DE2060197C3 - Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-Alkylsubstitutionsprodukten - Google Patents
Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-AlkylsubstitutionsproduktenInfo
- Publication number
- DE2060197C3 DE2060197C3 DE2060197A DE2060197A DE2060197C3 DE 2060197 C3 DE2060197 C3 DE 2060197C3 DE 2060197 A DE2060197 A DE 2060197A DE 2060197 A DE2060197 A DE 2060197A DE 2060197 C3 DE2060197 C3 DE 2060197C3
- Authority
- DE
- Germany
- Prior art keywords
- sulfur dioxide
- mercaptobenzothiazole
- amine
- preparation
- substitution products
- 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
- 238000000034 method Methods 0.000 title claims description 18
- 238000006467 substitution reaction Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 title description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 32
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- QVKPPRYUGJFISN-UHFFFAOYSA-N n-methyl-1,3-benzothiazol-2-amine Chemical compound C1=CC=C2SC(NC)=NC2=C1 QVKPPRYUGJFISN-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- -1 sulphurous acid Carbon atoms Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 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 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005349 heatable glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2060197A DE2060197C3 (de) | 1970-12-08 | 1970-12-08 | Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-Alkylsubstitutionsprodukten |
| US00204313A US3781297A (en) | 1970-12-08 | 1971-12-02 | Process for preparing 2-aminobenzothiazole and its n-alkyl substitution products from 2-mercaptobenzothiazole |
| IT32112/71A IT951603B (it) | 1970-12-08 | 1971-12-06 | Procedimento per la preparazione di 2 aminobenzotiazolo e suoi pro dotti di n alchilsostituzione |
| CA129,360A CA945166A (en) | 1970-12-08 | 1971-12-06 | Process for the preparation of 2-aminobenzothiazole and its n-alkyl substitution products |
| NLAANVRAGE7116744,A NL174827C (nl) | 1970-12-08 | 1971-12-06 | Werkwijze voor het bereiden van 2-aminobenzthiazool en daarvan afgeleide n-alkylsubstitutieprodukten. |
| IL38300A IL38300A (en) | 1970-12-08 | 1971-12-06 | The production of 2-aminobenzothiazole and its n-alkyl derivatives |
| JP9838171A JPS5421337B1 (enExample) | 1970-12-08 | 1971-12-07 | |
| ES397753A ES397753A1 (es) | 1970-12-08 | 1971-12-07 | Procedimiento para la obtencion de 2-aminobenzotiazol. |
| BE776408A BE776408A (fr) | 1970-12-08 | 1971-12-08 | Procede de preparation d'amino-2 benzothiazole et de ses produits de substitution n-alkyles |
| GB5697971A GB1336954A (en) | 1970-12-08 | 1971-12-08 | Process fot the preparation of 2-aminobenzothiazole and n-alkyl substituted derivatives thereof |
| FR7144118A FR2117556A5 (enExample) | 1970-12-08 | 1971-12-08 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2060197A DE2060197C3 (de) | 1970-12-08 | 1970-12-08 | Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-Alkylsubstitutionsprodukten |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2060197A1 DE2060197A1 (de) | 1972-06-15 |
| DE2060197B2 DE2060197B2 (de) | 1978-06-29 |
| DE2060197C3 true DE2060197C3 (de) | 1979-02-22 |
Family
ID=5790249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2060197A Expired DE2060197C3 (de) | 1970-12-08 | 1970-12-08 | Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-Alkylsubstitutionsprodukten |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3781297A (enExample) |
| JP (1) | JPS5421337B1 (enExample) |
| BE (1) | BE776408A (enExample) |
| CA (1) | CA945166A (enExample) |
| DE (1) | DE2060197C3 (enExample) |
| ES (1) | ES397753A1 (enExample) |
| FR (1) | FR2117556A5 (enExample) |
| GB (1) | GB1336954A (enExample) |
| IL (1) | IL38300A (enExample) |
| IT (1) | IT951603B (enExample) |
| NL (1) | NL174827C (enExample) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4447617A (en) * | 1982-04-14 | 1984-05-08 | Eastman Kodak Company | Process for the preparation of 2-amino-6-nitrobenzothiazole |
| TWI225488B (en) * | 1999-12-21 | 2004-12-21 | Janssen Pharmaceutica Nv | Derivatives of homopiperidinyl substituted benzimidazole analogues |
-
1970
- 1970-12-08 DE DE2060197A patent/DE2060197C3/de not_active Expired
-
1971
- 1971-12-02 US US00204313A patent/US3781297A/en not_active Expired - Lifetime
- 1971-12-06 CA CA129,360A patent/CA945166A/en not_active Expired
- 1971-12-06 NL NLAANVRAGE7116744,A patent/NL174827C/xx not_active IP Right Cessation
- 1971-12-06 IL IL38300A patent/IL38300A/xx unknown
- 1971-12-06 IT IT32112/71A patent/IT951603B/it active
- 1971-12-07 JP JP9838171A patent/JPS5421337B1/ja active Pending
- 1971-12-07 ES ES397753A patent/ES397753A1/es not_active Expired
- 1971-12-08 GB GB5697971A patent/GB1336954A/en not_active Expired
- 1971-12-08 FR FR7144118A patent/FR2117556A5/fr not_active Expired
- 1971-12-08 BE BE776408A patent/BE776408A/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2117556A5 (enExample) | 1972-07-21 |
| IL38300A (en) | 1975-02-10 |
| NL7116744A (enExample) | 1972-06-12 |
| CA945166A (en) | 1974-04-09 |
| ES397753A1 (es) | 1974-05-16 |
| US3781297A (en) | 1973-12-25 |
| IL38300A0 (en) | 1972-02-29 |
| DE2060197A1 (de) | 1972-06-15 |
| BE776408A (fr) | 1972-06-08 |
| DE2060197B2 (de) | 1978-06-29 |
| GB1336954A (en) | 1973-11-14 |
| NL174827C (nl) | 1984-08-16 |
| IT951603B (it) | 1973-07-10 |
| NL174827B (nl) | 1984-03-16 |
| JPS5421337B1 (enExample) | 1979-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2056569C3 (enExample) | ||
| DE69302848T2 (de) | Verfahren zur Herstellung von Guanidinderivativen | |
| DE2060197C3 (de) | Verfahren zur Herstellung von 2-Aminobenzothiazol und dessen N-Alkylsubstitutionsprodukten | |
| DE2551060A1 (de) | Verfahren zur herstellung von 2-mercaptobenzthiazol | |
| CH615168A5 (enExample) | ||
| DD148952A1 (de) | Verfahren zur herstellung von blutdrucksenkendem 6,7-dimethoxy-4-amino-2- eckige klammer auf 4-(2-furoyl)-1-piperazinyl eckige klammer zu chinazolinhydrochlorid | |
| DE2424372C3 (de) | Verfahren zur Herstellung von Isonitrosoacetaniliden | |
| EP0270815A1 (de) | Verfahren zur Herstellung von 5-aminosalicylsäure | |
| DE2444977A1 (de) | Verfahren zur herstellung von thiocarbamylsulfenamiden | |
| DE2532124C3 (de) | Verfahren zur Herstellung von 4-Amino-morpholin | |
| DE3015374A1 (de) | Verfahren zur herstellung von harnstoffen | |
| DE2800537C2 (de) | Verfahren zur Herstellung von 1-Amino-2-alkoxy-5-brom-benzolen | |
| AT206897B (de) | Verfahren zur Herstellung von neuen 4-Oxo-2-(halogenalkyl)-2,3-dihydro-[benzo-1,3-oxazinen] | |
| DE1046063B (de) | Verfahren zur Herstellung neuer, amoebicid wirkender Acetanilide | |
| AT206444B (de) | Verfahren zur Herstellung von neuen Pyridazinderivaten | |
| CH633278A5 (de) | Verfahren zur herstellung von 2-alkyl- bzw. 2-cycloalkyl-4-methyl-6-hydroxypyrimidinen. | |
| AT239243B (de) | Verfahren zur Herstellung von 2, 3-Dicyan-1, 4-dithia-anthrahydrochinon und -anthrachinon | |
| CH641792A5 (de) | Verfahren zur herstellung von 1,2,3-thiadiazol-5-yl-harnstoffen. | |
| AT360520B (de) | Verfahren zur herstellung von neuen thiazoli- dinderivaten und ihren salzen | |
| AT352092B (de) | Verfahren zur herstellung von acetoacetamid-n- sulfofluorid | |
| DE2816503A1 (de) | Verfahren zur herstellung von 2-mercaptobenzthiazol | |
| DE1202270B (de) | Verfahren zur Herstellung von substituierten Norbornylharnstoffen | |
| DE1543331A1 (de) | Verfahren zur Herstellung von N,N-disubstituierten p-Alkylmercaptoanilinen | |
| DE2716897A1 (de) | Verfahren zur herstellung aromatischer thioharnstoffe | |
| DE2633211B2 (de) | Verfahren zur Herstellung von 4-Carboxamido-5-cyano-2-imidazolon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| 8339 | Ceased/non-payment of the annual fee |