CN105130726A - Method for preparing cinnamyl aldehyde compounds - Google Patents
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Abstract
The invention provides a method for preparing cinnamyl aldehyde compounds. According to the method, under the nitrogen condition, propargyl alcohol is adopted as a raw material, a phosphorous acid aqueous solution is adopted as a medium, and the cinnamyl aldehyde compounds are synthesized in organic solvents. According to the method, the easily-obtained raw material and the cheap phosphorous acid aqueous solution are adopted, a reaction is conducted under the nitrogen condition, no ligand or peroxide or valuable catalyst or microwave radiation or other special reaction conditions are adopted, the reaction condition is simple, the product is high in selectivity and productivity, and good industrial application prospects are achieved.
Description
[technical field]
The present invention relates to organic synthesis field, be specifically related to a kind of preparation method of phenylacrolein compounds.
[background technology]
Phenylacrolein compounds is important organic synthesis raw material and intermediate, and aldehyde radical is easily converted into other useful functional compounds, as cyano group, carboxylic acid, hydroxyl and acid amides etc.Phenylacrolein compounds has a lot of unique character, in the fields such as essence and flavoring agent, household chemicals, medicine and foodstuff additive, have very important using value.As adjacent hydroxycinnamaldehyde has antibacterial, the various active such as anti-inflammatory, anticancer propagation, good effect is shown to the treatment of lung cancer; To chlorocinnamaldehyde, there is antibacterial and growth-promoting effect, can be used as fodder additives.Phenylacrolein compounds not only has excellent biological activity and also has changeable chemical structure, is one of focus of studying of organic synthesis and fine chemistry, about the exploration of this kind of compou nd synthesis route also constantly deeply.
Nineteen twenty-two, Meyer and Schueter proposes the method being generated alpha, beta-unsaturated ketone by strong acid catalyst propargyl alcohol through 1,3-rearrangement and isomerization.But traditional Meyer-Schueter rearrangement reaction, owing to using strong acid, needing the severe condition such as high temperature, and substrate is confined to the propargyl alcohol lacking β-H, and thus the application of this method is restricted.But due to its efficient Atom economy, this method causes the concern of investigator and carries out multiple improvement to improve its applicability.Such as, strong acid is replaced by metal catalyst (as: Ag, Au, Mo etc.).Vidari seminar, by Re catalyst propargyl alcohol, generates α, beta-unsaturated aldehyde (ketone) at 80 DEG C of temperature.The investigators such as Vicent adopt microwave irradiation technology, at 160 DEG C, generate a series of α by Ag catalyst, beta-unsaturated aldehyde (ketone) compound.Because these methods employ precious metal catalyst or special technology, be also unfavorable for widely using of Meyer-Schueter rearrangement reaction.QiGao seminar uses Lewis acid (FeCl
3) promoting that propargyl alcohol generates phenylacrolein compounds, the investigators such as Hall also generate target product by previously prepared fragrant boric acid catalysis propargyl alcohol through resetting.Although these two kinds of methods avoid the use of precious metal catalyst, also there is shortcomings such as needing dry environment, catalyzer needs pre-treatment to prepare.Therefore the method that new easy propargyl alcohol is converted into phenylacrolein compounds is subject to people's attention always.[reference: MeyerK.H.; Schuster, K.Chem.Ber.1922,55,819-821; á lvarez, J.G.; D í ez, J.; Vidal, C.; Vicent, C.Inorg.Chem.2013,52,6533-6542; Stefanoni, M.; Porta, A.; Luparia, M.; Zanoni, G.; Vidari, G.Chem.Eur.J.2009,15,3940 – 3944; Cadierno, V.; Crochet, P.; Garrido, S.E.G.; Gimeno, J.DaltonTrans.2010,39,4015 – 4031; Egi, M.; Yamaguchi, Y.; Fujiwara, N.; Akai, S.Org.Lett.2008,10,1867-1870; Cadierno, V.; Francos, J.; Gimeno, J.TetrahedronLett.2009,504773-4776;
a.; Hermosilla, F.C.; Cadierno, V.;
j.G; Otero, A.ChemCatChem2012,4,123-128; 9Douhaibi, A.S.E.; Judeh, Z.M.A.; Basri, H.; Moussa, Z.; Messali, M.; Qi, G.Synth.Commun.2011,41,533-540; Zheng, H.; Lejkowski, M.; Hall, D.G.Chem.Sci.2011,2,1305-1310.]
For the deficiency of aforesaid method, the propargyl alcohol developing to be easy to get is substrate, uses cheap catalyst (or promotor), and reaction conditions is simple, and easy and simple to handle, synthesis new way applied widely, has certain industrial application value.
[summary of the invention]
The object of the invention is exploitation one under nitrogen atmosphere, take propargyl alcohol as raw material, phosphorous acid aqueous solution is medium, in organic solvent the method for high conversion and high productivity synthesis phenylacrolein compounds.Goal of the invention of the present invention is achieved by the following technical solution:
Two kinds of structural formulas are
the preparation method of phenylacrolein compounds, comprise following steps:
Get propargyl alcohol compounds, phosphorous acid aqueous solution, solvent be placed in reaction vessel, mixing; Under nitrogen atmosphere, at temperature of reaction is 100 ~ 120 DEG C, Keep agitation reaction 2 ~ 10h, is cooled to room temperature after reaction terminates, with saturated sodium carbonate solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains target product.
In described structural formula I, R
1be H, F, Cl, Br, methyl, ethyl, the tertiary butyl, methoxyl group, to dimethylamino, trifluoromethyl, 2,4,6-trimethylammoniums.
In described structural formula II, R
2it is naphthyl.
In above-mentioned synthetic method, described propargyl alcohol compounds is selected from 1-phenyl-2-propine-1-alcohol, 1-is to fluorophenyl-2-propine-1-alcohol, 1-rubigan-2-propine-1-alcohol, 1-Chloro-O-Phenyl-2-propine-1-alcohol, 1-is to bromophenyl-2-propine-1-alcohol, 1-p-methylphenyl-2-propine-1-alcohol, 1-o-methyl-phenyl--2-propine-1-alcohol, 1-is to ethylphenyl-2-propine-1-alcohol, 1-is to tert-butyl-phenyl-2-propine-1-alcohol, 1-p-methoxyphenyl-2-propine-1-alcohol, 1-is to dimethylamino phenyl-2-propine-1-alcohol, 1-p-trifluoromethyl phenyl-2-propine-1-alcohol, 1-(2, 4, 6-trimethylphenyl)-2-propine-1-alcohol, 1-(1-naphthyl)-2-propine-1-alcohol, 1-(2-naphthyl)-2-propine-1-alcohol.
In above-mentioned synthetic method, in described reaction process, solvent for use is selected from least one in methylene dichloride, chloroform, ethyl acetate, ethanol, toluene.
In above-mentioned synthetic method, the mass concentration of described phosphorous acid aqueous solution is 30% ~ 70%.
In above-mentioned synthetic method, the mol ratio between described phosphorous acid aqueous solution and propargyl alcohol compounds is [2:1] ~ [1:1].Temperature of reaction is 100 ~ 120 DEG C, and the reaction times is 2 ~ 10h.
In above-mentioned synthetic method, the organic solvent in described extraction step is ethyl acetate, chloroform or methylene dichloride.
Experimentally result, a kind of method simply being prepared fragrant phenylacrolein compounds by propargyl alcohol provided by the present invention.The method has cheaper starting materials and is easy to get, answers the features such as system is simple, gained target product is easily separated, productive rate is high, operation is easy, safe and reliable.The problems such as the use strong acid existing for this method solving in other synthetic method, condition harshness, complicated operation, valuable catalyst mix.
[Brief Description Of Drawings]
Fig. 1 is the reaction formula that propargyl alcohol is converted into phenylacrolein compounds.
[embodiment]
Be described further synthetic method of the present invention below in conjunction with synthesis example of the present invention, it should be noted that, embodiment does not form the restriction to application claims protection domain.
As shown in Figure 1, the synthesis step being converted into phenylacrolein compounds by propargyl alcohol provided by the invention is: under nitrogen atmosphere encloses, by propargyl alcohol, phosphorous acid aqueous solution, (mol ratio 100 ~ 200% is based on propargyl alcohol, mass concentration is 30 ~ 70%), organic solvent is placed in reaction vessel, mixing; At temperature of reaction is 100 ~ 120 DEG C, Keep agitation reaction 2 ~ 10 hours, is cooled to room temperature after reaction terminates, washs with saturated sodium carbonate solution, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, thick product, through pillar layer separation, obtains phenylacrolein compounds.
Synthesis example 1
The synthesis of phenylacrolein
Add 0.2mmol1-phenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 91%.
1HNMR(400MHz,CDCl
3):δ9.70(d,J＝7.7Hz,1H),7.57-7.55(m,2H),7.49-7.42(m,4H),6.72(dd,J＝16.0,7.7Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.6,152.7,133.9,131.2,129.0,128.5,128.4.
Synthesis example 2
To the synthesis of fluorine phenylacrolein
Add 0.2mmol1-in the reactor to fluorophenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 88%.
1HNMR(400MHz,CDCl
3):δ9.69(d,J＝7.6Hz,1H),7.59-7.54(m,2H),7.44(d,J＝16.0Hz,1H),7.15-7.09(m,2H),6.65(dd,J＝16.0,7.6Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.4,165.42(d,J
C-F＝253.2Hz),151.3,130.4(d,J
C-F＝8.7Hz),130.2(d,J
C-F＝3.4Hz),128.3(d,J
C-F＝2.3Hz),116.3(d,J
C-F＝22.1Hz).
Synthesis example 3
To the synthesis of chlorocinnamaldehyde
Add 0.2mmol1-rubigan-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 85%.
1HNMR(400MHz,CDCl
3):δ9.70(d,J＝7.6Hz,1H),7.50(d,J＝8.5Hz,2H),7.45-7.40(m,3H),6.69(dd,J＝16.0,7.6Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.3,151.0,137.2,132.4,129.6,129.4,128.9.
Synthesis example 4
The synthesis of adjacent chlorocinnamaldehyde
Add 0.2mmol1-Chloro-O-Phenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 81%.
1HNMR(400MHz,CDCl
3):δ9.76(d,J＝7.7Hz,1H),7.94(d,J＝16.0Hz,1H),7.67(dd,J＝7.6,1.9Hz,1H),7.46(dd,J＝7.9,1.4Hz,1H),7.39-7.30(m,2H),6.71(dd,J＝16.0,7.7Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.6,148.0,135.1,132.0,131.9,130.5,130.3,127.8,127.3.
Synthesis example 5
To the synthesis of bromocinnamaldehyde
Add 0.2mmol1-in the reactor to bromophenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 83%.
1HNMR(400MHz,CDCl
3):δ9.71(d,J＝7.6Hz,1H),7.57(d,J＝8.4Hz,2H),7.44-7.39(m,3H),6.70(dd,J＝16.0,7.6Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.3,151.0,132.8,132.4,129.7,129.0,125.7.
Synthesis example 6
To the synthesis of methyl cinnamic aldehyde
Add 0.2mmol1-p-methylphenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 92%.
1HNMR(400MHz,CDCl
3):δ9.68(d,J＝7.7Hz,1H),7.47-7.43(m,3H),7.24(d,J＝8.0Hz,2H),6.68(dd,J＝15.9,7.7Hz,1H),2.39(s,3H).
13CNMR(100MHz,CDCl
3):δ193.7,152.8,141.9,131.3,129.8,128.5,127.7,21.5.
Synthesis example 7
The synthesis of adjacent methyl cinnamic aldehyde
Add 0.2mmol1-o-methyl-phenyl--2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 75%.
1HNMR(400MHz,CDCl
3):δ9.73(d,J＝7.7Hz,1H),7.78(d,J＝15.8Hz,1H),7.59(d,J＝7.3Hz,1H),7.35-7.31(m,1H),7.27-7.23(m,2H),6.67(dd,J＝15.8,7.7Hz,1H),2.48(s,3H).
13CNMR(100MHz,CDCl
3):δ193.6,150.2,137.9,132.7,131.0,131.0,129.5,126.7,126.5,19.7.
Synthesis example 8
To the synthesis of ethyl cinnamyl nitrile
Add 0.2mmol1-in the reactor to ethylphenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 93%.
1HNMR(400MHz,CDCl
3):δ9.68(d,J＝7.7Hz,1H),7.51-7.44(m,3H),7.26(d,J＝8.1Hz,2H),6.69(dd,J＝15.9,7.8Hz,1H),2.69(q,J＝7.6Hz,2H),1.25(t,J＝7.6Hz,3H).
13CNMR(100MHz,CDCl
3):δ193.8,152.9,143.2,131.5,128.6,128.6,127.7,28.8,15.2.
Synthesis example 9
To the synthesis of tertiary butyl phenylacrolein
Add 0.2mmol1-in the reactor to tert-butyl-phenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 95%.
1HNMR(400MHz,CDCl
3):δ9.69(d,J＝7.8Hz,1H),7.52-7.44(m,5H),6.70(dd,J＝15.9,7.8Hz,1H),1.33(s,9H).
13CNMR(100MHz,CDCl
3):δ193.8,155.0,152.8,131.2,128.3,127.8,126.0,34.9,31.0.
Synthesis example 10
The synthesis of p-met hoxycinnamic aldehyde
Add 0.2mmol1-p-methoxyphenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 70%.
1HNMR(400MHz,CDCl
3):δ9.65(d,J＝7.8Hz,1H),7.53(d,J＝8.7Hz,2H),7.43(d,J＝15.8Hz,1H),6.95(d,J＝8.8Hz,2H),6.61(dd,J＝15.8,7.8Hz,1H),3.86(s,3H).
13CNMR(100MHz,CDCl
3):δ193.7,162.2,152.7,130.3,126.7,126.5,114.5,55.4.
Synthesis example 11
To the synthesis of dimethylamino base phenylacrolein
Add 0.2mmol1-in the reactor to dimethylamino phenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 65%.
1HNMR(400MHz,CDCl
3):δ9.59(d,J＝7.9Hz,1H),7.46(d,J＝8.9Hz,2H),7.38(d,J＝15.7Hz,1H),6.69(d,J＝8.9Hz,2H),6.55(dd,J＝15.6,7.9Hz,1H),3.05(s,6H).
13CNMR(100MHz,CDCl
3):δ193.7,153.9,152.3,130.4,123.8,121.7,111.7,40.0.
Synthesis example 12
To the synthesis of trifluoromethyl phenylacrolein
Add 0.2mmol1-p-trifluoromethyl phenyl-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 10h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 74%.
1HNMR(400MHz,CDCl
3):δ9.75(d,J＝7.5Hz,1H),7.71-7.66(m,4H),7.51(d,J＝16.0Hz,1H),6.78(dd,J＝16.0,7.5Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.1,150.2,137.3,132.6(d,J
C-F＝32.9Hz),130.5,128.5,126.0(q,J
C-F＝3.8Hz),123.6(d,J
C-F＝272.4Hz).
Synthesis example 13
The synthesis of 2,4,6-trimethylammonium phenylacrolein
Add 0.2mmol1-(2,4,6-trimethylphenyl)-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 68%.
1HNMR(400MHz,CDCl
3):δ9.70(d,J＝7.7Hz,1H),7.68(d,J＝16.3Hz,1H),6.93(s,2H),6.41(dd,J＝16.3,7.7Hz,1H),2.36(s,6H),2.30(s,3H).
13CNMR(100MHz,CDCl
3):δ194.3,151.5,139.6,137.1,133.6,130.1,129.5,21.2,21.1.
Synthesis example 14
The synthesis of 3-(1-naphthyl)-propenal
Add 0.2mmol1-(1-naphthyl)-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 68%.
1HNMR(400MHz,CDCl
3):δ9.86(d,J＝7.7Hz,1H),8.34(d,J＝15.7Hz,1H),8.20(d,J＝8.4Hz,1H),7.96(d,J＝8.2Hz,1H),7.92(d,J＝7.7Hz,1H),7.83(d,J＝7.2Hz,1H),7.64–7.51(m,3H),6.85(dd,J＝15.7,7.7Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.6,149.3,133.7,131.6,131.1,131.0,130.9,128.9,127.2,126.4,125.7,125.4,122.7.
Synthesis example 15
The synthesis of 3-(2-naphthyl)-propenal
Add 0.2mmol1-(2-naphthyl)-2-propine-1-alcohol, 0.30mmol50wt% phosphorous acid aqueous solution in the reactor, 0.5mL methylene dichloride.Under nitrogen atmosphere, be heated to 110 DEG C, Keep agitation 2h, stopped reaction, is cooled to room temperature, adds saturated sodium carbonate solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 64%.
1HNMR(400MHz,CDCl
3):δ9.77(d,J＝7.7Hz,1H),8.00(s,1H),7.91-7.85(m,3H),7.69(dd,J＝8.6,1.7Hz,1H),7.65(d,J＝15.9Hz,1H),7.60-7.52(m,2H),6.84(dd,J＝15.9,7.7Hz,1H).
13CNMR(100MHz,CDCl
3):δ193.7,152.8,134.6,133.1,131.5,130.7,128.9,128.7,128.7,127.8,127.8,126.9,123.5。
Claims (6)
1. a preparation method for phenylacrolein compounds, comprises following step:
Get propargyl alcohol compounds, phosphorous acid aqueous solution, solvent be placed in reaction vessel, mixing; Under nitrogen atmosphere, at temperature of reaction is 100 ~ 120 DEG C, Keep agitation reaction 2 ~ 10h, be cooled to room temperature after reaction terminates, with saturated sodium carbonate solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains phenylacrolein compounds.There is following structural formula:
In described formula I, R
1be H, F, Cl, Br, methyl, ethyl, the tertiary butyl, methoxyl group, to dimethylin, trifluoromethyl, 2,4,6-trimethylammoniums.
In described general formula II, R
2it is naphthyl.
2. the preparation method of phenylacrolein compounds according to claim 1, it is characterized in that, described propargyl alcohol compounds is selected from 1-phenyl-2-propine-1-alcohol, 1-is to fluorophenyl-2-propine-1-alcohol, 1-rubigan-2-propine-1-alcohol, 1-Chloro-O-Phenyl-2-propine-1-alcohol, 1-is to bromophenyl-2-propine-1-alcohol, 1-p-methylphenyl-2-propine-1-alcohol, 1-o-methyl-phenyl--2-propine-1-alcohol, 1-is to ethylphenyl-2-propine-1-alcohol, 1-is to tert-butyl-phenyl-2-propine-1-alcohol, 1-p-methoxyphenyl-2-propine-1-alcohol, 1-is to dimethylaminophenyl-2-propine-1-alcohol, 1-p-trifluoromethyl phenyl-2-propine-1-alcohol, 1-(2, 4, 6-trimethylphenyl)-2-propine-1-alcohol, 1-(1-naphthyl)-2-propine-1-alcohol, 1-(2-naphthyl)-2-propine-1-alcohol.
3. the preparation method of phenylacrolein compounds according to claim 1, is characterized in that, in described reaction process, solvent for use is selected from least one in methylene dichloride, chloroform, ethyl acetate, ethanol, toluene.
4. the preparation method of phenylacrolein compounds according to claim 1, is characterized in that, the mass concentration of described phosphorous acid aqueous solution is 30% ~ 70%.
5. the preparation method of phenylacrolein compounds according to claim 1, is characterized in that, the mol ratio between phosphorous acid aqueous solution and propargyl alcohol compounds is [2:1] ~ [1:1].Temperature of reaction is 100 ~ 120 DEG C, and the reaction times is 2 ~ 10h.
6. the preparation method of phenylacrolein compounds according to claim 1, is characterized in that, the organic solvent in described extraction step is ethyl acetate, chloroform or methylene dichloride.
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|---|---|---|---|---|
| CN105503553A (en) * | 2016-01-27 | 2016-04-20 | 陕西师范大学 | Preparation method of alpha-beta-unsaturated carbonyl compound |
| CN109824490A (en) * | 2019-02-13 | 2019-05-31 | 上海拜乐新材料科技有限公司 | A kind of preparation method of cinnamic acid and its derivative |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503553A (en) * | 2016-01-27 | 2016-04-20 | 陕西师范大学 | Preparation method of alpha-beta-unsaturated carbonyl compound |
| CN109824490A (en) * | 2019-02-13 | 2019-05-31 | 上海拜乐新材料科技有限公司 | A kind of preparation method of cinnamic acid and its derivative |
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