WO2023125001A1 - 一种环状1,3-二酮二亚胺化合物及其合成方法与应用 - Google Patents

一种环状1,3-二酮二亚胺化合物及其合成方法与应用 Download PDF

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WO2023125001A1
WO2023125001A1 PCT/CN2022/138917 CN2022138917W WO2023125001A1 WO 2023125001 A1 WO2023125001 A1 WO 2023125001A1 CN 2022138917 W CN2022138917 W CN 2022138917W WO 2023125001 A1 WO2023125001 A1 WO 2023125001A1
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雷珺宇
张蔚
高玉李
义建军
洪柳婷
郝海军
张明革
李荣波
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中国石油天然气股份有限公司
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    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/20—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
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    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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  • the invention belongs to the field of organic synthetic chemistry, and specifically relates to a cyclic 1,3-diketodiimine compound, a synthesis method and an application thereof.
  • Open-chain ⁇ -diketodiimine is a class of ligands that have been widely studied in the past two decades. Because of its easy-to-change skeleton and nitrogen substituents, and its multifunctional tunability in terms of electronic and steric requirements, it has been It is widely used to stabilize metals with low price and low coordination number, and many of its metal complexes are active catalysts, for example, there are many applications in the fields of catalytic polymerization, organic synthesis and catalysis.
  • metal organic reagents such as Grignard reagents, organolithium reagents, alkyl zinc, alkyl aluminum reagents, etc.
  • Their chemical properties are very active, and they are easy to react with water, alcohol and other compounds with active hydrogen, resulting in their failure, so the purity requirements of the reaction solvent are very high.
  • most commercially available high-purity solvents are prepared by adsorbing small molecular compounds such as water and alcohol through molecular sieves, and the water content can reach below 100ppm. The effect is good, but the disadvantage of this method is that it consumes more power and costs more.
  • active metal reagents such as sodium metal and lithium aluminum hydride to reflux, but the risk factor of this method is too high and it is easy to cause accidents.
  • Some alcohol impurities are unavoidable in some chemical raw materials, but these impurities will greatly affect the quality of the product, such as methyl methacrylate, which is an important monomer in the production of organic glass, which can be removed by metal sodium reflux water, but alcohol compounds have low reactivity with metal sodium, which makes it difficult to remove alcohol compounds.
  • the object of the present invention is to provide a cyclic 1,3-diketone diimine compound and a synthesis method thereof, by which a cyclic 1,3-diketone containing a bulky hindered substituent is successfully prepared Diimine compounds.
  • the method is also applicable to the synthesis of cyclic 1,3-dikediimine with low steric hindrance, has a wide range of substrates, and is easy to operate in experiments, and the compound can be used to remove water and alcohol from solvents or chemical raw materials.
  • the present invention provides a cyclic 1,3-diketone diimine compound formed by condensation of cyclic 1,3-diketone and substituted aniline, which has the general formula I, II or III Structure:
  • R 1 and R 8 are independently selected from H, C 1 -C 5 saturated alkyl, preferably H or methyl;
  • n 1
  • R 2 -R 7 are selected from H, halogen, saturated alkyl of C 1 -C 10 , preferably selected from H, halogen, saturated alkyl of C 1 -C 5 , more preferably selected from H , chlorine, methyl, isopropyl.
  • R 1 and R 8 are independently selected from H, saturated C 1 -C 5 alkyl groups, preferably H and methyl groups.
  • the compound is selected from one or more of the following compounds:
  • 1,3-cyclohexanedione compounds and aniline or para-substituted aniline are heated to reflux in toluene in the presence of p-toluenesulfonic acid, followed by treatment with alkaline solution to obtain cyclic ⁇ -diketodiimine ( Bulletin of the Korean Chemical Society, 2004,25(2):163-4).
  • the inventors of the present invention have found that: under the same conditions of the above-mentioned documents, even if the reaction time is extended to 240 hours, the aniline and the cyclic ⁇ -diketone that are substituted at the 2,6 or 2,4,6 positions will not No sign of reaction.
  • the inventors of the present invention have attempted to synthesize cyclic ⁇ -dikediimines with 2,6-disubstituted large steric hindrances by all the methods for synthesizing cyclic ⁇ -diketodiimines in existing literature, such as direct method, iodine Ethane activates enaminone (Pure and Applied Chemistry, 2015, 87(9-10): 979-96), through enaminothione intermediate (Molecules, 2009, 14(6): 2278-85), through four Boron fluoride ethoxylate activates enaminone (Angewandte Chemie-International Edition, 2017,56(10):2632-5), etc., but it cannot make aniline with substituents at the 2 and 6 positions and 1,3-cyclic diketone react. Therefore, one of the tasks involved in the present invention is to explore the synthesis of corresponding cyclic ⁇ -diketodiimines with 2,6-position or 2,4,6-
  • the present invention also provides the synthetic method of above-mentioned compound, makes the compound with general formula I structure through following equation two-step reaction:
  • Step 1 The cyclic 1,3-diketone having the structure represented by the general formula IV and the substituted aniline having the structure represented by the general formula V are mixed in a molar ratio of 1:1 to 1:5 (preferably 1:1-1.2) 0.01-5 times the molar amount (preferably 1-2.5 times the molar amount) of an organic acid is catalyzed and refluxed in a benzene solvent for 1-24 hours, and treated with a 0.1-10M alkaline solution with an equimolar amount of the organic acid to obtain
  • Step 2 the enaminone with the structure shown in the general formula VI and the substituted aniline with the structure shown in the general formula VII in a molar ratio of 1:1 to 1:5 (preferably 1:1-1.2) at 0.01-5 times the molar ratio Amount (preferably 1-2.5 times the molar amount) of an organic acid catalyzed by reflux reaction in a benzene solvent for 10-120 hours to obtain the corresponding cyclic 1,3-diketone diimine organic acid salt, using an equimolar organic acid amount of 0.1-10M alkaline solution to obtain the cyclic 1,3-diketodiimine;
  • the above-mentioned synthetic method can be carried out according to the following specific steps:
  • Step 1 is shown in the following equation 1 (only for example, the reaction conditions of the present invention are not limited to the specific conditions shown in equation 1), the cyclic 1,3-diketone with the general formula IV and the cyclic 1,3-diketone with the general formula V structure
  • the substituted aniline is refluxed in a benzene solvent for 1-24 hours under the catalysis of 0.01-5 times the molar amount of an organic acid in a molar ratio of 1:1 to 1:5 to obtain an enaminone with a general formula VI structure;
  • Compounds 1a-1j are some representative enaminone compounds with general formula VI structure, but the enaminone compounds involved in the present invention are not limited to the following compounds:
  • Step 2 is as shown in the following equation 2 (only for example, the reaction conditions of the present invention are not limited to the specific conditions shown in equation 2), the enaminone with the general formula VI structure prepared by the first step reaction and the enaminone with the general formula VII
  • the substituted aniline of the structure is refluxed in a benzene solvent for 10-120 hours (preferably 30-120 hours) under the catalysis of 0.01-5 times the molar amount of an organic acid in a molar ratio of 1:1 to 1:5 to obtain the corresponding cyclic 1
  • 3-diketodiimine salt is treated with a 1M alkaline solution having an equimolar amount of an organic acid to obtain a cyclic 1,3-diketodiimine represented by the general formula I;
  • Compounds 2a-2k are some representative compounds with general formula I structure, but the compounds with general formula I involved in the present invention are not limited to these compounds:
  • the benzene solvent is benzene, toluene, xylene, diphenyl ether, trimethylbenzene, tetramethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1,2 - one or a combination of two or more of diphenylethane, ethylbenzene and diethylbenzene; the reaction temperature is 100-200°C.
  • the alkaline solution is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium tert-butoxide, tert-butoxide
  • the alkaline solution is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium tert-butoxide, tert-butoxide
  • the benzene solvent is mesitylene or a benzene solvent with a boiling point higher than or equal to mesitylene.
  • the benzene solvent having a boiling point higher than or equal to mesitylene includes one or a combination of two or more of tetramethylbenzene, dichlorobenzene, trichlorobenzene or diethylbenzene, and the reaction The temperature is 160-230°C.
  • the organic acid includes one or a combination of two or more of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and trifluoroformic acid.
  • the present invention also provides a method for removing water and alcohol compounds in the compound, which is carried out by the cyclic 1,3-diketodiimine provided by the present invention.
  • the cyclic 1,3-diketodiimine When the cyclic 1,3-diketodiimine is in contact with water and small molecule alcohols, the water and small molecule alcohols will be embedded in the cyclic 1,3-diketodiimine at a ratio of 1:1.
  • the crystal structure shows that they interact with two molecules of cyclic ⁇ -diimine in the form of hydrogen bonds; and the alcohol can only be completely removed under vacuum above 95°C, which proves that the cyclic 1,3- The hydrogen bond formed between the diketonediimine compound and the alcohol molecule is very strong.
  • this compound is applied to remove traces of water and alcohol compounds in solvents and chemical raw materials, and a certain amount of cyclic 1,3- Diketone diimine, let it stand for more than 1-10h, and filter to remove trace alcohol compounds in solvents or chemical raw materials, and its water content or alcohol content can be measured by Karl Fischer moisture analyzer or gas chromatography. at the level of 50ppm.
  • Fig. 1 is the gas chromatogram of the Hex (n-hexane) solution of the 0.1mol/L MeOH that is not processed in the obtained cyclic 1,3-dikediimine compound 2f in embodiment 4;
  • Fig. 2 is the gas chromatogram after the Hex (n-hexane) solution of 0.1mol/L MeOH is processed by the gained cyclic 1,3-diketone diimine compound 2f in embodiment 4;
  • Fig. 3 is the 1 H-NMR spectrum of the cyclic 1,3-dikediimine compound 2f obtained in Example 4 combined with a molecule of methanol.
  • the NMR spectrum was tested on a Bruker Mercury 400MHz nuclear magnetic resonance instrument in the Analysis and Testing Center of Beijing University of Chemical Technology (TMS is the internal standard, and the deuterated reagents are CDCl 3 , 99.8atom%D, with 0.03% (V/V)TMS unless otherwise specified)
  • TMS Trigger Chemical Technology
  • the high-resolution mass spectrum is tested by the Agilent G6500 Series Q-TOF mass spectrometer of Beijing University of Chemical Technology Advanced Center
  • the ultraviolet-visible spectrum is tested by the Hitachi U-3010 UV-visible spectrophotometer
  • the infrared spectrum is tested by the Nicolet 8700 infrared spectrometer.
  • X-ray single crystal diffraction was tested by Beijing University of Chemical Technology Japan Rigaku Gemin E single crystal X-ray diffractometer, and the melting point was measured by Tianjin Guoming Pharmaceutical RY-1 melting point apparatus.
  • This example provides the synthesis of cyclic 1,3-diketodiimine compound 2g, which specifically includes the following steps:
  • Volatile substances such as toluene were removed by a rotary evaporator, and the residue was added into dichloromethane until completely dissolved. Then add 1M aqueous sodium hydroxide solution in an equimolar amount to p-toluenesulfonic acid, and shake fully until the aqueous phase is weakly alkaline. The liquid was separated, the organic phase was collected, the aqueous phase was extracted three times with dichloromethane, and then the organic phases were combined and dried by adding anhydrous sodium sulfate. After filtration, the organic solvent was removed in vacuo, and the residue was dissolved by heating with toluene. After returning to room temperature, it was placed at -20°C for recrystallization.
  • This example provides the synthesis of cyclic 1,3-diketodiimine compound 2f, which specifically includes the following steps:
  • Example 1 for reaction monitoring and post-treatment methods, 4.30 g of a colorless 2f compound was obtained with a yield of 61%. Melting point: 174-175°C.
  • UV-Vis (CH2Cl2) ⁇ max 290nm ( ⁇ 19680).
  • This example provides the synthesis of cyclic 1,3-diketodiimine compound 2e, which specifically includes the following steps:
  • This example provides an application of a cyclic 1,3-diketodiimine compound 2f for removing methanol in n-hexane, which specifically includes the following steps:
  • MeOH MeOH in a 100ml volumetric flask, then dilute to 100ml with toluene (Tol), shake and shake well, and configure it as a 0.1mol/L MeOH toluene solution.
  • nPrOH nPrOH in a 100ml volumetric flask
  • dilute it to 100ml with n-hexane shake it well, and configure it as a 0.1mol/L nPrOH n-hexane (Hex) solution.
  • Hex 0.1mol/L nPrOH n-hexane

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Abstract

一种环状1,3-二酮二亚胺化合物及其合成方法与应用。该环状1,3-二酮二亚胺化合物具有如下通式、II或III所示的结构：其中，R1-R8各自独立地选自H、卤素、C1-C10的饱和烷基，n＝0或1或2。该类环状β-二亚胺对醇类化合物具有较强的结合能力，与醇类化合物以氢键方式结合后在95℃以上于真空下才能将醇类分子完全除去，可以应用于除去化合物中微量醇类化合物。

Description

一种环状1,3-二酮二亚胺化合物及其合成方法与应用 技术领域
本发明属于有机合成化学领域，具体涉及一种环状1,3-二酮二亚胺化合物和其合成方法及其应用。
背景技术
开链β-二酮二亚胺是近二十年来广为研究的一类配体，由于其骨架、氮原子取代基易于变化，在电子和空间需求方面具有多功能的可调性，于是被广泛应用于稳定低价低配位数的金属，其许多金属配合物是活性催化剂，例如在催化聚合、有机合成和催化领域有诸多应用。
环状的1,3-二酮二亚胺化合物合成报道很少，只限于一些位阻较小的脂肪胺，其应用鲜有报道。
在有机化学反应中，不可避免的使用一些金属有机试剂，如格氏试剂、有机锂试剂、烷基锌、烷基铝试剂等。它们的化学性质很活泼，易与水、醇等有活泼氢的化合物反应，而导致其失效，于是对反应溶剂的纯度要求很高。如今，市售的高纯度溶剂大多通过分子筛吸附水、醇等小分子化合物制备，含水量可以达到100ppm以下，但分子筛只有经过高温焙烧之后(至少350℃烧4小时)，除水、除醇的效果才好，该方法缺点在于耗电较多，成本较高。其次是加入金属钠、氢化铝锂等活泼金属试剂回流制备，但该方法危险系数太高，容易造成事故。
一些化工原料中很难避免的存在一些醇类杂质，但这些杂质会很大程度影响产品的品质，例如甲基丙烯酸甲酯，是生产有机玻璃的重要单体，其可以通过金属钠回流除去其中的水，但醇类化合物与金属钠反应活性较低，导致醇类化合物难以除去。
发明内容
为解决上述难题，本发明目的在于提供一种环状1,3-二酮二亚胺化合物及其合成方法，利用该方法成功制备了含有大位阻取代基的环状1,3-二酮二亚胺化合物。该方法同样适用于位阻小的环状1,3-二酮二亚胺的合成，适用底物范围广，实验操作简便，且该化合物可应用于溶剂或化工原料的除水、除醇。
为达到上述目的，本发明提供了一种由环状1,3-二酮和取代苯胺缩合生成的环状1,3-二酮二亚胺化合物，其具有通式Ⅰ、II或III所示的结构：
Figure PCTCN2022138917-appb-000001
通式I所示环状1,3-二酮二亚胺类化合物由于存在互变异构，其分子存在另外两种互变异构体，即通式II和通式III的结构，本专利中采用通式I表示。其中，R 1-R 8各自独立地选自H、卤素、C 1-C 10的饱和烷基，n＝0或1或2。
在上述化合物中，优选地：R 1、R 8各自独立地选自H、C 1-C 5的饱和烷基，优选选自H或甲基；R 2-R 7选自H、卤素、C 1-C 10的饱和烷基，优选选自H、卤素(优选包括氟、溴、氯、碘)、甲基、异丙基、乙基、丙基、正丁基、叔丁基；n＝1。
在上述化合物中，优选地：n＝1；R 1＝R 8＝H；当R 3＝R 6＝H时，R 2、R 4、R 5、R 7，为甲基、乙基、丙基、正丁基、叔丁基、异丙基、卤素中的一种，彼此相同或不同；当R 3＝R 6为甲基、乙基、丙基、叔丁基、异丙基、卤素中的一种，R 2、R 4、R 5、R 7，为甲基、乙基、丙基、正丁基、叔丁基、异丙基、卤素中的一种，彼此相同或不同。
在上述化合物中，优选地，取代基具体为R 1＝R 3＝R 6＝R 8＝H；R 2＝R 4＝R 5＝R 7＝iPr；n＝1。
在上述化合物中，优选地，取代基具体为R 1＝R 3＝R 6＝R 8＝H；R 2＝R 4＝R 5＝R 7＝CH 3；n＝1。
在上述化合物中，优选地，取代基具体为R 1＝R 8＝H；R 2＝R 3＝R 4＝R 5＝R 6＝R 7＝CH 3；n＝1。
在上述化合物中，优选地，取代基具体为R 1＝R 6＝R 8＝H；R 2＝R 3＝R 4＝H；R 5＝R 7＝iPr；n＝1。
在上述化合物中，优选地，取代基具体为R 1＝R 6＝R 8＝H；R 2＝R 3＝R 4＝CH 3；R 5＝R 7＝iPr；n＝1。
在上述化合物中，优选地，n＝1，R 1＝R 8＝H；当R 3＝R 6＝H时，R 2＝R 4＝R 5＝R 7，均为甲基或异丙基；当R 3＝R 6＝CH 3时，R 2＝R 4＝R 5＝R 7，均为甲基。
在上述化合物中，优选地，R 2-R 7选自H、卤素、C 1-C 10的饱和烷基，优选自H、卤素、C 1-C 5的饱和烷基，更优选选自H、氯、甲基、异丙基。
在上述化合物中，优选地，R 1、R 8各自独立地选自H、C 1-C 5的饱和烷基，优选自H、甲基。
在本发明的一些实施方式中，所述化合物选自以下化合物中的一种或多种：
化合物1：通式I中，R 1＝R 3＝R 6＝R 8＝H，R 2＝R 4＝R 5＝R 7＝iPr，n＝1；
化合物2：通式I中，R 1＝R 3＝R 6＝R 8＝H，R 2＝R 4＝R 5＝R 7＝CH 3，n＝1；
化合物3：通式I中，R 1＝R 8＝H，R 2＝R 3＝R 4＝R 5＝R 6＝R 7＝CH 3，n＝1；
化合物4：通式I中，R 1＝R 3＝R 5＝R 6＝R 7＝R 8＝H，R 2＝R 4＝iPr，n＝1；
化合物5：通式I中，R 1＝R 6＝R 8＝H，R 2＝R 3＝R 4＝CH 3，R 5＝R 7＝iPr，n＝1；
化合物6：通式I中，R 1＝R 3＝R 5＝R 6＝R 7＝H，R 2＝R 4＝iPr，R 8＝CH 3，n＝1；
化合物7：通式I中，R 3＝R 5＝R 6＝R 7＝R 8＝H，R 2＝R 4＝iPr，R 1＝CH 3，n＝1；
化合物8：通式I中，R 1＝R 3＝R 6＝R 8＝H，R 2＝R 4＝R 5＝R 7＝Cl，n＝1；
化合物9：通式I中，R 1＝R 8＝H，R 2＝R 3＝R 4＝R 5＝R 6＝R 7＝CH 3，n＝1。
环状β-二酮二亚胺类化合物的相关报道较少。1958年，陈德崙报道了1,3-环己二酮缩氨基胍的合成，并应用其进行抗菌实验，证明其对伤寒菌有抑制作用，但是收率很低(化学学报,1958,25(05):349-51)。1,3-环己二酮类化合物与苯胺或对位取代苯胺在对甲苯磺酸存在下，在甲苯中加热回流，随后通过碱性溶液处理即可得到环状β-二酮二亚胺(Bulletin of the Korean Chemical Society,2004,25(2):163-4)。但是，本发明的发明人研究发现：2,6位或2,4,6位均有取代的苯胺与环状β-二酮在上述文献相同的条件下，即使延长反应时间至240小时，也没有反应的迹象。本发明的发明人尝试已有文献中合成环状β-二酮二亚胺的所有方法合成2,6-二取代大位阻的环状β-二酮二亚胺，如直接法、经碘乙烷活化烯胺酮(Pure and Applied Chemistry,2015,87(9-10):979-96)、经烯胺硫酮中间体(Molecules,2009,14(6):2278-85)、经四氟化硼乙氧盐活化烯胺酮(Angewandte Chemie-International Edition,2017,56(10):2632-5)等，但无法使2、6位具有取代基的苯胺与1,3-环二酮进行反应。于是本发明涉及的工作之一就是探索合成相应的具有2,6位或2,4,6位取代大位阻的环状β-二酮二亚胺并研究其应用。
基于此，本发明还提供了上述化合物的合成方法，经如下方程式两步反应制得具有通式I结构的化合物：
步骤一、将具有通式IV所示结构的环状1,3-二酮与具有通式V所示结构的取代苯胺以1:1至1:5摩尔比(优选1:1-1.2)在0.01-5倍摩尔量(优选1-2.5倍摩尔量)的有机酸催化下于苯类溶剂中回流反应1-24小时，采用与有机酸等摩尔量的0.1-10M碱性溶液处理，得到具有通式VI所示结构的烯胺酮；
步骤二、将具有通式VI所示结构的烯胺酮与具有通式VII所示结构的取代苯胺以1:1至1:5摩尔比(优选1:1-1.2)在0.01-5倍摩尔量(优选1-2.5倍摩尔量)的有机酸催化下于苯类溶剂中回流反应10-120小时得到对应的环状1,3-二酮二亚胺有机酸盐，采用与有机酸等摩尔量的0.1-10M碱性溶液处理，得到所述环状1,3-二酮二亚胺；
Figure PCTCN2022138917-appb-000002
根据本发明的具体实施方案，优选地，上述合成方法可以按照以下具体步骤进行：
步骤一如下面方程式1所示(仅为示例，本发明的反应条件不限于方程式1所示的具体条件)，将具有通式IV的环状1,3-二酮与具有通式V结构的取代苯胺以1:1至1:5摩尔比在0.01-5倍摩尔量的有机酸催化下于苯类溶剂中回流反应1-24小时得到具有通式VI结构的烯胺酮；
Figure PCTCN2022138917-appb-000003
化合物1a-1j为一些代表性的具有通式VI结构的烯胺酮化合物，但本发明所涉及的烯胺酮化合物不仅限于以下化合物：
Figure PCTCN2022138917-appb-000004
步骤二如以下方程式2所示(仅为示例，本发明的反应条件不限于方程式2所示的具体条件)，将第一步反应制备的具有通式VI结构的烯胺酮与具有通式VII结构的取代苯胺以1:1至1:5摩尔比在0.01-5倍摩尔量的有机酸催化下于苯类溶剂中回流反应10-120小时(优选30-120小时)得到对应的环状1,3-二酮二亚胺盐，采用与有机酸等摩尔量的1M碱性溶液处理，得到通式I所示的环状1,3-二酮二亚胺；
Figure PCTCN2022138917-appb-000005
需要指出的是具有通式I的化合物在固态或溶液中可能存在如下方程式3所示的互变异构，三个互变异构结构是同一化合物：
Figure PCTCN2022138917-appb-000006
化合物2a-2k为一些代表性的具有通式I结构的化合物，但本发明所涉及的具有通式I的化合物不仅限于这些化合物：
Figure PCTCN2022138917-appb-000007
在上述合成方法中，优选地，步骤一中，所述苯类溶剂为苯、甲苯、二甲苯、二苯醚、三甲苯、四甲苯、氯苯、二氯苯、三氯苯、1,2-二苯乙烷、乙苯、二乙苯中的一种或两种以上的组合；反应温度为100-200℃。
在上述合成方法中，优选地，步骤一与步骤二中，所述碱性溶液为氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、叔丁醇钾、叔丁醇钠、二乙胺、三乙胺、吡啶中的一种或两种以上的组合。
在上述合成方法中，优选地，步骤二中，所述苯类溶剂为均三甲苯或者沸点高于或等于均三甲苯的苯类溶剂。
在上述合成方法中，优选地，所述沸点高于或等于均三甲苯的苯类溶剂包括四甲苯、二氯苯、三氯苯或二乙苯中的一种或两种以上的组合，反应温度为160-230℃。
在上述合成方法中，优选地，所述有机酸包括对甲苯磺酸、苯磺酸、甲磺酸和三氟甲酸中的一种或两种以上的组合。
本发明还提供了一种除去化合物中水、醇类化合物的方法，其是由本发明提供的环状1,3-二酮二亚胺所进行的。
采用环状1,3-二酮二亚胺与水、小分子醇类化合物接触时，水、小分子醇类化合物会以1:1的比例嵌在环状1,3-二酮二亚胺化合物之中，晶体结构表明它们以氢键的方式与两分子的环状β-二亚胺相互作用；并且只有在95℃以上于真空下才能将醇完全除去， 这证明环状1,3-二酮二亚胺化合物与醇分子间形成的氢键很牢固。于是利用该化合物这一特性，将其应用于除去溶剂、化工原料中微量的水和醇类化合物，向含有微量小分子醇类化合物的溶剂或化工原料中加入一定量的环状1,3-二酮二亚胺，静置1-10h以上，过滤，即可除去溶剂或化工原料中微量醇类化合物，其含水量或含醇量通过卡尔菲休水分测定仪或气相色谱测定均可达到低于50ppm的水平。
附图说明
图1为未经实施例4中所得环状1,3-二酮二亚胺化合物2f处理的0.1mol/L MeOH的Hex(正己烷)溶液的气相色谱图；
图2为0.1mol/L MeOH的Hex(正己烷)溶液经实施例4中所得环状1,3-二酮二亚胺化合物2f处理后的气相色谱图；
图3为实施例4中所得环状1,3-二酮二亚胺化合物2f结合一分子甲醇的 1H-NMR谱图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
本发明中所使用的分析表征仪器如下：
NMR光谱是在北京化工大学分析测试中心Bruker Mercury 400MHz核磁共振仪测试(TMS为内标，除特别说明外氘代试剂均采用CDCl 3,99.8atom％D,with 0.03％(V/V)TMS)、高分辨质谱是采用北京化工大学高精尖中心Agilent G6500 Series Q-TOF型质谱仪测试、紫外可见光谱采用日立U-3010型紫外可见分光光度计测试、红外光谱采用Nicolet 8700型红外光谱仪测试、X-射线单晶衍射采用北京化工大学日本理学牛津Gemin E型单晶X射线衍射仪测试、熔点采用天津市国铭医药RY-1型熔点仪测定。
实施例1
本实施例提供了环状1,3-二酮二亚胺化合物2g的合成，具体包括如下步骤：
步骤一 1c化合物的合成
在250ml单口瓶中加入11.21g(100mmol)1,3-环己二酮，1.90g(10.0mmol)对甲苯磺酸一水合物，19.50g(110mmol)2,6-二异丙基苯胺，加入100ml甲苯，加热回流反应10h。随后薄层色谱法监测(TLC，固定相为硅胶，展开剂比例为二氯甲烷：甲醇＝20:1)显示1,3-环己二酮原料点完全消失，并有一个新点产生。通过旋转蒸发仪将甲苯等易挥 发物质除去，残余物加入二氯甲烷直至完全溶解。随后加入与对甲基苯磺酸等摩尔量的1M氢氧化钠水溶液，充分摇晃，直至水相呈弱碱性。分液，收集有机相，用二氯甲烷萃取水相三次，之后合并有机相，加入无水硫酸钠干燥。过滤后，真空除去有机溶剂，残余物加入甲苯加热溶解，恢复室温后置于-20℃重结晶。第一次重结晶得到白色针状晶体20.63g，母液浓缩后第二次重结晶得到白色针状晶体2.02g，合计得到1c：22.65g。理论产量：27.14g，产率：83％。熔点：210-213℃。
1H NMR(400MHz)δ7.32–7.23(t, 3J H-H＝7.6Hz,1H,Ar-H),7.14(d, 3J H-H＝7.7Hz,2H,Ar-H),6.11(s,1H,NH),4.69(s,1H,＝CH),3.09–2.86(m,2H,CH(CH 3) 2),2.56(t, 3J H-H＝6.2Hz,2H,CH 2),2.28(t, 3J H-H＝6.5Hz,2H,CH 2),2.06–1.97(m,2H,CH 2),1.14(m,12H,CH(CH 3) 2)；
13C NMR(101MHz)δ197.38,165.12,146.53,131.93,128.70,123.87,99.12,36.43,29.19,28.44,24.51,23.22；
HR-MS m/z(％):calculated 272.2009,found 272.2056[M+H] +；IR(KBr,cm -1):3433.1,3192.3,2962.8,1598.1,1535.8,1467.1,860.0,806.6,774.9.UV-Vis(CH 2Cl 2)λ max 281nm(ε＝21740)。
步骤二 2g化合物的合成
在100ml单口瓶中加入1.36g(5.0mmol)化合物1c，0.95g(5.0mmol)对甲苯磺酸一水合物，0.68g(5.0mmol)2,4,6-三甲基苯胺，加入20ml均三甲苯，加热回流反应52h。经薄层色谱TLC分析，发现原料点消失，并有一个新点产生。通过旋转蒸发仪将溶剂除去，残余物加入二氯甲烷直至完全溶解(约20ml)。随后加入与对甲基苯磺酸等摩尔量的1M氢氧化钠水溶液，充分摇晃，直至水相呈弱碱性。分液，收集有机相，用10ml二氯甲烷萃取水相三次后合并有机相，采用无水硫酸钠干燥。过滤后，真空除去有机溶剂，残余物加入5ml甲醇静置，有白色固体析出，过滤，用少量甲醇洗涤，得到无色固体1.21g，理论产量：1.94g，产率:62％。190℃变黑，熔点：208-211℃。
1H NMR(400MHz)δ6.69–7.05(m,6H,Ar-H),5.07(s,1H,＝CH),4.26(s,1H,NH),2.85(s,2H,CH(CH 3) 2),2.58(s,1H,CH 2),2.41(s,1H,CH 2),2.23-2.36(m,4H,CH 2),1.95(s,3H,CH 3),1.82(s,6H,CH 3),1.05-1.26(m,10H,CH(CH 3) 2),0.89(s,2H,CH(CH 3) 2)；
HR-MS m/z(％):calculated 389.3020,found 389.2951(M ++H)；IR(KBr,cm -1):3442.37,2960.245,2865.749,1573.658,1598.725,1376948,1257.381,777.185.UV-Vis(CH 2Cl 2)λ max 295nm(ε＝19780)。
实施例2
本实施例提供了环状1,3-二酮二亚胺化合物2f的合成，具体包括如下步骤：
在100ml单口瓶中加入实施例1中步骤一的产物1c化合物2.72g(10.0mmol)，1.90g(10.0mmol)对甲苯磺酸一水合物，1.95g(11.0mmol)2,6-二异丙基苯胺，加入20ml均三甲苯，加热回流反应52h。
反应监测及后处理方法参考实施例1，得到无色2f化合物4.30g，产率：61％。熔点：174-175℃。
1H NMR(400MHz)δ7.27–6.82(m,6H,Ar-H),5.10(s,1H,＝CH),4.32(s,1H,NH),3.17(s,1H,CH(CH 3) 2),2.84(s,3H,CH(CH 3) 2),2.58(s,3H,CH 2),2.05(s,2H,CH 2),1.86(s,1H,CH 2),1.09-1.17(m,20H,CH(CH 3) 2),0.89(s,4H,CH(CH 3) 2)；
HR-MS m/z(％):calculated 431.3421,found 431.3465(M++H)；IR(KBr,cm -1):
3422.2,3233.8,3059.8,2959.1,2865.2,1602.3,1575.0,1524.7,1467.2,1435.5,1362.7,1264.4,1197.4.UV-Vis(CH2Cl2)λ max 290nm(ε＝19680)。
实施例3
本实施例提供了环状1,3-二酮二亚胺化合物2e的合成，具体包括如下步骤：
步骤一 化合物1b的合成
在250ml单口瓶中加入11.21g(100mmol)1,3-环己二酮，1.90g(10.0mmol)对甲苯磺酸一水合物，13.52g(110mmol)2,4,6-三甲基苯胺，加入100ml甲苯，加热回流反应10h，随后TLC监测及后处理方式参考化合物1c。第一次重结晶得到橙黄色块状晶体17.11g，母液浓缩后第二次重结晶得到橙黄色块状晶体1.73g，合计得到1b:18.84g。理论产量：22.93g，产率：82％。熔点：250-252℃。
1H NMR(400MHz)δ6.87(s,2H,Ar-H),5.84(s,1H,NH),4.69(s,1H,＝CH),2.52(t, 3J H-H＝5.6Hz,2H,CH 2),2.31(t, 3J H-H＝6.5Hz,2H,CH 2),2.26(s,3H,p-ArCH 3),2.12(s,6H,o-ArCH 3),2.03(m,2H,CH 2)；
13C NMR(101MHz)δ197.69,163.58,137.56,135.66,131.92,129.18,98.42,36.42,29.19,22.13,20.92,17.81；
ESI-MS m/z(％):calculated 229.32,found 230.01[M+H] +；IR(KBr,cm -1):3435.6,3236.2,2943.8,2918.3,1758.8,1567.6,1521.4,1431.0,1361.6,852.7,826.1,769.6.UV-Vis(CH 2Cl 2)λ max 281nm(ε＝23320)。
步骤二 2e的合成
反应操作同实施例2，其中仅将原料1c替换为1b。2e的分析数据：产率：67％。熔点：199-202℃。
1H NMR(400MHz)δ6.79(s,4H,Ar-H),5.30(s,1H,＝CH),4.80(s,1H,NH),2.50–2.24(m,4H,CH 2),2.22(s,6H,p-ArCH 3),2.02(s,12H,o-ArCH 3),1.88(hept, 3J H-H＝6.5Hz, 2H,CH 2). 13C NMR(101MHz)δ161.52,142.32,137.57,134.01,128.54,123.67,98.51,29.69,27.70,22.11,20.78,17.93；
HR-MS m/z(％):calculated 347.2482,found 347.2492(M ++H)；IR(KBr,cm -1):3435.6,3166.7,2935.4,2862.6,1697.7,1611.0,1574.0,1531.9,1480.5,1418.2,1259.1,1211.3.UV-Vis(CH 2Cl 2)λ max 290nm(ε＝26180)。
实施例4
本实施例提供了一种环状1,3-二酮二亚胺化合物2f的应用，用于除去正己烷中的甲醇，具体包括如下步骤：
取(0.01mol，0.32g，0.404ml)MeOH于100ml容量瓶中，随后用正己烷定容到100ml，振荡摇匀，配置为0.1mol/L MeOH的正己烷(Hex)溶液，并通过气相色谱确定0.1mol/L MeOH的正己烷(Hex)溶液中的甲醇含量，见图1。
取10ml 0.1mol/L MeOH/Hex溶液于50ml圆底瓶中，加入(1.0mmol，0.43g)化合物2f，振荡后静置2h，通过蒸馏的方法，将溶剂与化合物2f分离，随后通过气相色谱确定甲醇含量的变化(色谱柱为毛细管柱，检测器为氢火焰检测器，设置检测室温度为99℃，汽化室温度为99℃，柱室温度79℃)。气相色谱结果显示正己烷中甲醇已经被除去，见图2，同时过滤后的化合物2f固体常压下抽真空后，进行核磁氢谱分析，在化学位移为3.49ppm处有甲醇特征峰存在，证明甲醇已与化合物2f结合，核磁氢谱图见图3。
实施例5
取(0.01mol，0.32g，0.404ml)MeOH于100ml容量瓶中，随后用甲苯(Tol)定容到100ml，振荡摇匀，配置为0.1mol/L MeOH的甲苯溶液。取10ml 0.1mol/L MeOH/Tol溶液于50ml圆底瓶中，加入(1.0mmol，0.43g)化合物2f，振荡后静置2h，通过蒸馏的方法，将溶剂与化合物2f分离，随后通过气相色谱确定甲醇含量的变化(色谱柱为毛细管柱，检测器为氢火焰检测器，设置检测室温度为140℃，汽化室温度为140℃，柱室温度120℃)。气相色谱结果显示甲苯中甲醇已经被除去，化合物2f核磁氢谱分析，显示化合物2f结合了一分子甲醇。
实施例6
取(0.01mol，0.46g)EtOH于100ml容量瓶中，随后用正己烷定容到100ml，振荡摇匀，配置为0.1mol/L EtOH的正己烷(Hex)溶液。取10ml 0.1mol/L EtOH/Hex溶液于50ml圆底瓶中，加入(1.0mmol，0.43g)化合物2f，振荡后静置2h，后处理及检测方法参考实施例4。气相色谱结果显示正己烷中乙醇已经被除去，同时过滤后的化合物 2f固体常压下抽真空后，进行核磁氢谱分析，显示有一分子乙醇存在。
实施例7
取(0.01mol，0.60g)nPrOH于100ml容量瓶中，随后用正己烷定容到100ml，振荡摇匀，配置为0.1mol/L nPrOH的正己烷(Hex)溶液。取10ml 0.1mol/L nPrOH/Hex溶液于50ml圆底瓶中，加入(1.0mmol，0.43g)化合物2f，振荡后静置2h，后处理及检测方法参考实施例4。气相色谱结果显示正己烷中正丙醇已经被除去，同时过滤后的化合物2f固体常压下抽真空后，进行核磁氢谱分析，显示有一分子正丙醇存在。
实施例8
取(0.01mol，0.60g)iPrOH于100ml容量瓶中，随后用正己烷定容到100ml，振荡摇匀，配置为0.1mol/L iPrOH的正己烷(Hex)溶液。取10ml 0.1mol/L iPrOH/Hex溶液于50ml圆底瓶中，加入(1.0mmol，0.43g)化合物2f，振荡后静置2h，后处理及检测方法参考实施例4。气相色谱结果显示正己烷中异丙醇已经被除去，同时过滤后的化合物2f固体常压下抽真空后，进行核磁氢谱分析，显示存在一分子异丙醇。

Claims (23)

  1. 一种环状1,3-二酮二亚胺化合物，其中，该环状1,3-二酮二亚胺化合物具有如下通式、II或III所示的结构：
    Figure PCTCN2022138917-appb-100001
    其中，R 1-R 8各自独立地选自H、卤素、C 1-C 10的饱和烷基，n＝0或1或2。
  2. 根据权利要求1所述的化合物，其中，
    R 1、R 8各自独立地选自H、C 1-C 5的饱和烷基；
    R 2-R 7选自H、卤素、C 1-C 10的饱和烷基；
    n＝1。
  3. 根据权利要求2所述的化合物，其中，R 1、R 8各自独立地选自H或甲基。
  4. 根据权利要求2所述的化合物，其中，R 2-R 7选自H、卤素、甲基、异丙基、乙基、丙基、正丁基、叔丁基。
  5. 根据权利要求4所述的化合物，其中，所述卤素包括氟、氯、溴、碘。
  6. 根据权利要求1所述的化合物，其中，
    n＝1；
    R 1＝R 8＝H；
    当R 3＝R 6＝H时，R 2、R 4、R 5、R 7为甲基、乙基、丙基、正丁基、叔丁基、异丙基、卤素中的一种，彼此相同或不同；当R 3＝R 6为甲基、乙基、丙基、叔丁基、异丙基、卤素中的一种时，R 2、R 4、R 5、R 7为甲基、乙基、丙基、正丁基、叔丁基、异丙基、卤素中的一种，彼此相同或不同。
  7. 根据权利要求1所述的化合物，其中，R 1＝R 3＝R 6＝R 8＝H；R 2＝R 4＝R 5＝R 7＝iPr；n＝1。
  8. 根据权利要求1所述的化合物，其中，R 1＝R 3＝R 6＝R 8＝H；R 2＝R 4＝R 5＝R 7＝CH 3；n＝1。
  9. 根据权利要求1所述的化合物，其中，R 1＝R 8＝H；R 2＝R 3＝R 4＝R 5＝R 6＝R 7＝CH 3；n＝1。
  10. 根据权利要求1所述的化合物，其中，R 1＝R 6＝R 8＝H；R 2＝R 3＝R 4＝H；R 5＝R 7＝iPr；n＝1。
  11. 根据权利要求1所述的化合物，其中，R 1＝R 6＝R 8＝H；R 2＝R 3＝R 4＝CH 3；R 5＝R 7＝iPr；n＝1。
  12. 根据权利要求1所述的化合物，其中，n＝1，R 1＝R 8＝H；
    当R 3＝R 6＝H时，R 2＝R 4＝R 5＝R 7，均为甲基或异丙基；当R 3＝R 6＝CH 3时，R 2＝R 4＝R 5＝R 7，均为甲基。
  13. 根据权利要求1所述的环状1,3-二酮二亚胺化合物的合成方法，其中，该合成方法包括如下步骤：
    步骤一、将具有通式IV所示结构的环状1,3-二酮与具有通式V所示结构的取代苯胺以1:1至1:5摩尔比在0.01-5倍摩尔量的有机酸催化下于苯类溶剂中回流反应1-24小时，采用与有机酸等摩尔量的0.1-10M碱性溶液处理，得到具有通式VI所示结构的烯胺酮；
    步骤二、将具有通式VI所示结构的烯胺酮与具有通式VII所示结构的取代苯胺以1:1至1:5摩尔比在0.01-5倍摩尔量的有机酸催化下于苯类溶剂中回流反应10-120小时得到对应的环状1,3-二酮二亚胺有机酸盐，采用与有机酸等摩尔量的0.1-10M碱性溶液处理，得到所述环状1,3-二酮二亚胺；
    Figure PCTCN2022138917-appb-100002
  14. 根据权利要求13所述的方法，其中，步骤一中，具有通式IV所示结构的环状1,3-二酮与具有通式V所示结构的取代苯胺的摩尔比为1:1-1.2。
  15. 根据权利要求13所述的方法，其中，步骤一中，将具有通式IV所示结构的环状1,3-二酮与具有通式V所示结构的取代苯胺在1-2.5倍摩尔量的有机酸催化下于苯类溶剂中回流反应。
  16. 根据权利要求13所述的方法，其中，步骤二中，具有通式VI所示结构的烯胺酮与具有通式VII所示结构的取代苯胺的摩尔比为1:1-1.2。
  17. 根据权利要求13所述的方法，其中，步骤二中，将具有通式VI所示结构的烯胺酮与具有通式VII所示结构的取代苯胺在1-2.5倍摩尔量的有机酸催化下于苯类溶剂中回流反应。
  18. 根据权利要求13所述的方法，其中，步骤一中，所述苯类溶剂为苯、甲苯、二甲苯、二苯醚、三甲苯、四甲苯、氯苯、二氯苯、三氯苯、1,2-二苯乙烷、乙苯、二乙苯中的一种或两种以上的组合；反应温度为100-200℃。
  19. 根据权利要求13所述的方法，其中，步骤一与步骤二中，所述碱性溶液为氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、叔丁醇钾、叔丁醇钠、二乙胺、三乙胺、吡啶中的一种或两种以上的组合。
  20. 根据权利要求13所述的方法，其中，步骤二中，所述苯类溶剂为均三甲苯或者沸点高于或等于均三甲苯的苯类溶剂，反应温度为160-230℃。
  21. 根据权利要求20所述的方法，其中，所述沸点高于或等于均三甲苯的苯类溶剂包括四甲苯、二氯苯、三氯苯和二乙苯中的一种或两种以上的组合。
  22. 根据权利要求13所述的方法，其中，所述有机酸为对甲苯磺酸、苯磺酸、甲磺酸和三氟甲酸中的一种或两种以上的组合。
  23. 一种除去化合物中水、醇类化合物的方法，其是由权利要求1所述的环状1,3-二酮二亚胺化合物所进行的。
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