4,4-dimethyl-6-bromo-2-oxo-thiochroman | 133532-09-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫铬烷
• 英文名称: 4,4-dimethyl-6-bromo-2-oxo-thiochroman
• 英文别名: 6-bromo-4,4-dimethyl-3H-thiochromen-2-one
• CAS: 133532-09-9
• 化学式: C₁₁H₁₁BrOS
• 分子量: 271.178
• InChiKey: JXECCEUIYMEVLB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-6-bromo-2-oxo-thiochroman 、 三甲基乙炔基硅 、 在 双三苯基磷二氯化钯 氩 、 silica 作用下， 以 三乙胺 为溶剂， 反应 24.0h， 生成 4,4-Dimethyl-6-trimethylsilylethynyl-2-oxo-thiochroman
  参考文献：
  名称：

  Acetylenes disubstituted with a phenyl or heteroaryl group and a

  摘要：

  式为##STR1##的化合物，其中R.sub.1和R.sub.2是氢、1-6个碳的低烷基或卤素；R.sub.3是氢、1-6个碳的低烷基、卤素、OR.sub.11、SR.sub.11、OCOR.sub.11、SCOR.sub.11、NH.sub.2、NHR.sub.11、N(R.sub.11).sub.2、NHCOR.sub.11或NR.sub.11 COR.sub.11；X是O、S或NR'，其中R'是氢或1-6个碳的低烷基；Y是苯基或从吡啶基、噻吩基、呋喃基、吡嗪基、嘧啶基、吡咯基、噻唑基和噁唑基中选择的杂环基；A是(CH.sub.2).sub.n，其中n为0-5、3-6个碳的低支链烷基、3-6个碳的环烷基、2-6个碳和1或2个双键的烯基、2-6个碳和1或2个三键的炔基；B是氢、COOH或其药学上可接受的盐、COOR.sub.8、CONR.sub.9 R.sub.10、--CH.sub.2 OH、CH.sub.2 OR.sub.11、CH.sub.2 OCOR.sub.11、CHO、CH(OR.sub.12).sub.2、CHOR.sub.13 O、--COR.sub.7、CR.sub.7 (OR.sub.12).sub.2或CR.sub.7 OR.sub.13 O，其中R.sub.7是含有1-5个碳的烷基、环烷基或烯基，R.sub.8是1-10个碳的烷基或5-10个碳的环烷基，或R.sub.8是苯基或低烷基苯基，R.sub.9和R.sub.10独立地是氢、1-10个碳的烷基或5-10个碳的环烷基，或苯基或低烷基苯基，R.sub.11是低烷基、苯基或低烷基苯基，R.sub.12是低烷基，R.sub.13是2-5个碳的双价烷基基团，具有类视黄醇生物活性。

  公开号：

  US05399561A1
• 作为产物：
  描述：

  S-(4-bromophenyl) 3,3-dimethylthioacrylate 在 三氯化铝 作用下， 以 二氯甲烷 为溶剂， 生成 4,4-dimethyl-6-bromo-2-oxo-thiochroman
  参考文献：
  名称：

  Acetylenes disubstituted with a phenyl or heteroaryl group and a

  摘要：

  式为##STR1##的化合物，其中R.sub.1和R.sub.2为氢、1-6碳的低烷基或卤素；R.sub.3为氢、1-6碳的低烷基、卤素、OR.sub.11、SR.sub.11、OCOR.sub.11、SCOR.sub.11、NH.sub.2、NHR.sub.11、N(R.sub.11).sub.2、NHCOR.sub.11或NR.sub.11 COR.sub.11；X为O、S或NR'，其中R'为氢或1-6碳的低烷基；Y为苯基或从吡啶基、噻吩基、呋喃基、吡啶嗪基、嘧啶基、吡嗪基、噻唑基和噁唑基组成的杂环基；A为(CH.sub.2).sub.n，其中n为0-5，具有3-6碳的低支链烷基、具有3-6碳的环烷基、具有2-6碳和1或2个双键的烯基、具有2-6碳和1或2个三键的炔基；B为氢、COOH或其药用可接受盐，COOR.sub.8、CONR.sub.9 R.sub.10、--CH.sub.2 OH、CH.sub.2 OR.sub.11、CH.sub.2 OCOR.sub.11、CHO、CH(OR.sub.12).sub.2、CHOR.sub.13 O、--COR.sub.7、CR.sub.7 (OR.sub. 12).sub.2或CR.sub.7 OR.sub.13 O，其中R.sub.7为含有1至5个碳的烷基、环烷基或烯基，R.sub.8为1至10个碳的烷基或5至10个碳的环烷基，或R.sub.8为苯基或低烷基苯基，R.sub.9和R.sub.10独立地为氢、1至10个碳的烷基或5-10个碳的环烷基，或苯基或低烷基苯基，R.sub.11为低烷基、苯基或低烷基苯基，R.sub.12为低烷基，R.sub.13为2-5碳的二价烷基基团，具有类似视黄醇的生物活性。

  公开号：

  US05399561A1

文献信息

• Acetylenes disubstituted with a thienyl or furyl group and a
  申请人：Allergan

  公开号：US05599819A1

  公开（公告）日：1997-02-04

  Retinoid-like activity is exhibited by compounds of the formula ##STR1## where X is NR'; where R' is hydrogen or lower alkyl; R.sub.1, R.sub.2 and R.sub.3 are hydrogen or lower alkyl; R.sub.4 and R.sub.5 are hydrogen or lower alkyl with the proviso that R.sub.4 and R.sub.5 cannot both be hydrogen, A is thienyl, furyl; n is 0-5, and B is H, --COOH or a pharmaceutically acceptable salt, ester or amide thereof, --CH.sub.2 OH or an ether or ester derivative, or --CHO or an acetal derivative, or --COR.sub.1 or a ketal derivative where R.sub.1 is --(CH.sub.2).sub.m CH.sub.3 where m is 0-4, or a pharmaceutically acceptable salt thereof.

  化合物的公式为##STR1##，其中X为NR'，R'为氢或低碳基；R.sub.1、R.sub.2和R.sub.3为氢或低碳基；R.sub.4和R.sub.5为氢或低碳基，但是R.sub.4和R.sub.5不能同时为氢；A为噻吩基、呋喃基；n为0-5，B为H、--COOH或其药学上可接受的盐、酯或酰胺、--CH.sub.2 OH或其醚或酯衍生物、--CHO或其缩醛衍生物、或--COR.sub.1或其缩酮衍生物，其中R.sub.1为--(CH.sub.2).sub.m CH.sub.3，m为0-4，或其药学上可接受的盐。
• Acetylenes disubstituted with a phenyl group and a 2-substituted
  申请人：Allergan, Inc.

  公开号：US05162546A1

  公开（公告）日：1992-11-10

  Retinold-like activity is exhibited by compounds of the formula ##STR1## where X is S, O; R.sub.1, R.sub.2 and R.sub.3 are hydrogen or lower alkyl; R.sub.4 and R.sub.5 are hydrogen or lower alkyl with the proviso that R.sub.4 and R.sub.5 cannot both be hydrogen, R.sub.6 is hydrogen, lower alkyl, lower alkenyl, lower cycloalkyl or halogen; n is 0-5, and B is H, --COOH or a pharmaceutically acceptable salt, ester or amide thereof, --CH.sub.2 OH or an ether or ester derivative, or --CHO or an acetal derivative, or --COR.sub.1 or a ketal derivative where R.sub.1 l is --(CH.sub.2).sub.m CH.sub.3 where m is 0-4, or a pharmaceutically acceptable salt thereof.

  化合物的公式为##STR1##其中X为S，O；R.sub.1，R.sub.2和R.sub.3是氢或较低的烷基；R.sub.4和R.sub.5是氢或较低的烷基，但要注意R.sub.4和R.sub.5不能同时为氢，R.sub.6为氢，较低的烷基，较低的烯基，较低的环烷基或卤素；n为0-5，B为H，--COOH或其药学上可接受的盐，酯或酰胺，--CH.sub.2 OH或其醚或酯衍生物，或--CHO或其缩醛衍生物，或--COR.sub.1或其缩酮衍生物，其中R.sub.1为--(CH.sub.2).sub.m CH.sub.3，其中m为0-4，或其药学上可接受的盐。
• Acetylenes disubstituted with a heteroaromatic group and a 2-substituted
  申请人：Allergan, Inc.

  公开号：US05407937A1

  公开（公告）日：1995-04-18

  Retinoid-like activity is exhibited by compounds of the formula ##STR1## where X is S, O or NR'; where R' is hydrogen or lower alkyl; R.sub.1, R.sub.2 and R.sub.3 are hydrogen or lower alkyl; R.sub.4 and R.sub.5 are hydrogen or lower alkyl with the proviso that R.sub.4 and R.sub.5 cannot both be hydrogen, A is pyridazinyl, pyrimidinyl, pyrazinyl; n is 0-5, and B is H, --COOH or a pharmaceutically acceptable salt, ester or amide thereof, --CH.sub.2 OH or an ether or ester derivative, or --CHO or an acetal derivative, or --COR.sub.1 or a ketal derivative where R.sub.1 is --(CH.sub.2).sub.m CH.sub.3 where m is 0-4, or a pharmaceutically acceptable salt thereof.

  化合物的结构式为##STR1## 其中X为S，O或NR'；其中R'为氢或低级烷基；R.sub.1，R.sub.2和R.sub.3为氢或低级烷基；R.sub.4和R.sub.5为氢或低级烷基，但须注意R.sub.4和R.sub.5不能同时为氢；A为吡啶并嗪基、嘧啶基、吡嗪基；n为0-5；B为H、--COOH或其药学上可接受的盐、酯或酰胺、--CH.sub.2 OH或其醚或酯衍生物、--CHO或其缩醛衍生物、或--COR.sub.1或其缩酮衍生物，其中R.sub.1为--(CH.sub.2).sub.mCH.sub.3，m为0-4，或其药学上可接受的盐。
• Process and intermediates for preparing compounds having a disubstituted
  申请人：Allergan, Inc.

  公开号：US05248777A1

  公开（公告）日：1993-09-28

  A process is disclosed for the preparation of disubstituted acetylene derivatives having retinoic acid like biological activity, wherein 6-ethynyl-chroman, 6-ethynyl-thio chroman and 6-ethynyl-1,2,3,4-tetrahydroquinoline derivatives of the formula shown below are reacted in the presence of catalysts with halogenated phenyl or heteroaryl derivatives of the formula shown below to provide the disubstituted acetylenes. In the formulae the symbols have the following meanings. R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are hydrogen or lower alkyl groups (of 1-6 carbons) where R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 may be identical or different from one another) X is S, O or NR' where R' is hydrogen or lower alkyl, Z represents hydrogen, or a metal ion capable of forming a salt with the ethynyl moiety of the molecule, X' is a leaving group such as a halogen group, A is phenyl, or heteroaryl such as pyridinyl, thienyl, furyl, pyridazinyl, pyrimidinyl, pyrazinyl, thiazolyl or oxazolyl, n is an integer between 0 to 5, and B is H, --COOH or a pharmaceutically acceptable salt, ester or amide thereof, --CH.sub.2 OH or an ether or ester derivative, or --CHO or an acetal derivative, or --COR.sub.1 or a ketal derivative where R.sub.1 is an alkyl, cycloalkyl or alkenyl group containing 1 to 5 carbons. ##STR1##

  本发明公开了一种制备具有类视黄酸生物活性的二取代乙炔衍生物的过程，其中在催化剂的存在下，通过以下式子所示的6-乙炔基香豆素、6-乙炔基硫代香豆素和6-乙炔基-1,2,3,4-四氢喹啉衍生物与以下式子所示的卤代苯基或杂环基衍生物反应，以提供二取代乙炔衍生物。在式子中，符号具有以下含义。R.sub.1、R.sub.2、R.sub.3、R.sub.4和R.sub.5为氢或较低的烷基（1-6碳）基团，其中R.sub.1、R.sub.2、R.sub.3、R.sub.4和R.sub.5可以相同或不同）X为S、O或NR'，其中R'为氢或较低的烷基，Z表示氢或能够与分子的乙炔基团形成盐的金属离子，X'是卤素基团等离子体，A是苯基或杂环基，例如吡啶基、噻吩基、呋喃基、吡嗪基、嘧啶基、吡嗪啉基、噻唑基或噁唑基，n是0到5之间的整数，B是H、--COOH或其药学上可接受的盐、酯或酰胺，--CH.sub.2 OH或其醚或酯衍生物，或--CHO或其缩醛衍生物，或--COR.sub.1或其缩酮衍生物，其中R.sub.1是含有1到5个碳的烷基、环烷基或烯基基团。
• Compounds having a disubstituted acetylene moiety and retinoic acid-like
  申请人：Allergan, Inc.

  公开号：US05023341A1

  公开（公告）日：1991-06-11

  Disubstituted acetylene thiochroman containing derivatives of the formulae below wherein the symbols have the following meanings; R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are hydrogen or lower alkyl groups (of 1-6 carbons) where R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 may be identical or different from one another) X is S ##STR1##

  含有以下式子的二取代乙炔硫色烷衍生物，其中符号具有以下含义：R.sub.1，R.sub.2，R.sub.3，R.sub.4和R.sub.5是氢或较低的烷基（1-6个碳），其中R.sub.1，R.sub.2，R.sub.3，R.sub.4和R.sub.5可以相同也可以不同）X为S ## STR1 ##