微波-超声复合场辅助水介质砜类化合物合成
|
摘要
发展了一种微波-超声复合场下绿色高效合成砜类化合物的简便方法。以芳甲基氯和苯亚磺酸钠为原料,以水为反应介质,在微波-超声复合场辅助下合成了一系列芳甲基苯基砜。通过考察微波功率、超声功率、原料投料比、溶剂体积和反应时间等因素的影响,得出了苄基氯与苯亚磺酸钠之间模型反应的最优反应条件:微波功率为40 W,超声功率为50 W,苄基氯与苯亚磺酸钠的摩尔配比为1∶3,反应时间为5 min。在此条件下合成的苄基苯基砜产率为83%。相比常规油浴条件,在微波-超声复合场的强化下反应速率提升了约42倍。该方法具有较好的底物适应性,成功合成了23种砜类化合物。
A green,efficient and simple method for the synthesis of sulfones under combined microwave and ultrasound irradiation was developed. The aromatic methyl phenyl sulfones were synthesized from arylmethyl chlorides and sodium benzenesulfonates in aqueous media under combined microwave and ultrasound irradiation. The effects of microwave power,ultrasonic power,materials molar ratio,substrate concentration and irradiation time were investigated. The optimal conditions for the synthesis of benzyl phenyl sulfone are:microwave power,40 W; ultrasonic power,50 W; molar ratio of benzyl chloride and sodium benzene sulfonate,1∶ 3; reaction time,5 min. The obtained yield is 83% under these conditions. Compared with the reaction in oil bath,the reaction was accelerated about 42 times. Twenty three sulfones have been successfully synthesized with broad substrate generality.
A green,efficient and simple method for the synthesis of sulfones under combined microwave and ultrasound irradiation was developed. The aromatic methyl phenyl sulfones were synthesized from arylmethyl chlorides and sodium benzenesulfonates in aqueous media under combined microwave and ultrasound irradiation. The effects of microwave power,ultrasonic power,materials molar ratio,substrate concentration and irradiation time were investigated. The optimal conditions for the synthesis of benzyl phenyl sulfone are:microwave power,40 W; ultrasonic power,50 W; molar ratio of benzyl chloride and sodium benzene sulfonate,1∶ 3; reaction time,5 min. The obtained yield is 83% under these conditions. Compared with the reaction in oil bath,the reaction was accelerated about 42 times. Twenty three sulfones have been successfully synthesized with broad substrate generality.
引文
[1]Simpkins N S.Sulphones in Organic Synthesis[M].Oxford:Pergamum Press,1993:1-4.
[2]Trost B M.Chemical Chameleons Organosulfones as Synthetic Building Blocks[J].Bull Chem Soc Jpn,1988,61(1):107-124.
[3]Stephens C E,Felder T M,Sowell J W,et al.Synthesis and Antiviral/Antitumor Evaluation of 2-Amino-and 2-Carboxamido-3-arylsulfonylthiophenes and Related Compounds as a New Class of Diarylsulfones[J].Med Chem,2001,9(5):1123-1132.
[4]Crosignani S,Pretre A,Jorand L,et al.Discovery of Potent,Selective,and Orally Bioavailable Alkynylphenoxyacetic Acid CRTH2(DP2)Receptor Antagonists for the Treatment of Allergic Inflammatory Diseases[J].J Med Chem,2011,54(20):7299-7317.
[5]La Regina G,Coluccia A,Brancale A,et al.Indolylarylsulfones as HIV-1 Non-nucleoside Reverse Transcriptase Inhibitors:New Cyclic Substituents at Indole-2-carboxamide[J].J Med Chem,2011,54(6):1587-1598.
[6]Padmavathi V,Thriveni P,Sudhakar R G,et al.Synthesis and Antimicrobial Activity of Novel Sulfone-linked bis Heterocycles[J].Eur J Med Chem,2008,43(5):917-924.
[7]Yasuo I,Kazunari O,Shigeyuki I,et al.Studies on Sulfonylureas with Fusedheterocycles.Part 1.Synthesis of Novel Herbicidal Sulfonylurea Compounds with an Imidazo[1,2-α]pyridine Moiety[J].J Pestic Sci,1993,18(2):175-182.
[8]Vedula M S,Pulipaka A B,Venna C,et al.New Styryl Sulfones as Anticancer Agents[J].Eur J Med Chem,2003,38(9):811-824.
[9]Tai X,Yin X,Tan M,et al.Crystal Structure and Antitumor Activity of Tri[2-[N-(4'-methylbenzylsulfonyl)amino]ethyl]-amine[J].Chinese J Struct Chem,2003,22(4):411-414.
[10]Silvestri R,Artico M,Regina G L,et al.Anti-HIV-1 Activity of Pyrryl Arylsulfone(PAS)Derivatives:Synthesis and SARStudies of Novel Esters and Amidesat the Position 2 of the Pyrrole Nucleus[J].Il Farmaco,2004,59(3):201-210.
[11]Shaabani A,Hezarkhani Z,Shaabani S.Cellulose Supported Manganese Dioxide Nanosheet Catalyzed Aerobic Oxidation of Organic Compounds[J].RSC Adv,2014,4(110):64419-64428.
[12]Graybill B M.The Synthesis of Aryl Sulfones[J].J Org Chem,1967,32(9):2931-2933.
[13]Yuttapong S,Morgane P,Romain L,et al.Thioamide-Substituted Cinchona Alkaloids as Efficient Organocatalysts for Asymmetric Decarboxylative Reactions of MAHOs[J].Eur J Org Chem,2017,(29):4319-4323.
[14]Fu Y,Xu Q S,Li Q Z,et al.Efficient Synthesis of Aliphatic Sulfones by Mg Mediated Coupling Reactions of Sulfonyl Chlorides and Aliphatic Halides[J].Org Biomol Chem,2017,15(13):2841-2845.
[15]Chung T W,Chen C H,Lin C C,et al.Exploring a Sulfone Linker Utilizing Trimethyl Aluminum as a Cleavage Reagent:Solid-phase Synthesis of Sulfonamides and Ureas[J].Mol Divers,2012,16(3):463-476.
[16]Isabelle A T,Alexander B,Mickael D,et al.Synthesis of Chiral Thiazoline Ligands Tethered to a Sulfur Function and First Immobilization of a Thiazoline-Ligand[J].Heteroat Chem,2010,21(4):242-249.
[17]Frank W L,Thomas C M,David H G.Preliminary Investigations on Novel Camphor-derived Chiral Sulfones:Completely Stereoselective Formation of Tricyclicβ-Hydroxy Sulfones from 8-and 10-Functionalized Camphor Derivatives[J].Tetrahedron,2011,67(39):7517-7528.
[18]Seth R,Peter W.Water-accelerated Organic Transformations[J].Chem Commun,2001,(4):299-307.
[19]Riina K A,Nicholas E L.Suzuki Coupling of Aryl Chlorides with Phenylboronic Acid in Water,Using Microwave Heating with Simultaneous Cooling[J].Org Lett,2005,7(11):2101-2104.
[20]Lin C C,Hsieh T H,Liao P Y,et al.Practical Synthesis of N-Substituted Cyanamides via Tiemann Rearrangement of Amidoximes[J].Org Lett,2014,16(3):892-895.
[21]LI Yiqun.Synthesis of Sulfones by Phase-Transfers-Alkylation of Arenesulfinate Salts[J].Chem Res Appl,1997,9(3):311-313(in Chinese).李毅群.相转移催化芳基亚磺酸盐S-烷基化合成砜的研究[J].化学研究与应用,1997,9(3):311-313.
[22]Jack K C,Christian P.Synthesis of Sulfones by Phase-Transfer Alkylation of Arenesulfinate Salts[J].J Org Chem,1985,50(8):1327-1329.
[23]Yi H,Zhen C C,Zhang G L,et al.Organic Reactions in Ionic Liquids:An Efficient Method for the Synthesis of Aryl Sulfones by Alkylation of Sodium Arenesulfinates with Alkyl Halides[J].Chem Inform,2004,35(42):267-269.
[24]Varma R S.“Greener”Chemical Syntheses Using Mechanochemical Mixing or Microwave and Ultrasound Irradiation[J].Green Chem Lett Rev,2007,1(1):37-45.
[25]Katia M,Silvia T,Alessandro B,et al.Combined Microwaves/Ultrasound,A Hybrid Technology[J].Top Curr Chem,2016,374(6):79.
[26]Giancarlo C,Pedro C.The Combined Use of Microwaves and Ultrasound:Improved Tools in Process Chemistry and Organic Synthesis[J].Chem Eur J,2007,13(7):1902-1909.
[27]Peng Y Q,Song G H.Simultaneous Microwave and Ultrasound Irradiation:A Rapid Synthesis of Hydrazides[J].Green Chem,2001,3(6):302-304.
[28]Peng Y Q,Song G H.Combined Microwave and Ultrasound Accelerated Knoevenagel-Doebner Reaction in Aqueous Media:A Green Route to 3-Aryl Acrylic Acids[J].Green Chem,2003,5(6):704-706.
[29]Peng Y Q,Song G H.Dramatically Accelerated Synthesis ofβ-Aminoketones via Aqueous Mannich Reaction Under Combined Microwave and Ultrasound Irradiation[J].Synlett,2005,2005(14):2245-2247.
[30]Peng Y Q,Song G H.Surface Cleaning under Combined Microwave and Ultrasound Irradiation:Flash Synthesis of 4H-pyrano[2,3-c]Pyrazoles in Aqueous Media[J].Green Chem,2006,8(6):573-575.
[31]Ju Y H,Kumar D,Varma R S.Revisiting Nucleophilic Substitution Reactions:Microwave-Assisted Synthesis of Azides,Thiocyanates,and Sulfones in an Aqueous Medium[J].J Org Chem,2006,71(17):6697-6700.
[32]Mehdi K M,Kiumars B,Mohammad K.The Efficient and Chemoselective MoO3-Catalyzed Oxidation of Sulfides to Sulfoxides and Sulfones with H2O2[J].Can J Chem,2007,85(1):7-11.
[33]Shyam P K,Jang H Y.Synthesis of Sulfones and Sulfonamides via Sulfinate Anions:Revisiting the Utility of Thiosulfonates[J].J Org Chem,2017,82(3):1761-1767.
[34]Kiumars B,Mohammad M K,Mehdi S A.TAPC-Promoted Oxidation of Sulfides and Deoxygenation of Sulfoxides[J].J Org Chem,2010,75(18):6208-6213.
[35]Ryoichi K,Yutaka K,Tsuyoshi S.Transformation of Carbonates into Sulfones at the Benzylic Position via PalladiumCatalyzed Benzylic Substitution[J].Org Lett,2005,7(14):2973-2975.
[36]Asthana R S,Misra G S.Mixed Aromatic Aliphatic Sulfones[J].J Indian Chem Soc,1954,31:459-460.
[37]Abrunhosa I,Gulea M,Masson S.Efficient New Protocol to Synthesize Aromatic and Heteroaromatic Dithioesters[J].Synthesis,2004,(6):928-934.
[38]Dass G B,Roy M,Roy S,et al.Homolytic Displacement at Saturated Carbon in Organocobaloximes[J].J Chem Soc Perkin Trans 2,1990,(4):537-543.
[39]Yue G R,She X G,Zhang Z,et al.A Tandem Michael Addition-Rearrangement-Carbonylation by(4-Nitrophenylsulfonylmethyl)Benzene and Its Derivatives with Methacrylates under PTC[J].J Chem Res,2003,(9):559-561.
[40]Peng H J,Cheng Y F,Ni N T,et al.Synthesis and Evaluation of New Antagonists of Bacterial Quorum Sensing in Vibrio harveyi[J].Chem Med Chem,2009,4(9):1457-1468.
[41]Zhao M M,Qu C X,Lynch J E.Zn/Cu I-Mediated Coupling of Alkyl Halides with Vinyl Sulfones,Vinyl Sulfonates,and Vinyl Sulfonamides[J].J Org Chem,2005,70(17):6944-6947.
[42]Maloney K M,Kuethe J T,Linn K.A Practical,One-Pot Synthesis of Sulfonylated Pyridines[J].Org Lett,2011,13(1):102-105.
[2]Trost B M.Chemical Chameleons Organosulfones as Synthetic Building Blocks[J].Bull Chem Soc Jpn,1988,61(1):107-124.
[3]Stephens C E,Felder T M,Sowell J W,et al.Synthesis and Antiviral/Antitumor Evaluation of 2-Amino-and 2-Carboxamido-3-arylsulfonylthiophenes and Related Compounds as a New Class of Diarylsulfones[J].Med Chem,2001,9(5):1123-1132.
[4]Crosignani S,Pretre A,Jorand L,et al.Discovery of Potent,Selective,and Orally Bioavailable Alkynylphenoxyacetic Acid CRTH2(DP2)Receptor Antagonists for the Treatment of Allergic Inflammatory Diseases[J].J Med Chem,2011,54(20):7299-7317.
[5]La Regina G,Coluccia A,Brancale A,et al.Indolylarylsulfones as HIV-1 Non-nucleoside Reverse Transcriptase Inhibitors:New Cyclic Substituents at Indole-2-carboxamide[J].J Med Chem,2011,54(6):1587-1598.
[6]Padmavathi V,Thriveni P,Sudhakar R G,et al.Synthesis and Antimicrobial Activity of Novel Sulfone-linked bis Heterocycles[J].Eur J Med Chem,2008,43(5):917-924.
[7]Yasuo I,Kazunari O,Shigeyuki I,et al.Studies on Sulfonylureas with Fusedheterocycles.Part 1.Synthesis of Novel Herbicidal Sulfonylurea Compounds with an Imidazo[1,2-α]pyridine Moiety[J].J Pestic Sci,1993,18(2):175-182.
[8]Vedula M S,Pulipaka A B,Venna C,et al.New Styryl Sulfones as Anticancer Agents[J].Eur J Med Chem,2003,38(9):811-824.
[9]Tai X,Yin X,Tan M,et al.Crystal Structure and Antitumor Activity of Tri[2-[N-(4'-methylbenzylsulfonyl)amino]ethyl]-amine[J].Chinese J Struct Chem,2003,22(4):411-414.
[10]Silvestri R,Artico M,Regina G L,et al.Anti-HIV-1 Activity of Pyrryl Arylsulfone(PAS)Derivatives:Synthesis and SARStudies of Novel Esters and Amidesat the Position 2 of the Pyrrole Nucleus[J].Il Farmaco,2004,59(3):201-210.
[11]Shaabani A,Hezarkhani Z,Shaabani S.Cellulose Supported Manganese Dioxide Nanosheet Catalyzed Aerobic Oxidation of Organic Compounds[J].RSC Adv,2014,4(110):64419-64428.
[12]Graybill B M.The Synthesis of Aryl Sulfones[J].J Org Chem,1967,32(9):2931-2933.
[13]Yuttapong S,Morgane P,Romain L,et al.Thioamide-Substituted Cinchona Alkaloids as Efficient Organocatalysts for Asymmetric Decarboxylative Reactions of MAHOs[J].Eur J Org Chem,2017,(29):4319-4323.
[14]Fu Y,Xu Q S,Li Q Z,et al.Efficient Synthesis of Aliphatic Sulfones by Mg Mediated Coupling Reactions of Sulfonyl Chlorides and Aliphatic Halides[J].Org Biomol Chem,2017,15(13):2841-2845.
[15]Chung T W,Chen C H,Lin C C,et al.Exploring a Sulfone Linker Utilizing Trimethyl Aluminum as a Cleavage Reagent:Solid-phase Synthesis of Sulfonamides and Ureas[J].Mol Divers,2012,16(3):463-476.
[16]Isabelle A T,Alexander B,Mickael D,et al.Synthesis of Chiral Thiazoline Ligands Tethered to a Sulfur Function and First Immobilization of a Thiazoline-Ligand[J].Heteroat Chem,2010,21(4):242-249.
[17]Frank W L,Thomas C M,David H G.Preliminary Investigations on Novel Camphor-derived Chiral Sulfones:Completely Stereoselective Formation of Tricyclicβ-Hydroxy Sulfones from 8-and 10-Functionalized Camphor Derivatives[J].Tetrahedron,2011,67(39):7517-7528.
[18]Seth R,Peter W.Water-accelerated Organic Transformations[J].Chem Commun,2001,(4):299-307.
[19]Riina K A,Nicholas E L.Suzuki Coupling of Aryl Chlorides with Phenylboronic Acid in Water,Using Microwave Heating with Simultaneous Cooling[J].Org Lett,2005,7(11):2101-2104.
[20]Lin C C,Hsieh T H,Liao P Y,et al.Practical Synthesis of N-Substituted Cyanamides via Tiemann Rearrangement of Amidoximes[J].Org Lett,2014,16(3):892-895.
[21]LI Yiqun.Synthesis of Sulfones by Phase-Transfers-Alkylation of Arenesulfinate Salts[J].Chem Res Appl,1997,9(3):311-313(in Chinese).李毅群.相转移催化芳基亚磺酸盐S-烷基化合成砜的研究[J].化学研究与应用,1997,9(3):311-313.
[22]Jack K C,Christian P.Synthesis of Sulfones by Phase-Transfer Alkylation of Arenesulfinate Salts[J].J Org Chem,1985,50(8):1327-1329.
[23]Yi H,Zhen C C,Zhang G L,et al.Organic Reactions in Ionic Liquids:An Efficient Method for the Synthesis of Aryl Sulfones by Alkylation of Sodium Arenesulfinates with Alkyl Halides[J].Chem Inform,2004,35(42):267-269.
[24]Varma R S.“Greener”Chemical Syntheses Using Mechanochemical Mixing or Microwave and Ultrasound Irradiation[J].Green Chem Lett Rev,2007,1(1):37-45.
[25]Katia M,Silvia T,Alessandro B,et al.Combined Microwaves/Ultrasound,A Hybrid Technology[J].Top Curr Chem,2016,374(6):79.
[26]Giancarlo C,Pedro C.The Combined Use of Microwaves and Ultrasound:Improved Tools in Process Chemistry and Organic Synthesis[J].Chem Eur J,2007,13(7):1902-1909.
[27]Peng Y Q,Song G H.Simultaneous Microwave and Ultrasound Irradiation:A Rapid Synthesis of Hydrazides[J].Green Chem,2001,3(6):302-304.
[28]Peng Y Q,Song G H.Combined Microwave and Ultrasound Accelerated Knoevenagel-Doebner Reaction in Aqueous Media:A Green Route to 3-Aryl Acrylic Acids[J].Green Chem,2003,5(6):704-706.
[29]Peng Y Q,Song G H.Dramatically Accelerated Synthesis ofβ-Aminoketones via Aqueous Mannich Reaction Under Combined Microwave and Ultrasound Irradiation[J].Synlett,2005,2005(14):2245-2247.
[30]Peng Y Q,Song G H.Surface Cleaning under Combined Microwave and Ultrasound Irradiation:Flash Synthesis of 4H-pyrano[2,3-c]Pyrazoles in Aqueous Media[J].Green Chem,2006,8(6):573-575.
[31]Ju Y H,Kumar D,Varma R S.Revisiting Nucleophilic Substitution Reactions:Microwave-Assisted Synthesis of Azides,Thiocyanates,and Sulfones in an Aqueous Medium[J].J Org Chem,2006,71(17):6697-6700.
[32]Mehdi K M,Kiumars B,Mohammad K.The Efficient and Chemoselective MoO3-Catalyzed Oxidation of Sulfides to Sulfoxides and Sulfones with H2O2[J].Can J Chem,2007,85(1):7-11.
[33]Shyam P K,Jang H Y.Synthesis of Sulfones and Sulfonamides via Sulfinate Anions:Revisiting the Utility of Thiosulfonates[J].J Org Chem,2017,82(3):1761-1767.
[34]Kiumars B,Mohammad M K,Mehdi S A.TAPC-Promoted Oxidation of Sulfides and Deoxygenation of Sulfoxides[J].J Org Chem,2010,75(18):6208-6213.
[35]Ryoichi K,Yutaka K,Tsuyoshi S.Transformation of Carbonates into Sulfones at the Benzylic Position via PalladiumCatalyzed Benzylic Substitution[J].Org Lett,2005,7(14):2973-2975.
[36]Asthana R S,Misra G S.Mixed Aromatic Aliphatic Sulfones[J].J Indian Chem Soc,1954,31:459-460.
[37]Abrunhosa I,Gulea M,Masson S.Efficient New Protocol to Synthesize Aromatic and Heteroaromatic Dithioesters[J].Synthesis,2004,(6):928-934.
[38]Dass G B,Roy M,Roy S,et al.Homolytic Displacement at Saturated Carbon in Organocobaloximes[J].J Chem Soc Perkin Trans 2,1990,(4):537-543.
[39]Yue G R,She X G,Zhang Z,et al.A Tandem Michael Addition-Rearrangement-Carbonylation by(4-Nitrophenylsulfonylmethyl)Benzene and Its Derivatives with Methacrylates under PTC[J].J Chem Res,2003,(9):559-561.
[40]Peng H J,Cheng Y F,Ni N T,et al.Synthesis and Evaluation of New Antagonists of Bacterial Quorum Sensing in Vibrio harveyi[J].Chem Med Chem,2009,4(9):1457-1468.
[41]Zhao M M,Qu C X,Lynch J E.Zn/Cu I-Mediated Coupling of Alkyl Halides with Vinyl Sulfones,Vinyl Sulfonates,and Vinyl Sulfonamides[J].J Org Chem,2005,70(17):6944-6947.
[42]Maloney K M,Kuethe J T,Linn K.A Practical,One-Pot Synthesis of Sulfonylated Pyridines[J].Org Lett,2011,13(1):102-105.