1-Fluoro-2-adamantanol | 160833-79-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Fluoro-2-adamantanol
• 英文别名: 1-Fluoroadamantan-2-ol
• CAS: 160833-79-4
• 化学式: C₁₀H₁₅FO
• 分子量: 170.227
• InChiKey: CCWJZDLWMWZDPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Fluoro-2-adamantanol 在 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 以90%的产率得到1-Fluoro-2-adamantanone
  参考文献：
  名称：

  Solvolyses of Bicyclo[2.2.2]oct-1-yl and 1-Adamantyl Systems Containing an Ethylidene Substituent on the 2-Position: Typical Examples of Rate Enhancements Ascribed to Relief of F-Strain

  摘要：

  The first typical examples are described on the solvolysis rate enhancements ascribed to the relief of F-strain between an alkyl group and the leaving group atom directly attached to the reaction center. The rates and products of solvolyses in ethanol were studied for 2-methylene- and (Z)- and (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflates. Solvolyses were also conducted in ethanol and 2,2,2-trifluoroethanol (TFE) on 2-methylene- and (Z)- and (E)-2-ethylidene-1-adamantyl compounds having OMs, F, Cl, Br, or I asa leaving group. Ah the substrates gave the corresponding bridgehead substitution products as kinetic control products. The Z:E rate ratios at 25 degrees C were 217 +/- 6 for 2-ethylidenebicyclo[2.2.2]oct-1-yl triflates (ethanol) and 109 +/- Il(ethanol) and 117 fl(TFE)for 2-ethylidene-1-adamantyl mesylates. O-18 scrambling studies on the ethanolyses of(Z)- and (E)2-ethylidene-1-adamantyl mesylates showed that the titrimetrically determined Z:E rate ratios can be used as a measure of the rate ratios for the ionization step. The Z:E rate ratio in TFE at 25 degrees C for 2-ethylidene-1-adamantyl halides varied in the sequence F (ca. 70), Cl(1020 +/- 160), Br (2230 +/- 90), and I (9500 +/- 280). The significant increases in the rate ratio with the increase in the atomic size of halogen were explained in terms of the presence of F-strain in the Z substrates and its essential absence in the E substrates. Linear correlations were found in a plot of 1.36 x log[k(Z)/k(E)] against the MM2 steric energy difference between the Z and E isomers (slope 1.0) and against Hansch's Es, demonstrating the significance of F-strain effect in the enhanced rates of the (Z)-2-ethylidene-1-adamantyl system. These correlations showed an intercept of 0.8 kcal mol(-1), which suggested the greater stability of the (Z)-2-ethylidene-1-adamantyl cation than the corresponding E cation by this amount. Ab initio calculations (RHF/G-31G**) showed that the Z cation is more stable than the E cation by 1.0 kcal mol(-1), and that the large Z:E rate ratios are in part ascribed to the difference in the cation stability.

  DOI：

  10.1021/jo00094a012
• 作为产物：
  描述：

  1-Fluoro-2-adamantyl benzoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以92%的产率得到1-Fluoro-2-adamantanol
  参考文献：
  名称：

  Solvolyses of Bicyclo[2.2.2]oct-1-yl and 1-Adamantyl Systems Containing an Ethylidene Substituent on the 2-Position: Typical Examples of Rate Enhancements Ascribed to Relief of F-Strain

  摘要：

  The first typical examples are described on the solvolysis rate enhancements ascribed to the relief of F-strain between an alkyl group and the leaving group atom directly attached to the reaction center. The rates and products of solvolyses in ethanol were studied for 2-methylene- and (Z)- and (E)-2-ethylidenebicyclo[2.2.2]oct-1-yl triflates. Solvolyses were also conducted in ethanol and 2,2,2-trifluoroethanol (TFE) on 2-methylene- and (Z)- and (E)-2-ethylidene-1-adamantyl compounds having OMs, F, Cl, Br, or I asa leaving group. Ah the substrates gave the corresponding bridgehead substitution products as kinetic control products. The Z:E rate ratios at 25 degrees C were 217 +/- 6 for 2-ethylidenebicyclo[2.2.2]oct-1-yl triflates (ethanol) and 109 +/- Il(ethanol) and 117 fl(TFE)for 2-ethylidene-1-adamantyl mesylates. O-18 scrambling studies on the ethanolyses of(Z)- and (E)2-ethylidene-1-adamantyl mesylates showed that the titrimetrically determined Z:E rate ratios can be used as a measure of the rate ratios for the ionization step. The Z:E rate ratio in TFE at 25 degrees C for 2-ethylidene-1-adamantyl halides varied in the sequence F (ca. 70), Cl(1020 +/- 160), Br (2230 +/- 90), and I (9500 +/- 280). The significant increases in the rate ratio with the increase in the atomic size of halogen were explained in terms of the presence of F-strain in the Z substrates and its essential absence in the E substrates. Linear correlations were found in a plot of 1.36 x log[k(Z)/k(E)] against the MM2 steric energy difference between the Z and E isomers (slope 1.0) and against Hansch's Es, demonstrating the significance of F-strain effect in the enhanced rates of the (Z)-2-ethylidene-1-adamantyl system. These correlations showed an intercept of 0.8 kcal mol(-1), which suggested the greater stability of the (Z)-2-ethylidene-1-adamantyl cation than the corresponding E cation by this amount. Ab initio calculations (RHF/G-31G**) showed that the Z cation is more stable than the E cation by 1.0 kcal mol(-1), and that the large Z:E rate ratios are in part ascribed to the difference in the cation stability.

  DOI：

  10.1021/jo00094a012

文献信息

• Method of fluorination
  申请人：Hara Shoji

  公开号：US20060014972A1

  公开（公告）日：2006-01-19

  A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200° C. where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

  一种氟化方法，包括通过热力学或微波辐射或波长在微波区域附近的电磁波与一种通式为(I)的氟化试剂反应，反应单糖，低聚糖，多糖，由这些糖与蛋白质和脂质结合形成的复合糖和具有多元醇，醛，酮和多元醇的酸以及这些化合物的衍生物和缩聚物。根据该方法，可以在150到200°C的温度范围内安全地进行选择性的氟化反应，而在传统方法中难以进行。上述方法包括使用微波或波长在微波区域附近的电磁波辐射，可应用于除糖类以外的基质。当HF和碱组成的复合物在微波辐射下反应时，难以在传统方法中进行的特定位置的氟化反应高度选择性，高效地在短时间内安全进行。
• FLUOROADAMANTANE DERIVATIVE
  申请人：WANG Shu-zhong

  公开号：US20070129566A1

  公开（公告）日：2007-06-07

  Adamantane derivates which can be material compounds of a polymer excellent in etching resistance and having improved transmittance to light having a short wavelength, are produced by an economically advantageous process from readily available materials. A compound (10) is subjected to esterification reaction with a compound (11) to obtain a compound (12), which is subjected to fluorination in a liquid phase to obtain a compound (13), which is then subjected to hydrolysis or alcoholysis to obtain a compound (2), which is then reacted with a compound (15) thereby to obtain a compound (1). Here, A to J are —CFH— or —CF 2 —; RF is a perfluoroalkyl group or the like; X 10 is F or the like; Y 2 is H or OH; Y 3 is H or R F COO—; Y 4 is H, F or R F COO—; Y 5 is H, F, R F COO— or OH; Y 0 is H, F, —OCOCR 1 ═CH 2 or OH: R 1 is a hydrogen atom, a methyl group or the like; and X 11 is OH or a halogen atom:

  通过一种经济优势的过程，从易得材料中制备出具有优异蚀刻抗性和改善短波长光透射性的聚合物材料化合物的金刚烷衍生物。将化合物（10）与化合物（11）进行酯化反应，得到化合物（12），然后在液相中对化合物（12）进行氟化反应，得到化合物（13），然后对化合物（13）进行水解或醇解，得到化合物（2），然后将化合物（2）与化合物（15）反应，从而得到化合物（1）。其中，A至J为—CFH—或—CF2—；RF为全氟烷基或类似物；X10为F或类似物；Y2为H或OH；Y3为H或RFCOO—；Y4为H、F或RFCOO—；Y5为H、F、RFCOO—或OH；Y0为H、F、—OCOCR1═CH2或OH；R1为氢原子、甲基基团或类似物；X11为OH或卤素原子。
• METHOD OF FLUORINATION
  申请人：MITSUBISHI GAS CHEMICAL COMPANY, INC.

  公开号：EP1568703A1

  公开（公告）日：2005-08-31

  A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200°C where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

  一种氟化方法，包括使单糖、低聚糖、多糖、这些糖与蛋白质和脂类结合形成的复合糖、具有多元醇、多元醇的醛、酮和酸的糖、以及这些化合物的衍生物和缩合物与通式(I)代表的氟化剂进行热反应或在微波或波长在微波区域附近的电磁波照射下进行反应。根据该方法，可在 150 至 200°C 的温度范围内安全地进行所选位置的氟化反应，而在此温度范围内，根据传统方法很难进行反应。上述方法包括用微波或波长在微波区域附近的电磁波进行辐照，可用于糖类以外的基质。在微波辐照下反应由氟化氢和碱组成的复杂化合物时，在传统方法难以进行的特定位置上的氟化反应可在短时间内高效、安全地进行，且选择性高。
• METHOD OF FLUORINATION BY MICROWAVES
  申请人：Mitsubishi Gas Chemical Company, Inc.

  公开号：EP2189466A2

  公开（公告）日：2010-05-26

  A method of fluorination which comprises fluorinating a substrate by bringing the substrate and a fluorinating agent into reaction with each other under irradiation with at least one of microwave and electromagnetic wave having a wavelength around a microwave region; wherein the substrate is selected from the group consisting of monohydroxy alcohol; polyol having a plurality of hydroxyl groups; thiol; a compound having a carbonyl group or carboxyl group; an aromatic compound exhibiting an increased nucleophilicity due to the presence of an electron-attracting group; aromatic diazonium salt; oligosaccharide and polysaccharide; hydrocarbon having a cage shape; and epoxide; and the fluorinating agent is represented by general formula (I): wherein Y represents nitrogen atom or phosphorus atom, R0, R1 and R2 represent hydrogen atom or an alkyl or aryl group which may have substituents, the atom and the groups represented by R0, R1 and R2 may be the same with or different from each other, and two or three of the groups represented by R0, R1, and R2 may be bonded to each other to form a ring.

  一种氟化方法，包括在微波和波长在微波区域附近的电磁波中的至少一种的辐照下，使基质和氟化剂相互反应，从而使基质氟化；其中基质选自由单羟基醇组成的组；具有多个羟基的多元醇；硫醇；具有羰基或羧基的化合物；由于存在引电子基团而亲核 性增强的芳香族化合物；芳香族重氮盐；寡糖和多糖；具有笼形的碳氢化合物；以及环氧 物；氟化剂由通式(I)表示： 其中 Y 代表氮原子或磷原子，R0、R1 和 R2 代表氢原子或可带有取代基的烷基或芳基，R0、R1 和 R2 所代表的原子和基团可以彼此相同或不同，R0、R1 和 R2 所代表的两个或三个基团可以彼此键合形成环。
• Method of fluorination by microwaves
  申请人：Mitsubishi Gas Chemical Company, Inc.

  公开号：EP2189467A2

  公开（公告）日：2010-05-26

  A method of fluorination which comprises fluorinating a substrate by bringing the substrate and a complex compound comprising HF and a base into reaction with each other under irradiation with at least one of microwave and electromagnetic wave having a wavelength around a microwave region; wherein the substrate is selected from the group consisting of a compound having hydrogen atom activated by a substituent at the α position, the β-position or the γ-position, a silyl ether compound, a compound having an unsaturated group, hydroxyl group, halogeno group, amino group, diazo group, triazeno group or isocyano group as a functional group, a saccharide and a cyclic compound having a three-membered or greater ring which may have a heteroatom.

  一种氟化方法，包括在微波和波长在微波区域附近的电磁波中的至少一种波长的辐照下，使基质和由氢氟酸和碱组成的复合物相互反应，从而使基质氟化； 其中基质选自由下列组成的化合物：在α位、β位或γ位有被取代基活化的氢原子的化合物；硅烷基醚化合物；具有不饱和基团、羟基、卤基、氨基、重氮基团、三氮基团或异氰基作为官能团的化合物；糖类和具有三元或三元以上环且可能具有杂原子的环状化合物。