Chapters 10 and 11
-Carboxyl Group since a combination of
carbonyl and hydroxyl groups. (see below)
-nomenclature: common names usually
used.
-for IUPAC, simply add "oic acid" as suffix
Nomenclature
• Suffix is “oic”
• COOH always at end of chain and always the #1 carbon
• carbon understood to be #1 and therefore not stated as part
of the name
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Examples:
4-Bromopentanoic acid
heptanoic acid
2-ethyl-3-hydroxy-5-methyl-hexanoic acid
Common Carboxylic Acids
and where they are found:
Formic Acid---red ants and bee stings
Acetic Acid ---Vinegar
Butyric Acid-- Rancid Butter, Locker Rooms
Caproic, Caprylic,Capric - Goats
Lactic Acid (Hydroxy acid) - Muscles, anaerobic
respiration
Citric Acid (Hydroxy acid) - citrus fruits
Oxidation of Alcohol and
Carboxylic Acids
• Alcohol
• Ex: ethanol
Aldehyde
ethanal
Carboxylic Acid
ethanoic acid
-Fat + NaOH = soap
-if vegetable fat, softer soap
-hydrophobic portion dissolves dirt (if dirt non-soluble in water) and
hydrophilic portion attaches to water to be washed away
-in hard water (Mg and Ca), minerals will precipitate out to leave "ring"
around tub.
-detergents will not allow precipitation of minerals
HOW SOAPS AND DETERGENTS
WORK
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These types of energy interact and should be in proper balance. Let's
look at how they work together.
Let's assume we have oily, greasy soil on clothing. Water alone will not
remove this soil. One important reason is that oil and grease present in
soil repel the water molecules.
Now let's add soap or detergent. The surfactant's water-hating end is
repelled by water but attracted to the oil in the soil. At the same time,
the water-loving end is attracted to the water molecules.
These opposing forces loosen the soil and suspend it in the water.
Warm or hot water helps dissolve grease and oil in soil. Washing
machine agitation or hand rubbing helps pull the soil free.
Soap Diagram
Soap and Detergents
-Acid + Base
water and a salt
Formic Acid + Sodium Hydroxide
-important preservatives
-examples:
Sodium Benzoate: inhibits mold and bacteria
Calcium/Sodium
Propionate: cheese, cakes, bread
-relate to preservatives…see website on additives
H2O
Food additives
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Artificial additives and behavior website
Artificial colors website
List of additives and preservative website
Safety of food additives/list website
http://www.cspinet.org/reports/chemcuisine.
htm#Alphabetical
Carboxylic Esters and Flavors
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Ethyl Formate
Ethyl Butyrate
Methyl Butyrate
Octyl Acetate
Methyl Salicylate
Rum
Pineapple
Apple
Orange
Wintergreen
Esters are produced
when carboxylic
-Flavoring Agents
acids are heated
with alcohols in the
-Alcohol + Carboxylic Acid = Ester presence of an acid
catalyst. The catalyst
is usually
concentrated
-Ethanol + Formic acid
sulphuric acid.
-Methanol + Butyric Acid
Methyl Salicylate = Wintergreen
Wintergreen Lab
website-natural wintergreen
equation website
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Procedure:
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3 mLs. Methanol into test tube
.5 grams Salicylic Acid into test tube
Mix thoroughly
Add 10 drops of H2SO4(sulfuric acid) to test tube (this acts as a catalyst)
Place test tube into a beaker of water that is at 60-700C at keep test tube in this
beaker for approx. 10 minutes
– After 10 minutes, remove test tube and add hot water to fill test tube (do not add
more than 20 mLs. of hot water…use water from 600 beaker)
– Mix and detect odor…pour small amount onto a paper towel and detect odor
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Discussion:
– Thoroughly explain and show chemical equation for the formation of a carboxylic
ester and methyl salicylate in particular.
– Explain how/why esters are used in the food industry
– Explain the difference between “all natural” and “natural flavors” as it relates to
foods
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teaberry Ericaceae Gaultheria procumbens L.
Leaf: Alternate, simple, evergreen, oval to elliptical, 1 to 2 inches long,
minutely serrated, thickened with a wintergreen odor when crushed, leaves
appear whorled since they cluster at tips of plant; dark shiny green above,
much paler below often with black dots.
Flower: Monoecious; small (1/4 inch), white, urn-shaped, hanging from short
stems from leaf axils, appearing in mid to late summer.
Fruit: Red, round, 1/4 to 1/2 inch in diameter, hanging beneath the leaves, mild
wintergreen taste, ripen in late summer and persist into winter.
Twig: Slender, green turning brown with age.
Bark: Light brown.
Form: Low plant with a height of only 3 to 5 inches; stems shoot out of the
ground and end in a tight cluster of leaves.
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Drug patents
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A generic drug (pl. generic drugs, short: generics) is a drug which is produced and
distributed without patent protection. A generic must contain the same active
ingredients as the original formulation. In most cases, it is considered bioequivalent
to the brand name counterpart with respect to pharmacokinetic and
pharmacodynamic properties. By extension, therefore, generics are assumed to be
identical in dose, strength, route of administration, safety, efficacy, and intended
use. In most cases, generic products are not available until the patent protections
afforded to the original developer have expired. When generic products become
available, the market competition often leads to substantially lower prices for both
the original brand name product and the generic forms. The time it takes a generic
drug to appear on the market varies. Drug patents give twenty years of protection,
but they are applied for before clinical trials begin, so the effective life of a drug
patent tends to be between seven and twelve years.
Generic Drugs website
Pricing of Generic vs. Patent Drugs article
US vs. Canada and Drug laws article
OTC Analgesics (over the counter)
-aspirin (acetylsalicyclic acid)
-salicylic acid and willow tree bark
-1893 Bayer Company
-anti-coagulant
-anti-inflammatory
-anti-pyretic
-Reye's syndrome (NOT for children!)
-medline website
-Ibuprofen
-Advil, Motrin, Nuprin
-anti-inflammatory, fever reduction
-allergic reaction mimics Meningitis
-stomach upset side effect
medline website
-acetaminophen
-Tylenol
-fever reduction
-liver damage if alcohol use
-medline website
-naproxen sodium
-longer lasting than ibuprofen
-”Aleve”
-anti-inflammatory
-jaundice as side-effect
-medline website
Non-steroidal anti-inflammatory
drugs
• Salycilates: Aspirin (Acetylsalicylic Acid), Diflunisal,
Ethenzamide
• Arylalkanoic acids: Diclofenac, Indometacin, Sulindac
• 2-Arylpropionic acids (profens): Carprofen,
Flurbiprofen, Ibuprofen, Ketoprofen, Ketorolac, Loxoprofen,
Naproxen, Tiaprofenic acid,
• N-Arylanthranilic acids (fenamic acids): Mefenamic
acid – Pyrazolidine derivatives: Phenylbutazone
• Oxicams: Meloxicam, Piroxicam -- Coxibs: Celecoxib,
Etoricoxib, Parecoxib, Rofecoxib, Valdecoxib -Sulphonanilides: Nimesulide
OTC Analgesics
 Aspirin
 Ibuprofen
 Acetaminophen
 Naproxen Sodium
 Ketoprofen
Aspirin (acetylsalicylic acid)
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analgesic (against minor pains and aches)
antipyretic (against fever)
anti-inflammatory
antiplatelet (“blood-thinning”) effect and is used in long-term lowdoses to prevent heart attacks and cancer (high doses right after an
attack) (anticoagulant)
• Its primary undesirable side effects, especially in higher doses, are
gastrointestinal distress (including ulcers and stomach bleeding) and
tinnitus (ringing in ear)
• It is generally recommended that one seek medical help if symptoms
do not improve after a few days of therapy
• Children, including teenagers, are discouraged from using aspirin in
cold or flu symptoms as this has been linked with Reye's syndrome.
Aspirin (acetylsalicylic acid)
• coined by the Bayer
company of Germany
• Also known as ASA, ASS,
AAS (depending on language)
• bitter powder extracted from
willow bark eases aches and
pains and reduce fevers
• active extract of the bark,
called salicin (when oxidized
becomes salicylic acid)
2-(acetyloxy)benzoic acid
Formula
C9H8O4
C6H4(OCOCH3)CO
OH
Reye’s Syndrome
• Website-Aspirin and Reye’s Syndrome
• What is Reye's Syndrome?
• Reye's Syndrome is a disease which affects all organs of
the body, but most lethally the liver and the brain. Reye's
Syndrome is a two-phase illness because it is almost
always associated with a previous viral infection, such as
influenza, cold, or chicken pox. Scientists do know that
Reye's Syndrome is not contagious and the cause is
unknown. Reye's Syndrome is often misdiagnosed as
encephalitis, meningitis, diabetes, drug overdose,
poisoning, Sudden Infant Death Syndrome, or psychiatric
illness.
Aspirin and Salicylic Acid
• Aspirin or acetylsalicylic acid, is a derivative of salicylic acid that is a
mild, nonnarcotic analgesic useful in the relief of headache and muscle
and joint aches. The drug works by inhibiting the production of
prostaglandins, body chemicals that are necessary for blood clotting
and which also sensitize nerve endings to pain.
• The father of modern medicine was Hippocrates, who lived sometime
between 460 B.C and 377 B.C. Hippocrates was left historical records
of pain relief treatments, including the use of powder made from the
bark and leaves of the willow tree to help heal headaches, pains and
fevers.
• By 1829, scientists discovered that it was the compound called salicin
in willow plants which gave you the pain relief.
• Website on history of aspirin
• Aspirin info website
Ibuprofen
• nonsteroidal anti-inflammatory drugs (NSAIDs)
• works by reducing hormones that cause inflammation and
pain in the body(prostaglandins)
• marketed under various trademarks including Act-3,
Advil, Brufen, Herron Blue, Motrin, Nuprin, Dorival and
Nurofen
• used for relief of symptoms of arthritis, primary
dysmenorrheal, fever, and as an analgesic, especially
where there is an inflammatory component
• believed to work through inhibition of cyclooxygenase
(COX), thus inhibiting prostaglandin synthesis
• Severe allergic reactions mimic meningitis symptoms
• Ibuprofen
Ibuprofen
has a dosedependent duration of action
of approximately 4–8 hours,
which is longer than
suggested by its short half-life
• recommended dose varies
with body mass
•made available under
prescription in the United
Kingdom in 1969 yet now is
an over the counter drug
2-[4-(2-methylpropyl)phenyl]propanoic acid
Formula
C13H18O2
Acetaminophen (Paracetamol)
• a common analgesic and antipyretic drug that is
used for the relief of fever, headaches, and other
minor aches and pains
• major ingredient in numerous cold and flu
medications
• Tylenol
• Minimizes side-effects when combined with
opioid analgesics
• compounds contained in cinchona bark, similar to
the willow bark in aspirin (same salicylic acid)
• Liver damage has been linked to use of
acetaminophen and alcohol in combination
Acetaminophen (Paracetamol)
• Often combined with codeine (an
opioid) and caffeine
• paracetamol acts by reducing
production of prostaglandins, which
are involved in the pain and fever
processes, by inhibiting the
cyclooxygenase (COX) enzyme
• important differences between the
effects of aspirin and those of
paracetamol
- less side effects
- does not reduce blood clotting
- no detrimental side effects to the
lining of the stomach
N-(4-hydroxyphenyl)acetamide
Formula C8H9NO2
Naproxen
Sodium
• marketed under various trade names including: Aleve,
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Anaprox, Naprogesic, Naprosyn, Naprelan
non-steroidal anti-inflammatory drug (NSAID) commonly
used for the reduction of mild to moderate pain, fever,
inflammation and stiffness caused by conditions such as
arthritis
naproxen is capable of producing disturbances in the
gastrointestinal tract. Increases risk of cardiovascular
problems.
not recommended for use with NSAIDs of the salicylate
family
prescription drug Naprosyn in 1976, remains a
prescription drug is most of the world. However is OTC
in USA under trademark Aleve.
Naproxen Sodium
• member of the 2arylpropionic acid
(profen) family of
NSAIDs
• It is an odorless, white to
off-white crystalline
substance
• Prescribed for people
suffering from:
Formula C14H14O3
(+)-(S)-2-(6-methoxynaphthalen-2-yl)
propanoic acid
osteoarthritis, rheumatoid arthritis, psoriatic arthritis, gout,
ankylosing spondylitis, injury (like fractures), menstrual cramps,
tendonitis, bursitis, and the treatment of primary dysmenorrhea
Ketoprofen
• one of the propionic acid
class of non-steroidal antiinflammatory drug (NSAID)
with analgesic and
antipyretic effects. It acts by
inhibiting the body's
production of prostaglandin
• Brand names in the US are
Orudis and Oruvail
• 12.5 mg. OTC, greater
amounts are prescription
2-(3-benzoylphenyl)propanoic acid
Formula
C16H14O3
NSAIDS
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What is an NSAID?
Non-steroidal anti-inflammatory drug
How does it work?
Reduces inflammation, that leads to pain. Works
by inhibition of enzyme COX-1 or COX2…cyclooxygenase, which is needed to produce
Prostaglandins…chemical that increases swelling
and therefore pain
NSAIDS continued…
Why do NSAIDS bother the stomach?
• One type of prostaglandin is needed to
make the protective lining of the stomach.
So, if this chemical is reduced, the stomach
physiology is altered…pain or ulcer can
result.
How are COX-2 inhibitors different
than COX-1?
• COX-1 related to stomach, COX-2, is
not. So, new class of COX-2 inhibitors on
market…Celebrex (Vioxx,Bextra removed.
linked to increase cardiovascular risk)
Cox-1
• Cox-1 inhibitor: An agent that inhibits the action
of the enzyme cox-1 (cyclooxygenase-1). The
common anti-inflammatory drugs such as aspirin,
ibuprofen, and naproxen block the action of both
cox-1 and cox-2. Cox-1 inhibitors can reduce
inflammation, but they may also decrease the
natural protective mucus lining of the stomach.
Therefore, these medications can cause stomach
upset, intestinal bleeding, and ulcers. In some
cases, using a buffered form of a cox-1 inhibitor
can eliminate or reduce these adverse effects.
Cox-2 problems?
• As many of our readers know, Vioxx is a drug that belongs to a
category of drugs called the Cox-2 inhibitors since these drugs target
an enzyme in the stomach called Cox-2. Vioxx was recalled because it
increased the risk of heart attacks (tens of thousands of Vioxx patients
died from these heart attacks and others have suffered irreparable
damage to their cardiovascular systems).
• There are two other drugs on the market right now that belong to the
Cox-2 category: Celebrex and Bextra (they are sometimes sold by
other brand names outside the United States). When it was found that
Bextra was causing many cardiovascular complications, FDA directed
its maker, Pfizer, to add a warning to Bextra label. More research has
shown that Celebrex also has adverse side effects but the data is not
conclusive yet. Pfizer is insisting that while both Celebrex and Bextra
are Cox-2 drugs their molecular structure is different from that of
Vioxx, and hence, they are not as dangerous as Vioxx. This is their
main line of argument against recalling Celebrex and Bextra though
most medical experts think that in the interest of patient safety, both
these drugs should be recalled. (Related article: FDA issues an
advisory against Celebrex and Bextra)
Cox-2 problems cont.
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A private research team claims to have identified a unique action of the painkiller
Vioxx (search), which is independent of its anti-inflammatory action, that might
explain why it’s linked to heart attack and stroke and why other similar drugs
might not be.
The researchers say the findings should reassure patients about the cardiovascular safety
of other Cox-2 drugs (search), but two cardiologists contacted by WebMD remain
unconvinced.
Vioxx was withdrawn from the market by manufacturer Merck & Co. a month and a half
ago after research showed that long-term use doubled the risk of heart attack and stroke.
While some clinical trials have shown that another widely prescribed Cox-2, Pfizer’s
Celebrex (search), is more heart friendly than Vioxx, The Cleveland Clinic cardiologist
Steven E. Nissen, MD, says the jury is still out. Pfizer is a WebMD sponsor.
“The clinical evidence to date has not implicated [Celebrex],” he tells WebMD. “But
this drug has also has not been studied as carefully in patients with a high risk of
cardiovascular disease.”
Molecular Evidence
The newly reported study was conducted by researchers with Elucida Research of
Beverly, Mass., and published in the latest issue of the journal Atherosclerosis. Elucida
founder R. Preston Mason, PhD, says the two-year study uncovered important
differences in the action of the Cox-2 drugs. These important differences may be key to
linking Vioxx to cardiovascular disease risk.
Vioxx Websites
• Recent news
• Legal information
Celebrex in the news
• Website