3,4-bis(diphenylmethylene)-1,2-cyclobutanedione | 23596-82-9

• 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: 3,4-bis(diphenylmethylene)-1,2-cyclobutanedione
• 英文别名: 3,4-bis(diphenylmethylene)-cyclobutanedione；3,4-bis(diphenylmethylene)cyclobutanedione；3.4-Bis-(diphenylmethylen)-cyclobutandion-(1.2)；3,4-Bis-(diphenylmethylen)-cyclobutan-1,2-dion；3,4-Bis-(diphenylmethylen)-cyclobuta-1,2-dion；3.4-Bis-diphenylmethylen-cyclobutandion-(1.2)；3,4-Bis(diphenylmethylidene)cyclobutane-1,2-dione；3,4-dibenzhydrylidenecyclobutane-1,2-dione
• CAS: 23596-82-9
• 化学式: C₃₀H₂₀O₂
• 分子量: 412.488
• InChiKey: PLQSOQJQSXUCLN-UHFFFAOYSA-N

物化性质

• 沸点：
  625.5±65.0 °C(Predicted)
• 密度：
  1.240±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  3,4-bis(diphenylmethylene)-1,2-cyclobutanedione 在 氨 、 溴 作用下， 以 四氯化碳 为溶剂， 以34%的产率得到3,4-bis(diphenylmethylene)succinimide
  参考文献：
  名称：

  Structure, solid-state photochemistry and reactivity in asymmetric synthesis of 3,4-bis(diphenylmethylene)-N-methylsuccinimide

  摘要：

  The synthesis and structural features of 3,4-dihydro-3,4-bis(diphenylmethylene)-N-methylsuccinimide [3,4-bis(diphenylmethylene)-1-methyl-2,5-pyrrolidinedione (6b), C31H23NO1, M(r)=441.53] are described. (6b) crystallizes at room temperature in three polymorphic forms: (A) monoclinic P2(1), a=11.640(3), b=9.257(2), c=12.103(4)Angstrom, beta=114.83(1)degrees, V=1183.6(6)A(3) Z=2, F(000)=464, D-x=1.239gcm(-3), mu=0.72cm(-1), R(F)=0.077 for 1560 observations [I>3 sigma(I)]; (B) orthorhombic, Pbcn, a=9.964(1), b=20.181(3), c=11.622(3)Angstrom, V=2337.0(7)Angstrom(3), Z=4, F(000)=928, D-x=1.255gcm(-3), mu=0.73cm(-1), R(F)=0.044 for 1466 observations [I>3 sigma(I)]; (C) monoclinic, P2(1)/n, a=9.485(3), b=11.014(2), c=22.945(3)Angstrom, V=2369.9(9)Angstrom(3), Z=4, F(000)=928, D-x=1.238gcm(-3), mu=0.72cm(-1), R(F)=0.060 for 2200 observations [I>3 sigma(I)]. The (6b) molecule adopts a helical (prochiral) configuration with approximate C-2 symmetry in order to accommodate the steric hindrance between the aryl substituents; the conformation is very similar in the three polymorphs. Transformations between the different polymorphs can be induced easily, and it is possible to vary the amount of chiral polymorph in the crystallization mixture by seeding techniques and the use of acidic additives. Crystalline (6b) undergoes a photocyclization reaction to yield N-methyl-1,1,4-triphenyl-1,2-dihydronaphthalene-2,3-dicarboximide (8b). In the observed conformation of (6b), the intramolecular distances between the unsaturated carbon sites which join during the photochemical reaction are within 3.27-3.38 Angstrom. The solid-state photoreaction of the chiral polymorph A gives an optically active molecular product (8b) of 64% enantiomeric excess (e.e.), and represents a chiral enrichment process assisted by the crystal medium. The corresponding photochemical reactions with the racemic polymorphs B and C yield racemic (8b).

  DOI：

  10.1107/s0108768194014540
• 作为产物：
  描述：

  2-bromo-4-(diphenylmethylene)-3-(hydroxydiphenylmethyl)cyclobut-2-en-1-one 在 盐酸 、 硫酸 作用下， 以 甲醇 为溶剂， 生成 3,4-bis(diphenylmethylene)-1,2-cyclobutanedione
  参考文献：
  名称：

  环丁二烯醌的亚甲基类似物-II：2-卤代和2,2-二卤代-3,4-双（二苯基亚甲基）环丁酮的制备和反应

  摘要：

  已经制备了标题化合物（II，XVII；二氯和二溴衍生物），并且描述了化合物的一些新反应。

  DOI：

  10.1016/s0040-4020(01)98071-8

文献信息

• THE SYNTHESIS OF 3-BENZOYL-4-METHYLENECYCL0BUT-1-ENE AND 6-METHYLENE-1-OXASPIRO[2,3]HEX-4-ENE, AND THEIR RING EXPANSION INTO METHYLENECYCLOPENTENONES
  作者：Kozaburo Ueda、Fumio Toda

  DOI：10.1246/cl.1974.359

  日期：1974.4.5

  The reaction of 2,3,3-tribromo-1-diphenylhydroxymethyl-4-diphenylmethylenecyclobut-1-ene (I) with AgClO4 afforded new 4,5-dibromo-2,2-diphenyl-6-diphenylmethylene-1-oxaspiro [2,3]hex-4-ene (VI) and 3-benzoyl-1,2-dibromo-3-phenyl-4-diphenylmethylenecyclobut-1-ene (VIII), probably via the methylenecyclobutenylium ion (II). New acid-catalyzed ring expansion reaction of VI to afford 3,4-dibromo-2,2-diphenyl-5-diphenylmethylenecyclopent-3-en-1-one (XIV) and 2,3-dibromo-5,5-diphenyl-4-diphenylmethylenecyclopent-2-en-1-one (XV) was found.

  2,3,3-三溴-1-二苯基氢氧基甲基-4-二苯基亚甲基环丁烯 (I) 与 AgClO4 的反应生成了新化合物 4,5-二溴-2,2-二苯基-6-二苯基亚甲基-1-氧螺[2,3]六烯 (VI) 和 3-苯甲酰-1,2-二溴-3-苯基-4-二苯基亚甲基环丁烯 (VIII)，可能是通过亚甲基环丁烯阳离子 (II) 产生的。发现 VI 的新酸催化环扩张反应生成 3,4-二溴-2,2-二苯基-5-二苯基亚甲基环戊-3-烯-1-酮 (XIV) 和 2,3-二溴-5,5-二苯基-4-二苯基亚甲基环戊-2-烯-1-酮 (XV)。
• The Oxidation of 1,3-Butadienes with Nitric Acid into 2,5-Dihydrofurans
  作者：Fumio Toda、Eishiro Todo

  DOI：10.1246/bcsj.47.348

  日期：1974.2

  The oxidation of 3,4-bis(diphenylmethylene)-succinic anhydride (I), -1-benzylsuccinimide (VI), and -γ-butyrolactone (VIII) with nitric acid afforded the corresponding 2,5-dihydrofuran derivatives, III, VII, and IX respectively. The same oxidation of 3,4-bis(diphenylmethylene)cyclobutane-1,2-dione (XI) afforded 3,4-bis(diphenylhydroxymethyl)cyclobut-3-ene-1,2-dione (XIII), probably via the bicyclic cyclobutenedione intermediate (XII).

  用硝酸氧化 3,4-双（二苯基亚甲基）-丁二酸酐（I）、-1-苄基丁二酰亚胺（VI）和-γ-丁内酯（VIII），分别得到相应的 2,5-二氢呋喃衍生物 III、VII 和 IX。同样氧化 3,4-双（二苯基亚甲基）环丁烷-1,2-二酮 (XI)，得到 3,4-双（二苯基羟甲基）环丁-3-烯-1,2-二酮 (XIII)，可能是通过双环环丁二酮中间体 (XII)。
• Methylene Analogs of Cyclobutenedione. VI. Interconversion between 3,4-Dimethylcyclobut-3-ene-1,2-dione and 3,4-Dimethylenecyclobutane-1,2-dione
  作者：Fumio Toda、Nobuhiro Ooi

  DOI：10.1246/bcsj.46.1733

  日期：1973.6

  enolate anion (VIII), afforded III and IV in various ratios depending on the steric nature of the substituent R. Bromination of IV in 99% acetic acid afforded 3,4-bis(hydroxydiphenylmethyl)cyclobut-3-ene-1,2-dione (XI). Although the bromination of XI with phosphorus tribromide afforded IV, that with bromine afforded the 2,5-dihydrofuran derivative (XVII). The reaction of I with o-phenylenediamine to afford

  在 ROH（R=H、Me、Et 和 i-Pr）中用溴处理 3,4-双（二苯基甲基）环丁-3-烯-1,2-二酮 (I)，得到 3,4-双（二苯基亚甲基） )环丁烷-1,2-二酮 (IV) 和 3-二苯基甲基-4-烷氧基二-苯基甲基环丁-3-烯-1,2-二酮 (III) 的比例取决于 ROH 的 R 的空间体积。III 在 KOH-MeOH 中的溶液的酸化，其中 III 以烯醇阴离子 (VIII) 的形式存在，根据取代基 R 的空间性质以不同的比例提供 III 和 IV。 IV 在 99% 乙酸中的溴化得到3,4-双(羟基二苯基甲基)环丁-3-烯-1,2-二酮(XI)。虽然用三溴化磷对 XI 进行溴化得到 IV，但用溴化得到 2,5-二氢呋喃衍生物 (XVII)。
• Condensations of 3,4-Bis(diphenylmethylene)-1,2-cyclobutanedione with<i>o</i>-Phenylenediamine under Ionic and Radical Reaction Conditions
  作者：Zaiko Ro、Koichi Tanaka、Fumio Toda

  DOI：10.1246/bcsj.56.3193

  日期：1983.10

  The title condensations under ionic and radical reaction conditions gave 1,2-bis(diphenylmethylene)-1,2-dihydrocyclobuta[b]quinoxaline and 7,8-bis(diphenylmethylene)-7,8-dihydrobenzo[b][1,4]diazocine-6,9(5H,10H)-dione respectively.

  在离子反应和自由基反应条件下进行的标题缩合反应分别生成了 1,2-双（二苯基亚甲基）-1,2-二氢环丁基[b]喹喔啉和 7,8-双（二苯基亚甲基）-7,8-二氢苯并[b][1,4]二氮杂环辛-6,9(5H,10H)-二酮。
• Isolation of tetraphenyl-, pentaphenyl-, hexaphenyl-, and heptaphenyl-substituted tetramethylenecyclobutanes. Stable tetraradialenes
  作者：Koichi Tanaka、Fumio Toda

  DOI：10.1016/s0040-4039(00)78587-x

  日期：1980.1

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