Final Exam Review

CHE 321

Fall 2013

The final
Thursday, December 12, 8:00 10:45 AM Probably 18 multiple choice @ 5 pts, about 12 short answer @ 5 10 Rooms to be announced ONE index card Cover page at http://www.ic.sunysb.edu/Class/orgchem/che321/Exam_Cover.pdf
Synthesis library pKa table Chemical shift table IR peak table

Please remember to fill out

The undergraduate TA feedback survey
accessible from an email in your *@stonybrook.edu inbox Closes Thursday, December 12, at 7:00 AM

The official course evaluation

Accessible at https://stonybrook.campuslabs.com/courseeval/ Closes Monday, December 9, at 11:59 PM

Your presenters this evening are

Chapter 9: Jonathan Khan Chapter 10: Shawn Raghunandan Chapter 11: Pradeep Ravindra Chapter 12/Synthesis: Arthur Makarenko

Nuclear Magnetic Resonance Spectroscopy

Jonathan Khan
Solomons, T. W. G., Organic chemistry.

2013, Jonathan Khan. Under no circumstances may any part of this presentation be duplicated or used for commercial purposes. This material may not be reproduced for any use without explicit permission of the author.

Brief Review of Spectroscopy

Spectroscopy is defined as the interaction of matter with electromagnetic radiation (light).

The technique is always the same, expose a sample of your molecule to a specific type of electromagnetic radiation, collect data, the make a conclusion based off of the absorption/emission pattern of the molecule.

Spectroscopic Assays of CHE 321

Different forms of spectroscopy allow us to probe a molecule in various ways to gain different data about the molecule in question.
IR spectroscopy allows us to qualitatively analyze a molecule for the presence of functional groups
NMR spectroscopy allows us to quantitatively and qualitatively analyze a molecule for the presence of specific functional groups and the way in which they are associated.

NMR Spectroscopy
Certain atomic nuclei such as 1H and 13C behave as if they were bar magnets spinning around an axis. When placed into a strong magnetic field and subsequently irradiated with electromagnetic radiation (usually in the radio range), these nuclei absorb some of the energy in a process called magnetic resonance. Each chemically inequivalent proton will resonate at a different frequency characteristic of the functional group to which it belongs.

Applied Magnetic Fields

Normally, the spin axes of the spin-active nuclei in the molecule are disordered. When placed into a strong magnetic field, the spin axis of the spin-active nuclei align with the applied magnetic field.
Solomons, T. W. G., Organic chemistry.

Magnetic Resonance
When a pulse of electromagnetic radiation (specifically radio waves) is applied to the molecules in the magnetic field, it causes some of the spin-active nuclei to flip.
This causes the spin of the flipped nucleus to be aligned against the magnetic field. As the strength of the applied magnetic field increases, the energy required to flip the nuclei also increases

Solomons, T. W. G., Organic chemistry.

Chemical Shifts
For each nuclei resonating at a particular energy value, we see one signal on our spectrum corresponding to that energy value. An increase in resonance energy results in a higher ppm.

The position of the signal on the spectrum allows us to determine the chemical environment that the proton is sitting in.
For a standard proton spectrum, the value of the chemical shift will almost never go beyond 13ppm. Upfield and downfield are terms used to describe the position of the signal on the spectrum.
Downfield means at a higher ppm

Upfield means at a lower ppm

Shielding
Shielding is a term used to describe the relative strength of the induced magnetic field felt by the proton. Caused by circulating electrons The magnetic field felt by a particular proton can be either:
Stronger than the applied field
Deshielded proton, caused by a decrease in electron density. Electronegative functional groups such as carbonyls and halogens draw electrons away from other groups

Weaker than the applied field

Shielded proton, caused by an increase in electron density. sp3 carbons are a good example, many -bonds increase the electron density around a particular set of protons.

Solomons, T. W. G., Organic chemistry.

NMR Spectrum

Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Common Chemical Shifts and Their Meaning

Solomons, T. W. G., Organic chemistry.

Clicker Question
How many 1H signals will this molecule give?
A. 9 B. 10 C. 11 D. 12 E. 13 F. 14
Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Clicker Question
How many 1H signals will this molecule give?
A. 1 B. 3 C. 4 D. 5 E. 6 F. 7
Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Integration Values
The height of a signal is called the integral The height of each peak represents the relative number of protons in the molecule which resonate at a particular chemical shift.

Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Signal Splitting
Splitting is only seen in 1H spectra. Splitting arises due to changes in magnetic field caused by adjacent inequivalent protons.

Equivalent protons will not split each other.

Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Splitting
Splitting patterns can be predicted via the n+1 rule
N is the number of adjacent protons which are chemically inequivalent from our proton of interest. Addition of one to n, affords the splitting pattern. Protons used for n have to be chemically equivalent to each other, but inequivalent from the proton of interest. If there is more than one type of adjacent proton, such as on a double bond, the n+1 rule is done for as many proton types present. ABC because there is no free rotation around a double bond due to the pi bond. HA feels R and HB, HB feels HA and HC, while HC feels HB and R. therefore these protons are all in different chemical environments.

Pascals Triangle
Splitting for a particular proton can also be determined by using Pascals Triangle. Each row (n) represents the splitting pattern of a proton with (n) number of adjacent equivalent protons. If a particular proton has more than one type of adjacent proton, use Pascals triangle for each type of proton.
1 11 121 1331 14641 1 5 10 10 5 1 1 6 15 20 15 6 1 (0) (1) (2) (3) (4) (5) (6)

Clicker Question
How many peaks will the proton on the carbon be split into?
A. 1, singlet B. 2, doublet C. 3, triplet

D. 4, quartet
E. 4, doublet of doublets F. 6, triplet of doublets
Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

13C

Spectroscopy

Theoretically identical to proton spectroscopy. Rules for13C spectroscopy

No splitting No integration 1 peak per type of carbon

To interpret 13C spectra:

Find the peak

Go to the provided chart and match the chemical shift values to the corresponding functional group.

Clicker Question
How many 13C signals will this molecule give?
A. 11 B. 12 C. 13 D. 14 E. 15 F. 16
Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Clicker Question
How many 13C signals will this molecule give?
A. 1 B. 3 C. 4 D. 5 E. 6 F. 7
Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Exam Problems

 Since we are given the spectra of C, we will start with C.

Doublet at 9.75, 1H
Aldehyde

Move onto A.
Ozonolysis oxidizes olefins to carbonyls

Ozonolysis of A affords only C.

Therefore A is symmetrical

Multiplet at 2.75, 1H
-proton

Doublet at 1.0, 6H
Dimethyl

Oxidation with OsO4 affords a meso compound B.

Identifies the substitution pattern on olefin.

 And finally D
Reaction of A with CH2I2 and Zn(Cu) affords a hydrocarbon. CH2I2 and Zn(Cu) convert olefins into cyclopropanes via addition of a carbene.

Credit to Anthony Antonelli for this

Citations
All exam questions were taken from old exams posted on: http://www.ic.sunysb.edu/Class/orgchem/che321/oldexams.php All other images and figures were taken from: Solomons, T. W. G., Organic chemistry. Structures for the clicker questions were taken from: Ojima, I.; Chen, J.; Sun, L.; Borella, C. P.; Wang, T.; Miller, M. L.; Lin, S. N.; Geng, X. D.; Kuznetsova, L. R.; Qu, C. X.; Gallager, D.; Zhao, X. R.; Zanardi, I.; Xia, S. J.; Horwitz, S. B.; Mallen-St Clair, J.; Guerriero, J. L.; Bar-Sagi, D.; Veith, J. M.; Pera, P.; Bernacki, R. J., Design, synthesis, and biological evaluation of new-generation taxoids. J Med Chem 2008, 51 (11), 3203-3221.

Acknowledgements
Teaching me NMR
Joshua Seitz Jacob Vineberg Prof. Isaac Carrico Farhan Ahmed

Assistance with this presentation

Eman Kazi

Some kid named Peter Giattini

Formation & Reaction of Radicals

Heterolysis

A : B A+ + B:Reaction is heterolytic meaning we cleaved the bond giving the electrons to B creating an anion plus A a cation.

Formation & Reaction of Radicals

Homolysis

A:B

. A+

. B

Reaction is homolytic meaning we dissociated the bond and created two equal pieces. (two free radicals) Curved arrows should be half arrows Useful with alkanes with no functional group

Conditions for radical reaction

R O O R heat 2R O

Cl

Cl

2 Cl

In order for radical reaction to occur we need conditions of heat or light.

Radical Stability
We consider carbon radicals to be electron deficient. o o o Allylic > Benzylic >3 > 2 > 1
CH3 CH3 C CH3 > CH3 H C CH3 > CH3 H C H>H H C H

(positive inductive effect of alkyl groups stabilize radical)

Benzylic Radical

Resonance still holds true here with Benzylic radicals. The radical can be delocalized by the double bonds present in the benzene ring.

Allylic Radical
Allylic Radicals act similar to Benzylic radical in terms of resonance.

Radically Hideous

C H 2C CH 3

Equivalent to

Requires more energy to create and is less stable than Allylic, tertiary, secondary, and primary.

Mechanism of Radical Reactions

There are three steps in a radical reaction.
Initiation Propagation Termination

Initiation
In this step you create your two radical species.
Possible (common) initiation reactants
X:X (halogens)
Br, Cl,

RO:OR H:X
Br, Cl, F, etc..,

Initiation Mechanism with Cl:Cl

h (homolytic cleavage)

Cl

Cl

2 Cl

Propagation With CH4

There are multiple possible propagation step which is determined by the number of reactants.

Note that that the propagation step can occur more than twice

Propagation Continued

This can be done until all the Hydrogens have been replaced by Cl.

Termination
There are several termination steps.
Basically you need to radicals to react in order to cancel the reaction out.

Excess amounts of reactants

CH4 (large excess) + Cl2

h
CH3Cl (mainly) CH4 + Cl2 (large excess) h CCl4 (mainly)

Selectivity of Br and Cl
Bromine is more selective than Chlorine
Bromine tends to go for the more stable Radical Chlorine tends to go for the more available positions

Chlorine Selectivity
What is the major product? A B

A C

B D

Bromine & Chlorine

Radical addition of Alkenes

Generally HBr follows Markovnikovs rule

With peroxide
Anti-Markovnikovs rule
HBr RO OR heat H Br not Br H

Which is the correct Product?

Br HBr
RO:OR Heat

A
(via more stable 2o carbocation)

B
HBr RO-OR RO:OR Heat heat
Ch. 10 - 55

Br (via more stable 2o radical)

O Br H3C O
Heat

Br H3C

What are the products of the initiation step?

O H3 C O Br

A
H

O Br H2 C O

CH3 radical
O C O

P1
P2 T

Br

H3C

O Br HC 3 O HC 3 Br

CH

+
HC 3 O

O H3C O

Br

Br H3C O

Bond Energies and Delta H

Bond Energies
The amount in kJ it takes to break a bond

Observation of Delta H
Negative Delta H (exothermic) Positve Delta H (endothermic)

Bond Energies

Bond Energies
Which bond has a higher bond dissociation?

Bond Energies

Calculating Delta H
Never base your calculations off of
Reactants - Products This may work sometimes but not always.

To calculate Delta H
Use: bonds broke bonds formed

Calculating Delta H

a. -101 b. 117 c. 101

Delta H

The Delta H for step 3 is +8kJ mol-1 and 109 kJ mol-1 for step 2. A. True B. False

Chapter 11 Final Review

By Pradeep Ravindra

Physical Properties of Alcohols/Ethers

Boiling Point Ethers similar to hydrocarbons of same molecular weight Alcohols higher boiling points than ethers and hydrocarbons Solubility Ethers and alcohols of same molecular weight have similar solubility Alcohol solubility decreases as length of hydrocarbon chain attached increases (i.e. Butyl Alcohol > Pentyl Alcohol) Branching increases solubility (i.e. Isobutyl Alcohol > Butyl Alcohol)

Alcohol Capabilities
Lone pairs on oxygen atom make it both basic and nucleophilic. Hydroxyl (OH) groups are also very poor leaving groups. Lets examine what different scenarios there are. Basicity: The alcohol, in the presence of a strong acid (H-Cl, H-Br, H+), will become protonated, converting it into a great leaving group (H2O)

Alcohol as a Leaving Group: With the presence of a nucleophile, we have a substitution reaction, with the leaving group being water.

Therefore, by converting an alcohol to a group that departs as a weak base (i.e. H2O, CH3OH, CH3CH2OH), we form a good leaving group. This allows elimination and substitution reactions to occur.

Conversion of Alcohols into Alkyl Halides

Goal: Substitute an alcohol with a halogen Method: Treat the Alcohol with either a strong acid or a reagent that will convert it into a suitable leaving group Reagents: Hydrogen Halides (HCl, HBr, HI) Substitute a halide (SN2 for primary alcohols, SN1 for Secondary, Tertiary, Allylic, and Benzylic Alcohols). Phosphorus Tribromide (PBr3) Substitute a Br (SN2) Thionyl Chloride (SOCl2/Pyridine) Substitute a Cl for primary or secondary alcohols (SN2 Mechanism for both) Zinc Chloride (ZnCl2) Substitute a Cl for a primary (SN2) or secondary (SN1) Alcohol

Hydrogen Halides
Order of Reactivity Degree of alcohol: 3 > 2 > 1< methyl By acid: HI > HBr > HCl (HF is generally unreactive) Mechanism: SN1 for Secondary, Tertiary, Allylic, and Benzylic Alcohols SN2 for Primary Alcohols Remember for SN1, since a carbocation forms, hydride and methyl shifts will occur to stabilize it if able. Will produce both front and back attack products due to planar transition state of carbocation. For SN2, the reaction is concerted meaning that the nucleophile comes in from the back side of the leaving group as it leaves.

Other Ways to Make a Hydroxyl Group of an Alcohol a Good Leaving Group

Conversion to a sulfonate ester derivative: Common sulfonate esters: mesylates (OMs), tosylates (OTs), triflates (OTf) Reagents: 1. OMs, OTs, or OTf with pyridine 2. R-OH Group These reactions retain the configuration of the OH (no affect on stereochemistry) These sulfonate esters are very good leaving groups because the sulfonate anions that they become are very weak bases Useful for setting up a substitution reaction or elimination reaction

Sulfonate Esters

Forming Ethers by Intermolecular Dehydration of Alcohols

Earlier, it was mentioned that oxygens lone pairs make it both basic and nucleophilic Steps: 1. For the formation of diethyl ether, H2SO4 at a warm temperature is used to protonate the OH group, forming H2O+ in one molecule of ethanol. 2. Then, another molecule of ethanol by SN2 attacks the carbon bonded to the H2O+, forcing it to leave as water.

3. Finally, the H2O that left the first molecule of ethanol acts as a base and deprotonates the alcohol, forming diethyl ether

Williamson Synthesis of Ethers

SN2 Reaction of a sodium alkoxide with an alkyl halide, sulfonate, or sulfate Use: to synthesize an Ether from an Alcohol Method: Use a Hydride to pull off a proton from the Hydroxide to form a nucleophile, then have it react with an alkyl halide (halogens are good leaving groups) Reagents: R-OH, NaH, R-X (Alkyl Halide)

Synthesis of Ethers by Alkoxymercuration-Demercuration

Protecting Primary Alcohols

Using a tert-butyl ether, you can protect a hydroxyl group of a primary alcohol in order to carry out a reaction in different part of the molecule

Can be removed with a diluted acid

Silyl Ether Protecting Groups for Alcohols

Protecting groups allow you to use reagents in a synthesis that would otherwise unintentionally interact with the Alcohol group. Stable between pH 4 and 12
You can just write this as OTBS

TBS-Cl DMF

Synthesis Example
Starting with this reactant, make the product

??????

How to make an Epoxide

Alkene Epoxidation (turns an Alkene into an Epoxide) NOTE: MCPBA is a specific type of peroxy acid. RCO3H is the generic formula for a peroxy acid. They are equivalent reagents, for your purposes.

Example of use:

(Notice how you can abbreviate it over an arrow. Much simpler!)

Stereochemistry of Epoxidation
Recall that double bonds can be Cis or Trans

Epoxidation is a SYN Addition The oxygen atom can add to either face of an Alkene.
Therefore, if the molecule you form doesnt have a plane of symmetry, you end up with a Racemic (Equal amounts of R and S) Mixture. In the example below, since cis-2-Butene has a plane of symmetry, you actually form a MESO compound, meaning that it has no enantiomer (its suspected enantiomer is actually identical to it) If I had cis-2-pentene, would I form a meso compound after Epoxidation? Draw it out!

Uses of an Epoxide
So weve made an Epoxide. Whats so special about it? As it turns out, since three-membered rings are highly strained, epoxides are much more reactive towards Nucleophilic Substitution (SN) than other ethers Say I wanted to undergo Nucleophilic Substitution. How do we break this highly strained ring? Choose your poison: 1. Acid Nucleophile forms on more stable carbocation (usually higher degree carbon) 2. Base - Nucleophile forms on least sterically hindered carbon (usually lower degree carbon) Remember that the nucleophile comes in from the backside of the epoxide, so the nucleophile and the OH group will be anti with each other

Fill in the reagents

Answers

Review

Answers

Predict the product(s) formed when the following reactants are treated with excess H-Br:

Answers

Mechanism Practice

Mechanism Practice

Challenge your knowledge

CHAPTER 12 OVERVIEW

Arthur Makarenko

OXIDATION-REDUCTION

Oxidation- increasing the oxygen content or decreasing the hydrogen content of an organic molecule Reduction- opposite of oxidation, increasing the hydrogen content or decreasing the oxygen content of an organic molecule

REDUCING AGENTS
-lithium aluminum hydride reduces

aldehydes, ketones, esters, and carboxylic acids to alcohols. -sodium borohydride only reduces aldehydes and ketones to alcohols.

PRACTICE PROBLEMS
Would you use LiAlH4 or NaBH4 for the following reactions?

PRACTICE PROBLEMS
Would you use LiAlH4 or NaBH4 for the following reactions?

B A A

OXIDIZING AGENTS

PRACTICE PROBLEMS
What reagents are needed to carry out the following reactions?

A B C D E

PCC KMnO4 H2CrO4 H2CrO4 and KMnO4 All of them

PRACTICE PROBLEMS
What reagents are needed to carry out the following reactions?

A D
E

A B C D E

PCC KMnO4 H2CrO4 H2CrO4 or KMnO4 Any of them

ORGANOLITHIUM

GRIGNARDS REAGENTS
Exactly the same as the organolithium reaction!

Preparation of Grignard reagents:

GRIGNARDS REAGENTS
An ester can react with two equivalents of a Grignard reagent.

RESTRICTIONS OF ORGANOMETALLICS
Organometallic reagents cannot be prepared in the presence of these groups

In the presence of an alcohol, a protecting group may be implemented to carry out a organometallic reaction. To apply the TMS protecting group, react the alcohol with TMSCl. To remove it, react with fluoride.

SODIUM ALKYNIDES
Can also perform nucleophilic attack on carbonyls

ORGANOMETALLIC REAGENTS AS BASES

competition between a nucleophilicity and a basicity is the reason why organometallic reactions cannot be performed with certain functional groups.

SYNTHESIS REVIEW

Arthur Makarenko

PROPOSE A SYNTHESIS OF THE FOLLOWING COMPOUND FROM REACTANTS CONTAINING FOUR CARBON ATOMS OR LESS

A OR

Na NH3

H2 Lindlar

OR

H2 Lindlar

H2 Lindlar PCC

H2 Lindlar PCC

1. 2. H3O+

1. 2. H3O+

OR

H2 Lindlar PCC

1.

2. H3O+

H2 Lindlar PCC

1.

A
2. H3O+

H 2O HOH 3 O+ LDA

B
C

H2 Lindlar PCC

1.

2. H3O+

LDA

H2 Lindlar PCC

1.

2. H3O+

LDA

PROPOSE A SYNTHESIS OF THE FOLLOWING COMPOUND FROM REACTANTS CONTAINING FOUR CARBON ATOMS OR LESS

Which bond is best to break?

1.

2. H3O+

1.

2. H3O+

Li

1.

2. H3O+

A B

HBr PBr3 BOTH WORK

Li

1.

2. H3O+

Li
PBr3

1.

2. H3O+

Li
PBr3

1.

2. H3O+

PROPOSE A SYNTHESIS OF THE FOLLOWING COMPOUND FROM REACTANTS CONTAINING FOUR CARBON ATOMS OR LESS

F-

F-

1. NaH

2.

F-

1. NaH 1. 2. H3O+

2.

F-

1. NaH 1. 2. H3O+ PCC

2.

F-

1. NaH 1. 2. H3O+ PCC 1. 2. H3O+

2.

F-

1. NaH 1. 2. H3O+ PCC 1.

2.

Li
2. H3O+

F-

1. NaH 1. 2. H3O+ PCC 1.

2.

Li
2. H3O+ TMSCl