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KnoevenagelCondensationCatalysedbyAlumin

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KnoevenagelCondensationCatalysedbyAlumin

    α

    Kn oevenage l Con den sa t ion Ca ta ly sed by A lum ina

    M a, C h en L in , J i2M ao H ao , A i2Yo u Su n , C h an g 2J u n

    (),Sh ando ng U n ive r sity, J inan , 250100 D ep a r tm en t o f C h em ist ry

    A bstra c t T h e k no even age l co n den sa t io n o f ca rbo n y l com po u n d s w ith ac t ive

    . m e th y len e com po u n d s w a s ca r r ied o u t in th e p re sen ce o f a lum in a a s ca ta ly stT h is reac2

    . t io n affo rded h igh y ie ld in m ild reac t io n co n d it io nSygn if ican t im p ro vem en t s o f th e re2

    .ac t io n ra te s can b e ach ieved w h en th e reac t io n m ix tu re a re so n ica ted

    K no even age l co n den sa t io n , C a rbo n y l com poo u n d s, A c t ive m e th y len e Keyword s

    com po u n d s, A lum in a, U lt ra so n ic ir rad ia t io n.

    2. T h e k no even age l co n den sa t io n is a typ ica lly b a seca ta ly sed reac t io nT h e ca ta2

    , ly st s a re am m o n ia an d am m o n ium sa lt sp r im a ry an d seco n da ry am in e s an d th e ir 1 . . sa lt sT h e com m o n e s t ca ta ly s t is th e p ip e r id in e in a lco ho lic so lu t io nW eak ly b a s ic 2 , n ex ch an ge re s in spo ta s s ium f luo r ide an d ce s ium f luo r ide h ave a lso b een u sed a s io

    . tA lum a s g een u sed s a t d reagen t in o rgan ic syn talysinhalonbacatalysanthesis ca

    b u t it is o n ly recen t ly th a t sy stem a t ic in ve st iga t io n o f th e u se o f se lec ted reagen t s ab 2 3 6 7 so rb ed o n a lum in a h a s b een u n de r tak en . H av in g ac id ic an d b a sic site sa lum in a ,

    . is k now n to effec t m an y o rgan ic reac t io n s u n de r m ild co n d it io n sW e fo u n d th a t com 2

    m e rc ia l b a sic a lum in a ea sily p e rfo rm ed th e co n den sa t io n o f a rom a t ic a ldeh yde s w ith

    :m a lo n ic ac id in ch lo ro fo rm

    A l2O 3 () () + CH 2 CO 2H 2 A rCHO C CO 2H 2 2O + H A rCH CH C l3

    1 8

    1 2 5 7 8 4 6 3 P ro duc t

    N O N O C l C l 2 2 O 2N A r C l O

    8. T e eed s t tem tu reT iso n f p t f hreactionnharefluxperahelatiooroducogood

    , . p u r ity w a s ve ry ea syth e y ie ld s w e re h ighA lum in a a lso p e rfo rm ed th e co n den sa to n

    .o f m a lo no n it r ile w ith cyc lo h ex ano n e o r fu rfu ra l T h e reac t io n s w e re ve ry fa st

    () 10:m in a t room tem p e ra tu re w ith h igh y ie ld s

    A l2O 3 () () CH CN + + C CN 2 H 2O O 2 2 CH C l3

    9

α R ece ived M ay 25, 1998.

    ()() 6 卷第 3 1998 合成化学 H ECH EN G HU A XU E 233

    A l2O 3 () () + CH CN CH C CN 2 + H 2O CHO 2 2 CH C l O O 3

    10 8 10 S in ce u lt ra so u n d acce le ra te s m an y h e te ro gen eo u s reac t io n sin o rgan ic syn 2

    ,th e s is w e rea so n ed th a t app lica t io n o f so n ic w ave s co u ld b e b en ef ic ia l in o u r exp e r i2

    1, .A s it can b e seen f rom th e re su lt s m en t io n n ed in th e T ab le u lt ra so u n d ef2 m en t s

    . fec t ive ly p rom o ted th e k no even age l co n den sa t io n in th e p re sen ce o f a lum in aT h is 1. 580. 8m o d if ica t io n sho r ten ed th e rea t io n t im e f rom h to hh a t ref lu x tem p e ra tu re . 1.o f so lven tT h e sum m a r ised in T ab le re su lt s a re 3Kn oevenage l Con den sa t ion Ca ta ly sed by A lum ina 1Table

    b . . /. . M PBPaa- 1 1() () ()% P ro duc t Y ie ld H NM R ? T im e h IR Τcm ()?

    ( ) () 3300 2500, 1713 6. 9 s, 2H , 7. 3 7. 6 m , 5H , ()()1 196 197 8 1. 0 81 83 ( )1675, 1620, 750, 685 7. 8 , 1sH

    3300 2500, 1721 ()()( ) ()225 227 2 8 0. 8 92 90 5. 8 s, 2H , 7. 4 8. 2 m , 5H 1693, 1632, 864

    3300 2500, 1723 ( ) ()()()209 211 3 6. 5 s, 2H , 8. 0 8. 9 m , 5H 8 1. 2 78 80 1654, 1618, 823, 682

    3300 2500, 1722, ()()( ) ()160 162 4 8 1. 2 83 87 5. 8 s, 2H , 8. 0 8. 8 m , 5H 1688, 1622, 776

    3300 2500, 1732 ()()( ) ()199 200 5 8 1. 0 84 85 6. 2 s, 2H , 7. 2 8. 2 m , 5H 1680, 1607, 768

    3300 2500, 1718 ()()( ) ()192 193 6 8 1. 2 83 84 8. 1 s, 2H , 7. 5 8. 3 m , 5H 1693, 1625, 756

    3300 2500, 1723 ()()( ) ()185 187 7 8 1. 2 76 80 7. 2 s, 2H , 7. 7 8. 1 m , 5H 1625, 763, 669

    3300 2500, 1718 ()()( ) ()201 202 8 8 1. 5 78 83 7. 1 s, 2H , 7. 3 8. 0 m , 4H 1672, 1641, 739

    137 138 2930, 2215, 1605 () ()9 95 1. 8 m , 6H , 2. 7 m , 4H 10m in 1. 3/1445, 850 KP a

    3100, 3040, 2910 ()71 72 10 90 7. 0 7. 9 m , 4H 10m in 2212, 1450, 760

    a .T h e da ta in p a ren th e sis ind ica te sub jec t io n to u lt ra so und b .So lic sam p le s w e re rec ry sta llized f rom ace t ic ac id

    E xp e r im en ta l Sec t io n

    ( )T o a s t ir red so lu t io n o f ca rbo n y l com po u n d s 0. l 025m o an d ac t ive m e th y len e ( ) ( ) ( com po u n d s 0. 025m o l in ch lo ro fo rm 12m L w a s added a lum in a M e rck 90g 0.

    ) ()025m o lA lum in a w a s h ea ted a t 250? fo r 16h p r io r to u se. S t ir r in g w a s co n t in u ed

    . a t app rop r ia te tem p e ra tu re t ill com p le t io n o f th e reac t io nU lt ra so u n d w a s app lied to

    ()() 6 卷第 3 1998 234 合成化学 H ECH EN G HU A XU E

    . th e reac t io n m ix tu re w h en n ece s sa ryT h e coo led reac t io n m ix tu re w a s f ilte red an d

    . th e p rec ip ita te w a s w a sh ed w ith ch lo ro fo rmT h e com b in ed o rgan ic p h a se w a s evapo 2 ra ted an d th e so lid re sidu e w a s iso la ted b y f ilt ra t io n ch rom o to g rap h y th ro u gh a sho r t

    . p lu g o f silica ge l w ith d ich lo rom e th an eE vapo ra t io n o f so lven t fu rn ish ed p rac t ica lly

    . , . p u re p ro du c tGen e ra llyth e p u r if ica t io n w a s no t n ece ssa ryA ll p ro du c t s w e re ch a r2 1)(. . , , .. ac te r ized b y th e ir p h y s ica l an d sp ec t ra l ch a rac te r is t ic s mpH NM R IR e tc IR 1 Hsp ec t ra w e re m ea su red o n Sh im adzu IR 2408 sp ec t rom e te r. NM R sp ec t ra w e re reco rded o n J EO L 2FX 90Q sp ec t rom e te r an d refe ren ced to TM S.

    , In co n c lu sio n k no even age l co n den sa t io n o f ca rbo n y l com po u n d s w ith ac t ive m e th y len e com po u n d s can b e ca r r ied o u t w ith fa ir y ie ld s u sin g b a sic a lum in a a s ca ta2

    () a . :;ly stT h e im po r tan t fea tu re s o f th is m e tho do lo gy a re no requ irem en t o f b a se () () b ; . no u n de sirab le side reac t io ncm ild reac t io n co n d it io n an d h igh y ie ldN eve r2

    , th e le ssth e qu a lity o f th e a lum in a em po yed is som e t im e s c r it ica l an d th e com m e rc ia l

    .a lum in a m u s t b e t rea ted p r io r to u se

    Ref eren ce s

    1 Jo ne s, G. : O rgan ic R eac t io n s, 1967, 15, 204.

    2 , . ; , . ; , . . : . . . , 1966, 31, 1272. R andLH a ide rk ew ychDPo lin sk iRJJO rgC h em

    , . . ; , . . ; , . . : . , 1991, 32, 2811. 3 R anu BCB h a rBCSa rk a rDCT e t rah ed ro n L e t t

    , . . ; , . : , 1992, 48, 1327.4 R anu BCB h a rST e t rah ed ro n

    , . ; , . ; , . : . . . , 1990, 55, 781. R o sin iGGa la r in iRM a ro t taEJO rgC h em5

    , . . ; , . . : . . , 1994, 152.D h ava leDDP a t ilPNJC h emR e sea rch 6

    , . ; , . : . . , 1991, 131, 190.Ge rva sin iAA u ro uxAJC a ta l 7

    , . ; , . ; , . : . . , 1982, 12, 137. A zum aTYanag idaSSak u ra iHSyn thComm un8

    , . . ; , . : . . . , 1983, 48, 3837.L uch eJLP e t r ie rCJO rgC h em 9

    () M a, C. ; Sun , C. J. ; H ao , A. Y. : C h ine se J. Syn th. C h em. , 1998, 6 1, 8. 10

    A l2O 3 催化克脑文格尔缩合反

     林吉 郝爱 孙昌

    ()山东大学化学, 济南, 250100

     A l2O 3 催化下活泼亚甲基化合物和羰基化合物进行克脑文格尔缩合反, 在温和

     反应条件下得到较高收率的产 将超声波辐射应用于该缩合反应使反应速度明显提关键词 克脑文格尔缩合 羰基化合物 活泼亚甲基化合物 A l2O 3 超声波辐射

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