Term
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Definition
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Term
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Definition
| hydrocarbons that contain a C-C double bond (common) |
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Term
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Definition
| hydrocarbons that contain a C-C triple bond (rare) |
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Term
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Definition
| alkenes/alkynes have fewer hydrogens per carbon |
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Term
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Definition
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Term
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Definition
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Term
| hybridization of carbons in double bond |
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Definition
3 sp2 hybrid orbitals
120 degree plane
p orbital perpendicular to sp2 plane
1 sigma, 1 pi bond |
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Term
| does free rotation occur in double bonds? |
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Definition
| no, pi bonds need to be broken first |
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Term
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Definition
methyl groups are on the same side of the double bond
less stable because of steric strain
in the presence of acid changes to trans |
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Term
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Definition
| methyl groups are on different sides of the double bond |
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Term
| cis-trans isomerism can't occur if... |
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Definition
| if one of the double bond's carbon is attached to 2 identical groups |
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Term
| use EZ naming instead of cis-trans when... |
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Definition
| double bond has 3 or 4 different substituents |
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Term
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Definition
| higher ranked groups are on opposite sides of double bond |
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Term
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Definition
| if higher ranked groups are on the side side of the double bond |
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Term
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Definition
rank groups by atomic number
if decision can't be made by first atoms, look at second atoms ect. until you can find difference
multiple bonded atoms are equal to same number of single bonded atoms |
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Term
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Definition
| occur when two reactants add to form a single, new product with no atoms left over |
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Term
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Definition
| single reactant splits into two products, mostly a small molecule like H2O or HCl |
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Term
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Definition
| occur when two reactants exchange parts to yield two products |
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Term
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Definition
| occur when a single reactant undergoes a reorganization to yield a single isomeric product |
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Term
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Definition
| how a reaction occurs through bonds breaking/forming, relative rates, how electrons move/reorganize |
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Term
| how can a covalent bond break? |
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Definition
| symmetrical, unsymmetrical |
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Term
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Definition
| covalent bond breaks so that one electron remains with each product fragment |
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Term
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Definition
| covalent breaks so that both electrons remain with one fragment, leaving other fragment with vacant orbital |
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Term
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Definition
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Term
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Definition
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Term
| half-headed/fish-hook arrow |
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Definition
shows the movement of one electron
symmetrical bond-breaking (radical) |
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Term
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Definition
shows the movement of two electrons
unsymmetrical bond-breaking (polar) |
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Term
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Definition
radical
one bonding electron is donated by each reactant |
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Term
| unsymmetrical bond-making |
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Definition
polar
two bonding electrons are donated by one reactant |
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Term
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Definition
symmetrical
movement of single electrons
free-radicals |
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Term
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Definition
electrons move in pairs
more common reaction type
occur due to partial pos/neg charges in molecule |
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Term
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Definition
| made when electron rich atom shares a pair of electrons with electron poor atom |
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Term
| polar bonds break when... |
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Definition
| one atoms leaves with both electrons from the former bond |
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Term
| red electrostatic potential map |
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Definition
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Term
| blue electrostatic potential map |
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Definition
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Term
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Definition
| indicates movement of electrons |
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Term
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Definition
nucleus loving
attracted to positive charge
electron rich (-)
neg/neutrally charged
lone pairs (lewis base)
NH3, water, OH-, Cl- |
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Term
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Definition
electron loving
electron poor (+)
forms bonds by accepting electrons (lewis acid)
pos/neutrally charged |
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Term
| are sigma bonds reactive? |
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Definition
| NO! that's why alkanes aren't reactive because they only have 1 sigma bond |
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Term
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Definition
reactive
above/below the plane of the molecule
it's electron pair behaves as a nucleophile (base) |
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Term
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Definition
positively charged intermediate specie in a reaction
electrophile |
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Term
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Definition
| graphically depicts energy changes that occur during a reaction |
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Term
| vertical axis of energy diagram |
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Definition
| represents total energy of all reactants |
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Term
| horizontal axis of energy diagram |
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Definition
represents progress of reaction
reaction co-ordinate |
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Term
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Definition
energy of the reactants at the start
new C-H bond begins to form and H-Cl bond begins to break |
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Term
| why does energy increase when two reactants collide? |
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Definition
| electron clouds repel each other |
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Term
| what is required for a reaction to start? |
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Definition
| proper orientation and sufficient force of collision |
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Term
| first transition state (B) |
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Definition
structure of maximum energy
can't be isolated/directly observed
c=c pi bond is partially broken and new C-H bond is partially formed |
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Term
| activation energy (E act) |
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Definition
energy difference between reactants (A) and transition state (B)
measures how rapidly reaction occurs |
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Term
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Definition
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Term
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Definition
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Term
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Definition
energy of the carbocation
C-H bond is fully formed
reaction intermediate
entity that is formed during a reaction that reacts further |
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Term
| second transition state (D) |
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Definition
C-Cl bond is partially formed
has its own activation energy E act2 |
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Term
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Definition
energy of the products
C-Cl bond is fully formed |
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Term
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Definition
| difference in energy between reactants and products |
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Term
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Definition
| reactants has more energy than products |
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Term
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Definition
| products have more energy than reactants |
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Term
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Definition
used as an alternate mechanism when E act can't be reached
takes part in reaction, regenerates, goes under no net change
increases overall rate of reaction by providing a different pathway |
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Term
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Definition
| reaction of alkenes with hydrogen |
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Term
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Definition
biological catalysts
E act has to be low for biological reasons
manipulate reaction by providing series of small steps |
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Term
| uncatalyzed reactions have... |
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Definition
| large activation energies |
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Term
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Definition
reaction where HX is added to alkenes where a mixture is not obtained
obeys markovnikov's rule |
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Term
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Definition
H attaches to the carbon with more H's and X attaches to the carbon with more substituents
if both carbons have the same # substituents= mixture |
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Term
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Definition
planar (attack can happen on both sides of plane equally well)
pos carbon is sp2
3 substituents are oriented in an equilateral triangle
6 valance e- are used for the 3 sigma bonds
p orbitals are above/below plane
p orbital is vacant
alkyl groups donate e- to pos carbon |
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Term
| p orbital of carbocations are.... |
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Definition
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Term
| where do alkyl groups donate their e- to? |
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Definition
| positively charged carbon atom |
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Term
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Definition
most substituted
attached to more electron rich atom (primary, secondary, tertiary)
lower energy |
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Term
| rank carbocations by increasing stability |
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Definition
| methyl, primary, secondary, tertiary |
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Term
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Definition
h2o adds to alkenes to yield alcohols
takes place on treatment of alkenes with water and strong acid |
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Term
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Definition
final alcohol with a proton
second carbocation in hydration |
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Term
| hydration reaction conditions are severe because... |
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Definition
strong acid and high temperatures are used
causes sensitive molecules to be destroyed |
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Term
| biological hydration requirements |
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Definition
double bond to be next to carbonyl group
enzyme fumarase to help with hydration during food metabolism |
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Term
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Definition
halogens, such as Br2 and Cl2, are readily added to alkenes
trans |
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Term
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Definition
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Term
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Definition
halogenation of alkenes results in trans orientation
bromine ties up one face of the ring, forcing the other bromine to the opposite side
anti=stereochemical outcome of reaction, not stereochemistry |
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Term
| planar carbocation + Br2 --> |
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Definition
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Term
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Definition
| enzymes that carry out halogenation in marine organisms |
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Term
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Definition
addition of hydrogen to an alkene
needs a catalyst
heterogeneous process (catalyst doesn't dissolve)
occurs on surface of catalyst |
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Term
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Definition
hydrogenation
addition of H -or- removal of O |
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Term
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Definition
physical process
molecules/atoms stick to surface of catalyst |
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Term
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Definition
chemical process
pi electrons in alkene interact with metal through complexation |
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Term
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Definition
reduction/hydrogenation
cis orientation |
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Term
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Definition
| addition of O -or- removal of H |
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Term
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Definition
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Term
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Definition
cyclic ether with an oxygen atoms in a three membered ring
occurs by treatment of peryoxide, RCO3H |
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Term
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Definition
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Term
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Definition
| reaction where epoxides undergo acid-catalyzed ring opening reaction with water |
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Term
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Definition
product of hydrolysis
AKA dialcohol |
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Term
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Definition
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Term
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Definition
process of epoxidation followed by hydrolysis
addition of -OH to each carbon of C=C
trans, one face of double bond is blocked
trans |
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Term
| why does protonation of epoxide make it more reactive? |
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Definition
| C-O bond becomes more polar because of pos charge, susceptible to attack by water |
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Term
| hydroxylation of alkene in a single step |
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Definition
react alkene with KMnO4 in a basic solution
cis-diol
cleavage |
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Term
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Definition
| separation of double bond (KMnO4 acidic) |
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Term
| what functional groups are contained after cleavage? |
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Definition
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Term
| double bond that is tetra-substituted after cleavage... |
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Definition
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Term
| if 1 hydrogen is on the double bond after cleavage... |
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Definition
| one product is a carboxylic acid |
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Term
| if 2 hydrogens are present on 1 carbon of double bond after cleavage... |
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Definition
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Term
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Definition
| electrophile attacks the bond |
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Term
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Definition
| large molecule built by repetitive units of monomers |
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Term
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Definition
| individual units of monomers |
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Term
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Definition
| polymer built of sugar monomers |
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Term
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Definition
| polymers built from amino acid monomers |
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Term
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Definition
| polymer built from nucleotide monomers |
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Term
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Definition
| made from alkenes using a suitable polymerization catalyst |
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Term
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Definition
| initiation, propagation (repeats), termination |
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Term
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Definition
many substituted ethylenes that yield polymers
propelyne= polypropylene |
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Term
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Definition
compounds that have alternating double and single bonds
HX bonds adds differently than Br2 |
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Term
| conjugated compound + HX = |
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Definition
1, 2 addition
1, 4 addition |
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Term
| conjugated compound + Br2= |
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Definition
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Term
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Definition
carbocation that is next to double bond
more stable than non-allylic carbocations
resonance hybrid of 2 forms
resonance |
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Term
| why are allylic carbocations more stable? |
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Definition
symmetrical
all 3 carbons are sp2 (1 pi 1 sigma)
each carbon has a vacant p orbital |
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Term
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Definition
two individual carbocation structures
<-->
don't have to be equivalent |
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Term
| difference between resonance forms? |
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Definition
| position of pi bond electrons/lone pairs |
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Term
| similarities between resonance forms? |
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Definition
atoms are in same place
atom connections
3d shape |
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Term
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Definition
allylic carbocation has single unchanging structure that is a blend all its resonance structures
characteristics of both structures= share bonds/charges equally
more stable than individual resonance forms |
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Term
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Definition
more stability
electrons spread over a larger part of molecule |
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Term
| resonance does not follow... |
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Definition
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Term
| movement of lone pairs... |
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Definition
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Term
| resonance forms follow... |
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Definition
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Term
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Definition
hydrocarbons that contain C-C triple bonds
2 sp (1 sigma, 2 pi) |
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Term
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Definition
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Term
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Definition
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Term
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Definition
| compounds with both double and triple bonds |
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Term
| alkynes + 2 mol H2 + catalyst= |
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Definition
alkenes, then alkanes
can be stopped at alkene w/ lindlar catalyst |
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Term
| alkynes five cis alkenes when reduced because... |
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Definition
| hydrogenation occurs with syn stereochemistry |
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Term
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Definition
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Term
| 1 molar equivalent of HX yields... |
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Definition
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Term
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Definition
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Term
| bromine/chlorine + alkynes yields |
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Definition
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Term
| addition proceeds with... |
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Definition
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Term
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Definition
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Term
| hydrated internal alkyne yields... |
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Definition
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Term
| hydrated terminal alkyne yields... |
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Definition
one product
terminal alkynes are weakly acidic
acetylide anion--> terminal alkyne
terminal alkyne--> internal alkyne |
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Term
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Definition
formed when strong bases like NaNH2 remove terminal hydrogens
react with alkyl halides via nucleophilic attack |
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Term
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Definition
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Term
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Definition
C6H6
unsaturated
substitution reactions
planar, sp2, 120, perpendicular p orbitals |
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Term
| why is benzene less reactive than alkenes |
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Definition
| resonance makes it more stable |
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Term
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Definition
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Term
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Definition
| represents a general aromatic ring |
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Term
| ortho-disubstituted benzene |
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Definition
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Term
| meta- disubstituted benzene |
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Definition
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Term
| para-disubstituted benzene |
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Definition
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Term
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Definition
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Term
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Definition
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Term
| electrophilic aromatic substitution |
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Definition
electrophile reacts with aromatic ring and substitutes from on the the hydrogen
most common aromatic compound reaction
less reactive towards electrophiles, needs catalyst |
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Term
| why does first step of electrophilic aromatic substitution have a high Eact? |
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Definition
allylic carbocation isn't as stable as the original benzene ring
not as reactive to electrophiles |
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Term
| what does addition cause in aromatic rings? |
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Definition
| resonance stability to be lost, need to substitute |
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Term
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Definition
| way to introduce alkyl groups onto benzene ring (Friedel-Crafts) |
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Term
| Friedel-Crafts alkylation reaction limitations |
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Definition
only halogens can be used unless its attached to a ring
NO2, CN, SO3H, COR make benzene less reactive |
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Term
| Friedel-Crafts acylation reaction |
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Definition
| acyl group is introduced onto benzene ring |
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Term
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Definition
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Term
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Definition
H, OH make benzene ring more reactive
donate e- to ring
make ring more e- rich
causes positive carbocation to be stable
Eact lowered, reaction quickened |
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Term
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Definition
NO2, CHO, Cl make benzene ring less reactive
withdraw e- from ring
makes ring e- poor
makes pos carbocation more positive
raises Eact, slows reaction |
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Term
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Definition
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Term
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Definition
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Term
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Definition
deactivating
groups' positively polarized atom is directly attached to ring
=O-C-R, O=C-R, C=-N, O-N=O |
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Term
| ortho, para directing groups |
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Definition
activating (excludes halogens)
lone pairs on atoms directly bonded to ring
OH, NH2, Cl, Br |
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Term
| how do halogens affect benzene orientation? |
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Definition
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Term
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Definition
withdrawal/donation of e- through a sigma bond
due to EN difference between ring's groups |
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Term
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Definition
withdrawal/donation of e- through pi bond
due to p-orbital overlap between group and benzene ring |
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Term
| product distribution paralleles... |
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Definition
| stability of intermediate |
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Term
| amino group with lone pairs... |
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Definition
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Term
| what part of benzene ring reacts with KMnO4? |
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Definition
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Term
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Definition
place where KMnO4 attack the side chain of C-H bonds next to aromatic ring
radical intermediates |
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Term
| what are aromatic rings inert to? |
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Definition
reduction when under typical alkene hydrogenation conditions
needs high temp/pressure
KMnO4 unless it has alkyl groups |
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Term
| polycyclic aromatic compound |
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Definition
| multiple benzene rings fused together |
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Term
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Definition
| unusual behavior of cyclic conjugated molecules like benzene |
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Term
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Definition
aromatic compounds that contain atoms of two or more elements in their rings
6 pi e-
pyridine, pyrimidine, pyrrole, imidazole |
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Term
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Definition
| 1 pi e- on each of their ring's atoms (hexagon) |
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Term
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Definition
1 pi e- on each of the 4 atoms and 2 pi e-'s on N-H (lone pair)
(pentagon) |
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Term
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Definition
| methodology of working backwards to devise a synthetic route |
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Term
| nitration of benzene+ HNO3/H2SO4= |
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Definition
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Term
| sulfuration of benzene + SO3/H2SO4= |
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Definition
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Term
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Definition
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Term
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Definition
alkyne intermediate
rarely isolated |
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Term
| product of alkyne hydration? |
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Definition
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Term
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Definition
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Term
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Definition
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Term
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Definition
|
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Term
| which ortho/para resonance structure is most stable? |
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Definition
lone pairs on oxygen
more bonds |
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Term
| which meta directing ortho/para structure is least stable? |
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Definition
| one with + closest to the C because this creates too much strain |
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