CA1082941A

CA1082941A - Increasing chloroethylphosphonic acid-induced ethylene response in plants

Info

Publication number: CA1082941A
Application number: CA257,999A
Authority: CA
Inventors: Han S. Ku; Robert E. Holm
Original assignee: Diamond Shamrock Corp
Current assignee: Diamond Shamrock Corp
Priority date: 1975-09-08
Filing date: 1976-07-28
Publication date: 1980-08-05
Also published as: FR2322544A1; BR7605869A; MY8300011A; DE2640223A1; GB1554928A; CH615567A5; JPS5234929A; IT1069979B; AU505138B2; IL50424A; IL50424A0; PH13212A; AU1747876A

Abstract

ABSTRACT OF THE DISCLOSURE

A composition consisting essentially of 2-chloro-ethylphosphonic acid and certain imides, carbamates, or tetrachloroisophthalonitrile, increases the ability of 2-chloroethylphosphonic acid alone to cause the release of ethylene in plant tissue when applied to same.

Description

1(~8294~

INCREASING CHLOROETHYLPHOSPHONIC ACID-INDUCED ETHYLENE RESPONSE IN PLANTS

BACKGROUND OF THE INVENTION
The release of ethylene wlthin plant tissue is by now known to effect a wide variety of responses, such as increased rlpening, fruit abscission, increased growth ~^ rate, yield, etc.
One compound known to be capable of causing the release of ethylene in a wide varlety of plants is 2-chloro-r ethylphosphonic acid. See U. S. Patent 3,879,188. The com-pound is, however, both expensive and phytotoxic when used at the elevated concentrations sometimes needed.
':
STATEMENT OF THE INVENTION
Therefore, it ls an ob~ect of the present invention ; to provide a composition and method for increasing the ability of 2-chloroethylphosphonic acid to cause the release of ethylene in plant tissue.
; Thl~ and other ob~ects of the present inventlon will ' become apparent to those s~llled ln the art from the speclfica-tlon and claims that follow.
There has now been found a composition conslstlng essentially of 2-chloroethylphosphonlc acid and a compound ; from the group N-[(trichloromethyl)thio] phthalimlde, cis-N-~ [(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide, cis-;~ N-[(1,1,2,2-tetrachloromethyl)thio]-4-cyclohexene-1,2-dicar-boximide, ferric dimethyldithiocarbamate, ethylenebisdithio-carbamate manganese, ethylenebisdithiocarbamate zinc, methyl-- l-(butylcarbamoyl)-2-benzimidazolecarbamate, or tetrachloro-isophthalonitrlle. When a plant is contacted with a growth-regulating amount of said composition, the abillty of the s ~
: - 2 --' 1()8Z~41

2-chloroethylphosphonic acid to release ethylene in the plant tissue is increased. This ethylene release may be attributable to both chloroethylphosphonic acid degradation and the attendant triggering of ethylene production by the plant tissue. Therefore, one is enabled to employ less 2-chloroethylphosphonic acid, there-by avoiding undesirable side effects, or one may achieve greater growth regulating effects at the same 2-chloroethylphosphonic acid concentration. Further, since the compounds added to the phosphonic acid are fungicides, postharvest disease control is possible.

D CRIPTION OF T~E PREFERRED EMBODIMENTS
The use of 2-chloroethylphosphonic acid in plant growth regulation is described in U. S. Patent No. 3,879,188.
At least 15 different responses are attributed to the internal plant tissue ethylene release induced by the compound. These lnclude: 1) increased yields, 2) auxin activity, 3) inhibi-tion of terminal growth, control of apical dominance, increased branching and tillering, 4) altered biochemical composition of the plant, 5) abscission of foliage, flowers, and fruit, 6) hastened rlpening and color promotion in fruit, 7) increased flowering and frulting, 8) abortion or inhibition of flowering and seed development, 9) prevention of lodging, 10) stimula-tion of seed germination and breaking of dormancy, 11) resis-tance to freeze in~ury, 12) hormone or epinasty effects, 1~) interaction with other growth regulators, 14) interaction with herbicides, and 15) disease resistance. 2-Chloroethylphosphonic acid or precursors or deri~atives thereof are demonstrated in the _ ~5 _ ' 1~82g41 course of 128 specific examples of the patent to achieve one or more of these ethylene-induced responses in a wide variety of plants, seeds, fruits, and vegetables. The use of concen-trations within a range of from 10 to 48000 ppm or 0.1 to 16 kg/hectare is advocated.
According to the present in~ention, this ethylene release and the responses it induces are enhanced by the addition to 2-chloroethylphosphonic acid or a precursor thereof, of a compound selected from the group:
:.
N-[(trichloromethyl)thio] phthalimide:
;, O

~ \/ NSCCl3 C

cis-N-[(trichloromethyl)thio~-4-cyclohexene-1,2-dicarboximide:

~'' 1l ¢~ /
:"~ C~
:`

cis-N-[1,1,2,2-tetrachloroethyl)thio]-4-. cyclohexene-1,2-dicarboximide:
: ~ O

¢~ c I C

:: C Cl Cl .
.
. - 4 _ - lV82941 ferric dimethyldithiocarbamate:

~CP~)2NC~ Fe : ' ethylenebisdithiocarbamate manganese:
: S
: ICH2NH~ S
, ~Mn .. H2NHIC S~
; S -. -. ~, ethylenebisdlthiocarbamate zinc:

H2NHd ,S

" H2NHIC S

;,;
methyl~ butylcarbamoyl)-2-benzimidazole-'; carbamate:

; . .

~ ~ N /
t. CNH(CH2)3CH3 O

~',',~
' tetrachloroisophthalonitrile:
qN
~ @~C14 !,',' CN

-., ~ - 5 -In each instance, although the compound itself does not significantly increase internal plant tissue ethylene pro-duction, the quantity of ethylene which 2-chloroethylphosphonic acid causes to be released in the plant tissue is greatly in-creased. Thus, where previously from 50-5000 ppm of 2-chloro-ethylphosphonic acid alone would be employed, it is now possible, by the addition of from 25 to 10000 ppm of the additive compound, to reduce the amount of 2-chloroethylphosphonic acid to within a range of from 25 to 2500 ppm. Expressed in another fashion, from 0.25 to 5 kg/hectare of 2-chloroethylphosphonic acid is employed together with from o.25 to 10 kg/hectare of the addi-tive compound. Typically the components are present in a ratio of from 0.1 to 50 parts by weight of the additive compound per part of 2-chloroethylphosphonic acid, especially 0.5 to 2:1 parts.
The composition will generally be applied as an aqueous spray, this being most convenient and economical, although dustlng or other methods of application are possible.
Preparation of the aqueous formulation merely requires the dispersion of the materials at the stated concentration ranges, generally employing a nonphytotoxic surfactant, such as poly-oxyethylated sorbitan monolaurate.
The time of application of the active ingredient-; containing formulation is generally dependent upon the growth regulating effect desired, for example, before harvesting in the event that fruit abscission is the desired result, before ; marketing if fruit ripening is desired, etc. Usually it is `/ found that the combination of ingred~ents, probably because of the higher ethylene levels realized, achieves the desired effect 1 to 2 days earlier than with the use of 2-chloroethyl-phosphonic acid alone. Application itself may be by any con-r` venient method, typically by a low volume spray application or to run-off.

. . .

~082941 In order that those skilled in the art may more readily understand the present invention and certain preferred embodiments by which it may be carried into effect, the following speciflc examples are afforded.
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Aqueous formulations having the concentrations and compositions indicated in Table I are prepared. While the formulation in question is being stirred, sweet cherries (Bing) with stems are immersed therein for five seconds, removed and allowed to dry. The dried cherries are placed in 125 ml Erlenmeyer flasks and incubated at 24C daytime ~12 hours), 16C nighttime, 60~ relative humidity, and under a (day) light intensity of 3000 foot candles. At the lndicated intervals, the flasks are capped for 2 hours following which a gas phase :
sample is taken and analyzed on a gas chromatograph sensitive to lO ppb. Each result is the average of 3 tests, 5 cherries per test.

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From the table, the ability of the various compounds to increase the amount of ethylene release triggered by 2-chloroethylphosphonic acid is apparent, despite the ~act that the additives alone are without significant e~fect.

Aqueous ~ormulations of 2-chloroethylphosphonic acid (CEPA) and/or tetrachloroisophthalonitrile (TCIPN) are prepared at the concentrations shown in Table II. Each of the formulations i8 applied by spraying to 2 entire apple trees, ~ gallons per tree. At the indicated intervals lO apples are harvested from - each tree, measuring the pull force required to separate the fruit from the stem (as described by L. J. Edgerton, Hort Science, Vol. 6, No. 4, August 1971). m e apples are then placed in a sealed lO liter container for l hour prior to taking a gas sample for ethylene analysis as in Example l. Next, the fruit firmness is measured on an Effegi fruit tester. Finally, the color of the Rome apples (at 7 days) and the McIntosh (at ll days) is determined to ascertain the degree of redness.

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.. o 8 8 8 .,, ~ U~ ~ ~ o ~ E + + + O
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b~ C~ l~¢
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', ' 11)82~41 Synergystic ethylene release is noted as in Example 1.
Further, the known correlation between ethylene release and growth modification effects (e.g., abscission, firmness, and color) is confirmed.
In discussing the invention and in the claims, reference is made to the effect of the additive compounds on 2-chloroethylphosphonic acid. It should be recognized, however, that the enhancement of the ethylene-releasing effect is inde-pendent of the source of the 2-chloroethylphosphonic acid. Thus, the compound per se may be employed from the start or precursors thereof, such as the monoester, which degrade in situ to 2-chloroethylphosphonic acid, may be employed.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition consisting essentially of 2-chloroethylphosphonic acid and a compound selected from the group N-[(trichloromethyl)thio] phthalimide, cis-N-[(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide, cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide, ferric dimethyldithiocarbamate, ethylenebis-dithiocarbamate manganese, ethylenebisdithiocarbamate zinc, methyl-1-(butylcarbamoyl)-2-benzimidazolecarbamate, or tetrachloroisophthalonitrile, the ratio of said compound to said 2-chloroethylphosphonic acid is within the range of from 0.1 to 50:1 parts by weight.

2. The composition as in Claim 1 wherein the ratio of the compound to the 2-chloroethylphosphonic acid is within the range of from 0.5 to 2:1 parts by weight.

3. The composition of claim 1 which consists essentially of 2-chloroethylphosphonic acid and a compound selected from the group N-[(trichloromethyl)thio] phthalimide, cis-N-[(trichloromethyl)thio]-4-cyclohexene-1,2-dicarboximide, and cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide.

4. The composition of claim 1 which consists essentially of 2-chloroethylphosphonic acid and a compound selected from the group ferric dimethyldithiocarbamate, ethylenebisdi-thiocarbamate manganese, and ethylenebisdithiocarbamate zinc.

5. The composition of Claim 1 which consists essentially of 2-chloroethylphosphonic acid and methyl-1-(butylcarbomoyl)-2-benzimidazolecarbamate.

6. A composition consisting essentially of 2-chloroethylphosphonic acid and tetrachloroisophthalonitrile, the ratio of said nitrile to said acid being in the range of 0.1 to 50:1 parts by weight.

7. A method of increasing the ability of 2-chloro-ethylphosphonic acid to release ethylene in plant tissue, which method comprises contacting a plant with from about 0.25 to 5 kg/hectare of 2-chloroethylphosphonic acid in the presence from about 0.25 to 10 kg/hectare of a compound selected from the group consisting of N-[(trichloromethyl)thio] phthalimide, cls-N-[(trichloromethyl)thio3-4-cyclohexene-1,2-dicarboximide, cis-N-[(1,1,2,2-tetrachlor o ethyl)thio]-4-cyclohexene-1,2-di-carboximide, ferric dimethyldithiocarbamate, ethylenebisdithio-carbamate manganese, ethylenebisdithiocarbamate zinc, methyl-1-(butylcarbamoyl)-2-benzimidazolecarbamate, or tetrachloroiso-phthalonitrile,

8. A method of increasing the ability of 2-chloro-ethylphosphonic acid to release ethylene in plant tissue, which method comprises providing a mixture of 2-chloroethyl-phosphonic acid and a compound selected from the group con-sisting of N-[(trichloromethyl)thio] phthalimide, cis-N-[(tri-chloromethyl)thio]-4-cyclohexene-1,2-dicarboximide, cis-N-[(1,1,2,2-tetrachloroethyl)thio]-4-cyclohexene-1,2-dicarboximide, ferric dimethyldithiocarbamate, ethylenebisdithiocarbamate man-ganese, ethylenebisdithiocarbamate zinc, methyl-1-(butylcar-bamoyl)-2-benzimidazolecarbamate or tetrachloroisophthalonitrile in a ratio of from 0.1 to 50 parts of the compound per part of 2-chloroethylphosphonic acid, and applying a growth-regulating amount of said mixture to a plant.

9. A method as in Claim 8 wherein the ratio of the compound to the phosphonic acid is 0.5 to 2:1.