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I.

1
,
.
, ,
, .
D- (Cyc), 3H6N2O2, E1,
B (40.43%
7.93% ) A (15.72% N, 35.91% O ).

(54.5% ).
E1 O
R
O2, H2O O2, H2O OH
A C B
-NH3 -NH3 NH2
1. . ,
S- .
2. 6 .
, 1.
, Cyc N , , = NO .
3. , .
4. Cyc, , O
( N).
, , , Cyc .
Cyc A.
5. Cyc,
.
B,
. (7H14N2O4)
D, F (49.28%
C ). , D
-, : 4, 5, N 1.
6. D F .

-1-
,
.
7. D F ,
,
.

X, 6H7N3O.
O
N
OH
X , .
X W1W2
:
X + W1W2 Y + W2H (1); Y + H2O 6H5NO2 + Z (2);
Z + W1W2 4H8N2O2 + W2H (3).
8. X Z, ,
4H8N2O2 N.

2
.

,
Na+-.
,
, .
,
-, :
K2Cr2O7/H+ EtOH/H+ Fe/HCl HO(CH2)2NEt2/EtO-
A B C

1. , ,
.
2. .
.
H
N
N
O

-2-
3. ,
.
() (-) , ,
C7H7NO2, .

P450, .
H
P450 P450 P450 N
L1 [L2] L3 NH2
-N -N O
4. , N
, L2 L1 (67.16% , 12.78% ), -
,
, .
5.
.
, .
6. (pKa = 7.8
8.9 ).
( 7.4).
Na+-:



, Na-



.
7. , ,
, ,
,
( , ).
8.
.

-3-
3

. ,
A
- -,
, .
(CH2)18
O HN
O * O
O N HN O
N O HN NH O
* R *
O O NH N
A O *
NH O
(CH2)18 C
1. , A (R ).
:
.

, .

B1 B2. B1 , (60.43% C,
34.50% O, 5.07% H , - ,
500 /). B2 (36.09% C,
29.59% O, 4.67% H, 29.65% S , 6 SH- ).

.
2. B1 B2,
( ).
3. B2 .
4. ( /) B1 B2?
B1 : B2 .
5. B1 (3.0% ) B2
. ,
, -
( B1 B2 1.25 /3, 1.1 /3).

-4-
C
, .

, .
6. , C
? ?
7.
1 3 C ( 0.9 /3,
20 /)?
1 , (,
)?

-5-
II.
1

, . p
T T0
p0 = 1 . = 101325 = 760 . . :
p H 1 1
ln =- - ,
p0 R T T0
R = 8.31 /K; 0 [K].
1. , 1 . .

.
2. ( )
50-100.
.
a) , 17,
.
b) ,
10 (p = 0.1p0):
( 189C 1 ).
c) 150
1:1. ,
. .

.
, .
3. CaCl2.
a) ,
; .
b) , .
4.
t = 1C, ,

-6-
- = 2. , t = 8
60 .
5.
(),
100 .
, 112.
a) .
- 30 .
b) 104 , 20 .
- .
: ()
H(H2O) = 44.01 /; S
O
H() = 57.28 /.
t1 -t 2
v1
- : = 10 , v1 v2
v2
t1 t2, .

2
Au, Pd Pt, Basolo F.
Badley W. , ,
k = kH2O + kXCX.
M(dien)Cln+ + Br M(dien)Brn+ + Cl (1)
(dien (-); = Au, Pd, Pt):
(Br), / 2102 5102 8102
kAu 3.5 8.0 12.5
kPd103 1.0 1.0 1.0
kPt104 1.8 3.3 4.8
1. kH2O kBr Au, Pd, Pt.
2. (, %) kH2O k = f(CBr).

-7-
3. H2O
M(Et4dien)Cln+ + Br M(Et4dien)Brn+ + Cl (2)
(Et4dien (-)), k = k H 2O , :

ACln+ + 2H2O ACl(H2O)n+


2 (k1, k1);

ACl(H2O)n+ (n+1)+
2 A(H2O) 2 + Cl (k2);
A(H2O)(n+1)+
2 + Br ABrn+ + Cl + 2H2O (k3), A M(Et4dien).
4. (1),
: (2), :
(n1)+
ACl(H2O)n+
2 + Br AClBr(H2O) + H2 O (k4);
AClBr(H2O)(n1)+ ABrn+ + Cl + H2O (k5), A M(dien).
(2).
5. . ,
(): 9.23 (Au), 8.34 (Pd), 8.90 (Pt).
6. Au Pt,
#
: Pt# = 58, Au #
= 55 /; SPt# = 96, SAu = 17 /K.
G# 298K.
7. Au Pt
, Au

3

. ,
. ,
+-.
,
.
-8-
Na K F Cl
(IE), 5.14 4.34 17.4 13.0
(), 0.54 0.47 3.45 3.61
: 1 = 1.6010-19 ;
Ek = kz1z2/r12, k = 2.3010-28 , zi , r12
; + IE = + + -; + - = - + EA.
1. +-
,
.
2. ,
+-,
.
3. NaCl 251 .
(/) ?
4. NaCl 626 /
. .
5. CaCl2.
, Ca2+ Cl
-9.79 . : IE1 (Ca) = 6.15 , IE2 (Ca) = 11.92 .
6.
. , CaF 820 /.
CaF2,
CaF2 1221 /
, Ca() F() 178 79 /
.

-9-
III.
1
()
150 , II III
, .
1) 5% NaOH
O O 1) II
2) H3O+
I
O 2) CH3I 1) NaOH (.)
III
2) H3O+
1. HX,
NaX. , Na
II III.
E 3 PhOH C2H5OH H2
10.7 4.8 10.0 15.9 36
2. I III, 1 II III.
II 1.05 .. (3, ), 2.14 .. (3, ), 2.47 .. (2, );
III 1.04 .. (3, ), 2.38 .. (2, ), 11 .. (1, . ).

I, II III. ,
, :
1)
EAA [X] 1) 5% NaOH B
2) +
2) H3O , t
O HBr
1) NaOH (.) A
HBr (.)
C6H8 O 3
D 2) H3O+ t C
3. A D , ,
1 : 2.08 .. (3, ),
2.11 .. (2, ), 2.50 .. (2, ), 3.35 .. (2, ).

- (IV) ( ),
(V, ) :
O
1) 1) 5% NaOH 1) 1) 1) 5% NaOH
EAA E F G H
Br 2) H3O+ 2) (CH3O)2CO 2) O 2) H3O+
2)
IV
Br
1) (1 ) 1) 5% NaOH H2
K L M V [(1R,2R)-3--2-((Z)--2--1-)-
2) Br 2) H3O+ Pd/CaCO3
(CH3COO)2Pb ]

- 10 -
4. V, E -
(, ).

2
(I, C10H16O) ,
, .
Cinnamomum camphora ( (+)-),
( ()-).
XX
:
CaC2 NaCH(COOEt)2 EtONa 1) KOH / H2O
A B C D E
t EtOH EtOH 2) H3O+ / t 1) Br2 / OH-
C13H22O5 C11H16O4
2) EtOH / H+
1) EtONa 1) X, EtONa O O
F II
G +
Zn/Hg 2) CH 3 I 2) H 3O
C13H18O6 EtO OEt
HCl
O
1) H3O+
OH
Ac2O/t Na/Hg KCN 2) Ca(OH)2 I
HO H J K
III 3) t, -CO2
O C H O
10 16 2 O

1. A , ,
62.07% C, 10.34% H O; O, ,
. D .
6104, 1
( 3:2),
13 .
2. , , .
,
(), .
3. .
(, , , ) I?
I LiAlH4 (IVa)
(IVb) 9:91, LiBH(s-Bu)3 IVa IVb
2:98.
4. IVa IVb.

- 11 -
3
.


,
. ( ) ( ).
,
, . ,
(78886),
:
O MgBr
1) PBr3
1) I I
2) MgBr
A B C D BBr3
C10H12O3 2) H3O
+ 3) H3O+ C24H22O3 CuCl, Pd(0)
R3P CH2Cl2
BBr3 E
H NaOH CH2Cl2 1) NaH, DMF C27H19IO3
C78H88O6
EtOH
Y 2) Br(CH2)10I
X NaH G F
C78H88O6 DMF C78H91O6Br3 CuCl, Pd(0)
R3P

1 (3), (3),
(2) (4).
.
1% KMnO4,
.
1. 10123,
,
(
-, -, - ).
2. , ,
.
3. , ?

- 12 -
IV.
1
-
(10.00 ) 20.00 0.0500 AgNO3,
(III) , ,
0.0500 KSCN.
1. ,
,
5.50 .
: 0.030 , 0.040
0.050 . : a)
; b) KIO3 HNO3
,
. 33
.
; c) ,
; d)
30% , ;
.
2. ?
, .
? (KS = [Ag+][Hal])
: AgCl 1.81010; AgBr 5.31013; AgCN 1.41016;
.
3. (): Ca2+, Hg2+, MnO4, Fe2+,
RSH. ?
, .
4. (Fe3+)
1106.
0.05 -
, . 1, ?
? AgSCN KS = 1.11012.
- 13 -
2

.
:
(Kt+B)org + Anaq = (Kt+An)org + Baq ,
Kt+ (,
(C10H21)4N+), B , An .
.
0.010 HCl ( )
0.050 /
(C10H21)4N+Pic (
2,4,6-).
410 0.400.
A = cl ( --),
, 410(Pic) = 9.20103 11, l
, 1.00 .
1. -
.

Cl
2. - - KPic,

.
, 1.00104 /
[AuCl4] 0.0100 HCl, 0.915.

3. KAuCl
Pic
4
.

4. K Cl AuCl4
Pic K Pic

AuCl4
KCl - (C10H21)4Nl - [AuCl4].
5. 0.050 (C10H21)4NCl,
99.99% 100 .

3

,
()

- 14 -
. Sr, Ba,
Cs, Y, Pb W :
3: F 5: D
6 NaOH (NH4)2CO3
1
, 3: E 4: C
Sr, 0.5 H2SO4 1) Na2CO3,
Ba, Cs, Y, Pb
W, + 25 4
2 2) HCl
1 HNO3 K2CrO4, pH 6
6 NaOH
1
2 5: A 6: B

1. , F.
2. , .
3. .
( ):
238 241
13.2 241
458 237
U 239 240 Pu Am Np
... Pu Pu
240
, Pu,
(-, -, (n, ) ).

PuO2 ,
31 1986 .:
239 240 241
Pu, Pu Pu, Pu
(m1 = 3.0000 ). Pu(IV) (
N--N-),
Pu(IV). m2 3.4010 .
, 1 2011 .
m3 3.4008 .
4. .
5. (. %) Pu 1986 ., ,

. , , 241Pu 240Pu (x
y, ) x = 0.0168y2.
241Am :

N( 241 Am) = N 0 ( 241 Pu)


Pu
Am - Pu
(e - Pu t - Am t
-e ), l ,
: T = ln 2.

- 15 -
V.
1
1823 . NH3
, .
3.90 Cl2 520
4.79 Cln ( 90%), HCl
B. 0.1 (NH4)2CO3
A .
275 290 - D.
, ,
W, . %
-
m A, C D 1000 H2O
N MeCl MeN MeMe
A 65.0 9.33 2.33 2.00 3.24
C 65.0 9.33 2.25 2.07 3.67 = 90%,
D 65.0 9.33 2.32 1.98 3.68
tC = tD tA = 0.9tC.
1969 . . , , Cl, N-7
, .
1. , Cln, A, B, C D. , 4,
B .
2. C, D, ( ).
3. ,
, .
4. ( ).
5. , , ,
(NH4)2CO3. ,
pH ( H2CO3 K1 = 4.3107; K2 = 4.71011, NH3H2O
Kb = 1.8105).
6. , C D
, . ,
.
7.
, = hc / .

- 16 -
2
Y
(). (1.985 )
(2.512 ), 5 25 CCl4
.
4.497 D,
(3.286 33.00 2).
4.942 CuSO45H2O 20 H2O SO2
A(), 67 ().
A() , ,
() .
1. .
2. D (),
fH0(D()) = 105.4 /; S0(D()) = 184.0 /;
fH0(D()) = 102.7 /; S0(D()) = 177.3 /.
3. , D()
D(), D() Y 2.78 , D() 2.62 (2 )
3.51 (4 ).
4. A() ( ).
A() ().

3
, ,
, ,
.
1. KMnO4 H2SO4
, .
.
2. (NH4)6Mo7O24 -
(+4) D,
, 3.57% Mn 56.13% Mo . D

- 17 -
,
2/3. .
D .
3. K2Cr2O7 H2SO4
,
H2CrO6, 1H -
1011 ..
, CrNC5H5O5.
H2CrO6
H2CrO6 CrNC5H5O5.
4. H2CrO6 KOH
, 27.6% Cr,
20.8% K, .
.
.
5. (+6) H2O2
. KOH, B, ,
, 17.5% Cr, 39.5% K .
B .
.
6.
, .
30% , .
, ?
.

- 18 -