WO2017143598A1 - 一种α-羟基磷酸酯的制备方法 - Google Patents
一种α-羟基磷酸酯的制备方法 Download PDFInfo
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- WO2017143598A1 WO2017143598A1 PCT/CN2016/074736 CN2016074736W WO2017143598A1 WO 2017143598 A1 WO2017143598 A1 WO 2017143598A1 CN 2016074736 W CN2016074736 W CN 2016074736W WO 2017143598 A1 WO2017143598 A1 WO 2017143598A1
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- ketone
- diimine
- hydroxyphosphate
- hydroxy
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 16
- 239000010452 phosphate Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 229910000071 diazene Inorganic materials 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012327 Ruthenium complex Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- YXVSURZEXVMUAM-UHFFFAOYSA-N 1-(2-hydroxy-4,5-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC(C)=C(C)C=C1O YXVSURZEXVMUAM-UHFFFAOYSA-N 0.000 claims description 2
- MCDJUVXLLXTCFP-UHFFFAOYSA-N 1-(3,5-difluoro-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC(F)=CC(F)=C1O MCDJUVXLLXTCFP-UHFFFAOYSA-N 0.000 claims description 2
- YNPDFBFVMJNGKZ-UHFFFAOYSA-N 2'-Hydroxy-5'-methylacetophenone Chemical compound CC(=O)C1=CC(C)=CC=C1O YNPDFBFVMJNGKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- -1 inorganic Chemical compound 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
Definitions
- the present invention relates to a technique for preparing a phosphorus-containing compound, and in particular to a method for preparing a-hydroxyphosphate.
- A-hydroxyphosphates as a class of phosphorus-containing compounds, are important components of some antiviral agents, anticancer drugs, and enzymes, and have various biological functions.
- this compound is also widely used in the frontier molecular sciences, such as polymer materials, nanotechnology, bioprospecting, drug discovery and asymmetric catalysis; the compound can further synthesize derivatives with more complex structural units.
- Karasik, AA Sinyashin, OG Phosphorus Compounds: Advanced Tools in Catalysis and Material Science. Vol. 37, Eds.: Peruzzini, M.; Gonsalvi, L, Kazan, 2011, pp. 375-444.
- Sikorski , JA; Miller, MJ; Braccolino, DS Phosphorus, Sulfur and Silicon. 1993, 76, 115).
- the existing catalyst has the defects of harsh reaction conditions and large amount of catalyst; in the prior art, the application of the b-diimine-based di-b-diimide divalent rare earth complex has rarely been reported, and There is no report on the reaction of a bis-b-diimine divalent ruthenium complex to catalyze the reaction of a carbonyl compound with diethyl phosphite.
- the object of the present invention is to provide a method for preparing a-hydroxyphosphate, which is prepared by bis-b-diimine divalent ruthenium complex catalyzed by ketone and diethyl phosphite, and the reaction has higher reaction. Catalytic activity, low catalyst dosage, and good substrate application range. [0005] In order to achieve the above object, the technical solution adopted by the present invention is:
- a method for preparing a-hydroxyphosphate comprising the steps of: adding diethyl phosphite to a reactor under a nitrogen atmosphere, and adding a double b-diimine divalent ruthenium complex, mixing 5 ⁇ 6 minutes; then adding a ketone; synthesis reaction to obtain a-hydroxy phosphate; the molar ratio of the bis-b-diimine divalent ruthenium complex, diethyl phosphite, ketone is (1.2% - 1.5%) : (1.4 ⁇ 1.5) :1;
- the ketone is 2,4-diethoxyacetophenone, 2-hydroxy-5-methylacetophenone, 2-hydroxy-4,5-dimethylacetophenone or 1-(3, 5-difluoro-2-hydroxyphenyl)ethan-1-one;
- the molar ratio of the bis b-diimine divalent ruthenium complex, diethyl phosphite, and ketone is 1.3 ⁇ 3 ⁇ 4:1.5:1.
- the temperature of the synthesis reaction is room temperature, and the time is 38 to 45 minutes; first, the double b-diimine divalent ruthenium complex is mixed with diethyl phosphite, and then the ketone is added. There is a significant increase in the reaction yield.
- the bis b-diimine divalent ruthenium complex is first mixed with diethyl phosphite for 5 minutes; the synthesis reaction is carried out for 41 minutes.
- the present invention discloses a method for synthesizing ⁇ -hydroxy phosphate by a double b-diimine divalent europium complex catalyzed addition reaction of a ketone and diethyl phosphite; Under mild conditions (room temperature
- the catalyst dosage is only 1.3 mol%, and the reaction time is 41 minutes; and the catalyst of the present invention has a wide application range to substrates, and is suitable for aromatic ketones with different substituent positions and different electronic effects; and provides more options for industrial synthesis of ⁇ -hydroxy phosphate.
- the catalyst Yb(L 2 - Me ) 2 ( THF) was added under a nitrogen atmosphere in a 20 mL reaction flask, and then the phosphorous acid was added by a pipette. The ethyl ester was then stirred at room temperature, and then the ketone was added by a pipette. After reacting at room temperature, a drop was taken in a nuclear magnetic tube with a pipette, and a solution of CDC1 3 was added to prepare a ⁇ spectrum yield. The glove box was transferred out, the reaction was quenched with ethyl acetate and dissolved with EtOAc (EtOAc).
- EtOAc EtOAc
- the Yb(L n) 2 (THF) catalyst shows a good substrate suitability, and the corresponding ⁇ -hydroxy phosphate can be obtained in a high yield, and the benzene ring can be found.
- the electron effect of the radical has no obvious effect on the reaction, and the yield of more than 80% can be obtained, and the steric hindrance effect of the substituent on the benzene ring has no obvious influence on the reaction.
- the material also has good catalysis; in particular, the preparation method of the present invention can achieve high yield without solvent.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic 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
提供了一种α-羟基磷酸酯的制备方法,具体为在氮气气氛中,以酮和亚磷酸二乙酯为反应物,在有机配合物催化下,制备结构多样的α-羟基磷酸酯。该制备方法可在温和的条件下高活性地催化酮与亚磷酸二乙酯的反应,具有反应时间短,反应条件温和,且后处理方法方便、简单的优点。
Description
发明名称:一种 (X-羟基磷酸酯的制备方法
技术领域
[0001] 本发明涉及一种含磷化合物的制备技术, 具体涉及一种 a-羟基磷酸酯的制备方 法。
背景技术
[0002] a-羟基磷酸酯作为一类含磷化合物, 是一些抗病毒制剂、 抗癌药物、 及酶中的 重要组成部分, 具有多种生物功能。 同吋, 该化合物在前沿的分子科学领域也 具有广泛的应用, 如高分子材料, 纳米技术, 生物探测, 药物研发以及不对称 催化方面; 该化合物还能够进一步合成具有更加复杂的结构单元的衍生物 (参见 : Karasik, A. A.; Sinyashin, O. G. Phosphorus Compounds: Advanced Tools in Catalysis and Material Science. Vol. 37, Eds.: Peruzzini, M.; Gonsalvi, L, Kazan, 2011, pp. 375-444. ;Sikorski, J. A.; Miller, M. J.; Braccolino, D. S. Phosphorus, Sulfur and Silicon. 1993, 76, 115)。
[0003] 亚磷酸二乙酯与羰基化合物的加成反应 (即 Pudovik反应) , 是一种合成 ot-羟 基磷酸酯最直接、 最原子经济的方法; 目前文献所报道的用于催化羰基化合物 与亚磷酸二乙酯的氢磷化反应的催化体系种类较多, 主要有无机、 有机小分子 、 酸、 碱、 金属有机化合物。 但是现有催化剂存在反应条件苛刻、 催化剂用量 大等缺陷; 现有技术中, 以 b-二亚胺基为配体的双 b-二亚胺基二价稀土配合物 的应用鲜有报道, 更没有关于双 b-二亚胺基二价镱配合物催化羰基化合物和亚 磷酸二乙酯反应的报道。
技术问题
问题的解决方案
技术解决方案
[0004] 本发明的发明目的是提供一种 a-羟基磷酸酯的制备方法, 以双 b-二亚胺基二价 镱配合物催化酮和亚磷酸二乙酯制备得到, 反应具有更高的催化活性, 低催化 剂用量, 并有很好的底物适用范围。
[0005] 为达到上述目的, 本发明采用的技术方案是:
[0006] 一种制备 a-羟基磷酸酯的方法, 包括以下步骤, 氮气气氛下, 将亚磷酸二乙酯 加入反应器中, 再加入双 b-二亚胺基二价镱配合物, 混合 5〜6分钟; 然后加入 酮; 合成反应得到 a-羟基磷酸酯; 所述双 b-二亚胺基二价镱配合物、 亚磷酸二 乙酯、 酮的摩尔比为 (1.2%— 1.5%) : (1.4〜1.5) :1;
[0007] 所述酮为 2,4-二乙氧基苯乙酮、 2-羟基 -5-甲基苯乙酮、 2-羟基 -4,5二甲基苯乙酮 或者 1-(3,5-二氟 -2-羟基苯)乙 -1-酮;
[0008] 所述双 b-二亚胺基二价镱配合物的化学结构式如下:
[0009] 其中 Ar为 2-MeC 6H 4。 双 b-二亚胺基二价镱配合物的分子式可表示为:
[(2-Me-C 6H 4-NC(Me)CHC(Me)N-C 6H 4-2-Me)] 2 Yb(THF), 简称 Yb(L 2 Me) 2(THF)
[0010] 优选的技术方案中, 所述双 b-二亚胺基二价镱配合物、 亚磷酸二乙酯、 酮的摩 尔比为 1.3<¾:1.5:1。
[0011] 上述技术方案中, 所述合成反应的温度为室温, 吋间为 38〜45分钟; 先将双 b- 二亚胺基二价镱配合物与亚磷酸二乙酯混合, 再加入酮对反应收率有明显的提 升。
[0012] 优选的技术方案中, 先将双 b-二亚胺基二价镱配合物与亚磷酸二乙酯混合 5分 钟; 合成反应的吋间为 41分钟。
[0013] 上述技术方案中, 反应结束后进行提纯处理, 具体为加入乙酸乙酯溶解反应产 物, 然后旋干, 再用正己烷洗涤, 得到 a-羟基磷酸酯; 具体操作步骤属于常规 手段。
[0014] 上述技术方案可表示如下:
HO
- "、 OEf
发明的有益效果
有益效果
[0016] 本发明幵发了一种双 b-二亚胺基二价镱配合物催化酮和亚磷酸二乙酯的加成反 应合成 α -羟基磷酸酯的方法; 由于该催化剂的使用, 可以在温和条件下 (室温
) 高活性的催化酮和亚磷酸二乙酯合成 0C -羟基磷酸酯; 与现有的几种催化剂相 比, 在达到相同收率的情况下, 催化剂用量仅需 1.3 mol%, 反应吋间为 41分钟; 并且本发明公幵的催化剂对底物的适用范围较宽, 适用于不同取代基位置、 不 同电子效应的芳香酮; 为 α -羟基磷酸酯的工业化合成提供更多选择。
本发明的实施方式
[0017] 下面结合实施例对本发明作进一步描述:
[0018] 实施例 Yb(L 2(THF)催化酮和亚磷酸二乙酯合成 ot-羟基磷酸酯
[0019] 根据表 1的原料组成以及工艺参数, 在手套箱中, 在 20mL的反应瓶中氮气保护 下加入催化剂 Yb(L 2- Me) 2(THF), 然后用移液枪加入亚磷酸二乙酯, 然后在室温 下搅拌, 再用移液枪加入酮, 在室温下反应后, 用滴管吸取一滴于核磁管中, 加入 CDC1 3配成溶液, 计算 Ή谱产率。 转出手套箱, 用乙酸乙酯终止反应, 并 用适量的乙酸乙酯溶解, 旋蒸除去溶剂, 剩余固体用正己烷 (4x5 mL)洗涤, 得到 相应 ot-羟基磷酸酯。
[0020] 表 1 合成 ot-羟基磷酸酯的原料摩尔比例以及工艺参数
以上实施例可以看出, Yb(L n) 2(THF)催化剂显示出很好的底物适用能力, 都 能以很高的产率得到相应的 α-羟基磷酸酯, 可以发现苯环上取代基的电子效应对 该反应并没有明显的影响, 都能得到 80%以上的收率, 而苯环上取代基的位阻效 应对该反应也没有明显的影响, 对于一些具有共轭结构的底物, 也有良好的催 化; 尤其是本发明公幵的制备方法无需溶剂, 依然可以取得很高的产率。
Claims
[权利要求 1] 一种制备 a-羟基磷酸酯的方法, 包括以下步骤, 氮气气氛下, 将亚磷 酸二乙酯加入反应器中, 再加入双 b-二亚胺基二价镱配合物, 混合 5 〜6分钟; 然后加入酮; 合成反应得到 ot-羟基磷酸酯; 所述双 b-二亚 胺基二价镱配合物、 亚磷酸二乙酯、 酮的摩尔比为 (1.2<¾〜1.5%) : ( 1.4〜1.5) : 1;
所述酮为 2,4-二乙氧基苯乙酮、 2-羟基 -5甲基苯乙酮、 2-羟基 -4,5二甲 基苯乙酮或者 1-(3,5-二氟 -2-羟基苯)乙 -1-酮;
所述双 b-二亚胺基二价镱配合物的化学结构式如下:
其中 Ar为 2-MeC 6H 4。
根据权利要求 1所述制备 oc-羟基磷酸酯的方法, 其特征在于: 所述双 b -二亚胺基二价镱配合物、 酮的摩尔比为 1.3%: 1。
根据权利要求 1所述制备 oc-羟基磷酸酯的方法, 其特征在于: 所述亚 磷酸二乙酯、 酮的摩尔比为 1.5:1。
根据权利要求 1所述制备 oc-羟基磷酸酯的方法, 其特征在于: 所述合 成反应的温度为室温, 吋间为 38〜45分钟。
根据权利要求 4所述制备 oc-羟基磷酸酯的方法, 其特征在于: 合成反 应的吋间为 41分钟。
根据权利要求 1所述制备 oc-羟基磷酸酯的方法, 其特征在于: 先将双 b -二亚胺基二价镱配合物与亚磷酸二乙酯混合 5分钟。
[权利要求 7] 根据权利要求 1所述制备 oc-羟基磷酸酯的方法, 其特征在于: 反应结 束后进行提纯处理, 具体为加入乙酸乙酯溶解反应产物, 然后旋干, 再用正己烷洗涤, 得到 oc-羟基磷酸酯。
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Citations (3)
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CN102898482A (zh) * | 2012-11-08 | 2013-01-30 | 苏州大学 | 一种双金属茂基稀土胍基化合物及其制备方法及羟基亚磷酸酯类化合物的制备方法 |
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