DK145181B - Fremgangsmaade til fremstilling af n-tritylimidazoler eller deres salte - Google Patents
Fremgangsmaade til fremstilling af n-tritylimidazoler eller deres salte Download PDFInfo
- Publication number
- DK145181B DK145181B DK365771A DK365771A DK145181B DK 145181 B DK145181 B DK 145181B DK 365771 A DK365771 A DK 365771A DK 365771 A DK365771 A DK 365771A DK 145181 B DK145181 B DK 145181B
- Authority
- DK
- Denmark
- Prior art keywords
- imidazole
- methyl
- salts
- diphenyl
- tritylimidazoles
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 12
- 150000003839 salts Chemical class 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims description 4
- NPZDCTUDQYGYQD-UHFFFAOYSA-N 1-tritylimidazole Chemical class C1=NC=CN1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 NPZDCTUDQYGYQD-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- KXGOCPRLOMWVLP-UHFFFAOYSA-N 2,2,2-triphenylethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(CO)C1=CC=CC=C1 KXGOCPRLOMWVLP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 21
- -1 trityl halides Chemical class 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OQUZXBQWAJQVDT-UHFFFAOYSA-N 1-[(4-nitrophenyl)-diphenylmethyl]imidazole Chemical compound [O-][N+](=O)C1=CC=C(C=C1)C(N1C=CN=C1)(C1=CC=CC=C1)C1=CC=CC=C1 OQUZXBQWAJQVDT-UHFFFAOYSA-N 0.000 description 2
- AGUNPFIFLDXKPR-UHFFFAOYSA-N 2-trityl-1h-imidazole Chemical class C1=CNC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 AGUNPFIFLDXKPR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- PUPAEISFEMUGGB-UHFFFAOYSA-N 1-[(2-chlorophenyl)-diphenylmethyl]imidazole;hydrochloride Chemical compound Cl.ClC1=CC=CC=C1C(N1C=NC=C1)(C=1C=CC=CC=1)C1=CC=CC=C1 PUPAEISFEMUGGB-UHFFFAOYSA-N 0.000 description 1
- QKSNTYOXRXJCIO-UHFFFAOYSA-N 1-[(2-fluorophenyl)-diphenylmethyl]imidazole Chemical compound FC1=CC=CC=C1C(N1C=NC=C1)(C=1C=CC=CC=1)C1=CC=CC=C1 QKSNTYOXRXJCIO-UHFFFAOYSA-N 0.000 description 1
- NKQHFGWIQCTOMC-UHFFFAOYSA-N 1-[(2-methoxyphenyl)-diphenylmethyl]imidazole Chemical compound COC1=CC=CC=C1C(N1C=NC=C1)(C=1C=CC=CC=1)C1=CC=CC=C1 NKQHFGWIQCTOMC-UHFFFAOYSA-N 0.000 description 1
- QGCQRZWXVPJNLV-UHFFFAOYSA-N 1-[(3-chlorophenyl)-diphenylmethyl]imidazole Chemical compound ClC1=CC=CC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)N2C=NC=C2)=C1 QGCQRZWXVPJNLV-UHFFFAOYSA-N 0.000 description 1
- JTHKTPJTSOUNEJ-UHFFFAOYSA-N 1-[(3-fluorophenyl)-diphenylmethyl]imidazole Chemical compound FC1=CC=CC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)N2C=NC=C2)=C1 JTHKTPJTSOUNEJ-UHFFFAOYSA-N 0.000 description 1
- FFVGMRVBUJUFCU-UHFFFAOYSA-N 1-[(4-chloro-3-fluorophenyl)-diphenylmethyl]imidazole Chemical compound ClC1=C(C=C(C=C1)C(N1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)F FFVGMRVBUJUFCU-UHFFFAOYSA-N 0.000 description 1
- WKOLBYCXIHLIOB-UHFFFAOYSA-N 1-[(4-fluorophenyl)-diphenylmethyl]-1H-imidazol-1-ium chloride Chemical compound [Cl-].FC1=CC=C(C=C1)C([NH+]1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 WKOLBYCXIHLIOB-UHFFFAOYSA-N 0.000 description 1
- YQTMCFREYHEBEL-UHFFFAOYSA-N 1-[(4-fluorophenyl)-diphenylmethyl]imidazole Chemical compound C1=CC(F)=CC=C1C(N1C=NC=C1)(C=1C=CC=CC=1)C1=CC=CC=C1 YQTMCFREYHEBEL-UHFFFAOYSA-N 0.000 description 1
- USCIESAHBPSCKP-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)-diphenylmethyl]imidazole Chemical compound CSC1=CC=C(C=C1)C(N1C=CN=C1)(C1=CC=CC=C1)C1=CC=CC=C1 USCIESAHBPSCKP-UHFFFAOYSA-N 0.000 description 1
- KCENPJPWSWRZLS-UHFFFAOYSA-N 1-tritylbenzimidazole Chemical compound C1=NC2=CC=CC=C2N1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KCENPJPWSWRZLS-UHFFFAOYSA-N 0.000 description 1
- GQYGGOBEMDYZRZ-UHFFFAOYSA-N 2,4-dimethyl-1-tritylimidazole Chemical compound CC1=NC(C)=CN1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GQYGGOBEMDYZRZ-UHFFFAOYSA-N 0.000 description 1
- IQWYMGYULZCICZ-UHFFFAOYSA-N 2-methyl-1-tritylimidazole Chemical compound CC1=NC=CN1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IQWYMGYULZCICZ-UHFFFAOYSA-N 0.000 description 1
- CLZJOTRKHCNBAT-UHFFFAOYSA-N 3-[imidazol-1-yl(diphenyl)methyl]benzonitrile Chemical compound C(#N)C=1C=C(C=CC1)C(N1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 CLZJOTRKHCNBAT-UHFFFAOYSA-N 0.000 description 1
- LGEQKBQDFVOESR-UHFFFAOYSA-N 4,5-diphenyl-1-tritylimidazole Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 LGEQKBQDFVOESR-UHFFFAOYSA-N 0.000 description 1
- QRIBDBOJGGMYHW-UHFFFAOYSA-N 4-[imidazol-1-yl(diphenyl)methyl]benzonitrile Chemical compound C(#N)C1=CC=C(C=C1)C(N1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 QRIBDBOJGGMYHW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 201000002909 Aspergillosis Diseases 0.000 description 1
- 208000036641 Aspergillus infections Diseases 0.000 description 1
- 206010005098 Blastomycosis Diseases 0.000 description 1
- JPCJJVANGGNFHJ-UHFFFAOYSA-N C(C(O)C)(=O)[O-].C1(=CC=CC=C1)C([NH+]1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(C(O)C)(=O)[O-].C1(=CC=CC=C1)C([NH+]1C=NC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 JPCJJVANGGNFHJ-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241000223238 Trichophyton Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 201000003984 candidiasis Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000003893 lactate salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
(19) DANMARK (^3)
|j| (12) FREMLÆGGELSESSKRIFT on 145181 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENET
(21) Ansøgning nr. 3657/71 (51) lnt.CI.3 C 07 D 233/56 (22) Indleveringsdag 25· Jul. 1971 C07D235/08 (24) Løbedag 13- s ep. 1968 (41) Aim. tilgængelig 25· Jul. 1$71 (44) Fremlagt 27· S ep. 1982 (86) International ansøgning nr.
(86) International indleveringsdag (85) Videreførelsesdag -(62) Stamansøgning nr. 4429/68 (30) Prioritet - (71) Ansøger BAYER AKTIENGESELLSCRAFT, 5Ο9 Leverkusen, DE.
(72) Opfinder Karl-IIeinz Buechel, DE: Erich Regel, DE: Manfred Plempel, DE.
(74) Fuldmægtig Ingeniørfirmaet Budde, Schou & Co.
(54) Fremgangsmåde til fremstilling af N-tritylimidazoler eller deres salte.
Den foreliggende opfindelse angår en kemisk egenartet fremgangsmåde til fremstilling af N-tritylimidazoler eller deres salte.
Såvel de frie forbindelser som deres salte kan anvendes som antimyko-tika, især mod candidose, blastomykose, aspergillose og dermatomy-koser fremkaldt af Trichophyton- og Mikrosporiumarter. En del af 3 forbindelserne er endvidere kendt fra USA-patentskrift nr. 5.521.366 “ som plantebeskyttelsesmidler med fungicid virkning.
De ved fremgangsmåden ifølge opfindelsen fremstillede N-^ -tritylimidazoler har den almene formel I
i 2 145181 w
H
X 2 hvor R, R og R betyder hydrogen, alkyl med 1-4 carbonatomer eller 1 2 phenyl, hvorhos R og R tilsammen kan danne en anelleret benzenring, X betyder hydrogen, en alkylgruppe med 1-4 carbonatomer, halogen, nitro-, cyano-, trifluormethyl-, en S-alkyl- eller O-alkyl-gruppe med 1-4 carbonatomer, og n betyder 1 eller 2, idet n kan have forskellige betydninger i de enkelte benzenringe.
1 2
Alkylgrupperne R, R og R kan være både ligekædede og forgrenede.
Som salte af N-tritylimidazolerne I skal fortrinsvis nævnes salte med hydrogenhalogenidsyrerne, phosphorsyrerne, mono- og bifunktionelle carboxylsyrer og hydroxycarboxyIsyrer, såsom eddikesyre, propionsyre, maleinsyre, ravsyre, fumarsyre, vinsyre, • citronsyre, salicylsyre, sorbinsyre, mælkesyre og 1,5-naphthalendi-sulfonsyre. Af særlig interesse er hydrohalogenider, især chlorider, lactater og salicylater af N-tritylimidazolerne.
Den her omhandlede fremgangsmåde er ejendommelig ved, at et imidazolderivat med den almene formel II
R1 R fil)
H
3 145181 1 2 hvor R, R og R har den ovenfor anførte betydning, omsættes med en triphenylmethylcarbinol med den almene formel ill
OH
-1—Qf" Ψ xn hvor X og n har den ovenfor anførte betydning, eventuelt i et indifferent, højtkogende organisk opløsningsmiddel, eventuelt i nærværelse af et vandsugende middel, i temperaturområdet fra ca. 140° C til ca. 250°C, hvorefter det dannede N-tritylimidazol eventuelt overføres i et salt deraf.
Det må betragtes som overraskende og uforudseeligt, at reaktionskomponenterne under de anførte betingelser med høje temperaturer uden sønderdeling og under vandfraspaltning giver det ønskede reaktionsprodukt i godt udbytte og af god renhed.
I forhold til den fra USA-patentskrift nr. 5021.^66 kendte metode til fremstilling af forbindelser med formel I udmærker den her omhandlede fremgangsmåde sig ved, at det besværlige og omstændelige arbejde med de følsomme imidazolsalte og med de meget hydrolysefølsomme tritylhalogenider indgås. Den omhandlede fremgangsmåde er altså enklere og sikrere end den kendte metode.
Ved fremgangsmåden ifølge opfindelsen anvendes imidazolen sædvanligvis i overskud på op til ea. 100$. Når der arbejdes under tryk kan der eventuelt også anvendes molære mængder. Desuden kan det eventuelt også være hensigtsmæssigt at gennemføre vandfraspalt-ningen azeotropt i nærværelse af et højtkogende, indifferent organisk opløsningsmiddel, såsom xylen, chlorbenzener og lignende forbindelser, ved det pågældende opløsningsmiddels kogepunkt. Når der ikke anvendes opløsningsmidler, arbejdes fortrinsvis i temperaturområdet 4 145181 fra ca. 1T0°C til ca. 190°C.
For at lette vandfraspaltningen kan det eventuelt også være hensigtsmæssigt at arbejde i nærværelse af vandsugende midler, f.eks. jordalkalimetaloxider (MgO, BaO, CaO) samt Alo0_, sædvanlig-vis i omtrentlige molære mængder, eventuelt også i et overskud på op til fra ca. 2 til ca. 3 mol.
Eksempel 1 l-/p-Chlorphenyl-bis-phenyl-methyl7-imidazol
,-N
□ e<ft- JO""1 c6h5 1 Mol p-chlorphenyl-diphenylmethyl-carbinol blandes med ca. 2 mol imidazol og opvarmes uden opløsningsmiddel i 5 timer til ca. 180°C.
Efter afkøling omfældes reaktionsproduktet i xylen til fjernelse af overskydende imidazol. Efter fornyet omfældning i en blanding af benzen og letbenzin fås rent l-^P-chlorphenyl-bis-phenyl-methyl/--imidazol. Smp. l40-l43°C, udbyttet er 53$ af det teoretiske.
Også de nedenfor anførte forbindelser a) - w) kan fremstilles ved ovenstående fremgangsmåde.
Overføringen af de frie forbindelser i saltene sker på kendt måde.
Tabel
Smp., °C
a) 1*(Trisphenyl-methyl)-imidazol 226 - 227 b) l-(Trisphenyl-methyl)-2-methyl-imidazol 225 c) 1-(Trisphenyl-methyl)-2,4-dimethyl-imidazol 232 d) 1-(Trisphenyl-methyl)-4,5-diphenyl-imidazol 228 - 230 e) 1-(m-Cyanophenyl-diphenyl-methyl)-imidazol 119 f) 1-(p-Fluorphenyl-diphenyl-methyl)-imidazol 145 g) l-(p-Tolyl-diphenyl-methyl)-imidazol 128 h) 1-(Trisphenyl-methyl)-benzimidazol l80 - l8l 145181 5 i) l-(o-Chlorphenyl-diphenyl-raethyl)-imidazol 147 - 149 j) l-(m-Chlorphenyl-diphenyl-methyl)-imidazol 114 k) 1-(p-Bromphenyl-diphenyl-methyl)-imidazol 152 l) l-(o-Fluorphenyl-diphenyl-methyl)-imidazol 185 ni) l-(m-Fluorphenyl-diphenyl-methyl)-imidazol 174 n) l-(p-Nitrophenyl-diphenyl-methyl)-imidazol l6o - 170 o) l-(m-Trifluormethylphenyl-diphenyl-methyl)-imidazol 156 p) 1-(p-Cyanphenyl-diphenyl-methyl)-imidazol 164 q) l-(o-Methoxyphenyl-diphenyl-methyl)-imidazol 130 r) l-(p-Methylthiophenyl-diphenyl-methyl)-imidazol 142 s) l-(p-Fluorphenyl-diphenyl-methyl)-2-methyl-imidazol 199 t) 1- (p-Fluorphenyl-p-chlorphenyl-phenyl-methyl) -imidazol 144 u) l-(p-Chlorphenyl-m-fluorphe'nyl-phenyl-methyl)-imidazol 116 v) 1-(p-chlor-m-nitrophenyl-diphenyl-methyl)-imidazol 150 w) l-(p-Bromphenyl-p-chlorphenyl-phenyl-raethyl)-imidazol 140
Eksempel 2 I-(Triphenyl-methyl)-Imldazol
26 g (0,1 mol) triphenylmethylcarbinol smeltes med 13,6 g (0,2 mol) imidazol ved l6o°C under tilbagesvaling, og temperaturen holdes på l80°C i ca. 3» 5 timer. Derefter sættes smelten under vakuum (25 mm Hg, vandluftpumpe), medens temperaturen holdes ved l80°C i ca. JO minutter. Derved afdestillerer en del af det overskydende imidazol samt det fraspaltede vand. Remanensen omkrystalliseres fra tørt xylen. Der fås 22 g (70% af det teoretiske) 1-(trisphenyl--methyl)-imidazol, smp. 225-227°C
N-Triphenylmethyl-imidazolium-lactat.
31 g N-tritylimidazol opløses i aeetonitril ved opvarmning, hvorefter der tilsættes 10 g (0,11 mol) d,1-mælkesyre. Efter afdestillation af opløsningsmidlet krystalliseres remanensen ved overhældning med ether, det krystallinske produkt vaskes med ether og tørres.
Udbytte: 40 g farveløst krystalpulver med smp. 170-l8o°C.
N-Triphenyl-methyl-imidazolium-chlorid 31 g N-trityl-imidazol opløses i 400 ml carbontetrachlorid, hvorefter der ved stuetemperatur tilledes hydrogenchlorid. Derved udfældes hydroohloridet efter nogen tid, og det suges fra. Efter omkrystalli- 6 f45 ί 81 sation i en blanding af acetone og ether i forholdet 1:1 fås farveløse krystaller med smp. 155°C. Udbyttet = 33 g.
På analog måde fås følgende salte:
Smp. G
HF-Triphenylmethyl-imidazolium-maleat 106 - 117 " " tartrat 175 - l80 " " citrat 138 - 145 " " acetat 231 " " salicylat 145 - 168 n " sorbat 148 - ΙβΟ " " succinat 188 - 189 " " fumarat 200 - 206
1-(p-Chlorphenyl-bis-phenyl-methyl)-imidazolium-chlorid 128-30°C " " lactat 90°C
" " salicylat olie
1-(m-Chlorphenyl-bis-phenyl-methyl)-imidazolium-chlorid 153°C
1-(o-Chlorphenyl-bis-phenyl-methyl)-imidazolium-chlorid 159°U 1_(p-Fluorphenyl-bis-phenyl-methyl)-imidazolium-chlorid 110°C " " lactat 95°C
1-(o-Fluorphenyl-bis-phenyl-methyl)-imidazolium-lactat 110°C
1-(m-Fluorphenyl-bis-phenyl-raethyl)-imidazolium-lactat 120°C
1-(p-Fluorphenyl-bis-phenyl-methyl)-imidazolium-salicylat 8o°C
Claims (1)
- 7 145181 Patentkrav. Fremgangsmåde til fremstilling af N-trityl-imidazoler med den almene formel I R1 -N\ Xn 1 2 hvor R, R og R betyder hydrogen, alkyl med 1-4 carbonatomer eller 1 2 phenyl, hvorhos R og R tilsammen kan danne en anelleret benzenring, X betyder hydrogen, en alkylgruppe. med 1-4 carbonatomer, halogen, nitro-, cyano-,trifluormethyl-, en S-alkyl- eller O-alkylgruppe med 1-4 carbonatomer, og n betyder 1 eller 2, idet n kan have forskellige betydninger i de enkelte benzenringe, eller deres salte, kendetegnet ved, at et imidazolderivat med den almene formel II R1 r2'^w^'r (ii> H 1 2 hvor R, R og R har den ovenfor anførte betydning, omsættes med en triphenylmethylcarbinol med den almene formel III
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK365771A DK145181C (da) | 1968-09-13 | 1971-07-23 | Fremgangsmaade til fremstilling af n-tritylimidazoler eller deres salte |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK442968AA DK127114B (da) | 1967-09-15 | 1968-09-13 | Analogifremgangsmåde til fremstilling af N-tritylimidazoler eller salte deraf. |
| DK442968 | 1968-09-13 | ||
| DK365771 | 1971-07-23 | ||
| DK365771A DK145181C (da) | 1968-09-13 | 1971-07-23 | Fremgangsmaade til fremstilling af n-tritylimidazoler eller deres salte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK145181B true DK145181B (da) | 1982-09-27 |
| DK145181C DK145181C (da) | 1983-02-21 |
Family
ID=26067157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK365771A DK145181C (da) | 1968-09-13 | 1971-07-23 | Fremgangsmaade til fremstilling af n-tritylimidazoler eller deres salte |
Country Status (1)
| Country | Link |
|---|---|
| DK (1) | DK145181C (da) |
-
1971
- 1971-07-23 DK DK365771A patent/DK145181C/da active
Also Published As
| Publication number | Publication date |
|---|---|
| DK145181C (da) | 1983-02-21 |
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