JPH09241282A - New phosphorus-containing heterocyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new derivative comprising a 1-substituted phenyl-2- phospholene compound or phosphorane compound obtained by carrying out electrophilic substitution reaction of 1-phenyl-2phospholene, having herbicidal activity and useful for an active ingredient of herbicide. SOLUTION: This new phosphorus-containing heterocyclic compound is represented by formula I [R is H or a 1-6C alkyl; X is a 1-4C alkyl, a 1-4C alkoxy, amino, nitro, an acyl, carboxyl, cyano, hydroxyl, azide, mercapto, etc.; R<1> is a halogen or hydroxyl group; R<2> is hydroxyl group or R<1> and R<2> may together form a single bond; (n) is 1-5] and is useful as an active ingredient, etc., of herbicide. The compound is obtained by using 1-phenyl-2-phospholene represented by formula II as a starting raw material and subjecting phenyl group which is a substituent group on the phosphoric atom to electrophilic substitution reaction to afford a compound represented by formula III, as necessary, carrying out addition reaction with double bond of the phospholene ring to introduce a halogen group or hydroxyl group therein.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to novel phospholene compounds and phosphorane compounds having a substituted phenyl group.

[0002]

2. Description of the Related Art Substitutes in which a carbon atom, a nitrogen atom, a sulfur atom, or a selenium atom in place of an oxygen atom in a normal hemiacetal ring are replaced with a pseudo-sugar, an amino sugar, a thiosugar, and a selenosugar are variously studied. Has been done. On the other hand, phosphorus sugars in which the oxygen atom in the hemiacetal ring has been replaced with a phosphorus atom are difficult to chemically synthesize, and their structures, properties, physiological activities, etc. have not been studied much.

[0003]

Therefore, the present inventors have diligently studied a 1-phenyl-2-phosphorene derivative of an unsaturated five-membered heterocyclic compound containing a phosphorus atom, which constitutes the basic skeleton of a phosphorus sugar. As a result of research, they found that 1-substituted phenyl-2-phosphorene derivatives have herbicidal activity, and found a simple method for producing these compounds, and completed the present invention. That is, the present invention provides 1-substituted phenyl-2-
It is to provide a phospholene compound, a 1-substituted phenyl-2-phosphorane compound, a method for producing them and a herbicide containing them as an active ingredient. Hereinafter, the present invention will be described in detail.

[0004]

The present invention is a phospholene compound or a phospholene compound represented by the formula [I].

[0005]

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In the formula, R is a hydrogen atom or a linear or branched C _1-6 alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, a halogen atom, a fixed alkyl group or a lower alkoxy group. Represents a benzyl group which may have a substituent such as a group. X is a C _1-4 such as methyl or ethyl group which substitutes at any position of the benzene ring.
C _1-4 alkoxyl groups such as alkyl groups, methoxyl and ethoxyl groups, C _1-6 such as amino groups and methylamino groups
DiC _1-6 alkylamino group such as alkylamino group, dimethylamino group, acylamino group such as acetylamino group, benzoylamino group, C such as trifluoromethyl group
_1-6 haloalkyl group, acetyl, propionyl, benzoyl and other acyl groups, carboxyl group, cyano group, hydroxyl group, azido group, mercapto group, methylthio,
C _1-6 alkylthio group such as ethylthio, sulfonic acid group,
C _1-6 such as methoxycarbonyl and ethoxycarbonyl groups
Alkoxycarbonyl group, isocyano group or fluorine,
Represents a halogen atom such as chlorine or bromine. R ¹ represents a hydroxyl group or a halogen atom such as chlorine bromine, R ² represents a hydroxyl group, or R ¹ and R ² may be integrated to form a single bond. n represents an integer of 1 to 5, and when n is 2 or more, X may be the same or different.

More preferred examples of the substituent of the phenyl group are 3-nitro group, 4-nitro group, 3-amino group and 4-amino group.
Amino group, 3-acetylamino group, 4-acetylamino group, 3-dimethylamino group, 4-dimethylamino group, 3
-Acetyl group, 3-propionyl group, 3-chloro group, 4
-Chloro group, 2-chloro group, 4-fluoro group, 3-fluoro group, 2-fluoro group, 4-bromo group, 3-bromo group, 2-bromo group, 4-methyl group, 3-methyl group, 2 −
Methyl group, 4-methoxyl group, 3-methoxyl group, 2-
Methoxyl group, 2,4-dichloro group, 2,4-difluoro group, 2,4-dimethyl group, 2,4-dimethoxyl group,
Examples thereof include a 3-trifluoromethyl group and a 4-trifluoromethyl group.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced as follows.

(1) 1-Phenyl-2-phosphorene (I
Induced synthesis from I)

[0010]

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That is, using 1-phenyl-2-phosphorene (II) as a starting material, an electrophilic substitution reaction is performed on a phenyl group, which is a substituent on a phosphorus atom, to give a corresponding 1-substituted phenyl-2-phosphorene derivative. There is something to gain. Electrophilic substitution reactions that can be used in this reaction include nitration reaction, Friedel-Crafts reaction and halogenation reaction. These electrophilic substitution reactions are meta-oriented and a meta-substituted product is obtained as a main product.

Among the above electrophilic substitution reactions, the nitration reaction is carried out under ordinary nitration conditions such as mixed acid (nitric acid-acetic acid), nitric acid alone, nitric acid-acetic acid, nitrate-sulfuric acid, dinitrogen pentoxide, organic nitrate ester. , Nitronium tetrafluoroborate, etc. are reacted.

In this reaction, the m-nitride is the main product, and this nitrate is used as a reducing agent for ordinary reducing agents such as tin (II) chloride-hydrochloric acid and lithium aluminum hydride, and palladium. The corresponding m-amino compound [I-2] can be derived by reduction using catalytic reduction using a metal catalyst such as.

[0014]

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The Friedel-Crafts reaction is carried out under usual reaction conditions, for example, aluminum chloride and secondary chloride.
In the presence of Lewis acids such as iron and zinc chloride, acetyl chloride, propionyl chloride, benzoyl chloride, p-
It is carried out by reacting an acyl halide such as chlorobenzoyl chloride, an alkyl halide such as methyl chloride, methyl bromide, methyl iodide, chloroform, chloroform and methylene chloride.

The halogenation reaction is carried out under ordinary halogenation conditions such as halogen gas such as chlorine and bromine, thionyl chloride, thionyl bromide, sulfuryl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride and the like. Is performed.

(2) Production from 1-alkoxy-2-phosphorene derivative Further, the compound of the present invention is converted to 1-halogeno-2-phosphorene [IV] easily obtained from 1-alkoxy-2-phosphorene [III]. It can also be obtained by acting a substituted phenyl Grignard reactant.

[0018]

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That is, the starting 1-alkoxy-2-phosphorene [III] is reacted with a halogenating agent such as thionyl chloride, sulfuryl chloride or thionyl bromide to give the corresponding 1-halogeno-2-phosphorene [I].
V] was obtained, and (p-chlorophenyl) magnesium bromide, (p-methylphenyl) magnesium bromide, (p-methoxyphenyl) magnesium bromide, (m-chlorophenyl) magnesium bromide, bromide ( Bromide of m-methylphenyl) magnesium, (m-methoxyphenyl) magnesium bromide, (o-chlorophenyl) magnesium bromide, (o-methylphenyl) magnesium bromide, (o-methoxyphenyl) magnesium bromide, etc. Substituted phenyl) magnesium is reacted. .

Examples of the solvent used in this reaction include chain or cyclic ethers such as tetrahydrofuran, THF, diethyl ether, dioxane and dimethoxyethane. The reaction normally proceeds smoothly in the temperature range of 0 ° C to 60 ° C.

(3) Production of 1-alkoxy-2-phosphorane derivative A corresponding diol or halohydrin is produced by converting 1-alkoxy-2-phosphorene derivative into a diol or halohydrin using an osmium tetroxide catalyst. be able to.

[0022]

[Chemical 6]

That is, the 1-alkoxy-2-phosphorene derivative is obtained by allowing an oxidizing agent such as sodium chlorate to act in the presence of a catalytic amount of osmium tetroxide. Examples of the solvent used in this reaction include water, a mixed solvent of water and THF, and the like. The reaction normally proceeds smoothly in the temperature range of 0 ° C to 60 ° C.

The phosphorane compound may have various stereoisomers due to the asymmetric carbons at the 2- and 3-positions of the phosphorane ring, all of which are included in the compound of the present invention. In any of the reactions, the target compound can be obtained by post-treatment used in a general synthetic chemistry technique. The structure of the compound of the present invention is confirmed by NMR, MASS, IR spectrum and the like.

[0025]

Next, the present invention will be described in more detail with reference to examples.

(Example 1) 1- (m-nitrophenyl)
Of 2-phosphoren-1-oxide

[0027]

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In an ice bath, 0.71 g (0.004 mol) of 1-phenyl-2-phosphoren-1-oxide was dissolved in 2.5 ml of agricultural sulfuric acid, and 0.334 ml of fuming nitric acid was added dropwise with a dropping funnel, and the mixture was left as it was. 3 hours in an ice bath,
The mixture was stirred at room temperature for 22 hours. The reaction solution was added to ice water and extracted three times with 50 ml of chloroform. The solvent was distilled off under reduced pressure,
The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / methanol = 10/1),
0.713 g of (m-nitrophenyl) -2-phosphorene-1-oxide was obtained. 80% yield

Example 2 Synthesis of 3-methyl-1- (m-nitrophenyl) -2-phosphorene-1-oxide

[0030]

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3-Methyl-1-phenyl-2 in an ice bath
-Phosphorene-1-oxide 1.16 g (0.006
(mol) was dissolved in 3.94 ml of agricultural sulfuric acid, 0.52 ml of fuming nitric acid was added dropwise with a dropping funnel, and the mixture was kept in an ice bath for 3 times.
The mixture was stirred for 22 hours at room temperature. The reaction solution was added to ice water and extracted three times with 50 ml of chloroform. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate / methanol = 10/1).
Purified with 3-methyl- (m-nitrophenyl) -2-
1.01 g of phosphorene-1-oxide was obtained. 71% yield

[0032] ^{IR spectra: 1529,1351cm -1 1 H-} NMR (CDCl 3, δppm): 2.10
(S, 3H), 1.80-3.00 (m, 4H), 5.
95 (d, 1H, J = 25.0 Hz), 7.60-8.
60 (m, 4H) ¹³ C-NMR (CDCl ₃ , δppm): 20.30
(D, J = 18.03 Hz), 26.18 (d, J = 7)
0.18 Hz), 33.22 (d, J = 8.69H
z), 118.16 (d, J = 100.9 Hz), 12
4.53 (d, J = 12.03 Hz), 125.42
(D, J = 2.69 Hz), 129.26 (d, J = 1
1.36 Hz), 135.70 (d, J = 10.04H
z), 136.06 (d, J = 94.24 Hz), 14
7.22 (d, J = 14.04 Hz), 166.83
(D, J = 26.75 Hz)

(Example 3) 1- (m-aminophenyl)
Of 2-phosphoren-1-oxide

[0034]

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In an ice bath, 2.34 ml of hydrochloric acid and 1.76 g of tin (II) chloride dihydrate (0.0078 mo)
l) was mixed. When tin (II) chloride dihydrate was dissolved, the solution was taken out of the ice bath and stirred at room temperature for 10 minutes. In this solution, 1- (m-nitrophenyl) -2
-Phosphorene-1-oxide 0.58 g (0.002
6 mol) and 5 ml of chloroform were added, and the mixture was stirred in an ice bath for 4 hours and further for 44 hours. Pour the reaction solution into ice water,
Make basic with sodium hydroxide and then add chloroform 50
Extracted three times with ml. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 10/1) to give 0.40 g of 1
-(M-Aminophenyl) -2-phosphorene-1-oxide was obtained. Yield 80.8%

Example 4 Synthesis of 3-Methyl-1- (m-aminophenyl) -2-phosphorene-1-oxide

[0037]

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In an ice bath, 2.34 ml of hydrochloric acid and 1.86 g of tin (II) chloride dihydrate (0.0082 mo)
l) was mixed. When tin (II) chloride dihydrate was dissolved, the solution was taken out of the ice bath and stirred at room temperature for 10 minutes. In this solution, 3-methyl-1- (m-nitrophenyl) -2-phosphorene-1-oxide 0.64 g
(0.0027 mol) and 5 ml of chloroform were added,
The mixture was stirred in the ice bath for 4 hours and further for 44 hours. The reaction solution was poured into ice water, basified with sodium hydroxide and extracted with 50 ml of chloroform three times. The solvent was distilled off under reduced pressure,
The residue is purified by silica gel column chromatography (developing solvent: chloroform / methanol = 10/1),
0.52 g of 3-methyl-1- (m-aminophenyl)
2-Phosphorene-1-oxide was obtained. Yield 85.
6%

IR spectrum: 3344, 32
^{27,1601cm -1 1 H-NMR (CDCl} 3, δppm): 2.04
(S, 3H), 2.10-2.99 (mH), 3.
63 (brs, 2H), 5.85 (d, 1H, J = 2)
5.0 Hz), 6.68-7.28 (m, 4H) ¹³ C-NMR (CDCl ₃ , δppm): 20.52
(D, J = 17.36 Hz), 26.82 (d, J = 6)
9.51 Hz), 33.62 (d, J = 8.02H
z), 116.08 (d, J = 10.68 Hz), 11
7.61 (d, J = 2.67 Hz), 118.77
(D, J = 10.70 Hz), 124.93 (d, J =
131.67 Hz), 129.02 (d, J = 14.0)
2 Hz), 134.04 (d, J = 97.57 Hz),
146.58 (d, J = 14.02 Hz), 164.3
0 (d, J = 25.40 Hz)

(Example 5) 1- (p-chlorophenyl)
Of 2-phosphoren-1-oxide

[0041]

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20 ml of thionyl chloride was added to 5.00 g (0.038 mol) of 1-methoxy-2-phosphorene-1-oxide, and the mixture was stirred at room temperature for 2 days, and then 1-chloro-2-phosphorene was distilled from the reaction solution under reduced pressure. -1-oxide was obtained. On the other hand, p-bromochlorobenzene 3.
829 g (0.02 mol) and magnesium 0.48
A Grignard reagent was prepared from 6 g (0.02 mol), and 2.00 g (0.015 mol) of 1-chloro-2-phosphorene-1-oxide obtained above was added dropwise thereto with a dropping funnel. The reaction mixture was stirred at room temperature for 2 hours, then the reaction was stopped by adding 3 ice cubes, neutralized with 1N-hydrochloric acid, and then extracted 3 times with 30 ml of chloroform,
The organic layer was washed with 20 ml of a saturated aqueous solution of sodium hydrogen carbonate and then with 20 ml of water, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / methanol = 10/1) to obtain 1.11 g of 1- (p-chlorophenyl) -2-phospholen-1-oxide. Yield 34.7%

Example 6 Synthesis of 3-methyl-1- (p-chlorophenyl) -2-phosphorene-1-oxide

[0044]

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20 ml of thionyl chloride was added to 5.00 g (0.034 mol) of 3-methyl-1-methoxy-2-phospholen-1-oxide, and the mixture was stirred at room temperature for 2 days, and then distilled under reduced pressure from the reaction solution: 3- Methyl-1-chloro-2-phosphorene-1-oxide was obtained. On the other hand, p-
Bromochlorobenzene 1.310 g (0.0068 m
ol) and magnesium 0.165g (0.0068m
Ol)) to prepare the Grignard reagent, and to the 3-methyl-1-chloro-2-phosphorene-
0.75 g (0.0050 mol) of 1-oxide was added dropwise using a dropping funnel. The reaction mixture was stirred at room temperature for 2 hours, 3 ice particles were added to stop the reaction, and the mixture was neutralized with 1N-hydrochloric acid and then extracted 3 times with 30 ml of chloroform. The organic layer was 20 ml of a saturated aqueous sodium hydrogen carbonate solution. Then, after washing with 20 ml of water, the solvent was distilled off under reduced pressure.
The residue is purified by silica gel column chromatography (developing solvent: ethyl acetate / methanol = 10/1) to obtain 0.415 g of 3-methyl-1- (p-chlorophenyl) -2-phosphorene-1-oxide. It was Yield 38.0%

¹ H-NMR (CDCl ₃ , δppm):
2.05 (s, 3H), 1.80-3.00 (m, 4
H), 5.93 (d, 1H, J = 25.0 Hz), 7.
33-7.75 (m, 4H) ¹³ C-NMR (CDCl ₃ , δppm): 20.73
(D, J = 17.38 Hz), 27.13 (d, J = 7)
0.16 Hz), 33.75 (d, J = 8.69H),
119.89 (d, J = 99.57 Hz), 128.5
0 (d, J = 12.03 Hz), 131.64 (d, J
= 11.36 Hz), 132.40 (d, J = 97.5)
5 Hz), 137.73 (d, J = 3.36 Hz), 1
65.07 (d, J = 25.46H)

(Example 7) 2,3-dihydroxy-3-
Synthesis of methyl-1- (m-nitrophenyl) -2-phosphorane-1-oxide

[0048]

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3-methyl-1- (m-nitrophenyl)
2-phosphoren-1-oxide 0.541 g (0.0
(023 mol) was dissolved in a mixed solvent of 5 ml of water and 5 ml of THF, and 0.416 g of sodium chlorate (0.
039 mol) and a catalytic amount of osmium tetroxide were added, and
The mixture was stirred at 0 ° C for 4 days. After completion of the reaction, the solvent was distilled off under reduced pressure, the residue was dissolved in chloroform, dried over anhydrous sodium sulfate, the solvent was distilled off again under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: chloroform / methanol = 10/1), and the target 2,3-dihydroxy-3-methyl-1- (m-nitrophenyl) -2-phospholane-1-oxide 0.17
5 g were obtained. Yield 28.3% ¹ H-NMR (CDCl ₃ , δppm): 1.47
(S, 3H), 1.6-1.7 (m, 4H), 3.84
(D, 1H, J = 2.86 Hz), 5.38 (brs,
2H), 7.4-8.8 (m, 4H)

Example 8 2-Bromo-3-hydroxyl-1- (m-nitrophenyl) -2-phosphorane-1
-Synthesis of oxide

[0051]

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(M-Nitrophenyl) -2-phosphorene-1-oxide 0.742 g (0.0033 mol)
Was dissolved in a mixed solvent of 5 ml of chloroform and 20 ml of water, 2.0 ml of bromine was added thereto, and the mixture was stirred for 3 days, then saturated aqueous sodium sulfite solution was added and stirred for several minutes, and it was confirmed that the color of bromine disappeared. . The reaction solution was extracted three times with 30 ml of chloroform, and the solvent was distilled off under reduced pressure to obtain a crude product. Recrystallization from ethyl acetate gave pure 2-bromo-3-hydroxyl-1- (m-nitrophenyl)-.
0.321 g of 2-phospholane-1-oxide was obtained.
Yield 30.1% ¹ H-NMR (CDCl ₃ , δppm): 2.0-3.
2 (m, 4H), 4.0-4.8 (m, 2H), 7.6
-8.8. (M, 4H) The OH proton signal was unclear.

Example 9 Synthesis of 2-bromo-3-hydroxyl-3-methyl-1- (m-nitrophenyl) -2-phospholane-1-oxide

[0054]

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3-methyl- (m-nitrophenyl) -2
-Phosphorene-1-oxide 1.50 g (0.006
(3 mol) was dissolved in a mixed solvent of 5 ml of chloroform and 20 ml of water, 2.0 ml of bromine was added thereto, and the mixture was stirred for 3 days. Then, saturated aqueous sodium sulfite solution was added and stirred for several minutes to allow the color of bromine to disappear. confirmed. The reaction solution was extracted three times with 30 ml of chloroform, and the solvent was distilled off under reduced pressure to obtain a crude product. Recrystallize with ethyl acetate to give pure 2
-Bromo-3-hydroxyl-3-methyl-1- (m-
Nitrophenyl) -2-phosphorane-1-oxide
0.633 g was obtained. Yield 30.0% ¹ H-NMR (CDCl ₃ , δppm): 1.70
(S, 3H), 1.8-2.7 (m, 4H), 4.24
(D, 1H, J = 4.9 Hz), 6.10 (brs, 1
H), 7.7-8.6 (m, 4H) Examples of the compounds of the present invention produced as described above are summarized in Tables 1 and 2 below.

[0056]

[Table 101]

[0057]

[Table 102]

[0058]

[Table 103]

[0059]

[Table 2]

[0060]

As described above, the present invention is a novel one.
-Substituted phenyl-2-phospholen-1-oxide is provided by an industrially advantageous production method. Further, the compound of the present invention has herbicidal activity and is useful as a herbicide.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukihiro Kato 1-17-40 Nunobashi, Hamamatsu City, Shizuoka Prefecture

Claims (1)

[Claims] 1. The formula [I]: (In the formula, R is a hydrogen atom or a linear or branched C
_1-6 alkyl group, X is a C _1-4 alkyl group, C
_1-4 alkoxy group, amino group, C _1-6 alkylamino group, di C _1-6 alkylamino group, nitro group, acylamino group, C _1-6 haloalkyl group, acyl group, carboxyl group, cyano group, hydroxyl group , An azido group, a mercapto group, a C _1-6 alkylthio group, a sulfonic acid group, a C _1-6 alkoxycarbonyl group, an isocyano group or a halogen atom, R ¹ represents a halogen atom or a hydroxyl group, and R ²
Represents a hydroxyl group, or R ¹ and R ² may be integrated to form a single bond. n represents an integer of 1 to 5. Further, when n is 2 or more, X may be different from each other)