WO2014028281A1 - B-alkyl-substituted ammonia boranes - Google Patents
B-alkyl-substituted ammonia boranes Download PDFInfo
- Publication number
- WO2014028281A1 WO2014028281A1 PCT/US2013/053914 US2013053914W WO2014028281A1 WO 2014028281 A1 WO2014028281 A1 WO 2014028281A1 US 2013053914 W US2013053914 W US 2013053914W WO 2014028281 A1 WO2014028281 A1 WO 2014028281A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- alkyl
- compound
- compounds
- substituted
- Prior art date
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- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical class B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 52
- 239000001257 hydrogen Substances 0.000 claims description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- -1 hydride compounds Chemical class 0.000 description 39
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002915 spent fuel radioactive waste Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 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 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 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
- 0 CB(N(B(*)N(B1*)*)*)N1* Chemical compound CB(N(B(*)N(B1*)*)*)N1* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 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 1
- 238000003491 array Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl 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
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([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
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 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 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000003707 hexyloxy 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 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000002463 lignoceryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 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 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 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
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- UJGFGHBOZLCAQI-UHFFFAOYSA-N tris(phosphanyl) borate Chemical compound POB(OP)OP UJGFGHBOZLCAQI-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- Hydrogen has the potential to replace petroleum as the primary fuel for transportation and remote power applications.
- One significant hurdle that must be overcome is the development of safe (for example, ambient pressure and temperature, non-toxic), efficient (high gravimetric hydrogen density), and convenient (mild H 2 release conditions) storage methods for hydrogen.
- Boron-nitrogen containing chemical hydride compounds have received considerable recent attention as possible hydrogen storage materials due to their high gravimetric density and favorable kinetics of hydrogen release.
- Ammonia borane (AB, H 3 N-BH 3 , 19.6 wt % H 2 ) and /V-substituted derivatives of AB have been the focus numerous literature reports detailing hydrogen release conditions, and characterization and regeneration of spent-fuel material.
- R 1 is selected from H, or an optionally- substituted alkyl
- R is an optionally-substituted alkyl.
- a hydrogen storage system that includes at least one of the compounds disclosed herein. Also disclosed herein are methods for releasing hydrogen from any one of the above- described compounds or hydrogen storage systems.
- Figure 1 is a graph showing catalytic dehydrogenation of two prior art compounds (AB and MeAB) compared to two novel compounds 1 and 2 disclosed herein.
- R-group refers to a single atom (for example, a halogen atom) or a group of two or more atoms that are covalently bonded to each other, which are covalently bonded to an atom or atoms in a molecule to satisfy the valency requirements of the atom or atoms of the molecule, typically in place of a hydrogen atom.
- R-groups/substituents include alkyl groups, hydroxyl groups, alkoxy groups, acyloxy groups, mercapto groups, and aryl groups.
- Substituted or “substitution” refer to replacement of a hydrogen atom of a molecule or an R-group with one or more additional R-groups such as halogen, alkyl, alkoxy, alkylthio, trifluoromethyl, acyloxy, hydroxy, mercapto, carboxy, aryloxy, aryl, arylalkyl, heteroaryl, amino, alkylamino, dialkylamino, morpholino, piperidino, pyrrolidin-l-yl, piperazin-l-yl, nitro, sulfato or other R-groups.
- R-groups such as halogen, alkyl, alkoxy, alkylthio, trifluoromethyl, acyloxy, hydroxy, mercapto, carboxy, aryloxy, aryl, arylalkyl, heteroaryl, amino, alkylamino, dialkylamino, morpholino, piperidino, pyrrol
- alkyl refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, w-propyl, isopropyl, w-butyl, isobutyl, i-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
- a "lower alkyl” group is a saturated branched or unbranched hydrocarbon having from 1 to 6 carbon atoms. Preferred alkyl groups have 1 to 4 carbon atoms.
- Alkyl groups may be "substituted alkyls" wherein one or more hydrogen atoms are substituted with a substituent such as halogen, cycloalkyl, alkoxy, amino, hydroxyl, aryl, alkenyl, or carboxyl.
- a lower alkyl or (C 1 -C 6 )alkyl can be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, or hexyl;
- (C 3 -C 6 )cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl;
- (C 3 -C 6 )cycloalkyl(C 1 -C 6 )alkyl can be cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 2-cyclopropylethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, or 2-cyclohexylethyl;
- (C 1 -C 6 )alkoxy can be methoxy, ethoxy, prop
- hydroxy(C 1 -C 6 )alkyl can be hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- hydroxybutyl, 4-hydroxybutyl, 1-hydroxypentyl, 5-hydroxypentyl, 1 -hydroxyhexyl, or 6- hydroxyhexyl;
- (C 1 -C 6 )alkoxycarbonyl can be methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, or hexyloxycarbonyl;
- C 1 -C 6 )alkylthio can be methylthi
- B-substituted ammonia borane compounds having a structure of:
- R 1 is selected from H, or an optionally- substituted alkyl
- R is an optionally-substituted alkyl.
- R 1 is H. In certain embodiments, R 1 is a CrC 6 alkyl, particularly methyl. In certain embodiment, R is a C -C alkyl, particularly methyl.
- the compounds disclosed herein are useful as hydrogen storage materials.
- methods for storing and/or releasing hydrogen from the compounds described herein include releasing hydrogen from at least one B-alkyl substituted ammonia borane under conditions sufficient to produce at least one borazine, and optionally hydrogenating the borazine.
- the hydrogen may be released and/or added during the hydrogen storage cycle in any form.
- the hydrogen may be released and/or added as a formal equivalent of dihydrogen.
- a formal equivalent of dihydrogen is two hydrogen atoms, whether the hydrogen atoms are added to the substrate as dihydrogen (during hydrogenation), as hydride ions, or as protons.
- the combination of a hydride ion and a proton formally constitutes one equivalent of dihydrogen.
- the compounds are capable of releasing hydrogen both thermally and/or catalytically.
- Thermal release includes heating the compound at a sufficiently high temperature to affect release of at least one dihydrogen equivalent.
- the compound may be heated at a temperature of at least 50°C, particularly at least 150°C.
- Catalytic release of hydrogen includes contacting the compound with a metal halide catalyst at conditions sufficient for causing hydrogen release.
- the catalytic dehydrogenation optionally is conducted with heating such as at a temperature from 50 to 200°C, more particularly 50 to 80°C.
- the metal species of the metal halide catalyst may be selected, for example, from a transition metal, particularly a first-row transition metal.
- Illustrative metals include iron, cobalt, copper, nickel and illustrative halides include fluorine, chlorine, bromine, and iodine.
- the dehydrogenated product is a borazine compound having a structure of Formula II:
- each R is independently selected from H, or an optionally- substituted alkyl; and each R is independently an optionally- substituted alkyl.
- R 1 is H. In certain embodiments, R 1 is a CrC 6 alkyl, particularly methyl.
- R is a C -C alkyl, particularly methyl.
- R and R in the fully-dehydrogenated product is dependent upon the structure of the fully-charged (i.e., saturated) compound.
- the dehydrogenated product(s) may be regenerated by hydrogenating the dehydrogenated product(s).
- the dehydrogenated product(s) are also referred to herein as "spent fuel.”
- the hydrogen storage system may include at least one of the compounds described above.
- the hydrogen storage system may include a port for the introduction of hydrogen for subsequent storage. Similarly, it may include a tap or port for the collection of regenerated hydrogen gas.
- Such a hydrogen storage system may be incorporated into a portable power cell, or may be installed in conjunction with a hydrogen-burning engine.
- the hydrogen storage system may be used in or with a hydrogen-powered vehicle, such as an automobile.
- the hydrogen storage device may be installed in or near a residence, as part of a single-home or multi-home hydrogen- based power generation system. Larger versions of the hydrogen storage device may be used in conjunction with, or in replacements for, conventional power generating stations.
- the hydrogen storage system may also utilize one or more additional methods of hydrogen storage in combination with the presently disclosed compounds, including storage via compressed hydrogen, liquid hydrogen, and/or slush hydrogen.
- the hydrogen storage system may include alternative methods of chemical storage, such as via metal hydrides, carbohydrates, ammonia, amine borane complexes, formic acid, ionic liquids, phosphonium borate, or carbonite substances, among others.
- the hydrogen storage system may include methods of physical storage, such as via carbon nanotubes, metal-organic frameworks, clathrate hydrates, doped polymers, glass capillary arrays, glass microspheres, or keratine, among others.
- Extended heating of the mixture causes the intermediate species to converge to a single product, which is identified as the trimeric species hexamethylborazene 3 in the case of 1, and 2,4,6-trimethylborazene 4 in the case of 2, on the basis of their U B NMR chemical shifts.
- compound 3 was isolated in 71 % yield.
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Abstract
A compound having a structure of the formula (I) wherein R1 is selected from H or an optionally-substituted alkyl; and R2 is an optionally-substituted alkyl.
Description
B-ALKYL-SUBSTITUTED AMMONIA BORANES
This application claims the benefit of U.S. Provisional Application No. 61/683,073, filed August 14, 2012, which is incorporated herein by reference in its entirety.
BACKGROUND
Hydrogen has the potential to replace petroleum as the primary fuel for transportation and remote power applications. One significant hurdle that must be overcome is the development of safe (for example, ambient pressure and temperature, non-toxic), efficient (high gravimetric hydrogen density), and convenient (mild H2 release conditions) storage methods for hydrogen. Boron-nitrogen containing chemical hydride compounds have received considerable recent attention as possible hydrogen storage materials due to their high gravimetric density and favorable kinetics of hydrogen release. Ammonia borane (AB, H3N-BH3, 19.6 wt % H2) and /V-substituted derivatives of AB have been the focus numerous literature reports detailing hydrogen release conditions, and characterization and regeneration of spent-fuel material.
SUMMARY Disclosed herein is a compound having a structure of:
H H
R1 N B R2
H H wherein R1 is selected from H, or an optionally- substituted alkyl; and
R is an optionally-substituted alkyl.
Further disclosed herein is a hydrogen storage system that includes at least one of the compounds disclosed herein.
Also disclosed herein are methods for releasing hydrogen from any one of the above- described compounds or hydrogen storage systems.
The foregoing will become more apparent from the following detailed description, which proceeds with reference to the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing catalytic dehydrogenation of two prior art compounds (AB and MeAB) compared to two novel compounds 1 and 2 disclosed herein.
DETAILED DESCRIPTION
The following explanations of terms and methods are provided to better describe the present compounds, compositions and methods, and to guide those of ordinary skill in the art in the practice of the present disclosure. It is also to be understood that the terminology used in the disclosure is for the purpose of describing particular embodiments and examples only and is not intended to be limiting.
An "R-group" or "substituent" refers to a single atom (for example, a halogen atom) or a group of two or more atoms that are covalently bonded to each other, which are covalently bonded to an atom or atoms in a molecule to satisfy the valency requirements of the atom or atoms of the molecule, typically in place of a hydrogen atom. Examples of R-groups/substituents include alkyl groups, hydroxyl groups, alkoxy groups, acyloxy groups, mercapto groups, and aryl groups.
"Substituted" or "substitution" refer to replacement of a hydrogen atom of a molecule or an R-group with one or more additional R-groups such as halogen, alkyl, alkoxy, alkylthio, trifluoromethyl, acyloxy, hydroxy, mercapto, carboxy, aryloxy, aryl, arylalkyl, heteroaryl, amino, alkylamino, dialkylamino, morpholino, piperidino, pyrrolidin-l-yl, piperazin-l-yl, nitro, sulfato or other R-groups.
The term "alkyl" refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, w-propyl, isopropyl, w-butyl, isobutyl, i-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. A "lower alkyl" group is a saturated branched or unbranched hydrocarbon having from 1 to 6 carbon atoms. Preferred alkyl groups have 1 to 4 carbon atoms. Alkyl groups may be "substituted alkyls" wherein one or more
hydrogen atoms are substituted with a substituent such as halogen, cycloalkyl, alkoxy, amino, hydroxyl, aryl, alkenyl, or carboxyl. For example, a lower alkyl or (C1-C6)alkyl can be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, or hexyl; (C3-C6)cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; (C3-C6)cycloalkyl(C1-C6)alkyl can be cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 2-cyclopropylethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, or 2-cyclohexylethyl; (C1-C6)alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec-butoxy, pentoxy, 3-pentoxy, or hexyloxy; (C2-C6)alkenyl can be vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1- hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5- hexenyl; (C2-C6)alkynyl can be ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1- hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, or 5- hexynyl; (Ci-C6)alkanoyl can be acetyl, propanoyl or butanoyl; halo(C1-C6)alkyl can be
iodomethyl, bromomethyl, chloromethyl, fluoromethyl, trifluoromethyl, 2-chloroethyl, 2- fluoroethyl, 2,2,2-trifluoroethyl, or pentafluoroethyl; hydroxy(C1-C6)alkyl can be hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- hydroxybutyl, 4-hydroxybutyl, 1-hydroxypentyl, 5-hydroxypentyl, 1 -hydroxyhexyl, or 6- hydroxyhexyl; (C1-C6)alkoxycarbonyl can be methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, or hexyloxycarbonyl; (C1-C6)alkylthio can be methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, or hexylthio; (C2-C6)alkanoyloxy can be acetoxy, propanoyloxy, butanoyloxy, isobutanoyloxy, pentanoyloxy, or hexanoyloxy.
Disclosed herein are B-substituted ammonia borane compounds having a structure of:
H H
R1 N B R2
H H
Formula I
wherein R1 is selected from H, or an optionally- substituted alkyl; and
R is an optionally-substituted alkyl.
In certain embodiments, R1 is H. In certain embodiments, R1 is a CrC6 alkyl, particularly methyl.
In certain embodiment, R is a C -C alkyl, particularly methyl.
1 2
The compound in which R is H and R is methyl has a gravimetric hydrogen capacity of
1 2
8.9 wt hydrogen. The compound in which R is methyl and R is methyl has a gravimetric hydrogen capacity of 6.8 wt hydrogen.
The compounds disclosed herein are useful as hydrogen storage materials. In further embodiments disclosed herein, there are provided methods for storing and/or releasing hydrogen from the compounds described herein. For example, disclosed herein are hydrogen storage methods that include releasing hydrogen from at least one B-alkyl substituted ammonia borane under conditions sufficient to produce at least one borazine, and optionally hydrogenating the borazine. The hydrogen may be released and/or added during the hydrogen storage cycle in any form. For example, the hydrogen may be released and/or added as a formal equivalent of dihydrogen. A formal equivalent of dihydrogen is two hydrogen atoms, whether the hydrogen atoms are added to the substrate as dihydrogen (during hydrogenation), as hydride ions, or as protons. For example, the combination of a hydride ion and a proton formally constitutes one equivalent of dihydrogen.
Release of hydrogen from the compounds disclosed herein may be accomplished by several approaches. For example, the compounds are capable of releasing hydrogen both thermally and/or catalytically. Thermal release includes heating the compound at a sufficiently high temperature to affect release of at least one dihydrogen equivalent. For instance, the compound may be heated at a temperature of at least 50°C, particularly at least 150°C. Catalytic release of hydrogen includes contacting the compound with a metal halide catalyst at conditions sufficient for causing hydrogen release. The catalytic dehydrogenation optionally is conducted with heating such as at a temperature from 50 to 200°C, more particularly 50 to 80°C. The metal species of the metal halide catalyst may be selected, for example, from a transition metal, particularly a first-row transition metal. Illustrative metals include iron, cobalt, copper, nickel and illustrative halides include fluorine, chlorine, bromine, and iodine.
The dehydrogenated product is a borazine compound having a structure of Formula II:
Formula II
1 2 wherein each R is independently selected from H, or an optionally- substituted alkyl; and each R is independently an optionally- substituted alkyl.
In certain embodiments, R1 is H. In certain embodiments, R1 is a CrC6 alkyl, particularly methyl.
In certain embodiment, R is a C -C alkyl, particularly methyl.
1 2
The structure of R and R in the fully-dehydrogenated product is dependent upon the structure of the fully-charged (i.e., saturated) compound.
The dehydrogenated product(s) may be regenerated by hydrogenating the dehydrogenated product(s). The dehydrogenated product(s) are also referred to herein as "spent fuel."
The hydrogen storage system may include at least one of the compounds described above. The hydrogen storage system may include a port for the introduction of hydrogen for subsequent storage. Similarly, it may include a tap or port for the collection of regenerated hydrogen gas.
Such a hydrogen storage system may be incorporated into a portable power cell, or may be installed in conjunction with a hydrogen-burning engine. The hydrogen storage system may be used in or with a hydrogen-powered vehicle, such as an automobile. Alternatively, the hydrogen storage device may be installed in or near a residence, as part of a single-home or multi-home hydrogen- based power generation system. Larger versions of the hydrogen storage device may be used in conjunction with, or in replacements for, conventional power generating stations.
The hydrogen storage system may also utilize one or more additional methods of hydrogen storage in combination with the presently disclosed compounds, including storage via compressed hydrogen, liquid hydrogen, and/or slush hydrogen. Alternatively, or in addition, the hydrogen storage system may include alternative methods of chemical storage, such as via metal hydrides, carbohydrates, ammonia, amine borane complexes, formic acid, ionic liquids, phosphonium borate,
or carbonite substances, among others. Alternatively, or in addition, the hydrogen storage system may include methods of physical storage, such as via carbon nanotubes, metal-organic frameworks, clathrate hydrates, doped polymers, glass capillary arrays, glass microspheres, or keratine, among others.
Disclosed herein is the first synthesis of two novel boron-substituted AB derivatives 1 and 2 with 6.8 wt% H2 and 8.9 wt% H2, respectively. It was found that at 150 °C compounds 1 and 2 quickly and cleanly release 2 equivalents of H2 per molecule. Catalytic dehydrogenation conditions were developed (5 mol% CoCl2, 80 °C) and found that 1 and 2 each release ca. 2 equivalents of H2 in less than 20 minutes (Figure 1). Under identical catalytic dehydrogenation conditions, AB release ca. 2 equivalents in >150 minutes and N-Me-AB (MeAB) released ca. 1.5 equivalents H2 in >300 minutes. The favorable H2 release properties and high gravimetric hydrogen capacity of compounds 1 and 2 substantiate these compounds as potential hydrogen storage materials.
A synthesis scheme (Scheme 1) for the compounds disclosed herein is shown below.
Treating Li[MeBH3] with the appropriate commercially available amine-hydrochloride salt led to the loss of one equivalent of H2 and generated compounds 1 and 2 in 88% and 75% isolated yield, respectively.
R = Me, H 1 2
88% 75%
Scheme 1
Examples
7
Synthesis of Compound 1. To a stirring solution of Li[MeBH3] (0.135 H H
g, 3.77 mmol) in Et20 (10 mL) was added MeNH Cl (0.255 g, 3.77 e-N-B- e
H H
mmol). The slurry was allowed to stir for 1 hour, and then filtered 1
through an Acrodisc. The majority of the solvent (75%) was removed under reduced pressure and pentane was added to cause precipitation of the product. The solvent layer was removed by pipet and the solid residue was washed two times with pentane to give 1 as a white crystalline solid (0.191 g, 88% yield).
1H NMR (300 MHz, CD2C12): δ 3.35 (t br, 2H, N-H), 2.54 (t, 3JHH = 4.0 Hz, 3H, N-Me), 1.82 (q br, BH = 90 Hz, 2H, B-H), 0.20 (s br, 3H, B-Me). 13C NMR (125 MHz, THF-d8): δ 30.64, 0.49 (br). UB NMR (96.27 MHz, CD2C12): δ -11.17 (t, 3JBH = 95 Hz). HRMS (EI+) calcd. for C2H8NB (-H2) 57.074980 found 57.074987.
H H
Synthesis of Compound 2. To a stirring solution of Li[MeBH3] (0.075 g, ^_|\j_g_^
2.10 mmol) in Et20 (10 mL) was added NH4C1 (0.112 g, 2.10 mmol). H H
The slurry was allowed to stir for 1 hour, and then filtered through an ^
Acrodisc. The majority of the solvent (75%) was removed under reduced pressure and pentane was added to cause precipitation of the product. The solvent layer was removed by pipet and the solid residue was washed two times with pentane to give 2 as a white crystalline solid (0.072 g, 75% yield).
1H NMR (300 MHz, CD2C12): δ 3.37 (t br, 3H, N-H), 2.93 (q br, 4JBH = 90 Hz, 2H, B-H), -0.17 (s br, 3H, B-Me). UB NMR (96.27 MHz, CD2C12): δ -14.56 (t, 3JBH = 93 Hz).
Comparison of Rates and Extent of Dehydrogenation
Dehydrogenation experiments were performed using an automated gas burette apparatus, which enabled determination of both the rate and amount of hydrogen released. CoCl2 was selected as the catalyst for these studies. The results of the burette experiment are depicted in Figure 1. The B-methyl substituted linear AB derivatives 1 and 2 displayed a rapid rate of hydrogen release; in the case of 2, releasing ca. 1.75 equivalents of H2. Notably, both of the non-B -alkyl substituted compounds, MeAB and AB, displayed markedly slower rates of hydrogen release under these conditions. Ammonia borane released ca. 2 equiv. H2 in 150 minutes and MeAB released only ca. 1.25 equiv. H2 in 240 minutes. These results indicate that the novel 5-substituted AB derivatives 1 and 2 could potentially be useful as hydrogen storage materials, storing 6.8 wt.% and 8.9 wt.% hydrogen, respectively.
Regeneration
Facile recharging of spent material with fresh hydrogen equivalents is a critical for the widespread adoption of any chemical platform for hydrogen storage. In the case of ammonia borane, researchers have recently developed methods for the regeneration of a model AB spent fuel material, polyborazylene (PB), using digestion strategies based on benzenedidthol/Sn-H or hydrazine/NH . However, PB is just one of several potential products that can result from AB
dehydrogenation. It was found that under both thermal and catalytic conditions, 1 and 2 initially form a mixture of dehydrogenated compounds. Extended heating of the mixture (36 hours) causes the intermediate species to converge to a single product, which is identified as the trimeric species hexamethylborazene 3 in the case of 1, and 2,4,6-trimethylborazene 4 in the case of 2, on the basis of their UB NMR chemical shifts. After catalytic dehydrogenation of 1 in refluxing THF using our standard catalyst and loading (5 mol CoCl2), compound 3 was isolated in 71 % yield.
Me
R-N-^N-R
3 RH2N-BH2Me
catalytic (5 mol% CoCI2, 80°C)
or thermal (150 °C, no cat)
36 hours
1 R = Me 3 R = Me, isolated in 71 % yield
2 R = H 4 R = H, observed by 1 1 B NMR
Scheme 2. Single product formation in the dehydrogenation of 1 and 2.
A route to regenerate the fully charged compound 1 from the spent material 3 was developed and is illustrated in Scheme 3. Activation of 3 with 3 equiv. formic acid generates the BN-cyclohexane analog 5. A crystal of 5 suitable for single X-ray diffraction was isolated, which unambiguously confirms its structural assignment. Interestingly, additional equivalents of formic acid do not add to boron or break the central BN ring, even in 10-fold excess. However, addition of LiAlH4 to 5 does break apart the trimer and cleaves the B-0 bonds to install the B(H)2 moieties. (Treatment of 3 directly with L1AIH4 without pre-treatment with formic acid was not sufficient to break the ring; only unreacted starting material was recovered.) Workup using wet THF as a proton source gives 1, which was isolated in 46% yield.
Scheme 3. Regeneration of spent fuel trimer 3 to fully charged compound 1.
In view of the many possible embodiments to which the principles of the disclosure may be applied, it should be recognized that the illustrated embodiments are only preferred examples of the disclosure and should not be taken as limiting the scope of the disclosure.
Claims
1. A compound having a structure of:
H H
R1 N B R2 H H wherein R1 is selected from H or an optionally-substituted alkyl; and
R is an optionally-substituted alkyl.
2. The compound of claim 1, wherein R1 is selected from H and CrC6 alkyl.
3. The compound of claim 1, wherein R1 is H.
4. The compound of claim 1, wherein R1 is CrC6 alkyl.
5. The compound of claim 1, wherein R1 is methyl.
6. The compound of any one of claims 1 to 5, wherein R is CrC6 alkyl.
7. The compound of any one of claims 1 to 6, wherein R is methyl.
8. A hydrogen storage system comprising at least one compound of any one of claims 1 to
7.
9. A method for releasing hydrogen from at least one compound of any one of claims 1 to
7, the method comprising heating the at least one compound, contacting the at least one compound with a catalyst, or simultaneously heating the at least one compound and contacting the at least one compound with a catalyst.
10. The method of claim 9, wherein the catalyst is CoCl2.
11. The method of claim 9 or 10, wherein the method produces a compound having the structure of:
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WO2018107239A1 (en) | 2016-12-15 | 2018-06-21 | University Of Technology, Sydney | Hydrogen storage and delivery material |
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CN105949229A (en) * | 2016-06-29 | 2016-09-21 | 武汉大学苏州研究院 | Synthetic method of B-substituted aminoborane |
WO2018107239A1 (en) | 2016-12-15 | 2018-06-21 | University Of Technology, Sydney | Hydrogen storage and delivery material |
CN110603259A (en) * | 2016-12-15 | 2019-12-20 | 悉尼科技大学 | Hydrogen storage and delivery materials |
JP2020502166A (en) * | 2016-12-15 | 2020-01-23 | ユニバーシティ・オブ・テクノロジー・シドニーUniversity Of Technology Sydney | Hydrogen storage / supply materials |
EP3555108A4 (en) * | 2016-12-15 | 2020-05-20 | University Of Technology Sydney | Hydrogen storage and delivery material |
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