CN105017016B - A kind of method of simple synthesis propilolic alcohol - Google Patents

A kind of method of simple synthesis propilolic alcohol Download PDF

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CN105017016B
CN105017016B CN201510384739.1A CN201510384739A CN105017016B CN 105017016 B CN105017016 B CN 105017016B CN 201510384739 A CN201510384739 A CN 201510384739A CN 105017016 B CN105017016 B CN 105017016B
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zinc powder
propilolic alcohol
reaction
present
simple synthesis
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CN105017016A (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

Abstract

Disclosed by the invention is a kind of method of simple synthesis propilolic alcohol, and the present invention solves in prior art conventional method to water and air quite sensitive, it is impossible to realize mass-produced problem.The present invention comprises the following steps: (1) adds activated zinc powder, iodomethane or iodoethane, terminal alkyne, solvent in reaction vessel；It is stirred at room temperature to zinc powder disappearance；(2), after zinc powder is wholly absent, the carbonyls that organic solvent dissolves is added；(3) being stirred at room temperature, until carbonyls disappears stops reaction, reactant liquor i.e. obtains product after isolated and purified.The present invention has the advantages such as reaction condition is gentle, raw material is easy to get, easy to operate, reaction time is shorter and can be mass-produced.

Description

A kind of method of simple synthesis propilolic alcohol
Technical field
The present invention relates to the preparation method of a kind of propilolic alcohol, particularly relate to the terminal alkyne addition to carbonyls Reaction.
Background technology
Propilolic alcohol is important organic synthesis intermediate, and on the one hand it is widely used in natural products, medicine and complexity In the synthesis of macromolecular compound；On the other hand, the functional group of alkynyl and hydroxyl both flexible can pass through functional group Converting makes it have the biggest potential using value in terms of molecular diversity.
By terminal groups alkynes, the addition reaction of aldehydes or ketones can be prepared propilolic alcohol, course of reaction is generally by alkyl The active metal such as zinc, butyl lithium reagent first reacts generation alkynyl zinc or alkynyl lithium reagent with terminal alkyne, then to carbonyl compound Thing addition obtains propiolic alcohol compound.But, the metal reagent such as zinc alkyl and butyl lithium is sensitive to water electrode, needs strict control The water content of reaction system processed, reagent required to reaction and solvent, vessel all need strict anhydrous dry, and therefore reaction condition is severe Carve, operation inconvenience.
Summary of the invention
It is an object of the invention to avoid to use the raw material to water and air all quite sensitive in prior art, it is provided that a kind of The simple method synthesizing propilolic alcohol, thus realize large-scale production.
For solving the scarce limit of conventional art, technical scheme is as follows:
A kind of method of simple synthesis propilolic alcohol, comprises the following steps:
(1) adding activated zinc powder, iodine first (second) alkane, terminal alkyne, 1-METHYLPYRROLIDONE in reaction vessel, room temperature is stirred Mix to zinc powder disappearance；
(2) zinc powder is wholly absent, and adds the carbonyls that organic solvent dissolves；
(3) it is stirred at room temperature, uses silica gel thin-layer chromatography monitoring reaction process, until carbonyls disappears stops reaction, Reactant liquor i.e. obtains product after isolated and purified.
The course of reaction of the present invention is as follows: zinc powder and iodine first (second) alkane react generation zincon, then make with terminal alkyne With rear, then attack carbonyl, and then generate propilolic alcohol.
The reaction equation of the present invention is as follows:
。
Present invention achieves in an atmosphere, it is not necessary to add other catalyst and can realize zinc and react with iodine first (second) alkane, and Promote the addition of terminal alkyne and carbonyls, and then be advantageously implemented a large amount of productions of propilolic alcohol.In above-mentioned reaction equation: NMP is 1-METHYLPYRROLIDONE, and MeI is iodomethane, and EtI is iodoethane, and Zn Powder is zinc powder, and DCM is dichloromethane；R is Aryl, alkyl or alkyl；R1For aryl, alkyl or alkyl；R2For COOMe, H or COOEt.
Further, isolated and purified the specifically comprising the following steps that of reactant liquor in described step (3)
In reactant liquor, add saturated aqueous ammonium chloride and organic solvent, separate organic phase, aqueous phase organic solvent extracting Taking three times, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column i.e. obtains product after separating.
Further, described post separation condition of crossing is petroleum ether: ethyl acetate=10:1～20:1.
Preferably, described terminal alkyne is fat alkynes or aromatic alkyne；Described carbonyls is fatty aldehyde, aromatic aldehyde, fat Fat ketone or aromatic ketone.
Preferably, in described step (1), solvent is 1-METHYLPYRROLIDONE；In described step (2), organic solvent is dichloro Methane, toluene or n-hexane, preferably dichloromethane.
In order to reach higher productivity, between described carbonyls, terminal alkyne, activated zinc powder and iodine first (second) alkane Mol ratio be 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 in an atmosphere and reacts and promote the addition of alkynes and carbonyl with iodine first (second) alkane, reacts bar Part is gentle, thus has the advantage that can mass produce racemic propilolic alcohol；
2, the present invention need not add other catalyst, and the most directly using water electrode is the diethyl zinc of sensitivity, butyl Lithium, but by generating zincon in course of reaction and promoting the generation of reaction；The inventive method have reaction condition gentle, The advantages such as raw material is easy to get, easy to operate, reaction time is shorter；
3, the present invention is not only only applicable to the addition realizing alkynes in atmosphere to aldehyde, also achieve in atmosphere alkynes to ketone Addition reaction, range of application is more extensive.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of method of simple synthesis propilolic alcohol, the present embodiment is 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 1-METHYLPYRROLIDONE, 2h is stirred at room temperature, disappears to activated zinc powder Lose.
After zinc powder is wholly absent, add the dichloromethane solution of methyl benzoylformate (0.5 mmol, 1 equiv), silicon Glue thin-layer chromatography monitoring reaction process, is stirred at room temperature 12h, and raw material methyl benzoylformate disappears, and stops reaction, in reactant liquor Adding 10ml saturated aqueous ammonium chloride and dichloromethane, stir 10min, separate organic phase, aqueous phase dichloromethane extracts three Secondary, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:3.83 (1H, s ,-OH), 5.70 (1H, s, C*-H), 7.33-7.53 ( 8H ,m,C5-3H,C5-5H)。7.76-7.81( 2H ,m,C5-2H)。
Embodiment 2
The present embodiment is phenylacetylene to α, the reaction of α, α-trifluoroacetophenone addition, 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 1-METHYLPYRROLIDONE, 2h is stirred at room temperature, to zinc powder disappear.
After zinc powder is wholly absent, addition α, the dichloromethane solution of α, α-trifluoroacetophenone (0.5 mmol, 1 equiv), Silica gel thin-layer chromatography monitoring reaction process, is stirred at room temperature 12h, raw material α, and α, α-trifluoroacetophenone disappears, and stops reaction, to reaction Adding 10ml saturated aqueous ammonium chloride and dichloromethane in liquid, stir 10min, separate organic phase, aqueous phase dichloromethane extracts Taking three times, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:3.17 (1H, s ,-OH), 7.34-7.52 (8H, m, C5-3H, C5- 5H), 7.81-7.82( 2H ,dd,C5-2H)。
Embodiment 3
The present embodiment is phenylacetylene to benzaldehyde 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 pyrrolidone, 2h is stirred at room temperature, to activated zinc powder disappear.
After zinc powder is wholly absent, add the dichloromethane solution of benzaldehyde (0.5 mmol, 1 equiv), silica gel thin-layer chromatography Spectrum monitoring reaction process, is stirred at room temperature 12h, raw material benzaldehyde disappearance, stops reaction, adds the saturated chlorination of 10ml in reactant liquor Aqueous ammonium and dichloromethane, stir 10min, separates organic phase, and aqueous phase dichloromethane extracts three times, merges organic phase, full Washing with salt, anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:2.32 (1H, d ,-OH), 5.70 (1H, d, C*-H), 7.30-7.45 ( 8H ,m,C5-3H,C5-5H),7.61-7.62( 2H ,m,C5-2H)。
Embodiment 4
The present embodiment is phenylacetylene to methyl pyruvate 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 pyrrolidone, 2h is stirred at room temperature, to activated zinc powder disappear.
After zinc powder is wholly absent, adding the dichloromethane solution of methyl pyruvate (0.5 mmol, 1 equiv), silica gel is thin Layer chromatography monitoring reaction process, iodine cylinder develops the color, and 12h is stirred at room temperature, and raw material acetone acid methyl esters disappears, and stops reaction, to reactant liquor Middle addition 10ml saturated aqueous ammonium chloride and dichloromethane, stir 10min, separates organic phase, and aqueous phase dichloromethane extracts Three times, merging organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:1.79(3H, s ,-CH3), 3.53 (1H, s ,-OH), 3.84(3H, s ,- OCH3), 7.27-7.44 (3H, m, C5-3H),7.45-7.46( 2H ,m,C5-2H)。
Embodiment 5
The present embodiment is 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), MeI (6 mmol, 12 Equiv), phenylacetylene (2 mmol, 4 equiv), the 1-METHYLPYRROLIDONE of 0.5ml, 2h is stirred at room temperature, disappears to activated zinc powder Lose.
After zinc powder is wholly absent, adding the dichloromethane solution of hexahydrobenzaldehyde (0.5 mmol, 1 equiv), silica gel is thin Layer chromatography monitoring reaction process, iodine cylinder develops the color, and 12h is stirred at room temperature, and raw material hexahydrobenzaldehyde disappears, and stops reaction, to reactant liquor Middle addition 10ml saturated aqueous ammonium chloride and dichloromethane, stir 10min, separates organic phase, and aqueous phase dichloromethane extracts Three times, merging organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:1.09-1.34(5H, m ,-C6H11), 1.61-1.68(2H, m ,- C6H11), 1.78-1.85(2H, d ,-C6H11), 1.84 (1H, s ,-OH), 1.91-1.94(2H, d ,-C6H11) 7.28- 7.33 ( 3H ,m,C5-3H),7.41-7.46( 2H ,m,C5-2H)。
Embodiment 6
The present embodiment is 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 1-METHYLPYRROLIDONE, 2h is stirred at room temperature, to activated zinc Powder disappears.
After zinc powder is wholly absent, add the dichloromethane solution of methyl benzoylformate (0.5 mmol, 1 equiv), silicon Glue thin-layer chromatography monitoring reaction process, is stirred at room temperature 12h, and raw material methyl benzoylformate disappears, and stops reaction, in reactant liquor Adding 10ml saturated aqueous ammonium chloride and dichloromethane, stir 10min, separate organic phase, aqueous phase dichloromethane extracts three Secondary, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:3.73-3.83(3H, s ,-CH3) 4.28 (1H, s ,-OH), 7.22 (1H, t, C5-1H), 7.36-7.51 ( 5H ,m, C5-5H)。7.68-7.73( 3H ,m,C5-3H)。
Embodiment 7
Being the reaction to methyl benzoylformate addition of the 1-heptyne 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 1-METHYLPYRROLIDONE, 2h is stirred at room temperature, disappears to activated zinc powder Lose.
After zinc powder is wholly absent, add the dichloromethane solution of methyl benzoylformate (0.5 mmol, 1 equiv), silicon Glue thin-layer chromatography monitoring reaction process, is stirred at room temperature 12h, and raw material methyl benzoylformate disappears, and stops reaction, in reactant liquor Adding 10ml saturated aqueous ammonium chloride and dichloromethane, stir 10min, separate organic phase, aqueous phase dichloromethane extracts three Secondary, merge organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column separating-purifying obtains product.
The propilolic alcohol obtaining the present embodiment carries out proton nmr spectra detection, and testing result is as follows:
1H NMR(400MHz, CDCl3) δ ppm:0.89-0.92 (3H, t ,-CH3),1.25-1.59(6H,m,-CH2)
3.76 (1H, t ,-OCH3), 4.11 (1H, d ,-OH), 7.26-7.39 (3H, m, C5-3H), 7.66 (2H , m,C5-2H)。
Embodiment 8
The present embodiment differs only in embodiment 1: the MeI in embodiment 1 is replaced to EtI, and other react bar Part is constant.
Embodiment 9
The present embodiment is with the difference of embodiment 1: in the present embodiment, the addition of methyl benzoylformate is 0.5mmol, the addition of phenylacetylene is 1.5mmol, and the addition of activated zinc powder is 2mmol, and the addition of iodomethane is 4mmol, other reaction conditions are identical with the reaction condition of embodiment 1.
Embodiment 10
The present embodiment is with the difference of embodiment 1: carbonyls in the present embodiment, terminal alkyne, activated zinc powder with And the addition difference between iodoethane.In the present embodiment, the addition of methyl benzoylformate is 0.5mmol, adding of phenylacetylene Entering amount is 1.5mmol, the addition of activated zinc powder be the addition of 1.5mmol, EtI be 3mmol, organic solvent use just oneself Alkane, other reaction condition is identical with the reaction condition of embodiment 1.
The productivity of the propilolic alcohol that above-described embodiment 1-10 generates is detected, and lists the third of synthesis material and generation The chemical constitution of alkynol, the most as shown in table 1.
Table 1
By the result of the various embodiments described above: the present invention not only can realize terminal alkyne and generate third with aldehyde addition Alkynol, also can realize terminal alkyne and generate propilolic alcohol, and either terminal alkyne and aldehyde addition or terminal alkyne with ketone addition With ketone addition, it all can react in an atmosphere, and without adding other catalyst in production process；And the reaction of the present invention Mild condition, raw material are easy to get, easy to operate, reaction time is shorter, thus are especially suitable for mass producing propilolic alcohol.
Meanwhile, by above-mentioned yield results, the productivity of the present invention can reach more than 70%, and terminal alkyne is phenylacetylene More, now, when carbonyls is hexahydrobenzaldehyde, the productivity of propilolic alcohol even can reach 95% to Shi Xiaoguo, effective table The synthetic method effect of the bright present invention is the most excellent.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as using The design principle of the present invention, and carry out non-creativeness work on this basis and the change made, all should belong to the present invention's Within protection domain.

Claims (5)

1. the method for a simple synthesis propilolic alcohol, it is characterised in that comprise the following steps:
(1) in reaction vessel, activated zinc powder, iodomethane or iodoethane, terminal alkyne, solvent are added；It is stirred at room temperature to zinc powder and disappears Lose；
(2), after zinc powder is wholly absent, the carbonyls that organic solvent dissolves is added；
(3) being stirred at room temperature, until carbonyls disappears stops reaction, reactant liquor i.e. obtains product after isolated and purified；
In described step (1), solvent is 1-METHYLPYRROLIDONE；Organic solvent in described step (2) is dichloromethane, toluene Or n-hexane；Described terminal alkyne is fat end alkynes or aromatic end alkynes；Described carbonyls be fatty aldehyde, aromatic aldehyde, Aliphatic ketone or aromatic ketone.
The method of a kind of simple synthesis propilolic alcohol the most according to claim 1, it is characterised in that anti-in described step (3) Answer isolated and purified the specifically comprising the following steps that of liquid
Adding saturated aqueous ammonium chloride and organic solvent in reactant liquor, separate organic phase, aqueous phase organic solvent extracts one More than secondary, merging organic phase, saturated common salt is washed, and anhydrous sodium sulfate is dried, and concentrates, and silicagel column i.e. obtains product after separating.
The method of a kind of simple synthesis propilolic alcohol the most according to claim 2, it is characterised in that the post excessively of described silicagel column Separation condition is petroleum ether: ethyl acetate=10:1～20:1.
The method of a kind of simple synthesis propilolic alcohol the most according to claim 1, it is characterised in that in described step (2) Organic solvent is dichloromethane.
5. according to the method for a kind of simple synthesis propilolic alcohol described in any one of claim 1-4, it is characterised in that described carbonyl Mol ratio between compound, terminal alkyne, activated zinc powder and iodomethane or iodoethane is 1: (2～4): (3～6): (6～ 12).
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