(3R)-3-hydroxy-3',4'-didehydro-β,β-carotene | 752-29-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (3R)-3-hydroxy-3',4'-didehydro-β,β-carotene
• 英文别名: (3R)-3',4'-didehydro-β,β-caroten-3-ol；anhydrolutein III；(3R)-3',4'-anhydrolutein；(1R)-3,5,5-trimethyl-4-[(1E,3E,5E,7E,9E,11E,13E,15E,17E)-3,7,12,16-tetramethyl-18-(2,6,6-trimethylcyclohexa-1,3-dien-1-yl)octadeca-1,3,5,7,9,11,13,15,17-nonaenyl]cyclohex-3-en-1-ol
• CAS: 752-29-4
• 化学式: C₄₀H₅₄O
• 分子量: 550.868
• InChiKey: BMQNSHDVIYZULR-FKKUPVFPSA-N

物化性质

• 熔点：
  140-142 °C
• 沸点：
  686.0±34.0 °C(Predicted)
• 密度：
  0.982±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3R)-3-hydroxy-3',4'-didehydro-β,β-carotene 在 四氢呋喃 、 甲醇 、 sodium tetrahydroborate 、 potassium hydroxide 、 碘甲烷 作用下， 以 四氢呋喃 为溶剂， 反应 52.0h， 生成 lutein
  参考文献：
  名称：

  （3R，3'R，6'R）-叶黄素通过（3R）-3'，4'-脱水叶黄素合成（3R，3'R）-玉米黄质及其内消旋立体异构体

  摘要：

  的方法，已经开发了的部分合成（3 - [R，3' - [R）-zeaxanthin和（3 - [R，3'小号;内消旋）从可商购的（3 -zeaxanthin - [R，3' - [R，6' - [R）-lutein 。这涉及叶黄素脱水产物（即（3 R）-3'，4'-二氢-β，β-胡萝卜素-3-醇[（3 R）-3'，4'-脱水叶黄素]的区域选择性氢硼化，得到（3的混合物[R，3' - [R）-zeaxanthin和（3 - [R，3'小号;内消旋玉米黄质，然后通过酶介导的酰化作用分离这些类胡萝卜素。（3 - [R，3' - [R，6' - [R）-Lutein，（3 - [R，3' - [R）-zeaxanthin及其内消旋异构体累加在人体眼组织和预防年龄相关性黄斑变性的有牵连（AMD ）。 光学活性羟基类胡萝卜素-部分合成-手性拆分-区域选择性硼氢化-高共轭多烯

  DOI：

  10.1055/s-0031-1289662
• 作为产物：
  描述：

  叶黄素 在 硫酸 作用下， 以 丙醇 、 水 为溶剂， 反应 20.0h， 以92%的产率得到(3R)-3-hydroxy-3',4'-didehydro-β,β-carotene
  参考文献：
  名称：

  （3R，3'R，6'R）-叶黄素通过（3R）-3'，4'-脱水叶黄素合成（3R，3'R）-玉米黄质及其内消旋立体异构体

  摘要：

  的方法，已经开发了的部分合成（3 - [R，3' - [R）-zeaxanthin和（3 - [R，3'小号;内消旋）从可商购的（3 -zeaxanthin - [R，3' - [R，6' - [R）-lutein 。这涉及叶黄素脱水产物（即（3 R）-3'，4'-二氢-β，β-胡萝卜素-3-醇[（3 R）-3'，4'-脱水叶黄素]的区域选择性氢硼化，得到（3的混合物[R，3' - [R）-zeaxanthin和（3 - [R，3'小号;内消旋玉米黄质，然后通过酶介导的酰化作用分离这些类胡萝卜素。（3 - [R，3' - [R，6' - [R）-Lutein，（3 - [R，3' - [R）-zeaxanthin及其内消旋异构体累加在人体眼组织和预防年龄相关性黄斑变性的有牵连（AMD ）。 光学活性羟基类胡萝卜素-部分合成-手性拆分-区域选择性硼氢化-高共轭多烯

  DOI：

  10.1055/s-0031-1289662

文献信息

• Process For The Preparation of Beta and Alpha Cryptoxanthin
  申请人：KHACHIK Frederick

  公开号：US20100280286A1

  公开（公告）日：2010-11-04

  The present invention relates to a process for converting lutein and/or lutein esters to (3R)-β-cryptoxanthin and (3R,6′R)-α-cryptoxanthin, suitable for human consumption as dietary supplements, by employing safe and environmentally friendly reagents. (3R)-β-Cryptoxanthin and (3R,6′R)-α-cryptoxanthin are two rare food carotenoids that are not commercially available and the former exhibits vitamin A activity. In the first synthetic step, commercially available lutein and/or lutein esters are transformed into a mixture of dehydration products of lutein (anhydroluteins) in the presence of a catalytic amount of an acid. The resulting anhydroluteins are then converted to (3R)-β-cryptoxanthin (major product) and (3R,6′R)-α-cryptoxanthin (minor product) by heterogeneous catalytic hydrogenation employing transition elements of group VIII (Pt, Pd, Rh supported on alumina or carbon) in a variety of organic solvents under atmospheric pressure of hydrogen and at temperatures ranging from −15° C. to 40° C. Among these catalysts, Pt supported on alumina at 40° C. in ethyl acetate provides the best yield of (3R)-β-cryptoxanthin and (3R,6′R)-α-cryptoxanthin. Several homogeneous catalysts can also promote the regioselective hydrogenation of anhydroluteins to a mixture of (3R)-β-cryptoxanthin and (3R,6′R)-α-cryptoxanthin in low to moderate yields. The catalysts may be transition metal complexes such as palladium acetylacetonate, Rh(Ph 3 P) 3 Cl (Wilkinson's catalyst), [(C 6 H 11 ) 3 P[C 8 H 12 ][C 5 H 5 N] Ir + PF6 − (Crabtree catalyst), or [C 8 H 12 ][(MePh 2 P) 2 ]Ir + PF6 − . Among these, Wilkinson catalyst converts anhydroluteins to (3R)-β-cryptoxanthin and (3R,6′R)-α-cryptoxanthin in nearly quantitative yield. A novel feature of this invention is the regioselective hydrogenation of anhydroluteins while the highly conjugated polyene chain of these carotenoids remains intact.

  本发明涉及一种将叶黄素和/或叶黄素酯转化为（3R）-β-隐花黄素和（3R,6′R）-α-隐花黄素的过程，适合作为人类膳食补充剂，采用安全且环保的试剂。 （3R）-β-隐花黄素和（3R,6′R）-α-隐花黄素是两种罕见的食品类胡萝卜素，目前商业上不可获得，前者具有维生素A活性。在第一合成步骤中，商业上可获得的叶黄素和/或叶黄素酯在酸的催化下转化为叶黄素的脱水产物混合物（脱水叶黄素）。然后，通过使用过渡元素（Pt、Pd、Rh负载在氧化铝或碳上）在各种有机溶剂中，利用异质催化加氢将得到的脱水叶黄素转化为（3R）-β-隐花黄素（主要产物）和（3R,6′R）-α-隐花黄素（次要产物），在氢气大气压下，温度范围从-15°C到40°C。在这些催化剂中，40°C时在乙酸乙酯中负载Pt提供了（3R）-β-隐花黄素和（3R,6′R）-α-隐花黄素的最佳产率。几种均相催化剂也可以促进叶黄素的区域选择性加氢，将其转化为（3R）-β-隐花黄素和（3R,6′R）-α-隐花黄素的混合物，产率较低至适中。这些催化剂可以是过渡金属配合物，如醋酸钯、Rh(Ph3P)3Cl（威尔金森催化剂）、[(C6H11)3P[C8H12][C5H5N] Ir+PF6−（克拉布特里催化剂）或[C8H12][(MePh2P)2]Ir+PF6−。在这些催化剂中，威尔金森催化剂将脱水叶黄素转化为（3R）-β-隐花黄素和（3R,6′R）-α-隐花黄素，产率接近定量。本发明的一个新特点是在叶黄素的高度共轭多烯链保持完整的情况下对脱水叶黄素进行区域选择性加氢。
• Method for production of rare carotenoids from commercially available lutein
  申请人：——

  公开号：US20030220525A1

  公开（公告）日：2003-11-27

  Disclosed are processes for conversion of (3R,3′R,6′R)-lutein to (3R,6′R)-&agr;-cryptoxanthin, (3R)-&bgr;-cryptoxanthin, anhydroluteins I, II, and III (dehydration products of lutein), and a method for separating and purifying the individual carotenoids including the unreacted (3R,3′R)-zeaxanthin. The invention also includes two methods that transform (3R,3′R,6′R)-lutein into (3R,6′R)-&agr;-cryptoxanthin in excellent yields.

  披露了将(3R,3′R,6′R)-叶黄素转化为(3R,6′R)-α-隐花黄素、(3R)-β-隐花黄素、无水叶黄素I、II和III（叶黄素的脱水产物）的过程，以及一种分离和纯化单个类胡萝卜素的方法，包括未反应的(3R,3′R)-玉米黄质。该发明还包括两种将(3R,3′R,6′R)-叶黄素转化为(3R,6′R)-α-隐花黄素的方法，产率非常高。
• [EN] PROCESS FOR THE PREPARATION OF ALPHA- AND BETA-CRYPTOXANTHIN<br/>[FR] PROCESSUS DE PREPARATION D'ALPHA ET DE BETA-CRYPTOXANTHINE
  申请人：UNIV MARYLAND

  公开号：WO2005044769A1

  公开（公告）日：2005-05-19

  The present invention relates to a process for converting lutein and/or lutein esters to β-cryptoxanthin and α-cryptoxanthin, suitable for human consumption as dietary supplements, by employing safe and environmentally friendly reagents. In the first synthetic step, commercially available lutein and/or lutein esters are transformed into a mixture of dehydration products of lutein (anhydroluteins) in the presence of a catalytic amount of an acid. The resulting anhydroluteins are then converted to β-cryptoxanthin (major product) and α-cryptoxanthin (minor product) by heterogeneous catalytic hydrogenation employing transition elements of group VIII in a variety of organic solvents under atmospheric pressure of hydrogen. A novel feature of this invention is the regioselective hydrogenation of anhydroluteins while the highly conjugated polyene chain of these carotenoids remains intact.

  本发明涉及一种将叶黄素和/或叶黄素酯转化为β-隐子黄质和α-隐子黄质的过程，适合作为膳食补充剂供人类消费，采用安全和环保的试剂。在第一合成步骤中，利用商业上可获得的叶黄素和/或叶黄素酯在少量酸的存在下转化为叶黄素的脱水产物混合物（脱水叶黄素）。然后，利用过渡元素群VIII在各种有机溶剂中，在氢气大气压下进行异质催化加氢，将所得的脱水叶黄素转化为β-隐子黄质（主要产物）和α-隐子黄质（次要产物）。本发明的一个新特点是在保持这些类胡萝卜素高度共轭多烯链完整的情况下，对脱水叶黄素进行区域选择性加氢。
• Process for Synthesis of (3R,3'R)-Zeaxanthin and (3R,3'S;meso)-Zeaxanthin from (3R,3'R,6'R)-Lutein via (3R)-3',4'-Anhydrolutein
  申请人：Khachik Frederick

  公开号：US20090238933A1

  公开（公告）日：2009-09-24

  (3R, 3′R, 6′R)-Lutein and (3R, 3′R)-zeaxanthin are two dietary carotenoids that are present in most fruits and vegetables commonly consumed in the US and accumulate in the human plasma, major organs, and ocular tissues. Another stereoisomer of (3R, 3′R)-zeaxanthin that is not of dietary origin but is found in the human ocular tissues is (3R, 3′S; meso)-zeaxanthin. There is growing evidence that these carotenoids play an important role in the prevention of age-related macular degeneration (AMD) that is the leading cause of blindness in the U.S. and the Western World. In view of the potential therapeutic application of dietary lutein, (3R, 3′R)-zeaxanthin, and (3R, 3′S; meso)-zeaxanthin, the industrial production of these carotenoids is of considerable importance. The present invention provides a process for the partial synthesis of (3R, 3′R)-zeaxanthin and (3R, 3′S; meso)-zeaxanthin from a readily accessible dehydration product of (3R, 3′R, 6′R)-lutein, namely, (3R)-3′,4′-didehydro-β,β-caroten-3-ol [(3R)-3′,4′-anhydrolutein]. The process involves regioselective hydroboration of (3R)-3′,4′-anhydrolutein to a mixture of (3R, 3′R)-zeaxanthin and (3R, 3′S; meso)-zeaxanthin followed by separation of these carotenoids by enzyme-mediated acylation.

  (3R, 3′R, 6′R)-叶黄素和(3R, 3′R)-玉米黄质是两种膳食类胡萝卜素，存在于美国常见的大多数水果和蔬菜中，并在人类血浆、主要器官和眼组织中积累。另一种立体异构体(3R, 3′S; meso)-玉米黄质虽非膳食来源，但在人眼组织中发现。越来越多的证据表明，这些类胡萝卜素在预防年龄相关性黄斑变性（AMD）方面发挥重要作用，该病是美国和西方世界导致失明的主要原因。鉴于膳食叶黄素、(3R, 3′R)-玉米黄质和(3R, 3′S; meso)-玉米黄质的潜在治疗应用，这些类胡萝卜素的工业生产具有相当重要的意义。本发明提供了一种从(3R, 3′R, 6′R)-叶黄素的易得脱水产物(3R)-3′,4′-去氢β,β-类胡萝卜烯-3-醇[(3R)-3′,4′-anhydrolutein]部分合成(3R, 3′R)-玉米黄质和(3R, 3′S; meso)-玉米黄质的方法。该过程涉及对(3R)-3′,4′-anhydrolutein的区域选择性氢硼化，得到(3R, 3′R)-玉米黄质和(3R, 3′S; meso)-玉米黄质的混合物，然后通过酶介导的酰化分离这些类胡萝卜素。
• PROCESS FOR A DIRECT ONE-POT TRANSFORMATION OF LUTEIN TO BETA-CRYPTOXANTHIN VIA ITS ACETATE ESTER
  申请人：UNIVERSITY OF MARYLAND, COLLEGE PARK

  公开号：US20160115122A1

  公开（公告）日：2016-04-28

  The present invention relates to a process for converting commercially available lutein and/or lutein esters from extracts of marigold flower petals to (3R)-β-cryptoxanthin (major) and (3R,6′R)-α-cryptoxanthin (minor) in ratios ranging from 95:5 to 98:2 in a one-pot reaction at room temperature. Because the entire process can be carried out by employing safe and environmentally friendly food-grade reagents, the resulting mixture of these carotenoids is suitable for human consumption as a dietary supplement.

  本发明涉及一种将商业上可获得的金盏花花瓣提取物中的叶黄素和/或叶黄素酯转化为(3R)-β-隐球藻黄素(主要)和(3R,6′R)-α-隐球藻黄素(次要)的过程，其比例范围从95:5到98:2，在室温下进行一锅反应。由于整个过程可以使用安全、环保的食品级试剂进行，因此这些类胡萝卜素的混合物适合作为膳食补充剂供人类食用。