Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
-- 2
DISCLOSURE OF THE INVENTION
PROCESSOR THE PREPARATION OFF COMPOUND HAVING ANTI-
ULCER ACT IV IVY "
The invention refers to processes for the preparation
of the compound N-[2-[[[5-[(dimethylamino)methyl]-2-fur-
anyl]methyl]thio]ethyl]-N'-(3,4-methylenedioxybenzZulu-
nitro-l,l-ethanediamina of formula (I)
(CHINCH CH2-S-CH2CH2-N~
- / SHEEHAN (I)
SHEEHAN
Said compound, described in Canadian Patent No.
1,182,121, in the Applicant's name, endowed with high
anti ulcer activity and with practically no toxicity, may
be obtained according to the invention in high yields
and in higher purity degree in comparison to the method
described above wherein the reaction between 2-((2-
aminoethyl)thio-methyl)-5-(dimethylaminomethyl)-fuurn
and 1-nitro-2-methylthio-2-(3,4-methylenedioxybenzyl-
amino)-ethane, was reported.
According to one embodiment of the invention, 2-
(dimethylaminoethyl)-5-(R-methyl)furan (formula II)
',,
7 I
(CHINCH 2 (II)
wherein R is hydroxy, halogen, dime~:hylamino or trimethylam-
rnonium iodide, is reacted with the compound of formula (III)
2 2 \
OX (III)
SHEEHAN
wherein X may be O, S or a group of formula SHEEHAN.
When X is the SHEEHAN group, the compound I is directly
obtained, while, when X is oxygen or Selfware, treatment
with nitromethane of the compound obtained by reacting (II)
and (III) gives compound I.
The intermediate of formula III wherein X is SHEA can
be prepared starting from l-nitro-2,2-bis-(methylthio)-
ethene or from 2~(nitromethylene)-thiazolidine, according
to the following schemes:
I
SKYE 1
5 33 02N-CH
(IV) (V) (VI)
NH2 US
(VI) + NH3 > 02N-CH=C~ 2 2 ( I )
NH{~H2~
(VII)
In the above scheme, l-nitro-2,2-bis-(methylthio)-eth_
no (formula IV) is reacted with 3,4-methylenedioxybenzylamine
(formula V) to give l-nitro-2-methylthio-2-(3,4-methylenedio-
xybenzylamino)ethene (formula VI) which is treated with am-
mania to give N-(3,4-methylenedioxyben~yl)-1-nitroethenediami
no (formula VII) and the latter, added with ethylene sulfide,
yields the intermediate III.
Alternatively, the compound VI can be conveniently reacted
with cysteamine, or 2-aminoethanethiol, directly giving the
intermediate III.
Another scheme (Scheme 2) comprises treating nutria-
bis-(methylthio)-ethene (formula IV) with ammonia to give
1-nitro-2-amino-2-methylthio-ethene (VIII) which is reacted
with ethylene sulfide to give l-nitro-2-methylthio-2-(2 men-
captoethylamino)-ethene (formula IX) which is in turn treated
'~.~;,`
I
with 3,4-methylenedioxy-benzylamine TV), to give the
intermediate (III):
Scheme 2
/NH2 us /NH-CH2(~2SE
(IV)+ NH3 ~02N-CH=C + 2 2 -~~2N~=C~
\ SHEA SHEA
(VIII) (IX)
5 (IX) + (V) ~(III).
Compound IX can also be reacted with one of the compounds
of formula II, obtaining therefore the intermediate of the
following formula:
( 3)2NCH2 -CH2-s-cH2cH2NH-~-scH3
which, by treatment with 3,4-methylenedioxy-benzylamine (V),
gives compound I.
Finally, Scheme 3, much more simple and fast, yields in-
-termediate (III) by reacting 2-(nitromethylene)-thiazolidine
(formula X?, a known compound French Patent No. 2,384,765;
Germ Offend No. 2,734,070; S. B. Swahili et at.- Pestle. Vex
no. Nazi Conga. Entomb 1976, 153 - (KIWI. 89, 101812-
1978) and Chum. Abstr. 99, 70613v/, with 3,4-methylenedioxy-
benzylamine (formula V).
OX`.`
~7~9.Z
SCHEME 3
N
--SHEEHAN + (V) > (III) .
(X)
The intermediate of formula III wherein X is oxygen has
been in turn obtained by reacting 3,4-methylenedioxybenzyla
mine (formula V) with N,N-carbonyl-diimidazole, obtaining
N-(3,4-methylenedioxybenzyl)imidazol-carbonylamidee (formula
IX?, whose recovery is not necessary, but which is directly
reacted with cystarnine or 2-aminoethanethiole obtaining the
desired intermediate III (X= O) according to the following
scheme:
I N C N OH -C-N
(XI)
+ 2 SHEA HUSH (III).
In a similar way, but in higher yields, the urea III has
been obtained by reacting N-(3,4-methylenedioxybenzyl)imida-
zol-carbonylamide (formula XI) with cyst amine or dummy-
nodiethyldisulfide (formula XII) in a 2:1 ratio, obtaining
Boyce 3, 4-methylenedioxybenzylaminocarbonylaminoethyl)di-
sulfide (formula XIII) which, by simple reduction with zinc
and acetic acid gives the intermediate III
aye
-- 7 --
2 ll2C~2-S-S-Cl~2C~l2-N~12
( OH NH-C-NII-Cl1 SIEGE -So 2(III).
(XIII)
The intermediate of formula III wherein X is Selfware
is obtained, on the other hand, by condensing methyl-
nedioxybenzylisothioeyanate with cyst amine
The intermediates II are known and can be prepared a-
cording to E. W. Gill et at. (J. Chum. Sock 1958, 4728)
and 0. Moldenhauer et at. (Ann. 580, 169, 19s3? with
obvious changes of the methods described therein.
According to a modification of the above described me-
thuds for the preparation of compound I, the compounds
of formula III having R = chlorine or hydroxy can be tray-
stormed into the compound having R = SO which can be fee_
ted with the compound of formula:
2 2 \
OX
< 2
__
which can be obtained from compounds VII or VIII by
reaction with ethylene oxide.
According to another embodiment, compound I is
obtained starting from 2-(dimethylaminomethyl)-5-(2-
hydroxy)ethylthiomethyl-furan (formula XIV) with 2-
amino-2-(3,4-methylenedioxybenzylamino)-1-nitro-etthese
(formula VII, Scheme 1) in the presence of Nickel Rangy,
according to the following scheme:
(CHINCH CH2-S-CH2CH2-OH + H2N-C-NH-CH
SHEEHAN
(XIV) (vim)
3 (I).
The compound XIV can be optionally transformed into
the corresponding tessellate, which is then reacted with
compound (VII).
The following examples further illustrate the
invention without limiting the scope thereof.
EXAMPLE 1
a) l-Nitro-2-(3,4-methylenedioxybenzylamino)-2-(2-
mercaptoethylamino)-ethene - formula III:_X =
SHEEHAN; Scheme 1)
1-Nitro-2,2-bis-(methylthio)-ethene (33.05 g; 0.2 moles)
is added to l,1,2-trichloroethylene (200 ml) and the mixture
is reflexed to complete homogeneity. 3,4-MethylenedioxybeI-~y_
amine (15.1 g; 0.1 moles) dissolved in -the same solvent (100
ml) is then added to the boiling solution. Reflex is kept
for further 90 minutes, the solvent is then distilled off
under reduced pressure and the resize is purified by silica
gel column chromatography, eluding first with petroleum
ether, then with dichloromethane.
l-Nitro-2-methylthio-2-(3,4-methylenedioxybenzylammint)-
ethene (formula VI) is crystallized from dichloromethane-
ether. The antiquely pure product (16.7 g; 62% yield melts at 118-119C (not correct).
Selfware (Changer) = gala. % 11.95; found% 12.00.
The previously obtained compound (15.0 g; 0.056 moles)
is added to concentrated ammonia (200 ml) and the mixture
is stirred at room temperature for about 48 hours. After
evaporation under reduced pressure, the crude product
obtained is used in the following step: anyway, l-nitro~2-
amino-2-(3,4-methylenedioxybenzylamino)-ethene (formula VII)
can be crystallized from an alcohol, preferably 2-propanol
20 (12.9 g; yield 97%).-
The mercaptoethylation of the above compound has been
carried out with ethylene suIflde, according to the method
described by HER. Snyder et at. (J. Am. Chum. Sock 69,
2672-1947).
1-Nitro-2-amino-2-(3,4-methylenedioxyben~ylamino)--ethene,
I
-- 10 --
previously prepared (11.8 g; 0.05 moles), Tulane (50 ml)
and ethylene slide (3.0 g; 0.05 moles), are mixed in a
vessel under pressure. After closing the vessel, the mlxtu-
no is heated to 90-100C for 24 hours, under stirring. After
cooling and evaporation at reduced pressure, the crude pro-
duct is obtained which is purified according to the method of
WACO. Still et at. (J. Org. Chum. 43, 2923-1978)).
Elemental analysis: for C12H15N304S (297.33)
gala.% : C = 48.47; H = 5.08; N = 14.13; S = 10.78;
found% : C = 48.62; H - 5,12; N = 14.10; S = 10.52.
b) 2-(Dimethylaminomethyl)-5-chloromethyl-furan (formula II:
R = Of)
2-(Dimethylaminomethyl)-5-hydroxymethylfuran (15.6 g; 0.1
moles) prepared as described by EYE. Gill et at. (J. Chum.
Sock 1958, 4728), is dissolved in dichloromethane (100 ml)
and the solution is treated first with an hydrous hydrochloric
acid, then with phosphorus pentachloride, at room temperature
and in an heterogeneous phase. After about 4 hours the Shelley-
ruination is complete. The solid is collected and thoroughly
washed on the filter with dichloromethane to remove the pro-
spheres halides. The base is obtained by neat alkalinization
with 20% aqueous sodium hydroxide, and it is extracted with
dichloromethane. The organic solution, washed with water,
- dried (Nazi) and evaporated yields an oily residue (14.0 g;
yield 80.G%).
1~'27 I
-- 1 1 --
Chlorine (Schoerlillger~ - cowlick = 20.42; wound% = 20.77.
c) No / /5-/(Dimethylamino)methyl/-2-~uranyl/methyl/-
_ .
thi_/ethyl/-N'-(3,4-methylenedioxybenzyl)-2-nitro~~
ethenediamine (formula I)
Sodium metal, in small fragments (1.15 g; Ooze spa.), is
dissolved under nitrogen atmosphere, in absolute ethanol
ml). When all the metal is dissolved, l-nitro-2-(3,4-methy-
lenedioxybenzylamino)-2-(2-mercaptoethylamino)etheone (14.8g;
0.05 moles) is added. After heating to reflex for about 20
minutes, the mixture is left to cool and 2-(dimethylamino-
methyl)-5-chloromethyl-furan (8.7 g; 0.05 moles) dissolved
in absolute ethanol (50 ml) is slowly added under stirring.
The mixture is heated to 50-80C for about two hours, to
complete the reaction, then always at the same temperature,
water is added to slight turbidity. The mixture is left to
cool and then to stand overnight in the cold.
The crystallized product, melting at 98-102C (not eon-
feat), is recovered. Yield: 16.3 g (75%).
Elemental analysis for C H N 0 S (454.51)
20 26 4 5
gala. I: C = 55. 29; H = 5. 99; N = 12.90; S = 7.05;
found I: C = 55.39; H = 6.02; N = 12.79; S = 7.10.
The H-NMR spectrum confirms the structure of the compound:
(internal reference TAMS; solvent DMS0):
- - 2.1, s, 611; 2.7, m, OH; 3.4, s, OH; 3.7, d, 2~1; 3.85, s, OH;
4.3, s, OH; 6-7, m, OH aroma and SHEEHAN; 8 and 10, s broad, 211.
I I
-- 12 --
The compound is therefore identical to that obtained
according to Canadian Patent No. 1,182,121.
EXAMPLE 2
a) l-Nitro-2- (3,4-methylenedioxybenzylamino)-2- (Marquette-
ethylamino)-ethene (formula III: X = SHEEHAN; Scheme 3)
2-(Nitromethyl)thiazolidine (French Patent No.
2,384,765; Germ offend No. 2,734,070; SUB. Swahili et
at. - Pestle. venom. neurotoxic. 153, KIWI. 89,
101812) (7.3 g; 0.05 moles) is dissolved in a high-
boiling polar solvent, preferably Tulane or zillion
(100 ml). The mixture is reflexed in inert atmosphere,
then 3,4-methylenedioxybenzylamine (15.1 g; 0~1 moles)
is added drops in 30-40 minutes. When the addition
is over, reflex is continued for about 12 hours, then
the mixture is cooled, filtered, the filtrate is washed
with water, 10~ diluted hydrochloric acid, water, I
aqueous sodium hydroxide, then with water again; after
drying (McCoy) the solvent is evaporated under vacuum.
The residue, mainly constituted by the crude product, is
purified by silica gel (70-230 mesh) column chromatography
eluding with ethyl acetate-pekroleum ether. The analytic
gaily pure compound is obtained (10.1 g; 68% yield).
Elemental analysis for C H N O S (297.33)
12 15 3 4
gala. %: C = 48.47; H = 5.08; N = 14.13; S = 10.78
found I C = 48.53; H = 5.15; N = 14.08; S = 10.48
identical to that obtained in Example 1.
'I
b) No / /5-/(dimethylalnino)methy1/-2-furanyl/methyl/-
thi_/ethyl/N'-(2,4-methy1enedioxybenzyl)-2-nitro-11,1-
ethenediamine (formula I)
By reacting the intermediate III, obtained previously,
in the same manner as described in Example 1, the compound
identical to that of Example 1 is obtained (yield
72%).
EXAMPLE 3
. . . _ , . . = = =
a) 2,5-Bis-(dimethylaminomethyl)furan monoiodomethylate
(formula II, R = N(CH3)3I )
2,5-Bis-(dimethylaminomethyl)furan (9.9 g; 0.05 moles),
obtained as described by EYE. Gill et at. (J. Chum. Sock
1958, 4728) is dissolved in an hydrous acetonitrile (100 ml).
Iodomethane (7.1 g; 0.05 moles) is added drops to the
solution. After about 30 minutes, the qua ternary ammonium
salt starts to crystallize, which is collected and crystal
Zen from an alcohol, preferably ethanol (12.1 g; 71~ yield).
Iodine (Agony): cowlick = 37.3; found % = 36.9.
b) No _ /5-/(Dimethylamino)methyl/-2-furanyl/methyl/-
thio/ethyl/-N'-(3,4-[nethylenedioxybenzyl)-2-nitroo-1,1-
_thenedianine (formula T )
The previously prepared iodomethylate (6.8 g; 0.02 moles)
is dissolved in dimethylformamide (80 ml). nutria-
- methylenedioxybenzylamino)-2-(2-mercaptoethylaminoo)ethene,
prepared according to the Employ pa) (5.9 q; 0.02 moles),
I
- 14 -
is added -to the solution.
The mixture is heated under stirring at 80-120C in inert
atmosphere for about one day. After cooling the reaction
liquid is poured in water and ice, causing -the separation
of a gummy solid, which is collected by recantation, washed
again with water and crystallized from aqueous ethanol
(6.5 g; yield 72~): mop. 98-102C (not correct).
The compound obtained is identical to that prepared in
Example 1.
EXAMPLE 4
a) 2-(Dimethylaminomethyl)-5-chloromethyl-furan (formula II:
R = Of)
2,5-Bis-(chloromethyl)furan (16.5 g; 0.1 moles?, obtained
as described by O. ~oldenhauer et at. (Ann. 580, 169-1953?,
is dissolved in ether (200 ml) and added with dimethylamine
hydrochloride (8.1 g; 0.1 moles). The mixture is cooled to
0-5C, then an hydrous potassium carbonate (27.6 g; 0.2 moles)
is added in small portions under strong stirring, keeping the
same temperature and taking care that gas evolution is over
between one addition and -the other one. When the additions
are over, the temperature is allowed to raise to the room
temperature and the mixture is stirred for two additional
hours.
The inorganic salts present are filtered and the filtrate
is evaporated at reduced pressure. The crude product obtained,
impure of bis-substituted compound, is purified by the method
-- 15 --
o of I. C. Still et at. (J. Org. Chum. I 2923, 1978).
The desired pure product is obtained as a dense oil (12.4
g; 72~ yield), nearly colorless.
Chlorine (Schoeninger): gala.% = 20.42; found % = 20.33.
b) No / /5-/(Dimethylamino)methyl/-2-furanyl/methyl/-
thi_/ethyl/-N'-(3,4-methylenedioxybenzyi)-2-nitro--1,1-
ethenediamine (formula I)
By using the same method of the Example 1, the compound
of formula I identical to that of Example 1, is obtained
(yield 81~).
EXAMPLE 5
a)N-(2-Mercaptoethyl)-N'-(3,4-methylenedioxybenzyl)uurea
(formula III, X = O)
. . _
3,4-Methylenedioxybenzylamine (15.1 g; 0.1 moles) and
N,N'-carbonyldiimidazole (16.2 g; 0.1 moles) are dissolved
in an hydrous chloroform (200 ml). The solution is stirred at
room temperature for about 30 minutes, then cysteamine or 2-
aminoethanethiol (7.7 g; 0.1 moles), dissolved in an hydrous
chloroform (50 ml) is added thereto. The mixture is
stirred for further 30 minutes, then filtered and then the
filtrate is washed with water, 10~ hydrochloric acid, water
again, dried (McCoy) and the solvent is evaporated The gnu
de product obtained is crystallized from a mixture ethanol-
-~~ petroleum ether, obtaining the analytically pure product (13.2
g; 52~ yi~lcl).
I
- 16 -
Suffer (Sciloellinger): gala. I= 12.61; found -- 12.44.
Tile same intermediate may be obtained by an analogous
procedure, but in higher yields (75-80~) using cyst amine,
or 2,2'-diaminodiethyldisulfide (formula XII) instead of
2-aminoethanethiol. N,N'-8is-(3,4-methylenedioxybenzyl)-cysta
mine (formula XIII) is then cleaved into 2 moles of mercaptan
with zinc and acetic acid as described by OF Allen et at.
Org. Synch.- golf. vol. II, peg. 580.
b) No / /5-/(Dimethylamino)methyl/-2-furanyl/methyl/-
.
thio/ethyl/-N'-(3,4-methylenedioxybenzyl)urea
.
Sodium metal in small fragments (0.6 g; 0.025 moles) is
dissolved in absolute ethanol (100 ml). When all the metal
is dissolved, N-(2-mercaptoethyl)-N'-(3,4-methylenedioxyben-
zyl)urea (6.35 g; 0.025 moles) previously prepared is added
to the solution. The mixture is heated, under stirring, for 15
minutes an dafter cooling 2-(dimethylamino-methyl~-5-chlorome-
thyl-furan (4.35 g; 0.025 moles) dissolved in absolute eta
not (20 ml) is slowly added. The mixture is heated to about
70 for two hours, then cooled and water is added to slight
turbidity. After one night in the cold, the crystallized is
collected (7.40 g; 75,8~ yield) which is used in the next pus
sage.
A sample has been recrystallized for the elemental analysis.
_ Elemental analysis: for C H N O S (391.49)
19 25 3 4
7~3f~
0 gala. : C = 58.29; 1! = 6.43; N -- 10.73; S = 8.18
wound : C = 58.52; H = 6.25; N = 10.79; S = 8.10.
c) No / /5-_(Dimethy1amino)methyl/-2-furanyl/methyl/-
thi_/ethyl/-N'-(3,4-methylenedioxybenzyl)-2-nitro--1,1-
ethendiamine (formula I)
Nitromethane (3.5 g; 2.7 ml; 0.05 ml) and the previously
prepared urea derivative (19.5 g; OOZE moles) are intrude-
god into a flask immersed in an ice-salt bath; methanol (50
ml) and a solution of sodium hydroxide (2.1 g) in the same
volume of prickled water are added to the mixture, the fat
ton slowly so as the temperature does not exceed 10-15C. Du
ring the addition a precipitate, which can be diluted with
other methanol, is produced.
After stirring for 1 hour, diluted hydrochloric acid is
lo added to neutrality, then water to slight turbidity. After
standing overnight in the cold, the crystallized product is
collected, which, if not enough pure, is recrystallized
from aqueous ethanol (16.9 g; 77.8~); mop. 98-102C (not
correct). The compound is identical to that obtained in
Example 1.
EXAMPLE 6
No //S-/(Dimethylamino)methyl/-2-furanyl/methyl/thi_/--
ethyl/-N'-(3,4-methylenedioxybenzyl)-2-nitro-1,1-eethenediami-
.. . _ _ _ .. _ . ... _
no (formula I)
_
2-(Dimethylaminomethyl)-5-((2-hydroxy)ethyltilio-mmethyl)-
~7?~9~
Furman (4.30 9; 0.02 moles), and 2-a~ino-2-t3,4-methylene-
dioxybenzylamino)-l-nitro-ethene (VII) prepared according
to Example lay (6.43 g; 0.025 moles) are dissolved in
an hydrous Tulane (100 ml) under heating.
An hydrous Noreen (2.5 g) is added and the mixture
is reflexed under stirring for 12 hours. After cooling
the catalyst is filtered off and the filtrate is evapo-
rated to dryness. The crude product is then crystallized
from aqueous ethanol to purity (6.18 9; 68% yield): mop.
98-102C (not correct). The compound is identical to
that obtained in Example 1.
EXAMPLE 7
: 7
a)2-dimethylamino-methyl-5-(2'-tosyloxyeth~l)-thiomeethyl-
Furman
The compound has been obtained by known methods with
86~ yield.
Selfware (Schoeninger): gala. % = 17.35; found % = 17.24.
b) N-[2-[1[5-[~DimethYla ino)methyl]-2-furanyl]methyl]-
thio]ethyl]-N'-(3,4-methYlenedioxybenzyl)-2-nitro--
l,l-ethenediamine formula I)
The tessellate, prepared previously (7~4 g; 0.02 moles) is
dissolved in acetonitrile (70 ml). 2-Amino-2-(3,4-methylene-
dioxybenzylamino)-l-nitro-ethene (5.22 g; 0.022 moles) is ad-
dyed to the solution. The mixture is reflexed under stirring
I
_ 19 _
for 15 hours, and the solvent is then) evaporated off under
reduced pressure Ire crude product obtained is purified
by silica gel column chromatography, eluding with ethyl
acetate-methanol (7:3). The product obtained (5.3 g; 60.9%
yield) can be crystallized from aqueous ethanol; mop. 98-
102C; mixed mop. with the compound obtained in the Exam-
pie 1: 98-102C.
EXAMPLE 8
a) 3,4-Methylenedioxybenzylisothiocyanate
Carbon disulfide (38.1 g; 30.2 ml; 0.5 moles) and a cold
solution of sodium hydroxide (20 g; 0.5 ml) in water (45 ml)
are introduced in a flask immersed in an ice bath.
The mixture, at 10-15C, is added with 3,4-methylenedio-
xybenzylamine (75 g; 0.5 ml) in about 30'. Stirring is con-
tinted for further 30 minutes, and the mixture is then refly
Ted for about 2 hours. After cooling to 35C, ethyl chlorocar
borate (54.2 g; 47.5 ml; 0.5 moles) is slowly added and stir-
ring is continued for further 30 minutes at the same temperate
no.
When the reaction mixture is cooled at room temperature,
it is transferred into a separating funnel and the surnatant
is separated, dried (Nazi and the more volatile portion
is removed at 35-40C under vacuum, to give the pro-
duct enough pure for the following step (73 5 go 76% yield)
7~32
- 20 -
b)N-(2-Mercaptoethyl)-N'-(3,4-met:hylenedioxybenzyl)urea
.
(formula III: X = S)
. . _ .
A solution of 3,4-methylenedioxyisothiocyanate (joy 0.1
moles) in dichloromethane (80 ml) is cooled to 5C. 2-Amino-
ethanethiol (7.7g; 0.1 moles) diluted with dichloromethane
(50 ml) is added to the solution. The addition is slowly carried
out so that the reaction liquid does not exceed 10C. When
the addition is over, stirring is continued for one hour alto
wing the temperature to raise to the room one. The reaction
liquid, transferred into a separating funnel is washed with
water, 10% hydrochloric acid, water again, dried (McCoy), lit
toned and evaporated, obtaining the crude product as a no-
sidle, which is purified according to Still et at. (J. Org.
Chum. 43, 2923-1978). The product obtained (18.4 g; 68% yield)
is enough pure for the following step.
Selfware (Changer): gala. % = 23.71; found % = 23.83.
c) No //5-/(Dimethylamino)methyl/-2-furanyl/methyl/thio/--
ethyl/-N'-(3,4-methylenedioxybenzyl)thiourea
By reacting the previously prepared Thor with dummy
thylaminomethyl)-5-chloromethyl-furan (II, R = Of) in the
presence of sodium ethoxide, as described in the Example 5b),
the title compound is obtained (77% yield).
Elemental analYsls:for C191125N
_
cowlick: C = 55.99i H = G.18; N = 10.31; S = 15.73
phonically - 60.11; H -= 5.99; N = 10.29; S = 15.56.
I
d) No / /S-/(Dimethylamino)methyl/-2-lurdnyl/methyl/-
thio/ethyl/-N'-(3,4-methylenedioxyben~yl)-2-nitro--1,1-
ethenediamine (formula I)
By operating in the same way as in Example 5c), the come
pound of formula I has been obtained in a 81% yield, equal
to that obtained in the Example 1: mop. 98-102C; mop. (mixed):
98-102C.
_ ._
