TWI359802B - Bridge compound with n,n-dialkylamino group - Google Patents

Description

1359802 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel bridging compound having an n,n-dialkylamino group. [Prior Art]

The chemical structure of Cl Reactive Red 141 is as shown in the following formula.

S03H (a) 1 is a reactive red dye having two monochloro(3)-reactive groups, which is a commonly used high-temperature dye. However, CI Reactive Red 141 did not perform well when it was used for shallow concentration dyeing applications. ^ The discovery found that the structure of the linker 1,4_1,4-diamine (1,4-benzenediamine) • structure, the development of a new type of linkage. -15 SUMMARY OF THE INVENTION The present invention provides a novel bridging group compound having N,N_:alkylamino (N,Ndialkylamin〇), which is suitable as a bridging bridge between two molecules, such as a bridge between a dye and a dye. & 'The UV-absorbing agent and the UV 20 absorber between the two molecules of the bridging group, or the dye and the UV absorber between the two molecules of the bridge. The novel compound of the N,N-dialkylamino bridge in this month has a structural formula of 1359802. The formula is represented by the following formula (i): HN- I Ri (R), R" B-(CH2)m-N-(CH2 )fi一*B'

NH I R2 (I) wherein 5 R and R' are each independently selected from the group consisting of: hydrogen, halogen, hydroxy, carboxyl, sulfo, ® a group consisting of nitro (nitr〇), cyano (cyan.), Cb4 alkyl, Cm alkoxy, ureido, and amido;

Ri and R·2 are each independently a hydrogen atom, or (: 丨_4 alkyl; 10 R is a hydrogen atom, a Ci~4 alkylcarbonyl group, a phenyl group, a C|-4 leukoyl group, or a halogen group; a hydroxyl group, a carboxyl group, or a sulfonic acid group-substituted Cl_4 alkyl group; B and B' are each independently selected from the group consisting of: linear, _8〇2_, and _c〇nh-(CH2)n-S02- ;

1 and j are each independently an integer from 〇 to 3; and m and η are each independently an integer of 2 to 4, respectively. The compound of the formula (I) of the present invention is more preferably a compound represented by the following formula (Ia):

(R') j NH r2 (la) 20 wherein R, R, 11'', 111, 112, 1, ], 111, and 11 are as defined above. 1359802 In the compound of the formula (Ia) of the present invention, 'preferably, han and r are each independently selected from the group consisting of a hydrogen atom, a repeating acid group 'methyl group and a methoxy group'. In the compound of the formula (la) of the present invention, preferably R, is selected from the group consisting of hydrogenogen =, methylalkyl, ethane, -c2h4〇h'-C2H4S〇3H', \c〇c di and benzene. The group of rings. In the compound of the formula (Ia) of the present invention, it is preferred that the oxime and the oxime are each independently an integer of 1 or 2. In the compound of the formula (Ia) of the present invention, preferably, the paw and the η are each independently an integer of 2 or 3. The compound of the formula (I) of the present invention can be obtained by the following production methods: (1) Addition reaction using a compound of the formula (II) and a compound of the formula (1): >

B—(cH2)r-CH: :CH, (II), 5

H ΓΝ-

H to

H

The type is called to be a controllable part ^ H2 C-(H2 2CH Η c L I 2CH H c - , K H2 (c

H N. _R1 20 or 1359802 (2) An addition reaction is carried out using a compound of the formula (II) and a compound of the formula (III), and controlled by appropriate reaction conditions, to obtain a compound of the formula (V), (R)u

ΗΝ——B—(CH2)k—CH2CH2-N—H R1 (V) Next, a compound of the formula (V) and a compound of the formula (VI) are used for the reaction to obtain an asymmetric compound of the formula (VII).

(R.) , , , HN- I r2 -B, one (CH2)i—ch=ch2 (VI) (R)iv ΗΝ—;-tJ—−η—B (CH2)k—CH2CH2—N—CH2CH2 —(CH2)丨-Β_· (R')i

-NH R2 (VII) or (3) Use a mixture of formula (II) and formula (VI) in appropriate proportions (R)i

R2 15 1359802 (VI) and compound (III) are controlled by appropriate reaction conditions, R"

I (III) Η一Α-Η The addition reaction can be carried out to obtain the asymmetric compound formula (VII).

HN-I Ri (R)u J7^j—Β—(CH2)k—CH2CH2—Ν—CH2CH2—(CH2),—B1—(VII)

NHI r2 Further, under certain ratio conditions, the symmetrical formulas (IV) and (VIII) are obtained in addition to the asymmetric compound of the formula (VII) because of the different bonding modes. HN- (R)i R" B-(CH2)k-CH2CH2-N-CH2CH2-(CH2)k--β.

(R)i

-NH

I

HN-I r2 (R,), (IV) R" B'—(CH2),——CH2CH2—N—CH2CH2—(CH2),~g,__

(R.) j NHI R2 (VIII) 15 wherein R, R', R", heart, r2, B, B', i, and j are as defined above. k and 1 are each independently and are each an integer from 0 to 2. Preferred specific examples of the compound of the formula (la) of the present invention can be exemplified as follows, but are not limited thereto: 9 20 1359802 H2N-hCj^

So2ch2ch2—n- h2ch2co2s- H -nh2 (i)

Nh2 so2ch2ch2—N- h2ch2co2s ch2ch3 (2)

So2c h2ch2— n - h2ch2co2s ch3

Nh2 (3)

\— so2ch2ch2—N - h2ch2co2s

H h2n nh2 (5) h2n #10 (6) -so2ch2ch2—n- h2ch2co2s coch3

Nh2 so2ch2ch2—n- h2ch2co2s-ch2ch2so3h (7)

Vnh2 H03s

SOiH h2n- -so2ch2ch2—n—h2ch2co2s-

-NH 2

H 10 (9) 1359802 h3c

H2n

H2n H0V H2N especially -SO2CH2CH2-n-h2ch2co2s(10) S02CH2CH plant N-h2ch2co2s ch3 (14) -so2ch2ch plant N - h2ch2co2s ch3

Och3 nh2

Nh2 so3h -nh2 h3c

H2n

H2n ho3s h2n- (16) so2ch2ch plant N- h2ch2co2s ch3 (17) SO2CH2CH2—N- H2CH2C02S CH2CH3(22)

-so2c h2ch2— n - h2ch2co2s—^ ch2ch3 (24) -OCH3 nh2 nh2 so3h -nh2 h3c

H2n -so2ch2ch factory n- h2ch2co2s CH2CH3

-OCH3 nh2 11 (25)1359802 H2N- h2n

Ho3s h2n- h3c

H2n

10 h2n

-so2ch2ch2—n- h2ch2co2s ch2ch2oh (30) so2ch2ch2—N-h2ch2co2s ch2ch2oh(31) S02CH2CH2—N- h2ch2co2s ch2ch2oh(33) *S〇2CH2CH2—N - H2CH2CO2S ch2ch2oh (34) S02CH2CH2—N- H2C.H2CO2S CH2CH2so3H (39 ) so2ch2ch2—n- h2ch2co2s COCH3 12 (47) 1359802

:H2—N-] COCH3 (48) so2ch2ch2—N- h2ch2co2s

S03H nh2

NH 2

H2N so2ch2ch2—n- h2ch2co2s ch2ch2oh(52)

So3h h2n

Ho3s h2n

S02C H2CH2—N—h2ch2co2s ch2ch2oh(53) so2ch2ch2—N- h2ch2co2s ch2ch2oh

-NH,

0CH3

Nh2 h3c (54) nh9 h2n so2ch2ch2—N- h2ch2co2s ch2ch3(55)

And so3h

H,N

S02CH2CH2—N- h2ch2co2s CH2CH3

Nh2 13 (56). 1359802 The novel bridging compounds of the present invention can be further prepared into dye compounds via diazotization reaction 'coupling, addition reaction and condensation reaction. Specific examples of the dye compound of the present invention can be exemplified as follows, but are not limited thereto:

HO3SOH4C2O2S

Human 〇 OH NH-

, N, HN so3h S〇2CH2CH2

NH S〇2CH2CH2 and

〇" so2ch2ch2 n-ch2ch2oh so2ch2ch2 10 (70) The dye compound of the present invention can be fixed to natural or recycled fiber materials by various means, such as cotton, hemp, linen, hemp, ramie, mucus snail 14 1359802 萦, also applicable The fiber blended fabric containing hydroxyl fibers is dyed and printed by dyeing, cold dyeing, printing, digital printing, etc., and the obtained dye has the characteristics of high fixation, high dyeing depth and easy washing. Conventional and conventional dyeing methods are as follows: • 5 Dip dyeing method using well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as sodium carbite, sodium hydroxide) alone or Mixed use. The amount of inorganic salts and bases is not very important, and the inorganic neutral salt φ and the test can be added to the dye bath once or in portions according to conventional methods. In addition, it is also possible to add a dyeing aid according to a conventional method (for example, a leveling agent, a retarding agent, etc., the dyeing temperature is usually 10 degrees. (: -90. (:, preferably 40. 〇70. Cold press dyeing is a method of dyeing a substance to be dyed by using a well-known inorganic neutral salt such as anhydrous sodium sulfate and sodium hydride, and a well-known acid binder (such as sodium carbonate or sodium hydride), and then The resulting material is dyed in a roll form at room temperature. 15 Continuous dyeing is to make the well-known acid binder (such as sodium carbonate or sodium bicarbonate) and the dry dye solution ready to be dyed. The material is dry dyed, and then the obtained material is dry heat or steamed to fix the color. > Two cold-rolling dyeing method is to dye the material to be dyed with dye, then '..', machine neutral salt (such as sulfuric acid) For treatment with sodium or sodium sulphate, it is preferred to dry or steam solidify the treated material according to the usual 2 〇 method. For example, there is a single-phase printing method with a well-known acid chelating agent ( If the printing is destroyed, it is printed on the material to be printed and dried or steamed to fix the color. Containing a substance to be printed with a printing paste, the obtained substance 15 !3598 〇 2 π is contained in an inorganic neutral salt (such as sodium carbonate) at a temperature (90 C or above) and a well-known acid binder (such as The present invention is not limited to the dyeing or printing method of the preceding paragraph. [Embodiment] For the convenience of further explanation, the following examples will be more specifically described. The following examples are illustrative of the invention, and the scope of the patent application φ of the present invention is not limited thereby. For convenience of description, the compounds are all expressed in the form of free acid in the specification, but the compound 10 in the present invention is manufactured. Or when used, it often exists in the form of a water-soluble salt. Suitable salts may be alkali metal, alkaline earth metal, ammonium salt or organic amine salt. Among them, preferred are sodium salt, oblique salt, salt, salt or triethanolamine. (triethan〇iamine). Unless otherwise stated, the parts or percentages used in the examples are in units of weight 'temperature in degrees Celsius. C. 15 Example 1

20 Take 2.66 parts of p_Aminophenyl-fl-vinyl-sulphone dissolved in 20 parts of acetonitrile, add 10 parts of 25 ammonia water to react at room temperature for 24 hours, crystallize Filtration and drying gave the product structure as in formula (1). H2n

so2ch2ch2—N- h2ch2co2s Η

Ηη2 (1) Elemental analysis (Micro analysis):

Cl6H2lN304S2 calculated: C 50.11, H 5.52, N 10.96; 16 1359802 measured results: C 50.07 %, Η 5.39 %, N 10.32 % ; MS (m/z): calculated 383.5; measured value 384 ; 'H- NMR: 2.49 (2H, d, 8-H), 2.63 (2H, m, 9-H), 3.13 (2H, t, 7 6.78, 7-H), 3.37 (2 H, s, NH2j 6.14 (2H, s, NH2), 6.63 (2 5 H, d, J 8.67, Ar-H), 7.44 (2H, d, J 8.67, Ar-H); 13C-NMR: 38.5 - 40.2 (DMSO, o), 42.6 (1 C, CH2), 55.4 (1 C, CH2), 112.6 (2 C, Ar), 123.6 (1 C, q-Ar), 129.4 (2 C, Ar), 153.5 (1 C, q-Ar).

10 Example 2 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 carried out at 20 ° C for 1 hour while maintaining crystallization, filtration and drying to obtain a product. The structure is as shown in formula (65).

H2N

S02C h2ch2— nhch2ch3 15

(65) Elemental analysis: C10H丨6N202S Calculation result: C, 52.36 %; H, 7.03 %; N, 12.21 %; Measured result: C, 51.68%; H, 7.26 %; N, 12.04 % 20 MS (m/z): calcd. 229; found 229; 'H-NMR: 0.91 (3H, m, 10-H), 2.38 - 2.45 (2H, m, 9-H), 2.67 (2 H, t, J 7.16, 8-H), 3.1 9 (2 H, t, J 7.1 6, 7-H), 6.14 (2 H, s, NH2), 6.64 (2 H, d, J 8.66, Ar -H), 7.45 (2H, d, J 8.67, Ar-H); 17 1359802 13C-NMR: 13c: 15.3 (1 C, CH3), 39.0 - 40.6 (DMSO, 0), 43.3 (2 C, 2x CH2), 55.9 (1 C, CH2), Π3.1 (2 C, Ar), 124.1 (1 C, q-Ar), 129.8 (2 C, Ar), 154.0 (1 C, q-Ar). Then, 2.29 parts of the compound of the formula (65) and 83.83 parts of p-aminostyrene 5 were reacted at 150 ° C for 3 hours, cooled, recrystallized using butanol, filtered, and dried to give a product structure such as formula (2). ).

H2N_<Gk' SO2CH2CH2—N— H2CH2CO2S CH2CH3(2)

Element analysis (Micro analysis): 10

C|8H25N304S2 Calculation result: c, 52.53 %; H, 6.12%; N, 10.21 %; Measured result: C, 53.22 ° /. H, 6.45 %; N, 9.36 〇/〇 ; MS: (w/z): calculated 411.5; measured value 412. Example 3 1.83 parts of p-aminophenylethane were dissolved in 1 part of cyanide, and 3.87 parts of 40% methylamine was added, and the reaction was carried out at room temperature for 4 ^ when recrystallization was carried out using butanol. Filtration and drying gave the product structure as in formula (3). ’

Micro analysis: 20 1359802

Ci7H23N3〇4S2 Calculation result: C, 51.37 %; H, 5.83 %; N, 10.57 % ; Measured result: C, 51.37 %; Η, 5.79 %; N, 10.37 % ; MS: (m/z): Calculated value 397.5 ;. The measured value is 398. 5 Example 4 1.83 parts of p-aminostyrene and 0.45 parts of aniamine were added to the reaction tube, then 5 drops of acetic acid were added, and reacted at 12 ° C for 6 hours, cooled, crystallized, Transition, drying, to give the product structure 10 as in formula (4).

MS: (m/z): C22H25N304S2 Calculated 459.6; 460. • 15 Example 5 3 0 parts of ice water was added to 2.6 6 parts of m-aminostyrene stone 'after adding 1 part of 25% aqueous ammonia solution, reacted at room temperature for 24 hours, with a pH 12 alkaline solution containing 20% salt The mixture was sufficiently filtered to give an oily product structure of formula (5).

—S02CH2CH2—N- h2ch2co2s h2n nh2 20 (5) MS: (m/z): Cl6H2lN304S2 Calculated 383.5; 1359802 Example 6 10 parts of vinegar vinegar solution 1.92 parts of the compound of the formula (5) prepared in Example 5, followed by 0.42 parts of sodium acetate and 9.0 parts of oxygenated acetic anhydride at 40°. The reaction was carried out for 2 hours at C, and the product structure was isolated by a column to obtain the formula (6).

MS: (m/z): C18H23N305S2 Calculated 425.5; 425. 10 Example 7

2.66 parts of p-aminostyrene sulfone was dissolved in 20 parts of decane, and 3.25 parts of an aqueous solution of taurine (20 parts) was added, and pH 9 was controlled at room temperature with a 20% aqueous solution of sodium carbonate (Na2CO3). The reaction was carried out for 24 hours, crystallized, filtered, and dried to give a product structure of formula (7).

so2ch2ch2—N- h2ch2co2s ch2ch2so3h

Nh2 (7) MS: (m/z): Cl8H25N307S3 Calculated 491.6; 20 Examples 8 to 5 1 Referring to the synthesis of Examples 1 to 7, the structural formula of the compound of the following Examples (8) to (51) can be obtained. 20 1359802 Table Examples Compound Structure 8

(H5C2)HN

so2ch2ch2—N- h2ch2co2s—^ \ Η NH(C2H5)(8) ho3s 9 h2n- -so2c h2ch factory n - h2ch2co2s H(9) so3h

NH 2 10 H3co-<p>- h2n

So2ch2ch2—n- h2ch2co2s H

OCH3 nh2 (10) 11 h3co h2n

So2ch2ch2—n- h2ch2co2s OCH3

H och3

Nh2 h3co (11) 12

HzNHC) Π π o CNH(CH2)2S〇2CH2CH2—N-HzCH2C02S(H2C)2HNC h

Nh2 (12) 13 so3h

So:ch2ch: — n- h2ch2co:s H so3h

(13) 21 1359802 14

H,N

ί \—so2c h2ch2— n - h2ch2co2s—yV-7 U M NH, (14) 15

(H5c2)HN ί so2ch2ch2-n-h2ch2co2s—^” / — CH3 NH(C2H5) (15) 16

S02CH2CH2—N- h2ch2co2s ch3 (16)

So3h nh2 17

H3c〇-^y~ H->N so2CH2CH; 2_ N - H ch3 (17) :2ch2co2s 0CH3 nh2 18

(18) 19

SO2CH2CH2—N_ H2CH2CO2S' ch3 och3 H3CO (19)

0CH3 NH, —4------ 20 CNH(CH2):SO:CH:CH2-N-H:CH;CO;S(H:C);HNC CH3 ir—^ NH2 (20) 22 1359802 21 so3h

S02CH2CH Factory N- H2CH2C02S ch3 so3h

(21) 22 h2n (. so2ch2ch2—N-h2ch2co2s / ~~ CH2CH3

Nh2 (22) 23

(H5C2)HN "SO2CH2CH2-N-H2CH2CO2S· / — CH2CH3

Nh(c2h5) (23) 24

So2c h2ch factory N - h2ch2co2s. ch2ch3

(24) 25 h3co-^/- h2n CH2CH3 SO2CH2CH2-N-* H2CH2CO2S·

OCH, nh2 (25) 26

So2ch2ch2—n-h2ch2co:s ch,ch3 ch3 - h3c

(26) 27

OCH, CH2CH3 so2ch2ch2—N- h2ch2co2s

H3CO (27) 23 1359802

HzN_<C) η ------π 28 CNH(CH2>2S02CH2CH2—N - h2ch2co2s(h2c)2hnc ch2ch3(28) ir- NH2 29

S03H H*,N

S02CH2CH2— N- h2ch2co2s CH.CH,

SOjH

(29) 30 S02CH2CH2—N- h2ch2co2s ch2ch2oh (30) 31 h2n -so2c h2ch factory n - h2ch2co2s ch2ch2oh(31)

Nh2 32

(H5C2)HN S02CH2CH2—N- h2ch2co2s ch2ch2oh(32) NH(C2H5) 33

So2ch2ch2—n- h2ch2co2s

,so3h nh2 ch2ch2oh(33) 34 H3CO-^- h2n

So2ch2ch2—n- h2ch2co2s CHiCH^OH ;—^—och3 nh2 (34) 24 1359802 35

Ch3 so2ch2ch2—n- h2ch2co2s ch2ch2oh

(35)

(36)

H2N~〇J? '-PI 37 CNH(CH2>2S02CH2CH2-n_h2ch2co2s(h2c)2hnc ch2ch2oh (37) 38 so3h

So2ch2ch"n-h2ch2co2s ch2ch2oh (38)

39 h2n so2ch2ch2—n-h2ch2co2s ch2ch2so3h (39) nh2 40

(H5c2)HN so2ch2ch factory n-h2ch2co2s—^ \ CH2CH2S〇3H \H(C2Hs) (40) 41

So2c h2ch2- n - H2CH2CO; S ch2ch2so3h

(41) 25 1359802 42 h3co~~so2ch2ch2—N-H2CH2C02S—“OCH; / ~ ch,ch2so3h ~\ H,N - NH, ch2ch2so3h(42) 43

Och3 so2ch2ch2—n- h2ch2co2s

kcH2S03H h3c (43) 44

(44) h2n~C^ 45 o o II II CNH(CH2)2S02CH2CH2—N-H2CH2C〇2S(H2C)2HNC ch2ch2so3h nh2 (45) 46 so3h

So2ch2ch2—n-h2ch2co2s ch2ch2so3k so3h

(46) 47 so2ch2ch2—n-h2ch2co2s COCHj(47) 〇2s-〇- nh2 48

Ho3s H:N

So2ch2ch2—n-h2ch:co:s coch3

so3H NH, (48) 26 1359802

49

(49) 50

(50) 51

(51) Example 52 3.66 parts of p-aminostyrene sulfone was dissolved in 40 parts of cyanonane, and 5.2 parts of ethanolamine was added thereto, and reacted at room temperature for 12 hours, crystallized, filtered, and dried. The product structure is obtained as in formula (66).

H2N_^_S〇2CH2CH2-NHCH2CH2OH Formula (66) Elemental analysis (Micro analysis): 10 Cl0Hl6N2O3S Calculation result: C 49.17 %, Η 6.60 %, N 1 1.46 % ; Measurement result: C 48.92 %, Η 6.63 %, Ν 11.40 27 ; 1359802 MS (m/z): calculated value 244.3; measured value 245 ; *H-NMR : 1.81 (1 H, s, ΝΗ), 2.45-2.49 (m, DMSO), 2.67-2.72 (2 H , m, 8-H), 3.18-3.23 (2 H, m, 7-H), 4.44-4.48 (1 H, t, J 4.90, OH), 6.14 (2 H, s, NH2), 6.63 (2 H, d5 J 8.29, 5 Ar-H), 7.45 (2H, d, J 8.67, Ar-H);, 3C-NMR: 38.5-40.2 (m, DMSO), 43.0 (1 C, CH2), 51.1 (1 C, CH2), 55.6 (1 C, CH2), 60.1 (1 C, CH2), 112.6 (2 C, Ar), 123.7 (1 C, q-Ar), 129.4 (2 C, Ar), 153.5 (1 C, q-Ar). 10 Then 'take 5 parts of m-Aminophenyl-β-vinylsulphone dissolved in 50 parts of cyanonane, and add 5 parts of the compound of formula (66) to react at room temperature for 12 hours. Filtration and drying gave the product structure as in formula (52). NH2 h2n-

So2ch2ch 2~N — H21 ch2ch2oh ch2co2s

Φΐ5 (52) Elemental analysis (Micro analysis):

Ci8H25N305S2 Calculation results: C 50.57 %, Η 5.90 %, N 9.83 % ; Results: C 50.3 1 %, Η 5.85 %, N 9.7 1 % ; MS: (w/z): calculated value 427.6 ; measured value 428 . Examples 53 to 64 With reference to the synthesis of Example 52, the structural formula of the compound of the following Examples (53) to (64) can be obtained. 28 20 1359802 Table 2 Examples Compound Structure 53 η2ν_<Οκ_ so2ch2ch Factory Ν- h2ch2co2s ch2ch2oh(53)

So3h nh2 ho3s och3 54 h2n-

So2ch2ch2—ν- h2ch2co2s U2〇h -nh2 h3c (54) nh2 55 h2n- -so2ch2ch2—n- h2ch2co2s ch2ch3(55)

So3h 9 56 h2n

So2c h2ch2— n - h2ch2co2s-ch2ch3(56) -nh2 h3co 57 h2n- ,so3h -so2ch2ch2-n-h2ch2co2s

NH. ch2ch3(57) 29 1359802 58 h2n

Nh2 CH2CH3 (58) h2n- 59 -so2ch2ch2—N- h2ch2co2s ch2ch2so3h(59)

Nh2 60 so2ch2ch2—n- h2ch2co2s-ch2ch2so3h(60) so3h -NH-, H3CO h2n- so3h 61 ch3 S02CH2CH plant N-H2CH2C02S-r N>-NH, ch2ch2so3h (61) h2n 62

(62) 63

—OCH3 nh2 30 1359802

Application Example 1 1.92 parts of N,N-di-[2-(4'-aminophenyl)-sulphonylethyl] 5-amine (compound of formula (1)) was dispersed in 100 parts of ice water, followed by addition of red compound formula (67) Powder added, ho3soh4c2o2s

Ho3s/^/^/^so3h f Formula (67) Next, adjust the pH value to 5.5 with sodium bicarbonate, continue stirring at a temperature of 15-25 10 °C until the condensation reaction is completed, after salting out, filtration and brine filtration The washing procedure yields a red dye structure such as formula (68). It is used as a cellulose fiber. Dyeing dyeing has excellent dyeing properties. 31 1359802 ho3soh4c2o2s

HN- > so2ch2ch2

HO3SOH4C2O2S

NH hn_hCj^~ so2ch2ch2 Application Example 2 2.13 parts of N,N-bis-[2-(4'-Aminophenyl)sulphonylethyl] 5 -2-hydroxyethylamine (compound of formula (30)) was dispersed in 100 parts of ice water, followed by 3.0 The 32% HCl was thoroughly stirred, and 0.69 parts of sodium nitrite was added thereto, and stirring was continued at 0 to 5 ° C until diazotization was completed. 3.19 parts of 1-hydroxy-8-amino-naphthalene-3,6-di sulfonic acid φ was added to the previously obtained diazonium compound, and stirring was continued until the coupling reaction was completed to obtain a product structure of the formula (69). Ho3s·

Ch,ch2oh I ' so2ch2ch2—N—h2ch2co2s so3H

HChS ‘

S03H Formula (69) Next, 2.81 parts of 4-callo-sulfatoethylsulfone-aniline was dispersed in 30 parts of ice water, followed by adding 3.0 parts of 32% hydrochloric acid (HC1), fully stirred, and then adding 0.69 parts of sodium nitrite. Stirring was continued at 0 to 5 ° C until diazotization was completed, the above coupling product was added, and the acid value of 32 1359802 was adjusted to 5 with sodium hydrogencarbonate, and stirring was continued at a temperature of 15 to 25 ° C until the coupling reaction was completed. The naphtha dye structure was obtained by salting out, filtration and brine filtration to give the formula (70). Dyeing dyeing of cellulose fibers has excellent dyeing properties. Ho3soh4c2o2s

H03SOH4C202S - 〇

x~QjT Formula (.70) so2ch2ch2 n-ch2ch2oh so2ch2ch2 Test Example 1 Take 1 part of the dye of the application formula (70), completely dissolve in 100 parts of distilled water to prepare a dye liquid, and inject 20 parts of the dye liquid into the dyeing cup. 4.8 parts of Glauber's salt was added, and the dyeing solution was added to a total amount of 75 parts with distilled water, and then 320 g of a 10/liter soda lye aqueous solution was added. Take 4 parts of cotton flat woven fabric into the dyeing solution, lock the upper cover and shake it up and down to make the dye uniform. Put the dyeing cup into the thermostatic bath, start the rotating button, and warm up to 60 °C for 30 minutes. Minute fixing. After the dyeing is completed, the swatches are taken out and rinsed with cold water, and then subjected to general cleaning, dehydration, and drying procedures to obtain a navy blue dye having excellent dyeing depth and coloring rate. In summary, the present invention can indeed achieve the purpose of the invention by the disclosed technical idea, which is novel, progressive and industrially utilized, and is in conformity with the requirements of the invention patent. However, those disclosed above are preferred embodiments, and any changes or modifications made by the local origins are derived from the technical idea of the present invention and are easily inferred by those skilled in the art, without departing from the scope of the patent. 33 20 1359802 [Simple description of the diagram] None [Key component symbol description]

Claims (1)

1359802 ,,-•巧-Λ 〇 No. 96131389, revised page of January 101. X. Patent application scope: 1. An ankyl compound having N,N•dialkylamino group of the following formula (la), ψ -B-(CH2)m-Ν-(〇Η2)ή—B'- (R)i NH r2 (Ia) Ri 5 wherein R and R are independently selected from the group consisting of: hydrogen atom, sulfonic acid group a group consisting of ci 4 alkyl and C! _4 alkoxy; and I are each independently a hydrogen atom or a Ci 4 alkyl group; ίο R'' is a hydrogen atom, a Cl~4 burnt group, a phenyl group, ^4 alkyl or a tetraalkyl group substituted by a dentate, a hydroxyl group, a carboxyl group, or a sulfonic acid group; B and B are each independently selected from the group consisting of: s〇2 and c〇nh _(cH2)n_s〇2_ Ethnic group i and j are each independently an integer from 〇 to 3; and m and η are each independently an integer of 2 to 4, respectively. 2. The bridging compound having an anthracene-dialkylamino group as claimed in claim 1, wherein R and R are each independently selected from the group consisting of a hydrogen atom, a sulfonic acid group, a decyl group and a methoxy group. The ethnic group. 3 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ &lt;0 (^3 and the group consisting of benzene rings. 35 1359802 4. The bridging compound having N,N-dialkylamino group according to claim 1 wherein R and R' are the same and are selected From: a group consisting of a hydrogen atom, a sulfonic acid group, a Ci. 4 alkyl group, and a Ci 4 alkoxy group; 1 and R2 are the same and are a hydrogen atom or a Ci 4 alkyl group; 5 B and B' are the same and are selected from a group consisting of :-S〇2· and -CONH-(CH2)n -S02-; 1 is the same as j and is an integer from 〇 to 3; and m and π are the same and are integers from 2 to *. An abranched compound having an N,N•dialkylamino group in the i-th aspect of the patent application, wherein the compound of the formula (Ia) is a compound of the following formula (1), h2n ~~&lt;^~~^&gt;~- So2ch2ch factory y- h2ch2co2s ΝΗο (1) . 6—A bridging compound having a fluorene-dialkylamino group as the compound of the formula (Ia), wherein the compound of the formula (Ia) is a compound of the following formula (2) 'H2N~~^~^-S02ch2ch2-n - h2ch2co2s—/&quot; 15 CH2CH3 (2) . 7. The bridging compound having an N,N-dialkylamino group as claimed in claim i, wherein the compound of the formula (Ia) is a compound of the following formula (3), Η2ΝΌ~ch3 S〇2CH2CH2—ν—h2ch2co2s Nh2 36 (3) 20 1359802 8. The bridging compound having an N,N-dialkylamino group according to claim 1, wherein the compound of the formula (la) is a compound of the following formula (4), so2ch2ch plant N - h2ch2co2s I (4) . H2N^Z^ 9. The bridging compound having an N,N-dialkylamino group according to claim 1, wherein the compound of the formula (la) is a compound of the following formula (5), h2n so2ch2ch2—N - h2ch2co2s Η Ηη9 (5). </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; H2n So2ch2ch2- -Ν - Η!丨 coch3 ch2co2s- nh2 (6) . π. The bridging compound having a N,ν-dialkylamino group according to claim 1, wherein the compound of the formula (la) is a compound of the following formula (7), S02CH2CH2—N- h2ch2co2s ch2ch2so3h Nh2 (7) 12. The bridging compound having an N,N-dialkylamino group according to claim 1, wherein the compound of the formula (la) is a compound of the following formula (52), 37 15 1359802 h2n so2ch2ch2-N- H2ch2co2s ch2ch2oh Nh2 (52) 38