4. 5. 6.

N. Kh. Petrov and E. L. Frankevich, Khim. Fiz., ~, 389 (1983). P . P . Levin and V. A. Kuz'min, Izv. Akad. Nauk SSSR, Ser. Khim., 1901 (1987). V . A . Kuz'min and P. P. Levin, Izv. Akad. Nauk SSSR, Ser. Khim., 1421 (1986).

SYNTHESIS OF CROSS-CONJUGATED POLYENIC DIALDEHYDES AND CARBOXYLIC ACID ESTERS G. V. Kryshtal', D. Dvorak, Z. Arnol'd, and L. A. Yanovskaya

UDC 542.91:547.441.8:547.421

In earlier work [i], we developed a convenient method for the acetylization of arylidenemalonic dialdehydes (I) using ethyl orthoformate and catalytic amounts of perchloric acid. This method permits the preparation of the corresponding bis-diethyl acetals (II) in about 90% yield. In the present work, products (II) were used for the synthesis of cross-coupled dialdehydes (IV) and esters (V). Bis-acetals (II) smoothly add to vinyl ethyl ether in the presence of BF3.Et20 with the formation of the corresponding hexaethoxy derivatives (III). Independently of the ratio of the starting reagents, the reaction proceeds at both acetal groups. The best yields of ethoxyacetals (III) (60-87%) occurred using two moles of vinyl ethyl ether per mole bis-diethylacetal (II). The hydrolysis of ethoxyacetals (IIi) using an equimolar amount of water in CH3CO2H-CH3CO2Na led to branched unsaturated dialdehydes (IV), which undergo the Wittig reaction with carbomethoxymethylenetriphenylphosphorane to give the corresponding methyl esters of branched conjugated dicarboxylic acids (V). We used this method to obtain esters of cross-conjugated carboxylic acids from dialdehydes (I) [2]. CHO

CH(OEt)~

RCH=C /

HC(OEt)~R C H = / HClO~ "~ CHO CH(OEt)~ (Ia- c) (Ha--c) CH(OEt)CH2CH(OEt)z / ~ / --, RCH=C ---+ RCH=C \ \ CH(0Et)CH~CH(0Et).~ (IIIa- c) 9

0va--c)

, Ph3P~CtICO2CH, ~ RCH=C

/

~\oEt Bfs.Et~O

CH=CHCHO

CH=CHCH0 (IVa--c)

(CH=CH)2CO~CHa

\ (CH=CH)~C02CHz (Va--c) R -- Ph(a), p-CH3OCoH~(b), ~ > (c). S

The properties and spectral indices of the compounds synthesized are given in Table i. EXPERIMENTAL The product purity and reaction courses were monitored by thin-layer chromatography on Silufol plates using 20% ethyl acetate in benzene as the eluent with 12 as the developer. The PMR spectra were taken on a Varian DA-60-11 spectrometer at 60 MHz and Tesla BS-497 spectrometer at i00 MHz in CCI 4 or CDCI 3 relative to TMS as the internal standard. The IR spectra were taken on a UR-20 spectrometer in CHCI 3. The UV spectra were taken on a Specord UV-VIS spectrometer in ethanol.

N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. ii, pp. 26142616, November, 1987. Original article submitted February 25, 1987.

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TABLE i. Com- Yield. pound %

Yields and Indices of the Products Obtained* Bp or rap, t (p, mm Hg)

IR spec- UV spectrum (Xmax '31, cm -1 trum nm (e))

PMR spectrum (6. ppm, j, Hz)

I

(llla) 67

t40-t45 (O,2)

(IIIb)

87

t85-i90 (O,2)

(IIIc)

60

155-t60 (0,35)

OVa)

7t

(IVb~

75

t05-t07 (hexane-ether)

t688 t627 t6t0

116-117

t680 t600

(hexane-benzene 0re)

98

t43-144 (CCla-C6H6)

(Va)

62

93-95 (hexane)

1688 t621 1605 t568 t708 t622

(re)

69

1t5-117 (hexane)

17t0 t622

209 (19200) 247 (9700) 270 (14150) 340 (27700) 279 (72000) 364 (31OOO)

1,00-t,42 m (6CH~), 1,60-2,i0 m (2CH2), 3,2-3,8 m (6CH20:), 4,35-5,00 m (4Ctt).,: 6,83d (CH=, ]=8), 7,i-/,4 m (Ph) 0,9-0,3 m (6CH3), t,6-t,9 m (2CH~),3,2-3,6 m (6GH20) 3,7 s (CH30), 4,35-4,7 m (4CH), 6,7-7,t5 m (CH=, Ph) 0,9-0,3 m (6CH8), ' t,5:2,0 m (2CH2), 3,2:3,7 m (6CH20), 4,45-43 m (4CH)~ 6,67-7,2 rn .(CH=, 3CHarom) 6,45 d: d (2CH=, ]=i6,

]=7,5),

7,15-7,7 m (3CH=. Ph), 9,65 .d (2CHO, I=7,5) 3,86 s (CH~O), 6,4. d: ,d (2CH=,

]=t6, ]=7,5),

7,0-7,7 m (3CH=, Ph), 9,6 d, 9,7d (2CHO, ]=7,5) 207 (22287) 6,45 d: (2CH=, ]=i6, ]=7.5), 7J-8.0 m(3CH=, 240(11144) 3CH~om)0 9,7 d, 9;8 d (2CHO, 274 (12597) ]=7,5) 370 (31977) 2O4(15OOO) 3,72 s (2CH30), 5,9 d (2CH=, ]=16), 6,7-7,4m (TCH=, Ph) 245 (19500) 312(34900) 345 (33400) 2t0 (19000) 3,72 s, 3,74 s (2CH30). 5,9d (2CH=, 1=16), 248 (28000) 3t5 (33800) 6,7-7,4 m (7CH=, 3CHarom) 370 (45700)

*All the compounds have satisfactory elemental analysis data: C • 0.15, H • 0.12, S i 0.24; nD2~ 1.4865 (Ilia), 1.4960 (lllb), 1.4920 (IIlc). Preparation of Ethoxyacetals (III). A sample of 0.06 mole vinyl ethyl ether was added dropwise with stirring to a mixture of 0.03 mole (II) and several drops of BF3.Et20 not exceeding 35~ The mixture was stirred at about 20~ for 24 h. The mixture was then neutralized with ethanolic KOH and distilled. Preparation of Dialdehydes ($V). A sample of 0.01 mole ethoxyacetal (III) and 6 ml of a mixture obtained from i00 ml acetic acid and 17.0 g CH3CO2Na.3H20 was heated at reflux with stirring for 2-4 h and monitored by thin-layer chromatography. The mixture was cooled and poured onto ice. The precipitate formed was extracted with CH2CI 2. The organic layer was washed with water, aqueous NaHC03, and water and dried over MgSO~. The residue obtained after evaporation of the solvent was crystallized from a suitable solvent. Preparation of Methyl Esters of Dicarboxylic Acids (u A mixture of 0.001 mole dialdehyde (IVa or c) and 0.002 mole carbomethoxymethylenetriphenylphosphorane in 5 ml benzene was heated at reflux for 2-4 h with monitoring by thin-layer chromatography. After completion of the reaction, benzene was evaporated and the dry residue was extracted with ether. The extract was passed through AI203. Ether was evaporated and the residue was crystallized from hexane. The yields and indices of the esters obtained are given in Table i. CONCLUSIONS Methylenemalonaldehyde was used in a convenient method for the synthesis of 4-aryland 4-heteroarylmethylenehepta-2,5-diene-l,7-dials and dimethyl esters of 6-aryl- and 6heteroarylmethyleneundeca-2,4,7,9-tetraene-l,ll-dioic acid.

2430

LITERATURE CITED i~

2.

G. V. Kryshtal', D. Dvorak, Z. Arnol'd, and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser~ Khim., 921 (1986). Z. Arnol'd, V. Kral, G. V. Kryshtal', and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 457 (1984).

MOSSBAUER SPECTRA OF IRON CARBONYL COMPLEXES WITH SULFUR LIGANDS UDC 543.42:541.49:546.725:547.279.3

V. V. Matveev, B. I. Kolobkov, and A. I. Nekhaev

The reaction of sulfur and sulfur compounds with iron carbonyls leads to the formation of complexes A, B [i], C [2], D [3-5], E [6], and F [3]. All these types of complexes originate with complex A. For example, the addition of the Fe(CO) 3 group at the Fe-Fe and S-S bonds in A gives complex B, while F is formed by the replacement of one of the sulfur atoms into the Fe(CO) 3 fragment and the addition of a CO group coordinated with three metal atoms.

(CO)3Fe--

" ~' 3

"QF/e/~ (co) 3 B

A

(c~

s

xi

(CO) 3 F e - - F e

C (co) 3

T

/ \/s /\ R--s\

( C O ) 3 F e - - " ~e(CO) ' 3

Fe

\s--~ / Fe

(co) 3

(co) 3 E

D

(C()tl

i

~

(c~co-

(co)~ (co)a F

The Mossbauer spectral parameters of (II)-(V) were given by Haines [7] and Crow [8], while the halogenated phosphine-substituted cationic derivatives C were given by Haines et

al. [9]. In the present work, the Mossbauer spectral indices were analyzed for a series of previously unreported sulfur-containing iron carbonyl complexes. EXPERIMENTAL The Mossbauer spectra were obtained on an electrodynamic instrument with a cobalt-57 source in a chromium matrix. The results were treated on a computer using a gradient matrix minimization program. The isomer shifts were calculated relative to the center of the sodium nitroprusside doublet. RESULTS AND DISCUSSION The Mossbauer spectral indices of all these types of compounds proved similar, which indicates a similar state of the iron atoms in these complexes. This is also indicated by the temperature independence of the quadrupole splitting (Table i). A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. Ii, pp. 2616-2619, November, 1987. Original article submitted February 27, 1987.

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