CN108558949A - 一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 - Google Patents
一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 Download PDFInfo
- Publication number
- CN108558949A CN108558949A CN201810566310.8A CN201810566310A CN108558949A CN 108558949 A CN108558949 A CN 108558949A CN 201810566310 A CN201810566310 A CN 201810566310A CN 108558949 A CN108558949 A CN 108558949A
- Authority
- CN
- China
- Prior art keywords
- reaction
- phenyl
- nano
- phosphene
- solution
- 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.)
- Granted
Links
- -1 benzo phosphene Chemical compound 0.000 title claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- 229910000065 phosphene Inorganic materials 0.000 title claims abstract description 19
- 206010034962 Photopsia Diseases 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 title abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000007850 fluorescent dye Substances 0.000 abstract description 4
- 238000001215 fluorescent labelling Methods 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 235000010338 boric acid Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241000972773 Aulopiformes Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000010719 annulation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的新方法，属于有机合成领域。该方法首先合成一种新的Pd纳米粒子，以化合物Ⅰ为反应底物，经环化得到目标化合物Ⅱ，R1，R2代表苯基或取代苯基或C1‑5烷基。该方法选择好，收率达89%以上，便于工业化生产，能很好地促进苯并磷杂环戊二烯在有机发光功能材料(太阳能电池，有机发光二极管)、光致变色分子开关、生物荧光探针等方向的应用。
Description
技术领域
本发明涉及一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法，属于有机合成领域。
背景技术
磷杂环戊二烯具有独特的光学和电化学性质，在有机光电材料科学领域有着广泛的用途，磷杂环戊二烯中心的磷原子可以通过化学修饰的方法生成氧化物，硫化物，过渡金属配合物，季鏻盐等，特别是氧化物和硫化物，均表现出高的化学和热力学稳定性。苯并磷杂环戊二烯作为磷杂环戊二烯的一种特殊结构，被广泛地用于有机发光功能材料(太阳能电池，有机发光二极管)、光致变色分子开关、生物荧光探针等方向。
因此，合成苯并磷杂环戊二烯的方法越来越受到重视，但是与同类化合物苯并噻吩，苯并呋喃，吲哚的合成方法相比，其合成方法仍旧比较有限，因此，研发一种操作简便、只需使用简单催化剂就能实现苯并磷杂环戊二烯的合成，仍然具有十分重要的意义。
关于苯并磷杂环戊二烯的合成方法有很多，大致可分为三类：第一类是邻位含磷基团的苯乙炔通过分子内成环反应生成(Org.Lett.,2008,10:2263～2265；Chem.AsianJ.,2009,4:1729～1740；Org.Lett.,2015,17:1732～1734)；第二类是含磷化合物与另一化合物发生分子间反应生成(J.Am.Chem.Soc.,2013,135:16754～16757；Angew.Chem.Int.Ed.,2013,52:12975～12979；Adv.Synth.Catal.,2016,358:138～142；Green Chem.,2016,18:3522～3526；J.Am.Chem.Soc.,2016,138:7436～7441)；第三类是通过关键步骤为过渡金属催化的“一锅”多组分多步反应生成(Angew.Chem.Int.Ed.,2014,53:7543～7546；Org.Lett.,2015,17:5666～5669；Org.Lett.,2016,18:5436～5439)。但是这些合成方法存在步骤繁琐或反应条件苛刻或反应体系复杂或需要特殊的配体辅助催化等一些问题，因此，急需开发出一种简单高效的合成苯并磷杂环戊二烯的方法。
用简单、高效的Pd纳米粒子催化合成苯并磷杂环戊二烯目前未见报道。
发明内容
本发明的目的在于提供一种用Pd纳米粒子作为催化剂，高效合成苯并磷杂环戊二烯的方法，以促进苯并磷杂环戊二烯在有机发光功能材料(太阳能电池，有机发光二极管)、光致变色分子开关、生物荧光探针等方向的应用。
为实现本发明目的，首先合成一种新的Pd纳米粒子，以其为催化剂，化合物Ⅰ为反应底物，得到苯并磷杂环戊二烯目标化合物。
具体通过如下步骤实现：
其中，R1，R2代表苯基或取代苯基或C1-5烷基。取代苯基优选卤素、三氟甲基、C1-5烷基、C1-5烷氧基取代。
(1)配制苯胺与四氟硼酸的乙醇溶液，冰浴条件下向该溶液中滴加亚硝酸叔丁酯，室温下搅拌反应，过滤得到苯基重氮四氟硼酸盐；苯基重氮四氟硼酸盐用四氢呋喃溶解，室温下与醋酸钯的甲醇溶液搅拌均匀；冰浴条件下再滴加硼氢化钠甲醇溶液，滴加完室温下反应至反应充分；将反应液旋干、洗涤、干燥后得到钯纳米粒子。所述的苯胺、四氟硼酸与亚硝酸叔丁酯的摩尔比优选1:2.5:2.5；所述的苯基重氮四氟硼酸盐、醋酸钯与硼氢化钠摩尔比优选4:1:5。
(2)向反应瓶中加入化合物Ⅰ，甲苯溶剂及步骤(1)Pd纳米粒子，30℃-40℃下反应，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到化合物Ⅱ。
本发明优点：
合成了一种新的Pd纳米粒子，首次使用Pd纳米粒子高效催化合成了苯并磷杂环戊二烯，选择好，收率达89％以上，便于工业化生产，能很好地促进苯并磷杂环戊二烯在有机发光功能材料(太阳能电池，有机发光二极管)、光致变色分子开关、生物荧光探针等方向的应用。
具体实施方式
下面结合具体的实施例对本发明作进一步详细的说明。
实施例1：Pd纳米粒子的制备
向10ml反应瓶中先加入2ml乙醇溶剂，再加入5mmol苯胺、12.5mmol四氟硼酸，冰浴条件下向该混合溶液中滴加12.5mmol亚硝酸叔丁酯，恢复室温，反应0.5h，往反应液加少量乙醚，有白色沉淀生成，过滤、干燥得到苯基重氮四氟硼酸盐0.92g(4.8mmol)，收率为96％；向250ml反应瓶中加入4mmol苯基重氮四氟硼酸盐(用50ml四氢呋喃溶解)，再加入1mmol醋酸钯(用50ml甲醇溶解)，室温下搅拌10min～15min，反应液成桔红色，冰浴条件下再滴加5mmol硼氢化钠(50ml甲醇溶解)溶液，滴加完室温下反应1h至反应充分；将反应液旋干、洗涤、干燥后得到Pd纳米粒子。
实施例2：反应底物Ⅰ的制备
氮气保护下，向50ml反应瓶中加入2mmol化合物(1)，随后加入10ml无水乙醚和10ml无水四氢呋喃，将体系温度降温至-78℃，氮气下滴加2.1mmol正丁基锂的正己烷溶液(1.6M)，滴加完毕后在-78℃保温1小时(反应体系1)，另取一反应瓶，加入10ml无水乙醚和2.2mmol芳香基二氯化磷，降温至-78℃(反应体系2)，将反应体系1的溶液加入到反应体系2中，并保温15min，然后恢复室温继续反应1小时，向体系中加入20ml水。用乙酸乙酯萃取、旋干得粗品，经柱层析纯化得到相应的固体化合物Ⅰ，收率为84％～92％。
实施例3：苯并磷杂环戊二烯目标化合物Ⅱ的制备(举例不限于此)
化合物Ⅱ—01的制备
向10ml反应瓶中加入1mmol化合物Ⅰ—01(R1＝Ph，R2＝Ph)，3ml甲苯溶剂，3mg上述制得的Pd纳米粒子，30℃下反应0.5h，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到287mg(0.95mmol)化合物Ⅱ—01，白色固体，产率95％。
分析数据为:1H NMR(400MHz,CDCl3)δ:7.29-7.54(m,10H),7.60-7.80(5H)；13CNMR(100MHz,CDCl3)δ:124.70(d,JPC＝9.6Hz),126.62,128.95(d,JPC＝12.4Hz),128.96(d,JPC＝10.8Hz),128.97,129.23,129.96(d,JPC＝97.8Hz),130.75,132.27,132.54,132.75(d,JPC＝108.3Hz),133.26,136.58,138.74(d,JCP＝94.2Hz,C),141.64(d,JPC＝28.2Hz)；31PNMR(162MHz,CDCl3)δ＝39.3。
化合物Ⅱ—02的制备
向10ml反应瓶中加入1mmol化合物Ⅰ—02(R1＝Ph，R2＝4-甲氧基-苯基)，3ml甲苯溶剂，3mg上述制得的Pd纳米粒子，30℃下反应0.5h，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到305mg(0.92mmol)化合物Ⅱ—02，白色固体，产率92％。
分析数据为:1H NMR(400MHz,CDCl3)δ:3.76(s,3H),6.85(d,J＝8.8Hz,2H),7.25-7.52(m,7H),7.57-7.68(m,3H),7.73-7.79(m,2H)；13C NMR(100MHz,CDCl3)δ:55.28,114.41,124.28,125.19(d,JPC＝10.8Hz),128.05,128.59(d,JPC＝10.6Hz),128.89(d,JPC＝12.4Hz),128.96,130.21(d,JPC＝97.5Hz),130.73(d,JPC＝10.6Hz),132.18,132.41(d,JPC＝108.4Hz),133.18,134.16(d,JPC＝20.2Hz),138.24(d,JPC＝94.1Hz),142.04(d,JPC＝28.3Hz),160.13；31P NMR(162MHz,CDCl3)δ＝39.4。
化合物Ⅱ—03的制备
向10ml反应瓶中加入1mmol化合物Ⅰ—03(R1＝Ph，R2＝4-三氟甲基苯基)，3ml甲苯溶剂，4mg上述制得的Pd纳米粒子，30℃下反应0.5h，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到337mg(0.91mmol)化合物Ⅱ—03，类白色固体，产率91％。
分析数据为:1H NMR(400MHz,CDCl3)δ:7.32-7.53(m,8H),7.61-7.67(m,2H),7.73-7.78(m,2H),7.82(d,J＝8.1Hz,2H)；13CNMR(100MHz,CDCl3)δ:123.93(q,JCF＝273Hz),125.24,125.83,126.77,129.08(d,JPC＝12.4Hz),129.13,129.31(d,JPC＝98.3Hz),129.69(d,JPC＝10.7Hz),130.29(q,JCF＝32.4Hz),130.68(d,JPC＝10.9),132.54,132.65(d,JPC＝108.8Hz),133.43,136.06,137.38(d,JPC＝94.7Hz),138.89(d,JPC＝19.6Hz),141.14(d,JPC＝27.7Hz)；31P NMR(162MHz,CDCl3)δ＝39.5。
化合物Ⅱ—04的制备
向10ml反应瓶中加入1mmol化合物Ⅰ—04(R1＝Ph，R2＝2-溴-苯基)，3ml甲苯溶剂，4mg上述制得的Pd纳米粒子，35℃下反应0.5h，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到339mg(0.89mmol)化合物Ⅱ—04，白色固体，产率89％。
分析数据为:1H NMR(400MHz,CDCl3)δ:6.98-7.04(m,1H),7.19-7.23(m,1H),7.29-7.54(m,7H),7.59-7.78(m,4H),7.83-7.86(m,1H)；13C NMR(100MHz,CDCl3)δ:122.30,125.20,127.54,128.80(d,JPC＝12.5Hz),128.89(d,JPC＝102.6Hz),129.02,129.50(d,JPC＝10.5Hz),129.53,130.04,130.89(d,JPC＝10.9Hz),131.75(d,JPC＝107.8Hz),132.39,133.30,133.34,133.82,136.84(d,JPC＝94.2Hz),141.22(d,JPC＝28.4Hz),143.31(d,JPC＝19.5Hz)；31P NMR(162MHz,CDCl3)δ＝41.2。
化合物Ⅱ—05的制备
向10ml反应瓶中加入1mmol化合物Ⅰ—05(R1＝4-甲基苯基，R2＝Ph)，3ml甲苯溶剂，3mg上述制得的Pd纳米粒子，30℃下反应0.5h，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到339mg(0.89mmol)化合物Ⅱ—05，白色固体，产率89％。
分析数据为:1H NMR(400MHz,CDCl3)δ:2.31(s,3H),7.12(d,J＝8.0Hz,2H),7.27-7.48(m,6H),7.59-7.63(m,4H),7.72-7.79(m,2H)；13C NMR(100MHz,CDCl3)δ:21.47,124.49,126.54,128.85(d,JPC＝11.0Hz),128.91(d,JCP＝12.3Hz),128.99,129.67,129.70,130.11(d,JPC＝97.7Hz),130.74,132.22,132.65(d,JPC＝108.5Hz),133.20,135.51(d,JPC＝20.3Hz),138.64(d,JPC＝93.9Hz),139.04,141.85(d,JCP＝28.2Hz)；31P NMR(162MHz,CDCl3)δ＝39.1。
Claims (2)
1.一种合成苯并磷杂环戊二烯的方法，其特征在于，其通过如下方法实现：（1）配制苯胺与四氟硼酸的乙醇溶液，冰浴条件下向该溶液中滴加亚硝酸叔丁酯，室温下搅拌反应，过滤得到苯基重氮四氟硼酸盐；苯基重氮四氟硼酸盐用四氢呋喃溶解，室温下与醋酸钯的甲醇溶液搅拌均匀，冰浴条件下再滴加硼氢化钠甲醇溶液，滴加完室温下反应至反应充分；将反应液旋干、洗涤、干燥后得到钯纳米粒子；（2）向反应瓶中加入化合物Ⅰ， 甲苯溶剂及步骤（1）Pd纳米粒子，30℃-40℃下反应，TLC检测反应完全，经萃取、干燥，减压蒸馏除去溶剂，再经过柱层析纯化得到化合物Ⅱ；
其中，R1，R2代表苯基或取代苯基或C1-5烷基；取代苯基选卤素、三氟甲基、C1-5烷基或C1-5烷氧基取代。
2.根据权利要求1所述的合成苯并磷杂环戊二烯的方法，其特征在于，所述的苯胺、四氟硼酸与亚硝酸叔丁酯的摩尔比为1:2.5:2.5；所述的苯基重氮四氟硼酸盐、醋酸钯与硼氢化钠摩尔比为4:1:5。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566310.8A CN108558949B (zh) | 2018-06-04 | 2018-06-04 | 一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810566310.8A CN108558949B (zh) | 2018-06-04 | 2018-06-04 | 一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108558949A true CN108558949A (zh) | 2018-09-21 |
| CN108558949B CN108558949B (zh) | 2020-06-05 |
Family
ID=63552861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810566310.8A Expired - Fee Related CN108558949B (zh) | 2018-06-04 | 2018-06-04 | 一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108558949B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096337A (zh) * | 2018-10-08 | 2018-12-28 | 苏州大学 | 一种磷杂吲哚衍生物、苯并磷杂吲哚衍生物及其制备方法 |
| CN109180728A (zh) * | 2018-10-23 | 2019-01-11 | 佛山科学技术学院 | 一种咔唑基苯并磷杂环戊二烯衍生物及其制备方法 |
| CN113912639A (zh) * | 2021-11-19 | 2022-01-11 | 河南省科学院化学研究所有限公司 | 一种苯并噻咯衍生物的合成方法 |
| CN113999264A (zh) * | 2021-11-25 | 2022-02-01 | 郑州大学 | 一种卤代磷杂苊类化合物及其制备方法 |
-
2018
- 2018-06-04 CN CN201810566310.8A patent/CN108558949B/zh not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096337A (zh) * | 2018-10-08 | 2018-12-28 | 苏州大学 | 一种磷杂吲哚衍生物、苯并磷杂吲哚衍生物及其制备方法 |
| CN109096337B (zh) * | 2018-10-08 | 2019-11-22 | 苏州大学 | 一种磷杂吲哚衍生物、苯并磷杂吲哚衍生物及其制备方法 |
| CN109180728A (zh) * | 2018-10-23 | 2019-01-11 | 佛山科学技术学院 | 一种咔唑基苯并磷杂环戊二烯衍生物及其制备方法 |
| CN113912639A (zh) * | 2021-11-19 | 2022-01-11 | 河南省科学院化学研究所有限公司 | 一种苯并噻咯衍生物的合成方法 |
| CN113999264A (zh) * | 2021-11-25 | 2022-02-01 | 郑州大学 | 一种卤代磷杂苊类化合物及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108558949B (zh) | 2020-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108558949A (zh) | 一种用Pd纳米粒子催化合成苯并磷杂环戊二烯的方法 | |
| CN104991418B (zh) | 一种用于uv-led光固化的增感剂及其制备方法和应用 | |
| CN106008318B (zh) | 一种具有圆偏振发光性质的手性有机染料分子及其制备方法与应用 | |
| CN104557856A (zh) | 一种9,9-二芳基噻杂蒽-10,10-二氧化物的制备方法 | |
| Feng et al. | A facile access to substituted cationic 12-azapyrene salts by rhodium (iii)-catalyzed C–H annulation of N-arylpyridinium salts | |
| CN101462935B (zh) | 一种α-溴代苯乙酮类化合物的合成方法 | |
| CN104559286B (zh) | 一种三苯胺-氟化硼络合二甲基吡咯甲川衍生物有机染料及其制备方法 | |
| CN111484533A (zh) | 手性螺环膦-氮-膦三齿配体及其铱催化剂的制备方法和应用 | |
| Qi et al. | Copper-dipyridylphosphine-catalyzed hydrosilylation: enantioselective synthesis of aryl-and heteroaryl cycloalkyl alcohols | |
| CN106905169B (zh) | 一种乙烯基共轭三芳胺类电荷传输材料及其制备方法 | |
| CN109503667B (zh) | 三配体协同增强聚集诱导发光有机金属铂配合物发光材料 | |
| CN108610278B (zh) | 一种6-氨基-5-酰基苯并[a]咔唑类化合物的合成方法 | |
| Li et al. | Metal-free allylation of electron-rich heteroaryl boronic acids with allylic alcohols | |
| CN110885570B (zh) | 一种近红外染料的制备方法 | |
| CN109574906A (zh) | 一种3,3’-二吲哚基乙酸酯的制备方法 | |
| CN111285881B (zh) | 一种噻吩并[3,4-b]吲哚衍生物及其合成方法 | |
| CN109678908A (zh) | 一种以哒嗪衍生物为配体的双环金属铂（ii）配合物及其制备方法和应用 | |
| CN110078653A (zh) | 一种吲哚取代的9-苯基芴衍生物及其制备方法和用途 | |
| CN114149379B (zh) | 一种简单芳香羧酸与氰基取代的酯类化合物合成多取代噁唑产物的合成方法 | |
| CN111574427B (zh) | 一种2-吲哚-3-氧代吲哚啉类化合物的合成方法 | |
| CN103626791B (zh) | 一种合成3-氨基-4-氟苯硼酸的方法 | |
| CN108558595B (zh) | 一种对苯撑乙烯桥联三聚茚衍生物及其制备方法 | |
| CN111087323B (zh) | 四氰基蒽醌二甲烷小分子受体材料及其制备方法和应用 | |
| CN104558005B (zh) | 微波合成具有D‑π‑A结构的二阶非线性光学发色团的方法 | |
| CN102093334B (zh) | 一组稠环噻吩类化合物的合成方法 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200605 Termination date: 20210604 |