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TABLE I
Reaction of Methionine with Hydroxy Compounds in 16 N Xuljuric Acid at 155”
The reaction mixtures were prepared by weight and contained 50 mM of nn-methi-
onine, 100 mM of hydroxy compound, and 50 ml. of 18 N HzSOI. Methionine and
homocystine determinations were made on aliquots of a 1: 10 aqueous dilution of the
reaction mixture. All results are expressed as per cent of methionine initially
present, The determinations of homocystine and sulfonium salt were made at the
end of the reaction.
Methionine
Homo- julfonium
cystine phospho-
AftCr 15 min. tungstate*
mixing 1 hr.
-I
“ tt . . 100 21** 45**
cipitate formation and the low yield of phosphotungstate in the former case
and darkening of the reaction mixture in the second. The apparent lack
of reaction with phenol and ethanolamine is contradicted by the absence of
the self-decomposition of methionine, which suggests reversible sulfonium
salt formation depending on temperature. With the biologically occurring
hydroxy compounds, threonine and serine, the predominant reaction was
the decomposition of methionine according to Reaction 2. Several var-
iations in conditions were employed with serine (in order to prepare
the methylsulfonium salt of cystathionine (7)), all with negative results.
These included the use of phosphoric acid, 9 N’ and 36 N H&304, and (as
shown in Table I) the prior formation of the sulfate derivative of serine by
the use of concentrated sulfuric acid (8). /LPropiolactone readily formed
preferential elimination of the methyl group have long been utilized for the
preparation of S-substituted homocysteine derivatives from methionine
and organic halides (14, 15). Decreasing the concentration of acid de-
creases the rate of Reaction 3, 6 per cent methionine being formed on
refluxing for 4 hours in N HCl in comparison with approximately 40 per
cent in 6 N HCl (see Fig. 1).
Refluxing a solution of methionine methylsulfonium bromide in water
(pH 4.0) led, after 1 hour, to 64 per cent decomposition according to
pK 7.7 (see the next paragraph), this decomposition represents the be-
havior of the ion Me&+R(NH3+)COO- and it may be concluded that
dissociation of the carboxyl group makes the amino acid moiety the more
labile group. Elimination of the charge on the amino group intensifies this
effect: the sulfonium salt in the presence of 2 equivalents of alkali was
found to be completely decomposed after refluxing for 1 hour; i.e.
RSMezf + OH- - Me&S + ROH (4, b)
respectively, 63.7 and 92.1 per cent of the theory for Reaction 4, a. No
methionine was found by iodine titration and the loss of methyl groups was
91 per cent of the theory.
A solution of 0.0516 M methionine methylsulfonium bromide and 0.1052
M NaOH was refluxed for 1 hour. The decrease in alkalinity and the loss
0.D. D
10
D
3.0
A s C
of methyl groups were 101 and 99 per cent, respectively, of the theory for
Reaction 4, b. There was no evidence of olefin formation, as indicated by
the absence of bromination with iodate and bromide. The homoserine to
be expected from the reaction was isolated as the lactone by utilizing the
procedure of Livak et al. (22). The alkaline reaction mixture from 10
m&t of the methylsulfonium salt was neutralized with sulfuric acid and
evaporated to semidryness in vacua. The residue was treated with ethanol
and filtered from sodium sulfate. Alcohol was removed from the filtrate
116 METHIONINE SULFONIUM SALTS
SUMMARY
BIBLIOGRAPHY
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