• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Optically active pyrimidine derivatives of the general formula (I) wherein the symbol Z represents a group of the formula -(CH2)n- or -(CH2)n-O- in which n stands for an integer of 1 to 4 and each of the symbols X represents a nitrogen atom and each of the symbols Y represents -CH- or each of the symbols Y represents a nitrogen atom and each of the symbols X represents -CH-and their preparation. The compounds of formula I are valuable components in liquid crystalline mixtures, particularly in combination with nematic components and are thus utilizable for electro-optic purposes.
    公开号:SU867302A3
    申请号:SU782590454
    申请日:1978-03-15
    公开日:1981-09-23
    发明作者:Боллер Артур；Черегетти Марко；Шеррер Ханспетер
    申请人:Ф.Гоффманн Ля Рош И Ко., Аг (Фирма)；
    IPC主号:
    专利说明:

    Sifted on a short column from snliagel and then recrystallized from methylene chloride / methanol,. square 149.9 Cg t. 233 ,,
    Found,%: C 76.94; H 6.16 N 12.24
     NjO M.V. (343,430)
    Calculated,%: from 76.74; H 6.14J 12.09
    The starting compounds can be prepared as follows.
    In a solution of 88.6 g of 4-cyanobenzoic acid methyl ester in 190 ml of enzol and 70 ml of methanol, dry hydrogen chloride is added 3 hours later by transferring at 0 ° C. The reaction mixture is incubated for 5 days at + 5 ° C and then the imido ether is filtered off. After cooling to -40 ° C, 130 g of liquid ammonia are added to 178 g of this material, suspended in 300 ml of methanol, and shaken for 24 hours at + 70 ° C in an autoclave. After cooling the reaction mixture to room temperature and discharging ammonia, the crystallized product was filtered on a suction filter, and the crystals were washed with hexane and dried overnight under a vacuum obtained with a water jet pump. A 4-amidinobenzoic acid amide hydrochloride is obtained.
    46.07 g of 1- (4 - (+) - 2-methyl-1-butyloxyphenyl) -2-methoxyethylene are added dropwise to a solution of 2 ml of boto-trifluoride ethorate in 500 ml of ortricine acid, cooled in an ice bath. Then the reaction mixture is continued to stir at room temperature. After dilution with ether, extraction with 1N. with a solution of caustic soda and water and evaporation of the organic phase dried with sodium sulfate, (+) - 2-methyl-1-butyl-cyphenyl-methyl-tetradetal is obtained.
    7.33 g of 4 - (+) - 2-methyl-1-butyloxyphenyl-malone-tetraacetal is stirred overnight at 50 ° C with the introduction of nitrogen into 20 ml. ethanol in a place with 0.72 ml of water and 2 drops of concentrated sulfuric acid. By boiling the reaction mixture diluted with ether with an aqueous solution of sodium carbonate, it is possible to separate the acid (+) - 2-methyl-butyloxyphenyl-malonaldehyde obtained as a side effect of Duct from neutral 2- (4 - (+) - 2-methyl-1-butyloxyphenyl) Z-ethoxy-acrolein,,
    4.46 g of 2- (4 - (+) - 2-methyl-1-butylC) xyphenyl) -3-, ethoxyacrolein, 3.63 g of said 4-amI amide hydrochloride of Dinobenzoic acid and 0.0254 mol of sodium atate sate (obtained by dissolving 0., 584 g of sodium metal in methaNol) is suspended in J250 ml of methanol and stirred overnight at
    room temperature with the introduction of nitrogen. Then the yellow suspension is filtered on suction, washed with a small amount of ethanol and suspended for further purification in 1.4 liters of ether. The suspension is washed with water and filtered again. The hardly soluble amide of 4-G5- (4 - (+) - 2-methyl-1-butyloxyphenyl) -2-pyrimidinyl 1-benzoic acid is obtained.
    Analogously to example 1, the following compounds of formula 1 can be obtained.
    5- (4- (+) -3-methyl-1-pentyloxy-phenyl) -2- (4-cyanophenyl) -pyrimidine, m.p. 950С, t. 235.7 s, yield 89%,
    Found,%: C 77.28; H 6.49) N 11.76
    C, 2EN M.V. (357, 457)
    calculated,%: C 77.04; H 6.50, N 11.69
    5- (4- (+) -4-methyl-1-hexyloxyphenyl) -2- (4-cyanophenyl) -pyrimidine, m.p. 121-122 ° C, t. Osv. 238 ,, yield 78%.
    Found,%: C 77.60; H 6.78, N 11.31
    CQ4Has 3 ° (371.484) Calculated,%: C 77.64; H 6.81, N 11.25
    5- (4 - (+) -2-methyl-1-butylphenyl) -2- (4-cyanophenyl) -pyrimidine, m.p. 105.6 ° C; T. Osw, 206 ,, yield 84%. Found %: C 80.70 H 6.46; N 12, “6
    , Mo, M.V. (327.431) numerically,%: C 80.61; H 6.48; N 12.81
    5- (4 - (+) - 3 -methyl-1 -pentylphenyl) -2 (4-cyanophenyl) -Pyrimidine, m.p. 86,15CJ t. Rev. 212.2 ° C, yield 80%.
    Found %: from 80.90; H 6.79; N 12.31
    COO, H “,, NO,, M.V. (341.458) Calculated,%: C 81.08f H,
    11 12.31
    5- (4 - (- f) -4-methyl-1-hexylphenyl) -2- (4-cyanophenyl) -pyrimidine, m.p.
    80.4 ° C, so on. 204 ,, yield 91%.
    Found,%: C 81.09) H 7.09;
    N 11.82,
    .lsNi / M.V. (355.485) Calculated,%: C, 80.96; H 7.10; N 11.84
    The compounds obtained by the proposed method differ from the known optically active liquid crystal compounds by higher values, higher temperature,
    ranges of mesophases and high dielectric anisotropy (€ +20), which is confirmed by the data given in Table. 1 and tab. 2
    In tab. 1 shows the phase transition temperatures of known optically active liquid crystal compounds.
    In tab. 2 shows the phase transition temperature of the compounds obtained by the proposed method. Note: СX () TfinTj. -X T rmsektikika; cholesterol; monotropic transition; solid crystal-smectic transition temperature J smectic-cholesterol transition temperature; melting point in isotropic liquid. . f -, Table 2
    权利要求:
    Claims (2)
    [1]
    The invention The method of obtaining mesomorphic optically anti-derivative 4-cyanephenylpyrimidines of the general formula IJ 65 CgH; -CK-I / GDV Z is a group - (CH) „or (CH5.) P with n 1-4, characterized in that the compound is common where Z has the above in the form of optically active is subjected to dehydration. Sources of information, formulas P taken into account during the examination // "p-terphenyls and some chiral values,
    [2]
    2. David T. The preparation of the antipodes of .Q nitrlles. Chemical Review, 1948, 8673028, 1. Gray G.W., McDonnell O.G. Synthesis and liquid crystal properties of chiral alkyl cyanobiphenyls and compounds derived from biphenyls, Mo1. Cryst lig. Cryst. 1976.37, l89211. № 2, p. 257.
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    同族专利:
    公开号 | 公开日
    IT1095457B|1985-08-10|
    JPS53116387A|1978-10-11|
    FR2383921B1|1980-06-20|
    FR2383921A1|1978-10-13|
    NL7801718A|1978-09-20|
    CA1082706A|1980-07-29|
    GB1594085A|1981-07-30|
    IT7820740D0|1978-02-28|
    DE2811001A1|1978-10-05|
    DD137712A5|1979-09-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE4108448A1|1991-03-13|1992-09-17|Merck Patent Gmbh|High holding ratio electro=optical system - contg. liq. crystal mixt. with specified component and polymeric medium made from aromatic fluorine contg. precursor|
    DE4307243A1|1992-03-13|1993-10-14|Hoffmann La Roche|Prepn. of di:aryl cpds. useful for producing liquid crystal cpds. - involves coupling of aryl halide with aromatic boron acid derivs. using palladium catalyst|US4062798A|1975-09-19|1977-12-13|Hoffmann-La Roche Inc.|Phenylpyrimidine derivatives|US4528114A|1981-12-18|1985-07-09|Hoffmann-La Roche Inc.|Acetylenes|
    JPH0670020B2|1984-04-03|1994-09-07|チッソ株式会社|Substituted pyridazines|
    DE3515373A1|1985-04-27|1986-11-06|Merck Patent Gmbh, 6100 Darmstadt|NITROGENIC HETEROCYCLES|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH342177|1977-03-18|
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