CN113797977B - 一种钌催化剂及其应用 - Google Patents
一种钌催化剂及其应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 5
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 4
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012448 Lithium borohydride Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000000575 pesticide Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 150000003217 pyrazoles Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000006757 chemical reactions by type Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- JCEMPCVTIITKAC-UHFFFAOYSA-N dimethyl 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=C(F)C(F)=C(C(=O)OC)C(F)=C1F JCEMPCVTIITKAC-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
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- AGWVQASYTKCTCC-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenyl)methanol Chemical compound OCC1=C(F)C(F)=CC(F)=C1F AGWVQASYTKCTCC-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- UTVICBCTIZYQOA-UHFFFAOYSA-N methyl 2,3,5,6-tetrafluorobenzoate Chemical compound COC(=O)C1=C(F)C(F)=CC(F)=C1F UTVICBCTIZYQOA-UHFFFAOYSA-N 0.000 description 2
- PGJYYCIOYBZTPU-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzyl alcohol Chemical compound OCC1=C(F)C(F)=C(F)C(F)=C1F PGJYYCIOYBZTPU-UHFFFAOYSA-N 0.000 description 1
- IFXVJFVIUFAFNZ-UHFFFAOYSA-N 2-diphenylphosphorylbenzaldehyde Chemical compound O=CC1=CC=CC=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 IFXVJFVIUFAFNZ-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OSTIHFXUTPZJQL-UHFFFAOYSA-N fluoro benzoate Chemical compound FOC(=O)C1=CC=CC=C1 OSTIHFXUTPZJQL-UHFFFAOYSA-N 0.000 description 1
- -1 fluorobenzoic acid ester Chemical class 0.000 description 1
- VPLALCFPHOLSTP-UHFFFAOYSA-N fluoromethyl benzoate Chemical compound FCOC(=O)C1=CC=CC=C1 VPLALCFPHOLSTP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UXJRQNXHCZKHRJ-UHFFFAOYSA-N methyl 2,3,4,5,6-pentafluorobenzoate Chemical compound COC(=O)C1=C(F)C(F)=C(F)C(F)=C1F UXJRQNXHCZKHRJ-UHFFFAOYSA-N 0.000 description 1
- XQDSCGOSSYGRSM-UHFFFAOYSA-N methyl 2,3,5,6-tetrafluoro-4-(hydroxymethyl)benzoate Chemical compound COC(=O)C1=C(F)C(F)=C(CO)C(F)=C1F XQDSCGOSSYGRSM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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Abstract
本发明涉及农药和医药领域，具体地是制备一种钌催化剂，利用该催化剂催化多氟苯甲酸酯还原为多氟苯甲醇的应用。催化剂如下述式一所示，所述催化剂在催化多氟苯甲酸酯还原为多氟苯甲醇的应用。本发明的催化剂制备简单、廉价、稳定，应用于催化吡唑类化合物与含卤素芳环或杂环时，应用范围广，制备简单、收率高、反应条件温和。
Description
技术领域
本发明涉及农药和医药领域，具体地是制备一种钌催化剂，利用该催化剂催化多氟苯甲酸酯还原为多氟苯甲醇的应用。
背景技术
多氟苯甲醇是重要中间体，具有着独特的结构，其衍生物具有独特生物活性，在农药和医药等方面有重要的作用。
多氟苯甲酸酯还原为多氟苯甲醇是重要的合成途径之一。文献报道(Wei Li,Qi-Lin Zhou et al,Green Chemistry,2014，4081-4085)利用钌催化剂加氢，反应时间达数小时到数十小时，氢压需要50或以上的大气压，反应温度也要高于100摄氏度；苯环上仅有1-2个氟原子取代，且氟代苯甲酸酯只能且唯一为氟代苯甲酸甲酯；超过2个氟原子取代的苯甲酸酯还原并未见报道。
发明内容
本发明的目的在于提供一种钌催化剂，利用该催化剂催化多氟苯甲酸酯还原为多氟苯甲醇的应用。
为实现上述目的，本发明采用技术方案为：
一种钌催化剂，催化剂如下述式一所示，
钌催化剂的制备方法：
催化剂制备流程如下：
1)2-二苯基膦-苯甲醛与1，2-环己二胺反应生成含有磷、氮配体；
2)利用钌配合物(二氯化四(二甲基亚砜)合钌)，在溶剂N,N-二甲基甲酰胺中与上述配体反应生成式一所示催化剂。
进一步的说：
3.按权利要求2所述钌催化剂的制备方法，其特征在于：
1)按2:1mmol比例将2-二苯基膦-苯甲醛与1，2-环己二胺混合反应生成含有磷、氮配体；
2)向5mmol二氯化四(二甲基亚砜)合钌中，依次加入40mL N,N-二甲基甲酰胺，搅拌下加入5mmol上述制备获得磷、氮配体，在氮气条件下加热140℃左右回流2小时(约150分钟)后，冰浴条件下冷却至室温；
3)减压蒸出N,N-二甲基甲酰胺，冷却至室温，过滤固体，经无水甲醇冲洗，得红色固体式一所示催化剂。
更进一步的说：
1)将5mmol二氯化四(二甲基亚砜)合钌加入烘干的三颈圆底烧瓶中，依次加入40mL N,N-二甲基甲酰胺，搅拌下加入5mmol磷、氮配体，即结构式：
2)在氮气条件下加热回流150分钟后，冰浴条件下冷却至室温。
3)减压蒸出约30mL N,N-二甲基甲酰胺，冷却至室温，过滤固体，5mL无水甲醇冲洗3次，得红色固体如式一所示催化剂。
一种催化剂的应用，所述催化剂在催化多氟苯甲酸酯还原为多氟苯甲醇的应用。
一种多氟苯甲酸酯合成多氟苯甲醇的方法：
催化多氟苯甲酸酯还原反应通式如下：
将原料、还原剂和所述催化剂，在溶剂存在下，于压力釜中在1-5大气压氢气下，加热回流1-9小时即获得多氟苯甲醇。
优选：
(1)1.0mmol多氟苯甲酸酯、0.5-1.1mmol还原剂、0.01-5mol％催化剂，适量的四氢呋喃溶剂置于干燥的压力釜中。
(2)在1-5大气压氢气下，在20-100℃加热1-9小时。
(3)冷却至室温后，反应液过滤，滤液减压蒸馏，残液过柱分离。
所述原料为多氟苯甲酸酯或多氟苯二甲酸酯。
所述催化剂的用量为原料的0.01-5mol％，优选0.1-1mol％。
所述还原剂为硼氢化钠、硼氢化钾或硼氢化锂，优选硼氢化钠；其用量为原料的50-110mol％。
所述溶剂为四氢呋喃或甲基四氢呋喃，优选四氢呋喃。
所述反应温度在20-100℃，优选50-100℃。
本发明的优点是：
本发明催化剂成本低、制备工艺简单，催化剂效率高、稳定性好、适用范围广、反应条件温和。本发明采用钌催化剂，以半量到等量硼氢化钠为还原剂，在四氢呋喃或甲基四氢呋喃中还原，加热数小时完成多氟苯甲酸酯还原合成多氟苯甲醇。该方法方便易行，副产物少，且主要原料易得，适合商品工业化生产。
附图说明
图1为本发明实施例提供的催化剂核磁谱图。
具体实施方式
以下所述实施例用于进一步详细说明本发明。在这些实施例中，除非有特殊声明，所用药品均以毫摩尔(mmol)或克(g)或毫克(mg)计量，溶剂均以毫升(mL)计量。产物均经GC-MS验证，载气为He气，流量1mL/min；柱温150-200℃，升温速率10℃/min.。
本发明利用商品化中间体衍生配体制备和钌配合物制备新的钌催化剂，利用该催化剂催化多氟苯甲酸酯还原合成多氟苯甲醇。该催化剂催化效率高、制备工艺简单、反应条件温和、空气中稳定，且适用于催化活性较低、且在碱性较高的条件下易于脱氟的多氟苯甲酸酯合成。
实施例1：
反应式
将10mmol2-二苯基膦基-苯甲醛加入烘干的三颈圆底烧瓶中，加入100mL无水甲醇，加入5mmol 1，2-环己二胺。在氮气保护下室温搅拌12小时，加热回流3小时后，冰浴条件下冷却至0℃。抽滤，依次用冷的5mL无水乙醇、10mL乙醚各冲洗3次。得黄色固体为磷、氮配体，收率为81.7％。
实施例2：
反应式
氮气条件下，将5mmol的二氯化四(二甲基亚砜)合钌与40mL干燥处理后的N,N-二甲基甲酰胺加入干燥的圆底烧瓶中，搅拌下加入5mmol磷、氮配体。搅拌下加热至溶剂(N,N-二甲基甲酰胺)回流反应3小时。减压蒸出约30mL溶剂，残液冷却至室温，抽滤，依次用冷的无水甲醇冲洗3次。真空干燥后得红色催化剂，收率为87.9％。
实施例3：
反应式
于100mL高压釜中加入10.65g 2，3，5，6-四氟对苯二甲酸二甲酯、1.51g硼氢化钠、33.0mg上述实施例2获得催化剂、60mL四氢呋喃，通氢气5大气压保护下搅拌加热100℃反应5小时。反应液过滤，滤液减压蒸馏后残留物色谱分析，得到2，3，5，6-四氟-4-羟甲基-苯甲酸甲酯，收率为86.9％。
实施例4：
反应式
于100mL高压釜中加入8.32g 2，3，5，6-四氟苯甲酸甲酯、1.51g硼氢化钠、33.0mg上述实施例2获得催化剂、60mL四氢呋喃，通氢气5大气压保护下搅拌加热100℃反应5小时。反应液过滤，滤液减压蒸馏后残留物色谱分析，2，3，5，6-四氟苯甲醇，收率为81.6％。
实施例5：
反应式
于100mL高压釜中加入9.60g 2，3，4，5，6-五氟苯甲酸甲酯、1.51g硼氢化钠、33.0mg上述实施例2获得催化剂、60mL四氢呋喃，通氢气5大气压保护下搅拌加热100℃反应5小时。反应液过滤，滤液减压蒸馏后残留物色谱分析，2，3，4，5，6-五氟苯甲醇，收率为76.9％。
实施例6：
反应式
于100mL高压釜中加入2.08g 2，3，5，6-四氟苯甲酸甲酯、0.38g硼氢化钠、8.2mg上述实施例2获得催化剂、20mL四氢呋喃，通氢气5大气压保护下搅拌加热80℃反应8小时。反应液过滤，滤液减压蒸馏后残留物色谱分析，2，3，5，6-四氟苯甲醇，收率为78.1％。
实施例7：
反应式
于100mL高压釜中加入2.66g 2，3，5，6-四氟对苯二甲酸二甲酯、0.38g硼氢化钠、8.2mg上述实施例2获得催化剂、20mL四氢呋喃，通氢气5大气压保护下搅拌加热100℃反应8小时。反应液过滤，滤液减压蒸馏后残留物过柱(乙酸乙酯：石油醚＝1:1)，得产物2.09g，收率为87.8％。
实施例8：
反应式
于100mL高压釜中加入2.66g 2，3，5，6-四氟对苯二甲酸二甲酯、0.38g硼氢化钠、8.2mg上述实施例2获得催化剂、20mL四氢呋喃，通氢气5大气压保护下搅拌加热80℃反应8小时。反应液过滤，滤液减压蒸馏后残留物过柱(乙酸乙酯：石油醚＝1:1)，得产物1.92g，收率为80.7％。
实施例9：
反应式
于100mL高压釜中加入2.66g 2，3，5，6-四氟对苯二甲酸二甲酯、0.38g硼氢化钠、8.2mg上述实施例2获得催化剂、20mL四氢呋喃，通氢气2大气压保护下搅拌加热100℃反应8小时。反应液过滤，滤液减压蒸馏后残留物过柱(乙酸乙酯：石油醚＝1:1)，得产物1.98g，收率为83.2％。
实施例10：
于100mL高压釜中加入2.66g 2，3，5，6-四氟对苯二甲酸二甲酯、0.28g硼氢化钠、8.2mg上述实施例2获得催化剂、20mL四氢呋喃，通氢气5大气压保护下搅拌加热100℃反应8小时。反应液过滤，滤液减压蒸馏后残留物过柱(乙酸乙酯：石油醚＝1:1)，得产物1.89g，收率为79.4％。
Claims (7)
1.一种钌催化剂的应用，其特征在于：所述催化剂在催化多氟苯甲酸酯还原为多氟苯甲醇的应用；催化剂如下述式一所示，
式一
将原料、还原剂和催化剂，在溶剂存在下，于压力釜中在1-5大气压氢气下，加热回流1-9小时即获得多氟苯甲醇；
所述原料为多氟苯甲酸酯或多氟苯二甲酸酯；
所述还原剂为硼氢化钠、硼氢化钾或硼氢化锂，其用量为原料的50-110mol%。
2.按权利要求1所述钌催化剂的应用，其特征在于：所述钌催化剂的合成方法为：
1）2-二苯基膦-苯甲醛与1，2-环己二胺反应生成含有磷、氮配体；
2）利用二氯化四（二甲基亚砜）合钌，在溶剂N,N-二甲基甲酰胺中与上述配体反应生成式一所示催化剂。
3.一种权利要求1所述钌催化剂催化多氟苯甲酸酯合成多氟苯甲醇的方法，其特征在于：将原料、还原剂和催化剂，在溶剂存在下，于压力釜中在1-5大气压氢气下，加热回流1-9小时即获得多氟苯甲醇；
所述原料为多氟苯甲酸酯或多氟苯二甲酸酯。
4.按权利要求3所述的多氟苯甲酸酯合成多氟苯甲醇的方法，其特征在于：所述催化剂的用量为原料的0.01-5mol%。
5.按权利要求3所述的多氟苯甲酸酯合成多氟苯甲醇的方法，其特征在于：所述还原剂为硼氢化钠、硼氢化钾或硼氢化锂，其用量为原料的50-110mol%。
6.按权利要求3所述的多氟苯甲酸酯合成多氟苯甲醇的方法，其特征在于：所述溶剂为四氢呋喃或甲基四氢呋喃。
7.按权利要求3所述的多氟苯甲酸酯合成多氟苯甲醇的方法，其特征在于：所述加热回流的反应温度在20-100℃。
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