МСОС Лекции с поиском и закладками
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XMMMlfeCKMe ceoMcrea l,3-AMKap6oHMnbHblX coeAMHeHMM
Aei1creHe aMMHaKa Ha EAA npHBOAHT K 06pa3oeaHHto eHaMHHa
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0 0 |
NH3 |
NH2 |
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OEt H2o · Et |
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3.5. KOHAeHCaU,HA KHeBeHarenA EAA e npHCY,-CTBHH aMMHaKa npHBOAHT K |
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npOH3BOAHblM AerHApOnHPHAMHa (peaKL\H.A raH'4a) |
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Et |
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1/2 )l_ |
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EAA H |
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0 |
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NH3/EtOH/il |
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EtO |
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PeaKU,MIO raH'4a WMpOKO npHMeH.AIOT A/IA CMHTe3a AHn1APOnHPHAHHOB (AMnHHbl)
o o l/2 :
OMe NH3'EtOHfa
Meo
OMe |
R=N02 (H111¢eA111m1H): |
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R=OCHF |
2 |
(PHOAHmtH). |
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9
XMMM eCKMe CBOMCTBa 1,3-AHKap6oHMnbHblX COeAMHe MH
3.6. KOHAeHca411u1 1,3-AMKap60Hl1JlbHblX COeAMHeHHM C TpMaJ1KMJ10PTO OpM11aTaMM
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0 |
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Et |
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EtO)lJOEt Ac2O/ZnCl2/6 |
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I |
y |
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O |
O |
CH(OEth |
► EtO |
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O |
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= EtO |
OEt |
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OEt |
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H |
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3Ta peaKL4HA WIIIPOKO HCOOJlb3YeTCA 8 CMHTe3e reTepo4MKJl08 (HanpHMep, XHHOJIOHOB)
F |
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O |
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Cl |
)CC |
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I |
Cl |
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0
Cl |
DEM |
F |
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Mg(OEt=Cl
JIit F |
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[>--NH |
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Et |
JIit |
2 F |
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Cl |
F |
PhMe/T |
Cl |
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► |
OH |
HN |
.NH |
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Cl |
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OMSO |
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Et |
TsOH |
0 |
CH(OEt)J |
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OEt |
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0 |
OEt |
• |
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NaH |
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OMF |
Cl |
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0 |
F
.l l(Hnpoq>JlOKCaUHI-I
OEt NaOH
JIit
XMMMt.1ecKMe csoHcrsa l,3-AHKap6oHM/lbHblX coeAHHeHHM
4. 1,3-A1-1Kap60HM/lbHb1e coeAHHeHMR KaK Nu B npHcoeAMHeHMH M1-1xa311R
BO |
O |
o 0 |
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l |
k |
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EtO |
OEt |
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EIEtO |
NaOEt |
EtO |
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N |
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NaOEt\;: 0
EtO
0
00
EIO½Et
CNH2
HN-X
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0 |
E |
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I |
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----...11 |
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u |
n |
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-_.-1:► |
N |
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---1►► |
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► A |
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-EtQH |
l. |
N |
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H |
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H |
0 |
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R=X=H(CepoToH1-1H); |
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R=Me,X=H(MeKcaMl-lH}; |
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R=Me,X=Ac(MenaTOHl-1H). |
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1
XMMM eCKMe CBOMCTBa 1,3-AMKap60HM/lbHblX COeAMHeHMM
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5. 1,3-AHKap6oHH/1bHble COeAHHeHHfl e CHHTe3e aMHHOKHC/IOT |
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5.1. CMHTe3 -aMMHOKMCJlOTno peaK4MM POAMOHOBa |
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NH3 |
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0 |
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R)lH |
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HOYOH |
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HO OH |
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NH3/EIO: |
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H |
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O |
0 |
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RJlH |
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0 |
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1.HBr/AcOHfA |
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1.ICIIHCl/o |
0 |
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HO H |
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OH |
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• |
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2.NaOAc► |
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NH /AcOH/ |
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2. NaOAc |
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HO |
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HO |
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-CO2 |
Meo |
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3 |
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6era31.1H |
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OEM
------------0--------------------
s.2. CMHTe3 a.-aMMHOKMCnOT M3
_N_aNo --► |
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1 1 Et] |
Zn "" |
E |
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fEt |
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O |
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r |
"' |
O |
Ac20 |
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AcOH |
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,,,.. |
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a4eTaMMHOManOHOBOro 3<l>Mpa
t |
VOEt |
R-X"" |
0 |
0 |
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O |
HN |
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E101/oe, |
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'Ac |
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Et |
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NaO |
R HN-Ac |
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XMMH eCKMe CBOHCTBa 1,3-AHKap60HHnbHblX COeAHHeHH
npMMeHeHMe a4eraMMHOManOHOBOro 3<l>Mpa AJUI CMHTe3a npMPOAHblX AK
BnO
NaOH/PhMe/6
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BnO |
-Ac-(R)-Bot-OH |
N |
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H-(S)-Bot-OHH |
Et
1.NaOH/H20 2. H+ H / 20h\
-CO2 0
0
OH
BnO
N
H
Ac R,S)-Bot-OH
OH
0KC1,11Tp111maH H-(5-0H)-Trp OH
►
5.3. CHHTe3 cx.-aMMHOKMcnor M3 DEM c nOMOU4btO neperpynnMpOBKM Kyp4Myca
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0 |
Cl |
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OEt |
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DEM |
- |
1.NaOH(eq.) |
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► |
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NaOEt |
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OH
1.0PP•V
2. BnOH
-N;i
OEt
NEt3 /T►
Cbz-(R,S)-Nal-OEt
1
XMMM'-leCKHe csoMcrsa 1,3-AHKap6oHM/1bHblX coeAMHeHHM
6. feTepo41111<1u13a4111111 Ha OCHOBe 1,3-AHKap6oHH/lbHble CO HHeHHH
6.1. CMHTe3 npOM3BOAHblX mtpMMMAMHa KOHAeHca MeH C 1,3-6HHYK/leo<1>1,1naMM
ECA
Menuiypat.t1i1n
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0 |
3 •/ |
1 |
II |
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NA.N |
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H |
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H |
NaOEt/T |
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o
'Nl \ |
OE |
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o |
-0--N |
N |
I |
H2 |
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N1 |
X |
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HN |
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I\ |
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H2 |
/"II-.3N |
2 |
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...H, |
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0 |
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NaOEt/T |
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X |
I |
N/ |
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H |
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X=O 5apforrypoeas:i K-Ta X=S T11106ap6111rypoeas:i K-Ta
CMHTe3 6ap6HT'{paTOB |
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I> |
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NJLNH |
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0 |
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EtBr |
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y0 0 |
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0 0 H |
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t-fN |
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-.....,__ |
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DEM |
..., |
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EtBr EtO |
OEt |
2 |
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2 |
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N |
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EtO |
OEt |
NaOEt/ |
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NaOEt/T•o \ |
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NaOEt/ |
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S |
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H |
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AmBr |
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O O |
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8ep0HaJ1 (1906) |
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N |
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N)lN |
2 |
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0 |
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aOEt/ EtO |
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OEt H2 |
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- |
HN |
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- |
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NaOEt/T |
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A |
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S |
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N |
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1 |
H |
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T111oneHTaHan |
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XMMMlleCKMe CBOMCTBa l,3-AMKap6oHMnbHblX COeAMHeHMM
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MeTaMl-13011 HaTpl-1 |
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'""/'-.... .,OH |
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Ph\ |
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IPh |
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N |
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HO "-"" |
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EtO |
OEt |
1.PhNH-NHPh |
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-N |
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DEM |
---ti► EtO |
0 |
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o ... |
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... |
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... |
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NaOEt |
TsOH/PhH/ |
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2. Ts0H/Me2 |
CO |
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XvtMM ecK11e ceoMcrea 1,3-AMKap6oHMnbHblX coeAMHeHMM
AIIKOKCMMeTM/IMAeH08ble npOM380AHble 8 CMHTe3e a3011oe
ECA
CH(OEth |
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.. |
Ac |
O/ZnCli/6 |
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2 |
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0 |
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4, |
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EtO |
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N |
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I |
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OEt
=
0 |
N |
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y::::-,, |
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EtO |
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H 0 |
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N Hi-N
EtOH
0 NH2
H |
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2 |
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.. EtO |
H |
N |
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N |
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/ |
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1
XHMH\feCKHe ceoHcTea 1,3-AHKap6oHHnbHblX coeAHHeHHH
6.3. CMHTe3 HHAOnoe H3 npoM3BOAHblX EAA (peaK4MH ffnna-Kn1o1HreMaHa/4>1o1wepa) |
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ONHQ |
0 |
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1 |
. Mel |
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O |
0 |
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" |
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y NaOH |
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EAA |
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► |
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Jlo |
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0 |
{._;6- OEt 2. |
H2O |
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OEt ◄ |
Jlo |
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PhH/6 |
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o |
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PhN:N Cl |
[ |
O |
O |
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l |
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NaOH \ |
// |
HCI |
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0 |
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-AcONa► |
JLJL |
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•/;\ |
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=.. |
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'OEt |
-AcONa N |
OEt AcOH |
O |
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:= A |
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► |
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Ph-N N |
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Ph/ H |
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Et |
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peaK1.4MSl flna-KnMHreMaHa |
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peaK1.4M 4>Mwepa |
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o
EtO
O HN Meo
1
-EtOHKOH►
K
o O
0N H
Meo |
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l) |
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-CO2 |
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0I |
MeO |
U |
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N_N► |
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I |
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NH2 |
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y:H
I |
O |
N.,...N |
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H |
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NH 1. NaOH/H2O►Meo |
N |
N |
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H |
H |
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MeKcaM111H |
MenaTOHIIIH |
H |
► o |
+ |
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EtOH |
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HN |
_// |
"\. |
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XMMM'feCKHe csoi1crsa l,3-AHKap6oHMnbHblX coeAMHeHHM
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1. NaN02 /AcOH |
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Ot-Bu |
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1)2. |
Zn/AcOH► |
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0 |
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F |
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I |
o |
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o |
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O |
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H |
F |
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v)=N |
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H |
Pip*AcOH/T |
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I |
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1.TFA/OCM
2.POCl3/0MF Ot-Bu 0
1. NaOH/H20
2. EDC/HOBt
---- F
J.H2 NEl2
1