CN106432331B - 一种β-羰基磷酸酯类化合物及其制备方法 - Google Patents
一种β-羰基磷酸酯类化合物及其制备方法 Download PDFInfo
- Publication number
- CN106432331B CN106432331B CN201610826388.XA CN201610826388A CN106432331B CN 106432331 B CN106432331 B CN 106432331B CN 201610826388 A CN201610826388 A CN 201610826388A CN 106432331 B CN106432331 B CN 106432331B
- Authority
- CN
- China
- Prior art keywords
- oxo
- phosphoric acid
- acid ester
- ester type
- type compound
- 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.)
- Expired - Fee Related
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 14
- 235000019394 potassium persulphate Nutrition 0.000 claims description 14
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- 229940071536 silver acetate Drugs 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 229930195733 hydrocarbon Natural products 0.000 claims 3
- 150000002430 hydrocarbons Chemical class 0.000 claims 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052709 silver Inorganic materials 0.000 abstract description 16
- 239000004332 silver Substances 0.000 abstract description 16
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 7
- 125000003107 substituted aryl group Chemical group 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 150000008301 phosphite esters Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- -1 aryl olefin Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
- C07F9/4059—Compounds containing the structure (RY)2P(=X)-(CH2)n-C(=O)-(CH2)m-Ar, (X, Y = O, S, Se; n>=1, m>=0)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (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β‑羰基磷酸酯类化合物,具体结构式为:其中,R1为芳基或取代芳基;R2为烷基。以烯烃和H‑亚磷酸酯为原料,首次将银催化的自由基历程用于β‑羰基磷酸酯类化合物的合成中。在发明中,不需要加入任何的碱性添加剂,而且反应条件温和,易于实现规模化生产。实验结果表明,获得的β‑羰基磷酸酯类化合物的产率可高达70%。
Description
技术领域
本发明涉及化学合成领域,具体为一种β-羰基磷酸酯类化合物及其制备方法。
背景技术
β-羰基磷酸酯类化合物是一类非常重要的含磷有机中间体,具有广泛的生物活性,在药物以及合成研究中发挥着巨大的作用。自1898年米歇尔–阿尔布佐夫反应发现可以用来合成β-羰基磷酸酯以来,人们对β-羰基磷酸酯的合成研究就一直没有间断过,到目前为止已经发展了很多β-羰基磷酸酯的合成方法。虽然这些方法这些方法各有其优势,但也或多或少的存在着一些相应的问题。最近,以芳基烯烃和H-亚磷酸酯为反应原料,加入相应的碱性添加剂,在铜和铁的共催化作用下,可以有效地实现β-羰基磷酸酯的合成(Angew.Chem.Int.Ed.,2011,50,9097)。该方法巨大的优势就是以便宜易得的烯烃和H-亚磷酸酯为反应的原料,反应条件温和。但是需要使用双金属催化剂、碱性添加剂以及纯氧的反应氛围,这就限制了其进一步的大规模生产。
因此,改进现有的β-羰基磷酸酯类化合物及其制备方法,发展一种廉价、安全、并可以放大量生产的新方法是非常值得研究的课题。
发明内容
为了克服上述现有技术中的不足,本发明提供了一种以廉价易得的烯烃和H-亚磷酸酯类化合物作为反应的起始原料,银盐为催化剂,过硫酸钾为氧化剂,易于实现大规模生产的β-羰基磷酸酯类化合物及其制备方法。反应条件温和,不需要加入任何的碱性添加剂,只需要在溶剂中搅拌加热即可有效地得到各种取代的β-羰基磷酸酯类化合物。
本发明的目的是这样实现的:
一种β-羰基磷酸酯类化合物,其具体结构式为:
其中,R1为芳基或取代芳基;R2为烷基。
所述的β-羰基磷酸酯类化合物的制备方法为:
a)将具有结构(I)的烯烃和结构(II)的H-亚磷酸酯类化合物,催化剂银盐以及氧化剂过硫酸钾分散在溶剂乙腈中;
b)向步骤a)得到的混合物在25℃—80℃温度下反应6—18h,得到含有结构(III)的β-羰基磷酸酯类化合物;
所述R1为芳基,所述的芳基为苯基、萘基;
所述R1为取代芳基,所述的取代芳基为4-氯苯基、3-氯苯基、4-氟苯基、4-溴苯基、4-甲基苯基、4-硝基苯基、4-甲氧基苯基、3-三氟甲基苯基;
所述的R2为甲基、乙基、异丙基或正丁基;
所述的催化剂银盐为硝酸银、乙酸银、硫酸银或氧化银;
所述的氧化剂为过硫酸钾;
所述烯烃与H-亚磷酸酯的摩尔比为1:1—1:2;
所述烯烃与银盐的摩尔比为20:1—5:1;
所述烯烃与氧化剂过硫酸钾的摩尔比为1:1—1:3;
所述的反应温度为25℃—80℃;
所述的反应时间为6—18h。
积极有益效果:与现有化学合成领域相关技术相比,本发明以烯烃和H-亚磷酸酯为原料,首次将银催化的自由基历程用于β-羰基磷酸酯类化合物的合成中。在该法中,不需要加入任何的碱性添加剂,而且反应条件温和,易于实现规模化生产。实验结果表明,获得的β-羰基磷酸酯类化合物的产率可高达70%。
附图说明
图1为根据本发明实施例1,2,3制备的2-苯基β-羰基磷酸酯的核磁共振氢谱;
图2为根据本发明实施例1,2,3制备的2-苯基β-羰基磷酸酯的核磁共振碳谱;
图3为根据本发明实施例1,2,3制备的2-苯基β-羰基磷酸酯的核磁共振磷谱。
具体实施方式
下面结合附图及实施例,对本发明做进一步的说明:
一种β-羰基磷酸酯类化合物,其具体结构式为:
其中,R1为芳基或取代芳基;R2为烷基。
所述的一种β-羰基磷酸酯类化合物的制备方法,包括以下步骤:
a)将具有结构(I)的烯烃和结构(II)的H-亚磷酸酯类化合物,催化剂银盐以及氧化剂过硫酸钾分散在溶剂乙腈中;
b)向步骤a)得到的混合物在25℃—80℃温度下反应6—18h,得到含有结构(III)的β-羰基磷酸酯类化合物;
所述R1为芳基,所述的芳基为苯基或萘基;
所述R1为取代芳基,所述的取代芳基为4-氯苯基、3-氯苯基、4-氟苯基、4-溴苯基、4-甲基苯基、4-硝基苯基、4-甲氧基苯基或3-三氟甲基苯基;
所述的R2为甲基、乙基、异丙基或正丁基;
所述的催化剂银盐为硝酸银、乙酸银、硫酸银或氧化银;
所述的氧化剂为过硫酸钾;
所述烯烃与H-亚磷酸酯的摩尔比为1:1—1:2;
所述烯烃与银盐的摩尔比为20:1—5:1;
所述烯烃与氧化剂过硫酸钾的摩尔比为1:1—1:3;
所述的反应温度为25℃—80℃;
所述的反应时间为6—18h。
实施例1
在一个洁净的10毫升玻璃反应管中,依次加入醋酸银2.1毫克、过硫酸钾202毫克、苯乙烯26毫克、亚磷酸二乙酯37.5毫克,再在上述混合物中加入2毫升乙腈作溶剂,装上冷凝回流管,80℃反应8小时。反应结束后,直接将反应混合物旋干,所得剩余物再用石油醚和乙酸乙酯(体积比为3:1)过柱分离,得到41.6毫克浅黄色液体。
本实施例制备的产物的核磁共振氢谱如图1所示,核磁共振碳谱如图2所示,核磁共振磷谱如图3所示。从图谱中可以确认,获得的产物为2-苯基β-羰基磷酸酯。
实施例2
在一个洁净的10毫升玻璃反应管中,依次加入硝酸银4.2毫克、过硫酸钾178毫克、苯乙烯26毫克、亚磷酸二乙酯37.5毫克,再在上述混合物中加入2毫升乙腈作溶剂,装上冷凝回流管,60℃反应12小时。反应结束后,直接将反应混合物旋干,所得剩余物再用石油醚和乙酸乙酯(体积比为3:1)过柱分离,得到39.6毫克浅黄色液体。
本实施例制备的产物的核磁共振氢谱如图1所示,核磁共振碳谱如图2所示,核磁共振磷谱如图3所示。从图谱中可以确认,获得的产物为2-苯基β-羰基磷酸酯。
实施例3
在一个洁净的10毫升玻璃反应管中,依次加入醋酸银1.8毫克、过硫酸钾202毫克、苯乙烯26毫克、亚磷酸二乙酯41.2毫克,再在上述混合物中加入5毫升乙腈作溶剂,装上冷凝回流管,30℃反应18小时。反应结束后,直接将反应混合物旋干,所得剩余物再用石油醚和乙酸乙酯(体积比为3:1)过柱分离,得到24.5毫克浅黄色液体。
本实施例制备的产物的核磁共振氢谱如图1所示,核磁共振碳谱如图2所示,核磁共振磷谱如图3所示。从图谱中可以确认,获得的产物为2-苯基β-羰基磷酸酯。
在一个实施方案中,本发明提供的一种β-羰基磷酸酯类化合物的制备方法,其中将烯烃、H-亚磷酸酯类化合物,催化剂银盐以及氧化剂过硫酸钾分散在溶剂乙腈中;将得到的反应混合物通过搅拌加热,得到相应的β-羰基磷酸酯类化合物。
在本发明中,所述的催化剂一价银在氧化剂过硫酸钾的作用下可以生成相应的二价银,二价银再原位将H-亚磷酸酯类化合物氧化成H-亚磷酸酯自由基,自身则可被还原成一价银,从而进入到下一个催化循环中。生成的H-亚磷酸酯自由基可以加成到烯烃碳-碳双键中生成苄基自由基,苄基自由基又被二价银氧化成苄基碳正离子,然后溶剂中的水亲核进攻碳正离子,再经过进一步氧化则可得到最终的产物β-羰基磷酸酯类化合物。在整个催化循环中,银盐经历了一价银到二价银、二价银到一价银、一价银到二价银、二价银到一价银的转换过程。该方法首次将银催化的自由基反应用于β-羰基磷酸酯类化合物的合成中,其优势非常明显,不需要任何的碱性添加剂,反应原料、催化剂以及氧化剂廉价易得。
上述是对本发明优选的实施例的说明,以使本领域技术人员能够实现或使用本发明,对这些实施例的一些修改对本领域专业人员来说是显而易见的,本文中所定义的一般原理可以在不脱离本发明的范围或精神情况下,在其他实施例中实现。因此,本发明范围不受上述具体实施例的限制。
Claims (6)
1.一种β-羰基磷酸酯类化合物的制备方法,其特征在于,包括以下步骤:
将具有结构(I)的烯烃和结构(II)的H-亚磷酸酯类化合物加入到催化剂银盐以及氧化剂过硫酸钾中,通过在溶剂乙腈中加热反应,即可得到具有结构(III)的β-羰基磷酸酯类化合物:
所述的催化剂银盐为硝酸银、乙酸银或硫酸银;
其中, R1为苯基、萘基、4-氯苯基、3-氯苯基、4-氟苯基、4-溴苯基、4-甲基苯基、4-硝基苯基、4-甲氧基苯基或3-三氟甲基苯基;R2为甲基、乙基、异丙基或正丁基。
2.根据权利要求1所述的一种β-羰基磷酸酯类化合物的制备方法,其特征在于:所述烯烃与H-亚磷酸酯的摩尔比为1:1—1:2。
3.根据权利要求1所述的一种β-羰基磷酸酯类化合物的制备方法,其特征在于:所述烯烃与银盐的摩尔比为20:1—5:1。
4.根据权利要求1所述的一种β-羰基磷酸酯类化合物的制备方法,其特征在于:所述烯烃与氧化剂过硫酸钾的摩尔比为1:1—1:3。
5.根据权利要求1所述的一种β-羰基磷酸酯类化合物的制备方法,其特征在于:所述的反应温度为25oC—80oC。
6.根据权利要求1所述的一种β-羰基磷酸酯类化合物的制备方法,其特征在于:所述的反应时间为6—18h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610826388.XA CN106432331B (zh) | 2016-09-14 | 2016-09-14 | 一种β-羰基磷酸酯类化合物及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610826388.XA CN106432331B (zh) | 2016-09-14 | 2016-09-14 | 一种β-羰基磷酸酯类化合物及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106432331A CN106432331A (zh) | 2017-02-22 |
CN106432331B true CN106432331B (zh) | 2018-06-29 |
Family
ID=58168325
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610826388.XA Expired - Fee Related CN106432331B (zh) | 2016-09-14 | 2016-09-14 | 一种β-羰基磷酸酯类化合物及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106432331B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104497044A (zh) * | 2014-12-11 | 2015-04-08 | 华侨大学 | 一种高效制备β-羰基磷酸酯的方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008097483A2 (en) * | 2007-02-02 | 2008-08-14 | Neurogen Corporation | Methods for preparing aryl-substituted ketophosphonates |
-
2016
- 2016-09-14 CN CN201610826388.XA patent/CN106432331B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104497044A (zh) * | 2014-12-11 | 2015-04-08 | 华侨大学 | 一种高效制备β-羰基磷酸酯的方法 |
Non-Patent Citations (2)
Title |
---|
"A one-pot strategy to synthesize β-ketophosphonates: silver/copper catalyzed direct oxyphosphorylation of alkynes with H-phosphonates and oxygen in the air";Xin Chen et al.;《Chem. Commun.》;20150127;第51卷;第3846-3849页 * |
"Catalytic and Direct Oxyphosphorylation of Alkenes with Dioxygen and H-Phosphonates Leading to β-Ketophosphonates";Wei Wei et al.;《Angew. Chem. Int. Ed.》;20110824;第50卷;第9097-9099页 * |
Also Published As
Publication number | Publication date |
---|---|
CN106432331A (zh) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Potkin et al. | 5-(p-tolyl) isoxazol-3-amine-palladium (II) complex: Preparation, structure, and catalytic application in the Suzuki-Miyaura reaction in water | |
Yang et al. | A novel sustainable strategy for the synthesis of phenols by magnetic CuFe2O4-catalyzed oxidative hydroxylation of arylboronic acids under mild conditions in water | |
CN102633821B (zh) | 由嘧啶羧酸基配体构筑的铜配合物及其制备方法与应用 | |
Li et al. | Ligand-free nickel-catalyzed conversion of aldoximes into nitriles | |
But et al. | Organocatalytic Mitsunobu reactions with 3, 5-dinitrobenzoic acid | |
Zhang et al. | Highly efficient synthesis of multi-substituted allenes from propargyl acetates and organoaluminum reagents mediated by palladium | |
Zhang et al. | Screening commercial semiconductors for visible light driven asymmetric catalysis | |
Telvekar et al. | Oxidative decarboxylation of 2-aryl carboxylic acids using (diacetoxyiodo) benzene for preparation of aryl aldehydes, ketones, and nitriles | |
Zhu et al. | Bis (cyclohexanone) oxalyldihydrazone/copper (II) oxide-a novel and efficient catalytic system for Ullmann-type CN coupling in pure water | |
CN106432331B (zh) | 一种β-羰基磷酸酯类化合物及其制备方法 | |
Moriya et al. | Pd (II)-Catalyzed Asymmetric Fluorination of α-Aryl-α-cyanophosphonates with the Aid of 2, 6-Lutidine | |
CN103214328B (zh) | 一种α-溴代芳香酮类化合物的合成方法 | |
Sakakura et al. | Unusual Rate Acceleration in Brønsted Acid Catalyzed Dehydration Reactions: Local Hydrophobic Environment in Aggregated N‐(2, 6‐diphenylphenyl)‐N‐mesitylammonium Pentafluorobenzenesulfonates | |
Li et al. | The unprecedented C-alkylation and tandem C-/O-alkylation of phenanthrolinium salts with cyclic 1, 3-dicarbonyl compounds | |
Sandré et al. | First principles location of the transition state for formation of dimethyl ether in a zeolite | |
Zhang et al. | Selective Construction of Trefoil knots and a Molecular Borromean Ring Induced by Steric Hindrance of Thioether Ligands | |
Zhao et al. | Nucleophilic addition to C= O and C= N bonds by nucleophiles containing a diazo group | |
CN106673976B (zh) | 一种α-羟基环十五酮的制备方法 | |
CN106117225A (zh) | 苯并菲癸烷氧基桥连异辛烷氧基苯基卟啉金属Zn配合物的合成方法 | |
Menand et al. | TMAF-catalyzed conjugate addition of oxazolidinone and thiols | |
Liu et al. | RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes | |
CN107522741B (zh) | 一种磷酸酯类化合物的合成方法 | |
CN106117220A (zh) | 苯并菲十二烷氧基桥连异辛烷氧基苯基卟啉金属Zn配合物的合成方法 | |
Kawano et al. | Iodoarene-mediated one-pot preparation of 2, 4, 5-trisubstituted oxazoles from ketones | |
Zhang et al. | Palladium‐catalyzed Atroposelective Interannular C− H Arylation of Biaryl Aldehydes with Aryl Iodides Enabled by a Transient Directing Group Strategy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB03 | Change of inventor or designer information | ||
CB03 | Change of inventor or designer information |
Inventor after: Tang Lin Inventor after: Tan Meirong Inventor after: Xiao Huijin Inventor after: Qiao Xin Inventor after: Yang Dian Inventor before: Tan Meirong |
|
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: 20180629 Termination date: 20190914 |