Chapter 20-22: Organic Chemistry II

alipathic acids have an _____ group bonded to _____ while aromatic acids have a _____ group

alkyl; COOH; aryl (ring)

in IUPAC names, the carbon of the carbonyl is labeled number _____. the -e from the alkane is removed and the ending adds _____acid

one; -oic

aromatic acids are named as derivatives of _____ _____with ortho, meta, para substituents

bezoic acid

carboxylic acids have a high _____ _____ compared to alcohols, ketones, or aldehydes of similar molecular weight due to stable _____-_____ dimer

boiling point; hydrogen bond

carboxylic acid may dissociate in water to give a _____ and a _____ ion 

proton; carboxylate 

a reaction between carboxylic acid and water has a lower _____ than alcohol and water due to _____

EA; resonance

acetate ion _____ stable than alkoxide due to delocalization of negative charge over two oxygens

more

the magnitude of substituent effect depends on the _____ from the carboxyl group

distance

the more halide substituents on a molecule, the stronger the _____ effects and the stronger the _____

inductive; acid

electron-withdrawing groups enhance the _____ acid strength and electron donating groups _____ the acid strength

increase; decrease

acid strength effect are strongest for _____ and _____ positions

ortho; para

adding strong acid like, HCl, regenerates the _____ _____ through protonation 

carboxylic acid 

carboxylate salts of Na+, K+, Li+, and NH4+ are _____ in water

soluble

saponification

basic hydrolysis of fat and oils produces soap

primary alcohols and aldehydes are oxidized with _____ _____, cleavage of alkene with _____ produces carboxylic acid if vinylic hydrogen present

chromic acid, KMnO4

alkyl benzenes are oxidized to benzoic acid by hot _____ or hot _____ acid

KMNO4; chromic acid 

carboxylation of grignard reagents:

• grignard reagents react with CO2 to product, after protonation, _____ _____.

• reaction sometimes called “_____ _____” and increases the number of _____ in the molecule by one

carboxylic acid; CO2 insertion; carbons

basic or acidic hydrolysis of nitrile (-CN) produces a _____ _____. whole reaction adds extra _____ to molecule

carboxylic acid; carbon

acid derivatives: 

• -OH: _____ _____ 

• -Cl: _____ _____ 

• -OR’: _____ 

• -NH2: _____ 

• these interconvert via _____ _____ substitution 

• carboxylic acid 

• acid chloride 

• ester 

• amide 

• nucleophilic acyl 

in fischer esterification, reaction of carboxylic acid with alcohol under acidic conditions produces an _____. to drive equilibrium toward formation of products, use large excess of _____

ester; alcohol

synthesis of amides:

• heating this salt well above _____ degrees celsius drives off steam and forms an amides

100

LiAlH4 reduces carboxylic acids to _____ _____. the intermediate aldehyde reacts _____ with reducing agent than carboxylic acid 

primary alcohol; faster

the best reagents for converting carboxylic acids to acid chlorides is _____

SOCl2

esterification of acyl chloride is more _____ than the fischer esterificiation

efficient

ammonia and amines react with acid chlorides to give _____ in _____ synthesis

amides; amide

lactones are_____ _____. IUPAC names are derived by adding term lactone at end of parent _____. lactams are _____ _____. IUPAC names are derived by adding term lactam at the end of the parent _____

cyclic esters; acid; cyclic amides; acid

amide is a composite of a _____ _____ , _____, or _____. ammonium salts are converted to _____ at high temperatures

carboxylic acid; ammonia; amine; amides

amides are extremely weak _____

bases

atoms at the ends of triple bonds are _____ hybridized and a bond angle of _____

sp; 180

acid halides are the most _____ than carboxylic acid derivative. acid halides are also called _____ halides

reactive; acyl

acid halides are named by replacing the -ic acid suffix name with _____ and the halide name

-yl

anhydride means without _____

water

acid chloride is most _____ then _____

reactive; anhydrides

acid anhydrides are _____ derivatives of carboxylic acid

activated

acid anhydrides are named by replacing the word acid with _____

anhydride

nucleophilic acyl substitution is also called _____-_____ mechanism because the _____ is eliminated and the _____ is regenerated

addition-elimination; LG; carbonyl 

tetrahedral intermediate is when the _____ adds to the _____

nucleophile; carbonyl

more reactive can be _____ to less reactive derivatives

converted

in acid chloride to amide and anhydride to amide:

• ammonia yields _____ amide

• primary amine yields a _____ amide

• secondary amine yields a _____ amide

primary; secondary; tertiary

in ammonolysis (ester to amide), the nucleophile must be _____ or _____ amine. requires prolonged _____

NH3; primary; heating

alkoxide (-OR) is a strong _____ and isn’t usually good leaving group, except in _____ step

base; exothermic

hydrolysis of acids occur _____even in moist air with no acid or base catalyst 

heating with aqueous base or acid will hydrolyze a nitrile to a _____ _____

carboxylic acid

LiAlH4 or LAH reduces esters, acids, and acyl chlorides to _____ _____

primary alcohols

LiAlH4 reacts faster with _____ _____ than with aldehydes

acid chlorides

DIBAL is a _____ _____ agent that can reduce an esters to _____

reducing agent; aldehydes

grginards reagents add _____ to acid chlorides and esters to give rise to _____ after protonation

twice; alcohols

anhydride synthesis between the reaction of _____ _____ and _____ _____or salt

acid chloride; carboxylic acid

mechanism of beta-lactam acylation, includes the _____ attacking the carbonyl of the four membered ring. _____ reformed after tetrahedral intermediate and the _____ bond is eliminated and _____as the last step

nucleophile; carbonyl; nitrogen; protonated

in crossed claisen, no alpha carbons and no alpha hydrogens makes the carbon a good _____ 

electrophile

ketones are more _____ than esters and therefore more likely to _____to serve as an enolate in crossed claisen condensation

acidic; deprotonate

for typical acidities of carbonyl compounds, when an oxygen can’t give 100% to a specific carbon, the pka is _____. if one carbonyl occupied was surrounded by two lone pairs to make new double bonds, the molecule is more _____ and there is a _____ pka. becomes _____ if there is oxygen can give 100%

high; stable; higher; acidic

an enolate is a _____ and _____ _____

nucleophile; lewis base

conjugate additions for the michael reaction have unusually _____ double bonds

electrophilic

michael donors are _____ and michael acceptors are _____ (conjugated)

nucleophiles; electrophiles

attacks occurring at the beta position causes the oxygen atom to be numbered as the _____ atom counting from the nucleophile in a 1,4 addition

fourth

best way to make ester

acid + alcohol with H+

best way to make amide

acid chloride + amine with base

enolate formed using bulky bases like LDA goes for the easiest H and is ____ favored

kinetically

enolate formed using non-bulky bases like OH, NaOCH3 becomes the more substituted enolate and is ___ favored

thermodynamically

tautomerization goes from the ___ molecule to the ___ molecule in 1,4-addition to conjugated carbonyl (Michael Reaction)

enol; ketone (>99%)