A Computational Study of a Prebiotic Synthesis of α-Tocopherol,
Vitamin-E and Tocols
NIGEL AYLWARD
BMS Education Services Company,
Sea Meadow House,
Road Town, Tortola,
BRITISH VIRGIN ISLANDS
Abstract: - The prebiotic synthesis of α-tocopherol and the tocols is postulated as a copolymerization of the
planetary gases propyne, ethyne and carbon monoxide on a magnesium ion metalloporphyrin complex where
the ligands are bonded on the metal or nitrogen pyrrole sites as a two site catalyst. The order of addition of the
monomers to form the chroman residue of α-tocopherol is 2 ethyne, propyne, carbon monoxide, 2 ethyne,
carbon monoxide leading to bonding on the catalyst to give a chroman derivative. The phytyl side-chain is
formed from the successive addition of propyne and ethyne monomers where the isoprenoid residues formed
are subsequently hydrogenated. The separation of the catalyst is facilitated by hydrogen radicals to give α-
tocopherol. The reactions have been shown to be feasible from the overall enthalpy changes in the ZKE
approximation at the HF and MP2 /6-31G* level, and with acceptable activation energies.
Key-Words: - Prebiotic photochemical synthesis, α,β,γ,δ-tocopherol, ε,ζ,η-tocols, Mg.porphin.
Received: June 23, 2022. Revised: October 19, 2023. Accepted: November 21, 2023. Published: December 31, 2023.
1 Introduction
Tocopherals are natural products derived from
chroman, Figure 1, that are essential dietary factors
associated with reproduction, [1]. The structure of
α-tocopherol is representative of the group which
contains β, γ, and δ-tocopherol, Figure 4, which
differ only in the position and number of methyl
groups on the benzenoid ring, [2]. The same
configurations exist for the tocotrienols, except that
the hydrophobic side chain has three carbon-carbon
double bonds whereas the tocopherols have a
saturated side chain, [3]. They are isolated from
vegetables and seed-germ oils, [4]. The key-step in
the industrial synthesis of (all-rac)-α-tocopherol
(synthetic vitamin E) is the condensation reaction of
trimethylhydroquinone with the C20 building block
isophytol, [5], [6], [7]. Enzymatic synthesis has
been achieved, [8], and the synthesis of isophytol
from farnesene using genetic engineering, [9]. The
biosynthesis has been illucidated, [10], [11].
Vitamin E (tocochromanols) are clearly
established as essential compounds in vertebrate
species, [12]
Whilst natural α−Τocopherol has a single
stereoisomer RRR- α−tocopherol, tocotrienols
possess only the chiral stereocenter at C-2, and
naturally occurring tocotrienols exclusively possess
the (2R,3′E,7′E) configuration, [13].
Tocochromanols are widely used in feed
additives, medicine, food, cosmetics, and other
fields exerting their influence on physiological
functions based on its antioxidation properties,
including improving the body’s immunity, fertility,
possessing anti-cancer and anti-inflammatory
properties, heart protection, and nerve protection,
[14], [15], [16], [17]. Vitamin E is an antioxidant,
protecting polyunsaturated lipophilic molecules
from peroxidation, [18], [19], by free radicals such
as hydroxyl or oxygen radicals leading to free
radical chain-reactions. It also has biochemical and
therapeutical aspects, [20], [21]. Vitamin E is an
enzyme activity regulator for protein kinase
C (PKC), which plays a role in smooth
muscle growth, [22].
From a prebiotic perspective, [23], it is
desirable if the reactant molecules were present
from a supposed prebiotic atmosphere often held to
have been originally mildly reducing, [4], [24],
implying the presence of concentrations of carbon
monoxide, ammonia, water and hydrogen. It has
also been demonstrated that porphin present from
the time of photosynthesis, [25], may act as a
catalyst for the formation of sugars, [26] and
terpenes, [27].
This paper proposes a model for the catalytic
photochemically activated copolymerization of the
simple gases, propyne, ethyne and carbon monoxide
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where the order of addition to form the chroman
residue is 2 ethyne, propyne, carbon monoxide, 2
ethyne, carbon monoxide .Initiation of the
polymerization occurs with the addition of propyne
to the catalyst whilst termination and separation of
the catalyst is spontaneous. The synthesis of this
biochemical vitamin is postulated to be an example
of a general mechanism for the prebiotic synthesis
of poly unsaturated fatty acids and terpenes formed
over a considerable period of time.
The reactions described have been deduced as
kinetically and thermodynamically viable, but
photochemical excitation is required.
2 Problem Formulation
This proposed computational study of a plausible
synthesis of α-tocopherol involves the calculation
of the enthalpy changes for reaction intermediates in
the ZKE approximation and the calculation of
activation energies at the HF level. These activation
energies may all be accessible as the catalyst may
absorb appreciable photochemical activation, (0.21
h). The computations tabulated in this paper used
the GAUSSIAN09, [28].
The standard calculations at the HF and MP2
levels including zero-point energy corrections and
scaling, [29], are as previously published, [23]. The
charge transfer complexes are less stable when
calculated at the Hartree Fock level, [30], and
activation energies calculated at the HF level
without scaling are less accurate.
If the combined energy of the products is less
than the combined energy of the reactants it may
show that the reaction is also likely to be
spontaneous at higher temperatures. This paper uses
the atomic unit of energy, the hartree, [28].
1h = 627.5095 kcal.mol-1.1h = 4.3597482 x 10-18 J
Mulliken charges are in units of the electronic
charge.
3 Problem Solution
3.1 Total Energies (hartrees)
The initial reactants are deemed to be the simple
interstellar and planetary gases propyne, ethyne,
carbon monoxide and hydrogen, [31], formed from
elementary hydrocarbons such as methane and
propane, [32], [33], [34].
The intermediates required in this
copolymerization and the energies of the stable
complexes are shown in Table 1.
Table 1. MP2 /6-31G* total energies and zero point
energies (hartrees) for the respective equilibrium
geometries.
Molecule MP2 ZPE (HF)
hartree hartree
propyne (1) -116.24181 0.06010
Mg.porphin (2) -1185.12250 0.29262
Mg.1,2-dehydro 4-methyl-penta-1.3-dien-1-
yl.porphin (3) -1417.59302 0.43597
Mg.1,porphin.2-dehydro 4-methyl-penta-1.3-dien-
N1-yl porphin
(4) -1417.69182 0.41981
Mg.1,ethynyl.porphin.2-dehydro 4-methyl penta-
1,3-dien-N1-yl
(5) -1494.65328 0.44469
Mg.1,3-dehydro 1-didehydromethyl -5-methyl hexa-
2,4-dien-1-yl (6) -1494.63846 0.44477
Mg.1,3-dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin (7) -1495.94765 0.47258
Mg.1,porphin 3-dehydro 1,5-dimethyl hexa-2,4-
dien-1-yl.porphin (8) -1495.91438 0.46288
Mg.1,ethynyl.porphin 3-dehydro 1,5-dimethyl hexa-
2,4-dien-1-yl.porphin
(9) -1572.98448 0.50631
Mg.1,5-dehydro-3,7-dimethyl-octa-1,4,6-trien-
1yl.porphin
(10) -1573.12584 0.50303
Mg.1,porphin.5-dehydro-3,7-dimethyl-octa-1,4,6-
trien-1yl
(11) -1572.97938 0.50983
Mg.1,propynyl.porphin.5-dehydro-3,7-dimethyl-
octa-1,4,6-trien-1yl
(12) -1689.15483 0.56873
Mg.1,6-dehydro 1-didehydroethyl- 4,8-dimethyl
nona 2,5,7-trien-1-yl.porphin
(13) -1689.41858 0.56640
Mg.1,porphin. 6-dehydro 1-(1-didehydroethyl)- 4,8-
dimethyl nona 3,5,7-trien-1-yl
(14) -1689.30770 0.57224
Mg.1,carbonyl.porphin.4-dehydro 1-(1-
didehydroethyl) -4,8-dimethyl nona-2,5,7-trien-1yl
(15) -1802.19923 0.57899
Mg.1, 6-dehydro 1-oxo- 2,6,10-trimethyl undeca-
2,4,7,9-tetraen-1yl.porphin
(16) -1802.49088 0.58620
Mg.1,porphin.6-dehydro 1-oxo-2,6,10-trimethyl
undeca-2,4,7,9-tetraen-1yl
(17) -1802.46823 0.58960
Mg.1,ethynyl.porphin.6-dehydro1-oxo-2,6,10-
trimethyl undeca-2,4,7,9-tetraen-1yl
(18) -1879.50606 0.61897
Mg.1,7-dehydro 1-didehydromethyl-2-oxo-3,7,11-
trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin
(19) -1879.41356 0.62096
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Mg.1,porphin.7-dehydro 1-didehydromethyl-2-oxo-
3,7,11-trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin
(20) -1879.44501 0.61825
Mg.1,ethynyl.porphin.7-dehydro 1-
didehydromethyl-2-oxo-3,7,11-trimethyl dodeca
3,5,8,10-tetraen-N1-yl
(21) -1956.51343 0.64344
Mg.1,7-dehydro 1,2-didehydromethyl-3-oxo-4,8,12-
trimethyl trideca-4,6,9,11-tetraen-N1-yl. porphin.
(22) -1956.46672 0.65293
Mg.1, porphin.8-dehydro 1,2-didehydromethyl-3-
oxo-4,8,12-trimethyl trideca 4,6,9,11-tetraen-N1-
yl.porphin
(23) -1956.44701 0.65204
Mg.1,carbonyl.porphin.8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-trimethyl trideca-
4,6,9,11-tetraen-N1-yl. (24)
-2069.72987 0.66033
Mg.1,9-dehydro 1,4-dioxo.2,3-didehydromethyl-
5,9,13-trimethyl tetradec-5,7,10,12-tetraen-1-
yl.porphin (25)
-2069.59578 0.66033
Mg.1,porphin.9-dehydro 1,4-dioxo.2,3-
didehydromethyl-5,9,13-trimethyl tetradeca-
5,7,10,12-tetraen-1-yl.
(26) -2069.63917 0.66033
Mg.1,porphin.2-(3-dehydro 3,7-dimethyl-octa-
1,4,6-trien-1yl) 5,6-didehydromethyl 1,4-dioxo
cyclohexane N1-yl
(27) -2069.59573 0.660327
5,6-(didehydromethyl) 2-(3,7-dimethyl octa-1,4,6-
trien-1yl) 1,4-dihydroxy cyclohexane
(28) -2069.44254 0.65988
2-methyl 2-(4-methyl penta-1,3-dien-1yl) 5,7,8-
trimethyl 6-hydroxy chroman.
(29) -883.40972 0.42449
2-methyl 2-(4-methyl pentan-1yl) chroman
(30) -889.54152 0.48761
Mg.porphin-- -1185.00997 0.28821
3,7-dimethyl octane -392.81513 0.30136
2-methylbutane -196.99336 0.17139
2-methylbutene -195.79496 0.14578
H. -0.49823
OH. -75.52257 0.00911
OH- -75.51314 0.00885
H2O -76.19685 0.02298
H2 -1.14414 0.01059
_____________________________________
3.2 The Overall Stoichiometry for the
Formation of the α-tocopherol
Although Mg.porphin is here taken as the catalyst
for the reaction, the overall stoichiometry to form α-
tocopherol, Figure 1, from the primary reactants is
given as:
5CH3-C ≡ C-H + 6H-C ≡ C-H + 2CO + 9H2 →
C29H50O2
α-tocopherol
ΔH = -1.06648 h
The enthalpy change is negative indicating that
this may be the energetically favourable route to the
initial formation of the vitamin E, Figure 1.
Fig. 1: Atom numbering in α-tocopherol
To save computer time the molecule is split into
the chroman derivative, 2-methyl 2-(4-methyl
pentan-1yl) chroman, Figure 2, and the side chain
substituent alkane, 3,7-dimethyl octane, Figure 3.
Fig. 2: 2-methyl 2-(4-methyl pentan-1yl) chroman
Fig. 3: 3,7-dimethyl octane
The overall stoichiometry to form the 2-methyl
2-(4-methyl pentan-1yl) chroman is as follows:
3 CH3-C ≡ C-H + 4 H-C ≡ C-H + 2CO + 5H2 →
C19H30O2
ΔH = -0.67415 h
The overall stoichiometry to form the 3,7-
dimethyl octane, Figure 3, is as follows:
2 H-C ≡ C-H + 2 CH3-C ≡ C-H + 5H2 → C10H22
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ΔH = -0.41555 h
Finally, the two are combined according to the
equation,
2-methyl 2-(4-methyl pentan-1yl) chroman + 3,7-
dimethyl octane → tocopherol + H2
ΔH = --1.06648 h
The enthalpy change is negative indicating that
this may be the energetically favourable route to the
initial formation of the tocopherol series.
The intermediates by which these stoichiometric
reactions may have occurred are as follows.
Molecules are numbered consecutively.
Subsections depict alternatives to give some of
the many variations of the α-tocopherol structure.
A standard numbering of the atoms in the
tocopherol structure is given in Figure 1.
3.3 The Formation of Mg.1, 2-dehydro 4-
methyl-penta-1.3-diene.porphin
The prebiotic photochemically activated, surface
catalyzed synthesis of Mg.1,2-dehydro 4-methyl-
penta-1.3-diene.porphin has been described, [27],
where the catalyst was taken as Mg.porphin, [23],
[26]. The same catalyst is used in this synthesis of
vitamin E where the initial reactant is the gas
propyne. Here, those first reactions are summarized
and represented here as:
2 CH3-C ≡ C-H + Mg.porphin →
(1) (2)
Mg.1,2-dehydro 4-methyl penta-1,3-dien-1-
yl.porphin (3)
ΔH = -0.07948 h
The reaction appears feasible having been
excited photochemicaly on the surface catalyst.
The activation energy in these charge transfer
reactions or the formation of van der Waals
complexes is always achievable as the catalyst can
absorb considerable photochemical activation, 0.21
h, [26].
At this stage in the synthesis of vitamin E
analogues the long side-chains of from 1 to 3
isoprenoid groups may be added, [35], and
hydrogenated to produce various sterically specific
side-chains. These are postponed until later.
3.4 The formation of Mg.1,porphin.2-
dehydro 4-methyl penta-1,3-dien-N1-
yl
The Mg.1,2-dehydro 4-methyl penta-1,3-dien-1-
yl.porphin may be excited to a higher energy state
as,
Mg.1,2-dehydro 4-methyl penta-1,3-dien-1-
yl.porphin →
Mg.1,porphin.2-dehydro 4-methyl penta-1,3-dien-
N1-yl (4)
ΔH = 0.11318 h
Here the activation energy is the same as the
enthalpy change, [35].
3.5 The Formation of Mg.1,ethynyl.porphin.
2-dehydro 4-methyl penta-1,3-dien-N1-yl
The Mg.1,porphin.2-dehydro 4-methyl penta-1,3-
dien-N1-yl may add a further ethyne as,
H-C ≡ C-H + Mg.1,porphin.2-dehydro 4-methyl
penta-1,3-dien-N1-yl →
Mg.1,ethynyl.porphin.2-dehydro 4-methyl penta-
1,3-dien-N1-yl (5)
ΔH = -0.01192 h
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
HC
C
H
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The activation energy to form these van der
Waals’s complexes is either zero or very marginal,
as here.
3.6 The fORMATION of Mg.1, 3-dehydro 1-
didehydromethyl -5-methyl hexa-2,4-
dien-1-yl
The Mg.1,ethynyl.porphin.2-dehydro 4-methyl
penta-1,3-dien-N1-yl adducts may coalesce as,
Mg.1,ethynyl.porphin.2-dehydro 4-methyl penta-
1,3-dien-N1-yl →
Mg.1,3-dehydro 1-didehydromethyl -5-methyl hexa-
2,4-dien-1-yl (6)
ΔH = 0.01489 h
Although an asymmetric centre is created here
as R at C1 it is later converted to a transient
carbonium ion. The ethyne adduct here depicted
later provides the C2 of the chroman ring, yet to be
formed, and also the C2-methyl substituent of the
chroman ring system.
3.6.1 The Formation of γ, δ, and η-tocols
Failure of the ethyne adduct to bond as shown
above, but to be incorporated with both ethyne C
atoms bonded to adjacent monomers may lead to the
absence of a methyl group at C2 of the tocol, [35].
3.7 The Formation of Mg.1, 3-dehydro 1,5-
dimethyl hexa-2,4-dien-1-yl.porphin
The Mg.1,3-dehydro 1-didehydromethyl -5-methyl
hexa-2,4-dien-1-yl may be hydrogenated as,
H2 + Mg.1,3-dehydro 1- didehydromethyl -5-methyl
hexa-2,4-dien-1-yl →
Mg.1,3-dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin (7)
ΔH = -0.14972 h
This hydrogenation is exothermic without
activation energy.
3.8 The Formation of Mg.1,porphin 3-
dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin
The Mg.1,3-dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin may be excited to a higher energy state
as,
Mg.1,3-dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin →
Mg.1,porphin 3-dehydro 1,5-dimethyl hexa-2,4-
dien-1-yl.porphin (8)
ΔH = 0.024635 h
The activation energy was the same as the
enthalpy change.
3.9 The Formation of Mg.1,ethynyl.porphin
3-dehydro 1,5-dimethyl hexa-2,4-dien-1-
yl.porphin
The Mg.1,porphin 3-dehydro 1,5-dimethyl hexa-2,4-
dien-1-yl.porphin may add a further ethyne as,
Mg.1,porphin 3-dehydro 1,5-dimethyl hexa-2,4-
dien-1-yl.porphin + H-C ≡ C-H →
Mg.1,ethynyl.porphin 3-dehydro 1,5-dimethyl hexa-
2,4-dien-1-yl.porphin (9)
ΔH = 0.00914 h
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3.10 The Formation of Mg.1,5-dehydro-3,7-
dimethyl-octa-1,4,6-trien-1yl.porphin.
The Mg.1,ethynyl.porphin 3-dehydro 1,5-dimethyl
hexa-2,4-dien-1-yl.porphin adducts may coalesce as,
Mg.1,ethynyl.porphin 3-dehydro 1,5-dimethyl hexa-
2,4-dien-1-yl.porphin →
Mg.1,5-dehydro-3,7-dimethyl-octa-1,4,6-trien-
1yl.porphin (10)
ΔH = -0.14428 h
This reaction is without activation energy.
3.11 The Formation of Mg.1,porphin.5-
dehydro-3,7-dimethyl-octa-1,4,6-trien-
1yl.
The Mg.1,5-dehydro-3,7-dimethyl-octa-1,4,6-trien-
1yl.porphin may be excited to a higher energy state
as,
Mg.1,5-dehydro-3,7-dimethyl-octa-1,4,6-trien-
1yl.porphin →
Mg.1,porphin.5-dehydro-3,7-dimethyl-octa-1,4,6-
trien-1yl (11)
ΔH = -0.14251 h
This reaction is without activation energy.
3.12 The Formation of Mg.1,propynyl.
porphin.5-dehydro-3,7-dimethyl-octa-
1,4,6-trien-1yl.
The Mg.1,porphin.5-dehydro-3,7-dimethyl-octa-
1,4,6-trien-1yl may add a propyne adduct as,
CH3-C ≡ C-H + Mg.1,porphin.5-dehydro-3,7-
dimethyl-octa-1,4,6-trien-1yl →
Mg.1,propynyl.porphin.5-dehydro-3,7-dimethyl-
octa-1,4,6-trien-1yl (12)
ΔH = 0.07529 h
3.13 The formation of Mg.1, 6-dehydro 1-
didehydroethyl- 4,8-dimethyl nona
2,5,7-trien-1-yl.porphin
The Mg.1,propynyl.porphin.5-dehydro-3,7-
dimethyl-octa-1,4,6-trien-1yl adducts may coalesce
as,
Mg.1,propynyl.porphin.5-dehydro-3,7-dimethyl-
octa-1,4,6-trien-1yl →
Mg.1, 6-dehydro 1-didehydroethyl- 4,8-dimethyl
nona 2,5,7-trien-1-yl.porphin (13)
ΔH = -0.26582 h
The reaction is recorded as without activation
energy.
3.13.1 The Formation of γ and δ-tocopherol.
Failure to add a propyne monomer at this stage in
the syntheses, and the addition of ethyne in its place
may lead to an absence of a methyl group at C5 of
the tocol, [35].
3.14 The Formation of Mg.1,porphin. 6-
dehydro 1-(1-didehydroethyl) 4,8-
dimethyl nona 2,5,7-trien-1-yl.
The Mg.1, 6-dehydro 1-(1-didehydroethyl)- 4,8,-
dimethyl nona 2,5,7-trien-1-yl.porphin may be
excited to a higher energy state as,
Mg.1, 6-dehydro 1-(1-didehydroethyl)- 4,8,-
dimethyl nona 3,5,7-trien-1-yl.porphin →
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
H
C
CH3
HC
C
H
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
H
C
CH3
HC
C
H
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
H
C
CH3
HC
C
H
C
H
C
CH3
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
H
C
CH3
H
C
C
H
C
H
C
CH3
..
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Mg.1,porphin.6-dehydro 1-(1-didehydroethyl) 4,8-
dimethyl nona 3,5,7-trien-1-yl (14)
ΔH = 0.11608 h
The activation energy is the same as the enthalpy
change.
3.15 The Formation of Mg.1,carbonyl.
porphin. 4-dehydro 1-(1-
didehydroethyl) -4,8-dimethyl nona-
2,5,7-trien-1yl
The Mg.1,porphin. 6-dehydro 1-(1-didehydroethyl)
-4,8-dimethyl nona-2,5,7-trien-1yl may add a
carbonyl adduct as,
CO + Mg.1,porphin. 6-dehydro 1-(1-
didehydroethyl)- 4,8-dimethyl nona-2,5,7-trien-1yl
.→
Mg.1,carbonyl.porphin. 4-dehydro 1-(1-
didehydroethyl) 4,8-dimethyl nona-2,5,7-trien-1yl
(15)
ΔH = 0.13075 h
It is also inferred here that prototropic shifts
may occur along the side-chain where the enthalpy
change of the adduct in this excited state is
sufficient to provide the activation energy, 0.101 h.
This does result in a closer distance between the
charges of the charge transfer complex.
3.15.1 The Formation of ε, ζ and η-tocopherol
Failure to add a carbon monoxide monomer at this
stage in the syntheses may give rise to the tocol
analoque ε, ζ and η -tocol derivatives, [35], Figure
5.
3.16 The Formation of Mg.1,6-dehydro 1-
oxo-2,6,10-trimethyl undeca-2,4,7,9-
tetraen-1-yl.porphin
The Mg.1,carbonyl.porphin. 4-dehydro 1-(1-
didehydroethyl) -4,8-dimethyl nona-2,5,7-trien-1-yl
adducts may coallesce as,
Mg.1,carbonyl.porphin. 4-dehydro 1-(1-
didehydroethyl) -4,8-dimethyl nonan-2,5,7-trien-1-
yl →
Mg.1, 6-dehydro 1-oxo 2,6,10-trimethyl undeca-
2,4,7,9-tetraen-1yl.porphin (16)
ΔH = -0.28523 h
The reaction is without activation energy.
3.17 The Formation of Mg.1,porphin.6-
dehydro 1-oxo-2,6,10-trimethyl
undeca-2,4,7,9-tetraen-1yl.
The Mg.1,6-dehydro 1-oxo-2,6,10-trimethyl
undeca-2,4,7,9-tetraen-1yl.porphin may be excited
to a higher energy state and undergo prototropic
shifts as,
Mg.1,6-dehydro 1-oxo-2,6,10-trimethyl undeca-
2,4,7,9-tetraen-1yl.porphin →
Mg.1,porphin.6-dehydro 1-oxo-2,6,10-trimethyl
undeca-2,4,7,9-tetraen-1yl (17).
ΔH = 0.02567 h
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+
H
C
CH3
H
C
C
H
C
H
C
CH3
..
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The activation energy is the same as the enthalpy
change.
3.18 The Formation of Mg.1,ethynyl.
porphin.6-dehydro 1-oxo-2,6,10-
trimethyl undeca-2,4,7,9-tetraen-1yl.
The Mg.1,porphin.6-dehydro 1-oxo-2,6,10-trimethyl
undeca-2,4,7,9-tetraen-1yl may add another ethyne
molecule as adduct as,
H-C ≡ C-H + Mg.1,porphin.6-dehydro 1-oxo-
2,6,10-trimethyl undeca-2,4,7,9-tetraen-1yl.
→
Mg.1,ethynyl.porphin.6-dehydro 1-oxo-2,6,10-
trimethyl undeca-2,4,7,9-tetraen-1yl (18)
ΔH = 0.02889 h
This was the small activation energy.
3.19 The Formation of Mg.1,7-dehydro 1-
didehydromethyl-2-oxo-3,7,11-
trimethyl dodeca-3,5,8,10-tetraen-
1yl.porphin
The Mg.1,ethynyl.porphin.6-dehydro 1-oxo-2,6,10-
trimethyl undeca-2,4,7,9-tetraen-1yl adducts may
coalesce as,
Mg.1,ethynyl.porphin.6-dehydro 1-oxo-2,6,10-
trimethyl undeca-2,4,7,9-tetraen-1yl. →
Mg.1,7-dehydro 1-didehydromethyl-2-oxo-3,7,11-
trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin (19)
ΔH = 0.09428 h
This was also the activation energy.
3.20 The Formation of Mg.1,porphin.1-
didehydromethyl-2-oxo-3,7,11-
trimethyl dodeca-3,5,8,10-tetraen-N1-
yl.
The Mg.1,7-dehydro 1-didehydromethyl-2-oxo-
3,7,11-trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin
may be excited to a higher energy state as,
Mg.1,7-dehydro 1-didehydromethyl-2-oxo-3,7,11-
trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin →
Mg.1,porphin.7-dehydro 1-didehydromethyl-2-oxo-
3,7,11-trimethyl dodeca 3,5,8,10-tetraen-1yl.porphin
(20)
ΔH = -0.03387 h
No activation energy was recorded.
The hydrogenation was postponed until later to
gauge the reactivity.
3.21 The Formation of Mg.1,ethynyl.
porphin.7-dehydro 1-didehydromethyl-
2-oxo-3,7,11-trimethyl dodeca-3,5,8,10-
tetraenen-N1-yl.
A second ethyne may be added as adduct as,
H-C ≡ C-H + Mg.1,porphin.7-dehydro 1-
didehydromethyl-2-oxo-3,7,11-trimethyl dodeca
3,5,8,10-tetraen-1yl.porphin →
Mg.1,ethynyl.porphin.7-dehydro 1-
didehydromethyl-2-oxo-3,7,11-trimethyl dodeca
3,5,8,10-tetraen-N1-yl (21)
ΔH = -0.00542 h
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3.22 The Formation of Mg.1,8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-
trimethyl trideca-4,6,9,11-tetraen-N1-
yl.porphin.
The Mg.1,ethynyl.porphin.7-dehydro 1-
didehydromethyl-2-oxo-3,7,11-trimethyl dodeca
3,5,8,10-tetraen-N1-yl may coalesce as,
Mg.1,ethynyl.porphin.7-dehydro 1-dehydromethyl-
2-oxo-3,7,11-trimethyl dodeca 3,5,8,10-tetraen-N1-
yl →
Mg.1,8-dehydro 1,2-didehydromethyl-3-oxo-4,8,12-
trimethyl trideca-4,6,9,11-tetraen-N1-yl.porphin.
(22)
ΔH = 0.05516 h
The activation energy was the same as the enthalpy
change.
3.23 The Formation of Mg.1, porphin.8-
dehydro 1,2-didehydromethyl-3-oxo-
4,8,12-trimethyl trideca-4,6,9,11-
tetraen-N1-yl.
The adduct may be excited to a higher energy state
as,
Mg.1,porphin.8-dehydro 1,2-didehydromethyl-3-
oxo-4,8,12-trimethyl trideca 4,6,9,11-tetraen-N1-yl.
→
Mg.1, porphin.8-dehydro 1,2-didehydromethyl-3-
oxo-4,8,12-trimethyl trideca 4,6,9,11-tetraen-N1-yl.
(23)
ΔH = 0.01891 h
The activation energy was the same as the enthalpy
change.
3.24 The Formation of Mg.1,carbonyl.
porphin.8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-
trimethyl trideca-4,6,9,11-tetraen-N1-
yl.
A further carbonyl group may be added to the
Mg.1,porphin.8-dehydro 1,2-didehydromethyl-3-
oxo-4,8,12-trimethyl trideca-4,6,9,11-tetraen-N1-
yl.porphin as,
CO + Mg.1,porphin.8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-trimethyl trideca
4,6,9,11-tetraen-N1-yl.porphin →
Mg.1,carbonyl.porphin.8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-trimethyl trideca-
4,6,9,11-tetraen-N1-yl. (24)
ΔH = -0.25920 h
3.25 The Formation of Mg.1,9-dehydro 1,4-
dioxo.2,3-didehydromethyl-5,9,13-
trimethyl tetradeca-5,7,10,12-tetraen-1-
yl.porphin
The adducts on the catalyst may coalesce as,
Mg.1,carbonyl.porphin.8-dehydro 1,2-
didehydromethyl-3-oxo-4,8,12-trimethyl trideca-
4,6,9,11-tetraen-N1-yl. →
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Mg.1, 9-dehydro 1,4-dioxo.2,3-didehydromethyl-
5,9,13-trimethyl tetradeca-5,7,10,12-tetraen-1-
yl.porphin (25)
ΔH = 0.13413 h
3.26 The Formation of Mg.1,porphin.1,4-
dioxo.2,3-didehydromethyl-5,9,13-
trimethyl tetradeca-5,7,10,12-tetraen-
1-yl.
The Mg.1,9-dehydro 1,4-dioxo.2,3-
didehydromethyl-5,9,13-trimethyl tetradeca-
5,7,10,12-tetraen-1-yl.porphin may be excited to a
higher energy state as,
Mg.1,9-dehydro 1,4-dioxo.2,3-didehydromethyl-5-
9,13-trimethyl tetradeca-5,7,10,12-tetraen-1-
yl.porphin →
Mg.1,porphin.9-dehydro 1,4-dioxo.2,3-
didehydromethyl-5,9,13-trimethyl tetradeca-
5,7,10,12-tetraen-1-yl. (26)
ΔH = -0.04344 h
No activation energy was recorded for this
transition.
3.27 The Formation of Mg.1,porphin.2-(3-
dehydro 3,7-dimethyl-octa-1,4,6-trien-
1yl) 5,6-didehydromethyl 1,4-dioxo
cyclohexane N1-yl
The Mg.1,porphin.9-dehydro 1,4-dioxo.2,3-
didehydromethyl-5-9,13-trimethyl tetradeca-
5.7.10.12-tetraen-1-yl may cyclize as,
Mg.1,porphin.1,4-dioxo.2,3-didehydromethyl-5-
9,13-trimethyl tetradeca-5.7.10.12-tetraen-1-
yl.porphin →
Mg.1,porphin.2-(3-dehydro 3,7-dimethyl-octa-1,4,6-
trien-1yl) 5,6-didehydromethyl 1,4-dioxo
cyclohexane N1-yl (27)
ΔH = 0.21708 h
The activation energy for cyclisation was the same
as the enthalpy change.
3.28 The Formation of 5,6-didehydromethyl)
2-(3,7-dimethyl octa-1,4,6-trien-1yl) 1,4-
dihydroxy cyclohexane
The Mg.1,porphin.2-(3-dehydro 3,7-dimethyl-octa-
1,4,6-trien-1yl) 5,6-didehydromethyl 1,4-dioxo
cyclohexane N1-yl may separate from the catalyst
as a neutral molecule as.
Mg.1,porphin.2-(3-dehydro 3,7-dimethyl-octa-1,4,6-
trien-1yl) 5,6-didehydromethyl 4,6-dioxo
cyclohexane N1-yl →
Mg.porphin- - + 2H+ +
5,6-(didehydromethyl) 2-(3,7-dimethyl octa-1,4,6-
trien-1yl) 1,4-dihydroxy cyclohexane (28)
ΔH = -0.49000 h
The reaction is more favourable if mediated with
hydrogen or hydroxyl radicals [36].
H2O → H. + OH .
ΔH = 0.16472 h
-
N
N
N
Mg
N
CC
HCH3
CCCH3
H
+H
C
C H
3
H
C C
H
C
H
C
CH3
C
O
C
H
C
H..
..
HC
H
C
C
O
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The cis bonding of the C2 substituent ensures a
favourable orientation for further cyclization as
shown below and establish the asymmetry of the C2
carbon atom of the chroman as R. The activation
energy was 0.010 h.
3.29 The Formation of 2-methyl 2-(4-methyl
penta-1,3-dien-1yl) 5,7,8-trimethyl 6-
hydroxy chroman.
The 5,6-(didehydromethyl) 2-(3,7-dimethyl octa-
1,4,6-trien-1yl) 1,4-dihydroxy cyclohexane may
cyclize and hydrogenate as,
5,6-(didehydromethyl) 2-(3,7-dimethyl octa-1,4,6-
trien-1yl) 1,4-dihydroxy cyclohexane + 3H2 →
2-methyl 2-(4-methyl penta-1,3-dien-1yl) 5,7,8-
trimethyl 6-hydroxy chroman.(29)
ΔH = -0.29567 h
3.30 The Formation of 2-methyl 2-(4-methyl
pentan-1yl) chroman
This 2-methyl 2-(4-methyl penta-1,3-dien-1yl)
5,7,8-trimethyl 6-hydroxy chroman may be fully
hydrogenated as,
2-methyl 2-(4-methyl penta-1,3-dien-1yl) 5,7,8-
trimethyl 6-hydroxy chroman + 2H2 →
2-methyl 2-(4-methyl pentan-1yl) chroman (30)
ΔH = -0.10635 h
The α-tocopherol may be constituted as before.
3.31 The Formation of α-tocopherol.
Finally, the chroman is combined with the alkane,
3,7-dimethyl octane, according to the equation,
2-methyl 2-(4-methyl pentan-1yl) chroman + 3,7-
dimethyl octane → tocopherol + H2
ΔH = --1.06648 h
3.31.1 The Formation of Tocols
The postulated synthesis is the formation of a
specific tocol, α-tocopherol, formed from the
bonding of the, ethyne, propyne, carbon monoxide
and hydrogen facilitated by the catalyst Mg.porphin.
The energy changes in coordinating each of these
gases is minimal implying they all have comparable
probabilities of binding to the catalyst. However,
propyne may be a stronger nucleophile than ethyne,
and ethyne may be in greater concentration. A
copolymerization is expected with a full range of
different oligomers leading to a range of different
tocols, Figure 4 and Figure 5 where one or both of
the alkyne carbon atoms may contribute to the
sequence of backbone carbon atoms in the oligomer.
Table 2, depicts the source of the tocol
numbered carbon atoms leading to some
documented tocols, [35]. Ethyne is represented as e,
propyne as p, and carbon monoxide as co.
α-tocopherol
β-tocopherol
γ-tocopherol
δ-tocopherol
Fig. 4: A representation of the structure of tocols
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Table 2. Tocol oligomer sequence data. Tocol atom
number (At) and alkyne source, ethyne (e), propyne
(p) and carbon monoxide (co)
Toc
ol
At.
No.
2
At.
No.
3
At.
No.
4
At.
No.
5
At.
No.
6
At.
No.
7
At.
No.8
α
e
e
e
p
co
e
e
β
e
e
e
p
co
p
P
γ
e
e
e
e
co
e
e
δ
e
e
e
e
co
p
P
ε
p
p
e
p
p
e
e
ζ
p
p
e
p
p
p
P
η
p
p
e
e
e
p
P
A further range of different tocols are depicted in,
Figure 5.
, ε-tocol
ζ-tocol
η-tocol
Fig. 5: A representation of tocols. R-phytyl side-
chain
4 Conclusion
Predicated on a planetary atmosphere containing
simple gases such as propyne, ethyne, carbon
monoxide and a mildly reducing atmosphere
containing hydrogen gas the laws of chemical
thermodynamics and kinetics would appear
sufficient for the formation of vitamin E analoques
on its surface, provided in addition that the gases
ethyne and hydrogen cyanide would yield by free
radical reactions diacetylene cyanide, that has been
postulated as being a feasible source of the molecule
porphin and its analoques, [23], to synthesize the
photchemically activated surface catalyst
Mg.porphin, itself of extreme antiquity, [25].
However, the limited range of activation energies
involved in the long sequence of the
copolymerization would indicate the probable
formation of a large range of tocopherols and
associated trienols. All of these mentioned and
many with extended phytyl side chains are shown to
have been accessible from the polymerizations.
The purpose of this work is indicate the
expectation of such molecules being found on
planets that have the required reactant molecules
and physical conditions for this chemistry, and the
subsequent incorporation of such molecules into
later molecular development and biochemistry
where the original morphological structure may be
expected to be maintained, but sophisticted
incorporation into biochemical structures being
evolved over very large time frames. The
occurrence of this molecule in the present
biochemistry of plants and in cyanobacteria and
algae giving a protective function against
photooxidative damage in photosystem II, [37], [38]
does suggest that this may have occurred during the
history of the chemistry of the Earth.
The structure of these molecules strongly
suggests they arose from a copolymerizations, and
this sequence does support that conclusion.
Research work may determine the exact
utilization of the absolute symmetry of the phytyl
side chains.
Further work at a higher accuracy may alter the
values given here.
Acknowledgements:
Appreciation is expressed to Gaussian Corp. and Q-
chem.
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