3-Hydroxy-2,2-dimethylpropanal dimethyl acetal | 87395-22-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Hydroxy-2,2-dimethylpropanal dimethyl acetal
• 英文别名: 3,3-dimethoxy-2,2-dimethylpropanol；3,3-dimethoxy-2,2-dimethyl-propan-1-ol；3-hydroxy-2,2-dimethyl-propionaldehyde dimethyl acetal；3,3-Dimethoxy-2,2-dimethylpropan-1-ol
• CAS: 87395-22-0
• 化学式: C₇H₁₆O₃
• 分子量: 148.202
• InChiKey: OKWKPATVWIVZGI-UHFFFAOYSA-N

物化性质

• 沸点：
  85 °C(Press: 14 Torr)
• 密度：
  0.957±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-Hydroxy-2,2-dimethylpropanal dimethyl acetal 在 palladium on activated charcoal 盐酸 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 aluminum amalgam 、 正丁基锂 、 camphor-10-sulfonic acid 、 氢气 、 四氯化钛 、 对甲苯磺酸 、 乙酰氯 、 N,N'-二环己基碳二亚胺 、 pyridinium chlorochromate 、 potassium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 、 苯 为溶剂， 反应 40.5h， 生成 (3R,6S)-3-Methyl-6-((Z)-(2S,8S,9R)-2,8,9-trihydroxy-1,1-dimethyl-dec-5-enyl)-tetrahydro-pyran-2-one
  参考文献：
  名称：

  Stereocontrolled synthesis of the C(1)-C(17) half of boromycin

  摘要：

  DOI：

  10.1021/ja00359a041
• 作为产物：
  描述：

  2,2-二甲基-3-羟基丙醛 在 盐酸 、 原甲酸三甲酯 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 生成 3-Hydroxy-2,2-dimethylpropanal dimethyl acetal
  参考文献：
  名称：

  Metabolites of pentanedioic acid derivatives

  摘要：

  本发明涉及戊二酸衍生物。本发明还涉及含有这种化合物的药物组合物，以及将这种化合物和组合物用作降脂药物。

  公开号：

  US05055613A1

文献信息

• PROCESS FOR THE PRODUCTION OF NEOPENTYLGLYCOL USING FORMALDEHYDE WITH A LOW METHANOL CONTENT
  申请人：Sirch Tilman

  公开号：US20080004475A1

  公开（公告）日：2008-01-03

  A process is provided for the preparation of polymethylol compounds of formula (I): (HOCH 2 ) 2 —C—(R) 2 ,   (I) in which the radicals R independently of one another are each a further methylol group, an alkyl group having from 1 to 22 C atoms or an aryl or aralkyl group having from 6 to 22 C atoms, by (a) condensing aldehydes having from 2 to 24 C atoms with formaldehyde in an aldol reaction using tertiary amines as a catalyst to give alkanals of formula (II): in which the radicals R independently of one another are each as defined above, (b) then separating, by distillation, the reaction mixture obtained into a bottom product comprising predominantly the compounds of formula II and a low-boiling stream consisting of unconverted or partially converted starting materials, and (c) hydrogenating the distillation bottom, wherein the aldol reaction is carried out with an aqueous formaldehyde solution having a methanol content of 0.35 to 0.5% by weight of methanol, the low-boiling stream is separated off at a pressure of 1 to 3 bar and temperatures of 100 to 135° C. and completely or partially recycled into the aldol reaction. This procedure advantageously makes it possible specifically to prevent the formation of by-products and hence to increase the yield of the desired polymethylol compound. We have found that this object is achieved by a process for the preparation of polymethylol compounds of formula (I): (HOCH 2 ) 2 —C—(R) 2 ,   (I) in which the radicals R independently of one another are each a further methylol group, an alkyl group having from 1 to 22 C atoms or an aryl or aralkyl group having from 6 to 22 C atoms, by (a) condensing aldehydes having from 2 to 24 C atoms with formaldehyde in an aldol reaction using tertiary amines as a catalyst to give alkanals of formula (II): in which the radicals R independently of one another are each as defined above, (b) then separating, by distillation, the reaction mixture obtained (aldolization product) into a bottom product comprising predominantly the compounds of formula II and a low-boiling stream consisting of unconverted or partially converted starting materials, and (c) hydrogenating the distillation bottom, wherein the aldol reaction is carried out with an aqueous formaldehyde solution having a methanol content of 0.35 to 0.5% by weight, the separation of the low-boiling stream is effected at a pressure of 1.1 to 3 bar, preferably 1.5 bar, and a temperature of 100 to 135° C., preferably of 102 to 125° C., and the low-boiling stream is completely or partially recycled into the aldol reaction, preferably the entire low-boiling stream being recycled. In the aldol reaction, a partially converted starting compound of formula (III): can also be formed in which the radicals R independently of one another are each hydrogen or are as defined above. According to the invention, this partially converted starting compound of formula (III), together with the desired alkanal of formula (II), is separated from the other by-products and the unreacted starting compounds and reacted again in an aldol reaction with formaldehyde having a methanol content of 0.35% by weight to 0.5% by weight, using tertiary amines as a catalyst.

  提供了一种制备通式(I)的聚羟甲基化合物的方法：(HOCH2)2—C—(R)2，其中R基团彼此独立地分别为另一个羟甲基、具有1至22个碳原子的烷基、或具有6至22个碳原子的芳基或芳烷基，该方法包括：(a) 在叔胺催化剂存在下，通过醇醛反应将具有2至24个碳原子的醛与甲醛缩合，得到通式(II)的烷基醛：其中R基团彼此独立地如上定义，(b) 然后通过蒸馏将获得的反应混合物分离成主要包含通式(II)化合物的底部产物和由未转化或部分转化的起始材料组成的低沸点流，以及(c) 氢化蒸馏底部，其中醇醛反应使用含有0.35%至0.5%重量甲醇的甲醛水溶液进行，低沸点流在1至3巴的压力和100至135°C的温度下分离，并完全或部分循环回醇醛反应中。这种方法特别有利于防止副产物的形成，从而提高所需聚羟甲基化合物的收率。我们发现，通过一种制备通式(I)的聚羟甲基化合物的方法可以实现这一目标：(HOCH2)2—C—(R)2，其中R基团彼此独立地如上定义，该方法包括：(a) 在叔胺催化剂存在下，通过醇醛反应将具有2至24个碳原子的醛与甲醛缩合，得到通式(II)的烷基醛：其中R基团彼此独立地如上定义，(b) 然后通过蒸馏将获得的反应混合物（醇醛化产物）分离成主要包含通式(II)化合物的底部产物和由未转化或部分转化的起始材料组成的低沸点流，以及(c) 氢化蒸馏底部，其中醇醛反应使用含有0.35%至0.5%重量甲醇的甲醛水溶液进行，低沸点流的分离在1.1至3巴的压力下进行，优选1.5巴，温度为100至135°C，优选102至125°C，低沸点流完全或部分循环回醇醛反应中，优选整个低沸点流循环。在醇醛反应中，还可以形成部分转化的起始化合物通式(III)：其中R基团彼此独立地分别为氢或如上定义。根据本发明，这种部分转化的起始化合物通式(III)与所需的烷基醛通式(II)一起，从其他副产物和未反应的起始化合物中分离出来，并在叔胺催化剂存在下，使用含有0.35%重量至0.5%重量甲醇的甲醛进行再次醇醛反应。
• Poly(ethylene glycol) with Multiple Aldehyde Functionalities Opens up a Rich and Versatile Post-Polymerization Chemistry
  作者：Jan Blankenburg、Kamil Maciol、Christoph Hahn、Holger Frey

  DOI：10.1021/acs.macromol.8b02639

  日期：2019.2.26

  Two novel epoxide monomers 3,3-dimethoxy-propanyl glycidyl ether (DMPGE) and 3,3-dimethoxy-2,2-dimethylpropanyl glycidyl ether (DDPGE) were developed for the introduction of multiple aldehyde functionalities into the poly(ethylene glycol) (PEG) backbone. The acetal protecting group for the aldehyde functionality is stable against the harsh, basic conditions of the anionic ring-opening polymerization

  研发了两种新型环氧化物单体3,3-二甲氧基-丙氧基缩水甘油醚（DMPGE）和3,3-二甲氧基-2,2-二甲基丙氧基缩水甘油醚（DDPGE），用于将多种醛官能团引入聚乙二醇（ PEG）骨架。醛官能团的缩醛保护基团对阴离子开环聚合反应的苛刻碱性条件是稳定的。两种单体均可以受控方式与环氧乙烷（EO）进行均聚和无规共聚。获得了分子量（M n）在4500-20100 g / mol范围内且分散度（M w / M n）在1.06和1.14之间的共聚物。通过尺寸排阻色谱对聚合物进行表征，1 H NMR光谱法，以及关于它们的热性质的差示扫描量热法。通过MALDI-TOF验证了共聚的可控制特征。为了研究缩醛保护的醛官能团在聚醚链上的分布，通过原位1 H NMR动力学实验监测了两种单体与EO的共聚反应。这些测量结果显示，具有反应性比率对r EO = 0.96，r DMPGE = 1.04和r EO = 1.20，r
• A Novel Approach to the Synthesis of Taxol. A Synthesis of Optically Active 3,7-dibenzyloxy-4,8-di-<i>t</i>-butyl-dimethylsiloxy-5,5-dimethyl-6-<i>p</i>-methoxybenzyloxy-2-octanone by Way of Stereoselective Aldol Reactions
  作者：Teruaki Mukaiyama、Isamu Shiina、Kaku Sakata、Takayuki Emura、Keitarou Seto、Masahiro Saitoh

  DOI：10.1246/cl.1995.179

  日期：1995.3

  of diastereoselective aldol reaction between 4-benzyloxy-5-t-butyldimethylsiloxy-2,2-dimethyl-3-p-methoxy-benzyloxypentanal (3) and ketene silyl acetal 4 using MgBr2·OEt2 as a catalyst. The chiral pentanal 3 was synthesized either by asymmetric aldol reaction of both prochiral aldehyde 5 and ketene silyl acetal 4 using a chiral Lewis acid or by diastereoselective aldol reaction between the chiral aldehyde

  光学活性 3,7-dibenzyloxy-4,8-​​di-t-butyldimethylsiloxy-5,5-dimethyl-6-p-methoxybenzyloxy-2-octanone (2) 已通过 4-benzyloxy- 之间的非对映选择性羟醛反应合成5-叔丁基二甲基甲硅烷氧基-2,2-二甲基-3-对甲氧基-苄氧基戊醛(3)和乙烯酮甲硅烷基缩醛4，以MgBr2·OEt2为催化剂。手性戊醛 3 是通过使用手性路易斯酸的前手性醛 5 和烯酮甲硅烷基缩醛 4 的不对称羟醛反应合成的，或者通过衍生自 L-丝氨酸的手性醛 6 和衍生自异丁酸甲酯的烯醇锂之间的非对映选择性羟醛反应合成的。
• Oxidation of Allylic Alcohols by Means of Electrochemical Methodology. Novel Rearrangement of Prenol under Direct Anodic Oxidation Conditions
  作者：Shojiro Maki、Katsuhiro Konno、Hiroaki Takayama

  DOI：10.1246/cl.1995.559

  日期：1995.7

  Electrochemical oxidation of naturally occurring allylic alcohols is described. Under direct anodic oxidation conditions, prenol 1 was readily oxidized, followed by rearrangement presumably on the surface of the anodic electrode, to give 3-hydroxy-2,2′-dimethyl-1,1′-dimethoxy propane 2 in high yield, whereas geraniol 5 afforded citral 6 under the same conditions.

  描述了天然存在的烯丙醇的电化学氧化。在直接阳极氧化条件下，异戊二烯醇 1 很容易被氧化，随后可能在阳极电极表面发生重排，以高产率得到 3-羟基-2,2'-二甲基-1,1'-二甲氧基丙烷 2，而香叶醇 5 在相同条件下得到柠檬醛 6。
• Polysaccharide graft polymers containing acetal groups and their
  申请人：National Starch and Chemical Corporation

  公开号：US04866151A1

  公开（公告）日：1989-09-12

  Polysaccharide graft polymers which comprise an acetal-containing or aldehyde-containing homopolymer or copolymer grafted to a polysaccharide base have been prepared. The monomer repeating units in the homopolymer are derived from one or more ethylenically or allylically unsaturated monomers containing an acetal group or aldehyde group; The monomer repeating units in the copolymer are derived from the above monomer and derived from one or more ethylenically or allylically unsaturated monomers other than the acetal-containing or aldehyde-containing monomer. A and A' are independently a lower alkyl or A and A' together form at least a 5-membered cyclic acetal; with the proviso that the graft polymer contain no ##STR1## groups when the aldehyde groups are present. The aldehyde-containing graft polymers are useful for imparting wet strength to paper. Various novel acetal- and aldehyde-containing monomers have also been prepared; they can be graft polymerized to polysaccharide substrates or polymerized by conventional emulsion polymerization techniques with vinyl polymerizable monomers.

  已经制备出了包含缩醛基或醛基的同聚物或共聚物嫁接到多糖基底上的多糖嫁接聚合物。同聚物中的单体重复单元来自于一个或多个含有缩醛基或醛基的乙烯基或烯丙基不饱和单体；共聚物中的单体重复单元来自于上述单体和来自于一个或多个不含缩醛基或醛基单体的乙烯基或烯丙基不饱和单体。A和A'分别是较低的烷基或A和A'一起形成至少一个5元环缩醛基；但是嫁接聚合物在存在醛基时不包含##STR1##基团。含有醛基的嫁接聚合物对于赋予纸张湿强度很有用。还制备了各种新型含缩醛基和醛基的单体；它们可以嫁接聚合到多糖基底上或通过常规乳液聚合技术与乙烯基可聚合单体共聚合。