WO1986001207A1

WO1986001207A1 - Pyridopyrimidine derivatives and process for their preparation

Info

Publication number: WO1986001207A1
Application number: PCT/JP1985/000441
Authority: WO
Inventors: Noriaki Kihara; Tatsuyoshi Ishida; Shigeru Isayama; Takeshi Ishitoku; Hiroaki Tan; Katsuya Takahashi
Original assignee: Mitsui Petrochemical Industries, Ltd.
Priority date: 1984-08-06
Filing date: 1985-08-06
Publication date: 1986-02-27
Also published as: JPS6143190A; JPH0339508B2

Abstract

New compounds of formula (I) ADwhere R1 represents a phenyl group optionally substituted by a lower alkyl group, a group of formula (II) (where each of R5 and R6 represents H, a lower alkyl group, or a methyl group substituted by a phenyl group, or R5 and R6 taken together represent a C4 - C6 alkylene group) or a group of formula (III) (where n is 2 or 3, R7 represents H, a lower alkyl group, an aralkyl group, a lower alkoxycarbonyl group, an aralkyloxycarbonyl group or an acyl group); R2 represents H or a lower alkyl group; R3 represents H, a lower alkyl group, an aralkyl group, an aryl group, a lower alkyl group substituted by a hydroxyl group, a lower alkyl group substituted by a lower alkoxy group or a lower alkyl group substituted by a tetrahydropyranoxy group; R4 is H, a lower alkyl group or an aralkyl group BD are disclosed together with a method for their preparation. The compounds are useful as herbicides.

Description

Specification

Piri Dohi. Limidine derivative and method for producing the same

Technical field

The present invention relates to a novel pyridopyrimidine derivative useful as a herbicide and a method for producing the same.

BACKGROUND ART Compounds having a pyridopyrimidine structure include, for example, Chemical Volume Ab Chem. Ab 70. Volume 110,07 (199), Volume 90, Volume 54, 89,3 (19) 79), ibid. 93, 1114280 (19980), and 97, 18.2350 (19882) are known. However, the usefulness of these compounds for illustrious use has not been clarified at all.

The present inventors, Pyridhi. In the course of research on the limidine derivative, it was found that the novel compound of the present invention, which is different from that described in the above-mentioned literature, was successfully synthesized, and that the compound had an excellent herbicidal activity. Was.

Disclosure of the invention

The present invention is based on (1)-general formula [I] 丄 li 3

N ^C , NCI]

R " ^J- ^ [Wherein, is a phenyl group which may be substituted with a lower alkyl group, a general formula [π]

-[Π]

5 (where? _5,? E represents each hydrogen or a lower alkyl group or a phenyl group substituted methylation group, or? ₅ and R ₆ are bonded to the § alkylene group having 4 stone ό carbon.) A group represented by the general formula [ffl]

/ \

-N N-R 〔ffl〕

ι ο (where w is 2 or 5 j}, and R ₇ represents hydrogen, a lower alkyl group, an aralkyl group, a lower alkoxycarbonyl group, an aralkyloxycarbonyl group or an acyl group.) J, R ₂ is hydrogen or a lower alkyl group] 9, R 3 is hydrogen, a lower alkyl group, an aralkyl group, an aryl group, a hydroxyl-substituted lower alkyl group, a lower alkoxy-substituted lower alkyl group

15 or Tetrahidrohi. Lanoxy group-substituted lower alkyl groups j and? 4 are hydrogen, lower alkyl groups or aralkyl groups. The same applies hereinafter. And a pyridopyrimidine derivative represented by the formula:

In the present invention, a method for producing the novel pyridopyrimidine derivative includes:

20 ② General formula [IV] ]

Reacting a pyrimidinecarboxylic acid amide derivative represented by the formula with a formylating agent in the presence of a base,

⑤General formula [I-π]

[I-π]

R

Wherein, R it is among the? ₇ shows Ararukiru group and benzyl old Kishika Lupo two Le group. The same applies hereinafter. ] According to the invention of the present application. By hydrogenolysis of lymidine derivatives] 9, and ④General formula []-R [I-]

[In the formula, R represents an aralkyl group xylcarbonyl or an acyl group among R ₇ . The same applies hereinafter. By acid-decomposition of the pyridopyrimidine conductor according to the present invention represented by the following formula: R.

0

\ N N-R [I-IE]

Ξ-Ν

, ^ ¹ n, a method for producing a pyridopyrimidine derivative represented by the general formula [V]:

— R []

Wherein, R ₈ represents a halogen, an alkoxy group and by the group et chosen Ru group of the nitro group] 9 unsubstituted or by good phenyl group optionally j9 substituted methyl group or hydrogen. The same applies hereinafter. ). Limidine derivative and general formula [w]

R iT-Q 〔I〕

(Wherein, is a lower alkoxycarbonyl group, an aralkyl-substituted xycarbonyl group, and Q is chlorine or bromine; like the following.) A general formula [IV] characterized by reacting a compound represented by the following formula: ]

R ₉ 0 1 R

CI-

A process for producing a pyridopyrimidine derivative represented by the formula: The substance of the present invention is represented by the general formula [I]. In the formula, as the lower alkyl group of the “phenyl group optionally substituted with a lower alkyl group” for R !, a methyl group, an ethyl group, a propyl group, and isoprohi. A, a n-butyl group, an isobutyl group, a sec-butyl group, a プ -butyl group, etc., among which a methyl group and an ethyl group are preferred, and the number of substitution with a lower alkyl group is usually 1 or 3], Preferably, the number of substitutions is one. The phenyl group which may be substituted is preferably? Examples thereof include a 5-tolyl group and a V-ethylphenyl group. When R is a group represented by the formula (Π), R ₅ and R 6 are the same as those described above as the lower alkyl group, and the phenyl-substituted methyl group is a pendyl group, a diphenylmethyl group, or the like. the R ₅ and 'R _e are bonded to § alkylene group having 4 ¾ stone ό carbon, particularly preferably one carbon teaching is 5.

Regarding R ₇ where R! Is a group represented by one敉式[[pi!], The lower alkyl group can be exemplified those listed before, preferably a methyl group, E Ji group, Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a triphenylmethyl group. Of these, a benzyl group is preferable, and the aralkyl group is a benzyl group. Examples include diphenylenetinole, quinolone, and di-phenylene, and φ-chlorophenylmethyloxycarbonyl, among which benzyloxycarbonyl is preferred.The lower alkoxycarbonyl is preferably Ethoxycarbonyl group, ethoxycarbonyl Examples thereof include a nore group, a propoxycarbinole group, an isopropoxycarbonyl group, and a ptoxylcarbonyl group, and among them, the former two groups are preferable. Further, examples of the acyl group of R 7 include a formyl group, an acetyl group, an aromatic acyl such as a pionyl group, an aromatic acyl such as benzoyl and toluoyl, and among them, formyl and penzyl are preferred. Better. Examples of the lower alkyl group represented by? ₂ and? 3 include those listed above.Examples of the aralkyl group represented by R3 include those represented by R7, and the aryl group represented by phenyl group and 0. -Tolyl group, -tolyl group, p-tolyl group, 2,4-xylyl group, 2,5-xylyl group, 5,5-xylyl group, 3,4-xylyl group Among them, a phenyl group is preferable. Among them, a methylol group, an ethylol group and the like as the hydroxyl-substituted lower alkyl group, and a methoxymethyl group, ethoxymethyl and methoxethyl group as the lower alkoxy-substituted lower alkyl group And ethoxyxyl. Among them, methoxethyl is preferable. As the tetraalkylovironoxy-substituted lower alkyl group, 2-tetrahydryl is preferred. Lanoxhetyl group, 5-'tetrahydrovirano oxypropyl group and the like, among which the former is preferable, and the lower alkyl group and aralkyl group of R ₄ also include those listed above. Can be done. · Specific examples of these compounds are shown in Table 1.

Ordinary

Table 1 (continued

Table 1 (continued

P ¾ I

Table 1 (continued

Table 1 (continued)

Table 1 (continued

[Production invention1]

The substance of the present invention is represented by the general formula [IV] (however, specific examples of R i or _{4 in} the formula are the same as those described in the description of the present substance. The same applies to other compounds hereinafter). By reacting a limidinidine carboxylic acid amide derivative with a formylating agent in the presence of a base. The compound represented by the general formula [W] can be obtained by the method described in the present applicant's application and the application filed on the same date and entitled “New limidine derivative and its production method” or a method based on the method, and further described below. Reference example: Which method is used?

Examples of the formylating agent include N, N'-dimethylformamide, N, N'-getylformamide, methyl orthoformate, ethyl ethyl formate, methyl formate, and ethyl formate. However, N, N'-dimethylformamide and methyl formate are preferred. Examples of the base used in the reaction include NaII, NaNH ₂ , LiH ヽ LiNH ₂ , LiN iso-pr) ₂ , t-BOK ^ MeONa¾, among which ^ αίΓ and t-BuOK Ka is preferred.

In the reaction, the above-described formylating agent is also used as a solvent. Therefore, it is not necessary to use another solvent, but it may be used. In this case, other solvents such as hexane, benzene, toluene, and xylene may be used, such as hydrocarbon solvents, athenole, tetrahydrofuran, dithioxane, and dimethinoresnorreoxide. it can.

—General! : N] is usually used in a molar amount of 1 to 20 times, preferably 1 to 10 times the molar amount of the compound of the formula [N], and the base is usually used in a molar amount of 1 to 3 times. The reaction is usually carried out at a temperature of 20 to 25 (3 ° C, preferably 8 to 150 ° C) for 0.5 to 10 hours, depending on other conditions. Purification and isolation of the target compound can be carried out by a conventional method as described in Examples below.

[Invention of manufacturing method2]

A compound represented by the general formula [I-ΠΙ] according to the present invention. Lidohi. The lymidine derivative can be produced by hydrocracking the bilimidine derivative represented by the general formula [I-II] according to the present invention. The aralkyl groups for Ri include those listed for R ₇ . This method can also be applied to the case of penzinolexyl carboxy, among the aranolequinoleoxycanoleboninole groups of R ₇ . 1 ό

In this method, usually, 触媒炭素 -carbon Raney—Ni, pd0, etc. can be used as a hydrocracking catalyst. The amount of the catalyst used is 0.01 to 1 times (molar ratio) the compound [I--:]. The reaction solvent is usually methanol, ethanol, or iso. Loha. Alcohol, formic acid, acetic acid, and alcohol. Lo hee. Carboxylic acids such as ononic acid, or ethanol-formic acid, ethanol

-Acetic acid Using a mixed solvent and dioxane, usually under normal pressure or 10 atm, preferably under normal pressure or 5 atm under hydrogen pressure, at a temperature of 0 to 200 ° C, preferably 2 ° C. Incubate at 800 ° for 0.5 hours for 10 hours. Purification and isolation of the target substance are performed by a conventional method.

[Invention of manufacturing process 3]

The pyridovirimidine derivative represented by the general formula [I-] according to the present invention can also be obtained by acid-decomposing the pyridobilimidine derivative represented by the general formula [I-IV]. In the formula [I-II], examples of the aralkyl carbonyl group and the acyl group represented by? Include those listed in? ₇ .

Examples of the acid used in this method include sulfuric acid, SCI (gas), Ox Br (gas), and the like. These acids are used in an amount of 1% for the compound of the formula [I-ιν]. Water, 100-fold molar use, water, methanol, ethanol, dioxane, THF-pense, benzene, tonolenene, xylene, formic acid, acetic acid, pulp. The reaction is carried out in a solvent such as ononic acid at a temperature of 0 to 10 CTC, preferably 2 (3 to 5 CTC) for 0.5 to 10 hours. After the reaction, the desired product is purified and isolated by the method shown in the Examples.

[Purification invention4]

The pyridopyrimidine derivative represented by the general formula [IV] according to the present invention is a compound represented by the general formula [V]. The compound can be produced by reacting a lidopyrimidine derivative with a compound represented by the general formula [I:]. The pyridopyrimidine derivative of the general formula [V] can be produced in accordance with the method described in the present invention [Production invention. 1]. Wherein R ₈ is chlorine, odor mottle which halogen, main butoxy group, Puroho ⁰ Kin group, a lower alkoxy group such as Isopurobokishi group, methyl substituted by the a phenyl group which may optionally be nucleus-substituted by a two preparative port group Group, for example, specifically, a benzyl group, a J) -chlorophenylmethyl group, a p-methoxyphenylmethyl group or hydrogen, and preferably a benzyl group or hydrogen. '

On the other hand, examples of the compound represented by the general formula [M] include lower alkoxycarbonyl groups and aralkyloxycarbonyl groups listed as ₇ .

As the reaction solvent, aromatic hydrocarbons such as benzene, toluene and xylene, and ethers such as dioxane can be used, and preferably ^^.

In the solvent, 1 to 2 moles of the compound represented by the general formula [VI] is used per 1 mol of the derivative represented by the general formula [V], and the temperature is 15 to 80 ° C, preferably 20 to 20 ° C. React at 0 ° C for 1 to 20 hours. As a result, the desired compound of the general formula [IV] can be obtained.

(Usefulness of the substance of the present application)

The substance has excellent activity as a herbicide. That is, the present substance can be used as a paddy field and upland herbicide. The weeds targeted by herbicides are especially effective against paddy field weeds, tamagayari, scallops, fireflies, spatula, and other upland weeds such as paddy weeds, hie, mexispa, aobu and kogomekaari.

In order to use the substance of the present invention as a herbicide, the substance of the present invention alone or a mixture of the substance with a body, a surfactant, a dispersant, an auxiliary agent and the like is formulated into a wettable powder, an emulsion, a fine particle or a granule. Dilute to an appropriate concentration and spray or apply directly.

BEST MODE FOR CARRYING OUT THE INVENTION

The following are examples and test examples! ) The present invention will be specifically described.

Example 12 2-Dimethylamino-ό-ethylpyrido [4 -—, 3-].

Limidine-5 _ (ό Manufacturing iOON

Na-sodium sodium 240 (（0% in oil, 6 dishes 0 I) was washed with hexane and suspended in iV-dimethylformamide (Di) 5 / ^. Then, 2 - dimethyl Ryomi Bruno - N - Echiru - 4 - Mechiruhi ⁰ Li Mi di emissions - 5 - Karubonami de 1. 0 4 g of (5 mm o I) of the i solution {^ Q nd) was added, 1 5 The reaction was performed at 0 ° C for 1.5 hours. F is distilled off under reduced pressure and then water 0 was added and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline and dried over magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained residue was recrystallized from ethyl acetate-hexane to give pale yellow crystals (0.009) (yield: 55%).

5 Melting point: 1 3 1 to 13 2 ° C

Infrared absorption spectrum (a tablet; ^ ^-1 )

1 6 5 5, 1 0 2 5, 1 5 8 0

1 E-nuclear magnetic resonance spectrum (Heavy mouth Holm; p pm)

'(α) 1.3 5 (35 ", t, J ^ 7.0 Hz) ^ (6) 5.2 8 {6 Ξ ^ s), (5 · ιο 9 ό (2 ^ ヽ q, = 7.0 ^ )), (me ό 0.50 (1 ox, d, = 7 · 45 ”z), (7 · 24 (1 ^ 5”, d, J = 7. AH z) ^ 009. 2 3 (1 5 ", s)

Reference I "12-Dimethylamino-N-ethyl-4-4-Methylpyrimidine

-5-Carbonamide production

2-dimethylamino-4-methylmethyl. Limidine-5-carboxylate is esthenole 3.9.0 g (20 mmoI), etinolemin 9.09 (200 mmoI) and 2 ^ .Q of sodium methoxide 1.0 g (4 mo I) of the methanol solution was placed in an autoclave of 5 (3? ^) and reacted at 110 ° C for 3.5 hours. The obtained reaction mixture was poured into 200 ml of water. The ethyl acetate layer was washed with saturated saline and dried over magnesium sulfate.

After 20, ethyl acetate was distilled off under reduced pressure. The obtained residue was recrystallized from ethyl acetate-hexane to give 3.48 fi of colorless crystals (yield 84%). Melting point: 1 3 8 to 15 9 ° C

Infrared absorption spectrum (tablet; cm- ¹ )

3 9 2 0, 1 0 2 0, 1 5 8 8

1 H-Nuclear magnetic resonance spectrum (heavy-mouth mouth honolem; φτη)

(α) .25 (3 ff ^ t, J = 7.O ff z) ^ (δ) 2.5 3 {5 S s), (c) 5.20 (05 ", s), (me 3.4 3 (2,), (5.8 (1 ^, δa), 0 8.5 2 (1, s)

Reference Yi j 2 N - Echiru - 4 - methyl - 2 - (1 - arsenate ⁰ Perijiniru) arsenide. Production of limidine-5-carbonamide

N-Etinole-4-Mechinore--Mechinorechi. Limidine-5-Force Norrebon Amid 2.1 1 (10 mm o I)- Peridine and 52 g (Q.1 moI) were heated to reflux for 18 hours. After removing excess piperidine, the residue was poured into water 20 and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline and dried over magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue obtained was recrystallized from ethyl acetate-hexane to give.? Yellow crystals.

1.85 g was obtained (yield 75%).

Melting point: 107-108 ° C

Infrared absorption spectrum (a tablet; cm'- ¹ )

5 5 0 0, 1 0 3 5, Ί 5 8 5

1 H-nuclear magnetic resonance spectrum (Heavy holm; p p)

() 1.2 2 (5 t, = 7.0 ^ z),) 1.4 to 1.8 (ό T), (2. 50 (5ff ^ s), (d) 5.42H, m), (e) 3.7-4.0 (4T), (/) 5.8 (15 ", br), (8.29 Ix, s) The following compounds shown in Examples 2 to 18 were prepared in the same manner as in Example 1. Example 2 ό-ethyl-2- (1-hydroxyperidinyl) pyridine [4,5-d .] arsenide Li Mi Jin - 5 (O) - sign yield: 0 7% mp: 1 5 1 ~ 1 5 2 ° C infrared absorption spectrum (S § tablets; - ¹⁾ 1 0 5 5 1 0 2 2, 1 5 7 5

¹ H-nuclear magnetic resonance spectrum (heavy-mouthed holmes; pp) (α) 1.34 (3ί, / = square),) 1.5 to 2. (3 (ό5 "), ( And (3.93 ((5 "), (e) or 0ό27 (15", d, J = 7.AHz) ^ (or () 7.24 (15 \ d, / = 7.4 z z), () 9.2 1 ox, s) Implemented j 5 2 — (4 Penzisole-1-h. Pera Gininole)-ό-proh. d) E. limidine -.5 (.0 H on pale yellow oil: 74 ° h

,

Infrared absorption spectrum (Wa CZ; cm- ¹ ) 100, 102, 158 01 1-nuclear magnetic resonance spectrum (deuterated chloroform; ppm)

(α) 0.9 ό (5 Η ヽ t, J-SHz, (b) 1.7 6 (25 ",), (c) 2.5

(s, 5 "1) 2

Z "6 {), (s, TS) S 2 (z _E 6 = 1, PE i) Z 1 (S) Vl

-GO { ^z E 6 = f PE) Z '9 (S) Vl ^ ^ G,, H "20 · ~ ZZ · £ (, (s HZ) 9 9 {z E 9 = ί,?, IT) Les

ZZ l ^ OO / £ 8df / l3d Ι0Π0 / 98 O Example 4 2- (4-Penzyl-1-1-biperazinyl) -1-6-isobromovirido [4,3-d] pyrimidine-1 5 (6H) -one Yield: 70%

Melting point: 1 571: '

Infrared absorption spectrum (KBr tablets, cm—L)

1 6 6 0, 1 6 1 8, 1 5 7 6

1 H—Nuclear magnetic resonance spectrum (Heavy-mouthed form; ppm)

(a) l.35 (6H, d, J = 7Hz), (b) 2.50 (4H, t, J = 6Hz), (c) 3.55 (2H, s), (d) 3.97 (4H, t, J = 6 Hz) _N (e) 5.23 (1H; seq, J = 7 Hz), (f) or (g) 6.29

(1 H, d, J = 8 Hz) _s (f) or (g), 7.3 (repeated with 1 H, (h) signal), (h) 7 · 33 (5 H, s), (i) 9.22 (1H, s) Example 5 6-ethyl-12-ferrido [4,3-d] bilimidine

-5 (6H) —ON

Yield: 20%

Melting point: 143.0-143.1 ° C

Mass spectrum: 251 (molecular ion peak), 222

Infrared absorption spectrum (Nujur; ^-1 )

1643, 1 599

1 H—nuclear magnetic resonance spectrum (Heavy α-form; ppm)

(a) δ 1.42 ί 3,, t, J = 7.4), (b) 4.07 (2 Η, q, J = 7.4), (c) 6.7 1 (1H, dq, J = 0.9, 7.4), (d) 7.40 to 7.70 (4H, m), (e) 8.48 to 8.70 (2H, m), ( f) 9.7 0 (1 H, s)

Example 6 2- (4-Benzyl-1-biperazinyl) -1 6- (2-meth-quishethyl) pyrido [4,3-d] pyrimidine-1 5 (6H)

'On

Yield: 56%

Mass spectrum: 37 9 (molecular ion beak)

Infrared absorption spectrum (neat; cm- ¹ )

3 0 40, 2 9 40, 28 2 0, 1 6 6 0

1 H—nuclear magnetic resonance spectrum (double-mouthed form; ρρι)

(a) 2.5 2 (4H, m), (b) 3.32 (3H, s), (c) 3.55 (3H, s), (d) 3.9 3 (4H, m) (e) 6.2 3 (1 H, d, J = 7.9 Hz) (f) 7.3 2 (5 H, s), (g) 7.3 4 (l H, d _} J = 7.9 Hz), (h) 9.2 1 (1 H, s)

Performed (| 72- (4-Benzyl-1-piperazinyl) -1-6-benzylpyrid [4,3-d] Birimidin-1 5 (6H) -one Yield: 72

Melting point: 144-; L 45 ° C

Infrared absorption vector (KBr tablet; cm- ¹ )

1 6 5 5, 1 6 1 2, 1 5 70 ^L H—nuclear magnetic resonance spectrum (double-mouthed form; ppm)

(a) 2.50 (4H, m), (b) 3.54 (2H, s), (c) 3.97 (4Hm), (d) 5.09 (2H, s), (e) or (f) 6.25 (1 H, d, J = 7.4 Hz), (e) or (i) 7.3 (1 H, (g), (h) overlap with signal), (g) or (h) 7.30 (5H, s) , Fe) or (h) 7.32 (5H, s), (j)

9.24 C 1 H, s)

Implementation ij8 2- (4-benzyl-1-1-piperazinyl) -1-6-phenylbilide [4,3-d] pyrimidine-1-5 (6H) -one Yield: 52%

Melting point: 1 67-1 68

Infrared absorption spectrum (KBr tablet;-')

1 660, 1 623, 1 5 92, 1 580

'Η—nuclear magnetic resonance spectrum (double-mouthed form; ppm)

(a) 2.53 (4H, m), (b) 3.56 (2H, s), (c) 4.01 (4Hm), (d) or (e) 6.36 (1H, d, J = 7.0Hz ) _N (d) or (e) 7.4 (1 H, (f), (g) duplicated to signal),) 7.33 (5 H, s), (g) 7.4 (5 H, m), (h) 9.24 (1 H, s)

Performed! L 9 2-(4-Benzyl-1-1-piperazinyl) -1-6- [2- (2'-tetrahidrobilanyloxy) ethyl] -pyrido [4,3

-d:] pyrimidine 1 (6H) —on

Yield 60 Yield: 60%

Yellow oil

Infrared absorption spectrum (neat; cm ~ ^l )

1 6 5 0, 1 6 1 5, 1 5 7 3

1 H—nuclear magnetic spectrum (heavy mouth lophosolem; p pm)

(a) 1.3 to 2.0 (6H), (b) 2.52 (4H, m), (c) 3.56 (2Hs) _N (d) 3.4-4.3 (10H), (e) 4 δ 6 (l H, m), (f) or (h) 6.2 6 (1 H, d, J = 7.4 Hz) _s (g) 7.3 3 (5 H, s), (f) or (¾ 7.4 0 (1 H, d, J = 7.4 Hz), (i) 9.2 2 (1 H, s)

Example 10 102— (4-Benzyl-1-piperazinyl) pyrido [4,3 ′ ′ — d] pyrimidine-1 5 (6H) —one

Yield: 68%

Melting point: 2 0 1.0

Mass spectrum: 3 2 1 (molecular ion peak)

¹ H—nuclear magnetic resonance spectrum (double-mouthed form; p pm)

(a) 2.54 (4H, t, J = 5 Hz), (b) 3.56 (2H, s), (c) 4.02C4H, t, J = 5Hz, (d) 6.3 0 (1 H, d, J = 7 Hz), (e), (i) 728-7.40 (6 H, m), (g) 9.20 (1 H, s), (h) l 0.8 2 (1 H, br S)

Example 1 1 2 — (4-Benzyl-1- 1-piperazinyl) -1-6-ethyl-1 8-Methylbilide [4,3-d] pyrimidine-1 5 (6H)

'On

Yield: 5 3 ^

Melting point: 1 49 ~ 1 5 1

Infrared absorption spectrum KBr tablets, ^-1 )

6 58, 1 6 25, 1 5 7 5

¹ H—nuclear magnetic resonance spectrum (double-mouthed form; ppm)

(a) 1.3 3 (3 H, t, J "= 7.2), (b) 2.15 (3 H, d, J = 0.9), (c) 2.50 (4 H, m), (d) 3.5 6 ( 2 H, s), (e)

3.9 2 2 H, q, JT = 7.2), (f) 4.00 (4H, m), (g)

7.1 0 (1 H, q, J = 0.9), (h). 7.33 (5 H, s), (i) 9.23 (1 H, s)

Performed! J 1 26-ethyl-1 2- (4-benzyl-1-1-homobiperazinyl) pyrido [4,3-d] pyrimidin-1 5 (6H) -one Yield: 89

¹ H—nuclear magnetic resonance spectrum (double-mouthed form; ppm) · (a) 1.37 (3 H, t, J = 6.8 Hz) _x (b) l.7 to 2.2 (2 H, m) ヽ (c ) 2.5 to 3.0 (4H, m), (d) 3.66 (2H, s), (e) and (i) 3.8 to 4.2 (6H, m), (g) or (h) 6.29 (lH , d, J = 7.2

Hz), (h) or (g) 7.26 (1 H, d, J = 7.2 Hz), (i) 7.33

(5H, s), (j) 9.26 (1H, s) Example 13 6-Ethyl-2- (4-benzyl-1-1-piperazinyl) bilide [4,3-d] pyrimidine-1 5 (6H) -one Yield: 87%

Melting point: 1 16 ~ 1 18Ό

Infrared absorption spectrum (KBr tablet, cm- ¹ )

1 660, 1638

(a) 1.32 (3 H, t, J = 7 Hz), (b) 2.50 (4 H, t, J = 6 Hz) _% (c) 3.54 (2 H, s) _N (d) 3.76 to 4.08 ( 6 H, m)

(e) 6.24 (1 H, d,. J = 7 Hz), (f) 7.23 (1 H, d, J = 7 Hz) _N (g) 7.31 (5H, s), (h) 9.20 (lH. , S)

JI 14 6-Methyl-1- (4-benzyl-1-biradinyl) pyrid [4,3-d] pyrimidine-1 5 (6H) -one Yield: 96%

Viscous liquid

lH—nuclear magnetic resonance spectrum (double-mouthed form; Ppm)

(a) 2.50 (4H, m), (b) 3.48 (3H, s), (c) 3.55 (2H, s), (d) 3.96 (4H, m), (e) 6.24 (1 H, d, J = 8 Hz),

(f) 7.24 (1 H, d, J = 8 Hz), (g) 7.32 C 5 H, m), (h) 9.20 (1 H, s)

Practical study j 15 6—Pyr-1-yl cyclobut-2- (4-benzinole 1-piperazinyl) pyrido [4,3-d] pyrimidin-5 (6H) -one Yield: 71%

Melting point: 1 1 3 to 1 1 4

¹ H—nuclear magnetic resonance spectrum (dual chroma αform; <5: ppm)

(a) 0.8 to 1.3 (4H, m), (b) 2.51 (H, m) (c) 3 .:! to 3.4 (1H, m), (d) 3.55 (2H, m) s), (e) 3.9 7 (4H, m)

(f) 6.2 2 (1H, d), (g) 7.30 (1H, d), (h) 7.33 (5H, s), (i) 9.20 (1H, s)

Infrared absorption spectrum (KBr tablet; cm- ¹ )

2 8 0 0, 1 6 5 0, 1 6 1 5

Perform (J 1 6 2— (4-benzyl-1-1-piperazinyl) -1-6-ethyl-1

8—Benzylpyrido [4,3-d] -Pyrimidine-1- (5H) -one Yield: 63%

Melting point: 2 1 2.5

Mass spectrum: 4 3 · 6 (molecular ion peak)

¹ .eta. nuclear magnetic resonance scan Bae-vector (heavy black port Holm; ppm)

(a) 1.5 1 (3H, t, J = 7 Hz), (b) 2.5 1 (4H, t, J = 4.5 Hz), (c) 3.56 (2H, s), (d) 3.8 0 to 4.20 (8H, m), (e) 7.00 (1H, s)

Preparation of lj 1 7 6-Echinoleic 2- (4-benzyl-1- 1-biperazinyl) -pyrido [4,3-d] pyrimidin-5 (6H) -one 2- (4-Benzyl-1-piperazinyl) -1-N-ethyl-4-methynolepyrimidine-5-capillonamide2 · 389- (7mmo1) in N, N-dimethylformamide solution (20) 0.94. ^ (8.4 mmo 1) of potassium t-butoxide was added, and the reaction was carried out at 150 for 1 hour. When the reaction mixture was treated in the same manner as in Example 1, 0.93 ^ the same target product as in Example 13 was obtained (yield 38%).

Performed! J 18 6-Ethyl-1- (4-benzyl-1-1-piperazinyl) -pyrido [4,3-d] bilimidine-1-5 (6H) -one sodium hydride 0.10 ( After washing 2.5 mmo 1) in hexane with hexane, it was suspended in dimethyl sulfoxide (DMS 0) 2. Next, add a DMSO solution (3 ^) of 2-(4-1-benzene-1-biperazinole)-1-N-ethinol-1-4-methylpyrimidine-5-potassium ribomamide 0.68 ^ (2 mmo 1) at room temperature. after stirring 15 minutes, added dropwise Echiru formic acid 1.48 ^ (20 mmo 1) 50 X: 2 hours _σ example 1 was carried out in a place treated similarly reaction mixture, the same desired product as in example 13, 0.36 ^ Obtained (51% yield).

Preparation ll 19 6-Ethyl-1-8-methyl-1- (1-pipera'dinyl) pyrid [4,3-d] pyrimidin-5 (6H) -one Preparation of 2- (4-benzyl-1-1 —Piperazinole) 1 6—Echinole 1 8—Methinole pyrido [4,3-d] Pyrimidine 1 5 (6H) —On 300 M (0.83 Add ethanol 6, acetic acid 2 ^ and 10% palladium carbon 30 to mmo 1), and heat at 45 C for 3.5 hours in a hydrogen atmosphere. The reaction mixture is concentrated under reduced pressure except for palladium-carbon. Add water 20 to the concentrate and add carbon lime until foaming stops. The extract was extracted three times with a black mouth form 50, and the black mouth form layer was dried over sodium sulfate, concentrated and concentrated, and 6-ethyl-18-methyl-12- (1-biperazinyl pyrido [4, 3-d] Pyrimidin-5 (6H) -one was obtained as colorless crystals in 200 ^ (yield: 88 ヽ, melting point: 170-172 I:

Infrared absorption spectrum (KBr tablet; — ¹ )

1 657, 1 6 18, 1578,

¹ H—nuclear magnetic resonance spectrum (double-mouthed form; ρρπθ

(a) 1.33 (3Η, t, J = 7.2) _s (b) 1.66 (1 H, s), (c) 2.17 3 H, d, J = 1.3) (d) 2.94 (4 H, m) _% (e) 3.97 (6 H, m), (f) 7.1 0 Γ 1 H, q, J = 1.3), (g) 9.24 (1 H, s)

The compounds shown in Examples 20 to 28 below were prepared in the same manner as in Example 19.

XB.

Example 20 2- (1-piperazinyl) -1 6-n-propyl-1- [4,3-d] pyrimidin-5 (6H) -one Yield: 70%

Melting point: 143Ό Infrared absorption spectrum (KBr tablet; cm " ¹ )

3 3 2 5, 1 6 6 0, 1 6 2 2, 1 5 7 6

iH—nuclear magnetic resonance spectrum (deuterated dimethyl sulfoxide; ppm)

(a) 0.8 8 (3 H, t, J = 8 Hz) _s (b) 1.6 6 (2 H, m, (c) 2.75 (4 H, t, J = 6 Hz), (d) 2.8 ( 1 H, (c) and repetition),

(e) 3.7 6-3.9 1 Γ 6 H, m), (i) or (g) 6.2 2 (1 H, d, J = 8 Hz), (i) or (g) 7.7 3 (1 H, d , J = 8 Hz). (H) 9.0 3 1 H, s

Example 2 16-Isopropyl-1 2- (1-biperazinyl) monopyrid

C 4, 3-d] pyrimidin-5 (6H) -one Yield: 64%

Melting point: 16 1 X:

Infrared absorption spectrum (KBr tablet; cm- ¹ )

3 4 3 0, 1 6 5 2, 1 6 1 8, 1 5 8 4)

1 H—nuclear magnetic resonance spectrum (double-mouthed form; ppm)

(a) 1.3 1 C 6 H, d, J = 8 Hz), (b) 2.9 2 (4 H, bs), (c) 3.9 2 C 4 H, bs), (d) 5.0 5 (1 H, s eq, J = 8 Hz) (e) 6.2 (1 H, bs) _N (i) or (g) 6.2 9 (1 H, d, J = 8 Hz), (i) or (g) 7.83 (l H, d, J = 8 Hz), (h) 9.0 8 C 1 H, s) Example 2 2 6-Phenyl-1 2- (1 -pirazuryl) pyrido [4, 3

— D) Preparation of pyrimidine-1 (6H) -one Yield: 9 5 ^

Melting point: 100-105 (recrystallized from ether)

Infrared absorption spectrum (KB Γ tablet; α ^→ )

3 3 0 0, 1 6 5 0, 1 6 2 0, 1 5 9 0

¹ H—Nuclear Magnetic Resonance Spectrum (Heavy. Mouth Holm; ppm)

(a) 3.0 4 (4 H, m) (b) 4.0 4 (4 H, m), (c) or (d) 6.35 Γ 1 H, d, J = 7.4 Hz, (e) and f (c ) (D)) 7.4 (6H), (f) 9.2 2 Γ 1 H, s ^

J 2 3 6 —Benzyl-2- (1-biperazinyl) virido [4,3d] pyrimidine-1 5 (6H) —one

Yield: 41%

ra i! fi point: 1 6 0 to 1 6 3 Ό

Infrared absorption spectrum (KB r tablets, —l

3 4 0 0, 1 6 6 5, 1 6 1 5, 1 5 7 0

ιΗ—nuclear magnetic resonance spectrum f CDC l a, p pm)

(a) 3.0 8 (m, 4 H) _λ (b) 4.10 C m, 4 H) (c) 5.1 2 (s 2 H), (d) 6.28 (d, 1 H, J = 7.2 Hz) , (E) 7.32 (d 1 H, J = 7.2 Hz), (f) 7.34 (s, 5H), (g) 9.28 (s

1H)

Example 2 42- (1-Piperazinyl) pyrido [4,3-d] pyrimidin-5 (6H) -one Yield: 99%

Melting point: 252.8 (Ethanol recrystallization)

mas s.: 2 3 1] I Factory

R: (δ ppm in DMSO d-6)

(a) 2.87 C 4 H, b r. s), (b) 3.88 (4 H, b r. s), (c)

5.73 r iH, d, J = 7 Hz (d) 6.98 (l H, d, J = 7 Hz), (e) 9.0 2 C 1 H, s

Implementation l! 2 5 6-Ethyl-1- (1-piperazinyl) -18-benzyl-1-pyrido [4,3-d] pyrimidin-1 5 (6H) -one Yield: 56%

Melting point: 2 3 1.7

Mass spectrum: 3 49 (molecular ion peak)

Infrared absorption spectrum (KBr tablet, OT- ¹ )

34 0 0, 2 9 20, 1 6 5 4, 1 6 1 7, 1 5 7 4

[11—nuclear magnetic resonance spectrum (deuterated dimethyl sulfoxide; ppm)

(a) 1.24 (3H, t, J = 7 Hz), (b) 2.96 (4H, br.s), (c) 3.80-412 (8H, m), (d) 7.24 ( (5H, s), (e) 7.80 (1H, s), (f) _8. _6. (iH, s)

Example 26 6-Ethyl-1- (1-biperazinyl) pyrido [4,3-d] pyrimidine-1 5f6H) -one

Yield: 73% Melting point: 1 49 ~ 1 5 2

Infrared absorption spectrum KBr, CHC13; cnT ¹ )

1 6 5 5, 1 6 4 5, 1 6 2 0, 1 5 7 5

1 H—nuclear magnetic resonance spectrum (double-mouthed form; ppm)

(a) 1.3 4 Γ 3 H, t, J = 7 Hz) _N (b) 1.8 7 (1 H, b r.s

(c) 2.94 (4 H, t, J = 6 Hz) _x (d) and (e) 3.96 (6 H,) (f) or (g) 6.27 fl H, d, J = 8 Hz), ( f) or (g) 7.2 9 (1 H, d, J = 8 Hz) (h) 9.2 2 (1 H, s)

Example 2 7 6 1-ethyl-1 2 -— (1-homobiperazinyl pyrido [4,

3—d] pyrimidine-1 5 (6H) —on

Yield: 94%

(a) 1.34 (3 H, t, J = 7.2 Hz), (b) 1.59 Γ 1 H, s) (c) 1.8 to 2.1 (2 H, m), (d) 2.8 to 3.1 (4 H, m), (and (f) 3.8 to 4.1 f6H, m), (g) or (h) 6.2 7 (1H, d, J = 7.4 Hz) (h) or (g) 7.2 6 (l H, d, J = 7.4 Hz), (i)

9.2 3 (1 H, s)

Example 2 86-Methyl-1- (1-piperazinyl) pyrido [4,3-d] pyrimidin-5 (—6H) —one

Yield: 86%

Oil condition

¹ H—nuclear magnetic resonance spectrum (double-mouthed form; 3 ppm) (a) 2.93 (4H, m), (b) 3.50 (3H, s), (c) 3.94 (4Hm), (d) 4.40 (1 H, br. S ·), (e) 6.25 (1 H, d, J = 8 Hz) _N (f) 7.25 (1 H, d, J = 8 Hz) _N (g) 9 . 2 3 (1 H, s)

Example 29 Preparation of 96-ethyl-2- (1-piperazinyl) pyrido [4,3-d] birimidine-l-5 (6H) -one

2-C 4-benzyloxy 1-piperazinole) 1-6-ethynolepyrido [4,3-d] pyrimidine 1-5 (6H) -one 0. C 1.0 mmo 1) in ethanol 15 ^ and acetic acid 1 was added, and hydrogen gas at normal pressure was brought into contact for 50 and 2 hours in the presence of 5% Pd—C0.2. 5-C was removed from the reaction mixture, and the solution was dried under reduced pressure. After adding water and neutralizing with carbonated lime, extraction was performed with black-mouthed form. When the black form layer is treated in accordance with a conventional method, the same 6-ethyl-1- (1-piperazinyl:) pyrid [4,3-d] pyrimidine-1-5- (6) as the compound shown in Example 26 is obtained. H) -one was obtained in a yield of 0.08 ^ f 31).

Example 3 0 6 —Ethyl-1- (1-biperazinyl) bilide [4,3-d] bilimidine-1 5 (6H) —one of i¾

2— (4—Benzyroxycanoleboninole 1—biradininole) — 6—ethylpyridide! : 4, 3-d] pyrimidine-1 (6H) -one 0.45 ^ (1.1 mmo1) was reacted in 25 hydrogen bromide acetic acid solution 10 at room temperature for 2.0 hr. Was. After the reaction mixture was evaporated to dryness under reduced pressure, water was added and neutralized with potassium carbonate. K After extraction with loroform, treatment with a conventional method is the same as that of the compound shown in Example 26. 6-Ethyl-1- (1-biperazinyl) pyridine [4,3-d] pyrimidine-1 5 (6H) — 0.17 (59%) was obtained.

Reference Example 2— (4-formyl-1-piperazinyl) -1-6-isoprovirpyrido [4, '3-d] pyrimidine-l-5 (6H) -one

6-Isopropyl-2- [1-biperazinyl) pyridine [4,3-d] pyrimidin-5 (6H) -one 0.273 (lmmol) and formic acid 2.39- (50mmol :) were reacted at 80 for 1 hour. Was. The formic acid was distilled off under reduced pressure, and the residue was recrystallized from methylene chloride-hexane to obtain 0.253 ^ as white crystals (yield 80%).

Melting point: 1 92

Infrared absorption spectrum (KBr tablet; of ¹ )

16 58, 1616, 1 576

Ή—nuclear resonance spectrum (double-mouthed form: ppm)

(a) 1.38 (6H, d, J = 8 Hz), (b) 3.41 to 3.73 (4H, m), (c) 3.93 to 4.10 (4H, m), (d) 5.26 (1H, seq , J = 8Hz) (e) or (f) 6.35 (lH, d, J = 9Hz), (e) or) 7.40 (1H, d, J = 9Hz), (g) 8.16 (1H , s), () 9.27 (1 H, s)

Example 31 2- (4-ethoxycarbone-l-piperazinyl) -1 6

—Phenylpyrido [4,3-d] pyrimidine-1 5 (6H) —On manufacturing

2-C 4-benzyl-1-biperazinole) -6-pheninolepyrido [4,3-d] pyrimidine-1 5 (6H) -one 30.0 ^ (0.78mmo1) No ethyl carbonate 130 (1.2 mmol) was added to tetrahydrofuran 10 and reacted at 60 ° C. for 3 hours. The solvent was distilled off under reduced pressure, and the residue was washed with n-hexane to obtain pale yellow crystals 290 (yield 92).

Melting point: 1 9 2.3

Mass vector: 3 7 9 (Molecular ion beak)

Infrared absorption spectrum (KBr di sk; cirT ¹

1 6 9 5, 1 6 6 1, 1 6 2 4, 1 5 8 8

tH- nuclear magnetic co spectrum (CDC1 _3; ppm)

(a) 1.29Γ3H, t, J = 7), (b) 3.55 (4H, m), (c) 3.99 (4H, m), (d) 4.17 (2H, q, J = 7), (e) 6.3 4 (1H, d, J = 6) _N (f) 7.4 1 (6H, m) (g) 9.24 (1H, s.

伊 j 3 2 2— (4-benzyloxycarbonyl-1 1-piperazinyl)

-Production of 6-phenylvinyl [4,3-d] pyrimidine-5 (6H) -one

2- (4-benzyl-1 1-piperazinyl) -1 6-phenylpyrido [4,3-d] pyrimidine-1 5 (6H) -one 10 0 ^ (0.26mmo1) and benzylinoxycarbo Ninorechloride 90 Offl (5.7 7 mmo 1) In addition to de-o-furan 5, the mixture was heated at 60 X: for 3 hours. The solvent was distilled off under reduced pressure, and the residue was washed with n ^ xane to obtain pale yellow crystals 100 ^ (yield: 82, melting point: 173.3 C)

Mass spectrum: 44 1

Infrared absorption spectrum (nudule; cm- ¹ )

1 69 8, 1 6 60, 1 62 3

1H- NMR spectrum (CDC 1 _3; ppm)

(a) 3.6 1 (4H, m) (b) 4.00 (4H, m :), (c) 5.18 (2H, s), (d) 6.36 (1H, d, J = 7 ), (E) 7.37 "1 H, m), (f) 9.25 (1 H, m)

J 3 32-C 1-benzyloxycarbonyl-1 1-piperazinyl)

6-Ethylpyrido [4,3-d] pyrimidine 1 5 (6H

—On manufacturing

2- (4-Benzyl-1-piperazinyl) -1-6-phenylbilide [4,3-d] pyrimidine-1-5 (6H) -one and substituted ethyl ethyl carbonate]) The compound was synthesized in the same manner as in Example 31 using (4-benzyl-11-biperazinyl) -1-6-ethylpyrido [4,3-d] pyrimidin-15 (6H) -one and benzyl carbonate.

Yield: 83%

Infrared absorption spectrum (KBr tablets, cm- ¹

170 9, 1 6 60, 1 638 Nuclear magnetic resonance scan Bae click Honoré (C DC 1 _3; ppm)

(a) 1.35 (3 H, t) _x (b) 3.6 2 C 4 H, m) (c) 3.76-4.08 (6 H, m), (d) 5 20 C 2 H, s) (e) 6.25 (1 H d, J = 7 Hz) (f) 7.25 C 1 H, d, J = 7 Hz (g). 7. 3 6 (5 H, s, (h) 9.23 Γ 1 H, s ^

Formulation example as herbicide

Next, a description will be given of a compounding example of the invention. The figures indicate weight percentages.

Seven.

Formulation example (wettable powder)

'Compound of the present invention 10 ^ Higher alconyl sulfate ester sodium salt 3 Rin 8 7 ^ More than uniformly mixed and ground to form a wettable powder ₍

Pre-germination treatment test

Field soil was packed into porcelain pots with an inner diameter of 9 cm, and Aobu, Kogome and Ryari were sown. Immediately, 300 g of a wettable powder containing the specified compound per 1 are dispersed in 20 liters of water, and sprayed over the entire surface of the soil with a small sprayer from above the pot. After the treatment, the plants were placed in a greenhouse for one day and the herbicidal efficacy was examined.

Weeding effect

5 Complete withering 4 Weeding effect Large

3 Weeding effect Medium

2 Small weeding effect

1 Weeding effect

0 Invalid (normal)

Table 2 shows the results.

Industrial applicability

As described above, the novel compounds of the present invention are useful as herbicides _c

Claims

Scope of claim ω — General formula [ι]

[I]

[In the formula, is a phenyl group optionally substituted with a lower alkyl group, a general formula [Π]

[N]

, Hj 6

(Where R ₅ and R ₈ are each hydrogen, a lower alkyl group or a methyl group substituted with a phenyl group, or R ₅ and R ₆ are bonded to each other to represent an alkylene group having 4 to 6 carbon atoms.) Group or general formula []

■ Ν Ν— R ₇ ]

\ /

(CH ₂ ) _n

(Where n is 2 or 3), and R ₇ represents hydrogen, a lower alkyl group, an aralkyl group, a lower alkoxycarbonyl group, an aralkyloxycarbonyl group or an acyl group. R ₂ is hydrogen or a lower alkyl group; R ₃ is hydrogen, a lower alkyl group, an aralkyl group, an aryl group, a hydroxyl-substituted lower alkyl group, a lower alkoxy group-substituted lower alkyl group or Tetrahydroxy is a lower alkyl group substituted with a silane group. ] 9, R ₄ is hydrogen, a lower alkyl group or an aralkyl group. A pyridopyrimidine derivative represented by the formula:

(2) General formula (m

(M

Wherein R _t is a phenyl group which may be substituted with a lower alkyl group,

[H]

'

(Wherein R ₅ and R ₆ are each hydrogen, a lower alkyl group or a methyl group substituted with a phenyl group, or R ₅ and R ₆ are bonded to each other to represent an alkylene group having 4 to 6 carbon atoms.) Group or general formula (I)

N R

\ / [I]

CCH,)

n

(Where n is 2 or 3 der] 9, R ₇ is hydrogen, lower alkyl group, Ryo Lal Kinore group, ₃ exhibiting low及alkoxycarbonyl group, § Lal Kill O carboxymethyl carbonylation Honoré group or Ashiru group) in R ₂ is hydrogen or a lower alkyl group] 9, R ₃ is hydrogen, lower alkyl group, aralkyl group, aryl group, hydroxyl-substituted lower alkyl group, lower alkoxy-substituted lower group Lower alkyl group substituted with an alkyl group or tetrahydrovinyloxy group.

And R ₄ is hydrogen, lower alkyl group or aralkyl group. Wherein the pyrimidinecarboxylic acid amide derivative of formula (I) is reacted with a formylating agent in the presence of a base.

[I]

In the formula, R ₄ is the same as described above. A method for producing a pyridopyrimidine derivative represented by).

(3) ~ formula (I-I)

R ₇ - [I- Π]

o (where n is 2 or 0.3]), R ₇ is an aralkyl group, a benzyloxycarbonyl group] 9, R ₂ is hydrogen or a lower alkyl group, and R ₃ is

-7km, lower alkyl, alkyl, aryl, hydroxyl-substituted lower alkyl, lower alkoxy-substituted lower alkyl or tetrahydropyranoxy-substituted lower alkyl)]), ¾4 is hydrogen And a lower alkyl group or an aralkyl group. ), Wherein the pyridopyrimidine derivative represented by the formula (I) is hydrogenolyzed.

(Wherein, R ₂ to R ₄ are the same as described above.) C

(4) General formula [I-IV]-R [I-m

(Where n is or 3]), is an aralkyloxycarbonyl group or an acyl group] 9, R ₂ is hydrogen or a lower alkyl group], R ₃ is hydrogen, a lower alkyl group, An aralkyl group, an aryl group, a hydroxyl-substituted lower alkyl group, a lower alkoxy group-substituted lower alkyl group or a tetrahydropyrazoxy group-substituted lower alkyl group], 9, and R ₄ are hydrogen, a lower alkyl group or an aralkyl group. (1) wherein the pyridovirimidine derivative represented by the formula (1) is acid-decomposed.

[I — m

(Wherein, R ₂ ¾ stone R ₄ are the same. Above) the production method of pyridinium Dobiri derivative represented by _c

(Five)

[V]

During ί formula, eta 2 or 3 der] 9, beta ₈ is halogen, by the good phenyl group optionally by being nuclear substituted group selected from the group consisting of alkoxy groups and secondary preparative port group]? substituted Methyl or hydrogen], R ₂ is hydrogen or lower alkyl]], R ₃ is hydrogen, lower alkyl, aralkyl, aryl, hydrogen-blocked lower alkyl, lower alkoxy A substituted lower alkyl group or a tetrahydroxylanoxy group-substituted lower alkyl group] 9,

R ₄ is hydrogen, a lower alkyl group or an aralkyl group. And a compound represented by the general formula [VI]

η-Q an

(Wherein, is a lower alkoxycarbonyl group or an aralkyloxycarbonyl group), and Q is chlorine or bromine.) A compound represented by the general formula [IV ] ^f 'one [I one V]

_{_{(Wherein, n, R 2, R 3}} , R 4 and HZ "are the same. Above) the production method _c of pyridinium Dobiri thymidine derivative represented by the