CN105859557A - Preparation method of alpha, beta-unsaturated carboxylate compound - Google Patents
Preparation method of alpha, beta-unsaturated carboxylate compound Download PDFInfo
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- CN105859557A CN105859557A CN201610222368.1A CN201610222368A CN105859557A CN 105859557 A CN105859557 A CN 105859557A CN 201610222368 A CN201610222368 A CN 201610222368A CN 105859557 A CN105859557 A CN 105859557A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/80—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/56—Radicals substituted by oxygen atoms
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Abstract
The invention relates to the technical field of CO2 activation and conversion and related chemistry, relates to a method for synthesizing alpha, beta-unsaturated carboxylate by using CO2 as a C1 source, and especially relates to a method for synthesizing alpha, beta-unsaturated carboxylate based on (hetero)arylmethyl halide and trisubstituted allylsilane. The method is characterized in that a carboxylation reaction of (hetero)arylmethyl halide and trisubstituted allylsilane is realized under the catalysis of a Pd catalyst by using carbon dioxide as the C1 source. The invention mainly provides new simple external ligand-free nanometer catalysis system. CO2 is used as the C1 source to synthesize alpha, beta-unsaturated carboxylate. The catalysis system has the advantages of green and easily available reaction raw materials, mild reaction conditions, simple experiment operation, and good compatibility of function groups. CO2 is the plentiful, cheap, easily-available and renewable C1 source, so the method has large application values and large social and economic benefits.
Description
Technical field
The present invention relates to CO2Activating conversion and related chemistry technical field, relate to a kind of CO2As C1
The preparation method of the esters of alpha, beta, unsaturated carboxylic acids compound in source.
Background technology
Carbon dioxide is rich reserves, cheap and easy to get, nontoxic and reproducible C1Source, its catalyzed conversion is raw
The research becoming the fine chemicals of high added value has caused the extensive concern of researcher.In the past
In decades, many methods that are fixing and that convert about carbon dioxide have been in the news and [have seen: (a)
Carbon Dioxide as a Chemical Feedstock,ed.Aresta,M.Wiley-VHC,Weinheim,
2010.(b)Sakakura,T.；Choi,J.-C.；Yasuda,H.Chem.Rev.2007,107,2365.].At this
In a little methods, excessive metalcatalyzing activation C-M (Sn, B, Zn, Si) key, c h bond, C-X (Cl, Br,
I) key, C-O key insert carbon dioxide and form the process of new C C key is fix carbon dioxide at present main
Several ways.But above-mentioned method needs the addition of part (Phosphine ligands, nitrogen ligand, azepine carbenes)
Realize the fixing of carbon dioxide [to see: (a) Y.Tani, T.Fujihara, J.Terao, Y.Tsuji, J.Am.
Chem.Soc.,2014,136,17706.(b)T.Moragas,J.Cornella,R.Martin,J.Am.Chem.
Soc.,2014,136,17702.(c)L.Zhang,J.Cheng,B.Carry,Z.Hou,J.Am.Chem.Soc.,
2012,134,14314.].Thus develop a kind of simple nano catalystic system without additional part, utilize CO2
As C1Source synthesis α, β esters of unsaturated carboxylic acids has important Research Significance.
Summary of the invention
The invention provides one and utilize CO2As C1The method of source synthesis α, β esters of unsaturated carboxylic acids, should
Method uses generated in-situ Technique of Nano Pd to be catalyst, and catalysis carbon dioxide chemistry is converted into α, β unsaturation carboxylic
Acid esters.The method has that reaction raw materials green is easy to get, reaction condition is gentle, experimental implementation is simple, substrate is double
Capacitive is good, easily realize the advantages such as industrialization, thus has bigger using value and economic results in society.
The present invention is a kind of with halogenated methyl (miscellaneous) aromatic hydrocarbon, CO2, and three substituent group pi-allyl silicon be raw material,
It is catalyzed CO by suitable catalyst system and catalyzing2Convert, obtain α, beta-unsaturated carboxylic acid ester compounds.Reactional equation
Formula is as follows:
The technical scheme that the method uses is as follows:
The synthesis of esters of alpha, beta, unsaturated carboxylic acids compound: by palladium catalyst, additive, halogenated methyl (miscellaneous)
After aromatic hydrocarbon, three substituent group pi-allyl silicon, solvent are added sequentially to reactor, it is filled with carbon dioxide, then
Reactor is placed in oil bath reaction.
R on halogenated methyl aromatic hydrocarbon1Selected from fluorine, chlorine, bromine, nitro, ester group, methyl, methoxyl group or second
Epoxide；R1Ortho position, meta or para position at aromatic ring ring；Y is selected from bromine or chlorine；Aromatic ring is phenyl ring or naphthalene nucleus；
R on the miscellaneous aromatic hydrocarbon of described chloromethyl2Selected from methyl, bromine, nitro, ester group, methyl；R2At hetero-aromatic ring
3,4 or 5；Hetero-aromatic ring be thiphene ring (X=S), benzothiophene ring (X=S), furan nucleus (X=O),
Benzofuran ring (X=O), pyrrole ring (X=NTs) or benzopyrrole ring (X=NTs)；Three described replacements
R on base pi-allyl silicon3Selected from methyl, methoxyl group, chlorine or butyl.
Solvent is selected from toluene, normal hexane, oxolane, 1,4-dioxane, N,N-dimethylformamide, N, N-
Dimethyl acetylamide, dimethyl sulfoxide, dichloromethane, chloroform, acetone, acetonitrile, be single solvent
Or mixed solvent.
Range of reaction temperature is 20～150 DEG C, preferably 40～80 DEG C.
Reaction time range is 10～40h, preferably 12～24h.
Palladium catalyst selected from three (dibenzalacetone) two palladium, Palladous chloride., palladium, palladium acetylacetonate or
Diacetonitrile palladium chloride.
Additive selected from tetramethyl ammonium chloride, tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutyl ammonium bromide,
Tetrabutylammonium iodide, tetrabutylammonium acetate ammonium, four n-octyl ammonium bromide.
The mol ratio of halogenated methyl (miscellaneous) aromatic hydrocarbon and three substituent group pi-allyl silicon is 1:0.5～1:10.0.
Halogenated methyl (miscellaneous) aromatic hydrocarbon molar concentration in a solvent is 0.01mmol/mL～2mmol/mL.
Halogenated methyl (miscellaneous) aromatic hydrocarbon is 1:0.2～1:10 with the mol ratio of additive.
Halogenated methyl (miscellaneous) aromatic hydrocarbon is 1:0.01～1:0.5 with the mol ratio of catalyst.
Accompanying drawing explanation
Fig. 1 is compound 2a's1H-NMR。
Fig. 2 is compound 2b's1H-NMR。
Fig. 3 is compound 2c's1H-NMR。
Fig. 4 is compound 2d's1H-NMR。
Fig. 5 is compound 2e's1H-NMR。
Fig. 6 is compound 2f's1H-NMR。
Fig. 7 is compound 2g's1H-NMR。
Fig. 8 is compound 2h's1H-NMR。
Fig. 9 is compound 2i's1H-NMR。
Figure 10 is compound 2j's1H-NMR
Figure 11 is compound 2k's1H-NMR。
Figure 12 is compound 2l's1H-NMR。
Detailed description of the invention
Catalysis CO of the present invention2It is converted into α, the method for beta-unsaturated carboxylic acid ester, there is reaction raw materials
Green is easy to get, reaction condition is gentle, experimental implementation is simple, the compatible advantage such as good of substrate, shows good
Application prospect.
Below in conjunction with specific embodiment, the present invention is expanded on further.These embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The simple replacement that the present invention is done by technical staff in this field
Or within improvement belongs to the technical scheme that the present invention is protected.
Embodiment 1:(E) synthesis of-benzyl but-2-enoate (2a)
Accurately weigh three (dibenzalacetone) two palladium (11.4mg, 0.0125mmol), tetrabutyl ammonium bromide
(225.7mg, 0.7mmol) is also added sequentially to the reactor of 25mL, add oxolane (2.0mL),
Benzyl chlorine (63.3mg, 0.5mmol), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).It is then charged with dioxy
Change carbon to 1.0MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, reactor is delayed
Slow cool down, to room temperature, releases remaining carbon dioxide.Last removal of solvent under reduced pressure, uses petroleum ether/acetic acid second
Ester separates as eluant, silicagel column, and E-2-butenoic acid benzyl ester yield is 66%.1H NMR(400MHz,
CDCl3):δ7.39-7.28(m,5H),7.07-6.95(m,1H),5.93-5.84(m,1H),5.16(s,2H),
1.86 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,CDCl3):166.3,145.2,136.2,
128.6,128.2,128.1,122.5,65.9,18.0.
Embodiment 2:(E) synthesis of-4-fluorobenzyl but-2-enoate (2b)
Accurately weigh Palladous chloride. (4.4mg, 0.025mmol), tetrabutyl ammonium bromide (225.7mg, 0.7mmol) and depend on
In the secondary reactor joining 25mL, add oxolane (5.0mL), 1-chloromethyl-4-fluorobenzene (72.3mg,
0.5mmol), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).It is then charged with carbon dioxide to 2.0MPa.
Reactor is placed in 40 DEG C of oil baths reaction 24h.After reaction terminates, reactor is slowly cooled to room temperature,
Release remaining carbon dioxide.Last removal of solvent under reduced pressure, use petrol ether/ethyl acetate as eluant,
Silicagel column separates, and E-2-butenoic acid-4-fluoro-methylbenzyl ester yield is 81%.1H NMR(400MHz,CDCl3)
δ7.38–7.31(m,2H),7.09–6.94(m,3H),5.93–5.83(m,1H),5.13(s,2H),1.87(dd,J
=1.6,6,8Hz, 3H)；13C NMR(100MHz,CDCl3)δ166.2,162.6(d,1JC-F=245.1Hz),
145.3,132.1(d,4JC-F=3.2Hz), 130.1 (d,3JC-F=8.2Hz), 122.4,115.0 (d,2JC-F=21.5
Hz),65.2,18.0.
Embodiment 3:(E) synthesis of-4-chlorobenzyl but-2-enoate (2c)
Accurately weigh Palladous chloride. (4.4mg, 0.025mmol), tetrabutylammonium chloride (194.5mg, 0.7mmol)
And be added sequentially in the reactor of 25mL, add toluene (5.0mL), 1-chloromethyl-4-chlorobenzene (80.5mg,
0.5mmol), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).It is then charged with carbon dioxide to 3.0MPa.
Reactor is placed in 60 DEG C of oil baths reaction 20h.After reaction terminates, reactor is slowly cooled to room temperature,
Release remaining carbon dioxide.Last removal of solvent under reduced pressure, use petrol ether/ethyl acetate as eluant,
Silicagel column separates, and E-2-butenoic acid-4-benzyl chloride ester yield is 70%.1H NMR(400MHz,CDCl3):δ
7.35-7.28 (m, 4H), 7.09-6.95 (m, 1H), 5.93-5.84 (m, 1H), 5.13 (s, 2H), 1.88 (dd, J=
1.6,6.8Hz,3H)；13C NMR(100MHz,CDCl3):166.4,145.7,134.9,134.2,129.7,
128.9,122.5,65.3,18.2.
Embodiment 4:(E) synthesis of-4-bromobenzyl but-2-enoate (2d)
Accurately weigh palladium (5.6mg, 0.025mmol), tetrabutyl ammonium fluoride (183.0mg, 0.7
Mmol), 1-chloromethyl-4-bromobenzene (102.7mg, 0.5mmol) be added sequentially to the reactor of 25mL,
Add oxolane (5.0mL), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).It is then charged with dioxy
Change carbon to 1.5MPa.Reactor is placed in 55 DEG C of oil baths reaction 18h.After reaction terminates, reactor is delayed
Slow cool down, to room temperature, releases remaining carbon dioxide.Last removal of solvent under reduced pressure, uses petroleum ether/acetic acid second
Ester separates as eluant, silicagel column, and E-2-butenoic acid-4-bromobenzyl ester yield is 72%.1H NMR(400
MHz,CDCl3): δ 7.48 (d, J=8.4Hz, 2H), 7.24 (d, J=8.4Hz, 2H), 7.09 6.94 (m, 1H),
5.83 5.93 (m, 1H), 5.11 (s, 2H), 1.88 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,
CDCl3):166.2,145.6,135.2,131.7,129.8,122.3,122.2,65.1,18.1.
Embodiment 5:(E) synthesis of-2-ethoxybenzyl but-2-enoate (2e)
Accurately weigh diacetonitrile palladium chloride (5.5mg, 0.025mmol), tetrabutylammonium chloride (194.5mg,
0.7mmol) and be added sequentially in the reactor of 25mL, Isosorbide-5-Nitrae-dioxane (5.0mL), 1-chloromethyl are added
-2-ethoxybenzene (85.3mg, 0.5mmol), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).Then fill
Enter carbon dioxide to 2.5MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, will be anti-
Answer still to be slowly cooled to room temperature, release remaining carbon dioxide.Last removal of solvent under reduced pressure, use petroleum ether/
Ethyl acetate separates as eluant, silicagel column, and E-2-butenoic acid-2-ethyoxyl benzyl ester yield is 64%.1H
NMR(400MHz,CDCl3):δ7.36-7.31(m,1H),7.30-7.24(m,1H),7.08-6.96(m,1H),
6.95-6.84 (m, 2H), 5.95-5.86 (m, 1H), 5.24 (s, 2H), 4.05 (q, J=7.2Hz, 2H), 1.88 (dd,
J=1.6,6.8Hz, 3H), 1.40 (t, J=6.8Hz, 3H)；13C NMR(100MHz,CDCl3):166.5,
156.8,144.7,129.3,129.2,124.7,22.8,120.3,111.4,63.7,61.5,18.0,14.8；IR(neat,
cm-1):2980,2936,1721,1657,1604,1496,1453,1378,1292,1247,1177,1123,
1045,1012,971,928,838,754,688；HRMS(ESI)Calcd for C13H12O2NaS[M+
Na]+:243.0997；Found:243.0993.
Embodiment 6:(E) synthesis of-4-methylbenzyl but-2-enoate (2f)
Accurately weigh palladium acetylacetonate (7.6mg, 0.025mmol), tetrabutylammonium chloride (194.5mg, 0.7
Mmol) and be added sequentially in the reactor of 25mL, Isosorbide-5-Nitrae dioxane (3.0mL), 1-chloromethyl-4-are added
Methylbenzene (70.3mg, 0.5mmol), trimethoxy pi-allyl silicon (97.4mg, 0.6mmol).It is then charged with two
Carbonoxide is to 1.8MPa.Reactor is placed in 65 DEG C of oil baths reaction 16h.After reaction terminates, by reactor
It is slowly cooled to room temperature, releases remaining carbon dioxide.Last removal of solvent under reduced pressure, uses petroleum ether/acetic acid
Ethyl ester separates as eluant, silicagel column, and E-2-butenoic acid-4-methyl benzyl ester yield is 72%.1H NMR
(400MHz,CDCl3): δ 7.26 (d, J=8.0Hz, 2H), 7.16 (d, J=7.6Hz, 2H), 7.07-6.92
(m, 1H), 5.94-5.81 (m, 1H), 5.12 (s, 2H), 2.35 (s, 3H), 1.87 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,CDCl3):166.4,145.0,138.0,129.2,128.4,122.6,65.9,21.2,
18.0.
Embodiment 7:(E) synthesis of-4-methoxybenzyl but-2-enoate (2g)
Accurately weigh palladium acetylacetonate (7.6mg, 0.025mmol), tetrabutyl ammonium bromide (225.7mg, 0.7
Mmol) and be added sequentially in the reactor of 25mL, toluene (4.0mL), 1-chloromethyl-4-methoxybenzene are added
(78.3mg, 0.5mmol), trimethoxy pi-allyl silicon (68.6mg, 0.6mmol).It is then charged with carbon dioxide
To 1.8MPa.Reactor is placed in 70 DEG C of oil baths reaction 19h.After reaction terminates, reactor is the coldest
But to room temperature, remaining carbon dioxide is released.Last removal of solvent under reduced pressure, uses petrol ether/ethyl acetate to make
For eluant, silicagel column separates, and E-2-butenoic acid-4-methoxy benzyl ester yield is 67%.1H NMR(400
MHz,CDCl3): δ 7.36-7.27 (d, J=8.6Hz, 2H), 7.09-6.93 (m, 1H), 6.92-6.84 (d, J=
8.8Hz, 2H), 5.94-5.78 (m, 1H), 5.10 (s, 2H), 3.79 (s, 3H), 1.86 (dd, J=1.6,6.8Hz,
3H)；13C NMR(100MHz,CDCl3):166.4,159.6,145.0,130.1,128.3,122.6,113.9,
15.8,55.3,18.0.
Embodiment 8:(E) synthesis of-naphthalen-1-ylmethyl but-2-enoate (2h)
Accurately weigh Palladous chloride. (4.4mg, 0.025mmol), tetrabutyl ammonium bromide (225.7mg, 0.7mmol), 1-
Chloromethyl naphthalene (88.0mg, 0.5mmol) is also added sequentially to the reactor of 25mL, adds oxolane (5.0
ML), allyltrimethylsilane (97.6mg, 0.6mmol).It is then charged with carbon dioxide to 2.0MPa.Will be anti-
Still is answered to be placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, reactor is slowly cooled to room temperature, releases
Remaining carbon dioxide.Last removal of solvent under reduced pressure, uses petrol ether/ethyl acetate as eluant, silica gel
Post separates, and E-2-butenoic acid-naphthalene benzyl ester yield is 76%.1H NMR(400MHz,CDCl3):δ8.09-7.99
(m,1H),7.93-7.81(m,2H),7.61-7.50(m,3H),7.49-7.43(m,1H),7.11-6.98(m,1H),
5.95-5.84 (m, 1H), 5.65 (s, 2H), 1.87 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,
CDCl3):166.4,145.3,133.8,131.7,131.6 129.3 128.7,127.4,126.6,126.0,125.3,
123.7,122.5,64.3,18.1.
Embodiment 9:(E) synthesis of-(5-bromothiophen-2-yl) methyl but-2-enoate (2i)
Accurately weigh Palladous chloride. (4.4mg, 0.025mmol), tetrabutyl ammonium fluoride (183.0mg, 0.7
Mmol), 2-chloromethyl-5-bromothiophene (105.8mg, 0.5mmol) be added sequentially to the reactor of 25mL
In, add acetonitrile (5.0mL), allyltrimethylsilane (97.6mg, 0.6mmol).It is then charged with carbon dioxide
To 1.0MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, reactor is the coldest
But to room temperature, remaining carbon dioxide is released.Last removal of solvent under reduced pressure, uses petrol ether/ethyl acetate to make
For eluant, silicagel column separates, and E-2-butenoic acid-(5-bromothiophene)-1-methyl ester yield is 86%.
1H NMR(400MHz,CDCl3): δ 7.09-6.96 (m, 1H), 6.92 (d, J=3.6Hz, 1H), 6.84
(d, J=3.6Hz, 1H), 5.90-5.80 (m, 1H), 5.21 (s, 2H), 1.88 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,CDCl3):166.0,145.9,140.0,129.5,128.4,122.1,113.6,60.2,
18.1；IR(neat,cm-1):2949,1720,1658,1440,1375,1295,1255,1211,1174,1102,
1054,1013,986,967,836,798,742,689,562,522；HRMS(ESI)Calcd for
C9H9O2NaSBr[M+Na]+:284.9384,282.9404；Found:284.9395,282.9413.
Embodiment 10:(E) synthesis of-benzo [b] thiophen-2-ylmethyl but-2-enoate (2j)
Accurately weigh palladium acetylacetonate (7.6mg, 0.025mmol), tetrabutyl ammonium fluoride (183.0mg, 0.7
Mmol), 2-chloromethylbenzene bithiophene (91.3mg, 0.5mmol) be added sequentially to the reactor of 25mL,
Add oxolane (4.0mL), allyltrimethylsilane (97.6mg, 0.6mmol).It is then charged with carbon dioxide
To 2.0MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, reactor is the coldest
But to room temperature, remaining carbon dioxide is released.Last removal of solvent under reduced pressure, uses petrol ether/ethyl acetate to make
For eluant, silicagel column separates, and E-2-butenoic acid-(benzothiophene-2-methyl) ester yield is 71%.1H NMR
(400MHz,CDCl3):δ7.83-7.70(m,2H),7.38-7.28(m,3H),7.10-6.95(m,1H),
5.95-5.80 (m, 1H), 5.40 (s, 2H), 1.88 (dd, J=1.2,6.8Hz, 3H)；13C NMR(100MHz,
CDCl3):166.0,145.8,140.4,139.2,139.1,124.6,124.4,124.2,123.8,122.4,122.1,
61.1,18.1；IR(neat,cm-1):3057,2942,1721,1656,1458,1438,1375,1293,1254,
1172,1102,1014,968,860,834,747,727,688,581,497,476；HRMS(ESI)Calcd
for C13H12O2NaS[M+Na]+:255.0456；Found:255.0449.
Embodiment 11:(E) synthesis of-benzofuran-2-ylmethyl but-2-enoate (2k)
Accurately weigh palladium acetylacetonate (15.2mg, 0.05mmol), tetrabutyl ammonium fluoride (183.0mg, 0.7
Mmol), 2-chloromethyl benzofuran (83.3mg, 0.5mmol) be added sequentially to the reactor of 25mL,
Add acetonitrile (5.0mL), allyltrimethylsilane (97.6mg, 0.6mmol).It is then charged with carbon dioxide to 3.0
MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, reactor is slowly cooled to room
Temperature, releases remaining carbon dioxide.Last removal of solvent under reduced pressure, uses petrol ether/ethyl acetate as eluting
Agent, silicagel column separates, and E-2-butenoic acid-(benzofuran-2-methyl) ester yield is 86%.1H NMR(400
MHz,CDCl3):δ7.62-7.45(m,2H),7.36-7.18(m,2H),7.12-6.96(m,1H),6.77(s,1H),
6.02-5.82 (m, 1H), 5.26 (s, 2H), 1.87 (dd, J=1.6,6.8Hz, 3H)；13C NMR(100MHz,
CDCl3):165.9,155.2,152.1,145.9,128.0,124.8,122.9,122.1,121.3,111.4,106.9,
58.3,18.0；IR(neat,cm-1):3056,2917,2851,1724,1657,1607,1475,1454,1376,
1307,1294,1253,1172,1103,1015,989,968,946,876,835,812,752,685,638,
612；HRMS(ESI)Calcd for C13H12O3Na[M+Na]+:239.0684；Found:239.0678.
Embodiment 12:(E) synthesis of-(1-tosyl-1H-indol-3-yl) methyl but-2-enoate (2l)
Accurately weigh palladium acetylacetonate (7.6mg, 0.025mmol), tetrabutyl ammonium fluoride (183.0mg, 0.7
Mmol), N-p-toluenesulfonyl-2-chloromethyl indole (159.9mg, 0.5mmol) be added sequentially to 25
In the reactor of mL, add toluene (5.0mL), allyltrimethylsilane (97.6mg, 0.6mmol).Then
It is filled with carbon dioxide to 2.0MPa.Reactor is placed in 70 DEG C of oil baths reaction 24h.After reaction terminates, will
Reactor is slowly cooled to room temperature, and releases remaining carbon dioxide.Last removal of solvent under reduced pressure, uses oil
Ether/ethyl acetate separates as eluant, silicagel column, and E-2-butenoic acid-(N-is to Methyl benzenesulfonyl base indole-3-
Methyl) ester yield is 68%.
1H NMR(400MHz,CDCl3): δ 7.97 (d, J=8.4Hz, 1H), 7.77 (d, J=8.4Hz, 2H),
7.63 (s, 1H), 7.57 (d, J=7.8Hz, 1H), 7.39-7.29 (m, 1H), 7.28-7.16 (m, 3H),
7.05-6.93 (m, 1H), 5.89-5.80 (m, 1H), 5.29 (s, 2H), 2.32 (s, 2H), 1.86 (dd, J=1.6,6.8
Hz,3H)；13C NMR(100MHz,CDCl3):δ166.3,145.5,145.1,135.2,135.1,130.0,
129.6,127.0,125,5,125.0,123.4,122.3,119.8,117.6,113.7,57.6,21.6,18.0；IR
(neat,cm-1):3113,3053,2953,1720,1657,1597,1494,1447,1374,1174,1137,
1122,1101,1085,1018,973,813,748,670,598,578,537；HRMS(ESI)Calcd for
C20H19NO4NaS[M+Na]+:392.0932；Found:392.0921.
Claims (8)
1. the preparation method of a α, β unsaturated carboxylic ester compound, it is characterised in that: with carbon dioxide, halo
Methyl (miscellaneous) aromatic hydrocarbon and three substituent group pi-allyl silicon are raw material, under the effect of palladium catalyst, synthesize one
Series α, β unsaturated carboxylic ester compound, its feature synthetic route is as follows:
By palladium catalyst, additive, halogenated methyl (miscellaneous) aromatic hydrocarbon, three substituent group pi-allyl silicon, solvent
It is added sequentially in reactor, filling CO 2 to 0.2MPa～5.0MPa；Then reactor is placed in 20～
Reacting 10～40h in 150 DEG C of oil baths, reaction is cooled to room temperature after terminating, release residual carbon dioxide, obtain
The reactant liquor obtained is through post isolated α, β unsaturated carboxylic ester compound.
Method the most according to claim 1, it is characterised in that the described R on halogenated methyl aromatic hydrocarbon1Choosing
From fluorine, chlorine, bromine, nitro, ester group, methyl, methoxy or ethoxy；R1Ortho position, meta at aromatic ring
Or para-position；Y is selected from bromine or chlorine；Aromatic ring is phenyl ring or naphthalene nucleus；R on the miscellaneous aromatic hydrocarbon of described chloromethyl2Choosing
From methyl, bromine, nitro, ester group, methyl；R23,4 or 5 at hetero-aromatic ring；Hetero-aromatic ring is thiophene
Fen ring (X=S), benzothiophene ring (X=S), furan nucleus (X=O), benzofuran ring (X=O), pyrroles
Ring (X=NTs) or benzopyrrole ring (X=NTs)；The described R on three substituent group pi-allyl silicon3Selected from first
Base, methoxyl group, chlorine or butyl.Halogenated methyl (miscellaneous) aromatic hydrocarbon and the mol ratio of three substituent group pi-allyl silicon
For 1:0.5～1:10.0.
3. according to the method described in claims 1 or 2, it is characterised in that described palladium catalyst is selected from three (two
BENZYLIDENE ACETONE) two palladiums, Palladous chloride., palladium, palladium acetylacetonate or diacetonitrile palladium chloride；Halo first
Base (miscellaneous) aromatic hydrocarbon is 1:0.01～1:0.5 with the mol ratio of catalyst.
Method the most according to claim 1 and 2, it is characterised in that described additive is selected from tetramethyl chlorination
Ammonium, tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetrabutylammonium iodide, tetrabutyl vinegar
Acid ammonium, four n-octyl ammonium bromide；The mol ratio of halogenated methyl (miscellaneous) aromatic hydrocarbon and additive agent be 1:0.2～
1:10。
Method the most according to claim 3, it is characterised in that described additive selected from tetramethyl ammonium chloride,
Tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate ammonium,
Four n-octyl ammonium bromide；Halogenated methyl (miscellaneous) aromatic hydrocarbon is 1:0.2～1:10 with the mol ratio of additive.
6. according to the method described in claim 1,2 or 5, it is characterised in that solvent selected from toluene, normal hexane,
Oxolane, 1,4-dioxane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide,
Dichloromethane, chloroform, acetone, acetonitrile, be single solvent or mixed solvent；Halogenated methyl (miscellaneous)
Aromatic hydrocarbon molar concentration in a solvent is 0.01mmol/mL～2mmol/mL.
Method the most according to claim 4, it is characterised in that solvent selected from toluene, normal hexane, oxolane,
1,4-dioxane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, dichloromethane,
Chloroform, acetone, acetonitrile, be single solvent or mixed solvent；Halogenated methyl (miscellaneous) aromatic hydrocarbon is molten
Molar concentration in agent is 0.01mmol/mL～2mmol/mL.
Method the most according to claim 3, it is characterised in that solvent selected from toluene, normal hexane, oxolane,
1,4-dioxane, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, dichloromethane,
Chloroform, acetone, acetonitrile, be single solvent or mixed solvent；Halogenated methyl (miscellaneous) aromatic hydrocarbon is molten
Molar concentration in agent is 0.01mmol/mL～2mmol/mL.
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| CN115403465A (en) * | 2022-05-20 | 2022-11-29 | 湖南工程学院 | Preparation method for synthesizing organic carboxylic ester from carbon dioxide and olefin |
| CN115403465B (en) * | 2022-05-20 | 2023-08-18 | 湖南工程学院 | Preparation method for synthesizing organic carboxylic ester by carbon dioxide and olefin |
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