Gemini表面活性剂合成进展

:20035,:2003123(No.20243005,20243006)(02C431)33e2mail:[e-mail]31,213313(1.250100;2.422001;3.410082)Gemini,,Gemini,Gemini():O64712:A:10052281X(2004)0320349216ProgressinSynthesisinGeminiSurfactantsYaoZhigang1,2LiGanzuo133DongFenglan1HuAixi3(1.KeyLaboratoryforColloidandInterfaceChemistryofMinistryofEducation,ShandongUniversity,Jinan250100,China;2.DepartmentofChemistryandMaterialsScienceEngineering,ShaoyangCollege,Shaoyang422001,China;3.CollegeofChemistryandChemicalEngineering,HunanUniversity,Changsha410082,China)AbstractWithasystematicsummaryoftheprocessesandproceduresforthesynthesisofnearly100kindsofGem2inisurfactantsandadetailedcomparisonandclassificationofGeminisurfactantsaswellintermsoftheirstructuralfea2tures,thispaperisdesignatedtoproposesomenewideasofthedevelopmentofthesynthesisofGeminisurfactants,whicharededicatedforthepromotionoftheindustrializationofthenovelGeminisurfactants.Keywordsgeminisurfactants;dimericsurfactants;synthesisGemini(),,,[17],Gemini,,:,,();,,,,,Gemini,Gemini(27,36,18,8),,,GeminiGemini1.Gemini,,:16320045PROGRESSINCHEMISTRYVol.16No.3May,2004053162.18,16,,,:[8],:2CH3(CH2)nN(CH3)2+CH2BrCH2BrCH2(CH3)2N+(CH2)nCH3CH2(CH3)2N+(CH2)nCH3,HOCH2(CH2OCH2)3CH2OHPBr3BrCH2(CH2OCH2)3CH2Br[12],[20],[14]:12N,N,NN2[11],:2RBr+(CH3)2N(CH2)sN(CH3)2RN+(CH3)2(CH2)sN+(CH3)2R2Br-1213,,:,14,15,:16,,,,:,,,18,Gemini:1533Gemini,1920,,19:21,22,DNA21:ClCH2COOCH2CH2OOCCH2Cl+2(CH3)2NC12H252122:NHC(H2)3CHNH2COOHCH2NNNO2(CH2)xCH3COCl(CH2)xCH3CONHCCOOHH(CH2)3NHCH2NNNO2BOP(CH2)sNH2NH2(CH2)xCH3CONHCC(H2)3NHCH2NNNO2HCONH(CH2)sNHCOHCC(H2)3NHCNNO2NH2NHCO(CH2)xCH3a)H2,PdPCMeOHPHCOOHb)MeOHPHCl2224,25,26,,,:lv27,Gemini,,,,,,,lw911172023,,Gemini,,,,,,25316GeminiGemini,,(58),,1.(1):(2)28Gemini,,,:NH2CH2CH2NH2+2Cl(CH2)7CH3CH3(CH2)7NHCH2CH2NH(CH2)7CH3ClCH2COONa28,,29,3329:33:,30:3533Gemini31,2834,35,:36,:NH2CH2CH2NH2+2ClCH2COONaNaOOCCH2NHCH2CH2NHCH2COONa2CH3(CH2)10COCl36,,,ROOCCOHHCHCOOROHqROBrROCH2ClROOCCqORCROOCCH2ORHCCH2ORHCOORHCHCOORqOR34NaOH,H2O352.(),,,(1)45316(2)37:CH3(CH2)nCH2OH+HOPOOHOPOOHOHtoluener.t.CH3(CH2)nCH2OPOOHOH(CH2)4N+OH-MeOH[CH3(CH2)nCH2OPOOHO-2N+(CH3)4BrBrCH2OPOO-O(CH2)nCH3CH2OPOO-(O(CH2)nCH32N+(CH3)4H+3738:3937:POH25C12OOHOH1)NMe4OHPMeOH2)Br(CH2)sBrPCH3CN3)H3O+PH2O4)NaOEtPEtOH3940,:41,42:43:44,,3.(1)5533Gemini(2),LASSDSAESGemini,,,,4546:47:48,,49,5051,,,:48,6531652:53,:54,,,();55,56:2,2RCSO3HCOOH+HO(CH2CH2O)nHCOO(CH2CH2O)nCRSO3HOCCSO3HRNaOH5657,,:H3COH+H3C(CH2)10COClH3COCO(CH2)10CH3friesrearrangementH3COHCOH23C11sulfonateneutralizeH3CSO3NaOHCOH23C11ethanediamine5758,DOW,,:qOq2RCH2CH2(2RX)catqROqRSO3(HSO3Cl)solventqRSO3HOqRSO3HNaOH58lv,Gemini,,4.,R1OCH2COZHCH2O(CH2CH2O)nCH2COZHCH2OR2R1,R2:C6C20alkyloralkenylgroupsn:120Z:H,SO3H,PO(OH)2,CH2COOH,(CH2)2SO3Horasaltthereof59[56]7533GeminiR3AR1R2YAR1R2YR1:C5C22alkyl,hydroxy2substitutedorperfluorinatealkyl,oracylR2:C1C10alkyleneandhydroxysubstitutedderivativesthereofR3:aspacer,e.g:CH2,S,O,SSR4:C1C20orHA:CR4,M:H,Na,K,NH3Y:SO3M,OSO3M,OP(O)(OM)2,CH2COOM60[57]XCR2RCONR4R6YZCR1R3CONR5R7YZR,R1,R2,R3:C1C22alkyl,arylorHR4,R5:C1C6alkyorH;R6,R7:C2C6alkylorarylorHX:aspacer,S,SS,(CH2)nY:PO4,SO3Z:Na,K,etal.61[58]C(H2)2SH19C9ONHSO3NaSH19C9ONHSO3NaqOH19C9ONHSO3NaOH19C9ONHSO3Na[R1N_C2H4O)ba_C3H6O)dna_OH6C3bc_OH4C2bdNR2]m(C2H4Obe_(C2H5ObfYZ_OH6C3bg_OH4C2)ha,b,c,d,e,g:015Y,Z:HorCH2COOM,SO3M,C2H4SO3M,COC2H3(SO3M)COOM,P(O)(OM)2M,M:Na,K,etal.62[59](R2OOXH)R1(H(R1)O(R3)HOYR3(H)R1,R3:C6C18hydrocarbonchainsR2:aspacerX,Y:(C2H4O)a(C3H6O)bH,(C2H4O)c(C3H6O)dFRFR:CH2COOM,SO3M,P(O)(OM)2,C2H4SO3MM:K,Na,etal.63[60]Gemini,,:,11853169533Gemini2.:6473;7581,,,(APG),Gemini,:70,71;,67:69:7071,,:72:,,,77:81,90Dynol,,,,,,,,,,,Gemini1.063162.Gemini,1587,,,;88;8982,1966AndrewT.Guttmann,,82,,(1)8386,86,(2)87,(3)88:CH3_CH2)7CHCH_CH2)7CNH2O2(R4N)3PW4O2CH3_CH2)7COHCH_CH2)7CNBF3CH3O(C2H4O)nHCH3_CH2)7CMePEGHCOHH_CH2)7)CNClSO3HCHCl3,2535,2hNaOH88(4)89:1633GeminiGemini1.GeminiGemini,,1[84]:1GeminiFig.1SchematicrepresentationoftheGeminisurfactantstructure,:,_CH2bn,_C2H4Obx;,:q,qCHCHq,CC,Gemini1,,,,_CH2bn,_C2H4Obx,,,,,2.Gemini[84,85](),()(),:,;,,()Israelachvi2li[86]:(packingparameter)P=VPa0Lc,V;Lc;a0P1P3;1P3P1P2;1P2P1;P1;P1,,,CO2,AOT,,,P1,Gemini,,P1,AOT,:,Gemini,,,,,Gemini,,P,Va0Lc,,,Va0Lc,,P,,,3.,,,,26316,Gemini,,,,,,,,[1]RosenMJ.Chemtech.,1993,(3):3033[2]ZanaR.Curr.Opin.ColloidInterfaceSci.,1996,1(5):566571[3](ZhaoJX).(Prog.Chem.),1999,11(4):348357[4]MengerFM,KeiperJS.Angew.Chem.Int.Ed.,2000,39:19061920[5](TangSH),(HuangJB),(LiZC).(ChinaSurfactantDetergent&Cosmetics),2001,(6):2629[6](TangSH),(HuangJB),(LiZC).(ProgressinNaturalScience),2001,11(12):12401251[7]ZanaR.Adv.ColloidInterfac.,2002,97(1P3):205253[8]MengerFM,LittaluCA.J.Am.Chem.Soc.,1991,113:14511452[9]MengerFM,LittaluCA.J.Am.Chem.Soc.,1993,115:1008310090[10]ZhuYP,MasuyamaA,NakatsujiT,etal.Jpn.OilChem.Soc.,1991,40(5):473477[11]TaeSeongK,ToshiyukiK,YohjiN,etal.J.Am.Oil.Chem.Soc.,1996,73(7):907911[12](IsaoI),(CuiZG).(ChinaSurfactantDetergent&Cosmetics),2001,(3):2730[13]TaeSeongK,ToshikazuH,IsaoI.J.Am.Oil.Chem.Soc.,1996,73(1):6771[14](IsaoI)