler fortrinnsvis polyoksymetylener og blandingspolymerisater av formaldehyd resp. trioksan, mot innvirkning av varme og oksygen. polyacetals, preferably polyoxymethylenes and mixed polymers of formaldehyde or trioxane, against the effects of heat and oxygen.
Polyacetaler er polymerisater som inneholder følgende grunnbygningssten: Polyacetals are polymers containing the following building blocks:
R, betyr her et hydrogenatom og R. betyr et hydrogenatom eller en alkylgruppe, R, here means a hydrogen atom and R. means a hydrogen atom or an alkyl group,
f. eks. CH-gruppen. Spesiell betydning har polyacetaler av nevnte generelle formel, hvor såvel R, som også R. betyr et hydrogenatom, med andre ord hvor poly-acetalet er et polyoksymetylen. e.g. The CH group. Of particular importance are polyacetals of the aforementioned general formula, where both R and R mean a hydrogen atom, in other words where the polyacetal is a polyoxymethylene.
Det er kjent at høymolekylære polyoksymetylener som skal tjene til fremstil-ling av formlegemer som rør, profiler og sprøytestøpeartikler før forarbeidelsen må underkastes forskjellige stabiliseringspro-sesser. It is known that high molecular weight polyoxymethylenes which are to be used for the production of shaped bodies such as pipes, profiles and injection molded articles must be subjected to various stabilization processes before processing.
Således må f. eks. de etter kjente Thus, e.g. those after known
fremgangsmåter f. eks. ved polymerisa-sjon av formaldehyd, fremstilte høymole-kylære polyoksymetylener beskyttes ved blokering av endegruppene mot en etter den såkalte «glidelåsprinsippet» foregå-ende depolymerisering. For en endegruppe- methods e.g. by polymerization of formaldehyde, high-molecular polyoxymethylenes produced are protected by blocking the end groups against depolymerization taking place according to the so-called "zipper principle". For an end group-
forsegling er det kjent forskjellige fremgangsmåter f. eks. forestring eller foret-ring av oksyendegruppene. sealing, various methods are known, e.g. esterification or esterification of the oxygen end groups.
Blandingspolymerisatene av formaldehyd eller trioksan med f. eks. dietylen-glykolformol (difo) eller etylenoksyd inneholder en ustabil del som består av de endeplasserte formaldehydenheter. Ved si-den av den ved homopolymerisatene nevnte metode for forsegling av endegruppene lar det seg ved blandingpolymerisatene med spesielt godt resultat oppnå en ende-gruppestabilisering idet man fjerner disse ustabile deler ved hjelp av en termisk be-handling av blandingspolymerisatene. De-polymerisasjonen stopper i dette tilfelle ved oksyetylenenhetene. Videre er det nød-vendig å beskytte de nevnte polymerisater ved tilsetning av egnede stabilisatorer mot varme, oksydasjon og lysinnvirkning. The mixture polymers of formaldehyde or trioxane with e.g. diethylene glycol formalin (difo) or ethylene oxide contains an unstable part consisting of the end-placed formaldehyde units. In addition to the method for sealing the end groups mentioned for the homopolymers, end group stabilization can be achieved with particularly good results for the mixed polymers by removing these unstable parts by means of a thermal treatment of the mixed polymers. The de-polymerisation stops in this case at the oxyethylene units. Furthermore, it is necessary to protect the aforementioned polymers by adding suitable stabilizers against heat, oxidation and exposure to light.
Således er det f. eks. foreslått hydra-zin-, urinstoff- og thiourinstof f derivater, generelle syreamider, spesielt dikarbonsy-rediamider som virksomme stabilisatorer mot termisk spaltning av polyoksymetylener resp. av oksymetylen-blandingspolymerisater. Thus, it is e.g. proposed hydrazine, urea and thiourea derivatives, general acid amides, especially dicarboxylic acid diamides as effective stabilizers against thermal decomposition of polyoxymethylenes resp. of oxymethylene blend polymers.
For å øke bestandigheten mot oksydasjon ble det anbefalt tilsetninger av visse antioksydasjonsstoffer som fenoler, spesielt metylenbisfenoler og organiske svovelfor-bindelser. In order to increase resistance to oxidation, the addition of certain antioxidant substances such as phenols, especially methylene bisphenols and organic sulfur compounds, was recommended.
Den stabiliserende virkning av disse foreslåtte forbindelser er imidlertid delvis helt ufullkommen. Således tenderer f. eks. amider ofte til å trenge ut av den polymere. Polyamidet fører ofte til misfarvning, og er delvis bare dårlig forenelig med den polymere. Dessuten spiller en kombi-nasjon bestående av en termostabilisator og en oksydasjonsstabilisator synergistiske effekter en stor rolle, således at begge stabilisatorer må være avstemt mot hver-andre. The stabilizing effect of these proposed compounds is, however, partly completely imperfect. Thus tends, e.g. amides often penetrate the polymer. The polyamide often leads to discolouration, and is partly only poorly compatible with the polymer. Furthermore, a combination consisting of a thermostabilizer and an oxidation stabilizer plays a major role in synergistic effects, so that both stabilizers must be coordinated with each other.
Forbindelser som stabiliserer polyoksymetylener såvel mot termisk avbygning som også mot oksydasjon er hittil ikke kjent. Compounds which stabilize polyoxymethylenes both against thermal degradation and also against oxidation are not known to date.
Det er nu blitt funnet at forbindelser med den generelle formel I, som i det føl-gende betegnes som «amidbisfenoler» It has now been found that compounds of the general formula I, which are hereinafter referred to as "amide bisphenols"
hvori A betyr en enverdig fenolrest som er knyttet sammen med karbonylgruppen, fortrinnsvis i ortostilling, og B betyr en flere ganger alkylert fenols enverdige rest, idet hydroksylgruppen fortrinnsvis står i orto- eller para-stilling til metylengruppen har utmerkede stabiliserende virkning på polyoksymetylener. Som alkylsub-stituenter i B kan det stå alkylgrupper med fortrinnsvis 1—9 karbonatomer, f. eks. metyl-, etyl-, propyl-, isopropyl-, butyl-, isobutyl-, tert. butyl- og nonylgruppen. Antallet og plasseringen av disse alkylgrupper har ingen vesentlig innvirkning på stabilisatorvirkningen, imidlertid bør fe-nolene fortrinnsvis være dobbelt alkylert. in which A means a monovalent phenolic residue which is linked together with the carbonyl group, preferably in the ortho position, and B means a several times alkylated phenolic monovalent residue, the hydroxyl group being preferably in the ortho or para position to the methylene group having excellent stabilizing effects on polyoxymethylenes. Alkyl substituents in B can be alkyl groups with preferably 1-9 carbon atoms, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. the butyl and nonyl groups. The number and position of these alkyl groups has no significant effect on the stabilizer effect, however, the phenols should preferably be doubly alkylated.
Disse forbindelser med den generelle formel I er farveløse, krystallinske og i po-lare oppløsningsmidler lett oppløselige forbindelser. These compounds of the general formula I are colourless, crystalline and easily soluble compounds in polar solvents.
Det dreier seg her om stoffer som såvel inneholder en amidgruppering som også angir et usymmetrisk bisfenol. Helt avgjørende er imidlertid den mellom de to forskjellige fenoler innesluttede amid-inetylengruppering. These are substances which also contain an amide group which also indicates an unsymmetrical bisphenol. However, absolutely crucial is the amide-inethylene grouping enclosed between the two different phenols.
Det ble funnet at disse amid-bisfenoler formår å stabilisere polyoksymetylener samtidig såvel mot en termisk avbygning som også mot oksydasjon. Derved er den oksydasjonsstabiliserende virkning av amidbisfenolene som skal anvendes ifølge oppfinnelsen også minst likeverdig uten tilsetning av en kostabilisator som for de kjente bisfenoler som imidlertid krever en slik. It was found that these amide bisphenols are able to stabilize polyoxymethylenes at the same time against thermal degradation as well as against oxidation. Thereby, the oxidation-stabilizing effect of the amide bisphenols to be used according to the invention is also at least equivalent without the addition of a cost stabilizer as for the known bisphenols which, however, require such.
Amidbisfenolene har dessuten også følgende fordeler: De er lett fremstillbare, f. eks. ved kondensasjon av N-metylol-fenol-karbon- syreamider med de flere ganger alkylerte fenoler. The amide bisphenols also have the following advantages: They are easy to produce, e.g. by condensation of N-methylol-phenol-carbon- acid amides with the multiple alkylated phenols.
De lar seg meget lett anvende. Mens virkningen av noen egnede stabilisatorer avhenger av typen av tilblandingen til den polymere kan ved anvendelse av disse amidbisfenoler alle hittil vanlige meto-der til innblanding av stabilisatorer i den polymere anvendes uten at produktkvali-teten influeres som f. eks. innblandingen They are very easy to use. While the effect of some suitable stabilizers depends on the type of addition to the polymer, when using these amide bisphenols, all hitherto common methods for mixing stabilizers into the polymer can be used without the product quality being influenced, e.g. the interference
i knamaskin i smeiten, den mekaniske in a kneader in the smelter, the mechanical one
sammenblanding av fastpolymerisat og mixing of solid polymer and
faststabilisator eller optrekning fra et or-ganisk oppløsningsmiddel som f. eks. ace-ton, metanol eller dimetylformamid. solid stabilizer or raising from an organic solvent such as e.g. acetone, methanol or dimethylformamide.
De bevirker heller ikke ved lengre opp-varmning noen misfarvning av den polymere eller utsvedning. They also do not cause any discolouration of the polymer or sweating during prolonged heating.
De er godt forenlige med polyoksymetylenene. They are well compatible with the polyoxymethylenes.
De stabiliserer såvel homopolymerisater som også spesielt blandingspolymerisater av formaldehyd eller trioksan. They stabilize both homopolymers and especially mixed polymers of formaldehyde or trioxane.
Deres stabiliserende virkning økes dessuten betraktelig når man anvender dem dessuten med mindre mengder av en termostabilisator, f. eks. et dikarbonsyre-diamid, som malonsyrediamid eller ravsy-rediamid, videre ved at polyamid som me-toksymetyl-polykaprolactan eller polymere av N-vinyl-pyrrolidon, videre aromatiske aminer, f. eks. difenylamin eller et hydra-zin som tereftalsyrehydrazid eller et urin-stoffderivat som difenylurinstoff eller bis-(j-naftyltiourinstoff, spesielt imidlertid di-cyandiamid. Their stabilizing effect is also considerably increased when they are also used with smaller amounts of a thermostabilizer, e.g. a dicarboxylic acid diamide, such as malonic acid diamide or succinic acid rediamide, further in that polyamide such as methoxymethyl-polycaprolactan or polymers of N-vinyl-pyrrolidone, further aromatic amines, e.g. diphenylamine or a hydrazine such as terephthalic hydrazide or a urea derivative such as diphenylurea or bis-(j-naphthylthiourea), especially however dicyandiamide.
Det er vanligvis fordelaktig å stabilisere slike høymolekylære ifølge oppfinnelsen, som allerede er endegruppe stabiliserte enten det er ved acetylering ved homopolymerisater eller ved termisk avbygning ved blandingspolymerisater, enn-skjønt det prinsippielt imidlertid kan anvendes slike polymerisater som ikke er endegruppestabiliserte. It is usually advantageous to stabilize such high-molecular polymers according to the invention, which are already end-group stabilized, whether by acetylation in the case of homopolymers or by thermal degradation in the case of mixed polymers, although in principle such polymers that are not end-group stabilized can be used.
Til polyoksymetylenene settes det vanligvis 0,01—10 pst., fortrinnsvis 0,5—2 pst., amidbisfenol referert til vekten av det polymerisat som skal stabiliseres. Det kan også selvsagt anvendes blandinger av forskjellige amidbisfenoler. Videre kan det ofte være hensiktsmessig å anvende amid-bisfenolet eller amidbisfenolene sammen med andre i og for seg kjente varme- eller lysstabilisatorer. 0.01-10 per cent, preferably 0.5-2 per cent, of amide bisphenol is usually added to the polyoxymethylenes, based on the weight of the polymer to be stabilised. Mixtures of different amide bisphenols can of course also be used. Furthermore, it can often be appropriate to use the amide bisphenol or amide bisphenols together with other heat or light stabilizers known per se.
De følgende eksempler skal forklare fremgangsmåten ifølge oppfinnelsen nær-mere. Polyoksymetylenene som ble anvendt for disse forsøk var acetylerte homo polymerisater og blandingspolymerisater av trioksan og etylenoksyd med en redusert viskositet på 0,5—1,5 bestemt på en 0,5 pst.-ig oppløsning av den polymere i bu-tyrolacton ved 140° C under tilsetning av 2 pst. difenylamin som stabilisator. The following examples will explain the method according to the invention in more detail. The polyoxymethylenes used for these experiments were acetylated homopolymers and mixed polymers of trioxane and ethylene oxide with a reduced viscosity of 0.5-1.5 determined on a 0.5% solution of the polymer in butyrolactone at 140° C with the addition of 2% diphenylamine as stabilizer.
For å undersøke stabiliteten av de li-keledes med forbindelser med den generelle formel I stabiliserende høymolekyl-ære polyoksymetylener ble det målt vektstap av en prøve i prosent ved 230° C ved en oppvarmningstid på 45 minutter i luft. Det blir angitt vektstap pr. minutt. In order to investigate the stability of the stabilizing high molecular weight polyoxymethylenes, likewise with compounds of the general formula I, the weight loss of a sample was measured in percent at 230° C. with a heating time of 45 minutes in air. Weight loss per minute.
Eksempel 1. Example 1.
50 vektsdeler acetylert trioksan-homo-polymerisat oppslemmes i en oppløsning av 0,5 vektsdeler 2-metyl-4-oksy-5-isopro-pylbenzyl-salicylamid i 100 vektsdeler ace-ton og blandingen inndampes til tørrhet under mekanisk bevegelse. Mens en ustabilisert prøve, undersøkt etter den oven-nevnte metode på termostabilitet tapte 1,031 pst. av sin vekt viste den stabiliserte prøve under de samme betingelser et vektstap på 0,153 pst. 50 parts by weight of acetylated trioxane homopolymer is suspended in a solution of 0.5 parts by weight of 2-methyl-4-oxy-5-isopropylbenzyl-salicylamide in 100 parts by weight of acetone and the mixture is evaporated to dryness under mechanical agitation. While an unstabilized sample, examined according to the above-mentioned method for thermostability, lost 1.031 per cent of its weight, the stabilized sample under the same conditions showed a weight loss of 0.153 per cent.
Eksempel 2. Example 2.
5 vektsdeler av et blandingspolymerisat oppbygget av 98 vektsprosent trioksan og 2 vektsprosent etylenoksyd knas med 0,05 vektsdeler 2-metyl-4-oksy-5-isopro-pylbenzylsalicylamid i 15 minutter ved 200° C, mens en prøve av det stabiliserte produkt bare viser et vektstap på 0,053 pst., utgjør vektstapet av en sammenlig-ningsmessig undersøkt ustabilisert prøve derimot 0,635 pst. 5 parts by weight of a mixed polymer made up of 98% by weight trioxane and 2% by weight ethylene oxide are crushed with 0.05 parts by weight 2-methyl-4-oxy-5-isopropylbenzylsalicylamide for 15 minutes at 200° C, while a sample of the stabilized product only shows a weight loss of 0.053 per cent, the weight loss of a comparatively examined unstabilized sample, on the other hand, amounts to 0.635 per cent.
Eksempel 3. Example 3.
Det ble sammenknadd prøver av 5 vektsdeler av et blandingspolymerisat oppbygget av 98 vektsprosent trioksan og 2 vektsprosent etylenoksyd med 0,05 vektsdeler av et av de i følgende tabell anførte amidbisfenoler og 0,01 vektsdel dicyandi-amid i 15 minutter ved 200° C. De stabiliserte prøvers målte stabilitetsverdier er nedenfor sammenlignet med stabilitets-verdiene av en ustabilisert prøve. Samples of 5 parts by weight of a mixed polymer consisting of 98 percent by weight trioxane and 2 percent by weight ethylene oxide were kneaded together with 0.05 parts by weight of one of the amide bisphenols listed in the following table and 0.01 part by weight of dicyandiamide for 15 minutes at 200° C. The measured stability values of stabilized samples are compared below with the stability values of an unstabilized sample.
Eksempel 4. Example 4.
Det ble fremstillet prøver av 4 vektsdeler av et blandingspolymerisat oppbygget av 98 vektsprosent trioksan og 2 vektsprosent etylenoksyd, som ble stabilisert Samples were prepared of 4 parts by weight of a mixed polymer made up of 98 percent by weight trioxane and 2 percent by weight ethylene oxide, which was stabilized
henholdsvis med 0,028 vektsdeler av et av respectively with 0.028 parts by weight of one of
de i følgende tabell anførte «amidbisfeno- the "amide bispheno-
ler» og i et sammenligningsforsøk med 0,028 vektsdeler av det samme «Amidbisfenol» og dessuten med 0,008 vektsdeler di-cyandiamid ved oppvarming fra metano-lisk oppløsning. ler" and in a comparative experiment with 0.028 parts by weight of the same "Amidbisphenol" and also with 0.008 parts by weight of dicyandiamide when heated from a methanolic solution.
I den ovenfor angitte termostabili-tetsprøve viser prøvene følgende vektstap pr. minutt. In the above-mentioned thermostability test, the samples show the following weight loss per minute.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT26994/74A IT1044796B (en) | 1974-09-06 | 1974-09-06 | PGF BETA GANDOLFI |
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|---|---|
| NO753051L NO753051L (en) | 1976-03-09 |
| NO146358B true NO146358B (en) | 1982-06-07 |
| NO146358C NO146358C (en) | 1982-09-15 |
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| AT (1) | AT359215B (en) |
| BE (1) | BE833030A (en) |
| CA (1) | CA1056376A (en) |
| CH (1) | CH615908A5 (en) |
| CS (2) | CS190494B2 (en) |
| DE (1) | DE2539547A1 (en) |
| DK (1) | DK143939C (en) |
| FI (1) | FI752500A (en) |
| FR (2) | FR2313359A1 (en) |
| GB (1) | GB1498105A (en) |
| HU (1) | HU176654B (en) |
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| SE (1) | SE7509870L (en) |
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| ZA (1) | ZA755490B (en) |
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| IT1053781B (en) * | 1974-09-25 | 1981-10-10 | Erba C S P A Ora Farmitalia | OMEGA NOR CICLOALCIL 13.14 DEIDRO PROSTAGLANDINE |
| US4058564A (en) * | 1976-07-26 | 1977-11-15 | The Upjohn Company | Aliphatic 2-decarboxy-2-hydroxymethyl-13,14-didehydro-PG compounds |
| US4149006A (en) * | 1977-01-24 | 1979-04-10 | G. D. Searle & Co. | Prostaglandin derivatives having alkynyl, hydroxy and aryloxy junctions in the 2β side chain |
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1974
- 1974-09-06 HU HU74EA153A patent/HU176654B/en unknown
- 1974-09-06 IT IT26994/74A patent/IT1044796B/en active
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1975
- 1975-08-07 GB GB33048/75A patent/GB1498105A/en not_active Expired
- 1975-08-27 ZA ZA755490A patent/ZA755490B/en unknown
- 1975-08-28 AT AT665275A patent/AT359215B/en not_active IP Right Cessation
- 1975-09-02 DK DK394175A patent/DK143939C/en active
- 1975-09-03 BE BE159711A patent/BE833030A/en not_active IP Right Cessation
- 1975-09-05 DE DE19752539547 patent/DE2539547A1/en not_active Withdrawn
- 1975-09-05 FR FR7527360A patent/FR2313359A1/en active Granted
- 1975-09-05 SU SU752167370A patent/SU629872A3/en active
- 1975-09-05 CA CA234,843A patent/CA1056376A/en not_active Expired
- 1975-09-05 FI FI752500A patent/FI752500A/fi not_active Application Discontinuation
- 1975-09-05 NL NL7510517A patent/NL7510517A/en not_active Application Discontinuation
- 1975-09-05 SE SE7509870A patent/SE7509870L/en unknown
- 1975-09-05 JP JP50107940A patent/JPS51125045A/en active Pending
- 1975-09-05 CS CS756059A patent/CS190494B2/en unknown
- 1975-09-05 CS CS767640A patent/CS190498B2/en unknown
- 1975-09-05 NO NO753051A patent/NO146358C/en unknown
- 1975-09-05 CH CH1151475A patent/CH615908A5/en not_active IP Right Cessation
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1976
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Also Published As
| Publication number | Publication date |
|---|---|
| FR2315915B1 (en) | 1981-03-20 |
| SU629872A3 (en) | 1978-10-25 |
| NL7510517A (en) | 1976-03-09 |
| NO146358C (en) | 1982-09-15 |
| DE2539547A1 (en) | 1976-03-18 |
| ZA755490B (en) | 1977-04-27 |
| GB1498105A (en) | 1978-01-18 |
| DK394175A (en) | 1976-03-07 |
| AU8381275A (en) | 1977-02-10 |
| SE7509870L (en) | 1976-03-08 |
| JPS51125045A (en) | 1976-11-01 |
| DK143939B (en) | 1981-11-02 |
| IL48065A0 (en) | 1975-11-25 |
| ATA665275A (en) | 1980-03-15 |
| FR2313359A1 (en) | 1976-12-31 |
| CS190498B2 (en) | 1979-05-31 |
| CH615908A5 (en) | 1980-02-29 |
| CS190494B2 (en) | 1979-05-31 |
| FR2313359B1 (en) | 1980-05-30 |
| CA1056376A (en) | 1979-06-12 |
| NO753051L (en) | 1976-03-09 |
| BE833030A (en) | 1976-03-03 |
| DK143939C (en) | 1982-04-13 |
| AT359215B (en) | 1980-10-27 |
| FR2315915A1 (en) | 1977-01-28 |
| IT1044796B (en) | 1980-04-21 |
| FI752500A (en) | 1976-03-07 |
| HU176654B (en) | 1981-04-28 |
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