US2948753A - N-bis(p-dialkylaminophenyl)methyl sulfonamides - Google Patents
N-bis(p-dialkylaminophenyl)methyl sulfonamides Download PDFInfo
- Publication number
- US2948753A US2948753A US734419A US73441958A US2948753A US 2948753 A US2948753 A US 2948753A US 734419 A US734419 A US 734419A US 73441958 A US73441958 A US 73441958A US 2948753 A US2948753 A US 2948753A
- Authority
- US
- United States
- Prior art keywords
- bis
- methyl
- parts
- radicals
- sulfonamide
- 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.)
- Expired - Lifetime
Links
- -1 methyl sulfonamides Chemical class 0.000 title claims description 70
- 229940124530 sulfonamide Drugs 0.000 title claims description 24
- 150000003254 radicals Chemical class 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 150000005840 aryl radicals Chemical class 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- SONNWYBIRXJNDC-VIFPVBQESA-N phenylephrine Chemical class CNC[C@H](O)C1=CC=CC(O)=C1 SONNWYBIRXJNDC-VIFPVBQESA-N 0.000 claims 2
- 229910006074 SO2NH2 Inorganic materials 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 90
- 150000001875 compounds Chemical class 0.000 description 23
- 239000013078 crystal Substances 0.000 description 21
- 230000002378 acidificating effect Effects 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000000440 bentonite Substances 0.000 description 14
- 229910000278 bentonite Inorganic materials 0.000 description 14
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 150000003456 sulfonamides Chemical class 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FBEHFRAORPEGFH-UHFFFAOYSA-N Allyxycarb Chemical compound CNC(=O)OC1=CC(C)=C(N(CC=C)CC=C)C(C)=C1 FBEHFRAORPEGFH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000012264 purified product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 4
- MSFQEZBRFPAFEX-UHFFFAOYSA-N 4-methoxybenzenesulfonamide Chemical compound COC1=CC=C(S(N)(=O)=O)C=C1 MSFQEZBRFPAFEX-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 2
- ASSPUNAVLOJWPK-UHFFFAOYSA-N 4-[anilino-[4-(dimethylamino)phenyl]methyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)NC1=CC=CC=C1 ASSPUNAVLOJWPK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical group [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005236 alkanoylamino group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical class C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- SYQMMCZWJAEWEK-UHFFFAOYSA-N octadecane-1-sulfonamide Chemical class CCCCCCCCCCCCCCCCCCS(N)(=O)=O SYQMMCZWJAEWEK-UHFFFAOYSA-N 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- JZZPZVLDDWYVLE-UHFFFAOYSA-N 1-hydroxydecan-2-one Chemical compound CCCCCCCCC(=O)CO JZZPZVLDDWYVLE-UHFFFAOYSA-N 0.000 description 1
- LRRRPAGIIAWDEB-UHFFFAOYSA-N 10H-phenothiazine-3-sulfonamide Chemical compound C1=CC(=CC=2SC3=CC=CC=C3NC12)S(=O)(=O)N LRRRPAGIIAWDEB-UHFFFAOYSA-N 0.000 description 1
- YSASFQAGHCOYAL-UHFFFAOYSA-N 4-(diethylamino)benzenesulfonamide Chemical compound CCN(CC)C1=CC=C(S(N)(=O)=O)C=C1 YSASFQAGHCOYAL-UHFFFAOYSA-N 0.000 description 1
- JVFCCRJSBNUDDU-UHFFFAOYSA-N 4-phenylbenzenesulfonamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1C1=CC=CC=C1 JVFCCRJSBNUDDU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WCIQBUVXZZYFJP-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanol Chemical compound C1=CC(N(CC)CC)=CC=C1C(O)C1=CC=C(N(CC)CC)C=C1 WCIQBUVXZZYFJP-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- CRPAPNNHNVVYKL-UHFFFAOYSA-N hexadecane-1-sulfonamide Chemical class CCCCCCCCCCCCCCCCS(N)(=O)=O CRPAPNNHNVVYKL-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229940099273 magnesium trisilicate Drugs 0.000 description 1
- 229910000386 magnesium trisilicate Inorganic materials 0.000 description 1
- 235000019793 magnesium trisilicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- ZSJVRUWXJDVHQI-UHFFFAOYSA-N quinoline-6-sulfonamide Chemical compound N1=CC=CC2=CC(S(=O)(=O)N)=CC=C21 ZSJVRUWXJDVHQI-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 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
- 125000005628 tolylene group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/136—Organic colour formers, e.g. leuco dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
- C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/02—Diaryl- or thriarylmethane dyes derived from diarylmethanes
Definitions
- This invention relates to compounds which are derivatives of. bis(p-dialkylaminoaryl)methane in which nitrogen is linked to the methane carbon atom. It relates more particularly to compounds of said type having superior properties as compared to known compounds of said general class.
- An object of the present invention is to provide novel derivatives of bis(p-dialkylaminoaryl)methane, and especially of bis(p-dimethylaminophenyl)methane, in which the methane carbon atom thereof is linked to the nitrogen atom of a nitrogen-containing radical having a beneficial effect upon the properties of said derivatives.
- a further object of the present invention is to pro vide novel bis(p-dialkylaminoaryl) methyl derivatives of said type which are lightly colored or substantially colorless but which when contacted with acidic electron acceptors produce colored compositions.
- Another object of the present invention is to provide novel compounds of said type having superior stability as compared to N-bis (p-dimethylaminophenyl)methyl aniline (also known as N-phenyl leucoauramine) and derivatives of the latter, when embodied in manifold record systems of the type disclosed in US. Patents 2,505,470 and 2,548,366, for example.
- acidic electron acceptor materials such as acidic clays (for example, attapulgite, halloysite, kaolin.
- the compounds of the present invention are N-bis(pdialkylaminoaryl)methyl sulfonamides in which the alkyl groups of the dialkylamino radical each have 1 to 5 carbon atoms, and the aryl radicals are mononuclear aryl radicals. They include compounds which in themselves are colored (containing chromophoric groups) and compounds which are lightly colored, or colorless, or substantially colorless (free from chromophoric groups). Further, they include compounds which include in their molecules acidic groups containing a hydrogen cation (for example, a sulfonic acid or carboxylic acid radical), and compounds free from such acidic groups. In this connection it is noted that groups which do not contain a hydrogen cation, such as salts of acidic groups (e.g.,
- alkali metal, ammonium, organic base and other salts of carboxylic and sulfonic acids are included herein as being free from'acid groups containing a free hydrogen cation.
- alkyl radicals of the p-dialkylamino radicals ome Commethyl, ethyl, propyl, butyl and amyl radicals. pounds in which they are methyl or ethyl are preferred;
- the mononuclear aryl radicals include unsubstituted phenylene radicals and phenylene radicals containing one or more inert substituents such as alkyl, alkoxy, halogen or acylamino substituents; for example, tolylene,
- chlorophenylene bromophenylene, Compounds in which they are. mononuclear aryl. hydrocarbon radicals, and especially phenylene, are pre-Y methoxyphenylene, etc.
- the sulfonarnide radicals of the compounds. of present invention include various types of such radicals. f, Thus they include sulfonamide radicals in which the radi cal attached to the sulfon group is an alkyl, cycloalkyl, a sultani aralkyl, aryl,.or heterocyclic radical, or part of (in which the group is linked to diiferentjcarbon atoms of thesame' radical), a number of which are illustrated below.
- Patented Aug. '9, 1960 They also include radicals in which the hydrogen atom of the group is substituted by an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical. Preferably they are free from chromophoric groups and from acidic groups containing a hydrogen cation, which would interfere with their use as leuco electron-donor color reactants. They may, however, contain such substituents as alkyl, alkoxy, halogen, dialkylamino, acylamino and sulfonamido groups.
- N-bis (p-dialkylaminoaryl)methyl sulfonamides of the present invention have the formula wherein:
- R R R and R are each an alkyl radical having 1 to 5 carbon atoms (such as, methyl, ethyl, propyl, butyl or amyl),
- R is selected from the group consisting of alkyl (such as, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl or octadecenyl), cycloalkyl (such as, cyclopentyl, cyclohexyl or methyl cyclohexyl), aralkyl (such as, benzyl or phenylethyl), aryl (such as, phenyl, tolyl, xylyl, naphthyl, biphenyl or indene) and heterocyclic (such as, pyridyl, quinolyl, benzothiazyl, benzofuryl or pheuothiazyl) radicals, including substituted derivatives of such radicals and preferably those free from chromophoric groups and from acidic groups
- R R, R and R are methyl or ethyl
- the phenylene radicalls are mononuclear aryl hydrocarbon radicals
- R is hydrogen or methyl
- R is phenyl, tolyl, methoxyphenyl, or dimethylaminophenyl.
- the compounds of the present invention are soluble in a wide variety of non-polar organic solvents, such as benzene, toluene, kerosene, mineral oil, dioctylphthalate, chlorinated biphenyls, etc.
- non-polar organic solvents such as benzene, toluene, kerosene, mineral oil, dioctylphthalate, chlorinated biphenyls, etc.
- an acidic material such as bentonite, kaolin, felspar, monoor dibasic barium or calcium phosphates
- they produce generally greenish blue to violet colorations.
- the sulfonamido radical they possess relatively low volatility and high stability to air and light.
- the compounds of the present invention are useful in the formation of colored compounds or difierently colored compounds by contact with electron acceptor or acidic materials which cause a rearrangement of the chemical molecule with intensification of the color thereof, such as those enumerated above.
- Lightly colored, and especially colorless or substantially colorless, compounds of this invention are particularly useful in so-called colorless carbon papers and duplicating manifold record systems of the type referred to above, because of their superior stability both in the leuco form and in the colored form obtained by contact with an acidic electron acceptor.
- the leuco form they are stable to storage in containers open to the atmosphere, as well as when incorporated into record sheets of the type disclosed in US. Patents 2,548,366 and 2,712,507 and exposed to the atmosphere and to light.
- In the form of colored compounds formed by contact with acidic electron acceptors of the type referred to above they are stable to light and to the atmosphere, even when embodied as record sheet material exposed to sunlight.
- N-phenyl leucoaurarnine and related compounds which when incorporated into record sheet material of the type disclosed, for example, in U.S. Patents 2,548,366 and 2,712,507, are unstable and/or volatilize or rapidly become ineffective; and in contrast to the rapid fading of the color produced by contact of acidic clays with crystal violet lactone heretofore employed commercially. Further, they do not stain the skin when the record sheets are handled.
- Example 1 of the present application when the compound of Example 1 of the present application is substituted for the mixture of crystal violet lactone and methylene base employed in Example 1 of U.S.P. 2,548,366, the resulting sheets are stable during storage for long periods of time and when placed one above the other, with the claycoated surfaces upward, and marked with a stylus, a blue marking is de veloped on the clay-coated surface of the lower sheet where pressure was applied, which marking does not fade.
- the sulfonamidcs of the present invention can be prepared in various ways.
- the simplest method from the standpoint of availability of starting materials and apparatus required involves the condensation of a bis(p-dialkylaminoaryl)methyl hydrol having the formula R H Ra Rf AB R with a sulfonamide having the formula RHSOQNH wherein R R R R R R have the meaning given above, preferably in substantially equimolar amounts.
- the condensation is preferably carried out by heating in a solvent at a temperature between and C. (All ranges given herein, including the claims, are inclusive of the limits.)
- the general method of preparation preferably Consists in refluxing substantially equimolecular proportions of the benzhydrol and of the sulfonamide in a suitable solvent having a boiling point between 80 and 150 C., at least a fraction of each of the two reactants being soluble in the solvent.
- Suitable solvenm are for example, hydrocarbon solvents, such as petroleum hydrocarbons (such as 2,2,4-trimethylpentane and low boiling kerosene frac tions), aromatic hydrocarbons (such as benzene, toluene or xylene), and mixtures preferably having a boiling range between 80 and 150 C., and alcohols, such as ethyl, propyl or butyl alcohols or mixtures thereof.
- water formed in the reaction is preferably removed.
- the bis(p-dialkylaminoaryl)methyl sulfonamides thus obtained may be purified by recrystallization from a suitable solvent.
- hydrols which are suitable for use in the process: I Michlers hydrol: 4,4-bis(dimethylamino)benzhydrol 4,4'-bis(diethylamino) benzhydrol 4,4'-bis(dipropylamino)benzhydrol 4,4-bis(dibutylamino) benzhydrol 4,4'-bis( dimethylamino) -2,2'-dichloro-benzhydrol 4,4-bis( dimethylamino) 3,3-dimethyl-benzhydrol 4,4'-bis(diethylamino) -2,2'-dibromo-benzhydrol
- sulfonarnides which are suitable for use in the process, alone or in the formof mixtures of two or more of them Methane sulfonamide Ethane sulfonamide Propane sulfonamides Butane sulfonamides
- Example 1 water separator of the conventional type which continueagitator, and a reflux condenser connected to a ously collects the reflux condensate of water, benzene and toluene, separates the water from the hydrocarbons, and
- the crude product thus obtained was recrystallized first from benzene (about 400 parts by volume) and then from toluene (about 500 parts by volume), and dried in a vacuum drier.
- the crude crystals were dissolved in the hot solvent and adecolorizing carbon (Nuchar) was added in an amount about 1 to 5% of the weight of the crystals, after which the hot mixture was sludge filtered and the filtrate was allowed to cool, to crystallize the purified product.
- a toluene solution thereof was contacted with bentonite a blue coloration was produced.
- Example 3 The procedure of Example 2 was repeated using 37.4 parts ot p-methoxybenzenesulfonamide (0.2 mol) in place of the p-toluenesultonamide, and 500 parts by volume rather than 350 parts by volume of toluene.
- Example 4 The procedure of Example 3 was repeated using methane. A solution thereof in toluene gave a [blue color, when spotted on bentonite. i
- the hot reaction mixture after dilution with 25 0 parts by volume of toluene and reheating to produce a clear solution, was sludge filtered hot and the filtrate was allowed to cool to room temperature.
- the crude crystals were recrystallized from toluene (500 parts by volume) in the presence of a small amount of decolorizing charcoal (Nuchar) and dried as in Example 1.
- Example 6 A mixture of 30 parts of Michlers hydrol (90% strength, equivalent to 0.1 mol), 28.4 parts (0.1 mol) of p-di-n-butylaminobenzenesulfonamide (having a melting point 132-l34 and 250 parts by volume of toluene was heated to boiling and refluxed (112) for 48 hours to complete the condensation reaction. The mixture was then cooled to room temperature and filtered. The crystals were washed with 25 parts by volume of toluene and dried in a vacuum drier at 3035.
- Example 7 The procedure of Example 3 was repeated using 66.6 parts (0.2 mol) of octadecanesulfonamide in place of the p-methoxybenzenesulfonamide.
- Example 8 The procedure of Example 3 was repeated using 41.4 parts of l-naphthalenesulfonamide (0.2 mol) in place of the p-methoxybenzenesulfonamide.
- the product thus obtained as colorless crystals was 1- naphthylsulfonamido bis(p dimethylaminophenyl)- methane. When dissolved in toluene and spotted on bentonite, a blue coloration was produced.
- Example 9 A mixture of 30 parts of Michlers hydrol (0.1 mol of 100%), 20.5 parts of naphthosultam (0.1 mol of 100%), and 175 parts by volume of ethyl alcohol (213 denatured) was heated to boiling and refluxed (7880) for 50 hours. The mixture was then cooled to room temperature and filtered.
- the crystals were dissolved in 500 parts by volume of a mixture of equal volumes of toluene and isopropyl alcohol, at the boil. The solution was charged with 2 parts of decolorizing carbon (Nuchar) and sludge filtered. The filtrate was cooled to room temperature and filtered.
- decolorizing carbon Nuchar
- Example 10 The procedure of Example 3 was repeated using 31.6 parts (0.2 mol) of 3-pynidinesulfonamide in place of the p-methoxyphenylsulfonamide.
- the purified product thus obtained was 3-pyn'dylsulfonamido-bis (p-dimethylaminophenyl)methane having the formula CE: /CH3 CH3 l C Ha N N -H It was essentially colorless, and when dissolved in toluene and spotted on bentonite, gave a blue color.
- Example 11 A mixture of 32.6 parts of 4,4-bis(diethylamino)benz hydrol (0.1 mol of 100%, 15.7 parts of benzenesulfonamide (0.1 mol of 100%), and 200 parts by volume of ethyl alcohol (2B denatured) was heated to refluxing for 50 hours. The reaction mixture was sludge filtered hot, and the filtrate was cooled to 0 for 3 days.
- the tacky crystals thus obtained were filtered oil and dried in vacuo at 30-35
- the product was recrystallized from ethyl ether, yielding phenylsulfonamido-bis(p-diethylaminophenyl)methane, i.e., N-bis(p-diethylaminophenyl)methyl benzenesulfonamide, in the form of gray crystals melting at 155 uncorrected.
- phenylsulfonamido-bis(p-diethylaminophenyl)methane i.e., N-bis(p-diethylaminophenyl)methyl benzenesulfonamide
- Example 12 A mixture of 27 parts of Michlers hydrol (0.1 mol of 20.7 parts of Z-naphthalenesulfonamide (0.1 mol) and 200 parts by volume of toluene was refluxed at 112 for 40 hours, while removing water as in Example 1, until the condensation was complete. The reaction mixture was sludge filtered at room temperature. The filtrate was refrigerated to -10", and the crystals obtained were filtered off and dried.
- the crude crystals thus obtained were recrystallized from toluene.
- the purified product thus obtained as tan crystals having a melting point of 164, uncorrected, was 2-naphthylsulfonamido-bis(p-dimethylaminophenyDmethane.
- a solution thereof in toluene when spotted on paper coated with bentonite gradually gave a greenish blue color, which overnight became deep reddish blue.
- Example 13 32.6 parts of 4,4'-bis(diethylamino)benzhydrol (0.1 mol of 100%), 17.1 parts of p-toluenesulfonamide (0.1 mol), and 250 parts by volume of toluene was refluxed at 113 for 32 hours, while separating water as in Example 1. The reaction mixture was sludge filtered hot,
- the Michlers hydrol employed in certain of the examples was a technical product containing mineral acid impurities. Accordingly such examples include the addition of a small amount of sodium hydroxide to neutralize said impurities.
- Other neutralizing agents can be used similarly, such as sodium carbonate.
- N-bis(p-dialkylaminoaryl)methyl sulfonamides in which the alkyl groups of the dialkylamino radicals each have 1 to carbon atoms; the aryl radicals are each selected from the group consisting of phenylene and phenylene monosubstituted by a member of the group consisting of lower alkyl, lower alkoxy, fluorine, chlorine, bromine, di-lower alkylamino, lower alkanoylamino, and 'SO NH and the sulfonamide radicals have the formula:
- R represents a radical selected from the group consisting of (A) alkyl up to 18 carbon atoms; octadecenyl; cycloalkyl in which the ring contains 5 to 6 carbon atoms; phenyl-lower alkyl; (B) phenyl, tolyl, xylyl, naphthyl, biphenyl, indenyl, pyridyl, quinolyl, benzothiazyl, benzofuryl and phenothiazyl, and the radicals of (B) monosubstituted by a member of the group consisting of lower alkyl, lower alkaxy, fluorine,
- N-bis(p-dialkylaminoaryl)methyl alkyl sulfonamides having 1 to 18 carbon atoms in the alkyl group in which the alkyl groups of the dialkylamino radicals each have 1 to 2 carbon atoms, and the aryl radicals are mononuclear aryl hydrocarbon radicals.
- N-bis(p-dialkylaminoaryl)methyl aryl sulfonamides in which the alkyl groups of the dialkylarnino radicals each have 1 to 2 carbon atoms, and the aryl radicals are mononuclear aryl hydrocarbon radicals.
- N-bis(p-dialkylaminophenyl)methyl alkyl sulfonamides having 1 to 18 carbon atoms in the alkyl group the alkyl groups of the dialkylamino radicals each hav ing 1 to 2 carbon atoms.
- N-bis(p-dialkylaminophenyl)methyl aryl sulfonamides the alkyl groups of the dialkylamino radicals each having 1 to 2 carbon atoms and the aryl radical is a mononuclear aryl hydrocarbon radical.
Description
N-BIS(p-l) IALKYLAMINOPHENYDMETHYL SULFONAMIDES Frederick H. Kranz, Bufialo, N.Y., assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed May 12, 1958, Ser. No. 734,419
14 Claims. (Cl. 260-556) This invention relates to compounds which are derivatives of. bis(p-dialkylaminoaryl)methane in which nitrogen is linked to the methane carbon atom. It relates more particularly to compounds of said type having superior properties as compared to known compounds of said general class.
An object of the present invention is to provide novel derivatives of bis(p-dialkylaminoaryl)methane, and especially of bis(p-dimethylaminophenyl)methane, in which the methane carbon atom thereof is linked to the nitrogen atom of a nitrogen-containing radical having a beneficial effect upon the properties of said derivatives.
A further object of the present invention is to pro vide novel bis(p-dialkylaminoaryl) methyl derivatives of said type which are lightly colored or substantially colorless but which when contacted with acidic electron acceptors produce colored compositions.
Another object of the present invention is to provide novel compounds of said type having superior stability as compared to N-bis (p-dimethylaminophenyl)methyl aniline (also known as N-phenyl leucoauramine) and derivatives of the latter, when embodied in manifold record systems of the type disclosed in US. Patents 2,505,470 and 2,548,366, for example.
Other objects of the invention will in part be obvious and will in part appear hereinafter.
It is known that derivatives of benzhydrol and such compounds as crystalline violet lactone, when dissolved in non-polar solvents, such as, benzene, toluene or chlorinated biphenyl, and brought into contact with acidic electron acceptors such as kaolin, bentonite, attapulgite, silica gel, felspar, pyrophyllite, halloysite, magnesium trisilicate Zinc sulphate, zinc sulfide, calcium, fluoride, and calcium citrate, as well as organic acids such as tannic acid and benzoic acid, turn from colorless to a deep blue or violet shade.
Compounds which are derivatives of bis(p-dimethylaminophenyl)methane in which the nitrogen atom of a phenylamino radical replaces one of the methane hydrogen atoms, such as N-phenyl leucoaurarnine, i.e., N bis(pdimethylaminophenyl)methyl aniline, are known .com-
pounds which are colorless or substantially colorless, but
which constitute color-reactants of the electron donor type since they turn blue on coming into absorptive contact with acidic electron acceptor materials such as acidic clays (for example, attapulgite, halloysite, kaolin.
and bentonite), as well as aluminum sulfate, zeolite material, silica gel, magnesium trisilicate, and Zinc sulphide, among others. They have been proposed for use heretofore in solution in toluene or chlorinated biphenyl for printing in color on paper or other material coated or filled with such acidic materials. Thus, they have been proposed for use in so-called colorless carbon papers, impact printing papers and duplicating manifold record systems, for example, of the type disclosed in U.S.P. 2,505,470, wherein a solution of the N-bis(p-dimethy1- 2 aminophenyl)methyl aniline is provided in the form of discrete particles in conjunction with a sohd lnsulatmg material including an organic hydrophilic film-forming material and an acidic clay which, upon pressure by a stylus or impact, as by a typewriter key, causes combination of the color-forming reactant with the clay and a resulting colored mark; and, for example, of the type disclosed in U.S.P. 2,548,366, wherein the rear surface of each top sheet of a series of overlying sheets is coated.
with a dispersion of a suitable solution of the N-bis (p-dimethylaminophenyl)methyl aniline in a rupturable hydrophilic colloid film, and the adjacent top surface of the next underlying sheet is coated or filled with an electronacceptor acidic material, so that pressure of a stylus or impact upon the top sheet causes color formation on the surface containing the acidic material at the points 1 of pressure or impact. I
I have discovered that sulfonamide derivatives of bis-f (p-dimethylaminophenyl)methane and related compounds, in which the nitrogen atom of a sulfonamide replaces one of the methane hydrogen atoms, possess advantageous properties which render them particularly useful in systems of the above type.
The compounds of the present invention are N-bis(pdialkylaminoaryl)methyl sulfonamides in which the alkyl groups of the dialkylamino radical each have 1 to 5 carbon atoms, and the aryl radicals are mononuclear aryl radicals. They include compounds which in themselves are colored (containing chromophoric groups) and compounds which are lightly colored, or colorless, or substantially colorless (free from chromophoric groups). Further, they include compounds which include in their molecules acidic groups containing a hydrogen cation (for example, a sulfonic acid or carboxylic acid radical), and compounds free from such acidic groups. In this connection it is noted that groups which do not contain a hydrogen cation, such as salts of acidic groups (e.g.,
alkali metal, ammonium, organic base and other salts of carboxylic and sulfonic acids) are included herein as being free from'acid groups containing a free hydrogen cation.
colorless in the solid form (leuco form), which renders them of special utility in the manufacture of impact printing and duplicating materials of the types referred to above.
The alkyl radicals of the p-dialkylamino radicals ome Commethyl, ethyl, propyl, butyl and amyl radicals. pounds in which they are methyl or ethyl are preferred;
The mononuclear aryl radicals include unsubstituted phenylene radicals and phenylene radicals containing one or more inert substituents such as alkyl, alkoxy, halogen or acylamino substituents; for example, tolylene,
chlorophenylene, bromophenylene, Compounds in which they are. mononuclear aryl. hydrocarbon radicals, and especially phenylene, are pre-Y methoxyphenylene, etc.
ferred.
The sulfonarnide radicals of the compounds. of present invention include various types of such radicals. f, Thus they include sulfonamide radicals in which the radi cal attached to the sulfon group is an alkyl, cycloalkyl, a sultani aralkyl, aryl,.or heterocyclic radical, or part of (in which the group is linked to diiferentjcarbon atoms of thesame' radical), a number of which are illustrated below.
Patented Aug. '9, 1960 They also include radicals in which the hydrogen atom of the group is substituted by an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical. Preferably they are free from chromophoric groups and from acidic groups containing a hydrogen cation, which would interfere with their use as leuco electron-donor color reactants. They may, however, contain such substituents as alkyl, alkoxy, halogen, dialkylamino, acylamino and sulfonamido groups.
The N-bis (p-dialkylaminoaryl)methyl sulfonamides of the present invention have the formula wherein:
R R R and R are each an alkyl radical having 1 to 5 carbon atoms (such as, methyl, ethyl, propyl, butyl or amyl),
R is selected from the group consisting of alkyl (such as, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl, hexadecyl, octadecyl or octadecenyl), cycloalkyl (such as, cyclopentyl, cyclohexyl or methyl cyclohexyl), aralkyl (such as, benzyl or phenylethyl), aryl (such as, phenyl, tolyl, xylyl, naphthyl, biphenyl or indene) and heterocyclic (such as, pyridyl, quinolyl, benzothiazyl, benzofuryl or pheuothiazyl) radicals, including substituted derivatives of such radicals and preferably those free from chromophoric groups and from acidic groups containing a hydrogen cation (such as the alkyl, alkoxy, fluorine, chlorine, bromine, dialkylamino, acylamino or sulfamido derivatives of the radicals referred to above), and sultam radicals which are part of the same radicals jointly with R (such as, naphthsultam) R is selected from the group consisting of hydrogen and the radicals represented by R and are selected from the group consisting of the phenylene radical and substituted derivatives thereof, preferably those free from chromophoric groups and from acidic groups containing a hydrogen cation (such as the allryl, alkoxy, fluorine, chlorine, bromine, dialkylamino, acylamino or sulfamido derivatives thereof).
Those compounds are of particular value in which R R, R and R are methyl or ethyl, the phenylene radicalls are mononuclear aryl hydrocarbon radicals, R is hydrogen or methyl, and R is phenyl, tolyl, methoxyphenyl, or dimethylaminophenyl.
The compounds of the present invention are soluble in a wide variety of non-polar organic solvents, such as benzene, toluene, kerosene, mineral oil, dioctylphthalate, chlorinated biphenyls, etc. When applied as a solution in such solvents to a paper or other material coated with an acidic material, such as bentonite, kaolin, felspar, monoor dibasic barium or calcium phosphates, they produce generally greenish blue to violet colorations. In addition, by virtue of the sulfonamido radical, they possess relatively low volatility and high stability to air and light. These advantageous properties render the lightly colored to colorless sulfonamides of the present invention outstanding for use in systems of the above type.
Thus, the compounds of the present invention are useful in the formation of colored compounds or difierently colored compounds by contact with electron acceptor or acidic materials which cause a rearrangement of the chemical molecule with intensification of the color thereof, such as those enumerated above.
Lightly colored, and especially colorless or substantially colorless, compounds of this invention are particularly useful in so-called colorless carbon papers and duplicating manifold record systems of the type referred to above, because of their superior stability both in the leuco form and in the colored form obtained by contact with an acidic electron acceptor. Thus, in the leuco form they are stable to storage in containers open to the atmosphere, as well as when incorporated into record sheets of the type disclosed in US. Patents 2,548,366 and 2,712,507 and exposed to the atmosphere and to light. In the form of colored compounds formed by contact with acidic electron acceptors of the type referred to above, they are stable to light and to the atmosphere, even when embodied as record sheet material exposed to sunlight. This is in contrast to N-phenyl leucoaurarnine and related compounds, which when incorporated into record sheet material of the type disclosed, for example, in U.S. Patents 2,548,366 and 2,712,507, are unstable and/or volatilize or rapidly become ineffective; and in contrast to the rapid fading of the color produced by contact of acidic clays with crystal violet lactone heretofore employed commercially. Further, they do not stain the skin when the record sheets are handled.
For example, when the compound of Example 1 of the present application is substituted for the mixture of crystal violet lactone and methylene base employed in Example 1 of U.S.P. 2,548,366, the resulting sheets are stable during storage for long periods of time and when placed one above the other, with the claycoated surfaces upward, and marked with a stylus, a blue marking is de veloped on the clay-coated surface of the lower sheet where pressure was applied, which marking does not fade.
The sulfonamidcs of the present invention can be prepared in various ways. The simplest method from the standpoint of availability of starting materials and apparatus required involves the condensation of a bis(p-dialkylaminoaryl)methyl hydrol having the formula R H Ra Rf AB R with a sulfonamide having the formula RHSOQNH wherein R R R R R R have the meaning given above, preferably in substantially equimolar amounts. The condensation is preferably carried out by heating in a solvent at a temperature between and C. (All ranges given herein, including the claims, are inclusive of the limits.)
The general method of preparation preferably Consists in refluxing substantially equimolecular proportions of the benzhydrol and of the sulfonamide in a suitable solvent having a boiling point between 80 and 150 C., at least a fraction of each of the two reactants being soluble in the solvent. Suitable solvenm are for example, hydrocarbon solvents, such as petroleum hydrocarbons (such as 2,2,4-trimethylpentane and low boiling kerosene frac tions), aromatic hydrocarbons (such as benzene, toluene or xylene), and mixtures preferably having a boiling range between 80 and 150 C., and alcohols, such as ethyl, propyl or butyl alcohols or mixtures thereof. When effected in a hydrocarbon solvent, water formed in the reaction is preferably removed. The bis(p-dialkylaminoaryl)methyl sulfonamides thus obtained may be purified by recrystallization from a suitable solvent.
. The following are illustrative of hydrols which are suitable for use in the process: I Michlers hydrol: 4,4-bis(dimethylamino)benzhydrol 4,4'-bis(diethylamino) benzhydrol 4,4'-bis(dipropylamino)benzhydrol 4,4-bis(dibutylamino) benzhydrol 4,4'-bis( dimethylamino) -2,2'-dichloro-benzhydrol 4,4-bis( dimethylamino) 3,3-dimethyl-benzhydrol 4,4'-bis(diethylamino) -2,2'-dibromo-benzhydrol The following are illustrative of sulfonarnides which are suitable for use in the process, alone or in the formof mixtures of two or more of them Methane sulfonamide Ethane sulfonamide Propane sulfonamides Butane sulfonamides Pentane sulfonamides Hexane sulfonamides Octane sulfonamides Decane sulfonamides Dodecane sulfonamides, especially the normal primary Hexadecane sulfonamides, especially the normal primary Octadecane sulfonamides, especially the normal primary Octadecene sulfonamide (oleyl sulfonamide) Mixtures of sulfonamides derived from sulfuryl chloride reaction products of hydrocarbon mixtures Cyclopentane sulfonamide Cyclohexane sulfonamide Methyl-cyclohexane sulfonamide N-methyl-cyclohexane sulfonarnide Phenylmethane sulfonamide (benzyl sulfonamide) Phenylethane sulfonamide Benzene sulfonamide 4-toluene sulfonamide 4-chlorobenzene sulfonamide 4-methoxybenzene sulfonarnide 4-dimethylaminobenzene sulfonamide 4-diethylaminobenzene sulfonamide 4-di-n-butylaminobenzene sulfonamide N-methyl-benzene sulfonanu'de 1.3-benzene disulfonamide l-naphthalene sulfonarnide Z-naphthalene sulfonamide 4-diphenyl sulfonarnide 4-indene sulfonamide 3-py'ridine sulfonamide 6-quinoline sulfonamide Z-benzothiazole sulfonamide fi-benzothiazole sulfonamide S-benzofurane sulfonamide 3-phenothiazine sulfonamide Naphthosultam The invention will be illustrated by the following specific examples, but it is to be understood that it is not limited to the details thereof and that changes may be made without departing from the scope of the invention. The temperatures are in degrees centigrade and the parts and percentages are by weight, tmless designated as parts by volume. Where parts are by volume, the amount signifies the volume occupied by the same number of parts by weight of water at 4 C.
Example 1 water separator of the conventional type which continutagitator, and a reflux condenser connected to a ously collects the reflux condensate of water, benzene and toluene, separates the water from the hydrocarbons, and
returns the latter to the reaction. The charge was heated to boiling and refluxed (at about 100) for 40 hours,
while removing the water generated by the condensation reaction. The reaction mix 'ture was then cooled to room temperature, and the resulting needle-like crystals were separated by filtration.
The crude product thus obtained was recrystallized first from benzene (about 400 parts by volume) and then from toluene (about 500 parts by volume), and dried in a vacuum drier. In carrying out these recrystallizations, the crude crystals were dissolved in the hot solvent and adecolorizing carbon (Nuchar) was added in an amount about 1 to 5% of the weight of the crystals, after which the hot mixture was sludge filtered and the filtrate was allowed to cool, to crystallize the purified product.
The product thus obtained as white crystals having a melting point of 174-176, uncorrected, was phenylsulsulfonamidobis(pdimethylaminophenyl)methane of the formula Example 2 A mixture of 60 parts of Michlers hydrol, technical grade (equivalent to 0.2 mol of 100%), 34 parts of ptoluenesulfonamide (equivalent to 0.2 mol), 4 parts by volume of 25% aqueous sodium hydroxide and 350 parts by volume of toluene was refluxed for 32 hours as in Example 1, to complete the condensation reaction. The
mixture was then cooled and filtered. The crude prodnot thus obtained was recrystallized from 300 parts by volume of toluene in the presence of a small amount of a decolon'zing carbon (Nuchar).
The purified product thus obtained as white crystals melting at 180181, uncorrected, was p-tolysulfonamido bis(p dimethylaminophenyhmethane. When a toluene solution thereof was contacted with bentonite a blue coloration was produced.
Example 3 The procedure of Example 2 was repeated using 37.4 parts ot p-methoxybenzenesulfonamide (0.2 mol) in place of the p-toluenesultonamide, and 500 parts by volume rather than 350 parts by volume of toluene.
The purified product thus obtained as white crystals melting at -177, uncorrected, was p-methoxyphenylsulfonamido bis(p dimethylaminophenyl)methane. A solution thereof in toluene when spotted on bentonite.
Example 4 The procedure of Example 3 was repeated using methane. A solution thereof in toluene gave a [blue color, when spotted on bentonite. i
gave a blue color bite crystals? uncorrected, was pdimethyl e aminophenylsulfonamido bis(p-dimethylaminophenyl) Example A mixture of 51.8 parts of Michlers hydrol, technical grade (equivalent to 0.175 mol of 100%), 42.6 parts of p-diethylaminobenzenesulfonamide, 4 parts by volume of 25% aqueous sodium hydroxide, and 250 parts by volume of toluene was. boiled and refluxed for 12 hours, while continuously removing water as in Example 1. The hot reaction mixture, after dilution with 25 0 parts by volume of toluene and reheating to produce a clear solution, was sludge filtered hot and the filtrate was allowed to cool to room temperature. The crystals thus obtained were separated =by filtration and dried in a vacuum drier at about 40. The crude crystals were recrystallized from toluene (500 parts by volume) in the presence of a small amount of decolorizing charcoal (Nuchar) and dried as in Example 1.
The product thus obtained as white crystals melting at 145 -150, uncorrected, was p-diethylaminophenylsulfonamido bis(p dimethylaminophenyl)methane. A solution thereof in toluene produced a greenish blue color when spotted on bentonite.
Example 6 A mixture of 30 parts of Michlers hydrol (90% strength, equivalent to 0.1 mol), 28.4 parts (0.1 mol) of p-di-n-butylaminobenzenesulfonamide (having a melting point 132-l34 and 250 parts by volume of toluene was heated to boiling and refluxed (112) for 48 hours to complete the condensation reaction. The mixture was then cooled to room temperature and filtered. The crystals were washed with 25 parts by volume of toluene and dried in a vacuum drier at 3035.
The crystalline product thus obtained, p-di-n-butylaminophenylsulfonamido bis(p dimethylaminophenyl) methane, was essentially colorless and had a melting point of 171-173. A toluene solution thereof spotted on paper coated with bentonite produced a blue coloration.
Example 7 The procedure of Example 3 was repeated using 66.6 parts (0.2 mol) of octadecanesulfonamide in place of the p-methoxybenzenesulfonamide.
The product thus obtained as essentially colorless crystals was octadecylsulfonamido-bis(p-dimethylaminophenyl)methane having the formula:
Us: {I /CHs CH: IYTH CH:
CxsHavSOz When a solution thereof in toluene was spotted on bentonite, a blue coloration was obtained.
Example 8 The procedure of Example 3 was repeated using 41.4 parts of l-naphthalenesulfonamide (0.2 mol) in place of the p-methoxybenzenesulfonamide.
The product thus obtained as colorless crystals was 1- naphthylsulfonamido bis(p dimethylaminophenyl)- methane. When dissolved in toluene and spotted on bentonite, a blue coloration was produced.
Example 9 A mixture of 30 parts of Michlers hydrol (0.1 mol of 100%), 20.5 parts of naphthosultam (0.1 mol of 100%), and 175 parts by volume of ethyl alcohol (213 denatured) was heated to boiling and refluxed (7880) for 50 hours. The mixture was then cooled to room temperature and filtered.
The crystals were dissolved in 500 parts by volume of a mixture of equal volumes of toluene and isopropyl alcohol, at the boil. The solution was charged with 2 parts of decolorizing carbon (Nuchar) and sludge filtered. The filtrate was cooled to room temperature and filtered.
8 The nearly white crystalline product thus obtained was naphthosultamyl bis(p dimethylaminophenyl)methane having the formula Cg: 1?: CH3
) O CH; I OH:
It decomposed at 223 when heated. When a solution thereof in toluene was poured onto paper coated with hentonite clay, a blue coloration was obtained.
Example 10 The procedure of Example 3 was repeated using 31.6 parts (0.2 mol) of 3-pynidinesulfonamide in place of the p-methoxyphenylsulfonamide.
The purified product thus obtained was 3-pyn'dylsulfonamido-bis (p-dimethylaminophenyl)methane having the formula CE: /CH3 CH3 l C Ha N N -H It was essentially colorless, and when dissolved in toluene and spotted on bentonite, gave a blue color.
Example 11 A mixture of 32.6 parts of 4,4-bis(diethylamino)benz hydrol (0.1 mol of 100%, 15.7 parts of benzenesulfonamide (0.1 mol of 100%), and 200 parts by volume of ethyl alcohol (2B denatured) was heated to refluxing for 50 hours. The reaction mixture was sludge filtered hot, and the filtrate was cooled to 0 for 3 days. The tacky crystals thus obtained were filtered oil and dried in vacuo at 30-35 The product was recrystallized from ethyl ether, yielding phenylsulfonamido-bis(p-diethylaminophenyl)methane, i.e., N-bis(p-diethylaminophenyl)methyl benzenesulfonamide, in the form of gray crystals melting at 155 uncorrected. When dissolved in toluene and poured onto paper coated with bentonite, a greenish blue color was slowly produced, which overnight became deep reddish blue.
Example 12 A mixture of 27 parts of Michlers hydrol (0.1 mol of 20.7 parts of Z-naphthalenesulfonamide (0.1 mol) and 200 parts by volume of toluene was refluxed at 112 for 40 hours, while removing water as in Example 1, until the condensation was complete. The reaction mixture was sludge filtered at room temperature. The filtrate was refrigerated to -10", and the crystals obtained were filtered off and dried.
The crude crystals thus obtained were recrystallized from toluene. The purified product thus obtained as tan crystals having a melting point of 164, uncorrected, was 2-naphthylsulfonamido-bis(p-dimethylaminophenyDmethane. A solution thereof in toluene when spotted on paper coated with bentonite gradually gave a greenish blue color, which overnight became deep reddish blue.
Example 13 32.6 parts of 4,4'-bis(diethylamino)benzhydrol (0.1 mol of 100%), 17.1 parts of p-toluenesulfonamide (0.1 mol), and 250 parts by volume of toluene was refluxed at 113 for 32 hours, while separating water as in Example 1. The reaction mixture was sludge filtered hot,
the filtrate was cooled to and the resulting crystals were filtered ofr and dried in vacuo at 3035.
The product thus obtained as cream colored crystals melting at 142, uncorrected, was p-tolylsulfonamido-bis- (p-diethylaminophenyl) methane. When a solution thereof in toluene was spotted on bentonite, a greenish blue color formed gradually and became deep reddish blue overnight.
It will be evident to those skilled in the art that the invention not limited to the details of the foregoing illustrative examples and that changes can be made without departing from the scope of the invention.
Thus, instead of the hydrols and sulfonamides employed in the examples, others of those specified above may be substituted in equivalent amounts. Further instead of the hydrol, the corresponding bis (p-dialkylaminoaryDmethyl chloride or bromide may be used.
The Michlers hydrol employed in certain of the examples was a technical product containing mineral acid impurities. Accordingly such examples include the addition of a small amount of sodium hydroxide to neutralize said impurities. Other neutralizing agents can be used similarly, such as sodium carbonate.
I claim:
1. N-bis(p-dialkylaminoaryl)methyl sulfonamides in which the alkyl groups of the dialkylamino radicals each have 1 to carbon atoms; the aryl radicals are each selected from the group consisting of phenylene and phenylene monosubstituted by a member of the group consisting of lower alkyl, lower alkoxy, fluorine, chlorine, bromine, di-lower alkylamino, lower alkanoylamino, and 'SO NH and the sulfonamide radicals have the formula:
wherein:
R represents a radical selected from the group consisting of (A) alkyl up to 18 carbon atoms; octadecenyl; cycloalkyl in which the ring contains 5 to 6 carbon atoms; phenyl-lower alkyl; (B) phenyl, tolyl, xylyl, naphthyl, biphenyl, indenyl, pyridyl, quinolyl, benzothiazyl, benzofuryl and phenothiazyl, and the radicals of (B) monosubstituted by a member of the group consisting of lower alkyl, lower alkaxy, fluorine,
chlorine, bromine, di-lower alkylamino, lower alkanoylamino and -SO NH and the naphthosultam radical which is part of the same radical jointly with R and R represents a radical selected from the group consisting of hydrogen and the radicals represented by R 2. N-bis(p-dialkylaminoaryl)methyl alkyl sulfonamides having 1 to 18 carbon atoms in the alkyl group in which the alkyl groups of the dialkylamino radicals each have 1 to 2 carbon atoms, and the aryl radicals are mononuclear aryl hydrocarbon radicals.
3. N-bis(p-dialkylaminoaryl)methyl aryl sulfonamides in which the alkyl groups of the dialkylarnino radicals each have 1 to 2 carbon atoms, and the aryl radicals are mononuclear aryl hydrocarbon radicals.
4. N-bis(p-dialkylaminophenyl)methyl alkyl sulfonamides having 1 to 18 carbon atoms in the alkyl group the alkyl groups of the dialkylamino radicals each hav ing 1 to 2 carbon atoms.
5. N-bis(p-dialkylaminophenyl)methyl aryl sulfonamides the alkyl groups of the dialkylamino radicals each having 1 to 2 carbon atoms and the aryl radical is a mononuclear aryl hydrocarbon radical.
6. N-bis(p-dimethylaminophenyl)methyl alkyl sulfonamides having 1 to 18 carbon atoms in the alkyl group.
7. N-bis(p-dimethylaminophenyl)methyl cycloalkyl sulfonamides in which the cycloalkyl ring contains 5 to 6 carbon atoms.
8. N-bis(p-dimethylarninophenyl)methyl phenyl-lower alkyl sulfonamides.
9. N-bis (p-dimethylaminophenyl)methyl aryl sulfonamides in which the aryl radical is a mononuclear aryl hydrocarbon radical.
10. N-bis(p dimethylaminophenyl)methyl phenylsulfonarnide.
l1. N-bis(p-dimethylaminophenyl)methyl naphthylsulfonarnide.
12. N-bis(p dimethylaminophenyl)methyl p-tolylsulfonarnide.
l3. N-bis(p-dimethylaminophenyl)methyl p-methoxyphenylsulfonamide.
14. N-bis(p-dimethylaminophenyl)methyl p-dimethylaminophenylsulfonamide.
References Cited in the file of this patent Bogert et al.: I. Am. Chem. Soc., vol. 44, pp. 2612-21 (1922).
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2 948 753 August 9, 1960 Frederick H. Kranz It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
line 43 for "crystalline" read crystal for "'4-diphenyl sulfonamide" read column 6 line 2O for line 51 Example 2, for ulfon-a- -gcolumn 8, line 3'7, 100%) column 9, line ll Column 1,
column 5, line 46 4-biphenyl sulfonamide "phenylsul read phenyl "ptolysulfon-" read p-t0lyls Example 11, for "100% read for "alkaxy" read alkoxy Signed and sealed this 4th day of April 1961.
(SEAL) Att ERNEST W. SWIDER XXXXXXEEW ARTHUR w. CROCKER Attesting Ofiicer Acting Commissioner of Patents
Claims (1)
1. N-BIS(P-DIALKYLAMINOARYL)METHYL SULFONAMIDES IN WHICH THE ALKYL GROUPS OF THE DIALKYLAMINO RADICALS EACH HAVE 1 TO 5 CARBON ATOMS, THE ARYL RADICALS ARE EACH SELECTED FROM THE GROUP CONSISTING OF PHENYLENE AND PHENYLENE MONOSUBSTITURED BY A MEMBER OF THE GROUP CONSISTING OF LOWER ALKYL, LOWER ALKYL, FLUORINE CHLORIEN, BROMINE, DI-LOWER ALKYLAMINO, LOWER ALKANOYLAMINO, AND -SO2NH2, AND THE SULFONAMIDE RADICALS HAVE THE FORMULA:
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US3116257A (en) * | 1960-12-19 | 1963-12-31 | Pure Oil Co | Surdfactant compositions containing salts of vinylsulfonanilides |
US3143558A (en) * | 1960-01-06 | 1964-08-04 | Schering Ag | Aryl sulfonylthionylamides and derivatives thereof and methods of producing the same |
US3157677A (en) * | 1959-05-09 | 1964-11-17 | Basf Ag | Sulfonic acid salts of auramine |
US3193404A (en) * | 1959-03-19 | 1965-07-06 | Davis Chester | Associated dye salts and method of forming colored indicia therewith |
US3239564A (en) * | 1960-12-02 | 1966-03-08 | Reeder Earl | 2 n-substituted amino halobenzo-phenones |
US3377185A (en) * | 1964-11-18 | 1968-04-09 | Scott Paper Co | Arylmethane dye azides and method of forming colored indicia therewith |
US3404995A (en) * | 1965-09-20 | 1968-10-08 | Columbia Ribbon Carbon Mfg | Hectograph products and processes |
USRE30797E (en) * | 1977-11-09 | 1981-11-17 | Scott Paper Company | Associated dye salts and method of forming colored indicia therewith |
USRE30803E (en) * | 1977-11-09 | 1981-11-24 | Scott Paper Company | Colorless recording paper |
US4531139A (en) * | 1983-10-02 | 1985-07-23 | The Standard Register Company | Color developers for pressure-sensitive or heat-sensitive recording papers |
US4623391A (en) * | 1983-10-02 | 1986-11-18 | The Standard Register Company | Color developers for pressure-sensitive or heat-sensitive recording papers |
DE4010641A1 (en) * | 1990-04-03 | 1991-10-10 | Bayer Ag | COLOR IMAGE MIXTURE FOR PRINTING AND HEAT-SENSITIVE RECORDING SYSTEMS |
EP1138517A2 (en) * | 2000-03-27 | 2001-10-04 | Mitsui Chemicals, Inc. | Developer composition and heat sensitive recording material |
-
1958
- 1958-05-12 US US734419A patent/US2948753A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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None * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3193404A (en) * | 1959-03-19 | 1965-07-06 | Davis Chester | Associated dye salts and method of forming colored indicia therewith |
US3278327A (en) * | 1959-03-19 | 1966-10-11 | Warren S D Co | Colorless recording paper |
US3157677A (en) * | 1959-05-09 | 1964-11-17 | Basf Ag | Sulfonic acid salts of auramine |
US3143558A (en) * | 1960-01-06 | 1964-08-04 | Schering Ag | Aryl sulfonylthionylamides and derivatives thereof and methods of producing the same |
US3239564A (en) * | 1960-12-02 | 1966-03-08 | Reeder Earl | 2 n-substituted amino halobenzo-phenones |
US3116257A (en) * | 1960-12-19 | 1963-12-31 | Pure Oil Co | Surdfactant compositions containing salts of vinylsulfonanilides |
US3377185A (en) * | 1964-11-18 | 1968-04-09 | Scott Paper Co | Arylmethane dye azides and method of forming colored indicia therewith |
US3404995A (en) * | 1965-09-20 | 1968-10-08 | Columbia Ribbon Carbon Mfg | Hectograph products and processes |
USRE30797E (en) * | 1977-11-09 | 1981-11-17 | Scott Paper Company | Associated dye salts and method of forming colored indicia therewith |
USRE30803E (en) * | 1977-11-09 | 1981-11-24 | Scott Paper Company | Colorless recording paper |
US4531139A (en) * | 1983-10-02 | 1985-07-23 | The Standard Register Company | Color developers for pressure-sensitive or heat-sensitive recording papers |
US4623391A (en) * | 1983-10-02 | 1986-11-18 | The Standard Register Company | Color developers for pressure-sensitive or heat-sensitive recording papers |
DE4010641A1 (en) * | 1990-04-03 | 1991-10-10 | Bayer Ag | COLOR IMAGE MIXTURE FOR PRINTING AND HEAT-SENSITIVE RECORDING SYSTEMS |
EP1138517A2 (en) * | 2000-03-27 | 2001-10-04 | Mitsui Chemicals, Inc. | Developer composition and heat sensitive recording material |
EP1138517A3 (en) * | 2000-03-27 | 2004-02-04 | Mitsui Chemicals, Inc. | Developer composition and heat sensitive recording material |
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