phthalyl sulfite | 6538-31-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: phthalyl sulfite
• 英文别名: 2,4,3-Benzodioxathiepin, 1,5-dihydro-, 3-oxide；1,5-dihydro-2,4,3λ4-benzodioxathiepine 3-oxide
• CAS: 6538-31-4
• 化学式: C₈H₈O₃S
• 分子量: 184.216
• InChiKey: DSHBVBLXQUPREA-UHFFFAOYSA-N

物化性质

• 沸点：
  320.2±31.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  54.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  phthalyl sulfite 在 ruthenium trichloride sodium periodate 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 2.67h， 生成 1-(di-tert-butylphosphinomethyl)-2-(di-pyridin-2-ylphosphinomethyl)benzene
  参考文献：
  名称：

  PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, NOVEL CARBONYLATION LIGANDS AND CATALYST SYSTEMS INCORPORATING SUCH LIGANDS

  摘要：

  通用公式（I）的一种新的双齿配体及其用于乙烯基不饱和化合物羰基化的方法被描述。基团X1可以被定义为一个最多含有30个原子的一价烃基基团，其中至少含有一个氮原子，在18°C时在稀溶液中的pKb值在4和14之间，其中所述至少一个氮原子与Q2原子之间由1至3个碳原子分隔。基团X2被定义为X1、X3或X4，或者代表一个最多含有30个原子的一价基团，其中至少含有一个主要、次要或芳香环碳原子，其中每个所述一价基团分别通过所述至少一个主要、次要或芳香环碳原子连接到相应的Q2原子。Q1和Q2各自独立地代表磷、砷或锑。

  公开号：

  US20120330016A1
• 作为产物：
  描述：

  邻苯二甲酸二甲酯 在 lithium aluminium tetrahydride 、 氯化亚砜 作用下， 以 乙醚 为溶剂， 生成 phthalyl sulfite
  参考文献：
  名称：

  Riemschneider,R.; Wuscherpfennig,V., Zeitschrift fur Naturforschung. Teil B. Anorganische Chemie, organische Chemie, Biochemie, Biophysik, Biologie, 1962, vol. 17, p. 516 - 522

  摘要：

  DOI：

文献信息

• The Methoxycarbonylation of Vinyl Acetate Catalyzed by Palladium Complexes of [1,2-Phenylenebis(methylene)]bis[di(tert-butyl)phosphine]
  作者：Adam J. Rucklidge、George E. Morris、Alexandra M. Z. Slawin、David J. Cole-Hamilton

  DOI：10.1002/hlca.200690174

  日期：2006.8

  Palladium complexes of [1,2-phenylenebis(methylene)]bis[di(tert-butyl)phosphine] (1) catalyze the methoxycarbonylation of vinyl acetate (= ethenyl acetate) in the presence of methanesulfonic acid (Scheme 1). High selectivities to ester products can be obtained if free phosphine ligand is in excess over the amount of added acid (Table 1). Selectivities to methyl 2-acetoxypropanoate, a precursor to lactate

  [1,2-亚苯基双（亚甲基）]双[二（叔丁基）膦]（1）的钯络合物在甲磺酸的存在下催化乙酸乙烯酯（=乙烯基乙酸乙烯酯）的甲氧基羰基化（方案1）。如果游离膦配体超过所加酸的量（表1），则可获得对酯产物的高选择性。乳酸酯的前体2-乙酰氧基丙酸甲酯的选择性在低温和低压下可高达3.6：1（表2）。用i代替t BuPr基团导致较低活性的催化剂和较低的对支链产物的选择性。用萘二甲酰基部分取代亚苯基部分也产生较低的活性，但与基于亚苯基的类似物具有相似的选择性。作为丙烷而不是亚苯基双（亚甲基）接头的直链烃链接头导致催化效果差，除了丙烷-1，3-二基接头给出了良好的速率，但是支链选择性差（表5）。讨论了不同反应条件对催化的影响。新的基于二甲苯的二膦的合成2 - 5至四个与一个我镨基团取代吨卜基团的的P-原子1和配位体的还描述了基于1,2-和2,3-二甲基萘的图6和7（方案2和3）。
• [EN] PROCESS FOR THE CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS, NOVEL CARBONYLATION LIGANDS AND CATALYST SYSTEMS INCORPORATING SUCH LIGANDS<br/>[FR] PROCÉDÉ DE CARBONYLATION DE COMPOSÉS À INSATURATION ÉTHYLÉNIQUE, NOUVEAUX LIGANDS DE CARBONYLATION, ET SYSTÈMES CATALYSEURS COMPRENANT CES LIGANDS
  申请人：LUCITE INT UK LTD

  公开号：WO2010001174A1

  公开（公告）日：2010-01-07

  A novel bidentate catalytic ligand of general formula (I) is described. R represents a hydrocarbyl aromatic structure having at least one aromatic ring to which Q 1 and Q 2 are each linked, via the respective linking group, if present, on available adjacent atoms of the at least one aromatic ring. The groups X 3 and X 4 represent radicals joined via tertiary carbon atoms to the respective atom Q 1 and the groups X 1 and X 2 represent radicals joined via primary, or substituted aromatic ring carbon atom(s) to the respective atom Q 2. A and B represent an optional lower alkylene linking group. Q 1 and Q 2 each represent phosphorus, arsenic or antimony. A process for the carbonylation of ethylenically unsaturated compounds comprising reacting the compound with carbon monoxide in the presence of a source of hydroxyl groups, optionally, a source of anions and catalyst system obtainable by combining a metal of Group 8, 9 or 10 or a compound thereof and the bidentate ligand of general formula (I) is also described.

  描述了一种一般式(I)的新型双齿催化配体。其中，R代表至少具有一个芳香环的烃基芳香结构，其中Q1和Q2分别通过至少一个芳香环上可用的相邻原子的相应连接基（如果存在）连接。基团X3和X4代表通过第三级碳原子连接到相应原子Q1的基团，基团X1和X2代表通过主要或取代的芳香环碳原子连接到相应原子Q2的基团。A和B代表可选的较低烷基连接基。Q1和Q2分别代表磷、砷或锑。还描述了一种用于乙烯基不饱和化合物的羰基化的方法，包括将该化合物与一氧化碳在羟基源的存在下反应，可选地，与阴离子源和由结合第8、9或10族金属或其化合物以及一般式(I)的双齿配体的催化系统获得的催化剂。
• Ionic Pathways in the Photochemistry of Cyclic Sulfite Esters
  作者：Rick C. White、Benny E. Arney Jr、Jacob Perry、Nathan Thompson、Phil M. Pithan、Sebastian von Gradowski、Heiko Ihmels

  DOI：10.1002/jhet.2687

  日期：2017.3

  The photochemistry of cyclic carbonate esters proceeds by the photochemical extrusion of carbon dioxide to give 1, 3‐diradicals which produce oxiranes as well as other radical derived species. The corresponding cyclic sulfite esters, upon irradiation, give intermediates that are trapped by alcohols yet generate no oxiranes. These results are consistent with ionic intermediates.

  环状碳酸酯的光化学过程是通过二氧化碳的光化学挤压而进行的，从而产生1、3-二基自由基，这些基自由基产生了氧杂环丁烷以及其他自由基衍生物种。辐射后，相应的环状亚硫酸酯生成的中间体被醇捕获，但不生成环氧乙烷。这些结果与离子中间体一致。
• Crossover Point between Dialkoxy Disulfides (ROSSOR) and Thionosulfites ((RO)₂SS):  Prediction, Synthesis, and Structure
  作者：Eli Zysman-Colman、Neysa Nevins、Nicolas Eghbali、James P. Snyder、David N. Harpp

  DOI：10.1021/ja0559395

  日期：2006.1.1

  Isomeric preference between cyclic dialkoxy disulfides and thionosulfites is governed by the ring size of the heterocycle. Rings smaller than seven atoms prefer the thionosulfite connectivity, whereas larger rings or acyclic analogues favor the unbranched dialkoxy disulfide structure. Density functional calculations were employed to predict the crossover point at which both constitutional isomers are of comparable stability. Follow-up synthesis provides the previously unknown eight-membered ring dialkoxy disulficle 14 and seven-membered ring thionosulfite 15 from the same reaction. X-ray crystallography for all but one of the reaction products and complementary NMR analysis furnishes insights into both solid-state and solution conformations. A long-standing issue regarding the concerted vs catalyzed isomerization pathway between XSSX and X2S = S has been addressed for X = RO and shown to be acid dependent.
• Approaches to p-hydroxyphenoxymethylquinolines which avoid intermediate chloromethylquinolines for the synthesis of the LTD4 antagonist, RG 12525
  作者：M.K. O'Brien、A.W. Sledeski、L.K. Truesdale

  DOI：10.1016/s0040-4039(96)02361-1

  日期：1997.1

  As part of an effort to develop an industrial synthesis of the LTD(4) antagonist RG 12525 (1), several approaches to the intermediate (2-quinolinylmethoxy)phenol 3 were investigated that avoided the generation of the lachrymatory sensitizer alpha-chloro-2-methylquinoline 2. Utilization of a cyclic sulfate in place of alpha,alpha'-dichloro-o-xylene 4 showed promise as a selective dialkylating agent in the conversion of 3 to RG 12525 (1). (C) 1997, Elsevier Science Ltd. All rights reserved.