C O N C L U S I O N S

1. The cyanoamine complexes of cobalt catalyze under mild conditions the selective hydrogenation of dienones to unsaturated ketones.

2. Hydrogen adds to crotonolideneacetone predominantly at the C =C bond adjacent to the carbonyl group. The amount of formed 5-hepten-2-one in the catalyzate reaches 85%.

3. In contrast to pentacyanocobaltate, the cyanoamine complexes of cobalt catalyze the isomerization of 5-hepten-2-one to 4-hepten-2-one and 3-hepten-2-one.

L I T E R A T U R E C I T E D

1. 2. 3. 4.

5. 6.

G. M. Schwab and J. Mandre, J. Cats/., 12,103 (1968). L. Kh. Freidlin, L. L Gvinter, and L. N. Suvorova, Izv. Akad. Nauk SSSR, Ser. Khim., 1_.97--7, 838. O. Pir inger and A. Farcas , Phys. Chem., 49,321 (1966). L. L Gvinter, L. Kh. Freidlin, S. N. Suvorova, and S. L Shcherbakova, Izv. Akad. Nauk SSSR, Ser. Khim., 1974, 2619. L. Kh. Freidlin, N. V. Borunova, and L. L Gvinter, Dokt. Akad. Nauk SSSR, 20__~7, 1141 (1972). L. L Gvinter, L. Kh. Freidlin, N. V. Borunova, and G. Ya. Starodubskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 1972, 2318.

R E G I O S E L E C T I V I T Y OF R E A C T I O N OF N - A C E T Y L - q - A M I N O K E T O N E S

W I T H 2 , 5 , 6 - T R I A M I N O - 4 - H Y D R O X Y P Y R I M I D I N E

S. I. Z a v ' y a l o v , T . K. B u d k o v a , and G. I. E z h o v a

UDC 542.91:547,447.5:547.85

Previously [1 ] it was shown that the bromo derivatives of N-acetyl-~ -aminoketones react with 2,5,6- t r iaminc-4-hydroxypyrimidine (I) to give substituted pterins. As a continuation of this study, in the present paper the NMR method ~ was used to study the regioselectivity of the reaction of (I) with acetamidoacetone (II), N,N-diacetylaminoacetone (III), and 1-acetamido-l-bromoacetone (IV) in aqueous medium in the presence of various additives.

When 2,5,6-tr iamino-4-hydroxypyrimidine (I) is heated with (ID or (HI) and N2H 4 in aqueous solution (12 h, 100~ a mixture of the 6- and 7-methylpterins (V) and (VI), in an 8:2 ration is obtained in 50% yield:

o 0

H ~ -NH~ (ii) or (m) H

H~N N H_,N N N (i) (v) (vI)

B=CH3, RI=H(V); R=H, RI=CH3(VI)

The regioselectivity of this reaction can be attributed to the grea ter nucleophilicity of the amino group at C 5 of (I) [3], which forms the corresponding imino derivative (VII) with (II) (or {HI)). The conversion of (VID to (V) probably includes the successive steps of replacing the acetamido group by the hydrazino group, c~ida- tion of hydrazinoimine (VIII), and intramolecular cyclization of the intermediate iminohydrazone (IX):

* The difference in the chemical shifts of the protons at C 6 and C~ of the pterin molecule makes it possible to determine the ratio of the isomeric 6- and 7-substituted pterins in mixtures [2 ].

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2811-2813, December, 1977. Original ar t icle submitted April 19, 1977.

0568-5230/77/2612-2601507.50 �9 1978 Plenum Publishing Corporation 2601

N.I:I4 (I) (II) RN=C(CH.)CH~NHAo---* BN=C(CH.)CHzNHNHz (VII) ] N,H, (VIII.)

(ix) o

R = H 6 /

H2N N NH.,

The rep lacement of N2H 4 by Et2NH in the reac t ion of (I) with (II) o r (III) causes a complete shift of the s t r u c - tu ra l d i rec t iv i ty toward 7-methy lp te r in (VI).

ThiS in teres t ing case of reg iose lec t iv i ty can be explained if we s t a r t with the different ability of the i n t e r - media te imino der iva t ives {VII) and {X), which are found in a s ta te of equi l ibr ium with each o ther , to undergo in t r amolecu la r cyel izat ion. The (X) molecule has a d i r ec t conjugation chain of three multiple bonds, which faci l i ta tes the cleavage of a proton f rom the CH 2 group. The subsequent hydrolys is of acetyleneamine (XI) and in t ramolecu la r eycl iza t ion of a aldehyde (XII) should give 7 -methy l -7 ,8 -d ihydrop te r in (XIII), the dehydrogena- t ion of which with a tmospher ic oxygen leads to WI).

~-~ .NH 2 NHAc ~H NI-I~ NHAc HN/~W/ C ~ H HN'/~--'/ [CH

(X) \CH~ (XI)

0 0 A / NH2 _H20 ~ HN j~IN~"~

. ,% .N," ~ c.o

H (XlI) (X!~D

O2 ~* (VI)

The brominat ion product of compound (II), namely bromide (IV), reac ts with (I) in the p resence of e i ther N2H 4 o r Na2SO 3 to give a mix ture of (V) and (VI) in a r espec t ive ra t io of 8 :2 and 7 : 3 . In these react ions bromide (IV) evidently se rves as the source of pyrnvaldehyde, which under the influence of the above indicated additives also gives p re fe ren t i a l ly the 6-methyl i so m er (V) [3, 4].

(I1) B ~ AcNHCHBrCOCH3 H:O CHOCOCH3 (iv)

E X P E R I M E N T A L

The IR s p e c t r a were taken as KBr pel le ts on a UR-10 ins t rument , while the NMR spec t ra were taken in 1 N KOH solution on a DA-60-IL ins t rument , using TMS as the external s tandard. The TLC was run on Silufol UV-254 in the sys t em: i - P r O H - H 2 0 - N H 4 O H , 7 : 2 : 1 (detection of the f luorescen t spots in UV light).

React ion of 2 ,5 ,6 -Tr i amino-4 -hydroxypyr imid ine (I)with Acetamidoacetene (II) and N,N-Diacetylamino- acetone (HI). To a s t i r r e d suspension of 3 g (0.013 mole) of the (I) sulfate in 30 ml of wate r were success ive ly added 4.3 g (0.027 mole) of (III) [5] and 6 ml (0.106 mole) of 88% N2H 4 -H20, a f te r which the mix ture was r e - fluxed for 12 h, acidified with AcOH to pH 5-6, and the prec ip i ta te was f i l te red , washed in success ion with wa te r , acetone, and e ther , and then dr ied in vacuo at ~ 100~ We obtained 1.1 g (50%) of a mixture of (V) and (VI) in an 8 :2 ra t io (NMR spec t ra l data), Rf 0.48. The IR spec t rum of the obtained mixture coincided with the

s p e c t r u m of authentic (V) [1 ].

The reac t ion of (I) with (II) gave analogous resul ts [6 ].

A mixture of 0.5 g (0.0021 mole) of the (I) sulfate, 0.6 g (0.0052 mole) of (II), and 1.2 ml of Et2NH in 7 ml of wa te r was refluxed for 10 h, af ter which it was acidified with AcOH to pH 5-6, and the precipi ta te was f i l t e red and washed as desc r ibed above. We obtained 0.17 g (46%) of (VI) (]lt and NMR spec t ra l data) [1, 2],

Rf 0.48.

2602

React ion of 2 ,5 ,6-T r i amino-4-Hydroxypyr imid ine (I) with 1 -Ace tamido- l -b romoace tone (IV). To a s t i r r e d solution of 2 g (0.018 mole) of (II) and 0.03 g of LiC1 in 16 ml of conc. HC1 was gradual ly added 0.74 ml (0.014 mole) of Br2, a f te r which the mix tu re was s t i r r e d fo r another 3 h a t 2 0 ~ diluted with 15 ml of wa te r , t r ea t ed f i r s t with Ne~CO 3 to pH 7, and then with N~SO 3 to pH 8. To the reac t ion mix ture were added 2.08 g (0.009 mole) of the (I) sulfate and 2.2 g of Na2SO 3, the mix ture was s t i r r e d for 30 rain at ~ 20~ ref luxed for 6 h, acidified with AcOH to pH 5, and the reac t ion products were isolated as desc r ibed above. We obtained 1.15 g (78%) of a mix tu re of (V) and (VI) in a 7 : 3 ra t io (IR and NMR spec t ra l data), Rf 0.48.

The brominat ion of 2 g (0.018 mole) of (II) was run as indicated above. The reac t ion mix tu re was t r ea ted with Na2CO 3 to pH 7, and then in success ion were added 2.5 ml (0.044 mole) of 88% N2H 4 "H20 and 2.08 g (0.009 mole) of the (I) sulfate, a f te r which the mix tu re was ref luxed for 5 h and then acidified with AcOH. We i so - lated 0.66 g (44%) of a mix tu re of (V) and (VI) in an 8 :2 ratio.

C O N C L U S I O N S

1. The reac t ion of 2 ,5 ,6 - t r i amino-4-hydroxypyr imid ine with acetamidoacetone, its brominat ion product , o r N,N-diacetylaminoacetone in aqueous solution in the p re sence of hydraz ine gives mix tures of the 6- and 7 -methy lp te r ins in an 8 : 2 ratio.

2. The reac t ion of 2 ,5 ,6 - t r i amino-4-hydroxypyr imid ine with acetamidoacetone in aqueous diethylamine solution leads to 7-methylp ter in .

LITERATURE cITED

1. 2. 3. 4. 5. 6.

S. L Zav 'yalov, T. K. Budkova, and N. L Aronova, Izv. Akad. Nauk SSSR, Ser. Khim., 19__73_., 2136. C. B. S torm, R. Shiman, and S~ Kaufman, J. Org. Chem., 36, 3925 (1971). W. P f l e ide r e r , H. Zondler , and R~ Mengel, Ann. Chem~ 741, 64 (1970)o J. Semb, U. S. Pa tent 2477426 (1949); C. A., 44, 1146 {1950). S. L Zav 'yalov, I. F. Mustafaeva, and N. L Aronova, Izv. Akad. Nauk SSSR, Ser. Khim., 197____33, 2091. R. H. Wiley and O. H. Borum, J. Am. Chem. Soc~ 70, 2005 (1948).

P H O T O C H E M I C A L R E A C T I O N S O F ( C O ) 2 ( P P h 3 ) M n C s H 4 F e ( C O ) 2 C s H 5

a n d ( C O ) 2 ( P P h 3 ) M n C s H 4 C O F e ( C O ) 2 C s H 5 W I T H P P h 3

A. No N e s m e y a n o v , E . G. P e r e v a l o v a , L . I. L e o n t ' e v a , a n d E . V. S h u m i l i n a

UDC 541.14:547.1 '13:547.558.1

The synthesis of the o- (~-cyclopentadienyl)manganese(dicarbonyl) t r iphenylphosphine der iva t ives of v-cyclopentadienyldicarbonyl i ron (CO)2(PPh3)MnCsH4Fe(CO)2CsH5 (I) and (CO)2(PPh3)MnC5H4COFe(CO)2CsH 5 (II) was repor ted recent ly [1 ]. The photochemical react ions of (I) and (II) with PPh 3 were studied in the p r e s - ent paper .

Compound (D reac t s with PPh 3 when i r rad ia ted for a shor t t ime with UV light, and h e r e the CO group on the i ron atom is replaced by PPh 3 to give the diphosphine complex (III), which contains t r iphenylphosphine ligands on both the manganese and iron. The s t ruc tu re of (III) was conf i rmed by the NMR (Table 1) and IR (VCO 1938, 1915, and 1851 era- ' ) spec t ra .*

*We were unable to obtain (III) by the photochemical react ion of (IV) with PPh 3 under the same conditions.

M. V. Lomonosov Moscow State Universi ty. Trans la ted f ro m Izvest iya Akademii Nauk SSSR, Ser iya Khimicheskaya, No. 12, pp. 2813-2815, December , 1977o Original ar t ic le submitted Apri l 22, 1977o

0568-5230/77/2612-2603507.50 �9 1978 Plenum Publishing Corporation 2603