Beruflich Dokumente
Kultur Dokumente
1957
MONOCARBAMATES OF
1,%DIHYDROXY-3-ARYLOXYPROPANES
1595
Monocarbarnates of 1,2-Dihydroxy-3-aryloxypropanes
MANUEL M. BAIZER, JOHN R. CLARK,
AND
JOHN SWIDINSKY'
E0
R = alkyl or alkoxyl
I I a R = methoxyl
I1
OA
OB
with liquid ammonia, yielded the same monocarbamate as was obtained via the chlorocarbonate route.
a
H
We have found that the dioxolones I1 are obb
-CONHZ
H
tained
in very high yield by ester interchange bec
H
H
tween ICand diethyl carbonate in the presence of a
d
H
-COCl
H
--CONH2
catalytic amount of a metallic alkoxide.' The al-CONH2
H
koxide may be added from an external source or
This investigation was undertaken in order to may be formed in situ, e.g., by dissolving sodium
provide a satisfactory practical method for prepar- in molten IC.Upon completion of the ester intering the carbamates Ia and to determine by inde- change, the alkoxide is destroyed by the addipendent unequivocal synthesis whether the previ- tion of ammonium chloride and the excess diethyl
carbonate is recovered by distillation. The residous structural assignments have been correct.
Our results, reported here, are a new synthesis of ual crude cyclic carbonate is suspended in a
Ia that is suitable for manufacturing purposes and a suitable solvent (such as ethyl or isopropyl a h - .
confirmation of the structure disclosed for the mono- hol), ammonia gas is introduced, the system is
carbamate of 1,2-dihydroxy-3-(o-methoxyphenoxy) closed and the mixture is stirred at room tempropane
I n addition we have discovered a perature for 8-16 hours. After the first several
hitherto unnoted rearrangement of carbamates l e hours, the initial precipitate disappears and thereafter the somewhat turbid solution begins to deposit
and If.
crystals
copiously. Excess ammonia is expelled by
Synthesis. Monocarbamates of 1,2-dihydroxy-3aryloxypropanes (IC) have been prepared2p4 by heating, and from the cooled clarified solution8
treating a solution of ICwith one mole of phosgene, the crude product (SO-SO% yield) is recovered by
which was assumed6to react preferentially with the filtration. Recrystallization from alcohols or ethyl
primary alcohol group to yield the hydrcxychloro- acetate yields 60-65% of pure Ia.
.carbonates (Id) (not isolated); the latter were then
(6) B. J. Ludwig and E. C. Piech, J. Am. Chem. Soc., 73,
converted by aqueous ammonia to Ia. Alterna- 5894 (1951).
A
B
-CONH2
R
alkyl or alkoxyl
alkyl or alkoxyl
alkyl or alkoxyl
alkyl or alkoxyl
methoxyl
methoxyl
(7)'Other catalysts such as anhydrous potassium carbonate (cf. M. s. Morgan and L. H . Cretcher, J. Am. Chem.
Soc., 68, 783 (1946)) are also effective.
(8) An aliquot of the solution was taken to dryness
in vacuo. The weight of the residue indicated quantitative
conversion t o monocarbamates. A sample of the residue was
analyzed by Dr. Eric Smith, S. B. Penick and Co., using
infrared spectroscopy and was found to contain 70-7377, of
Ie. All other infrared data reported here were likewise
obtained by Dr. Smith.
1596
The results of the ammonolysis of IIa were studied in detail. From the mother liquors remaining
after the removal of pure Ie, melting in the range
93-97', there was obtained by careful fractional
crystallization, preferably from ethyl acetate, a
quantity of isomeric carbamate, m.p. 117-119",
shown below to have the structure If. The highermelting isomer was always obtained in minor yield,
but its formation was not suppressed by conducting
the ammonolysis at higher or lower temperatures or
under pres~ure.~
The infrared spectrum of If differs substantially from that of Ie in the "fingerprint region."
In particular If has a very strong absorption band
at 10.17 p which is completely absent in the spectrum of Ie.
Structural Investigation. As mentioned above,
the rea,ction of one mole of phosgene with IC was
assumed to take place at the primary alcohol
group and to lead from the chlorocarbonate to the
primary monocnrbamate. I n order to confirm this
structure, the qynthesis of If pictured in Chart I
was carried out.
VOL.
22
VIII
+
NaOCHaCeH5
0
'I
guaiacol
OH-
OCHz
OCONH~
OCONM,
DECEMBER 1957
MONOCARBAhIATEs OF ~,%DIHYDROXY-~-ARYTJOXYPROPANEB
Ie s o c i 2-+
6 ,\ OCH~CHCH~OCONH~
OSOCl
OCHa
I
VI11
+ AgOH
+OH
1597
l - C a r b a m m y - ~ h y d r o x y ~ ( ~ y p h e n o x y ) p r o p(Ie).
ane
To 396.4 g. (2.0 mole) of molten (100') 1,2dihydroxy-3(o-methoxyphenoxy)propane was added with stirring 5.6 g.
(0.1 mole) of sodium methylate and 472 g. (4.0 mole) of
diethyl carbonate. The mixture was heated with stirring,
and the ethanol which formed distilled at 79-84".When the
internal temperature was 130, heating was stopped, and
6 g. of ammonium chloride was added. The remainder of
the ethanol and excess diethyl carbonate were then distilled in vaew (25mm.) to an internal temperature of 130'.
The residue, crude dioxolone, IIa, was w d without purification for the next step. A small amount of the residue was
recrystallized from ethyl acetate; m.p. 68.4-69.0O.
A d . ' * Calcd. for CuHuOr: C, 58.92; H, 5.40. Found:
C,59.04;H, 5.30.
The still warm (50') crude molten IIa was mixed with 100
ml. isopropyl alcohol and added with stirring to a solution
of 68 g. (4 mole) of ammonia in 2400 ml. of the alcohol.
The mixture was stirred overnight at room temperature in
a tightly stoppered flask.At h t a dense almost unstirrable
precipitate formed which dissolved and then reprecipitated.
The 2-propanol and ammonia were removed in vaew (120
mm.) on a steam bath. The residue was dissolved in 2400
ml. of hot ethyl acetate, treated with charcoal, and filtered.
On cooling, 304 g. (63.4%) of Ie, m.p. 95-96.5' was obtained. No depression was observed in a mixture melting
point with Ie prepared by Murphey's' procedure from 1,Zdihydroxy&(o-methoxyphenoxy)propane, phosgene, and
ammonia. A second crop, 142 g. (28.4%), m.p. 90-105"was
obtained. This substance was rearranged (see separate
section on rearrangement) to yield 94 g. (19.5%) more of
Ie, m.p. 94.5-96.0'. Another 8.4 g. (1.7%) was obtained by
rearranging 15.4 g. (3.2%) of a third crop obtained from the
mother liquors of the rearranged second crop; m.p. 94.596.0'. The total of Ie was 406.4 g. (84.6%).
Isolation of l - h y d r ~ - ~ ~ r ~ ~ y ~ ( ~ ~ x y p h
propane (I,).A kilogram of partly solvenbfree (400g. solid)
mother liquor from several Ie preparations was recrystallized from 2 litera of ethyl acetate. The mother liquor was
(20) The rearrangement also occurred when the mixture
was heated under reflux for 24 hours, but in this case
ammonia eacaped and, although the yield of Ie was normal,
no useful product could be obtained from the mother
liquor.
(21) Melting points are corrected, boiling points are not.
(22) Microanalyses by Schwsrzkopf Microanalytical
Laboratory, Woodside, L. I., N. Y.
i598
VOL.
22
DECEMBER
1957
THE
[CoNTRIBUTION FROM
I599
MALLINCKRODT
CHEMICAL LABORATORY
AT HARVARD
UNIVERSITY]
Only two publications have thus far been concerned with cycloalkyltin compounds. 2*s Similarly,
organotin compounds containing secondary alkyl
groups have been the subject of only a small number of s t ~ d i e s . ~ - ~
Little is known of the position of cycloalkyl and
secondary alkyl groups in the cleavage series for
organotin compounds. It has been established that
(1) Present address: Department of Chemistry, Massachusetts Instit,ute of Technology, Cambridge 39, Mass.
(2) E. Krause and R. Pohland, Ber., 57, 542 (1924).
(3) T. S. Bobashinskaya and K. A. Kocheshkov, J . Gen.
Chem. (U.S.S.R.), 8 , 1850 (1938).
(4) Z. M. Manulkin, J . Gen. Chem. (U.S.S.R.), 14, 1047
(1944).
(5) F. Caujolle, M. Lesbre, D. Meynier, and A. Blaizot,
Compt. rend., 240, 1732 (1955).
(6) J. G. A. Luitjen and G. J. M. van der Kerk, Znvestigations in the Field of Organotin Chemistry, Tin Research
Institute, Greenford, England, 1955, p. 105.
the phenyl group is cleaved in preference to the cyclohexyl group by the action of concentrated hydrochloric acid on (cyclo-CaHll)2Sn(CsH,)z,s
thus showing that the latter group behaves
like an aliphatic group. However, no experiments
have been reported which determine the place of a
cycloalkyl group in the aliphatic organotin cleavage series. It was stated by Luitjen and van der
Kerk (ref. 6, p. 80) that secondary alkyl groups arc
cleaved from a tin atom prior to n-alkyl groups, but,
a quantitative product study of only one reaction4
+ IZ +(n-CJL)3Sn1 + sec.-CdHd
(n-CaH9)&K&H9-sec.