POLYENES

Polyene is a hydrocarbon with several carbon-carbon double bonds, especially one

having a chain of alternating single and double bonds. Polyenes are poly-unsaturated
organic compounds that contain at least three alternating double and single carbon–carbon
bonds. These carbon–carbon double bonds interact in a process known as conjugation
resulting in some unusual optical properties. Related to polyenes are dienes, where there
are only two alternating double and single bonds.

FUNCTIONALITY
Polyenes bind to ergosterol in the cell membrane of fungi and form aqueous pores
that promote leakage of intracellular ions and disrupt active transport mechanisms
dependent on membrane potential.
Organic dyes are polyenes with alternating single and double bonds.
Representative Polyenes

Amphotericin B is an example of a polyene antifungal (antimycotic) agent. C 47H73O17

Leukotriene A4 is a regulator of the immune response.

 Retinal is the chemical basis of animal vision..

Beta-carotene is red-orange pigment abundant in plants and fruits, notably carrots. Beta
carotene is oxidized to vitamin A in the body. Its color is due to the large number of
alternating single and double bonds

Polyacetylenes are a synthetic polymer of theoretical interest because they exhibit metallic
properties upon oxidation.

NOMENCLATURE
The term polyene simply implies the presence of several alkenes. To be more
specific, a diene has two C=C, a triene has 3 C=C etc. Polyenes are named in a similar
manner to alkenes themselves. The root name is based on the longest chain containing
both ends of all the alkene units. The chain is numbered so as to give the one of the alkene
units the lowest possible number (i.e. first point of difference). The locant for the lowest
numbered carbon of each alkene is used in the name. The appropriate multiplier (i.e. di- for
two, tri for three) is inserted before the -ene suffix. In order make the name pronounceable,
-a- is inserted after the root. If there is more than one C=C that can be E/Z, then the location
needs to be included with the locant, e.g. (2E,4Z)-
 Functional group is an alkene, therefore suffix = -ene. There are two alkenes, so
insert the multiplier -di.
The longest continuous chain is C4 therefore root plus "a" = buta. The C=C units are both at
the ends so we can number from either end. Locants for C=C units are therefore 1- and 3-
buta-1,3-diene or 1,3-butadiene
butadiene
CH2=CHCH=CH2
The longest continuous chain is C5 therefore root plus "a" = penta. The first point of
difference requires that we number from the right as drawn. Locants for C=C units are
therefore 1- and 3-. The C3=C4 alkene has E stereochemistry (E)-penta-1,3-diene or (E)-
1,3-pentadiene
pentadiene
CH3CH=CHCH=CH2
The longest continuous chain is C5 therefore root plus "a" = penta. The substituent is
a C1 alkyl group i.e. a methyl group. The first point of difference doesn't distinguish the
C=C. So, need to apply the first point of difference to the alkyl substituent. The first point of
difference requires that we number from the left as drawn. The methyl group locant is 2-.
Therefore the locants for C=C units are 1- and 4-
2-methylpenta-1,4-diene or 2-methyl-1,4-pentadiene
CH3C(CH3)=CHCH=CH2

PHYSICAL PROPERTIES
Some polyenes are brightly colored, an otherwise rare property for a hydrocarbon.
Normally alkenes absorb in the ultraviolet region of a spectrum, but the absorption energy
state of polyenes with numerous conjugated double bonds can be lowered such that they
enter the visible region of the spectrum, resulting in compounds which are coloured
(because they contain a chromophore). Thus many natural dyes contain linear polyenes,
e.g. beta-carotene, which is responsible for the color of carrots.

CHEMICAL and ELECTRICAL PROPERTIES

 Polyenes tend to be more reactive than simpler alkenes. For example, polyene-
containing triglycerides are reactive towards atmospheric oxygen. Polyacetylene, which
partially oxidized or reduced, exhibits high electrical conductivity. Most conductive polymers
are polyenes, and many have conjugated structures.

SOURCES
Polyene antimycotics, sometimes referred to as polyene antibiotics, are a class of
antimicrobial polyene compounds that target fungi. These polyene antimycotics are typically
obtained from some species of Streptomyces bacteria. The polyenes bind to ergosterol in
the fungal cell membrane and thus weakens it, causing leakage of K+ and Na+ ions, which
may contribute to fungal cell death. Amphotericin B, nystatin, and natamycin are examples
of polyene antimycotics. They are a subgroup of macrolides.

USES
Related to polyenes are dienes, where there are only two alternating double
and single bonds. The following polyenes are used as antibiotics for humans:
amphotericin B, nystatin, candicidin, pimaricin, methyl partricin, and trichomycin.

Figure 1. The polyene carotene is responsible for the orange colour of carrots.
Polyene Antifungal Drugs

Amphotericin, nystatin, and pimaricin interact with sterols in the cell membrane (ergosterol
in fungi, cholesterol in humans) to form channels through which small molecules leak from
the inside of the fungal cell to the outside.
Few fatty acids are polyenes. Another class of important polyenes are polyene
antimycotics.
The polyene antibiotics comprise a class of molecules that are toxic to fungi but not to
bacteria. They are produced by the bacteria Streptomyces. Although there are many
polyene antibiotics (KINSKY, 1967) only three are used clinically to treat fungal infections -
nystatin, amphotericin B, and candicidin. All three are used in the treatment of topical
infections, while only amphotericin B is used against systemic infections. Nystatin and
amphotericin Bare most frequently used clinically, and have been extensively studied
experimentally.

PREPARATION
Polyenes are synthesized from unsaturated materials having allylic hydroxyl groups,
which react with imidosulfides to produce sulfones. Removal of the sulfone group, e.g. by
reaction with alkyllithium and iodine, results in compounds in which the allylic carbons are
joined by a double bond. The reactions take place easily over wide temperature ranges. The
method is particularly advantageous in the synthesis of carotenoids from polyene alcohols,
being much simpler and easier to use than previous carotenoid syntheses.

ANALYSIS

Antifungal Drugs
Ruben Vardanyan, Victor Hruby, in Synthesis of Best-Seller Drugs, 2016
33.1 Polyenes
The polyene compounds are so named because of the alternating conjugated double bonds that
constitute a part of their macrolide ring structure (Fig. 33.1.). The polyene antibiotics are
produced by Streptomyces species. Polyenes target the ergosterols the main component of fungal
cell by destabilizing the plasma membrane and initiate cell lysis. Polyenes are also thought to
cause oxidative damage. The polyene antifungal agents—amphotericin-B (33.1.1) [22-
26], nystatin A1 (usually referred to as nystatin) (33.1.2) [27,28], and natamycin (33.1.3) [29,30]
—are the only three members of the polyene/macrolide group of antifungal drugs that are used to
treat human infections.
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Fig. 33.1. Antifungal polyene drugs.
Amphotericin B, discovered in 1956, represents a gold standard, the mainstay antifungal agent
for treatment of life-threatening mycoses and for most other mycoses, with the possible
exception of the dermatophytoses.
The drug must be administered intravenously and is associated with numerous side effects,
ranging from phlebitis at the infusion site to renal toxicity.
Nystatin was the first successful antifungal antibiotic to be developed, and it is still in general
use against Candida species.
Pimaricin (natamycin) is another polyene; it is used topically to treat superficial mycotic
infections of the eye. It is active against both yeasts and molds.
Read full chapter
ANALYTICAL METHODS
George Wypych, in PVC Degradation and Stabilization (Third Edition), 2015
10.5.4 FOURIER TRANSFORM INFRARED, FTIR
Polyene index, carboxyl index, characteristic group evaluation, and degradation depth profiling
are some of the most important utilities in PVC degradation studies for which FTIR data are
indispensable. Rather than to show a list of different application which would be too numerous to
be practical, assignment of various absorption bands is given below (Table 10.2).
Table 10.2. Assignment of absorption bands in PVC compounds.

Wavenumber, cm −1
Description Reference
3665 carboxylic acid –OH stretching 135
3200-3600 hydroxyl 135
3080-3700 hydroxyl 7
2970.8-2807.8 four bands of HCl absorption in gas-phase FTIR 158
Wavenumber, cm −1
Description Reference
2800-3600 hydroxyl 136
2730 aldehyde, C–H stretching 135
2220-2230 CO  – volatile product of UV irradiation
2 71
1780-1785 carbonyl of –COCl group 64,136,137
1740-1750 isolated carbonyl group (−CHCl–CO–CHCl–) 64,136,137
1737 acrylic impact modifier 138
1734 carbonyl 139
1733 carbonyl 135
1715-1720 carbonyl of –COOH group 64,136,137
1720 carbonyl 140
1700-1750 carbonyl of surface soiling agent 141
1650 polyene sequence 142,156
1630 CaCl 2 143
1606 cadmium octoate 144
1605 carbonyl conjugated with polyene 136
1600 polyene 139
1567 barium octoate + cadmium octoate (1:1) 144
1554 CdCl–carboxylate 145
1550 calcium stearate 146
1547 barium octoate 144
1543, 1588, 1622 zinc octoate 144
1540, 1580 metal stearates 147
1539 zinc stearate 146
1538-1545 metal lanolin fatty acids 157
1510, 1566 zinc stearate 144
1504 barium stearate 144
1450, 875 CaCO 3 143
1430, 1242 C–H 139
 Wavenumber, cm −1
Description Reference
1240 epoxy group 159
1150 CaSO 4 143
962 C–C 139
875 −C=C– stretching 148
823 epoxy group 159
692 C–Cl stretching in atactic configuration 149
685, 614 C–Cl 139
640 C–Cl stretching in syndiotactic diad 150
637, 1427 crystalline bands 151
635 C–Cl stretching in syndiotactic configuration 149
635, 604, 1427 crystalline bands 152
616,1435 amorphous bands 151
615,1435 amorphous bands 152
The majority of measurements are made using KBr pellets but thick samples are measured with
specular reflectance,153 and samples with damaged surface (e.g., UV exposed samples) by either
photoacoustical154 or micro-attenuated total reflectance.155 In some studies, microscopic
attachment is also used.
REFERENCE

Zotchev, Sergey B. (2003). "Polyene macrolide antibiotics and their applications in human
therapy". Current Medicinal Chemistry. 10: 211–223. Retrieved Agaust 25, 2019.

NCBI Bookshelf (1996). "Polyene Antifungal Drugs”. The University of Texas Medical
Branch at Galveston. Retrieved 25 August 2019.

Torrado, J. J.; Espada, R.; Ballesteros, M. P.; Torrado-Santiago, S. " Amphotericin B

formulations and drug targeting" Journal of Pharmaceutical Sciences 2008, volume 97, pp.
2405-2425. Retrieved August 25, 2019.

Lam, Jacky W. Y.; Tang, B. Z.; "Functional Polyacetylenes" Accounts of Chemical

Research 2005, volume 38, pp. 745-754. Retrieved August 25, 2019.

Hamilton-Miller (1973). "Chemistry and Biology of the Polyene Macrolide Antibiotics".

Bacteriological Reviews. American Society for Microbiology. 37 (2): 166–196. Retrieved
August 26, 2019.