close

Вход

Забыли?

вход по аккаунту

?

Formation of 1 2 4-Triazolin-5-ones from tert-Butylnitroacetylene and Phenylhydrazines.

код для вставкиСкачать
Table 1. Heterocycles synthesized from ( I J and dinucleophiles.
Product
Yield
I
M.P.( C)
b. p. ( C/torr)
NMR(CDCI',
TMS=O)&(ppm)
7.4(9H, m);
3.1 (6 H, s)
6.35(1 H,s);
3.1 (6H.s);
2.5(3H,s)
(4)
83
l50/0 I
( 7 1 , R =-S-CH=C(CH3)-
93
70-73
(7),R =-C,H,-CH~-(l,2)
89
106
( 8 ) . R =-CHI
90
I m/o.1
( 8 ) , R =-CH,--C,HS
93
75-76
( 8 ) . R =4-pyridyl
95
118- 120
(91, X = O , R ' = R ' = R'= H
81
90-9 I
(Y), X =S, R I = R* = R' = H [a]
70
87
( 9 ) . X = O , , R ' = R ' = H, R' = N O ,
74
164
71
163
60
139 -140
( 9 ) . X = 0. R ' = H, R 2 = N O 2 , R
(Y), X = 0,R ' = R' = R 3 =C1
'=Cl
108
6.8--7.8(6H, 2m);
3.06(6H,s)
2.4 (3H, s):
3.1 (6H.s)
7.3 ( 5 H, s);
40(2H,s).
3.0 (6 H.s)
3.2(6H,s);
7.8-8.5(4H.m)
7.3(4H.m);
3.1 (6H,s)
7.0(4H,m):
3.1(6H,s)
7.0-8.0(3H, 2m);
3.16(6H.s)
7.8-7.912 H, m),
3.2(6H,s)
7.03 ( 1 H, s);
3.23(6H,s)
[a] Thesecompounds have also been synthesized by I<. Nuqurajunand! I Ranga R U ~lndlan
,
J. Chem. 7, 964( 1969).
Thus phosgeneimmonium salts prove to be at least as
useful for the synthesis of heterocycles as the related thioformamide chlorides[71,which suffer from the disadvantage
that they can eliminate either HCI or HSR.
Experimental:
Synthesis of (6) : 1 mol of ( I ) and 1 mol of (2) are boiled
under reflux in chloroform for 2 hours until evolution of
HCI stops. The solvent is evaporated off and the residue
is treated with 2N KOH and extracted with methylene
chloride. The extract is dried over sodium sulfate, the
solvent evaporated off, and the residue distilled at
150"C/0.1 torr.
Sj2nthesis of compounds (7) to ( 9 ) : 1 mol of ( 3 ) , ( 4 ) ,
or ( 5 ) and 1 mol of ( I ) are boiled under reflux in chloroform for 1-2hours until evolution of HCI stops. The
solvent is then evaporated off and the residue washed
with ether, treated with a solution of 2 N KOH, and then
extracted with methylene chloride. The extract is dried
over sodium sulfate, filtered, and the solvent finally evaporated off.
Received. January 29, 1973 [Z 797b IE]
German version: Angew. Chem. 85, 446 (1973)
[I] Immonium Chemistry, Part 8.-Part 7: B. Le C/L,/,J. Mommurrrs,
B. Sfelunder, and H . G. Viehe, Angew. Chem. 85. 445 (1973): Angew.
Chem. internat. Edit. 12.404 (1973).
[2] 2. Junousek and H. G. Viehe, Angew. Chem. 83,615 (1971); Angew.
Chem. internat. Edit. / ( J , 574 (1971).
131 H . G. Viehe, Z. Junousrk, and M . A. Dr/frenne, Angew. Chem. (13,
616 (1971): Angew. Chem. internat. Edit 10, 575 (1971)
,
2. Janousek, Angew. Chem. 84,
[4] H . G . Viehr. Th. ruii v ~ c e and
991 (1972); Angew. Chem. internat. Edit. I / , 916 (1972)
[ 5 ] H . G. l'iehe and 2. Jnnousrk, Angew. Chem. 83, 614 (1971); Angew.
Chem. internat. Edit. 10, 573 (1971)
[6] 2. Junousek, Dissertation, Univ. Louvain 1972.
[7] H . Eilrnqsfeld and L. MAbius, Chem. Ber. Y8, 1293 (1965).
406
Formation of 1,2,4-Triazolin-5-0nes from tertButylnitroacetylene and Phenylhydrazined
By Ckcile Derycke, Volker Jager, Jean Paul Putzeys,
Maurice Van Meerssche, and Heinz Giinter Viehe"]
Electron-poor nitroacetylenes['] react with amines and
hydrazines to give P-nitroalkenylamines (2) and p-nitroalkylidenehydrazines ( 3 ) , respectively. Surprisingly, however, the reaction of ?err-butylnitroacetyleiie (1) with
phenylhydrazine ( 4 a ) in ethereal solution at 0°C gives
a new condensation product ( 5 a ) by less of water.
The IR spectrum of ( 5 a) shows an absorption at 2265 cm- '
which is attributed to the - C E N + O function. ( 5 n )
can be reduced to the corresponding nitrile ( 6 a ) by triethyl
phosphite in refluxing benzene[3! On standing for three
days at 0-C, ( 5 a ) undergoes isomerization, the rate of
which can be increased by refluxing in CHCI,. X-Ray
analysis shows theisomer to have the structure 3-tert-butyll-phenyl-1,2,4-triazolin-5-one
(7a).
The substituted phenylhydrazines ( 4 b) and ( 4 c) likewise
afford the compounds ( 7 h ) and (7c).
The nitrile oxides ( 5 ) and the triazolinones ( 7 ) can also
(8)
be obtained from 3,3-dimethyl-2-iodo-I-nitrobutene
and the phenylhydrazines ( 4 ) with KOH.
E.xperimenta1:
Synthesis of (5a) from ( I ) : Compound (1) (258mg,
2.03 mmol) in ether ( 5 ml) is added over 5 min with stirring
[*] C. Derycke, Dr. V. JBger, and Prof. Dr. H. G. Viehe
Lahoratoire d e Chimie Organique, Universite d e Louvain
Naamsestraat 96, B-3000 Louvain (Belgium)
J. P. Putzeys and Prof. Dr. M . Van Meerssche
Laboratoire d e Chimie Physique, Universit6 d e Louvain
Naamsestraat 96, B-3000 Louvain (Belgium)
( a ) , R1 = H
( h ) , R' = NO,
(c), R' = CH,
Table I . Properties of the compounds synthesized.
Product
(Oh)
M.p.
('C)
IR
(cm- ')
NMR
(TMS =0)6(ppm)
(5a)
88
86-87
2265
(6ai
62
5940
2195
(70)
71 [a]
209
1690
1.25(9H,s);
6.7.7.15 ( 5 H, m);
8.22 (1 H, s)
1.25 (9H,s);
7.25 (5H,m);
8.25(1H,s)
1.4(9H,s);
7.4,7.9(5H,m);
12.1 (1 H, s)
(761
73[a]
271.
1710
(7c)
Yield
87[a]
220
1685
1.4(9H, s);
7.9 (4 H, s);
11.7(1H, s)
1.4(9H, s);
2.3 (3H, s);
7.15,7.85(4H,m);
12.1 (1 H, s)
[a] F r o m ( l ) a n d ( l ) .
t o ( 4 a ) (216mg, 2mmol) in ether (5ml)at 0°C. The solvent
is immediately evaporated off and the residue recrystallized
from ether/petroleum ether (b. p. 4 M O " C ) to give 385 mg
(88%) of ( 5 a ) .
Synthesis of ( 7 a ) from (8): Compound (8) (510mg,
2mmol) in ether (5ml) is added with stirring to ( 4 a )
(216mg, 2mmol) in ether (5ml) and KOH (200mg) at
0°C. After the reaction mixture has stood for three days
the solvent is evaporated off and compound ( 7 a ) is
obtained by recrystallization of the residue from CHCl,/petroleum ether (b. p. 60-80°C); yield 91 mg (42%).
Reduction of ( 5 a ) to ( 6 a ) : Triethyl phosphite (665mg,
4mmol) is added to ( 5 a ) (225mg, 1.04mmol) in dry benzene (10ml) over 5min at room temperature. After
15minutes' heating on a water bath the mixture is diluted
with its own volume of benzene and shaken with 5%
H 2 S 0 , (20ml) to decompose excess phosphite. As soon
as the characteristic odor of this compound has d i s a p
[I] Nitroacetylenes, Part 4.-Part 3: V Jiiger and H . G . Viehe, Angew.
Chem. 82, 836 (1970); Angew. Chem. internat. Edit. 9, 795 (1970).
[2] V Jiiger and H. G . Viehe, Angew. Chem. 81, 259 (1969); Angew.
Chem. internat. Edit. 8, 273 (1969).
[3] C. Grundmann and H. D. frommeld, J. Org. Chem. 30, 2077 (1965),
and references cited therein.
Angew. Chrm. inturnur. Edlr.
/ Vol. 12 ( 1 9 7 3 ) !No. 5
peared the organic layer is washed four times with water
and the solvent is evaporated off. The remaining oil is
crystallized from ether/pentane to yield 123mg (62%) of
(6 a).
Received: January 29, 1973 [Z 797c I€]
German version: Angew. Chem. 85, 447 (1973)
Conversion of a Ketone or an Aldehyde
into the Next Higher Nitrile"]
By Ulrich Schollkopf and Ro/fSchriider[*l
In a previous cornmunicationIz1we described the synthesis
of N-( 1-arenesulfonyl- 1-alkenyl)formamides ( 4 ) from zmetalated arenesulfonylmethyl isocyanides (2) and carbony1 compounds (3) and their conversion into the next
higher carboxylic acid (5) by acid or alkaline hydrolysis.
The metalated isocyanides were obtained by reaction of
arenesulfonylmethyl isocyanides ( I ) with potassium tertbutoxide in tetrahydrofuran[*]. At that time we did not
engage in a detailed study of the question of which intermediates are involved in the hydrolysis step ( 4 ) + ( 5 ) " - l .
The
that 2-cyanoadamantane is formed in
the reaction of adamantanone with tosylmethyl isocyanide
in ethanol/dimethoxyethane in the presence of sodium
ethoxide suggested the intermediacy of the nitriles (6)
during alkaline hydrolysis and their general accessibility
from ( 4 ) .
NH-CHO
R ' R ~ C:
C:
(4)
SOzAr
-- II,O
H
I
R'-C-CO,H
I
R2 (5)
H
I
R'X-C-N
I
R 2 16)
This is actually found t o be the case. As we have shown
(Table 1) the nitriles ( 6 ) are formed in good yields when
N-( 1-arenesulfonyl-1-alkeny1)formamides( 4 ) are refluxed
['I
Prof. Dr. U. Schollkopf and Dr. R. Schroder
Organisch-Chemisches Institut der Universitat
34 Gottingen, Windausweg 2 (Germany)
407
Документ
Категория
Без категории
Просмотров
2
Размер файла
169 Кб
Теги
ones, butylnitroacetylene, phenylhydrazin, triazoline, formation, tert
1/--страниц
Пожаловаться на содержимое документа