JPH013187A - Pyrazolo[1,5-a]-1,3,5-benzotriazepine compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides novel pyrazolo[1,5-al-1,3,5-
The present invention relates to 1,3,5-benzotriazepine compounds.

[Background of the invention]

Conventionally, as a synthetic heterocyclic compound containing a pyrazole ring,
For example, compounds in which five shell rings are fused to a pyrazole ring such as virazolobenzimiguzole, pyrazolotriazole, imidazopyrazole, pyrazolopyrazole, and pyrazolotetrazole, pyrazolo[1',5':3.2]quinazolone, etc. Compounds in which six shell rings are fused to a pyrazole ring are widely known. Many of these compounds are useful in pharmaceuticals, agricultural chemicals, photographic additives, dyes, etc.

However, in the pyrazole ring, more multi-membered rings such as 7
Compounds in which shell rings are condensed are hardly known, and there are very few reported documents.

The inventors discovered pyrazolo [
As a result of intensive studies on 1,5-all, 3.5-1,3,5-benzotriazepine compounds, we succeeded in synthesizing a birazolobenzotriazepine compound having a sulfinyl group or a sulfonyl group, and the present invention I came to do this.

[Purpose of the invention]

The object of the present invention is therefore virazo 117[1,5-a]-1,3 having a sulfinyl or sulfonyl group.

An object of the present invention is to provide a 5-1,3,5-benzotriazepine compound.

[Structure of the invention]

The above objects of the present invention have been achieved by a pyrazolo[1,5-a]-1,3,5-1,3,5-benzotriazepine compound represented by -per[I] below.

-per[l] In the formula, R1 and R2 each represent an alkyl group or an aryl group, and R3, X and Y each represent a hydrogen atom or a substituent. m represents an integer of 0 to 4, and n represents 1 or 2. However, when "is 2 or more" 2, a plurality of R3s may be the same or different.

The present invention will be explained in more detail below.

- In per[I], the alkyl group represented by R1 and R2 is carbon! &1 to 32 are preferable,
It may be straight chain or branched.

The aryl group represented by R1 and R7 is preferably a phenyl group.

These alkyl groups and aryl groups may further have a substituent such as a long-chain hydrocarbon group or a polymer residue.

The substituent represented by R1 is not particularly limited, but typically includes a halogen atom, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy,
Examples include winter grasses such as acyl, acylami-7, acyloxy, thureide, carbamoyl, sulfonamide, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, cyanitro, hydroxyl, and carboxyl.

Among these, particularly preferred are a halogen atom, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. Examples of the halogen atom include chlorine, bromine, and iodine atoms, and the alkyl component is preferably a straight chain or branched one having 1 to 32 carbon atoms.

The substituent represented by X is not particularly limited, but is preferably a group that leaves in the presence of a reducing agent, such as a halogen atom such as a chlorine atom.

The substituent represented by Y is not particularly limited, but preferably includes a group that leaves under alkaline conditions or in the presence of a reducing agent.

Among these, it is preferable that X and Y are hydrogen atoms.

Next, typical examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

(Exemplary compounds) Pyrazolo[1,5-a]-1,3,5-1,3 of the present invention
, 5-benzotriazepine compounds can be obtained by various synthetic routes. As the simplest method, a phenylhydrazine compound having a nitro group at the 0-position and (i)
1- by reaction with a nitrile compound having 7 amino groups or (ii) an acetonitrile compound having a carbonyl group.
A scheme may be mentioned in which a (2-nitrophenyl)-3-substituted 15-aminopyrazole compound is obtained, the nitro group is reduced, the ring is condensed with carbon disulfide, and the compound is further oxidized.

〔Example〕

Hereinafter, the synthesis of the compound of the present invention will be explained by giving specific examples. The synthesized compound was confirmed by elemental analysis and FD mass spectrum.

Synthesis Example 1 (Synthesis of Exemplary Compound 1) ■ (A1) (Bl) (C,) (D,)
(E,) (
Compound 1) Co A, synthetic 0.2 mol of 0-nitrophenylhydracinto 0.23
80 mol of 3-aminocrotonitrile in dioxane
"nl was heated and refluxed for 2 hours. 400 In I!
The precipitated crystals were collected by filtration, dried, and recrystallized with ethanol to obtain 0.17 mol of A1.

FD mass spectrum: M+218 Elemental analysis value (C, ol (, oN, 02) calculated value (%)
C: 55,06 H: 4.62 N: 25,6
9 Actual measurement value (%) C: 55.25 H: 4.75
N: 250 ethanol solution in which 0.17 mol of artificial A1 of 25.77 open body B was suspended
After blowing hydrogen chloride gas into the Inl for 25 minutes while heating and refluxing it, the solvent was distilled off. The residue was recrystallized from a mixed solvent of ethanol and ether to obtain 0.15 mol of B1.

FD mass spectrum: M”254 Elemental analysis value (C, oH, l(1!N, 02) Calculated value (%
) C: 47.16 H: 4.35 N: 22
．． 00 Actual value (%) C: 47.01 H: 4.3
5 N: 450 In l of a methanol solution of 21.65 insects and 0.15 mol of B.
was reduced by passing hydrogen in the presence of a Pd/C catalyst at room temperature and pressure.

The catalyst was filtered off, the solvent was distilled off from the filtrate, and the residue was recrystallized from a methanol/ether mixed solvent to obtain 0.12 mol of C1.

FD mass spectrum: M+224 Elemental analysis value (C,.H,, (J!N,) Calculated value (%)
C: 53.45 +1: 5.83 N: 24.94
CI: 15.78 Actual value (%) C: 53,3511
:5.77 N:25.08 CI:15.94!1l
l = Exhaust J 1 0.12 mol C1,60 [nl carbon disulfide, 0.1
A mixed solution of 2 mol of sodium methoxide and 180 ml of methanol was heated and refluxed for 9 hours. The solvent was distilled off, the residue was suspended in water, washed, and then recrystallized using a lobe tar to yield 0.08 mol of Dl.

FD mass spectrum: M”230 Elemental analysis value (C,,)1.oN4S) Calculated value (%) C:57.37 +1:4.38 N
:24.33 S:13.92 Actual value (%) C:5
7.5011:4.44 N:24.26 S:]3.
781l- 0.08 mole of El anthropomorphism]),, 16+nj! A suspension of methyl iodide and 80 In R of methanol was heated for 1 hour.
Reflux (becomes a clear solution). The reaction solution was allowed to cool, neutralized with a 10% aqueous sodium hydroxide solution, and the precipitated crystals were collected by filtration.
After washing with water, it was recrystallized with toluene to obtain 0.06 mol of El.

FD mass spectrum: M+244 Elemental analysis value (C+ 2tl+ 2N-S) calculated value (%)
C:59. OOl(:4.95 N:22,933
:13.13 Actual value (%) C:59.171+:5
．． 06 N: 22.81 S: 12.96" 11 nibs and 1 reduction □ 0.06 mol of El to 230 to j! 70 mL of 35% hydrogen peroxide solution was slowly added dropwise to the solution dissolved in acetic acid, and the mixture was stirred at 60°C for 1 hour.
In 1 water was added, the mixture was neutralized with an aqueous sodium hydroxide solution, and then extracted with ethyl acetate. The solvent was distilled off from the extract, and the residue was recrystallized with acetonitrile to obtain 0.05 mol of Exemplified Compound 1 as white needle-like crystals.

FD mass spectrum: M+276 = 12- Elemental analysis value (C, 2B, , N-02S) calculated value (%)
C:52.1611:4.38 N:20,283:
11.60 Actual value (%) C:52,0311:4.
45N:20. ]B6S:11.72 Synthesis Example 2 (Synthesis of Exemplified Compound 2) (A2) (B2) (C2) (B2) (B2) (F2) (Compound 2) Synthesis of Intermediate A2 To 0-nitrophenylhydrazine Instead 2-2 draw 4
- 0.17 mol of A was synthesized in the same manner as in the synthesis of Intermediate A in Synthesis Example 1, except that methoxyphenylhydrazine was used.
2 (recrystallized with a toluene/hexane mixed solvent) was obtained.

FD mass spectrum: M+248 Elemental analysis value (C,, H, 2N, 03) Calculated value (%) C: 53,22 H: 4.87
N: 22.57 Actual value (%) C: 53.54
H: 5.08 N: 22.31 Synthesis of Intermediate B2 In exactly the same manner as the synthesis of Intermediate B1 in Synthesis Example 1,
0.14 mol of B2 was obtained from 0.17 mol of A2 (recrystallization was performed using a mixed solvent of i-propyl-ether).

FD mass spectrum: M”284 Elemental analysis value (C,,H,3CNN,03) Calculated value (%)
C:46.41 H:4.60 CN:12.45
N: 19.68 Actual value (%) C: 46.75 +
1:4.68 C1:11.92 N:19.56 East 1
” (q1a clear 1, and in the same manner as the synthesis of intermediate C1 in Synthesis Example 1,
0.11 mol of 02 was obtained from 14 mol of 82.

FD mass spectrum: M”254 Elemental analysis value (C,, II, fl!N, O) Calculated value (%)
C:51.87) 1:5.94 CG13.92
N: 21.99 Actual value (%) C: 52.00 +
1:5.84 C1:14.08 N:21.87 Tokun" Cleared 1 point above] and 0.11 mole of C2 and 220 mj! A mixture of triethyl orthoformate was heated to reflux for 10 minutes. The precipitate was collected by filtration, washed with acetone and ether, and then recrystallized from a methanol/ether mixed solvent to obtain 0.10 mol of B2.

FD mass spectrum: M”264 Elemental analysis value (C, 2H, 3CIN40) Calculated value (%)
C: 54.45 H: 4,95 Cp: 13,39 N
:21.17 Actual value (%) C:54.531(:4
．． 88 CCl 3.30 N: 21.24 min 1 body 1 pi 8 lambda 1 20% hydrochloric acid 200 mβ was added to 0.10 mol of B2, and the mixture was heated and refluxed for 2 hours. After distilling off the water, use 200 mf of water again.
After stirring, water was distilled off. Dilute the residue with methanol 30
The mixture was dissolved to 0 mN, 20 ml of carbon disulfide and 14 g of potassium hydroxide were added, and the mixture was heated and refluxed for 6 hours. The solvent was distilled off, the residue was suspended in water and adjusted to pl+5 with 5% hydrochloric acid, filtered and dried to obtain 0.08 mol of B2.

FD mass spectrum: M+260 Elemental analysis value (C12) 112N40S) Calculated value (%)
C: 55.37 H: 4.65 N: 21.52 S
:12,32 Actual value (%) C:55,25 N:4
．． 56 N: 21.60 S: 12.45 In exactly the same manner as the synthesis of intermediate E1 in A synthesis example 1 of F2,
FD with 0.05 mol of F2 obtained from 0.08 mol of B2
Mass spectrum: M”274 Elemental analysis value (C, 3H,, N, SO) Calculated value (%) C: 56.9114: 5.14 N:
20.42 S: 11.69 Actual value (%) C: 60
．． 09) 1:5.11 N:20.41 S:11.
According to the synthesis of compound 1 in Synthesis Example 1, 0.05 mol of F
By oxidizing 2, 0.04 mol of Exemplified Compound 2 was obtained as white needle-like crystals.

FD mass spectrum: M”306 Elemental analysis value (C, 311, 4N, 5O3) calculated value (%)
C:50,9711:4.61 N:18.29
S: 10.47 Actual value (%) C: 50.8811:
4.67 N: 18.35 S: 10.39 Synthesis Example 3
(Synthesis of Exemplified Compound 3) (E,) (Compound 3) A solution of 0.05 mol of Intermediate E synthesized in Synthesis Example 1 dissolved in 70°C of ethanol was heated to 35°C while maintaining the temperature at 5°C.
Slowly drop 30 mN of % hydrogen peroxide solution and leave it as it is for 2 hours.
Stir for hours. 600ml of water was added and extracted with ethyl acetate. The solvent was distilled off from the extract, and the residue was recrystallized from acetonitrile to obtain 0.025 mol of Exemplary Compound 3 as white sword-shaped crystals.

FD mass spectrum: M”260 Elemental analysis value (C, 211, 2N, OS) calculated value (%)
C:55.3711:4.65 N:21.523:
12.32 Actual value (%) C: 55.30 H: 4.
59 N: 21.67 S: 12.45 Synthesis Example 4 (Synthesis of Exemplified Compound 4) (Compound 2) (Compound 4)
To a solution of 0.02 mol of Exemplified Compound 2 synthesized in Synthesis Example 2 in 1-20 + n 1 of glacial acetic acid containing 2 g of sodium acetate, 0.031 mol of sul7lyl chloride was added at 40'C under a nitrogen atmosphere. Slowly add 1. at room temperature.
The mixture was stirred for 5 hours. The product was collected by filtration, washed with water, and then recrystallized with methanol to obtain 0.007 mol of Exemplified Compound 4 in the form of white needle-like crystals.

FD mass spectrum: M+340 Elemental analysis value (C, 311, 3CρN, 03S) Calculated value (
%) C: 45.82 H: 3.84 N: 16,44
S:9,4] Actual value (%) C:45.7111:3
,75 N:i6.42 S:9.60 Synthesis Example 5 (Synthesis of Exemplified Compound 5) (A5) (B5) (C5) CD5) (Compound 5
) for “Monkey” JAyo! After mixing 1 mole of ethyl myristate, 105+nβ of acetonitrile, 250+nN of birinone and 115g of natriram methoxide at 90°C, the mixture was heated for 1.5 hours.
It refluxed. After stirring for an additional 30 minutes at 90°C, leave to cool.
It was poured into ice water from step 1 and made acidic with concentrated hydrochloric acid. Filter the precipitated solid,
After washing with 5% hydrochloric acid and drying, methanol/acetonyl) l)
Recrystallization was performed using a mixed solvent of 0.655 mol of myristoylacetonitrile.

0.40 mol of this myristoylacetonitrile, 2-=
) o-4-chlorophenylhydrazine m acid mo, 4
An aqueous solution containing 0 mol and 33 g of sodium acetate 80
Iol was dissolved in 600 ml of alcohol and heated under reflux for 4.5 hours. Then 40% aqueous sodium hydroxide solution 40 +n j! was added, stirred for 30 minutes, and then allowed to cool. The precipitate was collected by filtration, suspended in 100 ml of water, acidified by adding concentrated hydrochloric acid until it became a transparent solution, stirred for 20 minutes, and then suspended in 100 ml of water.
00 m (l of seven tons) + fully lubricated. The precipitated solid was collected by filtration, dried, and reconsolidated with ethanol to obtain 0.27 mol of A5.

FD mass spectrum: M+456 Elemental analysis value (C22I■3.CβN402>Calculated value (%
) C: 57.7611 near, 49 CN: 15.5
0 N: 12.25 Actual value (%) C: 57.82
H Near, 44 CG45.58 N:12.20 Jonin
Synthesis of Compound 5 In the same manner as in Synthesis Example 1, 0.27 mol of the above A5 was hydrogenated and reduced to B9, cyclized to C5, methylated to B5, and then oxidized to obtain Osha crystals of Compound 5. Crystallization gave 0.07 mol of Exemplary Compound 5 in the form of pale yellow needle-like crystals.

FD mass spectrum: M+478 Elemental analysis value (C24H3SCβN, 02S) calculated value (%
) C: 60J7) 1 near, 36 N: +1.69
S: 6.69 Actual value (%) C: 60.12 H near, 31 N: 11.78 S: 6.78 Synthesis example 6 (
Synthesis of Exemplified Compound 6) (B6) (CB) (B6)
(E6) (Compound 6) "Mushi"Tokipu"" - Synthesis of A5 in Synthesis Example 5 using 0.40 mol of 0-nitrophenylhydranone-1 acid salt and 0.40 mol of benzoylacetonitrile as raw materials The reaction and treatment were carried out according to the procedure described in 1. 0.30 mol of A6 was obtained. Next, hydrogenation reduction and η-condensation ring closure were performed in the same manner as in the synthesis method of Intermediate C6 and Intermediate D1 in Synthesis Example 1 to obtain 0.14 mol of 06.

0.14 mol of 06.0.19 mol of 1-nitro-4-
After heating and refluxing a suspension of iodobenzene and 140+n1 methanol for 1.5 hours (becoming a clear solution),
It was treated in exactly the same manner as the synthesis of intermediate E in Synthesis Example 1, and 0.
0.6 mol of D6 was obtained.

FD mass spectrum: M+413 Elemental analysis value (C22HISN502S) calculated value (%)
C: 63.9114: 3.66 N: 16.94 S
Near, 75 actual value (%) C: 63,82 +1:3
, 61 N: 16.98 S Near, 82nd Saturday (Dan 10th)
1 (0.06 moles of D6 was dissolved in 120 mβ of tetrahydrofuran and hydrogenated using a Pd/C catalyst at room temperature and pressure. The catalyst was filtered off, and the solvent was distilled off from the filtrate. The residue was After adding 0.06 mol of pelargonic acid chloride dissolved in acetonitrile of Loom, 0.072 mol of triethylamine was added dropwise and stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and recrystallized with ethyl acetate. 0.04 mol of E6 was obtained.

Ft) Mass spectrum: M”523 Elemental analysis value (C3, I+33NSOS) calculated value (%)
C near 1.10 H: 6,35 N: 13,37 S
:6,12 Actual value (%) C near 1. Ol lI:6
．． 42 N: 13.42 S: 6.05 Compound 60E
According to the synthesis of Compound 1 in Weiyu Synthesis Example 1, 0.04 mol of E
6 was oxidized, and the obtained crude crystals were recrystallized from ethyl acetate to obtain 0.03 mol of Exemplified Compound 6.

FD mass spectrum: M”555 Elemental analysis value (C31Hz] NsOsS) Calculated value (%) C:87,0011:5.98 N:+
2.60 S: 5.77 Actual value (%) C: 67.1
0 H: 5.93 N: 12,55 S: 5.87 Synthesis Example 7 (Synthesis of Exemplary Compound 7) Synthesis example except that 1 mol of ethyl myristate was replaced with 1 mol of ethyl p-dodecylsulfonylbenzoate 0.42 mol of r+-rdecylsulfonylbenzoylacetonitrile was obtained in exactly the same manner as in 5.

84 mn of an aqueous solution containing 0.42 mol of this p-dodecylsulfonylbenzoylacetonite, 0.42 mol of 2-nitro-4-methoxycarbonylphenylhydranone hydrochloride, and 35 g of sodium acetate was dissolved in 630 ml of alcohol. The mixture was heated and refluxed for 5 hours. Next, 42 ml of 40% aqueous sodium hydroxide solution 1. was added, stirred for 30 minutes, and then allowed to cool. Collect the precipitate by filtration, 100 +n
The suspension was suspended in 1 ml of water, dissolved by adding concentrated hydrochloric acid, stirred for 30 minutes, and poured into 500 ml of acetonitrile. The precipitated solid was collected by filtration, dried, and reconsolidated with ethanol to obtain 0.20 mol of A7.

FDW SuX9) Le: M+606 elemental analysis value (C
291 (39Ctl'N40.S) Calculated value (%) C
:57,3711:6,47 CC5,84N:9.2
3 Actual value (%) C: 57.5111: 6.36 C
I! : 5.79 N: 9.25" 11 Yu! and color reduction - In the same manner as in Synthesis Example 1, 0.20 mol of the above A was hydrogenated and reduced to B7, cyclized to C7, methylated to D7, and then oxidized to obtain crude crystals of Compound 7, and ethyl acetate・0.06 mol of Exemplified Compound 7 was obtained by recrystallization with a hexane mixed solvent.

FD mass spectrum: M+628 Elemental analysis value (C31H-oN+0-52) Calculated value (%)
C: 59.2111: 6.41 N: 8.91 S
:10.20 Synthesis Example 8 (Synthesis r# of Exemplary Compound 18,)
(Compound 5) (Compound 18
) Exemplary compound 5 synthesized in Synthesis Example 5 0.05 mol and 2
150 mj of acetonitrile containing 30 ml of N aqueous sodium hydroxide solution! While cooling with water and stirring, add 0.05 mol of benzyl chloroformate and 15 mol of 4N aqueous sodium hydroxide solution.
After slowly dropping 51 °C into the mixture, the mixture was stirred for 1 hour. After neutralization with hydrochloric acid and cooling, the precipitated solid was collected by filtration, washed with water, and recrystallized with ethyl acetate to obtain 0.04 mol of the exemplary compound.

FD mass spectrum: M+612 Elemental analysis value (C3211,, (1!N40.S) Calculated value (%) C:62,68 +4:6.74 N:9,
14 S: 5.23 Actual value (%) C: 62.51
H:6.75N:9. +6 S: 5.32 [Effect of the invention] Novel pyrazolo[1,5-a]- obtained by the present invention
1,3,5-1,3,5-benzotriazepine compounds can be used in various applications such as pharmaceuticals, agricultural chemicals, photographic additives, and dyes.

In particular, as a photographic additive, it is useful as a coupler used in silver halide color photographic light-sensitive materials, and is a compound useful as an intermediate in dyes.

Applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] Pyrazolo[1,5-a] represented by the following general formula [I]
]-1,3,5-benzotriazepine compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 each represent an alkyl group or an aryl group, and R_3, X and Y each represent a hydrogen atom or a substituent. m represents an integer of 0 to 4, and n represents 1 or 2. However, when m is 2 or more, multiple R
_3 may be the same or different. ]