CN105017184A - Polysubstituted dihydrofuran-3-one compound and synthetic method therefor - Google Patents
Polysubstituted dihydrofuran-3-one compound and synthetic method therefor Download PDFInfo
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- CN105017184A CN105017184A CN201510395130.4A CN201510395130A CN105017184A CN 105017184 A CN105017184 A CN 105017184A CN 201510395130 A CN201510395130 A CN 201510395130A CN 105017184 A CN105017184 A CN 105017184A
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- HCOSYRNWFVOQOT-UHFFFAOYSA-N COc(cc1)ccc1C(C(C#Cc1ccccc1)=O)=O Chemical compound COc(cc1)ccc1C(C(C#Cc1ccccc1)=O)=O HCOSYRNWFVOQOT-UHFFFAOYSA-N 0.000 description 1
- HSVHHFBYPXELBI-UHFFFAOYSA-N COc1ccc(C2(O)OC(c3ccccc3)=CC2=O)cc1 Chemical compound COc1ccc(C2(O)OC(c3ccccc3)=CC2=O)cc1 HSVHHFBYPXELBI-UHFFFAOYSA-N 0.000 description 1
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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
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses a synthetic method of a polysubstituted dihydrofuran-3-one compound. The preparation method comprises: carrying out a reaction in methylbenzene to obtain the polysubstituted dihydrofuran-3-one compound at 80 DEG C by taking alkynyl diketone as a reaction raw material and water as an oxygen atom implanting reagent. The synthetic method disclosed by the invention has the advantages of efficient reaction and relatively high yield; water taken as an oxygen atom transfer reagent is green and environmental-friendly and low in price and economical; the reaction condition only needs room temperature without strong acids and strong alkali; a silver catalyst is relatively cheap; and reaction substrates are easily prepared.
Description
Technical field
The invention belongs to organic compound process application technical field, be specifically related to the polysubstituted dihydrofuran of a class-3-ketone compounds and green synthesis method thereof.
Background technology
Polysubstituted dihydrofuran-3-ketone structure is present among a series of heterogeneous ring compound with pharmacology important activity widely.Comprise jatrophone, geiparvarin, eremantholides, trachyspic acid, lychnophorolide A, ciliarin, 2-deoxysiphonarien furanone, longianone contain this structural unit in interior multiple cancer therapy drug and microbiotic.Therefore, polysubstituted dihydrofuran-3-ketone compounds has important synthesis meaning.But relatively less for the synthesis report of this structure, and often need the raw material by complexity, or loaded down with trivial details synthesis step realizes.Especially for the polysubstituted dihydrofuran-3-ketone containing hemiketal sensitive structure, synthesis difficulty is very big, before this and find no methodology and can synthesize this compounds.
Therefore find that a kind of simple, green, high efficiency low cost, compatibility are good, the novel method of environmental friendliness, mild condition and the economic and practical polysubstituted dihydrofuran of structure-3-ketone compounds just seems and be even more important.The present inventor finds that alkynyl diketone is the unique compounds that a class has how close potential point after deliberation, and the thinking that combination atom implants reaction can conveniently build a series of heterogeneous ring compound.Given this, the present invention devise silver-colored catalysis with alkynyl diketone and water for the reaction of the polysubstituted dihydrofuran-3-ketone compounds of preparation to be implanted by raw material by Sauerstoffatom.
Summary of the invention
Instant invention overcomes the shortcomings of conventional construction method, realize the method for the polysubstituted dihydrofuran of a kind of efficient structure-3-ketone compounds innovatively.The present invention uses common Lewis acid catalyst, with alkynyl diketone for raw material, be that Sauerstoffatom implants reagent with water, in reaction solvent, at 80 DEG C, have effectively achieved corresponding conversion, prepare such as formula the polysubstituted dihydrofuran-3-ketone compounds shown in (II).
Wherein, described reaction process is as shown in following reaction formula.
In above reaction formula,
Ar is phenyl ring, heterocycle, substituted benzene ring or substituted heterocycle.R is straight chained alkyl, branched paraffin or aryl.
Preferably, Ar is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-iodophenyl, 2-naphthyl, 3-thienyl, 2-benzothienyl, 2-benzofuryl.Preferably, R is phenyl, 4-p-methoxy-phenyl, 4-aminomethyl phenyl, normal-butyl, cyclopropyl.
In the present invention, Ar, R include but are not limited to above-mentioned group.
As above reaction formula, the present invention utilizes the alkynyl diketone shown in formula (I) as starting raw material, reagent is implanted as Sauerstoffatom using water, under the effect of catalyzer, react in reaction solvent, synthesize such as formula the polysubstituted dihydrofuran-3-ketone compounds shown in (II).
In the present invention, described starting raw material is 1:1-1:15 such as formula the mole dosage ratio of the alkynyl diketone shown in (I) and water.Preferably, both usage ratio are 1:3.
In the present invention, described catalyzer is AgOTf, AgNTf
2, AuCl
3, ScOTf etc.Preferably, described catalyzer is AgOTf.Wherein, the consumption of described catalyzer is the 1-20mol% such as formula the raw material alkynyl diketone shown in (I).Preferably, described catalyst levels is the 20mol% such as formula the raw material alkynyl diketone shown in (I).
In the present invention, described reaction solvent is any one or arbitrary combination of methyl alcohol, ethanol, Virahol, the trimethyl carbinol, water, DMSO, DMF, DMA, acetonitrile, acetone, tetrahydrofuran (THF), toluene, methylene dichloride, 1,2-ethylene dichloride, chloroform.Preferably, described solvent is toluene.
Building-up reactions of the present invention comprises the following steps: in reaction vessel, add alkynyl diketone, catalyzer, water, solvent, in nitrogen atmosphere, react to stirred at reflux condition in room temperature, obtain the polysubstituted dihydrofuran-3-ketone compounds shown in formula (II).Preferably, step is reacted at 80 DEG C of temperature.
In a specific examples, building-up reactions of the present invention is in reaction flask A, add alkynyl dione compounds (Xmmol), water (Y mmol), catalyst A gOTf (Z mmol), solvent (V mL), reaction system, in nitrogen atmosphere, stirs 4-24 hour at 80 DEG C.Monitoring reaction process.After completion of the reaction, directly the polysubstituted dihydrofuran-3-ketone compounds shown in target product formula (II) is obtained through column chromatography for separation.
The invention allows for according to the above-mentioned synthetic method of the present invention prepare such as formula the polysubstituted dihydrofuran-3-ketone compounds shown in (II),
Wherein, Ar is phenyl ring, heterocycle, substituted benzene ring or substituted heterocycle.R is straight chained alkyl, branched paraffin or aryl.
Preferably, Ar is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-iodophenyl, 2-naphthyl, 3-thienyl, 2-benzothienyl, 2-benzofuryl.Preferably, R is phenyl, 4-p-methoxy-phenyl, 4-aminomethyl phenyl, normal-butyl, cyclopropyl.
The invention allows for new alkynyl dione compounds, its structural formula such as formula shown in (II),
Wherein, Ar is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-iodophenyl, 2-naphthyl, 3-thienyl, 2-benzothienyl, 2-benzofuryl.R is phenyl, 4-p-methoxy-phenyl, 4-aminomethyl phenyl, normal-butyl, cyclopropyl.
The present invention has the following advantages: reaction is efficient, and yield is higher; Water as Oxygen transfer reagent, environmental protection, cheap economical; Reaction conditions is gentle, without the need to strong acid and strong base; Silver catalyst is relatively inexpensive; Reaction substrate is easily prepared.The present invention for reaction raw materials, implants reagent with water as Sauerstoffatom with the alkynyl diketone easily prepared, and under catalyst action, carries out atom implantation and is obtained by reacting polysubstituted dihydrofuran-3-ketone compounds.Operation is simple, and reaction conditions is gentle, is applicable to large-scale industrial production.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.Data given by following examples comprise concrete operations and reaction conditions and product.Product purity is identified by nuclear-magnetism.
The building-up reactions of the polysubstituted dihydrofuran of the present invention-3-ketone compounds, comprise the following steps: in reaction vessel, add alkynyl diketone, catalyzer, water, solvent, in nitrogen atmosphere, react to stirred at reflux condition in room temperature, obtain the polysubstituted dihydrofuran-3-ketone compounds shown in formula (II).Object product is obtained again through column chromatography for separation.
Wherein, polysubstituted dihydrofuran-3-ketone compounds as shown in table 1, is and synthesizes by the inventive method the product obtained, there is not yet open source literature and disclose these compounds.Owing to comprising jatrophone, geiparvarin, eremantholides, trachyspic acid, lychnophorolide A, ciliarin, 2-deoxysiphonarien furanone, longianone contains this furanone structure unit in interior multiple cancer therapy drug and microbiotic, and therefore these new compounds are potential transforms to above-mentioned known bioactive natural product.Meanwhile, these new compounds itself also probably also exist outstanding pharmaceutical activity.
Table 1 new alkynyl dione compounds of the present invention
Embodiment 1
The synthesis of compound 2a:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1a (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2a.Yield: 87%;
1h NMR (400MHz, DMSO) δ 8.52 (s, 1H), 8.05 (d, J=7.3Hz, 2H), 7.69 (t, J=6.7Hz, 1H), 7.61 (t, J=7.1Hz, 2H), 7.52 – 7.45 (m, 2H), 7.44 – 7.35 (m, 3H), 6.42 (s, 1H);
13c NMR (101MHz, DMSO) δ 200.0,183.2,136.8,133.4,129.2,129.0,128.3,127.2,125.4,104.7,97.8; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd forC
16h
12o
3252.0786, Found 252.0787.
Embodiment 2
The synthesis of compound 2b:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1b (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2b.Yield: 83%;
1h NMR (300MHz, DMSO) δ 8.43 (s, 1H), 8.04 (d, J=7.2Hz, 2H), 7.69 (t, J=7.3Hz, 1H), 7.61 (t, J=7.4Hz, 2H), 7.34 (d, J=8.1Hz, 2H), 7.19 (d, J=8.1Hz, 2H), 6.40 (s, 1H), 2.29 (s, 3H);
13cNMR (126MHz, DMSO) δ 200.1,183.1,138.3,133.9,133.3,129.2,128.9,128.4,127.2,125.3,104.9,97.8,20.7; IR (film) 1667,1626,1583,1524,1468,1376,1336,1275,1207,1127,1091,1069,1011,991,866,817,776,747,699,682cm
-1.HRMS (EI) Calcd for C
17h
14o
3266.0943, Found 266.0942.
Embodiment 3
The synthesis of compound 2c:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1c (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2c.Yield: 67%;
1h NMR (300MHz, DMSO) δ 8.40 (s, 1H), 8.03 (d, J=7.3Hz, 2H), 7.69 (t, J=7.3Hz, 1H), 7.60 (t, J=7.4Hz, 2H), 7.38 (d, J=8.6Hz, 2H), 6.94 (d, J=8.7Hz, 2H), 6.39 (s, 1H), 3.75 (s, 3H);
13cNMR (101MHz, DMSO) δ 200.2,183.0,159.8,133.3,129.2,128.9,128.4,127.2,126.9,113.7,104.8,97.8,55.2; IR (film) 2928,1665,1627,1588,1524,1467,1376,1276,1208,1172,1126,1087,1013,991,866,845,821,777,736,712,685cm
-1.HRMS (EI) Calcd for C
17h
14o
4282.0892, Found 282.0891.
Embodiment 4
The synthesis of compound 2d:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1d (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2d.Yield: 84%;
1h NMR (400MHz, DMSO) δ 8.59 (s, 1H), 8.07 (d, J=7.5Hz, 2H), 7.70 (d, J=8.2Hz, 3H), 7.67 – 7.59 (m, 4H), 7.55 (d, J=8.1Hz, 2H), 7.47 (t, J=7.2Hz, 2H), 7.37 (t, J=6.9Hz, 1H), 6.46 (s, 1H);
13c NMR (101MHz, DMSO) δ 200.0,183.3,140.9,139.6,135.9,133.4,129.3,129.0,128.4,127.7,127.3,126.8,126.1,104.6,97.9; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd for C
22h
16o
3328.1099, Found 328.1100.
Embodiment 5
The synthesis of compound 2e:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1e (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2e.Yield: 80%;
1h NMR (400MHz, DMSO) δ 8.59 (s, 1H), 8.05 (d, J=7.5Hz, 2H), 7.74 – 7.66 (m, 1H), 7.61 (t, J=7.5Hz, 2H), 7.51 (dd, J=8.5,5.5Hz, 2H), 7.23 (t, J=8.8Hz, 2H), 6.44 (s, 1H);
13c NMR (101MHz, DMSO) δ 199.8,183.3,162.5 (d,
1j
cF=245.2Hz), 133.5,133.1 (d,
4j
cF=2.7Hz), 129.2,128.3,127.8 (d,
3j
cF=8.6Hz), 127.3,115.3 (d,
2j
cF=21.8Hz), 104.2,97.8;
19f NMR (376MHz, DMSO) δ-113.00 (s, 1F); IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd for C
16h
11fO
3270.0692, Found 270.0690.
Embodiment 6
The synthesis of compound 2f:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1f (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2f.Yield: 79%;
1h NMR (400MHz, DMSO) δ 8.62 (s, 1H), 8.05 (d, J=7.0Hz, 2H), 7.74 – 7.66 (m, 1H), 7.65 – 7.58 (m, 2H), 7.48 (s, 4H), 6.44 (s, 1H);
13c NMR (101MHz, DMSO) δ 199.6,183.3,135.7,133.8,133.5,129.2,128.5,128.2,127.4,127.3,104.0,97.8; IR (film) 1620,1522,1482,1409,1353,1278,1227,1131,1092,1045,857,786,729,696cm
-1.HRMS (EI) Calcd for C
16h
11clO
3286.0397, Found 286.0396.
Embodiment 7
The synthesis of compound 2g:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1g (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2g.Yield: 85%;
1h NMR (400MHz, DMSO) δ 8.65 (s, 1H), 8.08 – 8.02 (m, 2H), 7.70 (t, J=7.4Hz, 1H), 7.65 – 7.58 (m, 4H), 7.41 (d, J=8.5Hz, 2H), 6.45 (s, 1H);
13c NMR (101MHz, DMSO) δ 199.5,183.3,136.1,133.5,131.4,129.2,128.2,127.7,127.3,122.4,104.1,97.8; IR (film) 2927,1630,1547,1523,1465,1378,1330,1300,1226,1127,1090,1007,930,888,824,797,773,732cm
-1.HRMS (EI) Calcd for C
16h
11brO
3329.9892, Found 329.9893.
Embodiment 8
The synthesis of compound 2h:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1h (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2h.Yield: 80%;
1h NMR (300MHz, DMSO) δ 8.60 (s, 1H), 8.04 (d, J=7.3Hz, 2H), 7.78 (d, J=8.2Hz, 2H), 7.74 – 7.66 (m, 1H), 7.61 (t, J=7.2Hz, 2H), 7.25 (d, J=8.1Hz, 2H), 6.44 (s, 1H);
13c NMR (101MHz, DMSO) δ 199.6,183.3,137.2,136.5,133.4,129.2,128.2,127.6,127.3,104.2,97.8,95.7; IR (film) 1625,1514,1483,1373,1258,1224,1171,1132,1082,859,784,718,686cm
-1.HRMS (EI) Calcdfor C
16h
11iO
3377.9753, Found 377.9749.
Embodiment 9
The synthesis of compound 2i:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1i (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2i.Yield: 76%;
1h NMR (400MHz, DMSO) δ 8.68 (s, 1H), 8.11 (s, 1H), 8.08 (d, J=5.3Hz, 2H), 8.03 – 7.97 (m, 1H), 7.96 – 7.90 (m, 2H), 7.71 (t, J=7.3Hz, 1H), 7.63 (t, J=7.5Hz, 2H), 7.59 – 7.49 (m, 3H), 6.50 (s, 1H);
13c NMR (101MHz, DMSO) δ 200.0,183.4,134.3,133.4,133.0,132.4,129.3,128.4,128.4,128.1,127.5,127.4,126.7,126.5,124.8,123.1,104.8,98.0; IR (film) 3056,1665,1623,1524,1463,1374,1284,1186,1126,1087,879,810,776,746,575cm
-1.HRMS (EI) Calcd forC
20h
14o
3302.0943, Found 302.0946.
Embodiment 10
The synthesis of compound 2j:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1j (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2j.Yield: 99%;
1h NMR (400MHz, DMSO) δ 8.47 (s, 1H), 8.02 (d, J=7.2Hz, 2H), 7.68 (t, J=6.8Hz, 1H), 7.63 – 7.57 (m, 3H), 7.53 (s, 1H), 7.10 (d, J=3.4Hz, 1H), 6.39 (s, 1H);
13c NMR (101MHz, DMSO) δ 199.5,182.9,138.3,133.4,129.2,128.5,127.3,127.0,125.4,123.9,103.4,97.8; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd forC
14h
10o
3s 258.0351, Found 258.0353.
Embodiment 11
The synthesis of compound 2k:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1k (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2k.Yield: 79%;
1h NMR (400MHz, DMSO) δ 9.02 (s, 1H), 8.07 (d, J=7.5Hz, 2H), 8.00 – 7.92 (m, 1H), 7.91 – 7.82 (m, 1H), 7.70 (t, J=7.0Hz, 1H), 7.62 (t, J=7.3Hz, 2H), 7.51 (s, 1H), 7.43 – 7.30 (m, 2H), 6.53 (s, 1H);
13c NMR (101MHz, DMSO) δ 198.3,182.9,140.5,139.2,138.9,133.6,129.3,128.2,127.3,125.0,124.6,124.2,122.5,122.3,103.0,97.6; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd for C
18h
12o
3s 308.0507, Found308.0509.
Embodiment 12
The synthesis of compound 2l:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1l (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2l.Yield: 70%;
1h NMR (300MHz, DMSO) δ 9.06 (s, 1H), 8.04 (d, J=7.5Hz, 2H), 7.73 – 7.65 (m, 2H), 7.64 – 7.53 (m, 3H), 7.37 – 7.22 (m, 2H), 7.14 (s, 1H), 6.59 (s, 1H);
13c NMR (126MHz, DMSO) δ 197.7,183.4,154.4,152.0,133.5,129.2,128.1,127.3,126.9,125.2,123.2,121.7,111.4,106.0,100.5,98.2; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd for C
18h
12o
4292.0736, Found 292.0732.
Embodiment 13
The synthesis of compound 2m:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1m (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2m.Yield: 74%;
1h NMR (300MHz, DMSO) δ 8.42 (s, 1H), 8.01 (d, J=8.9Hz, 2H), 7.48 – 7.43 (m, 2H), 7.41 – 7.35 (m, J=7.5,2.9Hz, 3H), 7.15 (d, J=8.9Hz, 2H), 6.27 (s, 1H), 3.88 (s, 3H);
13c NMR (101MHz, DMSO) δ 199.4,183.0,163.4,137.1,129.4,128.8,128.3,125.4,120.6,114.7,104.6,96.0,55.7; IR (film) 1697,1594,1501,1360,1258,1174,1023,803,697cm
-1.HRMS (EI) Calcd forC
17h
14o
4282.0892, Found 282.0890.
Embodiment 14
The synthesis of compound 2n:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1n (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2n.Yield: 86%;
1h NMR (300MHz, DMSO) δ 8.46 (s, 1H), 7.94 (d, J=8.2Hz, 2H), 7.49 – 7.43 (m, 3H), 7.43 – 7.36 (m, 4H), 6.34 (s, 1H), 2.42 (s, 3H);
13c NMR (126MHz, DMSO) δ 199.8,183.3,143.9,136.9,129.8,128.9,128.3,127.3,125.6,125.4,104.5,97.1,21.3; IR (film) 1629,1513,1464,1374,1176,1127,1085,750,715cm
-1.HRMS (EI) Calcd for C
17h
14o
3266.0943, Found 266.0945.
Embodiment 15
The synthesis of compound 2o:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1o (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2o.Yield: 78%;
1h NMR (400MHz, DMSO) δ 8.30 (s, 1H), 7.44 – 7.36 (m, 5H), 5.52 (s, 1H), 2.63 (t, J=7.6Hz, 2H), 1.71 – 1.60 (m, 2H), 1.47 – 1.35 (m, 2H), 0.93 (t, J=7.3Hz, 3H);
13c NMR (101MHz, DMSO) δ 200.2,193.1,136.7,128.8,128.2,125.4,104.1,99.8,30.0,27.4,21.7,13.6; IR (film) 1661,1617,1522,1482,1373,1328,1296,1266,1237,1214,1089,1000,817,734cm
-1.HRMS (EI) Calcd for C
14h
16o
3232.1099, Found 232.1098.
Embodiment 16
The synthesis of compound 2p:
By catalyst A gOTf (0.04mmol, 20mol%), water (0.6mmol, 3equiv.) with alkynyl diketone 1p (0.2mmol, 1equiv.) join in reaction tubes, then, after adding reaction solvent toluene (2mL), in nitrogen atmosphere, stir 12 hours under 80 DEG C of temperature of reaction.After being terminated by thin-layer chromatography monitoring reaction, after direct column chromatography for separation, obtain product 2p.Yield: 76%;
1h NMR (300MHz, DMSO) δ 8.28 (s, 1H), 7.37 (m, 5H), 5.56 (s, 1H), 2.21 – 1.99 (m, 1H), 1.26 – 1.06 (m, 4H);
13c NMR (101MHz, DMSO) δ 198.8,193.6,136.8,128.8,128.3,125.3,104.3,97.9,11.8,9.4,9.4; IR (film) 2934,1734,1616,1523,1481,1369,1225,1132,1076,1031,780,723,605cm
-1.HRMS (EI) Calcd for C
13h
12o
3216.0786, Found 216.0783.
Claims (8)
1. the synthetic method of a polysubstituted dihydrofuran-3-ketone compounds, it is characterized in that, with alkynyl diketone for reaction raw materials, take water as Oxygen transfer reagent, under the effect of silver catalyst, be obtained by reacting such as formula the polysubstituted dihydrofuran-3-ketone compounds shown in (II) in reaction solvent; Described reaction process is as shown in reaction formula;
Wherein, Ar is phenyl ring, heterocycle, substituted benzene ring or substituted heterocycle; R is straight chained alkyl, branched paraffin or aryl.
2. the synthetic method of polysubstituted dihydrofuran-3-ketone compounds as claimed in claim 1, it is characterized in that, described catalyzer is AgOTf, AgNTf
2, AuCl
3, or ScOTf; The consumption of described catalyzer is the 1-20mol% of alkynyl diketone.
3. the synthetic method of polysubstituted dihydrofuran-3-ketone compounds as claimed in claim 1, it is characterized in that, described solvent is any one or arbitrary combination of methyl alcohol, ethanol, Virahol, the trimethyl carbinol, water, DMSO, DMF, DMA, acetonitrile, acetone, tetrahydrofuran (THF), toluene, methylene dichloride, 1,2-ethylene dichloride, chloroform.
4. the synthetic method of polysubstituted dihydrofuran-3-ketone compounds as claimed in claim 1, is characterized in that, in described reaction, the mole dosage ratio of described alkynyl diketone and water is 1:1-1:15.
5. the synthetic method of polysubstituted dihydrofuran-3-ketone compounds as claimed in claim 1, it is characterized in that, described reaction comprises the following steps:
In reaction vessel, add alkynyl diketone, catalyzer, water, solvent, in nitrogen atmosphere, react to stirred at reflux condition in room temperature, obtain the polysubstituted dihydrofuran-3-ketone compounds shown in formula (II).
6. the synthetic method of polysubstituted dihydrofuran-3-ketone compounds as claimed in claim 5, it is characterized in that, described step is carried out at 80 DEG C.
7. the polysubstituted dihydrofuran-3-ketone compounds of method synthesis as described in any one of claim 1 ~ 6, it is characterized in that, its structure is such as formula shown in (II):
Wherein, Ar is phenyl ring, heterocycle, substituted benzene ring or substituted heterocycle; R is straight chained alkyl, branched paraffin or aryl.
8. a polysubstituted dihydrofuran-3-ketone compounds, is characterized in that, its structure is such as formula shown in (II):
Wherein, Ar is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 4-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-iodophenyl, 2-naphthyl, 3-thienyl, 2-benzothienyl, 2-benzofuryl; R is phenyl, 4-p-methoxy-phenyl, 4-aminomethyl phenyl, normal-butyl, cyclopropyl.
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