US3467658A - Quaternary leucoauramine compounds - Google Patents
Quaternary leucoauramine compounds Download PDFInfo
- Publication number
- US3467658A US3467658A US463942A US3467658DA US3467658A US 3467658 A US3467658 A US 3467658A US 463942 A US463942 A US 463942A US 3467658D A US3467658D A US 3467658DA US 3467658 A US3467658 A US 3467658A
- Authority
- US
- United States
- Prior art keywords
- group
- methyl
- leucoauramine
- quaternary
- nucleus
- 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
- 150000001875 compounds Chemical class 0.000 title description 53
- 125000000217 alkyl group Chemical group 0.000 description 36
- 125000000623 heterocyclic group Chemical group 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- -1 methoxyphenylene Chemical group 0.000 description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- 150000003335 secondary amines Chemical class 0.000 description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 238000005956 quaternization reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 3
- 235000005811 Viola adunca Nutrition 0.000 description 3
- 240000009038 Viola odorata Species 0.000 description 3
- 235000013487 Viola odorata Nutrition 0.000 description 3
- 235000002254 Viola papilionacea Nutrition 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229960000892 attapulgite Drugs 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000005343 heterocyclic alkyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- HORKYAIEVBUXGM-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoxaline Chemical class C1=CC=C2NCCNC2=C1 HORKYAIEVBUXGM-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- IMMDNRXGZICMBC-UHFFFAOYSA-N 4-[2-(diethylamino)ethyl]aniline Chemical compound CCN(CC)CCC1=CC=C(N)C=C1 IMMDNRXGZICMBC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- NQHJSXHQDXYWIC-UHFFFAOYSA-N O(CC)S(=O)(=O)O.N1CCNCC1 Chemical compound O(CC)S(=O)(=O)O.N1CCNCC1 NQHJSXHQDXYWIC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000172533 Viola sororia Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- YLZSIUVOIFJGQZ-UHFFFAOYSA-N bis[4-(dimethylamino)phenyl]methanol Chemical compound C1=CC(N(C)C)=CC=C1C(O)C1=CC=C(N(C)C)C=C1 YLZSIUVOIFJGQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 125000006849 chlorophenylene group Chemical group 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 238000010908 decantation Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000004826 dibenzofurans Chemical class 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- RHZNQEWFWUODFC-UHFFFAOYSA-N ethyl(dimethyl)azanium;ethyl sulfate Chemical compound CC[NH+](C)C.CCOS([O-])(=O)=O RHZNQEWFWUODFC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen 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
- 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
- leucoauramines of various types which compounds are colorless or essentially colorless, undergo a color reaction, changing to a deep blue or violet shade, when brought into adsorption contact with an acidic electron acceptor material such as attapulgite, bentonite, kaolin, a zeolite, silica gel, aluminum sulfate, and magnesium trisilicate or a solid organic acid such as succinic acid, benzoic acid, and fumaric acid
- an acidic electron acceptor material such as attapulgite, bentonite, kaolin, a zeolite, silica gel, aluminum sulfate, and magnesium trisilicate or a solid organic acid such as succinic acid, benzoic acid, and fumaric acid
- the under surface of a sheet of paper called the transfer sheet
- a composition containing the leucoauramine color precursor is coated with a composition containing the leucoauramine color precursor
- the top surface of another sheet of paper is coated with a composition containing an acidic material of the indicated type.
- leucoauramine compounds commonly employed for this purpose have not proved entirely satisfactory in practice. Thus, for example, they tend to migrate to the surface of the coating especially where a crack is formed in the coating as by folding of the paper. This action results in premature coloration and smudging of the copy sheet.
- leucoauramine compounds also respond slowly to color development following impact pressure. In addition, often these leucoauramines produce a blurry or fuzzy imprint on impact of printing or writing.
- leucoauramine compounds can be employed for this extremely useful application in such a manner that not only are the abovementioned and other disadvantages eliminated or substantially mitigated but an improved imprint on impact pressure is also produced.
- This unexpected result in obtained by introducing a quaternizable nitrogen atom into the leucoauramine compound and effecting quaternization of the same, with conversion of such leucoauramine compound from its non-ionic state to an ionic form.
- quaternary bis(p-dialkyla-minophenyl)-methyl amine derivatives in which the amino N attached to the methyl C constitutes part of the residue of a primary or secondary amine also containing at least one other nitrogen atom, which other nitrogen atom is capable of being quaternized.
- quaternary leucoauramine compoundsof the present invention comprise 1) those compounds having the formula R (rim R N R1/ R2 alkyl group, and A* is an anion; (2) those compounds having the formula wherein R, R R and A respectively have the same meaning as above,
- n represents a heterocyclic nucleus containing 5 to 6 ring members of which at least one is a nitrogen atom, n is an integer from 1 to 18, R is an alkyl group, and R and R may together with the bi atom also comprise a heterocyclic alkyl group; (3) those compounds having the formula wherein R, R R R n and A respectively have the same meaning as above, and X is a hydrogen or an alkyl group, an aryl group, an aralkyl group, or an alkaryl group; (4) those compounds having the formula wherein R, R R R X, n and A- respectively have the same meaning as above, and Y is an aryl group; and (5) those compounds having the formula 3 wherein R, R R R X, n and A- respectively have the same meaning as above, and Z is a heterocyclic nucleus containing to 6 ring members and connected to the N atom through a ring carbon atom.
- R is an alkyl group, which may have a straight-chain structure or a branched-chain structure. Usually, however, R is a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group. Ordinarily each R is the same, but they may be different as desired.
- Each phenylene group attached to the methyl C is generally a phenylene group per se.
- Either or both phenylene groups may, however, contain one or more substituents such as an alkyl group, an aralkyl group, an alkoxy group, group, or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the phenylene group.
- the tolylene, methoxyphenylene, and chlorophenylene groups comprise typical examples of such substituted phenylene groups.
- the heterocyclic nucleus represented by contains, as indicated, 5 to 6 ring members of which at least two are nitrogen atoms. One such nitrogen atom forms the linking point to the methyl C, and the other such nitrogen atom must be quaternizable. Besides carbon and nitrogen atoms, this heterocyclic nucleus may contain an oxygen atom and/or a sulfur atom as a ring member. In addition, such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus.
- substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nu
- heterocyclic nucleus also includes within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above.
- a typical S-membered heterocyclic nucleus of this type comprises the irnidazolidine nucleus;
- typical 6-membered heterocyclic nuclei of this type include the piperazine nucleus and the Z-methyl piperazine nucleus;
- a typical condensed heterocyclic nucleus of this type comprises the 1,2,3,4-tetrahydroquinoxaline nucleus.
- R represents the group introduced into the leucoauramine compound as the result of its quaternization.
- R may be an alkyl group, in which event it may be a straight-chain group or a branched-chain group. In such case, however, R is usually a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group.
- R may also be a cycloalkyl group such as the cyclohexyl group, or it may be an aralkyl group such as the benzyl group.
- the alkyl group represented by R may have a straightchain structure or a branched-chain structure.
- such alkyl group may contain a substituent such as a halogen or a hydroxyl group provided that such substituent is not itself reactive and is not rendered reactive by reason of its manner of association with the alkyl group.
- R is a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group.
- An example of such a substituted alkyl group is the hydroxy ethyl group.
- the anion represented by A- is, of course, the anion derived from the quatemizing agent utilized in producing the desired quaternary leucoauramine compound. Any quatemizing agent providing the appropriate R group may be employed for this purpose so that A represents whatever anion results from the use of such quatemizing agent. Ordinarily, however, A is a chloride, bromide or iodide anion or a mono-alkly sulfate anion. In the latter case the alkyl portion of the anion usually has 1 to 4 carbon atoms and is preferably a methyl group or an ethyl group. As will be appreciated, when A" is such a monoalkly sulfate anion, R is generally an alkly group corresponding to the alkyl portion of such anion.
- the heterocyclic nucleus represented by contains, as indicated, 5 to 6 ring members of which at least one is a nitrogen atom, such nitrogen atom providing the linking point to the methyl C. Besides carbon and nitrogen atoms, this heterocyclic nucleus may contain an oxygen atom and/or a sulfur atom as a ring member. In addition, such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus.
- substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus.
- heterocyclic nucleus also included within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above.
- Typical S-membered heterocyclic nuclei of this type include the imidazoline nucleus and the pyrazoline nucleus; typical 6-membered heterocyclic nuclei of this type include the piperidine nucleus and the morpholine nucleus; and typical condensed heterocyclic nuclei of this type include the indole nucleus, the benzotriazole nucleus, and the carbazole nucleus.
- the alkylene chain represented by --(CH may contain 1 to 18 carbon atoms as indicated.
- This alkylene chain may be branched in structure but is generally a straight-chain group.
- such alkylene chain may include an ether linkage or a thio linkage provided that such a linkage is not itself reactive and is not rendered reactive by reason of its manner of association with the alkylene chain.
- R represents an alkyl group of the same type as represented by R and, like R is usually a lower alkyl group having 1 to 4 carbon atoms. R and R are generally the same but may be different as desired. In addition, R and R together with the N atom to which they are attached may also comprise a heterocyclic alkly group, which may contain other hetero atoms such as oxygen in its ring. Typical examples of such heterocyclic alkyl groups include the piperidino group and the morpholino group.
- X may be hydrogen or any of several hydrocarbon groups.
- X is an alkyl group, it may be a straight-chain group or a branched-chain group, or it may have a cyclic structure. In such a case, however, X is usually a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group.
- X is an aryl group, it may be mononuclear or polynuclear.
- X is an aralkyl group or an alkaryl group, similar comments respectively apply to the alkyl portion and to the aryl portion of such a group.
- any such hydrocarbon group may contain a substituent such as an alkoxy group or a halogen provided that such substituent is itself Inert and is not rendered reactive by reason of its manner of association with the hydrocarbon group.
- the aryl group represented by Y may be mononuclear or polynuclear in structure.
- such aryl group may contain a substituent such as an alkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the aryl group.
- aryl groups include those groups respectively derived from benzene, naphthalene, anthracene and biphenyl.
- Z represents a heterocyclic nucleus having, as indicated, 5 to 6 ring members, one carbon atom of which serves as the linking point to the N atom attached to the methyl C.
- the hetero atom or atoms included in such heterocyclic nucleus may comprise oxygen, nitrogen and/or sulfur.
- such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus.
- heterocyclic nucleus also includes within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above.
- a typical S-membered heterocyclic nucleus of this type comprises the pyrrole nucleus; a typical 6-membered heterocyclic nucleus of this type comprises the pyridine nucleus; and typical condensed heterocyclic nuclei of this type include the benzofuran nucleus, the dibenzofuran nucleus, the benzothiazole nucleus, and the quinoline nucleus.
- the quaternary leucoauramine compounds of the present invention may be prepared by initially condensing a bis(p-dialkylaminophenyl)-methyl hydrol (or 4,4'-bis(dialkylamino)-benzhydrol) having the formula R on R wherein R has the same meaning as above and each phenylene group has the same scope as given above, with (1) a secondary amine having the formula it i.
- the initial condensation of the benzhydrol with the primary or secondary amine is conducted by refluxing substantially equimolar proportions of the two reactants in the presence of a solvent in which :both reactants are at least partially soluble and which has a boiling point between 60 and C.
- suitable solvents for this purpose include aromatic hydrocarbons such as benzene, toluene and xylene and alcohols such as methanol, ethanol, propanol and butanol.
- Solution of such leucoauramine compound is thereafter effected in a suitable nonpolar solvent such as one of the aromatic hydrocarbons at a temperature of about 50 to 70 C.
- a suitable nonpolar solvent such as one of the aromatic hydrocarbons
- the appropriate quaternizing agent is then added, preferably dropwise, to such solution.
- the quaternization reaction being mildly exothermic, there is a rise in temperature, usually on the order of 10 to 15 C., of the reaction mixture during the addition of the quaternizing agent.
- Quaternizing agents typically suitable for effecting the quaternization of the resulting leucoauramine compound include dimethyl sulfate, diethyl sulfate, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, cyclohexyl chloride, cyclohexyl bromide, benzyl chloride, and benzyl bromide.
- the quaternary leucoauramine compounds may be prepared by initially quaternizing the quaternizable nitrogen atom contained in the primary or secondary amine and then condensing the benzhydrol with the resulting quaternized primary or secondary amine.
- Such quaternization of the primary or secondary amine can be effected by treating the primary or secondary amine with a quaternizing agent providing the appropriate R group in the presence of a suitable solvent medium such as an alcohol.
- the benzhydrol can then be added to the resulting solution of the quaternized primary or secondary amine for condensation therewith; and the resulting quaternized leucoauramine compound can be recovered as by evaporation of the solvent medium.
- a quaternized primary amine typically suitable for this purpose comprises N,N-diethyl-N'-methyl trimethylene diammonium bromide; and a quaternized secondary amine typically suitable for this purpose comprises ([3-N- methylaminophenyl]methyl) ethyldimethyl ammonium ethyl sulfate.
- the quaternary leucoauramine compounds of the invention include a positively charged nitrogen atom and are thus ionic in nature.
- these quaternized compounds are insoluble in nonpolar solvents or media such as petroleum hydrocarbons, aromatic hydrocarbons, waxes and vegetable oils. Being ionizable, however, these quaternary leucoauramine compounds are readily soluble in water; and they also possess greater solubility in polar and semi-polar solvents such as ethanol and acetone than the corresponding unquaternized leucoauramine compounds.
- these quaternary leucoauramine compounds not only retain the color-producing property of the corresponding leucoauramines themselves, but improved results are obtained when such a quaternary leucoauramine compound is utilized as the color precursor in an impactprinting system.
- these quaternary leucoauramine compounds can be incorporated in the internal phase of an aqueous wax emulsion of the waterin-oil type for use as the coating on the transfer sheet of an impact-duplicating arrangement, with the result that migration of the quaternary leucoauramine compound through such coating is effectively prevented and the production of premature color development in the acidic-material coating on the associated copy sheet is avoided.
- the present quaternary leucoauramine compounds also produce an instantaneous, intense color formation on the copy sheet upon impact pressure in contrast to the relatively slow color formation encountered with many of the corresponding leucoauramines themselves.
- Such imprint on the copy sheet is clear and sharp as contrasted with the indistinct and otherwise unclear imprint frequently obtained when the corresponding leucoauramine compounds themselves are utilized as color precursors.
- Those quaternary leucoauramine compounds which are obtained by condensing a benzhydrol of the type indicated above with an N-alkyl piperazine followed by appropriate quaternization of the resulting condensation product are particularly effective in producing such improved results.
- Such compounds which constitute a preferred embodiment of the present invention, have the formula 1 to 4 carbon atoms.
- R is a methyl or ethyl group;
- R is a methyl or ethyl group or a benzyl group;
- R is a methyl or ethyl group.
- R, R and R are the same, in which case each may be a methyl group or an ethyl group.
- a quaternary leucoauramine compound according to claim 10 in which A- is a mono-alkyl sulfate anion.
- a quaternary leucoauramine compound having the wherein R is an alkyl group having 1 to 4 carbon atoms, R is a member selected from the class consisting of alkyl groups having 1 to 4 carbon atoms and phenyl alkyl having 1 to 4 carbon atoms in the alkyl moiety, R is an alkyl group having 1 to 4 carbon atoms, and A- is an anion selected from the class consisting of chloride, bromide, and iodide anions and mono-alkyl sulfate anions of which the alkyl portion has 1 to 4 carbon atoms.
- a quaternary leucoauramine compound having the formula R H /R R/ in R HzC CH2 wherein R and R are alkyl groups having 1 to 4 carbon atoms, R is a member selected from the class consisting of alkyl groups having 1 to 4 carbon atoms and benzyl groups and A- is an anion selected from the class consist'ing of chloride, bromide, and iodide anions and monoalkyl sulfate anions of which the alkyl portion has 1 to 4 carbon atoms.
- a quaternary leucoauramine compound selected' from the class consisting of (1) those compounds havingthe formula R H R wherein R is an alkyl group having 1 to 4 carbon atoms;
- R, R R and A respectively have the same meaning as above,
- n is an integer from 1 to 18, R is an alkyl group having 1 to 4 carbon atoms and R and R may together with the N atom form a piperidine group radical; (3) those compounds having the formula wherein R, R R R n and A- respectively have the same meaning as above, and X is a member selected from the group consisting of hydrogen, alkyl groups, having 1 to 4 carbon atoms, phenyl, benzyl and tolyl; (4) those compounds having the formula XC-Y(CH2)nN--Rn .A-
- R, R R R X, n and A respectively have the same meaning as above, and Y is an aryl group selected from the group consisting of phenyl, naphthyl, anthracyl 1 1 1 2 and biphenyl; and (5) those compounds having the for- 11.
- R is an alkyl mula group having 1 to 4 carbon atoms
- X is hydrogen or an alkyl group having 1 to 4 carbon atoms
- Y is phenyl.
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Description
United States Patent 3,467,658 QUATERNARY LEUCOAURAMINE COMPOUNDS Benjamin Lipka, Amherst, N .Y., assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed June 14, 1965, Ser. No. 463,942 Int. Cl. C07d 49/18, 51/70 U.S. Cl. 260-268 11 Claims ABSTRACT OF THE DISCLOSURE There are provided quaternary bis(p-dialkylaminophenyl)-methyl amine derivatives in which the amino N attached to the methyl C constitutes part of the residue of a primary or secondary amine also containing at least one other nitrogen atom, which other nitrogen atom is capable of being quaternized. These compounds are valuable as color precursors for colorless carbon paper and impact printing systems.
It is known that leucoauramines of various types, which compounds are colorless or essentially colorless, undergo a color reaction, changing to a deep blue or violet shade, when brought into adsorption contact with an acidic electron acceptor material such as attapulgite, bentonite, kaolin, a zeolite, silica gel, aluminum sulfate, and magnesium trisilicate or a solid organic acid such as succinic acid, benzoic acid, and fumaric acid This property finds extensive use in the production of colorless carbon paper, manifold record systems, and similar impact-printing arrangements. In geneal, in the preparation of such a system, the under surface of a sheet of paper, called the transfer sheet, is coated with a composition containing the leucoauramine color precursor; and the top surface of another sheet of paper, called the copy sheet, is coated with a composition containing an acidic material of the indicated type. When the transfer sheet is superimposed on the copy sheet and a written or imprinted impression is made on the top surface of the transfer sheet, the impression will be duplicated in color on the copy sheet at the point of pressure.
The leucoauramine compounds commonly employed for this purpose have not proved entirely satisfactory in practice. Thus, for example, they tend to migrate to the surface of the coating especially where a crack is formed in the coating as by folding of the paper. This action results in premature coloration and smudging of the copy sheet.
Some of these leucoauramine compounds also respond slowly to color development following impact pressure. In addition, often these leucoauramines produce a blurry or fuzzy imprint on impact of printing or writing.
I have now found that, surprisingly, leucoauramine compounds can be employed for this extremely useful application in such a manner that not only are the abovementioned and other disadvantages eliminated or substantially mitigated but an improved imprint on impact pressure is also produced. This unexpected result in obtained by introducing a quaternizable nitrogen atom into the leucoauramine compound and effecting quaternization of the same, with conversion of such leucoauramine compound from its non-ionic state to an ionic form.
According to the invention there are thus provided quaternary bis(p-dialkyla-minophenyl)-methyl amine derivatives in which the amino N attached to the methyl C constitutes part of the residue of a primary or secondary amine also containing at least one other nitrogen atom, which other nitrogen atom is capable of being quaternized.
These quaternary leucoauramine compoundsof the present invention comprise 1) those compounds having the formula R (rim R N R1/ R2 alkyl group, and A* is an anion; (2) those compounds having the formula wherein R, R R and A respectively have the same meaning as above,
represents a heterocyclic nucleus containing 5 to 6 ring members of which at least one is a nitrogen atom, n is an integer from 1 to 18, R is an alkyl group, and R and R may together with the bi atom also comprise a heterocyclic alkyl group; (3) those compounds having the formula wherein R, R R R n and A respectively have the same meaning as above, and X is a hydrogen or an alkyl group, an aryl group, an aralkyl group, or an alkaryl group; (4) those compounds having the formula wherein R, R R R X, n and A- respectively have the same meaning as above, and Y is an aryl group; and (5) those compounds having the formula 3 wherein R, R R R X, n and A- respectively have the same meaning as above, and Z is a heterocyclic nucleus containing to 6 ring members and connected to the N atom through a ring carbon atom.
As indicated, R is an alkyl group, which may have a straight-chain structure or a branched-chain structure. Usually, however, R is a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group. Ordinarily each R is the same, but they may be different as desired.
Each phenylene group attached to the methyl C is generally a phenylene group per se. Either or both phenylene groups may, however, contain one or more substituents such as an alkyl group, an aralkyl group, an alkoxy group, group, or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the phenylene group. The tolylene, methoxyphenylene, and chlorophenylene groups comprise typical examples of such substituted phenylene groups.
The heterocyclic nucleus represented by contains, as indicated, 5 to 6 ring members of which at least two are nitrogen atoms. One such nitrogen atom forms the linking point to the methyl C, and the other such nitrogen atom must be quaternizable. Besides carbon and nitrogen atoms, this heterocyclic nucleus may contain an oxygen atom and/or a sulfur atom as a ring member. In addition, such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus. This term heterocyclic nucleus also includes within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above. A typical S-membered heterocyclic nucleus of this type comprises the irnidazolidine nucleus; typical 6-membered heterocyclic nuclei of this type include the piperazine nucleus and the Z-methyl piperazine nucleus; and a typical condensed heterocyclic nucleus of this type comprises the 1,2,3,4-tetrahydroquinoxaline nucleus.
R represents the group introduced into the leucoauramine compound as the result of its quaternization. As indicated, R may be an alkyl group, in which event it may be a straight-chain group or a branched-chain group. In such case, however, R is usually a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group. R may also be a cycloalkyl group such as the cyclohexyl group, or it may be an aralkyl group such as the benzyl group.
The alkyl group represented by R may have a straightchain structure or a branched-chain structure. In addition, such alkyl group may contain a substituent such as a halogen or a hydroxyl group provided that such substituent is not itself reactive and is not rendered reactive by reason of its manner of association with the alkyl group. Usually, however, R is a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group. An example of such a substituted alkyl group is the hydroxy ethyl group.
The anion represented by A- is, of course, the anion derived from the quatemizing agent utilized in producing the desired quaternary leucoauramine compound. Any quatemizing agent providing the appropriate R group may be employed for this purpose so that A represents whatever anion results from the use of such quatemizing agent. Ordinarily, however, A is a chloride, bromide or iodide anion or a mono-alkly sulfate anion. In the latter case the alkyl portion of the anion usually has 1 to 4 carbon atoms and is preferably a methyl group or an ethyl group. As will be appreciated, when A" is such a monoalkly sulfate anion, R is generally an alkly group corresponding to the alkyl portion of such anion.
The heterocyclic nucleus represented by contains, as indicated, 5 to 6 ring members of which at least one is a nitrogen atom, such nitrogen atom providing the linking point to the methyl C. Besides carbon and nitrogen atoms, this heterocyclic nucleus may contain an oxygen atom and/or a sulfur atom as a ring member. In addition, such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus. This term heterocyclic nucleus also included within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above. Typical S-membered heterocyclic nuclei of this type include the imidazoline nucleus and the pyrazoline nucleus; typical 6-membered heterocyclic nuclei of this type include the piperidine nucleus and the morpholine nucleus; and typical condensed heterocyclic nuclei of this type include the indole nucleus, the benzotriazole nucleus, and the carbazole nucleus.
The alkylene chain represented by --(CH may contain 1 to 18 carbon atoms as indicated. This alkylene chain may be branched in structure but is generally a straight-chain group. In addition, such alkylene chain may include an ether linkage or a thio linkage provided that such a linkage is not itself reactive and is not rendered reactive by reason of its manner of association with the alkylene chain.
R represents an alkyl group of the same type as represented by R and, like R is usually a lower alkyl group having 1 to 4 carbon atoms. R and R are generally the same but may be different as desired. In addition, R and R together with the N atom to which they are attached may also comprise a heterocyclic alkly group, which may contain other hetero atoms such as oxygen in its ring. Typical examples of such heterocyclic alkyl groups include the piperidino group and the morpholino group.
As indicated, X may be hydrogen or any of several hydrocarbon groups. Where X is an alkyl group, it may be a straight-chain group or a branched-chain group, or it may have a cyclic structure. In such a case, however, X is usually a lower alkyl group having 1 to 4 carbon atoms; and preferably it is a methyl group or an ethyl group. Where X is an aryl group, it may be mononuclear or polynuclear. Where X is an aralkyl group or an alkaryl group, similar comments respectively apply to the alkyl portion and to the aryl portion of such a group. A typical example of such an aryl group is the phenyl group; a typical example of such an aralkyl group is the benzyl group; and a typical example of such as alkaryl group is the tolyl group. In addition, any such hydrocarbon group may contain a substituent such as an alkoxy group or a halogen provided that such substituent is itself Inert and is not rendered reactive by reason of its manner of association with the hydrocarbon group.
The aryl group represented by Y may be mononuclear or polynuclear in structure. In addition, such aryl group may contain a substituent such as an alkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the aryl group.
Typical examples of such aryl groups include those groups respectively derived from benzene, naphthalene, anthracene and biphenyl.
Z represents a heterocyclic nucleus having, as indicated, 5 to 6 ring members, one carbon atom of which serves as the linking point to the N atom attached to the methyl C. The hetero atom or atoms included in such heterocyclic nucleus may comprise oxygen, nitrogen and/or sulfur. In addition, such heterocyclic nucleus may contain one or more substituents such as an alkyl group, an aralkyl group, a hydroxyalkyl group, an alkoxy group or a halogen provided that any such substituent is itself inert and is not rendered reactive by reason of its manner of association with the heterocyclic nucleus. This term heterocyclic nucleus also includes within its scope a condensed or fused polynuclear group, part of which is comprised of the above-indicated 5- or 6-membered heterocyclic nucleus itself and which may also be substituted as indicated above. A typical S-membered heterocyclic nucleus of this type comprises the pyrrole nucleus; a typical 6-membered heterocyclic nucleus of this type comprises the pyridine nucleus; and typical condensed heterocyclic nuclei of this type include the benzofuran nucleus, the dibenzofuran nucleus, the benzothiazole nucleus, and the quinoline nucleus.
In general, the quaternary leucoauramine compounds of the present invention may be prepared by initially condensing a bis(p-dialkylaminophenyl)-methyl hydrol (or 4,4'-bis(dialkylamino)-benzhydrol) having the formula R on R wherein R has the same meaning as above and each phenylene group has the same scope as given above, with (1) a secondary amine having the formula it i.
wherein I N I and R respectively have the same meaning as above, or (2) a secondary amine having the formula R R and n respectively have the same meaning as above, or (3) a primary or secondary amine having the formula 3 wherein wherein R R X, Y and n respectively have the same meaning as above, or (5) a primary or secondary amine having the formula wherein R R X, Z and n respectively have the same meaning as above. The resulting leucoauramine compound is then treated with a quaternizing agent containing the appropriate R group to give the corresponding quaternary leucoauramine compound.
More particularly, the initial condensation of the benzhydrol with the primary or secondary amine is conducted by refluxing substantially equimolar proportions of the two reactants in the presence of a solvent in which :both reactants are at least partially soluble and which has a boiling point between 60 and C. Examples of suitable solvents for this purpose include aromatic hydrocarbons such as benzene, toluene and xylene and alcohols such as methanol, ethanol, propanol and butanol. Upon completion of the refluxing, the reaction mixture is cooled in order to precipitate the resulting leucoauramine compound, which is then separated as by filtration and which may be purified, if desired, by subsequent recrystallization from a suitable solvent. Solution of such leucoauramine compound is thereafter effected in a suitable nonpolar solvent such as one of the aromatic hydrocarbons at a temperature of about 50 to 70 C. The appropriate quaternizing agent is then added, preferably dropwise, to such solution. The quaternization reaction being mildly exothermic, there is a rise in temperature, usually on the order of 10 to 15 C., of the reaction mixture during the addition of the quaternizing agent. The resulting quaternary leucoauramine compound, :being insoluble in the nonpolar sol-vent, precipitates out during the course of the reaction and is subsequently separated as by filtration.
Examples of benzhydrols suitable for use in such initial condensation reaction include:
4,4'-bis(dimethylamino)-benzhydrol (Michlers hydrol) 4,4-bis(diethylamino)-benzhydrol 4,4'-bis (dibutylamino benzhydrol 4,4-bis dimethylamino) -2,2'-dichloro-benzhydrol.
Examples of primary and secondary amines that can be typically employed in such initial condensation reaction include:
N-methyl piperazine N-et-hyl piperazine 2-(2-dimethylaminoethyl) morpholine 4-(2-diethylaminoethyl) piperidine 6-dimethylaminoethyl indole 3-(3-diethylaminopropyl) indole N,N-dimethyl octamethylene diamine N-ethyl-N',N-dimethyl hexadecylmethylene diamine N-benzyl-N-methyl dodecylmethylene diamine 4(2-diethylaminoethyl) aniline 4- N,N-dimethylaminomet-hyl) -1-naphthyl amine 2- 4-dimethylaminobutyl -4-amino-pyridine 2-(3-diethylaminopropyl)-8-amino-quinoline 6- Z-dimethylaminoethyl) -2-methylamino-benzothiazole.
Quaternizing agents typically suitable for effecting the quaternization of the resulting leucoauramine compound include dimethyl sulfate, diethyl sulfate, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, cyclohexyl chloride, cyclohexyl bromide, benzyl chloride, and benzyl bromide.
Alternatively, the quaternary leucoauramine compounds may be prepared by initially quaternizing the quaternizable nitrogen atom contained in the primary or secondary amine and then condensing the benzhydrol with the resulting quaternized primary or secondary amine. Such quaternization of the primary or secondary amine can be effected by treating the primary or secondary amine with a quaternizing agent providing the appropriate R group in the presence of a suitable solvent medium such as an alcohol. The benzhydrol can then be added to the resulting solution of the quaternized primary or secondary amine for condensation therewith; and the resulting quaternized leucoauramine compound can be recovered as by evaporation of the solvent medium. A quaternized primary amine typically suitable for this purpose comprises N,N-diethyl-N'-methyl trimethylene diammonium bromide; and a quaternized secondary amine typically suitable for this purpose comprises ([3-N- methylaminophenyl]methyl) ethyldimethyl ammonium ethyl sulfate.
The quaternary leucoauramine compounds of the invention, as will be appreciated, include a positively charged nitrogen atom and are thus ionic in nature. As a result, in contrast to the corresponding leucoauramines themselves, these quaternized compounds are insoluble in nonpolar solvents or media such as petroleum hydrocarbons, aromatic hydrocarbons, waxes and vegetable oils. Being ionizable, however, these quaternary leucoauramine compounds are readily soluble in water; and they also possess greater solubility in polar and semi-polar solvents such as ethanol and acetone than the corresponding unquaternized leucoauramine compounds.
Moreover, these quaternary leucoauramine compounds not only retain the color-producing property of the corresponding leucoauramines themselves, but improved results are obtained when such a quaternary leucoauramine compound is utilized as the color precursor in an impactprinting system. For example, because of their watersolubility, these quaternary leucoauramine compounds can be incorporated in the internal phase of an aqueous wax emulsion of the waterin-oil type for use as the coating on the transfer sheet of an impact-duplicating arrangement, with the result that migration of the quaternary leucoauramine compound through such coating is effectively prevented and the production of premature color development in the acidic-material coating on the associated copy sheet is avoided. The present quaternary leucoauramine compounds also produce an instantaneous, intense color formation on the copy sheet upon impact pressure in contrast to the relatively slow color formation encountered with many of the corresponding leucoauramines themselves. Such imprint on the copy sheet, in addition, is clear and sharp as contrasted with the indistinct and otherwise unclear imprint frequently obtained when the corresponding leucoauramine compounds themselves are utilized as color precursors.
Those quaternary leucoauramine compounds which are obtained by condensing a benzhydrol of the type indicated above with an N-alkyl piperazine followed by appropriate quaternization of the resulting condensation product are particularly effective in producing such improved results. Such compounds, which constitute a preferred embodiment of the present invention, have the formula 1 to 4 carbon atoms. Preferably, R is a methyl or ethyl group; R is a methyl or ethyl group or a benzyl group; and R is a methyl or ethyl group. Generally, R, R and R are the same, in which case each may be a methyl group or an ethyl group. These three substituents may, however, be different, depending upon the R group provided by the quaternizing agent and/or the R group contained in the initial piperazine reactant.
The following examples will illustrate the invention:
EXAMPLE 1 A solution of 638 g. of Michlers hydrol (technical grade, 90% strength; 2.125 moles) and 213 g. (2.125 moles) of N-methyl piperazine in 3700 ml. of 95% methanol was heated at reflux temperature for 43 hours. The reaction mass was then cooled to room temperature and filtered. The filter cake was washed with 300 ml. of ethanol and dried in a vacuum oven at 40 to 45 C. The resulting crystalline, essentially colorless product, comprising bis(p-dimethylaminophenyl)-N methyl piperazinyl methane, melted at 174 C. It was thereafter recrystallized from toluene.
A 3-liter, 3-neck fiask, fitted with a condenser, an agitator, a thermometer and a dropping funnel, was charged with 264 g. (.075 mole) of such leucoauramine compound and 1320 ml. of dry benzene. The mixture was heated to C. to effect solution. To the hot solution was added dropwise 94.5 g. (71 ml.; 0.75 mole) of dimethyl sulfate over a period of about 1 hour. The temperature rose to 73 C.; and a white granular precipitate formed during such addition. The reaction mass was allowed to cool overnight; and the precipitate was then Collected on a Buchner funnel, using gentle suction, and was washed with 100 ml. of dry benzene. The washed product was covered with a polyethylene dam and suction-dried for 4 hours. After transfer to a vacuum drier, the product was further dried at room temperature overnight. The yield of N bis(p dimethylaminophenyl)- methyl-N,N-dimethyl piperazinium methyl sulfate was 317 g. (90% of theory); it melted at 156 to 158 C.
An aqueous solution of this quaternary leucoauramine compound gave an instantaneous intense blue-violet color upon contact with filter paper impregnated with succinic acid.
EXAMPLE 2 To a 75 C. solution (protected by a drying tube) of 35.2 g. (0.1 mole.) of bis(p-dimethyl-aminophenyl)-N'- methyl-piperazinyl methane (prepared as in Example 1) in 165 ml. of toluene, 15.4 g. (0.1 mole) of diethyl sulfate was added dropwise over 20 minutes. The resulting pale brown-yellow solution gradually became greenish, and an oily greenish product slowly separated. Heating was continued for an additional hour and 20 minutes. After cooling of the reaction mixture and decantation of the solvent, a brown gummy material remained. This residue was extracted with 100 ml. of hot C.) Skellysolve C (a petroleum hydrocarbon mixture having a boling point range of 88 to 99 C. and consisting pre dominantly of heptane) for about 20 minutes; then the solvent was decanted hot. The taffy-like residue was cooled to ambient temperature and then placed for a few minutes in an ice bath, during which time it changed to a resinous glass. After recovery, this resinous product was air-dried and ground, yielding a brownish powder. The yield of N [bis(p-dimethylaminophenyl) methyl]-N- ethyl-N'-methyl piperazinium ethyl sulfate was 37.6 g. (70% of theory).
When brought into contact with filter paper impregnated with attapulgite and with filter paper impregnated with bentonite, an aqueous solution of this quarternary leucoauramine compound gave respectively an intense blue-violet color and an intense blue color. Similar contact of such aqueous solution with filter paper impregnated with succinic acid gave an immediate intense blue color.
EXAMPLE 3 To a 100 C. solution (protected by a drying tube) of 35.2 g. (0.1 mole) of bis(p-dimethylaminophenyl)- N-methyl piperazinyl methane (prepared as in Example 1) in ml. of toluene, 12.6 g. (0.1 mole) of benzyl chloride was charged over 35 minutes. The solution slow- 1y darkened, and a precipitate gradually deposited. Heating was continued for hours at 100 to 110 C. After cooling of the reaction mixture to ambient temperature, a grey solid was recovered on a filter, successively washed with 100 ml. of toluene and 100 ml. of Skellysolve C, and then air-dried (using a protective plastic cover) for 4 hours. The yield of N-[bis(p-dimethylaminophenyl)- methyl]-N'-benzyl-N'-methyl piperazinium chloride was 33.4 g. (70% of theory).
When brought into contact with filter paper impregnated with attapulgite and with filter paper impregnated with bentonite, an aqueous solution of this quaternary leucoauramine compound gave respectively an intense blue-violet color and an intense blue color. Similar contact of such aqueous solution with filter paper impergnated with succinic acid gave an immediate intense blue coloration.
I claim:
1. A quaternary leucoauramine compound according to claim 10, in which A- is a mono-alkyl sulfate anion.
2. A quaternary leucoauramine compound having the wherein R is an alkyl group having 1 to 4 carbon atoms, R is a member selected from the class consisting of alkyl groups having 1 to 4 carbon atoms and phenyl alkyl having 1 to 4 carbon atoms in the alkyl moiety, R is an alkyl group having 1 to 4 carbon atoms, and A- is an anion selected from the class consisting of chloride, bromide, and iodide anions and mono-alkyl sulfate anions of which the alkyl portion has 1 to 4 carbon atoms.
3. A quaternary leucoauramine compound according to claim 9, in which R, R and R are each a methyl group.
4. A quaternary leucoauramine compound according to claim 9, in which R, R and R are each an ethyl group.
5. A quaternary leucoauramine compound according to claim 9, in which R is a benzyl group.
6. N [bis (p dimethylaminophenyl) methyl]-N',N'- dimethyl piperazinium methyl sulfate.
7. N [bis(p dimethylaminophenyl) methyl] N- ethyl-N'-methy1 piperazinium ethyl sulfate.
8. N [bis(p dimethylaminophenyl) methyl] N- benzyl-N-methyl piperazinium chloride.
9. A quaternary leucoauramine compound having the formula R H /R R/ in R HzC CH2 wherein R and R are alkyl groups having 1 to 4 carbon atoms, R is a member selected from the class consisting of alkyl groups having 1 to 4 carbon atoms and benzyl groups and A- is an anion selected from the class consist'ing of chloride, bromide, and iodide anions and monoalkyl sulfate anions of which the alkyl portion has 1 to 4 carbon atoms.
10. A quaternary leucoauramine compound selected' from the class consisting of (1) those compounds havingthe formula R H R wherein R is an alkyl group having 1 to 4 carbon atoms;
wherein R, R R and A" respectively have the same meaning as above,
is piperidine; n is an integer from 1 to 18, R is an alkyl group having 1 to 4 carbon atoms and R and R may together with the N atom form a piperidine group radical; (3) those compounds having the formula wherein R, R R R n and A- respectively have the same meaning as above, and X is a member selected from the group consisting of hydrogen, alkyl groups, having 1 to 4 carbon atoms, phenyl, benzyl and tolyl; (4) those compounds having the formula XC-Y(CH2)nN--Rn .A-
wherein R, R R R X, n and A respectively have the same meaning as above, and Y is an aryl group selected from the group consisting of phenyl, naphthyl, anthracyl 1 1 1 2 and biphenyl; and (5) those compounds having the for- 11. The compound of claim 10 wherein R is an alkyl mula group having 1 to 4 carbon atoms, X is hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y is phenyl.
N- g@N 5 References Cited 1/ \R UNITED STATES PATENTS 3,375,279 3/1968 MOffCflI 260-268 X ALEX MAZEL, Primary Examiner R3 10 D. G. DAUS, Assistant Examiner wherein R, R R R X, n and A- respectively have the same meaning as above, and Z is a heterocyclic nucleus US selected from the group consisting of piperidine, p p 106-22; 117--36.8; 260-239, 247.5, 250, 286, 288, 293, azine, methylpiperazine and quinoline nec ed to the 15 296, 304, 305, 308, 309.6, 309,7, 310, 313.1, 315, 326.15, Natom througharing carbon atom. 346.2, 501.15, 515, 537, 567.6, 570, 578, 583, 648, 650
130-1050 UNiTEn STATES PATENT OFFICE CERTIFICATE 0F CQRRECTION Patent No. 3, 7, 5 Dated September 16, 1969 Inventofls) Benjamin Lipka It is certified that error appears in theabove-identified patent and that said Letters Patent are hereby corrected as shown below:
In the claims, claim 10, line H? reading,
"together with the N atom form a piperidine group radical,"
should read "together with the atom form a piperidine group,-
line 70, that portion of the formula reading,
"K 0 Y (O'Hg) -NR .A"
should read v 4. "X N Y- (CH N-R2 .A""
ram) fittest:
Ed I L m m Matcher $2. wmEAM E. SW, J'R- J fittesfiimg Patents
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US46394265A | 1965-06-14 | 1965-06-14 |
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US463942A Expired - Lifetime US3467658A (en) | 1965-06-14 | 1965-06-14 | Quaternary leucoauramine compounds |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3874884A (en) * | 1971-10-27 | 1975-04-01 | Lamson Industries Ltd | Coating compositions |
US3936361A (en) * | 1973-03-26 | 1976-02-03 | Yasushi Takatori | Image recording member |
US5458793A (en) * | 1993-05-13 | 1995-10-17 | The Lubrizol Corporation | Compositions useful as additives for lubricants and liquid fuels |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3375279A (en) * | 1961-02-20 | 1968-03-26 | Air Reduction | Dialkynyl amines |
-
1965
- 1965-06-14 US US463942A patent/US3467658A/en not_active Expired - Lifetime
-
1966
- 1966-06-13 GB GB26287/66A patent/GB1082918A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3375279A (en) * | 1961-02-20 | 1968-03-26 | Air Reduction | Dialkynyl amines |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3874884A (en) * | 1971-10-27 | 1975-04-01 | Lamson Industries Ltd | Coating compositions |
US3936361A (en) * | 1973-03-26 | 1976-02-03 | Yasushi Takatori | Image recording member |
US5458793A (en) * | 1993-05-13 | 1995-10-17 | The Lubrizol Corporation | Compositions useful as additives for lubricants and liquid fuels |
US5560755A (en) * | 1993-05-13 | 1996-10-01 | The Lubrizol Corporation | Compositions useful as additives for lubricants and liquid fuels |
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GB1082918A (en) | 1967-09-13 |
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