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Orgo 2 > Final > Flashcards

Final Flashcards

1
Q

Electromagnetic radiation has properties of ?

A

particles and waves

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2
Q

product of frequency of wave and wavelength is?

A

speed of light

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3
Q

energy of each photon is ? to freq

A

proportional. E = hv

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4
Q

freq and wavelength are ?

A

inversely proportional

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5
Q

IR gives info about

A

functional groups

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6
Q

NMR gives info about

A

C-H chemical env

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7
Q

energy is not a continuum but exists at

A

discrete energy levels

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8
Q

energy diff between energy levels is

A

quantized

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9
Q

the molecule absorbs light when the phton has the energy that corresponds

A

exactly to delta E

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10
Q

functional groups are detected by Ir bc each bond type has a

A

characteristic delta E between vibrational states based on bond strength and length

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11
Q

Ir spec if a plot showing the

A

absorption of energy against freq of light

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12
Q

relationship between wave number and mass

A

lower mass = larger wavenumber or freq
higher mass = lower wavenumber or fre

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13
Q

relationship btwn bond strength and wavenumber

A

stronger the bond, the higher the force constant so the larger the wavenumber or freq

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14
Q

trend for wavenumbers in general from large to small

A

X-H then triple bonds then double bonds then single

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15
Q

relationship between wavenumber and hybridization

A

sp has higher then sp2 then sp3

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16
Q

relationship between wavenumber and ring strain

A

inc ring strain = larger wavenumber

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17
Q

relationship between wavenumber and conjugated systems

A

more resonance = lower wavenumber bc more single bond character

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18
Q

what 2 factors impact signal intensity

A

bond polarity and number of identical bonds present

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19
Q

relationship between dipole moment and signal intensity

A

more polar = stronger signal

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20
Q

relationship between number of identical bonds and signal intensity

A

more identical bonds = stronger signal

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21
Q

distribution of O-H bonds give rise to a

A

broad signal bc of H bonding

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22
Q

secondary amines have how many N-H signals?

A

1

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23
Q

primary amines have how many N-H signals?

A

2

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24
Q

mass spec is used to determine the ? of a molecule

A

molecular weight

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25
Q

e- impact ionization method uses a high energy e- which

A

strikes a vaporized molecule

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26
Q

Mass spec: energy rich molecule ejects an e- forming a + odd electron species called the

A

molecular ion (radical cation)

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27
Q

molecular ion passes btwn poles of a magnet and is deflected by the

A

magnetic field

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28
Q

Mass spec: which molecules get deflected more, smaller or larger?

A

smaller

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29
Q

intensity of peak is proportional to

A

percentage of each ion of diff mass in the sample

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30
Q

what is the molecular ion

A

molecular mass of the molecule minus an e-

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31
Q

what is the base peak

A

most abundant peak - 100% relative intensity
might not be the molecular ion peak

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32
Q

if base peak = molecular ion peak, then

A

no fragmentation occurred

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33
Q

what is the (M+1)+. peak

A

measures C-13
inc intensity w inc number of C

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34
Q

Characteristic ratio for Br on (M+2) peak

A

1:1

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35
Q

characteristic ratio for cl on (M+2) peak

A

3:1

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36
Q

NMr involves interaction btwn

A

EM radiation and nuclei of atoms

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37
Q

nuclei with odd number of protons have an intrinsic

A

nuclear spin

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38
Q

the nuclear spin creates a

A

small magnetic moment around the atom

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39
Q

nuclear spins are normally at ? but are aligned by a ?

A

random orientations, strong external magnetic field

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40
Q

spin state alpha

A

aligned w magnetic field, lower energy

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41
Q

spin state beta

A

against magnetic field, higher energy

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42
Q

when Em radiation is applied, nucleus in alpha spin state

A

absorbs energy of photon and flips to beta state

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43
Q

the difference in energy between alpha and beta spin states

A

is small and dependent on B0.

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44
Q

inc external magnetic field to

A

inc delta E between alpha and beta spin states

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45
Q

if a given nuclei has lots of e density, overall affect of b0 is weakened and the nuclei is said to be

A

shielded

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46
Q

if the nuclei has little e density, the nuceli is more affected by B0 and is

A

deshielded

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47
Q

downfield =

A

deshielded = less e- density = feels B0 more

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48
Q

upfield =

A

shielded = high e- density = feels B0 less

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49
Q

the main contributor to deshielding of vinylic and aryl protons is the induced magnetic field associated with pi electrons. what is this called

A

anisotropy

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50
Q

does anisotropy reinforce or oppose B0

A

reinforces

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51
Q

the intensity(not height, but area under signal) of NMR peak is dependent on

A

the number of chem equiv hydrogens giving rise to that signal

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52
Q

protons on adgacent carbons will interact and split eash other’s singles into

A

mulitplets

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53
Q

chemical shift of a proton is affected by

A

magnetic moment of adjacent protons

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54
Q

what is a J value

A

distance btwn peaks of a split pattern

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55
Q

protons coupled to each other have the same

A

J value

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56
Q

when does complex splitting occur

A

when neighbors are not chem equiv.

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57
Q

trans Hs on an alkene has ? J value than cis protons

A

higher

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58
Q

if OH signal is present in NMR, it is a

A

bs betweem 0.5 and 5

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59
Q

Does CNMR have spin-spin splitting

A

no

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60
Q

what does CNMR tell u

A

ho wmany diff carbon types there are

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61
Q

isolated dienes have

A

at least 1 sp3C between the alkenes

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62
Q

the single bond beteen 2 conjugated alkenes is relatively

A

short

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63
Q

there is max orbital overlap and e- delocalization on a conjugated diene if the 2 pi bonds are

A

coplanar

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64
Q

the two coplanar forms of a conjugated diene are

A

s-trans and s-cis

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65
Q

for MO diagrams, number of sp2 C

A

= number of p orbitals and psi`

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66
Q

traits of pericyclic rxns

A

e- move in loop, aromatic-like TS, concerted

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67
Q

electrocyclic rxns must be

A

fully conjugated polyene undergoes ring closure

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68
Q

sigmatropic rearrangements

A

2 db not conjugated
one sigma bond broken, one formed

69
Q

diels alder rxn

A

cycloaddition rxn of diene and alkene
alkene is a dienophile
ex of pericylic rxn
4+2 cycloaddition
mediated by heat

70
Q

the diene must be in the

A

s-cis conformation to react

71
Q

cis to diene–>endo–>

A

anti

72
Q

trans to diene–>exo–>

A

syn

73
Q

endo approach is favored bc of

A

orbital stabilization of hte TS

74
Q

endo product has subst. pointing ? relative to longest bridge

A

down

75
Q

symmetry allowed

A

Homo of diene matches with lumo of dienophile

76
Q

photochemical rxn

A

promotes HOMO, LUMO stays the same

77
Q

cope rearrangement

A

all C

78
Q

claisen rearrangement

A

allyl vinyl ethers
favors ketone until a benzene is present

79
Q

define aromaticity

A

special stability due to resonance delocalizationm of the pi e- in a cyclic conjugated system/cmpd

80
Q

huckel’s rule

A

planar
cyclic
fully conjugated
4n+2 e-

to be aromatic

81
Q

to be antiaromatic must be

A

planar
cyclic
fully conjugated
4pi e-

82
Q

in a frost circle, to be antiaromatic …

A

singly occupied MO or antibonding MO occupied

83
Q

benzylic halides react faster than primary and allylic halides bc of

A

TS stabilization by orbital mixing

84
Q

In EAS, what acts as the nuc

A

benzene

85
Q

what is the intermediatea called for the EAS rxns

A

cyclohexadienyl cation, or arenium ion or sigma complex

86
Q

limitations to friedel crafts alkylation

A

only alkyl halides ccan reaact
benzene can’t have strong EWG (NO2, CN, SO3H, ketones, aldehydes, CA, amides)
anilines do not undergo FCA- must protect with acyl chloride nd pyr

87
Q

benefits of FC acylation

A

no ccat. rearrangement

88
Q

if a subst. for EAS is activating, the rxn goes

A

faster

89
Q

halogens are weak deactivators but are

A

o/p directing

90
Q

aromatics more deactivated than a monohalobenzene cannot be

A

acylated or alkylated with FC. Add acyl gruop first

91
Q

requirements for SNAR

A

LG, EWG O/P to each other
Benzene is e-phile

92
Q

what is the intermediate for SNAR called

A

Meissenheimer called

93
Q

the rate of SNAR inc w

A

-inc numbet of EWG
-what LG it is (F>Cl>Br>I)

94
Q

Elimination addition requirements

A

LG

95
Q

intermediate for elimination addition rxn

A

benzyne

96
Q

nuc attack at a carbonyl happens at what orbital

A

pi*

97
Q

when do imines form

A

primary amine + carbonyl

98
Q

when do enamines form

A

secondary amine + carbonyl

99
Q

thioacetals have an acidic proton that can be deprotonated with

A

nBuLi

100
Q

what is a ylide

A

dipolar intermediate with opposite formal charges on adjacent atoms

101
Q

wittig reaction is highly selective for

A

ketones and aldehydes

102
Q

what will not react but are tolerated in a rxn with wittigs

A

esters, lactones, nitriles, amides

103
Q

what are not tolerated at all with wittigs

A

acidic groups (alc, amine, CA)

104
Q

wittig reagents from simple alkyl halides form the

A

Z alkene (kinetic product)

105
Q

wittig reagents with adhacent carbonyls form the

A

E alkene (thermo product)

106
Q

baeyer-villiger oxidation priority

A

H>3>2, Ph>1>methyl

107
Q

grignards react with?

A

acidic H–> protect free OHs

108
Q

what reagent selectively reduces CA in the presence of other carbonyls

A

BH3THF

109
Q

stabilization of carbonyls depend on

A

resonance

110
Q

most reactive CA derivation to least

A

acyl chloride, anhydrides, esters, amides

111
Q

what reagent do u use to get single addition of a c nuc to an acyl chloride

A

gilman

112
Q

addition of grignard to nitriles gives an

A

iminium

113
Q

iminium is hydrolyzed to

A

ketone

114
Q

how many equivalents of grignards is added to nitriles

A

1

115
Q

keto form is most common, but ? is the reactive species

A

enol

116
Q

enol form of carbonyl contributes to reactivity at

A

alpha c

117
Q

2 reasons for inc acidity of carbonyls relative to alkanes

A

1- induction from O
2- after deprotonation, (-) of enolate ion is stabilized by resonance

118
Q

are enols or enolates more reactive

A

enolates

119
Q

what is an aldol addition

A

addition of one enolate of a carbonyl with a second carbonyl

120
Q

what is the product of aldol condensation

A

alpha beta unsaturated ketone/aldehyde

121
Q

what happens when aldol addition is under heat and acid

A

aldol condensation

122
Q

what base to use for directed aldol addition

A

LDA

123
Q

what is a claisen condensation rxn

A

enolate of one ester reacts w a second ester

124
Q

the alkoxide that is used as a base is the same as the ester group to avoid

A

trans-esterification

125
Q

what is dieckmann cyclization

A

intramolecular claisen condensation

126
Q

for unsymmetric ketones, use LDA, THF, -78 for

A

least sterically hindered deprotonation
kinetic product

127
Q

for unsymmetric ketones, use -OMe, MeOH

A

for subst. enolate
thermo product

128
Q

the thermo enolate us formed under ? conditions

A

reversible, with alkoxide base in protic solvent and rt

129
Q

kinetic enolate is formed by ? conditions

A

irreversible, with SB, aprotic solvent and cold

130
Q

alpha, beta unsaturated ketones and aldehydes are prepared by

A
  1. aldol rxns with dehydration of aldol
  2. alpha halogenation of ketone or aldehyde followed by elimiation
131
Q

strong basic nucs react at the carbonyl carbon

A

Grignards and LAH
kinetic favored

132
Q

less basic nucs react at beta carbom

A

enolates, gilman, amines, thiolates, cyanide
therm0 favored

133
Q

what is michael addition

A

conjugate addition of an enolate to alpha, beta unsaturated ketone

134
Q

what is robinson annulation

A

michael addition followed by intramolecular aldol condensation

135
Q

what is the LG in hoffman elimination

A

quaternary amine

136
Q

hoffman elimiation gives what product

A

least subst. alkene

137
Q

what is the LG for nitrosation of alkylamines for secondary and tertiary amines

A

diazonium cation

138
Q

at C1 of an aldose, the carbonyl is an

A

aldehyde

139
Q

if there is a ketone anywhere else besides C1, it is a

A

ketose

140
Q

carbs are desugbated as D or L according to the sterochem of the highest numbered

A

chiral carbon of fischer

141
Q

what are the 4 stereoisomers of the aldotetroses

A

D and L erythrose, D and L threose

142
Q

stereoisomers of aldopentoses

A

ribose (all right), arabinose is only top. xylose is middle and lyxose is top 2

143
Q

pneumonic for aldohexoses

A

all altruists gladly make gum in gallon tanks

144
Q

numbers for aldohexoses

A

1 2 1,2, 3 1,3 2,3 1,2,3

145
Q

aldohexoses

A

allose altrose glucose mannose gulose idose galactose talose

146
Q

aldoses contain a ? and ? which react to form cyclic ?

A

aldehyde, alcohols, hemiacetals

147
Q

define anomers

A

carb isomers that differ only in stereochem of anomeric carbon

148
Q

subst that are right on the Fischer point ? and those on the left point ?

A

down, up

149
Q

to go from fischer to pyranose

A

manipulate so last OH is vertical

150
Q

what is mutarotation

A

alpha and beta anomers are in equilibrium and interconvert via open form when react w water

151
Q

anomeric carbon of pyranose and furanose form of ketose has both a

A

OH and CH2OH

152
Q

the anomeric effect stabilizes an EN subst. on the anomeric carbon by

A

orbital mixing

153
Q

the axial subst. is stabilized by interaction of a non-bonding e= pair on the ring O with the sigma star orbital which

A

lowers the energy of the overall molecule

154
Q

the EN group prefers to be

A

axial

155
Q

glycoside formation

A

anomeric OH is replaced by some other subst.

156
Q

in fischer glycosidation carbs react with

A

an alc in the presence of an acid catalyst

157
Q

fischer glycosidation is thermo controlled and favors formation of

A

pyranose over furanose

158
Q

anomeric effect causes ? stereoisomer to predominate over ?

A

alpha over beta

159
Q

the glycosol donor…

A

has a LG and is the e-phile

160
Q

the glycosol acceptor….

A

has one free OH and is the nuc

161
Q

in deoxy sugars a OH group is replaced with

A

H

162
Q

amino sugars have an amino group in place of a

A

OH

163
Q

amino acids are

A

amphoteric

164
Q

what is the pI

A

pH at which the aa exists largely in a neutral form

165
Q

when pH < pI

A

aa is +

166
Q

when pH > pI

A

aa is -

167
Q

the amino group can be protected using

A

BOC (deprotect w TFA) or FMOC (deprotect w piperidine)

168
Q

the c terminus is protected using

A

benzyl bromide (deprotect with H2, Pt)

169
Q

why use DCC

A

activates COOH to accelerate amide bond formation

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