CH7: Aldehydes + Ketones Flashcards

1
Q

Aldehyde, Ketone, Alcohol B.P. + Solubility

A

Aldehydes and Ketones can’t H bond to each other so their B.P. is much lower than the corresponding alcohol

They can, however, H bond with water making them soluble

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
2
Q

Aldehydes from primary alcohols

A

Oxidize with PCC to stop early

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
3
Q

How can aldehydes be made from esters, acyl chlorides, C.A. and nitriles?

A

C.A. can’t do-Convert to acyl chloride with SOCl2

Acyl chloride- 1) LiAH(O-t-Bu)3, Et2O, -78 2) H2O

Ester-DIBAL-H

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
4
Q

LiAH(O-t-Bu)3

A

Used with Et2O, -78 2) H2O to form aldehydes from acyl chlorides…prior to this, we can convert a C.A. to an acyl chloride

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
5
Q

DIABL-H

A

Converts ester to aldehyde

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
6
Q

How can ketones be made?

A

1) Ozonolysis of alkenes
2) Oxidation of secondary alcohols
3) Friedel-Crafts acylation
4) From alkynes through Markovnikov hydration
5) Nitriles + Organolithium/metallic

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
7
Q

Ozonolysis of alkenes

A

1) O3
2) Zn, HOAc

Both are used to split an alkene and form a ketone

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
8
Q

Aromatic ketones

A

Made by Friedel-Crafts acylation

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
9
Q

Oxidation of secondary alcohols

A

With Jones reagent, we form ketones

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
10
Q

Vinyl vs allyl

A

Vinyl is on the carbon of the D.B.

Allyl is one over

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
11
Q

Vinylic alcohol

A

Called an enol, they are relatively unstable, will change to a ketone

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
12
Q

Alkyne hydration

A

When an alkyne reacts with H2O and acid (H2SO4/HgSO4) a vinylic alcohol (enol) forms. This then converts to a ketone

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
13
Q

Enol

A

Vinylic alcohol that interconverts between this form and keto form

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
14
Q

Keto-Enol tautomerization

A

The changing from an enol (vinylic alcohol) to a keto form

Once the vinylic alcohol forms strong acid converts it in an equilibrium

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
15
Q

What is needed for keto-enol tautomerization

A

Strong acid, which has often already been used during alkyne hydration. The D.B. grabs the H

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
16
Q

Ketones from nitriles + organometallic/lithium

A

1) React organometallic with Nitrile (C t.b. N)

2) H3O+ hydrolysis

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
17
Q

Hydrolysis of H=N

A

Turns to H=O every time

How well did you know this?
1
Not at all
2
3
4
5
Perfectly
18
Q

Weak vs strong nucleophiles and carbonyl compounds

A

Weak need a catalys ex Lewis acid H-A to protonate the carbon

Strong ex. R: or H: can attack right away and shift the D.B. up

19
Q

Aldehyde vs ketone reactivity

A

Aldehydes are more reactive

1) Less electron pushing “R” groups
2) Less steric-hinderance

20
Q

Hemiacetal

A

A ketone or aldehyde in alcohol will form an eq mix with the corresponding hemiacetal. This has -OR and -OH on the same carbon

21
Q

Ketone and aldehyde in alcohol forms

A

Hemiacetal

22
Q

Noncyclic vs cyclic hemiacetals

A

Non-cyclic aren’t stable 5/6 membered rings are

23
Q

Hemiacetal formation can be catalyzed by:

A

Acid or base (alcohol) RO(-) or ROH
Acid is 3 steps
Base is 2 steps

24
Q

Aldehyde or Ketone + Water

A

Forms a hydrate (gem diol)…proton transfer occurs

25
Acetal
Two -OR groups on the same carbon
26
Acetal formation
An aldehyde or ketone can be reacted with ACID ONLY and excess alcohol to form it. Formation goes through the hemiacetal
27
How to go away from an acetal
Dilute acid catalyst
28
What is the key step in hemiacetal --> acetal formation
OR shifts db down to expell H2O+
29
Acetal formation from ketones vs aldehydes
Aldehydes formation is favored, however ketones can cyclicly form rings with acid catalyst. These cyclic acetals (formed by OH-CH2-CH2-OH are good protecting groups for ketones and aldehydes. Cyclic favors ketones.
30
Addition of primary and secondary amines + ketones/aldehydes
They form Immines with primary amines | They form Enamines with secondary amines
31
Immine
Primary amine and ketone/aldehyde. C=N:-R | Have a D.B. and a lone pair
32
Enamine
Secondary amine and ketone/aldehyde C-N:-R + R' | No D.B. or lone pair. STRONG ACID USED
33
Immine formation
Primary amine + carbonyl system with H3O+...there is also a proton transfer. The acid makes the OH a good L.G.
34
Enamine formation
Secondary amine + carbonyl system with HA...key step is removal of an H on the alpha carbon shifting everything back (final step)
35
Cyanohydrin formation
Carbonyl system + :C t.b.N: | The CN group can be reduced with LAH to a amine group or hydrolyzed to a carboxylic acid
36
Hydrolysis of a cyanohydrin yields
alpha-hydroxycarboxylic acid
37
Reduction of a cyanohydrin yields
beta-aminoalcohol
38
Wittig reaction
Aldehydes and ketones react with a phosphorous ylide to form an alkene with both isomers
39
Ylide
A neutral molecule with adjacent positive and negative charges
40
Phosphorus ylide formation
1) (C6H5)3P: attacks a primary or secondary alkyl halide via SN2 forming a salt 2) Base deptotonates this salt
41
Oxophosphatane
The 4 membered ring formed during the Wittig reaction
42
Tollen's test Ag(NH3)2+/H20
Distinguishes aldehydes from ketones Aldehydes react-Silver Ketones don't react-Nothing Alpha hydroxy ketone-Reacts (Silver)
43
Alpha hydroxy ketone
OH on alpha carbon