CN105541770B - A kind of aqueous synthesis method of the dihydropyran of 5 acyl group 3,4 - Google Patents

A kind of aqueous synthesis method of the dihydropyran of 5 acyl group 3,4 Download PDF

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CN105541770B
CN105541770B CN201610129647.3A CN201610129647A CN105541770B CN 105541770 B CN105541770 B CN 105541770B CN 201610129647 A CN201610129647 A CN 201610129647A CN 105541770 B CN105541770 B CN 105541770B
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phch
amide carbonyl
dihydropyrans
carbonyl class
class compound
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CN105541770A (en
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向德轩
梁春华
刘益林
向柏霖
张莉
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SHENYANG SUNSHINE PHARMACEUTICAL Co.,Ltd.
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Huaihua University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

The invention discloses a kind of aqueous synthesis method of the dihydropyran of 5 acyl group 3,4, by β amide carbonyl class compounds, 1,3 saturated dihalide hydro carbons compounds, alkali, catalyst, auxiliary agent, water mixing are reacted.The mol ratio of the β amide carbonyl class compounds and 1,3 saturated dihalide hydro carbons compounds is 1:1.0~1.4, the mol ratio of the β amide carbonyl class compounds and alkali is 1:2.0~3.0, the mol ratio of the β amide carbonyl class compounds and catalyst be 1:0.01~0.1, the reaction time is 4.0 12.0 hours.After reaction terminates, through filtering, the dihydropyran of 5 acyl group 3,4 is produced after recrystallization.The present invention has reaction condition gentle, and technique is simple, high income, environment-friendly advantage.

Description

A kind of aqueous synthesis method of 5- acyl groups -3,4- dihydropyran
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of aqueous synthesis method of 5- acyl groups -3,4- dihydropyran.
Background technology
Dihydropyran is the important hexa-atomic Oxygenic heterocyclic compounds of a class, biology and pharmaceutical activity with uniqueness, such as Zanamivir is a kind of medicine of resisiting influenza virus, and Benesudon can be as antibiotic usage, therefore causes and numerous have Chemical machine man and the concern of medicine scholar, are also to be studied one of most heterocyclic compounds in the past few decades.At present, permitted Many synthesis on dihydropyran are reported, from the point of view of synthetic methodology angle, can be largely classified into：Terminal Acetylenes hydrogen alkoxylate is cyclized Synthesis；Antielectron demand oxo-Diels-Alder reaction synthesis；Michael additions/cyclisation cascade reaction synthesis； Knoevenagel/oxo-Diels-Alder cascade reactions are synthesized.Although these methods respectively have feature and taken to varying degrees Very gratifying result was obtained, but undeniable is also more or less in them exist：Reactions steps are more, reaction bar Part require harshness, low yield, environmental pollution seriously etc. weak point.
The content of the invention
There is provided a kind of technique is simple, high income, environment-friendly 5- acyls in view of the deficiencies of the prior art by the present invention The aqueous synthesis method of base -3,4- dihydropyran.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of 5- acyl groups -3,4- dihydropyran Preparation method, β-amide carbonyl class compound, 1,3- saturated dihalide hydro carbons compound, alkali, catalyst, auxiliary agent, water are mixed into Row reaction, the mol ratio of β-amide carbonyl class compound and 1,3- the saturated dihalide hydro carbons compound is 1:1.0~1.4, institute The mol ratio for stating β-amide carbonyl class compound and alkali is 1:2.0~3.0, the β-amide carbonyl class compound and catalyst Mol ratio be 1:0.01~0.1, the reaction temperature is 0-40 DEG C, and the reaction time is 4.0-12.0 hours.Reaction knot Shu Hou, reaction solution is filtered through cooling, is dried, and 5- acyl group -3,4- dihydropyran is produced after recrystallization purification.
Reaction equation can be expressed as follows：
Described β-amide carbonyl class compound structure is：R1-COCH2CONH-R2,
Wherein described R1Group can be：Ph-、-CH3、-CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、- CH2CH(CH3)2、-(CH2)4CH3、-CH2C(CH3)3、PhCH2-、-OCH3、-OCH2CH3、-O(CH2)2CH3、-OCH(CH3)2、-O (CH2)3CH3、-OCH2CH(CH3)2、-O(CH2)4CH3、-OCH2C(CH3)3、CH2=CHCH2O-、PhCH2O-、4-CH3PhCH2O-、 4-(CH3O)PhCH2O-、4-ClPhCH2O-、4-BrPhCH2O-、3-CH3PhCH2O-、3-(CH3O)PhCH2O-、3- ClPhCH2O-、3-BrPhCH2O-、2-CH3PhCH2O-、2-(CH3O)PhCH2O-、2-ClPhCH2O- or 2-BrPhCH2O-；
The R2Group can be：-CH3、-CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、-CH2CH (CH3)2、-(CH2)4CH3、-CH2C(CH3)3、Ph-、biPhenyl、4-CH3Ph-、4-(CH3CH2)Ph-、4-[CH3(CH2)2] Ph-、4-[(CH3)2CH]Ph-、4-(PhCH2O)Ph-、4-CH3OPh-、4-(CH3CH2O)Ph-、4-(CH3(CH2)2O)Ph-、4- [(CH3)2CHO]Ph-、4-ClPh-、4-BrPh-、4-FPh-、4-NO2Ph-、4-CNPh-、4-[(CH3)2N]Ph-、4- (CH3O2C)Ph-、4-(CH3CH2O2C)Ph-、3-CH3Ph-、3-(CH3CH2)Ph-、3-[CH3(CH2)2]Ph-、3-[(CH3)2CH] Ph-、3-(PhCH2O)Ph-、3-CH3OPh-、3-(CH3CH2O)Ph-、3-(CH3(CH2)2O)Ph-、3-[(CH3)2CHO]Ph-、3- ClPh-、3-BrPh-、3-FPh-、3-NO2Ph-、3-CNPh-、3-[(CH3)2N]Ph-、3-(CH3O2C)Ph-、3-(CH3CH2O2C) Ph-、2-CH3Ph-、2-(CH3CH2)Ph-、2-[CH3(CH2)2]Ph-、2-[(CH3)2CH]Ph-、2-(PhCH2O)Ph-、2- CH3OPh-、2-(CH3CH2O)Ph-、2-(CH3(CH2)2O)Ph-、2-[(CH3)2CHO]Ph-、2-ClPh-、2-BrPh-、2- FPh-、2-NO2Ph-、2-CNPh-、2-[(CH3)2N]Ph-、2-(CH3O2C)Ph-、2-(CH3CH2O2C)Ph-、2,4-(CH3)2Ph-、3,4-(CH3)2Ph-、3,5-(CH3)2Ph-、3,4,5-(CH3)3Ph-、2,4-(CH3O)2Ph-、3,4-(CH3O)2Ph-、3, 5-(CH3O)2Ph-、3,4,5-(CH3O)3Ph-、2-CH3-4-ClPh-、2-CH3O-4-ClPh-、2-CH3-4-BrPh-、2-CH3O- 4-BrPh-, 2-furyl, 2-thienyl, 2-pyridyl, 3-pyridyl or 4-pyridyl；
Described 1,3- saturated dihalide hydro carbons compound structures are：XCH2CHR3CH2X,
Wherein X can be：Cl、Br、I；
R3Can be：-CH3、-CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、-CH2CH(CH3)2、-(CH2)4CH3、-CH2C(CH3)3、PhCH2-、Ph-、biPhenyl、4-CH3Ph-、4-(CH3CH2)Ph-、4-[CH3(CH2)2]Ph-、4- [(CH3)2CH]Ph-、4-(PhCH2O)Ph-、4-CH3OPh-、4-(CH3CH2O)Ph-、4-(CH3(CH2)2O)Ph-、4-[(CH3)2CHO]Ph-、4-ClPh-、4-BrPh-、4-FPh-、4-NO2Ph-、4-CNPh-、4-[(CH3)2N]Ph-、4-(CH3O2C)Ph-、 4-(CH3CH2O2C)Ph-、3-CH3Ph-、3-(CH3CH2)Ph-、3-[CH3(CH2)2]Ph-、3-[(CH3)2CH]Ph-、3- (PhCH2O)Ph-、3-CH3OPh-、3-(CH3CH2O)Ph-、2-(CH3O2C)Ph-、2-(CH3CH2O2C) Ph- or 2,4- (CH3)2Ph-。
The alkali can be Na, K and Cs hydroxide, carbonate, phosphate and acetate, preferably K2CO3。
The catalyst can for TBAB, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide or 18 hats six, preferably tetrabutylammonium chloride.
The auxiliary agent is ammonium acetate.
Further, the mol ratio of β-amide carbonyl class compound and 1,3- the saturated dihalide hydro carbons compound is 1:1.2.
Further, the mol ratio of the β-amide carbonyl class compound and alkali is preferably 1:2.4.
Further, the mol ratio of the β-amide carbonyl class compound and catalyst be 1:0.1.
Further, the mol ratio of the auxiliary agent and β-amide carbonyl class compound be 1.1:1.
Theoretically the present invention will be described below：
The mol ratio of β-amide carbonyl class compound and alkali has a major impact to reaction, β-amide carbonyl class compound and alkali Mol ratio it is too big when, reaction speed is slow, and β-amide carbonyl class compound conversion ratio is low；When too small, reaction speed is fast, while 1, The reaction of 3- saturated dihalide hydro carbons compound hydrolysis increases, and causes β-amide carbonyl class compound conversion ratio reduction.Therefore, it is of the invention The mol ratio of middle β-amide carbonyl class compound and alkali is 1:2.0~3.0, preferably 1:2.2~2.4.
The species of alkali is had a major impact to reaction, when alkalescence is too strong, and 1,3- saturated dihalide hydro carbons compound can be caused to occur Hydrolysis, reduction β-amide carbonyl class compound conversion ratio is low；When alkalescence is too weak, it is difficult to capture β-amide carbonyl class compound Hydrogen on methylene, causes reaction speed to reduce.Therefore, the present invention employed in alkali for Na, K and Cs hydroxide, Carbonate, phosphate and acetate, preferably K2CO3。
Catalyst is to reacting particularly significant.Because β-amide carbonyl class compound and 1,3- saturated dihalide hydro carbons compounds exist All do not dissolved in aqueous phase, it is difficult to directly react, so when not having catalyst, reaction is difficult directly to carry out；When catalytic amount too Hour, reaction speed is slow, low yield；When catalyst exceedes certain consumption, reaction speed and yield are also held essentially constant.
Auxiliary agent also has highly important influence to reaction.Ammonium acetate is as a kind of organic salt, after being dissolved in aqueous phase, can To play certain cushioning effect to reaction system, when being added without ammonium acetate or addition in reaction system very little, 1,3- bis- Alkyl halide hydrocarbon compound facile hydrolysis in aqueous phase, reduces reaction yield；When auxiliary dosage exceed it is a certain amount of when, reaction yield It is not further added by.
Compared with prior art, the present invention has advantages below：
1st, reaction condition is gentle, and technique is simple, is that 5- acyl group -3,4- dihydropyran is made through single step reaction；
2nd, reaction is carried out in aqueous phase, it is to avoid the use of organic solvent, and cost is low, and environment-friendly, the three wastes are few；
3rd, reaction yield is high, and product yield reaches as high as 96% more than 85%.
Embodiment
With reference to embodiment, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, NaOH 2.3mmol, TBAB 0.05mmol, ammonium acetate 1.2mmol, 1,3- dibromos are sequentially added Propane 1.15mmol and 30mL deionized water, stirs.After reaction solution continues stirring 8.0 hours at 10 DEG C, stop reaction, Through filtering, dry, 6- aniline -5- acetyl group -3,4- dihydropyran, product yield 89% are produced after recrystallization purification.
Embodiment 2：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H4CH31.0mmol is added in 50 millis Rise in round-bottomed flask, sequentially add KOH 2.3mmol, tetrabutylammonium chloride 0.05mmol, ammonium acetate 1.3mmol, 1,3- bis- Chloropropane 1.2mmol and 35mL deionized water, stirs.After reaction solution continues stirring 8.0 hours at 20 DEG C, stop anti- Should, through filtering, dry, 6- (4- methylanilines) -5- acetyl group -3,4- dihydropyran, product yield are produced after recrystallization purification 86%.
Embodiment 3：
By the β shown in following formula-amide carbonyl class compound CH3CH2-COCH2CONH-C6H4Cl 1.0mmol are added 50 In milliliter round-bottomed flask, K is sequentially added2CO32.4mmol, tetrabutylammonium chloride 0.10mmol, ammonium acetate 1.1mmol, 1,3- Diiodo propane 1.2mmol and 35mL deionized water, stirs.After reaction solution continues stirring 10.0 hours at 20 DEG C, stop Reaction, through filtering, is dried, and 6- (4- chloroanilines) -5- propiono -3,4- dihydropyran, product yield are produced after recrystallization purification 96%.
Embodiment 4：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, K is sequentially added2CO32.3mmol, TBAB 0.03mmol, ammonium acetate 1.2mmol, 1,3- dibromo Propane 1.15mmol and 30mL deionized water, stirs.After reaction solution continues stirring 8.0 hours at 25 DEG C, stop reaction, Through filtering, dry, 6- aniline -5- acetyl group -3,4- dihydropyran, product yield 95% are produced after recrystallization purification.
Embodiment 5：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C5H4N 1.0mmol are added in 50 millis Rise in round-bottomed flask, sequentially add K2CO32.2mmol, 4 bromide 0.03mmol, ammonium acetate 1.2mmol, 1,3- bis- N-Propyl Bromide 1.1mmol and 40mL deionized water, stirs.After reaction solution continues stirring 12.0 hours at 10 DEG C, stop anti- Should, through filtering, dry, 6- (4- amidos pyridine) -5- acetyl group -3,4- dihydropyran, product yield is produced after recrystallization purification 88%.
Embodiment 6：
By the β shown in following formula-amide carbonyl class compound CH3CH2-COCH2CONH-C6H51.0mmol is added in 50 millis Rise in round-bottomed flask, sequentially add Cs2CO32.2mmol, 18 six 0.05mmol of hat, ammonium acetate 1.2mmol, 1,3- bis- are bromo- 2- methylpropane 1.15mmol and 35mL deionized waters, stir.After reaction solution continues stirring 5.0 hours at 40 DEG C, stop Only react, through filtering, dry, 6- aniline -5- propiono -3- methyl -3,4- dihydropyran is produced after recrystallization purification, product is received Rate 87%.
Embodiment 7：
By the β shown in following formula-amide carbonyl class compound C6H5-COCH2CONH-CH31.0mmol is added at 50 milliliters In round-bottomed flask, K is sequentially added2CO32.4mmol, TBAB 0.07mmol, ammonium acetate 1.2mmol, 1,3- bis- are bromo- 2- methylpropane 1.2mmol and 30mL deionized waters, stir.After reaction solution continues stirring 8.0 hours at 30 DEG C, stop Reaction, through filtering, is dried, and 6- methylamine -5- benzoyl -3- methyl -3,4- dihydropyran is produced after recrystallization purification, and product is received Rate 87%.
Embodiment 8：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-CH2C6H51.0mmol is added in 50 millis Rise in round-bottomed flask, sequentially add K2CO32.4mmol, TBAB 0.03mmol, ammonium acetate 1.1mmol, 1,3- bis- Bromo- 2- triethanol propanes 1.1mmol and 30mL deionized water, stirs.After reaction solution continues stirring 12.0 hours at 10 DEG C, Stop reaction, through filtering, dry, 6- benzylamine -5- acetyl group -3- ethyl -3,4- dihydropyran, product are produced after recrystallization purification Yield 89%.
Embodiment 9：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C4H3O 1.0mmol are added in 50 millis Rise in round-bottomed flask, sequentially add K2CO32.2mmol, TBAB 0.03mmol, ammonium acetate 1.4mmol, 1,3- bis- Bromo- 2- methylpropanes 1.1mmol and 40mL deionized water, stirs.After reaction solution continues stirring 6.0 hours at 30 DEG C, Stop reaction, through filtering, dry, 6- (2- amidos furans) -5- acetyl group -3- methyl -3,4- dihydros are produced after recrystallization purification Pyrans, product yield 93%.
Embodiment 10：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, Na is sequentially added2CO32.4mmol, tetramethyl ammonium chloride 0.05mmol, ammonium acetate 1.2mmol, 1,3- dibromo Propane 1.2mmol and 30mL deionized water, stirs.After reaction solution continues stirring 12.0 hours at 25 DEG C, stop reaction, Through filtering, dry, 6- aniline -5- acetyl group -3,4- dihydropyran, product yield 85% are produced after recrystallization purification.
Comparative example 1：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, K is sequentially added2CO32.3mmol, ammonium acetate 1.2mmol, 1,3- dibromopropane 1.15mmol and 30mL go from Sub- water, stirs.After reaction solution continues stirring 8.0 hours at 25 DEG C, stop reaction, through filtering, dry, produced after purification 6- aniline -5- acetyl group -3,4- dihydropyran, product yield 5%.
Comparative example 2：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, K is sequentially added2CO32.3mmol, TBAB 0.03mmol, 1,3- dibromopropane 1.15mmol and 30mL deionized waters, stir.After reaction solution continues stirring 8.0 hours at 25 DEG C, stop reaction, through filtering, dry, weight 6- aniline -5- acetyl group -3,4- dihydropyran, product yield 67% are produced after crystallization and purification.
Comparative example 3：
By the β shown in following formula-amide carbonyl class compound CH3-COCH2CONH-C6H51.0mmol is added at 50 milliliters In round-bottomed flask, K is sequentially added2CO32.3mmol, DMF and 1,3- dibromopropane 1.15mmol, stirring Uniformly.After reaction solution continues stirring 8.0 hours at 25 DEG C, stop reaction, through filtering, dry, 6- is produced after recrystallization purification Aniline -5- acetyl group -3,4- dihydropyran, product yield 85%.
。

Claims (7)

1. a kind of aqueous synthesis method of 5- acyl groups -3,4- dihydropyrans, it is characterised in that：It is molten using water as reaction Agent, is 1 in molar ratio by β-amide carbonyl class compound and 1,3- saturated dihalide hydro carbons compound, alkali, auxiliary agent, catalyst：1.0 ~1.4：2.0~3.0：1.0~1.5：0.01~0.1 is well mixed, reaction 4.0-12.0 hours in the case where temperature is 0-40 DEG C, instead After should terminating, through filtering, 5- acyl group -3,4- dihydropyrans are obtained after recrystallization；
The reaction equation is：
Described β-amide carbonyl class compound structure is：R1-COCH2CONH-R2, wherein R1Group is：Ph-、-CH3、- CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、-CH2CH(CH3)2、-(CH2)4CH3、-CH2C(CH3)3、PhCH2-、- OCH3、-OCH2CH3、-O(CH2)2CH3、-OCH(CH3)2、-O(CH2)3CH3、-OCH2CH(CH3)2、-O(CH2)4CH3、-OCH2C (CH3)3、CH2=CHCH2O-、PhCH2O-、4-CH3PhCH2O-、4-(CH3O)PhCH2O-、4-ClPhCH2O-、4-BrPhCH2O-、 3-CH3PhCH2O-、3-(CH3O)PhCH2O-、3-ClPhCH2O-、3-BrPhCH2O-、2-CH3PhCH2O-、2-(CH3O) PhCH2O-、2-ClPhCH2O- or 2-BrPhCH2O-；
R2Group is：-CH3、-CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、-CH2CH(CH3)2、-(CH2)4CH3、- CH2C(CH3)3、Ph-、biPhenyl、4-CH3Ph-、4-(CH3CH2)Ph-、4-[CH3(CH2)2]Ph-、4-[(CH3)2CH]Ph-、 4-(PhCH2O)Ph-、4-CH3OPh-、4-(CH3CH2O)Ph-、4-(CH3(CH2)2O)Ph-、4-[(CH3)2CHO]Ph-、4- ClPh-、4-BrPh-、4-FPh-、4-NO2Ph-、4-CNPh-、4-[(CH3)2N]Ph-、4-(CH3O2C)Ph-、4-(CH3CH2O2C) Ph-、3-CH3Ph-、3-(CH3CH2)Ph-、3-[CH3(CH2)2]Ph-、3-[(CH3)2CH]Ph-、3-(PhCH2O)Ph-、3- CH3OPh-、3-(CH3CH2O)Ph-、3-(CH3(CH2)2O)Ph-、3-[(CH3)2CHO]Ph-、3-ClPh-、3-BrPh-、3- FPh-、3-NO2Ph-、3-CNPh-、3-[(CH3)2N]Ph-、3-(CH3O2C)Ph-、3-(CH3CH2O2C)Ph-、2-CH3Ph-、2- (CH3CH2)Ph-、2-[CH3(CH2)2]Ph-、2-[(CH3)2CH]Ph-、2-(PhCH2O)Ph-、2-CH3OPh-、2-(CH3CH2O) Ph-、2-(CH3(CH2)2O)Ph-、2-[(CH3)2CHO]Ph-、2-ClPh-、2-BrPh-、2-FPh-、2-NO2Ph-、2-CNPh-、 2-[(CH3)2N]Ph-、2-(CH3O2C)Ph-、2-(CH3CH2O2C)Ph-、2,4-(CH3)2Ph-、3,4-(CH3)2Ph-、3,5- (CH3)2Ph-、3,4,5-(CH3)3Ph-、2,4-(CH3O)2Ph-、3,4-(CH3O)2Ph-、3,5-(CH3O)2Ph-、3,4,5- (CH3O)3Ph-、2-CH3-4-ClPh-、2-CH3O-4-ClPh-、2-CH3-4-BrPh-、2-CH3O-4-BrPh-、2-furyl、2- Thienyl, 2-pyridyl, 3-pyridyl or 4-pyridyl；
Described 1,3- saturated dihalide hydro carbons compound structures are：XCH2CHR3CH2X, wherein X are：Cl, Br or I；
R3For：-CH3、-CH2CH3、-(CH2)2CH3、-CH(CH3)2、-(CH2)3CH3、-CH2CH(CH3)2、-(CH2)4CH3、-CH2C (CH3)3、PhCH2-、Ph-、biPhenyl、4-CH3Ph-、4-(CH3CH2)Ph-、4-[CH3(CH2)2]Ph-、4-[(CH3)2CH] Ph-、4-(PhCH2O)Ph-、4-CH3OPh-、4-(CH3CH2O)Ph-、4-(CH3(CH2)2O)Ph-、4-[(CH3)2CHO]Ph-、4- ClPh-、4-BrPh-、4-FPh-、4-NO2Ph-、4-CNPh-、4-[(CH3)2N]Ph-、4-(CH3O2C)Ph-、4-(CH3CH2O2C) Ph-、3-CH3Ph-、3-(CH3CH2)Ph-、3-[CH3(CH2)2]Ph-、3-[(CH3)2CH]Ph-、3-(PhCH2O)Ph-、3- CH3OPh-、3-(CH3CH2O)Ph-、2-(CH3O2C)Ph-、2-(CH3CH2O2C) Ph- or 2,4- (CH3)2Ph-；
The alkali is any one in Na, K and Cs hydroxide, carbonate, phosphate or acetate；
The catalyst is TBAB, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, 18 hats six In any one；
The auxiliary agent is ammonium acetate.
2. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute The mol ratio for stating β-amide carbonyl class compound and 1,3- saturated dihalide hydro carbons compounds is 1:1.2.
3. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute The mol ratio for stating β-amide carbonyl class compound and alkali is 1:2.4.
4. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute The mol ratio for stating β-amide carbonyl class compound and catalyst is 1:0.1.
5. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute The mol ratio for stating auxiliary agent and β-amide carbonyl class compound is 1.1:1.
6. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute Alkali is stated for potassium carbonate.
7. the preparation method of 5- acyl groups -3,4- dihydropyrans according to claim 1, it is characterised in that：Institute Catalyst is stated for tetrabutylammonium chloride.
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