BR112021003135A2 - process for preparing solketal amine through direct amination - Google Patents
process for preparing solketal amine through direct amination Download PDFInfo
- Publication number
- BR112021003135A2 BR112021003135A2 BR112021003135-9A BR112021003135A BR112021003135A2 BR 112021003135 A2 BR112021003135 A2 BR 112021003135A2 BR 112021003135 A BR112021003135 A BR 112021003135A BR 112021003135 A2 BR112021003135 A2 BR 112021003135A2
- Authority
- BR
- Brazil
- Prior art keywords
- dioxolane
- group
- methanamine
- methyl
- compound
- Prior art date
Links
- -1 solketal amine Chemical class 0.000 title claims abstract description 35
- 238000005576 amination reaction Methods 0.000 title abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 37
- HXOYWCSTHVTLOW-UHFFFAOYSA-N (2,2-dimethyl-1,3-dioxolan-4-yl)methanamine Chemical compound CC1(C)OCC(CN)O1 HXOYWCSTHVTLOW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 229940078552 o-xylene Drugs 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Chemical compound O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- QTEPTQCIMPFZJK-UHFFFAOYSA-N (2-butyl-2-ethyl-1,3-dioxolan-4-yl)methanamine Chemical compound CCCCC1(CC)OCC(CN)O1 QTEPTQCIMPFZJK-UHFFFAOYSA-N 0.000 claims description 4
- ZBRHMIMJIXENCB-UHFFFAOYSA-N (2-heptan-3-yl-1,3-dioxolan-4-yl)methanamine Chemical compound CCC(CCCC)C1OCC(O1)CN ZBRHMIMJIXENCB-UHFFFAOYSA-N 0.000 claims description 4
- TXGMDJVDOOACTP-UHFFFAOYSA-N (2-propan-2-yl-1,3-dioxolan-4-yl)methanamine Chemical compound CC(C)C1OCC(CN)O1 TXGMDJVDOOACTP-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- JGTWWUVJYCJLSI-UHFFFAOYSA-N [2,2-bis(2-methylpropyl)-1,3-dioxolan-4-yl]methanamine Chemical compound CC(C)CC1(CC(C)C)OCC(CN)O1 JGTWWUVJYCJLSI-UHFFFAOYSA-N 0.000 claims description 4
- QIFXIVJJYRSTFX-UHFFFAOYSA-N [2-methyl-2-(2-methylpropyl)-1,3-dioxolan-4-yl]methanamine Chemical compound CC(C)CC1(C)OCC(CN)O1 QIFXIVJJYRSTFX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical group 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- DFDWGIZZMBNYBV-UHFFFAOYSA-N [2-methyl-2-(2-methylpropyl)-1,3-dioxolan-4-yl]methanol Chemical compound CC(C)CC1(C)OCC(CO)O1 DFDWGIZZMBNYBV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- UBMAWZHVNAFHQL-UHFFFAOYSA-N (2-butyl-2-ethyl-1,3-dioxolan-4-yl)methanol Chemical compound CCCCC1(CC)OCC(CO)O1 UBMAWZHVNAFHQL-UHFFFAOYSA-N 0.000 claims description 2
- VNMRSUHVTDURNJ-UHFFFAOYSA-N (2-heptan-3-yl-1,3-dioxolan-4-yl)methanol Chemical compound CCCCC(CC)C1OCC(CO)O1 VNMRSUHVTDURNJ-UHFFFAOYSA-N 0.000 claims description 2
- LYQZNMYSUIDIML-UHFFFAOYSA-N (2-methyl-2-phenyl-1,3-dioxolan-4-yl)methanol Chemical compound C=1C=CC=CC=1C1(C)OCC(CO)O1 LYQZNMYSUIDIML-UHFFFAOYSA-N 0.000 claims description 2
- YSBURUZUPICNTK-UHFFFAOYSA-N (2-propan-2-yl-1,3-dioxolan-4-yl)methanol Chemical compound CC(C)C1OCC(CO)O1 YSBURUZUPICNTK-UHFFFAOYSA-N 0.000 claims description 2
- AUDDNHGBAJNKEH-UHFFFAOYSA-N 2-Phenyl-1,3-dioxolane-4-methanol Chemical compound O1C(CO)COC1C1=CC=CC=C1 AUDDNHGBAJNKEH-UHFFFAOYSA-N 0.000 claims description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- FKXRTSJSCQXMBP-UHFFFAOYSA-N [2,2-bis(2-methylpropyl)-1,3-dioxolan-4-yl]methanol Chemical compound CC(C)CC1(CC(C)C)OCC(CO)O1 FKXRTSJSCQXMBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052699 polonium Inorganic materials 0.000 claims description 2
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- SIJBDWPVNAYVGY-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxolane Chemical compound CC1(C)OCCO1 SIJBDWPVNAYVGY-UHFFFAOYSA-N 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 229910052570 clay Inorganic materials 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- FKUDINVNNOQDIO-UHFFFAOYSA-N O1C(C)(C)OCC1CNCC1OC(C)(C)OC1 Chemical compound O1C(C)(C)OCC1CNCC1OC(C)(C)OC1 FKUDINVNNOQDIO-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000007040 multi-step synthesis reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- KQIGMPWTAHJUMN-UHFFFAOYSA-N 3-aminopropane-1,2-diol Chemical compound NCC(O)CO KQIGMPWTAHJUMN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- YLUIKWVQCKSMCF-UHFFFAOYSA-N calcium;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Ca+2] YLUIKWVQCKSMCF-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 238000007070 tosylation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/28—Radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESSO PARA PREPARAR SOLKETAL AMINA ATRAVÉS DE AMINAÇÃO DIRETA. Revelou-se um processo para preparar uma solketal amina através de aminação direta. É possível obter solketal aminas por procedimento muito simples com características desejadas como simplicidade, baixo custo, alto rendimento e conversão, bem como baixo impacto ambiental.PROCESS TO PREPARE SOLKETAL AMINA THROUGH DIRECT AMINATION. A process for preparing a solketal amine through direct amination has been disclosed. It is possible to obtain solketal amines by a very simple procedure with desired characteristics such as simplicity, low cost, high yield and conversion, as well as low environmental impact.
Description
[0001] A presente invenção se refere a um processo para preparar uma solketal amina através de aminação direta.[0001] The present invention relates to a process to prepare an amine solketal through direct amination.
[0002] A preparação de solketal aminas raramente é relatada na literatura. Essas vias relatadas são usualmente processos de múltiplas etapas e também geram sais ou requerem condições relativamente adversas, tornando-as inviáveis para aplicação industrial.[0002] The preparation of solketal amines is rarely reported in the literature. These reported pathways are usually multi-step processes and also generate salts or require relatively adverse conditions, making them unfeasible for industrial application.
[0003] Danielmeier, K.; Steckhan, E. Tetrahedron 6 (5) (1995) p. 1181 - 1190 descreveram a síntese de 2,2-dimetil- 1,3-dioxolano-4-metanamina, um intermediário chave para seu trabalho, por via de múltiplas etapas. Primeiro, o gliceraldeído protegido foi transformado in situ em uma oxima e, em seguida, o último foi reduzido usando LiAlH4. Goubert et al. Tetrahedron 63 (2007) p.8255 - 8266 descreveram um processo de múltiplas etapas para obter 2,2- dimetil-1,3-dioxolan-4-il)metanamina. Para isso, trifenilfosfina, ftlimida e di-isopropilazodicarboxilato foram adicionados a uma solução de solketal para obter tosil solketal como intermediário. Em seguida, monoidrato de hidrazina foi adicionado a uma suspensão deste intermediário para propiciar o produto alvo. Além disso, uma via de múltiplas etapas através de 3-amino-propan-1,2- diol e dimetóxi propano foi proposta, porém uma quantidade significativa de sal é produzida como subproduto.[0003] Danielmeier, K.; Steckhan, E. Tetrahedron 6 (5) (1995) p. 1181 - 1190 described the synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine, a key intermediate for their work, via multiple steps. First, the protected glyceraldehyde was transformed in situ to an oxime and then the latter was reduced using LiAlH4. Goubert et al. Tetrahedron 63 (2007) p.8255 - 8266 described a multi-step process to obtain 2,2-dimethyl-1,3-dioxolan-4-yl)methanamine. For this, triphenylphosphine, phthlimide and diisopropylazodicarboxylate were added to a solketal solution to obtain tosyl solketal as an intermediate. Then, hydrazine monohydrate was added to a suspension of this intermediate to provide the target product. In addition, a multi-step route through 3-amino-propan-1,2-diol and dimethyl propane has been proposed, however a significant amount of salt is produced as a by-product.
[0004] Lemaire M. Synthesis 6 (1995) p.627 - 629 propôs a síntese de múltiplas etapas de aminas secundárias derivadas de solketal, usando solketal como material de partida. Inicialmente, o solketal foi convertido em seu mesilato, este intermediário foi submetido a refluxo com benzilamina em acetonitrila para dar a amina secundária. Além disso, este processo usou substâncias hostis como solvente. Recentemente, Mbakidi e Sandrine Journal of Molecular Liquids 252 (2018) p.218 - 224 descreveram a preparação de líquidos iônicos à base de solketal aminas. Para obter aminas secundárias e terciárias derivadas de solketal, uma síntese em múltiplas etapas foi realizada através da preparação de tosil solketal na primeira etapa. Após a tosilação, a aminação foi realizada com uma substituição auxiliada por micro-ondas com a amina apropriada.[0004] Lemaire M. Synthesis 6 (1995) p.627 - 629 proposed the multistep synthesis of secondary amines derived from solketal, using solketal as starting material. Initially, the solketal was converted to its mesylate, this intermediate was refluxed with benzylamine in acetonitrile to give the secondary amine. In addition, this process used hostile substances as a solvent. Recently, Mbakidi and Sandrine Journal of Molecular Liquids 252 (2018) p.218 - 224 described the preparation of ionic liquids based on solketal amines. To obtain secondary and tertiary amines derived from solketal, a multi-step synthesis was performed by preparing tosyl solketal in the first step. After tosylation, amination was carried out with a microwave-assisted replacement with the appropriate amine.
[0005] Hamid et al. J. Am. Chem. Soc. 131 (5) (2009) p.1766 - 1774 mostrou que solketal pode ser aminado com dimetilamina em 70 % de rendimento, usando [Ru(p- cimeno)Cl2]2 com a fosfina bidentada dppf ou DPEphos como catalisador.[0005] Hamid et al. J. Am. Chem. Soc. 131 (5) (2009) p.1766 - 1774 showed that solketal can be aminated with dimethylamine in 70% yield, using [Ru(p-cimene)Cl2]2 with the bidentate phosphine dppf or DPEphos as catalyst.
[0006] Ainda existe a necessidade de fornecer um processo para preparar solketal aminas com as características desejadas, como simplicidade, baixo custo, alto rendimento e conversão, bem como baixo impacto ambiental, que possa superar as desvantagens das técnicas anteriores.[0006] There is still a need to provide a process to prepare solketal amines with the desired characteristics, such as simplicity, low cost, high yield and conversion, as well as low environmental impact, which can overcome the disadvantages of the prior techniques.
[0007] Com propósitos de conveniência, antes da descrição adicional da presente revelação, certos termos empregados no relatório descritivo e exemplos são coletados no presente documento. Essas definições devem ser lidas à luz do restante da revelação e compreendidas por uma pessoa versada na técnica. Os termos usados no presente documento têm os significados reconhecidos e conhecidos por aqueles que são versados na técnica, no entanto, com propósitos de conveniência e integridade, termos particulares e seus significados são estabelecidos abaixo.[0007] For convenience purposes, prior to further description of the present disclosure, certain terms used in the descriptive report and examples are collected herein. These definitions should be read in light of the rest of the disclosure and understood by a person skilled in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for purposes of convenience and completeness, particular terms and their meanings are set out below.
[0008] Os artigos “um”, uma", "o" e "a" são usados para se referir a um ou a mais que um (isto é, a pelo menos um) objeto gramatical do artigo.[0008] The articles "a", a", "o" and "a" are used to refer to one or more than one (ie, to at least one) grammatical object of the article.
[0009] O termo “e/ou” inclui os significados “e”, “ou” e também todas as outras combinações possíveis dos elementos conectados a esse termo.[0009] The term “and/or” includes the meanings “and”, “or” and also all other possible combinations of the elements connected to that term.
[0010] Ao longo da descrição, incluindo as reivindicações, o termo "que compreende um" deve ser entendido como sendo sinônimo do termo "que compreende pelo menos um", salvo se especificado de outro modo, e "entre" deve ser entendido como sendo inclusivo dos limites.[0010] Throughout the description, including the claims, the term "comprising one" shall be understood to be synonymous with the term "comprising at least one", unless otherwise specified, and "between" shall be understood as meaning being inclusive of boundaries.
[0011] Deve ser observado que na especificação de qualquer faixa de concentração, qualquer concentração superior particular pode ser associada a qualquer concentração inferior particular.[0011] It should be noted that when specifying any concentration range, any particular higher concentration may be associated with any particular lower concentration.
[0012] Especifica-se que, na continuação da descrição, salvo se indicado de outro modo, os valores nos limites são incluídos nas faixas de valores que são dadas.[0012] It is specified that, in the continuation of the description, unless otherwise indicated, the values in the limits are included in the ranges of values that are given.
[0013] Como usado no presente documento, o termo "grupo hidrocarboneto" se refere a um grupo que contém ligações de carbono e hidrogênio. Um grupo hidrocarboneto pode ser linear, ramificado ou cíclico e pode conter um heteroátomo, como oxigênio, nitrogênio, enxofre, halogênio, etc.[0013] As used herein, the term "hydrocarbon group" refers to a group that contains carbon and hydrogen bonds. A hydrocarbon group can be linear, branched or cyclic and can contain a heteroatom such as oxygen, nitrogen, sulfur, halogen, etc.
[0014] Como usado no presente documento, o termo "alquila" significa um radical de hidrocarboneto saturado, que pode ser linear, ramificado ou cíclico, como metila, etila, n-propila, isopropila, n-butila, sec-butila, t- butila, pentila, n-hexila, ciclo-hexila.[0014] As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be linear, branched or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t - butyl, pentyl, n-hexyl, cyclohexyl.
[0015] Como usado no presente documento, o termo "alquenila" como um grupo ou parte de um grupo denota um grupo hidrocarboneto alifático contendo pelo menos uma ligação dupla carbono-carbono e que pode ser linear ou ramificado. O grupo pode conter uma pluralidade de ligações duplas na cadeia normal e a orientação sobre cada uma é independente de E ou Z. Grupos alquenila exemplificativos incluem, mas não estão limitados a, etenila, propenila, butenila, pentenila, hexenila, heptenila, octenila e nonenila. O grupo pode ser um grupo terminal ou um grupo em ponte.[0015] As used herein, the term "alkenyl" as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be linear or branched. The group can contain a plurality of double bonds in the normal chain and the orientation about each is independent of E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, and nonenyl. The group can be a terminal group or a bridged group.
[0016] Como usado no presente documento, o termo "arila" se refere a um grupo hidrocarboneto aromático monovalente, incluindo anel em ponte e/ou sistemas de anel fusionado, contendo pelo menos um anel aromático. Os exemplos de grupos arila incluem fenila, naftila e similares. O termo "arilalquila" ou o termo "aralquila" se refere a alquila substituída com uma arila. O termo "arilalcóxi" se refere a um alcóxi substituído com arila.[0016] As used herein, the term "aryl" refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like. The term "arylalkyl" or the term "aralkyl" refers to alkyl substituted with an aryl. The term "arylalkoxy" refers to an alkoxy substituted with aryl.
[0017] Como usado no presente documento, o termo "grupo cíclico" significa um grupo hidrocarboneto de anel fechado que é classificado como um grupo alicíclico, grupo aromático ou grupo heterocíclico. O termo "grupo alicíclico" significa um grupo hidrocarboneto cíclico com propriedades semelhantes às dos grupos alifáticos.[0017] As used herein, the term "cyclic group" means a ring-closed hydrocarbon group which is classified as an alicyclic group, aromatic group or heterocyclic group. The term "alicyclic group" means a cyclic hydrocarbon group with properties similar to those of aliphatic groups.
[0018] Como usado no presente documento, o termo "cicloalquila", como usado no presente documento, significa grupos cicloalquila contendo de 3 a 8 átomos de carbono, como por exemplo ciclo-hexila.As used herein, the term "cycloalkyl", as used herein, means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
[0019] O grupo heterocíclico também pode significar um grupo heterocíclico fusionado com um anel de benzeno em que os anéis fusionados contêm átomos de carbono juntamente com 1 ou 2 heteroátomos que são selecionados de N, O e S.[0019] Heterocyclic group can also mean a heterocyclic group fused with a benzene ring in which the fused rings contain carbon atoms together with 1 or 2 heteroatoms which are selected from N, O and S.
[0020] Como usado no presente documento, o termo "heterocicloalcano" significa um heterociclo saturado formalmente derivado de um cicloalcano substituindo um ou mais átomos de carbono com um heteroátomo.[0020] As used herein, the term "heterocycloalkane" means a saturated heterocycle formally derived from a cycloalkane by replacing one or more carbon atoms with a heteroatom.
[0021] Como usado no presente documento, a terminologia "(Cn-Cm)" em referência a um grupo orgânico, em que n e m são, cada um, números inteiros, indica que o grupo pode conter de n átomos de carbono a m átomos de carbono por grupo.[0021] As used herein, the terminology "(Cn-Cm)" in reference to an organic group, where neither are each whole numbers, indicates that the group may contain from n carbon atoms to m carbon atoms. carbon per group.
[0022] Como usado no presente documento, metais do grupo IB, IIB, IIIB, IVB, VB, VIB, VIIB e VIIIB são frequentemente denominados metais de transição. Esse grupo compreende os elementos com número atômico 21 a 30 (Sc a Zn), 39 a 48 (Y a Cd), 72 a 80 (Hf a Hg) e 104 a 112 (Rf a Cn).[0022] As used herein, group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB metals are often referred to as transition metals. This group comprises the elements with atomic number 21 to 30 (Sc to Zn), 39 to 48 (Y to Cd), 72 to 80 (Hf to Hg) and 104 to 112 (Rf to Cn).
[0023] Como usado no presente documento, o termo "Lantanídeos" se refere a metais com número atômico 57 a[0023] As used herein, the term "Lantanides" refers to metals with atomic number 57 to
71.71.
[0024] Como usado no presente documento, metal de terras raras (REM), como definido pela IUPAC, é um de um conjunto de dezessete elementos químicos na tabela periódica, especificamente os quinze lantanídeos, bem como escândio e ítrio. Os elementos de terras raras são cério (Ce), disprósio (Dy), érbio (Er), európio (Eu), gadolínio (Gd), hólmio (Ho), lantânio (La), lutécio (Lu), neodímio (Nd), praseodímio (Pr), promécio (Pm), samário (Sm), escândio (Sc), térbio (Tb), túlio (Tm), itérbio (Yb) e ítrio (Y).[0024] As used herein, rare earth metal (REM), as defined by the IUPAC, is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides as well as scandium and yttrium. The rare earth elements are cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd) , praseodymium (Pr), promethium (Pm), samarium (Sm), scandium (Sc), terbium (Tb), thulium (Tm), ytterbium (Yb) and yttrium (Y).
[0025] A presente invenção se refere a um processo para produzir um composto de solketal amina que tem a fórmula geral (I), em que o dito processo compreende reagir um composto que tem a fórmula geral (II) com um composto que tem a fórmula geral (III) na presença de um catalisador de metal suportado, R3R4NH (III) em que: - R1 e R2, idênticos ou diferentes um do outro, representam hidrogênio ou um grupo hidrocarboneto, - R3 e R4, idênticos ou diferentes um do outro, representam hidrogênio ou um grupo hidrocarboneto, que é opcionalmente interrompido por um ou vários heteroátomos e/ou que é opcionalmente substituído por um ou vários grupos funcionais.The present invention relates to a process for producing a solketal amine compound having the general formula (I), wherein said process comprises reacting a compound having the general formula (II) with a compound having the general formula (III) in the presence of a supported metal catalyst, R3R4NH (III) in which: - R1 and R2, identical or different from each other, represent hydrogen or a hydrocarbon group, - R3 and R4, identical or different from one another. another represents hydrogen or a hydrocarbon group, which is optionally interrupted by one or more heteroatoms and/or which is optionally substituted by one or more functional groups.
[0026] Através de estudos contínuos relativos ao processo aprimorado para preparar solketal aminas, o requerente constatou agora surpreendentemente que é possível obter vantajosamente solketal aminas por um procedimento muito simples. A presente invenção pode superar todas as desvantagens dos processos da técnica anterior.[0026] Through continuous studies concerning the improved process for preparing solketal amines, the applicant has now surprisingly found that it is advantageously possible to obtain solketal amines by a very simple procedure. The present invention can overcome all the disadvantages of prior art processes.
[0027] R1 e R2, independentemente um do outro, são escolhidos no grupo que consiste em: hidrogênio ou uma C1- C12 alquila linear ou ramificada, uma C4-C12 cicloalquila e uma arila.[0027] R1 and R2, independently of one another, are chosen from the group consisting of: hydrogen or a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl and an aryl.
[0028] De preferência, R1 e R2, independentemente um do outro, podem ser escolhidos no grupo que consiste em: hidrogênio, metila, etila, isopropila, n-propila, isobutila, n-butila, terc-butila, n-pentila, ciclopentila, ciclo-hexila e fenila.[0028] Preferably, R1 and R2, independently of one another, can be chosen from the group consisting of: hydrogen, methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl and phenyl.
[0029] R3 e R4, independentemente um do outro, são notavelmente escolhidos no grupo que consiste em: hidrogênio ou uma C1-C12 alquila linear ou ramificada, uma C4-C12 cicloalquila e uma arila.[0029] R3 and R4, independently of each other, are notably chosen from the group consisting of: hydrogen or a linear or branched C1-C12 alkyl, a C4-C12 cycloalkyl and an aryl.
[0030] Os grupos preferenciais para R3 ou R4 podem ser H ou alquila. Os grupos mais preferenciais para R3 ou R4 podem ser H ou C1-C5 alquila.[0030] Preferred groups for R3 or R4 may be H or alkyl. The most preferred groups for R3 or R4 can be H or C1-C5 alkyl.
[0031] De preferência, R3 e R4 são todos hidrogênio.[0031] Preferably, R3 and R4 are all hydrogen.
[0032] Uma modalidade preferencial é quando R4 e R2 da fórmula (I) são metila e R3 e R4 da fórmula (I) são hidrogênio.[0032] A preferred embodiment is when R4 and R2 of formula (I) are methyl and R3 and R4 of formula (I) are hydrogen.
[0033] Em outra modalidade, R1 da fórmula (I) é metila, R2 da fórmula (I) é isobutila, e R3 e R4 da fórmula (I) são hidrogênio.[0033] In another embodiment, R1 of formula (I) is methyl, R2 of formula (I) is isobutyl, and R3 and R4 of formula (I) are hydrogen.
[0034] Em uma terceira modalidade, R1 da fórmula (I) é metila, R2 da fórmula (I) é fenila e R3 e R4 da fórmula (I) são hidrogénio.[0034] In a third embodiment, R1 of formula (I) is methyl, R2 of formula (I) is phenyl and R3 and R4 of formula (I) are hydrogen.
[0035] Em uma quarta modalidade, R1 da fórmula (I) é isopropila e R2, R3 e R4 da fórmula (I) são hidrogênio.[0035] In a fourth embodiment, R1 of formula (I) is isopropyl and R2, R3 and R4 of formula (I) are hydrogen.
[0036] De preferência, R3 é hidrogênio e R4 é uma C1-C12 alquila linear ou ramificada, ou uma C4-C12 cicloalquila.[0036] Preferably, R3 is hydrogen and R4 is a linear or branched C1-C12 alkyl, or a C4-C12 cycloalkyl.
[0037] Vantajosamente, o composto da fórmula (I) pode ser escolhido no grupo que consiste em: 2,2-dimetil-1,3- dioxolano-4-metanamina, 2,2-di-isobutil-1,3-dioxolano-4- metanamina, 2-isobutil-2-metil-1,3-dioxolano-4-metanamina, 2-isopropil-1,3-dioxolano-4-metanamina, 2-butil-2-etil-1,3- dioxolano-4-metanamina, 2-fenil-1,3-dioxolano-4-metanamina 2-metil-2-fenil-1,3-dioxolano-4-metanamina e (2-(heptan-3- il)-1,3-dioxolan-4-il)metanamina.Advantageously, the compound of formula (I) can be chosen from the group consisting of: 2,2-dimethyl-1,3-dioxolane-4-methanamine, 2,2-diisobutyl-1,3-dioxolane -4-methanamine, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanamine, 2-isopropyl-1,3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1,3-dioxolane -4-methanamine, 2-phenyl-1,3-dioxolane-4-methanamine 2-methyl-2-phenyl-1,3-dioxolane-4-methanamine and (2-(heptan-3-yl)-1,3 -dioxolan-4-yl)methanamine.
[0038] O composto da fórmula (I) pode, notavelmente, ser um composto que tem a fórmula geral (IV): em que R4 e R2 têm o mesmo significado conforme definido acima.The compound of the formula (I) may notably be a compound having the general formula (IV): wherein R4 and R2 have the same meaning as defined above.
[0039] Vantajosamente, o composto da fórmula (IV) pode ser escolhido no grupo que consiste em: bis((2,2-dimetil- 1,3-dioxolan-4-il)metil)amina, bis((2,2-di-isobutil-1,3- dioxolan-4-il)metil)amina, bis((2-isobutil-2-metil-1,3- dioxolan-4-il)metil)amina, bis((2-isopropil-1,3-dioxolan-4- il)metil)amina, bis((2-butil-2-etil-1,3-dioxolan-4- il)metil)amina, bis((2-fenil-1,3-dioxolan-4-il)metil)amina, bis((2-metil-2-fenil-1,3-dioxolan-4-il)metil)amina e bis((2-(heptan-3-il)-1,3-dioxolano-4-il)metil)amina.Advantageously, the compound of formula (IV) can be chosen from the group consisting of: bis((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)amine, bis((2,2) -diisobutyl-1,3-dioxolan-4-yl)methyl)amine, bis((2-isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl)amine, bis((2-isopropyl) -1,3-dioxolan-4-yl)methyl)amine, bis((2-butyl-2-ethyl-1,3-dioxolan-4-yl)methyl)amine, bis((2-phenyl-1,3) -dioxolan-4-yl)methyl)amine, bis((2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl)amine and bis((2-(heptan-3-yl)-1 ,3-dioxolane-4-yl)methyl)amine.
[0040] Uma modalidade preferencial é quando R1 e R2 da fórmula (II) são metila. Neste caso, o composto está disponível comercialmente, por exemplo, sob o nome Augeo® SL191 ou Solketal. Este composto pode ser sintetizado por reação entre glicerol e acetona, sob condições clássicas bem conhecidas.[0040] A preferred embodiment is when R1 and R2 of formula (II) are methyl. In this case, the compound is commercially available, for example, under the name Augeo® SL191 or Solketal. This compound can be synthesized by reaction between glycerol and acetone, under well-known classical conditions.
[0041] Em outra modalidade, R1 da fórmula (II) é metila, R2 da fórmula (II) é isobutila. Neste caso, o composto está disponível comercialmente, por exemplo, sob o nome Augeo® Clean Plus. Este composto pode ser sintetizado por reação entre glicerol e metil-isobutil cetona, sob condições clássicas bem conhecidas.[0041] In another embodiment, R1 of formula (II) is methyl, R2 of formula (II) is isobutyl. In this case, the compound is commercially available, for example, under the name Augeo® Clean Plus. This compound can be synthesized by reaction between glycerol and methyl isobutyl ketone, under well-known classical conditions.
[0042] Numa terceira modalidade, R1 da fórmula (II) é metila, R2 da fórmula (II) é fenila. Neste caso, o composto está disponível comercialmente, por exemplo, sob o nome Augeo® Film HB. Este composto pode ser sintetizado por reação entre glicerol e acetofenona, sob condições clássicas bem conhecidas.[0042] In a third embodiment, R1 of formula (II) is methyl, R2 of formula (II) is phenyl. In this case, the compound is commercially available, for example, under the name Augeo® Film HB. This compound can be synthesized by reaction between glycerol and acetophenone, under well-known classical conditions.
[0043] Em uma quarta modalidade, R1 da fórmula (II) é isopropila e R2 da fórmula (II) é H. Neste caso, o composto é 2-isobutil-2-metil-1,3-dioxolano-4-metanol. Este composto pode ser sintetizado por reação entre glicerol e isobutiraldeído, sob condições clássicas bem conhecidas.[0043] In a fourth embodiment, R1 of formula (II) is isopropyl and R2 of formula (II) is H. In this case, the compound is 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol. This compound can be synthesized by reaction between glycerol and isobutyraldehyde, under well-known classical conditions.
[0044] Vantajosamente, o composto que tem a fórmula geral (II) é escolhido no grupo que consiste em: 2,2- dimetil-1,3-dioxolano-4-metanol, 2,2-di-isobutil-1,3- dioxolano-4-metanol, 2-isobutil-2-metil-1,3-dioxolano-4- metanol, 2-isopropil-1,3-dioxolano-4-metanol, 2-butil-2- etil-1,3-dioxolano-4-metanol, 2-fenil-1,3-dioxolano-4- metanol e 2-metil-2-fenil-1,3-dioxolano-4-metanol, e (2- (heptan-3-il)-1,3-dioxolan-4-il)metanol.Advantageously, the compound having the general formula (II) is chosen from the group consisting of: 2,2-dimethyl-1,3-dioxolane-4-methanol, 2,2-diisobutyl-1,3 - dioxolane-4-methanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, 2-isopropyl-1,3-dioxolane-4-methanol, 2-butyl-2-ethyl-1,3 -dioxolane-4-methanol, 2-phenyl-1,3-dioxolane-4-methanol and 2-methyl-2-phenyl-1,3-dioxolane-4-methanol, and (2-(heptan-3-yl) -1,3-dioxolan-4-yl)methanol.
[0045] R3 e R4 da fórmula (III) têm o mesmo significado conforme definido acima.[0045] R3 and R4 of formula (III) have the same meaning as defined above.
[0046] Vantajosamente, o composto que tem a fórmula geral (III) é escolhido no grupo que consiste em: NH3,[0046] Advantageously, the compound having the general formula (III) is chosen from the group consisting of: NH3,
(CH3)2NH, (C2H5)2NH, (C3H7)2NH, (C4H9)2NH e (C5H11)2NH.(CH3)2NH, (C2H5)2NH, (C3H7)2NH, (C4H9)2NH and (C5H11)2NH.
[0047] O composto que tem a fórmula geral (III) pode ser escolhido ainda no grupo que consiste em: 2,2-dimetil-1,3- dioxolano-4-metanamina, 2,2-di-isobutil-1,3-dioxolano-4- metanamina, 2-isobutil-2-metil-1,3-dioxolano-4-metanamina, 2-isopropil-1,3-dioxolano-4-metanamina, 2-butil-2-etil-1,3- dioxolano-4-metanamina, 2-fenil-1,3-dioxolano-4-metanamina 2-metil-2-fenil-1,3-dioxolano-4-metanamina e (2-(heptan-3- il)-1,3-dioxolan-4-il)metanamina.[0047] The compound having the general formula (III) can be chosen further from the group consisting of: 2,2-dimethyl-1,3-dioxolane-4-methanamine, 2,2-diisobutyl-1,3 -dioxolane-4-methanamine, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanamine, 2-isopropyl-1,3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1,3 - dioxolane-4-methanamine, 2-phenyl-1,3-dioxolane-4-methanamine 2-methyl-2-phenyl-1,3-dioxolane-4-methanamine and (2-(heptan-3-yl)-1 ,3-dioxolan-4-yl)methanamine.
[0048] A razão molar entre o composto que tem a fórmula geral (II) e o composto que tem a fórmula geral (III) no início da reação é de 1:1 a 1:50.[0048] The molar ratio between the compound having the general formula (II) and the compound having the general formula (III) at the start of the reaction is from 1:1 to 1:50.
[0049] Quando NH3 é empregado como reagente, a razão molar entre o composto que tem a fórmula geral (II) e amônia no início da reação é de 1:1 a 1:30 em uma modalidade.[0049] When NH3 is employed as a reactant, the molar ratio between the compound having the general formula (II) and ammonia at the beginning of the reaction is from 1:1 to 1:30 in one modality.
[0050] O catalisador de metal suportado de acordo com a presente invenção compreende pelo menos um metal na forma elementar e/ou pelo menos um composto de metal de pelo menos um elemento metálico.[0050] The supported metal catalyst according to the present invention comprises at least one metal in elemental form and/or at least one metal compound of at least one metal element.
[0051] O metal na forma elementar ou o metal compreendido no composto de metal pode ser escolhido no grupo que consiste em: (i) elementos do grupo IA, exceto hidrogênio, (ii) elementos do grupo IIA, (iii) elementos do grupo IIIA, (iv) elementos do grupo IVA, exceto carbono, (v) arsênio, antimônio, bismuto, telúrio, polônio e astatina, (vi) elementos dos grupos IB, IIB, IIIB, IVB, VB, VIB, VIIB e VIIIB, (vii) lantanídeos, (viii) actinídeos e (ix) misturas dos mesmos.[0051] The metal in elemental form or the metal comprised in the metal compound may be chosen from the group consisting of: (i) group IA elements, except hydrogen, (ii) group IIA elements, (iii) group elements IIIA, (iv) elements of group IVA, except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatin, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides, (viii) actinides and (ix) mixtures thereof.
[0052] De preferência, o metal na forma elementar ou o metal compreendido no composto de metal é escolhido no grupo que consiste em níquel, cobalto, cobre, estanho, alumínio, cromo, platina, paládio, ródio, rutênio, irídio, prata, ouro, cério, bismuto, rênio e qualquer combinação dos mesmos, mais preferencialmente escolhidos no grupo que consiste em níquel, cobalto, rutênio e misturas dos mesmos e mais preferencialmente níquel.[0052] Preferably, the metal in elemental form or the metal comprised in the metal compound is chosen from the group consisting of nickel, cobalt, copper, tin, aluminum, chromium, platinum, palladium, rhodium, ruthenium, iridium, silver, gold, cerium, bismuth, rhenium and any combination thereof, most preferably chosen from the group consisting of nickel, cobalt, ruthenium and mixtures thereof and most preferably nickel.
[0053] Em algumas modalidades, o catalisador de metal suportado compreende um e apenas um metal na forma elementar.[0053] In some embodiments, the supported metal catalyst comprises one and only one metal in elemental form.
[0054] Em algumas modalidades, o catalisador de metal suportado compreende pelo menos dois metais na forma elementar.[0054] In some embodiments, the supported metal catalyst comprises at least two metals in elemental form.
[0055] O composto de metal compreendido no catalisador de metal suportado é preferencialmente escolhido no grupo que consiste em: óxidos de metal, sais de metal e qualquer combinação dos mesmos. Os ditos sais podem ser escolhidos no grupo que consiste em haleto, nitrato, nitrito, carbonato, bicarbonato, sulfato, sulfito, tiossulfato, fosfato, fosfito, hipofosfito, formato, acetato e propionato.[0055] The metal compound comprised in the supported metal catalyst is preferably chosen from the group consisting of: metal oxides, metal salts and any combination thereof. Said salts can be chosen from the group consisting of halide, nitrate, nitrite, carbonate, bicarbonate, sulfate, sulfite, thiosulfate, phosphate, phosphite, hypophosphite, formate, acetate and propionate.
[0056] Em uma modalidade particular, o catalisador de metal suportado de acordo com a presente invenção compreende pelo menos um metal na forma elementar e pelo menos um óxido de metal.[0056] In a particular embodiment, the supported metal catalyst according to the present invention comprises at least one metal in elemental form and at least one metal oxide.
[0057] O suporte para o catalisador de metal não é particularmente limitado. Pode ser notavelmente um óxido de metal escolhido no grupo que consiste em óxido de alumínio (Al2O3), dióxido de silício (SiO2), óxido de titânio (TiO2), dióxido de zircônio (ZrO2), óxido de cálcio (CaO), óxido de magnésio (MgO), óxido de lantânio (La2O3), dióxido de nióbio (NbO2), óxido de cério (CeO2) e misturas dos mesmos. De preferência, o dito suporte é óxido de alumínio.[0057] The support for the metal catalyst is not particularly limited. It may notably be a metal oxide chosen from the group consisting of aluminum oxide (Al2O3), silicon dioxide (SiO2), titanium oxide (TiO2), zirconium dioxide (ZrO2), calcium oxide (CaO), calcium oxide magnesium (MgO), lanthanum oxide (La2O3), niobium dioxide (NbO2), cerium oxide (CeO2) and mixtures thereof. Preferably, said support is aluminum oxide.
[0058] O suporte também pode ser um zeólito. Os zeólitos são substâncias que têm uma estrutura cristalina e uma capacidade única de alterar os íons. Os versados na técnica podem compreender facilmente como obter esses zeólitos pelo método de preparação relatado, como o zeólito L é descrito no documento US 4503023 ou compra comercial, como ZSM disponível junto à ZEOLYST.[0058] The support can also be a zeolite. Zeolites are substances that have a crystal structure and a unique ability to change ions. Those skilled in the art can easily understand how to obtain these zeolites by the reported method of preparation, as zeolite L is described in US 4503023 or commercial purchase, as ZSM available from ZEOLYST.
[0059] O suporte de catalisador pode ser ainda Kieselguhr, argila ou carbono.[0059] The catalyst support can further be Kieselguhr, clay or carbon.
[0060] A carga do metal na forma elementar e/ou do metal compreendido no composto de metal no suporte depende do metal. Por exemplo, o carregamento de metal nobre no suporte pode ser compreendido de 0,5 % em peso a 20 % em peso com base no peso total do catalisador de metal suportado e, de preferência, de 2 % em peso a 10 % em peso. A carga de metal de base no suporte pode ser compreendida de 2 % em peso a 50 % em peso com base no peso total do catalisador de metal suportado e, de preferência, de 5 % em peso a 20 % em peso.[0060] The charge of the metal in elemental form and/or of the metal comprised in the metal compound in the support depends on the metal. For example, the loading of noble metal on the support can range from 0.5% by weight to 20% by weight based on the total weight of the supported metal catalyst, and preferably from 2% by weight to 10% by weight . The base metal loading on the support may range from 2% by weight to 50% by weight based on the total weight of the supported metal catalyst, and preferably from 5% by weight to 20% by weight.
[0061] Como usado no presente documento, os metais nobres são metais que normalmente são valiosos e resistentes à corrosão e oxidação no ar úmido. Exemplos de metais nobres são rutênio, ródio, paládio, prata, ósmio, irídio, platina e ouro.[0061] As used herein, noble metals are metals that are typically valuable and resistant to corrosion and oxidation in moist air. Examples of noble metals are ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.
[0062] Em oposição a um metal nobre, metal de base de acordo com a presente invenção se refere a metais relativamente baratos e comuns, que podem ser níquel,[0062] As opposed to a noble metal, base metal according to the present invention refers to relatively cheap and common metals, which may be nickel,
cobre, chumbo, zinco, ferro, alumínio, estanho, tungstênio, molibdênio, tântalo, cobalto, bismuto, cádmio, titânio, zircônio, antimônio, manganês, berílio, cromo, germânio, vanádio, gálio, háfnio, índio, nióbio, rênio e tálio.copper, lead, zinc, iron, aluminum, tin, tungsten, molybdenum, tantalum, cobalt, bismuth, cadmium, titanium, zirconium, antimony, manganese, beryllium, chromium, germanium, vanadium, gallium, hafnium, indium, niobium, rhenium and thallium.
[0063] O catalisador compatível inclui aqueles disponíveis comercialmente sob as designações comerciais “PRICAT CU 60/35”, “T-4419”, “PRICAT Ni 52/35”, “PRICAT Ni 62/15”, “T-8031”, “C18-HA”, “PRICAT Ni 20/15”, “T-4466”, “T-4489”, “HTC Ni 500”, “Ni 1404 T3/16 RS”, “Ni 5132 RS” (disponível junto à Johnson Matthey, Sud-Chemie ou BASF).[0063] Compatible catalyst includes those commercially available under the trade designations "PRICAT CU 60/35", "T-4419", "PRICAT Ni 52/35", "PRICAT Ni 62/15", "T-8031", "C18-HA", "PRICAT Ni 20/15", "T-4466", "T-4489", "HTC Ni 500", "Ni 1404 T3/16 RS", "Ni 5132 RS" (available from Johnson Matthey, Sud-Chemie or BASF).
[0064] O catalisador de acordo com a presente invenção poderia ser preparado por maneiras bem conhecidas, como método de impregnação de umidade incipiente (IWI).[0064] The catalyst according to the present invention could be prepared by well-known ways, such as incipient moisture impregnation (IWI) method.
[0065] A impregnação por impregnação incipiente, também chamada de impregnação capilar ou impregnação a seco, é uma técnica comumente usada para a síntese de catalisadores heterogêneos. Normalmente, o precursor de metal ativo é dissolvido em uma solução aquosa ou orgânica. Em seguida, a solução contendo metal é adicionada a um suporte de catalisador contendo o mesmo volume de poro que o volume da solução que foi adicionada. A solução adicionada em excesso ao volume de poro de suporte faz com que o transporte de solução passe de um processo de ação capilar para um processo de difusão, que é muito mais lento. O catalisador pode então ser seco e calcinado para expulsar os componentes voláteis da solução, depositando o metal na superfície do catalisador. O carregamento máximo é limitado pela solubilidade do precursor na solução. O perfil de concentração do composto impregnado depende das condições de transferência de massa dentro dos poros durante a impregnação e secagem.[0065] The impregnation by incipient impregnation, also called capillary impregnation or dry impregnation, is a commonly used technique for the synthesis of heterogeneous catalysts. Typically, the active metal precursor is dissolved in an aqueous or organic solution. Then, the metal-containing solution is added to a catalyst support containing the same pore volume as the volume of the solution that was added. The solution added in excess to the supporting pore volume causes the solution transport to go from a capillary action process to a diffusion process, which is much slower. The catalyst can then be dried and calcined to expel volatile components from the solution, depositing the metal on the catalyst surface. The maximum loading is limited by the solubility of the precursor in the solution. The concentration profile of the impregnated compound depends on the mass transfer conditions within the pores during impregnation and drying.
[0066] A razão de peso entre o catalisador e o composto da fórmula geral (II) no início da reação é de 1:1 a 1:50.[0066] The weight ratio between the catalyst and the compound of general formula (II) at the beginning of the reaction is from 1:1 to 1:50.
[0067] A reação pode ser realizada na ausência ou na presença de um solvente. De preferência, a reação é realizada sem o uso de qualquer solvente.[0067] The reaction can be carried out in the absence or presence of a solvent. Preferably, the reaction is carried out without the use of any solvent.
[0068] O solvente é normalmente escolhido com base em sua capacidade de dissolver os reagentes. Pode ser prótico, aprótico ou uma combinação de solventes próticos e apróticos. Solventes exemplares incluem tolueno, octano, o- xileno, m-xileno, p-xileno, benzeno, tetra-hidrofurano, n- butanol, t-butanol, 2-metilbutan-2-ol e acetonitrila. Solventes que compreendem funcionalidades de hidroxila ou funcionalidades de amina podem ser usados, desde que o solvente não participe na reação no lugar do reagente.[0068] The solvent is usually chosen based on its ability to dissolve the reactants. It can be protic, aprotic or a combination of protic and aprotic solvents. Exemplary solvents include toluene, octane, o-xylene, m-xylene, p-xylene, benzene, tetrahydrofuran, n-butanol, t-butanol, 2-methylbutan-2-ol and acetonitrile. Solvents comprising hydroxyl functionalities or amine functionalities can be used, as long as the solvent does not participate in the reaction in place of the reactant.
[0069] Os reagentes, com um solvente opcional, e o catalisador são tipicamente combinados em um vaso de reação e agitados para constituir a mistura de reação. A mistura de reação é tipicamente mantida à temperatura de reação desejada sob agitação por um tempo suficiente para formar as aminas na quantidade e rendimento desejados.[0069] The reactants, with an optional solvent, and the catalyst are typically combined in a reaction vessel and stirred to constitute the reaction mixture. The reaction mixture is typically held at the desired reaction temperature under stirring for a time sufficient to form the amines in the desired amount and yield.
[0070] De preferência, a temperatura de reação está na faixa de 150 a 200 °C.[0070] Preferably, the reaction temperature is in the range of 150 to 200 °C.
[0071] De preferência, o tempo de reação está na faixa de 10 a 20 horas.[0071] Preferably, the reaction time is in the range of 10 to 20 hours.
[0072] De acordo com a presente invenção, o hidrogênio pode ser opcionalmente introduzido no meio de reação nesta invenção.[0072] According to the present invention, hydrogen can be optionally introduced into the reaction medium in this invention.
[0073] Pode ser entendido pelo técnico no assunto que quando NH3 é usado como reagente, pode ser introduzido na forma de líquido ou gás e, de preferência, na forma de gás.[0073] It can be understood by the person skilled in the art that when NH3 is used as a reactant, it can be introduced in liquid or gas form, and preferably in gas form.
[0074] Quando a reação é realizada em fase líquida, NH3 e H2 podem ser misturados e introduzidos no meio de reação em uma modalidade. Na fase gasosa, a reação pode ser realizada sob uma pressão compreendida entre 1 e 100 bar, de preferência entre 1 e 20 bar.[0074] When the reaction is carried out in liquid phase, NH3 and H2 can be mixed and introduced into the reaction medium in one mode. In the gas phase, the reaction can be carried out under a pressure of between 1 and 100 bar, preferably between 1 and 20 bar.
[0075] A reação pode ser realizada na presença de ar, mas preferencialmente com uma atmosfera inerte, como N2, Ar ou CO2. Essas atmosferas podem ser introduzidas na mistura de reação exclusivamente ou na forma de mistura com NH3 e/ou H2.[0075] The reaction can be carried out in the presence of air, but preferably with an inert atmosphere such as N2, Ar or CO2. These atmospheres can be introduced into the reaction mixture exclusively or in the form of a mixture with NH3 and/or H2.
[0076] Quando a reação catalítica é realizada em um reator de leito fixo, o peso da velocidade espacial horária da reação de acordo com a presente invenção é de 1,0 a 4,0 h-1.[0076] When the catalytic reaction is carried out in a fixed bed reactor, the weight of the hourly space velocity of the reaction according to the present invention is 1.0 to 4.0 h-1.
[0077] Como usado no presente documento, a velocidade espacial horária em peso (doravante WHSV) é definida como o peso do fluxo de alimentação por unidade de peso do catalisador por hora.[0077] As used herein, the hourly space velocity in weight (hereinafter WHSV) is defined as the weight of the feed stream per unit weight of catalyst per hour.
[0078] O catalisador é tipicamente removido da mistura de reação usando qualquer técnica de separação sólido/líquido, como filtração, centrifugação e similares ou uma combinação de métodos de separação. O produto pode ser isolado usando técnicas de isolamento padrão, como destilação. A separação de tal catalisador heterogêneo é mais conveniente do que o catalisador homogêneo usado na técnica anterior.[0078] The catalyst is typically removed from the reaction mixture using any solid/liquid separation technique such as filtration, centrifugation and the like or a combination of separation methods. The product can be isolated using standard isolation techniques such as distillation. The separation of such a heterogeneous catalyst is more convenient than the homogeneous catalyst used in the prior art.
[0079] Além disso, o catalisador pode ser reutilizado. Se desejado, o catalisador pode ser regenerado por lavagem com metanol, água ou uma combinação de água e metanol e submetendo o catalisador lavado a uma temperatura de cerca de 100 °C a cerca de 500 °C por cerca de 2 a 24 horas na presença de oxigênio.[0079] In addition, the catalyst can be reused. If desired, the catalyst can be regenerated by washing with methanol, water or a combination of water and methanol and subjecting the washed catalyst to a temperature of about 100°C to about 500°C for about 2 to 24 hours in the presence of oxygen.
[0080] Vantajosamente, foi agora surpreendentemente constatado que a conversão do composto que tem a fórmula geral (II) é de pelo menos 50 % e a seletividade do composto que tem a fórmula geral (I) é de pelo menos 50 % usando o catalisador de Ni suportado.Advantageously, it has now surprisingly been found that the conversion of the compound having the general formula (II) is at least 50% and the selectivity of the compound having the general formula (I) is at least 50% using the catalyst of Ni supported.
[0081] A presente invenção se estende a uma composição, que é a mistura de reação do processo de acordo com a presente invenção, que compreende: - um composto que tem a fórmula geral (II), - um composto que tem a fórmula geral (III), R3R4NH (III) e - um catalisador de metal suportado, em que: - R1 e R 2, idênticos ou diferentes um do outro, representam hidrogênio ou um grupo hidrocarboneto, - R3 e R 4, idênticos ou diferentes um do outro, representam hidrogênio ou um grupo hidrocarboneto, que é opcionalmente interrompido por um ou vários heteroátomos e/ou que é opcionalmente substituído por um ou vários grupos funcionais.[0081] The present invention extends to a composition, which is the reaction mixture of the process according to the present invention, comprising: - a compound having the general formula (II), - a compound having the general formula (III), R3R4NH (III) and - a supported metal catalyst, in which: - R1 and R2, identical or different from each other, represent hydrogen or a hydrocarbon group, - R3 and R4, identical or different from one another. another represents hydrogen or a hydrocarbon group, which is optionally interrupted by one or more heteroatoms and/or which is optionally substituted by one or more functional groups.
[0082] Opcionalmente, a composição pode compreender ainda um solvente, que tem o mesmo significado conforme definido acima.[0082] Optionally, the composition may further comprise a solvent, which has the same meaning as defined above.
[0083] Opcionalmente, a composição pode compreender ainda hidrogênio.[0083] Optionally, the composition may further comprise hydrogen.
[0084] Opcionalmente, a composição pode compreender ainda um composto de solketal amina que tem a fórmula geral (I): em que R1, R2, R3 e R4 têm o mesmo significado conforme definido acima.Optionally, the composition may further comprise an amine solketal compound having the general formula (I): wherein R 1 , R 2 , R 3 and R 4 have the same meaning as defined above.
[0085] Os seguintes exemplos são incluídos para ilustrar as modalidades da invenção. Obviamente, a invenção não é limitada aos exemplos descritos.[0085] The following examples are included to illustrate embodiments of the invention. Obviously, the invention is not limited to the examples described.
PARTE EXPERIMENTAL Matérias-primasEXPERIMENTAL PART Raw materials
[0086] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) Pricat Nickel 52/35 (Johnson Matthey) Ni(NO3)2.6H2O (Sinopharm) Co(NO3)2.6H2O (Sinopharm) Pricat Nickel 52/35 (Johnson Matthey) 2,2-dimetil-1,3-dioxolano-4-metanol (Solvay) o-xileno (Sigma Aldrich) Exemplo 1 Preparação de catalisadorγ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) Pricat Nickel 52/35 (Johnson Matthey) Ni(NO3)2.6H2O (Sinopharm) Co(NO3)2.6H2O (Sinopharm) Pricat Nickel 52/35 (Johnson Matthey) 2,2-Dimethyl-1,3-dioxolane-4-methanol (Solvay) o-xylene (Sigma Aldrich) Example 1 Catalyst Preparation
[0087] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g foi impregnado por 8 % em peso de Ni usando o método de impregnação de umidade incipiente. Para isso, 0,4350 g de Ni(NO3)2.6H2O foi dissolvido em 0,5 g de H2O e a solução aquosa foi adicionada gota a gota a γ-Al2O3 enquanto se agitava. A mistura foi seca a 100 °C durante a noite e calcinada em ar estático a 400 °C usando uma taxa de aquecimento de 5 °C/min por 2 h. Exemplo 2 Preparação de catalisador[0087] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g was impregnated by 8% by weight of Ni using the incipient moisture impregnation method. For this, 0.4350 g of Ni(NO3)2.6H2O was dissolved in 0.5 g of H2O and the aqueous solution was added dropwise to γ-Al2O3 while stirring. The mixture was dried at 100 °C overnight and calcined in static air at 400 °C using a heating rate of 5 °C/min for 2 h. Example 2 Catalyst Preparation
[0088] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g foi impregnado por 10 % em peso de Ni usando o método de impregnação de umidade incipiente. Para isso, 0,5550 g de Ni(NO3)2.6H2O foi dissolvido em 0,5 g de H2O e a solução aquosa foi adicionada gota a gota a γ-Al2O3 enquanto se agitava. A mistura foi seca a 100 °C durante a noite e calcinada em ar estático a 400 °C usando uma taxa de aquecimento de 5 °C/min por 2 h. Exemplo 3 Preparação de catalisador[0088] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g was impregnated by 10 wt% Ni using the incipient moisture impregnation method. For this, 0.5550 g of Ni(NO3)2.6H2O was dissolved in 0.5 g of H2O and the aqueous solution was added dropwise to γ-Al2O3 while stirring. The mixture was dried at 100 °C overnight and calcined in static air at 400 °C using a heating rate of 5 °C/min for 2 h. Example 3 Catalyst Preparation
[0089] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g foi impregnado por 15 % em peso de Ni usando o método de impregnação de umidade incipiente. Para isso, 0,8800 g de Ni(NO3)2.6H2O foi dissolvido em 0,5 g de H2O e a solução aquosa foi adicionada gota a gota a γ-Al2O3 enquanto se agitava. A mistura foi seca a 100 °C durante a noite e calcinada em ar estático a 400 °C usando uma taxa de aquecimento de 5 °C/min por 2 h. Exemplo 4 Preparação de catalisador[0089] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g was impregnated by 15% by weight of Ni using the incipient moisture impregnation method. For this, 0.8800 g of Ni(NO3)2.6H2O was dissolved in 0.5 g of H2O and the aqueous solution was added dropwise to γ-Al2O3 while stirring. The mixture was dried at 100 °C overnight and calcined in static air at 400 °C using a heating rate of 5 °C/min for 2 h. Example 4 Catalyst Preparation
[0090] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g foi impregnado por 10 % em peso de Co usando o método de impregnação de umidade incipiente. Para isso, 0,5550 g de Co(NO3)2.6H2O foi dissolvido em 0,5 g de H2O e a solução aquosa foi adicionada gota a gota a γ-Al2O3 enquanto se agitava. A mistura foi seca a 100 °C durante a noite e calcinada em ar estático a 400 °C usando uma taxa de aquecimento de 5 °C/min por 2 h. Exemplo 5 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0090] γ-Al2O3 (Puralox SCCa-5/170, 154 m2/g, SASOL) 1 g was impregnated by 10 wt% Co using the incipient moisture impregnation method. For this, 0.5550 g of Co(NO3)2.6H2O was dissolved in 0.5 g of H2O and the aqueous solution was added dropwise to γ-Al2O3 while stirring. The mixture was dried at 100 °C overnight and calcined in static air at 400 °C using a heating rate of 5 °C/min for 2 h. Example 5 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0091] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador de Ni/Al2O3 a 8 % em peso foi pré-reduzido a 400 °C usando uma taxa de aquecimento de 5 °C/min por 1 h por 40 ml/min de H2. 1,5 mmol de 2,2-dimetil-1,3-dioxolano-4-metanol em 3 ml de o-xileno, 1 bar de H2 e 15 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 76 % de conversão de 2,2-dimetil-1,3-dioxolano-4- metanol, 70 % de seletividade de 2,2-dimetil-1,3-dioxolano- 4-metanamina e 22 % de seletividade de bis((2,2-dimetil- 1,3-dioxolan-4-il)metil)amina foram obtidos. Exemplo 6 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0091] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of 8 wt% Ni/Al2O3 catalyst was pre-reduced to 400 °C using a heating rate of 5 °C/min for 1 h per 40 ml/min of H2. 1.5 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 3 ml of o-xylene, 1 bar of H2 and 15 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 76% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 70% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 22% selectivity of bis(( 2,2-dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 6 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0092] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 95 mg de catalisador de Ni/Al2O3 a 10 % em peso foi pré-reduzido a 400 °C usando uma taxa de aquecimento de 5 °C/min por 1 h por 40 ml/min de H2. 1,5 mmol de 2,2-dimetil-1,3-dioxolano-4-metanol em 3 ml de o-xileno, 1 bar de H2 e 15 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 72 % de conversão de 2,2-dimetil-1,3- dioxolano-4-metanol e 94 % de seletividade de 2,2-dimetil- 1,3-dioxolano-4-metanamina, e 5 % de seletividade de bis((2,2-dimetil-1,3-dioxolan-4-il)metil)amina foram obtidos. Exemplo 7 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0092] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 95 mg of 10 wt% Ni/Al2O3 catalyst was pre-reduced to 400 °C using a heating rate of 5 °C/min for 1 h per 40 ml/min of H2. 1.5 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 3 ml of o-xylene, 1 bar of H2 and 15 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 72% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 94% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine, and 5% selectivity of bis( (2,2-dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 7 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0093] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador de Ni/Al2O3 a 15 % em peso foi pré-reduzido a 400 °C usando uma taxa de aquecimento de 5 °C/min por 1 h por 40 ml/min de H2. 1,5 mmol de 2,2-dimetil-1,3-dioxolano-4-metanol em 3 ml de o-xileno, 1 bar de H2 e 15 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 68 % de conversão de 2,2-dimetil-1,3- dioxolano-4-metanol, 73 % de seletividade de 2,2-dimetil- 1,3-dioxolano-4-metanamina e 18 % bis((2,2-dimetil-1,3- dioxolan-4-il)metil)amina foram obtidos. Exemplo 8 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0093] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of 15 wt% Ni/Al2O3 catalyst was pre-reduced to 400 °C using a heating rate of 5 °C/min for 1 h per 40 ml/min of H2. 1.5 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 3 ml of o-xylene, 1 bar of H2 and 15 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 68% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 73% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 18% bis((2,2) -dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 8 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0094] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador de Co/Al2O3 a 10 % em peso foi pré-reduzido a 500 °C usando uma taxa de aquecimento de 5 °C/min por 1 h por 40 ml/min de H2. 1,5 mmol de 2,2-dimetil-1,3-dioxolano-4-metanol em 3 ml de o-xileno, 1 bar de H2 e 15 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 17 % de conversão de 2,2-dimetil-1,3- dioxolano-4-metanol, 69 % de seletividade de 2,2-dimetil- 1,3-dioxolano-4-metanamina e 21 % bis((2,2-dimetil-1,3- dioxolan-4-il)metil)amina foram obtidos. Exemplo 9 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0094] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of 10% by weight Co/Al2O3 catalyst was pre-reduced to 500 °C using a heating rate of 5 °C/min for 1 h per 40 ml/min of H2. 1.5 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 3 ml of o-xylene, 1 bar of H2 and 15 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 17% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 69% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 21% bis((2,2) -dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 9 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0095] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador Pricat Nickel 52/35 (Jonhson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 5 °C/min por 1 h por 40 ml/min de H2. 15 mmol de 2,2-dimetil-1,3-dioxolano-4- metanol, 1 bar de H2 e 150 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 50 % de conversão de 2,2-dimetil-1,3-dioxolano-4- metanol e 66 % de seletividade de 2,2-dimetil-1,3- dioxolano-4-metanamina foram obtidos. Exemplo 10 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0095] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of Pricat Nickel 52/35 catalyst (Jonhson Matthey) was activated at 200 °C using a heating rate of 5 °C/min for 1 h per 40 ml/min of H2. 15 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol, 1 bar of H2 and 150 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 50% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 66% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 10 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0096] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. 1,5 mmol de 2,2-dimetil-1,3-dioxolano-4- metanol em 3 ml de o-xileno, 1 bar de H2 e 15 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 200 °C e mantida por 18 h. 85 % de conversão de 2,2- dimetil-1,3-dioxolano-4-metanol, 65 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina e 29 % bis((2,2- dimetil-1,3-dioxolan-4-il)metil)amina foram obtidos. Exemplo 11 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0096] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. 1.5 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 3 ml of o-xylene, 1 bar of H2 and 15 mmol of NH3 were charged to the reactor. The temperature was raised to 200 °C and maintained for 18 h. 85% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 65% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 29% bis((2,2) - dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 11 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0097] A reação catalítica na fase líquida foi realizada em autoclave vedada de 30 ml. 75 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. 15 mmol de 2,2-dimetil-1,3-dioxolano-4- metanol, 1 bar de H2 e 150 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 200 °C e mantida por 18 h. 50 % de conversão de 2,2-dimetil-1,3-dioxolano-4- metanol, 65 % de seletividade de 2,2-dimetil-1,3-dioxolano- 4-metanamina e 28 % bis((2,2-dimetil-1,3-dioxolan-4- il)metil)amina foram obtidos. Exemplo 12 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0097] The catalytic reaction in the liquid phase was carried out in a sealed 30 ml autoclave. 75 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. 15 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol, 1 bar of H2 and 150 mmol of NH3 were charged to the reactor. The temperature was raised to 200 °C and maintained for 18 h. 50% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 65% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 28% bis((2,2) -dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 12 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0098] A reação catalítica na fase líquida foi realizada em autoclave vedada de 100 ml. 1,0 g de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. 24 mmol de 2,2-dimetil-1,3-dioxolano-4- metanol em 50 ml de o-xileno, 1 bar de H2 e 180 mmol de NH3 foram carregados no reator. A temperatura foi elevada para 180 °C e mantida por 18 h. 63 % de conversão de 2,2- dimetil-1,3-dioxolano-4-metanol, 96 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina e 3 % bis((2,2- dimetil-1,3-dioxolan-4-il)metil)amina foram obtidos. Exemplo 13 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0098] The catalytic reaction in the liquid phase was carried out in a sealed 100 ml autoclave. 1.0 g of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. 24 mmol of 2,2-dimethyl-1,3-dioxolane-4-methanol in 50 ml of o-xylene, 1 bar of H2 and 180 mmol of NH3 were charged to the reactor. The temperature was raised to 180 °C and maintained for 18 h. 63% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 96% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine and 3% bis((2,2) - dimethyl-1,3-dioxolan-4-yl)methyl)amine were obtained. Example 13 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0099] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:30 e WHSV de 3,8 h-1 foi usada. 54 % de conversão de 2,2-dimetil-1,3-dioxolano-4-metanol, 75 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina foram obtidos. Exemplo 14 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0099] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:30 and WHSV of 3.8 h-1 was used. 54% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol, 75% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 14 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0100] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:30 e WHSV (velosidade espacial horária em peso) de 2,6 h-1 foi usada. 70 % de conversão de 2,2-dimetil-1,3- dioxolano-4-metanol e 78 % de seletividade de 2,2-dimetil- 1,3-dioxolano-4-metanamina foram obtidos. Exemplo 15 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0100] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:30 and WHSV (hourly spatial velocity by weight) of 2.6 h-1 was used. 70% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 78% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 15 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0101] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:30 e WHSV de 1,3 h-1 foi usada. 80 % de conversão de 2,2-dimetil-1,3-dioxolano-4-metanol e 73 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina foram obtidos. Exemplo 16 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0101] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:30 and 1.3 h-1 WHSV was used. 80% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 73% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 16 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0102] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:5 e WHSV de 1,3 h-1 foi usada. 82 % de conversão de 2,2-dimetil-1,3-dioxolano-4-metanol e 53 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina foram obtidos. Exemplo 17 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0102] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:5 and WHSV of 1.3 h-1 was used. 82% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 53% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 17 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0103] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por 125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:15 e WHSV de 1,3 h-1 foi usada. 89 % de conversão de 2,2-dimetil-1,3-dioxolano-4-metanol e 60 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina foram obtidos. Exemplo 18 Síntese de 2,2-dimetil-1,3-dioxolano-4-metanamina[0103] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per 125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:15 and WHSV of 1.3 h-1 was used. 89% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 60% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained. Example 18 Synthesis of 2,2-dimethyl-1,3-dioxolane-4-methanamine
[0104] A reação catalítica na fase gasosa foi realizada em um reator de leito fixo. 500 mg de catalisador Pricat Nickel 52/35 (Johnson Matthey) foram ativados a 200 °C usando uma taxa de aquecimento de 20 °C/h por 1 h por[0104] The catalytic reaction in the gas phase was carried out in a fixed bed reactor. 500 mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200 °C using a heating rate of 20 °C/h for 1 h per
125 ml/min de H2. A temperatura do reator foi mantida a 200 °C e 1 bar de pressão total durante a reação. 1,8 ml/h de 2,2-dimetil-1,3-dioxolano-4-metanol, a razão molar de reagente de 2,2-dimetil-1,3-dioxolano-4-metanol:H2:NH3 = 1:5:30 e WHSV de 1,3 h-1 foi usada. 81 % de conversão de 2,2-dimetil-1,3-dioxolano-4-metanol e 70 % de seletividade de 2,2-dimetil-1,3-dioxolano-4-metanamina foram obtidos.125 ml/min of H2. The reactor temperature was maintained at 200 °C and 1 bar total pressure during the reaction. 1.8 ml/h of 2,2-dimethyl-1,3-dioxolane-4-methanol, the molar ratio of 2,2-dimethyl-1,3-dioxolane-4-methanol reagent:H2:NH3 = 1 :5:30 and 1.3 h-1 WHSV was used. 81% conversion of 2,2-dimethyl-1,3-dioxolane-4-methanol and 70% selectivity of 2,2-dimethyl-1,3-dioxolane-4-methanamine were obtained.
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