1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene | 160058-98-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene
• 英文别名: 6-methoxy-1,1,10-trimethyl-1,2,3,4-tetrahydroanthracene；7-methoxy-4,4,9-trimethyl-2,3-dihydro-1H-anthracene
• CAS: 160058-98-0
• 化学式: C₁₈H₂₂O
• 分子量: 254.372
• InChiKey: IKLTXJHIFKOVOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene 在 三氯化铝 、 magnesium 、 乙硫醇 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 3-(1-Hydroxy-1-methyl-ethyl)-5,5,9-trimethyl-5,6,7,8-tetrahydro-anthracen-2-ol
  参考文献：
  名称：

  综合研究复杂的二萜。第20部分。1线性松果烷邻醌醌的全合成

  摘要：

  重排的线性松香烷二萜类化合物的简单全合成ø -quinone，umbrosone 1，已经通过完成反-1,2,3,4,9,9a -六氢-1,1-二甲基-6- methoxyanthracen-10（图4a H）-12t。

  DOI：

  10.1039/a809579e
• 作为产物：
  描述：

  2-(4-Methoxy-2-bromobenzyl)-3-methylcyclohex-2-en-1-one 在 palladium diacetate 三氟化硼乙醚 、 potassium tert-butylate 、 甲基锂 、 potassium carbonate 、 对甲苯磺酸 、 三苯基膦 作用下， 以 二甲基亚砜 、 甲苯 、 乙腈 为溶剂， 反应 129.0h， 生成 1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene
  参考文献：
  名称：

  Intramolecular Heck reaction strategy for the synthesis of functionalised tetrahydroanthracenes: a facile formal total synthesis of the linear abietane diterpene, umbrosone

  摘要：

  Rapid annulation employing an intramolecular Heck reaction yielded the functionalised 1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene 4a, a key intermediate for the linear diterpenoid quinone umbrosone (1), and the related compounds 4b-d. A similar strategy was also successfully adopted for the synthesis of the 9-methyl tetrahydroanthracene ester 5 and the tetrahydrodibenzo[a,d]cycloheptene ester 6. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.01.021

文献信息

• Synthesis of 6-Methoxy-1,1,10-trimethyl-1,2,3,4-tetrahydroanthracene, a Synthetic Intermediate of a Linear Abietane Diterpene, Umbrosone.
  作者：Takashi MATSUMOTO、Yoshio TAKEDA、Shuji USUI、Sachihiko IMAI

  DOI：10.1248/cpb.44.530

  日期：——

  Methyl 13-acetyl-12-methoxy-8, 11, 13-podocarpatrien-18-oate, prepared from (+)-dehydroabietic acid, was converted into methyl 12-methoxy-7-oxo-5, 8, 11, 13-podocarpatetraen-18-oate (9) by a series of reactions : haloform reaction, decarboxylation, Jones oxidation, and dehydrogenation. Reduction of 9 with sodium borohydride, followed by treatment of the resulting 7-hydroxy compound with boron trifluoride etherate, afforded a rearranged ester, methyl 6-methoxy-1, 10-dimethyl-1, 2, 3, 4-tetrahydroanthracene-1-carboxylate. This was further converted into 6-methoxy-1, 1, 10-trimethyl-1, 2, 3, 4-tetrahydroanthracene (14) by means of the following reactions : lithium aluminum hydride reduction, pyridinium chlorochromate oxidation, and Huang-Minlon reduction. Compound 14 was finally converted into the desired orthoquinone (1) according to the procedure of Ghosh and Ghatak. The synthetic 1 was shown to be identical with natural umbrosone by spectral comparisons.

  将由 (+)-脱氢松香酸制备的 13-乙酰基-12-甲氧基-8, 11, 13-podocarpatrien-18-oate 甲酯转化为 12-甲氧基-7-氧代-5, 8, 11, 13-甲酯podocarpatetraen-18-oate (9)经一系列反应：卤仿反应、脱羧、琼斯氧化、脱氢。用硼氢化钠还原9，然后用乙醚三氟化硼处理所得7-羟基化合物，得到重排酯，甲基6-甲氧基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸盐。通过氢化铝锂还原、氯铬酸吡啶鎓氧化和黄敏隆还原反应进一步转化为6-甲氧基-1,1,10-三甲基-1,2,3,4-四氢蒽(14) 。根据Ghosh和Ghatak的方法，化合物14最终转化为所需的邻醌(1)。通过光谱比较表明合成的 1 与天然 umbrosone 相同。
• Skeletal Rearrangements of Ring C Aromatic Diterpenoids
  作者：Richard C. Cambie、Carrie C. Liu、Clifford E. F. Rickard、Peter S. Rutledge

  DOI：10.1071/c97198

  日期：——

  The structure of a naphthalene derivative obtained by rearrangement of 13-methoxytotara-5,8,11,13-tetraen-7α-ol (2) has been revised to 5-(5′-isopropyl-6′-methoxy-2′-methyl-1′-naphthyl)-2-methylpent-2-ene (7). A minor oxidation product of 13-methoxytotara-8,11,13-triene (4) has been identified as 4-methoxy-3,3-dimethyl-7-(1′,3′,3′-trimethyl-2′-oxocyclohexanyl)isobenzofuran-1(3H)-one (16) and its structure confirmed by X-ray crystallography. Methyl 12-methoxypodocarpa-8,11,13-trien-19-oate (12) has been converted into an intermediate used in the synthesis of the linear diterpenoid umbrosone [3-(1′-hydroxy-1′-methylethyl)-5,5,9-trimethyl-5,6,7,8-tetrahydroanthracene-1,2-dione] (15).

  通过重排 13-甲氧基托塔拉-5,8,11,13-四烯-7α-醇 (2) 而得到的萘衍生物的结构 13-甲氧基托塔拉-5,8,11,13-四烯-7α-醇 (2) 的结构已修订为 5-(5′-异丙基-6′-甲氧基-2′-甲基-1′-萘基)-2-甲基戊-2-烯(7)。 (7).13-甲氧基托塔拉-8,11,13-三烯（4）的一个次要氧化产物被确认为 确定为 4-甲氧基-3,3-二甲基-7-(1′,3′,3′-三甲基-2′-氧代环己基)异苯并呋喃-1(3H)-酮(16)。 (16) 并通过 X 射线晶体学确认了其结构。甲基 12-甲氧基十二碳-8,11,13-三烯-19-酸甲酯（12）已转化为一种 中间体，用于合成线性二萜伞形酮 [3-(1′-羟基-1′-甲基乙基)-5,5,9-三甲基-5,6,7,8-四氢蒽-1,2-二酮] (15) 的中间体。 (15).
• First total synthesis of the linear abietane diterpenoid orthoquinone umbrosone
  作者：Keya Ghosh、Usha Ranjan Ghatak

  DOI：10.1016/s0040-4039(00)78225-6

  日期：1994.8

  The first total synthesis of the rearranged linear abietane diterpenoid orthoquinone, umbrosone (1), was accomplished through a simple convergent route via the tricyclic ketone 11.
• Rhodium(II)-Catalyzed Decomposition of 1-Diazo-4-(1- or 2-naphthyl)-2-butanones as a New Route to Rearranged Pimarane and Abietane Skeleta. Synthesis of Umbrosone
  作者：Paolo Manitto、Diego Monti、Giovanna Speranza

  DOI：10.1021/jo970631k

  日期：1997.9.1

  The Rh-2(OAc)(4)-catalyzed intramolecular Buchner reaction of 1-diazo-4-(1- or 2-naphthyl)butan-2-ones was examined as a potential route to abietane and rearranged abietane derivatives. Treatment of the alpha-diazo ketone 26 with catalytic amount of dirhodium tetraacetate in CH2Cl2 at 0 degrees C furnished the tetracyclic derivative 27 in good yield. Addition of TFA to 27 (in CH2Cl2) resulted in an acid-induced opening of the cyclopropane ring to give the 4a- and 10a-methyldihydrophenanthrenones 28 and 29 in nearly equal amounts. These compounds and their analogs appear to be suitable intermediates for the synthesis of diterpenoids containing aromatic A or C rings. When the diazo ketone 34 was decomposed under Rh(II) catalysis, a 10-methyldihydroanthracenone (i.e., 36) was obtained as the main product, besides minor amounts of the expected tetracyclic ketone 35. The extension of this result to the preparation of the methoxy-substituted dihydroanthracenone 39 (52% yield) was exploited in a new total synthesis of umbrosone (6), an unusual diterpenoid possessing a rearranged linear skeleton.
• Intramolecular Heck reaction strategy for the synthesis of functionalised tetrahydroanthracenes: a facile formal total synthesis of the linear abietane diterpene, umbrosone
  作者：Sujaya Sengupta、Ranjan Mukhopadhyay、Basudeb Achari、Asish Kr. Banerjee

  DOI：10.1016/j.tetlet.2005.01.021

  日期：2005.2

  Rapid annulation employing an intramolecular Heck reaction yielded the functionalised 1,1,10-trimethyl-6-methoxy-1,2,3,4-tetrahydroanthracene 4a, a key intermediate for the linear diterpenoid quinone umbrosone (1), and the related compounds 4b-d. A similar strategy was also successfully adopted for the synthesis of the 9-methyl tetrahydroanthracene ester 5 and the tetrahydrodibenzo[a,d]cycloheptene ester 6. (C) 2005 Elsevier Ltd. All rights reserved.