JPH02149582A - 6-aryloxy-1h-pyrazolo(1,5-b)-1,2,4-triazole compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> and R<2> are H, alkyl, etc.; L is alkylene or arylene; R<3> is imide or nitro; X is H, halogen, etc.; n1 and n2 are 0-5). EXAMPLE:The compound of formula II. USE:A synthetic intermediate for 1H-pyrazolo[1,5-b]-1,2,4-triazole-type magenta coupler having aryloxy substitutent at 6-site and useful as a silver halide color photographic material. It is advantageous in view of cost. PREPARATION:The objective compound is produced by (1) adding a phenol of formula R<4>OH (R<4> is alkyl or aryl) to a nitrile of formula R<3>-L-CN in the presence of an acid of formula HY (Y is acid radical), (2) reacting the obtained imide ester of formula III with an aminopyrazole of formula IV, (3) reacting the resultant amidine of formula V with hydroxylamine to obtain a compound of formula VI and (4) subjecting the product to dehydrative cyclization with a dehydration agent (preferably p-toluenesulfonic acid chloride).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides 1H-pyrazolo [l,! −
t-aryloxypyrazolo [/,
! -mutual)'+2y≠-triazole compound.

(Prior art) 1H-pyrazolo [/,! -dan〕-7. The 4c-triazoles are useful as magenta couplers that give excellent hue in silver halide photographic materials, and this is disclosed in JP-A No. 2003-120001, U.S. Pat. l
It is shown in No. l-0.67≠. Furthermore, % opening 4--
λ0P1717 has this 1H-pyrazolo[/,! It has been shown that high sensitivity and high gradation (r) can be obtained when the 4-position substituent of triatoryls is a furkyloxy, aryloxy, or heterocyclic okyne group.

Therefore, the 3rd position is substituted with 7-lyloxy, resulting in 91H-pyrazolo[/,! -dan〕-7. There has been a need to develop a synthetic intermediate suitable for producing λ,4L-) lyazole magenta couplers and which is advantageous in terms of cost.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a monomer having a 7-aryloxy substituent at the 6-position that is useful for silver halide color photographic light-sensitive materials.
H-pyrazolo [l,! t-aryloxy-1H-pyrazolo[7, 7゜co,≠-triazole-based magenta coupler synthesis intermediate]-/, 2. II
- To provide triazole compounds.

Cl! Means for Solving Problem 1) The present inventors have obtained 1H-pyrazolo [/l! -dan〕-7. As a result of extensive research to develop a cost-effective synthetic intermediate suitable for the production of λ,≠-triatoryl magenta couplers, t-aryloxy-1H-pyrazolo[l,! -see)'
+ ' r≠-6-aryloxy-1H-pyrazolo [/], which is important as a synthetic intermediate for triazole-based magenta couplers.

j-b2) -/, ko, Hiro-triazole compounds were discovered, and based on this knowledge, the present invention was accomplished.

That is, the present invention represents a group represented by the following general formula (1) (wherein R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyla ξ) group, or an anilino group. L represents an alkylene group or an arylene group. R3 represents an imido group or a nido group. X represents a hydrogen atom, a halogen atom, anl representing an alkylthio group or an arylthio group, and R2 represents an integer of 0-1. Note that R1, R
2 may be combined to form a ring. ) 6-aryloxy-1H-pyrazolo [/,! -b)-
/, 2. ≠-triazole compounds are provided.

In the present invention, among the compounds represented by the above general formula, R,
To explain R1L%X in detail, R1 and R are hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine, iodine)
, carbon number l~30 preferably /~l! an alkyl group (e.g. methyl, ethyl, isopropyl, t-butyl, cyclohexyl, decyl, benzyl, methoxyethyl, phenoxyethyl, J-(p-acetylamidophenyl)propyl), having 6 to 30 carbon atoms. Preferably a 7-aryl group of t to /j (e.g. phenyl, p-methoxyphenyl, 0-
methoxyphenyl, m-benzenesulfonamidophenyl, naphthyl), alkoxy groups, hydroxyl groups (e.g., methoxy, ethoxy, methoxyethoxy, phenoxyethoxy, -1(p-sulfonamidophenoxy) ethoxy, -benzenesulfonamidoethoxy, impropoxy, dodecyloxy)
, an aryloxy group having t to 301 carbon atoms, preferably 6 to 1 carbon atoms (e.g., phenoxy, p-methoxyphenoxy, 0
-methoxyphenoxy, co,≠-methΦdiphenoxy,
Tip 6-Medoxyphenoxy), an alkylamino group having 1 to 3 carbon atoms, preferably 1 to /j carbon atoms (for example, methyl ai
), eteramino, decylamino, dimethylamino, diethyl 7mino), carbon number 6 to J□, preferably j-/j
represents an anilino group (for example, phenylamino, 2-chloroanilino, N-methylanilino, 3-flucoacyanilino).

Preferably, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryoloxy group,
It is an alkylamino group.

L is a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, /, 10-tethylene, -CH, CH2-
0-CH2CH2-), substituted or unsubstituted phenylene group (e.g. tfd, t, 4t-:yunisine, /, J
-) Unishin, a n group in which R is a hydrogen atom or an alkyl group and n is 0 or /, or /,! -phinidine group, i, ≠-phenylene it's.

X is a hydrogen atom, a halogen atom (e.g. chlorine, bromine, iodine, fluorine), carbon number 1 to 301, preferably /-, 20
alkylthio groups (e.g. methylthio, benzylthio,
--cyanoethyl f,t,/-ethoxycarbonyltridecylthio), carbon number nor 30. Preferably /~2Q arylthio group C examples, t, aenylthio, λ-carboxy7enicylthio, λ-butoxyj-1-octylphenylthio, λ~pivaloylaminophenylthio, Hiro-
Methanesulfonylphenylthio, ≠-octanesulfonamidophenylthio). Preferably a hydrogen atom,
It is a halogen atom or an arylthio group.

Examples of the imide group represented by R3 include a phthalimide group and a succinimide group.

Specific examples of the ring formed by connecting R1 and R2 include a saturated or unsaturated hydrocarbon ring (e.g. benzene ring) or a petero ring (e.g. pyridine ring, pyrrole ring) having t~ as a member.
can be mentioned.

Below, in the present invention, representative t-7 lyloxy-1H
-Pyrazolo [l,! -dan] 'p2p≠-Specific examples of triazole compounds are shown below, but the invention is not limited thereto.

4L) λ) IJ) needle //) /l) /the law of nature) , 2ri Coro) 2.2) λ4L) The physical properties of the above-mentioned exemplified compounds are as follows.

melting point lri/, J~/rij,! 'C 19ko, O~iyr, z　c /4≠, 3~/17.0°C /lri, Q~i7o, roc 2/l, ni ~ 2/r, J’C 1tr, o ~ iy, z, o’c /12.2~itt,o0c λhiroλ, 3~λ≠≠63°C /rF, J~lri/, J °C λ/1. /~λit,z0c λλλ, λ~λ2! , 20C /71.3~/I1. ! 'C Ko13.3~λ/J,! 0C /60. ! ~/A! ,j0C xot,, x ~ xoy, o’c /io, 2~1t4c, o’C /J/, J~134A, 3°C /71.1～/r/ l　yr, r　〜/10 /4!1.　λ〜l　jO //r, 0~/koO il il /It, J~/ta1 2 pieces! ,! ~Co21 i1 The compound of the present invention can be prepared using the following reaction scheme ( can be synthesized.

) (wherein R-R%L, n1, n2, and X have the same meanings as above, R represents an alkyl group or an aryl group, and Y represents an acid group. group or arylthio group (IV), (V),
X may be introduced at any stage of (■), (■), or (1), and stages (IV) to (■) are indicated by <X>. ) An embodiment of the method for synthesizing the compound of the present invention will be described according to the above reaction scheme (1).

The method of obtaining imidoester (III) by adding alcohol or phenol (ROH) to nitrile (■) in the presence of acid (HY) is well known as the Pinner method (S, R, 5andier.

W, Karo, “Organic Functiona.
lGroup Preparations=, Vol.
J.

Academic (/ri72), Chapter, I
;H.

Henecka, P. Kurtz in “Met
Hodender Organischen Che
mie (Houben-Weyl)', Band■
, Georg Thieme (/rijJ), p, 4F7
~701. reference). - The preferred acids generally used are hydrogen halides, more preferably hydrogen chloride.

Ether, dioxane, etc. are preferred as the solvent, and when nitrile is poorly soluble, a mixed solvent with a haloalkane solvent such as chloroform may be used. Reaction temperature is 00C
to room temperature, and the product usually precipitates from the reaction solution.

In the step of obtaining cyamidine (V) by the reaction of imidoester (■) and 7minopyrazole (■), the preferred solvent is alcohol such as methanol or water. however,
In the case of water, the imidoester (II[) reacts with water and easily becomes a carboxylic acid ester, so during the reaction, first the imidoester (III) has an equivalent of /~λ, preferably 1.2
The decomposition of the diimidoester (II) can be prepared by dissolving an equivalent amount of 7minopyrazole (■) in water and adding the solid imidoester (I[[) to the vigorously stirred solution. The reaction between aminopyrazole (IV) and imidoester (I[[) is usually extremely fast. When using an alcohol such as methanol, the added layering is not very important. The reaction temperature is θ to 4Ao"c, preferably room temperature. Also, the molar ratio of (III) and (IV) is preferably 0.j:/-j:/, more preferably o,
Use with z:i to 2:l. Imidoesthetic/I/(II
When a salt of I) is used, a salt of amidine (Y) is obtained, but imidoester (III) does not necessarily have to be a salt. In addition, in this reaction, some (■) (R to R, L,
and the type of imidoester (III>).However, it is usually not necessary to isolate amidine (V) to obtain amidoxime compound 1), and the presence of (■) poses no problem. Used as is in the next reaction. If the presence of (■) is inappropriate, heating with ammonium chloride in methanol will convert all (■) to amidine (V).

To obtain the amidoxime compound (Vl), add l-2 oil amount, preferably /, to the amidine (V) solution obtained by the above method. Equivalent amount of hydroxylamine solution from 0 to 70°
C1 may preferably be added at room temperature. When the solvent used in the reaction is alcohol, the hydrochloride of hydroxylamine is dehydrochlorinated in alcohol with sodium alcoholade, and the by-produced common salt is filtered and added. When the reaction solvent is water, the hydrochloride or sulfate is reacted with a base such as potassium carbonate in water, and the! I'll add it. Since the amidoxime compound 1) usually crystallizes well, it can be isolated from the reaction solution relatively easily, but if it does not crystallize, an extraction operation is required.

The extraction operation is carried out in a bilayer system of water, or a saline solution and a water-immiscible organic solvent (e.g. ethyl acetate, dichloromethane, chloroform), or a bilayer system of saline solution and a water-immiscible organic solvent (e.g. A two-layer system of acetonitrile) is used.

The synthesis of the compound represented by general formula (I) by dehydration ring closure reaction of the compound represented by general formula (Vl) is preferably carried out using a suitable dehydrating agent in the presence of a base. In the reaction with a dehydrating agent, the reaction solvent is preferably dimethylacetamide, acetonitrile, tetrahydrofuran,
It is preferable to use a dehydrating agent such as dioxane in an amount sufficient for the reaction to proceed sufficiently (usually 1/'!k), and the reaction temperature is θ~ko! 0C1 reaction time Q,! A range of ˜j hours is preferred. As the dehydrating agent, in addition to p-)luenesulfonic acid chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, phosphorus oxychloride, thionyl chloride, etc. can be used, but p-)luene/sulfonic acid chloride is preferred. The dehydrating agent is/~
The range of j equivalents is preferred, and the range of l-1 equivalents is more preferred.

In addition to triethylamine, bases include tertiary amines such as diisopropylethylamine, pyridine,
≠-dimethylaminopyridine, pyrazole, etc. are used, and pyridine is preferred.

The amount of this base is O0! ~λ equivalent, preferably 1 equivalent. The ring-closing reaction of the addition reaction product of compound 1) and a dehydrating agent is carried out using an ether solvent such as tetrahydro7rane or dioxane, an alcohol solvent such as methanol, or an amide solvent such as dimethylacetamide, preferably with the above base. (usually 7 equivalents). The reaction temperature is O0C
-7o.

A range of 0C is preferred, more preferably room temperature to ro'
It is C. The reaction time is 0.3-. There is 2'IO time, more preferably /~ko waiting time.

Conditions other than the above are Tokukaisho! Tar/7/ri! can be carried out according to the method described in US Pat. No. 1f, 14LO, 61≠.

1H-pyrazolo [/,!] obtained according to the above formula (1). −
Although the Hirotriazole derivative '+2 can be separated and recovered from the reaction solution by a conventional method, it may also be used as a raw material for the subsequent reaction without any isolation if necessary. Suitable isolation methods include recrystallization, solvent extraction, filtration, column chromatography, thin layer chromatography, etc., used alone or in appropriate combinations.

(Effect of the invention) 6-aryloxy-1H-pyrazolo [/2.
If a triazole compound is used, 1H-pyrazolo- with an aryloxy substituent at the 6-position
[l,! -g)-/, 2,1IL-triazole-based magenta couplers can be easily synthesized in high yield, increasing the utility value of 1H-pyrazolo(/, j-b)-7,λ, Hiro-totrizole-based magenta couplers be able to.

(Example) Next, the method for synthesizing the compound of the present invention will be described in more detail based on Examples.

Acetonitrile! 0- to compound (co/)≠t.

Add 3P, stir at room temperature, and add triethylamine Jl.
rptl was added dropwise. After stirring for 30 minutes at room temperature, compound (2x) (obtained by the Pinner method from 7-thallimide acetonitrile, methanol and hydrochloric acid) rt,
oy was added and the mixture was stirred for 3 hours. A few crystals were collected from the reaction mixture, and 200 ytl of N, N-
Dimethylacetamide was added and dissolved, and the mixture was stirred at room temperature. On the other hand, dissolve hydroxylamine hydrochloride/l, 7F in methanol/70xl, add sodium methoxide,
A 2t% methanol solution was prepared by adding 4 Lr and λd, and the resulting common salt was dropped into the N,N-dimethylacetamide solution while going door to door. After the mixture was stirred at room temperature for 5 hours, the insoluble materials were removed. Add water to this p solution,
The obtained crystals were washed with water and dried to give compound (co3).
．． ! (yield 7/%).

Melting point: /Q, 2~/YJ, J °C 72,2-Dichloroethane 10OJ to compound (co≠) 3
/, Hiro 1 was added and dissolved, and 7.7 g of sulfuryl chloride was added dropwise thereto at room temperature. After stirring for 30 minutes, 1,-1 dichloroethane was distilled off under reduced pressure. On the other hand, compound (2
3)≠1. ry was dissolved in 100-proof N,N-dimethylacetamide, and the mixture prepared from the above-mentioned compound (2≠) and sulfuryl chloride was added to the N,N-dimethylacetamide of jOxtl.
The mixture was dissolved in N-dimethylacetamide and added dropwise over 3Q minutes at room temperature. After stirring for 7 hours, the reaction mixture was
of water was added to obtain an oily substance (stiffness). After removing the water by decantation, N,N-dimethylacetamide, 2/OxJ was added to the obtained oily substance and dissolved.
Add p-toluenesulfonyl chloride 20. while keeping the temperature below 0C. Add Of, followed by pyridine r, 3oy
was dripped. After stirring at room temperature for 2 hours, water was added to obtain an oil. After removing water with decantation/N, N
-Add and dissolve dimethylacetamide jOd, then methanol,! 00m, pyridine 1. Add JOri,
The mixture was stirred for 1 hour under heating and reflux conditions. After methanol was distilled off under reduced pressure, water was added to obtain an oil.

Water was removed by decantation, acetonitrile was added and stirred, and the obtained crystals were separated and dried to obtain the target exemplary compound (2). Obtained.

Melting point: / Octopus, O ~ / Rij, 5°C NMR: /u, /j (brs, 1H), 7. rNr.

0 (m% HiroH), g, z-7,2 (m, 7H), ≠,
ri, t(s, JH), 3. rij (tlJJ.

JHz, JH), 3.717 (J, JH), /, 3-/
, I (m, 4H), /, //(s, jH), 0,
Pj (t, J=7, JH2, jH), θ,! , t(s
, Ta 1-i), Synthesis of Example λ0 Exemplary Compound (Hiroshi) (Kota) (λr) (Exemplary Compound (≠)) Add compound (,2/) A Hiro and t to 200xl of methanol, and reduce the internal temperature to io 77.2xl of triethylamine was added dropwise to the mixture while stirring at a temperature below 100 m. Next, the compound (-2
J) Add 10rp (obtained from j-phthalimidozolobionitrile, methanol and hydrochloric acid by pinner method) and bring to room temperature! The mixture was stirred for 30 minutes.

On the other hand, hydroxylamine hydrochloride 2ry was mixed with methanol 2r
Dissolve in Otd and add 2t of sodium methoxide to this solution.
% methanol solution (ram) was added, and the resulting salt was passed from house to house, and the previous compound (2/) and compound (2/2) were mixed.
This product was added to the reaction solution obtained from (B). Then, after stirring at room temperature for 2 hours, too much water was added, and the obtained crystals were separated, washed with water, and dried to obtain the desired compound (λ7
) to obtain t, 7y (yield r7%).

Melting point: /6ri! ~i7i, o”c Add compound (λ7) to 4l-00xtt of N,N-dimethylacetamide, dissolve it by adding 7F, and bring the internal temperature to 100C.
p-) Luenesulfonyl chloride 31. ．． After adding Of, pyridine/4t and Tata were added dropwise, and the mixture was stirred at room temperature for 7 hours. On the other hand, /,λ−
Compound (ay-)zt, r in dichloroethane JOOrd
Add p and dissolve, add sulfuryl chloride 7,
Iytl was added dropwise. After stirring this for 70 minutes,
The λ-dichloroethane was distilled off under reduced pressure, and the resulting residue was dissolved in 10ml of N,N-dimethylacetamide and added to the reaction mixture obtained from the previous compound (27) at room temperature for 30 minutes. dripped. The mixture was stirred at room temperature for 7 hours, poured into ice water, and an oily substance was obtained. To the obtained oil were added 2 parts of methanol, 1 part of pyridine, and 1 part of pyridine to dissolve it, and after stirring under heating and reflux for 7 hours, it was poured into ice water, and 300 d of acetonitrile was added to the obtained oil, and the mixture was stirred. , count the precipitated crystals, and select the desired exemplified compound (+')
≠,t,oy (yield 34L%) was obtained.

Melting point 2/otsu5', (7~/jri,!0CNMR(CDC
/3): δ=IO1rij (brs.

1H) J, j-7,, r (m% IIH), 3. r-Hiro, / (m, IIH), 3.70C5, JH), 3°0J
(t, J=A, □Hz%, 2H), 0.7-/
.

ri(m,, IIH), 0.1!10(s, taH),
Example 3 Exemplified Compound (Rinodaiso/Hα (Co1) (Exemplified Compound (j)) Compound (21) It in acetonitrile JjOtxl.

Triethylamine 6/
, /xt were added dropwise, and the mixture was stirred for 1 minute.

After adding compound (JO) (obtained by the Pinner method from m-nitrobenzonitrile, methanol and hydrochloric acid) to the mixture at room temperature, the mixture was stirred for 5 hours and the precipitated crystals were collected. On the other hand, hydroxylamine hydrochloride 30
．． Dissolve ≠1 in methanol 300- and add 2r% methanol solution tj- of sodium methoxide to prepare a solution. This was added dropwise to the solution at room temperature while stirring. After stirring for 11 hours, water/l was added, and the obtained crystals were separated, washed with water, and dried to obtain the target compound (3/1) at 10 rp (yield to %).

Melting point: /G! , j ~ 11, 4.2 °CN, compound (31) 4 /f in N-dimethylacetamide 2jOytl
Melt it and add p- here while keeping the internal temperature below 1o0c.
Toluenesulfonyl chloride 3/≠7 was added, followed by dropwise addition of 13.0 ml of pyridine, and the mixture was stirred at room temperature for 2 hours.

Water/l was added thereto to obtain an oily substance. After removing water by decantation, 300xl of methanol and pyrazole//, 19 were added and dissolved, and the mixture was stirred at room temperature for 3 hours and then heated under reflux for 1 hour. This thing-
After standing overnight at room temperature, nine of the obtained crystals were taken to obtain the target exemplary compound <r)2o, 3PC yield 3j%).

Melting point: Co/lb, j N2/1. j 'CNMR(DM
S”6): δ=/J, AA(s.

1H) A, rt, ri(m, rH),! ,≠3(s,1
H), J, lo (S, JH), Example Hiroshi Exemplary Compound (
Synthesis of 10) (3/) (3,2) Exemplary compound (10) Add compound (31)/JJP to methanol roottt, and add compound (λ6) 162 at room temperature while stirring. The mixture was stirred at room temperature for 3 hours.

Meanwhile, 4 mL of hydroxylamine hydrochloride TP, OP
A solution was prepared by dissolving the salt in methanol and adding 1 liter methanol solution of sodium methoxytokozati, and adding this solution to the reaction solution while passing the generated common salt from house to house. Then, after stirring at room temperature for 3 hours, ethyl acetate
Subsequently, aqueous ammonia/lt was added to carry out an extraction operation. After drying the ethyl acetate layer with anhydrous sodium sulfate, it was concentrated using a rotary evaporator, and acetonitrile was added to the resulting residue and stirred. Nine precipitated crystals were collected and dried, yielding the target compound (3λ ) koj2
F (yield 5%) was obtained.

Melting point: izt, 3~irt,, r 0cN, Add compound (32) to 70yd of N-dimethylacetamide, dissolve, keep the internal temperature below 70°C, and add p-toluenesulfonyl chloride, IP. Next, pyridine 3. royt-dropped. After the mixture was stirred at room temperature for an hour, 200 ml of water was added to obtain an oily substance. Water was removed by decantation, and after death, 20xl of N,N-dimethylacetamide was added to dissolve, and 7.1091 of methanol-〇〇 #1 pyridine was added, and the mixture was stirred under heating under reflux for -hour. After cooling to room temperature, water! Water was removed by decantation from the oil obtained by adding θOsl,
Ethanol and 0 ydt were added and stirred. Take 9 precipitated crystals and obtain 10.7 crystals of the target exemplary compound (10) (
yield! 4! -%) was obtained.

Melting point: 2/6. /~λit,z　c NMR (DMSO-d6): δ=I2,70 (brs.

1H), 7.7-r, 0(m, HiroH), 4.77.2(
m, 4'H), t, JJ' (s, 1H), 3゜riu (
t%J-j, 7Hz%, 2H), J, Or(t, J=
j, 7Hz, JH), 2.7j (s.

jH), Examples! Synthesis of Exemplified Compound (Noko) (3J) Methanol 2JOtttlK Compound (33)≠7, add λ, and while stirring at room temperature triethylamine, 27
, 2td were added dropwise, and the mixture was stirred for 30 minutes. Compound (CoA) 7F was added thereto while stirring at room temperature.

3F was added and stirred for 3 hours. On the other hand, hydroxylamine hydrochloride 20. R14g of the salt was dissolved in 203yd of methanol and added with sodium methoxide λt% and methanol solution, and the resulting salt was added to the reaction solution while going door to door. Then, after stirring at room temperature for 5 hours! 00aI! 9 of the obtained crystals were washed with water and dried to obtain the target compound (3≠), 7≠, 6F (yield: r%).

Melting point: /6≠, 2~/4A, 20C N,N-dimethylacetamide/00RI to compound (
3≠) Add and dissolve J4C0jp, and add p-) luenesulfonyl chloride/! while keeping the internal temperature below 100C. , 7F, and then pyridine t, j2ffi
After dropping the mixture, the mixture was stirred at room temperature for 1 hour. On the other hand, /, 2−
Dichloroethane 100ml VC compound (2≠) Kohiro, 7
．． Add P and dissolve, here 3.3 of hesulfuryl chloride.
2d was added dropwise. This was stirred for 9 minutes, then the Kodichloroethane was distilled off under reduced pressure, and the resulting residue was dissolved in CoOd's N,N-dimethylacetamide to form the previous compound (3≠). The mixture was added dropwise to the reaction mixture obtained from the above at room temperature over 20 minutes. After stirring at room temperature for 1 hour, the mixture was poured into ice water to obtain an oily substance. The water was removed by decantation, and 700 tons of methanol was added to the resulting oily substance.
d, pyridine 4. Pt was added and dissolved, and after stirring under heating and reflux for - hours, it was poured into ice water to obtain an oily substance. The water was removed by decantation, and the obtained oil was purified by column chromatography to obtain the desired exemplary compound (/, 2) 3i, /PC yield! I got 11.

Melting point: /7r, J~It/#’C NMR (DMSO-d,): δz/J, /6 (brs.

1H), 7. ffj(s, 4!H), 4. j-7,2(
m, 7H), J,! -Hiroshi, / (m, 4'H), 3°/2
(t%J=j, 7Hz, uH), λ, aj (q,
Je=7, JHz%λH), /, J-/, ri(m,
taH), / , /l(s%AH),Q,ri! (t,
J=7.7Hz1 jH), o, jt (s.

Example t Synthesis of Exemplified Compound (/j) (C1) (3r) Compound (37) in methanol 300-6. /P is added, and sodium methoxide 2t% methanol solution /
Add 31 dropwise and at room temperature! After stirring for an hour, the apparatus was turned off overnight. Compound (co/)Pt, 7f was added to this mixture, and the mixture was stirred at room temperature for an hour. On the other hand, hydroxylamine hydrochloride 33. Dissolve ≠7 in methanol J j 0ILt, and add r% methanol solution to it.1. , Jml was added, and the resulting common salt was added dropwise to the reaction mixture consisting of (37) and (λl) while going door to door. The mixture was stirred at room temperature for 70 hours, and then allowed to stand overnight.The mixture was poured into water to obtain an oily substance. 200 ytl of isopropyl alcohol was added to the oil obtained by removing water by decantation and stirred, and the precipitated crystals were separated into 9
The residue was taken and dried to obtain 10 t,≠y of the target compound (3r) (yield t3%).

Melting point: /22.2-12t, 00c N,N-dimethylacetamide 720- to compound (3r
) Melt μop and keep the internal temperature below 100C Cy fk
ybE rap-toluenesulfonylchlor1.1)
' / 10F and then pyridine 41c7. Jf was added dropwise.

Drained water 21, which had been stirred for 3 hours at room temperature, was added to obtain an oily substance. Add 500ml of dimethylacetamide to the oily substance from which water was removed by decantation. Pyrazole≠0.7j/
The mixture was stirred at room temperature for 6 hours, and then left for two nights. Ethyl acetate/l and water/l were added to perform an extraction operation, and the obtained ethyl acetate layer was dried over anhydrous sodium sulfate, concentrated, and when 00 ml of isopropyl alcohol was added to this residue, crystals were precipitated. did. The crystals are collected and dried to obtain the desired exemplified compound (/j)/t
0P (yield 70%) was obtained.

Melting point: cott, ko~20ri, ooc NMR (DMSO-d,): δ=12. RiJ (brs.

jH), 7, r-r, o (m, 4'H),
6. -7, ko (m, 4CH), r, t! (CL, J=
7.1Hz, jH),! 6koj (s, jH), 3.7P
(s,jH),/,77(d,,T-7,1Hz.

JH), Now, t-aryloxy-j obtained by the present invention
H-Pyrazolo [/,! -See] -l, λ.

Using ≠-triazole compounds as synthetic intermediates, various 6
jH-pyrazolo [l,
! -See]-7. A 4t-) lyazole magenta coupler cannot be obtained. - As an example, t-aryloxy-jH-pyrazolo [
/, j-k]-l.

, shows a synthesis example of a 2,4'-triazole coupler.

Synthesis of Exemplified Compound (6)/Add the compound (λhiro) to 2-dichloroethane≠jO-, and at room temperature, add hesyl 7lyl chloride
, Iyd was added dropwise. After stirring for 30 minutes, under reduced pressure/
, 2-dichloroethane was distilled off.

On the other hand, exemplified compound (j) λ43F was added to 700xl of DMF.
Dissolve the above compound (2≠) and Sur7 here.
The solution prepared from lyl chloride was dissolved in 600 ml of DMF and added dropwise over 30 minutes at room temperature.

After stirring for 7 hours, water of 101 was added to the reaction mixture, and the obtained crystals were collected by F, washed with water, and dried to obtain the desired exemplary compound (A) 4'j≠y (collection rate 0%). I got it.

Melting point/lsr, 0~/72.00C Synthesis of compound (3) Reduced iron, zioy, ammonium chloride ramco i1p, acetic acid,
2Hirod and water JOOtttl were added, and the mixture was stirred for 1 hour under heating and reflux. Improper tool here/,! 1, and while heating under reflux again and stirring, exemplified compound (6) ≠ 3 F
was added over 3θ minutes. Thereafter, the mixture was refluxed and stirred for 1 hour, and the insoluble materials were collected separately and concentrated using a t-rotary evaporator. Methanol/
, jl and count the precipitated crystals to obtain the desired compound (
3) 37 pieces of 1 (yield 0%) were obtained.

Melting point: iro, r ~ ir3. z'c compound (Reference/)
Synthesis of N,N-dimethylacetamide 3≠01 and acetonitrile AOOtdVC compound (3ri) 2≠01 were dissolved, and the compound (see 〇) was added thereto while keeping the internal temperature below 200C.
/riop was added dropwise, and then 3 tons of pyridine and oy were added dropwise. After stirring at room temperature for 3 hours, extraction was performed by adding ethyl acetate tl and water/l, and the resulting ethyl acetate layer was washed three times with /l of water. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate, and then concentrated using a rotary evaporator. Add 00ml of acetonitrile to the obtained residue, count the precipitated crystals, and recrystallize again with 00d of acetonitrile to obtain the target compound (≠/)3≠OF (yield 2Q%) f! :Obtained.

Melting point near ! ~7　r C

Claims (1)

[Scope of Claims] A 6-aryloxy-1H-pyrazolo[1,5-\b\]-1,2,4-triazole compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, hydroxyl groups, alkoxy groups, aryloxy groups, alkylamino groups, or Represents an anilino group.L represents an alkylene group or an arylene group.R
^3 represents an imide group or a nitro group. X represents a hydrogen atom, a halogen atom, an alkylthio group or an arylthio group. n_1 and n_2 represent integers from 0 to 5. Note that R^1 and R^2 may be combined to form a ring. )