• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    1499508 3,3,3-Trifluoropropionic acid derivatives IMPERIAL CHEMICAL INDUSTRIES Ltd 5 Nov 1975 [6 Dec 1974] 52829/74 Heading C2C The invention comprises 3,3,3-trifluoropropionic acid derivatives of the formula wherein Ar is phenyl or naphthyl optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, or phenyl or phenoxy optionally substituted by halogen C 1-4 alkyl or C 1-4 alkoxy; X is or CH 2 or a valence bond; R<SP>1</SP> is hydroxy, amino, dimethylamino or C 1-6 alkoxy optionally substituted by carbamoyl, dialkyl carbamoyl or dialkylamino or by a pyridyl, halophenoxy or by a radical of the formula and R<SP>2</SP> is H or C 1-4 alkyl or CF 3 and for these compounds wherein R<SP>1</SP> is OH, the pharmaceutically acceptable salts thereof and their preparation by (a) reacting compounds of the formula where X is other than a valence bond, Z is halogen, alkene- or arene-sulphonyloxy, and when X is a valence bond, 2 is aryliodonium or 2-thienyl-iodonium, with salts of the formula wherein M<SP>+</SP> is a metal cation; (b) for compounds in which R<SP>1</SP> is OH, hydrolysing the corresponding C 1-6 alkyl esters; (c) for compounds in which R<SP>1</SP> is NH 2 , hydrolysing the corresponding nitriles; (d) for compounds in which R<SP>1</SP> is NH 2 or N(CH 3 ) 2 , reacting the corresponding acid halides with ammonia or dimethylamine (e) for compound in which R<SP>1</SP> is an optionally substituted alkoxy group, esterifying the corresponding acids; (f) for compounds in which R<SP>1</SP> is N(CH 3 ) 2 and R<SP>2</SP> is H, heating compounds of the formula with dimethylformamide and sodium hydride; and (g) for compounds wherein R<SP>2</SP> is other than CF 3 , in optically active forms, resolving the corresponding racemic compound or carrying out one of the above processes using optically active starting materials. Acid chlorides of the formula are obtained by reacting the corresponding acids with thionyl chloride. Ethyl 2 - hydroxy - 3,3,3 - trifluoro - 2 - trifluoromethylpropionate is obtained by esterifying the corresponding acid, resulting from the hydrolysis of 2-hydroxy-3,3,3-trifluoro-2-trifluoromethylpropionitrile sodium salt. 2 - (4 - Chlorobenzyloxy) - 3,3,3 - trifluoro- 2 - trifluoromethylpropionitrile is prepared by reacting 2 - hydroxy - 3,3,3 - trifluoro - 2- trifluoromethylpropionitrile sodium salt with 4-chlorobenzyl chloride. 2 - Chloromethyl - 6 - chloronaphthalene is prepared by reacting thionyl chloride with 6- chloro - 2 - hydroxymethylnaphthalene, resulting from the reduction of methyl 6-chloro-2-naphthoate, which is made by esterifying 6-chloro-2- naphthoic acid, obtained by treating 2-acetyl- 6-chloronaphthalene with sodium hypochlorite. 2 - [4 - (4 - Chlorophenyl)benzyloxy] - 3,3,3- trifluoro - 2 - trifluoromethylpropionitrile is obtained by reacting 2-hydroxy-3,3,3-trifluoro- 2 - trifluoromethylpropionitrile sodium salt with 4-(4-chlorophenyl)benzyl chloride. 4 - [4 - (4 - Chlorophenyl)phenoxymethyl chloride is prepared by reacting phosphorus pentachloride with sodium 4-(4-chlorophenyl)- phenoxymethylsulphonate, resulting from the reaction between 4-(4-chlorophenyl)phenol and sodium chloromethylsulphonate. 4 - Bi - phenyl - 2 - thienyliodonium chloride is obtained by reacting (diacetoxy iodo)-4- biphenyl and thiophene in the presence of acetic anhydride and trifluoroacetic acid. 4 - (4 - Chlorophenyl)phenyl - 2 - thienyliodonium trifluoroacetate is prepared by reacting thiophene and 4 - (4 - chlorophenyl) - (diacetoxyiodo)benzene, obtained by acetylating 4-(4- chlorophenyl)iodobenzene. (Œ) - Methyl - 2 - hydroxy - 3,3,3 - trifluoropropionate is obtained by esterifying the corresponding acid. 2 - Chloromethyl - 6 - methoxynaphthalene is obtained by reacting thionyl chloride with 2- hydroxymethyl-6-methoxynaphthalene, resulting from the reduction of methyl 6-methoxy-2- naphthoate.
    公开号:SU764608A3
    申请号:SU752195066
    申请日:1975-12-04
    公开日:1980-09-15
    发明作者:Брайан Хэйдок Дэвид；Патрик Каннингхэм Малхолланд Томас；Мейрик Торп Джеффри
    申请人:Империал Кемикал Индастриз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    where Ar is unsubstituted phenyl or naphthyl, the latter being optionally substituted by alkyl, C-Cx-alkoxy, phenol or phenoxy, which in turn can be replaced by halogen or alkyl or alkoxylyl, -radical /
    X is a group -CHj- or -OCHNd -;
    K is hydroxyl, C —C-alkoxyl;
    R is hydrogen or C. — C. — alkyl or
    GS.14
    -H
    OR their salts, or optically active isomers.
    The process is carried out by the interaction of the compounds form
    (“)
    And g
    where Ar and X are as defined above, and a halogen Z atom, with a salt of formula 1
    yrz;
    Meo -S- bot (s)
    where R and R have the above values, is a metal cation K or Ma at a temperature of 15-30 ° C in an inert solvent followed by isolation of the target product in the free
    i as, or if R
    hydroxyl then in
    as an additive salt of a pharmaceutically acceptable base or if R -. hydroxyl, and R is hydrogen or Cdalkyl, then in the form of an optically active isomer.
    It is most expedient to use as starting materials compounds of the formula i, in which R, hydroxyl, R is methyl, and compounds of formula 5, in which X is a methylene group.
    Example 1. 12.0 g of ethyl 2-hydroxy-3,3,3-trifluoro-2-tri-1 fluoromethylsprrpyrtic acid was added 6 drops to a stirred mixture of sodium hydride sodium (2.4 g 60% ns dispersion in oil) in 100 ml of dimethylformamide. The mixture was stirred for 4 hours nepeMettmBaMT and 8.4 g of 4-chlorobenzyl Chloride was added; stirring was continued for 6 days. See &amp; D is filtered off and the filtrate is urarivayut in a vacuum, coatings of OKHpyioT in vacuum titai pressure: 0.1 mHg, collect 9.9 g (54%) fractions with so kip. : 78-80 ° C; 32ЗЗ with; riocjie pbryoRyStaylizak And from pentane, ethyl 2- (4-chloro-6-benzyl-6-koi) -3.3, 3-triftr-2-trifluoromethyl-propionic acid ethyl ester is obtained from m.p. . Example 2. 54.6 g of 2-Rxy-3 ethyl ester, 3,3-trifluoro-2-trifluoromethyl acid Acetic acid under nitrogen atmosphere are added dropwise to the mixture under a nitrogen atmosphere with a mixture of 9.6 g of 60% - within 30 minutes. sodium hydride oil dispersion, from which the oil is washed with light petroleum ether, and 5 ml of dimethylformamide. The mixture was stirred for 1 hour at the crystalline temperature, then 43.1 g of 4- (4-chlorophenyl) benzyl chloride was added in one portion.
    The resulting solution was stirred under nitrogen for 120 hours.
    at ZO-ZZ S, then evaporated in vacuo. The residue is mixed with water and the mixture is extracted with ether. The ether extract is washed with water, in essence over sodium sulfate and evaporated. The residue is treated with a boiling light
    petroleum ether (bp. 40-60 s), the insoluble products are filtered off, the filtrate is treated with an active. charcoal, filtered, concentrated and cooled.
    Collect 42.3 g (55%) of crystals with so pl. 57-62.5 ° C, after recrystallization, (4-chlorophenyl) -benzyloxy-3,3,3-trifluoro-2-trifluoromethylpropionic ethyl ether is obtained
    Islota in the amount of 39.9 g (51%), so pl. 152-62.5 ° C.
    Similarly to the method described above, replacing 4- (4-chlorophenyl) benyl chloride with euquimolar amounts:
    a) 1-chloromethylnaphthalene,
    b) 1-chloromethyl-4-chloronaphthalene,
    c) 2-chloromethylnaphthalene,
    g) 1-chloromethyl-2-methylnaphthalene,
    d) 2-chloromethyl-b-chloronaphthalene, get iot: a) 48% ethyl ether
    2- (1-naphthylmethoxy) -3., 3,3-trifluoro-2-trifluoromethylpyrrpionic acid c. as a pure oil, according to analysis using thin-layer chromatography (those) on S10 i (ether system: petroleum ether - 1: 1 t.Kip. 40-60 C), X, Xmax (insoluble precipitate) cmI (ether carbonyl), b) 59% e ilrvogo. 2- (4-chloro-1-naphthylmethoxy) ester -3,3, 3-trifluoro-2-trifluoromethylprpionic acid in the form of pure oil according to the analysis of those (system, Varnish in a) NMR spectrum, (SDSe) T i, 4 -2.5), complex 6H, aromatic, 4.74 (singlet, 2H-Shr),
    S / 55 (singlet, 2H,, 8.60 (triplet, 3N, CH, CH, CH);
    S) 46% ethyl ester of 2- (2-naphthylmethoxy) -3, 3, 3-trifluoro-2-trifluoromethylpropyl acid in the form of pure 1gr oil according to TLC analysis
    (system, as in a). X A A "x 770 cm (ethereal carbonyl)}
    d) 72% of ethyl 2- (2-methyl-1-yaftilmethoxy) -3,3,3-trifluoro-2-trifTormethylpropyric acid,
    m.p. 53-54, s;
    d) 48%. Ethyl 2- (6-chloro-2-naphthylmethoxy) -3.3 W-trifluoro-2-trifluoromethylpropionic acid, m.p. 64-65 s, lrle purification on neutral At, stent: mixture of petroleum ether (bp 40-60 C) and sulfuric ether, 19: 2 ratio, and recrystallization from light petroleum ether (bp 40-60 ° WITH). Example 3. A stirred suspension of 750 mg of (4-chlorophenyl) -benzyloxy-3.3, 3-3-trifluoro-2-frifto methylpropionic acid in 10 ml of water is treated, a drop of m 4.50 MP of 0.4N aqueous solution gyD1) is added dropwise per liter. on three . The resulting mixture is quickly heated to 35 ° C, cooled and filtered. Wash the filtrate with ether, filter again, then evaporate in vacuo. The solid residue is dried in vacuo at 10 ° C for 12 hours, yielding 0.74 g (92% sodium salt of (4-chlorofenyl) benzylrksi-3, 3,3-trifluoro-2-trifluoro-2-trifluoromethylpropionic acid in the form of sesquihydrate, a solid product that does not melt below. EXAMPLE 4 A solution of 290 mg of 2- 4- {4-chlorophenyl) -benzyloxy-3,3, trifluoro-2-trifluoromethylpropionic acid and 106 mg of ethyl nicotinate in 10 ml of ether, left at room temperature for 18 hours. Then the solid residue is evaporated, dissolved in a large volume of methylene chloride and diluted with ether to give ethyl alcohol. inatnuyu salt of 2- {4- 4-chlorophenyl) -benziloksiZ 3-3, Z-trifluoro-2-methylpropionic trifluoro kislo.ty in an amount of 301 mg, m.p. 90-92 ° C. Example 5. A mixture of 17.2 g (T) of methyl 2-hydroxy-2-trifluoromethylpropionate and 20 ml of dimethylformamide was added dropwise at a stirred suspension of 4.2 g of a 60% oil dispersion, from which the oil was lightly punched out. Ether, in 200 ml of dimethylformamide. The mixture was stirred for 1 hour at room temperature, then 19.0 g of 4- (4-chlorophenyl) benzyl chloride was added. The mixture is stirred for 4 days, then the mixture is filtered, the filtrate is evaporated in vacuo, water is added and the mixture is extracted with ether. The extract is dried with sodium sulfate and the residue is evaporated and recrystallized from methanol and cyclohexane to obtain 26.4 g of an impure fraction (A) and 3.1 g (10%) of (+) methyl -2-4- (4-chlorophenyl) -benzyloxyP-3. 3,3,3-trifluoro-2-methi propionate, m.p. BZ-VB C. Repeat the above-described prs to an ice cream with the exception that 4- (4-chlorophenyl) -beenyl chloride is replaced with an equivalent amount of 1-chloro-methyl-4-chloronaphthalene, 2-chlorometh-6-hlbrnaphthalene, 2-chloromethylnaphthalene or 1 chloromethylnaphthalene, respectively: a) 18 g (65%) (. +) methyl 2- (4-chloro-1-naphthylmethoxy) -3,3,3-trifluoro-2-methylpropionate as an oil (18 g) having NMK spectrum (P, 6-2.8) multiplet, 6H, aromatic, 4.96 (singlet, 2H,), 6.16 Csletlet, ZN, OCH, 8.28 (singlet, ZN, -C- CHj); b) (± G methyl-2- (6-chloro-2-naphthyl-methoxy) -3.3, 3-trifluoro-2-methylpropionate, mp 105-1O6 ° C, yield 45% J c) (±) methyl-2- (2-naphthylmethoxy) -3, 3, 3-trifluoro-2-methylprypionate in the form of a solid product, so pl. 6567 ° С (from petroleum ether, bp 60-80 ° С); d) (+) methyl-2- (1-naphthylmethoxy) -3, 3,3-trifluoro-2-methylpropionate as an oil, its recrystallization from methanol leads to a substance with m.p. 31-33 C, yield 53%. Example 6 .. A mixture of 2.74 g of ethyl 2-hydroxy-3,3,3-trifluoro-. -2-trifluoromethyl propionic acid and 2 ml of dimethylformamide added dropwise at 0 ° C under nitrogen atmosphere. To a stirred mixture of 0.48 g of sodium hydride 60% oil dispersion, from which the oil is washed with light petroleum ether and 25 ml of dimethylformamide The mixture was stirred at room temperature for 30 minutes, then 2.30 g of 4- (4-chlorophenyl) phenoxymethyl chloride was added, stirring was continued for 3 days at 26 ° C, the mixture was evaporated in vacuo, the residue was mixed with water and the mixture was extracted with ether. The extract is washed with water, dried over sodium sulfate and evaporated. The residue is extracted with light: petroleum ether (bp 40g60s), the extract is purified by passing through a small column (cm) with neutral alumina. After crystallization from light petroleum ether (bp. 30-40 ° C), 3.0 g (8%) of ethyl 2-c- (4-chlorophenyl) -phenoxy-hydroxy-3, 3, 3-trifluoro- 2-trifluoromethylpropionic acid, so pl. 42-43 C. Example 7. A mixture of 0.36 g (±) (4-chlorophenyl) -benzyloxy-3 3,3-trifluoro-2-methylpropionic acid, 1.0 ml IN aqueous sodium hydroxide and 3.6 ml water stir to dissolve the acid. The mixture is filtered, the filtrate is washed with ether and evaporated in akumou. After crystallization from a mixture of ethyl acetate and light petroleum ether (bp 60-80 ° C), 0.3 I (79%) (t) sodium salt of (4-chlorophenyl) -ben zyloxy 3-3,3,3-trifluoro is obtained -2-methylpropionic acid, so pl. 271-272 ° С (with decomposition). Example 8. A solution of 4.15 g of (-) ephedrine in 100 ml of ether is added to a solution of 9.00 g of (t) 2-t4- (4-chlorophenyl) -benzyloxy-3,3,3-trifluoro-2-methylpropionic acids in 100 ml of ether. After 18 hours, the crystallized salt is filtered off and washed with ether. Filtration and washing water is stored (A). 4.6 g of the crystalline salt thus obtained with a mp. IGl-lGT Cj o (. -13 (s 2-3, methanol) three times cris S1Lt uyt from toluene: / pluchay (in) and combined mother liquids (C). Salt In (2.5 g), m.p. 169170 C, Cd. (C 1.8 / methanol) shake for 2 minutes with 200 ml of ether and 150 ml of 2N hydrochloric acid. The ether layer is separated, washed with water, cyujaT over sodium sulfate and evaporated to give 1, 3 g (29% of theoretical) of free Kielbah tp. 125-127 ° С, 3 ° (s 2.2, methanol). After two recrystallization from light petroleum ether. (Eg, boiling point 80-100 ° C) get 0.90 g (20% of theoretical) (+) (4-chlorophenyl) -benzyloxy -3,3,3-trifluoro-2-methylpropi onic acid in the form of prisms, mp 124-125 ° C. G (. (c 1.7 methanol). Combine the above-mentioned mother liquids (A and C) and evaporate. The remaining salts are converted into the corresponding free acid (4 , 4 g) Cd-0/4 ° (c 1.9, methanol) as described for salt B. 5.70 g of racemic acid (10.10 g in total) are added and this product in 100 ml of ether is treated with solution 4 , 65 g (+) ephedrine in 100 ml of ether. After three hours, the precipitated salt is collected and three times, crystallized from toluene, to obtain 4.6 g of salt, so pl. 169171С, (with 1.9, 4-ethanol). This salt is converted into the free acid (3.1 g v67% of the theoretical), so pl. 124-125 ° C ,, 7 ° (c 2.1, methanol), as described for salt B, and after recrystallization of the acid from cyclohexane, and then the light petroleum oligonate (so bp. SO-loO C get 1.7 g (38% of theoretical) (-) (4-chlorophenyl) -benzylok ciD-3, 3, 3-treifor-2-methylpropionic acid in the form of prisms, T.iuj. 124125 c, Cci., 85 ° (with 1.8, methanol). Example 9. In analogy to Example 5, using 2-chloromethyl-b-labels of synaphthalene, (+) - methyl-2- (B-methoxy-2-naphthylmethoxy) -3.3 is obtained , 3-trifluoro-2-methylpropionate As an oil, yield 43%, has a satisfactory mass spectrum and HMR spectrum (molecular ion: 328). Found:%: C 58.5, H 4.6; -16,154 3Calculated,%: C 58.5, H 4.6. At me r.: 10 .. Analogously to Example 2, but starting from methyl 2-hydroxy- 3, 3, 3-trifluoro-2-trifluoromethylpropionate, methyl 2-4- (4-chlorophenyl) benzyloxide} -3, 3,3-trifluoro-2-trifluoromethylpropionate, yield 40-60%, m.p. 61.5-62.5 s (from petroleum ether, so kip. 40-60 ° C). P p and -M y p 11. A mixture of (±) methyl-. -2-goxy-2-trifluoromethylpropionate (17, 2) and dimethylformamide (20 ml) are added dropwise at 0 ° C to a mixed suspension of sodium hydride (4.8 g, 50% colorless dispersion in oil, from which the oil is washed out with continuous ether, boil. 40-60 ° C) in dimethylformamide (200 ml). After stirring at. 4-phenylbenzyl chloride (20.25 g) is added to the room temperature for 1 hour and stirring is continued for 4 days, after which the suspension is poured into water (1 l) and the mixture is extracted with ether. The extracts are dried (N32.504.) Are evaporated and (+) methyl 2- t (4 phenyl) benzyl-3,3,3,3-trifluoro-2-methylpropionate is obtained in the form of an oil (28.1 g, 69%), pure according to thin layer chromatography (S i 0, 5% methanol-chloroform). Similarly, starting from (H) -methyl-2-hydroxy-2-trifluoromethylpropionate (8.6 g) and 4-chlorobenzyl chloride. (8.05 g), get (+) - methyl 2- (4-hlbrbenzyloxy) -3,3,3-trifluoro-2-methylpropionate as an oil (8.0 g, 43%), 92-98s ( 0, Tmm Hg). Example 12. Similarly to examples 1, 2, or 4 of two equivalents of BB sodium hydride and the corresponding starting acids obtained the target product of the formula. I; physico-chemical data (so pl.) and substituents Ar and R are given in the table .. Table
    iC-r -.;,. 7;: ..-.
    CH 4-Chlorophenyl
      4- (4-Chlorophenyl) -phenyl
    1-Naphthyl 4-Chloro-1-naphthyl
    .... .... -. ...,. ..- c ..-..-.-.- iii; iii-, .-. SNL 2-Naftyle
    98-99 130-133 101
    .118-121 or. 105106 (dimorphic)
    109-11
    权利要求:
    Claims (2)
    [1]
    Claim
    A method of obtaining a fluorinated alkanoic acid derivative of the general formula I where Ar '1 C , F 3' ArX-O-C-CO ^ (I) where Me * R <and R * are subjected to the formula
    ’Interaction With salt Me * oh-so-so *, (w) R 2 . metal cation K or Na
    nemephenyl or naphthyl, or substituted with halogen, alkyl or SC-Cd-alkoxyl, phenyl or phenoxy, which in turn can be replaced with halogen, alkyl or C ^ -C + - and l-strength, hydroxyl, C 4 -C 6 alkoxy hydrogen, C 4 -C 4 alkyl or trifluoromethyl;
    -SNd group -, -OCH nd * -, or salts thereof or optically active isomers, characterized in that the compound of formula K
    I
    R a
    Ar-x-z where
    Ag
    IX have the above descriptions, and
    - the ena halogen atom35 has the above meanings, at 15-30 ° C in an inert solvent, followed by isolation of the target product in free form or, when R 1 is hydroxyl, in the form of a pharmaceutically acceptable base addition salt, or when R 1 OH and R a is hydrogen or C 4 -Cd alkyl, then in the form of an optically active isomer.
    [2]
    2. The method according to claim 1, the difference with the fact that as the source of 4 · substances use compounds of the formula 1 ". in which R * is hydroxyl; R 1 is methyl / and the compounds of formula 5, in which X is a methylene group.
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    同族专利:
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    CH511786A|1968-01-11|1971-08-31|Hoechst Ag|Process for the preparation of phenoxyalkanecarboxylic acids, their salts and esters|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB52829/74A|GB1499508A|1974-12-06|1974-12-06|3,3,3-trifluoropropionic acid derivatives|
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