dibromomalonyl dichloride | 74539-43-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: dibromomalonyl dichloride
• 英文别名: dibromomalonic acid dichloride；dibromo-malonyl chloride；Dibrom-malonylchlorid；2,2-Dibromopropanedioyl dichloride
• CAS: 74539-43-8
• 化学式: C₃Br₂Cl₂O₂
• 分子量: 298.746
• InChiKey: BZQPHZCAGVMACP-UHFFFAOYSA-N

物化性质

• 熔点：
  39 °C
• 沸点：
  75-77 °C(Press: 15 Torr)
• 密度：
  2.459±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dibromomalonyl dichloride 在 锌 作用下， 以 乙酸乙酯 为溶剂， 生成 二氧化三碳
  参考文献：
  名称：

  Staudinger, H.; Bereza, S., Berichte der Deutschen Chemischen Gesellschaft, 1908, vol. 41, p. 4461 - 4465

  摘要：

  DOI：
• 作为产物：
  描述：

  二溴丙二酸 在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 生成 dibromomalonyl dichloride
  参考文献：
  名称：

  8H-Anhydro-4-hydroxy-2-oxo-1,3-thiazinium Hydroxides as Mesoionic 1,4-Dipoles

  摘要：

  The previously unknown 8H-anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides (1) were prepared and their 1,4-dipolar cycloaddition behavior was examined. In most cases, elimination of the proton in the 8-position of the mesoionic ring was observed to occur unless extremely reactive dipolarophiles were used. The S,N-ketene acetals were converted to the corresponding alpha-diazo ketones for further study.

  DOI：

  10.3987/com-93-s(b)16

文献信息

• Cyclic amic acid derivatives
  申请人：Banyu Pharmaceutical Co., Ltd.

  公开号：US06011174A1

  公开（公告）日：2000-01-04

  The present invention relates to a compound of the formula (I), or its pharmaceutically acceptable salt or ester: ##STR1## wherein Ar.sup.1 is an aryl group or a heteroaromatic ring group; Ar is a group of the formula ##STR2## each of Ar.sup.2 and Ar.sup.3 is an aryl group or a heteroaromatic ring group; Cy is an aryl group, a heteroaromatic ring group or an aliphatic ring group which may contain one or two oxygen atoms; A.sup.1 is a C.sub.1-4 chain hydrocarbon group; m is an integer of from 1 to 6; each of n and p is an integer of from 0 to 3; Q.sup.1 is a single bond, a group of the formula --CH.sub.2 O--, --OCH.sub.2 --, --CH.sub.2 S-- or --SCH.sub.2 --, or a C.sub.1-6 chain hydrocarbon group; Q.sup.2 is a single bond or a group of the formula --(CH.sub.2).sub.m -- or --(CH.sub.2).sub.n --W--(CH.sub.2).sub.p --; Q.sup.3 is a single bond, an oxygen atom, a sulfur atom, a methylene group, a vinylene group or a group of the formula --CO--, --NH--, --COO--, --OCO--, --CH.sub.2 CH.sub.2 --, --OCH.sub.2 --, --SCH.sub.2 --, --CH.sub.2 O--, --CH.sub.2 S--, --NHCO-- or --CONH--; R.sup.1 is a lower alkyl group; each of R.sup.2 and R.sup.3 is a hydrogen atom, a hydroxyl group or a lower alkyl group; W is an oxygen atom, a sulfur atom, a vinylene group or an ethynylene group; x is an integer of from 0 to 2; and y is 0 or 1; and an antitumor agent containing it as an active ingredient and intermediates for the production thereof.

  本发明涉及一个化合物，其化学式为(I)，或其药学上可接受的盐或酯：其中Ar.sup.1是芳基或杂芳环基；Ar是化学式中的一个基团##STR2##其中Ar.sup.2和Ar.sup.3各自是芳基或杂芳环基；Cy是芳基、杂芳环基或可能含有一个或两个氧原子的脂环基；A.sup.1是C.sub.1-4链烃基；m是从1到6的整数；n和p各自是从0到3的整数；Q.sup.1是一个单键，一个化学式--CH.sub.2 O--、--OCH.sub.2 --、--CH.sub.2 S--或--SCH.sub.2 --的基团，或一个C.sub.1-6链烃基；Q.sup.2是一个单键或一个化学式--(CH.sub.2).sub.m--或--(CH.sub.2).sub.n--W--(CH.sub.2).sub.p--的基团；Q.sup.3是一个单键，一个氧原子，一个硫原子，一个亚甲基基团，一个亚乙基基团，或一个化学式--CO--、--NH--、--COO--、--OCO--、--CH.sub.2 CH.sub.2 --、--OCH.sub.2 --、--SCH.sub.2 --、--CH.sub.2 O--、--CH.sub.2 S--、--NHCO--或--CONH--的基团；R.sup.1是一个较低的烷基基团；R.sup.2和R.sup.3各自是氢原子、羟基或较低的烷基基团；W是一个氧原子、一个硫原子、一个亚乙基基团或一个乙炔基团；x是从0到2的整数；y是0或1；以及包含它作为活性成分的抗肿瘤剂和其生产的中间体。
• An Approach to the Isoschizozygane Alkaloid Core Using a 1,4-Dipolar Cycloaddition of a Cross-Conjugated Heteroaromatic Betaine
  作者：Albert Padwa、Andrew C. Flick、Hyoung Ik Lee

  DOI：10.1021/ol0508779

  日期：2005.7.1

  [reaction: see text] A new strategy for the synthesis of the isoschizozygane alkaloid core has been developed that is based on a 1,4-dipolar cycloaddition reaction of a cross-conjugated heteroaromatic betaine. The resulting cycloadduct undergoes loss of COS, and further reduction delivers a 5a-aza-acenaphthylene intermediate that was transformed into the isoschizozygane skeleton upon treatment with

  [反应：见正文]基于交叉共轭杂芳族甜菜碱的1，4-偶极环加成反应，已开发出一种合成同工酶生物碱核心的新策略。所得的环加合物经历了COS的损失，并且进一步的还原产生了5a-氮杂-ph烯中间体，该中间体在用酸处理后被转化为异chi并zygane骨架。
• On the Intramolecular 1,4-Dipolar Cycloaddition Reaction of Thiazinium Betaines for the Construction of Aza-, Diaza-, and Polyaza-Heterocyclic Ring Systems
  作者：Albert Padwa、Steven J. Coats、Scott R. Harring、Lazaros Hadjiarapoglou、Mark A. Semones

  DOI：10.1055/s-1995-4032

  日期：1995.8

  A series of bicyclic anhydro-4-hydroxy-2-oxo-1,3-thiazinium hydroxides containing tethered π-systems are easily prepared from the reaction of thiolactams with 1,3-bielectrophiles. These cross-conjugated heteroaromatic betaines undergo regio- and stereospecific 1,4-dipolar cycloaddition in good yield to produce cycloadducts containing a carbonyl sulfide bridge which can be induced to lose COS on further heating. Two of the cycloadducts were characterized by single crystal X-ray determinations. Control of ring size in the final product of the cycloaddition can be achieved by variation of the dipolarophilic chain length. Entry to the [6,6,5]- and [6,6,6]pyridone ring systems was possible using phenylalkynyl-substituted thioamides. Intramolecular 1,4-dipolar cycloaddition of a thiazinium betaine dipole also occurs across an indolyl π-bond. With only one substituent group in the 9-position of the bicyclic betaine, the reaction takes an entirely different course unless a highly activated π-bond is incorporated into the tether. The preferred reaction with modestly activated π-systems corresponds to loss of the activated proton to produce an S,N-ketene acetal. When a ketene S,S-acetal group was incorporated onto the side chain, the 1,4-dipolar cycloaddition reaction was facilitated relative to proton loss.

  一系列含有联接π系统的双环无水-4-羟基-2-氧-1,3-噻唑鎓氢氧化物可以通过硫内酰胺与1,3-双电亲体的反应轻松制备。这些交错共轭的杂芳香族贝塔因在良好的产率下经历区域性和立体特异性的1,4-偶极环加成，生成含有羰基硫桥的环加成物，在进一步加热时可以诱导失去COS。通过单晶X射线测定对其中两个环加成物进行了表征。通过改变偶极亲核链的长度，可以控制环加成反应最终产物的环大小。使用苯基炔基取代的硫氨基可以实现对[6,6,5]-和[6,6,6]吡啶酮环系的导入。噻唑鎓贝塔因偶极的环内1,4-偶极环加成也发生在吲哚的π键上。在双环贝塔因的9位仅有一个取代基时，反应的路径会完全不同，除非在连结中加入一个高度活化的π键。与适度活化的π系统的优选反应对应于活化质子的失去，从而生成S,N-烯酮缩醛。当在侧链上引入烯酮S,S-缩醛基时，相较于质子失去，1,4-偶极环加成反应得以促进。
• Cycloaddition Reaction of Mesoionic Betaines as an Approach toward Trialkylindoline Alkaloids
  作者：Albert Padwa、Scott R. Harring、Mark A. Semones

  DOI：10.1021/jo970847m

  日期：1998.1.1

  cross-conjugated heteroaromatic betaine. This 1,4-dipole undergoes a subsequent intramolecular dipolar cycloaddition across the neighboring pi-bond, and the resulting cycloadduct is subsequently converted to the annulated lactam. A related annulation sequence leading to a key intermediate previously utilized in the synthesis of the (+/-)-vallesamidine has been developed which is based on the intramolecular dipolar

  跨束缚的吲哚π键上的脱水-4-羟基-2-氧-2-氧-1,3-噻嗪氢氧化物的分子内1,4-偶极环加成已用于构建epi-16,17-dihydroeburnamenine的五环骨架。3-乙基-3-（烯基）哌啶酮与二烯酮和三氟甲磺酸三甲基甲硅烷基酯在环境温度下的苯反应生成环吡啶酮，收率很高。最初的反应涉及形成N-乙酰乙酰基酰胺，然后用TMSOTf将其进一步转化为吡啶酮。发现整个过程以完全的立体特异性进行。用双烯酮和TMSOTf处理3-乙基-3-[（（E）-4-苯基-3-丁烯基] -2-哌啶酮）样品可产生63％收率的环加成物，其立体化学通过X射线晶体学研究得以阐明。该差向异构体Z-异构体产生了环化二氢吡啶酮的不同立体异构体。环化的机理涉及TMSOTf诱导的环化，然后去除质子并产生交叉缀合的杂芳族甜菜碱。该1，4-偶极分子经过相邻的π键进行分子内偶极分子环加成反应，然后将所得的环加合物转化为环状内酰
• Details associated with the bimolecular 1,4-dipolar cycloaddition reaction of cross-conjugated heteroaromatic betaines
  作者：Albert Padwa、Steven J. Coats、Mark A. Semones

  DOI：10.1016/0040-4020(95)00323-z

  日期：1995.6

  prepared from the reaction of 3H-thiolactams with 1,3-bielectrophiles. These cross-conjugated heteroaromatic betaines undergo regio- and diastereospecific 1,4-dipolar cycloaddition with electron-rich and electron-deficient π-bonds to produce 1,4-cycloadducts containing a carbonyl sulfide bridge. A representative betaine dipole and a 1,4-cycloadduct were characterized by single crystal X-ray determinations

  通过3H-硫代内酰胺与1,3-双亲电子试剂的反应，可以轻松地制备一系列3,3-二取代的双环脱水4-羟基-2-羟基-2-氧代-1,3-噻嗪鎓氢氧化物。这些交叉共轭的杂芳族甜菜碱经过区域和非对映异构的1,4-偶极环加成反应，并带有富电子和缺电子的π键，生成含有羰基硫桥的1,4-环加合物。通过单晶X射线测定来表征代表性的甜菜碱偶极子和1,4-环加合物。在某些情况下，最初形成的环加合物可以在进一步加热时失去COS。噻嗪甜菜碱的前沿轨道系数通过PM3哈密顿量的半经验MOPAC计算确定。1的HOMO