CN110317160A - A kind of new method red by C-H activated sulfonamides 2- phenyl isoindigo - Google Patents
A kind of new method red by C-H activated sulfonamides 2- phenyl isoindigo Download PDFInfo
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Abstract
The present invention relates to one kind using sulfonyl azide as coupling reagent, constructs the new method of the different Isatine derivatives of 2- phenyl to the red carry out sulfuryl amine of 2- phenyl isoindigo by transition metal-catalyzed aryl C-H priming reaction.The present invention is compared to traditional technology, and functional group tolerance is good, high income；Low temperature, safe ready have broad application prospects；By-product is only nitrogen, avoids and generates a large amount of by-product, improves atom utilization；Without carrying out the pre-activate of substrate, reaction condition is mild and the reaction time is short, reduces operation difficulty.
Description
Technical field
The invention belongs to technical field of organic synthetic chemistry, and in particular to one kind passed through using sulfonyl azide as coupling reagent
Metal catalytic aryl C-H priming reaction is crossed, to the red carry out sulfuryl amine of 2- phenyl isoindigo, constructs the different Isatine derivatives of 2- phenyl
New method.
Background technique
Red isoindigo is a kind of important structural unit, and analog has antibacterial, antimycotic and antiproliferative activity[1-4].Its
In, 2 phenyl of the red class compound of 2- phenyl isoindigo play an important role in antiplasmodial activities, therefore 2- phenyl isoindigo is red
It has received widespread attention in recent years[1].It is interesting that the study found that such compound can be enhanced by introducing amino group on phenyl
Anti-malarial activity[2].There are many method for establishing 2- phenylisatin[1,3], but when phenyl neighbour's substd, reaction yield is very
It is low, and the reaction of this kind of compound is mainly cycloaddition reaction, such as and alkene[3], olefine aldehydr[4]And indoles[5]Reaction.Therefore,
It is necessary to develop more effective, more flexible method to modify these compounds to obtain the red class compound of more 2- phenyl isoindigos
Derivative.
In recent years, transition metal-catalyzed C-H bond functionalization is widely used in constructing C-C key, C- heterodesmic, heterocycle[6].And N-
O is often used as homing device in C-H activation process, guides metallic catalyst close to some c h bond in molecule, to lead
Cause its selective splitting and with Post functionalization[6].Theoretically speaking the red N-O of 2- phenyl isoindigo can also be used as a guiding base
Group is used for C-H priming reaction, realizes the sulfuryl amine at the red phenyl ring ortho position of 2- phenyl isoindigo.
Summary of the invention
The present invention is realized using the red class compound of 2- phenyl isoindigo as raw material, and sulfonyl azide is coupling reagent, passes through transition
Metal catalytic aryl C-H priming reaction constructs the new method of the different Isatine derivatives of 2- phenyl to the red sulfuryl amine of 2- phenyl isoindigo.
The present invention solves the problems such as cumbersome reaction step in prior synthesizing method, severe reaction conditions, low atom utilization, reduces
Production cost, and by-product is only nitrogen, avoids environmental pollution, the present invention provides a kind of more mild, quickly, easy,
Safely, effectively, at low cost, good substrate applicability preparation method, has broad application prospects.
Technology path of the invention is using the red class compound of 2- phenyl isoindigo as substrate, using sulfonyl azide as coupling reagent,
Direct step coupling under room temperature；Its chemical equation is as follows:
Wherein:
R1For hydrogen, alkyl, alkoxy or ester group；
R2For hydrogen, alkyl, alkoxy, halogen or trifluoromethyl；
R3For alkyl, aminomethyl phenyl, methoxyphenyl, halogen phenyl or nitrobenzophenone.
Preparation step is as follows:
(1) the red class compound of 2- phenyl isoindigo, sulfonyl azide class compound, silver salt, acid and molten are added in clean reactor
Agent is stirred 1-5 hour at room temperature；
(2) after fully reacting, solvent is removed through vacuum distillation, residue is using silica gel column chromatography separating purification up to product.
Catalyst in step (1) is palladium carbon, tetrakis triphenylphosphine palladium, palladium acetate, palladium chloride, two (acetonitrile) dichlorides
Palladium, two (cyanophenyl) palladium chlorides, it is 1,1 '-two (diphenylphosphino) ferrocene palladium chloride, two (triphenylphosphine) palladium chlorides, double
(dibenzalacetone) palladium, tris(dibenzylideneacetone) dipalladium, chlorination Allylpalladium (II) dimer, (1,5- cyclo-octadiene) two
Palladium chloride (II), rhodium carbon, rhodium chloride, rhodium acetate, acetylacetonatodicarrhodium rhodium, bicyclooctene radium chloride dimer,
Dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer, (two (hexafluoro-antimonic acid) three acetonitrile (pentamethylcyclopentadiene base) rhodiums
(III)), triphenylphosphine radium chloride, ruthenium trichloride, triphenylphosphine ruthenic chloride, dichloro dicarbapentaborane bi triphenyl phosphine ruthenium, bis- (2- first
Base allyl) (1,5- cyclo-octadiene) ruthenium (II), p-cymene ruthenous chloride dimer, cobalt chloride, acetoacetyl cobalt, eight carbonyls
Two cobalts, dichloro (pentamethylcyclopentadiene base) close cobalt (III) dimer, pentamethylcyclopentadiene base carbonyl cobalt diiodide, (two
(hexafluoro-antimonic acid) three acetonitrile (pentamethylcyclopentadiene base) cobalt (III)), iridous chloride, dichloro (pentamethylcyclopentadiene) close iridium
(III) dimer, bis- (1,5- cyclo-octadiene) iridium chloride (I) dimer, methoxyl group (cyclo-octadiene) close one in iridium dimer
Kind or more than one.
Silver salt in step (1) is silver nitrate, silver acetate, silver carbonate, silver sulfate, utilized as silver methane sulfonate, trifluoromethayl sulfonic acid
Silver, p-methyl benzenesulfonic acid silver, double trifluoromethanesulfonimides silver, trifluoro-methane sulfonic acid silver, silver hexafluoroantimonate, silver tetrafluoroborate, six
One of fluorophosphoric acid silver or more than one.
Acid in step (1) is pivalic acid, adamantanecarboxylic acid, acetic acid, trifluoroacetic acid, one of benzoic acid or it is a kind of with
On.
Solvent in step (1) is trifluoroethanol, hexafluoroisopropanol, methylene chloride, 1,2- dichloroethanes, Isosorbide-5-Nitrae-dioxy six
Ring, tetrahydrofuran, acetonitrile, ethyl alcohol, methanol, toluene, water, N1,N3One of disubstituted imidazole class ionic liquid or it is a kind of with
On.
The red class compound of 2- phenyl isoindigo in step (1): sulfonyl azide class compound: catalyst: silver salt: sour mole is
1:(1.1 ~ 2.0): (0.01 ~ 0.05): (0.08 ~ 0.2): (0.5-2.0).
The reaction density of aryl-heterocyclic class compound is 0.1 ~ 0.5mol/L in step (1).
With nuclear magnetic resonance spectroscopy (1H NMR), carbon spectrum (13C NMR) and high resolution mass spectrum confirm it is red in 2- phenyl isoindigo
C-H activates the structure to form sulfonic acid amide derivatives, such as attached drawing 1, attached drawing 2.Wherein nuclear magnetic resonance figures use Varian INOVA-
400 type nmr determinations, with tetramethylsilane (TMS) for internal standard (0 ppm of δ), deuterated dimethyl sulfoxide is solvent；It is high
Resolution Mass Spectrometry is measured with Agilent 1946B mass spectrograph.
Compared to traditional synthetic method, the present invention is using sulfonyl azide class compound as coupling reagent, transition metal-catalyzed
Aryl C-H coupling reaction method that C-N key is formed efficiently on the red phenyl ring of 2- phenyl isoindigo have the advantages that many uniquenesses,
It embodies are as follows:
1. C-H coupling reaction of the present invention is red for substrate with 2- phenyl isoindigo, reaction rapidly, passes through one at room temperature
Step reaction efficiently and rapidly forms C-N key on phenyl ring, reduces reaction step and operation difficulty, save the cost；
2. substrate applicability of the present invention is wide, functional group tolerance is strong；Attack reagent reactivity is high, is 2- phenyl isoindigo
The development of red class drug leaves wide space；
3. synthetic route of the present invention is coupling reagent with sulfonyl azide, the by-product generated during the reaction is only
Nitrogen avoids and generates a large amount of wastes, Atom economy and environment friendly with higher.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the compounds of this invention 1
Fig. 2 is the nuclear-magnetism carbon spectrogram of the compounds of this invention 1
Specific implementation method
The invention will be further described With reference to embodiment, facilitates the understanding of the present invention.But it can not be with
This limits interest field of the invention, and interest field of the invention should be subject to claims elaborations.
Embodiment 1: the synthesis of compound 1
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, it is folded to Methyl benzenesulfonyl
Nitrogen (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), trifluoroethanol
(1.0 ml) is stirred 5 hours at room temperature after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 35.7 mg of target product, orange solids, yield 91%；1H NMR (400 MHz, DMSO-d 6 ) δ 9.07 (s, 1H), 7.89– 7.85 (m, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.75 – 7.70
(m, 2H), 7.60 – 7.55 (m, 1H), 7.47 (dd, J = 8.4, 1.6 Hz, 1H), 7.37 (t, J =
7.2 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.98 (d, J = 8.0 Hz, 2H), 2.19 (s,
3H); 13C NMR (100 MHz, DMSO-d 6 ) δ 183.82, 146.91, 143.36, 136.64, 136.10,
135.34, 135.11, 132.16, 131.97, 131.80, 129.60, 125.98, 125.72, 125.65,
122.97, 121.91, 118.74, 114.37, 20.92; HRMS (ESI): m/zCalculated value C21H16N2O4SNa+:
415.0723 measured value: 415.0720.
Embodiment 2: the synthesis of compound 1
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, it is folded to Methyl benzenesulfonyl
Nitrogen (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), silver tetrafluoroborate (3.9 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), trifluoroethanol (1.0 ml), argon
It is stirred at room temperature 5 hours after gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 23.5 mg of target product, orange solids, yield 60%.
Embodiment 3: the synthesis of compound 1
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, it is folded to Methyl benzenesulfonyl
Nitrogen (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), adamantanecarboxylic acid (36.1 mg, 0.20 mmol), and three
Fluoroethanol (1.0 ml) stirs 5 hours under 90 °C after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 30.6 mg of target product, orange solids, yield 78%.
Embodiment 4: the synthesis of compound 1
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, it is folded to Methyl benzenesulfonyl
Nitrogen (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), adamantanecarboxylic acid (36.1 mg, 0.20 mmol), and 1,
2- dichloroethanes (1.0 ml) stirs 5 hours under 90 °C after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 31.4 mg of target product, orange solids, yield 80%.
Embodiment 5: the synthesis of compound 1
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, it is folded to Methyl benzenesulfonyl
Nitrogen (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), adamantanecarboxylic acid (36.1 mg, 0.20 mmol), and six
Fluorine isopropanol (1.0 ml) stirs 5 hours under 90 °C after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 27.5 mg of target product, orange solids, yield 70%.
Embodiment 6: the synthesis of compound 2
(1) it is red (23.7 mg, 0.10 mmol) that 2- p-methylphenyl isoindigo is sequentially added in clean reactor, to methylbenzene
Sulfonyl azide (39.5 mg, 0.20 mmol), dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg,
0.005 mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), and three
Fluoroethanol (1.0 ml) stirs 5 hours at room temperature after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 36.2 mg of target product, orange solids, yield 89%；1H NMR (400 MHz, DMSO-d 6) δ 8.92 (s, 1H), 7.90 – 7.83 (m, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.73 –
7.66 (m, 2H), 7.37 (d, J = 8.0 Hz, 1H), 7.28 – 7.20 (m, 4H), 6.89 (d, J = 8.0
Hz, 2H), 2.37 (s, 3H), 2.15 (s, 3H); 13C NMR (100 MHz, DMSO-d 6) δ 184.10,
147.29, 143.75, 143.05, 136.99, 136.47, 135.92, 135.70, 132.39, 132.17,
129.99, 127.61, 127.50, 126.23, 123.26, 122.41, 116.70, 114.81, 21.56, 21.36;
HRMS (ESI): m/zCalculated value C22H18N2O4SNa+: 429.0879, measured value: 429.0882.
Embodiment 7: the synthesis of compound 3
(1) it is red (25.8 mg, 0.10 mmol) that 2- rubigan isoindigo is sequentially added in clean reactor, to methylbenzene sulphur
Acyl azide (39.5 mg, 0.20 mmol), and dichloro (pentamethylcyclopentadiene base) conjunction iridium (III) dimer (2.0 mg, 0.005
Mmol), double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), trifluoroethanol
(1.0 ml) is stirred 5 hours at room temperature after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 32.2 mg of target product, orange solids, yield 75%；1H NMR (400 MHz, DMSO-d 6) δ 9.30 (s, 1H), 7.91 – 7.84 (m, 1H), 7.78 (d, J = 7.6 Hz, 1H), 7.74 (d, J
= 4.4 Hz, 2H), 7.61 (dd, J = 8.8, 2.4 Hz, 1H), 7.51 (d, J = 2.4 Hz, 1H), 7.41
(d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.8 Hz, 1H), 7.08 (d, J = 8.0 Hz, 2H), 2.23
(s, 3H); 13C NMR (100 MHz, DMSO-d 6) δ 183.76, 146.95, 143.67, 135.97, 135.74,
135.34, 133.87, 132.04, 131.63, 131.44, 129.76, 129.44, 126.26 (2s), 123.11,
122.00, 120.10, 114.49, 20.99; HRMS (ESI): m/zCalculated value C21H15ClN2O4SNa+: 449.0333,
Measured value: 429. 449.0336.
Embodiment 8: the synthesis of compound 4
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, to chlorobenzenesulfonyl nitrine
(39.5 mg, 0.20 mmol), dichloro (pentamethylcyclopentadiene base) close iridium (III) dimer (2.0 mg, 0.005 mmol),
Double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), trifluoroethanol (1.0
Ml), stirred at room temperature 5 hours after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 36.3 mg of target product, orange solids, yield 88%；1H NMR (400 MHz, DMSO-d 6) δ 9.38 (s, 1H), 7.91 – 7.84 (m, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.74 –
7.68 (m, 2H), 7.60 – 7.53 (m, 1H), 7.53 – 7.46 (m, 3H), 7.43 – 7.30 (m, 4H);13C NMR (100 MHz, DMSO-d 6) δ 184.13, 146.96, 138.03, 137.89, 136.27, 135.41,
135.00, 132.28, 132.05, 131.92, 129.44, 128.07, 125.99, 125.38, 122.94,
122.02, 119.00, 114.42; HRMS (ESI): m/zCalculated value C20H13ClN2O4SNa+: 435.0177, measured value:
435.0178。
Embodiment 9: the synthesis of compound 5
(1) it is red (22.3 mg, 0.10 mmol) that 2- phenyl isoindigo is sequentially added in clean reactor, methylsulphur acyl azide
(24.2 mg, 0.20 mmol), dichloro (pentamethylcyclopentadiene base) close iridium (III) dimer (2.0 mg, 0.005 mmol),
Double trifluoromethanesulfonimides are silver-colored (7.8 mg, 0.02mmol), acetic acid (12.0 mg, 0.20 mmol), trifluoroethanol (1.0
Ml), stirred at room temperature 5 hours after argon gas displacement.
(2) after the reaction was completed, solvent is removed under reduced pressure, residue uses silica gel column chromatography (petrol ether/ethyl acetate=10/
1, v/v) it isolates and purifies, obtains 25.6 mg of target product, orange solids, yield 88%；1H NMR (400 MHz, DMSO-d 6) δ 9.27 (s, 1H), 7.84 (t, J = 7.6 Hz, 1H), 7.76-7.67 (m, 4H), 7.56 (t, J =
8.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 3.08 (s,
3H); 13C NMR (100 MHz, DMSO-d 6) δ 185.36, 147.48, 137.67, 134.93, 134.79,
132.25, 131.80, 131.66, 124.06, 123.71, 121.75, 120.91, 116.66, 114.24,
39.73; HRMS (ESI): m/zCalculated value C15H12N2O4SNa+: 339.0410, measured value: 339.0418.
Bibliography
1.Nepveu, F.; Kim, S.; Boyer, J.; Chatriant, O.; Ibrahim, H.; Reybier,
K.; Monje, M. C. ; Chevalley, S. Perio P.; Lajoie, B. H.; Bouajila, J.;
Deharo, E.; Sauvain, M.; Tahar, R.; Basco, L.; Pantaleo, A.; Turini, F.;
Arese, P.; Valentin, A.; Thompson, E.; Vivas, L.; Petit, S.; Nallet, J. P. J Med Chem 2010, 53, 699-714.
2.Najahi, E.; Rakotoarivelo, N. V. ; Valentin, A. ; Nepveu, F. Eur J Med Chem 2014, 76, 369-375.
3.Ramana, C. V.; Patel, P.; Vanka, K.; Miao, B.; Degterev, A.; European Journal of Organic Chemistry 2010, 2010, 5955-5966.
4.Ibrahim, H.; Furiga, A.; Najahi, E.; Pigasse Henocq, C.; J. P. Nallet,
J. P.; Roques, C. ; Aubouy, A.; Sauvain, M.; Constant, P.; Daffe, M.; Nepveu,
F. J Antibiot (Tokyo) 2012, 65, 499-504.
5.Kumar, C.; Ramana, C. V. Org Lett 2015, 17, 2870-2873.
6.X, J.; Hu, S.; Lu, Y.; Dong, Y.; Tang, W.; Lu, T.; Du, D. Advanced Synthesis & Catalysis 2015, 357, 923-927.
7.Liu, R. R.; Ye, S. C.; Lu, C. J.; Zhuang, G. L. Gao, J. R.; Jia, Y. X.;Angew Chem Int Ed Engl 2015, 54, 11205-11208.
8.Sambiagio, C.; Schonbauer, D.; Blieck, R.; Dao-Huy, T.; Pototschnig,
G.; Schaaf, P. ; Wiesinger, T.; Zia, M. F.; Wencel-Delord, J.; Besset, T. ;
Maes, B. U. W.; Schnurch, M. Chem Soc Rev 2018, 47, 6603-6743。
Claims (7)
1. one kind is using sulfonyl azide as coupling reagent, red to 2- phenyl isoindigo by transition metal-catalyzed aryl C-H priming reaction
Sulfuryl amine is carried out, the new method of the different Isatine derivatives of 2- phenyl is constructed；It is characterized in that being coupling with sulfonyl azide compound
Reagent quickly forms C-N key, chemical equation on the red phenyl ring of 2- phenyl isoindigo at room temperature are as follows:
Wherein:
R1For hydrogen, alkyl, alkoxy or ester group；
R2For hydrogen, alkyl, alkoxy, halogen or trifluoromethyl；
R3For alkyl, aminomethyl phenyl, methoxyphenyl, halogen phenyl or nitrobenzophenone.
2. the synthetic method of the different Isatine derivatives of 2- phenyl according to claim 1, it is characterised in that using following preparation
Step:
(1) the red class compound of 2- phenyl isoindigo, sulfonyl azide class compound, catalyst, silver salt are added in clean reactor,
Acid and solvent stir 1-5 hour at room temperature after argon gas displacement；
(2) after fully reacting, solvent is removed through vacuum distillation, residue is using silica gel column chromatography separating purification up to product.
3. preparation method according to claim 2, it is characterised in that the catalyst in step (1) is palladium carbon, four (triphenyls
Phosphine) palladium, palladium acetate, palladium chloride, two (acetonitrile) palladium chlorides, two (cyanophenyl) palladium chlorides, 1,1 '-two (diphenylphosphino) two cyclopentadienyl
Iron palladium chloride, two (triphenylphosphine) palladium chlorides, bis- (dibenzalacetone) palladiums, tris(dibenzylideneacetone) dipalladium, chlorination
Allylpalladium (II) dimer, (1,5- cyclo-octadiene) palladium chloride (II), rhodium carbon, rhodium chloride, rhodium acetate, acetylacetone,2,4-pentanedione three
Phenylphosphine rhodium carbonyl, bicyclooctene radium chloride dimer, dichloro (pentamethylcyclopentadiene base) close rhodium (III) dimer, (two
(hexafluoro-antimonic acid) three acetonitrile (pentamethylcyclopentadiene base) rhodium (III)), triphenylphosphine radium chloride, ruthenium trichloride, triphenylphosphine chlorine
Change ruthenium, dichloro dicarbapentaborane bi triphenyl phosphine ruthenium, bis- (2- methacrylics) (1,5- cyclo-octadiene) ruthenium (II), p-cymene dichloro
Change ruthenium dimer, cobalt chloride, acetoacetyl cobalt, cobalt octacarbonyl, dichloro (pentamethylcyclopentadiene base) and closes cobalt (III) dimerization
Body, pentamethylcyclopentadiene base carbonyl cobalt diiodide, (two (hexafluoro-antimonic acid) three acetonitrile (pentamethylcyclopentadiene base) cobalts
(III)), iridous chloride, dichloro (pentamethylcyclopentadiene) close iridium (III) dimer, bis- (1,5- cyclo-octadiene) iridium chlorides (I)
Dimer, methoxyl group (cyclo-octadiene) close one of iridium dimer or more than one.
4. preparation method according to claim 2, it is characterised in that the silver salt in step (1) is silver nitrate, silver acetate, carbon
Sour silver, silver sulfate, utilized as silver methane sulfonate, trifluoro-methane sulfonic acid silver, p-methyl benzenesulfonic acid silver, double trifluoromethanesulfonimides silver, trifluoro
One of utilized as silver methane sulfonate, silver hexafluoroantimonate, silver tetrafluoroborate, Silver hexafluorophosphate or more than one.
5. preparation method according to claim 2, it is characterised in that acid in step (1) be pivalic acid, adamantanecarboxylic acid,
One of acetic acid, trifluoroacetic acid, benzoic acid or more than one.
6. preparation method according to claim 2, it is characterised in that the red class compound of 2- phenyl isoindigo in step (1):
Sulfonyl azide class compound: catalyst: silver salt: sour mole is 1: (1.1 ~ 2.0): (0.01 ~ 0.05): (0.08 ~
0.2): (0.5-2.0).
7. preparation method according to claim 2, it is characterised in that the red class compound of 2- phenyl isoindigo is anti-in step (1)
Answering concentration is 0.1 ~ 0.5mol/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153011A (en) * | 2015-07-13 | 2015-12-16 | 常州大学 | Synthesis method of 2-sulfonyliminoindoline |
| CN107903260A (en) * | 2017-11-20 | 2018-04-13 | 中国医药集团总公司四川抗菌素工业研究所 | A kind of indoles and dihydropyridine ketone compound and its crystal form and preparation method |
| CN108640869A (en) * | 2018-05-29 | 2018-10-12 | 四川大学 | Transition metal-catalyzed C-H couplings efficiently prepare mebenil aryl-heterocyclic analog derivative |
| CN109336808A (en) * | 2018-11-01 | 2019-02-15 | 四川大学 | The green new method of transition metal-catalyzed C-H carbenoid coupling reaction synthesis C-C key and N heterocyclic derivative |
| CN109608395A (en) * | 2018-12-25 | 2019-04-12 | 四川大学 | Transition metal-catalyzed C-H activation/cyclization reaction efficiently synthesizes the green syt new method of isoquinilone derivatives |
-
2019
- 2019-07-08 CN CN201910607914.7A patent/CN110317160B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153011A (en) * | 2015-07-13 | 2015-12-16 | 常州大学 | Synthesis method of 2-sulfonyliminoindoline |
| CN107903260A (en) * | 2017-11-20 | 2018-04-13 | 中国医药集团总公司四川抗菌素工业研究所 | A kind of indoles and dihydropyridine ketone compound and its crystal form and preparation method |
| CN108640869A (en) * | 2018-05-29 | 2018-10-12 | 四川大学 | Transition metal-catalyzed C-H couplings efficiently prepare mebenil aryl-heterocyclic analog derivative |
| CN109336808A (en) * | 2018-11-01 | 2019-02-15 | 四川大学 | The green new method of transition metal-catalyzed C-H carbenoid coupling reaction synthesis C-C key and N heterocyclic derivative |
| CN109608395A (en) * | 2018-12-25 | 2019-04-12 | 四川大学 | Transition metal-catalyzed C-H activation/cyclization reaction efficiently synthesizes the green syt new method of isoquinilone derivatives |
Non-Patent Citations (2)
| Title |
|---|
| BINGFENG ZHU，等: "Iridium(III)-Catalyzed Direct C¢H Sulfonamidation of 2-Aryl-1,2,3-triazole N-Oxides with Sulfonyl Azides", 《ADV. SYNTH. CATAL》 * |
| MANIKANTHA MARASWAMI，等: ""Iridium(III)-Catalyzed Selective and Mild C-H Amidation of Cyclic N-Sulfonyl Ketimines with Organic Azides", 《ADV. SYNTH. CATAL.》 * |
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