5,5-二甲基-2-(苯氧基)-1,3,2-二氧磷杂环己烷 | 3057-08-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 5,5-二甲基-2-(苯氧基)-1,3,2-二氧磷杂环己烷
• 中文别名: 5,5-二甲基-2-苯氧基-1,3,2-二氧磷杂环己烷
• 英文名称: 5,5-dimethyl-2-phenoxy-[1,3,2]dioxaphosphinane
• 英文别名: 5,5-Dimethyl-2-phenoxy-[1,3,2]dioxaphosphorinan；5,5-Dimethyl-2-phenoxy-1,3,2-dioxaphosphinane
• CAS: 3057-08-7
• 化学式: C₁₁H₁₅O₃P
• 分子量: 226.212
• InChiKey: JSVDMQKVGLGYCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2934999090

反应信息

• 作为反应物：
  描述：

  5,5-二甲基-2-(苯氧基)-1,3,2-二氧磷杂环己烷 在 臭氧 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 7,7-Dimethyl-4-phenoxy-1,2,3,5,9-pentaoxa-4lambda5-phosphaspiro[3.5]nonane
  参考文献：
  名称：

  Khatib, F. el; Caminade, A. M.; Koenig, M., Phosphorus and Sulfur and the Related Elements, 1984, vol. 20, p. 55 - 66

  摘要：

  DOI：
• 作为产物：
  描述：

  2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷 在 水 、 potassium carbonate 作用下， 以 甲苯 为溶剂， 反应 8.0h， 生成 5,5-二甲基-2-(苯氧基)-1,3,2-二氧磷杂环己烷
  参考文献：
  名称：

  环状亚磷酸酯/亚磷酰胺的水解及其抑制-无环膦酸盐的可逆环化为环状亚磷酸酯

  摘要：

  使用简单的添加剂（如 KF、K2CO3、Et3N 和分子筛）有效抑制在有意添加的水存在下环状亚磷酸酯/亚磷酰胺 (OCH2CRR'CH2O)PX [X = OPh (1), NMe2 (2)] 的水解. 其中，K2CO3 的效果最好。环状 H-膦酸酯 (OCH2CRR'CH2O)P(O)H (3) 是亚磷酸酯 (OCH2CRR'CH2O)P(OH) 的互变异构形式，在胺水溶液存在下容易水解，生成无环膦酸酯盐 [H2NMe2]+[(HOCH2CRR'CH2O)P(O)(H)(O-)] (4) 可以在简单加热后恢复到 3。有趣的是，(OCH2CRR'CH2O)PX [X = Cl (I-III), NMe2 (2)] 在 K2CO3 存在下与苯酚和水的竞争反应只产生苯氧基衍生物，而不产生水解产物。

  DOI：

  10.1021/op034058k

文献信息

• Réactivité des phosphoramidures
  作者：J.F. Brault、P. Savignac

  DOI：10.1016/s0022-328x(00)93889-0

  日期：1974.2

  The Arbuzov reaction between conveniently substituted 1,3,2-dioxaphosphorinane and bromine gives an acyclic product. These reagents after condensation with primary amine and metallation have been converted to 2-oxo-1,3,2-dioxazaphosphorinane.

  方便取代的1,3,2-二氧杂膦啉与溴之间的Arbuzov反应得到无环产物。这些试剂与伯胺缩合并金属化后已转化为2-oxo-1,3,2-dioxazaphosphorinane。
• Spirooxyphosphoranes
  作者：F. Ramirez、M. Nagabhushanam、C.P. Smith

  DOI：10.1016/s0040-4020(01)82484-4

  日期：1968.1

  Spirooxyphosphoranes with quintuply-connected phosphorus were made from the reaction of phenanthrenequinone, benzil, biacetyl, and 1-phenylpropanedione with 5-membered and 6-membered cyclic phosphite esters and amides. The P31 NMR spectra were compared with those of the oxyphosphoranes derived from open-chain trimethyl and triphenyl phosphites. Further comparisons were made with spiroaminooxyphosphoranes

  带有五重连接磷的螺氧基磷烷是由菲醌，苯甲酰，联乙酰和1-苯基丙烷二酮与5元和6元环状亚磷酸酯和酰胺反应制得的。将P 31 NMR光谱与衍生自开链亚磷酸三甲酯和亚磷酸三苯酯的氧代膦酸酯的光谱进行了比较。与螺氨基氧基膦进行的进一步比较导致P 31的正值大大降低NMR位移，Δ≅20至23 ppm。6元环的影响可以忽略不计。在五元环丙氧基磷杂环戊烷中用氮取代内环氧导致位移的正值Δ≅5 ppm略有增加。用氮替代环外氧会导致位移的正值Δ≅2至4 ppm略有下降。亚磷酸亚乙酯和2，2-二甲基-13-丙二醇环状亚磷酸酯的苯酯对α-二羰基化合物的反应性低于相应的甲酯。
• Method for Producing Mono-Aminofunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof and Use Thereof
  申请人：Hill Michael

  公开号：US20110213061A1

  公开（公告）日：2011-09-01

  The invention relates to a method for producing mono-aminofunctionalized dialkylphosphinic acids and esters and salts thereof, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with acetylenic compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted with a hydrogen cyanide source to yield a mono-functionalized dialkylphosphinic acid derivative (VII) in the presence of a catalyst C, and d) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VII); is reacted to yield a mono-aminofunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst D or a reduction agent, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are the same or different and stand independently of each other, among other things, for H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 6 -C 18 aralkyl, C 6 -C 18 alkylaryl, and X stands for 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 protonized nitrogen base, and Y stands for a mineral acid, a carboxylic acid, a Lewis acid or an organic acid, n=0 to 4 and the catalysts A, B, C and D are formed by transition metals, 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氨基功能化二烷基膦酸和酯及其盐的方法，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，得到烷基膦酸盐或酯（II）；b）在催化剂B的存在下，将所得的烷基膦酸盐或酯（II）与式（V）的乙炔化合物反应，得到单官能化的二烷基膦酸衍生物（VI）；c）在催化剂C的存在下，将所得的单官能化的二烷基膦酸衍生物（VI）与氰化氢源反应，得到单官能化的二烷基膦酸衍生物（VII）；d）在催化剂D或还原剂的存在下，将所得的单官能化的二烷基膦酸衍生物（VII）反应，得到单氨基功能化的二烷基膦酸衍生物（III）。其中，R1、R2、R3、R4、R5、R6可以相同或不同，独立地代表H、C1-C18烷基、C6-C18芳基、C6-C18芳基烷基、C6-C18烷基芳基，X代表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，Y代表矿酸、羧酸、Lewis酸或有机酸，n=0至4，催化剂A、B、C和D由过渡金属、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形成。
• Method for Producing Mono-Carboxyfunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof by means of Vinylenes-Nitriles and Use Thereof
  申请人：Hill Michael

  公开号：US20110213059A1

  公开（公告）日：2011-09-01

  The invention relates to a method for producing mono-carboxyfunctional zed dialkylphosphinic acids and esters and salts thereof by means of vinylenes/nitriles, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with acetylenic compounds of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted with a hydrogen cyanide source to yield a mono-functionalized dialkylphosphinic acid derivative (VII) in the presence of a catalyst C, and d) the thus obtained monofunctionalized dialkylphosphinic acid derivative (VII); is reacted to yield a monocarboxyfunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst D, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are the same or different and stand independently of each other, among other things, for H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 6 -C 18 aralkyl, C 6 -C 18 alkylaryl, and X and Y are the same or different and stand independently of each other for 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 protonized nitrogen base, and the catalysts A, B and C are formed by 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 the catalyst D is an acid or a base.

  本发明涉及一种通过使用乙烯基/腈类化合物制备单羧基取代的二烷基膦酸和酯及其盐的方法，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，得到烷基膦酸，盐或酯（II）；b）在催化剂B的存在下，将所得的烷基膦酸，盐或酯（II）与式（V）的炔烃化合物反应，得到单功能化的二烷基膦酸衍生物（VI）；c）在催化剂C的存在下，将所得的单功能化的二烷基膦酸衍生物（VI）与氰化氢源反应，得到单功能化的二烷基膦酸衍生物（VII）；d）在催化剂D的存在下，将所得的单功能化的二烷基膦酸衍生物（VII）反应，得到单羧基取代的二烷基膦酸衍生物（III）。其中，R1，R2，R3，R4，R5，R6相同或不同且独立地代表H，C1-C18烷基，C6-C18芳基，C6-C18芳基烷基，C6-C18烷基芳基，X和Y相同或不同且独立地代表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/或质子化氮碱，催化剂A，B和C由过渡金属和/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，催化剂D是酸或碱。
• Method for Producing Mono-Aminofunctionalized Dialkylphosphinic Acids and Esters and Salts Thereof by Means of Acrylnitriles and Use Thereof
  申请人：Hill Michael

  公开号：US20110213078A1

  公开（公告）日：2011-09-01

  The invention relates to a method for producing mono-aminofunctionalized dialkylphosphinic acids and esters and salts thereof by means of acrylnitriles, characterized in that a) a phosphinic acid source (I) is reacted with olefins (IV) to yield an alkylphosphonic acid, salt or ester (II) thereof in the presence of a catalyst A, b) the thus obtained alkylphosphonic acid, salt or ester (II) thereof is reacted with an acrylnitrile of formula (V) to yield a mono-functionalized dialkylphosphinic acid derivative (VI) in the presence of a catalyst B, and c) the thus obtained mono-functionalized dialkylphosphinic acid derivative (VI) is reacted to yield a mono-aminofunctionalized dialkylphosphinic acid derivative (III) in the presence of a catalyst C or a reduction agent, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and stand independently of each other, among other things, for H, C 1 -C 18 alkyl, C 6 -C 18 aryl, C 6 -C 18 aralkyl, C 6 -C 18 alkylaryl and X stands for 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 protonized nitrogen base, and Y stands for a mineral acid, a carboxylic acid, a Lewis acid or an organic acid, n=an integer or fractional number of 0 to 4 and the catalysts A and C are formed by transition metals, 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 formed by compounds forming peroxides, peroxo compounds, azo compounds, alkali metals, alkaline earth metals, alkali hydrides, alkaline earth hydrides and/or alkali alcoholates and alkaline earth alcoholates.

  本发明涉及一种通过丙烯腈制备单氨基功能化二烷基膦酸和酯及其盐的方法，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，得到烷基膦酸盐或酯（II）；b）在催化剂B的存在下，将所得的烷基膦酸盐或酯（II）与式（V）的丙烯腈反应，得到一种单功能化的二烷基膦酸衍生物（VI）；c）在催化剂C或还原剂的存在下，将所得的单功能化的二烷基膦酸衍生物（VI）反应，得到一种单氨基功能化的二烷基膦酸衍生物（III）。其中，R1、R2、R3、R4、R5、R6、R7相同或不同且独立地代表H、C1-C18烷基、C6-C18芳基、C6-C18芳基烷基、C6-C18烷基芳基，X代表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/或质子化氮碱，Y代表矿酸、羧酸、路易斯酸或有机酸，n为0到4的整数或分数，催化剂A和C由过渡金属、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形成，催化剂B由形成过氧化物、过氧化物化合物、偶氮化合物、碱金属、碱土金属、碱金属氢化物、碱土金属氢化物和/或碱金属醇盐和碱土金属醇盐的化合物组成。