CN104945209B - A kind of synthetic method of 2-aminobutene 1,4-derovatives - Google Patents
A kind of synthetic method of 2-aminobutene 1,4-derovatives Download PDFInfo
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- CN104945209B CN104945209B CN201510397132.7A CN201510397132A CN104945209B CN 104945209 B CN104945209 B CN 104945209B CN 201510397132 A CN201510397132 A CN 201510397132A CN 104945209 B CN104945209 B CN 104945209B
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Abstract
The invention belongs to organic chemical industry and field of fine chemical, particularly to a kind of about the synthesis technique preparing 2-aminobutene-Isosorbide-5-Nitrae-derovatives.Phenylglyoxal derivant, imines being mixed with end alkynes, add Au catalyst, react, obtain 2-aminobutene-Isosorbide-5-Nitrae-derovatives under heating condition, productivity is 62～85%.This reaction is with raw material simple and easy to get, what one kettle way was easy has synthesized 2-aminobutene-1,4-derovatives, raw material all participates in the generation of product, reaction condition is gentle, has significantly high Atom economy, for synthesis 2-aminobutene-1,4-derovatives provides one efficiently, green new synthetic method.
Description
Technical field
The invention belongs to organic chemical industry and field of fine chemical, particularly to a kind of about the synthesis technique preparing 2-aminobutene-Isosorbide-5-Nitrae-derovatives.
Background technology
2-aminobutene-1,4-cyclohexadione compounds is widely present in natural product, medicine and has in bioactive compound.Additionally, 2-aminobutene-Isosorbide-5-Nitrae-dione compounds is also the important as precursors building the heterocyclic compounds such as pyrroles, hydrazine and furan, its construction method is always up the study hotspot of various countries' Scientific Research Workers.
At present, the synthetic method productivity reported in document is not high, and the response time is longer, and toxicity is bigger.Therefore the synthetic method developing simply efficient, green 2-aminobutene-1,4-derovatives has great importance.
Summary of the invention
Technical problem solved by the invention is to provide the catalysis of a kind of gold, and with phenylglyoxal derivant, imines and end alkynes for raw material, one-step method obtains trisubstituted 2-aminobutene Isosorbide-5-Nitrae-derovatives.The method is easy and simple to handle, and reaction condition is gentle.
Concrete technical scheme is: with phenylglyoxal derivant, secondary amine and end alkynes for raw material, after adding Au catalyst and appropriate organic solvent, and stirring reaction, 2-aminobutene-Isosorbide-5-Nitrae-derovatives is synthesized,
Reaction condition is: under air conditions, is heated to 50 DEG C, and the time of reaction is 8-12 hour,
The mol ratio of above-mentioned raw materials is, phenylglyoxal derivant: secondary amine: end alkynes=1:1.5:2；
Above-mentioned Au catalyst is auric chloride, gold chloride or auric bromide. etc., and the consumption of Au catalyst is the 5% of phenylglyoxal derivant molal quantity；
Above-mentioned phenylglyoxal derivant be phenylglyoxal, m-chloro phenylglyoxal, to chlorobenzoyl formaldehyde, to Bromophenacyl formaldehyde or to methoxybenzoyl formaldehyde；
Above-mentioned secondary amine is morpholine, hexahydropyridine, diethylamine etc.；
Above-mentioned end alkynes is phenylacetylene, to fluorobenzene acetylene, to amylbenzene acetylene, to methylbenzene acetylene etc.；
Course of reaction of the present invention and the structural formula of product obtained be:
Post-reaction treatment is easy, it is only necessary to simple chromatographic column separation method, using the mixed solvent of petroleum ether and ethyl acetate as eluant, it is possible to obtain pure 2-aminobutene-Isosorbide-5-Nitrae-diketone product.The compound of synthesis adopts1HNMR,13CNMR and high resolution mass spectrum characterize, and spectral data coincide with structure.
The beneficial effects of the present invention is: 2-aminobutene-1,4-cyclohexadione compounds is widely present in natural product, medicine and has in bioactive compound.We use phenylglyoxal derivant, secondary amine and end alkynes to be raw material first, and one-step method has been efficiently obtained by a series of 2-amino-2-butylene-Isosorbide-5-Nitrae-derovatives, and productivity is up to 62-85%.Reaction raw materials is simple and easy to get, mild condition, and cost is low.
Detailed description of the invention
Embodiment 1
By phenylglyoxal (1.0mmol), morphine woods (1.5mmol), phenylacetylene (2mmol), AuBr3The mixed solution of (the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) joins in 15mL test tube, it is heated to 50 DEG C, react 8 hours, silica gel column chromatography separates, and adopt the mixed solvent eluting of petroleum ether and ethyl acetate (volume ratio 1:1), the productivity obtaining 2-morphine woods-Isosorbide-5-Nitrae diphenylbutene-Isosorbide-5-Nitrae diketone is 82%.
1HNMR (400MHz, CDCl3) δ 8.02 (d, J=7.5Hz, 2H), 7.84 (d, J=7.4Hz, 2H), 7.57-7.55 (m, 1H), 7.49-7.44 (m, 3H), 7.36 (t, J=7.8Hz, 2H), 6.15 (s, 1H), 3.74 (s, 4H), 3.42-3.32 (m, 4H).13CNMR(75MHz,CDCl3)δ193.9,187.2,160.9,138.8,135.7,133.6,131.7,129.0,128.2,128.1,127.7,93.5,66.2,47.6,29.7.
HRMS(ESI)calcdforC20H19NO3([M+H])322.1443found322.1440.
Embodiment 2
Will to fluorobenzoyl formaldehyde (1.0mmol), morphine woods (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 8 hours, silica gel column chromatography separates, and adopt the mixed solvent of petroleum ether and ethyl acetate (volume ratio 1:1) to wash, the productivity obtaining 4-(4-fluorobenzene)-2-morphine woods-1-phenylbutene-Isosorbide-5-Nitrae diketone is 85%.
1HNMR(400MHz,CDCl3) δ 8.02 (d, J=7.1Hz, 2H), 7.85 (q, J=5.5Hz, 2H), 7.57-7.55 (m, 1H), 7.48 (t, J=7.5Hz, 2H), 7.04 (t, J=8.6Hz, 2H), 6.09 (s, 1H), 3.75 (s, 4H), 3.42-3.32 (m, 4H).13CNMR(75MHz,CDCl3)δ193.8,185.8,161.2,135.7,133.7,130.2,130.1,129.1,128.1,115.3,115.1,92.9,66.2,47.6.
HRMS(ESI)calcdforC20H18FNO3(M+H)340.1349found340.1352.
Embodiment 3
Will to toluyl formaldehyde (1.0mmol), morphine woods (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent eluting of petroleum ether and ethyl acetate (volume ratio 1:1), the productivity obtaining 4-(4-benzyl)-2-morphine woods-1-phenylbutene-Isosorbide-5-Nitrae diketone is 67%.
1HNMR(400MHz,CDCl3) δ 8.03 (d, J=7.8Hz, 2H), 7.74 (d, J=7.9Hz, 2H), 7.55 (d, J=7.2Hz, 1H), 7.47 (t, J=7.6Hz, 2H), 7.16 (d, J=7.9Hz, 2H), 6.15 (s, 1H), 3.73 (s, 4H), 3.40-3.30 (m, 4H), 2.36 (s, 3H).13CNMR(75MHz,CDCl3)δ186.96,160.79,142.28,133.55,129.01,128.93,128.08,127.88,93.54,66.20,47.55,21.56.
HRMS(ESI)calcdforC21H21NO3([M+H])336.1599found336.1601.
Embodiment 4
Will to amyl group phenylglyoxal (1.0mmol), morphine woods (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent eluting of petroleum ether and ethyl acetate (volume ratio 1:1), the productivity obtaining 4-(4-amylbenzene)-2-morphine woods-1-phenylbutene-Isosorbide-5-Nitrae diketone is 71%.
Embodiment 5
By phenylglyoxal (1.0mmol), morphine woods (1.5mmol), to chlorobenzene acetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent of petroleum ether and ethyl acetate (volume ratio 1:1) to wash, the productivity obtaining 1-(4-chlorobenzene)-2-morphine woods-4-phenylbutene-Isosorbide-5-Nitrae diketone is 79%.
Embodiment 6
By phenylglyoxal (1.0mmol), morphine woods (1.5mmol), to bromobenzene acetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent eluting of petroleum ether and ethyl acetate (volume ratio 1:1), the productivity obtaining 1-(4-bromobenzene)-2-morphine woods-4-phenylbutene-Isosorbide-5-Nitrae diketone is 72%.
Embodiment 7
By phenylglyoxal (1.0mmol), piperidines (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent of petroleum ether and ethyl acetate (volume ratio 1:1) to wash, the productivity obtaining 2-piperidines-Isosorbide-5-Nitrae diphenylbutene-Isosorbide-5-Nitrae diketone is 76%.
Embodiment 8
Will to toluyl formaldehyde (1.0mmol), piperidines (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent of petroleum ether and ethyl acetate (volume ratio 1:1) to wash, the productivity obtaining 4-(4-benzyl)-2-piperidines-1-phenylbutene-Isosorbide-5-Nitrae diketone is 73%.
Embodiment 9
By phenylglyoxal (1.0mmol), diethylamine (1.5mmol), phenylacetylene (2mmol), AuBr3(the 5% of phenylglyoxal derivant molal quantity) and 2mL first alcohol and water (volume ratio 10:1) mixed solution join in 15mL test tube, it is heated to 50 DEG C, react 10 hours, silica gel column chromatography separates, and adopt the mixed solvent eluting of petroleum ether and ethyl acetate (volume ratio 1:1), the productivity obtaining 2-diethylamine-Isosorbide-5-Nitrae diphenylbutene-Isosorbide-5-Nitrae diketone is 62%.
Claims (6)
1. a 2-aminobutene-1, the preparation method of 4-derovatives, it is characterized in that: described preparation method is, with phenylglyoxal derivant, secondary amine and end alkynes for raw material, after adding Au catalyst and organic solvent, heated and stirred is reacted, chromatographic column separates, eluting, obtain 2-aminobutene-Isosorbide-5-Nitrae-derovatives
Wherein, described phenylglyoxal derivant be phenylglyoxal, m-chloro phenylglyoxal, to chlorobenzoyl formaldehyde, to Bromophenacyl formaldehyde or to methoxybenzoyl formaldehyde；
Described end alkynes is phenylacetylene, to fluorobenzene acetylene, to amylbenzene acetylene or to methylbenzene acetylene.
2. the preparation method of 2-aminobutene-Isosorbide-5-Nitrae-derovatives as claimed in claim 1, it is characterised in that: the mol ratio of described raw material is, phenylglyoxal derivant: secondary amine: end alkynes=1:1.5:2.
3. the preparation method of 2-aminobutene-Isosorbide-5-Nitrae-derovatives as claimed in claim 1, it is characterised in that: described heating-up temperature is 50 DEG C, and the time of described reaction is 8-12 hour.
4. the preparation method of 2-aminobutene-Isosorbide-5-Nitrae-derovatives as claimed in claim 1, it is characterised in that: described Au catalyst is auric chloride, gold chloride or auric bromide., and the consumption of described Au catalyst is the 5% of described phenylglyoxal derivant molal quantity.
5. the preparation method of 2-aminobutene-Isosorbide-5-Nitrae-derovatives as claimed in claim 1, it is characterised in that: described secondary amine is morpholine, hexahydropyridine or diethylamine.
6. the preparation method of 2-aminobutene-Isosorbide-5-Nitrae-derovatives as claimed in claim 1, it is characterised in that: described eluting is, using the mixed solvent of petroleum ether and ethyl acetate as eluent.
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Effective date of registration: 20201228 Address after: 244100 1 Tongling Yi An Economic Development Zone, Anhui Patentee after: Tongling Huize Technology Information Consulting Co.,Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |
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