4-(1',1'-dimethylethyl)pentanal | 142722-53-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(1',1'-dimethylethyl)pentanal
• 英文别名: 4,5,5-trimethyl-hexanal；4,5,5-Trimethylhexanal
• CAS: 142722-53-0
• 化学式: C₉H₁₈O
• 分子量: 142.241
• InChiKey: NHBINGOOBNESIC-UHFFFAOYSA-N

物化性质

• 沸点：
  179.5 °C
• 密度：
  0.8385 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  、 、 2,5,5-Trimethylhexanal 、 4-(1',1'-dimethylethyl)pentanal 、 Human Menopausal Gonadotrophin 生成 、 7-甲基辛酸
  参考文献：
  名称：

  Method for Producing Isononanoic Acids from 2-Ethyl Hexanol

  摘要：

  从2-乙基己醇制备异壬酸的过程，其特点在于：(a)在催化剂的存在下，将2-乙基己醇脱水成辛烯；(b)在元素周期表第VIII族的过渡金属化合物的存在下，将步骤a)得到的辛烯与一氧化碳和氢反应，生成异壬醛；(c)将步骤b)得到的异壬醛氧化成异壬酸。

  公开号：

  US20150191410A1
• 作为产物：
  描述：

  3-Tert-butyl-6-methoxy-6-oxohexanoic acid 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 草酰氯 、 三氯溴甲烷 、 2-mercaptopyridine-1-oxide sodium salt 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 为溶剂， 反应 2.75h， 生成 4-(1',1'-dimethylethyl)pentanal
  参考文献：
  名称：

  Stereochemistry of the reversible cyclization of .omega.-formylalkyl radicals

  摘要：

  The reactions of 6-bromo-4-(1',1'-dimethylethyl)hexanal (4), 5-bromo-3-(1',1'-dimethylethyl)pentanal (11), and 5-bromo-4-(1',1'-dimethylethyl)pentanal (17) with tributylstannane have been investigated in detail. The major products are the debrominated aldehydes and cycloalkanols which arise from the cyclization of the intermediate omega-formylalkyl radicals. The stersochemical outcome of the cyclization of these radicals is dependent on the stannane concentration. At high concentrations of stannane the cyclization is essentially irreversible with the cycloalkoxy radicals being trapped before beta-scission can occur. Under these conditions the relative amount of cis and trans cycloalkanols formed are equal to the ratio of the rate constants for the two modes of cyclization; both 4 and 17 show a small preference for trans cyclization, but 11 gives equal amounts of the two diastereomers. When the stannane concentration is lowered, the lifetime of the cycloalkoxy radicals increases allowing beta-scission to occur. Thus, the cis and trans cycloalkoxy radicals approach a thermodynamic equilibrium which is reflected in the relative yields of the cis and trans cycloalkanols.

  DOI：

  10.1021/jo00044a034

文献信息

• Method for Producing Isononanoic Acid Esters, Starting from 2-Ethyl Hexanol
  申请人：Oxea GmbH

  公开号：US20150158805A1

  公开（公告）日：2015-06-11

  A Process for preparing carboxylic esters of a mixture of structurally branched C9 monocarboxylic acids proceeding from 2-ethylhexanol is characterized in that (a) 2-ethylhexanol is dehydrated to an octene mixture in the presence of a catalyst; (b) the octene mixture obtained in step a) is reacted in the presence of a transition metal compound of group VIII of the periodic table of the elements with carbon monoxide and hydrogen to give a mixture of isomeric isononanals; (c) the mixture of isomeric isononanals obtained in step b) is oxidized to a mixture of structurally branched C9 monocarboxylic acids; and (d) the mixture of structurally branched C9 monocarboxylic acids obtained in step c) is reacted with alcohols to give carboxylic esters.

  一种制备从2-乙基己醇出发的结构分支C9单羧酸酯混合物的方法，其特征在于 (a) 在催化剂存在下，将2-乙基己醇脱水成为辛烯混合物； (b) 在步骤a)中获得的辛烯混合物在元素周期表第VIII族的过渡金属化合物存在下与一氧化碳和氢反应，得到异辛醛的混合物； (c) 在步骤b)中获得的异辛醛混合物被氧化成结构分支的C9单羧酸的混合物；以及 (d) 在步骤c)中获得的结构分支C9单羧酸混合物与醇反应，得到羧酸酯。
• 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。
• PROCESS FOR PREPARING POLYALCOHOLS FROM FORMALDEHYDE HAVING A LOW FORMIC ACID CONTENT
  申请人：Sirch Timan

  公开号：US20080167506A1

  公开（公告）日：2008-07-10

  The invention relates to a process for preparing polymethylol compounds of the formula (I) (HOCH 2 ) 2 —C—R 2 (I) where the radicals R are each, independently of one another, a further methylol group or an alkyl group having from 1 to 22 carbon atoms or an aryl or aralkyl group having from 6 to 22 carbon atoms, by condensation of aldehydes having from 2 to 24 carbon atoms with formaldehyde in an aldol reaction using tertiary amines as catalyst to form alkanals of the formula (II) where the radicals R each independently have one of the abovementioned meanings, and subsequent hydrogenation of the latter. The particular inventive feature of this process is that the aldol reaction is carried out using an aqueous formaldehyde solution having a formic acid content of <150 ppm and preferably <100 ppm. In this way of carrying out the process, the formation of by-products can advantageously be prevented in a targeted manner and the yield of the desired polymethylol compound can thereby be increased.

  该发明涉及一种制备多羟甲基化合物的方法，其化学式为(I)(HOCH2)2—C—R2(I)，其中基团R分别独立地为另一个甲醇基团或具有1至22个碳原子的烷基基团或具有6至22个碳原子的芳香基或芳基烷基基团，通过将具有2至24个碳原子的醛与甲醛在醛缩反应中使用三级胺作为催化剂进行缩合，形成化学式(II)的脂醛，其中基团R各自独立地具有上述含义之一，并随后对其进行氢化。该方法的特殊创新特点在于，在使用含有甲醛的水溶液进行醛缩反应时，其甲酸含量小于150 ppm，最好小于100 ppm。通过采用这种方法进行处理，可以有针对性地防止副产物的形成，并从而增加所需多羟甲基化合物的产率。
• METHOD FOR PREPARING POLYMETHYLOLS
  申请人：Sirch Tilman

  公开号：US20120004472A1

  公开（公告）日：2012-01-05

  The present invention relates to a process for distilling an aqueous polymethylol mixture which comprises a polymethylol of the formula (I) (HOCH 2 ) 2 —C—R 2 (I) in which each R is independently a further methylol group or an alkyl group having 1 to 22 carbon atoms or an aryl or aralkyl group having 6 to 22 carbon atoms, a tertiary amine, water and the adduct of tertiary amine and formic acid (amine formate), which comprises performing the distillation in a distillation column which is connected at the bottom to an evaporator, the bottom temperature being above the evaporation temperature of the monoester of formic acid and polymethylol (polymethylol formate) which forms during distillation. The present invention further relates to a composition comprising polymethylol and 1 to 10 000 ppm by weight of polymethylol formate, and to the use thereof.

  本发明涉及一种蒸馏含水多羟甲基混合物的工艺，该混合物包含通式(I)的多羟甲基化合物(HOCH2)2—C—R2(I)，其中每个R独立地为另一个羟甲基团或具有1至22个碳原子的烷基团，或具有6至22个碳原子的芳基或芳烷基团，以及叔胺、水和叔胺与甲酸的加合物（胺甲酸酯），该工艺包括在连接于底部蒸发器的蒸馏塔中进行蒸馏，底部温度高于蒸馏过程中形成的一甲酸酯和多羟甲基化合物（多羟甲基甲酸酯）的蒸发温度。本发明还涉及包含多羟甲基化合物及1至10000ppm重量的多羟甲基甲酸酯的组合物及其用途。
• High linear regioselectivity in the rhodium-catalyzed hydro(deuterio)formylation of 3,4,4-trimethylpent-1-ene: The role of β-hydride elimination
  作者：Raffaello Lazzaroni、Roberta Settambolo、Giuliano Alagona、Caterina Ghio

  DOI：10.1016/j.molcata.2011.12.021

  日期：2012.4

  reaction steps along branched and linear pathways have been examined to elucidate the origin of reaction reversibility. The TS for the alkyl migratory insertion onto the CO coordinated to rhodium, higher than that for the alkyl-Rh intermediate formation, explains the reason why in deuterioformylation experiments at partial conversion the monodeuterated terminal olefin TMP1-1-d1 is obtained. This occurs

  在由未改性的Rh催化剂催化加氢甲酰化反应中的区域选择性已经研究了许多α-甲基替代烷-1-烯烃（3-甲基丁-1-烯MB 1，3-甲基戊-1-烯MP 1，3，（在20°C和100 atm CO / H 2的条件下）实验获得4-二甲基戊-1-烯DMP 1和3,4,4-三甲基戊-1-烯TMP 1）总压力），理论上为B3P86 / 6-31G *水平，Rh由LanL2DZ价基集中的有效核心电势描述。对于所有的底物，已经观察到相对于支化的一种（B）占主导地位的线性醛（L）的形成（L / B> 62/38）；在TMP 1（L / B = 95/5）的情况下，L异构体几乎是排他的产物。来自部分底物转化中断的类似氘代甲酰化实验的粗反应混合物的2 H NMR研究表明，在TMP 1的情况下仅通过支链β-氢化物消除的支链醛的前体支链烷基铑中间体主要生成末端氘代烯烃，并在较小程度上生成内部烯烃。支链烷基-Rh中间体