1,3-dihexadecanoyl-2-(9,12,15-octadecatrienoyl)glycerol | 32373-20-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 甘油脂
• 英文名称: 1,3-dihexadecanoyl-2-(9,12,15-octadecatrienoyl)glycerol
• 英文别名: α,α'-Dipalmitoyl-β-linoleoin；TG(16:0/18:3(9Z,12Z,15Z)/16:0)；1,3-di(hexadecanoyloxy)propan-2-yl (9Z,12Z,15Z)-octadeca-9,12,15-trienoate
• CAS: 32373-20-9
• 化学式: C₅₃H₉₆O₆
• 分子量: 829.342
• InChiKey: CXACRYNAENZONW-FJYSWILXSA-N

物化性质

• 熔点：
  28-30 °C
• 沸点：
  783.8±50.0 °C(Predicted)
• 密度：
  0.926±0.06 g/cm3(Predicted)
• 物理描述：
  Solid

计算性质

• 辛醇/水分配系数(LogP)：
  20.7
• 重原子数：
  59
• 可旋转键数：
  49
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲醇 、 1,3-dihexadecanoyl-2-(9,12,15-octadecatrienoyl)glycerol 在 platinum(IV) oxide 三氟化硼 、 氢气 作用下， 生成 10-((1R,2R)-2-Propyl-cyclopentyl)-decanoic acid methyl ester 、 10-((1R,2S)-2-Propyl-cyclopentyl)-decanoic acid methyl ester 、 9-((1R,2R)-2-Propyl-cyclohexyl)-nonanoic acid methyl ester 、 9-((1R,2S)-2-Propyl-cyclohexyl)-nonanoic acid methyl ester 、 9-((1R,2R)-2-Butyl-cyclopentyl)-nonanoic acid methyl ester 、 9-((1R,2S)-2-Butyl-cyclopentyl)-nonanoic acid methyl ester
  参考文献：
  名称：

  脂肪酸位置分布和三酰基甘油组成对热处理过程中脂质副产物形成的影响：III-环状脂肪酸单体研究

  摘要：

  AbstractThe influence of isomeric triacylglycerols (TG) containing 18:3n‐3 and 18:2n‐6 on the formation of cyclic fatty acid monomers (CFAM) after heat treatment was assessed. Diacid TG, containing linoleic acid (L) or linolenic acid (α‐Ln) along with palmitic acid (P), and positioned either in the central position (PLP and PLnP, respectively), or in one of the two outer positions (PPL and PPLn, respectively) were synthesized. Monoacid TG of trilinolein and trilinolenin mixed with tripalmitin were also prepared. The CFAM formed after heating were analyzed after total hydrogenation. The results obtained with the model TG were compared to another model consisting of a canola oil and its randomized counterpart. In diacid TG, the location of α‐Ln in the central position of the TG molecule (PLnP) greatly enhanced the formation of the CFAM upon heating at temperatures below 240°C. On the other hand, 18:3n‐3 in monoacid TG (LnLnLn) was highly resistant to CFAM formation within the same range of temperatures (180–220°C). The TG structure, more than the TG composition, seemed to explain the differences in the CFAM formation between the original canola oil and its interesterified counterpart. Like α‐Ln, 18:2n‐6 was more prone to cyclization when attached at the central position of the model TG. Conversely, the influence of the TG composition on the cyclization rate was less important for L than for α‐Ln. It was concluded that positioning the C18 polyunsaturated fatty acid in the central position of TG rendered the oils much more sensitive to the cyclization reaction upon heat treatment.

  DOI：

  10.1007/s11746-998-0318-y
• 作为产物：
  描述：

  Γ-十八碳三烯酸 、 1,3-双棕榈酸甘油酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氯化碳 为溶剂， 反应 2.5h， 生成 1,3-dihexadecanoyl-2-(9,12,15-octadecatrienoyl)glycerol
  参考文献：
  名称：

  含两种棕榈酸的对称和非对称三酰基甘油的合成及物理性质

  摘要：

  AbstractA series of symmetrical (ABA) and non‐symmetrical (AAB) triacylglycerol (TAG) isomers containing “A,” palmitic (P; 16:0) acid, and “B,” either oleic (O; 9c‐18:1), elaidic (E; 9t‐18:1), linoleic (L; 9c,12c‐18:2) or linolenic (Ln; 9c,12c,15c‐18:3) fatty acids were synthesized by esterification of the thermodynamically more‐stable 1,3‐di‐ or 1(3)‐monoacylglycerols [1,3‐DAG or 1(3)‐MAG], respectively. 1,3‐dipalmitoylglycerol (1,3P‐DAG) was esterified with O, L or Ln acid to prepare the symmetrical TAG isomers POP, PLP and PLnP, while the O‐ E‐, L‐ and Ln‐1(3)MAG precursors, synthesized or obtained commercially, were esterified with P acid to prepare the non‐symmetrical TAG isomers OPP, EPP, LPP and LnPP, respectively. The drop point(s), solid fat content and melting point values of the synthesized TAG were determined. The 1,3‐dipalmitoylglycerol (1,3P‐DAG) and 1(3)P‐MAG precursors were prepared, in multi‐gram quantities, by partial glycerolysis (glycerol/p‐toluenesulfonic acid) of tripalmitin. After fractionation by silica gel chromatography, the 1(3)P‐MAG and 1,3P‐DAG isomers (ca. 80% of total MAG or DAG) were purified (>98%) by crystallization from acetone [silver ion‐HPLC was utilized to determine the structural purities of the DAG (or MAG) precursors, and the synthesized TAG]. Esterification of the appropriate, thermodynamically more‐stable MAG or DAG precursors was found to be a very versatile method for synthesis (in 80–90% yields) of multi‐gram (3–5 g) quantities of symmetrical and non‐symmetrical TAG isomers, in chemical and structural purities of >96 and 97–99%, respectively.

  DOI：

  10.1007/s11746-007-1173-y

文献信息

• Regioisomeric Characterization of Triacylglycerols Using Silver-Ion HPLC/MS and Randomization Synthesis of Standards
  作者：Miroslav Lísa、Hana Velínská、Michal Holčapek

  DOI：10.1021/ac900150j

  日期：2009.5.15

  Silver-ion normal-phase high-performance liquid chromatography (HPLC) provides a superior separation selectivity for lipids differing in the number and position of double bonds in fatty acid chains including the resolution of triacylglycerol (TG) regioisomers under optimized conditions. Our silver-ion HPLC method is based on the coupling of three columns in the total length of 75 cm and a new mobile phase gradient consisting of hexane−acetonitrile−2-propanol which provides better resolution and also reproducibility in comparison to previously used mobile phases. In our work, the chemical interesterification (randomization) of single-acid TG standards is used for the generation of regioisomeric series of TGs, because it provides a random distribution of fatty acids in TGs at well-defined concentration ratios. The baseline separation of regioisomeric TG pairs containing up to three double bonds and the partial separation of TG regioisomers with four to seven double bonds are reported for the first time. Our silver-ion high-performance liquid chromatography/mass spectrometry (HPLC/MS) method is applied for the regioisomeric characterization of complex samples of plant oils and animal fat, where the results clearly demonstrate different preference of sn-2 occupation in plants (mainly unsaturated fatty acids) versus animal fat (mainly saturated fatty acids).

  银离子正相高效液相色谱（HPLC）为脂质提供了优越的分离选择性，这些脂质在脂肪酸链中双键的数量和位置上存在差异，包括在优化条件下对甘油三酯（TG）位置异构体的分辨。我们的银离子HPLC方法是基于三根总长度为75厘米的柱子耦合以及一个新的由己烷、乙腈和丙酮醇组成的移动相梯度，这相比于之前使用的移动相提供了更好的分辨率和重复性。在我们的工作中，利用单酸TG标准的化学酯交换（随机化）来生成TG的位置异构体系列，因为这可以在明确定义的浓度比下提供脂肪酸在TG中的随机分布。首次报道了含有最多三个双键的位置异构体TG对的基线分离以及含有四到七个双键的TG位置异构体的部分分离。我们的银离子高效液相色谱/质谱（HPLC/MS）方法应用于植物油和动物脂肪的复杂样品的位置异构体特性鉴定，结果清楚地展示了在植物（主要是不饱和脂肪酸）和动物脂肪（主要是饱和脂肪酸）中sn-2占位偏好的不同。
• Practical Syntheses of Triacylglycerol Regioisomers Containing Long-chain Polyunsaturated Fatty Acids
  作者：Benjamin H. Fraser、Patrick Perlmutter、Chakra Wijesundera

  DOI：10.1007/s11746-006-1001-9

  日期：2007.1

  AbstractDocosahexaenoic acid (DHA, 22:6n‐3) is known to protect against a range of degenerative disease conditions and aid in the development of eye and brain function in infants. In dietary lipids DHA is found primarily in the triacylglycerol (TAG) form. However, the effects of the positional distribution of DHA in TAG on lipid functional properties such as bioactivity and oxidative stability are not clearly understood. Studies on this subject for the most part are limited by a lack of regioisomerically pure TAG model compounds containing DHA or similar long‐chain (LC)‐polyunsaturated fatty acids (PUFA). This paper reports on the development of a practical procedure, based on chemical and enzymatic reactions, for the syntheses of regioisomerically enriched, symmetrical and unsymmetrical TAG isomers containing two palmitic acid and one of linoleic acid, linolenic acid, or DHA. 1,3‐Selective acylation of glycerol with vinyl esters of fatty acids catalyzed by Candida antarctica lipase and direct coupling with fatty acids in the presence of the coupling agents 1‐(3‐dimethylaminopropyl)‐3‐ethylcarbodiimide hydrochloride and 4‐dimethylaminopyridine furnished 1,3‐dihexadecanoyl‐2‐docosahexaenoyl glycerol and its unsymmetrical isomer 1,2‐dihexadecanoyl‐3‐docosahexaenoyl glycerol in 99 and 60% yield, respectively. Critical to the success of the unsymmetrical TAG synthesis is the demonstration that PUFA‐containing glycerol acetonides can readily survive appropriately tailored acid‐catalyzed conditions. In this way, sufficient quantities of highly regioisomerically enriched PUFA‐containing unsymmetrical monoacylglycerols (MAG) and TAG have now become routinely accessible. The methods are amenable to scale‐up and could be adopted for regioenriched synthesis of a wide range of TAG.
• Serebrennikova,G.A. et al., Journal of general chemistry of the USSR, 1963, vol. 33, p. 54 - 56
  作者：Serebrennikova,G.A. et al.

  DOI：——

  日期：——
• Synthesis and Physical Properties of Symmetrical and Non‐symmetrical Triacylglycerols Containing Two Palmitic Fatty Acids
  作者：R. O. Adlof、G. R. List

  DOI：10.1007/s11746-007-1173-y

  日期：2008.2

  AbstractA series of symmetrical (ABA) and non‐symmetrical (AAB) triacylglycerol (TAG) isomers containing “A,” palmitic (P; 16:0) acid, and “B,” either oleic (O; 9c‐18:1), elaidic (E; 9t‐18:1), linoleic (L; 9c,12c‐18:2) or linolenic (Ln; 9c,12c,15c‐18:3) fatty acids were synthesized by esterification of the thermodynamically more‐stable 1,3‐di‐ or 1(3)‐monoacylglycerols [1,3‐DAG or 1(3)‐MAG], respectively. 1,3‐dipalmitoylglycerol (1,3P‐DAG) was esterified with O, L or Ln acid to prepare the symmetrical TAG isomers POP, PLP and PLnP, while the O‐ E‐, L‐ and Ln‐1(3)MAG precursors, synthesized or obtained commercially, were esterified with P acid to prepare the non‐symmetrical TAG isomers OPP, EPP, LPP and LnPP, respectively. The drop point(s), solid fat content and melting point values of the synthesized TAG were determined. The 1,3‐dipalmitoylglycerol (1,3P‐DAG) and 1(3)P‐MAG precursors were prepared, in multi‐gram quantities, by partial glycerolysis (glycerol/p‐toluenesulfonic acid) of tripalmitin. After fractionation by silica gel chromatography, the 1(3)P‐MAG and 1,3P‐DAG isomers (ca. 80% of total MAG or DAG) were purified (>98%) by crystallization from acetone [silver ion‐HPLC was utilized to determine the structural purities of the DAG (or MAG) precursors, and the synthesized TAG]. Esterification of the appropriate, thermodynamically more‐stable MAG or DAG precursors was found to be a very versatile method for synthesis (in 80–90% yields) of multi‐gram (3–5 g) quantities of symmetrical and non‐symmetrical TAG isomers, in chemical and structural purities of >96 and 97–99%, respectively.
• Effect of fatty acid positional distribution and triacylglycerol composition on lipid by-products formation during heat treatment: III-Cyclic fatty acid monomers study
  作者：J. C. Martin、F. Lavillonnière、M. Nour、J. L. Sébédio

  DOI：10.1007/s11746-998-0318-y

  日期：1998.12

  AbstractThe influence of isomeric triacylglycerols (TG) containing 18:3n‐3 and 18:2n‐6 on the formation of cyclic fatty acid monomers (CFAM) after heat treatment was assessed. Diacid TG, containing linoleic acid (L) or linolenic acid (α‐Ln) along with palmitic acid (P), and positioned either in the central position (PLP and PLnP, respectively), or in one of the two outer positions (PPL and PPLn, respectively) were synthesized. Monoacid TG of trilinolein and trilinolenin mixed with tripalmitin were also prepared. The CFAM formed after heating were analyzed after total hydrogenation. The results obtained with the model TG were compared to another model consisting of a canola oil and its randomized counterpart. In diacid TG, the location of α‐Ln in the central position of the TG molecule (PLnP) greatly enhanced the formation of the CFAM upon heating at temperatures below 240°C. On the other hand, 18:3n‐3 in monoacid TG (LnLnLn) was highly resistant to CFAM formation within the same range of temperatures (180–220°C). The TG structure, more than the TG composition, seemed to explain the differences in the CFAM formation between the original canola oil and its interesterified counterpart. Like α‐Ln, 18:2n‐6 was more prone to cyclization when attached at the central position of the model TG. Conversely, the influence of the TG composition on the cyclization rate was less important for L than for α‐Ln. It was concluded that positioning the C18 polyunsaturated fatty acid in the central position of TG rendered the oils much more sensitive to the cyclization reaction upon heat treatment.