CN106631646B - The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound - Google Patents

The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound Download PDF

Info

Publication number
CN106631646B
CN106631646B CN201610735258.5A CN201610735258A CN106631646B CN 106631646 B CN106631646 B CN 106631646B CN 201610735258 A CN201610735258 A CN 201610735258A CN 106631646 B CN106631646 B CN 106631646B
Authority
CN
China
Prior art keywords
added
ethyl acetate
oxo
compound
cdcl
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.)
Expired - Fee Related
Application number
CN201610735258.5A
Other languages
Chinese (zh)
Other versions
CN106631646A (en
Inventor
何艳
范学森
张新迎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Normal University
Original Assignee
Henan Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henan Normal University filed Critical Henan Normal University
Priority to CN201610735258.5A priority Critical patent/CN106631646B/en
Publication of CN106631646A publication Critical patent/CN106631646A/en
Application granted granted Critical
Publication of CN106631646B publication Critical patent/CN106631646B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses it is a kind of (E) -4- oxo -2- butylene aldehyde compound synthetic method, belong to the synthesis technical field of aldehyde compound.Technical solution of the present invention main points are as follows: high allyl alcohols compound is dissolved in organic solvent, nitrous acid special butyl ester and oxidant is then added, be made in the presence of air or oxygen in 40-100 DEG C of reaction (E) -4- oxo -2- butylene aldehyde compound.Synthesis process of the present invention is one pot of tandem reaction, and high-efficient, raw material is easily prepared, and reaction is carried out at 100 DEG C or less, and mild condition is easy to operate, applied widely, the product configuration stereoselectivity height of substrate.

Description

The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound
Technical field
The invention belongs to the synthesis technical fields of aldehyde compound, and in particular to one kind (E) -4- oxo -2- butylene aldehydes The synthetic method of compound.
Background technique
As important organic synthesis intermediate, 4- oxo -2- butylene aldehyde compound is in fine chemistry industry and pharmaceutical chemistry Equal fields, which all have, to be widely applied, therefore the concern of chemist is also constantly subjected to the research of its synthetic method.Currently, such Compound is mainly synthesized by following approach: the hydrolysis, the oxidation of furan derivatives, 2- of dihydrofuran class compound under acid catalysis The oxidation of butylene-1,4-diol class compound and palladium chtalyst carbonylation etc..Although these methods can be synthesized effectively 4- oxo -2- butylene aldehyde compound, but there are still some urgent problems, such as expensive, the production of raw materials and reagents The configuration (E type and Z-type) of object is difficult to control, the poor compatibility of substrate functional group, severe reaction conditions and reaction step are cumbersome Deng these shortcomings are but also the practicability of the above method is very limited.In view of this, further study and develop from The raw material being easy to get, which sets out, synthesizes the simple and direct, efficient of 4- oxo -2- butylene aldehyde compound and selective high green new method tool There is important meaning.
Summary of the invention
The technical problem to be solved by the present invention is to provide the synthesis sides of one kind (E) -4- oxo -2- butylene aldehyde compound Method, the synthetic method directly obtain (E) -4- oxo -2- butylene from the raw material simply easily prepared, by one pot of tandem reaction Aldehyde compound, easy to operate, mild condition, wide application range of substrates are suitable for industrialized production.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, one kind (E) -4- oxo -2- butylene aldehydes Close the synthetic method of object, it is characterised in that: high allyl alcohols compound 1 is dissolved in organic solvent, nitrous acid is then added Special butyl ester and oxidant react in 40-100 DEG C (E) -4- oxo -2- butylene aldehydes chemical combination is made in the presence of air or oxygen Object 2, the reaction equation in the synthetic method are as follows:
Wherein R1For 1- naphthalene, 4- pyridyl group, 2- thienyl, phenyl or substituted-phenyl, taking on the substituted-phenyl phenyl ring One of Dai Jiwei fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxyl group are a variety of, and the position of substituent group is the neighbour on phenyl ring Position, meta or para position, R2For hydrogen, alkyl or phenyl, R3For hydrogen or alkyl, oxidant is tetramethyl piperidine nitrogen oxides (TEMPO) Or hydrogen peroxide (H2O2), organic solvent is toluene, acetonitrile, Isosorbide-5-Nitrae dioxane or dichloroethanes.
It further limits, the ratio between the amount of the substance that feeds intake of the high allyl alcohols compound 1 and nitrous acid special butyl ester For 1:1-3, the ratio between amount for the substance that feeds intake of the high allyl alcohols compound 1 and oxidant is 1:0.5-2.
Compared with the prior art, the present invention has the following advantages: (1) synthesis process be one pot tandem reaction, easy to operate, It is high-efficient；(2) raw material is easily prepared；(3) reaction is carried out at 100 DEG C or less, and mild condition is easy to operate；(4) substrate is applicable Range is wide；(5) product configuration stereoselectivity is high.Therefore, the present invention is the synthesis of (E) -4- oxo -2- butylene aldehyde compound Provide a kind of economical and practical and environmentally protective new method.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
1a (0.5mmol, 74mg) and dichloroethanes (DCE, 3mL) are added in the reaction flask of 25mL, nitrous is then added Sour spy's butyl ester (t-BuONO, TBN, 1mmol, 108 μ L) and TEMPO (1mmol, 78mg).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (54mg, 68%).The characterize data of the compound is as follows:1H NMR (400MHz,CDCl3)δ:7.00(dd,J1=15.6Hz, J2=7.6Hz, 1H), 7.55 (t, J=7.6Hz, 2H), 7.65-7.75 (m, 2H), 7.99-8.01 (m, 2H), 9.90 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:128.9,129.1, 134.2,136.3,139.2,142.1,189.8,192.8.MS:m/z 161[MH]+。
Embodiment 2
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).It is anti-in 70 DEG C of stirrings in air atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (40mg, 50%).
Embodiment 3
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).It is anti-in 70 DEG C of stirrings in a nitrogen atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (7mg, 8%).
Embodiment 4
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1.5mmol, 162 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).It is stirred in air atmosphere in 70 DEG C Then reaction 10 hours is added 8mL saturated sodium chloride solution quenching reaction, is extracted with ethyl acetate (8mL × 3), merge organic Phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (39mg, 48%).
Embodiment 5
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (0.5mmol, 54 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).It is anti-in 70 DEG C of stirrings in air atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (24mg, 30%).
Embodiment 6
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (1mmol, 156mg) is then added in (3mL).It is stirred to react in air atmosphere in 70 DEG C 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 2), merges organic phase, nothing Aqueous sodium persulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E)- 4- oxo -4- phenyl -2- crotonaldehyde 2a (56mg, 70%).
Embodiment 7
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.25mmol, 39mg) is then added in (3mL).It is anti-in 70 DEG C of stirrings in air atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=20:1) and is obtained yellow liquid product (E)- 4- oxo -4- phenyl -2- crotonaldehyde 2a (25mg, 31%).
Embodiment 8
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and H is then added in (3mL)2O2(0.5mmol, 51 μ L, 30wt% aqueous solutions).In oxygen (1atm) gas It is stirred to react under atmosphere in 70 DEG C 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, (8mL is extracted with ethyl acetate × 3), merge organic phase, anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) Obtain yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (4mg, 5%).
Embodiment 9
By method described in embodiment 1,1a (0.5mmol, 74mg) and toluene (3mL) are added in the reaction flask of 25mL, Then TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is added.It is anti-in 70 DEG C of stirrings under oxygen (1atm) atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (47mg, 58%).
Embodiment 10
By method described in embodiment 1,1a (0.5mmol, 74mg) and acetonitrile (3mL) are added in the reaction flask of 25mL, Then TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is added.It is anti-in 70 DEG C of stirrings under oxygen (1atm) atmosphere It answers 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge organic phase, Anhydrous sodium sulfate is dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (33mg, 41%).
Embodiment 11
By method described in embodiment 1,1a (0.5mmol, 74mg) and Isosorbide-5-Nitrae-dioxy six are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in ring (3mL).In 70 under oxygen (1atm) atmosphere It DEG C is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), close And organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Body product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (29mg, 36%).
Embodiment 12
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 40 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (34mg, 42%).
Embodiment 13
By method described in embodiment 1,1a (0.5mmol, 74mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 100 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product (E) -4- oxo -4- phenyl -2- crotonaldehyde 2a (50mg, 63%).
Embodiment 14
By method described in embodiment 1,1b (0.5mmol, 113mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2b (66mg, 55%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:6.75(dd,J1= 16.0Hz,J2=7.6Hz, 1H), 7.35-7.47 (m, 4H), 7.67 (dd, J1=8.0Hz, J2=0.8Hz, 1H), 9.88 (d, J =7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:119.7,127.8,129.8,132.8,133.8,139.25, 139.31,144.2,192.9,193.5.HRMS calcd for C10H8BrO2:238.9702[M+H]+,found: 238.9698。
Embodiment 15
By method described in embodiment 1,1c (0.5mmol, 83mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2c (56mg, 63%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:7.01(dd,J1= 15.6Hz,J2=7.2Hz, 1H), 7.34-7.39 (m, 1H), 7.51-7.57 (m, 1H), 7.66-7.70 (m, 2H), 7.78 (dd, J1=7.6Hz, J2=1.2Hz, 1H), 9.90 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:115.6(d,2JC-F =22.8Hz), 121.3 (d,2JC-F=21.4Hz), 124.7 (d,4JC-F=3.0Hz), 130.8 (d,3JC-F=7.2Hz), 138.3(d,3JC-F=6.9Hz), 139.6,141.2,163.0 (d,1JC-F=247.6Hz), 188.6 (d,4JC-F=2.7Hz), 192.6.HRMS calcd for C10H8FO2:179.0503[M+H]+,found:179.0505。
Embodiment 16
By method described in embodiment 1,1d (0.5mmol, 91mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2d (64mg, 66%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:7.01(dd,J1= 15.6Hz,J2=7.2Hz, 1H), 7.50 (t, J=8.0Hz, 1H), 7.62-7.86 (m, 2H), 7.87 (d, J=8.0Hz, 1H), 7.97 (d, J=1.6Hz, 1H), 9.90 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:126.9,128.9, 130.4,134.1,135.5,137.8,139.6,141.1,188.6,192.5.HRMS calcd for C10H8ClO2: 195.0207[M+H]+,found:195.0213。
Embodiment 17
By method described in embodiment 1,1e (0.5mmol, 81mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2e (52mg, 60%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.47(s,3H),7.00 (dd,J1=16.0Hz, J2=8.0Hz, 1H), 7.44-7.48 (m, 2H), 7.73 (d, J=16.0Hz, 1H), 7.79-7.82 (m, 2H), 9.91 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:21.4,126.2,128.9,129.4,130.6, 135.0,136.4,139.0,142.4,190.0,193.0.HRMS calcd for C11H11O2:175.0754[M+H]+, found:175.0759。
Embodiment 18
By method described in embodiment 1,1f (0.5mmol, 81mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2f (63mg, 72%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.39(s,3H),6.92 (dd,J1=16.0Hz, J2=7.6Hz, 1H), 7.27 (d, J=8.0Hz, 2H), 7.65 (d, J=15.6Hz, 1H), 7.83 (d, J =8.8Hz, 2H), 9.82 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:21.8,129.1,129.8,133.8, 138.9,142.4,145.4,189.2,192.9.MS:m/z 175[MH]+.HRMS calcd for C11H11O2:175.0754 [M+H]+,found:175.0758。
Embodiment 19
By method described in embodiment 1,1g (0.5mmol, 83mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering is spin-dried for, and is crossed silica gel post separation (petrol ether/ethyl acetate=20:1) and is obtained yellow liquid Product 2g (54mg, 61%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:6.93(dd,J1= 15.6Hz,J2=7.2Hz, 1H), 7.15 (t, J=7.6Hz, 2H), 7.63 (d, J=15.6Hz, 1H), 7.96-7.99 (m, 2H), 9.83 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:116.3(d,2JC-F=22.3Hz), 131.7 (d,3JC-F=9.8Hz), 132.7 (d,4JC-F=3.0Hz), 139.2,141.6,166.4 (d,1JC-F=254.9Hz), 188.1, 192.7.HRMS calcd for C10H8FO2:179.0503[M+H]+,found:179.0503。
Embodiment 20
By method described in embodiment 1,1h (0.5mmol, 104mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=10:1) and obtains yellow liquid Product 2h (68mg, 62%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:3.95(s,3H),3.98 (s, 3H), 6.92-7.01 (m, 2H), 7.57 (d, J=2.0Hz, 1H), 7.62 (dd, J1=8.0Hz, J2=2.0Hz, 1H), 7.75 (d, J=15.6Hz, 1H), 9.87 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:56.1,56.2, 110.1,110.5,124.2,129.6,138.6,142.2,149.7,154.5,187.7,193.0.HRMS calcd for C12H13O4:221.0808[M+H]+,found:221.0812。
Embodiment 21
By method described in embodiment 1,1i (0.5mmol, 120mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2i (76mg, 60%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.45(s,3H),6.48 (dd,J1=7.6Hz, J2=1.2Hz, 1H), 7.28-7.42 (m, 3H), 7.61 (d, J=7.6Hz, 1H), 10.29 (dd, J1= 7.6Hz,J2=0.8Hz, 1H)13C NMR(100MHz,CDCl3)δ:12.1,119.5,127.5,129.0,131.9,133.2, 135.6,139.4,151.6,192.2,198.9.HRMS calcd for C11H10BrO2:252.9859[M+H]+,found: 252.9865。
Embodiment 22
By method described in embodiment 1,1j (0.5mmol, 88mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2j (71mg, 75%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.31(s,3H),2.36 (d, J=1.6Hz, 3H), 6.13 (dd, J1=7.6Hz, J2=1.6Hz, 1H), 7.24-7.33 (m, 2H), 7.47-7.51 (m, 2H), 10.17 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3)δ:14.2,21.3,127.0,128.5,130.1, 132.5,134.4,135.3,138.6,153.5,191.5,198.0.HRMS calcd for C12H13O2:189.0910[M+H ]+,found:189.0911。
Embodiment 23
By method described in embodiment 1,1k (0.5mmol, 90mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2k (69mg, 72%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.38 (d, J= 1.2Hz,3H),6.17(dd,J1=7.2Hz, J2=1.6Hz, 1H), 7.20-7.25 (m, 1H), 7.39-7.42 (m, 2H), 7.48 (dd,J1=6.0Hz, J2=1.2Hz, 1H), 10.20 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:14.0, 116.3(d,2JC-F=22.6Hz), 120.6 (d,2JC-F=21.6Hz), 125.5 (d,4JC-F=3.1Hz), 130.5 (d,3JC-F =7.6Hz), 133.1,137.4 (d,3JC-F=5.6Hz), 152.4,162.6 (d,1JC-F=247.1Hz), 191.3,196.5 (d,4JC-F=2.0Hz) .HRMS calcd for C11H10FO2:193.0659[M+H]+,found:193.0663。
Embodiment 24
By method described in embodiment 1,1l (0.5mmol, 88mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2l (77mg, 74%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.38 (d, J= 1.6Hz,3H),6.16(dd,J1=7.6Hz, J2=1.6Hz, 1H), 7.36 (t, J=8.0Hz, 1H), 7.49-7.52 (m, 1H), 7.55-7.58 (m, 1H), 7.67 (t, J=1.6Hz, 1H), 10.20 (d, J=7.6Hz, 1H)13C NMR(100MHz,CDCl3) δ:14.0,127.8,129.5,130.0,133.2,133.4,135.0,137.1,152.4,191.4,196.5.HRMS calcd for C11H10ClO2:209.0364[M+H]+,found:209.0367。
Embodiment 25
By method described in embodiment 1,1m (0.5mmol, 120mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2m (98mg, 78%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.36 (d, J= 1.6Hz,3H),6.12(dd,J1=7.6Hz, J2=1.2Hz, 1H), 7.52-7.58 (m, 4H), 10.17 (d, J=7.6Hz, 1H).13C NMR(100MHz,CDCl3)δ:14.1,128.8,131.2,132.0,132.8,134.1,152.6,191.3, 196.8.HRMS calcd for C11H10BrO2:252.9859[M+H]+,found:252.9863。
Embodiment 26
By method described in embodiment 1,1n (0.5mmol, 111mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2n (100mg, 85%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.42 (d, J= 1.6Hz,3H),3.90(s,3H),3.93(s,3H),6.14(dd,J1=8.0Hz, J2=1.2Hz, 1H), 6.85 (d, J= 8.4Hz,1H),7.36(dd,J1=8.0Hz, J2=2.0Hz, 1H), 7.42 (d, J=2.0Hz, 1H), 10.21 (d, J= 7.6Hz,1H).13C NMR(100MHz,CDCl3)δ:14.7,56.0,56.2,109.9,111.1,125.4,127.7,131.1, 149.4,154.1,154.2,191.3,196.2.HRMS calcd for C13H15O4:235.0965[M+H]+,found: 235.0975。
Embodiment 27
By method described in embodiment 1,1o (0.5mmol, 106mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2o (90mg, 80%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.55 (d, J= 1.2Hz,3H),6.28(dd,J1=7.2Hz, J2=1.2Hz, 1H), 7.49-7.59 (m, 4H), 7.92 (m, 1H), 8.03 (d, J =8.0Hz, 1H), 8.12 (d, J=8.8Hz, 1H), 10.32 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ: 13.1,124.3,125.2,126.8,127.8,128.4,128.6,130.8,132.4,133.8,134.4,135.3,153.7, 192.1,200.1.HRMS calcd for C15H13O2:225.0910[M+H]+,found:225.0913。
Embodiment 28
By method described in embodiment 1,1p (0.5mmol, 82mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=10:1) and obtains yellow liquid Product 2p (52mg, 59%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.47 (d, J= 1.6Hz, 3H), 6.30 (d, J=7.2Hz, 1H), 7.54 (dd, J1=4.4Hz, J2=1.6Hz, 2H), 8.82-8.84 (m, 2H), 10.32 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:13.3,119.9,122.3,134.9,142.5, 150.7,191.3,197.0.HRMS calcd for C10H10NO2:176.0706[M+H]+,found:176.0701。
Embodiment 29
By method described in embodiment 1,1q (0.5mmol, 112mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2q (95mg, 80%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 6.34 (d, J= 7.6Hz,1H),7.43-7.50(m,7H),7.58-7.62(m,1H),7.91(dd,J1=7.2Hz, J2=1.2Hz, 2H), 9.84 (d, J=7.2Hz, 1H)13C NMR(100MHz,CDCl3)δ:128.8,128.9,129.8,130.1,130.2,130.7, 132.4,134.1,135.2,157.2,192.7,195.4.HRMS calcd for C16H13O2:237.0910[M+H]+, found:237.0908。
Embodiment 30
By method described in embodiment 1,1r (0.5mmol, 121mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2r (99mg, 78%).The characterize data of the compound is as follows:1H NMR(600MHz,CDCl3) δ: 6.33 (d, J= 7.8Hz, 1H), 7.13-7.16 (m, 2H), 7.46-7.48 (m, 5H), 7.93-7.95 (m, 2H), 9.84 (d, J=7.8Hz, 1H).13C NMR(150MHz,CDCl3)δ:116.2(d,2JC-F=21.9Hz), 129.0,129.7,130.3,130.6,131.6 (d,4JC-F=2.3Hz), 132.3,132.8 (d,3JC-F=9.9Hz), 157.0,166.3 (d,1JC-F=258.2Hz), 192.5, 193.8.HRMS calcd for C16H12FO2:255.0816[M+H]+,found:255.0840。
Embodiment 31
By method described in embodiment 1,1s (0.5mmol, 120mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2s (90mg, 71%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.03 (d, J= 1.2Hz, 3H), 7.30-7.37 (m, 2H), 7.68-7.71 (m, 1H), 7.82-7.84 (m, 1H), 8.04 (t, J=1.6Hz, 1H),9.63(s,1H).13C NMR(100MHz,CDCl3)δ:10.5,122.3,126.1,129.5,130.5,135.7, 137.7,137.8,148.0,189.4,193.3.HRMS calcd for C11H10BrO2:252.9859[M+H]+,found: 252.9861。
Embodiment 32
By method described in embodiment 1,1t (0.5mmol, 120mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2t (88mg, 70%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.08 (d, J= 1.6Hz, 3H), 7.38 (t, J=1.6Hz, 1H), 7.67 (dd, J1=6.8Hz, J2=2.0Hz, 2H), 7.84 (dd, J1= 6.8Hz,J2=1.6Hz, 2H), 9.69 (s, 1H)13C NMR(100MHz,CDCl3)δ:11.5,127.5,129.3,130.1, 132.3,139.1,148.6,190.9,194.4.HRMS calcd for C11H10BrO2:252.9859[M+H]+,found: 252.9861。
Embodiment 33
By method described in embodiment 1,1u (0.5mmol, 115mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow liquid Product 2u (91mg, 75%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.05 (d, J= 1.6Hz, 3H), 7.35 (d, J=1.6Hz, 1H), 7.73 (d, J=8.8Hz, 2H), 8.02 (d, J=8.4Hz, 2H), 9.65 (s, 1H).13C NMR(150MHz,CDCl3)δ:11.6,123.5(d,1JC-F=271.2Hz), 126.4 (d,4JC-F=3.6Hz), 128.9(d,3JC-F=5.9Hz), 130.9,135.1 (d,2JC-F=32.7Hz), 139.8,149.4,190.8,194.2.HRMS calcd for C12H10F3O2:243.0627[M+H]+,found:243.0631。
Embodiment 34
By method described in embodiment 1,1v (0.5mmol, 96mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2v (84mg, 82%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.04(s,3H),3.90 (s, 3H), 7.00 (d, J=9.6Hz, 2H), 7.39 (d, J=1.2Hz, 1H), 7.96 (d, J=9.2Hz, 2H), 9.68 (s, 1H).13C NMR(100MHz,CDCl3)δ:11.3,55.6,127.0,130.1,131.1,141.0,147.0,164.3, 190.7,194.7.HRMS calcd for C12H13O3:205.0859[M+H]+,found:205.0862。
Embodiment 35
By method described in embodiment 1,1w (0.5mmol, 106mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2w (67mg, 60%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3) δ: 2.10 (d, J= 1.2Hz, 3H), 7.34 (d, J=1.6Hz, 1H), 7.52-7.68 (m, 3H), 7.90-7.94 (m, 2H), 8.07 (d, J= 8.4Hz, 1H), 8.77 (d, J=8.8Hz, 1H), 9.68 (s, 1H)13C NMR(100MHz,CDCl3)δ:11.3,124.5, 125.5,126.9,128.6,128.7,130.0,130.2,134.0,134.1,134.8,143.0,147.4,194.9, 195.0.HRMS calcd for C15H13O2:225.0910[M+H]+,found:225.0915。
Embodiment 36
By method described in embodiment 1,1x (0.5mmol, 84mg) and dichloroethanes are added in the reaction flask of 25mL TBN (1mmol, 108 μ L) and TEMPO (0.5mmol, 78mg) is then added in (3mL).In 70 DEG C under oxygen (1atm) atmosphere It is stirred to react 10 hours, 8mL saturated sodium chloride solution quenching reaction is then added, is extracted with ethyl acetate (8mL × 3), merge Organic phase, anhydrous sodium sulfate are dry.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20:1) and obtains yellow solid Product 2x (67mg, 74%).The characterize data of the compound is as follows:1H NMR(400MHz,CDCl3)δ:2.18(s,3H),7.21 (t, J=4.4Hz, 1H), 7.37 (s, 1H), 7.78 (d, J=4.0Hz, 1H), 7.82 (d, J=4.0Hz, 1H), 9.68 (s, 1H).13C NMR(100MHz,CDCl3)δ:11.4,128.6,132.9,135.5,138.4,145.0,148.9,183.4, 194.7.HRMS calcd for C9H9O2S:181.0318[M+H]+,found:181.0317。
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. the synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound, it is characterised in that: by high allyl alcohols chemical combination Object 1 is dissolved in organic solvent, and nitrous acid special butyl ester and oxidant is then added, anti-in 40-100 DEG C in the presence of air or oxygen (E) -4- oxo -2- butylene aldehyde compound 2, the reaction equation in the synthetic method should be made are as follows:
Wherein R1For 1- naphthalene, 4- pyridyl group, 2- thienyl, phenyl or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring is One of fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxyl group are a variety of, and the position of substituent group is the ortho position on phenyl ring, meta position Or contraposition, R2For hydrogen, alkyl or phenyl, R3For hydrogen or alkyl, oxidant is tetramethyl piperidine nitrogen oxides, and organic solvent is first Benzene, acetonitrile, 1,4 dioxane or dichloroethanes.
2. the synthetic method of (E) -4- oxo -2- butylene aldehyde compound according to claim 1, it is characterised in that: institute The ratio between amount for the substance that feeds intake of the high allyl alcohols compound 1 and nitrous acid special butyl ester stated is 1:1-3, the high allyl The ratio between amount for the substance that feeds intake of alcohol compound 1 and oxidant is 1:0.5-2.
CN201610735258.5A 2016-08-26 2016-08-26 The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound Expired - Fee Related CN106631646B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610735258.5A CN106631646B (en) 2016-08-26 2016-08-26 The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610735258.5A CN106631646B (en) 2016-08-26 2016-08-26 The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound

Publications (2)

Publication Number Publication Date
CN106631646A CN106631646A (en) 2017-05-10
CN106631646B true CN106631646B (en) 2019-04-09

Family

ID=58851657

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610735258.5A Expired - Fee Related CN106631646B (en) 2016-08-26 2016-08-26 The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound

Country Status (1)

Country Link
CN (1) CN106631646B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976106B (en) * 2018-09-10 2021-02-19 河南师范大学 (E) Synthesis method of (E) -2-methylene-1, 4-butanedione compounds
CN108863750B (en) * 2018-09-10 2021-02-19 河南师范大学 Synthetic method of 2-butene-1, 4-diketone compound
CN109776308B (en) * 2019-02-21 2021-08-03 河南师范大学 Synthesis method of N- (3-cyanopropyl) formamide compound
CN109761845B (en) * 2019-02-21 2021-08-20 河南师范大学 Synthesis method of N-nitroso-4-aminobutyric acid ester compound
CN109896989B (en) * 2019-05-06 2021-09-10 河南师范大学 Synthesis method of 5-oxo-2H-aromatic ring [ g ] indole-1-oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
联烯酮及联烯醇的一些反应性能研究;何艳等;《中国化学会第八届有机化学学术会议暨首届重庆有机化学国际研讨会》;20131017;第29页

Also Published As

Publication number Publication date
CN106631646A (en) 2017-05-10

Similar Documents

Publication Publication Date Title
CN106631646B (en) The synthetic method of one kind (E) -4- oxo -2- butylene aldehyde compound
CN106588747B (en) A kind of synthetic method of aromatic ring simultaneously [a] carbazole compound
CN100391945C (en) S-(-)-indolyl-2-carboxylic acid synthesizing method
CN108033922B (en) Preparation method of 3-acyl quinoxalinone derivative
CN107141207B (en) Synthetic method of 3 '-acyl-2, 4' -dihydroxy benzophenone compound
CN109761943A (en) A kind of synthetic method of C-3 alkyl substituted cumarin derivative
CN106632214A (en) Synthetic method for cannabinol compound
CN110066254A (en) A kind of isothiazole -3- ketone compound and preparation method thereof
CN108640917A (en) A kind of synthetic method of indoles simultaneously [2,1-a] isoquinoline compound
CN106431800B (en) (E) synthetic method of -4- oxo -2- butylene aldehyde compound
CN107602452B (en) Synthetic method of 3-acyl pyridine compound
CN107629064B (en) A kind of synthetic method of Azacyclooctane and Furanones compound
CN106749071B (en) A kind of preparation method of aromatics 1,2,4,5- tetrazine compound
CN106946881B (en) A kind of amino replaces the synthetic method of naphtho- Quinolizinone type compounds
CN107739332A (en) A kind of synthetic method of the formic ether compounds of pyridine 3
CN107501278A (en) A kind of synthetic method of the ketone of 5H furans 2 and piperidines
CN107141258A (en) A kind of method that the acyl group pyrazole compound of side chain functionalitiesization 4 is synthesized by cyclic ketones hydrazone
CN106866654B (en) A kind of synthetic method of naphtho- quinolizine ketone -11- amides compound
CN109369495A (en) A kind of synthetic method of pyrrolidones
CN105348159B (en) A kind of thio Methomyl of lead compound and its synthetic method
CN108516952A (en) A kind of synthetic method of the hexa-atomic nitrogen-containing hetero cyclics of 3- acyl groups
CN108424416A (en) A kind of method of synthesis of indole [1,2-c] quinazoline compounds
CN106588644A (en) Synthesis method of carboxylic ester compound
CN111087402B (en) Method for asymmetrically synthesizing Epicocin G alkaloid of ETP natural product
CN102079720B (en) Method for preparing 1-benzylpiperidine-4-carboxaldehyde

Legal Events

Date Code Title Description
PB01 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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190409

Termination date: 20210826

CF01 Termination of patent right due to non-payment of annual fee