DE1049381B - - Google Patents
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- Publication number
- DE1049381B DE1049381B DENDAT1049381D DE1049381DA DE1049381B DE 1049381 B DE1049381 B DE 1049381B DE NDAT1049381 D DENDAT1049381 D DE NDAT1049381D DE 1049381D A DE1049381D A DE 1049381DA DE 1049381 B DE1049381 B DE 1049381B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- hydrazones
- solution
- alkyl
- water
- 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
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- 150000007857 hydrazones Chemical class 0.000 claims description 15
- -1 heterocyclic ketones Chemical class 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 150000005840 aryl radicals Chemical group 0.000 claims 1
- 125000004181 carboxyalkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 8
- 239000007858 starting material Substances 0.000 description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000005811 Viola adunca Nutrition 0.000 description 4
- 240000009038 Viola odorata Species 0.000 description 4
- 235000013487 Viola odorata Nutrition 0.000 description 4
- 235000002254 Viola papilionacea Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 244000172533 Viola sororia Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- UMRDPHHVVQUZIR-UHFFFAOYSA-N 2-methylthiadiazol-2-ium Chemical compound C[N+]1=NC=CS1 UMRDPHHVVQUZIR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- UTBVIMLZIRIFFR-UHFFFAOYSA-N 2-methylthio-1,3-benzothiazole Chemical compound C1=CC=C2SC(SC)=NC2=C1 UTBVIMLZIRIFFR-UHFFFAOYSA-N 0.000 description 1
- IKGZOUOHCCARCC-UHFFFAOYSA-N 3-methyl-2-methylsulfanyl-1,3-benzothiazol-3-ium Chemical compound C1=CC=C2[N+](C)=C(SC)SC2=C1 IKGZOUOHCCARCC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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 to ring carbon atoms
- C07D249/14—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
- C07D277/38—Nitrogen atoms
- C07D277/50—Nitrogen atoms bound to hetero atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
Es wurde gefunden, daß man Hydrazone heterocyclischer Ketone der allgemeinen Formel II erhält, wenn man quartäre Cyclammoniumsalze der allgemeinen Formel I mit wäßriger Hydrazinlösung umsetzt. '-.■■·.·■It has been found that hydrazones are heterocyclic Ketones of the general formula II obtained when quaternary cyclammonium salts of the general Formula I is reacted with aqueous hydrazine solution. '-. ■■ ·. · ■
/Y\/ Y \
C-S-RC-S-R
ze z e
Verfahren zur Herstellung von Hydrazonen heterocyclischer KetoneProcess for the preparation of hydrazones of heterocyclic ketones
Anmelder:Applicant:
Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden
Aktiengesellschaft,Corporation,
Ludwigshäfen/RheinLudwig ports / Rhine
+ H2N-NH2 + H 2 N-NH 2
/
X C=N-HN2+ HZ+ HSR/
XC = N-HN 2 + HZ + HSR
IIII
Dr. Hans Baumann, Ludwigshafen/Rhein, und Dr. Friedrich Arnemann, Mannheim,Dr. Hans Baumann, Ludwigshafen / Rhine, and Dr. Friedrich Arnemann, Mannheim,
sind als Erfinder genannt wordenhave been named as inventors
In diesen allgemeinen Formeln bedeutet jedes R einen Alkyl-, Carboxyalkyl-, Cycloalkyl-, Aralkyl- oder Arylrest, X einen — gegebenenfalls substituierten — zweiwertigen Alkylen-, o-Arylen- oder Azomethinrest, Y ein zweiwertiges Ringglied, wie z. B. ein Sauerstoff-, Schwefel-, Selenatom oder eine —NH= oder N (R)-Gruppe, worin R eine Alkyl- oder eine Aminogruppe darstellt, und ΖΘ ein Äquivalent eines Säureanions.In these general formulas, each R is an alkyl, carboxyalkyl, cycloalkyl, aralkyl or aryl radical, X is an - optionally substituted - divalent alkylene, o-arylene or azomethine radical, Y is a divalent ring member, such as. B. an oxygen, sulfur, selenium atom or an —NH = or N (R) group, in which R represents an alkyl or an amino group, and Ζ Θ one equivalent of an acid anion.
Die Ausgangsstoffe der allgemeinen Formel I sind, z. B. durch Umsetzung der entsprechenden Thione (III) bzw. der tautomeren Mercaptane (IV) mit alkylierenden Mitteln, wie Alkylhalogeniden, Dialkylsulfaten oder Chloressigsäureester, in bekannter Weise leicht herstellbar.The starting materials of the general formula I are, for. B. by implementing the corresponding thiones (III) or the tautomeric mercaptans (IV) with alkylating agents such as alkyl halides, dialkyl sulfates or chloroacetic acid ester, easily prepared in a known manner.
/Y\/ Y \
/YV/ Y V
X C = S -r=>i. X C-SHXC = S -r => i. X C-SH
H IIIH III
IVIV
Geeignete Ausgangsstoffe der allgemeinen Formel I sind also z. B. die Einwirkungsprodukte von Dimethylsulfat auf. die 2-Mercaptoverbindungen der Thiazol-, Oxazol-, Selenazol-, Imidazol-, Thiadiazol- oder Triazolreihe, an welche isocyclische gesättigte, ungesättigte oder aromatische Ringe ankondensiert sein können; die Ausgangsstoffe können Substituenten, wie Halogenatome, Alkyl-, Alkoxy-, Aryl-, Mercapto-, Alkylsulfonyl-, Sulfonamid-, Carbonsäureester- oder -amid-, Nitro-, Amino- oder Acylaminogruppcn, tragen.Suitable starting materials of the general formula I are therefore, for. B. the action products of dimethyl sulfate on. the 2-mercapto compounds of the thiazole, oxazole, selenazole, imidazole, thiadiazole or triazole series, to which isocyclic saturated, unsaturated or aromatic rings are fused can; the starting materials can have substituents such as halogen atoms, alkyl, alkoxy, aryl, mercapto, Alkylsulfonyl, sulfonamide, carboxylic acid ester or amide, nitro, amino or acylamino groups, wear.
Außer Dimethylsulfat kann man zur Herstellung der Ausgangsstoffe beispielsweise p-Toluolsulfonsäureäthylester, Chloressigsäureester, Äthylbromid oder Benzylchlorid verwenden.In addition to dimethyl sulfate, ethyl p-toluenesulfonate, for example, can be used to prepare the starting materials. Use chloroacetic acid ester, ethyl bromide or benzyl chloride.
Die Umsetzung der Ausgangsstoffe mit Hydrazin zu den Hydrazonen der allgemeinen Formel II erfolgt zweckmäßig in der Weise, daß man die quartären Verbindungen der allgemeinen Formel I oder ihre Lösung oder Suspension in eine wäßrige Hydrazinlösung einrührt. Zur Bindung der entstehenden Säure und gegebenenfalls auch des abgespaltenen Mercaptans fügt man vor dem Eintragen der quartären Verbindung oder gleichzeitig die erforderliche Menge eines säurebindenden Mittels, wie Alkalicarbonat, -bicarbonat oder -hydroxyd, Erdalkalioxyd oder -hydroxyd oder Pyridin, hinzu; man!kann auch einen entsprechenden Hydrazinüberschuß verwenden.The reaction of the starting materials with hydrazine to give the hydrazones of the general formula II takes place expediently in such a way that the quaternary compounds of general formula I or their solution or the suspension is stirred into an aqueous hydrazine solution. Adds to bind the acid formed and, if appropriate, also the mercaptan which has been split off before entering the quaternary compound or at the same time the required amount of an acid-binding compound Means, such as alkali carbonate, bicarbonate or hydroxide, alkaline earth oxide or hydroxide or Pyridine, added; you can also use a corresponding excess of hydrazine.
Die Verfahrensprodukte bilden sich im allgemeinen schon bei gewöhnlicher Temperatur rasch, zuweilen unter Wärmeentwicklung. In manchen Fällen ist . Kühlen erforderlich oder Erwärmen vorteilhaft.The products of the process generally form rapidly, sometimes even at ordinary temperature with heat development. In some cases it is. Cooling required or heating beneficial.
Die erfindungsgemäßen Hydrazone scheiden sich bereits während der Umsetzung in kristalliner Form oder als Öl aus. Bei leicht wasserlöslichen Hydrazonen empfiehlt es sich, bereits vor der Umsetzung indifferente Salze, insbesondere Natriumchlorid, zuzusetzen, damit die Hydrazone möglichst rasch und vollständigThe hydrazones according to the invention separate in crystalline form during the reaction or as oil. In the case of readily water-soluble hydrazones, it is advisable to make indifferent ones before the reaction Add salts, especially sodium chloride, so that the hydrazones are as quick and complete as possible
809 747/436809 747/436
ausfallen und weitere Umwandlungen, z. B. der Ketazinbildung, entzogen werderi. .fail and further conversions, e.g. B. the Ketazine formation is withdrawn. .
Die Ausbeuten sind im allgemeinen praktisch quantitativ. Überraschenderweise bilden sich keine nennenswerten Mengen Ketazine; die nach dem erfindungsgemäßen Verfahren erhaltenen Hydrazone sind vielmehr sofort sehr rein und brauchen im allgemeinen nicht weitergereinigt zu werden.The yields are generally practically quantitative. Surprisingly, no significant amounts of ketazines are formed; rather, the hydrazones obtained by the process according to the invention are immediately very clean and generally do not need to be cleaned any further.
Wenn die verfahrensgemäß erhaltenen Hydrazone vor der Weiterverarbeitung längere Zeit gelagert werden müssen, empfiehlt es sich, sie durch Umsetzen mit Säuren und gegebenenfalls mit komplexbildenden Salzen, wie Zinkchlorid, in ihre beständigen Salze oder Doppelsalze umzuwandeln. -■ ■ ■-If the hydrazones obtained according to the process are stored for a long time before further processing it is advisable to react them with acids and, if necessary, with complexing agents To convert salts, such as zinc chloride, into their permanent salts or double salts. - ■ ■ ■ -
Die auf die beschriebene Weise leicht herstellbaren Hydrazone sind wertvolle Zwischenprodukte, insbesondere für Farbstoffe.The hydrazones which can be easily prepared in the manner described are valuable intermediates, in particular for dyes.
Die in den nachfolgenden Beispielen genannten Teile sind Gewichtsteile. The parts mentioned in the following examples are parts by weight.
Man stellt zunächst durch Umsetzen von 2-Mercaptobenzthiazol mit Dimethylsulfat in folgender, hier nicht beanspruchter Weise das N-Methyl-2-methylmercaptobenzthiazoliummethosulfat her:One sets first by reacting 2-mercaptobenzothiazole with dimethyl sulfate in the following, not here claimed the N-methyl-2-methylmercaptobenzthiazolium methosulfate from:
Zu einer Lösung von 100 Teilen 2-Mercaptobenzthiazol in 600 Teilen Wasser und 120 Teilen 50%iger Natronlauge läßt man bei 0 bis 10° C unter Rühren allmählich 84 Teile Dimethylsulfat zulaufen. Das ausgefallene 2-Methylmercaptobenzthiazol wird abgesaugt und mit Wasser gewaschen, dann noch feucht mit 230 Teilen o-Dichlorbenzol verrührt,· wobei es sich in diesem löst, und nach Abtrennen der Wasserschicht unter Rühren bei 80° C allmählich mit 100 Teilen Dimethylsulfat versetzt. Man rührt 4 Stunden bei 80° C und dann einige.Stunden bei gewöhnlicher Temperatur. To a solution of 100 parts of 2-mercaptobenzothiazole in 600 parts of water and 120 parts of 50% strength Sodium hydroxide solution is allowed to gradually run in 84 parts of dimethyl sulfate at 0 ° to 10 ° C. with stirring. The unusual one 2-Methylmercaptobenzothiazole is filtered off with suction and washed with water, then still moist with 230 parts of o-dichlorobenzene stirred, in which case it dissolves in this, and after the water layer has been separated off 100 parts of dimethyl sulfate are gradually added with stirring at 80.degree. The mixture is stirred at 80 ° C. for 4 hours and then a few hours at normal temperature.
Das im o-Dichlorbenzol suspendierte N-Methyl-2-methylrnercaptobenzthiazqliummethosulfat wird in 100 Teilen Wasser gelöst. Man befreit die wäßrige Lösung vom o-Dichlorbenzol und rührt sie bei gewöhnlicher Temperatur allmählich in eine Lösung von 45 Teilen Hydrazinhydrat und 47,7 Teilen Natriumcarbonat in 300 Teilen Wasser ein. Dabei kristallisiert das N-Methylbenzthiazolon-(2)-hydrazon sofort als feinkristalliner Niederschlag aus. Man saugt ab, wäscht mit Wasser und trocknet unter vermindertem Druck bei 60 bis 70° C. Die Ausbeute beträgt 103 Teile, entsprechend 96% der Theorie, berechnet auf das angewendete 2-Mercaptobenzthiazol. Das Produkt schmilzt ohne weitere Reinigung bei 145 bis 146° C.The N-methyl-2-methylrnercaptobenzthiazqliummethosulfat suspended in the o-dichlorobenzene is dissolved in 100 parts of water. The aqueous solution is freed from o-dichlorobenzene and stirred at a normal rate Temperature gradually into a solution of 45 parts of hydrazine hydrate and 47.7 parts of sodium carbonate in 300 parts of water. The N-Methylbenzthiazolon- (2) -hydrazone immediately crystallizes as fine crystalline precipitate. It is suctioned off, washed with water and dried under reduced pressure Pressure at 60 to 70 ° C. The yield is 103 parts, corresponding to 96% of theory, calculated on the applied 2-mercaptobenzothiazole. The product melts at 145 without further purification up to 146 ° C.
Man stellt zunächst in hier nicht beanspruchter Weise aus 2,5-Dirnercapto-l,3,4-thiadiazol und Dimethylsulfat das 2,5-Bis-(methylmercapto-)N-methylthiadiazoliummethosulfat her:It is first prepared in a manner not claimed here from 2,5-Dirnercapto-l, 3,4-thiadiazole and dimethyl sulfate the 2,5-bis- (methylmercapto-) N-methylthiadiazolium methosulphate:
Zu einer Lösung von 150 Teilen 2,5-Dimercapto-1,3,4-thiadiazol in 1500 Teilen 2 η-Natronlauge-läßt man bei 10 bis 15° C unter kräftigem Rühren 320 Teile Dimethylsulfat fließen. Die meistens ölig sich abscheidende 2,5-Dimethylmercaptoverbindung wird ohne weitere Reinigung in 600 Teilen Toluol gelöst und mit 140 Teilen Dimethylsulfat 2 Stunden bei 110° C gerührt. Nach dem Erkalten fügt man 800 Teile Wasser hinzu und trennt die Toluolschicht ab.To a solution of 150 parts of 2,5-dimercapto-1,3,4-thiadiazole in 1500 parts of 2 η-sodium hydroxide solution is left at 10 to 15 ° C with vigorous stirring 320 Parts of dimethyl sulfate flow. The 2,5-dimethyl mercapto compound, which is usually deposited in an oily form, is dissolved in 600 parts of toluene without further purification and treated with 140 parts of dimethyl sulfate for 2 hours 110 ° C stirred. After cooling, 800 parts of water are added and the toluene layer is separated away.
Die wäßrige Lösung, die das 2,5-Bis-(methyl-The aqueous solution containing the 2,5-bis- (methyl-
ao mercapto-) N-methylthiadiazoliummethosulfat enthält, lührt man allmählich in eine Lösung von 50 Teilen Hydrazinhydrat und 30 Teilen Natriumchlorid in 25O1 Teilen Wasser ein, wobei sich das 2-Methylmercapto - 4 - methyl -1,3,4 - thiadiazolon - (5) -hydrazon der Formelao mercapto) N-methylthiadiazolium methosulphate is gradually introduced into a solution of 50 parts of hydrazine hydrate and 30 parts of sodium chloride in 250 1 part of water, the 2-methylmercapto - 4 - methyl -1,3,4 - thiadiazolone - ( 5) hydrazone of the formula
CH,S — CCH, S - C
= N-NH9 = N-NH 9
CH3 CH 3
kristallin ausscheidet. Man saugt es nach mehrstündigem Stehen in der Kälte ab, wäscht es mit Eiswasser und trocknet es bei vermindertem Druck. Die Ausbeute beträgt 148 Teile. Nach dem Umkristallisieren aus wäßrigem Methanol erhält man das Produkt in Form farbloser Nadeln vom Schmelzpunkt 165 bis 166° C, die sich am Licht allmählich grünlich verfärben. Es ist in Alkoholen, aromatischen Kohlenwasserstoffen, Eisessig und verdünnten wäßrigen Mineralsäuren leicht, in Wasser schwer löslich.precipitates in crystalline form. After standing for several hours in the cold, it is vacuumed and washed with ice water and dry it under reduced pressure. The yield is 148 parts. After recrystallization the product is obtained from aqueous methanol in the form of colorless needles with a melting point of 165 bis 166 ° C, which gradually turn green in the light. It's in alcohols, aromatic hydrocarbons, Glacial acetic acid and dilute aqueous mineral acids easily soluble in water.
In analoger Weise kann man die folgenden Hydrazone herstellen, die durch die angegebenen Schmelzpunkte bzw. durch die Lösungsfarbe ihrer durch oxydative Kupplung mit Dimethylanilin und Eisen(III)-chlorid nach Patent 963 176 entstehenden Derivate in einem Gemisch aus gleichen Teilen Methanol und Wasser charakterisiert sind:The following hydrazones can be prepared in an analogous manner, which are represented by the specified Melting points or by the solution color of their oxidative coupling with dimethylaniline and Iron (III) chloride according to patent 963 176 resulting derivatives in a mixture of equal parts Methanol and water are characterized by:
V C = N-NH 2
V
\O 2 N
\
104$ 381$ 104 381
Ausgangsstofi HydrazonStarting material hydrazone
P-V5 E" I LösungsfarbePV 5 E "I solution paint
NeTNeT
CH,CH,
C—SCoHs C — SCoH s
CtLOSOo0 CtLOSOo 0
N N-CH3 -N N-CH 3 -
C6H5-NH-CC 6 H 5 -NH-C
C-SCH,C-SCH,
Br©Br ©
HC SHC S
H3C-C C- SCH3 H 3 CC C- SCH 3
CH,CH,
HC SHC S
Il IIl I
HC C-SCH3 HC C-SCH 3
XN© X N ©
CH3 CH 3
CH,OSO,eCH, OSO, e
CH3OSO3 0 CH 3 OSO 3 0
C6H5NHC 6 H 5 NH
C-SCH,C-SCH,
CHa CH a
CH8OSO3 0 CH 8 OSO 3 0
CHoCONHCHoCONH
C-SCH,C-SCH,
CH,CH,
CH3OSO3 0 CH 3 OSO 3 0
O rfO rf
C2H5OC 2 H 5 O
C-S-CH,C-S-CH,
CH,CH,
CH-OSO,® /V0VCH-OSO, ® / V 0 V
C=N-NH"C = N-NH "
CH,CH,
N -N-CH3 N -N-CH 3
Il ΊIl Ί
C6H5-NH-C C=N-NH2 C 6 H 5 -NH-C C = N-NH 2
HC-—SHC - S
H3C-C C=N-NH2 H 3 CC C = N-NH 2
CH,CH,
HC SHC S
HC C=N-NH2 HC C = N-NH 2
CH3 CH 3
QH5NHQH 5 NH
C=N-NH,C = N-NH,
CH,CONHCH, CONH
N
CH3 N
CH 3
S/S /
C=N-NH,C = N-NH,
N
CH3 N
CH 3
C2H5OC 2 H 5 O
C=N-NH,C = N-NH,
N CH3 N CH 3
222222
134134
132 bis132 to
174 bis174 to
133133
BordoBordo
Grünstichigblau Greenish blue
Violettviolet
Violettviolet
Blaublue
Rotstichigblau Reddish blue
Grünstichigblau Greenish blue
AusgangsstofiStarting materials
HydrazonHydrazone
R0C I LösungsfarbeR 0 CI solution color
vy ö — \_< Χίοvy ö - \ _ < Χίο
C2H8 C 2 H 8
CH3OSO3 0 CH 3 OSO 3 0
C—SCH,C — SCH,
Ν<ί CH, Ν <ί CH,
CH,OSO,e CH, OSO, e
C-S-CH,C-S-CH,
w® CH2 w® CH 2
-C-C
/■/ ■
CH3 CH 3
NH2 -Nn NH 2 -N n
Ne CH3 Ne CH 3
C4H9 C 4 H 9
αΘ α Θ
C-S-CH,C-S-CH,
CH,OSO,e CH, OSO, e
N y N y
C — SCH,C - SCH,
Ν© CH3 Ν © CH 3
CH3SO4QCH 3 SO 4 Q
HC'HC '
CH,CH,
CH4SO4 0 CH 4 SO 4 0
C=N-NH,C = N-NH,
C2H5 C 2 H 5
ClCl
cc C=N-NH9 cc C = N-NH 9
C=N-NH,C = N-NH,
C=N-NH2 C = N-NH 2
■N' CH3 ■ N ' CH 3
C=N-NH0 C = N-NH 0
HCHC
Il -C C=N-NH5 II -CC = N-NH 5
'Ν CH3 173'Ν CH 3 173
118118
Erweichungspunkt bisSoftening point up to
bisuntil
8383
BlauviolettBlue violet
BlauviolettBlue violet
BlauviolettBlue violet
BordoBordo
Blaus ti chigrot Blue ti chi red
BlauviolettBlue violet
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1049381B true DE1049381B (en) | 1959-01-29 |
Family
ID=590019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1049381D Pending DE1049381B (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1049381B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4410616A1 (en) * | 1994-03-26 | 1995-09-28 | Pagg Produktions Ag Giswil | Accident protection device |
| WO2004078152A1 (en) * | 2003-03-05 | 2004-09-16 | Wella Aktiengesellschaft | Means and method for the simultaneous bleaching and dyeing of keratin fibres |
| US7070625B2 (en) | 2001-11-14 | 2006-07-04 | Wella Ag | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
| US7244278B2 (en) | 2003-12-16 | 2007-07-17 | Wella Ag | Agent and method for oxidative coloring of keratin fibers |
| US7291183B2 (en) | 2003-03-05 | 2007-11-06 | Wella Ag | Agent and method for dyeing keratin fibers |
| US7429274B2 (en) | 2003-12-16 | 2008-09-30 | Wella Ag | Agent and method for the oxidative coloring of keratin fibers |
-
0
- DE DENDAT1049381D patent/DE1049381B/de active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4410616A1 (en) * | 1994-03-26 | 1995-09-28 | Pagg Produktions Ag Giswil | Accident protection device |
| US7070625B2 (en) | 2001-11-14 | 2006-07-04 | Wella Ag | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
| WO2004078152A1 (en) * | 2003-03-05 | 2004-09-16 | Wella Aktiengesellschaft | Means and method for the simultaneous bleaching and dyeing of keratin fibres |
| US7291183B2 (en) | 2003-03-05 | 2007-11-06 | Wella Ag | Agent and method for dyeing keratin fibers |
| US7326254B2 (en) | 2003-03-05 | 2008-02-05 | Wella Ag | Means and method for the simultaneous bleaching and dyeing of keratin fibres |
| US7244278B2 (en) | 2003-12-16 | 2007-07-17 | Wella Ag | Agent and method for oxidative coloring of keratin fibers |
| US7429274B2 (en) | 2003-12-16 | 2008-09-30 | Wella Ag | Agent and method for the oxidative coloring of keratin fibers |
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