TWI363783B - Novel reactive dyestuff with n,n-dialkylamino bridge group - Google Patents

Description

1363783 IX. Description of the Invention: [Technical Field] The present invention relates to a novel reactive dye which is a bridging group of W, y-dialkylamino, especially one suitable for hydroxyl group-containing A new reactive dye for dyeing, cold dyeing, continuous dyeing, printing and digital printing of polyamine fibers.

10 [Prior Art] 15

The azo dye is a dye precursor composed of a diazo component and an even component, and is widely used because of its wide color gamut and high molecular absorption coefficient, and is used as a reactive dye for dark dyeing such as orange, red, navy, and black. Pigment precursor. The azo dyes are best known as the naphtha reactive dye CI Reactive Black 5, which was developed by the Hoechst Company in Germany in 1957. The sulphato-ethyl-sulphone (hereinafter referred to as SES) is the most famous. ) For its structure, this dye can dye fabrics to very dark colors.

HO3SOH4C2O2S

SO2C2H4OSO3H fiber reactive dyes have been used in the dyeing and finishing industry for many years. Nowadays, the development of reactive dyes is oriented towards the economics of higher fixation and higher dyeing. In order to surpass the high-durability and economical characteristics of CI Reactive Black 5, many teams have been involved in the development of research over the years. For example, in Hoyerst, Hoyer et al., 1980, published in US Pat. No. 4,244,258, 20 1363783 Sulfonyl is a bridging Tetraazo structure in which the dye can be as shown in formula (B).

In the U.S. Patent No. 5,629,410, the tetrazozo structure of an aminocarbonyl or aminosulfonyl bridge is disclosed in U.S. Patent No. 5,629,410, the disclosure of which is incorporated herein by reference. As shown in formula (C).

However, the new compounds developed by the above research team are still unable to meet market requirements due to their dyeing depth, hue shift, leveling and washing fastness, so there is an urgent need for improvement. 10 1363783 SUMMARY OF THE INVENTION Through a multi-party research experiment, it was found that a new compound containing a dialkylamino bridging group (shown in the following formula (D)) and #, a dialkylamino bridging group, can be applied to a reactive dye. The novel structures such as yellow, orange, red, navy, and 5 black can be synthesized to exhibit high color, high fixation, stable fiber and dye bonding, and excellent fastness characteristics. (^2) 0-3

(Rl)〇-3

R B-(CH 2 ) mN-(CH 2 ) n ^ B '- -NH 2 (D) 10 Accordingly, the present invention provides a novel reactive dye structure having a novel dialkylamine group as a bridging group, and the reactive dye is dyed. Cellulose fibers can exhibit good fixation, excellent dyeing, and excellent wash fastness and wet fastness properties. The structural formula of the novel reactive dye having an anthracene, fluorene-dialkylamino bridging group of the present invention is represented by the following formula (I):

Wherein, Ει and Ε2 are each independently selected from the group consisting of benzene, naphthalene, pyrazolone, monoazo, disazo, polyazo ( Polyzo) and a group of metal complex azo structures; (I) 1363783 R is hydrogen, CU4 alkyl, (: 丨.4 alkylcarbonyl, phenyl, argene (nitroso), or a Cw alkyl group substituted with a halogen, a hydroxy group, a carboxyl group, or a sulfonic acid group (suif0); (Rl) 〇-3 and (β·2)0 3 is 0 to 3 identical or different substituents, 5 and each independently selected from hydrogen, argin, hydroxyl, carboxyl, sulfonate, nitro, cyano, Cw alkyl, a group consisting of alkoxy, ureido, and amido; B and B' are each independently selected from the group consisting of a straight chain, -S02·, and #-C0NH-(CH2) a group consisting of k-S02-; 10 k is an integer of 1, 2, 3, 4, 5 or 6; z and Z' are each independently selected from -so2-u, -C0NH-(CH2)d-S02- U,-0-(CH2)r- C0NH-(CH2)d-S02-U, /3 -thiosulfatoethylsulfony l and -N(R')-U' group; d and r are each an integer of 2, 3 or 4; 15 U is -CH2CH2W or -CH=CH2; W is treated with alkali to leave a group of -Cl, -OS03H, _ -OPO3H 'quaternary ammonium, 11 pyridine, carboxypyridinium, methyl 0 to bite ( Methylpyridinium)

—N—C2H4SO3H 20 (carbonamidopyridinium), or 84; R_3 and R4 are each independently an atmosphere or Ci_4•••; U' is 〇:, --halopropionyl, α-halopropyl (α-haloacryloyl), β-halopropionyl, or α-^63783 α-haloacryloyl; R' is hydrogen or Cw alkyl; each independently is 0, An integer of 1 or 2, and i and j are not 0 at the same time, and melon and η are each independently an integer of 2, 3 or 4. In the reactive dye of the formula (I) of the present invention, wherein & and <2> can each independently be a ketamine structure, preferably a structure of the following formula (* indicates a coupling position):

Wherein G is a Ct.3 alkyl group, a carboxylic acid group or a c2_5 alkanocarboxylic acid group, and each of r5 and I is independently selected from the group consisting of hydrogen, halogen, hydroxyl, carboxyl, sulfonic acid, nitro, cyano, C!-4 A group consisting of a base and a CV4 alkoxy group. In the reactive dye of the formula (1) of the present invention, wherein & and e2 may each independently be a stupid structure, preferably a structure of the following formula (* indicates a coupling position): (1-2) wherein, (R? Wherein o-3 is 0 to 3 identical or different substituents, and 2〇 are each independently selected from the group consisting of an anion, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, a nitro group, a cyano group, a Cw alkyl group, and a Cm alkane. A group consisting of an oxy group, a C6 6 alkoxycarbonyl group, an amine carbaryl group 1363783 (carbamoyl), a C2-5 alkanoylamino group, and a C2-5 sulphuric acid group. Among the reactive dyes of the formula (I) of the present invention, ugly! And E2 may each independently be a naphthyl structure, preferably a structure of the following formula (* indicates a coupling position):

OH H03S" (1-3)

(1-4) 10 wherein Rl2 is selected from the group consisting of hydrogen, dentate, thiol, ruthenium, acid group, amine group, schlossyl group, cyano group, acetylamino group, ureido group, Cl-4 a group consisting of a base and a Cu4 alkoxy group. In the reactive dye of the formula (I) of the present invention, wherein Ei* E2 may each independently be a monoazo structure, preferably a structure of the following formula (* indicates a coupling position): nh2

, N=N '(Ρ·7)0·3

So3h (1-5) 15 1363783 ho3s N=N— (^7)0*3 (1-6) (R7)〇-3'

N=N

OH

NHR! u OH NH2 so3h

N=N—j^^Y〆',, ', , (R7)0~3

Nh2 oh ho3s

N=N —/(^7)0-3

Rl2 OH NH2 so3h

N=N- o -C-NH- so3h 10 (1-10)

11 1363783

(Ml) wherein (R7) 0_3 and R12 are as defined above;

R8 is hydrogen, Cm alkyl, C2_4 alkanoic acid group, or via a hydroxyl group, a cyano group, a thiol group, an acid group, a methoxycarbonyl group, an ethoxycarbonyl group, or a Acetoxy substituted Ci_4 alkyl; 10

R11 is nitrogen, Cl _4 alkyl, unsubstituted or substituted by halogen, thiol, sulfonic acid, nitro, Cm alkyl or alkoxy, or via, thiol, nitrogen Or a Ci~4 leuco group substituted by an acid group. In the reactive dye of the formula (1) of the present invention, wherein Ei* E2 may each independently be a bisazo structure, preferably a structure of the following formula (* indicates a coupling position):

H2N'

COOH -N=N-, NH2 pro (1^9) 0-3

N 15 (1-12) (Rl〇)〇-3 12 1363783

5

^7)0.3

(R7W

Wherein '(R7)〇-3, R11 and R12 are as defined above; (ROo·3 is 0 to 3 identical or different substituents, and each independently selected from halogen, hydroxy, carboxy, sulfonic acid, amine a group consisting of a nitro group, a cyano group, a cyano group, a C. 4 alkyl group, a C. 4 alkoxy group, a C2_6 alkoxycarbonyl group, an amine carbaryl group, a burnt amine group, and a C; 10 15 (Rio) o·3 are 0 to 3 identical or different substituents, and each independently selected from halogen, hydroxy, carboxy, sulfonate, amine, nitro, cyano, C,- a group consisting of a 4-alkyl group, a Cl.4 alkoxy group, a Gw alkoxycarbonyl group, an amine carbaryl group, a C2·5 decylamino group, and a C 2-4 oleic acid group; a group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, a nitro group, a cyano group, an ethyl decylamino group, a urea group, a Cl 4 alkyl group, and a C 4 alkoxy group. The soil is reacted in the formula (1) of the present invention. In the dye, El and E2 may each independently be a polyazo structure', preferably a structure of the following formula (* indicates a coupling position): σ 13 !363783

I can each be represented by '(Do·3 and Rii are as defined above; p is 2 in the reactive dye of the formula (1) of the present invention, and t or six ^ T Ji I and t ^ are independently metal-missing azo structures Preferably, the following 2 can be coupled to each other): . Constructor (*表(R7)〇.3—ώίΐ ί12 (Rl4)〇-3 *N=N—i

(I·16) Female 13 3 ^(S〇3H)〇.,

(1-17) wherein (R7)o-3, Rh, R12 and r13 are as defined above as '(Ri4)o·3 are 0 to 3 identical or different substituents and each = being selected from dentate, Keji, ruthenium, plum, nitro, cyano C" : = -4 alkoxy, C2-6 burnt oxygen county, amine brewing base, C25 burnt soil and C2 · 5 alkane tickic acid group Group. In the reactive dye of the formula (1) of the present invention, wherein ruthenium and E2 may each independently form a base structure, more (4) a structure of the following formula (* indicates a coupling position): 15 1363783

(S〇3H)〇.2 (II-1) In the reactive dye of the formula (I) of the present invention, wherein E, * E2 may each independently be a naphthyl structure, more preferably a structure of the following formula (* represents Coupling position 5):

-10 In the reactive dye of the formula (I) of the present invention, wherein ugly 1 and E2 are each independently a monoazo structure, more preferably a structure of the following formula (* indicates a coupling position):

(II-4) 15 15 1363783

OH

(Π-5)

(II-7)

ο .__, / 16 10 1363783

(Π-10) wherein s, t, and V are each independently an integer of 0, 1, or 2, and s + t + v is an integer of 0, 1, 2, or 3; X and y are each independently 〇, 1 or An integer of 2, and x + y is an integer of 0, 12 or 3. In the reactive dye of the formula (I) of the present invention, wherein Ei* E2 may each independently be a bisazo structure, more preferably a structure of the following formula (* indicates a coupling position):

(11-11)

COOH

(11-12) 17 1363783

(Π-13)

(Π-15) where χ and y are as defined above.

In the reactive dye of the formula (I) of the present invention, wherein E!* E2 may each independently be a metal-missing azo structure, more preferably a structure of the following formula (* indicates a coupling position):

(11-16) For convenience of description, in the specification, the compounds are all expressed in the form of a free acid, but the dyes of the present invention are often produced in the form of 18 1363783 in the form of a water-soluble salt, a suitable salt. It may be an alkali metal, an alkaline earth metal, a salt or an organic amine salt. Among them, a sodium salt, a potassium salt, a lithium salt, a salt or a triethanolamine salt is preferred. The dye of the present invention can be prepared by a known method, and the reaction sequence prepared by the method is not strictly limited, and the chromophore can be prepared first, and then the desired dye can be synthesized; or the dye can be prepared. In the process, the chromophore is synthesized. The dyes of the present invention are suitable for use in fibrous materials, especially cellulose fibers, and dyeing or printing of fibrous materials containing cellulose fibers. The fiber 10 material is not particularly limited and may be natural or regenerated cellulose fibers such as cotton, hemp, linen, hemp, ramie, mucilage, or fibrous materials containing cellulose fibers. The dyes of the invention are also suitable for dyeing and printing of fiber blended fabrics containing hydroxyl fibers. The dyes of the present invention can be fixed to the fibers in a variety of ways, particularly in the form of aqueous dye solutions and printing pastes. Dyeing and printing are carried out by means of dip dyeing, continuous dyeing, cold dyeing, printing and printing, and digital printing. The dyeing or printing according to the present invention can be carried out according to a conventionally known and conventional method. Exhaustion dyeing is carried out by using well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (e.g. Sodium carbonate, sodium hydroxide and sodium hydride are used singly or in combination. The amount of inorganic neutral salts and bases is not critical, and inorganic neutral salts and bases can be added to the dye bath once or in divided portions by conventional methods. In addition, it is also possible to add a dye aid (such as a leveling agent or a retarder) according to a conventional method. The dyeing temperature is usually between 40 ° C and 90 °. Oh, preferably 〇C. _ 1363783 Cold press dyeing is the substance to be dyed, padded with well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as sodium carbonate sodium hydroxide), and then in the room The resulting material was dyed in a roll form under temperature. 5 continuous dyeing method is to mix the well-known acid-bound hydrazine (such as sodium carbonate or sodium hydrogencarbonate) with the padding solution, and the material to be dyed is pad-dyed according to the usual method, and then the obtained material is dry-heated or steam-solidified; The two-bath padding method uses a dye to dry-dye the substance to be dyed, and then treats it with a well-known inorganic neutral salt (such as sodium sulphate or sodium sulphate), and it is preferred to dry the treated substance according to a usual method or Steamed solid 10 colors. The fabric printing method, for example, has a single-phase printing method, which is printed on a material to be printed with a printing paste containing a well-known acid binder (such as sodium hydrogencarbonate), and is dried or α-vaporized; the two-phase printing method includes The printed material is modified to incorporate the inorganic neutral salt 15 (such as sodium chloride) and the well-known acid binder (such as sodium hydroxide or sodium carbonate) in the south temperature (9 〇. 0 or above). The fixing of the solution in accordance with the method of the present invention is not limited to the dyeing or printing method of the preceding list. [Embodiment] For the sake of convenience, it is to be noted that the following embodiment will be described in more detail. The following examples are intended to illustrate the invention and the scope of the invention is not limited thereby. Wherein the compound is expressed in the form of a free acid, but the actual form may be a metal salt, more preferably an alkali metal salt, especially a sodium salt, unless otherwise specified. Otherwise, the parts or percentages used in the examples are In weight, the temperature is in degrees Celsius. 〇 is the unit. 20 1363783 Example 1 2_66 parts of p-Aminophenyl-fl-vinyl-sulphone was dissolved in 20 parts of acetonitrile, 10 parts of 25% ammonia water was added, and the reaction was carried out at room temperature. After 24 hours, it was crystallized, filtered, and dried to give a product structure of formula (1). H2N——S02CH2CH2-N-h2ch2co2s—^nh2 Η (1) Example 2 10 1.83 parts of p-aminostyrene sulfone is dissolved in 10 parts of cyanide, and 3.87 parts of 40% methylamine (methyl.amine) is added. The mixture was reacted for 4 hours at a temperature, and recrystallized using butanol, filtered, and dried to obtain a product structure of the formula (2).

S02CH2CH2—N- h2ch2co2s

I ch3 (2) Example 3 2.66 parts of p-aminostyrene sulfone was dissolved in 30 parts of cyanonane, 11.46 parts of 70% ethylamine was added, and the reaction was held at 2 〇 0 C for 1 hour while maintaining crystallization. Filtration and drying gave the product structure as in formula (3).

H2N

So2ch2ch2—nhch2ch3 21 (3) 20 1363783 Next, 2.29 parts of the compound of the formula (3) and 1.83 parts of p-aminostyrenesulfone were reacted at 150 ° C for 3 hours, cooled, recrystallized using butanol, filtered, and dried to obtain The product structure is as shown in formula (4). H2n~C^ SO2CH2CH2—N- h2ch2co2s· ch2ch3

Nh2 5 (4) Example 4 • 10 parts of acetic acid solution was added to 1.92 parts of the compound of the formula (1) obtained in Example 1, followed by the addition of 0.42 parts of sodium acetate and 9.0 parts of acetic anhydride. The reaction was carried out at 40 ° C for 2 hours, and the product structure was isolated by a column to obtain the formula (5). Λ—nh2 so2ch2ch2—N-h2ch2co2s-coch3 (5) Example 5 3.66 parts of p-aminostyrene sulfone was dissolved in 40 parts of cyanomethane, and 1.22 parts of ethanolamine was added thereto, and reacted at room temperature for 12 hours. Crystallize, filter, and dry to obtain a product structure such as formula (6) 〇

so2ch2ch2—NHCH2CH2OH (6) Next, take 5 parts of m-aminophenyl-β-

22 20 1363783 vinylsulphone) Dissolved in 50 parts of cyanogenic oxime, 5 parts of the compound of the formula (6), and reacted at room temperature for 12 hours, crystallized, filtered, and dried to obtain a product structure of the formula (7).

Examples 6 to 58 Referring to the synthesis of Examples 1 to 5, the structural formula of the bridging compound of the formulae (8) to (60) listed in Table 1 can be obtained. (Rl)〇-3 (^2)〇-3

10 Table 1 Example Compound Structure 6 <<》—S02CH2CH2—Ν - h2ch2co2s~<> h2n νη2 (8) ho3s so3h 7 H2N—/ V-SO2CH2CH2—N-H2CH2CO2S—^ nh2 Η (9)

•V Λ ν 23 1363783 8 h3o

H2n S02CH2CH2—N - H2CH2CO2S~^ OCHj

i M nh2 (10) 9

(11) 10

(12) II It 11

Nh2

CNH(CH2)2S02CH2CH2—N- H2CH2C〇2S (H2C>2HNC

H (13) 12

(14) ❿ 13 S02CH2CH2—N-h2ch2co2s~^ ^ h2n CH3 nh2 〇5) 14 ho3s h2n U3&amp; ^U3 ^^so2ch2ch^n-h2ch2co2s-^- SO^H nh2 ch3 (16)

24 1363783 15 H3CO~^ S〇2CH2CH2—N- h2ch2co2s~^ och3 h2n CHa nh2 ch3(17) 16

S〇2CH2CHr-N - H2CH2C〇2: ch3 h3c(18)

17

S02CH2CH2—N- H2CH2C〇2: och3 CH3 h3co(19)

18 CNI^CHASOjCHzCHrN- H2CH2C〇2S(H2C)2HNC ch3(20) ------ 19

(21) 20 N\_fj h2n ch2ch3(22) ζ y-S02CH2CH2—N-H2CH2C02S-

Nh2 21

12-n-h2c ch2ch3 so2ch2ch factory n-h2ch2co2;

So3h nh2 (23) 25 1363783 22 h3o

S〇2CH2CHr-N- H2CH2C〇2: CH; h2n s—OCH3 (24) 23

S02CH2CHr-N- H2CH2C02S

H3c och3 nh2 (25) 24

SO2CH2CH2—N- H2CH2C〇2: OCH3 CR2Clh K^cci (26) och3

25 h2n

^η2οη3 26 K2N~^y~ (27) N-H2C ch2ch2oh

S02CH2CH2—N- H2CH2CO2S

Nh2 (28) ^ \--SO2CH2CH2—N—H2CH2CO2S- 27

/ ~ ch2ch2oh h2n nh2 . (29) 28

N-H2C CH2CH2OH SO2CH2CH2—N- H2CH2CO2S·

So3h nh2 (30) 26 1363783 29 U3C0~^y^~ h2n SO2CH2CH2—N- H2CH2C02! CH:

i2CH2OH S~^ OCH3 nh2 (31)

(33) H2N-Qj ------ 32 CNH(CH2)2S〇2CH2CH2—N- H2CH2C〇2S(H2C)2HNC· ch2ch2oh (34)

Nh2 33

(35) 34 S02CH2CH2—N- h2ch2co2s. ch2ch2so3h (36)

Nh2 35

S02CH2CH2—N- H2CH2C〇2S· CH2CH2so3H

(37)

27 1363783 36

SO2CH2CH2—N- H2CH2C02: CH:

i2CH2S〇3H (38) 37

SO2CH2CH2—N- H2CH2CO2! CH: h2n

i2CH2S03H

OCH3 nh2 (39) 38

S02CH2CHr-N-H2CH2C02; (!m2CH2S〇3H(40)

39

S02CH2CH2—N- h2ch2co2 OCH3 iH2CH2S〇3HH3C〇(41)

ΓΊ 40

CNH(CH2)2S02CH2CH2—N - H2CH2C02S(H2C)2HNC d:H2CHiS〇3H

(42) 41

(43) 42

so2ch2ch2—N - H2CH2C02S—>> \h2 (44) 28 1363783 43

44

45 (45) H3CO~ί S02CH2CH2—N-H2CH2C〇2S~ζ V-OCHj 7~ c〇ch3 ~\ h2n 3 nh2 (46)

46 h2n (47)

S02CH2CH2--N- H2CH2C02S

(48) 47

(49) 48

(50) 29 1363783 49

SO2CH2CH2-N-H2CH2C〇2; CH2CH2OH

(51) 50

SO2CH2CH2—N - H2CH21 CH2CH2〇H(52)

0CH3 :C02S~^ NHz H3C 51 so2ch2ch2—n-h2c: CH2CH3(53) nh2 :h2co2s~^ 52 N—H2 CH2CH3 S03H SO2CH2CH2—N- H2CH2C02

Nh2 (54) 53 h2n h3c

So2ch2ch2—n - h2ch2co2s CH2CH3(55)

so3H

Nh2 54

(56) 55

SO2CH2CH2-N-H2CH2CO2S CH2CH2SO3H

NH2

S 30 1363783

(57)

(59) 58

Example 59 19.2 parts of the compound of the formula (1) was dispersed in i50 parts of ice water, followed by addition of 35. 4 parts of a 32% aqueous solution of hydrochloric acid (HC1), followed by the addition of 1 part of 5 parts of sodium nitrite. Stirring was continued at 0 to 5 ° C until diazotization completely gave the solution (A). After adding 28.1 parts of 4-(p-sulfatoethylsulfone) aniline and 25.6 parts of 32% hydrochloric acid aqueous solution to 0 C, 300 parts of water to form a dispersion solution 10, 7 2 parts of sodium arginate was added, and controlled in 〇 At ~5 ° C temperature until the heavy gasification reaction is complete. Then, 31.9 parts of 4·amino-5-hydroxy· 2,7-naphthalenedisulfonic acid powder was added, and 1 part of hydrogen carbonate was used.

31 1363783 5 Sodium (NaHC03) slowly adjust the pH of the reaction solution to 3, stir until the coupling reaction is complete. Next, the previously obtained solution (A) was added, and the pH of the reaction solution was adjusted to 5 using 21 parts of sodium hydrogencarbonate, and stirring was continued until the coupling reaction was completed. After salting out, filtration and drying, the product of the navy product is obtained as follows:

HO3SOH4C2O2S

n=n 乂IV s〇2c2H4- :Ν-Ν=0 Example 60 Add 28.1 parts of 4-(p_sulfatoethylsulfone) 10 aniline and 25.6 parts of 32% hydrochloric acid aqueous solution at 0 ° C, 300 parts of water to form a dispersion solution. Thereafter, 7.2 parts of sodium nitrite was added and controlled at a temperature of 0 to 5 ° C until the diazotization reaction was completed. Next, 31.9 parts of 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid powder was added, and the pH of the reaction mixture was adjusted to 2-3 using 10 parts of sodium hydrogencarbonate, and stirred until the coupling 15 was completed. ® In addition, 19.8 parts of the compound of the formula (2) was dispersed in 150 parts of ice water, and 25.6 parts of a 32% aqueous hydrochloric acid solution was added and thoroughly stirred, and then 7.1 parts of sodium nitrite was added thereto, and stirring was continued at 0 to 5 ° C until heavy. Nitriding is complete. The previously synthesized reaction solution was added, and the pH of the reaction solution was adjusted to 5 using 12 parts of sodium hydrogencarbonate, and stirring was continued until the coupling reaction was completed. After salting out, filtration and drying, a navy product is obtained. The structure of the product is as follows: 32 1363783

Example 61 20.6 parts of the compound of the formula (4) was dispersed in 150 parts of ice water 'Addition of 25.6 parts of 32% aqueous hydrochloric acid solution to the sandalwood mix', then add 7.1 parts of sodium nitrite, and continue to mix at 0 to 5 ° C. Until the diazotization is complete. Then join

10 15

31.9 parts of 4-冱111111〇-5-117&lt;11&gt;〇7-2,7-11&amp;卩111;11&amp;16116(^8111£&gt;〇114&amp;(^(1 powder' and adding 6 parts of carbonic acid Sodium hydride adjust the pH of the reaction solution to 2-3, and mix until the coupling reaction is complete. Add 28.1 parts of 4-(p-sulfatoethylsulfone) aniline and 25.6 parts of 32% hydrochloric acid solution to 0 C, 300 wound water to form a dispersion solution. Thereafter, 7.2 parts of sodium nitrite was added, and the control was carried out at 〇~5&lt;&gt;(: at a temperature until the heavy gasification reaction was completely 'added to the above coupling solution, and 12 parts of cesium carbonate was used to adjust the pH of the ruthenium to 5, The continuous-to-coupling reaction is completed. After salting out, transitioning and drying, a navy product is obtained. The structure of the product is as follows: HO3SOH4C2O2S ho3s I

N=N—^ ^— S02〇2H4. ;NCH2CH3

SO3H (64) Example 62 150 parts of water at 0 ° C were added to 36.1 parts of 1-amine phenyl-4-(β-acetazin 33 20 1363783 hard)-2-picic acid (l-aminobenzene-4-( P-sulfatoetliylsulfone)-2-sulfonic acid) and 30 parts of 32% aqueous hydrochloric acid solution were thoroughly stirred and dispersed. Then 7.2 parts of sodium nitrite was added until the diazotization reaction was completed, and 23.9 parts of 2-amino-5-na- 7-Supply acid (2-Amino-5-iiydroxynaphthalene-7-5 sulfonic acid) powder, using 12 parts of sodium hydrogencarbonate to adjust the pH of the reaction solution to 5, stirring until the coupling reaction is complete. 8 parts of sodium hydroxide and 3·9 parts of 40% methylamine were added and reacted at room temperature for 12 hours, salted out, filtered and dried to obtain a red product structure such as formula (65):

15 Add 31.1 parts of 2-methoxyl-5-(p· sulfatoethyl-sulfone) aniline and 25.6 parts of 32% hydrochloric acid aqueous solution at 0 ° C to 300 parts of water to form a dispersion solution, then add 7.2 parts of sodium nitrite. And controlled at 0~5 °C until the diazotization reaction is complete. Thereafter, 52 parts of the compound of the formula (65) was added, and the pH of the reaction mixture was adjusted to 5 using 12 parts of sodium hydrogencarbonate, and stirring was continued until completion of the coupling reaction. After salting out, filtration and drying, a red product is obtained. The structure of the product is as follows: 34 1363783

Example 63 5 150 parts of water at 0 ° C was added to 36.1 parts of 1-aminophenyl-4-(β-acetamidone)-2-carboxylic acid (1-aminobenzene-4-(p-sulfatoethyl sulfone) 2-sulfonic acid) and 30 parts of 32% aqueous hydrochloric acid solution were sufficiently disturbed to disperse, and then 7.2 parts of sodium nitrite was added and stirred until the diazotization reaction was completed. 18.8 parts of 2,4-diaminobenzene-l-sulfonic acid powder was added, and the pH of the reaction solution was adjusted to 2 using 5 parts of 10 sodium hydrogencarbonate, and stirred until the coupling reaction was completed to obtain a yellow solution. Separately, 21.3 parts of the compound of the formula (5) was dispersed in 150 parts of ice water, and 25.6 parts of a 32% aqueous hydrochloric acid solution was added thereto, and the mixture was thoroughly stirred, and then 7.2 parts of φ sodium nitrite was added thereto, and stirring was continued until the diazotization was completed. Further, the yellow solution was added to the above 15 and the pH of the reaction solution was adjusted to 5 using 12 parts of sodium hydrogencarbonate, and stirring was continued until the coupling reaction was completed. After salting out, filtration and drying, an orange product is obtained. The structure of the product is as follows:

35 1363783 Example 64 21.4 parts of the compound of the formula (7) was dispersed in i5 parts of ice water, and 25.6 wounds of 32% hydrochloric acid in water was added, and 7.1 parts of sodium sulfite was added to 0 to 5 Stirring was continued at ° C until diazotization completely gave a solution. 5 Add 28.1 parts of 4-(p_sulfatoethylsulfone) aniline and 25.6 parts of 32% hydrochloric acid solution to the solution of C, 300 damaged water to form a dispersion solution, then add 7_2 parts of sodium nitrite and control the temperature at 〇~5. Next, until the diazotization reaction element is fully 'added 31.9 parts of 4-amino-5-hydroxy-2,7_ naphthalenedisulfonic acid powder, and adjust the pH of the reaction solution to 3 ' using 〇 〇 part of sodium carbonate 10 until it is given up until The coupling reaction is complete. Next, the previously obtained diazonium compound solution (C) was added, and the pH of the reaction liquid was adjusted to 5' using 12 parts of sodium hydrogencarbonate, and stirring was continued until the coupling reaction was completed. After salting out, filtration and drying, a navy product is obtained. The product structure is as follows:

Example 65 Adding 28.1 parts of 4-(p-sulfatoethylsulfone) aniline and 25.6 parts of 32% hydrochloric acid aqueous solution to 0 C, 300-injured water to form a dispersion solution 20, then adding 7.2 parts of sodium nitrite and controlling At a temperature of 〇~5eC, 36 1363783 until the diazotization reaction was completely 'added 31.9 parts of 々-amino-S-hydroxy-ZJ-naphthalenedisulfonic acid powder, and the pH of the reaction solution was adjusted to 2-3 using 10 parts of sodium bicarbonate. Stir until the coupling reaction is complete. Add 8 parts of sodium hydroxide and 23.4 parts of 40% decylamine (11^11丫1 mad 11^116), react at room temperature for 5 hours for 12 hours, salt out, filter and dry to obtain red product such as structural formula (69) :

(69) After adding 28.1 parts of 3-(P_sulfatoethylsulfone) 10 aniline and 25_6 parts of 32% hydrochloric acid aqueous solution at 0 ° C and 300 parts of water to form a dispersion solution, add 7.2 parts of sodium nitrite, and control it in 〇~ At 5eC, until the diazotization reaction is complete, add 31.9 parts of 4-amino-5-hydroxy_l,7-naphthalenedisulfonicacid powder, and adjust the pH of the reaction solution to 3 with 10 parts of sodium bicarbonate. Stir straight to 15 to complete the coupling reaction. . Thereafter, 8 parts of sodium hydroxide and 54 parts of the formula φ (69) were added, and the mixture was stirred until the reaction was completed, and salted out and filtered to obtain a red product such as the formula (70):

37 (70) 1363783 Add 62.2 parts of 2-methoxyl-5-(P-sulfatoethyl-sulfone) aniline and 52 parts of 32% hydrochloric acid aqueous solution at 0 ° C, and mix thoroughly to form a dispersion solution, then add 14.4 parts. Sodium nitrite and controlled at a temperature of 0 to 5 ° C until the diazotization reaction is complete. Thereafter, 105 5 parts of the compound of the formula (70) was added, and the pH of the reaction solution was adjusted to 5 using 18 parts of sodium hydrogencarbonate, and stirring was continued until completion of the coupling reaction. After salting out, filtration and drying, a navy product is obtained. The asymmetric dye structure is as follows:

Examples 66 to 192

Referring to the synthesis of Examples 59 to 65, a reactive dye of the formula (72) to (198) having a dialkylamine as a bridging group can be obtained. EXAMPLES Dye Structures Hue 66

Navy Navy 38 67 1363783 68 69

HO3SOH4C2O2S

SO2C2H4 (74)

;N-NO navy blue

HO3SOH4C2O2S

HO3S , 0013⁄4 OH NH2

SOAH4. ;N-N=0 Navy (75)

70 71 72

nh2P::xoo HCbSOH^C^S SO2C2H4·

HO3SOH4C2O2S

SO2C2H4· (77) -N-N=0 N=〇 Navy Blue Navy

73

HO3SOH4CAS H03S0H4C202S

Navy blue navy (79)

SO2C2H4 -ch3 navy 39 74 1363783 75 76

77

Navy blue navy blue navy (83) 78 79

80 81 82

HO3SOH4C2O2S

HO3SOH4C202S ~〇^n=n

S〇2C2H4^ / H03S· ;n-ch3 -nch3 Navy Blue Navy Navy Blue Navy Blue Navy

SOjH tONHCCH^SOiC^W 40 (88)1363783 83

Navy

(89) 84 85

Navy blue navy (91) 86 87

Navy blue navy

(93)

Navy blue 88

Navy blue 41 1363783 90 91

SQAH^NCHzCH^OH (96) /2

92

(98) NH2 OH h〇3s, 93 94

(^―(四)丫 丫, -N=N SOAHU. • ur\ c·* H2C=HC〇2S(H2〇2HNOC H03s^ ^S〇3H(99)

-NCH2CH2OH

95 96 97 H03SOH4C202S〆

H03SOH4C202S HO3SOH4C202S

HO3SOH4C202S (101) Navy Blue Navy Blue Navy Blue Navy Navy Navy Blue Navy Navy Blue NH2

γ-Ν=Ν—^ ^r-N=N- —SO2C2H4.

?NC2H4S〇3H H〇3S*

SO3H (102) nh2 ohhGkn=nVtS~n=n^CVs

S〇2C2H44-NC2H4S〇3H H03S-

S03H ·.〆 42 (103)1363783 98 99

Navy blue navy

(105) 100 101 102

Navy blue navy blue navy

103 104

H03SOH4C2〇2S

H03SOH4C202S

so2c2H4^/2 S02C2Hv ;ncoch3 -NCOCH3 navy blue navy blue 43 1363783 105 106

Navy blue navy

107 (112)

Navy (113) 108

SO2C2H4--NH

Navy

109 110 111

Navy blue navy blue navy (117) 112

Navy blue 44 (118)1363783 113

Navy blue 114 (Π9)

SOjH j 2 red

(120) 115 116 117

Red red red 45 1363783 118

(124) Red 119 120 121 122

NCH2ai2〇H (125)

Nch2ch2so3h I2 (126)

(127)

Red red red red 46 (128) 1363783 123 124 125 126 127

:nch3

HO3SOH4C2O2S (129)

NCH,

;NCH,

HO3SOH4C2O2S

H03SOH4C2〇2S·

;Ν-Ν=0

;NCH2CH3 red red red red red 1363783 128

SO2C2H4

NCH2CH2SO3H red (134) 129 130

Red purple (136) 131

Purple (137) 132

Purple (138) 133

purple

48 (139)1363783 134 135

Purple red 136 137 138 139

BrH2CBrHCOCHN (141) ^ OC-NH 〇H h〇3'

HOjS^ ^ ^ ''SOjH ^V-n=n if

S02C2H4- ;nch2ch. Red (142)

(143)

-NCHjCHj

-ncochj so3h

N=N—^ ^— nh2

1 SOjH /={ H03S0RA02S—/ΉM=K S〇2C2H4- -N-N=0 Red Red Orange (Nrange) N ^ 140 49 1363783 141

142 \

S〇3H H03SOH4C202S

N=N

SO2C2H4*· nh2 N=N—^ ^^S〇2〇2H4-- (148) -nch3 Orange

-NCH2CH2OH orange

143 144

SO3H HO3SOH4C2O2S

SOjH

Nh2 J ^^0 NH2 (149) , C-NH(CH2)2S02C2H4-

SO2C2H4 (150)

-NCH2CH2OH Orange -nch3 Orange

145 146

HO3SOH4C2O2S -o

(151)

HO3SOH4C2O2S

Orange orange

50 1363783 147 148 149 150 151

HO3SOH4C2O2S

Orange

H03SOH4C202S h2n

N=N—^ ')—SO2C2H4· nh2(154)

-nch2ch2oh orange

OCH3

S03H / HO3SOH4C2O2S H2N

N=N’ 'N=N NH:

SOiH

SO2C2H4- -NCH3 Orange (155) HOOC-a, c2o2s - S03H SO3H Ν=Ν^^^Ν=Ν—^ ^—SO2C2H4 ;nch&gt; Orange (156)

HO3SOH4C2O2S

Orange (157) ·-/ ’, ο 51 1363783 152 153 154 155

COOH

S02C2H4- -N-N=0 HO3SOH4C2O2S h2n nh2

H〇3SOH4C202S S03H^C^n= Orange SO^I^OSO^ (158)

COOH

SOiH

SO2C2H4- -NCH3 h2n nh2

So3h so2c2h4oso3h (159)

S02C2H4- (160)

S02C2H4-J S02C2H40S03H (161} Orange -nch2ch2oh -nch2ch2so3h Orange Orange ‘, 5 / 52 1363783 156

yellow

157 158 (162)

Yellow (163)

yellow

159 (164)

Yellow 53 (165) 1363783 160

(166) yellow

161 162

(168) yellow yellow

163

Yellow ·./· N ^ 54 1363783 164

SO2C2H4OSO3H 2 yellow

165 (170)

Yellow 166

167 (171)

Yellow yellow 55 1363783 168

(174) Gray 169

Gray 170 (175)

(176) Gray 171

Navy (177) 172

Navy blue 56 (178) 1363783

Navy

(179) 174

Navy (180) 175

Navy

(181) 176

Navy blue 57 1363783

HOjSOH^OjS 177

H03SOH4C2〇2S

178 179

HO3SOH4C202S och3^C^~n=n

HO3SOH4C202S -C^~n=n

Nh2 oh -^G^n=n -〇^N=N

NCH2CH3 NCH2CH3 H〇3S,, S〇3H N=N—^ ^—; S02C2H4 S03H Navy Blue H〇3: ,0CH3 oh NH2

Navy (184)

Red 5 8 58 1363783 180

(186) Red 181

Red 182

Purple (188) 59 1363783 183

red

(189) 184

Orange 185

(190) HO3SOH4C2O2S HO3SOH4C2O2S

Orange (191) 186

Orange J, 60 (192) 1136783

Yellow blue purple

(194) 189

Dark green 190 (195)

Crimson och3 61 (196)1363783

SOiCjh/ 191

Nch2ch3 dark green

S02C2H40S03H (197) 192

Crimson (198)

(S Test Example 1 3 parts of the dye prepared in Example 59 was dissolved in 100 ml of water to prepare 30 parts/boost dye solution; 25 ml of alkali solution was used (using caustic soda 15 ml / 5 liters and Glauber's salt 30 parts) /L) is added to the dyeing solution and stirred evenly. The resulting mixture is poured into a Roller dye press, and then the cotton fabric is subjected to roller dyeing.

62 1363783, then rolled into a shaft. This form of cotton fabric was stored at room temperature for 4 hours. Then 'wash the navy blue dye first, then wash it with cold water, then wash it with boiling hot water for 1 〇-minute' and then soap with a boiling non-ionic detergent for 10 minutes. Finally, wash it with cold water and dry it. The cyan dye has excellent dyeing depth and coloring rate. Test Example 2 Three parts of the dye prepared in Example 60 were dissolved in 1 ml of water to prepare 30 parts/boost dye solution; 25 ml of alkali solution was used (using caustic soda 15 ml / 10 liter and thenardite 30) The mixture is added to the dyeing solution and uniformly stirred. The resulting mixture is poured into a Roller dye press, and then the cotton fabric is subjected to roller dyeing and then wound into a shaft shape. This form of cotton fabric was stored at room temperature for 4 hours. Then, the obtained navy blue dye is first washed with cold water, then washed with boiling hot water for a minute, then washed with boiling non-ionic detergent for 1 minute, and finally washed again with 15 cold water. After drying, it can be collected. The cyan dye has excellent dyeing and coloring. Test Example 3 100 parts of urea, 1 part of sodium nitrobenzenesulfonate, 20 parts of baking soda, 25 parts of sodium alginate, 815 parts of warm water, 1 part of total, obtained by stirring Additive paste. Three parts of the dye prepared in Example 62 were sprinkled on the above-mentioned one-part auxiliary paste and stirred rapidly. Cover the appropriate size of mercerized cotton twill with a 1〇〇mesh 45 degree twill print screen, and place the color paste on the 25 screen and go over the 〇··, 63 1363783 Dry in a 65 ° C oven for 5 minutes; put the dried cloth into a steamer and steam at atmospheric pressure saturated steam 102~i 〇 5 ° C for 10 minutes. Then, the obtained red dye is first washed with cold water, then washed with boiling hot water for 10 minutes, then soaped with boiling non-ionic detergent for 10 minutes, and finally washed with cold water for one time to obtain red dye with excellent quality. Dyeing and coloring rate. In summary, the present invention can achieve the purpose of development by the disclosed technical idea, which is novel, progressive and industrially utilized, and is in conformity with the requirements of the invention patent. However, the above-mentioned disclosures are preferred embodiments. Any changes or modifications made to the Department 10 are derived from the technical ideas of the case and are easily inferred by those familiar with the technology. The above-described embodiments are merely examples for convenience of description, and the scope of the claims of the present invention is subject to the scope of the patent application, and is not limited to the above embodiments. 15 [Simple description of the diagram] Benefits [Main component symbol description] 20 No" 64

Claims (1)

丄观/83 No. 97丨0丨362, revised page of December of the next year X. Patent application scope: h A new type of reactive dye with AMV-dialkylamino bridging group of formula (1): 5 (Rl)〇-3 R (^2)〇-3 N = N—E2-|z·^. (I) where, And E2 are each independently selected from the group consisting of stupid, naphthyl, pyrazolone, azo, disazo, polyazo and metal mismatched azo structures; R is hydrogen, Cm alkyl, C|_4 alkylcarbonyl, phenyl, nitroso, or a hydroxy, carboxy, or sulfonic acid group substituted C|_4 alkyl; (R|)〇-3 and (R2)〇_3 are 〇 to 3 The same or different substituents, each independently selected from the group consisting of hydrogen, a hydroxyl group, a carboxyl group, a sulfonic acid group, a nitro group, a cyano group, a C 4 · 4 base group, a C 4 . alkoxy group, a urea group And a group consisting of amine groups; B and B' are each independently selected from the group consisting of _s〇2- and -C0NH-(CH2)k-S02-; k is 1, 2, 3, 4, 5 Or an integer of 6; Z and Z, each independently selected from -so2-u, -C0NH-(CH2)d-S02-U, -0-(CH2)r-C0NH-(CH2)d-S02-U, yS a group consisting of -thiosulfatoethylsulfonyl and -N(R')-U'; d and r are each independently an integer of 2, 3 or 4; U is -CH2CH2W or -CH=CH2; W is removed by treatment with a base a group of -CM, -0S03H, 65 1363783 -OP〇3H, a quaternary ammonium salt, a pyridine, a carboxypyridyl group, a methylpyridyl group I3 N-C2H4SOjH carboamine group than bite group, or ~; R3 and R4 are each independently hydrogen or C|-4 alkyl; U is α, cold-halo fluorenyl (a, p_hai〇pr〇pi〇n ^), α-halopropene 5 base, β-dentate fluorenyl, or α-dentyl acrylonitrile; R' is hydrogen or C|_4 alkyl; 1 and J are each independently an integer of 〇, 1 or 2, And 丨 and j are not 0 at the same time; and m and η are each independently an integer of 2, 3 or 4. 10 20 2. A novel reactive dye having a dialkylamino bridging group as described in claim i, wherein R is hydrogen, C 4 alkyl, Ci 4 alkylcarbonyl, phenyl, nitroso, or a 4-alkyl group substituted with a hydroxyl group or a sulfonic acid group. 3. A novel reactive dye having a dialkylamino bridging group as described in claim i, wherein (R|) 〇 3 and 2) 〇 3 are 〇 to 3 identical or different substitutions And each independently selected from the group consisting of hydrogen, a sulfonic acid group, a Cm alkyl group, and a C alkoxy group. 4. A novel reactive dye having a #,沁 dialkylamino bridging group as described in the scope of the patent application, wherein 2 and 2 are each independently selected from -S02-U, -CONH-fHA-SOrU and - called the ruler,)..., the group formed. 5. If you apply for a patent scope! A novel reactive dye having a dialkylamino bridge as described in the section wherein ruthenium and osmium are each independently an oxazolinone structure. The structure is as follows: 66 丄/83 In the eighth, G is a Ci-3 alkyl group, a carboxylic acid group or a C2.5 alkanoic acid group, and the core and the heart are independently selected from the group consisting of hydrogen, halogen, hydroxyl, carboxyl, sulfonic acid group, nitro group, and murine group. A group consisting of C, 4 alkyl and C | 4 alkoxy. 6. A novel reactive dye having a dialkylamine-based bridge I as described in the scope of claim 2, wherein each of the phenyl structures and the fluorene structure is a structure of the following formula: 1 R7) 0-3 '(R7)〇_3 is 〇 to 3 identical or different substituents, and each independently selected from _, hydroxy, carboxy, sulfonate, amine, nitro, cyano, C, .4 alkane Group consisting of a group, a Cl 4 alkoxy group, a CM alkoxycarbonyl group, an amine methyl sulfonyl group, a &gt; C2.5 alkanoguanamine group, and a c2.5 alkanoic acid group. 7. A novel reactive dye having a dialkylamino bridge 15 group as described in claim 1, wherein each of Ej〇E2 is independently a naphthyl structural system: 0H And 67 1363783 a group consisting of, wherein r12 is selected from the group consisting of hydrogen, halogen, hydroxy, carboxy, carboxylic acid, amine, nitro, cyano, ethylamino, ureido, 〇1_4 炫, and C丨_ 4 groups of alkoxy groups. 8. A novel reactive dye having a TV, #-dialkylamino bridging group as described in claim 1, wherein ugly, and £2 are each independently a monoazo structure selected from: OH NHR,, 68 10 1363783 OH NH2 so3h '(R7)0O nh2 oh ,(民7)0-3 Ho3s n=n 广广^〆’, ':,, S03H and a group consisting of (R7)0.3, which is 0 to 3 identical or different substituents, and each independently selected from the group consisting of dentate, hydroxyl, carboxyl, sulfonate, amine, nitro, cyanide a group consisting of a C, a 4 alkyl group, a C, 4 alkoxy group, a C2·6 alkoxycarbonyl group, an amine carbenyl group, a Cw alkanoguanidino group, and a C2·5 alkanoic acid group; Rs is a hydrogen, Cm alkyl group, a C2 4 alkyl carboxylic acid group, or a Cm alkyl group substituted with a hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group, a fluorenyl phenyl phenyl group, an ethoxylated phenyl group, or an ethoxy group; 10 1363783 rh is hydrogen, Ci.4 alkyl, unsubstituted or substituted by halogen, benzyl, carboxy, sulfonate, nitro, Ci_4 alkyl or CU4 alkoxy, or via hydroxy, carboxy, cyanide a CH4 alkyl group substituted with a sulfonic acid group; and R12 is selected from the group consisting of hydrogen, halogen, hydroxyl, carboxyl, sulfonic acid group, amine group, nitro group, cyano group, ethyl fluorenyl group, ureido group, Cw alkane a group consisting of a C and a 4 alkoxy group. 9. A novel reactive dye having a dialkylamino bridging group as described in claim 1, wherein the E2g is independently a bisazo structure selected from the group consisting of: H2N (^9)0-3,(R10)0-3 NHRn •N=N COOH 10 (R7)0-3· (S〇3H)〇., λ and NHR, N = N - (foot 7) 0-3 group, wherein 1363783 (R7) o-3 is 0 to 3 identical or different substituents, and each is independently selected from the group consisting of i, hydroxyl Carboxyl group, sulfonic acid group, amine group, nitro group, cyano group, C, 4 alkyl group, Ci-4 alkoxy group, C2_6 alkoxycarbonyl group, amine carbenyl group, c2 5 alkane amine group and C2·5 burnt a group consisting of tickacid groups; 5 (R9) 0·3 are 0 to 3 identical or different substituents, and each independently selected from a functional group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, a nitro group a group consisting of a cyano group, a Ci-4 alkyl group, a C*.4 alkoxy group, a C2.6 alkoxycarbonyl group, an amine carbenium group, a c2 5 ^ alkanoguanamine group, and a C:2·5 alkanoic acid group. Groups; 3 (Rio) o·3 are 0 to 3 identical or different substituents, and each 1 〇 is independently selected from the group consisting of halogen, hydroxy, carboxyl, sulfonyl 'amine, nitro 'cyano, Cw a group consisting of an alkyl group, a C|_4 alkoxy group, a CM alkoxycarbonyl group, an amine carbaryl 'C2·5 succinylamine group, and a cz_5 benzoic acid group; Rii is hydrogen, C!-4 alkyl group, Benzene ring substituted with no substitution or hydroxyl, hydroxyl, carboxyl, % acid, nitro, C, .4 alkyl or C, · alkoxy Or C|~4 alkyl substituted by 15 ruthenium, ruthenium, cyano, or wall acid group; Ru is selected from hydrogen, halogen, thiol, dibasic 'an acid group' amine group, ® nitrate a group consisting of a cyano group, a cyano group, an acetamino group, a gland group, a Cw alkyl group, and a c, _4 alkoxy group; and the R!3 group is selected from the group consisting of hydrogen, dentate, meridine, slow base, and acid. A group consisting of a group, an amine group, a 20 nitro group, a cyano group, an ethyl decylamino group, a ureido group, a C, 4 alkyl group, and a Cw alkoxy group. 10. A novel reactive dye having a dialkylamino bridge group as described in claim 1, wherein E| and E2 are each independently a polyazo structure. The structure of the following formula: 7! 25 1363783 Wherein (R7)o·3 is 0 to 3 identical or different substituents, and each is independently selected from the group consisting of a hydroxyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amine group, a nitro group, a cyano group, and a 5 Cl-4 group. a group consisting of an alkyl group, a C!.4 alkoxy group, a C2.6 alkoxycarbonyl 'amine-mercapto' C25 alkane, a guanylamino group and a C2·5 alkanoic acid group; R|| is hydrogen, a benzene ring which is substituted with a halogen, a halogen group, a sulfonic acid group, a nitro group, a C, 4 alkyl group or a C, 4 alkoxy group, or a hydroxyl group or a carboxyl group. a C1~4 alkyl group substituted by a cyano group or a sulfonic acid group; and p is 2 or 3. 11. A novel reactive dye having a dialkylamino bridging group as described in claim 1, wherein each of ^ and e2 is independently a metal mismatched azo structure selected from: 72 1363783 (R7) 〇-3 is 0 to 3 identical or different substituents, and each independently selected from the group consisting of dentate, thiol, ruthenium, acid group, amine group, nitro group, cyano group, Cw a group consisting of an alkyl group, a Cm alkoxy group, a &lt;:2_6 alkoxycarbonyl group, an amine fluorenyl group, a c2.s aromatide group, and a C2_5 alkanoic acid group; 5 R|l is a mouse, C|· a benzene ring, or a trans group, a carboxyl group, or a cyanogen substituted by a thiol group, an unsubstituted group, or a carboxylic group, a sulfonic acid group, a nitro group, a C, 4 alkyl group or a C, .4 alkoxy group. a group or a sulfonic acid group substituted by a cl 4 alkyl group; _ Ru is selected from the group consisting of hydrogen, halogen, hydroxyl, carboxyl, acid group, amine group, nitro group, cyano group, acetylamino group, urea group, Cl_4 a group consisting of an alkyl group and a Ci 4 alkoxy group 10; the Ri3 group is selected from the group consisting of hydrogen, dentate, meridine, carboxyl group, acid group, amine group, succinyl group, ethyl amide group, urea group, a group consisting of C|·4 alkyl and 匚14 alkoxy; and 15 (Rl4) 〇-3 is 0 to 3 identical or different substituents, and each independently selected from the group consisting of dentate, hydroxyl, carboxyl, sulfonic acid, nitro, cyano, Cm alkyl and anthracene, -4 A group consisting of an oxy group, a c2_6 azeotrope (tetra), an amine carbaryl group, a c2 5 (10) amine group, and a C2-5 carboxy fluorenyl group. 12. A novel reactive dye having a μ沁 dialkylamino bridge 20 soil as described in the scope of claim 2, wherein ε &gt; ε 2 are each independently. The structure of the salivary ketone structure is as follows: (S〇3H) 〇.2 73 1363783 13. A novel reactive dye having a dialkylamino bridging group as described in claim 1, wherein each of £, and £2 is independently a naphthyl structure. Structure: 14. A novel reactive dye having a dialkylamino bridging group as described in claim 1, wherein the self-independent monoazo structure is selected from the group consisting of: 74 1363783 (so3H)x φ- (0CH3)j, and a group consisting of, wherein s, t, and v are each independently an integer of 0, 1, or 2, and s + is an integer of 0, 1, 2, or 3; X and y are each independently 0, 1, or 2 An integer, and X + y is an integer of 0. t + v , 2 or 3 75 10 1363783 15. A novel reactive dye having a TV,-dialkylamino bridging group as described in claim 1 wherein each of the two is independently a bisazo structure free: COOH (〇CH3)y And 76 丄允3783 ~〇- Its:; Each is independent. An integer of y, 0, 1, 2 or 3. 16. A novel reaction as described in the scope of application of the patent scope [where E 2 is independent of 3 nitrogen structure is a structure of the following formula: - each independently is a metal mismatch 10 H〇3S〇H4C202S n=n ( ^__ s〇2c2H4· ; NN=0 15 18. A novel reactive dye having a dialkylamino bridging group according to claim 1 wherein the formula (1) is a structure of the following formula (66) : 77 1363783 So2c2h4 NCHi 19. A novel reactive dye having a W-dialkylamino bridging group according to claim 1, wherein the formula (I) is a structure of the following formula (67): • 5 ho3soh4c2o2s , so2c2h4 - NCOCH3 20. A novel reactive dye having a TV-dialkylamino bridging group according to claim 1, wherein the formula (I) is a structure of the following formula (70): Equation (70) 〇 78