CN106518663A - Method for preparing alpha-acyloxy ketone compound - Google Patents
Method for preparing alpha-acyloxy ketone compound Download PDFInfo
- Publication number
- CN106518663A CN106518663A CN201610946542.7A CN201610946542A CN106518663A CN 106518663 A CN106518663 A CN 106518663A CN 201610946542 A CN201610946542 A CN 201610946542A CN 106518663 A CN106518663 A CN 106518663A
- Authority
- CN
- China
- Prior art keywords
- mmol
- group
- preferred
- reaction
- alkyl
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing an alpha-acyloxy ketone compound. According to the invention, simple and easily available alcohol and carboxylic acid are taken as the raw materials, under mediation of NBS(N-bromo-succinimide) and DBU(1,8-diazabicyclo(5.4.0)undec-7-alkene), the alpha-acyloxy ketone is prepared by a one-pot reaction. The method has the advantages of mild reaction condition, simple and easily available raw materials, wide substrate adaptation scope, no requirement of rigorous reaction conditions such as any metal catalyst, peroxy compounds, low or high temperature and water-free and oxygen-free conditions, metal pollution is avoided; and the method also has the advantages of stable technical condition, simple and safe operation, and easy purifying of the product.
Description
Technical field
The invention belongs to synthetic organic chemical art, is related to a kind of preparation method of alpha-acyloxy assimilation compound, specifically
It is related to a kind of direct method that alpha-acyloxy assimilation compound is synthesized using alcohol and carboxylic acid of NBS/DBU mediations.
Background technology
Alpha-acyloxy ketone（α-acyloxyketones）Compound is ground in chemical research, chemical industry, functional material and medicine
Sending out etc. has extremely significant meaning in practical application.Alpha-acyloxy assimilation compound structure fragment is widely present in natural product
In, often as the key structure skeleton of physiologically active molecule and drug molecule.Alpha-acyloxy ketone is risen in organic synthesis body
Important support effect.Research shows, the material containing the structure fragment has numerous biologic activity, such as antibacterial, antiinflammatory, anti-
Tuberculosis, convulsion, antitumor etc..
Traditional synthetic method is generally assimilation compound and toxic heavy metal Pb (OAc) 4, Tl (OAc)3, Hg(OAc)2Directly
It is reversed to answer（(a) J. D. Cocker, H. B. Henbest, G. H. Phillipps, G. P. Slater and D.
A. Thomas,J.Chem.Soc.,1965, 6; (b) M. E. Kuehne and T. C. Giacobbe,
J.Org.Chem.,1968, 33, 3359; (c) D. J. Rawilson and G. Sosnovsky,Synthesis,
1973, 567; (d) J. C. Lee, Y. S. Jin and J.-H. Choi, Chem.Commun., 2001, 956）,
Or be that carboxylate and α-halogenatedketone compound react（P. A. Levine and A. Walti, Org.Synth.Coll.,
1943, 2, 5）.This kind of method uses toxic heavy metal, big to environmental hazard.With the development of Green Chemistry, people seek one
Plant more efficient method to prepare the alpha-acyloxy assimilation compound with important synthesis meaning.In recent years, closed with high price iodate
Thing improves esterification rate as oxidant and obtains research and development as catalyst, peroxide, and details are as follows：
2005, M. Ochiai groups are reported with benzene iodide (PhI) and metachloroperbenzoic acid (m- CPBA) as catalysis
Agent and oxidant, make ketone generate α-acyl-oxygen carbonyl compound with the coupling of acetic acid oxidation catalysed cross, and the reaction can also select H2O2Make
For oxidant, Ac2O is used as acetyl oxidation reagent（M. Ochiai, Y. Takeuchi, T. Katayama, T. Sueda and
K. Miyamoto,J.Am.Chem.Soc.2005,127,12244）（Reaction equation is as follows）.
2011, M. Uyanik were reported with ketone and carboxylic acid and are carried out synthetic reaction as raw material, using H2O2/Bu4NI or
TBHP/ Bu4NI obtains similar α-acyl-oxygen carbonyl compound as oxidant and catalyst（M. Uyanik, D.
Suzuki, T. Yasui and K.Ishihara,Angew.Chem.,Int.Ed.2011,50,5331）（Reaction equation is as follows）.
2014, it was raw material in Bu that S. Gu chemical groups are reported again using ketone and benzyl alcohol4NI and peroxide TBHP
Under conditions of directly carry out catalysis oxidation cross-coupling reaction（Reaction equation is as follows）, the reaction only obtains medium yield（S.
Guo, J.-T. Yu, Q. Dai, H. Yang and J. Cheng, Chem.Commun.,2014,50,6240）.
2014, it was raw material in Bu that A.Sudalai groups are reported using ketone and toluene derivative4NI and peroxide
Catalysis oxidation cross-coupling reaction synthesis α-acyl-oxygen assimilation compound is carried out under conditions of TBHP directly（Reaction equation is as follows）, the reaction
Medium and preferable yield is obtained only（R.N.Reddi,P.K.Prasad and A.Sudalai,Org.Lett.2014,16,
5674）.
2014, it was raw material in Bu4NI and peroxide TBHP that Wang groups are reported using ketone and styrene derivative
Under conditions of, with benzene plus nitrile as solvent, carry out catalysis oxidation cross-coupling reaction and generate alpha-acyloxy ketone（Reaction equation is as follows）（F.
Zhu and Z-X. Wang, Tetrahedron 2014, 70, 9819）.
2015, Pan groups report using alkene and carboxylic acid be raw material under conditions of iodine and peroxide TBHP,
With triethylamine as alkali, DMSO is solvent, carries out oxidation acyloxylation reaction response and obtains alpha-acyloxy ketone（ B. Mondal, S.
C. Sahoo and S. C. Pan, Eur.J.Org.Chem.2015, 3135）（Reaction equation is as follows）.
Additionally, 2015, Wang groups also reported and be directly catalyzed propiophenone and 1-Phenylethanone. in α-C using 20mol% mantoquitas
(sp3) replace on H and generate α-acyl-oxygen carbonyl compound reaction, the reaction is being catalyst using CuI, and oxygen is used as reaction oxidation
Agent, achieves low to medium yield on the upper side, the higher reaction temperature of reaction needs（120oC) (J. Du, X.
Zhang,X. Sun and L. Wang,Chem.Commun.,2015,51,1043)（Reaction equation is as follows）.
Above research work, fully indicates the importance of alpha-acyloxy ketone compounds, and their synthesis is subject to chemistry
The great attention of family.But above-mentioned synthetic method is still using some poisonous metallic catalysts or using dangerous
Big peroxide is oxidant so as to limiting their extensive applications in organic synthesiss and medicinal chemistry art, institute
With, study a kind of simple, safe and efficient synthetic method be very in the urgent need to.
The content of the invention
The technical problem to be solved is that research design synthesizes alpha-acyloxy using raw material simple and easy to get
The method of assimilation compound, the method pass through " one kettle way " two-step reaction, and alpha-acyloxy assimilation is effectively obtained under shirtsleeve operation
Compound, by nonmetal catalyzed and not using the approach of peroxide realizing, reaction is gentle, convenient, economical.
Technical solution of the present invention is as follows：
A kind of preparation method of alpha-acyloxy assimilation compound, including：With formula（I）Shown alcohol and formula（II）Shown carboxylic acid is former for starting
Material, in mono- bromo-succinimides of N（NBS）And diazabicylo（DBU）Under conditions of mediation, formula is synthesized（III）It is shown
Alpha-acyloxy assimilation compound, reaction equation are as follows：
Wherein, R1For aryl, aralkyl, alkyl, cycloalkyl, halogen, ester group, alkoxyl or itrile group；R2For aryl, aralkyl,
Alkyl, cycloalkyl or hydrogen atom；R3For aryl, aralkyl, alkyl, cycloalkyl, alkynyl or thiazolinyl.
Further, described aryl includes monokaryon aromatic yl group and multinuclear aromatic yl group, such as phenyl, naphthyl, Herba Alii fistulosi base or
Phenanthryl etc., monokaryon aryl and multinuclear aryl can replace on one or more positions；When the monokaryon aryl to replace,
The alkyl of the preferred C1-C7 of substituent group, the alkoxyl of C1-C7, halogen, cyano group, acetyl group, nitro, alkoxy carbonyl group or ester group；
Further, described aryl includes the heteroaryl containing nitrogen, oxygen or sulphur atom, and described heteroaryl includes that substituent group takes
The heteroaryl in generation, the alkyl of the preferred C1-C7 of described substituent group, the alkoxyl of C1-C7, halogen, cyano group, acetyl group, nitro, alkane
Oxygen carbonyl or ester group；
Further, when described heteroaryl is monokaryon heteroaryl, preferred pyridine radicals, furyl, pyrrole radicals, imidazole radicals, thiazole
Base or methylthiophene base；When described heteroaryl is multinuclear heteroaryl, preferred xenyl, naphthyl, pyrrole radicals, thienyl, benzo
Furyl, indyl, quinolyl, imidazole radicals, pyrazolyl or pyridine radicals；
Further, described aralkyl represents aromatic yl elementary alkyl, and described aryl is as defined above, and described low alkyl group is
The alkyl of C1-C7；The aralkyl is unsubstituted aralkyl or substituted aralkyl, the preferred benzyl of unsubstituted aralkyl,
The preferred methoxy-benzyl of substituted aralkyl, methyl-benzyl, Fluoro-benz rLl, chlorobenzyl, nitrobenzyl, phenethyl or pyridine first
Base；
Further, described alkyl, is the straight or branched alkyl of C1-C20, the alkyl of preferred C1-C6, such as ethyl, propyl group,
Isopropyl, butyl, n-pentyl, isopentyl, hexyl, heptyl or octyl group；
Further, described cycloalkyl, is the cycloalkyl of C3-C10, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or gold
Firm alkane；
Further, described halogen, preferred fluorine, chlorine, bromine, iodine；Described ester, preferred methyl formate or Ethyl formate；It is described
Alkoxyl, preferred methoxyl group, ethyoxyl or propoxyl group；Described alkynyl, preferred propine, butine, phenyl-allylene or hexin；It is described
Thiazolinyl, preferred propylene, butylene, styrene or butylene.
In preparation method of the present invention, raw alcohol is 1 with the mol ratio of carboxylic acid:1～8, preferably 1:1～5.
In above-mentioned preparation method, consumption preferably 2 equivalents of described NBS and DBU.
In above-mentioned preparation method, described reaction, temperature are 0～100 DEG C, preferably 40～60 DEG C.
In above-mentioned preparation method, described reaction can be reacted in oxygen, nitrogen or air, preferably anti-in atmosphere
Should.
Preferably, the preparation method of alpha-acyloxy assimilation compound of the present invention, concrete steps include：Under room temperature, successively by alcohol,
The mixing of carboxylic acid, NBS and organic solvent, stirs 1h at 40～60 DEG C, is subsequently adding DBU, continues reaction 2h, obtains alpha-acyloxy ketone
Compound.
Described organic solvent be non-protonic solvent, including Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, acetonitrile, ethyl acetate,
Dimethyl sulfoxide, dichloromethane, chloroform, 1,2- dichloroethanes, 1,2- dimethoxy-ethanes, toluene, benzene or N, N- dimethyl formyl
Amine, preferred Isosorbide-5-Nitrae-dioxane.
The invention provides the preparation method of alpha-acyloxy assimilation compound, compared with the method for former report, the method is former
Expect that cheap and easily-available, reaction condition is gentle, Atom economy is high, substrate wide accommodation, yield are high, need not use any metal
The reaction condition of catalyst and per-compound oxidant etc.；This method also has short preparation period, stable process conditions, operation letter
Just the advantage of safety, easy purification of products, can carry out large-scale production.
Specific embodiment
The present invention is further illustrated below by specific embodiment, it should be understood that the preparation side of the embodiment of the present invention
Method is only used for illustrating the present invention, rather than limitation of the present invention；On the premise of present inventive concept, to present invention preparation
The simple modifications of method belong to the protection domain of application claims.
Embodiment 1：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.251g, yield 99%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.12 (d, J = 7.1 Hz, 2H), 8.03 (d, J =
7.1 Hz, 2H), 7.63-7.58 (m, 2H), 7.53-7.45 (m, 4H), 6.24 (q, J = 7.0 Hz, 3H),
1.70 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.7, 166.0, 134.5,
133.6, 133.3, 129.9, 129.5, 128.8, 128.5, 128.4, 71.9, 17.2; HRMS calc. for
C16H14O3Na (M+Na)+, 277.0841; found, 277.0846.
Embodiment 2：
Under room temperature, 4- methyl isophthalic acids-phenylpropanol (0.15 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White solid 0.239g, yield 89%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.11 (d, J = 7.0 Hz, 2H), 7.93 (d, J =
8.2 Hz, 2H), 7.60 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.9 Hz, 2H), 7.31 (d, J =
8.0 Hz,2H), 6.22 (q, J = 7.0 Hz, 1H), 2.44 (s, 3H), 1.69 (d, J = 7.0 Hz, 3H);13C NMR (CDCl3, 100 MHz, ppm): δ196.2, 166.0, 144.5, 133.2, 132.0, 129.9,
129.6, 129.5, 128.7, 128.4, 71.8, 21.7, 17.3; HRMS calc. for C17H16O3Na (M+Na
)+, 291.0997; found, 291.0999.
Embodiment 3：
Under room temperature, 1- phenethanol (0.122 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White solid 0.211g, yield 88%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.17 (d,J = 7.1 Hz, 2H), 8.00 (d, J =
7.1 Hz, 2H), 7.66-7.61 (m, 2H), 7.56-7.48 (m, 4H), 5.61 (s, 2H); 13C NMR
(CDCl3, 100 MHz, ppm): δ192.3, 166.0, 134.4, 133.9, 133.3, 130.0, 128.9,
128.5, 127.9, 66.5; HRMS calc. for C15H12O3Na (M+Na)+, 263.0684; found,
263.0685.
Embodiment 4：
Under room temperature, 4- methoxyl group -1- phenethanol (0.152 g, 1 mmol), benzene first are sequentially added in 50 mL round-bottomed flasks
Sour (0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).It is little in 60 DEG C of stirrings 1
When, DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction,
Concentrating under reduced pressure, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）
Obtain corresponding product alpha-acyloxy assimilation compound（White solid 0.230g, yield 85%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.17 (d, J = 7.1 Hz, 2H), 7.98 (d, J =
6.9 Hz, 2H), 7.62 (t, J = 7.5 Hz, 1H), 7.49 (t, J = 7.8 Hz, 2H), 7.00 (d, J =
6.9 Hz, 2H), 5.57 (s, 2H), 3.91 (s, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ
190.6, 166.1, 164.1, 133.3, 130.2, 130.0, 129.6, 128.4, 127.4, 114.1, 66.2,
55.5; HRMS calc. for C16H14O4Na (M+Na)+, 293.0790; found, 293.0791.
Embodiment 5：
Under room temperature, the fluoro- 1- phenethanol of 4- (0.14 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White solid 0.178g, yield 69%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.16 (d, J = 7.1 Hz,2H), 8.06-8.02 (m,
2H), 7.63 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 7.9 Hz,2H), 7.21 (t, J = 8.6 Hz,
2H), 5.57 (s, 2H); 13C NMR (CDCl3, 100 MHz, ppm): δ190.7, 166.2 (d, J = 254.5
Hz), 166.1, 133.4, 130.8 (d, J = 2.9 Hz), 130.6 (d, J = 9.4 Hz), 130.0,
129.3, 128.5, 116.1 (d, J = 21.9 Hz), 66.3; HRMS calc. for C15H11O3FNa (M+Na)+,
281.0590; found, 281.0593.
Embodiment 6：
Under room temperature, 4- chlorine 1- phenethanol (0.156 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White solid 0.233g, yield 85%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.16 (d, J = 7.1 Hz, 2H), 7.94 (d, J =
8.6 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.52-7.48 (m, 3H), 5.56 (s, 2H); 13C
NMR (CDCl3, 100 MHz, ppm): δ191.1, 166.0 140.4, 133.4, 132.7, 130.0, 129.3,
129.2, 128.5, 66.3; HRMS calc. for C15H11O3ClNa (M+Na)+, 297.0294; found,
297.0291.
Embodiment 7：
Under room temperature, the bromo- 1- phenethanol of 4- (0.2 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White solid 0.210g, yield 66%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.17-8.15 (m, 2H), 7.86 (d, J = 8.6 Hz,
2H), 7.68 (d, J = 8.6 Hz,2H), 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz,
2H), 5.55 (s, 2H); 13C NMR (CDCl3, 100 MHz, ppm): δ191.3, 166.0, 133.4, 133.1,
132.3, 130.0, 129.3, 129.3, 129.2, 128.5, 66.3; HRMS calc. for C15H11O3BrNa (M+
Na)+, 340.9789; found, 340.9791.
Embodiment 8：
Under room temperature, 3- Trifluoromethyl-1s-phenethanol (0.19 g, 1 mmol), benzene first are sequentially added in 50 mL round-bottomed flasks
Sour (0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).It is little in 60 DEG C of stirrings 1
When, DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction,
Concentrating under reduced pressure, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）
Obtain corresponding product alpha-acyloxy assimilation compound（White solid 0.170, yield 55%）
1H NMR (CDCl3, 400 MHz, ppm): δ8.26 (s, 1H), 8.19-8.14 (m, 3H), 7.91 (d,J = 7.8 Hz, 1H), 7.69 (t, J = 7.8 Hz, 1H), 7.66-7.62 (m, 1H), 7.51 (t, J =
7.9 Hz, 2H), 5.60 (s, 2H); 13C NMR (CDCl3, 100 MHz, ppm): δ191.2, 166.0,
134.9, 133.5, 131.6 (d, J = 33.0 Hz), 131.0, 130.3 (q, J = 3.4 Hz,Hz), 130.0,
129.6, 129.2, 128.5, 128.4, 124.8 (d, J = 4.1 Hz), 66.4;HRMS calc. for
C16H11O3F3Na (M+Na)+, 331.0558; found, 331.0561.
Embodiment 9：
Under room temperature, 1- fenipentols (0.164 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.260g, yield 92%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.13 (d, J = 7.1 Hz, 2H), 8.03 (J = 7.2
Hz, 2H), 7.62-7.59 (m, 2H), 7.54-7.46 (m, 4H), 6.14 (dd, J 1 = 5.4 Hz, J 2 = 7.9
Hz, 1H), 2.04-1.99 (m, 2H), 1.66-1.59 (m, 2H), 1.03 (t, J = 7.4 Hz, 3H); 13C
NMR (CDCl3, 100 MHz, ppm): δ196.5, 166.2, 134.9, 133.5, 133.2, 129.9, 129.6,
128.8, 128.5, 128.4, 75.6, 33.5, 19.0, 13.8; HRMS calc. for C18H18O3Na (M+Na)+,
305.1154; found, 305.1155.
Embodiment 10：
Under room temperature, 1- benzene hexanols (0.178 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.270g, yield 91%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.13 (d, J = 7.1 Hz, 2H), 8.03 (d, J =
7.1 Hz, 2H), 7.64-7.59 (m, 2H), 7.54-7.47 (m, 4H), 6.12 (t, J = 6.2 Hz, 1H),
2.06-2.01 (m, 2H), 1.59-1.53(m, 2H), 1.46-1.39 (m, 2H), 0.95 (t, J = 7.3 Hz,
3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.5, 166.2, 135.0, 133.5, 133.2, 129.9,
129.6, 128.8, 128.5, 128.4, 75.8, 31.2, 27.7, 22.4, 13.8; HRMS calc. for
C19H20O3Na (M+Na)+, 319.1310; found, 319.1311.
Embodiment 11：
Under room temperature, 1- naphthyl ethanol (0.172 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（White liquid 0.203g, yield 70%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.71 (d,J = 8.6 Hz, 1H), 8.18 (t, J =
7.1 Hz,2H), 8.07 (d, J = 8.3 Hz, 1H), 7.98 (dd, J 1 = 0.9 Hz,J 2 = 7.2 Hz, 1H),
7.92 (d, J = 7.6 Hz, 1H), 7.65-7.61 (m, 2H), 7.59-7.56 (m, 2H), 7.50 (t, J =
7.8 Hz, 1H), 5.59 (s, 2H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.0, 166.1,
134.0, 133.5, 133.4, 132.5, 130.3, 130.2, 130.0, 129.5, 128.5, 128.4, 127.5,
126.8, 125.7, 124.3, 67.9; HRMS calc. for C19H14O3Na (M+Na)+, 313.0841; found,
313.0844.
Embodiment 12：
Under room temperature, 2,3- dihydro -1- indanols (0.134 g, 1 mmol), benzoic acid are sequentially added in 50 mL round-bottomed flasks
(0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.222g, yield 88%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.12 (d, J = 7.1 Hz, 2H), 7.87 (d, J =
7.7 Hz, 1H), 7.70 (dt, J 1 = 1.1 Hz,J 2 = 7.6 Hz, 1H), 7.63-7.59 (m, 1H), 7.52-
7.46 (m, 4H), 5.67 (dd, J 1 = 4.8 Hz,J 2 = 8.0 Hz, 1H), 3.80 (dd, J 1 = 8.0 Hz,J 2 =
17.0 Hz, 1H), 3.23 (dd, J 1 = 4.8 Hz,J 2 = 17.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz,
ppm): δ200.4, 166.1, 150.4, 135.9, 134.7, 133.4, 130.0, 129.4, 128.4, 128.2,
126.7, 124.6, 74.5, 33.6; HRMS calc. for C16H12O3Na (M+Na)+, 275.0684; found,
275.0685.
Embodiment 13：
Under room temperature, 1 is sequentially added in 50 mL round-bottomed flasks, -1 alcohol of 2,3,4- tetrahydrochysenes-naphthalene (0.148 g, 1 mmol), benzene
Formic acid (0.183g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).1 is stirred at 60 DEG C
Hour, DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stop anti-
Should, concentrating under reduced pressure obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silica gel
Post）Obtain corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.245g, yield 92%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.19-8.16 (m, 2H), 8.09 (dd, J 1 = 1.1
Hz,J 2 = 7.8 Hz, 1H), 7.64-7.59 (m, 1H), 7.56 (dt,J 1 = 1.4 Hz,J 2 = 7.5 Hz,1H),
7.49 (t, J = 7.8 Hz,2H), 7.38 (t, J = 7.6 Hz, 1H), 7.32 (d, J = 7.7 Hz, 1H),
5.83 (dd, J 1 = 5.2 Hz,J 2 = 13.2 Hz, 1H), 3.36-3.28 (m, 1H), 3.21-3.15 (m, 1H),
2.60-2.54 (m, 1H), 2.52-2.41 (m, 1H); 13C NMR (CDCl3, 100 MHz, ppm): δ192.8,
165.8, 143.1, 133.9, 133.2, 131.7, 129.9, 129.8, 128.7, 128.4, 127.9, 127.0,
75.0, 29.3, 28.0; HRMS calc. for C17H14O3Na (M+Na)+, 289.0841; found, 289.0845.
Embodiment 14：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- ar-Toluic acids are sequentially added in 50 mL round-bottomed flasks
(0.204g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.241g, yield 90%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.04-7.99 (m, 4H), 7.61 (t,J = 7.4 Hz,
1H), 7.51 (t, J = 7.8 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 6.21 (q, J = 7.0 Hz,
1H), 2.44 (s, 3H), 1.69 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ
196.9, 166.1, 144.1, 134.5, 133.6, 129.9, 129.1, 128.8, 128.6, 126.7, 71.7,
21.7, 17.2; HRMS calc. for C17H16O3Na (M+Na)+, 291.0997; found, 291.0993.
Embodiment 15：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- methoxybenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.228g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.259g, yield 91%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.08-8.01 (m, 4H), 7.61 (t,J = 7.4 Hz,
1H), 7.51 (t, J = 7.8 Hz, 2H), 6.94 (d,J = 9.0 Hz,2H), 6.20 (q, J = 7.0 Hz,
1H), 3.89 (s, 3H), 1.68 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ
197.0, 165.7, 163.7, 134.6, 133.5, 132.0, 128.8, 128.6, 121.9, 113.7, 71.6,
55.5, 17.2; HRMS calc. for C17H16O4Na (M+Na)+, 307.0946; found, 307.0944.
Embodiment 16：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 3- ar-Toluic acids are sequentially added in 50 mL round-bottomed flasks
(0.204g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.250g, yield 93%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.03 (d, J = 7.8 Hz, 2H), 7.92 (d, J =
9.0 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.51 (t, J = 7.8 Hz, 2H), 7.41 (d, J =
7.6 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 6.23 (q, J = 7.0 Hz,1H), 2.43 (s, 3H),
1.70 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.8, 166.2, 138.2,
134.5, 134.1, 133.6, 130.4, 129.4, 128.8, 128.6, 128.3, 127.1, 71.8, 21.3,
17.2; HRMS calc. for C17H16O3Na (M+Na)+, 291.0997; found, 291.0991.
Embodiment 17：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- chlorobenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.234g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.266g, yield 92%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.07-8.01 (m, 4H), 7.63 (t, J = 7.4 Hz,
1H), 7.52 (t, J = 7.8 Hz,2H), 7.45 (d, J = 8.6 Hz,2H), 6.22 (q, J = 7.0 Hz,
1H), 1.70 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.5, 165.1,
139.8, 134.3, 133.7, 131.3, 128.9, 128.8, 128.5, 128.0, 72.1, 17.2; HRMS
calc. for C16H13O3ClNa (M+Na)+, 311.0451; found, 311.0453.
Embodiment 18：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- bromobenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.3g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).60 DEG C stir 1 hour, so
DBU (0.304 g, 2 mmol) is added afterwards, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, reduces pressure dense
Contracting, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain phase
The product alpha-acyloxy assimilation compound answered（White solid 0.300g, yield 90%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.02-7.97 (m, 4H), 7.64-7.60 (m, 3H),
7.52 (t, J = 7.9 Hz, 2H), 6.22 (q, J = 7.0 Hz,1H), 1.69 (d, J = 7.0 Hz, 3H);13C NMR (CDCl3, 100 MHz, ppm): δ196.5, 165.3, 134.3, 133.7, 131.8, 131.4,
128.9, 128.5, 128.4, 72.1, 17.3; HRMS calc. for C16H13O3BrNa (M+Na)+, 354.9946;
found, 354.9949.
Embodiment 19：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- nitrobenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.251g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.275g, yield 92%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.35-8.29 (m, 4H), 8.01 (t, J = 7.2 Hz,
2H), 7.66 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.9 Hz, 2H), 6.28 (q, J = 7.0 Hz,
1H), 1.74 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.0, 164.2,
150.8, 135.0, 134.2, 133.9, 131.0, 129.0, 128.5, 123.6, 72.8, 17.3; HRMS
calc. for C16H13NO5Na (M+Na)+, 322.0691, found, 322.0693.
Embodiment 20：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 4- trifluoromethylbenzene first are sequentially added in 50 mL round-bottomed flasks
Sour (0.285g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).It is little in 60 DEG C of stirrings 1
When, DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction,
Concentrating under reduced pressure, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）
Obtain corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.232g, yield 72%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.24 (d, J = 8.0 Hz, 2H), 8.01 (d, J =
7.2 Hz, 2H), 7.74 (d, J = 8.2 Hz, 2H), 7.64 (t, J = 7.3 Hz, 1H), 7.53 (t, J =
7.8 Hz, 2H), 6.26 (q, J = 7.0 Hz, 1H), 1.72 (d, J = 7.0 Hz, 3H); 13C NMR
(CDCl3, 100 MHz, ppm): δ196.3, 164.8, 134.7(d, J = 32.5 Hz), 134.3, 133.8,
132.8, 130.3, 128.9, 128.5, 125.5 (q, J = 3.7 Hz), 123.6 (d, J = 271.1 Hz),
72.4, 17.3; HRMS calc. for C17H13O3F3Na (M+Na)+, 345.0714; found, 345.0717.
Embodiment 21：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 2- chlorobenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.234g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.269g, yield 93%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.02 (t, J = 7.4 Hz, 2H), 7.98 (d, J =
7.1 Hz, 1H), 7.64 (t, J = 7.3 Hz, 1H), 7.53 (t, J = 7.9 Hz, 2H), 7.50-7.44
(m, 2H), 7.38-7.34 (m, 1H), 6.27 (q, J = 7.0 Hz, 1H), 1.69 (d,J = 7.0 Hz,
3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.4, 164.9, 134.1, 133.6, 132.8, 131.8,
131.1, 129.4, 128.8, 128.5, 126.6, 72.3, 17.1;HRMS calc. for C16H13O3ClNa (M+
Na)+, 311.0451; found, 311.0553.
Embodiment 22：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), the bromo- 5- methylbenzene of 2- are sequentially added in 50 mL round-bottomed flasks
Formic acid (0.321g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).1 is stirred at 60 DEG C
Hour, DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stop anti-
Should, concentrating under reduced pressure obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silica gel
Post）Obtain corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.306g, yield 88%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.03 (d, J = 7.7 Hz, 2H), 7.76 (d, J =
1.9 Hz,1H), 7.63 (t, J = 7.2 Hz, 1H), 7.56-7.51 (m, 3H), 7.18 (dd, J 1 = 2.2
Hz,J 2 = 8.2 Hz, 1H), 6.27 (q, J = 7.0 Hz, 1H), 2.37 (s, 3H), 1.69 (d, J = 7.0
Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.5, 165.6, 137.4, 134.4, 134.1,
133.8, 133.7, 132.3, 131.0, 128.8, 128.6, 118.5, 72.3, 20.8, 17.2; HRMS calc.
for C17H15O3BrNa (M+Na)+, 369.0102; found, 369.0104.
Embodiment 23：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 2- bromobenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.3 g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.280g, yield 84%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.01 (d, J = 7.2 Hz, 2H), 7.97 (dd, J 1
= 2.0 Hz,J 2 = 7.6 Hz, 1H), 7.69 (dd, J 1 = 1.2 Hz,J 2 = 7.6 Hz, 1H), 7.63 (t, J =
7.4 Hz, 1H), 7.52 (t,J = 7.8 Hz, 2H), 7.43-7.37 (m, 2H), 6.27 (q, J = 7.0 Hz,
1H), 1.69 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.4, 165.4,
134.4, 134.4, 133.7, 132.8, 131.8, 131.4, 128.8, 128.5, 127.2, 121.9, 72.4,
17.1; HRMS calc. for C16H13O3BrNa (M+Na)+, 354.9946; found, 354.9949.
Embodiment 24：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 2- iodo-benzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.372g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.296g, yield 78%）.
1H NMR (CDCl3, 400 MHz, ppm): δ8.02 (d, J = 7.2 Hz, 3H), 7.99 (dd, J 1
= 1.7 Hz,J 2 = 7.8 Hz, 1H), 7.66-7.61 (m, 1H), 7.53 (t, J = 7.8 Hz, 2H), 7.45
(dt, J 1 = 1.1 Hz,J 2 = 7.6 Hz, 1H), 7.20 (dt, J 1 = 1.7 Hz,J 2 = 7.7 Hz, 1H), 6.28
(q, J = 7.0 Hz, 1H), 1.70 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm):
δ196.4,165.8,141.4, 134.3, 134.2, 133.7, 133.0, 131.6, 128.9, 128.6, 128.0,
94.3, 72.5,17.2;HRMS calc.for C16H13O3INa (M+Na)+, 402.9807; found, 402.9809 .
Embodiment 25：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), 2- Phenylbenzoic acids are sequentially added in 50 mL round-bottomed flasks
(0.297g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 4 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.271g, yield 82%）.
1H NMR (CDCl3, 400 MHz, ppm): δ7.97-7.92 (m, 3H), 7.57 (t, J = 8.5 Hz,
2H), 7.50-7.45 (m, 3H), 7.41-7.6-35 (m, 6H), 5.96 (q,J = 7.0 Hz, 1H), 1.32
(d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.5, 167.6, 143.0,
141.4, 134.4, 133.5, 131.6, 130.8, 130.4, 130.0, 128.7, 128.6, 128.5, 128.0,
127.2, 127.2, 72.0, 16.8; HRMS calc. for C22H18O3Na (M+Na)+, 353.1154; found,
353.1151.
Embodiment 26：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), benzenpropanoic acid are sequentially added in 50 mL round-bottomed flasks
(0.225g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.262g, yield 93%）.
1H NMR (CDCl3, 400 MHz, ppm): δ7.96 (d, J = 7.2 Hz, 2H), 7.62 (t, J =
7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.24-7.22
(m, 3H), 6.00 (q, J = 7.0 Hz, 1H), 3.00 (t, J = 7.9 Hz,2H), 2.80-2.75 (m,
2H), 1.54 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.9, 172.3,
140.4, 134.4, 133.6, 128.8, 128.5, 128.5, 128.3, 126.3, 71.4, 35.5, 30.8,
17.1; HRMS calc. for C18H18O3Na (M+Na)+, 305.1154; found, 305.1157.
Embodiment 27：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol) is sequentially added in 50 mL round-bottomed flasks, acetic acid (0.09g,
1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C, be subsequently adding
DBU (0.304 g, 2 mmol), continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, concentrating under reduced pressure are obtained
Crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Produced accordingly
Thing alpha-acyloxy assimilation compound（Yellow liquid 0.161g, yield 84%）.
1H NMR (CDCl3, 400 MHz, ppm): δ7.97 (d, J = 7.2 Hz, 2H), 7.62 (t, J =
7.5 Hz, 1H), 7.51 (t, J = 7.8 Hz, 2H), 5.99 (q, J = 7.0 Hz, 1H), 2.17 (s,
3H), 1.56 (d, J = 7.1 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ196.9, 170.4,
134.5, 133.5, 128.8, 128.5, 71.4, 20.7, 17.1; HRMS calc. for C11H12O3Na (M+Na
)+, 215.0684; found, 215.0682.
Embodiment 28：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol) is sequentially added in 50 mL round-bottomed flasks, propanoic acid (0.111g,
1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C, be subsequently adding
DBU (0.304 g, 2 mmol), continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, concentrating under reduced pressure are obtained
Crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Produced accordingly
Thing alpha-acyloxy assimilation compound（Yellow liquid 0.175g, yield 85%）.
1H NMR (CDCl3, 400 MHz, ppm): δ7.97 (d,J = 7.7 Hz, 2H), 7.61 (t, J =
7.3 Hz, 1H), 7.50 (t, J = 7.8 Hz, 2H), 6.00 (q, J = 7.0 Hz,1H), 2.47-2.43 (m,
2H), 1.55 (d, J = 7.0 Hz, 3H), 1.18 (t,J = 7.0 Hz,3H); 13C NMR (CDCl3, 100
MHz, ppm): δ197.1, 173.9, 134.6, 133.5, 128.7, 128.4, 71.2, 27.3, 17.1, 8.9;
HRMS calc. for C12H14O3Na (M+Na)+, 229.0841; found, 229.0845.
Embodiment 29：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol), tetrolic acid are sequentially added in 50 mL round-bottomed flasks
(0.126g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow liquid 0.194g, yield 90%）.
1H NMR (CDCl3, 400 MHz, ppm): δ7.96 (d,J = 8.1 Hz, 2H), 7.63 (t,J =
7.4 Hz, 1H), 7.51 (t, J = 7.9 Hz, 2H), 6.05 (q, J = 7.0 Hz,1H), 2.03 (s, 3H),
1.60 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz, ppm): δ195.7, 152.8, 134.1,
133.7, 128.8, 128.5, 87.1, 72.7, 71.9, 17.1, 3.9; HRMS calc. for C13H12O3Na (M+
Na)+, 239.0684; found, 239.0687.
Embodiment 30：
Under room temperature, 1- phenylpropanol (0.136 g, 1 mmol) .beta.-methylacrylic acid are sequentially added in 50 mL round-bottomed flasks
(0.129g, 1.5 mmol), NBS（0.356g, 2 mmol) and 1,4- dioxane (2 mL).Stir 1 hour at 60 DEG C,
DBU (0.304 g, 2 mmol) is subsequently adding, continues reaction 2 hours (TLC detection reactions).Then, stopped reaction, decompression
Concentration, obtains crude product.Petroleum ether and the mixtures of eluents of ethyl acetate is finally used to rinse, rapid column chromatography（Silicagel column）Obtain
Corresponding product alpha-acyloxy assimilation compound（Yellow solid 0.109g, yield 50%）.
1H NMR (CDCl3, 500 MHz, ppm): δ7.98 (d,J = 7.2 Hz, 2H), 7.61 (t,J =
7.4 Hz, 1H), 7.50 (t, J = 7.9 Hz, 2H), 7.11-7.04 (m,1H), 6.05(q, J = 7.0 Hz,
1H), 5.96 (dq, J 1 = 1.6 Hz, J 2 = 15.6 Hz, 1H), 1.91 (dd, J 1 = 1.7 Hz, J 2 = 7.0
Hz, 3H), 1.58 (d, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 125 MHz, ppm): δ197.0,
165.7, 146.1, 134.5, 133.5, 128.8, 128.5, 121.9, 71.1, 18.1, 17.1; HRMS calc.
for C13H14O3Na (M+Na)+, 241.0841; found, 241.0845。
Claims (10)
1. a kind of preparation method of alpha-acyloxy assimilation compound, it is characterised in that include：With formula（I）Shown alcohol and formula（II）Institute
Show that carboxylic acid is initiation material, in mono- bromo-succinimides of N（NBS）And diazabicylo（DBU）Under conditions of mediation, reaction is closed
An accepted way of doing sth（III）Shown alpha-acyloxy assimilation compound, reaction equation are as follows：
Wherein, R1For aryl, aralkyl, alkyl, cycloalkyl, halogen, ester group, alkoxyl or itrile group；R2For aryl, aralkyl, alkane
Base, cycloalkyl or hydrogen atom；R3For aryl, aralkyl, alkyl, cycloalkyl, alkynyl or thiazolinyl.
2. preparation method according to claim 1, it is characterised in that：Described aryl includes monokaryon aromatic yl group and multinuclear
Aromatic yl group, such as phenyl, naphthyl, Herba Alii fistulosi base or phenanthryl, monokaryon aryl and multinuclear aryl can be taken on one or more positions
Generation；When the monokaryon aryl to replace, the alkyl of the preferred C1-C7 of substituent group, the alkoxyl of C1-C7, halogen, cyano group, acetyl
Base, nitro, alkoxy carbonyl group or ester group.
3. preparation method according to claim 1, it is characterised in that：Described aryl is included containing nitrogen, oxygen or sulphur atom
Heteroaryl, described heteroaryl include substituent group replace heteroaryl, the alkyl of the preferred C1-C7 of described substituent group, C1-C7
Alkoxyl, halogen, cyano group, acetyl group, nitro, alkoxy carbonyl group or ester group；
When described heteroaryl is monokaryon heteroaryl, preferred pyridine radicals, furyl, pyrrole radicals, imidazole radicals, thiazolyl or methyl thiazolium
Fen base；When described heteroaryl is multinuclear heteroaryl, preferred xenyl, naphthyl, pyrrole radicals, thienyl, benzofuranyl, indole
Base, quinolyl, imidazole radicals, pyrazolyl or pyridine radicals.
4. preparation method according to claim 3, it is characterised in that：Described aralkyl represents aromatic yl elementary alkyl, institute
The aryl stated defines same Claims 2 or 3, and described low alkyl group is the alkyl of C1-C7；The aralkyl is unsubstituted virtue
Alkyl or substituted aralkyl, the preferred benzyl of unsubstituted aralkyl, the preferred methoxy-benzyl of substituted aralkyl, methyl benzyl
Base, Fluoro-benz rLl, chlorobenzyl, nitrobenzyl, phenethyl or picolyl.
5. preparation method according to claim 1, it is characterised in that：
Described alkyl, is the straight or branched alkyl of C1-C20, the alkyl of preferred C1-C6, such as ethyl, propyl group, isopropyl, fourth
Base, n-pentyl, isopentyl, hexyl, heptyl or octyl group；
Described cycloalkyl, is the cycloalkyl of C3-C10, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl or diamantane (obsolete)；
Described halogen, preferred fluorine, chlorine, bromine, iodine；Described ester, preferred methyl formate or Ethyl formate；Described alkoxyl,
It is preferred that methoxyl group, ethyoxyl or propoxyl group；
Described alkynyl, preferred propine, butine, phenyl-allylene or hexin；Described thiazolinyl, preferred propylene, butylene, styrene or fourth
Alkene.
6. preparation method according to claim 1, it is characterised in that：Raw alcohol is 1 with the mol ratio of carboxylic acid:1～8, it is excellent
Select 1:1～5.
7. preparation method according to claim 1, it is characterised in that：The consumption of described NBS and DBU preferably 2 equivalents.
8. preparation method according to claim 1, it is characterised in that：Described reaction, temperature be 0～100 DEG C, preferably 40
～60 DEG C；Described reaction, can react in oxygen, nitrogen or air, preferably react in atmosphere.
9. preparation method according to claim 1, it is characterised in that：Concrete steps include：Under room temperature, successively by alcohol, carboxylic
The mixing of acid, NBS and organic solvent, stirs 1h at 40～60 DEG C, is subsequently adding DBU, continues reaction 2h, obtains alpha-acyloxy assimilation
Compound.
10. preparation method according to claim 9, it is characterised in that：Described organic solvent is non-protonic solvent, is wrapped
Include 1,4- dioxane, tetrahydrofuran, acetonitrile, ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform, 1,2- dichloroethanes, 1,
2- dimethoxy-ethanes, toluene, benzene or DMF, preferred Isosorbide-5-Nitrae-dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946542.7A CN106518663B (en) | 2016-10-26 | 2016-10-26 | A kind of preparation method of alpha-acyloxy ketone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946542.7A CN106518663B (en) | 2016-10-26 | 2016-10-26 | A kind of preparation method of alpha-acyloxy ketone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106518663A true CN106518663A (en) | 2017-03-22 |
| CN106518663B CN106518663B (en) | 2019-06-11 |
Family
ID=58293267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610946542.7A Active CN106518663B (en) | 2016-10-26 | 2016-10-26 | A kind of preparation method of alpha-acyloxy ketone compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106518663B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362794A (en) * | 2020-03-10 | 2020-07-03 | 河北科技大学 | Preparation method of α -acyloxyketone compound |
| CN111377814A (en) * | 2020-03-10 | 2020-07-07 | 河北科技大学 | Preparation method of α -acyloxyketone compound |
| CN111848445A (en) * | 2019-04-30 | 2020-10-30 | 帝斯曼知识产权资产管理有限公司 | Improved method for producing acyloxy enamine |
| CN113896631A (en) * | 2021-11-02 | 2022-01-07 | 华北水利水电大学 | Preparation method of ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964232A (en) * | 2011-08-30 | 2013-03-13 | 北京大学深圳研究生院 | Preparation method of ketone compound and its derivatives |
-
2016
- 2016-10-26 CN CN201610946542.7A patent/CN106518663B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964232A (en) * | 2011-08-30 | 2013-03-13 | 北京大学深圳研究生院 | Preparation method of ketone compound and its derivatives |
Non-Patent Citations (3)
| Title |
|---|
| FENG ZHU ET AL.: "Bu4NI-catalyzed a-acyloxylation reaction of ethers and ketones with aldehydes and tert-butyl hydroperoxide", 《TETRAHEDRON》 * |
| GIOVANNI W. AMARANTE ET AL.: "An approach for the enantioselective synthesis of biologically active furanones from a MoritaeBayliseHillman adduct", 《TETRAHEDRON》 * |
| SONGJIN GUO ET AL.: "The Bu4NI-catalyzed alfa-acyloxylation of ketones with benzylic alcohols", 《CHEMICAL COMMUNICATIONS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848445A (en) * | 2019-04-30 | 2020-10-30 | 帝斯曼知识产权资产管理有限公司 | Improved method for producing acyloxy enamine |
| CN111362794A (en) * | 2020-03-10 | 2020-07-03 | 河北科技大学 | Preparation method of α -acyloxyketone compound |
| CN111377814A (en) * | 2020-03-10 | 2020-07-07 | 河北科技大学 | Preparation method of α -acyloxyketone compound |
| CN113896631A (en) * | 2021-11-02 | 2022-01-07 | 华北水利水电大学 | Preparation method of ester |
| CN113896631B (en) * | 2021-11-02 | 2023-12-22 | 华北水利水电大学 | Preparation method of ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106518663B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shirini et al. | One-pot synthesis of various xanthene derivatives using ionic liquid 1, 3-disulfonic acid imidazolium hydrogen sulfate as an efficient and reusable catalyst under solvent-free conditions | |
| CN106518663A (en) | Method for preparing alpha-acyloxy ketone compound | |
| Karimi-Jaberi et al. | Tris (hydrogensulfato) boron as a solid heterogeneous catalyst for the rapid synthesis of α, α′-benzylidene bis (4-hydroxycoumarin) derivatives | |
| Shinde et al. | p-Toluenesulfonic acid doped polystyrene (PS-PTSA): solvent-free microwave assisted cross-coupling-cyclization–oxidation to build one-pot diversely functionalized pyrrole from aldehyde, amine, active methylene, and nitroalkane | |
| Dong et al. | Transformation of aldehydes or alcohols to amides at room temperature under aqueous conditions | |
| Senapak et al. | Brönsted acid-surfactant-combined ionic liquid catalyzed green synthesis of 2-alkyl and 2-arylbenzothiazoles in water: reusable catalyst and metal-free conditions | |
| CN103304393B (en) | A kind of synthetic method of benzil analog derivative | |
| CN105175328A (en) | Method for synthesizing quinoline derivative by utilizing arylamine, aromatic aldehyde and ketone | |
| Shen et al. | Dimethylbut-2-ynedioate mediated esterification of acids via sp3 C–N bond cleavage of benzylic tertiary amines | |
| Ziarati et al. | Pseudo five-component process for the synthesis of functionalized tricarboxamides using CuI nanoparticles as reusable catalyst | |
| CN105218540B (en) | A kind of preparation method of 3 thiocarbamoyl imidazoles of C simultaneously [1,2 a] pyridine compounds and their | |
| CN110804015B (en) | Preparation method of trans-disubstituted olefin | |
| CN106187890B (en) | A method of acridone derivatives are catalyzed and synthesized altogether using palladium-copper | |
| CN102093355B (en) | C-3 acylated indolizine compound and preparation method thereof | |
| CN115028564B (en) | Synthesis method of pyrrole derivative | |
| CN107915653B (en) | Method for preparing amide by catalyzing ester and amine to react | |
| CN105859718A (en) | Preparation method of copper-catalyzed nitrogen-containing polyheterocyclic compound | |
| CN115093372A (en) | Synthesis method of imidazole derivative | |
| CN105237466B (en) | A kind of method for synthesizing three substituted pyridine derivatives | |
| CN104761601B (en) | The synthesis of the tetrasulfonic acid base D glucopyranose sulfur hydrogen salts of 1 imidazoles of β 2,3,4,6 and purposes | |
| CN109265403B (en) | Synthesis method of benzimidazole and derivatives thereof | |
| CN103275003B (en) | A kind of preparation method of phenanthridone derivative | |
| Zhi et al. | New catalytic system for aminohalogenation of β-methyl-β-nitrostyrenes to give opposite regiochemistry | |
| CN104860864B (en) | The synthetic method of the alkynyl azole compounds of 2 carbonyl 5 | |
| CN115466171B (en) | Preparation method of 2, 3-dihydro-1H-cyclopenteno [ a ] naphthalene derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |