A novel synthesis of sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl] ester for use as an intermediate in the preparation of reactive dyes

Article abstract of DOI:10.1081/SCC-120004152

Sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl] ester 8, which is a key intermediate of reactive dyes was prepared in four steps in good overall yield under mild conditions from 2-aminoethanethiol and 2-bromoethanol.

Full text of DOI:10.1081/SCC-120004152

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A NOVEL SYNTHESIS OF SULFURIC ACID MONO-[2-(2-
AMINO-ETHANESULFONYL)-ETHYL] ESTER FOR USE AS
AN INTERMEDIATE IN THE PREPARATION OF REACTIVE
DYES
Young Zu Kim a & Jae Pil Kim a
a School of Materials Science & Engineering , College of Engineering , Seoul National
University , San 56-1, Shilim-dong, Kwanak-gu, Seoul, 151-742, Korea
Published online: 12 Dec 2006.
To cite this article: Young Zu Kim & Jae Pil Kim (2002) A NOVEL SYNTHESIS OF SULFURIC ACID MONO-[2-(2-AMINO-
ETHANESULFONYL)-ETHYL] ESTER FOR USE AS AN INTERMEDIATE IN THE PREPARATION OF REACTIVE DYES, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:10, 1601-1605, DOI:
10.1081/SCC-120004152
To link to this article: http://dx.doi.org/10.1081/SCC-120004152
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SYNTHETIC COMMUNICATIONS, 32(10), 1601–1605 (2002)
A NOVEL SYNTHESIS OF SULFURIC
ACID MONO-[2-(2-AMINO-
ETHANESULFONYL)-ETHYL] ESTER FOR
USE AS AN INTERMEDIATE IN THE
PREPARATION OF REACTIVE DYES
*
Young Zu Kim and Jae Pil Kim
School of Materials Science & Engineering, College of
Engineering, Seoul National University, San 56-1,
Shilim-dong, Kwanak-gu, Seoul 151-742, Korea
ABSTRACT
Sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl] ester 8,
which is a key intermediate of reactive dyes was prepared in
four steps in good overall yield under mild conditions from
2-aminoethanethiol and 2-bromoethanol.
Sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl] ester 8 repre-
sents one of the important sulphatoethylsulphone intermediates (SES) in
the synthesis of reactive dyes. Reactive dyes, which contain aliphatic SES
are more water-soluble than those, which contain aromatic SES. An aliphatic
SES requires a shorter dyeing time because of its water solubility. In addition,
dyes prepared from such intermediates contain bonds which are relatively
stable to acidic solutions and peroxide and survive the dyeing process well.
*Corresponding author. E-mail: kayam99@snu.ac.kr
1601
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1602
KIM AND KIM
Only a limited number of synthetic routes to aliphatic SES have been
reported. Of those, the synthesis of 2-(2-amino-ethylsulfanyl)-ethanol 3 has
been reported in the patent literature (Scheme 1).1 This method involves
refluxing mercapto-ethanol and 2-oxazolidinon in DGM (diethylene glycol
monomethyl ether) as a solvent. However, the procedure has some draw-
backs in terms of reaction conditions. High temperature (180ꢀC) is required
and the yield of lactam byproduct, which is produced by oxidation in 19%
yield, can be significant.
Scheme 1.
In this paper we report the development of a novel synthetic method
for the synthesis of sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl]
ester 8, which is summarized in Scheme 2.
Scheme 2.

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MONO-[2-(2-AMINO-ETHANESULFONYL)-ETHYL] ESTER
1603
Protecting 2-aminoethanethiol with di-tert-butyl dicarbonate gives
compound 5 in nearly quantitative yield.2–4 The purification of 5 is
simple. The reaction mixture is concentrated and then passed through a
pad of silica gel using a mixture of methanol and chloroform (1 : 9). Silica
gel column chromatography allowed the isolation of compound 5 in reason-
ably pure form in 93% yield.
Compound 6 was obtained in 85% yield using a procedure wherein
2-bromoethanol was added to a rapidly stirred mixture of 5 in a suspension
of aqueous sodium hydroxide/benzene at room temperature.5 It should be
noted that the use of methylene chloride as solvent was successful in this
reaction but gave compound 6 in only 22% yield.
These two steps are very simple and efficient. The overall yield for the
two steps is 80%.
The sulfone derivative of 6 (compound 7) was produced in quantita-
tive yield by oxidation with hydrogen peroxide in a mixture of methanol and
water.6,7 The reaction was performed under phase transfer conditions.
Methyltri-n-octylammonium chloride (Aliquat 336) was used as the phase-
transfer catalyst. This method involves shorter reaction times, milder reac-
tion conditions, greater convenience and higher yields.2,3 As a result,
compound 7 was obtained very pure without any chromatographic puri-
1
1
fication, as evidenced by H NMR. Both IR and H NMR confirmed that
the product obtained was sulfone and not the sulfoxide.
The desired product 8 was prepared via a series of simultaneous
reactions, that is, deprotecting the N-amino compound by cleavage of the
carbo-tert-butoxy group followed by the preparation of the sulfonate ester
from the alcohol (compound 7). The latter involved the use of chloro-
sulfonic acid and N,N-dimethylformamide as solvent.8
In conclusion the method described herein offers some distinct advan-
tages, such as mild reaction conditions, ease of operation and moderate to
good yields.
EXPERIMENTAL
Commercially available reagents were purchased from Aldrich and
1
Acros Synthesis. H NMR spectra (Bruker MSL 300 MHz) were recorded
using TMS as an internal standard, and deuteriochloroform or deuterium
oxide as solvents. IR spectra were recorded as thin films between sodium
chloride plates or KBr disks on a Prospect-IR (MIDAC Co.). Preparative
TLC was performed on silica gel plates (Merck, silica gel 60 F245), and silica
column chromatography were performed using Merck silica gel 60 (70–230
mesh ASTM).

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1604
KIM AND KIM
(2-Mercapto-ethyl)-carbamic acid tert-butyl ester (5): To a stirred
colorless solution of 2-aminoethanethiol hydrochloride 4 (9.8 g) in tetra-
hydrofuran (100 ml) at 0ꢀC was added hexane washed sodium hydride
(5.2 g, 60% in mineral oil). After 5 min, the bath was removed, the reaction
mixture was allowed to warm to room temperature and stirred for 10 min
further. The reaction mixture was then cooled to 0ꢀC and neat di-tert-butyl
dicarbonate (22.5 g) was added. After 20 min, the 0ꢀC bath was removed.
The reaction mixture was stirred for an additional 2 h at room temperature
then quenched with an aqueous solution of sodium bicarbonate. The reac-
tion mixture was poured into water and the resulting solution extracted with
ethyl acetate. The combined organic layer was dried over magnesium
sulfate, filtered and concentrated in vacuo to give essentially pure 5 (by
T.L.C.) in quantitative yield. The product was further purified by column
chromatography over a short column of silica gel; column inside diameter
25 mm, column length 400 mm and capacity of reservoir 500 ml (chloroform
as eluent). Yield: 7.5 g (95%). IR (KBr): nmax ¼ 1520 (-CO-N-), 1699 (-CO-),
1
2559.7 (-SH), 3356 (-NH-) cmꢁ1. H NMR (CDCL3): d (ppm): 1.40 (9H, s,
-C(CH3)3), 2.66 (2H, q, -N-CH2), 3.31 (2H, q, -S-CH2).
[2-(2-Hydroxy-ethylsulfanyl)-ethyl]-carbamic acid tert-butyl ester (6): In
a typical preparation of the sulfide, compound 5 (2.48 g), sodium hydroxide
(0.94 g), water (16 ml), methyltricapryl-ammonium chloride (ꢂ100 mg),
2-bromoethanol (1.79 g) and benzene (12.7 ml) were combined and stirred
vigorously with a mechanical stirrer for 2 h at ambient temperature. The
organic layer was then separated, washed with water, dried over magnesium
sulfate, and evaporated on a rotary evaporator to give 6, 3.1 g (85%) as
colorless oil, which was used without further purification. IR (KBr):
nmax ¼ 667 (-S-), 1047 (-C-OH), 1520 (-CO-N-), 1693 (-CO-), 3354 (-NH-)
cmꢁ1. 1H NMR (CDCL3): d (ppm): 1.40 (9H, s, -C(CH3)3), 2.66, 2.80 (4H, t,
S-CH2), 3.31 (q, -N-CH2), 3.75 (2H, t, -CH2, -O).
[2-(2-Hydroxy-ethanesulfonyl)-ethyl]-carbamic acid tert-buyl ester (7):
Compound 6 (7.52 g) was stirred in a mixture of water (15 ml) and metha-
nol (40 ml), sodium tungstate dihydrate (34 mg) and methyltricapryl-
ammonium chloride (ꢂ100 mg) was added at room temperature. A
solution aqueous hydrogen peroxide (10 ml) was then added dropwise to
this well-stirred clear solution at a rate such that the ensuing exotherm kept
the reaction mixture at about 60ꢀC. The reaction mixture was left for 2 h at
room temperature. After completion of the reaction, the mixture was treated
with 5% Pd/C (0.2 g) in order to decompose the remaining hydrogen
peroxide. After evolution of oxygen had ceased, the solution was filtered
and the solvent was then removed by evaporation under reduced pressure.
The residue was extracted with ethyl acetate and the organic layer was
separated, washed with water, dried over magnesium sulfate and evaporated

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MONO-[2-(2-AMINO-ETHANESULFONYL)-ETHYL] ESTER
1605
on a rotary evaporator to give a colorless liquid. Yield: 8.4 g (82%). IR
(KBr): nmax ¼ 501, 561, 1122, 1290 (-SO2-), 1520 (-CO-N-), 1699 (-CO-),
1
3373 (-NH-) cmꢁ1. H NMR (CDCL3): d (ppm): 1.49 (9H, s, -C(CH3)3),
3.28 (2H, t, -N-CH2), 3.35, 3.66 (4H, t, q, -SO2-CH2), 4.12 (2H, t, -
CH2-OH).
Sulfuric acid mono-[2-(2-amino-ethanesulfonyl)-ethyl] ester (8): To a
stirred solution of compound 7 (3.05 g) in DMF (9 ml) at 0–5ꢀC, chloro-
sulfonic acid (1.82 g, 1.3 eq.) was added dropwise. When the addition was
complete, the reaction mixture was allowed to react at 48ꢀC. The resulting
brown precipitate was filtered, washed with diethyl ether and dried in vacuo.
An analytical sample was obtained in the form of off-white crystals by
recrystallization by solution in water and precipitation with c-HCl to give
compound 8. Yield: 83%. m.p. 215–216ꢀC. IR (KBr): nmax ¼ 590, 1134, 1296
1
(-SO2-), 1066 (-C-N-), 1197 (-OSO3-) cmꢁ1. H NMR (D2O): d (ppm): 3.44
(2H, t, -N-CH2), 3.59 (4H, m, -SO2-CH2), 4.34 (2H, t, -CH2-O-).
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Received in the USA June 6, 2001

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