18 1 1811 1812 1813 182 1821 1822 1823 183 1831 1832 1833 1834 1835 184 1841 1842 1843 1844 1845 185 1851 1852 1853 1854 1855 1856 1857 20, 20 20 70
18 2 Environmentally BenignChemistry)(Environmentally Friendly Chemistry)(Clean Chemistry)
18 3 ( ) 80 9 3 ( )() () ( ) 3 700 2000
18 4 45 21 1811 1Atom economy Stanford B.M.Trost 1991 (Atom Economy) 1998 Zero emission zero emission 1A + B=C 2A + B=C+D
18 5 2 100 / 100 /100 100% DielsAlder =[ 82(28+54)] 100%=100% DA 1. N 2 N 2 + 85% H H H 2. Ph CH 3 + CH 20 ee:64% Ph CH 3 H CH H ( DA )
18 6 100%Wittig 1. 2 Ph 3 P = CH 2 () 2. C 2 Et HC Ph 3 PCHC 2 Et Me () Me R 1 CR 2 Ph 3 P + MeBr Ph 3 P = CH 2 80 4 R 1 R 2 C = CH 2 + Ph 3 P CH 2, 356 14 80 278 100% 100%
18 7 3 1 25% 100% 2 CH 3 CH=CH 2 + HCl CH 3 CH CH 2 + CH 3 CH CH 2 H Cl Cl H Ca ( H ) 2 2 CH 3 CH CH 2 + CaCl 2 + 2H 2 44.1% 1(TS1) CH 3 CH = CH 2 + H 2 2 76.3% TS1 CH 3 CH CH 2 + H 2 2EniChem H H CH 3 CH 3 CH 3 (PhP 3 )RhCl EtH, 25 CH 3 H H 31997 BCH 6 40% 3 80% 99%
18 8 Brown 40.1% BHC 1812
18 9 12 (1) (2) (3) (4) (5) () (6) (7) (8) ( ) (9) (10) (11) (12)
18 10 () 1813 RNH 2 +CCl 2 RNC+2HCl RNCR HRNC+R H RNHC 2 R C 2 CH 2 +C 2 RNC+H 2 RNC+R H RNHC 2 R C 2 C 2
18 11 C 2 C 1996 1821 19 95% 1840 1.5% 66 H 2, Pt 2 HN 3 H H
18 12 () P641 10% 8% 20 70 1.3107 300 2500 2 1822 1 P641 TS1 FeCl + H 2 2 2 60 H H H + H 2
18 13 2 Dimethyl CabonateDMCCH 3 CCH 3 4 90.1 1.069 g/cm 3 DMC 1992 DMC DMC PC DMC DMC DMC DMC A.B. C. DMC DMC DMC ADMS DMSCH 3 SCH 3 DMC
18 14 DMCDMS BClCCl DMCCH 3 CCH 3 DMC DMC DMC 2005 80%DMC CDMC DMC DDMC 53% R+M/2=105 DMC MTBE 4.5 DMC MTBE 2002 DMC DMC DMC SNPE BASF EniChem Ube1999 DMC 30 kt/a DMC 2002 DMC 10 kt/a DMC DMC 2002 99.5%DMC 8 400~9 800 CH 3 NC NC
18 15 /t 150 kt/a DMC DMC 425.1 /t 10% DMC 532.5 /t : CH 3 CH 3 NH 2 2 CH 3 H + 2 CH 3 CCH 3 NHCCH 3 CH 3 NC + 2 CH 3 H NH 2 NHCCH 3 NC 2 CH 3 H + C + 1/2 2 CH 3 CCH 3 + H 2 H 6 5 H H 2 C H CH 2 Cl + C C 6 H 5 CH 2 C 1823 C 2 C 2 C2 RMgX + C 2 RCMgX RC H Cat. RI Cu ( CH 3 ) 2 + C 2 Cu ( CCH 3 ) 2 RCCH 3 Cat. CH 2 = CH 2 + C 2 + H 2 CH 3 CH 2 CH P643
18 16 1831 1 (supercritical fluidscf) () ()
18 17 2 C 2 SCF Supercritical C 2 Extraction C 2 C 2 C 2 AC 2 31.1 7.4MPa BC 2 C sc C 2 (1) 40sc C 2 5 NBS 100%P644 (2)sc C 2 (3) (4) C 2 C 2 (364.2K)(73.8MPa) C 2 C 2 () ()
18 18 3 91 7.38Mpa 374 22Mpa 2398.1MPa 4 1822 Cagniard 1879 Hannay Hogarth 20 30 Pilat Gadlewicz 1950 1954 Zosol 70 Stahl ;1973 1978 1978
18 19 30 A A SCWSuperCritical Water xidization B C D 1832
18 20 H + FeCl 3 60 H H + FeCl 2 + HCl 22 2 1 00 % 99% P646 H H In, H 2 X X + 2RCH R R 1980 Breslow 700 Grieco
18 21 P647 1833 ionic liquid BF 4 PF 6 sc(tf) 3 96 FiedelCrafts CC 3 4 1 3 N AlCl 3 2 AlCl 3 HCl
18 22 1992 [ emim ]BF 4 12 AlCl 3 [center][center][center][ R 1 R 3 im ] + [ bmim ] + BF 4 PF 6 CF 3 S 3 (CF 3 S 2 ) 2 N C 3 C C4 F 9 S 3 CF 3 C (CF3 S 2 ) 3 C (C2 F 5 S 2 ) 3 C (C2 F 5 S 2N SbF6 AsF 6 () 4 2 Hirao 1 3 [ bmim ][ CF 3 S 3 ][ bmim ]Cl ( []X) YXLewisMXy MY(AgYNH 4 Y)AgXNH 3 HX HY :( Y )X X Lewis (MXy )[] [MnXny + 1 ] 5 F 7 2 )
18 23 : [ bmim ] + [ bmim ] [CF 3 S 3 ][ bmim ] [CF 3 C 2 ][ bmim ] [C 3 F 7 C 2 ] [ bmim ]PF 6 [ bmim ] [ (CF 3 S 2 ) 2N ] 20 [ bmim ] [ (CF 3 S 2 ) 2N ] 1. 4 % 400 2 ; 3 ( 2) : PF6 >Beti > Im BF4 >Me AsF6 IBrCl N
18 24 6 3 : ; ; 50 C 2 C 2 C 2 Alabama Rogers ( bmim) PF 6 [ bmim ] PF 6 20 steryoung
18 25 Bonh 30 [ emim ] (CF 3 S 2 ) 2N> 4V 400 : 3 (1) M1Doyle(Dupont) (2)A1Noda ( 3) () 7 1[ emim ] PF 6 [ bmim ] PF 6 1 99% 93%96% [ bmim ] PF 6 66%95% [ emim ] ClAlCl 3
18 26 [ emim ] ClAlCl 3 90 300900 1834 P649 1835 1 2 (MCPBA) ld ld 20 G( ) PTodaMYagiK.KiyoshigeChemCommun958(1988) 2 10 5d 3
18 27 3 60 2.5h 89 4 8 5 F.TodaTshigemasa ChemCommun,209(1989) P651 5 1(1g7mmol) FeCl 3 6H 2 (3.8814mm01) 50 2h 2 95 FToda KTanaaS1wata JrgChem543007(1989) 3 Grignard 0.5h F.TodaHTakumiHYamaguchiChemExp4507(1989) + + NaH 98 Glaser
18 28 6 1a(194so 1m01) 1 cl (5858 04m01)100125 25h 2a(171g 881) F TodaSHyodaKkadaKHirotsuChemCommun.,1531(1995) 7 4 1S (TsH) l0min, 96 PTodaHTakumiMAkehiChemCommun1270(1990) 8 (17.1g0.1mol)(10.44g0.06mol) 336(Aliquat 3361.280.03mol) 5rain 120'(2 20h 50mL 1 21 (7.54g61) 148149 9 2min 4h
18 29 60 A.RSardarianBKaboudin SynthCommun27543(1997) 10 323 () (100%) 1841 100 % 1 2 2 CH 3 CH 2 CH 2 X HX HX CH 3 CH=CH 2 CH 3 CHCH 3 X 1 100%1 98%
18 30 100% 3 CH 3 CH=CH 2 + H2 Ni CH 3 CH 2 CH 3 4 Michael(): 100 A 1842 B C 100 C 6 H 5 CH=CHCC 6 H 5 + CH 2 (CC 2 H 5 ) 2 C 6 H 5 CHCH 2 CC 6 H 5 98% CH(CC 2 H 5 ) 2 ()( ) 1843 100% 99% CN CH 3 CCH HCN CH 3 H 3 CH 3 CCH 3 CH 2 =CCCH 3 H 2 S 4 H CH3 α 47 CH 3 CH 3 C CH + C + CH 3 H CH 2 = CCCH 3 100 Pd
18 31 1844 CH 2 CH + CH CH Br AlCl3 3 3 2 + HBr 0~25 76% AlCl3 CH 2 CH + CH 3 2 =CH 2 1845 1846 1 2 DielsAlder 3 (1) ene (2) (3) 1,3 (4) (+) (): 0~25 H 3 C H C= H H 180 60% H 3 C H H H ene 100
18 32 1Claisen CH 2 CH = CH 2 H Claisen CH 2 CH = CH 2 ([3,3]) AB 100 2Cope ([3,3]) H KH, THF 100 CH 3 C H + H CH 2 C H H, H 2 CH 3 H CH CH 2 C H 100 CH + CH CH 3 H CH= CHCH 1851
18 33 P654 6 hυ H 3 C H H CH 3 H 3 C CH 3 1852 300MHz300GHz 12.21 1 1 1 99 l0 25 199 1022j ]
18 34
18 35 HMPA 95% 1854 EColi
18 36 1855 ( 60%) P657 1856 (Phase transfer) PT 20 70 20 70 DMSDMF HMPA
18 37 CNRX 1857 2 + + + + Na CN RCN + Q X Na X + Q CN + Q + X RX Q + CN + biocatalysis biotransformation 1
18 38 1 2 1 3 2 4