甲基硫基溴化物 | 18681-52-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫基化合物
• 中文名称: 甲基硫基溴化物
• 英文名称: methylsulfenyl bromide
• 英文别名: methyl sulfenyl bromide；methanesulfenyl bromide；methylsulfenylbromid；bromo-methyl-sulfane；methyl thiohypobromite
• CAS: 18681-52-2
• 化学式: CH₃BrS
• 分子量: 127.005
• InChiKey: VTACQRMNQIKUJV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2930909090

反应信息

• 作为反应物：
  描述：

  甲基硫基溴化物 、 苯酚 以 四氯化碳 为溶剂， 生成 2-羟基茴香硫醚
  参考文献：
  名称：

  Alkylmercaptophenols by Sulfenylation of Phenols

  摘要：

  DOI：

  10.1021/jo01045a076
• 作为产物：
  描述：

  methylthio radical 在 溴 作用下， 24.9 ℃ 、4.0 kPa 条件下， 生成 甲基硫基溴化物
  参考文献：
  名称：

  溴原子（2P3 / 2）+硫化氢.tautm反应的温度依赖性动力学研究。巯基+溴化氢和溴原子（2P3 / 2）+甲硫醇。甲硫醇+溴化氢。巯基和甲硫基自由基的形成热

  摘要：

  Time-resolved resonance fluorescence detection of Br(2P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br(2P3/2) H2S reversible SH + HBr (1, -1) and Br(2P3/2) + CH3SH reversible CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(-12) cm3 molecule-1 s-1 which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T], k-1 = (4.40 +/- 0.92) exp[(-971 +/- 73)/T], k2 = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and K-2 = (1.46 +/- 0.21) exp[(-399 +/- 41)/T]; errors are 2-sigma and represent precision only. By examining Br(2P3/2) equilibration kinetics following 355-nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(-10) cm3 molecule-1 s-1 has been obtained for the reaction CH3S + Br2 --> CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr, Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal mol-1: for reaction 1, DELTA-H298 = 3.64 +/- 0.43 and DELTA-H0 = 3.26 +/- 0.45; for reaction 2, DELTA-H298 = -0.14 +/- 0.28 and DELTA-H0 = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the following heats of formation for the RS radicals in units of kcal mol-1: DELTA-H(f)-degrees 0(SH) = 34.07 +/- 0.72, DELTA-H(f)-degrees 298(SH) = 34.18 +/- 0.68, DELTA-H(f)-degrees 0(CH3S) = 31.44 +/- 0.54, DELTA-H(f)-degrees 298(CH3S) = 29.78 +/- 0.44; errors are 2-sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our data is near the low end of the range of previous estimates and is 3-4 kcal mol-1 lower values derived from recent molecular beam photofragmentation studies.

  DOI：

  10.1021/j100185a025
• 作为试剂：
  描述：

  3-(苄氧羰基氨基)-1-丙醇 在 吡啶 、 甲基硫基溴化物 、 水 、 sodium methylate 、 silver trifluoromethanesulfonate 、 氰化汞 、 对甲苯磺酸 、 三乙胺 、 mercury dibromide 作用下， 以 甲醇 、 溶剂黄146 、 1,2-二氯乙烷 、 丙酮 、 乙腈 为溶剂， 反应 47.0h， 生成 N-benzyloxycarbonyl-3-aminopropyl 2,3-di-O-benzoyl-4-O-<2,3-di-O-(2-methylbenzoyl)-4-O-dichloroacetyl-α-L-rhamnopyranosyl>-6-O-(2-methylbenzoyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of fragments of a streptococcus pneumoniae type-specific capsular polysaccharide

  摘要：

  DOI：

  10.1016/s0040-4020(01)89206-1

文献信息

• Fluorinated Glycosyl Amino Acids for Mucin-Like Glycopeptide Antigen Analogues
  作者：Sarah Wagner、Christian Mersch、Anja Hoffmann-Röder

  DOI：10.1002/chem.200903294

  日期：2010.6.25

  development of immunotherapy against cancer. Mucin‐type glycopeptides have been successfully investigated as molecularly defined vaccine prototypes for triggering humoral immunity but are susceptible to rapid in vivo degradation. As a potential means to enhance the bioavailabilities of the antigenic structures, hydrolysis‐resistant carbohydrate analogues with fluorine substituents at positions C6, C2′ and

  粘蛋白糖蛋白在上皮肿瘤细胞上的异常糖基化概况代表了针对癌症的免疫疗法发展的有吸引力的靶结构。粘蛋白型糖肽已作为分子定义的疫苗原型成功进行了研究，可触发体液免疫，但易于在体内迅速降解。作为增强抗原结构生物利用度的潜在手段，合成了在位置C6，C2'和C6'具有氟取代基的耐水解碳水化合物类似物，并将其掺入粘蛋白MUC1的串联重复序列中。由此产生的伪糖肽可用于阐明化学修饰的抗体决定簇对代谢和免疫学特性的影响。
• Synthesis and immunological evaluation of MUC1 glycopeptide conjugates bearing N-acetyl modified STn derivatives as anticancer vaccines
  作者：An Xiao、Xiu-Jing Zheng、Chengcheng Song、Yue Gui、Chang-Xin Huo、Xin-Shan Ye

  DOI：10.1039/c6ob01092j

  日期：——

  problem. To solve this problem, several STn derivatives with N-acetyl modifications were synthesized and incorporated into a 20-amino acid MUC1 tandem repeat sequence. The modified STn-MUC1 glycopeptides were further connected to a carrier protein keyhole limpet hemocyanin (KLH). The immunological effects of these synthetic vaccine conjugates were evaluated using the BALB/c mouse model. The results showed

  糖蛋白MUC1是抗肿瘤疫苗开发的有吸引力的靶标。但是，MUC1的免疫原性仍然很弱。为了解决该问题，合成了几种具有N-乙酰基修饰的STn衍生物，并将其掺入20个氨基酸的MUC1串联重复序列中。修饰的STn-MUC1糖肽进一步与载体蛋白匙孔戚血蓝蛋白（KLH）连接。使用BALB / c小鼠模型评估了这些合成疫苗偶联物的免疫学作用。结果表明，疫苗V2引起与天然STn-MUC1抗原交叉反应的抗体的更高滴度。此外，引起的抗血清与STn-MUC1抗原阳性的肿瘤细胞反应，表明碳水化合物抗原修饰策略可能具有克服天然MUC1糖肽弱免疫原性的潜力。
• Biomimetic Synthesis of the Tumor-Associated (2,3)-Sialyl-T Antigen and Its Incorporation into Glycopeptide Antigens from the Mucins MUC1 and MUC4
  作者：Sebastian Dziadek、Constanze Brocke、Horst Kunz

  DOI：10.1002/chem.200400228

  日期：2004.9.6

  Among the tumor-associated saccharide antigens, the (2,3)-sialyl-T antigen has been identified as the most abundant glycan, found in several different carcinoma cell lines. According to a linear biomimetic strategy, the (2,3)-sialyl-T antigen was synthesized by a stepwise glycan chain extension of a protected galactosamine-threonine precursor. For the construction of immunostimulating antigens combining

  上皮肿瘤细胞上的糖蛋白通常表现出异常的糖基化特征。由葡糖胺转移的下调和唾液酸化过早导致的聚糖侧链的不完全形成导致另外的肽表位，其在粘蛋白型糖蛋白中变得可为免疫系统所接近。这些癌症特异性结构改变被认为是对肿瘤细胞进行选择性免疫攻击的有前途的基础。在与肿瘤相关的糖抗原中，（2,3）-唾液酸-T抗原已被确定为最丰富的聚糖，存在于几种不同的癌细胞系中。根据线性仿生策略，通过保护的半乳糖胺-苏氨酸前体的逐步聚糖链延伸合成（2,3）-唾液酸-T抗原。
• Synthetic Antitumor Vaccines Containing MUC1 Glycopeptides with Two Immunodominant Domains-Induction of a Strong Immune Response against Breast Tumor Tissues
  作者：Nikola Gaidzik、Anton Kaiser、Danuta Kowalczyk、Ulrika Westerlind、Bastian Gerlitzki、Hans Peter Sinn、Edgar Schmitt、Horst Kunz

  DOI：10.1002/anie.201104529

  日期：2011.10.10

  A shot in the arm for cancer treatment: Two MUC1 tetanus toxoid vaccines were synthesized and induced a strong immune response in mice. The antibodies elicited by the vaccines show a high selectivity for the tumor cells in mammary carcinoma tissues and also distinguish between tumor tissues at different stages.

  癌症治疗方面的一枪：合成了两种MUC1破伤风类毒素疫苗，并在小鼠中诱导了强烈的免疫反应。疫苗引发的抗体对乳腺癌组织中的肿瘤细胞显示出高选择性，并且还可以区分处于不同阶段的肿瘤组织。
• Synthesis of Organochalcogen Propargyl Aryl Ethers and Their Application in the Electrophilic Cyclization Reaction: An Efficient Preparation of 3-Halo-4-Chalcogen-2<i>H</i>-Benzopyrans
  作者：Benhur Godoi、Adriane Sperança、Davi F. Back、Ricardo Brandão、Cristina W. Nogueira、Gilson Zeni

  DOI：10.1021/jo900307k

  日期：2009.5.1

  atom of the electrophilic chalcogen species. Additional versatility in this process was demonstrated with respect to a diverse array of functionality in the aromatic ring at propargyl aryl ethers. These propargyl aryl ethers, bearing the chalcogen group, underwent highly selective intramolecular cyclizations when treated with I2 or ICl affording 3-iodo-4-chalcogen-2H-benzopyrans. The results demonstrated

  我们在本文中描述了通过乙炔化锂中间体与亲电子硫属元素（硫，硒，碲）物质的反应来合成各种有机硫属炔丙基芳基醚。直接与硫属元素原子键合的各种芳基和烷基用作亲电子试剂。结果表明，该反应不显着取决于键合至亲电子硫属元素物种的硫属元素原子上的芳环中取代基的电子效应。关于炔丙基芳基醚在芳环中的多种官能团，证明了该方法的其他通用性。这些带有硫属元素基的炔丙基芳基醚在经过I 2处理后经历了高度选择性的分子内环化反应或ICl得到3-碘-4-硫属元素-2H-苯并吡喃。结果表明，环化效率受芳环的空间效应的显着影响，这是因为环化反应在orto位置具有取代基的芳环比没有取代基的芳环的收率低。还研究了3-碘-4-硫属元素-2H-苯并吡喃的反应性。在Neghishi交叉偶联条件下处理4-硒代丁基苯并吡喃，以良好的收率提供相应的3-芳基苯并吡喃衍生物。另外，在没有任何助催化剂的情况下，使用铜催化的与硫醇的交叉偶联反应，我