butyl ethylphosphonite | 1929-44-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: butyl ethylphosphonite
• 英文别名: Butoxy(ethyl)phosphinic acid；butoxy(ethyl)phosphinic acid
• CAS: 1929-44-8
• 化学式: C₆H₁₅O₃P
• 分子量: 166.157
• InChiKey: ZATJRDFVXWVKJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  butyl ethylphosphonite 在 五氯化磷 作用下， 生成 ethyl-phosphonic acid butyl ester chloride
  参考文献：
  名称：

  Rasumow et al., Zhurnal Obshchei Khimii, 1957, vol. 27, p. 2394; engl. Ausg. S. 2455

  摘要：

  DOI：
• 作为产物：
  描述：

  n-Butyl-tert.-butylperoxy-ethylphosphonat 以 甲苯 为溶剂， 生成 butyl ethylphosphonite
  参考文献：
  名称：

  Sosnovsky,S.; Konieczny,M., Phosphorus and the Related Group V Elements, 1974, vol. 4, p. 255 - 264

  摘要：

  DOI：

文献信息

• Fragmentation-Related Phosphonylation of Nucleophiles Utilizing P-Alkyl 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide Precursors
  作者：Tamara Kovács、Laura Szandra Fülöp、György Keglevich

  DOI：10.1002/hc.21304

  日期：2016.3

  New P-alkyl 2,3-oxaphosphabicyclo-[2.2.2]octene 3-oxides were synthesized by the Bayer–Villiger oxidation of the corresponding 7-phosphanorbornene 7-oxides and were used as precursors for reactive alkylmetaphosphonates useful in the phosphonylation of alcohols. This is the first case that the reactivity of the two regioisomers formed by O-insertion was differentiated and that the fragmentation-related

  新的 P-烷基 2,3-氧杂磷杂双环-[2.2.2] 辛烯 3-氧化物是通过相应的 7-磷酰冰片烯 7-氧化物的 Bayer-Villiger 氧化合成的，并用作反应性烷基偏膦酸酯的前体，可用于醇的膦酰化. 这是第一个通过 O 插入形成的两种区域异构体的反应性不同的情况，并且在微波辅助条件下实现了导致膦酸酯的断裂相关的膦酰化。
• Method for the production of monohydroxy-functionalized dialkylphosphinic acids, esters, and salts using ethylene oxide, and use thereof
  申请人：Hill Michael

  公开号：US08987490B2

  公开（公告）日：2015-03-24

  A method for producing monohydroxy-functionalized dialkylphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with alkylene oxides of formula (V) in the presence of a catalyst B to obtain a monofunctionalized dialkylphosphinic acid derivative (III), catalyst A represents transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand, and catalyst B is a Lewis acid.

  一种生产单羟基功能化二烷基膦酸、酯和盐的方法，其特征在于a) 在催化剂A的存在下，将膦酸源(I)与烯烃(IV)反应，以获得烷基膦酸、其盐或酯(II)，b) 在催化剂B的存在下，将获得的烷基膦酸、其盐或酯(II)与化学式(V)的烷基氧化物反应，以获得单功能化的二烷基膦酸衍生物(III)，催化剂A代表过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物以及至少一种配体组成的催化剂系统，而催化剂B是一种路易斯酸。
• Method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ether and the use thereof
  申请人：Hill Michael

  公开号：US08987489B2

  公开（公告）日：2015-03-24

  A method for producing mono-carboxy-functionalized dialkylphosphinic acids, esters and salts using a vinyl ether. The method is characterized by the following steps: a) reacting a phosphinic acid source (I) with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, the salt or the ester (II) thereof, b) reacting the alkylphosphonous acid so obtained, the salt or the ester (II) thereof with a vinyl ether of formula (V) in the presence of a catalyst B to give a mono-functionalized dialkylphosphinic acid derivative (VI) and c) reacting this derivative (VI) with an oxidant or in the presence of a catalyst C to give a mono-carboxy-functionalized dialkylphosphinic acid derivative (III), wherein the catalysts A and C are transition metals and/or transition metal compounds, and the catalyst B is a peroxide-forming compound and/or a peroxo compound and/or an azo compound.

  使用乙烯醚生产单羧基功能化二烷基膦酸、酯和盐的方法。该方法的特征在于以下步骤：a) 在催化剂A的存在下，将膦酸源(I)与烯烃(IV)反应，得到烷基膦酸、其盐或酯(II)，b) 将所得的烷基膦酸、其盐或酯(II)与式(V)的乙烯醚在催化剂B的存在下反应，得到单功能化的二烷基膦酸衍生物(VI)，c) 将该衍生物(VI)与氧化剂或在催化剂C的存在下反应，得到单羧基功能化的二烷基膦酸衍生物(III)，其中催化剂A和C为过渡金属和/或过渡金属化合物，催化剂B为生成过氧化物的化合物和/或过氧化物和/或偶氮化合物。
• Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids—An Experimental and a Theoretical Study
  作者：Nikoletta Harsági、Réka Henyecz、Péter Ábrányi-Balogh、László Drahos、György Keglevich

  DOI：10.3390/molecules26175303

  日期：——

  It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2–C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80–98%, while the isolated yields fell in the range of 61–79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6–311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6–194.1 kJ·mol−1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

  众所周知，包括膦酸在内的P-酸不易直接酯化。然而，发现一系列烷基膦酸在微波（MW）辐射下与C2-C4醇在[bmim][BF4]存在下可以进行单酯化反应。选择性达到80-98％，而分离收率在61-79％的范围内。所开发的方法是一种绿色的P-酸酯化方法。在M062X/6-311+G(d,p)理论水平上进行的DFT计算（考虑了相应醇的溶剂效应）探索了三步机制，并证明了较高的活化焓（160.6-194.1 kJ·mol-1），只有通过MW辐射才能克服。[bmim][BF4]添加剂的主要作用是增加MW能量的吸收。计算还提出了离子液体中[BF4]阴离子的特定化学作用在另一种机制中的作用。
• Method for the Production of Alkylphosphonic Acids, Esters, and Salts by Oxidizing Alkylphosphonous Acids, and Use Thereof
  申请人：Hill Michael

  公开号：US20110251314A1

  公开（公告）日：2011-10-13

  The invention relates to a method for producing monocarboxy-functionalized dialkylphosphinic acids, esters, and salts, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to obtain an alkylphosphonous acid, the salt or ester (II) thereof, and b) the obtained alkylphosphonous acid, the salt or ester (II) thereof is reacted with an oxidizing agent or with an oxidizing agent and water or with oxygen and water in the presence of a catalyst B to obtain the alkylphosphonic acid derivative (III), wherein R 1 , R 2 , R 3 , R 4 are identical or different from each other and independently represent, inter alia, H, C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 6 -C 18 -aralkyl, C 6 -C 18 -alkylaryl, X and Y are identical or different from each other and independently represent H, C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 6 -C 18 -aralkyl, C 6 -C 18 -alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogenous base, and catalysts A and B are transition metals and/or transition metal compounds and/or catalyst systems composed of a transition metal and/or a transition metal compound and at least one ligand.

  本发明涉及一种生产单羧基功能化的二烷基膦酸、酯和盐的方法，其特征在于a) 在催化剂A的存在下，将膦酸源（I）与烯烃（IV）反应，以获得烷基膦酸、其盐或酯（II），b) 在催化剂B的存在下，将获得的烷基膦酸、其盐或酯（II）与氧化剂或氧化剂和水或氧气和水反应，以获得烷基膦酸衍生物（III），其中R1、R2、R3、R4相同或不同，独立地表示H、C1-C18烷基、C6-C18芳基、C6-C18芳基烷基、C6-C18烷基芳基，X和Y相同或不同，独立地表示H、C1-C18烷基、C6-C18芳基、C6-C18芳基烷基、C6-C18烷基芳基、Mg、Ca、Al、Sb、Sn、Ge、Ti、Fe、Zr、Zn、Ce、Bi、Sr、Mn、Cu、Ni、Li、Na、K和/或质子化的氮碱基，催化剂A和B是过渡金属和/或过渡金属化合物和/或由过渡金属和/或过渡金属化合物和至少一种配体组成的催化剂体系。