CN108276334A - A kind of preparation method of acridone and its derivative - Google Patents
A kind of preparation method of acridone and its derivative Download PDFInfo
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- CN108276334A CN108276334A CN201810125527.5A CN201810125527A CN108276334A CN 108276334 A CN108276334 A CN 108276334A CN 201810125527 A CN201810125527 A CN 201810125527A CN 108276334 A CN108276334 A CN 108276334A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention discloses the preparation methods of a kind of acridone and its derivative, and this method is using 2 halogenated diphenyl aminated compounds as substrate, and under CO gas atmosphere, the preparation of acridone and its derivative is realized by the carbonylation of palladium chtalyst.The reaction raw materials of this method are more easy to get, and reaction condition is mild；The method has been broken in traditional preparation methods, substrate needs the limitation of previously-introduced carbonyl functional group's precursor, using carbon monoxide as the direct sources of carbonyl, two C C keys are constructed by one step of carbonylation, best suit atom economy in organic synthesis, the theory of synthesis step economy and Green Chemistry, has developed organic procedures, also achieves the efficient preparation to acridones compound.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of carbonylation using palladium chtalyst synthesize acridone and
The method of its derivative.
Background technology
Acridone is as a kind of important nitrogenous heterocyclic molecular skeleton, and initial stage in natural products from extracting.
Application in terms of dyestuff and biological medicine is relatively broad, and with the continuous deepening of research, and acridone and its derivative are answered
Constantly expanded with range, such as effective profit is obtained in fluorescence probe, organic solar batteries, Organic Light Emitting Diode etc.
With such compound is because having unique property, so just increasingly being paid close attention to by researcher.
Acridones compound is typically to be prepared by the ring closure reaction of intermediate hexatomic ring, conjunction traditional at present
It is directly to be realized by C-N couplings or acid catalyzed friedel-crafts acylation cyclization at method, such as acid catalyzed 2- carboxyls
Diphenylamines cyclization；The nucleophilic displacement of fluorine of intramolecular, such as 2- cyano diphenylamines intramolecular cyclizations；Or 2- arylamine benzophenones
The cyclisation etc. of the intramolecular of object is closed, the common feature of these methods is the previously-introduced carbonyl functional group's precursor of substrate needs, such as
Carboxyl, cyano etc., and raw material acquisition is complex, condition is also relatively harsh.This limits these synthesis sides to a certain extent
The practical application of method.
Invention content
In view of the above problems, the present invention is intended to provide a kind of carbonylation method of new palladium chtalyst synthesizes acridone
And its derivative is not necessarily to previously-introduced carbonyl functional group's precursor using carbon monoxide as carbonyl source, carbon monoxide is not only cheap easy
, and atom economy in organic synthesis is best suited, the theory of synthesis step economy and Green Chemistry, reaction condition is mild,
Reaction is efficiently and with good functional group compatibility.
To achieve the goals above, the technical solution adopted in the present invention is as follows：It is with 2- halogenated diphenyl aminated compounds
Substrate realizes the preparation of acridone and its derivative by the carbonylation of palladium chtalyst under CO gas atmosphere.
Concrete operation step is：
(1) dry Schlenk is added in palladium catalyst, organophosphorus ligand and inorganic base together to manage, Schlenk is managed in
Atmosphere carbon monoxide is replaced by air；
(2) under CO gas atmosphere, anhydrous n,N-Dimethylformamide is added, is heated to 120 DEG C, stirs 30 points
Clock；
(3) 2- bromine diphenylamine substrates are added, reacts 12 hours, is cooled to room temperature under the conditions of 120 DEG C；
(4) saturated ammonium chloride solution is added and reaction is quenched, add and extracted with ethyl acetate after water, is column chromatography for separation, pure
Change.
Further, the 2- bromines diphenylamine substrate, palladium catalyst, organophosphorus ligand, inorganic base substance amount ratio
For：1.00∶0.05∶0.10∶3.00.
Further, the 2- bromines diphenylamine substrate is N- methyl -2- bromines diphenylamines, the bromo- 4 '-methyl of N- methyl -2-
The bromo- 4 '-tert-butyl diphenylamine of diphenylamines, N- methyl -2-, the bromo- 4 '-methoxy diphenylamines of N- methyl -2-, N- methyl -2- are bromo-
The bromo- 4 '-chlorodiphenyl amine of 4 '-fluorine diphenylamines, N- methyl -2-, the bromo- 4 '-isopropyl diphenyl amine of N- methyl -2-, N- methyl -2- are bromo-
The bromo- 4- methyldiphenylamines of 3 ', 5 '-dimethyl diphenylamines, N- methyl -2-, the bromo- 5- methyldiphenylamines of N- methyl -2-, N- methyl -
The bromo- 4- fluorine diphenylamines of 2-, the bromo- 4- chlorodiphenyls amine of N- methyl -2-, the bromo- 4- trifluoromethyls diphenylamines of N- methyl -2-, N- methyl -2-
Bromo- 4- trifluoromethoxies diphenylamines, N- ethyl -2- bromines diphenylamines, N- methylcyclopropyl groups -2- bromines diphenylamines, N- hexyl -2- bromines two
One kind in aniline, N- benzyl -2- bromines diphenylamines, 2- bromines triphenylamine, the bromo- 4- methyl triphenylamines of 2-, the bromo- 4- fluorine triphenylamines of 2-.
Further, the palladium catalyst is palladium bichloride.
Further, the organophosphorus ligand is tricyclohexyl phosphine tetrafluoroborate.
Further, the inorganic base is pivalic acid caesium.
Further, the CO gas atmosphere is a standard atmospheric pressure.
It has the beneficial effect that：Reaction raw materials are relatively simple easily in the preparation method of acridone and its derivative disclosed by the invention
, reaction condition is mild；The method has been broken in traditional preparation methods, and substrate needs previously-introduced carbonyl functional group's precursor
Limitation and reaction raw materials are not easy the deficiency prepared；This method passes through carbonylation using carbon monoxide as the direct sources of carbonyl
One step constructs two C-C keys, best suits the theory of atom economy in organic synthesis, synthesis step economy and Green Chemistry, hair
Organic procedures have been opened up, the efficient preparation to acridones compound is also achieved.
Description of the drawings
Fig. 1 is the reaction equation of the present invention；
Fig. 2 is the embodiment of the present invention 11H-NMR spectrum；
Fig. 3 is the embodiment of the present invention 113C-NMR spectrograms；
Fig. 4 is the embodiment of the present invention 2,91H-NMR spectrum；
Fig. 5 is the embodiment of the present invention 2,913C-NMR spectrograms；
Fig. 6 is the embodiment of the present invention 31H-NMR spectrum；
Fig. 7 is the embodiment of the present invention 313C-NMR spectrograms；
Fig. 8 is the embodiment of the present invention 41H-NMR spectrum；
Fig. 9 is the embodiment of the present invention 413C-NMR spectrograms；
Figure 10 is the embodiment of the present invention 5,111H-NMR spectrum；
Figure 11 is the embodiment of the present invention 5,1113C-NMR spectrograms；
Figure 12 is the embodiment of the present invention 5,1119F-NMR spectrograms；
Figure 13 is the embodiment of the present invention 6,121H-NMR spectrum；
Figure 14 is the embodiment of the present invention 6,1213C-NMR spectrograms；
Figure 15 is the embodiment of the present invention 71H-NMR spectrum；
Figure 16 is the embodiment of the present invention 713C-NMR spectrograms；
Figure 17 is the embodiment of the present invention 81H-NMR spectrum；
Figure 18 is the embodiment of the present invention 813C-NMR spectrograms；
Figure 19 is the embodiment of the present invention 101H-NMR spectrum；
Figure 20 is the embodiment of the present invention 1013C-NMR spectrograms；
Figure 21 is the embodiment of the present invention 131H-NMR spectrum；
Figure 22 is the embodiment of the present invention 1313C-NMR spectrograms；
Figure 23 is the embodiment of the present invention 1319F-NMR spectrograms；
Figure 24 is the embodiment of the present invention 141H-NMR spectrum；
Figure 25 is the embodiment of the present invention 1413C-NMR spectrograms；
Figure 26 is the embodiment of the present invention 1419F-NMR spectrograms；
Figure 27 is the embodiment of the present invention 151H-NMR spectrum；
Figure 28 is the embodiment of the present invention 1513C-NMR spectrograms；
Figure 29 is the embodiment of the present invention 161H-NMR spectrum；
Figure 30 is the embodiment of the present invention 1613C-NMR spectrograms；
Figure 31 is the embodiment of the present invention 171H-NMR spectrum；
Figure 32 is the embodiment of the present invention 1713C-NMR spectrograms；
Figure 33 is the embodiment of the present invention 181H-NMR spectrum；
Figure 34 is the embodiment of the present invention 1813C-NMR spectrograms；
Figure 35 is the embodiment of the present invention 191H-NMR spectrum；
Figure 36 is the embodiment of the present invention 1913C-NMR spectrograms；
Figure 37 is the embodiment of the present invention 201H-NMR spectrum；
Figure 38 is the embodiment of the present invention 2013C-NMR spectrograms；
Figure 39 is the embodiment of the present invention 211H-NMR spectrum；
Figure 40 is the embodiment of the present invention 2113C-NMR spectrograms；
Figure 41 is the embodiment of the present invention 2119F-NMR spectrograms.
Figure 42 is to add substrate in 1-21 of the embodiment of the present invention, obtain product and separate and collect the distribution situation of rate.
Specific implementation mode
In order to make those skilled in the art be better understood on technical scheme of the present invention, 1- below in conjunction with the accompanying drawings
42 and embodiment technical scheme of the present invention is further described, but scope of protection of the present invention is not limited thereto.
Embodiment 1
0.01mmol palladium bichlorides, 0.02mmol tricyclohexyl phosphines tetrafluoroborate and 0.6mmol pivalic acids caesium are added together
Enter dry Schlenk pipes, the atmosphere in Schlenk pipes is replaced into carbon monoxide by air, system is in a standard
Replaced in the carbon monoxide atmosphere of atmospheric pressure has pure carbon monoxide atmosphere with guarantee system three times；In CO gas
Under atmosphere, the n,N-Dimethylformamide of anhydrous 2mL is added, is heated to 120 DEG C, stirs 30 minutes；0.2mmol N- first is added
Base -2- bromine diphenylamines is reacted 12 hours under the conditions of 120 DEG C, is cooled to room temperature；4mL saturated ammonium chloride solutions are added to be quenched instead
Answer, add extracted with ethyl acetate after water 8mL, column chromatography for separation, purifying obtain acridone derivatives, which divides
Reach 78% from collection rate.
Embodiment 2-9,11-17
Difference from example 1 is that the 2- bromine diphenylamine substrates being added in embodiment 2-9 are respectively N- first
The bromo- 4 '-methyldiphenylamines of base -2-, the bromo- 4 '-tert-butyl diphenylamines of N- methyl -2-, the bromo- 4 '-methoxyl group hexichol of N- methyl -2-
The bromo- 4 '-fluorine diphenylamines of amine, N- methyl -2-, the bromo- 4 '-chlorodiphenyl amine of N- methyl -2-, the bromo- 4 '-isopropyl diphenyls of N- methyl -2-
Bromo- 3 ', the 5 '-dimethyl diphenylamines of amine, N- methyl -2-, the bromo- 4- methyldiphenylamines of N- methyl -2- carry out the N- in alternate embodiment 1
Methyl -2- bromine diphenylamines, other preparation processes are constant.
The 2- bromine diphenylamine substrates being added in embodiment 11-17 are respectively the bromo- 4- fluorine diphenylamines of N- methyl -2-, N- first
The bromo- 4- chlorodiphenyls amine of base -2-, the bromo- 4- trifluoromethyls diphenylamines of N- methyl -2-, the bromo- 4- trifluoromethoxies hexichol of N- methyl -2-
Amine, N- ethyl -2- bromines diphenylamines, N- methylcyclopropyl groups -2- bromines diphenylamines, N- hexyl -2- bromine diphenylamines come in alternate embodiment 1
N- methyl -2- bromine diphenylamines, other preparation processes are constant.
The rate that separates and collects of embodiment 2-9 is respectively 57%, 81%, 37%, 54%, 73%, 70%, 64%；
The rate that separates and collects of embodiment 11-17 is respectively 37%, 29%, 78%, 38%, 55%, 74%, 45%.
Embodiment 10
By 0.01mmol palladium bichlorides, 0.02mmol tricyclohexyl phosphines tetrafluoroborate, 0.6mmol pivalic acids caesium and 0.2mmo
Dry Schlenk pipes are added in the bromo- 5- methyldiphenylamines of N- methyl -2- together, by the atmosphere in Schlenk pipes by air
It is replaced into carbon monoxide, system is replaced in the carbon monoxide atmosphere of a standard atmospheric pressure three times with guarantee system with pure
Carbon monoxide atmosphere；Under CO gas atmosphere, the n,N-Dimethylformamide of anhydrous 2mL is added, is heated to 120
DEG C, it reacts 12 hours, is cooled to room temperature；4mL saturated ammonium chloride solutions are added, reaction are quenched, add use after water 8mL ethyl acetate into
Row extraction, column chromatography for separation, purifying obtain acridone derivatives, and the rate that separates and collects of the embodiment reaches 79%.
Embodiment 18-21
Embodiment 18-21 and embodiment 10 the difference is that, the 2- bromine diphenylamines bottom being added in embodiment 18-21
Object be respectively N- benzyl -2- bromines diphenylamines, 2- bromines triphenylamine, the bromo- 4- methyl triphenylamines of 2-, the bromo- 4- fluorine triphenylamines of 2- be used for replace
For the bromo- 5- methyldiphenylamines of N- methyl -2- in embodiment 10, other preparation processes are constant.
The rate that separates and collects of embodiment 18-21 respectively reaches 53%, 66%, 89%, 59%.
It will be depicted as table the case where adding substrate in 1-21 of the embodiment of the present invention, obtain product and separate and collect rate, such as schemed
Shown in 42, and the product of acquisition is passed through1H-NMR、13C-NMR or (19F-NMR) characterization is confirmed, and all unknown samples pass through
High resolution mass spectrum (HRMS) confirms.
The nuclear magnetic data of case study on implementation 1：1H NMR(400MHz,CDCl3) δ 8.54 (d, J=8.0Hz, 2H), 7.69 (t, J
=7.9Hz, 2H), 7.48 (d, J=8.7Hz, 2H), 7.27 (t, J=7.5Hz, 2H), 3.85 (s, 3H) ppm；13C NMR
(101MHz,CDCl3)δ178.0,142.4,133.7,127.6,122.3,121.1,114.7,33.5ppm.
The nuclear magnetic data of case study on implementation 2,9：1H NMR(400MHz,CDCl3) δ 8.57 (d, J=8.9Hz, 1H), 8.36 (s,
1H), 7.72 (t, J=8.6Hz, 1H), 7.59-7.49 (m, 2H), 7.44 (d, J=8.9Hz, 1H), 7.32-7.24 (t, 1H),
3.89(s,3H),2.48(s,3H)ppm.13C NMR(101MHz,CDCl3)δ178.0,142.4,140.7,135.2,133.6,
130.9,127.8,127.1,122.4,122.4,120.9,114.7,114.6,33.6,20.6ppm.
The nuclear magnetic data of case study on implementation 3：1H NMR(400MHz,CDCl3) δ 8.61 (d, J=8.5Hz, 2H), 7.84 (d, J
=9.2Hz, 1H), 7.79-7.70 (m, 1H), 7.55 (t, J=8.4Hz, 2H), 7.31 (dd, J=13.9,6.3Hz, 2H),
3.93(s,3H),1.44(s,9H)ppm.13C NMR(101MHz,CDCl3)δ178.1,144.1,142.3,140.5,133.5,
131.8,127.7,123.3,122.3,122.0,120.9,114.6,114.5,34.4,33.4,31.3ppm.HRMS(EI):
Exact mass calcd for C18H19NO.[M]+:265.1467,Found:265.1461.
The nuclear magnetic data of case study on implementation 4：1H NMR(400MHz,CDCl3) δ 8.55 (d, J=8.0Hz, 1H), 7.93 (s,
1H), 7.67 (d, J=8.1Hz, 1H), 7.51-7.40 (m, 2H), 7.38-7.21 (m, 2H), 3.93 (s, 4H), 3.84 (s, 3H)
ppm.13C NMR(101MHz,CDCl3)δ177.4,154.3,141.9,137.3,133.4,127.6,124.4,123.0,
121.6,120.8,116.5,114.5,106.5,55.7,33.6ppm.
The nuclear magnetic data of case study on implementation 5,11：1H NMR(400MHz,CDCl3) δ 8.53 (dd, J=8.0,1.7Hz, 1H),
8.18 (dd, J=8.8,3.1Hz, 1H), 7.73 (t, J=8.7Hz, 1H), 7.55-7.42 (m, 3H), 7.30 (t, J=7.5Hz,
1H),3.89(s,3H)ppm.13C NMR(101MHz,CDCl3)δ177.2,158.6,156.2,142.2,139.0,133.9,
127.5,122.1,121.9,121.6,121.3,116.9,116.8,114.7,112.0,111.7,33.9ppm.19F NMR
(376MHz,CDCl3)δ-121.3ppm.HRMS(EI):Exact mass calcd for C14H10FNO.[M]+:228.0780,
Found:228.0819.
The nuclear magnetic data of case study on implementation 6,12：1H NMR(400MHz,CDCl3) δ 8.48 (d, J=8.0Hz, 1H), 8.43
(d, J=2.5Hz, 1H), 7.71 (t, J=8.6Hz, 1H), 7.57 (dd, J=9.1,2.6Hz, 1H), 7.44 (dd, J=27.5,
8.9Hz,2H),7.30–7.25(m,1H),3.83(s,3H)ppm.13C NMR(101MHz,CDCl3)δ176.7,142.0,
140.5,133.9,133.5,127.4,126.9,126.4,122.8,122.0,121.4,116.5,114.8,33.6ppm.
The nuclear magnetic data of case study on implementation 7：1H NMR(400MHz,CDCl3) δ 8.58 (dd, J=8.0,1.3Hz, 1H), 8.43
(d, J=2.1Hz, 1H), 7.72 (t, J=7.9Hz, 1H), 7.63 (dd, J=8.8,2.2Hz, 1H), 7.50 (dd, J=11.6,
8.9Hz, 2H), 7.31-7.25 (m, 1H), 3.89 (s, 3H), 3.07 (p, J=7.0Hz, 1H), 1.34 (d, J=6.9Hz, 6H)
ppm.13C NMR(101MHz,CDCl3)δ178.0,142.3,141.7,140.8,133.5,132.8,127.6,124.3,
122.3,120.8,114.8,114.5,33.4,33.3,23.9ppm.HRMS(EI):Exact mass calcd for
C17H17NO.[M]+:251.1311,Found:251.1305.
The nuclear magnetic data of case study on implementation 8：1H NMR(400MHz,CDCl3) δ 8.47 (d, J=9.5Hz, 1H), 7.65 (t, J
=8.7Hz, 1H), 7.43 (d, J=8.6Hz, 1H), 7.23 (t, J=7.5Hz, 1H), 7.12 (s, 1H), 6.86 (s, 1H),
3.81(s,3H),2.96(s,3H),2.46(s,3H)ppm.13C NMR(101MHz,CDCl3)δ179.6,144.3,143.1,
142.2,141.8,132.9,127.4,126.0,123.8,120.7,119.0,114.3,112.8,34.3,24.4,
22.2ppm.
The nuclear magnetic data of case study on implementation 10：1H NMR(400MHz,CDCl3) δ 8.56 (d, J=7.7Hz, 1H), 8.35 (s,
1H), 7.71 (t, J=7.9Hz, 1H), 7.52 (dd, J=14.1,8.2Hz, 2H), 7.43 (d, J=8.8Hz, 1H), 7.31-
7.24(m,1H),3.87(s,3H),2.47(s,3H)ppm.13C NMR(101MHz,CDCl3)δ178.0,142.4,140.6,
135.2,133.6,130.9,127.8,127.0,122.3,122.3,120.9,114.7,114.6,33.5,20.6ppm.
The nuclear magnetic data of case study on implementation 13：1H NMR(400MHz,CDCl3) δ 8.73 (d, J=2.4Hz, 1H), 8.44 (d, J
=7.7Hz, 1H), 7.85-7.77 (m, 1H), 7.74-7.67 (m, 1H), 7.49 (dd, J=15.2,8.9Hz, 2H), 7.27 (t,
J=7.5Hz, 1H), 3.85 (s, 3H) ppm.13C NMR(101MHz,CDCl3)δ177.2,143.9,142.2,134.3,
129.6,127.5,125.4,123.1,122.8,122.1,121.4,115.6,115.0,33.8ppm.19F NMR(376MHz,
CDCl3)δ-61.7ppm.
The nuclear magnetic data of case study on implementation 14：1H NMR(400MHz,CDCl3) δ 8.49 (dd, J=8.0,1.5Hz, 1H),
8.36 (s, 1H), 7.72 (t, J=8.7Hz, 1H), 7.57-7.46 (m, 3H), 7.32-7.25 (m, 1H), 3.87 (s, 3H)
ppm.13C NMR(101MHz,CDCl3)δ177.1,143.2,142.3,140.8,134.2,127.6,127.1,122.8,
122.0,121.7,119.3,119.1,116.7,114.8,33.9ppm.19F NMR(376MHz,CDCl3)δ-
58.1ppm.HRMS(EI):Exact mass calcd for C14H10F3NO2.[M]+:294.0694,Found:294.0737.
The nuclear magnetic data of case study on implementation 15：1H NMR(400MHz,CDCl3) δ 8.59 (d, J=7.9Hz, 2H), 7.73 (d, J
=8.1Hz, 2H), 7.60-7.48 (m, 2H), 7.29 (q, J=6.4,4.9Hz, 2H), 4.52-4.42 (m, 2H), 1.56 (q, J
=6.1Hz, 3H) ppm.13C NMR(101MHz,CDCl3)δ178.1,141.5,133.9,128.1,122.5,121.2,
114.3,41.0,12.6ppm.
The nuclear magnetic data of case study on implementation 16：1H NMR(400MHz,CDCl3) δ 8.59 (dd, J=8.0,1.8Hz, 2H),
7.78-7.69 (m, 2H), 7.61 (d, J=8.7Hz, 2H), 7.29 (dd, J=14.5,7.2Hz, 2H), 4.40 (d, J=
5.6Hz, 2H), 1.34 (ddd, J=13.6,8.2,5.5Hz, 1H), 0.69 (q, J=6.1Hz, 2H), 0.53 (q, J=5.2Hz,
2H)ppm.13C NMR(101MHz,CDCl3)δ178.0,142.1,133.7,127.9,122.4,121.2,115.2,48.7,
9.7,4.4ppm.HRMS(EI):Exact mass calcd for C17H15NO.[M]+:249.1153,Found:
249.1148.
The nuclear magnetic data of case study on implementation 17：1H NMR(400MHz,CDCl3) δ 8.59 (d, J=8.7Hz, 2H), 7.74 (t, J
=7.9Hz, 2H), 7.50 (d, J=8.7Hz, 2H), 7.30 (t, J=7.5Hz, 2H), 4.51-4.19 (m, 2H), 2.05-1.87
(m, 2H), 1.62-1.23 (m, 11H), 0.91 (t, J=6.4Hz, 3H) ppm.13C NMR(101MHz,CDCl3)δ178.0,
141.7,133.8,127.9,122.4,121.1,114.5,46.2,31.7,29.3,29.2,27.1,26.9,22.6,
14.1ppm.HRMS(EI):Exact mass calcd for C21H25NO.[M]+:307.1934,Found:307.1831.
The nuclear magnetic data of case study on implementation 18：1H NMR(400MHz,CDCl3) δ 8.60 (dd, J=8.0,1.5Hz, 2H),
7.69–7.57(m,2H),7.41–7.18(m,9H),5.60(s,2H)ppm.13C NMR(101MHz,CDCl3)δ178.2,
142.5,135.4,134.0,129.2 127.8,127.7,125.6,122.5,121.6,115.2,50.8ppm.
The nuclear magnetic data of case study on implementation 19：1H NMR(400MHz,CDCl3) δ 8.59 (dd, J=8.0,1.1Hz, 2H),
7.70 (d, J=7.5Hz, 3H), 7.49 (t, J=7.0Hz, 2H), 7.37 (d, J=7.0Hz, 2H), 7.27 (t, J=7.5Hz,
2H), 6.76 (d, J=8.6Hz, 2H) ppm.13C NMR(101MHz,CDCl3)δ178.1,143.1,138.9,133.2,
131.1,130.0,129.6,127.2,121.7,121.5,116.8ppm.
The nuclear magnetic data of case study on implementation 20：1H NMR(400MHz,CDCl3) δ 8.58 (d, J=7.3Hz, 1H), 8.37 (s,
1H), 7.67 (dd, J=16.0,7.3Hz, 3H), 7.48 (s, 1H), 7.34 (dd, J=15.2,8.2Hz, 3H), 7.24 (d, J=
7.0Hz, 1H), 6.75 (d, J=8.3Hz, 1H), 6.66 (d, J=8.4Hz, 1H), 2.45 (s, 3H) ppm.13C NMR
(101MHz,CDCl3)δ178.1,143.0,141.3,139.1,134.8,133.1,131.3,131.1,130.1,129.6,
127.3,126.5,121.7,121.6,121.3,116.9,116.8,20.7ppm.
The nuclear magnetic data of case study on implementation 21：1H NMR(400MHz,CDCl3) δ 8.55 (t, J=7.2Hz, 1H), 8.25-
8.17 (m, 1H), 7.72 (dd, J=15.5,7.7Hz, 3H), 7.52 (d, J=7.5Hz, 1H), 7.40 (d, J=7.2Hz, 2H),
7.32-7.21 (m, 2H), 6.77 (t, J=7.4Hz, 2H) ppm.13C NMR(101MHz,CDCl3)δ177.4,158.9,
142.9,139.7,138.8,133.5,131.2,129.9,129.8,127.1,122.6,122.5,121.9,121.7,
120.9,119.0,118.9,116.8,111.6,111.3ppm.19F NMR(376MHz,CDCl3)δ-120.8ppm.HRMS
(EI):Exact mass calcd for C19H12FNO.[M]+:290.0936,Found:290.0976.
The basic principles and main features and advantage of the present invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiment obtained under bright technical solution should all cover among the scope of the claims of the present invention.
Claims (6)
1. the preparation method of a kind of acridone and its derivative, which is characterized in that concrete operation step is：
(1) dry Schlenk is added in palladium catalyst, organophosphorus ligand and inorganic base together to manage, by the gas in Schlenk pipes
Body atmosphere is replaced into carbon monoxide by air；
(2) under CO gas atmosphere, anhydrous n,N-Dimethylformamide is added, is heated to 120 DEG C, stirs 30 minutes；
(3) 2- bromine diphenylamine substrates are added, 120 DEG C are reacted 12 hours, are cooled to room temperature；
(4) saturated ammonium chloride solution is added and reaction is quenched, add extracted with ethyl acetate after water, column chromatography for separation, purifying；
Wherein, the 2- bromines diphenylamine substrate, palladium catalyst, organophosphorus ligand, inorganic base the amount ratio of substance be：1.00∶
0.05∶0.10∶3.00。
2. the preparation method of a kind of acridone and its derivative as described in claim 1, which is characterized in that the 2- bromines diphenylamines
Class substrate is N- methyl -2- bromines diphenylamines, the bromo- 4 '-methyldiphenylamines of N- methyl -2-, the bromo- 4 '-tertiary butyl hexichol of N- methyl -2-
The bromo- 4 '-methoxy diphenylamine of amine, N- methyl -2-, the bromo- 4 '-fluorine diphenylamines of N- methyl -2-, the bromo- 4 '-chlorodiphenyls of N- methyl -2-
The bromo- 4 '-isopropyl diphenyl amine of amine, N- methyl -2-, bromo- 3 ', the 5 '-dimethyl diphenylamines of N- methyl -2-, the bromo- 4- of N- methyl -2-
The bromo- 4- chlorine of the bromo- 5- methyldiphenylamines of methyldiphenylamine, N- methyl -2-, the bromo- 4- fluorine diphenylamines of N- methyl -2-, N- methyl -2- two
The bromo- 4- trifluoromethyls diphenylamines of aniline, N- methyl -2-, the bromo- 4- trifluoromethoxies diphenylamines of N- methyl -2-, N- ethyl -2- bromines
Diphenylamines, N- methylcyclopropyl groups -2- bromines diphenylamines, N- hexyl -2- bromines diphenylamines, N- benzyl -2- bromines diphenylamines, 2- bromine triphens
One kind in the bromo- 4- methyl triphenylamine of amine, 2-, the bromo- 4- fluorine triphenylamines of 2-.
3. the preparation method of a kind of acridone as described in claim 1 and its derivative, which is characterized in that the palladium catalyst
For palladium bichloride.
4. the preparation method of a kind of acridone as described in claim 1 and its derivative, which is characterized in that the organophosphite ligand
Body is tricyclohexyl phosphine tetrafluoroborate.
5. the preparation method of a kind of acridone as described in claim 1 and its derivative, which is characterized in that the inorganic base is
Pivalic acid caesium.
6. the preparation method of a kind of acridone as described in claim 1 and its derivative, which is characterized in that the carbon monoxide
Atmosphere is a standard atmospheric pressure.
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| WO2019163732A1 (en) * | 2018-02-26 | 2019-08-29 | 住友化学株式会社 | Compound and coloring resin composition |
| US11584852B2 (en) | 2018-02-26 | 2023-02-21 | Sumitomo Chemical Company, Limited | Compound and colored resin composition |
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| CN104844400A (en) * | 2015-04-13 | 2015-08-19 | 南京邮电大学 | Preparation method for 9-fluorenone and T type oligomeric phenylene skeleton compounds |
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| WO2019163732A1 (en) * | 2018-02-26 | 2019-08-29 | 住友化学株式会社 | Compound and coloring resin composition |
| US11584852B2 (en) | 2018-02-26 | 2023-02-21 | Sumitomo Chemical Company, Limited | Compound and colored resin composition |
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