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Flashcards in EVERYDAY flashcards Deck (157):
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Walk through the logic for determining which substitution or elimination reaction if....

R-group is tertiary

1. R-group is tertiary: No SN2

2. Is Nuc/Base a strong base?

Yes: alkene product via E2

No: Proceed to next question

3. Is the solvent polar protic?

Yes: substitution and or elimination via fast SN1 and E1; SN1 slightly preferred over E1

No: slow substitution and/or elimination via SN1, E2, and E1, or no reaction

6

(alkene reaction)

Provide the reagents for:

12) Hydrogenation

  1. REDUCTION WTF reaction
  2. No rearrangement
  3. Syn

6


Walk through the logic for determining which substitution or elimination reaction if....

R group is secondary

1. Is the Nuc/Base a strong base?

Yes: alkene product via E2

No, proceed to next question:

2. Is the Nuc/Base a good to moderate nucleophile?

Yes: substitution product via moderate speed SN2

No: proceed to next question:

3. Is the solvent polar protic?

Yes: substitution and or elimination via moderate speed SN1 and E1

No: substitution via slow SN2

7

(alkene reaction)

What is the function of:

H2O2

[Ozonolysis (Oxidative)]

Presumably used for oxidation

7


(alkene reaction)

What is the function for:

CH3-OH
[Alkoxymercuation]

Generic alcohol that substitutes for H2O in similar oxymercuration mechanism.

8

(alkene reaction)

What is the function of:

H2O2

[Radical Hydrohalogenation]

Creates a radical pathway for Anti-Markovnikov addition of H-X to a double bond

9

(alkene reaction)

What is the function of:

Hg(OAc)2
[Oxymercuration]

Functions like an X2 by creating an ion ring intermediate and allowing the Markovnikov addition of H2O to the double bond. Advantage is that it can be removed by NaBH4

9


(alkene reaction)

What is the function of:

OsO4
[Dihydroxylation/Diol formation]

By some orgo magic, can grab both sides of a double bond and eventually disappear for syn diol addition.

9


Alkene naming: Z

Z= zame (same)

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Alkene naming: E

E= oppositE

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Alkenes of 5 or more carbon atoms have what physical state?

Colorless liquids that are less dense than water

10

Are alkenes polar or non-polar?

Alkenes are non-polar

10

Alkenes of two, three and four carbon atoms have what physical state?

Gases at room temperature

10

C13 NMR: 0-50 ppm


C13 NMR: What region contains signals from sp3 hybridized carbon atoms?

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C13 NMR: 50-100 ppm



C13 NMR: What region contains signals from

(1) sp3-hybridized carbons that are deshielded by electronegative atoms, AND

(2) sp-hybridized carbon atoms

11

C13 NMR: 100-150 ppm


C13 NMR: What region contains signals from sp2 hybridized carbon atoms?

11

C13 NMR: 150-220 ppm (usually 200 ppm)



C13 NMR: What region contains signals from carbon atoms of carbonyl groups. Highly deshiedled.

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C13 NMR: What region contains signals from

(1) sp3-hybridized carbons that are deshielded by electronegative atoms, AND

(2) sp-hybridized carbon atoms

C13 NMR: 50-100 ppm

13



C13 NMR: What region contains signals from carbon atoms of carbonyl groups. Highly deshiedled.

C13 NMR: 150-220 ppm (usually 200 ppm)

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C13 NMR: What region contains signals from sp2 hybridized carbon atoms?

C13 NMR: 100-150 ppm

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C13 NMR: What region contains signals from sp3 hybridized carbon atoms?

C13 NMR: 0-50 ppm

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Draw a terpene unit

llama!!

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Draw propylene

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Draw phenyl

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draw methylene

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Draw Tosylate (OTs- )

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Draw vinyl

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Identify

Acetaldehyde

(Acet-aldehyde)

25

Identify

Decalin

26

Identify

Norbornane

27

Identify

Acetone

(acet-one)

this is a ketone

27

Identify

Acetic acid

28

Identify

Acetone

(acet-one)

 

this is a ketone

28

Identify

Acetaldehyde

(Acet-aldehyde)

28


Identify the common name

Benzene

29

Identify

Acetic acid

29

Identify the common name

Isobutylene

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Identify the common name

Vitamin A

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Identify the common name

Propylene

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Identify the common name of the alkenyl group

Methylene

The example is therefore named: methylenecyclopentane

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Identify the common name

Norbornene

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Identify the common name

Nicotinamide (niacin)

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Identify the common name

Ethylene

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Identify the common name of the alkenyl group

Vinyl

The example is therefore named: Vinylcyclopentane

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Identify the common name of the alkenyl group

Allyl

The example is therefore named: Allylcyclopentane

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Identify the common name:

38

Identify the common name:

40

Identify the common name:

41


Identify the common name:

42

Identify the common name:

44

Identify the common name:

44

Identify this common NMR pattern

Ethyl group

44

Identify the functional group in the IR spectra

Alcohol

44


Identify the functional groups in the IR spectra

Carboxylic Acid

44

Identify the functional groups in the IR spectra

Ketone

45


Identify this common NMR pattern

tert-butyl

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Identify this common NMR pattern

Isopropyl

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IR spectra: ester

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IR spectra: Alkane

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IR spectra: Alkane measurement

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IR spectra: Alkene

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IR spectra: Alkene measurement

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IR spectra: Alkyne

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IR spectra: Alkyne measurement

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IR spectra: Ketone measurement

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Isomerism with alkenes

  • For an alkene with one carbon-carbon double bond that can show cis, trans isomerism: two steroisomers possible
  • For an alkene with n carbon-carbon double bonds, each of which can show cis, trans isomerism: 2^n stereoisomers possible

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J value: cis

10 hz

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J value: geminal

2 hz

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J value: trans

15 hz

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Let's say your molecular formula has oxygen and you notice the below chemical shift, what does it imply?

  • +2.5 ppm

  • Oxygen of alcohol or ether

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Let's say your molecular formula has oxygen and you notice the below chemical shift, what does it imply?

  •     +3 ppm

  • Oxygen of an ester

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Let's say your molecular formula has oxygen and you notice the below chemical shift, what does it imply?

  •     +1 ppm

  • Carbonyl group

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(alkene reaction)

Name all anti-addition reactions

  1. Halogenation
  2. Halohydrin formation
  3. Oxymercuration
  4. Alkoxymercuration

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(alkene reaction)

Name all syn-addition reactions

  1. Hydroboration
  2. Syn-Diol Formation (OsO4 Oxidation)
  3. Syn-Diol Formation (KMnO4 Oxidation)
  4. Pt/Pd reduction

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(alkene reaction)

Provide the reagents for:

1) Acid catalyzed hydration

  1. Markovnikov
  2. Possible rearrangement
  3. Syn/anti do not apply

73

(alkene reaction)

Provide the reagents for:

10) Ozonolysis (Reduction step 2)

 

  • Oxidation/reduction WTF reaction
  • No rearrangement
  • Syn/anti do not apply

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(alkene reaction)

Provide the reagents for:

11) Ozonolysis (Oxidation step 2)

  • Oxidation/reduction WTF reaction
  • No rearragement
  • Syn/anti do not apply

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(alkene reaction)

Provide the reagents for:

2) Hydrohalogenation

  1. Markovnikov
  2. Possible rearrangement
  3. Syn/anti do not apply

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(alkene reaction)

Provide the reagents for:

3) Halogenation

  1. Markovnikov rules apply
  2. Bridge formation: No rearragement
  3. Anti

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(alkene reaction)

Provide the reagents for:

5) Oxymercuration

  1. Markovnikov rules apply
  2. Bridge formation: No rearrangement
  3. Anti

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(alkene reaction)

Provide the reagents for:

6) Alkoxymercuration

  1. Markovnikov rules apply
  2. Bridge formation: No rearrangement
  3. Anti

82

(alkene reaction)

Provide the reagents for:

7) Hydroboration

  1. ANTI-Markovnikov
  2. No rearrangement
  3. Syn

84

(alkene reaction)

Provide the reagents for:

8) Syn-diol formation (OsO4 oxidation method)

  1. Oxidation/reduction WTF reaction
  2. No rearragement
  3. Syn

85

(alkene reaction)

Provide the reagents for:

9) Syn-diol formation (KMnO4 method)

  1. Oxidation/reduction WTF reaction
  2. No rearrangement
  3. Syn

86

(alkene reaction)

Provide the reagents for:

13) Radical, Anti-Mark HX Addition

  1. ANTI-Markovnikov
  2. No rearragement
  3. Syn/anti does not apply

87

(alkene reaction)

Provide the reagents for:

4a) Halohydrin formation (alcohol)

  1. Markovnikov rules apply
  2. Bridge formation: No rearrangement
  3. Anti

88

(alkene reaction)

Provide the reagents for:

4b) Halohydrin formation (ether)

  1. Markovnikov rules apply
  2. Bridge formation: No rearrangement
  3. Anti

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Summary of E1 Versus E2 Reactions for Haloalkanes

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Summary of E1 Versus E2 Reactions for Haloalkanes

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Summary of E1 Versus E2 Reactions for Haloalkanes

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Summary of SN1 versus SN2 of haloalkanes

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Summary of SN1 versus SN2 of haloalkanes

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Summary of SN1 versus SN2 of haloalkanes

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Summary of SN1 versus SN2 of haloalkanes

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Summary of SN1 versus SN2 of haloalkanes

97


Summary of substitution vs. elimination reactions for haloalkanes

SN1/E1: not observed

SN2: only reaction

E2: not possible

SN1 reactions of methyl halides are never observed because the methyl cation is so unstable it is not observed in common solvents.

98


Summary of substitution vs. elimination reactions for haloalkanes

SN1/E1: primary reaction if: weak nucleophiles in polar protic solvents, such as water, methanol, and ethanol.

SN2: Primary reaction if: bases/nucleophiles where pka of the conjugate acid is 11 or less, as for example I- and CH3COO-

E2: Primary reaction if: bases/nucleophiles where pka of the conjugate acid is 11 or greater, as for example OH- and CH3CH2O-

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Summary of substitution vs. elimination reactions for haloalkanes

SN1/E1: Primary reaction if: poor nucleophiles/weak bases if the solvent is polar protic

SN2: Never observed b/c of extreme crowding around the tertiary carbon

E2: Main reaction with strong bases such as HO- and RO-

100


Summary of substitution vs. elimination reactions for haloalkanes

SN1/E1: not observed

SN2: primary reaction if: Good nucleophiles and weak base (I- or CH3COO-)
 

E2: primary reaction if: Strong, bulky bases [ (CH3)3CO-]

Neither SN1 nor E1 likely due to primary cations rarely being formed in solution

101

Walk through the logic for determining which substitution or elimination reaction if....

R-group is primary and sterically unhindered

1. R-group is primary: no SN1/ E1

2. Is the Nuc/Base a strong base and hindered?:

If yes, alkene product via E2 (rare)

If no, proceed to second question:

3. Is the Nuc/Base a good nucleophile?:

If yes, substitution product via rapid SN2 (common)

If no, substitution product via slow SN2

103


What are the only attractive forces between alkene molecules?

Dispersion forces

105


What does an HDI of zero indicate?

  • compound does not possess any rings or pi bonds

106


What does an HDI of 4 indicate?

  • Indicates the likely presence of an aromatic (benzene) ring

107

What is a phenyl group: draw it and list all abbreviations

A more specific reference for a certain type of aryl group:

In organic chemistry, the phenyl group or phenyl ring is a cyclic group of atoms with the formula C6H5. Phenyl groups are closely related to benzene. Phenyl groups have six carbon atoms bonded together in a hexagonal planar ring, five of which are bonded to individual hydrogen atoms, with the remaining carbon bonded to a substituent

In essence, it is a benzene ring with ONLY ONE substituent

Abbreviations:

  1. C6H5--
  2. Ph--

108


What is an aryl group: draw it and list all abbreviations

In the context of organic molecules, aryl refers to any functional group or substituent derived from an aromatic (benzene) ring.

In essence, it is any benzene ring with one or more substituents. VERY GENERAL.

Abbreviations:

  1. Ar--

 

109

What is the chemical shift?

4.5- 6.5 ppm

111

What is the chemical shift?

2-5 ppm

113

What is the chemical shift?

~0.9 ppm

114


What is the chemical shift?

~1.7 ppm

116


What is the chemical shift?

~2 ppm

118


What is the chemical shift?

6.5 -8 (normally 7) ppm

119


What is the chemical shift?

~12 ppm

120

What is the chemical shift?

~2.5 ppm

121


What is the chemical shift?

~1.2 ppm

122

What is the chemical shift?

~2-4 ppm

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What is the chemical shift?

~10 ppm

124


(alkene reaction)

What is the function for:

DMS (Dimethyl Sulfide) / Zn
[Ozonolysis (reductive)]

Presumably used for reduction

125

(alkene reaction)

What is the function of:

BH3 / THF
[Hydroboration]

EN difference between H and B actually favors H, giving H a negative charge and B a positive charge, which leads to the syn addition of BH3 to double bonds and the formation of a square intermediate

126

(alkene reaction)

What is the function of:

CH2Cl2 / CCl4
[General Addition, Halogenation]

Generic organic solvent. Doesn’t really do anything, but it’s designed to not get in the way

127

(alkene reaction)

What is the function of:

H2O
[Halohydrin Formation, Acid-Catalyzed Hydration]

Used as a nucleophile in the first and as a base to deprotonate in the second

128

(alkene reaction)

What is the function of:

H2O2
[Hydroboration]

Used with NaOH to remove BH2+ intermediate

129

(alkene reaction)

What is the function of:

Hg(CF3COO-)2
[Alkoxymercuration]

Functions the same as Hg(OAc)2

Functions like an X2 by creating an ion ring intermediate and allowing the Markovnikov addition of the alcohol to the double bond. Advantage is that it can be removed by NaBH4

130

(alkene reaction)

What is the function of:

HX, X = halogen
[General Addition]

Acidic H from polarized H-X bond easily adds to a double bond

131

(alkene reaction)

What is the function of:

KMnO4
[Dihydroxylation/Diol formation, Ozonolysis (Oxidative)]

  • K is just used to form a salt. Behaves like OsO4 under cold and dilute conditions (By some orgo magic, can grab both sides of a double bond and eventually disappear for syn diol addition.)
  • Under heat or acidic conditions, will follow the ozonolysis (oxidative) pathway

132

(alkene reaction)

What is the function of:

NaBH4
[Oxymercuration]

[Alkoxymercuration]

Used to remove Hg based intermediate

133

(alkene reaction)

What is the function of:

NaOH
[Hydroboration]

  • Used with H2O2 as a strong base to remove the BH2+ intermediate
  • Often used to supply OH-, which is used in deprotonation steps

134

(alkene reaction)

What is the function of:

X2, X= halogen
[Halogenation, Halohydrin Formation]

Most halogens are found as diatomic gases. Covalence allows X-X bond to break rather easily when polarized by a double bond

135

(alkene reaction)

What is the function of:

H2SO4
[Acid-Catalyzed Hydration]

Used as a strong acid generate hydronium ion (H3O+), which is a starting reactant for the hydration. A good strong acid to use since the conjugate base does not compete with the double bond of the alkene as a nucleophile.

136


What is the pka of:

CH2=CH2

CH2=CH2 pka=44

137

What is the pka of:

CH3CH3

CH3CH3 pka=50

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What is the pka of:

NH3

NH3 pka=36

141

What is the pka of:

HC[triple bond]CH

HC[triple bond]CH pka=25

142


What is the shift effect, and draw the NMR puzzle piece for:

  • The alpha position of an alkyl group near the oxygen of an alcohol or ether

Effect: +2.5 ppm

143


What is the shift effect, and draw the NMR puzzle piece for:

  •     The alpha position of an alkyl group near the oxygen of an ester

Effect: +3 ppm

144


What is the shift effect, and draw the NMR puzzle piece for:

  •     The alpha position of an alkyl group near the a carbonyl group

Effect: +1 ppm

145

What is the term used to classify benzene and its derivatives?

Arene or aromatic

146

~0.9 ppm

What is the chemical shift?

147


What is the pka of:

H2O

H2O pka = 15.7

147


What is the pka of:

HF

HF pka=3.2

148

~1.2 ppm


What is the chemical shift?

149

~1.7 ppm


What is the chemical shift?

150

~10 ppm

What is the chemical shift?

151

~12 ppm


What is the chemical shift?

152

~2 ppm


What is the chemical shift?

153

~2-4 ppm

What is the chemical shift?

154

~2.5 ppm

What is the chemical shift?

155

 

What does an HDI of 1 indicate?

  • Compound has either a ring or one pi bond

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