3-methyl-3-buten-2-one dimethyl acetal | 1855-71-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methyl-3-buten-2-one dimethyl acetal
• 英文别名: 3,3-dimethoxy-2-methylbutene；2,2-Dimethoxy-3-methyl-3-buten；3,3-dimethoxy-2-methyl-1-butene；3,3-dimethoxy-2-methyl-but-3-ene；3-methyl-but-3-en-2-one-dimethylacetal；3-Methyl-but-3-en-2-on-dimethylacetal；2-methyl-3,3-dimethoxy-1-butene；3,3-Dimethoxy-2-methyl-but-1-en；1-Butene, 3,3-dimethoxy-2-methyl-；3,3-dimethoxy-2-methylbut-1-ene
• CAS: 1855-71-6
• 化学式: C₇H₁₄O₂
• 分子量: 130.187
• InChiKey: CJFHJZULWBTLMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-3-buten-2-one dimethyl acetal 在 2,4-二硝基酚 、 sodium cyanoborohydride 、 对甲苯磺酰肼 作用下， 以 甲苯 为溶剂， 反应 12.67h， 生成 黑蚁素
  参考文献：
  名称：

  全反式无环类异戊二烯信息素成分的合成

  摘要：

  全反式无环类异戊二烯骨架是通过两步迭代序列制成的。该方法涉及由烯丙基醇形成的烯丙基乙烯基醚的克莱森重排和甲基异丙烯基酮的二甲基乙缩醛，然后通过重排形成的LiAlH 4还原α，β-不饱和酮。通过使用一锅脱氧反应来合成（E） -β-法呢烯，（E） -β-弹簧烯和树突蛋白，α，β-不饱和酮也被转化为2-甲基-1-丙烯基。

  DOI：

  10.1016/s0040-4020(01)86580-7
• 作为产物：
  描述：

  4-羟基-3-甲基-2-丁酮 在 磷酸 、 phosphorus pentoxide 、 铜 、 对甲苯磺酸 、 对苯二酚 作用下， 以 甲醇 为溶剂， 反应 0.25h， 生成 3-methyl-3-buten-2-one dimethyl acetal
  参考文献：
  名称：

  全反式无环类异戊二烯信息素成分的合成

  摘要：

  全反式无环类异戊二烯骨架是通过两步迭代序列制成的。该方法涉及由烯丙基醇形成的烯丙基乙烯基醚的克莱森重排和甲基异丙烯基酮的二甲基乙缩醛，然后通过重排形成的LiAlH 4还原α，β-不饱和酮。通过使用一锅脱氧反应来合成（E） -β-法呢烯，（E） -β-弹簧烯和树突蛋白，α，β-不饱和酮也被转化为2-甲基-1-丙烯基。

  DOI：

  10.1016/s0040-4020(01)86580-7

文献信息

• Isoprenoid chain elongations by Claisen rearrangements using acetals as precursors of vinyl ethers
  作者：Peter Baeckström、Lanna Li

  DOI：10.1016/s0040-4020(01)86579-0

  日期：1991.8

  Claisen rearrangements of allyl vinyl ethers, formed in situ by the acid catalyzed reaction of dimethyl acetals of acetaldehyde, acetone and isopropeny] methyl ketone with different types of allylic alcohols, have been compared. The primary, secondary and tertiary allylic alcohols used in the investigation were selected to serve as models for isoprenoid synthesis. The basis for two feasible methods

  比较了通过乙醛，丙酮和异丙基甲基酮的二甲基缩醛与不同类型的烯丙醇的酸催化反应原位形成的烯丙基乙烯基醚的克莱森重排。选择用于研究的伯，仲和叔烯丙醇作为类异戊二烯合成的模型。已经研究了可以迭代创建类异戊二烯链的两种可行方法的基础。
• Anthrapyridones, a novel group of antitumour non-cross resistant anthraquinone analogues. Synthesis and molecular basis of the cytotoxic activity towards K562/DOX cells
  作者：J Tarasiuk、B Stefańska、I Plodzich、K Tkaczyk-Gobis、O Seksek、S Martelli、A Garnier-Suillerot、E Borowski

  DOI：10.1038/sj.bjp.0704611

  日期：2002.3

  Multidrug resistance (MDR) to antitumour agents, structurally dissimilar and having different intracellular targets, is the major problem in cancer therapy. MDR phenomenon is associated with the presence of membrane proteins which belong to the ATP‐binding cassette family transporters responsible for the active drug efflux leading to the decreased intracellular accumulation. The search of new compounds able to overcome MDR is of prime importance. Recently we have synthesized a new family of anthrapyridone compounds. The series contained derivatives modified with appropriate hydrophobic or hydrophylic substituents at the side chain. The interaction of these derivatives with erythroleukemia K562 sensitive and K562/DOX resistant (overexpressing P‐glycoprotein) cell lines has been examined. The study was performed using a spectrofluorometric method which allows to continuously follow the uptake and efflux of fluorescent molecules by living cells. It was demonstrated that the increase in the lipophilicity of anthrapyridones favoured the very fast cellular uptake exceeding the rate of P‐gp dependent efflux out of the cell. For these derivatives, very high accumulation (the same for sensitive and resistant cells) was observed and the in vitro biological data confirmed that these compounds exhibited comparable cytotoxic activity towards sensitive and P‐gp resistant cell line. In contrast, anthrapyridones modified with hydrophylic substituents exhibited relatively low kinetics of cellular uptake. For these derivatives decreased accumulation in resistant cells was observed and the in vitro biological data demonstrated that they were much less active against P‐gp resistant cells in comparison to sensitive cells. We also studied, using confocal microscopy, the intracellular distribution of anthrapyridones in NIH‐3T3 cells. Our data showed that these compounds were strongly accumulated in the nucleus and lysosomes. British Journal of Pharmacology (2002) 135, 1513–1523; doi:10.1038/sj.bjp.0704611

  抗肿瘤药物的多重耐药性（MDR）是肿瘤治疗的主要问题，涉及结构各异、作用于不同细胞内靶点的药物。该现象与膜上的ATP结合盒家族转运蛋白有关，这些转运蛋白负责主动药物外排，从而减少细胞内药物的积累。 寻找能够克服MDR的新化合物具有重要意义。 我们最近合成了一类新型蒽酮衍生物，这些化合物在其侧链上带有适当的疏水或亲水取代基。 我们使用荧光分光法研究了这些衍生物与红白血病K562敏感型细胞及其抗性亚系K562/DOX（过表达P-糖蛋白）的相互作用。该方法可以实时跟踪活细胞对荧光分子的摄取和外排。 实验表明，增加蒽酮类化合物的脂ophilicity（脂溶性）有利于快速细胞摄取，超过P-糖蛋白依赖的外排速率。这些衍生物在敏感型和抗性细胞中均表现出非常高的积累，体外生物数据表明这些化合物对敏感型和P-糖蛋白抗性细胞系具有相似的细胞毒性。相反，带有亲水取代基的蒽酮类衍生物表现出相对较低的细胞摄取速率。 对于这些衍生物，在抗性细胞中观察到积累减少，体外生物数据显示它们在抗P-糖蛋白抗性细胞中的活性显著低于敏感型细胞。 我们还利用共聚焦显微镜研究了蒽酮类化合物在NIH-3T3细胞中的细胞内分布。实验数据显示，这些化合物主要在细胞核和溶酶体中积累。 British Journal of Pharmacology (2002) 135, 1513–1523; doi:10.1038/sj.bjp.0704611
• Acyclic terpenes
  申请人：MITSUBISHI KASEI CORPORATION

  公开号：EP0439058A1

  公开（公告）日：1991-07-31

  The present invention provides novel acyclic terpenes of the formula: which are useful as intermediates for the industrially advantageous production of sarcophytol A.

  本发明提供了式如下的新型无环萜烯： 的新型无环萜类化合物，它们可作为中间体，用于生产具有工业优势的肌醇 A。
• Process for producing all trans-form polyprenols
  申请人：KURARAY CO., LTD.

  公开号：EP0771778A2

  公开（公告）日：1997-05-07

  An all trans-form polyprenol is obtained by; (A) subjecting a 3,7-dimethyl-6-hydroxy-7-octen-1-ol derivative to five-carbon lengthening reaction m-times which comprises reacting with 2-methyl-3,3-dimethoxy-1-butene and reducing the carbonyl group of the resulting compound, to obtain an allyl alcohol derivative; (B) halogenating the hydroxyl group of the allyl alcohol derivative to convert it to form an allyl halide derivative; (C) allowing the allyl halide derivative to react with a polyisoprenyl sulfone derivative to form a sulfonated polyprenol derivative; and (D) subjecting the sulfonated polyprenol derivative to desulfonylation to obtain the all trans-form polyprenol.

  通过以下方法可以得到全反式多酚； (A) 将 3,7-二甲基-6-羟基-7-辛烯-1-醇衍生物进行五碳延长反应 m 次，包括与 2-甲基-3,3-二甲氧基-1-丁烯反应，并还原所得化合物的羰基，以获得烯丙醇衍生物； (B) 卤化烯丙醇衍生物的羟基，将其转化为烯丙基卤化物衍生物； (C) 让烯丙基卤化物衍生物与聚异戊烯基砜衍生物反应，形成磺化聚丙 烯醇衍生物；以及 (D) 将磺化聚丙稀酚衍生物进行脱磺化反应，得到全反式聚丙稀酚。
• A process for preparing all trans-form polyprenols
  申请人：Kuraray Co., Ltd.

  公开号：EP1031551A2

  公开（公告）日：2000-08-30

  The invention refers to a process comprising treating a compound represented by Formula (202):    wherein p and q each represent an integer of 0 or 1 or more; Y and Z each represent a hydrogen atom, or combine to form a carbon-carbon bond; R1 represents an alkyl group or an aryl group; and A represents a protective group of the hydroxyl group; with an alkali metal and a polycyclic aromatic compound to produce a compound represented by Formula (201): wherein p, q, Y and Z are as defined above; and R2 represents a hydrogen atom or the same protective group of the hydroxyl group as that represented by A.

  本发明涉及一种工艺，包括处理由式（202）代表的化合物： 其中 p 和 q 分别代表 0 或 1 或更多的整数；Y 和 Z 分别代表氢原子，或结合成碳-碳键；R1 代表烷基或芳基；A 代表羟基的保护基团； 用碱金属和多环芳烃化合物生成由式（201）表示的化合物： 其中 p、q、Y 和 Z 如上定义；R2 代表氢原子或与 A 所代表的羟基相同的保护基团。