2-butynyl 1-formate | 36678-14-5

• 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: 2-butynyl 1-formate
• 英文别名: But-2-ynyl formate
• CAS: 36678-14-5
• 化学式: C₅H₆O₂
• 分子量: 98.1014
• InChiKey: KIGVCODOBDNAOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  2-butynyl 1-formate 、 2-Butynyl phenylacetate 在 sodium hydride 、 甲烷磺酰基叠氮化物 作用下， 生成 2-butynyl 2-diazophenylacetate
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans

  摘要：

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.

  DOI：

  10.1021/jo00053a009
• 作为产物：
  描述：

  1,4-bis(formyloxy)but-2-yne 在 copper(I) oxide 己二酸 作用下， 生成 2-butynyl 1-formate
  参考文献：
  名称：

  Synthese von α-Acetylenalkoholen bzw. ihren Formiaten und Dialkylacetylenen

  摘要：

  DOI：

  10.1055/s-1973-22272
• 作为试剂：
  描述：

  2-Butynyl phenylacetate 在 palladium on activated charcoal rhodium(II) octanoate 、 2-丁炔-1-醇 、 2-butynyl 1-formate 、 氢气 、 sodium hydride 、 甲烷磺酰基叠氮化物 作用下， 以 乙酸乙酯 、 苯 为溶剂， 反应 2.5h， 生成 8-Methyl-3-oxo-3,3a,8,8a-tetrahydro-1H-indeno<1,2-c>furan
  参考文献：
  名称：

  Spectroscopy and Photochemistry of Phenylacetic Acid Esters and Related Substrates. The Stereoelectronic Dependence of the Aryl/Carboxyl Bichromophore Interaction

  摘要：

  The 254-nm-initiated Norrish Type II photofragmentation of the ethoxyethyl esters of a series of phenylacetic acids (1b-4b) has been studied in order to further elaborate the aryl/ester interaction that is photochemically and photophysically evident in these systems. The ethoxyethyl ester of benzonorbornene-1-carboxylic acid (5) has also been prepared and studied, as has a rigid tricyclic lactone (6) which places the chromophores in an optimal stereoelectronic relationship for interaction. The experimental work is accompanied by Hartree-Fock (HF), Natural Bond Orbital (NBO), and Configuration Interaction with Single Excitations (CIS) calculations on the methyl esters of phenylacetic acid (1a) and alpha-methoxyphenylacetic acid (4a). The calculations confirm extensive through-space (TS) and through-bond (TB) interactions between the aryl and ester pi* orbitals but fail to provide conformational or electronic arguments to explain the unusually high reactivity of the alpha-methoxy series.

  DOI：

  10.1021/jo00089a025

文献信息

• Kasper Annette M., Nash John J., Morrison Harry, J. Org. Chem, 59 (1994) N 10, S 2792-2798
  作者：Kasper Annette M., Nash John J., Morrison Harry

  DOI：——

  日期：——
• Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans
  作者：Albert Padwa、Frederick R. Kinder

  DOI：10.1021/jo00053a009

  日期：1993.1

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.
• Spectroscopy and Photochemistry of Phenylacetic Acid Esters and Related Substrates. The Stereoelectronic Dependence of the Aryl/Carboxyl Bichromophore Interaction
  作者：Annette M. Kasper、John J. Nash、Harry Morrison

  DOI：10.1021/jo00089a025

  日期：1994.5

  The 254-nm-initiated Norrish Type II photofragmentation of the ethoxyethyl esters of a series of phenylacetic acids (1b-4b) has been studied in order to further elaborate the aryl/ester interaction that is photochemically and photophysically evident in these systems. The ethoxyethyl ester of benzonorbornene-1-carboxylic acid (5) has also been prepared and studied, as has a rigid tricyclic lactone (6) which places the chromophores in an optimal stereoelectronic relationship for interaction. The experimental work is accompanied by Hartree-Fock (HF), Natural Bond Orbital (NBO), and Configuration Interaction with Single Excitations (CIS) calculations on the methyl esters of phenylacetic acid (1a) and alpha-methoxyphenylacetic acid (4a). The calculations confirm extensive through-space (TS) and through-bond (TB) interactions between the aryl and ester pi* orbitals but fail to provide conformational or electronic arguments to explain the unusually high reactivity of the alpha-methoxy series.
• Synthese von α-Acetylenalkoholen bzw. ihren Formiaten und Dialkylacetylenen
  作者：Walter HIMMELE、Werner FLIEGE、Helmut FRÖHLICH

  DOI：10.1055/s-1973-22272

  日期：——