1-Methoxy-3-pentyl-6,6a,7,8-tetrahydro-6,6-dimethyl-9H-dibenzopyran-9-one | 122700-13-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: 1-Methoxy-3-pentyl-6,6a,7,8-tetrahydro-6,6-dimethyl-9H-dibenzopyran-9-one
• 英文别名: 1-methoxy-6,6-dimethyl-3-pentyl-7,8-dihydro-6aH-benzo[c]chromen-9-one
• CAS: 122700-13-4
• 化学式: C₂₁H₂₈O₃
• 分子量: 328.452
• InChiKey: ZFMRLLOVOLJZBP-UHFFFAOYSA-N

物化性质

• 沸点：
  457.9±45.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-Methoxy-3-pentyl-6,6a,7,8-tetrahydro-6,6-dimethyl-9H-dibenzopyran-9-one 在 氨 、 lithium 、 N,N-二异丙基乙胺 、 1-丙烷硫醇钠 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 39.08h， 生成 Trifluoro-methanesulfonic acid (6aR,10aR)-1-methoxymethoxy-6,6-dimethyl-3-pentyl-6a,7,8,10a-tetrahydro-6H-benzo[c]chromen-9-yl ester
  参考文献：
  名称：

  Synthesis of (.+-.)-11-nor-9-carboxy-.DELTA.9-tetrahydrocannabinol. New synthetic approaches to cannabinoids

  摘要：

  A completely regioselective synthesis of (+/-)-11-nor-9-carboxy-DELTA-9-tetrahydrocannabinol (1), a principal human metabolite of DELTA-9-tetrahydrocannabinol (2), has been carried out in seven steps and 14% overall yield from apoverbenone (9) and the bis-MOM ether of olivetol. Condensation of 9 with the aryllithium derived from the bis-MOM ether of olivetol gives an unstable tertiary allylic alcohol that undergoes oxidative rearrangement to give enone 42. Reaction of 42 with acid results in hydrolysis of the MOM ethers and cyclization to benzopyranone 21. Conversion to MOM ether 39 followed by Li/NH3 reduction and trapping of the enolate with N-phenyltriflimide gives vinyl triflate 40 plus the isomer with a cis ring fusion. Palladium-catalyzed carboxylation, hydrolysis of the MOM ether, and separation from cis acid 41 gives pure 1. Model experiments employing unsubstituted resorcinol derivatives that lead to ester 27 are described, as are a number of alternative approaches to acid 1.

  DOI：

  10.1021/jo00004a027
• 作为产物：
  描述：

  3,5-二羟基戊苯 在 吡啶 、 iron(III) chloride 、 lithium aluminium tetrahydride 、 草酰氯 、 palladium on activated charcoal 、 potassium tert-butylate 、 甲基锂 、 氢气 、 lead(IV) tetraacetate 、 二甲基二环氧乙烷 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， -78.0~80.0 ℃ 、2.0 MPa 条件下， 反应 83.5h， 生成 1-Methoxy-3-pentyl-6,6a,7,8-tetrahydro-6,6-dimethyl-9H-dibenzopyran-9-one
  参考文献：
  名称：

  大麻素衍生物和四氢大麻酚 (THC) 的正式合成的 Diels-Alder 方法

  摘要：

  基于乙烯基色烯与缺电子亲二烯体的狄尔斯-阿尔德反应，我们开发了一种合成四氢大麻酚衍生物的策略。取代的乙烯基色烯可以与几种亲二烯体转化，以成功分离几种复杂的分子。这些分子已经含有类似大麻素的基本结构，并且对此类衍生物的进一步加工产生了 Δ 9 -四氢大麻酚的前体。该前体最具挑战性的步骤是最终通过二甲基二氧杂环己烷实现的环氧化步骤。

  DOI：

  10.1002/open.202000343

文献信息

• Regioselective synthesis of (.+-.)-11-Nor-9-carboxy-.DELTA.9-THC
  作者：John W. Huffman、Xuehai Zhang、Ming Jung Wu、H. Howard Joyner

  DOI：10.1021/jo00281a009

  日期：1989.9
• HUFFMAN, JOHN W.;ZHANG, XUEHAI;WU, MING-JUNG;JOYNER, HOWARD H., J. ORG. CHEM., 54,(1989) N0, C. 4741-4743
  作者：HUFFMAN, JOHN W.、ZHANG, XUEHAI、WU, MING-JUNG、JOYNER, HOWARD H.

  DOI：——

  日期：——
• HUFFMAN, JOHN W.;ZHANG, XUEHAI;WU, MING-JUNG;JOYNER, H. HOWARD;PENNINGTON+, J. ORG. CHEM., 56,(1991) N, C. 1481-1489
  作者：HUFFMAN, JOHN W.、ZHANG, XUEHAI、WU, MING-JUNG、JOYNER, H. HOWARD、PENNINGTON+

  DOI：——

  日期：——
• The Diels‐Alder Approach towards Cannabinoid Derivatives and Formal Synthesis of Tetrahydrocannabinol (THC)
  作者：Thomas Hurrle、Franziska Gläser、Manuel C. Bröhmer、Martin Nieger、Stefan Bräse

  DOI：10.1002/open.202000343

  日期：2021.5

  Based on the Diels‐Alder reaction of vinylchromenes with electron‐poor dienophiles, we developed a strategy for the synthesis of tetrahydrocannabinol derivatives. Substituted vinyl chromenes could be converted with several dienophiles to successfully isolate several complex molecules. These molecules already contain the cannabinoid‐like base structure and further processing of one such derivative led

  基于乙烯基色烯与缺电子亲二烯体的狄尔斯-阿尔德反应，我们开发了一种合成四氢大麻酚衍生物的策略。取代的乙烯基色烯可以与几种亲二烯体转化，以成功分离几种复杂的分子。这些分子已经含有类似大麻素的基本结构，并且对此类衍生物的进一步加工产生了 Δ 9 -四氢大麻酚的前体。该前体最具挑战性的步骤是最终通过二甲基二氧杂环己烷实现的环氧化步骤。
• Synthesis of (.+-.)-11-nor-9-carboxy-.DELTA.9-tetrahydrocannabinol. New synthetic approaches to cannabinoids
  作者：John W. Huffman、Xuehai Zhang、Ming Jung Wu、H. Howard Joyner、William T. Pennington

  DOI：10.1021/jo00004a027

  日期：1991.2

  A completely regioselective synthesis of (+/-)-11-nor-9-carboxy-DELTA-9-tetrahydrocannabinol (1), a principal human metabolite of DELTA-9-tetrahydrocannabinol (2), has been carried out in seven steps and 14% overall yield from apoverbenone (9) and the bis-MOM ether of olivetol. Condensation of 9 with the aryllithium derived from the bis-MOM ether of olivetol gives an unstable tertiary allylic alcohol that undergoes oxidative rearrangement to give enone 42. Reaction of 42 with acid results in hydrolysis of the MOM ethers and cyclization to benzopyranone 21. Conversion to MOM ether 39 followed by Li/NH3 reduction and trapping of the enolate with N-phenyltriflimide gives vinyl triflate 40 plus the isomer with a cis ring fusion. Palladium-catalyzed carboxylation, hydrolysis of the MOM ether, and separation from cis acid 41 gives pure 1. Model experiments employing unsubstituted resorcinol derivatives that lead to ester 27 are described, as are a number of alternative approaches to acid 1.