N OT15S
1490
Vol. 75
TABLE I IfAMMICK l < E A C T I o X S 11 ITH PICOLINIC ACID" AND VARIOUS CARBONYL COMPOUNDS Product
1'hcnyIpyridyIcarbiiiol'"
P yr~dyldiphenylcarbinol~ Phenylpyrldylmethylcarbirlold P-hlethoxyphenylpyridylcarbirioi
wi-Sitrophenyl pyridyl ketone Iii-
Sitroplienylpyridyliiictliyl< ,irbiiioI
/ ~ - ~ h ~ ~ J r O ~ l ~ l ~ l l y ~ [ ~ y ~ i t ~ y ~ ~ ~ l ~ ~ J l l l ~ ~
rrl c ~ i i - l ~ c t irotiipouiiti. ~yl Krfcrs to I-cactioil without sulveiit. I aiitl 2. e 'l'his i\ tlic iioiliug point.
Refers to reactioii with solvent
'I
TABLrs Acid
I1 Aldehyde
Pyrimidine-l-carbosylic Thiazole-2-carboxylic
Anisaldehyde Anisaldehyde
Benzaldehyde Anisaldehyde Betlzaldehyde ~-?\.Iethylthiazole-5-carbox- Benzaldehyde ylic Anisaldehyde 2-l\.lethyltiliazole.~-e~r~(j~Benzaldehyde ylic -$nisaldehy(ic 0- Sitrobeiizoic Bcrizaldehytlc :\riisalclehy(le 2,4 - l ) i i i i t r ( ~ l ~ c i i ~ ~ i L I3enzaldehydc .inisaldehydr ~~,j-Diiiiethylthiazole-2carboxylic
T eoc. mp.,
245 90
90 $13 y;j
175
178 178 175 175 163 l(i3
(p-
The reactions were carried out in anisaldehvde and, where the decarboxylation temperature of t h e acid was low enough, in benzaldehyde. All of the acids Seg. Seg. gave negative results in that they did not yield the expected carbinol, a coupling product between the Seg. Seg. decarboxylated acid and the carbonyl compound. xeg, Hammickl has shown that 2,4,6-trinitrobenzoic Seg. acid gives a negative reaction. Seg, The reaction was also carried out on various seg,methyl substituted picolinic acids, utilizing anisalxeg. dehyde as the carbonyl reactant and P-cymene as Seg. the solvent. The results are reported in Table 111. Seg. a411 of the methyl substituted picolinic acids gavc Seg. a positive Hammick reaction and the expected Leg. coupling products. TABLE 111
( J S LLETHYI,
SUBSTITUTED ~ ' I C U L I S I C ACIDS IS
3u GRAMSO F
ASISALDEH1.DE
AKD
30 GRAMSOF
P-CYMESE Methyl suhstitutcii picolinic acid"
'l
;;-lIethyl 4-Methyl 3-Methyl A-Methyl 1,fi-1)imethyl S.5grains ill eacli case
Product, p m e t h o x y p h e n y l carbinol
;i-l\Iethylpyridyi-
Temp.,
Yield, Grams
O C .
2.8
1ti-j
4-Methylpyridyl173 5-Methylpyridyl17'7 (;-Methylpyrid yl170 ~I-,ii-Ditiiethylpyritiyl173 csccpt for 4,0-dinictliylpicoli1iic x i ( l
tained in p-cymene. These findings are in agreeinetit with those previously reported by Tilford,3 Shelton and lTan Campen on the effect of solvents on this reaction. The experimental procedure was the same as that employed by Hammick.' The yields utilizing @-cymeneas solvent for the reaction are reported under yield as (b) in Table I. p-Nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, cinnamaldehyde and p-dimethylaminobenzaldehyde gave negative results both with and without the addition of solvents. In an attempt to extend the reaction to acids other than those successfully employed by Hammick, the reaction was carried out on the thiazole, pyrimidine and nitrobenzoic acids listed in Table 11. ( 3 ) C. H. Tilfurd, K . S. Shelt
