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56 Cards in this Set
- Front
- Back
- 3rd side (hint)
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resonance
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acidity
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groups that increase acidity
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COOH
NO2 CN SO3H HALOGENS |
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groups the increase basicity
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NH2
CH3 C2H5 OH OCH3 OC2H5 |
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alpha protons in aldehydes and ketones
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are acidic
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what mechanism when an alkene is made in alcohol dehydration?
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E1
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E2 mechanism, also yields and alkene. What are the cutting tools?
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secondary and tertiary halides do the E2 with Strong Bases:
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NaOH
NaOCH3 NaO2H5 NaNH2 t-butoxide LDA |
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how to clean house?
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excess NaNH2, NH3 in H2O
Double dehydrohalogenation |
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meta directors
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deactivate the ring by withdrawing electrons,
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they are:
NO2, COOH, SO3H, CN, NH4, CF3, CCL3, CBr3, C=O |
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O/P DIRECTORS
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activate the ring by donating electrons,
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they are
NH2, OH, CH3, C2H5, HALOGENS, O-CH3, O-C2H5 |
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Oxidation
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we add Os or remove Hs1
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1* alcohols oxidize into
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carboxy acids or aldehydes depending on reagents
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K2CR2O7 (or Jones reagent): COOH
PCC: ALDEHYDES 3* alcohols do not oxidize |
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2* alcohols with any of the oxidizing reagents give
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ketones
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Hydrolysis of an ester
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in acid yeilds COOH
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rxn is reversible
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base-promoted ester hydrolysis
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sponification
faster than in acid, but irreversible |
oh is consumed in rxn and is a reagent vs just a catalyst
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failure of a gringard
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a gringard will fail if an acidic group is present
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Diels-Alder
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a conjugated diene reacts with a dienophile to form a 6 C ring
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diene contributes 4 Cs to the ring
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hydrolysis of an anhydride
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yields 2 carboxy acids when an anhydride breaks in 2 halves
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Claisen Condensation
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react an ester with an alpha H in base to form a Beta Keto Ester
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always assume 2 moles of reactant
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The Dieckman Reaction
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with a diester and form 5 or 6 rings. An internal Claisen.
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look for a diester
A 4 carbon span is a 5 carbon ring, a 5 carbon span is a 6 carbon ring. |
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Wittig
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an aldehyde or ketone > alkene
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phosphorane
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esterification
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acid + alcohol > ester + h20
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Aldol
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look for an aldehyde or simple ketone in dilute acid or base with an alpha H
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reducing sugar
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when a hemiacetal group is present
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anomers
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alpha and beta glucose
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if the OH groups opposite to e/o are both pointing downward, it's alpha. If one is up, but the other is down, it's a beta sugar.
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sucrose
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a disaccharide which breaks down into glucose and fructose
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what group is missing on a sucrose molecule?
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hemiacetal, it's a non-reducing sugar
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sucrose sucks!
The only way this ring can open up and close ( go from alpha to beta) is if there was a hemiacetal group. |
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anomers differe in stereochemistry at
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C1
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electrophoresis
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separate out proteins based on charge
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Disulfide bonds in proteins
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-result from oxidation of RSH
-can be broken by reduction reactions -function to help maintain the shape of proteins -link two cysteine amino acid residues |
disulfide bonds are found in antibodies
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SN2
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100% inversion
bimolecular best in polar aprotic solvents ( no H-bonding) works best with strong nucleophiles (CN-) |
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SN1
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reactivity is faster for 3* halides
unimolecular, nucleophile independent(carbocation) partial inversion and partial recemization polar protic solvents |
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Gabriel Synthesis
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to make a 1* amine
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malonic ester synthesis
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used to make carboxy acids
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hoffman rearrangement
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look for an amide with 2 h2
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if N has R groups > NR
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hoffman elimination
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a 1* amine is best made by azide or gabriel synthesis. monoalkylation is tough to stop
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ligand
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a lewis base that is part of a complex ion
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the ligand and the metal center are joined by a coordinate covalent bond
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Amines
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organic derivatives or Ammonia
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NH3
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4* Amine
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salt
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when are amines water soluble?
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where there are fewer than 4 Cs
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due to H bonding
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are amines more basic than alcohols, ethers, or h2o?
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yes
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large Kb
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amide
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1. An organic compound, such as acetamide, containing the CONH2 radical.
2. A compound with a metal replacing hydrogen in ammonia, such as sodium amide, NaNH2. |
non-basic due to resonance stabilization
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amine geometry
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trigonal pyramidal
sp3 hybridization |
amines with 3 different substituents on the N are chiral
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what is unique about amine chirality as opposed to alkane chirality?
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amines cannot be resolved ( separated) into their two enantiomers because the two enantiomeric forms rapidly interconvert by Pyramidal Inversion
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what can be said about Aromatic amines and their basicity?
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they are less basic than aliphatic amines because their anion is rosnance stabilized.
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when an amine acts as a base, it accepts a proton.
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2 ways to makehttp://www.flashcardexchange.com/mycards/add/846418 a 1* Amine
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Azide synthesys and Gabriel Synthesis
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do nucleophiles attack benzene?
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no. benzene is only attacked by electrophiles, nucleophiles are repelled.
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2* Amines can react with an Aldehyde or Ketone to yield?
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an Enamine
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The Cope Elimination
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N-Oxide formation
Another reaction in which a nitrogen atom acts as a Nu This is a Syn Elimination Remove the H from the Beta C with most Hs |
3* Amines
hydroxide ion is displaced from hydrogen peroxide by the tertiary amine to give a hydroxy ammonium ion and hydroxide ion. hydroxide ion then removes a proton to give the amine oxide or N-oxide. |
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Hoffman Elimination
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Frome the less substituted alkene
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Hofmann degradation of amines
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use iodomethane to form 4* Ammonium Salts
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use methylation and NOT protonation to convert an amino group from a poor to a good LG for an elimination reaction
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Hofmann Rearrangement
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shroten the chain by one carbon and change the amide into an amine
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Claisen Rxn
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analogous to the Aldol Condensation
Form a Beta keto ester |
react an ester with an alpha H in base.
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Aldol Condensation
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When an aldehyde or simple ketone containing an alpha hydrogen is treated with dilute base or acid a reaction occurs whereby we form a beta-hydroxy carbonyl compound
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lactone
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cyclic ester
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why are aldehydes more reactive than ketones?
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because they are easier to attack
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enolization
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process by which a hydrogen attached to the alpha C of the carbonyl moves to the carbonyl O
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tautomers
constitutional isomers |
