CN109400496A - A kind of environment-friendly preparation method thereof of 1,3- diacetylene derivative - Google Patents
A kind of environment-friendly preparation method thereof of 1,3- diacetylene derivative Download PDFInfo
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- CN109400496A CN109400496A CN201811311751.XA CN201811311751A CN109400496A CN 109400496 A CN109400496 A CN 109400496A CN 201811311751 A CN201811311751 A CN 201811311751A CN 109400496 A CN109400496 A CN 109400496A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
Abstract
The present invention relates to the green synthesis methods of one kind 1,3- diacetylene derivative.This method is by the way that alkyl end acetylene compound (1), copper acetate (Cu (OAc) are added into Schlenk reaction flask2), di-t-butyl peroxide (DTBP) and solvent acetonitrile, reaction flask is placed under the conditions of certain temperature, air atmosphere and is stirred to react, reaction process is monitored through TLC or GC, until raw material fully reacting, it is post-treated to obtain target product 1,3- diacetylene derivative (I)；
Description
Technical field
The application belongs to organic synthesis field, and in particular to the synthetic method of one kind 1,3- diacetylene derivative.
Background technique
1,3- diacetylene derivative is widely present in drug molecule and bioactive molecule, medicine, in terms of
Using very extensive.In addition, 1,3- diacetylene is also very important synthon in organic synthesis and functional material.Therefore, 1,
The efficient preparation of 3- diacetylene derivative causes the extensive and long-term concern of chemists.
Inventors have found that prepare 1 in the prior art, the route of synthesis of 3- diacetylene derivative mainly pass through Terminal Acetylenes palladium,
Coupling reaction under the metal catalytics such as copper.However, being generally required in reaction system in the method for these conventional synthesis technologies
It adds expensive ligand and/or uses alkali, and the typically no high efficiency method developed specifically for the coupling of alkyl Terminal Acetylenes.Cause
This, finds a kind of more efficient, more cheap, more green side that 1,3- diacetylene derivative is prepared by alkyl Terminal Acetylenes coupling reaction
Method is still the project of a challenge.Inventor carries out alkyl Terminal Acetylenes coupling reaction building 1,3- diacetylene derivative
The research of series, it is further proposed that a kind of new preparation 1, the green method of 3- diacetylene derivative.According to the inventors knowledge, at present
It was reported there are no the prior art and prepares 1,3- fourth two specifically for alkyl Terminal Acetylenes coupling reaction under without ligand and alkali systems
The reaction of alkyne derivatives.
Summary of the invention
The purpose of the present invention is to overcome the deficiency in the prior art, provides the system of a kind of simple process, green high-efficient, low cost
The synthetic method of standby 1,3- diacetylene derivative, this method is with copper acetate (Cu (OAc) cheap and easy to get2) it is catalyst, with mistake
Aoxidizing di-t-butyl (DTBP) is oxidant, and acetonitrile is solvent, easily and with higher yield prepares 1,3- diacetylene
Derivative.
The preparation method of 1,3- diacetylene derivative provided by the invention, this method are original with alkyl end acetylene compound
Material, is prepared through the following steps:
Alkyl end acetylene compound (1), copper acetate (Cu (OAc) are added into Schlenk reaction flask2), two uncle of peroxidating
Butyl (DTBP) and solvent acetonitrile, reaction flask is placed under the conditions of certain temperature, air atmosphere and is stirred to react, and is supervised through TLC or GC
Reaction process is surveyed, until raw material fully reacting, post-treated to obtain target product 1,3- diacetylene derivative (I).
The preparation method of 1,3- diacetylene derivative provided by the invention, chemical equation can be expressed as (see formula one):
In the reaction of above-mentioned formula one, the reaction atmosphere is the air atmosphere of 1atm, also could alternatively be the nitrogen of 1atm
Gas atmosphere or other inert gas atmospheres consider, preferably air atmosphere from economic cost etc..
The post-processing operation is as follows: reaction solution being filtered by the glass dropper equipped with silica gel, ethyl acetate rinse
Filter cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane,
Obtain target product 1,3- diacetylene derivative (I).
In the compound that formula 1 and Formulas I indicate, in the compound that formula 1 and Formulas I indicate, R1Indicate 1 or more that it is connected
A substituent group, each R1It is independently from each other hydrogen, C6-C10Aryl, C5-C14Heteroaryl, C1-C12Alkyl；
R2Indicate C1-C6Alkyl, C3-C6Acyl group, C6-C10Aryl；
Wherein, the hetero atom of the heteroaryl is selected from O, S or N；
And above-mentioned each alkyl, alkoxy, aryl and heteroaryl can be further substituted with a substituent, the substitution
Base is selected from halogen or C1-C6Alkyl.
Preferably, R1Indicate its one or more substituent group connected, each R1It is independently from each other hydrogen, C6-C8Virtue
Base and C1-C10Alkyl；The wherein C6-C8Aryl and/or C1-C10Alkyl can be further substituted, and the substituent group is selected from halogen
Element or C1-C6Alkyl；
Preferably, R2Indicate C1-C5Alkyl and C3-C4Acyl group, wherein the C1-C5Alkyl and/or C3-C4Acyl group can be into
One step is substituted, and the substituent group is selected from halogen or C1-C2Alkyl.
In reaction of the invention, it is preferably added copper acetate (Cu (OAc)2) it is used as catalyst and the tertiary fourth of peroxidating two
Base (DTBP) is used as oxidant.
In reaction of the invention, the certain temperature is 25-100 DEG C, and temperature is most preferably 70 DEG C.
In reaction of the invention, the compound and Cu (OAc) of the formula 12Molar ratio be 1: 0.1~0.3, preferably
Ground, the compound and Cu (OAc) of formula 12Molar ratio be 1: 0.2；The compound of formula 1 and the molar ratio of DTBP are 1: 1~4, excellent
Selection of land, the compound of formula 1 and the molar ratio of DTBP are 1: 3.
In the reaction of the present invention, acetonitrile does not limit particularly as solvent, dosage, and those skilled in the art can
Conventional selection is carried out with the actual conditions according to reaction and/or adjusts its dosage.
The beneficial effects of the present invention are: proposing a kind of anti-without being coupled under ligand and alkali systems specifically for alkyl Terminal Acetylenes
The new method of 1,3- diacetylene derivative should be prepared, this method is using copper acetate cheap and easy to get as catalyst, to obtain in high yield
1, the 3- diacetylene target product of a series of nitrogenous special skeleton.This method is air without using ligand and alkali, reaction atmosphere,
Have the advantages that reaction substrate adaptation range is extensive, be simple and efficient, be economical and eco-friendly, particularly suitable for industrialized production.
Specific embodiment
Below in conjunction with specific embodiment, further detailed description is carried out to the present invention.
The synthesis of 1 compound I-1 of embodiment
1a (39.8mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvents tetrahydrofurane (1mL), reaction flask is placed in
70 DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
1.(81%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.41 (t, J=7.6Hz, 4H), 7.32 (t, J=7.6Hz,
2H), 7.24 (d, J=7.6Hz, 4H), 5.06 (s, 2H), 4.90 (s, 2H), 4.63 (s, 4H), 1.71 (s, 6H)；13C NMR
(100MHz, DMSO-d6) δ: 170.8,142.6,140.1,129.8,128.0,127.8,120.0,75.4,67.6,39.5,
20.3；HRMS m/z(ESI)calcd for C26H25N2O2([M+H]+) 397.1911, found 397.1919.
Embodiment 2
It is added without catalyst Cu (OAc)2, remaining condition is 0% with embodiment 1, the yield of target product I-1.
Embodiment 3
It is added without oxidant DTBP, remaining condition is 5% with embodiment 1, the yield of target product I-1.
Embodiment 4
Use CuCl2Instead of the Cu (OAc) in embodiment 12, remaining condition with embodiment 1, through TLC or GC monitoring react into
Journey, until raw material fully reacting (12 hours reaction time), passes through the glass dropper equipped with silica gel for reaction solution after the reaction was completed
Filtering, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows:
Ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 76%.
Embodiment 5
Use CuBr2Instead of the Cu (OAc) in embodiment 12, remaining condition with embodiment 1, through TLC or GC monitoring react into
Journey, until raw material fully reacting (12 hours reaction time), passes through the glass dropper equipped with silica gel for reaction solution after the reaction was completed
Filtering, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows:
Ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 42%.
Embodiment 6
The Cu (OAc) in embodiment 1 is replaced with CuO2, remaining condition monitors reaction process with embodiment 1, through TLC or GC,
To raw material fully reacting (12 hours reaction time), reaction solution after the reaction was completed is passed through into the glass dropper mistake equipped with silica gel
Filter, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows: second
Acetoacetic ester/n-hexane, the yield for obtaining target product I-1 is 32%.
Embodiment 7
The Cu (OAc) in embodiment 1 is replaced with CuCl2, remaining condition with embodiment 1, through TLC or GC monitoring react into
Journey, until raw material fully reacting (12 hours reaction time), passes through the glass dropper equipped with silica gel for reaction solution after the reaction was completed
Filtering, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows:
Ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 11%.
Embodiment 8
Catalyst Cu (OAc)2Inventory be 0.1 equivalent (0.02mmol), remaining condition is with embodiment 1, through TLC or GC
Reaction process is monitored, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with silica gel
Glass dropper filtering, ethyl acetate rinse filter cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation,
Eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 34%.
Embodiment 9
Catalyst Cu (OAc)2Inventory be 0.3 equivalent (0.06mmol), remaining condition is with embodiment 1, through TLC or GC
Reaction process is monitored, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with silica gel
Glass dropper filtering, ethyl acetate rinse filter cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation,
Eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 62%.
Embodiment 10
The DTBP in embodiment 1 is replaced with oxidant TBHP (tertbutanol peroxide), remaining condition is with embodiment 1, through TLC
Or GC monitors reaction process, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with
The glass dropper of silica gel filters, and ethyl acetate rinse filter cake filters and be concentrated under reduced pressure removing solvent, by residue through column chromatography point
From eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 33%.
Embodiment 11
The DTBP in embodiment 1 is replaced with oxidant BPO (benzoyl peroxide), remaining condition is with embodiment 1, through TLC
Or GC monitors reaction process, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with
The glass dropper of silica gel filters, and ethyl acetate rinse filter cake filters and be concentrated under reduced pressure removing solvent, by residue through column chromatography point
From eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 45%.
Embodiment 12
With oxidant PhI (OAc)2(iodobenzene acetate) replaces the DTBP in embodiment 1, remaining condition is the same as embodiment 1, warp
TLC or GC monitors reaction process, until raw material fully reacting (12 hours reaction time), passes through dress for reaction solution after the reaction was completed
There is the glass dropper of silica gel to filter, ethyl acetate rinse filter cake filters and is concentrated under reduced pressure removing solvent, residue is chromatographed through column
Separation, eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 12%.
Embodiment 13
The inventory of oxidant DTBP is 2.0 equivalents (0.4mmol), remaining condition is monitored with embodiment 1 through TLC or GC
Reaction process, until raw material fully reacting (12 hours reaction time), passes through the glass equipped with silica gel for reaction solution after the reaction was completed
The filtering of glass dropper, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, elution
Solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 51%.
Embodiment 14
The tetrahydrofuran in embodiment 1 is replaced with solvent acetonitrile, remaining condition is with embodiment 1, through TLC or GC monitoring reaction
Process, until raw material fully reacting (12 hours reaction time), passes through the glass drop equipped with silica gel for reaction solution after the reaction was completed
Pipe filtering, ethyl acetate rinse filter cake filter and are concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent
Are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 97%.
Embodiment 15
With solvent 1,2- dichloroethanes replaces the tetrahydrofuran in embodiment 1, remaining condition is with embodiment 1, through TLC or GC
Reaction process is monitored, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with silica gel
Glass dropper filtering, ethyl acetate rinse filter cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation,
Eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 50%.
Embodiment 16
The tetrahydrofuran in embodiment 1 is replaced with solvent n,N-Dimethylformamide, remaining condition is with embodiment 1, through TLC
Or GC monitors reaction process, until raw material fully reacting (12 hours reaction time), by reaction solution after the reaction was completed by being equipped with
The glass dropper of silica gel filters, and ethyl acetate rinse filter cake filters and be concentrated under reduced pressure removing solvent, by residue through column chromatography point
From eluting solvent are as follows: ethyl acetate/n-hexane, the yield for obtaining target product I-1 is 79%.
Embodiment 17
Reaction temperature is 90 DEG C, remaining condition monitors reaction process with embodiment 14, through TLC or GC, until raw material has reacted
(12 hours reaction time) entirely is filtered reaction solution after the reaction was completed by the glass dropper equipped with silica gel, ethyl acetate punching
Filter wash cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/just oneself
Alkane, the yield for obtaining target product I-1 is 86%.
Embodiment 18
Reaction temperature is 50 DEG C, remaining condition monitors reaction process with embodiment 14, through TLC or GC, until raw material has reacted
(12 hours reaction time) entirely is filtered reaction solution after the reaction was completed by the glass dropper equipped with silica gel, ethyl acetate punching
Filter wash cake filters and is concentrated under reduced pressure removing solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/just oneself
Alkane, the yield for obtaining target product I-1 is 81%.
The synthesis of 19 compound I-2 of embodiment
1b (29.0mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
2.(81%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.23-7.19 (m, 4H), 6.81 (d, J=8.4Hz, 4H),
6.74 (t, J=7.2Hz, 2H), 4.23 (s, 4H), 2.85 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ: 149.0,
129.4,118.2,114.3,75.9,67.8,42.4,38.7；HRMS m/z(ESI)calcd for C20H21N2([M+H]+)
289.1699, found289.1705.
The synthesis of 20 compound I-3 of embodiment
1c (39.8mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
3.(71%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.19 (t, J=8.0Hz, 4H), 6.79 (d, J=8.0Hz,
4H), 6.71 (t, J=7.2Hz, 2H), 5.17 (t, J=6.4Hz, 2H), 4.16 (s, 4H), 3.87 (d, J=6.4Hz, 4H),
1.69 (s, 6H), 1.68 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ: 148.2,135.2,129.4,121.3,118.0,
114.5,76.4,67.7,48.7,26.0,18.2；HRMS m/z(ESI)calcd for C28H33N2([M+H]+) 397.2638,
found 397.2642.
The synthesis of 21 compound I-4 of embodiment
1d (37.0mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
4.(93%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.50 (t, J=7.6Hz, 4H), 7.43 (t, J=7.2Hz,
2H), 7.28 (d, J=7.6Hz, 4H), 6.22 (d, J=16.8Hz, 2H), 5.97 (t, J=12.8Hz, 2H), 5.63 (d, J=
10.8Hz, 2H), 4.65 (s, 4H)；13C NMR (100MHz, DMSO-d6) δ: 164.6,141.1,130.2,129.1,128.8,
128.5,128.4,75.4,67.6,39.2；HRMS m/z(ESI)calcd for C24H21N2O2([M+H]+) 369.1598,
found 369.1602.
The synthesis of 22 compound I-5 of embodiment
1e (45.8mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
5.(94%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.17 (d, J=9.2Hz, 4H), 6.95 (d, J=8.8Hz,
4H), 5.05 (s, 2H), 4.90 (s, 2H), 4.57 (s, 4H), 3.77 (s, 6H), 1.68 (s, 6H)；13C NMR (100MHz,
DMSO-d6) δ: 170.9,158.8,140.2,135.1,129.2,119.6,114.8,75.5,67.7,55.8,39.6,20.4；
HRMS m/z(ESI)calcd for C28H29N2O4([M+H]+) 457.2122, found 457.2128.
The synthesis of 23 compound I-6 of embodiment
1f (42.6mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
6.(93%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.20 (d, J=8.0Hz, 4H), 7.12 (d, J=8.0Hz,
4H), 5.05 (s, 2H), 4.89 (s, 2H), 4.59 (s, 4H), 2.31 (s, 6H), 1.70 (s, 6H)；13C NMR (100MHz,
DMSO-d6) δ: 170.9,140.2,139.9,137.4,130.2,127.6,119.8,75.5,67.6,39.5,21.0,20.4；
HRMS m/z(ESI)calcd for C28H29N2O2([M+H]+) 425.2224, found 425.2230.
The synthesis of 24 compound I-7 of embodiment
1g (51.0mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
7.(90%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.41 (d, J=8.4Hz, 4H), 7.16 (d, J=8.4Hz,
4H), 5.07 (s, 2H), 4.92 (s, 2H), 4.58 (s, 4H), 1.69 (s, 6H), 1.28 (s, 18H)；13C NMR (100MHz,
DMSO-d6) δ: 170.9,150.4,140.2,140.0,127.2,126.5,119.9,75.6,67.6,39.7,34.8,31.5,
20.3；HRMS m/z(ESI)calcd for C34H41N2O2([M+H]+) 509.3163, found 509.3167.
The synthesis of 25 compound I-8 of embodiment
1h (46.6mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
8.(88%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.47 (d, J=8.8Hz, 4H), 7.29 (d, J=8.8Hz,
4H), 5.11 (s, 2H), 4.91 (s, 2H), 4.64 (s, 4H), 1.73 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ:
170.7,141.4,139.9,132.4,129.7,129.6,120.3,75.3,67.8,39.6,20.3；HRMS m/z(ESI)
calcd for C26H23Cl2N2O2([M+H]+) 465.1131, found 465.1139.
The synthesis of 26 compound I-9 of embodiment
1i (55.4mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
9.(86%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.61 (d, J=8.8Hz, 4H), 7.23 (d, J=8.4Hz,
4H), 5.12 (s, 2H), 4.91 (s, 2H), 4.64 (s, 4H), 1.74 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ:
170.7,141.9,139.9,132.7,129.9,120.8,120.4,75.3,67.8,39.3,20.3；HRMS m/z(ESI)
calcd for C26H23Br2N2O2([M+H]+) 553.0121, found 553.0125.
The synthesis of 27 compound I-10 of embodiment
1j (53.4mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
10.(80%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.78 (d, J=8.4Hz, 4H), 7.49 (d, J=8.4Hz,
4H), 5.15 (s, 2H), 4.91 (s, 2H), 4.71 (s, 4H), 1.77 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ:
170.7,146.3,139.8,128.3,128.2 (q, JC-F=16.0Hz), 126.8 (q, JC-F=2.6Hz), 125.7,120.8,
75.3,67.7,39.6,20.1；19F NMR (375MHz, DMSO-d6) δ: -61.0；HRMS m/z(ESI)calcd for
C28H23F6N2O2([M+H]+) 533.1658, found 533.1664.
The synthesis of 28 compound I-11 of embodiment
1k (42.6mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
11.(89%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.32-7.22 (m, 6H), 7.15 (d, J=6.8Hz, 2H),
5.02 (s, 2H), 4.88 (s, 2H), 4.65 (d, J=18.0Hz, 2H), 4.37 (d, J=18.0Hz, 2H), 2.20 (s, 6H),
1.67 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ: 170.8,141.1,139.9,135.7,131.7,129.4,128.8,
127.3,119.6,75.2,67.7,38.9,20.2,17.9；HRMS m/z(ESI)calcd for C28H29N2O2([M+H]+)
425.224 found 425.2228.
The synthesis of 29 compound I-12 of embodiment
1l (48.2mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
12.(88%yield)；1H NMR (400MHz, DMSO-d6) δ: 6.94 (s, 4H), 5.06 (s, 2H), 4.85 (s, 2H), 4.45
(d, J=8.0Hz, 4H), 2.24 (s, 6H), 2.14 (s, 12H), 1.67 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ:
170.4,139.6,137.8,137.7,135.9,129.9,119.7,75.3,67.8,38.8,20.9,20.0,18.4；HRMS
m/z(ESI)calcd for C32H37N2O2([M+H]+) 481.2850, found 481.2854.
The synthesis of 30 compound I-13 of embodiment
1m (49.8mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
13.(87%yield)；1H NMR (400MHz, DMSO-d6) δ: 8.01 (d, J=8.4Hz, 2H), 7.97 (d, J=8.0Hz,
2H), 7.86 (d, J=6.4Hz, 2H), 7.64-7.51 (m, 6H), 7.41 (t, J=6.0Hz, 2H), 4.87 (d, J=2.0Hz,
2H), 4.82 (t, J=6.8Hz, 4H), 4.44 (d, J=17.6Hz, 2H), 1.63 (s, 6H)；13C NMR (100MHz, DMSO-
D6) δ: 171.6,140.0,138.6,134.6,130.2,129.1,129.0,127.8,127.1,126.2,123.0,118.6,
75.5,68.1,39.6,20.3；HRMS m/z(ESI)calcd for C34H29N2O2([M+H]+) 497.2224, found
497.2228.
The synthesis of 31 compound I-14 of embodiment
1n (42.6mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
14.(85%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.37 (t, J=7.6Hz, 4H), 7.30 (d, J=6.8Hz,
2H), 7.25 (d, J=7.6Hz, 4H), 5.27 (s, 2H), 5.12 (s, 2H), 4.62 (s, 4H), 4.21 (s, 4H), 1.90 (s,
6H)；13C NMR (100MHz, DMSO-d6) δ: 172.0,140.1,137.1,129.1,128.2,127.9,116.3,75.6,
67.7,52.3,39.6,20.6；HRMS m/z(ESI)calcd for C28H29N2O2([M+H]+) 425.2224, found
425.2236.
The synthesis of 32 compound I-15 of embodiment
1o (45.4mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
15.(76%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.29 (t, J=7.6Hz, 4H), 7.21 (d, J=6.4Hz,
6H), 5.16 (s, 2H), 4.85 (s, 2H), 4.35 (s, 4H), 3.60 (t, J=6.8Hz, 4H), 2.86 (t, J=7.6Hz, 4H),
1.67 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ: 171.6,140.3,138.9,129.2,128.9,126.8,115.7,
76.0,67.1,50.6,46.8,34.5,20.4；HRMS m/z(ESI)calcd for C30H33N2O2([M+H]+)
453.2537 found 453.2545.
The synthesis of 33 compound I-16 of embodiment
1p (57.4mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
16.(72%yield)；1H NMR (400MHz, DMSO-d6) δ: 6.84 (t, J=7.6Hz, 4H), 6.71 (d, J=7.6Hz,
2H), 5.16 (s, 2H), 4.85 (s, 2H), 4.33 (s, 4H), 3.73 (s, 6H), 3.70 (s, 6H), 3.58 (t, J=6.4Hz,
4H), 2.78 (t, J=7.2Hz, 4H), 1.68 (s, 6H)；13C NMR (100MHz, DMSO-d6) δ: 171.7,149.2,147.9,
140.3,131.4,121.1,115.7,113.1,112.4,76.0,67.1,56.0,55.9,50.8,46.8,34.1,20.4；
HRMS m/z(ESI)calcd for C34H41N2O6([M+H]+) 573.2959, found 573.2969.
The synthesis of 34 compound I-17 of embodiment
1q (52.6mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
17.(80%yield)；1H NMR (400MHz, DMSO-d6) δ: 8.00 (d, J=7.6Hz, 4H), 7.77 (t, J=7.6Hz,
2H), 7.65 (t, J=7.6Hz, 4H), 5.49 (s, 2H), 5.24 (s, 2H), 4.79 (s, 4H), 1.82 (s, 6H)；13C NMR
(100MHz, DMSO-d6) δ: 171.3,139.1,138.9,134.9,129.7,128.5,121.0,76.0,67.7,38.4,
19.3；HRMS m/z(ESI)calcd for C26H25N2O6S2([M+H]+) 525.1149, found 525.1155.
The synthesis of 35 compound I-18 of embodiment
1r (55.4mg, 0.2mmol), Cu (OAc) are added into Schlenk reaction flask2(copper acetate, 7.2mg,
0.04mmol), DTBP (di-t-butyl peroxide, 87.6mg, 0.6mmol) and solvent acetonitrile (1mL), are placed in 70 for reaction flask
DEG C, be stirred to react under the conditions of air atmosphere, reaction process is monitored through TLC or GC, until (reaction time 12 is small for raw material fully reacting
When), reaction solution after the reaction was completed is filtered by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and subtracts
Pressure concentration removes solvent, by residue through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product I-
18.(82%yield)；1H NMR (400MHz, DMSO-d6) δ: 7.88 (d, J=8.0Hz, 4H), 7.44 (d, J=8.4Hz,
4H), 5.47 (s, 2H), 5.22 (s, 2H), 4.77 (s, 4H), 2.41 (s, 6H), 1.82 (s, 6H)；13C NMR (100MHz,
DMSO-d6) δ: 171.3,145.6,139.2,135.9,130.1,128.6,120.8,76.0,67.7,38.3,21.6,19.4；
HRMS m/z(ESI)calcd for C28H29N2O6S2([M+H]+) 553.1462, found 553.1468.
36 reaction mechanism Control experiment of embodiment
The TEMPO (2,2,6,6- tetramethyl piperidine oxides) or BHT of 3.2 equivalents are added into the reaction of embodiment 14
For (2,6- di-t-butyl) -4- methylphenol as free radical scavenger, the target product yield of the reaction is respectively 88% He
62%.
It follows that the reaction is not directed to free radical process, possible reaction mechanism of the invention can be derived such as following formula
It is shown:
Embodiment described above is merely a preferred embodiment of the present invention, and the simultaneously exhaustion of the feasible implementation of non-present invention.For
It is any apparent to made by it under the premise of without departing substantially from the principle of the invention and spirit for those skilled in the art
Change, should all be contemplated as falling within claims of the invention.
Claims (8)
1. one kind 1, the preparation method of 3- diacetylene derivative, which comprises the steps of: to Schlenk reaction flask
Alkyl end acetylene compound, copper catalyst, oxidant and solvent shown in middle addition formula 1, by reaction flask be placed in certain temperature and
It is stirred to react under the conditions of air atmosphere, obtains target product 1,3- diacetylene derivative (I) through post-processing after fully reacting；Reaction
Formula is as follows:
In the compound that formula 1 and Formulas I indicate, R1Indicate its one or more substituent group connected, each R1It selects independently of one another
From hydrogen, C6-C10Aryl, C5-C14Heteroaryl, C1-C12Alkyl；
R2Indicate C1-C6Alkyl, C3-C6Acyl group, C6-C10Aryl；
Wherein, the hetero atom of the heteroaryl is selected from O, S or N；
And above-mentioned each aryl, heteroaryl, alkyl and acyl group can be further substituted with a substituent, the substituent group is selected from
Halogen or C1-C6Alkyl.
2. the method according to claim 1, wherein R1Indicate its one or more substituent group connected, it is each
R1It is independently from each other hydrogen, C6-C8Aryl and C1-C10Alkyl；The wherein C6-C8Aryl and domain C1-C10Alkyl can be into one
Step is substituted, and the substituent group is selected from halogen or C1-C6Alkyl；
R2Indicate C1-C5Alkyl and C3-C4Acyl group, wherein the C1-C5Alkyl and/or C3-C4Acyl group can be further substituted,
The substituent group is selected from halogen or C1-C2Alkyl.
3. method according to claim 1 or 2, which is characterized in that be preferably added copper acetate (Cu in the method
(OAc)2) catalyst and di-t-butyl peroxide (DTBP) is used as to be used as oxidant.
4. method according to claim 1 to 3, which is characterized in that the certain temperature is 25-100 DEG C.
5. according to the method described in claim 4, it is characterized in that, temperature is most preferably 70 DEG C.
6. the method for -5 any one according to claim 1, which is characterized in that the compound and Cu (OAc) of the formula 12
Molar ratio be 1: 0.1~0.3；The compound of formula 1 and the molar ratio of DTBP are 1: 1~4.
7. method described in -6 any one according to claim 1, which is characterized in that the compound and Cu (OAc) of the formula formula 12
Molar ratio be 1: 0.2；The compound of formula 1 and the molar ratio of DTBP are 1: 3.
8. method described in -7 any one according to claim 1, which is characterized in that the post-processing operation is as follows: will be anti-
Liquid is answered to filter by the glass dropper equipped with silica gel, ethyl acetate rinse filter cake filters and be concentrated under reduced pressure removing solvent, will be remaining
Object is through column chromatography for separation, eluting solvent are as follows: ethyl acetate/n-hexane obtains target product 1,3- diacetylene derivative (I).
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