ethyl 3-(N,N,N',N'-tetramethyldiamidophosphoryloxy)benzoate | 501649-30-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 3-(N,N,N',N'-tetramethyldiamidophosphoryloxy)benzoate
• 英文别名: ethyl 3-{[bis(dimethylamino)phosphoryl]oxy}benzoate；ethyl 3-(bis(dimethylamino)phosphoryloxy)benzoate；ethyl 3-[bis(dimethylamino)phosphoryloxy]benzoate
• CAS: 501649-30-5
• 化学式: C₁₃H₂₁N₂O₄P
• 分子量: 300.294
• InChiKey: DOLSLRDJNSIFOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-(N,N,N',N'-tetramethyldiamidophosphoryloxy)benzoate 在 TMP₂Mg*2LiCl 、 BrCl₂C-CCl₂Br 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以80%的产率得到ethyl 3-{[bis(dimethylamino)phosphoryl]oxy}-4-bromobenzoate
  参考文献：
  名称：

  使用TMP2Mg2 LiCl进行芳烃的元和对位官能化的一般方法。

  摘要：

  DOI：

  10.1002/anie.200703382
• 作为产物：
  描述：

  3-羟基苯甲酸乙酯 、 双(二甲胺基)氯酸磷 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到ethyl 3-(N,N,N',N'-tetramethyldiamidophosphoryloxy)benzoate
  参考文献：
  名称：

  使用TMP2Mg2 LiCl进行芳烃的元和对位官能化的一般方法。

  摘要：

  DOI：

  10.1002/anie.200703382

文献信息

• Improved Air-Stable Solid Aromatic and Heterocyclic Zinc Reagents by Highly Selective Metalations for Negishi Cross-Couplings
  作者：Christos I. Stathakis、Sebastian Bernhardt、Valentin Quint、Paul Knochel

  DOI：10.1002/anie.201204526

  日期：2012.9.10

  Directed metalation using TMPMgCl⋅LiCl (TMP=2,2,6,6‐tetramethylpiperidide) and subsequent transmetalation with Zn(OPiv)2 leads to aryl and heteroaryl zinc pivalates. After solvent evaporation, easy‐to‐handle fine powders are obtained that retain most of their activity (>85 %) when exposed to air for 4 h. They smoothly undergo Negishi cross‐couplings, and technical‐grade solvents can be used without

  涉及金属化用TMPMgCl ⋅的LiCl（TMP = 2,2,6,6-四甲基）和用Zn（OPiv）随后转移金属化2所导致的芳基和杂芳基锌三甲基乙酸盐。溶剂蒸发后，将获得易于处理的细粉，当暴露于空气中4小时后，这些细粉可保留其大部分活性（> 85％）。它们可以平稳地进行Negishi交叉偶联，并且可以使用工业级溶剂而不会显着降低产量。
• PREPARATION AND USE OF MAGNESIUM AMIDES
  申请人：Clososki Giuliano Cesar

  公开号：US20100144516A1

  公开（公告）日：2010-06-10

  The present application relates to mixed Mg/Li amides of the general formula R 1 R 2 N—Mg—NR 3 R 4 .zLiY (II) wherein R 1 , R 2 , R 3 , and R 4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R 1 and R 2 together, or R 3 and R 4 together can be part of a cyclic or polymeric structure; and wherein at least one of R 1 and R 2 and at least one of R 3 and R 4 is other than H; Y is selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HaIO n , wherein n=3 or 4 and Hal is selected from Ci, Br and I; NO 3 ; BF 4 ; PF 6 ; H; a carboxylate of the general formula R x CO 2 ; an alcoholate of the general formula OR x ; a thiolate of the general formula SR x ; R x P(O)O 2 ; or SCOR x ; or SCSR x ; O n SR x , wherein n=2 or 3; or NO n , wherein n=2 or 3; and a derivative thereof; wherein R X is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>1; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases.

  本申请涉及一般式为R1R2N—Mg—NR3R4.zLiY（II）的混合Mg/Li酰胺，其中R1、R2、R3和R4分别选择自H、含有一个或多个杂原子的取代或未取代的芳基或杂环芳基、线性、支链或环状、取代或未取代的烷基、烯基、炔基或其硅基衍生物；且R1和R2在一起，或R3和R4在一起可以是环状或聚合物结构的一部分；并且至少有一个R1和R2以及至少一个R3和R4不是H；Y选择自F、Cl、Br、I、CN、SCN、NCO、HaIOn，其中n=3或4，Hal选择自Ci、Br和I；NO3；BF4；PF6；H；一般式为RxCO2的羧酸盐；一般式为ORx的醇盐；一般式为SRx的硫醇盐；RxP（O）O2；或SCORx；或SCSRx；OnSRx，其中n=2或3；或NOn，其中n=2或3；及其衍生物；其中RX为取代或未取代的芳基或杂环芳基、线性、支链或环状、取代或未取代的烷基、烯基、炔基或其衍生物，或H；m为O或1；z>1；以及混合Mg/Li酰胺的制备方法和这些酰胺的用途，例如作为碱。
• Preparation and use of magnesium amides
  申请人：Ludwig-Maximilians-Universitat München

  公开号：US08134005B2

  公开（公告）日：2012-03-13

  The present application relates to mixed Mg/Li amides of the general formula R1R2N—Mg(NR3R4)mX,.m zLiY (II) wherein R1, R2, R3, and R4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R1 and R2 together, or R3 and R4 together can be part of a cyclic or polymeric structure; and wherein at least one of R1 and R2 and at least one of R3 and R is other than H; X and Y are, independently, selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HaIOn, wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO3; BF4; PF6; H; a carboxylate of the general formula RXCO2; an alcoholate of the general formula ORX; a thiolate of the general formula SRX; RXP(O)O2; or SCORX; or SCSRX; OnSRx, wherein n=2 or 3; or NOn, wherein n=2 or 3; and a derivative thereof; wherein Rx is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>O; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases.

  本申请涉及一般式为R1R2N-Mg（NR3R4）mX，m zLiY（II）的混合Mg / Li氨基化合物，其中R1，R2，R3和R4分别选自H，含有一个或多个杂原子的取代或未取代芳基或杂芳基，线性，支链或环状，取代或未取代的烷基，烯基，炔基或其硅基衍生物; R1和R2在一起，或R3和R4在一起可以是环状或聚合物结构的一部分; 并且至少有一个R1和R2以及至少有一个R3和R不是H; X和Y分别选自F，Cl，Br，I，CN，SCN，NCO，HaIOn，其中n = 3或4且Hal选自Cl，Br和I; NO3; BF4; PF6; H;一般式为RXCO2的羧酸盐; 一般式为ORX的醇盐; 一般式为SRX的硫醇盐; RXP（O）O2; 或SCORX; 或SCSRX; OnSRx，其中n = 2或3; 或NOn，其中n = 2或3;及其衍生物; 其中Rx是含有一个或多个杂原子的取代或未取代的芳基或杂芳基，线性，支链或环状，取代或未取代的烷基，烯基，炔基或其衍生物，或H; m为O或1; z> O;以及混合Mg / Li氨基化合物的制备方法和这些氨基化合物的用途，例如作为碱。
• Preparation and Use of Magnesium Amides
  申请人：Knochel Paul

  公开号：US20090176988A1

  公开（公告）日：2009-07-09

  The present application relates to mixed Mg/Li amides of the general formula R1R2N—Mg(NR3R4)mX,m zLiY (II) wherein R 1 , R 2 , R 3 , and R 4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R 1 and R 2 together, or R 3 and R 4 together can be part of a cyclic or polymeric structure; and wherein at least one of R 1 and R 2 and at least one of R 3 and R is other than H; X and Y are, independently, selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HalO n , wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO 3 ; BF 4 ; PF 6 ; H; a carboxylate of the general formula R X CO 2 ; an alcoholate of the general formula ORX; a thiolate of the general formula SR X ; R X P(O)O 2 ; or SCOR X ; or SCSR X ; O n SR x , wherein n=2 or 3; or NO n , wherein n=2 or 3; and a derivative thereof; wherein R x is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>O; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases.

  本申请涉及到通式为R1R2N-Mg（NR3R4）mX，m zLiY（II）的混合镁/锂酰胺，其中R1，R2，R3和R4分别选择自H，含有一个或多个杂原子的取代或未取代芳基或杂芳基，线性，支链或环状，取代或未取代的烷基，烯基，炔基或其硅基衍生物; R1和R2在一起，或R3和R4在一起可以是一个环状或聚合物结构的一部分; 并且至少有一个R1和R2以及至少有一个R3和R不是H; X和Y分别选择自F; Cl; Br; I; CN; SCN; NCO; HalOn，其中n = 3或4，Hal选择自Cl，Br和I; NO3; BF4; PF6; H; 通式为RXCO2的羧酸盐; 通式为ORX的醇盐; 通式为SRX的硫醇盐; RXP（O）O2; 或SCORX; 或SCSRX; OnSRx，其中n = 2或3; 或NOn，其中n = 2或3; 及其衍生物; 其中R是取代或未取代的芳基或杂芳基，线性，支链或环状，取代或未取代的烷基，烯基，炔基或其衍生物，或H; m为O或1; z> O; 以及混合镁/锂酰胺的制备过程和这些酰胺的用途，例如作为碱。
• Direct Magnesiation of Polyfunctionalized Arenes and Heteroarenes Using (tmp)2Mg⋅2 LiCl
  作者：Giuliano C. Clososki、Christoph J. Rohbogner、Paul Knochel

  DOI：10.1002/anie.200701487

  日期：2007.10.8