CN111393479A - 一种亲核性磷烯类化合物的制备 - Google Patents
一种亲核性磷烯类化合物的制备 Download PDFInfo
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- CN111393479A CN111393479A CN202010390568.4A CN202010390568A CN111393479A CN 111393479 A CN111393479 A CN 111393479A CN 202010390568 A CN202010390568 A CN 202010390568A CN 111393479 A CN111393479 A CN 111393479A
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- 230000000269 nucleophilic effect Effects 0.000 title claims abstract description 11
- -1 phospho alkene compound Chemical class 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical class C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003983 crown ethers Chemical class 0.000 claims description 4
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- SLRCCWJSBJZJBV-UHFFFAOYSA-N alpha-isosparteine Natural products C1N2CCCCC2C2CN3CCCCC3C1C2 SLRCCWJSBJZJBV-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- SLRCCWJSBJZJBV-ZQDZILKHSA-N sparteine Chemical compound C1N2CCCC[C@@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-ZQDZILKHSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract 1
- 150000003017 phosphorus Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000002739 cryptand Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- 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
- C07F9/6581—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 and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6587—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 and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having two phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
本发明公开了一种亲核性磷烯类化合物的制备方法，属于化学医药制备领域。磷烯(RP)是一类具有六电子结构的一价磷化合物。作为碳卡宾的磷类似物，磷烯一直以来都是重要的有机磷试剂。由于自由的磷烯的不稳定性，所以化学家们利用磷烯分子的双性特征，合成了磷烯的Lewis酸和Lewis碱络合物。这两类络合的磷烯稳定性更高，反应性更容易调控，尤其是Lewis碱配位的亲核性磷烯。本发明使用前体磷的氢化物在冠醚/穴醚的存在下，低温下与碱反应可高产率地得到亲核性磷烯类化合物。所得到的目标产物可作为催化剂用于各种催化反应中。
Description
技术领域
本发明公开了一种亲核性磷烯类化合物的制备方法，属于化学医药制备领域。
背景技术
磷烯(RP)是一类具有六电子结构的一价磷化合物。作为碳卡宾的磷类似物，磷烯一直以来受到有机化学家们的广泛的关注，是重要的有机磷试剂。由于自由的磷烯在室温下不稳定，反应选择性较差，所以这类磷烯无法真正应用到合成化学中。于是化学家们利用磷烯分子的双性特征，合成了磷烯的Lewis酸络合物和Lewis碱络合物。这两类络合的磷烯与自由磷烯相比稳定性更高，反应性更容易调控。因此近三十年来，这两类磷烯是磷烯化学研究的主体。尤其是Lewis碱配位的亲核性磷烯，为了更好的研究磷烯的制备及其反应性，扩展其在合成化学中的应用，化学家们一直致力于发展磷烯新的合成方法。
发明内容
本发明使用前体磷的氢化物在冠醚/穴醚的存在下，低温下与碱在有机溶剂中反应，高产率地得到亲核性磷烯类化合物。所得到的亲核性磷烯类化合物可作为催化剂用于各种催化反应中。
本发明的优点是，本发明所使用的起始原料可通过常规的官能团转化制备，具有结构多样性。该反应产率高，操作简便。
技术方案
本发明所采用的方法是，将前体化合物、冠/穴醚、碱按1∶1∶1.2的比例溶于有机溶剂(主要是乙醚和四氢呋喃等极性比较大的有机溶剂)中，在-78℃下反应1～2小时。之后，抽干溶剂后用己烷洗(少量多次)，粗产物用重结晶提纯。
具体实施方式
为了充分公开本发明中亲核性磷烯的制备方法，下面结合实施例对本发明进行进一步描述。这些实施例只是为了对本发明进行描述，而不是对本发明进行限制。本发明的范围不受这些实施例的限制。本发明的范围在权利要求书中提出。
实施例1：
将前体化合物1(42mg，0.1mmol)和冠醚12-crown-4(20μl，0.12mmol)置于史莱克瓶中，加入1.5ml乙醚，在-78℃下加入新鲜制备的二异丙基氨基锂，低温搅拌反应2h，用真空泵抽干溶剂，粗产品用己烷(1ml*3)洗，再用乙醚溶剂低温下重结晶得到目标产物28mg，产率73％。
实施例2：
将前体化合物2(43mg，0.1mmol)和冠醚18-crown-6(32mg，0.12mmol)置于史莱克瓶中，加入2.0ml乙醚，在-78℃下加入叔丁醇钾(13mg，0.12mmol)，低温搅拌反应2h，用真空泵抽干溶剂，粗产品用己烷(1ml*3)洗，再用乙醚溶剂低温下重结晶得到目标产物27mg，产率69％。
实施例3：
将前体化合物3(45mg，0.1mmol)和冠醚15-crown-5(24μl，0.12mmol)置于史莱克瓶中，加入1.5ml乙醚，在-78℃下加入二-(三甲基硅基)氨基钠(22mg，0.12mmol)，低温搅拌反应2h，用真空泵抽干溶剂，粗产品用己烷(1ml*3)洗，再用乙醚溶剂低温下重结晶得到目标产物27mg，产率66％。
Claims (8)
1.亲核性磷烯类化合物。其结构如下：
2.权利要求1的制备方法，其特征在于，反应前体在有机溶剂中，一定温度下，通过碱与冠/穴醚拔除HX可以制得亲核性磷烯化合物。
3.权利要求2的制备方法，其特征在于，所述的有机溶剂包括：乙醚，四氢呋喃，己烷。
4.权利要求2的制备方法，其特征在于，所述的一定温度是指：-40℃～-78℃。
5.权利要求2的制备方法，其特征在于，所述的碱包括：LDA，t-BuLi，n-BuLi，NaH，NaN(SiMe3)2，KOtBu，KH，N-Heterocyclic Carbene，phosphazene，(+)-Spartein。
6.权利要求2的制备方法，其特征在于，所述的冠醚包括：12-crown-4，15-crown-5，18-crown-6；穴醚包括：Cryptand 2，2，1，Cryptand 2，2，2。
7.权利要求2的制备方法，反应前体的结构为
其中R包括：CH(SiMe3)2，C5Me5，CPh3
其中LB包括：
其中X包括：F，Cl，Br，I 。
8.权利要求7中，芳香基Ar具有以下结构：
其中R包括烷基、烷氧基、硝基、氰基、羧基、羧酸酯基、羟基、卤素、氨基及取代氨基等。
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2020
- 2020-05-11 CN CN202010390568.4A patent/CN111393479A/zh active Pending
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