CN1457338A - Process for preparation of aryltriazolinones - Google Patents
Process for preparation of aryltriazolinones Download PDFInfo
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- CN1457338A CN1457338A CN 01815631 CN01815631A CN1457338A CN 1457338 A CN1457338 A CN 1457338A CN 01815631 CN01815631 CN 01815631 CN 01815631 A CN01815631 A CN 01815631A CN 1457338 A CN1457338 A CN 1457338A
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- 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
- C07D249/12—Oxygen or sulfur atoms
Abstract
Provided are a novel process by which aryltriazolinones can be more easily prepared from more inexpensive raw materials at a low cost; and a novel process by which aryltriazolinones can be prepared simply and easily under safer and milder conditions at a low cost. Specifically, the invention provides a process for the preparation of aryltriazolinones (I) which comprises dehydrogenating an aryltriazolidinone (II) with an oxidizing agent; and a process for the preparation of aryltriazolinones (I), characterized by adding an alkali metal cyanate and an acid to an arylhydrazone (III) and further adding oxygen to the resulting mixture in the presence or absence of an oxidation catalyst. In the general formulae, X is halogeno or C1-6 lower alkyl; and n is an integer of 0 to 5, with the proviso that when n is 2 or above, Xs may be the same or different from each other.
Description
Technical field
The present invention relates to prepare aryl-1,2, the method for 4-triazoline-5-ketone more particularly, relates to preparation as being used for the aryl-1,2 of material of synthetic drugs and agrochemicals or their intermediate, 4-triazoline-5-ketone.
Background technology
Aryl-1,2,4-triazoline-5-ketone (aryltriazolinones) are as being used for the useful compound of material of synthetic drugs and agrochemicals or their intermediate, and have proposed their method of various preparations up to now.
For example, the international open communique WO 98/38176 of (1) PCT has described by following prepared in reaction aryltriazolinones.
In above-mentioned general formula, n is 0 or the integer of 1-5, and each X can be identical or different, is halogen atom, low alkyl group, rudimentary alkylhalide group etc.
In the method that is described in above-mentioned open communique (1); virtue hydrazone compound (3) must be separated in reactions steps; and owing to used expensive diphenyl phosphoryl azide (4) among the preparation method, the cost of preparation aryltriazolinones (5) uprises.Therefore, this method is industrial advantageous method hardly.
Therefore, need a kind of new method for preparing aryltriazolinones for preparing aryltriazolinones easily at lower cost of exploitation.
(2) corresponding with the international open communique WO of PCT 91/3470 Japanese patent gazette No.78322/1994 has described the method for preparation by the aryltriazolinones of following general formula (A) expression, it comprises with hypohalous acid or hypohalite handles the aryl triazoles alkane ketone of being represented by following general formula (AO)
In the formula, n is the integer of 1-3, and R is halogen atom, alkyl, alkylhalide group etc., and each is hydrogen, halogen atom (Cl, Br, I), low alkyl group etc. independently for X,
In the formula, n is the integer of 1-3, and R is halogen atom, alkyl, alkylhalide group etc., and each is hydrogen, halogen atom, low alkyl group etc. independently for X.
(3) the domestic open communique of the international patent application No.503253/1995 corresponding with the international open communique WO of PCT 93/23382 discloses the method for preparation by the aryltriazolinones of following general formula (B) expression:
In the formula, R is a low alkyl group, and each is halogen, low alkyl group, nitro, hydroxyl, NHSO independently for X
2R ' ,-N (SO
2R ')
2Or-N (R ') SO
2R ' (R ' be low alkyl group), n is the integer of 0-3,
It comprises in turn the aldehyde of using (i) C1-C3, (ii) cyanate and weak organic acid and (iii) hypochlorous acid or its salt or halogen are handled by general formula X
n-Ph-NHNH
2The aryl hydrazine of (Ph: phenylene, X: same as described above, n: same as described above) expression.
, in above-mentioned communique (2) and (3), both do not described and do not mentioned by general formula (A) or (B) aryltriazolinones of (in the formula, R is hydrogen (H)) expression and the method for preparing them yet.
The halogen, hypohalous acid and their salt that use in the dehydrogenation reaction owing to the method for preparing aryltriazolinones have corrodibility or pungency, must be careful when handling these a large amount of materials.Therefore, need a kind of method for preparing aryltriazolinones of not using these materials.
In addition, using hypohalous acid or its salt to prepare in the method for aryltriazolinones, hypohalous acid or its salt use with dilute solution usually, make that the quantitative change of reaction solution is big.Therefore, have following problem: batch output of aryltriazolinones is difficult to increase, and it is very big to contain the amount of waste water of halogen.And, in using the dehydrogenation reaction step of halogen, hypohalous acid or their salt, aryl hydrazone, cyanic acid and cyanate instability, thus be difficult to form simultaneously the reaction and the dehydrogenation reaction thereof of aryl triazoles alkane ketone.
Therefore, the present invention will solve these problems that exist in the above-mentioned prior art, and the purpose of this first invention provides a kind of new method for preparing aryltriazolinones, and this method can prepare aryltriazolinones more easily by using more cheap material with lower cost.
The purpose of this second invention provides a kind of new method for preparing aryltriazolinones, by this method, can not use halogen, hypohalous acid and their salt, with lower cost, prepares aryltriazolinones more easily under the condition of safety and gentleness.
Summary of the invention
First method for preparing aryltriazolinones of the present invention is the method for preparation by the aryltriazolinones of general formula (I) expression:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
This method comprises with oxygenant the step by the aryl triazoles alkane ketone dehydrogenation of general formula (II) expression:
In the formula, identical in X and n and the general formula (I).
In first method of the present invention, with oxygenant to aryl triazoles alkane ketone (II) dehydrogenation preferably carry out in the following manner: use in advance an alkali metal salt of cyanic acid and acid (preferably organic acid) with by the aryl hydrazone reaction of general formula (III) expression to form aryl triazoles alkane ketone, do not having catalyzer or having interpolation oxygenant in the condition downhill reaction liquid of oxide catalyst and need not aryl triazoles alkane ketone (II) is separated from reaction solution then:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
In first method of the present invention, oxygenant is any one in halogen, hypohalous acid, hypohalite, permanganate, hydrogen peroxide, peracid, alkyl hydroperoxide, nitric acid, dimethyl sulfoxide (DMSO) and the oxygen preferably, is more preferably hypohalite or oxygen.
In first method of the present invention, the reaction of an alkali metal salt of aryl hydrazone (III) and cyanic acid and acid is preferably carried out in the following manner: do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, use in advance formaldehyde with by the aryl hydrazine reaction of general formula (IV) expression forming aryl hydrazone by general formula (III) expression, and in the reaction solution that contains aryl hydrazone (III), add an alkali metal salt of cyanic acid and acid (preferably organic acid) and need not and will from reaction solution, separate by the compound that general formula (III) is represented:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
In first method of the present invention, can use the inorganic acid salt of aryl hydrazine to substitute aryl hydrazine (IV), and handle this inorganic acid salt with alkali.
According to first method of the present invention, the material that can use cheapness to buy as an alkali metal salt and the hypohalite or the oxygen of formaldehyde, cyanic acid, makes that aryltriazolinones (I) can be with lower cost preparation.In a better embodiment of first method of the present invention, the reaction of above-mentioned three steps can be carried out in a jar (reactor).In this case, do not need reaction intermediate (III) that isolated or purified forms and (II) in reaction process, and can in a container, promote these reactions to obtain target aryltriazolinones (I).A kind of industrial advantageous method for preparing aryltriazolinones so just is provided.The aryltriazolinones that is obtained by this method is used for the material of synthetic agrochemicals and medicine or their intermediate.
Second method of preparation aryltriazolinones of the present invention is the method for preparation by the aryltriazolinones of general formula (I) expression:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer,
This method comprises an alkali metal salt and the acid of adding cyanic acid in by the aryl hydrazone of general formula (III) expression:
In the formula, identical in X and n and the general formula (I),
In addition, also there be not catalyzer or existing under the condition of oxide catalyst to add oxygen, forming the dehydrogenation reaction of the aryl triazoles alkane ketone (II) that forms by the reaction of the aryl triazoles alkane ketone (II) of general formula (II) expression with by above reaction simultaneously,
In the formula, identical in X and n and the general formula (I).
In second method of the present invention, preferably preparation by the following method of aryltriazolinones by general formula (I) expression, this method be included in do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, with formaldehyde with by the aryl hydrazine reaction of general formula (IV) expression to form the aryl hydrazone of representing by general formula (III), and in reaction solution, add an alkali metal salt of cyanic acid and acid and need not the aryl hydrazone is separated from reaction solution, and do not having catalyzer or existing to add oxygen under the condition of oxide catalyst:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
In second method of the present invention, preferably, aryltriazolinones by general formula (I) expression also can prepare by the following method, this method comprises: use the inorganic acid salt of aryl hydrazine to substitute aryl hydrazine (IV), with formaldehyde and alkali and the reaction of this inorganic acid salt to form aryl hydrazone by general formula (III) expression, in reaction solution, add an alkali metal salt of cyanic acid and acid and need not aryl hydrazone (III) is separated from reaction solution, and do not having catalyzer or existing under the condition of oxide catalyst to add oxygen.
According to second method of the present invention, can use cheap commercial material, as an alkali metal salt, oxide catalyst and the oxygen of formaldehyde, cyanic acid, make that aryltriazolinones (I) can be with lower cost preparation under the condition of safety and gentleness.In a better embodiment of second method of the present invention, above-mentioned reaction can be carried out in a jar (reactor), in this case, does not need reaction intermediate (III) that isolated or purified forms and (II) in reaction process.
The dehydrogenation reaction that formation by carrying out aryl triazoles alkane ketone (II) simultaneously and being used for forms the aryl triazoles alkane ketone (II) of aryltriazolinones (I) can shorten the reaction times.The industrial advantageous method of preparation aryltriazolinones so just is provided.
The aryltriazolinones (I) that is obtained by this method is used for the material of synthetic agrochemicals and medicine or their intermediate.
Embodiment
Below, will describe the method for preparation aryltriazolinones of the present invention in detail.
In first method of preparation aryltriazolinones of the present invention, use oxygenant to aryl triazoles alkane ketone dehydrogenation, with the aryltriazolinones of preparation by following general formula (I) expression by general formula (II) expression.In a better embodiment of this method, by a series of following step of reaction, promptly first to phase III prepares by the aryltriazolinones of general formula (I) expression.Hereinafter, this method is also referred to as " first method ".
Fs
In general formula (I)-(IV), X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
Halogen atom is chlorine, bromine, fluorine or iodine.
When the X in the general formula (I)-(IV) was low alkyl group, this low alkyl group was the alkyl of 1-6 carbon atom, and can be straight chain or branched.The example of these groups comprises: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, 2-methyl butyl, neo-pentyl, n-hexyl, 4-methyl amyl, 2,3-dimethylbutyl, 1-ethyl-butyl, 1-ethyl-2-methyl-propyl, 1-methyl isophthalic acid-ethyl propyl, 1-methyl-2-ethyl propyl, 2-methyl isophthalic acid-ethyl propyl and 2-methyl-2-ethyl propyl.
In second method of preparation aryltriazolinones of the present invention, the oxidation by oxygen makes the aryl triazoles alkane ketone by following general formula (II) expression carry out dehydrogenation reaction, with the aryltriazolinones of preparation by following general formula (I) expression.In a better embodiment of this method, carry out simultaneously forming step by the aryl triazoles alkane ketone of general formula (II) expression from aryl hydrazone by general formula (III) expression, and the step of the aryltriazolinones that aryl triazoles alkane ketone (II) dehydrogenation that forms by above-mentioned steps is represented by general formula (I) with preparation.Hereinafter, this method is also referred to as " second method ".
Use is described in first method of preparation aryltriazolinones (I) and the identical compound of compound by general formula (I)-(IV) preparation.
At first, description is as first method of the preparation aryltriazolinones (I) of first invention.
First method of preparation aryltriazolinones (I)
In first method of preparation aryltriazolinones (I), use the aryl triazoles alkane ketone dehydrogenation of oxygenant in above-mentioned " phase III ", with the aryltriazolinones of preparation by general formula (I) expression to representing by general formula (II).
Preferably, aryl triazoles alkane ketone by general formula (II) expression used herein is synthetic in the following manner: the aryl hydrazine (or its inorganic acid salt) by general formula (IV) expression is reacted to form the aryl hydrazone by the general formula in " fs " (III) expression with formaldehyde (HCHO), make an alkali metal salt (alkali metal cyanate) and the acid-respons of the cyanic acid in aryl hydrazone and " subordinate phase " then, as shown in above-mentioned reaction equation.
In each stage of successive reaction in a jar, do not need isolated or purified as the aryl hydrazone (III) of intermediate product or as the aryl triazoles alkane ketone (II) of intermediate product, and by in the reaction solution that contains aryl hydrazone (III), adding an alkali metal salt and the acid (preferably organic acid) of cyanic acid, and not having catalyzer or existing under the condition of oxide catalyst in turn in the reaction solution that contains the aryl triazoles alkane ketone (II) that forms by above-mentioned reaction, to add oxygenant, the synthetic of target aryltriazolinones (I) can carry out with so-called batch mode in single reactor effectively.
In reaction as the aryl triazoles alkane ketone (II) of the oxidizing reaction in first method of the present invention and oxygenant, do not having catalyzer or existing under the condition of oxide catalyst, oxygenant only directly adds and contains in the reaction mixture of the aryl triazoles alkane ketone (II) that obtains by an alkali metal salt and acid treatment aryl hydrazone (III) with cyanic acid.So just carried out the reaction of phase III.
In first method of the present invention, a series of these are reflected under the existence of solvent and carry out.Solvent used herein is a solvent described later, and it does not have adverse influence to reaction, and can be partly dissolved aryl hydrazone (III) and aryl triazoles alkane ketone (II) preferably.
In first method of the present invention, the series reaction of fs to phase III is carried out under lower temperature, and can finish in short for some time, thereby can obtain the target compound (aryltriazolinones (I)) of high yield.
Synthetic (fs) of aryl hydrazone (III)
Below, with following above-mentioned step of reaction described the fs of the inventive method in more detail.In the fs of first method that preferably is used in preparation aryltriazolinones of the present invention (I), do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, make formaldehyde reaction in aryl hydrazine (IV) or its inorganic acid salt and the solvent to form corresponding aryl hydrazone (III).
Use the inorganic acid salt of aryl hydrazine to substitute aryl hydrazine (IV), do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, this inorganic acid salt only needs and alkali such as sodium hydroxide, and formaldehyde reacts.
The reaction of fs under atmospheric pressure, be generally-10 ℃ in temperature to the boiling point of the solvents that use, preferably carried out preferably 30 minutes to 5 hours 10 minutes to 24 hours under about 0 ℃ to+40 ℃.In this reaction, aryl hydrazine (IV) and formaldehyde in theory only need to use with equimolar amount.But the amount of the formaldehyde of use is generally, and for 1mol aryl hydrazine (IV), uses 1.0-2.0mol, preferably 1.0-1.2mol, and the common formalin that uses the formaldehyde that contains this tittle.
General on sale or be easy to according to being described on market usually by the aryl hydrazine of general formula (IV) expression or its inorganic acid salt as parent material, for example " organic synthesis " currently known methods of closing in the volume I 442-445 page or leaf (1956) synthesizes.
The example of alkali of alkaline purification that is used for the inorganic acid salt of aryl hydrazine comprises: sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, salt of wormwood and hydrated barta.Wherein, preferably use sodium hydroxide, potassium hydroxide etc.Though alkali only needs to use with the equimolar amount of the inorganic acid salt of aryl hydrazine in theory, the amount that is to use is generally, and for the inorganic acid salt of 1mol aryl hydrazine, uses 1.0-2.0mol, preferably 1.0-1.2mol.
The example that is used for the acid catalyst of aryl hydrazine (IV) and formaldehyde reaction comprises: mineral acid, example hydrochloric acid and sulfuric acid; Organic acid is as formic acid and acetate; Sulfonic acid is as tosic acid; Phosphoric acid is as phosphonic acids, phosphoric acid and tetra-sodium; And acid phosphate, as Alendronate, phosphonic acids potassium, dihydrogen phosphoric acid sodium, Kdp, trisodium phosphate and potassium pyrophosphate.
The example of alkaline catalysts comprises: mineral alkali, as sodium hydroxide, potassium hydroxide and yellow soda ash; And amine, as triethylamine, pyridine and 1,8-diazabicyclo (5.4.0)-7-hendecene.The amount of the catalyzer that uses is generally the 0.01-10 mole % of aryl hydrazine.
The example of solvent comprises: alcohol, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, methyl cellosolve, propyl carbinol, sec-butyl alcohol, isopropylcarbinol and the trimethyl carbinol; Ether, as tetrahydrofuran (THF) with diox; Nitrile is as acetonitrile and propionitrile; And organic acid, as formic acid and acetate.Can use the mixed solvent of above-mentioned solvent and water, preferably use the mixed solvent of the trimethyl carbinol and water.The amount of the solvent that uses is for example for 1mol aryl hydrazine (IV), to use 100-4000ml.
The amount of solvent can suitably change according to each reaction product and reaction conditions in following subordinate phase (stage of an alkali metal salt reaction of aryl hydrazone (III) and cyanic acid) and following phase III (stage of aryl triazoles alkane ketone (II) and oxidant reaction), and this amount can not be determined respectively.
Synthetic (subordinate phase) of aryl triazoles alkane ketone (II)
In the subordinate phase of first method that preferably is used in preparation aryltriazolinones of the present invention (I), an alkali metal salt (alkali metal cyanate) of the cyanic acid in aryl hydrazone (III) and the solvent and as acid (preferably organic acid) reaction of proton source to form aryl triazoles alkane ketone (II).An alkali metal salt by adding cyanic acid in the reaction soln that contains the aryl hydrazone (III) that obtains in the fs and as the organic acid of proton source, this reaction can be carried out in batches effectively.
The reaction of subordinate phase under atmospheric pressure, about usually-10 ℃ to+60 ℃ of temperature, preferably carried out preferably about 1-5 hour 1-24 hour under about 0 ℃ to+40 ℃.
Though an alkali metal salt of aryl hydrazone (III) and cyanic acid in theory only needs to use with equimolar amount,, the amount of an alkali metal salt of the cyanic acid of use is generally, and for 1mol aryl hydrazone (III), uses 1.0-3.0mol, preferably 1.0-1.5mol.
The example of an alkali metal salt of cyanic acid comprises: Zassol, potassium cyanate and calcium cyanate.Wherein, preferred Zassol.
Example as the acid of proton source comprises: phosphoric acid, as phosphonic acids, phosphoric acid and tetra-sodium; Phosphoric acid salt is as Alendronate, phosphonic acids potassium, dihydrogen phosphoric acid sodium, Kdp, trisodium phosphate and potassium pyrophosphate; And organic acid, as formic acid, acetate, propionic acid and butyric acid.Wherein, preferred organic acid.
Though acid as organic acid only need to use with the amount of an alkali metal salt equimolar amount of cyanic acid, the amount of the acid that is to use (preferably organic acid) is generally 1.0-1.2 equivalent (above equivalent about 20%), preferably 1.00-1.10 equivalent.
Use the solvent identical as this solvent with the fs.When with an organic solvent with the mixed solvent of water, the ratio of mixture of organic solvent and water be 100: 1 to 500 (organic solvent: water), preferably 100: 20 to 200 (organic solvents: water).The amount of the solvent that uses is for 1mol aryl hydrazone (III), to use 100-5000ml.
Synthetic (phase III) of aryltriazolinones (I)
In phase III of first method of preparation aryltriazolinones of the present invention (I), do not having catalyzer or existing under the condition of oxide catalyst, make oxidant reaction in aryl triazoles alkane ketone (II) and the solvent to form target aryltriazolinones (I).
This reaction under atmospheric pressure, about usually-10 ℃ to 60 ℃ of temperature, preferably carried out preferably about 2-8 hour 1-24 hour under about 0 ℃ to 40 ℃.
The example of oxygenant comprises: halogen, hypohalous acid, hypohalite, permanganate, hydrogen peroxide, peracid, alkyl hydroperoxide, nitric acid, dimethyl sulfoxide (DMSO) and oxygen.When needing, oxygenant can use in the presence of oxide catalyst.The example of halogen comprises: chlorine, bromine, iodine and fluorine.In these oxygenants, the clorox in the preferred hypohalite.
When hydrogen peroxide, peracid or alkyl hydroperoxide were used as oxygenant, the example of the oxide catalyst of use comprised:
The salt of iron group is as iron protochloride, ferrous bromide, ferrous sulfate, cobalt chloride, cobaltous bromide, rose vitriol, Xiao Suangu and cobaltous acetate;
Mantoquita is as cupric chloride (I), cupric bromide (I), cupric chloride (II), cupric bromide (II), copper sulfate and venus crystals; And
Vanadium Pentoxide in FLAKES, osmium oxide, selenium oxide, Tungsten oxide 99.999, sodium wolframate, molybdenum oxide, Sodium orthomolybdate, titanium tetrachloride and chromic oxide.
When oxygen was used as oxygenant, the example of oxide catalyst comprised:
The salt of iron group is as iron protochloride, iron(ic) chloride, ferrous bromide, iron bromide, ferrous sulfate, ferric sulfate, cobalt chloride, cobaltous bromide, rose vitriol, Xiao Suangu, cobaltous acetate and nickelous chloride;
The complex compound of iron group is as acetyl acetone iron (III), acetyl acetone cobalt (II), two (salicylidene) triethylenediamine cobalt (II) and chlorination six amminos nickelic (II);
Platinum family is as platinum and palladium;
The salt of platinum family is as Palladous chloride, acid chloride and platinum oxide;
The complex compound of platinum family closes rhodium and dichloro two (triphenyl phosphine) closes ruthenium as chlorine (triphenyl phosphine);
Mantoquita is as cupric chloride (I), cupric bromide (I), cupric chloride (II), cupric bromide (II), copper sulfate and venus crystals;
Copper complex closes copper as acetyl acetone copper (II) and two (quadrols);
Zinc salt is as zinc chloride;
Zinc complex closes zinc as three (quadrols);
Vanadic salts is as Vanadium Pentoxide in FLAKES;
Vanadium complexes closes vanadium as acetic oxide acetone; And
The salt of rare earth element is as Cerium II Chloride and means of samarium iodide.
These catalyzer use separately or two or more is used in combination.
In this reaction, aryl triazoles alkane ketone (II) and oxygenant in theory only use with the equimolar amount of need.But the amount of the oxygenant of use is generally, and for 1mol aryl triazoles alkane ketone (II), uses 1.00-1.40mol, preferably 1.00-1.10mol.More particularly, for example, the concentration of the aqueous sodium hypochlorite solution of use is about 5-25% (w/w), preferably is about 5-15%.When needs used oxide catalyst, its usage quantity was generally, and for the aryl triazoles alkane ketone (II) of 100mol%, used 0.01-10mol%, preferably 0.1-1mol%.
Solvent identical in use and fs and the subordinate phase is as solvent.With an organic solvent with the situation of the mixed solvent of water under, with as hereinbefore ratio of mixture with an organic solvent and water.The quantity of solvent of using is for 1mol aryl triazoles alkane ketone (II), to use 100-6000ml.
In first method of preparation aryltriazolinones of the present invention (I), preferably stirring reaction liquid leniently in each stage of first to phase III at least.Preferably, can be by in turn in single reactor, adding the required component of reaction, used being reflected in this reactor carried out with so-called batch mode.
After reaction is finished, the organic solvent in the mixed solvent (mixed solvent of organic solvent and water) is distilled from reaction solution, in the next process of preparation aryltriazolinones (I), reuse this organic solvent.Target aryltriazolinones (I) separates by common extraction liquids lock out operation, and perhaps behind organic solvent evaporation, target product is deposited in the water, collects by filtering then.For this target product of isolated or purified, can use following other method.After organic solvent distills from reaction mixture, target aryltriazolinones (I) is dissolved in the aqueous solution of alkali such as sodium hydroxide forming salt, and cleans this salt with organic solvent.Subsequently, add the mineral acid example hydrochloric acid and neutralize, precipitate target aryltriazolinones (I) thus.Leach sedimentary crystallization and water and clean, obtain highly purified aryltriazolinones (I).When needing, the target product that obtains like this can pass through the whole bag of tricks, as being further purified with organic solvent cleaning, column chromatography and recrystallize.
By suitable being used as of aryltriazolinones (I) that aforesaid method obtains, for example make the material of agrochemicals and medicine.
Second method of preparation aryltriazolinones (I)
Second method of preparation aryltriazolinones of the present invention (I) then, is described.In second method of the present invention, the step that forms the aryl triazoles alkane ketone of being represented by general formula (II) from the aryl hydrazone by general formula (III) expression (hereinafter, this step is called as " aryl triazoles alkane ketone (II) form step " sometimes) and carry out the aryltriazolinones of representing by general formula (I) with preparation not having catalyzer or exist under the condition of oxide catalyst simultaneously by the step of the dehydrogenation reaction by the oxygen oxidation aryl triazoles alkane ketone (II) that adds.
As shown in above-mentioned reaction formula, form in the step at aryl triazoles alkane ketone (II), react to form aryl hydrazone with formaldehyde and the aryl hydrazine of representing by general formula (IV) or its inorganic acid salt, make an alkali metal salt (alkali metal cyanate) and the acid-respons of aryl hydrazone and cyanic acid then by general formula (III) expression.
The step of the dehydrogenation reaction of aryl triazoles alkane ketone (II) is carried out in an alkali metal salt and acid by adding cyanic acid in by the aryl hydrazone of general formula (III) expression and do not having catalyzer or existing in the condition downhill reaction liquid of oxide catalyst to add oxygen simultaneously.
In these successive reactions in a jar, do not need isolated or purified as the aryl hydrazone (III) of intermediate product or as the aryl triazoles alkane ketone (II) of intermediate product, and, by an alkali metal salt of adding cyanic acid in the reaction solution that contains aryl hydrazone (III) and the step of acid (preferably organic acid) formation aryl triazoles alkane ketone (II), with carry out simultaneously not having catalyzer or exist under the condition of oxide catalyst by the step of the dehydrogenation reaction by adding the oxygen oxidation, promptly being reflected in the single reactor of two stages carried out simultaneously, can synthesize target aryltriazolinones (I) effectively thus.
In second method of the present invention, a series of these reactions are carried out in the presence of solvent usually.Solvent used herein does not have adverse influence to reaction, and can be partly dissolved aryl hydrazone (III) and aryl triazoles alkane ketone (II) preferably.
In second method of the present invention, a series of these were reflected in the short time to be finished, thereby can obtain the aryltriazolinones (I) of high yield.
Then, will be main with reference to first method of second method of preparation aryltriazolinones (I) and preparation aryltriazolinones (I), the difference for preparing the method etc. of parent material, it is described in more detail.
Synthesizing of aryl hydrazone (III)
With with in first method of the invention described above, form the identical method of aryl hydrazone (III), the synthetic aryl hydrazone (III) that is used to form the aryl triazoles alkane ketone (II) in second method that is used for preparing aryltriazolinones of the present invention (I).
That is to say, do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, make the formaldehyde reaction in aryl hydrazine (IV) or its inorganic acid salt and the solvent, to form aryl hydrazone (III).
Simultaneously, in second method of the present invention, use " inorganic acid salt of aryl hydrazine " to substitute the aryl hydrazine (IV) that conduct forms the material of aryl hydrazone (III), it is similar to above-mentioned first method.In this case, in second method of the present invention, make inorganic acid salt and the alkali and the formaldehyde reaction of aryl hydrazine, preferably use the reaction solution of the aryl hydrazone (III) contain gained and need not aryl hydrazone (III) is separated from reaction solution, with synthesizing aryl Triazolinones (I).
As aryl hydrazine (IV) or its inorganic acid salt, alkaline catalysts, acid catalyst and solvent, under identical condition, use aforementioned those materials in " the synthesizing of aryl hydrazone (III) " of first method.But the amount of the reaction solvent of use is preferably, and for 1mol aryl hydrazine (IV), uses 300-3000ml.
Synthesizing of aryltriazolinones (I)
In the step of the aryltriazolinones (I) that forms second method that is used in preparation aryltriazolinones of the present invention (I) preferably, in the reaction solution of the aryl hydrazone (III) that contains above-mentioned gained, add an alkali metal salt (alkali metal cyanate) of cyanic acid and as the acid (preferably organic acid) of proton source, and do not having catalyzer or existing under the condition of oxide catalyst, in reaction solution, further introduce (adding) oxygen and be used for dehydrogenation reaction, form target aryltriazolinones (I) thus.
The step that forms aryltriazolinones (I) is about-10 ℃ to+100 ℃ usually of temperature, preferably carried out preferably about 1-10 hour 1-24 hour under about 0 ℃ to 60 ℃.
Though an alkali metal salt of aryl hydrazone (III) and cyanic acid in theory only needs to use with equimolar amount,, the amount of an alkali metal salt of the cyanic acid of use is generally, and for 1mol aryl hydrazone (III), uses 1-5mol, preferably 1-3mol.
The example of an alkali metal salt of cyanic acid is included in the identical compound that is used for synthesizing aryl triazolidine ketone (II) in above-mentioned first method.Wherein, preferred Zassol and potassium cyanate.
Example as the acid of proton source comprises: with the identical acid that is used for synthesizing aryl triazolidine ketone (II) in above-mentioned first method.Though only need using this acid with the equimolar amount of an alkali metal salt of cyanic acid,, its usage quantity is generally the 0.5-3.0mol of an alkali metal salt of 1mol cyanic acid, preferably 0.5-1.1mol.
The example of oxide catalyst comprises:
The salt of iron group is as iron protochloride, iron(ic) chloride, ferrous bromide, iron bromide, ferrous sulfate, ferric sulfate, cobalt chloride, cobaltous bromide, rose vitriol, Xiao Suangu, cobaltous acetate and nickelous chloride;
The complex compound of iron group is as acetyl acetone iron (III), acetyl acetone cobalt (II), two (salicylidene) triethylenediamine cobalt (II) and chlorination six amminos nickelic (II);
Platinum family is as platinum and palladium;
The salt of platinum family is as Palladous chloride, acid chloride and platinum oxide;
The complex compound of platinum family closes rhodium and dichloro two (triphenyl phosphine) closes ruthenium as chlorine (triphenyl phosphine);
Mantoquita is as cupric chloride (I), cupric bromide (I), cupric chloride (II), cupric bromide (II), copper sulfate and venus crystals;
Copper complex closes copper as acetyl acetone copper (II) and two (quadrols);
Zinc salt is as zinc chloride;
Zinc complex closes zinc as three (quadrols);
Vanadic salts is as Vanadium Pentoxide in FLAKES;
Vanadium complexes closes vanadium as acetic oxide acetone; And
The salt of rare earth element is as Cerium II Chloride and means of samarium iodide.
These catalyzer use separately or two or more is used in combination.In these oxide catalysts, preferred cupric salt is as copper sulfate and venus crystals.The usage quantity of oxide catalyst is the 0.01-10mol% of the aryl hydrazone (III) of 100mol%, preferably 0.1-1mol%.
The introducing of oxygen (adding) is undertaken by reactive system being placed oxygen atmosphere or oxygen being blown into reaction solution or air is blown into reaction solution in the dehydrogenation reaction step.Pressure in the oxygen adition process in the reactive system is generally 1-10 normal atmosphere (1 * 10
3-1 * 10
4HPa), 1-3 normal atmosphere (1 * 10 preferably
3-3 * 10
3HPa).
Use is used for the identical solvent of the synthetic of aryl triazoles alkane ketone (II) of above-mentioned first method as solvent, for example with an organic solvent with the mixed solvent of water.With as hereinbefore ratio of mixture with an organic solvent and water.The quantity of solvent of using is for 1mol aryl hydrazone (III), to use 100-5000ml, preferably 300-4000ml.
The step that forms aryltriazolinones (I) is carried out with so-called batch mode ideally by in turn add the required component of step of reaction in same reactor.
After reaction is finished, the organic solvent in the mixed solvent that uses is distilled from reaction solution, in the next process of preparation aryltriazolinones (I), reuse this organic solvent.Target aryltriazolinones (I) separates by common extraction liquids lock out operation, and perhaps behind organic solvent evaporation, target product is deposited in the water, collects by filtering then.When needing, target product (I) can pass through the whole bag of tricks, is further purified as column chromatography and recrystallize.
For this target product of isolated or purified (I), can use following other method.After organic solvent distilled from above-mentioned reaction mixture, the aryltriazolinones (I) in the aqueous solution dissolving water of adding mineral alkali then cleaned it with organic solvent.Subsequently, add the mineral acid example hydrochloric acid with in and the salt of aryltriazolinones (I), precipitate target product (I) thus.Leach sedimentary crystallization and water and clean, obtain highly purified aryltriazolinones (I).
By suitable being used as of aryltriazolinones (I) that aforesaid method obtains, for example make the material of agrochemicals and medicine.
In first method of preparation aryltriazolinones of the present invention (I), be reflected at and carry out under the lower temperature and finish with the short time, thereby can obtain the target compound aryltriazolinones (I) of high yield.The separation of final objective product aryltriazolinones (I) be easy to by, for example solvent distillation carries out.
In better embodiment of the present invention, if being reflected in the jar of above-mentioned all stages (first to the phase III) carried out, then their available a spot of energy promote, the result can provide the aryltriazolinones of target compound-purifying with lower cost.In addition, the method for preparing aryltriazolinones of the present invention can be preferably in industrial large-scale application, that is, this method is industrial advantageous method.
Particularly in second method of preparation aryltriazolinones of the present invention, compare with the ordinary method of using hypohalite or halogen to carry out oxidizing reaction, present method is used the oxygen oxidation in dehydrogenation step, therefore can under the condition of safety and gentleness, obtain target compound easily with lower cost.
In better embodiment of the present invention, can in same container, carry out simultaneously with the dehydrogenation reaction step and the step of the intermediate aryl triazoles alkane ketone (II) that forms target compound of oxygen oxidation, thereby can shorten the reaction times.Therefore, this method can be preferably in industrial large-scale application, that is, this method is industrial advantageous method.
Embodiment
Further describe the present invention with reference to following examples, in any case but should be noted that the present invention is not limited to these embodiment.
Embodiment 1
1-phenyl-1,2, the preparation of 4-triazole-5-ketone
In one 2 liters four neck flasks, stir the 250ml trimethyl carbinol and 54g phenylhydrazine, and in ice-water bath, the solution of gained is cooled to 5 ℃.In solution, add 0.1g acetate, and drip the formalin 20 minutes of 43.8g 36%.After dripping, use frozen water cooling and stirring reaction mixture 15 minutes.Subsequently, once add 35.8g Zassol slurries in the 100ml water.After adding, the temperature of reaction mixture has raise 10 ℃.
After the adding of Zassol is finished, reaction mixture is cooled to 5 ℃, and dripped 39g acetate 10 minutes.After dripping, remove ice-water bath, in room temperature (24 ℃) with reaction mixture stir about 2 hours.
After 2 hours stirring, reaction mixture is cooled to about 10 ℃, drip 335g by 39g chlorine with contain 12% the chlorine bleach liquor 50 minutes of the aqueous solution preparation of 44.3g sodium hydroxide.After dripping, use frozen water cooling and stirring reaction mixture 60 minutes, then, further stirred 5 hours in room temperature.
In whipping process, be settled out brown crystallization.Also clean by the crystallization of filtering collecting precipitation with 300ml water.Air-dry these crystallizations are to obtain 68.5g (productive rate: above-mentioned target compound 85%).The fusing point of this compound is 182-183 ℃.
Embodiment 2
1-(2,4 dichloro benzene base)-1,2, the preparation of 4-triazole-5-ketone
In one 2 liters four neck flasks, place the 250ml trimethyl carbinol and 50g 2,4 dichloro benzene hydrazonium salt hydrochlorate, and with this flask of nitrogen purging.Then, at the aqueous sodium hydroxide solution of 25 ℃ of addings by the 9.8g dissolution of sodium hydroxide is obtained in 49ml water.At stir about after 10 minutes, reaction mixture is carried out the frozen water cooling, and 10 ℃ of formalins that drip 20.5g 36% 10 minutes.After dripping, use frozen water cooling and stirring reaction mixture 30 minutes.
At 10 ℃, be suspended in Zassol in the 80ml water by using dropping funnel in reaction mixture, once to add 20.1g.Use 10ml to wash out the Zassol that sticks on the dropping funnel, and scavenging solution is injected flask.
Subsequently, after Zassol adds, dripped 18.4g acetate immediately 10 minutes.
Then, remove frozen water cooling bath, and with reaction mixture stirring at room 2 hours.In whipping process, temperature of reaction raises about 5 ℃ and also gets back to room temperature (25 ℃) at leisure.
Once more reaction mixture is carried out frozen water cooling, and the aqueous sodium hypochlorite solution of 10 ℃ of Dropwise 35 7g 5% 40 minutes.After dripping, use frozen water cooling and stirring reaction mixture 1 hour, then, further stirred 4 hours in room temperature.In whipping process, be settled out brown crystallization.Clean by crystallization and the water that filters collecting precipitation.Air-dry these crystallizations are to obtain 46.8g (productive rate: above-mentioned target compound 87%).The fusing point of this compound is 188-189 ℃.
Embodiment 3
1-(2-aminomethyl phenyl)-1,2, the preparation of 4-triazole-5-ketone
In one 5 liters four neck flasks, stir the 1000ml trimethyl carbinol and 238g 2-methylphenylhydrazine hydrochloride.In gained solution, add aqueous sodium hydroxide solution by the 63g dissolution of sodium hydroxide is obtained in 300ml water.After having stirred about 15 minutes, in ice-water bath, reaction mixture is cooled to 5 ℃, and drips the formalin 45 minutes of 131g36%.After dripping, use frozen water cooling and stirring reaction mixture 20 minutes.Subsequently, the 117g Zassol that once adds in the 600ml water is starched.After adding, the temperature of reaction mixture has raise 15 ℃.After the adding of Zassol is finished, reaction mixture is cooled to 5 ℃, and dripped 110g acetate 20 minutes.After dripping, remove frozen water cooling bath, in room temperature with reaction mixture stir about 3 hours.
After 3 hours stirring, reaction mixture is cooled to about 10 ℃, and drips the chlorine bleach liquor 90 minutes of 1000g 12%.After dripping, use frozen water cooling and stirring reaction mixture 60 minutes, then, further stirred 5 hours in room temperature.
Then, under agitation reaction mixture is heated at leisure about 100 ℃ from reaction mixture, distilling out the trimethyl carbinol, and concentrate it.A moment later, by filtering the water cleaning of collecting the resistates that solidifies and using 1000ml.The coarse crystallization of dry gained is also cleaned to obtain 207g (productive rate: above-mentioned target compound 79%) with the 500ml Di Iso Propyl Ether.The fusing point of this compound is 148-149 ℃.
Embodiment 4
1-(2,4 dichloro benzene base)-1,2,4-triazole-5-ketone
In one 2 liters four neck flasks, the 30g dissolution of sodium hydroxide in 170ml water, and is added the 700ml trimethyl carbinol.This mixture is carried out water cooling, and at 20 ℃ of formalins that add 59g 36%.Then, added 137g 2,4 dichloro benzene hydrazonium salt hydrochlorate 10 minutes.After adding, 20 ℃ of stirred reaction mixtures 2 hours.In frozen water cooling bath, this reaction mixture is cooled to 10 ℃, and once adds 144g potassium cyanate, 150ml water and 370mg neutralized verdigris (II) monohydrate.Use the oxygen blow reaction vessel, and drip the mixture 20 minutes of 109g acetic acid and 100ml water immediately.After being added dropwise to complete, place oxygen atmosphere to stir 5 hours reaction mixture at 10 ℃, further stirred 3 hours at 55 ℃ then.
Under reduced pressure, from reaction mixture, distill out the trimethyl carbinol and make it concentrated.In enriched material, add 200ml toluene.Then, the aqueous sodium hydroxide solution with 60ml 40% extracts this mixture three times.Clean water layer twice with 200ml toluene, and add the spissated hydrochloric acid of 200ml.The crystallization of filtering-depositing, twice of usefulness 200ml water cleaning and drying, 130g (productive rate: above-mentioned target compound 88%) obtained.The fusing point of this compound is 188-189 ℃.
Embodiment 5
1-(2,4 dichloro benzene base)-1,2, the preparation of 4-triazole-5-ketone
In one 2 liters four neck flasks, add in the 700ml trimethyl carbinol and the 170ml water at 20 ℃ of formalin and 0.1g acetic acid with 59g 36%.Then, added 113g 2,4 dichloro benzene hydrazine 10 minutes, then stirred 2 hours.In frozen water cooling bath, this reaction mixture is cooled to 10 ℃, and once adds 144g potassium cyanate, 150ml water and 370mg neutralized verdigris (II) monohydrate.Then, air is blown in the reaction solution, and drips the mixture 20 minutes of 109g acetic acid and 100ml water immediately.After being added dropwise to complete, this reaction mixture was stirred 8 hours with being blown into the air method at 10 ℃, further stirred 3 hours at 55 ℃ then.
Under the pressure that reduces, from reaction mixture, distill out the trimethyl carbinol and make it concentrated.By filtering the water cleaning of collecting the resistates that solidifies and using 400ml.The dry raw crystallization is to obtain 137g (productive rate: above-mentioned target compound 93%).The fusing point of this compound is 188-189 ℃ (from the toluene recrystallize).
Embodiment 6-13
With the method synthetic aryltriazolinones with different substituents identical with embodiment 4 or embodiment 5.The structure and the fusing point thereof of aryltriazolinones are listed in table 1.
Table 1
| ????X n | Fusing point (℃) | |
| Embodiment 6 | ????2-Cl | ????155-156 |
| Embodiment 7 | ????4-Cl | ????265-267 |
| Embodiment 8 | ????2-F | ????164-165 |
| Embodiment 9 | ????3-F | ????231-232 |
| Embodiment 10 | ????2-Br | ????150-151 |
| Embodiment 11 | ????2，3-Cl 2 | ????194-195 |
| Embodiment 12 | ????2，5-Cl 2 | ????183-185 |
| Embodiment 13 | ????2，6-Cl 2 | ????243-244 |
| Embodiment 14 | ????2，4-Cl 2 | ????208-209 |
| Embodiment 15 | ????2，4-F 2 | ????231-232 |
| Embodiment 16 | ????3-Me | ????183-184 |
| Embodiment 17 | ????4-Me | ????211-212 |
| Embodiment 18 | ????2-Et | ????149-151 |
| Embodiment 19 | ????2-nPr | ????113-114 |
| Embodiment 20 | ????2-iPr | ????153-154 |
| Embodiment 21 | ????2，3-Me 2 | ????190-192 |
| Embodiment 22 | ????2，4-Me 2 | ????146-148 |
| Embodiment 23 | ????2，5-Me 2 | ????135-137 |
| Embodiment 24 | ????2，6-Me 2 | ????167-168 |
| Embodiment 25 | ????2-Me，6-Et | ????143-144 |
| Embodiment 26 | ????2-Me，3-Cl | ????197-198 |
| Embodiment 27 | ????2-Me，4-Cl | ????192-193 |
| Embodiment 28 | ????2-Me，5-Cl | ????187-188 |
| Embodiment 29 | ????2-Me，6-Cl | ????198-199 |
| Embodiment 30 | ????4-Me，5-Cl | ????159-161 |
| Embodiment 31 | ????2，4，6-Cl 3 | ????268-269 |
Numeral on the phenyl ring of the above-mentioned general formula of numeral before element or the alkyl.For example, 2,3-Cl
2Expression chlorine is attached on the 2-position and 3-position of phenyl ring in the above-mentioned general formula.
Cl: chlorine, F: fluorine, Br: bromine, Me: methyl, Et: ethyl, nPr: n-propyl, iPr: sec.-propyl
Industrial applicability
As mentioned above, be used for preparing the first method of aryltriazolinones of the present invention as the method for preparing aryltriazolinones, it is easy to by using more cheap material to carry out more easily with lower cost, and be used for preparing the second method of aryltriazolinones of the present invention as the method for preparing aryltriazolinones, it can under the condition of safety and gentleness, be carried out with lower cost more easily. The first method and the second method particularly suitable are in the large-scale industrial production of the aryltriazolinones of the material that can be used for preferably making agricultural chemicals and medicine.
Claims (8)
1. method for preparing by the aryltriazolinones of general formula (I) expression:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer,
Described method comprises with oxygenant the step by the aryl triazoles alkane ketone dehydrogenation of general formula (II) expression:
In the formula, identical in X and n and the general formula (I).
2. method according to claim 1, it is characterized in that, described with oxygenant to aryl triazoles alkane ketone dehydrogenation carry out in the following manner: use an alkali metal salt of cyanic acid and acid and aryl hydrazone reaction in advance by general formula (III) expression, formation is by the aryl triazoles alkane ketone of general formula (II) expression, adds oxygenant in the condition downhill reaction liquid of oxide catalyst and need not aryl triazoles alkane ketone is separated from reaction solution not having catalyzer or exist then:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
3. method according to claim 1 and 2 is characterized in that: described oxygenant is any in halogen, hypohalous acid, hypohalite, permanganate, hydrogen peroxide, peracid, alkyl hydroperoxide, nitric acid, dimethyl sulfoxide (DMSO) and the oxygen.
4. method according to claim 2, it is characterized in that, the reaction of an alkali metal salt of described aryl hydrazone (III) and cyanic acid and acid is carried out in the following manner: do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, use formaldehyde and the aryl hydrazine reaction of representing by general formula (IV) in advance, formation is by the aryl hydrazone of general formula (III) expression, and an alkali metal salt of interpolation cyanic acid need not aryl hydrazone (III) is separated from reaction solution with acid in the reaction solution of gained:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
5. method according to claim 4 is characterized in that: the inorganic acid salt with the aryl hydrazine substitutes described aryl hydrazine (IV), and uses alkaline purification.
6. method for preparing by the aryltriazolinones (I) of general formula (I) expression:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer,
Described method comprises an alkali metal salt and the acid of adding cyanic acid in by the aryl hydrazone of general formula (III) expression:
In the formula, identical in X and n and the general formula (I),
And then, there be not catalyzer or existing under the condition of oxide catalyst to add oxygen, form the dehydrogenation reaction of the aryl triazoles alkane ketone (II) that forms by the reaction of the aryl triazoles alkane ketone (II) of general formula (II) expression with by previous reaction simultaneously,
In the formula, identical in X and n and the general formula (I).
7. the method for preparing aryltriazolinones (I) according to claim 6, it is characterized in that: described method be included in do not have catalyzer or have acid catalyst or the condition of alkaline catalysts under, with formaldehyde and the aryl hydrazine reaction of representing by general formula (IV), formation is by the aryl hydrazone of general formula (III) expression, and in reaction solution, add an alkali metal salt of cyanic acid and acid and need not aryl hydrazone (III) is separated from reaction solution, and then do not having catalyzer or existing to add oxygen under the condition of oxide catalyst:
In the formula, X is the low alkyl group of halogen atom or 1-6 carbon atom, and n is the integer of 0-5, and when n be that a plurality of X can be identical or different when being not less than 2 integer.
8. the method for preparing aryltriazolinones (I) according to claim 6, it is characterized in that, described method comprises: use the inorganic acid salt of aryl hydrazine to substitute aryl hydrazine (IV), with formaldehyde and alkali and the reaction of described inorganic acid salt, formation is by the aryl hydrazone of general formula (III) expression, in reaction solution, add an alkali metal salt of cyanic acid and acid and need not aryl hydrazone (III) is separated from reaction solution, and then do not having catalyzer or existing under the condition of oxide catalyst to add oxygen.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP239566/00 | 2000-08-08 | ||
| JP239566/2000 | 2000-08-08 | ||
| JP2000239566 | 2000-08-08 | ||
| JP193655/2001 | 2001-06-26 | ||
| JP193655/01 | 2001-06-26 | ||
| JP2001193655A JP3863736B2 (en) | 2000-08-08 | 2001-06-26 | Process for producing aryltriazolinones |
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| CN1457338A true CN1457338A (en) | 2003-11-19 |
| CN100418956C CN100418956C (en) | 2008-09-17 |
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| JP (1) | JP3863736B2 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910139B (en) * | 2008-01-10 | 2012-09-26 | 北兴化学工业株式会社 | Process for production of phenyltriazolinone |
| CN104672157A (en) * | 2015-02-12 | 2015-06-03 | 山东潍坊润丰化工股份有限公司 | Method for preparing aryl triazolinone |
| CN109912522A (en) * | 2017-12-12 | 2019-06-21 | 北京颖泰嘉和生物科技股份有限公司 | The method for preparing triazoline-thion compound |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016526539A (en) | 2013-06-20 | 2016-09-05 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Aryl sulfide and aryl sulfoxide derivatives as acaricides and insecticides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4980480A (en) * | 1989-09-08 | 1990-12-25 | Fmc Corporation | Production of triazolinones |
| US5256793A (en) * | 1992-05-13 | 1993-10-26 | Fmc Corporation | Triazolinone ring formation in tert-butanol |
| JP3728324B2 (en) * | 1997-02-26 | 2005-12-21 | 北興化学工業株式会社 | 1-Substituted-4-carbamoyl-1,2,4-triazol-5-one derivatives and herbicides |
-
2001
- 2001-06-26 JP JP2001193655A patent/JP3863736B2/en not_active Expired - Fee Related
- 2001-07-30 WO PCT/JP2001/006543 patent/WO2002012203A1/en active Application Filing
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910139B (en) * | 2008-01-10 | 2012-09-26 | 北兴化学工业株式会社 | Process for production of phenyltriazolinone |
| TWI402260B (en) * | 2008-01-10 | 2013-07-21 | Hokko Chem Ind Co | Method for producing phenyl triazolinone |
| CN104672157A (en) * | 2015-02-12 | 2015-06-03 | 山东潍坊润丰化工股份有限公司 | Method for preparing aryl triazolinone |
| CN104672157B (en) * | 2015-02-12 | 2017-06-27 | 山东潍坊润丰化工股份有限公司 | A kind of preparation method of aryltriazolinones |
| CN109912522A (en) * | 2017-12-12 | 2019-06-21 | 北京颖泰嘉和生物科技股份有限公司 | The method for preparing triazoline-thion compound |
| CN109912522B (en) * | 2017-12-12 | 2021-04-13 | 北京颖泰嘉和生物科技股份有限公司 | Process for preparing triazolinethione compounds |
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| JP2002179655A (en) | 2002-06-26 |
| WO2002012203A1 (en) | 2002-02-14 |
| CN100418956C (en) | 2008-09-17 |
| JP3863736B2 (en) | 2006-12-27 |
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| CX01 | Expiry of patent term |