JPH049360A - 5-aminolevulinic acid alkyl ester or its salt, production thereof and herbicide compound using the ester as active component - Google Patents

Abstract

NEW MATERIAL:The 5-aminolevulinic acid alkyl ester of formula 1 (R<1> is >=2C alkyl) or its salt. EXAMPLE:Octyl 5-aminolevulinate hydrochloride. USE:An active component for herbicide. If has excellent spreadability to a plant and ifs herbicidal activity is not restricted to the circumference of the attached part but extended to the part other than the attached part to cause the withering of the bud, etc. It has extremely high herbicidal activity in addition to biodegradability, selectivity and safety. PREPARATION:The objective compound of formula I or its salt can be produced with a simple procedure on an industrial scale at a low cost by reacting a 5-aminolevulinic acid compound of formula II (R<2> is H or amino-protecting group) or ifs reactive derivative with an alcohol of formula III and, if amino- protecting group is present, eliminating the protecting group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a 5-amylpurinate alkyl ester or a salt thereof, a method for producing the same, and a herbicide containing these as active ingredients.

[Prior art and problems to be solved by the invention] It has been disclosed that 5-amylpuric acid, a natural amino acid, has low toxicity and acts as a biodegradable light-requiring herbicide (Specially Notified). No. 1983-502814). In other words, 5-amylpuronic acid is the pro-W form of tetrapyrrole, and when 5-amylpuronic acid is sprayed on plants, the production of tetravirol is promoted, so in the presence of light, active oxygen is generated by the catalytic action of tetravirol. This occurs and causes the leaves of the plant to wither and die.

Furthermore, in general, it is necessary for a herbicide to be put into practical use to adhere to a plant by spraying and to kill the plant itself. However, highly hydrophilic compounds such as 5-amylpuronic acid have poor adhesion to plants and do not contribute much to the production of t1 tetrapyrrole, most of which falls into the soil during spraying. As a result, the herbicidal activity is low, such as the re-occurrence of leaf rot even after the leaves of the plants turn white and wither, resulting in problems that are unsatisfactory in practical terms. Also,
Since herbicidal activity is limited only to the area around the attachment point, uneven spraying can cause immediate regrowth.

Therefore, an object of the present invention is to provide a novel compound that is safe, biodegradable, selective, and has practical herbicidal activity, a method for producing the same, and a herbicide using the same.

[Means to solve the problem]

Under these circumstances, the present inventor has conducted intensive research and has found that 5-amylpurinic acid alkyl ester or its salt has new herbicidal activity and benefits for plants that are not found in 5-amylpurinic acid. It was discovered that it has a good spreadability.
The present invention has now been completed.

That is, the present invention provides a 5-amyl-purinate alkyl ester or a salt thereof represented by the general formula (1) (wherein R' represents an alkyl group having 2 or more carbon atoms), and a method for producing the same. The present invention provides a herbicide as an ingredient.

In the 5-amyl-purinate alkyl ester of the present invention, R1 is an alkyl group having 2 or more carbon atoms, but when used as a herbicide, from the viewpoint of herbicidal activity, R1 is an alkyl group having 4 to 2 carbon atoms.
4 alkyl groups, particularly 4 to 16 alkyl groups, are preferred. Specific examples include ethyl group, propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, lauryl group, valmityl group, stearyl group, etc. Straight chain alkyl group; branched alkyl groups such as isopropyl group, isobutyl group, 5ec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, 2-octyldecyl group and the like.

Examples of the salt include inorganic salts such as hydrochloric acid, sulfuric acid, nitric acid, and nitrous acid; and salts of organic acids such as acetic acid, lactic acid, citric acid, and butyric acid.

The 5-amyl-purinate alkyl ester or salt thereof of the present invention can be obtained by a general method for synthesizing amino acid esters, and can be produced, for example, according to the following reaction formula.

(In the formula, R' has the same meaning as above, and R2 represents a hydrogen atom or a protecting group for an amino group).

That is, alcohol (
5-amyl-purinate alkyl ester or its salt (I) is produced by reacting III) and removing the protecting group for the amino group, if present.

Examples of reactive derivatives of 5-amylpurinic acid whose amino groups may be protected include acid halides, mixed acid anhydrides, and the like. Such a reactive derivative may be used as an isolated raw material, but it can also be used as a reaction mixture without being isolated.

In the reaction when unbonded m5-amylpuronic acid is used as a raw material, first, a condensing agent such as thionyl chloride is added dropwise to alcohol (III) at about 0 to 20°C under normal pressure, and then 5-
Add milpuric acid.

Here, thionyl chloride is used to convert 5-milpuric acid into acid chloride, and for this purpose, phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, oxalyl chloride, etc. can also be used in place of thionyl chloride. However, since these easily react with alcohol (III) and the amino group of 5-amylpuronic acid and are deactivated, alcohol It is preferable to react with (■).

Although it is possible to use 5-amylpuronic acid itself as a raw material, there is a possibility that the polycondensation reaction between the raw materials takes priority over esterification, and to prevent this, it is necessary to keep the raw material concentration at a low concentration. Therefore, it is more effective to use a salt such as 5-7 milpurate hydrochloride. In addition, if the reaction temperature is below about 0°C, the raw material alcohol (I[I) may solidify, and if it is above about 20°C, thionyl chloride, etc. may decompose and evaporate at this point, so the above-mentioned It is preferable to maintain a temperature range of . Further, specific examples of the alcohol (In[) that can be used include 1-butanol, 1-pentanol, ■-hexanol, l-heptatool, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, Linear alkyl alcohols such as 1-dodecanol, tridecanol, tetradecanol, pentadecanol, and hexadecanol, as well as their isomers such as 2-butanol, 2-methyl-1-propanol, and 2-methyl-2 Branched alkyl alcohols such as -propanol and 2,2-dimethyl-1-propanol can also be used.

Next, in order to prevent both the reaction system and the raw materials from containing moisture, a means such as a nitrogen seal is applied, and the temperature is gradually raised to about 60 to 90 °C, preferably about 70 to 80 °C. The reaction is completed by maintaining the temperature within the range for about 1 to 3 hours. If the reaction temperature is below about 60°C, it will take time to complete the reaction, and if it is above about 90°C, the reaction system may become colored, so it is preferable to maintain the temperature within the upper 8°C range.

After the reaction, under reduced pressure of about 10 to 30 mmHg,
Reaction byproducts such as sulfur dioxide, hydrogen chloride, and unreacted thionyl chloride are distilled off. Next, the salt of the 5-amylpurinate alkyl ester of the present invention can be obtained by adding a solvent having lower polarity than the alcohol, such as ether, hexane, or chloroform, to crystallize it, and separating it by filtration. .

Furthermore, by performing ion exchange or the like using an anion exchange resin, the 5-amylpurinate alkyl ester or other salt of the present invention can be obtained.

The above method is a good method in that it requires few reaction steps, but
When introducing an alkyl group having about 10 or more carbon atoms or a tertiary alkyl group such as a tert-butyl group as an ester, the reaction activity of the alcohol is low and the reaction may not proceed smoothly. It is preferable to protect the amino group of 5-amylpurinic acid or a salt thereof using an appropriate protecting group, then perform esterification, and then remove the protecting group, as the yield is higher.

The protecting group (R2) for the amino group in this method is:
Protecting groups for amino groups used in ordinary peptide synthesis are used, such as acetyl, benzoyl, tert-
Carbonyl compounds such as butoxycarbonyl and benzyloxycarbonyl can be used, with benzyloxycarbonyl group being particularly preferred in terms of ease of elimination.

To synthesize 5-amylpurinic acid with a protected amino group as a raw material, for example, 5-amylpurinic acid or its salt is made into an aqueous solution with a weak base such as IJium or potassium hydrogencarbonate, and stirred at room temperature. Below, it is preferred to add and react an ethereal solution of an active carbonyl compound such as benzyloxycarbonyl chloride.

Here, the solvent may be any solvent as long as it is insoluble in water and does not react with carbonyl compounds such as benzyloxycarbonyl chloride, and in addition to ether, hexane, benzene, etc. can also be used.

After the reaction is completed, the ether layer is removed, the aqueous layer is washed with ether, etc., the pH is acidified to about 1 to 3 using about 1 to 6N hydrochloric acid, and the product is washed with ethyl acetate, chloroform, dichloromethane, etc. Extract. The extracted organic layer is
After drying with anhydrous sodium sulfate, anhydrous magnesium sulfate, etc., the solvent is evaporated to dryness under reduced pressure to obtain 5T milpuric acid with a protected amino group, such as 5- Benzyloxycarboxamide levulinic acid is obtained.

The obtained amino group-protected 5-amylpurinic acid, such as 5-benzyloxycarboxamide levulinic acid,
The ester raw material alcohol (III
) and a non-volatile acid catalyst such as phosphoric acid or sulfuric acid, followed by heating and refluxing and separating the produced water using a DeanStark apparatus or molecular sieve, it can be easily led to an ester.

A trace amount of the acid catalyst used in the reaction was removed by washing the reaction solution with water, and after drying in the same manner as described above, evaporation to dryness under reduced pressure produced an ester of 5-amylpurinate with a protected amino group, e.g. -benzyloxycarboxamide revulinic acid alkyl ester is obtained. The product can also be purified by recrystallization using n-hexane, isooctane, or the like.

The protective group of the 5-benzyloxycarboxamide revulinic acid alkyl ester can be removed by a conventional hydrogenolysis reaction, for example, in the presence of a small amount of a catalyst in which palladium is supported on carbon.
This can be achieved by reacting in a solvent such as methanol, ethanol, propatool, or ethyl acetate under a hydrogen atmosphere of 1 atm or in a hydrogen stream at room temperature.

The reaction product is filtered to remove the catalyst, and then evaporated to dryness under reduced pressure to obtain the desired 5-amylpurinate alkyl ester. Alternatively, if the reaction is carried out in the presence of an acid such as hydrogen chloride or by adding a reactive double acid and evaporating to dryness, the product can be obtained as a salt such as 5-amylpurinate alkyl ester hydrochloride.

The 5-amyl-purinate alkyl ester and its salt of the present invention have excellent spreading properties when made into an aqueous solution, so that when sprayed on the surface of a plant, it spreads thinly and uniformly over the surface. There is. This is because the 5-amyl-purinate alkyl ester and its salt of the present invention have an amino group, which is a hydrophilic part, and an alkyl group, which is a hydrophobic part, at both ends of the molecule, and therefore exhibit a surface-active effect. It is estimated that this is due to

Conventionally, when using compounds with high water solubility and poor adhesion to plants, such as amino acids such as 5-amylpuronic acid, as herbicides, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, and Add a spreading agent such as oxyethylene alkyl phenyl ether, etc.
Next, the 5-amylpurinate alkyl ester and its salt of the present invention have the property of directly adhering to the plant surface, so a spreading agent is not particularly necessary, and it is more Efficient.

Furthermore, the 5-amylpurinic acid alkyl ester and its salt of the present invention are significantly superior to 5-amylpurinic acid in terms of herbicidal activity. That is, the herbicidal effect of 5-amylpurinic acid causes the death of plants secondary to the whitening and withering limited to the sprayed surface, but the 5-amylpurinic acid alkyl ester of the present invention and its Since salt kills not only the sprayed area but also the areas that have not been sprayed, it actually has the effect of preventing recurrence even if the spraying is uneven. It is speculated that this is because 5-amylpurinate alkyl ester and its salt efficiently adhere to the surface of the sprayed part, are absorbed at the adhered part, and move within the plant body.

When the 5-amyl-purinate alkyl ester and its salt of the present invention are used as a herbicide, it is preferably used as a spray solution in the form of a solution, suspension or emulsion. Examples of solvents used in this case include water, methanol,
Impropatol, lower alcohols such as isobutanol, ethylene or propylene glycol, acetone,
Examples include xylene, kerosene, benzene, methylnaphthalene, and cyclohexanone. The content of 5-amylpurinate alkyl ester and its salt in the spray liquid is approximately 5 to 30 mmol/1, particularly 15 to 25 mmol/1.
Setting it to 1 gives preferable results.

Furthermore, the herbicide of the present invention is prepared in the form of a wettable powder by adsorbing 5-amylpurinate alkyl ester or its salt on bulking agents such as talc, diatomaceous earth, silica, and calcium nitrate of various particle sizes; When used, it can also be suspended in water and sprayed.

The amount of spraying of the herbicide of the present invention is approximately 30 to 30 per square meter.
It is preferable to set it to about 50 m1.

The herbicide of the present invention may contain, to the extent that the effects of the present invention are not impaired.
Other herbicides, surfactants, and spreading agents can also be used in combination.

〔Effect of the invention〕

The novel 5-amylpurinate alkyl ester and its salt of the present invention have good spreadability to plants, and at the same time,
The herbicidal activity is not limited only to the area around the adhesion layer, but also causes death in areas other than the sprayed area, so the herbicidal activity is extremely high.

In addition, the biodegradability of conventional 5-amylpuronic acid,
It also has selectivity, and the secondary products produced by hydrolysis of the ester bond of the compound of the present invention are only 5-amylpuronic acid and alcohols, so it is not inferior to 5-amylpuronic acid in terms of safety. . Furthermore, the compound of the present invention can be produced by simple means, and even an alkyl group having about 10 or more carbon atoms can be efficiently introduced as an ester, so it can be produced industrially advantageously. can.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these Examples.

Example 1 0.5 ml of thionyl chloride was added dropwise to 3 ml of 1-octanol under water cooling, and then 50 ml of 5-amylpurine hydrochloride was added dropwise to 3 ml of 1-octanol.
Added 0 ■. While stirring, the reaction temperature was raised from room temperature to 80°C and maintained for about 2 hours. After confirming the completion of the reaction, the mixture was allowed to cool to room temperature, and then volatile components were distilled off under reduced pressure of 10 mm) Ig. Thereafter, hexane was added to crystallize and precipitate the product, which was then filtered, washed, and dried to obtain 826 mg of 5-amylpurinate octyl ester hydrochloride, with a yield of 99%.

The obtained product was confirmed to have the following structural formula from the results of 'H-NMR and infrared absorption spectrum (Nujol method). The measured values and structural formula are shown below.

'H-NMR (90MHz, CDCj23) δ
(ppm): 0.87 (t, 3H, CH3) 1.00-1.75 (b, 12H, 1 mouth H2 1)
4.05 (t, 2H, Co Roro H2) 2, 45-3.
05 (m, 4)1. COCH2CH2C0)4,
30 (b, 211. COCl12N)8, 28
(b, 3H, NH3C1) Infrared absorption spectrum (Nujol method, Cm-') 1730 (':;C=0
) 2860 (-CH,-) 2950 (-CH2-) 3250 (Nl13) Structural formula % Formula % (1) Same as Example 1 except that 1-hexanol was used instead of 1-octatool as the raw material. As a result of implementation, 5
-Amylpurinate hexyl ester hydrochloride 662 mg
was obtained, with a yield of 88%.

The obtained product was confirmed to have the following structural formula from the results of 'H-NMR and infrared absorption spectrum (Nujol method).

'H-NMR (90MHz, mouth DC1,)
δ (ppm): 0, 90 (t, 3H, Ct
13) 1, 10-1.80 (b, 41(,beCLh)2
．． 45-3.12 (m, 4H, mouth 0CH2CH2CO
) 4.05 (t, 2H, [: [1 Roro H2) 4, 30
(b, 2H, C0CH2N)8, 25 (b, 3
H, NH, Cl) Infrared absorption spectrum (Nujol method, cm-') 1730 C=0 > 2850 (-CH,-) 2920 (-CH2-) 3250 (NH3) Structural formula % Formula % (2) Next By ion-exchanging the 5-amylpurinate alkyl ester hydrochloride obtained in (1), 5-
Amyl puric acid T alkyl ester was obtained.

That is, an anion exchange resin was packed in a glass column with an inner diameter of 10 mm to a height of about 20 cm, and about 100 ml of IN sodium hydroxide aqueous solution was poured into the column to completely form the DH type, and then the sodium hydroxide was completely removed with ion-exchanged water. Thereafter, 400 µm of 5-amylpurinate hexyl ester hydrochloride dissolved in about 10-mer ion-exchanged water was added to the top of the column, and the column was allowed to pass through the column for about 10 minutes while adding ion-exchanged water. 5-Amylpurinate hexyl ester hydrochloride is ion-exchanged while passing through the column to obtain an aqueous solution of 5-amylpurinate hexyl ester, which is then concentrated to dryness under reduced pressure to obtain 339μ of 5-amylpurinate hexyl ester. I got it.

Example 3 The same procedure as in Example 1 was carried out except that 1-octanol was used as the raw material and l-heptatool was used. As a result, 665 μm of 5-amylpuronic acid hebutyl ester hydrochloride was obtained.
The yield was 83%.

The obtained product was confirmed to have the following structural formula from the results of 'H-NMR and infrared absorption spectrum (Nujol method).

'H-NMR (90MHz, COCl a) δ
(ppm): 0.88 (t, 3H, CH,) 1, 10-2.85 (b, IOH, lid CH2 edition) 2
, 43-3.15 (b, 4)1. COCH2Cl
1. CD) 4, 05 (t, 3H, CD0CH2) 4
,07-4.70 (b, 2H,C0CH2N)7,
70-8.90 (h, 3H, NH3Cl) Infrared absorption spectrum (Nujol method, cm"") 1730
(N C=0) 2850 (-CH,-) 2920 (-CH,-) 3250 (-NH,) Structural formula % Formula % Example except that 1-nonanol was used instead of 1-octanol as the raw material As a result of carrying out the same procedure as in 1, 647 ml of 5-amylpurinate nonyl ester hydrochloride was obtained, with a yield of 74%.

The obtained product was confirmed to have the following structural formula from the results of -NMR and infrared absorption spectrum (Nujol method).

'H-NMR (90MHz, CDCI!I)
δ (ppm): 0, 89 (t, 38. CL) 1, 05-1.80 (h, 14H, -eCH, ga)
2, 45-3.10 (b, 4H, [:[l['H2
CH2[:D)4,05 (t, 2H,C00CR2
) 4.05-4.60 (b, 2H, C mouth CHIN) 7
, 90-8.75 (b, 2H, NH, CJ) Infrared absorption spectrum (Nujol method, am-') 173
c=o to 0 > 2850 (-CH,-) 2930 (-C)1. -) 3250 (N)! ,) Structural formula As a result of carrying out the same procedure as in Example 1 except that 1-octatool was used as the raw material and 1-decanol was used, 5-amyl-
642 ml of puric acid decyl ester hydrochloride was obtained, with a yield of 70%.

The obtained product was confirmed to have the following structural formula from the results of 'H-NMR and infrared absorption spectrum (Nujol method).

'H-NMR (90MHz, CDCj2-) δ
(ppm): 0, 90 (t, 3H, CH3) 1, 00-1.95 (b, 16H, fcH2+i) 2
, 35-3.10 (b, 4H, ['DC)1. ['
H,cO)4,05 (t, 2H,C00CH2)4
, 05-4.59 (b, 2H, C0CH, N) 7,
99-8.85 (b, 2H, NH, CI) Infrared absorption spectrum (Nujol method, cm-') 1730
c=o > 2850 (-CH,-) 2930 (-C)12-) 3250 (NH,) Structural formula (1) 500 mg of 5-amylpurinate hydrochloride and hydrogen carbonate) 650 mg of IJium was added to 5 ml of water. 5d of ether and 0.0% of benzyloxycarbonyl chloride were dissolved and stirred at room temperature. Added W. After stirring for about 2 hours and the generation of carbon dioxide gas stopped, 0.3 ml of benzyloxycarbonyl chloride and 325 ml of sodium carbonate were added. (The reason for conducting the reaction in two parts is to allow the reaction to proceed gradually.) After stirring for about 2 hours and confirming the generation of carbon dioxide gas and the completion of the reaction, the aqueous layer was diluted with ether. Wash twice and pH 1.5 using 6N hydrochloric acid.
After that, acidic organic matter was extracted with ethyl acetate.

For the extracted layer, anhydrous sodium sulfate was added to adsorb water, and then this was removed by filtration, the solvent was dried under reduced pressure, and the obtained solid was recrystallized with a mixed solvent of ethyl acetate and hexane to give pale yellow crystals 630. .3 mg was obtained.

Take 300 mg of the obtained crystals and add 30 m of benzene.
Dean-3 tar with 0.088 d of 1-dodecanol and 5 ml of p-toluenesulfonic acid hydrate.
The mixture was heated to reflux using a k apparatus, and completion of the reaction was confirmed by thin layer chromatography (TLC) after about 3 hours.

The reaction solution was washed with a saturated aqueous sodium bicarbonate solution, then with water, the organic layer was dried over anhydrous sodium carbonate, the sodium carbonate was removed by filtration, and the mixture was evaporated to dryness under reduced pressure to obtain white crystals. It was done. The crystals were recrystallized from hexane to obtain 370.3 mg of 5-benzyloxycarboxamide dodecyl ester, with a yield of 71% compared to 5-amylpuronic acid.

The obtained product was confirmed to have the following structure from the results of 'H-NMR and infrared absorption spectrum (Nujol method).

') I-NMR (90MHz, CDCji! 3)
δ (ppm): 0, 87 (t, 3H
, CH3) 1, 27 (s, 18) 1. -(CH2) 9)1.
45-1.80 (b, 2nd, -mouth H2-) 2.67
(s, 4H, -CO-H, -CH2-C0-)3.9
0 4.25 (m, 4H, N-C) lz', C Rororo H2-) 5, 15 (s, 2H, Ph-CL-)
5, 25-5.60 (b, LH, Ni1) 7, 36
(s, 5H, Ph) Infrared absorption spectrum (Nujol IL cm-') 3
310 (NH) c=o at 1725 > c=o at 1690 > Structural formula (2) 300 mg of the obtained 5-benzyloxycarboxamide revulinic acid dodecyl ester was dissolved in 10-methanol, and IN salt Wl1me, 5 % palladium-supported carbon catalyst was added and stirred at room temperature under a hydrogen atmosphere.

After confirming the completion of the reaction, the catalyst was removed by filtration and evaporated to dryness under reduced pressure. The obtained crystals were recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 260.1 mg of 5-amylpurinate dodecyl ester hydrochloride, with a yield of 94%.

The obtained crystal was confirmed to have the following structure by 1-NMR and infrared absorption spectrum (Nujol method).

')l-NMR(90M)lz, CDCR3)
δ (ppm): 0, 87 (t, 3H, C)l,
) 1, 27(s, 18H, -(CH=) 9-) 1.4
4-1.75 (b, 211.-mouth H2-) 2, 46-
3.10 (b, 4H, -CD-CH, -CH2-C
0-)4.03 (t,2H,-COD-CH2-)4
, 15-4.46 (b, LH, -N)l-CD-)
7, 95-8.45 (b, 3H, -NH,CJ)
Infrared absorption spectrum (Nujol method, Cm-') 3
250 (-NH, CA) 1750 C=O) 1730 (N C=0) Example 7 The same operation as in Example 6 was performed except that 1-hexadecanol was used instead of 1-dodecanol, and 5 -Benzyloxycarboxamide revulinic acid hexadecyl ester 4
81.7■, then 400mg of this was used to prepare 5-amylpurinate hexadecyl ester hydrochloride 297.1■
were obtained, with yields of 87% and 92%, respectively.

It was confirmed that each product had the following structure from the results of 'H-NMR and infrared absorption spectrum (Nujol method).

5-benzyloxycarboxamide revulinic acid hexadecyl ester'H-NMR (90 MHz, CDCl δ (p
pm): 0, 87 (t, 3H, C)1. ) 1.27(s, 28tl, -(CL) 14-)2, 6
9 (s, 4H, -CD-CH, -CH, -'CD-
)3゜90-4.22 (rn, 4H, -N CH-
, C0D-CL-)5,12 (s, 2H, Ph C
H2) 5, 25-5.65 (b, LH, NH) 7,
36 (s, 3H, Ph) Infrared absorption spectrum (Nujol method, am-') 3
310 (NH) 1725 (C=0) 1685 (C=(+) Structural formula 5-amylpurinate hexadecyl ester hydrochloride')l
-NMR (90MHz, CDCj! a/DMSO-
d) δ (ppm): 0.88 (b, 3)1.
-C1 (3) 1, 29 (S, 28) 1. -(CH2
) l, -) 2,50-2.90 (m, 4H, -
CD-CH, -CH2-CD) 3.80-4.15 (m
, 4H, -CD-0-CH, -, N-CH, -CD-)
8, 30-8.70 (b, 3H, NH3C1) infrared absorption spectrum (Nujol method, cm-') 325
0 (-N)1. cjri 1750 (C=0) 1730 (C=0) Structural formula 5-amylpurinate octyl ester hydrochloride obtained in Example 1 was dissolved in distilled water to make 30 mmol/1,
This was sprayed on various plants at a rate of 50 mj'/m', and the effects were evaluated 4 days later. The results are shown in Table-1.

As shown in Table 1, the herbicidal activity of 5-amylpurinate octyl ester hydrochloride is highly selective to dicotyledons.

Furthermore, 5-amyl-purinate alkyl ester hydrochloride obtained in Examples 2 to 5 and 5-amyl-purinate hexyl ester obtained in Example 2 also showed similar herbicidal activity.

Test Example 2 A 30 mmol/l aqueous solution of 5-amyl lipric acid nonyl ester hydrochloride obtained in Example 4, a 30 mmol/l aqueous solution of commercially available 5-amylpurinate hydrochloride, and 30 +++ mol of commercially available 5-amylpurinate hydrochloride. /
A mixture of 1% commercially available spreading agent in an aqueous solution was sprayed once on each cucumber wheel using a brush on the upper surface of the leaves, and the results were evaluated for discoloration of the leaf surface one day later. -2.

As can be seen from Table 2, 5-amyl lipric acid nonyl ester hydrochloride has superior herbicidal activity compared to conventional herbicides containing spreading agents.

Table Test Example 3 Example 1~? A 30 mmol/Il aqueous solution of 5-amylpurinate alkyl ester hydrochloride obtained in step 1, and a 30 mmol/β aqueous solution of commercially available 5-amylpurinate hydrochloride mixed with 1% of a commercially available spreading agent, Each half of the leaves of a cucumber wheel was coated with a brush, and the subsequent progress and regeneration state after 30 days were evaluated. The results are shown in Table 3.

From the results shown in Table 3, the 5-amylpurinate alkyl ester hydrochloride of the present invention has an effect on plant growth, although it is slightly more motile than 5-amylpurinate hydrochloride. , it can be seen that it also has the effect of suppressing recurrence.

As shown in the Examples and Test Examples above, the 5-amylpurinate alkyl ester and its salt of the present invention are extremely useful as herbicide ingredients.

It can also be used as a surfactant.

that's all Applicant: Cosmo Research Institute Co., Ltd.

Claims (1)

[Claims] 1. 5-aminolevulin represented by the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (wherein R^1 represents an alkyl group having 2 or more carbon atoms) Acid alkyl ester or its salt. 2. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, R^2 represents a hydrogen atom or a protecting group for an amino group) 5-Aminolevulinic acids or their reactivity Derivatives include formula (III) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^1 represents an alkyl group having 2 or more carbon atoms) is reacted with an alcohol to protect the amino group. 2. The method for producing a 5-aminolevulinic acid alkyl ester or a salt thereof according to claim 1, which comprises removing the group if it exists. 3. A herbicide comprising the 5-aminolevulinic acid alkyl ester or its salt according to claim 1 as an active ingredient.