CN107954872A - A kind of synthetic method of malonic acid ester type compound - Google Patents

A kind of synthetic method of malonic acid ester type compound Download PDF

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CN107954872A
CN107954872A CN201711342257.5A CN201711342257A CN107954872A CN 107954872 A CN107954872 A CN 107954872A CN 201711342257 A CN201711342257 A CN 201711342257A CN 107954872 A CN107954872 A CN 107954872A
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CN107954872B (en
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唐建生
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Hunan First Normal University
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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
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups

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Abstract

The invention discloses a kind of synthetic method of malonic acid ester type compound, this method uses 3 halo propine ester type compounds shown in formula 1, the alcohol shown in formula 2, water as raw material, under conditions of palladium catalyst and alkali, it is placed in air atmosphere and is reacted at room temperature, prepares the malonic acid ester type compound shown in formula 3：

Description

A kind of synthetic method of malonic acid ester type compound
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of synthetic method of malonic acid ester type compound.
Background technology
1,3- dicarbonyl compound particularly malonic acid esters are important organic synthesis intermediates, adjacent two in molecule A electron withdrawing group causes the hydrogen on methylene to be easy to be substituted by other groups, can be alkylated, alkoxylate, acyl group A variety of substitution reactions such as change, hydroxylating and amidatioon, reactivity is higher, is widely used in medicine, pesticide, spices and dye It is a kind of particularly important Fine Organic Chemical product in the fields such as material.
Since malonic acid ester type compound has above-mentioned excellent properties, develop the simply efficient synthetic method of such compound Research causes the broad interest of scientist.Traditionally, malonate is synthesized by malonic acid and alcohol direct polycondensation.But this kind of side Method usually requires more exacting terms, and the scope of application of functional group is also smaller, and easily generates the by-product of toxic effect Thing.
Synthesis for malonic acid ester type compound, the prior art are also widely reported substantial amounts of synthetic method, wherein Substantial amounts of research work has also been made by seminar where inventor.Money distance of travel of roc etc. report 3- halo propine ester type compounds with Water, alcohol synthesize the reaction of malonic acid ester type compound (referring to prior art literature (1) " alkynes under conditions of DABCO is as alkali The research of functional group reactions synthesis of cyclic compound and malonate ", money distance of travel of roc,《Chinese Ph.D. Dissertation's full-text database I volumes of engineering science and technology》, the 02nd phase in 2017；(2)“Synthesis of Malonates from 3-Halopropynoates, Alcohols, and Water Using DABCO ", Peng-Cheng Qian etc., Synthesis 2015,47,3309- 3314).This method using 3- iodine/bromine alkynes ester compounds as raw material, reacted at ambient temperature using DABCO as alkali 8 it is small when, obtain one The malonic acid ester type compound of series, and there is good yield and substrate adaptability (referring to following formula one).
In fact, the reaction participated in for alkynes halogen compound, inventor also have made extensive and intensive studies.Wherein, Inventor reported a kind of 3- iodopropynyls amides compound in 2015 with water, the coupling reaction of alcohol (referring to the prior art Document (3) " Palladium-Catalyzed Alcoholysis of 3-Iodopropynamides:Selective Synthesis of Carbamoylacetates ", Jian-Sheng Tang etc., Synthesis 2015,47,108-112； (4) " research of palladium chtalyst alkynes halogen compound coupling reaction ", Tang Jiansheng,《Chinese Ph.D. Dissertation's full-text database engineering science and technology I Volume》, the 02nd phase in 2017.), in this study, inventor has found, although the structure of reaction raw materials and foregoing 3- iodopropynyls Ester type compound is similar, but the reaction of 3- iodopropynyls amides compound and water, alcohol must be under conditions of palladium catalyst It could occur, and the reaction time is longer, it is necessary to (referring to following formula two) when 12 is small.
Inventor chances in experimental study, for 3- halo propine ester type compounds and water, alcohol in DABCO conducts The reaction of malonic acid ester type compound is synthesized under conditions of alkali, by adding a certain amount of palladium catalyst, reaction yield has carried Rise, more it is surprising that adding the speed that palladium catalyst can significantly increase the reaction of the reaction, the reaction time is by original 8 it is small when rapid drawdown be 5 minutes.On this basis, inventor proposes a kind of method of improved synthesis malonic acid ester type compound, This method can significantly improve reaction efficiency, shorten the reaction time.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of conjunction of improved malonic acid ester type compound Into method.This method carries out anti-using 3- halo propine ester type compound, water, alcohol as raw material under conditions of palladium catalyst/alkali Should, malonic acid ester type compound is prepared, significantly reduces the reaction time.
To realize the purpose of foregoing invention, the present invention is achieved through the following technical solutions：3- halos third shown in formula 1 Alcohol, water shown in alkynes ester type compound, formula 2, under conditions of palladium catalyst and alkali, are placed in air atmosphere and carry out at room temperature anti- Should, prepare the malonic acid ester type compound (formula three) shown in formula 3.
Wherein [Pd] represents palladium catalyst, selected from Pd (OAc)2、Pd(dba)2、PdCl2、PdCl2(PPh3)2In it is any one Kind or several mixtures.Further preferably, the palladium catalyst is Pd (OAc)2。
Any one of alkali in DBACO, triethylamine.Further preferably, alkali is selected from DBACO.
X represents halogen, further, may be selected from chlorine, bromine, iodine.
R1Represent C1-20Substituted or unsubstituted alkyl, C3-C20Substituted or unsubstituted heterocyclic radical.
Preferably, the C1-20Substituted or unsubstituted alkyl be C1-C20Substituted or unsubstituted alkyl, C2-C20 Substituted or unsubstituted alkenyl, C6-C20Substituted or unsubstituted aryl, C3-C20Substituted or unsubstituted cycloalkyl.
R2Represent C1-20Substituted or unsubstituted alkyl.
Preferably, the C1-20Substituted or unsubstituted alkyl be C1-C20Substituted or unsubstituted alkyl, C2-C20 Substituted or unsubstituted alkenyl.
Wherein, substituent can be selected from C in foregoing each " substituted "1-C6Alkyl, C2-C6Alkenyl, C6-12Aryl, C6-12Aryl-C2Alkenyl-, C6-12Aryl-C1-6Alkyl-, C1-C6Alkoxy, halogen, nitro ,-CN.
It is further preferred that R1Represent C1-6Alkyl, C6-12Aryl, C6-12Aryl-C1-6Alkyl, C6-12Aryl-C2Alkenyl- C1-6Alkyl；R2Represent C1-6Alkyl, C2-C6Alkenyl C1-6- alkyl, C6-12Aryl-C1-6Alkyl, C6-12Aryl-C2Alkenyl-C1-6Alkane Base.
It is further preferred that R1Represent methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, positive penta Base, isopentyl, neopentyl, phenyl, naphthyl, benzyl, phenyl alkenylene methylene；R2Represent methyl, ethyl, propyl group, isopropyl, Normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, pi-allyl, benzyl, phenylene vinylene methylene.
Herein, unless otherwise specified, the hetero atom of the heterocyclic radical and/or heteroaryl should be understood to that this area is normal The hetero atom species seen, such as O, S or N can be selected from.
Optionally, the reaction of formula three can be selected to be in or be not in other organic solvents and carried out, when selection is not other When being carried out in organic solvent, it is to be understood that i.e. described reaction can increase the inventory of raw alcohol, with corresponding raw alcohol Solvent as reaction at the same time；When the other organic solvents of selection are as reaction dissolvent, the organic solvent can be selected from Acetonitrile, butyronitrile, tetrahydrofuran.Preferably, the selecting response of formula three carries out under conditions of acetonitrile is as solvent.
According to the reaction described in formula three, the 3- halo propine ester type compounds shown in formula 1：Alcohol shown in formula 2：Water：Palladium is urged Agent：The molar ratio of alkali is 1:1~4:1~4:0.001~0.05:1~4, it is preferable that the 3- halo propine shown in formula 1 Ester type compound：Alcohol shown in formula 2：Water：Palladium catalyst：The molar ratio of alkali is 1:2:2:0.01:2.
In the present invention, unless otherwise specified, the addition of solvent should be understood to the additive amount of this area routine, i.e., with Make reaction mass fully dissolve and uniformly diffusion subject to.
In the present invention, the DABCO has implication known in the field, its chemical name is Isosorbide-5-Nitrae-diazabicylo 【2.2.2】Octane.
According to the reaction described in formula three, its type testing operation is as follows：To being equipped with the reaction bulb of magnetic stirring apparatus, successively The 3- halo propine ester type compound shown in the formula 1 of foregoing mol ratio, the alcohol shown in formula 2, water, palladium catalyst, alkali are added, so After add a certain amount of acetonitrile as reaction dissolvent, stirring reaction 5 minutes under room temperature and air atmosphere are placed in, through GC or TLC points Analysis detection, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Washing, ether extraction, anhydrous sodium sulfate drying, Vacuum distillation removes solvent, and residue is separated (normal hexane/ethyl acetate is eluent) through silica gel column chromatography obtains target production Thing 3.
The beneficial effects of the invention are as follows：A kind of synthetic method of improved synthesis malonic acid ester type compound is proposed, should Method significantly reduces the reaction time, improves reaction by adding minimal amount of (1%-2%) palladium catalyst into reaction Efficiency while target product yield also slightly raising.
Embodiment
Below in conjunction with specific embodiment, further detailed description is carried out to the present invention.
Embodiment 1
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-A is sequentially added Thing 62.4mg (0.2mmol), ethanol 18.4mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-A, colourless liquid, yield 95%.
Embodiment 2
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-A is sequentially added Thing 62.4mg (0.2mmol), methanol 12.8mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-B, colourless liquid, yield 96%.
Embodiment 3
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-A is sequentially added Thing 62.4mg (0.2mmol), isopropanol 24mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-C, colourless liquid, yield 81%.
Embodiment 4
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-A is sequentially added Thing 62.4mg (0.2mmol), n-amyl alcohol 35.2mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-D, colourless liquid, yield 91%.
Embodiment 5
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-A is sequentially added Thing 62.4mg (0.2mmol), allyl alcohol 23.2mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-E, colourless liquid, yield 86%.
Embodiment 6
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-B is sequentially added Thing 57.2mg (0.2mmol), methanol 12.8mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-F, colourless liquid, yield 94%.
Embodiment 7
To being equipped with the 25mL reaction bulbs of magnetic stirring apparatus, the 3- iodopropynyl esters chemical combination shown in formula 1-C is sequentially added Thing 44.8mg (0.2mmol), ethanol 18.4mg (0.4mmol), water 7.2mg (0.4mmol), Pd (OAc)2、0.45mg (1mol%), DABCO44.8mg (0.4mmol), then adds 2mL acetonitriles as reaction dissolvent, is placed in room temperature and air atmosphere Lower stirring reaction 5 minutes, through GC or TLC analysis detections, confirms that the reaction was complete.By the mixed liquor after reaction through saturation Na2S2O3Wash Wash, ether extraction, anhydrous sodium sulfate drying, vacuum distillation removes solvent, residue is separated through silica gel column chromatography (normal hexane/ Ethyl acetate is eluent) obtain target product 3-G, colourless liquid, yield 76%.
Embodiment 8
Carry out feed intake reaction and post processing as described in Example 1, difference be without using organic solvent acetonitrile, with And the addition of ethanol is 2mL, target product 3-A, colourless liquid, yield 92% are obtained.
Comparative example 1
By " Synthesis of Malonates from 3-Halopropynoates, Alcohols, and Water The method that Using DABCO ", Peng-Cheng Qian etc., Synthesis 2015,47,3309-3314 is reported, namely be not added with Enter palladium catalyst, remaining condition is the same as embodiment 1.When reacting 5 minutes, being detected by GC, target product yield is only 8% or so, The reaction was continued extend to the reaction time for 8 it is small when, target product yield 92%.
Comparative example 2
Palladium acetate catalyst is substituted using copper acetate as catalyst, remaining condition is the same as embodiment 1.After testing, 5 points are reacted Zhong Hou, target product yield are only 6%, the reaction was continued extend to 8 it is small when, target product yield 78%.
Applicant states that the present invention illustrates the synthetic method of the present invention, but not office of the invention by above-described embodiment It is limited to above-described embodiment, those skilled in the art is it will be clearly understood that carry out preparation method of the invention and operation various It is conventional to replace, select and/or adjust, all fall within protection scope of the present invention and the open scope.

Claims (10)

  1. A kind of 1. synthetic method of malonic acid ester type compound, it is characterised in that the 3- halo propine esters chemical combination shown in formula 1 Alcohol, water shown in thing, formula 2, under conditions of palladium catalyst and alkali, are placed in air atmosphere and are reacted at room temperature, preparation obtains Obtain the malonic acid ester type compound shown in formula 3；
    Wherein [Pd] represents palladium catalyst, selected from Pd (OAc)2、Pd(dba)2、PdCl2、PdCl2(PPh3)2In any one or Several mixtures；
    Any one of alkali in DBACO, triethylamine；
    X represents halogen；
    R1Represent C1-20Substituted or unsubstituted alkyl, C3-C20Substituted or unsubstituted heterocyclic radical；
    R2Represent C1-20Substituted or unsubstituted alkyl；
    Substituent in respectively " substituting " can be selected from C1-C6Alkyl, C2-C6Alkenyl, C6-12Aryl, C6-12Aryl-C2Alkenyl-, C6-12Aryl-C1-6Alkyl-, C1-C6Alkoxy, halogen, nitro ,-CN.
  2. 2. according to the method described in claim 1, it is characterized in that, the palladium catalyst is Pd (OAc)2。
  3. 3. according to the method described in claim 1, it is characterized in that, the alkali is selected from DBACO.
  4. 4. the according to the method described in claim 1, it is characterized in that, R1Represent C1-20Substituted or unsubstituted alkyl choosing From C1-C20Substituted or unsubstituted alkyl, C2-C20Substituted or unsubstituted alkenyl, C6-C20Substituted or unsubstituted virtue Base, C3-C20Substituted or unsubstituted cycloalkyl；The R2The C of expression1-20Substituted or unsubstituted alkyl be selected from C1-C20's Substituted or unsubstituted alkyl, C2-C20Substituted or unsubstituted alkenyl.
  5. 5. according to the method described in claim 4, it is characterized in that, R1Represent C1-6Alkyl, C6-12Aryl, C6-12Aryl-C1-6Alkane Base, C6-12Aryl-C2Alkenyl-C1-6Alkyl; R2Represent C1-6Alkyl, C2-C6Alkenyl C1-6- alkyl, C6-12Aryl-C1-6Alkyl, C6-12Aryl-C2Alkenyl-C1-6Alkyl.
  6. 6. according to the method described in claim 5, it is characterized in that, R1Represent methyl, ethyl, propyl group, isopropyl, normal-butyl, different Butyl, the tert-butyl group, n-pentyl, isopentyl, neopentyl, phenyl, naphthyl, benzyl, phenyl alkenylene methylene；R2Expression methyl, Ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl, pi-allyl, benzyl, phenyl are sub- Ethene methylene.
  7. 7. according to claim 1-6 any one of them methods, it is characterised in that the optional use of the reaction or without using another Outer organic solvent, one or more of mixtures of the organic solvent in acetonitrile, butyronitrile, tetrahydrofuran.
  8. 8. according to the method described in claim 1-7 any one, it is characterised in that the 3- halo propine esters shown in formula 1 Compound：Alcohol shown in formula 2：Water：Palladium catalyst：The molar ratio of alkali is 1:1~4:1~4:0.001~0.05:1~4.
  9. 9. according to the method described in claim 8, it is characterized in that, 3- halo propine ester type compounds shown in formula 1：The institute of formula 2 The alcohol shown：Water：Palladium catalyst：The molar ratio of alkali is 1:2:2:0.01:2.
  10. 10. according to the method described in claim 1-10 any one, it is characterised in that to the reaction bulb for being equipped with magnetic stirring apparatus In, sequentially add the 3- halo propine ester type compound shown in the formula 1 of foregoing mol ratio, the alcohol shown in formula 2, water, palladium chtalyst Agent, alkali, then add a certain amount of acetonitrile as reaction dissolvent, stirring reaction 5 minutes under room temperature and air atmosphere are placed in, through GC Or TLC analysis detections, confirm that the reaction was complete, by the mixed liquor after reaction through saturation Na2S2O3Washing, ether extraction, anhydrous slufuric acid Sodium is dried, and vacuum distillation removes solvent, by residue through the isolated target product 3 of silica gel column chromatography.
CN201711342257.5A 2017-12-14 2017-12-14 Method for synthesizing malonate type compound Expired - Fee Related CN107954872B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354511A (en) * 2021-06-09 2021-09-07 湖南第一师范学院 Synthesis method of gem-1, 3-eneyne compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113354511A (en) * 2021-06-09 2021-09-07 湖南第一师范学院 Synthesis method of gem-1, 3-eneyne compound

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