(Z)-α-propylidene-γ-butyrolactone | 52216-89-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (Z)-α-propylidene-γ-butyrolactone
• 英文别名: α(Z)-Propylidene-γ-butyrolactone；(Z)-2-propylidene-γ-butyrolactone；(Z)-3-propylidenedihydrofuran-2(3H)-one；α-cis-Propyliden-γ-butyrolacton；(3Z)-3-propylideneoxolan-2-one
• CAS: 52216-89-4
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: BQZOCIXOOMBTEJ-UTCJRWHESA-N

物化性质

• 沸点：
  70-75 °C(Press: 0.6 Torr)
• 密度：
  1.147±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-α-propylidene-γ-butyrolactone 以73%的产率得到
  参考文献：
  名称：

  HENIN, F.;MORTEZAEI, R.;PETE, J. -P., SYNTHESIS, BRD, 1983, N 12, 1019-1021

  摘要：

  DOI：
• 作为产物：
  描述：

  1-(2-oxooxolan-3-yl)propyl acetate 生成 (Z)-α-propylidene-γ-butyrolactone
  参考文献：
  名称：

  ITOKAWA, HIDEJI;OSHIMA, TOSHIYUKI;MATSUMOTO, HAJIME;MIHASHI, SUSUMU, J. PHARM. SOC. JAP., 1984, 104, N 8, 839-847

  摘要：

  DOI：

文献信息

• Stereoselective Synthesis of (<i>E</i>)- or (<i>Z</i>)-α-Alkylidene-γ-butyrolactone from γ-Butyrolactone and Bis[ethoxy(thiocarbonyl)] Disulfide and Mechanistic Studies of the Effect of Metal Complexes on the Stereoselection
  作者：Syuichi Matsui

  DOI：10.1246/bcsj.60.1853

  日期：1987.5

  with an aldehyde to afford exclusively (E)-α-alkylidene-γ-butyrolactone. Interestingly, when the reaction was quenched below −20 °C or when it was carried out in the presence of metal complex such as zinc chloride, copper(I) iodide, or tributyltin chloride, (Z)-α-alkylidene-γ-butyrolactone was obtained as the major product. The stereoselectivity of this reaction was sensitive to the reaction temperature

  在 2.2 当量二异丙基氨基锂 (LDA) 存在下，用双 [乙氧基（硫代羰基）] 二硫化物处理 γ-丁内酯，生成 O-乙基 S-（四氢-2-氧代-3-呋喃基）二硫代碳酸酯的烯醇锂，其反应用醛生成仅 (E)-α-亚烷基-γ-丁内酯。有趣的是，当反应在 -20 °C 以下猝灭或在金属络合物（如氯化锌、碘化铜（I）或氯化三丁基锡、（Z）-α-亚烷基-γ-丁内酯）存在下进行时作为主要产品获得。该反应的立体选择性对反应温度和所用金属阳离子敏感。
• New Methods for Stereoselective Synthesis of α-Alkylidene-γ-butyrolactones Using Monoanion of<i>O</i>-Ethyl<i>S</i>-(Tetrahydro-2-oxo-3-furanyl) Thiocarbonate and Dianion of α-Mercapto-γ-butyrolactone
  作者：Kazuhiko Tanaka、Hideki Uneme、Nobuyuki Yamagishi、Rikuhei Tanikaga、Aritsune Kaji

  DOI：10.1246/bcsj.53.2910

  日期：1980.10

  The lithium enolates of O-ethyl S-(tetrahydro-2-oxo-3-furanyl) dithiocarbonate and thiocarbonate were found to be efficient reagents for the stereoselective synthesis of α-alkylidene-γ-butyrolactones from carbonyl compounds. The dianion of α-mercapto-γ-butyrolactone was successfully generated by treatment of α-mercapto-γ-butyrolactone with 2.2 equivalents of lithium diisopropylamide in the presence

  发现 O-乙基 S-(四氢-2-氧代-3-呋喃基)二硫代碳酸酯和硫代碳酸酯的锂烯醇化物是从羰基化合物立体选择性合成 α-亚烷基-γ-丁内酯的有效试剂。α-巯基-γ-丁内酯的二价阴离子是在-78°C、N,N,N',N'-四甲基乙二胺存在下，用2.2当量的二异丙基氨基锂处理α-巯基-γ-丁内酯而成功生成的。四氢呋喃。由此形成的二价阴离子已被用于从羰基化合物有效和立体选择性地合成 α-亚烷基-γ-丁内酯。
• A new synthesis of α-methylene lactones
  作者：Alistair W. Murray、Robert G. Reid

  DOI：10.1039/c39840000132

  日期：——

  The α-formylation of γ-and δ-lactones and the high yield conversion in to their respective α-methylene γ-and δ-lactones are described.

  描述了δ-和δ-内酯的δ-甲酰化反应以及将其高产率转化为各自的δ-亚甲基δ-和δ-内酯的过程。
• Temperature Effects on Stereocontrol in the Horner−Wadsworth−Emmons Condensation of α-Phosphono Lactones
  作者：Jose S. Yu、David F. Wiemer

  DOI：10.1021/jo070722+

  日期：2007.8.1

  The Horner−Wadsworth−Emmons condensation of some α-phosphono lactones has been examined for conditions that impact product stereochemistry. The temperature employed to quench the reaction was found to be a major factor. For example, after the diethyl phosphonate derivative of γ-butyrolactone was treated with potassium hexamethyldisilazane, 18-crown-6, and propionaldehyde at −78 °C in THF, an aliquot

  对某些α-膦酰基内酯的霍纳-沃兹沃思-埃蒙斯缩合反应进行了影响产物立体化学的条件研究。发现用于淬灭反应的温度是主要因素。例如，将γ-丁内酯的二乙基膦酸酯衍生物在THF中在-78°C下用六甲基二硅氮烷钾，18-crown-6和丙醛处理后，等分试样转移到约30°C的烧瓶中，几乎得到Z -烯烃产物，尽管允许其在数小时内升温至室温，却非常有利于E-烯烃。
• Asymmetric Hydrogenation of Olefins with Aprotic Oxygen Functionalities Catalyzed by BINAP-Ru(II) Complexes
  作者：Tetsuo Ohta、Tsutomu Miyake、Nobuo Seido、Hidenori Kumobayashi、Hidemasa Takaya

  DOI：10.1021/jo00107a014

  日期：1995.1

  Cyclic alpha,beta-unsaturated ketones, alkylidene lactones, and alkenyl ethers have been hydrogenated in high enantiomeric excesses by use of BINAP-Ru(II) complexes (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) as catalysts. 2-Alkylidenecyclopentanones were hydrogenated in the presence of [RuCl(BINAP)(benzene)]Cl, Ru2Cl4(BINAP)2(NEt(3)), or Ru(OCO CH3 )(2)(BINAP) in up to 98% ee, while in the case of 2-benzylidene- and 2-(3-phenylpropylidene)cyclopentanones, enantiomeric excesses of the hydrogenation were below 50% under the same conditions. The sense of asymmetric induction as well as the enantioselectivity (95% ee) obtained in the hydrogenation of (E)-2-propylidene-gamma-butyrolactone were the same as those of the (Z)-isomer. Lactones, 2- and 4-alkylidene-gamma-butyrolactones, were converted to the corresponding saturated gamma-butyrolactones in 95% ee. Hydrogenation of diketene with the catalytic system derived from RuCl[(S)-BINAP](benzene)}Cl and triethylamine or complex Ru2Cl4[(S)-BINAP](2)(NEt(3)) established a new synthetic route to (R)-4-methyl-2-oxetanone, a promising monomer of biodegradable polymers, in up to 97% selectivity and 92% ee. Alkenyl ethers, 2-methylenetetrahydrofuran, and 2-methyl-3,4-dihydrofuran have also been hydrogenated to give 2-methyltetrahydrofuran in 91 and 87% ee, respectively.