CN112174893B - 一种2,4,5-三甲基-1h-咪唑啉甲酸盐的合成方法及用途 - Google Patents
一种2,4,5-三甲基-1h-咪唑啉甲酸盐的合成方法及用途 Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 8
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 150000004675 formic acid derivatives Chemical class 0.000 claims abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- NWYYWIJOWOLJNR-RXMQYKEDSA-N l-valinol Chemical compound CC(C)[C@H](N)CO NWYYWIJOWOLJNR-RXMQYKEDSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 238000002447 crystallographic data Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- -1 nitrogen-containing compound Chemical class 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000003814 drug Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTBPTNCGZUOCBK-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole Chemical compound CC1=NC(C)=C(C)N1 PTBPTNCGZUOCBK-UHFFFAOYSA-N 0.000 description 1
- GSPFRBUPJBNHHJ-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole;formic acid Chemical compound OC=O.CC=1N=CNC=1C GSPFRBUPJBNHHJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000003937 GIAO Methods 0.000 description 1
- 241001417524 Pomacanthidae Species 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C253/00—Preparation of carboxylic acid nitriles
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/02—Formic acid
- C07C53/06—Salts thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
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Abstract
一种有如下结构式及晶胞参数的手性化合物的合成方法是无水无氧条件下，用催化剂钯配合物1％mol做催化剂，称取2,3‑丁二酮0.86g及5.0g甲酸铵，放入250mL两口烧瓶中，加入无水甲醇100mL做溶剂，回流反应30小时后，柱层析分离，用石油醚/二氯甲烷(1/9)洗脱，将收集的最后组分点自然挥发，得单晶2,4，5‑三甲基‑1H‑咪唑啉甲酸铵盐；该化合物(Ⅰ)的用途是作为催化剂在二苯甲酮亚胺与三甲基硅腈反应苯乙酮与三甲基硅腈的反应中显示了一定的催化效果，其转化率分别达87及91％。
Description
一、技术领域
本发明涉及一种化合物的制备方法及用途，特别涉及一种含氮化合物及其制备方法，确切地说是一种2,4,5-,三甲基-1H-咪唑甲酸盐的合成方法及用途。
二、背景技术
2，4,5-,三甲基-1H-咪唑啉甲酸盐是一种很重要药物中间体，其合成方法及应用已有文献报道【1-2】
参考文献：
1.1-(2-Hydroxy-3-methoxypropyl)-2-(arylazo)imidazoles，Salwinska,Ewa；Suwinski,Jerzy Polish Journal of Chemistry(1981),55,(7-8),1677-9.
2.Protonation and phase effects on the NMR chemical shifts ofimidazoles and pyrazoles:experimental results and GIAO calculations，Claramunt,Rosa M.；Lopez,Concepcion；Garcia,Maria Angeles；Denisov,Gleb S.；Alkorta,Ibon；Elguero,Jose，New Journal of Chemistry(2003),27,(4),734-742。
三、发明内容
本发明旨在为有机合成领域特别是制备手性药物提供一种简便的合成方法，所要解决的技术问题是遴选相应的原料并建立相应的方法合成咪唑啉衍生物药物。
(一)本发明所称的化合物是以下化学式(Ⅰ)所示的化合物：
其化学名称：2,4,5-,三甲基-1H-咪唑啉甲酸盐咪唑啉甲酸铵盐。
该化合物(Ⅰ)的合成方法是2,3-丁二酮与甲酸铵在无水甲醇溶剂中回流反应30小时，该化学反应式如下：
本化合物2，4，5-三甲基-1H-咪唑啉甲酸铵盐的合成方法包括合成、分离和纯化，所述的合成是无水无氧条件下，用催化剂钯配合物1％mol做催化剂，称取2,3-丁二酮0.86g及5.0g甲酸铵，放入250mL两口烧瓶中，加入无水甲醇100mL做溶剂，回流反应30小时后，柱层析分离，用石油醚/二氯甲烷(1/9)洗脱，将收集的最后组分点自然挥发，得单晶2，4，5-三甲基-1H-咪唑啉甲酸铵盐。
该反应的反应机理可推测如下：
2,3-丁二酮在已合成的钯催化剂催化作用下，一步形成咪唑啉衍生物，再与甲酸铵产生的甲酸作用，形成目标化合物铵盐。
其作为催化剂在二苯甲酮亚胺与三甲基硅腈反应及苯乙酮与三甲基硅氰的反应中显示了一定的催化效果，其转化率分别达89％及91％。
四、附图说明
图1是2，4，5-三甲基-1H-咪唑啉甲酸铵盐化合物(I)的单晶衍射图。
五、具体实施方式
1.手性钯配合物的制备
(1)[1,4-(4R)-二异丙基－2－噁唑啉基]苯的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl21.4054g(10.64mmol),40ml氯苯,1,4-二氰基苯5.0236g(39.2mmol),L-缬氨醇16.2075g,将混合物在高温下回流60h,停止反应,减压以除去溶剂,,将剩余物用水溶解,并用CHCl3(20mLx2)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂,将粗产品用石油醚/二氯甲烷(4:1)柱层析,得浅绿色粘稠状液体,产率52％；白色晶体,熔点:48-50℃,[a]5 D＝+111.9°(c＝0.429,CHCl3)；1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝7.97(s,4H),4.39～4.43(t,3.18Hz,1H),4.09～4.15(m,2H),1.85～1.86(m,1H),(d,J＝6.24Hz,6H),0.86～0.96(d,J＝6.24Hz,6H).13CNMR 18.13,19.03,32.85,70.26,72.76,128.10,128.16,130.32,162.82.IR:3273,2976,2960,2932,2889,2869,1643,1512,1469,1408,1382,1366,1350,1320,1296,1276,1214,1180,1108,1077,1047,1014,971,955,900,891,838,726,698,675,659,540.HRMS(EI):m/z(％):calcd forC18H24N2O2:300.1838；found:300.1833。
(2)双{[1,4-(4S)-二异丙基－2－噁唑啉基苯]氯化钯}配合物的制备
100mL两口瓶中,无水无氧条件下,加入氯化钯1.5603g(4.92mmol),1,4-(4R)-二异丙基－2－噁唑啉基苯1.0435g(3.48mmol)，氯苯30mL将混合物在高温下回流48h,停止反应,减压以除去溶剂,,将剩余物三氯甲烷及乙醇溶解，自然挥发，得红褐色配合物得晶体，产率：92％；m.p.:>200℃,[a]5 D＝+512.8°(c 0.0564,CH3OH)；1H NMR(600MHz,CDCl3),δ`ppm8.81(s,8H,ArH),4.61-4.63(m,4H,CH×4),4.53(t,J＝9.6Hz,4H,CH×4),4.44(t,J＝8.5Hz,4H,CH×4),3.07-3.10(m,4H),1.18and 1.15(dd,J＝6.7,7.2Hz,24H,CH3×4)；13CNMR(150MHz,CDCl3)δppm 166.8,130.1(×2),129.3,72.0,69.1,30.7,19.0,15.6；νmax(cm-1)3487,3049,2957,2929,2872,1642,1609,1572,1509,1480,1464,1416,1379,1331,1288,1246,1178,1141,1123,1099,1045,1018,959,933,899,854,804,770,722,693,438；Elemental analysis for C36H48N4Cl4O4Pd2,found C 45.26％,H 5.06％,N 5.86％；requires C 45.32％,H 5.24％,N 5.48％；
2.2，4，5-三甲基-1H-咪唑甲酸盐咪唑啉甲酸铵盐的制备
无水无氧条件下，用催化剂钯配合物1％mol做催化剂，称取2,3-丁二酮0.86g及5.0g甲酸铵，放入250mL两口烧瓶中，加入100mL氯苯做溶剂，回流反应30小时后，柱层析分离，用石油醚/二氯甲烷(1/100)洗脱，将收集的最后组分点自然挥发，得单晶4,5-二甲基-1H-咪唑甲酸盐；元素分析数据C7H12N2O2，理论值：C：53.83％；H：7.74％；N：17.94％；实测值：C 53.95％；H：7.82％；N：18.02％；HRMS(C7H12N2O2,m/e)：理论值：156.0899；实测值：156.0912.；1HNMR(600MHz,CDCl3,27℃),产率65％；1HNMR(400MHz,CDCl3,27℃),δ(ppm)＝8.60(br,2H),8.01(m,1H),2.36(S,3H),2.05(s，6H),13CNMR(150MHz,CDCl3,27℃)165.8,140.7,123.6,11.6,8.9；IR(KBr):3199,2927，2787，2703，1670，1581，1442，1376,1346，1171，963，758，630；
化合物晶体数据如下：
晶体典型的键长数据：O(1)-C(5)
晶体典型的键角数据：
3.二苯甲酮亚胺与三甲基硅腈的缩合反应应用
称取1mmol二苯甲酮亚胺和三甲基硅腈0.2mL放置于25mL小烧瓶中，加入2.0mL二氯甲烷0.1mmol化合物I，常温下搅拌5h，取少量样品做核磁检测，转化率达:89％；1H NMR(600MHz,CDCl3,27℃)δ7.23–7.59(m,10H),4.10(s,2H)；
称取1mmol苯乙酮和三甲基硅腈0.3mL放置于25mL小烧瓶中，加入2.0mL二氯甲烷0.1mmol化合物I，常温下搅拌38h，取少量样品做核磁检测，转化率达:91％；1H NMR(600MHz,CDCl3,27℃)1H NMR(300MHz,CDCl3):δ7.38–7.58(m,5H),1.86(s,3H；CH3),d＝0.17(s,9H,(CH3)3Si)。
Claims (2)
1.一种有如下结构式(I)及晶胞参数的手性化合物的合成方法，其特征在于：无水无氧条件下，用钯配合物1％mol做催化剂，称取2,3-丁二酮0.86g及5.0g甲酸铵，放入250mL两口烧瓶中，加入无水甲醇100mL做溶剂，回流反应30小时后，柱层析分离，用石油醚/二氯甲烷1:9洗脱，将收集的最后组分点自然挥发，得单晶2,4，5-三甲基-1H-咪唑啉甲酸铵盐；
所述化合物(I)在296K温度下，牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以ω-θ扫描方式收集衍射数据，晶体属单斜晶系，C2/m，其晶胞参数：/>α＝90°；/>β＝99.310°；/>γ＝90°；
所述钯配合物的制备：
(1)[1,4-(4R)-二异丙基－2－噁唑啉基]苯的制备
在100mL两口瓶中，无水无氧条件下，加入无水ZnCl21.4054g，40ml氯苯,1,4-二氰基苯5.0236g，L-缬氨醇16.2075g，将混合物加热回流60h，停止反应，减压以除去溶剂，将剩余物用水溶解，并用CHCl3 20mLx2萃取，有机相用无水硫酸钠干燥，旋转除去溶剂，将粗产品用石油醚/二氯甲烷4:1柱层析，得浅绿色粘稠状液体；
(2)双{[1,4-(4S)-二异丙基－2－噁唑啉基苯]氯化钯}配合物的制备
100mL两口瓶中，无水无氧条件下，加入氯化钯1.5603g，1,4-(4R)-二异丙基－2－噁唑啉基苯1.0435g，氯苯30mL将混合物在高温下回流48h，停止反应，减压以除去溶剂，将剩余物三氯甲烷及乙醇溶解，自然挥发，得红褐色配合物的晶体。
2.根据权利要求1中所述化合物(Ⅰ)的用途，其特征是在二苯甲酮亚胺与三甲基硅腈反应、苯乙酮与三甲基硅腈的反应中作为催化剂。
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