formaldehyde - Sciencemadness Dot Org

REACTIONS WITH INORGANIC AGENTS 129
peroxide, formaldehyde, and nitrogen compounds. Formaldehyde, amionium
sulfate, and 3 per cent hydrogen peroxide give hexamethylene
triperoxide diamine, ]\ T (CH202CH2)3N 5 . This product may also be obtained
from hexamethylenetetramine and hydrogen peroxide 40,83 . Von
Gireewald** 1 obtained an explosive peroxygen derivative by the reaction of
formaldehyde, hydrazine sulfate, and peroxide at 4(K50°C.
SCB>0(aq) H- Ha02 + N2H4-H2S04
/
^ CH^rN-N
\
CH2—0
+ H2SCU -f 3H2C
CH2—O
Hydrogen Sulfide and Sulfides. Hydrogen sulfide dissolves readily in
iqueous formaldehyde forming partially snlfuretted analogs of methylene
tnd polyox'ymethylene glycols as indicated in the following equations:
HSH + HOCHaOH -> HOCHsSH + H20
2HOCHaSH -> HSCHaOCH*SH
HOCHsSH + HSCHflOCH.SH -+ HSCH2SCH2OCH2SH -f H20
Baumann 10 isolated mixed products of the above type by ether-extraction
of commercial formaldehyde which had been saturated with hydrogen
sulfide and maintained at a temperature of 10-12°C for 14 days. The
products were viscous oils which gradually hardened and possessed a garlic.
odor. In the presence of dilute hydrochloric acid, Baumann obtained a
solid, crystalline product which melted at 97-103°C after crystallization
from ether. Analysis of this product indicated the empirical formula^
CJETgOSs, All these products are soluble in alcohol, ether, and benzene.
They exhibit the chemical characteristics of mercaptans, producing disulfides
on reaction with iodine. Water solutions give yellow precipitates
with lead acetate which decompose on warming with formation of lead
sulfide. They dissolve readily in dilute alkali, from which they are precipitated
on acidification.
Crystalline hydrogen sulnde-formaldehyde reaction products known as
formthionals are also obtained by saturating 37 per cent formaldehyde with
hydrogen sulfide at temperatures in the neighborhood of 40 to 50°C S2 -
Heat is evolved by the reaction and product is precipitated, almost completely
solidifying the reaction mixture. A product of this type obtained
from neutral formaldehyde melted at S0°C after crystallization from chloroform
and contained 51.5 per cent sulfur. When pure, these compounds
are colorless and have little odor.
Under strongly acidic conditions, trithiane or trithioformaldehyde,
(CH2S)3, is the principal reaction product of formaldehyde and hydrogen
sulfide and is precipitated in practically quantitative yield 55 . Sulfuretted