DE1518823B - Process for the preparation of N-sulfonyl-iminocarbonic acid ester amides - Google Patents
Process for the preparation of N-sulfonyl-iminocarbonic acid ester amidesInfo
- Publication number
- DE1518823B DE1518823B DE1518823B DE 1518823 B DE1518823 B DE 1518823B DE 1518823 B DE1518823 B DE 1518823B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- acid esters
- cyanate
- substituted
- amides
- 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 ester amides Chemical class 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 title description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N 420-05-3 Chemical class OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 4
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 125000000565 sulfonamide group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- YIYZHARUXWKUEN-UHFFFAOYSA-N benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1.NS(=O)(=O)C1=CC=CC=C1 YIYZHARUXWKUEN-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 5
- 230000001264 neutralization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UGMKNMPRUHJNQK-UHFFFAOYSA-N (4-methylphenyl) cyanate Chemical compound CC1=CC=C(OC#N)C=C1 UGMKNMPRUHJNQK-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atoms Chemical group C* 0.000 description 4
- 150000001913 cyanates Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- UUKCNYOTIPWWTR-UHFFFAOYSA-N 2-cyanatobenzoic acid Chemical class OC(=O)C1=CC=CC=C1OC#N UUKCNYOTIPWWTR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- BBFPNAQMYBOJLI-UHFFFAOYSA-N (2,4-dimethylphenyl) cyanate Chemical compound CC1=CC=C(OC#N)C(C)=C1 BBFPNAQMYBOJLI-UHFFFAOYSA-N 0.000 description 2
- MUAFEFAYKJZTHJ-UHFFFAOYSA-N (4-acetylphenyl) cyanate Chemical compound CC(=O)C1=CC=C(OC#N)C=C1 MUAFEFAYKJZTHJ-UHFFFAOYSA-N 0.000 description 2
- GUGZCSAPOLLKNG-UHFFFAOYSA-N (4-cyanatophenyl) cyanate Chemical compound N#COC1=CC=C(OC#N)C=C1 GUGZCSAPOLLKNG-UHFFFAOYSA-N 0.000 description 2
- TXTQURPQLVHJRE-UHFFFAOYSA-N 3-nitrobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 TXTQURPQLVHJRE-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMTQKQLZBRJCLI-UHFFFAOYSA-N (2-cyanatophenyl) cyanate Chemical compound N#COC1=CC=CC=C1OC#N SMTQKQLZBRJCLI-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
- UFKLQICEQCIWNE-UHFFFAOYSA-N (3,5-dicyanatophenyl) cyanate Chemical compound N#COC1=CC(OC#N)=CC(OC#N)=C1 UFKLQICEQCIWNE-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
- BDVNNPOIBWADPU-UHFFFAOYSA-N (4-chlorophenyl) cyanate Chemical compound ClC1=CC=C(OC#N)C=C1 BDVNNPOIBWADPU-UHFFFAOYSA-N 0.000 description 1
- PMTLRCDQMKXMRZ-UHFFFAOYSA-N 1H-imidazole-2-sulfonamide Chemical class NS(=O)(=O)C1=NC=CN1 PMTLRCDQMKXMRZ-UHFFFAOYSA-N 0.000 description 1
- MOPMIZNLSWJZQK-UHFFFAOYSA-N 2,2,2-trichloroethyl cyanate Chemical compound ClC(Cl)(Cl)COC#N MOPMIZNLSWJZQK-UHFFFAOYSA-N 0.000 description 1
- FWNAJBHKFGDWAL-UHFFFAOYSA-N 2-acetylbenzenesulfonamide Chemical compound CC(=O)C1=CC=CC=C1S(N)(=O)=O FWNAJBHKFGDWAL-UHFFFAOYSA-N 0.000 description 1
- QZBOWJXHXLIMGD-UHFFFAOYSA-N 2-cyanobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1C#N QZBOWJXHXLIMGD-UHFFFAOYSA-N 0.000 description 1
- MOXDGMSQFFMNHA-UHFFFAOYSA-N 2-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1O MOXDGMSQFFMNHA-UHFFFAOYSA-N 0.000 description 1
- GNDKYAWHEKZHPJ-UHFFFAOYSA-N 2-nitrobenzenesulfonimidic acid Chemical compound NS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O GNDKYAWHEKZHPJ-UHFFFAOYSA-N 0.000 description 1
- ZLZNHLVBJWGUCV-UHFFFAOYSA-N 3-acetylbenzenesulfonamide Chemical compound CC(=O)C1=CC=CC(S(N)(=O)=O)=C1 ZLZNHLVBJWGUCV-UHFFFAOYSA-N 0.000 description 1
- LTOFQPCBIZPXFH-UHFFFAOYSA-N 3-cyanobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC(C#N)=C1 LTOFQPCBIZPXFH-UHFFFAOYSA-N 0.000 description 1
- OQPPWRYNXRWUAQ-UHFFFAOYSA-N 3-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC(O)=C1 OQPPWRYNXRWUAQ-UHFFFAOYSA-N 0.000 description 1
- VNUVBVTWBBODSV-UHFFFAOYSA-N 4-(dimethylamino)benzenesulfonamide Chemical compound CN(C)C1=CC=C(S(N)(=O)=O)C=C1 VNUVBVTWBBODSV-UHFFFAOYSA-N 0.000 description 1
- CSATVXJBGFVJES-UHFFFAOYSA-N 4-acetylbenzenesulfonamide Chemical compound CC(=O)C1=CC=C(S(N)(=O)=O)C=C1 CSATVXJBGFVJES-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
- UZECCNDOASGYNH-UHFFFAOYSA-N 4-cyanobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(C#N)C=C1 UZECCNDOASGYNH-UHFFFAOYSA-N 0.000 description 1
- DIRCLGLKRZLKHG-UHFFFAOYSA-N 4-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(O)C=C1 DIRCLGLKRZLKHG-UHFFFAOYSA-N 0.000 description 1
- DKCWFFVGFICMGR-UHFFFAOYSA-N 4-methylsulfanylbenzenesulfonamide Chemical compound CSC1=CC=C(S(N)(=O)=O)C=C1 DKCWFFVGFICMGR-UHFFFAOYSA-N 0.000 description 1
- QWKKYJLAUWFPDB-UHFFFAOYSA-N 4-nitrobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 QWKKYJLAUWFPDB-UHFFFAOYSA-N 0.000 description 1
- HMAKCHLSXJDBPZ-UHFFFAOYSA-N 9H-carbazole-1-sulfonamide Chemical class C12=CC=CC=C2NC2=C1C=CC=C2S(=O)(=O)N HMAKCHLSXJDBPZ-UHFFFAOYSA-N 0.000 description 1
- LTXCNWPUJJDTSK-UHFFFAOYSA-N C(#N)C1=C(C=CC=C1)OC#N Chemical class C(#N)C1=C(C=CC=C1)OC#N LTXCNWPUJJDTSK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OBFSMFKFSRHASW-UHFFFAOYSA-N ClC1=C(C(=CC=C1)C)OC#N Chemical compound ClC1=C(C(=CC=C1)C)OC#N OBFSMFKFSRHASW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N Nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- BFVDUDOXDKMMSP-UHFFFAOYSA-N O(C#N)C1=C(C=CC=C1)S(=O)(=O)O Chemical compound O(C#N)C1=C(C=CC=C1)S(=O)(=O)O BFVDUDOXDKMMSP-UHFFFAOYSA-N 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N Sulfamide Chemical group NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- VLMOSYXUVIVLAZ-UHFFFAOYSA-M [O-]C#N.N1=CC=CC2=CC=CC=C12 Chemical class [O-]C#N.N1=CC=CC2=CC=CC=C12 VLMOSYXUVIVLAZ-UHFFFAOYSA-M 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000008331 benzenesulfonamides Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000004643 cyanate ester 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
- AAYHAFZXFMIUSN-UHFFFAOYSA-N cyclohexanesulfonamide Chemical compound NS(=O)(=O)C1CCCCC1 AAYHAFZXFMIUSN-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
- ZCRZCMUDOWDGOB-UHFFFAOYSA-N ethanesulfonimidic acid Chemical compound CCS(N)(=O)=O ZCRZCMUDOWDGOB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RMSHYQAVCSUECE-UHFFFAOYSA-N hexane-1-sulfonamide Chemical compound CCCCCCS(N)(=O)=O RMSHYQAVCSUECE-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M isothiocyanate Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- QUSFOLYSOPZYIK-UHFFFAOYSA-N naphthalen-1-yl cyanate Chemical compound C1=CC=C2C(OC#N)=CC=CC2=C1 QUSFOLYSOPZYIK-UHFFFAOYSA-N 0.000 description 1
- KJPLRQFMMRYYFL-UHFFFAOYSA-N naphthalen-2-yl cyanate Chemical compound C1=CC=CC2=CC(OC#N)=CC=C21 KJPLRQFMMRYYFL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ABOYDMHGKWRPFD-UHFFFAOYSA-N phenylmethanesulfonamide Chemical compound NS(=O)(=O)CC1=CC=CC=C1 ABOYDMHGKWRPFD-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- SJMCLWCCNYAWRQ-UHFFFAOYSA-N propane-2-sulfonamide Chemical compound CC(C)S(N)(=O)=O SJMCLWCCNYAWRQ-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
- URMKWAIIKFEUKR-UHFFFAOYSA-N quinoline-2-sulfonamide Chemical class C1=CC=CC2=NC(S(=O)(=O)N)=CC=C21 URMKWAIIKFEUKR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- BZKBCQXYZZXSCO-UHFFFAOYSA-N sodium hydride Inorganic materials [H-].[Na+] BZKBCQXYZZXSCO-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
Description
ROCNROCN
in der R die oben angegebene Bedeutung hat, mit Sulfonsäureamiden der allgemeinen Formelin which R has the meaning given above, with sulfonic acid amides of the general formula
R1C-SO2-NH2),R 1 C-SO 2 -NH 2 ),
in der R1 die oben angegebene Bedeutung hat und y für eine ganze Zahl von 1 bis 3 steht, wobei zwei Sulfonamidgruppen nicht in o-Stellung zueinander stehen, bei Temperaturen zwischen — 20 und + 200° C, vorzugsweise von 0 bis 150° C, gegebenenfalls in einem Verdünnungsmittel und gegebenenfalls in Anwesenheit einer Base umsetzt.in which R 1 has the meaning given above and y is an integer from 1 to 3, two sulfonamide groups not being in the o-position to one another, at temperatures between -20 and + 200.degree. C., preferably from 0 to 150.degree , optionally in a diluent and optionally in the presence of a base.
Die nach diesem Verfahren herstellbaren Verbindungen sind neu und haben die allgemeinen FormelnThe compounds that can be prepared by this process are new and have the general formulas
3535
4040
NH
— Ο—C-NHSO2R1 NH
- Ο — C-NHSO 2 R 1
4545
Es wurde gefunden, daß man neuartige N-Sulfonyliminokohlensäureesteramide erhält, wenn man Cyansäureester der allgemeinen FormelIt has been found that novel N-sulfonyliminocarbonic acid ester amides can be obtained obtained when cyanic acid esters of the general formula
R(OCN)x R (OCN) x
in der R einen Halogenalkylrest oder einen aromatischen Rest, der gegebenenfalls durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Alkyl-, Cycloalkyl-, Aryl-, Acylamino-, Dialkylamino-, Nitro-, Halogen-, Alkoxy-, Aroxy-, Acyloxy-, Alkyl- · carbonyl-, Arylcarbonyl-, -carbonsäureester, Alkylsulfonyl-, Arylsulfonyl-, -sulfonsäureester, Alkylmercapto-, Arylmercapto- und Acylmercapto- substituiert . sein kann, und χ eine ganze Zahl von 1 bis 3 bedeutet, wobei zwei OCN-Gruppen nicht in o-Stellung zueinander stehen, mit Sulfonsäureamiden der allgemeinen Formel ...in which R is a haloalkyl radical or an aromatic radical which is optionally substituted by one or more identical or different radicals from the group consisting of alkyl, cycloalkyl, aryl, acylamino, dialkylamino, nitro, halogen, alkoxy, aroxy, Acyloxy, alkyl · carbonyl, arylcarbonyl, carboxylic acid esters, alkylsulfonyl, arylsulfonyl, sulfonic acid esters, alkyl mercapto, aryl mercapto and acyl mercapto substituted. can be, and χ denotes an integer from 1 to 3, where two OCN groups are not in the o-position to one another, with sulfonic acid amides of the general formula ...
R1 —SO2NH2 R 1 -SO 2 NH 2
in der R1 für einen aliphatischen, aromatischen oder heterocyclischen Rest steht, der durch einen oderin which R 1 is an aliphatic, aromatic or heterocyclic radical which is replaced by an or
VR-O-C-NHSO2^rR1 VR-OC-NHSO 2 ^ rR 1
in welchen R, R1, χ und y die oben angegebene Bedeutung haben.in which R, R 1 , χ and y have the meaning given above.
Halogenalkylreste R sind z.B. Kohlenwasserstoffreste mit bis zu 12 C-Atomen, die vorzugsweise in a- oder jS-Stellung zum sauerstofftragenden C-Atom Halogenatome tragen. Als aliphatische Reste R1 seien vorzugsweise gradkettige oder verzweigte Alkylreste mit 1 bis 12 Kohlenstoffatomen genannt. Als aromatische Reste R und R1 kommen aromatische Kohlenwasserstoffreste mit bis zu 20 Kohlenstoffatomen im Ringsystem in Betracht. Die aromatischen Reste R bzw. R1 können als Substituenten beispielsweise tragen: Alkyl-, Aryl-, Alkylamino-, Acylamino-, Nitro-, Halogen-, Alkoxy-, Aroxy-, Acyloxy-, Carbonyl-, Carboxyl-, Carbonester, -amid-, Sulfonyl-, Sulfonsäureester, -amid-, Acyl-, Cyano-, Rhodanid-, Alkylmercapto-, Arylmercapto- oder Acylmercaptogruppen.Haloalkyl radicals R are, for example, hydrocarbon radicals with up to 12 carbon atoms, which preferably carry halogen atoms in the a- or jS-position to the oxygen-carrying carbon atom. Aliphatic radicals R 1 are preferably straight-chain or branched alkyl radicals having 1 to 12 carbon atoms. Possible aromatic radicals R and R 1 are aromatic hydrocarbon radicals with up to 20 carbon atoms in the ring system. The aromatic radicals R or R 1 can carry, for example, as substituents: alkyl, aryl, alkylamino, acylamino, nitro, halogen, alkoxy, aroxy, acyloxy, carbonyl, carboxyl, carbon esters, - amide, sulfonyl, sulfonic acid esters, amide, acyl, cyano, rhodanide, alkyl mercapto, aryl mercapto or acyl mercapto groups.
Die als Ausgangsverbindungen verwendeten Cyansäureester können gemäß eigenen älteren Vorschlägen durch Umsetzung von hydroxylgruppenhaltigen Verbindungen mit Halogencyaniden bei Temperaturen, vorzugsweise unterhalb +650C, gegebenenfalls in einem Lösungsmittel in Gegenwart einer Base hergestellt werden. The cyanate ester used as starting compounds can be prepared according own earlier proposals by the reaction of hydroxyl-containing compounds at temperatures Halogencyaniden are preferably prepared below +65 0 C, optionally in a solvent in the presence of a base.
Es können für das erfindungsgemäße Verfahren z. B. folgende Cyansäureester eingesetzt werden:It can be used for the inventive method, for. B. the following cyanic acid esters are used:
Phenylcyanat,Phenyl cyanate,
Mono- und Polyalkylphenylcyanate, wieMono- and polyalkylphenyl cyanates, such as
3-Methyl-, 4-Isododecyl-, 4-Cyclohexyl-,3-methyl-, 4-isododecyl-, 4-cyclohexyl-,
2-tert.-Butyl-, 3-Trifluormethyl-,2-tert-butyl, 3-trifluoromethyl,
2,4-Dimethyl-, 3,5-Dimethyl-, 2,6-Diäthyl-,2,4-dimethyl-, 3,5-dimethyl-, 2,6-diethyl-,
4-Allyl-2-methoxyphenylcyanat;
Arylphenylcyanate, wie 4-Cyanatodiphenyl,4-allyl-2-methoxyphenyl cyanate;
Arylphenylcyanates, such as 4-cyanatodiphenyl,
4,4'-Biscyanatodiphenyl;
Dialkylaminophenylcyanate, wie 4-Dimethyl-4,4'-biscyanatodiphenyl;
Dialkylaminophenyl cyanates, such as 4-dimethyl
amino-, 4-Dimethylamino-3-methylphenyl-amino-, 4-dimethylamino-3-methylphenyl-
cyanat;
Acylaminophenylcyanate, wie Acetylamino-cyanate;
Acylaminophenyl cyanates, such as acetylamino-
phenylcyanat;phenyl cyanate;
Nitrophenylcyanate, wie 4-Nitro-, 3-Nitro-,Nitrophenyl cyanates, such as 4-nitro-, 3-nitro-,
4-Nitro-3-methyl, S-Nitro-o-methyl-phenyl-4-nitro-3-methyl, S-nitro-o-methyl-phenyl-
cyanat;
Halogenphenylcyanate, wie 2-Chlor-, 3-Chlor-,cyanate;
Halophenyl cyanates, such as 2-chloro, 3-chloro,
4-Chlor-, 2,4-Dichlor-, 2,6-Dichlor-,4-chloro, 2,4-dichloro, 2,6-dichloro,
3-Brom-, 2-Chlor-6-methyl-phenylcyanat;
Cyanatophenylcarbonsäure, -ester, -amide, wie3-bromo-, 2-chloro-6-methyl-phenyl cyanate;
Cyanatophenylcarboxylic acids, esters, amides, such as
4-Cyanatobenzoesäure, 2-Cyanatobenzoe-4-cyanatobenzoic acid, 2-cyanatobenzoic acid
säureäthylester, 2-Cyanatobenzoesäure-acid ethyl ester, 2-cyanatobenzoic acid
morpholid und -diäthylamid;
Cyanatophenylsulfonsäure, -ester, -amide, wiemorpholide and diethylamide;
Cyanatophenylsulfonic acid, esters, amides, such as
4-Cyanatobenzolsulfonsäure;
Alkoxyphenylcyanate, wie 2-Methoxy-,4-cyanatobenzenesulfonic acid;
Alkoxyphenyl cyanates, such as 2-methoxy,
3-Methoxy-, 4-Cyanatodiphenyläther;
Acyloxyphenylcyanate, wie 3-Acetoxyphenyl-3-methoxy, 4-cyanatodiphenyl ethers;
Acyloxyphenyl cyanates, such as 3-acetoxyphenyl
cyanat;cyanate;
Acylphenylcyabate, wie 4-Acetylphenylcyanat;
Cyanophenylcyanate, wie 2,3-Dicyano-Acylphenylcyabates such as 4-acetylphenylcyanate;
Cyanophenyl cyanates, such as 2,3-dicyano
1,4-dicyanatobenzol;
α- Und /3-Naphthylcyanat, Anthrachinylcyanate,1,4-dicyanatobenzene;
α- and / 3-naphthyl cyanate, anthrachinyl cyanate,
wie 1,4-Dicyanätoanthrachinon;
Chinolincyanate, wie 5-Cyanatochinolin;
1,4-Phenylendicyanat, 1,5-Naphthylendicyanat,such as 1,4-dicyanetoanthraquinone;
Quinoline cyanates such as 5-cyanatoquinoline;
1,4-phenylene dicyanate, 1,5-naphthylene dicyanate,
1,3,5-Tricyanatobenzol,
4,4'-Biscyanatodiphenyldimethylmethan,1,3,5-tricyanatobenzene,
4,4'-biscyanatodiphenyldimethylmethane,
4,4'-Biscyanatodiphenyl-cyclohexan-l,l;
2,2 '-Biscyanato-dinaphthyl, 4-Methylmercapto-4,4'-biscyanatodiphenyl-cyclohexane-l, l;
2,2'-biscyanato-dinaphthyl, 4-methylmercapto-
phenylcyanat, 3-N,N-Dimethylcarbamyl-phenylcyanate, 3-N, N-dimethylcarbamyl-
phenyl-cyanatphenyl cyanate
und die Cyansäureester folgender Alkohole:and the cyanic acid esters of the following alcohols:
ft/S^-Trichloräthanol, ^,ß-Trifluoräthanol,
/S,^,/S-Tribromäthanol, ft/S-Dichloräthanol.ft / S ^ -Trichloroethanol, ^, ß-Trifluoroethanol,
/ S, ^, / S-tribromoethanol, ft / S-dichloroethanol.
Na2CO3, NaNH2, NaH, NaOCH3, Na oder tert.-Amine, wie z. B. Triäthylamin.Na 2 CO 3 , NaNH 2 , NaH, NaOCH 3 , Na or tert-amines, such as. B. triethylamine.
Die Reaktion wird durch Zusammengeben der Komponenten, vorzugsweise in einem flüssigen Medium, in einem Verhältnis Cyanatgruppe zu SuIfamidgruppe wie 1:1, gegebenenfalls in Anwesenheit einer Base, durchgeführt. Ein Überschuß eines Reaktionspartners stört im allgemeinen nicht. Die Reaktionsprodukte fallen meist, gegebenenfalls nach Einengen des Lösungsmittels, aus und können, gegebenenfalls nach Neutralisation, isoliert werden.The reaction is carried out by combining the components, preferably in a liquid medium, in a ratio of cyanate group to sulfamide group of 1: 1, optionally in presence a base. An excess of a reactant does not generally interfere. The reaction products usually precipitate, if appropriate after concentration of the solvent, and can, if appropriate after neutralization, are isolated.
Die erfindungsgemäßen N-Sulfonyl-iminokohlensäureesteramide sind neu und können als wertvolle Zwischenprodukte für Pharmazeutika verwendet wer-The N-sulfonyl-iminocarbonic acid ester amides according to the invention are new and can be used as valuable intermediates for pharmaceuticals
den. π . ·ιιthe. π . · Ιι
Zu einem Gemisch aus 7,6 g (0,05 Mol) Benzolsulfonamid und 30 ml Aceton werden IO ml einer O,lnormalen wäßrigen NaOH-Lösung gegeben und dann 6,65 (0,05 Mol) 4-Methylphenylcyanat zugesetzt. Temperaturanstieg von Raumtemperatur auf 450C. Die klare Lösung erstarrt schlagartig; nach dem Absaugen wird der Rückstand mit dem 4- bis 5fachen Volumen Wasser verrührt, erneut abgesaugt und neutralgewaschen. 10,2 g (= 71% der Theorie) des10 ml of an O, lnormal aqueous NaOH solution are added to a mixture of 7.6 g (0.05 mol) of benzenesulfonamide and 30 ml of acetone, and then 6.65 (0.05 mol) of 4-methylphenyl cyanate are added. Temperature rise from room temperature to 45 ° C. The clear solution suddenly solidifies; After suctioning off, the residue is stirred with 4 to 5 times the volume of water, suctioned off again and washed until neutral. 10.2 g (= 71% of theory) of the
NHNH
3535
Als Sulfonsäureamide können beispielsweise eingesetzt werden: Methansulfonamid, Äthansulfonamid, Isopropansulfonamid, Hexansulfonamid, Oyclohexansulfonamid, Phenylmethansulfonamid, Benzolsulfonamid, Benzoldisulfonsäurediamid, Benzoltrisulfontriamid, α- oder /S-Naphthalinsulfonamid, 2-, 3- oder 4-Toluolsulfonamid, 2-, 3- oder 4-Chlor (Brom, Fluor)-benzolsulfonamid, 2-, 3- oder 4-Hydroxybenzolsulfonamid, 2-, 3- oder 4-Dimethylaminobenzolsulfonamid, 2-, 3- oder 4-Nitrobenzolsulfonamid, 2-, 3- oder 4-Acetylbenzolsulfonamid, 2-, 3- oder 4-Methoxy-(Äthoxy-, Isopropoxy-)-benzolsulfonamid, 2-, 3- oder 4-Methylmercaptobenzolsulfonamid, 2-, 3- oder 4-Cyanobenzolsulfonamid, ferner Benzolsulfonamide mit mehr als einem der beispielsweise oben aufgezählten Substituenten mit Naphthylsulfonamide, die ein- oder mehrfach die bei den Benzolderivaten aufgezählten Substituenten tragen, Chinolinsulfonamide, Carbazolsulfonamide, Phenylpyrazonlonsulfonamide, Imidazolsulfonamide.The following can be used as sulfonic acid amides, for example: methanesulfonamide, ethanesulfonamide, Isopropanesulfonamide, hexanesulfonamide, cyclohexanesulfonamide, phenylmethanesulfonamide, benzenesulfonamide, Benzoldisulfonsäurediamid, Benzoltrisulfontriamid, α- or / S-naphthalenesulfonamid, 2-, 3- or 4-toluenesulfonamide, 2-, 3- or 4-chlorine (bromine, fluorine) -benzenesulfonamide, 2-, 3- or 4-hydroxybenzenesulfonamide, 2-, 3- or 4-dimethylaminobenzenesulfonamide, 2-, 3- or 4-nitrobenzenesulfonamide, 2-, 3- or 4-acetylbenzenesulfonamide, 2-, 3- or 4-methoxy- (ethoxy-, Isopropoxy -) - benzenesulfonamide, 2-, 3- or 4-methylmercaptobenzenesulfonamide, 2-, 3- or 4-Cyanobenzenesulfonamide, also benzenesulfonamides with more than one of the substituents listed above, for example, with naphthylsulfonamides, the carry one or more of the substituents listed for the benzene derivatives, quinolinesulfonamides, Carbazole sulfonamides, phenylpyrazole sulfonamides, imidazole sulfonamides.
Als Lösungsmittel kommen z. B. organische Lösungsmittel, wie Alkohole, Ketone, Äther, Nitrile, Ester, Amide, aromatische und aliphatisch^, gegebenenfalls nitrierte oder halogenierte Kohlenwasserstoffe oder Wasser, in Betracht. Es seien hier beispielsweise genannt: Methanol, Äthanol, Aceton, Diäthyläther, Acetonitril, Essigester, Dimethylformamid, Ben? zol, Petroläther, Nitrobenzol, Nitromethan, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol.As a solvent, for. B. organic solvents such as alcohols, ketones, ethers, nitriles, Esters, amides, aromatic and aliphatic ^, optionally nitrated or halogenated hydrocarbons or water. Examples include: methanol, ethanol, acetone, diethyl ether, Acetonitrile, ethyl acetate, dimethylformamide, ben? zol, petroleum ether, nitrobenzene, nitromethane, chloroform, Carbon tetrachloride, chlorobenzene.
Als die Reaktion fördernde Basen können beispielsweise in katalytischen bis molaren Mengen zugesetzt werden: Alkalihydroxyde, -carbonate, -amide, -hydride, -alkoholate, -metalle, z.B. NaOH, KOH,The bases which promote the reaction can be added, for example, in catalytic to molar amounts are: alkali hydroxides, carbonates, amides, hydrides, alcoholates, metals, e.g. NaOH, KOH,
30 vom F. 165° C werden so erhalten. C14H14N2O3S (290): 30 with a mp of 165 ° C are obtained. C 14 H 14 N 2 O 3 S (290):
Berechnet:Calculated:
C 57,9, H 4,82, N 9,65, O 16,5, S 11,0%; gefunden:C 57.9, H 4.82, N 9.65, O 16.5, S 11.0%; found:
C 58,08, H 4,91, N 9,93, O 16,71, S 10,65%.C 58.08, H 4.91, N 9.93, O 16.71, S 10.65%.
Analog Beispiel 1 erhält man aus 10 g (0,05 Mol) 3-Nitrobenzolsulfonamid, 6,65 g (0,05 Mol) 4-Methylphenylcyanat und 8 ml !normaler wäßriger NaOH-Lösung 12,8 g (= 77% der Theorie) desAnalogously to Example 1, 6.65 g (0.05 mol) of 4-methylphenyl cyanate are obtained from 10 g (0.05 mol) of 3-nitrobenzenesulfonamide and 8 ml! normal aqueous NaOH solution 12.8 g (= 77% of theory) des
NHNH
/-* -KTXJ cn —ν \/ - * -KTXJ cn -ν \
H,CH, C
vom F. 162bisl64°C.
C14H13N3O5S (335):from 162 to 64 ° C.
C 14 H 13 N 3 O 5 S (335):
Berechnet:Calculated:
C 50,1, H 3,88, N 12,53, O 23,9, S 9,55%; : gefunden:C 50.1, H 3.88, N 12.53, O 23.9, S 9.55%; : found:
C 50,50, H 4,19, N 12,50, O 23,95, S 9,70%. ~C 50.50, H 4.19, N 12.50, O 23.95, S 9.70%. ~
Analog Beispiel 1 erhält man aus Benzolsulfonamid und 2,4-Dimethylphenylcyanat mit 74%iger Ausbeute dasAnalogously to Example 1, benzenesulfonamide and 2,4-dimethylphenyl cyanate are obtained in a 74% yield that
vom F. 146 bis 147° C.from 146 to 147 ° C.
'/ 5'/ 5
C15H16N2O3S (304):C 15 H 16 N 2 O 3 S (304):
Berechnet:Calculated:
C 59,3, H 5,25, N 9,2, O 15,8, S 10,5%;C 59.3, H 5.25, N 9.2, O 15.8, S 10.5%;
Molgewicht 304;
gefunden:Molecular weight 304;
found:
C 59,29, H 5,55, N 9,22, O 15,83, S 10,5%.C 59.29, H 5.55, N 9.22, O 15.83, S 10.5%.
Molgewicht 313.Molecular weight 313.
Analog Beispiel 1 erhält man aus 4-Acetylphenylcyanat und Benzolsulfonamid dasAnalogously to Example 1, 4-acetylphenyl cyanate is obtained and benzenesulfonamide that
8,55 g(0,05 Mol) o-Toluolsulfamid werden in Aceton gelöst, dann 5 ml n-NaOH und anschließend 7,35 g (0,05 Mol) 2,4-Dimethylphenylcyanat zugegeben. Temperaturanstieg bis 38° C. Nach einer Stunde wird mit 150 ml Wasser verdünnt. Ein Ol scheidet sich ab, das bald erstarrt. Ausbeute: 12,3 g (= 77 % der Theorie) des8.55 g (0.05 mol) of o-toluenesulfamide are dissolved in acetone, then 5 ml of n-NaOH and then 7.35 g (0.05 mol) 2,4-dimethylphenyl cyanate was added. Temperature rise to 38 ° C. After an hour, with 150 ml of water diluted. An oil separates out, that soon froze. Yield: 12.3 g (= 77% of theory) of the
CH,CH,
H,C—C—<f V-O-C—NH-SO, —H, C — C— <f V-O-C — NH-SO, -
CH3 NH CH 3 NH
V-o—C—NH-SO.V-o-C-NH-SO.
CH,CH,
2020th
vom F. 173 bis 175° C.
C15H14N2O4S (318):from 173 to 175 ° C.
C 15 H 14 N 2 O 4 S (318):
Berechnet ... C 56,6, H 4,40, N 8,80, O 20,15%; • gefunden .... C 56,54, H 4,45, N 9,02, O 20,26%.Calculated ... C 56.6, H 4.40, N 8.80, O 20.15%; • Found .... C 56.54, H 4.45, N 9.02, O 20.26%.
7,65 g (0,05MoI) 3-Chlorphenylcyanat und 8,55 g (0,05 Mol) o-Toluolsulfamid werden in 30 ml Aceton gelöst. Dann wird so lange lnormale wäßrige NaOH zugesetzt, bis keine Wärmetönung mehr festgestellt wird (insgesamt 50 ml). Es scheidet sich ein öl mit Kristallen ab. Nach kurzer Zeit wird mit wenig HCl neutral gestellt, abgesaugt, gewaschen, auf Ton gepreßt. Ausbeute: 8,1 g (= 50% der Theorie) des7.65 g (0.05 mol) 3-chlorophenyl cyanate and 8.55 g (0.05 mol) of o-toluenesulfamide are dissolved in 30 ml of acetone. Then normal aqueous NaOH is used for so long added until no more exothermicity is detected (50 ml in total). An oil separates with it Crystals. After a short time, the mixture is made neutral with a little HCl, filtered off with suction, washed and pressed onto clay. Yield: 8.1 g (= 50% of theory) of the
ClCl
\. NH \. NH
/~\—O—C—NH- SO/ ~ \ —O — C — NH — SO
3535
4040
vom F. 115 bis 116° C.
C14H13ClN2O3S (324,5):from 115 to 116 ° C.
C 14 H 13 ClN 2 O 3 S (324.5):
Berechnet:Calculated:
C 51,8, H 4,00, N 8,65, O 14,7, S 9,87, Cl 10,95%; gefunden:C 51.8, H 4.00, N 8.65, O 14.7, S 9.87, Cl 10.95%; found:
C 51,51, H 4,17, N 8,93, O 14,61, S 9,80, Cl 11,10%.C 51.51, H 4.17, N 8.93, O 14.61, S 9.80, Cl 11.10%.
das durch Absaugen isoliert wird. F. 155 bis 156° C. C16H18N2O3S (318):which is isolated by suction. F. 155 to 156 ° C. C 16 H 18 N 2 O 3 S (318):
Berechnet:Calculated:
C 60,4, H 5,66, N 8,80, O 15,1, S 10,05%;C 60.4, H 5.66, N 8.80, O 15.1, S 10.05%;
Molgewicht 318.
gefunden:Molecular weight 318.
found:
C 60,29, H 5,72, N 8,84, O 15,02, S 10,00%.C 60.29, H 5.72, N 8.84, O 15.02, S 10.00%.
Molgewicht 322.Molecular weight 322.
Analog Beispiel 6 erhält man aus 8,7 g Trichloräthylcyanat und 7,6g Benzolsulfamid 11,4g (= 70% der Theorie) desAnalogously to Example 6, 11.4 g (= 70%) are obtained from 8.7 g of trichloroethyl cyanate and 7.6 g of benzenesulfamide the theory) des
NH
Cl3C-CH2-O-C-NHSO2 NH
Cl 3 C-CH 2 -OC-NHSO 2
F. 156 bis 157° C.
C9H9Cl3N2O3S (331,5):F. 156 to 157 ° C.
C 9 H 9 Cl 3 N 2 O 3 S (331.5):
Berechnet:Calculated:
C 32,6, H 2,27, N 8,44, O 14,5, S 9,66%;
gefunden:C 32.6, H 2.27, N 8.44, O 14.5, S 9.66%;
found:
C 32,17, H 2,73, N 8,52, O 14,40, S 9,38%.C 32.17, H 2.73, N 8.52, O 14.40, S 9.38%.
Analog Beispiel 6 erhält man aus 2 Mol Benzolsulfamid und 1 Mol Phenylenbiscyanat (1,4) dasAnalogously to Example 6, 2 moles of benzenesulfamide and 1 mole of phenylene biscyanate (1,4) are obtained
vom F. 265 bis 267° C.from 265 to 267 ° C.
C20-H18N4O6S (474):C 20 -H 18 N 4 O 6 S (474):
Berechnet:Calculated:
C 50,65, H 3,76, N 11,80, 0 20,30%; gefunden:C 50.65, H 3.76, N 11.80, 0 20.30%; found:
C 50,77, H 4,01, N 11,92, 0 20,01%.C 50.77, H 4.01, N 11.92, 0 20.01%.
bei 400C gehalten. Nach 1 Stunde wird in Wasser gerührt und das kristallisierteheld at 40 ° C. After 1 hour, the mixture is stirred in water and the crystallized
5555
6o NH 6o NH
r1 MU cn _# Nir 1 MU cn _ # Ni
durch Absaugen gewonnen. Ausbeute: 13,5 g (= 76% der Theorie). F. 193 bis 194° C.obtained by suction. Yield: 13.5 g (= 76% of theory). F. 193 to 194 ° C.
Erhitzt man 3,8 g (0,025MoI) Benzolsulfonamid3.8 g (0.025 mol) of benzenesulfonamide are heated
10 g 3-Nitrobenzolsulfamid werden in Aceton und 3,3 g (0,025 Mol) 4-Methylphenylcyanat zusammen mit 5 ml In-NaOH auf 900C, so bildet sich ein öl, das bei etwa 700C zu kristallisieren beginnt.10 g of 3-nitrobenzenesulfamide are dissolved in acetone and 3.3 g (0.025 mol) of 4-methylphenyl cyanate together with 5 ml of In-NaOH at 90 ° C., an oil which begins to crystallize at about 70 ° C. is formed.
suspendiert, 14 ml Triäthylamin und dann 7,65 g 4-Chlorphenylcyanat zugegeben. Die Temperatur wirdsuspended, 14 ml of triethylamine and then 7.65 g of 4-chlorophenyl cyanate were added. The temperature will
Nach dem Absaugen, Neutralwaschen mit Wasser erhält man 5,2 g (= 73% der Theorie) des gleichen Produktes wie im Beispiel 1 (identisches IR-Spektrum, F. 163 bis 164° C).After filtering off with suction and washing neutral with water, 5.2 g (= 73% of theory) of the same are obtained Product as in Example 1 (identical IR spectrum, mp 163 to 164 ° C).
Theorie) des gleichen Produktes wie im Beispiel 1 oder 10 (identisches IR-Spektrum).Theory) of the same product as in Example 1 or 10 (identical IR spectrum).
Analog Beispiel 9 erhält man aus a-Naphthylcyanat und Methansulfonsäureamid dasAnalogously to Example 9, α-naphthyl cyanate and methanesulfonic acid amide give the
NHNH
-C-NH-SO3-CH,-C-NH-SO 3 -CH,
Beim Erhitzen von 3,3 g (0,025 Mol) 4-Methylphenylcyanat und 3,8 g (0,025 Mol) Benzolsulfonamid I0 ohne Lösungsmittel und ohne Basenzusatz auf 135° C (innerhalb von 2 Stunden) erstarrt die Masse beim Abkühlen, und man erhält nach Verrühren mit Alkohol, Absaugen und Neutralwaschen 5 g ( = 70% der vom F. 151 bis 153°C (aus Alkohol).When 3.3 g (0.025 mol) of 4-methylphenyl cyanate and 3.8 g (0.025 mol) of benzenesulfonamide 10 are heated to 135 ° C. (within 2 hours) without a solvent and without the addition of a base, the mass solidifies on cooling, and after Stirring with alcohol, suction and neutral washing 5 g (= 70% of the temperature from 151 to 153 ° C (from alcohol).
Claims (1)
Family
ID=
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