SI9400003A - Process for the preparation of biphenyl derivatives - Google Patents
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- SI9400003A SI9400003A SI9400003A SI9400003A SI9400003A SI 9400003 A SI9400003 A SI 9400003A SI 9400003 A SI9400003 A SI 9400003A SI 9400003 A SI9400003 A SI 9400003A SI 9400003 A SI9400003 A SI 9400003A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/51—Y being a hydrogen or a carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/52—Y being a hetero atom
- C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
- C07C311/57—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
- C07C311/58—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to hydrogen atoms or to acyclic carbon atoms
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
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Description
kjer X predstavlja v danem primeru zaščiteno formilno skupino in pomeni R grupacijo, ki je sama inertna za reakcijske pogoje sinteze, npr. -CN, označen s tem, da spojino s splošno formulo:
pri čemer je X definiran kot zgoraj, presnovimo s substituirano fenilhalogensko spojino s formulo:
Ha I
pri čemer Hal pomeni npr. brom. Spojine so dragoceni vmesni produkti za sintezo zdravil.
HOECHST AKTIENGESELLSCHAFT
Postopek za pripravo bifenilnih derivatov
Izum se nanaša na posebne bifenilne derivate in na postopek za njihovo pripravo.
Pri pripravi učinkovitih snovi, kot npr. zdravil za obolenja srčnega obtoka, so se izkazali bifenilni derivati kot važni vmesni produkti pri postopku priprave. V EP-A 503 162 je npr. opisana priprava sestavkov za znižanje krvnega tlaka, ki vsebujejo kot učinkovito snov spojine tipa angiotenzin Π-receptorskega antagonista, ki imajo posebno substituiran bifenilni sistem.
Opisali so že različne postopke za pripravo substituiranih bifenilnih derivatov, npr. derivati fenilboronske kisline se dajo pripajati z aril halogenidi ob uporabi katalizatorjev prehodnih kovin, npr. paladija. Ustrezne reakcije so opisali R.B. Miller et al. v Organometallics 1984, 3,1261, ali A. Zuzuki et al. v Synthetic Commun. 11(7), 513 (1981).
Izum se nanaša na postopek za pripravo bifenilnih derivatov s splošno formulo (I)
X
R (D kjer je
X v danem primeru zaščitena formilna skupina, zlasti pa pomeni -CHO ali -CH(OR’)OR2,
R1, R2 sta neodvisno drug od drugega (Cx-C6) alkil ali pomenita R1 in R2 skupaj alkilensko skupino -(CH2)n, pri čemer n pomeni 2, 3, 4 ali 5, in J'e
R grupacija, kije sama inertna za reakcijske pogoje sinteze.
Pri postopku v smislu izuma pripravimo iz znanih, v danem primeru zaščitenih formilbenzen halogenidov, npr. bromidov ali jodidov, preko Grignardove reakcije derivate boronske kisline s formulo (II) (glej npr. H. Feulner et al.; Chemische Berichte 123 (1990) 1841 do 1843), pri čemer
X
stoji skupina X v formuli (II) za grupacijo CHO ali za ustrezno zaščiteno formilno skupino, npr. acetal. Spojine s splošno formulo (II) nato s pripajanjem s substituiranimi fenil halogenskimi spojinami s formulo (III), ki jih lahko dobimo po znanih metodah, presnovimo v bifenilne spojine s formulo (I)
Ho I
A pri čemer pridejo v poštev kot halogenska grupacija (Hal) za spojine s splošno formulo (III) prednostno bromidi in jodidi, zlasti prednostno bromidi, in je R definiran kot zgoraj.
Namesto derivatov boronske kisline s formulo (II) lahko za postopek v smislu izuma uporabimo tudi ustrezne estre boronske kisline, ki jih lahko npr. sintetiziramo iz ustreznih derivatov brommetilbenzenboronske kisline.
Spajanje obeh fenilnih derivatov s formulama (II) in (III) v ustrezno bifenilno spojino lahko izvedemo ob uporabi katalizatoija, prednostno paladijevega katalizatorja. Reakcijske pogoje lahko variiramo glede na reaktivnost izhodnih snovi, prednostno uporabimo temperaturno območje od okoli 20°C do 150°C in tlak 1 bar do 5 barov. Kot topila pridejo v poštev npr. zmesi iz benzena ali toluena z alkoholi, zlasti etanolom.
Kot substituent R v spojinah s splošno formulo (I) pridejo v poštev vse grupacije, ki se same ne spremenijo ob reakcijskih pogojih, uporabljenih za spajanje obeh fenilnih obročev. Kot substituent R so zlasti primerne naslednje skupine:
R = -F, -Cl, -NO2, -(CH2)m-COOR3,
-(CH^-CONHR3, -(C^-CN, -so2nh-coor3, -so2nh-co-nhr3, -so2nh-so2-r3, -nhso2r3
N—N
-so2nr4, pri čemer je R3 vodik, (Cj-C^alkil, (C3-C6)cikloalkil ali (Cj-C^alkil^Cj-C^dldoalkil, pomeni R4 skupino =C-N(CH3)2 in je m 0,1,2,3 ali 4.
Namesto spajanja obeh fenilnih sistemov preko derivata boronske kisline lahko izvedemo pripravo bifenilnih derivatov s formulo (I) tudi ob uporabi cink-halogenfenilnih derivatov, kositer-metilfenilnih derivatov ali Grignardovih spojin.
Priprava zaščitene formilne grupacije in priprava Grignardovih reagentov poteče po znanih metodah.
Izum se nanaša tudi na spojine s splošno formulo (I) kot take, pri čemer so prednostne spojine, v katerih R pomeni SO2NHCOOR3, SO2NHCONHR3, SO2NHSO2R3 ali SO2NR4, pri čemer sta SO2NHCONHR3in SO2NR4 posebno prednostna, kot tudi na spojine s splošno formulo (III) kot take, pri čemer so prednostne spojine, v katerih R pomeni SO2NHCOOR3, SO2NHCO-NHR3 ali SO2NH-SO2R3, pri čemer je SO2NHCONHR3 posebno prednosten.
Izum podrobneje pojasnjujemo z naslednjimi primeri.
Primer 1
Postopek za pripravo 4-formil-2’-N,N-dimetilaminoformilbifenilsolfonamida
CHO
la) 4-brombenzaldehid-dietilacetal
K 2,7 g amonijevega nitrata v 65 ml (1,1 mol) brezvodnega etanola dodamo 100 g (0,54 molov) staljenega 4-brombenzaldehida in 90 ml (0,54 molov) trietilestra ortomravljinčne kisline. Po 18 urah pri sobni temperaturi odfiltriramo in naalkalimo s piperidinom (~ pH 10). Naslovno spojino dobimo z destilacijo v vakuumu.
Dobitek: 90%
Vrel.: (pri 0,067 mbarih) = 110 do 115°C.
lb) 4-formilbenzenboronska kislina
V atmosferi argona nadslojimo 3,65 g magnezijevih opilkov s 15 ml brezvodnega THF in dodamo 0,5 ml 1,2-dibrometana. Rahlo segrevanje vodi do burne reakcije. Po prenehanju odpipetiramo topilo s pipeto, dodamo 40 ml brezvodnega THF in dodamo 1/3 raztopine 32 g produkta 1 a) v 30 ml brezvodnega THF. Reakcijo začnemo z Red-Al in segrevanjem. Ostanek produkta iz 1 a) sedaj dokapavamo 35 minut. Po končanem dokapavanju kuhamo še 1 uro pod refluksom.
Grignardov produkt dokapavamo sedaj k raztopini 33,5 ml tributilborata v atmosferi argona v 50 ml THF, ohlajeni na -68°C. Po 30 minutah odstranimo hlajenje. Nastavek mešamo sedaj 1 uro pri sobni temperaturi. Sedaj uparimo, olje barve medu prevzamemo v 100 ml etra in dodamo 80 ml ledeno mrzle H2SO4 (IM). Etrsko fazo odločimo in še dvakrat ekstrahiramo s 50 ml etra, uparimo in dodajamo 30%-ni (6N) KOH, dokler ne nastopi alkalna reakcija (pH 14). Dodamo 70 ml H2O in v visokem vakuumu azeotropsko odvzamemo butanol pri 35 do 40°C. Ta postopek še enkrat ponovimo s 50 ml H2O. Ostanek nakisamo z 1 M H2SO4 (pH 1) in kuhamo 30 minut. S filtriranjem dobimo naslovno spojino kot svetlo rumeno trdno snov.
Tal.: 255 do 260°C.
Ic) 4-formil-2’-N,N-dimetilaminoformilbifenilsulfonamid
K 7 g (0,024 molom) 2-brom-N,N-dimetilaminijoformilbenzensulfonamida in 0,7 g trifenilfosfina (0,1 ekvivalent) v 100 ml toluena dodamo 5,7 g natrijevega karbonata (2 ekvivalenta) v 30 ml tople vode. Dobro splaknemo z argonom in pri 60°C dodamo 0,3 g paladijevega acetata (0,05 ekvivalentov) v protitoku argona. Po 10 minutah k medtem črno rjavi reakcijski raztopini stresemo 4 g spojine iz 1 b (1,1 ekvivalent) v 70 ml etanola v protitoku argona. Nato nastavek segrejemo na temperaturo vrelišča in kuhamo 3,5 ure pri refluksu. Po ohlajenju topilo odstranimo v vakuumu. Ostanek prevzamemo v 150 ml etilacetata in 5 x izperemo z nasičeno raztopino natrijevega karbonata. Organsko fazo posušimo z magnezijevim sulfatom in filtriramo preko sloja kizelgura. Po odstranitvi topila v vakuumu dobimo 8 g naslovne spojine kot rjavo, delno kristalno surovo snov. To lahko čistimo s kuhanjem v okoli 30 ml etilacetata.
Dobitek: 83%
Rf = 0,4 (E/H 2/1); MS (M + 1) = 317; tal.: 161°C
Analogno iz ustreznih eduktov pripravimo spojine primerov 2 do 6. Te so navedene v tabeli 1 s strukturo in fizikalnimi podatki.
Tabela 1
CHO
R
Primer št. | R | MS (M + 1) |
2 | -CO2C2H5 | 255 |
3 | -CN | 208 |
4 | ^0' ^^N-tritil | 493 |
5 | -SO2NHCONHC3H7 | 347 |
6 | -nhso2cf3 | 330 |
Primera 7 in 8 opisujeta pripravo vmesnih produktov s splošno formulo III.
Primer 7
Priprava 2-brombenzen-n-propilsulfonilsečnine
3,5 g (15 mmolov) 2-brombenzensulfonamida in 4,1 g K2CO3 kuhamo v 40 ml dimetoksipropana 1 uro pri refluksu. Sedaj dobrizgamo 3 ml n-propilizocianata in po nadaljnjih 12 urah pustimo ohladiti na 0°C, naravnamo pH na 5-6 s 5%-no raztopino NaHSO4 in 2 x ekstrahiramo z etil acetatom. Združene organske faze uparimo po sušenju z MgSO4. S prekristalizacijo iz etilacetata dobimo naslovno spojino.
Rf = 0,5 (E/H 2/1); MS (M + 1) = 321
Primer 8
Postopek za pripravo 2-jodbenzen-n-propilsulfonilsečnine
8a) 2-jodbenzensulfonamid
3,5 g 2-aminobenzensulfonamida v 25 ml konc. H2SO4 (98%) segrevamo na 60°C, dokler ne dobimo bistre raztopine, in nato ohladimo z dodatkom 20 g ledu na 0°C. Previdno po kapljicah dodajamo 1,45 g NaNO2 (raztopljenega v 4 ml vode), tako da temperatura ne preseže 5 do 6°C. Zatem reakcijsko zmes 3 ure mešamo pri 5 do 6°C. Po dodatku 3,75 g kalijevega jodida (raztopljenega v 25 ml vode) po kapljicah mešamo nastalo rdečo zmes ponovno 18 ur. Po dodatku 50 ml vode odfiltriramo nastopajočo oborino in večkrat izperemo z vodo. Dobljeno trdno snov raztopimo v etil acetatu, izperemo 1 x z 0,2 N raztopino natrijevega tiosulfata in 2 x z vodo in topilo odstranimo. Kot dobitek dobimo 4 g rahlo rumenkaste snovi (dobitek 62%). Tal.: 197-198°; IR (nujol): 3360,3255,1562 cm1; MS (Μ+): 283
8b) 2-jodbenzen-n-propilsulfonilsečnina
3,92 g trdnega K^CC^ naenkrat dodamo k mešani raztopini 2-jodbenzensulfonamida (4 g v 40 ml acetona) in kuhamo pri refluksu v atmosferi dušika, n-propilizocianat dokapamo k segretemu reakcijskemu nastavku, ki ga nato kuhamo 2 uri pri refluksu, ohladimo na sobno temperaturo in uparimo do suhega. Po dodatku 200 ml vode naravnamo ohlajeni reakcijski nastavek z 2N HCI na pH 4 in filtriramo. Oborino prekristaliziramo iz acetona/izopropiletra. Dobitek naslovne spojine znaša 4,lg.
Tal.: 211-212°C, IR (nujol); 3406,3368,1715,1565,1539 cm1; MS (M+): 368 xH-NMR-podatki naslovnih spojin primerov 1,2,3,5,8a in 8b so zbrani v tabeli 2.
Tabela 2:
1: (DMSO-d6) d = 2,68 (s, 3 H); d = 2,72 (s, 3 H), d = 7,2 (s, 1 H); d = 7,25 do
7,35 (m, 1 H); d = 7,45 do 7,75 (m, 4 H); d = 7,95 (d, J = 8 Hz, 1 H); d = 8,05 do 8,15 (m, 2 H); d = 10,1 (s, 1 H).
2: (CDC13) d = 1,0 (t, J = 7 Hz, 3 H); d = 4,1 (q, J = 7 Hz, 2 H); d = 7,3 do 7,6 (m, 5 H); d = 7,85 do 8,0 (m, 3 H); d = 10,1 (s, 1 H).
3: (CDC13) d = 7,2 do 7,8 (m, 6 H); 7,95 do 8,05 (m, 2 H); d = 10,1 (s, 1 H).
5. (DMSO-d6) d = 1,0 (t, J = 7 Hz, 3 H); d = 1,3 (dq, J = 7 Hz, 2 H); d = 2,85 (dd, J = 7 Hz, J = 9,5 Hz, 2 H); d = 6,1 (t, J = 7 Hz, 1 H); d = 7,1 do 7,4 (m, 1 H); d = 7,4 do 7,8 (m, 4 H); d = 7,9 do 8,1 (m, 3 H); d = 9,9 (s, 1 H); d = 10,1 (s, 1 H).
8a. (CDCy5,17 (s, I, NH^; 7,23 do 7,52 (td aromati 2H); 8,08 do 8,20 (dd, aromati 2H)
8b: (CDC13) 0,82 (t, J = 7,5 CH^ 3H); 1,45 (m, CH2, 2H; 3,14 (m, CH2, 2H); 6,39 (t, CONH, IH); 7,29 (dt, J = 1,5 aromati); 7,54 (td, J = 8,15 aromati); 8,13 (m, aromati) 7,59 (s, SO2NH, IH).
Okrajšave: E H
Red-Al
THF tritil etilacetat n-heptan natrijev dihidrido-bis-(2-metoksi-etoksi)-aluminat tetrahidrofuran trifenilmetil
Za
HOECHST AKTIENGESELLSCHAFT:
PATENTNI ZAHTEVKI
Claims (9)
1. Postopek za pripravo spojine s splošno formulo (I)
X kjer predstavlja
X v danem primeru zaščiteno formilno skupino in
R pomeni grupacijo, ki je sama inertna za reakcijske pogoje sinteze, označen s tem, da spojino s splošno formulo (II)
X kjer je X definiran kot zgoraj, presnovimo s substituirano fenilhalogensko spojino s formulo (III)
Ηα I
O (lil) pri čemer stoji substituent Hal za halogensko grupacijo in je R definiran kot zgoraj.
2. Postopek po zahtevku 1, označen s tem, da imajo v formuli (I) substituenti naslednje pomene:
X je -CHO ali -CHtOR^OR2,
R1, R2 sta neodvisno drug od drugega (Cj-CJalkil ali pomenita R1 in R2 skupaj alkilensko skupino -(CH2)n, pri čemer n pomeni 2,3,4 ali 5 in je
R -F, -Cl, -NO2, -(CH2)m-COOR3,
-(CH2)m-CONHR3, -(CH^-CN,
-so2nh-coor3, -so2nh-co-nhr3,
-so2nh-so2-r3, -nhso2r3
N-N
O - tri til - P 0 3 R 3 , -NH-S02-CF3 ali
-so2nr4, pri čemer pomeni R3 vodik, (C^C^alkil, (C3-C6)cikloalkil ali (C1-C6)alkil-(C3-C6)cikloalkil, pomeni R4 skupino =C-N(CH3)2 in je m enak 0,1,2, 3 ali 4.
3. Postopek po zahtevku 1, označen s tem, da pripajanje spojine s splošno formulo (II) s spojino s splošno formulo (III) poteče z uporabo katalizatorja prehodne kovine paladija.
4. Spojina s splošno formulo (I)
X
R (I) kjer imajo substituenti naslednje pomene:
il
X pomeni -CHO ali -CH(OR‘)OR2, pri čemer
R1, R2 pomenita neodvisno drug od drugega (C^C^alkil ali R1 in R2 skupaj alkilensko skupino -(CH2)n, pri čemer n pomeni 2,3,4 ali 5, in je
R -F, -Cl, -NO2, -(CH2)m-COOR3,
-(CH2)m-CONHR3, -(CH^-CN,
-so2nh-coor3, -so2nh-co-nhr3,
-so2nh-so2-r3, -nhso2r3
N—N (L·) N- tri til -PO,R3, -NH-SO2-CF3 ali
N
-SO2NR4, pri čemer je R3 vodik, (C1-C6)alkil, (C3-C6)cikloalkil ali (C1-C6)alkil-(C3-C6)cikloalkil, pomeni R4 skupino =C-N(CH3)2 in je m enak 0,1,2,3 ali 4.
5. Spojina po zahtevku 4, označena s tem, da v formuli (I)
R pomeni SO2-NR4 ali SO2NHCONHR3, pri čemer pomeni
R3 vodik ali (C^CJalkil in
R4 skupino =C-N(CH3)2.
6. Uporaba spojine, pripravljene po enem od zahtevkov 1 do 4, kot vmesnega produkta za sintezo učinkovitih snovi.
7. Uporaba spojine po enem od zahtevkov 4 ali 5 kot vmesnega produkta za sintezo angiotenzin II-receptorskih antagonistov.
8. Spojina s splošno formulo (III)
Ηα I
O kjer imajo substituenti naslednji pomen:
Hal je brom ali jod (lil)
R je -SO2NH-COOR3, -SO2NH-CO-NHR3, -SO2NH-SO2-R3, pri čemer pomeni R3 vodik, (Cj-C^alkil, (C3-C6)cikloalkil ali -(Cj-C^alkil^Cg-C^cikloalkil.
9. Spojina po zahtevku 8, označena s tem, da je v formuli III R enak -SO2NH-CO-NHR3, pri čemer R3 pomeni (Cj-C^alkil.
23485-xii-93-mn
Za
HOECHST AKTIENGESELLSCHAFT:
Povzetek
Izum se nanaša na postopek za pripravo spojine s splošno formulo (I)
X kjer
X predstavlja v danem primeru zaščiteno formilno skupino in pomeni R grupacijo, ki je sama inertna za reakcijske pogoje sinteze, npr. -CN, označen s tem, da spojino s splošno formulo (II)
X
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DE4300137 | 1993-01-06 |
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US (2) | US5618975A (sl) |
EP (1) | EP0606065B1 (sl) |
JP (1) | JP3586288B2 (sl) |
KR (1) | KR940018349A (sl) |
CN (1) | CN1096511A (sl) |
AT (1) | ATE183732T1 (sl) |
AU (1) | AU677247B2 (sl) |
BR (1) | BR9400018A (sl) |
CA (1) | CA2112795A1 (sl) |
CZ (1) | CZ1494A3 (sl) |
DE (1) | DE59408646D1 (sl) |
DK (1) | DK0606065T3 (sl) |
ES (1) | ES2136669T3 (sl) |
FI (1) | FI940032A (sl) |
GR (1) | GR3031852T3 (sl) |
HR (1) | HRP940001A2 (sl) |
HU (1) | HUT67406A (sl) |
IL (1) | IL108262A0 (sl) |
NO (1) | NO301878B1 (sl) |
NZ (2) | NZ272704A (sl) |
PL (1) | PL301778A1 (sl) |
SI (1) | SI9400003A (sl) |
SK (1) | SK694A3 (sl) |
TW (1) | TW348175B (sl) |
ZA (1) | ZA9418B (sl) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2167384A1 (en) | 1994-05-16 | 1995-11-23 | Hideki Ushio | Process for producing tetrazole compound and intermediate therefor |
FR2737721B1 (fr) | 1995-08-08 | 1997-09-05 | Roussel Uclaf | Nouveaux composes biphenyles, leur procede de preparation et les intermediaires de ce procede, leur application a titre de medicament et les compositions pharmaceutiques les contenant |
ATE209620T1 (de) * | 1996-03-13 | 2001-12-15 | Basf Ag | Verfahren zur herstellung von nitrobiphenylen |
KR19990069877A (ko) * | 1998-02-13 | 1999-09-06 | 성재갑 | 나프토퀴논 구조를 갖는 사이클린-의존 키나아제 저해제 화합물 |
DE102005022362B4 (de) * | 2005-05-10 | 2016-12-15 | Studiengesellschaft Kohle Mbh | Verfahren zur decarboxylierenden C-C Verknüpfung von Carbonsäuren mit Kohlenstoffelektrophilen |
US9957622B2 (en) | 2009-07-23 | 2018-05-01 | Field Upgrading Limited | Device and method of obtaining diols and other chemicals using decarboxylation |
US9206515B2 (en) | 2009-07-23 | 2015-12-08 | Ceramatec, Inc. | Method of producing coupled radical products via desulfoxylation |
US9051656B2 (en) * | 2009-07-23 | 2015-06-09 | Ceramatec, Inc. | Electrochemical synthesis of aryl-alkyl surfacant precursor |
WO2011011521A2 (en) * | 2009-07-23 | 2011-01-27 | Ceramatec, Inc. | Decarboxylation cell for production of coupled radical products |
US8506789B2 (en) * | 2009-07-23 | 2013-08-13 | Ceramatec, Inc. | Method of producing coupled radical products |
US9493882B2 (en) | 2010-07-21 | 2016-11-15 | Ceramatec, Inc. | Custom ionic liquid electrolytes for electrolytic decarboxylation |
WO2012018418A2 (en) | 2010-08-05 | 2012-02-09 | Ceramatec, Inc. | Method and device for carboxylic acid production |
WO2012103135A2 (en) | 2011-01-25 | 2012-08-02 | Ceramatec, Inc. | Production of fuel from chemicals derived from biomass |
US8853463B2 (en) | 2011-01-25 | 2014-10-07 | Ceramatec, Inc. | Decarboxylation of levulinic acid to ketone solvents |
JP7023080B2 (ja) | 2016-10-31 | 2022-02-21 | 東ソー株式会社 | 芳香族化合物の製造方法 |
US20210261501A1 (en) * | 2018-09-25 | 2021-08-26 | Lonza Solutions Ag | Method for Preparation of Potassium 5-Iodo-2-Carboxybenzene Sulfonate |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3624142A (en) * | 1964-09-10 | 1971-11-30 | Merck & Co Inc | Substituted biphenyl acetic acid derivatives |
ATA937274A (de) * | 1973-12-17 | 1978-02-15 | Thomae Gmbh Dr K | Verfahren zur herstellung neuer araliphatischer ketone |
DE2362589A1 (de) * | 1973-12-17 | 1975-07-10 | Thomae Gmbh Dr K | Neue araliphatische ketone und carbinole und verfahren zu ihrer herstellung |
US5068424A (en) * | 1988-06-17 | 1991-11-26 | Nitrokemia Ipartelepek | Process for preparing arylsulphonyl-isocyanates and addition derivatives thereof |
EP0424317A3 (en) * | 1989-10-19 | 1991-09-25 | Ciba-Geigy Ag | Pyrimidines |
FR2659655B1 (fr) * | 1990-03-19 | 1992-07-24 | Union Pharma Scient Appl | Nouveaux derives d'oxypyrazole antagonistes des recepteurs a l'angiotensine ii ; leurs procedes de preparation, compositions pharmaceutiques les contenant. |
CA2058198A1 (en) * | 1991-01-04 | 1992-07-05 | Adalbert Wagner | Azole derivatives, process for their preparation, and their use |
IE920175A1 (en) * | 1991-02-11 | 1992-08-12 | Zeneca Ltd | Nitrogen heterocycles |
US5162340A (en) * | 1991-05-10 | 1992-11-10 | Merck & Co., Inc. | Substituted 1-(2h)-isoquinolinones bearing acidic functional groups as angiotensin ii antagonists |
TW300219B (sl) * | 1991-09-14 | 1997-03-11 | Hoechst Ag | |
US5130439A (en) * | 1991-11-18 | 1992-07-14 | Lo Young S | Tetrazolylphenylboronic acid intermediates for the synthesis of AII receptor antagonists |
EP0550313A1 (fr) * | 1991-12-30 | 1993-07-07 | Synthelabo | Nouveaux dérivés de 2-(tétrazol-5-yl)-(1,1'-biphényle), leur préparation et leur utilisation comme intermédiaires de synthèse |
-
1993
- 1993-06-08 TW TW082104523A patent/TW348175B/zh active
- 1993-12-23 NZ NZ272704A patent/NZ272704A/en unknown
- 1993-12-23 NZ NZ250577A patent/NZ250577A/en unknown
- 1993-12-28 JP JP33392993A patent/JP3586288B2/ja not_active Expired - Fee Related
-
1994
- 1994-01-03 HR HR940001A patent/HRP940001A2/xx not_active Application Discontinuation
- 1994-01-04 IL IL10826294A patent/IL108262A0/xx unknown
- 1994-01-04 AU AU53029/94A patent/AU677247B2/en not_active Ceased
- 1994-01-04 SI SI9400003A patent/SI9400003A/sl unknown
- 1994-01-04 HU HU9400018A patent/HUT67406A/hu unknown
- 1994-01-04 SK SK6-94A patent/SK694A3/sk unknown
- 1994-01-04 ZA ZA9418A patent/ZA9418B/xx unknown
- 1994-01-04 DE DE59408646T patent/DE59408646D1/de not_active Expired - Lifetime
- 1994-01-04 CA CA002112795A patent/CA2112795A1/en not_active Abandoned
- 1994-01-04 KR KR1019940000065A patent/KR940018349A/ko not_active Application Discontinuation
- 1994-01-04 PL PL94301778A patent/PL301778A1/xx unknown
- 1994-01-04 DK DK94100048T patent/DK0606065T3/da active
- 1994-01-04 ES ES94100048T patent/ES2136669T3/es not_active Expired - Lifetime
- 1994-01-04 NO NO940023A patent/NO301878B1/no unknown
- 1994-01-04 AT AT94100048T patent/ATE183732T1/de active
- 1994-01-04 CN CN94100164A patent/CN1096511A/zh active Pending
- 1994-01-04 EP EP94100048A patent/EP0606065B1/de not_active Expired - Lifetime
- 1994-01-04 CZ CZ9414A patent/CZ1494A3/cs unknown
- 1994-01-04 FI FI940032A patent/FI940032A/fi unknown
- 1994-01-04 BR BR9400018A patent/BR9400018A/pt not_active Application Discontinuation
-
1995
- 1995-05-24 US US08/449,396 patent/US5618975A/en not_active Expired - Lifetime
- 1995-05-24 US US08/449,389 patent/US5633400A/en not_active Expired - Lifetime
-
1999
- 1999-11-17 GR GR990402946T patent/GR3031852T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
NZ272704A (en) | 1997-02-24 |
IL108262A0 (en) | 1994-04-12 |
KR940018349A (ko) | 1994-08-16 |
EP0606065B1 (de) | 1999-08-25 |
CZ1494A3 (en) | 1994-08-17 |
CN1096511A (zh) | 1994-12-21 |
HRP940001A2 (en) | 1996-06-30 |
GR3031852T3 (en) | 2000-02-29 |
ES2136669T3 (es) | 1999-12-01 |
ATE183732T1 (de) | 1999-09-15 |
US5618975A (en) | 1997-04-08 |
TW348175B (en) | 1998-12-21 |
AU677247B2 (en) | 1997-04-17 |
US5633400A (en) | 1997-05-27 |
NO940023L (sl) | 1994-07-07 |
JP3586288B2 (ja) | 2004-11-10 |
AU5302994A (en) | 1994-07-14 |
NO940023D0 (no) | 1994-01-04 |
JPH06234690A (ja) | 1994-08-23 |
CA2112795A1 (en) | 1994-07-07 |
EP0606065A1 (de) | 1994-07-13 |
HU9400018D0 (en) | 1994-05-30 |
BR9400018A (pt) | 1994-07-26 |
FI940032A (fi) | 1994-07-07 |
HUT67406A (en) | 1995-04-28 |
SK694A3 (en) | 1994-08-10 |
NO301878B1 (no) | 1997-12-22 |
DE59408646D1 (de) | 1999-09-30 |
DK0606065T3 (da) | 2000-03-13 |
ZA9418B (en) | 1994-08-18 |
PL301778A1 (en) | 1994-07-11 |
FI940032A0 (fi) | 1994-01-04 |
NZ250577A (en) | 1997-02-24 |
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