ORGO TEST 3- CARBOXYLIC ACIDS

Grignard Trend (strongest to weakest)

I > Br > Cl > > > F

Carboxylation of Grignard Reagent

1. Mg

2. CO2

3. H3O+

Acetal Formation

1. start with an aldehyde or a ketone. NO CARBOX ACID

2. react with 2 equivalents of alcohol (R-OH)

3. the alcohol is the nucleophile

4. the order is acid nuc nuc acid nuc nuc

5. the acids only protonate, the nucs either add on or deprotonate

Reagents that Oxidize to Carboxylic Acids/Make them

1. Na2Cr2O7/H2SO4/H2O/heat

2. KMNO4/OH-/heat

3. ozonolysis of an alkene

4. carboxylation of grignard (the thing with CO2)

LiAlH4

1. reduces a carboxylic acid to a primary alcohol. ALWAYS a PRIMARY alcohol. reduces basically everything except alkenes and alkynes

2. the carbonyl carbon takes an H from the Li thing but the arrow is coming from the bond of H to Al (idk why?)

3. the oxide? that was the carbonyl oxygen then attacks the Al of the AlH3 situation and Li is just floating around

4. the Al stuff can still react so basically acid workup happens where the bond of the now FOUR Al things takes an H from an acid and the Al thing just comes off

5. you should end up with FOUR PRIMARY ALCOHOLS and some like water and Li and Al

Imine Formation

1. start with ONLY KETONE or ALDEHYDE, not carboxylic acid

2. needs primary AMINE

3. the amine adds SN2-like at first

4. there is a “leave as water” step

5. in the end there is a C to N DOUBLE BOND

Enamine formation

1. the same as imine formation

2. SECONDARY AMINE USED

3. in the end there is a C to C DOUBLE BOND bc u take a beta hydrogen

Wittig Reaction

1. KETONE/ALDEHYDE to ALKENE

2. use the PPh3 ylid thing

3. forms a box at some point

4. u should end up with at least O double bond PPh3

5. unstable ylid=CIS

6. stable ylid=adjacent EWG and resonance stablized=TRANS

Least Stable to Most Stable, Most Reactive to Least Reactive

1. acid chloride

2. anhydride

3. imide

4. aldehyde

5. ketone

6. lactone

7. ester

8. lactom

9. amide

10. nitrile

11. imine

12. carboxylate

Carboxylic Acid Reactions that are Acidic Conditions

1. esterification

2. acetal formation

3. imine formation

4. PROTONATE THE CARBONYL OXYGEN

Carboxylic Acid Reactions that are Basic Conditions

1. Saponification

2. Grignard

3. Reduction

4. Amidation?

5. DEPROTONATE

Acidity

1. alkyl groups=negliglable effect

2. halogens=higher EN means higher acidity

3. the closer halogens are to the carbonyl, the more acidic they are

4. double and triple bond=more acidic

Acid Catalyzed Esterification

1. need an alcohol and some acid

2. carbonyl oxygen deprotonates the acid (except sometimes the alc takes an H from the acid?? idk bro)

3. shuffle stuff around until water leaves

4. you should end up with carbonyl bound to an oxygen thats bound to an R group

5. the O next to R in the product is always from the nucleophile/alcohol

Making Acid Chlorides

1. Use Thionyl Chloride

2. the carbonyl O is NOT getting protonated here, it really doesnt do anything

3. the OH oxygen on carbox acid attacks the sulfur bc the sulfur really wants electrons

4. one of the chlorides leaves but it comes back later and adds onto the carbonyl carbon

5. that rlly big thing with the O connected to the sulfur leaves at some point

Base Reaction

1. base will deprotonate that OH

2. then u can do like SN2 with the resulting carboxylate

Synthesis of Symmetrical Anhydride

1. use a catalyst like P2O5, POCl3, or P4H10

2. its that thing with the like 2 carbonyls and O in the middle connecting them

Synthesis of Asymmetrical Anhydrides

1. use a base like NEt3, ofc that deprotonates to make ur carboxylate

2. do some SN2 type stuff on a carbonyl with a LG

3. the leaving group leaves duh

4. boom anhydride

Decarboxylation

1. simple carbox acids dont do allat

2. u need alpha-beta-keto carbox acid

3. malonic acid and its relatives like to decarboxylate tho

4. u need heat 

5. its kind of like a cyclic mechanism, basically a CO2 should be leaving or else yikes

6. the carbonyl with the R group on it takes the H from OH, then u should see that CO2 should leave idk

7. should be forming a ketone

Saponification

1. “base” attaches to carbonyl

2. that O-R thing gets kicked off

3. the kicked off O-R deprotonates the base that got added, forms that ion thing

4. the ion thing gets protonated by acid, done

Acid Cat. Hydrolysis: Amide to Carboxylic Acid

1. acidic conditions, so acid protonates O of carbonyl first

2. then the water/base/nucleophile? attacks the carbonyl carbon

3. then water deprotonates the water that just got added, that new water turns into H3O+

4. the nitrogen takes an H from h3o+ (becomes water), the whole nitrogen group thing leaves and the carbonyl oxygen slams down its lone pair

5. then the water deprotonates the carbonyl oxygen, becomes H3O+, that H3O+ protonates the nitrogen thing that came off

6. then done 2 products

NaBH4 in Alcohol Solution

1. some type of cyclic situation is happening first, so the carbonyl oxygen takes an H from the alcohol solvent. then the bond between a H and the like OCH3 part of the alcohol attacks the B. then the bond between BH3 and H attacks the carbonyl carbon

2. thats it

3. reduces aldehydes and ketones, nothing else really

Acid Catalyzed Hydrolysis of Nitriles in Acid

1. use H2SO4 in water and heat

2. the water takes an H from the H2SO4. VERY IMPORTANT. becomes H3O+

3. then the nitrogen takes an H from. H3O+

4. do the resonance structure where a lone pair ends up on nitrogen and there is a double bond instead of triple

5. water attacks the carbon of that double bond

6. another water deprotonates the attached water

7. the lone pairs on nitrogen take an H from the new H3O+

8. tautomerization-aka the lone pair on oxygen slams down to form carbonyl, the double bond with nitrogen is kicked out and turns into lone pair on N

9. then you deprotonate the carbonyl oxygen with water

10. boom done, but the product is lowkey still prone to hydrolysis