• 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:
    2-Phenyl-5-benzimidazol-2'-yl-furanes of the formula <IMAGE> (1) in which R1 is a sulphonic acid group or an ester or amide thereof, a carboxylic acid group or an ester or amide thereof, a cyano group, a trifluoromethyl group or an alkyl- or arylsulphonyl group, R2 is alkyl having 1 to 8 carbon atoms, alkenyl having 3 or 4 carbon atoms, cyclohexyl, hydroxyalkyl having 2 to 4 carbon atoms, alkoxyalkyl having a total of 3 to 6 carbon atoms, carboxyalkyl having 2 to 6 carbon atoms, carbalkoxyalkyl having a total of 3 to 6 carbon atoms, cyanoalkyl having 2 to 4 carbon atoms, carbamoylalkyl which has 1 to 6 carbon atoms in the alkyl moiety and is unsubstituted or substituted on the nitrogen atom by 1 or 2 alkyl having 1 to 3 carbon atoms, benzyl which is unsubstituted or substituted by chlorine, methyl or methoxy, dialkylaminoalkyl having a total of 3 to 7 carbon atoms or phenethyl and, if n is the number 0, also hydrogen, R3 is hydrogen, alkyl having 1 to 6 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, cyanoalkyl having 2 to 4 carbon atoms, carboxyalkyl having 2 or 3 carbon atoms, carbamoylmethyl which is unsubstituted or substituted on the nitrogen atom by 1 or 2 alkyl having 1 to 3 carbon atoms, alkoxycarbonylalkyl having a total of 3 to 6 carbon atoms, alkenyl having 3 or 4 carbon atoms or benzyl which is unsubstituted or substituted by chlorine or methyl, R4 is hydrogen, chlorine, bromine, fluorine, carboxyl carbalkoxy having a total of 2 to 5 carbon atoms, alkoxyalkoxycarbonyl having a total of 4 to 6 carbon atoms, benzyloxycarbonyl, cyano, sulpho, alkylsulphonyl having 1 to 4 carbon atoms, carbamoyl or sulphamoyl which are unsubstituted or substituted by 1 or 2 alkyl groups having 1 to 4 carbon atoms, or sulphonic acid phenyl ester or trifluoromethyl, R5 is hydrogen, chlorine or methyl, R6 is hydrogen or chlorine, n is the number 0 or 1 and A(-) is a colorless anion equivalent to the cation of the fluorescent brightener, their preparation as well as their use for optically brightening organic materials are disclosed.
    公开号:SU1075988A3
    申请号:SU782581900
    申请日:1978-02-20
    公开日:1984-02-23
    发明作者:Рудольф Мейер Ханс；Вебер Курт
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the chemical technology of textile materials, in particular to the technology of optical bleaching of textile materials. The known method of optical bleaching of textile materials by treating them with an aqueous solution of 2-phenyl-5-benzimide sol - () - yl-furans i derivatives However, the degree of whiteness is achieved when using the known derivatives of 2-phenyl-5-benzimidazole ( 2) -il-furatsov, not high enough. The purpose of the invention is to increase the degree of whiteness of textile materials. The aim is achieved in that according to the method of optical bleaching of textile materials by treating them with an aqueous solution of 2-phenyl-5-benine, zimidazole- (2) -yl-furan derivatives, as mentioned derivatives use compounds of the general formula (®Kz) l (J) where R.-COOH, COOCH, cyano, trifluoromethyl, methylsulfonyl ethylsulfonyl, phenylsulfonium My, S020C6H5, OjOC jHj OCH-j, or 5O.JH, V2 g where YI - hydrogen, methyl, sshllil, hydroxyethyl, mego-toxiethyl or dimethylaminopropyl, which ELF is to be quaternized, Yj vodor metilf 8d or methyl, ethyl, CM-butyl, allyl, or CH2CgH5; Rj is hydrogen, methyl, ethyl, hydroxy ethyl, methyl cyan., Ethyl acetate, CHjCgH5, CHjCOHH or N; . - hydrogen or chlorine; Rf is hydrogen, chlorine or methyl; Г - О or 1, А - CH, 5qi, С1, въ or CHj-CjHj-S .0,05 with their concentration in the range of 0/4% of the weight of the material. Specified in. In the examples, percentages are by weight. Example 1. To a hot solution of 26.7 g of 2- (4-chlorophenyl) -furan-5-aldehyde (content 77.4%) and 29.25 g of 3-amino-4-ethyl phenobenzenesulfonic acid phenyl ester in 200 ml of monomethyl ethylene glycol ether was added with 21.3 ml of an aqueous 40% sodium bisulfite solution. The mixture is stirred for 2 hours at room temperature, diluted with 40 ml of water and cooled. The precipitated product is squeezed out on a suction filter, washed with methanol and water and dried under vacuum, after which 40.4 g (84% of theory) of a compound of the formula is obtained which after recrystallization from petroleum ether and monomethylglycol ether glycol glycol separates into almost colorless crystals from m.p. 171 ° C. .. Example 2. 20.7 g of 2- (4-chlorophenyl) -furan-5-aldehyde and 20.1 g of 2-methylamino-4-methylsulfonyl-aniline are heated to a boil in 60 wi of ethanol for 20 minutes with reverse reflux. . 40 ml of nitrobenzene are added, ethanol is distilled off and the temperature is raised to the boiling point of nitrobenzene. After 5 minutes, the temperature of the reflux is allowed to cool, mixed with 40 ml of methanol, the precipitate formed is pressed on a suction filter, washed with methanol and dried in vacuo. This gives 22.3 g of a compound of the formula From the dichlorobenzene and ethylene glycol monomethyl ether, it is released in almost colorless crystals with m.p. 235C. According to Example 1 or 2, of the corresponding 2-phenyl-furan-5-aldehyde and o-phenylenediamines, compounds of the formula Rach, RZ, 4-7 are given the values given in Table 1. Example 3. 22, Зг2 - (, 4-chloroenide) -furan-5-carboxylic acid in 9.7 mp of thionyl chloride, 60 ml of toluene and 0.8 ml of dimethylformamide are heated for 1 h with reverse reflux and the solution is completely evaporated in vacuo. To the solid residue, a solution of 24.3 g of 3-amino-4-L-butylaminobenzenesulfonic acid amide in 150 m of glacial acetic acid is added in portions, 9.0 g of anhydrous sodium acetate is added and stirred for 1 hour at room temperature. The mixture is then heated for 3 hours at reflux temperature, cooled and stirred with 150 ml of water. The precipitated product is filtered, washed with water and dried. 39.7 g (92% of theory) of a compound of the formula sogimj, m.p. 260®C after recrystallization from O-dichlorobenzene and ethylene glycol monomethyl ether. Example 4. 38.8 g of sulfoxides of the formula are stirred for 3 hours with reverse reflux in 300 ml of chlorobenzene, 23 ml of thionyl chloride and 1 ml of dimethylformamide, after which the release of hydrogen chloride ends. The resulting solution is cooled to 5 ° C, the crystalline precipitate is sucked off, washed with xylene and dried in vacuum at 80 ° C. 30.6 g of the sulfonic acid chloride of the formula are obtained. After recrystallization from xylene, the sample melts at. 9.0 g of the compound of formula 42 in 60 ml of ethylene glycol monomethyl ether and 4.9 ml of pyridine are heated to 80 ° C for 15 minutes, and it goes into solution. Upon cooling to 5 ° C and adding 60 ml of water, the reaction product crystallizes out. It is pressed on a suction filter, washed with water and dried over calcium chloride in vacuo at room temperature. 7.5 g of Kp% of the theoretical sulphate ester of the formula sof ecuf cHf- oei is obtained. After recrystallization from tetrachloride carbon, the product melts at 146 G. Example 5 To a solution of 7.73 g of compound (3) in 40 ml of dimethylformamide at 1200 s at While stirring, 2.3 ml of dimethyl sulfate are added dropwise, after which they are stirred for another 30 minutes at this temperature, 3, then cooled and diluted with 40 ml of isopropanol. The crystallized product is filtered off with suction, washed with isopropanol, and dried under vacuum at. 9.75 g (95% of theory) of a compound of the formula SOeCH, -tCHjOSof is obtained. The compound can be directly used for bleaching polyacrylonitrile, or it can be purified by recrystallization from water. It is planted in the form of luminous crystals with m.p. 276 ° C. In a similar way, compounds of the general formula where 1-7 A are obtained are as indicated in Table 2. Example 6. To a solution of 4.73 g of a compound of the formula (EO) in 50 ml of dioxane and 30 ml of chlorobenzene, 1.14 ml of dimethyl sulfate are added dropwise. At the end of the addition, the mixture is stirred for another 1 h at this temperature, wrung out with a suction filter with a hot filter and washed again with toluene. Obtain 5.7 g (95% of theory) of the compound of the formula .SOa "HHHz jN iCHj), .and-cnjosof
    which can be recrystallized from alcohol (m.p.).
    Example 7. To 100 ml of water was added 0.2 g of sodium nitrate, 0.2 g of 80% sodium chlorite, 0.2 g of oxalic acid, or an equivalent amount of another organic or inorganic acid suitable for this purpose. 1 g of the bleach of formula (44) is dissolved in 1000 ml of water. 1.5 ml of this stock solution is added to the above solution. The resulting treatment bath is heated to, then 3 grams of heavy polyacryl fabric is added, the temperature is raised within 10-15 minutes to 95-98s and the bath is maintained for 60 minutes at this temperature. The fabric is then rinsed with cold water and dried at 60 ° C for 20 minutes. The treated fabric has a degree of whiteness, 20 characterized by a 245 degree whiteness index on the Ziba-Geigy scale; with good light fastness. Effects with an index of 205-260 degrees, whiteness is obtained with compounds of the formulas (2), 75 (3), (5) -C7), (9), (10), (12), (14), (15), (17) - (20), (23), (25) - (28), (30),. (31), (33), (34), (36), (41), (43), ( 47), (49) (54), (56), (57), (59), (60), (63), (65) C67), (70) - (76), (79), (82 ), (84) - (88) - and ,,, (102) - (105).
    Example 8. To 100 ml of water, 0.1 g of oxalic acid, 0.1 g of sodium acetate, 0.0125 g of sodium bisulfate and 0.025 g of polyphosphate are added as complexing agent.
    l A solution of an optical brightener, a solution of 1 g of a compound of formula 1.44) in 1000 ml of water is obtained. 6 ml. this stock solution is added
    to the described solution. 40 received
    The whitening bath is heated, then a 3-g modified polyacrylonitrile cable is introduced into it. The temperature is raised to 98 ° C for 10-15 minutes and the material is processed for 45-30 minutes at this temperature. Then the material is washed with cold water and dried. In this case, the degree of whiteness reaches 200 kg of whiteness on the Ciba-Geigy scale. The effect of 165-200 degrees JQ whiteness is obtained with compounds of the formulas (47), (49) - (53), (56), (57), (59) (61), (63) - (69), (71) - (76), (79), (81) (88), (102) and (103).
    Example 9. An aqueous 55 solution is obtained which, with respect to the weight of the bleached material, contains 0.3% of the bleach of formula (44). This solution is heated to. Then a modified poly-60 ether fabric is introduced into the solution. Bath module 1:25. The temperature is raised to 30 ° C over 30 minutes and left for 30 minutes at this temperature. Then cool for 15 minutes before, then 5
    the fabric is washed with running cold water and dried with an iron. The treated fabric has a degree of whiteness, characterized by a 220 degree Cib-Geigy scale. Effects of 215-230 degrees of whiteness are obtained with compounds of the formulas (46), (50) - (57), (59), (61), (63) - (65), (72), (73), (75) , (76), (82) - (85) and (88).
    Example 10. A freshly formed, stretched polyacrylate wet tow (dry weight: 3, O g) is immersed for 10 seconds in a 100 mm water bath containing 0.0005% bleach of formulas (44), (47) or (GE). The pH of the oxalic acid solution is 4. Then the rope is washed for a short time with water and dried at 90-100 C. Thus, polyacrylonitrile fiber with a bleaching effect of 165–200 degrees of whiteness on the Ziba-Geigy scale is obtained.
    Bleaching can also be carried out at pH 6 (established by the addition of sodium acetate). Increased, for example, to the temperature of the bleaching solution increases the rate of bleaching.
    Higher bleaching effects are achieved by increasing the bleach concentration, for example, to 0.005%.
    EXAMPLE 11 Acetylcellulose tissue is introduced at a bath module of 1: 30-1: 40 and at a temperature in a solution containing 0.15% of the compound of formula (47) per fiberized material. The temperature of the finishing bath is adjusted to 90-95 ° C and kept at this temperature for 30-45 minutes. After washing and drying the fabric, the effect of bleaching is 215 degrees of whiteness on the Diba-Geigy scale. The effects of 210-220 degrees of whiteness are obtained with compounds of the formulas (50), (51), (63), (65) (66), (79) and (81) - (84).
    Example 12. Polyamide fabric. Da-6 was introduced wet at a bath modulus of 1:30 and temperature in an aqueous solution of pH 9.5, containing 0.2% of a compound of formula (f44) calculated on the fibrous material. Used for. 10 min. - the temperature is brought up and left for 20 min at this temperature. After washing and drying, the treated fabric is ironed at 180 ° C. It has a whiteness equal to 250 degrees on the Ciba-Geigy scale. Effects of 225245 degrees of whiteness are obtained with compounds of the formulas (47), (49) - (54), (56), (61), (59), (63), (64), (66) - (69), ( 72), (73), (75), (76), (79), (84), (85) and (88)
    Example 13. An aqueous solution is obtained containing 0.3 g of a bleach of formula (51), 0.3 g of adduct of 35 mol of ethylene oxide and 1 mol of stearyl alcohol, 0.3 g of an adduct of 8 mol of ethylene oxide and 1 mol of octylphenol, 270 ml of deionized water and 30 ml of ethanol (95%. Cellulose fabric is plus in this solution (-absorption of the solution is 60%). Then the fabric is dried in a drying cabinet at. The fabric has a bleaching degree equal to 215 degrees of whiteness on a scale Tsiba-Geigi Effects 185- 220 degrees of whiteness is obtained with compounds of formulas (52), (56), (59), (70), (72), (75), 76) and (85). Example 14 (comparative). The polyacrylonitrile fabric is treated on a dyeing device with a 1:25 bath module in an aqueous solution containing per liter: 1 g of adduct of 35 mol of ethylene oxide with 1 mole of stearic alcohol, 0.25 ml of acetic acid (80%), and 0.05, 0.1 and 0.4% with respect to the weight of the fabric compared to bleach. The fabric is introduced into the bath at and the temperature is raised within 30 minutes to 97 seconds. This temperature is maintained for 30 minutes, and then the bath is cooled for 15 minutes to Tivs. The treated fabric is watered with water and dried with an iron heated to 1600s. Compounds of formulas (H), C57) are used as a bleach (74L and a known compound used by a known method. The degree of whiteness of fabrics treated in this manner is determined on a Ciba-Geigy whiteness scale using a spectrophotometer. The results are shown in Table 3. Thus, the invention provides an increase in the degree of whiteness of textile materials. Table
    Ct
    CE Ct
    n n n
    sn,
    n n n
    here N
    with"
    n
    se
    n n
    n n
    n se
    n
    se
    n
    n
    n se
    n n
    n n
    n n
    se
    n ii
    n
    Ct
    II
    221
    ,, 208
    ,
    SOjCH, 205,271
    coaxially
    329 soon H, CF, 204
    .H,
    232
    189
    at 207
    117 f, U 199
    Continuation of table 1
    Continued table. 2
    Sn CI.ICN ci
    SO OCgllj. СН Ct
    Ct
    CH.
    SOjOC Hg
    3
    205
    57 74 185 230
    Famous Bleach125 Tel
    ,
    Continued table. 2
    220 (with
    decomposition)
     213
    n n
    257-262
    Vg
    Table3
    215 260 260
    110
    权利要求:
    Claims (1)
    [1]
    METHOD FOR OPTICAL WHITENING OF TEXTILE MATERIALS by treating them with an aqueous solution of 2-phenyl-5-benzimidazole- (2 4 ) -yl-furan derivatives, characterized in that, in order to increase the brightness, the compounds of the general formula are used as these derivatives where R ^ - COOH, COOCHj, cyanide group, trifluoromethyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl
    SO 2 OC 6 H 5 , so 2 oc 2 h 4 och-, ΟΟΜΥ 4 Υ 2 OR SOjNY ^ y ^, where Y {is hydrogen, methyl / allyl, hydroxyethyl, methoxyethyl or dimethylaminopropyl, which can be quaternized with CH ;
    Υ 2 is hydrogen or methyl; R 2 is methyl, ethyl, D-butyl, g allyl, CH. CN or CH 2 C 6 H 5 ;
    - hydrogen, methyl, ethyl, hydroxyethyl, methylcyanine, ethyl acetate, CH 2 C 6 H CH CONH 2 or CjH ^ CN;
    R4 is hydrogen or chlorine;
    Re is hydrogen, chlorine or methyl;
    η is 0 or 1;
    A is CH3SO4, C1, Br or
    С1ЦС 6 il "-so , with their concentration in solution of 0.050.4% by weight of the material.
    SU., „1075988
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1075988A3|1984-02-23|Method for optically bleaching textile materials
    CA1099727A|1981-04-21|Benzofuranyl-benzimidazoles
    DE2248772B2|1979-07-26|Pyrazoline compounds
    CA1084061A|1980-08-19|Divinyl stilbenes as optical brighteners
    DE2704825C3|1979-11-29|Fluorescent dyes, processes for their production and their use for tinting organic materials white
    US3900419A|1975-08-19|Benzofurans
    US4264325A|1981-04-28|Phenyl-benzimidazolyl-furanes for optical brightening of organic materials
    DE1296121B|1969-05-29|Optical brighteners
    US4429133A|1984-01-31|2&#39;-Benzothiazolyl-and 2&#39;-benzoxazolyl-2-benzimidazoles
    US4110246A|1978-08-29|Mixture of benzoxazole derivatives
    US4309551A|1982-01-05|Quaternized, bridged benzimidazolylbenzimidazoles, processes for their preparation and their use
    US4791205A|1988-12-13|Bisbenzoxazolylnaphthalenes containing sulfonate or sulfonamide groups, a process for their preparation and their use
    EP0011824B1|1981-10-14|Benzofuranyl-benzimidazoles, process for their preparation and their use in the optical bleaching of organic materials
    US3637672A|1972-01-25|Azole compounds
    US3427307A|1969-02-11|Benzoxazole optical brighteners
    CA1148955A|1983-06-28|Cationic compounds of the naphthalimide series, process for their preparation and their use
    US4271293A|1981-06-02|Benzofuranyl-benzimidazoles
    US3649633A|1972-03-14|4 naphthalimido pyrazolium salts
    US3288786A|1966-11-29|Naphthotriazole optical brighteners
    US3862179A|1975-01-21|2-stilbenyl-4-styryl-v-triazoles
    US3849331A|1974-11-19|4-naphthalimido cycloammonium-acrylic fiber compositions
    US3657139A|1972-04-18|Pyrene derivatives as optical brighteners
    US3547952A|1970-12-15|7-mercapto-coumarins
    US3394144A|1968-07-23|1-amino-2-dicarboximidoalkoxy-4-hydroxyanthraquinones
    US3642799A|1972-02-15|Sulphonium naphthalimides
    同族专利:
    公开号 | 公开日
    FR2392989B1|1980-06-13|
    CH619337B|
    CH638805A5|1983-10-14|
    CH619337A|1980-09-30|
    LU76819A1|1978-10-18|
    SE7801991L|1978-08-23|
    SE444318B|1986-04-07|
    DE2807008A1|1978-08-24|
    AU3347978A|1979-08-30|
    JPS53105529A|1978-09-13|
    US4189589A|1980-02-19|
    GB1574891A|1980-09-10|
    ES467154A1|1979-01-16|
    BR7801032A|1978-12-19|
    FR2392989A1|1978-12-29|
    MX150275A|1984-04-10|
    JPH0141161B2|1989-09-04|
    NL7801882A|1978-08-24|
    AR226809A1|1982-08-31|
    ATA124478A|1979-09-15|
    AU513775B2|1980-12-18|
    DD137939A5|1979-10-03|
    CA1111044A|1981-10-20|
    BE864138A|1978-08-21|
    AT356053B|1980-04-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE1469227A1|1964-12-31|1970-06-04|Bayer Ag|Furan compounds|
    DE1594841A1|1966-01-14|1970-07-23|Bayer Ag|Whitening agents|
    CH544179A|1970-12-09|1973-12-28|Ciba Geigy Ag|Use of quaternized benzofuranyl-benzimidazoles as optical brighteners for textile organic materials|
    DE2346316C2|1973-09-14|1985-02-14|Bayer Ag, 5090 Leverkusen|Process for the preparation of 2-furylbenzimidazoles|
    CH616422A5|1974-05-23|1980-03-31|Sandoz Ag|US4264325A|1977-02-22|1981-04-28|Ciba-Geigy Corporation|Phenyl-benzimidazolyl-furanes for optical brightening of organic materials|
    CH645359A5|1978-11-20|1984-09-28|Ciba Geigy Ag|STORAGE-STABLE, CONCENTRATED AQUEOUS SOLUTION OF BENZIMIDAZOLIUM BRIGHTENERS.|
    DE2954597C2|1978-11-20|1994-03-31|Ciba Geigy|Process for the preparation of benzimidazolium compounds, aqueous solutions of these benzimidazolium compounds, their preparation and their use|
    DE2854428A1|1978-12-16|1980-06-26|Basf Ag|METHOD FOR PRODUCING 2-IMIDAZOLINES|
    CH645941A5|1980-02-05|1984-10-31|Sandoz Ag|STABLE BRIGHTENING SOLUTIONS AND THEIR PRODUCTION.|
    US4542222A|1980-12-29|1985-09-17|Ciba-Ceigy Corporation|Benzimidazoles|
    DE3425151A1|1984-07-07|1986-01-16|Henkel KGaA, 4000 Düsseldorf|HAIR DYE|
    DE19500195A1|1995-01-05|1996-07-11|Bayer Ag|Use of white-tinted plastics for tinting paper coating slips and such white-tinted paper coating slips|
    DE60137422D1|2000-07-04|2009-03-05|Showa Denko Kk|METHOD FOR PRODUCING A BENZOLDIMETHANOL COMPOUND|
    AU2006325294B2|2005-10-31|2012-10-11|Merck Sharp & Dohme Corp.|CETP inhibitors|
    US8362268B2|2008-05-30|2013-01-29|University Of Notre Dame Du Lac|Anti-bacterial agents from benzo[d]heterocyclic scaffolds for prevention and treatment of multidrug resistant bacteria|
    CA2768832A1|2009-07-23|2011-01-27|Vanderbilt University|Substituted benzoimidazolesulfonamides and substituted indolesulfonamides as mglur4 potentiators|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    LU76819A|LU76819A1|1977-02-22|1977-02-22|
    [返回顶部]