Reactions of Ethylenimines. IV. With Carbon Disulfide - Journal of the

Regioselective Ring Expansion of 3,3-Dimethylaziridin-2-carboxylate and a Photochemical Entry to the Penem Nucleus. James D. White , Takuya Furuta...
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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