CS256566B1 - Method of growth stimulator or regulator production - Google Patents

Abstract

Plant growth stimulator and / or regulator based on organic halogen compounds is produced catalytic or non-catalytic chlorination of .beta.-butyrolactone at temperature of 80 to 200 ° C until the index is reached refraction nD25 = 1.4700 to 1.4780 (1.4755 to 1.4760. It is separated from the chlorination product hydrogen chloride and optionally unconverted ω-butyrolactone and / or the chlorination product saponified or neutralized by alkali metal. The product is suitable for production biologically active substances in the chemical industry.

Description

The invention relates to the production of a plant growth promoter or regulator, respectively. production of active components of stimulators or growth regulators based on organic halogen compounds, using substitution chlorination.

In agriculture and forestry, many compounds have long been successfully applied as physiologically active substances such as auxinoids, kinins and retardants, although the biochemical nature of their action is still subject to various hypotheses [Audus J. J .: Plant Science Monographs. London-New York (1963); Turkey R. Ch., Polykarpova F. Ja .: Vegetatiinnoe Growth of Plants with Growth Primer, Moscow (1966)]. Growth regulators have different structures [Appel P., Natr. L .: Biochem Physiol. At. 1976, 169; Wegler, R .: Chemie der Pflanzenschutz und Shadlingsbekamppfungsmittel, Band 4. Springer Verlag, Berlin-Heidelberg-New York (1977)]. Succinic acid is known to stimulate plant growth and to explain the biochemical effect of quantum biochemistry [Blagoveshchenskij A.V., Rachmanov R.R .: Amber Kislota and Urozheva Promotion, Tashkent (1966); Blagoveshchenskij A.V., Rachmanov R.R .: Biochimicheskaya nature enhances the importance of amber kisloty. Izdatefstvo Moskovskogo Gusudarstvennogo Universiteta, Moskva (1970)] as well as organic sludges from anodic] oxidation of aluminum, containing mainly succinic acid (cf. No. 229 411), maleic anhydride, maleic acid, salts and esters (cf. 318) as well as by-products from the production of cyclohexanone by oxidation of cyclohexane (cf. author's certificate 220 936 etc.) An effective growth regulator should also be dichloroisobutyric acid and its salts (U.S. Pat. (Prieber: Bull. Soc. Chem. France 1954, p. 199).

These and other known plant growth regulators and stimulators are interesting, but are increasingly being applied in practice, but understandably, they still do not sufficiently address the needs of intensive agricultural crop production and forestry. Thus, the range of potent plant growth promoters and plant growth regulators is expanded to include other production methods of the present invention.

According to the invention, the process for the production of a stimulator and / or a plant growth regulator as well as active components of stimulators and / or growth regulators, based mainly on organic halogen compounds, is carried out by substituting non-catalytically or catalytically chlorinated χ-butyrolactone at 80-200 ° C to until a refractive index of n _D ²⁵ = 1.4700 to 1.4780, preferably 1.4755 to 1.4760. Hydrogen chloride and optionally unconverted β-butyrolactone are separated from the chlorination product and / or the chlorination product is saponified and / or neutralized with an alkali metal compound, preferably a carbonate or bicarbonate.

An advantage of the method for producing the stimulator and / or plant growth regulator of the present invention is feasibility in one technological step with good yields, even on a type plant. It does not require demanding insulation. Then raw material availability, low energy consumption and virtually wastelessness of the whole process.

The products of chlorination of χ-butyrolactone are mainly α-chloro-γ-butyrolactone, α, α'-dichloro-t-butyrolactone, χ-chlorobutyric acid and α, χ-dichlorobutyric acid. However, it is appropriate to isolate and recirculate unreacted β-butyrolactone from the reaction product. Neutralization or saponification of the chlorination products, either with alkali metal carbonates or bicarbonates or, at lower temperatures, with alkali metal hydroxides (taking care to avoid dechlorination or dehydrochlorination of the χ-butyrolactone chlorination products) gives rise to the corresponding alkali salts. chlorination products can be applied in the form of solutions, in particular dilute aqueous solutions with a concentration of 1: 10 ^-3 to 1: 10 ^-5 = by weight, but also in the form of dispersions, emulsions, possibly together with other organic substances, pesticides, fertilizers, especially liquid They can also be applied by spraying only the active ingredients themselves, and it is suitable to associate them with the application of pesticides, fertilizers or preservatives.For the impregnation of the grain in seed preparation, it can even be applied in powder form, It is advisable to use non-plugging an appreciable effect of a plant growth promoter and / or regulator.

In the case of catalytic chlorination of χ-butyrolactone, the usual halogenation catalysts are used, such as Lewis acids, but also antimony trioxide, antimony trichloride and the like. From the chlorination product, it is advisable to separate hydrogen chloride, which would make it difficult to manipulate the stimulator or growth regulator, causing corrosion and the like. The chlorination product may optionally be stabilized, for example by the addition of 1 to 3% urea or hexymethylenetetraamine.

When saponifying the chlorination product, care must be taken to avoid chlorine splitting off. It is therefore appropriate to neutralize and saponify the chlorination product at a temperature of 0 to 50 ° C.

The production process according to the invention can be carried out batchwise, semi-continuously or continuously. Unconverted χ-butyrolactone should be recycled.

Further characteristics of the production method and utility properties of the stimulator and / or plant growth regulator, including woody species, are evident from the examples.

256560

Example 1

Stages of known methodology [A. Murina et al., Biology 35, 937 (1980)] determine the germination and length of corn roots of the TO 440 variety and the stage of the Hojchus methodology [R. Hojčuš a í: Instructions for Exercises in Plant Physiology, Nature, Bratislava (1981)] germination and length of hypocotyl spring barley variety Opal depending on the concentration of aqueous solution of chlorinated χ-butyroiactone. The chlorinated χ-butyrolactone itself has the following composition (in% by weight): α-chloro-γ-butyrolactone-26.4; α, α'-dichloro-γ-butyrolactone ~ 12.7; χ-butyrolactone - 12.6; α, χ-dichlorobutyric acid = 31.4; χ-chlorobutyric acid = 13.4. The results obtained are summarized in Table 1 and are the arithmetic mean of three replicates. At the same time, the effect of an aqueous solution of chlorinated β-butyrolactone was tested under a light ramp with similar variants in a three-week experiment. This is done by sowing 30 grains of Opal spring barley in small containers containing 200 g of soil and 200 g of washed quartz sand with the same fertilization and, after emergence, unit to a number of dc 20 plants. The grain is used as such pickled in distilled water (control) or pickled in aqueous chlorinated β-butyrolactone solutions of various concentrations. Pickle 50 g of grain in 60 cm ^{3 of} aqueous solution for 24 h. In those variations where the grain has not been pickled, it is applied to the plants 7 days after sprouting, spraying with solutions of chlorinated β-butyrolactone of varying concentration as well as neutralized at a dose of 5 cm ³ per pot. Each variant has 4 repetitions. The results obtained in Table 1 are the arithmetic mean of the values obtained. Statistical evaluation is done by analysis of variance. The optimum in terms of grain germination, root length and hypocotyl is the concentration of solution 3. 10 ~ ³ ° / wt.

Table 1

Type and concentration of aqueous solution (»/ w / w)

Weight of above-ground mass of spring barley - dry matter [%] grain stained spraying stand

Control (distilled water) 100.0 - Α-Naphthylacetic acid o konc. 3. 10 ^-3 % 115.7 115.1 o konc. 3.10 ^-4 % 111.1 110.8 Aqueous chlorinated solution χ-butyrolactone on concentration 3 .10 ^-1 % 89.7 90.9 3.10 ² % 106.0 105.1 3.10 ³ % 126.6 128.4 3. 10 “ ⁴ % 118.2 120.7 3. 10 ⁵ % 124.6 125.0 Weight of evidence P 0,05 14,54 differences P 0.01 19.44

2SSS68

Variation End- Grain yield Straw harvest Quantity Weight 1000 Hay yield friction [° / o] L% J productive grains (HTZ) [%] [% offshoes [%] weight] 1983 1984 1983 1984 [%]

CO co σ »τ-ί co

WHAT

WHAT

OO

ABOUT CO CDCO4 OO ΙΟ ΙΌ O 05 C * s rd about 05 CO CO 05 05 rd about ^ CO about rd rd 00 CM O O rd rd what what rd H rd rd rd rd rd rd rd rd

O CO <N o θ co oo o O CM CO OO CO

CO rd CM 05 what rd 00 CM ts m

CO CM CO 05 oo rd CM

ABOUT CO rd ^ cq Otoo CD rd m CD rd CM rd I cmio I O> WHAT about O rd rd ' rd O 1 ABOUT 05 CO rd rd rd rd rd rd rd rd

CD C0_ ABOUT. CO CM about ABOUT) cm o I 1 1 and O rd ABOUT 05 rd rd 1 > CD 1 * d 00 rd rd rd rd rd rd rd

CD WHAT WHAT CDT \ 00 WHAT CM about about what oo I co oo 1 about 00 D ABOUT ABOUT about 05 1 o o 1 ABOUT m rd rd rd rd rd rd

O O 05 O O 05 rd rd

WHAT

ABOUT

CM

O o

rd t CO rd in i>

O o

ABOUT

rd and lf5 CM ABOUT. l> and rd 05 co 1 rd θθ I oo • sr CM rd rd ABOUT * O 05 1 ABOUT about rd rd rd rd rd rd

ABOUT

ABOUT

03 CD WHAT rd Cv CM CO ED rd [ 1 1 what <o O rd rd » 1 rd l ABOUT about rd rd rd rd rd rd

CD 05 00 05 about 10 co cm I tjT co I what ABOUT 00 CM CM 1 O rd l about rd rd rd rd rd rd

what about 05 ^ 10 what σϊ

CD ABOUT tx <D UD o o CD 00 about !>. I 1 what, Tfl CO rd CD ABOUT) CM rd 1 1 o 1 ABOUT »- r> rd rd rd rd rd N what \ r and N co WHAT 1 ( 1 1 1 1 1 and lf5 rd about about about about o o o about o o 1 rd rd rd rd rd rd id rd oo • CL CL WHAT WHAT WHAT WHAT CO CO CO what

they

O ΰ tí 5t W o 14

S fl

O g ω 44>. β-γ o + ->

S nS o o j

C3 fl '§ * cu fl cu O s · ® fl wn Sr o ⁴⁴ ' 5? ^w fl §

O g cu 44 3 H O t

4 ” ¹ 4_t yw N tí o o PLi f-.

s * .3 o S £ Φ o w + »

ABOUT . . ι — 1 ω & * £ te w rt O I cl a

W o

t> N O Λ Ά 14 .S t Ό CU N CL f-i

Example 3

The active substance of the plant growth regulator is prepared by chlorination of t-butyrolactone. Weigh 2 moles (172.2 g) of β-butyrolactone into a glass chlorinator, which was heated to 150 ° C with an oil bath. After heating, chlorine in the amount of 8.74 is fed to the bottom of the chlorinator with χ-butyrolactone. . 10 ~ ² mol / min. Uncatalyzed chlorination is checked by continuous sampling of small samples to determine the refractive index at 25 degrees Celsius. Chlorination is terminated on reaching n _D ²⁵ - 1.4755 to 1.4760. The reaction time at 150 ° C for 6.5 h and at ^170,? C

4.2 h. The chlorinated β-butyrolactone obtained has the following composition (in% by weight): α-chloro-γ-butyrolactone = 26.4; α-ω-dichloro-γ-butyrolactone equals 12.7; χ-butyrolactone - 12.6; α, χ-dichlorobutyric acid - 31.4 and χ-chlorobutyric acid = 13.4.

Fig. 1 a d 4

The procedure is similar to that in Example 3, except that only 1.5 wt. (calculated on χ-butyrolactone) antimony trichloride and chlorination temperature 145 + 1 ° C. The chlorinated χ-butyrolactone obtained, catalyzed by chlorination for 7 h, contains (in% by weight):

37.1 α-chloro-γ-butyrolactone; 21.2 α, α-dichloro-γ-butyrolactone; 3,7 χ-butyrolactone;

11.2 χ-chlorobutyric acid and 25.3 α, χ-dichlorobutyric acid. It is distilled under reduced pressure (2.67 kPa).

A portion is converted to a mixture of potassium salts by treatment with potassium bicarbonate at 10-20 ° C.

Claims (2)

Process for the production of a stimulator and / or a plant regulator as well as active components of a stimulator and / or a growth regulator, based mainly on organic halogen compounds, characterized in that χ-butyrolactone is substituted non-catalytically or catalytically chlorinated at 80 to 200 ° C reaching a refractive index n _D ²⁵ = 1.4700 to 1.4780, preferably 1.4755 to 1.4760, z According to the invention of the chlorination product, hydrogen chloride and optionally unconverted β-butyrolactone are separated and / or the chlorination product is saponified and / or neutralized with an alkali metal compound. 2. Method according to claim 1, characterized in that the neutralization is preferably carried out with a carbonate or a bicarbonate.