Hydrogen Sulfide Scavenging by 1,3,5-Triazinanes.

Comparison of
the Rates of Reaction
J an M. Bakke* and J anne B. Buhaug
Department of Chemistry, Norwegian University of Scienceand Technology, NO-7491 Trondheim, Norway
The reacti on of 1,3,5-tri ethyl -1,3,5-tri azi nane (1b) and 1,3,5-tri methyl -1,3,5-tri azi nane (1c) wi th
sodi um hydrogen sul fi de has been studi ed. The products were the correspondi ng thi adi azi nanes
2and di thi azi nanes 3. The rates of the reacti on, together wi th that of 1,3,5-tri s(2-hydroxyethyl )-
1,3,5-tri azi nane (1a), were studi ed by
1
H NMR spectroscopy. Thei r rel ati ve rates of reacti on
wi th HS
-
were as fol l ows: 1c, 1; 1b, 19; 1a, 31. The rates of hydrol ysi s were studi ed for the
same three compounds. I n thi s reacti on, the rel ati ve rates were as fol l ows: 1c, 1; 1b, 12; 1a, 24.
The reacti ons of 1,3,5-tri oxane (4a) and 2,4,6-tri methyl -1,3,5-tri oxane were al so studi ed. These
two compounds di d not react wi th HS
-
or were hydrol yzed under the condi ti ons used for the
reacti ons of 1a-c.
Introduction
Di hydrogen sul fi de, H
2
S, i s present i n l ow concentra-
ti ons i n natural gas from many sources. Because of i ts
obnoxi ous characteri sti cs,
1
i t i s necessary to remove i t
duri ng processi ng, before the end use. 1,3,5-Tri s(2-
hydroxyethyl )-1,3,5-tri azi nane (1a, l ater tri azi nane) i s
an effecti ve scavenger i n thi s process. We have reported
a study of the products from the reacti on of tri azi nane
wi th H
2
S and al so i ts rate of hydrol ysi s as a functi on of
pH and temperature.
2
I n 1a, the hydroxyl groups on the
si de chai ns i ncrease the hydrophi l i ci ty of the mol ecul e,
maki ng i t emi nentl y sui ted for reacti ons i n the aqueous
phase. However, i t mi ght be of i nterest to remove H
2
S
di rectl y i n the wel l i tsel f, where the medi um mi ght have
a more hydrophobi c character. For thi s purpose, more
l i pophi l i c si de chai ns mi ght be of i nterest. We have
therefore i nvesti gated the reacti ons between H
2
S and
two such substances wi th methyl or ethyl groups at the
ni trogen atoms of the tri azi nane ri ng, 1,3,5-tri ethyl -
1,3,5-tri azi nane (1b, l ater ethyl tri azi nane) and 1,3,5-
tri methyl -1,3,5-tri azi nane (1c, l ater methyl tri azi nane).
We have al so studi ed the reacti ons of two oxygen
heterocycl i c compounds, 1,3,5-tri oxane (4a) and 2,4,6-
tri methyl -1,3,5-tri oxane (4b), wi th H
2
S.
Results and Discussion
Products from the Reaction of the Nitrogen
Heterocyclic Compounds1a-c with H
2
S. The prod-
ucts from the reacti on of 1a wi th H
2
S were i denti fi ed
as 3,5-bi s(2-hydroxyethyl )-1,3,5-thi adi azi nane (2a) and
5-(2-hydroxyethyl )-1,3,5-di thi azi nane (3a). The i denti -
fi cati on was carri ed out by extensi ve use of NMR
spectroscopy.
2
We have used the same techni ques for
the i denti fi cati on of the products from the reacti ons of
1b and 1c wi th H
2
S/HS
-
.
1b was reacted wi th 2 equi v of NaHS at pH 10.0. By
anal ogy wi th the reacti on of 1a wi th HS
-
under the
same condi ti ons, the formati on of 3,5-di ethyl -1,3,5-
thi adi azi nane (2b) and 5-ethyl -1,3,5-di thi azi nane (3b),
i n addi ti on to ethyl ami ne, was expected. The NMR
spectroscopy data (Tabl e 3) confi rmed thi s. The
1
H NMR
spectrum of the reacti on mi xture showed thi s to contai n
unreacted 1b(15%), 2b(8%), and 3b(10%), i n addi ti on
to ethyl ami ne (67%). I n an experi ment i n whi ch 1bwas
reacted wi th 1 equi v of NaHS, onl y 2b and ethyl ami ne
were formed, supporti ng the previ ous assi gnments.
I n the reacti on mi xture wi th 2 equi v of HS
-
, a
nonaqueous phase was observed i n the aqueous reacti on
mi xture after 4 weeks at room temperature. A
1
H NMR
spectrum of the nonaqueous l ayer showed i t to contai n
compounds 2band 3bi n rel ati ve amounts of 1:7. At the
same ti me, a
1
H NMR spectrum of the remai ni ng
aqueous phase showed that 2b was present but there
were onl y traces of 3b. Thi s observati on corresponds
wel l wi th the assi gnment of compounds 2b and 3b
because substi tuti on of a ri ng ni trogen wi th sul fur
woul d make the mol ecul e l ess pol ar. 1,3,5-Tri thi ane has
a l ow sol ubi l i ty i n water.
I n the previ ous experi ments, 1b was reacted wi th a
sol uti on of sodi um hydrogen sul fi de. Upon H
2
S removal ,
an aqueous sol uti on of 1bwoul d react wi th gaseous H
2
S.
We therefore performed a reacti on under these condi -
ti ons by bubbl i ng H
2
S through an aqueous sol uti on of
1b. After 10 mi n, a
1
H NMR spectrum showed that 3b
and ethyl ami ne had been formed. Nei ther 1b nor 2b
was found, i ndi cati ng that the reacti on was compl ete
under these condi ti ons.
The products from the reacti on of 1c were i nvesti -
gated by fi rst reacti ng them wi th 2 equi v of NaHS at
pH 10.0. The reacti on was expected to proceed i n the
same way as those of 1a and 1b, wi th the formati on of
3,5-di methyl -1,3,5-thi adi azi nane (2c) and 5-methyl -
1,3,5-di thi azi nane (3c), i n addi ti on to methyl ami ne. The
reacti on was very sl ow, but after 3 days, a preci pi tate
of whi te, needl e-shaped crystal s was observed. The
crystal s and the mother l i qui d were i nvesti gated by the
same NMR techni ques as those used previ ousl y. The
data are gi ven i n the Experi mental Secti on (Tabl e 4).
The resul ts were i n accordance wi th the reacti on path
i n Scheme 1, 1c reacted wi th HS
-
to gi ve 2c, and thi s
reacted further wi th HS
-
to gi ve 3c. The crystal s were
i denti fi ed as 3c.
Onl y traces of the si gnal s from 3c were observed i n
the
1
H and
13
C NMR spectra of the reacti on mi xture.
The proposed structure of 3c corresponds wel l wi th thi s
* To whom correspondence shoul d be addressed. Tel .: +477-
3594095. Fax: +4773594256. E-mai l : jan.bakke@nt.ntnu.no.
1962 I nd. Eng. Chem. Res. 2004, 43, 1962-1965
10.1021/i e030510c CCC: $27.50 2004 Ameri can Chemi cal Soci ety
Publ i shed on Web 04/02/2004
because the di thi azi nane compound wi th two sul fur
atoms i n the ri ng i s expected to be the l east water-
sol ubl e of the components i n the reacti on mi xture.
Agai n, i t was i mportant to see i f the same products
were formed when 1c was reacted wi th gaseous H
2
S.
The gas was bubbl ed through an aqueous sol uti on of
1c for 23 mi n. A
1
H NMR spectrum was recorded. Thi s
showed that al l of the starti ng materi al had di sap-
peared, whi l e methyl ami ne and di thi azi nane 3c had
been formed. Thi s was consi stent wi th the resul ts for
1a and 1b, whi ch al so formed the correspondi ng di thi -
azi nane compounds upon reacti on wi th H
2
S. The resul ts
are summari zed i n Scheme 1.
Reactions with the Oxygen Heterocyclic Com-
pounds 4a,b (Chart 1). I n 4a and 4b, the ni trogen
atoms of 1a-c have been substi tuted wi th oxygen
atoms. Oxygen i s more el ectronegati ve than ni trogen,
and thi s mi ght make the carbon atoms of the ri ng more
el ectrophi l i c. Compounds 4aand 4bmi ght therefore be
more reacti ve both toward HS
-
and toward hydrol ysi s.
Accordi ngl y, we reacted the two compounds wi th HS
-
and moni tored the reacti on by
1
H NMR spectroscopy.
However, nei ther 4anor 4breacted wi th HS
-
. Because
the reacti on wi th the ni trogen heterocycl es 1a-c was
pH dependent, we vari ed the pH of the reacti on from
10 to 7, but no reacti on wi th HS
-
was observed. The
compounds were al so stabl e for several days toward
hydrol ysi s at thi s pH range. Thi s di fference i n reacti vi ty
was probabl y caused by the di fference i n basi ci ty
between compounds 1and 4. The reacti ng speci es i n the
case of the tri azi nanes was not 1 but 1H
+
. The anal o-
gous 4H
+
woul d not have been formed under the appl i ed
condi ti ons, and the el ectrophi l i ci ty of 4woul d be l ower
than that of 1H
+
.
Kinetic Investigations. (a) Hydrolysis. To study
the reacti vi ty of the tri azi nanes 1a-c toward H
2
S/HS
-
,
i t was necessary to fi rst determi ne thei r rates of
hydrol ysi s, an i mportant si de reacti on. We have re-
ported the ki neti cs of the hydrol ysi s of 1a.
1
The rate of
the reacti on fol l owed the rate l aw (1), where [T] i s the
concentrati on of the tri azi nane i nvesti gated, k
1
the rate
constant for the uncatal yzed reacti on, and k
2
that for
the catal yzed one. Wi th constant pH
The concentrati on of tri azi nane was moni tored by
1
H
NMR spectroscopy. The observed fi rst-order rate con-
stants for the hydrol ysi s reacti ons of 1band 1c at three
di fferent pHs are gi ven i n Tabl e 1. From these and eq
2, k
1
and k
2
for 1band 1c were cal cul ated. The resul ts,
together wi th the rate constants for 1a,
3
are al so gi ven
i n Tabl e 1.
Tabl e 1 shows that the uncatal yzed hydrol ysi s reac-
ti on as expressed by k
1
was i nsi gni fi cant compared to
the catal yzed one. I t i s, furthermore, evi dent that 1c
was the most stabl e and 1a the l east stabl e toward
hydrol ysi s of the three tri azi nanes i nvesti gated. Thi s
i ndi cated that 1c mi ght be used at a l ower pH than 1b
and parti cul arl y 1a for H
2
S scavengi ng. From k
2
i n
Tabl e 1, i t was possi bl e to cal cul ate the hal f-l i fe of each
of the three scavengers at di fferent pHs. Thi s i s shown
by the graphs i n Fi gure 1.
Once the rates of hydrol ysi s for the three tri azi nanes
had been establ i shed, thei r reacti ons wi th H
2
S/HS
-
were studi ed at pH l evel s where the rates of hydrol ysi s
were l ow enough to be negl ected. I t shoul d be noted that
these experi ments were carri ed out on rather di l ute
sol uti ons of tri azi nane, 0.1 vol %. I n concentrated
sol uti ons where the acti vi ty of water i s l ower, the rate
Scheme 1
Chart 1
Figure 1. Hal f-l i ves of 1a-c at di fferent pHs.
Table 1. Rate Constants for the Hydrolysis of 1a-c at
Different pHs and Temperatures
compd pH kobs (10
-4
s
-1
) k1 (10
-5
s
-1
) k2 (10
5
M
-1
s
-1
)
1a 10.0 2.0 ( 0.1
9.0 15 ( 1 7 ( 2 14 ( 1
8.0 143 ( 1
1b 10.0 1.2 ( 0.1
9.0 7.9 ( 0.1 7 ( 3 6.9 ( 0.1
8.0 70 ( 1
1c 10.0 0.05 ( 0.01 3 ( 4 0.58 ( 0.03
9.0 0.55 ( 0.01
8.0 6.8 ( 0.1
7.5 18 ( 1
-d[T]/dt ) k
1
[T] + k
2
[T][H
+
] (1)
k
obs
) k
1
+ k
2
[H
+
] (2)
I nd. Eng. Chem. Res., Vol . 43, No. 9, 2004 1963
of hydrol ysi s woul d be expected to be sl ower than those
reported here.
(b) Reactions with HS
-
. I ntroductory experi ments
i ndi cated that the rate of the reacti on between sodi um
NaHS wi th tri azi nane 1ai s dependent on the pH of the
medi um, and a reacti on mechani sm expl ai ni ng thi s
poi nt was proposed.
2
I t was, therefore, reasonabl e to
assume that protonated (hydroxyethyl )tri azi ne (TH
+
)
was the reacti ng speci es. I n the i nvesti gated pH regi on,
HS
-
i s compl etel y domi nati ng i n the H
2
S/HS/S
2-
equi -
l i bri a.
4
From thi s, the reacti on was assumed to be of
second order wi th the rate l aw (3).
The hydrol ysi s reacti on can be negl ected because of
the pH range of the anal yses. The concentrati on of the
protonated tri azi nane i s rel ated to pH through K
a
:
Substi tuti ng for [TH
+
] i n eq 3 gi ves
where k
3
) kK
a
-1
.
I f the ki neti c experi ments are carri ed out at constant
pH, [H
+
] wi l l be constant. Thi s resul ts i n an apparent
second-order reacti on, wi th k
2
) k
3
[H
+
]. The new rate
expressi on i s
Thi s can be si mpl i fi ed further by keepi ng the concentra-
ti on of HS
-
constant. Thi s i s done by runni ng the
experi ment wi th excess HS
-
([HS
-
] g 10[T]). The
change i n [HS
-
] then becomes negl i gi bl e, and the
reacti on can be consi dered a pseudo-fi rst-order reacti on.
Onl y one parameter (the concentrati on of the tri azi nane)
needs to be moni tored over ti me, and the rate expressi on
i s
where
By moni tori ng of [T], k
1
wi l l be obtai ned from eq 7. The
other rate constants k
2
and k
3
can be cal cul ated from
k
1
, [H
+
], and [HS
-
]. I t shoul d be noted that an anal o-
gous set of equati ons coul d be deri ved i n whi ch [T] was
kept constant and [HS
-
] moni tored. I n pri nci pl e, thi s
coul d be done si mpl y by use of a sul fi de-sensi ti ve
el ectrode. However, despi te consi derabl e effort, we were
not abl e to get reproduci bl e resul ts by that approach.
We therefore chose to run the ki neti c i nvesti gati ons
at constant pH, wi th a 10-fol d excess of NaHS and
moni tori ng of [T] by
1
H NMR spectroscopy. Acetoni tri l e
was used as an i nternal standard. The resul ts from the
ki neti c i nvesti gati ons of the reacti ons of NaHS wi th 1a,
1b, and 1c at di fferent pHs are gi ven i n Tabl e 2. From
these data, wi th constant pH and [HS
-
], the rate
constants k
3
) kK
a
-1
were obtai ned and are al so gi ven
i n Tabl e 2. I t contai ns a measure of the basi ci ty of the
ami no ni trogen of 1 as expressed by K
a
. There i s no
reason to bel i eve that K
a
wi l l be very di fferent for the
three tri azi nanes i nvesti gated and, furthermore, the
basi ci ty of the ami no groups wi l l be an i ntegrated part
of the reacti vi ty of the tri azi nanes. We, therefore,
consi der that the k
3
obtai ned gi ves a val i d expressi on
of the rel ati ve reacti vi ty of the three tri azi nanes toward
H
2
S/HS
-
.
Conclusion
I n the previ ous secti ons, the stabi l i ty toward hydrol y-
si s and reacti vi ty toward HS
-
/H
2
S of the three tri azi -
nanes 1a-c were exami ned. From Tabl e 2, the stabi l i ty
toward hydrol ysi s was 1c > 1b > 1a, wi th the rate of
hydrol ysi s of 1c onl y ca.
1
/
20
that of 1a, i ndi cati ng that
1c mi ght have an advantage for H
2
S removal under
condi ti ons where hydrol ysi s woul d be a probl em.
However, a compari son of the rate constants for the
reacti on of HS
-
wi th 1a-c (Tabl e 2) shows that 1c not
onl y reacted sl ower i n the hydrol ysi s reacti on but al so
reacted sl ower i n the reacti on wi th HS
-
; 1c reacted onl y
1
/
30
as fast as 1a. I n addi ti on, the product from the
reacti on of 1c wi th 2 equi v of HS
-
, 3c, was barel y
sol ubl e i n water; thi s al one woul d excl ude i t as an
i ndustri al H
2
S scavenger.
Experimental Section
Instrumentation and Chemicals. NMR spectra
were recorded on Bruker DPX 300 or 400 MHz i nstru-
ments. El ectron i mpact mass spectrometry (EI MS)
spectra were obtai ned on a Fi nni gan MAT 95 XL
spectrometer. Sul fi de detecti ons were performed usi ng
an Ori on Sure-Fl ow Combi nati on Si l ver/Sul fi de el ec-
trode, model 9616. An Ori on Sure-Fl ow Combi nati on
el ectrode, model 8172, was used for al l pH measure-
ments.
Al l buffered sol uti ons were made by adjusti ng the pH
of a 0.50 M Na
2
HPO
4
sol uti on wi th aqueous HCl or sol i d
Na
2
CO
3
. Aqueous sol uti ons of 1band 1c were provi ded
by Dynea Oi l Fi el d Chemi cal s, Randaberg, Norway.
Reactionbetween1bandHS
-
. 1b(8.6 g, 5.0 mmol )
and NaHS (0.54 g, 9.7 mmol ) were di ssol ved i n a
buffered water sol uti on at pH 10.0 (10 mL). The reacti on
was run at room temperature. The reacti on products
were i denti fi ed by NMR spectroscopy, and the NMR
data and thei r assi gnments are presented i n Tabl e 3.
I n an equi mol ar reacti on, 1b(0.086 g, 0.50 mmol ) and
Na
2
S (0.038 g, 0.48 mmol ) were di ssol ved i n a buffered
water sol uti on at pH 10.0. 2b and ethyl ami ne were
i denti fi ed as reacti on products by NMR spectroscopy.
The experi ment wi th gaseous H
2
S was performed by
bubbl i ng the concentrated gas through a sol uti on of 1b
(0.429 g, 2.50 mmol ) i n water (50 mL) for 10 mi n. An
NMR anal ysi s of the reacti on mi xture reveal ed that onl y
3b and ethyl ami ne were present.
Reaction between 1c and HS
-
. 1c (0.65 g, 5.0
mmol ) and NaHS (0.54 g, 9.7 mmol ) were di ssol ved i n
-d[T]/dt ) k[TH
+
][HS
-
] (3)
K
a
) [T][H
+
]/[TH
+
] (4)
-d[T]/dt ) k
3
[T][H
+
][HS
-
] (5)
-d[T]/dt ) k
2
[T][HS
-
] (6)
-d[T]/dt ) k
1
[T] (7)
k
1
) kK
a
-1
[H
+
][HS
-
] (8)
Table 2. Rate Constants (k
3
) kKa
-1
) for the Reaction of
1a-c with [HS
-
] ) 0.48 M at 22 C
compd pH k
1
(10
-3
s
-1
) k
3
(10
7
M
-2
s
-1
)
11.0 0.41 ( 0.01
1a 10.5 1.3 ( 0.1 9.1 ( 0.2
10.0 4.3 ( 0.1
11.0 0.21 ( 0.01
1b 10.5 0.61 ( 0.01 5.6 ( 0.4
10.0 2.6 ( 0.1
11.0 0.014 ( 0.003
1c 10.5 0.056 ( 0.002 0.29 ( 0.03
10.0 0.14 ( 0.01
1964 I nd. Eng. Chem. Res., Vol . 43, No. 9, 2004
a buffered water sol uti on (10 mL) at pH 10.0. The
reacti on was run at room temperature, and the reacti on
mi xture was anal yzed by NMR spectroscopy. The NMR
data and thei r assi gnments are gi ven i n Tabl e 4.
After 3 days, whi te crystal s were fi l tered from the
sol uti on and washed wi th water. The crystal s were
anal yzed by NMR spectroscopy, EI MS, and hi gh-resol u-
ti on mass spectrometry (HRMS).
1
H NMR (400 MHz,
CDCl
3
): 2.69 (s, N-CH
3
), 4.09 (s, N-CH
2
-S), 4.42
(s, S-CH
2
-S).
13
C NMR (400 MHz, CDCl
3
): 60.0 (N-
CH
3
), 37.6 (N-CH
2
-S), 34.4 (S-CH
2
-S). EI MS (70 eV)-
m/z (%rel ati ve i ntensi ty): 137.1 (M +2, 1.4), 135.1 (M
+
,
16), 89.0 (9), 70.1 (2), 57.1 (18), 46.0 (4), 45.0 (4), 44.0
(18), 43.0 (3), 42.0 (12), 41.0 (1). HRMS (70 eV) m/z:
cal cd for 3c, 135.01771; found, 135.01765.
I n the experi ment wi th gaseous H
2
S, the concentrated
gas was bubbl ed through a sol uti on of 1c (0.32 g, 0.25
mmol ) i n water (50 mL) for 23 mi n. Onl y 3c and
methyl ami ne were found i n the reacti on mi xture, whi ch
was anal yzed by
1
H NMR spectroscopy.
Reactions with the Oxygen Heterocyclic Com-
pounds4aand4b. 4a(0.23 g, 2.5 mmol ) was di ssol ved
i n a buffered sol uti on (50 mL) at pH 10.0, and Na
2
S
(0.19 g, 2.4 mmol ) was added. The sol uti on was l eft at
room temperature for 3 days, after whi ch no new
reacti on products were observed i n the NMR spectra.
I n another experi ment, 4a (0.23 g, 2.5 mmol ) was
di ssol ved i n water (50 mL), and NaHS (0.14 g, 2.4 mmol )
was added. The pH of the sol uti on was adjusted to 7.0.
No change was observed i n the NMR spectra.
The methyl -substi tuted tri oxane 4b(0.33 g, 2.5 mmol )
was di ssol ved i n water (50.0 mL). NaHS (0.14 g, 2.4
mmol ) was added, and the pH was adjusted to 10.0. The
sol uti on was anal yzed by
1
H NMR spectroscopy, and
after 3 days, the pH was l owered to 7.0. No change was
observed i n the NMR spectra.
Hydrolysis. The rates of hydrol ysi s of 1a-c were
determi ned by di ssol vi ng the compounds i n 0.5 M Na
2
-
HPO
4
buffers of the desi red pH i n an NMR tube. The
concentrati ons of tri azi nane i n the sol uti ons were 0.10
vol %. The hydrol ysi s was fol l owed by recordi ng of
1
H
NMR spectra wi th fi xed i nterval s (1-3 mi n), usi ng
acetoni tri l e as an i nternal standard. From each spec-
trum, the concentrati ons of 1a-c were cal cul ated and
the rate constants k
obs
, k
1
, and k
2
determi ned.
Reactions with HS
-
. I nvesti gati on of the reacti on
rate between tri azi nanes 1a-c and HS
-
was performed
by mi xi ng known amounts of three sol uti ons i n an NMR
tube:
(a) Solution 1 (0.10 mL). Tri azi nane 1a, 1b, or 1c
(0.25 mmol ) and acetoni tri l e (i nternal standard, 0.0103
g, 0.25 mmol ) were di ssol ved i n D
2
O (5.0 mL).
(b) Solution 2(0.10mL). NaHS (0.14 g, 0.25 mmol )
was di ssol ved i n D
2
O (5.0 mL).
(c) Solution 3(0.80mL). A 0.50 M sol uti on of Na
2
-
HPO
4
was di ssol ved i n D
2
O.
Before mi xi ng, the pH i n al l three sol uti ons was
adjusted to the desi red pH. Sol uti ons 1 and 3 were
mi xed fi rst, and the ti me was started when sol uti on 2
was added.
1
H NMR spectra were recorded wi th fi xed
i nterval s and the tri azi nane concentrati ons determi ned
for each of them. From these data, the observed rate
constants k
1
, k
2
, and k
3
were determi ned.
Literature Cited
(1) Worl d Heal th Organi zati on. Envi ronmental Heal th Cri teri a
18: Hydrogen Sul fi de, Geneva, Swi tzerl and, 1981.
(2) Bakke, J. M.; Buhaug, J.; Ri ha, J. Hydrol ysi s of 1,3,5-Tri s-
(2-hydroxyethyl )hexahydro-s-tri azi ne and I ts Reacti on wi th H2S.
I nd. Eng. Chem. Res. 2001, 40 (26), 6054.
(3) Buhaug, J. B. I nvesti gati on of the Chemi stry of Li qui d H2S
Scavengers. Ph.D. Thesi s, Norwegi an Uni versi ty of Sci ence and
Technol ogy, Trondhei m, Norway, 2002.
(4) CRC Handbook of Chemistry and Physics, 78th ed.; Li de,
D. J., Edi tor i n Chi ef; CRC Press: New York, 1997.
Received for review June 17, 2003
Revised manuscript received February 9, 2004
Accepted February 18, 2004
I E030510C
Table 3. NMR Data for the Products of the Reaction between 1b and NaHS
1
H NMR
(ppm) mul ti pl i ci ty J (Hz)
13
C NMR
(ppm)
1
H NMR
coupl i ng to
(ppm)
NOESY
coupl i ng to
(ppm) compd
1.04-1.11 t 11.2 2.70 al l other si gnal s ethyl ami ne
t 11.2 3.09 3b
t 11.7 2.82 2b
t 16.5 2.55 1b
2.55 q 7.3 46.7 1.04-1.11 1.04-1.11, 3.40 1b
2.70 q 7.2-7.3 35.6 1.04-1.11 1.04-1.11 ethyl ami ne
2.82 q 7.2-7.3 46.9 1.04-1.11 1.04-1.11, 3.76, 4.12 2b
3.09 q 7.3-7.4 42.7 1.04-1.11 1.04-1.11, 4.66 3b
3.4 s, br 71.7 1.04-1.11, 2.55 1b
3.76 s 71.7 1.04-1.11, 2.82, 3.76 2b
4.12 s + s 32.5 + 54.2 1.04-1.11, 2.82, 3.76 2b+ 3b
4.66 s 56.1 1.04-1.11, 3.09 3b
Table 4. NMR Data for the Products of the Reaction
between 1c and NaHS
1
H NMR
(ppm) mul ti pl i ci ty
13
C NMR
(ppm)
NOESY
coupl i ng to
(ppm) compd
2.27 s 41.9 3.25 1c
2.38 s 28.8 methyl ami ne
2.47 s 43.1 3.65, 4.02 2c
3.25 s, br 77.5 2.27 1c
3.65 s 77.6 2.55, 4.02 2c
4.02 s 58.5 2.55, 3.65 2c
I nd. Eng. Chem. Res., Vol . 43, No. 9, 2004 1965