CN102603523A - Preparation method of allyl esters - Google Patents
Preparation method of allyl esters Download PDFInfo
- Publication number
- CN102603523A CN102603523A CN2012100802802A CN201210080280A CN102603523A CN 102603523 A CN102603523 A CN 102603523A CN 2012100802802 A CN2012100802802 A CN 2012100802802A CN 201210080280 A CN201210080280 A CN 201210080280A CN 102603523 A CN102603523 A CN 102603523A
- Authority
- CN
- China
- Prior art keywords
- cdcl
- nmr
- iodide
- allyl ester
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 OC(Cc1cc(**C(O)=O)cc2ccccc12)=O Chemical compound OC(Cc1cc(**C(O)=O)cc2ccccc12)=O 0.000 description 3
- VRPJIFMKZZEXLR-UHFFFAOYSA-N CC(C)(C)OC(NCC(O)=O)=O Chemical compound CC(C)(C)OC(NCC(O)=O)=O VRPJIFMKZZEXLR-UHFFFAOYSA-N 0.000 description 1
- ZHUUFKGRYKWCTF-UHFFFAOYSA-N O=C(CN(C(c1ccccc11)=O)C1=O)OC1C=CCCC1 Chemical compound O=C(CN(C(c1ccccc11)=O)C1=O)OC1C=CCCC1 ZHUUFKGRYKWCTF-UHFFFAOYSA-N 0.000 description 1
- MCZOLRQCTOGDFF-UHFFFAOYSA-N O=C(c(cc1)ccc1Cl)OC1c2ccccc2CCC1 Chemical compound O=C(c(cc1)ccc1Cl)OC1c2ccccc2CCC1 MCZOLRQCTOGDFF-UHFFFAOYSA-N 0.000 description 1
- WQINSVOOIJDOLJ-UHFFFAOYSA-N OC(CN(C(c1c2cccc1)=O)C2=O)=O Chemical compound OC(CN(C(c1c2cccc1)=O)C2=O)=O WQINSVOOIJDOLJ-UHFFFAOYSA-N 0.000 description 1
- QIAFMBKCNZACKA-UHFFFAOYSA-N OC(CNC(c1ccccc1)=O)=O Chemical compound OC(CNC(c1ccccc1)=O)=O QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 description 1
- NZPQMXVWZDXOHT-UHFFFAOYSA-N OC(CNOC(c1ccccc1)=O)=O Chemical compound OC(CNOC(c1ccccc1)=O)=O NZPQMXVWZDXOHT-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N OC(c(cc1)ccc1Cl)=O Chemical compound OC(c(cc1)ccc1Cl)=O XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a preparation method of allyl esters, which comprises the following steps: using acid derivative and olefin as reaction substrates; using iodide as a catalyst, using tert-butyl hydroperoxide as an oxidizing agent; reacting through biradical cross coupling reaction to obtain allyl esters. The iodide selects from cuprous iodide, tetramethyl-ammonium iodide, tetraethylammonium iodide, tetrabutyl ammonium iodide or tetraheptylammonium iodide. The invention discloses a new preparation method of allyl esters, the allyl esters can be manufactured directly by means of biradical cross-coupling, therefore, the process step is simple and reliable, the yield ratio is higher, and the better effect is achieved.
Description
Technical field
The present invention relates to a kind of preparation method of allyl ester, belong to the organic synthesis field.
Background technology
Allyl ester is one type of very important compound, extensively is present among natural product that physiologically active is arranged, the drug molecule, and is also visible often in synthetic intermediate.
At present, the method for preparing allyl ester mainly contains: people such as Junzo Otera reported vinyl carbinol and acid under the effect of organic fluorine reagent, prepare allyl ester (referring to Angew.Chem.Int.Ed.2002,41,4117-4119); People such as B.M.Choudary reported allyl alcohol and acid under natural kaolinite effect, prepare allyl ester (referring to Green Chem., 2000,2,67-70); People such as S.J.Kulkarni reported zeolite is participated under the microwave action allyl alcohol and acid preparation allyl ester (referring to Green Chem., 2006,8,368-372); People such as Brindaban C.Ranu reported allyl alcohol and carboxylic acid halides prepare allyl ester (referring to Green Chem, 2003,5,44-46); People such as M.Christina White reported catalytic acid of a series of palladiums and olefin oxidation coupling prepare allyl ester (referring to J.Am.Chem.Soc..2004,126,1346-1347; And J.Am.Chem.Soc..2006,128,9032-9033; And Angew.Chem.Int.Ed.2008,47,6448-6451; And J.Am.Chem.Soc.2011,133,12584-12589); People such as Yoshinori Yamamoto reported catalytic alkene of palladium and acid-respons prepare allyl ester (referring to J.Am.Chem.Soc.1998,120,3809-3810); People such as Michael J.Krische reported catalytic alkene of iridium and acid-respons prepare allyl ester (referring to Org.Lett., Vol.10, No.3,2008,513-515); Bernhard Breit seminar also reported catalytic alkene of rhodium and acid-respons prepare allyl ester (referring to J.Am.Chem.Soc.2011,133,20746-20749); Simultaneously this seminar also reported catalytic alkynes of rhodium and acid-respons prepare allyl ester (referring to J.Am.Chem.Soc.2011,133,2386-2389, Chem.Sci., 2012,3,789-793); Kiyotaka Onitsuka seminar reported the catalytic allyl halide of ruthenium and carboxylate salt prepared in reaction allyl ester (referring to J.Am.Chem.Soc.2010,132,1206-1207); Kalman J.Szab seminar reported catalytic alkene of palladium and acid anhydrides under the borane reagent effect, prepare allyl ester (referring to J.Org.Chem.2011,76,1503-1506); Masahiko Hayashi seminar report cross ester and tetrahydrobenzene under the catalysis of copper, prepare allyl ester (referring to Adv.Synth.Catal.2008,350,2639-2644).
Although the method for synthesis of allyl ester is numerous at present, much all used transition metal in these methods, wherein some catalyzer (like Ru, Rh, Pd, Ir) is relatively more expensive; And some catalystsystem is more loaded down with trivial details; Some reactant preparation trouble, price is more expensive, and the use range of substrate is narrow simultaneously; Bigger limitation is arranged, limited its large-scale application.Therefore, develop that a kind of cost is low, toxicity is lower, and the method for preparing allyl ester easy and simple to handle, active operation significance had.
Summary of the invention
The object of the invention provides a kind of preparation method of allyl ester.
For achieving the above object; The technical scheme that the present invention adopts is: a kind of preparation method of allyl ester is a reaction substrate with acid derivative and alkene, is catalyzer with iodide; Tertbutyl peroxide is an oxygenant, obtains said allyl ester through the diradical cross-coupling reaction;
The structural formula of said acid derivative is:
R wherein
1Be selected from: naphthyl, styryl, cyclopropyl, cyclohexyl, styroyl or single substituted aryl
R wherein
2Be selected from: the ester group of hydrogen, methyl, the tertiary butyl, methoxyl group, cyanic acid, C1～C6, nitro, carboxamido-group, halogen, trifluoromethyl, methylsulfonyl, the amino of Methyl benzenesulfonyl base protection, the hydroxyl of ethanoyl protection;
Said olefin selected from the following compounds represented by structural formula:?
n is 0 to 5;
Said iodide are selected from cuprous iodide, Tetramethylammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide or four n-heptyl ammonium iodides.
In the preceding text; Reaction can be reacted with the saturated sodium sulfite cancellation earlier after accomplishing; Then with ETHYLE ACETATE or dichloromethane extraction; Use anhydrous sodium sulfate drying again, silica gel adsorbs vacuum and revolves dried solvent, carries out simple column chromatography with the mixed solvent of ETHYLE ACETATE and sherwood oil then and just can get final product.
When the Selection of Oxidizer peroxy tert-butyl alcohol, its consumption is 1～5 equivalent, is preferably 1.5 equivalents.
Said catalyzer, reactant are all market-oriented commodity, can directly buy to obtain.
In the technique scheme, the temperature of reaction of said diradical cross-coupling reaction is 60～100 ℃, and the reaction times is 6～12 hours.Preferably, temperature of reaction is 80 ℃, and the reaction times is 8 hours.
In the technique scheme, in molar weight, said catalyst consumption is 5～40% of an acid derivative.Preferred 20%.
In the technique scheme, the mol ratio of said acid derivative and alkene is 1: 3～5.
In the technique scheme, the used solvent of said diradical cross-coupling reaction is selected from one or more in hexanaphthene, the trimethyl carbinol, acetonitrile, 1 and the benzene.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention has developed a kind of preparation method of new allyl ester, adopts the mode of diradical cross-coupling directly to make allyl ester, and process step is simple and reliable, and yield is higher, has obtained effect preferably.
2. the present invention adopts iodide to prepare allyl ester as catalyst; Avoided using traditional expensive catalysts, make reaction safer more green more economical, and reaction conditions has been gentle; Aftertreatment is simpler, carries out simple column chromatography after reaction is accomplished and just can get final product.
3. this present invention's catalystsystem can both be obtained good and even outstanding productive rate to general acid derivative and alkene etc., and functional group is compatible high, and with respect to traditional method, the use range of substrate is comparatively extensive.
4. used raw material acid verivate and the alkene of the present invention, and catalyzer is all the commercially produced product of wide material sources, be simple and easy to; In addition, compared to traditional method, the present invention has improved the utilising efficiency of atom with acid derivative and alkene as starting raw material greatly, meets the requirement and the direction of contemporary Green Chemistry development.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
Bu successively packs in the reaction flask
4NI (20mol%), compound 1a (2mmol, 313.2mg), tertbutyl peroxide (TBHP) (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL; This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 88%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236(
35Cl)，238(
37Cl).IR(KBr，cm
-1)：v?1716.
Embodiment two
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), hexanaphthene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 68%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236?(
35Cl)，238(
37Cl).IR(KBr，cm
-1)：v?1716.
Embodiment three
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), second cyanogen 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 50%.
1HNMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236(
35Cl)，238(
37Cl).IR(KBr，cm
-1)：v?1716.
Embodiment four
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), trimethyl carbinol 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 34%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236(
35Cl)，238(
37Cl).IR(KBr，cm
-1)：v?1716.
Embodiment five
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), 1 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 64%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236(
35Cl)，238(
37Cl).IR(KBr，cm
-1)：v?1716.
Embodiment six
The Bu4NI (20mol%) that packs into successively in the reaction flask, and compound 1b (2mmol, 244.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3b, yield is 90%.
1HNMR(400MHz，CDCl
3)δ8.07-8.04(m，2H)，7.56-7.52(m，1H)，7.45-7.41(m，2H)，6.03-5.98(m，1H)，5.85-5.82(m，1H)，5.52-5.51(m，1H)，2.17-1.94(m，3H)，1.91-1.79(m，2H)，1.75-1.66(m，1H)；
13C?NMR(100MHz，CDCl
3)δ166.2，132.8，132.7，130.7，129.5，128.2，125.6，68.5，28.3，24.9，18.9.MS：Anal.Calcd.For?C
13H
14O
2：202，Found：202.IR(KBr，cm
-1)：v?1715.
Embodiment seven
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1c (2mmol, 280.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3c, yield is 89%.
1HNMR(400MHz，CDCl
3)δ8.09-8.05(m，2H)，7.12-7.08(m，2H)，6.03-5.99(m，1H)，5.84-5.81(m，1H)，5.50-5.49(m，1H)，2.16-1.95(m，3H)，1.89-1.82(m，2H)，1.74-1.68(m，1H)；
13C?NMR(100MHz，CDCl
3)δ166.9，165.2，164.3，132.9，132.1，132.0，126.9，125.5，115.4，115.2，68.7，28.3，24.9，18.9.MS：Anal.Calcd.For?C
13H
13FO
2：220，Found：220.IR(KBr，cm
-1)：v?1716.
Embodiment eight
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1d (2mmol, 402.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3d, yield is 88%.
1HNMR(400MHz，CDCl
3)δ7.91(d，J＝8.5Hz，2H)，7.56(d，J＝8.5Hz，2H)，6.02-6.00(m，1H)，5.83-5.81(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.91-1.77(m，2H)，1.74-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.3，133.0，131.5，131.0，129.5，127.7，125.4，68.8，28.2，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 79BrO
2：280，C
13H
13 81BrO
2：282，Found：280(
79Br)，282(
81Br).IR(KBr，cm
-1)：v?1717.
Embodiment nine
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1e (2mmol, 304.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3e, yield is 80%.
1HNMR(400MHz，CDCl
3)δ8.01(d，J＝8.8Hz，2H)，6.91(d，J＝8.8Hz，2H)，6.01-5.97(m，1H)，5.84-5.81(m，1H)，5.49-5.48(m，1H)，3.85(s，3H)，2.15-1.93(m，3H)，1.88-1.81(m，2H)，1.73-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.9，163.1，132.5，131.5，125.9，123.1，113.4，68.1，55.3，28.4，24.9，18.9.MS：Anal.Calcd.For?C
14H
16O
3：232，Found：232.IR(KBr，cm
-1)：v?1707.
Embodiment ten
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1f (2mmol, 304.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3f, yield is 70%.
1HNMR(400MHz，CDCl
3)δ7.67-7.63(m，1H)，7.58-7.57(m，1H)，7.36-7.31(m，1H)，7.10-7.06(m，1H)，6.03-5.97(m，1H)，5.86-5.80(m，1H)，5.51-5.49(m，1H)，3.84(s，3H)，2.19-2.03(m，2H)，2.02-1.77(m，3H)，1.75-1.64(m，1H)；
13C?NMR(100MHz，CDCl
3)δ166.0，159.4，132.8，132.0，129.2，125.6，121.9，119.1，114.0，68.63?55.33?28.3，24.9，18.9.MS：Anal.MS：Anal.Calcd.For?C
14H
16O
3Na：255，Found：255.IR(KBr，cm
-1)：v?1712.
Embodiment 11
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1g (2mmol, 296.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3g, yield is 87%.
1H?NMR(400MHz，CDCl
3)δ＝7.68(d，J＝16.0Hz，1H)，7.52-7.50(m，2H)，7.37-7.35(m，3H)，6.44(d，J＝16.0Hz，1H)，6.01-5.97(m，1H)，5.80-5.77(m，1H)，5.41-5.40(m，1H)，2.14-1.90(m，3H)，1.85-1.78(m，2H)，1.70-1.63(m，1H)；
13C?NMR(100MHz，CDCl
3)δ166.5，144.4，134.4，132.7，130.1，128.8，127.9，125.7，118.5，68.1，28.3，24.8，18.8.MS：Anal.Calcd.ForC
15H
16O
2：228，Found：228.IR(KBr，cm
-1)：v?1713.
Embodiment 12
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1h (2mmol, 356.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3h, yield is 86%.
1HNMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.44(d，J＝8.5Hz，2H)，6.02-5.97(m，1H)，5.84-5.81(m，1H)，5.51-5.50(m，1H)，2.16-1.93(m，3H)，1.88-1.81(m，2H)，1.72-1.69(m，1H)，1.33(s，9H)；
13C?NMR(100MHz，CDCl
3)δ166.1，156.2，132.5，129.4，127.9，125.8，125.1，68.2，34.9，31.0，28.4，24.9，18.9.MS：Anal.Calcd.For?C
17H
22O
2：258.1620，Found：258.1621.IR(KBr，cm-1)：v.1716.
Embodiment 13
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1i (2mmol, 380.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3i, yield is 82%.
1HNMR(400MHz，CDCl
3)δ8.31(s，1H)，8.24(d，J＝7.8Hz，1H)，7.80(d，?J＝7.8Hz，1H)，7.60-7.55(m，1H)，6.05-6.01(m，1H)，5.86-5.81(m，1H)，5.55-5.53(m，1H)，2.21-1.80(m，5H)，1.78-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ164.9，133.3，132.8，131.6，131.1，130.7，129.3，129.3，129.2，129.2，128.9，126.5，126.5，126.4，126.4，125.2，69.3，28.3，24.9，18.9.MS：Anal.Calcd.For?C
14H
13F
3O
3：270.0868，Found：270.0874.IR(KBr，cm
-1)：v1721.
Embodiment 14
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1j (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3j, yield is 84%.
1H?NMR(400MHz，CDCl
3)δ8.02-8.01(m，1H)，7.95-7.92(m，1H)，7.53-7.49(m，1H)，7.40-7.34(m，1H)，6.04-5.99(m，1H)，5.85-5.79(m，1H)，5.51-5.49(m，1H)，2.15-1.79(m，5H)，1.76-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ164.9，134.3，133.1，132.7，132.4，129.6，129.5，127.7，125.3，69.0，28.3，24.9，18.8.MS：Anal.Calcd.For?C
13H
14 35ClO
2：237，C
13H
14 37ClO
2：239，Found：237(M+1
+)，(
35Cl)，239(M+1
+)，(
37Cl).IR(KBr，cm
-1)：v?1718.
Embodiment 15
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1k (2mmol, 400.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3k, yield is 84%.
1H?NMR(400MHz，CDCl
3)δ8.25(d，J＝8.3Hz，2H)，8.03(d，J＝8.3Hz，2H)，6.07-6.03(m，1H)，5.85-5.83(m，1H)，5.544-5.536(m，1H)，3.10(s，3H)，2.20-1.81(m，5H)，1.77-1.70(m，1H)；
13C?NMR(100MHz，CDCl
3)δ164.4，143.9，135.4，133.4，130.4，127.3，124.9，69.5，44.2，28.1，24.8，18.7.MS：Anal.Calcd.For?C
14H
16O
4S：280.0769，Found：280.0767.IR(KBr，cm
-1)：v1714.
Embodiment 16
Bu successively packs in the reaction flask
4NI (20mol%), and compound 11 (2mmol, 474.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 31, yield is 78%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.7Hz，2H)，7.42(d，J＝8.7Hz，2H)，6.71(s，1H)，6.02-5.98(m，1H)，5.84-5.81(m，1H)，5.49-5.48(m，1H)，2.16-1.93(m，3H)，1.89-1.81(m，2H)，1.74-1.67(m，1H)，1.52(s，9H)；
13CNMR(100MHz，CDCl
3)δ165.9，152.3，142.7，132.7，130.8，125.7，124.7，117.2，80.9，68.3，28.3，28.1，24.8，18.9.MS：Anal.Calcd.For?C
18H
23NO
4：217.1627，Found：217.1629.IR(KBr，cm
-1)：v?1734，1711.
Embodiment 17
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1m (2mmol, 358.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3m, yield is 52%.
1H?NMR(400MHz，CDCl
3)δ8.40(s，1H)，8.00(d，J＝8.6Hz，2H)，7.64(d，?J＝8.6Hz，2H)，6.02-5.99(m，1H)，5.84-5.81(m，1H)，5.50-5.49(m，1H)，2.21(s，3H)，2.16-1.94(m，3H)，1.91-1.80(m，2H)，1.75-1.67(m，1H)；
13CNMR(100MHz，CDCl
3)δ169.0，165.9，142.3，132.9，130.7，125.9，125.5，118.7，68.5，28.3，24.9，24.6，18.8.MS：Anal.Calcd.For?C
15H
17NO
3：259.1208，Found：259.1215.IR(KBr，cm
-1)：v?1712，1687.
Embodiment 18
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1n (2mmol, 360.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3n, yield is 47%.
1H?NMR(400MHz，CDCl
3)δ8.08(d，J＝8.6Hz，2H)，7.16(d，J＝8.6Hz，2H)，6.02-5.98(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.31(s，3H)，2.16-1.93(m，3H)，1.90-1.78(m，2H)，1.74-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ168.8，165.3，154.1，132.9，131.1，128.3，125.5，121.4，68.6，28.3，24.9，21.1，18.8.MS：Anal.Calcd.For?C
15H
16O
4：260.1049，Found：260.1044.IR(KBr，cm
-1)：v?1761，1713.
Embodiment 19
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1o (2mmol, 584.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3o, yield is 72%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.7Hz，2H)，7.70(d，J＝8.1Hz，2H)，7.32(d，J＝8.1Hz，2H)，7.04(d，J＝8.7Hz，2H)，6.03-5.99(m，1H)，?5.81-5.78(m，1H)，5.48-5.47(m，1H)，2.45(s，3H)，2.16-1.92(m，3H)，1.88-1.79(m，2H)，1.74-1.66(m，1H)；
13C?NMR(100MHz，CDCl
3)δ164.6，152.5，145.5，132.8，131.7，131.0，129.6，129.2，128.1，125.0，121.9，68.6，28.0，24.6，21.4，18.5.MS：Anal.Calcd.For?C
20H
20O
5S：395，Found：395.IR(KBr，cm
-1)：v?1710.
Embodiment 20
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1p (2mmol, 334.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3p, yield is 66%.
1H?NMR(400MHz，CDCl
3)δ8.28(d，J＝8.9Hz，2H)，8.22(d，J＝8.9Hz，2H)，6.08-6.03(m，1H)，5.85-5.83(m，1H)，5.55-5.54(m，1H)，2.19-1.97(m，3H)，1.93-1.82(m，2H)，1.78-1.72(m，1H)；
13C?NMR(100MHz，CDCl
3)δ164.2，150.3，136.1，133.5，130.6，124.9，123.3，69.7，28.2，24.8，18.7.MS：Anal.Calcd.For?C
13H
13NO
4：247，Found：247.IR(KBr，cm-1)：v.1710.
Embodiment 21:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1q (2mmol, 294.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3q, yield is 72%.
1H?NMR(400MHz，CDCl
3)δ8.15(d，J＝8.4Hz，2H)，7.74(d，J＝8.4Hz，2H)，6.06-6.02(m，1H)，5.84-5.81(m，1H)，5.53-5.52(m，1H)，2.19-1.95(m，3H)，1.94-1.79(m，2H)，1.76-1.69(m，1H)；
13C?NMR(100MHz，CDCl
3)δ?164.3，134.4，133.4，132.0，129.9，124.9，117.9，116.0，69.4，28.1，24.7，18.6；MS：Anal.Calcd.For?C
14H
13NO
2：227，Found：227.IR(KBr，cm
-1)：v?1709.
Embodiment 22:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1r (2mmol, 272.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3r, yield is 88%.
1H?NMR(400MHz，CDCl
3)δ7.91(d，J＝7.6Hz，1H)，7.37-7.33(m，1H)，7.23-7.19(m，2H)，5.99-5.97(m，1H)，5.86-5.83(m，1H)，5.492-5.488(m，1H)，2.60(s，3H)，2.13-1.79(m，5H)，1.70-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ167.2，139.7，132.6，131.6，131.4，130.4，130.1，125.6，125.5，68.2，28.3，24.8，21.7，18.8.MS：Anal.Calcd.For?C
14H
16O
2：216.1150，Found：216.1148.IR(KBr，cm
-1)：v?1712.
Embodiment 23:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1s (2mmol, 344.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3s, yield is 76%.
1H?NMR(400MHz，CDCl
3)δ8.93(d，J＝8.6Hz，1H)，8.17(d，J＝7.2Hz，1H)，7.96(d，J＝8.3Hz，1H)，7.84(d，J＝8.2Hz，1H)7.61-7.57(m，1H)，7.51-7.43(m，2H)，6.03-6.00(m，1H)，5.93-5.91(m，1H)，5.624-5.619(m，1H)，2.16-1.93(m，4H)，1.89-1.80(m，1H)，1.75-1.70(m，1H)；
13C?NMR(100MHz，CDCl
3)δ167.2，133.7，133.0，132.9，131.2，130.0，128.4，127.7，127.5，?126.0，125.7，125.6，124.4，68.6，28.4，24.9，18.9；MS：Anal.Calcd.ForC
17H
16O
2：252.1150，Found：252.1153.IR(KBr，cm
-1)：v?1712.
Embodiment 24
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1t (2mmol, 256.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3t, yield is 73%.
1H?NMR(400MHz，CDCl
3)δ7.80-7.79(m，1H)，7.54-7.52(m，1H)，7.09-7.07(m，1H)，6.01-5.99(m，1H)，5.83-5.80(m，1H)，5.47-5.46(m，1H)，2.10-1.93(m，3H)，1.86-1.83(m，2H)，1.72-1.65(m，1H)；
13C?NMR(100MHz，CDCl
3)δ161.8，134.3，133.1，132.9，132.0，127.5，125.4，68.8，28.2，24.8，18.8.MS：Anal.Calcd.For?C
11H
12O
2S：208，Found：208.IR(KBr，cm
-1)：v?1705.
Embodiment 25
Bu successively packs in the reaction flask
4NI (50mol%), and compound 1u (2mmol, 382.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3u, yield is 86%.
1H?NMR(400MHz，CDCl
3)δ7.11(d，J＝3.5Hz，1H)，6.44(d，J＝3.5Hz，1H)，6.03-5.99(m，1H)，5.80-5.77(m，1H)，5.49-5.47(m，1H)，2.15-1.92(m，3H)，1.87-1.79(m，2H)，1.72-1.60(m，1H)；
13C?NMR(100MHz，CDCl
3)δ157.2，146.5，133.2，127.1，125.0，119.7，113.7，69.0，28.1，24.7，18.7.MS：Anal.Calcd.For?C
11H
11 79BrO
3：269.9892，C
11H
11 81BrO
3：272，Found：?269.9893(
79Br)，272(
81Br).IR(KBr，cm
-1)：v?1715.
Embodiment 26
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1v (2mmol, 324.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3v, yield is 65%.
1H?NMR(400MHz，CDCl
3)δ
1H?NMR(400MHz，CDCl
3)δ7.67(d，J＝7.9Hz，1H)，7.59(d，J＝8.5Hz，1H)，7.52(s，1H)，7.45-7.41(m，1H)，7.31-7.27(m，1H)，6.05-6.02(m，1H)，5.86-5.84(m，1H)，5.58-5.57(m，1H)，2.18-2.14(m，1H)，2.07-1.83(m，4H)，1.74-1.70(m，1H)；
13C?NMR(100MHz，CDCl
3)δ159.2，155.6，145.8，133.4，127.4，126.9，125.1，123.6，122.6，113.6，112.3，69.3，28.2，24.8，18.8.MS：Anal.Calcd.For?C
15H
14O
3：242.0943，Found：242.0942.IR(KBr，cm
-1)：v?1721.
Embodiment 27
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1w (2mmol, 352.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3w, yield is 93%.
1H?NMR(400MHz，CDCl
3)δ8.18(d，J＝8.2Hz，1H)，7.42-7.41(m，2H)，7.31-7.27(m，1H)，6.04-6.00(m，1H)，5.93-5.90(m，1H)，5.674-5.668(m，1H)，4.14(s，3H)，2.17-1.96(m，4H)，1.94-1.85(m，1H)，1.77-1.71(m，1H)；?
13C?NMR(100MHz，CDCl
3)δ161.8，140.4，134.4，132.4，126.1，125.2，?122.8，122.4，121.6，109.0，68.2，35.8，27.9，24.4，18.6.MS：Anal.Calcd.ForC
15H
16N
2O
2Na：279.1109，Found：279.1115.IR(KBr，cm
-1)：v?1712.
Embodiment 28
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1x (2mmol, 362.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3x, yield is 71%.
1H?NMR(400MHz，CDCl
3)δ7.91-7.89(m，2H)，7.77-7.75(m，2H)，6.01-5.98(m，1H)，5.74-5.72(m，1H)，5.345-5.339(m，1H)，4.45(s，2H)，2.13-1.97(m，2H)，1.90-1.63(m，4H)；
13C?NMR(100MHz，CDCl
3)δ167.4，166.8，134.1，133.4，131.9，124.8，123.5，69.8，39.0，28.0，24.7，18.5.MS：Anal.Calcd.For?C
16H
15NO
4Na：308.0899，Found：308.0890，IR(KBr，cm
-1)：v?1745.1721.
Embodiment 29
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1y (2mmol, 300.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3y, yield is 79%.
1H?NMR(400MHz，CDCl
3)δ7.28-7.25(m，2H)，7.20-7.18(m，3H)，5.95-5.91(m，1H)，5.68-5.65(m，1H)，5.26-5.25(m，1H)，2.94(t，J＝7.8Hz，2H)，2.61(t，J＝7.8Hz，2H)，2.08-1.94(m，2H)，1.85-1.79(m，1H)，1.74-1.57(m，3H)；
13C?NMR(100MHz，CDCl
3)δ172.4，140.4，132.6，128.3，?128.2，126.1，125.6，68.0，36.1，31.0，28.2，24.8，18.7；MS：Anal.Calcd.ForC
15H
18O
2：230.1307，Found：230.1303.IR(KBr，cm
-1)：v?1730.
Embodiment 30
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1z (2mmol, 172.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3z, yield is 79%.
1H?NMR(400MHz，CDCl
3)δ5.96-5.92(m，1H)，5.72-5.68(m，1H)，5.26-5.24(m，1H)，2.12-1.95(m，2H)，1.90-1.83(m，1H)，1.80-1.69(m，2H)，1.67-1.56(m，2H)，1.00-0.96(m，2H)，0.86-0.81(m，2H)；
13C?NMR(100MHz，CDCl
3)δ174.5，132.5，125.7，67.8，28.2，24.8，18.8，13.1，8.4，8.3.MS：Anal.Calcd.For?C
10H
14O
2：166.0994，Found：166.0992.IR(KBr，cm
-1)：v1722.
The embodiment hentriaconta-
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1aa (2mmol, 256.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3aaa, yield is 82%.
1H?NMR(400MHz，CDCl
3)δ5.88-5.84(m，1H)，5.62-5.59(m，1H)，5.17-5.16(m，1H)，2.25-2.15(m，1H)，2.04-1.93(m，2H)，1.84-1.56(m，9H)，1.42-1.30(m，2H)，1.22-1.12(m，3H)；
13C?NMR(100MHz，CDCl
3)δ175.5，132.3，125.7，67.2，43.2，28.9，28.8，28.2，25.6，25.3，25.3，24.7，18.7.MS：Anal.Calcd.For?C
13H
20O
2：208.1363，Found：208.1460.IR(KBr，cm
-1)：v?1726.
Embodiment 32
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1ab (2mmol, 372.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3aba, yield is 79%.
1H?NMR(400MHz，CDCl
3)δ7.99(d，J＝8.3Hz，1H)，7.82(d，J＝8.2Hz，1H)，7.76-7.74(m，1H)，7.51-7.43(m，2H)7.40-7.38(m，2H)，5.92-5.88(m，1H)，5.69-5.66(m，1H)，5.27-5.26(m，1H)，4.03(s，2H)，2.05-1.89(m，2H)，1.83-1.75(m，1H)，1.65-1.62(m，2H)；1.57-1.51(m，1H)
13C?NMR(100MHz，CDCl
3)δ171.2，133.7，132.7，132.0，130.8，128.6，127.9，127.8，126.1，125.6，125.4，125.4，123.8，68.6，39.4，28.1，24.8，18.7；MS：Anal.Calcd.ForC
18H
18O
2：266.1307，Found：266.1306.IR(KBr，cm
-1)：v?1726.
Embodiment 33
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1ac (2mmol, 172.0mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3aca, yield is 75%.
1H?NMR(400MHz，CDCl
3)δ7.01-6.92(m，1H)，5.97-5.93(m，1H)，5.86-5.82(m，1H)，5.74-5.71(m，1H)，5.32-5.31(m，1H)，2.12-1.96(m，2H)，1.92-1.86(m，4H)，1.80-1.71(m，2H)，1.68-1.60(m，1H)；
13C?NMR(100MHz，CDCl
3)δ166.2，144.4，132.5，125.8，123.1，67.7，28.3，24.8，18.9，17.9.MS：Anal.Calcd.For?C
10H
15O
2：167，Found：167(M+1
+)，IR(KBr，cm
-1)：v?1716.
Embodiment 34
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1ad (2mmol, 358.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ada, yield is 81%.
1H?NMR(400MHz，CDCl
3)δ7.82-7.80(m，2H)，7.52-7.49(m，1H)，7.45-7.41(m，2H)，6.82(s，1H)，6.01-5.98(m，1H)，5.74-5.71(m，1H)，5.36-5.35(m，1H)，4.22(d，J＝2.5Hz，2H)，2.13-1.98(m，2H)，1.89-1.86(m，1H)，1.80-1.76(m，2H)，1.67-1.63(m，1H)；
13C?NMR(100MHz，CDCl
3)δ169.6，167.4，133.6，133.3，131.5，128.4，127.0，124.8，69.4，41.9，28.0，24.6，18.5.MS：Anal.Calcd.For?C
15H
17NO
3：259，Found：259.IR(KBr，cm
-1)：v1742.1652.
Embodiment 34
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1ae (2mmol, 350.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3aea, yield is 67%.
1H?NMR(400MHz，CDCl
3)δ6.00-5.97(m，1H)，5.72-5.69(m，1H)，5.33-3.32(m，1H)，5.05(s，1H)，3.90(d，J＝5.1Hz?2H)，2.12-1.97(m，2H)，1.88-1.85(m，1H)，1.77-1.62(m，3H)，1.45(s，9H)；
13C?NMR(100MHz，CDCl
3)δ169.8，155.6，133.0，124.9，79.5，68.9，42.4，28.2，28.0，24.6，18.5.MS：Anal.Calcd.For?C
13H
21NO
4Na：278，Found：278.IR(KBr，cm
-1)：v?1735，?1699.
Embodiment 35
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1af (2mmol, 418.4mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3afa, yield is 63%.
1H?NMR(400MHz，CDCl
3)δ7.35-7.30(m，5H)，5.99-5.95(m，1H)，5.70-5.68(m，1H)，5.40(s，1H)，5.32-5.31(m，1H)，5.12(s，2H)，3.95(d，J＝5.6Hz，2H)，2.11-1.96(m，2H)，1.88-1.60(m，4H)；
13C?NMR(100MHz，CDCl
3)δ169.5，156.1，136.1，133.1，128.2，127.9，127.8，124.8，69.1，66.7，42.7，27.9，24.6，18.4.MS：Anal.Calcd.For?C
16H
19NO
4Na：312.1212，Found：312.1171.IR(KBr，cm
-1)：v?1731.
Embodiment 36:
Bu successively packs in the reaction flask
4NI (50mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), cyclopentenes (0.72mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ab, yield is 63%.
1H?NMR(400MHz，CDCl
3)δ7.96(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.18-6.16(m，1H)，5.94-5.93(m，2H)，2.62-2.57(m，1H)，2.45-2.35(m，2H)，2.00-1.94(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.6，139.1，137.9，130.9，129.1，129.0，128.5，81.4，31.1，29.8.MS：Anal.Calcd.ForC
12H
11 35ClO
2K：261，C
12H
11 37ClO
2K：263，Found：261(
35Cl)，263(
37Cl).IR(KBr，cm
-1)：v?1714.
Embodiment 37:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetramethyl-ethylene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ac, yield is 68%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.41(d，J＝8.5Hz，2H)，4.84(s，2H)，1.81(s，3H)，1.78(s，3H)，1.74(s，3H)；
13C?NMR(100MHz，CDCl
3)δ165.9，139.2，132.1，131.0，129.0，128.6，122.6，66.4，20.9，20.3，16.7.MS：Anal.Calcd.For?C
13H
15 35ClO
2Na：261.0658，C
13H
15 37ClO
2Na：263.0629，Found：261.0648(
35Cl)，263.0571(
37Cl).IR(KBr，cm
-1)：v?1719.
Embodiment 38:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), allyl benzene (1.056mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ad, yield is 61%.
1H?NMR(400MHz，CDCl
3)δ8.01(d，J＝8.7Hz，2H)，7.42(d，J＝8.5Hz，4H)，7.35-7.32(m，2H)，7.29-7.25(m，1H)，6.74(d，J＝15.9Hz，1H)，6.43-6.36(m，1H)，4.97(dd，J＝6.5，1.1Hz，2H)；
13C?NMR(100MHz，CDCl
3)δ165.5，139.4，136.0，134.5，131.0，128.7，128.6，128.1，126.6，122.9，65.8.MS：Anal.Calcd.For?C
16H
13 35ClO
2Na：295.0502，C
16H
13 37ClO
2Na：297.0472，Found：295.0485(
35Cl)，297.0434(
37Cl).IR(KBr，cm
-1)：v?1719.
Embodiment 39:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), naphthane (1.08mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ae, yield is 85%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.6Hz，2H)，7.38(d，J＝8.6Hz，2H)，7.35-7.33(m，1H)，7.27-7.23(m，1H)，7.20-7.16(m，2H)，6.24(t，J＝4.5Hz，1H)，2.96-2.76(m，2H)，2.14-2.01(m，3H)，1.91-1.86(m，1H)；
13CNMR(100MHz，CDCl
3)δ165.2，139.2，137.9，134.3，131.0，129.5，129.0，129.0，128.5，128.1，126.0，70.8，29.1，28.9，18.9.MS：Anal.Calcd.ForC
17H
15 35ClO
2Na：309.0658，C
17H
15 37ClO
2Na：311.0629，Found：309.0647(
35Cl)，311.0580(
37Cl).IR(KBr，cm
-1)：v?1712.
Embodiment 40:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), indane (0.98mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3af, yield is 77%.
1H?NMR(400MHz，CDCl
3)δ7.95(d，J＝8.6Hz，2H)，7.48(d，J＝7.5Hz，1H)，7.34(d，J＝8.6Hz，2H)，7.30-7.29(m，2H)，7.24-7.20(m，1H)，6.42(dd，J＝7.0，4.0Hz，1H)，3.20-3.12(m，1H)，2.96-2.88(m，1H)，2.65-2.56(m，1H)，2.26-2.18(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.5，144.3，140.8，139.2，131.0，129.0，128.8，128.5，126.7，125.6，124.8，79.1，32.3，30.2.MS：Anal.Calcd.For?C
16H
13 35ClO
2Na：295.0502，C
16H
13 37ClO
2Na：297.0472，Found：295.0472(
35Cl)，297.0458(
37Cl).IR(KBr，cm
-1)：v?1715.
Embodiment 41:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), vinyl cyclohexane (1.128mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ag, yield is 73%.
1H?NMR(400MHz，CDCl
3)δ7.98(d，J＝8.6Hz，2H)，7.40(d，J＝8.6Hz，2H)，5.40(t，J＝7.2Hz，1H)，4.83(d，J＝7.2Hz，2H)，2.27-2.14(m，4H)，1.58-1.57(m，6H)；
13C?NMR(100MHz，CDCl
3)δ165.7，147.2，139.1，130.9，128.9，128.5，114.9，61.3，36.9，29.0，28.3，27.7，26.5.MS：Anal.Calcd.For?C
15H
17 35ClO
2Na：287.0815，C
15H
17 37ClO
2Na：289.0785，Found：287.0797(
35Cl)，289.0721(
37Cl).IR(KBr，cm
-1)：v?1719.
Embodiment 42:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), 2h (1.8g), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ah, yield is 64%.
1HNMR(400MHz，CDCl
3)δ7.97(d，J＝8.7Hz，2H)，7.41-7.38(m，4H)，7.28-7.26(m，8H)，6.12(d，J＝9.2Hz，1H)，5.49(dt，J＝9.1，6.5Hz，1H)，1.90-1.72(m，2H)，0.95-0.91(t，J＝7.5Hz，3H).；
13C?NMR(100MHz，CDCl
3)δ164.8，145.0，141.5，139.1，139.0，131.0，129.5，129.1，128.6，128.3，128.2，127.8，127.6，127.4，126.5，74.9，28.2，9.5.MS：Anal.Calcd.ForC
24H
21 35ClO
2Na：399.1128，C
24H
21 37ClO
2Na：401.1098，Found：399.1132?(
35Cl)，401.1118(
37Cl).IR(KBr，cm
-1)：v?1718.
Embodiment 43:
Bu successively packs in the reaction flask
4NI (20mol%), and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), 2i (1.666g), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3ai, yield is 98%.
1H?NMR(400MHz，CDCl
3)δ8.01(d，J＝8.3Hz，2H)，7.43(d，J＝8.3Hz，2H)，7.34-7.24(m，6H)，7.20-7.15(m，4H)，4.87(s，2H)，1.92(s，3H)；
13CNMR(100MHz，CDCl
3)δ165.5，142.9，141.8，141.3，139.2，130.9，129.5，129.4，128.6，128.1，127.9，127.0，127.0，126.9，126.8，67.3，18.3.MS：Anal.Calcd.For?C
23H
19 35ClO
2Na：385.0971，C
23H
19 37ClO
2Na：387.0942，Found：385.0945(
35Cl)，387.0918(
37Cl).IR(KBr，cm
-1)：v?1710.
Embodiment 43:
The CuI (20mol%) that packs into successively in the reaction flask, and compound 1a (2mmol, 313.2mg), TBHP (0.4mL), tetrahydrobenzene (0.8mL), benzene 8mL.This system heating after about 8 hours under 80 ℃ of conditions in air then, the saturated sodium sulfite cancellation, with ethyl acetate extraction (40mL * 3), anhydrous sodium sulfate drying, through simple column chromatography get final product oxidation products 3a, yield is 88%.
1HNMR(400MHz，CDCl
3)δ7.98(d，J＝8.5Hz，2H)，7.40(d，J＝8.5Hz，2H)，6.03-5.99(m，1H)，5.84-5.80(m，1H)，5.50-5.49(m，1H)，2.17-1.93(m，3H)，1.89-1.78(m，2H)，1.75-1.67(m，1H)；
13C?NMR(100MHz，CDCl
3)δ165.2，139.0，132.9，130.9，129.1，128.5，125.4，68.8，28.3，24.8，18.8.MS：Anal.Calcd.For?C
13H
13 35ClO
2：236，C
13H
13 37ClO
2：238，Found：236(
35Cl)，?238(
37Cl).IR(KBr，cm
-1)：v?1716。
Claims (5)
1. the preparation method of an allyl ester, it is characterized in that: with acid derivative and alkene is reaction substrate, is catalyzer with iodide, tertbutyl peroxide is an oxygenant, obtains said allyl ester through the diradical cross-coupling reaction;
The structural formula of said acid derivative is:
R wherein
1Be selected from: naphthyl, styryl, cyclopropyl, cyclohexyl, styroyl or single substituted aryl
R wherein
2Be selected from: the ester group of hydrogen, methyl, the tertiary butyl, methoxyl group, cyanic acid, C1～C6, nitro, carboxamido-group, halogen, trifluoromethyl, methylsulfonyl, the amino of Methyl benzenesulfonyl base protection, the hydroxyl of ethanoyl protection;
Said olefin selected from the following compounds represented by structural formula:
n is 0 to 5;
Said iodide are selected from cuprous iodide, Tetramethylammonium iodide, tetraethyl ammonium iodide, tetrabutylammonium iodide or four n-heptyl ammonium iodides.
2. the preparation method of allyl ester according to claim 1, it is characterized in that: the temperature of reaction of said diradical cross-coupling reaction is 60～100 ℃, the reaction times is 6～12 hours.
3. the preparation method of allyl ester according to claim 1, it is characterized in that: in molar weight, said catalyst consumption is 5～40% of an acid derivative.
4. the preparation method of allyl ester according to claim 1, it is characterized in that: the mol ratio of said acid derivative and alkene is 1: 3～5.
5. the preparation method of allyl ester according to claim 1, it is characterized in that: the used solvent of said diradical cross-coupling reaction is selected from one or more in hexanaphthene, the trimethyl carbinol, acetonitrile, 1 and the benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100802802A CN102603523A (en) | 2012-03-23 | 2012-03-23 | Preparation method of allyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100802802A CN102603523A (en) | 2012-03-23 | 2012-03-23 | Preparation method of allyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102603523A true CN102603523A (en) | 2012-07-25 |
Family
ID=46521373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100802802A Pending CN102603523A (en) | 2012-03-23 | 2012-03-23 | Preparation method of allyl esters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102603523A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187165A (en) * | 2020-02-06 | 2020-05-22 | 南京先进生物材料与过程装备研究院有限公司 | Method for continuously preparing allyl ester by using microchannel reaction device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388166A (en) * | 2001-05-24 | 2003-01-01 | 中国石化上海石油化工股份有限公司 | Prepn of high-toughness and high-flowability modified polypropylene |
| CN101265392A (en) * | 2008-04-23 | 2008-09-17 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives methacrylic ester |
-
2012
- 2012-03-23 CN CN2012100802802A patent/CN102603523A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388166A (en) * | 2001-05-24 | 2003-01-01 | 中国石化上海石油化工股份有限公司 | Prepn of high-toughness and high-flowability modified polypropylene |
| CN101265392A (en) * | 2008-04-23 | 2008-09-17 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing rosin or rosin derivatives methacrylic ester |
Non-Patent Citations (1)
| Title |
|---|
| M AL-MASUM: "Palladium-Catalyzed Hydrocarboxylation of Allenes", 《J. AM. CHEM. SOC》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111187165A (en) * | 2020-02-06 | 2020-05-22 | 南京先进生物材料与过程装备研究院有限公司 | Method for continuously preparing allyl ester by using microchannel reaction device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110404587B (en) | Supported cluster catalyst and preparation and application thereof | |
| CN108101733B (en) | Method for preparing polyaryl substituted naphthalene derivative by ruthenium catalysis reaction of fluoroarylone and tolane | |
| CN102584509A (en) | Preparation method of amide | |
| CN114933511B (en) | Method for quickly converting carboxyl into aldehyde group | |
| CN108148070B (en) | Synthetic method of furanone isoquinolone compound | |
| CN114716361B (en) | Method for synthesizing chiral spiro indenone-pyrrole compound | |
| CN101735095B (en) | Alpha-amide carbonyl class compound, derivative and synthesis method thereof | |
| CN102603523A (en) | Preparation method of allyl esters | |
| CN108707116B (en) | 2-alkyl substituted benzimidazole derivative and preparation method thereof | |
| CN114588929B (en) | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction | |
| CN102351621A (en) | Method for preparing N-sulfonyl amidine | |
| CN102617441B (en) | N-hydroxy ester preparation method | |
| CN111704558B (en) | Method for preparing phenyl-2- (2' -cyanophenyl) acetylene compounds by palladium catalysis | |
| CN111995553B (en) | Method for preparing benzoic acid-S-phenyl ester compound by cuprous catalysis | |
| CN110156673B (en) | Method for preparing quinoline compound by catalysis of zirconocene dichloride | |
| CN112920072A (en) | NOBIN biaryl compound and synthetic method thereof | |
| CN110746353A (en) | Aromatic compound and preparation method and application thereof | |
| JP6588924B2 (en) | Process for producing biphenylamines from anilides by ruthenium catalysis | |
| CN110294686B (en) | Green preparation method of alpha-ketoamide | |
| CN109053556A (en) | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application | |
| CN113754544B (en) | Preparation method of polysubstituted (E) -trifluoromethyl olefin | |
| CN103539734B (en) | The preparation method of 3-allyl group quinoline | |
| CN113717033B (en) | Benzyl ether compound and synthesis method thereof | |
| CN110981702B (en) | Efficient synthesis method of 2, 3-dibromophenol or derivatives thereof | |
| CN115160163B (en) | Method for synthesizing phenol-oxygen-substituted enaminone by promoting enaminone and phenol coupling reaction through DBDMH |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120725 |