DE1241835B - Process for the preparation of 1, 3-disubstituted 5-amino-1, 2, 4-triazoles - Google Patents
Process for the preparation of 1, 3-disubstituted 5-amino-1, 2, 4-triazolesInfo
- Publication number
- DE1241835B DE1241835B DE1965F0046813 DEF0046813A DE1241835B DE 1241835 B DE1241835 B DE 1241835B DE 1965F0046813 DE1965F0046813 DE 1965F0046813 DE F0046813 A DEF0046813 A DE F0046813A DE 1241835 B DE1241835 B DE 1241835B
- Authority
- DE
- Germany
- Prior art keywords
- cyanate
- acid hydrazide
- optionally
- triazoles
- amino
- 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
- -1 1, 3-disubstituted 5-amino-1, 2, 4-triazoles Chemical class 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 150000003852 triazoles Chemical class 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BDVNNPOIBWADPU-UHFFFAOYSA-N (4-chlorophenyl) cyanate Chemical compound ClC1=CC=C(OC#N)C=C1 BDVNNPOIBWADPU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001913 cyanates Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UGMKNMPRUHJNQK-UHFFFAOYSA-N (4-methylphenyl) cyanate Chemical compound CC1=CC=C(OC#N)C=C1 UGMKNMPRUHJNQK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 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 compound [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
- 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
- RMNOKYKUILWHMR-UHFFFAOYSA-N (4-methyl-2-sulfanylphenyl) cyanate Chemical compound CC1=CC(=C(C=C1)OC#N)S RMNOKYKUILWHMR-UHFFFAOYSA-N 0.000 description 1
- XEGLCJPLASCMIK-UHFFFAOYSA-N 1H-imidazole-2-sulfonohydrazide Chemical compound N1C(=NC=C1)S(=O)(=O)NN XEGLCJPLASCMIK-UHFFFAOYSA-N 0.000 description 1
- KPWDGTGXUYRARH-UHFFFAOYSA-N 2,2,2-trichloroethanol Chemical compound OCC(Cl)(Cl)Cl KPWDGTGXUYRARH-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
- ZCLXQTGLKVQKFD-UHFFFAOYSA-N 3-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1 ZCLXQTGLKVQKFD-UHFFFAOYSA-N 0.000 description 1
- FSFGOBLZOQKGFL-UHFFFAOYSA-N 4-acetylbenzenesulfonohydrazide Chemical compound CC(=O)C1=CC=C(S(=O)(=O)NN)C=C1 FSFGOBLZOQKGFL-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
- CXVHUSXCRPOYKL-UHFFFAOYSA-N 4-hydroxybenzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=C(O)C=C1 CXVHUSXCRPOYKL-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- VUQUURTXAPNOEC-UHFFFAOYSA-N 4-methylsulfanylbenzenesulfonohydrazide Chemical compound CSC1=CC=C(S(=O)(=O)NN)C=C1 VUQUURTXAPNOEC-UHFFFAOYSA-N 0.000 description 1
- QSFQGKRLZCXSPE-UHFFFAOYSA-N 4-nitrobenzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 QSFQGKRLZCXSPE-UHFFFAOYSA-N 0.000 description 1
- ALLNAVCIMOJNMN-UHFFFAOYSA-N 4-phenylpyrazol-3-one Chemical compound O=C1N=NC=C1C1=CC=CC=C1 ALLNAVCIMOJNMN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- DMLNILXOWVXYBZ-UHFFFAOYSA-N 9H-carbazole-1-sulfonohydrazide Chemical compound N1C2=CC=CC=C2C2=C1C(S(=O)(=O)NN)=CC=C2 DMLNILXOWVXYBZ-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-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
- 101100219382 Caenorhabditis elegans cah-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 229910018954 NaNH2 Inorganic materials 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 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
- PAJAHHSOSQAXRR-UHFFFAOYSA-N [4-(dimethylamino)-3-methylphenyl] cyanate Chemical compound CN(C1=C(C=C(C=C1)OC#N)C)C PAJAHHSOSQAXRR-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 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
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- AOHLYBLFCMSIFD-UHFFFAOYSA-N cyclohexanesulfonohydrazide Chemical compound NNS(=O)(=O)C1CCCCC1 AOHLYBLFCMSIFD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- YOSRAPGXBADCSA-UHFFFAOYSA-N hexane-1-sulfonohydrazide Chemical compound CCCCCCS(=O)(=O)NN YOSRAPGXBADCSA-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VKHZYWVEBNIRLX-UHFFFAOYSA-N methanesulfonohydrazide Chemical compound CS(=O)(=O)NN VKHZYWVEBNIRLX-UHFFFAOYSA-N 0.000 description 1
- 239000000401 methanolic extract Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QUSFOLYSOPZYIK-UHFFFAOYSA-N naphthalen-1-yl cyanate Chemical compound C1=CC=C2C(OC#N)=CC=CC2=C1 QUSFOLYSOPZYIK-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000010915 one-step procedure Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XBCFRZRVCDUSGX-UHFFFAOYSA-N phenylmethanesulfonohydrazide Chemical compound NNS(=O)(=O)CC1=CC=CC=C1 XBCFRZRVCDUSGX-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- YSWKNOTVKJDDGM-UHFFFAOYSA-N propane-2-sulfonohydrazide Chemical compound CC(C)S(=O)(=O)NN YSWKNOTVKJDDGM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- WCTWEMPLTHNDLQ-UHFFFAOYSA-N quinoline-2-sulfonohydrazide Chemical compound C1=CC=CC2=NC(S(=O)(=O)NN)=CC=C21 WCTWEMPLTHNDLQ-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229950004616 tribromoethanol Drugs 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)
Description
Verfahren zur Herstellung von 1,3-disubstituierten 5-Amino- 1 2,4-triazolen 3-Amino-1,2,4-triazole bilden sich bei Dehydratation von Acyl-aminoguanidinen (J. T h i e 1 e, K.Heidenreich, Ber., 26, 2598 [1893], und J. Thiele, W. Manchot, Ann., 303, 33 [1898]): 3-Acylamino-1.2,4-triazole erhält man auch aus Benzoyl-dicyanamid und Hydrazin (USA.-Patentschrift 2 399 598 = C. A., 40, 4227 [1946]): Es wurde nun gefunden, daß man 1,3-disubstituierte 5-Amino-t,2,4-triazole erhält, wenn man 1 Mol eines Sulfonsäurehydrazids der allgemeinen Formel 1 R1-SO2-NH-NH2 (1) in der R1 für einen gegebenenfalls substituierten aliphatischen oder gegebenenfalls substituierten aromatischen oder heterocyclischen Rest steht, gegebenenfalls stufenweise mit 2 Mol eines Cyansäureesters der allgemeinen Formel 11 R-O-CN (II) in der R einen Halogenalkyl- oder einen gegebenenfalls substituierten aromatischen Rest, der auch mit heterocyclischen Resten verbunden sein kann, bedeutet, bei Temperaturen zwischen etwa 0 und etwa 180 C, vorzugsweise 20 bis 120 C, gegebenenfalls in einem Verdünnungsmittel und gegebenenfalls in Anwesenheit einer Base, umsetzt. Die nach dem erfindungsgemäßen Verfahren erhältlichen Verbindungen sind neu und haben die allgemeine Formel III in der R und R1 die oben angegebene Bedeutung haben.Process for the preparation of 1,3-disubstituted 5-amino-1 2,4-triazoles 3-Amino-1,2,4-triazoles are formed on dehydration of acyl-aminoguanidines (J. T hie 1 e, K. Heidenreich, Ber., 26, 2598 [1893], and J. Thiele, W. Manchot, Ann., 303, 33 [1898]): 3-Acylamino-1,2,4-triazoles are also obtained from benzoyl-dicyanamide and hydrazine (US Pat. No. 2,399,598 = CA, 40, 4227 [1946]): It has now been found that 1,3-disubstituted 5-amino-t, 2,4-triazoles are obtained if 1 mole of a sulfonic acid hydrazide of the general formula 1 R1-SO2-NH-NH2 (1) is used in R1 for one optionally substituted aliphatic or optionally substituted aromatic or heterocyclic radical, optionally stepwise with 2 mol of a cyanate of the general formula 11 RO-CN (II) in which R is a haloalkyl or an optionally substituted aromatic radical which can also be linked to heterocyclic radicals , means, at temperatures between about 0 and about 180 ° C., preferably 20 to 120 ° C., optionally in a diluent and optionally in the presence of a base. The compounds obtainable by the process according to the invention are new and have the general formula III in which R and R1 have the meaning given above.
Das Verfahren sei an Hand der folgenden beispielhaften Reaktionsgleichungen erläutert: Es kann in einer Stufe durchgeführt werden, indem man von vornherein 2 Mol Cyansäureester auf 1 Mol Sulfonsäurehydrazid einwirken läßt und direkt die Triazole (III) erhält: Die Temperaturgrenzen liegen zwischen etwa 0 und etwa 180cd.The process is explained with the aid of the following reaction equations as an example: It can be carried out in one stage by allowing 2 mol of cyanate to act on 1 mol of sulfonic acid hydrazide from the outset and the triazoles (III) to be obtained directly: The temperature limits are between about 0 and about 180cd.
Man kann das Verfahren aber auch schrittweise durchführen, indem man zunächst die Zwischenprodukte IV herstellt und diese mit einem weiteren Mol Cyansäureester in die Triazole (III) überführt. The procedure can also be carried out step-by-step by one first prepares the intermediates IV and this with a further mol Cyanic acid ester converted into the triazoles (III).
Dabei können auch die offenen 2 : 1-Addukte V gegebenenfalls isoliert und nachträglich durch Erhitzen in einem Lösungsmittel in die Triazole (III) übergeführt werden. Man kann ferner durch Um- setzung von 2 Mol ROCN mit 1 Mol R1SO2NHNH2 in der Kälte zunächst die 2 : 1-Additionsverbindungen V herstellen und diese durch Erhitzen in die Triazole (III) überführen: Da das zweite Mol Cyansäureester nur als CN-Quelle dient ist es für die zweite Stufe der Reaktion gleichgültig ob R2 R ist oder davon verschieden ist. R2OCN soll lediglich in die Gruppe der gemäß vorherstehender Definition von ROCN für die Reaktion verwendbaren Cyansäureester fallen.The open 2: 1 adducts V can also optionally be isolated and subsequently converted into the triazoles (III) by heating in a solvent. Furthermore, by reacting 2 moles of ROCN with 1 mole of R1SO2NHNH2 in the cold, the 2: 1 addition compounds V can first be prepared and these can be converted into the triazoles (III) by heating: Since the second mole of cyanate only serves as a CN source, it is irrelevant for the second stage of the reaction whether R2 is R or is different from it. R2OCN is only intended to fall into the group of cyanic acid esters which can be used for the reaction according to the above definition of ROCN.
Halogenalkylreste R sind z. B. Kohlenwasserstoffreste mit bis zu 12 Kohlenstoffatomen, die vorzugsweise in ;-Stdlung Fluor-, Brom-. Chlor- oder Jodatome tragen. Haloalkyl radicals R are, for. B. hydrocarbon residues with up to 12 carbon atoms, preferably in; -Stdlung fluorine, bromine-. Chlorine or iodine atoms wear.
Als aliphatische Reste R, seien vorzugsweise geradkettige oder verzweigte Alkylreste mit l bis 12 Kohl.llstoffatomen genannt. Als aromatische Reste R und R1 kommen aromatische Kohlen wasserstoffreste mit bis zu 20 Kohlenstoffatomen im Ringsystem in Betracht. Die aromatischen Reste R bzw. Aliphatic radicals R are preferably straight-chain or branched Called alkyl radicals with 1 to 12 carbon atoms. As aromatic radicals R and R1 are aromatic hydrocarbon residues with up to 20 carbon atoms in the Ring system into consideration. The aromatic radicals R and
R1 können als Substituenten beispielsweise tragen: Alkyl-. Aryl-. Alkylamino-. Acylamino-, Nitro-.R1 can have, for example, as substituents: alkyl-. Aryl. Alkylamino-. Acylamino, nitro.
Hilogen-. Alkoxy-. Aroxy-, Acyloxy-, Carbonyl-, Carboxyl-, Carbonester, -amid- Sulfonyl-, Sulfonsäureester. -amid-. Acyl-. Cyano-. Rhodanid-. Alkylmerkupto-' Arylmerkapto- oder Acylmerkaptogruppein.Hilogen-. Alkoxy. Aroxy, acyloxy, carbonyl, carboxyl, carbon esters, -amid- sulfonyl, sulfonic acid esters. -amid-. Acyl-. Cyano. Rhodanide-. Alkyl mercup- ' Aryl mercapto or acyl mercapto groups.
Die als A usgangsverbind ungen verwendeten Cyansäureester sind bekannt. The cyanic acid esters used as starting compounds are known.
Es können für das erfindungsgemäße Verfahren z. B. folgende Cyansäureester eingesetzt werden: Phenylcyanat. Mono- und Polyalkylphenylcyanate, die 3-Nlethyl-. 4-lsododecyl-, 4-Cyclohexyl-, 2-tert.-Butyl-. 3-Trifluormethyl-. ',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 3-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, wie2-Methoxy-, 3-Methoxy-, 4-Isopropoxyphenylcyanat; Phenoxyphenylcyanate, wie 4-Cyanatodiphenyläther; Acyloxyphenylcyanate, wie 3-Acetoxyphenylcyanat; Acylphenylcyanate, wie 4-Acetylphenylcyanat; 4-Methylmerkaptophenylcyanat und 3-N,N-Dimethylcarbamylphenylcyanat, sowie .Æ- und t;-Naphthylcyanat und Chinolincyanate, wie 5-Cyanatochinolin, und die Cyansäureester beispielsweise folgender Alkohole: ß,ß,ß-Trichloräthanol, ß,ß,ß-Trifluoräthanol, p,fS -Tribromäthanol, ß,ß-Dichloräthanol, H - (CF2 - Cfl.)5CH2OH Als Sulfonsäurehydrazide können, gegebenenfalls in Form ihrer sauren Salze, wie z. B. Hydrochlorid, beispielsweise eingesetzt werden: Methansulfonsäurehydrazid, Athansulfonsäurehydrazid, Isopropansulsonsäurehydrazid, Hexansulfonsäurehydrazid, Cyclohexansulfonsäurehydrazid, Phenylmethansulfonsäurehydrazid, Benzolsulfonsäurehydrazid, α- oder ß-Naphthalinsulfonsäurehydrazid, 2-, 3- oder 4-Toluolsulfonsäurehydrazid, 2-, 3- oder 4-Chlor-(Brom-, Fluor-) benzolsulfonsäurehydrazid, 2-, 3- oder 4-Hydroxybenzolsulfonsäurehydrazid, 2-, 3- oder 4-Dimethylaminotenzolsulfonsäurehydrazid, 2-, 3- oder 4-Nitrobenzolsulfonsäurehydrazid, 2-, 3- oder 4-Acetylbenzolsulfonsäurehydrazid, 2-, 3- oder 4-Methoxy-(Athoxy-, Isopropoxy-) benzolsulfonsäurehydrazid, 2-, 3- oder 4-Methylmerkapto-benzolsulfonsäurehydrazid, Chinolinsulfonsäurehydrazide, Carbazolsulfonsäurehydrazide, Phenylpyrazolonsulfonsäurehydrazide, Imidazolsulfonsäurehydrazide. It can be used for the inventive method, for. B. the following cyanic acid esters are used: phenyl cyanate. Mono- and polyalkylphenylcyanates, the 3-Nlethyl-. 4-isododecyl-, 4-cyclohexyl-, 2-tert-butyl-. 3-trifluoromethyl-. ', 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; : Nitrophenylcyanate. like 4-nitro-. 3-nitro. 4-nitro-3-methyl, 3-nitro-6-methyl-phenyl cyanate; Halophenyl cyanates, like 3-chloro-. 3-chlorine-. 4-chlorine, 2,4-dichloro, 2,6-dichloro, 3-bromo, 4-fluoro, 4-iodo-, 2-chloro-6-methyl-phenyl cyanate; Cyanatophenylcarboxylic acids, esters, amides, such as 4-cyanatobenzoic acid, 2-cyanatobenzoic acid ethyl ester, 2-cyanatobenzoic acid morpholide and diethylamide; Cyanatophenylsulphonic acid, esters, amides, such as 4-cyanatobenzenesulphonic 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; Acylphenylcyanate, such as 4-acetylphenyl cyanate; 4-methyl mercaptophenyl cyanate and 3-N, N-dimethylcarbamylphenyl cyanate, as well as .Æ- and t; -naphthyl cyanate and quinoline cyanates, such as 5-cyanatoquinoline, and the cyanic acid esters of the following alcohols, for example: ß, ß, ß-trichloroethanol, ß, ß, ß-trifluoroethanol, p, fS -tribromoethanol, ß, ß-dichloroethanol, H - (CF2 - Cfl.) 5CH2OH as sulfonic acid hydrazides can, optionally in the form of their acid salts, such as. B. hydrochloride, for example the following are used: methanesulphonic acid hydrazide, athanesulphonic acid hydrazide, isopropanesulphonic acid hydrazide, Hexanesulfonic acid hydrazide, cyclohexanesulfonic acid hydrazide, phenylmethanesulfonic acid hydrazide, Benzenesulfonic acid hydrazide, α- or ß-naphthalenesulfonic acid hydrazide, 2-, 3- or 4-toluenesulphonic acid hydrazide, 2-, 3- or 4-chloro (bromine, fluoro) benzenesulphonic acid hydrazide, 2-, 3- or 4-hydroxybenzenesulphonic acid hydrazide, 2-, 3- or 4-dimethylaminotenzenesulphonic acid hydrazide, 2-, 3- or 4-nitrobenzenesulphonic acid hydrazide, 2-, 3- or 4-acetylbenzenesulphonic acid hydrazide, 2-, 3- or 4-methoxy- (ethoxy-, isopropoxy-) benzenesulphonic acid hydrazide, 2-, 3- or 4-methylmercaptobenzenesulfonic acid hydrazide, quinoline sulfonic acid hydrazide, carbazole sulfonic acid hydrazide, Phenylpyrazolone sulfonic acid hydrazide, imidazole sulfonic acid hydrazide.
Als Vcrdünnungsmittel kommen z. B. organische Lösungsmittel, wie Alkohole, Ketone, Äther, Nitrile, Ester, Amide, aromatische und aliphatische, gegebenenfälls nitrierte oder halogenierte Kohlenwasserstoffe oder Wasser in Betracht. Es seien hier beispielsweise genannt: Methanol, Äthanol, Aceton, Diäthyläther, Acetonitril, Essigester, Dimethylformamid, Benzol, Petroläther, Nitrobenzol, Nitromethan, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol. As diluents, for. B. organic solvents, such as Alcohols, ketones, ethers, nitriles, esters, amides, aromatic and aliphatic, if necessary nitrated or halogenated hydrocarbons or water. Be there named here for example: methanol, ethanol, acetone, diethyl ether, acetonitrile, Ethyl acetate, dimethylformamide, benzene, petroleum ether, nitrobenzene, nitromethane, chloroform, Carbon tetrachloride, chlorobenzene.
Als die Reaktion fördernde Basen können beispielsweise in katalytischen bis molaren Mengen zugesetzt werden: Alkalihydroxide, -carbonate, -amide. -hydride. -alkoholate. -metalle, z. B. NaOH, KOH. Na-CO:1, K2CO:3. Li2CO:3, NaHCO:, NaNH2, NaH, NaOCH:Bn KOCH5. Na, sowie entsprechende Erdalkaliderivate, wie z. B. Ca(OH)2, Ba(OH)2, CaH2, oder tertiäre Amine, wie z. B. Triäthylamin, Diäthylanilin, Pyridin, Chinolin. As the reaction promoting bases, for example, in catalytic until molar amounts are added: alkali hydroxides, carbonates, amides. hydrides. alcoholates. metals, e.g. B. NaOH, KOH. Na-CO: 1, K2CO: 3. Li2CO: 3, NaHCO :, NaNH2, NaH, NaOCH: Bn KOCH5. Na, and corresponding alkaline earth derivatives, such as. B. Ca (OH) 2, Ba (OH) 2, CaH2, or tertiary amines, such as. B. triethylamine, diethylaniline, pyridine, Quinoline.
Zur Durchführung der Reaktion in einer Stufe gibt man die Komponenten im Molverhältnis Cyansäureestergruppe zu Sulfäydrazidgruppe gleich 2 :1 zusammen, vorzugsweise in einem flüssigen Medium und gegebenenfalls unter Zusatz einer Base, und erwärmt auf die Reaktionstemperatur. Im allgemeinen fallen die Triazole aus und können, gegebenenfalls nach Einengen des Lösungsmittels, durch Absaugen isoliert und so von den in Lösung bleibenden abgespaltenen Phenolen getrennt werden. To carry out the reaction in one stage, the components are added in the molar ratio of cyanate ester group to sulfaydrazide group equal to 2: 1 together, preferably in a liquid medium and optionally with the addition of a base, and heated to the reaction temperature. In general, the triazoles precipitate and can, if appropriate after concentrating the solvent, isolated by suction and so separated from the split off phenols that remain in solution.
Bei der zweistufigen Verfahrensweise stellt man zunächst das Zwischenprodukt IV her. Dann wird dieses mit 1 Mol Cyansäureester, vorzugsweise in einem flüssigen Medium und gegebenenfalls in Anwesenheit einer Base, umgesetzt. Die Reaktion verläuft dann in gleicher Weise wie bei der einstufigen Verfahrensweise. Man kann auch zunächst durch Umsatz von 2 Mol ROCN mit 1 Mol R,SO NHNH2 das Zwischenprodukt V, gegebenenfalls stufenweise über IV, herstellen und anschließend durch Erhitzen, gegebenenfalls in einem Lösungsmittel, ringschließen. In the two-stage procedure, the intermediate product is prepared first IV ago. Then it will be this with 1 mole of cyanate, preferably in a liquid medium and optionally in the presence of a base. The reaction then proceeds in the same way as in the one-step procedure. The intermediate product can also be obtained first by reacting 2 moles of ROCN with 1 mole of R, SO NHNH2 V, if necessary in stages via IV, and then by heating, optionally in a solvent, ring-closing.
Die neuen Triazolderivate (III) sind wertvolle Zwischenprodukte für die Herstellung von Pharmazeutika. The new triazole derivatives (III) are valuable intermediates for the manufacture of pharmaceuticals.
Beispiel 1 6,8 g (0,02 Mol) des aus α-Naphthylcyanat und Benzolsulfonsäurehydrazid hergestellten Produktes werden mit 3,1 g (0,02 Mol) 4-Chlorphenylcyanat in 30 ml Propanol 8 Stunden am Rückfluß gekocht.Example 1 6.8 g (0.02 mol) of the product prepared from α-naphthyl cyanate and benzenesulphonic acid hydrazide are refluxed for 8 hours with 3.1 g (0.02 mol) of 4-chlorophenyl cyanate in 30 ml of propanol.
Nach etwa der Hälfte der Zeit wurde 1 ml Triäthylamin zugesetzt. Nach Abkühlen und Absaugen fallen 3,7 g (51"/(, der Theorie) des vom F. 194 bis 197 C aus; starke Banden bei 6,08 und 6,43 .About half the time, 1 ml of triethylamine was added. After cooling and suctioning off, 3.7 g (51 "/ (of theory) des from m.p. 194 to 197 ° C; strong bands at 6.08 and 6.43.
Analyse: C18H14N4O3S (Molgewicht 366) Berechnet: C 59,00. H 3,85, N 15,30, 0 13,10, S 8.75%; gefunden: C 59,07, H 3.97, N 15,35, 0 13,44, S 8,74%.Analysis: C18H14N4O3S (molecular weight 366) Calculated: C 59.00. H 3.85, N 15.30, 0 13.10, S 8.75%; found: C 59.07, H 3.97, N 15.35, 0 13.44, S 8.74%.
Beispiel 2 2,9 g (10 mMol) ß-N-(Phenoxy-imino-methyl)-benzolsulfonsäurehydrazid (hergestellt aus Phenylcyanat und Benzolsulfonsäurehydrazid) werden mit 1,23 g Phenylcyanat in 30 ml Xylol 1 Stunde am Rückfluß gekocht. Nach Abdestillieren des Xylols wird der teils kristalline Rückstand mit Äther gewaschen und auf Ton gestrichen. 2 g (63% der Theorie) des vom F. 162 bis 163 C.Example 2 2.9 g (10 mmol) of β-N- (phenoxy-imino-methyl) -benzenesulfonic acid hydrazide (prepared from phenyl cyanate and benzenesulfonic acid hydrazide) are refluxed with 1.23 g of phenyl cyanate in 30 ml of xylene for 1 hour. After the xylene has been distilled off, the partly crystalline residue is washed with ether and painted on clay. 2 g (63% of theory) of the from F. 162 to 163 C.
Analyse: C14H12N4O3S (Molgewicht 316) Berechnet: C 53,20, H 3.80. N 17,70, 0 15,20, 5 10,10%; gefunden: C 53.82, H 4.08, N 17.74. 0 15,36, S 9,35%.Analysis: C14H12N4O3S (molecular weight 316) Calculated: C 53.20, H 3.80. N 17.70, 0 15.20, 5 10.10%; found: C 53.82, H 4.08, N 17.74. 0 15.36, S 9.35%.
IR-Spektrum: Starke Banden bei 6,03 und 6,43 µ. IR spectrum: strong bands at 6.03 and 6.43 μ.
Beispiel 3 4,6 g (14,5 mMol) p-N-k2,4-Dimethylphenoxy)-imino-methyl]-benzolsulfonsäurehydrazid (hergestellt aus 2,4-Dimethylphenylcyanat und Benzolsulfonsäurehydrazid) werden mit 2,3 g (15 mMol) 4-Chlorphenylcyanat 5 Minuten in 30 ml Toluol unter Rückfluß gekocht. 2,4 g (480/o der Theorie) des vom F. 188 bis 190=C (Zersetzung) fallen aus und werden durch Absaugen isoliert.Example 3 4.6 g (14.5 mmol) of pN-k2,4-dimethylphenoxy) -imino-methyl] -benzenesulfonic acid hydrazide (prepared from 2,4-dimethylphenyl cyanate and benzenesulfonic acid hydrazide) are mixed with 2.3 g (15 mmol) of 4- Chlorophenyl cyanate refluxed in 30 ml of toluene for 5 minutes. 2.4 g (480 / o of theory) des from F. 188 to 190 = C (decomposition) precipitate and are isolated by suction.
Analyse: C16HI6N40:sS (Molgewicht 344) Berechnet ... C 55,80, H 4,68, 0 13,90, S 9,30%; gefunden ... C 55,74, H 5,05, 0 13,99, S 9,42%.Analysis: C16HI6N40: sS (molecular weight 344) Calculated ... C 55.80, H 4.68, 0 13.90, S 9.30%; Found ... C 55.74, H 5.05, 0 13.99, S 9.42%.
IR-Spektrum: Starke Banden bei 6,08 und 6,45 µ. IR spectrum: strong bands at 6.08 and 6.45 μ.
Beispiel 4 In eine Lösung von 13,3 g (100 mMol) 4-Methylphenylcyanat in 50 ml Äthanol werden 8.6 g (50 mMol) Benzolsulfonsäurehydrazid eingetragen. Example 4 In a solution of 13.3 g (100 mmol) of 4-methylphenyl cyanate 8.6 g (50 mmol) of benzenesulfonic acid hydrazide are added to 50 ml of ethanol.
Nach anfänglicher Selbsterwärmung auf 45 C wird weitere 2 Stunden unter Rückfluß gekocht. Beim Abkühlen kristallisieren 9,2 g Substanz aus. Diese wird mit vier Portionen zu je 25 ml kaltem Methanol extrahiert, der Methanolextrakt eingedampft. Man erhält so 5 g des vom F. 150 bis 154C.After initial self-heating to 45 ° C., the mixture is refluxed for a further 2 hours. 9.2 g of substance crystallize out on cooling. This is extracted with four portions of 25 ml of cold methanol each, and the methanol extract is evaporated. This gives 5 g of des from F. 150 to 154C.
Analyse: C13H14N4O3S (Molgewicht 330) Berechnet . . C 54,50, H 4,27, N 17,00, 0 14 50" .,; gefunden . . C 54,84. H 4,38, N 16.63, 0 14.37t'".Analysis: C13H14N4O3S (molecular weight 330) calculated. . C 54.50, H 4.27, N 17.00, 0 14 50 ".,; Found.. C 54.84. H 4.38, N 16.63, 0 14.37t '".
Molgewicht: berechnet 330, gefunden 331. Molecular weight: calculated 330, found 331.
IR-Spektrum: Starke Banden bei 6,10 und 6,54 .. IR spectrum: strong bands at 6.10 and 6.54 ..
Beispiel 5 13,3 g (0,1 Mol) 4-Methylphenylcyanat werden in 50ml Alkohol vorgelegt und 8,6 g (0.05 Mol) Benzolsulfonsäurehydrazid und 2 ml Triäthylamin eingetragen. Nach 2stündigem Rückflußkochen wird mit Wasser versetzt: es fällt ein Öl aus, das langsam zäh und teils kristallin wird. Nach Streichen auf Ton erhält man 7,3 g (44"!o der Theorie) des gleichen Produktes wie im Beispiel 4 (identisches IR-Spektrum). Example 5 13.3 g (0.1 mol) of 4-methylphenyl cyanate are dissolved in 50 ml of alcohol submitted and registered 8.6 g (0.05 mol) of benzenesulfonic acid hydrazide and 2 ml of triethylamine. After refluxing for 2 hours, water is added: an oil precipitates which slowly becomes tough and partly crystalline. After brushing on clay, 7.3 g (44 "! O the theory) of the same product as in Example 4 (identical IR spectrum).
F. 155 bis 157 C (aus Alkohol).F. 155 to 157 C (from alcohol).
Beispiel 6 Zu einer Suspension von 8,6 g (0.05 Mol) Benzolsulfonsäurehydrazid in 50 ml Alkohol giht man 15,3 g (0,1 Mol) 4-Chlorphenylcyanat. Die exotherme Reaktion wird unter 0 C gehalten. Der enttandene Brei wird abgesaugt und gewaschen. Man erhält 15,8 g (66% der Theorie) des weitere 20010 unreineres Produkt erhält man aus dem Filtrat. F. 11X'C.Example 6 15.3 g (0.1 mol) of 4-chlorophenyl cyanate are added to a suspension of 8.6 g (0.05 mol) of benzenesulphonic acid hydrazide in 50 ml of alcohol. The exothermic reaction is kept below 0.degree. The resulting pulp is suctioned off and washed. 15.8 g (66% of theory) are obtained a further 20010 impure product is obtained from the filtrate. F. 11X'C.
Analyse: C20H16Cl2N4O4S (Molgewicht 479) Berechnet: C 50,10, H 3,34, Cl 14,80, N 11,70, 0 13,30, S 6,70>i/n; gefunden: C 50,51, H 3,56, Cl 14,80, N 11,57, 0 13,28, S 6,60%.Analysis: C20H16Cl2N4O4S (molecular weight 479) Calculated: C 50.10, H 3.34, Cl 14.80, N 11.70, 0 13.30, S 6.70> i / n; found: C 50.51, H 3.56, Cl 14.80, N 11.57, 0 13.28, S 6.60%.
6,5 g dieses Produktes werden 15 Minuten in 30 ml Toluol am Rückfluß gekocht. Nach Verrühren mit Äther werden 3 g (63% der Theorie) des vom F. 166 bis 167 C durch Absaugen gewonnen.6.5 g of this product are refluxed in 30 ml of toluene for 15 minutes. After stirring with ether, 3 g (63% of theory) of the from the F. 166 to 167 C obtained by suction.
Analyse: C14H11CIN4O3S (Molgewicht 350,5) Berechnet: C48,0, H3,l4, Cl l0,l5 16,00, O 13,70, O 13,70, S 9,14°lo; gefunden: C 48,0, H 3,21, Cl 10,10, N 15,92, 0 13,78, S 9,29%.Analysis: C14H11CIN4O3S (molecular weight 350.5) Calculated: C48.0, H3, l4, Cl 10, 15 16.00, O 13.70, O 13.70, S 9.14 ° lo; found: C 48.0, H 3.21, Cl 10.10, N 15.92, 0 13.78, S 9.29%.
IR-Spektrum: Starke Banden bei 6,10 und 6,45 . IR spectrum: strong bands at 6.10 and 6.45.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1965F0046813 DE1241835B (en) | 1965-08-04 | 1965-08-04 | Process for the preparation of 1, 3-disubstituted 5-amino-1, 2, 4-triazoles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1965F0046813 DE1241835B (en) | 1965-08-04 | 1965-08-04 | Process for the preparation of 1, 3-disubstituted 5-amino-1, 2, 4-triazoles |
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| Publication Number | Publication Date |
|---|---|
| DE1241835B true DE1241835B (en) | 1967-06-08 |
Family
ID=7101255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1965F0046813 Pending DE1241835B (en) | 1965-08-04 | 1965-08-04 | Process for the preparation of 1, 3-disubstituted 5-amino-1, 2, 4-triazoles |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1241835B (en) |
-
1965
- 1965-08-04 DE DE1965F0046813 patent/DE1241835B/en active Pending
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