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Chapter 10: Organohalides
part of OCHEM Test 3
92
Organic Chemistry
Undergraduate 2
07/01/2017

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Term
rules for naming alkyl halides
Definition
1: find the longest chain and name it as the parent
+if a 2bl or triple bond is present, the parent chain must contain it
2: number the C atoms of the parent chain, starting at the end nearer the first substituent, whether alkyl or halo
3: number each substituent
+if more than 1 of the same kind of substituent is present, number each, and use the prefixes di-, tri-, tetra-, and so on
+if different halogens are present, number all and list them in alphabetical order
4: if the parent chain can be numbered from either end, start at the end nearer the substituent that has alphabetical priority
Term
some alkyl halides are named by first citing the ______ and then citing the ______
Definition
name of the alkyl group
halogen
Term
geometry of alkyl halides
Definition
tetrahedral
Term
bond length in alkyl halides vs. size of halogen bonded to the C
Definition
directly proportional

bond lengths increase with increasing size of the halogen
Term
bond strength in alkyl halides vs. size of halogen bonded to the C
Definition
inversely proportional

bond strengths decrease with increasing size of the halogen
Term
Carbon-halogen bonds are...
Definition
polar
Term
many halomethanes have...
Definition
dipole moments
Term
alkyl halides behave as ______ in polar rxns
Definition
electrophiles
Term
alkyl halides behave as electrophiles in ______ rxns
Definition
polar
Term
some ways to prepare alkyl halides
Definition
-radical halogenation of alkanes
-allylic bromination of alkenes
-alkyl halides from alcohols
Term
the sequence of steps in radical halogenation of alkanes
Definition
initiation, propagation, termination
Term
radical halogenation of alkanes continues to produce...
Definition
di- and polysubstituted products
Term
if more than 1 type of ______ is present during the radical halogenation of an alkane, more than 1 type of monosubstituted product is formed
Definition
H
Term
if more than 1 type of H is present during the radical halogenation of an alkane,...
Definition
more than 1 type of monosubstituted product is formed
Term
the reactivity order of different types of H towards chlorination
Definition
tertiary > secondary > primary
Term
why the reactivity order of different types of H towards chlorination is tertiary > secondary > primary
Definition
because of bond dissociation energies for formation of the alkyl radicals
Term
the stability order of alkyl radicals
Definition
tertiary > secondary > primary
Term
rxn of ______ with NBS causes bromination at the position allylic to the 2bl bond
Definition
an alkene
Term
rxn of an alkene with ______ causes bromination at the position allylic to the 2bl bond
Definition
NBS
Term
rxn of an alkene with NBS causes ______
Definition
bromination at the position allylic to the 2bl bond
Term
the mechanism by which allylic bromination of alkenes occurs
Definition
a radical chain mechanism
Term
how the radical chain mechanism occurs in allylic bromination of alkenes
Definition
1: Br• abstracts an allylic H 2: the allylic radical reacts with Br2 to form an allylic bromide, plus Br•
Term
______ occurs at the allylic position because an allylic C-H bond is weaker than most other C-H bonds, and the allylic radical is more stable
Definition
allylic bromination of alkenes
Term
allylic bromination of alkenes occurs at ______ because an allylic C-H bond is weaker than most other C-H bonds, and the allylic radical is more stable
Definition
the allylic position
Term
allylic bromination of alkenes occurs at the allylic position because...
Definition
an allylic C-H bond is weaker than most other C-H bonds, and the allylic radical is more stable
Term
reasons for stability of an allylic radical
Definition
-the C with the unpaired electron is sp2 hybridized, and its p orbital can overlap with the p orbitals of the 2bl bond C's -the radical intermediate is thus stabilized by resonance +the stability is due to delocalization (spreading out) of the unpaired electron over an extended pi network -reaction of the allylic radical with Br2 can occur at either end of the pi orbital system +a mixture of products may be formed if the alkene is unsymmetrical +these products aren's usually formed in equal quantities: rxn to form the more substituted 2bl bond is favored -products of allylic bromination can be dehydrohalogenated to form dienes
Term
in an allylic radical, the ______ is sp2 hybridized, and its p orbital can overlap with the p orbitals of the 2bl bond C's
Definition
C with the unpaired electron
Term
in an allylic radical, the C with the unpaired electron is ______, and its p orbital can overlap with the p orbitals of the 2bl bond C's
Definition
sp2 hybridized
Term
in an allylic radical, the C with the unpaired electron is sp2 hybridized, and its ______ can overlap with the p orbitals of the 2bl bond C's
Definition
p orbital
Term
in an allylic radical, the C with the unpaired electron is sp2 hybridized, and its p orbital can overlap with ______
Definition
the p orbitals of the 2bl bond C's
Term
the radical intermediate of an allylic radical is stabilized by...
Definition
resonance
Term
how resonance stabilizes allylic radicals
Definition
because the unpaired electron is spread out over an extended pi network
Term
rxn of the allylic radical with Br2 can occur at...
Definition
either end of the pi orbital system
Term
a mixture of products may form at the end of an allylic radical rxn if...
Definition
the alkene is unsymmetrical
Term
why the mixture of products at the end of an allylic radical rxn is unequal
Definition
the rxn to form the more substituted 2bl bond is favored
Term
products of allylic bromination reactions can be ______ to form dienes
Definition
dehydrohalogenated
Term
products of allylic bromination reactions can be dehydrohalogenated to form ______
Definition
dienes
Term
______ alkyl chlorides, bromides, or iodides can be prepared by the rxn of a tertiary alcohol with HCl, HBr, or HI
Definition
tertiary
Term
tertiary ______ can be prepared by the rxn of a tertiary alcohol with HCl, HBr, or HI
Definition
alkyl chlorides, bromides, or iodides
Term
tertiary alkyl chlorides, bromides, or iodides can be prepared by ______ with HCl, HBr, or HI
Definition
the rxn of a tertiary alcohol
Term
tertiary alkyl chlorides, bromides, or iodides can be prepared by the rxn of a tertiary alcohol with ______
Definition
HCl, HBr, or HI
Term
reaction of ______ alcohols occurs under more drastic conditions, which may destroy other acid-sensitive functional groups
Definition
secondary or primary
Term
reaction of secondary or primary alcohols occurs under ______, which may destroy other acid-sensitive functional groups
Definition
more drastic conditions
Term
reaction of secondary or primary alcohols occurs under more drastic conditions, which may...
Definition
destroy other acid-sensitive functional groups
Term
______ can be formed by treatment of the corresponding alcohols with SOCl2 or PBr3, respectively
Definition
primary and secondary alkyl chlorides and bromides
Term
primary and secondary alkyl chlorides and bromides can be formed by ______ with SOCl2 or PBr3, respectively
Definition
treatment of the corresponding alcohols
Term
primary and secondary alkyl chlorides and bromides can be formed by treatment of the corresponding alcohols with ______
Definition
SOCl2 or PBr3, respectively
Term
the rxn conditions of the formation of primary and secondary alkyl chlorides
Definition
mild, less acidic, and less likely to cause acid-catalyzed rearrangements
Term
______ can be prepared using either (CH3CH2)2 NSF3 or HF in a pyridine
Definition
alkyl fluorides
Term
alkyl fluorides can be prepared using either ______ or ______ in a pyridine
Definition
(CH3CH2)2 NSF3 HF
Term
alkyl fluorides can be prepared using either (CH3CH2)2 NSF3 or HF in a ______
Definition
pyridine
Term
organohalides react with Mg to produce...
Definition
organimagnesium halides (RMgX)
Term
Grignard reagents
Definition
organomagnesium halides, RMgX
Term
______ can be formed from alkyl, alkenyl, and aryl halides
Definition
Grignard reagents
Term
Grignard reagents can be formed from ______
Definition
alkyl, alkenyl, and aryl halides
Term
is steric hinderance a barrier to the formation of Grignard reagents?
Definition
no
Term
in Grignard reagents, the ______ bonded to Mg is negatively polarized and is nucleophilic
Definition
C
Term
in Grignard reagents, the C bonded to ______ is negatively polarized and is nucleophilic
Definition
Mg
Term
in Grignard reagents, the C bonded to Mg is ______ and is nucleophilic
Definition
negatively polarized
Term
in Grignard reagents, the C bonded to Mg is negatively polarized and is ______
Definition
nucleophilic
Term
Grignard reagents react with ______ to form hydrocarbons
Definition
weak acids
Term
Grignard reagents react with weak acids to form ______
Definition
hydrocarbons
Term
______ can react with Li to form alkyllithiums
Definition
alkyl halides
Term
alkyl halides can react with ______ to form alkyllithiums
Definition
Li
Term
alkyl halides can react with Li to form ______
Definition
alkyllithiums
Term
______ can combine with CuI to form lithium diorganocopper compounds (R2CuLi), which are known as Gilman reagents
Definition
alkyllithiums
Term
alkyllithiums can combine with ______ to form lithium diorganocopper compounds (R2CuLi), which are known as Gilman reagents
Definition
CuI
Term
alkyllithiums can combine with CuI to form ______, which are known as Gilman reagents
Definition
lithium diorganocopper compounds (R2CuLi)
Term
alkyllithiums can combine with CuI to form lithium diorganocopper compounds (R2CuLi), which are known as ______
Definition
Gilman reagents
Term
Gilman reagents
Definition
lithium diorganocopper compounds (R2CuLi)
Term
______ can react with alkyl halides (except for fluorides) to form hydrocarbon products
Definition
lithium diorganocopper compounds (R2CuLi)
Term
lithium diorganocopper compounds (R2CuLi) can react with ______ (except for fluorides) to form hydrocarbon products
Definition
alkyl halides
Term
lithium diorganocopper compounds (R2CuLi) can react with alkyl halides (except for ______) to form hydrocarbon products
Definition
fluorides
Term
lithium diorganocopper compounds (R2CuLi) can react with alkyl halides (except for fluorides) to form ______
Definition
hydrocarbon products
Term
______ rxns are useful for forming large molecules from small pieces
Definition
organometallic coupling
Term
organometallic coupling rxns are useful for ______
Definition
forming large molecules from small pieces
Term
organometallic coupling rxns can be carried out on...
Definition
alkyl, vinyl, and aryl halides
Term
the mechanism for organometallic coupling rxns is not...
Definition
a typical polar nucleophilic substitution
Term
Suzuki-Miaura rxn
Definition
Pd catalyzed coupling of aryl or vinyl organotin reagents with organohalides
Term
oxidation in ochem
Definition
a rxn that results in a loss of electron density by a C
Term
oxidation of a C may be due to...
Definition
-bond formation between C and more eneg atom (usually O, N, or halogen)
-bond breaking between C and less eneg atom (usually H)
Term
examples of oxidation of a C include ______ and reduction of alkenes with Br2
Definition
chloronation of alkanes
Term
examples of oxidation of a C include chloronation of alkanes and ______
Definition
reduction of alkenes with Br2
Term
reduction in ochem
Definition
rxn that results in a gain of electron density by a C
Term
reduction of a C may be due to...
Definition
-bond formation between C and less eneg atom
-bond breaking between C and more eneg atom
Term
examples of reduction of a C include ______, and reduction of an alkene with H2
Definition
conversion of a Grignard reagent to an alkene
Term
examples of reduction of a C include conversion of a Grignard reagent to an alkene, and ______
Definition
reduction of an alkene with H2
Term
______ is/are at the lowest oxidation level and ______ is/are at the highest level
Definition
alkanes CO2
Term
a rxn that converts a compound from a lower oxidation level to a higher oxidation level is...
Definition
an oxidation
Term
a rxn that converts a compound from a higher oxidation level to a lower oxidation level is...
Definition
a reduction
Term
cations typically form under (acidic or basic) conditions
Definition
acidic
Term
anions typically form under (acidic or basic) conditions
Definition
basic
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