CN104087968A - Selective electrochemical reduction method of halogenated picolinic acid or salt compound thereof - Google Patents
Selective electrochemical reduction method of halogenated picolinic acid or salt compound thereof Download PDFInfo
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- CN104087968A CN104087968A CN201410264884.1A CN201410264884A CN104087968A CN 104087968 A CN104087968 A CN 104087968A CN 201410264884 A CN201410264884 A CN 201410264884A CN 104087968 A CN104087968 A CN 104087968A
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- Prior art keywords
- acid
- reduction method
- electrochemical reduction
- haloperidid
- selective electrochemical
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Links
- 230000009467 reduction Effects 0.000 title claims abstract description 33
- -1 salt compound Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- 239000007769 metal material Substances 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 62
- KCDNYRPDKSGQCM-UHFFFAOYSA-N 4-[4-(3-chlorophenyl)-4-(pyrrolidine-1-carbonyl)piperidin-1-yl]-1-(4-fluorophenyl)butan-1-one Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(C=2C=C(Cl)C=CC=2)(C(=O)N2CCCC2)CC1 KCDNYRPDKSGQCM-UHFFFAOYSA-N 0.000 claims description 32
- 235000019253 formic acid Nutrition 0.000 claims description 31
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003929 acidic solution Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 abstract description 10
- 150000002367 halogens Chemical group 0.000 abstract description 7
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XTMUXJBJCMRWPG-UHFFFAOYSA-N 3-chloropyridine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=C1Cl XTMUXJBJCMRWPG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NBSITWJPOCDKDQ-UHFFFAOYSA-N C(=O)O.ClC=1C=NC=CC1 Chemical compound C(=O)O.ClC=1C=NC=CC1 NBSITWJPOCDKDQ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 0 *c1c(*)c(*)nc(*)c1* Chemical compound *c1c(*)c(*)nc(*)c1* 0.000 description 1
- SKURPVMALGSJSE-UHFFFAOYSA-N 3,4,5-trichloropyridine-2-carboxylic acid Chemical class OC(=O)C1=NC=C(Cl)C(Cl)=C1Cl SKURPVMALGSJSE-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- YVAVJQVBQRFJKV-UHFFFAOYSA-N C(=O)O.NC=1C=C(C=NC1)Cl Chemical compound C(=O)O.NC=1C=C(C=NC1)Cl YVAVJQVBQRFJKV-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UOYPZVOTNMVWHZ-UHFFFAOYSA-N formic acid 2,3,5-trichloropyridine Chemical compound C(=O)O.ClC=1C=NC(=C(C1)Cl)Cl UOYPZVOTNMVWHZ-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a selective electrochemical reduction method of halogenated picolinic acid or a salt compound of the halogenated picolinic acid, which comprises the following steps: taking an acid solution as a reaction medium, adding halogenated picolinic acid shown in the formula (II) or a salt compound of the halogenated picolinic acid into the acid solution to obtain an electrolytic reaction solution, carrying out an electrolytic reaction in an electrolytic cell which takes a chemical inert material as an anode and a metal material as a cathode, acidifying the electrolytic reaction solution after the electrolytic reaction is finished, and recovering to obtain a selective reduction product shown in the formula (I); in the invention, under the existence of 3-and 5-position or 3-position halogen substituent groups, 6-position halogen of polyhalogenated picolinic acid can be reduced and removed with high selectivity through electrolytic reaction.
Description
(1) technical field
The present invention relates to the electrochemical reduction method of the salt compounds of haloperidid formic acid or haloperidid formic acid, be specifically related under the existence of 3-position and 5-position or 3-position halogenic substituent by the optionally method of the halogenic substituent of the 6-position of reductive halogenation pyridine carboxylic acid or its esters compound of electrolysis.
(2) background technology
Recently, the derivative that has been found that some the haloperidid formic acid (as 3,5-lontrel, 3-chloropyridine formic acid etc.) that contains hydrogen in 6-position not only has weeding activity but also can be used as treatment and the medicine of prevention senile dementia and diabetes.Therefore, need to prepare some the haloperidid formic acid that contains hydrogen in these 6-positions from corresponding 6-position halo derivatives, wherein many such as 3,6-lontrel, 3,5, the chloro-pyridine carboxylic acid of 6-tri-, 4-amino-3, the derivative of 5,6-, tri-chloro-pyridine carboxylic acids and so on is commercially available.
Although the chemical reduction dehalogenation of haloperidid is known, for example, referring to United States Patent (USP) 4,087,431 and 4,783,536, wherein utilize respectively hydrazine hydrate and zinc powder as reductive agent, the selective difference of the method and the low shortcoming of material use efficiency.On the other hand, electrolytic reduction is very effective, especially has very high selectivity for the reduction of haloperidid formic acid.United States Patent (USP) 4,217,185 disclose the method that 3,4,5,6-4 chloro pyridine formic acid electrolytic reduction is prepared 3,6-lontrel.United States Patent (USP) 7,666 in addition, 293 disclose electrolytic reduction 4-amino-3, and the chloro-pyridine carboxylic acid of 5,6-tri-is prepared 4-amino-3, the method for 6-bis-chloro-pyridine carboxylic acids.From above-mentioned two patents, we can find that on haloperidid formic acid molecule, 4-and 5-position halogen the most easily reduce to remove.Therefore, for haloperidid formic acid, retaining under the prerequisite of 5-halogen, the 6-position halogen that optionally reduce is seemingly impossible.In addition, yet do not prove 3-and 6-halogen that relevant report of more easily reducing in electrolytic reduction at present.
(3) summary of the invention
Now, we are surprised to find by experiment: taking acidic solution as reaction medium, by haloperidid formic acid or its esters compound dissolution or be partly dissolved wherein, carry out electrolytic reduction reaction, the halogen energy highly selective that haloperidid formic acid or its esters compound are 6 is reduced.
The technical solution used in the present invention is:
The selective electrochemical reduction method of the salt compounds of a kind of haloperidid formic acid or haloperidid formic acid, described selective electrochemical reduction method is: taking acidic solution as reaction medium, the salt compounds of the haloperidid formic acid shown in formula (II) or haloperidid formic acid is added and in acidic solution, obtains electrolytic reaction liquid, taking chemical inert material as anode, in electrolyzer taking metallic substance as negative electrode, carry out electrolytic reaction, electrolytic reaction finishes rear electrolytic reaction liquid through acidifying, reclaims and obtains the selective reduction product shown in formula (I); The pH of described electrolytic reaction liquid in reaction process is controlled at 1～6; Described acidic solution is formed by solvent and supporting electrolyte mixed preparing, wherein said solvent is the mixed solvent of water or water and organic solvent, and described supporting electrolyte is the mixture of one or more arbitrary proportions in organic acid, mineral acid, acid-salt; In described electrolytic reaction process, be-0.2～-1.4V with respect to Ag/AgCl (3.0M KCl) reference electrode cathode potential;
In formula (I) or formula (II), X represents Cl or Br; Y represents H, F, Cl, Br, amino, hydroxyl or C1～C4 alkyl; Z represents H, F, amino, hydroxyl or C1～C4 alkyl; And in the time that X is Cl, Y can not be Br.
The salt compounds of the haloperidid formic acid described in the present invention, concrete as: haloperidid sodium formiate, haloperidid potassium formiate, haloperidid lithium formate, haloperidid ammonium formiate, preferably haloperidid sodium formiate.
The said term of the present invention " halogen " or " halo " refer to Cl or Br.
According to the common practise of this area, the reduction potential ratio of bromine is with reference to the high about 0.5V of chlorine electromotive force (less negative value), and first bromine is always reduced, and therefore, in the time that X is Cl, Y can not be Br.
When X of the present invention is Cl, cathode potential is-0.6～-1.4V, and when preferably X is Cl, Y is also Cl.
When X of the present invention is Br, cathode potential is-0.2～-1.2V, and when preferably X is Br, Y is also Br.
The pH of preferred electrolytic reaction liquid of the present invention in reaction process is 3～5; In described electrolytic reaction liquid, the content of the salt compounds of described haloperidid formic acid or haloperidid formic acid can be 0.5wt%～20wt%, is preferably 5wt%～10wt%.
In the mixed solvent of water of the present invention and organic solvent, described organic solvent can be alcohol, tetrahydrofuran (THF), dimethyl formamide or the N,N-DIMETHYLACETAMIDE of C1～C4.
Solvent described in the present invention is preferably water.
Concrete, supporting electrolyte of the present invention is the mixture of one or more arbitrary proportions in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, formic acid, acetic acid, propionic acid, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, ammonium sulfate, preferably adopts phosphate-buffered salt as supporting electrolyte
The proper temperature of electrolytic reaction of the present invention is 5～90 DEG C, and preferably temperature is 20～60 DEG C, particularly preferably 30～40 DEG C.
When electrolysis, cathode potential is with respect to standard A g/AgCl (3.0M Cl
-) electrode is-0.2～-1.2 volt for Br, is-0.6～-1.4 volt for Cl.For Br, preferably electromotive force is-0.2～-0.6 volt; For Cl, preferably electromotive force is-0.6～-1.0 volt.Corresponding current density changes according to the change in concentration of the salt compounds of haloperidid formic acid in electrolytic reaction liquid or haloperidid formic acid, and applicable electrolysis cathode current density is 1～20A/dm conventionally
2, preferably 3～7A/dm
2.
Reaction related in selective electrochemical reduction of the present invention is described below:
(1) neutralization reaction:
(2) cathodic reaction:
(3) anodic reaction:
2(OH
-)→1/2O
2+H
2O+2e
-
or
H
2O→1/2O2+2H
++2e
-
(4) total reaction:
The present invention carries out required electrolytic reduction by the generally well-known technology in this area.Usually, by raw material haloperidid formic acid or its esters compound dissolution or be partially dissolved in solvent, add a certain amount of supporting electrolyte, then in electrolyzer, pass into enough electric currents, until obtain the reduction of required degree, after electrolytic reaction finishes, by further acidification reaction liquid and utilize traditional technology to reclaim product.
Anode can be any chemical inert material, as platinum, graphite, carbon, nickel, cobalt or the metal oxide such as silver suboxide, or alloy such as nickelalloy (as: Hastelloy C) and the stainless steel.
Similarly, negative electrode can, from many material preparations, comprise mercury, lead, iron, tin, zinc or silver, preferably silver.
Electrode can be the form of tabular, shaft-like, wire, screen cloth, netted, ulotrichy or sheet, the screen cloth of preferred development.Male or female also can be made up of the coating being coated on another kind of material, for example: the metal oxide containing precious metals such as ruthenium oxide is applied on titanium metal.
Most preferred negative electrode is active silver electrode, described active silver electrode by being anodic oxidation under the condition of 0.3～1.3 volt in electromotive force in the aqueous solution that contains halide-ions, then the polarity reversal of electrode is carried out to cathodic reduction and obtain, halide-ions described here refers to Cl
-or Br
-.For example, non-activated silver electrode is immersed in the liquid caustic that contains halide-ions and it is carried out to anodic oxidation, some silver of electrode surface are transformed to jellied silver chloride and silver suboxide mixture, and simultaneously by surperficial roughen, then the polarity reversal of electrode is reduced.Activation step comprises the final value that electromotive force is increased to at least 0.3 volt from 0 volt of initial value, preferably 0.9 volt, the sedimental reduction of silver chloride and silver suboxide needs the negative polarization of negative electrode, and 0.3～1.3 volt of value that cathode potential finishes to reach from oxidation step conventionally gradually reduces numerical value-0.5 volt or less.In the method, in liquid caustic, the concentration of halide-ions is 0.2～5 mol/L, and preferred halogen ion concentration is 0.5～2 mol/L; OH
-concentration be 0～5 mol/L, preferred OH
-ionic concn is 0.5～2 mol/L.In the method, do not need any silver to join in liquid caustic.Preferably in undivided cell, silver cathode is carried out to activation treatment, anode used can be any chemical inert material, for example: platinum, graphite, carbon, metal oxide such as silver suboxide, it is to be noted, alloy such as Hastelloy C can not use, because the alloy anode of Hastelloy C and so on easily corrodes under the halogen ion of high density exists.If needed, also can use separator that electrolyzer is divided into independently negative electrode and anolyte compartment, available separator material has, Teflon, asbestos and the glass of various negatively charged ion and cationic exchange membrane, porous.The state of disturbance of shape, internal structure and the solution of electrolyzer is not crucial factor.Proper temperature for silver cathode activation is 5～80 DEG C, and preferably temperature is 20～60 DEG C, and Optimal Temperature is 20～40 DEG C.
Electrolysis can intermittently be carried out or carry out in continuous or semicontinuous mode.Electrolyzer can be the steel basin that contains electrode or the flow cell channel of any traditional design.Electrolyzer can be that single chamber groove also can diaphragm sell, preferably diaphragm sell.Available separator material has, Teflon, asbestos and the glass of various negatively charged ion and cationic exchange membrane, porous, and preferably perfluoro sulfonic acid membrane is as the barrier film of electrolyzer.
Although preferably emit oxygen as anodic reaction, also can use many other anodic reactions.Comprise emitting or producing carbonic acid gas or form valuable by product by the oxidation of organic reactant by the oxidation of the protective substance such as formate or oxalate of chlorine molecule and molecular bromine.
Beneficial effect of the present invention is mainly reflected in: under the existence of 3-and 5-position or 3-position halogenic substituent, the 6-position halogen of many haloperidids formic acid can remove by electrolytic reaction in highly selective realization reduction.
(4) embodiment
Below in conjunction with embodiment, the invention will be further described, and protection scope of the present invention is not limited to this.
The preparation of embodiment 1 active silver electrode
In undivided cell, adopt the screen cloth silver of expansion as working electrode, apparent size is 0.1cm × 10cm × 10cm, the graphite of identical apparent size is anode, the anode and cathode 2cm of being separated by.Electrolytic solution is the aqueous solution of 1000mL2.9wt% sodium-chlor+2wt% sodium hydroxide, and it is static that electrolytic solution keeps.Then logical direct current is oxidized silver electrode, and current density is 50mA/cm
2, dropping to after 0.9 volt until electrode potential, upset polarity is reduced to silver electrode, and current density is 100mA/cm
2, after rising to-0.8 volt, electrode potential stops energising, and temperature of reaction is controlled at 25 DEG C, and bath voltage is at 2.5～3.5V.Take out silver electrode, immerse in deionized water for subsequent use.
Embodiment 2 electrolytic synthesis 3,5-lontrel (3,5-D)
Barrier film sheet frame groove is electrolysis reactor, and perfluoro sulfonic acid membrane is barrier film, and the expansion screen cloth silver of activation is negative electrode, and netted 316 stainless steels are anode.The 0.25mol/L phosphate buffer solution of 1000mL pH=4 is catholyte, and the quality of throwing first 3,5,6-trichloropyridine formic acid (3,5,6-T, 98wt%) in catholyte is 20 grams; 4wt% aqueous sodium hydroxide solution is anolyte.In electrolytic process, use pH=3～5 of the sulfuric acid control cathode liquid of 30wt%, in catholyte, substep is added 3,5 of 30 grams, material, 6-T, and temperature control is 30～35 DEG C, current density control is 3A/dm
2.Pass into 4F/mol3, after 5,6-T electric weight, stop electrolysis.After catholyte is transferred in beaker, add sulfuric acid to regulate pH=1, then the temperature to 5 of control cathode liquid DEG C is carried out crystallization, filter and obtain 32.5 grams of white crystalline solid, after high-efficient liquid phase analysis, wherein contain 3,5-D98.2wt%, with isopyknic methylene dichloride to filter rear mother liquor carry out 3 times extraction, after vaporing away extraction agent, obtain 8 grams of white powders, after high-efficient liquid phase analysis, wherein contain 3,5-D93.7wt%.
Embodiment 3～embodiment 9
Embodiment 3～embodiment 9 carries out according to the experiment parameter of table 1, and all the other operate with embodiment 2.
Experiment condition and the result of 3,5-D prepared in table 11000mL scale electrolysis dechlorination
a
ataking activation expansion screen cloth silver as negative electrode, pass into the electric weight of 4F/mol reaction substrate.
Embodiment 10～embodiment 13
Embodiment 10～embodiment 13 carries out according to the experiment parameter of table 2, and all the other operate with embodiment 2.
3-chloropyridine formic acid (3-C), 5-amino-3-chloropyridine formic acid (5-A-3-C), 3, experiment condition and the result of 5-dibromo pyridine formic acid (3,5-DB) are prepared in table 21000mL scale electrolysis dechlorination
ataking activation expansion screen cloth silver as negative electrode, pass into the electric weight of 4F/mol reaction substrate.
btaking activation expansion screen cloth silver as negative electrode, pass into the electric weight of 6F/mol reaction substrate.
Claims (10)
1. the selective electrochemical reduction method of the salt compounds of a haloperidid formic acid or haloperidid formic acid, it is characterized in that described selective electrochemical reduction method is: taking acidic solution as reaction medium, the salt compounds of the haloperidid formic acid shown in formula (II) or haloperidid formic acid is added and in acidic solution, obtains electrolytic reaction liquid, taking chemical inert material as anode, in electrolyzer taking metallic substance as negative electrode, carry out electrolytic reaction, electrolytic reaction finishes rear electrolytic reaction liquid through acidifying, recovery obtains the selective reduction product shown in formula (I), the pH of described electrolytic reaction liquid in reaction process is controlled at 1～6, described acidic solution is formed by solvent and supporting electrolyte mixed preparing, wherein said solvent is the mixed solvent of water or water and organic solvent, and described supporting electrolyte is the mixture of one or more arbitrary proportions in organic acid, mineral acid, acid-salt, in described electrolytic reaction process, be-0.2～-1.4V with respect to Ag/AgCl (3.0M KCl) reference electrode cathode potential,
In formula (I) or formula (II), X represents Cl or Br; Y represents H, F, Cl, Br, amino, hydroxyl or C1～C4 alkyl; Z represents H, F, amino, hydroxyl or C1～C4 alkyl; And in the time that X is Cl, Y can not be Br.
2. selective electrochemical reduction method as claimed in claim 1, is characterized in that X is Cl, and described cathode potential is-0.6～-1.4V.
3. selective electrochemical reduction method as claimed in claim 2, is characterized in that Y is Cl.
4. selective electrochemical reduction method as claimed in claim 1, is characterized in that X is Br, and described cathode potential is-0.2～-1.2V.
5. selective electrochemical reduction method as claimed in claim 4, is characterized in that Y is Br.
6. selective electrochemical reduction method as claimed in claim 1, it is characterized in that described anode is platinum, graphite, carbon, nickel, cobalt or silver suboxide, or described anode is nickelalloy or stainless material, described negative electrode is mercury, lead, iron, tin, zinc or silver.
7. selective electrochemical reduction method as claimed in claim 6, is characterized in that described negative electrode is for silver, and silver cathode is by containing Cl
-or Br
-the aqueous solution in, anodic oxidation under the condition that is 0.3～1.3V in electromotive force, then carries out cathodic reduction by electrode and activates.
8. selective electrochemical reduction method as claimed in claim 1, is characterized in that in the mixed solvent of described water and organic solvent alcohol, tetrahydrofuran (THF), dimethyl formamide or N,N-DIMETHYLACETAMIDE that described organic solvent is C1～C4.
9. selective electrochemical reduction method as claimed in claim 1, is characterized in that described supporting electrolyte is the mixture of one or more arbitrary proportions in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, formic acid, acetic acid, propionic acid, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, ammonium sulfate.
10. selective electrochemical reduction method as claimed in claim 1, is characterized in that in described electrolytic reaction liquid, the content of the salt compounds of described haloperidid formic acid or haloperidid formic acid is 0.5wt%～20wt%.
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