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145 Cards in this Set

  • Front
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azido-
RN3
diazo
RN2+
determination of enantiomeric rotation
cannot be determined by structure, only experiment
stereoisomers
differ only by how atoms are oriented in space
E/Z
Z is when highest priority on same side
R/S
R is CW, S is CCW
diastereoisomers
stereoisomers that are not mirror images
possible stereoisomers
with n stereocenters, 2^n
meso compound
molecule with 2 or more chiral centers with a plane of symmetry (no optical activity)
torsional strain
when cyclic molecules must assume conformations with eclipsed interactions
nonbonded strain
sterric hindrance when atoms/groups compete for the same space
nucleophilicity of nucleopiles with same attacking atom
increases with basicity with same attacking atom
nucleophilicity in protic solvents
doesn't correlate to basicity, instead usually large nucleophiles that can shed solvent are better (I-,HS-,RS- > Br-, HO-, RO-, CN-, N3- > NH3, Cl-, F-, RCO2- > H2O, ROH > RCO2H
nucleophilicity in aprotic solvents
because nucleophiles are naked so basicity is again defines strength of nucleophile (F- > Cl- > Br- > I-)
leaving group ability
best groups are weak bases (can accept electron pair) (I- > Br- > Cl- > F-) (best groups are TsO-, H2O, NH3, worst groups are OH-, NH2-, RO-)
SN1 conditions
stabilized intermediate by polar/protic solvent, needs good leaving group, favored by bulky nucleophiles at more substituted carbons
SN2 conditions
strong nucleophile, less substituted carbons, best in apolar solvents, less bulky nucleophiles work
degrees of unsaturation
N=(1/2)(2n+2-m)

N is number of double bonds or rings
formula: CnHm
E1 conditions
highly polar solvent, branched carbon chains, good leaving group, weak and low concentration of nucleophiles, favored over SN1 by higher temperatures (hard to control, though)
E2 conditions
sterric hindrance is less of an issue for E2 than SN2 (no backside attack), strong base favors E2 and weak lewis base/good nucleophile favors SN2
anti-Markovnikov halide addition to alkene
radical addition of halogen (Br plus hv)
1,2 diol from alkene
cold, dilute potassium permanganate
oxidation of alkenes (carboxyllic acids and ketones)
Add potassium permangante, hydroxide, heat followed by acidic workup (break through double bond form carboxyllic acid for singly substituted and ketone for double substituted, CO2 for terminal)
ozonolysis
alkene can be turned into aldehyde by ozone in dichloromethane followed by zinc and water (alcohol formation is sodium borohydride and methanol)
alkene to epoxide
peroxycarboxylic acids (m-chloroperoxybenzoic acid)
polymerization of alkene
radical carbon, heat high pressure (radical mechanism, sometimes anionic or cationic)
n-butyl lithium
acts as base to form acetylide ion which can nucleophilically attack an alkyl halide to add that R group
alkyne to cis alkene
H2, Pd, barium sulfate and quinoline
alkyne to trans alkene
sodium, liquid ammonia
hydroboration of alkynes
internal: add BH3 to form BR3 (R=alkene), then acetic acid to form three enols (tautomerize to ketone)
terminal: must start with BR2H with H2O2 and hydroxide (aldehyde/enol)
alkyne oxidation to acids
internal: potassium permanganate/hydroxide followed by acidic workup
terminal: ozone in carbon
tetrachloride followed by water workup
aromatic halogenation
Br: Br2/FeBr3, Cl: Cl2/FeCl3 (AlCl3), F: multisubstituted, I: not reactive
aromatic sulfonation
sulfur trioxide and sulfuric acid with heat (adds SO3H)
aromatic nitration
nitric acid and sulfuric acid (passes through nitronium ion electrophilic intermediate, which loses proton)
Friedel-Crafts acylation
carbocation electrophile (acyl chloride) is incorporated with AlCl3 to add carbonyl onto ring
activating and ortho/para
NH2, NR2, OH, NHCOR, OR, OCOR, R (all electron-donating)
deactivating and ortho/para
halogens (weakly electron withdrawing)
deactivating and meta
NO2, SO3H, carbonyls (COOH, COOR, COR, CHO) (electron withdrawing)
aromatic reduction
H2, Rh/C at high temperature and pressure
acid/ester reduction
LAH, acid (acid to alcohol, ester to ether)
ketone/aldehyde reduction
sodium borohydride and acid (both form alcohols)
aniline to phenol
nitrous acid/sulfuric acid to form diazonium salt, addition of acid displaces to form phenol
alcohol to alkene
sulfuric acid and heat, hydride shift can occur to form more substituted double bond
conversion of OH leaving group
acid to form water, tosyl chloride to form tosylate
alcohol to alkyl halide
SOCl2 to form inorganic ester which is displaced by chloride to form alkyl halide (PBr3 for bromide)
PCC reagent
converts primary alcohol to aldehyde
secondary alcohol to ketone
sodium dichromate, sulfuric acid OR CrO3 and sulfuric acid in acetone
primary alcohol to acid
sodium dichromate and sulfuric acid OR CrO3 and sulfuric acid in acetone OR potassium permanganate
phenol to quinone
sodium dichromate and sulfuric acid
Michael addition
form enolate carbanion by strong base (LDA, KH) by anstraction of proton between two carbonyls, adds to beta carbon of alpha,beta-unsaturated carbonyl compound
hydrate formation
addition of water to carbonyl
acetal formation
addition of alcohol to aldehyde
ketal formation
addition of alcohol to ketone
cyanohydrin formation
addition of cyanide to carbonyl (OH and CN on same carbon)
imine formation
addition of ammonia to carbonyl (reactive pair of lone pair electrons on nitrogen after addition)
aldol condensation
in base, enolate from one carbonyl adds to another carbonyl (acid, enol) to form beta-hydroxy ketone (heat and base allows for elimination to alpha,beta-unsaturated carbonyl)
Wittig reaction
formation of ylide after reacting (C6H5)3P with alkyl halide (phosphonium salt), ylide attacks carbonyl, cyclic mechanism forms C-C double bond (strong P=O bond formed drives reaction)
oxidation of carbonyls to acids
potassium permanganate, CrO3, silver oxide, hydrogen peroxide
reduction of carbonyl to alcohol
LAH or sodium borohydride
Wolff-Kishner reduction
carbonyl is converted to hydrazone, releases N2 when heated in base to alkane (mercury and zinc in HCl works for compounds unstable in base)
ester from acid
under acidic conditions, addition of alcohol and release of water as carbonyl group reforms
formation of acid chloride
add SOCl2, PCl3, or PCl5 (for bromide add PBr3)
beta-keto acid decarboxylation
ketone oxygen grabs acid proton, which adds to C=O acid group and sigma bond connecting acid to alpha carbon breaks to form enol (ketone) and CO2
acid halide reactions
hydrolysis to carboxylic acid, conversion to ester and HCl by alcohol addition, amide formation in excess ammonia (2 equiv.), F-C acylation, reduction by H2/Pd/BaSO4 to aldehyde
anhydride synthesis
acid chloride plus carboxylic salt or form cyclic anhydride to a 5 or 6 membered ring
anhydride reactions
hydrolysis to 2 acids, ammonia cleavage to amide and acid, ester conversion by alcohol, F-C acylation with AlCl3 to add acid part to ring
formation of amides
react acid chloride with amine (not teritary, no hydrogens to lose)
amide to amine
LAH reduction (no carbon atom is lost, as in Hoffmann rearrangement)
Hoffmann rearrangement
addition of BrO- to amide, Br adds to nitrogen, proton is removed from nitrogen to form a negatively charged nitrogen, R group attacks nitrogen while lone pairs attack CO carbon and Br acts as leaving group (nitrene is negatively charged nitrogen, isocynate is back-to-back O,C,N double bonds with N bound to R
ester reactions
hydrolysis (saponification) by acid or base, conversion to amide (NH3 displaces), transesterification (exhange of alcohols), Grignard addition (forms tertiary alcohol through ketone intermediate), Claisen condensation to beta-keto ester, hydrolysis by LAH to 2 alcohols (CO and OR bond split)
Claisen condensation
enolate ester adds to another ester to form beta-keto ester and an alcohol leaving group
reactivity of acid derivatives
acyl halides > anhydrides > esters > amides
amine synthesis
react alkyl halide with ammonia, to prevent extra reactions with alkyl halides NH3 should be joined with o-phthalic acid to form phthalimide (good nucleophile when deprotonated) to react with alkyl halide followed by NaOH to remove phthalic acid group
nitro compound to aniline compound
addition of zinc and dilute HCl
nitrile to amine
LAH reduction
carbonyl to amine
add amine to form imine, then H2 and Nickle (Raney Nickle) to reduce to amine (amine formed has one greater carbon connectivity than starting amine)
amine to alkene
excess MeI to form quaternary ammonium iodide salt, Ag2O/H2O forms ammonium hydroxide salt, heat displaces nitrogen group to form less substituted alkene
carbon tetrachloride
nonpolar, inert solvent
chloroform
polar, nonflammable solvent
dochloromethane
polar, nonflammable solvent
DIBAL (diisobutylaluminum hydride)
selective reduction of esters, amides, and nitriles to aldehydes
dicyclohexylborane
hydroboration of alkyne derivatives (anti-Markovnikov hydration)
dioxane
good solvent for dissolving water and organic substrates
DMD (dimethyldioxirane)
epoxidation of alkenes
DMF (dimethylforamide)
polar aprotic solvent
DMSO (dimethylsulfoxide)
polar aprotic solvent
Et2O (diethyl ether)
medium polarity solvent
Hg(OAc)2 (mercuric acetate)
oxymercuration (hydration of alcohol without unwanted rearrangements on carbocation formation), sodium borohydride is second step
HgSO4 (mercuris sulfate)
Markovnikov of alkynes
metaperiodic acid (HIO4)
oxidative cleavage of 1,2-diols
LDA (lithium diisopropylamine)
strong, hindered base
Lindlar's catalyst
Pd/CaCO3/Pb(OAc)2/quinoline; reduces alkynes to cis-alkenes
mCPBA (m-chloroperbenzoic acid)
epoxidation of alkenes
sodium nitrite (NaNO2)
diazotization of amines (with HCl)
NBS (N-bromosuccinimide)
adds bromine at allylic site
NCS (N-chlorosuccinimide)
adds chlorine at allylic site
Osmium tetroxide (OsO4)
Dihydroxylation of alkenes (1,2-diols)
triphenylphosphine (PPh3)
making wittig reagents
tetrahydrofuran (THF)
medium polarity solvent
Zn(Hg) (zinc amalgam)
Clemmensen reduction with HCl
extraction
transfer dissolved compound from one solvent into another in which it is more soluble so impurities left in first solvent
gravitation filtration
isolation of product in filtrate and leave impurities in solid (hot solvent)
vacuum filtration
isolation of solid product from filtrate
recrystalization
impure crystals dissolved in minimum amount of hot solvent and as it is cooled, the crystals reform and leave impurities behind
mixed solvent system of recrystalization
crude compound dissolves in solvent where it is highly soluble, add another solvent in which compound is less soluble in drops until crystals appear, heat solution and cool slowly for crystals
sublimation
heated solid turns directly to gas at low pressure and elevated temperature (cooled on cold finger), leaves impurities behind as they don't sublime
simple distillation
separate liquids that boil below 150 C and at least 25 C apart
vacuum distillation
boil above 150 C and at least 25 C apart (low pressure to prevent decomposition)
fractional distillation
separate liquids that boil less than 25 C apart (vaporation then condensation up a tube so material becomes more and more separated)
TLC
nonpolar compounds migrate the fasted (highest Rf values), solid phase is polar for silica gel, viewing spots by UV or iodine staining
electrophoresis migration velocity
v = (Ez/f)
E is electric field strength, z is net charge of molecule, f is frictional coefficient (depends on mass/shape)
IR
molecular vibrations (stretching, bending, rotating), fingerprint region is 1500-400 1/cm
IR peaks (alkanes, alkenes, alkynes, aromatic, alcohols)
alkane: 2800-3000 (C-H), 1200 (C-C)
alkene: 3080-3140 (=C-H), 1645 (C=C)
alkyne: 2200 (C,C), 3300 (C,H)
aromatic: 2900-3100 (C-H), 1475-1625 (C-C)
alcohols: 3100-3500 (broad)
IR peaks (ethers, aldehydes, ketones, acids, amines)
ether: 1050-1150 (C-O)
aldehyde: 2700-2900 ((O)C-H), 1725-1750 (C=O)
ketone: 1700-1750 (C=O)
acid: 1700-1750 (C=O), 2900-3300 (O-H)
amine: 3100-3500 (sharp)
NMR chemical shifts
CH3, CH2, CH, alyllyic hydrogens (.8-2.3); ketone alpha hydrogens, benzylic hydrogens, alkyne terminal hydrogens, alpha amine hydrogens (connected to carbon connected to nitrogen) (2-3); CH connected to I, Br, Cl, F, O (2.8-4.7); terminal alkene, internal alkene (4.5-5.5); aromatic hydrogens (7-7.5); aldehyde hydrogens (9-10); acid hydrogens (10-13)
coupling constant and Karplus curve
coupling constant is space between individual peaks of a pattern (same for two sets of hydrogens acting on each other), Karplus curve shows that the coupling constant is maximized when protons are anti and high when they are syn but lowest when angle between is 90 degrees
coupling constant and aliphatics
vicinal is a good amount lower than geminal
coupling constant and olefinic
maximum in trans on neighboring carbons, medium in cis on neighboring carbons (there is a small coupling between protons on the same carbon)
multiple couplings
make tree diagram with first coupling and couple this based on next sets of similar protons
sugar stereochemistry
losest OH on left is L and right is D
epimers
diastereoisomers that differ at one carbon
sugar straight chain to ring
any group on right in Fischer projection points down and groups on left point up, carbonyl carbon becomes chiral
anomers
beta is when C1 OH and CH2OH are in cis and alpha is when they are in trans, alpha is less favored because OH is made axial
Benedicts solution
Cu(OH)2, oxidizes reducing sugars that have OH on their C1 carbon
specific rotation
specific rotation=observed rotation divided by concentration (g/mL) times length (dm) (depends on number of molecules that are encountered)
alkane properties
higher moleculer weight means higher MP/BP/density, branching reduces MP/BO (fewer van der waal forces as liquid and less packing ability as solid)
alkane nomenclature
1. find longest chain
2. number chain so substiuents get lower numbers
3. name substituents (use di, tri if more than one of same group)
4. assign each substituent at number
5. list substituents in alphabetical order (ignore di,tri..., tert, sec, or n but NOT cyclo, iso, neo)
sec and iso butyl
sec is when methyl is on carbon connected to main chain and iso is when it is one further away
alkene properties
Higher MW means higher MP/BP, terminal alkenes have lower BP, trans alkenes have higher MPs (better packing) and cis alkenes have higher BPs (polarity)
alkyne properties
BPs are slightly higher than corresponding alkenes, internal alkynes have higher BPs than terminal, larger dipole moments than alkenes, terminal alkynes are relatively acidic
alcohol properties
higher BPs than hydrocarbons and ketones/aldehydes (lower than acids), weakly acidic (phenol more acidic, slightly soluble in water), H-bonding
ether properties
no H-bonding, low BPs, only slightly polar/soluble in water, mostly inert
ether cleavage
high temperature and acid, ether oxygen is protonated and nucleophile adds to less hindered R in SN2 (in SNI less hindered side leaves to form bulkier carbocation)
aldehyde/ketone properties
dipole moments cause elevation in BP but not as much as alcohols
carboxylic acid properties
can form H-bonded dimers, resonance of anion, stability of salt increased by electron withdrawing groups (dicarboxylic acid), alpha hydrogens are acidic
amine properties
BPs are greater than alkanes and less than alcohols (not as great H-bonding and none in tertiary amines), sp3 hybridization (flipping around lone pair), alkyl amines are even more basic as alkyl groups can stabilize the charge, aniline is less basic (electron density removed)
ultraviolet spectrum electron transitions
π->π* transitions are easier than n->π* transitions even though the second involve lower energy difference (HOMO->LUMO transitions)
pinacol rearrangement
1,2-diol becomes a ketone in acid through a cationic intermediate following a OH2 leaving group and an R group migrates
protection of alcohols
protection from basic conditions involves the addition of dihydropyran to form a tetrahydropyranol ether, acid can remove protecting group
acetoacetic ester synthesis
ester plus any carbonyl in base to form alcohol leaving group after addition (acidic workup)
Cope rearrangement
1,5-dienes
carboxylic acid preparation
alkyl halide (RX) plus Magnesium in THF solvent, then bubble CO2 through to make RCOOH
epimers and anomers
an anomer is a specific type of epimer that has reversed position at the C-1 carbon of sugars (epimers are those that are stereoisomers with differences at 1 of any carbons)
terpenes
derived from isoprene units (C5H8)n
steroids
terpenoid lipid with 4 rings