CN104379814A - Anodic oxidation of organic substrates in the presence of nucleophiles - Google Patents
Anodic oxidation of organic substrates in the presence of nucleophiles Download PDFInfo
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- CN104379814A CN104379814A CN201380031601.2A CN201380031601A CN104379814A CN 104379814 A CN104379814 A CN 104379814A CN 201380031601 A CN201380031601 A CN 201380031601A CN 104379814 A CN104379814 A CN 104379814A
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- alkyl
- aryl
- organic compound
- general formula
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- Prior art date
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- 239000000758 substrate Substances 0.000 title claims description 9
- 230000003647 oxidation Effects 0.000 title description 3
- 238000007254 oxidation reaction Methods 0.000 title description 3
- 239000012038 nucleophile Substances 0.000 title 1
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000012429 reaction media Substances 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 35
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 11
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012434 nucleophilic reagent Substances 0.000 claims description 47
- 238000005868 electrolysis reaction Methods 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- 150000001721 carbon Chemical group 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- -1 C 1-C 6alkyl-carbonyl oxygen Chemical compound 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 150000002892 organic cations Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000005099 aryl alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002075 main ingredient Substances 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 2
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical compound N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CRDYSYOERSZTHZ-UHFFFAOYSA-N selenocyanic acid Chemical compound [SeH]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- HEVMDQBCAHEHDY-UHFFFAOYSA-N (Dimethoxymethyl)benzene Chemical compound COC(OC)C1=CC=CC=C1 HEVMDQBCAHEHDY-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000003115 supporting electrolyte Substances 0.000 description 17
- 150000002431 hydrogen Chemical class 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 150000001241 acetals Chemical class 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 13
- FIMHASWLGDDANN-UHFFFAOYSA-M methyl sulfate;tributyl(methyl)azanium Chemical compound COS([O-])(=O)=O.CCCC[N+](C)(CCCC)CCCC FIMHASWLGDDANN-UHFFFAOYSA-M 0.000 description 13
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 238000006056 electrooxidation reaction Methods 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003153 chemical reaction reagent Substances 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
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- 238000006359 acetalization reaction Methods 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000006198 methoxylation reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 1
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 1
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 125000000320 amidine group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000004122 cyclic 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 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
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
This invention refers to a process of anodic substitution comprising the electrolyzing the liquid reaction medium in an electrochemical cell comprising a cathode and an anode, whereas the liquid reaction medium comprises an organic compound with at least one carbon bound hydrogen atom, a nucleophilic agent, and an ionic liquid in a proportion of at least 10 % by weight, and whereas the said hydrogen atoms are replaced at least partially with the nucleophilic group of said nucleophilic agent. Preferably, a gas diffusion layer electrode is used as anode.
Description
The present invention relates to a kind of method that anode replaces, it is included in the electrolytes in electrochemical cells precursor reactant medium comprising negative electrode and positive electrode, wherein this liquid reaction medium comprises and has at least one key and be connected to the organic compound of the hydrogen atom of carbon, nucleophilic reagent and account for the ionic liquid of ratio of at least 10 % by weight, and wherein this hydrogen atom replaced by the nucleophilic group of this nucleophilic reagent at least partly.In a preferred embodiment of the invention, gas diffusion layers electrode is used as anode.Preferred nucleophilic reagent is fatty alcohol and aliphatic carboxylic acid.Preferred ionic liquid is the quaternary ammonium compound under normal atmosphere (1 bar) with the fusing point being less than 200 DEG C.
Matrix nucleophilic reagent exist under anodic oxidation (within the scope of this invention also referred to as electrochemical oxidation) for organic electrochemistry in allow a kind of important reaction type carrying out anode replacement.Different nucleophilic reagents can be used for (Eberson & Nyberg, Tetrahedron1976,32,2185) in this valuable synthesis electrolysis.Utilize the alkanol as methyl alcohol, the alkoxylate (EP 1348043B, EP 1111094 A) of matrix can be carried out.Utilize as HCOOH, CH
3cOOH or CF
3the acid of COOH, can carry out the acyloxylation effect (EP 1111094A) of matrix.And known fluoridizing can be used as a kind of mode optionally introducing fluorine.(Fuchigami, Organic Electrochemistry, the 4th edition, (editor: Lund & Hammerich), Dekker, New York, the 2001,1035th page).Total, if the first step provides sufficiently stable cation group thus the attack of nucleophilic reagent can produce the product be substituted from matrix except de-electronation, then can preferably carry out this anode replacement.
Such as can technical scale use anode to replace in the dual methoxylation through methyl substituted aromatic substance, produce corresponding acetal.First methoxylation step is provided as the ether of intermediate product and follow-up methoxylation produces acetal in battery/mono-processing procedure.By the mode of this grace, by toluene derivative as the p-t-Butylbenzaldehyde from p-tert-butyltoluene can synthesis of aromatic aldehyde (DE2848397).
But this electrosynthesis also exists shortcoming, such as, show the limited substrate range for the acetalization through methyl substituted aromatic substance.If substituting group be electronics repulsive-type maglev as the tertiary butyl in above industrial example, then the acetalization of toluene derivative that contraposition is substituted could success.If the non-electronic repulsive-type maglev of para-orienting group, then selectivity is extremely low.This problem be not resolved in decades.
Such as, and if a kind of non-required reaction path is followed in the reaction that the obvious problem that anode replaces is nucleophilic reagent and matrix, ring compound such as ethylene carbonate and nucleophilic reagent react under open loop.Therefore, ethylene carbonate ring replacement usually not by nucleophilic reagent but group approach carry out.
Unexpectedly, a kind of method replacing (transformation efficiency, selectivity, current productive rate and the accessibility for the large-scale organic compound of anode replacement) by utilizing macroion liquid electrolyte concentration generally can improve anode is found.
The method also allows to carry out tending to nucleophilic side reaction such as the anode of the organic compound of the ring-opening reaction of cyclic carbonate and replaces.
The invention provides a kind of method that anode replaces, it comprises the following steps:
A) providing package is connected to the organic compound of the hydrogen atom of carbon atom containing at least one key;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of this organic compound and nucleophilic reagent;
C) this liquid reaction medium of electrolysis is replaced by the nucleophilic group of this nucleophilic reagent to make described hydrogen atom at least partially,
It is characterized in that this liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
The method that this anode replaces is the special case of electrochemical oxidation.
Utilize the key character that the liquid reaction medium comprising the ionic liquid of the ratio accounting at least 10 % by weight is method according to the present invention.
Within the scope of this invention, term ionic liquid refers to have under normal atmosphere (1 bar) be less than 200 DEG C, is preferably less than 150 DEG C, is especially preferably less than the salt (compound of positively charged ion and negatively charged ion) of the fusing point of 100 DEG C.
Possible ionic liquid also comprises the mixture of different ionic liquid.
Preferred ionic liquid comprises the organic compound as positively charged ion (organic cation).Depend on the chemical valence of negatively charged ion, ionic liquid can comprise other positively charged ions, and it comprises the metallic cation except organic cations.The positively charged ion of especially preferred ionic liquid is only organic cation, or when multivalent anions, different organic cations mixture.Suitable organic cation comprise in specific words heteroatoms as nitrogen, sulphur, oxygen or phosphorus; In specific words, organic cation comprises ammonium group (ammonium cation), oxygen
group (oxygen
positively charged ion), sulfonium group (sulfonium cation) Huo Phosphonium group (phosphonium cation).
In one particular embodiment, the organic cation of ionic liquid is ammonium cation, and it is for the present invention:
-there is the non-aromatic compound of localization positive charge on nitrogen-atoms, such as have trivalent nitrogen compound (quaternary ammonium compound) or
-there is trivalent nitrogen compound, one of them key is double bond, or
-there is delocalized positive charge and at least one nitrogen-atoms in aromatic ring system, the preferably aromatic substance of 1 to 3 nitrogen-atoms.
Preferred organic cation is quaternary ammonium cation, on nitrogen-atoms, preferably have 3 or 4 aliphatic substituting groups, especially preferably C
1-C
12those of alkyl; This aliphatic substituting group can optionally be replaced by hydroxyl.
Within the scope of this invention, term C
1-C
12alkyl comprises straight chain or branched chain and saturated or unsaturated C
1-C
12alkyl.C
1-C
12alkyl is preferably saturated.
Equally preferably comprise and have 1 to 3, especially 1 or 2 nitrogen-atoms is as the organic cation of the heterocyclic system of the composition of member ring systems.Monocycle, bicyclic aromatic or non-aromatic ring system.For example, the bicyclic system be described in WO 2008/043837 can be mentioned.The bicyclic system of WO 2008/043837 is the diazabicyclo derivative preferably formed by 7 Yuans rings and 6 Yuans rings, and it comprises amidine
group; Especially 1,8-diazabicylo (5.4.0) 11 carbon-7-alkene can be mentioned
positively charged ion.
Especially preferred ammonium cation is quaternary ammonium cation, imidazoles
positively charged ion, pyrimidine
positively charged ion and pyrazoles
positively charged ion.
Ionic liquid can comprise inorganic or organic anion.This negatively charged ion is described in such as above-mentioned WO03/029329, WO 2007/076979, WO 2006/000197 and WO 2007/128268.
Be preferably selected from following negatively charged ion:
Formula R
aoSO
3 -alkyl sulfate,
Wherein R
afor C
1-C
12alkyl, perfluor C
1-C
12alkyl or C
6-C
10aryl, preferred C
1-C
6alkyl, perfluor C
1-C
6alkyl or C
6-aryl (tosylate);
Formula R
asO
3 -alkyl azochlorosulfonate,
Wherein R
afor C
1-C
12alkyl, preferred C
1-C
6alkyl;
Formula (R
asO
2)
2n
-two alkyl sulfonyl imide,
Wherein R
afor C
1-C
12alkyl or perfluor C
1-C
12alkyl, preferred C
1-C
6alkyl or perfluor C
1-C
6alkyl;
Halogen ion, particularly chlorion, bromide anion or iodide ion;
Accurate halogen ion is as thiocyanate ion, dicyanamide;
Formula R
acOO
-carboxylate radical,
Wherein R
afor C
1-C
12alkyl, preferred C
1-C
6alkyl, especially acetate moiety;
Phosphate radical, especially formula R
ar
bpO
4 -acidic phosphates root,
Wherein R
aand R
bbe respectively C independently of one another
1-C
6alkyl; Particularly, R
aand R
bfor identical alkyl (such as dimethyl phosphate radical or diethylphosphate root); And
Phosphonate radical, particularly formula R
apO
3 -monoalkyl-phosphonic acid root,
Wherein R
afor C
1-C
6alkyl.
Suitable ionic liquid in scope of the present invention is such as alkylsurfuric acid tetra-allkylammonium (as methyl tributyl ammonium (MTBS)) or two (alkyl sulphonyl) imide tetra-allkylammonium (as two (trifluoromethyl sulfonyl) imide methyltributylammoni,m (MTB-TFSI) or two (trifluoromethyl sulfonyl) imide four octyl group ammonium).
Ionic liquid or its mixture account for the ratio of whole liquid reaction medium should up at least 10 % by weight, and preferably at least 25 % by weight, more preferably at least 50 % by weight, especially at least 65 % by weight.
The electrode of any applicable electrochemical oxidation process can be used as anode and negative electrode.Those skilled in the art can determine which kind of electrode is applicable to.
In a preferred embodiment of the invention, at least one gas diffusion layers electrode is used as anode.
Gas diffusion layers (GDL) electrode can be known and be made up of substrate and the microporous layers comprised as the carbon granule of main ingredient by fuel cell technology.Especially at US 4,748,095, US 4,931,168 and US5,618, describe suitable GDL in 392.The instruction of those documents is incorporated to herein by reference.Suitable GDL can be buied from such as Ballard Power Systems Inc., Freudenberg FCCT KG (such as the g. of H2315 series) or SGL Group.
The microporous layers (MPL) that GDL generally comprises layer of fibers or substrate and is made up of the carbon granule sticked each other.The degree of hydrophobization can change in the mode of adjustable wetting and ventilation property.
For the GDL electrode of method of the present invention preferably not containing the catalyzer be carried on electrode surface.
GDL electrode package for method of the present invention contains substrate and comprises the microporous layers as the carbon granule of main ingredient, preferably carbon black.
GDL electrode for method of the present invention can according to US 6,103,077, and finally utilization can be buied component and be manufactured as substrate and carbon granule.
Negative electrode is preferably selected from Pt, Pb, Ni, graphite, felt material as coal or graphite felt goods, stainless steel and GDL electrode.
Method according to the present invention step a) in the organic compound that provides generally can be and comprise at least one direct key and be connected to carbon atom and any organic compound of the hydrogen atom that be replaced by nucleophilic group under the condition that can replace at anode.Certainly, the mixture of organic compound can also be utilized.Suitable person be with at least one nucleophilic reagent, with the ionic liquid and optionally and the organic compound of solvent and/or additive combination of ratio accounting at least 10 % by weight, allow to be formed and there is the liquid reaction medium of ionic conductivity, thus electrolysis can be applied replace to cause anode.
Preferably, the direct key of hydrogen atom is connected to the carbon atom of the part into alkyl.According to the present invention, 1,2 or 3 direct key of hydrogen atom is connected to this carbon atom.The allyl system carbon atom of the diene of the tertiary carbon atom of the preferred alkane of this carbon atom or naphthenic hydrocarbon, alkene or cycloolefin or correspondence, be positioned at the alpha position of the aromatic hydrocarbons structure division of relative alkylaromatic hydrocarbon carbon atom, be positioned at the carbon atom of the alpha position of the nitrogen-atoms of relative acid amides or be positioned at the carbon atom of alpha position of Sauerstoffatom of relative ether.
Preferably represent according to organic compound of the present invention and there is the alkyl or alkenyl that at least one direct key is connected to the hydrogen atom of carbon atom.Especially preferred organic compound is alkane or the naphthenic hydrocarbon that (i) has that at least one direct key is connected to the hydrogen atom of tertiary carbon atom; (ii) there is at least one direct key and be connected to the alkene of the hydrogen atom of allyl system carbon atom or the diene of cycloolefin or correspondence; (iii) there is the alkylaromatic hydrocarbon that at least one direct key is connected to the hydrogen atom of the carbon atom of the alpha position being positioned at relative aromatic hydrocarbons structure division; (iv) there is the acid amides that at least one direct key is connected to the hydrogen atom of the carbon atom of the alpha position being positioned at relative nitrogen-atoms; Or (v) has at least one direct key and is connected to the ether of the hydrogen atom of the carbon atom of the alpha position being positioned at relative Sauerstoffatom, ester, carbonic ether or acetal.
Organic compound can comprise and is essentially stable functional group at reaction conditions.Suitable functional group comprises carbonyl, thiocarbonyl, ester, thioesters, acid amides, oxygen base ketonic oxygen base, carbamate, urea, hydroxyl, alkylsulfonyl,-sulfinic acid ester, sulphonate, sulfuric ester, ether, amine, nitrile etc. and combination thereof.
In one embodiment of the invention, step a) in the organic compound that provides be the compound being selected from general formula I,
Wherein
X is O, N-R
3or CR
4r
5,
R
1be selected from C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, formyl radical, C
1-C
6alkyl-carbonyl and C
1-C
6alkoxy carbonyl,
If wherein X is CR
4r
5group, R
1also can be C
1-C
6alkoxyl group,
If wherein X is N-R
3or CR
4r
5group, R
1also can be C
1-C
6alkyl-carbonyl oxygen base,
R
2be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
3-C
12cycloalkyl and C
6-C
10aryl,
R
3be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, formyl radical, C
1-C
6alkyl-carbonyl and C
1-C
6alkoxy carbonyl,
R
4and R
5independently selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl and C
1-C
6alkoxyl group,
Or R
1and R
2and 5-to 7-element heterocycle is formed together with X-(the C=O)-O of its key company, it can comprise at least one and be selected from O, S, NR
cor other the heteroatoms of C=O or containing heteroatomic group, wherein R
cbe selected from hydrogen, alkyl, cycloalkyl and aryl,
Or X is CR
4r
5group and R
1and R
4and with its key with carbon atom together with form 3 to 7 Yuans carbocyclic rings.
Preferably, X is O, CH
2or NR
3, wherein R
3for C
1-C
4-alkyl or C
1-C
4-alkyl-carbonyl.
In a preferred embodiment, R
1and R
2and 5-to 7-element heterocycle is formed together with X-(the C=O)-O of its key company, it can comprise at least one and be selected from O, S, NR
cor other the heteroatoms of C=O or containing heteroatomic group, wherein R
cbe selected from hydrogen, alkyl, cycloalkyl or aryl.In this embodiment, X is preferably O, CH
2or NR
3, wherein R
3for C
1-C
4-alkyl or C
1-C
4-alkyl-carbonyl.And, in this embodiment, R
1and R
2together for being selected from formula-CH
2-CH
2-,-CH
2-CH
2-CH
2-and-CH (C
xh
2x+1)-CH
2-group, wherein x is 1,2,3 or 4.
In another embodiment of the invention, step a) in the organic compound that provides be the compound being selected from general formula I a,
Wherein
X is O, CH
2or NR
3, wherein R
3for C
1-C
4-alkyl or C
1-C
4-alkyl-carbonyl,
A is alkylidene group, and it is selected from-CH
2-,-CH
2-CH
2-,-CH
2-CH
2-CH
2-,-CHR
7-,-CHR
7-CH
2-,-CH
2-CHR
7-,-CHR
7-CH
2-CH
2-,-CH
2-CHR
7-CH
2-, and-CH
2-CH
2-CHR
7-, wherein R
7for C
1-C
6alkyl,
R
6for hydrogen or C
1-C
6alkyl.
Preferably, X is O or-CH
2-, A is-CH
2-or-CHR
7-, wherein R
7for C
1-C
4-alkyl, and R
6for hydrogen or C
1-C
4-alkyl.
The example of suitable general formula I and the organic compound of Ia is ethylene carbonate, propylene carbonate, (4-methyl isophthalic acid, 3-bis-
alkane-2-ketone) and gamma-butyrolactone.
In one embodiment of the invention, step a) in the organic compound that provides be the compound being selected from general formula I I,
Z-CHR
8R
9(II)
Wherein
Z is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group ,-NR
10r
11group and C
1-C
6alkoxyl group,
R
8be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl,
If wherein Z is C
6-C
10aryl or C
1-C
6-allyl group, R
8also can be C
1-C
6alkoxyl group,
R
9be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, C
6-C
10aryl-C
1-C
6alkyl, and C
3-C
12cycloalkyl, or
R
8and R
9form C together
4-C
7-alkylidene group or C
4-C
7-alkenylene, and
R
10and R
11independently selected from hydrogen, C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, and C
1-C
6alkyl-carbonyl,
Or wherein
Z, R
8and R
9be C independently
1-C
6alkyl.
Preferably, Z is C
6-C
10aryl or the C be substituted
6-C
10aryl, and R
8and R
9independently selected from hydrogen, C
1-C
6alkyl and C
1-C
6alkoxyl group, especially preferably, Z is C
6-C
10aryl or the C be substituted
6-C
10aryl, and R
8and R
9independently selected from hydrogen, C
1-C
4-alkyl and C
1-C
4-alkoxyl group.
Also preferred, Z is C
1-C
6alkoxyl group, R
8be selected from hydrogen and C
1-C
6alkyl, and R
9be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, C
6-C
10aryl and the C be substituted
6-C
10aryl, especially preferably, Z is C
1-C
4-alkoxyl group, R
8be selected from hydrogen and C
1-C
4-alkyl, and R
9be selected from hydrogen, C
1-C
4-alkyl, C
1-C
4-alkoxyl group, C
6-C
10aryl and the C be substituted
6-C
10aryl.
The example of the organic compound of suitable general formula I I is toluene, phenmethyl methyl ether and benzaldehyde dimethyl acetal.
Within the scope of this invention, term C
1-C
6alkyl comprises straight chain or branched chain and saturated or unsaturated C
1-C
6alkyl.Preferably, C
1-C
6alkyl is saturated.C
1-C
6the example of alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl and n-hexyl.
Also the Alliyl moieties in alkoxyl group is applicable to above about the note of alkyl.
Within the scope of this invention, term " cycloalkyl " represents usually have 3 to 12 carbon atoms, the preferably cycloaliphatic groups of 5 to 8 carbon atoms, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norcamphane base, two rings [2.2.2] octyl group or adamantyl.
Within the scope of this invention, term C
6-C
10aryl refers to list or multi-cyclic aromatic alkyl.C
6-C
10aryl is preferably phenyl or naphthyl.
Within the scope of this invention, the C that is substituted of term
6-C
10aryl refers to have 1 to 3 aromatic hydrogen atom be substituted, preferably the list of 1 hydrogen atom or multi-cyclic aromatic alkyl.Preferably, this substituting group is independently selected from C
1-C
6alkyl and C
1-C
6alkoxyl group.Substituting group is preferably located in contraposition.This substituent example is p-methoxyl group, the p-tertiary butyl or p-methyl.
Step b in method according to the present invention) in, a kind of liquid reaction medium of the ionic liquid, organic compound and the nucleophilic reagent that comprise the ratio accounting at least 10 % by weight is provided.
Step b) in nucleophilic reagent used can be the mixture of any reagent or reagent, this reagent provides stable and can utilize the nucleophilic reagent of the hydrogen atom of nucleophilic group substituted organic compound during anode replaces under electrolysis conditions.
The general formula that anode according to the present invention replaces is
R-H+Nu
-→R-Nu+H
++2e
-，
Wherein R-H is organic compound as above and Nu
-for nucleophilic reagent.Importantly, this formula left side comprises two kinds of materials that can not react each other, and wherein this does not represent the fact removing two electronics from system.
By Nu
-the nucleophilic reagent represented might not be electronegative.Nucleophilic reagent in scope of the present invention can be such as pyridine (C
5h
5n).In this case, the substitution product of positively charged is obtained.
Nucleophilic reagent in scope of the present invention is the compound with nucleophilic group.Nucleophilic group or nucleophilic reagent itself can be used as nucleophilic reagent with having at least one key and be connected in the nucleophilic substitution reaction of the organic compound of the hydrogen atom of close carbon atoms.In the process of nucleophilic substitution reaction, this hydrogen atom is replaced by nucleophilic group.In some cases, nucleophilic group is equal to nucleophilic reagent (such as pyridine (C
5h
5n)).Within the scope of this invention, term nucleophilic reagent refers to aggressive reagent (such as C
5h
5n, RO
-and RCOO
-, and comprise ROH, RCOOH), and term nucleophilic group refers to displacement group (such as RO
-or RCOO
-but not ROH or RCOOH).
Preferred nucleophilic reagent of the present invention is selected from HO
-, RO
-, ROH, RCOO
-, RCOOH, NO
2 -, NO
3 -, N
3 -, OCN
-, SCN
-, RSO
3 -, SeCN
-, CN
-, Cl
-, Br
-and I
-, and R represents alkyl or aryl, preferred alkyl.Especially preferred nucleophilic reagent of the present invention is RO
-, ROH, RCOO
-or RCOOH.
Utilize nucleophilic reagent HO
-, RO
-, RCOO
-or NO
3 -anode replace and cause the formation of C-O key:
R-H+R ' COO
-→ R-OCOR '+H
++ 2e
-(effect of anode acyloxylation)
R-H+R ' O
-→ R-OR '+H
++ 2e
-(anode oxyalkylation)
R-H+HO
-→ R-OH+H
++ 2e
-(anode hydroxylation)
R-H+NO
3 -→ R-ONO
2+ H
++ 2e
-(anode nitrification)
R-H+R’SO
3 -→R-OSO
2R’+H
++2e
-。
Utilize nucleophilic reagent N
3 -, OCN
-or NO
2 -anode replace and cause the formation of C-N key:
R-H+N
3 -→ R-N
3+ H
++ 2e
-(anode change nitrogenization)
R-H+OCN
-→R-NCO+H
++2e
-
R-H+NO
2 -→ R-NO
2+ H
++ 2e
-(anode nitration effect).
Utilize nucleophilic reagent CN
-anode replace and cause the formation of C-C key:
R-H+CN
-→ R-CN+H
++ 2e
-(anodic cyanation effect).
Nucleophilic reagent in scope of the present invention is the compound with nucleophilic group, and such as water (has nucleophilic group HO
-), alcohol (such as has nucleophilic group RO
-formula ROH person), carboxylic acid (such as has nucleophilic group RCOO
-formula RCOOH person), nitrous acid or its salt (has nucleophilic group NO
2 -), nitric acid or its salt (has nucleophilic group NO
3 -), hydrazoic acid or its salt (has nucleophilic group N
3 -), isocyanic acid or its salt (has nucleophilic group OCN
-), isothiocyanic acid or its salt (has nucleophilic group SCN
-), sulfonic acid (such as has nucleophilic group RSO
3 -formula RSO
3h person), different selenocyanic acid or its salt (has nucleophilic group SeCN
-), prussic acid or its salt (has nucleophilic group CN
-), hydrochloric acid or its salt (has nucleophilic group Cl
-), hydrogen bromide or its salt (has nucleophilic group Br
-) or hydrogen iodide or its salt (there is nucleophilic group I
-), wherein R represents alkyl or aryl, preferred alkyl.
Preferred nucleophilic reagent of the present invention is the alcohol of formula III
R
12OH (III)
Or the carboxylic acid of formula IV
R
13COOH (IV)，
Wherein R
12and R
13for C
1-C
12alkyl or C
1-C
12perfluoroalkyl, preferred C
1-C
6alkyl or C
1-C
6-perfluoroalkyl, especially preferably C
1-C
6alkyl.
In a particular embodiment of the process of the present invention, nucleophilic reagent does not comprise F
-.Therefore, in this specific embodiment, nucleophilic reagent does not comprise provides F
-compound (fluorizating agent).And in this specific embodiment, ionic liquid does not comprise this fluorizating agent.
Nucleophilic reagent (with regard to nucleophilic group) is preferably in the scope of 1:1 to 99:1 (nucleophilic reagent: organic compound) with the mol ratio of organic compound, is more preferably 2:1 to 99:1.
In a particular embodiment of the process of the present invention, step a) in the organic compound that provides be the compound being selected from general formula V,
Y-CH
2R
14(V)
Wherein
Y is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group and-NR
10r
11group,
R
14be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl and C
3-C
12cycloalkyl,
R
10and R
11as mentioned above,
And nucleophilic reagent is the alcohol of formula III as above,
Wherein in the process of anode method of substitution, two hydrogen atoms are subsequently by-OR
12group displacement, the acetal of production VI
Y-C(OR
12)
2R
14(VI)。
In one embodiment, the invention provides a kind of method that anode by comprising the steps replaces the acetal of preparation general formula VI as above:
A) organic compound of general formula V as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of this organic compound and general formula III as above;
C) this liquid reaction medium of electrolysis is to form the acetal of general formula VI,
It is characterized in that this liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
Preferably, at least one gas diffusion layers electrode is used as anode.
Toluene conversion is become benzaldehyde dimethyl acetal for utilizing methyl alcohol by an example of this acetal method.
In a particular embodiment of the process of the present invention, step a) in the organic compound that provides be the compound being selected from general formula V,
Y-CH
2R
14(V)
Wherein
Y is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group and-NR
10r
11group,
R
14be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl and C
3-C
12cycloalkyl,
R
10and R
11as mentioned above,
And nucleophilic reagent is the alcohol of formula III as above,
Wherein in the process of anode method of substitution, two hydrogen atoms are subsequently by-OR
12base is replaced, the acetal of production VI
Y-C (OR
12)
2r
14(VI), and
The acetal of its Chinese style VI is hydrolyzed subsequently, the aldehydes or ketones of production VIa
Y-COR
14(VIa)。
In one embodiment, the invention provides a kind of method being replaced the aldehydes or ketones of preparation general formula VIa as above by anode, it comprises the steps:
A) organic compound of general formula V as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of this organic compound and general formula III as above;
C) this liquid reaction medium of electrolysis is to form the acetal of general formula VI,
D) acetal of this general formula VI is hydrolyzed to form the aldehydes or ketones of general formula VIa,
It is characterized in that this liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
Preferably, at least one gas diffusion layers electrode is used as anode.
Toluene conversion becomes benzaldehyde dimethyl acetal and benzaldehyde dimethyl acetal to be hydrolyzed into phenyl aldehyde subsequently for utilizing methyl alcohol by an example of this preparation method.The scheme can known according to technology skilful person is hydrolyzed step.
Within the scope of this invention, term " liquid reaction medium " comprises the reaction medium of liquid phase under representing the reaction conditions replaced at anode.This liquid phase comprises enough organic compound and replaces to allow anode.Liquid phase not necessarily comprises the organic compound in homogeneous solution form, as long as contacted with the electrode (particularly anode) of electrochemical cell by enough organic compound.Therefore, liquid reaction medium can comprise in homogeneous solution, the organic compound of colloidal solution, molecular dispersions, Emulsion Phase or disperse phase.Finally, also the gas stream including organic compounds can be introduced in liquid reaction medium.
Liquid reaction medium in electrochemistry oxygen electrochemical cell comprises the ionic liquid of the ratio accounting for total liquid reaction medium at least 10 % by weight, a certain amount of organic compound dissolved and a certain amount of nucleophilic reagent dissolved wherein wherein.Method according to the present invention without any need for other solvent or additive to set up the anode substitution reaction with high conversion and fine selectivity.Particularly, ionic liquid used also works as conductivity salt (ionogen).
In one embodiment of the invention, liquid reaction medium does not comprise in fact other solvent or other additives, and quick-dissolving agent and other additives account for the gross weight of liquid reaction medium lower than 1 % by weight.
If liquid reaction medium comprises organic solvent, it is preferably selected from acetonitrile, ether, halogenation alkane, tetramethylene sulfone and composition thereof.
In a specific embodiments of the present invention, liquid reaction medium comprises at least one other additives as redox mediators and/or supporting electrolyte.
Redox mediators is used in indirect electrolytic.The representative instance of redox mediators is 2,2,6,6-tetramethyl pyridine-1-oxyradical (TEMPO), triarylamine are as three (2,4-dibromo phenyl) amine or halogenide is as bromide or iodide (Steckhan, Angewandte Chemie 1986,98,681-699).
In the present invention, preferred redox mediators is bromide or iodide salt, and especially bromide salt is as alkali bromides salt or tetraalkylphosphonium bromide ammonium salt.
In a specific embodiments of the present invention, liquid reaction medium comprises bromide as other additives or iodide salt.Preferably, in this specific embodiments, GDL electrode is used as anode and ionic liquid to account for total liquid reaction medium 30 to 70 % by weight, preferably 40 to 50 % by weight ratio and use.
Preferably, in this specific embodiments, step a) in the organic compound that provides be the compound being selected from general formula VII,
Y-CR
15 2H (VII)
Wherein
Y is described above,
R
15for C
1-C
12alkoxyl group, preferred C
1-C
6alkoxyl group,
And this nucleophilic reagent is the alcohol of formula III as above, wherein in the process of anode method of substitution, two hydrogen atoms are by-OR
10group displacement, the adjacent ester of production VIII,
Y-CR
15 2(OR
12)(VIII)。
In one embodiment, the invention provides a kind of method being replaced the adjacent ester of preparation general formula VIII as above by anode, it comprises the steps:
A) organic compound of general formula VII as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of this organic compound, bromide or iodide salt and general formula III as above;
C) acetal of this liquid reaction medium of electrolysis so that formation general formula VII,
It is characterized in that this liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
Preferably, at least one gas diffusion layers electrode is used as anode.
Compare the intervention alkoxylation process of the relevant current productive rate of record in prior art people such as (, Tetrahedron, 1986,42,553-560) Grosse Brinkhaus, this intervention alkoxylation process of acetal extremely adjacent ester is improved.
In one embodiment of the invention, step a) in the carboxylic acid of the organic compound that provides to be the compound of general formula I a as above and nucleophilic reagent be formula as above (IV).The carboxylic acid of the nucleophilic acid preferred formula IV within the scope of this embodiment, wherein R
13for C
4-C
12alkyl, preferably has the C of the tertiary carbon atom being in alpha position
4-C
6alkyl.Method of the present invention allows the organic compound (as ethylene carbonate or propylene carbonate) utilizing carboxylic acid anode to replace (acyloxylation effect) formula Ia, unexpectedly, it relates to and easily utilizes nucleophilic reagent to make ethylene carbonate open loop, even if acid is medium nucleophilic reagent.
Therefore, in one embodiment, the invention provides a kind of method being prepared the acyloxylation organic compound of general formula I b by anode replacement,
Wherein X, A and R
6as above described in the scope of general formula I a and
Wherein R
13for C
1-C
12alkyl or C
1-C
12perfluoroalkyl, preferred C
1-C
6alkyl or C
1-C
6-perfluoroalkyl, especially preferably has the C of the tertiary carbon atom being in alpha position
4-C
6alkyl, it comprises the steps:
A) organic compound of general formula I a as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the carboxylic acid of this organic compound and general formula I V as above;
C) the acyloxylation organic compound of this liquid reaction medium of electrolysis so that formation general formula I b,
It is characterized in that this liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
About the summary being suitable as the structure possibility of the electrolytic cell of the electrochemistry oxygen electrochemical cell of method of the present invention can see such as Pletcher & Walsh, Industrial Electrochemistry, the 2nd edition, 1990, London, the 60th page of ff.
Suitable electrochemical cell for electrochemical oxidation is non-separation type battery and separation type battery.Non-separation type battery only comprises an ionogen part usually; Separation type battery has two or more this part.(one pole) in parallel or connect (bipolar) single electrode can be connected.In a suitable embodiment, the electrochemical cell for electrochemical oxidation is the monopolar cell comprising GDL anode and negative electrode.In the embodiment that another is suitable, the electrochemical cell for electrochemical oxidation is the battery of the stacked electrode with bipolar connection.
In a preferred embodiment, electrochemistry oxygen electrochemical cell is plate and frame battery.At least one GDL electrode is preferably comprised for the plate and frame battery in method of the present invention.The battery of the type is primarily of being generally rectangular electrode plate and the frame composition around it.It can by polymer materials, and such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene difluoride (PVDF), PTFE etc. make.Battery lead plate and the frame be associated often are engaged with each other to form assembly unit.By being pressed together by this plate and frame unit a plurality of, the storehouse assembled according to the make of pressure filter can be obtained.And other frame unit (such as receiving interval gauze etc.) can insert in storehouse.
According to known anode substitution technique, nucleophilic group is consequently utilized to replace carbon bond hydrogen atom even at least partially by this liquid reaction medium of electrolysis, restricted condition is the ionic liquid that liquid reaction medium used comprises the ratio accounting at least 10 % by weight, then can carry out according to method of the present invention.
One or more anode and one or more negative electrode are placed in liquid reaction medium.According to the present invention, preferably at least anode is GDL electrode.Produce current potential (voltage) between the anode and the cathode, (anode replaces to cause oxidizing reaction at anode, namely the nucleophilic group utilizing carbon bond to connect replaces the hydrogen atom that one or more carbon bond connects), and cause reduction reaction (being mainly hydrogen evolution) at negative electrode.
Preferably, anode substitution reaction is carried out with the constant current applied; Namely circulate under constant voltage and constant current.Certainly also can as US 6,267, described in 865, interrupt the electric current by current cycle.
Step c) in the current density that applies in the scope that expert knows.Step c) in the current density that uses preferably at 10 to 250mA/cm
2scope in, more preferably at 10 to 100mA/cm
2scope in.
By ordinary method, anode substitution product can be separated from reaction medium preferably by distillation.The ordinary method known by those skilled in the art can carry out the distillation of reacting ejecta.Suitable device for the fractionation by distillation comprises distillation tower as tray-type column, and it can be furnished with bubble-cap, sieve plate, screen tray, filler, internals, valve, side exit etc.The interval wall type tower being furnished with side exit, recirculation part etc. is especially suitable.Two or the combination of plural distillation tower can be used for distillation.Other suitable devices are that vaporizer is as thin-film evaporator, falling-film evaporator, Sambay vaporizer etc. and combination thereof.
The liquid reaction medium comprising the ionic liquid of the ratio accounting at least 10 % by weight is utilized to have favourable influence to an at least following parameter in the method for the invention: the accessibility of the selectivity of nucleophilic substitution, the transformation efficiency of nucleophilic substitution reaction, current productive rate, space-time yield, battery life and the organic compound on a large scale for anode replacement.If GDL electrode is used as anode in addition, then this positive effect even can more show.Be not limited to any theory, the intermediate product of the nucleophilic substitution reaction of organic compound by inference, if the cation group such as produced during anodization step is by ionic liquid, stable and this ionic liquid system uses with GDL anode combination, then this is stablized even more preferably.
Embodiment
The following example is for further illustrating the present invention.
Comparative example 1
In the non-separation type electrolytic cell of 100ml, utilize graphite (10cm
2) anode and stainless steel cathode (10cm
2), electrolysis 6.5g toluene, 34.1g methyl alcohol, 2.6g reach 7F as the methyl tributyl ammonium (MTBS, 6 % by weight) of supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the toluene conversion of display 65%, the benzaldehyde dimethyl acetal selectivity of 7% and 2% current productive rate.The result of this experiment summarized by table 1.
Embodiment 2
In the non-separation type electrolytic cell of 100ml, utilize graphite (10cm
2) anode and stainless steel cathode (10cm
2), electrolysis 7.5g toluene, 17.0g methyl alcohol, 25.5g reach 7F as the methyl tributyl ammonium (MTBS, 51 % by weight) of supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the toluene conversion of display 88%, the benzaldehyde dimethyl acetal selectivity of 32% and 15% current productive rate.The result of this experiment summarized by table 1.
Embodiment 3
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 13.1g toluene, 29.5g methyl alcohol and 9.8g reach 7F as the methyl tributyl ammonium (MTBS, 12 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 87%, the benzaldehyde dimethyl acetal selectivity of 22% and 9% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 4
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 13.1g toluene, 29.5g methyl alcohol and 9.8g reach 7F as the methyl tributyl ammonium (MTBS, 25 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 89%, the benzaldehyde dimethyl acetal selectivity of 29% and 13% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 5
In the non-separation type electrolytic cell of 100ml, utilize commercially available GDL (from the H2315IX11CX45 of Freudenberg, 10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 13.1g toluene, 29.5g methyl alcohol and 9.8g reach 8F as the methyl tributyl ammonium (MTBS, 51 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 98%, the benzaldehyde dimethyl acetal selectivity of 45% and 21% current productive rate.The result of this experiment summarized by table 1.
Embodiment 6
In the non-separation type electrolytic cell of 100ml, utilize commercially available GDL (from the Sigracet GDL 25BC of SGL Group, 10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 7.9g toluene, 17.9g methyl alcohol and 26.9g reach 7F as the methyl tributyl ammonium (MTBS, 51 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 96%, the benzaldehyde dimethyl acetal selectivity of 45% and 23% current productive rate.The result of this experiment summarized by table 1.
Embodiment 7
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 7.6g toluene, 17.2g methyl alcohol and 25.8g reach 6F as the methyl tributyl ammonium (MTBS, 51 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 97%, the benzaldehyde dimethyl acetal selectivity of 48% and 25% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 8
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 8.1g toluene, 18.3g methyl alcohol and 27.4g reach 6F as the methyl tributyl ammonium (MTBS, 51 % by weight) of supporting electrolyte.Current density is 65mA/cm
2.GC analyze the toluene conversion of display 94%, the benzaldehyde dimethyl acetal selectivity of 49% and 27% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 9
In the non-separation type electrolytic cell of 100ml, utilize graphite (10cm
2) anode and stainless steel cathode (10cm
2), electrolysis 4.9g toluene, 10.9g methyl alcohol and 36.8g are as methyl tributyl ammonium (MTBS, the 70 % by weight) 6F of supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the toluene conversion of display 81%, the benzaldehyde dimethyl acetal selectivity of 30% and 15% current productive rate.The result of this experiment summarized by table 1.
Embodiment 10
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 5.2g toluene, 11.7g methyl alcohol and 39.4g reach 6F as the methyl tributyl ammonium (MTBS, 70 % by weight) of supporting electrolyte.Current density is 34mA/cm
2.GC analyze the toluene conversion of display 93%, the benzaldehyde dimethyl acetal selectivity of 50% and 28% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 11
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 5.9g toluene, 13.2g methyl alcohol and 44.4g are as two (trifluoromethyl sulfonyl) imide 1-ethyl-3-methyl-imidazoles of supporting electrolyte
(EMimid-TFSI, 70 % by weight) reach 6F.The current density applied is 34mA/cm
2.GC analyze the toluene conversion of display 98%, the benzaldehyde dimethyl acetal selectivity of 50% and 30% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 12
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 5.6g toluene, 12.7g methyl alcohol and 42.8g reach 6F as two (trifluoromethyl sulfonyl) imide methyltributylammoni,m (MTB-TFSI, 70 % by weight) of supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the toluene conversion of display 98%, the benzaldehyde dimethyl acetal selectivity of 50% and 32% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Embodiment 13
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 6.0g toluene, 13.5g methyl alcohol and 45.4g reach 5.5F as two (trifluoromethyl sulfonyl) imide methyltributylammoni,m (MTB-TFSI, 70 % by weight) of supporting electrolyte.The current density applied is 60mA/cm
2.GC analyze the toluene conversion of display 95%, the benzaldehyde dimethyl acetal selectivity of 54% and 35% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.The result of this experiment summarized by table 1.
Table 1: the acetalization of toluene
Comparative example 14
In the non-separation type electrolytic cell of 100ml, utilize graphite (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 6.7g benzaldehyde dimethyl acetal and 37.6g methyl alcohol and 0.45g reach 2.5F as the Sodium Bromide (1 % by weight) of amboceptor/supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the benzaldehyde dimethyl acetal transformation efficiency of display 18%, the adjacent ester selectivity of phenylformic acid of 49% and 7% current productive rate.
Comparative example 15
In the non-separation type electrolytic cell of 100ml, utilize graphite (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 6.1g benzaldehyde dimethyl acetal and 33.9g methyl alcohol and 0.82g reach 2.5F as the Tetrabutyl amonium bromide (2 % by weight) of amboceptor/supporting electrolyte.The current density applied is 34mA/cm
2.GC analyze the benzaldehyde dimethyl acetal transformation efficiency of display 24%, the adjacent ester selectivity of phenylformic acid of 59% and 11% current productive rate.
Embodiment 16
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 5.2g benzaldehyde dimethyl acetal, 21.2g methyl alcohol and as the 23.1g methyl tributyl ammonium (MTBS, 45 % by weight) of amboceptor and 2.2g Tetrabutyl amonium bromide (4 % by weight) 5F.The current density of application is 34mA/cm
2.GC analyze the benzaldehyde dimethyl acetal transformation efficiency of display 72%, the adjacent ester selectivity of phenylformic acid of 68% and 20% current productive rate.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.
Embodiment 17
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 4.9g benzaldehyde dimethyl acetal, 20.2g methyl alcohol and reach 5F as the 21.8g methyl tributyl ammonium (MTBS, 42 % by weight) of amboceptor and 5.1g Tetrabutyl amonium bromide (10 % by weight).The current density applied is 34mA/cm
2.GC analyze the benzaldehyde dimethyl acetal transformation efficiency of display 31%, the adjacent ester selectivity of phenylformic acid of 83% and 10% current productive rate.According to US6,103,077, utilize carbon black to manufacture GDL electrode.
Embodiment 18
In the non-separation type electrolytic cell of 100ml, utilize GDL (10cm
2) as anode and stainless steel cathode (10cm
2), electrolysis 5.6g ethylene carbonate, 27g PIVALIC ACID CRUDE (25) and 22.3g reach 4.7F as two (trifluoromethyl sulfonyl) imide four octyl groups ammonium (41 % by weight) of supporting electrolyte.The current density applied is 10mA/cm
2.NMR and GC analyzes the ethylene carbonate transformation efficiency of display 67%, 4-(tertiary butyl) carbonyl Oxy-1,3-bis-
the productive rate of alkane-2-ketone is 18%.According to US 6,103,077, carbon black is utilized to manufacture GDL electrode.
Claims (19)
1. a method for anode replacement, it comprises the following steps:
A) providing package is connected to the organic compound of the hydrogen atom of carbon atom containing at least one key;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of described organic compound and nucleophilic reagent;
C) liquid reaction medium described in electrolysis is replaced by the nucleophilic group of nucleophilic reagent to make described hydrogen atom at least partially,
It is characterized in that described liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
2. method as claimed in claim 1, wherein said anode is gas diffusion layers electrode.
3. method as claimed in claim 2, wherein said gas diffusion layers electrode package is containing substrate and comprise the microporous layers of carbon granule as main ingredient.
4. method as claimed in claim 2, wherein said gas diffusion layers electrode package is containing substrate and comprise the microporous layers of carbon black as main ingredient.
5. the method any one of claim 1-4, wherein said ionic liquid has the organic cation comprising ammonium.
6. the method any one of claim 1-5, wherein said organic compound is selected from as follows: (i) has alkane or the naphthenic hydrocarbon that at least one direct key is connected to the hydrogen atom of tertiary carbon atom; (ii) there is at least one direct key and be connected to the alkene of the hydrogen atom of allyl system carbon atom or the diene of cycloolefin or correspondence; (iii) there is the alkylaromatic hydrocarbon that at least one direct key is connected to the hydrogen atom of the carbon atom of the alpha position being in relative aromatic hydrocarbons structure division; (iv) there is the acid amides that at least one direct key is connected to the hydrogen atom of the carbon atom of the alpha position being in relative nitrogen-atoms; Or (v) has at least one direct key and is connected to the ether of the hydrogen atom of the carbon atom of the alpha position being in relative Sauerstoffatom, ester, carbonic ether or acetal.
7. the method any one of claim 1-5, wherein said organic compound is the compound of formula I,
Wherein
X is O, N-R
3or CR
4r
5,
R
1be selected from C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, formyl radical, C
1-C
6alkyl-carbonyl and C
1-C
6alkoxy carbonyl,
If wherein X is CR
4r
5group, R
1also can be C
1-C
6alkoxyl group,
If wherein X is N-R
3or CR
4r
5group, R
1also can be C
1-C
6alkyl-carbonyl oxygen base,
R
2be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
3-C
12cycloalkyl and C
6-C
10aryl,
R
3be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, formyl radical, C
1-C
6alkyl-carbonyl and C
1-C
6alkoxy carbonyl,
R
4and R
5independently selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl and C
1-C
6alkoxyl group,
Or R
1and R
2and 5-to 7-element heterocycle is formed together with X-(the C=O)-O group of its key company, it can comprise at least one and be selected from O, S, NR
cor other the heteroatoms of C=O or containing heteroatomic group, wherein R
cbe selected from hydrogen, alkyl, cycloalkyl and aryl,
Or X is CR
4r
5group and R
1and R
4and with its key with carbon atom together with form 3 to 7 Yuans carbocyclic rings.
8. the method any one of claim 1-5, wherein said organic compound is the compound of formula I,
Wherein
X is O, CH
2or NR
3, wherein R
3for C
1-C
4-alkyl or C
1-C
4-alkyl-carbonyl,
A is for being selected from-CH
2-,-CH
2-CH
2-,-CH
2-CH
2-CH
2-,-CHR
7-,-CHR
7-CH
2-,-CH
2-CHR
7-,-CHR
7-CH
2-CH
2-,-CH
2-CHR
7-CH
2-, and-CH
2-CH
2-CHR
7-alkylidene group,
Wherein R
7for C
1-C
6alkyl,
R
6for hydrogen or C
1-C
6alkyl.
9. the method any one of claim 1-5, wherein said organic compound is the compound of formula II,
Z-CHR
8R
9(II)
Wherein
Z is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group ,-NR
10r
11group and C
1-C
6alkoxyl group,
R
8be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl,
If wherein Z is C
6-C
10aryl or C
1-C
6-allyl group, R
8also can be C
1-C
6alkoxyl group,
R
9be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, C
6-C
10aryl-C
1-C
6alkyl and C
3-C
12cycloalkyl, or
R
8and R
9form C together
4-C
7-alkylidene group or C
4-C
7-alkenylene, and
R
10and R
11independently selected from hydrogen, C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, and C
1-C
6alkyl-carbonyl,
Or wherein
Z, R
8and R
9be C independently
1-C
6alkyl.
10. the method any one of claim 1-9, wherein said nucleophilic reagent is selected from water, alcohol, carboxylic acid, nitrous acid or its salt, nitric acid or its salt, hydrazoic acid (hydrozoic acid) or its salt, isocyanic acid or its salt, isothiocyanic acid or its salt, sulfonic acid, different selenocyanic acid or its salt, prussic acid or its salt, hydrogenchloride or its salt, hydrogen bromide or its salt or hydrogen iodide or its salt.
11. methods any one of claim 1-9, wherein said nucleophilic reagent is selected from as follows:
The alcohol of formula III
R
12OH (III)
Or the carboxylic acid of formula IV
R
13COOH (IV)，
Wherein R
12and R
13for C
1-C
12alkyl or C
1-C
12perfluoroalkyl.
Method any one of 12. claim 1-9, wherein said nucleophilic reagent does not comprise fluorizating agent.
Method any one of 13. claim 1-12, wherein said liquid reaction medium comprises the additive being selected from bromide salt and iodide salt in addition.
14. methods any one of claim 1-13, wherein said electrochemical cell is non-separation type battery.
15. methods any one of claim 1-14, wherein said negative electrode is selected from Pt, Pb, Ni, graphite, felt material as coal or graphite felt goods, stainless steel and GDL electrode.
16. 1 kinds replace the method preparing the acetal of general formula VI by anode,
Y-C(OR
12)
2R
14(VI)
It is by the organic compound of general formula V,
Y-CH
2R
14(V)
Wherein
Y is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group and-NR
10r
11group,
R
12for C
1-C
12alkyl or C
1-C
12perfluoroalkyl,
R
14be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl and C
3-C
12cycloalkyl,
R
10and R
11independently selected from hydrogen, C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, and C
1-C
6alkyl-carbonyl
It comprises the steps:
A) organic compound of general formula V as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of described organic compound and general formula III as claimed in claim 11;
C) acetal of liquid reaction medium described in electrolysis so that formation general formula VI,
It is characterized in that described liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
17. 1 kinds replace the method preparing the aldehydes or ketones of general formula VIa by anode,
Y-COR
14(VIa)
It is by the organic compound of general formula V
Y-CH
2R
14(V)
Wherein
Y is selected from C
6-C
10aryl, the C be substituted
6-C
10aryl, C
1-C
6-allyl group and-NR
10r
11group,
R
12for C
1-C
12alkyl or C
1-C
12perfluoroalkyl,
R
14be selected from hydrogen, C
1-C
6alkyl, C
1-C
6alkoxy-C
1-C
6alkyl, C
6-C
10aryl-C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl and C
3-C
12cycloalkyl,
R
10and R
11independently selected from hydrogen, C
1-C
6alkyl, C
6-C
10aryl, the C be substituted
6-C
10aryl, and C
1-C
6alkyl-carbonyl,
It comprises the steps:
A) organic compound of general formula V as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of described organic compound and general formula III as claimed in claim 11;
C) acetal of liquid reaction medium described in electrolysis so that formation general formula VI;
D) acetal of general formula VI is hydrolyzed to form the aldehydes or ketones of general formula VIa,
It is characterized in that described liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
18. 1 kinds of methods by the adjacent ester of anode replacement preparation formula VIII,
Y-CR
15 2(OR
12) (VIII)
It is by the organic compound of general formula VII
Y-CR
15 2H (VII)
Wherein
Y is described above,
R
12for C
1-C
12alkyl or C
1-C
12perfluoroalkyl,
R
15for C
1-C
12alkoxyl group,
It comprises the steps:
A) organic compound of general formula VII as above is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the alcohol of described organic compound, bromide or iodide salt and general formula III as claimed in claim 11;
C) acetal of liquid reaction medium described in electrolysis so that formation general formula VII,
It is characterized in that described liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
19. 1 kinds of methods by the acyloxylation organic compound of anode replacement preparation formula Ib,
It is by the organic compound of general formula I a as claimed in claim 8,
Wherein
X, A and R
6as claim 8 described in the scope of general formula I a and
R
13for C
1-C
12alkyl or C
1-C
12perfluoroalkyl,
It comprises the steps:
A) organic compound of general formula I a as claimed in claim 8 is provided;
B) in the electrochemical cell comprising negative electrode and positive electrode, providing package contains the liquid reaction medium of the carboxylic acid of described organic compound and general formula I V as claimed in claim 11;
C) the acyloxylation organic compound of liquid reaction medium described in electrolysis so that formation general formula I b,
It is characterized in that described liquid reaction medium comprises the ionic liquid of the ratio accounting at least 10 % by weight in addition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12172250.8 | 2012-06-15 | ||
| EP12172250 | 2012-06-15 | ||
| PCT/EP2013/061555 WO2013186094A2 (en) | 2012-06-15 | 2013-06-05 | Anodic oxidation of organic substrates in the presence of nucleophiles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104379814A true CN104379814A (en) | 2015-02-25 |
Family
ID=48628629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380031601.2A Pending CN104379814A (en) | 2012-06-15 | 2013-06-05 | Anodic oxidation of organic substrates in the presence of nucleophiles |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP2861785A2 (en) |
| JP (1) | JP2015527483A (en) |
| KR (1) | KR20150023709A (en) |
| CN (1) | CN104379814A (en) |
| CA (1) | CA2876566A1 (en) |
| TW (1) | TW201400469A (en) |
| WO (1) | WO2013186094A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of electrochemical oxidation synthesis method of amide and its application |
| CN109930171A (en) * | 2019-04-12 | 2019-06-25 | 天津理工大学 | A kind of method of green high-efficient synthesis acetal |
| CN111394747A (en) * | 2020-04-10 | 2020-07-10 | 浙江工业大学 | Green electrochemical synthesis method of 2-acyloxy aniline derivatives |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3321250A1 (en) * | 2016-11-15 | 2018-05-16 | Covestro Deutschland AG | Electrochemical method for the production of arylalkylcarbonates and diaryl carbonates |
| WO2019016903A1 (en) * | 2017-07-19 | 2019-01-24 | 宇部興産株式会社 | Nonaqueous electrolytic solution and electricity storage device using same |
| CN113046772B (en) * | 2021-03-18 | 2022-03-04 | 南华大学 | Electrochemical synthesis method of 4-selenopyrazole derivative |
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| DE3820895A1 (en) * | 1988-06-21 | 1989-12-28 | Basf Ag | PYRETHROIDS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR CONTROLLING PESTIES |
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- 2013-06-05 CA CA2876566A patent/CA2876566A1/en not_active Abandoned
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- 2013-06-05 KR KR20157000674A patent/KR20150023709A/en not_active Withdrawn
- 2013-06-05 JP JP2015516554A patent/JP2015527483A/en not_active Withdrawn
- 2013-06-05 CN CN201380031601.2A patent/CN104379814A/en active Pending
- 2013-06-05 EP EP13729287.6A patent/EP2861785A2/en not_active Withdrawn
- 2013-06-14 TW TW102121221A patent/TW201400469A/en unknown
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| US4405816A (en) * | 1980-12-24 | 1983-09-20 | Hoechst Aktiengesellschaft | 4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetal |
| WO1998000580A1 (en) * | 1996-06-28 | 1998-01-08 | E.I. Du Pont De Nemours And Company | In-situ halogenation of compounds in an electrochemical cell |
| US20010019020A1 (en) * | 1999-12-22 | 2001-09-06 | Basf Aktiengesellschaft | Process for electrochemical oxidation of organic compounds |
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| CN109321940A (en) * | 2018-11-30 | 2019-02-12 | 西南大学 | A kind of electrochemical oxidation synthesis method of amide and its application |
| CN109930171A (en) * | 2019-04-12 | 2019-06-25 | 天津理工大学 | A kind of method of green high-efficient synthesis acetal |
| CN109930171B (en) * | 2019-04-12 | 2020-01-17 | 天津理工大学 | A kind of green and efficient method for synthesizing acetal |
| CN111394747A (en) * | 2020-04-10 | 2020-07-10 | 浙江工业大学 | Green electrochemical synthesis method of 2-acyloxy aniline derivatives |
| CN111394747B (en) * | 2020-04-10 | 2021-03-30 | 浙江工业大学 | Green electrochemical synthesis method of 2-acyloxy aniline derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015527483A (en) | 2015-09-17 |
| TW201400469A (en) | 2014-01-01 |
| WO2013186094A3 (en) | 2014-07-24 |
| CA2876566A1 (en) | 2013-12-19 |
| EP2861785A2 (en) | 2015-04-22 |
| WO2013186094A2 (en) | 2013-12-19 |
| KR20150023709A (en) | 2015-03-05 |
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