CURS 12 COMPU I DICARBONILICI Kernel for Word to PDFSATURA Demo I

n funcie de poziia reciproc a grupelor carbonil se disting compui: - 1,2 sau dicarbonilici - 1,3 sau dicarbonilici - 1,4 sau dicarbonilici

Kernel for Word to PDF Demo

COMPUI 1,2-DICARBONILICI
CH=O CH=O glioxal CH3 C=O CH=O Kernel metilglioxal CH3 C=O C6H5 C=O C6H5 C6H5 C=O C=O

CHWord CH=O 3 C=O to PDF Demo for diacetil (2,3-butandiona) fenilglioxal

benzil

Metode de obinere

Kernel for Word to PDF Demo

1. Glioxalul, cea mai simpl dialdehid, se obine prin oxidarea glicolului cu aer, pe catalizator de cupru.
CH2 CH2 OH OH O2 Cu; 300 C CH=O CH=O
0

2 H2O

Kernel for Word to PDF Demo

2. Benzilul se obine prin oxidarea benzoinei.
C 6H5 C 6H5 C=O CH OH oxidare C6H5 C6H5 C=O C=O

benzoina

Kernel benzil for Word to PDF Demo

Proprieti fizice 1,2-Dicetonele se caracterizeaz prin culoarea galben. Grupa este o grup cromofor . Word to PDF Demo Kernel for Glioxalul i diacetilul sunt lichide galbene. Benzilul este galben deschis. Proprieti chimice Compuii 1,2-dicarbonilici prezint propriet i Demo chimice Kernel for Word to PDF monocarbonilici, dar i unele proprieti specifice. 1)Glioxalul, sub aciunea bazelor, trece n acid glicolic.
CH=O CH=O glioxal HO CH=O

comune

compuilor

Kernel COOH
acid glicolic

for Word to PDF Demo

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2)Transpoziia benzilic, reacie catalizat de ionul hidroxil

C 6H5 C 6H5 C=O C=O NaOH, tC Kernel
0

for Word to PDF Demo

C6H5 C OH COOH acid benzilic (acid hidroxidifenilacetic)

C6H5

transpozitie benzilica

benzil

3)Reacia de oxidare cu ap oxigenat

CH3 CH3 C=O C=O + H2O2

Kernel for Word to PDF Demo

2 CH3COOH acid acetic

diacetil

Kernel for Word to PDF Demo

HO COOH

4)Reacie de ngustare de ciclu

O O HO

Kernel for Word to PDF Demo

1,2-ciclohexandiona acid hidroxiciclopentancarboxilic

COMPUI 1,3-DICARBONILICI
CH=O CH2 CH=O dialdehida malonica CH3 C O aldehida acetilacetica (formilacetona) CH2 CH=O

Kernel for Word to PDF Demo

C6H5 C O CH2 C O C 6H5 CH3 C O CH2 C O CH3

Kernel for Word to PDF Demo

benzoilacetofenona (dibenzoilmetan)

acetilacetona

Metode de obinere Condensarea esterilor cu cetone se formeaz -dicetone

O R C OR' + CH3 C R" EtO -Na+ R C CH2 C O R"

Kernel for Word to PDF Demo

componenta esterica

- R'-OH O O componenta metilenica Kernel for Word to

PDF Demo

Proprieti chimice I. Reacii specifice grupei metilen 1. Reacia de C-alchilare

Kernel for Word to PDF Demo

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R C O

CH

C O

R + CH3I

R C

CH

R+ I

Kernel for Word PDF Demo O to CH 3 O

halogenura primara dicetona

anion enolat

2. Reacia de C-acilare

Kernel for Word to PDF Demo

R C O CH C O R + CH3COCl R C O CH C O R + Cl

COCH3

3. Reacia de O-alchilare

Kernel for Word to PDF Demo

R C O CH C O R R C O CH C O R + CH3 O CH2 Cl R C CH

O C R + Cl

OCH2OCH3

II. Reacii specifice grupei carbonil 1. Adiia apei

Kernel for Word to PDF Demo

OH OH C R tetrol

R C O

CH2

C O

R + 2H-OH

R C CH2

OH Kernel for WordOH to PDF Demo

2. Adiia alcoolilor
OH R C O CH2 C O R + 2R'-OH R C CH2 OR' OH C OR' R

Kernel for Word to PDF Demo

3. Adiia amoniacului
R C O CH2 C O R + 2NH3 -2H2O R C NH CH2 C NH R diimina

Kernel for Word to PDF Demo

4. Adiia hidrazinei
R C O CH2 C O R + 2H2N NH2 hidrazina -2H2O R C CH2 C R dihidrazona

Kernel for Word to PDF Demo

5. Adiia fenilhidrazinei
R C O CH2 C O R + 2C6H5 HN NH2 -2H2O fenilhidrazina R C CH2 C6H5
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N NH2

N NH2

C N

R NH

difenilhidrazona

N NH Kernel for Word to PDF Demo

C6H5

6. Adiia hidroxilaminei
R C O CH2 C

Kernel for Word to PDF Demo

-2H2O R C CH2 C R dioxima N OH N OH

R + HO NH2 hidroxilamina O

COMPU I CARBONILICI NESATURA Kernel for Word to PDF Demo I

CETENE Compuii carbonilici nesaturai cu dublele legturi C=O i C=C cumulate se numesc cetene. Se disting: Kernel for Word to PDF Demo o aldocetene: RCH=C=O, incolore o cetocetene: R2C=C=O, colorate
CH3 C6H5 C C O C C O

CH Kernel 3

C6H5 Demo for Word to PDF difenilcetena (rosie)

dimetilcetena (galbena)

Cetena i metilcetena sunt gaze. Celelalte cetene sunt lichide. Cetena i aldocetenele sunt incolore. Cetocetenele sunt colorate.

Kernel for Word to PDF Demo

COMPUI CARBONILICI , NESATURAI Numele acestor compui se formeaz dup regulile generale. Poziia legturii duble se marcheaz prin cifre sau prin literele alfabetului grecesc, ncepnd cu atomul de carbon vecin cu grupa carbonil. Kernel for Word to PDF Demo
CH3 CH=CH CH=O CH3 CH=CH C CH3 O 3-penten-2-ona ( -pentenona) C6H5 CH2 CH CH=O propenal (acroleina)

2-butenal ( - butenal) (aldehida crotonica) CH3

Kernel for Word to PDF Demo

CH=CH CH=O 3-fenilpropenal (aldehida cinamica)

CH=CH CH=CH CH=O hexadienal (aldehida sorbica)

Kernel for Word to PDF Demo

Metode de obinere 1. Oxidarea alcoolilor nesaturai
R CH=CH CH2 OH R to CH=CH CH=O Kernel for Word PDF Demo MnO2 in solvent inert

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CH2=CH CH2 OH alcool alilic

HC C CH2

oxidare

CH2=CH CH=O to PDF Demo Kernel for Word acroleina

oxidare

OH alcool propargilic

Kernel for Word to PDF Demo

aldehida propargilica

HC C

CH O

2. Condensarea crotonic (vezi compuii carbonilici) Proprieti fizice

Kernel for Word to PDF Demo

Sunt substane lichide, iar termenii superiori solizi. Acroleina are miros neccios. Aldehida crotonic are miros aromat. Kernel for Word to PDF Demo Aldehida cinamic este un ulei cu miros de scor ioar i este folosit n parfumerie. Aldehida propargilic are miros neptor. Proprieti chimice I.Reacii de adiie Kernel for Word to PDF Demo

1. Adiia halogenilor
R CH=CH CH=O + X2 (Cl, Br) R CH CH CH=O

X Demo Kernel for Word toXPDF

2. Adiia hidracizilor
R CH=CH CH=O + HX X = Cl, Br, I
2 Kernel for Word to PDF Demo

R CH CH X

CH=O

3. Adiia acidului cianhidric

R CH=CH C O

Kernel R + HCN

for Word PDF Demo R CH to CH 2 C R

CN O

4. Adiia amoniacului
R CH=CH C O R + H NH2 R CH CH2 C R Kernel for Word to PDF Demo NH2
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5. Adiia aminelor primare

R CH=CH C O

Kernel for Word to PDF Demo

R CH CH2 C NHR O R

R + H NHR

6. Adiia compuilor organo-metalici

CH3

Kernel for Word to PDF Demo

CH3 CH=CH CH R + MgXOH OH

CH=CH CH=O + R-MgX

II.Reacii de reducere
R CH=CH C O

Kernel for Word to PDF Demo

Pd R CH2 CH2 C O R

R + H2

Kernel for Word to PDF Demo

R CH=CH C O R + H2 Pt R CH2 CH2 C O R R CH2 CH2 C OH alcool saturat R

compus carbonilic saturat

R CH=CH C O

R + H2

Kernel for Word to PDF Demo LiAlH4

R CH=CH CH R OH alcool nesaturat

CHINONELE

Kernel for Word to PDF Demo

Chinonele sunt dicetone ciclice , nesaturate, cu inel de ase atomi. Nomenclatur

for to PDF Demo Numele chinonelor Kernel se formeaz Word din numele hidrocarburilor aromatice la care se adaug sufixul chinon. Poziiile grupelor carbonil se noteaz prin cifre sau prin notaiile orto i para. Nu exist meta-chinone.
O O

Kernel for Word to PDF Demo O

O O p-chinona O

CH3

toluchinona Kernelo-chinona for Word to PDF Demo

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O O PDF Demo Kernel for Word to O O

O 1,4-naftochinona O

Kernel for Word to PDF Demo O

O

1,2-naftochinona

amfi-naftochinona
O

O 9,10-antrachinona

Kernel for Word to PDF Demo

1,2-antrachinona

O 1,4-antrachinona

Kernel for Word to PDF Demo

O O 9,10-fenantrenchinona

Metode de obinere

Kernel for Word to PDF Demo

1.Oxidarea fenolilor monohidroxilici
OH CH3 (SO3K)2NO nitrozodisulfonat Kernel de potasiu O CH3

for Word to PDF Demo

O
O

2-metilfenol
OH

Kernel oxidare

for Word to PDF Demo

- naftol

O 1,4-naftochinona

Kernel for Word to PDF Demo

2.Oxidarea fenolilor dihidroxilici
OH OH pirocatechina Ag2O O O

Kernel for Word to PDF Demo o-benzochinona

(rosie)

174

OH CrO3

Kernel for Word to PDF Demo

OH hidrochinona

O p-benzochinona Kernel for (galbena)

Word to PDF Demo

3.Oxidarea diaminelor aromatice

NH2

Kernel for WordNH to PDF DemoO

PbO2/H2SO4; FeCl3; K2Cr2O7 - 2[H] + 2H2O - 2NH3 O

NH2 p-fenilendiamina

Kernel for WordNH to PDF Demo p-benzochinona

p-chinonimina

4.Oxidarea aminofenolilor
OH

Kernel for Word to PDF Demo

oxidare

NH2 1,4-aminofenol

Kernel for Word to PDF Demo 1,4-naftochinona

O
2 2 7 2 5 Kernel for Word to PDF Demo

5.Oxidarea antracenului se formeaz antrachinon

K Cr O sau aer/V O

Proprieti fizice Stare de agregare Chinonele sunt substane solide, cristalizate, colorate de la galben la rou nchis. Solubilitate Chinonele sunt substane puin solubile n ap i volatile, sunt solubile n solveni organici. 0 Kernel for Word to PDF Demo p-Benzochinona formeaz cristale galbene, cu p.t.=116 C, volatile, antrenabile cu vapori de ap , care sublimeaz chiar la temperatura camerei. Are miros neptor.
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Kernel for Word to PDF Demo

o-Benzochinona este roie, instabil, distil fr descompunere. Proprieti chimice Kernel for Word to PDF Demo I.Reacii de adiie 1.Adiia hidroxilaminei

Kernel for Word to PDF Demo

O + NH2OH _HO
2

OH + NH2OH _HO
2

N OH

Kernel for Word to PDF Demo

N OH monoxima NO p-nitrozofenol N OH dioxima

2.Adiia anilinei
O + 2C6H5NH2 - H2 O C6H5

Kernel for Word to PDF Demo

O NH C6H5 + 2C H NH (exces) 6 5 2 HN O 2,5-anilinochinona
2 Kernel for Word to PDF Demo

N C6H5 NH C6H5 C6H5 HN N C6H5 azofenina (rosu inchis)

- 2H O

3.Adiia anhidridei acetice se formeaz triacetilhidroxihidrochinona

O

Kernel for Word to PDF Demo OCOCH 3

+ (CH3CO)2O / CH3COOH (aditie) OCOCH3 (CH3CO)2O _ CH COOH 3

OCOCH3

OCOCH3 OCOCH3

OH to PDF Demo Kernel for Word

4.Adiia bisulfitului de sodiu se formeaz acizi sulfonici ai difenolului corespunz tor

O + NaHSO3 O OH OH

Kernel for Word to PDF Demo

SO3Na

Kernel for Word to PDF Demo

176

5. Adiia acidului clorhidric (adiie 1,4) are loc o izomerizare

O + HCl O

Kernel Demo OHfor Word to PDF OH

H Cl Cl

O for Word to PDF Kernel OH Demo

6. Adiia acidului cianhidric

O + HCN O OH OH

Kernel for Word to PDF Demo

CN cianhidrochinona

Kernel for Word to PDF Demo

7. Adiia clorului
O + Cl2 O H H + Cl2 Cl Cl Kernel H to H for Word Cl Cl O dicloroderivat O O H + Cl2 Cl Demo H Cl - 2HCl Cl Cl Cl Cl O cloranil (tetraclorochinona) (are proprietati fungicide)

PDF

O tetracloroderivat (instabil)

Kernel for Word to PDF Demo

II.Reacii de reducere
O +2H , 2e OH

Kernel for Word to PDF Demo

hidrochinona OH

Kernel for Word lor to PDF Demo Chinonele formeaz cu hidrochinonele (raport molar 1:1) combinaii colorate numite chinhidrone.

Kernel for Word to PDF Demo

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