JPS60172982A - Pyrazolo(1,5-b)(1,2,4)triazole derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 and R2 are H, (substituted) alkyl or (substituted) phenyl; X is H, halogen, acyl, nitroso or (substituted) amino; Y is H or aralkyl]. EXAMPLE:7-Acetyl-1-benzyl-2,6-dimethylpyrazolo[1,5-b][1,2,4]triazole. USE:A magenta coupler for color photographic material. PREPARATION:The objective compound can be produced e.g. by (1) reacting the compound of formula II (R3 is methyl; R4 is alkyl) (e.g. 2,5-dimethyl-1,3,4-oxadiazole) with benzylamine, (2) treating with an amination agent (e.g. hydroxylamine- O-sulfonic acid) and HI to obtain the compound of formula III (e.g. 1-amino-4- benzyl-3,5-dimethyltriazolium iodide), and (3) subjecting the compound to the cyclization condensation reaction in the presence of the acid anhydride of formula IV [R5 is (substituted) alkyl or (substituted) phenyl] (e.g. acetic anhydride) and a base.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel azapentalene compounds, pyrazolo[
1,5-b][1,2,4]) This relates to lyazole derivatives.

(Background of the invention) It has a nitrogen atom at the bridgehead position, and this nitrogen atom and another
A general formula with a minimum of 2 and a maximum of 6 nitrogen atoms, in which 10 π electrons can interact, including the lone pair of nitrogen atoms...: Three movable double bonds. show.

・; Indicates nitrogen or carbon atom.

The 5-5 fused polycyclic compound represented by is commonly called "azabenthalene". Until now, this compound has been studied mainly from the viewpoint of structural chemistry, interest as a physiologically active substance, and interest as a magenta coupler in photochemistry (J, Elgureo, R, Jacquier,
S, Mign.

nac-Mondon, J., He1erocyclic.
, chem6, 10, 411 (1973), H, Ko
ga, M., Hirobe, T., Okamoto, C.
hem, Pharm, Bul2, 22,482 (19
74) , J., Bailey, J., C.S., Perk.
in I 2047 (1977) Special Publication Showa 47-2741
No. 1, Japanese Unexamined Patent Application Publication No. 1129586 (see No. 1129586, etc.).

As a result of various studies on such azapentalene compounds, the present inventors discovered that a new bone-core azapentalene compound represented by the following general formula (II) exhibits extremely excellent properties as a magenta coupler for color photographs. Based on this knowledge, the present invention was accomplished.

(Structure of the Invention) That is, the present invention provides a general formula (wherein R and R2 represent a group selected from a hydrogen atom, an alkyl group, and a phenyl group, and these groups may be the same or different from each other; may have a substituent. Also, X is a hydrogen atom, a halogen atom, an acyl group,
Y represents a nitroso group, a heamino group or a substituted amine group, and Y represents a hydrogen atom or an aralkyl group. ) A pyrazolo[1,5-bl[1,2°4co-triazole derivative] is provided.

In the compounds of the present invention, the alkyl groups R1 and R2 include lower alkyl groups such as methyl, ethyl, propyl, and butyl groups to higher alkyl groups having up to 22 carbon atoms, for example,
It means a pentyl group, hexyl group, heptyl group, octyl group, tesyl group, undecyl group, tridecyl group, octadecyl group, etc., and may be linear or branched.

Further, the halogen atom of X means chlorine, bromine, iodine, etc., and the acyl group means an acyl group derived from an aliphatic or aromatic carboxylic acid. Moreover, as the substituted amine group of X, two substituents may form a ring structure containing the nitrogen atom of the amino group.

In the compound of the present invention, R and R2 are within a range acceptable as a coupler for color photography, and X is a coupling-off group or a group for introducing the leaving group and is photochemically acceptable. This is the base.

Next, the pyrazolo [ of the present invention represented by general formula (II)]
1,5-bl [1,2,4]) Typical lyazole derivatives are illustrated below.

6H13 Next, the method for synthesizing the pyrasolo[1,5-b][1,2,'4] triazole derivative of the present invention represented by the general formula (II') will be exemplified below.

Reaction step (1) (fir) (IV) t4 m (■) 1-In the description, the starting material oxadiazole (m) can be synthesized by the method described in Ber, Vol. 32, p. 797 (1899). I can do it.

As the 7-mining agent for (IV), hydroxylamine O-
Sulfonic acid, 0-(2,4-dinitrophenyl)hydroxylamine, 0-diphenylphosphorylhydroxylamine, etc. are effective. The compound (vl) of the present invention is obtained by cyclization condensation of N-aminotriaturium yossite (V) with an acid anhydride in the presence of a base. As the acid anhydride, a mixed acid anhydride with trimethyl acetic acid may be used.

(VT) can be further deacylated and reduced to prepare the compounds (■) and (■) of the present invention. These deacylation and reduction treatments themselves can be carried out using conventional methods.

/-' Reaction step (2) (IX) (X) (M) (If R6 is a methyl group, (IX) (R .

=CH3) can be synthesized (J, Heteroccl, c
hem, vol. 11, p. 423, 197°).

In dehydrating and cyclocondensing (XI), use a dehydrating agent J and p
- In addition to toluenesulfonyl chloride, notanesulfonyl chloride, trifluoromethanyl chloride,
Phosphorous oxychloride, thionyl chloride, etc. can be used.

G Reaction Step (3) ノ(■)(xllI)(X) Luav 5-Aminopyrazole (IX) can be synthesized in the same manner as shown in Step (2). When (IX) is reacted with imidoester hydrochloride, (X) is produced together with (Xl), but when an excess amount of ammonium chloride is added to the reaction solution and heated to reflux, (X) is converted to (X[). . (Xli)
is subjected to oxidative ring closure to obtain the compound (Xll) of the present invention. As the oxidizing agent, lead tetraacetate, N-halogenosuccinimide,
Bromine etc. are used.

Although the desired compound obtained in the reaction steps (1) to (3) described in - may be subjected to the subsequent reaction without being isolated in any way, it is usually isolated and purified by a suitable isolation means. Examples of such means include solvent extraction, recrystallization, filtration, column chromatography, and thin layer chromatography.

A compound corresponding to the general formula (II) in which R,, R2 is either an alkyl group or a phenyl group and further has a substituent is a compound corresponding to the general formula (II) in which R, R2 is either an alkyl group or a phenyl group, and further has a substituent. Although it can be obtained directly by these steps, the basic skeleton of the present invention, pyrazolo-[1,5-bl[1
, 2, 4]) After forming a lyazole ring, it may be induced into a desired substituent by a subsequent reaction. If necessary, the derivative may be derived using a compound in which X has an acyl group and Y has a protecting group such as a benzyl group. For example, as shown in Example 7 below, the amine group on the compound of the present invention can be derived into acid anilide 13 etc. by a known method.

When using the compound of the present invention as a magenta coupler in a photographic system, aromatic -
In order to adjust the coupling reaction rate of the primary amine with the oxidation product and to reduce the amount of silver used, an appropriate cuff-pulling leaving group (X in the general formula (II) above) is introduced.

A general method for introducing a coupling-off group will be explained below.

(1) Method for connecting oxygen atoms The 4-equivalent mother coupler of the present invention, pyrazolo [1°5-bl
A triazole coupler is reacted with an oxidation product of an aromatic-grade amine to form a dye, which is hydrolyzed in the presence of an acid catalyst to form a ketone form, which is then converted into a ketone form.
Hydrogenation using d-carbonic acid as a catalyst, reduction with Zn-acetic acid, or reduction treatment with sodium borohydride to give 7-
Humanroxypyraturo[1,5-b]triazur can be synthesized. By reacting this with various halides, the desired coupler connecting oxygen atoms can be synthesized. (U.S. Patent No. 3,926,631, JP-A-57-70
(Refer to No. 817) (2) Methods for connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The first method involves nitrosating the coupling active site with a suitable nitrosating agent as described in U.S. Pat. 7-amino-pyrathro[l,5-b] triazole is reacted with various halides to produce mainly amide compounds. Method 2 follows the directions described in U.S. Pat. No. 3,725,067;
Namely; Suitable 1\Rogenating agent 1 For example, sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N
- Halogenate the 7-position with bromosuccinimide or the like, and then oxidize the nitrogen heterocycle with a suitable base catalyst, triethylamine, sodium hydroxide, zaazabicyclo[2,2,2]octane by the method described in Japanese Patent Publication No. 56-45135. , anhydrous potassium carbonate, etc., to synthesize a coupler linked to the 7-position with a nitrogen atom. Among compounds linked by oxygen atoms, compounds having a phenoxy group at the 7th position can also be synthesized by this method.

The third method is an effective method when introducing a 6π or 10π electron system aromatic nitrogen heterocycle into the 7th position.
．． As described in No. 36577, more than twice the molar amount of 6π with respect to the 7-halogen compound synthesized by the second method.
Or add a 10π-electron aromatic nitrogen heterocycle to 50°
Heating at ~150°C without solvent, or in an aprotic polar solvent such as dimethyformaldehy, sulfolane or hexamethylphosphotriami-1ζ at 30°C to 150°C.
By heating at °C, an aromatic nitrogen heterocyclic group connected via a nitrogen atom can be introduced at the 7-position.

(3) Method for linking sulfur atoms Couplers substituted with an aromatic mercapto or heterocyclic mercapto group at the 7-position can be prepared by the method described in U.S. Pat. Synthesis is achieved by dissolving disulfide in a halogenated hydrocarbon solvent, converting it to sulfenyl chloride with J4H hydrogen or sulfuryl chloride, and adding it to a 4-pyrazolo[1,5-b] triazole coupler dissolved in an aprotic solvent. I can do it. A method for introducing an alkylmercapto group into the 7-position is described in US Pat. No. 4.
264.723, that is, a method in which a mercapto group is introduced into the coupling active position of the coupler and a halide is applied to the mercapto group, and S-(alkylthio)isothiourea, salt-tolerant (or bromine-hydrochloric acid) are used in one step. The method of synthesizing the two is effective.

(Effects of the Invention) The compound of the present invention thus obtained is useful as a magenta coupler for color photography. It also has the ability to be used in medicine as a physiologically active substance.

The compound of the present invention is coupled with an oxidation product of an aromatic-grade amine to produce a magenta dye having an extremely good hue and having better light and heat fastness than conventional pyrazolone dyes. Illustrated compounds are shown in the drawing, and 4-N-ethyl-
N-(2-methanesulfonamidoethyl)amino-2-
Comparison of the dye synthesized from the oxidation product of methylaniline and the dye synthesized from the comparative coupler (a) of the following formula in terms of absorption in ethyl acid 1. Shown. Note that the maximum concentration of each absorption spectrum was normalized to 1.0 for comparison. In addition, the main performance of each dye is summarized in the table below. As can be seen from the figure, the dye obtained from the compound of the present invention has almost the same maximum input position as the base element from the comparative coupler (a), and there is no subabsorption in the vicinity of 400 to 43 Onm. , the long wavelength side C tail is sharply cut, and as shown in the table below, the molar absorbance coefficient is also sufficiently large, and it can be seen that when used in a color photographic material, it is advantageous in terms of color reproduction.

Moreover, the compound of the present invention can be used as a coupler in Japanese Patent Publication No. 47-2
No. 7411 provides a magenta dye with much better light fastness than the compound disclosed in No. 7411.

of wood (maximum absorption wavelength + 60 nm) (/maximum absorption wavelength ε
The following is a more detailed explanation of the present invention based on examples.

Example 1 (Illustrative compound 1.2.3 according to reaction step (1)
(A) Synthesis of 1-amino-4-benzyl-3,5-dimethyltriazolium iodide (V) ■e ◎ (III) (IV) ff) In the following examples, (V) Unless otherwise specified, use this 1-amino-4-benzyl-3゜5-dimethyltriazolium iodide as i) 2,5-dimethyl-1 obtained by thermal decomposition of tetraacetylhydrazine.
,3,4-oxacyatool (III) 19g (0
, 19 mol) and benzylamine 31 g (0, 2
9 mol) at 110°C for 4 hours to form 4-benzyl-3,5-dimethyl-1,2,4-triatool (I
V) 26g was obtained. Yield 73%, melting point 125-127°C
.

Hydroxylamine-〇-sulfonic acid 66g (0,58
mol ) and 40 g of potassium hydroxide (85%, 0.61
mol) of potassium hydroxylamine-O-sulfonate and the above triazole (IV)
75g (0.4mol) at 80-90°C't'
After reacting for 6 hours and returning to room temperature, the pH was adjusted to 8 to 9 with a 50% aqueous potassium carbonate solution. The generated potassium sulfate was filtered off, and the filtrate was extracted three times with chloroform. 44 g (59%) of the starting material, triazole, was recovered from this filtered chloroform extract. The aqueous layer was cooled to 57%
When the pH was adjusted to 3 with an aqueous solution of hydroiodic acid, crystals were precipitated.

The crystals were filtered and recrystallized from ethanol at -20°C to obtain 39 g (31%) of (V) as pale yellow crystals.

(ii) C)-(2,4-dinitrophenyl)hydroxylamine (J, Org) as aminating agent.

Chem, 38 1239 (1973)), (V) was synthesized as follows.

4-Henjiru 1.2.4-) Rear tool (IV) 3
5g (0,,l 9+*ol) in dichloroethane 3
In addition to the 0.0m solution, 25g (0,13+ool) of 0-(2,4-dinitrophenyl)hydroxylamine was added little by little (approx.
(over 5 minutes) and stirred for a further 2 hours at this temperature. After dichloroethane was distilled off under reduced pressure, the residue was dissolved in 100 m of water, and the pH was adjusted to 3 with a 57% aqueous solution of hydroiodic acid. 2,4-dinitrophenol precipitates out,
It was removed by extraction with ethyl acetate (3 times). The aqueous layer was concentrated and the residue was recrystallized from ethanol to obtain (V) in a yield of 70%.
Obtained in %.

In addition, as an aminating agent, 0-diphenylphosphinylhydroxylamine (SynthesiS, 592
(1982), Tet rahedr.

The procedure is almost the same when using A.N. Lett, 23.3835 (1982), but in this case, after treatment with hydroiodic acid, diphenylphosphinic acid is recovered by filtration (more than 90%) without extraction. )We were able to.

(B) Synthesis of 7-acetyl-1-benzyl-2,6-dimethylvirazolo[1,5-bl [1,2,4] triazole (1) N-aminotriazorium iodide (V) 8 g (0, 0
25+*ol) in DMF (dimethylformamide)
Dissolve in 50ml of water, add 40ml of acetic anhydride, and heat at 120°C.
heated to. Then add 12.5g of sodium acetate,
The mixture was stirred at 120-130°C for 4 hours. After removing DMF, acetic anhydride, etc. under reduced pressure, the mixture was made basic with a saturated aqueous sodium carbonate solution, extracted with chloroform, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown oil. Ta. This was purified using a silica gel column in a solvent system of n-hexane-ethyl acetate, and 7-acetyl-1-benzyl-2,6-dimethylpyrazolo[1,5-
bl [1,2,4] ) Riazole (1) 3.2g
(47%). Melting point 105-107℃ □Nuclear magnetic resonance spectrum (CDCl2) δ (ppm)
: 2.36 (3H, s) 2.43-Saku 3H, s) 2.60 (3H, s) 5.80 (2H
, s) 7.0-7.2 (2H) 7.2-7.36 (3H
) (c) i-benzyl-2,6-dimethylvirazolo[1,
2 g (7,5 mmol) of F+-bl [1,2,4]) lyazole (2) was dissolved in 20+ nJl of ethanol, 20 m of concentrated hydrochloric acid was added thereto, and the mixture was heated to reflux. Removal of the ethanol under reduced pressure, basification with a saturated aqueous solution of sodium bicarbonate, and extraction with ethyl acetate yielded nearly pure deacetylated l-benzyl-2.
,6-dumethylvirazolo[1,5-bl [1,2,4
) Riazole (-do-), 1.6 g (95%) was obtained. Melting point 87-88℃ Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 2.32 (3H, s) 2.44 (
3H, s) 5.02 (2H, s) 5.22 (LH,
s) 7.10-7.40 (5H) (D) I H-2,6
-dumethylpyrazolo[1,5-b] [1,2,4]
Synthesis of triazole (3) l-benzyl-2,6-dimethylpyrazolo[1,5-b
] [l, 2.4] ) Riazole (2) 1 , 6
g (7.1 mmol) in liquid ammonia width approx. 0.8 g
The target IH-2,6-
0.67 g (70%) of dimethylpyrazolo[1,5-b] [1,2,4] triazole (3) was obtained as colorless crystals. Melting point 274-275℃ (decomposition) High acid analysis 136 (M”, 100%) Elemental analysis value C
(%) H (%) N (%) Theoretical value 52.93 5.
92 41.15 Measured value 52.85 8.02 41
．． 0'1 nuclear magnetic co-duck spectrum (CDCl2: pyridine-d5 = 1:l) δ (ppm): 2.35 (3H, s) 2.43 (3
H,s) 5.50 (IH,s) <Example 2> (Synthesis of Exemplary Compound 3 according to Reaction Step (2)) 5-Amino-3 obtained by reaction of 3-aminocrotononitrile and hydrazine aquarium -Methylpyranol (
IX) 2,4 g (25 mmol) and triethyl orthoacetate 6,0 g (37 mmol) were heated under reflux in 20 mQ of toluene for about 10 hours, and then the toluene was distilled off to give the crude product (X) as an oil. Obtained.

Nuclear magnetic resonance spectrum (CDCI3) δ (ppm): 1.28 (3H, t, J = 7°5) 1
．． 96 (3H, s) 2.22 (3H.

s) 4.19 (2H, q, J=7.5) 5.50 (I
H, s) Hydroxylamine ljj acid kjl 2, 6 g (
Dissolve 37■of) in 20ml of methanol and stir at 0°C.
7.4 ml of 8% sodium methoxide methanol solution was added. The precipitated common salt was removed by filtration and added to the methanol solution of (X) at 0°C. After the addition was completed, the temperature was returned to room temperature, stirred for about 1 hour, methanol was distilled off, and the resulting crystals were washed with chloroform.
2 g (83%) obtained. Melting point 180-185℃ (decomposed) Nuclear magnetic resonance spectrum (DMSO-d6) δ (ppm
): 1.87 (3H, s) 2.12 (3H, s) 5
．． 65 (LH,s) Elemental analysis value C (%) H (%) N (%) Theoretical value 4
8,74 8.54 38.34 measurement value 4B, 88
13.63 3f3. lo(XI) 1,5 g (
9.7 mmol) of tetrahydrofury (THF) 1
50m, Q, and add 1.2 g of triethylamine, then add 2.2 g of P-)luenesulfonic acid chloride in portions at room temperature. After stirring for 30 minutes, further 150 m
1 of THF was added and heated under reflux for 7 hours. The amine salt formed as a precipitate was filtered off, the filtrate was concentrated, and the resulting residue was purified by chromatography to obtain 30.9 g (68%). The physical property values of No. 3 completely matched those obtained in <Example 1>. In addition, a small amount of 4 (melting point 250-255℃
(decomposition)) was obtained as a by-product.

<Practice/Example 3) (Illustrative compound 5 according to reaction step (1)
synthesis) N-aminotriazolium E-cyto' shown in Example 1
(V) 5 g (16 mmal), 5 equivalents of lauric anhydride 30 g (79 mmol) and tripropylamine 11 g (77 mmol) were heated in 100 ml DMF at 140-150° C. for about 10 hours. DMF was removed using an evaporator, ethyl acetate was added, and the precipitated unreacted lauric anhydride was removed by filtration, and the filtrate was transferred to a separating funnel, and a 2N aqueous sodium hydroxide solution was added thereto and thoroughly shaken to separate the layers. The aqueous layer was further extracted twice with ethyl acetate, and the ethyl acetate layer was washed with saturated brine and dried over magnesium sulfate.
After adding 0m water and heating under reflux for about 4 hours, ethanol was removed and the mixture was extracted with ethyl acetate. After normal post-treatment and purification with a silica gel column, 0.8 g (14
%)Obtained.

Nuclear magnetic resonance spectrum (CDCl2) δ (ppm): 0.88 (3H, brt, J = ~7) 1
．． 30 (20H, brs)2.40 (3H,s)2.
60 (2H, t, J=7°5) 5.03 (2H, s)
5.25 (IH.

s) 7, 10-7, 45 (5H) This 1-benzyl compound was reduced with sodium in liquid ammonia to obtain an exemplary compound light that is sparingly soluble in organic solvents other than alcohol in a yield of about 90%. Melting point: 154-155°C (Example 4) (Synthesis of Exemplary Compound 6) 7.2 g of n-hebutanoic acid (55 Kaku 01) was dissolved in dimethylformamide (D
MF) was dissolved in 15 mJ1, 7.9 g (55 mmol) of tri-n-propylamine was added thereto, and then DMF
trimethylacetyl chloride 6 dissolved in IOmu,
1 g (51 mmol) was added dropwise. After stirring for 10 minutes at room temperature, N-aminotriazolium iodide (V
) 5 g (15.8 mmol) and 11°3 g (79 mmol) of tri-n-propylamine were gradually added.
It was heated to 50°C and stirred at that temperature for about 5 hours. DMF
After distilling off the and amine under reduced pressure, 2N aqueous sodium hydroxide solution 10
The mixture was extracted with ethyl acetate three times, and the extract was washed with water and saturated brine, and dried over magnesium sulfate.

After filtration, it was concentrated under reduced pressure, and the residual liquid was purified by silica gel chromatography to obtain (Vl) (R5=, -C6H,3)
2.9g (45%) of the product was obtained.

When this was deacylated and debenzylated by the methods shown in (C) and (D) of Example 1, 1° to 0 g (68%) of 6 could be obtained. Melting point 105-110
°C Nuclear magnetic resonance spectrum (DMSC)-d6) δ (ppm
): 0.85 (3H, brt, J=-7) 1.32
(8H,brs)2.45 (3H,s)2.58(
2H, t, J = 7.5) 5.60 (IH, s) <Example 5> (Synthesis of Exemplary Compound 7 according to reaction step (1)) (V) l, Og (3, 16 mmol) in anhydrous D
Dissolve in 8 mJlj of MF, add 3.6 g (15,8+n++ol) of benzoic anhydride and 2.3g (15,8+**1ol) of tri-n-propylamine to the solution, and heat and stir at 130°C for 24 hours. did. After distilling off DMF and tri-propylamine under reduced pressure, exchange 30 m of ethanol.
10 m of concentrated hydrochloric acid was added and the mixture was heated under reflux for 5 days.

After evaporating ethanol and concentrated hydrochloric acid under reduced pressure, the residue was extracted with ethyl acetate, dried, concentrated, and purified by silica gel chromatography to obtain 0.2 g (22%) of the 1-benzyl compound.

Nuclear magnetic resonance spectrum (CDCI3) δ (ppm): 2.35 (3H, s) 4.95 (2H
,s)5.65 (IH,s)7.05-7.50 (
8H) 7.80 (2H, dd, J=9, 0,
1, 5) 0.2 g (0.69 mmol) of the 1-benzyl compound was reduced with 0.05 g of sodium in liquid ammonia to obtain 12 g (87%) of the desired 7.

Melting point ~190°C (decomposition) <Example 6> (Exemplary compound 8 according to reaction step (1).
Synthesis of 9) 1, OOg (32 mmol) of (V) to 15+n
KL's N-methylpyrrolidone was added to the mixture, stirred at room temperature, 2.93 g of methoxycarbonylpropionic anhydride and 4.8 m4 of tripropylamine were sequentially added thereto, and the mixture was heated at 130°
The mixture was heated on a C oil bath for 3 hours. After cooling, it was diluted with ethyl acetate and washed with water (loo+n sentences x 2). The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and 30 ml of methanol and 20 ml of concentrated hydrochloric acid were added thereto, followed by heating under reflux for 7 hours. After cooling, ethanol was concentrated under reduced pressure and the remaining liquid was poured into 100 mJL of ice water to neutralize it to pH 7.
Extracted with ethyl acetate (50 mJljX3). The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and purified using a silica gel column (20 g) to give 8°, 18 g (1
7%) was obtained as an oil.

Nuclear magnetic resonance spectrum (CDCl2) δ (ppm): 2.42 (3H, s) 2.60-3
．． 15 (4H, m) 3.63 (3H, s) 5.02
(2H, s) 5.26 (IH, s) 7.12-7.50
(5H, m) Elemental analysis value C (%) H (%) N (%) Theoretical value 8
4.41 8.08 18.78 Experimental value [14,22
fl, 30 18.55 This N-benzyl compound was reduced with sodium in the same manner as above to obtain Exemplified Compound 9 in a yield of about 80%. Melting point 120-122°C <Example 7> (Exemplary compound 11 according to reaction step (1)
．． 12, 13. Synthesis of 14)
150 m+mol) of anhydrous 4-(p-nitrophenyl)
Butyric acid and 57 mJL (300+*mol) of tripropylamine were dissolved in 150ml of DMF. This mixture was heated under stirring on an oil bath at 130°C for 4 hours, then at 140°C.
It was heated on an oil bath at 160°C for 2 hours and then for 6 hours on an oil bath at 160°C. After DMF was distilled off under reduced pressure, it was dissolved in ethyl acetate, and this ethyl acetate solution was washed with a 2N aqueous NaOH solution (twice). After drying the ethyl acetate layer over anhydrous magnesium sulfate, it was concentrated and subjected to silica gel column chromatography (600 g of silica gel, eluent: hexane:
Ethyl acetate = 2:l-1+1) and 7.6g (45
%) (7) (Vl)(R,=(CH2) 3C6H
4-No. 2) was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 2.40 (3H,5)l-8-3
, 3 (12H, m) 5.80 (2H, s) 7.0~7
．． 4 (9H, m) 8.1 (4H.

m) 7,6 g (13+m+*ol) ノ(Vl) as E
It was dissolved in a mixed solvent of 150 mL of tOH and 50 mL of concentrated hydrochloric acid, and heated under reflux for 10 hours. After adding 100 mj of water, ethanol was removed by concentrating under reduced pressure. After neutralization with aqueous ammonia, extraction was performed with ethyl acetate, and the ethyl acetate layer was dried over anhydrous magnesium sulfate. After concentration, it was subjected to silica gel column chromatography (140 g of silica gel, eluent: hexane; ethyl acetate = 1:1) (■) (R = (
3.8 g (76%) of CH2)3C8H4No2) was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 2.03 (2H, m) 2.44 (
3H, s) 2.58-2. ．． 85 (4H, m) 5.0
2 (2H, s) 5.20 (IH, s) 7.04~7
．． 40 (7H, m)8.04 (2H, d, J=8.
0) 18g of reduced iron in 80mJ1 of isopropyl alcohol (
0.32 mol), ammonium chloride 1.3 g (2
5+m+*ol) and 8 ml of water were added, and the mixture was heated with vigorous stirring until it reached reflux. Add 0.2 of concentrated hydrochloric acid to this
After adding mM, the mixture was heated under reflux for 30 minutes. To this, 0 g (47,9+smol) of the above nitro compound 18 was added little by little over 20 minutes, and the mixture was further heated under reflux for 1 hour. It was filtered through Celite, and the Celite was thoroughly washed with ethanol. The filtrate was concentrated, dissolved in ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. Concentrate to obtain the crude aniline product ((■) R=-CCH2) 3C6
15.8 g (95%) of H4NH2) were obtained.

Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 1.95 (2H, m) 2.38 (3
H, s) 2.40-2.76 (4H, m) 3.36
(2H,br)4.97 (2H,s)5.20(IH
, s) 6.53 (2H, m) 6.91 (2H, m) 7
．． 00 to 7.38 (5H, m) 15.8 g (45.7 m) of this aniline compound was added to 200 m of refluxed liquid ammonia and stirred. 2.6 g (0.11+1 ol) of metallic sodium was added little by little to this. Ammonium chloride was added little by little to this, and the mixture was left to stand overnight to remove ammonia. 2NH of the residue
It was dissolved in CI aqueous solution and washed with ethyl acetate. The aqueous layer was neutralized with aqueous ammonia, and the precipitate was collected by filtration. The precipitate was washed with water and then with acetonitrile and dried to yield 7.9 g (68%) of almost pure 11.

Melting point 199-203°C Nuclear magnetic resonance spectrum (CDC13+DMSO-d6) δ (ppm): 1.88 (2H, br, quint
et, J= ~7)2.41 (3H,s)2.3~
2.8 (4H)5.42 (IH,s)6.56 (
2H, d, J=8.5) 6.90 (2H, d, J=8.
5) Mass spectrometry spectrum 255 (M”, 20%) 136 (100).

119 (90) 106 (50) Infrared absorption spectrum (KBr) 3340.1605,1507,1380°1270
3.00 g (11.7 mmol) of cm' 11 was added to 50 ml of acetonitrile, 25 ml of N,N-dimethylacetamide was added thereto, and the mixture was heated under stirring until it reached a reflux state. Add acid chloride' (@-CH20-◎-5O2
-◎-OCH(n-C,CH2,)C0C1)7.19
g (12,9m+1ol) in acetonitrile solution (2
0 ml) was added dropwise over 20 minutes, and the mixture was further refluxed for 20 minutes. Furthermore, the above acid chloride 0.72g (0.13m intestine 01
) was added dropwise over 10 minutes, and reflux was continued for 30 minutes. After cooling, 500m of water
The mixture was poured into a liquid and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (300 g of silica gel, eluent chloroform:methanol = 60:l) to obtain 7.25 g (
80%) of 12 (solid) was obtained.

Elemental analysis value C (%) H (%) N (%) S (%) Theoretical value 6
9,85 8.88 9,02 4.13 Measured value 1 (8
,996,908,804,07 Mass spectrometry (FD) 77
6 (M”, b, p) Nuclear magnetic resonance spectrum (CDC
l2) δ (ppm): 0.86 (3H, brt, J=7)1
．． 0~2.2 (20H, m) 2.38 (3H, s)2
．． 5~2.8 (4H, m) 4゜68 (IH, brt
,,J=6)5.05 ('2H,s)5.45(IH
, s) 6.9-7.4 (13H, m) 7.7-7.9
(4) (, m) 8.17 (IH, 5) 11.6 (IH,
br) 3.3g (4,3 intestinal fat 01) of benzyl body 12 was TOo
The mixture was stirred at C for 3 hours. After cooling, the catalyst was removed by filtration and the filtrate was concentrated. Silica gel column chromatography (silica gel 90g, eluent chloroform:methanol = 1
:0-30:l) to obtain 2.7 g (92%) of 13 as a solid.

Mass spectrometry (FD) 687 (M++2.50%) 686
(M++1,100) 685 (M”, 30) 4.25g (6,20+wol) of 13 and THF50m
1 was added to 100 ml of dichloromethane and dissolved by stirring at room temperature. Add to this 795mg (5-95m++ol
) was added to the mixture, and the mixture was stirred at room temperature for 15 minutes. After washing with water (150mMX2), it was dried over anhydrous magnesium sulfate. After concentration, it was subjected to silica gel column chromatography (100 g of silica gel, eluent: chloroform:methanol = 50:1 to 30:1) to obtain 144.04 g (90%) as a solid.

Mass spectrometry (FD) 722,721.720 (9 near:
9) 220 (b, p) <Example 8> (Synthesis of Exemplary Compound 15.16) rl-
rN-1 1 b L L , 1.79 g (7,00+*mol) and N
, N-dimethylamide 15 mJL acetonitrile 30
In addition, the mixture was heated and stirred until it became reflux-like IE. To this, acid chloride C(t-C5H1,) 2 c61 (30
CH(n-C4H8)COCl] 2.83 g (7,
70m+wol) of acetonitrile solution (10m!; L
) was added dropwise over 15 minutes, and reflux was continued for an additional 30 minutes. After cooling, the mixture was poured into 300 m of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography (
100g of silica gel.

The eluent was fractionated with chloroform:methanol (70:l),
Obtained 3.12 g (76%) of 15 as a solid.

Elemental analysis value C (%) H (%) N (%) Theoretical value?
3.81 8.77 11.95 Measured value 73. E14
8.95 11.93 Nuclear magnetic resonance spectrum (CDC
13) δ (ppm): 0,50~1,00 (7
H.

m)1. oO~2.16 (26H, m) 2.44 (3
H, S) 2.46-2.80 (4H.

m) 4.66 (IH, t, J=6.0) 5.44 (
IH, s) 6.90-7.34 (6H.

m) 7.64 (IH, d, J=9.0) 7.87 (L
H, br, s) 3, l Og (5, 29 mmol) of 15 and TH
50 ml of F was added to 100 mM dichloromethane and dissolved by stirring at room temperature. To this was added 706 mg (5.29 mmol) of N-chlorosuccinimide, and further io
Stir for a minute. After washing with water (150ml x 2), it was dried over anhydrous magnesium sulfate. After concentration, acetonitrile was added to crystallize, and the mixture was heated to reflux once. After cooling, filter
After washing with acetonitrile and drying, 2.4g of 16
(73%) obtained as a solid.

Elemental analysis value C (%) H (%) N (%) CI (%) Theoretical value 69,71 8.12 11.29 5.72 Measured Eies, 3e8.2111.255.78 Nuclear magnetic resonance spectrum (c Dc 13) δ (ppm): 0
．． 48-1.00 (7H.

m) 1.06-2.18 (26H, m) 2.45
(3H, s) 2.48-2.82 (4H.

m) 4.67 (IH, t, J = 6.0) 6.65
(18, d, J=8.5) 6.91~7.34 (6H
, m) 7.87 (IH, s) <Example 9) (Combination of Exemplary Compounds 32, 33.17 〆1\2 /-\1〆 〆-
-) composition) 2.93g (5, OOOgol) of 15 in 25mJL
of acetic acid and stirred at room temperature. 586 mg (5,00+ mol) of isoamyl nitrite was added dropwise to this, and 1
Stir for hours. This was washed 300 meters over a tree, and the deposited precipitate was collected by filtration and washed with water. It was dried under reduced pressure to obtain 322.95 g (96%) of the 7-nitroso compound as a solid. Melting point: Approximately 95℃ 2.85g (4,63■ garden o1) of 7-nitroso compound 32
was dissolved in 50 mM ethanol and heated to reflux under a nitrogen atmosphere. To this, 4.38 g (2
A sti acid solution (10 mmol) of 3.1 mmol was added dropwise over 10 minutes. After continuing reflux for another 30 minutes,
Cooled. This was poured into 150ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to dryness. In this way, a complex of 7-amino-7-isomer 53 and tin was obtained.

Free 33 can be obtained by treatment with base, but is susceptible to air oxidation. Here, the complex was used in the next reaction as is.

This 7-ami7 body 33 was dissolved in 25 mM of pyridine, and the solution was stirred while cooling with water under a nitrogen stream. Add acid chloride [
H(CF2)8COCII 2.15 g (4,63
mmol) was added dropwise, and the mixture was further stirred for 1 hour. This was poured into 250 mJL of water and extracted with ethyl acetate. The ethyl acetate layer was washed with 2N1ji acid and then with water. The ethyl acetate layer was dried over 42 grams of anhydrous magnesium sulfate and then concentrated. Silica gel column solomatography (150 g of silica gel.

The eluate was fractionated with chloroform:methanol-1oo:l), and the eluate was concentrated to dryness to yield 3.43 g (72%
) was obtained.

Nuclear magnetic resonance spectrum (CDC13) δ ('ppm): 0.52 to 1.01 (7H.

m) 1.02 to 2.15 (26H, m) 2.42 (
3H, S) 2.46-2.78 (4H.

m) 4.60 (IH, t, J-6, 0) 6.30 (
IH,tt,J=51.0,5. ．． 0) 7°45 (IH
,'d, J28.5) 6.85~7°36 (6H, m
)8.90 (LH,brs)10.0 (lH,br
s) 10.3 (IH, brS) <Example 1O) (Exemplary compound 21 according to reaction step (2)
(Phantom (X) Trimethyl orthoisocaproate could be synthesized from incapro 4nitrile via imidoester hydrochloride in a yield of about 50%. Boiling point 75-77℃/28mmHge 19-8g of this orthoester ( 0.11 mol) and (IX
) 10,9 g (0,1 mol) was heated under reflux in 200 mjL of toluene for about 24 hours, and then!・When the toluene was distilled off under reduced pressure, the crude product (X) was obtained as an oil.
A methanol solution of hydroxylamine prepared from 7g (0.17"°1) and 34mM of 28% sodium methoxide was added at 0°C, stirred at room temperature for 1 hour, and methanol was distilled off under reduced pressure.

Chloroform was added to the residue, 12 g (52%) of precipitated powder crystals of (X[) were collected by filtration, the crystals were dissolved in trahydrofuran (3 sentences), and 13. By adding 1 g (6 mmol) of p-toluenesulfonic acid chloride and performing the same operation as in Example 2, 7.1 g (65%) was obtained. Melting point lO ~ 142°C Mass spectrometry 192 (M”) 136 (b, p) Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 0.90 (6H, d, J=6) 1.
55-1.90 (3H) 2.45 (3H.

s) 2.90 (2H, brt, J=7) 5.60 (
IH, 5) 13-3 (IH) Example 1i) (Illustrative compound 2 according to reaction step (3) 2-ethylhexanoic acid chloride to 2-ethylhexanenitrile is Org, Syn, Col I.

Vol. 3, p. 490 (1955), it was dissolved in 1 equivalent of methanol, and 1 equivalent of dry hydrogen chloride gas was absorbed into the solution using O'C.

When the mixture was left in a refrigerator (~5°C) for about 20 days, crystals of methylimide ester hydrochloride precipitated, so ether was added thereto and filtered.

Yield: 48% This imidoester salt alcohol 1j! log(51,6m+5
at) and (IX) 5 g (51, 5+w+*ol)
and were stirred at 40°C in 150mu of methanol. After about 7 hours, TC (SjO2, chloroform:ethanol-4
Looking at 1), two sports were observed. The low pole spot has the (X) structure. When an excess amount of ammonium chloride is added to this solution and the mixture is heated under reflux for about 2 hours, (X) disappears and only XI) is left. Methanol is distilled off under reduced pressure,
Add 50 mJ1 of chloroform and 10 mJL of methanol to the residue.
was added to filter out adulterous material. After concentrating the filtrate, it was purified using a small amount of silica gel column to obtain 8 g (70%) of (Xll) as an oil.

Nuclear magnetic resonance spectrum (CDCI3: CD30D=3:2) δ (ppm
)': 0.7-1.2 (6H) 1.2-1.6 (4H
) 1.6-2.1 (4H)2.

32 (3H, s) 2.80 (IH, quinte
t, J=7) 5.70 (3H, broad) 6.20
(IH, 5) (XI) 2,6 g (12m++ol) for 50m
5-8 g of lead tetraacetate (12
mmol) was added little by little under a nitrogen stream. After the addition was completed, the mixture was heated under reflux for 3 hours. Acetic acid was removed under reduced pressure, extracted three times with a 30:1 mixed solvent of chloroform and ethanol, washed with a saturated aqueous sodium bicarbonate solution and brine, and dried over magnesium sulfate. After filtration and concentration, 22 was purified by silica gel chromatography to obtain O,1
5g (5.7%) obtained. Melting point 110-115°C + Mass spectrometry 220 (M), 155,130 Nuclear magnetic resonance spectrum (CDC13) δ (ppm): 0.7-1.2 (6H) 1.2-1
．． 55 (4H) 1. 55-2.20 (4H)2
．． 45 (3H, s) 2.95 (LH, quintet,
J-7) 5.62 (IH, 5) 12.6 (IH) <Example 12> (Exemplary compound 2 according to reaction step (2)
Synthesis of 3) (IX) (X) Trimethyl acetate (OR)-4-(p-nitrophenyl)
9.2 g (34 m
Peng of) and 3-7 minnow 5-methylvirasol (IX
) 5 g (51 mu l) and 100 g of toluene. After heating under reflux for 20 hours in mu, toluene was distilled off under reduced pressure.
The obtained crude (X) was dissolved in 100 mJ1 of methanol. In the same manner as in Example 2, add 3,5 g (
A methanol solution of hydroxylamine prepared from 50+*mol) of hydroxylamine hydrochloride was added at 0°C, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. When the solution was poured into water 141 without stirring, a precipitate was formed, which was filtered by absorption and thoroughly washed with dichloromethane for 7 hours to obtain powder crystals of (XI). Yield 6.7g
(65%) Melting point: 165-166°C Dissolve 2 g (6.6 mmol) of (X[) in 80 mJL of tetrahydrofuran (THF) and 0.73 g (7°3
mol) of triethylamine was added and stirred. 1.4 g of P-)luenesulfonic acid chloride (7.3 m layer 01) dissolved in 50 ml of THF was slowly added into it.
After the addition is complete, stir for about 15 minutes, remove the precipitated triethylamine hydrochloride by filtration, and add loml of TH.
Washed with F. The filtrate was heated under reflux for about 7 hours under a nitrogen stream, then THF was distilled off under reduced pressure, and the remaining solution was dissolved in a small amount of methanol, poured into 100 ml of water, and stirred to produce a light brown precipitate. When it was suction filtered and recrystallized from a mixed solvent of acetonitrile and methanol, 231.2g (63%
) was obtained. Melting point 203-212℃ Mass spectrometry 285 (
M”) 149 (b, p) Nuclear magnetic resonance spectrum (DM
SO-d6) δ (ppm): 2.05 (2H, m)
2.45 (3H, s) 2.56-2.86 (4H, m
)5.60 (LH,s)7.25 (2H,d, J
= 8.0) 8.05 (2H, d, J = 8.0) <Example 13> (Synthesis of Exemplary Compounds 24 and 26.29) 20 g of reduced iron in isopropyl alcohol room J1
(0.36 mol) and ammonium chloride 1.4 g
(2,8+*mol) and 10 ml of water were added and heated with vigorous stirring until a reflux state was reached. Next, 0.3 m of concentrated hydrochloric acid was added and the mixture was heated under reflux for 30 minutes. 23 to this
15.2 g (53, 2 mmol) was added little by little over 20 minutes, and the mixture was heated under reflux for 1 hour. It was filtered through Celite and washed well with ethanol. After concentrating the filtrate, it was dissolved in 2N HCI aqueous solution and washed with ethyl acetate. The aqueous layer was neutralized with aqueous ammonia, and the precipitate was collected by filtration.

The precipitate was washed with water, then with acetonitrile, and dried to yield nearly pure 2410.13 g (80%). Melting point ~180℃ Nuclear magnetic resonance spectrum (DMS O-d6') δ (p
pm): 1.90 (2H, br, quintet, J
= ~7) 2.46 (3H, s) 2.3 ~ 2.8 (4
H) 5.60 (IH, s) 6.55 (2H, d, J
= 8.5) 6.93 (2H, d, J = 8.5) 3.6 g (14,0 Peng 01) of 24 was dissolved in a mixed solvent of 30 ml of N,N-dimethylacetamide and 60 ml of acetonitrile. and heated to reflux. To this, acid chloride [(t
C3Hi□)2C6H30CH(n-C6H,3)CO
An acetonitrile solution (20 ml) of 6.1 g (15,4+IIIaol) of CI] was poured over 20 minutes, and the mixture was further heated under reflux for 30 minutes. After cooling, the mixture was poured into 300 ml of water and extracted with ethyl acetate. After washing with saturated saline, drying over anhydrous magnesium sulfate, concentrating, and separating and purifying with silica gel column chromatography, 267.0 g (81
%) was obtained.

Nuclear magnetic resonance spectrum (CDCl2) δ (P pm): 0. 50-1. 00 (7
H.

m) 1.00-2.15 (30H, m) 2.45 (
3H, S) 2.46-2.80 (4H.

m) 4.68 (lH, t, J=6.5) 5.60 (
IH, s) 6.88-7.33 (6H.

m) 7.66 (IH, d, J=9.0) 7.88 (I
H, br, s) 3, 1 g (5,00 mmol) of 26 at 25 mJ
of acetic acid and stirred at room temperature. Isoamide nitrite + 11,586 mg (5,00 mmol) was added dropwise to this.
The mixture was further stirred for 1 hour. This was slowly added to 300 m of water, and the deposited precipitate was collected by filtration and washed with water. It was dried under reduced pressure to obtain 2.9 g (91%) of 7-nitrone as a solid. Melting point: Approximately 90℃2.9 g (4,5+u+o
Dissolve the 7-nitroso form of l) in 50ml of ethanol,
It was heated to reflux under a nitrogen stream. To this was added a concentrated hydrochloric acid solution (1
0 mJ1) was added dropwise over 10 minutes. After heating under reflux for an additional 30 minutes, the mixture was cooled, poured into 150 ml of water, and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to dryness to obtain a complex of 7-amino compound and tin. This was used in the next reaction without converting it into a free amine.

To this 7-amino compound, 100 mJ1 of toluene and 2°5-dimethyl-1,3,4-oxadiazole were added.

0.49 g (5.0+ smol) was added and heated and refluxed for about 5 hours. This was poured into 250ml of water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, concentrated, and separated and purified using silica gel column chromatography to obtain 292.2 g (70%) as a solid. Melting point ~120℃ Nuclear magnetic resonance spectrum (CD
Cl2) δ (ppm): 0.48-1. 00 (,7
H.

m)1. 05-2.20 (30H, m) 2.43
(3H, s) 2.46 (6H, s) 2.46-2.8
0 (4H, m) 4.67 (IH, t.

J=6.5) 6.60 (LH, d, J=8゜5)6
．． 90-7.35 (6H, m) 7.85 (IH, s) <Example 14> (Synthesis of exemplified compound 34) Commercially available 3-
8.3 g (0.1 mol) of aminopyrazole and 22.2 g (0.15 mol) of triethyl orthoformate were dissolved in 100+nJJ of toluene and heated under reflux for about 10 hours.

After distilling off toluene under reduced pressure, the residue was dissolved in 50 ml of methanol, and 4 g of io (
A methanol solution of hydroxylamine prepared from 0.15 mol) of hydroxylamine hydrochloride was added at 0°C, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. Thereafter, methanol was distilled off under reduced pressure at as low a temperature as possible, and dichloromethane was added to the residual liquid to precipitate (X[) (R6=R7=H) as crystals. Yield: 8.2 g (65%) 5 g (40 s+ol) of this amidoxime was reacted with P=)luenesulfonic acid chloride and triethylamine in THF as shown in <Example 2>, and then heated to reflux to form a silica gel. By purifying with column chromatography, 2.6 g (60%) of 34 could be obtained. Melting point 200-205℃ Nuclear magnetic resonance spectrum CDMSO-d6) δ (ppm
): 5.75 (IH, d, J = 2°5) 7.53 (I
H, d, J = 2.5) 8.50 (IH, s) <Example 15> (Synthesis of Exemplified Compound 35) 5 8.3 g (0.1 mol) of 3-7 minovirazole and ortho-4-(p -nitrophenyl)trimethyl acetate 27
．． From 1 g (0.1 mol), (XI) (R8=H, R7=
-(CH2)3C6H, No2) was able to be obtained in an amount of 19 g (69%). 5 g of this amidoxime (18
3.1 g (68%) of 35 could be obtained from f).

Melting point 165-170℃ Nuclear magnetic resonance spectrum (DMSO-d6) δ (ppm
) :2. Q4 (2H, m) 2.55-2.86 (4
H, m) 5.78 (IH, d.

J=2.5) 7.25 (2H, d, J=8゜0)7
．． 54 (IH, d, J=2.5) 8.05 (2H,
d, J=8.0)

[Brief explanation of the drawing]

The drawing shows the absorption spectrum of macenta dye. A... Absorption spectrum of the dye produced from the exemplified compound B... Absorption spectrum of the dye produced from the exemplified compound 13 C... Absorption spectrum of the dye produced from the comparative coupler (a) 46 Applicant: Fuji Photo Film Co., Ltd. Agent, Patent Attorney FF1IJ (Toshizo flo, 50 - Procedural Amendment (Spontaneous) May 15, 1985 Manabu Shiga, Commissioner of the Patent Office 1, Indication of Case Patent Application No. 27745 of 1988 ?9 Name of the invention Pyrazolo [1,5-bl [1,2,4] triazol derivative 3, Person making the amendment Relationship to this case Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520)
Fuji Photo Film Co., Ltd. Representative: Sho Ohnishi 4, Agent address: 6, 7th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo Number of inventions increased by amendment O 8, Statement of contents of amendment ( amend the "Detailed Description of the Invention" column) as follows. (1) Correct "maximum of 6 items" in line 11 of page 2 to "maximum of 7 items". (2) From the last line of the same page to the first line of the third page, ``5-5 fused polycyclic compounds are commonly called ``azapentalene''. This compound is corrected to ``A 5-5 fused polycyclic compound (a type of azapentalene)''. (3) Insert [and O-mesitylenesulfonylhydroxylamine] after "0-diphenylphosphorylhydroxylamine" on page 17, lines 6-7. (4) Correct the 2nd line of page 18. (5) Delete rDMFJ on the second line of page 18. (6) Change “Konoro Chloroho” in line 16 of page i30 to “
This will be corrected to "Chloropho". (7) On the 31st page, second line, next to “I got it.”
Add melting point 180-181'OJ. (8) Page 34, line 7 [1-benzyl-2,6
Correct -J to ``l-benzyl-2,6-J.'' (9) Correct ``tripropyl'' in line 5 of page 39 to ``tri-n-propyl.'' (10) Correct the structural formula of Exemplary Compound 12 on page 45, line 10 as follows. n -C, oH2゜H3 (11) Correct the structural formula of Exemplary Compound 14 in the first line of page 46 as follows. (12) Correct the structural formula of compound (XI) in the first line of page 59 as follows. (13) rO, 90 (6H, d
. Correct "J=6" to "0.O0 (8H, d, J=7J). (14) Correct "absorption filtration" in the first line of page 65 to "suction filtration".

Claims (1)

[Claims] (1) General formula (in the formula, R and R2 represent a group selected from a hydrogen atom, an alkyl group, and a phenyl group, and these groups may be the same or different from each other, and these groups have a substituent. Also, X may be a hydrogen atom f, a halogen atom, an acyl group,
pyrazolo[1,5-b] [1,2゜4] represented by a nitrone group, an ami7 group or a substituted amino group, and Y represents a hydrogen atom or an aralkyl group)
Triazole derivative.