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Condensation of Dichloromethylenedimethyl-ammonium Chloride (УPhosgene Immonium ChlorideФ) with N N-Dialkylcarboxamides.

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Pyrocatechol reacts with (1) in the same manner as phenol,
forming the analogous immonium salt (6), which is
characterized by its facile hydrolysis to o-phenylene carbonate.
Ammonolysis of ( I ) with liquid ammonia gives dimethylcyanamide in 35% yield. Reaction of ( 1 ) with two moles
of dimethylamine yields tetramethylurea dichloride, which
forms tetramethylthiourea on treatment of the reaction
mixture with an aqueous solution of sodium sulfide. Even
very weak primary amines produce the corresponding
chloroformamidines (7) with ( I ) .
(7)
p
-+
3
N=C-N\
R
Condensation of Dichloromethylenedimethylammonium Chloride (“Phosgene Immonium
Chloride”)“*’ with N,N-Diakylcarboxamidestl]
By Zdenek Janousek and Heinz Gunter Viehe“]
Dedicated to Professor F. Bohlmann on the occasion of his
50th birthday
We have found the immonium salt dichloromethylenedimethylammonium chloride ( I ) to undergo condensation
with CH active compoundsrz1.Thus when compound ( I )
(0.2 mol) and N,N-dimethylcarboxamides (2) (0.1 mol)
[or their a-chloro immonium chloride derivatives (3)] are
refluxed together in CHzCIz or CHCI, for one to three
hours, the new 1,3-dichloromalonylcyanines( 4 ) are formed
in high yields. During the reaction, heating is continued
until the evolution of HCl ceases and a clear solution
results. Compounds ( 4 a ) -( 4 d ) crystallize on removal
of the solvent ; they may be recrystallized from benzene/
CH’CI,.
Compounds ( 4 ) are 1,3-dielectrophileswhich permit facile
cyclization reactions‘’].
CH3
H360 F1
N=C,
Cl0
H3C/
c1
Solvent,
temp. (“c)
II
NMR (CDCI,),
6 (TMS=O)
Cpd.
R
(7a)
p-COOC,H,
CHzC1,
40
96
(7bl
P-NO,
CIC,H,
1rK-i10
80
(7c)
2,4-(NO,),
ClC,H,
80
87
1.23 (3H/s), 3.08 (6H/s),
4.30 (2H/m), 6.82 (2H/d),
7.92 (2H/d)
3.22 (6H/s), 6.93 and
8.16 (4H/2 doublets,
J = 9 Hz)
2.83 (6H/s), 7-9 (3 H)
To synthesize N,N-dimethyl-N‘-p-nitrophenyl-0-phenylisourea (8b), a solution of sodium phenoxide (3.48g,
30 mmol) in dioxane (80 ml) is added to a solution of ( 7 b )
(6.83 g, 30mmol) in dioxane (200ml). After 3 hours’
stirring at 40°C the precipitated NaCl is filtered off and
the solvent is removed. The oily product is purified by
column chromatography on silica gel, yield 3.1 g (3573,
m.p. 98-99°C (from ether); NMR (CDCI,): 6=3.08
(6H,s),7.95 (2H,d,J= 8 Hz), the other doublet being covered
by the multiplet at 6 = 6.73-7.30 ppm (7H); IR (CHC1,):
1640, 1578, 1500, 1330 cm-’; mass spectrum: 286 (Mf),
209,192,72.
Received: December 28,1970 [ Z 447a IE]
German version: Angew. Chem. 83,614 (1971)
Publication delayed at authors’ request
[I] Immonium Chemistry, Part I.
[2] See Z. Janousek and H. G. Viehe, Angew. Chem. 83, 615 (1971);
Angew. Chem. internat. Edit. 10, 574 (1971); H. G. Viehe, 2. Janousek,
and M.-A. Defrenne, Angew. Chem. 83, 616 (1971); Angew. Chern.
internat. Edit. 10, 575 (1971).
[3] 2. Arnold, Collect. Czech. Chem. Commun. 24,4048 (1959).
[4] A. Senning, Chem. Rev. 65,388 (1965).
[ S ] N . N . Jarovenko and A. S. Vasilev, Zh. Gen. Chem. USSR 29,3786
(1959); Chem. Abstr. 54, 19466 (1960).
[6] N . N . Jarouenko et al., Zh. Gen. Chem. USSR 36, 1309 (1966);
Chem. Ahstr. 65, 16885f (1966).
171 We thank Mr. R. Merenyi (Brussels) for his advice.
181 E. Kiihle and B. Anders, French Pat. I405732 (1965); Chem. Ahstr.
64, 9603 (1966).
574
0
+ R-CH2-C-N(CH3),
1
f 3)
R
I
Cpd. R
Yield
M. p. (“C) NMR (CDCI,), 6 (TMS = 0) (ppm)
(%)
(4b)
H
C,H,
91
88
114-116
65-67
(4c)
(4d)
C,H,
C1
90
88
oil
94
(4a)
3.66 (12H/s), 5.88 (1 H/s)
1.2 (3H/t), 2.7 (2H/m), 3.28
and 3 57 (12 H 7 singlets)
3.58 (12 His) 7.4 (5 Hjm)
3.68(12H/s)
Hydrolysis of a suspension of (4a)-(4d) with aqueous
NaHCO, solution (one hour’s stirring) produces the
malonylamides (5 a)-(5d), which can be recrystallized
from ether after extraction from the reaction mixture with
CH’Cl, and evaporation of the solvent.
H,O
(4)
R,
/c0N(CH3)2
NaHCOJ- HF,CON(CH3),
f5 )
[*] Dipl.-Chem. Z. Janousek and Prof. Dr. H. G. Viehe
Laboratoire de Chimie Organique
Universite de Louvain
Naamsestraat 96, B-3000 Louvain (Belgium)
[**I Trade name (Aldrich).
Angew. Chem. internat. Edit. / Vol. 10 (1971) J No. 8
Cpd.
Yield
M. p. ("C) IR (CO) (cm- l )
Ref.
[a]
75-76
149
92
~31
("A)
70
75
78
73
(Sa)
(5bj
(Sc)
(5d)
1640 (broad)
1648
1642
1650
-
[41
-
[a] B.p. 104"Cj0.6 torr
Treatment of ( 4 a ) - ( 4 c ) with H,S in CH,Cl, in the
presence of a threefold excess of triethylamine gives the
substituted malonylthioamides ( 6 a)-(6 c ) .
H S
(4)
R,
,cSN(CH3)2
H'
'CSN(CH,),
2
c
(c,H,),N
(6)
Cpd.
Yield
NMR (CDCI,), F (TMS=O) (ppm)
M.p.("C)
(%)
(6a)
70
106-107
(66)
83
117-118
(6c)
55
193
~~~
[2] See [l] and H. G. Viehe, Z . Janousek, and M.-A. Defrenne, Angew.
Chem. 83, 616 (1971); Angew. Chem. internat. Edit. 10, 575 (1971); Z .
Janousek. Thbse de Doctorat, Louvain 1911; G. de Voghel, Mem. de
Licence, Louvain 1971.
[3] H. Bredereck, Chem. Ber. 94,2278 (1961).
141 R. Burgada, C. R. Acad. Sci. Paris 258, 1532 (1964).
3.42 and 3.53 (12H/2 singlets),
4.37 (2H/s)
1.05 (3H/t), 2.23 (2H/m), 3.33 and
3.48 (12H/2 singlets), 3.92 (I H/t)
3.18 and 3.52 (12H/2 singlets),
5.76 (IH/s), 7.30 (5M/s)
Reaction of Dichloromethylenedimethylammonium
Chloride ("Phosgene Immonium Chloride")[**1
with Carbonyl-Activated Methylene Groups[']
By Heinz Giinter Viehe, Zdenek Janousek, and Marie-Agnes
Defrenne"'
Dedicated to Professor F. Bohlmann on the occasion of his
50th birthday
The immonium salt dichloromethylenedimethylammonium
chloride ( 1 ) reacts readily with protic compounds"' via
chlorine substitution. Reaction with N,N-dimethylcarboxamides yields the new and versatile dichloromalonylcyanines (2), thus demonstrating the high reactivity of ( 1 )
towards active methylene groups['I.
R
~
Cpd.
IR (CHCI,) (cm- ')
Mass spectrum
(6a)
(66)
(6c)
1510,1388,1113,1097
1500,1387,1278
1505,1387,1278
190 (M'), 157,146,92,88
218 (M+), 189,146,130,98
266 (M+),233,189, 178,157
Reaction of ( 4 a ) with liquid methylamine and subsequently
with concentrated KOH solution at - 10°C produces
hexamethylmalonylamidine (7) ; yield 61 '4. b. p. 75"C/
0.5 torr, NMR (CDCI,): 6=2.85 (12H,s),3.08 (6H,s), 3.38
ppm (2H,s); IR (film): 1610,1370,1260, 1117,1050cm-';
mass spectrum: 184 (M+),169, 154,140.
1. CH,NH,
c'=N- CH,
A similar condensation is now described for ( I ) with
carbonyl-activated methylene compounds such as cycloalkanones, phenylacetone, acetophenone, ethyl malonate,
and acetoacetates.
Cycloalkanones (3) react with ( I ) in refluxing chloroform,
either by monocondensation (n= 2,3,4) or by dicondensation ( n = l ) to give the immonium chlorides ( 4 ) or the
trichloropentamethinecyanines(5). Hydrolysis of ( 4 ) and
( 5 ) gives the amides ( 6 ) and the diamide (7) respectively.
The overall yields of ( 6 a ) , (6b), and ( 6 c ) amount to 72,
87, and 75% respectively.
C,=N- CH,
In contrast, reaction of (4a) with liquid dimethylamine
yields tetrakis(dimethy1amino)cyanine (8) ;compound (8)
can be separated from dimethylammonium chloride as the
perchlorate, m. p. 174"C, which is only sparingly soluble
B
in water. The NMR spectrum (CDCI,) shows only one
peak for all the N-CH, groups at 6 = 3.02 ppm and one
proton at 6=3.60ppm; IR (CHCI,): 1530, 1432, 1400,
1100cm-'.
Received: December 28,1970 [Z 447 b IE]
German version: Angew. Chem. 83,615 (1971)
Publication delayed at authors' request
[I] Immonium Chemistry, Part 2.-Part 1: H. G. Viehe and Z . Janousek,Angew. Chem. 83,614 (1971); Angew. Chem. internat. Edit. 10, 573
(1971).
Angew. Chem. internat. Edit. 1 Vol. I0 (1971) f No. 8
(7) 78%
p] Prof. Dr. H. G. Viehe, Dip[.-Chem. Z. Janousek, and DipLChem.
M.-A. Defrenne
Universite de Louvain
Laboratoire de Chimie Organique
Naamsestraat 96, B-3000 Louvain (Belgium)
[**I Trade name (Aldrich).
575
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condensation, immonium, dichloromethylenedimethyl, ammonium, уphosgene, dialkylcarboxamides, chloride
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