TABLE I a-.4LKYL-a-O-R.ITKOBE~ZYL~l.~LOS.~l~ES
R
Yield, x" Alethud Metliod A u
It
...
E t hyl 60. 1 n-Propyl 53.1 Isopropyl 4.0 n-But yl 67.2 Isobutyl ... sec-Butyl 3.9 After one distillation.
___-
UP, OC (mm)
c
158 (0 7 ) 164 ( 0 9 ) 174 (2 0) 188 ( 1 . 6 ) 1 8 0 ( 1 75) l96(4 5 )
...
43.3 ... 50,2 37.2
Found, 5----
59.58 60.33 60.4d 61 77 61.39 61.43
H
N
6.65 6 77
4 . 70 4.42 4.24 4.4.5 4.12 4.48
6.X8
7.10 6.08 6.78
I llu
Yield.
11
K'
l\Iethod
Ethyl n-Propyl Isopropyl n-Butyl Isobrit yl sec-Butyl Ethyl n-Propyl Isopropyl
CO2C?I16 COXzHj COzCzHj C02C2Hj COzC2Hj COzC2Hj COyH COZH COzH
c c
n-Butyl Isobutyl sec-Butyl Ethyl n-Propyl Isopropyl n-Biit yl Isob11tyl
eo211 CO2H COlH H I1 I1 I1 H
SCHEME
(uiin)
ur
C C C C 1) I) 1)
5:3,6 72.5 76.8 79.8 71.7 72.5 76.0 73.2 85.4
1) 1)
7% 1 8.5 4
11 E E 1: I< E
xx 4 49 9 32 1 33 3 30 8 31 6
1 7 8 ( 1 8)" 62-63 1ox- 109 184(2 2 ) l68(1 5 ) 82-$3 140 dec 127 dec 103-1 06 131 decb 97-99 111 dech 120 devh 134 (1 0 ) 14,5 (0 8 ) 118-119* 155 (1 2 ) 83-84
1
R
I
R +
NO,
bCOOEt
CHzCCOOEt COOEt I SaBH, pd-C *
~
NO2
COOEt
m \
I
OH
i
O
O
-
H
N
I
OH
I
0H water arid acidified with acetic. acid. T h e prodi1c.t wac extracted into chlorofoim, and the extract wa5 dried and distilled.
IG---
----Calcd,
c
mp. ' C
13
N
6 3 . 8 8 6 . 4 6 5x2 64.99 6.86 5 . 0 5 64.99 6 . 8 6 3 . 0 5 65.98 7 . 2 2 4 . 8 1 65.98 7 . 2 2 4 . 8 1 65.98 7 . 2 2 4 . 8 1 61.27 5 . 5 3 j Y 6 62.65 6 . W 6.62 58.43 6.3T , 5 2 4 60.47 6 . 2 0 5 . 4 3 68.88 6 . 4 6 5 . 3 2 59.78 6.76 4.98 .59.78 6 . 7 6 4 . 9 8 69.12 6 . 8 1 7 . 3 3 7 0 . 2 . 5 7 . 3 2 6.8.3 70.25 7 . 3 2 6.83 71.24 7 . 7 6 6 . 3 9 71.24 7 . 7 6 6 . 3 9 Uried at room temperature under va(:uiiin.
7--
FUlIlld,
C
63.93 64.77 64.67 66 41 66.16 65.80 60.09 62.61 58.34 60. 19 64.12 60.70 59 . 90 60.23 70.29 7 0 . 00 71.51 70.06 Ilried
'.b&
n
6.56 6.81 6.60 7.37 7.40 6.95 5.73 6.16 6.02 6.06 6.59 6.88 6 . 5,5 6.68 7.32 7 .33 7.72 7.8.5 a t YOo
--
N
4.115 4.8:: 5.22 5.05 4.71 4.64 5.60 5 71 4.02 5.49 5.51
-5.27 5 , :35 7.96 6.83 6 , 92 6.29 6.71 under
Method B.-A mixture of the appropriale a-alkylnialoiiate (0.05 mole) i n dry benzene (40 ml) and sodium ( 0 . 0 5 mole) was heated under reflux until solution was complete. o-Xtrobenzyl bromide (0.0525 mole) was added over 10 min and the mixture was heated under reflux o n the water bath for a further 10 min. T h e solvent was evaporated and the product was isolated a?; i n method A. Reductive Cyclization of a-Alkyl-m-o-nitrobenzylmalonates. Method C.'--.4 stream of nitrogen was bubbled through a vigorously stirred solution of yaR1-I~(0.05 mole) i n 0 . 5 -\- XaOH 16 ml/g of o-nitro estei,). Palladirlm-charcoal (lor;) was shaken with a little water to form a sliirry aiid t,his wab carefully added t o the borohydride solution. A solution of the o-nitm ester (0.025 mole) in dioxane (3 ml/g of o-nitro ester) was added over 5 min and the mixture was stirred for a further 1 hr and filtered through Celite. T h e filtrate was acidified with concentrated HCl to yield the cyclic hydroxamic acid either as a n oil or as a solid. Oily products were ext,racted into chloroform and di.3tilled, and solids were filtered, dried, and recrystallized. (4) h similar method has been previuurlj describedZdb u t molar proport i m e x e r e incorrectly stated, and t h e present m e t h o d a\.oids a possible fire
hazard.
