Oxygen Containing Reactions Flashcards
1
Q
What are typical nucleophiles?
A
Alcohols, amines, hydrides
2
Q
What are typical electrophiles?
A
Carbonyl carbon, phosphate groups
3
Q
Only a ___ reactive molecule can form a ____ reactive molecule
A
More; less
4
Q
Nucleophiles = Lewis ____
A
Bases
5
Q
Alcohol attacks carbonyl C of COOH => ______
A
Ester
6
Q
Alcohol attacks ketone/aldehyde => ______
A
Hemiketals/hemiacetals
7
Q
Across a row, nucleophilicity _____
A
Increases
8
Q
Good leaving group = _____ in solution
A
Stable
9
Q
Atoms that leave as ____ = great LGs
A
Gases
10
Q
_____ electron shells (_____ periods) => _____ charges => ______ LG and _____ nucleophile
A
More; higher; distribute; good LG; bad nucleophile
11
Q
Weaker nucleophile can be an LG through _________ _______ reaction
A
Nucleophilic substitution
12
Q
Best nucleophile = ______ _______
A
Strong base
13
Q
Nitrogen = ______ nucleophilic than oxygen
A
More nucleophilic
14
Q
Boiling point of OH goes _____ with molecular weight and ______ with branching
A
Up with MW; down with branching
15
Q
OH has higher melting/boiling points than alkanes due to ______
A
Hydrogen bonding
16
Q
OH typically acts as ____
A
Nucleophile
17
Q
Alcohols = electron _____ group
A
Donating
18
Q
Electron withdrawing groups make alcohols more ______
A
Acidic by drawing electron density away from acidic proton => increased partial positive charge
19
Q
Electron donating groups make molecules more ____
A
Basic by stabilizing positive charge
20
Q
Alkyl groups = electron ______ groups
A
Donating
21
Q
Trend of alcohol acidity
A
Greater number of EDGs => weaker acid
22
Q
Strongest to weakest alcohol acid:
A
Methyl > primary OH > secondary > tertiary
23
Q
_____ OH has most _____ groups (which are _____)
A
Tertiary OH has most alkyl groups (EDGs) => makes it want to pick up proton (basic)
24
Q
Hydrocarbons = electron _____
A
Electron donating
25
Alcohols = _____ LG b/c ______
Bad LG b/c reactive in solution
26
Alcohols become better LG by being _____ or ______
Protonated or converted to ester (sulfonate)
27
Formation of sulfonates = what type of reaction?
Nucleophilic substitution (OH = nucleophile)
28
Commonly used sulfonates = ____ and _____
Tosylates and mesylates
29
Sulfonates are useful for _____
Protection of alcohols (prevents OH from acting as acid or undergoing undesired reactions)
30
Ethers
R-O-R
- Non-reactive
- Usually shows up as solvent
31
Amines are ____ nucleohpile and _____ LG compared to O
Better nucleophile; worse LG
32
When N only appears w/ 3 bonds => ______
Draw in a lone pair
33
N acts as a nucleophile where lone pair attacks ______
Positive charge
34
Electron ______ groups on amine _____ basicity
Withdrawing; decrease
| Donating; increase
35
Electrophiles usually have ______
Positive charge
| Almost always carbonyls
36
Carbonyl has ______ stereochemistry
Planar => leaves space above and below to be attacked
37
Carbonyl C has a partial ______ charge
Positive
38
Carbonyl becomes more ______ by e- ______ groups
Stable; donating
| Reactive; withdrawing
39
Most reactive carboxylic acid derivative = ______
Acyl chloride
| - Cl pulls e- density
40
Least reactive COOH derivative = ______
Amide (O=CNH2)
| - N donates e- density to C
41
If a carbonyl has a good LG => it will undergo ______
Nucleophilic substitution
| - Cl or -OR groups leave
42
If a carbonyl does not have a good LG => it will undergo ______
Nucleophilic addition
| - Aldehydes and ketones
43
Which is less reactive: ketone or aldehyde?
Ketone b/c it has an R group (EDG)
44
Racemic mixture
Equal amounts of R and S
45
Stereoselective
Prefers either R or S
| - If bulk group that hinders approach of nucleophile from one side
46
Stereospecific reaction
100% and/or 0% of unique stereoisomer is formed
47
Lone pair on O in COOH amide, and ester ______ to carbonyl C
Donate e- density
48
Carbonyls ______ OH as LG
Improve
49
______ quality of COOH makes it vulnerable to ______
Planar; nucleophilic attack
50
COOH derivatives can participate in
Nucleophilic substitution
51
COOH make strong ____ bonds w/ each other => form ____, which increase ______
Hydrogen bonds; dimers; boiling point
52
COOH = most soluble in ______ solvents
Nonpolar solvents b/c able to solvate in dimer form w/o H bonds of dimer being disrupted
53
Electron ______ groups on alpha carbon stabilize conjugate base => ______ acidity of COOH/OH
Withdrawing; increase
54
Carboxylic acid derivatives = formed by ______ ______
Nucleophilic substitution
55
______ ______ = most reactive COOH derivative
Acid halide due to EWG nature of halide
56
Most reactive COOH derivative to least:
Acyl halide > anhydride > ester > amide
57
More stable the LG => more likely to undergo ______ ______
Nucleophilic substitution
58
Anhydride
O=COC=O
| - Ester w/ two carbonyls
59
Anhydride has carboxylate anion LG = stabilized by ______
Resonance
60
Hydrolysis of amides = only possible under ______ ______ ______
Extreme chemical conditions
| - High temperature, strong acid
61
Transesterification
Alcohols react with esters
| - One alkoxy group (RO) is substituted for another in ester
62
Intramolecular formation of ester = ______
Lactone
63
Cyclic amides formed in intramolecular reactions = ______
Lactams
64
Carbonyl carbon = substrate for ______
Acyl substitution
65
Stronger base = stronger ______ = poor ______
Bond; LG
66
Aldehydes and ketones undergo ______ reactions b/c ______
Addition reactions b/c they don't have an LG
67
Aldehydes and ketones exist at room temperature as ______-______ ______
Keto-enol tautomers
68
Tautomerization = ______
Movement of single proton
- Shift from carbonyl to alkene w/ alcohol
- Deprotonation of alpha carbon + protonation of carbonyl oxygen
69
Tautomers exist at ______, and are NOT a ______
Exist at equilibrium; are NOT a resonance
70
Asymmetric ketons form two different enolates: ______ enolate and ______ enolate
Kinetic enolate (less substituted enolate) and thermodynamic enolate (more substituted double bond)
71
Additional alcohol added to hemiacetal/hemiketal =>
Acetal/ketal
| - OR group replaces OH group
72
Acetals/ketals = good ______ ______
Protecting groups
73
Aldehyde/ketons react w/ amines via ______ ______ to form ______ and ______
Nucleophilic addition => imines and enamines
- Imine = similar to carbonyl (C=N)
- Enamine = alkene w/ amine substituent
74
Organometallic reagents (R-) and hydride ions (H-) react w/ aldehydes/ketones via ______ ______ to form ______
Nucleophilic addition => alcohols
| - AKA Grignard reagents
75
H- is hidden in hydride reagents like ______ and ______
NaBH4 and LiAlH4
76
Cyanohydrin
NItrile (CN-) and OH attached to same carbon
77
Phosphoric acid
Similar to carbonyl due to polar P=O bond
78
When heated, phosphoric acids => ______ ______
Phosphoric anhydrides
79
Reduction = ______
Nucleophilic addition of hydride to carbonyl
- Increase in bonds to H or R groups
- Loss of bonds to O or halogen
80
Oxidation = ______
Nucleophilic addition of O to carbon (EWG)
- Increase in bonds to O or halogen
- Loss of C-H bonds
81
Oxidizing agents have several ______ ______
Several O atoms
| - K2Cr2O7, PCC, O2
82
Reducing agents have several ______ ______
Several H atoms
| - LiAlH4, NaBH4, H2
83
Oxidation of COOH to CO2 = ______
Decarboxylation
84
Aldol condensation = ______
Carbonyl nucleophile attacks another carbonyl
| - Due to alpha carbon (adjacent to carbonyl C) being a nucleophile
85
Carbohydrates
Carbon chains w/ alcohol on each carbon except for one
| - That one has aldehyde/ketone
86
Aldoses
Carbohydrates w/ aldehydes
87
Ketoses
Carbohydrates w/ ketones
88
Human body can only assimilate ______ carbohydrates
D carbohydrates
89
Carbohydrate w/ same structure except configuration around single chiral center
Epimers
90
Anomeric carbon
Only C attached to 2 O's
91
Alpha anomer
```
OH group (on C1) and methoxy group (on C6) are on opposite sides of carbon ring
- Alpha = opposite
```
92
Beta anomer
C1 OH and C6 methoxy are on same sides of ring
93
Alpha vs. beta mnemonic
AO that's some BS
94
5 membered ring
Furnaose
95
6 membered ring
Pyranose
96
Sucrose
1,1' alpha linkage b/w glucose and fructose
| - Only one that's 1,1
97
Maltose
Alpha 1,4' b/w 2 glucose
98
Lactose
Beta 1,4 galactosidic linkage b/ galactose and glucose
99
Cellulose
Beta 1,4 b/w chain of glucose
100
Amylose (starch)
Alpha 1,4 b/w chain of glucose
101
Amylopectin + glycogen
Alpha 1,4 b/w branched chain of glucose w/ alpha 1,6 glucosidic linkages forming branches
102
Gabriel synthesis of amino acids
N is protected in pthalimide => acts as nucleophile
103
Strecker synthesis of amino acids
Aldehyde mixed w/ potassium cyanide and ammonium chloride
104
Base catalyzed lipid breakdown
Saponification
105
Saturated fatty acid
Higher melting points due to easy stacking (no kinks)
106
Unsaturated fatty acid
Kinks => do not solidify easily => lower melting point
| - All double bonds are cis
107
Nucleic acid synthesis (phosphodiester bond formation)
O at 3' C of one nucleotide attacks P at 5' end of another
| - OH acts as LG = nucleohpilic substitution reaction
