DE2757111A1 - PHTHALAMID AND NICOTINE ACIDS AND THEIR USE IN PLANT GROWTH REGULATORS - Google Patents

Description

DR. BERG DIPL-ING. STAPF DIPL-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS 2/5 / I I

P.O. Box 8602 45, 801) 0 Munich 86

■ 6-

Attorney's File 28 'j' ^ j December 21, 1977

Be / Ro

Γ-Τ. LOlJI Γ, / MI5T0URI / UFA

"Phthalic acid and nicotinic acid !! and their uses in Oflam'.env / uchsregulierenden Ilmittel "

uiese ürinoun .; concerns new phthalanic acids and liikotinsäux-en and their salts. These compounds are used as active ingredients suitable in plant growth regulating preparations. In particular, the invention relates to compounds of the general formula

C - OR (I)

G-IiH-R ² 09-21-1098A

«09827/0805

'(089) 9882 72 Mauerkircherslr 45 8000 Munich 80 banks

9882 ⁷ J Telegrams Bayerische Vereinsbank Munich 45J100

98S274 BERGSTAPFPATtNT Munich Hyno-Bank Munich 3890002624

983310 TELEX 05 24 560 BERG <J Posischeck Munich 653 4 J- 808

.tr.

2757 η ι

v.'orin Ii '.7ass only ο ff or I / icdrigciII-iyl, Ii, carbon or nitrogen, Rp is pyridyl, substituted pyridyl, or "if R is nitrogen, R _{2 can be} substituted phenyl, as they are 3 salts suitable for sun use in agriculture.

The term "substituted pyridyl" as used herein refers to! test the general formulas

X ^

where ^ each of the radicals X and Y, independently of the other, Halogen, GF ,, Il-lower alkyl and li-lower alkoxy, ujt der I have given that in the 4-position v / each X is still Y chlorine may if the nitrogen atom is in the 3-3 position.

The term "substituted phenyl", v / i ο used here denotes residues of the general formula

wherein X and Y have the meaning defined above.

Go as it is used here includes the designation "for; sowing ?, in agriculture suitable oalze" Alkalii.i (it;: ll · » substituted amine ^ v / ie Isopropylaiain- and i'ri-

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Uthylamine and ammonium salts.

The terms "lower alkyl" and "lower alkoxy" include Alkyl and alkoxy radicals with 1 to 4 carbon atoms.

The phthalamic acids can be prepared by adding a stoichiometric equivalent of the appropriate amino pyridins into a slurry containing phthalic anhydride and contains chloroform. After stirring at room temperature, the precipitate can be filtered and air-dried will. The following examples serve to explain the preparation of the phthalamic acids.

example 1

To a slurry containing 0.1 mol of phthalic anhydride and 100 ml of chloroform, 0.1 mol of 3-amino-2-chloropyridine is added in one portion with stirring. The reaction mixture is stirred for 24 hours; is filtered and the precipitate dried in the air and giving N- (2-chloro-3-pyridyl) phthalamic acid having a melting point of 2O3 ° C (yield = 87 ^c Pl

Analysis:

Calculated 12.81 Cl, 10.12 N found 12.94 Cl, 10.37 N

Following the procedure of Example 1, the following compounds can be prepared.

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Example connection analysis

'Calculated Found

2 li- (6-nethoxy-3-pyridyl) phthalamic acid 61.80 C, 4.44 K, 10.30 H 61.94 C, 4.42 II

3 U- (5-bromo-2-pyridyl) phthalamic acid 8.72 H, 24.88 3r 8.69 IT, 24.75 Br

4 N- (4,6-Dimethy1-2-pyridyl) -phthalamide-

Acid 66.65 C, 5.22 H, 10.36 II 66.53 C, 5.28 H

ο 10.35 K

OO N> -J

CD QO O

AO

The sodium salt of the new phthalamic acids can be prepared by stirring a stoichiometrically equivalent amount of 50% aqueous NaOII and 400 ml of water for a 0.1 LIo 1 reaction for one hour, according to this process Make the following connections.

Example connection

5 iiatrium salt of Ii- (5-chloro-2-i> yridyl) phthalamic acid

6 Hatriuni salt of IT- (2-chloro-3-pyridyl) phthalamic acid

The ammonium and substituted amine salts can according to the in the following examples,

Example 7

To a suspension of 0.1 LIoI of iI- (2-chloro-3-pyridyl) phthalamic acid and 500 ml of iithyl ether, 0.11 kol of isopropylamine is added in one portion with stirring to form the isopropylarain salt. Iiach stirring for 24 hours at 25 to 30 ⁰ C is collected by filtration a Peststoff and dried in air. The product obtained} melting point 147-148 ⁰ C in 100; ftiger yield.

Analysis:

Calculated 57.23 C, 5.40 H, 10.56 Cl, 12.61 K found 57.6J C, 5.45 H, 10.71 Cl, 12.59 N

Example 8

The procedure of Example 6 is used to prepare

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ΛΛ

of the propyl salt of lI- (5-3rom-2-pyriuyl) phthalamido acid; Melting point 145 - 146 ° C., in 87% yield.

Analysis:

Calculated 50.54 C, 4.77 Ii ₁ 11.05 K found 50.42 G, 4.73 H, 10.99 H.

The ICotinic acids of the present invention can be prepared by adding 0.1 ml of appropriately substituted aniline or aminochloropyridine to a suspension of 0.1 ml of 2,3-pyridinedicarboxylic anhydride and 100 ml of chloroform. After stirring for 24 hours at -5-3O ⁰ C, the pests are collected by filtration and dried at 25-30 ⁰ O in the air. The compounds of Examples 9-16 are summarized in Table I below and prepares: aan by the preceding procedure.

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2757 Ί1 1

N O

U-! O) -P

N

O ^

^ fH

ΓΜ Φ

· ■ +

CI

OJ

CM
¹ ^ O SH νο '■ 1- VO Φ • S I ^ • V φ IO CTi ro O = O W • ΙίΛ O ^ i ' M (
O I. O O-1 I. J U ϋ O Ο-ι O = O Λ (M Φ Vj " C- J Φ U • ι ΙΓ \ *> -P U C71 (Ό f Φ φ ΙΓΛ 05
^ i O ΙΓ \ Ο> C—

C- CO VO

CPi CT>

Pin code

H Φ U

Ü cn

(M

H I Φ

• Η · Η <ϋ Pi

OJ

CTi

Ι <Λ

OvJ

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Table I (continued)

σ us co

σ cc ο

example

13 H 15 16

CF, N \ Cl

Melting point ⁰ C

Cl 150 -

184 -

163 -

(d)

CP 182 -

C-OH
C-IiIIR,

Il ^c

Yield percent C err. sef

Qo

82

95

Percent H percent IT

insane -ref. err. fief,

51.91 51.47 2.90 3.02 15.13 15.47 48.79 48.68 2.34 2.25 3.13 3.04 54.20 54.08

2.92

, 8i

54.20 54.07 2.92 2, SS

3, is

(a) Recrystallization from methyl alcohol

(b) Recrystallization from heptane / isopropyl alcohol

(c) Recrystallization from ITaOH / HCl

(d) Recrystallization from isopropyl alcohol

27 57 1 II

Dia. ".: at he can '.vie follows produced v / eruen.

Example 17

71 g (0.3 Hol) Jortrifluoridäthernt / Tc ^ H, -) _O 0 «BP., _ J7 at once to o An exothermic reaction causes the temperature to rise from 21 to 33 C, Kaη refluxes the gas for 4 hours while stirring. After cooling to -10 G, 1000 ml of a Ί0 >> - aqueous solution of sodium bicarbonate are slowly added at -10 ° C to 0 ° C. iiach is collected for 30 minutes at 0 to 10 G the solid by filtration, mixed with V / ater to neutrality and dried in air at 25 - 3O ⁰ C. The product of Methylester of N- (2-chloro-3- pyridyl) phthalamic acid, melting point 110-112 ° C., is obtained in 76% yield. After two recrystallizations from heptane / isopropyl alcohol, it has a melting point of 122-124 ° C.

Analysis:

The gross formula G ₁ ^ H ₁₁ ClN ₂ O,

requires, jS: 57.84 G, 3.31 Ii, 12.20 Gl, 9.64 N found, γό: 57.88 G, 3.57 H, 12.45 Gl, 9.41 N

The compounds of general formula I described above are effective for modifying the development of both the male (Flag) as well as the female (cob) reproductive components of the maize plants. The designation iind-

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/ IS

tion of the "development of the reproductive component" of the Laispflanze is to be understood in such a way that the normally proceeding development of the component is modified up to maturity '.virä. Such: Ioäifications are very easy to observe as inhibition of the plume growth, inhibition of the side branches of the pahn, change in the number of pistons, shape, position, Grain count, speed of the larvae moving, etc.

The invention relates to changing the development of the reproductive components of healthy maize plants, including an effective, non-lethal amount of the acids of the general formula I on the shark plant before or during the early stages of development of the corresponding reproductive component, here called reproductive differentiation is referred to, applies. As a result of such an application, the flag greetings may be decreased or the flag will be eliminated, thereby reducing the activity of producers of hybrid seeds, the flags of the maize plants of Hand to remove, diminish, or eliminate. Furthermore, the amount of land per unit area of land can be increased be when you have a v / ineffective!. 'close the active ingredient before or during the early stages of piston development.

The term "active ingredient" is used here for acids of the general formula I.

According to these novel objects of the present invention

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Ah

v / ground compounds 1-1C by the following procedure examined.

ice cream A

May plants of the variety A-619 v / erden pe sows and diluted to a uniform stock. All weak or late emerged plants removed prior to chemical application, the active ingredient i.ian formulated by the addition of 50 or 100 mg of active compound to 7.5 ml acetone and 7.5 ml water. 0.25 ^ Tv / een 20 is added as surfactant. Using a "Devilbiss No. 1 52 ^IJ spray device , the ulais plants are sprayed during the early stages of reproductive differentiation (at a ratio of 10 mg or 20 mg per plant)»

LIaη examines the results by comparing the treated plants with control plants that were not chemically treated. Dry Coat are to be considered with regard to the change of the reproductive development to be effective in Llaispflanzen, v / hen by treating an inhibition of at least 25 ° / ° of Fahnenseitenastbildung compared to the Kontrollpflanzen.besteht.

According to the foregoing procedure, it was found that compounds 1, 2, 5, 6 and 9-11 are effective in inhibiting 50 to 74 / S of pendentives. It was also found that compounds 3, 7, 8 and 12 to 16,;: inhibit 5 to 49 V ° of side plume development.

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Flowering was inhibited, as shown in the table II can be found.

Table II

Link; cm of B lUbe

Control 224

1 67

3 152

4 75

Example B.

In a further experiment, U- (2-chloro-3-pyridyl) phthalamic acid is used in the case of maize plants in the formulation described above. The observed response includes changing the piston height, increasing speed of loophole and partial sterility. The reactions observed are illustrated in Table III.

Table III

Treatment ratio kg / ha ₁₅ (a) Kolßnhöhe 48 ° / o male ^a ) day 12 ^ ^a 'day 0 (cm) 73 sterility Day 9 ^ 0 0 54 O 1.12 1.12 57 0 1.12 0 0 52 80 1.12 0.56 0.56 60 88 1.12 0 0 48 75 1.12 1.12 1.12 55 89 0.56 0 0 48 68 0.56 0.56 0.56 95 0.56 0 74 0.56 88

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Before. Incurrence of the chamois counted.

What is stated above includes the invention; the application of phthulamic acids before or during the early stages of reproductive differentiation. The reproductive differentiation takes place at different times, depending on the variety of the ..Ictis plants as well as the environmental factors. For example, male reproductive differentiation in G-aspe-LIais (G-aspe corn) begins during kernel formation, while reproductive differentiation in Llais A-61Q occurs within the first 8 to 12 days after seedling emergence. It is up to those skilled in the art to determine when reproductive differentiation occurs, for example, for illustrative purposes only, uses for most of the varieties used in the American Midwest are in the range of 5 to 25 days after emergence the seedlings. The varieties used in other countries may require applications ranging from 1 to 40 post emergence. The following example explains that for maize of variety A-619, applications between 7 to 12 days after emergence of the seeds are preferred _β

Example C

Corn variety A-619 is cultivated in cultivation containers at a ratio of 64,000 plants per hectare. Treat these plants one with 0.56 to 1.68 kg / ha with one formulation

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the compound 6, 30 ', Ό acetone, 0.25 ' / '» Twee η 20 and a sufficient length of V / asaer, the formulation; is used in a ratio of 320 l / ha. Some applications are earlier, on or before the 12th day after the oaat emerges. Other applications take place later after 12 days after the seeds emerge; after the harvest, the yield of the treated plants is compared with that of the untreated control plants. Table IV explains the results of this experiment.

Table IV

Late application

g / bowl Control yield Early application 1300 2060 1940 2940 1650 1540 1740 1680 1700 1740 1910 2170 1810 2430 1850 2230 1770 1730

1720 1660 1390 1480 1130

By -1773 2057 1476

cut

In the practice of the invention, the active ingredient can alone or used in conjunction with a material referred to in the art as an adjuvant and either described in liquid or solid. The production of plant growth-regulating preparations is mixed the active ingredient with an adjuvant including diluents, stretching agents, carriers and conditioning agents

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teln with the formation of preparations in the form of finely divided particulate solids, granules, pellets, wettable powders, dusts, solutions and aqueous dispersions or emulsions. It can therefore use the active ingredient an adjuvant, v / ie a finely divided particulate gen solid, a liquid vegetable solvent Origin, water, a wetting agent, dispersant or Emulsifying agents or any combination of these agents be used"

To typical finely divided solid carriers and extenders, those in the plant growth regulating preparations Suitable for this invention include talc, clays, pumice stone, silicon dioxide, diatomaceous earth, quartz, Fuller's earth, Sulfur, powdered cork, powdered wood, walnut shell flour, chalk, ta.bak dust, charcoal and the like. Typical liquid diluents include Stoddard solvents, Acetone, alcohols, glycols, ethyl acetate, benzene and the like. The preparations regulating the growth of plants of this invention, particularly in the form of liquids and wettable powders, usually contain sufficient amounts of one or more surface-active agents to dissolve a given preparation in water or in oil easier to make dispersible. The term "surface-active! .Litt el" includes wetting agents, dispersants, Suspending agents and emulsifying agents. Such surfactants are well known and will be

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for detailed examples to the U3 patent writ 2,547,724, columns 5 and 4 are referred to.

In general, the V / l in irkstoffe ^J Orué a preparation applied which contains one or more adjuvants which support the use of the active substance by a uniform distribution. The application of liquid and particulate, solid preparations of the "active ingredient" can be carried out by means of conventional methods, for example using 3prUngeraten, Stüub _c ; erät, i3aun- and hand sprayers and spray atomizers. The preparation can also be used from plug generators as dust or as a spray v / earth.

The formulations of this invention generally contain about 1 to 99 parts of active ingredient, about 1 to 50 parts surface-active agent and etv / a 4 to 94 solvents, all parts being parts by weight based on total weight the preparation.

When selecting a suitable application ratio of the active ingredient, it must be pointed out that the exact application ratios are also dependent on the type of application, the plant variety, the soil conditions and various other factors known to those skilled in the art. Although a ratio of about 0.056 to 5.6 kg / ha is preferred higher ratios of up to 56 kg / ha,

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used depending on the factors given above.

However, the invention does not include the use phytotoxic conditions that have a herbicidal effect exercise. It should also be noted that one or more applications can be used to control the acclaimed success; to achieve.

Although this invention ix ,: with regard to specific modifications it is not restricted by this, since the Faciunann has different equivalents, Changes and codifications can be made, without deviating from uei.i inventions

Patent claims :

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Claims (1)

Claims ι CWTI P - JMH. - Ag, wherein R is hydrogen or lower alkyl, R _{1 is} carbon or nitrogen, R _{2 is} pyridyl, substituted pyridyl, or when R _{1 is} nitrogen, R _{2 can be} substituted phenyl and their salts suitable for use in agriculture. 2. Compound according to claim 1 of the general formula 0 η C-OH C-NH-R ₉ , 0
wherein R _{2 is} pyridyl or substituted pyridyl, 3. Compound according to claim 2, wherein R _{2 is} substituted pyridyl. 4. A compound according to claim 2, that it is N- (2-chloro-3-pyridyl) phthalamic acid is. 5. A compound according to claim 2 that it is the sodium salt 809827/0805 a, of N- (2-chloro-3-pyridyl) -phthalamid8 acid. 6. A compound according to claim 1 of the general formula wherein R _{2 is} pyridyl, substituted pyridyl, or substituted phenyl. 7. Plant growth regulating preparation, thereby characterized in that it contains from 1 to 99 parts by weight of a compound of the general formula Il C-OH C-NH-R ₉ , Il ^ wherein R is hydrogen or lower alkyl, R _{1 is} carbon or nitrogen, R _{2 is} pyridyl, substituted pyridyl, or when R _{1 is} nitrogen, R _{2 can be} pyridyl, substituted pyridyl or substituted phenyl, and their salts suitable for use in agriculture, wherein the remaining parts contain one or more suitable carriers, dispersants or diluents and / or adjuvants. Θ. Preparation according to claim 7 »characterized in that g · - 809827 / 080S indicates that the active ingredient compound has the general formula wherein R _{2 is} pyridyl or substituted pyridyl. 9. Preparation according to claim 8, characterized in that R _{2 is} substituted pyridyl. 10. Preparation according to claim 8, characterized in that the compound H- (2-chloro-3-pyridyl) phthalamic acid is· 11. Preparation according to claim 8, characterized in that the compound is the sodium salt of N- (2-chloro-3-pyridyl) phthalamic acid. 12. Preparation according to claim 7 »characterized in that the compound is the general Formula has It C-OH C - NHR ₀ , it £ wherein R _{2 is} pyridyl, substituted pyridyl, or substituted phenyl. 809827/0805 2757 I Il λ '). Process for changing the development of the reproductive components of a Llais plant, thereby
~ ei: e η η ζ verifies that an effective, non-lethal amount of a connection can be found on the Lais plant
the all, one formula v / orin R .Vasserütoff or i.'iedrigalkyl, R.carbon
or nitrogen, R _{0 is} pyridyl, substituted pyridyl, or when R, is nitrogen, R 1 is pyridyl, substituted
May be pyridyl or substituted phenyl, and their
suitable salts for use in the farmer reeds. 14 ο method according to claim 13, characterized in that a connection of the
general formula is used wherein R _{0 is} pyridyl or substituted pyridyl. ' I ¹ J, method of claim 14, characterized GEK e η η ζ η et verifiable, that is in the compound used R 2 is substituted pyridyl. B09827 / 080S _ 27 57 1 16. The method genai3 claim 14, dadurc h r-, e 1: e ii η ζ eic L a et that one uses IT— (2- chloro-3-pyridyl) -phtiialaiuidsäure as compound. 17. The method according to claim 14, characterized in that C e 1: e η η ζ e i c h η e t that the sodium salt is used as a compound of iT- (2-chloro-5-pyridyl) phthalamic acid used. 15. The method according to claim Yj, characterized in j; e indicates that a compound of the general formula is used CX Il C-OH C - KHR, wherein Rp is pyridyl, substituted pyridyl or substituted Is phenyl. 609827 / 080S