Organic Chemistry 217/12 - Organic Chemistry 3.pdfIn Organic Chemistry, “oxidation” is all about...
Transcript of Organic Chemistry 217/12 - Organic Chemistry 3.pdfIn Organic Chemistry, “oxidation” is all about...
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Organic Chemistry
It’s all about the charges!
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Predict the products:
A B
C D
E
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Resonance Hybrid
the true structure of benzene is a resonance
hybrid of two structures
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“Oxidation” of Alcohols
Organic chemistry looks at “oxidation” differently than
we discussed in redox reactions where “oxidation”
was all about losing electrons.
In Organic Chemistry, “oxidation” is all about gaining
OXYGEN!
The more oxygen attached to the carbon, the more
“oxidized” the carbon is considered.
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CH3CH3 no oxygen, lowest oxidation possible
CH3CH2OH 1 oxygen, it is “oxidized” ethane
CH3CH2C=O 2 oxygens (2 bonds, so 2 O)
CH3CH2C=O 3 oxygens (high as it gets)
H
OH
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How do we oxidize it?
With a strong oxidizer!
Strong oxidizers are typically metal ions (like
Cr3+ or Mn7+) with a lot of oxygens on them:
MnO4- or Cr2O7
2-
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CH3CH2OH CH3CH2COOH
same as
CH3CH2C=O
A weaker oxidizer (like HNO3 or PCC) would
take it up in oxidation, but not all the way!
Na2Cr2O7
OH
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Aldehydes and Ketones
-C=0 (a “carbonyl” group)
|
An aldehyde is a terminal carbonyl.
CH3CH2CHO
A ketone is an internal carbonyl.
CH3COCH3 CH3 CH3 C
O
CH3 CH2 CH
O
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Aldehydes and Ketones contain the carbonyl group
aldehydes = at least 1 side H
ketones = both sides R groups
many aldehydes and ketones
have pleasant tastes and
aromas
some are pheromones
formaldehyde = H2C=O pungent gas
formalin = a preservative
wood smoke, carcinogenic
acetone = CH3C(=O)CH3 nail-polish remover
O
C
formaldehyde
acetone
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Aldehyde Odors and Flavors butanal = butter
vanillin = vanilla
benzaldehyde = almonds
cinnamaldehyde = cinnamon
O
H
C CH2CH2CH3
O
CH
HC
O
C C
H
H
H
OO
HO
HO
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Ketone Odors and Flavors acetophenone = pistachio
carvone = spearmint
ionone = raspberries
muscone = musk
O
CH3C
O CH3
O
H3C
C
CH3
CH2
CH3
CH3H3C O
C CH3CCH
H
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Reactions aldehydes and ketones are generally
synthesized by the oxidation of alcohols
therefore, reduction of an aldehyde or ketone
results in an alcohol
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Carbonyl Group
C=O group is highly polar
many reactions involve addition across C=O,
with positive part attached to O
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Addition to C=O
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Naming Aldehydes
An aldehyde is named by taking the root alkane, dropping the “-e” and adding “-al”. The carbonyl is considered the “1” position, so there is no ambiguity in numbering.
CH3 CH2 CH
O
propanal
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Naming ketones
A ketone is named by taking the root alkane,
dropping the “-e” and adding “-one”. The
position must be numbered in larger alkanes.
CH3 CH3 C
O propanone
or
2-propanone
CH3 CH3 C
O
CH2 CH2
CH3 C
O
CH2 CH2 CH3
2-pentanone
3-pentanone
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Carboxylic Acids
A carboxylic acid is also a carbonyl containing compound, but it also has a hydroxide group on the carbonyl carbon.
They are named by dropping the “-e” and adding “-oic acid”
Again, the position normally need not be numbered as it is always the “1” position.
CH3 CH2 C
O
OH Propanoic acid
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Carboxylic Acids RCOOH
sour tasting
weak acids
citric acid
found in citrus fruit
ethanoic acid = acetic acid
vinegar
methanoic acid = formic acid
insect bites and stings
O
OHCH
O
OHCCH3
OH
O
HO C C
CH2 C
C
O
O
OH
OH
CH2
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Carboxylic Acids made by the oxidation of
aldehydes and alcohols
OH on the end of the chain
always on main chain
has highest precedence
C of group always C1
position not indicated in name
change ending to oic acid
H3C CH2
OH
H3C
O
C OH
oxidation
ethanoic acidethanol
oxidation
O
CH
O
COH
benzaldehyde benzoic acid
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Naming Carboxylic Acids
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Esters
An “ester” is a product of the dehydration of a carboxylic acid and an alcohol.
Esters usually have pungent, fruity aromas.
Ethylbutanoate is pineapple smell. Methylbutanoate is apple.
Esters are named by combining the name of the carboxylic acid and alcohol that they came from, using the carboxylic acid as the root (drop the “-oic acid” and add “-oate” and the alcohol as a prefix.
CH3 CH2 C
O
OH
Propanoic acid
+ CH3 CH2 OH
Ethanol
H+
CH3 CH2 C
O
OCH2CH3
Ethyl propanoate.
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Esters R–COO–R
sweet odor
made by reacting carboxylic acid
with an alcohol
RaCOOH + RbOH RaCOORb +
H2O
name alkyl group from alcohol,
then acid name with oate ending
precedence over carbonyls, but not
carboxylic acid
number from end with ester group
O
COH
C CH3
O
O
aspirin
methyl butanoate
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Naming Esters
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What would you call this molecule?
CH3 O CH3 CH2
O
CH2 CH2 CH2 C Ethyl pentanoate
CH3
CH3 O CH2
O
CH3 CH2 CH CH2 C 2-methyl-ethyl pentanoate
The carbonyl is considered the 1-position
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Ethers
Ethers are kind of like baby esters! If you
dehydrate two alcohols, you get an ether!
CH3 CH2 CH3 OH OH + CH3 CH3 CH2 O
Ethers are named by naming the 2 alcohols separately as substituent
groups (in alphabetical order)and adding “ether”
Methyl ethyl ether
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More ethers
Name this!
O CH3 CH3
CH2 O CH3 CH3 CH2 CH2
CH3 O CH CH3 CH2
Br
Methyl propyl ether
Dimethyl ether
1-bromoethyl methyl ether
The “O” position is always at the “1” position.
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Amines
Contain –NH2 group or a substituted version (-NHCH3, -N(CH3)2)
Are named by naming the corresponding alkane and adding amine.
CH3CH2NH2 Ethylamine
Amines are bases!!! (Think NH3)
Amine chemistry is dictated by the “N” and the resulting basicity.
Amines and carboxylic acids are very important in biochemistry.
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Amines N containing organic molecules
very bad smelling
form when proteins decompose
organic bases
name alkyl groups attached to the N, then add the word amine to the end
H3C CH2
NH2
ethylamine
H3C CH2
NHH3C
ethylmethylamine H2NCH2CH2CH2CH2CH2NH2
cadaverine
putrescine H2NCH2CH2CH2CH2NH2
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Amines many amines are biologically active
dopamine – a neurotransmitter
epinephrine – an adrenal hormone
pyridoxine – vitamin B6
alkaloids are plant products that are alkaline and biologically active toxic
coniine from hemlock
cocaine from coca leaves
nicotine from tobacco leaves
mescaline from peyote cactus
morphine from opium poppies
HO
HO
CH2CH2NH2
dopamine
N
N
CH3
nicotine
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Amine Reactions
weak bases
react with strong acids to form ammonium salts
RNH2 + HCl → RNH3+Cl−
react with carboxylic acids in a condensation
reaction to form amides
RCOOH + HNHR’ RCONHR’ + H2O
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Formulas