Uroporphyrin 3¹

Abstract

UROPORPHYRIN 4389min., 0.5 g. of sodium acetate in 10 ml. of acetic acid was added and air passed in for 24 hr. to precipitate the crystalline product (29 mg., 667,). Its solution in 250 ml. of chloroform was filtered through alumina (Grade V) and the filtrate concentrated to 30 ml. The crystals which separated were dissolved in 60 ml. of hot chloroform. After concentrating to 30 ml. and cooling, flat needles (23 mg.), m.p. >350", separated from the solution. The visible spectrum of a chloroform solution recorded spectrophotometrically was of the "etio" type in contrast to that noted visually": maxima (and e) a t 521 mp (13 X lo3), 558 mp (7.1 X lo3), 598 mp(5.1 X lo3) and 655 mp (4.5 X lo3).Anal. Calcd. for C36H38N400: C , 66.04; H, 5.85; I T , 8.56; OEt, 27.53. Found: C, 66.24; H , 5.90; N, 8.63; OEt, 27.23. (b).-When this synthesis was carried out in the same way except that an equivalent amount of 707, perchloric acid was used instead of the hydriodic acid, aeration precipitated about 1 mg. (27,) of a product shown spectroscopically to contain 0.27 mg. of porphyrin.(c).-The aldehyde \'Ib (102 mg.) was heated with concentrated hydrochloric acid on the steam-bath. The precipitate was dissolved in chloroform, the solution filtered through a column of deactivated alumina and concentrated. The product which crystallized (7 mg.) had the same visible spectrum in chloroform as did that of method ( a ) above. In acetic acid-hydrochloric acid both had strong bands a t 626 and 575 mp, a very weak one a t 530 mp. Evidently Fischer observed the first two bands and a third band due to an impurity.12 1,4-Dimethyl-2 ,J-dicarbethoxyporphin-5,8-dipropionicAcid-6,7-diacetic Acid Tetramethyl Ester.-The pyrromethanes VIa (16 mg.) and Ie (26 mg.) were dissolved in 25 ml. of acetic acid, and acetic acid containing 0.16 ml. of 56% hydriodic acid was added. After 20 min., 0.5 g. of anhydrous sodium acetate was added. Aeration precipitated 16 mg. (407,) of the crystalline product, m.p. 250.5-251.5'.Anal. Calcd. for C42H48N4o12: C, 63.15; H , 5.80; S , 7.01; alkoxy (as OMe), 23.31. Found: C, 62.90; H, 5.7i; K, 6.89; alkoxy (as OMe), 22.38.2,3-Dimethylporphin-6,7-diacetic 4,5,pionic Acid Hexamethyl Ester.--ii solution of 175 mg. of the pyrromethene hydrobromide \;,a1 122 mg. of the pyrromethane IC and 300 mg. of anhydrous sodium acetate in 200 ml. of acetic acid was heated on the steam-bath for 1 hour. The cooled solution was then aerated for 1 hour. The crystalline but impure product (100 mg.) was separated and washed with acetic acid, then with ether. I t was esterified with methanolic hydrogen chloride, brought into chloroform, the solution filtered through deactivated alumina and the chloroform replaced by methanol. Crystallized again from chloroform-methanol it formed tiny bent hairs (82 mg., 3370), m.p. 233-238' after sintering and a solid phase change from 230". Paper c h r o m a t~g r a p h y~~ of the free acid showed only the hexacarboxylic acid spot. I t was degraded to coproporphyrin 2 methyl ester, m.p. 285-287" (uncor.).

Total Synthesis of [α,γ‐14C2]Uroporphyrin III

“…These batches were worked up separately. When freed quantitatively from porphyrins without metal atom and purified to constant radioactivity, the hemin (7) obtained had a mean radioactivity of 1.65 pCi/mmol, corresponding to 0.21 % specific incorpora-…”

“…A specific degradation was carried out to show that the 14C radioactivity of the isolated hemin (7) resided only in the a-and y-methine groups and that the biosynthesis of [ 7) from [~t,y-'~C,]uroporphyrinogen 111 was thus direct and unaccompanied by isomeri~ation'~]. Methylating fission of (7) by 67 % hydriodic acid and paraformaldehyde (10) (ll), C 0 2 C H 3 instead of COzH …”

“…Methylating fission of (7) by 67 % hydriodic acid and paraformaldehyde (10) (ll), C 0 2 C H 3 instead of COzH …”

Some 5,5′-Free Pyrroketones

“…to Vb, Vc and IVb, IVc respectively from 2,4-din1ethyl-3-ethylpyrrole or its 5-carbethoxy derivative. Altl~ougl~ our sequence gives symmetrical lietones more directly, ~~nsymmetrical ones are reached through pyrroillethane inter~nediatcs whose purity must be scrutinized (8).…”

Syntheses With 5-Dibromomethyl- And 5-Formyl-Pyrromethenes

“…T h e two previously known unsymmetrical 5,5'-dibromo-pyromethenes had been obtained from dipyrrylmethanes (8,9). Bromine also converted IVe into the symmetrical IVf.…”