unusual product of the reaction of keto-stabilized sulfur ylides with acrylonitrile

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  • UNUSUAL PRODUCT OF THE REACTION OF KETO-STABILIZED

    SULFUR YLIDES WITH ACRYLONITRILE

    G. A. Toistikov, F. Z. Galin, and S. N. Lakeev UDC 541.91:547.512

    Monostabilized sulfur ylides react with Michael acceptors to give 1,2-disubstituted cyclopropanes [1]. In a study of amido-substituted keto-stabilized sulfur ylides (I), (II) [2], we discovered that the reaction of (I) or (II) with an equimolar amount of acrylonitrile at 80"C over 90 rain in MeCN gives rearrangement to the 1,1-disubstituted cyclopropane derivatives (III) and (V), respectively. Under the same conditions, the reaction of ylide (I) with methyl acrylate leads to a 1:1 mixture of cis- and trans-1,2-disubstituted eyclopropanes (IVa) and (IVb) whereas for (II) only one isomer (VI) is formed.

    0 I1

    \A 0 I1 N 1~ +/ /V V \ - - s

    o (1)

    o I1

    I1 1 / \1 o CN

    ( I I I )

    0 tl

    , :hA= o ~/~/ \ /~

    h

    (Ira)

    0 II

    ~/ \ / - " , it II "- o o

    ( i i )

    CN

    /P\CO,I~Ie /t

    0 II

    COl/vie -I-- : '~AN 7

    li I o ~ \CO,Me

    (IV:b) 0

    II II o o

    (v)

    o 11

    /:\CO ,hie :~A. CO,Me ~7~/ N/N/N/

    II II o o

    (VI)

    1-Cyano-l-(2-phthalimido-l-propanone)cyclopropane (III) was obtained in 75% yield, mp 154-155"C. IR spectrum (v, cm'l): 1715, 1775, 2210. PMR spectrum in CDCI 3 (6, ppm, J, Hz): 1.75 d (CH s, J = 7), 1.95 m (CH2), 5.53 q (CH, J = 7), 7.95 s (C6H4). IzC NMR spectrum in CDCI 3 (6, ppm): 14.69 q (CH3), 18.28 s (CI), 21.74 t, 23.17 t (CH2), 53.72 d (CH), 120.24 s (CN), 197.59 s (CO), 124.16 d, 132.84 s, 135.29 d, 167.70 s (phthalyl).

    Institute of Chemistry, Bashkir Science Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimieheskaya, No. 5, pp. 1187-1188, May, 1990. Original article submitted October 24, 1989.

    i068 0568-5230/90/3905-I068512.50 01990 Plenum Publishing Corporation

  • Methyl ester of 2-(2-Phthalimido- l-propanone)-l-cyciopropanecarboxylic acid (IVa) and (IVb) was obtained in 82% yield as an oil. IR spectrum (v, cm-1): 1710, 1720, 1775. PMR spectrum in CDC13 (6, ppm): mixture 1.64 d, 1.72 d (CH s, J~ = 7 Hz), 2.15-2.58 m (CH, CH2), 3.57 s, 3.69 s, 4.95 q, 5.01 q (CH, J = 7 Hz), 7.70-7.94 m (C6H4). 13C NMR spectrum in CDCl s (5, ppm): mixture 14.10 q (CHs) , 17.17 t, 17.95 t (CH2), 24.29 d, 26.24 d (C1), 24.48 d, 26.27 d (C2), 52.22 q, 52.09 q (CO2C_Hs), 54.57 d, 54.76 d (CH), 172.20 s (CO2), 201.96 s (CO), 123.50 d, 123.64 d, 131.92 s, 134.34 d, 167.50 s (phthalyl).

    1-Cyano-l-(3-phthaiimido-l-propanone)cyclopropane (V) was obtained in 86% yield, mp 82-84~ IR spectrum (v, cm-1): 1620, 1720, 2260. PMR spectrum in CDC1 z (6, ppm): 1.65 nar. m (CH2), 3.31 t (CH 2, J = 7 Hz), 4.00 t (CH 2, J -- 7 Hz), 7.75 m (C6H4). aZC NMR spectrum in CDCI 3 (8, ppm): 19.78 s (C1), 21.67 t (CH2), 32.70 t (COCH2), 40.02 t (CH2N), 119.91 s (CN), 119.23 s (CO), 123.31 d, 131.99 s, 134.08 d, 167.89 s (phthalyl).

    Methyl ester of 2-(3-phthalimido-l-propanune)-l-cyclopropanecarboxylic Acid (VI) was obtained in 88% yield, m~ 73-75"C. IR spectrum (v, cmq): 1620, 1700, 1725, 1775. PMR spectrum in CDC1 s (5, ppm): 1.45 m (CH2), 2.07-2.50 m (2H, CH), 3.06 t (CH2CO, J = 7 Hz), 3.70 s (COnCHs), 3.98 t (CH2N, J = 7 Hz), 7.78 m (C6H5). 13C NMR spectrum in CDCI z (5, ppm): 17.28 t (CH~.), 24.11 d (C1), 28.99 d (C2), 32.78 t (CH2CO), 41.66 t (CHIN), 52.12 q (CO2CH,), 123.21 d, 131.98 s, 133.99 d, 167.90 s (phthalyl), 172.13 s (CO2), 204.59 s (CO).

    l~

    2.

    LITERATURE CITED

    B. M. Trost and L. S. Melvin, Sulfur Ylides, Academic Press, New York, San Francisco--London (1978), p. 102.

    G~ A. Tolstikov, F. Z. Galin, and S. N. Lakeev, Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, 1209 (1989).

    THE REACTION OF DIMETHYL DISULFIDE WITH PHENYLACETYLENE

    UNDER PHASE TRANSFER CATALYSIS CONDITIONS

    S. V. Amosova, V. A. Potapov, and N. A. Lasitsa UDC 542.97:547.279,1:547.538.241

    The reaction of diethyl disulfide with phenylacetylene in the presence of potassium hydroxide at 110-120~ leads to styryl ethyl sulfide and 1,2-di(ethylthio)-l-phenylethene [1].

    We are the first to report the possibility of synthesizing acetylenic sulfides from the corresponding acetylenes and disulfides under phase transfer catalysis conditions. Thus, the reaction of dimethyl disulfide with phenylacetylene at 90-9YC for 7 h in toluene in the presence of 85% solid sodium hydroxide and dibenzo-18-crown-6 as the phase transfer catalyst gave methyl phenylethynyl sulfide (I) in 16% yield, (Z)-styryl methyl sulfide (II) in 16% yield, and (Z)- 1,2-di(methylthio)- 1 -phenylethene (III) in 23% yield. In the absence of dibenzo- 18-crown-6, the yields of (I)-(III) are only 1-2%. When 90-92% potassium hydroxide is used under the same conditions (i.e., when the water content in the react/on mixture is reduced), sulfide (I) is obtained in 20% yield (not optimized) and ethene (III) is obtained in 4% yield.

    85~ K0H 90-920. KOH (I) + (I I) q- (III) ~ Mo2S2 q- PhC--~CH ~ (1) -F (t l i )

    These results indicate the following pathways for the formation of the reaction products.

    Irkutsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1188-1189, May, 1990. Original article submitted November 14, 1989.

    0568-5230/90/3905-1069 $12.50 9 990 Plenum Publishing Corporation ! 069

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