Term
| the rate-limiting step of nuceleophilic acyl substitution? |
|
Definition
| the addition step is rate limiting |
|
|
Term
| factors that determine the reactivity of carboxylic acid derivatives? |
|
Definition
| both steric and electronic factores |
|
|
Term
| more/less polarized acid derivatives are more/less reactive |
|
Definition
| more polarized acid derivatives are more reactive |
|
|
Term
| you can convert _____ reactive derivatives into _______ reactive derivatives |
|
Definition
| you can convert more reactive derivatives into less reactive derivatives |
|
|
Term
| order of reactivity of derivatives: |
|
Definition
| acid chloride> acid anhydride> thirster> esters> (aldehydes > ketones > carboxlic acids)> amides |
|
|
Term
| hydrolysis of der with water yields? |
|
Definition
|
|
Term
| alcoholysis of der with alcohol yields? |
|
Definition
|
|
Term
| aminolysis of der with ammonia or amine yields? |
|
Definition
|
|
Term
| reduction of der with hydride reducing agent yields? |
|
Definition
|
|
Term
| reduction of amide with hydride reducing agent? |
|
Definition
|
|
Term
| carboxylic acids can be converted to acid chlorides with? |
|
Definition
|
|
Term
| Acid Anhydrides are usually formed by? |
|
Definition
| heating the corresponding carboxylic acid to remove 1 eq. of water |
|
|
Term
| Sn2 reaction of a carboxylate and an alkyl halide yields? |
|
Definition
|
|
Term
| acid-catalyzed reaction of a carboxylic acid and an alcohol yields? aka? |
|
Definition
ester
reaction aka Fischer esterification |
|
|
Term
| Fischer esterification (what, reversible/irreversible, etc) |
|
Definition
ester produced by acid-catalyzed reaction of carboxylic acid and an alcohol
-mineral water makes the acyl carbon more reactive towards the alcohol
- can be driven to completion by removine the water or by using a large excess of alcohol |
|
|
Term
| amides are difficult to form from carboxylic acids because? what can be used? |
|
Definition
| because amines convert the carboxylic acids to carboxylate salts that no longer have electrophilic carbons. DCC can be used in labs. |
|
|
Term
| what is used to convert carboxylic acids to amides? |
|
Definition
|
|
Term
| reduction of carboxylic acids to alcohols? |
|
Definition
|
|
Term
| carboxylic acid halides prepared by? |
|
Definition
| reacting carboxylic acid with SOCl2 or PBr3 |
|
|
Term
| Acyl halides are ____ reactive |
|
Definition
|
|
Term
| acyl halides react with _____ to form carboxylic acids. the reaction mixture usually contains a ____ to scavenge the ___ produced. |
|
Definition
water
Reaction mixture contains a base to scavenge the HCl produced. |
|
|
Term
| Acid halides react with _________ to form anhydrides |
|
Definition
|
|
Term
| acyl halides react with _______ to form esters. _____ added to ____. |
|
Definition
alcohols
base added to scavenge HCl |
|
|
Term
| reactivity order of alcohols |
|
Definition
| Primary > Secondary > Tertiary |
|
|
Term
| acid chlorides react with _____ to give amides. To scavenge the HCl? |
|
Definition
ammonia & amines
To scavenge HCl, either 2 eq of ammonia/amine must be used OR NaOH must be present |
|
|
Term
| LiAlH4 reduced acid halides to ______? |
|
Definition
|
|
Term
| Reaction of acid halide with grignard yields? |
|
Definition
|
|
Term
| reaction of acid halide with organocopper reagent yields? |
|
Definition
ketone
*does not occur with any other carboxylic acid derivatives |
|
|
Term
| acid anhydride can be prepared by reaction of carboxylate anions with? (for symmetrical/unsymmetrical?) |
|
Definition
acid chlorides
symmetrical and unsymmetrical can be prepared through this route |
|
|
Term
| acid anhydrides react more slowly than? |
|
Definition
|
|
Term
| often used to prepare acetate esters? |
|
Definition
|
|
Term
| reactions of acid anhydrides efficient/inefficient? why? |
|
Definition
| inefficient because half of molecule is unused |
|
|
Term
| 3 methods of preparing esters? |
|
Definition
1. Sn2 reaction of a carboxylate anion with an alkyl halide
2. fischer esterification
3. reaction of an acid chloride with an alcohol in the presence of base |
|
|
Term
| ester are less reactive than _____ & _____? |
|
Definition
| acid halides and acid anhydrides |
|
|
Term
| hydrolysis: loss of alkoxide ion yields a __________ which is deprotonated to give a ________ anion. |
|
Definition
| loss of alkoxide ion yields a carboxylic acid which is deprotonated to give a carboxylate anion |
|
|
Term
| usual route of acidic hydrolysis? |
|
Definition
| reverse of Fischer esterification |
|
|
Term
| ester can be converted into amides by? easier to start with? |
|
Definition
heating with ammonia/amines
but it's easier to start with acid chlorides |
|
|
Term
| LiAlH4 reduces esters to ? |
|
Definition
|
|
Term
| DIBAH at -78 degrees C reduces esters to ? |
|
Definition
|
|
Term
| ester react _______ to produce tertiary alcohols with _____ |
|
Definition
| esters react TWICE WITH GRIGNARDS to produce tertiary alcohols with 2 IDENTICAL SUBSTITUENTS |
|
|
Term
| amides prepared by reaction of ? |
|
Definition
| acid chlorides with ammonia/amines |
|
|
Term
| hydrolysis of amides is different from the hydrolysis of other acid derivatives because ? |
|
Definition
| the conditions are more severe |
|
|
Term
| acid hydrolysis of amides occurs by addition of water to a ___________, followed by ______________________. |
|
Definition
| acid hydrolysis of amides occurs by addition of water to a protonated amide, followed by loss of ammonia or an amine |
|
|
Term
| basic hydrolysis of amides occurs by attack of ___, followed by _____________. |
|
Definition
| basic hydrolysis of amides occur by attack of HO-, followed by loss of -NH2 |
|
|
Term
| LiAlH4 reduces amides to ? |
|
Definition
|
|
Term
|
Definition
|
|
Term
| __________ & ___________ react to form a polyamide |
|
Definition
| diamine & diacid chloride |
|
|
Term
| ___________ & ____________ react to form a polyester |
|
Definition
|
|
Term
|
Definition
|
|
Term
| NMR characteristics for carboxylic acid derivatives? |
|
Definition
| not useful to distinguish among carboxylic acid derivatives |
|
|
Term
| acid hydrolysis of amides occurs by addition of water to a ___________, followed by ______________________. |
|
Definition
| acid hydrolysis of amides occurs by addition of water to a protonated amide, followed by loss of ammonia or an amine |
|
|
Term
| basic hydrolysis of amides occurs by attack of ___, followed by _____________. |
|
Definition
| basic hydrolysis of amides occur by attack of HO-, followed by loss of -NH2 |
|
|
Term
| LiAlH4 reduces amides to ? |
|
Definition
|
|
Term
|
Definition
|
|
Term
| __________ & ___________ react to form a polyamide |
|
Definition
| diamine & diacid chloride |
|
|
Term
| ___________ & ____________ react to form a polyester |
|
Definition
|
|
Term
|
Definition
|
|
Term
| NMR characteristics for carboxylic acid derivatives? |
|
Definition
| not useful to distinguish among carboxylic acid derivatives |
|
|
