III Õèìè÷åñêèå ñâîéñòâà
1. Ðåàêöèè íóêëåîôèëüíîãî ïðèñîåäèíåíèÿ:
Ìåõàíèçì ðåàêöèè
H H δ-O H O– H
\ δ+ δ- - \ δ+ / \ / +H2O |
C = O + Z: C Ñ H – C – OH
/ / δ- / \ |
H H Z H Z Z
1) ðåàêöèè ñ ñèíèëüíîé êèñëîòîé:
O– OH
| Í+ β α|
CH3 – C = O + HCN CH3 – CH – CN CH3 – CH – CN
| (öèàíãèäðèíû)
H íèòðèë-α-ãèäðîêñè
ïðîïèîíîâîé êèñëîòû
2) ðåàêöèè ñ ãèäðîñóëüôèòîì íàòðèÿ:
O – OH
+ - | | – +Na +
CH3 – C = O + Na(HSO3) CH3 – CH – SO3H CH3 – CH – SO3
|
H â ýòó ðåàêöèþ âñòóïàþò íå âñå êåòîíû: òîëüêî òå, êîòîðûå èìåþò
ãðóïïó –ÑÍ3 èëè àëèôàòè÷åñêèé öèêë õîòÿ áû ñ îäíîé ñòîðîíû
îò êàðáîíèëüíîé ãðóïïû
OH
2 1 |
CH3 – CH – SO3Na
(ãèäðîêñèñóëüôîíàòû)
1 – ãèäðîêñèýòàíñóëüôîíàò íàòðèÿ – 1
3) ðåàêöèè ñî ñïèðòîì (òîëüêî äëÿ àëüäåãèäîâ):
O–
δ+ δ– | +H+ +H+
CH3 – C = O + CH3OH CH3 – CH CH3 – CH – OH
| | |
H OCH3 OCH3
1-ìåòîêñèýòàíîë-1
H – O+ – H H – O+ – CH3
| - H2O + +CH3OH |
CH3 – CH CH3 – CH CH3 – CH
| | | - Í+
OCH3 OCH3 O – CH3
O – CH3
|
CH3 – CH
|
O – CH3
(àöåòàëè)
1, 1 – äèìåòîêñèýòàí
4) ðåàêöèè ñ ðåàêòèâîì Ãðèíüÿðà:
OMgCl OH
δ+ δ- δ- δ+ | + Í2Î |
CH3 – C = O + CH3MgCl CH3 – CH CH3 – CH – CH3
| |
H CH3
5) ðåàêöèè ñ àììèàêîì:
ðåàêöèè ñ àììèàêîì ó àëüäåãèäîâ è êåòîíîâ èäóò ïî ðàçíîìó
à) àëüäåãèäû
O– OH
| |
CH3 – C = O + NH3 CH3 – CH CH3 – CH
| | | - H2O
H NH3+ NH2
CH3 – CH = NH
èìèíû, ýòàíàëüäèìèí, àöåòàëüäèìèí(NH – èìèíî ãðóïïà)
á) êåòîíû
CH3
|
α – + CH3 – C = O
CH3 – C = O + C2H5O – CH2 – C = O
| -Ñ2H5OH |
CH3 CH3
O– OH O
| +Í2Î | ||
CH3 – C – CH2 – C = O CH3 – C – CH2 – C – CH3
| | |
CH3 CH3 CH3
CH3 O NH2 O
| || +NH3 5 4| 3 2|| 1
CH3 – C = CH – C – CH3 CH3 – C – CH2 – C – CH3
|
CH3
4–àìèíî–4–ìåòèëïåíòàíîí–2
6) ðåàêöèè ñ ïðîèçâîäíûìè àììèàêà:
O– OH
| | - H2O
CH3–C=O + NH2–OH CH3–CH CH3–CH CH3–CH=N–OH
| ãèäðîêñèëàìèí +| | (îêñèìû)
H NH2 – OH NH – OH ýòàíàëüäîêñèì
+CH3–CÍ=O
CH3–C=O + NH2–NH2 CH3–CH=N–NH2 CH3–CH=N–N=CH–CH3
| ãèäðàçèí ýòàíàëüãèäðàçîí àçèíû
Í (ýòàíàëüäàçèí)
CH3 – C = O + NH2 – NH – C6H5 CH3 – CH = N – NH
| ôåíèëãèäðàçèí |
H
ýòàíàëüôåíèëãèäðàçîí
2. Ðåàêöèè êîíäåíñàöèè:
1) àëüäîëüíàÿ êîíäåíñàöèÿ:
-
(C 2H5O) Na –
CH3 – C = O CH2 – C = O
| - C 2H 5OH |
H – Na + H
O– OH
– | +H2O |
CH3 – C = O + CH2 – C = O CH3 – CH – CH2 – C = O CH3 – CH – CH2 – C = O
| | | |
H H H H
(àëüäîëü)
3 – ãèäðîêñèáóòàëü
2) êðîòîíîâàÿ êîíäåíñàöèÿ:
OH
| t
CH3 – CH – CH2 – C = O CH3 – CH = CH – C = O
| –H2O |
H H
êðîòîíîâûé àëüäåãèä
áóòåí – 2 – àëü
3) êîíäåíñàöèÿ Êàííèööàðî (òîëüêî äëÿ àëüäåãèäîâ):
 ðåàêöèþ âñòóïàþò òîëüêî òå àëüäåãèäû, ó êîòîðûõ íåò àòîìà Í â α – ïîëîæåíèè
NaOH
H – C = O H – C = O + CH3OH
| 50% |
H ONa
- C = O NaOH - CH2
| + H – C =O | + H – C = O
H | 50% OH |
H ONa
áåíçèëîâûé ôîðìèàò íàòðèÿ
ñïèðò
CH3 CH3
| |
CH3 – C – C = O + H – C = O CH3 – C – CH2 + H – C = O
| | | | | |
CH3 H H CH3 OH ONa
4) êîíäåíñàöèÿ Òèùåíêî (òîëüêî äëÿ àëüäåãèäîâ):
(C2H5O) 3Al
CH3 – C = O + CH3 – C = O CH3 – C = O
| | |
H H O – CH2 – CH3
ýòèëàöåòàò (ýòèëîâûé ýôèð óêñóñíîé êèñëîòû)
5) êîíäåíñàöèÿ Êëÿéçåíà:
OH
|
- Ñ = O +C2H5ONa - CH – CH2 – C = O t CH = CH – C = O
| + CH3 – C = O | - H2O |
H | H H
H
êîðè÷íûé
àëüäåãèä
6) êîíäåíñàöèÿ Ïåðêèíà:
O–
C2H5ONa |
CH3 – C = O + CH3 – C = O CH3 – CH – CH2 – C = O
| | | –H2O
H O – C = O O – C = O
| |
CH3 CH3
àíãèäðèä óêñóñíîé êèñëîòû
OH
| t
CH3 – CH – CH2 – C = O CH3 – CH = CH – C = O + CH3 – C = O
| -H2O | |
O – C = O OH OH
êðîòîíîâàÿ êèñëîòà óêñóñíàÿ
êèñëîòà
2. Ðåàêöèè îêèñëåíèÿ:
1) îêèñëåíèå àëüäåãèäîâ
à) ðåàêöèÿ ñåðåáðÿíîãî çåðêàëà
OH
|
CH3 – CH = O + Ag2O CH3 – C = O + 2Ag
ONH4
|
CH3 – CH = O +2[ Ag(NH3)2]OH CH3 – C = O + 2Ag + 3NH3 + H2O
á) ðåàêöèÿ ñ ôåëèíãîâîé æèäêîñòüþ
O O
|| ||
C – ONa C – ONa
| |
CHOH + Cu(OH)2 + CH3 – C = O CHOH + Cu2O + CH3 – C = O
| | | |
CHOH H CHOH OH
| |
C – OÊ C – OÊ
|| ||
O O
ñîëü âèííîé êèñëîòû
â) ðåàêöèÿ ñ ôóêñèíñåðíèñòîé êèñëîòîé:
+
Í – ÑÍ = Î
2) îêèñëåíèå êåòîíîâ:
[O]
CH3 – C – CH3 H – C = O + CH3 – C = O
|| | |
O OH OH
I
CH3 – C = O + CH3 – CH2 – CH – C = O
[O] | | |
CH3–CH2–C–CH–CH2–CH3 OH CH3 OH
|| | II
O CH3 CH3 – CH2 – C = O + CH3 – CH2 – C – CH3
| ||
OH O
Ïðàâèëî Ïîïîâà – ðàñùåïëåíèå ïðîèñõîäèò â áîëüøåé ñòåïåíè ïðè íàèìåíåå ãèäðîãåíèçèðîâàííîì óãëåðîäíîì àòîìå
3. Ðåàêöèè âîññòàíîâëåíèÿ:
[H]
CH3 – C – CH3 CH3 – CH – CH3
|| |
O OH
[H]
CH3 – C = O CH3 – CH2 – OH
|
H
5. Ðåàêöèè ïîëèìåðèçàöèè (òîëüêî äëÿ àëüäåãèäîâ):
n H – C = O [ – CH2 – O – ]n
|
H ïàðàôîðìàëüäåãèä (ïîëèôîðìàëüäåãèä)
Ìîãóò îáðàçîâàòüñÿ öèêëè÷åñêèå ñîåäèíåíèÿ
O CH2 – O
/ \ / \
3 H – C = O CH2 CH2 O CH2
| | | èëè | |
H O O CH2 O
\ / \ /
CH2 O – CH2
òðèîêñèìåòèëåí òåòðàîêñèìåòèëåí
6. Ðåàêöèÿ çàìåùåíèÿ:
Cl O
α ð | ||
CH3 – CH2 – C = O + Cl2 CH3 – CH – CÍ + HCl
|
H
O Cl
|| |
CH3 – C + PCl5 CH3 – CH + POCl3
| |
H Cl
Cl
|
CH3 – C – CH3 + PCl5 CH3 – C – CH3 + POCl3
|| |
O Cl
Äàòà äîáàâëåíèÿ: 2015-09-03 | Ïðîñìîòðû: 1181 | Íàðóøåíèå àâòîðñêèõ ïðàâ
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