CN110372628A - Interior sulfamide compound and preparation method thereof - Google Patents

Interior sulfamide compound and preparation method thereof Download PDF

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CN110372628A
CN110372628A CN201910616230.3A CN201910616230A CN110372628A CN 110372628 A CN110372628 A CN 110372628A CN 201910616230 A CN201910616230 A CN 201910616230A CN 110372628 A CN110372628 A CN 110372628A
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interior
aryl
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hydrogen
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CN110372628B (en
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刘文博
钟大猷
刘卫
吴笛
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Wuhan University WHU
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D275/00Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D275/00Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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 ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D275/00Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D279/00Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/021,2-Thiazines; Hydrogenated 1,2-thiazines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D285/00Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D513/00Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04Ortho-condensed systems
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    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0803Compounds with Si-C or Si-Si linkages
    • C07F7/081Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract

The present invention provides a kind of interior sulfamide compounds and preparation method thereof.Specific method of the invention is that catalyst C, sulfonamide B, oxidant D are added in organic solvent to react, by separating-purifying, obtain a kind of interior sulfamide compound E or it is to be detected after the reaction was completed, after adding oxidant F reaction, into isolating and purifying, interior sulfonyl imide compounds G is obtained.Catalyst needed for this method is cheap and easy to get, the low iron complex of toxicity.When using sulfonamide H, by after completion of the reaction, then being additionally added under conditions of another oxidant F according to above method, sulfonyl imide compounds in one pot process are realized.Prepared interior sulfonamide and interior sulfonyl imide compounds are widely used in pharmaceutical chemistry, materials chemistry and organic synthesis field.

Description

Interior sulfamide compound and preparation method thereof
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of interior sulfamide compound and preparation method thereof.
Background technique
Sulfonamide structure skeleton is widely present in some drug macromoleculars with broad spectrum antibiotic activity, be it is a kind of very Important structure fragment plays an important role in new drug synthesis.It is emphasized that interior sulfonamides structure has well Water solubility and stability, be considered as lactams skeleton equivalent, and be widely used in the structural modification of drug (such as Fig. 3 institute Show), thus in field of medicinal chemistry by the extensive concern of scientists [a) Mustafa, A.Chem.Rev.1954,54, 195–223.b)Inagaki,M.;Tsuri,T.;Jyoyama,H.; Ono,T.;Yamada,K.;Kobayashi,M.;Hori, Y.;Arimura,A.;Yasui,K.;Ohno,K.; Kakudo,S.;Koizumi,K.;Suzuki,R.;Kato,M.;Kawai, S.;Matsumoto,S.J.Med. Chem.2000,43,2040–2048.c)Donkor,I.O.Curr.Med.Chem.2000, 7,1171–1188.d) Wells,G.J.;Tao,M.;Josef,K.A.;Bihovsky,R.J.Med.Chem.2001,44, 3488–3503. e)Lebegue,N.;Gallet,S.;Flouquet,N.;Carato,P.;Pfeiffer,B.;Renard, P.;Léonce,S.; Pierré,A.;Chavatte,P.;Berthelot,P.J.Med.Chem.2005,48,7363– 7373.f)Lad,N.P.; Kulkarni,S.;Sharma,R.;Mascarenhas,M.;Kulkarni,M.R.;Pandit, S.S. Piperlongumine.Eur.J.Med.Chem.2017,126,870-878.], in addition, this class formation can also be applied In certain heterocyclic compounds and natural products fully synthetic [a) Davison, E.C.;Fox,M.E.;Holmes, A.B.; Roughley,S.D.;Smith,C.J.;Williams,G.M.;Davies,J.E.;Raithby,P.R.;Adams,J.P.; Forbes,I.T.;Press,N.J.;Thompson,M.J.J.Chem.Soc.,Perkin Trans. 12002,12,1494– 1514.b)Storer,R.I.;Takemoto,T.;Jackson,P.S.;Brown,D.S.; Baxendale,I.R.;Ley, S.V.Chem.Eur.J.2004,10,2529–2547.].The method for synthesizing this class formation at present mainly includes (1) Diels- Alder cyclization [a) Rassadin, V.A.;Grosheva,D.S.; Tomashevskii,A.A.;Sokolov, V.V.Chem.Heterocycl.Compd.2013,49,39–65.b) Greig,I.R.;Tozer,M.J.;Wright, P.T.Org.Lett.2001,3,369–371.];(2) cyclization olefin metathesis (RCM) [a) McReynolds, M.D.; Dougherty,J.M.;Hanson,P.R.Chem.Rev.2004, 104,2239–2258.b)Karsch,S.;Freitag, D.;Schwab,P.Metz,P.Synthesis 2004, 1696–1712.];(3) free cyclization [Ueda, M.;Miyabe, H.;Nishimura,A.;Miyata,O.; Takemoto,Y.;Naito,T.Org.Lett.2003,5,3835–3838.]; (4) intramolecular Heck reaction [a) Khalifa, A.;Conway,L.;Geoghegan,K.;Evans,P.Tetrahedron Lett.2017,58, 4559–4562.b)Laha,J.K.;Sharma,S.;Kirar,S.;Banerjee, U.C.J.Org.Chem.2017,82,9350-9359.] etc..
Currently, the synthetic method of the interior sulfonamide backbones of catalysis is rarely reported, and it is only limitted to benzenesulfonyl azide substrate point Amination in son synthesizes benzene sulfinyl amine structure skeleton.In recent years with the fast development of enzymic catalytic reaction, Arnold, Fasan and Hartwig seminar reports arylsulfonyl nitrine substrate enzymatically in succession, and intramolecular amination occurs, obtains Sulfonamide structure in the benzo of rigidity, [a) McIntosh, J.A. with good chemo-selective and enantioselectivity; Coelho,P.S.;Farwell,C.C.;Wang,Z.J.;Lewis,J.C.;Brown, R.;Arnold, F.H.Angew.Chem.,Int.Ed.2013,52,9309–9312.b)Hyster,T.K.; Farwell,C.C.;Buller, A.R.;McIntosh,J.A.;Arnold,F.H.J.Am.Chem.Soc.2014, 136,15505–15508.c)Prier, C.K.;Zhang,R.K.;Buller,A.R.;Brinkmann-Chen,S.; Arnold,F.H.Nat.Chem.2017,9, 629–634.d)Singh,R.;Bordeaux,M.;Fasan,R. ACS Catal.2014,4,546–552.e)Singh,R.; Kolev,J.N.;Sutera,P.A.;Fasan,R.ACS Catal.2015,5,1685–1691.f)Dydio,P.;Key, H.M.;Hayashi,H.;Clark,D.S.; Hartwig,J.F..J.Am.Chem.Soc.2017,139,1750–1753.]. Metallic catalyst Cobalt Porphyrin and iridium imines compound can also be catalyzed the inner molecular reaction of aryl sulfonic acid amides, synthesize sulfonamide in benzo [Ruppel,J.V.; Kamble,R.M.;Zhang,X.P..Org.Lett.2007,9,4889–4892;Ichinose,M.; Suematsu, H.;Yasutomi,Y.;Nishioka,Y.;Uchida,T.;Katsuki,T.Angew.Chem., Int.Ed.2011, 50,9884–9887.].In short, these methods are not easy to obtain there are catalyst structure complexity, and price is high Your the disadvantages of, it is often more important that, the reaction substrate of these methods is all confined to arylsulfonyl nitrine substrate, and it is rigid to be only used for synthesis Sulfonamide product in the benzo of property.
Summary of the invention
In order to solve defect of the existing technology, the object of the present invention is to provide a kind of interior sulfamide compound and its Preparation method synthesizes interior sulfonamide and interior sulfonyl imide compounds with the new method that iron complex is catalyzed.
To achieve the above object, the interior sulfamide compound that one aspect of the present invention provides, it is characterised in that: including interior sulphur Amides compound E and interior sulfamide compound G;
The molecular structural formula of the interior sulfamide compound E is as follows:
The molecular structural formula of the interior sulfamide compound G is as follows:
Wherein R1、R2、R3、R4、R5It is independently;N, which appoints, is derived from 0,1 or 2;
The R1Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino;
The R2Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino;
The R3Optionally from hydrogen, alkyl, alkenyl, aryl;
The R4Optionally from hydrogen, alkyl, alkenyl, aryl;
The R5Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino.
The preparation method for the interior sulfamide compound that another aspect of the present invention provides, it is characterised in that: including following step It is rapid:
Iron complex catalyst C, stock sulfonamide B, oxidant D are added in organic solvent and are stirred to react, is passed through after reaction Separating-purifying is crossed, interior sulfamide compound E is obtained;In raw material dosage, iron complex catalyst C, stock sulfonamide B, oxidation The mass ratio of the material range of agent D is 0.01:1:1 to 0.5:1:5;
Obtained interior sulfamide compound E is using sulfonamide B as raw material, and reaction equation is as follows:
Alternatively, iron complex catalyst C, stock sulfonamide H, oxidant D to be added in organic solvent and be stirred to react, detect After the reaction was completed, after adding oxidant F reaction, into isolating and purifying, interior sulfonyl imide compounds G is obtained;In raw material dosage On, the iron complex catalyst C, stock sulfonamide H, oxidant D, oxidant F the mass ratio of the material range be 0.01:1:1:1 To 0.5:1:5:2;
Obtained interior sulfamide compound G is using sulfonamide H as raw material, and reaction equation is as follows:
Wherein R1、R2、R3、R4、R5It is independently;N, which appoints, is derived from 0,1 or 2;
The R1Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino;
The R2Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino;
The R3Optionally from hydrogen, alkyl, alkenyl, aryl;
The R4Optionally from hydrogen, alkyl, alkenyl, aryl;
The R5Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, Alkyl amine group or arylamino.
The structure of the oxidant F is Ar2I(OCOCF3)2, wherein Ar2Appoint and is derived from phenyl, substituted phenyl, naphthalene, takes The naphthalene in generation;
The iron complex catalyst C is the complex compound that molysite and ligand are formed;Wherein molysite optionally from trivalent iron salt or Person's divalent iron salt, structural formula are Fe (X)2Or Fe (X)3;X is optionally from following anion: Cl、Br、 I、AcO、TfO、 ClO4 、BF4 Or SbF6 ;Wherein ligand is appointed and is derived from such as flowering structure:Wherein R6Appoint and is derived from hydrogen, the alkyl of C1-C6, phenyl or substituted phenyl;Wherein R7、R8、R9Independent substituent group respectively, it is identical or Person is different;R7、R8、R9Appoint and is derived from hydrogen, the alkyl of C1-C6 or containing fluoroalkyl, aryl, heteroaryl, alkoxy, alkyl amine group, virtue Base amino;Wherein the ratio of the amount of the substance of iron and ligand is 1:1 to 1:3;
The oxidant D is high price iodide, appoints and is derived from oxygen iodobenzene or Ar1I(OCOR)2;Wherein Ar1Appoint and is derived from phenyl, takes Phenyl, naphthalene or the substituted naphthalene in generation;Wherein R appoints the alkyl for being derived from C1-C6 or containing fluoroalkyl.
Preferably, the ratio of the amount of the substance of the iron and ligand is 1:2.
Further, the fluoroalkyl that contains is iodobenzene acetate, trifluoroacetic acid iodobenzene, pivalic acid iodobenzene, dimethyl malonic acid It is any in iodobenzene or benzoic acid iodobenzene.
Further, the temperature being stirred to react is 20 degrees Celsius to 120 degrees Celsius;The separating-purifying is column layer It is any in analysis, recrystallization or distillation.
Further, the organic solvent is optionally from the combination of following solvent or solvent: acetonitrile, the tert-butyl alcohol, 1, 2- dichloroethanes, methylene chloride, tetrahydrofuran, methyl tertiary butyl ether(MTBE), dioxane, dimethyl sulfoxide, N, N '-dimethyl formyl Amine, trifluoroethanol, benzene,toluene,xylene or chlorobenzene.
Further, the organic solvent is acetonitrile or 1,2- dichloroethanes.
In above-mentioned reaction, molecular sieve, which is added, can be improved the yield of reaction, and wherein molecular sieve is optional certainlyMolecular sieve,Molecular sieve,Molecular sieve, preferablyMolecular sieve;
The invention has the advantages that and the utility model has the advantages that
(1) this method realizes the synthesis of interior sulfamide compound using iron catalyst cheap and easy to get for the first time, reaction It is easy to operate, reaction efficiency height, good economy performance;
(2) oxidant is added by situ, realizes one kettle way and prepare interior sulfonyl imide compounds, is interior sulfimide Synthesis provide a kind of completely new method;
(3) the lesser iron catalyst of toxicity is used, heavy-metal residual in synthesized product and anti-can be effectively reduced It should pollution to environment itself.
Detailed description of the invention
Fig. 1 is sulfamide compound E reactional equation schema in the present invention;
Fig. 2 is sulfamide compound G reactional equation schema in the present invention;
Fig. 3 is the representative bioactive molecule structure containing interior sulfonamide backbones.
Specific embodiment
By following detailed description it will be further appreciated that the features and advantages of the invention.Provided embodiment is only pair The explanation of the method for the present invention, remaining content without limiting the invention in any way announcement.
Embodiment 1: using phenylpropyl alcohol sulfonamide as standard substrate, to the reaction condition of the interior sulfonamide synthesis of iron catalysis
It is studied:
Wherein, footnote a is that reaction is operated at 60 degrees Celsius;Footnote b indicates reaction that molecular sieve is not added;Wherein [Fe] is Molysite;Shown in ligand structure L1-L7 as drawn by table;The relative molecular weight that mol% refers to, equiv represent equivalent, and alkali represents normal With inorganic base, solvent refers to organic solvent, volume 2mL;Wherein DMF is N, and N '-dimethyl formamide, MeCN is second Nitrile, DCE 1,2- dichloroethanes, Isosorbide-5-Nitrae-dioxane are dioxane, toluene is toluene.Wherein, ligand refers to multiple tooth nitrogen Ligand, oxidant are oxidants, and yield refers to total nuclear-magnetism yield of interior sulfonamide and interior sulfimide, with equal trimethoxy-benzene For internal standard compound.PhI(OAc)2It is iodobenzene acetate, PhI (OCOCF3)2It is trifluoroacetic acid iodobenzene, PhI (DMM) is dimethyl malonic acid Iodobenzene, PhI (OPiv)2It is pivalic acid iodobenzene.
3- phenylisothiazole alkane -1,1- dioxy [3-Phenylisothiazolidine 1,1-dioxide]:
White solid,1H NMR(400MHz,CDCl3)δ7.54–7.31(m,5H),4.76–4.70(m, 2H),3.44– 3.29 (m, 1H), 3.20 (m, J=12.6,10.6,7.6Hz, 1H), 2.80-2.73 (m, 1H), 2.45-2.34 (m, 1H)
Embodiment 2:
3- (4- aminomethyl phenyl) isothiazolidine -1,1- dioxy [3- (4-Tolyl) isothiazolidine 1,1- dioxide]:
Ferrous perchlorate (5.1mg, 0.02mmol) and ligand L 2 (8.2mg, 0.04mmol) are first weighed in 4mL reaction flask In, 1.0mL acetonitrile is added and is dissolved, stirs 30 minutes, after complexes ira situ, weighs at room temperatureMolecular sieve (50.0mg), pivalic acid iodobenzene (163.8mg, 0.4mmol) and to first class phenylpropyl alcohol sulfonamide substrate (42.3mg, 0.2mmol) add Enter in reaction system, add the dissolution of 1.0mL acetonitrile, at 80 DEG C, reacts 2h, filtering, the appropriate saturated sodium bicarbonate of filter cake Washing, water phase are extracted with dichloromethane 3 times (3 × 10mL), merge organic phase, and saturated common salt is washed, at anhydrous sodium sulfate drying It manages, after desolventizing, column chromatography for separation (methylene chloride/petroleum ether=1:1~methylene chloride) obtains interior sulfonamide 3- (4- methylbenzene Base) isothiazolidine 1,1- dioxy (33.7mg, 80%), white solid.1H NMR(400MHz, CDCl3) δ 7.29 (d, J= 8.1Hz, 2H), 7.19 (d, J=7.9Hz, 2H), 4.70 (dt, J=9.0,5.9Hz, 1H), 4.43 (br s, 1H), 3.36 (ddd, J=12.1,8.0,3.8Hz, 1H), 3.21 (ddd, J=12.7,10.3,7.6Hz, 1H), 2.75 (dtd, J=11.0, 7.0,3.8Hz,1H),2.46–2.37(m,1H),2.35(s,3H).
Embodiment 3:
3- (4- methoxyphenyl) isothiazolidine -1,1- dioxy [3- (4-Methoxyphenyl) isothiazolidine 1,1-dioxide]
White solid;Yield 86%;1H NMR(400MHz,CDCl3) δ 7.32 (d, J=8.8Hz 2H), 6.90 (d, J= 8.8Hz 2H),4.79–4.63(m,1H),4.50(br s,1H),3.81(s,3H),3.45–3.32 (m,1H),3.25–3.17 (m,1H),2.76–2.68(m,1H),2.44–2.34(m,1H);13C NMR(100 MHz,CDCl3)δ159.8,132.0, 127.5,114.5,58.0,55.5,48.5,32.4;HRMS(ESI+) calc'd for C10H13NNaO3S[M+Na]+: 250.0508,found 250.0513.
3- phenylisothiazole alkane -1,1- dioxy [3-Phenylisothiazolidine 1,1-dioxide]
White solid
1H NMR(400MHz,CDCl3)δ7.54–7.31(m,5H),4.76–4.70(m,2H),3.44– 3.29(m,1H), 3.20 (m, J=12.6,10.6,7.6Hz, 1H), 2.80-2.73 (m, 1H), 2.45-2.34 (m, 1H)
Embodiment 4:
3- (4- nitrobenzophenone) isothiazolidine -1,1- dioxy [3- (4-Nitrophenyl) isothiazolidine 1,1- dioxide]
White solid;Yield 52%;1H NMR(400MHz,CDCl3) δ 8.25 (d, J=8.7Hz, 2H), 7.62 (d, J= 8.7Hz, 2H), 4.85 (m, J=7.9Hz, 1H), 4.74 (br s, 1H), 3.40 (ddd, J=12.3,7.3,2.7Hz, 1H), 3.21 (td, J=12.0,7.6Hz, 1H), 2.88 (ddd, J=13.8,7.1,4.6Hz, 1H), 2.50-2.25 (m, 1H);13C NMR(100MHz,CDCl3)δ148.0,147.9,127.0,124.5,57.2, 48.2,32.0;HRMS(ESI+)calc'd for C9H10ClNNaO2S[M+Na]+:265.0253,found 265.0254.
Embodiment 5:
3- (3- methoxyphenyl) isothiazolidine -1,1- dioxy [3- (3-Methoxyphenyl) isothiazolidine 1,1-dioxide]
White solid;Yield 66%;1H NMR(400MHz,CDCl3) δ 7.30 (t, J=7.9Hz, 1H), 6.97 (d, J= 8.2Hz, 2H), 6.87 (d, J=8.2Hz, 1H), 4.75-4.67 (m, 1H), 4.55 (br s, 1H), 3.82 (s, 3H), 3.44- 3.29(m,1H),3.24–3.16(m,1H),2.81–2.73(m,1H),2.45–2.37 (m,1H);13C NMR(100MHz, CDCl3)δ160.2,141.9,130.3,118.2,114.0,111.6,58.2, 55.5,48.2,32.2;HRMS(ESI+) calc’d for C10H13NNaO3S[M+Na]+:250.0508,found 250.0513.
Embodiment 6:
3- (3- bromophenyl) isothiazolidine -1,1- dioxy [3- (3-Bromophenyl) isothiazolidine 1,1- dioxide]
White solid;Yield 74%;1H NMR(400MHz,CDCl3) δ 7.56 (s, 1H), 7.46 (dd, J=7.9, 1.0Hz, 1H), 7.35 (d, J=7.8Hz, 1H), 7.30-7.21 (m, 1H), 4.73-4.65 (m, 2H), 3.43-3.31 (m, 1H), 3.19 (m, J=12.5,11.0,7.6Hz, 1H), 2.79 (m, J=10.4,7.3,3.4 Hz, 1H), 2.49-2.28 (m, 1H);13C NMR(100MHz,CDCl3)δ142.7,131.7,130.8, 129.2,124.8,123.2,57.5,48.2,32.1; HRMS(ESI+)calc’d for C9H10BrNNaO2S [M+Na]+:297.9508,found 297.9509.
Embodiment 7:
3- (2- methoxyphenyl) isothiazolidine -1,1- dioxy [3- (2-Methoxyphenyl) isothiazolidine 1,1-dioxide]
White solid;Yield 77%;1H NMR(400MHz,CDCl3) δ 7.45 (dd, J=7.6,1.5Hz, 1H), 7.34- 7.28 (m, 1H), 7.00-6.97 (m, 1H), 6.90 (d, J=8.2Hz, 1H), 4.96 (dd, J=8.3,7.0Hz, 1H), 3.86 (s,3H),3.34–3.27(m,1H),3.24–3.16(m,1H),2.84–2.76(m, 1H),2.45–2.35(m,1H);13C NMR(100MHz,CDCl3)δ156.6,129.5,127.5,127.3, 121.2,110.7,55.5,54.4,48.2,30.4; HRMS(ESI+)calc’d for C10H13NNaO3S [M+Na]+:250.0508,found 250.0505.
Embodiment 8:
3- (2- bromophenyl) isothiazolidine -1,1- dioxy [3- (2-Bromophenyl) isothiazolidine 1,1- dioxide 2h])
White solid;Yield 61%;1H NMR(400MHz,CDCl3) δ 7.73 (dd, J=7.8,1.6Hz, 1H), 7.54 (dd, J=8.0,1.1Hz, 1H), 7.42-7.34 (m, 1H), 7.18 (td, J=7.7,1.7Hz, 1H), 5.16 (dd, J= 14.8,6.7Hz, 1H), 4.70 (br s, 1H), 3.33 (ddd, J=12.1,7.1,3.7Hz, 1H), 3.23-3.12 (m, 1H), 3.06–2.98(m,1H),2.30–2.20(m,1H);13C NMR(100MHz, CDCl3)δ139.7,133.1,129.8, 128.5,127.6,121.8,57.2,48.0,30.1;HRMS(ESI+) calc'd for C9H10BrNNaO2S[M+Na]+: 297.9508,found 297.9505.
Embodiment 9:
3- (4- chlorphenyl) isothiazolidine -1,1- dioxy [3- (4-Chlorophenyl) isothiazolidine 1,1- dioxide]
White solid;Yield 80%;1H NMR(400MHz,CDCl3) δ 7.34-7.32 (m, 4H), 4.71 (t, J= 6.6Hz,1H),4.66(br s,1H),3.36–3.30(m,1H),3.22–3.14(m,1H),2.79– 2.71(m,1H), 2.38–2.27(m,1H);13C NMR(100MHz,CDCl3)δ138.9,134.4,129.3, 127.5,57.6,48.3,32.3; HRMS(ESI+)calc’d for C9H10ClNNaO2S[M+Na]+: 254.0013,found 254.0013.
Embodiment 10:
3- (4- bromophenyl) isothiazolidine -1,1- dioxy [3- (4-Bromophenyl) isothiazolidine 1,1- dioxide]
White solid;Yield 75%;1H NMR(400MHz,CDCl3) δ 7.50 (d, J=8.3Hz, 2H), 7.29 (d, J= 8.4Hz, 2H), 4.87-4.59 (m, 2H), 3.35 (ddd, J=10.9,7.6,3.1Hz, 1H), 3.26-3.13 (m, 1H), 2.85–2.70(m,1H),2.44–2.25(m,1H);13C NMR(100MHz, CDCl3)δ139.5,132.3,127.9, 122.4,57.6,48.3,32.2;HRMS(ESI+)calc'd for C9H10BrNNaO2S[M+Na]+:297.9508,found 297.9512.
Embodiment 11:
3- (4- trifluoromethyl) isothiazolidine -1,1- dioxy [3- (4- (Trifluoromethyl) phenyl) isothiazolidine 1,1-dioxide]
White solid;Yield 88%;1H NMR(400MHz,CDCl3) δ 7.64 (d, J=8.2Hz, 2H), 7.54 (d, J= 8.2Hz, 2H), 4.87-4.79 (m, 2H), 3.37 (ddd, J=12.3,7.5,3.2Hz, 1H), 3.27-3.14 (m, 1H), 2.84–2.80(m,1H),2.47–2.26(m,1H);13C NMR(100MHz, CDCl3) δ 144.6 (q, J=1.0Hz), 130.8 (q, J=32.4Hz), 126.5,126.1 (q, J=3.8Hz), 124.0 (q, J=270.5Hz), 57.6,48.2,32.1;19F NMR(376MHz,CDCl3)δ–62.61(s); HRMS(ESI+)calc'd for C10H10F3NNaO2S[M+Na]+: 288.0277,found 288.0282.
Embodiment 12:
3- (3- aminomethyl phenyl) isothiazolidine -1,1- dioxy [3- (3-Tolyl) isothiazolidine 1,1- dioxide]
White solid;Yield 89%;1H NMR(400MHz,CDCl3)δ7.30–7.25(m,1H),7.24 –7.12(m, 3H),4.72–4.68(m,1H),4.51(br s,1H),3.39–3.33(m,1H),3.25–3.17 (m,1H),2.78–2.73 (m,1H),2.46–2.38(m,1H),2.37(s,3H).
Embodiment 13:
3- (2- aminomethyl phenyl) isothiazolidine -1,1- dioxy [3- (2-Tolyl) isothiazolidine 1,1- dioxide]
White solid;Yield 81%;1H NMR(400MHz,CDCl3) δ 7.58 (d, J=7.4Hz, 1H), 7.30-7.23 (m, 1H), 7.21 (dd, J=7.2,1.2Hz, 1H), 7.17 (d, J=7.2Hz, 1H), 4.97 (t, J=6.8Hz, 1H), 4.51 (br s, 1H), 3.35 (ddd, J=12.3,7.8,4.3Hz, 1H), 3.21 (ddd, J=12.6,9.8,7.6Hz, 1H), 2.78 (ddd, J=11.6,10.2,5.8Hz, 1H), 2.37 (s, 3H), 2.37-2.28 (m, 1H)
Embodiment 14:
3- phenyl -1,2- thiazan -1,1- dioxy [3-phenyl-1,2-thiazinane 1,1-dioxide]
White solid;Yield 70%;1H NMR(400MHz,CDCl3) δ 7.43-7.29 (m, 5H), 4.59 (dd, J= 11.9,3.4Hz, 1H), 4.24 (br s, 1H), 3.33-3.19 (m, 1H), 3.01 (td, J=13.1,5.2 Hz, 1H), 2.43- 2.23 (m, 2H), 2.06 (ddd, J=13.9,5.9,3.0Hz, 1H), 1.73 (ddd, J=17.1,13.0,8.5Hz, 1H)
Embodiment 15:
3- methyl -2,3- dihydrobenzo isothiazolidine -1,1- dioxy [3-methyl-2,3-dihydrobenzo [d] isothiazole 1,1-dioxide]
White solid;Yield 70%;1H NMR(400MHz,CDCl3) δ 7.78 (d, J=7.7Hz, 1H), 7.64 (t, J= 7.5Hz, 1H), 7.54 (t, J=7.4Hz, 1H), 7.40 (d, J=7.7Hz, 1H), 4.82-4.78 (m, 1H), 1.63 (d, J= 6.4Hz,3H).
Embodiment 16:
2,3- dihydrobenzo isothiazolidine -1,1- dioxy [2,3-Dihydrobenzo [d] isothiazole 1,1- dioxide]
White solid;Yield 50%;1H NMR(400MHz,CDCl3) δ 7.80 (d, J=7.8Hz, 1H), 7.62 (td, J =7.6,1.1Hz, 1H), 7.56-7.51 (m, 1H), 7.40 (d, J=7.7Hz, 1H), 4.81 (br s, 1H), 4.54 (s, 2H).
Embodiment 17:
3- ((trimethyl silicon substrate) acetenyl) isothiazolidine -1,1- dioxy [3- ((trimethylsilyl) ethynyl) isothiazolidine 1,1-dioxide]
Yellow solid;Yield 53%;1H NMR(400MHz,CDCl3)δ4.59–4.22(m,2H), 3.31–3.20(m, 1H),3.19–3.14(m,1H),2.86–2.66(m,1H),2.61–2.40(m,1H), 0.17(s,9H);13C NMR (100MHz,CDCl3)δ102.0,91.2,46.7,46.0,30.9,-0.21; HRMS(ESI+)calc'd for C8H15NNaO2SSi[M+Na]+:240.0485,found 240.0489.
Embodiment 18:
3,3- dimethyl isothiazolidine -1,1- dioxy [3,3-dimethylisothiazolidine 1,1-dioxide]
White solid;Yield 68%;1H NMR(400MHz,CDCl3) δ 4.06 (br s, 1H), 3.23 (t, J=7.5Hz, 2H), 2.29 (t, J=7.5Hz, 2H), 1.40 (s, 6H);13C NMR(100MHz,CDCl3)δ 57.9,48.3,37.0,29.7; HRMS(ESI+)calc’d for C5H11NNaO2S[M+Na]+:172.0403, found 172.0404.
Embodiment 19:
3- methyl-isothiazol alkane -1,1- dioxy [3-methylisothiazolidine 1,1-dioxide]
White solid;Yield 74%;
1H NMR(400MHz,CDCl3)δ4.04(br s,1H),3.76–3.68(m,1H),3.26–3.20 (m,1H), 3.17-3.09 (m, 1H), 2.55-2.48 (m, 1H), 2.09-1.99 (m, 1H), 1.33 (d, J=6.3Hz, 3H)
Embodiment 20:
Method one: ferrous perchlorate (5.1mg, 0.02mmol) and L1 (8.1mg, 0.04mmol) are first weighed and is reacted in 4mL In bottle, 1.0mL acetonitrile is added and is dissolved, stirs 30 minutes, after complexes ira situ, weighs at room temperatureMolecular sieve (50.0mg), dimethyl malonic acid iodobenzene (167.0mg, 0.5mmol) and corresponding sulfonamide substrate (38.6mg, 0.2mmol), it is added in reaction system, adds the dissolution of 1.0mL acetonitrile, at 80 DEG C, react 2h, filtering, filter cake is used appropriate full It is washed with sodium bicarbonate, water phase is extracted with dichloromethane 3 times (3 × 10mL), merges organic phase, and saturated salt solution cleaning is anhydrous Sodium sulphate is dried, and after removing solvent, column chromatography for separation (methylene chloride/petroleum ether=1:1~methylene chloride) is obtained in five yuan Sulfonamide 3- amyl isothiazolidine -1,1- dioxy and hexa-atomic interior sulfonamide 3- butyl isothiazine alkane -1,1- dioxy are the mixed of 3:5 It closes object (32.6mg, 85%).
Method two: first weighing ferrous perchlorate (5.1mg, 0.02mmol) and L6 (10.1mg, 0.06mmol) is anti-in 4mL It answers in bottle, 1.0mL acetonitrile is added and is dissolved, stirs 30 minutes, after complexes ira situ, weighs at room temperatureMolecular sieve (50.0mg), dimethyl malonic acid iodobenzene (162.5mg, 0.5mmol) and corresponding sulfonamide substrate (38.6mg, 0.2mmol), it is added in reaction system, adds the dissolution of 1.0mL acetonitrile, at 80 DEG C, react 2h, filtering, filter cake is used appropriate full It is washed with sodium bicarbonate, water phase is extracted with dichloromethane 3 times (3 × 10mL), merges organic phase, and saturated salt solution cleaning is anhydrous Sodium sulphate is dried, and after removing solvent, column chromatography for separation (methylene chloride/petroleum ether=1:1~methylene chloride) is obtained in five yuan Sulfonamide 3- amyl isothiazolidine -1,1- dioxy and hexa-atomic interior sulfonamide 3- butyl isothiazine alkane -1,1- dioxy ratio are 2:1's Mixture (28.6mg, 75%).
3- amyl isothiazolidine -1,1- dioxy [3-Pentylisothiazolidine 1,1-dioxide]
Colourless liquid;1H NMR(400MHz,CDCl3)δ4.31(br s,1H),3.61–3.53(m,1H), 3.26–3.15 (m,1H),3.13–3.06(m,1H),2.59–2.43(m,1H),2.12–1.97(m,1H), 1.64–1.53(m,2H),1.42– 1.15 (m, 6H), 0.89 (t, J=6.8Hz, 3H);13C NMR(100 MHz,CDCl3)δ55.4,48.2,36.1,31.6, 30.0,25.9,22.6,14.1;HRMS(ESI+)calc'd for C8H17NNaO2S[M+Na]+:214.0872,found 214.0873.
3- butyl isothiazine alkane -1,1- dioxy [3-Butyl-1,2-thiazinane 1,1-dioxide]
Colourless liquid;1H NMR(400MHz,CDCl3)δ3.74(br s,1H),3.50–3.43(m,1H), 3.20(dt,J =13.3,3.5Hz, 1H), 2.98-2.72 (m, 1H), 2.28-2.12 (m, 2H), 1.84-1.80 (m, 1H), 1.52-1.14 (m, 7H), 0.90 (t, J=7.0Hz, 3H);13C NMR(100MHz,CDCl3)δ 56.8,49.6,35.6,30.7,27.6, 23.2,22.5,14.1.
Embodiment 21:
3- phenyl -1,2- thiophene azete alkane -1,1- dioxy [3-Phenyl-1,2-thiazetidine 1,1-dioxide]
MS=183.04
Embodiment 22:
[Tetrahydro-1H,3H-isothiazolo[4,3-c]isothiazole 2,2,5,5-tetraoxide]
MS=211.99
Embodiment 23:
Isothiazolidine -1,1- dioxy [isothiazolidine 1,1-dioxide]
MS=121.02
Embodiment 24:
3- methyl -6- phenyl -1,2- isothiazine alkane -1,1- dioxy [3-methyl-6-phenyl-1,2-thiazinane 1,1-dioxide]
MS=225.08
Embodiment 25:
1,2- isothiazine alkane -1,1- dioxy [1,2-thiazinane 1,1-dioxide]
MS=135.04
Embodiment 26:
Methyl -3,4, -2 hydrogenated naphthalene of 6,7,8,9- hexahydro [2,3-e] and isothiazine alkane -3- carboxyl -1,1- dioxy [methyl 3,4,6,7,8,9-hexahydro-2H-naphtho[2,3-e][1,2]thiazine-3-carboxylate 1, 1-dioxide]
MS=295.09
Embodiment 27:
(E) -5- (3,5- di-t-butyl -4- hydroxy-benzylidene isothiazine alkane -1,1- dioxy [(E) -5- (3,5-di- tert-butyl-4-hydroxybenzylidene)isothiazolidine 1,1-dioxide]
MS=337.17
Embodiment 28:
- 3 carbonyl -1,1- dioxy [methyl isothiazolidine-3-carboxylate 1,1- of methyl-isothiazol alkane dioxide]
MS=179.03
Embodiment 29-42:
Ferrous perchlorate (5.2mg, 0.02mmol) and ligand L 2 (8.0mg, 0.04mmol) are first weighed in 4mL reaction flask In, 1.0mL acetonitrile is added and is dissolved, stirs 30 minutes, after complexes ira situ, weighs at room temperatureMolecular sieve (50.0mg), pivalic acid iodobenzene (163.8mg, 0.4mmol) and corresponding sulfonamide H (0.2mmol) are added in reaction system, then 1.0mL acetonitrile is added, after TLC monitoring fully reacting is reacted at 80 DEG C, trifluoroacetic acid iodobenzene is added into reaction system (103.1mg, 0.24mmol) reacts 1h again at 80 DEG C, then filters, and filter cake is washed with appropriate saturated sodium bicarbonate, water phase It is extracted with dichloromethane 3 times (3 × 10mL), merges organic phase and is cleaned with saturated salt solution, anhydrous sodium sulfate is dried, and is taken off After solvent, column chromatography for separation (methylene chloride/petroleum ether=1:1~methylene chloride) obtains interior sulfonyl imide compounds G.
Embodiment 29:
3- phenyl -4,5- dihydro isothiazole -1,1- dioxy [3-phenyl-4,5-dihydroisothiazole 1,1- dioxide]
White solid;Yield 88%;1H NMR(400MHz,CDCl3) δ 8.03 (dd, J=8.4,1.2Hz, 2H), 7.74- 7.61 (m, 1H), 7.53 (t, J=7.7Hz, 2H), 3.75-3.61 (m, 2H), 3.56-3.35 (m, 2H)
Embodiment 30:
3- (4- aminomethyl phenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (4-Tolyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;1H NMR(400MHz,CDCl3) δ 7.92 (d, J=8.3Hz, 2H), 7.32 (d, J=8.3Hz, 2H), 3.65 (dd, J=8.2,6.4Hz, 2H), 3.43 (dd, J=8.1,6.5Hz, 2H), 2.45 (s, 3H)
Embodiment 31:
3- (4- nitrobenzophenone) -4,5- dihydro isothiazole -1,1- dioxy [3- (4-Nitrophenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;Yield 75%;1H NMR(400MHz,CD3CN)δ8.42–8.28(m,2H), 8.28–8.15(m, 2H), 3.76 (dd, J=8.0,6.3Hz, 2H), 3.47 (dd, J=7.9,6.3Hz, 2H);13C NMR(100MHz,CD3CN)δ 177.2,151.9,137.5,131.1,124.9,45.4,35.1;HRMS (ESI+)calc'd for C9H8N2NaO4S[M+ Na]+:263.0097,found 263.0093.
Embodiment 32:
3- (3- methoxyphenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (3-Methoxyphenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;Yield 81%;1H NMR(400MHz,CDCl3) δ 7.63-7.58 (m, 1H), 7.52 (d, J= 7.7Hz, 1H), 7.42 (t, J=8.0Hz, 1H), 7.19 (dd, J=8.2,2.4Hz, 1H), 3.87 (s, 3H), 3.75-3.55 (m,2H),3.56–3.31(m,2H);13C NMR(100MHz,CDCl3)δ176.0, 160.1,132.2,130.2,121.6, 121.4,113.3,55.7,44.4,33.7;HRMS(ESI+)calc'd for C10H11NNaO3S[M+Na]+:248.0352, found 248.0352.
Embodiment 33:
3- (3- bromophenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (3-Bromophenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;Yield 78%;1H NMR(400MHz,CDCl3)δ8.16(s,1H),8.05–7.90(m, 1H), 7.80-7.77 (m, 1H), 7.44-7.40 (m, 1H), 3.64 (dd, J=8.3,6.2Hz, 2H), 3.46 (dd, J=8.1, 6.3Hz,2H);13C NMR(100MHz,CDCl3)δ174.6,137.5,132.9,132.1,130.8, 127.7,123.5, 44.4,33.6;HRMS(ESI+)calc'd for C9H8BrNNaO2S[M+Na]+: 295.9351,found 295.9347.
Embodiment 34:
3- (2- methoxyphenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (2-Methoxyphenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;1H NMR(400MHz,CDCl3) δ 8.15 (dd, J=7.9,1.8Hz, 1H), 7.66-7.48 (m, 1H), 7.09-7.04 (m, 1H), 7.01 (d, J=8.5Hz, 1H), 3.93 (s, 3H), 3.82 (t, J=7.2Hz, 2H), 3.35 (t, J=6.8Hz 2H);13C NMR(100MHz,CDCl3)δ178.0,160.5, 135.8,132.5,121.4,120.1, 112.0,55.8,44.2,37.9;HRMS(ESI+)calc'd for C10H11NNaO3S[M+Na]+:248.0352,found 248.0352.
Embodiment 35:
3- (2- bromophenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (2-Bromophenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;1H NMR(400MHz,CDCl3) δ 7.71 (dd, J=7.8,1.3Hz, 1H), 7.66 (dd, J= 7.6,1.9Hz, 1H), 7.46 (dd, J=7.5,1.4Hz, 1H), 7.43-7.38 (m, 1H), 3.94-3.68 (t, 2H), 3.45 (t,2H);13C NMR(100MHz,CDCl3)δ178.9,134.6,133.6,133.3, 131.0,128.0,121.2,44.7, 37.4;HRMS(ESI+)calc'd for C9H8BrNNaO2S[M+Na]+: 295.9351,found 295.9350.
Embodiment 36:
3- (4- chlorphenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (4-Chlorophenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;Yield 85%;1H NMR(400MHz,CDCl3) δ 7.96 (d, J=8.6Hz, 2H), 7.51 (d, J= 8.5Hz,2H),3.82–3.57(t,2H),3.56–3.36(t,2H);13C NMR(100MHz, CDCl3)δ174.8,141.4, 130.5,129.8,129.4,44.5,33.6;HRMS(ESI+)calc'd for C9H8ClNNaO2S[M+Na]+:251.9856, found 251.9860.
Embodiment 37:
3- (4- bromophenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (4-Bromophenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;1H NMR(400MHz,CDCl3) δ 7.88 (d, J=8.6Hz, 2H), 7.68 (d, J=8.6Hz, 2H), 3.67–3.60(t,2H),3.50–3.41(t,2H);13C NMR(100MHz,CDCl3)δ 174.9,132.8,130.5, 130.1,129.9,44.4,33.6;HRMS(ESI+)calc'd for C9H8BrNNaO2S[M+Na]+:295.9351,found 295.9353.
Embodiment 38:
3- (4- trifluoromethyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (4- (Trifluoromethyl) phenyl)-4,5-dihydroisothiazole 1,1-dioxide]
White solid;Yield 92%;1H NMR(400MHz,CD3CN) δ 8.21 (d, J=8.2Hz, 2H), 7.87 (d, J= 8.3Hz, 2H), 3.75 (t, J=7.9,6.3Hz, 2H), 3.53-3.32 (t, 2H);13C NMR (100MHz,CD3CN)δ 177.7,135.9 (q, J=1.0Hz), 135.1 (q, J=32.5Hz), 130.6,126.9 (q, J=3.8Hz), 124.7 (q, J =270.2Hz), 45.3,34.9;19F NMR(376MHz, CD3CN)δ–63.77(s);HRMS(ESI+)calc'd for C10H8F3NNaO2S[M+Na]+:286.0120, found 286.0118.
Embodiment 39:
3- (4- methoxyphenyl) -4,5- dihydro isothiazole -1,1- dioxy [3- (4-Methoxyphenyl) -4,5- dihydroisothiazole 1,1-dioxide]
White solid;Yield 78%;1H NMR(400MHz,CDCl3) δ 7.99 (d, J=8.9Hz, 2H), 7.00 (d, J= 8.9Hz,2H),3.90(s,3H),3.74–3.58(t,2H),3.49–3.35(t,2H);13C NMR(100MHz,CDCl3)δ 175.0,164.9,131.6,123.5,114.7,55.8,44.5,33.4;HRMS (ESI+)calc'd for C10H11NNaO3S [M+Na]+:248.0352,found 248.0356.
Embodiment 40:
3- methyl -4,5- dihydro isothiazole -1,1- dioxy [3-Methyl-4,5-dihydroisothiazole 1,1- dioxide]
White solid;1H NMR(400MHz,CDCl3)δ3.31–3.24(t,2H),3.23–3.16(t,2H), 2.34(s, 3H).
Embodiment 41:
Methyl -4,5- dihydro isothiazole -3- carbonyl -1,1- dioxy [methyl 4,5-dihydroisothiazole-3- carboxylate 1,1-dioxide]
MS=177.01
Embodiment 42:
(E) -3- (1- allyl) -4,5-4,5- dihydro isothiazole -1,1- dioxy [(E) -3- (prop-1-en-1-yl) - 4,5-dihydroisothiazole 1,1-dioxide]
MS=159.04.

Claims (8)

1. a kind of interior sulfamide compound, it is characterised in that: including interior sulfamide compound E and interior sulfamide compound G;
The molecular structural formula of the interior sulfamide compound E is as follows:
The molecular structural formula of the interior sulfamide compound G is as follows:
Wherein R1、R2、R3、R4、R5It is independently;N, which appoints, is derived from 0,1 or 2;
The R1Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino;
The R2Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino;
The R3Optionally from hydrogen, alkyl, alkenyl, aryl;
The R4Optionally from hydrogen, alkyl, alkenyl, aryl;
The R5Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino.
2. a kind of preparation method of sulfamide compound interior as described in claim 1, it is characterised in that: the following steps are included:
Iron complex catalyst C, stock sulfonamide B, oxidant D are added in organic solvent and are stirred to react, through excessive after reaction From purification, interior sulfamide compound E is obtained;In raw material dosage, iron complex catalyst C, stock sulfonamide B, oxidant D The mass ratio of the material range is 0.01:1:1 to 0.5:1:5;
Obtained interior sulfamide compound E is using sulfonamide B as raw material, and reaction equation is as follows:
Alternatively, iron complex catalyst C, stock sulfonamide H, oxidant D are added in organic solvent and are stirred to react, detection reaction After the completion, after adding oxidant F reaction, into isolating and purifying, interior sulfonyl imide compounds G is obtained;In raw material dosage, institute State iron complex catalyst C, stock sulfonamide H, oxidant D, oxidant F the mass ratio of the material range be 0.01:1:1:1 to 0.5: 1:5:2;
Obtained interior sulfamide compound G is using sulfonamide H as raw material, and reaction equation is as follows:
Wherein R1、R2、R3、R4、R5It is independently;N, which appoints, is derived from 0,1 or 2;
The R1Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino;
The R2Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino;
The R3Optionally from hydrogen, alkyl, alkenyl, aryl;
The R4Optionally from hydrogen, alkyl, alkenyl, aryl;
The R5Optionally from hydrogen, alkyl, alkenyl, aryl, substituted aryl, alkoxy, phenol oxygroup, alkylthio group, phenol sulfenyl, alkyl Amido or arylamino.
The structure of the oxidant F is Ar2I(OCOCF3)2, wherein Ar2Appoint and is derived from phenyl, substituted phenyl, naphthalene, substituted naphthalene Base;
The iron complex catalyst C is the complex compound that molysite and ligand are formed;Wherein molysite is optionally from trivalent iron salt or two Valence molysite, structural formula are Fe (X)2Or Fe (X)3;X is optionally from following anion: Cl、Br、I、AcO、TfO、ClO4 、BF4 Or SbF6 ;Wherein ligand is appointed and is derived from such as flowering structure:Wherein R6Appoint and is derived from hydrogen, the alkyl of C1-C6, phenyl or substituted phenyl;Wherein R7、R8、R9Independent substituent group respectively, it is identical or Person is different;R7、R8、R9Appoint and is derived from hydrogen, the alkyl of C1-C6 or containing fluoroalkyl, aryl, heteroaryl, alkoxy, alkyl amine group, virtue Base amino;Wherein the ratio of the amount of the substance of iron and ligand is 1:1 to 1:3;
The oxidant D is high price iodide, appoints and is derived from oxygen iodobenzene or Ar1I(OCOR)2;Wherein Ar1Appoint be derived from phenyl, replace Phenyl, naphthalene or substituted naphthalene;Wherein R appoints the alkyl for being derived from C1-C6 or containing fluoroalkyl.
3. the preparation method of sulfamide compound in as claimed in claim 2, it is characterised in that: the object of the iron and ligand The ratio of the amount of matter is 1:2.
4. the preparation method of sulfamide compound in as claimed in claim 2 or claim 3, it is characterised in that: described to contain fluoroalkyl It is any in iodobenzene acetate, trifluoroacetic acid iodobenzene, pivalic acid iodobenzene, dimethyl malonic acid iodobenzene or benzoic acid iodobenzene.
5. the preparation method of sulfamide compound in as claimed in claim 2 or claim 3, it is characterised in that: described to be stirred to react Temperature be 20 degrees Celsius to 120 degrees Celsius;The separating-purifying is any in column chromatography, recrystallization or distillation.
6. such as the preparation method of claim 4 or the interior sulfamide compound, it is characterised in that: described to be stirred to react Temperature is 20 degrees Celsius to 120 degrees Celsius;The separating-purifying is any in column chromatography, recrystallization or distillation.
7. the preparation method of sulfamide compound in as claimed in claim 2 or claim 3, it is characterised in that: described is organic molten Agent is optionally from the combination of following solvent or solvent: acetonitrile, the tert-butyl alcohol, 1,2- dichloroethanes, methylene chloride, tetrahydrofuran, first Base tertbutyl ether, dioxane, dimethyl sulfoxide, N, N '-dimethyl formamide, trifluoroethanol, benzene,toluene,xylene or chlorine Benzene.
8. the preparation method of sulfamide compound in as claimed in claim 7, it is characterised in that: the organic solvent is second Nitrile or 1,2- dichloroethanes.
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