2-Formyl-3-methyl-cyclopropane-1,1-dicarboxylic acid dimethyl ester | 95054-70-9

• 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-Formyl-3-methyl-cyclopropane-1,1-dicarboxylic acid dimethyl ester
• 英文别名: Dimethyl 2-formyl-3-methylcyclopropane-1,1-dicarboxylate
• CAS: 95054-70-9
• 化学式: C₉H₁₂O₅
• 分子量: 200.191
• InChiKey: QDMGMTWZVNXOCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Formyl-3-methyl-cyclopropane-1,1-dicarboxylic acid dimethyl ester 在 四(三苯基膦)钯 作用下， 以 二甲基亚砜 为溶剂， 反应 0.33h， 生成 (2R,5R)-2-Isopropenyl-5-methyl-cyclopent-3-ene-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Pd(O) promoted rearrangement of 2-(1,3-butadienyl)cyclopropane- 1,1-dicarboxylate esters to 2-alkenyl-3-cyclopentene-1,1-dicarboxylate esters

  摘要：

  DOI：

  10.1016/s0040-4039(00)88436-1
• 作为产物：
  描述：

  dimethyl 2-[(1E,3E)-5-methoxy-5-oxopenta-1,3-dienyl]-3-methylcyclopropane-1,1-dicarboxylate 、 三苯基膦 、 臭氧 生成 2-Formyl-3-methyl-cyclopropane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  MONPERT A.; MARTELLI J.; GREE R.; CARRIE R., TETRAHEDRON LETT., 1981, 22, NO 21, 1961-1964

  摘要：

  DOI：

文献信息

• 11 Hydroxy methyl 11-deoxyprostaglandin E.sub.1
  申请人：Ayerst, McKenna and Harrison Limited

  公开号：US04161608A1

  公开（公告）日：1979-07-17

  A process for preparing 11-deoxyprostaglandin E.sub.1, E.sub.2 and E.sub.3 and analogs thereof is realized by treating an appropriate di(lower)alkyl 3-(optionally substituted)-2-formylcyclopropane-1,1-dicarboxylate with an ylid prepared from a Wittig reagent of formula (AlkO).sub.2 POCH.sub.2 CO--(c)-CH.sub.3 in which Alk is an alkyl containing one to three carbon atoms and (c) is either (CH.sub.2).sub.q wherein q is an integer from 1 to 6 or cis CH.sub.2 CH.dbd.CH(CH.sub.2).sub.r wherein r is an integer from 0 to 3 to obtain the corresponding compound of formula: ##STR1## in which R.sup.2 is hydrogen, lower alkyl or CH.sub.2 OR.sup.3 wherein R.sup.3 is lower alkanoyl, R.sup.4 is lower alkyl and (c) is as defined herein. The latter compound is reduced with an alkali metal borohydride to yield the corresponding alcohol derivative. Condensation of this alcohol derivative or preferably its corresponding tetrahydropyran-2-yl ether derivative with a triester of formula CH(COOR.sup.6).sub.2 --(a)-(CH.sub.2)pCOOR in which R and R.sup.6 are lower alkyl, (a) is CH.sub.2 CH.sub.2, cis CH.dbd.CH or C.tbd.C and p is an integer from 2 to 4, gives the corresponding cyclopentanonetriester of formula ##STR2## in which (a), (c), p, R, R.sup.4 and R.sup.6 are as defined herein, R.sup.5 is hydrogen or tetrahydropyran-2-yl, respectively, and R.sup.7 is hydrogen or lower alkyl; the lactonized form of the cyclopentanonetriester being obtained from said alcohol derivative in which R.sup.2 is CH.sub.2 OR.sup.3 wherein R.sup.3 is lower alkanoyl. In the instance when R.sup.5 is tetrahydropyran-2-yl the cyclopentanonetriester is treated with an acid to give the corresponding compound in which R.sup.5 is hydrogen. The instant compound is then treated with a base under aqueous conditions, followed by optional esterification and acylation to give the desired 11-deoxy-prostaglandin derivatives of formula ##STR3## in which (a), (c) and p, are as defined herein, (b) is trans CH.dbd.CH, R is hydrogen or lower alkyl, R.sup.1 is hydrogen or lower alkanoyl and R.sup.2 is hydrogen, lower alkyl or CH.sub.2 OR.sup.3 wherein R.sup.3 is hydrogen or lower alkanoyl. The derivatives possess prostaglandin-like biological activity and methods for their use are given.

  一种制备11-去氧前列腺素E.sub.1，E.sub.2和E.sub.3及其类似物的方法，通过将适当的二（较低）烷基3-（可选取取代基）-2-甲酰基环丙烷-1,1-二羧酸酯与由公式（AlkO）.sub.2 POCH.sub.2 CO-制备的Wittig试剂的ylid处理，其中Alk是含有1至3个碳原子的烷基，（c）是（CH.sub.2）.sub.q，其中q是1至6的整数，或者是顺式CH.sub.2 CH=CH（CH.sub.2）.sub.r，其中r是0至3的整数，以得到相应的化合物的公式：##STR1## 其中R.sup.2是氢，较低的烷基或CH.sub.2 OR.sup.3，其中R.sup.3是较低的烷酰基，R.sup.4是较低的烷基，（c）如上所定义。后一种化合物用碱金属硼氢化物还原，得到相应的醇衍生物。将此醇衍生物或者更好的是其相应的四氢吡喃-2-基醚衍生物与公式CH（COOR.sup.6）.sub.2 --（a）-（CH.sub.2）pCOOR的三酯缩合，其中R和R.sup.6是较低的烷基，（a）是CH.sub.2 CH.sub.2，顺式CH=CH或C.tbd.C，p是2至4的整数，得到相应的环戊烷三酯的公式：##STR2## 其中（a），（c），p，R，R.sup.4和R.sup.6如上所定义，R.sup.5分别为氢或四氢吡喃-2-基，R.sup.7为氢或较低的烷基；从所述醇衍生物中得到环戊烷三酯的内酯形式，其中R.sup.2为CH.sub.2 OR.sup.3，其中R.sup.3为较低的烷酰基。当R.sup.5为四氢吡喃-2-基时，用酸处理环戊烷三酯，得到相应的化合物，其中R.sup.5为氢。然后在水性条件下将瞬时化合物处理为碱，随后进行可选的酯化和酰化，得到所需的公式：##STR3## 其中（a），（c）和p如上所定义，（b）为顺式CH=CH，R为氢或较低的烷基，R.sup.1为氢或较低的烷酰基，R.sup.2为氢，较低的烷基或CH.sub.2 OR.sup.3，其中R.sup.3为氢或较低的烷酰基。这些衍生物具有类似前列腺素的生物活性，并提供了其使用方法。
• Cyclopentanone derivatives
  申请人：Ayerst McKenna and Harrison Ltd.

  公开号：US04036856A1

  公开（公告）日：1977-07-19

  A process for preparing 11-deoxyprostaglandin E.sub.1, E.sub.2 and E.sub.3 and analogs thereof is realized by treating an appropriate di(lower)alkyl 3-(optionally substituted)-2-formylcyclopropane-1,1-dicarboxylate with an ylid prepared from a Wittig reagent of formula (AlkO).sub.2 POCH.sub.2 CO-(c)-CH.sub.3 in which Alk is an alkyl containing one to three carbon atoms and (c) is either (CH.sub.2).sub.q wherein q is an integer from 1 to 6 or cis CH.sub.2 CH=CH(CH.sub.2).sub.r wherein r is an integer from 0 to 3 to obtain the corresponding compound of formula: ##STR1## in which R.sup.2 is hydrogen, lower alkyl or CH.sub.2 OR.sup.3 wherein R.sup.3 is lower alkanoyl, R.sup.4 is lower alkyl and (c) is as defined herein. The latter compound is reduced with an alkali metal borohydride to yield the corresponding alcohol derivative. Condensation of this alcohol derivative or preferably its corresponding tetrahydropyran-2-yl ether derivative with a triester of formula CH(COOR.sup.6).sub.2 --(a)-(CH.sub.2)pCOOR in which R and R.sup.6 are lower alkyl, (a) is CH.sub.2 CH.sub.2, cis CH=CH or C.tbd.C and p is an integer from 2 to 4, gives the corresponding cyclopentanonetriester of formula ##STR2## in which (a), (c), p, R, R.sup.4 and R.sup.6 are as defined herein, R.sup.5 is hydrogen or tetrahydropyran-2-yl, respectively, and R.sup.7 is hydrogen or lower alkyl; the lactonized form of the cyclopentanonetriester being obtained from said alcohol derivative in which R.sup.2 is CH.sub.2 OR.sup.3 wherein R.sup.3 is lower alkanoyl. In the instance when R.sup.5 is tetrahydropyran-2-yl the cyclopentanonetriester is treated with an acid to give the corresponding compound in which R.sup.5 is hydrogen. The instant compound is then treated with a base under aqueous conditions, followed by optional esterification and acylation to give the desired 11-deoxyprostaglandin derivatives of formula ##STR3## in which (a), (c) and p, are as defined herein, (b) is trans CH=CH, R is hydrogen or lower alkyl, R.sup.1 is hydrogen or lower alkanoyl and R.sup.2 is hydrogen, lower alkyl or CH.sub.2 OR.sup.3 wherein R.sup.3 is hydrogen or lower alkanoyl. The derivatives possess prostaglandin-like biological activity and methods for their use are given.

  一种制备11-去氧前列腺素E.sub.1，E.sub.2和E.sub.3及其类似物的方法，通过处理适当的二（较低）烷基3-（可选地取代的）2-甲酰基环丙烷-1,1-二羧酸酯与由公式（AlkO）.sub.2 POCH.sub.2 CO-（c）-CH.sub.3的Wittig试剂制备的ylid反应，其中Alk是含有1至3个碳原子的烷基，（c）是（CH.sub.2）.sub.q，其中q是1至6的整数，或cis CH.sub.2 CH=CH（CH.sub.2）.sub.r，其中r是0至3的整数，以获得相应的化合物的公式：##STR1##其中R.sup.2是氢，低烷基或CH.sub.2 OR.sup.3，其中R.sup.3是低脂肪酰基，R.sup.4是低烷基，（c）如上所定义。后一化合物通过碱金属硼氢化物还原，得到相应的醇衍生物。将该醇衍生物或其相应的四氢吡喃-2-基醚衍生物与公式CH（COOR.sup.6）.sub.2-（a）-（CH.sub.2）pCOOR的三酯缩合，其中R和R.sup.6是低烷基，（a）是CH.sub.2 CH.sub.2，cis CH=CH或C.tbd.C，p是2至4的整数，得到相应的环戊烷三酯的公式：##STR2##其中（a），（c），p，R，R.sup.4和R.sup.6如上所定义，R.sup.5分别为氢或四氢吡喃-2-基，R.sup.7为氢或低烷基；从所述醇衍生物中获得所述环戊烷三酯的内酯形式，其中R.sup.2是CH.sub.2 OR.sup.3，其中R.sup.3是低脂肪酰基。在R.sup.5为四氢吡喃-2-基的情况下，将环戊烷三酯处理为酸，得到相应的R.sup.5为氢的化合物。然后在水性条件下用碱处理该化合物，随后进行可选的酯化和酰化，以得到所需的公式：##STR3##其中（a），（c）和p如上所定义，（b）为trans CH=CH，R为氢或低烷基，R.sup.1为氢或低脂肪酰基，R.sup.2为氢，低烷基或CH.sub.2 OR.sup.3，其中R.sup.3为氢或低脂肪酰基。这些衍生物具有类似前列腺素的生物活性，并给出了它们的使用方法。
• US4006136A
  申请人：——

  公开号：US4006136A

  公开（公告）日：1977-02-01
• US4036856A
  申请人：——

  公开号：US4036856A

  公开（公告）日：1977-07-19
• US4089898A
  申请人：——

  公开号：US4089898A

  公开（公告）日：1978-05-16