US20200140610A1 - Catalysts - Google Patents
Catalysts Download PDFInfo
- Publication number
- US20200140610A1 US20200140610A1 US16/723,333 US201916723333A US2020140610A1 US 20200140610 A1 US20200140610 A1 US 20200140610A1 US 201916723333 A US201916723333 A US 201916723333A US 2020140610 A1 US2020140610 A1 US 2020140610A1
- Authority
- US
- United States
- Prior art keywords
- group
- optionally substituted
- hydrogen
- heteroaryl
- iii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 80
- 239000003446 ligand Substances 0.000 claims abstract description 65
- 230000008569 process Effects 0.000 claims abstract description 62
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 150000002118 epoxides Chemical class 0.000 claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 18
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 15
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002596 lactones Chemical class 0.000 claims abstract description 15
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006467 substitution reaction Methods 0.000 claims abstract description 5
- -1 heteroaliphatic Chemical group 0.000 claims description 194
- 125000003118 aryl group Chemical group 0.000 claims description 143
- 239000001257 hydrogen Substances 0.000 claims description 125
- 229910052739 hydrogen Inorganic materials 0.000 claims description 125
- 125000001072 heteroaryl group Chemical group 0.000 claims description 123
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 97
- 125000002723 alicyclic group Chemical group 0.000 claims description 87
- 125000001931 aliphatic group Chemical group 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 54
- 125000003342 alkenyl group Chemical group 0.000 claims description 50
- 150000004820 halides Chemical group 0.000 claims description 50
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- 125000002947 alkylene group Chemical group 0.000 claims description 48
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 48
- YSZSLPRWNYBWRS-LSFNHRITSA-N (2S,9S,12R)-2-cyclohexyl-12-[2-(3,4-dimethoxyphenyl)ethyl]-24,27-dimethoxy-11,18,22-trioxa-4-azatetracyclo[21.2.2.113,17.04,9]octacosa-1(25),13(28),14,16,23,26-hexaene-3,10-dione Chemical compound COC1=C(C=C(C=C1)CC[C@@H]2C3=CC(=CC=C3)OCCCOC4=C(C=C(C=C4OC)[C@@H](C(=O)N5CCCC[C@H]5C(=O)O2)C6CCCCC6)OC)OC YSZSLPRWNYBWRS-LSFNHRITSA-N 0.000 claims description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 45
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 43
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 43
- 125000003545 alkoxy group Chemical group 0.000 claims description 42
- 229910052717 sulfur Inorganic materials 0.000 claims description 38
- 125000000304 alkynyl group Chemical group 0.000 claims description 37
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 36
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 34
- 125000004414 alkyl thio group Chemical group 0.000 claims description 31
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 claims description 30
- 125000004104 aryloxy group Chemical group 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 30
- 125000003277 amino group Chemical group 0.000 claims description 27
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 24
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 24
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical group 0.000 claims description 23
- 125000000732 arylene group Chemical group 0.000 claims description 22
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical group [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 21
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 17
- 239000012986 chain transfer agent Substances 0.000 claims description 17
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 claims description 17
- 150000002825 nitriles Chemical group 0.000 claims description 16
- 125000005110 aryl thio group Chemical group 0.000 claims description 15
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical group [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 claims description 15
- 125000004450 alkenylene group Chemical group 0.000 claims description 14
- 125000004419 alkynylene group Chemical group 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 14
- 125000001188 haloalkyl group Chemical group 0.000 claims description 14
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 14
- 150000002466 imines Chemical class 0.000 claims description 14
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 14
- QMYYTRKPOYDXKT-UHFFFAOYSA-N [O-][N+](=O)S(=O)[N+]([O-])=O Chemical compound [O-][N+](=O)S(=O)[N+]([O-])=O QMYYTRKPOYDXKT-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 239000005977 Ethylene Chemical group 0.000 claims description 8
- 125000002560 nitrile group Chemical group 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 125000001033 ether group Chemical group 0.000 claims description 7
- 125000005549 heteroarylene group Chemical group 0.000 claims description 7
- 125000003375 sulfoxide group Chemical group 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 229910052783 alkali metal Chemical group 0.000 claims description 4
- 150000001340 alkali metals Chemical group 0.000 claims description 4
- 239000002168 alkylating agent Substances 0.000 claims description 4
- 229940100198 alkylating agent Drugs 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 172
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 101
- 239000000243 solution Substances 0.000 description 60
- 239000000047 product Substances 0.000 description 47
- 239000011777 magnesium Substances 0.000 description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 36
- 0 [1*]C1=C([2*])C2=C3C(=C1[2*])c([5*])c1[3*](B)c4c([5*])C5=C6C(=C([2*])C([1*])=C5[2*])c([5*])c5*([3*])c(c2[5*])C52(C)(C)C3C14(C)(C)C62 Chemical compound [1*]C1=C([2*])C2=C3C(=C1[2*])c([5*])c1[3*](B)c4c([5*])C5=C6C(=C([2*])C([1*])=C5[2*])c([5*])c5*([3*])c(c2[5*])C52(C)(C)C3C14(C)(C)C62 0.000 description 32
- 239000002904 solvent Substances 0.000 description 30
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 238000011144 upstream manufacturing Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 150000007942 carboxylates Chemical group 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 8
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 229920000379 polypropylene carbonate Polymers 0.000 description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 150000003462 sulfoxides Chemical class 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000004956 cyclohexylene group Chemical group 0.000 description 5
- 235000019439 ethyl acetate Nutrition 0.000 description 5
- 125000005553 heteroaryloxy group Chemical group 0.000 description 5
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 4
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- UXNAJEJHYUOTLY-UHFFFAOYSA-N [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(C)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCC)CC(C)(C)CN([H])(C4)[Ni]312C Chemical compound [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(C)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCC)CC(C)(C)CN([H])(C4)[Ni]312C UXNAJEJHYUOTLY-UHFFFAOYSA-N 0.000 description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 229960004132 diethyl ether Drugs 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000002921 oxetanes Chemical class 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000011982 enantioselective catalyst Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical group C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical group C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- SFJRUJUEMVAZLM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxymethyl]oxirane Chemical compound CC(C)(C)OCC1CO1 SFJRUJUEMVAZLM-UHFFFAOYSA-N 0.000 description 2
- NCTSLPBQVXUAHR-UHFFFAOYSA-N 3,5-ditert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1 NCTSLPBQVXUAHR-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- UYRSLWPKZKASRB-UHFFFAOYSA-N 4-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C(O)=C1 UYRSLWPKZKASRB-UHFFFAOYSA-N 0.000 description 2
- WQNTWZJPCLUXQC-UHFFFAOYSA-N 5-tert-butyl-2-hydroxybenzene-1,3-dicarbaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C=O)=C1 WQNTWZJPCLUXQC-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- NPYIWQBVGZTXKK-UHFFFAOYSA-N CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC1 Chemical compound CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC1 NPYIWQBVGZTXKK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- KCYCAIORHBSNBV-UHFFFAOYSA-N [H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(C)CC(C)(C)CN5(C)CC6=CC(C(C)(C)C)=CC7=C6O6[Ni]1(C)(O4[Ni]635C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN35CCN6(CC3)CC3=CC(C(C)(C)C)=CC7=C3O3[Ni]1(C)(O4[Ni]356C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2([H])C5=C(C=CC=C5)N([H])(C4)[Ni]312C Chemical compound [H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(C)CC(C)(C)CN5(C)CC6=CC(C(C)(C)C)=CC7=C6O6[Ni]1(C)(O4[Ni]635C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN35CCN6(CC3)CC3=CC(C(C)(C)C)=CC7=C3O3[Ni]1(C)(O4[Ni]356C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2([H])C5=C(C=CC=C5)N([H])(C4)[Ni]312C KCYCAIORHBSNBV-UHFFFAOYSA-N 0.000 description 2
- RNBNWTOUSONTEJ-BAUTXCBNSA-N [H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(C)CC(C)(C)CN5(C)CC6=CC(C(C)(C)C)=CC7=C6O6[Ni]1(C)(O4[Ni]635C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Mg]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Mg]32(C)O56.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCCC)CC(C)(C)CN([H])(C4)[Ni]312C Chemical compound [H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(C)CC(C)(C)CN5(C)CC6=CC(C(C)(C)C)=CC7=C6O6[Ni]1(C)(O4[Ni]635C)N([H])(C7)CC(C)(C)C2.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Mg]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Mg]32(C)O56.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCCC)CC(C)(C)CN([H])(C4)[Ni]312C RNBNWTOUSONTEJ-BAUTXCBNSA-N 0.000 description 2
- RPPXGLZJMXVEBS-UHFFFAOYSA-N [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCCC)CC(C)(C)CN([H])(C4)[Ni]312C Chemical compound [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCC)CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2(CCCC)CC(C)(C)CN([H])(C4)[Ni]312C RPPXGLZJMXVEBS-UHFFFAOYSA-N 0.000 description 2
- DSBXVGWLKWBHIX-XLUVCVKHSA-N [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2([H])CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Ni]32(C)O56.[H]N12CCCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Mg]13(C)O5[Mg]764C)C2 Chemical compound [H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN5([H])CC(C)(C)C2)CN2([H])CC(C)(C)CN([H])(C4)[Ni]312C.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Ni]32(C)O56.[H]N12CCCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Mg]13(C)O5[Mg]764C)C2 DSBXVGWLKWBHIX-XLUVCVKHSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical group CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- RVJVAMZRPQBPEE-UHFFFAOYSA-N cyclohex-2-ene-1,1-diol Chemical compound OC1(O)CCCC=C1 RVJVAMZRPQBPEE-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 150000007976 iminium ions Chemical class 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical group C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical group CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- JXRIGNBVDJINOQ-UHFFFAOYSA-N n,n',2,2-tetramethylpropane-1,3-diamine Chemical compound CNCC(C)(C)CNC JXRIGNBVDJINOQ-UHFFFAOYSA-N 0.000 description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical group CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical compound OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229960002920 sorbitol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 1
- 125000006648 (C1-C8) haloalkyl group Chemical group 0.000 description 1
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 1
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BVOMRRWJQOJMPA-UHFFFAOYSA-N 1,2,3-trithiane Chemical compound C1CSSSC1 BVOMRRWJQOJMPA-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000005926 1,2-dimethylbutyloxy group Chemical group 0.000 description 1
- 125000005923 1,2-dimethylpropyloxy group Chemical group 0.000 description 1
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical compound C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- IMLSAISZLJGWPP-UHFFFAOYSA-N 1,3-dithiolane Chemical compound C1CSCS1 IMLSAISZLJGWPP-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- KXSWSFNGQCBWQA-UHFFFAOYSA-N 1a,2,7,7a-tetrahydronaphtho[2,3-b]oxirene Chemical compound C1C2=CC=CC=C2CC2C1O2 KXSWSFNGQCBWQA-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- OHCMANJUZNNOQW-UHFFFAOYSA-N 2,4,4-trimethylcyclohexene-1-carbaldehyde Chemical compound CC1=C(C=O)CCC(C)(C)C1 OHCMANJUZNNOQW-UHFFFAOYSA-N 0.000 description 1
- KQXZMAACKJIRJE-UHFFFAOYSA-N 2-(2-methoxyethoxymethyl)oxirane Chemical compound COCCOCC1CO1 KQXZMAACKJIRJE-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- DQBPICZFQWJEKL-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxymethyl]oxirane Chemical compound COCCOCCOCC1CO1 DQBPICZFQWJEKL-UHFFFAOYSA-N 0.000 description 1
- CBTRJEXEEWVQHL-UHFFFAOYSA-N 2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound COCCOCCOCCOCC1CO1 CBTRJEXEEWVQHL-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- JFDMLXYWGLECEY-UHFFFAOYSA-N 2-benzyloxirane Chemical compound C=1C=CC=CC=1CC1CO1 JFDMLXYWGLECEY-UHFFFAOYSA-N 0.000 description 1
- 125000003858 2-ethylbutoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])O*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005924 2-methylpentyloxy group Chemical group 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical compound N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- ONJRTQUWKRDCTA-UHFFFAOYSA-N 2h-thiochromene Chemical compound C1=CC=C2C=CCSC2=C1 ONJRTQUWKRDCTA-UHFFFAOYSA-N 0.000 description 1
- VGMRMWXCAIUHCW-UHFFFAOYSA-N 3-(bromomethyl)-5-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(CBr)=C(O)C(C=O)=C1 VGMRMWXCAIUHCW-UHFFFAOYSA-N 0.000 description 1
- CGRJJOYCFCCGPX-UHFFFAOYSA-N 3-ethyloxetane Chemical compound CCC1COC1 CGRJJOYCFCCGPX-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VJQHJNIGWOABDZ-UHFFFAOYSA-N 3-methyloxetane Chemical compound CC1COC1 VJQHJNIGWOABDZ-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000005925 3-methylpentyloxy group Chemical group 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 description 1
- KWIVRAVCZJXOQC-UHFFFAOYSA-N 3h-oxathiazole Chemical compound N1SOC=C1 KWIVRAVCZJXOQC-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- GDRVFDDBLLKWRI-UHFFFAOYSA-N 4H-quinolizine Chemical compound C1=CC=CN2CC=CC=C21 GDRVFDDBLLKWRI-UHFFFAOYSA-N 0.000 description 1
- UKGCFMYYDATGNN-UHFFFAOYSA-N 6,6a-dihydro-1ah-indeno[1,2-b]oxirene Chemical compound C12=CC=CC=C2CC2C1O2 UKGCFMYYDATGNN-UHFFFAOYSA-N 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RWTINXZZGKXSKZ-CQGYESPNSA-N B.CC(C)(C)C1=CC(C=O)=C(O)C(CBr)=C1.CC(C)(C)C1=CC(C=O)=C(O)C(CSCCCSCC2=CC(C(C)(C)C)=CC(C=O)=C2O)=C1.CC(C)(CN)CN.CC1(C)C/N=C/C2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)/C=N/C1.CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CO.SCCCS.[NaH] Chemical compound B.CC(C)(C)C1=CC(C=O)=C(O)C(CBr)=C1.CC(C)(C)C1=CC(C=O)=C(O)C(CSCCCSCC2=CC(C(C)(C)C)=CC(C=O)=C2O)=C1.CC(C)(CN)CN.CC1(C)C/N=C/C2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)/C=N/C1.CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CO.SCCCS.[NaH] RWTINXZZGKXSKZ-CQGYESPNSA-N 0.000 description 1
- DBFXRMISOQJIHA-UHFFFAOYSA-N B.CC(C)(C)C1=CC(C=O)=C(O)C(CN2CCN(CC3=CC(C(C)(C)C)=CC(C=O)=C3O)CC2)=C1.CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1 Chemical compound B.CC(C)(C)C1=CC(C=O)=C(O)C(CN2CCN(CC3=CC(C(C)(C)C)=CC(C=O)=C3O)CC2)=C1.CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1 DBFXRMISOQJIHA-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- YHGOPRZDWHBSIF-IWSWGKSLSA-N C#CCOCC1CO1.C1=CC=C(COCC2CO2)C=C1.C1=CC=C(OCC2CO2)C=C1.C1=COC(COCC2CO2)=C1.C1COC(COCC2CO2)C1.C=CCOCC1CO1.CC(C)(C)OCC1CO1.CC(C)CCCC(C)C1CCC2C3CC=C4C[C@@H](OC(=O)OCC5CO5)CCC4(C)C3CCC12C.CC(C)OCC1CO1.CC1=CC(OCC2CO2)=CC=C1.CCCCOCC1CO1.CCOC(=O)OCC1CO1.COC(=O)OCC1CO1.COCC1CO1.COCCOCC1CO1.ClCOCC1CO1.O=C(OCC1CO1)C1=CC=CC=C1 Chemical compound C#CCOCC1CO1.C1=CC=C(COCC2CO2)C=C1.C1=CC=C(OCC2CO2)C=C1.C1=COC(COCC2CO2)=C1.C1COC(COCC2CO2)C1.C=CCOCC1CO1.CC(C)(C)OCC1CO1.CC(C)CCCC(C)C1CCC2C3CC=C4C[C@@H](OC(=O)OCC5CO5)CCC4(C)C3CCC12C.CC(C)OCC1CO1.CC1=CC(OCC2CO2)=CC=C1.CCCCOCC1CO1.CCOC(=O)OCC1CO1.COC(=O)OCC1CO1.COCC1CO1.COCCOCC1CO1.ClCOCC1CO1.O=C(OCC1CO1)C1=CC=CC=C1 YHGOPRZDWHBSIF-IWSWGKSLSA-N 0.000 description 1
- GNDSRXYPTPNBAR-UHFFFAOYSA-N C.CC(C)(C)C1=CC(C=O)=C(O)C(CBr)=C1.CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 Chemical compound C.CC(C)(C)C1=CC(C=O)=C(O)C(CBr)=C1.CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 GNDSRXYPTPNBAR-UHFFFAOYSA-N 0.000 description 1
- LSCODWUHQTXWIM-UHFFFAOYSA-N C1=CC=C(C2OCC3OC3CO2)C=C1.C1=CC=C(C2OCC3OC3CO2)C=C1.C1CCC2(CC1)OCC1OC1CO2.C1OCC2OC2CO1 Chemical compound C1=CC=C(C2OCC3OC3CO2)C=C1.C1=CC=C(C2OCC3OC3CO2)C=C1.C1CCC2(CC1)OCC1OC1CO2.C1OCC2OC2CO1 LSCODWUHQTXWIM-UHFFFAOYSA-N 0.000 description 1
- CUEWRDQTPIOQEG-UHFFFAOYSA-N C1OC(c2ccccc2)OCC2OC12 Chemical compound C1OC(c2ccccc2)OCC2OC12 CUEWRDQTPIOQEG-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- UEUWTGLGZVYFMB-UHFFFAOYSA-N C=C1CC(=O)OC1=O.CC12CCC(C(=O)OC1=O)C2(C)C.CC1=CC(=O)OC1=O.O=C1C=CC(=O)O1.O=C1C=CCC(=O)O1.O=C1CC2=C(C=CC=C2)C(=O)O1.O=C1CCC(=O)O1.O=C1CCCC(=O)O1.O=C1CCNC(=O)O1.O=C1COCC(=O)O1.O=C1OC(=O)C2=C1C=CC=C2.O=C1OC(=O)C2CC12.O=C1OC(=O)C2CC=CCC12.O=C1OC(=O)C2CCCC12.O=C1OC(=O)C2CCCCC12 Chemical compound C=C1CC(=O)OC1=O.CC12CCC(C(=O)OC1=O)C2(C)C.CC1=CC(=O)OC1=O.O=C1C=CC(=O)O1.O=C1C=CCC(=O)O1.O=C1CC2=C(C=CC=C2)C(=O)O1.O=C1CCC(=O)O1.O=C1CCCC(=O)O1.O=C1CCNC(=O)O1.O=C1COCC(=O)O1.O=C1OC(=O)C2=C1C=CC=C2.O=C1OC(=O)C2CC12.O=C1OC(=O)C2CC=CCC12.O=C1OC(=O)C2CCCC12.O=C1OC(=O)C2CCCCC12 UEUWTGLGZVYFMB-UHFFFAOYSA-N 0.000 description 1
- GDZREYBOVODIQQ-CQFHKPFHSA-N CC1(C)C/N=C/C2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)/C=N/C1 Chemical compound CC1(C)C/N=C/C2=C(O)C(=CC(C(C)(C)C)=C2)CSCCCSCC2=CC(C(C)(C)C)=CC(=C2O)/C=N/C1 GDZREYBOVODIQQ-CQFHKPFHSA-N 0.000 description 1
- OXDCDEZDLNVCGJ-UHFFFAOYSA-N CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1 Chemical compound CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1 OXDCDEZDLNVCGJ-UHFFFAOYSA-N 0.000 description 1
- ZQHDIYIPULXTFT-UHFFFAOYSA-N CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC2=C(C=CC=C2)NCC2=C(O)C(=CC(C(C)(C)C)=C2)CNC1.CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 Chemical compound CC1(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN2CCN(CC2)CC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC2=C(C=CC=C2)NCC2=C(O)C(=CC(C(C)(C)C)=C2)CNC1.CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 ZQHDIYIPULXTFT-UHFFFAOYSA-N 0.000 description 1
- QOVFZUCMOBLBBH-UHFFFAOYSA-N CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC2=C(C=CC=C2)NCC2=C(O)C(=CC(C(C)(C)C)=C2)CNC1 Chemical compound CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC2=C(C=CC=C2)NCC2=C(O)C(=CC(C(C)(C)C)=C2)CNC1 QOVFZUCMOBLBBH-UHFFFAOYSA-N 0.000 description 1
- FGDGSJFIJJWANA-UHFFFAOYSA-N CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CCCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CN(CCC(=O)OC)CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.COC(=O)CCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.O=C=O Chemical compound CC1(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNC1.CCCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CN(CCC(=O)OC)CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.COC(=O)CCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.O=C=O FGDGSJFIJJWANA-UHFFFAOYSA-N 0.000 description 1
- GZYXPXGNODDCBD-UHFFFAOYSA-N CC1(C)OC(=O)C(C)(C)OC1=O Chemical compound CC1(C)OC(=O)C(C)(C)OC1=O GZYXPXGNODDCBD-UHFFFAOYSA-N 0.000 description 1
- QLOYPKMEKVVONZ-UHFFFAOYSA-N CC1(C)OC(=O)C(C)(C)OC1=O.CC1OC(=O)C(C)OC1=O.O=C1CCC(=O)OC1 Chemical compound CC1(C)OC(=O)C(C)(C)OC1=O.CC1OC(=O)C(C)OC1=O.O=C1CCC(=O)OC1 QLOYPKMEKVVONZ-UHFFFAOYSA-N 0.000 description 1
- USYFFEUORQASRF-UHFFFAOYSA-N CC1(C)OC1=O Chemical compound CC1(C)OC1=O USYFFEUORQASRF-UHFFFAOYSA-N 0.000 description 1
- DHIJCCFOCGAODX-UHFFFAOYSA-N CC1CC(=O)C1.CC1CCCC1=O.CCC1CC(=O)C1.O=C1CCCCCO1.O=C1CCCCO1.O=C1CCCO1 Chemical compound CC1CC(=O)C1.CC1CCCC1=O.CCC1CC(=O)C1.O=C1CCCCCO1.O=C1CCCCO1.O=C1CCCO1 DHIJCCFOCGAODX-UHFFFAOYSA-N 0.000 description 1
- AESYSRBITQXXBF-UHFFFAOYSA-N CCCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CN(CCC(=O)OC)CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.O=C=O Chemical compound CCCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CN(CCC(=O)OC)CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1.O=C=O AESYSRBITQXXBF-UHFFFAOYSA-N 0.000 description 1
- JEJYCPXDNNOWNR-UHFFFAOYSA-N CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 Chemical compound CN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=C(O)C(=CC(C(C)(C)C)=C2)CN(C)CC(C)(C)C1 JEJYCPXDNNOWNR-UHFFFAOYSA-N 0.000 description 1
- AJQFDRMJJBOUNR-CPSCLPLWSA-L CO.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Mg]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Mg]32(C)O56.[Li]OC1=C2C=C(C(C)(C)C)C=C1CNCC(C)(C)CNCC1=CC(C(C)(C)C)=CC(=C1O[Li])/C=N/CC(C)(C)C/N=C/2 Chemical compound CO.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Mg]56(C)/N(=C\4)CC(C)(C)C/N5=C/C4=C5C(=CC(C(C)(C)C)=C4)CN([H])(CC(C)(C)C1)[Mg]32(C)O56.[Li]OC1=C2C=C(C(C)(C)C)C=C1CNCC(C)(C)CNCC1=CC(C(C)(C)C)=CC(=C1O[Li])/C=N/CC(C)(C)C/N=C/2 AJQFDRMJJBOUNR-CPSCLPLWSA-L 0.000 description 1
- QHOLAKOPVYBJJR-UHFFFAOYSA-N COC(=O)CCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1 Chemical compound COC(=O)CCN1CC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)CNCC2=CC(C(C)(C)C)=CC(=C2O)CNCC(C)(C)C1 QHOLAKOPVYBJJR-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KYZIXHLDWJBHDI-UHFFFAOYSA-N Cc1(C)c(C)(C)C(=O)OC1=O Chemical compound Cc1(C)c(C)(C)C(=O)OC1=O KYZIXHLDWJBHDI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VZHUBBUZNIULNM-UHFFFAOYSA-N Cyclohexyl butanoate Chemical compound CCCC(=O)OC1CCCCC1 VZHUBBUZNIULNM-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BVMWIXWOIGJRGE-UHFFFAOYSA-N NP(O)=O Chemical compound NP(O)=O BVMWIXWOIGJRGE-UHFFFAOYSA-N 0.000 description 1
- WZMXYZJAIFGCJE-UHFFFAOYSA-N O=C(C1)OCCC1C(CCCC1)OC1=O Chemical compound O=C(C1)OCCC1C(CCCC1)OC1=O WZMXYZJAIFGCJE-UHFFFAOYSA-N 0.000 description 1
- JDLXBOMBSIYZDS-UHFFFAOYSA-N O=C1OC(CC(CCO2)C2=O)CC1 Chemical compound O=C1OC(CC(CCO2)C2=O)CC1 JDLXBOMBSIYZDS-UHFFFAOYSA-N 0.000 description 1
- LDMLCFMTXNIMCI-UHFFFAOYSA-N O=C=O.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(CCC(=O)OC)CC(C)(C)CN5([H])CC6=C7C(=CC(C(C)(C)C)=C6)CN(CCC)(CC(C)(C)C1)[Ni]21(C)O4[Ni]53(C)O71.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN6(CCC(=O)OC)CC(C)(C)CN([H])(C4)[Ni]136C)CN5([H])CC(C)(C)C2.[H]N12CCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Ni]13(C)O5[Ni]764C)C2 Chemical compound O=C=O.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(CCC(=O)OC)CC(C)(C)CN5([H])CC6=C7C(=CC(C(C)(C)C)=C6)CN(CCC)(CC(C)(C)C1)[Ni]21(C)O4[Ni]53(C)O71.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN6(CCC(=O)OC)CC(C)(C)CN([H])(C4)[Ni]136C)CN5([H])CC(C)(C)C2.[H]N12CCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Ni]13(C)O5[Ni]764C)C2 LDMLCFMTXNIMCI-UHFFFAOYSA-N 0.000 description 1
- PMXSALOWIQVHSN-UHFFFAOYSA-N O=C=O.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(CCC)CC(C)(C)CN5([H])CC6=C7C(=CC(C(C)(C)C)=C6)CN(CCC)(CC(C)(C)C1)[Ni]21(C)O7[Ni]53(C)O41.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN6(CCC(=O)OC)CC(C)(C)CN([H])(C4)[Ni]136C)CN5([H])CC(C)(C)C2.[H]N12CCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Ni]13(C)O5[Ni]764C)C2 Chemical compound O=C=O.[H]N12CC3=C4C(=CC(C(C)(C)C)=C3)CN3(CCC)CC(C)(C)CN5([H])CC6=C7C(=CC(C(C)(C)C)=C6)CN(CCC)(CC(C)(C)C1)[Ni]21(C)O7[Ni]53(C)O41.[H]N12CC3=CC(C(C)(C)C)=CC4=C3O3[Ni]15(C)O1C6=C(C=C(C(C)(C)C)C=C6CN6(CCC(=O)OC)CC(C)(C)CN([H])(C4)[Ni]136C)CN5([H])CC(C)(C)C2.[H]N12CCN3([H])CC4=C5C(=CC(C(C)(C)C)=C4)CN4([H])CC(C)(C)CN6([H])CC7=CC(C(C)(C)C)=CC(=C7O7[Ni]13(C)O5[Ni]764C)C2 PMXSALOWIQVHSN-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- JZFICWYCTCCINF-UHFFFAOYSA-N Thiadiazin Chemical compound S=C1SC(C)NC(C)N1CCN1C(=S)SC(C)NC1C JZFICWYCTCCINF-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229910007340 Zn(OAc)2.2H2O Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-M diphenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-M 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LOZWAPSEEHRYPG-UHFFFAOYSA-N dithiane Natural products C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 description 1
- MNQDKWZEUULFPX-UHFFFAOYSA-M dithiazanine iodide Chemical compound [I-].S1C2=CC=CC=C2[N+](CC)=C1C=CC=CC=C1N(CC)C2=CC=CC=C2S1 MNQDKWZEUULFPX-UHFFFAOYSA-M 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052730 francium Chemical group 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical group [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 150000002243 furanoses Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 1
- 125000006609 n-nonyloxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical group OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- GMQOZFVOGGIFIX-UHFFFAOYSA-N oxathiazolidine Chemical compound C1COSN1 GMQOZFVOGGIFIX-UHFFFAOYSA-N 0.000 description 1
- SWYHWLFHDVMLHO-UHFFFAOYSA-N oxetan-3-ylmethanol Chemical compound OCC1COC1 SWYHWLFHDVMLHO-UHFFFAOYSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940032159 propylene carbonate Drugs 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005717 substituted cycloalkylene group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical group CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical group C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical compound C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/08—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/23—Calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Definitions
- the present invention relates to the field of polymerisation catalysts, and systems comprising said catalysts for polymerising carbon dioxide and an epoxide, a lactide and/or lactone, and/or an epoxide and an anhydride.
- CO 2 carbon dioxide
- phosgene petrochemical feedstocks
- One of the developing applications of CO 2 is the copolymerization with epoxides to yield aliphatic polycarbonates. The development of effective catalysts to make such a process profitable is the subject of continuous research.
- WO2013/034750 discloses the copolymerisation of an epoxide with CO 2 in the presence of a chain transfer agent using a catalyst of a class represented by formula (I):
- cyclohexene oxide (CHO) received special interest, as the product, poly(cyclohexene carbonate) (PCHC) shows a high glass transition temperature and reasonable tensile strength.
- PCHC poly(cyclohexene carbonate)
- Ethylene oxide, propylene oxide and butylene oxide have also received interest as they produce polymers (polyalkylene carbonates, such as PPC) with elastomeric properties which are useful in many applications e.g. films.
- the asymmetric catalysts referred to herein represent a novel and inventive means of catalysing the polymerisation of carbon dioxide with various monomers to produce useful polymer products with good activity and selectivity.
- M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Ni(II), Mn(II), Mg(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Ni(III)-X, Mn(III)-X, Fe(III)-X, Ca(II), Ge(II), AI(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2 or Ti(IV)-(X) 2 ;
- R 1 and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted al
- R 1 and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
- R 3A and R 3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkeny
- the invention extends to methods of preparation of ligands, complexes and catalysts according to the second aspect and first aspect respectively or as otherwise defined herein.
- a process of asymmetric N-substitution of a symmetrical ligand having a tetraaminophenol coordination sphere comprising the following steps:
- a process for the reaction of (i) carbon dioxide with an epoxide, (ii) an anhydride and an epoxide, and/or (iii) a lactide and/or a lactone in the presence of a catalyst according to the first aspect, optionally in the presence of a chain transfer agent.
- the sixth aspect of the invention provides a product of the process of the fifth aspect of the invention.
- an aliphatic group is a hydrocarbon moiety that may be straight chain or branched and may be completely saturated, or contain one or more units of unsaturation, but which is not aromatic.
- the term “unsaturated” means a moiety that has one or more double and/or triple bonds.
- the term “aliphatic” is therefore intended to encompass alkyl, alkenyl or alkynyl groups, and combinations thereof.
- An aliphatic group is preferably a C 1-20 aliphatic group, that is, an aliphatic group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
- an aliphatic group is a C 1-15 aliphatic, more preferably a C 1-12 aliphatic, more preferably a C 1-10 aliphatic, even more preferably a C 1-8 aliphatic, such as a C 1-6 aliphatic group.
- An alkyl group is preferably a “C 1-20 alkyl group”, that is an alkyl group that is a straight or branched chain with 1 to 20 carbons.
- the alkyl group therefore has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
- an alkyl group is a C 1-15 alkyl, preferably a C 1-12 alkyl, more preferably a C 1-10 alkyl, even more preferably a C 1-8 alkyl, even more preferably a C 1-6 alkyl group.
- C 1-20 alkyl group examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1,1-dimethylpropyl group, 1,2-d
- Alkenyl and alkynyl groups are preferably “C 2-20 alkenyl” and “C 2-20 alkynyl”, more preferably “C 2-15 alkenyl” and “C 2-15 alkynyl”, even more preferably “C 2-12 alkenyl” and “C 2-12 alkynyl”, even more preferably “C 2-10 alkenyl” and “C 2-10 alkynyl”, even more preferably “C 2-8 alkenyl” and “C 2-8 alkynyl”, most preferably “C 2-6 alkenyl” and “C 2-6 alkynyl” groups, respectively. Alkene and alkyne should be understood accordingly.
- a heteroaliphatic group is an aliphatic group as described above, which additionally contains one or more heteroatoms.
- Heteroaliphatic groups therefore preferably contain from 2 to 21 atoms, preferably from 2 to 16 atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 11 atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to 7 atoms, wherein at least one atom is a carbon atom.
- Particularly preferred heteroatoms are selected from O, S, N, P and Si.
- the heteroatoms may be the same or different.
- An alicyclic group is a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridging and spiro-fused) ring system which has from 3 to 20 carbon atoms, that is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
- an alicyclic group has from 3 to 15, more preferably from 3 to 12, even more preferably from 3 to 10, even more preferably from 3 to 8 carbon atoms, even more preferably from 3 to 6 carbons atoms.
- the term “alicyclic” encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups.
- the alicyclic group may comprise an alicyclic ring bearing one or more linking or non-linking alkyl substituents, such as —CH 2 -cyclohexyl.
- alkyl substituents such as —CH 2 -cyclohexyl.
- examples of the C 3-20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.
- a heteroalicyclic group is an alicyclic group as defined above which has, in addition to carbon atoms, one or more ring heteroatoms, which are preferably selected from O, S, N, P and Si.
- Heteroalicyclic groups preferably contain from one to four heteroatoms, which may be the same or different. Heterocyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.
- An aryl group is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms.
- An aryl group is preferably a “C 6-12 aryl group” and is an aryl group constituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like.
- examples of “C 6-10 aryl group” include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group.
- a heteroaryl group is an aryl group having, in addition to carbon atoms, from one to four ring heteroatoms which are preferably selected from O, S, N, P and Si.
- a heteroaryl group preferably has from 5 to 20, more preferably from 5 to 14 ring atoms.
- examples of a heteroaryl group include pyridine, imidazole, methylimidazole and dimethylaminopyridine.
- alicyclic, heteroalicyclic, aryl and heteroaryl groups include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazin
- halide or “halogen” are used interchangeably and, as used herein mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom, a bromine atom or a chlorine atom, and more preferably a fluorine atom.
- a haloalkyl group is preferably a “C 1-20 haloalkyl group”, more preferably a “C 1-15 haloalkyl group”, more preferably a “C 1-12 haloalkyl group”, more preferably a “C 1-10 haloalkyl group”, even more preferably a “C 1-8 haloalkyl group”, even more preferably a “C 1-6 haloalkyl group” and is a C 1-20 alkyl, a C 1-15 alkyl, a C 1-12 alkyl, a C 1-10 alkyl, a C 1-8 alkyl, or a C 1-6 alkyl group, respectively, as described above substituted with at least one halogen atom, preferably 1, 2 or 3 halogen atom(s).
- C 1-20 haloalkyl group examples include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.
- An alkoxy group is preferably a “C 1-20 alkoxy group”, more preferably a “C 1-15 alkoxy group”, more preferably a “C 1-12 alkoxy group”, more preferably a “C 1-10 alkoxy group”, even more preferably a “C 1-8 alkoxy group”, even more preferably a “C 1-6 alkoxy group” and is an oxy group that is bonded to the previously defined C 1-20 alkyl, C 1-15 alkyl, C 1-12 alkyl, C 1-10 alkyl, C 1-8 alkyl, or C 1-6 alkyl group respectively.
- C 1-20 alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-pentade
- An aryloxy group is preferably a “C 5-20 aryloxy group”, more preferably a “C 6-12 aryloxy group”, even more preferably a “C 6-10 aryloxy group” and is an oxy group that is bonded to the previously defined C 5-20 aryl, C 6-12 aryl, or C 6-10 aryl group respectively.
- An alkylthio group is preferably a “C 1-20 alkylthio group”, more preferably a “C 1-15 alkylthio group”, more preferably a “C 1-12 alkylthio group”, more preferably a “C 1-10 alkylthio group”, even more preferably a “C 1-8 alkylthio group”, even more preferably a “C 1-6 alkylthio group” and is a thio (—S—) group that is bonded to the previously defined C 1-20 alkyl, C 1-15 alkyl, C 1-12 alkyl, C 1-10 alkyl, C 1-8 alkyl, or C 1-6 alkyl group respectively.
- An arylthio group is preferably a “C 5-20 arylthio group”, more preferably a “C 6-12 arylthio group”, even more preferably a “C 6-10 arylthio group” and is an thio (—S—) group that is bonded to the previously defined C 5-20 aryl, C 6-12 aryl, or C 6-10 aryl group respectively.
- An alkylaryl group is preferably a “C 6-12 aryl C 1-20 alkyl group”, more preferably a preferably a “C 6-12 aryl C 1-16 alkyl group”, even more preferably a “C 6-12 aryl C 1-6 alkyl group” and is an aryl group as defined above bonded at any position to an alkyl group as defined above.
- the point of attachment of the alkylaryl group to a molecule may be via the alkyl portion and thus, preferably, the alkylaryl group is —CH 2 -Ph or —CH 2 CH 2 -Ph.
- An alkylaryl group can also be referred to as “aralkyl”.
- a silyl group is preferably a group —Si(R s ) 3 , wherein each R s can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R s is independently an unsubstituted aliphatic, alicyclic or aryl. Preferably, each R s is an alkyl group selected from methyl, ethyl or propyl.
- a silyl ether group is preferably a group OSi(R 6 ) 3 wherein each R 6 can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R 6 can be independently an unsubstituted aliphatic, alicyclic or aryl.
- each R 6 is an optionally substituted phenyl or optionally substituted alkyl group selected from methyl, ethyl, propyl or butyl (such as n-butyl or tert-butyl (tertiary butyl)).
- exemplary silyl ether groups include OSi(Me) 3 , OSi(Et) 3 , OSi(Ph) 3 , OSi(Me) 2 (tertiary butyl), OSi(tertiary butyl) 3 and OSi(Ph) 2 (tertiary butyl).
- a nitrile group (also referred to as a cyano group) is a group CN.
- An imine group is a group —CRNR, preferably a group —CHNR 7 wherein R 7 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 7 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 7 is an alkyl group selected from methyl, ethyl or propyl.
- An acetylide group contains a triple bond —C ⁇ C—R 9 , preferably wherein R 9 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- R 9 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- the triple bond can be present at any position along the alkyl chain.
- R 9 is unsubstituted aliphatic, alicyclic or aryl.
- R 9 is methyl, ethyl, propyl or phenyl.
- An amino group is preferably —NH 2 , —NHR 10 or —N(R 10 ) 2 wherein R 10 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silyl group, aryl or heteroaryl group as defined above. It will be appreciated that when the amino group is N(R 10 ) 2 , each R 10 group can be the same or different. In certain embodiments, each R 10 is independently an unsubstituted aliphatic, alicyclic, silyl or aryl. Preferably R 10 is methyl, ethyl, propyl, SiMe 3 or phenyl.
- An amido group is preferably —NR 11 C(O)— or —C(O)—NR 11 — wherein R 11 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 11 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 11 is hydrogen, methyl, ethyl, propyl or phenyl. The amido group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
- An ester group is preferably —OC(O)R 12 — or —C(O)OR 12 — wherein R 12 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 12 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 12 is hydrogen, methyl, ethyl, propyl or phenyl. The ester group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
- a sulfoxide is preferably —S(O)R 13 and a sulfonyl group is preferably —S(O) 2 R 13 wherein R 13 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 13 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 13 is hydrogen, methyl, ethyl, propyl or phenyl.
- a carboxylate group is preferably —OC(O)R 14 , wherein R 14 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 14 is unsubstituted aliphatic, alicyclic or aryl.
- R 14 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.
- R 19 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 19 is unsubstituted aliphatic, alicyclic or aryl.
- R 19 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.
- An acetamide is preferably MeC(O)N(R 15 ) 2 wherein R 15 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 15 is unsubstituted aliphatic, alicyclic or aryl. Preferably R 15 is hydrogen, methyl, ethyl, propyl or phenyl.
- a phosphinate group is preferably a group —OP(O)(R 16 ) 2 or —P(O)(OR 16 ) wherein each R 16 is independently selected from hydrogen, or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- R 16 is aliphatic, alicyclic or aryl, which are optionally substituted by aliphatic, alicyclic, aryl or C 1-6 alkoxy.
- R 16 is optionally substituted aryl or C 1-20 alkyl, more preferably phenyl optionally substituted by C 1-6 alkoxy (preferably methoxy) or unsubstituted C 1-20 alkyl (such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl).
- C 1-6 alkoxy preferably methoxy
- unsubstituted C 1-20 alkyl such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl.
- a sulfinate group is preferably —OSOR 17 wherein R 17 can be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- R 17 is unsubstituted aliphatic, alicyclic or aryl.
- R 17 is hydrogen, methyl, ethyl, propyl or phenyl.
- a carbonate group is preferably OC(O)OR 18 , wherein R 18 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R 18 is optionally substituted aliphatic, alicyclic or aryl.
- R 18 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl or adamantyl.
- R is hydrogen, an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- R is hydrogen or aliphatic, alicyclic or aryl.
- the epoxide substrate is not limited.
- the term epoxide therefore relates to any compound comprising an epoxide moiety.
- epoxides which may be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C 10 H 16 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C 11 H 22 O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides) or substituted or unsubstituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-(2-(2-(
- the epoxide moiety may be a glycidyl ether, glycidyl ester or glycidyl carbonate.
- glycidyl ethers, glycidyl esters and glycidyl carbonates include:
- the epoxide substrate may contain more than one epoxide moiety, i.e. it may be a bis-epoxide, a tris-epoxide, or a multi-epoxide containing moiety.
- epoxide moiety examples include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may lead to cross-linking in the resulting polymer.
- the skilled person will appreciate that the epoxide can be obtained from “green” or renewable resources.
- the epoxide may be obtained from a (poly)unsaturated compound, such as those deriving from a fatty acid and/or terpene, obtained using standard oxidation chemistries.
- the epoxide moiety may contain —OH moieties, or protected —OH moieties.
- the —OH moieties may be protected by any suitable protecting group.
- suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxypheny
- the epoxide preferably has a purity of at least 98%, more preferably >99%.
- an epoxide is intended to encompass one or more epoxides.
- the term “an epoxide” refers to a single epoxide, or a mixture of two or more different epoxides.
- the epoxide substrate may be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide and cyclohexene oxide.
- Suitable oxetanes include unsubstituted or substituted oxetanes (preferably substituted at the 3-position by halogen, alkyl (unsubstituted or substituted by —OH or halogen), amino, hydroxyl, aryl (e.g. phenyl), alkylaryl (e.g. benzyl)).
- Exemplary oxetanes include oxetane, 3-ethyl-3-oxetanemethanol, oxetane-3-methanol, 3-methyl-3-oxetanemethanol, 3-methyloxetane, 3-ethyloxetane, etc.
- anhydride relates to any compound comprising an anhydride moiety in a ring system (i.e. a cyclic anhydride).
- anhydrides which are useful in the present invention have the following formula:
- each R a1 , R a2 , R a3 and R a4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more of R a1 , R a2 R a3 and R a4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, or can be taken together to form a double bond.
- Each Q is independently C, O, N or S, preferably C, wherein R a3 and R a4 are either present, or absent, and can either be or , according to the valency of Q. It will be appreciated that when Q is C, and is , R a3 and R a4 (or two R a4 on adjacent carbon atoms) are absent.
- the anhydrides may be obtained from “green” or renewable resources. Preferable anhydrides are set out below.
- lactone relates to any cyclic compound comprising a-C(O)O— moiety in the ring.
- lactones which are useful in the present invention have the following formula:
- m is 1 to 20 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20), preferably 2, 4, or 5; and R L1 and R L2 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl.
- R L1 and R L2 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms.
- R L1 and R L2 on each carbon atom may be the same or different.
- R L1 and R L2 are selected from hydrogen or alkyl.
- the lactone has the following structure:
- lactide is a cyclic compound containing two ester groups.
- lactides which are useful in the present invention have the following formula:
- R L3 and R L4 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl.
- R L3 and R L4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms
- m′ 2 or more
- the R L3 and R L4 on each carbon atom may be the same or different or one or more R L3 and R L4 on adjacent carbon atoms can be absent, thereby forming a double or triple bond.
- the compound has two moieties represented by (—CR L3 R L4 ) m′ , both moieties will be identical.
- m′ is 1, R L4 is H, and R L3 is H, hydroxyl or a C 1-6 alkyl, preferably methyl.
- the stereochemistry of the moiety represented by (—CR L3 R L4 ) m′ can either be the same (for example RR-lactide or SS-lactide), or different (for example, meso-lactide).
- the lactide may be a racemic mixture, or may be an optically pure isomer.
- the lactide has the following formula:
- lactone and/or lactide used herein encompasses a lactone, a lactide and a combination of a lactone and a lactide.
- lactone and/or lactide means a lactone or a lactide.
- Preferred optional substituents of the groups R a1 , R, R 2 , R a3 , R a4 , R L1 , R L2 , R L3 and R L4 include halogen, nitro, hydroxyl, unsubstituted aliphatic, unsubstituted heteroaliphatic unsubstituted aryl, unsubstituted heteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, and carboxylate.
- M 1 and M 2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Ni(III)-X, Mn(III)-X, Fe(III)-X, Ca(II), Ge(II), AI(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X) 2 or Ti(IV)-(X) 2 ;
- R 1 and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted al
- each of the occurrences of the groups R 1 and R 2 may be the same or different.
- R, and R 2 are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio.
- each occurrence of R 2 is the same.
- each occurrence of R 2 is the same, and is hydrogen.
- R 2 is hydrogen and R 1 is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C 1-6 alkyl (e.g.
- haloalkyl alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, tertiary butyl, isopropyl, methyl, methyloxy, hydrogen, nitro, dimethylsulfoxide, trialkylsilyl for example triethylsilyl, silyl ether, halogen or phenyl.
- R is tertiary butyl and R 2 is hydrogen.
- each occurrence of R can be the same or different, and R 1 and R 2 can be the same or different.
- each occurrence of R is the same.
- each occurrence of R 1 is the same, and each occurrence of R 2 is the same, and R, is different to R 2 .
- R 1 is the same, and R 1 is different to R 2 .
- R 3A and R 3B can be a disubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or heteroalkynyl group which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or may be a disubstituted aryl or cycloalkyl group which acts as a bridging group between two nitrogen centres in the catalyst of formula (I).
- R 3A or R 38 is an alkylene group, such as dimethylpropylene
- the R 3A or R 3B group has the structure —CH 2 —C(CH 3 ) 2 —CH 2 —.
- alkyl, aryl, cycloalkyl etc groups set out above therefore also relate respectively to the alkylene, arylene, cycloalkylene etc groups set out for R 3A or R 3B , and may be optionally substituted.
- exemplary options for R 3A and R 3B include ethylene, 2,2-dimethylpropylene, 2,2-fluoropropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene, 2,2-fluoropropylene, propylene, cyclohexylene or phenylene.
- R 3A or R 3B is cyclohexylene, it can be the racemic, RR- or SS-forms.
- R 3A or R 3B are selected from ethylene, propylene, a substituted propylene, such as 2,2-di(alkyl)propylene, phenylene, or cyclohexylene, more preferably R 3A or R 3B are 2,2-di(methyl)propylene.
- R 3A is different to R 3B . It will also be appreciated that when at least one occurrence of E 3 , E 4 , E 5 and E 6 is different to a remaining occurrence of E 3 , E 4 , E 5 and E 6 , R 3A can be the same as, or different to R 3B .
- R 3A when R 3A is different to R 3B , R 3A can be optionally substituted alkylene (for example, optionally substituted propylene, e.g. 2,2-dimethylpropylene, 2,2-fluoropropylene or propylene), or optionally substituted cycloalkylene (such as cyclohexylene), and R 3B can be optionally substituted arylene (such as phenylene or biphenylene), or optionally substituted alkylene (for example, optionally substituted propylene, e.g. 2,2-dimethylpropylene, 2,2-fluoropropylene, ethylene or propylene).
- alkylene for example, optionally substituted propylene, e.g. 2,2-dimethylpropylene, 2,2-fluoropropylene, ethylene or propylene.
- R 3A is 2,2-dimethylpropylene
- R 3B is phenylene
- R 3A is a disubstituted cycloalkylene which acts as a bridging group between two nitrogen centres in the catalyst of formula (I), and R 3B is 2,2-dimethylpropylene.
- R 3A is 2,2-dimethylpropylene
- R 3B is propylene or ethylene
- R 3A is propylene
- R 3B is 2,2-dimethylpropylene
- E 3 , E 4 , E 5 and E 6 are each independently selected from N, NR 4 , O or S.
- the skilled person will understand that when any of E 3 , E 4 , E 5 or E 6 are N, is . It will also be understood that when any of E 3 , E 4 , E 5 or E 6 are NR 4 , O or S, is .
- R 3A and R 3B are the same, at least one occurrence of E 3 , E 4 , E 5 or E 6 is different to a remaining occurrence of E 3 , E 4 , E 5 and E 6 .
- each E 3 , E 4 , E 5 and E 6 is NR 4 , but at least one of the R 4 groups is different from a remaining R 4 groups.
- E 3 , E 4 , E 5 or E 6 is different to a remaining occurrence of E 3 , E 4 , E 5 and E 6 , and at least one occurrence of E 3 , E 4 , E 5 or E 6 is NR 4 , at least one of the remaining E 3 , E 4 , E 5 and E 6 groups is selected from N, O or S.
- each E 3 , E 4 , E 5 and E 6 may be the same or different.
- each E 3 , E 4 , E 5 and E 6 are the same.
- each of E 3 , E 4 , E 5 and E 6 are the same, preferably each of E 3 , E 4 , E 5 and E 6 are NR 4 , more preferably each of E 3 , E 4 , E 5 and E 6 are NH.
- E 3 and E 5 may be the same, E 3 and E 4 may be the same, E 4 and E 6 may be the same, E 4 and E 5 may be the same, E 5 and E 6 may be the same, and/or E 3 and E 6 may be the same. It is preferred that E 3 and E 5 are the same, and E 4 and E 6 are the same, and E 3 and E 5 are different to E 4 and E 6 , preferably E 3 and E 5 are S or O and E 4 and E 6 are N or NR 4 (such as NH).
- E 3 and E 4 can be the same, and E 5 and E 6 can be the same, and E 3 and E 4 are different to E 5 and E 6 , preferably E 3 and E 4 are S and E 5 and E 6 are N or NR 4 (such as NH).
- each R 4 is independently selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl.
- at least one R 4 is hydrogen.
- At least one R 4 is may be different to a remaining R 4 group/s.
- each R 4 is the same, it is preferably selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl.
- R 4 examples include hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tertiary butyl, benzyl, phenyl, -alkyl-C(O)—OR 19 (as defined hereinabove for example methyl propanoate), alkyl nitrile of the formula -alkyl-C ⁇ N or alkyl ketone/aldehyde of the formula alkyl-C(O)—R 19 .
- a further exemplary option is methylpyridine.
- each E 3 , E 4 , E 5 and E 6 is NR 4 , and one of the R 4 groups is different, preferably E 4 is different. More preferably one of the R 4 groups is selected from an optionally substituted alkyl or heteroalkyl. Still more preferably one of the R 4 groups is selected from methyl, ethyl, propyl, butyl or -alkyl-C(O)—OR 19 as defined hereinabove, for example methyl propanoate. Preferably the remaining R 4 groups are hydrogen.
- each E 3 , E 4 , E 5 and E 6 is NR 4 , and two of the R 4 groups are different, preferably E 3 and E 5 are different or E 4 and E 5 are different. More preferably two of the R 4 groups are selected from an optionally substituted alkyl or heteroalkyl. Still more preferably two of the R 4 groups are selected from methyl, ethyl, propyl, butyl or -alkyl-C(O)—OR 19 as defined hereinabove, for example methyl propanoate. Preferably the remaining R 4 groups are hydrogen.
- E 3 , E 4 , E 5 and E 6 are NR 4 , and two of E 3 , E 4 , E 5 and E 6 are N. More preferably two of E 3 , E 4 , E 5 and E 6 are NH and two of E 3 , E 4 , E 5 and E 6 are N. Still more preferably, E 4 and E 6 are NH and E 3 and E 5 are N, or E 3 and E 5 are NH and E 4 and E 6 are N.
- E 3 , E 4 , E 5 and E 6 are S, and two of E 3 , E 4 , E 5 and E 6 are NR 4 . More preferably two of E 3 , E 4 , E 5 and E 6 are S, and two of E 3 , E 4 , E 5 and E 6 are NH. Still more preferably E 3 and E 5 are S, and, E 4 and E 6 are NH.
- each R 5 is independently selected from hydrogen, and optionally substituted aliphatic or aryl. More preferably, each R 5 is independently selected from hydrogen, and optionally substituted alkyl or aryl. Even more preferably, each R 5 is the same, and is selected from hydrogen, and optionally substituted alkyl or aryl. Exemplary R 5 groups include hydrogen, methyl, ethyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. Even more preferably, each R 5 is hydrogen.
- both occurrences of E 1 are C and both occurrences of E 2 are the same, and selected from O, S or NH. Even more preferably, both occurrences of E, are C and both occurrences of E 2 are O.
- Each X is independently selected from OC(O)R x , OSO 2 R x , OS(O)R x , OSO(R x ) 2 , S(O)R x , OR x , phosphinate, halide, nitro, hydroxyl, carbonate, amino, amido and optionally substituted aliphatic, heteroaliphatic (for example silyl), alicyclic, heteroalicyclic, aryl or heteroaryl.
- each X is independently OC(O)R x , OSO 2 R x , OS(O)R x , OSO(R x ) 2 , S(O)R x , OR x , halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (e.g. branched alkyl), heteroalkyl, (for example silyl), aryl or heteroaryl.
- each X is independently OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO 2 R x .
- Preferred optional substituents for when X is aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl include halogen, hydroxyl, nitro, cyano, amino, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
- Each X may be the same or different and preferably each X is the same.
- R x is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl.
- R x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl.
- Preferred optional substitutents for R x include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl (e.g. optionally substituted alkyl, aryl, or heteroaryl).
- Exemplary options for X include acetate, trifluoroacetyl, octanoate, carbonate, 2-ethylhexanoate, cyclohexylbutyrate, dimethyl sulfonyl, ethyl, methyl, methyloxy, isopropyloxy, tertiary butyloxy, halogen (such as chloride, bromide, iodide, fluoride), diisopropylamide or bis(trimethylsilyl)amide phenoxy, n-butyloxy, salicylate, dioctyl phosphinate, diphenyl phosphinate etc.
- X is acetate.
- M 1 and M 2 are independently selected from Zn(II), Cr(III), Cr(II), Co(III), Co(II), Cu(II), Ni(II), Ni(III), Mn(III), Mn(II), Mg(II), Fe(II), Fe(III), Ca(II), Ge(II), Ti(II), AI(III), Ti(III), V(II), V(III), Ge(IV) or Ti(IV).
- M 1 and M 2 are independently selected from Zn(II), Cr(III), Co(II), Mn(II), Mg(II), Ni(II), Ni(III), Fe(II) and Fe(III), even more preferably, M 1 and M 2 are independently selected from Zn(II), Cr(III), Co(II), Mn(II), Ni(II), Ni(III), Mg(II), Fe(II), and Fe(III), and even more preferably, M 1 and M 2 are independently selected from Zn(II), Ni(II), Ni(III) and Mg(II). Still more preferably M 1 and M 2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M 1 and M 2 are the same. Most preferably M 1 and M 2 are the same and are Ni(II) or Mg(II).
- G When G is not absent, it is a group which is capable of donating a lone pair of electrons (i.e. a Lewis base). G can be a nitrogen-containing Lewis base. Each G may be neutral or negatively charged. If G is negatively charged, then one or more positive counterions will be required to balance out the charge of the complex. Suitable positive counterions include group 1 metal ions (Na + , K + , etc), group 2 metal ions (Mg 2+ , Ca 2+ , etc), imidazolium ions, a positively charged optionally substituted heteroaryl, heteroaliphatic or heteroalicyclic group, ammonium ions (i.e. N(R 12 ) 4 + ), iminium ions (i.e.
- R 12 ) 2 C ⁇ N(R 12 ) 2 + such as bis(triphenylphosphine)iminium ions) or phosphonium ions (P(R 12 ) 4 + ), wherein each R 12 is independently selected from hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl.
- exemplary counterions include [H-B] + wherein B is selected from triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
- G is preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate and water. More preferably, G is independently selected from water, an alcohol (e.g methanol), a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole (for example, N-methyl imidazole), pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc), an ether (dimethyl ether, diethylether, cyclic ethers, etc), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc), an amine, an alkyl amine
- G can be independently selected from optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide, an amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate.
- G may be a halide; hydroxide; hydride; water; a heteroaryl, heteroalicyclic or carboxylate group which are optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile.
- G is independently selected from halide; water; a heteroaryl optionally substituted by alkyl (e.g. methyl, ethyl etc), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile. It will be understood that one or both instances of G may be negatively charged (for example, halide).
- G is an optionally substituted heteroaryl.
- G groups include chloride, bromide, pyridine, methylimidazole (for example N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).
- the G group when a G group is present, the G group may be associated with a single M metal centre as shown in formula (I), or the G group may be associated with both metal centres and form a bridge between the two metal centres, as shown below in formula (Ia):
- R 1 , R 2 , R 3A , R 3B , R 4 , E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , R 5 , M, G and X are as defined for formula (I). It will also be appreciated that X may form a bridge between the two metal centres.
- the catalysts of the first aspect may be associated with solvent molecules such as water, or alcohol (e.g. methanol or ethanol). It will be appreciated that the solvent molecules may be present in a ratio of less than 1:1 relative to the molecules of catalyst of the first aspect (i.e. 0.2:1, 0.25:1, 0.5:1), in a ratio of 1:1, relative to the molecules of catalyst of the first aspect, or in a ratio of greater than 1:1, relative to the molecules of catalyst of the first aspect.
- solvent molecules such as water, or alcohol (e.g. methanol or ethanol). It will be appreciated that the solvent molecules may be present in a ratio of less than 1:1 relative to the molecules of catalyst of the first aspect (i.e. 0.2:1, 0.25:1, 0.5:1), in a ratio of 1:1, relative to the molecules of catalyst of the first aspect, or in a ratio of greater than 1:1, relative to the molecules of catalyst of the first aspect.
- the catalysts of the first aspect may form aggregates.
- the catalyst of the first aspect may be a dimer, a trimer, a tetramer, a pentamer, or higher aggregate.
- each occurrence of R 2 and R 5 are H, E, is C and E 2 is O, S or NH (preferably E 2 is O).
- both occurrences of R are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio;
- R 2 is hydrogen;
- R 3A and R 3B are the same or different, and are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene;
- E 3 to E 6 are the same or different and are selected from NR 4 , S, N or O;
- R 4 is hydrogen, an optionally substituted alkyl or heteroalkyl;
- each X is the same, and is selected from OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, ary
- both occurrences of R are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio;
- R 2 is hydrogen;
- R 3A is a substituted or unsubstituted cycloalkylene or alkylene and R 3B is a substituted or unsubstituted alkylene or arylene;
- each occurrence of E 3 to E 6 is NR 4 ;
- R 4 is hydrogen;
- each X is the same, and is selected from OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO 2 R x , R x is alkyl, alkenyl, al
- both occurrences of R are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio;
- R 2 is hydrogen;
- R 3A and R 3B are the same and are substituted or unsubstituted alkylene;
- each of E 3 , E 4 , E 5 and E 6 is NR 4 wherein one of the R 4 groups is different from a remaining R 4 group and is selected from an optionally substituted alkyl or heteroalkyl and the remaining R 4 group/s are hydrogen;
- each X is the same, and is selected from OC(O)R x , OR x , halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO 2 R
- both occurrences of R are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio;
- R 2 is hydrogen;
- R 3A and R 3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene;
- E 3 to E 6 are selected from N, NR 4 , S or O;
- R 4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
- each X is the same, and is selected from OC(O)R x , OR x , or OSO 2 R x , R x is alkyl, alkenyl, alkynyl, hetero
- both occurrences of R are the same, and are selected from an optionally substituted alkyl;
- R 2 is hydrogen;
- R 3A and R 3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and substituted or unsubstituted arylene;
- each occurrence of E 3 to E 6 is NR 4 ;
- R 4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
- each X is the same, and is selected from OC(O)R x , OR x , or OSO 2 R x ,
- R x is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl;
- M 1 and M 2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M 1 and M 2 are independently selected from Ni(II),
- both occurrences of R are the same, and are tertiary butyl;
- R 2 is hydrogen;
- R 3A and R 3B are selected from butylene, benzylene, ethylene, propylene, 2,2-dimethylpropylene;
- each occurrence of E 3 to E 6 is NR 4 ;
- R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl, or -alkyl-C(O)—OR 19 as defined hereinabove, preferably methyl propanoate;
- each X is the same, and is OAc;
- M 1 and M 2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II).
- M 1 and M 2 are independently selected from Ni(II), Ni(III), or Mg(II).
- M 1 and M 2 are the same, and are selected from Ni(II) or Mg(II); wherein:
- Exemplary catalysts of the first aspect are as follows:
- R 1 and R 2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
- R 3A and R 3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkeny
- Y is selected from hydrogen, lithium, sodium, potassium, rubidium, caesium, or francium. More preferably Y is either hydrogen or lithium.
- both occurrences of R 1 are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio;
- R 2 is hydrogen;
- R 3A and R 3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene;
- E 3 to E 6 are N, NR 4 , S or O;
- R 4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
- both occurrences of R are the same, and are selected from an optionally substituted alkyl;
- R 2 is hydrogen;
- R 3A and R 3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and substituted or unsubstituted arylene;
- each occurrence of E 3 to E 6 is NR 4 ;
- R 4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
- both occurrences of R 1 are the same and are tertiary butyl;
- R 2 is hydrogen;
- R 3A and R 3B are selected from tertiary butylene, benzylene, ethylene, propylene, 2,2-dimethylpropylene;
- each occurrence of E 3 to E 6 is NR 4 ;
- R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl, or -alkyl-C(O)—OR 19 as defined hereinabove, preferably methyl propanoate;
- the ligand of formula (II) is:
- R 1 is tertiary butyl
- R 2 is hydrogen
- R 3 is 2,2-dimethylpropylene
- R 4 is selected from methyl, ethyl, propyl, or butyl
- the ligand of formula (II) is:
- R 3 is selected from 2,2-dimethylpropylene, propylene, or ethylene; or the ligand of formula (II) is:
- R is methyl or hydrogen; or the ligand of formula (II) is:
- R 1 is tertiary butyl
- R 2 is hydrogen
- R 3 is 2,2-dimethylpropylene
- R 4 is methyl, ethyl, propyl, or butyl.
- R 4 is methyl.
- the ligand of formula (II) comprises at least one N-substituent, and may be selected from:
- R 1 is tertiary butyl
- R 2 is hydrogen
- R 3 is 2,2-dimethylpropylene
- R 4 is selected from methyl, ethyl, propyl, or butyl; or:
- R 1 is tertiary butyl
- R 2 is hydrogen
- R 3 is 2,2-dimethylpropylene
- R 4 is methyl, ethyl, propyl, or butyl.
- R 4 is methyl.
- the invention extends to methods of preparation of ligands, complexes and catalysts according to the second aspect and first aspect respectively or as otherwise defined herein.
- the symmetrical ligand comprises formula (IV):
- R, and R 2 are as defined above in relation to the second aspect, and R 3 is defined as R 3A or R 3B in relation to the second aspect.
- the symmetrical ligand of formula (IVa) is:
- the optionally substituted alkylene is selected from an optionally substituted methylene or ethylene.
- step (a) comprises reacting the symmetrical ligand with a protecting reagent comprising an optionally substituted alkyl group.
- the protecting reagent is an aldehyde, more preferably an aldehyde selected from formaldehyde or benzaldehyde.
- step (a) comprises protecting two or more of the amino groups of the coordination sphere of the symmetrical ligand by forming bridging groups between the adjacent amino or phenolic groups.
- the bridging groups are the optionally substituted alkylene, and are selected from an optionally substituted methylene or ethylene.
- the product of step (a) comprises a pair of optionally substituted alkylene bridges between adjacent nitrogen atoms of the coordination sphere.
- step (a) is conducted in the presence of a solvent which may be any suitable solvent for the protecting reagent, for example methanol or THF.
- a solvent which may be any suitable solvent for the protecting reagent, for example methanol or THF.
- step (a) comprises contact with the protecting reagent for sufficient time to complete or substantially complete the reaction. Suitable contact times are between 30 minutes and 15 hours, more preferably for between 2 hours and 8 hours, most preferably for around 6 hours.
- step (a) is conducted at a suitable temperature.
- suitable temperatures may be in the range ⁇ 25 to 75° C., for example 0 to 50° C., typically 15-30° C. such as room temperature (around 21° C.).
- step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with an N-substituting agent by for example hydroamination with an alkene (such as an acrylate or acrylonitrile) or by using an alkylating agent.
- an alkene such as an acrylate or acrylonitrile
- the substituent is an R 4 group, as defined hereinabove.
- one or more of the amino groups is substituted to form an NR 4 group.
- step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent. More preferably step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent by reacting the product of step (a) with an N-substituting agent.
- the N-substituting agent is an alkylating agent or an alkene such as an activated alkene for example an alkyl acrylate, alkyl methacrylate, alkyl vinyl ketone or acrylonitrile, more preferably the alkylating agent comprises the formula R 4 X.
- X is a halide, tosylate or triflate, more preferably X is iodine.
- R 4 X is selected from iodomethane, iodoethane, 1-iodopropane or 1-iodobutane.
- step (b) is conducted in the presence of a solvent which may be any suitable solvent for N-substituting agent, for example methanol, dichloromethane, or THF.
- a solvent which may be any suitable solvent for N-substituting agent, for example methanol, dichloromethane, or THF.
- step (b) comprises contact with the N-substituting agent for sufficient time to complete or substantially complete the reaction. Suitable contact times are between 12 and 22 hours, more preferably between 14 and 18 hours, most preferably for around 16 hours.
- step (b) is conducted at a suitable temperature.
- suitable temperatures may be between 20° C. to 90° C., more preferably between 23° C. to 80° C., most preferably at around 25-50° C.
- the method may further comprise step (c) hydrolysing the optionally substituted alkylene bridging groups between the adjacent amino groups.
- step (c) is performed by reacting the product of step (b) with an acid, more preferably with HCl and subsequently isolating the material
- the method may further comprise upstream steps of formation of the symmetrical ligand having a tetraaminophenol coordination sphere.
- the method further comprises upstream steps of formation of the symmetrical ligand comprising formula (IV):
- R 1 and R 2 are as defined above in relation to the second aspect, and R 3 is defined as R 3A or R 3B in relation to the second aspect.
- the method further comprises upstream steps of formation of the symmetrical ligand comprising formula (IVa):
- the upstream steps comprise (1) formation of a symmetrical ligand having a tetraiminophenol coordination sphere, and (2) reduction of the imine groups to amine groups.
- upstream step (1) comprises formation of a symmetrical ligand having a tetraiminophenol coordination sphere from a compound of formula (III):
- R 1 and R 2 are as defined hereinabove.
- More preferably upstream step (1) comprises reacting a compound of formula (III) with an amine of formula H 2 N—R 3 —NH 2 , wherein R 3 is as defined hereinabove.
- Upstream step (1) may be conducted in the presence of a suitable solvent, an acid and an electrolyte.
- the solvent may be any suitable solvent for the reactants of upstream step (1), for example methanol or THF. More preferably the solvent is methanol.
- upstream step (2) comprises reacting the product of upstream step (1) with a reducing agent.
- Suitable reducing agents are known to those skilled in the art, for example sodium borohydride or hydrogen.
- upstream step (2) is conducted in the presence of a solvent, which may be any suitable solvent for the reactants of upstream step (2), for example methanol or THF. More preferably the solvent is methanol.
- a solvent which may be any suitable solvent for the reactants of upstream step (2), for example methanol or THF. More preferably the solvent is methanol.
- the process comprises the following steps:
- the process comprises the following steps:
- the asymmetrical ligand produced is that according to the second aspect.
- the ligand according to the second aspect is that of formula (IIa):
- R 1 is tertiary butyl
- R 2 is hydrogen
- R 3 is 2,2-dimethylpropylene
- R 4 is selected from methyl, ethyl, propyl, or butyl.
- R1 is tertiary butyl; R 2 is hydrogen; R 3 is 2,2-dimethylpropylene.
- the catalysts of the first aspect are capable of polymerising (i) carbon dioxide and an epoxide, (ii) an epoxide and an anhydride, and (iii) a lactide and/or a lactone. Therefore, in a fifth aspect of the invention there is provided a process for the reaction of carbon dioxide with an epoxide, an anhydride with an epoxide, or a lactide and/or a lactone in the presence of a catalyst according to the first aspect.
- the process of the fifth aspect may be carried out in the presence of a chain transfer agent.
- Suitable chain transfer agents include the chain transfer agents, for example as defined by formula (II), in WO 2013/034750, the entire contents of which are hereby incorporated by reference.
- the chain transfer agent may be water, or may comprise at least one amine (—NHR), alcohol (—OH) or thiol (—SH) moiety.
- chain transfer agents useful in the second aspect include water, mono-alcohols (i.e. alcohols with one OH group, for example, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol), diols (for example, 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, catechol and cyclohexenediol), triols (glycerol, benzenetriol, 1,2,4-butanetriol, tris(methylalcohol)propane,
- diamines for example 1,4-butanediamine
- diamines for example 1,4-butanediamine
- diamine terminated polyethers diamine terminated polyesters
- mono-carboxylic acids for example, 3,5-di-tert-butylbenzoic acid
- dicarboxylic acids for example, maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid
- tricarboxylic acids for example, citric acid, 1,3,5-benzenetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid, preferably citric acid
- mono-thiols dithoils, trithiols, and
- the chain transfer agent is selected from cyclohexene diol, 1,2,4-butanetriol, tris(methylalcohol)propane, tri(methylalcohol)propane, tri(methylalcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and di-ethylene glycol, propylene glycol, tris(methylalcohol)nitropropane, tris(methylalcohol)ethane, 2,2-bis(methylalcohol)-1,3-propanediol, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.
- the process of the fifth aspect may be carried out in the presence of a solvent.
- solvents useful in the third aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, tetrahydrofuran (THF), etc.
- the epoxide may be any compound comprising an epoxide moiety.
- the epoxide may be purified (for example by distillation, such as over calcium hydride) prior to reaction with carbon dioxide or the anhydride.
- the epoxide may be distilled prior to being added to the reaction mixture comprising the catalyst.
- the process of the fifth aspect of the invention may be carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 20 atmospheres, more preferably at 1 or 10 atmospheres.
- the catalysts used in the process of the second aspect allow the reaction to be carried out at low pressures.
- the process of the fifth aspect of the invention may be carried out at a temperature of about 0° C. to about 250° C., preferably from about 40° C. to about 160° C., even more preferably from about 50° C. to about 120° C.
- the duration of the process may be up to 168 hours, such as from about 1 minute to about 24 hours, for example from about 5 minutes to about 12 hours, e.g. from about 1 to about 6 hours.
- the process temperature for copolymerisations of carbon dioxide and an epoxide, may be used to control the product composition.
- the temperature of the process of the fifth aspect which involves reacting carbon dioxide and an epoxide is increased, the selectivity of the catalyst towards the formation of cyclic carbonate is also increased.
- the catalysts and processes may operate at temperatures up to 250° C.
- the process of the fifth aspect of the invention may be carried out at low catalytic loading.
- the catalytic loading for the process is preferably in the range of 1:1,000-300,000 catalyst:epoxide, more preferably in the region of 1:10,000-100,000 catalyst:epoxide, even more preferably in the region of 1:50,000-100,000 catalyst:epoxide.
- the catalytic loading for the process is preferably in the range of 1:1,000-300,000 catalyst:total monomer content, more preferably in the region of 1:10,000-100,000 catalyst:total monomer content, even more preferably in the region of 1:50,000-100,000 catalyst:total monomer content.
- the ratios above are molar ratios.
- the catalysts of the first aspect and in particular catalysts wherein both M 1 and M 2 are selected from Ni(II) and Mg(II), have high activity and selectivity for producing polycarbonates by reacting carbon dioxide and an epoxide, optionally in the presence of a chain transfer agent, and preferably at temperatures between about 40° C. to about 160° C.
- the reaction times for the process of the second aspect can be less than 12 hours, and preferably from about 2 to about 6 hours.
- the process of the fifth aspect can be carried out in a batch reactor or a continuous reactor.
- the sixth aspect of the invention provides a product of the process of the fifth aspect of the invention. All preferred features of the fifth aspect of the invention apply to the sixth aspect of the invention mutatis mutandis.
- polymer chains which are terminated at substantially all ends with hydroxyl groups i.e. polycarbonate polyols or polyester polyols.
- substantially it is meant that at least 90% of the resultant polymer chains, preferably at least 95% of the resultant polymer chains, and even more preferably at least 98%, and even more preferably at least about 99% of the resultant polymer chains are terminated at all ends in hydroxyl groups.
- the process of the second aspect In order for at least 90% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 4 equivalents of chain transfer agent, relative to the amount of catalyst. In order for at least 95% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 10 equivalents of chain transfer agent, relative to the amount of catalyst. In order for at least 98% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the fifth aspect to be carried out in the presence of at least about 20 equivalents of chain transfer agent, relative to the amount of catalyst. Thus, polyols obtained by the process of the fifth aspect are considered to form part of the sixth aspect of the invention.
- the chain transfer agent referred to in the fifth aspect may be used to control the molecular weight (M n ) of the polymer products of the sixth aspect.
- the molecular weight (M n ) of the polymer products of the sixth aspect is greater than about 200 g/mol.
- the molecular weight (M n ) of the polymer products of the sixth aspect may be from about 200 g/mol to about 200,000 g/mol.
- the molecular weight of the polymers produced by the fifth aspect can be measured by Gel Permeation Chromatography (GPC) using, for example, a GPC-60 manufactured by Polymer Labs, using THF as the eluent at a flow rate of 1 ml/min on Mixed B columns, manufactured by Polymer Labs. Narrow molecular weight polystyrene standards can be used to calibrate the instrument.
- GPC Gel Permeation Chromatography
- polycarbonate polyols and polyester polyols having a M n of from about 200 g/mol to about 20,000 g/mol, preferably less than about 10,000 g/mol by adding a chain transfer agent to the process of the fifth aspect.
- polymers having a M n of greater than about 20,000 g/mol from the process of the fifth aspect.
- the polymer having a M n of greater than about 20,000 g/mol is a polycarbonate or a polyester, even more preferably a polycarbonate.
- the polymer having a M n of greater than about 20,000 g/mol is a polycarbonate and is produced carrying out the process of the fifth aspect without adding a chain transfer agent (CTA).
- CTA chain transfer agent
- the polymers produced by the fifth aspect may be produced to have a polydispersity index (PDI) of less than about 2, more preferably less than about 1.5, and even more preferably less than about 1.2. Furthermore, it is possible to control the molecular weight distribution so as to produce multi-modal or broad molecular weight distribution polymers by addition of one or more chain transfer agent(s).
- PDI polydispersity index
- the polymers produced by the process of the fifth aspect are useful building blocks in the preparation of various copolymeric materials.
- the polymers produced by the process of the fifth aspect may undergo further reaction, for example to produce polymeric products such as polyureas or polyamines. These processes and reactions are well known to the skilled person (for example, refer to WO2013/034750).
- the polycarbonate or polyester polyols produced by the process of the fifth aspect may be used in various applications and products which conventionally use polyols, including adhesives (such as hot melt adhesives and structural adhesives), a binder (such as forest product binders, foundry core binders and rubber crumb binders), coatings (such as powder coatings, transport, e.g. automotive or marine coatings, fast cure coatings, self-healing coatings, top coats and primers, varnishes, and coatings for marine applications, e.g.
- adhesives such as hot melt adhesives and structural adhesives
- a binder such as forest product binders, foundry core binders and rubber crumb binders
- coatings such as powder coatings, transport, e.g. automotive or marine coatings, fast cure coatings, self-healing coatings, top coats and primers, varnishes, and coatings for marine applications, e.g.
- elastomers such as cast elastomers, fibres/spandex elastomers, footwear elastomers, RIM/RRIM elastomers, synthetic leather elastomers, technical microcellular elastomers and TPU elastomers
- flexible foams such as viscoelastic foams
- rigid foams such as rigid and flexible panels, moulded rigid foams, aerosol gap filling foam, spray foams, refrigeration foams, pour-in-place foams, and foam slabs
- sealants such as glazing sealants for commercial, industrial and transport (e.g. automotive) applications, and construction sealants).
- the polyamines and polyureas can be processed using methods standard techniques known in the art, such as foaming.
- polycarbonate and polyester polyols produced by the process of the fifth aspect may be mixed with other polyols prior to further use or reaction.
- the polycarbonates and in particular, polycarbonates having a M n of greater than about 20,000 g/mol (e.g. produced without adding chain transfer agent to the process of the fifth aspect) may have a number of beneficial properties including high strength, high toughness, high gloss, high transparency, low haze, high gas (e.g. oxygen and carbon dioxide) or water barrier properties, flame resistance, UV resistance, high durability, rigidity and stiffness, compatibility with plasticizers, broad dimensional stability temperature, biodegradability and biocompatibility, and modulus of elasticity and yield strength comparable to LDPE.
- these polymers may be used in various applications and products, such as electronic components, construction materials, data storage products, automotive and aircraft products, security components, medical applications, mobile phones, packaging (including bottles), optical applications (such as safety glass, windscreens, etc).
- Ligands H 2 L 1-4 were prepared by the following method:
- a tetraaminophenol ligand may be formed by the following process (steps 1 and 2):
- the yellow reaction mixture was allowed to cool to room temperature, and left stirring for 24 hours, after which a bright orange precipitate was filtered and washed with cold ( ⁇ 78° C.) methanol (1.85 g, 95%).
- the product was suspended in methanol (180 mL).
- the suspension was cooled to 0° C. and NaBH 4 (2.65 g, 69.9 mmol) was added slowly.
- NaBH 4 was added, the red-orange suspension turned to a clear solution. Water was added slowly, and the solution turned cloudy. Once precipitate started to form, the mixture was left overnight and H 2 L 11 was filtered off as a white solid (1.21 g, 88%).
- R 4 X (iodomethane, iodoethane, 1-iodopropane or 1-iodobutane, 104 mmol) was added to a stirred solution of this white powder (10.4 mmol) in anhydrous THF (120 mL) at 25° C. until the reaction was deemed to be complete. A white precipitate formed in the reaction mixture and was collected by suction filtration. The filter cake was washed with THF. The resultant white powder was transferred to a round bottom flask and dried under high vacuum for several hours. This was dissolved (7.3 mmol) in MeOH and concentrated HCl (aq) (1:1) and placed in a heating block set to 75° C.
- H 2 L 3 1 H NMR (400 MHz, CDCl 3 ) ⁇ 7.11 (m, 2H), 6.84 (m, 2H), 3.76 (s, 2H), 3.52 (s, 2H), 3.50 (m, 4H), 2.54 (s, 2H), 2.48 (m, 2H), 2.38 (s, 2H), 2.32 (s, 2H), 2.30 (s, 2H), 2.20 (s, 2H), 1.59 (m, 2H), 1.34 (s, 18H), 0.93 (s, 6H), 0.91 (s, 6H).
- the asymmetric ligand H 2 L 6 was prepared using the following method:
- H 2 L 6 1 H NMR (400 MHz, CDCl 3 ) ⁇ 7.14-7.05 (m, 2H), 7.05-6.96 (m, 2H), 5.37-5.27 (s, 4H), 3.89-3.81 (s, 4H), 3.70-3.63 (s, 4H), 2.67-2.62 (s, 4H), 2.55-2.49 (s, 2H), 1.35 (s, 18H), 0.99-0.90 (s, 6H).
- the asymmetric ligand H 2 L 7 was prepared using the following method:
- N,N′-dimethyl-2,2-dimethyl-1,3-propanediamine was prepared by reaction of 2,2-dimethyl-1,3-propanediamine (166 mmol) with ethyl formate (80 mL) followed by reduction with LiAlH 4 (10 g) in diethyl ether (250 mL).
- the asymmetric ligands Li 2 L imine 8-10 and H 2 L 9-10 were prepared using the following method:
- the asymmetric ligands H 2 L 12-13 were prepared using the following methods:
- IR cm ⁇ 1 , neat: 3301, 2955, 2907, 2869, 1741, 1480, 1216, 1100.
- the ligands H 2 L 14-15 were prepared by the following method:
- H 2 L 14 1 H NMR (CDCl 3 , 400.1 MHz): ⁇ 7.16 (m, 2H), 6.89 (m, 2H), 3.93 (m, 2H), 3.71 (m, 6H), 2.56 (s, 4H), 2.50 (s, 4H), 1.26 (s, 18H), 0.98 (d, 12H)
- 1,3-propanedithiol (0.56 mL, 5.5 mmol) was dissolved in EtOH (50 mL) in a fumecupboard. A solution of C (3 g, 11.1 mmol) in EtOH (50 mL) was added dropwise over 15 minutes and the mixture stirred overnight. The solvent was removed under vacuum and distilled water (50 mL) was added. The product was extracted with DCM (2 ⁇ 30 mL), dried over NaSO 4 and the solvent removed under vacuum.
- the yellow precipitate (0.25 g, 0.44 mmol) was dissolved in dry MeOH (50 mL) before NaBH 4 (0.2 g, 4.4 mmol) was added in portions. The solution was stirred for 2 hours after which the solvent was removed under vacuum. Water (50 mL) was added to the crude and the pH brought up to 6-7 by adding AcOH dropwise. The product (H 2 L 15 ) was extracted with DCM (2 ⁇ 25 mL), dried over NaSO4 and the solvent removed under vacuum.
- Example 10 Polymerisation of CO 2 and CHO at 100° C. and 0.01 Mmol of [LM 2 (OAc) 2 ]
- Example 11 Polymerisation of CO 2 and CHO at 130° C. and High Pressure with [LM 2 (OAc) 2 ]
- Example 12 Polymerisation of CO 2 and PO with [LM 2 (OAc) 2 ]
- Example 13 Polymerisation of CO 2 and PO with [L 1 Ni 2 (OAc) 2 ] in the Presence of a Starter—PPG-425
- Example 14 Polymerisation of CO 2 and PO with [L 1 Ni 2 (OAc) 2 ] in the Presence of a Starter—1,6-hexanediol
- Example 15 Polymerisation of CO 2 and PO with [L 1 Ni 2 (OAc) 2 ] in the Presence of a Solvent—toluene
- Example 16 Polymerisation of CO 2 and PO with [L 1 Ni 2 (OAc) 2 ] in the Presence of a Solvent—n-butyl acetate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
- The present invention relates to the field of polymerisation catalysts, and systems comprising said catalysts for polymerising carbon dioxide and an epoxide, a lactide and/or lactone, and/or an epoxide and an anhydride.
- Environmental and economic concerns associated with depleting oil resources have triggered a growing interest in the chemical conversion of carbon dioxide (CO2), so as to enable its use as a renewable carbon source. CO2 is, despite its low reactivity, a highly attractive carbon feedstock, as it is inexpensive, virtually non-toxic, abundantly available in high purity and non-hazardous. Therefore, CO2 could be a promising substitute for substances such as carbon monoxide, phosgene or other petrochemical feedstocks in many processes. One of the developing applications of CO2 is the copolymerization with epoxides to yield aliphatic polycarbonates. The development of effective catalysts to make such a process profitable is the subject of continuous research.
- In WO2009/130470, the contents of which are incorporated herein by reference in their entirety, the copolymerisation of an epoxide with CO2 using a catalyst of a class represented by formula (I) was described:
- WO2013/034750, the contents of which are incorporated herein by reference in their entirety, discloses the copolymerisation of an epoxide with CO2 in the presence of a chain transfer agent using a catalyst of a class represented by formula (I):
- Various compounds according to formula (I) above were tested for their ability to catalyse the reaction between different epoxides and carbon dioxide.
- In each of these tested catalysts, both occurrences of R3 were the same and all occurrence of R4 were the same (referred to hereinafter as symmetric catalysts).
- Among the epoxides employed in the copolymerization reactions of the prior art, cyclohexene oxide (CHO) received special interest, as the product, poly(cyclohexene carbonate) (PCHC) shows a high glass transition temperature and reasonable tensile strength. Ethylene oxide, propylene oxide and butylene oxide have also received interest as they produce polymers (polyalkylene carbonates, such as PPC) with elastomeric properties which are useful in many applications e.g. films.
- The inventors have now surprisingly found that the asymmetric catalysts referred to herein represent a novel and inventive means of catalysing the polymerisation of carbon dioxide with various monomers to produce useful polymer products with good activity and selectivity.
- According to a first aspect of the present invention, there is provided a catalyst of formula (I):
- wherein:
M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Ni(II), Mn(II), Mg(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Ni(III)-X, Mn(III)-X, Fe(III)-X, Ca(II), Ge(II), AI(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2 or Ti(IV)-(X)2;
R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
R3A and R3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
E1 is C, E2 is O, S or NH or E, is N and E2 is O;
E3, E4, E5 and E6 are each independently selected from N, NR4, O and S, wherein when any of E3, E4, E5 or E6 are N, is , and wherein when any of E3, E4, E5 or E6 are NR4, O or S, is ; R4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
X is independently selected from OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, S(O)Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and
G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base;
and wherein: -
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- According to a second aspect of the present invention, there is provided a ligand of formula (II):
- wherein:
R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
R3A and R3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
E1 is C, E2 is OY, S or NH or E, is N and E2 is O;
Y is hydrogen or an alkali metal;
E3, E4, E5 and E6 are each independently selected from N, NR4, O and S, wherein when any of E3, E4, E5 or E6 are N, is , and wherein when any of E3, E4, E5 or E6 are NR4, O or S, is ; R4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl; -
- and wherein:
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- In a third aspect of the present invention, the invention extends to methods of preparation of ligands, complexes and catalysts according to the second aspect and first aspect respectively or as otherwise defined herein.
- In a fourth aspect of the present invention, there is provided a process of asymmetric N-substitution of a symmetrical ligand having a tetraaminophenol coordination sphere, the process comprising the following steps:
-
- a) protecting the amino groups of the coordination sphere of the symmetrical ligand with an optionally substituted alkylene;
- b) asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent.
- In a fifth aspect of the invention, there is provided a process for the reaction of (i) carbon dioxide with an epoxide, (ii) an anhydride and an epoxide, and/or (iii) a lactide and/or a lactone in the presence of a catalyst according to the first aspect, optionally in the presence of a chain transfer agent.
- The sixth aspect of the invention provides a product of the process of the fifth aspect of the invention.
- For the purpose of the present invention, an aliphatic group is a hydrocarbon moiety that may be straight chain or branched and may be completely saturated, or contain one or more units of unsaturation, but which is not aromatic. The term “unsaturated” means a moiety that has one or more double and/or triple bonds. The term “aliphatic” is therefore intended to encompass alkyl, alkenyl or alkynyl groups, and combinations thereof. An aliphatic group is preferably a C1-20 aliphatic group, that is, an aliphatic group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an aliphatic group is a C1-15aliphatic, more preferably a C1-12aliphatic, more preferably a C1-10aliphatic, even more preferably a C1-8aliphatic, such as a C1-6aliphatic group.
- An alkyl group is preferably a “C1-20 alkyl group”, that is an alkyl group that is a straight or branched chain with 1 to 20 carbons. The alkyl group therefore has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alkyl group is a C1-15alkyl, preferably a C1-12alkyl, more preferably a C1-10alkyl, even more preferably a C1-8alkyl, even more preferably a C1-6alkyl group. Specifically, examples of “C1-20 alkyl group” include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like.
- Alkenyl and alkynyl groups are preferably “C2-20alkenyl” and “C2-20alkynyl”, more preferably “C2-15alkenyl” and “C2-15alkynyl”, even more preferably “C2-12alkenyl” and “C2-12alkynyl”, even more preferably “C2-10alkenyl” and “C2-10alkynyl”, even more preferably “C2-8alkenyl” and “C2-8alkynyl”, most preferably “C2-6alkenyl” and “C2-6alkynyl” groups, respectively. Alkene and alkyne should be understood accordingly.
- A heteroaliphatic group is an aliphatic group as described above, which additionally contains one or more heteroatoms. Heteroaliphatic groups therefore preferably contain from 2 to 21 atoms, preferably from 2 to 16 atoms, more preferably from 2 to 13 atoms, more preferably from 2 to 11 atoms, more preferably from 2 to 9 atoms, even more preferably from 2 to 7 atoms, wherein at least one atom is a carbon atom. Particularly preferred heteroatoms are selected from O, S, N, P and Si. When heteroaliphatic groups have two or more heteroatoms, the heteroatoms may be the same or different.
- An alicyclic group is a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic (including fused, bridging and spiro-fused) ring system which has from 3 to 20 carbon atoms, that is an alicyclic group with 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. Preferably, an alicyclic group has from 3 to 15, more preferably from 3 to 12, even more preferably from 3 to 10, even more preferably from 3 to 8 carbon atoms, even more preferably from 3 to 6 carbons atoms. The term “alicyclic” encompasses cycloalkyl, cycloalkenyl and cycloalkynyl groups. It will be appreciated that the alicyclic group may comprise an alicyclic ring bearing one or more linking or non-linking alkyl substituents, such as —CH2-cyclohexyl. Specifically, examples of the C3-20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl and cyclooctyl.
- A heteroalicyclic group is an alicyclic group as defined above which has, in addition to carbon atoms, one or more ring heteroatoms, which are preferably selected from O, S, N, P and Si. Heteroalicyclic groups preferably contain from one to four heteroatoms, which may be the same or different. Heterocyclic groups preferably contain from 5 to 20 atoms, more preferably from 5 to 14 atoms, even more preferably from 5 to 12 atoms.
- An aryl group is a monocyclic or polycyclic ring system having from 5 to 20 carbon atoms. An aryl group is preferably a “C6-12 aryl group” and is an aryl group constituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like. Specifically, examples of “C6-10 aryl group” include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group.
- A heteroaryl group is an aryl group having, in addition to carbon atoms, from one to four ring heteroatoms which are preferably selected from O, S, N, P and Si. A heteroaryl group preferably has from 5 to 20, more preferably from 5 to 14 ring atoms. Specifically, examples of a heteroaryl group include pyridine, imidazole, methylimidazole and dimethylaminopyridine.
- Examples of alicyclic, heteroalicyclic, aryl and heteroaryl groups include but are not limited to cyclohexyl, phenyl, acridine, benzimidazole, benzofuran, benzothiophene, benzoxazole, benzothiazole, carbazole, cinnoline, dioxin, dioxane, dioxolane, dithiane, dithiazine, dithiazole, dithiolane, furan, imidazole, imidazoline, imidazolidine, indole, indoline, indolizine, indazole, isoindole, isoquinoline, isoxazole, isothiazole, morpholine, napthyridine, oxazole, oxadiazole, oxathiazole, oxathiazolidine, oxazine, oxadiazine, phenazine, phenothiazine, phenoxazine, phthalazine, piperazine, piperidine, pteridine, purine, pyran, pyrazine, pyrazole, pyrazoline, pyrazolidine, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, quinoline, quinoxaline, quinazoline, quinolizine, tetrahydrofuran, tetrazine, tetrazole, thiophene, thiadiazine, thiadiazole, thiatriazole, thiazine, thiazole, thiomorpholine, thianaphthalene, thiopyran, triazine, triazole, and trithiane.
- The term “halide” or “halogen” are used interchangeably and, as used herein mean a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom, a bromine atom or a chlorine atom, and more preferably a fluorine atom.
- A haloalkyl group is preferably a “C1-20 haloalkyl group”, more preferably a “C1-15 haloalkyl group”, more preferably a “C1-12 haloalkyl group”, more preferably a “C1-10 haloalkyl group”, even more preferably a “C1-8 haloalkyl group”, even more preferably a “C1-6 haloalkyl group” and is a C1-20 alkyl, a C1-15 alkyl, a C1-12 alkyl, a C1-10 alkyl, a C1-8 alkyl, or a C1-6 alkyl group, respectively, as described above substituted with at least one halogen atom, preferably 1, 2 or 3 halogen atom(s). Specifically, examples of “C1-20 haloalkyl group” include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.
- An alkoxy group is preferably a “C1-20 alkoxy group”, more preferably a “C1-15 alkoxy group”, more preferably a “C1-12 alkoxy group”, more preferably a “C1-10 alkoxy group”, even more preferably a “C1-8 alkoxy group”, even more preferably a “C1-6 alkoxy group” and is an oxy group that is bonded to the previously defined C1-20 alkyl, C1-15 alkyl, C1-12 alkyl, C1-10 alkyl, C1-8 alkyl, or C1-6 alkyl group respectively. Specifically, examples of “C1-20 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso-hexyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-eicosyloxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2-dimethylpropoxy group, 2-methylbutoxy group, 1-ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2-ethylbutoxy group, 2-methylpentyloxy group, 3-methylpentyloxy group and the like.
- An aryloxy group is preferably a “C5-20 aryloxy group”, more preferably a “C6-12 aryloxy group”, even more preferably a “C6-10 aryloxy group” and is an oxy group that is bonded to the previously defined C5-20 aryl, C6-12 aryl, or C6-10 aryl group respectively.
- An alkylthio group is preferably a “C1-20 alkylthio group”, more preferably a “C1-15 alkylthio group”, more preferably a “C1-12 alkylthio group”, more preferably a “C1-10 alkylthio group”, even more preferably a “C1-8 alkylthio group”, even more preferably a “C1-6 alkylthio group” and is a thio (—S—) group that is bonded to the previously defined C1-20 alkyl, C1-15 alkyl, C1-12 alkyl, C1-10 alkyl, C1-8 alkyl, or C1-6 alkyl group respectively.
- An arylthio group is preferably a “C5-20 arylthio group”, more preferably a “C6-12 arylthio group”, even more preferably a “C6-10 arylthio group” and is an thio (—S—) group that is bonded to the previously defined C5-20 aryl, C6-12 aryl, or C6-10 aryl group respectively.
- An alkylaryl group is preferably a “C6-12 aryl C1-20 alkyl group”, more preferably a preferably a “C6-12 aryl C1-16 alkyl group”, even more preferably a “C6-12 aryl C1-6 alkyl group” and is an aryl group as defined above bonded at any position to an alkyl group as defined above. The point of attachment of the alkylaryl group to a molecule may be via the alkyl portion and thus, preferably, the alkylaryl group is —CH2-Ph or —CH2CH2-Ph. An alkylaryl group can also be referred to as “aralkyl”.
- A silyl group is preferably a group —Si(Rs)3, wherein each Rs can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each Rs is independently an unsubstituted aliphatic, alicyclic or aryl. Preferably, each Rs is an alkyl group selected from methyl, ethyl or propyl.
- A silyl ether group is preferably a group OSi(R6)3 wherein each R6 can be independently an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, each R6 can be independently an unsubstituted aliphatic, alicyclic or aryl.
- Preferably, each R6 is an optionally substituted phenyl or optionally substituted alkyl group selected from methyl, ethyl, propyl or butyl (such as n-butyl or tert-butyl (tertiary butyl)). Exemplary silyl ether groups include OSi(Me)3, OSi(Et)3, OSi(Ph)3, OSi(Me)2(tertiary butyl), OSi(tertiary butyl)3 and OSi(Ph)2(tertiary butyl).
- A nitrile group (also referred to as a cyano group) is a group CN.
- An imine group is a group —CRNR, preferably a group —CHNR7 wherein R7 is an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R7 is unsubstituted aliphatic, alicyclic or aryl. Preferably R7 is an alkyl group selected from methyl, ethyl or propyl.
- An acetylide group contains a triple bond —C≡C—R9, preferably wherein R9 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. For the purposes of the invention when R9 is alkyl, the triple bond can be present at any position along the alkyl chain. In certain embodiments, R9 is unsubstituted aliphatic, alicyclic or aryl. Preferably R9 is methyl, ethyl, propyl or phenyl.
- An amino group is preferably —NH2, —NHR10 or —N(R10)2 wherein R10 can be an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, a silyl group, aryl or heteroaryl group as defined above. It will be appreciated that when the amino group is N(R10)2, each R10 group can be the same or different. In certain embodiments, each R10 is independently an unsubstituted aliphatic, alicyclic, silyl or aryl. Preferably R10 is methyl, ethyl, propyl, SiMe3 or phenyl.
- An amido group is preferably —NR11C(O)— or —C(O)—NR11— wherein R11 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R11 is unsubstituted aliphatic, alicyclic or aryl. Preferably R11 is hydrogen, methyl, ethyl, propyl or phenyl. The amido group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
- An ester group is preferably —OC(O)R12— or —C(O)OR12— wherein R12 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R12 is unsubstituted aliphatic, alicyclic or aryl. Preferably R12 is hydrogen, methyl, ethyl, propyl or phenyl. The ester group may be terminated by hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group.
- A sulfoxide is preferably —S(O)R13 and a sulfonyl group is preferably —S(O)2R13 wherein R13 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R13 is unsubstituted aliphatic, alicyclic or aryl. Preferably R13 is hydrogen, methyl, ethyl, propyl or phenyl.
- A carboxylate group is preferably —OC(O)R14, wherein R14 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R14 is unsubstituted aliphatic, alicyclic or aryl. Preferably R14 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.
- In an -alkylC(O)OR19 or -alkylC(O)R19 group, R19 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R19 is unsubstituted aliphatic, alicyclic or aryl. Preferably R19 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl or adamantyl.
- An acetamide is preferably MeC(O)N(R15)2 wherein R15 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R15 is unsubstituted aliphatic, alicyclic or aryl. Preferably R15 is hydrogen, methyl, ethyl, propyl or phenyl.
- A phosphinate group is preferably a group —OP(O)(R16)2 or —P(O)(OR16) wherein each R16 is independently selected from hydrogen, or an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R16 is aliphatic, alicyclic or aryl, which are optionally substituted by aliphatic, alicyclic, aryl or C1-6alkoxy. Preferably R16 is optionally substituted aryl or C1-20 alkyl, more preferably phenyl optionally substituted by C1-6alkoxy (preferably methoxy) or unsubstituted C1-20alkyl (such as hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl).
- A sulfinate group is preferably —OSOR17 wherein R17 can be hydrogen, an aliphatic, heteroaliphatic, haloaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above.
- In certain embodiments, R17 is unsubstituted aliphatic, alicyclic or aryl. Preferably R17 is hydrogen, methyl, ethyl, propyl or phenyl.
- A carbonate group is preferably OC(O)OR18, wherein R18 can be hydrogen, an aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. In certain embodiments, R18 is optionally substituted aliphatic, alicyclic or aryl. Preferably R18 is hydrogen, methyl, ethyl, propyl, butyl (for example n-butyl, isobutyl or tert-butyl), phenyl, pentafluorophenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, trifluoromethyl, cyclohexyl, benzyl or adamantyl.
- It will be appreciated that where any of the above groups are present in a Lewis base G, one or more additional R groups may be present, as appropriate, to complete the valency. For example, in the context of an amino group, an additional R group may be present to give RNHR10, wherein R is hydrogen, an optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl group as defined above. Preferably, R is hydrogen or aliphatic, alicyclic or aryl.
- Any of the aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, haloalkyl, alkoxy, aryloxy, alkylthio, arylthio, alkylaryl, silyl, silyl ether, ester, sulfoxide, sulfonyl, carboxylate, carbonate, imine, acetylide, amino, phosphinate, sulfonate or amido groups wherever mentioned in the definitions above, may optionally be substituted by halogen, hydroxy, nitro, carboxylate, carbonate, alkoxy, aryloxy, alkylthio, arylthio, heteroaryloxy, alkylaryl, amino, amido, imine, nitrile, silyl, silyl ether, ester, sulfoxide, sulfonyl, acetylide, phosphinate, sulfonate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl groups (for example, optionally substituted by halogen, hydroxy, nitro, carbonate, alkoxy, aryloxy, alkylthio, arylthio, amino, imine, nitrile, silyl, sulfoxide, sulfonyl, phosphinate, sulfonate or acetylide).
- It will be appreciated that although in formula (I), the groups X and G are illustrated as being associated with a single M1 or M2 metal centre, one or more X and G groups may form a bridge between the M1 and M2 metal centres.
- For the purposes of the present invention, the epoxide substrate is not limited. The term epoxide therefore relates to any compound comprising an epoxide moiety. Examples of epoxides which may be used in the present invention include, but are not limited to, cyclohexene oxide, styrene oxide, propylene oxide, butylene oxide, substituted cyclohexene oxides (such as limonene oxide, C10H16O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, C11H22O), alkylene oxides (such as ethylene oxide and substituted ethylene oxides) or substituted or unsubstituted oxiranes (such as oxirane, epichlorohydrin, 2-(2-methoxyethoxy)methyl oxirane (MEMO), 2-(2-(2-methoxyethoxy)ethoxy)methyl oxirane (ME2MO), 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)methyl oxirane (ME3MO), 1,2-epoxybutane, glycidyl ethers), vinyl-cyclohexene oxide, 3-phenyl-1,2-epoxypropane, 1,2- and 2,3-epoxybutane, isobutylene oxide, cyclopentene oxide, 2,3-epoxy-1,2,3,4-tetrahydronaphthalene, indene oxide, and functionalized 3,5-dioxaepoxides. Examples of functionalized 3,5-dioxaepoxides include:
- The epoxide moiety may be a glycidyl ether, glycidyl ester or glycidyl carbonate. Examples of glycidyl ethers, glycidyl esters and glycidyl carbonates include:
- The epoxide substrate may contain more than one epoxide moiety, i.e. it may be a bis-epoxide, a tris-epoxide, or a multi-epoxide containing moiety. Examples of compounds including more than one epoxide moiety include bisphenol A diglycidyl ether and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. It will be understood that reactions carried out in the presence of one or more compounds having more than one epoxide moiety may lead to cross-linking in the resulting polymer.
- The skilled person will appreciate that the epoxide can be obtained from “green” or renewable resources. The epoxide may be obtained from a (poly)unsaturated compound, such as those deriving from a fatty acid and/or terpene, obtained using standard oxidation chemistries.
- The epoxide moiety may contain —OH moieties, or protected —OH moieties. The —OH moieties may be protected by any suitable protecting group. Suitable protecting groups include methyl or other alkyl groups, benzyl, allyl, tert-butyl, tetrahydropyranyl (THP), methoxymethyl (MOM), acetyl (C(O)alkyl), benzolyl (C(O)Ph), dimethoxytrityl (DMT), methoxyethoxymethyl (MEM), p-methoxybenzyl (PMB), trityl, silyl (such as trimethylsilyl (TMS), t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS)), (4-methoxyphenyl)diphenylmethyl (MMT), tetrahydrofuranyl (THF), and tetrahydropyranyl (THP).
- The epoxide preferably has a purity of at least 98%, more preferably >99%.
- It will be understood that the term “an epoxide” is intended to encompass one or more epoxides. In other words, the term “an epoxide” refers to a single epoxide, or a mixture of two or more different epoxides. For example, the epoxide substrate may be a mixture of ethylene oxide and propylene oxide, a mixture of cyclohexene oxide and propylene oxide, a mixture of ethylene oxide and cyclohexene oxide, or a mixture of ethylene oxide, propylene oxide and cyclohexene oxide.
- The skilled person will also understand that substituted and unsubstituted oxetanes can be used in place of, and in addition to, the epoxides of the second aspect of the invention. Suitable oxetanes include unsubstituted or substituted oxetanes (preferably substituted at the 3-position by halogen, alkyl (unsubstituted or substituted by —OH or halogen), amino, hydroxyl, aryl (e.g. phenyl), alkylaryl (e.g. benzyl)). Exemplary oxetanes include oxetane, 3-ethyl-3-oxetanemethanol, oxetane-3-methanol, 3-methyl-3-oxetanemethanol, 3-methyloxetane, 3-ethyloxetane, etc.
- The term anhydride relates to any compound comprising an anhydride moiety in a ring system (i.e. a cyclic anhydride). Preferably, the anhydrides which are useful in the present invention have the following formula:
- Wherein m″ is 1, 2, 3, 4, 5, or 6 (preferably 1 or 2), each Ra1, Ra2, Ra3 and Ra4 is independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl; or two or more of Ra1, Ra2Ra3 and Ra4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, or can be taken together to form a double bond. Each Q is independently C, O, N or S, preferably C, wherein Ra3 and Ra4 are either present, or absent, and can either be or , according to the valency of Q. It will be appreciated that when Q is C, and is , Ra3 and Ra4 (or two Ra4 on adjacent carbon atoms) are absent. The skilled person will appreciate that the anhydrides may be obtained from “green” or renewable resources. Preferable anhydrides are set out below.
- The term lactone relates to any cyclic compound comprising a-C(O)O— moiety in the ring. Preferably, the lactones which are useful in the present invention have the following formula:
- Wherein m is 1 to 20 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20), preferably 2, 4, or 5; and RL1 and RL2 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl. Two or more of RL1 and RL2 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms. When m is 2 or more, the RL1 and RL2 on each carbon atom may be the same or different. Preferably RL1 and RL2 are selected from hydrogen or alkyl. Preferably, the lactone has the following structure:
- The term lactide is a cyclic compound containing two ester groups. Preferably, the lactides which are useful in the present invention have the following formula:
- Wherein m′ is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, (preferably 1 or 2, more preferably, 1) and RL3 and RL4 are independently selected from hydrogen, halogen, hydroxyl, nitro, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, carboxylate or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylaryl or alkylheteroaryl. Two or more of RL3 and RL4 can be taken together to form a saturated, partially saturated or unsaturated 3 to 12 membered, optionally substituted ring system, optionally containing one or more heteroatoms, When m′ is 2 or more, the RL3 and RL4 on each carbon atom may be the same or different or one or more RL3 and RL4 on adjacent carbon atoms can be absent, thereby forming a double or triple bond. It will be appreciated that while the compound has two moieties represented by (—CRL3RL4)m′, both moieties will be identical. Preferably, m′ is 1, RL4 is H, and RL3 is H, hydroxyl or a C1-6alkyl, preferably methyl. The stereochemistry of the moiety represented by (—CRL3RL4)m′, can either be the same (for example RR-lactide or SS-lactide), or different (for example, meso-lactide). The lactide may be a racemic mixture, or may be an optically pure isomer. Preferably, the lactide has the following formula:
- The term “lactone and/or lactide” used herein encompasses a lactone, a lactide and a combination of a lactone and a lactide. Preferably, the term “lactone and/or lactide” means a lactone or a lactide.
- Preferred optional substituents of the groups Ra1, R, R2, Ra3, Ra4, RL1, RL2, RL3 and RL4 include halogen, nitro, hydroxyl, unsubstituted aliphatic, unsubstituted heteroaliphatic unsubstituted aryl, unsubstituted heteroaryl, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, and carboxylate.
- In the first aspect of the invention, there is provided a catalyst of formula (I):
- wherein:
M1 and M2 are independently selected from Zn(II), Cr(II), Co(II), Cu(II), Mn(II), Mg(II), Ni(II), Fe(II), Ti(II), V(II), Cr(III)-X, Co(III)-X, Ni(III)-X, Mn(III)-X, Fe(III)-X, Ca(II), Ge(II), AI(III)-X, Ti(III)-X, V(III)-X, Ge(IV)-(X)2 or Ti(IV)-(X)2;
R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
R3A and R3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
E1 is C, E2 is O, S or NH or E1 is N and E2 is O;
E3, E4, E5 and E6 are each independently selected from N, NR4, O and S, wherein when any of E3, E4, E5 or E6 are N, is , and wherein when any of E3, E4, E5 or E6 are NR4, O or S, is ; R is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
X is independently selected from OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, S(O)Rx, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amino, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl; and
G is absent or independently selected from a neutral or anionic donor ligand which is a Lewis base;
and wherein: -
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- Preferably, each of the occurrences of the groups R1 and R2 may be the same or different.
- Preferably R, and R2 are independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio. Preferably each occurrence of R2 is the same. Preferably, each occurrence of R2 is the same, and is hydrogen.
- Even more preferably, R2 is hydrogen and R1 is independently selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl ether and optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, such as hydrogen, C1-6alkyl (e.g. haloalkyl), alkoxy, aryl, halide, nitro, sulfonyl, silyl and alkylthio, for example, tertiary butyl, isopropyl, methyl, methyloxy, hydrogen, nitro, dimethylsulfoxide, trialkylsilyl for example triethylsilyl, silyl ether, halogen or phenyl. Most preferably R, is tertiary butyl and R2 is hydrogen.
- Each occurrence of R, can be the same or different, and R1 and R2 can be the same or different. Preferably each occurrence of R, is the same. Preferably, each occurrence of R1 is the same, and each occurrence of R2 is the same, and R, is different to R2. The skilled person will appreciate that when each occurrence of R1 is different, this adds to the asymmetry of the catalyst.
- It will be appreciated that the groups R3A and R3B can be a disubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl or heteroalkynyl group which may optionally be interrupted by an aryl, heteroaryl, alicyclic or heteroalicyclic group, or may be a disubstituted aryl or cycloalkyl group which acts as a bridging group between two nitrogen centres in the catalyst of formula (I). Thus, where R3A or R38 is an alkylene group, such as dimethylpropylene, the R3A or R3B group has the structure —CH2—C(CH3)2—CH2—. The definitions of the alkyl, aryl, cycloalkyl etc groups set out above therefore also relate respectively to the alkylene, arylene, cycloalkylene etc groups set out for R3A or R3B, and may be optionally substituted. Exemplary options for R3A and R3B include ethylene, 2,2-dimethylpropylene, 2,2-fluoropropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene, 2,2-fluoropropylene, propylene, cyclohexylene or phenylene. When R3A or R3B is cyclohexylene, it can be the racemic, RR- or SS-forms. Preferably R3A or R3B are selected from ethylene, propylene, a substituted propylene, such as 2,2-di(alkyl)propylene, phenylene, or cyclohexylene, more preferably R3A or R3B are 2,2-di(methyl)propylene.
- When each occurrence of E3, E4, E5 and E6 is the same, R3A is different to R3B. It will also be appreciated that when at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6, R3A can be the same as, or different to R3B.
- Preferably, when R3A is different to R3B, R3A can be optionally substituted alkylene (for example, optionally substituted propylene, e.g. 2,2-dimethylpropylene, 2,2-fluoropropylene or propylene), or optionally substituted cycloalkylene (such as cyclohexylene), and R3B can be optionally substituted arylene (such as phenylene or biphenylene), or optionally substituted alkylene (for example, optionally substituted propylene, e.g. 2,2-dimethylpropylene, 2,2-fluoropropylene, ethylene or propylene).
- In a first preferred embodiment, R3A is 2,2-dimethylpropylene, and R3B is phenylene.
- In a second preferred embodiment, R3A is a disubstituted cycloalkylene which acts as a bridging group between two nitrogen centres in the catalyst of formula (I), and R3B is 2,2-dimethylpropylene.
- In a third preferred embodiment, R3A is 2,2-dimethylpropylene, and R3B is propylene or ethylene.
- In a fourth preferred embodiment, R3A is propylene, and R3B is 2,2-dimethylpropylene.
-
- When R3A and R3B are the same, at least one occurrence of E3, E4, E5 or E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- Preferably when at least one occurrence of E3, E4, E5 or E6 is different to a remaining occurrence of E3, E4, E5 and E6, each E3, E4, E5 and E6 is NR4, but at least one of the R4 groups is different from a remaining R4 groups.
- Alternatively, when at least one occurrence of E3, E4, E5 or E6 is different to a remaining occurrence of E3, E4, E5 and E6, and at least one occurrence of E3, E4, E5 or E6 is NR4, at least one of the remaining E3, E4, E5 and E6 groups is selected from N, O or S.
- It will be understood that when R3A is different to R3B, each E3, E4, E5 and E6 may be the same or different.
- Preferably, when R3A is different to R3B, each E3, E4, E5 and E6 are the same. When each of E3, E4, E5 and E6 are the same, preferably each of E3, E4, E5 and E6 are NR4, more preferably each of E3, E4, E5 and E6 are NH.
- It will be understood that E3 and E5 may be the same, E3 and E4 may be the same, E4 and E6 may be the same, E4 and E5 may be the same, E5 and E6 may be the same, and/or E3 and E6 may be the same. It is preferred that E3 and E5 are the same, and E4 and E6 are the same, and E3 and E5 are different to E4 and E6, preferably E3 and E5 are S or O and E4 and E6 are N or NR4 (such as NH). Alternatively, E3 and E4 can be the same, and E5 and E6 can be the same, and E3 and E4 are different to E5 and E6, preferably E3 and E4 are S and E5 and E6 are N or NR4 (such as NH).
- Preferably each R4 is independently selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. Preferably, at least one R4 is hydrogen. At least one R4 is may be different to a remaining R4 group/s. When each R4 is the same, it is preferably selected from hydrogen, and an optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl or heteroaryl. Exemplary options for R4 include hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, tertiary butyl, benzyl, phenyl, -alkyl-C(O)—OR19 (as defined hereinabove for example methyl propanoate), alkyl nitrile of the formula -alkyl-C≡N or alkyl ketone/aldehyde of the formula alkyl-C(O)—R19. A further exemplary option is methylpyridine.
- Preferably each E3, E4, E5 and E6 is NR4, and one of the R4 groups is different, preferably E4 is different. More preferably one of the R4 groups is selected from an optionally substituted alkyl or heteroalkyl. Still more preferably one of the R4 groups is selected from methyl, ethyl, propyl, butyl or -alkyl-C(O)—OR19 as defined hereinabove, for example methyl propanoate. Preferably the remaining R4 groups are hydrogen.
- Preferably each E3, E4, E5 and E6 is NR4, and two of the R4 groups are different, preferably E3 and E5 are different or E4 and E5 are different. More preferably two of the R4 groups are selected from an optionally substituted alkyl or heteroalkyl. Still more preferably two of the R4 groups are selected from methyl, ethyl, propyl, butyl or -alkyl-C(O)—OR19 as defined hereinabove, for example methyl propanoate. Preferably the remaining R4 groups are hydrogen.
- Preferably two of E3, E4, E5 and E6 are NR4, and two of E3, E4, E5 and E6 are N. More preferably two of E3, E4, E5 and E6 are NH and two of E3, E4, E5 and E6 are N. Still more preferably, E4 and E6 are NH and E3 and E5 are N, or E3 and E5 are NH and E4 and E6 are N.
- Preferably two of E3, E4, E5 and E6 are S, and two of E3, E4, E5 and E6 are NR4. More preferably two of E3, E4, E5 and E6 are S, and two of E3, E4, E5 and E6 are NH. Still more preferably E3 and E5 are S, and, E4 and E6 are NH.
- Preferably each R5 is independently selected from hydrogen, and optionally substituted aliphatic or aryl. More preferably, each R5 is independently selected from hydrogen, and optionally substituted alkyl or aryl. Even more preferably, each R5 is the same, and is selected from hydrogen, and optionally substituted alkyl or aryl. Exemplary R5 groups include hydrogen, methyl, ethyl, phenyl and trifluoromethyl, preferably hydrogen, methyl or trifluoromethyl. Even more preferably, each R5 is hydrogen.
- Preferably both occurrences of E1 are C and both occurrences of E2 are the same, and selected from O, S or NH. Even more preferably, both occurrences of E, are C and both occurrences of E2 are O.
- Each X is independently selected from OC(O)Rx, OSO2Rx, OS(O)Rx, OSO(Rx)2, S(O)Rx, ORx, phosphinate, halide, nitro, hydroxyl, carbonate, amino, amido and optionally substituted aliphatic, heteroaliphatic (for example silyl), alicyclic, heteroalicyclic, aryl or heteroaryl. Preferably each X is independently OC(O)Rx, OSO2Rx, OS(O)Rx, OSO(Rx)2, S(O)Rx, ORx, halide, nitrate, hydroxyl, carbonate, amino, nitro, amido, alkyl (e.g. branched alkyl), heteroalkyl, (for example silyl), aryl or heteroaryl. In particularly preferred embodiments, each X is independently OC(O)Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx. Preferred optional substituents for when X is aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl include halogen, hydroxyl, nitro, cyano, amino, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Each X may be the same or different and preferably each X is the same.
- Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl. Preferably, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl. Preferred optional substitutents for Rx include halogen, hydroxyl, cyano, nitro, amino, alkoxy, alkylthio, or substituted or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl (e.g. optionally substituted alkyl, aryl, or heteroaryl).
- Exemplary options for X include acetate, trifluoroacetyl, octanoate, carbonate, 2-ethylhexanoate, cyclohexylbutyrate, dimethyl sulfonyl, ethyl, methyl, methyloxy, isopropyloxy, tertiary butyloxy, halogen (such as chloride, bromide, iodide, fluoride), diisopropylamide or bis(trimethylsilyl)amide phenoxy, n-butyloxy, salicylate, dioctyl phosphinate, diphenyl phosphinate etc. Preferably X is acetate.
- M1 and M2 are independently selected from Zn(II), Cr(III), Cr(II), Co(III), Co(II), Cu(II), Ni(II), Ni(III), Mn(III), Mn(II), Mg(II), Fe(II), Fe(III), Ca(II), Ge(II), Ti(II), AI(III), Ti(III), V(II), V(III), Ge(IV) or Ti(IV). Preferably, M1 and M2 are independently selected from Zn(II), Cr(III), Co(II), Mn(II), Mg(II), Ni(II), Ni(III), Fe(II) and Fe(III), even more preferably, M1 and M2 are independently selected from Zn(II), Cr(III), Co(II), Mn(II), Ni(II), Ni(III), Mg(II), Fe(II), and Fe(III), and even more preferably, M1 and M2 are independently selected from Zn(II), Ni(II), Ni(III) and Mg(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same. Most preferably M1 and M2 are the same and are Ni(II) or Mg(II).
- It will be appreciated that when M1 or M2 is Cr(III), Co(III), Mn(III), Ni(III) or Fe(III), the catalyst of formula (I) will contain an additional X group co-ordinated to the metal centre, wherein X is as defined above. It will also be appreciated that when M1 or M2 is Ge(IV) or Ti(IV), the catalyst of formula (III) will contain two additional X group co-ordinated to the metal centre, wherein X is as defined above. It will be understood that when M1 or M2 is Ge(IV) or Ti(IV), both G may be absent.
- When G is not absent, it is a group which is capable of donating a lone pair of electrons (i.e. a Lewis base). G can be a nitrogen-containing Lewis base. Each G may be neutral or negatively charged. If G is negatively charged, then one or more positive counterions will be required to balance out the charge of the complex. Suitable positive counterions include group 1 metal ions (Na+, K+, etc), group 2 metal ions (Mg2+, Ca2+, etc), imidazolium ions, a positively charged optionally substituted heteroaryl, heteroaliphatic or heteroalicyclic group, ammonium ions (i.e. N(R12)4 +), iminium ions (i.e. (R12)2C═N(R12)2 +, such as bis(triphenylphosphine)iminium ions) or phosphonium ions (P(R12)4 +), wherein each R12 is independently selected from hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl. Exemplary counterions include [H-B]+ wherein B is selected from triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
- G is preferably independently selected from an optionally substituted heteroaliphatic group, an optionally substituted heteroalicyclic group, an optionally substituted heteroaryl group, a halide, hydroxide, hydride, a carboxylate and water. More preferably, G is independently selected from water, an alcohol (e.g methanol), a substituted or unsubstituted heteroaryl (imidazole, methyl imidazole (for example, N-methyl imidazole), pyridine, 4-dimethylaminopyridine, pyrrole, pyrazole, etc), an ether (dimethyl ether, diethylether, cyclic ethers, etc), a thioether, carbene, a phosphine, a phosphine oxide, a substituted or unsubstituted heteroalicyclic (morpholine, piperidine, tetrahydrofuran, tetrahydrothiophene, etc), an amine, an alkyl amine trimethylamine, triethylamine, etc), acetonitrile, an ester (ethyl acetate, etc), an acetamide (dimethylacetamide, etc), a sulfoxide (dimethylsulfoxide, etc), a carboxylate, a hydroxide, hydride, a halide, a nitrate, a sulfonate, etc. It will be appreciated that one or both instances of G can be independently selected from optionally substituted heteroaryl, optionally substituted heteroaliphatic, optionally substituted heteroalicyclic, halide, hydroxide, hydride, an ether, a thioether, carbene, a phosphine, a phosphine oxide, an amine, an alkyl amine, acetonitrile, an ester, an acetamide, a sulfoxide, a carboxylate, a nitrate or a sulfonate. G may be a halide; hydroxide; hydride; water; a heteroaryl, heteroalicyclic or carboxylate group which are optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile. Preferably, G is independently selected from halide; water; a heteroaryl optionally substituted by alkyl (e.g. methyl, ethyl etc), alkenyl, alkynyl, alkoxy (preferably methoxy), halogen, hydroxyl, nitro or nitrile. It will be understood that one or both instances of G may be negatively charged (for example, halide). Preferably, one or both instances of G is an optionally substituted heteroaryl. Exemplary G groups include chloride, bromide, pyridine, methylimidazole (for example N-methyl imidazole) and dimethylaminopyridine (for example, 4-methylaminopyridine).
- It will be appreciated that when a G group is present, the G group may be associated with a single M metal centre as shown in formula (I), or the G group may be associated with both metal centres and form a bridge between the two metal centres, as shown below in formula (Ia):
- Wherein R1, R2, R3A, R3B, R4, E1, E2, E3, E4, E5, E6, R5, M, G and X, are as defined for formula (I). It will also be appreciated that X may form a bridge between the two metal centres.
- The skilled person will understand that, in the solid state, the catalysts of the first aspect may be associated with solvent molecules such as water, or alcohol (e.g. methanol or ethanol). It will be appreciated that the solvent molecules may be present in a ratio of less than 1:1 relative to the molecules of catalyst of the first aspect (i.e. 0.2:1, 0.25:1, 0.5:1), in a ratio of 1:1, relative to the molecules of catalyst of the first aspect, or in a ratio of greater than 1:1, relative to the molecules of catalyst of the first aspect.
- The skilled person will understand that, in the solid state, the catalysts of the first aspect may form aggregates. For example, the catalyst of the first aspect may be a dimer, a trimer, a tetramer, a pentamer, or higher aggregate.
- It will be appreciated that the preferred features described above for the catalyst of the first aspect may be present in combination mutatis mutandis.
- For example, each occurrence of R2 and R5 are H, E, is C and E2 is O, S or NH (preferably E2 is O).
- Preferably, both occurrences of R, are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; R3A and R3B are the same or different, and are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene; E3 to E6 are the same or different and are selected from NR4, S, N or O; R4 is hydrogen, an optionally substituted alkyl or heteroalkyl; each X is the same, and is selected from OC(O)Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; each G (where present) is independently selected from halide; water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile; M1 and M2 are independently selected from Mg(II), Zn(II), Cr(II), Cr(III)-X, Co(II), Co(III)-X, Mn(II), Ni(II), Ni(III)-X, Fe(II), and Fe(III)-X, preferably M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Preferably M, and M2 are the same, and are selected from Ni(II) or Mg(II).
- Preferably, both occurrences of R, are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; R3A is a substituted or unsubstituted cycloalkylene or alkylene and R3B is a substituted or unsubstituted alkylene or arylene; each occurrence of E3 to E6 is NR4; R4 is hydrogen; each X is the same, and is selected from OC(O)Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; each G (where present) is independently selected from halide; water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile; M1 and M2 are independently selected from Mg(II), Zn(II), Cr(II), Cr(III)-X, Co(II), Co(III)-X, Mn(II), Ni(II), Ni(III)-X, Fe(II), and Fe(III)-X, preferably M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same, and are selected from Ni(II) or Mg(II).
- Preferably, both occurrences of R, are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; R3A and R3B are the same and are substituted or unsubstituted alkylene; each of E3, E4, E5 and E6 is NR4 wherein one of the R4 groups is different from a remaining R4 group and is selected from an optionally substituted alkyl or heteroalkyl and the remaining R4 group/s are hydrogen; each X is the same, and is selected from OC(O)Rx, ORx, halide, carbonate, amino, nitro, alkyl, aryl, heteroaryl, phosphinate or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; each G (where present) is independently selected from halide; water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile; M1 and M2 are independently selected from Mg(II), Zn(II), Cr(II), Cr(III)-X, Co(II), Co(III)-X, Mn(II), Ni(II), Ni(III)-X, Fe(II), and Fe(III)-X, preferably M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same, and are selected from Ni(II) or Mg(II).
- Preferably both occurrences of R, are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; R3A and R3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene; E3 to E6 are selected from N, NR4, S or O; R4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl; each X is the same, and is selected from OC(O)Rx, ORx, or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; each G (where present) is independently selected from halide; water; a heteroaryl optionally substituted by alkyl, alkenyl, alkynyl, alkoxy, halogen, hydroxyl, nitro or nitrile; M1 and M2 are independently selected from Mg(II), Zn(II), Cr(II), Cr(III)-X, Co(II), Co(III)-X, Mn(II), Ni(II), Ni(III)-X, Fe(II), and Fe(III)-X, preferably M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same, and are selected from Ni(II) or Mg(II); wherein:
-
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- More preferably, both occurrences of R, are the same, and are selected from an optionally substituted alkyl; R2 is hydrogen; R3A and R3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and substituted or unsubstituted arylene; each occurrence of E3 to E6 is NR4; R4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl; each X is the same, and is selected from OC(O)Rx, ORx, or OSO2Rx, Rx is alkyl, alkenyl, alkynyl, heteroalkyl, aryl, heteroaryl or alkylaryl; M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same, and are selected from Ni(II) or Mg(II); wherein:
-
- i) R3A is different from R38; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- Still more preferably, both occurrences of R, are the same, and are tertiary butyl; R2 is hydrogen; R3A and R3B are selected from butylene, benzylene, ethylene, propylene, 2,2-dimethylpropylene; each occurrence of E3 to E6 is NR4; R4 is selected from hydrogen, methyl, ethyl, propyl, butyl, or -alkyl-C(O)—OR19 as defined hereinabove, preferably methyl propanoate; each X is the same, and is OAc; M1 and M2 are independently selected from Mg(II), Ni(II), Ni(III)-X and Zn(II). Still more preferably M1 and M2 are independently selected from Ni(II), Ni(III), or Mg(II). Preferably M1 and M2 are the same, and are selected from Ni(II) or Mg(II); wherein:
-
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and Ee.
- Exemplary catalysts of the first aspect are as follows:
- More preferably the catalyst of formula (I) is:
- In the second aspect of the invention, there is provided a ligand of formula (II):
- wherein:
R1 and R2 are independently selected from hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl group, a silyl ether group, a sulfoxide group, a sulfonyl group, a sulfinate group or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkylthio, arylthio, alicyclic or heteroalicyclic group;
R3A and R3B are independently selected from optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene, may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
R5 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl; E, is C, E2 is OY, S or NH or E1 is N and E2 is O;
Y is hydrogen or an alkali metal;
E3, E4, E5 and E6 are each independently selected from N, NR4, O and S, wherein when any of E3, E4, E5 or E6 are N, is , and wherein when any of E3, E4, E5 or E6 are NR4, O or S, is ; R4 is independently selected from H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
and wherein: -
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- All of the preferred features defined hereinabove in relation to the first aspect apply in relation to the second aspect. In particular, all of the preferred features in relation to the groups R1, R2, R3A, R3B, R4, R5, E1, E2, E3, E4, E5, and E6 apply equally to the second aspect.
- Preferably Y is selected from hydrogen, lithium, sodium, potassium, rubidium, caesium, or francium. More preferably Y is either hydrogen or lithium.
- Preferably both occurrences of R1 are the same, and are selected from hydrogen, halide, amino, nitro, sulfoxide, sulfonyl, sulfinate, silyl, silyl ether and an optionally substituted alkyl, alkenyl, aryl, heteroaryl, alkoxy, aryloxy or alkylthio; R2 is hydrogen; R3A and R3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene and substituted or unsubstituted arylene; E3 to E6 are N, NR4, S or O; R4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
- wherein:
-
- iii) R3A is different from R3B; and/or
- iv) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- More preferably, both occurrences of R, are the same, and are selected from an optionally substituted alkyl; R2 is hydrogen; R3A and R3B are selected from substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and substituted or unsubstituted arylene; each occurrence of E3 to E6 is NR4; R4 is selected from hydrogen, or optionally substituted alkyl or heteroalkyl;
-
- wherein:
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- Still more preferably, both occurrences of R1 are the same and are tertiary butyl; R2 is hydrogen; R3A and R3B are selected from tertiary butylene, benzylene, ethylene, propylene, 2,2-dimethylpropylene; each occurrence of E3 to E6 is NR4; R4 is selected from hydrogen, methyl, ethyl, propyl, butyl, or -alkyl-C(O)—OR19 as defined hereinabove, preferably methyl propanoate;
-
- wherein:
- i) R3A is different from R3B; and/or
- ii) at least one occurrence of E3, E4, E5 and E6 is different to a remaining occurrence of E3, E4, E5 and E6.
- More preferably still, the ligand of formula (II) is:
- wherein:
R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene; and R4 is selected from methyl, ethyl, propyl, or butyl;
or the ligand of formula (II) is: - or the ligand of formula (II) is:
- or the ligand of formula (II) is:
- or the ligand of formula (II) is:
- wherein:
R3 is selected from 2,2-dimethylpropylene, propylene, or ethylene;
or the ligand of formula (II) is: - or the ligand of formula (II) is:
- or the ligand of formula (II) is:
- wherein:
R is methyl or hydrogen;
or the ligand of formula (II) is: - or the ligand of formula (II) is:
- wherein:
R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene; and R4 is methyl, ethyl, propyl, or butyl. Preferably R4 is methyl. - More preferably still, the ligand of formula (II) comprises at least one N-substituent, and may be selected from:
- wherein:
R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene; and R4 is selected from methyl, ethyl, propyl, or butyl;
or: - R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene; and R4 is methyl, ethyl, propyl, or butyl. Preferably R4 is methyl.
- In the third aspect, the invention extends to methods of preparation of ligands, complexes and catalysts according to the second aspect and first aspect respectively or as otherwise defined herein.
- In the fourth aspect of the present invention, there is provided a process of asymmetric N-substitution of a symmetrical ligand having a tetraaminophenol coordination sphere, the process comprising the following steps:
-
- a) protecting at least two of the amino groups of the coordination sphere of the symmetrical ligand with an optionally substituted alkylene;
- b) asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent.
- Preferably the symmetrical ligand comprises formula (IV):
- wherein:
R, and R2 are as defined above in relation to the second aspect, and R3 is defined as R3A or R3B in relation to the second aspect. - More preferably therefore, the symmetrical ligand of formula (IVa) is:
- Preferably the optionally substituted alkylene is selected from an optionally substituted methylene or ethylene.
- Preferably the optionally substituted alkylene is derived from a protecting reagent. Preferably therefore step (a) comprises reacting the symmetrical ligand with a protecting reagent comprising an optionally substituted alkyl group. Preferably the protecting reagent is an aldehyde, more preferably an aldehyde selected from formaldehyde or benzaldehyde.
- Preferably step (a) comprises protecting two or more of the amino groups of the coordination sphere of the symmetrical ligand by forming bridging groups between the adjacent amino or phenolic groups. Preferably the bridging groups are the optionally substituted alkylene, and are selected from an optionally substituted methylene or ethylene.
- Preferably the product of step (a) comprises a pair of optionally substituted alkylene bridges between adjacent nitrogen atoms of the coordination sphere.
- Preferably step (a) is conducted in the presence of a solvent which may be any suitable solvent for the protecting reagent, for example methanol or THF.
- Preferably step (a) comprises contact with the protecting reagent for sufficient time to complete or substantially complete the reaction. Suitable contact times are between 30 minutes and 15 hours, more preferably for between 2 hours and 8 hours, most preferably for around 6 hours.
- Preferably step (a) is conducted at a suitable temperature. Suitable temperatures may be in the range −25 to 75° C., for example 0 to 50° C., typically 15-30° C. such as room temperature (around 21° C.).
- Preferably step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with an N-substituting agent by for example hydroamination with an alkene (such as an acrylate or acrylonitrile) or by using an alkylating agent.
- Preferably the substituent is an R4 group, as defined hereinabove. Preferably therefore, one or more of the amino groups is substituted to form an NR4 group.
- Preferably step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent. More preferably step (b) comprises asymmetrically N-substituting one or more of the protected amino groups of the product of step (a) with a substituent by reacting the product of step (a) with an N-substituting agent.
- Preferably the N-substituting agent is an alkylating agent or an alkene such as an activated alkene for example an alkyl acrylate, alkyl methacrylate, alkyl vinyl ketone or acrylonitrile, more preferably the alkylating agent comprises the formula R4X. Preferably X is a halide, tosylate or triflate, more preferably X is iodine. In one preferred embodiment, R4X is selected from iodomethane, iodoethane, 1-iodopropane or 1-iodobutane.
- Preferably step (b) is conducted in the presence of a solvent which may be any suitable solvent for N-substituting agent, for example methanol, dichloromethane, or THF.
- Preferably step (b) comprises contact with the N-substituting agent for sufficient time to complete or substantially complete the reaction. Suitable contact times are between 12 and 22 hours, more preferably between 14 and 18 hours, most preferably for around 16 hours.
- Preferably step (b) is conducted at a suitable temperature. Suitable temperatures may be between 20° C. to 90° C., more preferably between 23° C. to 80° C., most preferably at around 25-50° C.
- The method may further comprise step (c) hydrolysing the optionally substituted alkylene bridging groups between the adjacent amino groups.
- Preferably the hydrolysing of step (c) is performed by reacting the product of step (b) with an acid, more preferably with HCl and subsequently isolating the material Optionally, the method may further comprise upstream steps of formation of the symmetrical ligand having a tetraaminophenol coordination sphere.
- Preferably the method further comprises upstream steps of formation of the symmetrical ligand comprising formula (IV):
- wherein:
R1 and R2 are as defined above in relation to the second aspect, and R3 is defined as R3A or R3B in relation to the second aspect. - More preferably therefore, the method further comprises upstream steps of formation of the symmetrical ligand comprising formula (IVa):
- Preferably the upstream steps comprise (1) formation of a symmetrical ligand having a tetraiminophenol coordination sphere, and (2) reduction of the imine groups to amine groups.
- Preferably upstream step (1) comprises formation of a symmetrical ligand having a tetraiminophenol coordination sphere from a compound of formula (III):
- wherein R1 and R2 are as defined hereinabove.
- More preferably upstream step (1) comprises reacting a compound of formula (III) with an amine of formula H2N—R3—NH2, wherein R3 is as defined hereinabove.
- Upstream step (1) may be conducted in the presence of a suitable solvent, an acid and an electrolyte.
- The solvent may be any suitable solvent for the reactants of upstream step (1), for example methanol or THF. More preferably the solvent is methanol.
- Preferably upstream step (2) comprises reacting the product of upstream step (1) with a reducing agent.
- Suitable reducing agents are known to those skilled in the art, for example sodium borohydride or hydrogen.
- Preferably upstream step (2) is conducted in the presence of a solvent, which may be any suitable solvent for the reactants of upstream step (2), for example methanol or THF. More preferably the solvent is methanol.
- In one preferred embodiment, the process comprises the following steps:
-
- (a) forming a symmetrical ligand having a tetraiminophenol coordination sphere;
- (b) reducing the imino groups of the product of step (a) to amino groups;
- (c) protecting the amino groups of the product of step (b) with an optionally substituted alkylene;
- (d) asymmetrically N-substituting one or more of the protected amino groups of the product of step (c) with a substituent;
- (e) hydrolysing the optionally substituted alkylene groups of the product of step (d) to remove the alkylene bridging group;
- (f) optional neutralisation of the product of step (e).
- In a more preferred embodiment, the process comprises the following steps:
-
- (a) reacting a compound of formula (III) with an amine of formula H2N—R3—NH2 to form a ligand having a tetraiminophenol coordination sphere;
-
- (b) reducing the imino groups of the product of step (a) to amino groups;
- (c) protecting the amino groups of the product of step (b) by forming bridging groups between the adjacent amino groups, wherein the bridging groups are optionally substituted alkylenes;
- (d) asymmetrically N-substituting one or more of the protected amino groups of the product of step (c) with an N-substituting agent;
- (e) hydrolysing the optionally substituted alkylene groups of the product of step (d);
- (f) optional neutralisation of the product of step (e);
- wherein R1, R2, R3, R4 and X are as defined in relation to the second aspect.
- Preferably the asymmetrical ligand produced is that according to the second aspect.
- Preferably, the ligand according to the second aspect is that of formula (IIa):
- wherein:
R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene; and R4 is selected from methyl, ethyl, propyl, or butyl. - Preferably in formula IV, R1 is tertiary butyl; R2 is hydrogen; R3 is 2,2-dimethylpropylene.
- In a fifth aspect of the invention, the catalysts of the first aspect are capable of polymerising (i) carbon dioxide and an epoxide, (ii) an epoxide and an anhydride, and (iii) a lactide and/or a lactone. Therefore, in a fifth aspect of the invention there is provided a process for the reaction of carbon dioxide with an epoxide, an anhydride with an epoxide, or a lactide and/or a lactone in the presence of a catalyst according to the first aspect.
- The process of the fifth aspect may be carried out in the presence of a chain transfer agent. Suitable chain transfer agents include the chain transfer agents, for example as defined by formula (II), in WO 2013/034750, the entire contents of which are hereby incorporated by reference. For example, the chain transfer agent may be water, or may comprise at least one amine (—NHR), alcohol (—OH) or thiol (—SH) moiety.
- Examples of chain transfer agents useful in the second aspect include water, mono-alcohols (i.e. alcohols with one OH group, for example, 4-ethylbenzenesulfonic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, phenol, cyclohexanol), diols (for example, 1,2-ethanediol, 1-2-propanediol, 1,3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, catechol and cyclohexenediol), triols (glycerol, benzenetriol, 1,2,4-butanetriol, tris(methylalcohol)propane, tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylolpropane, preferably glycerol or benzenetriol), tetraols (for example, calix[4]arene, 2,2-bis(methylalcohol)-1,3-propanediol, di(trimethylolpropane)), polyols (for example, D-(+)-glucose, dipentaerythritol or D-sorbitol), dihydroxy terminated polyesters (for example polylactic acid), dihydroxy terminated polyethers (for example poly(ethylene glycol)), acids (such as diphenylphosphinic acid), starch, lignin, mono-amines (i.e. methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine), diamines (for example 1,4-butanediamine), triamines, diamine terminated polyethers, diamine terminated polyesters, mono-carboxylic acids (for example, 3,5-di-tert-butylbenzoic acid), dicarboxylic acids (for example, maleic acid, malonic acid, succinic acid, glutaric acid or terephthalic acid, preferably maleic acid, malonic acid, succinic acid, glutaric acid), tricarboxylic acids (for example, citric acid, 1,3,5-benzenetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid, preferably citric acid), mono-thiols, dithoils, trithiols, and compounds having a mixture of hydroxyl, amine, carboxylic acid and thiol groups, for example lactic acid, glycolic acid, 3-hydroxypropionic acid, natural amino acids, unnatural amino acids, monosaccharides, disaccharides, oligosaccharides and polysaccharides (including pyranose and furanose forms). Preferably, the chain transfer agent is selected from cyclohexene diol, 1,2,4-butanetriol, tris(methylalcohol)propane, tri(methylalcohol)propane, tri(methylalcohol)butane, pentaerythritol, poly(propylene glycol), glycerol, mono- and di-ethylene glycol, propylene glycol, tris(methylalcohol)nitropropane, tris(methylalcohol)ethane, 2,2-bis(methylalcohol)-1,3-propanediol, 1,3,5-benzenetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,4-butanediamine, 1,6-hexanediol, D-sorbitol, 1-butylamine, terephthalic acid, D-(+)-glucose, 3,5-di-tert-butylbenzoic acid, and water.
- The process of the fifth aspect may be carried out in the presence of a solvent. Examples of solvents useful in the third aspect include toluene, diethyl carbonate, dimethyl carbonate, dioxane, dichlorobenzene, methylene chloride, propylene carbonate, ethylene carbonate, acetone, ethyl acetate, tetrahydrofuran (THF), etc.
- When the process of the fifth aspect involves the reaction of an epoxide, the epoxide may be any compound comprising an epoxide moiety. The epoxide may be purified (for example by distillation, such as over calcium hydride) prior to reaction with carbon dioxide or the anhydride. For example, the epoxide may be distilled prior to being added to the reaction mixture comprising the catalyst.
- The process of the fifth aspect of the invention may be carried out at a pressure of 1 to 100 atmospheres, preferably at 1 to 40 atmospheres, such as at 1 to 20 atmospheres, more preferably at 1 or 10 atmospheres. The catalysts used in the process of the second aspect allow the reaction to be carried out at low pressures.
- The process of the fifth aspect of the invention may be carried out at a temperature of about 0° C. to about 250° C., preferably from about 40° C. to about 160° C., even more preferably from about 50° C. to about 120° C. The duration of the process may be up to 168 hours, such as from about 1 minute to about 24 hours, for example from about 5 minutes to about 12 hours, e.g. from about 1 to about 6 hours.
- The process temperature, for copolymerisations of carbon dioxide and an epoxide, may be used to control the product composition. When the temperature of the process of the fifth aspect which involves reacting carbon dioxide and an epoxide is increased, the selectivity of the catalyst towards the formation of cyclic carbonate is also increased. The catalysts and processes may operate at temperatures up to 250° C.
- The process of the fifth aspect of the invention may be carried out at low catalytic loading. For example, when the reaction involves copolymerisation of carbon dioxide and an epoxide, the catalytic loading for the process is preferably in the range of 1:1,000-300,000 catalyst:epoxide, more preferably in the region of 1:10,000-100,000 catalyst:epoxide, even more preferably in the region of 1:50,000-100,000 catalyst:epoxide. When the process involves copolymerisation of an epoxide and an anhydride, or the reaction of a lactide and/or lactone, the catalytic loading for the process is preferably in the range of 1:1,000-300,000 catalyst:total monomer content, more preferably in the region of 1:10,000-100,000 catalyst:total monomer content, even more preferably in the region of 1:50,000-100,000 catalyst:total monomer content. The ratios above are molar ratios.
- The catalysts of the first aspect, and in particular catalysts wherein both M1 and M2 are selected from Ni(II) and Mg(II), have high activity and selectivity for producing polycarbonates by reacting carbon dioxide and an epoxide, optionally in the presence of a chain transfer agent, and preferably at temperatures between about 40° C. to about 160° C. Thus, the reaction times for the process of the second aspect can be less than 12 hours, and preferably from about 2 to about 6 hours.
- The process of the fifth aspect can be carried out in a batch reactor or a continuous reactor.
- It will be appreciated that the various features described above for the process of the fifth aspect may be present in combination mutatis mutandis. All preferred features of the first aspect apply equally to the fifth aspect and may be present in combination mutatis mutandis.
- The sixth aspect of the invention provides a product of the process of the fifth aspect of the invention. All preferred features of the fifth aspect of the invention apply to the sixth aspect of the invention mutatis mutandis.
- When the process of the fifth aspect is carried out in the presence of a chain transfer agent, it produces polymer chains which are terminated at substantially all ends with hydroxyl groups (i.e. polycarbonate polyols or polyester polyols). By “substantially”, it is meant that at least 90% of the resultant polymer chains, preferably at least 95% of the resultant polymer chains, and even more preferably at least 98%, and even more preferably at least about 99% of the resultant polymer chains are terminated at all ends in hydroxyl groups. In order for at least 90% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 4 equivalents of chain transfer agent, relative to the amount of catalyst. In order for at least 95% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the second aspect to be carried out in the presence of at least about 10 equivalents of chain transfer agent, relative to the amount of catalyst. In order for at least 98% of the resultant polymer chains to be terminated at all ends with hydroxyl groups, it is preferred for the process of the fifth aspect to be carried out in the presence of at least about 20 equivalents of chain transfer agent, relative to the amount of catalyst. Thus, polyols obtained by the process of the fifth aspect are considered to form part of the sixth aspect of the invention.
- The chain transfer agent referred to in the fifth aspect may be used to control the molecular weight (Mn) of the polymer products of the sixth aspect. Preferably, the molecular weight (Mn) of the polymer products of the sixth aspect is greater than about 200 g/mol. The molecular weight (Mn) of the polymer products of the sixth aspect may be from about 200 g/mol to about 200,000 g/mol. The molecular weight of the polymers produced by the fifth aspect can be measured by Gel Permeation Chromatography (GPC) using, for example, a GPC-60 manufactured by Polymer Labs, using THF as the eluent at a flow rate of 1 ml/min on Mixed B columns, manufactured by Polymer Labs. Narrow molecular weight polystyrene standards can be used to calibrate the instrument.
- It is possible to produce polycarbonate polyols and polyester polyols having a Mn of from about 200 g/mol to about 20,000 g/mol, preferably less than about 10,000 g/mol by adding a chain transfer agent to the process of the fifth aspect.
- It is also possible to produce polymers having a Mn of greater than about 20,000 g/mol from the process of the fifth aspect. Preferably, the polymer having a Mn of greater than about 20,000 g/mol is a polycarbonate or a polyester, even more preferably a polycarbonate. Preferably, the polymer having a Mn of greater than about 20,000 g/mol is a polycarbonate and is produced carrying out the process of the fifth aspect without adding a chain transfer agent (CTA).
- The polymers produced by the fifth aspect may be produced to have a polydispersity index (PDI) of less than about 2, more preferably less than about 1.5, and even more preferably less than about 1.2. Furthermore, it is possible to control the molecular weight distribution so as to produce multi-modal or broad molecular weight distribution polymers by addition of one or more chain transfer agent(s).
- The polymers produced by the process of the fifth aspect (e.g. polycarbonates such as PCHC or PPC), are useful building blocks in the preparation of various copolymeric materials. The polymers produced by the process of the fifth aspect may undergo further reaction, for example to produce polymeric products such as polyureas or polyamines. These processes and reactions are well known to the skilled person (for example, refer to WO2013/034750).
- The polycarbonate or polyester polyols produced by the process of the fifth aspect may be used in various applications and products which conventionally use polyols, including adhesives (such as hot melt adhesives and structural adhesives), a binder (such as forest product binders, foundry core binders and rubber crumb binders), coatings (such as powder coatings, transport, e.g. automotive or marine coatings, fast cure coatings, self-healing coatings, top coats and primers, varnishes, and coatings for marine applications, e.g. oil rigs), elastomers (such as cast elastomers, fibres/spandex elastomers, footwear elastomers, RIM/RRIM elastomers, synthetic leather elastomers, technical microcellular elastomers and TPU elastomers), flexible foams (such as viscoelastic foams), rigid foams (such as rigid and flexible panels, moulded rigid foams, aerosol gap filling foam, spray foams, refrigeration foams, pour-in-place foams, and foam slabs) and sealants (such as glazing sealants for commercial, industrial and transport (e.g. automotive) applications, and construction sealants). The polyamines and polyureas can be processed using methods standard techniques known in the art, such as foaming.
- It will be understood that the polycarbonate and polyester polyols produced by the process of the fifth aspect may be mixed with other polyols prior to further use or reaction.
- The polycarbonates, and in particular, polycarbonates having a Mn of greater than about 20,000 g/mol (e.g. produced without adding chain transfer agent to the process of the fifth aspect) may have a number of beneficial properties including high strength, high toughness, high gloss, high transparency, low haze, high gas (e.g. oxygen and carbon dioxide) or water barrier properties, flame resistance, UV resistance, high durability, rigidity and stiffness, compatibility with plasticizers, broad dimensional stability temperature, biodegradability and biocompatibility, and modulus of elasticity and yield strength comparable to LDPE. Thus, these polymers may be used in various applications and products, such as electronic components, construction materials, data storage products, automotive and aircraft products, security components, medical applications, mobile phones, packaging (including bottles), optical applications (such as safety glass, windscreens, etc).
-
- Ligands H2L1-4 were prepared by the following method:
- A tetraaminophenol ligand may be formed by the following process (steps 1 and 2):
- To a round-bottomed flask was added 4-tert-butyl-2,6-diformylphenol (1.20 g, 5.80 mmol), NaClO4 (2.81 g, 23.2 mmol), acetic acid (0.66 mL, 11.6 mmol) and methanol (90 mL). This solution was heated to 70° C. whilst stirring, as the solution started to boil, 2,2-dimethyl-1,3-propanediamine (0.70 mL, 5.8 mmol) was added slowly in methanol (30 mL). The yellow reaction mixture was allowed to cool to room temperature, and left stirring for 24 hours, after which a bright orange precipitate was filtered and washed with cold (−78° C.) methanol (1.85 g, 95%). The product was suspended in methanol (180 mL). The suspension was cooled to 0° C. and NaBH4 (2.65 g, 69.9 mmol) was added slowly. As NaBH4 was added, the red-orange suspension turned to a clear solution. Water was added slowly, and the solution turned cloudy. Once precipitate started to form, the mixture was left overnight and H2L11 was filtered off as a white solid (1.21 g, 88%).
- To a solution of the resulting product (20.8 mmol) in methanol (500 mL) was added a formaldehyde solution (37% in water, 104 mmol) at room temperature (RT). The reaction was stirred at RT for 15 h after which the reaction mixture was filtered and the filter cake was washed with MeOH and water. The resultant white powder was transferred to a round bottom flask. Toluene was added and evaporated under reduced pressure to azeotrope off the residual water giving the desired product as a white powder (17.2 mmol). R4X (iodomethane, iodoethane, 1-iodopropane or 1-iodobutane, 104 mmol) was added to a stirred solution of this white powder (10.4 mmol) in anhydrous THF (120 mL) at 25° C. until the reaction was deemed to be complete. A white precipitate formed in the reaction mixture and was collected by suction filtration. The filter cake was washed with THF. The resultant white powder was transferred to a round bottom flask and dried under high vacuum for several hours. This was dissolved (7.3 mmol) in MeOH and concentrated HCl(aq) (1:1) and placed in a heating block set to 75° C. whilst refluxing and stirred for 15 h. After this time, the slightly yellow solution was allowed to cool to RT and was neutralized with a saturated aqueous solution of K2CO3, inducing the product to precipitate out of solution as a white solid. This solid was collected and dried.
- H2L1: 1H NMR (400 MHz, CDCl3) δ 7.05 (d, J=2.4 Hz, 1H), 7.02 (d, J=2.4 Hz, 1H), 6.89 (d, J=2.5 Hz, 1H), 6.85 (d, J=2.5 Hz, 1H), 3.74 (s, 2H), 3.61 (s, 2H), 3.54 (s, 2H), 3.51 (s, 2H), 2.50 (s, 2H), 2.39 (s, 2H), 2.37 (s, 2H), 2.29 (s, 2H), 2.27 (s, 3H), 1.30 (3) (s, 9H), 1.29 (6) (s, 9H), 0.93 (s, 6H), 0.92 (s, 6H).
- MS (ESI) m/z: 567.5 ([M+H]+, 100%).
- H2L2: 1H NMR (400 MHz, CDCl3) δ 7.08 (m, 2H), 6.87 (m, 2H), 3.77 (s, 2H), 3.58 (s, 2H), 3.53 (s, 4H), 2.55 (s, 2H), 2.53 (q, J=7.0 Hz, 2H), 2.41 (s, 2H), 2.33 (s, 4H), 1.34 (s, 9H), 1.33 (s, 9H), 1.07 (t, J=7.0 Hz, 3H), 0.94 (s, 6H), 0.92 (s, 6H).
- MS (ESI) m/z: 581.5 ([M+H]+, 100%).
- H2L3: 1H NMR (400 MHz, CDCl3) δ 7.11 (m, 2H), 6.84 (m, 2H), 3.76 (s, 2H), 3.52 (s, 2H), 3.50 (m, 4H), 2.54 (s, 2H), 2.48 (m, 2H), 2.38 (s, 2H), 2.32 (s, 2H), 2.30 (s, 2H), 2.20 (s, 2H), 1.59 (m, 2H), 1.34 (s, 18H), 0.93 (s, 6H), 0.91 (s, 6H).
- MS (ESI) m/z: 595.5 ([M+H]+, 100%), 581.5 ([M-CH3+H]+, 30%).
- H2L4: 1H NMR (400 MHz, CDCl3) δ 7.11 (m, 2H), 6.83 (m, 2H), 3.75 (s, 2H), 3.51 (m, 6H), 2.53 (s, 2H), 2.49 (m, 2H), 2.38 (s, 2H), 2.32 (s, 2H), 2.30 (s, 2H), 1.55 (m, 2H), 1.34 (s, 18H), 0.94 (q, J=7.3 Hz, 3H), 0.93 (s, 6H), 0.91 (s, 6H).
- MS (ESI) m/z: 609.5 ([M+H]+, 100%), 595.5 ([M-CH3+H]+, 10%), 581.5 ([M-CH2CH3+H]+, 10%).
-
- 4-tert-butyl-2,6-diformylphenol (4 mmol) and 1,3-diamino-2,2-dimethylpropane (2 mmol) were each dissolved in EtOH (15 mL and 10 mL respectively). The solutions were warmed to boiling then the solution of amine added dropwise with stirring giving an immediate colour change to a deeper yellow. After stirring overnight the precipitate was collected, washed with cold ethanol (2×5 mL), pentane (1×5 mL) then dried under vacuum, giving 4. 1H NMR (CDCl3) δ: 14.45 (br s, 2H), 10.56 (s, 2H), 8.45 (s, 2H), 7.94 (s, 2H), 7.55 (s, 2H), 3.58 (s, 4H), 1.34 (s, 18H), 1.15 (s, 6H).
- 4 (0.4 mmol) was dissolved in THF (10 mL) and treated with LiHMDS (0.8 mmol) in THE (3 mL) causing the bright yellow solution to change to a greenish yellow solution. After 30 mins a solution of 1,2-diaminobenzene (0.4 mmol) was added in THF (10 mL) over 10 mins with rapid stirring. After stirring overnight the colour had again returned to bright yellow. The solution was concentrated to 2 mL and layered with heptane (10 mL) and allowed to stand. The yellow solid that precipitated after 1 day was collected and washed with pentane (2×5 mL) then dried under vacuum. 1H NMR (CDCl3) δ: 9.51 (s, 2H), 7.91 (s, 2H), 7.45 (d, 2H), 7.38 (d, 2H), 6.74 (s, 4H), 3.4 (br s, 4H), 1.34 (s, 18H), 0.62 (s, 6H).
- 5 (0.2 mmol) was dissolved in dry MeOH (25 mL) under nitrogen in a dried 3-neck round-bottomed flask. HCl in EtOH was added (1.2 mmol) and the solution stirred for 10 minutes before NaBH4 (2 mmol) was added in portions. The solution was stirred for 2 hours after which the solvent was removed under vacuum. Water (20 mL) was added to the crude and the pH brought up to 6-7 by adding AcOH dropwise. The product (H2L510) was extracted with DCM (2×25 mL), dried over NaSO4 and the solvent removed under vacuum.
- 1H NMR (CDCl3) δ: 7.2-7.35 (m, 2H), 7.19 (s, 1H), 7.01 (s, 1H), 6.85-6.95 (m, 4H), 4.32 (s, 4H), 4.26 (br s, 2H), 4.08 (s, 2H), 2.59 (s, 4H), 2.42 (s, 2H), 1.32 (s, 18H), 1.16 (s, 6H). 13C NMR (CDCl3) δ: 154.4, 141.7, 138.0, 129.2, 128.4, 126.9, 125.4, 125.1, 124.9, 122.4, 119.2, 111.3, 59.5, 54.2, 46.5, 35.1, 34.1, 31.7, 24.6.
-
- The asymmetric ligand H2L6 was prepared using the following method:
- B was formed by reacting 4-tert-butylsalicylaldehyde (15 mmol) with piperazine (7.5 mmol) and formaldehyde (15 mmol) in glacial acetic acid (25 mL) at 120° C. The white precipitate was collected and washed with ethanol and diethyl ether.
- A solution of 2,2-dimethyl-1,3-propanediamine (6.4 mmol) in MeOH (60 mL) was added dropwise over 6 h to a refluxing solution of B(6.4 mmol) in MeOH (300 mL). After a further 10 h reflux, the solution was cooled to RT and the bright yellow supernatant decanted from a bright yellow solid. The residue was re-dissolved in DCM and co-evaporated with MeOH until a yellow precipitate formed. The resulting solids were collected by filtration, washed with MeOH, pentane and dried under high vacuum for 2 h. This gave a yellow powder (5.0 mmol). A solution of this yellow powder in THF/MeOH (3:1) was treated with solid NaBH4. The resulting white suspension was allowed to stir for 1 h at RT, then partitioned between NaHCO3 (2M, aq) and DCM. The organic phase was separated and dried over Na2SO4, then evaporated to dryness to yield H2L6.
- H2L6: 1H NMR (400 MHz, CDCl3) δ 7.14-7.05 (m, 2H), 7.05-6.96 (m, 2H), 5.37-5.27 (s, 4H), 3.89-3.81 (s, 4H), 3.70-3.63 (s, 4H), 2.67-2.62 (s, 4H), 2.55-2.49 (s, 2H), 1.35 (s, 18H), 0.99-0.90 (s, 6H).
-
- The asymmetric ligand H2L7 was prepared using the following method:
- C was prepared by reacting 4-tert-butylsalicylaldehyde (129 mmol) with formaldehyde (193 mmol) in HBr (48% aq, 970 mmol) with a few catalytic drops of H2SO4 at 70° C. for 16 hours. The solution was cooled, diluted and extracted with methylene chloride (30 mL), giving C. N,N′-dimethyl-2,2-dimethyl-1,3-propanediamine was prepared by reaction of 2,2-dimethyl-1,3-propanediamine (166 mmol) with ethyl formate (80 mL) followed by reduction with LiAlH4 (10 g) in diethyl ether (250 mL).
- A solution of 3-(bromomethyl)-2-hydroxy-5-tert-butylbenzaldehyde C (48.4 mmol) in THF (40 mL) was added to a stirred solution of N,N′-dimethyl-2,2-dimethyl-1,3-propanediamine (22.0 mmol) in THF (20 mL) giving a yellow suspension. A solution of triethylamine (61.6 mmol) in THF (10 mL) was added dropwise. The reaction mixture was stirred for 2 h after which time it was partitioned between EtOAc and water. The organic extracts were combined, and dried over Na2SO4 before evaporation to dryness to yield an orange oil. The crude product was dissolved in MeOH (50 mL) and treated with a solution of LiOH (88 mmol) in MeOH (75 mL). After standing overnight the yellow crystalline precipitate was isolated by filtration, washed with ice cold MeOH and dried under high vacuum overnight. This gave a yellow microcrystalline solid (27.6 mmol). A solution of 2,2-dimethyl-1,3-propanediamine (3.52 mmol) in EtOH (18 mL) was added dropwise over 6 h to a suspension of the latter yellow microcrystalline solid (3.49 mmol) and the resulting yellow solution was allowed to stir for a further 8 h. The solvent was removed completely and the yellow solid residue was suspended in pentane and collected by filtration, washed with pentane and dried under high vacuum for 2 h. This gave a yellow powder (2.8 mmol). A suspension of this yellow powder in dry EtOH was treated with a solution of HCl in diethyl ether (2M). Next, solid NaBH4 was added in one portion. The resulting white suspension was allowed to stir for 1 h at RT then partitioned between NaHCO3 (2M, aq) and DCM. The organic phase was separated and dried over Na2SO4 then evaporated to dryness to yield H2L7.
- H2L7: 1H NMR (400 MHz, CDCl3) δ 7.05-6.95 (m, 4H), 5.37-5.27 (s, 4H), 3.81-3.74 (s, 4H), 3.72-3.65 (s, 4H), 2.52-2.45 (s, 4H), 2.45-2.40 (s, 4H), 2.29-2.24 (s, 6H), 1.34-1.24 (s, 18H), 1.01-0.92 (d, J=5.5 Hz, 6H).
-
- The asymmetric ligands Li2Limine 8-10 and H2L9-10 were prepared using the following method:
- Preparation of Li2Limine 8-10:
- To a solution of D (56.3 mmol) in EtOH (500 mL) was added 2,2-dimethyl-1,3-propanediamine (28.2 mmol) and MgSO4 (281.5 mmol). Reaction mixture was stirred 3 h at RT. After this time, reaction medium was filtered, filter cake was washed with DCM, and the mother liquor was evaporated in vacuo to yield a yellow solid. The latter was solubilised in MeOH, and the reaction medium was cooled to 0° C. NaBH4 (258.0 mmol) was added by portion. Reaction mixture was allowed to stir overnight at RT. After this time, solvents were evaporated in vacuo. DCM and water were added, phases were separated, and the aqueous phase was extracted with DCM. The organic layers were combined and dried over Na2SO4.
- Solvents were evaporated in vacuo to yield a product that was purified by recrystallization (DCM/MeOH, 20.9 mmol). To a solution of this purified product (17.5 mmol) in THF (200 mL) was added HCl (1M, 400 mL). Reaction mixture was refluxed overnight. After this time, DCM was added, phases were separated, and the aqueous phase was extracted with DCM. The organic layers were combined and dried over Na2SO4. Solvents were evaporated in vacuo to yield a crude product that was purified by recrystallization (DCM/heptane, 15.9 mmol). The latter product (9 mmol) was next solubilised in MeOH (150 mL) and LIOH (36 mmol) was added. Reaction mixture was stirred for 1 h at RT. After this time, a yellow precipitate had formed, was collected by filtration, and washed with ice-cold MeOH. To a suspension of this yellow product (1 equiv.) in MeOH was added dropwise and over 6 h a solution of the appropriate diamine (2,2-dimethyl-1,3-propanediamine, 1,3-propanediamine or ethylenediamine, 1 equiv.) in MeOH at RT. Reaction mixture was then stirred overnight at RT. After this time, a yellow precipitate had formed, was collected by filtration, and washed with ice-cold MeOH. Products were identified as Li2Limine 810.
- Preparation of H2L9-10:
- To a suspension of Li2Limine 9-10 (1 equiv.) in MeOH was added HCl (1.25M in EtOH, 6 equiv.) and NaBH4 (20 equiv.). Reaction mixture was stirred overnight at RT. After this time, solvents were evaporated in vacuo. DCM and water were added, phases were separated, and the aqueous phase was extracted with DCM. The organic layers were combined, washed with brine and dried over Na2SO4. Solvents were evaporated in vacuo to yield H2L9-10.
- H2L9: 1H NMR (400 MHz, CDCl3) δ 6.96 (d, J=2.5 Hz, 2H), 6.95 (d, J=2.5 Hz, 2H), 3.83 (s, 8H), 2.65 (t, J=6.5 Hz, 4H), 2.51 (s, 4H), 1.78-1.73 (m, 2H), 1.25 (s, 18H), 1.01 (s, 6H).
- MS (ESI) m/z: 525.4 ([M+H]+, 100%)
- H2L10: 1H NMR (400 MHz, CDCl3) δ 6.97 (d, J=2.5 Hz, 2H), 6.95 (d, J=2.5 Hz, 2H), 3.82 (s, 4H), 3.80 (s, 4H), 2.84 (s, 4H), 2.52 (s, 4H), 1.26 (s, 18H), 0.97 (s, 6H). MS (ESI) m/z: 511.3 ([M+H]+, 100%)
-
- The asymmetric ligands H2L12-13 were prepared using the following methods:
- For the preparation of H2L11, see example 1.
- Preparation of H2L12:
- To a solution of H2L11 (5.4 mmol) in MeOH (100 mL) was added benzaldehyde (6.5 mmol) and the reaction stirred at RT for 3 h. The white precipitate formed was isolated by filtration and washed with cold MeOH (3.78 mmol). A solution of this white product (0.78 mmol) in MeOH (10 mL) and DCM (5 mL) was treated with methyl acrylate (0.94 mmol) and the reaction stirred at RT for 16 h after which the solvent was removed in vacuo to yield a white powder (0.74 mmol). To a solution of this white powder (0.14 mmol) in THF (10 mL) was added aq. 1M HCl until pH 3 was obtained (ca. 4 mL) and the reaction stirred at RT for 3 h. Neutralisation with aq. K2CO3 followed by extraction with DCM afforded H2L12 (0.04 mmol).
- MS (ES/CI) m/z: 639.4 ([M+H]+, 100%)
- IR (νC=O, cm−1, neat): 3300, 2955, 2907, 2869, 1741, 1611, 1465, 1395, 1362, 1298, 1216.
- Preparation of H2L13:
- To a solution of H2L11 (9.0 mmol) in MeOH (125 mL) was added methyl acrylate (19.0 mmol) and the reaction stirred at RT for 16 h. The white solid formed was isolated by filtration and washed with cold MeOH. Recrystallisation from hot EtOH gave H2L13.
- H2L13: 1H NMR (400 MHz, CDCl3) δ 7.33 (d, J=2.5 Hz, 2H), 6.75 (d, J=2.5 Hz, 2H), 3.75 (s, 6H), 3.42 (br s, 4H), 3.20 (br s, 4H), 2.94 (br s, 4H), 2.69 (t, J=2.7 Hz, 4H), 2.32 (br s, 4H), 1.42 (s, 18H), 0.88 (s, 12H), 0.24 (br s, 4H).
- MS (ES/CI) m/z: 725.3 ([M]+, 100%)
- IR (cm−1, neat): 3301, 2955, 2907, 2869, 1741, 1480, 1216, 1100.
-
- The ligands H2L14-15 were prepared by the following method:
- 2,2-dimethyl-1,3-propanethiol (5 mmol) was added to a stirred and degassed solution of KOH (20 mmol) in ethanol (50 ml). The mixture was stirred until all components form a homogeneous solution. Then C (10 mmol) was added as a solid to the reaction which slowly dissolves to form a bright yellow solution. The reaction was allowed to stir under nitrogen atmosphere for 20 h. 1M HCl(aq) was then added until the reaction mixture reached acidicity (pH=2) and formed a white suspension. This mixture was extracted with DCM, the organic extracts combined and concentrated in vacuo to give an oil. This was purified on silica. A solution of 2,2-dimethyl-1,3-propanediamine (3.4 mmol) in MeOH (100 ml) was added dropwise to a stirred solution of this purified oil (2.8 mmol) in MeOH (200 ml) at RT under air. The reaction was allowed to stir for 20 h at RT, during which time a yellow precipitate formed. The precipitate was collected by filtration and washed with cold MeOH, affording a yellow solid. A MeOH solution (50 mL) of this yellow product (1.9 mmol) was prepared under nitrogen and allowed to stir at RT. Under a flow of nitrogen, NaBH4 (19.0 mmol) was added portion-wise as a solid and the mixture allowed to stir for a further 16 h. The resulting colourless solution was then quenched by the addition of water. The mixture was extracted with EtOAc, the organic fractions combined, washed with water and saturated aqueous NaCl solution and all volatiles were removed in vacuo to afford H2L14
- H2L14: 1H NMR (CDCl3, 400.1 MHz): δ 7.16 (m, 2H), 6.89 (m, 2H), 3.93 (m, 2H), 3.71 (m, 6H), 2.56 (s, 4H), 2.50 (s, 4H), 1.26 (s, 18H), 0.98 (d, 12H)
- MS (CI) m/z: 587.4 [M+H]+
- 1,3-propanedithiol (0.56 mL, 5.5 mmol) was dissolved in EtOH (50 mL) in a fumecupboard. A solution of C (3 g, 11.1 mmol) in EtOH (50 mL) was added dropwise over 15 minutes and the mixture stirred overnight. The solvent was removed under vacuum and distilled water (50 mL) was added. The product was extracted with DCM (2×30 mL), dried over NaSO4 and the solvent removed under vacuum. The product (was purified by column chromatography (95:5 Cyclohexane:EtOAc) to give a light yellow oil (54%) 1H NMR (CDCl3) δ: 11.22 (s, 2H), 9.90 (s, 2H), 7.60 (d, 2H), 7.45 (d, 2H), 3.79 (s, 4H), 2.61 (t, 4H), 1.93 (q, 2H), 1.35 (s, 18H).
- The half macrocycle (0.484 g, 0.99 mmol) was dissolved in MeOH (35 mL). A solution of 2,2-dimethyl-1,3-propane (0.12 mL, 0.99 mmol) in MeOH (25 mL) was added dropwise over 30 minutes and the solution stirred overnight. A yellow precipitate was filtered off and washed with MeOH. 1H NMR (CDCl3) δ: 13.74 (br s, 2H), 8.34 (s, 2H), 7.37 (s, 2H), 7.17 (s, 2H), 3.83 (s, 4H), 3.48 (s, 4H), 2.64 (t, 4H), 1.98 (m, 2H), 1.31 (s, 18H), 1.08 (s, 6H).
- The yellow precipitate (0.25 g, 0.44 mmol) was dissolved in dry MeOH (50 mL) before NaBH4 (0.2 g, 4.4 mmol) was added in portions. The solution was stirred for 2 hours after which the solvent was removed under vacuum. Water (50 mL) was added to the crude and the pH brought up to 6-7 by adding AcOH dropwise. The product (H2L15) was extracted with DCM (2×25 mL), dried over NaSO4 and the solvent removed under vacuum.
- 1H NMR (CDCl3) δ: 7.22 (s, 2H), 6.88 (s, 2H), 4.01 (s, 4H), 3.66 (s, 4H), 2.50 (s, 4H), 2.38 (t, 4H), 1.6 (q, 2H), 1.29 (s, 18H), 1.06 (s, 6H). 13C NMR (CDCl3) δ: 153.3, 141.6, 126.6, 125.3, 123.8, 121.0, 57.6, 54.0, 34.7, 34.0, 31.6, 30.3, 29.8, 29.5, 24.5. ESI-MS: 559.3 ([M+H]+, 100%).
-
- The complexes [L1-15M2(X2)] were prepared using the following method:
- General Procedure:
- To a suspension of H2L15 (1 equiv.) in MeOH was added the appropriate metal precursor M(X)2 (2 equiv.; Ni(OAc)2.4H2O, Mg(OAc)2.4H2O or Zn(OAc)2.2H2O). Reaction mixture was stirred overnight at RT. After this time, solvents were evaporated and excess water/AcOH was removed by azeotrope with toluene to yield the desired complexes [L1-15M2(X)2].
- [L1Ni2(OAc)2]: MS (ES) m/z: 741.3 ([M−OAc]+, 100%).
- IR (νC=O, cm−1, neat): 1581, 1410.
- [L2Ni2(OAc)2]: MS (ES/CI) m/z: 753.2 ([M−OAc]+, 100%).
- IR (νC=O, cm−1, neat): 1581, 1413.
- [L2Zn2(OAc)2]: MS (ES/CI) m/z: 751.2 ([M−2AcO−+HCO2 −]+, 100%).
- IR (νC=O, cm−1, neat): 1603, 1383.
- [L3Ni2(OAc)2]: MS (ES/CI) m/z: 767.2 ([M−OAc]+, 100%).
- IR (νC=O, cm−1, neat): 1581, 1413.
- [L3Mg2(OAc)2]: 1H NMR (400 MHz, MeOD) δ 7.02 (m, 4H), 3.74 (d, J=18.9 Hz, 4H), 3.6 (d, J=8.9 Hz, 4H), 2.46 (d, J=8.7 Hz, 4H), 2.44 (m, 2H), 2.41 (d, J=8.7 Hz, 2H), 1.90 (s, 6H), 1.54 (m, 2H), 1.30 (s, 9H), 1.28 (s, 9H), 0.96 (s, 6H), 0.95 (s, 6H), 0.84 (t, J=7.3 Hz, 3H).
- MS (ES/CI) m/z: 685.3 ([M−2OAc]+, 100%).
- IR (νC=O, cm−1, neat): 1607, 1395.
- [L4Ni2(OAc)2]: MS (ES/CI) m/z: 781.2 ([M−OAc]+, 100%).
- IR (νC=O, cm−1, neat): 1581, 1413.
- [L7Ni2(OAc)2]: MS (ES/CI) m/z: 739.2 ([M−2OAc+O2CH]+, 100%).
- IR (νC=O, cm−1, neat): 1581, 1414.
- [L9Mg2(OAc)2]: 1H NMR (400 MHz, CD3OD) δ 7.01 (s, 4H), 4.00 (d, J=3.6 Hz, 2H), 3.97 (d, J=3.7 Hz, 2H), 3.27 (d, J=12.0 Hz, 2H), 3.21 (d, J=12.0 Hz, 2H), 3.05-2.99 (m, 2H), 2.79-2.70 (m, 4H), 2.64 (d, J=11.6 Hz, 2H), 1.94-1.76 (m, br, 4H), 1.25 (s, 18H), 1.23 (s, 3H), 1.01 (s, 3H).
- MS (ESI) m/z: 615.3 ([M−2AcO−+HCO2 −]+, 100%).
- [L9Ni2(OAc)2]: MS (ESI) m/z: 683.2 ([M−2AcO−+HCO2 −]+, 100%). IR (νC=O, cm−1, neat): 1566, 1477.
- [L9Ni2(OAc)2]: MS (ESI) m/z: 683.2 ([M−2AcO+HCO2 −]+, 100%). IR (νC=O, cm−1, neat): 1566, 1477.
- [L10Ni2(OAc)2]: MS (ESI) m/z: 669.1 ([M−2OAc+O2CH]+, 100%). IR (νC=O, cm−1, neat): 1566, 1477.
- [L13Ni2(OAc)2]: MS (ES/CI) m/z: 855.2 ([M−2AcO−−2CH3+HCO2]+, 100%), 809.2 ([M−2AcO−−2CH3+1 HCO2 −]+, 80%).
- IR (νC=O, cm−1, neat): 1573, 1480.
- [L14Ni2(OAc)2]: IR (νC=O, cm−1, neat): 1566 and 1413.
- [L15Ni2(OAc)2]: MS (CI) m/z: 717 ([M−2AcO−+HCO2 −]+, 100%).
- IR (νC=O, cm−1, neat): 1562 and 1410.
-
- The complex [Limine 8Mg2(OAc)2] was prepared using the following method:
- Preparation of [Limine 8M2(OAc)2]:
- To a suspension of Li2Limine 8 (1 equiv.) in MeOH was added Mg(OAc)2.4H2O (2 equiv.). Reaction mixture was stirred overnight at RT. After this time, solvents were evaporated. Pentane was added and the reaction mixture was filtered. Filtrate was evaporated to yield complex [LimineMg2(OAc)2] as a slightly yellow solid.
- Limine 8Mg2(OAc)2: 1H NMR (400 MHz, CD3OD) δ 8.13 (d, J=2.0 Hz, 2H), 7.31 (d, J=2.7 Hz, 2H), 7.26 (d, J=2.7 Hz, 2H), 4.09-4.03 (m, 4H), 3.31-3.26 (m, 2H), 2.86-2.79 (m, 2H), 2.66 (d, J=11.3 Hz, 2H), 2.22-2.14 (m, 2H), 1.90-1.40 (s, br, 6H), 1.31 (s, 18H), 1.21 (s, 3H), 1.16 (s, 3H), 1.14 (s, 3H), 1.02 (s, 3H).
- MS (ESI) m/z: 639.3 ([M−2AcO−+HCO2 −], 100%).
- [LM2(OAc)2] (0.01 or 0.025 mmol) was dissolved in cyclohexene oxide (25 or 50 mmol) in a Schlenk. The vessel was degassed, charged with CO2 (1 bar) and heated at 100° C. with magnetic stirring for the right time, giving poly(cyclohexene carbonate). The polymer contained >99% carbonate linkages and was produced with >99% selectivity in all cases. The asymmetric ligands L1-L4 having N-substitution demonstrate superior activity, productivity (turnover number) and activity under low loadings. All the asymmetric complexes demonstrate excellent selectivity for polymer, activity under low pressures and narrow polydispersity polymers. The results are shown in Table 1.
-
TABLE 1 Copolymerisation of CHO and CO2 using [LM2(OAc)2] Vol Conversion CHO T P Time (PCHC + Cyclic Catalyst cat:CHO (mL) (° C.) (bar) (h) vs CHO [L1Ni2(OAc)2] 1:5000 5 100 1 3 44% [L1Ni2(OAc)2] 1:1000 2.5 100 1 1.17 51.8 [L2Ni2(OAc)2] 1:5000 5 100 1 3 44% [L3Ni2(OAc)2] 1:5000 5 100 1 3 47% [L4Ni2(OAc)2] 1:5000 5 100 1 3 48% [Limine 8Mg2(OAc)2] 1:1000 2.5 100 1 4 32.55% [L9Ni2(OAc)2] 1:1000 2.5 100 1 3 27.9% [L9Mg2(OAc)2] 1:1000 2.5 100 1 3 43.23% Selec- Catalyst tivity TON TOF PDI Mn [L1Ni2(OAc)2] 100% 2203 734 1.254 12600 [L1Ni2(OAc)2] 99.9% 518 443 1.018/ 16300/ 1.051 9200 [L2Ni2(OAc)2] 100% 2212 737 1.29 13100 [L3Ni2(OAc)2] 100% 2370 790 1.234 12900 [L4Ni2(OAc)2] 100% 2381 794 1.241 12900 [Limine 8Mg2(OAc)2] 100% 326 81 [L9Ni2(OAc)2] 99.5% 279 93 1.042/ 12700/ 1.095 5300 [L9Mg2(OAc)2] 100% 432 144 1.035/ 20400/ 1.196 6600 - [LxM2(OAc)2] (0.0148 mmol) was added to a dried Schlenk tube and dried under vacuum for 60 minutes. CHO (15 mL, 148.26 mmol) was added under N2 via a syringe, the mixture was transferred to a reactor under pressure 0.2 bar CO2. Reactor vessel was heated to 130° C., then pressured to 10 bar and stirred for 1-2 hours, after which the vessel was cooled to 5° C., the pressure slowly released and a sample taken for GPC/NMR analysis. The results are shown in Table 2.
-
TABLE 2 Comparison of catalytic activity of equivalent Ni and Mg complexes under identical conditions for CHO and CO2 (10 bar) copolymerisation at 1:10,000 loading. Conversion Vol (PCHC + CHO T P Time Cyclic Selec- Catalyst cat:CHO (mL) (° C.) (bar) (h) vs CHO tivity TON TOF PDI Mn [L11Mg2(OAc)2] 1:10000 15 130 10 2 44.2% 100% 4420 2210 1.192 15100 [L11Ni2(OAc)2] 1:10000 15 130 10 2 51.6% 98.5% 5156 2578 1.264 29400 [L1Ni2(OAc)2] 1:10000 15 130 10 1 44.5% 99.8% 4450 4450 1.234 21300 - Although the symmetrical magnesium catalyst [L11Mg2(OAc)2] and nickel catalyst [L11Ni2(OAc)2] perform well and have high selectivity and activity (TOF) the asymmetric catalyst [L1Ni2(OAc)2] has a far superior activity and produces the same turn-over-number in half the time. This clearly demonstrates the unexpected benefits that an asymmetric catalyst can give over a symmetric catalyst.
- [LxM2(OAc)2] (0.0043-0.21 mmol) was dissolved in propylene oxide (211 mmol) in a Schlenk tube and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the desired temperature ° C. The solution was stirred mechanically for the desired time, giving poly(propylene carbonate) as a white solid with a high selectivity for polymer and >99% carbonate linkages. The catalysts showed excellent activity, producing a high yield of polymer. The catalysts demonstrated significantly improved selectivity and activity when compared to symmetric catalyst [L1Ni2(OAc)2] and could be used at a much lower catalyst loading. The results are shown in Table 3.
-
TABLE 3 Copolymerisation of PO and CO2 using [LM2(OAc)2] Selectivity T P Time for Polymer Catalyst cat:PO (° C.) (bar) (h) polymer yield PDI Mn [L1Ni2(OAc)2] 1:5000 80 20 9 85% 6.8 g 1.027/ 34000/ 1.032 16900 [L2Ni2(OAc)2] 1:5000 80 20 9 89% 8 g 1.027/ 42600/ 1.030 21200 [L3Ni2(OAc)2] 1:5000 80 20 9 87% 7.8 g 1.025/ 38900/ 1.028 19300 [L1Ni2(OAc)2] 1:1000 70 20 16 87% 19 g 1.034/ 44500/ 1.030 22300 [L1Ni2(OAc)2] 1:50000 90 20 16 80% 2.2 g 1.1 19700 [L7Ni2(OAc)2] 1:1000 80 20 1 90% 8.5 g 1.02/ 17000/ 1.03 8600 [L11Ni2(OAc)2] 1:1000 80 20 16 75% 10.4 g 1.12 15200 - [L1Ni2(OAc)2] (0.21 mmol) and PPG-425 (4.3 mmol) was dissolved in propylene oxide (211 mmol) in a Schlenk tube and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the 80° C. The solution was stirred mechanically for the 6 hrs, giving a poly(propylenecarbonate) diol (9.2 g) as a clear viscous oil with a high selectivity for polymer and >99% carbonate linkages.
- [L1Ni2(OAc)2] (0.21 mmol) and 1,6-hexanediol (8.4 mmol) was dissolved in propylene oxide (211 mmol) in a Schlenk tube and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the 80° C. The solution was stirred mechanically for 12 hrs, giving a poly(propylenecarbonate) diol (6.4 g) as a clear viscous oil with a high selectivity for polymer and >99% carbonate linkages.
- [L1Ni2(OAc)2] (0.021 mmol) was dissolved in propylene oxide (106 mmol) in a Schlenk tube and a further 7.5 mL of dry toluene was added and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the 80° C. The solution was stirred mechanically for the 16 hrs, giving a toluene solution of poly(propylenecarbonate) which was isolated (5 g) as a white powder with a high selectivity for polymer and >99% carbonate linkages.
- [L1Ni2(OAc)2] (0.021 mmol) was dissolved in propylene oxide (106 mmol) in a Schlenk tube and a further 7.5 mL of dry n-butyl acetate was added and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the 80° C. The solution was stirred mechanically for 16 hrs, giving an n-butyl acetate solution of poly(propylenecarbonate) which was isolated (4.7 g) as a white powder with a high selectivity for polymer and >99% carbonate linkages.
- [L1Ni2(OAc)2] (0.105 mmol) was dissolved in tert-butyl glycidyl ether (105 mmol) in a Schlenk tube and the solution transferred into a pre-dried 100 mL stainless steel Parr pressure vessel using a syringe. The vessel was charged with CO2 (20 bar) and heated to the 80° C. The solution was stirred mechanically for 16 hrs, giving poly(tert-butylether 1,2-glycerol carbonate) which was isolated (8.6 g) as a white powder with a high selectivity for polym for polymer and >99% carbonate linkages.
- All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.
- Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
- The invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed
Claims (47)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/723,333 US20200140610A1 (en) | 2014-07-22 | 2019-12-20 | Catalysts |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB201412986A GB201412986D0 (en) | 2014-07-22 | 2014-07-22 | Catalysts |
GB201412990A GB201412990D0 (en) | 2014-07-22 | 2014-07-22 | Catalysts |
GB1412992.8 | 2014-07-22 | ||
GB1412990.2 | 2014-07-22 | ||
GB1412986.0 | 2014-07-22 | ||
GB201412992A GB201412992D0 (en) | 2014-07-22 | 2014-07-22 | Catalysts |
PCT/GB2015/052114 WO2016012785A1 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US201715327806A | 2017-01-20 | 2017-01-20 | |
US16/723,333 US20200140610A1 (en) | 2014-07-22 | 2019-12-20 | Catalysts |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2015/052114 Continuation WO2016012785A1 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US15/327,806 Continuation US10556988B2 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
Publications (1)
Publication Number | Publication Date |
---|---|
US20200140610A1 true US20200140610A1 (en) | 2020-05-07 |
Family
ID=53776894
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/327,677 Active US10030102B2 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US15/327,806 Active US10556988B2 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US16/014,079 Active US10774180B2 (en) | 2014-07-22 | 2018-06-21 | Catalysts |
US16/723,333 Pending US20200140610A1 (en) | 2014-07-22 | 2019-12-20 | Catalysts |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/327,677 Active US10030102B2 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US15/327,806 Active US10556988B2 (en) | 2014-07-22 | 2015-07-22 | Catalysts |
US16/014,079 Active US10774180B2 (en) | 2014-07-22 | 2018-06-21 | Catalysts |
Country Status (15)
Country | Link |
---|---|
US (4) | US10030102B2 (en) |
EP (2) | EP3180121B1 (en) |
JP (2) | JP6730273B2 (en) |
KR (2) | KR102523483B1 (en) |
CN (2) | CN106536047B (en) |
AU (2) | AU2015293702B2 (en) |
BR (2) | BR112017001086B1 (en) |
ES (1) | ES2962669T3 (en) |
MX (2) | MX2017000880A (en) |
MY (1) | MY181918A (en) |
PL (1) | PL3171975T3 (en) |
RU (2) | RU2696272C2 (en) |
SG (2) | SG11201700233XA (en) |
TW (2) | TWI675700B (en) |
WO (2) | WO2016012786A1 (en) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0807607D0 (en) | 2008-04-25 | 2008-06-04 | Imp Innovations Ltd | Catalyst |
GB201308978D0 (en) | 2013-05-17 | 2013-07-03 | Imp Innovations Ltd | Method for producing polymers and block copolymers |
BR112017001086B1 (en) | 2014-07-22 | 2020-12-15 | Econic Technologies Ltd | CATALYST, BINDER, ASYMMETRIC N-SUBSTITUTION PROCESS OF A SYMMETRIC BINDER, PROCESS, AND, PRODUCT |
GB201514506D0 (en) | 2015-08-14 | 2015-09-30 | Imp Innovations Ltd | Multi-block copolymers |
GB201515350D0 (en) * | 2015-08-28 | 2015-10-14 | Econic Technologies Ltd | Method for preparing polyols |
JP7096243B2 (en) | 2016-11-11 | 2022-07-05 | ダウ グローバル テクノロジーズ エルエルシー | Semi-batch process for making polycarbonate polyols through copolymerization of carbon dioxide and oxylan |
GB201703323D0 (en) * | 2017-03-01 | 2017-04-12 | Econic Tech Ltd | Method for preparing polyols |
GB201703324D0 (en) * | 2017-03-01 | 2017-04-12 | Econic Tech Ltd | Method for preparing polyether carbonates |
GB201703384D0 (en) | 2017-03-02 | 2017-04-19 | Econic Tech Ltd | Process for the production of Tetraaminobiphenol macrocyclic ligands; and novel Tetraaminobiphenol macrocyclic ligands |
GB201717459D0 (en) | 2017-10-24 | 2017-12-06 | Econic Tech Limited | Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates |
CN112262169A (en) | 2018-04-18 | 2021-01-22 | 沙特阿美技术公司 | Anomeric isomerization of poly (alkylene carbonate) polymers |
US11180609B2 (en) | 2018-08-02 | 2021-11-23 | Saudi Aramco Technologies Company | Sustainable polymer compositions and methods |
US11634539B2 (en) | 2018-09-24 | 2023-04-25 | Saudi Aramco Technologies Company | Polycarbonate block copolymers and methods thereof |
JP2022519024A (en) | 2019-01-31 | 2022-03-18 | ダウ グローバル テクノロジーズ エルエルシー | Purification process for polyether carbonate polyols |
GB201906214D0 (en) | 2019-05-02 | 2019-06-19 | Econic Tech Ltd | A polyol block copolymer, compositions and processes therefor |
GB201906210D0 (en) | 2019-05-02 | 2019-06-19 | Econic Tech Limited | A polyol block copolymer, compositions and processes therefor |
GB202003003D0 (en) | 2020-03-02 | 2020-04-15 | Econic Tech Ltd | A polyol block copolymer |
GB202003002D0 (en) | 2020-03-02 | 2020-04-15 | Crane Ltd | Method of preparation of a polyol block copolymer |
WO2021262845A1 (en) | 2020-06-24 | 2021-12-30 | Saudi Aramco Technologies Company | Polyol compositions and methods |
GB202017531D0 (en) | 2020-11-05 | 2020-12-23 | Econic Tech Limited | (poly)ol block copolymer |
US20230026948A1 (en) | 2021-06-23 | 2023-01-26 | Saudi Aramco Technologies Company | Polyol compositions and methods |
KR20240036722A (en) | 2021-08-11 | 2024-03-20 | 에코닉 테크놀로지 엘티디 | Method for producing surfactants by copolymerization of epoxide and CO2 using a mixture of macrocyclic binary metal catalyst and double metal cyanide catalyst |
GB202115335D0 (en) | 2021-10-25 | 2021-12-08 | Econic Tech Ltd | Surface-active agent |
CN116284711A (en) * | 2022-03-23 | 2023-06-23 | 聚碳氧联新材料科技(无锡)有限公司 | Composition, catalyst for preparing polyester, and preparation method and application thereof |
GB2626546A (en) | 2023-01-25 | 2024-07-31 | Econic Tech Ltd | Surface-active agent |
GB2626989A (en) | 2023-02-10 | 2024-08-14 | Econic Tech Ltd | Surface-active agent |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013034750A2 (en) * | 2011-09-08 | 2013-03-14 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
US20130172524A1 (en) * | 2010-09-14 | 2013-07-04 | Novomer, Inc. | Catalysts and methods for polymer synthesis |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63280086A (en) | 1987-05-12 | 1988-11-17 | Hiroyoshi Shirai | Dinuclear complex of salt thereof and langmuir-blodgett membrane |
US20090062110A1 (en) * | 2006-02-08 | 2009-03-05 | Sumitomo Chemical Company Limited | Metal complex and use thereof |
JP2007238601A (en) | 2006-02-08 | 2007-09-20 | Sumitomo Chemical Co Ltd | Polynuclear metal complex modified product and application thereof |
CN102290584A (en) * | 2007-03-09 | 2011-12-21 | 独立行政法人产业技术综合研究所 | Electrode catalyst for fuel cell |
GB0807607D0 (en) | 2008-04-25 | 2008-06-04 | Imp Innovations Ltd | Catalyst |
US20140107333A1 (en) * | 2011-06-16 | 2014-04-17 | Shengqian Ma | Polyhedral cage-containing metalloporphyrin frameworks, methods of making, and methods of using |
GB201111928D0 (en) * | 2011-07-12 | 2011-08-24 | Norner As | Process |
BR112017001086B1 (en) | 2014-07-22 | 2020-12-15 | Econic Technologies Ltd | CATALYST, BINDER, ASYMMETRIC N-SUBSTITUTION PROCESS OF A SYMMETRIC BINDER, PROCESS, AND, PRODUCT |
-
2015
- 2015-07-22 BR BR112017001086-0A patent/BR112017001086B1/en active IP Right Grant
- 2015-07-22 KR KR1020177004888A patent/KR102523483B1/en active IP Right Grant
- 2015-07-22 MX MX2017000880A patent/MX2017000880A/en unknown
- 2015-07-22 AU AU2015293702A patent/AU2015293702B2/en active Active
- 2015-07-22 JP JP2017524121A patent/JP6730273B2/en active Active
- 2015-07-22 PL PL15745548.6T patent/PL3171975T3/en unknown
- 2015-07-22 CN CN201580038784.XA patent/CN106536047B/en active Active
- 2015-07-22 BR BR112017001081-0A patent/BR112017001081B1/en active IP Right Grant
- 2015-07-22 MX MX2017000884A patent/MX2017000884A/en unknown
- 2015-07-22 EP EP15745549.4A patent/EP3180121B1/en active Active
- 2015-07-22 JP JP2017524122A patent/JP6728162B2/en active Active
- 2015-07-22 ES ES15745548T patent/ES2962669T3/en active Active
- 2015-07-22 SG SG11201700233XA patent/SG11201700233XA/en unknown
- 2015-07-22 EP EP15745548.6A patent/EP3171975B1/en active Active
- 2015-07-22 SG SG11201700229VA patent/SG11201700229VA/en unknown
- 2015-07-22 US US15/327,677 patent/US10030102B2/en active Active
- 2015-07-22 KR KR1020177004890A patent/KR102480993B1/en active IP Right Grant
- 2015-07-22 TW TW104123691A patent/TWI675700B/en active
- 2015-07-22 WO PCT/GB2015/052115 patent/WO2016012786A1/en active Application Filing
- 2015-07-22 CN CN201580038785.4A patent/CN106536048B/en active Active
- 2015-07-22 WO PCT/GB2015/052114 patent/WO2016012785A1/en active Application Filing
- 2015-07-22 AU AU2015293703A patent/AU2015293703B2/en active Active
- 2015-07-22 TW TW104123690A patent/TWI660778B/en active
- 2015-07-22 US US15/327,806 patent/US10556988B2/en active Active
- 2015-07-22 RU RU2017105138A patent/RU2696272C2/en active
- 2015-07-22 MY MYPI2017700218A patent/MY181918A/en unknown
- 2015-07-22 RU RU2017105139A patent/RU2706004C2/en active
-
2018
- 2018-06-21 US US16/014,079 patent/US10774180B2/en active Active
-
2019
- 2019-12-20 US US16/723,333 patent/US20200140610A1/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130172524A1 (en) * | 2010-09-14 | 2013-07-04 | Novomer, Inc. | Catalysts and methods for polymer synthesis |
WO2013034750A2 (en) * | 2011-09-08 | 2013-03-14 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10556988B2 (en) | Catalysts | |
AU2015214217B2 (en) | Catalyst | |
JP2020509128A (en) | Method for preparing polycarbonate ether polyol | |
US20230100282A1 (en) | Method for preparing polyether carbonates | |
US20200339749A1 (en) | Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates | |
JP2024050584A (en) | Method for quenching polymerization process | |
US20200062898A1 (en) | Method for preparing polyols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ECONIC TECHNOLOGIES LTD, GREAT BRITAIN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHAPMAN, ANDY;CHARTOIRE, ANTHONY;LEELAND, JAMES;AND OTHERS;SIGNING DATES FROM 20170208 TO 20170612;REEL/FRAME:051348/0023 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STCV | Information on status: appeal procedure |
Free format text: NOTICE OF APPEAL FILED |
|
STCV | Information on status: appeal procedure |
Free format text: NOTICE OF APPEAL FILED |
|
STCV | Information on status: appeal procedure |
Free format text: APPEAL BRIEF (OR SUPPLEMENTAL BRIEF) ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |