DK142457B - Process for the preparation of 2-hydrazinobenzothiazoles. - Google Patents
Process for the preparation of 2-hydrazinobenzothiazoles. Download PDFInfo
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- DK142457B DK142457B DK547573AA DK547573A DK142457B DK 142457 B DK142457 B DK 142457B DK 547573A A DK547573A A DK 547573AA DK 547573 A DK547573 A DK 547573A DK 142457 B DK142457 B DK 142457B
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- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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Description
(11) FREMLÆGGELSESSKRIFT 142^+57 DANMARK (5i) int. ci.3 c 07 d 277/82 §(21) Ansegning nr. 5^75/75 (22) indleveret den 9· 1975 (24) Lebedag 9· Okt. 1975 (44) Ansegningen fremlagt og fremlæggelsesskriftet offentliggjort den 5 « nOV · 1 9^0(11) PUBLICATION MANUAL 142 ^ + 57 DENMARK (5i) int. ci.3 c 07 d 277/82 § (21) Application No. 5 ^ 75/75 (22) filed on 9 · 1975 (24) Life Day 9 · Oct. 1975 (44) The application submitted and the writ published on 5 «nOV · 1 9 ^ 0
DIREKTORATET FORDIRECTORATE OF
PATENT-OG VAREMÆRKEVÆSENET (30) Prioritet begæret fra denPATENT AND TRADE MARKET (30) Priority requested from it
10. okt. 1972, 296581, USOct 10 1972, 296581, US
(71) ELI LILLY AND COMPAUY, 507 East McCarty Street, Indianapolis, Indiana 46205, US.(71) ELI LILLY AND COMPAUY, 507 East McCarty Street, Indianapolis, Indiana 46205, US.
(72) Opfinder: Charles Jackson Barnett, 4529-å Lakeway Drive, Indianapolis# Indiana, US. ~ (74) Fuldmægtig under sagens behandling:(72) Inventor: Charles Jackson Barnett, 4529 Å Lakeway Drive, Indianapolis # Indiana, US. ~ (74) Plenipotentiary in the proceedings:
Ingeniørfirmaet Budde, Schou & Co.The engineering company Budde, Schou & Co.
(54) Fremgangsmåde til fremstilling af 2-hydrazinobenzothIazoler.(54) Process for the preparation of 2-hydrazinobenzothiazole.
Den foreliggende opfindelse angår en forbedret fremgangsmåde til fremstilling af 2-hydrazinobenzothiazoler ved omsætning af de tilsvarende 2-aminobenzothiazoler med hydrazin.The present invention relates to an improved process for preparing 2-hydrazinobenzothiazoles by reacting the corresponding 2-aminobenzothiazoles with hydrazine.
Den omhandlede fremgangsmåde er en "omaminering", hvilket udtryk betegner ombytningen af en aminogruppe med en anden, herunder udvekslingen af en aminogruppe med en hydrazinogruppe, se Houben Weyl, Methoden Der Organischen Chemie, bind 10/2, 278 (Georg Thieme Verlag, Stuttgart, 1967), Ann. 686, 134 (1965), J. Amer.The present process is an "omamination" which means the exchange of one amino group with another, including the exchange of one amino group with a hydrazino group, see Houben Weyl, Methods Der Organischen Chemie, Vol. 10/2, 278 (Georg Thieme Verlag, Stuttgart , 1967), Ann. 686, 134 (1965), J. Amer.
Chem. Soc. 74, 1648 (1952), J. Amer. Chem. Soc. 82, 3971 (1960), og J. Gen. Chem. U.S.R. (engelsk oversættelse) 29^, 2036 (1959).Chem. Soc. 74, 1648 (1952), J. Amer. Chem. Soc. 82, 3971 (1960), and J. Gen. Chem. U.S.R. (English translation) 29 ^, 2036 (1959).
Sidstnævnte blandt disse litteratursteder rapporterer om fremstilling af og forsøg på fremstilling af talrige 2-hydrazinobenzo- 2 U2457 thiazoler ved omsætning af hydrazin med 2-aminobenzothiazol og forskellige ringsubstituerede 2-aminobenzothiazoler. Imidlertid var resultaterne mindre end helt tilfredsstillende. Nogle af reaktionerne gav intet hydrazinobenzothiazol-produkt. Usubstitueret 2-aminobenzothiazol gav det ønskede produkt, men ledsaget af en væsentlig mængde o-amino-thiophenol dannet ved ringåbning og isoleret som disulfidet. Kun carboxy-substituerede aminobenzothiazoler gav gode udbyttere.The latter among these literature sites reports on the preparation of and attempts to prepare numerous 2-hydrazinobenzo-2 U2457 thiazoles by reaction of hydrazine with 2-aminobenzothiazole and various ring-substituted 2-aminobenzothiazoles. However, the results were less than perfectly satisfactory. Some of the reactions yielded no hydrazinobenzothiazole product. Unsubstituted 2-aminobenzothiazole yielded the desired product, but accompanied by a substantial amount of o-amino-thiophenol formed by ring opening and isolated as the disulfide. Only carboxy-substituted aminobenzothiazoles gave good yields.
Den foreliggende opfindelse består nu i en særlig fremgangsmåde til fremstilling af 2-hydrazinobenzothiazoler med formlen:The present invention now consists in a particular process for the preparation of 2-hydrazinobenzothiazoles of the formula:
y'-KY'-K
R---^^p>NH-NHs hvori hver enkelt af substituenterne R indbyrdes uafhængigt betegner hydrogen, halogen, alkyl med 1 til 3 carbonatomer, alkoxy med 1 til 3 carbonatomer eller alkylthio med 1 til 3 carbonatomer, og n er 0, 1 eller 2, ved hvilken man omsætter de tilsvarende 2-amino-benzothiazolforbindelser med formlen JL /ncr,)s hvori R og n har den ovenfor anførte betydning, og hvert indbyrdes uafhængigt betegner hydrogen eller methyl, med hydrazin, navnlig i form af hydrazin-hydrat, og fremgangsmåden er ejendommelig ved, at omsætningen foregår i nærværelse af i det mindste en katalytisk mængde syre eller ved anvendelse af syreadditionssalte af udgangsmaterialerne og fortrinsvis i nærværelse af et indifferent opløsningsmiddel. Således som benyttet i den foreliggende beskrivelse med krav betegner "halogen" brom, chlor og fluor.R --- ^^ p p> NH-NHs wherein each of the substituents R ind independently represents hydrogen, halogen, alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 3 carbon atoms or alkylthio of 1 to 3 carbon atoms, and n is 0, 1 or 2, wherein the corresponding 2-amino-benzothiazole compounds of formula JL / ncr are reacted, wherein R and n are as defined above and each independently represents hydrogen or methyl, with hydrazine, in particular in the form of hydrazine hydrate, and the process is characterized in that the reaction takes place in the presence of at least a catalytic amount of acid or by using acid addition salts of the starting materials and preferably in the presence of an inert solvent. As used in the present specification with claims, "halogen" represents bromine, chlorine and fluorine.
De herved fremkomne 2-hydrazinobenzothiazolforbindelser er anvendelige som udgangsmaterialer for fremstillingen af s-triazolo-(3,4-b)benzothiazolforbindelser med formlen: ,.u 2 142457 3 hvori R og n har den ovenfor anførte betydning, og R er hydrogen eller en lavere alkylgruppe. Disse forbindelser er anvendelige som midler til bekæmpelse af sygdomsfremkaldende organismer hos planter.The resulting 2-hydrazinobenzothiazole compounds are useful as starting materials for the preparation of s-triazolo (3,4-b) benzothiazole compounds of the formula: wherein R and n are as defined above and R is hydrogen or a lower alkyl group. These compounds are useful as agents for controlling disease-causing organisms in plants.
Anvendelsen af en syre er kritisk for den foreliggende fremgangsmåde. Syrens identitet er imidlertid ikke kritisk. Det er mest hensigtsmæssigt at anvende en mineralsyre såsom saltsyre, hydrobromidsyre eller svovlsyre. Imidlertid er også organiske syrer tilfredsstillende såsom eddikesyre, benzoesyre, myresyre, malonsyre, oxalsyre, p-toluensulfonsyre, phenyleddikesyre og citronsyre, som alle har vist sig operable ved fremgangsmåden ifølge opfindelsen.The use of an acid is critical to the present process. However, the identity of the acid is not critical. It is most convenient to use a mineral acid such as hydrochloric acid, hydrobromic acid or sulfuric acid. However, organic acids are also satisfactory such as acetic acid, benzoic acid, formic acid, malonic acid, oxalic acid, p-toluenesulfonic acid, phenylacetic acid and citric acid, all of which have been found operable in the process of the invention.
Syren kan føres til reaktionsblandingen på en hvilken som helst af flere forskellige måder. Den kan tilsættes særskilt eller der kan tilføres som salt af enten 2-aminobenzothiazolforbindelsen eller hydrazinen.The acid can be passed to the reaction mixture in any of several different ways. It may be added separately or may be added as salt of either the 2-aminobenzothiazole compound or hydrazine.
Mængden af tilført syre er ikke kritisk. En lille katalytisk mængde forbedrer udbyttet af produkt væsentligt i forhold til det udbytte, der fås, når der slet ikke anvendes syrer. Imidlertid er større mængder ikke skadelige. I almindelighed skrider den her omhandlede fremgangsmåde fremad, når man anvender syrer i forholdet fra 0,1 til 1,0 moldel syre for hver moldel hydrazin. Et foretrukket forhold er fra 0,33 til 0,5 moldel syre pr. moldel hydrazin.The amount of acid added is not critical. A small catalytic amount significantly improves the yield of product over the yield obtained when no acids are used at all. However, larger quantities are not harmful. Generally, the process of the present invention proceeds when using acids in the ratio of 0.1 to 1.0 moldal acid for each mold hydrazine. A preferred ratio is from 0.33 to 0.5 molds of acid per minute. mold hydrazine.
Medens man inden for den kendte teknik ofte har benyttet overskud af hydrazin, der til dels tjener som opløsningsmiddel, har det dog nu vist sig, at anvendelsen af et overfor reaktionen indifferente opløsningsmiddel er at foretrække. Opløsningsmidlet skal være et sådant, som er blandbart med hydrazin, og som I kombination med reagenserne giver en tilbagesvalingstemperatur på mindst ca. 100°C og foretrinsvis højere temperaturer såsom i intervallet fra 120°C til 150°C. Foretrukne opløsningsmidler indbefatter alkylendioler med 2 til 4 car-bonatomer såsom ethylenglycol, propylenglycol, 1,4-butandiol og 2,3--butandiol, di- og tri(ethylen og propylen)-glycoler, herunder diethy-lenglycol, triethylenglycol, dipropylenglycol og tripropylenglycol, monoalkylethere af ethylen og propylenglycoler, hvor alkyldelen indeholder 1-4 carbonatomer, såsom ethylenglycolmonomethylether, ethylenglycol monoethylether, ethylenglycol-mono-n-butylether og propylengly-colmonomethylether, monoalkylethere af di- og tri(ethylen og propylen)- 4 142457 -glycoler med 1 til 4 earbonatomer i alkyldelen såsom diethylenglyeol-monomethylether, diethylenglycolmonoethylether og diethylenglycol-mono--n-butylether, triethanolamin, sulfolan og dimethylsulfoxid. Således som her benyttet skal udtrykket alkylendioler med 2 til 4 carbonatomer i alkyldelen forstås som kun non-gem-dioler. Skønt vand ikke er et foretrukket opløsningsmiddel,, er mindre mængder deraf dog ikke skadelige for reaktionen. Derfor er det acceptabelt at tilføre hydrazinen som en hvilken som helst af de talrige kommerciel tilgængelige former, der indbefatter vand.However, while in the prior art excess hydrazine, which partly serves as a solvent, has often been used, it has now been found that the use of a solvent inert to the reaction is preferable. The solvent must be one which is miscible with hydrazine and which, in combination with the reagents, gives a reflux temperature of at least approx. 100 ° C and preferably higher temperatures such as in the range of 120 ° C to 150 ° C. Preferred solvents include alkylene diols having 2 to 4 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol and 2,3-butanediol, di- and tri (ethylene and propylene) glycols, including diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, monoalkyl ethers of ethylene and propylene glycols wherein the alkyl moiety contains 1-4 carbon atoms such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether and propylene glycol monomethyl ether, monoalkyl ethers of di- and tri (ethylene and propylene) with 1 to 4 earbon atoms in the alkyl moiety such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n-butyl ether, triethanolamine, sulfolane and dimethyl sulfoxide. As used herein, the term alkylene diols having 2 to 4 carbon atoms in the alkyl moiety is to be understood as only non-gem diols. However, although water is not a preferred solvent, smaller amounts thereof are not detrimental to the reaction. Therefore, it is acceptable to supply the hydrazine as any of the numerous commercially available forms including water.
Det er ikke kritisk, at 2-aminobenzothiazolen og hydrazinen benyttes i noget specifikt forhold til hinanden. Inden for den kendte teknik har man ofte anvendt et stort overskud af hydrazin. Det har nu imidlertid vist sig i tilfælde med nogle af 2-aminobenzothiazolforbin-delserne, at dannelsen af biprodukter forøges ved højere hydrazinkoncentrationer. Hertil kommer, at da reaktionen forbruger reaktanterne i kun ækvimolære mængder, er anvendelsen af et overskud af hydrazin ineffektiv. Gode resultater er opnået ved praktiseringen af den foreliggende opfindelse med forhold fra 1 til ikke mere end ca. 10 molære andele af hydrazin pr. molære andel af 2-aminobenzothiazolen. De bedste resultater er opnået med en mængde fra ca. 3 til ca. 5 molære andele af hydrazin pr. molær andel af 2-aminobenzothiazolen.It is not critical that the 2-aminobenzothiazole and hydrazine be used in any specific relationship to one another. In the prior art, a large excess of hydrazine has often been used. However, it has now been found, in the case of some of the 2-aminobenzothiazole compounds, that the formation of by-products is increased at higher hydrazine concentrations. In addition, since the reaction consumes the reactants in only equimolar amounts, the use of an excess of hydrazine is ineffective. Good results have been obtained in the practice of the present invention with ratios of from 1 to no more than ca. 10 molar proportions of hydrazine per molar proportion of the 2-aminobenzothiazole. The best results are obtained with an amount of approx. 3 to approx. 5 molar proportions of hydrazine per molar proportion of the 2-aminobenzothiazole.
Temperaturen, ved hvilken reaktionen gennemføres, er ikke kritisk. I almindelighed forløber reaktionen ved temperaturer over 100°C og derover. Typisk har temperaturer fra 100 til 150°C vist sig at give gode resultater. De bedste resultater fås i almindelighed ved temperaturer på 120-150°C. Typisk udfældes det ønskede produkt i reaktionsblandingen og skilles fra ved filtrering. Imidlertid kan andre konventionelle adskillelsesfremgangsmåder anvendes. De ved den foreliggende fremgangsmåde fremstillede produkt er sædvanligvis af høj renhed, i nogle tilfælde så høj som 38^; men om ønsket kan det fraskildte produkt renses ved konventionelle fremgangsmåder.The temperature at which the reaction is carried out is not critical. In general, the reaction proceeds at temperatures above 100 ° C and above. Typically, temperatures from 100 to 150 ° C have been found to give good results. The best results are generally obtained at temperatures of 120-150 ° C. Typically, the desired product is precipitated in the reaction mixture and separated by filtration. However, other conventional separation methods can be used. The product of the present process is usually of high purity, in some cases as high as 38 but if desired, the separated product can be purified by conventional methods.
De følgende eksempler tjener til nærmere belysning af fremgangsmåden ifølge opfindelsen.The following examples serve to elucidate the method of the invention.
55
Eksempel 1 142457 2-HydrazinobenzothiazolEXAMPLE 1 2-Hydrazinobenzothiazole
Til en opslæmning af 30 g (0,2 mol) 2-aminobenzothiazol i 150 ml ethylenglycol sættes 23,7 S (0,4 mol) 85$ hydrazin-hydrat og 13,7 g (0,2 mol) hydrazin-monohydrochlorid. Blandingen omrøres under en nitro-genatomosfære og opvarmes til en temperatur på 140°C i 2 timer. Produktet udkrystalliserer ved afkøling. Efter tilsætning af 5C ml vand og omrøring filtreres materialet, vaskes med 100 ml vand i 3 portioner og tørres i vakuum ved 60°C. Der fås 29,9 g (90,0# af det teoretiske udbytte) 2-hydrazinobenzothiazol med smeltepunkt 194-19'°C, og som ved praktisk forsøg (titrering) viser en renhed på 97,0#. Omkrystallisation fra ethanol giver 20 g med smeltepunkt 198-199°C ''smeltepunkt ifølge litteraturen 199-200°C, jfr. I. A. Solov'eva og A. G. Guseva, J. Gen. Chem. U.S.S.R. 29, 2036 (1959))· Der fås yderligere 4 g med smeltepunkt 196,5-198,5°C som udbytte i anden omgang.To a slurry of 30 g (0.2 mole) of 2-aminobenzothiazole in 150 ml of ethylene glycol is added 23.7 S (0.4 mole) of $ 85 hydrazine hydrate and 13.7 g (0.2 mole) of hydrazine monohydrochloride. The mixture is stirred under a nitrogen atom atmosphere and heated to a temperature of 140 ° C for 2 hours. The product crystallizes on cooling. After addition of 5C ml of water and stirring, the material is filtered, washed with 100 ml of water in 3 portions and dried in vacuo at 60 ° C. There is obtained 29.9 g (90.0 # of theoretical yield) of 2-hydrazinobenzothiazole, m.p. 194-19 ° C, which, in a practical test (titration), shows a purity of 97.0 #. Recrystallization from ethanol gives 20 g of melting point 198-199 ° C melting point according to literature 199-200 ° C, cf. I. A. Solov'eva and A. G. Guseva, J. Gen. Chem. U.S.S.R. 29, 2036 (1959)) · An additional 4 g of melting point 196.5-198.5 ° C is obtained as a second yield.
Eksempel 2 5,O-Dimethyl-2-hydrazinobenzothiazol 5,0 g (0,028 mol) 5,6-dimethyl-2-aminobenzothiazol, 3,49 g (0,056 mol) 85# hydrazinhydrat og 1,99 g (0,028 mol) hydrazin-monohydrochlorid omsættes ved fremgangsmåden ifølge eksempel 1. Der fås 5,6-dimethyl-2-hydrazinobenzothiazol i 62#'s udbytte og med smeltepunkt 223-228°C. Forsøgsmæssig afprøvning (titrering) viser en produktrenhed på 97,2#. Omkrystallisation fra ethanol giver et materiale, der smelter ved 235-237°C (sønderdeling).Example 2.5 O-Dimethyl-2-hydrazinobenzothiazole 5.0 g (0.028 mol) 5,6-dimethyl-2-aminobenzothiazole, 3.49 g (0.056 mol) 85 # hydrazine hydrate and 1.99 g (0.028 mol) hydrazine Monohydrochloride is reacted by the procedure of Example 1. 5,6-dimethyl-2-hydrazinobenzothiazole is obtained in 62% yield and mp 223-228 ° C. Experimental testing (titration) shows a product purity of 97.2 #. Recrystallization from ethanol gives a material which melts at 235-237 ° C (dec.).
Analyse beregnet for CgH-QNy3: C = 55,93#, H = 5,74#, N = 21,74# og S = 16,59#Analysis calculated for C 6 H -NO 3: C = 55.93 #, H = 5.74 #, N = 21.74 #, and S = 16.59 #
Funde t: C = 55,96#, H = 5,78#, N = 21,55# og S = 16,72#Found t: C = 55.96 #, H = 5.78 #, N = 21.55 #, and S = 16.72 #
Eksempel 3 4-Chlor-2-hydrazinobenzothiazol 10,09 g (0,0543 mol) 4-chlor-2-aminobenzothiazol, 6,45 g '0,109 mol) 85#'s hydrazin-hydrat og 3,72 g (0,109 mol) hydrazin-monohydrochlorid omsættes ved fremgangsmåden ifølge eksempel 1. Der fås 99,77 g (90# af det teoretiske) 4-chlor-2-hydrazinobenzothiazol med smeltepunkt 226-229°C. Forsøgsmæssig afprøvning ('titrering) viser en produktrenhed på 96,2#. Omkrystallisation fra isopropanol giver 7,2 g produkt med smeltepunkt 239-24l°c .Example 3 4-Chloro-2-hydrazinobenzothiazole 10.09 g (0.0543 mole) of 4-chloro-2-aminobenzothiazole, 6.45 g '0.109 mole) 85 # of hydrazine hydrate and 3.72 g (0.109 mole) ) hydrazine monohydrochloride is reacted by the procedure of Example 1. 99.77 g (90 # of theory) of 4-chloro-2-hydrazinobenzothiazole are obtained, mp 226-229 ° C. Experimental testing ('titration') shows a product purity of 96.2 #. Recrystallization from isopropanol gives 7.2 g of product, mp 239-24l ° c.
6 1424576 142457
Analyse beregnet for C^H^N^CIS: C = 42,11#, H = 5,03#, N = 21,05#, S = 16,06# og Cl = 17,76#Analysis calculated for C ^H ^N NCIS: C = 42.11 #, H = 5.03 #, N = 21.05 #, S = 16.06 #, and Cl = 17.76 #
Fundet: C = 42,07#, H = 2,94#, N = 20,82#, S = 16,11# og Cl = 17,81#Found: C = 42.07 #, H = 2.94 #, N = 20.82 #, S = 16.11 #, and Cl = 17.81 #
Eksempel 4 4-Methoxy-2-hydrazlnobenzothiazol 5,0 g (0,028 mol) 4-methoxy-2-aminobenzothiazol, 5,3 g (0,057 mol) 85#Ts hydrazin-hydrat og 1,9 g (0,028 mol) hydrazin-monohydrochlorid omsættes ved fremgangsmåden ifølge eksempel 1. Der fås 4,65 g 4-methoxy--2-hydrazinobenzothiazol med smeltepunkt 215-220°C, med en renhed på 97,1# som forsøgsmæssig afprøvet (titrering). Den analytiske prøve (omkrystalliseres fra methanol) har et smeltepunkt på 224-226,5°C.Example 4 4-Methoxy-2-hydrazinobenzothiazole 5.0 g (0.028 mol) 4-methoxy-2-aminobenzothiazole, 5.3 g (0.057 mol) 85 # Ts hydrazine hydrate and 1.9 g (0.028 mol) hydrazine monohydrochloride is reacted by the procedure of Example 1. 4.65 g of 4-methoxy-2-hydrazinobenzothiazole, mp 215-220 ° C, is obtained, with a purity of 97.1 # as experimentally tested (titration). The analytical sample (recrystallized from methanol) has a melting point of 224-226.5 ° C.
Analyse beregnet for CgH^N^OS: C = 49,21#, H = 4,65#, N = 21,52# og S = 16,42#Analysis calculated for CgH ^N₂O: C = 49.21 #, H = 4.65 #, N = 21.52 #, and S = 16.42 #
Funde t: C = 49,25#, H - 4,54#, N = 21,67# og S = 16,40#Found t: C = 49.25 #, H - 4.54 #, N = 21.67 #, and S = 16.40 #
Eksempel 5 4-Methyl-2-hydrazinobenzothiazolExample 5 4-Methyl-2-hydrazinobenzothiazole
En blanding af 11,95 g '0,049 mol) 4-metyl-2-aminobenzothiazol-hydrc bromid og 8,60 g (0,15 mol) 85#'s hydrazin-hydrat i 40 ml ethylengly-col opvarmes under nitrogen til en temperatur på 140°C i 2 timer. Blandingen afkøles til stuetemperatur, og der tilsættes 40 ml vand. Produktet, som begynder at udfælde under afkølingsperioden, filtreres fra, vaskes med vand og tørres i vakuum ved 6o°C. Der iagttages 8,50 g (95# af det teoretiske udbytte) 4-methyl-2-hydrazinobenzothiazol med smeltepunkt 165-168°C. Tyndtlagschromatografi af det rå produkt viser, at det er frit for udgangsmateriale og i det væsentlige rent. Den analytiske prøve har et smeltepunkt på l67-l69°C (efter omkrystallisation fra ethanol).A mixture of 11.95 g (0.049 mole) of 4-methyl-2-aminobenzothiazole hydride bromide and 8.60 g (0.15 mole) of 85 # hydrazine hydrate in 40 ml of ethylene glycol is heated under nitrogen to a temperature of 140 ° C for 2 hours. The mixture is cooled to room temperature and 40 ml of water is added. The product which begins to precipitate during the cooling period is filtered off, washed with water and dried in vacuo at 60 ° C. 8.50 g (95% of theoretical yield) of 4-methyl-2-hydrazinobenzothiazole, mp 165-168 ° C, are observed. Thin-layer chromatography of the crude product shows that it is free of starting material and substantially pure. The analytical sample has a melting point of 167-169 ° C (after recrystallization from ethanol).
Analyse beregnet for CpH^N^S: C = 55,61#, H = 5,06#, N = 25,44# og S = 17,39#Analysis calculated for Cp H 2 N 2 S: C = 55.61 #, H = 5.06 #, N = 25.44 #, and S = 17.39 #
Fundet: C = 55,84#, H = 4,98#, N = 25,44# og S = 17,68#Found: C = 55.84 #, H = 4.98 #, N = 25.44 #, and S = 17.68 #
Eksempel 6 7 142457 6-Methoxy-2-hydrazinobenzothiazol 2,70 g (0,015 mol) 6-methoxy-2-aminobenzothiazol, 1,77 g '0,05 mol) o5$'s hydrazin-hydrat og 1,05 g ''0,015 mol) hydrazin-monohydro-chlorid omsættes ved fremgangsmåden ifølge eksempel 1, hvilket giver 2,0-5 g ^ 90$ af det teoretiske) 6-methoxy-2-hydrazinobenzothiazol med smeltepunkt 172-175°C, som ved titrering viser sig at være 97,0% rent (smeltepunkt er ifølge litteraturen 168-169°C, jfr. USA-patent-skrift nr. 2.073.600).Example 6 7 6-Methoxy-2-hydrazinobenzothiazole 2.70 g (0.015 mole) of 6-methoxy-2-aminobenzothiazole, 1.77 g of 0.05 mole of orazine hydrate and 1.05 g of 0.015 mole of hydrazine monohydrochloride is reacted by the procedure of Example 1 to give 2.0-5 g of $ 90 of the theoretical 6-methoxy-2-hydrazinobenzothiazole, mp 172-175 ° C, which, upon titration, shows say to be 97.0% pure (melting point according to the literature is 168-169 ° C, cf. US Patent No. 2,073,600).
Eksempel 7 6-lVlethylthio-2-hydrazinobenzothiazol 10,0 g (0,05 mol) 6-methylthio-2-aminobenzothiazol, 0,05 g (0,10 mol) 85$'s hydrazin-hydrat og 5»5 g (0,05 mol hydrazin-mono-hydroehlorid omsættes ved fremgangsmåden ifølge eksempel 1, hvilket giver 9,95 g (92,5$ af det teoretiske udbytte) 6-methylthio-2-hydra-zinobenzothiazol med smeltepunkt 175-176°C. Forsøgsmæssig afnrøvning (titrering) viser en produktrenhed på 98,0$.Example 7 6-Ylethylthio-2-hydrazinobenzothiazole 10.0 g (0.05 mole) of 6-methylthio-2-aminobenzothiazole, 0.05 g (0.10 mole) of 85 $ hydrazine hydrate and 5.5 g ( 0.05 moles of hydrazine monohydrochloride are reacted by the procedure of Example 1 to give 9.95 g (92.5 $ of theoretical yield) of 6-methylthio-2-hydrazinobenzothiazole, mp 175-176 ° C. drying (titration) shows a product purity of $ 98.0.
Den analytiske prøve smelter ved 17o-lo0°C (omkrystalliseret fra ethanol).The analytical sample melts at 170 ° C (recrystallized from ethanol).
Analyse beregnet for CyH^N^: C = 45,47$, H - 4,29$, N = 19,89$ og S - 50,50$Analysis calculated for CyH 2 N 2: C = 45.47 $, H - 4.29 $, N = 19.89 $, and S - 50.50 $
Fundet: C = 45,69$, H = 4,50$, N = 19,67$ og S - 50,65$Found: C = $ 45.69, H = $ 4.50, N = $ 19.67, and S - $ 50.65
Eksempel 8-14Examples 8-14
Der gennemføres talrige omsætninger af 4-methyl-2-aminobenzo-thiazol-hydrobromid med hydrazin-hydrat ved fremgangsmåden ifølge opfindelsen, idet opløsningsmidlet varieres. De anvendte opløsningsmidler, reaktionstiderne, reaktionstemperaturerne og udbytterne af produkter er som følger: 8 142457Numerous reactions of 4-methyl-2-aminobenzo-thiazole hydrobromide with hydrazine hydrate are carried out in the process of the invention, varying the solvent. The solvents used, the reaction times, the reaction temperatures and the yields of products are as follows: 8 142457
Opløsningsmiddel Reaktionstid Reaktions- Udbytte af __ _ temperatur produkt diethylenglycol 80 minutter 14Q°C 91/ propylenglycol 2 timer l40°C 93/® 2,3-butandiol 3 timer 125°C 86/ triethanolamin 3 timer 134-140°C 91/ sulfolan 5 1/2 timer 129°C 85/ dimethylsulfoxid 4 timer 125°C >95/ ethylenglycol- 5 1/2 timer 110°C 85/ monomethyletherSolvent Reaction time Reaction Yield of __ temperature product diethylene glycol 80 minutes 14 ° C 91 / propylene glycol 2 hours 140 ° C 93 / 2,3-butanediol 3 hours 125 ° C 86 / triethanolamine 3 hours 134-140 ° C 91 / sulfolane 5 1/2 hours 129 ° C 85 / dimethyl sulfoxide 4 hours 125 ° C> 95 / ethylene glycol 5 1/2 hours 110 ° C 85 / monomethyl ether
Eksempel 15 4-Methyl-2-hydrazinobenzothiazol 10,95 g (O,04 mol) 4-methyl-2-dimethylaminobenzothiazol-hydro-bromid, 8,01 g (0,12 mol) 85/'s hydrazin-hydrat og 33 ml ethylenglycol sammenblandes ved stuetemperatur, og blandingen opvarmes til l4o°C under nitrogenatmosfære. Reaktionsblandingen holdes ved denne temperatur natten over. Efter 39 timers reaktionstid afkøles blandingen, fortyndes med 33 ml vand og filtreres til udskillelse af den ønskede 4--methyl-2-hydrazinobenzothiazol-forbindelse. Denne vaskes med vand og tørres i 2 timer ved 65°C i vakuum hvorved fås 5*43 g produkt som svarende til et udbytte på 79/. En NMR analyse af produktet viser, at det indeholder ca. 5-ca. 10% af udgangsmaterialet. Smeltepunkter er 161-166°C.Example 15 4-Methyl-2-hydrazinobenzothiazole 10.95 g (0.04 mol) 4-methyl-2-dimethylaminobenzothiazole hydrobromide 8.01 g (0.12 mol) 85 µg hydrazine hydrate and 33 ml of ethylene glycol is mixed at room temperature and the mixture is heated to 140 ° C under a nitrogen atmosphere. The reaction mixture is kept at this temperature overnight. After 39 hours reaction time, the mixture is cooled, diluted with 33 ml of water and filtered to separate the desired 4-methyl-2-hydrazinobenzothiazole compound. This is washed with water and dried for 2 hours at 65 ° C in vacuo to give 5 * 43 g of product corresponding to a yield of 79 /. An NMR analysis of the product shows that it contains approx. 5-C. 10% of the starting material. Melting points are 161-166 ° C.
Eksempel 16 4-Methyl-2-hydrazinobenzothiazol 8.21 g (0,05 mol) 4-methyl-2-aminobenzothiazol, 1,14 g (0,017 mol) hydrazin-monohydrochlorid, 1,96 g (0,033 mol) 85/’s hydrazin-hydrat og 4l ml ethylenglycol sammenblandes, og blandingen opvarmes under ^-atmosfære til 140°C. Disse reaktionsbetingelser fortsætter man med i 15 timer. Derpå tillades reaktionsblandingen at afkøle langsomt til stuetemperatur, og -udelukkende af bekvemmelighed- opbevares den under N2~atmosfære natten over. 45 ml vand tilsættes til reaktionsblandingen om morgenen for at fremtvinge krystallisation. Derpå filtreres reaktionsblandingen for at fraskille den ønskede 4-methyl-2-hydrazinobenzothiazol-forbindelse. Den tørres i vakuum natten over ved 6o°C. Udbyttet er 9 142467 8,00 g svarende til i-:9# af det teoretiske, og produktets smeltepunkt er 143-Ir)l°c. Ikke-vandig titrering viser, at produktet er o5,8# rent.Example 16 4-Methyl-2-hydrazinobenzothiazole 8.21 g (0.05 mole) of 4-methyl-2-aminobenzothiazole, 1.14 g (0.017 mole) of hydrazine monohydrochloride, 1.96 g (0.033 mole) of 85 µg hydrazine Hydrate and 4 ml ml of ethylene glycol are mixed and the mixture is heated under 140 atmosphere to 140 ° C. These reaction conditions are continued for 15 hours. The reaction mixture is then allowed to cool slowly to room temperature and, for convenience only, is stored under N 2 atmosphere overnight. 45 ml of water is added to the reaction mixture in the morning to force crystallization. The reaction mixture is then filtered to separate the desired 4-methyl-2-hydrazinobenzothiazole compound. It is dried in vacuo overnight at 60 ° C. The yield is 9.00 g corresponding to i: 9 # of theory, and the melting point of the product is 143 ° C. Non-aqueous titration shows that the product is o5.8 # pure.
Eksempel 17 4-Chlor-2-hydrazinobenzothiazol 2,0 g (0,108 mol) 4-chlor-2-aminobenzothiazol opløses i 10 ml diethylenglycol-monomethylether, og der tilsættes 0,9 ml koncentreret HC1 under omrøring. 1,92 g 8578 s hydrazin-hydrat sættes derefter til blandingen, og reaktionsblandingen opvarmes til 110°C under N^-atmos-fære på oliebad. Reaktionen fortsættes i 22 timer, idet slutreaktions-temperaturen er 120°C. 4-chlor-2-hydrazinobenzothiazol-produktet isoleres ved tilsætning af vand og fraskilleIse ved filtrering, hvorved fås 1,69 g produkt {!%%' s udbytte) med smeltepunkt 232-235°C·Example 17 4-Chloro-2-hydrazinobenzothiazole 2.0 g (0.108 mol) of 4-chloro-2-aminobenzothiazole are dissolved in 10 ml of diethylene glycol monomethyl ether and 0.9 ml of concentrated HCl is added with stirring. 1.92 g of 8578 s of hydrazine hydrate is then added to the mixture and the reaction mixture is heated to 110 ° C under N 2 atmosphere on an oil bath. The reaction is continued for 22 hours with the final reaction temperature being 120 ° C. The 4-chloro-2-hydrazinobenzothiazole product is isolated by the addition of water and separated by filtration to give 1.69 g of product (% yield), mp 232-235 ° C.
Eksempel 18 9-Methyl-2-hydrazinoben2othiazolExample 18 9-Methyl-2-hydrazinobenzylothiazole
Til en suspension af 5>0 g (0,03 mol) 4-methyl-2-aminobenzothia-zol i 20 ml ethylenglycol sættes 5,4 g (0,09 mol) 85^'s hydrazinhydrat og 2,75 g (0,046 mol) eddikesyre. Blandingen opvarmes til 126°C under ^“atmosfære i 3 timer. Efter afkøling og fortynding med ca. et halvt rumfang vand krystalliserer produktet. Der fås 4,73 g (87(3 af det teoretiske) 4-methyl-2-hydrazinobenzothiazol. Produktet identificeres ved tyndtlagschromatografi og viser sig at være praktisk taget. rent.To a suspension of 5> 0 g (0.03 mole) of 4-methyl-2-aminobenzothiazole in 20 ml of ethylene glycol is added 5.4 g (0.09 mole) of 85 L of hydrazine hydrate and 2.75 g (0.046 mole) acetic acid. The mixture is heated to 126 ° C under 3 atmosphere for 3 hours. After cooling and dilution with approx. half a volume of water crystallizes the product. 4.73 g (87 (3 of theory) of 4-methyl-2-hydrazinobenzothiazole) is obtained. The product is identified by thin layer chromatography and proves to be practically pure.
Eksempel 19 4-Methyl-2-hydrazinobenzothiazol 443 g (1,71 mol) 4-methyl-2-methylaminobenzothiazol-hydrobromid sættes under omrøring til 1,7 liter ethylenglycol. 400 g (6,75 mol) 85;* hydrazin-hydrat tilsættes i flere portioner. Reaktionsblandingen opvarmes til 130-135°C under ^-atmosfære og holdes ved denne temperatur i ca. 4 timer og afkøles derefter langsomt under omrøring. Produktet isoleres ved tilsætning af vand og skilles fra ved filtrering. Det tørres dernæst natten over i vakuumovn, hvilket giver 275,5 g (90$3*s udbytte) 4-methyl-2-hydrazinobenzothiazol. nmr-spektret stemmer overens med et referancespektrum og viser intet bevis for tilstedeværelse af udgangsmateriale eller anden urenhed. Ikke-vandig titrering * 142457 ίο viser, at produktet er 97*5% rent.Example 19 4-Methyl-2-hydrazinobenzothiazole 443 g (1.71 mol) of 4-methyl-2-methylaminobenzothiazole hydrobromide are added with stirring to 1.7 liters of ethylene glycol. 400 g (6.75 mol) of 85; * hydrazine hydrate are added in several portions. The reaction mixture is heated to 130-135 ° C under an atmosphere and maintained at this temperature for approx. 4 hours and then cool slowly with stirring. The product is isolated by the addition of water and separated by filtration. It is then dried overnight in a vacuum oven to give 275.5 g (90 $ 3 * s yield) of 4-methyl-2-hydrazinobenzothiazole. the nmr spectrum corresponds to a reference spectrum and shows no evidence of the presence of starting material or other impurity. Non-aqueous titration * 142457 shows that the product is 97 * 5% pure.
Forbindelser fremstillet ifølge den foreliggende opfindelse og med den almene formel R-—— ^-NH-NHa hvori R og n har de ovenfor anførte betydninger, er kendt som anvendelige som udgangsmaterialer til fremstilling af s-triazolo-(3,4-b)-benzo-thiazol'-forbindelser med formlen <ν\ .11Compounds prepared according to the present invention and of the general formula R - - - -NH-NHa wherein R and n have the meanings given above are known as useful as starting materials for the preparation of s-triazolo- (3,4-b) -benzo-thiazole'-compounds of formula <ν \ .11
R*-C=NR * -C = N
2 hvori R er hydrogen eller lavere alkyl såsom methyl.2 wherein R is hydrogen or lower alkyl such as methyl.
Uanset ad hvilken synthesevej s-triazolo0,4-b)benzothiazol-forbindelserne er fremstillet, er de anvendelige som midler til bekæmpelse af plantepathogene organismer, især fungale organismer og især den organisme, der fremkalder rissvidning (Pirieularia oryzae).Irrespective of the synthesis pathway of the s-triazolo0,4-b) benzothiazole compounds, they are useful as agents for controlling plant pathogenic organisms, especially fungal organisms and especially the organism that causes rice widening (Pirieularia oryzae).
Forbindelserne, der skal anvendes som udgangsmaterialer ved fremgangsmåden ifølge den foreliggende opfindelse, har formlen X~ø[^X(R,)a hvori R, R·*" og n har de ovenfor anførte betydninger. Det er tilgængelige forbindelser. Mange er kommercielt tilgængelige. Alle kan syntetiseres ved kendte syntesemetoder. En bekvem metode er Hugerschoffs reaktion: se Heterocyclic Compounds, bind 5 udgivet af Elderfield Cpå John Wiley & Sons, Inc.,.New York, 1957) side 506.The compounds to be used as starting materials in the process of the present invention have the formula X ~ ø [X (R,) a wherein R, R · and n are as defined above. Compounds available are available. Many are commercially available. All can be synthesized by known synthetic methods. A convenient method is Hugerschoff's reaction: see Heterocyclic Compounds, Vol. 5 published by Elderfield C, on John Wiley & Sons, Inc., New York, 1957) page 506.
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|---|---|---|---|
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| JPS5350330A (en) * | 1976-10-19 | 1978-05-08 | Mitsui Toatsu Chem Inc | Controlling agents against bacterial leaf blight on rice plants |
| EP0028406A1 (en) * | 1979-10-31 | 1981-05-13 | Gaf Corporation | Copolymerizable, ultraviolet light absorber N-benzothiazoloazines |
| DE2947489A1 (en) * | 1979-11-24 | 1981-06-04 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING 2,2'-IMINO-BIS-BENZTHIAZOLE COMPOUNDS |
| EG17986A (en) * | 1985-08-09 | 1991-08-30 | Lilly Co Eli | Synthesis of tricyclazole |
| CN103833674B (en) * | 2014-03-13 | 2016-01-27 | 杭州师范大学 | A kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole |
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