FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See section 10, rule 13)
1. Title of the invention: MOLECULAR GELATORS FOR CONTAINING OIL SPILLAGE
2. Applicant(s)
NAME NATIONALITY ADDRESS
HINDUSTAN
PETROLEUM
CORPORATION LTD.
Indian Hindustan Petroleum Corporation
Ltd, Petroleum House, 17
Jamshedji Tata Road, Churchgate,
Mumbai 400020, India
3. Preamble to the description
COMPLETE SPECIFICATION
The following specification particularly describes the invention and the manner in which it
is to be performed.
1
2
TECHNICAL FIELD
[0001] The subject matter described herein in general relates to peptide-based compounds that
are able to form gels. The subject matter further relates to methods of making peptide-based
compounds, gels including such compounds. The peptide-based compounds can be used to
5 control hydrocarbon spill by gel formation while allowing recovery of said compounds and
hydrocarbon.
BACKGROUND
[0002] A gel can be defined as a solution in which the solid, also known as a gelator, is meshed
to form a rigid or semi-rigid mixture results. Depending on the structural nature of gel networks,
10 gels can be simply divided into chemical gels and physical gels. In the case of chemical gels, the
aggregation units at different levels are connected into three-dimensional networks via covalent
bonds whereas in physical gels, the molecules of a gelator aggregate into network structure via
various non-covalent interactions, which are considerably weaker than covalent bonds.
[0003] Physical gelation of water and solvents include polymers, micro- or nano-particles, and
15 low-molecular mass organic compounds (LMMGs). The gels formed by latter are named
supramolecular gels or molecular gels and can be used for gelation of oil from oil–water
mixtures for oil spill recovery. The spilled oil is transformed from a liquid into semi-solid or
rubber-like materials floating on the surface of water by introducing LMMGs into the oil
contaminated water.
20 [0004] Jadhav and co-workers have disclosed a new class of sugargelators that can selectively
gel (solidify) the oil phase from an oil–water mixture at room temperature. The process for
preparation of gelators is easy and environmentally benign. Further, the gelators can be
recovered and reused multiple times (Angew. Chem. Int. Ed. 2010, 49, 7695 –7698).
[0005] Kar and co-workers have disclosed supramolecular hydrogelation of a composite
25 including single walled nanotubes (SWNTs) and amphiphilic dipeptide carboxylates (Chem.
Commun., 2012, 48, 8389–8391).
[0006] Kar and co-workers have disclosed dipeptide-based long-chain acids/salts capable of
efficiently gelating organic solvents and water. The xerogels prepared from the organogels
5
10
15
20
25
showed t
8648).
[0007] T
wherein,
C10 alky
compoun
[0008] T
solvent.
contactin
[0009] T
hydrocar
I to obtai
gel comp
[0010] T
better un
summary
not inten
intended
[0011] T
and mod
disclosur
time-depend
he present d
R1 is substi
l; and n is
nd of Formul
he present d
The presen
ng the compo
he present
rbon, the me
in a gel. The
prising a com
hese and ot
nderstood w
y is provided
nded to ident
to be used t
hose skilled
difications ot
re includes a
dent adsorpti
disclosure rel
tuted or uns
1 to 3. The
la I.
disclosure fu
nt disclosure
ound of Form
disclosure
thod compri
present disc
mpound of Fo
ther features
with referen
d to introduc
tify key feat
o limit the sc
d in the art w
ther than tho
all such vari
on of dyes s
SU
lates to a com
Formul
ubstituted C
e present di
urther relates
e further re
mula I with a
further rel
ising contact
closure furth
ormula I and
s, aspects an
nce to the f
ce a selection
tures or esse
cope of the c
DETAILED
will be awar
ose specifica
iations and m
3
such as cryst
UMMARY
mpound hav
la I
C10 to C25 alk
isclosure als
s to a gel com
elates to a
solvent.
lates to a
ting the hydr
her relates to
d a solvent.
nd advantage
following d
n of concept
ntial feature
claimed subj
D DESCRIP
re that the p
ally describe
modification
tal violet (La
ving the Form
kyl; R2 is ind
so relates to
mprising a c
method of p
method of
drocarbon wi
o a method o
es of the pr
description a
ts in a simpl
es of the clai
ject matter.
PTION
present disclo
ed. It is to be
ns. The disc
angmuir 200
mula:
dependently
o a method
compound of
producing a
containing
ith the comp
f reclaiming
resent subjec
and append
lified form.
imed subjec
osure is subj
e understood
closure also
09, 25(15), 8
substituted
of preparin
f Formula I
gel compr
the spill
pound of For
g solvent from
ct matter w
ded claims.
This summa
ct matter, nor
bject to varia
d that the pr
includes all
8639–
C1 to
g the
and a
rising
of a
rmula
m the
ill be
This
ary is
r is it
ations
resent
such
4
steps, features, compositions and compounds referred to or indicated in this specification,
individually or collectively and any and all combinations of any or more of such steps or
features.
Definitions
5 [0012] For convenience, before further description of the present disclosure, certain terms
employed in the specification, and examples are collected here. These definitions should be read
in the light of the remainder of the disclosure and understood as by a person of skill in the art.
The terms used herein have the meanings recognized and known to those of skill in the art,
however, for convenience and completeness, particular terms and their meanings are set forth
10 below.
[0013] The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at
least one) of the grammatical object of the article.
[0014] The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning
that additional elements may be included. Throughout this specification, unless the context
15 requires otherwise the word “comprise”, and variations, such as “comprises” and “comprising”,
will be understood to imply the inclusion of a stated element or step or group of element or steps
but not the exclusion of any other element or step or group of element or steps.
[0015] The term “including” is used to mean “including but not limited to”. “Including” and
“including but not limited to” are used interchangeably.
20 [0016] The term "hydrocarbon(s)" refers to organic compounds that are made of hydrogen and
carbon atoms. The source of the hydrocarbons may be from crude oils and refined petroleum
products. Crude oil and other petroleum fractions may include compounds with hetero atoms like
nitrogen, oxygen, sulfur, halogens and metallic elements along with hydrocarbons.
[0017] The term "gel" refers to a colloidal suspension of a solid dispersed in liquid and appear
25 like semi solid.
[0018] The term “CRN” means cracked run naptha (mainly comes from the Fluidized Catalytic
Cracking (FCC) unit in the refinery).
[0019] The term “SRN” means straight run naphtha, which comes from direct distillation of
crude oil.
30 [0020] The term “diesel” means a specific fractional distillate of petroleum crude oil between
200 °C and 350 °C at atmospheric pressure.
5
10
15
20
25
[0021] R
range for
brevity a
recited a
ranges en
recited. F
to includ
include s
individua
140.6 °C
[0022] T
dual purp
easily rec
gelators
systems.
Formula:
wherein,
C10 alkyl
[0023] T
[0024] T
products
a mixture
[0025] T
or hydroc
[0026] In
Ratios, conce
rmat. It is to
and should b
s the limits
ncompassed
For example
de not only
sub-ranges,
al amounts,
C, and 141.3
he present d
pose as oil
covered from
have the po
In one im
:
R1 is substi
l; and n is 1 t
he present d
he molecula
such as stra
e of oil and w
he compoun
carbon.
n one implem
entrations, am
o be underst
be interprete
of the range
d within that
, a temperatu
the explicitl
such as 145
including fra
°C, for exam
disclosure re
or hydrocarb
m the gel inc
otential for
mplementatio
tuted or uns
to 3.
disclosure als
ar gelators o
aight run nap
water emulsi
nds of Formu
mentation, th
mounts, and
ood that suc
ed flexibly t
e, but also to
t range as i
ure range of
ly recited lim
5 °C to 155
actional amo
mple.
elates to a c
bon remova
cluding the
selective ex
on, the pres
Formul
substituted C
so relates to
of Formula I
phtha, gasoli
ion.
ula I can be
he present di
5
d other nume
ch range for
to include n
o include all
if each num
f about 140 °
mits of abo
5 °C, 150 °
ounts, within
class of amp
al from wate
amphiphilic
xtraction of
ent disclosu
la I
C10 to C25 alk
a method of
can be used
ine, diesel fr
used for rem
isclosure rela
erical data m
rmat is used
not only the
l the individ
merical value
C to about
ut 140 °C t
C to 170 °
n the specifi
phiphilic gel
er. These ab
c gelators an
f oil in wate
ure relates
kyl; R2 is ind
f preparing th
d for the co
ractions and
mediation of
ates to a com
may be pres
merely for
e numerical
dual numeric
e and sub-ra
180 °C shou
to about 180
C, and so
ied ranges, s
lators which
bsorbed hydr
nd oil by hea
er systems
to a compo
dependently
he compoun
ntainment o
crude oil in
f a release of
mpound havi
ented herein
convenience
values expl
cal values or
ange is expl
uld be interp
0 °C, but al
forth, as we
such as 142.
h can be use
rocarbons ca
ating the gel
and water i
ound having
substituted
nd of Formul
of spilled ref
ndividually a
f spilled crud
ing the Form
n in a
e and
licitly
r sublicitly
preted
lso to
ell as
2 °C,
ed for
an be
l. The
in oil
g the
C1 to
la I.
finery
and as
de oil
mula:
5
10
15
wherein,
n is 1 to 3
[0027] In
Formula:
wherein,
n is 1 to 3
[0028] In
Formula:
wherein,
to 3.
[0029] In
R1 is unsub
3.
n another im
:
R1 is unsub
3.
n yet anothe
:
R1 is unsub
n one implem
stituted C10 t
mplementati
stituted C13 t
er implemen
stituted C15
mentation, th
Formul
to C25 alkyl;
on, the pre
Formul
to C18 alkyl;
tation, the p
Formul
alkyl; R2 is
he present di
6
la I
R2 is indep
sent disclos
la I
R2 is indep
present discl
la I
independent
isclosure rela
pendently sub
sure relates
pendently sub
losure relate
tly substitute
ates to a com
bstituted C1
to a compo
bstituted C1
es to a comp
ed C1 to C10
mpound havi
to C10 alkyl
ound having
to C10 alkyl
pound havin
0 alkyl; and n
ing the Form
l; and
g the
l; and
ng the
is 1
mula:
5
10
15
wherein,
substitute
with C1 to
[0030] In
wherein,
heteroato
and n is 1
[0031] In
Formula:
wherein,
heteroato
and n is 1
R1 is subs
ed with a he
o C3 alkyl; a
n one implem
R1 is unsub
om selected
to 3.
n another im
:
R1 is unsub
om selected
to 3.
stituted or u
eteroatom se
and n is 1 to
mentation, th
bstituted C1
from O, N a
mplementati
bstituted C1
from O, N a
Formul
unsubstitute
elected from
3.
he present di
Formul
0 to C25 alky
and S, where
on, the pre
Formul
3 to C18 alky
and S, where
7
la I
ed C10 to C
m O, N and S
isclosure rela
la I
yl; wherein
ein the heter
sent disclos
la I
yl; wherein
ein the heter
C25 alkyl; w
S, wherein t
ates to a com
R2 is C1 to
roatom is su
sure relates
R2 is C1 to
roatom is su
wherein R2 i
the heteroato
mpound havi
C10 alkyl su
ubstituted wi
to a compo
C10 alkyl su
ubstituted wi
s C1 to C10
om is substi
ing the Form
ubstituted w
ith C1 to C3 a
ound having
ubstituted w
ith C1 to C3 a
alkyl
ituted
mula:
with a
alkyl;
g the
with a
alkyl;
5
10
15
[0032] In
Formula:
wherein,
selected
3.
[0033] In
wherein,
substitute
[0034] In
wherein,
is further
n yet anothe
:
R1 is unsubs
from O, N a
n one implem
R1 is sub
ed with S wh
n one implem
R1 is unsubs
r substituted
er implemen
stituted C15
and S, where
mentation, th
stituted or
hich is furthe
mentation, th
stituted C10 t
with C1 to C
tation, the p
Formul
alkyl; where
ein the hetero
he present di
Formul
unsubstitute
er substitute
he present di
Formul
to C25 alkyl;
C3 alkyl; and
8
present discl
la I
ein R2 is C1 t
oatom is sub
isclosure rela
la I
ed C10 to C
d with C1 to
isclosure rela
la I
wherein R2
n is 1 to 3.
losure relate
to C10 alkyl s
bstituted with
ates to a com
C25 alkyl; w
C3 alkyl; an
ates to a com
is C1 to C5 a
es to a comp
substituted w
h C1 to C3 al
mpound havi
wherein R2
nd n is 1 to 3
mpound havi
lkyl substitu
pound havin
with a hetero
lkyl; and n is
ing the Form
is C1 to C5
.
ing the Form
uted with S w
ng the
oatom
s 1 to
mula:
alkyl
mula:
which
5
10
15
[0035] In
Formula:
wherein,
is further
[0036] In
Formula:
wherein,
further su
[0037] In
Formula:
wherein,
further su
n another im
:
R1 is unsubs
r substituted
n yet anothe
:
R1 is unsub
ubstituted w
n yet anothe
:
R1 is unsub
ubstituted w
mplementati
stituted C13 t
with C1 to C
er implemen
bstituted C15
ith C1 to C3 a
er implemen
bstituted C1
ith C1 to C3 a
on, the pre
Formul
to C18 alkyl;
C3 alkyl; and
tation, the p
Formul
alkyl; wher
alkyl; and n
tation, the p
Formul
3 to C18 alky
alkyl; and n
9
sent disclos
la I
wherein R2
n is 1 to 3.
present discl
la I
rein R2 is C
is 1 to 3.
present discl
la I
yl, R2 is C1 t
is 1 to 3.
sure relates
is C1 to C5 a
losure relate
1 to C5 alkyl
losure relate
to C5 alkyl
to a compo
lkyl substitu
es to a comp
l substituted
es to a comp
substituted
ound having
uted with S w
pound havin
with S whi
pound havin
with S whi
g the
which
ng the
ich is
ng the
ich is
5
10
15
[0038] In
wherein,
substitute
[0039] In
wherein,
is further
[0040] In
Formula:
wherein,
is further
n one implem
R1 is sub
ed with S wh
n one implem
R1 is unsubs
r substituted
n another im
:
R1 is unsubs
r substituted
mentation, th
stituted or
hich is furthe
mentation, th
stituted C10 t
with C1 to C
mplementati
stituted C13 t
with C1 to C
he present di
Formul
unsubstitute
er substitute
he present di
Formul
to C25 alkyl;
C3 alkyl; and
on, the pre
Formul
to C18 alkyl;
C3 alkyl; and
10
isclosure rela
la I
ed C10 to C
d with C1 to
isclosure rela
la I
wherein R2
n is 1 to 2.
sent disclos
la I
wherein R2
n is 1 to 2.
ates to a com
C25 alkyl; w
C3 alkyl; an
ates to a com
is C1 to C5 a
sure relates
is C1 to C5 a
mpound havi
wherein R2
nd n is 1 to 2
mpound havi
lkyl substitu
to a compo
lkyl substitu
ing the Form
is C1 to C5
2.
ing the Form
uted with S w
ound having
uted with S w
mula:
alkyl
mula:
which
g the
which
5
10
15
[0041] In
Formula:
wherein,
further su
[0042] In
Formula:
wherein,
further su
[0043] In
wherein,
substitute
n yet anothe
:
R1 is unsub
ubstituted w
n yet anothe
:
R1 is unsub
ubstituted w
n one implem
R1 is sub
ed with S wh
er implemen
bstituted C15
ith C1 to C3 a
er implemen
bstituted C1
ith C1 to C3 a
mentation, th
stituted or
hich is furthe
tation, the p
Formul
alkyl; wher
alkyl; and n
tation, the p
Formul
3 to C18 alky
alkyl; and n
he present di
Formul
unsubstitute
er substitute
11
present discl
la I
rein R2 is C
is 1 to 2.
present discl
la I
yl, R2 is C1 t
is 1 to 2.
isclosure rela
la I
ed C10 to C
d with C1 to
losure relate
1 to C5 alkyl
losure relate
to C5 alkyl
ates to a com
C25 alkyl; w
C3 alkyl; an
es to a comp
l substituted
es to a comp
substituted
mpound havi
wherein R2
nd n is 1.
pound havin
with S whi
pound havin
with S whi
ing the Form
is C1 to C5
ng the
ich is
ng the
ich is
mula:
alkyl
5
10
15
[0044] In
wherein,
is further
[0045] In
Formula:
wherein,
is further
[0046] In
Formula:
wherein,
further su
n one implem
R1 is unsubs
r substituted
n another im
:
R1 is unsubs
r substituted
n yet anothe
:
R1 is unsub
ubstituted w
mentation, th
stituted C10 t
with C1 to C
mplementati
stituted C13 t
with C1 to C
er implemen
bstituted C15
ith C1 to C3 a
he present di
Formul
to C25 alkyl;
C3 alkyl; and
on, the pre
Formul
to C18 alkyl;
C3 alkyl; and
tation, the p
Formul
alkyl; wher
alkyl; and n
12
isclosure rela
la I
wherein R2
n is 1.
sent disclos
la I
wherein R2
n is 1.
present discl
la I
rein R2 is C
is 1.
ates to a com
is C1 to C5 a
sure relates
is C1 to C5 a
losure relate
1 to C5 alkyl
mpound havi
lkyl substitu
to a compo
lkyl substitu
es to a comp
l substituted
ing the Form
uted with S w
ound having
uted with S w
pound havin
with S whi
mula:
which
g the
which
ng the
ich is
5
10
15
20
[0047] In
Formula:
wherein,
further su
[0048] In
Formula:
The IUP
palmitam
the comp
[0049] In
be used i
stimulus-
[0050] T
one impl
to produ
solvent in
gel comp
n yet anothe
:
R1 is unsub
ubstituted w
n yet anothe
:
PAC name
midobutanam
pound of For
n one implem
in such appli
-responsive a
he compoun
lementation,
ce a gel. In
n order to p
prising conta
er implemen
bstituted C1
ith C1 to C3 a
er implemen
of the com
mido) butano
rmula I.
mentation, th
ications as ti
advanced m
nds of Formu
the compou
n another im
produce a ge
acting the co
tation, the p
Formul
3 to C18 alky
alkyl; and n
tation, the p
C15H31
mpound of
oic acid. The
he compoun
issue engine
aterials.
ula I can be
unds of Form
mplementatio
el. The prese
ompound of
13
present discl
la I
yl, R2 is C1 t
is 1.
present discl
NH
O HN
O
S
Formula II
Formula II
e present dis
nds of Formu
ering, drug d
used to form
mula I can b
on, the comp
ent disclosur
Formula I w
losure relate
to C5 alkyl
losure relate
COOH
S
I is 4-(meth
sclosure rela
ula I and ge
delivery, sep
m gels havin
e added to o
pounds of F
re also relate
with a solven
es to a comp
substituted
es to a comp
thylthio)-2-(4
ates to a met
els synthesiz
paration of b
ng numerou
one or more
Formula I ca
es to method
nt. The term
pound havin
with S whi
pound havin
4-(methylthi
thod of prep
ed therefrom
biomolecules
s application
solvents in
an be added
d for produc
m solvent refe
ng the
ich is
ng the
io)-2-
paring
m can
s, and
ns. In
order
d to a
cing a
fers to
14
a polar solvent, non-polar solvent and mixtures thereof. In another implementation, the solvent
comprises water, an organic solvent, or mixtures thereof. Solvents can be nonpolar such as, for
example, hydrocarbons like pentane, cyclopentane, hexane, cyclohexane, benzene, toluene,
xylene, 1,4-dioxane, chloroform, diethyl ether or mixtures thereof. In one implementation, the
5 solvents can be polar, aprotic solvents such as, for example, dichloromethane, tetrahydrofuran,
ethyl acetate, acetone, dimethylformamide, acetonitrile, pyridine, carbon disulfide, benzonitrile,
or dimethyl sulfoxide. In another implementation, the solvent can be polar protic solvents such as
alcohols and carboxylic acids including, but not limited to, formic acid, n-butanol, isopropanol,
n-propanol, ethanol, methanol, acetic acid, ethylene glycol, propylene glycol, glycerin, or water.
10 Mixtures of solvents can also be used herein. In one implementation, the solvent can be a
mixture of water with a hydrocarbon. In another implementation, the solvent is a hydrocarbon. In
another implementation, the solvent is selected from crude oil, or a petroleum product.
[0051] The present disclosure also relates to method of containing the spill of a hydrocarbon, the
method comprising contacting the hydrocarbon with the compound of Formula I to obtain a gel.
15 [0052] In one implementation, a method of recovering crude oil, or petroleum product from a
spill of crude oil, or the petroleum product comprises: (a) forming a gel comprising the crude oil,
or the petroleum product and a compound of formula I; (b) collecting the gel; and (c) reclaiming
the crude oil or the petroleum product from the gel.
[0053] In another implementation, method of reclaiming solvent and a compound of Formula I
20 from the gel comprising the solvent and the compound of Formula I.
Examples
[0054] The disclosure will now be illustrated with working examples, which is intended to
illustrate the working of disclosure and not intended to take restrictively to imply any limitations
on the scope of the present disclosure. Other examples are also possible which are within the
25 scope of the present disclosure.
Example 1
Synthesis of compound of Formula II
[0055] The compound of Formula II was synthesized according to Scheme 1.
Scheme 1
15
H2N COOH
R2 SOCl2
dry MeOH H3N COOMe
R2
aq NaHCO3
EtOAc
H2N COOMe
R2
R1 Cl
O
R1 NH
O
COOMe
R2
dry DCM
DCC
HOBT, DMAP i. NaOH, MeOH
ii. HCl R1 NH
O
COOH
R2
H2N COOMe
R2
H2N COOH
R2
dry Py
dry DCM
R1 NH
O R2
HN
O
COOMe
R2
i. NaOH, MeOH
ii. HCl
R1 NH
O R2
HN
O
COOH
R2
Py = Pyridine
DCC = N,N'-Dicyclohexylcarbodiimide
HOBT = Hydroxybenzotriazole
DMAP = 4-Dimethylaminopyridine
R1 = -C15H31
R2 = -CH2CH2SCH3
[0056] Methionine (4.47g, 10 mM) was dissolved in dry MeOH followed by 1.1 equivalent
addition of SOCl2 (2.4 mL, 33 mM) at room temperature. The reaction mixture was then stirred
5 at room temperature for 2 hours. After 2 hours stirring the reaction desired compound was
extracted in ethyl acetate after addition of aqueous solution of NaHCO3. Solvent removal from
the organic phase yielded methyl ester of methionine.
[0057] The acid chloride of palmitic acid, C15H31COOH (1 equiv, 8.7 g, 30 mM) was dissolved
in dry DCM. To this solution methyl ester of Methionine (1.1 equiv, 5.9 g, 33 mM) was added
10 followed by pyridine (1.1 equiv). The reaction mixture was allowed for overnight stirring at
room temperature followed by filtration to collect the filtrate. Organic phase was then washed
with 1N HCl solution followed by washing with aqueous solution of Na2CO3 and then by brine.
Solvent removal from the organic phase yielded the ester protected monopeptide compound. The
ester protected long chain amide was then purified through column chromatography using 60-
15 120 mesh silica gel and ethyl acetate/hexane as eluent.
[0058] The ester protected monopeptide compound (12 g, 30 mM) was hydrolyzed using 1 N
NaOH (1.1 equiv) in MeOH for 6 h with stirring at room temperature followed by acidification
by 1N HCl. The corresponding carboxylic acid was extracted in ethyl acetate from MeOH
solvent. Organic solvent was then removed to obtain the desired product, monopeptide
20 carboxylic acid.
[0059] Monopeptide carboxylic acid (11.6 g, 30 mM) was dissolved in dry DCM where methyl
ester protected L-amino acid (1.1 equiv, 5.9 g, 33 mM) was added followed by DCC (7.4 g, 33
16
mM), HOBT (4.8 g, 33 mM) and DMAP (4.4 g, 33 mM). After overnight reaction the organic
phase was washed with 1N HCl solution followed by washing with aqueous solution of Na2CO3
and then by brine. Organic solvent was then removed to obtain the ester protected dipeptide
product. The ester compound is hydrolyzed using 1 N NaOH (1.1 equiv) in MeOH followed by
5 acidification using HCl results the final product. The final product was then purified through
column chromatography using 60-120 mesh silica gel and ethyl acetate/toluene as eluent.The
product 10.4 g (67 % with respect to carboxylic acid) was characterized by proton NMR and
mass spectrometry. 1H NMR (500 MHz, CDCl3):  = 7.33-7.32 [d, 1H], 6.56-6.54 [d, 1H], 4.74-
4.67 [m, 2H], 2.58-2.53 [m, 4H], 2.24-2.21 [m, 3H], 2.11-2.06 [m, 8H], 2.05-1.96 [m, 1H], 1.63-
10 1.61 [m, 2H], 1.28-1.24 [m, 24H], 0.89-0.86 [m, 3H]; E.A: calculated for C26H50N2O4S2: C,
60.19; H, 9.71; N, 5.40. Found: 60.10; 9.79; 5.33; ESI-MS: m/z: 541.4296 (M+ =
C26H50N2O4S2Na+), m/z (calculated): 541.3065 (M+ = C26H50N2O4S2Na+)
Example 2
Gelation Study with crude oil
15 [0060] In a typical procedure, 10 mg of the gelator compound of Formula II was added to 0.5 ml
of crude oil in a glass vial with an internal diameter (i.d.) of 10 mm. The mixture was warmed
gently to dissolve the solid compound in crude oil. Then the solution was allowed to cool slowly
to room temperature without disturbance. After few minutes, the solid aggregate mass was found
to be stable to inversion of the glass vial, and then the compound was recognized to form a gel.
20 [0061] To calculate minimum gelation concentration (MGC), gelator was added gradually from
1 mg to higher amount in required solvent/oil (0.5 ml) and the above process (heating and
cooling) was repeated until gel was formed.
[0062] Gel melting temperature was determined by typical tube inversion method. The vial
containing the gel, as prepared above was immersed in the oil-bath ‘upside down’ and slowly
25 heated. The temperature at which the viscous gel melted down was recorded as Tgel.
Gelation Study with CRN:
[0063] The gelation process for crude oil was repeated but taking 5 mg of CRN (Table 1).
Gelation Study with SRN:
17
[0064] The gelation process for crude oil was repeated but taking but taking 4 mg of SRN (Table
1) .
Gelation Study with Diesel:
[0065] The gelation process for crude oil was repeated but taking but taking 5 mg of Diesel oil
5 (as reported in Table 1).
Table 1: Gelation abilities of compound of Formula II in different hydrocarbons
Liquids Amount of
oil (ml)
Weight of
gelator (mg)
MGC (%,
w/v)
Tgel (oC)
Crude 0.5 10 2 90
CRN 0.5 5 1 85
SRN 0.5 4 0.8 80
Diesel 0.5 5 1 82
[0066] All these four oil samples were converted to the gel phase using very less amount of the
gelator where the minimum gelation concentration (MCG) vary from 0.8 to 1 w/v% for different
oil cuts. This work actually is the first example citing gelation of crude oil by amino acid based
10 gelator compound and gelation of the crude oil demands higher MCG (2 w/v%) than the cuts.
From the table it is quite evident that best gelation ability of the gelator is exhibited for SRN
followed by CRN/diesel and crude oil
Example 3
Selective Gelation of crude oil from a Biphasic Mixture of Oil and Water
15 [0067] In a typical procedure, 0.5 mL of crude oil and 0.5 mL of water were taken in a sample
tube to which 10 mg of the gelator compound of Formula II (as required to attain at least MGC)
was added (Table 2). The gelator was then solubilized in this two-phase solution by heating.
After the mixture was cooled to room temperature, the crude oil layer was gelated, keeping the
water layer intact in the liquid state.
20 Selective Gelation of CRN from a Biphasic Mixture of Oil and Water:
18
[0068] The gelation process was repeated as that of crude oil but taking 6 mg of CRN (as
reported in Table 2) instead of crude oil.
Selective Gelation of SRN from a Biphasic Mixture of Oil and Water:
[0069] The gelation process was repeated as that of crude oil but taking 5 mg of SRN (as
5 reported in Table 2) instead of crude oil.
Selective Gelation of Diesel from a Biphasic Mixture of Oil and Water:
[0070] The gelation process was repeated as that of crude oil but taking 6 mg of Diesel oil (as
reported in Table 2) instead of crude oil.
Table 2: Gelation abilities of compound of Formula II in various oil-water mixture
Liquids Amount
of oil (ml)
Weight of
gelator (mg)
Amount of
aq phase (ml)
MGC (%,
w/v)
Crude-water 0.5 10 0.5 2
CRN-Water 0.5 6 0.5 1.2
SRN-Water 0.5 5 0.5 1
Diesel-Water 0.5 6 0.5 1.2
10 [0071] This table signifies that the gelator compound can selectively and effectively convert the
oil phase into the gel phase in oil-water mixture. Presence of water demands more gelator
compound for gelation as the minimum gelation concentration (MCG) in presence of water is
little bit higher than that of previous cases (in absence of water). Here also, the gelation ability of
the gelator is superior for SRN than other oils.
15 Example 4
Selective Gelation of crude oil from a Biphasic Mixture of Oil and Salt Solution:
[0072] In a typical procedure, 0.5 mL of crude oil and 0.5 mL of 3.5% of NaCl solution
(equivalent salt concentration to that of sea water) were taken in a sample tube to which 10 mg of
the gelator compound of Formula II was added (Table 3). The gelator was then solubilized in this
20 two-phase solution by heating. After the mixture was cooled to room temperature, the crude oil
layer was gelated, keeping the water layer intact in the liquid state.
19
Selective Gelation of CRN from a Biphasic Mixture of Oil and Salt Solution:
[0073] Gelation process mentioned above with crude oil was repeated with 6 mg of CRN (as
reported in Table 3).
Selective Gelation of SRN from a Biphasic Mixture of Oil and Salt Solution:
5 [0074] Gelation process mentioned above with crude oil was repeated with 5 mg of SRN (as
reported in Table 3).
Selective Gelation of Diesel from a Biphasic Mixture of Oil and Salt Solution:
[0075] Gelation process mentioned above with crude oil was repeated with 6 mg of Diesel oil (as
reported in Table 3).
10 Table 3: Gelation abilities of compound of formula II in various oil-sea water mixture
Liquids Amount of
oil (ml)
Weight of
gelator (mg)
Amount of aq
phase (ml)
MGC
(%, w/v)
Crude-Sea Water 0.5 10 0.5 2
CRN-Sea Water 0.5 6 0.5 1.2
SRN-Sea Water 0.5 5 0.5 1
Diesel-Sea water 0.5 6 0.5 1.2
Example 5
Oil Spill Recovery:
Oil spill recovery was performed taking 10 ml of SRN over 20 ml of water. An ethanolic
15 solution of the compound of Formula II (0.25 g in 5 mL of Ethanol, 5 w/v%; only 2.5 ml of the
ethanolic solution was used for 10 ml of SRN) was added to the SRN-water mixture and allowed
to stand for about 15 min where SRN phase was transformed to the gel keeping the water layer
intact in the liquid state. The gel phase was filtered off and processed to recover the oil.
Example 6
20 Reclaiming solvent from Gel
20
[0076] 10 ml of SRN was transformed into gel phase using 80 mg of compound of Formula II.
The gel was then subjected to vacuum distillation for oil phase recovery. After successful
distillation 8.9 ml of SRN was recovered leaving white powder of the gelator compound with
89% of solvent recovery. The vacuum distillation was carried out at 60oC for 1 hour.
5 Advantages gained in the example illustrative process in this subject matter:
[0077] Environmentally benign amino acid based phase selective gelator has been developed for
oil phase gelation from a mixture of oil and water. The gelators efficiently work even at a very
low concentration and at room temperature. The gelators find application in marine oil spill
recovery.Oil from the gel can be recovered and gel can be recycled and reused for number of
10 cycles without loss of activity
[0078] Although the subject matter has been described in considerable detail with reference to
certain examples and implementations thereof, other implementations are possible. As such, the
spirit and scope of the appended claims should not be limited to the description of the preferred
examples and implementations contained therein.
15
20
25
5
10
15
20
I/We Cla
1. A
F
2. T
3. T
4. T
5. T
h
C
6. T
w
7. T
C
8. A
C
F
9. A
10. A
aim:
compound
ormula I
where
R1 is s
R2 is i
n is 1
The compoun
The compoun
The compoun
The compoun
eteroatom se
C3 alkyl.
The compoun
which is furth
The compoun
C1 to C5 alkyl
compound
C15H31 NH
O
S
ormula II
method of
gel compri
having the F
ein,
substituted o
independent
to 3.
nd as claimed
nd as claimed
nd as claimed
nd as claim
elected from
nd as claim
her substitute
nd as claime
l substituted
having the F
HN
O COO
preparing th
sing a comp
Formula:
or unsubstitu
ly substitute
d in claim 1,
d in claim 1,
d in claim 1,
med in claim
m O, N and
med in claim
ed with C1 to
ed in claim
with S whic
Formula:
OH
S
he compound
ound as clai
21
uted C10 to C2
ed C1 to C10 a
, wherein R1
, wherein R1
, wherein R1
1, wherein
S, wherein
1, wherein
o C3 alkyl.
1, wherein R
ch is further
d as claimed
imed in Claim
25 alkyl;
alkyl;
1 is unsubstit
1 is unsubstit
1 is unsubstit
R2 is C1 to
the heteroat
n R2 is C1 to
R1 is unsubs
substituted w
in claim 1.
m 1 and a so
tuted C10 to C
tuted C13 to C
tuted C15 alk
C10 alkyl su
tom is subst
o C5 alkyl su
stituted C13 t
with C1 to C
olvent.
C25 alkyl.
C18 alkyl.
kyl.
ubstituted w
tituted with
ubstituted w
to C18 alkyl,
3 alkyl.
with a
C1 to
with S
R2 is
22
11. The gel as claimed in claim 10, wherein the solvent comprises water, an organic solvent,
or mixtures thereof.
12. A method for producing a gel comprising contacting the compound as claimed in claim
1 with a solvent.
5 13. The method as claimed in claim 12, wherein the solvent is selected from water, an
organic solvent, or mixtures thereof.
14. The method of claim 12, wherein the solvent is a hydrocarbon.
15. The method of claim 12, wherein the solvent comprises a mixture of a hydrocarbon and
water.
10 16. A method of containing the spill of a hydrocarbon, the method comprising contacting the
hydrocarbon with the compound as claimed in claim 1 to obtain a gel.
17. A method of reclaiming solvent and a compound as claimed in claim 1 from the gel as
claimed in claim 10.