methyl 1,2,3,4-tetrahydro-1-oxo-2-naphthaleneglyoxalate | 57763-56-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: methyl 1,2,3,4-tetrahydro-1-oxo-2-naphthaleneglyoxalate
• 英文别名: α,1-Dioxo-tetrahydro-2-naphthaleneacetic Acid Methyl Ester；(+/-)-(1-Oxo-1,2,3,4-tetrahydro-<2>naphthyl-glyoxylsaeure-methylester；(1-oxo-1,2,3,4-tetrahydro-[2]naphthyl)-glyoxylic acid methyl ester；(1-Oxo-1,2,3,4-tetrahydro-[2]naphthyl)-glyoxylsaeure-methylester；Methyl oxo(1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl)acetate；methyl 2-oxo-2-(1-oxo-3,4-dihydro-2H-naphthalen-2-yl)acetate
• CAS: 57763-56-1
• 化学式: C₁₃H₁₂O₄
• 分子量: 232.236
• InChiKey: XDAVYSFOCVKRDF-UHFFFAOYSA-N

物化性质

• 熔点：
  65.5-66.5 °C
• 沸点：
  385.7±32.0 °C(Predicted)
• 密度：
  1.262±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2918300090

反应信息

• 作为反应物：
  描述：

  methyl 1,2,3,4-tetrahydro-1-oxo-2-naphthaleneglyoxalate 在 palladium on activated charcoal 、 镍 氢氧化钾 、 高氯酸 、 氢气 作用下， 以 甲醇 为溶剂， 生成 (R)-1,2,3,4-tetrahydronaphthalene-2-carboxylic acid
  参考文献：
  名称：

  Schoofs,A. et al., Bulletin de la Societe Chimique de France, 1976, p. 1215 - 1221

  摘要：

  DOI：
• 作为产物：
  描述：

  草酸二甲酯 、 3,4-二氢-1(2H)-萘酮 在 base 作用下， 以10.4%的产率得到methyl 1,2,3,4-tetrahydro-1-oxo-2-naphthaleneglyoxalate
  参考文献：
  名称：

  Evidence for ketene intermediates in the decarbonylation of 2,4-dioxo acids and esters and 2-oxobutanedioic acid esters

  摘要：

  The mechanism by which alpha, gamma-dioxo carboxylic acid esters 1 and 2-oxobutanedioic acid diesters 2 lose CO was explored. The compounds, 5,5-dimethyl-2,4-dioxohexanoic acid ethyl ester, 1a, alpha,2-dioxocyclohexaneacetic acid ethyl ester, 1b, and alpha,1-dioxotetrahydro-2-naphthaleneacetic acid ethyl ester, 1c, lose CO at 170-190-degrees-C to yield the corresponding beta-keto esters 3a-c. When compounds 1 or the parent acids 4 were heated to 170-190-degrees-C with water in a sealed reactor, they yielded ketones resulting from replacement by H of C(O)CO2R from 1 or C(O)CO2H from 4. beta-Keto esters suffered replacement by H of the carbethoxy group to yield the corresponding ketones when heated with water at about 105-degrees-C. Acylketenes, such as 4,4-dimethyl-1-pentene-1,3-dione, 6a, 2-oxocyclohexylidenemethanone, 6b, 1-oxotetrahydro-2-naphthylidenemethanone, 6c, 3-methyl-1-butene-1,3-dione, 6d, and 1-butene-1,3-dione, 6e, are implicated as the common intermediates that react with water to form beta-keto acids that subsequently decarboxylate to yield the ketones 5. Intense IR frequencies in the region of 2120-2140 cm-1, characteristic of ketenes, are observed when 1,2, or 3 is subjected to GC-FTIR analysis with the injector and light pipe at 280-degrees-C. Loss of carbon monoxide and alcohol at high temperature is required to form 6 from 1, while only the loss of alcohol at lower temperature is needed to form 6 from 3.

  DOI：

  10.1021/jo00018a018

文献信息

• Arylmagnesium bromide additions to 1-tetralone-2-acetic acid followed by catalytic hydrogenolysis: stereochemical consequences
  作者：Carl Djerassi、George R. Pettit、Delbert L. Herald、Dale R. Sanson

  DOI：10.1021/jo00018a030

  日期：1991.8

  A Stork reaction route (7 --> 1b) was utilized to synthesize 1-tetralone-2-acetic acid methyl ester (1a) from 1-tetralone. Addition of a 2'-(o-methoxyphenyl) magnesium bromide to this ketone followed by palladium-catalyzed hydrogenation of the intermediate cis lactones (2, verified by X-ray crystal structure determination of 2a, Figure 1), afforded predominantly a 1,2-cis tetralin (3) accompanied by smaller yields of the corresponding 1,2-trans tetralin (4). The stereochemical consequences of this reaction sequence was unequivocally established by X-ray crystal structure elucidation of 1,2-cis methyl ester 3b (Figure 2) and 1,2-trans carboxylic acid 4a (Figure 3). Stereochemical assignments for the analogous diastereoisomeric sets 3c-f and 4c-f were obtained by high-field (400-MHz) H-1 and C-13 NMR correlations with the crystal structures. The overall reaction pathway illustrates a useful approach to 1,2-cis-alkylated tetralins and certain sterically hindered 1,2-trans-alkylated tetralins.
• The Synthesis of Analogs of the Sex Hormones. An Analog of Equilenin Lacking the Phenolic A Ring
  作者：W. E. Bachmann、Donald G. Thomas

  DOI：10.1021/ja01847a068

  日期：1941.2
• Buchta; Galster; Luther, Chemische Berichte, 1949, vol. 82, p. 126,130
  作者：Buchta、Galster、Luther

  DOI：——

  日期：——
• MINAMI NOBUYOSHI; SUZUKI YASUSHI, YAKUGAKU DZASSI. YAKUGAKU ZASSNI, J. PHARM. SOS. JAR. <YKKZ-AJ>, 1975, 95+
  作者：MINAMI NOBUYOSHI、 SUZUKI YASUSHI

  DOI：——

  日期：——
• Evidence for ketene intermediates in the decarbonylation of 2,4-dioxo acids and esters and 2-oxobutanedioic acid esters
  作者：David W. Emerson、Richard L. Titus、Rowena M. Gonzalez

  DOI：10.1021/jo00018a018

  日期：1991.8

  The mechanism by which alpha, gamma-dioxo carboxylic acid esters 1 and 2-oxobutanedioic acid diesters 2 lose CO was explored. The compounds, 5,5-dimethyl-2,4-dioxohexanoic acid ethyl ester, 1a, alpha,2-dioxocyclohexaneacetic acid ethyl ester, 1b, and alpha,1-dioxotetrahydro-2-naphthaleneacetic acid ethyl ester, 1c, lose CO at 170-190-degrees-C to yield the corresponding beta-keto esters 3a-c. When compounds 1 or the parent acids 4 were heated to 170-190-degrees-C with water in a sealed reactor, they yielded ketones resulting from replacement by H of C(O)CO2R from 1 or C(O)CO2H from 4. beta-Keto esters suffered replacement by H of the carbethoxy group to yield the corresponding ketones when heated with water at about 105-degrees-C. Acylketenes, such as 4,4-dimethyl-1-pentene-1,3-dione, 6a, 2-oxocyclohexylidenemethanone, 6b, 1-oxotetrahydro-2-naphthylidenemethanone, 6c, 3-methyl-1-butene-1,3-dione, 6d, and 1-butene-1,3-dione, 6e, are implicated as the common intermediates that react with water to form beta-keto acids that subsequently decarboxylate to yield the ketones 5. Intense IR frequencies in the region of 2120-2140 cm-1, characteristic of ketenes, are observed when 1,2, or 3 is subjected to GC-FTIR analysis with the injector and light pipe at 280-degrees-C. Loss of carbon monoxide and alcohol at high temperature is required to form 6 from 1, while only the loss of alcohol at lower temperature is needed to form 6 from 3.