DE1219031B - Process for the preparation of new 1,2,4-triazole derivatives - Google Patents
Process for the preparation of new 1,2,4-triazole derivativesInfo
- Publication number
- DE1219031B DE1219031B DEF45503A DEF0045503A DE1219031B DE 1219031 B DE1219031 B DE 1219031B DE F45503 A DEF45503 A DE F45503A DE F0045503 A DEF0045503 A DE F0045503A DE 1219031 B DE1219031 B DE 1219031B
- Authority
- DE
- Germany
- Prior art keywords
- cyanate
- new
- acid ester
- general formula
- preparation
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- -1 cyanic acid ester Chemical class 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 150000001913 cyanates Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BBFPNAQMYBOJLI-UHFFFAOYSA-N (2,4-dimethylphenyl) cyanate Chemical compound CC1=CC=C(OC#N)C(C)=C1 BBFPNAQMYBOJLI-UHFFFAOYSA-N 0.000 description 1
- URTZFIYCFJKKMP-UHFFFAOYSA-N (2-acetamidophenyl) cyanate Chemical compound C(C)(=O)NC1=C(C=CC=C1)OC#N URTZFIYCFJKKMP-UHFFFAOYSA-N 0.000 description 1
- OBFSMFKFSRHASW-UHFFFAOYSA-N (2-chloro-6-methylphenyl) cyanate Chemical compound ClC1=C(C(=CC=C1)C)OC#N OBFSMFKFSRHASW-UHFFFAOYSA-N 0.000 description 1
- TWLCCEYEPIGFLI-UHFFFAOYSA-N (2-methyl-5-nitrophenyl) cyanate Chemical compound CC1=CC=C([N+]([O-])=O)C=C1OC#N TWLCCEYEPIGFLI-UHFFFAOYSA-N 0.000 description 1
- SHBUQGBESNZMCH-UHFFFAOYSA-N (2-nitrophenyl) cyanate Chemical class [O-][N+](=O)C1=CC=CC=C1OC#N SHBUQGBESNZMCH-UHFFFAOYSA-N 0.000 description 1
- MHPDOOHLJBFGCC-UHFFFAOYSA-N (2-phenoxyphenyl) cyanate Chemical compound N#COC1=CC=CC=C1OC1=CC=CC=C1 MHPDOOHLJBFGCC-UHFFFAOYSA-N 0.000 description 1
- DSNBORYPFYZWQD-UHFFFAOYSA-N (2-sulfanylphenyl) cyanate Chemical compound SC1=C(C=CC=C1)OC#N DSNBORYPFYZWQD-UHFFFAOYSA-N 0.000 description 1
- YVOQQUGUJXFKOC-UHFFFAOYSA-N (3-chlorophenyl) cyanate Chemical compound ClC1=CC=CC(OC#N)=C1 YVOQQUGUJXFKOC-UHFFFAOYSA-N 0.000 description 1
- KWKSWTHGKCZLRO-UHFFFAOYSA-N (3-cyanatophenyl) acetate Chemical compound C(C)(=O)OC=1C=C(C=CC1)OC#N KWKSWTHGKCZLRO-UHFFFAOYSA-N 0.000 description 1
- MUAFEFAYKJZTHJ-UHFFFAOYSA-N (4-acetylphenyl) cyanate Chemical compound CC(=O)C1=CC=C(OC#N)C=C1 MUAFEFAYKJZTHJ-UHFFFAOYSA-N 0.000 description 1
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 description 1
- BFVDUDOXDKMMSP-UHFFFAOYSA-N 2-cyanatobenzenesulfonic acid Chemical compound O(C#N)C1=C(C=CC=C1)S(=O)(=O)O BFVDUDOXDKMMSP-UHFFFAOYSA-N 0.000 description 1
- UUKCNYOTIPWWTR-UHFFFAOYSA-N 2-cyanatobenzoic acid Chemical class OC(=O)C1=CC=CC=C1OC#N UUKCNYOTIPWWTR-UHFFFAOYSA-N 0.000 description 1
- QMPJPRZCWNIROK-UHFFFAOYSA-N 4-cyanatobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(OC#N)C=C1 QMPJPRZCWNIROK-UHFFFAOYSA-N 0.000 description 1
- GHGHLOPGAVHMGL-UHFFFAOYSA-N 4-cyanatobenzoic acid Chemical compound OC(=O)C1=CC=C(OC#N)C=C1 GHGHLOPGAVHMGL-UHFFFAOYSA-N 0.000 description 1
- ZTRQVHHKKXTICK-UHFFFAOYSA-N CC(C(C=C1)(N(C)C)N(C)C)C=C1OC#N Chemical compound CC(C(C=C1)(N(C)C)N(C)C)C=C1OC#N ZTRQVHHKKXTICK-UHFFFAOYSA-N 0.000 description 1
- LUJFRWQSNIMCEY-UHFFFAOYSA-N CC(C)OC(C=CC(OC#N)=C1OC)=C1OC Chemical compound CC(C)OC(C=CC(OC#N)=C1OC)=C1OC LUJFRWQSNIMCEY-UHFFFAOYSA-N 0.000 description 1
- VLMOSYXUVIVLAZ-UHFFFAOYSA-N N#CO.C1=CC=C2N=CC=CC2=C1 Chemical class N#CO.C1=CC=C2N=CC=CC2=C1 VLMOSYXUVIVLAZ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- CYVJDAZADUDFIL-UHFFFAOYSA-N [2-(morpholine-4-carbonyl)phenyl] cyanate Chemical compound O(C#N)C1=C(C(=O)N2CCOCC2)C=CC=C1 CYVJDAZADUDFIL-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BGAXIYISGQEDGE-UHFFFAOYSA-N ethyl 2-cyanatobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OC#N BGAXIYISGQEDGE-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- VALRGUZAMAZVHY-UHFFFAOYSA-N quinolin-5-yl cyanate Chemical compound C1=CC=C2C(OC#N)=CC=CC2=N1 VALRGUZAMAZVHY-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/14—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung neuer 1, 2, 4-Triazol-derivate Es wurde gefunden, daß man neue 1,2,4-Triazolderivate erhält, wenn man einen Cyansäureester der allgemeinen Formel ROCN, worin R einen gegebenenfalls substituierten aromatischen Rest bedeutet, mit etwa der halbmolaren Menge eines Dithiokohlensäureesterhydrazids der allgemeinen Formel in der R1 einen aliphatischen Rest und R2 einen gegebenenfalls substituierten aromatischen Rest bedeutet, bei Temperaturen zwischen - 20 bis 100"C in einem Lösungsmittel umsetzt und das entstandene 1,2,4-Triazolderivat der allgemeinen Formel in der R, R1 und R2 die oben angegebenen Bedeutungen besitzen, in üblicher Weise isoliert.Process for the preparation of new 1, 2, 4-triazole derivatives It has been found that new 1,2,4-triazole derivatives are obtained if a cyanic acid ester of the general formula ROCN, where R is an optionally substituted aromatic radical, with about the half molar amount of a dithiocarbonic acid ester hydrazide of the general formula in which R1 is an aliphatic radical and R2 is an optionally substituted aromatic radical, is reacted in a solvent at temperatures between -20 to 100 "C, and the resulting 1,2,4-triazole derivative of the general formula in which R, R1 and R2 have the meanings given above, isolated in the customary manner.
Als aromatische Reste R bzw. R2 kommen aromatische Kohlenwasserstoffreste mit bis zu 20 Kohlenstoffatomen im Ringsystem in Betracht. Die aromatischen Reste können als Substituenten beispielsweise tragen: Alkyl-, Aryl-, Alkylamino-, Acylamino-, Nitro-, Halogen-, Alkoxy-, Aroxy-, Acyloxy-, Carbonyl-, Carboxyl-, Carbonester, -amid, Sulfonyl-, Sulfonsäureester, -amid, Acyl-, Cyano-, Rhodanid-, Alkylmerkapto-, Arylmerkapto- oder Acylmerkaptogruppen. Aromatic hydrocarbon radicals come as aromatic radicals R and R2 with up to 20 carbon atoms in the ring system. The aromatic leftovers can carry as substituents, for example: alkyl, aryl, alkylamino, acylamino, Nitro, halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl, carbon esters, -amid, sulfonyl, sulfonic acid ester, amide, acyl, cyano, rhodanide, alkyl mercapto, Aryl mercapto or acyl mercapto groups.
Als aliphatische Reste R1 seien vorzugsweise geradkettige oder verzweigte Alkylreste mit 1 bis 12 Kohlenstoffatomen genannt. Aliphatic radicals R1 are preferably straight-chain or branched ones Called alkyl radicals with 1 to 12 carbon atoms.
Die als Ausgangsverbindungen verwendeten Cyansäureester können gemäß älteren Vorschlägen des Erfinders durch Umsetzung von hydroxylgruppenhaltigen Verbindungen mit Halogencyaniden bei Temperaturen, vorzugsweise unterhalb +65"C, gegebenenfalls in einem Lösungsmittel in Gegenwart einer Base hergestellt werden. The cyanic acid esters used as starting compounds can according to older proposals by the inventor by reacting compounds containing hydroxyl groups with halogen cyanides at temperatures, preferably below +65 "C, if appropriate be prepared in a solvent in the presence of a base.
Es können für das erfindungsgemäße Verfahren z. B. folgende Cyansäureester eingesetzt werden: Phenylcyanat, Mono- und Polyalkylphenylcyanate wie 3-Methyl-, 4-Isododecyl-, 4-Cyclohexyl-, 2-tert.-Butyl-, 3-Trifluormethyl-, 2,4-Dimethyl-, 3,5-Dimethyl-, 2,6-Diäthyl-, 4-Allyl-2-methoxyphenylcyanat; Arylphenylcyanate wie 4-Cyanatodiphenyl, Dialkylaminophenylcyanate wie 4-Dimethylamino-, 4-Dimethylamino-3-methylphenylcyanat ; Acylaminophenylcyanate wie Acetylaminophenylcyanat; Nitrophenylcyanate wie 4-Nitro-, 3-Nitro-, 4-Nitro-3-methyl, 3-Nitro-6-methyl- phenylcyanat; Halogenphenylcyanate wie 2-Chlor-, 3-Chlor-, 4-Chlor-, 2,4-Dichlor-, 2,6-Dichlor-, 3-Brom-, 4-Fluor-, 4-Jod-, 2-Chlor-6-methyl- phenylcyanat; Cyanatophenylcarbonsäure, -ester, -amide wie 4-Cyanatobenzoesäure, 2-Cyanatobenzoesäureäthylester, 2-Cyanatobenzoesäuremorpholid und -diäthylamid; Cyanatophenylsulfonsäure, -ester, -amide wie 4-Cyanatobenzolsulfonsäure; Alkoxyphenylcyanate wie 2-Methoxy-, 3-Methoxy-, 4-Isopropoxyphenylcyanat ; Phenoxyphenylcyanate wie 4-Cyanatodiphenyläther ; Acyloxyphenylcyanate wie 3-Acetoxyphenylcyanat; Acylphenylcyanate wie 4-Acetylphenylcyanat; 4Methylmerkaptophenylcyanat und 3-N,N-Dimethylcarbamylphenylcyanat; sowie a- und p-Naphthylcyanat und Chinolincyanate wie 5-Cyanatochinolin. It can be used for the inventive method, for. B. the following cyanic acid esters are used: phenyl cyanate, mono- and polyalkylphenyl cyanates such as 3-methyl-, 4-isododecyl, 4-cyclohexyl, 2-tert-butyl, 3-trifluoromethyl, 2,4-dimethyl, 3,5-dimethyl, 2,6-diethyl, 4-allyl-2-methoxyphenyl cyanate; Arylphenylcyanates such as 4-cyanatodiphenyl, dialkylaminophenyl cyanates such as 4-dimethylamino, 4-dimethylamino-3-methylphenyl cyanate ; Acylaminophenyl cyanates such as acetylaminophenyl cyanate; Nitrophenyl cyanates such as 4-nitro, 3-nitro-, 4-nitro-3-methyl, 3-nitro-6-methyl-phenyl cyanate; Halophenyl cyanates such as 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,6-dichloro, 3-bromine, 4-fluoro, 4-iodo-, 2-chloro-6-methyl-phenyl cyanate; Cyanatophenyl carboxylic acids, esters, amides such as 4-cyanatobenzoic acid, 2-cyanatobenzoic acid ethyl ester, 2-cyanatobenzoic acid morpholide and diethylamide; Cyanatophenylsulfonic acid, esters, amides such as 4-cyanatobenzenesulfonic acid; Alkoxyphenyl cyanates such as 2-methoxy, 3-methoxy, 4-isopropoxyphenyl cyanate; Phenoxyphenyl cyanate such as 4-cyanatodiphenyl ether; Acyloxyphenyl cyanates such as 3-acetoxyphenyl cyanate; Acyl phenyl cyanates such as 4-acetylphenyl cyanate; 4methyl mercaptophenyl cyanate and 3-N, N-dimethylcarbamylphenyl cyanate; as well as a- and p-naphthyl cyanate and quinoline cyanates such as 5-cyanatoquinoline.
Als für das Verfahren Verwendung findende Dithiokohlensäureesterhydrazide seien beispielsweise genannt: : S-Alkyl- (-äthyl,-isopropyl,-dodecyl)-N2-phenyl-dithiokohlensäureesterhydrazid sowie die entsprechenden, im Benzolkern ein- oder mehrmals folgende Substituenten besitzenden Derivate: Alkyl-(mit 1 bis 8 Kohlenstoffatomen), Nitro-, Alkoxy-(mit 1 bis 4 Kohlenstoffatomen), Phenoxy-, Dialkylamino- (mit 1 bis 4 Kohlenstoffatomen pro Alkylrest), Acetyl-, Propionyl-, Isobutyryl-, Benzoyl-, Alkylmerkapto- (mit 1 bis 4 Kohlenstoffatomen) oder Phenylmerkaptorest sowie Chloratome. Dithiocarbonic acid ester hydrazides used for the process are for example mentioned: S-alkyl- (-ethyl, -isopropyl, -dodecyl) -N2-phenyl-dithiocarbonic acid ester hydrazide and the corresponding substituents which follow one or more times in the benzene nucleus Own derivatives: alkyl (with 1 to 8 carbon atoms), nitro, alkoxy (with 1 to 4 carbon atoms), phenoxy, dialkylamino (with 1 to 4 carbon atoms per alkyl radical), acetyl, propionyl, isobutyryl, benzoyl, alkyl mercapto (with 1 to 4 carbon atoms) or phenyl mercapto radical and chlorine atoms.
Als Verbindung mit einem anellierten aromatischen Ringsystem- sei
beispielhaft das S-Methyl-N2-naphthyl-dithiokohlensäureesterhydrazid genannt.
Das
Verfahren sei am Beispiel der Umsetzung von Phenylcyanat mit S-Methyl-N2-phenyl-dithiokohlensäure-
Man kann die Komponenten zur Durchführung des Verfahrens in beliebiger Reihenfolge, vorzugsweise in einem der genannten Verdünnungsmittel, zusammengeben. Sie setzen sich im Molverhältnis Cyansäureester zu Dithiokohlensäureesterhydrazid wie 2 : 1 um und werden vorzugsweise im genannten Verhältnis von 2 : 1 eingesetzt. Ein Uberschuß-an einer der genannten Komponenten über das angegebene Verhältnis hinaus kann gegebenenfalls verwendet werden und hat keinen nachteiligen Einfluß auf den Reaktionsverlauf. Die Verfahrensprodukte - fallen, gegebenenfalls nach Einengen-des Lösungsmittels, aus und werden durch Absaugen isoliert. Die neuen Triazolderivate sind wertvolle Zwischenprodukte zur Herstellung von Pharmazeutika. You can use the components for carrying out the process in any Combine sequence, preferably in one of the diluents mentioned. They sit in the molar ratio of cyanate to dithiocarbonate hydrazide such as 2: 1 µm and are preferably used in the stated ratio of 2: 1. An excess of one of the components mentioned above the specified ratio also can be used if necessary and has no adverse influence on the course of the reaction. The products of the process - fall, if necessary after concentration Solvent, and are isolated by suction. The new triazole derivatives are valuable intermediate products in the manufacture of pharmaceuticals.
Beispiel 1 11,9 g (0,1 Mol) Phenylcyanat und 9,9 g (0,05 Mol) S-Methyl-N2-phenyl-dithiokohlensäureesterhydrazid werden bei 0. bis 10°C in 50 ml Aceton zusammengegeben. Nach 2stündigem Stehen bei Zimmertemperatur ist schwache Gelbfärbung eingetreten. Example 1 11.9 g (0.1 mol) of phenyl cyanate and 9.9 g (0.05 mol) of S-methyl-N2-phenyl-dithiocarbonic acid ester hydrazide are combined in 50 ml of acetone at 0 to 10 ° C. After standing for 2 hours Pale yellow color has occurred at room temperature.
Nach Abziehen des Lösungsmittels bei 35"C im Vakuum bleiben 22 g eines ölig-festen Rückstandes, aus dem nach Verrühren mit Äther und Umkristallisieren aus Alkohol 10 g (= 58,50/0 der Theorie) des vom Fp. 120,5"C erhalten werden.After the solvent has been stripped off at 35 "C. in vacuo, 22 g of an oily-solid residue remain, from which, after stirring with ether and recrystallization from alcohol, 10 g (= 58.50 / 0 of theory) of the of m.p. 120.5 "C can be obtained.
Analyse: C16H14N4OS2 (342).Analysis: C16H14N4OS2 (342).
Berechnet C 55,8, H 4,1, N 16,4, 0 4,68, S 18,70/0; Molgewicht 342; gefunden C 56,18, H 4,31, N 16,58, 0 5,02, S 18,650/o; Molgewicht 346/347. Calculated C 55.8, H 4.1, N 16.4, 0 4.68, S 18.70 / 0; Molecular weight 342; found C 56.18, H 4.31, N 16.58, 0 5.02, S 18.650 / o; Molecular weight 346/347.
Beispiel 2 Aus den gleichen Komponenten wie im Beispiel 1 erhält man nach lstündigem Erhitzen in Benzol auf 50 bis 60"C das gleiche Produkt wie im Beispiel 1 (identisches IR-Spektrum). Example 2 Obtained from the same components as in Example 1 after heating in benzene at 50 to 60 "C for 1 hour, the same product as in Example 1 (identical IR spectrum).
Beispiel 3 Zu einer auf 0°C abgekühlten Lösung von 15,3 g (0,1 Mol) 3-Chlorphenylcyanat in 30 ml Aceton gibt man 9,9 g (0,05 Mol) S-Methyl-N2-phenyldithiokohlensäureesterhydrazid. Unter Erwärmen und gleichzeitigem Lösen der letztgenannten Komponente tritt Reaktion ein. Nach einiger Zeit kristallisieren 6,1 g (= 32,50/0 der Theorie) des in Form farbloser Kristalle vom Fp. 870C aus.Example 3 9.9 g (0.05 mol) of S-methyl-N2-phenyldithiocarbonic acid ester hydrazide are added to a solution, cooled to 0 ° C., of 15.3 g (0.1 mol) of 3-chlorophenyl cyanate in 30 ml of acetone. A reaction occurs with heating and simultaneous dissolution of the last-mentioned component. After some time, 6.1 g (= 32.50 / 0 of theory) of the crystallize in the form of colorless crystals with a melting point of 870C.
Aus dem Filtrat erhält man nach Abziehen des Lösungsmittels weitere 17,5 g eines ölig-kristallinen Rückstandes, aus dem analog Beispiel 1 weitere 5 g des gleichen Produktes gewonnen werden können. More are obtained from the filtrate after the solvent has been stripped off 17.5 g of an oily-crystalline residue, from which, analogously to Example 1, a further 5 g of the same product can be obtained.
Analyse: C16Hl3CIN4OS2 (376,5).Analysis: C16H13CIN4OS2 (376.5).
Berechnet C 51,0, H 3,46, N 14,9, 0 4,25, S 17,0, Cl 9,450/o; gefunden C 51,03, H 3,82, N 14,78, 0 4,94, S 17,0, Cl 8,700/0. Calculated C 51.0, H 3.46, N 14.9, 0 4.25, S 17.0, Cl 9.450 / o; found C 51.03, H 3.82, N 14.78, 0 4.94, S 17.0, Cl 8.700 / 0.
Beispiel 4 Analog Beispiel 1 erhält man mit 14,7 g (0,1 Mol) 2,4-Dimethylphenylcyanat statt 11,9 g (0,1 Mol) Phenylcyanat 10,1 (= 550/0 der Theorie) des vom Fp. 97"C.Example 4 Analogously to Example 1, 14.7 g (0.1 mol) of 2,4-dimethylphenyl cyanate are obtained instead of 11.9 g (0.1 mol) of phenyl cyanate 10.1 (= 550/0 of theory) of m.p. 97 "C.
Analyse: C18H18N40S2 (370).Analysis: C18H18N40S2 (370).
Berechnet C 58,4, H 4,86, N 15,1, 0 4,32, S 17,30/0; Molgewicht 370; gefunden C 58,38, H 5,09, N 14,80, 0 4,71, S 17,350/o; Molgewicht 371 bis 375. Calculated C 58.4, H 4.86, N 15.1, 0 4.32, S 17.30 / 0; Molecular weight 370; found C 58.38, H 5.09, N 14.80, 0 4.71, S 17.350 / o; Molecular weight 371 to 375.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF45503A DE1219031B (en) | 1965-03-12 | 1965-03-12 | Process for the preparation of new 1,2,4-triazole derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF45503A DE1219031B (en) | 1965-03-12 | 1965-03-12 | Process for the preparation of new 1,2,4-triazole derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1219031B true DE1219031B (en) | 1966-06-16 |
Family
ID=7100527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF45503A Pending DE1219031B (en) | 1965-03-12 | 1965-03-12 | Process for the preparation of new 1,2,4-triazole derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1219031B (en) |
-
1965
- 1965-03-12 DE DEF45503A patent/DE1219031B/en active Pending
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