CN109020922A - A kind of preparation method of cyclic sulfonamide class compound - Google Patents
A kind of preparation method of cyclic sulfonamide class compound Download PDFInfo
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- -1 cyclic sulfonamide Chemical class 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 229940124530 sulfonamide Drugs 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims abstract description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 9
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 150000008331 benzenesulfonamides Chemical class 0.000 abstract description 5
- 238000005755 formation reaction Methods 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- OIZINMVCRAJMNL-UHFFFAOYSA-N piperazine 1,2-thiazole Chemical compound N1CCNCC1.S1N=CC=C1 OIZINMVCRAJMNL-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RXAWIEZRQHNLNA-UHFFFAOYSA-N 2-benzylbenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1CC1=CC=CC=C1 RXAWIEZRQHNLNA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PYMJVPGREIGFJB-UHFFFAOYSA-N 2-benzyl-4-chlorobenzenesulfonamide Chemical compound C(C1=CC=CC=C1)C1=C(C=CC(=C1)Cl)S(=O)(=O)N PYMJVPGREIGFJB-UHFFFAOYSA-N 0.000 description 1
- WHSWULHICGDHGQ-UHFFFAOYSA-N 2-benzyl-4-methylbenzenesulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C(CC=2C=CC=CC=2)=C1 WHSWULHICGDHGQ-UHFFFAOYSA-N 0.000 description 1
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 230000003208 anti-thyroid effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 229940043671 antithyroid preparations Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- JYJVVHFRSFVEJM-UHFFFAOYSA-N iodosobenzene Chemical compound O=IC1=CC=CC=C1 JYJVVHFRSFVEJM-UHFFFAOYSA-N 0.000 description 1
- GRTPAOVVVLZLDP-UHFFFAOYSA-N n-benzylbenzenesulfonamide Chemical class C=1C=CC=CC=1S(=O)(=O)NCC1=CC=CC=C1 GRTPAOVVVLZLDP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D281/00—Heterocyclic compounds containing rings of more than six members having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D281/18—Eight-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of cyclic sulfonamide class compound, and this method is using benzenesulfonamides and nitromethane as raw material, with Fe2+Or Fe3+As catalyst, under the induction of visible light, pass through the formation reaction synthesis middle ring sulfonamide compounds of C-N/C-C key.Reaction step of the present invention is short, easy to operate, and without stringent anhydrous and oxygen-free condition, and catalyst is low in cost, environmentally friendly, can be with higher regioselectivity and medium to higher yield synthesis of cyclic sulfamide compound.
Description
Technical field
The present invention relates to a kind of preparation methods of middle ring sulfamide compound, more particularly to one kind with the substitution of ortho position benzyl
Benzenesulfonamide compounds and nitromethane be raw material, using iron chloride or frerrous chloride as catalyst, in luring for visible light
It leads down, the method that cyclic sulfonamide class compound is prepared by the formation reaction of C-N/C-C key.
Background technique
Sulfamide compound is that one kind contains tri- kinds of heteroatomic heterocyclic compounds of S, N, O.This kind of compound has more
Kind pharmacological activity all shows good pharmacology at many aspects such as antithyroid, antitumor, antimycotic, antiviral, antidepression
Activity is molecule drug candidate useful in medicine research and development.Sulfamide compound is due also to its hypotoxicity, high efficiency, Gao Xuan
It is selecting property, environmentally friendly, and by as Insecticides (tech) & Herbicides (tech) and fungicide, it is widely used in pesticide field.
Due to the good application prospect of pyrazole compound, a variety of methods for preparing pyrazole compound established by successive and
Report, specifically includes that
1, Friedel-Crafts reaction
Rudolph in 1978, A.A. etc. (J.Org.Chem.1978,43,1218) are using o-aminophenyl methyl formate
Raw material obtains heptatomic ring shape sulfamide compound by six-step process.This method reports heptatomic ring shape sulfonamide for the first time
Synthesis, but reactions steps of this method is longer.
2, intramolecular aziridineization is reacted
Robert in 2010, H.D. etc. (Bioorg.Med.Chem.Lett.2010,20,7483) are taken using ortho position alkenyl
The benzenesulfonamides in generation are raw material, and Cu (I) is catalyst, and iodosobenzene is oxidant, and acetonitrile is solvent, prepares molecule
Interior nitrogen heterocycle propane compound, then the open loop under the attack of nucleopilic reagent, obtain target compound.This method can be medium to good
Good yield synthesising target compound, but when nucleopilic reagent attack generation open loop, the bad control of regioselectivity.Also, it is former
Expect that synthesis step is longer.
3, asymmetric reduction aminating reaction
The one sulfonamide that Zhou in 2017, Y.G. etc. (Chem.Commun., 2017,53,1704) utilize tert-butyl to replace
It for raw material, is deprotected under the catalysis of bronsted acid, then passes through asymmetric reduction amination under the action of palladium catalyst, it can be with
Target compound is obtained with preferable yield.This method can obtain target compound with the higher ee value of preferable yield, but
Need to use palladium catalyst during being, expensive and environment is unfriendly.
4, other synthetic methods
Chemler in 2007, S.R. etc. (J.Am.Chem.Soc., 2007,129,12948) are using alkenes compounds
Raw material, at Cu (OTf)3Catalytic action under, be added chiral ligand occur phosphinylidyne aminating reaction, can be synthesized with higher yield
Cyclic sulfonamide class compound, but this method still needs chiral ligand, and reaction temperature is higher.
In conclusion at present it has been reported that synthesis sulfamide compound method it is each advantageous, but more or less
There are a little deficiencies, some severe reaction conditions, acutely, some need noble metal catalyst, some reaction steps are longer and region
Selectivity is bad.
Summary of the invention
Technical problem to be solved by the present invention lies in providing, a kind of synthesis step is shorter, and selectivity is higher, and catalyst is honest and clean
Valence is easy to get, the preparation method of safe and non-toxic cyclic sulfonamide class compound.
Solving technical solution used by above-mentioned technical problem is: in air atmosphere, by benzene sulfonamide shown in Formulas I
Compound, iron chloride or frerrous chloride, nitromethane are uniformly mixed, and under 60~100 DEG C and visible light illumination, are stirred to react 6
~15 hours, obtain cyclic sulfonamide class compound shown in Formula II.
In formula I above, Formula II, R1、R2And R3It is independent to represent H, C1~C4Alkyl, C1~C2Appoint in alkoxy, halogen
It anticipates one kind, preferably R1、R2And R3It is independent to represent H, methyl, methoxyl group, any one in Cl.
Molar ratio preferably 1 ﹕ of above-mentioned preparation method, the benzenesulfonamides and iron chloride or frerrous chloride
(0.2~1.0)；Preferred 1:(40~2000 of molar ratio of the benzenesulfonamides and nitromethane).
Above-mentioned preparation method is stirred to react 6~10 hours further preferably under 80~90 DEG C and visible light illumination.
The present invention is using the benzenesulfonamides replaced as raw material, with Fe3+Or Fe2+As catalyst, in visible light
Under induction, cyclic sulfonamide class compound is prepared by the formation reaction of C-N/C-C key.Compared with prior art, system of the present invention
The major advantage of Preparation Method is:
(1) present invention can obtain target compound with higher regioselectivity, and reaction step is short.
(2) present invention does not need the catalyst of expensive high poison, and catalyst is low in cost, environmentally friendly.
(3) operation of the present invention is easy, does not need stringent anhydrous and oxygen-free operation.
(4) present invention can prepare the medium-ring compound of more difficult synthesis.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply mode.
Embodiment 1
In air atmosphere, be added in the round-bottomed flask dry to 25mL 24.7mg (0.1mmol) 2- benzyl benzene sulfonyl chloride,
3.2mg (0.02mmol) iron chloride and 10mL (0.2mol) nitromethane, in the case where 80 DEG C and 5 light blue color LED lamplights shine, stirring 6
Hour, reaction solution is washed 3 times with saturated sodium bicarbonate aqueous solution, ethyl acetate extraction, organic phase saturated sodium-chloride is added
Aqueous solution washs three times, carries out pillar layer separation as eluent for the mixed liquor of 1:5 using the volume ratio of ethyl acetate and petroleum ether,
Obtain 7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5- dioxide 24.9mg, yield 96%, reaction
Equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.92 (d, J=8.0Hz, 1H), 7.58
(d, J=7.6Hz, 1H), 7.51-7.41 (m, 2H), 7.29 (t, J=7.2Hz, 1H), 7.23 (t, J=7.6Hz, 1H), 7.16
(t, J=7.6Hz, 2H), 5.17 (dd, J=15.7,11.0Hz, 1H), 4.90 (d, J=13.7Hz, 1H), 4.43 (d, J=
10.6Hz, 1H), 4.18 (d, J=15.8Hz, 1H), 3.86 (d, J=13.7Hz, 1H)；13C NMR(100MHz,CDCl3)δ
142.65,142.52,140.02,137.91,134.49,132.89,131.44,130.94,130.66,130.06,128.66,
128.03,48.76,39.15；ESI-HRMS calculated value C14H13NO2SNa([M+Na]+) 282.0559, measured value 282.0562.
Embodiment 2
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- benzyl -4- methyl benzenesulfonamide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 2- methyl -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5-
Dioxide 24.0mg, yield 88%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.75 (d, J=8.0Hz, 1H), 7.46
(d, J=7.6Hz, 1H), 7.35 (s, 1H), 7.33-7.25 (m, 1H), 7.20-7.12 (m, 2H), 6.98 (d, J=8.0Hz,
1H), 5.13 (dd, J=15.6,11.2Hz, 1H), 4.84 (d, J=14.0Hz, 1H), 4.43 (d, J=10.8Hz, 1H), 4.14
(dd, J=15.6,1.6Hz, 1H), 3.78 (d, J=13.6Hz, 1H), 2.36 (s, 3H)；13C NMR(100MHz,CDCl3)δ
143.66,141.20,138.50,138.42,136.59,132.07,130.03,129.55,129.17,128.70,127.19,
127.12,47.32,37.67,21.32；SI-HRMS calculated value C15H15NO2SNa([M+Na]+) 296.0716, measured value
296.0722。
Embodiment 3
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- benzyl -5- methyl benzenesulfonamide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 3- methyl -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5-
Dioxide 20.2mg, yield 74%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.72 (s, 1H), 7.44 (d, J=
8.0Hz, 2H), 7.30-7.22 (m, 2H), 7.16-7.11 (m, 2H), 5.13 (dd, J=15.6,11.2Hz, 1H), 4.82 (d, J
=14.0Hz, 1H), 4.43 (d, J=10.4Hz, 1H), 4.14 (dd, J=16.0,2.0Hz, 1H), 3.80 (d, J=14.0Hz,
0H),2.26(s,3H；13C NMR(100MHz,CDCl3)δ141.39,140.88,136.68,136.42,135.53,133.64,
131.38,129.94,129.53,129.19,129.01,127.11,47.29,37.32,20.77；SI-HRMS calculated value
C15H15NO2SNa([M+Na]+) 296.0716, measured value 296.0720.
Embodiment 4
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- benzyl -4- methoxybenzenesulphoismide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 2- methoxyl group -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,
5- dioxide 8.1mg, yield 28%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.85 (d, J=8.8Hz, 1H), 7.45
(d, J=7.6Hz, 1H), 7.29 (t, J=7.2Hz, 1H), 7.21-7.15 (m, 2H), 7.05 (d, J=2.4Hz, 1H), 6.66
(d, J=8.8Hz, 1H), 5.15 (dd, J=16.0,11.2Hz, 1H), 4.87 (d, J=13.6Hz, 1H), 4.36 (d, J=
11.2Hz, 1H), 4.17 (d, J=15.6Hz, 1H), 3.84 (s, 3H), 3.78 (d, J=13.6Hz, 1H)；13C NMR
(100MHz,CDCl3)δ162.78,140.91,140.60,136.61,133.44,130.95,130.11,129.56,
129.20,127.28,117.55,110.27,,55.53,47.41,37.87；SI-HRMS calculated value C15H15NO3SNa([M+Na
]+) 312.0665, measured value 312.0666.
Embodiment 5
In the present embodiment, with the 2- benzyl benzene sulfonyl chloride in equimolar 2- benzyl -4- chlorobenzene sulfonamide alternative embodiment 1,
Other steps are same as Example 1, obtain chloro- 7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5, the 5- titanium dioxide of 2-
Object 22.1mg, yield 74%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.84 (d, J=8.4Hz, 1H), 7.55
(d, J=1.6Hz, 1H), 7.47 (d, J=7.6Hz, 1H), 7.33 (t, J=7.6Hz, 1H), 7.24-7.15 (m, 3H), 5.14
(dd, J=16.0,11.2Hz, 1H), 4.86 (d, J=13.6Hz, 1H), 4.48 (d, J=10.4Hz, 1H), 4.18 (d, J=
16.0Hz, 1H), 3.81 (d, J=13.6Hz, 1H)；13C NMR(100MHz,CDCl3)δ140.41,140.31,139.81,
138.92,136.43,131.32,130.14,130.08,129.63,129.44,127.56,126.69,47.29,37.52；
SI-HRMS calculated value C14H12ClNO2SNa([M+Na]+) 316.0619, measured value 316.0170.
Embodiment 6
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- (2- methylbenzyl) benzsulfamide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 11- methyl -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5-
Dioxide 17.5mg, yield 64%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.95 (d, J=8.0Hz, 1H), 7.68
(d, J=8.0Hz, 1H), 7.43 (t, J=7.6Hz, 1H), 7.22 (d, J=8.0Hz, 1H), 7.18 (d, J=8.8Hz, 1H),
7.08 (t, J=7.2Hz, 1H), 7.03 (d, J=7.2Hz, 1H), 5.13 (dd, J=15.6,10.8Hz, 1H), 4.68 (d, J=
14.4Hz, 1H), 4.55 (d, J=10.8Hz, 1H), 4.18 (dd, J=15.6,2.0Hz, 1H), 4.11 (d, J=14.4Hz,
1H),2.65(s,3H)；13C NMR(100MHz,CDCl3)δ142.02,138.76,137.64,137.56,137.53,132.45
(2C),131.65,128.93,127.87,126.94,126.55,47.87,33.49,21.59；SI-HRMS calculated value
C15H15NO2SNa([M+Na]+) 296.0716, measured value 296.0717.
Embodiment 7
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- (4- methylbenzyl) benzsulfamide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 9- methyl -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5-
Dioxide 23.2mg, yield 85%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.94 (d, J=7.6Hz, 1H), 7.56
(d, J=7.6Hz, 1H), 7.45 (t, J=7.2Hz, 1H), 7.35 (d, J=8.0Hz, 1H), 7.22 (d, J=7.6Hz, 1H),
7.09 (d, J=7.6Hz, 1H), 6.96 (s, 1H), 5.14 (dd, J=15.6,11.2Hz, 1H), 4.85 (d, J=14.0Hz,
1H), 4.37 (d, J=10.8Hz, 1H), 4.13 (d, J=14.4Hz, 1H), 3.82 (d, J=14.0Hz, 1H), 2.27 (s,
3H)；13C NMR(100MHz,CDCl3)δ141.15,138.95,138.04,137.00,136.29,133.06,131.43,
130.27,129.91,129.80,128.66,126.52,47.39,37.33,20.78；SI-HRMS calculated value C15H15NO2SNa
([M+Na]+) 296.0716, measured value 296.0721.
Embodiment 8
In the present embodiment, with the 2- benzyl benzene sulfonyl in equimolar 2- (1- phenylethyl) benzsulfamide alternative embodiment 1
Chlorine, other steps are same as Example 1, obtain 12- methyl -7,12- dihydro -6H- dibenzo [d, g] [1,2] thiazole piperazine -5,5-
Dioxide 17.5mg, yield 64%, reaction equation are as follows:
The structural characterization data of products therefrom are as follows:1H NMR(400MHz,CDCl3) δ 7.86 (d, J=8.0Hz, 1H), 7.74
(d, J=8.0Hz, 1H), 7.58 (d, J=7.6Hz, 1H), 7.48 (t, J=7.6Hz, 1H), 7.32 (t, J=8.0Hz, 1H),
7.18-7.09 (m, 3H), 5.35-5.28 (m, 1H), 5.20 (dd, J=16.0,11.2Hz, 1H), 4.42 (d, J=10.8Hz,
1H), 4.16 (d, J=17.6Hz, 1H), 1.79 (d, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ145.51,
143.31,141.16,135.65,133.10,129.46,129.34,128.40,126.93,126.83,126.26,125.98,
47.43,34.97,19.23；SI-HRMS calculated value C15H15NO2SNa([M+Na]+) 296.0716, measured value 296.0720.
Iron chloride used in above-described embodiment 1~8 can also be replaced with the frerrous chloride of equimolar amounts, can get and phase
Answer the product yield that embodiment is close.
Claims (5)
1. a kind of preparation method of cyclic sulfonamide class compound, it is characterised in that: in air atmosphere, by benzene shown in Formulas I
Sulfamide compound, iron chloride or frerrous chloride, nitromethane are uniformly mixed, and under 60~100 DEG C and visible light illumination, are stirred
It mixes reaction 6~15 hours, obtains cyclic sulfonamide class compound shown in Formula II；
In Formulas I, Formula II, R1、R2And R3It is independent to represent H, C1~C4Alkyl, C1~C2Any one in alkoxy, halogen.
2. the preparation method of cyclic sulfonamide class compound according to claim 1, it is characterised in that: the R1、R2With
R3It is independent to represent H, methyl, methoxyl group, any one in Cl.
3. the preparation method of cyclic sulfonamide class compound according to claim 1 or 2, it is characterised in that: the benzene
The molar ratio of sulfamide compound and iron chloride or frerrous chloride is 1 ﹕ (0.2~1.0).
4. the preparation method of cyclic sulfonamide class compound according to claim 1 or 2, it is characterised in that: the benzene
The molar ratio of sulfamide compound and nitromethane is 1:(40~2000).
5. the preparation method of cyclic sulfonamide class compound according to claim 1 or 2, it is characterised in that: 80~90
DEG C and visible light illumination under, be stirred to react 6~10 hours.
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| US6433187B1 (en) * | 1998-12-17 | 2002-08-13 | Tularik Inc. | Certain polycyclic compounds useful as tubulin-binding agents |
| CN101817775A (en) * | 2010-04-30 | 2010-09-01 | 浙江工业大学 | Preparation method of 2-pyrrole benzenylsulfonylamide compound |
| EP3093287A1 (en) * | 2015-05-15 | 2016-11-16 | Fundació Institut Català D'investigació Quimica | An iodine catalysed process for preparing heterocyclic nitrogen-containing compounds |
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| US6433187B1 (en) * | 1998-12-17 | 2002-08-13 | Tularik Inc. | Certain polycyclic compounds useful as tubulin-binding agents |
| CN101817775A (en) * | 2010-04-30 | 2010-09-01 | 浙江工业大学 | Preparation method of 2-pyrrole benzenylsulfonylamide compound |
| EP3093287A1 (en) * | 2015-05-15 | 2016-11-16 | Fundació Institut Català D'investigació Quimica | An iodine catalysed process for preparing heterocyclic nitrogen-containing compounds |
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