eee ti 
vaieeene : 
cs deta ht na Sao oy Bt ae ae Fy es Siero % 
+ ak ey jaa ‘ 
“Notes « ON SCIENTIFIC RESEARCH, Mery 145 
 Adilition products e Shae aegis: a, We Eton below, without entering into 
2x cert details or theoretical discussions, on a spacious paper by H. Meerwein') 
in which some interesting reactions are dealt with of bodies being of special interest for us. 
_ Addition of desoxybenzoin (benzylphenylketone) to cinnamic aldehyde takes place 
when the solution of these bodies in methyl alcohol is treated, at reduced temperature, 
with ‘sodium methoxide. The aldehydes resulting, $-phenyl 6-desyl propionic aldehyde, 
CsHs- “CH: CO. ia H; melts at 176.5 to 177°. Its constitution was proved by its oxid-— 
ation to the. corresponding acid (dehydroamaric acid) which 
CoHs- CH: CHz-CHO could be prepared by synthesising desoxybenzoin with benzal- 
n nalonic ester and subsequent saponification and splitting-off of CO,. On adding 
a solution of sodium in methyl! alcohol to a cold solution of connamic and phenylacetic 
a aldehydes, ‘the latter turns yellow. 
When sodium methoxide is added again after the Entel of phenylacetic alde- 
‘hyde has disappeared, and the solution, after some standing, is heated gently oe a 
reflux condenser, the primary addition-product, «, 8-diphenylglutaric aldehyde, 
transformed into 8, y-diphenyl valerolactone; m. p. 123 to 123.5°, which CoH. cr: CH,- ay 
on treatment with KMnO, is oxidised to «, @-diphenylglutaric acid; ones 
methyl ester, m.p. 84 to 85°. This acid occurs-also in a stereo- CoHs- cH. CHs: CO: 
isomeric modification of indistinct melting point.. 
On addition of phenylacetic aldehyde to benzylidene gectophedode primarily 
«, 8, d-triphenyl-0-keto-n-valeric aldehyde is formed which on heating is rearranged into 
8, é-triphenyl valerolactone. The corresponding acid, «, @, 0-triphenyl-d-hydroxy-n-valeric 
acid, m. p. 143 to 143.59, is stable; on heating up to 150° m vacuo i. is reconverted 
; into the lactone, m: p. 138 to 139°,- : 
C;H;-CH-CO | C,Hy-CH-CO.H 
pe a O Pieiialece | . 
Cs;Hs-CH-CH.-CH:C,H; -CoHs- CH: CH,-CH (OH) CoH, 
_ On adding phenylacetic aldehyde to ethyl benzylidene acetoacetate, in ethylalcoholic 
“solution, by means of sodium ethoxide a mixture of a difficultly and a readily soluble. 
p product is formed. The former is @,{- diphenyl-y-carbethoxy-0- -keto-n- -capronic aldehyde; 
oe: 149°, 
CsHs: CH CH: Cs Hs 
C,H;0CO-CH CHO 
| 
CO-CHs 
es a, 3-Diphenyl-/-carbethoxy-0-keto-n-capronic aldehyde. 
s The readily soluble body is a product of a rearrangement of the former one. 
_ The addition-product of phenylacetic aldehyde and ethyl benzylidene acetoacetate 
‘is split up on distillation in vacuo, but, strange to Say, not again into’ its original 
“components, but to «phenylcinnamic aldehyde and ethyl acetoacetate. 
e-Phenylcinnamic aldehyde was prepared synthetically by Meerwein pee riding to 
Claisen’s direction’s given for such condensations: — shaking of a mixture of phenyl- 
acetic aldehyde, benzaldehyde, water, and potash solution —; m. p. 949; oxime, m. p. 
165 to 166°; phenylhydrazone, m. p. 125 to 126°. 
The addition-product from phenylacetic acid and ethyl benzylidene acetoacetate 
adds, on treatment with alcoholic hydrogen chloride, the elements of alcohol forming 
*) Journ. f. prakt. Chem. ll, 97 (1918), 225. 
/ 
