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(51) International Patent Classification: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
C07C 303/02 (2006.01) KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD,
ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI,
(21) International Application Number: NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD,
PCT/IN20 11/000106 SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR,
(22) International Filing Date: TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
23 February 201 1 (23.02.201 1) (84) Designated States (unless otherwise indicated, for every
(25) Filing Language: English kind of regional protection available): ARIPO (BW, GH,
GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG,
(26) Publication Language: English ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ,
(30) Priority Data: TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
522/MUM/2010 26 February 2010 (26.02.2010) IN EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
(72) Inventor; and SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
(71) Applicant : GHARDA, Keki Hormusji [IN/IN]; Gharda GW, ML, MR, NE, SN, TD, TG).
House, 48 Hill Road, Bandra (West), Mumbai 400 050,
Maharashtra (IN). Declarations under Rule 4.17 :
— as to the identity of the inventor (Rule 4.17 (i))
(74) Agent: DEWAN, Mohan; R . K . Dewan & Company,
Trade Mark & Patent Attorneys, Podar Chambers, — as to the applicant's entitlement to claim the priority of
SA.Brelvi Road, Fort, Mumbai 400 001 Maharashtra the earlier application (Rule 4. 17(Hi))
(IN).
— of inventorship (Rule 4.1 7(iv))
(81) Designated States (unless otherwise indicated, for every
Published:
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, — without international search report and to be republished
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, upon receipt of that report (Rule 48.2(g))
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
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(54) Title: A PROCESS FOR THE MANUFACTURE OF TRIFLIC ACID
(57) Abstract: The present invention relates to a process for the preparation of triflic acid by chloroxidation.
A PROCESS FOR THE MANUFACTURE OF TRIFLIC ACID
BACKGROUND
formula CF 3SO3H. It is one of the strongest acids and is mainly used in research as
resistant to both oxidation and reduction. In the laboratory, triflic acid is useful in
and alkylation of alkenes, which are very important to the petroleum industry.
These triflic acid derivative catalysts are very effective in isomerizing straight
chain or slightly branched hydrocarbons that can increase the octane rating of
There are various processes available for the synthesis of Triflic acid, viz.
of its barium salt, followed by its reaction with sulfuric acid to evolve Triflic acid
(Hazeldine & Kidd, JCS 1954, 4228). However, mercury is a poisonous metal and
CH 3 SO 3H + 4 HF CF 3 SO2F + H 20 + 1.5 H2
The resulting CF 3S0 2F is hydrolyzed and the resulting triflate salt is preprotonated.
Alternatively, trifluoromethanesulfonic acid arises by oxidation of
trifluoromethylsulfenyl chloride:
available.
Accordingly, it is desirable to develop a synthetic route for Triflic acid using
readily available raw material and which obviates the use of poisonous chemicals.
It is an object of the present invention to provide a synthetic route for Triflic acid
using easily available raw materials.
It is another object of the present invention to provide a synthetic route for Triflic
acid that obviates the use of poisonous/toxic chemicals.
SUMMARY OF AN INVENTION
In accordance with the present invention there is provided a process for the
preparation of triflic acid, said process comprising the following steps:
Typically, benzyl trifluoro methyl sulphide is at least one selected from the group
consisting of unsubstituted benzyl trifluoro methyl sulphide and substituted benzyl
trifluoro methyl sulphide.
Typically, the aromatic group is at least one selected from the group consisting of
aromatic hydrocarbon, heterocyclic aromatic hydrocarbon and polycyclic aromatic
hydrocarbon.
Typically, the aromatic hydrocarbon is at least one selected from the group
consisting of Benzene, Toluene, o, p, m-Xylene, Benzophenone, substituted
benzophenone, acetophenone, substituted acetophenone, tri methyl benzene,
tetramethyl benzene and pentamethyl benzene.
Typically, the heterocyclic aromatic hydrocarbon is at least one selected from the
group consisting of furan, pyridine, pyrazine, imidazole, Pyrazole, oxazole and
thiophene.
Typically, the polycyclic aromatic hydrocarbon is at least one selected from the
group consisting of naphthalene, anthracene and phenanthrene.
Typically, the halogen group is at least one selected from the group consisting of
fluorine, chlorine, bromine and iodine.
In accordance with one of the embodiment the substituent is at least one selected
from the group consisting of ortho chlorobenzyl chloride, 4-chloromethyl
methylene dioxy benzene, 1-chloromethyl naphthalene, bis-2, 4-chloromethyl
toluene and tris 2,4,6-chloromethyl toluene and bis-9,10-chloromethyl anthracene.
Typically, the ratio of benzyl trifluoro methyl sulphide to chlorine is in the range of
about 1: 6 moles.
Preferably, step (a) is carried out at a pressure of about 0.5 to 0.9 kg/cm 2.
Typically, the amount of thionyl chloride is about 1 to about 1.5 moles per mole of
triflic acid monohydrate.
Preferably, the amount of thionyl chloride is about 1.1 to about 1.2 moles per mole
of triflic acid monohydrate.
Preferably, the step of dehydrating triflic acid monohydrate with thionyl chloride is
carried out at a temperature of about 50 to about 60°C.
Typically, benzyl trifluoro methyl sulphide is at least one selected from the group
consisting of unsubstituted benzyl trifluoro methyl sulphide and substituted benzyl
trifluoro methyl sulphide.
Typically, the aromatic group is at least one selected from the group consisting of
aromatic hydrocarbon, heterocyclic aromatic hydrocarbon and polycyclic aromatic
hydrocarbon.
Typically, the aromatic hydrocarbon is at least one selected from the group
consisting of Benzene, Toluene, o, p, m-Xylene, Benzophenone, substituted
benzophenone, acetophenone, substituted acetophenone, tri methyl benzene,
tetramethyl benzene and pentamethyl benzene.
Typically, the heterocyclic aromatic hydrocarbon is at least one selected from the
group consisting of furan, pyridine, pyrazine, imidazole, Pyrazole, oxazole and
thiophene.
Typically, the polycyclic aromatic hydrocarbon is at least one selected from the
group consisting of naphthalene, anthracene and phenanthrene.
Typically, the halogen group is at least one selected from the group consisting of
fluorine, chlorine, bromine and iodine.
In accordance with one of the embodiment the substituent is at least one selected
from the group consisting of ortho chlorobenzyl chloride, 4-chloromethyl
methylene dioxy benzene, 1-chloromethyl naphthalene, bis-2, 4-chloromethyl
toluene and tris 2,4,6-chloromethyl toluene and bis-9,10-chloromethyl anthracene.
Typically, the ratio of benzyl trifluoro methyl sulphide to chlorine is in the range of
about 1: 6 moles.
The quantity of water used for hydrolysis is about 400 to about 1000 ml per mole
of trifluoromethyl sulphonyl chloride. Preferably, the quantity of water used for
hydrolysis is about 600 to about 750 ml per mole of trifluoromethyl sulphonyl
chloride. Monohydrate form of Triflic acid is then converted to anhydrous form
using a dehydrating agent such as thionyl chloride without using any solvent.
Typically, Triflic acid monohydrate is treated with thionyl chloride at a
temperature of about 40°C to about 80°C, preferably at 50 to 60°C to get crude
anhydrous Triflic acid.
Typically, the amount of thionyl chloride is about 1 to about 1.5 moles per mole of
Triflic acid monohydrate. The obtained crude Triflic acid is then further purified
by vacuum distillation to get Triflic acid having a purity more than 99.5%.
The above synthesis of triflic acid represents the only synthesis, which does not
use the rather aggressive reaction condition in which electrochemical fluorination
of methanesulfonyl chloride is carried out using HF as well as other synthesis
where ozone depleting substances are used.
The present invention will now be explained below in further detail with examples
of specific embodiments. However, it should be understood that the present
invention is by no means restricted to the specific examples given below.
Example 1 :
Example 2 :
Then water was removed from the reaction mass and the obtained Triflic acid
monohydrate was vacuum distilled to get 167 gm of Triflic acid monohydrate with
88% purity.
170 gm (88% pure) hydrated Triflic acid was treated with 143 gm of thionyl
chloride at 50 to 55°C and maintained at same temperature till no evolution of off
gases. Crude anhydrous Triflic acid was then vacuum distilled to get anhydrous
149 gm of Triflic acid having purity more than 99.5%.
TECHNICAL ADVANCEMENT
The present invention provides a simple and feasible route of synthesis of
triflic acid using easily available raw materials.
The present invention obviates the use of poisonous/toxic chemicals.
The present invention obviates the use of strong oxidizing agents.
While considerable emphasis has been placed herein on the specific steps of the
preferred process, it will be appreciated that additional steps can be made and that
many changes can be made in the preferred steps without departing from the
principles of the invention. These and other changes in the preferred steps of the
invention will be apparent to those skilled in the art from the disclosure herein,
whereby it is to be distinctly understood that the foregoing descriptive matter is to
be interpreted merely as illustrative of the invention and not as a limitation.
Claims:
1. A process for the preparation of triflic acid, said process comprising the
following steps:
a) treating a mixture of benzyl trifluoro methyl sulphide and water with
chlorine gas in a reactor maintained at a temperature of about 5°C to
about 30°C and at a pressure of about 0. 1 to 1.2 kg/cm 2 to form a reaction
mixture;
b) mamtaining the reaction mixture at a temperature of about 5°C to about
20°C for a period of about 4 to about 8 hours at 0.1 to 1.0 kg/cm 2
pressure;
c) raising the temperature of the reaction mixture to about 25 °C to about
45°C followed by maintaining the reaction mixture at 25 °C to 45°C and
at pressure of about 0.1 to 1.0 kg/cm to form a biphasic mixture
containing an organic layer and an aqueous layer;
d) separating the organic layer from the biphasic mixture followed by
distilling said organic layer to obtain trifluoromethylsulponyl chloride;
and
e) hydrolyzing trifluoromethylsulphonyl chloride at a temperature of about
70 to about 120°C and at a pressure of about 3 to 6 kg/cm 2 to form triflic
acid having a purity of about 99.5 %.
2. The process as claimed in claim 1, wherein the benzyl trifluoro methyl sulphide
is at least one selected from the group consisting of unsubstituted benzyl
trifluoro methyl sulphide and substituted benzyl trifluoro methyl sulphide.
3. The process as claimed in claim 1, wherein the benzyl trifluoro methyl sulphide
is a substituted benzyl trifluoro methyl sulphide, wherein the substituent is at
least one selected from the group consisting of aromatic group and halogen
group.
4. The process as claimed in claim 3, wherein the aromatic group is at least one
selected from the group consisting of aromatic hydrocarbon, heterocyclic
aromatic hydrocarbon and polycyclic aromatic hydrocarbon.
8. The process as claimed in claim 3, wherein the halogen group is at least one
selected from the group consisting of fluorine, chlorine, bromine and iodine.
9. The process as claimed in claim 3, wherein the substituent is at least one
selected from the group consisting of ortho chlorobenzyl chloride, 4-
chloromethyl methylene dioxy benzene, 1-chloromethyl naphthalene, bis-2, 4-
chloromethyl toluene and tris 2,4,6-chloromethyl toluene and bis-9,10-
chloromethyl anthracene.
10. The process as claimed in claim 2, wherein the substituted benzyl trifluoro
methyl sulphide is ortho chlorobenzyl trifluoromethyl sulphide.
11. The process as claimed in claim 1, wherein the ratio of benzyl trifluoro methyl
sulphide to chlorine is in the range of about 1: 6 moles.
12. The process as claimed in claim 1, wherein said hydrolyzing step comprises
hydrolyzing trifluoromethylsulponyl chloride with water to form a triflic acid
monohydrate and dehydrating triflic acid monohydrate with thionyl chloride at
a temperature of about 40 to about 80°C to yield crude anhydrous triflic acid
followed by removing the impurities from the crude triflic acid by vacuum
distillation to obtain pure triflic acid.
13. The process as claimed in claim 12, wherein the amount of thionyl chloride is
about 1 to 1.5 moles per mole of triflic acid monohydrate.
14. The process as claimed in claim 1, wherein said hydrolyzing step comprises
hydrolyzing trifluoromethylsulponyl chloride in presence of at least one
inorganic base selected from the group consisting of sodium hydroxide and
potassium hydroxide and at least one aliphatic alcohol selected from the group
consisting of methanol, ethanol, isopropyl alcohol and mixtures thereof to form
a hydrolyzed mass followed by neutralization using at least one mineral acid
selected from the group consisting of hydrochloric acid and sulphuric acid and
distillation to obtain pure triflic acid.