CN101824027A - Polysubstituted tetrahydroquinoline derivative with optical activity and synthetic method and use thereof - Google Patents
Polysubstituted tetrahydroquinoline derivative with optical activity and synthetic method and use thereof Download PDFInfo
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Abstract
The invention discloses a polysubstituted tetrahydroquinoline derivative with optical activity and a synthetic method and a use thereof. The synthetic method comprises the following steps: taking palladium as a catalyst, and mixing an indole compound, an alkyne compound and an organic mixed solvent together for carrying out indole cyclization reaction, wherein the organic mixed solvent consists of acetonitrile, DMF or DMSO and aromatic acid, such as alkyl acid or benzoic acid. As an important molecular cut block, the polysubstituted tetrahydroquinoline derivative has a certain optical activity and is a great green emission substance. The synthetic method firstly uses the palladium as the catalyst and leads the indole compound and the alkyne compound to generate the polysubstituted tetrahydroquinoline derivative under the condition of taking air or oxygen as an oxidant. The method greatly keeps the atom economy and has a plurality of advantages of high yield, simple conditions, easy obtainment of raw materials, simple reaction equipment, easy realization of industrial production and the like.
Description
Technical field
The present invention relates to tetrahydroquinoline derivative, relate in particular to and have photoactive polysubstituted tetrahydroquinoline derivative and synthetic method thereof, belong to the tetrahydroquinoline derivative field.
Background technology
Aromaticity parent nucleus compounds with polyaryl replacement has the attention that extensively is subjected to people in electrochemistry, photochemistry and field of functional materials, because this compounds has reliable stability, strong electron transfer capacity and solid fluorescence character (J.R.Lakowicz.Principles of FluorescenceSpectroscopy; Plenum Press:New York, 1999; U.Mitschke, P.J.
Mater.Chem.2000,10,1471; C) M.D.Watson, A.Fechtenkotter, K.Mullen.Chem.Rev.2001,101,1267).This compound that has caused the polyaryl of synthetic this compounds and development of new to replace becomes one of research focus.Therefore prepare the important means that some novel polyaryl substitution compounds with special skeleton promote its physical activity often, find easyly, the synthetic method of polysubstituted tetrahydroquinoline derivative is significant efficiently.
Summary of the invention
One of purpose of the present invention provide a class new have a photoactive polysubstituted tetrahydroquinoline derivative;
Two of purpose of the present invention provides a kind of method of synthetic above-mentioned polysubstituted tetrahydroquinoline derivative;
The objective of the invention is to be achieved through the following technical solutions:
One class has photoactive polysubstituted tetrahydroquinoline derivative, and its structure is shown in the general formula I:
Wherein, R
1Or R
2Be selected from hydrogen atom, alkyl, halogen, carbonyl, hydroxyl, itrile group, ester group, benzyl, alkoxyl group or trifluoromethoxy; Described alkyl is preferably the C1-10 alkyl;
R
3Or R
4Be selected from hydrogen atom, benzyl, alkyl or substituted alkyl; Described alkyl is C preferably
1-10Alkyl, described substituted alkyl is hydroxyethyl preferably;
R
5, R
6, R
7Or R
8Be selected from hydrogen atom, aryl, alkyl or substituted alkyl; Described aryl is phenyl preferably; Described alkyl is C preferably
1-10Alkyl, described substituted alkyl is arylalkyl preferably, is more preferably phenylalkyl;
Another object of the present invention provides a kind of method of synthetic above-mentioned compound of Formula I;
Another object of the present invention is achieved through the following technical solutions:
A kind of method of synthetic above-mentioned compound of Formula I may further comprise the steps:
Under the oxygenant protection, be catalyzer with the palladium, Benzazole compounds, acetylene compound and organic mixed solvent are mixed be carried out to the indole ring reaction, promptly;
In order to reach better synthetic effect, the molar ratio of described Benzazole compounds and alkynes is preferably 1-10: 2-10, more preferably 1: 2.5;
Described oxygenant can be an air or oxygen; Preferably, described oxygenant is the oxygen of 1atm.
Described palladium is selected from PdCl
2, Pd (OAc)
2, Pd (OPiv)
2, Pd (OTFA)
2, Pd (OTf)
2, Pd (PhCOO)
2, Pd (CH
3CN)
2Cl
2, Pd (CH
3CN)
4(BF
4)
2Or Pd (PhCN)
2Cl
2
Described Benzazole compounds is various Benzazole compounds, preferably from the N-skatole, and the N-benzylindole, N-(2 hydroxyethyl) indoles, 6-methyl-N skatole, indoles, the 6-chloro-indole, 6-fluoro indole, 6-cyanoindole, the 6-nitroindoline, 6-ester group indoles, 7-skatole or 2,3-dihydro-1H-pyrroles [3,2,1-ij] quinoline;
Described acetylene compound is the alkynes of various replacements, is preferably the diaryl acetylene or derivatives thereof, arylalkyl alkynes or alkyl alkynes; Preferred, described diaryl acetylene is a dibenzenyl, and described arylalkyl alkynes is phenylalkyl alkynes;
Described organic mixed solvent is made up of according to the volume ratio of 10-1: 1-10 the aromatic acid of acetonitrile, DMF or DMSO and alkyl acid or benzoic acids; Preferably, described mixed solvent is made up of according to the volume ratio of 1-10: 10-1 (more preferably 1: 1) the aromatic acid of acetonitrile, DMF or DMSO and alkyl, alkyl acid or benzoic acids.Wherein, described alkyl acid C preferably
1-17Alkyl acid; The aromatic acid of described benzoic acids, preferably acetic acid (AcOH).
The temperature of described one-tenth indole ring reaction is preferably 0-150 ℃, is preferably 15-25 ℃.
Confirm through overtesting, compound of Formula I of the present invention is as a kind of important molecule stripping and slicing, has certain optical activity, under the 380nm irradiation, its fluorescent emission intensity is 1-3 a times of standard substance oxine aluminium, and wavelength region is very narrow, drops on the 500-560nm zone, be a kind of good green emission material, can be used to prepare luminescent material.
The present invention is catalyzer with the palladium first, at air or oxygen is under the condition of oxygenant Benzazole compounds and acetylene compound to be generated polysubstituted tetrahydroquinoline derivative, and products therefrom has good optical activity after measured.The inventive method has kept Atom economy greatly, has the yield height, and condition is simple, and raw material is easy to get, and conversion unit is simple, is easy to plurality of advantages such as suitability for industrialized production
Description of drawings
The synthetic route chart of Fig. 1 compound of Formula I of the present invention.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, advantage of the present invention and characteristics will be more clear along with description.But these embodiment only are exemplary, scope of the present invention are not constituted any restriction.It will be understood by those skilled in the art that and down can make amendment or replace without departing from the spirit and scope of the present invention, but these modifications and replacing all fall within the scope of protection of the present invention the details of technical solution of the present invention and form.
The preparation of embodiment 1 compound 1
Get a reaction tubes; the oxygen protection of 1atm adds 4.5mg palladium, 25.0 μ L N-skatoles down; 89.0mg tolane, 1.0mL acetonitrile and acetic acid mixed solvent (acetonitrile and acetic acid are formed according to 1: 1 volume ratio), 25 ℃ of reactions within 36 hours finish.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for the post separation and obtains pure product 48.0mg, productive rate 78%.
IR：(KBr)v
max?1596，1484，1296，1199，739，694cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.56(d，J＝7.6Hz，2H)，7.29-7.13(m，9H)，7.10-6.85(m，8H)，6.80-6.67(m，4H)，6.60-6.48(m，3H)，6.31(t，J＝7.4Hz，1H)，6.14(d，J＝7.6Hz，2H)，5.49(s，1H)，3.61(s，3H)，2.91(s，3H)；
13C?NMR：(100MHz，CDCl
3)δ146.8，145.9，144.6，144.4，139.4，136.2，135.9，135.83，135.78，129.6，129.5，129.1，128.7，128.6，128.1，127.9，127.6，127.1，126.82，126.78，126.4，126.3，125.8，120.7，119.1，118.5，117.0，115.0，111.8，110.7，108.6，62.4，60.5，37.6，32.6；MS(70eV)：m/z(％)：616.6(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
46H
36N
2(M)
+616.2873，found?616.2869.
The preparation of embodiment 2 compounds 2
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 41.4mg N-benzylindole down, the 89.0mg tolane, and 1.0mL DMF and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for the post separation and obtains pure product 50.0mg, productive rate 65%.
IR：(KBr)v
max?1599，1485，1351，909，737，698cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.51-7.48(m，2H)，7.25-7.04(m，22H)，7.03-6.81(m，7H)，6.68(t，J＝7.6Hz，2H)，6.50-6.43(m，3H)，6.37(t，J＝7.4Hz，1H)，6.14(d，J＝7.6Hz，2H)，5.70(s，1H)，5.31?&?5.17(ABq，J
AB＝16.4Hz，2H)，4.39&4.28(ABq，J
AB＝17.6Hz，2H)；
13C?NMR：(100MHz，CDCl
3)δ147.6，145.3，144.7，143.0，140.5，138.5，138.2，137.6，136.2，135.7，135.45，135.42，129.9，129.7，129.5，128.8，128.7，128.6，128.22，128.17，127.6，127.5，127.3，127.1，126.9，126.80，126.76，126.6，126.5，126.2，126.0，125.9，121.3，119.1，119.0，117.9，115.8，112.9，112.4，109.3，63.1，59.0，55.2，50.0；MS(70eV)：m/z(％)：769[M+1]
+，91(100)；HRMS?m/z(ESI)calcd?for?C
58H
45N
2(M+H)
+769.3577，found?769.3574.
The preparation of embodiment 3 compounds 3
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 32.2mg N-(2 hydroxyethyl) indoles down, the 89.0mg tolane, and 1.0mL DMSO and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 42.5mg, productive rate 63%.
IR：(KBr)v
max?1597，1481，1466，1029，738，696cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.58(d，J＝7.6Hz，2H)，7.30-7.18(m，9H)，7.08(t，J＝7.4Hz，1H)，7.01-6.75(m，11H)，6.56-6.51(m，3H)，6.36(t，J＝7.4Hz，1H)，6.18(d，J＝7.6Hz，2H)，5.62(s，1H)，4.13-4.08(m，2H)，3.83-3.81(m，2H)，3.70-3.59(m，3H)，3.43-3.37(m，1H)，1.67(s，1H)，1.18(s，1H)；
13C?NMR：(100MHz，CDCl
3)δ146.8，145.8，143.7，143.5，139.7，139.3，135.9，135.7，135.6，135.2，129.6，129.4，129.3，128.7，128.6，128.2，127.8，127.5，127.2，127.1，126.9，126.6，126.3，126.2，126.0，121.3，119.3，119.1，117.6，115.7，113.2，111.1，109.1，62.6，61.5，60.1，59.9，53.2，48.7；MS(70eV)：m/z(％)：676.4(100)[M]
+；HRMS?m/z(ESI)calcd?forC
48H
41N
2O
2(M+H)
+677.3162，found?677.3155.
The preparation of embodiment 4 compounds 4
Get a reaction tubes, the oxygen protection adds 4.5mg PdCl down
2, 29.0mg 6-methyl-N skatole, the 89.0mg tolane, 1.0mL acetonitrile and acetic acid mixed solvent, 85 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 40.0mg, productive rate 63%.
IR：(KBr)v
max?2924，1493，696cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.60(d，J＝7.6Hz，2H)，7.32-7.15(m，8H)，7.03(d，J＝8.4Hz，1H)，6.98-6.88(m，4H)，6.87-6.78(m，3H)，6.75-6.64(m，3H)，6.58(d，J＝6.8Hz，2H)，6.43-6.36(m，2H)，6.12(d，J＝7.6Hz，2H)，5.45(s，1H)，3.63(s，3H)，2.86(s，3H)，2.14(s，3H)，1.92(s，3H)；
13C?NMR：(100MHz，CDCl
3)δ146.9，145.6，144.5，142.6，139.6，139.3，136.3，136.0，135.5，134.0，129.7，129.48，129.46，129.2，128.5，128.3，128.0，127.5，127.4，127.2，127.1，126.9，126.8，126.3，126.2，126.0，125.8，123.6，122.2，118.6，116.9，111.4，110.8，108.1，62.6，60.5，37.9，32.7，21.3，20.2；MS(70eV)：m/z(％)：644.7(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
48H
41N
2(M+H)
+645.3264，found?645.3258.
The preparation of embodiment 5 compounds 5
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 29.0mg 6-methyl-N skatole down, the 89.0mg tolane, and 1.0mL acetonitrile and acetic acid mixed solvent, 5 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 40.0mg, productive rate 63%.
IR：(KBr)v
max?3294，2953，1726，1686，1530，1444，1263，1069cm
-1；
1H?NMR：(300MHz，CDCl
3)δ9.38(brs，1H)，7.88(d，J＝8.7Hz，1H)，7.19(s，1H)，7.10(d，J＝8.1Hz，1H)，3.91(s，3H)，3.89(s，3H)，2.98-2.89(m，1H)，1.22(d，J＝6.9Hz，6H)；
13C?NMR：(100MHz，CDCl
3)δ164.7，161.5，147.4，135.3，127.5，125.1，122.4，111.8，108.7，52.6，51.8，34.3，24.0；MS(70eV)：m/z(％)：275.2(55)[M]
+，228.2(100)；HRMS?m/z(ESI)calcd?for?C15H17NO4Na(M+Na)
+298.10498，found?298.10506.
The preparation of embodiment 6 compounds 6
Get a reaction tubes, the protection of the oxygen of 1atm adds 4.5mg palladium, 20.4mg indoles down, the 89.0mg tolane, and 1.0mL acetonitrile and acetic acid mixed solvent (acetonitrile and acetic acid are formed according to 1: 1 volume ratio), 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 43.7mg, productive rate 73%.
IR：(KBr)v
max?3245，2919，1599，1478，1440，1098，738，693cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.90(s，1H)，7.73(d，J＝7.6Hz，2H)，7.32-7.17(m，10H)，7.08-7.04(m，2H)，6.99-6.74(m，11H)，6.59(d，J＝6.8Hz，2H)，6.44(d，J＝8.0Hz，1H)，6.33(d，J＝7.4Hz，1H)，6.22(d，J＝7.6Hz，2H)，5.78(s，1H)，4.30(s，1H)；
13C?NMR：(100MHz，CDCl
3)δ147.3，145.6，143.8，143.4，140.1，139.1，136.3，135.7，135.0，129.7，129.5，129.2，128.45，128.39，128.2，127.5，127.3，127.2，126.9，126.8，126.5，126.4，126.3，126.0，121.5，121.0，119.1，118.8，117.0，116.5，116.4，114.4，110.6，62.7，52.6；MS(70eV)：m/z(％)：588.5(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
44H
33N
2(M+H)
+589.2639，found?589.2629.
The preparation of embodiment 7 compounds 7
Get a reaction tubes, the oxygen protection adds 4.5mg Pd (CH down
3CN)
2Cl
2, the 30.3mg6-chloro-indole, the 89.0mg tolane, 1.0mL DMSO and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 39.0mg, productive rate 59%.
IR：(KBr)v
max?3418，2925，1599，1483，731，697cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.91(s，1H)，7.70(d，J＝8.0Hz，2H)，7.32(t，J＝7.6Hz，2H)，7.27-7.15(m，7H)，7.00-6.88(m，5H)，6.80-6.68(m，5H)，6.58(d，J＝7.6Hz，2H)，6.46(d，J＝1.6Hz，1H)，6.29(d，J＝8.4Hz，1H)，6.19(d，J＝8.0Hz，2H)，5.70(d，J＝2.0Hz，1H)，4.40(d，J＝2.0Hz，1H)；
13C?NMR：(100MHz，CDCl
3)δ147.1，145.8，144.2，142.7，140.6，138.5，135.7，135.4，135.2，133.7，129.6，129.3，129.0，128.6，128.3，127.9，127.6，127.45，127.41，127.2，127.1，126.7，126.5，126.2，124.8，121.7，119.8，119.7，116.9，116.6，115.2，113.6，110.6，62.2，52.2；MS(70eV)：m/z(％)：656.3(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
44H
31Cl
2N
2(M+H)
+657.1859，found?657.1857.
The preparation of embodiment 8 compounds 8
Get a reaction tubes, the protection of the oxygen of 1atm adds 4.5mg palladium, 27.0mg 6-fluoro indole down, the 89.0mg tolane, and 1.0mL acetonitrile and acetic acid mixed solvent (acetonitrile and acetic acid are formed according to 1: 1 volume ratio), 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 52.0mg, productive rate 83%.
IR：(KBr)v
max?1723，1485，1251，1169，695cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.91(s，1H)，7.73(d，J＝7.6Hz，2H)，7.34-7.17(m，8H)，7.15-7.10(m，1H)，7.05(d，J＝2.0Hz，1H)，7.00-6.88(m，4H)，6.85-6.75(m，3H)，6.65-6.52(m，4H)，6.45-6.32(m，2H)，6.22(d，J＝7.2Hz，2H)，5.66(s，1H)，4.19(s，1H)；
13CNMR：(100MHz，CDCl
3)δ157.3(d，J＝251.0Hz)，155.0(d，J＝251.1Hz)，147.7，145.4，142.91，142.89，141.4，139.6，138.6，135.5，135.44，135.36，131.34，129.7，129.2，129.1，128.6，128.4，127.6，127.3，127.2，126.73，126.68，126.6，126.4(d，J＝8.0Hz)，122.6，117.2(d，J＝7.6Hz)，116.9(d，J＝4.6Hz)，115.6(d，J＝23.4Hz)，114.9(d，J＝7.8Hz)，112.4(d，J＝23.0Hz)，111.4(d，J＝9.6Hz)，109.9(d，J＝26.5Hz)，103.9(d，J＝24.2Hz)，62.5，52.6；MS(70eV)：m/z(％)：624.3(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
44H
30F
2N
2(M)
+624.2371，found?624.2368.
The preparation of embodiment 9 compounds 9
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 29.0mg 6-cyanoindole down, the 89.0mg tolane, and 1.0mL acetonitrile and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 38.2mg, productive rate 60%.
IR：(KBr)v
max?2215，1727，1604，1497，1247，695cm
-1；
1H?NMR：(400MHz，AcOH-d4)δ7.82(d，J＝7.6Hz，2H)，7.41-7.29(m，7H)，7.27-7.19(m，4H)，7.13(dd，J＝8.0，1.2Hz，1H)，7.07-6.90(m，5H)，6.88(s，1H)，6.78(t，J＝7.6Hz，2H)，6.64(d，J＝8.4Hz，3H)，6.22(d，J＝8.0Hz，2H)，5.90(s，1H)；
13C?NMR：(100MHz，AcOH-d4)δ148.4，147.1143.8，142.9，139.0，137.8，136.6，136.2，136.0，133.1，131.8，130.5，130.2，129.9，129.8，129.6，128.9，128.7，128.4，128.2，128.1，127.9，127.1，125.4，124.9，124.7，121.2，120.6，117.8，117.0，114.9，113.0，102.4，98.1，62.8，51.7；MS(70eV)：m/z(％)：638.4(100)[M]
+；HRMS?m/z(ESI)calcd?for?C
46H
30N
4Na(M+Na)
+661.2363，found?661.2367.
The preparation of embodiment 10 compounds 10
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 32.4mg 6-nitroindoline down, the 89.0mg tolane, and 1.0mL DMF and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 27.4mg, productive rate 40%.
IR：(KBr)v
max?3352，2925，1724，1463，1330，1271，695cm
-1；
1H?NMR：(400MHz，DMSO-d6)δ11.6(s，1H)，8.39(d，J＝2.8Hz，1H)，7.83-7.71(m，5H)，7.50-7.24(m，11H)，7.08-6.95(m，3H)，6.85-6.77(m，1H)，6.73-6.65(m，3H)，6.58-6.51(m，3H)，6.30-5.98(m?3H)；
13C?NMR：(100MHz，DMSO-d6)δ149.8，146.8，145.4，142.4，141.4，140.0，137.7，137.4，135.2，135.0，134.4，134.3，128.9，128.8，128.7，128.4，127.6，127.0，126.8，126.3，125.3，125.2，124.7，122.1，116.6，115.7，115.6，113.8，112.9，111.6，61.2，49.6；MS(70eV)：m/z(％)：678.3[M]
+，84(100)；HRMS?m/z(ESI)calcd?for?C
44H
30N
4O
4Na(M+Na)
+701.2159，found701.2163
The preparation of embodiment 11 compounds 11
Get a reaction tubes, the protection of the oxygen of 1atm adds 4.5mg palladium, 31.4mg 2 down, 3-dihydro-1H-pyrroles [3,2,1-ij] quinoline, and the 89.0mg tolane, 1.0mL acetonitrile and acetic acid mixed solvent, 25 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 47.1mg, productive rate 70%.
IR：(KBr)v
max?2924，2856，1728，1487，1444，1263，1111，1074，1032，798，748，698cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.57(d，J＝7.2Hz，2H)，7.30-7.15(m，8H)，7.00-6.86(m，4H)，6.79-6.69(m，8H)，6.54(d，J＝6.8Hz，2H)，6.25-6.05(m，3H)，5.35(s，1H)，4.02-3.95(m，2H)，3.42-3.32(m，1H)，3.22-3.12(m，1H)，2.96-2.83(m，2H)，2.70-2.54(m，2H)，2.20-2.06(m，2H)，1.98-1.88(m，1H)，1.80-1.72(m，1H)；
13C?NMR：(100MHz，CDCl
3)δ146.6，145.9，144.8，141.0，139.4，139.1，136.3，136.1，135.9，133.2，129.62，129.58，129.1，128.4，128.3，128.0，127.5，127.1，126.8，126.6，126.3，126.2，125.7，125.6，125.1，123.8，121.4，120.8，118.8，117.7，117.0，116.1，114.1，111.9，62.2，60.2，48.9，43.9，28.0，24.7，23.0，21.7；MS(70eV)：m/z(％)：668.5(100)[M]
+；HRMS?m/z(ESI)calcdfor?C
50H
40N
2(M)
+668.3186，found?668.3187.
The preparation of embodiment 12 compounds 12
Get a reaction tubes, oxygen protection adds 4.5mg palladium, 25.0 μ L N-skatoles down, 88.0 μ L 1-benzene hexins, and 1.0mL DMSO and acetic acid mixed solvent, 45 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 32.0mg, productive rate 56%.
IR：(KBr)v
max?2957，2927，1724，1479，1261，1073，739cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.46(t，J＝7.4Hz，2H)，7.39-7.35(m，3H)，7.28-7.22(m，2H)，7.18-7.08(m，4H)，7.05-6.95(m，3H)，6.84(s，1H)，6.73(d，J＝6.8Hz，2H)，6.47(d，J＝8.0Hz，1H)，6.40(t，J＝7.4Hz，1H)，4.69(s，1H)，3.64(s，3H)，2.75(s，3H)，2.18-2.09(m，1H)，2.04-1.97(m，1H)，1.95-1.87(m，2H)，1.24-1.17(m，4H)，0.81(t，J＝7.0Hz，3H)，0.74-0.66(m，4H)，0.41(t，J＝6.8Hz，3H)；
13CNMR：(100MHz，CDCl
3)δ145.9，143.7，143.0，140.5，139.9，138.0，137.0，135.7，129.4，129.2，128.5，128.4，128.3，127.7，126.9，126.4，126.1，125.4，120.8，118.8，118.6，117.7，115.4，112.1，111.5，108.8，64.0，59.2，38.6，33.6，32.7，31.0，25.5，25.5，23.0，21.9，14.2，13.5；MS(70eV)：m/z(％)：576.6[M]
+，144.2(100)；HRMSm/z(ESI)calcd?for?C
42H
43N
2(M-H)
+575.3421，found?575.3405.
The preparation of embodiment 13 compounds 13
Get a reaction tubes, oxygen protection adds 9.0mg palladium, 50.0 μ L N-skatoles down, 180.0 μ L 5-decine, and 1.0mL DMF and acetic acid mixed solvent, 10 ℃, reaction finishes within 36 hours.Add shrend and go out, ethyl acetate extraction 3 times is washed extraction liquid once with saturated sodium bicarbonate after allowing, and saturated common salt is washed once, and anhydrous magnesium sulfate drying was spin-dried for post and separates, and obtained pure product 37.0mg, productive rate 35%.
IR：(KBr)v
max?2957，2929，2859，1482，1464，1259，742cm
-1；
1H?NMR：(400MHz，CDCl
3)δ7.59(d，J＝8.0Hz，1H)，7.35(d，J＝7.2Hz，1H)，7.17-7.07(m，3H)，7.04(t，J＝7.0Hz，1H)，6.74(t，J＝7.2Hz，1H)，6.53(d，J＝8.0Hz，1H)，6.29(s，1H)，4.68(s，1H)，3.50(s，3H)，2.76(s，3H)，2.62-2.54(m，1H)，2.34-2.27(m，1H)，2.08-1.91(m，4H)，1.76-1.63(m，2H)，1.60-1.45(m，3H)，1.40-0.96(m，7H)，1.02(t，J＝6.6Hz，3H)，0.92-0.70(m，8H)，0.73(t，J＝7.2Hz，3H)，0.63(t，J＝6.2Hz，3H)，0.51-0.38(m，1H)；
13C?NMR：(100MHz，CDCl
3)δ143.6，143.4，141.7，135.9，135.6，128.2，127.2，125.6，124.9，120.5，119.5，118.3，118.2，115.6，112.6，110.8，108.9，64.9，57.6，38.7，32.8，32.6，32.4，31.9，31.2，26.7，26.2，25.6，25.2，23.6，23.4，23.2，22.5，14.1，13.9；MS(70eV)：m/z(％)：536.4[M]
+，144(100)；HRMS?m/z(ESI)calcd?for?C
38H
51N
2(M-H)
+535.4047，found535.4047.
The photolytic activity test of test example 1 compound of Formula I of the present invention
Supply test agent: the compound that embodiment 1-13 is prepared is numbered compound 1-13 respectively;
Testing installation: FL4500 fluorescent emission instrument;
Touchstone product: oxine aluminium;
Test method: at first be test for the uv-absorbing situation of test agent, find institute's test sample product have at the 350nm place the last one absorption peak.Attempting wavelength light about 350nm on the FL4500 fluorescent emission instrument to the situation that excites of sample, the exciting that is selected in the 380nm wavelength light at last is best conditions down, tests out the solid fluorescence of standard substance and confession test agent more respectively.
Test-results: very big for test agent in 520nm place fluorescence intensity, be that the fluorescence intensity 1-3 of standard substance is doubly many, wherein, the fluorescence intensity of compound 1 is standard substance oxine aluminium (Alq
3) more than 3 times, simultaneously wavelength of fluorescence almost all drops on 500-560nm interval (light emitting region of green glow), test-results shows that compound of Formula I of the present invention is good green emission source, can be applicable to prepare the green emission material.
Claims (10)
1. polysubstituted tetrahydroquinoline derivative, its structural formula are shown in the general formula I:
R
1Or R
2Be selected from hydrogen atom, alkyl, halogen, carbonyl, hydroxyl, itrile group, ester group, benzyl, alkoxyl group or trifluoromethoxy;
R
3Or R
4Be selected from hydrogen atom, benzyl, alkyl or substituted alkyl;
R
5, R
6, R
7Or R
8Be selected from hydrogen atom, aryl, alkyl or substituted alkyl.
2. according to the described polysubstituted tetrahydroquinoline derivative of claim 1, it is characterized in that:
Work as R
1Or R
2When being alkyl, described alkyl is C
1-10Alkyl;
Work as R
3Or R
4Be selected from aryl, when alkyl or substituted alkyl, described aryl is a phenyl; Described alkyl is C
1-10Alkyl; Described substituted alkyl is a hydroxyethyl;
Work as R
5, R
6, R
7Or R
8When being selected from alkyl or substituted alkyl; Described alkyl is C
1-10Alkyl, described substituted alkyl is an arylalkyl; Preferably, described arylalkyl is a phenylalkyl.
3. the method for the described compound of Formula I of synthetic claim 1 comprises: under the oxygenant protection, be catalyzer with the palladium, Benzazole compounds, acetylene compound and organic mixed solvent mixed be carried out to the indole ring reaction, promptly.
4. it is characterized in that in accordance with the method for claim 3: described oxygenant is an air or oxygen; Preferably, described oxygenant is the oxygen of 1atm.
5. in accordance with the method for claim 4, it is characterized in that: the molar ratio of described Benzazole compounds and acetylene compound is 1-10: 2-10, is preferably 1: 2.5.
6. it is characterized in that in accordance with the method for claim 3: described palladium is selected from PdCl
2, Pd (OAc)
2, Pd (OPiv)
2, Pd (OTFA)
2, Pd (OTf)
2, Pd (PhCOO)
2, Pd (CH
3CN)
2Cl
2, Pd (CH
3CN)
4(BF
4)
2Or Pd (PhCN)
2Cl
2
7. in accordance with the method for claim 3, it is characterized in that: described Benzazole compounds is various Benzazole compounds, preferably from the N-skatole, the N-benzylindole, N-(2 hydroxyethyl) indoles, 6-methyl-N skatole, indoles, 6-chloro-indole, 6-fluoro indole, the 6-cyanoindole, 6-nitroindoline, 6-ester group indoles, 7-skatole or 2,3-dihydro-1H-pyrroles [3,2,1-ij] quinoline.
8. in accordance with the method for claim 3, it is characterized in that: described acetylene compound is the alkynes of various replacements, preferably from the diaryl acetylene or derivatives thereof, and arylalkyl alkynes or alkyl alkynes; Preferred, described diaryl acetylene is a dibenzenyl, and described arylalkyl alkynes is phenylalkyl alkynes.
9. it is characterized in that in accordance with the method for claim 3: described organic mixed solvent is made up of according to the volume ratio of 10-1: 1-10 the aromatic acid of acetonitrile, DMF or DMSO and alkyl acid or benzoic acids; Preferably, described mixed solvent, more preferably is made up of according to 1: 1 volume ratio according to 1-10: 10-1 the aromatic acid of acetonitrile, DMF or DMSO and alkyl, alkyl acid or benzoic acids; Wherein, described alkyl acid C preferably
1-17Alkyl acid; The aromatic acid of described benzoic acids, preferably acetic acid.
10. in accordance with the method for claim 3, it is characterized in that: the temperature of described one-tenth indole ring reaction is 0-150 ℃, is preferably 15-25 ℃.
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|---|---|---|---|---|
| CN105859687A (en) * | 2016-03-30 | 2016-08-17 | 阜阳欣奕华材料科技有限公司 | Compound, organic electroluminescent device and display device |
-
2010
- 2010-04-02 CN CN 201010138037 patent/CN101824027B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| 《Angew. Chem.》 20080416 Nobuyoshi Umeda et al. Fluorescent Naphthyl- and Anthrylazoles from the Catalytic Coupl of Phenylazoles with Internal Alkynes through the Cleavage of Multiple C-H Bonds 第4083-4086页 1-10 第120卷, * |
| 《Chem. Eur. J.》 20080612 Yao-Ting Wu et al. Palladium-Catalyzed Formation ofHighly Substituted Naphthalenes from Arene and Alkyne Hydrocarbons 第6697-6703页 1-10 第14卷, * |
| 《J. AM. CHEM. SOC.》 20090805 Nicolas Guimond et al. Isoquinoline Synthesis via Rhodium-Catalyzed Oxidative Cross-Coupling/ Cyclization of Aryl Aldimines and Alkynes 第12050-12051页 1-10 第131卷, * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859687A (en) * | 2016-03-30 | 2016-08-17 | 阜阳欣奕华材料科技有限公司 | Compound, organic electroluminescent device and display device |
| CN105859687B (en) * | 2016-03-30 | 2018-05-25 | 阜阳欣奕华材料科技有限公司 | A kind of compound, organic electroluminescence device and display device |
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