DE1445673A1 - Process for the preparation of new substituted diaminopyridines - Google Patents
Process for the preparation of new substituted diaminopyridinesInfo
- Publication number
- DE1445673A1 DE1445673A1 DE19641445673 DE1445673A DE1445673A1 DE 1445673 A1 DE1445673 A1 DE 1445673A1 DE 19641445673 DE19641445673 DE 19641445673 DE 1445673 A DE1445673 A DE 1445673A DE 1445673 A1 DE1445673 A1 DE 1445673A1
- Authority
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- Germany
- Prior art keywords
- general formula
- compound
- pyridine
- denotes
- nitro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Dr. Expl.Dr. Expl.
Die Srflndung betrifft die Herstellung neuer therapeutisch wertvoller Verbindungen der allgemeinen For»elThe invention concerns the manufacture of new therapeutic valuable compounds of the general formula
in der JC ein Stickstoffatom oder die CH-Gruppierung bedeutet, R ein Wasserstoff atom, eine sich von Kohlensäuremonoestern, von, vorzugsweise substituierten, Benzooeauren oder von Mono- oder Dicarbonsäuren mit 1 bis 6 C-Atomen sieh herleitende, gegebenenfalls durch einen Morpholinoreet substituierte, Aeylgruppe ist, R , R3 und R gleich oder verschieden sind und die gleiche Bedeutung wie R BK- habenin which JC denotes a nitrogen atom or the CH group, R denotes a hydrogen atom, one which is derived from carbonic acid monoesters, from, preferably substituted, benzoic acids or from mono- or dicarboxylic acids with 1 to 6 carbon atoms, and is optionally substituted by a morpholinoreet, Aeylgruppe, R, R 3 and R are identical or different and have the same meaning as R BK-
und ausaerden noch Halogen, eine Trifluormothyl, Cyan-, Rbodan-, Alkyl-, Mercapto-» Alkylthio-, Aoylthle-, Hydroxy», m and halogen, a trifluoromothyl, cyano, rbodane, alkyl, mercapto, »alkylthio, aoylthle, hydroxy», m
Alkoxy-, Aoyloxy-, Vitro-, Carboxy*, Carbathoxy- oder Alkrlamittogrwppe sein kennen und R5 ein Vasserstoffatom oder eis Acylrest der oben genannten Art ist«Know being alkoxy, aoyloxy, vitro, carboxy *, carbathoxy or alkrlamittogrppe and R 5 is a hydrogen atom or acyl radical of the type mentioned above «
Iteter den Subs ti tuen tea, die Alkylgruppen sind oder solche enthalten, werden Jene bevorsugt, die 1 bis 6 Kohlenstoffatom«Iteter denotes the substituents that are or are alkyl groups contain those with 1 to 6 carbon atoms «
Si· oben genannten Bensoee&uren können einfach oder mehrfach substituiert «ein. Hierbei kennen folgende ßubetituenteaThe abovementioned benzoic acids can be substituted one or more times. The following ßubetituentea know here
909805/0973909805/0973
BAD OWQ'NALBAD OWQ'NAL
auftreten s Halogene tome, Hydroxy-, Trifluormethyl-=, Alkyl-· Alkoxy», Acyloxy-, Amino-, Alkylaad.no->, Acylamino-, Cyan», Rhodan-, Nitro-, Mercapto-», Alkylthio-, Acylthlo-, Caroxy-, Carb&thoxy« und Carhaninogruppen. Auch bei diesen Substi«» tuenten gilt hinsichtlich der Acylgruppierungen und der Alkylgruppen die oben angeführte Einschränkung bzw ο Bevorzugung»occur s halogen atoms, hydroxy-, trifluoromethyl- =, alkyl- Alkoxy », acyloxy, amino, alkylaad.no->, acylamino, cyano», Rhodan, nitro, mercapto », alkylthio, acylthlo, caroxy, Carb & thoxy «and carhanino groups. Even with these nouns «» In terms of acyl groups and alkyl groups, the above restriction or ο preference »
Die neuen Verbindungen haben wertvolle pharmakologiache Eigenschaften» Sie zeichnen sich durch eine hohe anti« phlogistische Wirkung tue»The new compounds have valuable pharmacological properties Properties »They are characterized by a high anti« do phlogistic effect »
Zur Herstellung der neuen Verbindungen geht »an so vor, dass aan in an sich bekannter Veise in einer Verbindung der allgemeinen FormelTo prepare the new compounds, the procedure is to use a method known per se in a compound of the general formula
■indestens oina Nitrogruppe in Gegenwart eines Katalysators, vorzugsweise Raney-Niokel, bei erhöhter Temperatur und bei erhShtem Druck unter Bildung einer Verbindung der allgemeinen FormelAt least one nitro group in the presence of a catalyst, preferably Raney Niokel, at elevated temperature and at elevated pressure with formation of a compound of the general formula
IIIIII
hydriert und dann gleichseitig oder nacheinander Aminogruppe und/oder da« »entrale Stickstoff atom aoyliert und gegebenenfalle einen oder mehrere der Suba ti tuenten weiter umsetzt.hydrogenated and then aoylated amino groups on the same side or one after the other and / or the "" central nitrogen atom and, if applicable, one or more of the subatuents continues to implement.
BAD 909805/0973BATH 909805/0973
Ss empfiehlt sieh, die Hydrierung der Nitrogruppen bei etwa 70* C und bei eine« Druck Ton etwa 20 bie 30 ätu durchzuführen. Aueβer äaney~Niekel können noch folgende Katalysatoren verwendet werden: Palladium-Mohr oder Palladium oder Palladiumhydroxyd auf Trägermaterial vie Bariumsulfat oder Caloiunoarbonat. Die Reduktion kann auch mit Sink/Salzsäure, Zinn/Salzsäure, Zinn(II)ohlorid/ Salzsäure oder Sisen/Salzsäure oder Salzen des Schwefelwasserstoffe in Alkohol/Wasser bei etwa 70* bis etwa 120* C oder »it aktivierte» Aluminium in wasserhaltigem Äther bei 20* bis kO· C durchgeführt werden.It is recommended to carry out the hydrogenation of the nitro groups at about 70 ° C and at a pressure of about 20 to 30 ° C. The following catalysts can also be used aside from the general rule: Palladium black or palladium or palladium hydroxide on a carrier material such as barium sulfate or carbonate carbonate. The reduction can also be carried out with sink / hydrochloric acid, tin / hydrochloric acid, tin (II) chloride / hydrochloric acid or iron / hydrochloric acid or salts of hydrogen sulphides in alcohol / water at about 70 * to about 120 * C or »it activated» aluminum in hydrous ether can be carried out at 20 * to kO · C.
Zur partiellen Acylierung der «substituier tea Aminogruppen kaam beispielsweise das entsprechende Säurshalegeeld oder Säureamfaydrid verwendet werden. Zweokmäeslgerwelse sollte» hierbei Temperaturen unter 70* C, vorzugsweise Temperaturen swiaoaen etwa 30 und etwa 50* C, eingehalten werde»· Bie Reaktionszeiten betragen im allgemeinen weniger «Is.eine Stunde» Man kann die Acylierung aber auch unter Verwendung entsprechender Seter durchführen» In diesem falle werden höhere Temperaturen, beispielsweise von 150 bis I8e* C, eingehalten. Λ For the partial acylation of the substituted amino groups, for example, the appropriate acid halide or acid amphydride can be used. Two-legged catfish should “here, temperatures below 70 ° C, preferably temperatures between about 30 and about 50 ° C, are maintained”. The reaction times are generally less than “one hour” In this case, higher temperatures, for example from 150 to 18e * C, are maintained. Λ
Bie Acylierung des zentralen Stickstoff atoms, die vorzugsweise naohtrttellch erfeigen soll, kann ebenfalls mit Säure* halogeniden oder Säureanhydriden, jedoch bei Temperaturen oberhalb von etwa 70* C1 vorzugsweise zwischen etwa 80 und etwa 120* C, durchgeführt werdene Hierbei werden längere Reaktloneseifcen, beispielsweise von drei Stunden» b«n9tigt.Atom Bie acylation of the central nitrogen, which should preferably erfeigen naohtrttellch may also halides with acid * or acid anhydrides, but at temperatures above about 70 * C 1 preferably between about 80 and about 120 * C, performed becoming Here, longer Reaktloneseifcen, e.g. of three hours "required".
BAD 909805/0973BATH 909805/0973
- h -Beispiel 1- h - example 1
2-PlienylaBiino-5-aiBino-pyridin2-PlienylaBiino-5-aiBino-pyridine
2 g 2-Plienylamino-'5-nitro-pyridin werden in 600 ml Meth anol in Gegenwart von 30 g Raney-Hiokel bei 70° C und 20 bis 30 attt hydriert« Kach dem Abdampfen des Lösungsmittels wird der Rückstand im Vakuum destilliert. Die Base geht bei 0,5 lorr ' zwischen 190 und 200° C über und hat nach dem Umkristallisieren aus Isopropanol einen Schmelzpunkt von 156° O.2 g of 2-plienylamino-'5-nitro-pyridine are in 600 ml of methanol in the presence of 30 g Raney-Hiokel at 70 ° C and 20 to 30 attt hydrogenated. After the solvent has evaporated, the residue is distilled in vacuo. The base goes at 0.5 lorr ' between 190 and 200 ° C above and has after recrystallization from isopropanol has a melting point of 156 ° O.
Beispiel ,2
2-Phenylamino-5-acetamino-pyridin Example , 2
2-phenylamino-5-acetaminopyridine
18,5 g 2«-Hienylaminq-5~amino-pyridin werden in 40 ml Dioxan bei 40 bis -50° C mit 9»5 ml Acetanhydrid umgesetzt. Nach kurzer Zeit fällt die genannte Verbindung aus« Sie wird aus Bioxan umkristallisiert. Fp. 177° C.18.5 g of 2'-hienylamineq-5-aminopyridine are dissolved in 40 ml of dioxane reacted at 40 to -50 ° C with 9 »5 ml of acetic anhydride. To The compound mentioned precipitates out for a short time. It is recrystallized from bioxane. Mp. 177 ° C.
Beispiel 3
2«Phenylamino-5-propionylamino-pyridin Example 3
2 «phenylamino-5-propionylamino-pyridine
56 g 2-Phenylamino-5-amind-pyridin werden analog Beispiel 2 mit 59 g Propionsäureanhydrid in 100 ml Dioxan umgesetzt· Die Verbindung wird aus Aethanol umkristallisiert« Pp. 172° C.56 g of 2-phenylamino-5-amine-pyridine are reacted analogously to Example 2 with 59 g of propionic anhydride in 100 ml of dioxane. The compound is recrystallized from ethanol.
N«£2-Phenylamino-pyridyl- (5Jy -carbaminsäureäthyleBterN «2-Phenylamino-pyridyl- (5Jy -carbamic acid ethyl ether
C8H5OCO-HHC 8 H 5 OCO-HH
9,3 g 2-Phenylamino-5-aiaino-pyridin werden in 30 ml Dioxan und 6 ιοί Pyridin mit 4»8 ml Chlorameisönsäureäthyle3ter bei 40 "bio 50° 0 umgesetzt. Nach 1 Stunde wird das Lösungsmittel im Vakuum abdestilliert, der Rückstand in Chloroform gelöst und mit Wasser gewasohen. Danach wird das Chloroform abdestilliert und der Rückstand aus Aethanol umkristallisiert. Fp. 141° 9.3 g of 2-phenylamino-5-aiainopyridine are dissolved in 30 ml of dioxane and 6 ιοί pyridine with 4 »8 ml chloroformic acid ether 40 "bio 50 ° 0 implemented. After 1 hour, the solvent distilled off in vacuo, the residue dissolved in chloroform and washed with water. The chloroform is then distilled off and the residue is recrystallized from ethanol. M.p. 141 °
2-(H-Phenyl-N-propionylamino)-5-acetamino-pyridin CH5 CO-HH-2- (H-phenyl-N-propionylamino) -5-acetaminopyridine CH 5 CO-HH-
10 g 2-ihenylamino-5-acetainino-'pyridin werden mit 6*3 g Propionßäureanhydrid in 40 ml Dioxan 5 Stunden gekocht. Nach dem Ab» destillieren des Dioxane wird der Rückstand in Benzol gelöst und mit verdünnter Natronlauge gewaschen· Das Benzol wird abdestil liert und der Rückstand aus Aethanol umkristallisiert. Fp. 146 - 148° C.10 g of 2-ihenylamino-5-acetainino-pyridine are mixed with 6 * 3 g of propionic anhydride boiled in 40 ml of dioxane for 5 hours. After the ab » distilling the dioxane, the residue is dissolved in benzene and washed with dilute sodium hydroxide solution. The benzene is distilled off and the residue is recrystallized from ethanol. Mp. 146-148 ° C.
Beispiel 6
2-(H-Phenyl-5-propionylaraino)-5-propionylamino-pyridin Example 6
2- (H-phenyl-5-propionylaraino) -5-propionylamino-pyridine
COC8H5 COC 8 H 5
12 g 2-Phenylaittinö-5-propionylamino-pyridin werden mit 7»2 g12 g of 2-phenylaittino-5-propionylamino-pyridine are mixed with 7 »2 g
Propionsäureanhy&rid in 40 ml· Moxan wie in Beispiel 5 umgesetzt und aufgearbeitet. Die Verbindung wird aus Aethanol-Benzin-Gemisoh umkristallisiert· Fp. 124° C.Propionic anhydride in 40 ml · moxane reacted as in Example 5 and worked up. The connection is made from ethanol-gasoline-Gemisoh recrystallized · mp. 124 ° C.
V 909805/097 3V 909805/097 3
K«·-Phenyl-Ϊ!«· f'3-£oetaiainoDyridyl«(2)K «· -Phenyl-Ϊ!« · F'3- £ oetaiainoDyridyl «(2)
. GOOO8H55 . GOOO 8 H 55
15 g 2~Pheny"läiiii2ip«-5—aoetaiaino—pyridin Lmd 6&3 ial Chlorameisen« RäureäthylirStfT ii/erden in 30 ml Dioxan mit 11,3 S Kaliiuncar-"bonat 3 Stv.na.mi gekocht» Daiaaoli i^ird filtriert und das Dioxan ab&estilliei'ts JDer Riickstaiid wird aus Aethanol siert» ip, 160° 0»15 g of 2 pheny "läiiii2ip" -5-aoetaiaino-pyridine Lmd 6 & 3 ial chlor ants "RäureäthylirStfT ii / earth in 30 ml of dioxane with 11.3% potassium carbonate 3 Stv.na.mi cooked" Daiaaoli i ^ ird filtered and the dioxane from &estilliei'ts JThe residue is siert from ethanol »ip, 160 ° 0»
Beisp_iel_8Example_8
K-Phenyl-H-^S-propion^rlaraino-pyridyl- (2 )j -oarehaminsäureäthylester K-phenyl-H- ^ S-propion ^ rlaraino-pyridyl- (2) j -oarehamic acid ethyl ester
O3H6 CO-HH-O 3 H 6 CO-HH-
000C2H5 000C 2 H 5
15 g 2-Phenylamino.~5-propionylamino-pyridin9 6 ml Chlorameisensäureäthylester und 10,7 g Kaliumcarbonat v/erden in 40 ml Dioxan wie in Eeispiel 7 umgeeetat und aufgearbeitet· Ip· 159° 0* -15 g of 2-phenylamino. ~ 5-propionylamino-pyridine 9 6 ml of ethyl chloroformate and 10.7 g of potassium carbonate v / earth in 40 ml of dioxane as in Example 7, converted and worked up Ip 159 ° 0 * -
^dyl-. (2) J-carbaminaäureäthylester ^ dyl-. (2) I-carbamic acid ethyl ester
20 g IT*f2«PhenylaittJjiopyridyl-(5)j--car:baittinsä1U2ieätljyl€steri, 7,5 al Chlorameisenaäureäthyl&3ter und 13,5 g Kaliumcarbonat werden in 150 ml Benzol analog Beispiel 7 umgesetzt und die VerbihäUäÄ aus Aethanol-Benzin-Gemiach umkristallisiert.20 g IT * f2 «PhenylaittJjiopyridyl- (5) j - car : baittinsä 1 U2ieätljyl € ster i , 7.5 al chloroformic acid ethyl & 3ter and 13.5 g potassium carbonate are converted in 150 ml benzene as in Example 7 and the VerbihäUäÄ from ethanol-gasoline -Gemiach recrystallized.
° BAD ° BATH
2« (S-BMngrl<4k4* eMorbemaamino) ^5-2 «(S-BMngrl <4k4 * eMorbemaamino) ^ 5-
10 g S-l^-Hiejfl^laMijaopyrid^l-(5 10 g Sl ^ -Hiejfl ^ laMijaopyrid ^ l- (5
15 f 5 gp-0hlorBiBisioylsthlorld und 12 β Kaliumcarbonat werdoiL ia Beausol 5 Stunden gekocht. Anschließend v/ird sinu? VereeijTung waaseriialtigcs Dimetliylformaiaid 2Ugege"bea und 1 Stunde veitergekooht» B&a Lösungsiaittel wird danach abdeatilliert und der Stickstand aus Aethanol umkxistallisiert· Fp · 190° Go15 f 5 gp-0hlorBiBisioylsthlorld and 12 β potassium carbonate werdoiL ia Beausol cooked for 5 hours. Then v / ird sinu? Defense Waaseriialtigcs Dimetliylformaiaid 2Ugege "bea and 1 hour continued »B & a solvent is then distilled off and the nitrogen stand was crystallized from ethanol · mp · 190 ° Go
2-(3-lrifluoreethylph«Qylainino )-5-asino-pyridin2- (3-Irifluoroethylph «Qylainino) -5-asino-pyridine
wird analogbecomes analog
Beispiel! lait Haney-Hickel hydriert und aufgearbeitet· Die Base siedet bei 0,5 Torr bei 190 bis 192° C. Sie bildet mit Maleinsäure ein kristallines SaIa, das nach dem Umkristal lisieren aus Isopropanol bei 115° C schmilzt·Example! lait Haney-Hickel hydrogenated and worked up · The Base boils at 0.5 torr at 190 to 192 ° C. It forms with maleic acid a crystalline salt which, after the recrystalline lize from isopropanol at 115 ° C melts
)-5-acetamino-pyridin) -5-acetaminopyridine
101 £ 2" C5-3Erifluorfltethylphenylamino )-5-amino-»pyridin werden adt 58 «1 Acetanhydrid in 200 al Bensol analog Beispiel 2 um-101 £ 2 "C5-3Erifluorfltethylphenylamino) -5-amino-» pyridine adt 58 «1 acetic anhydride in 200 al Bensol analogous to Example 2
gesetat. Die Yerbindung wird aus Aethanol umkristallisiert. 156« 0^budget. The compound is recrystallized from ethanol. 156 «0 ^
909805/09 7 3 s 909805/09 7 3 s
· (3-Srifluoinaethylphenylainino )-5-propionylamino-pyridin· (3-Srifluoinaethylphenylainino) -5-propionylamino-pyridine
80 g S-C^-Trifluorräethylpheiiylamino'J-S-ajaino-pyridiii·» werden mit 41 g Propionaäureaohydrid analog Beispiel 12 in 200 ml Benzol umgesetzt* Das Rohprodukt wird aus Isopropanol umkristallisiert. Pp« 166° Co80 g of S-C ^ -Trifluorräethylpheiiylamino'J-S-ajaino-pyridiii · »become with 41 g of propionic aohydride analogous to Example 12 in 200 ml Benzene converted * The crude product is recrystallized from isopropanol. Pp «166 ° Co
Bei.QP.igl. 14.At.QP.igl. 14th
rmetliylphenylaminoj|-pyridyl-(5 )j «=oarbamin säureäthylestermethylphenylaminoj | -pyridyl- (5) j "= carbamine acid ethyl ester
65 g 2-(3-Irifluormetliylphenylamino)-5-aEiino-pyridin werden mit 24* 5 ml Chlorameieenaäureäthylester in 200 ml Aceton und 30 ml iyridin analog Beispiel 4 umgesetzt· Die Verbindung wird aus Aethanol urakristallisiert. Pp. 175° C·65 g of 2- (3-irifluoromethylphenylamino) -5-aEiino-pyridine become with 24 * 5 ml of ethyl chloroformate in 200 ml of acetone and 30 ml of iyridine reacted analogously to Example 4. The compound is uracrystallized from ethanol. Pp. 175 ° C
2- (H-3-Irif luorme thylphenyl-H-propionylamino )-5-propionylamino pyridin2- (H-3-Irifluoromethylphenyl-H-propionylamino) -5-propionylamino pyridine
C-H-CO-NHC-H-CO-NH
15 g 2-(3-Irifluormethylphenylamino)-5-propionylamino-pyridin werden mit 6,5 g Propionsäufeanhy&rid in 50 ml Dioxan analog Beispiel 5 umgesetet und aufgearbeitet· Die Verbindung wird aus Aethanol-Benzin-eemisoft umkristallisiert. Fp. 118° C.15 g of 2- (3-irifluoromethylphenylamino) -5-propionylamino-pyridine are analogous with 6.5 g of propionic anhydride in 50 ml of dioxane Example 5 reacted and worked up · The compound is recrystallized from ethanol-gasoline-eemisoft. M.p. 118 ° C.
; BAD ORIGINAL; BATH ORIGINAL
909805/097 3909805/097 3
1616
K- ( ^-IDrifluor^ifcylpnenyl )~H«> fB-ace taminopyridyl- (2 jj -carbaminsäureätliylesterK- (^ -IDrifluoro ^ ifcylpnenyl) ~ H «> fB-ace taminopyridyl- (2 jj -carbamic acid ethyl ester
14,7 g ^14.7 g ^
4,8 β ChlorameisenBäureäthylester und 8,7 g Kaliumcarbonat werden. In 40 ml Dioxan analog Beispiel 7 umgesetzt» Die Verbindung wird aas Aetiisaiol-Benain-Gemisch umkristallisiert. fp. 13€° 0.4.8 β ethyl chloroformate and 8.7 g potassium carbonate will be. Reacted in 40 ml of dioxane analogously to Example 7. The compound is recrystallized from an acetiol-benain mixture. fp. € 13 ° 0.
o8aroatiqfleategy 9 ml öhloraaeiscnsäureäthylester und 16 g Xalittsoar^Gsiat werden in 100 ial Metnyläthylketon analog Bei spiel ? Ovgesetst· IMe Verbindung wird aus Benzol-Benzino8aroatiqfleateg y 9 ml öhloraaeiscnsäureäthylester and 16 g Xalittsoar ^ Gsiat are in 100 ial methyl ethyl ketone analogous to example? Ovgesetst · IMe compound is made from benzene-gasoline ueferletallisiert. Pp. 100 bis 102° C.ueferletallized. Pp. 100 to 102 ° C.
1818th
10,1 g 2-(3-Trilluoraetliylph«iylaHiino)-5-aaino--pyridin werden in 40 Dl Mooea» tmd 5 ml Pyridin mit 7 g p-Cnlorbenzoylohlorid bei 40-50* H ufflgaeetat. Hach. 2 Stunden wird das Dioian im Yakuaa abdeetilliert, 4er Rückatand in 150 nl heißem Benzol10.1 g of 2- (3-Trilluoraetliylph «iylaHiino) -5-aaino - pyridine become in 40 Dl Mooea »tmd 5 ml pyridine with 7 g p-chlorobenzoylochloride at 40-50 * H ufflgaeetat. Huh. 2 hours the Dioian will be in Yakuaa distilled off, 4 residue in 150 nl hot benzene
gülDa·» und ait heißem Wasser gewaschen» Beim Abkühlen kristal-IiB!.s:et diö Verbindung sue dem Benzol aus» Nach dem Uiakristal-Linieren*aus Diozau liegt der Schmelzpunkt bei 208° G· gülDa · » and washed with hot water» When cooling down, crystal-IiB ! .s: et diö connection sue the benzene from »According to the Uiakristal-Linieren * from Diozau the melting point is 208 ° G ·
f. J 2- {^-l'rif luoj^aetiijrlpIienylaEiino| -pyridyl™ ( 5 Jr idhlidf. J 2- {^ -l'rif luoj ^ aetiijrlpIienylaEiino | -pyridyl ™ (5 Jr idhlid
aaidiaorpholidaaidiaorpholid
>-oo-Ha> -oo-ha
■Μ'■ Μ '
20 g E--) 2" ßf-Tr.tfluöriT.öthylpiienylaniinoJ -pyridyl-»( 5 )r -a20 g of E - -) 2 "ßf-Tr.tfluoriT.öthylpiienylaniinoJ -pyridyl -» (5) r -a
hergestellt analog Baiapisl 4 aus 2— (3 üjaino )^!5»ari5jio~py.?idin und phenyleater.. wordsn mit 9 g Ilorpholin b©i 140° C Tuagesetzt. Haeh 30 Mnuten wird die Sclaaalss in Benaol golösu und alt verd» Hatronlaugö gewaschen» Das Bensol X'/irrt abdestilliert und der Rückstand aus Asthanol-Benzin-GemisQli luiikristallisiert. 3?p, 84 - 86° C» .produced analogously to Baiapisl 4 from 2 - (3 üjaino) ^! 5 »ari5jio ~ py.? idin and phenyleater .. wordsn with 9 g of Ilorpholin at 140 ° C Tuageset. After 30 minutes the Sclaaalss in Benaol is golösu and old verd »Hatronlaugö washed» The Bensol X '/ errt distilled off and the residue from asthanol-gasoline-GemisQli luiikristallisiert. 3? P, 84 - 86 ° C ».
2-H- ( 3-Trif luox^inethylphenyl)- (4-chlorbensamino amiiiopyridin2-H- (3-trifluoxylinethylphenyl) - (4-chlorobensamino amiiiopyridine
-CP5 ΪΟ-f ^)-Cl-CP 5 ΪΟ-f ^) - Cl
20 g N-^- ji-2rifluorinethylphenylaminoj -pyridyl- (5)|-earbamin-. säureäthyleater v/erden mit* 14 g p-Chlorbenzoylchlorid in 100 ml Dioxan bei Siedetemperatur in Gegenwart von 14 g Kaliumcarbonat umgesetzt. Nach 2 Stunden wird filtriert und das Pil trat im Vakuum eingedampft. Der Rückstand wird aus·Benzol umkristallisiert. Pp. 135° 0· .20 g of N - ^ - ji-2rifluorinethylphenylaminoj -pyridyl- (5) | -earbamin-. acid ethyl ether v / earth with * 14 g of p-chlorobenzoyl chloride in 100 ml Dioxane at boiling point in the presence of 14 g of potassium carbonate implemented. After 2 hours it is filtered and the Pil occurred in the Evaporated in vacuo. The residue is recrystallized from benzene. Pp. 135 ° 0 ·.
«AD - 11 -«AD - 11 -
9098 05/097 39098 05/097 3
2121
1!~| £~ /i^Trif ittOCTrtethylphenylaininoj «-pyridyl- (5 )\ "-carbaminBauremorpholinoäthyleeter w 1! ~ | £ ~ / i ^ Trif ittOCTrtethylphenylaininoj «-pyridyl- (5 ) \ " -carbamineBauremorpholinoäthyleeter w
15 g N-=-fi?- |3~ Trifluormethylphftnylaininoj.· pyridyl·" (5 )V «°ca.rbami.n« säureplienylet«tc?r v/prdeh mit 10r5 g Mor'pLiolinäthanol v/ie in Beispiel 19 l>escliriel)en umgeeatert und aufgearbeitet. Das Hydrochlorid wird aus Isopropanol umkristalliöiert. Ί?ρ. 200° C15 g N - = - fi - |? 3 ~ Trifluormethylphftnylaininoj · · pyridyl "(5) V" ° ca.rbami.n "säureplienylet" tc rv / prdeh with 10 r 5 g Mor'pLiolinäthanol v / ie in example.? 19 liters of escliriel) en breathed and worked up. The hydrochloride is recrystallized from isopropanol. Ί? Ρ. 200 ° C
BeiapielBeiapiel 2222nd
2-(4-Pentyloxyphenylamino)~5~amino~pyridin2- (4-pentyloxyphenylamino) ~ 5 ~ amino ~ pyridine
2-(4-Pentyloatypahenyiamino)»5-nitro-pyi>idin wird analog Beispiel .1 mit Eaney-Nickel hydriert und aufgearbeitet« Die Base siedet bei 0r5 Sorr awischen 225 und 235° C.2- (4-Pentyloatyp a henyiamino) »5-nitro-pyi> idin .1 is hydrogenated analogously to Example Eaney with nickel and worked" The base boils at 0 r 5 Sorr awischen 225 and 235 ° C.
2~(4-Pentylcacyphenylamino J-S-acetamino-pyridin2 ~ (4-Pentylcacyphenylamino J-S-acetaminopyridine
C6 H1 x C 6 H 1 x
26 g .2-(4-Pentylozyphenyl*aiflino)-5-aaiino-pyridin werden mit Acetanhydrid in 100 ml Benzol analog Beispiel 2 umgesetzt. Die Verbindung wird aus Aethanol umkristallisiert. Fp. 167° C.26 g of 2- (4-pentylozyphenyl * aiflino) -5-aaiino-pyridine are mixed with Acetic anhydride reacted in 100 ml of benzene analogously to Example 2. The compound is recrystallized from ethanol. M.p. 167 ° C.
OADOAD
2^Pfieny3Liömino-5-saUoyloylamino-pyridin "n 2 ^ Pfieny3L i ömino-5-saUoyloylamino-pyridine " n
909805/0973909805/0973
- 12 -- 12 -
11 g 2~Pheaylamino-5-amino-pyridin werden mit 13 g Salicylsäurephenyleater 2 Stunden au£ 180° .0 erhitzt· Nach dem Abkühlen wird in Aethanol gelöst, woraus die Verbindung mit einem Mol Kristallalkohol kristallisiert. Pp. 171° C.11 g of 2-pheaylamino-5-aminopyridine are mixed with 13 g of salicylic acid phenyl ether Heated to £ 180 ° .0 for 2 hours · After cooling, it is dissolved in ethanol, from which the compound with crystallized from one mole of crystalline alcohol. Pp. 171 ° C.
.-SE.-SE
909805/097 3909805/097 3
Claims (2)
Dr.No/Ha28ο8.1964
Dr.No/Ha
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED0045303 | 1964-08-29 | ||
| DED0045302 | 1964-08-29 | ||
| DE19641795499 DE1795499A1 (en) | 1964-08-29 | 1964-08-29 | New substituted diaminopyridines |
| DED0045302 | 1964-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE1445673A1 true DE1445673A1 (en) | 1969-01-30 |
| DE1445673C DE1445673C (en) | 1973-06-07 |
Family
ID=
Also Published As
| Publication number | Publication date |
|---|---|
| DE1795499A1 (en) | 1972-02-10 |
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