Some Derivatives of 3-Bromobenzaldehyde FRANK D. POPP Clarkson College of Technology, Potsdarn, N. Y.
I N CONNECTION with the work of this laboratory it was necessary to prepare a large series of derivatives of 3-bromobenzaldehyde. T h e new compounds which were prepared are reported here. They are included in Table I. EXPERIMENTAL Condensation with Ethyl Cyanoacetate. Equimolar amounts of the 3-bromobenzaldehyde and ethyl cyanoacetate in
and the mixture was heated for 15 minutes. Cooling, filtration, and recrystallization from ethanol gave the thiosemicarbazone (Table I ) . Other Derivatives. Mixtures of 0.01 mole of 3 - b m o benzaldehyde and 0.01 mole of the appropriate reagent were heated in ethanol for 20 min., cooled, filtered, and recrystallized from ethanol to give the materials listed in Table I.
Table I. Derivatives of 3-Bromobenzaldehyde Analysis Yield RH, Cyclopropanecarboxyhydrazide
p-Bromophenylhydrazine 1-Amine-3-nitroguanidine
Thiosemicarbazide p-Fluoroaniline Ethyl cyanoacetate
N
49.46 44.10 33.58 37.22 56.14 51.43
4.15 2.85 2.82 3.12 3.26 3.60
10.49 7.91 24.48 16.28 5.04 5.00
M.P.,
70
"C.
73 86 56 92 93 64
144-146 133-134 211-212 207-208 41-42 98-99
Formula CIIHIIN2BrO C 13HlaN2Br2 CFHsNiBrOz CaHsN3BrS CISHgNBrF C12HloNBr02
dioxane were teated with piperidine as previously described (1) to give the product listed in Table I. Reaction with Thiosemicarbazide. A hot solution of 0.91 gram (0.01 mole) of thiosemicarbazide in 30 ml. of water and 2 ml. of glacial acetic acid was added to 1.85 grams (0.01 mole) of 3-bromobenzaldehyde in 25 ml. of ethanol
VOL. 9 , No. 3,JULY 1964
C
Calcd. H
c
Found H
N
49.79 44.17 33.88 36.80 56.17 51.81
4.03 2.72 2.93 3.65 3.10 3.67
10.59 8.17 24.72 16.05 5.11 4.76
LITERATURE CITED F'D', ' Org.
25, 646 (1960).
RECEIVED for review December 26, 1963. Accepted January 29, 1964.
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