Dimethyl (phenylsulfinyl)methylphosphonate | 58496-74-5

• 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: Dimethyl (phenylsulfinyl)methylphosphonate
• 英文别名: (dimethylphosphoryl)methyl phenyl sulfoxide；Dimethylphosphorylmethylphenylsulfoxid；Dimethyl [(benzenesulfinyl)methyl]phosphonate；dimethoxyphosphorylmethylsulfinylbenzene
• CAS: 58496-74-5
• 化学式: C₉H₁₃O₄PS
• 分子量: 248.24
• InChiKey: COSVJZJLHYOVNY-UHFFFAOYSA-N

物化性质

• 沸点：
  402.5±28.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Dimethyl (phenylsulfinyl)methylphosphonate 在 (二氯碘)-苯 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 以51%的产率得到α-chloro-α-dimethoxyphosphorylmethyl phenyl sulfoxide
  参考文献：
  名称：

  α-磷酸亚砜VIII。α-磷酰亚砜的α-氯化立体化学

  摘要：

  描述了在存在和不存在吡啶的情况下用碘代二氯乙烷和磺酰氯对α-磷酰基亚砜1的氯化，以及使用（+）-（S）-α-二甲氧基磷酰基甲基对甲苯基亚砜1a对该反应的立体化学研究。发现在亚磺酰基的立体化学控制下发生了1至相应的α-氯-α-磷酰基亚砜2的转化，并导致非对映异构体混合物。α-碳原子上的不对称诱导程度和手性亚磺酰基中心在1中的消旋化取决于反应条件。在（+）-（S）-1a的氯化反应中形成的主要非对映异构体的结构即，通过X射线分析求出（+）-（S）c（S）s -α-氯-α-二甲氧基磷酰基甲基对甲苯基亚砜2a。通过直接方法解析该结构，并将其精炼为R = 0.081。氯化α-磷酰基亚砜1的实验数据表明在两个手性中心（C和S）都保留了构型，并且该立体化学可以通过假设涉及形成带正电荷的叶立德的加成消除机理来合理化。

  DOI：

  10.1016/s0040-4020(01)85289-3
• 作为产物：
  描述：

  氯甲基苯硫醚 在 sodium periodate 作用下， 以 水 、 丙酮 为溶剂， 生成 Dimethyl (phenylsulfinyl)methylphosphonate
  参考文献：
  名称：

  A new and convenient synthesis of 2-deoxy-D-ribose from 2,4-O-ethylidene-D-erythrose

  摘要：

  DOI：

  10.1021/jo01328a029

文献信息

• α-Phosphoryl sulfoxides. XI. Sulfenylation of α-phosphoryl sulfoxides and a general synthesis of optically active ketene dithioacetal mono-S-oxides
  作者：Marian Mikołajczyk、Wanda H. Midura、Blanka Wladislaw、Francisco C. Biaggio、Liliana Marzorati、MichałW. Wieczorek、Jarosław Błaszczyk

  DOI：10.1016/s0040-4020(96)01175-1

  日期：1997.2

  α-phosphoryl sulfoxides 1 with S-methyl methanethiosulfonate and phenylselenenyl bromide, respectively, affording α-methylsulfenyl- and α-phenylselenenyl-α-phosphoryl sulfoxides 8 and 9 are described. Sulfenylation of (+)-(S)-dimethoxyphosphorylmethyl p-tolyl sulfoxide 2 gave a mixture of optically active diastereoisomers of the sulfoxide 8a which is a key substrate in the Horner-Wittig synthesis of enantiomeric

  硫基化和α -磷酰基亚砜的selenenylation 1与S-甲基methanethiosulfonate和苯硒基溴，分别得到α-methylsulfenyl-和α-苯硒基-α -磷亚砜8和9中描述。（+）-（S）-二甲氧基磷酰基甲基对甲苯基亚砜2的亚磺酰化得到了亚砜8a的旋光非对映异构体的混合物，这是对映体烯酮二硫缩醛单S-氧化物10的Horner-Wittig合成的关键底物。确定了10个几何异构体的比例并进行了简要讨论。E的晶体和分子结构报道了-1-对甲苯基亚磺酰基-1-甲基亚磺酰基-2-苯基-乙烯10a。
• Reductive Cyclization of Ketones Tethered to Activated Olefins Mediated by Magnesium in Methanol
  作者：Ge Hyeong Lee、Eun Bok Choi、Eun Lee、Chwang Siek Pak

  DOI：10.1021/jo00085a036

  日期：1994.3

  The reductive cyclizations of various ketones tethered to activated olefins such as alpha,beta-unsaturated esters, nitriles, sulfoxides, and sulfides were mediated by magnesium in dry methanol in the presence of mercuric chloride. When treated with magnesium in dry methanol at -23-degrees-C all of the ketones except nitrile 9 (42%) and 5-oxa-8-keto-2-enoate 5 (13%) gave excellent yields (79-98%) of mono- and bicyclic alcohol products resulting from carbon-carbon bond formation between the beta-carbon of the activated olefin and the carbonyl carbon. The reaction was accelerated by the catalytic amount of mercuric chloride, although the stereoselectivity was not affected by the catalyst. For all the substrates except 8-keto-2-enoate 3 and 5-aza-8-keto-2-enoate 6, the configuration of the major product was trans between the hydroxy and (methoxycarbonyl)methyl groups. The product isomer ratios were independent of the substrate geometry (E or Z). In contrast to the ketones, aldehydes tethered to alpha,beta-unsaturated esters gave products of simple reduction of the double bond and/or saturated alcohols instead of the cyclized products. When the reaction temperature was lowered, the yields of cyclized product were significantly affected by the production of appreciable amounts of saturated product, but the stereoselectivity was not improved. Under the same reaction conditions alpha,beta-unsaturated sulfoxide 16 gave deoxygenated sulfide 18 (85%) as the major product along with a small amount (9%) of cyclized product 19t. In contrast, sulfone 17 underwent desulfonylation instead of cyclization to give olefin 20 (54%). With excess magnesium (15 equiv), however, alpha,beta-unsaturated sulfoxide 16 gave cyclized sulfide 19t (95%) via deoxygenated sulfide 18. Both 16Z and 16E afforded product 19t as a single isomer. It is suggested that the reductive cyclization of the alpha,beta-unsaturated esters and nitriles proceed by means of nucleophilic attack of a beta-carbon radical anion, formed by initial electron transfer from magnesium metal to the activated olefin, on the carbonyl group. The cyclization of the alpha,beta-unsaturated sulfide proceeds by nucleophilic attack of the ketyl on the olefinic double bond.
• Stereospecific reductive desulfurization of vinyl sulfoxides with tert-butyllithium and an internal proton source
  作者：Paula G. Theobald、William H. Okamura

  DOI：10.1021/jo00289a059

  日期：1990.1
• Wladislaw, Blanka; Marzorati, Liliana; Biaggio, Francisco C., Phosphorus, Sulfur and Silicon and the Related Elements, 1996, vol. 111, p. 186
  作者：Wladislaw, Blanka、Marzorati, Liliana、Biaggio, Francisco C.、Mikolajczyk, Marian

  DOI：——

  日期：——
• Mikolajczyk Marian, Midura Wanda H., Grzejszczak Slawomir, Tetrahedron, 50 (1994) N 27, S 8053-8072
  作者：Mikolajczyk Marian, Midura Wanda H., Grzejszczak Slawomir

  DOI：——

  日期：——