-













































:

:

(OH). .

.

ROH, R - . , ; , ; , , :

CH3

OH

CH3-C-CH3 H2C=CH-CH2OH

򠠠

OH

-

CH2OH CH2 -CH2 CH2-CH-CH2

Cl OH OH OH OH

򠠠

(b- )

(-OH), , . R , , .

.

.

, , ( ). , .

H R R


R-C-OH R-C-OH R-C-OH


H H H

頠 頠

.

IUPAC , . . . , OH-. , (), () () , .

, , CH3OH . , , , CH3OH, :

OH OH

CH3 CH2OH CH3 CH CH3 CH3 C CH2CH3

렠 렠

CH3

() , (. ).

.

. -OH .

C5H11OH=C5H12O :

OH OH


CH3CH2CH2CH2CH2OH CH3CHCH2CH2CH3 CH3CH2CHCH2CH3

-1 -2 -3

CH3 CH3 OH CH3 CH3


CH3CCH2CH3 CH3CHCHCH3 CH3CHCH2CH2OH CH3CH2CHCH2OH


OH

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

.

. - .

..,C ..,C

/100

H2O

IUPAC

CH3OH

CH3CH2OH

CH3CH2CH2OH

CH3CH(OH)CH3

CH3(CH2)2CH2OH

(CH3)2CHCH2OH

CH3CH(OH)CH2CH3

(CH3)3COH

CH3 (CH2)3CH2OH

CH3 (CH2)4CH2OH

CH3(CH2)5CH2OH

CH3(CH2)6CH2OH

CH3 (CH2)12CH2OH

-1

-2

-1

2--1

-2

2--2

-1

-1

-1

-1

-1

-

-

-

-

-

-

-

-

-

-97

-115

-126

-86

-90

-108

-114

26

-79

-52

-34

-15

38

65

78

97

83

118

108

100

83

138

157

176

195

-

¥

¥

¥

¥

7,9

10,2

12,5

2,3

0,6

0,2

0,05

-

. , , , . OH- , :

R R R R

H-O H-O H-O H-O

. 5 / (20,93*103 /).[ 50-100 / (209,34*103 - 418,68*103 /)].

- :

R

R H O H

H-O H-O H O

R

( ). , ( ).

.

.

, ࠠ . ٸ , :

RX + H-OH R-OH + HX

X:Cl, Br, I; :

CH3Br + HOH NaOH CH3OH + NaBr + H2O

SN2 SN1 . :

RI > RBr > RCl >> RF

, .

, , , ( ):

OH


CH3CHCH3

-2

NaOH

CH3CHCH3

H2O

Cl CH3 CH=CH2

2-

.

. :

+

H-O-H

+ H2O H2O +

RCH=CH2 + H+ RCHCH3 R-CH-CH3 RCHCH3 + H3O

OH

300-350 C :

OH

300-350 C

CH3CH=CH2 + H2O CH3CHCH3

Al2O3 -2

- .

. (BH3)2 , . H2O2

6RCH=CH2 + (BH3)2 2(RCH2CH2)3B 6 RCH2CH2OH + 2B(OH)3

OH- -

, , , - .

- BH3 (), BH3.

H H H H

H:B B B

H H H H

BH3 , , - . , OH-.

H2O2 OH-

C=C + H-B - C-C- -C-C-

H B H OH


H-B = H-BH2, H-BR2

, - H-OH - .

CH3 CH3

(BH3)3 H2O2, OH-

CH3 -C- CH3 =CH2 CH3 -C-CH2-CH2OH

CH3 CH3

3,3--1 3,3--1

()

. , (, , ), , , , .

- : , ; .

( ).

RMgX ( R: ; X: Cl, Br, I) Rli . . , :

O +

RMgX + H-C RCH2O-MgX

H H2O

RCH2OH

O + H+

RLi + H-C RCH2O-Li

H

O R

RMgX + RC CHO-Mg+X

H R H2O R

CH-OH

O H+ R

RLi + RC CHO-Li+ 򠠠

H

(RH)

R R

RMgX + C=O R- CO-Mg+X

R R H2O R

R- C-OH

R R H+ R

RLi + C=O R- CO-Li+

R R

:

O

CH3CH2MgBr + H-C CH3CH2CH2OH

䠠 H -1

( )

OH

O

CH3CH2MgI + CH3C CH3CH2CHCH3

H -2

( )

O OH

CH3MgCl + CH3CCH3 CH3CCH3

CH3

- 2--2

䠠 ( )

- , . , , - . - .


Cd+=Od-

H2O

-C-OMgX - C- OH + Mg(OH)X

R: MgX

d- d+ R R H+

Mg2+ + X- + H2O

Mg(OH)X , , (HCl, H2SO4), .

, , , .

H2C -CH2 + RMgX RCH2CH2HMgX RCH2CH2OH

H2O

O + 2

, - , - s- .

.

.

350-400 C , 21,27

+ 22 3

, ().

400 200 /2 , .

.

4.          (, , -, -) . ( , R = H):

H2O

R─CH=CH2 + H2SO4 R─CH─CH3 RCHCH3 + H2SO4

| |

OSO3H OH

R R

| H+ |

C=CH2 + H2O C─CH3

| / |

R R OH

, ó , ( ). +.

, , , (, , , .), :

6126 225 + 22

; , - , .

1. O-H

. - . : > > . , , , , , :

2ROH + 2Na 2RONa + H2

( : 3Na, 25Na). ( , ..). .

, , . , . , Mg, Zn, Cd, Al , , . :

2CH3OH + Zn (CH3)2 (CH3O)2Zn + 2CH4

. - , , :

CH3ONa +H2O CH3OH + NaOH

:

ROH + NaOH RONa + H2O

, , :

H Br-

½

ROH + HBr R¾O+¾H

( ). , :

HO RO

½ ½

ROH + SO2 SO2 + H2O

½ ½

HO HO

HO RO

½ ½

2ROH + SO2 SO2 + 2H2O

½ ½

HO RO

O O ** OH H¾O+¾H

║ H+ ║ ROH ½ ½ -H2O

R¾C¾OH R¾C+¾OH ** R¾C¾OH R¾C¾OH R¾C+¾OH

½ ½ ½

-ࠠ R-O+¾H R-O R-O

O

R¾C¾OR

, . ( H2SO4) . . .

:

NaOH + HNO3 = NaNO3 + H2O

, , , , , :

+ + - → 2

. , ( ), ; ( , , ) . , 18. , RCOOH , 218.

. :

ROH + ClN=O → RO─N=O + HCl

3ROH + PCl3 → (RO)3P + 3HCl

O O

║ ║

ROH + Cl─C─CH3 → RO─C─CH3 + HCl

O O

║ ║

ROH + Cl─C─Cl → RO─C─CCl + HCl

2. ¾O .

 

.

:

3(CH3)3COH + PBr3 → 3(CH3)3CBr + P(OH)3

PBr3 PI3 :

3C2H5OH + PBr3 → 3C2H5Br + P(OH)3

.

SN2, SN1. :


Br-

RCH2OH + H+ → R¾CH2 ¾O+¾O → RCH2Br + H2O SN2

½

H

R R -H2O R Br- R

R¾C¾OH + H+ → R¾C¾O+¾H R¾C+ → R¾C¾Br SN1

R R ½ R R

H

( + ZnCl2 ). : >>.

3. OH , .

 

. ( ) ~375 :

Al2O3

3─2͠ 2=2 + 2

.

. , , .

, , :

Cu

RCH2OH → R−C−H + H2

200-300 C ║

O

:

R

\ Cu

CHOH → R−C−R + H2

/ 200-300 C ║

R O

. : KMnO4, K2Cr2O7 H2SO4. , :

RCH2OH + [O] → R─C─H + H2O

O

R

\

CHOH + [O] → R−C−R + H2O

/ ║

R O

:

OH O

½ [O] ║

CH3CHCH3 → CH3CCH3

-2 -2

, , C¾C(OH):

() O O CH3

║ ║ ½

H¾C¾OH + CH3CH2C¾CHCH3

-ࠠ 2--3

CH3 O O CH3

½ [O] () ║ ║ ½

CH3CH2 ¾ C¾OH CH3 ¾C¾OH + CH3C¾CHCH3

½ -ࠠ 2--3

CH3CHCH3

2,3--3 O O

() ║ ║

CH3CCH3 + CH3CH2CCH3

-2

, ()

( ) . , . 1,2- , . , . . , , , ; , .

 

.

:

ClCH2─CH2Cl + 2H2O → HOCH2─CH2OH + 2HCl

ClCH2─CH2OH + H2O → HOCH2─CH2OH + HCl

:

O O

║ ║

C2H5O─C─(CH2)n─C─OC2H5 + 8Na+6C2H5OH → HOCH2─(CH2)n─CH2OH +8C2H5ONa

3CH2=CH2 + 4H2O + 2KMnO4 → 3HOCH2─CH2OH + 2KOH + 2MnO2

. , ClCH2─CH2OH. .

() :

H3 H3C CH3 H3C CH3

½ | | 2H2O | |

2 C=O + 2Mg + I2 → CH3─C─C─CH3 → CH3─C─C─CH3

½ | | | |

CH3 IMgO OMgI HO OH

-1,4 ( , ) -2--1,4 (2─≡─2).

, :

250 C H2O

2CH2=CH2 +O2 Ag CH2¾CH2 H+ HOCH2CH2OH

\ /

O

a-

, , . , -, . , .

1.    HCl HBr, ( PCl5 SOCl2).

2.    :

O O O

║ ║ ║

HOCH2─CH2─O─C─R R─C─O─CH2─CH2─O─C─R

3.    . , :

[O] [O]

HOCH2─CH2OH → HOCH2─C=O → O=C─C=O

½ │ │

H H H

4.    ( ) ( ). , , , ( -) ( ):

H

+ │

CH2─CH2 → CH2─CH → CH3─CH + H+

│ │ │ ║

H+ OH OH O O

H

, , :

3 3 3 3 3

│ │ ½ │ │

3─C ¾─3 → +──3 → 3─ ─ ─3 + +

│ │ ½ ½ │ ║

͠ 3 3 Π

+ │

5.    1,2-, ( , ):

2─

2─͠ +

│ + =─3 ─3

2─͠ │ +, 2

͠ 2─

1,3- , .

, .. - :

, .

(-1,2,3). ; . . 17, . . 290.

, ( ). , ; .

.

, . .

(500) , ( ):

2=─3 + l2 → CH2=CH─CH2Cl + HCl

1,3--2

Cl OH Cl

│ │ │

CH2=CH─CH2Cl + Cl2 + H2O → CH2─CH─CH2 + HCl

:

Cl OH Cl ͠ ͠

│ │ │ │ │ │

CH2─CH─CH2 + 22 → CH2─CH─CH2 + 2Hl

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

()

: -, - . : . HCl , α- 2──2Cl β- H2OH─CHCl─CH2OH.

2──2

\ /

2Cl──2Cl H2OH─CHCl─CH2Cl

2──2l

\ /

, , , :

2──=

|

H2OH─C─CH2OH

H2OH─C─CH2OH

1,3- H2Cl─C─CH2Cl . .

, (, )

(-1,2,3,4) . H2=H─C=CH2 :

O O

║ ║

C=CH2 +Br2 CH─CH2Br 2AgO CCH3 CH─CH2─OCCH3 +Br2

│ ║ ║

C=CH2 CH─CH2Br CH─CH2─OCCH3

O

O O O O

║ ║ ║ ║

CHBr─CH2─OCCH3 2AgOCCH3 CH3CO─CH─CH2─OCCH3 +4H2O

│ │

CHBr─CH2─OCCH3 CH3CO─CH─CH2─OCCH3

║ ║ ║

O O O

2CH2─CH─CH─CH2

│ │ │ │

OH OH OH OH

, , .

() (2)4 . (. . 262) . :

Ca(OH)2

3─= + 4= + 2Π C(CH2OH)4 + H─C─OH

│ ║

H O

CH2─CH─CH─ ─CH2 CH2─CH─CH─ ──CH2

│ │ │ │ │ │ │ │ │ │ │

OH OH OH OH ͠ OH OH OH OH ͠

򠠠

, , . . , ( Adonis vernalis), , , , . , .

.

.

\ \

=─ ⠠ ── ( ―

/ │ /│ ║

͠ ͠

). :

\ \

=─ Û ──

/ │ /│ ║

͠ ͠

, (─ ─, NO2 .), -

. , ( ) :

2=͠ → 3─ ─

│ ║

͠

() , , +-:

͠ ͠

│ ** _ │ │

2=─ ─͠ → 2─=Π + → 3─ =

**

δ- . .

, , . , . (.. ):

ClHgCH2─C=O + 2Me → CH2=C─OMe + MeCl + Hg, Me = Li Na.

│ │

H H

( ) ( , , ):

KOH

ROH + HC≡CH RO─CH=CH2

Me2+; 70C

R─C─OH + HC≡CH R─C─O─CH=CH2

║ ║

O O

, . , ( ) : nCH3COOCH=CH2

H2O

- ¾2── C2── ─ - ─2──2── ──

│ │ │ │

3─Π C3─Π ͠ ͠

║ ║

O O n /3 n/3

򠠠 򠠠

2=─2 . , . , :

+OH-

CH2=CH─CH3 + Cl2 CH2=CH─CH2Cl CH2=CH─CH2OH

-HCl

. ≡─2, :

CuC≡CCu

≡ + 2Π ≡─2

, ; , , , , .

2─≡─2 -1,3:

H3PO4

2─≡─2͠ 2ї2

- H2O │ │

H2C CH2

\ /

O

NaPO3

2ї2 CH2=CH─CH=CH2

│ │ - H2O

H2C CH2

\ /

O

 

, (1837 .), , , . , , , . -, -, - .

.

- . - .

OH OH OH OH OH OH

Cl OH

CH3 OH

렠 -렠 -렠 OH

OH OH

Br Br Cl

Br NO2 2,4,6 - 렠 2--4-

.

.

. , . .,

, /3

-, 1,2-

-, 1,3-

-, 1,4-

41

30

11

36

182

191,5

202,8

202,5

1,072

1,0465

1,034

1,035

; - . (9. 100. ), - ; . - , , .

(, ) : -, - - . , , . ( ) : 300 C

C6H5SO3Na + Na OH C6H5OH + Na2SO3

(450-500) , Cu2+ ():

: Cu2+

C6H5Cl +H2O C6H5OH +HCl

() . :

3─ ─3 3─ ─3

+ │ 2 │

+ 3─=2 → → →


→ + 3─ ─3

1,3∙10-10.

, , , (1,8∙10-5). (8% 15). . (+41) , . , , , , , .

:

ArOH + NaOH ArO- Na+ + H2O

( ) , , . .

, :

H

½ H+ H+ H+

O O O O

½ ║ * ║ * ║

* *


* *

( ) - - , . , ό ( ) --

1.    (. ).

2.    :

ArONa + RI → ArOR + NaI

ArONa + (CH3O)2SO2 → ArOCH3 + CH3O─SO2ONa

3.    ( ) , ( ) :

ArONa + Cl─ C─R ArO─ C─R + NaCl

║ ║

O O

O=C─R

ArONa + O ArO─C─R + R─ C─ONa

│ ║ ║

O=C─R O O

4.    PCl5 , , . , PCl5 PCl3. PCl3 , ( ). POCl3 .

5.    :

ArOH + Zn → ArH + ZnO

, --. .

, . ─, σ- I:

O¾H O O¾H

½ (1) ║ (2) ½

+ A+

/\ ½

H A A

I

, , . I , , , - - ( ). :

OH O

Br ½ Br Br ║ Br

HNO3


½ H3C NO2

Br

- - , ( ) . ˸ : Br<SO3H<H. .

.

- -, 2,4- , , 2,4,6- ( ). - - , , (, ) .

:

OH OH O

½ Br ½ Br Br ║ Br

+3Br2 +Br2

-3HBr -HBr

Br Br Br

, .. - , , . .

O¾H O

Br ½ Br Br ║ Br


Br Br-Br Br Br + Br- + H+

.

-, 100 -, 2,4-.

.

(~30%-), ( ). - -, - , - . - , - -. 2,4- 2,4-.

, , , 2,4-, , . , . .

.

 

-:


─ + HO─N=O → HO─ ─N=O

-:


HO─ ─N=O ↔ O= =N─O


- .

. , , .

2 ( ):

ONa OH O

│ │ C

ONa

+ CO2 →

( ) , :

ONa OH ONa

½ NaOH ½ C

+ CCl4 O + NaCl + H2O

ONa OH H

½ NaOH ½ C

+ CHCl3 O + NaCl + H2O

- ( -):

͠ OH

│ ZnCl2 │

+ RCH=CH2

RCH─CH3

C ( ) ( ), :

OH OH OH

│ HCl │ H2O (H+) │

+ XCN

│ │

X─C=NH X─C=O

(X=H, )

, , . () , . , . : , . , . 150 , , ~300. , ( ). ( , , ) . 1909 . - .

:

OH

½ CH2OH


OH OH OH

½ ½ ½

+ CH2O OH CH2

½

½

CH2OH

½

CH2OH


OH OH OH

½ ½ ½

CH2 CH2

OH

OH OH OH OH

½ ½ ½

CH2 ¾CH2 CH2

½                                                                                ½

CH2OH CH2

OH ½

OH ½ OH

½ CH2

CH2 OH ½

½ CH2

CH2 ½

½


, , , . , - - , , .

, -n-:

CH3

(H+) ½

CH3COCH3 + 2C6H5OH HO¾ ¾C¾ ¾OH + H2O

½

CH3

2,2--(4'-)- (.. ) , .

: - , - - . , , .

, :

t C

─ ── → ─ + 2

HO O HO

, , (, Ag+), -:

OH O

[O]

+ H2O

OH O

(-) - :

SO3Na ONa

+ NaOH + 2Na2SO3

SO3Na ONa

. , . ( ) (-1,3):

OH O

½ H2C CH2

+ 2H

H2C O

OH CH2

, , , . , , , . , .

, :

OH

O2N NO2


½ OH

NO2

 

 

. :

ONa OH

½ ½

+ CO2

ONa OH

½

O=C¾OH

.

-:


= = + 2 ─ ─


, , -.

, .

, () :

HO HO

HO¾ ¾C¾OH HO¾ + CO2

HO O HO

.

, . .

.

( ):

H2N HO

H+

¾NH2 + 3H2O ¾OH + 3NH+


H2N HO

.

1,2,4- , - .

:

OK OH

KO ½ OK HO ½ OH

H+

6 + 6 + 6K+

KO ½ OK HO ½ OH

OK OH


2012 , .