• 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:
    Benzofuranes are obtained by intramolecular condensation of aromatic oxo compounds having an oxymethylene group in ortho position. The condensation is effected with strongly alkaline agents in solution or in an alkali metal hydroxide melt. The products are useful as scintilators and optical brighteners.
    公开号:SU730305A3
    申请号:SU721819281
    申请日:1972-08-09
    公开日:1980-04-25
    发明作者:Зам Вильфрид；Хорн Антон
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the preparation of valuable intermediates for various organic syntheses, for example for the production of dyes, scintillators, optical brighteners, pharmaceutical preparations, specifically, to methods for the preparation of new furan compounds of the general formula where R is a hydrogen atom, a lower alkyl or phenyl group; R2 together means a lower alkylene group or a condensed benzene ring; n is O or 1, and if n is O, X is a substituted nitro, cyano, carboxy, carboxyalkyl group, phenyl, naphthyl, styryl, benzoxazolyl, or naphthoxazyl; if n is 1, X is a carbon-carbon simple bond, phenylene, biphenylene, terphenylene, naphthyl styryl, biphenyly / schden, stilbile, furylene, tenylene, and the existing double bonds in group X are conjugated with double bonds of the benzofuran residue . The purpose of the invention is to obtain new furan compounds with a wide range of properties, including Siological activity. This goal is achieved by synthesizing these compounds based on the intermolecular condensation of aldehyde in the presence of a strong base 1. A method for the preparation of furan compounds of general formula 1 is described, in that a compound of the general formula: cos / cc ongX-ci 20 co. and
    where R, R, R2, X
    and n have the meanings
    exposed to strong bases.
    For particularly resistant to strong bases and heat-resistant compounds of formula 2 or 3, alkaline melts without a solvent can be used. Condensation can also be carried out in a highly organic organic solvent, for example in tetramethyl urea, N-methyl pyrrolidone, acetonitrile or pyridine.
    Preferred are, in particular, solvents such as dimethylformamide, hexamethylphosphoric acid amide, diethylformag.1id, and dimethylacetamide.
    Solvents can be used individually or as mixtures thereof,
    Aluminum hydroxide, amides, hydrides, alcohols, sulphides, and strongly basic ion exchange resins are used as strong bases for the reaction and condensation.
    Preferred bases for this condensation reaction are hydroxides, amides, sodium or potassium alcohols,
    In carrying out the condensation reaction in an alkaline melt, such condensing agents among those listed above are used that melt without decomposition. In particular, lithium, sodium or potassium hydroxide is used.
    The said condensing agents are used both individually and as mixtures thereof.
    The amount of the condensing agent used varies in a wide range (from an equivalent amount in the solvent medium to a fourfold excess when conducting the reaction in the melt).
    When a solvent is used, the reaction temperature is between -20 ° C and the boiling point of the solvent taken. When the reaction is carried out in the melt, the temperature range is limited below by the melting point of a given eutectic mixture, and above - by the decomposition temperature of the components in the melt. Example 1. II, 5g of o-formyl- (4-cyanbenzyloxy) benzene is dissolved; in 100 ml of dimethylformamide (daFA), add 11.2 g of KOH and heat it for 30 minutes at. Then pour ZOI. Ml of ice water and the crystalline precipitate is sucked off, which is dried in vacuum at. 9.8 g of a dry product of formula 1 (, H, H; X p-cyanophenyl) are obtained, t, mp, 141-143 ° С .
    Example 2, 17.2 g of 2-naphthol-1-aldehyde in 150 ml, CMF was added to a mixture of 6.0 g of sodium methoxide and 14.1 g of p-cyanbenzyl chloride. The mixture is boiled for 30 minutes, cooled.
    The reaction mass was transferred to a solution of 250 ml of ice-cold water and 250 ml of methanol. The precipitated product is sucked off, dried and recrystallized from 300 ml of n-butanol with the addition of activated charcoal. 24.6 g of a compound of formula 2 (3-benzo;, X p-cyanophenyl) are obtained, m, mp, 162-163.5 ° C.
    14.35 g of the obtained compound are dissolved in 150 1-liter of DMF, 8.4 g of KOH are added and stirred at room temperature for 1 hour. Then poured into 1.5 liters of ice-water, set with p.s. medium 5-7, the precipitate formed is filtered off with suction, and the precipitate is water and dried under vacuum at 60 ° C. 13.2 g of crude product are obtained, m.p., pl, 1-7-7 ° C, which is recrystallized from
    Q 2.00 ml of n-butanol with the addition of activated carbon. 9.5-g is obtained. Compounds of formula 1 (4,5-benzo; p O, X p-cyanophenyl).
    The same compound is obtained in good yield by intermolecular condensation of the corresponding starting aldehyde of formula 2 in the presence of CO in the medium of the solvents listed in the table, with,
    I
    Output, g
    Solvent
    Analogously to Example 2, a compound of formula 2 is obtained, wherein R, 3-benzo, x p-nitrophenyl, which is condensed in DIFA medium in the presence of KOH to form the compound of formula 1 (R + R2-4,5-benzo, nitrophenyl), t, pl, 218-220 С
    P and measures 3. 17.2 g of 2-naphthol-1-aldehyde is boiled for 30 minutes with 15.2 g of cinnamic acid chloride and 6.2 g of sodium methoxide in 150 ml of DMF. The solution is cooled and poured into a mixture of 250 ml of methanol and 250 ml of ice-water, the resulting residue is filtered off with suction, dried and recrystallized from 250 ml of butanol. 18 g of colorless crystals of the compound of formula 2 (R2, 2,3-benzo; X styryl) are obtained, mp 137.5138, 5 ° C,
    权利要求:
    Claims (2)
    [1]
    14.4 g of the obtained compound and 8.4 g of KOH are stirred for 2 hours at 150 ml of DMF, cooled and treated as described in example.
    [2]
    2. The crude product is recrystallized from 400 ml of n-butanol with the addition of activated charcoal. 8.7 g of compound of formula 1 (Rg 4.5 benz X styrene) are obtained, t, pl.174-176 C. Example 4. 58 g of salicylaldehyde sodium salt and 50.0 g of 4,4-bis-chloromethiphenyl are boiled in 900 ml of DMF. After the usual treatment, 83.8 g of crystalline crude product of the formula 2 (n 1, 4-biphenylene) are obtained, m.p. 193-195 ° C, 21.1 g of this compound is heated to boiling with 22.4-g. potassium butyrate in 250 ml of DMF for 6 hours in a stream of nitrogen. The solution is cooled, the precipitate formed is filtered off, rinsed with methanol and dried under vacuum. 9.2 g of a crude product of the formula 1 (R, RH; 4-biphenylene) are obtained. The products are recrystallized from 500 ml of methyl benzoate with the addition of activated carbon. The purified product melts higher. Example 5, 15 g of a compound of formula 2 (, 4-biphenylene) is mixed in a melt of 20 g of KOH or 20 g of NaOH in a porcelain crucible for 30 minutes. Then the mixture is allowed to cool, and then poured it into. 500 ml of water and neutralized with concentrated hydrochloric acid. The precipitate is filtered off with suction, the crude product is treated as described in example 4. 4.8 g of compound of formula 1 are obtained, the properties of which are described in example 4. Example 6.9.6 g of 1-formyl-2- (4-carbomethoxybenzyloxy) naphthalene The mixture is dissolved at 100 ml of dimethylformamide at comatographic temperature and treated with 3.36 g of potassium hydroxide. Then stirring is carried out for 60 minutes at 70 ° C, cooling with ice and stirring the precipitate in 300 ml of ice-cooled 1N hydrochloric acid. After 15 minutes, suction is performed, washing with water until there are no chlorine ions and drying under vacuum at 60 ° C. Thus, 8.8 g of the product of formula 1 (, R + 4.5 benzo; X p-carboxyphenyl) are obtained. .pl. . Example 7. 5.74 g of 1-formyl-2- (4-cyanonaphthylmethylenoxy) benzene is dissolved in 50 ml of dimethylformade. 1.4 g of potassium hydroxide is added and the mixture is stirred for 60 minutes at room temperature. Then the precipitate is poured into a mixture of 100 ml of ice water and 50 ml of methanol, brought to neutral with 2N hydrochloric acid, sucked off precipitate and washed with water. After drying under vacuum at 60. C, 5, 1. g of the product of formula 2 (.e, X 4-cyanonaphthyl), m.p., 127-128 ° C, are obtained. By analogy with example-6 receive the compound of formula 1, where, H; ; X 4-cyanonaphthyl, so pl. , and a compound of formula 1, where H- (CHj. and X 4-cyanonaphthyl, m.p. Example 8. 32 g of 1-formyl-2- (4-carbomethoxynaphthylmethylenoxy) benzene is dissolved in 150 ml of dimethyl-acetamide. Then 12 g of sodium hydroxide is added at 20 s. For 1 h, they are aged at 70 ° C. After that, everything is poured into 500 ml of ice water, precipitated with 2 n hydrochloric acid, sucked off, washed with water until chlorine ions are absent and dried under vacuum at. In a similar manner, 25.6 g of the product of the formula 1 (; X 4-carboxynaphthyl) are obtained, mp 222-223 ° C. Example 9. 20 g of the compound of the formula 2 (); X is a simple bond at carbon-carbon) is treated in 100 ml of boiling dimethylformamide with 8 g of potassium t-butylate for 30 minutes. Upon cooling, 15.3 g of the compound of formula 1 are obtained, R, a) X-simple bond to carbon-carbon) m.p. 197-198 ° C. Example 10. Analogously to Example 9 is prepared from a compound of Formula 3, in which. R + R2 means, on the one hand, a 2,3-benzo group, on the other hand, hydrogen atoms; , X-simple carbon-carbon bond, compound of formula 1, in which R.-f-R, 2 means, on the one hand, a 2,3-benzo group, on the other hand, hydrogen atoms, n-1, U-simple carbon-carbon bond), mp. 171 C. By analogy with example 10, a compound of formula 1 is obtained in which X is phenylene, m.p. HUA-ZOV With, a compound of formula 1, in which Rj.H,,, another, X-phenyl, so pl. , and also with: the rendering of the formula X, in which. X-styryl, e.d. 290C. Example 11. Of 21.3 g of a compound of formula 2 (R,, Xn-cyanophenyl) in 250 ml of dimethylformamide together with 6 g of sodium methoxide and 15 g of potassium t-butylate are prepared in a manner analogous to that described in Example B, 18.9 g product of the formula (; X-p-cyanophenyl), m.p.140-142 C. Claims of the invention The method of obtaining furan compounds of the general formula
     „- -.„ ... I ...-- / .. ,,.
    730.305;:,:: ,,,
    "ABOUT
    where R means a hydrogen atom, a lower alkyl or phenyl group;
    RJJ and Rg are hydrogen atoms, lower alkyl or alkoxy groups, or RV and R, together they mean a lower alkylene group or a fused benzene ring;
    n is O or 1, and if n is O, X is a substituted nitro, cyano, carboxy, carboxyalkyl group, phenyl, naphthyl, styryl, benzoxazolyl, or naphthoxazyl; if n is 1, .X means a simple carbon-carbon bond, phenylec, biphenylene, terphenylene, naphthylene, styrene, biphenylethylene, stilbile furylene, shadowed, and the double bonds in X are conjugated to the double bonds of the benzofuran residue.
     J V. ,,
    . , l., 4 a
    by combining
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    同族专利:
    公开号 | 公开日
    FR2149489A1|1973-03-30|
    DK136717C|1978-05-01|
    CH562237A5|1975-05-30|
    IT1049523B|1981-02-10|
    NO137276B|1977-10-24|
    DK136717B|1977-11-14|
    CA986514A|1976-03-30|
    NO137276C|1978-02-01|
    US3864333A|1975-02-04|
    JPS528311B2|1977-03-08|
    FR2149489B1|1977-12-23|
    GB1414670A|1975-11-19|
    JPS4828464A|1973-04-14|
    DD101397A5|1973-11-05|
    SE401834B|1978-05-29|
    DE2238628A1|1973-03-29|
    DE2238628B2|1978-10-26|
    BR7205493D0|1973-09-20|
    ES405653A1|1975-07-01|
    BE787580A|1973-02-14|
    AU474787B2|1976-08-05|
    AU4544072A|1974-02-14|
    AT320632B|1975-02-25|
    NL7210835A|1973-02-15|
    引用文献:
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    US3994879A|1972-12-18|1976-11-30|Hoechst Aktiengesellschaft|Process for the preparation of benzofuran compounds|
    DE2306515A1|1973-02-09|1974-08-15|Bayer Ag|BENZO-DIFURANE COMPOUNDS|
    CH635839A5|1976-08-04|1983-04-29|Sandoz Ag|METHOD FOR PRODUCING N-SUBSTITUTED AND QUATERNATED BENZIMIDAZOLES AND THE USE THEREOF.|
    LU78135A1|1977-09-16|1979-05-23|Ciba Geigy Ag|PROCESS FOR THE PREPARATION OF BENZODIFURANS|
    EP0010063B1|1978-10-04|1982-12-29|Ciba-Geigy Ag|Process for the preparation of furanyl-benzazoles|
    DE2904829A1|1979-02-08|1980-08-14|Bayer Ag|METHOD FOR PRODUCING BENZIMIDAZOLYLBENZOFURANE|
    JPS588632U|1982-02-09|1983-01-20|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH1192671A|CH562237A5|1971-08-13|1971-08-13|
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