Χημεία γ λυκείου θετικής κατ 3 τεύχος

.

3

5

.

5

5.1

7

22

26

5.2

36

41

51

5.3

64

69

79

87

88

96

100

104

113

122

124

129

133

142

152

159

161

173

6

. . 179

. . 183

. . 186

. 191

. 193

. 198

. 205

.

209

211

5.4

221

228

. 252

. 255

. . 259

. . 262

. . 265

. . 272

280

323

324

329

.

7

5.1 H

:

.

I

:

(Lewis)

(

)

.

: :

1. ,

.

.

2.

, spin

.

.

3. , (

) .

8

:

( )

, .

.

2:

( * )

1 s 1 s

( )

:

1.

( ).

2.

(* ).

3.

, .

4.

.

( Hund, Pauli)

-

2,

.

.

9

:

.

, .

,

.

.

() ()

: s-s, s-p p-p

.

.

10

.

.

.

.

: p-p (

).

( ).

. .

.

I Y I I Y E

a) F2: F:

E , 2p

F .

F : 1s2 2s2 2p5

.

11

) 2: :

E , 2py 2pz

.

, , , p

, p-p .

.

) 2: N2

:

p .

, ,

, p , p-p

, :

: 1s2 2s2 2p4

: 1s2 2s2 2p3

12

.

) 2S: 2S

:

E

, o 1s H

3pY 3pZ S

.

I Y E

, Pauli

Hund :

C : 1s2 2s2 2p2

.

13

. ,

p .

( )

: ( ) ,

( ). O

.

:

.

CH4 (sp3 - )

L. Pauling CH4

.

C :

: 1s1

2s 2pz. ' ,

, .

4 .

(CH4) 4 (2s , 2p , 2py , 2pz ) 4 (1s)

4 , 4

C : 1s2 2s2 2p2

C : 1s2 2s1 2p3

2p 2s.

14

C : 1s2 sp3 sp3 sp3 sp3

2s 2p.

4 CH4 .

''(2s , 2p , 2py , 2pz

)

( ), .

2s 2p ,

( ) , sp3

( 3 3 p ):

sp3 .

.

, .

sp3

( ).

.

109, 28. sp3 (

).

.

15

. sp3

(1s1), .

(sp3-s)

:

1) 109, 28 .

2) ( ).

3)

,

sp3 .

s-sp3

sp3-sp3

.

.

CH4

16

C2H4 (sp2 - )

,

CH2 = CH2 > C = C

.

17

.

: sp2-s. C

sp2 - sp2 pz - pz.

:

1) 120 .

2) .

3) .

4) .

sp2 .

> C = C < . .

, BF3

:

1s22s22px12py

2pz ( )

F:

1s22s22px22py

22pz1 (

18

B ,

. BF3

2s 2p. , :

1s22s12px12py

1pz .

2s

2p , sp2(

2 2 p ):

5B _ sp2

sp2 B p F

, :

5.8 sp2

B 2p F.

C2H2 (sp - )

,

CH CH C C .

C :

: 1s1

2s 2pz. ' ,

, :

C : 1s2 2s2 2p2

.

19

2s

2p , sp.

2s 2p

sp

.

. .

HC CH, C (

sp-s), C ( sp-

p) ( p-p), .

:

1) 180 .

2) .

3) .

4) .

sp .

C C .

C : 1s2 2s1 2p3

2p 2s.

2py 2pz C : sp sp

sp .

1s2 .

20

(BeF2 )

. :

Be: 1s22s2

F: 1s22s22px22py

22pz1

Be ,

. BeF2

2s 2p. , :

1s22s12px12py2pz

.

21

, Be

BeF2 , s + p p + p.

BeF2 .

. , Be BeF2 s p Be

sp . sp

Be p F ,

:

5.6 sp Be p F BeF

2.

22

:

Ta C ( ) :

6C : 1s2 2s2 2p2

, C , ,

.

C sp3

109, 28o.

C sp2

120o.

C sp

180o.

To () sp2 ( ),

(Be) sp ( ).

.

.

.

, C,

C .

, C,

C .

1. ,

.CH3CH = CHCH3 .CH3CH2OH . CH3CH = .CH2 = CH-C C H

:

sp3 .

24

2. (,,, ) :

C

H

H

C

H C CH

H

H

H

H

C CH H

a.

C . C

sp2 C sp3 . a,

120o C sp2 .

109,5 C

sp3.

. C sp . 180.

3. C ;

a. C3C CC3

. C3C2C C

. C3C=C2

a. C

, C. C .

. C

, C.

. C sp2

C 120o. C .

)

)

.

25

1. .

1 2 3 4 5 6 7

2 2| ||

OH O

N C CH CH CH CH C H C H

2. :

. CO2 . ||

O

H C H . CH3NH2

3. ,

:

. . 2 2

4. / sp2 :

. C2H4 II. C2H6 III. C3H6

a. . . . . . . .

( Chemistry 2001)

5. . H-CN

. .

( Chemistry 2006)

6. .

2 1 .

( Chemistry 2007)

26

1

1. -

. HC CH .

(2004/. 1)

. p-p .

(2005/. 1)

. s p sp .

(2005/. 1)

. , C sp2sp2

.

(2007/. 1)

. CHCCH3 .

(.2008/. 2)

. ,

.

(.2007/. 1)

. ,

.

(2008/. 1)

. ,

.

(.2008/. 1)

. , C

sp2 sp3.

(.2008/. 1)

.

27

. sp2 .

(.2006/. 1)

. ( )

( ).

(.2003/. 2)

. CH3CH2CN .

(.2000/. 1)

. .

(2006/. 6)

. (CH3CHO) ().

( 2008/.1)

. p-p .

( 2009/. 1)

. 2-, 3 3CH - C C - CH , .

( 2011/. 1)

2. CH CH :

. 1, 4 . 3, 2 . 2, 3 . 2, 2.

(.2004/. 3)

3. CH2 = CH2 C :

. sp - s.

. sp2 - sp2.

. sp2 - sp2 pz pz.

. sp - s pz pz.

(.2004/. 5)

4. sp2-sp2 :

28

. CH4 . CH3-CH3 . CH2 = CH2 . CH CH.

(.2002/. 5)

5. Z=7. (N2) :

. .

. . .

(.2002/. 5)

6. CH2=CH2 C .............

sp2-s. C .............

............. ............ ............... .

(.2002/. 5)

7. C CH :

. 2 3 . . 4 1 . . 1 4 . . 3 2 .

(..2003/. 5)

8. CH2=CH-Cl, ()

:

. sp3 sp3 . sp sp . sp2 sp . sp2 sp2 .

(.2003/. 2)

9. O () :

. s s . sp3 p . p p . sp2 s.

(.2004/. 5)

10. CH2=CH-CH=CH2 :

. 8 3 . . 9 2 . . 10 1 . . 8 2 .

.

29

(2005/M. 5)

11. CH3CH2CH2CH=O :

.10 3 . . 9 4 . . 13 . . 12 1 .

(E.E.2005/M. 4)

12. ,

.

1. CH3C . 1-

2. CH3CHO .

3. CH3CH2CH2OH .

4. CH3COONa .

5. CH3COOCH2CH3 .

.

(..2005/. 4)

13. ;

. CH2=CHCH=CH2. . CH3CH2CH3. . CH3CH=CH2. . CH CCH3.

(2007/. 5)

14. (CH2=C2) : . sp2s

. sp2 px . pzpz . sp2sp2 .

(.2007/. 5)

15. sp2 ;

. CH3-CH3 . CH2=CH2 . HCCH . CH4

30

(.2005/. 5)

16. CH3-CC-CH3:

. 3, 1 . 8, 1 . 9, 2 . 3, 2.

(2000/. 5)

17. CH CCH=CH2 :

. 6 2 . . 6 3 . . 7 2 . . 7 3 .

(2008/. 5)

18. CH2=C=CH2 :

. 4 4 . 2 6 . 6 2 . 5 3.

(.2008/. 5)

19. CH3CCH :

. 2 2 . . 7 1 .

. 5 2 . . 6 2 .

(.2006/. 5)

20. :

. s-s .

. s-p .

. p-p .

. p-p ( ).

(.2003/. 2)

21. 1 2 3 4 5 3CH C - C = CH - CH .

.

31

2C 3C :

. sp sp3 . . sp sp2 .

. sp3 sp2 . . sp sp .

(2009/. 5)

22. CH2=CH-CH2-Br :

. 9 . 5 4

. 7 2 . 8 1 .

(. 2009/. 5)

23. 3 3CH - C C - CH :

. 3, 1 . 8, 1 . 9, 2 . 3, 2.

(2000/. 5)

24. sp-sp :

. 2 2CH = CH . CH CH . 2CH = CHCl . 3 3CH - CH .

(. 2009/. 5)

25. ;

. CCl4 . C2H4 . CH3CHO . C2H2.

(O 2004/.1)

26. F3 :

. p-sp . p-sp2 . p-sp3 . s-sp2.

: 9F. 5B

( 2008/.4)

27. 2CH = CH - C CH ;

. . . . .

32

(. 2009/. 5)

28. 2 , C

:

. sp2 sp2 sp sp. . sp sp sp3 sp3.

. sp sp sp2 sp2. . sp2 sp2 sp3 sp3.

( 2010/. 5)

29. sp2-sp2 :

. 3 3CH - CH . . 2 2CH = CH . . CH CH . . 4CH .

(. 2010/. 5)

30. :

. sp2 sp2 p p . . sp2 sp3 p p .

. sp sp p p . . sp3 sp3 p p .

(2010/. 5)

31. C H :

. sp-s . . sp-sp .

. sp2-s . . sp3-s .

(. 2010/. 5)

32. 3CH C - CH ;

. 2 6 . . 4 3 . . 6 2 . . 7 1 .

(. 2010/. 5)

33. 2 3 2HC C - CH = CH

:

.

33

. sp3 sp3 . sp sp2 . sp2 sp3 . sp3 sp.

(2011/. 5)

34. sp :

. BeF2 . BF3 . CH4 . C2H4.

(. 2011/. 5)

35. 2 2CH C CH , :

. () p

. () p () 3 2sp sp

. () p () 2 2sp sp

. () p () 2sp sp

( 2012/. 5)

36. 3 3CH C C CH CH CH :

. 9 4 . 5 2 . 13 3 . 11 5

(2012/. 5)

37.

(. 2012/. 3)

2

1. :

. CH3CH2C . CH2 = CH2 . CH CH.

(.2002/. 6)

34

2. 1C2=2C-3C 4C 1

4, .

. () () ;

. ;

. .

(2002/. 3+4+6)

3. 6C 9F.

. ;

.

. Lewis 4CF ,

.

. ( ) 4CF

.

(.2004/. 1+2+3+3)

4. 6C 1H .

.

, .

. 4CH Lewis.

. 4CH ,

.

(.2007/. 2+2+4)

5. 2-, .

.

( 2003/. 5)

6. : 6C, 8O, 19K.

.

35

. 8 82-.

.

. Lewis K2CO3 CO2.

. CO2 ,

.

( 2011/. 0,5+1,5+2+3)

7. :

C .

(. 2012/. 1+2)

36

5.2

.

. : , , .

| | | | | .. C C , C C = O , C C N | | | |

. :

.

| | | .. C = C , C C , C C C | | |

.

. :

.. | | |C C C| | |

, | | |C C C| | |

C|

. : .

C C .. | | C C

, C,

, .

|| C / \

| | C C

| | C C \ / O

.

37

C C | |

. .

..:

(CH4, C2H6, ..).

.

:

. C

.

.

.

( CH2 ).

. () .

. .

(H/C)

C ()

H/C

CH2 + 2

RH 1

H/C

C = C

| |

CH2 2

H/C

C C CH2 - 2 2

H/C CH2 2 3

38

: R CH2+1, . = 0

. ( CH2+1)

(CH2+2) .

.

39

() (.)

|

C OH

|

CH2+1OH CH2+2O 1

ROH

| |

C O C

| |

CH2+1OCH2+1 CH2+2O 1, 1

ROR 2

+ =

C H CH = O CHO

||

O

CH2+1CHO CH2O 0

RCHO 1

| | |

C C C

| || |

CH2+1COCH2+1 CH2O 1, 1

RCOR 3

+ =

C OH COOH

||

O

CH2+1CO CH2O2 0

RCOOH 1

+ 1 =

| |

C O C COOC

|| | |

CH2+1COOCH2+1 CH2O2 0, 1

RCOOR 2

+ + 1=

C N CN

CH2+1CN CH2-1 0

RCN 1

+ 1=

|

C NH2

|

CH2+1NH2 CH2+3N 1

RNH2

X: Cl, Br, I CH2+1X (X=Cl, Br, I) 1

RX

:

) .

.

) , | |C

O

40

,

.

.

41

I.U.P.A.C

, :

1

C.

2

C.

3

.

(1 C) -

(2 C) -

(3 C) -

(4 C) -

(5 C) -

(6 C) -

(7 C)

...

( ) - -

(1 ) - -

(1 ) - -

(2 ) - -

(3 ) - -

()

()

()

()

( )

()

42

1 3 .

:

CH2 CH2 CH2 CH3

4C

CH2=CH2

2C

CH3 C CH

3C

CH3 CH2 OH

2C

H C OH HCOOH || O

-

1C

:

C, , 2 .

C 2 .

CH3 CH2 CH ||

3C

CH3 C CH3 ||

44

sec (secondary = ) C, C

C.

tert (tertiary = ) C,

C.

(RX)

RX,

.

:

CH3CH2 Cl

CH3Br

, , ( ) ,

, .

:

CH3CH2 Cl

CH3Br

(RNH2)

RNH2 , , :

RNH2 - -

CH3CH2NH2

(ROR )

ROR , ,

.

.

45

:

CH3 O CH2CH2

CH3 O CH3

(RCOOR)

RCOOR,

(RCOO), (R ) .

RCOO R

:

CH3COO CH3 HCOO CH2CH2CH3

(RCOO : Na )

RCOOM ,

.

:

CH3COONa

HCOOK

1. .

C .

46

i. CH3CH2CH CH3 iii. CH3CH2CH CH2CH3 | | CH2CH3 CH2CH2OH

ii. CH3CH2CH2C CH3 iv. CH2CH2CH2CH2C CH3 || | || CH2 OH CH2

2.

,

. ,

.

,

.

,

. ,

.

COOH

COOR

CN

CHO

\ /C C C/ || \

O

OH

NH2

OR

C C

> C = C <

| | C C | |

.

47

X

R

:

1 2 3 4

i. CH2 = CH CH2 CH3

7 6 5 4 3 2 1

ii. CH3 CH2 CH = CH CH2 CH2 CH2OH

1 2 3 4 5 6 7

CH3 CH2 CH = CH CH2 CH2 CH2OH (

) .

CH3 CH3 | | iii. CH3 CH2 CH CH2 CH2 CH3 CH3 CH2 CH CH2 CH2 CH3 1 2 3 4 5 6 6 5 4 3 2 1

6 5 4 3 2 1 1 2 3 4 5 6 iv. CH2 CH2 CH2 CH2 C CH3 CH2 CH2 CH2 CH2 C CH3 | || | || OH O OH O

| | |C C C| || |

O

( ).

3. ( )

. C

C

.

:

1 2 3 4 5

i. CH3 CH = CH CH2 CH3 2 3

4 3 2 1

ii. CH3 CH2 CH2 CH2 1

48

1 2 3 4 5 iii. CH3 CH CH2 CH2 CH3 2 | 1 2 3 4

iv. C C CH2 CH3 1

4. , : )

)

, ().

:

4 3 2 1

i. CH3 CH = CH C 2

4 3 2 1

ii. CH3 CH = CH CH2 2 1

6 5 4 3 2 1 iii. CH2 = CH CH2 C CH2 CH3 5 3 || 5 4 3 2 1

iv. CH2 = CH CH2 CH2 CHO 4

: COOH, CN, CHO,

, .

5. ,

.

.

:

4 3 2 1

i. CH3 CH CH2 C 3

|

.

49

6 5 4 3 2 1

ii. CH3 CH CH2 CH2 C CH3 5 2

| ||

OH O

5 4 3 2 1 iii. CH2 = CH CH CH2 CH2 OH 3 4 1 | Cl 5 4 3 2 1 iv. CH3 CH CH2 CH CHO 2 4 | | OCH3 OH

6.

C

.

:

5 4 3 2 1

i. CH3 CH2 CH CH2 CH2 3 1

|

CH3 CH3 |

ii. CH3 CH2 CH CH2 CH CH2 COOH 3 5

7 6 | 5 4 3 2 1

CH2CH3

1 2 3 4 5 iii. CH2 = CH CH CH2 CH3 3 1 | C3 6 5 4 3 2 1 iv. CH3 C = CH CH2 C CH3 5 4 2 | || CH3 O

: ,

, ,

. , , .

.

51

: ,

.

: :

i.

ii.

:

.

: :

i.

ii.

iii.

: .

:

i. 4 C :

C C C C , C C C | C ii. 5 C :

C | C C C C C , C C C C , C C C | | C C

:

.

52

:

i. C C C = C , C C = C C

ii. C C C , C C C |

: .

:

.. .. ..

CvH2v-2 C3H4 CH3 C CH

C3H4 CH2 = C = CH2

CvH2v+2O C2H6O CH3 CH2 OH

C2H6O CH3 O CH3

CvH2vO

C3H6O CH3 CH2 CH || O

C3H6O CH3 C CH3 || O

CvH2vO2 C2H4O2 CH3 COOH

C2H4O2 HCOO CH3

:

.

:

1. C5H12;

CvH2v+2. .

5 :

i. C C C C C.

.

55

: .

( C ,

, 6 .)

C5H8 :

CH CCH2CH2CH3 1

CH3C CCH2CH3 2

CH CCHCH3 | CH3 ( .)

5 :

C |

. C C C C C . C C C C . C C C

| | C C

: i. C = C = C C C, ii. C = C C = C C,

iii. C = C C C = C, iv. C C = C = C C.

( C C = C C = C ii C C C = C = C i.)

: i. C = C = C C, ii. C = C C = C . | | C C ( C = C C C ii.) || C

: .

(

6 .)

C5H8 :

CH2 = C = CH CH2 CH3 1,2

CH2 = CH CH = CH CH3 1,3

CH2 = CH CH2 CH = CH2 1,4

56

CH3 CH = C = CH CH3 2,3

CH2 = C = CCH3

| CH3

1,2

CH2 = CH C = CH2 | CH3

1,3

4. C5H10O;

CH2O , ,

.

.

5 :

C | . C C C C C . C C C C . C C C | | C C || , C , .

|| : C C C C C .

( , .)

: i. C C C C , ii. C C C C .

| || || |

C C ( C C C C i.) | C = C | : C C C | || C ( C .)

.

57

C5H10O :

CH3 CH2 CH2 CH2 CH || O

CH3 CH2 CH CH | || CH3 O

2

HCCH2 CHCH3 || | CH3

3

CH3 | CH3 C CH | || CH3 O

.

5 :

. C C C C C . C C C C|C

.

C|

C C C|C

, | |C C C| || |

O

,

.

: i. C C C C C,ii. C C C C C. || || ( 2 4 ).

: C C C C || | C : .

( 5 .)

58

C5H10O :

CH3CCH2CH2CH3 2 ||

CH3CH2CCH2CH3 3 || CH3 C C - CH3 || | CH3

;

:

1| 2| . C C | | 2 .

. 1

2 .

. 1

2 .

. ,

1 2.

. i. ,

1 2. ii.

, 1

2.

5. C5H12O;

CH2+2O.

.

.

61

CH3CH2CH2CH2CH3 1 CH3CH2CHCH3 2 | CH3 6.

C5H10O2;

CH2O2 , ,

,

.

.

5 :

C | . C C C C C, . C C C C, . C C C | | C C

: C C C C C . || ( - C

.)

: i. C C C C , ii. HO C C C C. | || || | C O C C | : i. C C C , | || C C5102 :

CH3CH2CH2CH2C || CH3 CH2 CH C 2 | || CH3

62

CH3CHCH2C 3 | || CH3 CH3 | CH3 C C | || CH3

1 2

||

O

C C O C 1C C 2C

. 1C 2C

. C

1C C 2C.

1C.

2 2 2 3||

O

H C O CH CH CH CH

2 3|| |

3O CH

H C O CH CH CH 2-

2 3|| |

3O CH

H C O CH CH CH 1-

3 2 2 3||

O

CH C O CH CH CH

3 3|| |

3O CH

CH C O CH CH

3 2 2 3||

O

CH CH C O CH CH

3 2 2 3||

O

CH CH CH C O CH

3|

3 3||

CH

O

CH CH C O CH

7. C5H11Cl;

64

5.3

:

, , , , -

- .

.

: (-C=C-),

(-C C-), ( C=O , ), (-C N).

..

( < 0).

1.

: A B

C = C + AB - C C -

,

C .

. .

CH3CH=CH2 + H2 Ni / Pd/ Pt CH3CH2 CH3

. 2: Cl2 , Br2 , I2 CCl4 CH3CH=CH2 + Br2 CH3CH CH2 Br Br

T Br2 CCl4 .

Br2 , . Br2

. , Br2

, Br2

.

.

65

. : HI , HBr, HCl CH3CH=CH2 + HCl CH3CH-CH3 ( arkovnikov) Cl

H arkovnikov:

( +)

. C

( C ).

CH3CH2CH2Cl.

: HI > HBr > HCl

. H2O: + -

H2SO4

CH3CH=CH2 + H2O CH3CHCH3 OH

H H2O arkovnikov. :

+

, :

CH2=CH2 + H2O CH3CH2OH

2.

: +AB -C C - + AB - C = C - - C C

: 2,r2,Cl2,HCl,HBr,HI

.

. ( ,, ,

a) 1 .

Markovnikov.

66

a. .

Ni, Pt, Pd + H2 CH3C CH + H2 CH3CH=CH2 CH3CH2CH3 Ni, Pt, Pd

Lindlar ( d / CaCO3 ) 1 .

. 2: Cl2 , Br2 , I2 CCl4 + Br2

CH3C CH + Br2 CH3C Br =CHBr CH3CBr -CHBr CCl4 Br Br

( ) Br2 ,CCl4.

. : HI , HBr, HCl

H arkovnikov.

Cl

+ HCl CH3C CH + HCl CH3C CH2 CH3CCH3 Cl Cl

( arkovnikov)

. .

g,HgSO4 CH3C CH + 2 CH3C= CH2 CH3CCH3 H2SO4 OH O

,

.

( )

. H H2O arkovnikov OH

. :

+

:

CH CH + H2O CH3CH=O

.

67

3. (C N)

2 2.

CH3C N + 2H2 Ni,Pt,Pd CH3CH2NH2 (1o )

+

CH3C N + 2 2 CH3COOH + NH3

OH-

4. /

:

R1 R1 : 2, CN, RMgX ( Grignard)

C+ = O- + A+B- R2C+ O-A+

R2 B-

C+ = O- . +

-

. [H+ CN- , R-(MgX)+ ]

arkovnikov

.

C sp2 sp3.

, , .

R C=O

.

R CH2=O > RCH=O > R2C=O > PhCH=O > PhC=O > Ph2C=O

R : Ph : -C6H5

68

a. 2

CH3CH=O + H2 CH3CH2OH

: + 2 i,Pt,Pd

CH3CCH3 + H2 CH3CHCH3

O OH : + 2

i,Pt,Pd

M .

. HCN ( )

CH3 C+=O- + H+ CN- CH3CHCN H2SO4 CH3-CH-COOH + NH3

OH +2 H2O OH

2 2

( )

. Grignard .

Franois Grignard RMgX

Grignard .

(> C = O) :

R1 R1 R1

C+ = O- + R-(MgX)+ R2C

+ O- MgX R2C+ OH + Mg(OH)X

+ H2O R2 R

- R

-

( ).

. ,

() RMgX .

+ H2O

CH2=O + RMgX RCH2OMgX R-CH2OH + Mg(OH)X

(RCH=O) . + H2O

.

69

CH3CH=O + CH3MgX CH3CHOgX CH3CHOH + Mg(OH)X CH3 CH3

.

CH3 + H2O CH3

CH3CCH3 + CH3CH2MgX CH3CCH2CH3 CH3CCH2CH3 + Mg(OH)X O OMgX OH

CH3OH Grignard.

Grignard

Grignard Mg RX

() .

RX + Mg RMgX

RMgX .

RMgX + H2O RH + Mg(OH)X

1. 2 ;

;

. . 2-

. C3C=C2 + 2 CH3CHCH3 2- ( )

OH

C3C=C2 + 2 CH3CH2CH2 1- ( )

Markovnikov 2- .

. C3C=CC3 + 2 CH3CHCH2CH3 2-

OH

2-, , .

70

2. Grignard

:

a. 2--2- . 1- . 2-

Grignard , :

i. (-OH).

ii. 0 ,

.

. C3

C3-C2 CC3 OH

-OH, (-C3,

C3C2-). . H

.

i. R R RCOR -C3 Grignard

CH3CH2MgX :

CH3 + H2O CH3

CH3CCH3 + CH3CH2MgX CH3CCH2CH3 CH3CCH2CH3 + Mg(OH)X O OMgX OH

ii. R R RCOR, R -C3 R

C3C2- Grignard CH3MgX :

CH3 + H2O CH3

CH3CCH2CH3+ CH3MgX CH3C CH2CH3 CH3C CH2CH3 + Mg(OH)X O OMgX OH

.

71

. CH3CH2CH2

H 1- ,

-OH. .

CH2=O + CH3CH2MgX CH3CH2CH2OMgX + H2O CH3CH2CH2OH + Mg(OH)X

. CH3CHCH2CH3 2- OH

-OH, (-C3,

C3C2-). . 2-

, , RCO (

).

i. R RCO -C3 Grignard

CH3CH2MgX :

+ H2O

CH3CH=O + CH3CH2MgX CH3CHOgX CH3CHCH2CH3 + Mg(OH)X

CH3CH2 OH

ii. R RCO CH3CH2- Grignard

C3MgX :

+ H2O CH3CH2CH=O + CH3MgX CH3CH2CHOgX CH3CHCH2CH3 + Mg(OH)X

CH3 OH

3. a r=58.

a. Na .

. a :

i) 2 ;

ii) i ; C=12, O=16, H=1.

. CH2O :

Mr =12+2+ 16=58 =3

72

: C36 :

CH3CH2CH=O

CH3CCH3 O

. C36 C 2

C, CH3C CH arkovnikov :

g, Hg2SO4

CH3C CH + 2 CH3C= CH2 CH3CCH3 H2SO4 OH O

2 .

ii) .

.

CH3CH2CH=O + 2 CH3CH2CH2

4. =2,5 g/L .

a. .

. :

i) 2 ;

ii) HCl ; C=12, O=16,

H=1.

. .

V

4,22mM

4,22

V

M

m

4,22

V

M

mn r

rr

Mr= 22,4 Mr=56

C2 :

r=12 +2=56 14=56 =4

: C48 :

CH2 = CHCH2CH3 1

CH3CH = CHCH3 2

.

73

CH2 = CCH3 | CH3

. i) To 2 Markovnikov

.

CH2 = CCH3 + 2 CH3CCH3 | | CH3 CH3 ii) 2- . Cl

C . 2- HCl

2-.

CH3CH = CHCH3 + HCl CH3CHCH2CH3 Cl

1.

.

. . . . . . . . . + H2 CH2=CH2

. CH3CH2CH=CH2 + HCl . . . . . . . . ( )

. CH3CH=CH2 + Cl2 . . . . . .

. CH3CH(CH3)CH=CH2 + 2 . . . . . . . . . . ( )

. CH3CCH + . . . . . . . CH3COCH3

. . . . . . . . + Cl2 CH3CH2C=CCH3 Cl Cl . HCCH + . . . . . CH3CH3

. HCCH + 2 . . . . . . .

. CH2=CH2+H2

. CH3CCH +2r2 . . . . . . . . . . .

74

. CH3CH2CCH +2HCl . . . . . . . . . . .

. CH3CH(CH3)CH=CH2 + Br2 . . . . . . . . . . . . . . . . . . . + HCl CH3CH CH2CH3 ( ) Cl +H2O . . . . . . . . + HCHO . . . . . . > CH3CH2CH2OH -Mg(OH)Br

+H2O . CH3CHMgCl + CH3CHO . . . . . . . > . . . . . . . + . . . . . . . CH3

+H2O

. CH3CH2gCl + CH3CH2CHO . . . . . . . . . . .> . . . . . . . + . . . . . . .

CH3 CH3 CH3

+H2O

. CH3C-MgCl + . . . . . . CH3-C C-CH3 > . . . . . . . . + . . . . . CH3 Cl MgO CH3

. CH3CH2CHO + H2 > . . . . . .

. CH3CCH3 + H2 . . . . . . O + 2H2O . CH3CH2CHO + HCN . . . . . . . > . . . . . . + . . . . . . .

2. :

. H2 Cl2 :

i.

ii. -2.

. 2 Cl2 :

i.

ii. -2.

. HBr :

i.

ii. .

.

75

. 2 :

i.

ii.2- 2SO4.

. 2 :

i. C2H2

ii. H2SO4 HgSO4.

. r .

. 2 i 1-.

. r 2-.

. , 1-.

. Mg 2-- .

. HCN :

i. ,

ii. ,

iii. ().

. CH3MgX :

i. ,

ii. .

3. HCl .

.

, .

, .

[: CH2=CH2]

4. 2 , :

. .

. .

. , HCCH .

. .

76

5. 2 1- :

. 1- . . 2-. . . . .

6. :

. .

. .

. .

. .

7. H2SO4 HgSO4 .

2 HBr

. Mg . 2.

:

. . . 1-. . . . 2-.

8. 2

;

. CH3CH=CH2 . HCCH . CH3CN . CH2=CH2

9. Grignard 2

2- ;

. CH3CH2CH2MgCl

. CH3CHCH2MgCl CH3

. CH3MgCl

. CH3CH2MgCl

10. Grignard .

+2

: + > . 2,3 2 .

+ ;

. 3- .

.

77

. .

. .

. .

11. :

Ni +HCl +Mg

+ 2 > > > H2SO4 + 2 > Hg/HgSO4 +2 + > 2

;

. . . . . 1-. . 2-.

12. H Mg

(). 3 2 . :

. . . . . . . 2- .

13. 10 g :

3 3 2 2 2 2CH CH, CH C CH, CH CH C CH, CH CHCH CH CH .

2 ;

. HC CH . 3CH C C . 3 2CH CH C CH . 2 2 2CH CHCH CH CH .

.

(. )

14. 2

;

. 3 2CH CH CH . 3CH C CH . 3CH CN . 2 2CH CH . HC CH

78

15. Grignard; Grignard

, .

.

79

1

1. -

. Grignard HCH= ,

.

(.2001/. 1)

. Grignard (RMgX) (HCHO)

(RCH2OH) Mg(OH)X.

(..2003/. 1 . . 2010/ 2)

. Grignard

.

(.2004/. 2)

. CHCH CH2=CHOH.

(.2003/. 2)

. Markovnikov:

,

( +) .

(.2005/. 2)

. .

(..2005/. 2)

. HCl, 1,2

.

(2007/. 1-2011/. 1)

. Grignard .

(..2007/. 2)

. Grignard .

(.2008/. 2)

80

. (CHO) Grignard

(CH3OH).

(2008/. 1)

. Grignard (HCH=O)

.

(..2008/. 2-. 2009/. 1)

. .

(. 2011/. 1)

. .

(. 2012/. 2)

2. -

. 2 3 3CH - C - CH 1-.

(..2005/. 2- .2007/. 2)

. HCl CH3-CH=CH2 3 3CH - CH - CH .

Cl

(..2001/. 1)

. Grignard .

(.2000/. 1)

. (HCH=O) Grignard

.

(. 2007/ 1)

. 2 .

(. . 2009/. 2)

. .

(O 2005/.1)

.

81

. 2 .

(O 2005/.1)

. RC N .

(. 2009/. 1)

. 2-.

(. 2008/.2)

.

.

(. 2007/. 2)

. .

( 2005/. 1)

. 3CH CHO (HCHO) .

( 2010/. 1)

. Grignard

.

(. 2010/. 2)

. Grignard (RMgX)

.

(. 2010/. 2)

3. HC 1-, :

. 1,2- . 1,1- . 2,2-

. 2,3- .

(2001/. 6)

4. ,

.

+ CH3CH2OH

(.2001/. 4)

82

5. HCN C3H6O .

,

.

(.2001/. 8)

6. Grignard (RMg) (CHO)

:

. . . . . .

. , , Grignard

(RMgX) .

(..2003/. 5)

7. CH3CHBr2 HBr :

. CH2=CH2 . CH2=CH - C . Br - CH = CH Br . CHCH.

(.2003/. 5)

8. :

HC CH + H2O ( )

CH3- C-CH3 +HCN B

O

(.2005/. 4)

9. ,

.

( Grignard) +( )

CH3

( ) 2( )g OH X

H3C-C-CH3

OH

(.2008/. 6)

.

83

10. Grignard (RMgX) (CH3COCH3)

:

. . . . . . . .

(2000/. 5)

11. Grignard (R-Mg-X) :

. (, HCH=O)

....................... .

. ....................... .

(..2001/. 4)

12. 2

:

. 3 2CH CH C N . 3 2CH CH = CH . 3CH C CH . 3 2 2CH CH CH MgX .

(.2006/. 5)

13.

.

( )

( )

1. HCl . 2

2. Cl2 .

3. H2O . 1,2

4. H2 . 2

.

, .

. .

(.2006/. 4+2)

84

14. Grignard CH3-CH2-MgX

CH3-CO-CH3 :

CH3

. 3 3CH - C - CH . 3 2 2 3CH - CH - CH - CH - CH

OH OH

CH3 CH3

. 3 3CH - CH - CH - CH . 3 2 3CH - C - CH - CH

OH OH

(2009/. 5)

15. :

Grignard , ,

..................... .

(..2009/. 3)

16. , , : 2+ RMgCl()

2() + () 2 - + g()Cl

(. 2007/.6)

17. :

. CH3CH=O .C6H5COCH3 .CH3COCH2CH3 . HCH=O.

( 2007/. 4)

18. :

2 2

2 4 4

H O H ORMgCl

5 12H SO /HgSO (C )H O

, .

(. 2010/. 6)

19. Hg, HgSO4,

H2SO4;

.

85

. . . . . . . .

(. 2010/. 5)

20. :

. . . 2- .

(. 2011/. 5)

21. ;

2, H2SO4 HgSO4, .

.

(. 2012/. 1+2)

23. Grignard (RMgX) .

;

. . . .

(. 2012/. 5)

2

1. :

() () CH3CH=CH2 + HCl ( )

() + Mg CH3-CH-MgCl ()

CH3

() + () ()

() + H2O CH3-CH-CH2OH () +Mg(OH)Cl

CH3

(2000/. 9)

2. CH3MgCl CH3CH2CH2CH=O

. :

86

. CH3MgCl CH3-C-CH2-CH3 .

. CH3CH2CH2CH2MgCl CH2= .

. (CH3)3 C MgCl CH2= .

. CH3CH2CH2MgCl CH3CH=O .

.

.

(O 2006/.5)

3. HCN ,

2 . .

(2011/. 2)

.

87

:

,

:

C C - C=C + AB : 2,Cl2,Br2,I2,H2O A B

( ) .

( sp3 sp2) .

1. RX

a ( )

(Cl,Br,I) :

RCHCH2 + KOH RCH=CH2 + KX + H2O

H X : CH3CH2Br + KOH

CH2=CH2 + KBr + H2O

CH2=CHCH2CH3 + KBr + H2O

CH3CHCH2CH3 + KOH ( 20%)

Br CH3CH=CHCH3 + KBr + H2O

( 80%)

, ,

Saytzeff : ,

,

.

2. RX2

a ( )

(Cl,Br,I)

.

Saytzeff.

88

()

, :

CH3CH2CHCl2 + 2KOH CH3C CH + 2KCl + 2H2O

CH3CHCH2Cl + 2KOH CH3C CH + 2KCl + 2H2O

Cl

() ,

:

Cl CH2CH2CH2CH2Cl + 2KOH CH2=CHCH=CH2 + 2KCl + 2H2O

3. ROH ( )

H2SO4 1700C .

. H2SO4, 170

0C

CH3CH2CH2OH CH3CH=CH2 + H2O

Saytzeff. H2SO4 1700C

CH3CHCH2CH3 CH3CH=CHCH3 CH2=CHCH2CH3.

A 1400C :

. H2SO4, 1400C

2 CH3OH CH3OCH3 + H2O

.

1. 2 ,

. ;

, C

( Saytzeff).

90

3. . .

,

, ,

(, ). :

Cl | CH3C CH3 + 2KOH C3C CH + 2KCl + 2H2O | Cl Cl | CH3CH2CH + 2KOH C3C CH + 2KCl + 2H2O | Cl

CH3CH CH2 + 2KOH C3C CH + 2KCl + 2H2O | | Cl Cl

4. :

. 1 2

. 1 2

. CH3CH2CH2OH 0

2 4.H SO , 170 C CH3CH = CH2 + H2O 1

CH3CH = CH2 + 42SOH CH3CHCH3 (2

| (Markovnikov)

. CH2 = CHCH2CH3 + H X CH3CHCH2CH3 ( Markovnikov)

|

X

|

CH3CHCH2CH3 + KOH CH3C = CHCH3 + KX + H2O

2 ( Saytzeff)

.

91

5. :

. 1 1,2

. 1 2

.

. CH3CH2CH2CH2Cl + KOH CH3CH2CH = CH2 + KCl + H2O

CH3CH2CH = CH2 + Br2 4CCl CH3CH2CHCH2

| |

Br Br

. CH3CH2CH2CH2Cl + KOH CH3CH2CH = CH2 + KCl + H2O

CH3CH2CH = CH2 + H OH 42SOH CH3CH2CHCH3 (Markovnikov)

|

OH

. CH2 = CH2+ Cl2 2CCl CH2 CH2

| | Cl Cl

CH2 CH2 + 2NaOH CH CH + 2NaCl + 2H2O

| |

Cl Cl

1. :

1700C, H2SO4 . CH3CH2CH2OH > . . . . . . . . + . . . . . . .

1700C, H2SO4 . CH3CHCH2CH3 > . . . . . . . . . + . . . . . . . . OH . . . . . . . . . + KOH > CH2=CH2 + . . . . . . + . . . . . . . . CH3CH2CHCH3 + KOH >. . . . . . . . . + KCl + H2O

Cl

. . . . . . . + . . . . . . CH3CCH + 2KCl + 2H2O

92

. . . . . .

. CH3CH(Cl)CH(Cl)CH3 + . . . . . > . . . . . . + 2NaCl + 2H2O

. CH3CHBrCH2CH2CH2r + 2KOH > . . . . . . + . . . . . . . + . . . . . . . + g +C + 2 170

0C, 2S4 + 2

. CH3CH2CHCH3 > B> > > E> Z

Cl

2. :

a :

. 1,1

. 1,1 .

. 2,3-.

.

. .

. 2-

. 2--3 .

3. :

. H2SO4 ( 1700C) 1-.

2.

. a 1 .

Cl.

. Cl 1 .

a.

. Cl2 .

a.

. H2SO4 ( 1700C) 2 .

Cl2 .

. a 2 .

r2 .

.

93

. a 1,2 .

2.

. .

2.

. H2SO4 ( 1700C) 1 .

r2 . .

. a 1 .

r2 . 2.

4. .

.

C3H 7Cl , .

5. Br2 C3H6 (A)

NaOH, .

, .

6. NaOH 2 ,

:

. 2,3 . . . .

7. :

.

. 1

. 2

. .

8. 2 :

. 1 , . 2 . , . .

.

95

. 2-. .1-. . -2- . . 2-.

14. NaOH 3- 2-

:

. -2-. . 3--1-. . . . .

15. Mg

1700C

2 Ni ;

. . . -2- . . 2- . . 2- .

16. K 2,2 ,

:

. 1 . 2 . . 1.

17. :

2 4 2o

2 4

.H SO H O

3 2 H SO170 CCH CH OH X

:

. . . . .

(. )

18. HBr /1

19. :

. 3- 2--2 . 2- 2- . 2,2- 1-

. 2-

(. )

20. 1- 2-;

96

1

1.-

. Saytseff, ,

.

(.2004/. 2)

. 2 2.

(.2004/. 2)

. , 2SO4 1700C, (-C C-H).

(..2002/. 1)

. 3 2 3CH - CH - CH - CH 1-.

(..2001/. 1)

. Cl 1,1 .

(.2006/. 2)

. HBr 2- 2- 2- 1-

.

(. O 2006/.1)

2. :

. CH3-CH-CH3 + a .+.. + 2

Cl

. NH3 + H2O +

. CH3C =CHCH3 + HBr ( )

CH3

(..2003/. 5)

.

97

3. ,

() , () ().

CH3-CH=CH-CH3 2 4/r CCl (A) 2 a , , () 2 , ()

(.2003/. 6)

4. NaOH:

. CH3CH2CH3 . CH3CH2OH . CH C-CH3 . CH3CH2CH2Cl.

(2004/. 5)

5. :

CH3CH2CH=CH2 + HBr ( )

CH3CH2CH2CHBr2+2aOH + 2 + 22

(..2007/. 2+2)

6. .

. (CH2=CH2) . (CH3CH2OH).

(..2008/. 2)

. (ROH) ................

(..2004/. 2)

3CH

7. 3 2 3CH CH CH CH CH

Cl

NaOH :

98

3CH 3CH

. 2 2 3CH = CH - CH - CH - CH . 3 3CH - CH = CH - CH - CH

2CH 3CH

. 3 2 2 3CH - CH - CH - C - CH . 3 2 3CH - CH - CH = C - CH .

(. 2009/. 5)

8. : 2H O+RMgClHCH = O () +Mg(OH)Cl

2 4

0

H SO

3 2 2170 C() CH CH = CH +H O

N (RMgCl), (B), ().

(. 2009/. 6)

9. 2- 2SO4;

. 2- . . 1- . 2-

(. 2011/. 5)

10. : 3 2 3 ( ) 3 3 2|

Cl

CH CH C HCH NaOH CH CH CHCH NaCl H O

:

. Markovnikov . Saytzev

. .

(2012/. 5)

2

1. 2- ( CH3-CH2-CH-CH3),

Br

NaOH.

.

99

.

.

.

.

(..2003/. 4+4)

2. :

2 4.H SO ,

2 3 2 CH = CH - CH + H O

2 4 4

||H SO /Hg/HgSO

2 3 2 3

O

+ H O CH - C- CH - CH

.

(.2007/. 8)

3. :

NaOH 2-

2-.

(. 2010/. 2)

4. ,

, , .

2 4 2 2

2 4

4

Br / CCl H O H / Ni2KOH

v 2v Hg,H SO HgSO

( )

C H (B) ( ) ( )

(. 2012/. 8)

100

()

.

C A + B C B + A

1. X RX

O C+- X-

. RX

:

Na, RCN, ROR, RNH2, RCOOR , RC CNa

H : RI > RBr > RCl >> RF

:

a. a

NaOH

:

H2O RX + NaOH ROH + NaX

: H2O CH3CH2Cl + NaOH CH3CH2OH + NaCl

NaOH HCl

:

CH3CH2Cl + NaOH CH3=CH2 + aCl + H2O

. (KCN)

(KCN) (RCN),

:

R+ - X- + - : R Y + X-

.

101

RX + KCN RC N + KX

H+ RC N + 2H2O

RCOOH + NH3

:

CH3Cl + KCN CH3CN + KCl

H+ CH3CN +2H2O CH3COOH + NH3

. (RONa)

(RONa)

RX ROa , .

RX + RONa ROR + NaX

:

2CH3I + CH3ONa CH3OCH3 + NaI

( )

CH3I + CH3CH2ONa CH3CH2OCH3 + NaI

()

(RONa) :

ROH + Na RONa + 1/2H2

. 3

3 . :

1 RX + NH3 RNH3X

2 (KOH NaOH) .

RNH3X + KOH RNH2 + KX + H2O

:

+KOH

CH3I + NH3 CH3NH3I CH3NH2 + KI + H2O .

:

CH3 + NH2 CH3NH2 + H

102

.

:

RX + RCOONa RCOOR + NaX

:

CH3I + CH3COONa CH3COOCH3 + NaX

CH3CHCH3 + CH3COONa CH3COOCHCH3 + NaX

I CH3

T (RCOONa )

:

RCOOH + NaOH RCOONa + H2O

RCOOH + Na RCOONa + H2

. (RC Ca)

(RC Ca) .

RX + RC CNa RC CR + NaX

:

CH3CHCH3 + CH3C CNa CH3C CCHCH3 + NaI

I CH3

T (RC CNa) :

RC CH + Na RC CNa + H2

2. ROH

a. (SOCl2)

SOCl2 Cl:

ROH + SOCl2 RCl + SO2 + HCl

:

CH3CH2OH + SOCl2 CH3CH2Cl + SO2(g) + HCl(g)

! SO2 HCl RX

.

.

103

.

H2SO4

RCOOH + ROH RCOOR + H2O

:

H2SO4

CH3COOH + CH3CHCH3 CH3COOCH CH3 + H2O CH3 ( H2SO4).

.

3. RO

:

H2SO4

RCOOR + H-OH RCOOH + ROH

( NaH )

:

RCOOR + NaOH RCOONa + ROH.

:

CH3CH2COOCH3 + NaOH CH3CH2COONa + CH3OH

4. CVH2V+2

-C-H- C-C- , .

.

(

).

+ 2 RX + HX 2 : Cl2 Br2

.

.

:

CH4 + Cl2 CH3Cl + HCl

CH3Cl + Cl2 CH2Cl2 + HCl

104

CH2Cl2 + Cl2 CHCl3 +HCl

CHCl3 + Cl2 CCl4 + HCl

5. .

1-, ,

a.

2RC CH Na RC CNa 1/ 2H

.. 3 3 2CH C CH Na CH C CNa 1/ 2H

CH CH a.

2CH CH Na NaC CNa H

2ROH Na RONa 1/ 2H

.. 3 2 3 2 2CH CH OH Na CH CH ONa 1/ 2H

2RCOOH Na RCOONa 1/ 2H

.. 3 3 2CH COOH Na CH COONa 1/ 2H

6 5 6 5 2C H OH Na C H ONa 1/ 2H

a, a a

,

.

RC CNa X R' RC CR' NaX

RONa X R' ROR' NaX

RCOONa X R' RCOOR' NaX

1. KCN ,

. HCl .

NaOH .

,

r=130.

A, B, , .

C=12, O=16, H=1.

.

105

CH2+1Cl .

CH2+1Cl + KCN CH2+1CN + KCl

H+ CH2+1CN +2H2O CH2+1COOH + NH3 (B)

.

: CH2 2.

NaOH :

CH2+1Cl + NaOH CH2+1OH + NaCl

()

:

CH2+1COOH + CH2+1OH CH2+1COOCH2+1 + H2O

()

rE= 130 = 28 + 46 = 130 28 = 84 = 3.

C36, :

C3C=C2. :

C3C=C2 + HCl > CH3CHCH3 () 2-

Cl

: To A Markovnikov.

CH3CHCH3 + KCN CH3CHCN + KCl Cl CH3

H+ CH3CH CN + 2H2O CH3CHCOOH + NH3 CH3 CH3

(B)

CH3CHCH3 + NaOH CH3CHCH3 + NaCl

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Χημεία γ λυκείου θετικής κατ 3 τεύχος