Exam 3 reagents

General reaction of a thioacetal?

ketone → sulfur+ replaces oxygen + R group

What reagent can remove thioacetals?

H2/Raney Ni

How can you remove the carbonyl from a ketone?

Using Zn(hg)/ HCl, or H2NNH2/KOH

What are the 3 additions of nitrogen nucleophiles?

Amine (NH3 or primary) → imine, Amine (secondary) + ald/ket → enamine, Hydrazine (H2NNH2) or Hydroxil (HO-NH2)→ hydrazone or oxime

What is reductive amination?

imine → secondary amine

What reagents can be used for reductive amination?

H2/Ni, pt/Pd , ***or*** 1. NaBH4 2. H+ wkup, ***or*** 1. LiAlH4 2. H+ wkup

What are the reagents to change an aldehyde/ketone to an imine?

What reagents can be used to turn an imine to an aldehyde/ketone?

H2O/H+

What can you make from a secondary amine with an aldehyde/ketone?

enamine

What are the reagents to turn a secondary amine + aldehyde/ketone → enamine?

Secondary amine + H+

For secondary amine + ald/ket → enamine, if the adjacent C are different, take the H+ that gives you the ___________ alkene

more substituted

What can you make from a hydrazine and an ald/ekt?

hydrazone

What are the reagents used to turn an ald/ket into a hydrazone?

Hydrazine (H2NNH2)/H+

What can you make from an ald/ket and a hydroxil?

oxime

What reagents are used to turn an ald/ket into an oxime?

hydroxil (HO-NH2)

How can you turn a primary alcohol into an aldehyde?

A weak oxidizer

How can you turn an aldehyde into a carboxylic acid?

Strong oxidizer

What are the 2 oxidations of aldehydes?

A.) Jones or KMnO4 B.) 1. Ag2 prime, -OH 2. H3O+

What are the 7 ways to synthesize amines?

1\.) reductive amination

2\.) Reduction of amides

3\.) Reduction of nitriles

4\.) Reduction of nitro

5\.) Reduction of an azide

6\.) Reduction of an oxime

7\. ) Alkylation of amines

What are the steps to synthesize an amine using reductive amination?

start with an aldehyde/ket → imine → reduce the imine → amine

(\*there should be an H in the imine in the picture)

What reagents reduce an imine to an amine?

NaBH4/H+ wkup, or H2/ metal catalyst

What kind of amine is formed from reductive amination?

Secondary amine

How can you turn an amide into an amine?

Reduction

What is the result of an amide and 1. LiAlH4 2. H+ wkup?

an amine

What reagents turn an amide into an amine?

1\. LiAlH4 2. H+ wkup

Do methods to remove carbonyls work with amides?

No

How can you turn a nitro group off a benzene into an amine?

reduction

What reagent turns a nitro group off a benzene into an amine?

H2/Ni

What are the steps of the reduction of an azide?

SN2 reaction → reduction

What are the steps of the reduction of an oxime?

Create oxime → reduce

What amines can react in alkylation?

primary, secondary, tertiary

What happens first in an alkylation of an amine?

SN2

Why is there a secondary reaction in the alkylation of an amine?

the newly formed amine can react again with the starting alkyl halide to create a secondary amine

What reagent changes an amine to a salt? (benzene)

NaNO3/HCl

What is the result of an ald/ket with a primary amine and H+?

an imine

What is the result of an imine and 1.NaBH4 2. H+ wkup or 1. H2/metal catalyst

a secondary amine

What is the result of an amide and 1. LiAlH4 2. H+wkup?

a primary amine

What is the result of a nitrile and 1. LiAlH4 2. H+ wkup?

a primary amine

What is the result of a nitro group off a benzene and H2/Ni?

An aniline

What is the result of an azide, 1. NaN3 2. LiAlH4 2. H+ wkup?

a primary amine

What is the result of An epoxide , 1. NaN3 2. H+ wkup 3. LiAlH4 4. LiAlH4 5. H+ ?

An alcohol and amine on either side of the original double bond, trans stereochemistry

What is the result of an oxime and 1. LiAlH4 2. H+ wkup?

an amine

What is the result of an alkyl halide and an amine (any classification)?

1. an amine → second reaction with original alkyl halide → secondary amine

What is the result of an amine off a benzene ring and NaNO3/HCl?

\+N2 off the benzene

What are the ways you can synthesize COOH?

1\. Oxidation of Alkenes

2\. Ozonolysis

3\. Oxidation of primary alcohols

4\. Oxidation of aldehydes

5\. Oxidizing the benzylic position

6\. Hydrolysis of nitriles

7\. Carbonation of grignards

How can you for COOH from an alkene?

Oxidation using KMnO4

What is the result of an alkene and KMnO4?

2 Carboxylic acids

How can you make COOH from an alkene (second way)?

Ozonolysis, using reagents of 1. O3 2. H2O2

What is the result of an alkene and 1. O3 2. H2O2?

COOH

How can you make COOH from a primary alcohol?

H2CrO4 (jones)

What is the result of a primary alcohol and jones?

COOH

How can you make COOH from an aldehyde?

Jones or KMnO4 or 1. Ag2, -OH 2. H3O+

What is the result of an aldehyde and Jones?

COOH

What is the result of an aldehyde and KMnO4?

COOH

What is the result of an aldehyde and 1. Ag2O, -OH 2. H3O+?

COOH

What is the result of a benzene and KMnO4?

COOH on the benzylic positions (as long as there is a hydrogen available)

How can you create COOH off a benzene ring?

KMnO4

Under what conditions can hydrolysis of nitriles be performed?

Acidic and basic

What are the reagents used to create COOH from a nitrile, under acidic conditions?

H+/H2O/heat or H3O+/heat

What is the result of a nitrile and H+/H2O/heat or H3O+/heat?

COOH

What are the reagents used to create COOH from a nitrile?

1. -OH, H2O, heat 2. H+ wkup

What is the result of a nitrile and 1. -OH, H2O, heat 2. H+ wkup?

COOH

How can you create COOH from grignards?

CO2 and H+

What is the result of a grignard , CO2, and H+?

COOH

What are the reactions of COOH?

1\. Fischer Esterification

2\. COOH with diazomethane

3\. Amide formation

4\. Acid chloride formation

5\. Decarboxylation

\

What is the result of a COOH , ROH and H+?

an ester (fischer esterification)

Making a lactone

Making a hemiacetal

What is the result of COOH and diazomethane (CH2N2) ?

An ester

What is the result of COOH , primary amine, and heat?

An amide

What is the result of COOH and SOCl2 or PCl5?

acid chloride

What are the two types of decarboxylation?

beta-keto acid, malonic acid/diacid

What is the result of a beta-keto acid and heat?

ketone and CO2 (decarboxylation)

What is the result of malonic Acid/Diacid and heat?

COOH and CO2

What reagent turns beta-keto acid into a ketone and CO2?

heat

What reagent turns malonic acid/diacid into COOH and CO2?

heat

What can react with H2O nucleophile?

1\. Acid Chlorides

2\. Acid Anhydrides

3\. Esters

4\. Amides

\

How can you form COOH from acid chloride?

H2O, pyridine

What is the result of an acid chloride, H2O, and pyridine?

COOH + HCl

How can you form COOH from acid anhydride?

H2O

What is the result of an acid anhydride and H2O?

COOH

What is the result of an asymmetric anhydride and H2O?

2 COOH forms

How can you form COOH from an ester?

H2O/H+ (acid) or H2O, -OH, H+ wkup (base)

What is the result of an ester and H2O/H+?

COOH

What is the result of an ester and H2O, -OH, H+wkup?

COOH

What is the name of the base reaction of ester and H2O?

Saponification

How can you make COOH from an amide?

H3O+/H+ (acid) or -OH, H2O, H+ (basic)

What is the result of an amide and H3O+/H+?

COOH and NH3

What is the result of an amide, -OH/H2O/H+?

COOH

What is your nucleophile in hydrolysis?

H2O

What do you form with an alcohol as your nucelophile?

an ester

What will react with an alcohol nuc?

1\. Acid chloride

2\. Acid anhydride

3\. Esters

How can you form an ester from an acid chloride?

alcohol, pyridine

What is the result of an acid chloride, and alcohol, and pyridine?

ester

How can you make an ester from an anhydride?

alcohol

What is the result of an acid anhydride with an alcohol?

an ester

What is the name of the reaction of an ester with an alc nuc?

transesterification

How can you make an ester from an ester and alcohol?

alcohol/H+

What is the result of an ester, alcohol, and H+?

ester

What can react with an amine nuc?

1\. Acid chloride

2\. Anhydride

3\. Ester