CA1249601A - Process for the preparation of substituted phenylhydrazines - Google Patents
Process for the preparation of substituted phenylhydrazinesInfo
- Publication number
- CA1249601A CA1249601A CA000498246A CA498246A CA1249601A CA 1249601 A CA1249601 A CA 1249601A CA 000498246 A CA000498246 A CA 000498246A CA 498246 A CA498246 A CA 498246A CA 1249601 A CA1249601 A CA 1249601A
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- Prior art keywords
- process according
- formula
- hydrazine
- reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
- C07D231/38—Nitrogen atoms
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
- C07D231/38—Nitrogen atoms
- C07D231/40—Acylated on said nitrogen atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the preparation of a substituted phenyl-hydrazine by the reaction of a substituted chlorobenzene with hydrazine or hydrazine hydrate. Compounds of the general formula are reacted with hydrazine or hydrazine hydrate to form compounds of the formula I
A process for the preparation of a substituted phenyl-hydrazine by the reaction of a substituted chlorobenzene with hydrazine or hydrazine hydrate. Compounds of the general formula are reacted with hydrazine or hydrazine hydrate to form compounds of the formula I
Description
~2496(~1 The invention relates to a new process for the preparation of substituted phenylhydrazines uhich can be used as intermed;ate products for the synthesis of herbi-cidal active compounds.
It is a~ready known that substituted phenyLhydra-zines are obtained when substituted anilines are first diazotised with sodium nitrite in the presence of an acid and then reduced in a second stage, for example ~ith tin-II
chloride, aqain in the presence of an acid Scompare, for example, Houben-~eyl, "Methoden der organischen Chemie"
~"Methods of Organic Chemistry"), Yolume X, 2; page 203, Thieme Verla~ Stuttgart 1967).
The d~sadvantage of this process is that the yield and purity of the reaction products thus obtainable is often not satisfactory, a fact uhich ;s due on the one hand to the general disadvantages of a multi-stage reaction method and on the other hand ;t is also attributable to special problems in both stages. Thus, for example, the preparation of the diazonium salts ~1st stage), uhen using, as start~ng compounds, anilines ~ith hydrophobic substitu-ents, often succeeds only poorly in the required aqueous med1um. A further difficulty in the diazotisation is that side-reactions, such as, for example, azo coupling, are possible and do also occur. The reduction of the diazonium salts ~2nd stage) also often does not take place completely, and this again contributes to contamination and lo~ering of yield.
It has b-en found that cubstituted phenylhydrazines of the formula (S) R1 Cl R3-(X)n ~ NH-NH2 ~I) ~2 Cl Le A 23 492-Foreign Countries lZ49601
It is a~ready known that substituted phenyLhydra-zines are obtained when substituted anilines are first diazotised with sodium nitrite in the presence of an acid and then reduced in a second stage, for example ~ith tin-II
chloride, aqain in the presence of an acid Scompare, for example, Houben-~eyl, "Methoden der organischen Chemie"
~"Methods of Organic Chemistry"), Yolume X, 2; page 203, Thieme Verla~ Stuttgart 1967).
The d~sadvantage of this process is that the yield and purity of the reaction products thus obtainable is often not satisfactory, a fact uhich ;s due on the one hand to the general disadvantages of a multi-stage reaction method and on the other hand ;t is also attributable to special problems in both stages. Thus, for example, the preparation of the diazonium salts ~1st stage), uhen using, as start~ng compounds, anilines ~ith hydrophobic substitu-ents, often succeeds only poorly in the required aqueous med1um. A further difficulty in the diazotisation is that side-reactions, such as, for example, azo coupling, are possible and do also occur. The reduction of the diazonium salts ~2nd stage) also often does not take place completely, and this again contributes to contamination and lo~ering of yield.
It has b-en found that cubstituted phenylhydrazines of the formula (S) R1 Cl R3-(X)n ~ NH-NH2 ~I) ~2 Cl Le A 23 492-Foreign Countries lZ49601
- 2 -in uh;ch R1 and R2 represent hydro~en or chlorine, R3 represents halogenoalkyl, X represents oxygen, sulphur, sulphinyL or sulphonyl and n represents a number 0 or 1, are obtained ~hen substituted chlorobenzenes of the for~ula ~II) R1 Cl R3-¦X)n ~ -Cl ~II) R Cl in ~hich R~, R2, R3, X and n have the abovementioned meanings~
are reacted ~ith hydrazine or hydrazine hydrate in the pre-sence of a diluent, if appropriate under elevated pressure, 5 at temperatures between 60C and 160C.
It must be regarded as distinctly surprising that ~ith the aid of the process according to the invention the desired substituted phenylhydrazines are obtained in h;gh yields and good purity, since according to the state of the 0 art it uas not to be expected that, ~iven that in the starting product of the formula ~II) there are at least three chlorine atoms available for the substitution reac-tion according to the invention, only one product ~ould be formed selectively.
The process according to the invention has a number of advantages. These include, for examp~e, the single-stage reaction method in an organic so~vent, ~hereby so~u-bility problems ~hen using hydrophobic starting materials are avoided. The expensive isolation of intermediate pro-ducts is a~so avoided. ~ further advantage of the process according to the invention is the easy accessibil~ty of the substituted chlorobenzenes of the formula ~II) uhich can be Le A 23 492-Foreign Countries used as starting compounds.
~ith the aid of the process according eO the inven-tion, there are preferably obtained those substituted phenyLhydrazines of the formula (I) 5 in ~h;ch R1 and R2 represent hydrogen or chlorine, X represents oxygen, sulphur, sulphinyl or sulphony~, R3 represents straight-chain or branched halogeno-a~kyl ~ith 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and n represents a number 0 or 1.
Particularly preferentially, there are obtained compounds of the formula ~) in ~hich R1 and R2 represent hydrogen or chlorine, R3 represents difluoromethyl, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluoro-chloronethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, tetrafluorochloroethyl, tri-fluorochloroethyl, trifluorodichloroethyl, di-fluorotrichloroethyl, difluorotriohlorocthyl, di-p~ fluorodichloroethyl, tetrachlorofluoroethyl or pentachloroethyl, X represents sulphur, sulphinyl or sulphonyl and 2S n represents a number 0 or 1.
Ifo for example, 1,2,3-trichloro-5-trifluoromethyl-benzene and hydrazine hydrate are used as starting mater-ials, the course of the reaction in the process accordin~
to the invention can be represented by the follo~ing 30 equation: ~
Le A 23 492 -Foreign Countries 12~g601 J:l 2N-N~2 ~ ~ase -~Cl Cl fl F3C ~ -NH-N~2 The formula ~II) provides a general definition of the substituted chlorobenzenes required as starting mater-ials for carry;ng out the process according to the inven-tion.
Preferred compounds of the formula ~II) are those in ~h~ch R1, R2, R3, X and n represent those radicals ~hich have already been ment;oned as preferred for these subst;tuents and ind;ces in the context of the description of the end products of the formu~a tI).
The substituted chlorobenzenes of the formula ~II) are knoun (compare, for example, DE-OS ~German Published Specificat;on) 2,644,641; DE-OS (German Publ;shed Specifi-cation) 2,333,848; Japanese Patent 49/2108; J. Fluorin*Chem. 9, 113-126 ~1977); Ind. Eng. Chem. 39, 378-380 ~1947)) or can be prepared analogously to processes knoun in prin-ciple. The process according to the invention can, ;f des;red, be carried out in the presence of a suitable diluent. PrefPrably, diluents are used in the process according to the ;nvent;on.
Suitable diluents are v;rtually all inert organ;c so~vents. These in particular include polar or dipolar aprotic solvents such as a~cohols, for example methanol, ethanol, n- or i-propanol or ethylene glycol, or ethers, such as, for example, dioxane, d;methoxyethane or d;ethyl-ene glycol d;methyl ether, or sulphox;des, such as, for example, d;methylsulphox;de. Part;cularly preferred dilu-ents are dioxane and n-propanol.
Le A 23 492-Foreign Countries lZ4~601 Further particularly preferred di~uents are ~eakl~
basic solvents, such as, for example, pyridine.
The process accordinq to the invention is in general carried out at temperatures betueen ~60C and ~160C. The temperature range of bet~een ~80C and ~140C, especially betueen ~100C and 120C, is preferred. The reactions are ;n general carried out under normal prcssure.
Ho~ever, depending on the boiling point of the di~uent used it can also be of advantage to appl~ the pressure required to reach the requisite reaction temperature. In these cases, the process is in general carried out in the pres-sure range of from 1 to 30 bar, preferably from 1 to 20 bar.
To carry out the process according to the inven-tion, 1.0 to 10.0 moles, preferab~y 2.0 to 8.0 ~oles, especially 3.0 to 7.0 moles, of hydrazine or hydrazine hydrate are in general emp~oyed per mole of substituted chlorobenzene of the formula ~II).
The reaction is carried out by heating the reac-tants, dissolved in the appropriatc diluent, to the requi-site reaction temperature for 8 to 60 hours (the course of the reaction during this time can be folloued by, for example, gas chromatography); uhen using lou-boiling dilu-ents it ~ay be necessary to uork under pressure in order to reach the required reaction temperature.
For uorking up, the solvent is distilled off~ the residue is taken up in uater, the mixture is brought to pH 10 uith aqueous sodium hydroxide solution and the pro-duct is extracted ~ith a ~ater-immiscible solvent. The combined organic phases are, if necessary, a~ain uashed ~ith concentrated aqueous sodium chloride solution, dried and concentrated in vacuo.
The crude products of the formula ~I), thus obtained, can either be purified by distillation or be crystallised from a suitable solvent, such as, for example, n-hexane.
The substituted phenylhydrazines of the formula ~I) Le ~ 23 492-Foreign Countries 124s6al are valuable intermediate products and are suitable, for example, for the synthesis of herbicidally active 5-acyl-amino-1-phenyl-pyrazoles, which are described, for example, in German published patent applications DE-OS 3,402,308 or DE-OS 34 20 985.9.
Thus, new 5-aminopyrazoles of the formula (III) ~ NH2 ¦ (III) C ~ ~ Cl R ~ R
tX,)n R
in which R4 represents cyano or alkylaminocarbonyl and Rl, R2, R3, X and n have the abovementioned meaning are obtained when acrylonitrile derivatives of the formula (IV) ~ CN
C2H O-CH=C R4 (IV) in which R4 has the abovementioned meaning and phenylhydrazines of the formula (I) /
R3-(X)n ~ NH-NH2 (I) R Cl in which R , R2, R3, X and n have the abovementioned : - 6 -12~9601 meaning are either initially reacted in a first stage, if approp-riate in the presence of a diluent, such as, for exampLe, glacial acetic acid or ethanol, and, if appropriate, in the presence of a reaction assistant, such as, for exanple, sod;um acetate, at temperatures bet~een -20C and ~20C, to give the phenylhydrazine derivatives of the formula CV) R Cl ~3-lX~ H-CH=C ~ (V) in uh;ch R~, R2, R3, R~, X and n have the abovement;oned meaning these then being cyclised in a second stage, if appropriate in the presence of a diluent, such as, for example, ethyl-ene ~lycol monoethyl ether, at te~peratures betueen ~50C
and ~150C, or are directly cyclised in a single reaction step, ~ithout isolation of the intermediate stage of the formula ~V), if appropriate in the presence of a diluent such as, for example, ethylene glycol monoethyl ether or ethanol, at temperatures bet~een ~50t and ~150C.
~he acrylon~trile derivatives of the formula ~IV) are knoun ~compare European Patent 34,945 or DE-OS ~6erman Published Specification) 3,129,429).
Neu herbicidally active substituted 5-acylamino-1-phenylpyrazoles of the formula ~VI) _____,R4 ~`N ~ ~-CO-R
Cl ~ Cl ~VI) R~Rt (X) ,3n Le ~ 23 492-Forei~n ~ountrie~
124~960~
in ~hich R1, RZ, R3, R4, X and n have the abovementioned meaning and R5 represents hydrogen, or alkyL, alkenyl or aLkinyL, or opt;onaLLy substituted cycLoalkyL, or alkoxyalkyl, alkylthioalkyl or halogenoalkyl, or optionally substituted aryl are obtained uh~n 5-s~inop~ra~oLes of the formuLa tI~I) N~N NH2 ~III) Cl ~ Cl R
(X)n R
in which R1, R2, R3, R4, X and n have the abovementioned meaning are reacted ~ith acyLating agents of the formuLa tVII) R5 - C0 - A (VII) 15 in which R5 has the abovementioned meaning and A represents an ac~ivating leaving group, such as, for exampLe, haLogen, or a radicaL R5-Co-o, wherein 2û R5 has the abovementloned meaning, if appropriate in the presence of a d;Luent, such as, for exampLe, chLoroform, and, if appropriate, ln the presence of an acid acceptor, such as, for example, triethyLamine, at temperatures between -20 and +150C.
~o carry out this process, in general 1 to 20 moles, preferabLy 1 to 15 moLes, of acyLating agent of the formula Le A 23 492 -Foreign Countries 124~601 _ 9 _ (VII) snd, in general, 1 to 3 mo~es, preferabLy 1 to 2 mo~es, of acid acceptor are employed per mole of S-amino-pyrazoLe of the formula ~III). The conduct of the reaction, uorking up and isolation of the end products of the formula ~VI) are performed in the customary manner. The acylating agents of the formula ~VII) are generally kno~n.
PrcParation Exaoples Example 1 ~3C~NH-NH2 Cl 6.2 ~ ~0.025 ~ole) of 3,4,5-trichloro-trifluoro-methylbenzene and 6.25 9 ~0.125 ~ole) of hydrazine hydrate in 12 ml of pyridine are heated at 115-120C, under reflux, for 48 hours. To uork up the nixture, the solvent is dis-tilled off, the residuc is taken up in uater and three extractions, each with about 30 ml of methylene chloride, are carried out. The combined organic phases are dried over magnesium sulphate, concentrated in vacuo and then distilled.
5.1 9 ~83X of theory)of 2,6-dichloro-4-trifluoro-~ethylphenylhydrazine, of meltin~ point 56 - 57C, are obtained, the naterial being 90X pure as determined by gas chromatography.
Example 2 C ~
~ 3C-~_NH_NH2 C ~ _ 200 9 (0.704 mole) of 2,3,4,5-tetrach~oro-tri-fluoromethylbenzene and 24û ml (247.2 9/4.94 moles) of hydrazine hydrate in 500 ml of dioxane are heated at 100-105C, under reflux, for 14 hours. The heavy ~aqueous) phase is separated off from the cooled t~o-phase reaction Le ~ 23 492-Foreign Countries 124~6(~
-- ~o --m;xture and the or~anic phase is concentrated to dryness in vacuo. The residue is suspended in 600 ml of water and 100 ml of methylène chloride, the pH is brought to 10 ~ith 10X strength aqueous sodium hydroxide solution, and the mixture is slowly heated to bet~een 30C and 35C, in the course of ~hich t~o clear phases form from the cloudy suspension. The nixture is alloued to cool to roon tem-perature, the organic phase is separated off, ~ashed ~;th 200 ml of concentrated aqueous sod;um chlor;de solut;on and dried over ma3nesium sulphate, and the solvent is removed in vacuo. The crude product, in 370 ml of boiling hexane, is stirrcd for 3 to 4 hours, the mixture is then cooled for 15 hours at bet~een 0C and 5C and is filtered cold, and the f;lter residue is dried in vacuo at 50C for 2 to 3 hours.
146 9 ~71.2X of theory) of 2,3,6-tr;chloro-4-tr;-fluoromethyl-phenylhydrazine, of nelting point 67 to 70C, are obtained, the material be;ng 96X pure as determined by gas chromatography.
Example 3 0 _ CL
F~C-S~NH-NH2 O C~
85 ~ tO.27 mole) of 1,2,3-trichloro-5-trifluoro-methylsulphonylbenzene in 68 ml of dioxane are added drop~ise to 41 9 (0.82 mole) of hydraz;ne hydrate in 136 ml of d;oxane at bet~een 20C and 40C, u;th stirring. After comple-tion of the addition, the mixture is stirred under reflux for 2 hours at 100-105C. ~hen the reaction mixture has cooled, water is added and the resu~ting precipitate is filtered off, dried and recrystallised from toluene.
68 9 ~81X of theory) of 2,6-dichloro-4-trifluoro-methylsulphonyl-phenylhydrazine of melting point 135 to 137c, are obta;ned.
The follo~;ng substituted phenylhydraz;nes of the Le A 23 492-Foreign Countries formula ~I) can be obtained analogously and in accordance ~ith the Qeneral ~tat-nents concernino the preparation method:
Rt Cl R3-(X)n ~ NH-NH2 ~I) R2 Cl 5 Table 1 Exampl eR1 R2 X R3 n melting point / C
No I~L.~
4 H ~ S CF3 1 60 - 62 Cl Cl S c~3 6 Cl H S02 CF3 B H H S02 CClF2 9 H ~ SO CF3 Preparation of the st~rtin9 co-Poun-d O C~
~3C-S~=~CI
A m;xture of 1,123 g ~4.6 molcs) of 4-trifluoro-methylsulphonylchlorobenzene, 11.5 g ~0.13 mole) of iron-~II) sulphide and 11.5 g ~0.045 mole) of iodine is treated ~ith chlorine at bet~een 100C and 120C. The reaction is follo~ed by ~as chromatography and is stopped ~hen the mixture contains 36% of the desired product. ~orking up is by fractional d;stillation.
554 g ~38.5X of theory) of 3,4,5-tr;chlorotri-fluoromethylsulphonylbenzene, of boiling point 143C at 22 mbar and melting point 102C to 103C, are obtained.
Le A 23 492-Foreign Countries lZ~9601 Example of the proparati~n of ~ h~rbieidaLly ~ctive compound ,~
H~N ~ NH-C0-e2~5 ~VI-1) tl ~ Cl ~f~
To a suspension of 3.5 9 ~0.01 mole) of 5-amino-4-cyano-1-~2,6-dichloro-4-tr;fluoromethylthio-phenyl)-pyra-S zole in 30 ml of chloroform there are added at 0C, ~ithstirrln~, f1rst tO ml 10.11 mole) of prop;onyl chlor;de and thereafter 1.8 ml ~0.02 mole) of pyr;dine in 15 ml of chloroform. A clear solut;on is obta;ned, ~hich after completion of the addition is stirred for a further 20 hours at room temperature. The solution thus obtained is evaporated to dryness. For ~orkin~ up, the residue is taken up ;n S0 ml of ethanol, aqueous ammonia ;s added until an alkaline reaction is obtained, the m;xture ;s heated for 10 m;nutes under reflux, the volatile const;tu-ents are removed ;n vacuo, the residue 1s taken up in100 ml of chloroform, the solution is ~ashed u;th ~ater, then u;th 2N aqueous hydrochloric ac;d and aga;n with uater and is dried over sodium sulphate, and the solvent is removed in vacuo. 3.4 9 ~83X of theory) of 5-propionyl-am;no-4-cyano-1-~2,6-d;chloro-4-trifluoromethylth;ophenyl)-pyrazole, of me~ting point 153 to 156C, are obtained.
Preparatlon of the start;ng compounds Cl ~C-S~ ~ -~H ~ c~ y t~ tN ~V-1) Cl 6.1 9 (0.05 mole) of ~thoxymethylenenalonodinitrile are added, ~ith stirring, to a suspension of 13.9 y (0.05 mole) of (2,6-dichloro-4-trifluoromethylthio)-pheny~hydra-Le A 23 492 -Foreign Countries 12496~)1 zine and 2.1 ~ C0.025 mole) of sodium acetate in 25 nL of g~acial acetic acid. ~fter compLetion of the addition, stirring is continued for an hour at room temperature and the solid thus obtained is filtered off, ~ashed succes-siveLy ~ith ~ater, aqueous sodium bicarbonate solution andagain uith uater, and then dried. 15.8 ~ ~89X of theory) of 1-~2,2-dicyanoethen-1-yl)-2-~2,6-dichloro-4-trifluoro-~ethylthiophenyl)-hydrazine of meltlng point 160C are obtained.
____", tN
Nb`~3-- N 112 Cl R~ Cl (lII-l) SCF~
14.1 ~ ~0.04 nole) of 1-t2,2-dicyanoethen-1-yl)-2-~2,6-dichloro-4-trifluoromethylth;o-phenyl)-hydrazine in 30 ml of ethylene glycol monoethyl ether are heated under reflux for 2 hours. The hot solution is treated ~ith active charcoal, filtered and diluted ~ith 60 ml of ~ater.
The precipltate uhich separates out is filtered off and dried. 9.8 9 ~70Z of theory) of 5-amino-4-cyano-1-~2,6-dichloro-4-trifluoronethylthiophenyl)-pyrazole, of melting polnt 185 to 187C, are obtained.
Use ExanPle In the use example ~hich follo~s, the compound sho~n belo~ is employed as the comparison substance:
CN
~ .
N~N~ NH-tO-c2Hs t~ ~ Cl (~) 4-Cyano-5-propionylam1no-1-(2,4,6-trichlorophenyl)-pyrazole ~kno~n from DE-OS ~6erman Published Specification) 3,226,513).
Le ~ 23 492-Foreign Countries 12~9601 Example A
Pre-emergence test SoLvent: 5 parts by we;ght of acetone Emuls;fier: 1 part by weight of aLkyLaryL poLygLycoL ether To produce a suitabLe preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of soLvent, the stated amount of emuL-sifier is added and the concentrate is diluted with ~ater to the desired concentration.
Seeds of the test plants are so~n in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, onLy the amount of active compound appLied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in X damage in comparison to the development of the untreated control. The figures denote:
OX = no action ~like untreated controL) 100X = total destruction In this exampLe the compound according to Preparation Example ~VI-I), for example, exhibits a distinct superiority in herbicidal activity and in crop pLant seLectivity compared to the prior art; this is particuLarLy true of wheat.
Le A 23 492-Foreign Countries
are reacted ~ith hydrazine or hydrazine hydrate in the pre-sence of a diluent, if appropriate under elevated pressure, 5 at temperatures between 60C and 160C.
It must be regarded as distinctly surprising that ~ith the aid of the process according to the invention the desired substituted phenylhydrazines are obtained in h;gh yields and good purity, since according to the state of the 0 art it uas not to be expected that, ~iven that in the starting product of the formula ~II) there are at least three chlorine atoms available for the substitution reac-tion according to the invention, only one product ~ould be formed selectively.
The process according to the invention has a number of advantages. These include, for examp~e, the single-stage reaction method in an organic so~vent, ~hereby so~u-bility problems ~hen using hydrophobic starting materials are avoided. The expensive isolation of intermediate pro-ducts is a~so avoided. ~ further advantage of the process according to the invention is the easy accessibil~ty of the substituted chlorobenzenes of the formula ~II) uhich can be Le A 23 492-Foreign Countries used as starting compounds.
~ith the aid of the process according eO the inven-tion, there are preferably obtained those substituted phenyLhydrazines of the formula (I) 5 in ~h;ch R1 and R2 represent hydrogen or chlorine, X represents oxygen, sulphur, sulphinyl or sulphony~, R3 represents straight-chain or branched halogeno-a~kyl ~ith 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and n represents a number 0 or 1.
Particularly preferentially, there are obtained compounds of the formula ~) in ~hich R1 and R2 represent hydrogen or chlorine, R3 represents difluoromethyl, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluoro-chloronethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, tetrafluorochloroethyl, tri-fluorochloroethyl, trifluorodichloroethyl, di-fluorotrichloroethyl, difluorotriohlorocthyl, di-p~ fluorodichloroethyl, tetrachlorofluoroethyl or pentachloroethyl, X represents sulphur, sulphinyl or sulphonyl and 2S n represents a number 0 or 1.
Ifo for example, 1,2,3-trichloro-5-trifluoromethyl-benzene and hydrazine hydrate are used as starting mater-ials, the course of the reaction in the process accordin~
to the invention can be represented by the follo~ing 30 equation: ~
Le A 23 492 -Foreign Countries 12~g601 J:l 2N-N~2 ~ ~ase -~Cl Cl fl F3C ~ -NH-N~2 The formula ~II) provides a general definition of the substituted chlorobenzenes required as starting mater-ials for carry;ng out the process according to the inven-tion.
Preferred compounds of the formula ~II) are those in ~h~ch R1, R2, R3, X and n represent those radicals ~hich have already been ment;oned as preferred for these subst;tuents and ind;ces in the context of the description of the end products of the formu~a tI).
The substituted chlorobenzenes of the formula ~II) are knoun (compare, for example, DE-OS ~German Published Specificat;on) 2,644,641; DE-OS (German Publ;shed Specifi-cation) 2,333,848; Japanese Patent 49/2108; J. Fluorin*Chem. 9, 113-126 ~1977); Ind. Eng. Chem. 39, 378-380 ~1947)) or can be prepared analogously to processes knoun in prin-ciple. The process according to the invention can, ;f des;red, be carried out in the presence of a suitable diluent. PrefPrably, diluents are used in the process according to the ;nvent;on.
Suitable diluents are v;rtually all inert organ;c so~vents. These in particular include polar or dipolar aprotic solvents such as a~cohols, for example methanol, ethanol, n- or i-propanol or ethylene glycol, or ethers, such as, for example, dioxane, d;methoxyethane or d;ethyl-ene glycol d;methyl ether, or sulphox;des, such as, for example, d;methylsulphox;de. Part;cularly preferred dilu-ents are dioxane and n-propanol.
Le A 23 492-Foreign Countries lZ4~601 Further particularly preferred di~uents are ~eakl~
basic solvents, such as, for example, pyridine.
The process accordinq to the invention is in general carried out at temperatures betueen ~60C and ~160C. The temperature range of bet~een ~80C and ~140C, especially betueen ~100C and 120C, is preferred. The reactions are ;n general carried out under normal prcssure.
Ho~ever, depending on the boiling point of the di~uent used it can also be of advantage to appl~ the pressure required to reach the requisite reaction temperature. In these cases, the process is in general carried out in the pres-sure range of from 1 to 30 bar, preferably from 1 to 20 bar.
To carry out the process according to the inven-tion, 1.0 to 10.0 moles, preferab~y 2.0 to 8.0 ~oles, especially 3.0 to 7.0 moles, of hydrazine or hydrazine hydrate are in general emp~oyed per mole of substituted chlorobenzene of the formula ~II).
The reaction is carried out by heating the reac-tants, dissolved in the appropriatc diluent, to the requi-site reaction temperature for 8 to 60 hours (the course of the reaction during this time can be folloued by, for example, gas chromatography); uhen using lou-boiling dilu-ents it ~ay be necessary to uork under pressure in order to reach the required reaction temperature.
For uorking up, the solvent is distilled off~ the residue is taken up in uater, the mixture is brought to pH 10 uith aqueous sodium hydroxide solution and the pro-duct is extracted ~ith a ~ater-immiscible solvent. The combined organic phases are, if necessary, a~ain uashed ~ith concentrated aqueous sodium chloride solution, dried and concentrated in vacuo.
The crude products of the formula ~I), thus obtained, can either be purified by distillation or be crystallised from a suitable solvent, such as, for example, n-hexane.
The substituted phenylhydrazines of the formula ~I) Le ~ 23 492-Foreign Countries 124s6al are valuable intermediate products and are suitable, for example, for the synthesis of herbicidally active 5-acyl-amino-1-phenyl-pyrazoles, which are described, for example, in German published patent applications DE-OS 3,402,308 or DE-OS 34 20 985.9.
Thus, new 5-aminopyrazoles of the formula (III) ~ NH2 ¦ (III) C ~ ~ Cl R ~ R
tX,)n R
in which R4 represents cyano or alkylaminocarbonyl and Rl, R2, R3, X and n have the abovementioned meaning are obtained when acrylonitrile derivatives of the formula (IV) ~ CN
C2H O-CH=C R4 (IV) in which R4 has the abovementioned meaning and phenylhydrazines of the formula (I) /
R3-(X)n ~ NH-NH2 (I) R Cl in which R , R2, R3, X and n have the abovementioned : - 6 -12~9601 meaning are either initially reacted in a first stage, if approp-riate in the presence of a diluent, such as, for exampLe, glacial acetic acid or ethanol, and, if appropriate, in the presence of a reaction assistant, such as, for exanple, sod;um acetate, at temperatures bet~een -20C and ~20C, to give the phenylhydrazine derivatives of the formula CV) R Cl ~3-lX~ H-CH=C ~ (V) in uh;ch R~, R2, R3, R~, X and n have the abovement;oned meaning these then being cyclised in a second stage, if appropriate in the presence of a diluent, such as, for example, ethyl-ene ~lycol monoethyl ether, at te~peratures betueen ~50C
and ~150C, or are directly cyclised in a single reaction step, ~ithout isolation of the intermediate stage of the formula ~V), if appropriate in the presence of a diluent such as, for example, ethylene glycol monoethyl ether or ethanol, at temperatures bet~een ~50t and ~150C.
~he acrylon~trile derivatives of the formula ~IV) are knoun ~compare European Patent 34,945 or DE-OS ~6erman Published Specification) 3,129,429).
Neu herbicidally active substituted 5-acylamino-1-phenylpyrazoles of the formula ~VI) _____,R4 ~`N ~ ~-CO-R
Cl ~ Cl ~VI) R~Rt (X) ,3n Le ~ 23 492-Forei~n ~ountrie~
124~960~
in ~hich R1, RZ, R3, R4, X and n have the abovementioned meaning and R5 represents hydrogen, or alkyL, alkenyl or aLkinyL, or opt;onaLLy substituted cycLoalkyL, or alkoxyalkyl, alkylthioalkyl or halogenoalkyl, or optionally substituted aryl are obtained uh~n 5-s~inop~ra~oLes of the formuLa tI~I) N~N NH2 ~III) Cl ~ Cl R
(X)n R
in which R1, R2, R3, R4, X and n have the abovementioned meaning are reacted ~ith acyLating agents of the formuLa tVII) R5 - C0 - A (VII) 15 in which R5 has the abovementioned meaning and A represents an ac~ivating leaving group, such as, for exampLe, haLogen, or a radicaL R5-Co-o, wherein 2û R5 has the abovementloned meaning, if appropriate in the presence of a d;Luent, such as, for exampLe, chLoroform, and, if appropriate, ln the presence of an acid acceptor, such as, for example, triethyLamine, at temperatures between -20 and +150C.
~o carry out this process, in general 1 to 20 moles, preferabLy 1 to 15 moLes, of acyLating agent of the formula Le A 23 492 -Foreign Countries 124~601 _ 9 _ (VII) snd, in general, 1 to 3 mo~es, preferabLy 1 to 2 mo~es, of acid acceptor are employed per mole of S-amino-pyrazoLe of the formula ~III). The conduct of the reaction, uorking up and isolation of the end products of the formula ~VI) are performed in the customary manner. The acylating agents of the formula ~VII) are generally kno~n.
PrcParation Exaoples Example 1 ~3C~NH-NH2 Cl 6.2 ~ ~0.025 ~ole) of 3,4,5-trichloro-trifluoro-methylbenzene and 6.25 9 ~0.125 ~ole) of hydrazine hydrate in 12 ml of pyridine are heated at 115-120C, under reflux, for 48 hours. To uork up the nixture, the solvent is dis-tilled off, the residuc is taken up in uater and three extractions, each with about 30 ml of methylene chloride, are carried out. The combined organic phases are dried over magnesium sulphate, concentrated in vacuo and then distilled.
5.1 9 ~83X of theory)of 2,6-dichloro-4-trifluoro-~ethylphenylhydrazine, of meltin~ point 56 - 57C, are obtained, the naterial being 90X pure as determined by gas chromatography.
Example 2 C ~
~ 3C-~_NH_NH2 C ~ _ 200 9 (0.704 mole) of 2,3,4,5-tetrach~oro-tri-fluoromethylbenzene and 24û ml (247.2 9/4.94 moles) of hydrazine hydrate in 500 ml of dioxane are heated at 100-105C, under reflux, for 14 hours. The heavy ~aqueous) phase is separated off from the cooled t~o-phase reaction Le ~ 23 492-Foreign Countries 124~6(~
-- ~o --m;xture and the or~anic phase is concentrated to dryness in vacuo. The residue is suspended in 600 ml of water and 100 ml of methylène chloride, the pH is brought to 10 ~ith 10X strength aqueous sodium hydroxide solution, and the mixture is slowly heated to bet~een 30C and 35C, in the course of ~hich t~o clear phases form from the cloudy suspension. The nixture is alloued to cool to roon tem-perature, the organic phase is separated off, ~ashed ~;th 200 ml of concentrated aqueous sod;um chlor;de solut;on and dried over ma3nesium sulphate, and the solvent is removed in vacuo. The crude product, in 370 ml of boiling hexane, is stirrcd for 3 to 4 hours, the mixture is then cooled for 15 hours at bet~een 0C and 5C and is filtered cold, and the f;lter residue is dried in vacuo at 50C for 2 to 3 hours.
146 9 ~71.2X of theory) of 2,3,6-tr;chloro-4-tr;-fluoromethyl-phenylhydrazine, of nelting point 67 to 70C, are obtained, the material be;ng 96X pure as determined by gas chromatography.
Example 3 0 _ CL
F~C-S~NH-NH2 O C~
85 ~ tO.27 mole) of 1,2,3-trichloro-5-trifluoro-methylsulphonylbenzene in 68 ml of dioxane are added drop~ise to 41 9 (0.82 mole) of hydraz;ne hydrate in 136 ml of d;oxane at bet~een 20C and 40C, u;th stirring. After comple-tion of the addition, the mixture is stirred under reflux for 2 hours at 100-105C. ~hen the reaction mixture has cooled, water is added and the resu~ting precipitate is filtered off, dried and recrystallised from toluene.
68 9 ~81X of theory) of 2,6-dichloro-4-trifluoro-methylsulphonyl-phenylhydrazine of melting point 135 to 137c, are obta;ned.
The follo~;ng substituted phenylhydraz;nes of the Le A 23 492-Foreign Countries formula ~I) can be obtained analogously and in accordance ~ith the Qeneral ~tat-nents concernino the preparation method:
Rt Cl R3-(X)n ~ NH-NH2 ~I) R2 Cl 5 Table 1 Exampl eR1 R2 X R3 n melting point / C
No I~L.~
4 H ~ S CF3 1 60 - 62 Cl Cl S c~3 6 Cl H S02 CF3 B H H S02 CClF2 9 H ~ SO CF3 Preparation of the st~rtin9 co-Poun-d O C~
~3C-S~=~CI
A m;xture of 1,123 g ~4.6 molcs) of 4-trifluoro-methylsulphonylchlorobenzene, 11.5 g ~0.13 mole) of iron-~II) sulphide and 11.5 g ~0.045 mole) of iodine is treated ~ith chlorine at bet~een 100C and 120C. The reaction is follo~ed by ~as chromatography and is stopped ~hen the mixture contains 36% of the desired product. ~orking up is by fractional d;stillation.
554 g ~38.5X of theory) of 3,4,5-tr;chlorotri-fluoromethylsulphonylbenzene, of boiling point 143C at 22 mbar and melting point 102C to 103C, are obtained.
Le A 23 492-Foreign Countries lZ~9601 Example of the proparati~n of ~ h~rbieidaLly ~ctive compound ,~
H~N ~ NH-C0-e2~5 ~VI-1) tl ~ Cl ~f~
To a suspension of 3.5 9 ~0.01 mole) of 5-amino-4-cyano-1-~2,6-dichloro-4-tr;fluoromethylthio-phenyl)-pyra-S zole in 30 ml of chloroform there are added at 0C, ~ithstirrln~, f1rst tO ml 10.11 mole) of prop;onyl chlor;de and thereafter 1.8 ml ~0.02 mole) of pyr;dine in 15 ml of chloroform. A clear solut;on is obta;ned, ~hich after completion of the addition is stirred for a further 20 hours at room temperature. The solution thus obtained is evaporated to dryness. For ~orkin~ up, the residue is taken up ;n S0 ml of ethanol, aqueous ammonia ;s added until an alkaline reaction is obtained, the m;xture ;s heated for 10 m;nutes under reflux, the volatile const;tu-ents are removed ;n vacuo, the residue 1s taken up in100 ml of chloroform, the solution is ~ashed u;th ~ater, then u;th 2N aqueous hydrochloric ac;d and aga;n with uater and is dried over sodium sulphate, and the solvent is removed in vacuo. 3.4 9 ~83X of theory) of 5-propionyl-am;no-4-cyano-1-~2,6-d;chloro-4-trifluoromethylth;ophenyl)-pyrazole, of me~ting point 153 to 156C, are obtained.
Preparatlon of the start;ng compounds Cl ~C-S~ ~ -~H ~ c~ y t~ tN ~V-1) Cl 6.1 9 (0.05 mole) of ~thoxymethylenenalonodinitrile are added, ~ith stirring, to a suspension of 13.9 y (0.05 mole) of (2,6-dichloro-4-trifluoromethylthio)-pheny~hydra-Le A 23 492 -Foreign Countries 12496~)1 zine and 2.1 ~ C0.025 mole) of sodium acetate in 25 nL of g~acial acetic acid. ~fter compLetion of the addition, stirring is continued for an hour at room temperature and the solid thus obtained is filtered off, ~ashed succes-siveLy ~ith ~ater, aqueous sodium bicarbonate solution andagain uith uater, and then dried. 15.8 ~ ~89X of theory) of 1-~2,2-dicyanoethen-1-yl)-2-~2,6-dichloro-4-trifluoro-~ethylthiophenyl)-hydrazine of meltlng point 160C are obtained.
____", tN
Nb`~3-- N 112 Cl R~ Cl (lII-l) SCF~
14.1 ~ ~0.04 nole) of 1-t2,2-dicyanoethen-1-yl)-2-~2,6-dichloro-4-trifluoromethylth;o-phenyl)-hydrazine in 30 ml of ethylene glycol monoethyl ether are heated under reflux for 2 hours. The hot solution is treated ~ith active charcoal, filtered and diluted ~ith 60 ml of ~ater.
The precipltate uhich separates out is filtered off and dried. 9.8 9 ~70Z of theory) of 5-amino-4-cyano-1-~2,6-dichloro-4-trifluoronethylthiophenyl)-pyrazole, of melting polnt 185 to 187C, are obtained.
Use ExanPle In the use example ~hich follo~s, the compound sho~n belo~ is employed as the comparison substance:
CN
~ .
N~N~ NH-tO-c2Hs t~ ~ Cl (~) 4-Cyano-5-propionylam1no-1-(2,4,6-trichlorophenyl)-pyrazole ~kno~n from DE-OS ~6erman Published Specification) 3,226,513).
Le ~ 23 492-Foreign Countries 12~9601 Example A
Pre-emergence test SoLvent: 5 parts by we;ght of acetone Emuls;fier: 1 part by weight of aLkyLaryL poLygLycoL ether To produce a suitabLe preparation of active com-pound, 1 part by weight of active compound is mixed with the stated amount of soLvent, the stated amount of emuL-sifier is added and the concentrate is diluted with ~ater to the desired concentration.
Seeds of the test plants are so~n in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, onLy the amount of active compound appLied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in X damage in comparison to the development of the untreated control. The figures denote:
OX = no action ~like untreated controL) 100X = total destruction In this exampLe the compound according to Preparation Example ~VI-I), for example, exhibits a distinct superiority in herbicidal activity and in crop pLant seLectivity compared to the prior art; this is particuLarLy true of wheat.
Le A 23 492-Foreign Countries
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a substituted phenylhydrazine of the formula (I) (I) in which R1 and R2 represent hydrogen or chlorine, R3 represents halogenoalkyl, X represents oxygen, sulphur, sulphinyl or sulphonyl and n represents a number 0 or 1, which process comprises reacting a substituted chlorobenzene of the formula (II) (II) in which R1, R2, R3, X and n are as defined above, with hydrazine or hydrazine hydrate, at a temperature between 60 and 160°C.
2. A process according to claim 1, wherein the reaction is carried out at a temperature between 80 and 140°C.
3. A process according to claim 2, wherein the reaction is carried out at a temperature between 100 and 120°C.
4. A process according to claim 1, wherein 1 to 10 moles of hydrazine or hydrazine hydrate are employed per mole of substituted chlorobenzene of the formula (II).
5. A process according to claim 4, wherein 2 to 8 moles of hydrazine or hydrazine hydrate are employed per mole of substi-tuted chlorobenzene of the formula (II).
6. A process according to claim 5, wherein 3.0 to 7.0 moles of hydrazine or hydrazine hydrate are employed per mole of substi-tuted chlorobenzene of the formula (II).
7. A process according to claim 1, 2 or 4 wherein the reaction is carried out in contact with a diluent.
8. A process according to claim 1, 2 or 4 wherein the reaction is carried out at an elevated pressure.
9. A process according to claim 1, wherein the reaction is carried out in contact with an inert organic solvent.
10. A process according to claim 9 wherein said inert organ-ic solvent comprises dioxane, n-propanol or pyridine.
11. A process according to claim 1, 2 or 4 wherein in the starting materials R3 represents straight-chain or branched halogenoalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.
12. A process according to claim 1, 2 or 4 wherein in the starting materials R3 represents difluoromethyl, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, trifluoroethyl, tetra-fluoroethyl, pentafluorethyl, tetrafluorochloroethyl, trifluoro-chloroethyl, trifluorodichloroethyl, difluorotrichloroethyl, difluorodichloroethyl, tetrachlorofluoroethyl or pentachloroethyl, and X represents sulphur, sulphinyl or sulphonyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843447211 DE3447211A1 (en) | 1984-12-22 | 1984-12-22 | METHOD FOR PRODUCING SUBSTITUTED PHENYL HYDRAZINES |
| DEP3447211.8 | 1984-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1249601A true CA1249601A (en) | 1989-01-31 |
Family
ID=6253765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000498246A Expired CA1249601A (en) | 1984-12-22 | 1985-12-20 | Process for the preparation of substituted phenylhydrazines |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0187285B1 (en) |
| JP (1) | JPH0694452B2 (en) |
| AT (1) | ATE46144T1 (en) |
| BR (1) | BR8506414A (en) |
| CA (1) | CA1249601A (en) |
| DD (1) | DD242223A5 (en) |
| DE (2) | DE3447211A1 (en) |
| DK (1) | DK593785A (en) |
| HU (1) | HU196955B (en) |
| ZA (1) | ZA859747B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3631003A1 (en) * | 1986-09-12 | 1988-03-24 | Bayer Ag | METHOD FOR PRODUCING 4-SUBSTITUTED 1-ARYL-5-AMINO-PYRAZOLES |
| DE3712204A1 (en) * | 1987-04-10 | 1988-10-27 | Bayer Ag | 3-HALOGENALKYL-1-ARYL-PYRAZOLE |
| DE3937282A1 (en) * | 1989-11-09 | 1991-05-16 | Hoechst Ag | METHOD FOR PRODUCING ALKYL (3-CHLORPHENYL) SULPHONES |
| DE69904448T2 (en) * | 1998-02-26 | 2003-10-23 | Massachusetts Institute Of Technology, Cambridge | METAL-CATALYZED ARYLATIONS AND VINYLATIONS OF HYDRAZINES, HYDRAZONES, HYDROXYLAMINES AND OXIMES |
| US6235936B1 (en) | 1998-02-26 | 2001-05-22 | Massachusetts Institute Of Technology | Metal-catalyzed arylations of hydrazines, hydrazones, and related substrates |
| KR20090121392A (en) * | 2007-03-16 | 2009-11-25 | 바스프 에스이 | Process for preparing 2,6-dichloro-4-(trifluoromethyl)phenylhydrazine using mixtures of dichloro-fluoro-trifluoromethylbenzenes |
| CA2679858A1 (en) * | 2007-03-16 | 2008-09-25 | Basf Se | Process for preparing substituted phenylhydrazines |
| CN106045876B (en) * | 2016-06-07 | 2018-02-09 | 四川福思达生物技术开发有限责任公司 | A kind of synthetic method of p-hydrochloride |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2015405A1 (en) * | 1970-04-01 | 1971-10-21 | Farbenfabriken Bayer Ag, 5090 Lever Kusen | Biocidal pentahalophenylhydrazines |
| DE3420985A1 (en) * | 1983-10-15 | 1985-04-25 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED 5-ACYLAMINO-1-PHENYLPYRAZOLE |
| DE3501323A1 (en) * | 1985-01-17 | 1986-07-17 | Bayer Ag, 5090 Leverkusen | 1-ARYL-4-NITROPYRAZOLE |
-
1984
- 1984-12-22 DE DE19843447211 patent/DE3447211A1/en active Pending
-
1985
- 1985-12-09 DE DE8585115641T patent/DE3572804D1/en not_active Expired
- 1985-12-09 AT AT85115641T patent/ATE46144T1/en not_active IP Right Cessation
- 1985-12-09 EP EP85115641A patent/EP0187285B1/en not_active Expired
- 1985-12-19 DK DK593785A patent/DK593785A/en not_active Application Discontinuation
- 1985-12-19 JP JP60284470A patent/JPH0694452B2/en not_active Expired - Fee Related
- 1985-12-20 DD DD85284918A patent/DD242223A5/en unknown
- 1985-12-20 BR BR8506414A patent/BR8506414A/en unknown
- 1985-12-20 CA CA000498246A patent/CA1249601A/en not_active Expired
- 1985-12-20 ZA ZA859747A patent/ZA859747B/en unknown
- 1985-12-20 HU HU854916A patent/HU196955B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0694452B2 (en) | 1994-11-24 |
| DE3447211A1 (en) | 1986-06-26 |
| HUT39724A (en) | 1986-10-29 |
| JPS61155360A (en) | 1986-07-15 |
| DK593785A (en) | 1986-06-23 |
| ZA859747B (en) | 1986-08-27 |
| EP0187285B1 (en) | 1989-09-06 |
| ATE46144T1 (en) | 1989-09-15 |
| DE3572804D1 (en) | 1989-10-12 |
| BR8506414A (en) | 1986-09-02 |
| DD242223A5 (en) | 1987-01-21 |
| EP0187285A3 (en) | 1988-04-20 |
| DK593785D0 (en) | 1985-12-19 |
| EP0187285A2 (en) | 1986-07-16 |
| HU196955B (en) | 1989-02-28 |
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