2,2-dimethylolbutanal | 41966-25-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethylolbutanal
• 英文别名: dimethylolbutanal；dimethylol butyraldehyde；2,2'-bis(hydroxymethyl)butanal；2,2-Bis(hydroxymethyl)butanal
• CAS: 41966-25-0
• 化学式: C₆H₁₂O₃
• 分子量: 132.159
• InChiKey: YYKMQUOJKCKTSD-UHFFFAOYSA-N

物化性质

• 沸点：
  284.1±30.0 °C(Predicted)
• 密度：
  1.101±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

安全信息

• 海关编码：
  2912491000

反应信息

• 作为反应物：
  描述：

  2,2-dimethylolbutanal 在 samarium(III) isopropoxide 、 氢气 、 铜 作用下， 以 乙醇 、 水 为溶剂， 115.0 ℃ 、3.5 MPa 条件下， 以97.4 %的产率得到三羟甲基丙烷
  参考文献：
  名称：

  一种制备2,2-二羟甲基丁醛和三羟甲基丙烷的方法

  摘要：

  本发明提供了一种制备2,2‑二羟甲基丁醛(DMB)和三羟甲基丙烷(TMP)的方法。该方法以甲醛、正丁醛和仲醇为原料，在有机碱的催化剂下发生羟醛缩合反应，过程中在催化剂的催化下发生Meerwein‑Ponndorf‑Verley(MPV)反应以抑制Cannizzaro反应的发生，减少甲酸的生成，得到高含量2,2‑二羟甲基丁醛(DMB)的缩合反应液，反应液加氢得到三羟甲基丙烷(TMP)。本发明所述方法具有缩合收率高，副产物少，TMP总收率高，成本低等优点。

  公开号：

  CN116874349A
• 作为产物：
  描述：

  正丁醛 在 聚合甲醛 、 Ca(OH)2 作用下， 生成 2,2-dimethylolbutanal
  参考文献：
  名称：

  Process for the preparation of 2,2-dimethylolalkanals

  摘要：

  本发明揭示了一种制备2,2-二甲基醇基醛的方法，其中甲醛与式RCH.sub.2CHO（I）的醛反应，其中R表示直链或支链烷基基团，碳原子数最多为12，该基团可以被1到3个碳原子的烷基或烷氧基取代，在此情况下，式I的醛与甲醛的摩尔比为1:8至20，在存在0.01至0.5摩尔（每摩尔式I的醛）的催化剂的条件下，在温度为5℃至100℃的范围内进行反应，所述催化剂基本上由碱金属或碱土金属的氢氧化物或碳酸盐或非支链三级脂肪胺组成。

  公开号：

  US04247485A1

文献信息

• METHOD FOR THE CONTINUOUS PRODUCTION OF AN AMINE USING AN ALUMINUM-COPPER CATALYST
  申请人：Ernst Martin

  公开号：US20110172430A1

  公开（公告）日：2011-07-14

  Process for the continuous preparation of an amine by reaction of a primary or secondary alcohol, aldehyde and/or ketone with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines at a temperature in the range from 60 to 300° C. in the presence of a catalyst comprising copper oxide and aluminum oxide, wherein the reaction takes place in the gas phase and the catalytically active composition of the catalyst before reduction with hydrogen comprises PS from 20 to 75% by weight of aluminum oxide (Al 2 O 3 ), from 20 to 75% by weight of oxygen-comprising compounds of copper, calculated as CuO, from 0 to 2% by weight of oxygen-comprising compounds of sodium, calculated as Na 2 O, and less than 5% by weight of oxygen-comprising compounds of nickel, calculated as NiO, and the shaped catalyst body has a pellet shape having a diameter in the range from 1 to 4 mm and a height in the range from 1 to 4 mm.

  通过在60至300°C温度范围内，在气相中存在铜氧化物和氧化铝的催化剂的情况下，通过将一级或二级醇、醛和/或酮与氢气和从氨、一级和二级胺组成的氮化合物中选择的氮化合物反应，连续制备胺的过程，其中在还原之前，催化剂的催化活性组成包括氧化铝（Al2O3）的重量百分比为20至75%，氧化铜的重量百分比为20至75%，计为CuO的氧化物的重量百分比为0至2%，计为Na2O的氧化物的重量百分比为小于5%，计为NiO的氧化物的重量百分比为小于5%，并且成型催化剂体具有直径在1至4毫米范围内和高度在1至4毫米范围内的颗粒形状。
• Hydrogenation of methylolalkanals
  申请人：Maas Steffen

  公开号：US20070282135A1

  公开（公告）日：2007-12-06

  Process for the catalytic hydrogenation of methylolalkanals of the general formula where R 1 and R 2 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 33 carbon atoms, in the liquid phase by means of hydrogen over a hydrogenation catalyst, wherein hydrogen is used in a molar ratio to methylolalkanal of greater than 1.

  对一般公式为的甲醇烷醛的催化加氢过程，在液相中通过氢气在加氢催化剂上进行，其中氢气与甲醇烷醛的摩尔比大于1，其中R1和R2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33个碳原子的芳香基团或芳基基团。
• 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。