JPH02268102A - Freshness-keeping agent for cut flower - Google Patents

Abstract

PURPOSE:To obtain the subject formulation making cut flower have long life in a state of before finishing of blooming without fading, possible to use as pre-treating agent or post-treating agent and exhibiting effect even in low concentration containing tetrapyrazinoporphyrazine derivative. CONSTITUTION:The subject formulation contains from 1X10<-4> to 0.1wt.% compound expressed by the formula [M is H (2H), metal, metallic oxide or metallic halide], etc. Said formulation does not induce coloring of flower nor problem of waste water as exhibits effect even in low concentration. Especially exhibits effect to withering phenomena such as fading of rose, inversion of petal, crooked neck, fading of leaf and defoliation. From 1X10<-4> to 0.1wt.% organic solvent such as DMF or acetone may be added to the formulation to improve solubility of active compound in water, or the formulation may be used by mixing with other additives (e.g. bactericide) or other freshness-keeping agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel freshness-keeping agent for cut flowers containing a tetrapyrazinovolfilazine derivative.

[Conventional technology]

Freshness maintaining agents for cut flowers are broadly divided into pre-treatment agents and post-treatment agents.

Pretreatment agents are used by producers to water cut flowers for a short period of time after they are harvested and prior to shipping, and the effect is carried over until the time when consumers arrange them in water.

STS (silver complex salt Ag(SzOy)z''-, which is produced by mixing silver sulfate and sodium thiosulfate in a fixed ratio of 1:4 or 1:8), which is a typical life-saving agent, has 197
It was discovered by Veen (Netherlands) et al. in 1988, and it became widely used because it showed a great life-extending effect on flowers (mainly carnations and sweet peas) that withered due to the production of ethylene.

As mentioned above, STS is effective in prolonging the life of flowers that lose their ornamental value due to ethylene (wilting, falling buds, falling flowers), but it is effective in prolonging the life of flowers that lose their ornamental value due to ethylene (withering, falling buds, falling flowers), but it also shows the effect of extending the life of flowers that lose their ornamental value due to ethylene (withering, falling buds, falling flowers). (roses, gerberas, dahlias, etc.) have no life-prolonging effect, and even flowers that do have STS effects depending on the type.
Because the treatment concentration and immersion treatment time etc. of
Usage requires precision. In addition, there are problems with wastewater due to the presence of ions, and in the Netherlands, wastewater is being collected and
An alternative to TS is desired.

Post-treatment agents are used continuously by retailers while selling cut flowers or by consumers in vases to extend flower life and improve quality.

Bacteria and fungi can easily grow on the cut ends of cut flower stems, clogging the ducts and inhibiting water absorption, so to prevent this, the mixture is made with mainly ingredients such as weed killer, plant preparation, and nutrients. . For example, sho tang (hanamochi extension)
8-Hydroxyquinoline (bacteria, promotes water absorption, closes stomata and improves water balance, reduces sensitivity to ethylene), aluminum sulfate, vitamin C, alcohol, vinegar, surfactants, etc. is used.

JP-A-63-166801 discloses the effect of metal phthalocyanine on maintaining the freshness of cut flowers. Although it lasts a long time in flowering, it is not necessarily a sufficient freshness-preserving agent as it colors the flowers and causes chemical damage to the leaves.

[Problem to be solved by the invention]

As mentioned above, STS has problems such as handling methods, wastewater treatment, and fading, and JP-A-63-166801 has problems such as coloration due to chemicals, chemical damage, and the inability to extend the flower life in the state before full bloom. There is.

[Means to solve the problem]

As a result of studying the above-mentioned problems, the present invention shows a life-extending effect before full flowering, can be used as a pre-treatment agent and a post-treatment agent, and is effective even at low concentrations, so it does not discolor flowers and can be used in wastewater. The purpose of the present invention is to provide a freshness-keeping agent containing a tetrapyrazinovolfilazine derivative that is free from problems. Furthermore, the product of the present invention also has a g* effect.

The product of the present invention can be applied to any cut flowers, such as roses and carnesian flowers.

Examples of the tetrapyrazinovolfilazine derivatives of the present invention include the following.

Those expressed by formulas (1) and (2) are conventionally known.

Formula -LyuD- In the formula, RI Rz is RI=Rz, hydrogen, methyl group, ethyl group, carbamoyl group, phenyl group or furyl group, RI-t-butyl group and R, #hydrogen, or R1 and R2 together make C+. R2°-, M represents hydrogen (2H), a metal, a metal oxide, or a metal halide.

Niyu IL In the formula, M has the same meaning as above.

February 10, 1989 and February 1, 1989 according to the invention of the present inventors
Patent application filed on the 6th (Japanese Patent Application No. 1-32143, 1'-
No. 32144, No. 1-32145, No. 1-37108
and No. 1-37109) Formulas (3) to (8
)English; In the formula, R3-R11 are the same or different, hydrogen, carboxyl group, substituted phenyl group, substituted furyl group, optionally substituted thienyl group, phenoxy group or phenylthio group, or R2 and R4Rs and Rb RI and R,
RI and R1, each of which may be substituted or substituted, respectively, with the proviso that R1 to R1 are not all hydrogen.

M has the same meaning as above.

In the formula, Z represents a hydrogen atom, and R1 to R0 are the same or different, an alkyl group, a haloalkyl group, an alkenyl group, an aryl group, an alkaryl group, an aralkyl group, a heterocyclic group, a heterocyclic-substituted alkyl group or an alkyl-substituted heterocyclic group, k, 1. m and n represent integers from 0 to 2, k+I+
m+n is at least l, and M has the same meaning as above.

-Formula Ichihito 50- In the formula, Z represents a hydrogen atom, and RI S ” Rl l
are the same or different and represent a mono- or di-substituted amino group or an alkoxy group, 9% q, r% t is 0 to 2
, p+q+r+t is at least 1, and M has the same meaning as above.

i engineering i1- During the ceremony, M has the same meaning as above.

In the formula, 2 represents a hydrogen atom, and R111 to R■ are the same or different and each represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an ester group, an amide group, or a phenylthio group which may have a substituent. Indicates the group, u%
v% ” s 3' represents an integer from 0 to 4,
+w+y is at least 1, and M has the same meaning as above.

Base 1 Tech 1 ・:” x ”’1,, 1100
1. -1 substituents may be present, )M' represents hydrogen (2H), metal, metal oxide, metal halide, metal hydroxide, acyl metal, alkoxy metal or siloxy metal.

Among these widths, R1-R in formula (3) is particularly preferable.
1° is a carboxyl group, and in formula (4), R11 to formula (7), R19 to R2t are ethyl.

When used as a pretreatment agent, the above-mentioned tetrapyrazinovolphyrazine derivative preferably has an I
．． 1% by weight, optionally with DMF, acetone, methanol, etc. to improve solubility in water.
Adding 1X10-'~0.5 weight percent of solvent;
What is necessary is to prepare a treatment liquid and immerse the cut flowers in it, or it is also possible to continue immersing the cut flowers in the same treatment liquid as described above and use it as a post-treatment agent.

The tetrapyrazinovolfirazine derivative of the present invention may be used in combination with other additives (bactericides, etc.) or other commercially available freshness maintaining agents, and the additives may be used after using the product of the present invention. You may also use other commercially available freshness maintaining agents.

[Synthesis example]

Production examples of compounds represented by formulas (3) to (8) are shown below.

Production Example I R+ + ~Rl4-G O! Cz H
2.74 g (0,Ol mat) of the compound of formula (4) where M=Cu, 2.3-dicyano-5,6-dinitoxycarponylvirazine and 0 cuprous chloride.
．． 5R (0,0O5 mol) was placed in a flask equipped with a cooling tube, and first stirred at 100-110°C for 1 hour.
It was then heated at 150-200"C for 30 minutes. After the black-blue product was cooled to room temperature, 10% ammonia water 2
Washed with 0 ttrl and 20 IR1 diluted hydrochloric acid. It was further washed with 30 ml of water and 20 d of ethanol. Since the product was soluble in chloroform, it was dissolved and washed with a saturated aqueous sodium bicarbonate solution and a saturated aqueous NaCl solution. After chloroform was distilled off under reduced pressure, 3.2 g of a black-blue solid (Compound A) was obtained by column purification (methanol/ethyl acetate = 115). Yield 27.6%, UVλmax 645 nm
(CHCI,), IR2955cm-' 1713c
m- Elemental bone i (%) Ikkoshu l-- and 1l- C49,249,68 H3,33,45 N 1 B, 1 19.32Cu
5.4 5.48 Production Example 2 R', ~
3 g (0.01 mol) of the compound 2.3-dicyano-5,6-dinitoxycarbonylpyrazine of the above formula (3), which is R,,--COOH,M-VO, and 1 g (6.3 m + 5 mol) of vanadium trichloride. ) and 0.05 g of ammonium vanadate were placed in a flask equipped with a condenser, stirred at 100-110°C for 1 hour, and then heated to 150°C.
Heated at ~200°C for 30 minutes. After washing the black-rimmed product, column purification (ethyl acetate) yielded 2.9 g of solid.

Next, this solid was heated under reflux for 30 minutes to 1 hour in 100 d of a 5% aqueous potassium hydroxide solution. Thereafter, the solid was made weakly acidic with hydrochloric acid, and the precipitated solid was collected by filtration and washed with acetone and water to obtain 1.5 g of a dark green solid (compound B). Yield 64.4%
, UV of aqueous solution of Na salt 1m 645mm (water), rR34g3cm-'1734C1
-' Elemental analysis (%) 1 constant JL- 41.5 111m 4 0.9 0 1.5 0.85 23.9 5.2 2 3.8 6 5.42 Expressed by the above formula (5) 1.74 g (5 mmol) of the compound being treated
, vanadium trichloride 0.4g (2,54mso1),
A catalytic amount of ammonium vanadate was added to 20 d of quinoline and reacted for 3 hours at 150"C in a flask equipped with a condenser. After cooling, it was made weakly acidic with dilute hydrochloric acid and filtered, and the obtained solid was reduced to 10%. Washing with aqueous ammonia, water, and ethanol gave 1.8 g of a black solid (compound C). Yield: 38%.
, UV λmax 694nm (DMF) λ
max 710 (CHCf,) Elemental analysis (%): ] Constant "L--" L-view Jl.

C5B, 8 5 9.2 2H5,55
,48 N 31.5 30.7
1V 3.3
3.4 9 [Example] Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Compound A14) Formula, RII-RIa = C0zCt
Hs.

Weigh 158d of M=Cu), D M F, 600
#1, then diluted to 300d with tap water (5
0pp-).

This was designated as a freshness maintaining agent Asa. Similarly, 10p
The one adjusted to pm was defined as A1°, and the one adjusted to 51)+111 was defined as As.

Compound B (te3) formula, R1-R1゜--CO, H, M
-VO) and compound C (formula (5), RIS~R3, -agent Bs, C+o were prepared.

We purchased carnations (item name: Nora to Pink) that had not been treated with commercially available life-extending agents or other chemicals, and selected ones with constant length, number of leaves, and flower condition.

Freshness maintaining agent A. , A1°, C1°, tap water, and Fresh Keep Flower (Fuji Sugar Co., abbreviated as FK) were placed in three test tubes each containing lO−, and the carnations were immersed in the test tubes and exposed to 500 lux. The indoor light was kept on at around 23°C day and night. An amount of solution corresponding to the steaming # and lt was added every day and observed. The result is the Hanamochi Index [This month's agriculture 31 (10) 40-44 (1987)
) are shown in Table 1.

a: Freshness standard rating (5, 4, 3, 2, 1, 0) n: Number of flowers by freshness Standard freshness rating (for carnations) 5: Both flowers and leaves have lost their freshness, and are not seen. , upright.

Completely droopy ■: Slight droop is seen and the flowers have lost some activity.

: Although there is considerable drooping of the neck, the flowers are still suitable for viewing.

: Some of the flowers are inactive and drooping.

: Flowers are inactive and droopy.

: Flowers wither, their heads droop, and they have no lifespan.

The number of days the flowers lasted. (Same below).

From Table 1, all showed a life extension effect of 6 to 10 days compared to tap water.

FK showed discoloration as the number of days of soaking increased, but the product of the present invention was bright and did not cause any coloring to the flowers.

Example 2 Commercially available roses (product name: Carte Plants - White) that had not been treated with life-extending agents or other chemicals were purchased, and roses with constant length, number of leaves, flower condition, etc. were selected.

Freshness maintaining agent A. , A1゜, C1゜, tap water, and Chrysal (■ Chrysal Japan, abbreviated as CR) were placed in three test tubes each containing 10-10% of each. A rose was immersed in the test tubes, and a 500 lux indoor light was placed. The temperature was kept at around 23°C day and night. An amount of solution corresponding to the amount of transpiration was added every day and observed. Table 2 shows the results expressed in flower retention index.

Freshness standard rating (for roses): When the flowers have begun to open, the leaves are fresh and there is no drooping at all.

; Flowering, without drooping neck, and leaves are fresh.

The leaves are in full bloom, but the freshness of the leaves has decreased a little.

: Some of the petals are inactive and slightly sagging.

1: Flowers as a whole are inactive, leaves lack freshness, and are droopy.

O: Flowers and leaves are completely unbearable for ornamentation, and the flowers have no lifespan.

Table 2. According to Table 2 of the freshness maintenance test for roses (product name: Carte Branze - White), all of them showed a lifespan extension effect of 2 to 5 days compared to tap water.

It was found that the product of the present invention has good flower retention even before it has fully bloomed.

In addition, the way CR flowers bloom is such that the petals fall outwards, which is markedly different from the general way roses bloom, which is considered undesirable.

Example 3 Roses (product name: Sonia Pink) were purchased, and the length, number of leaves,
We selected flowers that had a constant flower condition.

Freshness maintaining agent A. , As Bs, tap water, and CR were each placed in test tubes in triplicate for 10 d each. The roses were continued to be immersed in it and observed in the same manner as in Example 1. Furthermore, A1. Roses were soaked in water for 3 hours and then soaked in tap water (Aol.). Table 3 shows the results expressed as flower retention index.

Table 3. According to Table 3 of freshness maintenance test for roses (product name: Sonia Pink), all of them had a lifespan extension effect of 1 to 5 days compared to tap water.

Similar to Example 2, CR had flowers that bloomed differently from the general blooming of roses, and moreover, significant discoloration of the flowers was observed.

The product of the present invention has a long flower life even before it fully blooms, and
Preprocessing AI. A similar or even greater effect was observed.

Furthermore, in the leaves, tap water and CR cause discoloration, yellowing, withering, and falling of leaves at a relatively early stage, but the product of the present invention
It remained vibrantly green for a long time.

〔Effect of the invention〕

The freshness maintaining agent commonly used in the products of the present invention allows cut flowers to last longer in the state before they fully bloom, and does not fade.

In particular, rose wilt usually manifests itself as faded flowers, inverted petals, drooping necks, discoloration of leaves, and falling leaves, and freshness-preserving agents are effective against all of these wilt phenomena. As a result of the desired zero test, it was recognized that the product of the present invention is effective against all of them.

Claims (1)

[Claims] A freshness maintaining agent for cut flowers containing a tetrapyrazinovolfilazine derivative.