1-acetoxybuta-1,3-diene | 35694-20-3

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-acetoxybuta-1,3-diene
• 英文别名: 1-acetoxybutadiene；(E)-buta-1,3-dien-1-yl acetate；1-Acetoxy-1,3-butadiene；[(1E)-buta-1,3-dienyl] acetate
• CAS: 35694-20-3；1515-76-0
• 化学式: C₆H₈O₂
• 分子量: 112.128
• InChiKey: NMQQBXHZBNUXGJ-SNAWJCMRSA-N

物化性质

• 沸点：
  60-61 °C40 mm Hg(lit.)
• 密度：
  0.96 g/mL at 20 °C(lit.)
• 闪点：
  92 °F
• 稳定性/保质期：
  1. 如果遵照规格使用和储存，则不会分解，未有已知危险反应，避免接触氧化物。 2. 在长期储存后会发生聚合，可根据需要通过蒸馏进行纯化。该试剂属于高度挥发和易燃的化学品，建议在干燥低温处保存，并在通风橱中使用。

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险等级：
  3
• 储存条件：
  在2°C至-8°C下保存

制备方法与用途

用途

1-乙酰氧基-1,3-丁二烯在有机合成中主要用于与亲二烯体发生Diels-Alder反应。该反应生成的产物不仅在环上引入了乙酰氧基，还便于进一步的化学修饰。由于乙酰氧基的存在使得分子中的烯键更加富电子，更容易与亲二烯体进行Diels-Alder反应。反式异构体具有较高的反应活性，因此直接使用顺反异构体混合物也可生成高度区域选择性的产物或单一产物。当使用缺电子性强的亲二烯体时，反应可以在室温下进行；若亲二烯体位阻较大，则需在较高温度下进行。如果产物结构适当，在较高的反应温度下，乙酰氧基会自动消去，直接生成相应的芳香化合物。

类别

有毒物品

毒性分级

中毒

急性毒性

• 大鼠经口LD₅₀：710毫克/公斤

刺激数据

• 皮肤接触（兔子）：0.1毫克/24小时，中度刺激

可燃性危险特性

可燃；加热分解时释放刺激烟雾

储运特性

库房通风、低温干燥保存

灭火剂

干粉、泡沫、砂土、二氧化碳及雾状水

反应信息

• 作为反应物：
  描述：

  1-acetoxybuta-1,3-diene 在 PBS buffer 、 antibody H₁₁ 作用下， 以 乙腈 为溶剂， 生成 巴豆醛
  参考文献：
  名称：

  抗体H11的催化性能

  摘要：

  已显示抗体H11的催化活性主要在于其将1-乙酰氧基丁二烯水解成巴豆醛并促进中间烯醇与N-烷基马来酰亚胺的环加成的能力。该结论基于以下事实：烯醇在溶液中互变异构化太快而不能作为有效的中间体，并且在H11的反应条件下，巴豆醛和N-乙基马来酰亚胺不会发生环加成反应。作为对H11的化学结构进行了解的第一步，化学修饰实验表明，酸性氨基酸，酪氨酸，赖氨酸和组氨酸而不是精氨酸的反应会抑制H11介导的反应。

  DOI：

  10.1002/ijch.199600023
• 作为产物：
  描述：

  2-acetoxy-2,5-dihydrothiophene-1,1-dioxide 在 二氧化硫 作用下， 生成 1-acetoxybuta-1,3-diene
  参考文献：
  名称：

  Competition between Hetero-Diels−Alder and Cheletropic Addition of Sulfur Dioxide. Theoretical and Experimental Substituent Effects on the Relative Stability of 3,6-Dihydro-1,2-oxathiin-2-oxides (Sultines) and 2,5-Dihydrothiophene-1,1-dioxides (Sulfolenes). Anomeric Effects in Sultine and 6-Substituted Derivatives

  摘要：

  At low temperature and in the presence of CF3COOH, SO2 undergoes Diels-Alder additions with (E)-1-acetoxybutadiene (8d) giving a 1:10 mixture of diastereomeric 6-acetoxysultines (9d + 10d). The Van't Hoff plot for equilibria 8d + SO2 reversible arrow 9d + 10d led to Delta H-r = -7.0 +/- 0.3 kcal/mol, Delta S-r = -42 +/- 3 cal . mol(-1) . K-1. At 20 degrees C, 8d underwent a slow cheletropic addition with SO2 giving 2-acetoxysulfolene (11d, Delta Hr congruent to -11.5 kcal/mol), the structure of which was established by single-crystal X-ray diffraction studies. (E)-Chloro (8e) and (E)-bromobutadiene (8f) did not undergo Diels-Alder additions with SO2, even in the presence of protic or Lewis acid promoters. Low yields of 2-chloro- (11e) and 8-bromosulfolene (11f) were obtained at 20 degrees C. The structure of 11e was confirmed by single-crystal X-ray diffraction. The potential energy hypersurfaces of the Diels-Alder and cheletropic additions of SO2 to butadiene (8a), (E)-piperilene (8b), (E)-1-methoxy- (8c), (E)-1-acetoxy- (8d), and (E)-1-chlorobutadiene (8e) were studied by ab initio quantum calculations at the MP2/6-31G* level. In agreement with the experiment, 6-substituted sultines 9X and 10X were less stable than the corresponding 2-substituted sulfolenes 11X for X = Me, OAc, Cl. With X = OMe, the two diastereomeric 6-methoxysultines (9c, 10c) and 8-methoxysulfolene (11c) were calculated to have similar stabilities. This is attributed to a stabilizing thermodynamic anomeric effect or gem-sulfinate/methoxy disubstitution effect in 9c, 10c. Such effects were not detected for sulfinate/acetoxy (9d, 10d) and sulfinate/chloro (9e, 10e) disubstitutions. The relative instability of 8-acetoxy- (11d) and 2-chlorosulfolene (11e) compared with their cycloaddents is attributed to repulsive interactions between the SO2 moieties and the 2-substituents. The Alder endo mode of [4 + 2] cycloaddition of SO2 is predicted to be faster than the "anti-Alder mode" of additions for dienes 8X, X = Me, OMe, OAc, Cl. The resulting diastereomeric sultines 9X and 10X, respectively, exist as equilibria (energy barrier: ca. 5-6 kcal/mol) of two conformers 9X reversible arrow 9X, 10X reversible arrow 10X. In general, the conformers 9X, 10X with pseudoaxial S=O group are preferred (conformational anomeric effect of the sulfinate moiety). Repulsive interactions between pseudoaxial S=O and polar cis-6-substituents (e.g.: X = OMe, OAc) in 9X may render conformers 9X (with the S-O and 6-X groups in pseudoequatorial positions) as stable as conformers 9X. The calculations predict the existence of conformational anomeric effects of 2-3 kcal/mol for the gem-sulfinate/methoxy (9c, 10'c) and gem-sulfinate/acetoxy disubstitution (9d, 10'd).

  DOI：

  10.1021/jo981679g

文献信息

• Chemical transformation of substrates using nonmetallic, organic catalyst compositions
  申请人：The Regents of the Univerisity of California

  公开号：US06369243B1

  公开（公告）日：2002-04-09

  A method is provided for catalytically transforming a functional group within a first reactant by reaction with a second reactant in the presence of a nonmetallic, organic catalyst composition composed of a heteroatom-containing activator and an acid, or a salt of a heteroatom-containing activator and an acid. Exemplary first reactants are &agr;,&bgr;-unsaturated carbonyl compounds such as &agr;,&bgr;-unsaturated ketones and &agr;,&bgr;-unsaturated aldehydes. The heteroatom of the activator is a Group 15 or Group 16 element such as nitrogen, oxygen, sulfur or phosphorus, and exemplary heteroatom-containing activators are amines. Chiral heteroatom-containing activators can be used to catalyze enantioselective reactions, such that a chiral product is obtained from a chiral or achiral starting material in enantiomerically pure form.

  提供了一种方法，通过在非金属有机催化剂组合物的存在下，使第一反应物中的一个官能团与第二反应物发生反应，从而催化转化它。该催化剂组合物由含杂原子的活化剂和酸组成，或者由含杂原子的活化剂和酸的盐组成。示例第一反应物是α,β-不饱和羰基化合物，如α,β-不饱和酮和α,β-不饱和醛。活化剂的杂原子是第15组或第16组元素，如氮、氧、硫或磷，示例含杂原子的活化剂是胺。手性含杂原子的活化剂可用于催化对映选择性反应，从而从手性或不手性的起始物质中获得对映纯形式的手性产物。
• [EN] RAF-DEGRADING CONJUGATE COMPOUNDS<br/>[FR] COMPOSÉS CONJUGUÉS DE DÉGRADATION DE RAF
  申请人：QUARTZ THERAPEUTICS INC

  公开号：WO2018200981A1

  公开（公告）日：2018-11-01

  The present disclosure provides, inter alia, RAF-Degrading Conjugate Compounds that are useful in the treatment of cancer and other RAF related diseases. Also provided are, pharmaceutical compositions, methods of treatment, and kits comprising a RAF- Degrading Conjugate Compound.

  本公开提供了用于治疗癌症和其他与RAF相关疾病的RAF降解共轭化合物。还提供了药物组合物、治疗方法和包含RAF降解共轭化合物的试剂盒。
• Bis(oxazoline) and Bis(oxazolinyl)pyridine Copper Complexes as Enantioselective Diels−Alder Catalysts:  Reaction Scope and Synthetic Applications
  作者：David A. Evans、David M. Barnes、Jeffrey S. Johnson、Thomas Lectka、Peter von Matt、Scott J. Miller、Jerry A. Murry、Roger D. Norcross、Eileen A. Shaughnessy、Kevin R. Campos

  DOI：10.1021/ja991191c

  日期：1999.8.1

  the use of this chiral catalyst in more complex Diels−Alder processes, are described. Similarly, the cationic copper complex 9a, [Cu((S,S)-t-Bu-pybox)](SbF6)2, is effective in the Diels−Alder reactions of monodentate acrolein dienophiles while the closely related complex, 9d [Cu((S,S)-Bn-pybox)](SbF6)2, is the preferred Lewis acid catalyst for acrylate dienophiles in reactions with cyclopentadiene.

  已经研究了由双（恶唑啉）铜配合物催化的 Diels-Alder 反应的范围。特别是，[Cu((S,S)-t-Bu-box)](SbF6)2 (1b) 已被证明可以催化 3-propenoyl-2-oxazolidinone (2) 和一系列的 Diels-Alder 反应。具有高对映选择性的取代二烯。这种阳离子复合物也已成功用于类似分子内过程的催化。描述了 ent-Δ1-四氢大麻酚、ent-莽草酸和 isopulo'upone 的全合成，其特点是在更复杂的 Diels-Alder 过程中使用这种手性催化剂。类似地，阳离子铜配合物 9a，[Cu((S,S)-t-Bu-pybox)](SbF6)2，在单齿丙烯醛亲二烯体的 Diels-Alder 反应中是有效的，而密切相关的配合物 9d [Cu ((S,S)-Bn-pybox)](SbF6)2,
• Solid-phase synthesis of heterocycles via palladium-catalyzed annulation
  作者：Yao Wang、Tai-Nang Huang

  DOI：10.1016/s0040-4039(98)02337-5

  日期：1998.12

  Solid-phase linked o-iodoanilines (4) and o-iodophenol (9) reacted with 1,3- and 1,4-dienes in the presence of palladium acetate to generate highly substituted indolines, tetrahydroquinolines, hydrobenzofurans and hydrobenzopyrans, which provided an efficient way for making heterocyclic molecule libraries.

  在乙酸钯存在下，固相连接的邻碘苯胺（4）和邻碘苯酚（9）与1，3-和1，4-二烯反应生成高度取代的二氢吲哚，四氢喹啉，氢苯并呋喃和氢苯并吡喃。制备杂环分子文库的有效方法。
• Regioselective Rhodium-Catalyzed Hydroformylation of 1,3-Dienes to Highly Enantioenriched β,γ-Unsaturated Aldehyes with Diazaphospholane Ligands
  作者：Avery L. Watkins、Clark R. Landis

  DOI：10.1021/ol102797t

  日期：2011.1.7

  Regioselective and enantioselective rhodium-catalyzed hydroformylation of 1,3-dienes with chiral bisdiazaphospholane ligands yields β,γ-unsaturated aldehydes that retain a C═C functionality for further conversion. The reaction conditions are mild, featuring low catalyst loadings (0.5 mol %), pressures readily obtained in glass bottles, and convenient reaction times (1.5−12 h). Optimized reaction conditions

  带有手性双二氮杂膦烷配体的1,3-二烯的区域选择性和对映体选择性的铑催化加氢甲酰化生成β，γ-不饱和醛，其保留C═C官能度以用于进一步转化。反应条件温和，具有催化剂用量低（0.5 mol％），在玻璃瓶中容易获得的压力以及方便的反应时间（1.5-12 h）。优化的反应条件可产生高对映体选择性（> 90％ee），区域选择性（88-99％），并转化为10,1,3-二烯，涵盖多种取代模式，转化为β，γ-不饱和醛（99％）。

表征谱图