• 专利附录
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    • 专利摘要:

    公开号:SU957766A3
    申请号:SU792835389
    申请日:1979-10-15
    公开日:1982-09-07
    发明作者:Дория Джанфедерико；Ромео Чириако；Луиза Корно Мария；Лаурия Франческо；Сберзе Пьеро；Тиболла Марчеллино
    申请人:Карло Эрба С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the preparation of new compounds — substituted 2-cyclopropyl chromones of the general form OO djl-CHRs (P CHg where R is hydrogen or alkyl, unsubstituted or ea: Cj-Cf alkanoyloxy group or H-group: where R4 and R are each independent. MO from each other alkyl alkyl or alkenyl, furyl, thienyl or pyridyl each of which is unsubstituted or substituted by methyl, D L S Hg or the group -V g where R, R. and U are each independently of each other hydrogen atom or group - (O ) ft-Rj, where P is an integer, is O or 1, and Rg is alkyl C ,, - C, or their salts. Neither have antiallergic activity. There is a known method for producing 4-oxychromones by cyclizing condensation products of o-hydroxyacetophenones with anhydride in the presence of acid F. The purpose of the invention is to obtain new substituted 2-cyclopropylchromones of formula I with valuable biologically active properties. Qut-f jiHRg ICU CK-tUBs where R, R / j and R have the indicated meanings, are cyclized in the presence of an acid catalyst, such as hydrochloric acid, at the boiling point of the reaction medium in an inert organic solvent selected from the group comprising methanol, ethanol, dioxane, tetrahydrofuran, ben EOL, toluene and acetic acid or mixtures thereof, and the desired product of formula I is isolated, where R is a hydrogen atom, in free form or in as a salt and / or translates it into a compound of Formula-1, where R is alkyl, unsubstituted or substituted by a C-Cd-alkanoyloxy group or group
    ъ
    where R4 and R have the indicated meanings, and the target product is isolated or converted into a compound of formula I, where R is a hydrogen atom, and the target product is isolated in free form or
    in the form of salt. I
    As acid catalyst
    can be used besides hydrochloric, hydroiodic, sulfuric or formic acids.
    Example. Methyl-3-valeroyl-4-hydroxybenzoate (9 g), dissolved in anhydrous benzene (100 ml) and pyridine (10 ml), was reacted with 2-phenylcyclopropyl-1-t-carbonyl chloride at room temperature for 20. hours. The organic solution is washed with diluted HC1, 5% NaHCOj and water, then evaporated to dryness in vacuo to give an oil (17 g), which is dissolved in 2-butanone (150 ml) and then reacted with anhydrous (18.6 g) while stirring at reflux temperature for 5 hours. After cooling, the reaction mixture is poured into ice-water and extracted with ethyl acetate after neutralization. The organic phase is separated and evaporated in vacuo to a dry residue to obtain crude material (15.4 g), which is treated with 99% formic acid (30 mp) at reflux temperature for: 30 minutes. After cooling, the reaction mixture is poured onto ice with water and the residue is filtered off, washed thoroughly with water and recrystallized from ethyl acetate to obtain trans-b-carbomethoxy-3-propyl-2- (-2 phenylcyclopropyl) chromone (6.7 g) with m. square 171-173c, which is reacted with 10% KOH in a 95% ethanol solution (105 ml) at reflux temperature for 30 minutes. After cooling, the reaction mixture was acidified with 23% HC1, concentrated in vacuo and diluted with ice water. The residue is filtered / washed with water and recrystallized from ethyl acetate to give trans-6-carboxy-3-propyl-2- (2-phenylcyclopropyl) -chromone (5.4 g) with m.p. 195-196 S.
    Using a similar procedure and the outcome of their suitable 3-alkanoyl-4-hydroxybenzoates, the following compounds are obtained:
    TRANS-6-Carboxy-3-methyl-2- (2-phenylcyclopropyl) -chromone
    Trans-6-Carboxy-3-ethyl-2- (2-phenycyclopropyl) -hromo, and so on. pl. 217-218 ° C
    Trans-6-Carboxy-3-isopropyl-2- (2-phenylcyclopropyl) -chromone;
    Trans-6-Carboxy-3-butyl-2- (2-phenylcyclopropyl) -chromone, so pl. 198199C.
    Example 2: Using the procedure of Example 1 and starting from the appropriate trans-2-arylcyclic-propyl-1-carbonyl chloride, the following compounds were prepared.
    trans-b-carboxy-3-ethyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone, m.p. 226-228c;
    TRANS-6-Carboxy-3-ethyl-2- 2- (3-methylphenyl) -cyclopropyl-chromone
    trans-6-carboxy-3-propyl-2- (2-methylphenyl) -cyclopropyl-chromone, so pl. -206-207 0;
    Trans-6-Carboxy-3-propyl-2- 2- (4-methylphenyl) -cyclopropyl} -chromone, m.p. 215-216 ° 0;
    Trans-6-Carboxy-3-propyl-2- 2- (3-methylphenyl) -cyclopropyl-chromone, m.p. 177-178 seconds;
    Trans-6-Carboxy-3-propyl-2- 2- (2-methoxyphenyl) -cyclopropyl-chromone, m.p. 161-163C;
    Trans-6-Carboxy-3-propyl-2- 2- (3-methoxyphenyl) -cyclopropyl-chromone, m.p., 158-i60 C.
    Trans-6-Carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl} -chromone, m.p. 137-138 0.
    Trans-6-Carboxy-3-propyl-2- 2-. - (2-ethylphenyl) -cyclopropyl-chromone, t. square 211-212 ° C;
    Trans-6-Carboxy-3-propyl-2- 2- (3-ethoxyphenyl) -cyclopropyl-chromone m. pl. 208-209 ° C .;
    Trans-6-Carboxy-3-propyl-2-L2- (2,5-dimethylphenyl) -cyclopropyl-chromo. n. m.p. 161-163 ° C;
    trans-6-Carbo-side of si-3-propyl- (2,3-dimethoxyphenyl) -cyclopropyl-chromium, so pl. 184-186 ° C;
    Trans-6-Carboxy-3-propyl-2- 2- (2,5-dimethoxyphenyl) -cyclopropyl-chromone, m.p. 180-181 ° C;
    trans-6-carboxy-3-propyl-2- 2- (2-methoxy-3-ethoxyphenyl) -cyclopropyl-chromone, m.p. 205-207 seconds;
    trans-6-Carboxy-3-propyl-2- (2- (2-ethoxy-3-methoxyphenyl) -cyclopropyl) -chromone, m.p. 219-220s;
    trans-b-carboxy-3-allyl-2- 2 - (2-methylphenyl) .- cyclopropyl chromone, m.p. 189-190 ° C;
    trans-b-carbomethoxy-3-propyl-2- 2- (3-methylphenyl) -cyclopropyl-chromone; m.p. 115-117 ° C; Trans-6-Car6omethoxy-3-propyl-2- 2- (2-methoxyphenyl1-cyclopropyl-chromone, mp 125-127 ° C. Example 3. Using the procedures of Example 1 and starting from the appropriate trans-2-heteroarylcyclopropyl -1-carbonyl chlorides, the following are obtained from the following: trans-6-Carboxy-3-propyl-2- 2- (5-methyl-2-furyl) -cyclopropyl 3-chromo, m.p., ab6-169 ° C; Trans-6-Carboxy-3-propyl-2- 2- (5-methyl-2-thienyl) -cyclopropyl chromium, mp 179-181 ° C; trans-6-Carboxy-3-propyl-2- 2- (2-thienyl) -cyclopropyl-lame, mp 196-197 ° C .; trans-6-carbomethoxy-3-propyl-2- 2- (5-methyl-2-thienyl) -cyclopropyl-chromone, mp 151-153 C; trans-6-Carbo etoxy-3-propyl-2- 2- (2-pyridyl) -cyclopropyl-1-chromone, mp 180-182 ° C; trans-6-Carboxy-3-propyl-2- 2- (2-pyridyl) -cyclopropyl-chromone , mp 209-210C; EXAMPLE 4. Trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cycloprop2 -chro mona tert-Butyl ether trans-6-carboxy-3-propyl (4,3 d) react with trifluoroacetic acid (30.2 ml) at room temperature for 6 hours. Trifluoroacetic acid is distilled off in vacuo and the residue is diluted with ice; the precipitate is filtered off and washed with water until neutral reaction. Crystallization from zantanol gives trans-6-ka.rboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone, (3.2 g) with m. pl. 206-207 ° C. . Using the same procedure, the following compounds were obtained: trans-6-Carboxy-3-propyl-2- 2- (3-methoxyphenyl) -cyclopropyl-chromium m.p. 158-170s; trans-b-carboxy-3-propyl-2- (2-. - (2-methoxyphenyl) -cyclopropyl-chromone, mp 161-163 C. Example 9: tert-butyl ester trans- 6-carboxy-3-propyl-2- 2- (5-; -methyl-2-furyl) -cyclopropyl-chromone (4.25 g) is reacted with trimethylsilyl iodide (2 g of 1.42 ml) in tetrachloride carbon (5Q ml) in a /, nitrogen atmosphere during stirring, at room temperature for 2 hours and then at 50 ° C for 2 hours. After cooling the reaction, the mixture is diluted with ethyl ether and extracted with 2% MaNSO3 ; the aqueous LAYER is separated and acidified by addition of 23% HC1. The precipitate of filters ipx and washed with water until neutral. Crystallization from isopropyl alcohol gives trans-6-carboxy-3-propyl-2-2- (5-methyl-2-furyl) -cyclopropid-1-chromone (2.35 g) with m. mp 166-169 C. Analogously, trans-6-carboxy-3-propyl-2- 2- (5-methyl-2-thienyl) -cyclopropyl-chromone, mp 179181 C is prepared. -6-Carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone (8 g) is reacted with ethyl iodide (5.4 g) and anhydrous Ki2CO} (6.3 g) in dimethylformamide (70 ml) while stirring at room temperature for 4 hours. After dilution with ice water, the precipitate is flushed and crystallized. isopropyl ether. Get trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone ethyl ether (7.8 g) with so pl. 118120 C. Similarly, according to the method, IU1T trans-6-carboxy-3-propyl-2- 2- (5-methyl-2-furyl) -cy.c Lopropyl-chromone ethyl ether with m.p. 76-78 ° C. Example 7. Trans-6-Carboxy-3-propyl-2- 2- (2-methylphenyl) -cyc-. lopropyl-chromone (5 g) is reacted with chloromethyl pivalate (5 ml) and triethylamine (2 ml) in dimethylformamide (40 ml) for 2 hours. After cooling, the mixture is diluted with ice water and extracted with ethyl acetate; the organic layer is washed with 5% NaHCOj and water. After evaporation in vacuo to a dry residue, the residue is recrystallized from isopropyl ether. Trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-2-chromone pivaloyloxymethyl ester (3.65 g) is obtained. IR spectrum: () ether -. 1735 () chromone - 1640 cm. . Example 8 Trans-6-Carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone (3.6 g) is reacted with 1-chloro-2-diethylaminoethanol (2.7 g) and anhydrous K2CO5 (2.8 g) in dimethylformamide (40 ml) during entrapment for 8 hours. After dilution with water, the precipitate is filtered and washed with water until neutron reaction; Recrystallization from isopropyl ether gives trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) cyclopropyl-chromone 2-diethylaminoethyl ester (2.2 g) c. m.p. 89-90 ° C. . PRI me R 9. Trans-6-Carboxy-3-propyl-2-2-2-methylphenyl) -cy1O1-propyl} -chromone (12 g) is reacted with thionyl chloride (6 ml) in dioxane ( 120 ml) at room temperature for 3 hours, and then the mixture is evaporated to dryness in vacuo. The residue was dissolved in dioxane (80 ml) and triethylamine (2 cm) and reacted with 2-diethylamino ethanol. (4 ml) at room temperature for 20 hours. After dilution with water, the precipitate is filtered, dissolved in ethyl ether (100 ml) and treated with a stoichiometric amount of HC1 in ether. The precipitate was filtered off, washed with ethyl ether and dissolved in water. Alkalization using filtering gives 6-carboxy-3-propyl-3- 2- (2-methylphenyl) cyclopropyl-chromone 2-diethylaminoethyl ester (7.8 g) with m.p. VE-EO C. IR spectrum; -9 (С С) ether of 1720 -3 () chromone - 1640 1610 cmЛ Example. Using the method of examples 1 and 2 and starting from the suitable ter-butyl esters of trans-6-carboxy-3-propyl-2-substituted chromones, I get the following compounds: trans-6-carboxy-3-propyl-2-. (Methylphenyl)) -cyclopropyl-chromone tert-butyl ether: oily product. IR spectrum: -5 (С 0) ether -17.10 () chromone 1640 ... SMP. TRANS-6-Carboxy-3-propyl-2- 2- (5-methyl-2-furyl) -cyclopropyl-chromone tert.-butyl ether: oily product. IR spectrum: - (С 0) ether - 1720 cm () chromone - 1645 cm. -6-Carboxy-3-propyl-2- (2-phenylcyclopropyl) -chromone Art. pl, 92-94 0; TRANS-6-Carboxy-3-propyl-2- 2- (2-methylphenyl1-cyclopropyl-chroMone 2-diethylaminoethyl ether with mp 8–90 sec.
    Mr (Codij) o.eoCh) (-snSNSz)
    1.55 (mJ (-SNSNGSNz)
    1.87 (t) (- (JH-CH)
    2.521S) КНз)

    2.50-2.90 (t) (-CHgCUgCHs - 1H -.-)
    2.95Н) l-OCHgCHgNO 4Л9 (and (-OtHgCHzNO6 .96-7.64 (g) (pyridium / 1 protons 7.:7 (with (} ((-8 chromone / 1yg gigroton)
    8.32 ((f, (f) ((-7, -)
    8.93 (0; (C-5 ---)
    PRI me R 13. trans-6-Carboxy-2 n. NaOH. Then the resulting solution
    -3-propyl-2- (6-: methyl-2-pyridyl) -concentrated in vacuo and diluted with cyclopropyl chromone (1.6 g), dissolved with acetone. The precipitate is filtered in stoichiometric amount of 65 and washed with acetone. Get trans SNG
    CU2 EXAMPLE 11. Trans-6-Carboxy i -Z-propyl-2- 2- (b-methyl-2-pyridyl) cyclopropyl -chromone- (0.6 g) reacts with ethyl iodide (0, 54 g) and anhydrous KjCO (Of63 g) in dimethylformamide (7 ml) with stirring and at room temperature for 6 hours. After dilution with ice water, the precipitate is filtered and recrystallized from n-Hexane to form 0.4 g of trans-6-carboethoxy-3-propyl-2- 2- (6-methyl-2-pyridyl) -cyclopropyl-chromone with m.p. . 95-97 s. Example 12. Trans-6-Carboxy-3-propyl-2- 2- (6-methyl-2-pyridyl) -cyclopropyl-chromone (1.3 g) reacts with. SpCfj (0.6 ml) in a San disk disk (30 ml) with heating under reflux for 1 hour. Then the reaction mixture is evaporated to dryness under vacuum. The residue is dissolved in anhydrous, dioxane. (30 ml) containing triethylamine (0.5 ml) and reacting with 2-diethylaminoethanol (1 ml) at room temperature for 24 hours. After dilution with water, the precipitate is extracted with ethyl acetate and the resulting solution is evaporated to dryness in vacuo. The residue obtained is purified using a silica gel chromatographic column and a mixture of benzethyl acetate L as an eluent. The result of this is 0.4 g of trans-6-car-, boxy-3-propyl-2- 2- (6-methyl-2-pyridyl) -cyclopropyl-chromone 2 - :: d-ethyl ethyl ester as an oil.
    -6-car, xy-3-propyl-2-; 2- (6-methyl-2-pyridyl) -cyclopropyl-chromone sodium salt with m. Pl. .
    Example 14, trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) cyclopropyl-chromone sodium salt (2.5 g) was dissolved in a small amount of water and acidified 23 % hydrochloric acid. The precipitate is filtered and washed with water until neutral pH. Crystallization from methanol gives trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone, m.p. 206-207®С.
    EXAMPLE 15 Sodium salt of trans-6-carboxy-3-propyl-2- 2- 2-methylphenyl) -cyclopropyl-1-chromone (5.15 g) is reacted with lHCO3 (1.25 g) in water (30 ml) at 100 ° C until complete dissolution. After cooling, a precipitate is obtained, which is filtered off and washed with ice water. The sodium salt of trans-6-carboxy-3-propyl is obtained. (2-methylphenyl) -cyclopropyl-chromone (4.3 g) with mp; elimination is 300 ° C.
    Example 16. Trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromo (4.8 g) pivaloyloxymethyl ester (4.8 g), prepared in accordance with Example 15, is reacted with a 1% solution potassium hydroxide in 95% ethanol (68 ml) at reflux for 30 minutes. After cooling, the reaction mixture is acidified and the precipitate is filtered off. The precipitate is washed with ethanol and water until neutral pH. Crystallization from ethanol yields 3.1 g of trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) cyclopropyl-chromone, m.p. 206-207 ° C.
    EXAMPLE 17 Trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) -cyclopropyl-chromone 2-diethylaminoethyl ester, prepared in accordance with Example 10, reacts with a 1% solution of KOH in 95% ethanol (68 ml) at reflux for 30 minutes. After cooling, the reaction mixture was added 1L 1 of 23% salt -. Acidic acid, filter the precipitate washed with ethanol and water until neutral pH. Crystallization from ethanol yields 2.93 g of trans-6-carboxy-3-propyl-2- 2- (2-methylphenyl) iclopropyl-chromo monomer, m.p. 206207 ° C.
    The compounds of the formula I are characterized by antiallergic activity and therefore can be used as drugs for the prevention and treatment of all diseases of an allergic nature, such as asthma, allergic inflammation, hay fever, urticaria and dermatoses. The antiallergic activity of the compounds of the formula I is demonstrated, for example, by the fact that they are active during the passive sensitivity test.
    -coat (test for PCAID) of rats, carried out in accordance with the method of Goose J., Blair AMJN. An important specificity of the compounds of the formula I is that they exhibit high anti-allergic activity also when administered orally.
    The table shows the values of activity obtained during the test for PCS
    rats after oral administration, for a number of proposed compounds,. marked with the indices K 13423, K 13262, K 13462, K 13449, K 13456, in comparison with the well-known antiallergic preparation with the kinolium sodium DiSodium Gromoglucate (DSCG).
    The activity values are expressed for the Kg value. This is the dosage of the active compound, which is able to halve the activity of the serum used dp sensitization:.
    AT
    H
    DR - 1
    de B - dosage of antagonist compound, mg / kg; DR is the dosage coefficient (the antilog of the distance between the logarithmic functions of the dosage effect for serum in the presence and absence of an antagonist). The value of K in this case does not depend on the dosage of the drug and the concentration of the reagent used in sensitization. The lower the Kg value, the higher the anti-allergic activity.
    Antiallergic activity was determined by suppressing 1% -ono-mediated PPPCS according to the Goose I i Blair method using antibodies produced in rats according to Method J, Immunology.
    Test compounds were administered orally 15 minutes before antigen administration. At least 6 animals were used for each dosage. For the proposed compounds were evaluated
    seven-day indicative acute toxicity after oral administration. For example, for compound K 13262, 400 mg / kg was observed for rats.
    The compounds of formula I also possess anti-ulcer activity: they are active against the suppression of stress-induced ulcers in rats that are subject to limitation of mobility in a water bath for 40 minutes in accordance with the method of Tahagi K. and Okabe S. The compounds of formula I have the same bronchodilatory activity; they are active in eliminating bronchospasm caused by administering histamine mors to their pigs in accordance with the method of KanzeH and Rossler. Compounds of formula I can be administered in the usual way. For example, orally and parenterally, with a daily dosage, preferably 0.515 kg / mg, and with inhalation, preferably at a daily dosage of 0.5-100 mg, preferably 0.5-25 mg, or locally, for example as a cream containing 0.5–5 mg, preferably 1–2 mg of active principle per 100 mg of cream. The nature of the pharmaceutical preparations containing the proposed compounds together with pharmaceutically acceptable carriers or diluents depends on the method of administration. The preparations can be made in the usual way and with the use of ordinary ingredients. For example, compounds of formula I may be administered E in the form of aqueous or oily solutions or suspensions, aerosols, as well as powders, tablets, pills, gelatin capsules, syrups, drops, suppositories, creams or lotions for topical administration. Thus, for oral administration, pharmaceutical preparations containing compounds of the formula I are in the form of tablets, pills or gelatin capsules, which comprise the active substance together with diluents, such as, for example, lactose, dextrose sucrose, mannitol, sorbitol, cellulose lubricants, for example, silica, talc, stearic acid, magnesium or calcium stearate, and / or polyethylene glycols, or they may contain binders, for example starches, gelatin, methylcellulose, carboxymethylcellulose, gum arabic tragacanth, polyvinyl irrolidon; disintegrating agents, for example starches, alginic acid, alginates, sodium starch glycolate; gas mixtures, dyes, sweeteners, wetting agents, such as lecithin, polysorbits, lauryl sulfates, and in the general case nontoxic and headlight macologically inactive substances. Used in pharmaceuticals. Said pharmaceutical preparations can be prepared in a known manner, for example, by blending, granulating, tabletting, sugar coating or film coating. For the treatment of allergic asthma, the compounds of the formula I can be administered by inhalation. For this purpose, the respective preparations can be a suspension or solution of the active ingredient, preferably in the form of a salt, such as sodium, in water, and are intended for administration using a conventional vehicle. In the alternative, the preparations can be a suspension or solution of the active ingredient in a conventional liquefied propellant, such as dichlorodifluoromethane or dichlorotetrafluoroethane, and are intended for administration using a pressurized balloon, i.e. aerosol packaging. If the drug is insoluble in the propellant, it may be necessary to add a co-solvent, such as ethanol, dipropylene glycol, isopropyl myristate, and / or surface active substance to the resulting composition in order to suspend the drug in the propellant medium. Surfactants can be any substances commonly used for this purpose, such as non-ionic surfactants such as lecithin. The compounds of formula I may also be prescribed in the form of powders with a suitable spray device. In this case, fine particles of powders of the active ingredient may be mixed with a diluent, such as lactose. In addition, compounds of formula I may be prescribed for administration via subcutaneous or internal injections in the usual way. . In addition to ingesting, the compounds of formula 1 can be used in topical topical formulations, for example in the form of creams, lotions or pastes, for the treatment of dermatological diseases. For such formulations, the active ingredient may be cMeiiiaH with conventional oil-like or emulsifying sensing media.
    Table continuation
    Note. K 13423 - trans-6-carboxy-3-propyl-2 2- (2-methylphenyl) -cyclopropyl-chromone;
    K 13262 - trans-6-carboxy-3-propyl-2-C2-phenylcyclopropyl) -chromone;
    K 13449 - trans-6-carboxy-3-propyl-2-L2- (3-methoxyphenyl) -cyclopropyl-chromone ;.
    K 13456 - trans-6-carboxy-3-propyl-2-2-C5-methyl-2-furyl) -cyclo-. propyl-chromone.
    权利要求:
    Claims (1)
    [1]
    Claim
    The method of obtaining substituted 2-cyclo ~ 20 lopropylchromones of General formula I
    I where'id
    BjOOC
    In 2 sn 2
    - a hydrogen atom or alkyl ; £ -c ~ CrO 'unsubstituted or where is it Co x cn — cnp 3
    CH £
    R ^, R 2 and R ^ have the indicated meanings, they undergo cyclization in the presence. _____ ΐ per- :.
    30 alkanoyloxy-substituted C 5 -C r 'yly group: -And> 4 where R4 and Rg each independent from each mo. friend is lower alkyl;
    ; Rz 2 is alkyl C ^ -Cg or alkenyl C, -C 4 ;
    Rg is furyl, thienyl or pyridyl, each of which is unsubstituted or substituted with meth * * 6.
    scrap or group
    R 7 where R 6 and R 7 are each independently a hydrogen atom or group - (COfl-Rg., Where η is an integer equal to 0 or 1, and Rg-alkyl is CjpCfc, or their salts, characterized in that the compound of General formula II:
    an acid catalyst, such as hydrochloric acid, at the boiling point of the reaction medium in an inert organic solvent selected from the group consisting of methanol, ethanol, dioxane / tetrahydrofuran, benzene, toluene and acetic acid or mixtures thereof, and the desired product of formula I is isolated, where R <- hydrogen, in free form or in salt form and / or convert it into a compound of formula I, wherein R (_ C ^ -C 2 0alkil, unsubstituted or substituted C 2 -C ^ -alkanoiloksigruppoy or group '-r - where Rj and Rf have the indicated values, and select the target Recreatives Products or convert it into a compound of formula I, wherein R <- hydrogen atom, and the desired product is isolated in free form or salt form g.
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    JPS5726683A|1982-02-12|
    JPS6222989B2|1987-05-20|
    BE869407A|1978-11-16|
    JPS6222993B2|1987-05-20|
    ZA784023B|1979-07-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS62108276U|1985-12-25|1987-07-10|
    JPS6455214U|1987-10-01|1989-04-05|
    JPH03117696U|1989-12-19|1991-12-05|
    JPH0390889U|1989-12-29|1991-09-17|
    JPH0390892U|1989-12-29|1991-09-17|
    CA2668870A1|2008-06-10|2009-12-10|Tomohiro Numajiri|Wind turbine generator and method for constructing the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT26399/77A|IT1093451B|1977-08-02|1977-08-02|IT2-CYCLOPROPIL-REPLACED CHROMONES|
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