desiccator over sulfuric acid. The material was triturated with acetone, filtered, and placed in a vacuum desiccator over potassium hydroxide pellets. There was obtained 1.O g. of a colorless solid, m.p. 105" dec.
[ C O X T R I B U r I O K FROM THE
Anal Calcd. for C ~ € € I ~ N O ~ . H C, C I :39.72, 11, 0 6 7 , S,6.62. Found: C, 39.81; H , 6.96; N,6.82. K.4LAXALOU, 5TICiIILAN
RESEARCH LABORArORIES O F THEU P J O H N
CO.]
Some Reactions of Glycidaldehyde Diethylacetal BY JOHN B. ITRIGHT RECEIVED JUNE 12, 1956 Glyciddldehyde diethylacetal ( I ) was found to react readily with lithium alurnirium hydride, alcohols atid mercaptaiis (ethyl mercaptaii) with opening of the oxirane ring. Treatment with potassium thiocyanate gave thioglycidaldehyde diethyl acetal (111). The latter substance with diethylamine gave p-diethylamino-or-mercaptopropionaldehydediethylacetal. The acetals obtained in this reaction were cleaved with acid to the corresponding aldehydes.
Glycidaldehyde diethylacetal (I) is a highly versatile intermediate that may be prepared readily in good yield from acrolein diethylacetal.1 I n the previous paper2are reported the reactions of various amines with this compound. In this paper we wish to report some additional studies on the chemistry of this substance. Reduction of glycidaldehyde diethylacetal with lithium aluminum hydride gave lactaldehyde diethylacetal (11) in excellent yield.
potassium thiocyanate3 gave thioglycidaldehyde diethyl acetal (111) in good yield. Reaction with alcohols and with mercaptans (ethyl mercaptan) gave the corresponding P-alkoxylactaldehyde diethylacetals (IV) and P-ethylmercaptolactaldehyde diethylacetal (V),respectively. The latter reactions were carried out using methods identical to those that have beeii used with propylene oxide and in which the oxirane ring is known to open in such a manner as to give a secondary hydroxyl group. The structure of these comOH OCzHj ,0CzH5 pounds is assigned on the basis LiAlHl LiAlH4 I / of this analogy with propylene t-CHs-C--CH r-------+ CHs-CH-CH \ \ oxide. The acetals I V and V were I1 OCaHs OCzHj cleaved with acid to give the corSEI O C ~ H ~ responding /?-alkoxylacetaldehydes OCIHj CaHs VI and @-ethylmercaptolactalde/ (C&)2S€I \ CII~---cH--c'H S-CH~--LII-CH hyde (VII), respectively. \ \s/' \ Thioglycidaldehyde diethyl acctal VI11 OCPH~ 111 OCzHn (111) reacted with diethylamine to I €I+ give a compound thought to be the KSCK (IIC1) aminomercaptan VTII. However, i I when this compound mas subjected SH OCaHj CZH5 to distillation under reduced pres/ \ CHZ-CH--CH HCI. S-CHn-CH-CHO sure only thioglycidaldehyde di'\ / ethyl acetal was isolated, indicating I OC2II; C2HS IS that diethylamine is probably split l KOII out readily from this compound. + R = CiII;, ~ z - C I I ~ , ~ Treatment of crude undistilled VI1 I with dilute hydrochloric acid gave OH OCzl-I; OH i /3-diethylamino-amercaptopropionI1 + / ROCHz-CH---CHO aldehyde hydrochloride (IX). ROCH-~H-CH '~ ( HISOi j Infrared spectra of the aldehydes IY 0C.I-I. VI VI, VI1 and IX indicated that these i 011 OC?llj 0 11 compounds contain no carbonyl i i CmI-IsSll I / 11 ' I group and hence probably exist in --f C2H,SCII.: --Cl1-- C H O L-C~lliSCII~--CI-I-CLI + a dimeric (or polymeric) form. '\ Lactaldehyde is reported4 to exist v OCPHj VI1 in a similar dimeric form. The infrared spectrum of this substance was The aldehydes VI. T'II and IX were tested for identical with that of the product from the reduc- their antiviral activity. The results5 of these tests tion of pyruvaldehyde diethylacetal, indicating that are indicated in Table I. the opening of the oxirane ring with lithium aluAcknowledgments.-We wish to thank Dr. minum hydride proceeded in a manner to give a sec- James L. Johnson and his associates for the infra(3) (a) J . 31. Stewart and H. P. Cordts, i b i d . , 74, 5880 (1052); ondary hydroxyl group. Treatment of glycidaldehyde diethylacetal with ( h ) H. R. Snyder, 5. If. Stewart and J B. Ziegler, i b i d , 69, 21'172
t
-L;.
4
'I
~
~
-
~
( I ) D I. Weisblat. r f al , TIIXS J O U K K A L , 7 5 , 5895 (1953). f 2 ) J B . Wright, E . H . Lincoln and R . V. Heinzelman, ibid., 79, 1(is10 (1'367).
(1947). . . (4) A. Wohl, B e y . , 41, 3599 (1908). ( 5 ) For these results we are indebted t u the St.it1 or of Infectious Diseases.
uiir Ilejidrtiiil-111
April 5, 1957
REACTIONS O F GLYCIDALDEHYDE DIETHYLACETAL TABLE I ANTIVIRAL ACTIVITY Virus Newcastle Influenza (N.J.K.D .) (PR-8)
Compound
1 2 3 4
CzH~OCHzCHOHCHO( V I ) C4HgOCHzCHOHCHO (VI) CzHsSCHzCHOHCHO (VII) HCl.(CzH5)2NCHzCHCHO (IX)
I
+" -b
++
+" E
+
SH a -I-+ = >5Oy0 survivors, = 10-50% survivors, - =
