CN1170816C - N,N'-disubstituted aniline aromatic diformylamine, its derivative and its prepn process and use - Google Patents
N,N'-disubstituted aniline aromatic diformylamine, its derivative and its prepn process and use Download PDFInfo
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- CN1170816C CN1170816C CNB011262834A CN01126283A CN1170816C CN 1170816 C CN1170816 C CN 1170816C CN B011262834 A CNB011262834 A CN B011262834A CN 01126283 A CN01126283 A CN 01126283A CN 1170816 C CN1170816 C CN 1170816C
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Abstract
The present invention relates to N, N'-dibasic anilino fragrance lumichrome amide with the following structural formula and a perylene derivative, a synthetic method and a purpose thereof. X= phenyl, naphthyl, pyridyl, pyrrolyl or furyl, n=0, 1, 2. The N, N'-dibasic anilino fragrance lumichrome amide with the following structural formula and the perylene derivative thereof are formed by a method that fragrant lumichrome amide abuttal is educed in biphenyl. The present invention has the advantages of easily obtained raw materials, low price, simple synthetic method, bland reaction conditions and high yield; the present invention is a novel benzidine substituted intermediate body with no carcinogenesis toxicity, and can be used for synthesizing an environment protection type azo dye.
Description
Technical field
The present invention relates to a kind of N, N '-disubstituted benzenes amido fragrance diformamide and derivative, preparation method and purposes.
Technical background
P-diaminodiphenyl (Benzidine) and p-diaminodiphenyl based dye be the developing history in existing over one hundred year up till now.From German Bottinger in 1884 first with synthetic first substantive dyestuff of p-diaminodiphenyl---Congo red (Congo Red) afterwards, the production development of p-diaminodiphenyl based dye is very rapid.Because p-diaminodiphenyl based dye chromatogram is complete, excellent property, many characteristics such as cheap, therefore in dyeing such as fiber, silk, fiber crops, leather, be widely used, for a long time, the p-diaminodiphenyl based dye maintains the leading position always, occupies crucial status in dyestuffs industries.
Yet, after p-diaminodiphenyl invention ten surplus year, German Rehn just suspects that p-diaminodiphenyl has carcinogenic toxicity, until after 1954 through bladder cancer patients statistic data researchs in a large number, confirmed that p-diaminodiphenyl, 2-naphthylamines, 4-phenylaniline etc. belong to carcinogenic substance.What carinogenicity was the strongest in carcinogenic aromatic amine is the 2-naphthylamines, secondly is p-diaminodiphenyl, and it caused being respectively the latent period of bladder cancer 16 years, 20 years and 22 years.
In recent years, along with environment protection, cleaning procedure, green chemical industry product cause extensive attention day by day in countries in the world." second batch of consumer's goods regulations " (The Second Consumer GoodsOrdinance) of German Government promulgation on July 16th, 1994 clearly stipulated 22 kinds of forbiddings such as p-diaminodiphenyl, 2-naphthylamines, 4-phenylaniline aromatic amine in the 3rd group of AI group of MAK and AII category, relates to the production of 118 kinds of dyestuffs thus.Therefore, develop that no carcinogenic toxicity p-diaminodiphenyl substitutes intermediate and dyestuff is very urgent.
Leather is the important industry of China, no matter is sold inside the country market, and still foreign exchange earning all plays crucial effect.It 50% or more is black dyes that leather coloring uses, and black dyes most popular be direct black BN (C.I. directly deceives 38), cheap because of this dyestuff, pitch black degree is good, thereby usage quantity is bigger.But the intermediate that this dyestuff uses in synthetic is p-diaminodiphenyl, therefore, develops that no carcinogenic toxicity p-diaminodiphenyl substitutes intermediate and dyestuff is more urgent for leather industry.
Up to the present, existing p-diaminodiphenyl is that its general formula of intermediate is as follows:
X=-SO
2NH-,-CONH-,-NHCONH-,-NH-,-CH=CH-etc., R
1, R
2=-H ,-SO
3H ,-NO
2,-COOH etc.
Wherein effect p-diaminodiphenyl commonly used preferably substitutes intermediate and is, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminobenzil disulfonic acid (DSD acid), 4,4 '-diamino-diphenylamine and derivative, 4,4 thereof '-diaminobenzene sulfonanilide (DABSA) can directly deceive 38 to replace C.I. with its synthesizing black dyestuff.
With these intermediate institute synthetic black dyess, its structure is as follows:
C.I. directly deceive 38
Directly black M
C.I. directly deceive 166
C.I.. ACID BLACK 234
These p-diaminodiphenyl substitute intermediate, particularly 4,4 '-diaminobenzene formylaniline and 4,4 '-the diaminobenzene sulfonanilide, its abutment both sides phenyl ring is copline not, makes the conjugated system of formed dye molecule by " partitions ", so two relatively independent color development systems of dye molecule formation, can carry out intramolecular colorant match to a certain extent, when dyeing, can obtain black by the intramolecularly colorant match.
But, these p-diaminodiphenyl substitute intermediate will directly carry out reactions such as nitrated, reduction, sulfonation, chlorosulphonation in building-up process, reaction conditions is not gentle, simultaneously, also produce a large amount of waste gas, waste residue, contaminated wastewater environment, etching apparatus, so the mass production of this class intermediate is restricted, so the good and environment amenable no carcinogenic toxicity p-diaminodiphenyl of exploitation use properties substitutes the practical significance that intermediate has suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of N, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof is the intermediate that substitutes of benzidine dye.
Another object of the present invention provides a kind of synthetic above-mentioned N, the synthetic method of N '-disubstituted benzenes amido fragrance two formyls and sulfonamide derivatives thereof.
A further object of the present invention just provides a kind of synthetic above-mentioned N, and the purposes of N '-disubstituted benzenes amido fragrance diformamide and derivative thereof can be used as the raw material that synthesizes azoic dyestuff.
N of the present invention, the structural formula of N '-disubstituted benzenes amido fragrance diformamide and derivative thereof can be expressed as follows:
Wherein: the phenyl that X=R replaces, phenyl, naphthyl, pyridyl, pyrryl, furyl, thienyl, quinolyl, pyrazolyl or pyrimidyl, R=Cl, NO
2, SO
3H or CH
3, n=0,1,2.
N of the present invention, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof can be following structural formulas:
R=Cl, NO
2, SO
3H or CH
3, n=0,1,2;
n＝0，1，2；
n＝0，1，2；
x＝CH
2，NH，O，S，y＝0，N，n＝0，1，2；
x＝CH
2，NH，O，S，z＝0，N，n＝0，1，2；
n＝0，1，2；
N=0,1,2 compound such as grade.
Above-mentioned N of the present invention, the synthetic method of N '-disubstituted benzenes amido fragrance two formyls and sulfonamide derivatives thereof can be synthetic with conventional aromatic dioctyl phthalate chloride method.
Mol ratio with aromatic dimethyl chloride compound and aromatic diamine compound is 1: during 1-2, at water or/and in the organic solvent, in room temperature to 80 ℃ following reaction 1-5 hour, thereby generate above-mentioned product N, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof.Wherein, described aromatic diamine compound structural formula is,
Described aromatic dimethyl chloride compound molecule formula is ClC (O)-X-C (O) Cl, X=phenyl wherein, naphthyl, pyridyl, pyrryl, furyl, thiophene or thiazole, n=0,1,2.
N of the present invention, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof can be with conventional method in azoic dyestuff synthetic, as diazo component and coupling component coupling, thus the further polyazo dye of synthetic various form and aspect.
N of the present invention, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof can aromatic dimethyl chloride compound and aromatic diamine compound be raw material, generate N by reactions such as condensations, N '-disubstituted benzenes amido fragrance diformamide series derivates.
The used raw material of synthetic method of the present invention is easy to get, and is cheap, and Industrial products are mostly arranged, the reaction conditions gentleness, and yield can reach more than 90%, and the water that uses is green solvent, thereby meets the requirement of Green Chemistry industry.
Substituting intermediate with other p-diaminodiphenyl compares, intermediate of the present invention has its outstanding feature, promptly adopt isophthaloyl amine or pyridine diformamide or other heterocycle diformamide as abutment, because the existence of two amide group, make abutment phenyl ring (heterocycle) and both sides phenyl ring have certain dihedral, the electronic cloud flowability of whole molecule is obstructed relatively, make not copline of amide group both sides phenyl ring, like this, use its synthetic dyestuff, its dyestuff both sides spectral quality has independence, can carry out colorant match at intramolecularly; Simultaneously, because abutment phenyl ring (heterocycle) and both sides phenyl ring be copline not, with its synthetic dye molecule tool with certain kindliness, good water solubility, be easy to infiltrate the inside that is colored fabric and dye thoroughly, and do not make its feel hardening and keep its original characteristics constant, be that a kind of p-diaminodiphenyl preferably substitutes intermediate, have certain industrial prospect.
Embodiment
To help further to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
(0.84g 5mmol), is back to no bubble and emits to add m-phthalic acid in sulfur oxychloride (5ml).Take out excessive sulfur oxychloride, stand-by.
With 2 of 10mmol (2.1g), 4-diamino benzene sulfonic acid sodium is dissolved in the water of 10ml, at room temperature slowly adds above-mentioned m-phthaloyl chloride, in 30-60min, add, simultaneously, drip sodium carbonate solution, regulate pH value and be not less than 8.0, stirring 60-90min slowly drips 1: 1 (hydrochloric acid soln of water/36%HCl), make its pH value 2-2.5, the adularescent precipitation is separated out, and filters drying, get white meal, yield 93%.
Reaction formula is as follows:
(1) chloride
(2) condensation reaction
The m-phthalic acid that adopts, m-phthaloyl chloride, 2,4-diaminobenzene SULPHURYL CHLORIDE all has industrial goods.
. product:
M=506.56, ultimate analysis C
20H
18N
4O
8S
2: calculated value C, 47.42%; H, 3.59%; N, 11.06%; S, 12.66%; O, 25.77%; Measured value: C, 47.32%; H, 3.50%; N, 11.01%.
1H-NMR(DMSO)：10.66(s，2H)，8.51(s，1H)，8.14(d，2H)，7.87(s，2H)，7.69-7.56(m，5H)，4.89(br，4H).
13C-NMR(DMSO)：165.6，140.8，135.0，134.5，131.3，131.1，129.0，128.4，127.5，117.6，114.0.
IR(KBr)：3413，3081，2593，1675，1605，1529，1498，1417，1331，1197，1075，1021，876，832
Embodiment 2
(0.84g 5mmol), is back to no bubble and emits to add m-phthalic acid in sulfur oxychloride (5ml).Take out excessive sulfur oxychloride, stand-by.
The Ursol D of 10mmol (0.15g) is dissolved among the HAc of 10ml, at room temperature slowly add above-mentioned m-phthaloyl chloride, in 30-60min, add, drip sodium carbonate solution, regulate the pH value and be not less than 6.0-8.0, stir 60-90min, then, slowly drip 1: 1 (hydrochloric acid soln of water/36%HCl), make its pH value 2-2.5, filter, get product, yield 93%.
Product:
M=346.42, ultimate analysis C
20H
18N
4O
2: calculated value C, 69.34%; H, 5.25%; N, 16.18%; O, 9.24%; Measured value: C, 69.31%; H, 5.15%; N, 16.09%.
1H-NMR(DMSO)：10.00(s，2H)，8.42(s，1H)，8.03(d，2H)，7.61(t，3H)，7.39(d，4H)，6.55(d，4H)，4.95(s，4H).
13C-NMR(DMSO)：164.5，145.5，135.8，130.3，128.6，128.3，126.9，122.4，114.0.IR(KBr)：3367，2589，1639，1534，1516，1426，1321，1255，897，876，817，793.
Embodiment 3
With 10mmol (2 of 2.1g, 4-diamino benzene sulfonic acid sodium is dissolved in the water of 10ml, at room temperature slowly adds dimethyl chloride between the pyridine after the aforesaid method chloride, in 30-60min, add, simultaneously, drip sodium carbonate solution, regulating pH value is 6.0-8.0, and stirring 60-90min slowly drips 1: 1 (hydrochloric acid soln of water/36%HCl), make its pH value 2-2.5, the adularescent precipitation is separated out, and filters drying, get white meal, yield 95%.
Product:
M=507.55, ultimate analysis C
19H
17N
5O
8S
2: calculated value C, 44.96%; H, 3.84%; N, 13.80%; S, 12.64%; O, 25.22%; Measured value: C, 44.76%; H, 3.80%; N, 13.64%.
1HNMR(DMSO)：11.41(s，2H)，7.50-8.4(m，7H)，7.88(s，2H)，4.52(br，4H).
13CNMR(DMSO)：163.2，147.8，140.1，132.2，131.1，129.0，127.9，125.6，113.2，111.4.IR(KBr)：
3405，3020，1698，1605，1585，1527，1448，1414，1326，1203，1078，1017，872，841，748.
Embodiment 4
With 10mmol (2 of 2.1g, the 4-diamino is dissolved in the Ursol D of 10mmol (0.15g) among the HAc of 10ml, at room temperature slowly adds dimethyl chloride between above-mentioned pyridine, in 30-60min, add, simultaneously, drip sodium carbonate solution, regulating pH value is 6.0-8.0, and stirring 60-90min slowly drips 1: 1 (hydrochloric acid soln of water/36%HCl), make its pH value 2-2.5, the adularescent precipitation is separated out, and filters drying, get white meal, yield 95%.
Product:
M=347.41, ultimate analysis C
19H
17N
5O
2: calculated value C, 65.68%; H, 4.94%; N, 20.16%; O, 9.21%; Measured value: C, 65.58%; H, 4.843%; N, 20.06%.
1HNMR(DMSO)：11.42(s，2H)，7.54-8.51(m，9H)，7.85(s，2H)，4.52(br，4H).
13CNMR(DMSO)：161.2，146.8，141.1，133.2，131.1，129.0，127.9，125.6，113.2，101.4.IR(KBr)：
3405，3020，1697，1604，1585，1528，1447，1414，1316，1203，1068，1017，882，841，758.
Embodiment 5
M=494.53, ultimate analysis C
18H
16N
5O
8S
2: calculated value C, 43.71%; H, 3.27%; N, 14.16%; S, 12.97%; O, 25.88%; Measured value: C, 43.62%; H, 3.20%; N, 14.11%.
1HNMR(DMSO)：11.44(s，2H)，7.50-8.4(m，6H)，7.86(s，2H)，4.52(br，4H).
13CNMR(DMSO)：164.1，147.9，140.1，136.2，134.1，128.1，128.9，126.7，114.2，111.4.IR(KBr)：
3405，3021，1698，1604，1589，1526，1467，1410，1326，1204，1078，1018，876，841，747.
Embodiment 6
M=495.52, ultimate analysis C
17H
15N
6O
8S
2: calculated value C, 41.20%; H, 3.08%; N, 18.29%; S, 12.94%; O, 25.83%; Measured value: C, 41.10%; H, 3.01%; N, 18.24%.
1HNMR(DMSO)：11.45(s，2H)，8.46(s，1H)，7.88(s，2H)，4.58(br，4H).
13CNMR(DMSO)：166.1，149.9，140.1，137.2，134.1，129.1，128.7，126.5，113.2IR(KBr)：
3408，3023，1697，1607，1589，1526，1467，1419，1326，1224，1077，1017，876，851，746.
Embodiment 7
M=334.39, ultimate analysis C
18H
16N
5O
2: calculated value C, 64.65%; H, 4.83%; N, 20.95%; O, 9.57%;
Measured value: C, 64.60%; H, 4.76%; N, 20.81%.
1HNMR(DMSO)：11.44(s，2H)，7.55-8.57(m，8H)，7.84(s，2H)，4.54(br，4H).
13CNMR(DMSO)：166.2，145.8，142.1，134.2，130.1，120.0，126.9，124.6，112.2，100.4.IR(KBr)：
3406，3020，1698，1605，1585，1528，1449，1416，1316，1202，1067，1010，882，841，759.
Embodiment 8
M=336.38, ultimate analysis C
18H
16N
4O
3: calculated value C, 64.27%; H, 4.80%; N, 16.66%; O, 14.27%;
Measured value: C, 64.16%; H, 4.68%; N, 16.53%.
1HNMR(DMSO)：11.44(s，2H)，7.50-8.4(m，6H)，7.86(s，2H)，4.52(br，4H).
13CNMR(DMSO)：164.1，147.9，140.1，136.2，134.1，128.1，128.9，126.7，114.2，111.4.IR(KBr)：
3405，3021，1698，1604，1589，1526，1467，1410，1326，1204，1078，1018，876，841，747.
Embodiment 9
M=352.45, ultimate analysis C
18H
16N
4O
2S: calculated value C, 61.34%; H, 4.59%; N, 15.90%; S, 9.10%, O, 9.08%; Measured value: C, 61.23%; H, 4.50%; N, 15.81%.
1HNMR(DMSO)：11.43(s，2H)，7.49-8.53(m，8H)，7.85(s，2H)，4.51(br，4H).
13CNMR(DMSO)：165.1，146.9，141.1，136.2，137.1，127.1，129.9，128.7，114.1，111.3.IR(KBr)：
3407，3028，1690，1603，1589，1526，1468，1411，1328，1200，1070，1017，876，840，749.
Embodiment 10
M=512.59, ultimate analysis C
18H
16N
4O
2S
3: calculated value C, 42.17%; H, 3.15%; N, 10.93%; S, 18.77%, O, 24.97%; Measured value: C, 42.11%; H, 3.10%; N, 10.83%.
1HNMR(DMSO)：11.34(s，2H)，7.51-8.45(m，6H)，7.88(s，2H)，4.42(br，4H).
13CNMR(DMSO)：163.1，147.8，140.6，136.7，134.1，128.1，128.9，126.7，114.2，111.4.IR(KBr)：
3405，3021，1698，1604，1589，1526，1467，1410，1329，1200，1071，1017，875，842，746.
Embodiment 11
M=556.62, ultimate analysis C
24H
20N
4O
8S
2: calculated value C, 51.78%; H, 3.63%; N, 10.07%; S, 11.52%, O, 23.01%; Measured value: C, 51.63%; H, 3.51%; N, 10.12%.
1H-NMR(DMSO)：10.69(s，2H)，8.54(s，1H)，8.18(d，2H)，7.89(s，2H)，7.69-7.56(m，10H)，4.89(br，4H).
13C-NMR(DMSO)：167.6，140.9，134.0，134.9，131.2，131.5，129.8，128.8，127.9，117.0，114.0.
IR(KBr)：3419，3081，2598，1678，1606，1527，1498，1419，1336，1198，1075，1021，876，838
Embodiment 12
M=396.48, ultimate analysis C
24H
20N
4O
2: calculated value C, 72.70%; H, 5.09%; N, 14.13%; O, 8.07%; Measured value: C, 72.58%; H, 5.03%; N, 14.06%.
1HNMR(DMSO)：11.42(s，2H)，7.54-8.51(m，9H)，7.85(s，2H)，4.52(br，4H).
13CNMR(DMSO)：161.2，146.8，141.1，133.2，131.1，129.0，127.9，125.6，113.2，101.4.IR(KBr)：
3405，3020，1697，1604，1585，1528，1447，1414，1316，1203，1068，1017，882，841，758.
Embodiment 13
M=348.40, ultimate analysis C
18H
16N
6O
2: calculated value C, 62.05%; H, 3.64%; N, 24.13%; O, 9.18%; Measured value: C, 62.01%; H, 3.60%; N, 24.03%.
1HNMR(DMSO)：11.40(s，2H)，7.44-8.50(m，8H)，7.83(s，2H)，4.51(br，4H).
13CNMR(DMSO)：164.1，145.9，140.1，136.0，137.1，126.1，129.9，128.9，114.1，111.8.IR(KBr)：
3407，3027，1692，1603，1588，1529，1468，1411，1321，1201，10767，1017，879，840，741.
Embodiment 14
M=508.54, ultimate analysis C
18H
16N
4O
8S
2: calculated value C, 42.51%; H, 3.18%; N, 16.53%; S, 12.61%, O, 25.17%; Measured value: C, 42.43%; H, 3.13%; N, 16.45%.
1H-NMR(DMSO)：10.56(s，2H)，8.49(s，1H)，8.14(m，2H)，7.85(s，2H)，7.69-7.59(m，4H)，4.89(br，4H).
13C-NMR(DMSO)：165.8，140.3?135.3，134.7，131.3，131.6，129.7，128.5，127.5，117.8，114.0.
IR(KBr)：3419，3087，2599，1675，1606，1529，1498，1418，1331，1197，1078，1021，876，839
Embodiment 15
M=557.61, ultimate analysis C
23H
19N
5O
8S
2: calculated value C, 49.54%; H, 3.44%; N, 12.56%; S, 11.50%, O, 22.96%; Measured value: C, 49.46%; H, 3.40%; N, 12.46%.
1HNMR(DMSO)：11.46(s，2H)，7.54-8.58(m，8H)，8.23(s，1H)，7.75(s，2H)，4.52(br，4H).
13CNMR(DMSO)：166.2，140.8，143.1，133.2，131.1，129.0，126.9，125.9，113.0，101.2.IR(KBr)：
3409，3020，1698，1604，1585，1529，1447，1414，1316，1201，1064，1017，883，841，751.
Embodiment 16
M=1080.11, ultimate analysis C
40H
31N
12O
17S
4: calculated value C, 44.48%; H, 2.90%; N, 12.57%; S, 11.88%, O, 25.18%; Measured value: C, 44.58%; H, 2.82%; N, 12.47%; S, 11.75%.
Use N, N '-disubstituted benzenes amido fragrance diformamide and derivative synthetic dyestuff thereof
1.N, the dissolving and the diazotization of N '-disubstituted benzenes amido fragrance diformamide and derivative thereof:
In the 400ml beaker of stirring is housed, any product among the embodiment 1-15 of adding 0.01mol, be N, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof all with to carry out diazotization according to a conventional method synthesize following dyestuff, this example product 3.2g (0.01mol) of example 1, with 20ml water with its furnishing pulpous state, regulating pH with aqueous sodium carbonate is 6.5～7.0, so that all dissolvings, add quick stirring of 5.4ml hydrochloric acid then it is separated out, add 10g ice and be cooled to below 5 ℃, add the sodium nitrite solution of 3.8g (0.02mol), it is blue that the congo-red test paper inspection becomes, the starch-kalium iodide test paper becomes little indigo plant, keeps Sodium Nitrite acid sodium little excessive, and it is complete to react 4 hours diazotization, ehrlich reagent detects no amino and is terminal point, and urea destroys excessive nitrite
2. coupling for the first time:
In the 100ml beaker, add 30ml water and 3.41g (0.01mol) H-acid,, make it molten entirely with 150g/l sodium carbonate solution adjust pH about 6.5.In 30min H-acid is splashed into N gradually, in N '-disubstituted benzenes amido fragrance diformamide diazonium liquid, 10 ℃ are stirred 2h down.Sampling does not observe H-acid fluorescence under ultraviolet lamp be terminal point.
3. p-Nitroaniline diazotization:
Add 2.7ml hydrochloric acid, water and 1.38g (0.01mol) p-Nitroaniline in the 100ml beaker of stirring is housed, heating makes it molten entirely.Start stirring adding 20g ice and be cooled to rapidly below 0 ℃, once pour 30% sodium nitrite solution that is equivalent to 0.7g (0.01mol) into and carry out diazotization.Solution becomes clarification gradually, keeps starch potassium iodide paper to become little indigo plant, and it is blue that congo-red test paper becomes.The ehrlich reagent inspection does not have amino substance and is terminal point.Urea destroys excessive nitrite.
4. coupling for the second time:
Above-mentioned p-Nitroaniline diazonium salt solution is poured in the coupled reaction liquid, stirred and mixed in 1 hour, dripped sodium carbonate solution in 1～1.5 hour to regulate about pH6.5, continue reaction 1 hour.Sampling launches with chromatograph paper, and no monoazo-dyes is terminal point.
5. coupling for the third time:
Pour 20ml water and 1.1g (0.01mol) mphenylenediamine in the 50ml beaker into, heating makes it molten entirely.Be cooled to room temperature, pour in the two coupled reaction liquid, stirred 1～2 hour, in 1 hour, transfer pH7.5～8.Continue reaction 2.5～3h.. sampling and launch with chromatograph paper, no disazo dyes is terminal point.Heat up about 40 ℃, 10% sodium-chlor is saltoutd, and regulates about pH6.5 with hydrochloric acid, stirs about 30min, filters.Filter cake is dried under infrared lamp.Test (dyeing, measure maximum absorption wavelength etc.), dying leather with it, can to obtain blue light black, dyes that polyamide fibre, silk are thick, that fur and wool can obtain blue light is black.
Claims (10)
1. N, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, structural formula is as follows:
Wherein: the phenyl that X=R replaces, phenyl, naphthyl, pyridyl, pyrryl, furyl, thienyl, quinolyl, pyrazolyl or pyrimidyl, R=Cl, NO
2, SO
3H or CH
3, n=0,1,2.
2. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structural formula is as follows:
, R=Cl wherein, NO
2, SO
3H or CH
3, n=0,1,2.
3. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structural formula is as follows:
n＝0，1，2。
4. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structural formula is as follows:
n＝0，1，2。
5. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structural formula is as follows:
x＝CH
2，NH，O，S，y＝0，N，n＝0，1，2。
6. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structure is as follows:
X=CH
2, NH, O, S, z=0 or N, n=0,1,2.
7. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structure is as follows:
，n＝0，1，2。
8. a kind of N as claimed in claim 1, N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, its structure is as follows:
，n＝0，1，2。
9. N as claimed in claim 1, the synthetic method of N '-disubstituted benzenes amido fragrance diformamide and derivative thereof, it is characterized in that in water and organic solvent, the mol ratio of aromatic dimethyl chloride compound and aromatic diamine compound is 1: during 1-2, in room temperature to 80 ℃ following reaction 1-5 hour, described aromatic diamine compound structural formula is:, described aromatic dimethyl chloride compound molecule formula is: ClC (O)-X-C (O) Cl, X=phenyl wherein, naphthyl, pyridyl, pyrryl, furyl or thiophene, n=0,1,2.
10. N as claimed in claim 1, the purposes of N '-disubstituted benzenes amido fragrance diformamide and derivative thereof is characterized in that being used for the intermediate of synthetic azoic dyestuff.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262834A CN1170816C (en) | 2001-07-19 | 2001-07-19 | N,N'-disubstituted aniline aromatic diformylamine, its derivative and its prepn process and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011262834A CN1170816C (en) | 2001-07-19 | 2001-07-19 | N,N'-disubstituted aniline aromatic diformylamine, its derivative and its prepn process and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1335303A CN1335303A (en) | 2002-02-13 |
| CN1170816C true CN1170816C (en) | 2004-10-13 |
Family
ID=4666304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011262834A Expired - Fee Related CN1170816C (en) | 2001-07-19 | 2001-07-19 | N,N'-disubstituted aniline aromatic diformylamine, its derivative and its prepn process and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1170816C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002100295A2 (en) | 2001-03-08 | 2002-12-19 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers as anti-infective agents |
| EP2471527A3 (en) | 2003-03-17 | 2012-12-12 | The Trustees Of The University Of Pennsylvania | Facially amphiphillc polymers and oligomers and uses thereof |
| KR20120107142A (en) | 2004-01-23 | 2012-09-28 | 더 트러스티스 오브 더 유니버시티 오브 펜실베니아 | Facially amphiphilic polyaryl and polyarylalkynyl polymers and olygomers and uses thereof |
| CN105646267A (en) * | 2016-02-25 | 2016-06-08 | 东华大学 | Aromatic diamine monomer and preparation method thereof |
-
2001
- 2001-07-19 CN CNB011262834A patent/CN1170816C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1335303A (en) | 2002-02-13 |
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