CN114341096A - 制备二醛的方法 - Google Patents
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- 238000000034 method Methods 0.000 claims abstract description 17
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 8
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- PHYLJLLXKWRRQU-UHFFFAOYSA-N 2-[3-(2-hydroxy-1-methoxypropan-2-yl)phenyl]-1-methoxypropan-2-ol Chemical compound C1(=CC(=CC=C1)C(COC)(C)O)C(COC)(C)O PHYLJLLXKWRRQU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- MXZUXLVHHRHACS-UHFFFAOYSA-N 2-methyl-2-[4-(2-methyloxiran-2-yl)phenyl]oxirane Chemical compound C=1C=C(C2(C)OC2)C=CC=1C1(C)CO1 MXZUXLVHHRHACS-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
- C07C47/133—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group containing rings
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
公开了一种制备二醛的两步法。在该方法中,首先用醇溶剂将二‑环氧化物水解成中间体,然后对该中间体进行双频哪醇重排以获得二醛。该二醛可用作化学中间体,特别是用于制备烯醇醚化合物的方法中,烯醇醚化合物可用于以下应用中:作为增塑剂、稀释剂、润湿剂、聚结助剂,以及作为化学过程中的中间体。
Description
技术领域
本申请大体涉及化学。特别地,本申请涉及由二-环氧化物(diepoxide)制备二醛的新方法。
背景技术
单-环氧化物(mono-epoxide)至单醛的重排反应在化学领域是公知的。然而,二-环氧化物重排成二醛的方法鲜为人知。例如,当试图进行双官能重排时,普通的路易斯酸(Lewis acid)和布朗斯台德酸(Bronsted acid)会导致低聚并产生复杂的产物混合物。
二醛是特别有用的化学中间体,以制备例如烯醇醚等材料。希望能有一种由二-环氧化物制备二醛的有效方法。本文公开的发明描述了制备二醛的两步法,其中首先用醇溶剂将二-环氧化物水解成中间体,然后对该中间体进行双频哪醇重排(double-Pinacolrearrangement)以获得二醛。
发明内容
本发明在所附权利要求中提出。
在一个实施例中,本发明包含一种由二-环氧化物制备二醛的方法,该方法包含:
a)在碱的存在下将醇与二-环氧化物合并以形成第一混合物;
b)加热所述第一混合物以形成第二混合物;
c)将酸加入到第二混合物中以形成第三混合物;以及
d)从第三混合物中分离二醛。
具体实施方式
定义:
在本说明书和跟随的权利要求中,将提及许多术语,这些术语应定义为具有以下含义。
“醇”是指含有一个或多个羟基的化学品。
“醛”是指含有一个或多个-C(O)H基团的化学品。
如本文所用,术语“一个/种(a/an)”和“该/所述”表示一个/种或多个/种。
如本文所用,术语“和/或”在两个或多个项目的列表中使用时,是指所列项目中的任何一个可以单独使用,或可以使用所列项目中的两个或更多个的任何组合。例如,如果组合物被描述为含有组分A、B和/或C,则该组合物可以含有:单独的A;单独的B;单独的C;A和B的组合;A和C的组合;B和C的组合;或A、B和C的组合。
如本文所用,术语“包含(comprising/comprises/comprise)”是开放式的过渡术语,用于从该术语之前所述的对象过渡到该术语之后所述的一个或多个要素,其中在过渡术语之后列出的一个或多个要素不一定是构成该对象的仅有的要素。
如本文所用,术语“具有(having/has/have)”具有与上文提供的“包含”相同的开放式含义。
如本文所用,术语“包括(including/includes/include)”具有与上文提供的“包含”相同的开放式含义。
本文提出了一种通过新的合成方法将二-环氧化物直接转化为二醛的方法。
单-环氧化物至单醛的重排反应是公知的。然而,当试图将范围扩展至二醛到二-环氧化物的重排时,几乎没有化学选项。例如,当试图进行双官能重排时,普通的路易斯酸和布朗斯台德酸会导致低聚并产生复杂的产物混合物。发明人测试了三苯碳四氟硼酸盐(tritylium tetrafluorborate)、三氟化硼、氯化锌、甲基磺酸、固载酸(例如AmberlystTM15、NafionTMNR50),所有这些都导致低聚。已筛选的其他催化剂包括高岭土、膨润土、沸石Y、酸性氧化铝和硅胶。这些方法都没有导致反应。
我们发现了一种两步法,该方法将芳香族二-环氧化物甲醇分解成二甲醇,然后进行酸催化的重排,以成功地制备二醛。
该方法包括:
a)在碱的存在下将醇与二-环氧化物合并以形成第一混合物;
b)加热所述第一混合物以形成第二混合物;
c)将酸加入到第二混合物中以形成第三混合物;以及
d)从第三混合物中分离二醛。
适用于该方法的二-环氧化物包括:1,3-双(2-甲基环氧乙烷-2-基)苯、1,4-双(2-甲基环氧乙烷-2-基)苯、1,3-双(环氧乙烷-2-基)苯、1,4-双(环氧乙烷-2-基)苯、4,4'-双(2-甲基环氧乙烷-2-基)-1,1'-联苯,和2,6-双(2-甲基环氧乙烷-2-基)萘,和其混合物。
适用于该方法的酸包括:乙酸、甲酸、氯乙酸、二氯乙酸、三氯乙酸,和三氟乙酸,及其混合物。
适用于该方法的醇包括:甲醇、乙醇、正丙醇和异丙醇、正丁醇和仲丁醇,及其混合物。
本发明可以通过以下实例进一步说明,但是应当理解,除非另有明确说明,否则这些实例仅出于说明目的而被包括,并不旨在限制本发明的范围。
缩写:
wt%为重量百分比;hrs或h为小时;mm为毫米;m为米;GC为气相色谱法(gaschromatography);℃为摄氏度;min为分钟;tR为保留时间(retention time);g为克;mmol为毫摩尔;mol为摩尔;mL为毫升;L为升;μL为微升。
实例
实例1:制备2,2'-(1,4-亚苯基)双(1-甲氧基丙-2-醇)[2]
将KOH(49.2g,788mmol)溶解在MeOH(400mL)中,MeOH包含在1L的4颈圆底烧瓶中,该烧瓶装有热电偶、顶部搅拌器和回流冷凝器顶部的氮气入口。在加入KOH的过程中,内部温度达到60℃并通过加热套保持在该温度。在1.5小时期间加入1,4-双(2-甲基环氧乙烷-2-基)苯[1]。通过1H NMR监测反应(取等分试样并且溶解在DMSO-d6中)。一旦二-环氧化物完全消耗,将反应冷却至环境温度,逐滴加入乙酸(47.3g,788mmol)。一旦完成加入,用旋转蒸发器在减压下除去挥发物。将残余物溶于250mL甲苯中,然后用250mL水洗涤。使用分液漏斗,用250mL的EtOAc反萃取水层。合并有机物,用MgSO4干燥,同时用5g活性炭处理。过滤混合物,并用旋转蒸发器在减压下除去挥发物。2,2'-(1,4-亚苯基)双(1-甲氧基丙-2-醇)[2]分离为白色固体。LC-MS(柱A)tR:3.80分钟(精确质量:254.15m/z,发现值:254.2m/z)/。
实例2:制备2,2'-(1,4-亚苯基)二丙醛[3]
然后将2,2'-(1,4-亚苯基)双(1-甲氧基丙-2-醇)[2]溶解在甲酸(88%,98.0g)中,该甲酸包含在500mL的4颈圆底烧瓶中,该烧瓶装有热电偶、顶部搅拌器和回流冷凝器顶部的氮气入口。将混合物加热至100℃。6小时后,加入另外的甲酸(98.0g)。再过2小时后,GC表明>99%转化为2,2'-(1,4-亚苯基)二丙醛[3]。然后使用旋转蒸发器在减压下除去挥发物。将残余物溶解在250mL甲苯中,然后用NaHCO3饱和溶液洗涤。层分离后,有机物用MgSO4干燥,过滤,然后浓缩。然后在150℃/1mmHg下对粗材料进行Kugelrohr-蒸馏,以分离2,2'-(1,4-亚苯基)二丙醛[3]为无色的油。GC-MS tR:14.47分钟(精确质量:190.10m/z,发现值:190.1m/z)。
实例3:制备2,2'-(1,3-亚苯基)双(1-甲氧基丙-2-醇)5和2,2'-(1,3-亚苯基)二丙醛[6]
使用本文上述的二甲醇的制备方法,以与2,2'-(1,4-亚苯基)双(1-甲氧基丙-2-醇)[2]相似的方式制备2,2'-(1,3-亚苯基)双(1-甲氧基丙-2-醇)[5]。[LC-MS(柱B)tR:4.55分钟,4.68分钟(精确质量:254.15m/z,发现值:254.2m/z)]。使用本文上述的二醛制备方法制备2,2'-(1,3-亚苯基)二丙醛[6]。GC-MS tR:14.22分钟(精确质量:190.10m/z,发现值:190.1m/z)。
仪器参数——具有Agilent 5975B VL MSD的Agilent 6890N GC
样品制备:用甲苯将100μL样品稀释至1mL;柱:DB-530m×0.25mm×0.25μm;烘箱升温:0-4.5分钟在40℃;以20℃/分钟的速度升温至280℃,保持85分钟;注射器:温度——250℃;分流——65mL/min;载体流速——1.3mL/min;体积——1.0μL;MS:传输线——280℃;离子源温度——230℃;质量范围为——34-700amu。
条件——Agilent 1100LC:
·样品制备:DMSO中2-3mg/mL
·柱A:ZorbaxTM XDB-C18×4.6mm,5μm
·柱B:PoroshellTM EC-C1850×4.6mm,2.7μm
·柱温度:40℃
·进样体积:2μL
·DAD:190-600nm收集
·泵条件:初始——97%水(2.5mM NH4OAc)(溶剂A)和3%乙腈(溶剂B)
·梯度:
时间(min) | %溶剂A | %溶剂B | 流量(mL/min) |
0 | 97 | 3 | 1.0 |
10 | 0 | 100 | 1.0 |
25 | 0 | 100 | 1.0 |
25.1 | 97 | 3 | 1.0 |
30 | 97 | 3 | 1.0 |
·用Micromass LCT质谱仪获得质谱,该质谱仪与LC耦合。使用电喷雾电离,以正离子和负离子两种模式收集质谱。在柱后加入乙酸铵(50mM在MeOH中)(0.1mL/min)以提高电离效率。ES+/ES-扫描范围为60-3300amu(25和75V)。
本发明已参考本文所公开的实施例进行了详细描述,但是应当理解,在本发明的精神和范围内可以实现变化和修改。
Claims (4)
1.一种由二-环氧化物制备二醛的方法,所述方法包含:
a)在碱的存在下将醇与二-环氧化物合并以形成第一混合物;
b)加热所述第一混合物以形成第二混合物;
c)将酸加入到所述第二混合物中以形成第三混合物;以及
d)从所述第三混合物中分离二醛。
2.根据权利要求1所述的方法,其中,所述二-环氧化物选自包含以下的组:1,3-双(2-甲基环氧乙烷-2-基)苯、1,4-双(2-甲基环氧乙烷-2-基)苯、1,3-双(环氧乙烷-2-基)苯、1,4-双(环氧乙烷-2-基)苯、4,4'-双(2-甲基环氧乙烷-2-基)-1,1'-联苯,和2,6-双(2-甲基环氧乙烷-2-基)萘,和其混合物。
3.根据权利要求1所述的方法,其中,所述醇选自以下构成的组:甲醇、乙醇、正丙醇和异丙醇、正丁醇和仲丁醇,及其混合物。
4.根据权利要求1所述的方法,其中,所述酸选自以下构成的组:乙酸、甲酸、氯乙酸、二氯乙酸、三氯乙酸,和三氟乙酸,及其混合物。
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