环己基苯基甲酮合成方法的研究
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摘要
环己基苯基甲酮是一种重要的医药、染料中间体。本论文通过对环己基苯基甲酮合成方法的研究，为环己基苯基甲酮这一产品的工业化生产向着“绿色化工”方向发展迈出了探索性的一步。具体研究工作可分为以下几点：
1、对传统的环己基苯基甲酮的生产工艺进行改进，用三氯化磷取代原有工艺中所用的二氯亚砜，不但避免了有毒气体二氧化硫的生成，并且简化了操作工艺，节省能耗。同时对改进工艺的反应条件进行了优化，在适宜的反应条件下，得环己基苯基甲酮收率为81.3％。
2、将几种固体酸催化剂应用于制备环己基苯基甲酮的Friedel-Crafts酰基化反应，对它们的催化活性进行了考察，筛选出了一种适合本反应体系的固体酸催化剂。对于这一部分又可分为以下四方面工作：
(1)考察了H-β型、H-Y型、HZSM-5型三种型号的沸石，分别对焙烧温度、催化剂比用量、反应温度及反应时间对产品环己基苯基甲酮收率的影响进行了实验分析，得到了适宜的反应条件。
(2)对AlCl_3负载于阳离子交换树脂上的固体超强酸应用于本反应的催化活性进行了考察。对催化剂比用量、反应温度、反应时间对产品环己基苯基甲酮收率的影响进行了实验分析，得到了适宜的反应条件。
(3)对SO_4~(2-)／M_xO_y固体超强酸应用于本反应的催化活性进行了考察，主要分析了SO_4~(2-)／Al_2O_3型和SO_4~(2-)／ZrO_2型固体超强酸的焙烧温度、比用量以及反应时间、反应温度对产品环己基苯基甲酮收率的影响，得到了适宜的反应条件。
(4)考察了磷钨杂多酸对本反应的催化活性。对催化剂比用量、反应温度及反应时间对本反应产品收率的影响进行了实验分析，得到了适宜的反应条件
3、用环己基甲酸作为本Friedel-Crafts酰基化反应的酰基化试剂，解决了原反应物环己基酰氯的腐蚀性问题。考察了沸石型催化剂对本反应体系的催化活性，得到了适宜的反应条件，在此条件下环己基苯基甲酮收率为12.8％。
Methanone cyclohexylphenyl is an important organic medium material of medicine and dyestuff.In this thesis,the synthesis of methanone cyclohexylphenyl was studied.The problem of producing methanone cyclohexylphenyl to "Enviromentally Friendly Chemistry" was settled exploringly.Main studies as follows:
1 The traditional route of methanone cyclohexylphenyl synthesis was improved.Phosphor trichloride substituded dimethylsulfoxide in the old route.The method avoided letting out toxic gas sulfur dioxide,simplified operation craftswork and saved energy. Operation craftwork was experimented and analyzed.In the suitable operating conditions,the yield of methanone cyclohexylphenyl was 81.3%.
2 Several solid acidic catalysts were used and studied in the Friedel-Crafts acylation reaction of synthesis of methanone cyclohexylphenyl.Their catalysis activities were studied to select a better solid acidic catalyst fitting this system.This study divided into four parts as follows:
(l).The three types of H- P ,H-Y and HZSM-5 zeolites were studied.The effection of calcination temperature,specific use of catalysts,reaction temperature and reaction time to the methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(2).The application of the solid superacids-cation exchange resin A1C13 in methanone cyclohexylpheny synthesis was studied.The effection of specific use of catalyst, reaction temperature and reaction time to the methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(3) The application of the SO2"4/MxOy solid superacid in methanone cyclohexylpheny synthesis was studied. Calcination temperature of SO2 4/Al2O3 and SO2yZr02,specific use of catalysts, reaction temperature and reaction time to effect methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(4). The application of the tungstophosphoric heteropoly acid in methanone cyclohexylpheny synthesis was studied. Specific use of catalyst, reaction temperature and reaction time to effect methanone cyclohexylphenyl yiely were analyzed.The suitable operating conditions were got.
3 Cyclohexyl acid was used in acylation reagent of Friedel-Crafts acylation reaction and the
eroding problem of the old reactant cyclohexyl acyl chloride was solved.The catalysis activity of zeolites in this reaction was studied. The suitable operating conditions were got.In the condition,the yield of methanone cyclohexylphenyl was 12.8%.
1、对传统的环己基苯基甲酮的生产工艺进行改进，用三氯化磷取代原有工艺中所用的二氯亚砜，不但避免了有毒气体二氧化硫的生成，并且简化了操作工艺，节省能耗。同时对改进工艺的反应条件进行了优化，在适宜的反应条件下，得环己基苯基甲酮收率为81.3％。
2、将几种固体酸催化剂应用于制备环己基苯基甲酮的Friedel-Crafts酰基化反应，对它们的催化活性进行了考察，筛选出了一种适合本反应体系的固体酸催化剂。对于这一部分又可分为以下四方面工作：
(1)考察了H-β型、H-Y型、HZSM-5型三种型号的沸石，分别对焙烧温度、催化剂比用量、反应温度及反应时间对产品环己基苯基甲酮收率的影响进行了实验分析，得到了适宜的反应条件。
(2)对AlCl_3负载于阳离子交换树脂上的固体超强酸应用于本反应的催化活性进行了考察。对催化剂比用量、反应温度、反应时间对产品环己基苯基甲酮收率的影响进行了实验分析，得到了适宜的反应条件。
(3)对SO_4~(2-)／M_xO_y固体超强酸应用于本反应的催化活性进行了考察，主要分析了SO_4~(2-)／Al_2O_3型和SO_4~(2-)／ZrO_2型固体超强酸的焙烧温度、比用量以及反应时间、反应温度对产品环己基苯基甲酮收率的影响，得到了适宜的反应条件。
(4)考察了磷钨杂多酸对本反应的催化活性。对催化剂比用量、反应温度及反应时间对本反应产品收率的影响进行了实验分析，得到了适宜的反应条件
3、用环己基甲酸作为本Friedel-Crafts酰基化反应的酰基化试剂，解决了原反应物环己基酰氯的腐蚀性问题。考察了沸石型催化剂对本反应体系的催化活性，得到了适宜的反应条件，在此条件下环己基苯基甲酮收率为12.8％。
Methanone cyclohexylphenyl is an important organic medium material of medicine and dyestuff.In this thesis,the synthesis of methanone cyclohexylphenyl was studied.The problem of producing methanone cyclohexylphenyl to "Enviromentally Friendly Chemistry" was settled exploringly.Main studies as follows:
1 The traditional route of methanone cyclohexylphenyl synthesis was improved.Phosphor trichloride substituded dimethylsulfoxide in the old route.The method avoided letting out toxic gas sulfur dioxide,simplified operation craftswork and saved energy. Operation craftwork was experimented and analyzed.In the suitable operating conditions,the yield of methanone cyclohexylphenyl was 81.3%.
2 Several solid acidic catalysts were used and studied in the Friedel-Crafts acylation reaction of synthesis of methanone cyclohexylphenyl.Their catalysis activities were studied to select a better solid acidic catalyst fitting this system.This study divided into four parts as follows:
(l).The three types of H- P ,H-Y and HZSM-5 zeolites were studied.The effection of calcination temperature,specific use of catalysts,reaction temperature and reaction time to the methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(2).The application of the solid superacids-cation exchange resin A1C13 in methanone cyclohexylpheny synthesis was studied.The effection of specific use of catalyst, reaction temperature and reaction time to the methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(3) The application of the SO2"4/MxOy solid superacid in methanone cyclohexylpheny synthesis was studied. Calcination temperature of SO2 4/Al2O3 and SO2yZr02,specific use of catalysts, reaction temperature and reaction time to effect methanone cyclohexylphenyl yield were analyzed.The suitable operating conditions were got.
(4). The application of the tungstophosphoric heteropoly acid in methanone cyclohexylpheny synthesis was studied. Specific use of catalyst, reaction temperature and reaction time to effect methanone cyclohexylphenyl yiely were analyzed.The suitable operating conditions were got.
3 Cyclohexyl acid was used in acylation reagent of Friedel-Crafts acylation reaction and the
eroding problem of the old reactant cyclohexyl acyl chloride was solved.The catalysis activity of zeolites in this reaction was studied. The suitable operating conditions were got.In the condition,the yield of methanone cyclohexylphenyl was 12.8%.
引文
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[2] Yoshmao T.Trofuml O.Unsymmetrical ketone sythesis via palladium catalyzed carbonylation of organic halides Tetradron Lett 1983,24:3869
[3] Rudolf P.Gregor W.Carbonylation of aliphatic hydrocarbons in the presence of HF/SbF5 Chem. Ber. 1976,100:984
[4] Yasuhide Y.Terukiyo H. The Neitzescu reation Nippon Kafaku Zasshi 1961,82:1563
[5] Ngoc Tugett LT,Hebd CR. Transformation of acid chloride into corresponding ketones using organocopper( I ) Intermediates Seances Acid Sci.Ser.C. 1977,16:579
[6] Hatsuo Maeda,Junko O kamoto,Hidenobu Ohmori. Reactions of In Situ Formed Acyl Tributyphosphonium Ions with Grignard Reagents as an Effective Route to ketone from Acid chlorides Tetrahedron Lett. 1996,37(30) :5381-5384
[7] Tadayo Miyasaka,Hideaki Monobe and Shunsaku Noguchi. Reaction of (Z)-phenyl 2-pyridyl Ketone O-Acyloximes(PPAO) with Grignard Reagents:A convenient and highly chemoselective synthesis of ketones Chemistry Letters 1986,449-452
[8] James H.Clark, Andrew J. Butterworth, Stewart, J.Tavener , et al. Environmentally Friendly Chemistry Using Supported Reagent Catalysts:Chemically-Modified Mesoporous Solid Catalysts J.Chem.Tech.Biotechnol. 1997, 68:367-376
[9] James H.Clark, Stephen R Cullen, Simon J Barlow, et al. Environmentally Friendly Chemistry using Supported Reagent Catalysts:Structure-Property Relationships for Clayzic J.Chem.Soc.Perkin Tran. 1994:1117-1130．
[10] Tony W.Bastock,James H.Clark, Philip Landon, et al. Competitive Alkylation Reactions in the Montmorillonite-FeCl3-catalysed Acylation of Aromatic Substrates J.Chem.Research(S) 1994, 104-105
[11] Chrlstopher N.Rhodes, David R.Brown. Surface Properties and Porosities of Sillica and Acid-treated Montmorillonite Catalyst Supports:Influence on Activities of Supported ZnCl2 Alkylation Catalysts J.Chem.Soc.Faraday Trans. 1993, 89(9) : 1387-1391
[12] David K.Brown, Howell G.M.Edwards, Dennis W.Farwell, et al. FT-Raman spectroscopic study of the active sites on silica-supported ZnCl2 catalysts J.Chem.Soc., Faraday Trans. 1996, 92(6) : 1027-1029
[13] Yin Dong hong, Yin Dulin, Fu Zaihui. The Regioselectivity of Friedel-Crafts Acylation of Anisole
Using Microwave Modified ZnCl2/HY Zeolite Catalysts 分子催化 1998, 12(6) :401-402
[14] 季小慎，王雪峰，严久凤．硅胶介质对微波辐射下AlCl3催化Friedel-Crafts反应的促进作用催化学报 1997, 18 (5) :436-438
[15] Jack M.Miller, David Wails, J.Stephen Hartman, et al. Friedel-Crafts catalysis using supported reagents Synthesis,characterization and catalytic applications of sol-gel-derived aluminosilicates J.Chem.Soc., Faraday Trans. 1997, 93(4) :2439-2444
[16] Mitsuo Kodomari , Shinkichi Tagushi. Friedel-Crafts Arylmethylation of Aromatics with Bis(chloromethyl)benzenes Catalysed by Zinc Chloride Supported on Silica Gel J.Chem.Research(S) 1996, 240-241
[17] Anjali.P.Deshmukh, Kamlesh J.Padiya, Manikrao M.Salunkhe. Friedel-Crafts Acylation Reaction using Polymer Supported Aluminium Chloride J.Chem.Research(S) 1999, 568-569
[18] Shu.Kobayashi, Satoshi Nagayama. A Microencapsulated Lewis Acid .A New Type of Polymer-Suppported Lewis Acid Catalyst of Wide Utility in Organic Synthesis J.Am.Chem.Soc. 1998, 120, 2985-2986
[19] I.Hachiya , Shu Kobayashi , Shunsuke Iwamoto. Catalytic Friedel-Crafts Acylation of Benzene,Chlorobenzene,and Fluorobenzene Using a Novel Catalyst System,Hafnium Triflate and Trifluoromethanesulfonic Acid Tetrahedron Lett. 1995, 36:409
[20] Hiroyuki Kusama , Koichi Narasaka. Friedel-Crafts Acylation of Arenes Catalyzed by Bromopentacarbonylrhenium( I )Bull.Chem.Soc.Jpn.1995, 68:2379-2383
[21] Jun Izumi, Teruaki Mukaiyama. The Catalytic Friedel-Crafts Acylation Reaction of Aromatic Compounds with Carboxylic Anhydrides Using Combined Catalyst System of Titanium(IV)Chloride Tris(trifluoromethanesulfonate) and Trifluoromethane Acid Chemistry Letters 1996, 739-740
[22] J.R.Desmurs. Surprising Catalytic Activity of Bismuth(III) Triflate in the Friedel-Crafts Acylation Reaction Tetrahedron Lett. 1997, 38:8871-8874
[23] Atsushi Kawacla, Shuichi Mitamura, Shu Kobayachi. Ln(OTf)3-LiClO4 as Reusable Catalyst System for Friedel-Crafts Acylation Chem.Commun. 1996, 183-184
[24] Kawada A , Mitamura S , Kobayashi S. Lanthanide Trifluoromethanesulfonates as Reusable Catalysts:Catalytic Friedel-Crafts Acylation J.Chem.Soc., Chem.Commun. 1993, 1157-1158
[25] Kawada.A, Mitamura S, Kobayashi S. Scandium trifluoromethanesulfonate,A Novel Catalyst for Friedel-Crafts Acylation Synlett, 1994, 545-546
[26] Hachiya.I, Moriwaki M, Kobayashi S.Hafnium(IV) Trifluoromethanesulfonate,An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reations Bull.Chem.Soc.Jpn. 1995, 68:2053-
2060
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