间氟甲苯控制氧化合成间氟苯甲醛
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摘要
间氟苯甲醛是重要的有机合成中间体,可广泛地应用于医药、农药、塑料添加剂等精细化学品的合成。本文通过采用不同的氧化剂氧化间氟甲苯合成间氟苯甲醛,重点研究了氧气,二氧化锰和三氧化二锰的氧化效果,分别研究了它们的氧化工艺条件以及固体氧化剂的循环利用,并初步探讨了它们的氧化机理。
考察了Co/Mn/Br含水氧化体系对间氟苯甲醛产率的影响,当醋酸-水混合溶剂中水含量为10%时,产率最高为15.80%;二氧化锰氧化的最佳条件为:反应温度为90℃,硫酸质量浓度为70%,反应时间为6h,间氟甲苯与二氧化锰的摩尔比为1∶1.6,产率最佳值为56.02%;三氧化二锰氧化的最佳条件为:反应温度为50℃,硫酸质量浓度为70%,反应时间为8h,间氟甲苯与三氧化二锰的摩尔比为1∶2.4,产率最佳值为75.38%。二氧化锰氧化性较强,副产物较多,醛的选择性较低,而三氧化二锰具有很好的选择性。并对最终产物进行了气质、红外、核磁分析。
废液硫酸和硫酸锰通过处理可以循环利用,在硫酸锰溶液中加入碳酸氢铵将其转化为碳酸锰,通过在370℃的马弗炉中灼烧6h得到二氧化锰,将二氧化锰在650℃下灼烧1h得到三氧化二锰。实现了固体氧化剂的绿色循环利用。
m-Fluorobenzaldehyde was an important organic synthesis intermediate,and can be widely applied in fine chemicals synthesis,such as medicine,pesticides,plastics additives. This paper mainly introduced different oxidation methods,but oxygen,manganese dioxide and manganese sesquioxide were mainly studied.Oxidation conditions and the recycling of solid oxidation were studied.Their mechanisms were initially discussed.
Co/Mn/Br catalyst system containing water,which was effect on the yield of m-fluorobenzaldehyde was studied.When the water content of the acetic acid-water mixed solvents was 10%,the yield was 15.80%.The optimum reaction conditions of manganese dioxide oxidation were as follows:the temperature was 90℃,the concentration of H_2SO_4 was 70%,the time was 6h,the molar ratio of m-fluorotoluene and manganese dioxide was 1:1.6, the yield was 56.02%.The optimum reaction conditions of manganese sesquioxide oxidation were as follows:the temperature was 50℃,the concentration of H_2SO_4 was 70%,the time was 8h,the molar ratio of m-fluorotoluene and manganese sesquioxide was 1:2.4,the yield was 75.38%.The oxidability of manganese dioxide was very strong,so the by-products were more,the selectivity of m-fluorobenzaldehyde was lower.Manganese sesquioxide had the good selectivity,m-Fluorobenzaldehyde was analyzed through GC-MS,IR,NMR.
Waste H_2SO_4 and MnSO_4 can be handled through recycling.MnCO_3 was obtained by joining NH_4HCO_3 in MnSO_4,which was baked for 6h at 370℃,then translated into MnO_2. Mn_2O_3 was obtained by baking MnO_2 at 650℃for 1h.The solid oxidant recycling was achieved.
考察了Co/Mn/Br含水氧化体系对间氟苯甲醛产率的影响,当醋酸-水混合溶剂中水含量为10%时,产率最高为15.80%;二氧化锰氧化的最佳条件为:反应温度为90℃,硫酸质量浓度为70%,反应时间为6h,间氟甲苯与二氧化锰的摩尔比为1∶1.6,产率最佳值为56.02%;三氧化二锰氧化的最佳条件为:反应温度为50℃,硫酸质量浓度为70%,反应时间为8h,间氟甲苯与三氧化二锰的摩尔比为1∶2.4,产率最佳值为75.38%。二氧化锰氧化性较强,副产物较多,醛的选择性较低,而三氧化二锰具有很好的选择性。并对最终产物进行了气质、红外、核磁分析。
废液硫酸和硫酸锰通过处理可以循环利用,在硫酸锰溶液中加入碳酸氢铵将其转化为碳酸锰,通过在370℃的马弗炉中灼烧6h得到二氧化锰,将二氧化锰在650℃下灼烧1h得到三氧化二锰。实现了固体氧化剂的绿色循环利用。
m-Fluorobenzaldehyde was an important organic synthesis intermediate,and can be widely applied in fine chemicals synthesis,such as medicine,pesticides,plastics additives. This paper mainly introduced different oxidation methods,but oxygen,manganese dioxide and manganese sesquioxide were mainly studied.Oxidation conditions and the recycling of solid oxidation were studied.Their mechanisms were initially discussed.
Co/Mn/Br catalyst system containing water,which was effect on the yield of m-fluorobenzaldehyde was studied.When the water content of the acetic acid-water mixed solvents was 10%,the yield was 15.80%.The optimum reaction conditions of manganese dioxide oxidation were as follows:the temperature was 90℃,the concentration of H_2SO_4 was 70%,the time was 6h,the molar ratio of m-fluorotoluene and manganese dioxide was 1:1.6, the yield was 56.02%.The optimum reaction conditions of manganese sesquioxide oxidation were as follows:the temperature was 50℃,the concentration of H_2SO_4 was 70%,the time was 8h,the molar ratio of m-fluorotoluene and manganese sesquioxide was 1:2.4,the yield was 75.38%.The oxidability of manganese dioxide was very strong,so the by-products were more,the selectivity of m-fluorobenzaldehyde was lower.Manganese sesquioxide had the good selectivity,m-Fluorobenzaldehyde was analyzed through GC-MS,IR,NMR.
Waste H_2SO_4 and MnSO_4 can be handled through recycling.MnCO_3 was obtained by joining NH_4HCO_3 in MnSO_4,which was baked for 6h at 370℃,then translated into MnO_2. Mn_2O_3 was obtained by baking MnO_2 at 650℃for 1h.The solid oxidant recycling was achieved.
引文
[1]梁诚.含氟中间体及其精细化学品现状与发展[J].中国石油和化工经济分析,2003,(14):49-55.
[2]程隆新.氟化技术在医药和农药上的应用[J].杭州化工,1993(1):18-26.
[3]孙卫芬.间甲苯胺合成间氟苯甲醛的研究[M].南京理工大学,2007.
[4]董成国,左识之,倪家宝.对氟苯甲醛的合成研究[J].染料工业,2001,38(3):32-34.
[5]陈红飙,林原斌,刘展鹏等.邻氟苯甲醛的合成研究[J].有机氟工业,2003,(4):3-5.
[6]Selvam T.,Singh A.P.J.Chem.Soc.,Chem.Commun.,1995,883-884.
[7]Sigh A.P.,Selvam T.Appl.Catal.A.Gen.,1996,143:111-124.
[8]韩雪峰,孔洁,韩丽.KMnO_4-Al_2O_3氧化法制备苯甲酸[J].廊坊师范学院学报,2005,21(4):106-1075.
[9]朱宪,缪伶,王彬等.苯甲醛的清洁生产工艺研究[J].环境科学,2004,25:21-26.
[10]顾红,王遵尧.Mn_2O_3氧化法合成对氯苯甲醛[J].染料与染色,2004,41(4):212-214.
[11]徐高扬,李泉,郑纯智,许兴友.邻氯苯甲醛合成新工艺[J].IM&P化工矿物与加工,2002,(10):17-19.
[12]刘俊峰.二氧化锰氧化间甲酚制取间羟基苯甲醛[J].浙江化工,1999,30(2):31-33.
[13]Iwahama T.,Sakaguchi S.,Terahedron Lett.,1995,36:6923.
[14]赵崇涛,朱则善,曾春柏等.硫酸锰电生媒质微粒MnO_2氧化甲苯制备苯甲醛[J].福建师范大学学报,1995,11(3):60-65.
[15]崔宝秋,李金毅.有机电合成氟代苯甲醛新进展介绍[J].辽宁师专学报,2000,2(4):36-38.
[16]尹学琼,陈忠秀,蒋群等.芳烃氧化制备芳酸研究的进展[J].煤炭转化,1999,22(1):19-22.
[17]杨宏,李军,姜国平.双氧水氧化法合成邻氟苯甲酸工艺研究[J].有机氟工业,2006(4):12-13.
[18]汪树清.烷基芳香烃氧化反应的研究进展[J].石油化工高等学校学报,1998,11(2):40-46.
[19]Kevin Auty,Bruce C.Gilbert,C.Barry Thomas,et al.The selective oxidation of toluenes tobenzaldehydes by Cerium(Ⅲ),hydrogen peroxide and bromide ion[J].Journal of Molecular Catalysis A.,1997,117:279-287.
[20]吴泽彪,盛梅,林西平.甲苯气相氧化制苯甲醛[J].膜科学与技术,2000,20(6): 29-32.
[21]Jin S.Yoo.Gas phase oxygen oxidation of alkylaromatics over CVD Fe/Mo/borosilicate molecular sieve,Fe/Mo/DBH Ⅶ,oxidative dehydrogenation of alkylaromatics[J].Applied Catalysis A.,1996,142:19-29.
[22]Centi G.,Perathoner S..Site isolation in iron-molybdate-based catalysts for side chain oxidation of alkylaromatics[J].Topics in Catalysis,2001,15(2-4):145 - 151.
[23]Centi G.,Perathoner S.,Tonini S..Synthesis of 3-fluorobenzaldehyde by gas-phase selective oxidation on Fe-Mo oxide/boralite catalysts[J].Topics in Catalysis,2000:195-204.
[24]Aguilar Elguezabal A.,Cortes Corberan V..Selective oxidation of toluene on V_2O_5/TiO_2/SiO_2 catalysts modified with Te,Al,Mn and K_2SO_4[J].Catalysts Today,1996,32:265-272.
[25]Frank Konietzni,Uwe Kolb,Uwe Dingerdissen,et al.AMM-Mn_xSi-Catalyzed selective oxidation of toluene[J].Journal of Catalysts,1998,176:527-535.
[26]Dmitri A.Bulushev,Lioubov Kiwi-Minsker,Vladimir I.,et al.Effect of potassium doping on the structural and catalytic properties of V/Ti-oxide in selective toluene oxidation[J].Applied Catalysis A.General 2000,202:243-250.
[27]肖春妹,李国情.甲苯液相空气催化氧化技术研究进展[J].化工生产与技术,2006,13(2):46-50.
[28]户安军,吕春绪,李斌栋.甲苯类化合物的选择性氧化[J].化学进展,2007,19(2/3):292-302.
[29]Partenheimer W..Catalysis Today,1995,23:69-158.
[30]Mannepalli Lakshmi Kantan.An improved process for selective liquid-phase air oxidation of toluene[J].Catalysis Letters,2002,81:223-232.
[31]乔艳辉,滕俊江.液相催化氧化法制备邻羟基苯甲醛[J].茂名学院学报,2005,15(4):26-29.
[32]阳卫军,郭灿城.金属卟啉化合物及其对烷烃的仿生催化氧化[J].应用化学,2004,21(6):541-545.
[33]佘远斌,王兰芝,宋旭锋等.金属卟啉类催化剂的合成、构效关系及在催化氧化碳氢化合物中的应用[J].精细化工,2005,22(6):401-408.
[34]王兰芝,佘远斌,徐未芝等.金属卟啉类模拟酶催化剂研究[J].化学进展,2005,17(4):678-685.
[35]童金辉,李臻,夏春谷.环境友好催化氧化研究进展[J].化学进展,2005,17(1):96-110.
[36]李鸿波,曾伟,杜瑛等.冠醚化Schiff碱[J].有机化学,2002,22(6):397-404.
[37]周智明,李连友,徐巧等.仿生催化剂-Salen金属络合物催化不对称环氧化烯烃的基础[J].有机化学,2005,25(4):347-354.
[38]孙伟,夏春谷.金属卟啉催化烯烃环氧化及反应机理研究[J].化学进展,2002,14(5):8-17.
[39]Mukaiyama T.,Yamada T.Bull.Chem.Soc.Jpn.,1995,68:17-35.
[40]Murahashi S.I.,Komiya N.Catal.Today,1998,41:339-349.
[41]李建章,李慈,秦圣英.仿生氧载体均相催化性能研究现状[J].西南民族学院学报,1998,24(4):420-424.
[42]曹志红,刘文明,项学明.La-OMS-2催化剂催化甲苯氧化制苯甲醛[J].石油化工,2006,35(11):1069-1073.
[43]Yasutaka I.,Kouichi N.,Mitsuhiro T.,et al.A Novel Catalysis of N-Hydroxyphthalimide in the Oxidation of Organic Substrates by Molecular Oxygen[J].J.Org.Chem.,1995,60:3934-3935.
[44]Xavier B.,Isabel W.C.E.A.,Ellwood S.,et al.A New Catalytic System for the Selectivity Aerobic Oxidation of Large Ring Cycloalkane to Ketones[J].Organic Process Research & Development,2003,7:426-428.
[45]Yasutaka I.,Satoshi S..A new strategy for alkane oxidation with O_2 using N-hydroxyphthalimide(NHPI)as a radical catalyst[J].Catalysis Surveys from Japan,1999,3:27-35.
[46]Babak K,Jamshid R.An improved protocol for aerobic oxidation of acetals to esters catalyzed by N-hydroxy phthalimide(NHPI)and lipophilic Co(Ⅱ)complexes[J].Journal of Molecular Catalysis A.Chemical,2005,226:165-169.
[47]Asushi Y.,Yoshiaki H.,Takahiro I.,et al.Catalytic Oxidation of Alkylbenzenes with Molecular Oxygen under Normal Pressure and Temperature by N-Hydroxy phthalimide Combined with Co(OAc)_2[J].J.Org.Chem.,1997,62:6810-6813.
[48]刘耀华,崔鹏,孙靖,杨帆等.离子液体中芳烃侧链分子氧催化氧化反应研究[J].高等学校化学学报,2006,27(12):2314-2318.
[49]方岩雄,顾浩,张赛丹等.离子液体中氧化反应研究进展[J].精细化工,2005,22(6):451-454.
[50]Choudhary V.R.,Dumbre D.K.,Uphade B.S.,et al.Solvent-free oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide using transition metal containing layered double hydroxides and/or mixed hydroxides[J].Journal of Molecular Catalysis A.,2004,215:129-135.
[51]Singh A.P.,Selvam T..Liquid phase oxidation reactions over chromium silicalite-1(CrS-1)molecular sieves[J].Journal of Molecular Catalysis A.,1996,113:489-497.
[52]John David O.Anderson and Walter Scrivens.Fluorinated and chlorinated benzaldehydes[J],US 6297405,2001.
[53]蔡敏敏,魏运洋,蔡春等.氧气液相氧化法制备邻硝基苯甲醛[J].化学反应工程与工艺,2002:18(1):23-26.
[54]蔡敏敏,魏运洋,蔡春等.氧气液相氧化邻硝基甲苯制备邻硝基苯甲醛-反应条件的研究[J].染料工业,2002:39(2):39-41.
[55]蔡敏敏,魏运洋,吕春绪.氧气液相氧化邻硝基甲苯制取邻硝基苯甲醛[J].南京理工大学学报,2006:22(2):197-200.
[56]蔡敏敏,曹阳,魏运洋等.氧气液相氧化邻硝基甲苯合成邻硝基苯甲醛-溶剂对反应的影响[J].染料工业,2002,9(1):39-40.
[57]张金生,边鲁宁,李丽华.离子液体的合成研究与应用进展[J],化学与生物工程,2007,1(24):7-9.
[58]Kenneth R.Seddon,AnnegretStark,Green Chemistry,2002,4:119-123.
[59]Backstrom H.L..J.Am.Chem.Soc.,1927,(49):1460.
[60]Peter D.Metelski,Victor A.Adamian.Mechanistic Role of Benzylic Bromides in the Catalytic Autoxidation of Methylarenes[J].Inorg.Chem.,2002,(39):2434-2439.
[61]陈书阁.γ型化学二氧化锰的合成[J].无机盐工业,I997,(3):17-20.
[62]夏熙.电池组二氧化锰[M].袁光钰译.北京:轻工业出版社,1997:19-34.
[63]杜献.对醇氧化的一些特殊氧化剂的探讨[J].井冈山学院学报(自然科学),2006:27(12):66-67.
[64]Goldman I.M.,J.Org.Chem.,34,1979(1969).
[65]张立珠,陈忠林,马军等.水溶液中新生态MnO_2对苯酚的氧化作用及机理研究[J].环境科学,2006,27(5):941-944.
[66]双喜,丽丽,嘎日迪.液相沉淀法制备纳米Mn_2O_3[J].内蒙古石油化工,2005,(11):12-13.
[67]陈志文,张庶元,谭舜等.纳米Mn_2O_3的制备及其ESR研究[J].波谱学杂志,1997,14(5):443-448.
[68]陈志文,张庶元,谭舜等.纳米Mn_2O_3的制备及其分形凝聚[J].中国科学技术大学学报,1998,28(2):227-229.
[69]何建玲,孙德胜,王遵尧.用Mn_2O_3法合成对羟基苯甲醛[J].当代化工,2004,33(1):4-7
[70]严新,宋萌,林周等.用Mn_2O_3氧化法合成对羰基苯磺酸[J].江苏化工,2004,32(4):31-33.
[71]王琪,刘继泉.空气间接氧化制备对叔丁基苯甲醛的新工艺[J].青岛科技大学学报,2005,26(2):106-108.
[72]Wendt H.,Schneider H.Reaction kinetics and reaction techniques for mediated oxidation of methylarenes to aromatic ketones[J].Ibid,1986,16:134-146.
[73]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,(4):743-747.
[74]李刚,王武明.中国锰业状况[J].四川化工,1993,(2):5-7.
[75]胡国荣,周玉琳,彭忠东.用工业硫酸锰制取高纯碳酸锰的工艺研究[J].中国锰业,2007,25(2):14-17.
[76]陈书阁.碳酸锰分解氧化工艺条件的探讨[J].无机盐工业,1994,(6):20-21.
[77]谌曙永.碳酸锰热解生成二氧化锰的试验研究[J].中国锰业,1991,9(6):21-24.
[78]Marba'n G.,Teresa Valde's-Soli's,Antonio B..Fuertes,Mechanism of low temperature selective catalytic reduction of NO with NH_3 over carbon-supported Mn_3O_4[J].Phys.Chem.Chem.Phys.,2004,6,453-464.
[2]程隆新.氟化技术在医药和农药上的应用[J].杭州化工,1993(1):18-26.
[3]孙卫芬.间甲苯胺合成间氟苯甲醛的研究[M].南京理工大学,2007.
[4]董成国,左识之,倪家宝.对氟苯甲醛的合成研究[J].染料工业,2001,38(3):32-34.
[5]陈红飙,林原斌,刘展鹏等.邻氟苯甲醛的合成研究[J].有机氟工业,2003,(4):3-5.
[6]Selvam T.,Singh A.P.J.Chem.Soc.,Chem.Commun.,1995,883-884.
[7]Sigh A.P.,Selvam T.Appl.Catal.A.Gen.,1996,143:111-124.
[8]韩雪峰,孔洁,韩丽.KMnO_4-Al_2O_3氧化法制备苯甲酸[J].廊坊师范学院学报,2005,21(4):106-1075.
[9]朱宪,缪伶,王彬等.苯甲醛的清洁生产工艺研究[J].环境科学,2004,25:21-26.
[10]顾红,王遵尧.Mn_2O_3氧化法合成对氯苯甲醛[J].染料与染色,2004,41(4):212-214.
[11]徐高扬,李泉,郑纯智,许兴友.邻氯苯甲醛合成新工艺[J].IM&P化工矿物与加工,2002,(10):17-19.
[12]刘俊峰.二氧化锰氧化间甲酚制取间羟基苯甲醛[J].浙江化工,1999,30(2):31-33.
[13]Iwahama T.,Sakaguchi S.,Terahedron Lett.,1995,36:6923.
[14]赵崇涛,朱则善,曾春柏等.硫酸锰电生媒质微粒MnO_2氧化甲苯制备苯甲醛[J].福建师范大学学报,1995,11(3):60-65.
[15]崔宝秋,李金毅.有机电合成氟代苯甲醛新进展介绍[J].辽宁师专学报,2000,2(4):36-38.
[16]尹学琼,陈忠秀,蒋群等.芳烃氧化制备芳酸研究的进展[J].煤炭转化,1999,22(1):19-22.
[17]杨宏,李军,姜国平.双氧水氧化法合成邻氟苯甲酸工艺研究[J].有机氟工业,2006(4):12-13.
[18]汪树清.烷基芳香烃氧化反应的研究进展[J].石油化工高等学校学报,1998,11(2):40-46.
[19]Kevin Auty,Bruce C.Gilbert,C.Barry Thomas,et al.The selective oxidation of toluenes tobenzaldehydes by Cerium(Ⅲ),hydrogen peroxide and bromide ion[J].Journal of Molecular Catalysis A.,1997,117:279-287.
[20]吴泽彪,盛梅,林西平.甲苯气相氧化制苯甲醛[J].膜科学与技术,2000,20(6): 29-32.
[21]Jin S.Yoo.Gas phase oxygen oxidation of alkylaromatics over CVD Fe/Mo/borosilicate molecular sieve,Fe/Mo/DBH Ⅶ,oxidative dehydrogenation of alkylaromatics[J].Applied Catalysis A.,1996,142:19-29.
[22]Centi G.,Perathoner S..Site isolation in iron-molybdate-based catalysts for side chain oxidation of alkylaromatics[J].Topics in Catalysis,2001,15(2-4):145 - 151.
[23]Centi G.,Perathoner S.,Tonini S..Synthesis of 3-fluorobenzaldehyde by gas-phase selective oxidation on Fe-Mo oxide/boralite catalysts[J].Topics in Catalysis,2000:195-204.
[24]Aguilar Elguezabal A.,Cortes Corberan V..Selective oxidation of toluene on V_2O_5/TiO_2/SiO_2 catalysts modified with Te,Al,Mn and K_2SO_4[J].Catalysts Today,1996,32:265-272.
[25]Frank Konietzni,Uwe Kolb,Uwe Dingerdissen,et al.AMM-Mn_xSi-Catalyzed selective oxidation of toluene[J].Journal of Catalysts,1998,176:527-535.
[26]Dmitri A.Bulushev,Lioubov Kiwi-Minsker,Vladimir I.,et al.Effect of potassium doping on the structural and catalytic properties of V/Ti-oxide in selective toluene oxidation[J].Applied Catalysis A.General 2000,202:243-250.
[27]肖春妹,李国情.甲苯液相空气催化氧化技术研究进展[J].化工生产与技术,2006,13(2):46-50.
[28]户安军,吕春绪,李斌栋.甲苯类化合物的选择性氧化[J].化学进展,2007,19(2/3):292-302.
[29]Partenheimer W..Catalysis Today,1995,23:69-158.
[30]Mannepalli Lakshmi Kantan.An improved process for selective liquid-phase air oxidation of toluene[J].Catalysis Letters,2002,81:223-232.
[31]乔艳辉,滕俊江.液相催化氧化法制备邻羟基苯甲醛[J].茂名学院学报,2005,15(4):26-29.
[32]阳卫军,郭灿城.金属卟啉化合物及其对烷烃的仿生催化氧化[J].应用化学,2004,21(6):541-545.
[33]佘远斌,王兰芝,宋旭锋等.金属卟啉类催化剂的合成、构效关系及在催化氧化碳氢化合物中的应用[J].精细化工,2005,22(6):401-408.
[34]王兰芝,佘远斌,徐未芝等.金属卟啉类模拟酶催化剂研究[J].化学进展,2005,17(4):678-685.
[35]童金辉,李臻,夏春谷.环境友好催化氧化研究进展[J].化学进展,2005,17(1):96-110.
[36]李鸿波,曾伟,杜瑛等.冠醚化Schiff碱[J].有机化学,2002,22(6):397-404.
[37]周智明,李连友,徐巧等.仿生催化剂-Salen金属络合物催化不对称环氧化烯烃的基础[J].有机化学,2005,25(4):347-354.
[38]孙伟,夏春谷.金属卟啉催化烯烃环氧化及反应机理研究[J].化学进展,2002,14(5):8-17.
[39]Mukaiyama T.,Yamada T.Bull.Chem.Soc.Jpn.,1995,68:17-35.
[40]Murahashi S.I.,Komiya N.Catal.Today,1998,41:339-349.
[41]李建章,李慈,秦圣英.仿生氧载体均相催化性能研究现状[J].西南民族学院学报,1998,24(4):420-424.
[42]曹志红,刘文明,项学明.La-OMS-2催化剂催化甲苯氧化制苯甲醛[J].石油化工,2006,35(11):1069-1073.
[43]Yasutaka I.,Kouichi N.,Mitsuhiro T.,et al.A Novel Catalysis of N-Hydroxyphthalimide in the Oxidation of Organic Substrates by Molecular Oxygen[J].J.Org.Chem.,1995,60:3934-3935.
[44]Xavier B.,Isabel W.C.E.A.,Ellwood S.,et al.A New Catalytic System for the Selectivity Aerobic Oxidation of Large Ring Cycloalkane to Ketones[J].Organic Process Research & Development,2003,7:426-428.
[45]Yasutaka I.,Satoshi S..A new strategy for alkane oxidation with O_2 using N-hydroxyphthalimide(NHPI)as a radical catalyst[J].Catalysis Surveys from Japan,1999,3:27-35.
[46]Babak K,Jamshid R.An improved protocol for aerobic oxidation of acetals to esters catalyzed by N-hydroxy phthalimide(NHPI)and lipophilic Co(Ⅱ)complexes[J].Journal of Molecular Catalysis A.Chemical,2005,226:165-169.
[47]Asushi Y.,Yoshiaki H.,Takahiro I.,et al.Catalytic Oxidation of Alkylbenzenes with Molecular Oxygen under Normal Pressure and Temperature by N-Hydroxy phthalimide Combined with Co(OAc)_2[J].J.Org.Chem.,1997,62:6810-6813.
[48]刘耀华,崔鹏,孙靖,杨帆等.离子液体中芳烃侧链分子氧催化氧化反应研究[J].高等学校化学学报,2006,27(12):2314-2318.
[49]方岩雄,顾浩,张赛丹等.离子液体中氧化反应研究进展[J].精细化工,2005,22(6):451-454.
[50]Choudhary V.R.,Dumbre D.K.,Uphade B.S.,et al.Solvent-free oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide using transition metal containing layered double hydroxides and/or mixed hydroxides[J].Journal of Molecular Catalysis A.,2004,215:129-135.
[51]Singh A.P.,Selvam T..Liquid phase oxidation reactions over chromium silicalite-1(CrS-1)molecular sieves[J].Journal of Molecular Catalysis A.,1996,113:489-497.
[52]John David O.Anderson and Walter Scrivens.Fluorinated and chlorinated benzaldehydes[J],US 6297405,2001.
[53]蔡敏敏,魏运洋,蔡春等.氧气液相氧化法制备邻硝基苯甲醛[J].化学反应工程与工艺,2002:18(1):23-26.
[54]蔡敏敏,魏运洋,蔡春等.氧气液相氧化邻硝基甲苯制备邻硝基苯甲醛-反应条件的研究[J].染料工业,2002:39(2):39-41.
[55]蔡敏敏,魏运洋,吕春绪.氧气液相氧化邻硝基甲苯制取邻硝基苯甲醛[J].南京理工大学学报,2006:22(2):197-200.
[56]蔡敏敏,曹阳,魏运洋等.氧气液相氧化邻硝基甲苯合成邻硝基苯甲醛-溶剂对反应的影响[J].染料工业,2002,9(1):39-40.
[57]张金生,边鲁宁,李丽华.离子液体的合成研究与应用进展[J],化学与生物工程,2007,1(24):7-9.
[58]Kenneth R.Seddon,AnnegretStark,Green Chemistry,2002,4:119-123.
[59]Backstrom H.L..J.Am.Chem.Soc.,1927,(49):1460.
[60]Peter D.Metelski,Victor A.Adamian.Mechanistic Role of Benzylic Bromides in the Catalytic Autoxidation of Methylarenes[J].Inorg.Chem.,2002,(39):2434-2439.
[61]陈书阁.γ型化学二氧化锰的合成[J].无机盐工业,I997,(3):17-20.
[62]夏熙.电池组二氧化锰[M].袁光钰译.北京:轻工业出版社,1997:19-34.
[63]杜献.对醇氧化的一些特殊氧化剂的探讨[J].井冈山学院学报(自然科学),2006:27(12):66-67.
[64]Goldman I.M.,J.Org.Chem.,34,1979(1969).
[65]张立珠,陈忠林,马军等.水溶液中新生态MnO_2对苯酚的氧化作用及机理研究[J].环境科学,2006,27(5):941-944.
[66]双喜,丽丽,嘎日迪.液相沉淀法制备纳米Mn_2O_3[J].内蒙古石油化工,2005,(11):12-13.
[67]陈志文,张庶元,谭舜等.纳米Mn_2O_3的制备及其ESR研究[J].波谱学杂志,1997,14(5):443-448.
[68]陈志文,张庶元,谭舜等.纳米Mn_2O_3的制备及其分形凝聚[J].中国科学技术大学学报,1998,28(2):227-229.
[69]何建玲,孙德胜,王遵尧.用Mn_2O_3法合成对羟基苯甲醛[J].当代化工,2004,33(1):4-7
[70]严新,宋萌,林周等.用Mn_2O_3氧化法合成对羰基苯磺酸[J].江苏化工,2004,32(4):31-33.
[71]王琪,刘继泉.空气间接氧化制备对叔丁基苯甲醛的新工艺[J].青岛科技大学学报,2005,26(2):106-108.
[72]Wendt H.,Schneider H.Reaction kinetics and reaction techniques for mediated oxidation of methylarenes to aromatic ketones[J].Ibid,1986,16:134-146.
[73]梁慧锋,马子川,刘占牛.新生态二氧化锰的性质及pH值影响除砷效果的研究[J].无机化学学报,2006,(4):743-747.
[74]李刚,王武明.中国锰业状况[J].四川化工,1993,(2):5-7.
[75]胡国荣,周玉琳,彭忠东.用工业硫酸锰制取高纯碳酸锰的工艺研究[J].中国锰业,2007,25(2):14-17.
[76]陈书阁.碳酸锰分解氧化工艺条件的探讨[J].无机盐工业,1994,(6):20-21.
[77]谌曙永.碳酸锰热解生成二氧化锰的试验研究[J].中国锰业,1991,9(6):21-24.
[78]Marba'n G.,Teresa Valde's-Soli's,Antonio B..Fuertes,Mechanism of low temperature selective catalytic reduction of NO with NH_3 over carbon-supported Mn_3O_4[J].Phys.Chem.Chem.Phys.,2004,6,453-464.