CN105541582A - MBH reaction of alpha, beta-unsaturated ketone and allyl acetate - Google Patents
MBH reaction of alpha, beta-unsaturated ketone and allyl acetate Download PDFInfo
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- CN105541582A CN105541582A CN201610008630.2A CN201610008630A CN105541582A CN 105541582 A CN105541582 A CN 105541582A CN 201610008630 A CN201610008630 A CN 201610008630A CN 105541582 A CN105541582 A CN 105541582A
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- acetic acid
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- acid ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses an MBH reaction of alpha, beta-unsaturated ketone and allyl acetate. The reaction comprises the following steps that 1, alpha, beta-unsaturated ketone, acetic acid and a catalyst are added into solvent and stirred, then Pd(PPh3)4 and allyl acetate are added, and the mixture reacts for 22-26 hours in a stirred mode at the temperature of 50 DEG C-70 DEG C; 2, a reaction product obtained in the step 1 is decompressed, the solvent is steamed away, and residues are subjected to column chromatography separation to obtain alpha-allyl substituted alpha, beta-unsaturated ketone. Adopted allyl acetate is easier to prepare, and alpha, beta-unsaturated ketone with the open chain is used. Because acetic acid is added, alpha, beta-unsaturated ketone is prevented from generating the MBH reaction by itself.
Description
Technical field
The MBH that the present invention relates to alpha, beta-unsaturated ketone and allyl acetic acid ester reacts.
Background technology
Morita-Baylis-Hillman (MBH) reaction forms the very important building-up reactions of C-C.This reaction of atomic good economy performance, and can polyfunctional compound be formed, apply very wide in organic synthesis and pharmaceutical synthesis.React although α, β-unsaturated compound MBH can occur smoothly with electrophilic reagents such as aldehyde, 1,2-diketone, imines, but the alkylated reaction of MBH is still challenging.Bibliographical information, can there is MBH alkylated reaction with allyl halide in ring-type alpha, beta-unsaturated ketone.And relative to allyl halide, allyl alcohol and ester thereof are more easily prepared usually.But relevant α, β-unsaturated compound and allyl ester or the intermolecular MBH alkylated reaction of allyl alcohol, yet there are no report.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and utilizes allyl acetic acid ester and alpha, beta-unsaturated ketone that MBH occurs to react, the short-cut method of the alpha, beta-unsaturated ketone that preparation α-allyl group replaces.
In order to solve the problems of the technologies described above, the MBH that the invention provides a kind of alpha, beta-unsaturated ketone and allyl acetic acid ester reacts, and comprises the steps:
1), in solvent, first add alpha, beta-unsaturated ketone, acetic acid and catalyzer stir, then add Pd (PPh
3)
4with allyl acetic acid ester, in 50 ~ 70 DEG C of stirring reactions 22 ~ 26 hours (being preferably 60 DEG C of stirring reactions 24 hours);
Described alpha, beta-unsaturated ketone: acetic acid: catalyzer: Pd (PPh
3)
4: the mol ratio of allyl acetic acid ester is 1: 1.9 ~ 2.1: 0.9 ~ 1.1: 0.08 ~ 0.12: 2.9 ~ 3.1 (being preferably 1: 2: 1: 0.1: 3);
The general formula of alpha, beta-unsaturated ketone is
The general formula of allyl acetic acid ester is
2), by step 1) the reaction product pressure reducing and steaming solvent of gained, residue, through column chromatography for separation, obtains the alpha, beta-unsaturated ketone that α-allyl group replaces.
Improvement as the MBH of alpha, beta-unsaturated ketone of the present invention and allyl acetic acid ester reacts:
Ar in the general formula of alpha, beta-unsaturated ketone is following arbitrary: p-MeC
6h
4, o-MeC
6h
4, m-MeC
6h
4, m-MeOC
6h
4, P-MeOC
6h
4, Ph, p-FC
6h
4, p-ClC
6h
4, p-BrC
6h
4, m-NO
2c
6h
4, P-NO
2c
6h
4, P-CF
3c
6h
4, 2-naphthyl.
Namely, corresponding alpha, beta-unsaturated ketone is followed successively by respectively: p-methylphenyl vinyl ketone, o-methyl-phenyl-vinyl ketone, a methyl phenyl vinyl ketone, m-methoxyphenyl vinyl ketone, p-methoxyphenyl vinyl ketone, phenyl vinyl ketone, to fluorophenyl vinyl ketone, rubigan vinyl ketone, to bromophenyl vinyl ketone, m-nitro base vinyl ketone, p-nitrophenyl vinyl ketone, p-trifluoromethyl phenyl vinyl ketone, 2-naphthylethenyl ketone.
Further improvement as the MBH of alpha, beta-unsaturated ketone of the present invention and allyl acetic acid ester reacts:
Allyl acetic acid ester is following arbitrary:
R in general formula is H, and allyl acetic acid ester is allyl acetate;
R in general formula is Ph, and allyl acetic acid ester is acetic acid 3-allyl ester;
R in general formula is o-MeOC
6h
4, allyl acetic acid ester is acetic acid 3-o-methoxyphenyl allyl ester;
R in general formula is p-FC
6h
4, allyl acetic acid ester is that acetic acid 3-is to fluorophenyl allyl ester;
R in general formula is p-ClC
6h
4, allyl acetic acid ester is acetic acid 3-rubigan allyl ester;
R in general formula is
allyl acetic acid ester is (E)-2-methyl-3-allyl yl acetate.
Further improvement as the MBH of alpha, beta-unsaturated ketone of the present invention and allyl acetic acid ester reacts: catalyzer is P (n-Bu)
3.
Further improvement as the MBH of alpha, beta-unsaturated ketone of the present invention and allyl acetic acid ester reacts: described step 2) column chromatography in, eluent used is by ethyl acetate: sherwood oil=1: the volume ratio of 100 is obtained by mixing.
Further improvement as the MBH of alpha, beta-unsaturated ketone of the present invention and allyl acetic acid ester reacts: described step 1) in, solvent is Isosorbide-5-Nitrae-dioxane.
Preferred version of the present invention is specific as follows:
In the Isosorbide-5-Nitrae-dioxane solution (2mL) of alpha, beta-unsaturated ketone 1 (0.1mmol) and acetic acid (12.0mg, 0.2mmol), add P (n-Bu)
3(20.2mg, 0.1mmol).After this mixed solution stirs 1 minute, add Pd (PPh
3)
4(11.6mg, 0.01mmol) and allyl acetic acid ester 2 (0.3mmol).By this mixed solution at 60 DEG C, stirring reaction 24 hours.Pressure reducing and steaming solvent, residue is separated through column chromatography (silica gel, ethyl acetate: eluent is made in sherwood oil=1/100), can obtain the alpha, beta-unsaturated ketone 3 that required α-allyl group replaces.
The present invention has following technical superiority: the allyl acetic acid ester that (1) uses more easily is prepared, and uses the alpha, beta-unsaturated ketone of general open chain.(2) because adding acetic acid, thus alpha, beta-unsaturated ketone self generation MBH reaction is avoided.(3) productive rate is high, reaction conditions is gentle.
Embodiment
Embodiment 1, utilize the MBH reaction method of alpha, beta-unsaturated ketone and allyl acetic acid ester, carry out following steps successively:
1), in the Isosorbide-5-Nitrae-dioxane solution (2mL) of alpha, beta-unsaturated ketone (0.1mmol) and acetic acid (12.0mg, 0.2mmol), tributylphosphine P (n-Bu) is added
3(20.2mg, 0.1mmol).After this mixed solution stirs 1 minute, add Pd (PPh
3)
4(11.6mg, 0.01mmol) and allyl acetic acid ester (0.3mmol).By this mixed solution at 60 DEG C, stirring reaction 24 hours.
Alpha, beta-unsaturated ketone is specially 1a p-methylphenyl vinyl ketone;
Allyl acetic acid ester is specially 2a allyl acetate;
2), by step 1) reaction product of gained revolve steam except desolventizing (namely, 1,4-dioxane), residue is through column chromatography purification, select 200-300 object silica gel, using ethyl acetate: sherwood oil=1: 100 (volume ratios) are as eluent, and the elutriant of gained revolves and steams to obtain 2-methylene-1-(p-tolyl) pent-4-en-1-one (3aa).
Embodiment 2 ~ 18, as described in Table 1, change alpha, beta-unsaturated ketone, allyl acetic acid ester accordingly, all the other are equal to embodiment 1; Thus obtain the alpha, beta-unsaturated ketone of α as described in Table 1-allyl group replacement.
Alpha, beta-unsaturated ketone be specially the p-methylphenyl vinyl ketone of 1a-m, o-methyl-phenyl-vinyl ketone, a methyl phenyl vinyl ketone, m-methoxyphenyl vinyl ketone, p-methoxyphenyl vinyl ketone, phenyl vinyl ketone, to fluorophenyl vinyl ketone, rubigan vinyl ketone, to bromophenyl vinyl ketone, m-nitro base vinyl ketone, p-nitrophenyl vinyl ketone, p-trifluoromethyl phenyl vinyl ketone, 2-naphthylethenyl ketone;
Allyl acetic acid ester is specially the allyl acetate of 2a-f, acetic acid 3-allyl ester, acetic acid 3-o-methoxyphenyl allyl ester, acetic acid 3-to fluorophenyl allyl ester, acetic acid 3-rubigan allyl ester, (E)-2-methyl-3-allyl yl acetate.
Table 1
2-methylene-1-(p-tolyl)pent-4-en-1-one3aa
Yield：82％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.68(d，J＝8.0Hz，2H)，7.24(d，J＝8.0Hz，2H)，6.95-5.83(m，2H)，5.64(s，1H)，5.17-5.09(m，2H)，3.22(d，J＝6.4Hz，2H)，2.41(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.5，146.5，143.0，135.0，134.9，129.8，128.9，125.5，117.1，36.4，21.6；HR-MS(EI-TOF)(M
+)calculatedforC
13H
14O186.1045，found186.1049。
2-methylene-1-(o-tolyl)pent-4-en-1-one3ba
Yield：71％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.34-7.30(m，1H)，7.25-7.18(m，3H)，5.97-5.87(m，2H)，5.65(d，J＝0.8Hz，1H)，5.19-5.11(m，2H)，3.21(d，J＝7.2Hz，2H)，2.30(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：199.9，147.8，138.9，136.2，135.1，130.8，129.8，129.7，127.9，125.0，117.1，34.8，19.7；HR-MS(EI-TOF)(M
+)calculatedforC
13H
14O186.1045，found186.1048。
2-methylene-1-(m-tolyl)pent-4-en-1-one3ca
Yield：64％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.56-7.53(m，2H)，7.36-7.29(m，2H)，5.95-5.85(m，2H)，5.67(d，J＝0.8Hz，1H)，5.18-5.10(m，2H)，3.22(dt，J＝6.8，1.0Hz，2H)，2.40(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.9，146.5，138.1，137.7，135.0，133.0，129.9，128.0，126.8，126.4，117.1，36.2，21.3；HR-MS(EI-TOF)(M
+)calculatedforC
13H
14O186.1045，found186.1044。
1-(3-methoxyphenyl)-2-methylenepent-4-en-1-one3da
Yield：80％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.36-7.28(m，3H)，7.09-7.06(m，1H)，5.95-5.84(m，2H)，5.69(d，J＝0.8Hz，1H)，5.17-5.10(m，2H)，3.84(s，3H)，3.22-3.21(d，J＝6.8Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.4，159.5，146.3，139.0，134.9，129.1，126.4，122.2，118.5，117.2，113.9，55.4，36.2；HR-MS(EI-TOF)(M
+)calculatedforC
13H
14O
2202.0994，found202.0998。
1-(4-methoxyphenyl)-2-methylenepent-4-en-1-one3ea
Yield：76％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.83-7.79(m，2H)，6.94-6.91(m，2H)，5.94-5.84(m，1H)，5.77(d，J＝1.2Hz，1H)，5.58(d，J＝0.8Hz，1H)，5.16-5.08(m，2H)，3.86(s，3H)，3.21(d，J＝6.8Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：196.5，163.2，146.5，135.0，132.0，130.1，124.2，117.1，113.5，55.4，36.7；HR-MS(EI-TOF)(M
+)calculatedforC
13H
14O
2202.0994，found202.0993。
2-methylene-1-phenylpent-4-en-1-one3fa
Yield：78％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.76-7.74(m，2H)，7.55-7.51(m，1H)，7.45-7.41(m，2H)，5.95-5.85(m，2H)，5.67(d，J＝0.8Hz，1H)，5.18-5.09(m，2H)，3.22(dt，J＝6.8，1.1Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.7，146.4，137.7，135.0，132.2，129.5，128.2，126.5，117.2，36.2；MS(EI)：m/z172.1(M
+)，171.1，129.1，128.1，105.1，77.1，51.1，39.1。
1-(4-fluorophenyl)-2-methylenepent-4-en-1-one3ga
Yield：73％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.82-7.79(m，2H)，7.14-7.09(m，2H)，5.94-5.83(m，2H)，5.63(d，J＝0.8Hz，1H)，5.17-5.10(m，2H)，3.21(dt，J＝6.8，1.0Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：196.1，165.5(d，J＝252.1Hz，)，146.3，134.8，133.8(d，J＝3.0Hz)，132.1(d，J＝8.9Hz)，125.9，117.3，115.3(d，J＝21.5Hz)，36.3；HR-MS(EI-TOF)(M
+)calculatedforC
12H
11FO190.0794，found190.0795。
1-(4-chlorophenyl)-2-methylenepent-4-en-1-one3ha
Yield：72％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.72-7.69(m，2H)，7.43-7.40(m，2H)，5.93-5.83(m，2H)，5.65(d，J＝0.8Hz，1H)，5.17-5.10(m，2H)，3.21(dt，J＝6.8，1.0Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：196.4，146.3，138.7，136.0，134.7，130.9，128.6，126.5，117.4，36.2；HR-MS(EI-TOF)(M
+)calculatedforC
12H
11ClO206.0498，found206.0498。
1-(4-bromophenyl)-2-methylenepent-4-en-1-one3ia
Yield：66％.yellowoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.64-7.57(m，4H)，5.93-5.83(m，2H)，5.65(s，1H)，5.17-5.11(m，2H)，3.21(d，J＝6.4Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：196.5，146.2，136.4，134.7，131.5，131.0，127.2，126.6，117.4，36.1；HR-MS(EI-TOF)(M
+)calculatedforC
12H
11BrO249.9993，found249.9995。
2-methylene-1-(3-nitrophenyl)pent-4-en-1-one3ja
Yield：69％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：8.56(t，J＝1.8Hz，1H)，8.40(ddd，J＝8.4，2.2，1.0Hz，1H)，8.08(dt，J＝7.6，1.2Hz，1H)，7.67(t，J＝8.0Hz，1H)，6.03(t，J＝1.4Hz，1H)，5.96-5.85(m，1H)，5.72(s，1H)，5.21-5.14(m，2H)，3.25(d，J＝6.8Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：195.1，148.0，145.9，139.2，134.9，134.3，129.6，128.1，126.5，124.2，117.8，35.9；HR-MS(EI-TOF)(M
+)calculatedforC
12H
11NO
3217.0739，found217.0742。
2-methylene-1-(4-nitrophenyl)pent-4-en-1-one3ka
Yield：80％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：8.30(dt，J＝8.8，2.1Hz，2H)，7.86(dt，J＝9.2，2.0Hz，2H)，6.04(t，J＝1.4Hz，1H)，5.95-5.85(m，1H)，5.71(s，1H)，5.20-5.14(m，2H)，3.24(dt，J＝6.8，1.0Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：195.7，149.7，146.2，143.1，134.4，130.1，128.8，123.5，117.7，35.7；HR-MS(EI-TOF)(M
+)calculatedforC
12H
11NO
3217.0739，found217.0742。
2-methylene-1-(4-(trifluoromethyl)phenyl)pent-4-en-1-one31a
Yield：65％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.82(d，J＝8.0Hz，2H)，7.71(d，J＝8.0Hz，2H)，5.98(s，1H)，5.95-5.85(m，1H)，5.69(s，1H)，5.19-5.13(m，2H)，3.23(d，J＝6.8Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：196.5，146.2，140.9，134.6，129.6，128.0，125.3(q，J＝3.7Hz)，117.5，35.8；HR-MS(EI-TOF)(M
+)calculatedforC
13H
11F
3O240.0762，found240.0764。
2-methylene-1-(naphthalen-2-yl)pent-4-en-1-one3ma
Yield：86％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：8.26(s，1H)，7.93-7.85(m，4H)，7.60-7.51(m，2H)，6.00-5.90(m，2H)，5.73(d，J＝0.8Hz，1H)，5.22-5.12(m，2H)，3.28(d，J＝6.8Hz，2H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.7，146.6，135.2，135.0，134.9，132.3，131.1，129.4，128.2，128.1，127.8，126.8，126.2，125.5，117.3，36.4；HR-MS(EI-TOF)(M
+)calculatedforC
16H
14O222.1045，found222.1042。
(E)-2-methylene-5-phenyl-1-(p-tolyl)pent-4-en-1-one3ab
Yield：82％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.70(d，J＝7.6Hz，2H)，7.37-7.20(m，7H)，6.50(d，J＝16.0Hz，1H)，6.32-6.25(m，1H)，5.89(s，1H)，5.67(s，1H)，3.37(d，J＝6.8Hz，2H)，2.41(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.5，146.7，143.1，137.4，134.9，132.4，129.8，128.9，128.5，127.2，126.7，126.2，125.8，35.6，21.6；HR-MS(EI-TOF)(M
+)calculatedforC
19H
18O262.1358，found262.1359。
(E)-5-(2-methoxyphenyl)-2-methylene-1-(p-tolyl)pent-4-en-1-one3ac
Yield：61％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.71(d，J＝8.0Hz，2H)，7.42(dd，J＝7.6，1.6Hz，1H)，7.25-7.17(m，3H)，6.92-6.80(m，3H)，6.33-6.25(m，1H)，5.89(d，J＝0.8Hz，1H)，5.66(d，J＝0.8Hz，1H)，3.83(s，3H)，3.38(dd，J＝7.0，1.0Hz，2H)，2.41(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.7，156.4，146.9，143.0，135.0，129.8，128.9，128.2，127.3，127.0，126.6，126.4，125.6，120.6，110.9，55.5，36.0，21.6；HR-MS(EI-TOF)(M
+)calculatedforC
20H
20O
2292.1463，found292.1467。
(E)-5-(4-fluorophenyl)-2-methylene-1-(p-tolyl)pent-4-en-1-one3ad
Yield：71％.Whitesolid.Mp：72-74℃；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.69(d，J＝8.0Hz，2H)，7.33-7.23(m，4H)，7.00-6.95(m，2H)，6.46(d，J＝16.0Hz，1H)，6.23-6.16(m，1H)，5.88(s，1H)，5.67(s，1H)，3.35(d，J＝6.8Hz，2H)，2.41(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.4，162.1(d，J＝244.8Hz)，146.6，143.1，134.9，133.5，131.2，129.8，129.0，127.6(d，J＝7.8Hz)，126.4(d，J＝2.1Hz)，125.8，115.4(d，J＝21.0Hz)，35.6，21.6；HR-MS(EI-TOF)(M
+)calculatedforC
19H
17FO280.1263，found280.1262。
(E)-5-(4-chlorophenyl)-2-methylene-1-(p-tolyl)pent-4-en-1-one3ae
Yield：77％.Whitesolid.Mp：76-78℃；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.69(d，J＝8.0Hz，2H)，7.29-7.23(m，6H)，6.47(d，J＝16.8Hz，1H)，6.30-6.22(m，1H)，5.88(s，1H)，5.68(s，1H)，3.36(d，J＝7.2Hz，2H)，2.41(s，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.4，146.4，143.1，135.8，134.9，132.8，131.2，129.7，129.0，128.6，127.5，127.4，125.9，35.6，21.6；HR-MS(EI-TOF)(M
+)calculatedforC
19H
17ClO296.0968，found296.0968。
(E)-4-methyl-2-methylene-5-phenyl-1-(p-tolyl)pent-4-en-1-one3af
Yield：50％.Colorlessoil；
1HNMR(400MHz，CDCl
3)，δ(ppm)：7.72(d，J＝8.0Hz，2H)，7.31-7.17(m，7H)，6.38(s，1H)，5.86(s，1H)，5.68(s，1H)，3.34(s，2H)，2.41(s，3H)，1.90(d，J＝1.6Hz，3H)；
13CNMR(100MHz，CDCl
3)，δ(ppm)：197.5，146.3，143.1，138.2，135.8，134.9，129.8，129.0，128.8，128.1，127.8，126.2，125.8，42.9，21.6，17.9；HR-MS(EI-TOF)(M
+)calculatedforC
20H
20O276.1514，found276.1517。
The alpha, beta-unsaturated ketone that α of the present invention-allyl group replaces can be used for the preparation that natural product etc. has physiologically active molecule.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
1. the MBH of alpha, beta-unsaturated ketone and allyl acetic acid ester reacts, and it is characterized in that comprising the steps:
1), in solvent, first add alpha, beta-unsaturated ketone, acetic acid and catalyzer stir, then add Pd (PPh
3)
4with allyl acetic acid ester, in 50 ~ 70 DEG C of stirring reactions 22 ~ 26 hours;
Described alpha, beta-unsaturated ketone: acetic acid: catalyzer: Pd (PPh
3)
4: the mol ratio of allyl acetic acid ester is 1:1.9 ~ 2.1:0.9 ~ 1.1:0.08 ~ 0.12:2.9 ~ 3.1;
The general formula of alpha, beta-unsaturated ketone is
The general formula of allyl acetic acid ester is
2), by step 1) the reaction product pressure reducing and steaming solvent of gained, residue, through column chromatography for separation, obtains the alpha, beta-unsaturated ketone that α-allyl group replaces.
2. the MBH of alpha, beta-unsaturated ketone according to claim 1 and allyl acetic acid ester reacts, and it is characterized in that:
Ar in the general formula of alpha, beta-unsaturated ketone is following arbitrary: p-MeC
6h
4, o-MeC
6h
4, m-MeC
6h
4, m-MeOC
6h
4, P-MeOC
6h
4, Ph, p-FC
6h
4, p-ClC
6h
4, p-BrC
6h
4, m-NO
2c
6h
4, P-NO
2c
6h
4, P-CF
3c
6h
4, 2-naphthyl.
3. the MBH of alpha, beta-unsaturated ketone according to claim 2 and allyl acetic acid ester reacts, and it is characterized in that:
Allyl acetic acid ester is following arbitrary:
R in general formula is H, and allyl acetic acid ester is allyl acetate;
R in general formula is Ph, and allyl acetic acid ester is acetic acid 3-allyl ester;
R in general formula is o-MeOC
6h
4, allyl acetic acid ester is acetic acid 3-o-methoxyphenyl allyl ester;
R in general formula is p-FC
6h
4, allyl acetic acid ester is that acetic acid 3-is to fluorophenyl allyl ester;
R in general formula is p-ClC
6h
4, allyl acetic acid ester is acetic acid 3-rubigan allyl ester;
R in general formula is
allyl acetic acid ester is (E)-2-methyl-3-allyl yl acetate.
4. the alpha, beta-unsaturated ketone according to claim 1,2 or 3 and the MBH of allyl acetic acid ester react, and it is characterized in that: described catalyzer is P (n-Bu)
3.
5. the MBH of alpha, beta-unsaturated ketone according to claim 4 and allyl acetic acid ester reacts, and it is characterized in that: described step 2) column chromatography in, eluent used is by ethyl acetate: the volume ratio of sherwood oil=1:100 is obtained by mixing.
6. the MBH of alpha, beta-unsaturated ketone according to claim 4 and allyl acetic acid ester reacts, and it is characterized in that: described step 1) in, solvent is Isosorbide-5-Nitrae-dioxane.
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| CN108727179A (en) * | 2018-07-18 | 2018-11-02 | 信阳师范学院 | A kind of alpha, beta-unsaturated ketone of α-allyl substitution, the synthetic method of ester or nitrile compound |
| CN110066231A (en) * | 2019-05-24 | 2019-07-30 | 江苏师范大学 | A kind of azepine β-substitution Morita-Baylis-Hillman type compound and its synthetic method |
| CN110283078A (en) * | 2019-07-10 | 2019-09-27 | 南京工业大学 | Polysubstituted 1, 4-diene compound and preparation method thereof |
| CN111233645A (en) * | 2020-03-31 | 2020-06-05 | 浙江大学 | Method for preparing tri-substituted cyclopentene by MBH/Wittig domino reaction of vinylon insertion |
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| CN103553931A (en) * | 2013-10-24 | 2014-02-05 | 中国科学院化学研究所 | Method for synthesizing chiral diketone compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108727179A (en) * | 2018-07-18 | 2018-11-02 | 信阳师范学院 | A kind of alpha, beta-unsaturated ketone of α-allyl substitution, the synthetic method of ester or nitrile compound |
| CN108727179B (en) * | 2018-07-18 | 2021-04-30 | 信阳师范学院 | Synthetic method of alpha-allyl substituted alpha, beta-unsaturated ketone, ester or nitrile compound |
| CN110066231A (en) * | 2019-05-24 | 2019-07-30 | 江苏师范大学 | A kind of azepine β-substitution Morita-Baylis-Hillman type compound and its synthetic method |
| CN110066231B (en) * | 2019-05-24 | 2021-06-25 | 江苏师范大学 | Aza beta-substituted Morita-Baylis-Hillman type compound and synthetic method thereof |
| CN110283078A (en) * | 2019-07-10 | 2019-09-27 | 南京工业大学 | Polysubstituted 1, 4-diene compound and preparation method thereof |
| CN111233645A (en) * | 2020-03-31 | 2020-06-05 | 浙江大学 | Method for preparing tri-substituted cyclopentene by MBH/Wittig domino reaction of vinylon insertion |
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