• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    This invention relates to compounds having the formulae <IMAGE> (I) +TR <IMAGE> (II) in which: R1 represents hydrogen, a halogen atom or a lower alkyl radical, a lower alkoxy radical or a lower alkylthio radical; R2 represents hydrogen or a lower alkyl, aralkyl, aryl, carboxy or alkoxycarbonyl radical; R3 represents hydrogen, a C1-12 alkyl radical, or an aralkyl or aryl radical, optionally substituted on the aromatic nucleus with one or more halogen atoms or hydroxy, nitro, cyano, carboxamido, carboxy, alkoxycarbonyl, lower alkyl, lower alkoxy or trifluoromethyl groups; and n is zero or 1. Said new compounds possess therapeutically useful blood-platelet aggregation inhibiting properties and also anti-thrombotic, anti-sludge, antalgic and anti-inflammatory properties.
    公开号:SU910122A3
    申请号:SU782593002
    申请日:1978-03-24
    公开日:1982-02-28
    发明作者:Буажегрэн Робер；Гашон Мишель；Маффран Жан-Пьер；Мэр Жерар
    申请人:Паркор (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to new derivatives of thienopyridine, which can be used as physiologically active substances.
    A known method of producing · thieno (2,3 - s) -pyridines of the formula
    -PYRIDINES which is hydrolyzed to a compound
    consisting in the fact that the compounds of the formula (- G 'CH-C-CO g C 2 H 5 [GT
    S clearly cyclize to give a compound of the formula
    followed by decarboxylation of DI
    A method of obtaining known thienopyridines in the literature is not described.
    The purpose of the invention is the expansion of the range of derivatives of thienopyridine β by
    The goal is achieved by obtaining thieno- (2,3-c} -or (3-2-c ^ -pyridines of the General formula
    where R 1 is hydrogen;
    R 2 is hydrogen, lower alkyl, phenyl, carboxy;
    R is hydrogen, lower alkyl, phenyl benzyl, unsubstituted or substituted in the ring by halogen, cyano, lower alkoxy, or carbomethoxy;
    η = 0, I, the distinguishing feature of which is that the compounds of the general formula
    s-to 3
    where R, R, R, η have the above meanings, are oxidized with potassium permanganate at 40-56 ° C in acetone, the target product is isolated or hydrolyzed to obtain compounds of formula I and II when η = I and R'l and have the above meanings , is hydrogen.
    The starting reagents are prepared by known methods.
    Example I. 5-0 ~ Chlorobenzyl-4oxo-4,5,6,7-tetrahydrothieno- (3,2-c) pyridine.
    To a solution of 6.5 g (24.6 mmol) of 5-0 chlorobenzyl-4,5,6,7-tetragi rotieno (. 3,2-s) -pyridine in 250 cm 'of acetone, stirred and heated to 40 ° C, 15.59 g (98.6 mmol of finely ground potassium permanganate are added in portions. The reaction proceeds at the boiling point of the solvent under reflux. After addition at 40 ° C, it is cooled and filtered through a silica layer for 30 minutes. Evaporation of the filtrate to dryness gives a solid a substance that crystallizes from dieopropyl ether. White crystals: mp 60 ° C, yield 55%.
    Example 2. 5-Benzyl-4 ~ oxo-4,5,6,7-tetrahydrothieno- (3,2-s) -pyridine.
    Follow the procedure of example 1, but proceed from 5 ~ benzyl ~ 4,5,6,7-tetrahydrothiano- (3,2-c) -pyridine. White crystals: t n A54 ° C, t KWn (0.05 mm Hg) 115 ° C, 64% yield. ·
    Example 3. 5-I-Chlorobenzyl-4oxo-4,5,6,7-tetrahydrothieno- (3,2-c) pyridine.
    Follow the procedure of example 1, but proceed from 5-I ~ chlorobenzyl ~ 4,5,6,7-tetrahydrothieno (3,2-s) - pyridine. White crystals: t 120 ° С (ethanol-diiso propyl ether), 66% yield.
    Example 4. 6 ~ 0 ~ Chlorobenzyl-7oxo-4,5,6,7-tetrahydrothieno- (2,3-c) pyridine.
    Follow the procedure of example 1, but proceed from 6-0-chlorobenzyl-4.5.6.7-tetrahydrothieno (2.3-s) -pyridine. Crystals of pale yellow color: tp ^ 30 ° C (diisopropyl ether), yield 45%.
    Example 5. 5 ~ Acetyl-4 ~ oxo4,5,6,7-tetrahydrothieno- (3,2-s) - pyridine.
    Follow the procedure of example 1, but proceed from 5-acetyl-4,5,6,7-tetrahydrothieno (3,2-c) -pyridine. Ivory crystals: 90 b C (diisopropyl ether), 46% yield.
    Example 6. 4-0xo-5-0 ~ chlorobenzoyl-4,5,6,7-tetrahydrothieno- (3, 2-s) -; pyridine.
    Follow the procedure of example 1, but proceed from 5-0 ~ chlorobenzoyl-4,5,6,7, tetrahydrothieno- (3,2, s) -pyridine. White crystals: 148 ° C (ethanol-diisopropyl ether), yield 57%.
    Example 7, 4-Oxo-4,5,6,7 tetrahydrothieno- (.3,2, -c) -pyridine.
    The mixture was stirred at room temperature for 4 hours, initially heterogeneous 13.6 g (0.069 mol) of 5-acetyl-4-oxo-4,5,6,7-tetrahydrothieno (3,2-c) -pyridine (. Example 5 ), 50 cm of ethanol and 50 cm ^ b of N. hydrochloric acid. It is concentrated in vacuo, the residue is slightly alkalinized by the addition of sodium hydroxide and extracted with methylene chloride. The organic extracts are washed with water, dried over sodium sulfate and evaporated to dryness. The residue is crystallized from a mixture of isopropanol and diisopropyl ether.
    White crystals: 94 * 12, 70% yield.
    Example 8. 5-0-cyanobenzyl-4-oxo-4, 5,6,7-tetrahydrothieno - (. 3,
    2-c) -pyridine. 5
    Follow the procedure of example 1, but come from 5-0-cyanobenzyl-4,5,6,7tetrahydrothieno (3,2-s) -pyridine. White crystals: 1 15 ° С (diisopropyl ether-isopropanol), 10 yield 69%. .
    Example 9. 5-0-Carbomethoxybenzyl-4 ~ oxo ~ 4,5,6,7-tetrahydrothieno (3,2-s) ~ pyridine.
    Receive, following the procedure of example 15, measure 1, but starting from 5-0-carbomethoxy-4,5,6,7-tetrahydrothieno (3,2-s) pyridine. White crystals: ^ PA 98 ° C (diisopropyl ether - isopropanol), yield 61%. 20
    Example 10. 6-0-Chlorobenzoyl-7-oxo-4,5,6,7-tetrahydrothieno- (2,
    3-c) -pyridine.
    Receive, following the methodology of the example. 1, but based on 6 ~ 0 ~ xporbenzoyl-4,5 ~ 25
    6.7-tetrahydrothieno - (2,3-c) -pyridine. White crystals: ΈπΛ '150 ° C (ethanol-diisopropyl ether), yield 39%.
    ’Example II .6-Acetyl-7-oxo-4,5,
    6.7-tetrahydrothieno- (2,3-c) -pyridine.
    Receive, following the procedure of example 1, but the yield of 6-acetyl-4,5,6,7-tetrahydrothieno (2,3-c) -pyridine. White crystals: 92 ° C, yield 43%.
    Example 12. 7-Oxo-4,5,6,7 tetrahydrothieno- (2,3 ~ s) -pyridine.
    Receive, following the procedure of example 7, but based on 6-acetyl ~ 7-oxo-4,5, - 40
    6.7-tetrahydrothieno- (2,3-c) -pyridine (example 11). White crystals: t 120 ° С (diisopropyl ether-isopropanol), yield 66%.
    Example 13. 6-Benzyloxycarbonyl ~ 5-benzyl-4-oxo-4,5,6,7-tetrahydrothieno- (3,2-s) -pyridine.
    Receive, following the methodology · example
    1, but starting from 6-benzyloxycarbonyl-5-benzyl-4,5,6,7-tetrahydrothieno · 50 (3,2-s) -pyridine. White crystals: t: nf4 72 ° С (cyclohexane), yield 53%.
    Example 14. 6-Carboxy-5-benzyl-4-oxo-4,5,6,7-tetrahydrothieno- JS (3,2-c) -pyridine ..
    "Obtained by saponification of 6-benzyloxy-carbonyl-5-benzyl-4-oxo-4,5,6,7-tetrahydrothieno (3,2-s) -pyridine."
    | Kristaply pink: 258 ° C (isopropanol-ethanol /, yield 70%.
    Example 15. 6- (3,4,5, -Trimethoxybenzyloxycarbonyl) -5- (3,4,5trimethoxybenzyl) -4-oxo-4,5,6,7tetrahydrothieno (3,2-c) pyridine. .
    Receive, following the procedure of example 1, from 6- (3,4,5 ~ trimethoxybenzyloxycarbonyl) ~ 5 ~ (3,4,5-trimethoxybenzyl) -4,5,6,7-tetrahydrothieno (3.2 ~ c) ~ pyridine. Cristal whitish color: 55 ° C, yield 48%.
    Example 16. 6-Carboxy-5- (3, 4,5-trimethoxybenzyl) -4-oxo-4,5,6,7-tetrahydrothieno (3,2-c) pyridine.
    Obtained by saponification of 6- (3,4,5 - trimethoxybenzyloxycarbonyl) -5- (3,4,5 “trimethoxybenzyl) -4 ~ oxo ~ 4,5,6,7 tetrahydrothieio (3,2-c) -pyridine (Example 15) . Beige crystals: tp ^ 208 ° C (isopropanol), yield 65%.
    Example 17. 4-phenyl-b-acetate 7-oxo-4,5,6,7-tetrahydrothieno (2,3-c) -pyridine.
    The following 4-phenyl ~ 6 ~ acetyl-4,5,6,7-tetrahydrothieno-f 2,3 ~ c> -pyridine are obtained, following the procedure of Example 1. White crystals:% A 1 3.2 ° С (cyclohexane ethyl acetate), yield 20%.
    Example 18. 4-phenyl-7-oxo-
    4.5.6.7-tetrahydrothieno- (2,3-s) -pyridine.
    Receive, following the procedure of example 7, starting from 4-phenyl ~ 6 ~ acetyl-7-oxo-
    4.5.6.7- tetrahydrothieno- (2,3-s) - pi-. ridin (example 17). White crystals: t P d 16СР С (diisopropyl ether-isopropanol), yield 68%.
    Proof of compound structure:
    Compound 1 IR spectrum (KB_), Ί) cm: СО 1645. Nuclear Magnetic Resonance Spectrum (CDClj) o: 7.30 (Ch. 4H); 7.20 (q, 2H, J 4.5 Hz); 4.80
    (S, 2H); 3.55 (t, 2H, J6 Hz); 3.00 (t, 2H, EbHz).
    Compound 2
    IR spectrum (KB ^), e) cm: C 0 1645.
    Compound 3
    IR spectrum (KB £ 1. $ Cm: ^ C0 1640.
    Nuclear Magnetic Resonance Spectrum (CDC1) cC Ί, 30 (q, 2H, J 4.5 Hz); 7.25 (S, 4il); 4.70 (S, 2H);
    3.55 (t, 2H, J 6 Gp); 3.05 (t, 2H, J
    Hz).
    . Compound 4
    IR spectrum (KB ^), Ό s.m ~: СО 1655.
    Nuclear Magnetic Resonance Spectrum (СОС1 Э ) <Г: 7.30 (t, 4Н); 7.15 (q, 2H, J 4.5 Hz); 4.85 (S.2H); 3.60 (t, 2H, J 6 Hz); 2.90 (t, 2H, J 6 Hz).
    Compound 5
    IR spectrum (KBr), 'V & m- ^ o 1680.
    Nuclear Magnetic Resonance Spectrum (CDC1 3 ) (T: 7.35 (q, 2H, J 4.5); 4.30 (t, 2H,
    3.15 (t, 2H, J 7 Hz); 2.65
    Compound 6
    IR spectrum, L> cm 4 ; With
    -1700.
    NMR spectrum (С0С1з) сГ; 7.40 7.30 (q, 2H, J 4.5 Hz); 4.45 J 6 Hz); 3.25 (t, 2H, J = 6 Hz).
    J .7 Hz) (S, 3H).
    1665
    910122 8 (S.2H ·); 4.80 (q, 2H, J 15 Hz); 4.30 (m, 1H); 3.40 (t, 2H).
    Compound 14
    IR spectrum (KB 0 ), 4> s.M ~ ^ · СО 16 ΙΟΙ 730.
    NMR spectrum (OMSOD e ) sG: 7H); 4.60 (q, 2H, J 15 Hz);
    (tn, 1H); 3.35 (t, 2H).
    Compound I5
    IR spectrum (KB o), 1 :
    1740.
    Compound 16
    IR spectrum (KB ), 3000; СО I590-1740.
    NMR spectrum (CF COOH): (Q, 2H, j 4.50 Hz); 6.80 (S, to: 7.30 (S,
    4.30
    CO 1655OH 2500 (S, 4H); (t, 2H,
    7.40
    2H); 4.70 (Wi, 1H;
    Compound 7
    IR spectrum (HPC), l): СО 16351665; NH 2300.
    NMR spectrum (CDCl-j) (G: 7.60 (S, 1H); 7.15 (q, 2H, J 4.5 Hz); 3.60 (t, 2H, J 7 Hz); 3.05 (t, 2Η, ϋ7Γπ)
    Compound 8
    IR spectrum (KB ': C0 1645;
    With "N 2230 cm.
    NMR spectrum (CDCI3) (G: 7.50 (t, 4H); 7.20 (q, 2H, J 4.5 Hz); 4.85 (S, 2H); 3.65 (t, 2H, J 7 Hz).
    Compound 9
    IR (KB 2 ), 3) cm ~: СО '' Compound 10
    IR spectrum (HF „), and) cm“ 4 : СО 1685.
    Nuclear Magnetic Resonance Spectrum (CDCU) i: 7.25 (S,
    4H); 7.20 (q, 2H, J 4.5 Hz); 4.25 (t, 2H, J 7 Hz); 3.00 (t, 2H, J 7 Hz),
    Compound 1g
    NMR spectrum (CDCl % ) cT: 7.30 (q, 2H, J 4.5); 4.20 (t, 2H, J7 Hz); 2.90 (t, 2H, J 7 Hz); 2.60 (s, ss).
    Compound 12
    IR spectrum (KB-), l) cm ' 4 : СО 1630; ΝΗ 3215.
    Compound 13
    IR spectrum (KB 2 ), with M ′ 4 : СО 16501755.
    Spectrum: NMR (SOSC) SG: 7.30 (t, UN); 7.30 (q, 2H, J 4.5 Hz); 5.10
    1635166525
    Compound 17
    IR spectrum (HF), cm: СО 1655-1705. NMR spectrum (CDCI ^ cf: 7.25 (m, 5H); 7.15 (q, 2H, 3 4.5 Hz);
    4,50 (hl, ZN); 2.60 (s, 3H).
    Compound 18
    IR spectrum (CV 9 ), ί) cm ~ ^:
    СО 1655 ..
    NMR spectrum (CDCIj) <ί: 7.20 (S, 5 Η); 7.05 (g, 2 Η, J 4.5 Hz); 350-4.60 (m, 3H).
    Note: S - chitglet; d is a doublet; t is a triplet; q quartet; m is the multiplet.
    权利要求:
    Claims (2)
    [1]
    ..T-A-icl% g where R is hydrogen; R is hydrogen, lower alkyl, phenyl, carboxy; hydrogen, lower alkyl, phenyl benzyl, unsubstituted or substituted in the ring by halogen, cyano, lower alkoxy or carbomethoxy; p 0.1, the distinguishing feature of which is that the compounds of the general formula (and where R, R, R, n have the above values are oxidized with potassium permanganate at 40-56 seconds in acetone, the target product is isolated or hydrolyzed for the preparation of compounds of formula 1 and 11, when n 1 and f 2. R and R are as indicated, R is hydrogen. The starting reagents are prepared by known methods. Example I. 5-0-Chlorobenzyl-4 oxo-4,5,6 , 7-tetrahydrothieno {3,2-c pyridine. To a stirred and heated to a solution of 6.5 g (24.6 mmol) 5 chlorobenz 1-4, 5,6,7 tetrahydrothieno C 3,) is pyridine and in 250 cm of acetone, 15.59 g (98.6 mmo of finely ground LIA permanganate is added in portions. The reaction proceeds at the refluxing temperature of the solvent with a reflux condenser. After the addition is completed, the mixture is cooled for 30 minutes and filtered through a layer silicon dioxide. Evaporation of the filtrate to dryness gives a solid, which is crystallized from diisopropyl ether. White crystals: mp = 60 ° C, yield 55%. Example 2. 5-Benzyl-4-oxo-4, 5,6,7-tetrahydrothieno- (3,2-e) -pyridine. The procedure of Example I is followed, but is derived from 5-benzyl-4,5,6,7-tetrahydrothieno- (3,2-c) -pyridine. White crystals: tp 54C, (0.05 mm Hg), yield 64%. Example 3. 5-P-Chlorobenzyl-4oxo-4, 5,6,7-tetrahydrothieno-C3, 2-e) pyridine. The procedure of Example 1 is followed, but is derived from 5-And-chlorobenzyl-4,5,6,7-tetrahydrothieno 3,2-c) pyridine. White crystals: t 120 ° С (ethanol-diisopropyl ether), - yield 66%. Example 4 6-0-Chlorobenzyl-7oxo-4, 5,6,7-tetrahydrothieno- (2, 3-c pyridine. Follow the procedure of Example 1, but proceed from 6-0-chlorobenzyl-4,5.6.7- tetrahydrothieno-f2 .3-c} -pyridine. Pale yellow crystals: (diisopropyl ether), yield 45%. Example 5. 5-Acetyl-4-oxo4, 5,6,7-tetrahydrothieno- (3,2-s) - pyridine. The procedure of Example 1 is followed, but comes from 5-acetyl-4,5,6,7-tetrahydrothieno- (3, 2-e) -pyridine. Ivory crystals: tf (diisopropyl ether, 46% yield. Example 6 4-Oxo-5-0-chlorobenzoyl-4, 5,6,7-tetrahydrothieno (3, 2-e) -pyridine. Follow the procedure of Example I, but is based on 5-0-chl Orbenzoyl-4,5,6,7, tetrahydrothieno- (3,2, c) -pyridine. White crystals: (ethanol-diisopropyl ether), 57% yield. Example 7. 4-Oxo-4,5,6, 7 tetrahydrothieno- (3,2, -c / -pyridine. The mixture is stirred at room temperature for 4 hours, initially heterogeneous 13.6 g (0.069 mol) of 5-ace - TIL-4-OXO-4,5,6,7-tetrahydrothieno (3,2-s) -pyridine (. Example 5), 50 cm of ethanol and 50 cm 6 of hydrochloric acid. Concentrate under vacuum, slightly alkalize the residue by addition of sodium hydroxide and extract with methylene chloride. The organic extracts are washed with water, dried over sodium sulfate and evaporated to dryness. The residue is crystallized from a mixture of isopropanol and diisopropyl ether. 5 White crystals: t- ,. 94, yield 70%. Example 8. H-O-cyanobenzyl-4-OXO-4, 5,6, 7-tetragi roteno- (-3, 2-c) -pyridine. The procedure of Example 1 is followed, but is derived from 5-0-cyanobenzyl-4,5,6,7 tetrahydrothieno- (3,2-e) -pyridine. White crystals: .C (diisopropyl ether-isopropanol, 69% yield. Example 9. 5-0-Carbomethoxybenzyl-4-oxo-4, 5,6,7-tetrahydrothieno- (3,2-s) -pyridine. This is obtained following the procedure of Example 1, but the result is from 5-0-carbomethoxy-4, 5,6,7-tetrahydrothieno- (3,2-c) pyridine. White crystals: PL (diisopropyl ether - iso-propanol), yield 61%. Example 10. 6-0-Chlorobenzoyl-7-OXO-4, 5,6,7-tetrahydrothieno- (2, 3-e) -pyridine. Prepared following the procedure of Example I, but starting from 6-0- chlorobenzoyl-4,5- 6,7-tetrahydrothieno- (2,3-c) -pchridine White crystals: -LpA (ethanol-diisopropyl ether), yield 39%. i EXAMPLE 11.6-Acetyl-7-oxo-4,5, - 6,7-tetrahydrothieno-1,2, 3-d J-pyridine. This is obtained following the procedure of Example 1, but iso d of 6-acetyl-4,5,6,7-tet rahydrothieno-2,3-e) -pyridine. White crystals: 1 .., yield 43%. Example 12. 7-Okeo-4,5,6,7 tetrahydrothieno- (2,3-e) -pyridine. Polupagot, following the procedure of example 7, but an approach from 6-acetyl-7-oxo-4,5, 6, 7-tetrahydrothieno - {; 2, 3-e) -pyridine (example and). White Cretalls: t pl 120 ° С (diisopropyl ether etherisopropanol), yield 66%. Example 13. 6-Benzyloxycarbonyl-5-benzyl-4-ocean-4, 5,6,7-tetrahydrothieno- (3, 2-e) -pyridine. This is obtained according to the procedure of Example 1, but starting from 6-benzyloxycarbonyl-5-benzyl-4,5,6,7-tetrahydrothieno (3,2-e) -pyridine. White Cretallas: t 72 ° C (cyclohexane, yield Example 14. 6-Carboxy-5-ben ZIL-4-OXO-4,5,6,7-tetrahydrothieno (3,2-e) -pyridine .. Prepared by sizing 6-benzyloxycarbonyl-5-benzyl-4-ocean-4,5,6,7 tetrahydrothieno- (3,2-e) -pyridine. 26 | Pink color chapters: t 258С (isopropanol-ethanol, 70% yield. Example 15. 6- (3,4,5, -Trimethochebenzyloxycarbonyl) -5- (3,4,5trimethoxybenzyl) -4-oxo-4,5,6,7 tetrahydrothieno- (3,2-e) -pyridine. Get , following the procedure of Example 1, from 6- (3,4,5-t {) imethoxybenzyl oxycarbonyl) -5- (3,4,5-trimethoxybenzyl) -4,5,6,7-tetrahydrothieno- (3,2-e pyridine. Christaples belovatog colors: tp 55 ° C, yield 48%. Example 16. 6-KarGukey-5- {3, 4,5-trimethoxybenzyl) -4-ocean-4,5,6,7-tetrahydrothieno- (3,2- e) -pyridine. Prepared by saponification of 6- (3,4,5-trimethoxybenzyloxycarbonyl) -5- (3,4,5 trimethoxybenzyl) -4-ocean-4,5,6,7 tetrahydrothieno (3, 2-e) -pyridine (Example 15). Beige crystals: tf / 208C (isopropanol), yield 65%. Example 17. 4-phenyl-6-acetyl7-OXO-4, 5,6,7-tetrahydrothieno (2,3-с) - pyridine. Receive, following the method of example 1, from 4-phenyl-6-acetyl-4,5,6,7-t $ trahydrothieno- (2,3-c-pyridine. White crystals: t 13. (cyclohexane-ethyl acetate), vimod 20%. Example 18. 4-phenyl-7-oxo4, 5,6, 7-tetrahydro-hyeno- (2,3-e) -pyridine. This is prepared according to the procedure of Example 7, starting from 4-phenyl-6- acetyl-7-ocean4,5,6,7-tetrahydrothieno- (2,3-e) -pi-pyridine (Example 17). White crystals: t rp 16CPC (diisopropyl ether-isopropanol), yield 68%, Proof structures of compound Compound 1 IR spectrum (KV), 1) cm: CO. Nuclear Magnetic Resonance Spectrum (CDCl1): 7.30 (m, 4H); 7.20 (q, 2H, J 4.5 Hz); 4.80 (s, 2H); 3.55 (t, 2H, J6 Hz); 3.00 (t, 2H, ibHz). Compound 2 Spectrum (KV), -V e: C O 1645. Compound 3 IR spectrum (KV -d) 1640. NMR spectrum (CDC1), 30 (q, 2H, J 4.5 Hz); 7.25 ( S, 4ii); 4.70 (5.2H); 3.55 (t, 2H, J 6, 05 (t, 2H, J 6 Hz). Compound 4 1 IR spectrum (KKf), CO 165 NMR spectrum (CDCljjtf: 7.30 (W, 4H); 7, 15 (q, 2H, J 4.5 Hz); 4.85 (S, 2H); 3.60 (t, 2H, J 6 Hz); 2.90 (t, 2H, J 6 Hz). Compound 5 IR spectrum (KVg), 1 l CO 1680. NMR spectrum () "G: 7.35 (q, 2H, J 4.5); 4.30 (t, 2H, J 7 Hz 3.15 ( t, 2H, J 7 Hz); 2.65 (S, 3H) - Compound 6 IR spectrum (1ГВ, 1, -ilcM; CO 1665 -1700, NMR spectrum (SOSTS) sG: 7.40 (5.4 n 7.30 (q, 2H, J 4.5 Hz); 4.45 (t, 2H, J 6 Hz); 3.25 (t, 2H, J 6 Hz). Compound 7 IR spectrum (KVd), iDcM: CO 16351665; NH 2300. NMR spectrum (COClS) (f: 7.60 (S, 1H); 7.15 (q, 2H, J 4.5 Hz); 3.60 (t, 2H, J 7 Hz);, 05 (t, 2H, J7nx Compound 8 IR spectrum (KV,: CO 1645; C "N 2230 cm. NMR spectrum (CDClj) cf: 7.50 (m, 4H); 7.20 (q , 2H, J 4.5 Hz); 4.85 (S, 2H); 3.65 (t, 2H, J 7 G Compound 9 IR spectrum (KV-,), l) cm CO 1635 Compound 10 IR spectrum (KV n), L) cm-: CO 16651685. NMR spectrum (CDCla): 7.25 (S, 4H) ; 7.20 (q, 2H, J 4.5 Hz); 4.25 (t, 2H, J 7 Hz); 3.00 (t, 2H, J 7 Hz) Compound 11 NMR spectrum (COC1) cG: 7.30 (q, 2H, J 4,5); 4.20 (t, 2H, J7 Hz); 2.90 (t, 2H, J 7 Hz); 2.60 (S, W). Connection 12 IR spectrum, CO 1630; NH 3215. Compound 13 IR spectrum (КВ2), СМ-: СО 16501755. Spectrum; NMR (CDCl5) cf: 7.30 (m, YUN); 7.30 (q, 2H, J 4.5 Hz); 5.10 2 (s, 2№); 4.80 (q, 2H, J 15 Hz); 4, 3.40 (t, 2H). Compound 14 IR-spectrum (KB „), - l) cm: CO 16101730. Nuclear Magnetic Resonance Spectrum (OMSODeJcT: 7.30 (S, 7H); 4.60 (q, 2H, J 15 Hz); 4.30 (m, lH); 3.35 (t, 2n). Compound I 5 IR- spectrum (KB
    [2]
    2.),: CO 16551740. Connection 16 "K-spectrum (KV,), OM-OH 2500ZOOO; CO 1590-1740. Nuclear Magnetic Resonance Spectrum (CF COOH) (f: 7.40 q ,, 2H, 7 4.50 Hz); 6.80 (S, 2H); , 00 (sous, 2H, 3–16 Hz); 4.70 (yvi, 1H; 3.95 (6. ZN); 3.90 CvY, 2 n), 3.60 VM, 2H). Compound 17 IR spectrum (CV), cm: CO 1 655-1705. Nuclear Magnetic Resonance Spectrum (CO1a, a) cG: 7.25 (t, 5H); 7.15 (q, 2H, 3 4.5 Hz); , 50 (t, 3N); 2.60 (5, 3M). Compound 18 NK-spectrum (KBj,) l) CO 1655 .. NMR spectrum (CDClj) G: 7.20 (S.SH); , 05 (g, 2H, J 4.5 Hz); 350-4,60 m, ЗН). Note: S-sinlet; d - doublet; t is a triplet; q vartet; m - multiplet. The invention of the method of producing thieno- (2, 3dc) whether (3,2-e) -pyridines of the general formula fjQ g- (C) "- to (U de R, - hydrogen; hydrogen, lower alkyl, phenyl, and carboxy ; R is hydrogen, lower alkyl, phenyl, benzyl, unsubstituted or substituted in the ring by halogen, cyano, lower alkoxy or carbmethoxy; u 0.1;
    9
    characterized by combining sp of the general formula
    R2
    -R
    II 1
    VOJn
    or
    | 0
    iiAcln-;
    E
    91012210
    1 ° where R, R, R 3, n are as defined above, is oxidized with permanganate carbonyl when DO-3B C in acetone, the target product is isolated or hydrolyzed to obtain compounds of formula 1 or P when n 1 and R and I have the above values, R is hydrogen.
    Information sources,
    10 taken into account in the examination 1. Michel Farnicr. Recherches en seril heterocycligue, - J. Canadien de Chimi, 1976, V.54, f 7, p.l0661068.
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    US3845065A|1972-02-18|1974-10-29|Merck & Co Inc|4-oxo-4,5-dihydrothienopyridines|
    US3903095A|1972-02-18|1975-09-02|Merck & Co Inc|Certain substituted-thieno{8 3,2-c{9 -pyridines|AT368504B|1977-10-15|1982-10-25|Boehringer Sohn Ingelheim|METHOD FOR PRODUCING NEW 4-PHENYL-THIENO--PIPERIDINE|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB13209/77A|GB1576511A|1977-03-29|1977-03-29|Thieno andpyridines process for their preparation and therapeutic applications thereof|
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