NO131119B - - Google Patents
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- NO131119B NO131119B NO04578/70A NO457870A NO131119B NO 131119 B NO131119 B NO 131119B NO 04578/70 A NO04578/70 A NO 04578/70A NO 457870 A NO457870 A NO 457870A NO 131119 B NO131119 B NO 131119B
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- alkyl
- dione
- denotes
- acetoxy
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- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000003431 steroids Chemical class 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000003110 anti-inflammatory effect Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000001054 cortical effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- SNAYLCYCEXREJX-WWSDEZETSA-N [(3r,8s,9s,10s,13s,14s)-17-acetyl-10,13,16-trimethyl-11-oxo-1,2,3,4,5,6,7,8,9,12,14,15-dodecahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C(=O)[C@@H]2[C@@]3(C)CC[C@@H](OC(=O)C)CC3CC[C@H]2[C@@H]2CC(C)=C(C(C)=O)[C@]21C SNAYLCYCEXREJX-WWSDEZETSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- BZWJDKJBAVXCMH-UHFFFAOYSA-N 1-diazopropane Chemical compound CCC=[N+]=[N-] BZWJDKJBAVXCMH-UHFFFAOYSA-N 0.000 description 2
- -1 5- methylpregnane-11, 20-dione Chemical compound 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229940121363 anti-inflammatory agent Drugs 0.000 description 2
- 239000002260 anti-inflammatory agent Substances 0.000 description 2
- WLXALCKAKGDNAT-UHFFFAOYSA-N diazoethane Chemical compound CC=[N+]=[N-] WLXALCKAKGDNAT-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000003128 pregnanes Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PFJVIOBMBDFBCJ-UHFFFAOYSA-N (1z)-1-diazobutane Chemical compound CCCC=[N+]=[N-] PFJVIOBMBDFBCJ-UHFFFAOYSA-N 0.000 description 1
- CBYCRMIWATZBBW-RDQPJNLGSA-N (8r,9s,10s,13s,14s)-17-ethyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15-dodecahydro-1h-cyclopenta[a]phenanthrene Chemical class C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC=C(CC)[C@@]1(C)CC2 CBYCRMIWATZBBW-RDQPJNLGSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FUFLCEKSBBHCMO-UHFFFAOYSA-N 11-dehydrocorticosterone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)C(=O)CO)C4C3CCC2=C1 FUFLCEKSBBHCMO-UHFFFAOYSA-N 0.000 description 1
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MFYSYFVPBJMHGN-ZPOLXVRWSA-N Cortisone Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 MFYSYFVPBJMHGN-ZPOLXVRWSA-N 0.000 description 1
- MFYSYFVPBJMHGN-UHFFFAOYSA-N Cortisone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)(O)C(=O)CO)C4C3CCC2=C1 MFYSYFVPBJMHGN-UHFFFAOYSA-N 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229960004544 cortisone Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B39/00—Equipment to decrease pitch, roll, or like unwanted vessel movements; Apparatus for indicating vessel attitude
- B63B39/06—Equipment to decrease pitch, roll, or like unwanted vessel movements; Apparatus for indicating vessel attitude to decrease vessel movements by using foils acting on ambient water
- B63B39/061—Equipment to decrease pitch, roll, or like unwanted vessel movements; Apparatus for indicating vessel attitude to decrease vessel movements by using foils acting on ambient water by using trimflaps, i.e. flaps mounted on the rear of a boat, e.g. speed boat
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Ocean & Marine Engineering (AREA)
- Actuator (AREA)
- Steroid Compounds (AREA)
Description
Fremgangsmåte til fremstilling av nye 16/V-alkyl-ll-oxygenerte steroider av pregnanrekken. Process for the production of new 16/V-alkyl-11-oxygenated steroids of the pregnane series.
Foreliggende oppfinnelse angår en fremgangsmåte til fremstilling av nye 16(3-alkyl-ll-oxygenerte steroider av pregnanrekken. The present invention relates to a method for the production of new 16(3-alkyl-11-oxygenated steroids of the pregnane series.
De 16|3-alkyl-steroider som fåes ved fremgangsmåten ifølge oppfinnelsen er for-delaktige mellomprodukter som kan over-føres til 16[3-alkylkortikalsteroider. Sistnevnte forbindelser har en ytterst sterk an-tiinflammatorisk virkning som er betyde-lig sterkere enn de opprinnelige kortikal-steroiders antiinnflammatoriske virkning, og de er særlig effektive til behandling av artrit og lignende sykdommer. De gir kor-tisonlignende virkning i ytterst små doser, hvorved uønskede bivirkninger gjøres minst mulige. Det er nytt at 16(5-alkylsteroider har denne virkning, da alle tidligere sub-stituerte modifikasjoner av kortikalsteroider med økende antiinflammatoriske virk-ninger har omfattet innføring av a-substi-tuenter. The 16[3-alkyl steroids obtained by the method according to the invention are advantageous intermediates which can be transferred to 16[3-alkyl cortical steroids. The latter compounds have an extremely strong anti-inflammatory effect which is significantly stronger than the anti-inflammatory effect of the original cortical steroids, and they are particularly effective in the treatment of arthritis and similar diseases. They provide a cortisone-like effect in extremely small doses, whereby unwanted side effects are kept to a minimum. It is new that 16(5-alkyl steroids have this effect, as all previously substituted modifications of cortical steroids with increasing anti-inflammatory effects have included the introduction of α-substituents.
I fremgangsmåten ifølge oppfinnelsen kan der som utgangsmaterialer brukes 16(3-alkyl-3-substituert ll-oxygenert-16-preg-nen-20-on eller et 16(3-alkyl-3-substituert ll-oxygenert-16-allopregnen-20-on som tilsvarer følgende generelle formel: In the method according to the invention, 16(3-alkyl-3-substituted 11-oxygenated-16-preg-nen-20-one or a 16(3-alkyl-3-substituted 11-oxygenated-16-allopregen-20-one) can be used as starting materials 20-on which corresponds to the following general formula:
I denne generelle formel betegner X In this general formula, X denotes
hydrogen eller halogen, Y betegner hydrogen i a-eller (3-stillingen, Z betegner oxygen, dioxolan, a- eller (3-acyloxy eller hy-droxy, R betegner alkyl og R' betegner en hydroxyl-gruppe eller oxygen. I 5(6) -stil- hydrogen or halogen, Y denotes hydrogen in the a- or (3-position, Z denotes oxygen, dioxolane, a- or (3-acyloxy or hydroxy, R denotes alkyl and R' denotes a hydroxyl group or oxygen. I 5 (6) -style-
lingen kan en dobbeltbinding være tilstede eller ikke være tilstede. ling, a double bond may or may not be present.
De ovenfor angitte A<1>(<i->16-alkyl-utgangsmaterialer for fremgangsmåten ifølge oppfinnelsen, nemlig 16-alkyl-3-substitu-erte-ll-oxygenerte-16-pregnen-20-oner eller 16-alkyl-3-substituerte-ll-oxyge-nerte-16-allopregnen-20-oner kan fremstilles ved å omsette de tilsvarende 16-pregnener eller 16-allopregnener med dia-zoalkaner som diazometan, diazoetan, diazopropan eller diazobutan, hvorved der dannes de tilsvarende 3-substituerte-ll-oxygenerte-16a, 17a-alkylenazopregnan-azo-allopregnan-20-oner som tilsvarer føl-20-oner eller 3-substituerte-ll-oxygenerte-gende generelle formel: The above-mentioned A<1>(<i>16-alkyl starting materials for the process according to the invention, namely 16-alkyl-3-substituted-11-oxygenated-16-pregnen-20-ones or 16-alkyl-3 -substituted-11-oxygen-nerte-16-allopregnen-20-ones can be prepared by reacting the corresponding 16-pregnenes or 16-allopregnes with diazoalkanes such as diazomethane, diazoethane, diazopropane or diazobutane, whereby the corresponding 3- substituted-11-oxygenated-16a, 17a-alkylenazopregnan-azo-allopregnan-20-ones corresponding to fur-20-ones or 3-substituted-11-oxygenated general formula:
i hvilken R', X, Y og Z har de ovenfor angitte betydninger, mens R" betegner hydrogen eller alkyl. Også her kan en dobbeltbinding være tilstede eller ikke være tilstede i 5(6)-stillingen. Ved oppvarmning av disse forbindelser utvikles nitrogen og der dannes primært de tilsvarende 16-alkyl-3-substituerte-ll-oxygenerte-16-pregnen-20-oner eller 16-alkyl-3-substituerte-l 1 -oxygenerte-16-allopregnen-20-oner som altså er utgangsmaterialer for fremgangsmåten ifølge oppfinnelsen og som nevnt tilsvarer følgende generelle formel: I en foretrukken utførelsesform for oppfinnelsen brukes der som utgangsmateriale 3a-acetoxy-16(3-metyl-16-preg-nen-ll,20-dion som tilsvarer følgende generelle formel: Det er funnet at 3a-acyloxy-16(3-alkyl-16-pregnen-ll,20-dionene kan hydreres i nærvær av hydreringskatalysatorer som palladium på kalsiumkarbonat så at der dannes 3a-acyloxy-16(3-alkylpregnan-ll,20-dioner som tilsvarer følgende generelle formel: in which R', X, Y and Z have the meanings given above, while R" denotes hydrogen or alkyl. Here, too, a double bond may or may not be present in the 5(6) position. When these compounds are heated, nitrogen is evolved and there primarily the corresponding 16-alkyl-3-substituted-11-oxygenated-16-pregnen-20-ones or 16-alkyl-3-substituted-11-oxygenated-16-allopregnen-20-ones are formed, which are therefore starting materials for the method according to the invention and as mentioned corresponds to the following general formula: In a preferred embodiment of the invention, 3a-acetoxy-16(3-methyl-16-preg-nen-11,20-dione is used as starting material which corresponds to the following general formula: it has been found that the 3a-acyloxy-16(3-alkyl-16-pregnan-11,20-diones can be hydrogenated in the presence of hydrogenation catalysts such as palladium on calcium carbonate so that 3a-acyloxy-16(3-alkylpregnan-11,20- diones corresponding to the following general formula:
i hvilken R betegner alkyl og R"' betegner acyl. in which R denotes alkyl and R"' denotes acyl.
De forbindelser som fåes ved fremgangsmåten ifølge oppfinnelsen kan lett overføres til 16(3-metyl-kortikalsteroider som er effektive anti-inflammatoriske mid-ler. Et eksempel på en slik fremgangsmåte er følgende: Et 16|3-alkyl-3a, 17a-dihydroxypreg-nan-ll,20-dion bromeres hvorved der dannes et 16a-alkyl-21-brom-3a, 17a-dihy-droxypregnan-ll,20-dion. Denne forbindelse omsettes med et acyleringsmiddel hvorved der dannes et 16[3-alkyl-3a, 17a-21-trihydroxypregnan-ll,20-dion-21-acylat. Ved omsetning av sistnevnte forbindelse med et oxyderingsmiddel som N-bromsuc-cin-imid eller kromsyre dannes der et 16(3-alkyl-17a, 21-dihydroxypregnan-3,11,20-trion-21-acylat. Ved bromering av sistnevnte forbindelse dannes der et 16(3-alkyl-4-brom-17a, 21-dihydroxypregnan-3,11,20- trion-21-acylat. Denne forbindelse omsettes med semikarbazid-hydroklorid, hvorved der dannes 3-semikarbazonet av et 16(3-alkyl-17a, 21-dihydroxy-4-pregnen-3,11,20-trion-21-acylat. Sistnevnte forbindelse omsettes med pyrodruesyre i vandig eddiksyre hvorved der dannes 16|3-alkyl-17a, 21-di-hydroxy-4-pregnen-3,ll,20-trion-21- acy-lat. Denne forbindelse kan også betegnes The compounds obtained by the method according to the invention can easily be transferred to 16(3-methyl-cortical steroids which are effective anti-inflammatory agents. An example of such a method is the following: A 16|3-alkyl-3a, 17a-dihydroxypreg -nan-11,20-dione is brominated to form a 16a-alkyl-21-bromo-3a,17a-dihydroxypregnan-11,20-dione This compound is reacted with an acylating agent to form a 16[3-alkyl -3a, 17a-21-trihydroxypregnan-11,20-dione-21-acylate. When the latter compound is reacted with an oxidizing agent such as N-bromosuccinimide or chromic acid, a 16(3-alkyl-17a, 21- dihydroxypregnan-3,11,20-trione-21-acylate On bromination of the latter compound, a 16(3-alkyl-4-bromo-17a, 21-dihydroxypregnan-3,11,20- trione-21-acylate. This compound is reacted with semicarbazide hydrochloride, whereby the 3-semicarbazone of a 16(3-alkyl-17a, 21-dihydroxy-4-pregnene-3,11,20-trione-21-acylate is formed. The latter compound is reacted with pyruvic acid in aqueous acetic acid, whereby 16|3-alkyl-17a,21-di-hydroxy-4-pregnene-3,11,20-trione-21-acylate is formed.This compound can also be termed
16(3-alkyl-kortisonacylat og er et effektivt anti-inflammatorisk middel. 16(3-alkyl cortisone acylate) and is an effective anti-inflammatory agent.
I det følgende beskrives som eksempel en utførelsesform for oppfinnelsen. In the following, an embodiment of the invention is described as an example.
Eksempel: Example:
Fremstilling av 3a- acetoxy- 16\ 5- metylpregnan- 11, 20- dion. Preparation of 3a-acetoxy- 16\ 5- methylpregnane-11, 20-dione.
En oppløsning av 200 mg 3a-acetoxy-16-metyl-16-pregnen-ll,20-dion (fremstil-let således som det beskrives i det følgende) A solution of 200 mg of 3α-acetoxy-16-methyl-16-pregnene-11,20-dione (prepared as described below)
i 20 ml metanol ble tilsatt 200 mg kataly- 200 mg of catalyst was added to 20 ml of methanol
sator bestående av palladium på kalsium- sator consisting of palladium on calcium-
karbonat med 25 pst. palladium. Blandin- carbonate with 25 percent palladium. Blendin-
gen ble omrørt i hydrogenatmosfære (1 gen was stirred in a hydrogen atmosphere (1
atm. trykk, 25° C) inntil opptagelsen av hydrogen var avsluttet. Blandingen ble derpå filtrert, filtratet ble inndampet til tørrhet og residuet omkrystallisert fra en blanding av eter og hexan, hvorved man fikk rent 3a-acetoxy-16|3-metylpreg-nan-ll,20-dion som nåler med smeltepunkt atm. pressure, 25° C) until the uptake of hydrogen had ended. The mixture was then filtered, the filtrate evaporated to dryness and the residue recrystallized from a mixture of ether and hexane, whereby pure 3α-acetoxy-16|3-methylpregnan-11,20-dione was obtained as needles with melting point
CHC1 CHC1
160-162° C. X maks; 160-162° C. X max;
5,80, 5,85, 8,0 (a)nCHCl3=+ 96° (C = 1,00). 5.80, 5.85, 8.0 (a) nCHCl 3 = + 96° (C = 1.00).
Analyse: Analysis:
Beregnet for C^H.^O,: C 74.19 pst., Calculated for C^H.^O,: C 74.19 per cent,
H 9.33 pst." H 9.33 percent."
Funnet: C 74.15 pst., H 9.15 pst. Found: C 74.15 per cent, H 9.15 per cent.
Det 3a-acetoxy-16-metyl-16-pregnen- The 3α-acetoxy-16-methyl-16-pregnene-
11,20-dion som ble brukt som utgangsmate- 11,20-dione which was used as starting feed-
riale i dette eksempel fremstilles ved å gå rial in this example is produced by walking
ut fra den kjente forbindelse 3a-acetoxy-16-pregnen-ll,20-dion og å anvende føl- starting from the known compound 3α-acetoxy-16-pregnene-11,20-dione and using follow-
gende fremgangsmåte: following procedure:
I en 500 ml 3-halset kolbe forsynt med In a 500 ml 3-necked flask provided with
kjøler, tilvirkningstrakt og tilførselsled- cooler, production funnel and supply line
ning for nitrogen ble anbragt 20 g kalium- ning for nitrogen was placed 20 g of potassium
hydroxyd i 90 ml vann, 100 ml metanol og 100 ml eter. En oppløsning av 10 g N-metyl-N-nitrosotosylamid i 50 ml eter ble anbragt hydroxide in 90 ml of water, 100 ml of methanol and 100 ml of ether. A solution of 10 g of N-methyl-N-nitrosotosylamide in 50 ml of ether was placed
i tilvirkningstrakten. in the production funnel.
Diazometan ble dannet ved å oppvarme Diazomethane was formed by heating
kolben til 40—50° C og forsiktig tilsette oppløsning av N-metyl-N-nitrosotosylamid i eter fra tilvirkningstrakten. Man brukte nitrogen til å drive diazometanet inn i en oppløsning av 20 g 3a-acetoxy-16-pregnen- flask to 40-50° C and carefully add solution of N-methyl-N-nitrosotosylamide in ether from the production funnel. Nitrogen was used to drive the diazomethane into a solution of 20 g of 3a-acetoxy-16-pregnene-
11,20-dion i 100 ml tetrahydrofuran og 120 11,20-dione in 100 ml of tetrahydrofuran and 120
ml eter. Man lot prosessen fortsette inntil oppløsningen forble gul i flere timer. Pro- ml of ether. The process was allowed to continue until the solution remained yellow for several hours. Pro-
duktet, 3a-acetoxy-16ct, 17a-metylen-azo-pregnan-ll,20-dion, ble da utfelt fra reak-sjonsblandingen i rikelige mengder. Ef ter 16 timers henstand ble blandingen filtrert, the product, 3α-acetoxy-16ct,17α-methylene-azo-pregnan-11,20-dione, was then precipitated from the reaction mixture in copious amounts. After 16 hours of standing, the mixture was filtered,
produktet vasket med eter og tørret i luf- the product washed with ether and dried in air
ten. Dets smeltepunkt er 186—190° C (spaltning). ten. Its melting point is 186-190° C (decomposition).
37,4 g 3a-acetoxy-16a, 17a-metylen-azo-pregnan-ll,20-dion blev anbragt i en 500 ml rundkolbe og oppvarmet på olje- 37.4 g of 3α-acetoxy-16α, 17α-methylene-azo-pregnane-11,20-dione was placed in a 500 ml round-bottomed flask and heated on oil
bad 1 vakuum (trykk 0,6 mmHg). Der ble anbragt et manometer og en 12 liters kolbe i ledningen mellom rundkolben og opp-fangningsbeholderen foran vakuumpum- bath 1 vacuum (pressure 0.6 mmHg). A pressure gauge and a 12 liter flask were placed in the line between the round flask and the collection container in front of the vacuum pump.
pen. Da oljebadets temperatur nådde 180° pretty. When the oil bath temperature reached 180°
C begynte 3a-acetoxy-16a, 17a-metylen-azo-pregnan-ll,20-dionet å smelte under utvik- C, the 3a-acetoxy-16a, 17a-methylene-azo-pregnan-11,20-dione began to melt during develop-
ling av nitrogen. Det maksimale trykk som ble nådd var 83 mm. Efter 10 minutters henstand ved 180—182° C ble smeiten av- ling of nitrogen. The maximum pressure reached was 83 mm. After a 10-minute rest at 180-182° C, the smelting was
CH OH CH OH
kjølet. Den hadde en lmg^ s = 249, E%, cooled. It had a lmg^ s = 249, E%,
191. Smeiten ble tatt opp i omkring 150 ml aceton og oppløsningen filtrert gjennom diatoméjord. Den ble derpå inndampet til et volum på omkring 100 ml og eter ble langsomt tilsatt til den kokende oppløsning inntil krystallisasjon inntraff. De erholdte krystaller besto av 3a-acetoxy-16-metyl-16-pregnen-ll,20-dion med smeltepunkt 191. The melt was taken up in about 150 ml of acetone and the solution filtered through diatomaceous earth. It was then evaporated to a volume of about 100 ml and ether was slowly added to the boiling solution until crystallization occurred. The crystals obtained consisted of 3α-acetoxy-16-methyl-16-pregnene-11,20-dione with m.p.
OTT OTT OTT OTT
166—167° C. I maks 249. Em 9300. 166—167° C. I max 249. Em 9300.
På lignende måte fikk man ved å bruke In a similar way one obtained by using
diazo-etan, 3a,-acetoxy-16-etyl-16-pregnen 11,20-dion og diazopropan, 3a-acetoxy-16-propyl-16-pregnen-ll,20-dion. diazo-ethane, 3α,-acetoxy-16-ethyl-16-pregnene 11,20-dione and diazopropane, 3α-acetoxy-16-propyl-16-pregnene-11,20-dione.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US375670A | 1970-01-19 | 1970-01-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO131119B true NO131119B (en) | 1974-12-30 |
NO131119C NO131119C (en) | 1975-04-09 |
Family
ID=21707431
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO4578/70A NO131119C (en) | 1970-01-19 | 1970-11-30 |
Country Status (6)
Country | Link |
---|---|
US (1) | US3628487A (en) |
JP (1) | JPS4920435B1 (en) |
FR (1) | FR2075649A5 (en) |
GB (1) | GB1327487A (en) |
NO (1) | NO131119C (en) |
SE (3) | SE371405B (en) |
Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
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US3742893A (en) * | 1972-04-14 | 1973-07-03 | W Stelling | Water-jet propulsion and steering system for a multi-section prime-mover ship |
DE2407989C2 (en) * | 1974-02-20 | 1982-08-12 | Festo-Maschinenfabrik Gottlieb Stoll, 7300 Esslingen | Working cylinder for pneumatic or hydraulic pressure media |
US4410193A (en) * | 1979-11-14 | 1983-10-18 | Howard D U | Remotely adjustable compensator for centering steering systems |
US4534577A (en) * | 1979-11-14 | 1985-08-13 | Howard D U | Remotely adjustable steering compensator |
US4418931A (en) * | 1979-11-14 | 1983-12-06 | Howard D U | Remotely adjustable steering compensator |
US4644893A (en) * | 1984-08-06 | 1987-02-24 | International Hydraulic Systems, Inc. | Position indicating apparatus for use in a boat leveling system |
US4742794A (en) * | 1986-09-08 | 1988-05-10 | Bennett Marine, Inc. | Trim tab indicator system |
US4854259A (en) * | 1988-10-14 | 1989-08-08 | Sta-Rite Industries, Inc. | Improved trim-tab control system for power boats |
US5117741A (en) * | 1990-01-16 | 1992-06-02 | Sta-Rite Industries, Inc. | Double wall hydraulic cylinder |
JPH0462297U (en) * | 1990-10-09 | 1992-05-28 | ||
US5474013A (en) * | 1993-03-05 | 1995-12-12 | Trim Master Marine, Inc. | Trim tab auto-retract and multiple switching device |
US6460212B2 (en) | 1993-10-04 | 2002-10-08 | Kelley Company, Inc. | Dock leveler having an inflatable member |
US6711774B2 (en) | 1993-10-04 | 2004-03-30 | Kelley Company, Inc. | Dock leveler having an inflatable member |
US5450643A (en) * | 1993-10-04 | 1995-09-19 | Kelley Company Inc. | Edge-of-dock leveler |
GB2300893B (en) * | 1995-05-19 | 1999-06-09 | Monroe Auto Equipment Co | Method and apparatus for delivering fluid and/or electric signals |
US5881666A (en) * | 1997-06-13 | 1999-03-16 | Crews, Jr.; L. Jeremy | Watertight trim tab actuator |
US6532889B1 (en) * | 2000-07-14 | 2003-03-18 | Tracker Marine, L.L.P. | Aluminum fishing boat |
US20040221404A1 (en) * | 2003-04-28 | 2004-11-11 | Brian Bender | Double-wall inflatable column assembly for a dock leveler |
US7503089B2 (en) | 2005-04-05 | 2009-03-17 | Rite-Hite Holding Corporation | Inflatable actuator for a dock leveler deck |
EP1915289A1 (en) * | 2005-08-08 | 2008-04-30 | MULLER, Peter A. | Watercraft steering mechanism and trimmer |
US8216007B2 (en) * | 2006-02-27 | 2012-07-10 | Steven Clay Moore | Methods and arrangements for rapid trim adjustment |
ITVI20060143A1 (en) * | 2006-05-11 | 2007-11-12 | Besenzoni Spa | LINEAR HYDRAULIC ACTUATOR |
WO2008106807A1 (en) | 2007-03-05 | 2008-09-12 | Mueller Peter A | Double trim hatch |
US7905193B2 (en) | 2007-12-28 | 2011-03-15 | Johnson Outdoors Inc. | Trim tabs |
GR20090100402A (en) * | 2009-07-20 | 2011-02-18 | Ν. Τριανταφυλλης & Σια Ο.Ε., | Self-bearing ecological system for the dynamic correcting swing of the floating position of a floating means by change of the whole hydrodynamic flow of the hull |
CH704369A2 (en) | 2011-01-18 | 2012-07-31 | Peter A Mueller | Stages trim tab. |
US9260161B2 (en) | 2011-11-12 | 2016-02-16 | Malibu Boats, Llc | Surf wake system for a watercraft |
US9580147B2 (en) | 2011-09-16 | 2017-02-28 | Malibu Boats, Llc | Surf wake system for a watercraft |
US9802684B2 (en) | 2013-10-11 | 2017-10-31 | Mastercraft Boat Company, Llc | Wake-modifying device for a boat |
US8833286B1 (en) | 2013-10-11 | 2014-09-16 | Mastercraft Boat Company, Llc | Wake-modifying device for a boat |
US10358189B2 (en) | 2013-10-11 | 2019-07-23 | Mastercraft Boat Company, Llc | Wake-modifying device for a boat |
US9669903B2 (en) | 2014-02-04 | 2017-06-06 | Malibu Boats, Llc | Methods and apparatus for facilitating watercraft planing |
US9891620B2 (en) | 2015-07-15 | 2018-02-13 | Malibu Boats, Llc | Control systems for water-sports watercraft |
US10035571B1 (en) * | 2016-01-15 | 2018-07-31 | Joseph R. Langlois | System for attitude control and stabilization of a marine craft |
US10994807B2 (en) * | 2016-01-15 | 2021-05-04 | Joseph R. Langlois | Transom mounted bracket for a fluid hinge trim tab system |
US10676166B1 (en) | 2017-04-04 | 2020-06-09 | Skier's Choice, Inc. | Surf wake forming systems and methods with gyroscope force vector translation |
US10040522B1 (en) | 2017-04-04 | 2018-08-07 | Skier's Choice, Inc. | Surf wake forming system with dual actuated trim tab |
US11370508B1 (en) | 2019-04-05 | 2022-06-28 | Malibu Boats, Llc | Control system for water sports boat with foil displacement system |
US11932356B1 (en) | 2020-08-24 | 2024-03-19 | Malibu Boats, Llc | Powered swim platform |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2790426A (en) * | 1952-06-11 | 1957-04-30 | Mueller Otto | Fluid device having joints in swiveled fluid conducting relationship |
US3177837A (en) * | 1961-11-08 | 1965-04-13 | Sea Trim Corp | Boat stabilizing unit |
US3431031A (en) * | 1965-01-28 | 1969-03-04 | Wiz Corp | Vehicle brake operator |
US3479063A (en) * | 1968-12-24 | 1969-11-18 | Flexfloat Eng Co | Fluid pressure tightened joint |
-
1970
- 1970-01-19 US US3756A patent/US3628487A/en not_active Expired - Lifetime
- 1970-11-27 GB GB5642970A patent/GB1327487A/en not_active Expired
- 1970-11-30 NO NO4578/70A patent/NO131119C/no unknown
- 1970-12-14 JP JP45111660A patent/JPS4920435B1/ja active Pending
- 1970-12-28 SE SE7017570A patent/SE371405B/xx unknown
- 1970-12-28 SE SE7316532A patent/SE383306B/en unknown
-
1971
- 1971-01-18 FR FR7101478A patent/FR2075649A5/fr not_active Expired
-
1973
- 1973-12-06 SE SE7316532A patent/SE7316532L/ unknown
Also Published As
Publication number | Publication date |
---|---|
SE371405B (en) | 1974-11-18 |
SE383306B (en) | 1976-03-08 |
SE7316532L (en) | 1973-12-06 |
JPS4920435B1 (en) | 1974-05-24 |
NO131119C (en) | 1975-04-09 |
FR2075649A5 (en) | 1971-10-08 |
US3628487A (en) | 1971-12-21 |
GB1327487A (en) | 1973-08-22 |
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