benzyl(fluoromethyl)sulfane | 2924-74-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzyl(fluoromethyl)sulfane
• 英文别名: monofluoromethylbenzyl thioether；Fluoromethylsulfanylmethylbenzene
• CAS: 2924-74-5
• 化学式: C₈H₉FS
• 分子量: 156.224
• InChiKey: PREZBOFRYJAPOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  benzyl(fluoromethyl)sulfane 在 水 、 氯 作用下， 生成 fluoromethanesulfonyl chloride
  参考文献：
  名称：

  Fluoroalkanesulfonyl chlorides

  摘要：

  DOI：

  10.1021/jo01324a027
• 作为产物：
  描述：

  苄基氯甲基硫醚 在 氢氟酸 作用下， 生成 benzyl(fluoromethyl)sulfane
  参考文献：
  名称：

  Petrow; Sokol'skii, Zhurnal Obshchei Khimii, 1957, vol. 27, p. 2711,2713; engl. Ausg. S. 2751, 2753

  摘要：

  DOI：

文献信息

• Synthesis of Monofluoromethylthioesters from Aldehydes
  作者：Shi-Huan Guo、Meng-Yue Wang、Gao-Fei Pan、Xue-Qing Zhu、Ya-Ru Gao、Yong-Qiang Wang

  DOI：10.1002/adsc.201800136

  日期：2018.5.2

  A direct and efficient approach to the synthesis of monofluoromethylthioesters from aldehydes has been developed. The synthetic method features mild reaction conditions, good tolerance of functional groups, a broad substrate scope, and especially no metal involved in the reaction. The approach has the potential to be an important tool for the late‐stage functionalization of advanced synthetic intermediates

  已经开发了直接和有效的由醛合成单氟甲基硫代酯的方法。该合成方法具有温和的反应条件，对官能团的良好耐受性，广泛的底物范围，特别是没有金属参与反应。该方法有可能成为高级合成中间体后期功能化的重要工具，并可能在药物化学中找到许多应用。
• Direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH₂F: the accelerating effect of α-fluorine substitution
  作者：Xiao Shen、Min Zhou、Chuanfa Ni、Wei Zhang、Jinbo Hu

  DOI：10.1039/c3sc51831k

  日期：——

  An efficient and direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH2F 1 has been developed. In contrast to the previously known detrimental effect of α-fluorine substitution on SN2 reactions, the current monofluoromethylation is accelerated by the α-fluorine substitution. Based on a mechanistic study, a new reactivity of sulfoximine (as a radical monofluoromethylation reagent) is disclosed.

  一种高效且直接的单氟甲基化反应已被开发，用于O、S、N和P亲核试剂和PhSO(NTs)CH2F 1。与之前已知的α-氟取代对SN2反应的负面影响不同，目前的单氟甲基化反应因α-氟取代而加速。基于机制研究，揭示了亚磺酰胺作为自由基单氟甲基化试剂的新反应性。
• (1S)-(−)-N-Monofluoromethylthio-7,7-dichloro-2,10-camphorsultam: An optically pure reagentfor asymmetric monofluoromethylthiolation
  作者：He Zhang、Qilong Shen

  DOI：10.1016/j.tet.2021.132508

  日期：2021.11

  The development of an optically pure monofluoromethylthiolating reagent based on Oppolzer's camphorsultam auxiliary (1S)-(−)-N-monofluoromethylthio-7,7-dichloro-2,10-camphorsultam 1b was described. Reagents 1b reacted with two types of substrates including oxazolone and oxindole derivatives with good to excellent enantioselectivities under mild conditions, thus representing the first available method

  描述了基于 Oppolzer 的樟脑磺胺辅助剂 (1S)-(-)- N -monofluoromethylthio-7,7-dichloro-2,10-camphorsultam 1b的光学纯单氟甲硫基化试剂的开发。试剂1b与两种类型的底物反应，包括恶唑酮和羟吲哚衍生物，在温和条件下具有良好到优异的对映选择性，因此代表了我们获得单氟甲基硫醇化立体中心的第一种可用方法。
• α-Fluorination of Sulfides with<i>N</i>-Fluoropyridinium Triflates
  作者：Teruo Umemoto、Ginjiro Tomizawa

  DOI：10.1246/bcsj.59.3625

  日期：1986.11

  The reaction of sulfides possessing α-hydrogen with various N-fluoropyridinium salts was examined. While the fluorinating power increased in the order of N-fluoro-2,4,6-trimethylpyridinium triflate 12, and 3 no longer produced the α-fluoro sulfide. Triflate 1 was more reactive than the corresponding tetrafluoroborate 4. Thus, it was shown that 1 satisfactorily fluorinated various kinds of sulfides under very mild conditions, giving α-fluoro sulfides. A two-step mechanism, oxidative fluorination of sulfur and Pummerer-type rearrangement, was proposed for the fluorination. The corresponding α-fluoro sulfoxide or sulfones were easily prepared from the sulfides by successive fluorination–oxidation procedure.

  我们研究了具有α-氢的硫化物与各种N-氟吡啶盐的反应。氟化能力按以下顺序增加：N-氟-2,4,6-三甲基吡啶三氟甲磺酸盐1 < N-氟吡啶三氟甲磺酸盐2 < N-氟-3,5-二氯吡啶三氟甲磺酸盐3，而α-氟硫化物的产率则按以下顺序递减：1 > 2，3不再产生α-氟硫化物。三氟甲磺酸盐1的反应性优于相应的四氟硼酸盐4。因此，研究表明，1在非常温和的条件下能有效氟化各种硫化物，生成α-氟硫化物。我们提出了一种两步机制，即硫的氧化氟化和Pummerer型重排，用于氟化反应。相应的α-氟亚磺酸盐或磺酮可通过连续的氟化-氧化过程轻松从硫化物中制备。
• Electrophilic monofluoromethylation of O-, S-, and N-nucleophiles with chlorofluoromethane
  作者：Wei Zhang、Lingui Zhu、Jinbo Hu

  DOI：10.1016/j.tet.2007.08.043

  日期：2007.10

  to be a useful electrophilic monofluoromethylating agent for a variety of O-, S-, and N-nucleophiles. The reaction is not sensitive to the radical scavenger such as nitrobenzene, which strongly supports an SN2 mechanism rather than an SET mechanism. Although most of these products (fluoromethyl ethers, sulfides, and amines) can be isolated with good purity, some of these compounds do intend to decompose

  已经发现CH 2 ClF是用于多种O-，S-和N-亲核试剂的有用的亲电单氟甲基化剂。该反应对自由基清除剂如硝基苯不敏感，硝基清除剂强烈支持S N 2机理而不是SET机理。尽管可以分离出大多数此类产品（氟代甲基醚，硫化物和胺），并且纯度高，但是其中一些化合物确实打算在存储过程中分解（通过脱氟）。尝试用CH 2 ClF，CH 2 FI或FCH 2 OTs作为单氟甲基化剂进行碳亲核试剂的亲电单氟甲基化，但没有成功。