CN114892190A - 光电催化制备氯普鲁卡因的方法 - Google Patents
光电催化制备氯普鲁卡因的方法 Download PDFInfo
- Publication number
- CN114892190A CN114892190A CN202210549098.0A CN202210549098A CN114892190A CN 114892190 A CN114892190 A CN 114892190A CN 202210549098 A CN202210549098 A CN 202210549098A CN 114892190 A CN114892190 A CN 114892190A
- Authority
- CN
- China
- Prior art keywords
- chloroprocaine
- photoelectrocatalysis
- preparing
- electrolyte
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229960002023 chloroprocaine Drugs 0.000 title claims abstract description 36
- VDANGULDQQJODZ-UHFFFAOYSA-N chloroprocaine Chemical compound CCN(CC)CCOC(=O)C1=CC=C(N)C=C1Cl VDANGULDQQJODZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229960004919 procaine Drugs 0.000 claims abstract description 16
- MFDFERRIHVXMIY-UHFFFAOYSA-N procaine Chemical compound CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 MFDFERRIHVXMIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- -1 transition metal sulfide Chemical class 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001804 chlorine Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 206010002091 Anaesthesia Diseases 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000037005 anaesthesia Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 210000005036 nerve Anatomy 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003589 local anesthetic agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- MBDUKNCPOPMRJQ-UHFFFAOYSA-N 4-amino-2-chlorobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(Cl)=C1 MBDUKNCPOPMRJQ-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000036982 action potential Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960002038 chloroprocaine hydrochloride Drugs 0.000 description 1
- SZKQYDBPUCZLRX-UHFFFAOYSA-N chloroprocaine hydrochloride Chemical compound Cl.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1Cl SZKQYDBPUCZLRX-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- 238000002692 epidural anesthesia Methods 0.000 description 1
- VABUHUZDQFBOBL-UHFFFAOYSA-N ethanol;n-ethylethanamine Chemical compound CCO.CCNCC VABUHUZDQFBOBL-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000018405 transmission of nerve impulse Effects 0.000 description 1
Images
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
- C25B3/01—Products
- C25B3/11—Halogen containing 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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
- C25B3/07—Oxygen containing 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
- C25B3/09—Nitrogen containing 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
- C25B3/20—Processes
- C25B3/21—Photoelectrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明公开了一种光电催化制备氯普鲁卡因的方法,包括((Ⅰ)组装光电解池和(Ⅱ)光电催化反应等步骤。本发明以廉价的氯盐作为卤源,通过绿色温和的光电催化方法与普鲁卡因反应制备氯普鲁卡因,避免了有毒且昂贵的试剂和原料的使用,可大幅度降低制备成本。与传统制备氯普鲁卡因的方法相比,本发明中所使用的光电催化方法反应条件温和、制备工艺简便且对氯普鲁卡因的选择性高,为氯普鲁卡因的绿色制备提供了新的思路和方法。
Description
技术领域
本发明属于光电催化有机合成领域,具体涉及一种光电催化制备氯普鲁卡因的方法。
背景技术
氯普鲁卡因又叫纳噻卡因,化学名为2-二乙氨基-4-氨基-2-氯苯甲酸乙酯,分子式为C13H19ClN2O2,是一种高效的局部麻醉药,能通过提高神经产生电冲动的阈值和减慢神经冲动的生成速度及降低动作电位的生成率,阻碍神经冲动的产生和传递而起作用。氯普鲁卡因在临床上主要用于浸润麻醉、神经阻滞麻醉、骶管和硬膜外麻醉,因其起效快、持续时间长、麻醉后恢复快等优点在临床研究中需求较大。
目前,氯普鲁卡因的合成方法主要是以2-氯-4-氨基苯甲酸与氯化亚砜的酰氯化反应或2-氯-4-氨基苯甲酸甲酯与二乙胺乙醇反应为主(盐酸氯普鲁卡因的化学合成研究[D].浙江大学,2009.;Synlett.1994,1,68-70.),虽然这些方法反应效率较高,但需要使用大量有机溶剂及有毒的试剂、且原料价格昂贵,很难得到广泛的应用。
发明内容
本发明是为了解决现有氯普鲁卡因制备方法中存在使用大量有机溶剂及有毒的试剂、且原料价格昂贵的缺点而提出的,其目的是提供一种光电催化制备氯普鲁卡因的方法,减轻对化石资源的依赖,开发化学品绿色生产工艺。
本发明是通过以下技术方案实现的:
一种光电催化制备氯普鲁卡因的方法,其特征在于:包括以下步骤:
(Ⅰ)组装光电解池
将负载光阳极催化剂的导电基底作为光阳极、将阴极催化剂作为阴极,与电解液一起组装成光电解池;
(Ⅱ)光电催化反应
在电解液中加入普鲁卡因乙腈溶液,在光照强度和偏压条件下,氯离子在光阳极活化为氯自由基和氯气,并与普鲁卡因反应生成氯普鲁卡因,而水在阴极还原产生氢气。
在上述技术方案中,所述阳极催化剂为二氧化钛、钒酸铋、三氧化钨、氧化锌或氧化铁中的任意一种。
在上述技术方案中,所述导电基底为FTO或ITO。
在上述技术方案中,所述阴极催化剂为过渡金属氧化物、过渡金属磷化物、过渡金属硫化物、过渡金属氮化物、过渡金属硼化物、铂基催化剂、钯基催化剂、钌基催化剂、铑基催化剂、镍基催化剂或铜基催化剂中的任意一种或几种的混合物。
在上述技术方案中,所述电解液为氯化钠、氯化钾或氯化钙中的任意一种或几种混合的水溶液。
在上述技术方案中,所述电解液的质量浓度为10g/L~100g/L。
在上述技术方案中,所述普鲁卡因的乙腈溶液的质量浓度为0.1g/L~10g/L。
在上述技术方案中,所述普鲁卡因乙腈溶液与电解液的体积比为1:(5~10)。
在上述技术方案中,所述步骤(Ⅱ)光电催化反应中光照强度为100mW·cm-2~500mW·cm-2。
在上述技术方案中,所述步骤(Ⅱ)光电催化反应中偏压为0V~2V。
本发明的有益效果是:
本发明提供了一种光电催化环己烷制备环己酮的方法,以廉价的氯盐作为卤源,通过绿色温和的光电催化方法制备氯普鲁卡因,避免了有毒试剂及昂贵原料的使用,可大幅度降低生产成本。与传统氯普鲁卡因合成方法相比,本发明中所使用的光电催化方法反应条件温和、制备工艺简便,为氯普鲁卡因的绿色制备提供了新的思路和方法。
附图说明
图1是本发明光电催化制备氯普鲁卡因的方法的原理示意图;
图2是本发明实施例1中光阳极催化剂二氧化钛的扫描电镜图;
图3是本发明实施例1中光阳极的X射线衍射图;
图4是本发明实施例1中制备的氯普鲁卡因的气相色谱图。
对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,可以根据以上附图获得其他的相关附图。
具体实施方式
为了使本技术领域的人员更好地理解本发明技术方案,下面结合说明书附图并通过具体实施方式来进一步说明本发明光电催化甘油选择性氧化制备二羟基丙酮的方法的技术方案。
一种光电催化制备氯普鲁卡因的方法,其特征在于:包括以下步骤:
(Ⅰ)组装光电解池
将负载光阳极催化剂的导电基底作为光阳极、将阴极催化剂作为阴极,与电解液一起组装成光电解池;
所述阳极催化剂为二氧化钛、钒酸铋、三氧化钨、氧化锌或氧化铁中的任意一种;导电基底为FTO或ITO。
所述阴极催化剂为过渡金属氧化物、过渡金属磷化物、过渡金属硫化物、过渡金属氮化物、过渡金属硼化物、铂基催化剂、钯基催化剂、钌基催化剂、铑基催化剂、镍基催化剂或铜基催化剂中的任意一种或几种的混合物。
所述电解液为氯化钠、氯化钾或氯化钙中的任意一种或几种混合的水溶液;电解液的质量浓度为10g/L~100g/L。
(Ⅱ)光电催化反应
在电解液中加入质量浓度为0.1g/L~10g/L的普鲁卡因乙腈溶液,普鲁卡因乙腈溶液与电解液的体积比为1:(5~10);在光阳极施加100mW·cm-2~500mW·cm-2光照强度和0V~2V偏压条件下,氯离子在光阳极活化为氯自由基和氯气,并与普鲁卡因反应生成氯普鲁卡因,而水在阴极还原产生氢气。
所述0V~2V偏压为相对于参比电极(Ag/AgCl)的电压。
实施例1
(Ⅰ)将2mL质量浓度为0.1g/L的普鲁卡因乙腈溶液加入10mL质量浓度为70g/L的NaCl溶液中;
(Ⅱ)将步骤(Ⅰ)得到的溶液作为电解液,负载TiO2的FTO和铂片分别作为光阳极和阴极组装成电解池,然后在AM 1.5G光照(100mW cm-2)、1.6V偏压下反应10h,反应原理图如图1所示;负载TiO2纳米棒阵列的FTO的扫描电镜图如图2所示,TiO2纳米棒的长度约为1μm,直径80nm~100nm;负载TiO2的FTO光阳极材料的X射线衍射图如图3所示,TiO2呈现出典型的金红石相结构,没有其他杂质产生。
(Ⅲ)反应结束后,向反应液中加入1mL乙酸乙酯萃取,取上层油状液体,用气相色谱检测产物,结果如图4所示,氯普鲁卡因产率为23.2%。
实施例2
(Ⅰ)将2mL质量浓度为0.2g/L的普鲁卡因乙腈溶液加入10mL质量浓度为40g/L的KCl溶液中。
(Ⅱ)将步骤(Ⅰ)得到的溶液作为电解液,负载WO3的FTO和镍片分别作为光阳极和阴极组装成电解池,AM 1.5G光照(200mW cm-2)、1.8V偏压下反应15h,反应原理图如图1所示;
(Ⅲ)反应结束后,向反应液中加入1mL乙酸乙酯萃取,取上层油状液体,用气相色谱检测产物,氯普鲁卡因产率为18.1%。
实施例3
(Ⅰ)将1mL质量浓度为0.5g/L的普鲁卡因乙腈溶液加入10mL质量浓度为50g/LCaCl2溶液中。
(Ⅱ)将步骤(Ⅰ)得到的溶液作为电解液,负载BiVO4的FTO和氧化铜分别作为光阳极和阴极组装成电解池,AM 1.5G光照(400mW cm-2)、1.4V偏压下反应24h,反应原理图如图1所示;
(Ⅲ)反应结束后,向反应液中加入1mL乙酸乙酯萃取,取上层油状液体,用气相色谱检测产物,氯普鲁卡因产率为27.6%。
本发明化学原理方程式:
本发明采用光电化学方法,以廉价的氯盐为电解质及卤源,避免使用有毒且昂贵的卤化试剂,利用卤素离子捕获光生空穴产生的卤素自由基或卤素单质与普鲁卡因发生自由基链式反应得到氯普鲁卡因。与传统氯普鲁卡因合成方法相比,该反应过程条件温和,无需有机溶剂、额外的氧化剂,为氯普鲁卡因的绿色制备提供了新的思路和方法。
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种光电催化制备氯普鲁卡因的方法,其特征在于:包括以下步骤:
(Ⅰ)组装光电解池
将负载光阳极催化剂的导电基底作为光阳极、将阴极催化剂作为阴极,与电解液一起组装成光电解池;
(Ⅱ)光电催化反应
在电解液中加入普鲁卡因乙腈溶液,在光照强度和偏压条件下,氯离子在光阳极活化为氯自由基和氯气,并与普鲁卡因反应生成氯普鲁卡因。
2.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述阳极催化剂为二氧化钛、钒酸铋、三氧化钨、氧化锌或氧化铁中的任意一种。
3.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述导电基底为FTO或ITO。
4.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述阴极催化剂为过渡金属氧化物、过渡金属磷化物、过渡金属硫化物、过渡金属氮化物、过渡金属硼化物、铂基催化剂、钯基催化剂、钌基催化剂、铑基催化剂、镍基催化剂或铜基催化剂中的任意一种或几种的混合物。
5.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述电解液为氯化钠、氯化钾或氯化钙中的任意一种或几种混合的水溶液。
6.根据权利要求5所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述电解液的质量浓度为10g/L~100g/L。
7.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述普鲁卡因的乙腈溶液的质量浓度为0.1g/L~10g/L。
8.根据权利要求7所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述普鲁卡因乙腈溶液与电解液的体积比为1:(5~10)。
9.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述步骤(Ⅱ)光电催化反应中光照强度为100mW·cm-2~500mW·cm-2。
10.根据权利要求1所述的光电催化制备氯普鲁卡因的方法,其特征在于:所述步骤(Ⅱ)光电催化反应中偏压为0V~2V。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210549098.0A CN114892190A (zh) | 2022-05-20 | 2022-05-20 | 光电催化制备氯普鲁卡因的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210549098.0A CN114892190A (zh) | 2022-05-20 | 2022-05-20 | 光电催化制备氯普鲁卡因的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114892190A true CN114892190A (zh) | 2022-08-12 |
Family
ID=82724528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210549098.0A Pending CN114892190A (zh) | 2022-05-20 | 2022-05-20 | 光电催化制备氯普鲁卡因的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114892190A (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100105969A1 (en) * | 2007-03-09 | 2010-04-29 | Junichi Yoshida | Method of producing iodizing agent, and method of producing aromatic iodine compound |
-
2022
- 2022-05-20 CN CN202210549098.0A patent/CN114892190A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100105969A1 (en) * | 2007-03-09 | 2010-04-29 | Junichi Yoshida | Method of producing iodizing agent, and method of producing aromatic iodine compound |
Non-Patent Citations (1)
Title |
---|
ZHENHUA LI ET. AL.: "Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode", 《NATURE COMMUNICATIONS》, vol. 12, pages 6698 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11136679B2 (en) | Electrochemical and photoelectrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and 2,5-diformylfuran | |
Nath et al. | Stand-alone photoconversion of carbon dioxide on copper oxide wire arrays powered by tungsten trioxide/dye-sensitized solar cell dual absorbers | |
He et al. | High sensitivity of TiO2 nanorod array electrode for photoelectrochemical glucose sensor and its photo fuel cell application | |
JP6101276B2 (ja) | 酸素及び/又は水素の電気化学的発生のための装置及び方法 | |
US4303486A (en) | Methods of photocatalytic decarboxylation of saturated carboxylic acid | |
US10077500B2 (en) | Water splitting catalyst, and method for producing oxygen and hydrogen using the same | |
JP3995051B2 (ja) | 有機光触媒を用いた水の電気分解方法 | |
CH645819A5 (de) | Verfahren und photochemische reaktionseinrichtung fuer die endoenergetische erzeugung von oxydations- und reduktionsprodukten. | |
US11473205B2 (en) | Electrochemical oxidation of aromatic aldehydes in acidic media | |
CN103872174B (zh) | 一种Au修饰TiO2纳米棒阵列光阳极的制备方法 | |
CN112264004A (zh) | 基于钨酸盐的催化材料及其在水氧化产过氧化氢中的应用 | |
Na et al. | Bio-inspired model of photosystem II: supramolecular assembly of an electron mediator into an SnO 2 photoanode co-sensitized by a porphyrin photosensitizer and ruthenium molecular catalyst | |
CN114892190A (zh) | 光电催化制备氯普鲁卡因的方法 | |
CN109092288A (zh) | 一种二氧化碳电化学还原锡铅合金催化剂的制备及应用 | |
KR20210082686A (ko) | 포스포몰리브드산수화물의 환원 공정을 이용한 수소 생산 방법 및 수소 생산 시스템 | |
Singh et al. | Anderson polyoxometalate supported Cu (H2O)(phen) complex as an electrocatalyst for hydrogen evolution reaction in neutral medium | |
Huang et al. | Sustainable electrochemical gold dissolution process based on triboelectric nanogenerator | |
CN107354477A (zh) | 一种异烟酸的合成方法 | |
Xiao et al. | Reaction kinetics of photoelectrochemical water and 5-hydroxymethylfurfural oxidation on rutile nanorod photoanode with Ge doping and core/shell structure | |
CN113106470A (zh) | 一种适用于电化学氮还原的钒掺杂二氧化钛/石墨烯电催化剂及其制备方法 | |
McCafferty et al. | Light-driven generation of chlorine and hydrogen from brine using highly selective Ru/Ti oxide redox catalysts | |
CN115094448B (zh) | 光电催化环己烷制备环己酮的方法 | |
WO2021138961A1 (zh) | 一种新型七氧化四钛纳米管改性二氧化铅电极制备技术 | |
CN102618880A (zh) | 光氯碱电解电池及采用该光氯碱电解电池生产Cl2和NaOH的方法 | |
JPS60235831A (ja) | アニリンポリマ−の合成法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220812 |