giao trinh hoa huu co cua dh su pham tphcm

8/7/2019 Giao Trinh Hoa Huu Co Cua DH Su Pham TpHCM

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!"##$$%#!'()*#"+,'-

./"*012'231'Cl Br

'4'4',#'4'

56(7*###$89:/&---96('; )! ? #@ ? 9: / 96 ) #!"##$A(BC-

./"*

Cl Br

ClCl

Cl

821D#',#',1E7121#'$F01',#',$-!"!#"()*+,!-#,A##C-=3G#"##$H'./"*01'012121'231'

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!"#- 9:1;+,()9Q&>#;8#)#RSQT#U,

!V!&N27*';


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#-;&$%(&

HC CH

Cl

ClHC==CHCl Cl HC CHClCl2 2

2 2

+ +

"-+&(+&0!3*"=)6#?!##?!


3/67

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-*(!.**(%#!#/(!#0*1"'/2\R1HE2Y'PR1EH2HE\1RY1H2E2Y'PE1RY1EH22H2E\R1RY1HE2Y'PR1RY1EH2HE3&.*"1/.552Y',

152H52ZZ`152a'R1X$\ENP?!


4/67

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-.R1XH1R1HX1 R1XHRY1R1RYHX1

R1XH50R152HX

R1XH5R15HX/0*. -

23121X121XAC21XAC01X!#)#5"##$$$)!;)!-/0*.1# R21XRRY1XARC01XR8RY'6#4'8,#'4'---(B#)#528#6(B#)#58#6,!#!-/0*#

231XR1321X1X

@,!B(4;4T#;;(;8&?7;#)#4))#5-./"*#!&?(#&7#)#4(&-

Cl

NH

NH

Na NH2

2

23NH

_**+

_

NH

50%50%

+

33

3*

Co

OHOH

OH

NO NONO

Cl

Cl

Cl

_ _+

2 2 2

_

?567857@02


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5

C C XZ

O+Z C C C C +

XZ

_

[O_

] O+

Chm nhanh

123

C C XZYO +

_

Y Z C C X C C + Y

X

Z

_

_

O

[ O_]

516,

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A)#(."$!&B,4C@28(-]A7FC4A?C

C C

Br

Br

CH

CH

H

HBr

Br

CH

CH

H

H

+ I-Br

H

H

CH

CH

Br

I+_

_

_

3 3

33

3

3

I

_

=AR8R>#8C4A#?C

C C

Br

Br

CH

CH

H

HBr

BrCH CH

HH

+ I-Br

H

H

CH

CH

Br

I+_

_

_

3

3 33

3

3

I

_

)#'*)!4,!#)#] #$"*6##$)($4#&&7&'67##$$-

Y C CH X C C X C C X_ _

__

YH+


6/67

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7/67

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77

77DE

F7DF7DF7DF7D,F7D@IJ9K8B9:L23eLMIEÀ0C2Ea0'0A2MC2U025A0C2À0C0'a2A2MCPJ$LM'?F*=#)('(+'H,#

!V!&RWREWR'WWRN-RN4!&9)&e8I-6!&$c9)&RX)!"*+-

LM1EHI4LM1IEJ'7$720121EH2U4A012C2UHUE20121EH2e40121eHeE20121H250121210H2520HA25CA0C2H25#2N+( R1XHRYeR1eHRYX

Cl Br ClLiCH - CH - CH -Li

3 2 2 CH - CH - CH -Br3 2 2+

+

#)(,(+(,+

A012C2H2520125H0A0C2H'2A0C0'H0A0C2HIA0C2IH

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PLMIEH2J$'2ALMCPJ$HJ$HIE'J)&6"6(##)47#!E8'8G88='8G88J$8$8E8----

#"+(,++6'"N

RIXHRY13R1HRY13IEF#)("P'+(+0KQ

LA0C232H2'H022À0C212a0'F$'7


8/67

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R5 HH HH HH HH HH R 1 HH HH HH

Re HH HH HH HH HH R HRX HH HH HH HH HH R2U HH HH HH HRIX 1 HH HH HH HH R2" H HH HH HR2E 1 HH HH HH R2 1 1 HH 1R0' 1 HH HH HH H RPJ$ 1 1 HH 1IIJ!&)!)6SIJ!7SJ4!&)!(4)6S

KF//.=f#'=RXHIACRIXAGC

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9/67

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JJ6"6(##,#'4$B9696,&,(:'(;#!#-

Br MgBr+ Mg

+ HOH+ Mg

ete khan

Br

OH\J!&9)&)*##&'-

=G#'52-JJ


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10

\;96(3J!&,!4&?9)&(3"/#*#?(T9)&&7&'#c#&


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11

2&,\A0C2H'011'HP\1212'H'1210H'2\LM'HE2LMEH'11E+(,+N(77DE

?/Ae*J1JJR0JJRM\e*J11RD+,#!,)96#!,#

P+(,+KN(Q;(-/9-,J0R1J2R1J1RR2J1R`RPJaHX1

"J$;#J$;#2J$;#0J$;#Pf#E;#9625J2HRR1J2H5RJ'2H`PaR1J2H2'R132HJ0R1AJ2C10A,,CE;#00RIXHJX0R0JH0IE'=/#e6B$F)7)&842!&9)&-À02C0JHa'1 H' A02C0J H]1' À02CPJHa'1='#'HE'0='#'À02C0JHaE1'0='$#'D+$:,&:M-à./"*02J202J3

à 20A02C2J02J3à 20A02C0J02J3 20

HLM1e9-ALMC0JH1ALMC0J1LMALMC0J32HALMC23

01e211LLALMC0J3HALMC232i##(B6#"6JJ6(


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9D$02MHJ'0A2MC0J3A2MC2J3 10'H5Y1]15H

/;M,PH2EA''0SMZZC2E2H22'PHP0A0CPHP''PH202A02C2'2H2'

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13/67

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!-3/

LGI2LMN(1/)',!%5##H#'C

0121#''#A]'#'CS 012121#''#A'#'CS01A2C01#'$'#A$'#'C-\=)696!;()*#'"6-23121A0C01LM12112121#'''##'1$'##'$F'#]''#'121AC121G','A0C21A0C2J#'

4/*.44P5C9=!,?O#((Y;(;"$&A&^-I#--CR132HA2P((YZCR1AC0

R132-E2LS2--22R12121

4'6GL@5:8@5@?FJEU5QB8@5@?FQBEB@A5PV5WQI5:84R13H`2aR1214!2Y5Se'PSA0lFC0'RRY3H`2aR1ACRY2#4!?B(3RH`PaR2H,"6e'PRRYH`PaR2HRY]?"65Y'RXH`PaR2HX,"6e'P


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4PGL@5:8@D5B9N-RIXH2RIXH2RHXIRIXHR2IXRHXIRIXH212R212IXR2121HXIH#'$;#RIXHRYRRY1IXRRY1HXI

""84'#!,'#'$;#2#6,96?##'$;#0-7(##'$;#0#&(;c"6#)e96,#&(;-

CH

CHCH Li

CH

CH

CH C

CH

CH

CH

CH

CH C CH

CH

CH

OH

CHCH CH

CH

O3

3

3

3

3

3

3

3 3

3 3

3+

Izopropyl liti Diizopropylxeton Triizopropylcacbinol

56#)#T)!;(;)68/#9;'&V4RV96V-./"*;(;!8;(;&)V#6(;96)!7-5'6"*'4'!8#B'67#/#9;'&(#)*#*##&B7#&


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15

=#!##'47'*47('6#T;(;#&4&'!76!"&'6B#-D+$:!"":##&/$F7*-R5HRH5F7DE5GB=/,W0W2MWA0C2WA0C0=/$F1b01b2M1bA0C21bA0C01

489S9X89F75Y]&RHRY RRYHXP((YPZZ

$Y]?&RHRY RRYHXP((YZ

RXHRY RRYHXXP((YZ

ARC2HRY RRYHRX"

R2'HRY R2RYH'XP

5,9#)*?9#)-RHX RXHXU'2

=#!e#A'YU'2C#@#'$;#0'61$'#'#!&*?!1$'#'-#'$;#2!&)#6#'$;#-5'6#'$;##6#/$F#67*-0C01H'YAU'2C A0C01'H2&


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16

#' 4 #B #& 4! V #


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?#!'#B$()*#(# 2296###'8,)&>##?PA=4


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18

2121H1A1212111CH2\J!&,&,&''#'$)!50((?!


19/67

19

CH

C C

OH OH

CHH

CH

C

OH

C

OH

CH CH

C C

CH

C

O H

C

CH

CHCH

CH

C C

OH

OH

H

O

O

OO

O

_

+

++

+

2

2

+

_ +O

6 66 66 6

66

6

6

5 55 5

5

55

55

5

H H H H H H

H

H

H

H

CH

C C

OH OH

CHH

CH

C

OH

C

OH

CH CH

C C

CH

C

O H

C

CH

CHCH

CH

C C

OH

O

H

H

O

O

OO

O

_

+

++

+

2

2

+

_ +O

6 66 66 6

66

6

6

6

5 55 5

5

55

55

5

CH

CH

CHCH

CH

CH

CH

CH CH

CH

6 6 6

6

6 6

6

6

6

65 5 5

5

5

5

5

5

5 5

4C58MBFEA5P@57@8MBFEC57@YG'#'e6#'!?&8476#&9:*8?)!2pZZ96((>#)!lZ-

1f#

CH CH

CHCH

CH

CH CH

CH

CH CH

CH

CHCl

Cl

Cl

OH OH

OH

OH

HO HOCl Cl400oC

3 2 2

2

2 22

2

2

2

2 2+;

CHCH

CH

CH

CH

CH

CHCH

CH

CH

OH

OHOH

OH

HOC22

2

2

2

2

22

2

2 2

CH

H O

H

Ni

Al(OR)

C H OH

H O

OH

OH

3

5

O

2

1=/#=)*''#'#@#&!&&"*?

21AC12D"&231H221AC12H050((Y2P((2521A52C1252H0G'#'#&&"*#;#B#;#?#!#)6-


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20

$Y]'e6#T#&9:*()*#)-&(A7FC96AD8eC1f#\IF1'

CH

CH

CH

CH

CH

CH

CH CH

CH

CHOH

OH

2

2

2

2

2

2

2 2

22

2

CH

H O

H

OH

OH

3

O2

Br

Br COCH COCHO

OCOCH OCOCHC CH

CH

CH

CH

Br

Br

CH

CH

CH CH

CHCH

CH

CHOCOCH

OCOCH

OCOCH

OCOCH2

2

2

2233

3

3

3 3

3

3BrBr

AgOCOCH AgOCOCH+

+

+ +

+ 4

\D8e1]'

CH

CH

CH

CH

CH

CH

CH CH

CH

CH OH

OH

2

2

2

2

2

2

2

2

CH

H O

H

OH

OH

O

2

Br

Br

O

C CH

CH

CH

CHBr

Br

CH

CH

CH

CH2

2

2

Br+ +

+

+4KMnOKOH

H

OH

OH

O

2

=


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21

4"5WQI5:8JVMFQB@I659R85RLGLAFP8D-G*#Y=79:B_'96"##$-$Y='6"+,96)*#&&7-

OH

OH12

4

OH

12

12 3

4

56

//

HO

HO

HO

1//1 2

a/ p-Terphenyl-2-ol a/ Biphenyl-2,4,4,6-tetrol/

b/ 2,5-Diphenylphenol b/ (p-Hydroxiphenyl)phlorogluxinol b/ 2-Phenyl-1-naptola/ khong^

/

4*=MF@FNB9RLY#*(&'?4$*#)*#4-$Y5#!,?O#9)&$F47-

LM105H5LM1H520#YJ)&R?#-EF8'9644/)!)&4/(^(!-LLH'HY22LM1'HLM1'HLM1H'"Y,((j#!$F-#-

C

CH

CH

H C O OH C

CH

CH

OH

O

CH

CH

3

33

3

3

3O2 100oC+

Cumen Cumen-hydropeoxit Phenol Axeton 5)6#E2C

OHO

2Br

HBr

2

4

+

-Menton ( 3-Oxo-p-mentan) (1-Metyl-4-izopropylphenol)

Timol


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22

4+O5QB8UL567@5Z8[78EB9NC9:8\-LM11 LM11HH

Y=*'LM11H5 LM115HH2D":#'#"-LM1H'1RA"CLM11RH'LM1HA0C2LM110H0?$&96)7)64$4#&,`(;"+$:#


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23

$Y=$)!&77J'44''*!&9)&5P0Y50((-J!&E4)-

OH3

/

2NH HSO NH4

Noi hap 150oC-

2-Naptol 2-Naptylamin #Y=$)!J!@,!9)Y4!7*';##9)&$;4B7-LM1HUPZZLLHU

456765N8D;0M24Y'&J!&"+"6#&44#,`#&


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24

OH

3_

22 2+ CH =CH-CH -O-SO Ar

HO

CH =CH-CH

ArSO H( orto; para)-AlylphenolAlyl arensufonat

5"6#'HEN0c?!#7'#96A7FC##-

O

O

OHH

(CH )C (CH )

(CH )

(CH )(CH )

(CH ) (CH )

(CH ) (CH )C

CC

C

C

CC

C C(CH )

(CH )C

(CH )C

O OO

H

3

3

3

33

3

3

3

33

333

3

333

3

3

3

33

3

3

[ O ]

Do,_( )

PbO

C H6 6

_H

O

HO

OH

HO

OH

HH

COOH

HO

Axit mezotactricAxit maleic

CC

CC

C

C

O H

H

COOH

COOHCOOH

KMnO KMnOKMnO44 4

Axit oxalic Phenol


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25

4*#]*

HO

OH

HO

OH

HO

CH3 OH

OH

OH OH

OH

OH

Phenol (or, m, p-) Crezol Timol Cacvacrol Catechol Rezoxinol

OH

OH

OH

OH OH

OH

OH

OH

OH

OHOH

Hydroquinon

Pirogalol Hydroxihydroquinon Phloroyluxinol 1-naptol 2-naptol

HO

C

C

C C

C H

C H

C H

C H

HO

OHH

H

5

5

5

5

2

2

2

2

OH

Antranol Hexestrol Stinbestrol \(#8/#&*#96#(>#/?'&?&8#"*#!####&7#';74!4-UUFF=)',!%5


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26

'121_22__0801],1217',_220>#21I'1801,,1'12801,

>#*":96-

3

O

CO

CH

CHCH CHCH

O

2222

3

H C

Oxolan

(Tetrahydrofuran) Oxiran 2-Etyl-2-metyloxyran

(1,2-Epoxi-2-metylbutan)

(2-Metyl-1,2-epoxibutan)

-9N8PDFR8XF:989[G@*EIVIP=

O-CH

O-C H

O-CH

O-CH

CH=CH-CH CH =CH-CH

OH

3

3

3

3

22 5

Anisole

Phenetole

AnetoleEugenol

2

4*=4P5@FER1HRY1R11RYH2,20S2P((Y#

HO-C H3

2 2 5 2

O2

22

Oxolan

(Tetrahydrofuran)

C H-OH5

+ C H - O - C H +55

Al OHO+

2

to cao

;

OHOH + H O

H SO42

to cao

H O

4L57L*JEB9NDQ#'HR1XX'8#,##)---

Br-C H2 2 5 2 2C H-ONa

5+ C H - O - C H +

55NaBr

-O-Na I- - O -NaI

+ +


27/67


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28

59:/#Rc#


29/67

29

)#7)!965,! 7 )6,>#$F-5', c5(B-#6',c52-

O2

+

+2+

+OO

H

Br_

OH

OH C

O

CH H

2

H C C H Br

SN

C C

H

H H

H

3

O

CH

2 2

3

H C

+

5+CH

CH53

++

+

O OO

H

OHO

C

O

CH H

2

2

CH C HC C

HH H

H

CH3

CH

OH

C H

HO-C H

_HO

5[-="OA=NC

e6"7"+


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30

)X

7JJ=1e6)*#B#)#&&7##$'"+,"##$762#6$)!7;!-


31/67

31

22

22

CH -CHOCH -[CH ] -CHO

CH -[CH ] -CHO

4

4

2

*(1-Naphtyl)axetaldehyt

**Naphtalen-1-axetandehyt

*6,6-(1,4-Xiclohexylen)dihexanal

**Xiclohexan-1,4-dihexanal 5F!-C/5&!%$H1;+$$-3/-#/,)#$&0$!-31/==3"H,)&>#3#,H(-"O7# N7"01111111111,#,"021111#J"0`2a21111$#E" @=F!"!#"$!%$!&'=&0VWP$


32/67

32

T&$&=)*#233*'6,84()*#"+,#&2#*-\D&9)'6,-\\D&$c)6#!,-

CH CH CH CH

CH CH CH CH -C=C=OCH=C=O =C=O222

2 223

3

* Dibutylxeten; ** 2-Butylhex-1-en-1-on * Phenylxeten ** Xiclohexylidenmetanon =&!"#=54QJF75JVMF@5@?F=4884----

CH

CH -CH

CHO

C-CH

O

OCo

2

+O

2[O]

2[O]

CrO Cl

MnO /H SO

hay CrO /H SO

22

2

2

2

4

4

4

3

3

2

2

3

O

H O

H O

H O

+

+

+

++

+2

2

2

3

to

to

Axetophenon

Tetralin Tetralon

CH ONO

HCHO H O600-700 C

2 2

o

+ +

CH =CH

CHO

O

O2

+[Co(CO) ]

ZnCl

PdCl /CuCl

2

22

2

24

3

3

2

2

3

OH O

+

+

+

+

22

2

3CH

O

CH CHO

2

2o

+

+

50 C

C=CH

R

R

R

R

R RR

R

RO

O

C CH -C-

O

1

11

22

233 3

R-CH=CH CO H RCH CH CHO R-CH-CHO ?PL567@FR7@A5PF5CB

O

HgSO / H

2

224

3

O

H O

+

+

toO

CH CHO

+

C=CH

3R-CH=CH H R-C- CH

H


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33

@6Y=\G7'-

22

H O ++ O22

R

R RR

R R

OO

C C

111

2 2H

OH

C

X

X OH

HO-

\\,&1=!"+,7'#"-

CH Cl CHO +2H O

22

HClMnO,

K6Y=,&""-,&""&-"XR121HACR13HH2

R121HA0ZZCR13H2ARC21HARC23HH25'6,,#Y,#',#'78c#'$;##&3c3$B6-R131R1R131R35,&'65PJ$A0CPc9#"'B'41#)*###$'#&?##$!)-

C C

OH OH

NaIO C=O O=CR

R R

R

R

RR

R

NaIO H O1

12

2

33

444 4 2

+ + + +

T6YWY=

5B9R8L5N=\J)&J-ARC2RR3H0

+

CH

CH

C

C

O

O

O

O

Ca C O CaCO2

2

3

to

\J)&$-=7$%,##$,'#9)&,'6,47'*I8=---)!;(;0ZZ(PZZ-5#&,O7#c"-


34/67

34

200110H2H20H01H2H2?'6F75@EF@I55QB8UB8MBEU5DBV85P5V9J8=.)&,!&'6e'P8e'A11EC0>#2YJ""64!#"+,#',P-.+R'Q#

LM12'H2LM2H'L15A0C2LM22.'H,+R:$J

RIXH12M-----RH2MHIXACRIXH1A2MC0-----RHIXACRIXHRY1'-----RRYHIX'RIXHRY15-----RRYHIXACZ8678=

5L57L5889MD5='F@0`a,24bFMDBF755M9#H''H'

3

3+ +CH C O3

Cl

H

CH CHO HCl

AlCl

?L57L5889MD5J5H''35

H O

3 32+ +

+OCH

OC

23

Cl

H

CH O CHO

HCl

ZnCl

CH O CH=NH

HAnizol Anizaldehyd

NH NH3_ +

@L57L9BD9M=B9D5J=*#4'))&'0Y18?!


35/67


36/67

36

X$F

CH - C - CH CH - CH=CH3 3 2HOO

H

O

CH - C - CHH O

O

+O

_H O2

[ ]3+

CH =C-CH

OH

3- O

2

OH

_

2 22

O

O_

_

=*# ;7 (B #& 7 4 $ ( c " ":# H ># 1 )* ###$'^*?B$:&AR#7#C-

C - C - CH C=C

3 3H

O

C - C - CH

O 3

OH

3

HCH

CH

C H 3

3

56CH

C HC H

CH6

6 55

* *

(R)-3-Phenylbutan-2-on (S)-3-Phenylbutan-2-on/67&767)6,8$F#)*###$'#& "+

$)!'- 5 '6 7' , 7 )6 47 ' & * '6 ! &'O7-

C - CH 3

3 2

HOO

O+O

+

+_

3 +3O+ 2

OO_

C H 356 C H6 5

Br

BrCHBrC4

H O

K68^VLMFKcI5783Hg_XHX

2N$/ZJ"/>"8"/08"/S>@08;/R8:/R-@9:5')*!8(*8?!


37/67

37

e;#6';


38/67

38

;#,'96,')6##'964#!'-

+O CHCH

3

33

3OH

OCH

OCH o

1-Metoxyxiclohexen

t

]6$7)647"+$:!7)6,-

+

+ +O

O

O CHCH 33OHH O

H

Xiclohexanon2

d5678MIPGL@,!)!7;?"496-

3H C=O

2 O O

O

3CH -CH=O

O

O O

CHCH

CH3

33

3Trioxymetylen Parandehyd

)!*&"":#O#7'#$F-

C O CO

_

+

+C

O

O

N-YO

H O

OHH

2

:NH - Y

NH YNHY

2

2 Imin

./"*1.)&50

C O _+

C N

CHCHCHCH

CH

CH 33

3 33

3

3

H O

OH

H

HHH

:NH

NH2 2

N

N N

H

HH

Axetaldehyt-amoniac

Trime hoa/

C O _ ++

C

N

NN

N

+ 2HCHO

3

H O

OH

2H OH

H

H HH

:NH

NH2 2

HH

Axetaldehyt-amoniac

Tetrame hoa/

N

2

Urotropin 4#"*9)&50Y0##


39/67

39

+ +

N

N

NCH COOH3

333HNO :NH

NUrotropin

3HCHO +

NO

NOO NN

N

N

Hexogen22

2

1.)&R52A7C*F7'6"+,7$F#OO-LM1H251LMLM1351LMH2EF'"'

_+

CH

CH CH3

3

3

3

3 3H O3CH NH

2

Trime hoa/

2

3HCHON

N

N2 3CH = N - CH

1 .)& 251A",'7C- !


40/67

40

+,J/$

H C - CH=O2

O

O

O

O 3

33CH -CH=OH -CH - CH - C - CH

OH

2CH =C-CHOH

CH=O CH - OH

H

H

2 2

2

+

+H

H

O

O+

+

_ HO+

"

CH - CH - C - CH

OH OHO

+

+

_H

/$

CH - C -CH -H CH - C - CH

CH=O CH - CH - C - CH CH - CH - C - CH

OH

O

O

H O_ 22

2

2

2

3 3

33

OH

ROH

RO

O

_OO

O

OO_ _

O_

+

9

CH = CH - C - CHCH - CH - C - CHOH

O

O

H O2

23 3

OH O

O

_

+H

+,1$P"YQ#)#]^##$#-

- CH - CH -CH=O - CH - CH -CH=O - CH - CH-CHO - CH=CH -CHO

O

O

OH OH H O

H

H

+

+

+

+

O

O_

_

+

2

2 2

2 HCacbocation andehyt xinamic

1$#)#]#$A#$##$C(^##$-

- CH - CH -CH=O - CH - CH -CH=O - CH=CH -CHO

O O

OH OHH O

O__+

2H Cacbanion andehyt xinamic

HO

_

__

HO

?.FR8XF:L567[B9Re\5&77'*(;'6496c?!


41/67

41

O

O

+

2

2

HO

CHO O=

(100%

(76%

NaOH/H O

25 C, 4h

NaOH/H O

25 C, 10h \J!&B"96,-3")(;),596"-

CH -CH=O CH - C -CH CH - CH - CH - C -CH CH - CH=CH -C - CHO OOH

H OO

+_

2

23 33 3 3 33

\J!&


42/67

42

H - CH=CH - CH - CH=O

H O

H

+O

2

2

2

3

3

3

3toCH - CH - CH - CH - CH OH

CH - CH=CH - CH - CH OH

222

2

2Ni ,

LiAlH4

Ete.. .

Pent-1-ol

Peta-3-en-1-ol

\!&7362-=HPà3121H2

1 J!&i'OO1?-=#'6"FY$F-

O

2 2 22HO

_C H OH t o2

2

2

2 2 2C=O + H N-NH C=N-NH R - CH - R + N + H O

R

R

R

R

11

1...

Hydrazin Hydrazon

5

1 J!&'77?-+1U96"":#'-

C=O

C H

CH4[H]

Zn-Hg

HCl

C H CH CH H O+ 2 2

3

35

5

6

6

+

1J!&4!9)&,'-G(*((&968(*?4!&$)!5-

C=OC H

CHC H CH CH

H O+

2

2

233

35

5 5

6

6 6 +CH

CHS

SC

C H

CH

2

2

2

2

CH

CH

SH

SH

22

2

H

Ni

CH

CH

HS

HS+_

Axetophenon

?567FQJF75=fV9J8-D+$:,&$)!,&*,)&-1=#!='-RHÀ50C2aHRH

1=#!J'-RHÀ#Ca21RH21=#!E"#-RHÀ,Ca21RH2=#!=',&()*#"96)7#62H#@,&"-1244/-2RH2A44YI2HY;(;C2R


43/67

43

f%98FR4&,&(6!,&7*(##"4#&!&*,&4!*#'967-HH10H1

HLMH1LM2H1

_

2 22

+

CHO CH OH COOCOOH

KOH 50% H

H O

+

+

OO

1 567BX9CF 2

3

33 33CH CHO + CH CHO CH COOCH CH

Al(OEt)

J567?9^FBF75GB"4#&9)&,3

_

2

OOH

CHO CH - C

Benzoin

CNO

_687=

\J!&$%'-01HX2X21HX\J!!96)7-&!&96(:)&7-

22

2

CHO H O+CHO

O N

HNO / H SO43


44/67

44

WE^`\ 4 bFMD5EV9J8 V (1 ,!'$ 9!S $ !+&a4 $#$F'#'-"*


45/67

45

CC

CH

CH

O

O

CH

C

O

C

O

CH

O O

OO

OH

CH

CH

HO

CH

CH

HOO HO

O

2H O2_

__

3

3

3

33

33

3

2,3-Dimetylbenzoquinon -.6I#

C CCHCH O

O

CH

C

O

C O

CH

O

OO

OOH

CH CHHO

CHCH

O

O +H O2

__

_

C C C C

OH

_

OH

O_5

5

5

5

5

5

5

56

66

6 6

6 6

6

+ OHOH

*#


46/67

46

@7?KJ 5 5 :I 8 5 GF=5&77'B&7,#&(;*(;&*##"+*964&';#&-J128P1"*"*#$%,_'8(&"*'$)#7[Md"*'4;!-

CH - C - CH - C - CH

OO O

OH

33 2 33CH - C=CH - C - CH

Dang xeton Dang enol

O

CH

3 33 3C C

O

H OO

CC

CHCH

CHC

H

.

C

H

H

?F758OA5P7VIG=J!&4'&6"*'#&


47/67

47

!-3/

LM

_g5=e6)*#B#)#@#&&7#,##$,'#AC-5NEF5GB-=3*'6,()#S32)!'*'6,(#-$-=#R5&7###$''49)R'*6c*,(&-002,()#*#)!-23121S0131,()#/(7*#)-!1121,(#*#)!-23AC2131,(#/(7*#)!-

COOH COOH

COOH

HOOCAxit thom

,

8=44"5L57L5QB8[@7@A5PVB5QB8D5G@C&0V;+$I%5


48/67

48

,4F5PBM5DFR8XF:V5L57L8P[G@*EIVIP

D644#&&7,O7#31,'#02,#230C,7#'#0`2a2,$#1,,'#

A0C2,F$#`2a0,'#0`2aP,7#`2aP,"#0`2aL,?#LM3,X7#

D64#&>#4#&&70,,#AUC3,7'#23,#'#A]C3,O7#2,7'#11LP1,'#22,?#,#711LP1,F'#LM1,$F#11LP1,'#56#67;?,4--- -49NF:@F758M_85GF8PA5P85GF87F7D# &0/)',V&0;+$U+,I%(L!%)%(M!%#,O);%(+,J%(+,I%(011,'01`2aM11'11`2a[11D#"'1121I''

C

O

C CH CH CH CH C

C OO

O

22 2

Xiclohexancacbonyl Butan-1,2,4-tricacbonyl

= 4QJF75@57@@5:8hI@@F7XF:FQJF7585:L>#Y"##$-14,&$%244/9)&,I*,/-14,&$%IP822lYH8---*+)*2,"#T(&31#&7*#&,&$%IP822lYH8---*+)*#,)7-

C C

2

2 2CH - CH - RCOOH R-COOH + H O

KMnO+

4

R

R

R-COOH R-COOHKMnO

H SO

4

4

+

2

H

H"

"


49/67

49

$Y=6#'>#)*###$'-#'$;##,#6#'$;##,*##,-

C CH CH CHCH C

O

2

2

2

R- CH -OH

COOH

R-COOH

+R R

R-CHO

R - COOH +2H

""

[O] [O]

OH

RR[O] R - CH -

R - CH - COOHR - COOH"

"

2

[O]

[O]

2

2Ancol bc I

Ancol bc II

4I6JL5N@57@V5WQI5:85QB8#26KR>ZPZJ"8>R8>>R80"8"0R

###Q#

RgH2AXH>#1CR1Hg1./"*02MH505H2M

#26K+(,R/0#-.6+#R15H2R1H50#26K'H,6R/$@-.+#

R1'0H22R1H0'R1A2MC0H22R1H02M 4589NDDFR8F7DA5P@5:89Y##2.R$+:0P:(MQ# R5HI5ACR5A2CR

52YH01'050#2.R:$R+>-2RIXH2RIXRHXIR'H2ReRHe#2.R>0+>-5H5R5HR5R'#2.+-1H'231'1#6A"6(#,#&W2C-X-5ACP2HY2-2232HH20121032HH2A0C21F#-.+*AJ)&7'C-RXH2A2MC2R1A2MC2R12-*"*#!&J48'$17---HA0C2131H0


50/67

50

J> 4*


51/67


52/67

52

O

H 23

COOH COOH COOH COOHCOOH

CH OH Cl NO

+I, H +R > -I -I > +R -I, -R

pKa 4,2 4,37 4,54 3,98 3,43 92'(+(886',6,+#

RH5R5H2 2RHIARC2H2 RH5R5H2 2RH5202R5H2H2\2'(+'(66# RH252R0H52

R C O

O

H CH =N=N:

_O O+

+2

CH - N N:O+

3

R C O

O

O_

R C N

O

OCH3 2+

4(&.#!L!&',)./9!-CM

R C O

O

HO+

R C O

O

O_

H J!#'96#!&73?(!&79c'6g#&7-+,

R C O

O

H

_O O

+R C O

O

O_

R C

OH

Y

Y

YHO

__

ANE

5567@FRIEE9FLB024X$F8>#,-

\-.+ -0H50015PHD)&"*#!;PH052H27,,7"#)*-

R C O

O

H

O

O

+

+

2

O

3

R C O

O

O_

R C N

O

3 2

+H

H O__

ANE

NH"

NH

H

NH

2O

R C H

O

2


53/67

53

\-.-X,9#)-J!&;:#Y;(;-&


54/67

54

5#R#&&7&'#c4!V"##$#'"+"6-/9c9;##4&*#;!&-

HCOOH H CO2 2

Tia tu ngoai

Os

,,

+

HCOOH H CO2 +

H SO

42

dd 04&$:;)9c9;)66;7)!;(;#96)6#,-

CH COONa 2+4 3

+ NaOH CH Na COto

I$*#"+$:;)8#)##*"AJ!&?"#4C-

C H -CH -COOAg + BrCCl

76oC

C H -CH - Br CO AgBr6 5 56

42 2 + +22

&


55/67

55

R - CH - CH - COOH R - C - CH - COOH2 2 2O

+ H O2

[O]

menAxit--oxo cacboxylic

2

1X'62*,1,##$,'#-

R - CH - CH - COOH R - CH - C - COOH2 2 2O

+ H O2

[O]

Axit--oxo cacboxylic

2

SeO2

9-."J

=6(4;!&76?!


56/67

56

CH =CH - CH -Cl CH =CH - CH -CN CH =CH - CH - COOHCuCN dd HCl

to2 2 2 2 2 2

Axit butan-3-enoic #2"$/-

CH [CH ] - CH -COOH2

2

CH

CH [CH ] CBr- COBr

CH

CH [CH ] CBr- COOCH

[CH ] COK [CH ] COH Quinolin 160-170oC

CH [CH ] - C -COOC[CH ] CH [CH ] CH=C - COOCH

CH

CH

dd KOH dd KOH

HO+ HO+

CH [CH ] - C - COOH

CH

CH [CH ] -CH=C- COOH

CH

3

3 3

3 3

3

2

2 2

2

2

99 9

8

8

CH

3

33

3

3 9

9

3

3

3 33

22

2

3

3

3

3

3

3

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

PBr

Br

CH OH

Axit 2-decyl propenoic Axit 2-metyldodecan-2-enoic @#M,.6 -

CH =CH - CH CH =CH - CN

2

2 2 22oC

HO+

3

3

3

2

22

2

3 + O 2NH+ + 6H O

CH =CH - CN+

2H OCH =CH - COOH + NH

450

Xuc tac/ /

C#2..(K ,'#l00---8>4OCFNF-231HE2E21E1 4O5QB8-1=/,7*),)&"#&;&_#!J96J2-02b231b 1P8[lAHCP82MA18HRC8[PA18HRC

1.:/(96$)!9:/8;)!")AHRC/,!7-23121W0131W021.:/()!9:/8 #&(#?8?c/,#?W?-D;&4,(


57/67

57

C C

CH COOH

H H

C C

COOH

CH

H

H

3

3

>

..........

........

.....

1$F')**'4(:'67/,V)!#96))!#2#!,7'#A#?C?9)&,O7#A?C-

C C

COOH

H H

C C

HOOC

H

H

...

_ O+ C C

OOHO

OO

_

H

1f&96*'#4*96M8L#*-

CHH

3_

O +O

OH

O

OO

_H

CH =CH -CH -CH -COOH

"

++

H O2

CH+

Valerolacton

2 2 2 O3

68U45:I85GFU89NFGBA5PB578M_L'5DFR8XF:5QB8cI58MFGD/#^*96


58/67

58

HOOC

COOH HOOC

COOH

Axit phtalic[ 1,2-benzendicacboxylic]

Axit izophtalic[ 1,3-benzendicacboxylic]

pK1&2

COOHCOOH

Axit terephtalic[ 1,4-benzendicacboxylic]

2,58 5,62 4F758O_","#&7!)!'+/,7*)7,-=/,!7"4#,##,-

_ D,#&4!V*796?7;#>##!#-

COOH

COOHCOOH

COOH COOK

COOK

COOC H

COOC H2

2

5

5

COOK

COOC H2 5

KOH KOH

H O

H O

H O

C H OHC H OH

2

2

2

2

2

25 5

H O_

__

_

,,'#96,7'#"+$:"##$,'*,()#-_H2_2_0_H2,7'#96?7'#&&7 2*(;$:4'&$)!RX84!96"##$,'#,7##$,'#V2##$?9)&RX-5671"'!&9)&')*"#?B()*#",VP##$-

H

2

2 52

C H Br

2

2

22

2

2

5

_H C

C O

OEt

C O

OEt

Na(EtONa)

_ OH+

HC

C

C

O

O

OEt

OEt

O_

Br O_ CH -CH -CH

COOEt

COOEt

CH -CH -CH

COONa

COONaCH - CH - CH -COOH

dd +2NaOH _ C H OH

t o

_CO

t,O+

3

3

3

D,"+*"96-

COOH

COOH

C2

2 C22 2

2

_

o

_

tCH

CH

COOH

COOH

CH

CH

C

O

C

O

O

H O H O

O

O

Oto

;

Ahydrit succ inicAnhydrit phtalic


59/67

59

8

")%**(%#%!&78#!3>##!#!,##$,'#$%B&74?B()*#"+,)!&7##!,##$,'#-./"*$%g-

_+

_

_C

O

C

OO

O

OHR

R Y

Y

HO

('67;?"+,^*-=(&g'6 'AXCRX ', RYR1RY ", RYRRY ]? 5285RR1528R5R 7"967" 51R51 ,",7#

5152R5152 "F 50R50 F 1R11 J,, =#!3$%&7#`$%5>#&7#&5,-

C C2 2 CCC C OOHR R

NH NH

NH

N-OH

NH

NR

Cl NR

RR R R C

Axit hydroxycinic Amidin Amidoxim Imido clorua Nitril Xeten

*%UU.)&XN8'8E8-49NFGBJ2K[2KP/Y66QY"Y '02ME0lNN7'#','"J'$7E'O'I'#']'"J'$7E'O'

4B9YI@9:Y"6'#

RCOOH R - C - Cl

POCl

SO

CO

HClPCl

SOCl

COCl

5

3

2

22

2 HCl

HCl

O

+

+

+

+


60/67

60

2N.O+#

R - C - Cl

HCl

HCl

O

+ +

++

HBr

HI

R - C - Br

R - C - I

O

O

RCOOH R - C - Cl22 2H O

O

+++

C

C

O

O

OC

C

O

O

Cl

Cl

4O@5:8JD#*#&?*#;)!!-

O+

O

C C

O O

Cl ClR R

_

"

" :

=/#&*#(>#?-.6#)##;5#'A5C

33

22

22

2H O

+O O

C

O

ClR

"

"

"

HOR

HOAr

NaOOCR

H-NH

H-NR

NaN

_

RCOOH

RCOOR"

RCOOAr

RCOOCOR"

RCO-NH

RCO-NR"

RCON

+

+

+

+

+

+

+

HCl

HCl

HCl

NaCl

HCl

HCl

NaCl

+(+(#)##;#'A5C-

3 3

+ OOC C

C

OO

ClR R"

"

+

R

R

R1/R"MgBr

2/H O

1/ R"MgBr

2/ H OR"

OH

!V!& RNWR'WREWR5"?$;(;7(;96$&4/!#';&4-


61/67

61

-..#

2 2C C

C

OO

ClR R

R OH

H

Pd

H

Pd

HH

H 5#@"6)!(**"c!"6#(;#9)&J"E

P9)&7;/$;

' 6 A J) & R?7C ># "6 # 4! 4 e8 11$,7"-6e'P965EP#)'-=)6)*4!#',$%+()*#?#!('96B(4;/#)*#&


62/67

62

Y=6,##$,'#9)'-f'6)&^*8()*#&"*;B-e6!&;:#9)&,'6,-

RHRY RRYH2

CH -COOH + CH - CH -OH CH -COOCH -CH + H O Kcb

Kcb=[CH COOCH CH ][H O]

[CH COOH][CH CH OH]

3

3

33

3

33

3

2

2

22

2

2

2

= 4

H SO4

4O@5:8


63/67


64/67

64

#@/-.++(,+#=*#'$;#-

R C

O

O R

R

R

CR

+ +

,

, 22 R-MgX

C

R

R

R OHMgXO

""

""

"

ROMgX

H O

HO-Mg-X_ _

#C/-..#.)#9)&,e' P8---76#6$:4!$)!5Y#'82Y$7>(#7#96*#'$;#A?9),C-

R C

O

O R CR OH ++ ,, 2

R OH

H

H

C H OHNa 5

?5676F7DD98JE9F5G8[FR4

#4/-..( -#&5>##'!?**6?#!,1,##$,'#-

R - C - OC H

O

H - CH - C - OC H

O

C H -ONa

R - C - CH - COOC H + C H -OH

O

2 2 2 25 5 55

522

2+

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66

OR- C

O

OO

OO

2R-COO-

H OCOR

+ RCOOOH

HO

_

_

_ _

...

-.-#

'$F'""*9)&",#,()*#,,7#-

323

3+ +CHO (CH O) O

CH COONa

CH COOHCH = CH - COOH

-.S3PAQ

C

C

O

O

O

C

COOH

O

C

C

O

O

+

AlCl H SO

_H O2

23 4

"'#,11$F'$F#^

C

CO

O

O

C

C

O

O

+ZnCl H SO

_ H O2

2 4

OH

2

2

HO OH

,

Phenolphtalein

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