CN105585473A - Method for preparing propiolic acid compounds - Google Patents
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- CN105585473A CN105585473A CN201610146701.5A CN201610146701A CN105585473A CN 105585473 A CN105585473 A CN 105585473A CN 201610146701 A CN201610146701 A CN 201610146701A CN 105585473 A CN105585473 A CN 105585473A
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Abstract
The invention discloses a method for preparing propiolic acid compounds. An ionic type iron (III) complex containing monoimide functionalized imidazolium cations is taken as the single-component catalyst, carbon dioxide is taken as the carboxylation reagent, and various propiolic acid compounds are prepared through carboxylation reaction of terminal alkyne under normal pressure. The terminal alkyne substrate relates to phenylacetylene, substituted phenylacetylene, heterocyclic aryne, aromatic diyne or aliphatic series terminal alkyne. The method for preparing the propiolic acid compounds through carboxylation reaction of terminal alkyne and carbon dioxide under the catalysis of the iron-based catalyst is provided for the first time. Compared with the prior art, the method has the advantages that the catalyst is more environmentally friendly, synthesis is easier, reaction conditions are mild, and catalytic activity and functional group tolerance are unchanged or improved.
Description
Technical field
The invention belongs to the preparing technical field of organic compound, be specifically related to the preparation method of propiolic acid compounds.
Background technology
Propiolic acid compounds is the important intermediate of synthetic fine chemicals, medical molecule, for example, by heterocyclic compounds such as reaction synthesizing coumarin, flavones such as cycloaddition; In addition, they are also one of decarboxylation cross-coupling reaction preparation important source material of replacing alkynes, therefore propiolic acid compounds synthetic paid close attention to widely always (referring to Goo β en, L.J., Rodr í guez, N., ManjolinhoF., Langea, P.P.,Adv.Synth.Catal., 2010,352,2913). In prior art, the method of synthetic propiolic acid compounds is mainly the oxidation carboxylation reaction of alkynes, using formaldehyde or carbon monoxide as carboxylated reagent, but formaldehyde or carbon monoxide exist, and price is more expensive, toxicity is very large and operate the shortcomings such as inconvenience, therefore makes the application of these methods be restricted. There is bibliographical information to utilize organometallic reagent (as RMgBr) can prepare propiolic acid compounds, but organometallic reagent exists price, to air-sensitive and not easy-operating shortcoming, therefore the new method of the synthetic propiolic acid compounds of exploitation has good application prospect.
In recent years, a lot of preparation methods avoid using expensive organometallic reagent, such as with (1,10-phenanthrolene)-bis-(triaryl phosphine) copper nitrate is catalyst, can realize the carboxylation reaction of various aliphatic Terminal Acetylenes and aromatic series Terminal Acetylenes, but for aromatic series Terminal Acetylenes, need under five atmospheric conditions, carry out; WithN,N,N’N’-tetramethylethylenediamine is under the condition of part, can realize the Terminal Acetylenes of stannous chloride catalysis and the carboxylation reaction of carbon dioxide, reaction condition gentleness, under room temperature normal pressure, can complete, but catalyst system and catalyzing does not almost have activity for the aromatic series Terminal Acetylenes of electron deficient, only have part is changed into N-heterocyclic carbine, while increasing the consumption of catalyst, could be realized the carboxylated of the aromatic series Terminal Acetylenes of electron deficient simultaneously, but productive rate is lower, practical application has little significance; The carboxylation reaction system of the Terminal Acetylenes of silver catalyst catalysis and carbon dioxide does not need to add part, and catalyst amount is not high, and still, this reaction system still needs two atmospheric carbon dioxide, and the activity of most of substrate is on the low side; The carboxylation reaction condition of the Terminal Acetylenes of catalysis of rare-earth compound and carbon dioxide is gentleer, but substrate also only limits to common Terminal Acetylenes, containing aldehyde radical, cyano group etc. does not relate to the responsive Terminal Acetylenes of organometallic reagent (as RMgBr etc.), and rare earth compound price is more expensive, to air-sensitive, be not easy to operation. Therefore the carboxylation reaction that, exploitation catalyst efficient, green, cheap and easy to get, easy to use, that substrate applicability is wide is realized Terminal Acetylenes and carbon dioxide has great novelty and using value.
Summary of the invention
The object of this invention is to provide a kind of method of preparing propiolic acid compounds, taking molecular formula as [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) be single-component catalyst containing ionic iron (III) complex of single imines functionalization glyoxaline cation, carbon dioxide, as carboxylated reagent, is prepared various propiolic acid compounds by the carboxylation reaction of Terminal Acetylenes.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of method of preparing propiolic acid compounds, comprises the following steps: to add successively in reactor catalyst, cesium carbonate, terminal alkyne compound andN,N-dimethyl formamide; Then pass into carbon dioxide, in 40～70 DEG C, stirring reaction 12～20 hours under normal pressure; Then obtain propiolic acid compounds through hcl acidifying.
Catalyst is ionic iron (III) complex, is a kind of ionic iron (III) complex containing single imines functionalization glyoxaline cation, and molecular formula is [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl), its molecular structural formula is as follows:
Further, after reaction finishes, reactant liquor is cooled to room temperature, then pass through successively water dilution, hcl acidifying, extracted with diethyl ether, the ether layer saturated sodium-chloride then extraction being obtained washs, then through anhydrous sodium sulfate drying, last solvent removed in vacuo, obtains target product propiolic acid compounds.
The invention also discloses the application in the carboxylation reaction of catalysis terminal alkyne compound and carbon dioxide as single-component catalyst of ionic iron (III) complex.
Being prepared as of ionic iron (III) complex, joins chloride in the tetrahydrofuran solution of anhydrous ferric trichloride, under room temperature, reacts; Then vacuum pumps solvent, residue through hexane washing, drain, then with oxolane extraction, Centrifugical extraction liquid, shifts clear liquid; Finally in clear liquid, add hexane recrystallization, under room temperature, separating out yellow crystals is ionic iron (III) complex; Described chloride is [{ (RNC (CH3))NCHCHN(CH2Ph) } CH] Cl, wherein R is 2,6-diisopropyl phenyl.
In technique scheme, terminal alkyne compound is phenylacetylene, substitutedphenylethynyl, heterocycle aryne or diine; Such as phenylacetylene, 4-methylbenzene acetylene, 4-tert-butyl benzene acetylene, 4-acetenyl biphenyl, 4-methoxybenzene acetylene, 4-bromobenzene acetylene, 4-chlorobenzene acetylene, 4-fluorobenzene acetylene, 2-fluorobenzene acetylene, 3-fluorobenzene acetylene, 4-trifluoromethyl phenylacetylene, 2-thiophene acetylene, Isosorbide-5-Nitrae-diacetylene-benzene, 4-nitrobenzene acetylene, 1-hexin, 4-acetenyl cyanophenyl or 4-acetylenylbenzene formaldehyde.
In technique scheme, in amount of substance, cesium carbonate is 1.8～2.5 times of terminal alkyne compound consumption, and catalyst amount is terminal alkyne compound 3～6%, and preferred, cesium carbonate is 2 times of terminal alkyne compound consumption, and catalyst amount is terminal alkyne compound 5%.
In preferred technical scheme, the stirring reaction time is 16～18 hours.
The present invention is further open to be reacted and obtains propiolic acid compounds with carbon dioxide by terminal alkyne compound under ionic iron (III) is complex-catalyzed.
Above-mentioned course of reaction can represent as follows:
Due to the utilization of technique scheme, the present invention compared with prior art has the following advantages:
The present invention adopts iron (III) complex as single-component catalyst first, taking carbon dioxide as carboxylated reagent, has realized the carboxylation reaction of Terminal Acetylenes under normal pressure, make propiolic acid compounds, this reaction condition gentleness, productive rate is high, especially can under normal pressure, complete; There is inexpensive, green, eco-friendly feature, and catalyst structure is clear and definite, component is single, synthetic method is simple, air-stable is easy to operate simultaneously, is conducive to large-scale industrialization application. Especially preparation method disclosed by the invention has good applicability to various Terminal Acetylenes, especially cyano-containing, aldehyde radical etc. are also had to good tolerance to the Terminal Acetylenes of the responsive functional group of organometallic reagent (as RMgBr etc.), solved prior art and only can be suitable for the defect of some terminal alkyne compound; The propiolic acid compounds that contains various functional groups for preparation, enrich propiolic acid compounds structure a kind of new method is provided.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment mono-: (molecular formula is [{ (RNC (CH containing ionic iron (III) complex of single imines functionalization glyoxaline cation3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl)) and synthetic
By [{ (RNC (CH3))NCHCHN(CH2Ph) } CH] Cl (R is 2,6-diisopropyl phenyl) (0.40 gram, 1.0 mMs) joins (0.16 gram of anhydrous ferric trichloride, 1.0 mMs) tetrahydrofuran solution in, react 3 hours at 25 DEG C, vacuum pumps solvent, hexane washing, drain, with oxolane extraction, centrifugal, clear liquid shifts, in clear liquid, add hexane recrystallization, under room temperature, separate out yellow crystals, productive rate 93%.
Product is carried out to elementary analysis, and result is as shown in table 1.
Table 1 is containing ionic iron (III) the complex results of elemental analyses of single imines functionalization glyoxaline cation
| C：（%） | H：（%） | N：（%） | |
| Theoretical value | 51.64 | 5.42 | 7.53 |
| Actual value | 51.70 | 5.38 | 7.66 |
Because the complex of iron has paramagnetism, so it is not carried out to nuclear-magnetism sign.
This complex is to exist with the form of ion pair, wherein [FeCl4]-Characterize by Raman spectrum, find that it is at 333cm-1There is characteristic peak at place, is consistent with theory report.
Cationic moiety [{ (RNC (the CH of complex3))NCHCHN(CH2Ph)}CH]+(R is 2,6-diisopropyl phenyl) characterizes by mass spectrum, finds that it has a molecular ion peak at 360.2443 places, and this molecular ion peak is 360.2440 in theory, and actual measurement is with theoretical basically identical.
Prove that gained compound is target compound.
Embodiment bis-: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2, the 6-diisopropyl phenyl) phenylacetylene of catalysis and carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), phenylacetylene (55 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 97%.
Product is dissolved in to CDCl3In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,CDCl3,TMS):δ7.63-7.61(m,2H,Ar-H),7.51-7.47(m,1H,Ar-H),7.42-7.38(m,2H,Ar-H)ppm。
Embodiment tri-: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-methylbenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-methylbenzene acetylene (63 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 65 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 90%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.52(d,J=8.0Hz,2H,Ar-H),7.29(d,J=8.0Hz,2H,Ar-H),2.36(s,3H,CH 3)ppm。
Embodiment tetra-: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-tert-butyl benzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-tert-butyl benzene acetylene (90 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 20 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 88%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.58(d,J=8.0Hz,2H,Ar-H),7.51(d,J=8.0Hz,2H,Ar-H),1.30(s,9H,CH 3)ppm。
Embodiment five: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-acetenyl biphenyl of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-acetenyl biphenyl (89.1 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 65 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 88%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.81-7.73(m,6H,Ar-H),7.52(t,J=8.0Hz,2H,Ar-H),7.44(t,J=8.0Hz,1H,Ar-H)ppm。
Embodiment six: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-methoxybenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (16.8 milligrams, 0.03 mM, 6mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-methoxybenzene acetylene (65 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 20 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 85%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.59(d,J=8.0Hz,2H,Ar-H),7.03(d,J=8.0Hz,2H,Ar-H),3.82(s,3H,CH 3)ppm。
Embodiment seven: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-bromobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (29.3 milligrams, 0.9 mM), 4-bromobenzene acetylene (90.5 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 50 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 90%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.68(d,J=8.0Hz,2H,Ar-H),7.58(d,J=8.0Hz,2H,Ar-H)ppm。
Embodiment eight: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-chlorobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-chlorobenzene acetylene (68.3 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 50 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 93%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.67(d,J=12.0Hz,2H,Ar-H),7.55(d,J=8.0Hz,2H,Ar-H)ppm。
Embodiment nine: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-fluorobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-fluorobenzene acetylene (57 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 40 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 95%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.75-7.73(m,2H,Ar-H),7.38-7.33(m,2H,Ar-H)ppm。
Embodiment ten: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 2-fluorobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 2-fluorobenzene acetylene (58 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 40 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 94%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.72(td,J 1=7.4Hz,J 2=1.4Hz,1H,Ar-H),7.66-7.60(m,1H,Ar-H);7.40(t,J=9.2Hz,1H,Ar-H),7.33(t,J=7.6Hz,1H,Ar-H)ppm。
Embodiment 11: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-trifluoromethyl phenylacetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (8.4 milligrams, 0.015 mM, 3mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-trifluoromethyl phenylacetylene (82 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 40 DEG C, reacts 12 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 96%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.90-7.85(m,4H,Ar-H)ppm。
Embodiment 12: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 2-thiophene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 2-thiophene acetylene (50 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 90%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.91(dd,J 1=5.2Hz,J 2=1.2Hz,1H,Ar-H),7.70(dd,J 1=3.8Hz,J 2=1.0Hz,1H,Ar-H),7.23(dd,J 1=5.2Hz,J 2=3.6Hz,1H,Ar-H)ppm。
Embodiment 13: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2, the 6-diisopropyl phenyl) Isosorbide-5-Nitrae-diacetylene-benzene of catalysis and carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), Isosorbide-5-Nitrae-diacetylene-benzene (63.1 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 18 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 90%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.71(s,4H,Ar-H)ppm。
Embodiment 14: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 1-hexin of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (40.8 milligrams, 1.25 mMs), 1-hexin (58 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 70 DEG C, reacts 20 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 58%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ2.37(t,J=6.8Hz,2H,CH2),1.59(m,2H,CH2),1.58(m,2H,CH2),0.95(t,J=6.4Hz,3H,CH3)ppm。
Embodiment 15: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-acetenyl cyanophenyl of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-acetenyl cyanophenyl (63.6 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 50 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 93%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.96(d,J=8.0Hz,2H,Ar-H),7.84(d,J=12.0Hz,2H,Ar-H)ppm。
Embodiment 16: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-acetylenylbenzene formaldehyde of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-acetylenylbenzene formaldehyde (65.1 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 50 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 88%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ10.10(s,1H,CHO),8.01(d,J=8.0Hz,2H,Ar-H),7.88(d,J=8.0Hz,2H,Ar-H)ppm。
Embodiment 17: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 3-fluorobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 3-fluorobenzene acetylene (58 microlitres, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 40 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 96%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ7.57-7.48(m,3H,Ar-H),7.44-7.39(m,1H,Ar-H)ppm。
Embodiment 18: [{ (RNC (CH3))NCHCHN(CH2Ph)}CH][FeCl4] (R is 2,6-diisopropyl phenyl) the 4-nitrobenzene acetylene of catalysis and the carboxylation reaction of carbon dioxide
In reaction bulb, add successively catalyst (14.0 milligrams, 0.025 mM, 5mol%), cesium carbonate (32.6 milligrams, 1.0 mMs), 4-nitrobenzene acetylene (73.6 milligrams, 0.5 mM),N,N-dimethyl formamide (3 milliliters), passes into carbon dioxide, at 55 DEG C, reacts 16 hours under normal pressure. Reaction is cooled to room temperature, dilute with water, and hcl acidifying, extracted with diethyl ether, ether layer washs with saturated sodium-chloride, anhydrous sodium sulfate drying, solvent removed in vacuo obtains product, and productive rate is 90%.
Product is dissolved in to DMSO-d 6In (about 0.4mL), tube sealing, under room temperature on UnityInova-400 type NMR instrument measure characterize:1HNMR(400MHz,DMSO-d 6,TMS):δ8.31(d,J=8.0Hz,2H,Ar-H),7.94(d,J=8.0Hz,2H,Ar-H)ppm。
Claims (10)
1. a method of preparing propiolic acid compounds, is characterized in that, comprises the following steps: to add successively in reactor catalyst, cesium carbonate, terminal alkyne compound andN,N-dimethyl formamide; Then pass into carbon dioxide, in 40～70 DEG C, stirring reaction 12～20 hours under normal pressure; Then obtain propiolic acid compounds through hcl acidifying; The molecular structural formula of described catalyst is as follows:
。
2. prepare according to claim 1 the method for propiolic acid compounds, it is characterized in that: after reaction finishes, reactant liquor is cooled to room temperature, then pass through successively water dilution, hcl acidifying, extracted with diethyl ether, then ether layer saturated sodium-chloride extraction being obtained washs, through anhydrous sodium sulfate drying, last solvent removed in vacuo, obtains propiolic acid compounds again.
3. the method for preparing according to claim 1 propiolic acid compounds, is characterized in that: described terminal alkyne compound is phenylacetylene, substitutedphenylethynyl, heterocycle aryne, fragrant diine or aliphatic Terminal Acetylenes.
4. prepare according to claim 3 the method for propiolic acid compounds, it is characterized in that: described terminal alkyne compound is phenylacetylene, 4-methylbenzene acetylene, 4-tert-butyl benzene acetylene, 4-acetenyl biphenyl, 4-methoxybenzene acetylene, 4-bromobenzene acetylene, 4-chlorobenzene acetylene, 4-fluorobenzene acetylene, 2-fluorobenzene acetylene, 3-fluorobenzene acetylene, 4-trifluoromethyl phenylacetylene, 2-thiophene acetylene, Isosorbide-5-Nitrae-diacetylene-benzene, 4-nitrobenzene acetylene, 1-hexin, 4-acetenyl cyanophenyl or 4-acetylenylbenzene formaldehyde.
5. the method for preparing according to claim 1 propiolic acid compounds, is characterized in that: in amount of substance, cesium carbonate is 1.8～2.5 times of terminal alkyne compound consumption, and catalyst amount is terminal alkyne compound 3～6%.
6. the method for preparing according to claim 5 propiolic acid compounds, is characterized in that: in amount of substance, cesium carbonate is 2 times of terminal alkyne compound consumption, and catalyst amount is terminal alkyne compound 5%; The stirring reaction time is 16～18 hours.
7. ionic iron (III) complex application in the carboxylation reaction of catalysis terminal alkyne compound and carbon dioxide as single-component catalyst; The molecular structural formula of described ionic iron (III) complex is as follows:
。
8. application according to claim 7, is characterized in that: described terminal alkyne compound is phenylacetylene, substitutedphenylethynyl, heterocycle aryne, fragrant diine or aliphatic Terminal Acetylenes; 3～6mol% that the consumption of described ionic iron (III) complex is terminal alkyne compound.
9. application according to claim 8, it is characterized in that: described terminal alkyne compound is phenylacetylene, 4-methylbenzene acetylene, 4-tert-butyl benzene acetylene, 4-acetenyl biphenyl, 4-methoxybenzene acetylene, 4-bromobenzene acetylene, 4-chlorobenzene acetylene, 4-fluorobenzene acetylene, 2-fluorobenzene acetylene, 3-fluorobenzene acetylene, 4-trifluoromethyl phenylacetylene, 2-thiophene acetylene, Isosorbide-5-Nitrae-diacetylene-benzene, 4-nitrobenzene acetylene, 1-hexin, 4-acetenyl cyanophenyl or 4-acetylenylbenzene formaldehyde; The 5mol% that the consumption of described ionic iron (III) complex is terminal alkyne compound.
10. a propiolic acid compounds, is characterized in that: described propiolic acid compounds is reacted and obtains with carbon dioxide by terminal alkyne compound under ionic iron (III) is complex-catalyzed; The molecular structural formula of described ionic iron (III) complex is as follows:
Described terminal alkyne compound is phenylacetylene, substitutedphenylethynyl, heterocycle aryne, fragrant diine or aliphatic Terminal Acetylenes.
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| CN106565623A (en) * | 2016-10-31 | 2017-04-19 | 苏州大学 | Method of synthesizing heteroaromatic formic ether compound |
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| CN107353194A (en) * | 2017-06-18 | 2017-11-17 | 大连理工大学 | A kind of preparation method of propine acid compounds |
| CN111377810A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Synthetic method of propiolic acid |
| CN113149827A (en) * | 2021-04-19 | 2021-07-23 | 华南理工大学 | Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide |
| CN114874088A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院上海高等研究院 | Acetylenic acid and preparation method thereof |
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| CN107353194A (en) * | 2017-06-18 | 2017-11-17 | 大连理工大学 | A kind of preparation method of propine acid compounds |
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| CN113149827A (en) * | 2021-04-19 | 2021-07-23 | 华南理工大学 | Method for synthesizing alkynoic acid by using terminal alkyne and carbon dioxide |
| CN114874088A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院上海高等研究院 | Acetylenic acid and preparation method thereof |
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