CN104072500A - 2,3-dibenzylamine quinoxaline imidazole onium salt and synthesis method thereof - Google Patents
2,3-dibenzylamine quinoxaline imidazole onium salt and synthesis method thereof Download PDFInfo
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- CN104072500A CN104072500A CN201410110143.8A CN201410110143A CN104072500A CN 104072500 A CN104072500 A CN 104072500A CN 201410110143 A CN201410110143 A CN 201410110143A CN 104072500 A CN104072500 A CN 104072500A
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- quinoxaline
- dibenzylamine
- quinoxaline imidazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention relates to quinoxaline imidazole onium salt, and in particular relates to 2,3-dibenzylamine quinoxaline imidazole onium salt and a synthesis method thereof. The method comprises the following steps: adding 2,3-dichloro-quinoxaline and benzylamine in amount of substance ratio of 1:(5-6) in a reaction still, reacting for 3-5 hours at 110-130 DEG.C; cooling to room temperature to obtain a reaction product, adding n-hexane, stirring to obtain white precipitate, suction-filtering to obtain white solid, washing by using deionized water, vacuum-drying to obtain 2,3-dibenzylamine quinoxaline; weighing 2, 3-dibenzylamine quinoxaline, NH4PF6 and triethyl orthoformate in substance mole ratio of 1: 1.2: 8, mixing, reacting for 5-8 hours at 110-120 DEG.C, filtering to obtain a yellow solid, respectively washing by using cold water and ethanol, vacuum-drying, recrystallizing to obtain the product. By using the prepared 2,3-dibenzylamine quinoxaline imidazole onium salt, the n-heterocyclic carbenes with excellent catalysis can be synthesized.
Description
Technical field
The present invention relates to quinoxaline imidazole salts, be specifically related to 2,3-dibenzyl amido quinoxaline imidazole salts and synthetic method thereof.
Background technology
Since Arduengo successfully isolates stable N-heterocyclic carbine (NHC) for the first time, N-heterocyclic carbine research obtains fast development in the past for 20 years; N-heterocyclic carbine shows the prospect more wide than traditional organic phosphine as the surrogate of organic phosphine in homogeneous catalysis, in recent years, becomes gradually the important organic ligand of Organometallic Chemistry and inorganic chemistry; Due to N-heterocyclic carbine " push-pull " mechanism cause this class part uniqueness coordination feature (Angew. Chem., Int. Ed.,
2002, 41,1290 – 1309; Chem. Rev.,
2004, 248,2239 – 2246; Coord. Chem. Rev.,
2007, 251,610 – 641.), thus N-heterocyclic carbine can effectively be stablized activator metal center and produces superior catalytic performance.
Imidazoles, benzoglyoxaline etc. are the synthetic N-heterocyclic carbine of basic construction unit, due to preparation easily and catalytic performance feature excellent and that be easy to reclaim enjoy Organometallic Chemistry researchist's favor; By utilizing the imidazoles N-heterocyclic carbine that different transition metal synthesizes to embody excellent performance: Pd title complex is applied to linked reaction (the Inorg. Chem. such as Mizoroki – Heck and Suzuki – Miyaura C – C
2009, 48,6924-6933; J. Am. Chem. Soc.,
2009, 131,9076 – 9085; Organometallics,
2009, 28,5244-5255; Organometallics.,
2009, 28,2640-2642); Ag, Au title complex except catalytic performance, part of compounds even embody the pharmaceutical properties such as antibacterial, anticancer (Chem. Soc. Rev.,
2008, 37,1776-1782. Chem. Soc. Rev.,
2008, 37,1998-2001); Ni matching object reveal good catalysis Kumada C-C linked reaction character (Organometallics.,
2009, 28,909-914; Organometallics.,
2009, 28,1336-1349); Mn matching object reveal original position synthesis catalytic performance (Organometallics.,
2009, 28,2505-2511) etc.; Quinoxaline imidazole salts derivative is easy to modify, and by the modification to the upper R group of N, is expected to prepare that structure is abundant, the arbine complex of excellent performance, also can the impact of systematic study substituting group on azepine Cabbeen and complexes stability thereof.
Summary of the invention
The invention provides the synthetic method of 2,3-dibenzyl amido quinoxaline imidazole salts, the present invention has reached the object that reduces raw material consumption, Reaction time shorten, raising reaction yield, simplifies experimental implementation.
Described 2,3-dibenzyl amido quinoxaline imidazole salts structural formula is:
。
Its preparation method carries out according to the following steps:
(1) 2,3-dichloro-quinoxaline and benzylamine are joined in reactor by the ratio 1:5-6 of amount of substance, put into
110-130 degree in baking oven, reaction 3-5 hour.
(2) obtain reaction product after being down to room temperature, add the normal hexane of 50 times of reaction product volumes, after stirring, go out
Existing white precipitate.
(3) suction filtration obtains white solid, and with deionized water rinsing, vacuum-drying obtains 2 of white, 3-dibenzyl
Amido quinoxaline.
(4) take 2,3-dibenzyl amido quinoxaline, NH
4pF
6with triethyl orthoformate according to the ratio 1 of amount of substance:
1.2:8 mixes, at 110-120 degree reaction 5-8 hour.
(5) filter and obtain yellow solid, cold water, ethanol rinse respectively, and recrystallization after vacuum-drying, to target
Product carries out infrared spectra and X-ray diffraction analytical test.
Utilization prepare 2,3-dibenzyl amido quinoxaline imidazole salts, can synthesize the N-heterocyclic carbine of catalytic performance excellence; Simultaneously, quinoxaline imidazole salts derivative is easy to modify, by to introducing the modification N of the R group of different electronic effects, be expected to prepare that structure is abundant, the arbine complex of excellent performance, can the impact of systematic study substituting group on azepine Cabbeen and complexes stability thereof; The present invention has that raw material consumption is few, the reaction times is short, yield is high, simple operation and other advantages.
Accompanying drawing explanation
Fig. 1: the synthetic route of compound.
Fig. 2: the infrared spectrum of 2,3-dibenzyl amido quinoxaline.
Fig. 3: the molecular structure of 2,3-dibenzyl amido quinoxaline.
Fig. 4: the infrared spectrum of 2,3-dibenzyl amido quinoxaline imidazole salts.
Fig. 5: the molecular structure of 2,3-dibenzyl amido quinoxaline imidazole salts.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and embodiment is for the present invention being described rather than for limiting the scope of the invention.
Embodiment 1 preparation 2,3-dibenzyl amido quinoxaline imidazole salts
(1), by 0.02mol 2,3-dichloro-quinoxaline and 11mL benzylamine join in the reactor of 50 mL, add
Heat keeps 5 hours to 110 ℃.
(2) reaction solution in reactor is poured in round-bottomed flask, added 220mL normal hexane, stir 30 minutes
After clock there are a large amount of white precipitates in bottom.
(3) suction filtration obtains white solid, and rinses (10mL * 3) with large water gaging, and vacuum-drying, obtains 2,3-
Dibenzyl amido quinoxaline, productive rate 92%; With the structure of ultimate analysis, infrared and X ray single crystal diffractometer deterministic compound, ultimate analysis: calculated value (molecular formula): C, 77.62; H, 5.92; N, 16.46; Measured value: C, 77.25; H, 5.83; N, 15.99; Infrared spectrum is shown in Fig. 2,3350cm
-1the peak of left and right is the stretching vibration of N-H, 3057 cm
-1place is the stretching vibration of Ar-H, 1654 cm
-1this has illustrated the existence of piperazine at place.The structure of the compound that X-ray single crystal diffraction solves is shown in Fig. 3.
(4) take above-mentioned product 0.01mol, 0.012mol NH
4pF
6triethyl orthoformate with 12 mL
120 degree reactions 5 hours, suction filtration obtains yellow solid.
(5) cold water, ethanol rinse respectively (10mL * 3), by recrystallization after sample vacuum-drying, after obtain
Yellow rhabdolith, productive rate 70%; With ultimate analysis, infrared spectrum characterization compound, the structure of X-ray single crystal diffractometer deterministic compound; Ultimate analysis: calculated value (molecular formula): C, 55.65; H, 3.86; N, 11.29; Measured value: C, 55.09; H, 3.67; N, 11.05; Infrared spectrum is shown in Fig. 4, and we can find out that, after formation imidazole salts, obvious variation has occurred corresponding infrared spectra, particularly at 3350 cm
-1the strong absorption peak of left and right has disappeared, and this explanation N-H key has disappeared, and meets the constructional feature forming after salt; The structure of the compound that X-ray single crystal diffraction solves is shown in Fig. 5.
Embodiment 2 preparation 2,3-dibenzyl amido quinoxaline imidazole salts
(1), by 0.02mol 2,3-dichloro-quinoxaline and 11mL benzylamine join in the reactor of 50 mL, add
Heat keeps 4 hours to 120 ℃.
(2) reaction solution in reactor is poured in round-bottomed flask, added 220mL normal hexane, stir 30 minutes
After clock there are a large amount of white precipitates in bottom.
(3) suction filtration obtains white solid, and rinses with large water gaging, and vacuum-drying, obtains 2,3-dibenzyl amido quinoline
Quinoline, productive rate 92%; Structure with ultimate analysis, infrared and X ray single crystal diffractometer deterministic compound.Ultimate analysis: calculated value (molecular formula): C, 77.62; H, 5.92; N, 16.46; Measured value: C, 77.25; H, 5.83; N, 15.99; The structure of the compound that infrared spectrum and X-ray single crystal diffraction solve is respectively with Fig. 2 and Fig. 3.
(4) take above-mentioned product 0.01mol, 0.012mol NH
4pF
6triethyl orthoformate with 12 mL
115 degree reactions 7 hours, suction filtration obtains yellow solid.
(5) cold water, ethanol rinse respectively 3 times, by recrystallization after sample vacuum-drying, after obtain yellow bar-shaped
Crystal, productive rate 76%; With ultimate analysis, infrared spectrum characterization compound, the structure of X-ray single crystal diffractometer deterministic compound; Ultimate analysis: calculated value (molecular formula): C, 55.65; H, 3.86; N, 11.29; Measured value: C, 55.09; H, 3.67; N, 11.05; The structure of the compound that infrared spectrum and X-ray single crystal diffraction solve is respectively with Fig. 4 and Fig. 5.
Embodiment 3 preparation 2,3-dibenzyl amido quinoxaline imidazole salts
(1), by 0.2mol 2,3-dichloro-quinoxaline and 110mL benzylamine join in the reactor of 250 mL, add
Heat keeps 3 hours to 130 ℃.
(2) reaction solution in reactor is poured in round-bottomed flask, added 2200mL normal hexane, stir 30 minutes
After clock there are a large amount of white precipitates in bottom.
(3) suction filtration obtains white solid, and rinses with large water gaging, and vacuum-drying, obtains 2,3-dibenzyl amido quinoline
Quinoline, productive rate 89%; Point plate is determined product and purity, with ultimate analysis, infrared and X ray single crystal diffraction
The structure of instrument deterministic compound; Ultimate analysis: calculated value (molecular formula): C, 77.58; H, 5.87; N,
16.56; Measured value: C, 77.32; H, 5.81; N, 15.94; The structure of the compound that infrared spectrum and X-ray single crystal diffraction solve is respectively with Fig. 2 and Fig. 3.
(4) take above-mentioned product 0.1mol, 0.12mol NH
4pF
6triethyl orthoformate 110 with 120 mL
Degree reaction 8 hours, suction filtration obtains yellow solid.
(5) cold water, ethanol rinse respectively 3 times, by recrystallization after sample vacuum-drying, after obtain yellow bar-shaped crystalline substance
Body, productive rate 74%; Point plate is determined product and purity, ultimate analysis: calculated value (molecular formula): C, 55.57;
H, 3.84; N, 11.24; Measured value: C, 55.04; H, 3.64; N, 11.12; The structure of the compound that infrared spectrum and X-ray single crystal diffraction solve is respectively with Fig. 4 and Fig. 5.
Claims (3)
1.2,3-dibenzyl amido quinoxaline imidazole salts, for the synthesis of N-heterocyclic carbine, is characterized in that: described 2,3-dibenzyl amido quinoxaline imidazole salts structural formula is:
。
2. as claimed in claim 12, the preparation method of 3-dibenzyl amido quinoxaline imidazole salts, is characterized in that comprising the steps:
(1) 2,3-dichloro-quinoxaline and benzylamine are joined in reactor by the ratio 1:5-6 of amount of substance, in 110-130 degree, reaction 3-5 hour;
(2) obtain reaction product after being down to room temperature, add normal hexane, after stirring, occur white precipitate;
(3) suction filtration obtains white solid, and with deionized water rinsing, vacuum-drying obtains 2 of white, 3-dibenzyl amido quinoxaline;
(4) take 2,3-dibenzyl amido quinoxaline, NH
4pF
6mix according to the ratio 1:1.2:8 of amount of substance with triethyl orthoformate, at 110-120 degree reaction 5-8 hour;
(5) filter and obtain yellow solid, cold water, ethanol rinse respectively, and after vacuum-drying, recrystallization obtains described product.
3. as claimed in claim 22, the preparation method of 3-dibenzyl amido quinoxaline imidazole salts, is characterized in that: the volume of described normal hexane is 50 times of reaction product volume.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592126A (en) * | 2015-01-06 | 2015-05-06 | 江苏大学 | Method for synthesizing N, N-di-(p-methylbenzoate)benzimidazole onium salt |
| CN114380753A (en) * | 2020-10-21 | 2022-04-22 | 中国医学科学院药物研究所 | Aryl or heteroaryl substituted quinoxaline-2, 3-diamine compound and antibacterial application thereof |
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| JP2000171974A (en) * | 1998-12-09 | 2000-06-23 | Fuji Photo Film Co Ltd | Photopolymerizable composition and photothermosensitive recording material using the composition |
| JP2000292758A (en) * | 1999-02-05 | 2000-10-20 | Fuji Photo Film Co Ltd | Surface plasmon optical modulating device |
| CN101701066A (en) * | 2009-11-11 | 2010-05-05 | 洛阳师范学院 | Polyether-loaded N-heterocyclic carbene-palladium compound and preparation method and application thereof |
| CN103483267A (en) * | 2012-06-13 | 2014-01-01 | 上海赛迦化工产品有限公司 | Diverse arylimidazole quaternary ammonium salt, preparation method and application thereof |
-
2014
- 2014-03-24 CN CN201410110143.8A patent/CN104072500A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000171974A (en) * | 1998-12-09 | 2000-06-23 | Fuji Photo Film Co Ltd | Photopolymerizable composition and photothermosensitive recording material using the composition |
| JP2000292758A (en) * | 1999-02-05 | 2000-10-20 | Fuji Photo Film Co Ltd | Surface plasmon optical modulating device |
| CN101701066A (en) * | 2009-11-11 | 2010-05-05 | 洛阳师范学院 | Polyether-loaded N-heterocyclic carbene-palladium compound and preparation method and application thereof |
| CN103483267A (en) * | 2012-06-13 | 2014-01-01 | 上海赛迦化工产品有限公司 | Diverse arylimidazole quaternary ammonium salt, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHANMUGANATHAN SARAVANAKUMAR等: "Influence of anellation in N-heterocyclic carbenes: Novel quinoxaline-anellated NHCs trapped as transition metal complexes", 《CHEM. COMMUN.》, 4 January 2006 (2006-01-04) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104592126A (en) * | 2015-01-06 | 2015-05-06 | 江苏大学 | Method for synthesizing N, N-di-(p-methylbenzoate)benzimidazole onium salt |
| CN114380753A (en) * | 2020-10-21 | 2022-04-22 | 中国医学科学院药物研究所 | Aryl or heteroaryl substituted quinoxaline-2, 3-diamine compound and antibacterial application thereof |
| CN114380753B (en) * | 2020-10-21 | 2024-02-27 | 中国医学科学院药物研究所 | Aryl or heteroaryl substituted quinoxaline-2, 3-diamine compound and antibacterial application thereof |
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