Exam 3 Flashcards
1
Q
_____ acids give up H+ more readily.
A
stronger
2
Q
The more _____ the conjugate base, the stronger the original acid is.
A
stable
3
Q
The more stable the conjugate base, the _____ the original acid is.
A
stronger
4
Q
The greater the EN of the atom/group, the _____ its acidity.
A
greater
5
Q
The greater the EN of the atom/group, the greater its acidity. (ONLY across a _____ on periodic table).
A
row
6
Q
Rank sp, sp2, and sp3, from least acidic to most acidic:
A
sp3 < sp2 < sp
7
Q
Rank C, N, O, and F, from least acidic to most acidic:
A
C < N < O < F
8
Q
The larger the size of an atom, the _____ its acidity.
A
greater
9
Q
The larger the size of an atom, the greater its acidity. (ONLY down a _____ on periodic table).
A
column
10
Q
Rank I-, Br-, Cl-, and F-, from least acidic to most acidic:
A
F- < Cl- < Br- < I-
11
Q
_____ - The charge is spread out farther throughout the molecule.
A
delocalization
12
Q
The greater the delocalization/resonance, the _____ the acidity.
A
greater
13
Q
The greater the delocalization/resonance, the more _____ the conjugate base, and thus the _____ the acidity.
A
stable, greater
14
Q
More resonance leads to _____ pKa, and _____ acidity.
A
less, more
15
Q
_____ _____ -> More EN atoms on an acid -> More stable the conjugate base -> more acidity.
A
Inductive Effect
16
Q
Inductive Effect -> More EN atoms on an acid -> More _____ the conjugate base -> _____ acidity.
A
stable, more
17
Q
Inductive Effect: Acidity _____ as more EN groups are added near the atom.
A
increases
18
Q
Inductive Effect: Acidity increases as more _____ groups are added near the atom.
A
EN
19
Q
The Inductive Effect _____ the farther away the EN atoms are from the anion (conjugate base).
A
decreases
20
Q
The Inductive Effect decreases the _____ away the EN atoms are from the anion (conjugate base).
A
farther
21
Q
Basicity Trends are the _____ of Acidity Trends.
A
opposite
22
Q
Bases need to have some sort of _____ _____.
A
lone pair
23
Q
Carbon usually will NOT be a base, unless it has a _____ _____ on it.
A
lone pair
24
Q
If a base _____ resonance upon protonation, it is a worse base.
A
loses
25
If a base loses _____ upon protonation, it is a worse base.
resonance
26
If a base loses resonance upon protonation, it is a _____ base.
worse
27
A base needs its _____ to be resonance stabilized, in order to be a strong base.
cations
28
Inductive effect leads to _____ basic atoms/molecules.
less
29
pKa = \_\_\_\_\_Ka.
pKa = -logKa
30
Keq = 10^pKa[\_\_\_\_\_] - pka[\_\_\_\_\_]
HB+ - HA
31
Keq also = 10^pKa\_\_\_\_\_ - pKa\_\_\_\_\_
right - left
32
HA + B -\> _____ + \_\_\_\_\_
A- + HB+
33
The molecule that can protonate the most is also the best \_\_\_\_\_.
acid
34
The molecule that can deprotonate the most is also the best \_\_\_\_\_.
base
35
We use _____ arrows in acid/base chemistry.
mechanistic
36
Start arrows from where electrons _____ and point them to where electrons _____ \_\_\_\_\_.
start, end up
37
\_\_\_\_\_ - Donates electrons. Electron source.
nucleophile
38
\_\_\_\_\_ - Accepts electrons. Electron sink.
electrophile
39
Nucleophile - _____ electrons. Electron source.
donates
40
Electrophile - _____ electrons. Electron sink.
accepts
41
Nucleophile: Donates high energy electrons. Usually a _____ charged or _____ species with a pair of electrons in a high energy orbital.
negatively, neutral
42
Electrophile: _____ charged / _____ species with empty atomic orbitals or low energy antibonding orbitals.
positively, neutral
43
Reactions happen when you have a flow of _____ between molecules.
electrons
44
\_\_\_\_\_ happen when you have a flow of electrons between molecules.
Reactions
45
The nucleophile _____ electrons to the electrophile.
donates
46
The closer the _____ is to the \_\_\_\_\_, the more likely the reaction will take place.
HOMO (Highest occupied molecular orbital), LUMO (Lowest unoccupied molecular orbital)
47
Reaction steps: 1) Determine _____ /\_\_\_\_\_. 2) Figure out the bonds being _____ /\_\_\_\_\_. 3) Start _____ at nucleophile and end at electrophile.
nucleophile, electrophile, broken, made, arrow
48
In regular Alkene reactions, usually the halogen goes to the _____ substituted side UNLESS _____ is involved.
more, resonance
49
Carbocation stability order for substitution: _____ \> _____ \> \_\_\_\_\_.
tertiary \> secondary \> primary
50
\_\_\_\_\_ _____ -\> C is more electron donating than H. _____ \_\_\_\_\_ -\> Partial overlap of the sigma orbital of adjacent C-H or C-C bond of the alkyl group.
inductive stabilization, hyper conjugation
51
Inductive stabilization -\> C is more _____ donating than H.
electron
52
Hyper conjugation -\> Partial overlap of the _____ orbital of adjacent _____ or _____ bond of the alkyl group.
sigma, C-H, C-C
53
\_\_\_\_\_ - Preference to form a bond at one atom over the other.
regioselectivity
54
Due to Hammond's Postulate, in the energy diagram, the rate determining step is endothermic. This means the TS looks more like the \_\_\_\_\_.
carbocation
55
Resonance stabilization is _____ important than substitution.
more
56
\_\_\_\_\_ _____ - When H-X is added across an unsymmetrical alkene, X prefers to bond with the most substituted C, and H bonds to the least substituted C (after resonance).
Markovnikov's Rule
57
Markovnikov's Rule - When H-X is added across an unsymmetrical alkene, _____ prefers to bond to the most substituted C, and _____ bonds to the least substituted C (after resonance).
X, H
58
\_\_\_\_\_ - Addition of water, H/OH across double bond.
hydration
59
hydration - Addition of water, _____ /\_\_\_\_\_ across double bond.
H/OH
60
Resonance _____ substitution.
\>
61
In hydration reactions, the _____ usually goes to the more substituted side, while the _____ usually goes to the less substituted side (after resonance).
OH, H
62
In alkene reactions, the first step is that the alkene "attacks" the \_\_\_\_\_.
proton
63
In most reactions, the first step is that the _____ "attacks" the proton.
nucleophile
64
\_\_\_\_\_ _____ - H/OR added across alkene (where R is any Carbon group).
alcohol addition
65
Alcohol addition - _____ /\_\_\_\_\_ added across alkene (where R is any Carbon group).
H/OR
66
In alkene reactions, an acid helps _____ \_\_\_\_\_ to get the reaction going. Then that particular _____ serves in the rest of the reaction.
generate catalyst, catalyst
67
\_\_\_\_\_ _____ - The nucleophile and electrophile are in the same molecule.
intramolecular reaction
68
Intramolecular reaction - The nucleophile and electrophile are in the _____ molecule.
same
69
Intramolecular reactions happen _____ than Intermolecular reactions.
faster
70
Intermolecular reactions - Two _____ molecules interact.
separate
71
Under _____ conditions -\> only neutral/positive intermediates around. Only exceptions are non-basic anions (Br-, Cl-).
acidic
72
Under acidic conditions -\> only neutral/positive _____ around. Only exceptions are non-basic anions (Br-, Cl-).
intermediates
73
\_\_\_\_\_ _____ - Migration of a H, or alkyl group, to an electron deficient carbon (C+). Driving force is making a more stable C+ or to relieve strain.
carbocation rearrangement
74
Carbocation Rearrangement - Migration of a \_\_\_\_\_, or _____ \_\_\_\_\_, to an electron deficient carbon (C+). Driving force is making a more stable C+ or to relieve strain.
H, alkyl group
75
If an atom is sp2, it has a _____ \_\_\_\_\_ shape. This means that if a new group is added to it (if no chiral centers were present before), then it could be added to both the _____ or \_\_\_\_\_.
trigonal planar, top, bottom
76
For these particular reactions, if you are _____ chiral centers, you are always going to get a mixture of products.
creating
77
For these particular reactions, if you are creating chiral centers, you are always going to get a _____ of products.
mixture
78
If your SM had 0 chiral centers and you make a new chiral center in the product, you will have a _____ \_\_\_\_\_ of \_\_\_\_\_.
1:1 mixture of enantiomers
79
If your SM had a chiral center and new chiral centers are made in the product, you will have a _____ of \_\_\_\_\_.
mixture of diastereomers
80
\_\_\_\_\_ = No chiral centers.
achiral
81
Achiral = _____ chiral centers.
no
82
The Bromonium ion must have both Br's on _____ or _____ (they have to be the same).
wedges, dashes
83
The Bromonium ion opening goes through a _____ mechanism. i.e. The I- has to get to the _____ of the _____ \_\_\_\_\_ orbital for the stereochemistry.
SN2, backside, sigma star
84
\_\_\_\_\_ - Chiral center changes (inverts).
inversion
85
\_\_\_\_\_ - Stereochemistry of the starting material affects the stereochemistry of the product.
stereospecificity
86
Having _____ alkene geometry will give a different diastereomer of your product in the end.
opposite
87
Addition of X/OH: _____ goes to least substituted C. _____ goes to most substituted C. (AFTER resonance!)
X, OH
88
In the addition of X/OH, _____ is in excess, allowing it to be used as a base.
H2O
89
Addition of ROH/X: _____ goes to least substituted C. _____ goes to most substituted C. (AFTER resonance!)
X, OR
90
In the addition of ROH/X, _____ is in excess, allowing it to be used as a base.
CH3OH
91
Keep in mind, in most addition reactions, _____ occurs to the side being added, when breaking up the bromonium/iodonium/chloronium ion.
inversion
92
For Hydrogenation reactions (both alkene and alkyne), you need some sort of _____ for the H2 to work off of.
metal (Pd, Pt, or Ni)
93
Usually a hydrogenation reaction converts an alkyne to an alkane. However, if you add a \_\_\_\_\_, then you can convert the alkyne to an alkene.
poison
94
\_\_\_\_\_ - Hinders the catalyst of hydrogenation reactions on alkynes, so the hydrogenation reaction will go only once instead of twice.
poison
95
Examples of a "poison":
Pb(OAC)2, quinoline
96
Dissolving metal reduction is used to convert an alkyne to a _____ \_\_\_\_\_.
trans alkene
97
Dissolving metal reduction uses _____ or _____ paired with \_\_\_\_\_.
Li (pure metal), Na (pure metal), NH3 (l)
98
Dissolving metal reduction DOES NOT work on a _____ \_\_\_\_\_.
terminal alkyne
99
If you want to make a terminal alkyne an alkene, then you will need _____ \_\_\_\_\_ via a _____ reaction, instead of dissolving metal reduction.
Lindlar's catalyst, hydrogenation
100
\_\_\_\_\_ - Add alkyl group to a terminal alkyne.
Alkylation
101
Alkylation needs a _____ \_\_\_\_\_ to deprotonate the terminal H on the alkyne, as well as a _____ alkyl halide to add.
strong base (NaNH2), primary
102
3 Steps to Organic Synthesis:
1) Count C's on SM and product. Do you need to add more C's? 2) Determine functional groups. How do they change? How can you interconvert them? 3) Work backwards (Retrosynthetic Analysis)
