1-bromo-2-(tert-butoxymethyl)benzene | 137395-70-1

• 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: 1-bromo-2-(tert-butoxymethyl)benzene
• 英文别名: 1-bromo-2-[(2-methylpropan-2-yl)oxymethyl]benzene
• CAS: 137395-70-1
• 化学式: C₁₁H₁₅BrO
• 分子量: 243.143
• InChiKey: WZGZWOFWQZGSSX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-bromo-2-(tert-butoxymethyl)benzene 在 吡啶 、 lithium aluminium tetrahydride 、 溴乙烷 、 氯化亚砜 、 乙醚 、 氯仿 、 magnesium 作用下， 生成 tert-butyl-(2-chloromethyl-benzyl)-ether
  参考文献：
  名称：

  的制备ø - ，米- ，和p -烷氧基-和苯氧基- methylbenzy氯化物

  摘要：

  DOI：

  10.1039/jr9540002819
• 作为产物：
  描述：

  叔丁醇 、 2-溴溴苄 在 sodium hydride 作用下， 生成 1-bromo-2-(tert-butoxymethyl)benzene
  参考文献：
  名称：

  Substrate regulation of product distribution in the reactions of arylchromium carbene complexes with alkynes

  摘要：

  The reactions of arylcarbene complexes with alkynes were examined for six of the nine possible substitution patterns for mono- and dioxygenated aryl substituents of the carbene carbon. The product distributions were found to be highly dependent on a number of factors, including solvent, temperature, concentration of alkyne, and the nature of the aryl substituent. The product distributions were determined in nearly all cases for phenol and indene products and in some cases for furans, cyclobutenones, and cyclopentenediones, which were minor products in these reactions. The product distribution for the reaction of each arylcarbene complex was determined as a function of both temperature and alkyne concentration, since the combined product distribution profiles provided a much more sensitive measure of the relative influences of the aryl substituents on the reaction outcome. Furthermore, this distribution profile was determined for the reactions with 3-hexyne and I-pentyne for each carbene complex. A series of monosubstituted arylcarbene complexes were examined to identify the effects of oxygen substituents at various positions on the aryl ring. The m-methoxy group has no effect on the product distribution, whereas the o-methoxy group influences the distribution by its ability to chelate to the metal center and the p-methoxy group influences the distribution by its ability to donate electrons by resonance. The product distributions from the reactions of the 2,3-, 2,4-, and 2,5-dimethoxy complexes followed the profile expected from the simple sum of the profiles of the monomethoxyl complexes. In all cases where an effect was observed, higher concentrations of alkyne led to a higher selectivity for phenol over indene products. The dependence of the product distribution on the concentration of the alkyne substrate is suggested to be due to a process in which a second molecule of alkyne coordinates to the metal center and determines the chemical outcome of an intermediate that has covalently incorporated the first alkyne. It is further suggested that the special ability of an alkyne to display this effect is related to the ability of an alkyne to readily switch from a 2 to a 4 e- donor. This phenomenon of substrate regulation of product distribution is termed the allochemical effect, and a mechanistic explanation is developed that features this proposed process and that is refined to accommodate the observed effects of solvent, temperature, chelation, and steric and electronic effects that have been observed for the reaction of carbene complexes and alkynes.

  DOI：

  10.1021/ja00024a040

文献信息

• Saccharin sulfonic acid catalyzed N-Boc protection of amines and formation of tert-butyl ethers from alcohols
  作者：F. Shirini、M. A. Zolfigol、M. Abedini

  DOI：10.1007/bf03246047

  日期：2010.9

  (SaSA), as a stable reagent is easily prepared by the reaction of saccharin with neat chlorosulfonic acid at room temperature. This compound is able to catalyze conversion of amines to their corresponding N-Boc protected amines with (Boc)2O. Alcohols were also converted to their corresponding tert-butyl ethers. All reactions took place under mild conditions giving the desired products in good to high

  通过在室温下使糖精与纯净的氯磺酸反应，可以容易地制备作为稳定试剂的糖精磺酸（SaSA）。该化合物能够用（Boc）2 O催化胺转化为其相应的N- Boc保护的胺。醇也被转化为其相应的叔丁基醚。所有反应均在温和条件下进行，以高至高收率得到所需产物。
• An Activatable Photosensitizer Targeted to γ‐Glutamyltranspeptidase
  作者：Mayumi Chiba、Yuki Ichikawa、Mako Kamiya、Toru Komatsu、Tasuku Ueno、Kenjiro Hanaoka、Tetsuo Nagano、Norbert Lange、Yasuteru Urano

  DOI：10.1002/anie.201704793

  日期：2017.8.21

  hydroxymethyl selenorhodamine green (gGlu-HMSeR) as a photo-inactive compound that would be specifically cleaved by the tumor-associated enzyme γ-glutamyltranspeptidase (GGT) to generate the potent photosensitizer HMSeR. gGlu-HMSeR has a spirocyclic structure and is colorless and does not show marked phototoxicity toward low-GGT-expressing cells or normal tissues upon irradiation with visible light. In contrast

  我们采用基于螺环化的策略来设计γ-谷氨酰羟甲基硒代罗丹明绿（gGlu-HMSeR）作为一种无光活性化合物，该化合物将被肿瘤相关酶γ-谷氨酰转肽酶（GGT）特异性裂解，从而产生有效的光敏剂HMSeR。gGlu-HMSeR具有螺环结构，无色，在可见光照射下，对表达低GGT的细胞或正常组织没有明显的光毒性。相反，HMSeR主要采取开放结构，着色并在照射时产生活性氧。因此，γ-谷氨酰基作为光动力疗法（PDT）的肿瘤靶向部分，开启了肿瘤细胞特异性的光毒性作用。为了验证该系统，我们采用了鸡绒膜尿囊膜（CAM），广泛用于药物毒性初步评估的模型。gGlu-HMSeR处理后的光辐照导致选择性消融了植入的肿瘤球体，而不会损害健康组织。
• Silver-Assisted Oxidative Isocyanide Insertion of Ethers: A Direct Approach to β-Carbonyl α-Iminonitriles
  作者：Leiyang Zhao、Bingxin Liu、Qitao Tan、Chang-Hua Ding、Bin Xu

  DOI：10.1021/acs.orglett.9b03590

  日期：2019.11.15

  silver-assisted oxidative coupling of simple ethers with tert-butyl isocyanide was realized in the presence of DDQ. The direct synthesis of high density functional β-carbonyl α-iminonitriles was achieved in a single step with high yields through the synergetic cascade isocyanide insertion into C(sp3)–H bond, where the isocyanide was used as crucial “CN” and “C═N” sources and the tert-butoxyl group acted as the

  在DDQ存在下，实现了简单醚与叔丁基异氰化物的有效银辅助氧化偶联。通过将协同级联异氰酸酯插入C（sp 3）-H键中，异氰酸酯被用作关键的“ CN”和“ C═N”源和叔丁氧基作为羰基源。已经证明了β-羰基α-亚胺的不同反应性。
• Red‐Shifted Fluorogenic Substrate for Detection of <i>lac</i> Z‐Positive Cells in Living Tissue with Single‐Cell Resolution
  作者：Hiroki Ito、Yu Kawamata、Mako Kamiya、Kayoko Tsuda‐Sakurai、Shinji Tanaka、Tasuku Ueno、Toru Komatsu、Kenjiro Hanaoka、Shigeo Okabe、Masayuki Miura、Yasuteru Urano

  DOI：10.1002/anie.201808670

  日期：2018.11.26

  describe the development of a red‐shifted fluorogenic substrate for β‐galactosidase, SPiDER‐Red‐βGal, based on a silicon rhodol scaffold and a carboxylic group as the intramolecular nucleophile. LacZ‐positive cells were successfully labeled with SPiDER‐Red‐βGal at single‐cell resolution in living samples, which enabled us to visualize different cell types in combination with GFP markers.

  的大肠杆菌的lac编码Ž基因β半乳糖苷酶是一种广泛使用的报告，但很少合成底物可用于与活样品中的单细胞分辨率检测其活性。我们最近报道的荧光底物SPiDER-βGal适合于此目的，但其水解产物显示绿色荧光发射，因此需要与绿色荧光蛋白（GFP）标记结合使用的红移类似物。在本文中，我们描述了一种基于β-半乳糖苷酶的红移荧光底物SPiDER-Red-βGal的开发，该底物基于硅rhodol支架和一个作为分子内亲核试剂的羧基。紫胶Z阳性细胞已成功在活体样品中以单细胞分辨率用SPiDER-Red-βGal标记，这使我们能够结合GFP标记物观察不同的细胞类型。
• Selective Ablation of β-Galactosidase-Expressing Cells with a Rationally Designed Activatable Photosensitizer
  作者：Yuki Ichikawa、Mako Kamiya、Fumiaki Obata、Masayuki Miura、Takuya Terai、Toru Komatsu、Tasuku Ueno、Kenjiro Hanaoka、Tetsuo Nagano、Yasuteru Urano

  DOI：10.1002/anie.201403221

  日期：2014.6.23

  We have developed an activatable photosensitizer capable of specifically inducing the death of β‐galactosidase‐expressing cells in response to photoirradiation. By using a selenium‐substituted rhodol scaffold bearing β‐galactoside as a targeting substituent, we designed and synthesized HMDESeR‐βGal, which has a non‐phototoxic spirocyclic structure owing to the presence of the galactoside moiety. However

  我们开发了一种可激活的光敏剂，能够特异性地诱导表达β-半乳糖苷酶的细胞对光辐射的死亡。通过使用带有β-半乳糖苷作为目标取代基的硒取代的Rhodol支架，我们设计并合成了HMDESeR-βGal，由于半乳糖苷部分的存在，它具有非光毒性的螺环结构。但是，β-半乳糖苷酶有效地将HMDESeR-βGal转化为光毒性的HMDESeR，其主要以开放的x吨形式存在。这种结构变化导致可见光吸收的急剧恢复以及产生单线态氧（1 O 2）的能力。将HMDESeR-βGal应用于黑腹果蝇幼虫 仅在后部区域表达β-半乳糖苷酶的翼盘，以高特异性通过光辐射诱导表达β-半乳糖苷酶的区域中的细胞死亡。