JPH0860015A - Production of c.i.reactive blue 19 - Google Patents
Production of c.i.reactive blue 19Info
- Publication number
- JPH0860015A JPH0860015A JP7156459A JP15645995A JPH0860015A JP H0860015 A JPH0860015 A JP H0860015A JP 7156459 A JP7156459 A JP 7156459A JP 15645995 A JP15645995 A JP 15645995A JP H0860015 A JPH0860015 A JP H0860015A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- acid
- reaction
- phosphate buffer
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 title abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000008363 phosphate buffer Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000985 reactive dye Substances 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 abstract description 2
- 235000019799 monosodium phosphate Nutrition 0.000 abstract description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000001488 sodium phosphate Substances 0.000 abstract 2
- 239000007853 buffer solution Substances 0.000 abstract 1
- 229910000397 disodium phosphate Inorganic materials 0.000 abstract 1
- 235000019800 disodium phosphate Nutrition 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 sulfate ester Chemical class 0.000 description 4
- 229910017489 Cu I Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- QZZSAWGVHXXMID-UHFFFAOYSA-N 1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 QZZSAWGVHXXMID-UHFFFAOYSA-N 0.000 description 1
- ZGDOXWZYKDETSP-UHFFFAOYSA-N 1-amino-4-hydroxy-9,10-dioxoanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC(S(O)(=O)=O)=C2N ZGDOXWZYKDETSP-UHFFFAOYSA-N 0.000 description 1
- DGUUUMZJGDNBAC-UHFFFAOYSA-N 2-(3-aminophenyl)sulfanylethanol Chemical compound NC1=CC=CC(SCCO)=C1 DGUUUMZJGDNBAC-UHFFFAOYSA-N 0.000 description 1
- JYVVXBDNAPHKAI-UHFFFAOYSA-N 2-hydroxy-n-phenylethanesulfonamide Chemical compound OCCS(=O)(=O)NC1=CC=CC=C1 JYVVXBDNAPHKAI-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004045 reactive dyeing Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/505—Anthracene dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反応性染料の分野に関
する。ドイツ連邦共和国特許公報Ａ−９６５９０２号に
よって始めて開示されたシー・アイ・リアクティブブル
ー１９（C.I.Reactive Blue 19 ）は、織物を鮮明な青
色に反応性染色するための最も重要な反応性染料の一つ
である。FIELD OF THE INVENTION This invention relates to the field of reactive dyes. CI Reactive Blue 19, first disclosed by the German patent publication A-965902, is one of the most important reactive dyes for the reactive dyeing of textiles into a bright blue color. Is.
【０００２】[0002]
【化４】 この染料の重要性は、一方では使用に際しての高い堅ろ
う度に、他方で染色の高い鮮明度に起因している。[Chemical 4] The importance of this dye is due on the one hand to a high fastness in use and on the other hand to a high sharpness of the dyeing.
【０００３】[0003]
【従来の技術】文献の多くの例で示されている合成方法
は、ブロモアミン酸(bromamine acid)から出発し、３−
（ヒドロキシエチルスルホニル）−アニリンと縮合反応
させるものである。これにより、オキシスルホンブルー
と呼ばれる着色した化合物が得られ、これは、その後硫
酸でエステル化するために多少費用のかかる方法で分
離、精製しなければならない。2. Description of the Prior Art The synthetic methods given in many examples in the literature start with bromamine acid and
(Hydroxyethylsulfonyl) -aniline for condensation reaction. This gives a colored compound called oxysulfone blue, which has to be separated and purified in a somewhat costly manner for subsequent esterification with sulfuric acid.
【０００４】合成経路は、以下の通りである：The synthetic route is as follows:
【０００５】[0005]
【化５】 CuI Clを触媒として使用し、混合物が窒素雰囲気下にあ
るかどうかにより少量の銅粉末を加える。例えば、T.
D. Tuong, M. Hida, 日本化学会、43号（1970年）、176
3頁のような多くの研究により、このような条件下での
活性触媒は、CuI化合物であることが示されている。収
率は高くとも５０％であるが、CuCO3 のようなCuII塩
も、例えば、CAS No. 70:79158j 及びCAS No. 43:6193g
のような幾つかの刊行物により説明されている。[Chemical 5] Cu I Cl is used as a catalyst and a small amount of copper powder is added depending on whether the mixture is under a nitrogen atmosphere. For example, T.
D. Tuong, M. Hida, Chemical Society of Japan, No. 43 (1970), 176
Many studies, such as page 3, have shown that the active catalyst under these conditions is the Cu I compound. Although the yield is at most 50%, Cu II salts such as CuCO 3 are also suitable, for example CAS No. 70: 79158j and CAS No. 43: 6193g.
Are described by several publications such as.
【０００６】T. D. Tuong, M. Hida, J.C.S. Perkins I
I, (1974) 676 頁により、ｐＨ１０までは反応速度が増
大するすることが報告された。この場合において、異な
った化学量論が明らかに用いられ、ｐＨが９を超える
と、望ましくない副生成物であるオキサミン酸がより多
く生成され、従って目的染料の収量は低下する。さら
に、CuI 塩を用いる触媒系では高ｐＨ値で反応速度が低
下する。TD Tuong, M. Hida, JCS Perkins I
I, (1974) p. 676, reported that the reaction rate increased up to pH 10. In this case, a different stoichiometry is obviously used, and when the pH is above 9, more undesired by-product oxamic acid is produced, thus reducing the yield of the target dye. In addition, catalyst systems using Cu I salts have a slower reaction rate at high pH values.
【０００７】Z. Vrba, Collect. Czech. Chem. Commu
n., 46(1) (1981)により、反応速度は用いられる炭酸塩
の量に依存することが報告された。ここでは、この反応
が、リン酸塩を用いた場合にも同様に機能するが、酢酸
塩を使用した場合には機能しないことも報告されてい
る。これらの全ての反応は、Zollinger, Color Chemist
ry, VCH Verlagsgesellschaft, Weinheim, 205-208, (1
991)中で説明されている。Z. Vrba, Collect. Czech. Chem. Commu
n., 46 (1) (1981) reported that the reaction rate depends on the amount of carbonate used. It is also reported here that this reaction works similarly when using phosphate, but not when using acetate. All these reactions are based on Zollinger, Color Chemist
ry, VCH Verlagsgesellschaft, Weinheim, 205-208, (1
991).
【０００８】上記した全ての刊行物は、オキシスルホン
ブルーを経由する方法及び類似した触媒系の使用を開示
している。さらに、中国特許１０３４０１２Ａ号によっ
て、ブロモアミン酸と３−（スルファートエチルスルホ
ニル）−アニリンからC.I. Reactive Blue 19 を直接合
成する方法が示されたが、この実験方法で収量を再現す
ることはできず、また制御することも困難であった。ま
た使用する触媒については、何ら言及されていない。こ
こで好ましい方法は、３−（ヒドロキシエチルメルカプ
ト）−アニリンを経由する方法である。All of the above publications disclose the process via oxysulfone blue and the use of similar catalyst systems. Further, Chinese Patent No. 1034012A showed a method for directly synthesizing CI Reactive Blue 19 from bromoamic acid and 3- (sulfatoethylsulfonyl) -aniline, but the yield could not be reproduced by this experimental method, It was also difficult to control. Further, no mention is made of the catalyst used. The preferred method here is via 3- (hydroxyethylmercapto) -aniline.
【０００９】[0009]
【発明が解決しようとする課題】本発明の課題は、シー
・アイ・リアクティブブルー１９の製造方法を改善し、
上記した従来技術の欠点を克服することにある。The object of the present invention is to improve the method for producing the C.I. Reactive Blue 19,
It is to overcome the drawbacks of the prior art described above.
【００１０】[0010]
【課題を解決するための手段】驚くべきことに、この課
題は、微細に分割された状態である、すなわち大きな表
面積を有する元素状の銅を触媒系として使用し、リン酸
塩緩衝剤を緩衝系として使用し、好ましくはｐＨ７以下
で反応を実施することによって達成される。Surprisingly, the task is to use elemental copper in the finely divided state, ie having a large surface area, as a catalyst system and buffering a phosphate buffer. It is achieved by using it as a system, preferably by carrying out the reaction at pH 7 or lower.
【００１１】本発明は、下記一般式（Ｉ）The present invention has the following general formula (I):
【００１２】[0012]
【化６】 〔式中、Ｚは、-CH2CH2-OSO3M 、-CH=CH2 又は-CH2CH2-
SSO3M 基を表し、Ｍは、水素又はアルカリ金属、好まし
くはLi、Na又はK を表す〕で示される反応性染料の製造
方法に関し、この方法は、下記一般式（II）[Chemical 6] [In the formula, Z is -CH 2 CH 2 -OSO 3 M, -CH = CH 2 or -CH 2 CH 2-.
SSO 3 M group, M is hydrogen or an alkali metal, preferably Li, Na or K], which is represented by the following general formula (II)
【００１３】[0013]
【化７】 で示されるブロモアミン酸を下記一般式（III)[Chemical 7] The bromoamine acid represented by the following general formula (III)
【００１４】[0014]
【化８】 〔式中、Ｘは、Ｏ又はＳを表す〕で示される３−（スル
ファートエチルスルホニル）−アニリンと、元素状銅及
びリン酸塩緩衝剤の存在下において反応させ、形成され
る生成物を単離することからなる。Embedded image [Wherein X represents O or S] is reacted with 3- (sulfatoethylsulfonyl) -aniline represented by the formula (I) in the presence of elemental copper and a phosphate buffer to form a product formed. Consists of isolating.
【００１５】本発明に従った反応もまた触媒の量、緩衝
剤濃度、ｐＨ、温度及び反応物の濃度により影響を受け
る。一般式（Ｉ）の染料は、硫酸エステル型、すなわち
Ｚが-CH2CH2OSO3Mであることが好ましい。ｐＨが７を超
える範囲において、ビニル型、すなわちＺが-CH=CH 2 で
ある化合物が主として形成される。従って、反応の出発
時点では、ｐＨが７以下、特に６．０〜６．８であるこ
とが好ましい。The reaction according to the invention also comprises the amount of catalyst, buffer.
Affected by agent concentration, pH, temperature and reactant concentration
It The dyes of general formula (I) are of the sulfate ester type, ie
Z is -CH2CH2OSO3It is preferably M. pH exceeds 7
Vinyl type, that is, Z is -CH = CH 2so
Some compounds are formed primarily. Therefore, the start of the reaction
At this time, the pH should be 7 or less, especially 6.0 to 6.8.
And are preferred.
【００１６】微細に分割されたCu0 は、６０％を超える
量の硫酸エステル型と２０％のビニル型を形成するよう
に反応を触媒することが見出された。銅は、通常の粉
末、銅ビーズ又は銅片として、加えられるか又は反応の
前に還元及び沈澱させられて、場合によっては、例えば
ジメチルホルムアミド又はＥＤＴＡのような試薬を用い
て活性化して製造され得る。用いられる銅の量は、ブロ
モアミン酸に対し４〜１６重量％、特に５〜８重量％で
あることが好ましい。例えばセラミック又はプラスチッ
クのような多種の担体材料とともにCu0 を用いること又
は銅の金網として用いることが可能であり、これにより
銅の量を、例えば４〜６重量％のように、著しく減少さ
せることができ、銅の金網を使用した場合には事実上の
消費量を測定することは困難になる。It has been found that finely divided Cu 0 catalyzes the reaction to form greater than 60% sulfate form and 20% vinyl form. Copper is prepared as conventional powder, copper beads or copper pieces, added or reduced and precipitated prior to the reaction, and optionally activated with reagents such as dimethylformamide or EDTA. obtain. The amount of copper used is preferably 4 to 16% by weight, particularly 5 to 8% by weight, based on bromoamine acid. It is possible to use Cu 0 with various carrier materials such as ceramics or plastics or to use it as a wire mesh of copper, thereby significantly reducing the amount of copper, for example 4-6% by weight. However, it is difficult to measure the actual consumption when the copper wire mesh is used.
【００１７】ｐＨを望ましい範囲に調整するためにNaH2
PO4 及びNa2HPO4 の混合物をリン酸塩緩衝剤として使用
することが好ましい。リン酸塩緩衝剤の濃度は、ブロモ
アミン酸に対し５〜１５重量％であることが好ましい。
塩の代わりに、水酸化ナトリウム溶液で中和し、特定の
ｐＨ範囲に調整したリン酸を使用することも可能であ
る。リン酸塩緩衝剤を、例えば、シュウ酸ナトリウムと
の混合物として使用することも可能である。NaH 2 in order to adjust the pH to the desired range
It is preferred to use a mixture of PO 4 and Na 2 HPO 4 as the phosphate buffer. The concentration of the phosphate buffer is preferably 5 to 15% by weight based on bromoamine acid.
Instead of salt, it is also possible to use phosphoric acid neutralized with sodium hydroxide solution and adjusted to a specific pH range. It is also possible to use phosphate buffers, for example as a mixture with sodium oxalate.
【００１８】本発明に従った方法を実施する際には、望
まれる主生成物（硫酸エステル型）の他に、この染料の
ビニル型及び副生成物として４−Ｈ−１−アミノ−２−
スルホ−アントラキノン及び４−ヒドロキシ−１−アミ
ノ−２−スルホ−アントラキノンもまた生成される。個
々の組成は、広い範囲で制御され得るものであり、すな
わち反応温度及び銅の量を減少させた場合には、反応時
間は長くなるが、副生成物の濃度は低くなる。しかし、
反応時間が長引くとより多くのビニル型の形成が不可避
となる。達成され得る硫酸エステルの最高量は、７０％
である。一般式（III)の出発物質の最終的な残留物が反
応するならば、硫酸エステル染料はさらにビニル化され
る。目的生成物に応じて、用いられる化学量論及び温度
によって、この系を制御することが可能である。In carrying out the process according to the invention, in addition to the desired main product (sulphate ester form), 4-H-1-amino-2- as vinyl form and by-product of this dye.
Sulfo-anthraquinone and 4-hydroxy-1-amino-2-sulfo-anthraquinone are also produced. The individual compositions can be controlled over a wide range, that is, when the reaction temperature and the amount of copper are reduced, the reaction time is longer, but the by-product concentration is lower. But,
Prolonged reaction time inevitably leads to the formation of more vinylic forms. The maximum amount of sulfate that can be achieved is 70%
Is. If the final residue of the starting material of general formula (III) has reacted, the sulfate ester dye is further vinylated. Depending on the desired product, it is possible to control this system by the stoichiometry and temperature used.
【００１９】硫酸エステルをよい収量で得るために、一
般式（II）及び一般式（III)の反応物の割合を１：１〜
１：１．３、特に１：１〜１：１．１とし、反応温度を
６０〜９５℃、特に７０〜９０℃とする。反応時間は、
５〜４５分である。In order to obtain the sulfate ester in good yield, the ratio of the reactants of the general formula (II) and the general formula (III) is 1: 1 to 1.
The reaction temperature is 60 to 95 ° C., particularly 70 to 90 ° C., and the reaction temperature is 1: 1.3, particularly 1: 1 to 1: 1.1. The reaction time is
5 to 45 minutes.
【００２０】反応溶液の後処理のためには、例えば珪藻
土のような濾過助剤を添加して混合物を濾過し、得られ
た澄んだ溶液（濾液）を濃縮し、乾燥、好ましくは噴霧
乾燥し、目的染料のナトリウム塩（Ｍ＝Ｎａ）を得るの
が適している。さらにナトリウム塩を精製することが重
要である場合には、例えば、代表的な気孔サイズが１ｎ
ｍである酢酸セルロースのような商業的に入手できるナ
ノフィルトレーション(nanofiltration)膜のような特別
な膜を使用して行うことが可能である。For post-treatment of the reaction solution, a filter aid such as diatomaceous earth is added and the mixture is filtered, the resulting clear solution (filtrate) is concentrated and dried, preferably spray dried. It is suitable to obtain the sodium salt of the target dye (M = Na). If it is important to further purify the sodium salt, for example, a typical pore size of 1n
It can be done using a special membrane, such as a commercially available nanofiltration membrane, such as cellulose acetate, which is m.
【００２１】高純度品の要望、特に鮮明な品質を得るた
めに、溶解度のより低いカリウム塩が形成されるが、KC
l を使用して染料を塩析することが可能である。フィル
ター上の残留物は、次の反応に再使用できる。これによ
り、使用されるリン酸塩緩衝剤の量を著しく減少するこ
とができる。In order to obtain the demand for high-purity products, especially clear quality, potassium salts with lower solubility are formed.
It is possible to salt out the dye using l. The residue on the filter can be reused in the next reaction. This can significantly reduce the amount of phosphate buffer used.
【００２２】使用される銅は、反応中に銅塩に酸化され
て部分的に消費され、電気化学的方法で溶液から分離さ
れる。しかし、本発明に従った方法においては、少量
（５重量％まで）のCuI 塩は許容されるが、反応におけ
る銅を主として金属体(Cu0) として使用することが必須
要件である。The copper used is oxidized to the copper salt during the reaction, partially consumed and separated from the solution by electrochemical methods. However, in the process according to the invention, it is essential to use copper in the reaction mainly as the metal body (Cu 0 ), although small amounts (up to 5% by weight) of Cu I salts are acceptable.
【００２３】[0023]
合成実験 ０．１ｍｏｌ（７１．８ｇ、５３．２重量％濃度）のブ
ロモアミン酸を０．１ｍｏｌ（３１．６６ｇ、８８．７
５重量％濃度）の溶解した３−（スルファートエチルス
ルホニル）−アニリン（ｐＨ６．３）に加え、均一な分
散物が形成されるまで混合物を攪拌する。０．１２ｍｏ
ｌのリン酸二水素ナトリウム、０．２ｍｏｌのリン酸水
素二ナトリウム及び６ｇの銅粉末を加える。混合物を９
０℃に加熱し、この間にｐＨは５．６に低下する。反応
が終了した際に、ｐＨを一定に保つ。反応は、わずか１
５分後に終了する。（登録商標）Cellite を加え、混合
物を濾過して浄化する。その後、濾液を噴霧乾燥するか
又はKCl を用いて塩析する。 収量（ブロモアミン酸に対して）：〜７０％ 純度（ＨＰＬＣ） ：６０．７１％の硫酸エステル染料 濾液 ：１９．４４％のビニル染料 フィルター上の残留物を再使用する場合には、緩衝剤の
量及び場合によっては必要なブロモアミン酸の量が、そ
の後の処理において減少する。Synthesis experiment 0.1 mol (31.66 g, 88.7) of 0.1 mol (71.8 g, 53.2% by weight concentration) of bromoamine acid.
5% strength by weight) dissolved 3- (sulfatoethylsulfonyl) -aniline (pH 6.3) and the mixture is stirred until a homogeneous dispersion is formed. 0.12mo
l Sodium dihydrogen phosphate, 0.2 mol disodium hydrogen phosphate and 6 g copper powder are added. Mix 9
Heat to 0 ° C., during which time the pH drops to 5.6. The pH is kept constant when the reaction is complete. Only 1 reaction
It ends in 5 minutes. ® Cellite is added and the mixture is clarified by filtration. The filtrate is then spray dried or salted out with KCl. Yield (based on bromoamine acid): ~ 70% Purity (HPLC): 60.71% Sulfate Dye Filtrate: 19.44% Vinyl Dye If the residue on the filter is reused, buffer The amount and possibly the amount of bromoamic acid required is reduced in subsequent treatments.
【００２４】反応混合物が適した濃度である場合には、
可溶性成分（エステル染料、ビニル染料）を濾過するこ
とが可能である。残留物は、ブロモアミン酸、銅及びリ
ン酸塩から成る。ブロモアミン酸がそれ以上反応しない
オキサミン酸に転換しないことが保証される。残留物に
さらに銅粉末及び３−（スルファートエチルスルホニ
ル）−アニリンを加えて反応させることが可能である。If the reaction mixture is of suitable concentration,
It is possible to filter soluble components (ester dyes, vinyl dyes). The residue consists of bromoamic acid, copper and phosphate. It is ensured that the bromoamic acid does not convert to oxamic acid which does not react any further. It is possible to add copper powder and 3- (sulfatoethylsulfonyl) -aniline to the residue for further reaction.
Claims (10)
SSO3M 基を表し、Ｍは、水素又はアルカリ金属を表す〕
で示される反応性染料の製造方法であって、下記一般式
（II） 【化２】 で示されるブロモアミン酸を下記一般式（III) 【化３】 〔式中、Ｘは、Ｏ又はＳを表す〕で示される３−（スル
ファートエチルスルホニル）−アニリンと、元素状銅及
びリン酸塩緩衝剤の存在下において反応させ、形成され
る生成物を単離することからなることを特徴とする上記
方法。1. A compound represented by the following general formula (I) [In the formula, Z is -CH 2 CH 2 -OSO 3 M, -CH = CH 2 or -CH 2 CH 2-.
Represents an SSO 3 M group, and M represents hydrogen or an alkali metal]
A method for producing a reactive dye represented by the following general formula (II): Bromamic acid represented by the following general formula (III) [Wherein X represents O or S] is reacted with 3- (sulfatoethylsulfonyl) -aniline represented by the formula (I) in the presence of elemental copper and a phosphate buffer to form a product formed. A method as described above, characterized in that it comprises isolating.
が、水素、ナトリウム又はカリウムであることを特徴と
する請求項１に記載の方法。2. Z is —CH 2 CH 2 —OSO 3 M, wherein M is
The method according to claim 1, wherein is hydrogen, sodium or potassium.
７以下、特に６．０〜６．８であることを特徴とする請
求項１又は２に記載の方法。3. The method according to claim 1, wherein at the start of the reaction, the pH of the reaction medium is 7 or less, particularly 6.0 to 6.8.
えるか又は上記反応の前の還元及び沈澱により新たに調
製することを特徴とする請求項１〜３のいずれかに記載
の方法。4. The elemental copper is added as copper powder, copper particles or copper pieces, or is newly prepared by reduction and precipitation before the above reaction. Method.
重量％で使用することを特徴とする請求項１〜４のいず
れかに記載の方法。5. Elemental copper 4 to 16% by weight, in particular 5 to 8
Method according to any of claims 1 to 4, characterized in that it is used in a weight percentage.
て使用することを特徴とする請求項１〜４のいずれかに
記載の方法。6. The method according to claim 1, wherein copper is used together with a carrier material or as a wire mesh of copper.
塩緩衝剤として使用することを特徴とする請求項１〜６
のいずれかに記載の方法。7. A mixture of NaH 2 PO 4 and Na 2 HPO 4 is used as a phosphate buffer.
The method described in any one of.
してリン酸塩緩衝剤を製造することを特徴とする請求項
１〜６のいずれかに記載の方法。8. The method according to claim 1, wherein phosphoric acid and a sodium hydroxide solution are added to produce a phosphate buffer.
５〜１５重量％で使用することを特徴とする請求項１〜
８のいずれかに記載の方法。9. A phosphate buffer is used in an amount of 5 to 15% by weight, based on bromoamine acid.
8. The method according to any one of 8.
９０℃であることを特徴とする請求項１〜９のいずれか
に記載の方法。10. The reaction temperature is 60 to 95 ° C., especially 70 to 95 ° C.
90 degreeC, The method in any one of Claims 1-9 characterized by the above-mentioned.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4422160:6 | 1994-06-24 | ||
| DE4422160A DE4422160C2 (en) | 1994-06-24 | 1994-06-24 | Process for the production of C.I. Reactive Blue 19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0860015A true JPH0860015A (en) | 1996-03-05 |
Family
ID=6521432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7156459A Pending JPH0860015A (en) | 1994-06-24 | 1995-06-22 | Production of c.i.reactive blue 19 |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0860015A (en) |
| KR (1) | KR100373997B1 (en) |
| CN (1) | CN1072249C (en) |
| BR (1) | BR9502922A (en) |
| CH (1) | CH689425A5 (en) |
| DE (1) | DE4422160C2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481531B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Preparation method of reactive dye KN-R |
| CN101481536B (en) * | 2008-12-12 | 2013-01-16 | 天津德凯化工股份有限公司 | Preparation of brilliant blue KN-R |
| CN101481533B (en) * | 2008-12-12 | 2013-06-19 | 天津德凯化工股份有限公司 | Preparation of reactive dye |
| CN101481532B (en) * | 2008-12-12 | 2012-10-10 | 天津德凯化工股份有限公司 | Preparation of brilliant blue dye KN-R |
| CN101481535B (en) * | 2008-12-12 | 2013-06-19 | 天津德凯化工股份有限公司 | Preparation of dye brilliant blue KN-R |
| KR101154986B1 (en) | 2010-03-08 | 2012-06-12 | 이화산업 주식회사 | Composition of reactive blue dyes |
| CN103540165B (en) * | 2013-10-12 | 2015-11-18 | 浙江闰土研究院有限公司 | Improve method and the product of dark lifting force in Reactive Blue 19 100 dyestuff |
| CN103880713B (en) * | 2014-04-16 | 2015-05-13 | 南京大学盐城环保技术与工程研究院 | Method for recycling bromaminic acid from production wastewater of reactive brilliant blue KN-R of vinyl sulfone type dye |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE965902C (en) * | 1949-07-19 | 1957-09-19 | Hoechst Ag | Process for fixing water-soluble organic compounds on substrates with a fibrous structure |
| CH469055A (en) * | 1966-02-02 | 1969-02-28 | Sandoz Ag | Process for the preparation of an anthraquinone dye |
| DE59301662D1 (en) * | 1992-05-04 | 1996-03-28 | Ciba Geigy Ag | Fiber-reactive anthraquinone dyes, process for their preparation and their use |
| DE4230095A1 (en) * | 1992-09-09 | 1994-03-10 | Basf Ag | Formazan-based reactive dyes and hydrazones |
-
1994
- 1994-06-24 DE DE4422160A patent/DE4422160C2/en not_active Expired - Fee Related
-
1995
- 1995-06-19 CH CH01790/95A patent/CH689425A5/en not_active IP Right Cessation
- 1995-06-22 JP JP7156459A patent/JPH0860015A/en active Pending
- 1995-06-22 CN CN95109172A patent/CN1072249C/en not_active Expired - Fee Related
- 1995-06-23 KR KR1019950017012A patent/KR100373997B1/en not_active Expired - Fee Related
- 1995-06-23 BR BR9502922A patent/BR9502922A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CH689425A5 (en) | 1999-04-15 |
| DE4422160C2 (en) | 2003-02-27 |
| KR960001047A (en) | 1996-01-25 |
| CN1072249C (en) | 2001-10-03 |
| KR100373997B1 (en) | 2003-05-09 |
| DE4422160A1 (en) | 1996-01-04 |
| BR9502922A (en) | 1996-02-27 |
| CN1127277A (en) | 1996-07-24 |
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