Fatty alcohol

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Fatty alcohol

Fatty alcohols (or long-chain alcohols) are usually high-molecular-weight, straight-chain primary
alcohols, but can also range from as few as 4-6 carbons to as many as 22-26, derived from
natural fats and oils. The precise chain length varies with the source. [1][2] Some commercially
important fatty alcohols are lauryl, stearyl, and oleyl alcohols. They are colourless oily liquids (for
smaller carbon numbers) or waxy solids, although impure samples may appear yellow. Fatty
alcohols usually have an even number of carbon atoms and a single alcohol group (-OH)
attached to the terminal carbon. Some are unsaturated and some are branched. They are widely
used in industry. As with fatty acids, they are often referred to generically by the number of
carbon atoms in the molecule, such as "a C12 alcohol", that is an alcohol having 12 carbons, for
example dodecanol.
Contents
[hide]

1 Production and occurrence

o

1.1 From natural sources

1.2 From petrochemical sources

2 Applications
o

2.1 Nutrition
3 Safety

3.1 Human Health

3.2 Environment

3.3 Aquatic Organisms

4 Common names and related compounds

5 References

6 External links

Production and occurrence[edit]

Most fatty alcohols in nature are found as waxes which are esters with fatty acids and fatty
alcohols.[1] They are produced by bacteria, plants and animals for purposes of buoyancy, as
source of metabolic water and energy, biosonar lenses (marine mammals) and for thermal
insulation in the form of waxes (in plants and insects).[3]Fatty alcohols were unavailable until the
early 1900s. They were originally obtained by reduction of wax esters with sodium by
the BouveaultBlanc reduction process. In the 1930s catalytic hydrogenation was
commercialized, which allowed the conversion of fatty acid esters, typically tallow, to the
alcohols. In the 1940s and 1950s, petrochemicals became an important source of chemicals,
and Karl Ziegler had discovered the polymerization of ethylene. These two developments opened
the way to synthetic fatty alcohols.

From natural sources[edit]

The traditional and still important source of fatty alcohols is fatty acid esters. Wax esters were
formerly extracted from sperm oil, obtained from whales. An alternative plant source is jojoba.
Fatty acid triesters, known as triglycerides, are obtained from plant and animal sources. These
triesters are subjected to transesterification to give methyl esters, which in turn are hydrogenated
to the alcohols. Although tallow is predominantly C16-C18, the chain lengths from plant sources
are more variable (C6-C24). Higher alcohols (C20C22) can be obtained from rapeseed or
mustard seed. Midcut alcohols (C12-C14) are obtained from coconut or palm oil.

From petrochemical sources[edit]

Fatty alcohols are also prepared from petrochemical sources. In the Ziegler
process, ethylene is oligomerized using triethylaluminium followed by air oxidation. This process
affords even-numbered alcohols:
Al(C2H5)3 + 18 C2H4 Al(C14H29)3
Al(C14H29)3 + 1.5 O2 + 1.5 H2O 3 HOC14H29 + 0.5 Al2O3
Alternatively ethylene can be oligomerized to give mixtures of alkenes, which are
subjected to hydroformylation, this process affording odd-numbered aldehyde, which is
subsequently hydrogenated. For example, from 1-decene, hydroformylation gives the
C11 alcohol:
C8H17CH=CH2 + H2 + CO C8H17CH2CH2CHO
C8H17CH2CH2CHO + H2 C8H17CH2CH2CH2OH
In the Shell higher olefin process, the chain-length distribution in the initial
mixture of alkene oligomers is adjusted so as to more closely match market
demand. Shell does this by means of an intermediate metathesis reaction.[4] The
resultant mixture is fractionated and hydroformylated/hydrogenated in a
subsequent step.

Applications[edit]
Fatty alcohols are mainly used in the production of detergents and surfactants.
They are components also of cosmetics, foods, and as industrial solvents. Due
to theiramphipathic nature, fatty alcohols behave as nonionic surfactants. They
find use as emulsifiers, emollients and thickeners in cosmetics and food
industry. About 50% of fatty alcohols used commercially are of natural origin, the
remainder being synthetic.[1]

Nutrition[edit]
Very long chain fatty alcohols (VLCFA), obtained from plant waxes
and beeswax have been reported to lower plasma cholesterol in humans. They
can be found in unrefined cereal grains, beeswax, and many plant-derived
foods. Reports suggest that 520 mg per day of mixed C24C34 alcohols,
including octacosanol andtriacontanol, lower low-density lipoprotein (LDL)
cholesterol by 21%29% and raise high-density lipoprotein cholesterol by 8%

15%.[citation needed] Wax esters arehydrolyzed by a bile salt

dependent pancreatic carboxyl esterase, releasing long chain alcohols and fatty
acids that are absorbed in the gastrointestinal tract. Studies of fatty alcohol
metabolism in fibroblasts suggest that very long chain fatty alcohols, fatty
aldehydes, and fatty acids are reversibly inter-converted in a fatty alcohol cycle.
The metabolism of these compounds is impaired in several inherited
human peroxisomal disorders, including adrenoleukodystrophy and SjgrenLarsson syndrome.[5]

Safety[edit]
Human Health[edit]
Fatty alcohols are relatively benign materials, with LD50s (oral, rat) ranging from
3.1-r g/kg for hexanol to 6 -8 g/kg for octadecanol. [1] For a 50 kg person, these
values translate to more than 100 g. Tests of acute and repeated exposures
have revealed a low level of toxicity from inhalation, oral or dermal exposure of
fatty alcohols. Fatty alcohols are not very volatile and the acute lethal
concentration is greater than the saturated vapor pressure. Longer chain (C12C16) fatty alcohols produce fewer health effects than short chain (< C12). Short
chain fatty alcohols are considered eye irritants, while long chain alcohols are
not.[6] Fatty alcohols exhibit no skin sensitization.[7]
Repeated exposure to fatty alcohols produce low level toxicity and certain
compounds in this category can cause local irritation on contact or low-grade
liver effects (essentially linear alcohols have a slightly higher rate of occurrence
of these effects). No effects on the central nervous system have been seen with
inhalation and oral exposure. Tests of repeated bolus dosages of 1-hexanol and
1-octanol showed potential for CNS depression and induced respiratory distress.
No potential for peripheral neuropathy has been found. In rats, the no
observable adverse effect level (NOAEL) ranges from 200 mg/kg/day to
1000 mg/kg/day by ingestion. There has been no evidence that fatty alcohols
are carcinogenic, mutagenic, or cause reproductive toxicity or infertility. Fatty
alcohols are effectively eliminated from the body when exposed, limiting
possibility of retention or bioaccumulation.[7]
Margins of exposure resulting from consumer uses of these chemicals are
adequate for the protection of human health as determined by the Organization
for Economic Co-operation and Development (OECD) high production volume
chemicals program.[6][8]

Environment[edit]
Fatty alcohols up to chain length C18 are biodegradable, with length up to C16
biodegrading within 10 days completely. Chains C16 to C18 were found to
biodegrade from 62% to 76% in 10 days. Chains greater than C18 were found to
degrade by 37% in 10 days. Field studies at waste-water treatment plants have
shown that 99% of fatty alcohols lengths C12-C18 are removed. [7]
Fate prediction using fugacity modeling has shown that fatty alcohols with chain
lengths of C10 and greater in water partition into sediment. Lengths C14 and
above are predicted to stay in the air upon release. Modeling shows that each
type of fatty alcohol will respond independently upon environmental release. [7]

Aquatic Organisms[edit]
Fish, invertebrates and algae experience similar levels of toxicity with fatty
alcohols although it is dependent on chain length with the shorter chain having
greater toxicity potential. Longer chain lengths show no toxicity to aquatic
organisms.[7]

Chain Size

Acute Toxicity for fish

Chronic Toxicity for fish

< C11

1100 mg/l

0.1-1.0 mg/l

C11-C13

0.1-1.0 mg/l

0.1 - <1.0 mg/l

C14-C15

NA

0.01 mg/l

>C16

NA

NA

This category of chemicals was evaluated under the Organization for Economic
Co-operation and Development (OECD) high production volume chemicals
program. No unacceptable environmental risks were identified. [8]

Common names and related compounds[edit]

Name

Carbon atoms Branches/saturated?

Formula

tert-Butyl alcohol

4 carbon atoms

C4H10O

tert-Amyl alcohol

5 carbon atoms

C5H12O

3-Methyl-3-pentanol

6 carbon atoms

C6H14O

Ethchlorvynol

7 carbon atoms

C7H9ClO

1-Octanol (capryl alcohol)

8 carbon atoms

C8H18O

2-ethyl hexanol

8 carbon atoms branched

pelargonic alcohol (1-nonanol)

9 carbon atoms

1-Decanol (decyl alcohol, capric alcohol)

10 carbon
atoms

Undecyl alcohol (1-undecanol, undecanol,

Hendecanol)

11 carbon
atoms

Lauryl alcohol (Dodecanol, 1-dodecanol)

12 carbon
atoms

Tridecyl alcohol (1-tridecanol, tridecanol,

isotridecanol)

13 carbon
atoms

Myristyl alcohol (1-tetradecanol)

14 carbon
atoms

Pentadecyl alcohol (1-pentadecanol,

pentadecanol)

15 carbon
atoms

cetyl alcohol (1-hexadecanol)

16 carbon
atoms

palmitoleyl alcohol (cis-9-hexadecen-1-ol)

16 carbon
atoms

Heptadecyl alcohol (1-n-heptadecanol,

heptadecanol)

17 carbon
atoms

stearyl alcohol (1-octadecanol)

18 carbon
atoms

Nonadecyl alcohol (1-nonadecanol)

19 carbon
atoms

arachidyl alcohol (1-eicosanol)

20 carbon
atoms

Heneicosyl alcohol (1-heneicosanol)

21 carbon
atoms

behenyl alcohol (1-docosanol)

22 carbon

unsaturated

atoms

erucyl alcohol (cis-13-docosen-1-ol)

22 carbon
atoms

lignoceryl alcohol (1-tetracosanol)

24 carbon
atoms

ceryl alcohol (1-hexacosanol)

26 carbon
atoms

1-heptacosanol

27 carbon
atoms

montanyl alcohol, cluytyl alcohol, or 1octacosanol

28 carbon
atoms

1-nonacosanol

29 carbon
atoms

myricyl alcohol, melissyl alcohol, or 1triacontanol

30 carbon
atoms

1-dotriacontanol

32 carbon
atoms

geddyl alcohol (1-tetratriacontanol)

34 carbon
atoms

Cetearyl alcohol

unsaturated

C32H66O