Mumma—Hess’s rearrangement
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 1, January, 2011
195
with a reflux condenser. The mixture was heated in an oil bath to
(1.66 g, 10 mmol) and NꢀMP were sequentially placed into the
flask prior filled with argon. Triethylamine (2.8 mL, 20 mmol)
and imidoyl chloride (3.53 g, 10 mmol) were added with vigorꢀ
ous stirring. The mixture was placed into an oil bath, and the
temperature of the reaction mixture was elevated to 120 °C and
kept for 8 h. After the reaction was completed, the product was
precipitated into a 2% aq. ammonia, sequentially washed with
1% aq. sodium disulfite and water, dried in a vacuum drying oven
at 60—70 °C until the weight was constant. Characteristic visꢀ
cosity (η) was 0.26 dL g– (an Ostwald viscometer (∅ = 0.56 mm),
7
0—80 °C and kept for 2 h after complete homogenization of the
reaction solution. An excess of thionyl chloride was evaporated.
The product was recrystallized from octane or hexane. The yield
was 94%, m.p. 81.2—81.8 °C. Found (%): C, 67.94; H, 4.27;
N, 8.02. C H N Cl . Calculated (%): C, 68.15; H, 4.00;
2
0
14
2
2
–
1
N, 7.94. IR, ν/cm : 1636 (C=N); 695 (C—Cl).
Polycarboxyimidates were obtained in a 50ꢀmL twoꢀneck
flask equipped with a stirrer, inlet and outlet for argon. An acid
1
(
1.66 g, 10 mmol) and NꢀMP were sequentially placed into the
–
1
flask prior filled with argon. Triethylamine (2.8 mL, 20 mmol)
and imidoyl chloride (3.53 g, 10 mmol) were added with vigorꢀ
ous stirring. The mixture was placed into an oil bath, and the
temperature of the reaction mixture was elevated to 70—80 °C.
After the reaction was completed, the product was precipitated
into a 2% aqueous ammonia, sequentially washed with 1% aq.
sodium disulfite and water, dried in a vacuum drying oven at
DMF, 20 °C). The yield was quantitative. IR (KBr), ν/cm :
13
1787 (C=O). C NMR (DMSOꢀd ), δ: 164.5 (C(2), C(2´));
6
121.7—134.4 (C ).
Ar
References
1
. V. V. Korshak, Khimicheskoe stroenie i temperaturnye khaꢀ
rakteristiki polimerov [Chemical Structure and Thermal Charꢀ
acteristics of Polymers], Khimiya, Moscow, 1970, 419 pp.
(in Russian).
6
(
0—70 °C until the weight was constant. Characteristic viscosity
η) was 0.24 dL g–1 (an Ostwald viscometer (∅ = 0.56 mm),
–
1
DMF, 20 °C). IR (KBr), ν/cm : 1687 (C=N); 1710 (C=O);
1
1
212, 1076 (C—O). 13C NMR (DMSOꢀd ), δ: 139.5 (C(1));
6
2
3
. K. V. Vatsuro, G. L. Mishchenko, Imennye reaktsii v orgaꢀ
nicheskoi khimii [Named Reactions in Organic Chemistry],
Khimiya, Moscow, 1976, 471 pp. (in Russian).
. E. Pretsch, P. Bullmann, C. Affolter, Structure Determinaꢀ
tion of Organic Compounds, Springer, Berlin, 2000.
64.4 (C(2)); 120.4—135.2 (CAr).
NꢀPhenylꢀsubstituted polydiacylamides. A. A sealed tube with
polycarboxyimidate (1 g) was heated for 10 h at 150 °C. A polyꢀ
mer obtained was dissolved in DMF upon heating, then precipiꢀ
tated into water, and dried in a vacuum drying oven at 60—70 °C
until the weight was constant. The yield was quantitative. IR
KBr), ν/cm–1: 1791 (C=O). C NMR (DMSOꢀd ), δ: 165.1
13
(
(
6
C(2), C(2´)); 120.4—135.4 (CAr).
B. A oneꢀstep synthesis was performed in a 50ꢀmL twoꢀneck
flask equipped with a stirrer, inlet and outlet for argon. An acid
Received December 29, 2009;
in revised form August 3, 2010