trans-2-(p-methoxystyryl)-4,4-dimethyl-1,3-oxathiane | 561329-01-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: trans-2-(p-methoxystyryl)-4,4-dimethyl-1,3-oxathiane
• 英文别名: 2-[2-(4-methoxy-phenyl)ethenyl]-4,4-dimethyl-1,3-oxathiane；2-[(E)-2-(4-methoxyphenyl)ethenyl]-4,4-dimethyl-1,3-oxathiane
• CAS: 561329-01-9
• 化学式: C₁₅H₂₀O₂S
• 分子量: 264.389
• InChiKey: WNOIPMUAKOZTMT-RMKNXTFCSA-N

物化性质

• 沸点：
  393.4±42.0 °C(Predicted)
• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  43.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-溴-4-丙-1-烯-2-基苯 、 trans-2-(p-methoxystyryl)-4,4-dimethyl-1,3-oxathiane 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以76%的产率得到4-(p-methoxyphenyl)-2,2-diphenyl-3,4-dihydro-2H-thiopyran
  参考文献：
  名称：

  A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes

  摘要：

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00179-0
• 作为产物：
  描述：

  3-甲基-2-丁烯酸乙酯 在 lithium aluminium tetrahydride 、 三氟化硼乙醚 、 sodium ethanolate 、 sodium 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 氨 为溶剂， 反应 39.83h， 生成 trans-2-(p-methoxystyryl)-4,4-dimethyl-1,3-oxathiane
  参考文献：
  名称：

  A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes

  摘要：

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00179-0

文献信息

• A novel tandem [4++2] cycloaddition–elimination reaction of 4,4-dimethyl-2-styryl-1,3-oxathianes with olefins
  作者：Kiyoharu Nishide、Shin-ichi Ohsugi、Manabu Node

  DOI：10.1016/s0040-4039(99)02064-x

  日期：2000.1

  A novel tandem [4++2] cycloaddition–elimination reaction of 1,3-oxathianes 1a,b with olefins promoted by titanium tetrachloride to give 3,4-dihydro-2H-thiopyrans 3 was developed. 4,4-Dimethyl-2-styryl-1,3-oxathiane (1a) was used as a synthetic equivalent of a highly reactive thiocinnamaldehyde. Geminal dimethyl substituents at the 4-position of 1,3-oxathianes 1 are an intrinsic part of this cycloaddition–elimination

  一种新型串联[4 + 2] 1,3- oxathianes的环加成-消除反应1A，b通过促进烯烃四氯化钛，得到3,4-二氢-2- ħ -thiopyrans 3被开发。4,4-二甲基-2-苯乙烯基-1,3-氧杂蒽（1a）被用作高反应性硫肉桂醛的合成等同物。在1,3- oxathianes 4-位偕二甲基的取代基1是此环加成-消除反应的固有部分。
• 1,3-Oxathianes as perfuming and flavoring ingredients
  申请人：——

  公开号：US20020155960A1

  公开（公告）日：2002-10-24

  The present invention relates to the perfumery and flavor industry. It concerns more particularly the use of a compound of formula (I) as perfuming or flavoring ingredient 1 wherein R 1 and R 2 represent simultaneously or a independently a linear or branched alkyl or alkenyl group containing 1 to 4 carbon atoms, R 3 represents a hydrogen, a cycloalkyl or a cycloalkenyl group, possibly substituted, a furanyl group, possibly substituted, a linear or branched alkyl or alkenyl group containing 1 to 12 carbon atoms, possibly substituted, or a linear or branched alkyl or alkenyl group containing 1 to 4 carbon atoms terminated by a carboxyl ester or amide group; and R 4 represents a hydrogen or a linear alkyl group containing 1 to 4 carbon atoms. Substituents groups of R 3 can be for example C 1 -C 3 alkyl or alkenyl groups, an aromatic ring or C 5 -C 7 cycloalkyl or cycloalkenyl groups, possibly substituted by methyl or ethyl groups.

  本发明涉及香水和香精行业。本发明尤其涉及式（I）化合物作为香水或香料成分的用途 1 其中 R 1 和 R 2 同时或各自代表含有 1 至 4 个碳原子的直链或支链烷基或烯基、 R 3 代表氢、可能被取代的环烷基或环烯基、可能被取代的呋喃基、可能被取代的含 1 至 12 个碳原子的直链或支链烷基或烯基、或以羧酸酯或酰胺基团为末端的含 1 至 4 个碳原子的直链或支链烷基或烯基；以及 R 4 代表氢或含有 1 至 4 个碳原子的直链烷基。 R 3 的取代基团可以是例如 C 1 -C 3 烷基或烯基、芳香环或 C 5 -C 7 环烷基或环烯基，可能被甲基或乙基取代。
• 1,3-oxathianes as perfuming and flavouring ingredients
  申请人：FIRMENICH SA

  公开号：EP1229032B1

  公开（公告）日：2005-04-20
• US6559109B2
  申请人：——

  公开号：US6559109B2

  公开（公告）日：2003-05-06
• A novel tandem [4++2] cycloaddition–elimination reaction: 2-alkenyl-4,4-dimethyl-1,3-oxathianes as synthetic equivalents for α,β-unsaturated thioaldehydes
  作者：Shin-ichi Ohsugi、Kiyoharu Nishide、Manabu Node

  DOI：10.1016/s0040-4020(03)00179-0

  日期：2003.3

  The first tandem cationic [4(+)+2] polar cycloaddition-elimination reaction of 1-thia-1,3-butadienyl cations B with olefins to afford directly 3,4-dihydro-2H-thiopyrans D is described. The cations B were easily accessible by treatment of monothioacetals A, particularly the 2-alkenyl-4,4-dimethyl-1,3-oxathianes 1, with a hard Lewis acid. In this novel reaction, 2-alkenyl-4,4-dimethyl-1,3-oxathianes were utilized as synthetic equivalents for highly reactive alpha,beta-unsaturated thioaldehydes. The effect of geminal dimethyl substituents on the oxathianes 1 and the mechanistic aspect of the reaction are considered. The reaction's asymmetric version was also investigated using a chiral oxathiane 4 derived from (-)-(IR,2R,5R)-2-(I-mercapto-l-methylethyl)-5-methylcyclohexanol. Although the enantioselectivities were moderate, the whole process can be done under odorless conditions. (C) 2003 Elsevier Science Ltd. All rights reserved.