GB1587179A - Preparation of azo dyestuffs - Google Patents
Preparation of azo dyestuffs Download PDFInfo
- Publication number
- GB1587179A GB1587179A GB20710/78A GB2071078A GB1587179A GB 1587179 A GB1587179 A GB 1587179A GB 20710/78 A GB20710/78 A GB 20710/78A GB 2071078 A GB2071078 A GB 2071078A GB 1587179 A GB1587179 A GB 1587179A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- process according
- denotes
- weight
- coupling
- 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.)
- Expired
Links
- 238000002360 preparation method Methods 0.000 title description 2
- 238000005859 coupling reaction Methods 0.000 claims abstract description 50
- 230000008878 coupling Effects 0.000 claims abstract description 49
- 238000010168 coupling process Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 heterocyclic amine Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000000975 dye Substances 0.000 claims abstract description 19
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 claims abstract description 5
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 5
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims abstract description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 62
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 37
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 6
- ACCLIXSHFMDCLV-UHFFFAOYSA-N 3-[n-(2-phenylethyl)anilino]propanenitrile Chemical compound C=1C=CC=CC=1N(CCC#N)CCC1=CC=CC=C1 ACCLIXSHFMDCLV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XMXLBDNVSIHRRA-UHFFFAOYSA-N 4,5-dimethyl-1,3-thiazol-2-amine Chemical compound CC=1N=C(N)SC=1C XMXLBDNVSIHRRA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- MIHADVKEHAFNPG-UHFFFAOYSA-N 2-Amino-5-nitrothiazole Chemical compound NC1=NC=C([N+]([O-])=O)S1 MIHADVKEHAFNPG-UHFFFAOYSA-N 0.000 description 2
- 229940018167 2-amino-5-nitrothiazole Drugs 0.000 description 2
- KZHGPDSVHSDCMX-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazol-2-amine Chemical compound COC1=CC=C2N=C(N)SC2=C1 KZHGPDSVHSDCMX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000006149 azo coupling reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000008049 diazo compounds Chemical class 0.000 description 2
- 229940013688 formic acid Drugs 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 229960005130 niridazole Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229940095574 propionic acid Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JSKJAICVFPRVHJ-UHFFFAOYSA-N 2,1-benzothiazol-3-amine Chemical compound C1=CC=CC2=C(N)SN=C21 JSKJAICVFPRVHJ-UHFFFAOYSA-N 0.000 description 1
- YKBXWAQJCNUBTG-UHFFFAOYSA-N 2-amino-5-nitro-1,3-thiazole-4-carbonitrile Chemical compound NC1=NC(C#N)=C([N+]([O-])=O)S1 YKBXWAQJCNUBTG-UHFFFAOYSA-N 0.000 description 1
- CFKZMYPOJOKAAD-UHFFFAOYSA-N 2-amino-5-nitrothiophene-3-carbonitrile Chemical compound NC=1SC([N+]([O-])=O)=CC=1C#N CFKZMYPOJOKAAD-UHFFFAOYSA-N 0.000 description 1
- XVGHZFWFGXDIOU-UHFFFAOYSA-N 2-aminothiophene-3-carbonitrile Chemical compound NC=1SC=CC=1C#N XVGHZFWFGXDIOU-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZTTPWPKJVSSSMW-UHFFFAOYSA-N 3-(n-benzylanilino)propanenitrile Chemical compound C=1C=CC=CC=1N(CCC#N)CC1=CC=CC=C1 ZTTPWPKJVSSSMW-UHFFFAOYSA-N 0.000 description 1
- XAIYKSRYTHOEOI-UHFFFAOYSA-N 3-[n-[(2,4-dibutylphenyl)methyl]anilino]propanenitrile Chemical compound CCCCC1=CC(CCCC)=CC=C1CN(CCC#N)C1=CC=CC=C1 XAIYKSRYTHOEOI-UHFFFAOYSA-N 0.000 description 1
- PQLVDLKCNMMUGJ-UHFFFAOYSA-N 3-[n-[(2-chlorophenyl)methyl]anilino]propanenitrile Chemical compound ClC1=CC=CC=C1CN(CCC#N)C1=CC=CC=C1 PQLVDLKCNMMUGJ-UHFFFAOYSA-N 0.000 description 1
- XNWPRTZGZZOGPZ-UHFFFAOYSA-N 3-[n-[(2-methoxyphenyl)methyl]anilino]propanenitrile Chemical compound COC1=CC=CC=C1CN(CCC#N)C1=CC=CC=C1 XNWPRTZGZZOGPZ-UHFFFAOYSA-N 0.000 description 1
- WVPXMWPWTFFUAO-UHFFFAOYSA-N 3-[n-[(4-ethylphenyl)methyl]anilino]propanenitrile Chemical compound C1=CC(CC)=CC=C1CN(CCC#N)C1=CC=CC=C1 WVPXMWPWTFFUAO-UHFFFAOYSA-N 0.000 description 1
- ZQHZFXCBCHVEPM-UHFFFAOYSA-N 3-[n-[(4-methylphenyl)methyl]anilino]propanenitrile Chemical compound C1=CC(C)=CC=C1CN(CCC#N)C1=CC=CC=C1 ZQHZFXCBCHVEPM-UHFFFAOYSA-N 0.000 description 1
- FOGBUCFVTAHWCG-UHFFFAOYSA-N 3-[n-[2-(2,4-dichlorophenyl)ethyl]anilino]propanenitrile Chemical compound ClC1=CC(Cl)=CC=C1CCN(CCC#N)C1=CC=CC=C1 FOGBUCFVTAHWCG-UHFFFAOYSA-N 0.000 description 1
- KTTZVWOIYVUBCD-UHFFFAOYSA-N 3-[n-[2-(2,4-dimethoxyphenyl)ethyl]anilino]propanenitrile Chemical compound COC1=CC(OC)=CC=C1CCN(CCC#N)C1=CC=CC=C1 KTTZVWOIYVUBCD-UHFFFAOYSA-N 0.000 description 1
- HYDDTOQQCGXRDE-UHFFFAOYSA-N 3-[n-[2-(2,4-dimethylphenyl)ethyl]anilino]propanenitrile Chemical compound CC1=CC(C)=CC=C1CCN(CCC#N)C1=CC=CC=C1 HYDDTOQQCGXRDE-UHFFFAOYSA-N 0.000 description 1
- JYQBOTPAEHEOJE-UHFFFAOYSA-N 3-[n-[2-(2-chlorophenyl)ethyl]anilino]propanenitrile Chemical compound ClC1=CC=CC=C1CCN(CCC#N)C1=CC=CC=C1 JYQBOTPAEHEOJE-UHFFFAOYSA-N 0.000 description 1
- IOIDIMIIKMOHCS-UHFFFAOYSA-N 3-[n-[2-(3-methoxyphenyl)ethyl]anilino]propanenitrile Chemical compound COC1=CC=CC(CCN(CCC#N)C=2C=CC=CC=2)=C1 IOIDIMIIKMOHCS-UHFFFAOYSA-N 0.000 description 1
- LLBOFZAXUGJRIW-UHFFFAOYSA-N 3-[n-[2-(4-butoxyphenyl)ethyl]anilino]propanenitrile Chemical compound C1=CC(OCCCC)=CC=C1CCN(CCC#N)C1=CC=CC=C1 LLBOFZAXUGJRIW-UHFFFAOYSA-N 0.000 description 1
- UQCZNFYBGRCKCK-UHFFFAOYSA-N 3-[n-[2-(4-methoxyphenyl)ethyl]anilino]propanenitrile Chemical compound C1=CC(OC)=CC=C1CCN(CCC#N)C1=CC=CC=C1 UQCZNFYBGRCKCK-UHFFFAOYSA-N 0.000 description 1
- VODPTGJRYMDDQS-UHFFFAOYSA-N 3-[n-[2-(4-methylphenyl)ethyl]anilino]propanenitrile Chemical compound C1=CC(C)=CC=C1CCN(CCC#N)C1=CC=CC=C1 VODPTGJRYMDDQS-UHFFFAOYSA-N 0.000 description 1
- OYZHSRJEUNAFRV-UHFFFAOYSA-N 3-nitrothiophen-2-amine Chemical compound NC=1SC=CC=1[N+]([O-])=O OYZHSRJEUNAFRV-UHFFFAOYSA-N 0.000 description 1
- OYAHSBDYBOBAAQ-UHFFFAOYSA-N 3-phenyl-1,2,4-thiadiazol-5-amine Chemical compound S1C(N)=NC(C=2C=CC=CC=2)=N1 OYAHSBDYBOBAAQ-UHFFFAOYSA-N 0.000 description 1
- XYTUTNQRQLAZLK-UHFFFAOYSA-N 4,5-dimethyl-1,3-thiazol-2-amine;hydrochloride Chemical compound Cl.CC=1N=C(N)SC=1C XYTUTNQRQLAZLK-UHFFFAOYSA-N 0.000 description 1
- OUQMXTJYCAJLGO-UHFFFAOYSA-N 4-methyl-1,3-thiazol-2-amine Chemical compound CC1=CSC(N)=N1 OUQMXTJYCAJLGO-UHFFFAOYSA-N 0.000 description 1
- NDWBXTNRCBNGAK-UHFFFAOYSA-N 4-methyl-5-nitro-1,3-thiazol-2-amine Chemical compound CC=1N=C(N)SC=1[N+]([O-])=O NDWBXTNRCBNGAK-UHFFFAOYSA-N 0.000 description 1
- IGOFERRFCRPIHL-UHFFFAOYSA-N 4-methyl-5-nitrothiophen-2-amine Chemical compound CC=1C=C(N)SC=1[N+]([O-])=O IGOFERRFCRPIHL-UHFFFAOYSA-N 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- XPYJFCKUPMJFHE-UHFFFAOYSA-N 4-nitro-1,3-benzothiazol-2-amine Chemical compound C1=CC=C2SC(N)=NC2=C1[N+]([O-])=O XPYJFCKUPMJFHE-UHFFFAOYSA-N 0.000 description 1
- GISCGLDZXOXKBZ-UHFFFAOYSA-N 5-aminothiophene-2-carbonitrile Chemical compound NC1=CC=C(C#N)S1 GISCGLDZXOXKBZ-UHFFFAOYSA-N 0.000 description 1
- LVZXKIHSMKEBRO-UHFFFAOYSA-N 5-bromothiophen-2-amine Chemical compound NC1=CC=C(Br)S1 LVZXKIHSMKEBRO-UHFFFAOYSA-N 0.000 description 1
- QLBGRINOCGRGMD-UHFFFAOYSA-N 5-methylsulfonyl-1h-1,2,4-triazol-3-amine Chemical compound CS(=O)(=O)C1=NC(N)=NN1 QLBGRINOCGRGMD-UHFFFAOYSA-N 0.000 description 1
- SQBCSDZTDXLTLE-UHFFFAOYSA-N 5-nitro-2,1-benzothiazol-3-amine Chemical compound C1=CC([N+]([O-])=O)=CC2=C(N)SN=C21 SQBCSDZTDXLTLE-UHFFFAOYSA-N 0.000 description 1
- PSRZQUKEUSRHJJ-UHFFFAOYSA-N 5-nitrothiophen-2-amine Chemical compound NC1=CC=C([N+]([O-])=O)S1 PSRZQUKEUSRHJJ-UHFFFAOYSA-N 0.000 description 1
- UHZHEOAEJRHUBW-UHFFFAOYSA-N 5-phenyl-1,3,4-thiadiazol-2-amine Chemical compound S1C(N)=NN=C1C1=CC=CC=C1 UHZHEOAEJRHUBW-UHFFFAOYSA-N 0.000 description 1
- VMNXKIDUTPOHPO-UHFFFAOYSA-N 6-chloro-1,3-benzothiazol-2-amine Chemical compound C1=C(Cl)C=C2SC(N)=NC2=C1 VMNXKIDUTPOHPO-UHFFFAOYSA-N 0.000 description 1
- KOYJWFGMEBETBU-UHFFFAOYSA-N 6-ethoxy-1,3-benzothiazol-2-amine Chemical compound CCOC1=CC=C2N=C(N)SC2=C1 KOYJWFGMEBETBU-UHFFFAOYSA-N 0.000 description 1
- YGUOZZPTJINEMV-UHFFFAOYSA-N 6-ethoxy-5-methoxy-1,3-benzothiazol-2-amine Chemical compound C1=C(OC)C(OCC)=CC2=C1N=C(N)S2 YGUOZZPTJINEMV-UHFFFAOYSA-N 0.000 description 1
- ZYHNHJAMVNINSY-UHFFFAOYSA-N 6-methylsulfonyl-1,3-benzothiazol-2-amine Chemical compound CS(=O)(=O)C1=CC=C2N=C(N)SC2=C1 ZYHNHJAMVNINSY-UHFFFAOYSA-N 0.000 description 1
- GPNAVOJCQIEKQF-UHFFFAOYSA-N 6-nitro-1,3-benzothiazol-2-amine Chemical compound C1=C([N+]([O-])=O)C=C2SC(N)=NC2=C1 GPNAVOJCQIEKQF-UHFFFAOYSA-N 0.000 description 1
- SOEMXHBNLXIWET-UHFFFAOYSA-N 7-chloro-5-nitro-2,1-benzothiazol-3-amine Chemical compound ClC1=CC([N+]([O-])=O)=CC2=C(N)SN=C21 SOEMXHBNLXIWET-UHFFFAOYSA-N 0.000 description 1
- OCXZGGDYPSVGEW-UHFFFAOYSA-N 7-nitro-2,1-benzothiazol-3-amine Chemical compound [O-][N+](=O)C1=CC=CC2=C(N)SN=C21 OCXZGGDYPSVGEW-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 101100111635 Caenorhabditis elegans bir-1 gene Proteins 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UXDKVBJDZDRIKL-UHFFFAOYSA-N ethyl 2-amino-5-nitrothiophene-3-carboxylate Chemical compound CCOC(=O)C=1C=C([N+]([O-])=O)SC=1N UXDKVBJDZDRIKL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0823—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by CN
-
- 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
- C09B41/00—Special methods of performing the coupling reaction
- C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
- C09B41/002—Special methods of performing the coupling reaction characterised by the coupling medium containing a solvent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The dyes are prepared by coupling a diazonium compound of a heterocyclic amine of aromatic character, from the thiazole, benzothiazole, benzisothiazole, thiadiazole, triazole or thiophene series, which optionally contains further substituents in the aromatic nucleus, with a coupling component, in a solvent or dispersant consisting of a mixture of 90-15 % by weight of an aliphatic alcohol having a chain length of 4-6 C atoms and a water-solubility of at most 15 % by weight at 15 DEG C, and 10-85 % of water, at -20 DEG C to +20 DEG C, in the presence of an acid. The process gives high yields of very pure products.
Description
(54) PREPARATION OF AZO DYESTUFFS
(71) We, CASSELLA AKTIENGESELLSCHAFT, formerly Cassella
Farbwerke Mainkur Aktiengesellschaft, a body corporate organised under the laws of the Federal Republic of Germany, of 526 Hanauer Landstrasse, 6000 Frankfurt (Main) 61, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement::- The present invention relates to an improvement in or modification of the process described in our Patent Specification No. 1 535 894 (Application 4023/77), hereinafter referred to as our " main" specification, which describes and claims a process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound with a coupling component of a defined type, at a temperature of from 0 to 80"C and in the presence of an acid, in a solvent or dispersing medium comprising a mixture of from 90 to 15% by weight of an aliphatic alcohol containing from 4 to 6 C atoms and having a solubility in water of not more than 15% by weight at 150C, and 10 to 85% by weight of water.
Azo dyestuffs are conventionally manufactured by coupling either a mineral acid aqueous solution or a suspension of a diazonium salt of an amino compound with an aqueous mineral acid or alkaline solution or suspension of a coupling component.
According to German Auslegeschrift 2,139,311, coupling of a diazo component with a coupling component is carried out in an acid liquid medium, preferably in water and/or a water-soluble organic solvent, for example isopropanol.
According to German Auslegeschrift 1,927,453, azo pigments are obtained by azo coupling in organic solvents, such as, for example, benzene, toluene and chlorobenzene, inter alia, which have a water content of at most 10%.
German Offenlegungsschrift 2,058,299 describes carrying out azo coupling in an anhydrous organic, water-insoluble solvent, whilst in addition German Offenlegungsschrift 2,509,560 also describes the use of water-miscible (hydrophilic) solvents.
In many cases impure azo dyestuffs are obtained by these hitherto known processes, especially if the solubility properties of the diazo componets or coupling components in the reaction media are unfavourable. In general, a decrease in yield is also associated with the occurrence of impurities in the azo dyestuff. Furthermore, in some of the known processes, the coupling reaction proceeds very slowly, so that uneconomically long reaction times are required.
Our main Specification relates to a process by means of which the disadvantages associated with the processes known hitherto can be avoided.
The process of our main Specification is particularly suitable for the manufacture of azo dyestuffs using appropriately stabilised diazo compounds of a diazotisable aromatic amine of the general formula I
wherein X1, X2 and X, denote hydrogen or certain substituents which do not confer water-solubility, or of an aminoazo compound of the general formula II
wherein X4 to X8 denote hydrogen or certain substituents which do not confer watersolubility.
Coupling components in the process of our main Specification which have been described are tertiary, aromatic amines of the general formula
wherein X, and Xfi have the meaning indicated above and X9 and Xl0 denote optionally substituted alkyl radicals containing 1 to 4 C atoms, and heterocyclic coupling components of the general' formula
wherein X1l denotes hydrogen or has the meaning of Xg and X10.
According to the present invention there is provided a process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound with a coupling component, the diazonium compound being derived from a heterocyclic amine of aromatic character of the thiazole, benzthiazole, benzisothiazole, thiadiazole, triazole and thiophene series, which can optionally also contain further substituents in the aromatic nucleus, and the coupling being effected in a solvent or dispersing agent consisting of a mixture of 90 to 15% by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 15"C, and 10 to 85% by weight of water, at temperatures between -200C and +20 C in the presence of an acid.
A solvent or dispersing agent consisting of 60 to 30% by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 15"C, and 40 to 70% by weight of water is preferably used in carrying out the process according to the invention.
Examples of aliphatic alcohols, having a chain length of 4 to 6 C atoms, which are contained as a mixing component in the solvents or dispersing agents to be employed according to the invention are n-butanol, iso-butanol, n-amyl alcohols diethylcarbinol, isobutylcarbinol, n-hexanol and iso-hexanol.
n-Butanol and iso-butanol are preferred.
Advantages of the process according to the invention arise from the overall physico-chemical properties of the two-phase system to be employed, according to the invention, as the solvent or dispersing agent. The solubility in water of the aliphatic alcohols to be employed is particularly important here.
The solubilities in water of the preferred alkanols, n-butanol and iso-butanol are 6.8 and 7.4% by weight, respectively, at 15 C.
Conversely, ar this temperature the take-up of water by n-butanol is 27.3% by weight and of isobutanol is 16.0% by weight.
The process according to the invention can be carried out in two stages by introducing a solution of a heterocyclic diazonium compound in an aqueous or concentrated inorganic or organic acid into a mixture of a coupling component and the solvent or dispersing agent.
The solution of the heterocyclic diazonium compound to be introduced is prepared, in a reaction stage prior to the coupling, by diazotising a diazotisable heterocyclic amine in an aqueous or concentrated inorganic or organic acid with a diazotising agent. The reaction temperature in this procedure can also be kept between -200C and +20"C, preferably - 100 and + 5 C, by external cooling. In principle, suitable acids for ,lose according to the invention are all the strong inorganic and organic acids known for diazotisation of amines and coupling in an acid medium.
Examples of suitable inorganic acids are hydrochloric acid, hydrobromic acid, sulphuric acid or phosphoric acid. Examples of possible acids from the organic acid series are formic acid, acetic acid, chloroacetic acid and propionic acid.
The salts of nitrous acid, in particular the alkali metal salts, such as, for example, sodium nitrite, or potassium nitrite, or substances which produce nitrous acid, such as nitrosylsulphuric acid, can be used as the diazotising agents.
It can be desirable to buffer the reaction mixture in order to accelerate the coupling and in order to trap the acid liberated during the coupling. For this purpose, buffer substances which are in themselves known can be added to the reaction mixture. Known buffer substances are, inter alia, alkali metal salts of relatively weak acids, for example sodium acetate.
The diazo compound used is derived from a heterocyclic amine of aromatic character of the thiazole, benzthiazole, benzisothiazole, thiadiazole, triazole and thiophene series, which can optionally also contain further substituents in the aromatic nucleus.
Examples which may be mentioned are the following heterocycluic amines: 2amino -4 - methyl - thiazole, 2 - amino - 4,5 - dimethyl - thiazole, 2 - amino - 5nitro - thiazole, 2 - amino - 4 - methyl - 5 - nitro - thiazole, 2 - amino - 4 - cyano - 5nitro - thiazole, 2 - amino - 4 tn'.fluoro - methyl - 5 - nitro - thiazole, 2 - amino - 4 phenyl - 5 - nitro - thiazole, 2 - amino - benzthiazole, 2 - amino - 6 - methoxy - benzthiazole, 2 - amino - 6 - ethoxy - benzthiazole, 2 - amino - 5 - methoxy - 6 - ethoxybenzthiazole, 2 - amino - 6 - chlorobenzthiazole, 2 - amino - 4 - nitro - benzthiazole, 2 - amino - 6 - nitro - benzthiazole, 2 - amino - 6 - methylsulphonyl - benzthiazole, 3 - amino - 2,1 - benzoisothiazole, 3 - amino - 5 - nitro - 2,1 - benzisothiazole, 3amino - 5 - nitro - 7 - chloro - 2,1 - benzisothiazole, 3 - amino - 7 - nitro - 2,1 - benzisothiazole, 2 - amino - 5 - phenyl - 1,3,4 - thiadiazole, 2 - amino - 4 - phenyl - 1,3,5thiadiazole, 2 - amino - 1,3,4 - triazole, 2 - amino - 5 - methylsulphonyl - 1,3,4 - triazole, 2 - amino - 5 - bromo - thiophene, 2 - amino - 5 - cyano - thiophene, 2 - amino5 - nitro - thiophene, 2 - amino - 4 - methyl - 5 - nitro - thiophene, 2 - amino - 3nitro - thiophene, 2 - amino - 3 - cyano - 5 - nitro - thiophene, 2 - amino - 5 - nitrothiophene - 3 - carboxylic acid ethyl ester and 2 - amino - 3 - cyano - thiophene.
Possible coupling components are tetriary, aromatic amines of the general formula
I'
wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, in particular chlorine atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2.
Examples of coupling components of this type are: N - benzyl - N - cyanoethylaniline, N - (2' - chloro - benzyl) - N - cyanoethyl - aniline, N - (4' - methylbenzyl) - N - cyanoethyl - aniline, N - (4' - ethyl - benzyl) - N - cyanoethyl - aniline,
N - (2',4' - di - n - butyl - benzyl) - N - cyanoethyl - aniline, N - (2' - methoxybenzyl) - N - cyanoethyl - aniline, N - phenethyl - N - cyanoethyl - aniline, N - (2'chloro - phenethyl) - N - cyanoethyl - aniline, N - (2' - bromo - phenethyl) - Ncyanoethyl - aniline, N - (2',4' - dichloro - phenethyl) - N - cyanoethyl - aniline, N (4' - methyl - phenethyl) - N - cyanoethyl - aniline, N - (4' - n - butyl - phenethyl) N-cyanoethyli- aniline, N - (2',4' - dimethyl - phenethyl) - N - cyanoethyl - aniline,
N - (3' - methoxy - phenethyl) - N - cyanoethyl - aniline, N - (4' - methoxy - phenethyl) - N - cyanoethyl - aniline, N - (4' - n - butoxy - phenethyl) - N - cyanoethylaniline and N - (2',4' - dimethoxy - phenethyl) - N - cyanoethyl - aniline.
The process according to the invention is particularly suitable for carrying out the coupling of the diazonium compound of an amine of the general formula III'
wherein R1 denotes a hydrogen atom or a methyl, cyano or trifluoromethyl group, or
IV'
wherein R2 denotes a hydrogen atom or a nitro group, R3 denotes a hydrogen atom or a methoxy group, R4 denotes a hydrogen or chlorine atom or a methoxy, ethoxy, nitro or methylsulphonyl group, with a coupling component of the general formula I'
wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, in particular chlorine atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2, dyestuffs of the general formula II'
wherein D denotes a thiazole radical of the general formula
or a benzthiazole radical of the general formula
and R, Rl, R2, F3, R4 and n have the above meanings, being obtained in very good yield and purity.
The manufacture of dyestuffs of the general formula V
wherein n has the meaning indicated above, by the process according to the invention by using a diazonium compound of an amine of the general formula IIIa
and a coupling component of the general formula I'
wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, in particular chlorine atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2, is particularly advantageous.
The azo dyestuffs, usually obtained in good yield and purity by the process according to the invention, can either be separated out by driving off, by means of steam, the aliphatic alcohol used as the solvent or can be isolated by immediate filtration and, if appropriate, subsequent washing of the residue with the aliphatic alcohol used. The solvent employed can be regenerated from the filtrate, also by distillation, if appropriate using steam.
The aliphatic alcohols recovered in both working up processes can be re-used in a further batch, taking into consideration their water content.
The process according to the invention for the manufacture of azo dyestuffs has been found particularly advantageous for the manufacture of azo dyestuffs which are obtained only in a very impure form by coupling the heterocyclic diazo compound with a coupling component in an aqueous, mineral acid solution, if appropriate while buffering with sodium acetate. Furthermore, it has been found advantageous when coupling components which are very sparingly soluble in acids are used, for example, N phenethyl - N - ,,8 - cyanoethyl - aniline, which is coupled industrially in 50% strength sulphuric acid, which is no longer acceptable for reasons of environmental protection.
Azo dyestuffs can be manufactured industrially from this coupling component in a simple manner in high yield and purity by the process claimed.
Example 1.
36.3 parts by weight of 2-amino-5-nitro-thiazole are dissolved in 600.0 parts by weight of 65% strength sulphuric acid and diazotised with a solution of 17.9 parts by weight of sodium nitrite in 35.0 parts by weight of water at - 10 C. After subsequently stirring the mixture at - 100C for 1* hours, the diazo solution is allowed to run rapidly into a suspension, cooled to 0 C, of 58.5 parts by weight of N-phenethyl
N-cyanoethyl-aniline in 320.0 parts by weight of isobutanol and the mixture is then further stirred for about 2 hours at a temperature rising to 200 C. The dyestuff formed is then filtered off and washed with 75.0 parts by weight of 48% strength sulphuric acid.The acid dyestuff paste is then suspended in aqueous sodium hydroxide solution at pH 9-10, the suspension is stirred at 60"C for 1 hour and filtered again and the residue is washed with water until neutral and dried. The dyestuff is a dark blue powder which dissolves in concentrated sulphuric acid to give a brown-coloured solution.
75.0 parts by weight of the dyestuff of the formula
are obtained. This dyestuff has a purity of 97%, determined by physical comparison measurements against a crystalline sample.
Example 2.
34.2 parts by weight of 42% strength nitrosylsulphuric acid are allowed to run into a suspension of 16.4 parts by weight of 2-amino-4,5-dimethylthiazole hydrochloride in 100 parts by weight of glacial acetic acid at + 15 C. After subsequently stirring the mixture for one hour, the diazo solution is allowed to run into a suspension of 26.3 parts by weight of N-phenethyl-N-cyanoethyl-aniline, 160.0 parts by weight of isobutanol and 200.0 parts by weight of water at 0 C. The mixture is then further stirred overnight at a temperature rising to room temperature.The dyestuff which has separated out is then filtered off, washed thoroughly, first with 160.0 parts by weight of isobutanol and then with water, and dried, It is a red powder which dissolves in concentrated sulphuric acid to give a red-coloured solution. 26.7 parts by weight of the dyestuff of the formula
are obtained. This dyestuff has a purity of 98.2%, determined against a crystalline sample.
Example 3.
If 18.0 parts by weight of 2-amino-6-methoxy-benzthiazole are coupled with 26.3 parts by weight of N-phenethyl-N-cyanoethyl-aniline as described in Example 2, 32.6 parts by weight of the dyestuff of the formula
are obtained. This dyestuff has a purity of 94.5%, determined against a crystalline sample. The dyestuff is a red powder which dissolves in concentrated sulphuric acid to give a red-coloured solution.
The dyestuffs listed in the table are manufactured by the process described above:
No. Diazo component Coupling component Solvent
1.
lic g3C-C-N o N isobutanol 'S, xc-N C'L N/ CH2'Ca28 2. n i-Na, 2 2 CEZ-CBZ-CN \S' 3. BsCzO--H 5 CH2-CH2 n-butanol Ncii -Ca N sz - 2 2 4 83c-o2s t 5%-Na2 3 c82cu2 isobutanol Cn2-CN 5. BsC20-$,r"-2 C82 i sobutanol Ca2-CH2-CN N N 6. 5 cx Cx s8 < X,C82-CH2(3 N 2 n-butanol CBZ-CIIZ-CS No. Diazo component Coupling component Solvent
7. EC - CB Q Xo CB2 CB2 n-butanol NC-C8-C-NH2 - CI!2-CH2-CN - - C-CO-OCZBS 8. . c-xx 5 2; s - isobutanol 2 S- 2 ,'CH22-CN 9 83C-C - X O ,CH2 isobutanol a,c-c,,, cl > CB2-CB2-CH 10. F3C-C - N s n 5 CB2"Cz2 > H3 isobutanol 02N-Cv5,C-Na2 s CB2-CH2-CX 11. Hscoir H ozoCH2~CH2 n-amyl alcohol H5C20 S -NH2 sC82-CH2-CH lx'12 7 n-butanol 12. 82 O N B2N 13 O x n 2 5 rCH2 13. CHZ-C 2 'CE2-CB2-CN 'L 14. HC - CH O NoCU24E2 isobutanol N O2x 5C-Ns2 - 'CH2-C112-CN - -- N -' 15. sc- 2t N oCg2 isobutanol 02X-C~ v -a2 s CRZ-CIIZ-CW 16. X ( & 2 t ) n-butanol C1X) 2 sCEX2-Cli2-C!f L7. OzH E P-x / cu,-ce, Cla-CH2-CB No. Diazo component Coupling component Solvent
18. - xl' CH2 isobutanol HCC-NH2 BCNIS-HA2 H 19. H3C-C - Cr O CH2 CH3 isobutanol O2NCsCNH2 CH2-CE2-CN 20. o ~c c- 5 ,ce2-c2\2 n-hexanol 2 > S- 2 2H2CX 21. 5 c - N 5 ,cm2 isobutanol 2 CS-C '22 s Cg2-Cz2-Ch 22. 3aV12 \/mi\ K cH2cH:mCffi\H3 isobutanol - C2-CH2-CN o2x1 23. c-u e CH2-CH2-CN dicthylc & bir1 ---/ CS1-CISeCN 24. 02 rg2 4 cg2-ce2 e isobutariol 2. o,x,rXb OE-h' N,Q n-butanol 25. a,e -o,s-E,,-Naz C82-CtlZ-CN CH22-CN H 26. 8C - Cn-N02 CH2-C2 n-butanol soCsS,C-8H2 2 2 CH3 H CC - CII CII2CN2CH2 27. H3CCl' CU pl CR2~CH2dCH3 isobutyl z3c-css,C-M2 -CX2-CH2-CN carbinol 28. S3C0 2 CH2 CH2 CN isobutanol -'CH2CH2CN No. Diazo component Coupling component Solvent
29. CH2CH2, 29. CBZ-CH1-CH isobutanol 02 GCS3 30. HC < C2#CR3 isobutanol 5 2 S 2 CS2-C82-CN 31. 02N^S -Sg2 5 X/CCH2CCIIH2\ n-butanol 2 2 " II EZ CH , C82-CH2AC44t) OZN-C,S'C'hgZ -ca2-Cu2-CN 33. 8c - CII < cu2t n-butanol Br-C~s,c-hfB2 CH2-CH2-CX 34. BC ac - C-CN w:2C H2 CH2-CB2(3 O2x5C-.NH2 132CII2-CN 35. 11Cr. - C-CNCHZ-CH;2 ECsS,C-hE2 ON C n-butanol C4H9(n) II3C-C - N I \II( 36. BC n3C-C - N O CH29n isobutanol sCB2-CB2-UN C1 37 3 5 N/CB24R2 isobutanol n,c-c,,,c-NH2 J cuz^ca2 U isobutanol HO - N oCHo-CB2 l' -'22 SC C-NH - n-butanol 38. fl3C-C2 S' 2 CIIZ-CBZ-CN No. Diazo component Coupling component Solvent
39. z5c2o tS,c~a2 5 ,cz2-cz2 t L/ n-butanol CH2C2Cx 40. O2NBCCl' S sCB2-CB2-C isobutanol H2H2CN Br 41. H3CoJ5-b'H2 S 5 , CH2-cB2q3 isobutanol H3COiSr-hZ OCH3 42. BC N o C82~CB2 isobutanol 42. o,N-, S'E'NH1 43. HHc3COj CIIZCBZ-C 5 2 NH2 CH2-CB2CN iobutanol WHAT WE CLAIM IS:- 1.A process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound with a coupling component, the diazonium compound being derived from a heterocyclic amine of aromatic character of the thiazole, benzthiazole, benzisothiazole, thiadiazole, triazole and thiophene series, which can optionally also contain further substituents in the aromatic nucleus, and the coupling being effected in a solvent or dispersing agent consisting of a mixture of 90 to 15 by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 1SOC, and 10 to 85% by weight of water, at temperatures between -20"C and + 1200C in the presence of an acid.
2. A process according to claim 1, wherein the coupling is carried out in a solvent or dispersing agent consisting of a mixture of 60 to 30% by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 150C, and 40 to 70% by weight of water.
3. A process according to claim 1 or claim 2, wherein n-butanol or iso-butanol is employed as the aliphatic alcohol.
4. A process according to any one of claims 1 to 3, wherein the solution of a diazonium compound in an aqueous or concentrated inorganic or organic acid is introduced into a mixture of a coupling component and the solvent or dispersing agent.
5. A process according to any one of claims 1 to 4, wherein the reaction is carried out at temperatures between --10"C and + 15 C.
6. A process according to any one of claims 1 to 5, wherein hydrochloric acid, hydrobromic acid, sulphuric acid or phosphoric acid is employed as the acid.
7. A process according to any one of claims 1 to 5, wherein formic acid, acetic acid, chloroacetic acid or propionic acid is employed as the acid.
8. A process according to any one of claims 1 to 7, wherein sodium nitrite, potassium nitrite or nitrosylsulphuric acid is employed as the diazotising agent.
9. A process according to any one of claims 1 to 8, wherein a coupling component of the general formula I':
wherein R denotes a phenyl radical which is optionally mono-substituted or disubsti
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (15)
- **WARNING** start of CLMS field may overlap end of DESC **.No. Diazo component Coupling component Solvent39. z5c2o tS,c~a2 5 ,cz2-cz2 t L/ n-butanol CH2C2Cx 40. O2NBCCl' S sCB2-CB2-C isobutanol H2H2CN Br 41. H3CoJ5-b'H2 S 5 , CH2-cB2q3 isobutanol H3COiSr-hZ OCH3 42. BC N o C82~CB2 isobutanol 42. o,N-, S'E'NH1 43. HHc3COj CIIZCBZ-C 5 2 NH2 CH2-CB2CN iobutanol WHAT WE CLAIM IS:- 1.A process for the manufacture of an azo dyestuff which comprises coupling a diazonium compound with a coupling component, the diazonium compound being derived from a heterocyclic amine of aromatic character of the thiazole, benzthiazole, benzisothiazole, thiadiazole, triazole and thiophene series, which can optionally also contain further substituents in the aromatic nucleus, and the coupling being effected in a solvent or dispersing agent consisting of a mixture of 90 to 15 by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 1SOC, and 10 to 85% by weight of water, at temperatures between -20"C and + 1200C in the presence of an acid.
- 2. A process according to claim 1, wherein the coupling is carried out in a solvent or dispersing agent consisting of a mixture of 60 to 30% by weight of an aliphatic alcohol, having a chain length of 4 to 6 C atoms and a solubility in water of at most 15% by weight at 150C, and 40 to 70% by weight of water.
- 3. A process according to claim 1 or claim 2, wherein n-butanol or iso-butanol is employed as the aliphatic alcohol.
- 4. A process according to any one of claims 1 to 3, wherein the solution of a diazonium compound in an aqueous or concentrated inorganic or organic acid is introduced into a mixture of a coupling component and the solvent or dispersing agent.
- 5. A process according to any one of claims 1 to 4, wherein the reaction is carried out at temperatures between --10"C and + 15 C.
- 6. A process according to any one of claims 1 to 5, wherein hydrochloric acid, hydrobromic acid, sulphuric acid or phosphoric acid is employed as the acid.
- 7. A process according to any one of claims 1 to 5, wherein formic acid, acetic acid, chloroacetic acid or propionic acid is employed as the acid.
- 8. A process according to any one of claims 1 to 7, wherein sodium nitrite, potassium nitrite or nitrosylsulphuric acid is employed as the diazotising agent.
- 9. A process according to any one of claims 1 to 8, wherein a coupling component of the general formula I':wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, in particular chlorine atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2, is employed.
- 10. A process according to any one of claims 1 to 9, wherein the diazonium compound of an amine of the general formula III'wherein R1 denotes a hydrogen atom or a methyl, cyano or triuoromethyl group; or the general! formula IV'wherein R2 denotes a hydrogen atom or a nitro group, R, denotes a hydrogen atom or a methoxy group and R4 denotes a hydrogen or chlorine atom or a methoxy, ethoxy, nitro or methylsulphonyl group, and a coupling component of the general formula I'wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2, are employed.
- 11. A process according to any one of claims 1 to 10 wherein the diazonium compound of an amine of the general formula IIIaand a coupling component of the general formula I'wherein R denotes a phenyl radical which is optionally mono-substituted or disubstituted by halogen atoms, or alkyl or alkoxy groups having a chain length of C1 to C4 and n denotes the numbers 1 or 2, are employed.
- 12. A process according to claim 10 or 11, which employs a coupling component of the said formula I' wherein R denotes a phenyl radical which is monosubstituted or disubstituted by chlorine atoms.
- 13. A process according to claim 1, substantially as herein described.
- 14. A process for the manufacture of an azo dyestuff, the process being substantially as herein described in any of the Examples.
- 15. An azo dyestuff when manufactured according to a process according to any one of claims 1 to 14.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772722768 DE2722768A1 (en) | 1977-05-20 | 1977-05-20 | METHOD OF MANUFACTURING AZO DYES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1587179A true GB1587179A (en) | 1981-04-01 |
Family
ID=6009438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB20710/78A Expired GB1587179A (en) | 1977-05-20 | 1978-05-19 | Preparation of azo dyestuffs |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5410332A (en) |
| CH (1) | CH633308A5 (en) |
| DE (1) | DE2722768A1 (en) |
| FR (1) | FR2391253A2 (en) |
| GB (1) | GB1587179A (en) |
| IT (1) | IT1158719B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN169343B (en) * | 1986-04-05 | 1991-09-28 | Cassella Farbwerke Mainkur Ag | |
| US4987502A (en) * | 1986-10-06 | 1991-01-22 | Eastman Kodak Company | Anti-wear disk drive system |
| JP3318109B2 (en) * | 1994-03-25 | 2002-08-26 | ダイスタージャパン株式会社 | Water-insoluble monoazo dye |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE471540A (en) * | 1946-03-01 | |||
| FR1537367A (en) * | 1966-09-22 | 1968-08-23 | Ciba Geigy | Process for the production of azo pigment dyes |
-
1977
- 1977-05-20 DE DE19772722768 patent/DE2722768A1/en not_active Withdrawn
-
1978
- 1978-05-18 JP JP5834078A patent/JPS5410332A/en active Pending
- 1978-05-19 GB GB20710/78A patent/GB1587179A/en not_active Expired
- 1978-05-19 IT IT23616/78A patent/IT1158719B/en active
- 1978-05-19 FR FR7814871A patent/FR2391253A2/en active Pending
- 1978-05-22 CH CH551378A patent/CH633308A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IT7823616A0 (en) | 1978-05-19 |
| DE2722768A1 (en) | 1978-11-30 |
| CH633308A5 (en) | 1982-11-30 |
| FR2391253A2 (en) | 1978-12-15 |
| JPS5410332A (en) | 1979-01-25 |
| IT1158719B (en) | 1987-02-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |