methyl 2,6-diisocyanatohexanoate | 45158-78-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 2,6-diisocyanatohexanoate
• 英文别名: L-lysine diisocyanate；Methyl N~2~,N~6~-bis(oxomethylidene)-L-lysinate；methyl (2S)-2,6-diisocyanatohexanoate
• CAS: 45158-78-9
• 化学式: C₉H₁₂N₂O₄
• 分子量: 212.205
• InChiKey: AYLRODJJLADBOB-QMMMGPOBSA-N

物化性质

• 沸点：
  142-144 °C(Press: 4 Torr)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  85.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,6-diisocyanatohexanoate 在 sodium hydroxide 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 64.0h， 生成
  参考文献：
  名称：

  探索具有不同氢键基序的胶凝剂家族中的分子识别途径

  摘要：

  我们报告了使用简单的合成方法，使用一系列不同的氢键连接基团（氨基甲酸酯，酰胺，尿素，硫脲和二酰基肼）合成的胶凝剂家族，其中烷基链连接至l-赖氨酸甲酯的氨基在异氰酸酯或酰氯化学上。这些化合物使有机溶剂如甲苯或环己烷胶凝的能力可以直接与连接基团形成分子间氢键的能力有关。一般而言，结构溶剂的能力可以被认为是：硫脲<氨基甲酸酯<酰胺<脲-二酰肼。此过程已通过热测量，扫描电子显微镜（SEM）以及红外和圆二色性光谱学证实。通过去保护甲酯基团，我们已经证明了疏水基团和亲水基团之间的平衡是必不可少的-如果系统具有太多的亲水性（例如，二酰基肼，尿素），由于在有机介质中的溶解度低，它将不会形成凝胶。但是，通过将甲酯转化为羧酸，可以增强基于酰胺和氨基甲酸酯键的不太有效的胶凝剂。此外，随后将酸与第二种组分（二氨基十二烷）混合进一步增强了形成网络的能力，并且在使用酰胺的情况下，生成了一种双组分凝胶，该凝胶可以固定各

  DOI：

  10.1016/j.tet.2007.03.120
• 作为产物：
  描述：

  230.0~238.0 ℃ 、33.0 kPa 条件下， 以77%的产率得到methyl 2,6-diisocyanatohexanoate
  参考文献：
  名称：

  イソシアネートの製造方法

  摘要：

  【課題】ホスゲンを使用せずにイソシアネートを製造する際に、イソシアネートを収率良く、安定して連続的に製造することができる、イソシアネートの製造方法を提供する。【解決手段】カルバメート化合物を熱分解して、イソシアネートを得る、イソシアネートの製造方法であって、次の工程を含む、製造方法。カルバメート化合物を含む反応物を反応器に供給する供給工程；特定の条件下にて、カルバメート化合物を熱分解して、イソシアネートを得る熱分解工程；及び、前記イソシアネートを反応器より回収する回収工程。【選択図】なし

  公开号：

  JP2023092840A

文献信息

• Solvent–gelator interactions—using empirical solvent parameters to better understand the self-assembly of gel-phase materials
  作者：William Edwards、Cecile A. Lagadec、David K. Smith

  DOI：10.1039/c0sm00843e

  日期：——

  By studying a family of L-lysine bis-urea gelators with variable peripheral groups in different solvents, a more detailed understanding of the way in which gelator fibres interact with the surrounding solvent environment is obtained. In all cases, these gelators establish the same hydrogen bonding molecular recognition pathways—however, this process is mediated by the nature of the solvent. In terms of Kamlet–Taft parameters, the α parameter of the solvent (hydrogen bond donor ability) has primary importance in controlling whether the gelator can establish a hydrogen bond network; the β parameter (hydrogen bond acceptor ability) plays a secondary role in tuning the thermal stability of the gel, and the π* parameter (polarisability) controls the solvation of the peripheral groups on the gelator by the solvent, and hence tunes the gel stability and the ability of the gelator to establish fibre–fibre interactions, as evidenced by scanning electron microscopy imaging. Considering solvent parameters allows us to gain a unique insight into hierarchical assembly processes at different length scales, i.e., molecular scale gelator–gelator interactions, and nanoscale fibre–fibre and fibre–solvent interactions. These processes are at the heart of developing effective models for the dynamic assembly of gel-phase soft materials.

  通过研究在不同溶剂中具有可变周边基团的L-赖氨酸双脲凝胶剂家族，我们获得了对凝胶剂纤维与周围溶剂环境相互作用方式的更详细理解。在所有情况下，这些凝胶剂都建立了相同的氢键分子识别途径——然而，这一过程受到溶剂性质的调节。根据Kamlet-Taft参数，溶剂的α参数（氢键供体能力）在控制凝胶剂是否能建立氢键网络方面具有首要重要性；β参数（氢键受体能力）在调节凝胶的热稳定性方面起次要作用，而π*参数（极化性）控制溶剂对凝胶剂周边基团的溶剂化作用，从而调节凝胶的稳定性和凝胶剂建立纤维间相互作用的能力，这通过扫描电子显微镜成像得到证实。考虑溶剂参数使我们能够独特地洞察不同长度尺度上的层次组装过程，即分子尺度的凝胶剂-凝胶剂相互作用，以及纳米尺度的纤维-纤维和纤维-溶剂相互作用。这些过程是开发动态组装凝胶相软材料有效模型的核心。
• In situ organogelation at room temperature: direct synthesis of gelators in organic solvents
  作者：Masahiro Suzuki、Yasushi Nakajima、Mariko Yumoto、Mutsumi Kimura、Hirofusa Shirai、Kenji Hanabusa

  DOI：10.1039/b401683a

  日期：——

  Organogels are formed through a conventional organogelation involving a heating process and an in situ organogelation at room temperature. The conventional organogelation is carried out by dissolution of gelators by heating, while the in situ organogelation is performed by mixing of highly reactive methyl 2,6-diisocyanatohexanoate (LDI) or 2-isocyanatoethyl 2,6-diisocyanatohexanoate (LTI) and alkylamines. The in situ organogelation produced the organogels within several seconds after mixing. The organogels prepared by the in situ organogelation showed quite similar FT-IR spectra and SEM photographs to those formed by conventional organogelation. Moreover, the in situ organogelation using LTI and octylamine as well as dodecylamine produced organogels of acetone, ethyl acetate, and acetonitrile that gelators 5 and 6 cannot gel through conventional organogelation.

  有机凝胶是通过传统的有机凝胶化和在室温下的原位有机凝胶化过程形成的。传统的有机凝胶化是通过加热溶解凝胶剂进行的，而原位有机凝胶化是通过将高度反应性的甲基 2,6-二异氰酸酯己酸酯（LDI）或 2-异氰基乙基 2,6-二异氰酸酯己酸酯（LTI）与烷基胺混合进行的。原位有机凝胶化在混合后几秒钟内就产生了有机凝胶。通过原位有机凝胶化制备的有机凝胶在傅里叶变换红外光谱（FT-IR）和扫描电子显微镜（SEM）照片上与通过传统有机凝胶化形成的有机凝胶表现出相似性。此外，使用 LTI 及辛胺和十二胺进行的原位有机凝胶化也产生了丙酮、乙酸乙酯和乙腈的有机凝胶，而凝胶剂 5 和 6 通过传统有机凝胶化无法形成凝胶。
• Controlled Self-Assembly-Synthetic Tunability and Covalent Capture of Nanoscale Gel Morphologies
  作者：Ian A. Coates、David K. Smith

  DOI：10.1002/chem.200900858

  日期：2009.6.22

  structures: We report a synthetically simple yet structurally rich gelator that self‐assembles through hydrogen bonding under different cooling regimes into different nanoscale morphologies (see figure), which can be covalently captured and stabilised by alkene metathesis.

  调整结构：我们报道了一种合成简单但结构丰富的胶凝剂，该胶凝剂通过在不同冷却方式下的氢键结合而自组装成不同的纳米级形态（见图），可通过烯烃复分解共价捕获并稳定化。
• Biodegradable and temperature-responsive polyurethanes for adriamycin delivery
  作者：Xianke Sun、Hui Gao、Guolin Wu、Yinong Wang、Yunge Fan、Jianbiao Ma

  DOI：10.1016/j.ijpharm.2011.04.007

  日期：2011.6

  To develop biodegradable polymers with temperature-sensitivity, a series of polyurethanes consisting of poly (ethylene glycol) (PEG) and L-lysine ester diisocyanate (LDI) were synthesized, and the structure and molecule weight of the polymers were examined by H-1 NMR, FT-IR, gel permeation chromatography (GPC). The solution properties of the copolymers were studied by turbidity measurement and size measurement. Polyurethanes could form nanoparticles by sonication in water. No temperature-sensitivity was observed with the polyurethane nanoparticles composed of PEG1000 and PEG1500. On the contrary, LDI-PEG600 exhibited a reversible temperature-responsive behavior in aqueous solution. The transition temperature (T-c) of LDI-PEG600 with methyl ester of LDI was higher than that of LDI-PEG600 with butyl ester side chain. The polymers were then used to encapsulate adriamycin (ADR) by the dialyzing method from dimethylformamide solution against water. ADR could be successfully encapsulated into the polyurethane nanoparticles. The ratio of ADR release from polymeric nanoparticles increased sharply above the T-c, while the release was suppressed below the T-c. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.
• ENZYMATIC CONJUGATION OF BIOACTIVE MOIETIES
  申请人：Quaedflieg Peter Jan Leonard Mario

  公开号：US20110045530A1

  公开（公告）日：2011-02-24

  The present invention relates to a method for selective conjugation of bioactive moieties to a polymer or polymerisable compound. The method is more specifically related to the selective conjugation of bioactive moieties to a pendant carboxylic acid, ester or thioester group in which the pendant group is part of a polymer or a polymerisable compound, wherein the method comprises contacting the polymer or polymerisable compound with a hydrolytic enzyme to catalyse the conjugation between the bioactive moiety and the pendant carboxylic acid, ester or thioester group. The conjugation of the bioactive moieties may occur prior to, during or after polymerization of the polymerisable compound. The conjugation of the bioactive moieties may also occur after the polymer is given a form.