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80 Cards in this Set
- Front
- Back
What is a carboxyl group?
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A carbonyl attached to a hydroxyl group
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Acetic acid is derived from __ via fermentation
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ethanol
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acid or base
what are CA's? |
acid
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When a CA does give away a proton, the leftover electrons are resonated b/w ___ atoms
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two oxygen
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CA has a hydrogen bond ___ and ___ in the same functional group, leading to ____ intermolecular forces and ___ B.P.'s
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donor, acceptor, large, high
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The carbonyl carbon is ____
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electropositive
*so it makes it a great electrophile |
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CA's have the ___ priority in nomenclature
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highest
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t or f
CA's occur widely in nature and are synthesized by all living organisims |
t
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CA's are always named by adding the suffix...
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-oic acid
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What are the common and IUPAC names of the first 3 carboxylic acids?
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methanoic acid => formic acid
ethanoic acid => acetic acid propanoic acid => propionic acid |
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Cyclic carboxylic acis are usually names as what?
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cycloalkane CA's
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Salts of CA's are named beginning with the ___, followed by the ____.
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cation, name of the acid with the ending -ate
Ex) Sodium hexanoate |
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What is a dicarboxylic acid?
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Molecules with two carboxyl groups on the same molecule
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What are the first 6 straight chain terminal dicarboxylic acids?
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oxalic
malonic succinic glutaric adipic pimelic |
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polar or non polar
What are CA's? |
polar
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Can CA's form hydrogen bonds with each other?
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yes
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As a result of hydrogen bonding CA's can form what?
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dimers
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Define dimers?
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pairs of molecules connected by two hydrogen bonds
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Multiple hydrogen bonds ___ the boiling and melting point of CA's
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elevate
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BP ___ with increasing MW
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increase
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CA's acidity is due to what?
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resonance stabilization of the carboxylate anion
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What happens when the hydroxyl proton dissociates from the acid?
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The negative charge left on the carboxylate group is delocalized b/w the two oxygen atoms
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Name 2 ways to stabilize the negative charge to increase acidity:
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1. electron withdrawing groups (halides)
2. groups that allow more resonance stabilization (benzyl or allyl) |
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How does electron withdrawing groups influence acidity?
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Absorbs the negative charge and increases acidity
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How does electron donating groups influence acidity?
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Donates additional electron density and destabilizes the negative charge, making the compound less acidic
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In dicarboxylic acids, one -COOH group influences the other, making the compound what?
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more acidic
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Beta-dicarboxylic acids are notable for what?
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high acidity of the alpha-hydrogens located on the carbon b/w the two carboxyl groups
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CA's are the most ___.
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oxidized
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CA's can be prepared via oxidation of...
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aldehydes, primary alcohols, and certain alkylbenzenes
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What oxidant is normally used to oxidize CA's?
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KMnO4
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Why can't secondary and tertiary alcohols be oxidized to carboxylic acids?
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B/c of valence limitations
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Organometallic reagents react with ___ to form ___.
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CO2, CA's
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Give an example of an organometallic reagent
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Grignard reagents
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Carboxylation of organometallic reagents is useful for the conversion of ___ alkyl halides into CA's
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tertiary
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Carboxylation of organometallic reagents adds ___ carbon atom to the chain
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one
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Nitriles are also called what?
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cyanides
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HYDROLYSIS OF NITRILES
The cyanide anion carries the ___ charge on the ___ atom, making it a great ___, but not a great ___. |
negative, carbon, nucleophile, base
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HYDROLYSIS OF NITRILES
The cyanide anion will displace __ and ___ halides in a typical SN2 fasion |
primary and
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HYDROLYSIS OF NITRILES
Nitriles can be hydrolyzed under either __ or __ conditions |
acidic, basic
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HYDROLYSIS OF NITRILES
This reaction allows for the conversion of ___ into ___. |
alkyl halides, CA's
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HYDROLYSIS OF NITRILES
As in the carboxylation reaction, an additional __ is introduced into the chain |
carbon
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What do long chain carboxylic acids form when they react with sodium or potassium hydroxide?
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salt
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How do you make soap?
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by mixing fat (triglycerides) with lye (sodium hydroxide)
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Why can salts solvate nonpolar organic compounds in aqueous solutions?
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They possess both a nonpolar tail and polar carboxylate head
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Define micelles
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soap molecules that arrange themselves in spherical structures
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SOAP FORMATION
The ___ face outward, where they can be solubilized by water, the ___ are oriented inward where it is protected |
polar heads, nonpolar hydrocarbon chains
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Many of the reactions in which CA's participate proceed via a single mechanism called what?
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nucleophilic acyl substitution
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Nucleophilic acyl substitution is similary to...
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nucleophilic addition to a carbonyl
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Carboxylic acids and esters can only be reduced by __ and not the less reactive ___.
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LiAlH4, NaBH4
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most or least
CA's occupy the ___ oxidized end of the oxidation-reduction continuum |
most
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yes or no
Can CA's be further oxidized? |
no
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LAH reduces CA's to ___.
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alcohols
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Show reduction of a CA mechanism
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carboxylic acid => aldehyde => alcohol
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Reduction of a CA occurs by nucleophilic ____ of ____ to the carbonyl group
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addition, hydride
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How do you synthesize esters?
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react CA's with alcohols under acidic conditions
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Ester formation is a ____ reaction, so ___ is a side product.
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condensation, water
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ESTER FORMATION
In acidic conditions, the ___ on the C=O can be protonated. This enchances the ___ of the bond, putting more ___ charge on the C, and making it ___ susceptible to nucleophilic attack |
O, polarity, positive
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ESTER FORMATION
This condensation reaction occurs most rapidly with ___ alcohols |
primary
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Whats another name for acyl halides?
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acid halides
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What are acyl halides?
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Compounds with carbonyl groups bonded to halides
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How is thionyl chloride written?
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SOCl2
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What does thionyl chloride do?
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A reagent that can convert CA's into acyl halides
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reactive or nonreactive
Acid cholorides. |
reactive
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Acid chlorides are frequently used as ____ in the conversion of CA's to ___ and ___.
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intermediates, esters and amides
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What biochemical pathway is decarboxylation most common in?
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Krebs Cycle
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What is decarboxylation?
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loss of a carbon
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Whenever we want to get rid of a carbon on the MCAT, it will be lost in the form of ___?
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CO2
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t or f
Acid chlorides are most stable and least reactive |
f
Acid chlorides are the least stable and the most reactive |
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____ and other ____ may spontaneously decarboxylate when heated.
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1,3 Dicarboxylic acids and other beta-keto acids
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DECARBOXYLATION
the carboxyl group is lost and replaced with what? |
hydrogen
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DECARBOXYLATION
Because both the electrophile and nucleophile are in the same molecule, the reaction proceeds.... |
through a six membered ring transition state
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DECARBOXYLATION
The ___ that is initially formed from the destruction of the ring tautomerizes to the more stable __ form. |
enol, keto
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The more stable the ___ is, the more likely it is that the ___ will leave
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conjugate base, proton
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CA stability is determined by what 3 factors?
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-periodic trends (electronegativity, and thus, induction)
-size of the anion (HF is a weaker acid than HI) -resonance |
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The acidity of a CA is enhanced by...
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resonance b/w its oxygen atoms
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Primary alcohols or aldehydes can be ___ by CA's
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oxidized
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What 2 ways can CA's be synthesized?
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-from the carbocation of organometalic reagents
-by hydrolyzing nitriles |
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Carboxylic acids can be reduced to primary alcohols or stopped at the aldehyde level with a...
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bulky hydride reagent
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CA's with long chains form soaps when neutralized with ___ or ___.
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NaOH or KOH
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1,3 Dicarboxylic acids and other beta-keto acids may spontaneously decarboxylate when heated producting...
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a ketone and carbon dioxide
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