CN105017016A - Method for synthesizing propiolic alcohol in simple mode - Google Patents

Method for synthesizing propiolic alcohol in simple mode Download PDF

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Publication number
CN105017016A
CN105017016A CN201510384739.1A CN201510384739A CN105017016A CN 105017016 A CN105017016 A CN 105017016A CN 201510384739 A CN201510384739 A CN 201510384739A CN 105017016 A CN105017016 A CN 105017016A
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zinc powder
propiolic alcohol
reaction
carbonyl compound
simple synthesis
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CN105017016B (en
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陈伟
张文
赵刚
蒲林
刘继峰
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Chengdu Zhipulai Biomedicine Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/28—Alcohols containing only six-membered aromatic rings as cyclic part with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/34—Monohydroxylic alcohols containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
    • C07C33/48—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts with unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing propiolic alcohol in a simple mode. The method solves the problems of extreme sensitivity on water and air in a traditional method and difficult realization on massive production in prior art. The method comprises the following steps: 1)adding activated zinc powder, iodomethane or iodoethane, terminal acetylene, and a solvent in a reaction container; stirring at room temperature until the zinc powder disappears; 2)after the zinc powder is completely disappeared, adding a carbonyl compound dissolved by an organic solvent; and 3)stirring at room temperature and stopping the reaction until the carbonyl compound disappears, and separating a reaction solution and purifying to obtain the product. The method has the advantages of mild reaction condition, easily available raw materials, convenient operation, short reaction period and large scale production.

Description

A kind of method of simple synthesis propiolic alcohol
Technical field
The present invention relates to a kind of preparation method of propiolic alcohol, what be specifically related to is the addition reaction of terminal alkyne to carbonyl compound.
Background technology
Propiolic alcohol is important organic synthesis intermediate, and it is widely used in the synthesis of natural product, medicine and complicated macromolecular cpd on the one hand; On the other hand, the functional group of alkynyl and these two kinds of flexible of hydroxyl can make it in molecular diversity, have very large potential using value by functional group conversions.
Propiolic alcohol can be obtained to the addition reaction of aldehydes or ketones by terminal group alkynes, reaction process is generally first reacted with terminal alkyne by the active metal such as zinc alkyl(s), butyllithium reagent to generate alkynyl zinc or alkynyl lithium reagent, then obtains propiolic alcohol compound to carbonyl compound addition.But the metal reagent such as zinc alkyl(s) and butyllithium is responsive to water electrode, needs the strict water-content controlling reaction system, strict anhydrous drying is all needed, therefore severe reaction conditions to the required reagent of reaction and solvent, vessel, operation inconvenience.
Summary of the invention
The object of the invention is to avoid use the raw material to water and air all quite sensitive in prior art, a kind of method of simple synthesis propiolic alcohol is provided, thus realizes scale operation.
For solving the scarce limit of conventional art, technical scheme of the present invention is as follows:
A method for simple synthesis propiolic alcohol, comprises the following steps:
(1) in reaction vessel, add activated zinc powder, iodine first (second) alkane, terminal alkyne, N-Methyl pyrrolidone, stirring at room temperature disappears to zinc powder;
(2) zinc powder completely dissolve, adds the carbonyl compound of organic solvent dissolution;
(3) stirring at room temperature, adopt silica gel thin-layer chromatography monitoring reaction process, until carbonyl compound disappearance stopped reaction, namely reaction solution obtains product after separation and purification.
Reaction process of the present invention is as follows: zinc powder and iodine first (second) alkane react and generates zincon, then with terminal alkyne effect after, then attack carbonyl, and then generate propiolic alcohol.
Reaction formula of the present invention is as follows:
。
Present invention achieves in an atmosphere, zinc can be realized and iodine first (second) alkane reacts without the need to adding other catalyzer, and facilitate the addition of terminal alkyne and carbonyl compound, and then be conducive to a large amount of productions realizing propiolic alcohol.In above-mentioned reaction formula: NMP is N-Methyl pyrrolidone, MeI is methyl iodide, and EtI is iodoethane, and Zn Powder is zinc powder, and DCM is methylene dichloride; R is aryl, alkyl or alkyl; R 1for aryl, alkyl or alkyl; R 2for COOMe, H or COOEt.
Further, in described step (3), the concrete steps of reaction solution separation and purification are as follows:
In reaction solution, add saturated aqueous ammonium chloride and organic solvent, be separated organic phase, aqueous phase organic solvent extraction three times, merges organic phase, and saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, and namely silicagel column obtains product after being separated.
Further, described post separation condition is excessively sherwood oil: ethyl acetate=10:1 ~ 20:1.
Preferably, described terminal alkyne is fatty alkynes or aromatic alkyne; Described carbonyl compound is alkanoic, aromatic aldehyde, aliphatic ketone or aromatic ketone.
Preferably, in described step (1), solvent is N-Methyl pyrrolidone; In described step (2), organic solvent is methylene dichloride, toluene or normal hexane, is preferably methylene dichloride.
In order to reach higher productive rate, the mol ratio between described carbonyl compound, terminal alkyne, activated zinc powder and iodine first (second) alkane is 1: (2 ~ 4): (3 ~ 6): (6 ~ 12).
The present invention compared with prior art, has the following advantages and beneficial effect:
1, the present invention can realize zinc powder and iodine first (second) alkane reacts and promotes the addition of alkynes and carbonyl in an atmosphere, and reaction conditions is gentle, and thus having can the advantage of scale operation racemize propiolic alcohol;
2, the present invention need not add other catalyzer, zinc ethyl, butyllithium that also directly not use water electrode be sensitivity, but by generating zincon and promote the generation of reaction in reaction process; The advantages such as the inventive method has reaction conditions gentleness, raw material is easy to get, easy to operate, reaction time is shorter;
3, the present invention is not only only applicable to realize the addition of alkynes to aldehyde in atmosphere, also achieves in atmosphere that alkynes is to the addition reaction of ketone, and range of application is more extensive.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A method for simple synthesis propiolic alcohol, in the present embodiment be phenylacetylene to methyl benzoylformate addition reaction, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), phenylacetylene (2 mmol, 4 equiv), 0.5ml N-Methyl pyrrolidone, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add methyl benzoylformate (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, stirring at room temperature 12h, raw material methyl benzoylformate disappears, and stopped reaction, adds 10ml saturated aqueous ammonium chloride and methylene dichloride in reaction solution, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merges organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:3.83(1H,s,-OH), 5.70(1H,s,C ＊-H), 7.33-7.53 ( 8H ,m,C 5-3H,C 5-5H)。7.76-7.81( 2H ,m,C 5-2H)。
Embodiment 2
Be the reaction of phenylacetylene to α, α, α-trifluoroacetophenone addition in the present embodiment, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), phenylacetylene (2 mmol, 4 equiv), 0.5ml N-Methyl pyrrolidone, stirring at room temperature 2h, disappears to zinc powder.
After zinc powder completely dissolve, add α, α, α-trifluoroacetophenone (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, stirring at room temperature 12h, raw material α, α, α-trifluoroacetophenone disappears, and stopped reaction, adds 10ml saturated aqueous ammonium chloride and methylene dichloride in reaction solution, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merges organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:3.17(1H,s,-OH), 7.34-7.52(8H,m, C 5-3H, C 5-5H), 7.81-7.82( 2H ,dd,C 5-2H)。
Embodiment 3
In the present embodiment be phenylacetylene to phenyl aldehyde addition reaction, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), phenylacetylene (2 mmol, 4 equiv), 0.5mlN-methyl-2-pyrrolidone, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add the dichloromethane solution of phenyl aldehyde (0.5 mmol, 1 equiv), silica gel thin-layer chromatography monitoring reaction process, stirring at room temperature 12h, raw material benzaldehyde disappearance, stopped reaction, adds 10ml saturated aqueous ammonium chloride and methylene dichloride in reaction solution, stirs 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merges organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:2.32(1H,d,-OH), 5.70(1H,d,C ＊-H), 7.30-7.45 ( 8H ,m,C 5-3H,C 5-5H),7.61-7.62( 2H ,m,C 5-2H)。
Embodiment 4
In the present embodiment be phenylacetylene to Pyruvic Acid Methyl ester addition reaction, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), phenylacetylene (2 mmol, 4 equiv), 0.5mlN-methyl-2-pyrrolidone, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add Pyruvic Acid Methyl ester (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, iodine cylinder develops the color, stirring at room temperature 12h, and raw material acetone acid methyl esters disappears, stopped reaction, in reaction solution, add 10ml saturated aqueous ammonium chloride and methylene dichloride, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merge organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:1.79（3H,s,-CH 3）,3.53(1H,s,-OH), 3.84（3H,s,-OCH 3）, 7.27-7.44 ( 3H ,m,C 5-3H),7.45-7.46( 2H ,m,C 5-2H)。
Embodiment 5
In the present embodiment be phenylacetylene to hexahydrobenzaldehyde addition reaction, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), the N-Methyl pyrrolidone of MeI (6 mmol, 12 equiv), phenylacetylene (2 mmol, 4 equiv), 0.5ml, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add hexahydrobenzaldehyde (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, iodine cylinder develops the color, stirring at room temperature 12h, and raw material hexahydrobenzaldehyde disappears, stopped reaction, in reaction solution, add 10ml saturated aqueous ammonium chloride and methylene dichloride, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merge organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:1.09-1.34（5H,m,-C 6H 11）, 1.61-1.68（2H, m,-C 6H 11）, 1.78-1.85（2H, d,-C 6H 11）,1.84(1H,s,-OH) , 1.91-1.94（2H, d,-C 6H 11）7.28-7.33 ( 3H ,m,C 5-3H),7.41-7.46( 2H ,m,C 5-2H)。
Embodiment 6
In the present embodiment be 3-bromobenzene acetylene to methyl benzoylformate addition reaction, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), 3-bromobenzene acetylene (2 mmol, 4 equiv), 0.5ml N-Methyl pyrrolidone, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add methyl benzoylformate (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, stirring at room temperature 12h, raw material methyl benzoylformate disappears, and stopped reaction, adds 10ml saturated aqueous ammonium chloride and methylene dichloride in reaction solution, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merges organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm: 3.73-3.83（3H,s,-CH 3）4.28(1H,s,-OH), 7.22(1H,t, C 5-1H), 7.36-7.51 ( 5H ,m, C 5-5H)。7.68-7.73( 3H ,m,C 5-3H)。
Embodiment 7
Be the reaction of 1-heptyne to methyl benzoylformate addition in the present embodiment, concrete operation step is as follows:
In air, in 25ml round-bottomed flask, add activated zinc powder (3 mmol, 6 equiv), MeI (6 mmol, 12 equiv), 1-heptyne (2 mmol, 4 equiv), 0.5ml N-Methyl pyrrolidone, stirring at room temperature 2h, disappears to activated zinc powder.
After zinc powder completely dissolve, add methyl benzoylformate (0.5 mmol, 1 equiv) dichloromethane solution, silica gel thin-layer chromatography monitoring reaction process, stirring at room temperature 12h, raw material methyl benzoylformate disappears, and stopped reaction, adds 10ml saturated aqueous ammonium chloride and methylene dichloride in reaction solution, stir 10min, be separated organic phase, aqueous phase dichloromethane extraction three times, merges organic phase, saturated common salt is washed, anhydrous sodium sulfate drying, concentrated, silicagel column separating-purifying obtains product.
Carry out proton nmr spectra detection to the propiolic alcohol that the present embodiment obtains, detected result is as follows:
1H NMR（400MHz，CDCl 3）δppm:0.89-0.92(3H,t,-CH 3),1.25-1.59(6H,m,-CH 2)
3.76(1H，t，-OCH 3),4.11 (1H，d，-OH),7.26-7.39 ( 3H ,m, C 5-3H), 7.66 (2H ,m,C 5-2H)。
Embodiment 8
The difference of the present embodiment and embodiment 1 is only: the MeI in embodiment 1 is replaced to EtI, and other reaction conditionss are constant.
Embodiment 9
The difference of the present embodiment and embodiment 1 is: in the present embodiment, the add-on of methyl benzoylformate is 0.5mmol, the add-on of phenylacetylene is 1.5mmol, the add-on of activated zinc powder is 2mmol, and the add-on of methyl iodide is 4mmol, and other reaction conditionss are identical with the reaction conditions of embodiment 1.
Embodiment 10
The present embodiment is from the difference of embodiment 1: the add-on in the present embodiment between carbonyl compound, terminal alkyne, activated zinc powder and iodoethane is different.In the present embodiment, the add-on of methyl benzoylformate is 0.5mmol, the add-on of phenylacetylene is 1.5mmol, and the add-on of activated zinc powder is the add-on of 1.5mmol, EtI is 3mmol, organic solvent adopts normal hexane, and other reaction conditions is identical with the reaction conditions of embodiment 1.
The productive rate of the propiolic alcohol that above-described embodiment 1-10 generates is detected, and lists the chemical structure of the propiolic alcohol of synthesis material and generation, specifically as shown in table 1.
Table 1
Known by the result of the various embodiments described above: the present invention not only can realize terminal alkyne and aldehyde addition generates propiolic alcohol, also can realize terminal alkyne and ketone addition generates propiolic alcohol, and be no matter terminal alkyne and aldehyde addition or terminal alkyne and ketone addition, it all can react in an atmosphere, and without the need to adding other catalyzer in production process; And reaction conditions of the present invention is gentle, raw material is easy to get, easy to operate, reaction time is shorter, be thus very applicable to scale operation propiolic alcohol.
Meanwhile, known by above-mentioned yield results, productive rate of the present invention can reach more than 70%, when terminal alkyne is phenylacetylene, effect more, now, when carbonyl compound is hexahydrobenzaldehyde, the productive rate of propiolic alcohol even can reach 95%, effectively shows that synthetic method effect of the present invention is extremely excellent.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as adopt principle of design of the present invention, and the change carried out non-creativeness work on this basis and make, all should belong within protection scope of the present invention.

Claims (7)

1. a method for simple synthesis propiolic alcohol, is characterized in that, comprise the following steps:
(1) in reaction vessel, activated zinc powder, methyl iodide or iodoethane, terminal alkyne, solvent is added; Stirring at room temperature disappears to zinc powder;
(2), after zinc powder completely dissolve, the carbonyl compound of organic solvent dissolution is added;
(3) stirring at room temperature, until carbonyl compound disappearance stopped reaction, namely reaction solution obtains product after separation and purification.
2. the method for a kind of simple synthesis propiolic alcohol according to claim 1, is characterized in that, in described step (3), the concrete steps of reaction solution separation and purification are as follows:
In reaction solution, add saturated aqueous ammonium chloride and organic solvent, be separated organic phase, aqueous phase with organic solvent extraction once more than, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate drying is concentrated, and namely silicagel column obtains product after being separated.
3. the method for a kind of simple synthesis propiolic alcohol according to claim 2, is characterized in that, the post separation condition excessively of described silicagel column is sherwood oil: ethyl acetate=10:1 ~ 20:1.
4. the method for a kind of simple synthesis propiolic alcohol according to claim 1, is characterized in that, described terminal alkyne is fatty end alkynes or aromatic end alkynes; Described carbonyl compound is alkanoic, aromatic aldehyde, aliphatic ketone or aromatic ketone.
5. the method for a kind of simple synthesis propiolic alcohol according to claim 1, is characterized in that, in described step (1), solvent is N-Methyl pyrrolidone; Organic solvent in described step (2) is methylene dichloride, toluene or normal hexane.
6. the method for a kind of simple synthesis propiolic alcohol according to claim 5, it is characterized in that, the organic solvent in described step (2) is methylene dichloride.
7. the method for a kind of simple synthesis propiolic alcohol according to any one of claim 1-6, it is characterized in that, the mol ratio between described carbonyl compound, terminal alkyne, activated zinc powder and methyl iodide or iodoethane is 1: (2 ~ 4): (3 ~ 6): (6 ~ 12).
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108503505A (en) * 2018-05-11 2018-09-07 中国石化长城能源化工（宁夏）有限公司 A method of preparing propilolic alcohol using Isosorbide-5-Nitrae-butynediols
CN110404587A (en) * 2019-08-22 2019-11-05 安徽大学 A kind of support type cluster catalyst and its preparation and application

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108503505A (en) * 2018-05-11 2018-09-07 中国石化长城能源化工（宁夏）有限公司 A method of preparing propilolic alcohol using Isosorbide-5-Nitrae-butynediols
CN110404587A (en) * 2019-08-22 2019-11-05 安徽大学 A kind of support type cluster catalyst and its preparation and application
CN110404587B (en) * 2019-08-22 2022-07-12 安徽大学 Supported cluster catalyst and preparation and application thereof

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