CN106946682A - A kind of preparation method of propine acid compounds - Google Patents
A kind of preparation method of propine acid compounds Download PDFInfo
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- CN106946682A CN106946682A CN201710203363.9A CN201710203363A CN106946682A CN 106946682 A CN106946682 A CN 106946682A CN 201710203363 A CN201710203363 A CN 201710203363A CN 106946682 A CN106946682 A CN 106946682A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
The present invention relates to CO2Activating conversion and related chemistry technical field, be related to it is a kind of synthesize propine acid compounds method.It is characterized in that：In the presence of outer doping and alkali, Terminal Acetylenes and CO are realized2Directly reaction generates propine acid compounds.The applicable Terminal Acetylenes class substrate of the present invention is related to phenylacetylene, substitutedphenylethynyl, heterocycle aryne or aliphatic Terminal Acetylenes etc..Compared with prior art, the present invention is mainly to provide a kind of new simple reaction system.Using potassium carbonate, as alkali, quaternary ammonium salt, as additive and conveniently, the acetonitrile of post processing is as solvent for reaction, and still belong to the first time report.The reaction system have without transition-metal catalyst, experimental implementation is simple, raw material is cheap and easily-available, it is environment-friendly the features such as, with larger application value and economic results in society.
Description
Technical field
The present invention relates to CO2Activating conversion and related chemistry technical field, be related to a kind of propine acid compounds
Preparation method.
Background technology
Carbon dioxide is rich reserves, cheap and easy to get and reproducible C1Resource, high added value is generated by its activating conversion
The research of fine chemicals caused the extensive concern of people.In the past few decades, many passes are reported
In carbon dioxide fixation and the method for conversion [referring to：(a)Sakakura,T.；Choi,J.-C.；Yasuda,
H.Chem.Rev.2007,107,2365.(b)Q.Liu；L.Wu；R.Jackstell；M.Beller,Nat.Commun.2015,
6,5933.].Propine acid compounds are important synthetic intermediates, are widely used in synthesis fine chemicals, pharmaceutical molecules etc..
So the synthesis of propine acid compounds is constantly subjected to extensive concern.In the prior art, the side of propine acid compounds is synthesized
Method is mainly the oxidation carboxylation reaction of alkynes, and using formaldehyde or carbon monoxide as carboxylated reagent, but this method has CO
The problems such as toxicity is big.There is document report to promote CO using transition metal-catalyzed or cesium carbonate in the recent period2Third is prepared with Terminal Acetylenes reaction
Alkynes acid compounds, but have that transition-metal catalyst is expensive, part is huge and synthesize high boiling solvent difficult, used
The problems such as difficulty are post-processed [referring to (a) Dingyi Yu；Yugen Zhang,PNAS,2010,47,20189.(b)Hao
Cheng；Bei Zhao；Yingming Yao；Chengrong Lu.Green Chem.,2015,17,1675；(c)Manoj
Trivedi；a Abhinav Kumarb；Nigam P.Rath.Dalton Trans.,2015,44,20874；(d)Seung
Hyo Kim；Kwang Hee Kim；Soon Hyeok Hong.Angew.Chem.Int.Ed.2014,53,771；(e)Xiao-
Huan Liu；Jian-Gong Ma；Zheng Niu；Guang-Ming Yang；Peng
Cheng.Angew.Chem.Int.Ed.2015,54,988].Also once had been reported that using carbon dioxide and Terminal Acetylenes be raw material without metal
Propine acid compounds are generated in catalyst system and catalyzing, but alkali TBD used and cesium carbonate are costly, and the DMF used etc.
Solvent post processing difficulty is [referring to document (a) Yu Dingyi, Zhang Yugen, Green Chem., 2011,13,1275；(b)
X.Wang,Y.N.Lim,C.Lee,H.-Y.Jang,B.Y.Lee,Eur.J.Org.Chem.2013,1867].Therefore urged without metal
Agent, low cost and it is easy to the new method of propine acid compounds of post processing there is good application prospect.
The content of the invention
A kind of system the invention provides non-metal catalyst, without part promotes CO2With Terminal Acetylenes reaction generation propiolic acid
The method of class compound.This method has the advantages that reaction cost is low, experimental implementation is simple, easily realize industrialization.
The present invention is one kind with Terminal Acetylenes and CO2For raw material, in the case where additive and alkali promote, Terminal Acetylenes is with carbon dioxide organic
Reacted in solvent, generate propine acid compounds, reaction equation is as follows：
The technical scheme that this method is used is as follows：
The synthesis of propiolic acid：Additive, alkali, solvent and Terminal Acetylenes are added sequentially to after autoclave in glove box,
CO is filled with outside glove box2.Autoclave is closed, is put into oil bath pan and starts reaction.
Characterized in that, organic solvent includes：Toluene, n-hexane, tetrahydrofuran, 1,4- dioxane, dichloromethane, three
Chloromethanes, acetonitrile.Preferential tetrahydrofuran, acetonitrile, 1,4- dioxane.
Range of reaction temperature is 20 DEG C~150 DEG C, preferably 75 DEG C~100 DEG C.
Reaction time range is 4~36 hours, preferably 15~24 hours.
Alkali is selected from potassium carbonate, sodium carbonate, sodium acetate, potassium acetate etc..It is preferred that potassium carbonate.
Additive is selected from methylene diacetate ammonium, tetrabutylammonium chloride, TBAB, tetrabutylammonium iodide, tetrabutyl vinegar
Sour ammonium, four n-octyl ammonium bromides, cetyl trimethylammonium bromide, ten alkyl trimethyl ammonium bromides, tetrabutyl ammonium nitrate, tetramethyl
Base ammonium iodide, sodium trifluoroacetate, sodium sulphate, ammonium acetate, methyltriphenylphosphonium bromide, tetrafluoro boric acid tri-butyl phosphine, ammonium nitrate,
Sodium nitrate, potassium nitrate, sodium sulfite etc..It is preferred that tetrabutylammonium acetate ammonium and tetrabutyl ammonium nitrate.
The amount of organic solvent is 3~10mL.
The mol ratio of terminal alkyne compound and alkali is 1:0.5~10, preferably 1:4.
The mol ratio of terminal alkyne compound and additive is 1:0.1~5, preferably 1:1.5.
CO2Pressure is 0.1MPa~6MPa, preferably 1MPa.
Brief description of the drawings
Brief description of the drawings
Fig. 1 is phenylpropiolic acid in embodiment 11H nuclear magnetic spectrograms.
Fig. 2 is phenylpropiolic acid in embodiment 113C nuclear magnetic spectrograms.
Fig. 3 is 2- methoxybenzene propiolic acids in embodiment 21H nuclear magnetic spectrograms.
Fig. 4 is 2- methoxybenzene propiolic acids in embodiment 213C nuclear magnetic spectrograms.
Fig. 5 is this propiolic acid of 4- chlorine in embodiment 31H nuclear magnetic spectrograms.
Fig. 6 is this propiolic acid of 4- chlorine in embodiment 313C nuclear magnetic spectrograms.
Fig. 7 is 3- bromobenzene propiolic acids in embodiment 41H nuclear magnetic spectrograms.
Fig. 8 is 3- bromobenzene propiolic acids in embodiment 41H nuclear magnetic spectrograms.
Fig. 9 is to bromobenzene propiolic acid in embodiment 51H nuclear magnetic spectrograms.
Figure 10 is to bromobenzene propiolic acid in embodiment 513C nuclear magnetic spectrograms.
Figure 11 is 3- fluorobenzene propiolic acids in embodiment 61H nuclear magnetic spectrograms.
Figure 12 is 3- fluorobenzene propiolic acids in embodiment 613C nuclear magnetic spectrograms.
Figure 13 is 4- ethyl phenylpropiolic acids in embodiment 71H nuclear magnetic spectrograms.
Figure 14 is 4- ethyl phenylpropiolic acids in embodiment 713C nuclear magnetic spectrograms.
Figure 15 is 2- propiolic acid thiophene in embodiment 81H nuclear magnetic spectrograms.
Figure 16 is 2- propiolic acid thiophene in embodiment 813C nuclear magnetic spectrograms.
Figure 17 is 4- propyl group phenylpropiolic acids in embodiment 91H nuclear magnetic spectrograms.
Figure 18 is 4- propyl group phenylpropiolic acids in embodiment 913C nuclear magnetic spectrograms.
Figure 19 is to fluorobenzene propiolic acid in embodiment 101H nuclear magnetic spectrograms.
Figure 20 is to fluorobenzene propiolic acid in embodiment 1013C nuclear magnetic spectrograms.
Embodiment
Propiolic acid method is generated under alkali promotion the invention provides one kind, this method has reaction green, experimental implementation
Simply, the advantages of easily realizing industrialization, shows good application prospect.
With reference to specific embodiment, the present invention is expanded on further.Embodiment is merely to illustrate the present invention rather than limit
The scope of the present invention processed.The simple replacement or improvement that technical staff in the art is done to the present invention belong to institute of the present invention
Within the technical scheme of protection.
Embodiment 1：The synthesis of phenylpropiolic acid
In glove box it is accurate measure potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined acetonitrile (5.0mL), phenylacetylene (102mg, 1mmol), be added sequentially to the anti-of 25mL
Answer in kettle, CO is filled with outside glove box2(0.1MPa).Capping kettle, is placed in 90 DEG C of oil baths and reacts 4h., will after reaction terminates
Reactor is slowly cooled to room temperature, and then slowly releases remaining gas.Remaining reaction solution is transferred to single port bottle in reactor,
Add 1M hydrochloric acid and be acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, (is washed through silica gel post separation
De- agent：Petrol ether/ethyl acetate=6/1) obtain phenylpropiolic acid 124mg, yield is 85%.1H NMR(400MHz,CDCl3)δ
11.03(s,1H),7.65–7.57(m,2H),7.53–7.34(m,1H),7.22(d,2H).13C NMR(101MHz,CDCl3)δ
159.00,133.34,131.22,128.70,119.06,89.20,80.13.
Embodiment 2：The synthesis of 2- methoxybenzene propiolic acids
In glove box it is accurate measure sodium carbonate (312mg, 3mmol, 300mol%), tetrabutyl ammonium nitrate (304mg,
1mmol, 100mol%), refined THF (5.0mL), 2- Methoxy-phenylacetylenes (132mg, 1mmol), be added sequentially to 25mL
Reactor in, CO is filled with outside glove box2(4MPa).Capping kettle, is placed in 30 DEG C of oil baths and reacts 36h.After reaction terminates,
Reactor is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution is transferred to single port in reactor
Bottle, adds 1M hydrochloric acid and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, through silica gel post separation
(eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 2- methoxybenzene propiolic acid 158mg, yield is 90%.1H NMR
(400MHz,CDCl3)δ10.42(s,1H),7.65(d,1H),7.54(t,1H),7.04(dd,2H),4.01(s,3H).13C
NMR(101MHz,CDCl3)δ161.90,158.72,135.22,132.87,120.60,110.91,108.40,86.20,
84.07,55.88.
Embodiment 3：The synthesis of 4- chlorobenzene propiolic acids
Accurately potassium carbonate (552mg, 4mmol, 400mol%), positive TBAB are measured in glove box
(644.6mg, 2mmol, 200mol%), refined dichloromethane (5.0mL), 4- chlorobenzenes acetylene (136.5mg, 1mmol), according to
It is secondary to be added in 25mL reactor, CO is filled with outside glove box2(2MPa).Capping kettle, is placed in 60 DEG C of oil baths and reacts
18h.After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.It is remaining anti-in reactor
Answer liquid to be transferred to single port bottle, add 1M hydrochloric acid and be acidified to PH=1, be extracted with ethyl acetate, collect organic phase, be removed in vacuum molten
Agent, through silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 4- chlorobenzene propiolic acid 145mg, yield is 80%
。1H NMR(400MHz,MeOD)δ7.56(d,2H),7.44(d,2H)；13C NMR(101MHz,MeOD)δ155.02,136.63,
133.91,128.85,118.28,83.73,81.37.
Embodiment 4：The synthesis of 4- methyl phenylpropiolic acids
Accurately sodium acetate (123mg, 1.5mmol, 150mol%), tetrabutylammonium acetate ammonium are measured in glove box
(451.5mg, 1.5mmol, 150mol%), refined n-hexane (5.0mL), to methyl phenylacetylene (116mg, 1mmol), according to
It is secondary to be added in 25mL reactor, CO is filled with outside glove box2(0.5MPa).Capping kettle, is placed in 100 DEG C of oil baths and reacts
24h.After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.It is remaining anti-in reactor
Answer liquid to be transferred to single port bottle, add 1M hydrochloric acid and be acidified to PH=1, be extracted with ethyl acetate, collect organic phase, be removed in vacuum molten
Agent, through silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain to methyl phenylpropiolic acid 147mg, yield is
92%.1H NMR(400MHz,CDCl3)δ7.44(d,2H),7.30(d,2H),2.37(s,3H).13C NMR(101MHz,
CDCl3)δ159.10,142.01,133.36,129.49,115.97,89.86,79.84,21.78.
Embodiment 5：Synthesis to bromobenzene propiolic acid
Accurately potassium carbonate (552mg, 4mmol, 400mol%), four n-octyl ammonium bromides are measured in glove box
(2734.0mg, 5mmol, 500mol%), refined acetonitrile (5.0mL), to bromobenzene acetylene (181mg, 1mmol), successively plus
Enter into 25mL reactor, CO is filled with outside glove box2(1.5MPa).Capping kettle, is placed in 110 DEG C of oil baths and reacts 28h.
After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution in reactor
Single port bottle is transferred to, 1M hydrochloric acid is added and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, pass through
Silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain to bromobenzene propiolic acid 178mg, yield is 79%.1H
NMR(400MHz,MeOD)δ7.57(d,2H),7.46(d,2H)；13C NMR(101MHz,MeOD)δ154.98,134.00,
131.86,124.91,118.69,83.78,81.49.
Embodiment 6：The synthesis of 3- fluorobenzene propiolic acids
Accurately potassium carbonate (345.5mg, 2.5mmol, 250mol%), tetramethyl ammonium acetate are measured in glove box
(226.4mg, 2mmol, 200mol%), refined Isosorbide-5-Nitrae-dioxane (5.0mL), 3- fluorobenzene acetylene (120mg, 1mmol),
It is added sequentially in 25mL reactor, CO is filled with outside glove box2(3MPa).Capping kettle, is placed in 100 DEG C of oil baths and reacts
18h.After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.It is remaining anti-in reactor
Answer liquid to be transferred to single port bottle, add 1M hydrochloric acid and be acidified to PH=1, be extracted with ethyl acetate, collect organic phase, be removed in vacuum molten
Agent, through silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 3- fluorobenzene propiolic acid 137mg, yield is 84%
。1H NMR (400MHz, MeOD) δ 7.49-7.38 (m, 2H), 7.33 (d, J=9.2Hz, 1H), 7.25 (t, J=8.4Hz, 1H)
.13C NMR(101MHz,MeOD)δ161.11,154.89,130.57,128.56,121.47,119.00,117.79,83.30,
81.10.
Embodiment 7：The synthesis of 4- ethyl phenylpropiolic acids
Accurately potassium carbonate (221mg, 1.6mmol, 160mol%), tetrabutylammonium acetate ammonium are measured in glove box
(451.5mg, 1.5mmol, 150mol%), refined THF (5.0mL), 4- Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylenes (130mg, 1mmol), successively
It is added in 25mL reactor, CO is filled with outside glove box2(2MPa).Capping kettle, is placed in 80 DEG C of oil baths and reacts 20h.
After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution in reactor
Single port bottle is transferred to, 1M hydrochloric acid is added and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, pass through
Silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 4- ethyl phenylpropiolic acid 149mg, yield is 86%.1H
NMR(400MHz,CDCl3)δ9.62(s,1H),7.55(d,2H),7.25(t,2H),2.70(q,2H),1.26(t,3H).13C
NMR(101MHz,CDCl3)δ158.79,148.15,133.47,128.30,116.18,89.75,79.80,29.05,15.14.
Embodiment 8：The synthesis of 2- propiolic acid thiophene
Accurately potassium carbonate (552mg, 4mmol, 400mol%), methyltriphenylphosphonium bromide are measured in glove box
(1074.7mg, 3mmol, 300mol%), refined acetonitrile (5.0mL), 2- thiophene acetylenes (108mg, 1mmol), successively
It is added in 25mL reactor, CO is filled with outside glove box2(1MPa).Capping kettle, is placed in 120 DEG C of oil baths and reacts 12h.
After reaction terminates, reactor is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution in reactor
Single port bottle is transferred to, 1M hydrochloric acid is added and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, pass through
Silica gel post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 2- propiolic acid thiophene 118.6mg, yield is 78%.1H
NMR(400MHz,MeOD)δ7.69(d 1H),7.60–7.55(m,1H),7.15(t,1H)；13C NMR(101MHz,MeOD)δ
155.08,136.21,131.26,127.48,119.04,84.63,79.00.。
Embodiment 9：The synthesis of 4- propyl group phenylpropiolic acids
In glove box it is accurate measure potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined acetonitrile (5.0mL), 4- propyl group phenylacetylene (144mg, 1mmol), be added sequentially to
In 25mL reactor, CO is filled with outside glove box2(1.3MPa).Capping kettle, is placed in 50 DEG C of oil baths and reacts 24h.Reaction
After end, reactor is slowly cooled to room temperature, remaining gas is then slowly released.Remaining reaction solution transfer in reactor
To single port bottle, add 1M hydrochloric acid and be acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, through silica gel
Post separation (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain 4- propyl group phenylpropiolic acid 165mg, yield is 88%.1H NMR
(400MHz,CDCl3)δ10.81(s,1H),7.56(d,2H),7.23(d,2H),2.64(t,2H),1.67(dd,2H),0.96
(t,3H).13C NMR(101MHz,CDCl3)δ158.91,146.65,133.37,128.87,116.22,89.77,79.86,
38.13,24.16,13.72.
Embodiment 10：Synthesis to fluorobenzene propiolic acid
In glove box it is accurate measure potassium carbonate (552mg, 4mmol, 400mol%), tetrabutylammonium acetate ammonium (451.5mg,
1.5mmol, 150mol%), refined toluene (5.0mL), to fluorobenzene acetylene (120mg, 1mmol), be added sequentially to 25mL
Reactor in, CO is filled with outside glove box2(0.7MPa).Capping kettle, is placed in 75 DEG C of oil baths and reacts 16h.Reaction terminates
Afterwards, reactor is slowly cooled to room temperature, then slowly releases remaining gas.Remaining reaction solution is transferred to list in reactor
Mouth bottle, adds 1M hydrochloric acid and is acidified to PH=1, be extracted with ethyl acetate, collect organic phase, solvent is removed in vacuum, through silicagel column point
From (eluant, eluent：Petrol ether/ethyl acetate=6/1) obtain to fluorobenzene propiolic acid 126mg, yield is 77%.1H NMR
(400MHz,MeOD)δ7.71(dd,2H),7.32(t,2H)；13C NMR(101MHz,MeOD)δ165.18,162.68,
155.16,135.05,134.96,115.93,115.70,84.09,80.43。
Claims (5)
1. a kind of preparation method of propine acid compounds, it is characterised in that in the case where additive and alkali promote, Terminal Acetylenes and titanium dioxide
Carbon reacts in organic solvent, generates propine acid compounds, and synthetic route is as follows：
Comprise the following steps：
(1) additive, alkali, Terminal Acetylenes, organic solvent are added into autoclave, is then charged with carbon dioxide and closes autoclave, in oil
Reacted in bath under magnetic agitation；
(2) the propiolic acid salt compounds crude product that step (1) is obtained is added water, is acidified, is then extracted with ethyl acetate, obtains
Propiolic acid crude product purified by silica gel post is separated, and is finally separating to obtain propine acid product；
Reaction temperature is 20 DEG C~150 DEG C；Reaction pressure is 0.1MPa~6MPa；4~36 hours reaction time；
Described Terminal Acetylenes general structure isIt is miscellaneous that wherein R is selected from substituted or unsubstituted aliphatic group, aryl radical, fragrance
Ring group；
The additive is selected from tetramethyl ammonium acetate, tetrabutylammonium chloride, TBAB, tetrabutylammonium iodide, the tetrabutyl
Ammonium acetate, four n-octyl ammonium bromides, cetyl trimethylammonium bromide, ten alkyl trimethyl ammonium bromides, tetrabutyl ammonium nitrate, four
Methylpyridinium iodide ammonium, sodium trifluoroacetate, sodium sulphate, ammonium acetate, methyltriphenylphosphonium bromide, tetrafluoro boric acid tri-butyl phosphine, nitric acid
One or two kinds of mixing in ammonium, sodium nitrate, potassium nitrate, sodium sulfite；The mol ratio of Terminal Acetylenes and additive is 1:0.1~5.
2. preparation method as claimed in claim 1, it is characterised in that the alkali is selected from potassium carbonate, sodium carbonate, sodium acetate, second
One kind in sour potassium；Terminal Acetylenes is 1 with the mol ratio of alkali used:0.5~10.
3. preparation method as claimed in claim 1 or 2, it is characterised in that the organic solvent is toluene, n-hexane, tetrahydrochysene
At least one solvent in furans, 1,4- dioxane, dichloromethane, chloroform, acetonitrile.
4. preparation method as claimed in claim 1 or 2, it is characterised in that the molar concentration of Terminal Acetylenes is 0.01~2mmol/mL.
5. preparation method as claimed in claim 3, it is characterised in that the molar concentration of Terminal Acetylenes is 0.01~2mmol/mL.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110330420A (en) * | 2019-07-31 | 2019-10-15 | 湖南大学 | The preparation method of the acid of different substituents |
| 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 |
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| CN103168022A (en) * | 2010-08-20 | 2013-06-19 | 巴斯夫欧洲公司 | Process for preparing a propiolic acid or a derivative thereof |
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| CN103168022A (en) * | 2010-08-20 | 2013-06-19 | 巴斯夫欧洲公司 | Process for preparing a propiolic acid or a derivative thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111377810B (en) * | 2018-12-31 | 2023-05-05 | 中国石油化工股份有限公司 | Synthesis method of propiolic acid |
| CN110330420A (en) * | 2019-07-31 | 2019-10-15 | 湖南大学 | The preparation method of the acid of different substituents |
| CN110330420B (en) * | 2019-07-31 | 2020-07-10 | 湖南大学 | Process for preparing acids with different substituents |
| 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 |
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