MXPA97004000A - Benzopiran dyes and their intermed products - Google Patents

Abstract

The present invention relates to benzopyran dyes of the formula I, wherein n is 1 or 2, X 1 is oxygen or imino, X 2 is cyano or carbamoyl, R 1 and R 2 are independently including C 1 -C 13 alkyl, provided that the sum total of the carbon atoms present in R1 and R2 is at least 10, and R3 is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, carbamoyl, mono- or di (C1-C4 alkyl) carbamoyl, sulfamoyl either mono- or di (C1-C4 alkyl) sulfamoi

Description

BENZOPYRANE DYES AND THEIR INTERMEDIATE PRODUCTS The present invention relates to bensapyrene dyes of the formula I where n is 1 or 2, XI is oxygen imino, X2 is cyano or carbamsi 1 or, R1 and R2 are independently of each other C1-C1 alkyl, provided that the sum total of the carbon atoms present in R1 and R2 is when minus 10, and R3 is hi royepo, alkyl 3a C1-C6, alco-i Cl-C6 ,? halogen, cyn, or ro, c, rmayl, mono- or di-C1-C4 alkyl) carbamo? it, sulfa oyl or either mono- or di (C 1 -C 4 alkyl) sulfoxide, also refers to somacamine fights and their intermediates, and to the use of novel dyes for dyeing or printing synthetic materials. US-A-T ", 880 B? > 9 presents benzamino dyes.

However, it has been found that these products have non-sati fi cial application properties, especially uid in addition to > : I td-? . AND-. > or object of 33 r s t inv * ion offer t i ntu e. '. o | p? Not new! what ix n n pi op i e is li lic I > vi? v * -? > > -_ > - •! - > , e »μec J 33 mount a ei e affinity ei. "3 Hemo-? Found that the object of Jogra me before ln I nt '-?: • < l1. Fn.'? I | i ?? < ifif? -tipli ^ f ] i? ü? =. e the formula I. O lier a 3 u 13 o that in uentre en ~ > frulas ai vai gn nma y can u r ra i fi gt = td > chain, HIV, Rl, R2 and R7 are each, for example, melil, eti lo, propi lo, isoproi, butyl, t ^> obu < butyl, piif, i 3 or, j? ppi'uti lo, neopepfc t 3 o, i> -jr I -jn- it 13 o, lie I l or 2 - li 1 μent il. P1 and R7 They can also be, each, for example, heòti lo- or > "i 3o, 3-UÍJ J p.nlu, i .un ?. i 11, norp l, i njunni lo, de > . ? lo, r '> t _- > odo > ilo, und > ~ > > 13, dodei i 3 o, > r i ec i 3 o o 1 oi r i uec 1 i " 'I ii? L? -'-? Njrw > L ej ¡; > oo > : h t i > .i, ísononil, r.od '.- »:? ln > - » 1 - . 1 -n »i? 'ÍIJI' uncle are names irivia J s derived from alcohole, de roceso 'o (see Fn? -?" Loped la of Industri al pheup - > iry de Jlman, * edition, vo3 Al, p-1g, 790 a 293, 0 a-, fto vo.? 10, pa > -, 14 84 &.) P ™ 'can - also, by * »jtímplp, eo: '1, e!, O. \ ?, propose 1, i - propo; - 1, buloM, j soboio; - 1, sec-bn 1, l, er fc - bf 1 t., T, t 111". i, 1, 1 -lo in i 3 o, 1, neop nt i lo? 1, tert- μent 1 lo :, ¡¡, * tí; í 1 nur r 1 gold, bromine, mono-? > b in im l i 1 > ai b-imcn ln, mono- or luen > 11 the 11th arbon 13 or, mono- or dipropyl Icarbamoyl, mono- or diisopropylcarbonyl, mono- or dibutylbalayl, N-met i 1-N-but icarba oi it, mono- or d imet i lsul f oi lo, mono- or dietary i Isul fa oi lo, mono- or ipro i lsul f oi lo, mono- or di isopro i 1 sul fa oi lo, mono - or dibut i lsul fa oi lo obien N ~ me 11-N-et 11 ^ ul f oi lo. Preference is given to benopuryl dyes of the formula I where Pl and R2 are, indepently lence among them, alkyl C5-C13, specifically C3-C10 alkyl. Particular preference is given to ben opiran dyes of the formula I wherein P3 is hydrogen, methyl or chlorine, especially hydrogen. Is it given ad? Canvas 3 mind preference to ben dyes opirano? formula I where is i ino. Special preference is given to the dyes of ben; op? R-no of formula I where X2 is iano. The present invention provides iminocouminal adducts of formula II where p is 3 or 2, Pl and R2 are independently C1-C13 alkyl, provided that the total sum of the carbon atoms present in R1 and R2 is greater than 10, and P3 is hydrogen), C1-6alkyl C 6, C 1 -C 6 alkoxy, halogen, cyano, nitro, carba oyl, mono- or di (C 1 -C 4 alkyl) carbamoyl, sulfa oyl or mono- or di (C 1 -C 4 alkyl) sulfa oi 1 o. The no-maps of the formula II can be obtained in a conventional manner, for example by condensing a 3 i i i i 1 a 1 due from 3 to formula III where Pl and P2 are each as defined above, with a Clanomet and IbencImidapol of formula IV where n and R3 are each as defined above. R ondensación, segi'm described for example in US-A-3,533,730 or in US-A-4,299,959, is generally carried out in a diluent (such as alcohol or N , Nd? Et i 1 form id) in the presence of a l rte, for example μ (pendí na obi ef i pi rro! JIIJ GH) aie μer. be a ambien e or a t eipp -? high, l s f? ¡? ? (O cíuma ri nai-i laughs 3 af or 'or 1 to TT - »on pous e; p ta 1 mind'? 'H il' to p '" eμ- > ra > in dye *, 7> N. '?) | I? Rdi!' I the formula T. FA CÍ in en, ,, a nono oo ari na '"le 1 To formula 13 in a di luie t i.on aloni tri lo or else ut > - 1 to i? Hi-e to the uil oC1 ~ Cé, "F? Dt 'method t; -? onoc p ^ v r > e and is covered by, for example, in J ÜO HI. IUU Uf. -A - 3 BC '869. l or novel dyes -, of lien,.' op i ra not of] formula T are? '? ! 13 o-, for 1 eñ i r or for impremi r - * í er t a I e- > For example: μol i entere, pol? am? da -3 or else pol? -i? bonus I os. P-t r 1"i"; i;? In this case, they are matte and they are the same, as, for example, fiber *.

Together, tidy or non-woven- », polyester or pollinated compounds or a polyester and cotton blend. I > > . dye- »of ben opirano uncle the μri? -3erd and invention = > On top of that, it was also used to dye what were you doing?)? i'- ?, p »_ > For example, elon or b io skin e - .. The bents of the third invention are remarkable- because of their good affinity. They produce bright dyeings, fl ood, and prints with red tones. The examples illustrate the 3a < nvem? ? T \ "l" G.TF.MPL 1 A 400 ml of methanol were added 41.6 g of 1 -.? Imino-3- (benz imidaso1-2- i1) -7-di.pent the inocoumar i i na 8.6 g of malanitrile and 3 g of formic acid The mixture was refluxed for 12 hours under stirring, then cooled and the resulting precipitate was removed by melt filtration, washing with methanol and drying, leaving 42.3 g of the of the formula ((HPLC purity 92V «> EXAMPLE 2 To 400ml of methanol 44.4 g of l-imino-3 ~ (bi in imidazole -2- i1) ~ 7-d ihe were added: <i> inocoum ri , 8.6 g of malonitrile and 3 g of formic acid This mixture was heated under stirring in an autoclave at a temperature of 100-105 ° C under a possible autogenous pressure of 3 to 3.2 bar L stirring continued at a set temperature for 2 hours When the mixture was cooled and decompressed, the resulting precipitate was removed by filtration with suction, washed with methanol and dried, leaving 44.4 g of the 1-fold dye (HPLC purity: 93 *) EXAMPLE 3 Example 2 was repeated with a reaction time of only 1 hour, giving a similar result EXAMPLE 4 Example 2 was remitted with only 1 g of formic acid as a taliser, giving a similar result. Example 1 with 1 g of titanium titrated tet as catalyst, provides ndo a similar result. EXAMPLE 6 Example 2 was repeated with 47.2 g of 2-1 ml non-3- (ben imida zol-2-? 1) -7- ihepti laminocoumar na, proportion n 48. 2 g of the dye of the. formula (Purity 92.5% HPLCí) FJEMPI 0 7 Example 1 was repeated replacing l s S.6 g malonitplo by 14.7 g of ethyl cyanoacetate, 43.0 g of propor ionando. dye of the formula (purity by HPL.C: VA) EXAMPLE 8 The was repeated. Example 2 43.0 g of 2-imino (zol-2 benz imid 1) -7- (N-pen i l-N-I? i lamino) coum ri na, p opor ionando 43.4 g of nte of formula (purity by HPLC: 93.4%) EXAMPLE 9 15.7 g (0.1 mole) of 2-cyano and 1-benzimidazole and 27.7 g (0.1 mole) of 4-d ipent i la nosa were cned. 100 ml of methane !, mixed with 1 ml of pi rol. I donated and stirred at 40 ° C for 3 hours. After cooling to room temperature, it was removed by the precipitate by filtration with suction and washed with 40 ml of methanol, leaving 26.8 g of a compound of 1-mul The method of Example 9 also provided the imi quouma bouts that appear in the list in the following

Claims (7)

1. CLAIMS 1. Benzopi anus dyes of the formula I where n is 1 or 2, XI is either oxygen, X2 is cyano or cartiam ilo, Pl and P2 are, independently of each other, C1-C13 alkyl, provided that the sum total of the carbon atoms present in Pl and P2 is at least 10, and P3 is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, cyano, nitro, carba oyl, mono- or di- (3-chloro Cl-
2. C4) carbamo? The sulfamoyl is either mono- or di (C 1 -C 4 alkyl) or 1, 2, or 2, benzapyrano dyes according to claim 3, wherein R 1 and R 2 are independently C 5 -alkyl. C13
3. 3. Benzopyran dyes according to claim 1, wherein R3 is hydrogen, methyl or C l or.
4. 4. Benzopyran dyes according to claim 3 in the rei indicates ion 1 where XI is i ino.
5. 5. Benzopyran dyes according to claim 1 wherein XI is cyano.
6. 6. Iminocoumarins of the formula II where n is 1 or 2, P.1 and P.2 are, independently of each other, alkyl C1-C1.3, provided that the total sum of the carbon atoms present in R1 and P.2 is at least 10 and R 3 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, cyano, nitro, carbamoyl, mono- or di (C 1 -C 4 alkyl) carbamoyl, sulfamoyl or mono- or di (C 1 -C alkyl) - C4) s? Lf moi lo,
7. 7. The use of the benzopyran dyes of the claim 1 to dye or print synthetic materials.