• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Gegenstand der Erfindung sind Pyrimidinderivate der allgemeinen Formel (n) worin R für einen Alkylrest mit 1 bis 6 Kohlenstoffatom(en) oder einen, gegebenenfalls durch 1 oder mehr Halogenatom(e) substituierten, Arylrest steht und X Chlor oder Brom oder einen, gegebenenfalls 1-oder mehrfach substituierten, Arylsulfonyloxyrest bedeutet. Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung dieser Verbindungen, bei welchem 2,6-Di-(amino)-pyrimidinderivate der allgemeinen Formel worin X die oben angegebene Bedeutung hat, mit Säureanhydriden der allgemeinen Formel worin R die oben angegebenen Bedeutungen hat, in Gegenwart von Wasser und Wasserstoffperoxyd umgesetzt werden und das erhaltene Produktgemisch oder die reinen Pyrimidinderivate der allgemeinen Formel la, Ib, Ic beziehungsweise Id abgetrennt werden und gegebenenfalls die reinen Pyrimidinderivate der allgemeinen Formel la, Ib beziehungsweise Ic beziehungsweise Gemische derselbenhydrolysiert werden und/oder gegebenenfalls die Pyrimidinderivate der allgemeinen Formel Id mit Säureanhydriden der allgemeinen Formel III, worin R die oben angegebenen Bedeutungen hat, umgesetzt werden.
    公开号:SU1556538A3
    申请号:SU874202934
    申请日:1987-07-10
    公开日:1990-04-07
    发明作者:Ведреш Андраш；Сантаи Чаба；Штефко Бела；Крайдль Янош；Немеш Андраш；Блашко Габор；Богш Эрик；Мате Денеш；Хегедюш Иштван；Суховски Адриенн；Мештер Тамаш
    申请人:Рихтер-Гедеон Ведьесети Дьяр Рт (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the preparation of pyrimidine derivatives of the general formula
    X
    (Y
    fyJSIH
    7
    TN
    (I)
    where X - Y is the N (0) group of the MSWC, where R is hydrogen (Id) or
    COR group ,. where R is C - Cfc - alkyl (ib), a R is hydrogen,
    / or X and Y are the group N (OCOR) C (NH) -, where R is C {-C6-alkyl, and hydrogen (1a), or the group RCO-, where R is d-Cf, is alkyl (ic) , Z - chlorine, bromine or substituted once or several times With-C3 alkyl
    Oj
    scrap, in the case of the necessary arylsulfonyloxy group, of the starting products in the synthesis of the hypotensive agent — 6-amino-1,2-dihydro-1-hydroxy-2-amino-4-piperidinopyrimidine.
    The purpose of the invention is to simplify the process, increase the yield of the target product and expand the range of products obtained.
    Example 1. 2-Acetamido-chloro-6-aminopyrimidine-1-oxide (1b) and 6-amino-1,2-dihydro-1-acetoxy-2-imino-4-chloro-pyrimidine (la).
    5.0 g (0.035 mol) of 2,6-diamino-β-chloropyrimidine is dissolved in 70 ml of anhydrous ethanol and 7 ml of 70% aqueous hydrogen chloride is added dropwise to this solution with stirring at 6 ° C for 0.5 h. hydrogen peroxide solution and 1 ml of acetic anhydride. The mixture was stirred at 60 ° C for another 2 hours. After cooling, the flocculated crystals were filtered off, washed with ethanol and then dried. 2.67 g (38%) of 2-acetamido-4-chloro 6-aminopyrimidine-1-oxide are obtained.
    IR spectrum (KVg):, 1690, 1640, 1610 cmH
    The mother liquor is evaporated in vacuo, the residue is mixed with 20 ml of water, and the mixture is left overnight in a refrigerator. The crystals are filtered, washed with water and then dried. Get
    Crystals of 0.77 g (11%) of the compound. The IR, UV and NMR spectra of the product are identical to those specified in Example 1.
    PRI me R 3. 6-Acetamido-1,2 hydro-1-acetoxy-2-imino-chloridine and 6-amino-1,2-dihydro-1-aceto -2-imino-chloropyrimidium.
    20
    In 170 ml of tert-butanol at 50
    10, 17.28 g (0.12 mol) of 2,6-di-α-chloropyrimidine are introduced and then 17 ml of a 30% aqueous solution of hydrogen peroxide is added. To the resulting solution is added during
    J5 1 h 36 ml acetic anhydride. The sm is stirred for another 1 h at the indicated temperature, then cooled to 1 and left for 2 h. The precipitated crystals are filtered, washed two (20 ml total) with water, then twice (20 ml each time) with ethanol and dried. 15 g (62%) of products are obtained which consists of 30% of the diacetyl compound and 79% of the mono acetyl compound.
    25 dineni. To the mother liquor, a solution of 6 g of pyrosulfite nat in 12 ml of water is added and then another 170 ml in the mixture is stirred at room temperature for 0.5 h, then evaporated in
    30 cuum Up to half the volume and pH to pH 6 with an aqueous solution of sodium alkali. The mixture is cooled for chi, the precipitated filter is filtered and washed three times (each time with 20 m water and dried. This gives 2tk g (10
    1.7 g () of 6-amino-1,2-dihydro-1-ace-35 mono-acetyl compound, IR and
    1Toxy-2-imino-4-chloropyrimidine.
    IR spectrum (KBG):, 1730, 1660, 1570, 1550 smn.
    , UV spectrum (Eson), I aad:, 276, 325 them,
    NMR spectrum (CDC13 +): 2.7 (S, 3N); 7.98 (s, 1H).
    EXAMPLE 2. 6-Amino-1,2-dihydro-1-acetoxy-2-imino-4-chloropyrimidine.
    5 g (0.035 mol) of 2,6-diamino-α-chloropyrimidine are dissolved in 50 ml of anhydrous tetrahydrofuran, 7 ml of a 70% aqueous hydrogen peroxide solution are added dropwise to the solution at 0 ° C for 0.5 h, and 16 ml of acetic anhydride. The mixture is stirred at 60 ° C for another 2 hours. After evaporation of the tetrahydrofuran, the residue is mixed with 50 ml of water and left overnight in a refrigerator. 4.00 g (57%) of the title compound are obtained. Further cooling gives the second fraction.
    40
    45
    50
    55
    The PMR spectra of the compound are identical to the dinine in Example 1,
    IR spectrum of diacetyl compound (KVg): 1720, 1690, 1600, 1570 cm4
    PRI me R. 6 Acetamido-1,2 hydro-1-acetoxy-2-imino-h-chloropymidine.
    A mixture of 3.2 g (0.02 mol) 6-amine 2-dihydro-1-hydroxy-2-imino-chloro-pyrimidine and 30 ml of acetic anhydride was stirred at room temperature for 1 hour and then mixed with 20 ether. The white crystals are filtered, washed with simple erom and then dried. G (80%) of the compound is obtained, the physical constants of which coincide with the indicated example 3.
    EXAMPLE 5-6-Amino-1,2-digo-po-1-hydroxy-2-imino-chloropyrimidine.
    1.5 g (10 mol) of 2,6-diamino-4-pyrimidine is dissolved in 20 ml without

    538 &
    crystals, 0.77 g (11%) of the compound. The IR, UV and NMR spectra of the product are identical to those specified in example 1.
    PRI me R 3. 6-Acetamido-1,2-di-hydro-1-acetoxy-2-imino-chloropyrimidine and 6-amino-1,2-dihydro-1-acetoxy- -2- imino-chloropyrimidii.
    In 170 ml of tert-butanol at 50 ° C
    17.28 g (0.12 mol) of 2,6-diamino-β-chloropyrimidine are introduced and then 17 ml of a 30% aqueous solution of hydrogen peroxide is added. To the resulting solution was added over
    1 h 36 ml of acetic anhydride. The mixture was stirred for another 1 hour at the same temperature, then cooled to 15 ° C and left for 2 hours. The precipitated crystals were filtered, washed twice (20 ml total) with water, then twice (20 ml each time) with ethanol and dried. 15 g (62%) of the product are obtained, which consists of 30% of the diacetyl compound and 79% of the mono acetyl compound. A solution of 6 g of sodium pyrosulfite in 12 ml of water and then another 170 ml of water are added to the mother liquor. The mixture was stirred at room temperature for 0.5 h, then evaporated in vacuo To half the volume and adjusted to pH 6 with an aqueous solution of sodium alkali. The mixture is cooled overnight, the precipitated product is filtered off, washed three times (each time with 20 ml) with water and dried. Get 2tk g (10%)
    mono-acetyl compound, IR and
    0
    five
    0
    five
    The PMR spectra of the compound are identical to the compound in Example 1,
    IR spectrum of diacetyl compound (KBr): 1720, 1690, 1600, 1570 cm4.
    PRI me R. 6 Acetamido-1,2-di-hydro-1-acetoxy-2-imino-h-chloropyri-midin.
    A mixture of 3.2 g (0.02 mol) of 6-amino-1, 2-dihydro-1-hydroxy-2-imino-chloropyrimidine and 30 ml of acetic anhydride is stirred at room temperature for 1 hour and then mixed with 200 ml. simple ether. The white crystals are filtered, washed with ether and then dried. This gives g (80%) of the compound, the physical constants of which are the same as those given in Example 3.
    Example 5-6-Amino-1,2-dihydro-1-hydroxy-2-imino-chloropyrimidine.
    1.5 g (10 mol) of 2,6-diamino-4-chloropyrimidine is dissolved in 20 ml of anhydrous tetrahydrofuran. Under stirring at the boiling point, a mixture of 10 ml of acetic anhydride and 2 ml of a 70% aqueous solution of hydrogen peroxide is added to the resulting solution for 30 minutes. The mixture is boiled for 8 h, evaporated in vacuo to one third of the volume, and the residue is adjusted to pH 8 with aqueous 0% sodium alkali solution. Cool-JQ mixture is given overnight. The crystals are filtered, washed with water and then dried. 1.0 g (63%) of the title compound is obtained.
    IR Spectrum (CCS):, ЗЗЮ, 1660, 15 1630 cm
    Ui-spectrum (MeON), I "ax: 230, 29/4 nm.
    EXAMPLE 6 6-Amino-1,2-dihydro-1-acetoxy-2-imino-4-chloropyrimide-20 dine and 6-acetamido-1,2-dihydro-1-ethotoxy -2-imino | - chloropyrimidine.
    , 32 g (0.03 mol) of 2,6-diamino - - chloropyrimidine and 9.3 ml of 30%
    of many anhydride. The mixture was then stirred for another 2 hours at 60 ° C, then the solvent was removed in vacuo, and the residue was cooled overnight. The precipitated material is filtered off, washed with tetrahydrofuran and then dried. 77 g (68/0) of the title compound are obtained, mp 196-200 ° C.
    IR spectrum (KBG): 1720, 1690, 1600, 1580, 1500.
    UV spectrum (EcOH), WaKC: 252, 285, 321 nm.
    NMR spectrum (CDC13 + TFA d): 2.J8 (S, 3N); 2.48 (S, 3N); 2.55 (S, 3N); 7.42 (s, zi); 7S46 and 7.98 (dd, (4H).
    Example 6-amino-1,2-dihydro-1-acetoxy-2-imino-p-toluene sulfonyloxypyrimidine.
    2.8 g (0.001 mol) of 2,6-diamino-α-tosyloxypyrimidine are suspended in 70 ml of anhydrous ethanol. Under stirring, 5 ml of a 70% aqueous solution of hydrogen peroxide and a 25% aqueous solution of hydrogen peroxide are added dropwise to the resulting suspension at P ° C with stirring.
    and after that 3 ml of acetic anhydride. When heated to BO ° C, a clear solution is obtained, which slowly takes on an opal color when standing. By thin layer chromatography it is determined that the reaction is complete and a small amount of the diacetyl compound is also formed along with the indicated compound. 0.35 g of solid is separated by filtration. 35 Ethanol is evaporated and the residue is cooled. After decantation of water and absorption of the residue in ethanol, a crystalline product is obtained. Yield 1.95 g of the indicated compound.
    at 60 ° C in 150 ml of water. 18 ml of acetic anhydride is added dropwise to the solution at ° C with stirring over kO min. The reaction mixture is stirred at this temperature for another 1.5 h, then cooled to 15 ° C and after 2 h, the precipitate is filtered off. The product is washed with water and then dried. 1.5 g (20%) of 6-acetamido-1,2-dihydro-1-acetoxy-2-α-amino-4-chloropyrimidine are obtained.
    The mother liquor is adjusted to pH 6 with an aqueous solution of sodium alkali and allowed to cool overnight. The crystals are filtered, washed with water and then dried. 1.2 g (20%) of 6-amino-1,2-dihydro-1-ace-to-2-imino-chloropyrimidine are obtained. The physical constants of the product are identical with the data of the corresponding products given in examples 3 and 1.
    PRI me R 7. 6-Acetamido-1,2-di-hydro-1-acetoxy-2-imino-4-p-toluenesulfonyloxypyrimidine.
    8 g (0.3 mol) of 2,6-diamino-tosyloxypyrimidine are suspended in 1200 ml of anhydrous tetrahydrofuran. To the suspension at room temperature, 40 ml of a 70% aqueous solution of hydrogen peroxide is added dropwise with stirring, resulting in a clear solution. To the latter, 200 ml of vinegar is added with stirring at 40 ° C for 1 h.
    Jq
    15
    20
    of many anhydride. The mixture was then stirred for another 2 hours at 60 ° C, then the solvent was removed in vacuo, and the residue was cooled overnight. The precipitated material is filtered off, washed with tetrahydrofuran and then dried. 77 g (68/0) of the title compound are obtained, mp 196-200 ° C.
    IR spectrum (KBG): 1720, 1690, 1600, 1580, 1500.
    UV spectrum (EcOH), WaKC: 252, 285, 321 nm.
    NMR spectrum (CDC13 + TFA d): 2.J8 (S, 3N); 2.48 (S, 3N); 2.55 (S, 3N); 7.42 (s, zi); 7S46 and 7.98 (dd, (4H).
    Example 6-amino-1,2-dihydro-1-acetoxy-2-imino-p-toluene sulfonyloxypyrimidine.
    2.8 g (0.001 mol) of 2,6-diamino-α-tosyloxypyrimidine are suspended in 70 ml of anhydrous ethanol. With stirring, 5 ml of a 70% aqueous solution of hydrogen peroxide are added dropwise to the suspension obtained at P ° C with stirring.
    and after that 3 ml of acetic anhydride. When heated to BO ° C, a clear solution is obtained, which slowly takes on an opal color when standing. By thin layer chromatography it is determined that the reaction is complete and a small amount of the diacetyl compound is also formed along with the indicated compound. 0.35 g of solid is separated by filtration. The ethanol is evaporated and the residue is cooled. After decantation of water and absorption of the residue in ethanol, a crystalline product is obtained. Yield 1.95 g of the indicated compound.
    IR spectrum (KBG):, 1720, 1560, 1660, 1600.
    IF spectrum (ЕСОН), а «: 2kk, 260Sh, 322 nm.
    NMR spectrum (CDClb + TFA d) 2.44 (S, 3H); 3.50 (S, 3N); 7.53 (s, 1H); 7.48 and 8.00 (dd, tH).
    PRI me R 9. 6-Amino-1,2-dihydro-1-propionoxy-2-imino-chloropyrimidine.
    8.5 g (0, м mol) of 2,6-diamino-4-х-chloropyrimidine are dissolved in a mixture of 80 ml of tert-butanol and 5.3 ml of a 70% aqueous solution of hydrogen peroxide. The solution is heated before and while stirring, 18 ml of propionic anhydride is added dropwise at such a rate that the temperature of the reaction mixture is
    60 + 2 ° C. At the end of the addition, the reaction mixture is stirred at 2 m at the same temperature and then cooled to room temperature. After 2 h, the precipitated product is filtered off, washed with cold ethanol and then dried. 6.3 g (9%) of the title compound are obtained. During the night, another 0.6 g of product drops out of the mother liquor.
    IR spectrum (KVg): 17bO (). NMR spectrum (DMSO-dfc): 1.16 (s, 3N, CH); 2.65 (g, 2Ы, СН); 7, bO (s, 1H, c fi-H); 7.62 (broad, 1H, HN).
    Example 10. b-Amino-1,2-dihydro-1-acetoxy-2-h1-amino-chloropyrimidine and 6-acetamido-1,2-dihydro-1-acetoxy--2-imino-4-chloropyrimidine.
    In a mixture of k3 ml of ethyl acetate and 3 ml of a 70% aqueous solution of hydrogen peroxide is dissolved at 50 ° C, 32 g (0.03 mol) of 2,6-diamino-chloropyrimidine. min 12 ml of acetic anhydride. The mixture was stirred at that temperature for another 0.5 hour, then allowed to cool overnight. The precipitated crystals are filtered, washed with ethyl acetate and dried. 1.80 g (25%) of 6-acetamido-1,2-dihydro-2-acetoxy-2-imino-chloropyrimidine are obtained.
    The mother liquor is extracted with kQ ml of a 10% aqueous solution of sodium alkali and twice with 0 ml of water. Then the organic phase is evaporated in vacuum to half its volume, the precipitate is filtered off and washed with water. 1.25 g (20%) of 6-amino-1,2-dihydro-1-acetoxy-2-imino-chloropyrimidine are obtained. During the night, another 0.6 g (10%) of the product falls out of the combined aqueous-alkaline phase.
    Example 11. 6-Acetamido-1-acetoxy-2-imino-mesitylenesulfonyloxy-1,2 dihydropyrimidine.
    5.8 g (0.15 mol) of 2, 1-diamino-6-mesitylenesulfonyloxypyrimidine in 600 ml of tetrahydrofuran are suspended in a 1000 ml carbon flask equipped with a stirrer, a reflux condenser, and a 1000 ml dropping funnel. Under stirring, 20 ml (27j2 g) of a 70% aqueous solution of hydrogen peroxide are added to the suspension, a clear solution is formed. The solution is heated gradually in an oil bath. When temperature reaches 0 ° C, add


    100 ml (108.1 g, 1.06 mol) of acetic anhydride are added dropwise at a rate such that the temperature does not exceed 60 ° C. At the end of the addition, the mixture is stirred at 60 ° C for an additional 2 hours. Then, in a bath of 60 ° C, the tetrahydrofuran is removed in vacuo and the residue is allowed to cool. The precipitated substance is filtered and washed with tetrahydrofuran. 3.6 g (56.5%) of the title compound are obtained in the form of a white crystalline substance, which melts with decomposition at 162-163 ° C.
    Found,%: С kS, 3b; H k, 3b; N 13.95; s 7.76.
    SPN "2bMdOv8.
    Calculated,%: 9.99; H, N 13.72; S 7.85.
    IR spectrum (KBG):, 1720, 1695, 1580, 1200, 1175, U50 cm.
    NMR spectrum (DMF): 2.10, 2.25, 2/35 (3N, S); 2.6 (6H); 2.6 (-CH); 6.6 (1H, S, 5-H); 6.85 (2H, S H1, 51-H).
    The method according to the invention allows increasing the yield of the target compound from 20-21 to 9-50% and eliminating the use of readily decomposing peroxides.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining pyrimidine derivatives of total, fbrmuly
    Y
    BUT
    where X-Y is the group H (0) SMSH, where RJ is hydrogen (id), or the group COR, where R is C (-Cb alkyl (1c), a is hydrogen,
    or XY is the group N (OCOR) C (NH) -, where R is C - (- Cb alkyl, and U is hydrogen (la), or the group RCO-, where R is C - Se-alkyl (ic), Z - chlorine, bromine or substituted once or repeatedly with C (-Co-alkyl, if necessary arylsulfonyloxy-group,
    by oxidation of 2,6-diaminopyrimidine of the general formula
    H2N
    N
    Y
    N
    NH9155653810
    where Z has the indicated values, the presence of an acid anhydride of the total
    peroxide compound, about tl and h and-formulas y y and with the fact that, with the aim of simplified (.
    process, increase the yield of the target, where R is C-C6-alkyl,
    product and expansion assortment, and 2-20 mol of water and the resulting compound of the products obtained, as nen (la) or (is), or (1c), or
    the peroxide compound is used by the ne-mixture (la), (ic) is isolated or hydrogen hydroxide and the process is carried out to prepare the compound (id).
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1181657A|1966-03-31|1970-02-18|Ici Ltd|Pyrimidine Derivatives and Compositions Containing them|
    CH638216A5|1977-02-04|1983-09-15|Hoffmann La Roche|OXADIAZOLOPYRIMIDINE DERIATES.|
    HU177601B|1978-10-27|1981-11-28|Egyt Gyogyszervegyeszeti Gyar|New process for preparing 6-piperidino-2,4-diamino-pyrimidine-3-oxide|
    CA1179344A|1981-07-15|1984-12-11|Jean-Claude Muller|Process for the preparation of 6-¬3,6-dihydro-1- pyridyl| pyrimidine-3-oxides|
    HU196067B|1986-07-10|1988-09-28|Richter Gedeon Vegyeszet|Process for production of 6-amin-1,2-dihydro-1-hydroxi-2-imino-4-piperidin-piramidin|US5051429A|1984-10-12|1991-09-24|Warner-Lambert Co.|"Pyrimidine derivatives"|
    FR2632954B1|1988-06-15|1990-11-16|Norchim Sarl|PROCESS FOR THE PREPARATION OF PYRIMIDINE-N-OXIDES|
    US4959475A|1989-01-04|1990-09-25|Lonza Ltd.|Process for the production of 2,4-diamino-6-piperidinyl-pyrimidine-3-N-oxide|
    FR2781481B1|1998-07-24|2000-09-15|Oreal|NOVEL 2-AMINO, 4-ALKYLAMINO PYRIMIDINE 3-OXIDES AND COMPOSITION COMPRISING THE SAME|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU862856A|HU196061B|1986-07-10|1986-07-10|Process for production of pirimidine-derivatives|LV930038A| LV5243A3|1986-07-10|1993-01-18|Saturation of pirimidine derivatives|
    LTRP853A| LT2198B|1986-07-10|1993-08-13|THE PIRIMIDINE'S WAY OF RECEIVING|
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