• 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:
    The present invention relates to novel aromatic alkane derivatives represented by the following general formula (I): <IMAGE> (I) wherein Ar stands for a substituted or unsubstituted phenyl or naphtyl group, R1 stands for a methyl, ethyl or isopropyl group and R2 stands for a hydrogen atom or a methyl group, or R1 and R2 together with the carbon to which they are attached jointly represent a substituted or unsubstituted cycloalkyl group, and R3 stands for a fundamental group of an alcohol which is usually used in a form of R3OH as to natural or synthetic pyrethroids, and also to processes for the preparation of these compounds and the uses of these compounds. These compounds of the present invention have excellent insecticidal and acaricidal activities while the toxicities of these compounds are very low.
    公开号:SU1524808A3
    申请号:SU843806472
    申请日:1984-10-22
    公开日:1989-11-23
    发明作者:Накатаки Киюоси；Нумата Сатоси；Кодака Кеньи；Ода Кенджо；Сираиси Сиро；Удагава Такатоси
    申请人:Мицуи Тоатцу Кемикалз, Инк (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing new derivatives of aromatic alkanes of the general formula:

    ; AG-C-CH2CH2B5 (1
    g
    de Ag - naphthyl; phenyl unsubstituted or substituted by identical or different substituents, such as halogen, lower alkyl, lower haloalkyl, lower alkoxy lower gadoidalkeniloksi-, nizpvsy haloalkoxy, lower apkenil, lower galoidal- kenil, Cj-alkynyloxy, lower alkoxyalkyl, lower alkoxy sicarbonyl, lower halonalkoxycarbonyl, phenoxy, methylenedioxy, and cyanogroup;
    methyl, ethyl, isopropyl; hydrogen or methyl, and R, together with the carbon atom to which they are attached, form a cycloapkyl group Cj-C possibly substituted by a halogen atom; groups of general formula:
     J
    -CH-r4
    ,
    or
    TO,
    AT,
    t-x
    (Ii)
    B.
    (Iii)
    (Cv)
    where A is oxygen, R is hydrogen; RJ - phenylmercaptote, benzyl,
    a benzoyl, or pyridyloxy, or phenoxy group, optionally substituted by a halogen atom or a C, -C-alkoxy group; R ,, R is hydrogen, a halogen atom;
    RI is tetrahydrophthalimidyl with insecticide-acaricidal activity and can be used in agriculture.
    The aim of the invention is to obtain new aromatic derivatives.
    0
    five
    about
    five
    0
    five
    0
    five
    0
    five
    alkanes that exhibit higher insecticidal and acaricidal activity.
    Example 1 Preparation of 1- (3- -Phenoxyphenyl) -A- (4-mets1phenyl) -4- -methylpentane
    1. 1- (3-phenoxyphenle) -A- (4-methylphenyl) -4-methyl-2-pentane and 1- (3-phenoxyphenyl) -4- (4-methylphenyl) -4-methyl -1-pentane.
    a) To 50 ml of ethanol was added 5.3 g of 2- (4-methylphene1) -2-methyl-3-butanone, 6.0 g of 3-phenoxybenzaldehyde and 6.0 g of KOH, and the mixture was stirred at room temperature. temperature for 1 h 20 min. Then the reaction mixture is poured into 300 ml of water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated under reduced pressure and 10.4 g of crude 1- (3-phenoxyphenyl) -4- (4-methylphenyl) -4-methyl-1-penten-3-one is obtained, then the crude the product is purified by column chromatography on 250 g of silica gel (eluent-benzene) to give 6.8 g of pure 1- (3-phenoxyphenyl) -4- (4-methylphenyl) -4-methyl-1-penten-3-one, Front ° 1.6121.
    V;:,; 7c, cm-: 1680, 1605, 1570, 1485, 1240, 1055.
      h, ppm: 1.47 (singlet, 5H); 2.32 (singlet, SN); 6.3-7.6 (multiplet, 15H).
    b) 1.4 g of lithium aluminum hydride was added to 10 ml of dry ether and a solution was carefully added dropwise.
    9.7 g of aluminum chloride in 20 ml of ether. Then, the solution obtained by adding 7.4 g of 1- (3-phenoxyphenyl) -4- (4-methylmethyl) -4-methyl-1-penten-3-one, obtained as described in the above, is added dropwise to the mixture. Stage a, in 10 ml of ether, and refluxing for 30 minutes. Ethyl acetate and then water were added dropwise to the reaction mixture while cooling, and the mixture was extracted with benzene. The benzene extract is washed with water and dried, and the solvent is evaporated under reduced pressure. The residue is purified by column chromatography on silica gel (150 g), a mixture of benzene and hexane 1: 2 is used as eluent, and 3.6 g of a mixture of 50% 1- (3-phenoxyphenyl) -4- (4-methyl-phenyl) -4 is obtained -met-2-pentene and
    50% of 1- (3-phenoxyphenyl) -4- (4-methylphenyl) -4-methyl-1-pentene. 1.5882.
    20, rn
    CH4 (SG4GI mmks
    cm-: 1590, 1500, U95, 1455,, 1225, 980, 825, 700.
    , ppm: 1.32 (singlet.
    about gms
    6H “1/2); 1.36 (singlet, 6H1 / 2); 2.28 (singlet, zni / 2); 2.31 (singles years, GH) 1/2); 2.43 (doublet, I - p 7.1 Hz, 2H 1/2: corresponds to megylenic protons in 1-pentene); 3.32 (doublet, I 5.7 Hz, 2Hl1 / 2: corresponds to methylene protons in 2- -pentene); 5.5-6.4 (multiplet, 2H); 6.6-7.4 (multiplet, 13H).
    2. 1- (3-Phenoxphenyl) -4- (4-methylphenyl) -4-metshshentan.
    To 30 ml of ethyl acetate was added and
    are benzene. The benzene extract is washed with water, the residue is dried. The residue is purified by column chromatography on 210 g of silica gel (eluent is benzene) and 5.9 g of pure 1- - (3-phenoxyphenyl) -4- (3-trifluoromethyl phenyl) -4-methyl-1-penten-3-one is obtained . pg - 1.5820.
    CHMSTI. ,,
    ten
    ““ COP, SM-: I690j 1610, 1590, 1580, 1490, 1460, 1330, 1240, 1165, 1125, 1075, 1060, 1000, 980, 805, 705, 695.
    b) To 10 MP of dry ether added. 0.75 g of lithium aluminum hydride and
    a solution of 5.0 g without aqueous aluminum chloride in 20 ml of dry ether is added dropwise. A solution is then added dropwise to the mixture.
    1.9 g of a mixture of 502 1- (3-phenok-20 by dissolving 4.4 g of 1- (3-phenoxyfesiphenyl) -4- (4-methylphenyl) -4-methyl-yl) -4- (3-trifluoromethylphenyl)) is dissolved -4-me-2-pentene and 50% 1- (3-phenoxyphenyl) -til-1-penten-3-one obtained on
    -4- (4-metsh1fensh1) -4-methyl-1-pentenadium a, in 20 ml of dry ether, and
    1524808
    are benzene. The benzene extract is washed with water, the residue is dried. The residue is purified by column chromatography on 210 g of silica gel (eluent is benzene) to obtain 5.9 g of pure 1- - (3-phenoxyphenyl) -4- (3-trifluoromethyl-phenyl) -4-methyl-1-penten-3-one . pg - 1.5820.
    CHMSTI. ,,
    ““ COP, SM-: I690j 1610, 1590, 1580, 1490, 1460, 1330, 1240, 1165, 1125, 1075, 1060, 1000, 980, 805, 705, 695.
    b) To 10 MP of dry ether, add 0.71 g of lithium aluminum hydride and
    a solution of 5.0 g of anhydrous aluminum chloride in 20 ml of dry ether is added dropwise. A solution is then added dropwise to the mixture.
    and 0.4 g of 5% palladium over coal was added, and then the mixture was stirred under an overpressure of 20 kg / cm with gaseous hydrogen at room temperature. After 3 hours, the palladium-carbon was removed by filtration and the ethyl acetate was evaporated under reduced pressure.
    The residue was purified by column chromatography on 50 g of silica gel (a mixture of benzene and hexane 1: 2 was used as an eluent) to obtain 1.8 g of the desired 1- (3-phenoxyphenyl) -4- (4-methylphenyl) -4-methylpentane.
    10.0
    thirty
    n in
    . mchs
    1.5710.
    cm: 1595, 1495, 1260, 1225, 820, 700.
      ppm: 1.24 (singlet, 6H); 1.0-1.7 (multiplet, 4H); 2.25 (singlet, SN); 2.42 (triplet, I 7.5 Hz, 2H) 5 6.55-7.25 (multiplet, 13H).
    Example 2. Preparation of 1- (3- -phenoxyphenyl) -4- (3-trifluoromethylphenyl) -4-methylpentane.
    1. Preparation of 1- (3-phenoxyphenyl) -4- - (3-trifluoromethylphenyl) -4-methyl-2- -pentene and 1- (3-phenoxyphenyl) -4- (3--trifluoromethylphenyl) -4-methyl- 1-pentene.
    a) To 30 ml of ethanol, 4.3 g of 2- (3-trifluoromethylphensh1) -2-methyl-3-butanol was added, 3.7 g of 3-phenoxybenne was boiled under reflux for 25 minutes. While cooling with ice water, this acetate is added to the reaction mixture and then water. The reaction mixture is extracted with benzene, the benzoic extract is washed with water, and the dried solvent is evaporated under reduced pressure to obtain 4.4 g of residue.
    The residue is purified by column chromatography on 100 g of silica gel (as the eluent, a mixture of b ash and 1: 2 hexane) is used to obtain 2.2 g of a mixture of 70% 1- (3-phenoxyphenyl-4- (3-trifluoromethylphenyl) -4- methyl- -2-pentene and 30% 1- (3-phenoxyphenyl-4- (3-trifluoromethylphenyl) -4-methyl35
    40
    -pentene. .
    , UUCTklU
     / iax
    1.5517,
    45
    50
    SM: 1590, 1500, 130 1260, 1220, 1175, 1140, 1080, 705 695.,
    eHtAis ppm: 1.40 (singlet, 6H); 2.45 (doublet, I - 6.9 Hz, 2H "30/100: corresponds to methylene to protons in 1-pentene); 3.31 (duplicate I 4.8 Hz, 2H 70/100: corresponding to methylene protons in 2-pentene) 3.5-6.4 (multiplet, 2H); 6.45-7, (multiplet, 13H).
    2. 1- (3-phenoxyphenyl) -4- (3-trizaldehyde and 1.0 g KOH, and a mixture of fluoromethinelphenyl) -4-methpentane. stir at room temperature. To 25 ml of ethyl acetate is added overnight. The reaction mixture is poured into 300 ml of water and extraHE1, 2 g of a mixture of 70% 1- (3-phenoxyphenyl-4- (3-trifluoromethylfenkl) -4-methyl
    boil with reflux for 30 minutes. While cooling with ice water, ethyl acetate was added to the reaction mixture, and then water. The reaction mixture is extracted with benzene, the benzene extract is washed with water, dried, the solvent is evaporated under reduced pressure and obtain 4.4 g of residue.
    The residue is purified by column chromatography on 100 g of silica gel (a mixture of benzene and hexane 1: 2 is used as eluent) to obtain 2.2 g of a mixture of 70% 1- (3-phenoxyphenyl) -4- (3-trifluoromethylphenyl) -4-methyl - -2-pentene and 30% 1- (3-phenoxyphenyl) - -4- (3-trifluoromethylphenyl) -4-methyl1
    -pentene. .
    , UUCTklU
     / iax
    1.5517,
    five
    0
    SM: 1590, 1500, 1305, 1260, 1220, 1175, 1140, 1080, 705, 695.,
    eHtAis ppm: 1.40 (singlet, 6H); 2.45 (doublet, I - 6.9 Hz, 2H “30/100: corresponds to methylene protons in 1-pentene); 3.31 (doublet, I 4.8 Hz, 2H 70/100: corresponds to methylene protons in 2-pentene); 3.5-6.4 (multiplet, 2H); 6.45-7.6 (multiplet, 13H).
    2. 1- (3-Phenoxyphenyl) -4- (3-three fluoromethylphenyl) -4-metpentane. To 25 ml of ethyl acetate was added.
    fluoromethylphenyl) -4-metnpentane. To 25 ml of ethyl acetate was added.
    1.2 g of a mixture of 70% 1- (3-phenoxyphenyl) - -4- (3-trifluoromethylfencl) -4-methyl71524808
    2-penthen and 30Z 1- (3-phenoxyphenyl) - -4- (3-trifluoromethyphenyl) -4-methyl-1- -pentene, and 0.40 g of 5Z palladium on coal, and the mixture is displaced under overpressure and 20 kg / After 8 hours, palladium-carbon was removed by filtration, the solvent was evaporated under reduced pressure, and 1.2 g of residue was obtained. The residue is purified by column chromatography on 25 g of silica gel (a mixture of benzene and hexane 1: 2 is used as eluent), to obtain 0.8 g of 1- (3-phenoxyphenyl) -4- (3-trifluoromethylphenyl) -4-metnpentane
     f (. l g t
    Hd
    to
    15
    . clean
    "1.5373.
    cm-: 1580, 1480, 1330,
    1245, 1210, 1160, 1120, 1170, 695, 680.
      h / m 1.31 (singlet, 6H); 1.1-1.8 (multiplet, 4H); 2.47 (triplet, I - 6.6 Hz, 2H) | 6.6-7.6 (multi-bullet, 13H),
    Example 3. Preparation of 1- (3- -phenoxy-4-ch1) torphenyl) -4- (4-ethoxyphenyl) -4-methylpentane.
    1. Preparation of 1- (3-phenoxy-4-fluoro-phenyl) -4- {4-ethoxyphenyl) -4-methyl-2- -pentene and 1- (3-phenoxy-4-fluorophenyl) -4- ( 4-ethoxyphenyl) -4-metsh1-1-pentene.
    a) In the same way as described in step a in 1. of example 2, 12.0 g of residue are obtained using
    6.2 g of 2- (4-ethoxyphenyl) -2-methyl-3-β-butanone and 6.5 g of 3-phenoxy-4-fluoro-benzaldehyde. The residue is purified by column chromatography on 200 g of silica gel (eluent is benzene) to obtain
    5.8g 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxy-1) -4-methyl-1-penten-3-one.
    1.5900.
    cm-: 1690, 1610, 1590, 1510, 1490, 1290, 1270, 1250, 1210, 1185, 1120, 1060, 820, 750, 690.
    b) In the same way as described in stage b in 1. in example 2, receive
    3.9g residue using 4.1g
    20
    25
    thirty
    35
    40
    15.7
    pc
    I ia ".c
    eight
    -4-fluorophenyl) -4- (4-ethoxyphenyl) -4-methyl-1-pentene.
     - 1.5745.
    VM-HC, cm-: 1610, 1585, 15 1490, 1290, 1245, 1210, 1180, 1115 1045.65, 825, 690.
    HMS, ppm: 1.2-1.5 (cartoon
    lash,); 2.39 (doublet, I -7.1 2H 55/100: corresponds to methylenes to protons in 1-pentene); 3.27 (double
    1-5.0 Hz, 2HG45 / 100: corresponds to methylene protons in 2-pentene
    .3.8-4.1 (multiplet, 2H) j 5.4-6.3 (multiplet, 2H); 6.5-7.4 (multiplet, 12H).
    2. 1- (3-Phenoxy-4-fluorophenyl) -4- (4-ethoxy-1) -4-methylpentane. In the same way as described in
    2. Example 2, restore 0.9 g of a mixture of 45% 1- (3-phenoxy-4-fluorophenyl-4- (4-ethoxyphenyl) -4-methyl-2-penta and 55% 1- (3-phenoxy- 4-fluorophenide) -4- (4-ethoxyphenyl) -4-methyl-1-penta and obtain 1.0 g of residue. The residue is purified on a 20 g silica gel column chromatograph (using benzene mixture as eluent
    and hexane 2: 3), and 0.80 g of 1- (3-phenoxy-4-fluorophenyl) -4- (4-is syphenyl) -4-metshpentane is obtained.
     . 1.5578.
     , cm-: 1585, 1510, 1490 1290, 1270, 1240, 1210, 1180, 1115 1045,820, 750, 685.
    ppm: 1.22 (singlet
    6H); 1.36 (triplet, I 6.9 Hz, HH 2.39 (triplet, I 7.7 Hz, 2H); 3.91 (quartet, 1 6.9 Hz, 2H); 1, 1.7 (multiplet , 4H); 6.5-7.4 (mule tiplet, 12H).
    Example 4. Preparation of 1- (3- -phenoxyphenyl) -4- (3,4-methyl dioxyphenyl) -4-methylpentane.
    1. Preparation of 1- (3-phenoxyphenyl) 5 - (3,4-methyl 1-dioxyphenyl) -4-methyl--1-pentene and 1- (3-phenoxyphenyl) -4- - (3,4-methy-ene-dioxyphenyl) -4 -methyl -2-pentene.
    a) A mixture of 10 g of 2- (3,4-methylenediamine
    1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxy-50 syphenyl) -2-methyl-3-butanone, 9.6 g
    3-Phenoxybenzaldehyde, 50 ml of ethanol and 2 g of KOH are stirred at 30 minutes. After that, the reaction mixture is drunk in 300 ml of water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated off under reduced pressure and 23 g of residue are obtained.
    phenyl) -4-methyl-1-penten-3-one obtained above in a. The residue is purified by column chromatography on 80 g of silica gel (a mixture of benzene and hexane 2: 3 is used as eluent), and 1.44 g of a mixture of 45% 1- (3-phenoxy-4-fluorophenyl) -4- (4- ethoxyphenyl) -4- -methyl-2-pentene and 55% 1- (3-phenoxy
    o
    five
    0
    five
    0
    five
    0
    eight
    -4-fluorophenyl) -4- (4-ethoxyphenyl) -4-methyl-1-pentene.
     - 1.5745.
    VM-HC, cm-: 1610, 1585, 1510, 1490, 1290, 1245, 1210, 1180, 1115, 1045.65, 825, 690.
    HMS, ppm: 1.2-1.5 (multiplet,); 2.39 (doublet, I -7.1 Hz, 2H 55/100: corresponds to methylene protons in 1-pentene); 3.27 (doublet,
    1-5.0 Hz, 2HG45 / 100: corresponds to methylene protons in 2-pentene);
    .3.8-4.1 (multiplet, 2H) j 5.4-6.3 (multiplet, 2H); 6.5-7.4 (multiplet, 12H).
    2. 1- (3-Phenoxy-4-fluorophenyl) -4- (4-ethoxy-1) -4-methylpentane. In the same way as described in
    2. Example 2, restore 0.9 g of a mixture of 45% 1- (3-phenoxy-4-fluorophenyl) - -4- (4-ethoxyphenyl) -4-methyl-2-pentene and 55% 1- (3 -phenoxy-4-fluorophenide) -4- (4-ethoxyphenyl) -4-methyl-1-pentene and obtain 1.0 g of residue. The residue is purified by column chromatography on 20 g of silica gel (benzene mixture is used as eluent
    and hexane 2: 3), and 0.80 g of 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxyphenyl) -4-metsh1pentana is obtained.
     . 1.5578.
     , cm-: 1585, 1510, 1490, 1290, 1270, 1240, 1210, 1180, 1115, 1045.820, 750, 685.
    ppm: 1.22 (singlet.
    6H); 1.36 (triplet, I 6.9 Hz, 3N); 2.39 (triplet, I 7.7 Hz, 2H); 3.91 (quartet, 1 6.9 Hz, 2H); 1.0-1.7 (multiplet, 4H); 6.5-7.4 (multiplet, 12H).
    Example 4. Preparation of 1- (3- -phenoxyphenyl) -4- (3,4-methyl, dioxyphenyl) -4-methylpentane.
    1. Preparation of 1- (3-phenoxyphenyl) -4-5 - (3,4-methylenedioxyphenyl) -4-methyl--1-pentene and 1- (3-phenoxyphenyl) -4- - (3,4-methyedioxyphenyl ) -4-methyl--2-pentene.
    a) A mixture of 10 g of 2- (3,4-methylenedioxyphenyl) -2-methyl-3-butanone, 9.6 g
    3-Phenoxybenzaldehyde, 50 ml of ethanol and 2 g of KOH are stirred at for 30 minutes. After that, the reaction mixture is drunk in 300 ml of water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated off under reduced pressure and 23 g of residue are obtained.
    The residue is purified by column chromatography on silica gel (eluent is benzene), and 15.3 g of pure 1- - (3-phenoxyphenyl) -4- (3,4-methylenedioxy-phenyl-3-one) are obtained. ,
     , 1.6208.
    MA KS, CM-: 1705, 1620, 1600, 1590, 1515, 1495, 1460, 1250, 1080, 1070, 1050, 940, 825, 690.
     ppm: 1.43 (singlet, 4H); 5.85 (singlet, 2H); 6.36-7.70 (multiplet, 14H).
    B) In the same way as described in b of step 1 of Example 1, 12 g of 1- (3-phenoxyphenyl) -4- (3,4-methylenedioxy-phenyl) -4-metsh1-1-penten-3-one obtained At the top of the a, they are processed and 2.0 g of a mixture of 40% 1- (3-phenoxy-phenes1) -4- (3,4-methylenedioxyphenyl) -4-methyl-2-pentene and 60% 1- (3 - -Phenoxyphenyl) -4- (3,4-methylenedioxyphenyl) -4-methyl-1-pentene.
    Pi
    one
    1.5966.
     rcc cm-: 1660, 1590, 1510, 1495, 1455, 1250, 1220, 1050, 945, 820, 700.
    if tms, ppm: 1.2-1.3 (multiplet, 6H); 2.39 (doublet, 1-5.9 Hz, 2H 60/100: corresponds to methylene protons of 1-pentene); 3.29 (doublet, I 5.4 Hz, 2H "40/100: corresponds to methylene protons of 2-pentene); 5.4-6.4 (multiplet, 4H); 6.5-7.4 (multiplet, 12H).
    2. 1- (3-Phenoxyphensh1) -4- (3,4-methylenedioxyphenyl) -4-methylpentane.
    As described in 2. example 1, a mixture of 1- (3-phenoxyphenip) -4- (3,4-methylenedioxyphenyl) -4-methyl-1-pentene and 1- (3-phenoxyphenyl) -4- ( 3,4-β-methylenedioxyphenyl) -4 methyl-2-pentene, prepared in step 1 above, is treated to give 1- (3-phenoxyphenyl) -4- (3,4-methylenedioxyphenyl) -4-metsh1enpentane quantitatively
    P
    70.0
    D
    about UUCTblM
    maize
     1.5824.
    , cm-: 1570, 1490, 1475, | 1430, 1235, 1200, 1150, 1095, 1025, 925, 800, 740, 680.
    ; “Frv c, ppm: 1.07-1.70 (multiplet, 4H); 1.23 (singlet, 6H); 2.46 (triplet, 2H); 5.82 (singlet, 2H); 6.5-7.4 (multiplet, 12H).
    Example 5. Obtaining 1- (3-, -phenoxyphenyl) -4- (4-methoxyphenyl) -4- -methylpentane.
    1. 1- (3-Phenoxyphenyl) -4- (4-methoxy phenyl) -4-methyl-1-pentene and 1- (3-phenoc-
    1524808
    ten
    0
    syphenyl) -4- (4-methoxyphenyl) -4-methyl-2-pentene.
    a) A mixture of 10 g of 2- (4-methoxyphenyl) - -2-methy-1-3-butanone, 33.7 g of 3-phenobisibenzaldehyde, 80 ml of methanol and 4.0 g of KOH are stirred at AO C for 2 hours, and then processed as described in a and stage 1 of example 1, and receive 25 g of 1- (3-phenoxyphenyl) - -4- (methoxyphenyl) -4-metnp-1-penten-3-one. p j
    . VMcTkiff
    - 1,6094.
     1680, 1600, 1575,
    5 1480, 1230, 1050, 880, 825, 750, 685.
     ppm: 1.44 (singlet, 6H); 3.69 (singlet, ZN); 6, behind-7.61 (multiplet, 15H).
    B) In the same way as described in b of stage 1 of example 1 ,. 23.7 g of 1- (3-phenoxyphenyl) -4- (4-methoxyphenyl) -4-methyl-1-penten-3-one, semi
    9.0 g of a mixture of 40% 1- (3-phenoxyphenyl) -4- (4-methoxyphenyl) -4-methyl-2-pentene and 60% 1- - (3-fvnoxyfenkp) - 4- (4-methoxyphenyl) -4-methyl-1-pentene. 1.5948.
    Lp a
     "", Cm-: 1620, 1590, 1520,
    1500, 1450, 1255, 1220, 1190, 1040, 835, 700.
     ppm: 1.20-1.40 (multiplet, 6H); 2.40 (doublet, 1 - 6.5 Hz, 2H 60 / 100i corresponds to meth-foam protons in 1-pentene); 3.28 (doublet, 1-5.6 Hz, 2H 40/100: corresponds to methylene protons in 2-pentaVe); 3.6-3.8 (multiplet, ЗН); 5.2-6.4 (multiplet, 2H) j 6.6-7.4 (multiplet, 13H).
    In the same manner as described in 2 examples, a mixture of 1- (3-phenoxy-phenyl) -4- (4-methoxyphenyl) -4-metsh1-2-pentene and 1- (3-phenoxyphenyl) -4- (4- -methoxyphenyl) -4-methyl-1-pentene, prepared above in step 1, and 1- - (3-phenoxyphenyl) -4- (4-methoxyphenyl) -4-methylpentane in quantitative yield.
    one
    five
     9.1
    mystic
     MOM
    1.5774.
    cm-: 1610, 1580, 1515, 1485, 1250, 1215, 1180, 1035, 825, 755, 690.
    t "ppm: 0.88-1.73 (multiplet, 4H); 1.26 (singlet, 6H); i 2.46 (triplet, 2H); 3.73 (singlet, OH), 6.6-7.4 (multiplet, 1-ЗН).
    h15
    Example 6 Preparation of 1- (3-β-pheno-1-cis-4-fluorophenyl) -4- (4-methoxy-phenyl) -4-mWnppentane
    1. A mixture of 7.6 g of 2- (4-methoxyphenyl) -2 -2-methyl-3-buta-ol, 8.5 g of 3-phenoxy-4-fluorobenzaldehyde, 30 ml of methanol and 2 g of KOH are stirred for 2 hours. . The reaction mixture is treated in the same manner as described in step 1 of example 1, and 5 g of 1- (3-phenoxy-4-fluorophenip) -4- (4-methoxy-diphenyl) -4-metsh-1 -penten-3 is obtained. -one, 1.6058.
    ni
    V.. cm- ; 1680, 1605, 1580,
    1420, 1290, 1270, 1D50, 1205, 1180, 1105, 1060, 1030, 980, 825, 745, 680.
    “Gms J ppm: 1.45 (singlet, 4H); 3.74 (singlet, ZN); 6.26-7.61 (multiplet, 15H).
    In the same manner as described in b of step 1 of Example 1, 4.2 g of 1- (3-phenoxy-4-fluorofensch1) -4- (4-methoxy-xiphenyl) -4-methyl-1-penten-3-one are treated with , obtained above in 1, and obtain 2.8 g of a mixture of 50% 1- (3-phenoxy-4-fluorophenyl) -4- (4-methoxyphenyl) -4-metsh-2-pentene and 50% 1- (Z-phenoxy-1-fluorophenyl) -4- (4-methoxyphenyl) -4-methyl-1

    -pentene.
    and, 9
    P
    Cystics
     1.5764.
    cm: 1605, 1585, 1510 1490, 1290, 1270, 1245, 1210, 1180, 1110, 1035, 825, 680.
    Vccii o tms
    ppm: 1.2-1.4 (m


    plet, 6H); 2.38 (doublet, I 6.8 Hz 2H "50/100: corresponds to methylene protons of 1-pentene); 3.40 (doublet, I 5.6 Hz, 2H 50/100: corresponding to methylene protons of 2-pentene); 3.6-3.8 (multiplet, ЗН); 5.2-6.3 (multiplet, 2H); 6.5-7.4 (multiplet, 12H),
    2. In the same way as described in 2, Prime 1, a mixture of 1- (3-fenoc Si-4-fluorofensch1) -4- (4-methoxyphenyl) -4-methyl-2-pentene and 1- (3- phenoxy-4-fluorophenyl) -4- (4-methoxyphenyl) -4-methyl-1-pentene, obtained above in 1., and 1- (3-phenoxy-4-fluorophenyl) -4- ( 4-methosphenyl) -4-methylpentane. 1.5642.
    1C, with
    m "kg, cm-: 1620, 1600, 1520


    1500, 1430, 1285, 1260, 1220, 1195, 1175, 1125, 1040, 835, 755, 695.
     ppm: 0.92-1.67 (multiplet, 4H); 1.22 (singlet, 6H); .
    0
    12
    2.39 (triplet, 2H); 3.68 (singlet, ZN); 6.5-7.4 (multiplet, 12H).
    Example 7 Preparation of 1- (3- -Phenoxyphenyl) -4- (4-chlorophenyl) -4-methyl-hexane
    In the same manner as described in the example, 3- (4-chlorophenyl) -3-methyl-2-pentanone and 3-phenoxybenzaldehyde are treated and 1- (3-phenoxyphenyl) -4- - (4-chlorophenyl) - 4-methylgvsane.
    P
    it, t
    g
    qUCTtiu
    1.5748,
    five
    ““ “Cm: 1590, 1500, 1455, 1260, 1220, 1020, 825, 700.
    tm s ppm; 0.63 (triplet, I 7 Hz, ЗН); 1.08-1.9 (multiplet, 6H); 1.21 (singlet, SN); 2.44 (triplet, 2H); 6.6-7.4 (multiplet, 13H).
    Example 8. Preparation of 1- (3-phenoxyphenyl) -4- (4-chlorofensh1) -4-methylpentane.
    The same as described in. As an example, an equivalent mixture of 5 V, / -dimethyl- (4-chlorofensh1) -acetaldehyde and 3-phenoxyacetophenone is treated to obtain 1- (3-phenoxyphenyl) -4- (4-chlorophenfs1) -4-methylpentane. nV - 1.5786.
    0
     tiplet, 12H).
    vTJ iIc, cm-: 1600, 1520, 1500, 1430, 1300, 1285, 1220, 1170, 1125, 1020, 830, 765, 695.
    tms, ppm: 0,, 72 (multiplet, 4H); 1.26 (singlet, 6H); 2.42 (triplet, 2H); 6.67-7.40 (mul0
    five
    0
    Example 9. Obtaining 1- (3- -phenoxyphenyl) -4- (4-isopropoxyphenyl) -4-methylpentane.
    1. A mixture of 5.0 g of 1- (3-phenoxyphenyl) -4- (4-methoxyphenyl) -4-methylpentane, 30 MP of a 47% aqueous solution of hydrogen bromide and 30 ml of acetic acid is refluxed in for 8 hours. The reaction mixture is poured into water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated under reduced pressure, the residue is purified by column chromatography on silica gel (eluent is benzene), and 4.2 g of 1- (3-phenoxy-phenyl) -4- (4-hydroxy-phenesh1) - 4-methylpene
    1.5870.
    , cm-: 3400, 1610, 1580,
    1515, 1485, 1440, 1240, 1210, 825, 755, 690, 675.
     ppm: 1.00-1.68
    13
    (multiplet, 4H); 1.20 (singlet, 6H); 2.43 (triplet, 2H); 5.52 (broad singlet, 1H); 6.56-7.38 (multiplet, 13H).
    2. A mixture of 0.5 g of 1- (3-phenoxyphenyl) -4- (4-hydroxy-1) -4-methylpentane, 1.5 g, 3 ml of isopropyl bromide and 20 ml of dimethylformamide is stirred for 2 h. The reaction mixture is drunk in water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated under reduced pressure, the residue is purified by column chromatography on silica gel (eluent is benzene), and 0.3 g is obtained - (3-phenoxyphenyl) -4- (4-isopropoxy-phenyl) -4- methylpentane.
    15
    " about
    , UUC T hlU MOIHC
     1.5682.
    cm
    1605, 1580, 1510, 1485, 1380, 1245, 1120, 955, 825, 755, 68.
      ppm: 1.02-1.71 (multiplet, 16H); 2.45 (triplet, 2H); 4.28-4.56 (multiplet, 1H); 6.57 - 7.88 (multiplet, 13H).
    Example 10. Preparation of 1- (3- -phenoxy-4-fluorophenyl) -4- (4-difluoro-methoxy-phenyl) -4-methylpentane.
    1. As described in Example 9, 1 g of 1- (3-phenoxy-4- -fluorophenyl) -4- (4-methoxyphenyl) -4- -methylpentane is treated to give 0.6 g of 1- - (3 -phenoxy-4-fluorophenyl) -4- (4-hydroxyphenyl) -4-metsh1pentana.
    Front, 1.5760.
    chkstyi
    fAd COP
    CM
    3360, 1620, 1285, 1220,
    1600, 1130,
    1520, 1500, 1435, 840, 760, 700.
      ppm: 1.02-1.67 (multiplet, 6H); 1.21 (singlet, 6H); 2.39 (triplet, 2H); 5.24 (broad singlet, 1H); 6.52-7.35 (multiplet, 12H).
    2. Chlorodifluoromethane is passed through a mixture of 0.5 g of 1- (3-phenoxy-4-α-fluorophenyl) -4- (4-hydroxyphenyl) -4-methylpentane, obtained above in 1., 1.0 g of KOH and 20 ml of acetonitrile under stirring at 60 ° C for 30 minutes. Regulatory mixture is drunk in water and extracted with benzene. The benzene extract is washed with water, dried, the solvent is evaporated under reduced pressure, the residue is purified by column chromatography on silica gel (eluent benzene), and 0.4 g of 1- (3-fenok
    ); ,
    1524808
    14
    0
    five
    0
    five
    0
    si-4-fluorophenyl) -4- (4-difluoromethoxy-phenyl) -4-methylpentane.
    15, t Immerste
    1.5414. 1600,
    five
    “„ Ns I -. , 1520, 1500, 1435, 1395, 1285, 1220, 1140, 1050, 840, 820, 760, 700.
     ppm: 1.02-1.72 (multiplet, 4H); 1.25 (singlet, 6H); 2.42 (triplet, 2H); 6.39 (triplet, I - 35 Hz, 1H); 6.68-7.39 (multiplet, 12H).
    Example 11. Preparation of 1- (3- -phenoxy-4-fluorofensch1) -4- (4-ethoxyphenyl) -4-methylpentane.
    1. To 6.4 g of 3-phenoxy-4-fluorobenzyl bromide, 7 ml of triethyl phosphite was added and the mixture was stirred at 140 ° C for 7 hours. After cooling, 13.1 g of the reaction mixture was purified by column chromatography on silica gel (benzene eluent ) and 6.3 g of diethyl-3-phenoxy-4-fluorobenzyl phosphonate are obtained.
    Г «к7, см: 1590, 1515, 1490, 1270, 1250, 1025, 960, 795.
    “/ Tms, ppm: 1.04-1.50 (multiplet, 5H); 2.93 (doublet, I 21 Hz, 2H); 3.70-4.17 (multiplet, Q 4H); 6.84-7.38 (multiplet, 8H).
    2. Preparation of 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxyphenyl) -4-methyl-1-pentene.
    A solution of 3.0 g of diethyl-3-phenoxy-4-fluorobenzylphosphonate and 10 ml of dry dimethyl-cellosolve are added dropwise to a solution of 0.36 g of 60% sodium hydroxide 5 in 10 ml of dry dimethyl cellosolve. and the mixture is stirred at for 30 minutes. Then a solution of 1.55 g of 3- (4-ethoxyfennl) -3- -methyl-butyl glucose was added dropwise to the mixture in 5 ml of dry dimethyl cellosolve and stirred
    at 50 ° C for 1 hour. The reaction mixture is drunk into water and extracted with benzene. The benzene extract is washed with water, dried with anhydrous sodium sulfate, the solvent is evaporated, the residue is purified by column chromatography on silica gel, and 2.49 g of 1- (3-phenoxy-4-fluorofan) -4- - (4-ethoxyphenyl) -4- is obtained methyl 1-pentene.
    p W 1,5902.
     , cm-: 1610, 1590, 1515, 1425, 1395, 1370, 1295, 1275, 1255, 1215, 1185, 1120, 1050, 970, 825, 750, 690.
    - " five
     h / mnp: 1.28 (singlet, 6H); 1.38 (triplet, I 7 Hz, 3N); 2.36 (doublet, 1 - 8 Hz, 2H); 3.89 (quartet, I - 7 Hz, 2H); 5.54-6.25 (multiplet, 2H); 6.57-7.32 (multiplet, 12H),
    3, Preparation of 1- (3-phenoxy-4-fluoro-phenyl) -4- (4-ethoxyphenyl) -4-methyl-pentane.
    A mixture of 2.0 g of 1- (3-phenoxy-4-fluorophenyl) -4- (4-ethoxy-1) -4-methyl-1-pentene, 0.2 g of 52 palladium on carbon, and 40 ml of ethyl acetate are placed in an autoclave with a capacity of 200 ml, where hydrogen gas is introduced under an overpressure of 10 kg / cm, and stirred at for 3 hours. After cooling, the reaction mixture is filtered, the solvent is evaporated, the residue is purified by column chromatography on a sniggel, and 1.7 g of 1- is obtained ( 3-phenoxy-4-fluoro-phenyl) -4- (4-ethoxyphenyl) -4-metsh1pentana.
    pb
    I
    1.5578.
    The IR and NMR spectra of the above product are identical to the spectra of the product obtained in example 3,
    Example 12 Triphenylphosphine and 3-phenoxy-4-fluoroben zyl bromide Z-phenoxy-4-fluoroben zil bromide taken in a slight excess are mixed in a benzene flask. Hermetically sealed flask is allowed to stand at room temperature overnight to form | NI crystals. The crystals are collected by filtration, washed with benzene
    dried 40 mmol of the obtained bromium a are added to a solution of 40 mmol of phenyl lithium in 150 ml of dry ether in a stream of nitrogen gas, and the mixture is stirred in a stream of nitrogen gas for 3 hours. The precipitated lithium bromide is filtered off, and 40 mmol of 3- (4-toxyphenyl) -3- -methylbutylaldehyde is added to the filtrate while cooling, and the mixture is heated to remove ether and stirred at 65 ° C for 3 hours. The reaction mixture is then drunk into water and extracted with benzene, the benzene extract is washed with water, dried, the solvent is evaporated, the solvent is purified by column chromatography on silica gel to obtain 1- (3- -phenoxy-4-fluoropensh1) -4- (4-ethoxyphenyl) -4-ethyl-1 -penthen. nj 1,5902.
    ten
    524808
    The IR and NMR spectra of the indicated product are identical to the spectra of the product obtained in accordance with 2. example 11.
     Example 13. Preparation of 1- (3- -benzoylphenyl) -4- (3-bromo-4-ethoxyphenyl) -4-methylpentane.
    1. 1- (3-Benzoylphenyl) -4- (3-bromo-4-ethoxyphenyl) -4-methyl-1-pentene.
    0.1 g of 60% sodium hydride was added to 5 ml of anhydrous dimethyl cellosolve, 0.9 g of diethyl-3-benzoyl benzylphosphonate (prepared in accordance with the first example of Example 11) and a mixture of stirred at 50 ° C for 30 nins. Then a solution of 0.6 g of 3- (3-bromo-4-ethoxyphene-1) -3-methylbutanal in 2 ml of dimethyl-cellosolve is added dropwise to the mixture, and stirring is carried out at 80 ° C for 1 hour. After cooling, the reaction mixture is drunk into water, extracted with benzene, the benzene extract is washed with water, dried and evaporated under reduced pressure. . The residue is purified by column chromatography on silica gel (eluent-benzene), and 0.7 g of the desired compound is obtained.
    15
    20
    25
    0
    product,
    „Go. About
    , t appetite mine
    1510, 1480,
    1.6129.
    cm: 1670, 1610, 1590, 1460, 1400, 1290, 1270, 1060, 970, 810, 720.
     tgls t ppm: 1.32 (singlet, 5 6H); 1.46 (triplet, I 7 Hz, ЗН); 2.44 (doublet, I 7 Hz, 2H); 4.04 (quartet, I 7 Hz, 2H); 5.95 (doublet-triplet, I 14 Hz)} 6.72 (doublet, I 9 Hz, 1H); 7.0-7.8 (multiplet, 11H).
    2. 1- (3-Benzoylphenyl) -4- (3-bromo-4-ethoxyphenyl) -4-metsh1pentane.
    In the same way as described in 2. of Example 2, 1- (3-benzoylphenyl) -4- (3-bromo-4-ethoxyphenyl) -4-methylpentane is treated and 1- (3-benzoylphenyl) - 4- (3-bromo-4-ethoxyphenyl) -, -4-methylpentane.
    0
    0
     .
    I IfUCTtlM
     m "".
    five
    1.5908.
    , cm-: 1670, 1610, 1510, 1500, 1480, 1400, 1330, 1290, 1260, 1060, 930, 810, 720.
     , h, ppm: 1.23 (singlet, 6H); 1.42 (triplet, I 7 Hz, ЗН); 1.48 (multiplet, 4H); 2.51 (triplet, I - 7 Hz, 2H); 3.97 (quartet, I - - 7 Hz, 2H); 6.66 (doublet, I 8 Hz, 1H); 6.98 (double doublet, I - 8. Hz,
    17
    2 Hz, tH); 7.20-7.0 (multiplet, 8H) 7.68 (double doublet, Hz, 2 Hz 2H).
    Example 14 Preparation of 1- {3- -benzylphenyl) -4- (4-ethoxyphenyl) -4- methylpentane.
    1. 1- (3-Benzylphenyl) -4- (4-ethoxyphenyl) -4-metsh1-1-penten,
    To the 5 ml of dry ether was added 1.0 and. lithium aluminum hydride and adding a solution of 0.7 g of aluminum chloride in 10 ml of dry ether. A solution of 0.54 g of 1- (3-benzoylphenyl) -4- (4-ethoxyphenyl) -4-methyl-1-pentene (prepared in accordance with 1 of Example 12) in 2 ml of dry ether is added dropwise to


      ppm: 1.30 (singlet,
    7 Hz, 3N);
    fridge for 30 minutes After cooling to room temperature, ethyl acetate was added dropwise to the mixture. The mixture is drunk in ice water and extracted with benzene. The benzene extract is washed with water, dried, evaporated under reduced pressure, purified by column chromatography on silica gel (1: 2 mixture of benzene and hexane), and 0.45 g of the product is obtained,
    p 1,5892,
     “.. ks, cm-: 1620, 1610, 1590, 1520, 1260, 1190, 1050, 970, 840, 770, 7Д, 710.
    tms
    6H); 1.38 (triplet, I 2.38 (doublet, I 7 Hz, 2H); 3.83 (singlet, 2H); 3.90 (quartet, I 7 Hz, 2H); 5.82 (doublet, triplet, I 14 Hz, 7 Hz, 1H); 6.70 (doublet, .1 9 Hz, 2H) 4 6.80-7.20 (multiplet, 11H).
    2, 1- (3-Benzylfensh1) -4- (4-ethoxyphenyl) -4-methylpentane,
    In the same way as described in 2 of Example 2, the 1- - (3-benz1phenyl) -4- (4-toxyphenyl) - -4-methyl-1-pentene, obtained above according to 1, is reduced, and 1- (3-benzylphenyl) -4- (4-ethoxyfensh1) -4-metsh1pentane,
    1.5640,
    cm: 1600, 1510, 1490, 1470, 1240, 1180, 1110, 1040, 920, 820, 690
      h, ppm: 1.22 (singlet, 6H) i 1.38 (triplet, I 7 Hz, 3N); 1.46 (multiplet, 4H); 2.41 (triplet I 7 Hz, 2H); 3.84 (singlet, 2H);
    10.0 p
    , 4WcTbiu
     .WITH
    0
    five
    18
    3.90 (quartet, 1-7 Hz, 2H); 6.65 (doublet, I - 8 Hz, 2H), 6.80-7.30 (multiplet, 11H).
    Example 15 Preparation of 2- (4- -methylphenyl) -2-methyl-3-butanone (starting compound),
    To 50 ml of dry ether, 9.0 g of magnesium shavings and 100 mg of 1 as a catalyst are added, and 25 ml of methyl iodide are gradually added dropwise. The reaction mixture was heated under reflux for 30 minutes. After that, 200 ml of dry benzene is added to the reaction mixture and heated to 80 ° C to remove ether from the reaction mixture. A solution of 45.6% solane, o-dimers1-40-methylbenzylnitrile in 50 ml of benzene is added dropwise to the reaction mixture. After boiling under reflux for 3 hours, the reaction mixture is carefully added while cooling with ice water.
    5 150 ml 6 n, HCt. After refluxing for 1 h, the mixture was cooled to room temperature and the benzene layer was separated. The benzene solution is rinsed with water.
    0 and dried over anhydrous sodium sulfate, the benzene is evaporated under reduced pressure, and 45.2 g of residue are obtained. The residue is distilled under reduced pressure and 20.0 g (94-95 ° C / 5 mm Hg, Art.) Of pure 2- (45
    0
    five
    0
    five
    -methylphenyl) -2-methyl-3-butanone,
    , h, ppm: 1.41 (singlet.
    l ssG4
     tms
    6H); 1.81 (singlet, SN); 2.31 (singlet, SN); 7.07 (singlet, 4H),
    Example 16. Obtaining 2- (4- -chlorophenyl) -2-methyl-3-butanone,
    To 100 ml of dry ether was added 13.0 g of magnesium chips and I, as a catalyst, then carefully added dropwise to add 66 g of methyl iodide, and the reaction mixture was heated under reflux for 1 hour. Then, in the reaction the mixture is added 150 ml of dry benzene and heated to 80 ° C to remove ether from the reaction mixture,
    A solution of 45 g of o-dimethyl-4-chlorobenzonitrile-1 in 30 ml of benzene is added dropwise to the reaction mixture, and refluxing is carried out for 3 hours. While cooling with ice water, the reaction mixture is carefully added. ml 6 N, HCt "After that the mixture is boiled
    under reflux for 48 hours. After cooling to room temperature, the benzene layer is separated. The benzene solution is washed with water, dried, the solvent is evaporated under reduced pressure, and 52 g of residue are obtained. The residue is distilled {and 43.0 g (104 ° C / mm Hg) of pure 2- (4-chlorophenyl) -2-methyl-3-β-butanone are obtained,
     - 1.5254.
     . , cm: 1730, 1500, 1380 1370, 1140, 1115, 1020, 840, 690,
      ppm: 1.43 (singlet, 6H); 1.85 (singlet, SN); 7.16 (doublet, 1l, - 9.1 Hz, 2H); 7.28 (doublet, - 9.1 Hz, 2H), the last two signals are of the AB type.
    Example 17 Preparation of 2- (4- -methoxyphenyl) -2-methyl-3-butanone
    Analogously to example 15, 51.4 g (106-111 ° C / 4 mm Hg, Art.) Of pure 2- (4-methoxyphenyl) -2-methyl-3-β-butanone are obtained using 58 g in, o-dimetcn-4 - methoxybenzylnitrile.
    P
    1.1
    , dtststi
    1.5230
    , 1705, 1610, 1515 1465, P55, 1305, 1250, 1185, 830.
    tms t ppm: 1.38 (6H singlet); 1.80 (singlet, SN); 3.69 (singlet, ZN); 6.78 (doublet, -9.0 Hz); 7.10 (doublet, 1 d 9.0 Hz, 2H), the last two signals are of the AB type,
    Example 18 Preparation of 2- (3, -methylenedioxyphenyl) -2-methyl-3-butanone,
    Analogously to example 15, 83.2 g (11b-117 C / 0.9 mm Hg, Art.) Of pure 2- (3,4-methyl-1-dioxyphenyl) -2-methyl-3-butanone are obtained using 93 g of d, of dimethyl-3,4-mexican-benzylnitropyl.
    pd .1,5306. VM "CTV," cm-: 1710, 1510, 1500, 1490 ,, 1430, 1230, 1130, 1110, 1035, 930, 810, 680,
     , h, ppm: 1.39 (singlet, 6H); 1.85 (singlet, SN); 5.88 (singlet, 2H); 6.6-6.8 (cartoon,
    ZN)
    Example 19 Preparation of 2- (4-α-ethoxyphenyl) -2-metsh1-3-butanone,
    Analogously to example 15, 44.0 g (mm Hg) of pure 2- (4-ethoxyphenyl) -2-metsh-1-3-butanone are obtained.
    go
    1 CLEAN 11
    "" "
    1.5122,
    cm: 1700, 1510, 1250, 1180.
     ppm: 1.3-1.5 (multiplet, 9H); 1.82 (singlet, SN); 2.97 (quartet, I - 7.2 Hz, 2H); 6.76 (doublet, - 8.7 Hz, 2H); 7.08 (doublet, 1dr-8.7 Hz, 2H), the last two signals are of the AB type.
    Example 20 Preparation of 2- (3-β-trifluoromethylphenyl) -2-methyl-3-butanone,
    Analogously to example 16, 10 g o / o (α-dimethyl-3-trifluoromethylbenzylnitrile) is treated and 9.6 g of residue is obtained. The residue is purified by column chromatography on 200 g of silica gel (eluent benzene) and 4.3 g of pure 2 are obtained. - (3-trfluoromethylphenyl) -2-methyl-3-butanone.
     make
    cm-: 1700, 1330, 1235,
    five
    0
    five
    0
    five
    0
    five
     1160, 1125, 1070, 800, 700.
    The compounds obtained according to the proposed method (according to Example 11) are presented in Table. one,
    The compounds of formula (I) exhibit insecticidal activity against sanitary parasitic insects - a fly, a mosquito, a cockroach, an agricultural parasitic insect - delphacids, cicadas, caterpillars, butterflies, leaf beetles, aphids, grinders, mites. The compounds obtained are effective for combating insects that parasitize stored grains, such as scabies, red granary and rice weevil, in addition, they can be used to control non-pathogenic parasites on animals. They have not only a killing effect, but also a deterrent effect, and they do not exhibit a phytotoxic effect on Solapacede plants. In addition, the compounds of formula (I) have a very weak toxic effect on mammals. In addition, these compounds are largely safe for fish and can be used to combat aquatic parasitic insects - mosquito larvae and blood-sucking insects, and can be applied from air over large areas, including lakes, marshes, ponds and rivers.
    The following recipes are prepared using them as
    the active substance of the compound of formula (I).
    Example 21: 20 parts of the subject compound, 10 hours, Sorpol 355S (a registered trademark for a mixture of non-ionic surfactant and anionic surface-active agent, Toho Chemical Indubcrial, Co Ltd) and 70 parts of xylene are mixed and mixed to obtain an emulsifiable concentrate .
    Example 22 In 10 parts of acetone, 1 part of the proposed compound is dissolved and 99 parts of clay are added to the powder to dissolve the solution, after which the acetone is evaporated and a dust is obtained.
    Example 23. To 20 parts of the proposed compound are added 5 parts of surfactant, the mixture is thoroughly mixed and 75 parts of diatomaceous earth are added to it. The mixture is stirred in a grinder and a wettable powder is obtained.
    Example 24. To 0.2 parts of the proposed compound was added 2 parts of meta-tolyl-L-methylcarbamate and then 0.2 parts of PAP (the registered trade name of the modifier is acidic isopropyl phosphate, supplied by Nippon Chemical In - nustr. Co. ltd). The mixture is dissolved in
    10 parts of acetone and 97.6 parts of clay are added to the solution to produce dust. The mixture is stirred in a grinder, the acetome is evaporated and a dust is obtained.
    Example 25. KO, 2h. the proposed compound is added 2 hours, Ofunack (the registered trade name of the product supplied by Mitsui toatsu Chemicals, inel) ,. and then 0.2 parts of the described PAP is added, the Mixture is dissolved in 10 hours, acetone and 97.6 hours are added to the solution, clays to produce dust. The mixture is stirred in a crusher, the acetone is evaporated and a dust is obtained.
    Example 26, To 0.1 part of the proposed compound, 0.5 part of piperonyl butoxide is added, the mixture is dissolved in kerosene and 100 hours, of oil, solution are obtained.
    Example 27, To a mixture of 0.5 hours, of the expected compound and 5 hours, described above, Ofunack was added 5 hours, Sorpol sn-200 (a registered trademark of a mixture of non-ionic surfactant and anionic surfactant,
    one
    1524808
    22
    0
    five
    WITH
    five
    0
    five
    0
    five
    0
    five
    Toho Chemicals Industrial Co., Ltd), the mixture is dissolved in 89.5 parts of xylene and an emulsifiable concentrate is obtained.
    Example 28. A solution formed by mixing 0.4 h of the proposed compound, 2.0 parts of piperonyl butoxide, 6 h. xylene and 7, 6 parts of deodorized kerosene are loaded into an aerosol vessel, the valve part is attached to it, through the valve part under pressure of 84 hours, fuel (liquefied petroleum gas) and an aerosol is obtained.
    Example 29. In an appropriate amount of chloroform, 0.05 g of the proposed compound is dissolved, the solution is uniformly applied to the surface of an asbestos plate having a size of 2.5 cm "1.5, 3 cm (thickness), and a heated fumigation agent is obtained for placement on a heated stove.
    Example 30. In 20 ml of methanol, 0.5 g of the proposed compound is dissolved, the solution is evenly mixed with stirring with 99.5 g of a combustible carrier (mixture of tubular powder, pyrethrum powder and wood flour in the ratio 3: 5: 1). The methanol is evaporated and 150 ml of water are added. The mixture is thoroughly mixed, and the kneaded mixture is molded, dried and dried; the anti-mosquito coil is drained.
    Example 31, To a mixture of 1 part of the proposed compound, 3 parts of Ofunack, described above, 2 hours. Serogen 7A (carboxymethyl cellulose) and 2 hours. Sunekisu (sodium ligninsulfonate). 92 hours, clays and a suitable amount of water are added, the mixture is granulated, sieved and granules are obtained.
    Example 32. Describes emulsifiable concentrates are presented in table. 1, was prepared in the same manner as described in Example 21.
    Emulsifiable concentrates, each of which contains a predetermined amount of the active ingredient, are prepared by mixing the ingredients. Emulsifiable concentrates containing large amounts of QiZ active ingredient can be obtained by mixing the active ingredient with a surface active agent without a solvent, and these emulsifiable concentrates are suitable for application from air, which uses a reduced amount for dispersion.
    231524808
    Example 33. Use 5.20
    and 60 parts of the proposed compound.
    Get wettable powders as well
    as described in example 23.
    The proposed compound is applied
    usually in the amount of 1-300 g, preferably 2-100 g, most preferably in the amount of 5-20 g of the active ingredient per 10 are.
    The proposed compounds have excellent insecticidal and acaricidal activity and are very little toxic to fish.
    The described compounds a to g are tested as comparative and in the same way as the proposed compounds. All tests were performed twice, namely, each result was expressed as an average value obtained from the two data. Compounds for comparison are the following:
    a) 0,0-dimethyl-0- (2,2-dichloroin-yl) phosphate (DVDR);
    b) 0,0-diethyl-0- (3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (OFUNAC);
    c) diethyl 2-isopropsh-1-4-methyl-6-pyrimidinyl phosphorothionate (Diazinon
    d) 8-methyl-H- (methylcarbamoyloxy) - thioacetamidate (Metomyl);
    e) 2,2,2-trichloro-1,1-bis (p-chlorophenyl) ethanol (Keltan);
    f) sodium salt of pentachlorophenol (PCP sodium salt);
    g) 3-phenoxy-o / -cyanobenzsh1-c / -isopropyl-4-chlorophenylacetate (fenvalerate)
    h) 3-phenoxybenzene-1- 2- (4-ethoxy-α-, nyl) -2-methyl or 1-methyl ether
    Test 1. Effect on scoop ordinary.
    The emulsifiable concentrate of the test compound obtained in Example 21 is diluted with water to a predetermined concentration. The leaves of the sweet potato are soaked in diluted solution. The leaves of lettuce are dried and placed to plastic cups with a diameter of 10 cm, k 10 cups of scoops in the third age stage are freely placed in each cup. After 48 hours, the number of dead and live larvae is counted, and the mortality is calculated.
    Characteristics of the proposed compounds are given in table. 2; test results - in the table. 3,
    Test 2. Action on the cyclone rice.
    24
    Four or five rice sprouts, each of which has three leaflets, are bundled and sprayed with 3 ml of the same concentration of the soot concentrate, as in test 1. The bundle is dried, covered with a metal mesh cylinder and 10 adult females of the cyclone rice are loosely placed. After 48 hours, the number of dead adults is counted.
    The test results are presented in table. four.
    Test 3. The action on the Prusak. An i1 ml solution of test compound 6 with acetone of a given concentration is poured into a high Petri dish with a diameter of
    9 cm and 9 cm high. The Petri dish is left to stand to evaporate the acetone. The upper part of the inner wall of the Petri dish is covered with oil to prevent adult -oso-disintegration,
    beat the black person from the Petri dish. In each Petri dish freely placed 10 adult females of Prusak. After 48 h, the number of dead individuals is counted. . Test results are presented.
    in tab. five.
    Test 4. Effect on the spider mite duplex mite.
    The kidney disk of the legume leaf (diameter 20 mm) is perforated with a plug punch and placed on a cotton adsorbent impregnated with water, and 20 adult spider mite mites are loosely placed on top and left to stand for 1 hour. As in Test 1 and 2, a diluted emulsifiable concentrate of the test compound with a final concentration of 200 ppm is applied in an amount of 3 ml using
    application apparatus having a diameter of 20 cm and a height of 60 cm. After 24 hours, the number of dead individuals is counted.
    The test results are presented in table. 6.,
    Test 5. Toxic effect on fish.
    A 60 cm wide, 30 cm high and 40 cm high water tank is filled with water. 10 carp at the age of 1 year, having a body length of about 5 cm, freely placed in a container give them the opportunity to adapt
    25
    to medium in tank. A solution of the test compound in acetone is introduced into water in such a way that the concentration in water is 1-0.1 h / ppm when the specified acetone solution is added in an amount of 1 vol., Per 100 ob.h. water. After 48 hours, the number of dead and carps was counted and the effect of the test compound on the carps was checked.
    The test results are shown in Table. 7
    Test 6. In 10 ml of acetone, 2 mg of the proposed compound is dissolved. The solution is applied to the larva of the common scoop, which is in the third stage of growth, in the amount of 1 µl per larva using a microsyringe. After application, the larvae are placed in a cup (diameter 10 cm, height 5 cm) made of polyethylene and lettuce leaves are fed there. After 48 h, the number of live and dead larvae is counted and mortality is calculated. In one test, 20 larvae were used per compound. The test was carried out three times. The results are presented as mean values. Compounds 1-69 are used. Mortality is 100%.
    Test 7. In 1 ml of acetone, 0.05 ml of the proposed compound is dissolved.
    The solution is applied to the abdomen of an adult female of a cyclone rice in the amount of 0.5 µl per cyclotte using a cycling syringe. The treated larvae were loosely placed in a metal mesh cylinder and rice seeds were spread inside it, after which the cylinder was left to stand in the room. For each compound, 20 adult female cyclists are used. 48 hours after the treatment, the number of live and dead tsikadok is counted.
    Mortality is 100% when using any of compounds 1-69.
     Test 8. The test is carried out similarly to test 1, with each of the emulsifiable concentrates of the proposed compounds, and these concentrates are prepared in accordance with Example 32. The results are the same as in Test 1.
    Test 9, As described in Example 22, three kinds of jacks are obtained; Dust containing 0.1 h. Active10
    52480826
    go ingredient and 99.9 hours of carrier; dust containing 1 part of the active ingredient and 99 parts of the carrier, and dust containing 10 hours of the active ingredient and 50 parts of the carrier. Five rice sprouts with 12–18 cm ,, are planted in plastic pots (10 cm in diameter) and covered with a metal mesh cylinder having a diameter of 7 cm, a height of 15 cm, and an opening size of 16 mesh. In the cylinder freely placed 15 adult female of the Tsikadki rice. This construction, with the circulating apparatus freely enclosed within it, is placed in a dust spraying apparatus. Dyct is applied in an amount of 4 kg / acre. After 4 hours, the number of dead and live tsikadok is counted. For each of compounds 1-69, the mortality is 100% for all three types of dust. When using Tzumacid (meta-tolyl-N-methylcarbamate) as a comparative compound, the mortality in the case of three types of dust, taken in the specified time range is 15
    20
    25
    ke, O, 20 and 100%.
    0
    five
    0
    Test 10. In accordance with Example 33, three types of wettable powder are obtained: powder containing {5 parts of the active ingredient, 20 parts of the active ingredient and 60 parts of the active ingredient. Each wettable powder is diluted with water to an active ingredient concentration of 100 ppm. The solution is applied to pre-prepared cabbage sprouts, having 3-4 leaves, in an amount of 20 ml per sprout using a sprayer. The sprouts thus treated were kept in a greenhouse for 2 days, and then 2 leaves were torn off and placed in a container of polyethylene 10 cm in diameter and 5 cm high in laboratory conditions. In each vessel on the leaves are placed freely on 10 bred larvae scoops. After 72 hours, the number of dead and live larvae is counted and mortality is calculated.
    In the case of using each of compounds 1-69, the mortality is 100%.
    Test 11. The emulsifiable concentrate prepared according to Example 5 is diluted with water to form a solution, the concentration of the active ingredient in which is 100 ppm.20 ml of solution 2715
    (dust with the help of a sprayer on cabbage seedlings at the stage of 3-4 leaves.
    The pollinated cabbage seedlings are left to stand at room temperature for 48 hours or 30 days and then the leaves of the seedlings are removed and placed in a plastic cup (diameter 10 cm, height 5 cm) in which 10 larvae of common butterfly larvae are placed. 3rd age stage. After 48 h thereafter, the number of dead and living larvae is counted, and the Mortality is calculated.
    The test results are shown in Table. eight.
    权利要求:
    Claims (1)
    [1]
    Formula inventions
    n and
    The method of obtaining derivatives of aromatic alkanes by formula (I) i
    t ..
    Ar-C-CH2CH2Kj
    i
    de Ar - naphtha is not substituted or substituted by the same or different substituents, such as halogen atom, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkenyl, lower haloalkenyl, lower hado alkyloxyloxy. -alkynyl - OXI-, lower alkoxyalkyl, lower alkoxycarbonyl, lower haloalkoxycarbonyl, phenoxy, methylenedioxy, and cyano; yetil, ethyl, isopropyl; hydrogen or mesl;
    RV
    RI
    shsh R 4 and R, together with carbon i
    the genus to which they are attached form a cycloalkyl group C J-C „possibly substituted by a halogen atom; - groups of general formula,
    Re
    28
    -СИ-О
    i, h
    at.
    where a R. RS
    oxygen, SNoCH; hydrogen;
    fenpmercapto-, benzyl, benz-ZOH1, or pyridyloxy-, or phenoxy, possibly substituted by a halogen atom or a C -C-alkoxy; K, hydrogen, halogen atom; K | - tetrahydrophthalimidyl,
    characterized in
    aldehyde of general formula
    Ag-dno
    what
    I
    where r
    one
    7
    Ag
    have the indicated meanings
    subjected to interaction with the connection of the general formula
    (Rj) 3 P CH-R where R 9 is phenyl, or a compound of the general formula
    About i
    ) Mr. -R-SN2V ",
    where is lower alkyl;
    R, 5 group of general formula
    0
    35
    6
    .
    where a
    RS-R,
    have the indicated meanings
    under Wittig reaction conditions, the resulting olefin of the general formula
    B1 AG-С-СН2СН СНВ „
    Ba where Ar ,, R. ,, Rj, R are indicated
    meanings
    subjected to recovery in an organic solvent on Pd / C.
    29
    Compound
    The substituents in the sheep formula (1) -.H Physical properties
    I R, I D I wedged, X I N foundo, t I Formulas
    Ag
    CH5
    CP,
    V
    SNI,
    sn.
    CH
    J-chj
    -t-o-opv - .p
        N8.19H 7.98
    S,
     - 1.5373 С 75.36С 75.21
    H 6.32H 6.40
    Cjhso
    mon, CHjCHj
     O-UL- sCHj-CH, .5824 with 80.18 ° 80.01
      7.00, 7.14
    5CHjO.
    6СН, 07С1
    all
    9 ™ 3N
    SNS
    CH-0
    10 CTFjO-II
    С1152480830
    Table 1
    Table 2
    Physical properties
     - 1.5373 С 75.36С 75.21
    H 6.32H 6.40
    T 14.31G 14.18
     1.5578 C 79.56 C 79.67
    H 7.45H 7.54
    F 4.84F 4.79
    S ../
    Hlrz
    4jH ,, o,
    C, L / °
    c fio
    SN "" CIO
    s.L.
    S, VO
    31
    1524808
    32
    Prodolmi, 2
    33
    From the day
    Zshmstitsl I OSHLL formulas (I)
    TO
    ich ich11Is etoLeg
    I..I.1JJ
    J I X, X (and Clearly, X
    (i clear x i
    25 CHCljCFjO-Lou SI ,. (, 551 С 65, 65, G, 0,
     5.7 and 5.5
    -v
    26 C1-Q.
    cn c
    J —CH, - / 3 ° O 1.5833 with 72.18 ° 72.06,
     6.06H 5.91
    C1 17.76 C1 17.92
    27
    St, np
    , -c „,% - O
    C, I, 0 28 s, n, d.
    29 "" "-OCHj sn, -sy
    .about
    30, CH, -CHj- Po-1.5925 C 79.95
    H If / h
    / cn
    CjHgO l
    5726 C 83.90 H 7.82
     D. -CH, - "/
    "SNRgO -On-SN, SN, -CH2-G% O 1.5528 C 75.73
     6 | 61
    33 L-SzN, 0-O-CH, CH, -Sn, -GT
     W / H 8.30
    34 CCNVO
    ABOUT
    Sn, Sn, Sn, - / T 7-
    IJ 7.82
    35 CMjClCFzO- - Sn, CH, -CH, 1.5959 C 70.18
    .-H 6I12
    C1 7.97 F 8.54
    1524808
    34
    Prolong the table. 2
    ich ich11Is etoLeg
     (and clearly, X
    (And clearly, XI ornum
    C1 U, 79С1 U.93
    T 7.93F 7, B7
    H 6.06 H 5.91
    C1 17.76 C1 17.92
    1.3602 C 82.72 H 7.23 F 5.45
    C 82.88, N 7.11 F 5.37
    S.I / 0
    p - 1.5638 C 80.34 H 8.19
    C 80.21 H 8.34
    “WV.
    1.5618 C 82.84 H 7.51 F 5.24
    C 82.75 H 7.63 F 5.16
    С 79.79 Н 7.68 S в, 43
    C 83.90 H 7.82
    From 83.70 to 7.96
    y “w.
    C 75.61 AND 6.75 F 9.45
    H.-.O.
    from 83.39
    H 8.43 LUR,
    C 84.15 N 7.99
    WITH,
    C 70.06 H 6.19 C1 8.11 F 8.43
    C ,, H, P1F, 0,
    Continued t "bl, 2
    37
    152480838
    Promshtsh with. 2
    39
    1524808
    40 Continuation of table 2
    1524808
    Table 3
    42
    Continued table. four
    The number of individuals in the state
    knockdown (shock).
    43152А808
    Table 5
    44 Continuation of table 7
    45 Continued table. eight
    1524808
    46
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    同族专利:
    公开号 | 公开日
    US4661501A|1987-04-28|
    GB2120664B|1986-07-30|
    KR870001463B1|1987-08-12|
    SE8302464D0|1983-05-02|
    KR840004703A|1984-10-24|
    CA1227799A|1987-10-06|
    AU1461983A|1983-11-24|
    DE3317908A1|1983-12-22|
    FR2527203B1|1987-06-19|
    CH658046A5|1986-10-15|
    HU191607B|1987-03-30|
    JPS58201737A|1983-11-24|
    NL8301656A|1983-12-16|
    GB2120664A|1983-12-07|
    RU1837764C|1993-08-30|
    SE8302464L|1983-11-19|
    FR2527203A1|1983-11-25|
    IT1203651B|1989-02-15|
    IN157031B|1986-01-04|
    NZ204104A|1986-06-11|
    GB8312249D0|1983-06-08|
    BR8302590A|1984-01-17|
    US4814340A|1989-03-21|
    DE3317908C2|1993-09-02|
    SE463455B|1990-11-26|
    AU544708B2|1985-06-13|
    IT8348307D0|1983-05-17|
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    法律状态:
    优先权:
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