DE2231463A1 - MEANS OF INFLUENCING PLANT GROWTH - Google Patents

Description

relating to agents for influencing plant growth

The invention relates to compounds that can be used to control plant growth as well on the use of these compounds as active ingredients in agents for the above purpose.

Namely, it has been found that certain jithansulfinic acids and their oxygen or sulfur esters and certain ethanesulfinamides can be used to stimulate plant growth to regulate or modify. When applied to the location of the plants, these compounds develop the most diverse properties that influence and regulate the growth of plants, with of course the. Effect depends on various variables, such as the species

- 2 ~

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of the "treated plants", their age and the treatment time, of the length and concentration of the agent used or. the connection used and their special preparation * Among the effects on plant growth that have been observed are to name the acceleration and unification of the Ripening of fruits, acceleration of the Leaf rejection, promotion of flowering, stimulation of sprouting (in the case of tuberous plants or the seed germination Connections prevent the herbaceous part from predominating in tuberous plants, which otherwise leads to that lateral rungs are formed and that the formation of roots on Torah tribes is increased, which is the reason for the shrinking of the tomato leaves and the withering of the plants. A biological response such as that achieved using the compounds according to the invention used in agriculture can be used to significantly increase productivity, while at the same time working hours and other costs are reduced.

The agents according to the invention for influencing and Regulation of plant growth are compounds of general Formula: q

X-GH ₂ CH ₂ -SA _n (I),

wherein X can stand for. a chlorine, bromine ^ or iodine atom or

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one of the following groups: hydroxy; Alkoxy with "up to 3 carbon atoms; aryloxy with" up to 10 carbon atoms; Alkylthio with up to 3 carbon atoms; aralkoxy with up to 10 carbon atoms; acyloxy with up to 4 carbon atoms; alkylsulfonyloxy, in which the alkyl group contains up to 3 carbon atoms; arylsulfonyloxy, nitro, monoalkylamino or dialkylamino, in which each alkyl group contains up to 6 carbon atoms; or "X stands for A ¹ E ¹ , VfOriii A ¹ oxygen and R 'the 2- (dimethylcarbaraoyl) -1-methylvinyl-, the 2- (diethylcarbamoyl) -1-methyl vinyl - or the 2- (Methoxycai ^ oriyl) ~ 1-methyl vinyl group.

In the Eoriael above, A stands for the following groups: The group -Y-S, in which ^ is oxygen or sulfur, with the proviso that

if Y is oxygen, R can have the following meanings: Alkyl has up to 20 Carbon atoms; Aryl with up to 10 carbon atoms; Aralkyl with up to 10 carbon atoms; Alkenyl with up to 8 carbon atoms; Alkynyl with up to 4 carbon atoms; 2- (dimethylcarbaraoyl) -1-methy.! Vinyl, 2- (methyl-

carboxooyl) ~ 1 -methylvinyl, 2- (Hethoxycarbonyl) -

ο
1-πι et hy! Vinyl; or ZR, where Z is a -alkyl ene

ρ with up to 4 carbon atoms and R alkylthio with up to

to 3 carbon atoms, alkoxy with up to 4 carbon atoms, aralkoxy with up to 10 carbon atoms, hydroxy or a ß-substituted ethanesulfiny1oxyhälft e may be, in which the ß-substituent is identical: n with the ß-Öubstituenten in formula 1 by X is represented;

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- 4th

and ν / eil η Y means sulfur, E the following meanings Has:

Alkyl rait "up to 8 carbon atoms; optionally substituted with chlorine or bromine; Aralky.1, wherein the alkyl group contains up to 4 carbon atoms;

and Ii can also stand for hydrogen if X is oxygen and X has one of the meanings given above, except for A ¹ R ¹ }

Another meaning for A is the group:

- ^E 3

R ^ and R can be identical or different and represent hydrogen, alkyl ait up to 20 carbon atoms or aralkyl with up to 10 carbon atoms; and being either one or both

Z M Ε " C. '

Br and E ^{can stand for IrY 1} , in which Ir is alkylene with up to 4 carbon atoms and Y ^{1 is} hydroxy- or ß-haloethane sulf: i.nyloxy, where the ß-halo substituent is chlorine, bromine or iodine, with the following proviso: If Y ^{1 is} hydroxy, X represents one of those mentioned above for X.

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- 5 -

Groups except A'fi ', and when Y' ß-haloethanesulfonyloxy is, X stands for chlorine, bromine or

7th

Iodine, if Ή / stands for hydrogen, Zl

E also represented: krjl rait up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, cycloalkyl with up to 8 carbon atoms or IrY, in which Έ / die

ρ
Above meaning liat and Y for alkylthio with up to 3 carbon atoms or alkoxy with up to 4 carbon atoms

7. - Il

Atoms stands; v; if E ^ is hydrogen, E also represented: a substituted phenyl of the formula:

v / orin Z 'for alkyl with up to zn 3 carbon atoms, alkylthio with up to 3 carbon atoms, alkoxy with up to

3 carbon atoms, alkylsulfonyl with up to 3 carbon atoms, Is chlorine, bromine, mitro or trifluoromethyl; "

Zl '

and if E ^ is hydrogen, alkyl or aryl,

4th
E can also represent hydroxy or alkoxy with up to

4 carbon atoms.

In the means according to the invention are self-evident in addition to the active ingredient, the usual additives are present.

The following is to be said about the above formula I:

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When A is the group - X - represents R, the active compound correspond ϊ e of the formula:

X - CII ₂ CH ₂ - S - Y - R (II),

wherein X, X and R have the above meanings.

As examples of this class of the invention Connections are mentioned:

2- (benzyloxy) ethyl 2-chloroethanesulfinate, Hexyl-2-iodäthansulfinat, ■ S-isopropyl-2-bromoethantliiosulfinate, Allyl 2-hydroxyethanesulfinate, 2-propoxyethanesulfinic acid, Methyl 2- (2-naphthoxy) ethanesulfinate, Octyl 2- (ethylthio) ethanesulfinate » S-methyl-2- (nethylthio) ethanthiosulfinate, S-Ben2yl-2- (ben2, yloxy) ethanthiosuli'inate), 2- (propionyl oxy) ethanesulfinic acid, 2- (ethylthio) ethyl-2-acetoxyethanesulfinate, 2- (ethylsulfonyl) ethanesulfinic acid, Propargyl-2-mesylethanesulfinate, Ethyl 2- (phenylsulfonyloxy) ethanesulfinate, Hexylr-2-nitroethansuli inat 2- (butylamino) ethanesulfinic acid Propyl 2- (dipropylamino) ethanesulfinate, 2 ~ diethylamino) ethanesulfinic acid,

ethyl-2- / ~ 2- (methylcarbaraoyl) -1-methylvinyl 7-eth-

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sulfinate mid

Ethyl 2- / 2- (methoxycarbonyl) -1 -methylvinyD ^ ethereal sulfinate.

Within the general class of compounds in which A represents the group - O - R are certain Species preferred, i.e. those compounds wherein X is chlorine, bromine or an alkoxy group of up to 3 carbon atoms and R has the following meanings: hydrogen, alkyl with up to 20 carbon atoms, aryl with '

up to 10 carbon atoms, alkenyl with up to 8 carbon atoms,

p alkynyl with up to 4 carbon atoms or ZR ″, where Z is alkylene

ρ
with up to 4 carbon atoms and R alkylthio with up to J carbon atoms or alkoxy with up to 4 carbon atoms or hydroxy

means; and in which, if X is chlorine, R ~ can also stand for a β-chloroethanesulfiriyloxy group.

Examples of such connections are:

2-ethoxyethyl-2-chloroethanesulfinate, propyl-2-bro! ⁱ iä.thansulf inat, 2-ynoic acid Bropjäthansulf, phenyl-2-bromätharisulf inat, lfaphthyl-2-chloräthansulfinat, 2- (iithylthio) ethyl-2-bromäthansulfinat, ■ 2-methoxypropyl-2-bromäthansulfinat, 2-butoxypropyl-2 chloroethanesulfinate and propynyl-2-bromoethanesulfinate.

Among this preferred class of compounds are certain

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Compounds particularly effective for influencing plant growth, namely compounds in where X is chlorine and R is an AUtyl group with up to 20 carbon atoms or an alkenyl group with up to 8 carbon atoms represent.

Examples of this preferred subclass are:

Methyl-2-chloroethane sulfate, Alayl-2-chloroethane sulf inate, 3 ~ butenyl-2-chloroethanesulfinate, heptyl-2-chloroethanesulfinate, Decyl-2-chloroethanesulfinate and J-pentenyl ^ chloroethanesulfinate.

Other preferred compounds in the class of compounds according to formula I, in which A represents the group X-R, are those in which X is alkoxy with up to J carbon atoms, Aralkoxy with up to 10 carbon atoms or acyloxy with up to to 4 carbon atoms; also compounds in which A is for the group - 0 - R is where R is hydrogen; or those in which X is chlorine, aralkoxy with up to to 10 carbon atoms or alkoxy with up to 3 carbon atoms and A is the group -0-1? represents where R is Alkyl with up to 20 carbon atoms, aralkyl with up to 10 carbon atoms or alkenyl with up to 8 carbon atoms; or those in which X is chlorine or bromine and A is the group - S - R, in which R is ß-chloroethyl, ß-bromoethyl, Is alkyl with up to 5 carbon atoms or benzyl.

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If A represents the group - - Br, then

^X 4 IT

speak the compounds according to the invention of the general formula:

O R ^J

X ~ GE ₀ ClU -SN ^ (HI)

7th H

viorin X, R ^ and R have the above meaning

Examples of this class of invention are:

2-Br om-N- (3-hydr oxypropyl) athansulfinajnid, 2-IIydroxy-N-octylethanesulfinamide,

N-benzyl-2-ethoxyethanesulfinamide,

2-penoxyethanesulfinamide,

II-Allyl-2- (benzyl oxy) ethanesulfynamide 2- (Isopropylthio) ethanesulfinanilide, 2-Ac et oxy-N-hydroxyätiiansulfinamid, 2-Me sy 1-1ί- / ~ 2- (Me thyl thi ο) ä thyl_7ä thansul f inamid, 2- (phenylsulfonyloxy) ethanesulfinamide, 2-Nitroäi | hansulf inanilid,

N-Methox3f - 2- (dimethylamino) ethaiisulfinanilide _> '

2 ~ / ^ - (Dimethylcarbamoyl) -1-methylvinyl_7ethanesulfin-

4-tpluid4d,

N- (5-But4nyl) -2-methoxyethanesulfinamide,

- 10

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2-chloro-l? -HydrQxyäthansulfinai3id and

2- (butylamino) -N- (cyclohexyl) ethanesulfinamide.

Under the general class of compounds according to Formula I, vmrin A is the group;

represents, some species are particularly "preferred, namely those compounds in which A is the group

H represents.

In these two groups, R stands for hydrogen, aryl with up to 10 carbon atoms, alkyl with up to 20 carbon atoms, aralkyl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, cycloalkyl with up to 8 C atoms, alkoxy with up to 4 C atoms or for R ^ Y ¹ , in which R ^ are alkylene with up to 4 C atoms and Y ^{1 is} hydroxy or alkylthio with up to 3 C atoms; E can also be a substituted phenyl of the formula:

- 11 -

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- 11 -

represent,

wherein Z 'represents alkyl with up to 3 carbon atoms, alkylthio with "up to 3 carbon atoms, alkoxy with up to 3 ~ carbon atoms, Alkylsulfonyl with up to 3 carbon atoms, chlorine, bromine, Nitro or trizluoromethyl; X means chlorine, bromine, Iodine or alkylsulfonyloxy when the alkyl group is up to contains to 3 carbon atoms, with the proviso that, if X is alkylsulfonyloxy, E is hydrogen, alkyl with up to 6 carbon atoms or aryl with up to 10 carbon atoms

stands.

Examples of compounds of this class are:

2-BrOm-N- (3-hydroxypropyl) ethanesulfinamide, 2-bromo-N-octylethanesulfinamide, 2-bromo-N-benzylethanesulfinamide, 2-chloro-II-heptylethanesulfinamide, 2-bromo-oc, cx, a-trif luorethansulf in-3-toluidid, 2- (iithyl sulfonyl oxy) athansulfinamid, 2-chloro-2 '- (methylthio) athansulfinanilid, 2-chloro-3 '- (ethylsulfonyl) ethanesulfinanilide, 2-chloro-2'-bromoethanesulfinanilide, 2-bromo-N-methoxyethanesulfinamide, 2-bromo-N- (3-butenyl) ethanesulfinamide,

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2-chloro-N-propox: yethanesulfinamide, 2 ~ bromine ~ 2'-chloroethanesulfinanilide.

The compounds of this class seem to be most effective against plant growth wherein. X stands for chlorine, bromine or iodine. Preferred types of this subclass include compounds wherein X is chlorine and R stands for hydrogen, alkyl with up to 8 carbon atoms, cycloalkyl with up to 6 carbon atoms, alkenyl with up to 5 carbon atoms, aralkyl with up to 8 carbon atoms, unsubstituted phenyl or with chlorine, bromine or trifluoromethyl substituted phenyl.

Examples of this preferred subclass are:

2-chloroethanesulfinamide 2-chloro-N-heptylethanesulfinamide N-amyl-2-chloroethanesulfinamide N- (2-butenyl) -2-chloroethanesulfinami d N-phenyl-2-chloroethanesulfinamide N- (2-pentenyl) -2-chloroethanesulfinamide 2-chloroethanesulfine-4-toluidide, N-phenethyl-2-chloroethanesulfinamide.

Many of the compounds mentioned here, in particular all compounds of Formula I, in which A is the group:

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represents were not previously known. The invention therefore also includes new compounds of the formula:

X - CH ₂ CH ₂ - S - AI,

where A is for the group:

in the latter, R ^ and R, which can be the same or different, represent hydrogen or alkyl with up to 20 carbon atoms or aralkyl with up to 10 carbon atoms; and where either B? or R or both can represent R ^ Y ¹ , in which Br is alkylene with up to 4 carbon atoms and Y ^{1 is} hydroxy- or β-haloethanesulfinyloxy, in which the β-halogen substituent is chlorine, bromine or iodine, with the proviso that if Y 'is hydroxy, X represents one of the groups described above for X with the exception of A ¹ R ¹ and that, if Y ^{1 is} β-haloethanesulfinyloxy, Z is chlorine, bromine or iodine; if R ^ is hydrogen, R can also represent:

Aryl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms,

5 2 S cycloalkyl with up to 8 carbon atoms or R "i, in which Br

2
has the above meaning and Y stands for alkylthio with up to 3 carbon atoms or alkoxy with up to 4 carbon atoms; When R is hydrogen, R can also stand for a substituted phenyl of the formula:

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14 -

where Z ¹ for alkyl with up to 3 carbon atoms, alkyl -

thio with up to 3 carbon atoms, alkoxy with up to 3 carbon atoms,

Alkylsulfonyl with up to 3 carbon atoms, chlorine, bromine,

Represents nitro ^ or trifluoriaethyl; and, if Ή / is hydrogen, alkyl or aryl, R can also stand for hydroxy or alkoxy with up to 4 carbon atoms and X represents chlorine, bromine, iodine, hydroxy or alkoxy with up to 3 carbon atoms, aryloxy with up to to 10 carbon atoms, alkylthio with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms, acyloxy with up to 4 carbon atoms, alkylsulfonyloxy, in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy, nitro, Honoalkylamino or dialkylamino, in which each alkyl group contains up to 6 carbon atoms, or A ¹ R ¹ , in which A ^{1 is} oxygen and R ^{1 is} 2- (dimethylcarbamoyl) -1-methylvinyl, 2- (methylcarbamoyl) -1-: nethylvinyl. Or Is 2- (methoxycarbonyl) -1-methylvinyl. ■

A can also stand for the group - Y - R, in which Y is oxygen and RV / hydrogen, X then represents bromine, hydroxy, alkoxy with up to 3 carbon atoms, alkylthio with up to 3 carbon atoms, acyloxy with up to to 4 carbon atoms, aryloxy with up to 10 carbon atoms, alkylsulfonyloxy, in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy _t aralkoxy with up to 10 carbon atoms, nitro or mono-

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dialkylamino, in which each alkyl group has up to 6 carbon atoms contains.

Furthermore, A can stand for the group - Y - R, in which T is oxygen and E represents one of the following groups: Alkyl with 6 to 20 carbon atoms, aralkyl with up to 10 carbon atoms, alkynyl with up to 4 carbon atoms, alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms, 2- (dimethylcarbamoyl) -1-methyl-vinyl, 2- (methylcarbamoyl) -1-methylvinyl, 2- (Hethoxycarbonyl) -1-methylvinyl or ZR, where Z is alkylene with up to 4

C atoms and. R for alkylthio with up to 3 carbon atoms, Alkoxy with up to 4 carbon atoms, aralkoxy with up to 10 carbon atoms, hydroxy or a ß-substituted one Ethanesulfinyloxy radical, in which the ß-substituent is identical is with the ß-substituent represented by X in formula I, and X is chlorine, bromine or iodine.

Furthermore, A can represent the group - Y- R, in which Y is oxygen and R has the following meaning: Alkyl with up to 20 carbon atoms, aralkyl with up to 10 carbon atoms, Alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms, alkynyl with up to 4 carbon atoms, 2- (dimethylcarbamoyl) -1-methylvinyl, 2- (methylcarbamoyl) -1-methylvinyl, 2- (i-iethoxycarbonyl) -i-methyl-

P.
vinyl or ZR, where Z is alkylene with up to 4 G-

2
Atoms and R for alkyl thio with up to 3 carbon atoms, alkoxy with up to 4 carbon atoms, hydroxy or a ß-substituted ethanesulfino radical, in which the ß-substituent is identical to that represented by X in formula I.

- 16 -

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place; X then represents for hydroxy _T alkoxy with up to carbon atoms, aryloxy with up to 10 carbon atoms, aralkoxy with up to 10 carbon atoms, alkylthio with up to 3 carbon atoms, acyloxy with up to 4 carbon atoms , Alkylsulfonyloxy, in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy, nitro, mono- or dialkylamino, in which each alkyl contains up to 6 carbon atoms, or for A ¹ R ¹ , in which A 'is oxygen and R ^{1 is} 2 - (Dimethylcarbamoyl) -1-methylvinyl, 2- (Kethylcarbainoyl) -I-methylvinyl or 2- (I-ethboxycarbonyl) -1-methylvinyl represented. Finally, A can represent the group -Y- R, v / orin Ϊ means sulfur and R represents alkyl with up to 8 carbon atoms, optionally substituted by chlorine or bromine, or aralky.l, in which the alkyl group contains up to 4 carbon atoms; X is then chlorine, bromine, hydroxy, alkoxy with up to 3 Carbon atoms, aryloxy with up to 10 carbon atoms, alkylthio with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms, acyloxy with up to 4 carbon atoms, alkylsulfonyloxy, in which the alkyl group has up to 3 carbon atoms Atoms contains, arylsulfonyloxy, mitro or mono- or dialkylaminο, in which each alkyl group contains up to 6 carbon atoms.

The novel compounds according to the above formula I, in which A represents the group - X - R, can be used in divided into the following classes:

I. Sulphine acids

Compounds in which X is bron, hydroxy, alkoxy with up to f: u 3 carbon atoms, alkylthio with up to su 3 carbon atoms,

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Acyloxy with up to 4 carbon atoms, aryloxy with up to 10 carbon atoms, alkylsulfonyloxy, in which the alkyl group / Contains up to 3 carbon atoms, arylsulfonyloxy, aralkoxy with up to 10 carbon atoms, ifitro- or mono- or dialkylamino, wherein each alkyl group contains up to 6 carbon atoms; Y is oxygen and E. is hydrogen.

II. SuIfic acid first

Compounds in which X is chlorine, bron or iodine and Y is oxygen and E can stand for the following groups: alkyl with 6 to 20 carbon atoms, aralkyl with up to 10 C atoms, alkynyl with up to 4 C atoms, alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms, 2- (Dineth.ylcarbamoyl) -1 ~ methylvinyl, 2- (Hethylcarbanoyl) 1-methylvinyl, 2 ~ (hetboxycarbonyl) -1 »methylvinyl or

ρ
ZR, where Z denotes alkylene with up to 4 carbon atoms

ρ
and -E 'stands for the following groups: alkylbhio-mib up to 3 carbon atoms, alkoxy with up to 4 carbon atoms, aralkoxy and up to 10 carbon atoms, hydroxy or a ß-suboti buierten ibhansulfinyloxyest, v / orin der ß-substituent with the ß-Sub.sbitueriten represented by X in i'oriael I. idea bisch isb.

Furthermore, compounds in which X has the following meanings

hab: hydrox'oxy, alkoxy inLb to ku 5 C-Abomeri, aryloxy nit bit; to 10 carbon atoms, aralkoxy r.ib up to 10 carbon atoms,

Alk./lthio mib up to J O-Atoneri, Acyloxy nib "up to

4 G-Atji.'ien, AlkyLnulfon; / loxy _} viorin the alkyl group bio

to 3 C-Λbone enbhäl / b, kry] j'ni £ onylozzj ^ liiUro, lioiiu-

odor i- ^; -: il kyi amino, v / cu-iu J · ..: '!: ^ Uz. / ircv.i.fj-j Ί · ί: ι? .α 6 ν, _- ^ \: ο:

2 ü VJ> i U 4 / Ui 'μ BAD ORfG] NAL

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- IS -

contains', or A ¹ H ¹ , where A ^{1 is} oxygen and R ^{1 is} 2- (diraethylcarbamoyl) -1-methylvinyl, 2- (diethylcarbamoyl) -Ί-methylvinyl or 2- (nethoxycarbonyl) -1-diethylvinyl be; Ϊ stands for an oxygen atom and E has the following meanings: alkyl with up to 20 carbon atoms, aralkyl with up to 1Ü carbon atoms, alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms, alkynyl with up to to 4 carbon atoms, 2- (dimethylcarbamoyl) -1-methylvinyl, 2- (riothylcarbanoyl) -1-methylvinyl, 2- (Hethoxycarbonyl) - '! methyl vinyl or ZR ¹ T, where Z is alkyl ene

p with up to 5 carbon atoms and 11 " for alkylthio with" up to

to 3 C-Aboaen, alkoxy with up to 4 C-atoms, aralkoxy with up to 10 G-atoms or one ß-substituted one Ethanesulf inoresb, in which the ß-substituent is identical is with the ß-substituenton represented by X in formula I, stand.

111. Tlii ο su 1.f insäure ο s t c l *

Compounds in which X stands for chlorine, bromine, hydroxyl, alkoxy KL t ^) In to :> C atoms, aryloxy with up to 10 carbon atoms, alkyl, thio with up to 5 carbon atoms, aralkoxy with up to 10 C atoms, Asyl oxy with up to ^L V C atoms, Alk'yLtHiiiVinylo. ::, /, in which the alkyl ^ rupric JS contains CA tome, kvj !. ru 1. t'onyl oxy, Hitro or Hono- or Dialkyl Qiü. uo, wo rhi, any alkylt; doll up to 6 carbon atoms tuiiifilb, wiihreud Y L - ^ .'- CeL bed tub ü and R Γϋι> alkyl with bu; 'Mi i'i O- ^ tj-iun, f; ir; t: benorii "aLLf; substituted with C: ii:.> I? Fr.iur * i'r ·· * -; o ^! ' R · ^ f.-i ι.;: .- / !, vx-rln die / llkyl ^ runpe bi ^ l -J- / u: ^ :: r-. -1; 11. i \ t ί, .-; ί · Ί:.

;, .ι Ι

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Particular examples of these novel compounds include:
2-Isopropoxyätliansulfinsäure
2-I? Ormylethanesulfinic acid,
2-phenoxyethanesulfinic acid,
2- (methylthio) ethanesulfinic acid, 2- (benzyloxy) ethanesulfinic acid, 2- (mesyloxy) ethanesulfinic acid,
2- (tosyloxy) ethanesulfinic acid,
Octyl-2-bromoethanesulfinate,
Allyl-2 ~ iodethanesulfinate,

3- (propylthio) propyl-2-hydroxyethane sulfinate, 2- (Mmethylcarbamoyl) -1 ~ methylvinyl ~ 2-phenoxy ~ ethansulXinate,

2- (2-acetoxyethanesulfinyloxy) ethyl-2-acetoxyethanesulfinate, -

Methyl 2-nitroethanesulfinate, S- (s-butyl) -2-methoxyethanthiosulfinate, S- (3-pentyl) -2-pheiioxyäthanthiosulfinat and S-benzyl-2-acetoxyethanthiosulfinate.

Within this general class of novel compounds, certain species of soxfohl in are suitable Both the acid and the ester subclass are particularly good at influencing and regulating vegetation. In this regard, compounds of the formula I are preferred in which X is bromine, chlorine or alkoxy with up to 3 carbon atoms and A for the group - 0 - E, wherein: R has the following meaning: alkyl with 6 to

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Carbon atoms, alkynyl with up to 4 carbon atoms, alkenyl with

up to 8 carbon atoms, aryl with up to 10 carbon atoms,

ρ
or ZE, where Z is alkylene with up to 4 carbon atoms

2
and E for alkylthio with up to 3 carbon atoms and

Alkoxy with up to 4 carbon atoms or hydroxyl; means

2
X chlorine, R can also be a ß-chloroethanesulfinyl

oxyrest represented. Very excellent effects are obtained with compounds according to formula I in which X stand for Broia and A for the OH group.

Particular examples of novel compounds in the sulfinic acid subclass include:

2-methoxyethanesulfinic acid, 2-ethoxyethanesulfinic acid, 2- (butyryloxy) ethanesulfinic acid, 2-acetoxyethanesulfinic acid, 2- (benzyloxy) ethanesulfinic acid and 2- (furfuryloxy) ethanesulfinic acid.

iSpecific examples of novel compounds in the »sulfinic acid ester subclass include:

Phenethyl-2-chloroethanesulfinate, FIe thy 1-2- (benzyloxy) ethanesulfinate, Ally 1-2- (phenethyl oxy) ethanesulfinate, benzyl 2- (benzyloxy) ethanesulfinate, Amyl 2-chloroethanesulfinate, 3-butenyl-2-chloroethanesulfinate,

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Allyi-2-methoaqrathansulfinat, Decyl-2-ethoxyethanesulfinate,. -

Benzyl 2-propoxyethanesulfinate and 3-pentenyl-2-isopropyl oxyethanesulfinate.

Particular examples of novel compounds from the thiosulfuric acid ester subclass include:

S- (2-0hloräth.yl) -2-chloräthanth.iosulfinat, S-isopropyl-2-chloroethanthiosulfinate, S-benzyl-2-chloroethanthiosulfinate, S ~ (2-bromoethyl) -2-bromoethanthiosulfinate and ß-Benzyl-2-bromoethanthiosulfinate.

The compounds of the invention can be applied to seeds before sowing or to the soil surrounding the plants or to plants before or after emergence in order to modify growth and / or regulate ZiL; if necessary, they can also be applied to the ripening of the harvested. To stimulate, regulate and / or modify parts of plants. For their use, the compounds according to the invention, which are either solid or liquid at ambient temperature, can be prepared in a manner known per se, for which purpose additives and / or modifying agents known in agricultural chemistry can optionally be used. Preparations are made

to © -
in the form of wettable powders, granules, pellets,

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Solutions, emulsifiable concentrates, emulsions or pastes.

For use for plants during or after growth, preparations are preferably used which supply the plant with the active ingredient in liquid or paste form. These "preferred preparations thus include" wettable powders, solutions, emulsifiable concentrates, emulsions and pastes. Wettable powders are water-dispersible preparations which contain the active ingredient in a proportion of 10 to 90% and in addition an inert solid carrier, for example a natural clay or a synthetic mineral filler, such as that obtained from silica or silicate. Optionally, these wettable powders can also contain 3 to 10 % of a dispersant and, if necessary, 0 to 10 % stabilizers and / or other additives, such as agents to facilitate the introduction or adhesives. The term "solution" means both aqueous and non-aqueous solutions of the compounds according to the invention. Some of them are water soluble and can be applied in aqueous solution at a concentration of up to 10%. Other compounds according to the invention are less or hardly soluble in water, but have better solubility in non-aqueous solvents and can be prepared and used at concentrations of up to 0%. The emulsifiable concentrates which can be used according to the invention usually contain, in addition to the solvent, and

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optionally an auxiliary solvent, 10 to 50% (w / v) active ingredient, 2 to 20 % (w / w aoI.) emulsifiers and 0 to 20 % corresponding additives, such as stabilizers, penetrants and corrosion inhibitors. The pastes are prepared in such a way that a stable, mobile product is obtained and usually contain 10 to 60 % active ingredient, 2 to 20 % additives and. as a carrier water or an organic liquid in which the active ingredient is essentially insoluble.

Solid preparations of the compounds according to the invention may be desirable for use over the entire growth period, ie immediately when planting or in the early stages of growth or for other specialized types of application. Such solid preparations are dry, dust-like masses, granulates and pellets. The dry dusty powders usually correspond in their composition to the wettable powders, but without dispersants and normally contain 0.5 to 10% active ingredient. The powdery agents can also be prepared as concentrates, which are then usually diluted with solid titanium substances before use outdoors with the help of an appropriate mixing device. Granules and pellets are usually produced so that their grain size is between 0.13 and 1.3 mm, their production being carried out with the aid of the known methods of agglomeration, compression or impregnation. In general, the granules contain about 0.5 to 25 % active ingredient in addition to additives such as stabilizers,

- 24 2098 84 / U20

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- 24 -

Retardants, binders, etc. (The percentages here always mean% by weight).

In order to influence the effects described above " and to achieve modification of the vegetation, The agents according to the invention can be applied directly to the plant fruit, seeds, or leaves can be applied to the surrounding soil or to leaves and soil at the same time. The intensity of the application depends on the method used and other factors, such as the active ingredient itself, the preparation used in each case, the type of plants coming into Fx ^ age, the wax turns stage of the The latter and the type of effect as well on local conditions, e.g. temperature, air and soil humidity, chemical composition of the soil and the like. For outdoor plants in In a normal environment, amounts between 0.06 and 24 kg / ha are generally suitable for the growth of the plant breed to influence in the desired sense. For most purposes the preferred amounts are between 0.12 and 6.0 kg / ha. For use on the pea fruit or the harvest can be the applied amount between 1 and 20,000 ppin (parts per million, calculated on the total fruit weight), whereby n from 100 to 4,000 ppm are preferred.

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The above-described compounds according to the invention according to formula I, in which A represents the group -X-R, can be prepared as follows:

I sulfinic acids

The B-substituted ethanesulfinic acids, in which the ß-Subsktuent I a halogen (chlorine, bromine or iodine), the alkylsulfonyloxy, Arylsulfonyloxy, nitro, alkoxy, acyloxy, Aryloxy or aralkoxy group can be prepared by reaction of a ß-substituted Ethanesulfinyl chloride of the formula IV:

(IV)

wherein X is one of the groups mentioned above, with water, This Realction is usually in an inert organic solvents, such as ether, and the by-product hydrogen chloride, which is produced in the reaction is best removed by bubbling oxygen through the reaction mixture.

The B-substituted athansulfinic acids, in which the ß-X carbon the ethane group is bonded to nitrogen or sulfur, i.e. where X is a mono- or dialkylamino- or alkylthio group can be prepared

- 26 -

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26 -

the with the help of conversions that the ring burst of Athylenepisulfon with barium hydroxide are analogous (see G. Hesse et al, Ghem. Ber., 90, 2106 (1957) »With help this method can be two (mono- or dialkylamino) ethanesulfinic acids be prepared by reacting a primary or secondary amine with ethylene episulfone; on the other hand, if one wants to produce athenesulfinic acids which are substituted in the 2-position with alkylthio groups alkyl mercaptan and ethylene episulfone are suitable reactants. This leads to reactions it is advisable to use an inert solvent, like ether, through.

2-Hydroxyethanesulfinic acid, the sulfinic acid, in the X represents the hydroxyl group can be produced from the barium salt of 2-hydroxyethanesulfinic acid by means of Acidification and removal of the barium union with the help of an acidic ion exchange resin, such as Amberlit IRC-5Q -Aß or Dowex 5OV / or with sulfuric acid. From the resulting aqueous solution, the free acid is then isolated by lyophilization. The barium salt of 2-Hydroxyäthansulfinsäure is a known compound and can be prepared according to the method described in the above reference (G. Hesse et al. Cheni. Bei '., 90, 2106 (1968).

2. Sulphic acid ester

Many of the ß-substituted ethanesulfinic acid esters described above, especially those in which X is halogen (chlorine, bromine or iodine), alkoxy, acyloxy, aryloxy, aralkoxy,

_ 27 -

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Is aryl sulfonyl oxy, alkyl sulfonyl oxy or nitro and where R is alkyl, alkenyl, alkynyl, alkylthioalkyl, Alkoxyalkyl, aralkoxyalkyl or halogenated alkyl can be prepared by reacting a ß-substituted Äthansulfinylchlorides of the formula ¥ with a hydroxy compound according to formula VI, as from the Equation I below shows:

: 0 0

X-CH ₂ CH ₂ J-Cl + "ROH * X-CH ₂ CH ^ OR _Gleichim g ι

V VI

wherein X and R have the meaning set out in more detail above. This reaction is carried out advantageously in an inert solvent such as ether, and at reaction temperatures below Umgebungstemperatui. ¹ Because of the highly reactive nature of the sulfinyl chloride, the reaction is preferably carried out in an inert (nitrogen) atmosphere.

The esters of ß-substituted ethanesulfinic acid, wherein X has the above meaning and R is aralkyl or aryl can be prepared by reacting one Metal salt, e.g. the sodium, potassium or thallium salt a hydroxyl compound of the formula VII with a ß-substituted ethanesulfinyl acid chloride, as shown in Equation II. The reaction is expediently carried out in an inert solvent, like ether or benzene and carried out in an inert atmosphere.

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O O

T t

X-CH ₂ CH ₂ S-Cl + ROM> X-CH ₂ CHgSOR + MCl

Equation II

The esters of ß-substituted ethanesulfinic acid in which the ester group has a "vinyloxy character, ie in which E is 2- (mono- or dimethylcarbamoyl) -1-methylvinyl or 2- (methoxycarbonyl) -i-methylvinyl" and in which the ß-substituent , X, the same as in the esters prepared according to equation ~ ' _r Ϊ above, can be prepared by reacting a metal salt of the corresponding acetoacetic acid amide or ester, for example the thallium or silver salt (formula VIII) with a β-substituted ethanesulfinyl chloride the JPorrael V. This eeaction can be represented by equation III:

ZO-CH-O-CH ₅ + X-CH ₂ CH ₂ -O-Cl? XC ^ CHgsWoi-C-5

CH-, VIII V 5

wherein Z is methoxy, monomethylamino or dimethylamine and M is a metal ion, e.g. a thallium or silver ion, is. The reaction is expediently carried out in an inert solvent such as tetrahydrofuran, in uel-

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brazen that as. Occurring by-product of the reaction .MetallSälz is only slightly soluble, so that the metal is easily can be recovered for reuse.

The ß-substituted ethanesulfinates, in which the ß-substituent "is a group of the yinyloxy type, ie in which Σ is A ¹ E ', where A ^{1 is} oxygen and E' is 2- (mono- or dimethy lcarbamoyl) -1-methylvinyl or 2- (Ke thoxyearbonyl) -1-methyl vinyl can be prepared by reacting a 2-chloroethanesulfinic acid ester with a metal salt of an acetoacetic acid amide or ester according to iOrmel VIII above. The reaction is expediently carried out in an inert solvent such as ether or tetrahydrofuran.

According to. Equations I, II and III above 2-Ghloräthansulfinate can also be used as a starting material serve for the synthesis of the 2-hydroxyethanesulfinates according to the invention. Ground in this synthesis the 2-Hydroxyäthansulfinate produced by reaction their 2-chloro analogues with silver hydroxide. The reaction is expediently carried out in ether, whereby the Silver hydroxide is generated in situ by the action of moist ether on silver oxide.

The ß-substituted ethanesulfinates, in which X is alkylthio, Monoalkylamino or dialkylamino can be used with a two-step synthesis from the 2-chlorathanesulfinates getting produced. In the first stage, a 2-chloroethane prepared according to equation I ^ II or III

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sulfinate by the action of an organic "basic Catalyst, such as triethylamine, to form an ethensulfinate dehydrochlorinated. The reaction is expediently iä. an inert organic solvent such as benzene ^ carried out, adding sufficient base to the reaction mixture to remove the by-produced hydrogen chloride to record. In the second action stage, this will be : Intermediate product ethene sulfinate reacted with an alkyl mercaptan or a mono- or dialkylamine, so that the desired β-substituted ethanesulfinate is obtained. The reaction is usually carried out in an inert organic solvent, which is preferably the same as that used for the dehydrochlorination carried out.

III. Thiosulfinic acid esters

The ß-substituted ethanthiosulfinates, wherein X Halogen (chlorine, bromine or iodine), alkoxy, aryloxy, aralkyloxy, acyloxy, arylsulfonyloxy, alkylsulfonyloxy or denotes nitro and in which R denotes an alkyl or aralkyl group, can be prepared with the aid of a 4-step synthesis scheme, using as starting material a bis (ß-substituted ethyl) disulfide of the formula X used:

(XCH ₂ CH ₂ S-) ₂ (IX),

where X has the above meaningj the disulfides according to l? orrael IX

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are identical to the bis (ß-substituted ethyl) disulfides, which are used to produce the bis-substituted ethanesulfenyl chlorides in the above-described sulphine production. In the. first stage of the four-stage sequence \ cLrd the Bi s- (ß- substituted ethyl) disulfide according to Foriael IX reacted with molecular chlorine,

. 'being in a halogenated alkane solvent such as Chloroform, works. A ß-substituted ethanesulfenyl chloride according to formula X is obtained:

XCH ₂ CH ₂ -S-Cl (X)

In the second stage v / ß-substituted ithanesulfenyl chloride according to formula X reacted with phthalimide and an N- (ß-substituted ethylthio) phthalimide is obtained Formula XI:

N-SCH ₂ CH ₂ -X

(XI) Ö

The reaction is expediently in an inert Solvent carried out, such as dimethylformamide. The intermediate according to formula XI is then reacted with a mercaptan of the formula XTI:

E-SH (XII),

-

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\\ Torin E is alkyl or Ar alkyl, so that one is a Msulfide according to formula XIII contains:

(XIII)

The reaction carried out according to one of K.S. Boustany and A.B. Sullivan, Tetrahedron Letters, 354-7 (1970) ^ e wrote en general method is expediently carried out in an "inert organic solvent such as benzene. In the final stage of the four-step process, a disulfide of the formula XII is mixed with metachloroperbenzoic acid to the corresponding ß-substituted ethanthiosulfinate implemented. This Eeaktion, which according to one of A. Schoberl and A. Wagner, Methods of Organic Chemistry, 9} 691 (1955) is the technique described expediently in a chlorinated alkane, such as chloroform, carried out as a solvent.

The ß-substituted ethanthiosulfinate, in which the ß-substituent X is mono- or dialkylamino or alkylthio, can be prepared with H ^ .lfe in a four-step process which is somewhat analogous to that described above for other β-substituted atanthiosulfinates. Here, a bis-disulfide of the formula XIV:

E-S-S-E (XIV),

where E is alkyl or aralkyl, in a halogenated alkane, such as chloroform, as a solvent with -molecular Chlorine reacted, εο that one alkyl or aralkylsulfenyl

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Chloride of formula XV is obtained;

HSCl (ZV) ι

which is an intermediate sulfenyl chloride then reacted with phthalimide ". This as an intermediate accruing sulfenyl chloride is then added with phthalimide a Jf-substituted phthalimide of the formula XVI reacted; -

OTD

The Eeaktian is expediently in an inert Solvent such as dimethylformamide * carried out. In the third stage of the process, 'that is called product obtained N-substituted phthalimide "implemented with a ß-substituted ethyl meroaptan of the formula XVII:

X-CH ₂ OH ₂ -SH. (XVII)

wherein X is mono- or Malkylamino- or Ethylthiq, so that a disulfide of formula XVIII is obtained;

■; '-X-CH ₂ CH ₂ SSR:;. ■ (XVIII)

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The reaction is two-way in an inert aromatic solvents such as benzene. In the final stage, a disulfide of the formula XVIII is used Metachlorobenzoic acid to your desired thiosulfinic acid ester implemented. The output stage is also expedient carried out in a halogenated alkane such as chloroform as a solvent.

The ß-substituted ithansulfinamides (d, h, the compounds according to formula I, in which A is the group;

represents, in which the Aciidsatierstoff unsubstituted and the ß-substituent X is chlorine, bromine or iodine, alkoxy, acyloxy, aryloxy, aralkoxy, alkylsulfonyloxy, Arylsulfonyloxy or Hitro means), can be prepared v / earth, by reaction of a ß-substituted JLthanesulfinylchlorides the formula

X-CH ₂ GH ₂ -S-Cl (XIX)

where X has the above meaning, with anhydrous Ammonia. The reaction is expediently anter nitrogen in an anhydrous solvent, such as anhydrous

~ 35 -

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- 35 -

Ether, carried out. It has been found to be useful that sulfonyl chloride is added dropwise to a solution of Add ammonia in anhydrous ether, keeping the solution at -10 to -40 °. In this way the reaction can normally be fully carried out in the time that is necessary to remove the sulfinic chloride. to admit plus the time it takes to bring the reaction mass to ambient temperature by natural convection bring to. The N-monosubstituted and the Ν, ϊί-disubstituted ethanesulfinamides can be used in an analogous manner according to formula I, in which X is one of the abovementioned Is substituents, but with the exception of those compounds wherein the amide nitrogen with a β-haloethanesulfinyloxyalkyl group is substituted, are prepared by reacting a sulfine chloride according to IOrmel XIX above with a primary or secondary amine the formula XK:

(XX)

wherein R- ^ and R is one of the groups mentioned in formula I for R ^ and R except ß-haloethanesulfinyloxyalkyl. This reaction is carried out anolog the above-described preparation of unsubstituted amides, wherein applying the same reaction conditions.

The ß-substituted ethanesulfinamides, in which the ß-substituent is a group of the vinyloxy type, e.g. in which XA ^{1 is} R ¹ -, where A ^{1 is} oxygen and R ^{1 is} 2- (methylcarbamoyl) -1 -methylvinyl, 2- (dimethylcarbamoyl) -1-ethyl-

- 36 -

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is vinyl or 2- (Methoxycarbcnyl) -1-methylvinyl, can be produced by implementing the appropriate 2-Chloräthansulfinairiides, prepared as above, with a metal salt of the corresponding acetoacetic acid amide or ester, e.g. the thallium or silver salt according to formula ZZI:

0 OM

ZC-CH = C-CH ₃ - (XZI),

wherein Z is methoxy, monomethylamine © or dimethyl amino represents and M represents a metal ion, e.g. a thallium or silver ion. The reaction is expedient carried out in an inert organic solvent such as ether or tetrahydrofuran.

The P-haloathanesulfinamides prepared as above can axich as starting material for the synthesis of 2-Hydroxyäthansulfinamide according to the invention are used. The latter are produced by reacting their 2-halogen analogs with silver hydroxide. The reaction is expediently carried out in ether, with the silver hydroxide in situ by the action of moist Ether is produced on silver oxide.

The ß-substituted ethanesulfinamides, where Z is alkyl

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thio, monoalkylamino or dialkylamino, can from the 2-Chroräthansuifinamiden with the help of one two-step process can be produced. In the first stage, a chloroethanesulfinamide prepared as above is used with the aid of an organic base as a catalyst, such as triethylamine, is dehydrochlorinated to form the ethensulfinamide. The reaction is conveniently carried out in an inert organic solvent such as benzene, with so much base is used that this is the by-product absorbs formed hydrogen chloride. In the second stage the Äthensulfinamid formed as an intermediate is reacted with an alkyl mercaptan or a mono- or Dialkylamide, so that the desired ß-substituted Äthansulfinamid receives. One works expediently in an inert organic solvent, which is preferably is the same as that for dehydrochlorination was used.

The ß-position halogen-substituted ethanesulfinamides, in which the amide nitrogen is substituted with a ß-haloethanesulfinyloxyalkyl group can be prepared are made by reacting a ß-Halogenäthansulfinamides, wherein the amide nitrogen is substituted with hydroxyalkyl, with a ß-haloethanesulfinyl chloride of the formula XIX above. It is advisable to work in an inert atmosphere, e.g. in nitrogen, and in an anhydrous one Solvents, such as anhydrous ether.

In the following examples both the manufacture like the use of the compounds according to the invention

- 38 -

a ü ο β ü λ / ι.no

1A-41 599

illustrate, parts by weight and parts by volume are in the same ratio as the kilogram to the liter. The structure of the compounds was confirmed in all cases by infrared spectrum, nuclear magnetic resonance, optical spectrum and elemental analysis.

In the following examples, "w" means parts by weight and "v" vol .- (parts.

Example 1

2-chloroethanesulfinic acid

Cl-CH ₂ CH ₂ -S-OH

Bis (2-chloroethyl) disulfide was oxidatively chlorinated as follows according to the general method of IB Douglass and EV Eorton, Journal of Organic Chemistry, 33 ₅ 2104 (1968): Bis (2-chloroethyl) disulfide (38.0 w) was' e abandoned in a reaction kettle »containing glacial acetic acid (24.0 ν;) and the mixture was cooled to 10 °. ¹ Chlorine gas was introduced into the cooled solution at such a rate that the reaction mixture was maintained at approximately 10 °. The addition of chlorine was continued until the deep orange color of the reaction mixture disappeared. The solution was then distilled under reduced pressure and a clear liquid was obtained, 2-chloroethanesulphinyl chloride (50.4 w), b.p. 81 to under reduced pressure (12 torr).

'1A-41 599' - 39 -

To a solution of 2-chloroethanesulfinyl chloride, < in ether (250 v) vnirde water (3.6 w) was added in one portion. The reaction mixture was left at room temperature for 1 hour held with a vigorous stream of nitrogen passed through vnirde. ! Laughs at the end of this time the reaction solution was concentrated to a colorless liquid (26.4 w) by distillation in vacuo. Another Purification of this liquid by molecular distillation

ο —4

at 73 and 1 x 10 Torr resulted in a colorless one

viscous oil, 2-chloroethanesulfinic acid (14.5 w).

Example 2

(2-ethyl) hexyl-2-chi ο rä thansul f inat

0 t.

According to Example 1 was prepared, with stirring, 2-Chloräthansulfinylchlorid (16.2 w), cooled to -5 to -30 ⁰ C and treated under nitrogen at m ο spliäre dropwise ait 2-ilthylhexanol (13.0 \ r). After everything had been added, the external cooling was removed and the reaction mixture was allowed to stand at room temperature for 16 h. Distillation through a 2 cm Vigreux column gave a clear white liquid, (2-ethyl) hexyl-2-chloroethanesulfinate (14.7%); Bp 110 to 112 ° under reduced pressure (0.3 Torr).

. - 40 -

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Example 2.

Butyl-2-chloroethanesulfinate Cl-GH ₀ GH ₀ S-OO ,, H _n

et d. H-y

2-chloroethanesulfinyl chloride (16.2 w), prepared according to Example 1 was dissolved in dry ether (130v) and the solution cooled to -15, whereupon normal butanol was added dropwise under a nitrogen atmosphere became. After everything had been added, the reaction mixture was allowed to warm to room temperature and it was driven Solvent off by vacuum distillation. A colorless liquid, butyl 2-chloroethanesulfinate, was obtained (18.5 w) ..

Example

2- (chloroethanesulfinyloxy) ethyl-2-chloroethanesulfinate O O

To a solution of 2-Ohiorethansulfinylchlorid (14.7 w) prepared according to Example 1, in dry ether (40 v) was ethylene glycol (6.2) dropwise under Nitrogen atmosphere and added with stirring, wherein the temperature was kept at -20 ° by external cooling. After everything was added the reaction was allowed to take place mixture to warm to room temperature and drove the

- 41 -

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! solvent through. Vacuum distillation a "b. Examination of the residue by gas-liquid chromatography revealed more than one main component. The residue was then redissolved in dry ether (200 V) and further with 2-chloroethanesulfinylochloride (14.7 ^VJ ) ^w ^ ^e Treated above. Using the same procedure as above, an oily residue was obtained, which after purification by molecular distillation (in a wiped film molecular still) as a colorless liquid 2- (GhI ο advises hansul f inyl oxyXthyl-2-chloroethanesulfinate (8.5 w) yielded; bp. 110 to 115 ° unfer

—4 reduced pressure (1 χ 10 "~ iPorr).

Example 5

2- (ethylthio) ethyl-2-chloroethanesulfinate 0

To a solution of 2-chloroethanesulfinyl chloride (14.7 Vi) in dry ether (200 v}, 'the under nitrogen atmosphere was kept at about -10 °, slowly became a solution of ethyl 2-hydroxyethyl sulfide (10 6 w) in dry ether (50 v) added, after that, the reaction mixture on Warmed up to room temperature, it was evaporated under reduced pressure. The remaining oil was sent through a still for molecular distillation and obtained 2- (ethylthio) ethyl-2-chloroethanesulfinate (15> 4 · w) with a b.p. of 95 to -100 ° under extended pressure (1 χ 10 "*" Torr).

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Example 6

Phenyl 2-chloroethanesulfinate

.Cl-GH ₀ CH ₀ -SO-

A suspension of thallium (l) phenoxide (28.6 w) in dry ether (100 v) was rapidly treated with 2-chloroethanesulfinyl chloride, prepared according to Example 1. The slurry was stirred vigorously for 1 h at room temperature with exclusion of moisture. The thallium (I) chloride was filtered off and after evaporation of the ether solution obtained as ^ iltrat an oil remained, which after molecular distillation in a "wiped film" device at 70 to 75 ° (1 χ ΙΟ "" ⁴ "Torr) Phenyl-2-chloroethanesulfinate (122 v /) resulted as a mobile liquid.

Example 7

With the aid of the procedure used in the preceding examples, the following were others according to the invention Connections made:

I:

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1A-41 599 0 TABLE I. 0 X-CH ₂ CH ₂ SYR 0 R. X 0 -CH ₅ Fp. Or Kp. In ⁰ ° C
(Torr) Cl 0 -CHgCH ₃ 74 - 76 (4.0) Cl 0 -CH (CH ₃ ) g 62 - 64 (Ο.75) Cl 0 64 - 67 (Ο.15) Cl 0 -CH ₂ (CHg) ₆ CH ₃ 55 - 60 (1 χ 10 ~ ⁴ ) Cl 0 -CH ₂ (CHg) ₁₀ CH ₃ 116 -117 (Ο.25) Cl O -CHg (CHg) ₁₄ CH ₃ not determined Cl 0 -CHg (CHg) ₁₈ CH ₃ 27-29 Cl 0 -CH ₂ - ^ J) 48-49 Cl 0 -CH ₂ CH = CH ₂ not determined Cl 0 -CHgC ^ CH 70 - 75 (1 x ΙΟ "" ⁴ ) Cl 0 -CH ₂ CH ₂ O (CHg) ₃ CH ₃ . 80 - 85 (l χ ΙΟ " ⁴ ) Cl 0 -CHgCH ₂ -OH 70 - 75 (1. x ΙΟ " ⁴ ) Cl 0 -CH ₃ not determined Br -CH ₂ (CHg) ₄ CH ₃ 58 - 60 (O.JO) Br -CH ₃ 85 - 90 (1 χ ΙΟ " ⁴ ) ^ \ J w Xl ^ fc -CH, 44 (0.15) -OCCH, not determined

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- 44- -

Example 8 2-chloroethanesulfinamide

O H

Bis (2-chloroethyl) disulfide was used according to the general Method of I.B. Douglass and R.V. Norton, Journal of Organic Chemistry, 33, 2104 (1968) oxidatively as follows chlorinated: bis (2-chloroethyl) disulfide (38.0 w) was into a real barrel filled with glacial acetic acid (24.0 w) given up and the mixture cooled to 10 °. Ch.lo.rgas was introduced into the cooled solution at a rate at which the reaction mixture remained at about 10 ° C. The addition of chlorine was continued until the deep orange The color of the reaction mixture disappeared. Then the Dissolve, distilled under reduced pressure, and obtained a clear liquid, 2-chloroethanesulfinyl chloride (50.4 w); Bp 32 to 84 under reduced pressure (12 i'orr).

2-chloroethanesulfinyl chloride (22 w) was added dropwise under Stir to a solution of anhydrous ammonia (5.1 w) in dry ether (150 v) added under a nitrogen atmosphere was kept at -40 °. After the mixture reached room temperature, it was filtered and the filtrate was evaporated to dryness by vacuum distillation. The residue from evaporation of the filtrate and the filter cake were both extruded with dry acetone. The extracts were combined and the solvent through

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Vacuum distillation driven off - awake recrystallization of the residue 'from dry acetone gave a white solid, 2-chloroethanesulfinamide (7.2 w), Mp. 78 "to 80 °.

Example 9

2-chloroethanesulfinanilide

Cl-GH ₀ CH ₀ SF - //

d. C. ι

2-chloroethanesulfinyl chloride prepared according to Example 1 (29 »4 v;) was added dropwise with stirring to a solution of freshly distilled aniline (57 »2 w) in dry Ether (400 v) added, taking under a nitrogen atmosphere and worked at a temperature between -10 and 0 °. When everything was done, that was left Warm the reaction mixture to room temperature and filtered it. After evaporation of the filtrate in vacuo, a white pesticide remained, that of toluene-hexane recrystallizes vrarde and turns out to be 2-chloroethanesulfinanilide (21.0 w) with a m.p. 78 to 80 °.

Example 10

N-benzyl-2-chloroethanesulfinamide 0

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- 46

2-Chlaräthansulfinyl ~ prepared according to Example 1 chloride (7j4 w) was added dropwise to a solution of Benzylamine (10.7 w) in dry ether (130 v) added, \ * obei under a nitrogen atmosphere and from -10 to 0 ° was worked. After the reaction mixture Ambient temperature, it was filtered and the filtrate evaporated in vacuo. It stayed a solid residue which, after recrystallization from toluene-hexane, turns into N-benzyl-2-chloroethanesulfinamide (6.0 w) from pp. 54 to 55 °.

Example 11_

2-chloro-H- (2-hydroxyethyl) ethanesulfinamide

-S-N

To a solution of 2-aminoethanol cooled to -5 (12.2 w) in dry ether (JOO v) was added dropwise with stirring 2 ~ chloroethanesulfinyl chloride (14.7 g)> produced according to Example 1, under a nitrogen atmosphere added. After the reaction mixture had warmed to room temperature, it was filtered and the filtrate concentrated by vacuum distillation. The residue was purified by a molecular distillation device and 2-chloro-N- (2-hydroxyethyl) ethanesulfinamide was obtained

- 47 -

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(1.9 w); 160 ° bp under reduced pressure (Vx 10 "Torr).

Example 12

2-chloro-N- (2-ethylthioethyl) ethanesulfinamide

OH ■ -,

f / V.

2-chloroethanesulfinyl chloride (3.7 w), prepared according to Example 1, in dry ether (50 v) was under a Nitrogen atmosphere and with stirring a solution of freshly distilled 2-aminoethylethyl sulfide (5.3 w) ' in dry ether (100 v) added, the reaction mixture being kept at -35 °. After that The reaction mixture had warmed to room temperature, it was filtered and the solvent removed from the filtrate Distilled off under high vacuum at room temperature. Kan received 2-chloro-N- (2-ethylthioethyl) ethanesulfinamide (4.0 w).

Example 13,

2- (Kethylsulfinyloxy) ethanesulfinacid

Bis (2-hydroxyethyl) disulfide is prepared by adding 30% hydrogen peroxide (503 w) to 2-mercaptoethanol (624 w) at 55 to 60 ° in the course of 2 hours. After cooling, the reaction mixture is stirred for a further 16 hours at room temperature. The crude product (577 w) was isolated by stripping off the water at 100 and 20 torr.

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1A-41 599

became. The bis (2-hydroxyethyl) disulfide (30.8 w) and triethylamine (40.4 w) prepared as above were dissolved in Iiethylenechlorid (400 v) and the solution was methanesulfonyl chloride (45.8 v. ^R ) in methylene chloride (60 v ) added dropwise under an inert atmosphere. The exothermic reaction was kept in check by external cooling so that the reaction mixture "remained at 20 to 25 °. After standing for 48 hours at room temperature, it was filtered and the methylene chloride solution filtered off was washed with water, dried over magnesium sulfate and evaporated under reduced pressure. Man received bis / "2- (methylsulfonyloxy) ethyl_7disulfide (39.0 w) as an oil.

The crude bis / ~ 2- (methylsulfonyloxy) ethyl_7disulfid oil, prepared as above, was carried out according to I.B. Douglass and R.V. Norton, Journal of Organic Chemistry, 33, 2104 (1968) oxidatively chlorinated, the procedure being carried out as in Example 1, but without the product being distilled; rather, the volatile impurities were evaporated under reduced pressure at room temperature and 2- (methylsulfonyloxy) ethanesulfinyl chloride was obtained than oil.

With the 2- (methylsulfonyloxy) ethanesulfinyl chloride prepared as above (10.3 w) was a solution of anhydrous ammonia (1.7 w) in methylene chloride (200 v) added dropwise at -20 ° under a nitrogen atmosphere. Afterwards the reaction mixture assumed room temperature it was evaporated in vacuo and the residue extracted with dry acetone. When the

- 49 -

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Acetone extract left an amber-colored oil, that crystallized when standing,.! fold. Recrystallize from methylene chloride petroleum ether one obtained light brown solid, 2- (methylsulfonyloxy) ethanesulfin amide (2.0 w), melting point 64 to 65 °.

Be is ρ ie 1 14

The above examples were worked and obtained with appropriate starting materials, the following compounds according to the invention:

TABLE II:

- 50 209884/1420 '

- 50 - CH ₃ 223U63 1A-41 599 • TABLE II ητι f nu \
v / Xl \ ν / Π-jr / p -C (CH ₃ ) ₃ 0 R ¹
a. • -CH (CH ₃ ) (C ₂ H ₅ ) Pp. Or Kp. In ⁰ C (Torr)
H. ■■ ',,, X-GH ₂ CH ₂ SN <^ 2 -CH ₂ (CH ₂ ) ₂ CH ₅ 85 (2 χ 10 *)
95-100 (1 x 10 ") R ¹ ■ -CH ₂ (CH ₂ ) ^ CH ₃ 90-100 (1 x IQ " ⁴ ) X H
H -CH ₂ (CHg) ₆ CH ₃ 67-69 Cl
Cl H O 50 (1 χ 10 ~ ⁴ )
H Cl H Ό 100 (1 x 10 "*) Cl H ⁰¹ TA 100 (1 x 10 ~ ⁴ ) Cl H 100 (2 χ 10 " ⁴ ) Cl H 100 (2 χ 10 " ⁴ ) Cl H 72-75 Cl H 65-65 Cl H 7O-72 Cl H Cl H Cl

115-114 80-85 91-92.5

Ports. TABLE II:

20988Α / Η20

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1A-41 599

Continued TABLE II

Fp. Or Ep. In ⁰ C (Torr)

Cl

/ Λ-OCH,

Cl H Cl H Cl H

Cl Cl Cl Br

-CH

-CH ₂ CH = CH ₂

Br H Cl H O
Λ CH ^ S-O- H ψ
0

CH

₂ ~ ζ ^

-OCH, 95-96

85-100 (dee) 90-105 (dec) 85-95 (1 x ΙΟ * ⁴ )

5 ^ -55

25th

not determined

92-94
25th

85-90 (1 χ ίο "" ⁴ )

82-84

- 52

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- 52 -

Example 15 Detachment of fruits

Havel oranges (Washington variety) were harvested in such a way that that the respective fruit is about 10 cm long Branch with two clusters of leaves. The necessary to peel the fruit from the cut branch Pulling force was 6.4 to 7.3 kg. The oranges still hanging on the branch with the leaves then became divided into groups of 5 each, those with methyl 2-chloroethanesulfinate and 2-chloroethanesulfinanilide in aqueous solution in various concentrations up to were sprayed to drain. A comparison group was sprayed with water only. After 2 days some started Oranges that have been treated with higher concentrations of the active ingredient fall off the branches, while the fruits in the comparison groups remained firmly attached to the branches. From Table III goes the Active ingredient concentration and the number of fruits detached 7 days after treatment.

TABEL

III

Treatment

water

Methyl 2-chloroethanesulfinate Methyl 2-chlorate sulfinate Methyl 2-chloroethanesulfinate 2-chloroethanesulfinanilide 2-chloroethanesulfinanilide 2-chloroethanesulfinanilide

Spray- . Number of Zv; ο ig Conc detached tration Oranges (ppm) 2 4000 5 2000 5 1000 3 4000 4th 2000 5 1000 4th

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- 53 -

Example 16 maturation

Green tomatoes picked in the open ground were made at random separated into a treatment group and a comparison group. The tomatoes in the treatment group were with an aqueous solution (concentration 1000 ppm) of Methyl 2-chloroethanesulfinate, which is 0.2% surfactant Agent contained, coated. The tomatoes in the comparison group were coated with a solution containing the active ingredient not included. Eighteen days after treatment, all of the tomatoes in the treated group were completely red during in the comparison group, the first two tomatoes only slowly began to turn red 20 days after treatment.

Example 17

Experience has shown that under normal conditions only 4-0 % of the seeds of the pointed burdock germinate. In the present experiment, 50 pointed burdock seeds were placed in pure water or in an aqueous solution (1000 ppm) of methyl 2-chloroethanesulfinate for 1 hour. The seeds were sown and allowed to germinate for 10 days. Treatment with methyl 2-chloroethanesulfinate increased the germination power of the seeds by 25% compared to the comparison experiment.

209884 / .U20

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At s ρ ie 1 18

Promoting the sprouting of tubers

24 yellow tubers of cypergrass (nutsedge) vmrden 10 min in an aqueous solution (100 ppm) Iietiiyl-2-cliloräthan- · sulfinate inserted, patted dry and tightly closed in a bottle. For comparison, the same was used Number of tubers treated with pure water and stored above in a sealed bottle. 6 days after treatment, all (100%) of those with the active substance had Solution-treated tubers sprouted, while in the comparative experiment only 81% had sprouted. In addition, the number of sprouts formed per tuber increased from 1.3 in the comparison group to 1.6 in the treated group. It was therefore found that treatment with riethyl-2-chloroethane sulfate inate the expulsion favored and suppressed the normal dominance of the summit shoot, so that side shoots can sprout.

Example 19

Repelling the leaves

Individual orange tree branches (Washington Navel Orange) were treated with an aqueous solution of various compounds according to the invention. The compounds in question were prepared as a 2000 ppn solution in water which contained 0.2 % surface-active agent. 100 ml of the solutions were sprayed onto a single orange tree branch as a foliar spray. 7 days after treatment

- 55 -209B84 / U20

-1A-41 599

"some leaves on the treated branches stiff, although still green, and began to fall off. The leaf-repellent effect of the substances concerned, 6 weeks after treatment, is shown in the table. Leaf repulsion was determined according to four classifications: 1 to 10%, 11 to 30%, 31 to 60 % and 61 to 100 % shed leaves, calculated on the originally present.

TABLE 17:

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- 56-

TABLE IV Tested connection;

Comparative experiment K-llethyl-2-chloroethanesulfinaraid N-ethyl-2-chloroethanesulfinariiä N-isopropyl-2-chloroethane disulfinamide H-tert-butyl-2-clilorethanesulfinamide N-sec-butyl-2- chloroethanesulfinamide N-butyl-2-chloroethanesulfinamide N-Heyyl-2-chloroethanesulfinamide N-octyl-2-chloroethanesulfinamide N-benzyl-2-chloroethanesulfinamide iI-Gyclohexyl-2-chloroethanesulfinamide N-2-chloroethanesulfinanilide 2.2 "flour oräthaxisulfinanilid 2,3'-dichloroethanesulfinanilide 2,4'-dichloroethanesulfinamide 2-chloro-a, a, a-trifluoroethanesulfin-3-toluid

2-chloroethanesulfinajnid Methyl 2-chloroethanesulfinate Ethyl 2-chloj'ethanesulfinate Isopropyl 2-chloroethanesulfinate Hexyl 2-chloroethanesulfinate Octyl-2-chloroethanesulfinate *

Sheet rejection 2 ζ in % 0 - 60 31 - 100 61 - 100 61 - 30th id 11 - 30th d 11 - 100 61 - 100 61 - 100 61 - 60 31 - 100 d ol 30th li - 10 1 - 30th 11 - 10 1 - 10 1 - 60 31 - 10 1 - 10 1 - 10 1 - 30th 11 - 10 1 -

2098 8 4 / U20

Example 20 Ripening Fruits

Picked, green, untreated bananas were divided up and divided into treatment groups at random. the Treatment consisted of spraying the individual treatment groups except for one group retained for comparison with an aqueous solution (1000 ppm) of one of the following compounds according to the invention:

2-chloroethanesulfinanilide, 2.2 «dichlorethanesulfinanilide, 2-chloroethanesulfinamide and N-hexyl-2-chloroethanesulfinamide. In all cases the treated bananas turned completely yellow 2 to 5 days / earlier than the untreated ones.

Example 21. _ü

Promoting the sprouting of tubers

24 yellow cypergrass tubers (nutsedge) were placed in an aqueous solution (100 ppm) of 2-chloroethanesulfinanilide for 10 minutes, patted dry and tightly closed in a bottle. For comparison, an equal number of tubers were treated with pure water and stored in a sealed bottle as above. 3 days after treatment, all (100 %) of the tubers treated with the active ingredient solution had sprouted , while in the comparison experiment only 78% had spilled. In addition, the number of sprouts formed per tuber increased from 1.3 in the comparison group to 1.5 in the treated group.

- 58 209884 / U2Ü -

1A-41 599

example

22nd

Ripe fruits

Greenhouse-grown adult green cherry tomatoes were harvested and randomly divided into treatment groups and a control group that included 20 ml of an aqueous solution (100 ppm) of the present invention in question were sprayed. The tomatoes were inspected at certain intervals to determine the degree of keenness. Which scored 4 days after treatment Results are given in Table Y.

TABEL

Number of fruits green colored ripe treatment 34 0 4th Comparative experiment 18th 7th 12th 2-chloroethanesulfinanilide 17th 14th 7th N-hexyl-2-chloroethanesulfine
amide 7th 23 ' 5 2-chloroethanesulfinamide 18th 11 5 2,2'-dichloroethanesulfine
anilide Example 23

Ripe fruits

Fully grown tomato plants, cultivar UF 145-21-4 in a plot of 1.25 × 3 m were sprayed until they dripped off with an aqueous solution containing 1000 ppm as active ingredient

- 59 -209884 / 1-420

223U63

11-41 599 - 59 -

2-chloroethanesulfinanilide and, as an additive, 1 % acetone, 0.5% surfactant and 10 % propylene glycol. For comparison purposes, another plot of the same size in the same field was sprayed with the otherwise same spray solution, but containing no active ingredient. The foliage was somewhat damaged in both the comparative spray and the treatment spray. The tomatoes were damaged 13 days after treatment from the two sprayed plots as well as from a plot not sprayed at all, which was used for further comparison purposes. Immediately after picking, the fruits were sorted into green, pink and red tomatoes. Table VI shows how much% by weight ripe ( red) fruits were present in the individual plots.

TABLE VI

Treatment . % red fruits%

in parcels

Comparative experiment 40.0 -

not sprayed (comparison) 39 ₅ 5 - 0.5

2-chloroethanesulfinanilide 66.8 +26.8

Example 24

Ripe fruits

Another attempt was made to test the ripening ability of the compounds of the present invention of green harvested tomatoes to examine. For this purpose, plants grown in the greenhouse were fully grown Tomatoes picked and straight: '/ ohl in groups

209884 / H2Q- ~ ^6Ü "

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- 60 -

divided by 10 pieces each. The chemicals used for treatment were in water / acetone solution of one A concentration of 1000 ppm was set and each group of tomatoes was immersed in one of the solutions containing the active ingredient for 1 hour contained "or placed in the comparison solution without active ingredient. The individual tomatoes in the respective Groups were rated daily for their coloration as follows: green (0 points), 'pale (1 point), semi-orange (2 points), full orange (3 points) and red or ripe (4 points). When "all of the tomatoes in a group are fully ripe the result is 40 points, i.e. 100%. The percentage of ripeness measured daily is given for the individual active ingredients in Table VII.

TABLE VII:

- 61 -

209884/1420

TABEL

VII

O CO OO OO

Maturity treatment in 1 % - - days after treatment 6th 7th 8th 11 14- 18th Comparative experiment 0 2 3 4th 15th 28 43 58 85 93 2-chloroethansuli'inamide 10 0 3 VJi 8th 88 93 93 93 98 100 N-Kethyl-N-phenyl-2-chloroethane
sulfinamide 8th 20th 35 50 · 73 80 90 _ 95 _v 100 - 100 100 2-chloroethanesulfine-3-toluid ■ 8th 15th 33 45 , 60 78 80 85 95 100 100 L ^T -0ctyl-2-chloroethanesulfinamide 8th 18th 30th 53 65 83 95 95 100 100 100 K-allyl-2-chloroethanesulfinamide VJl 13th 35 58 73 73 78 80 85 98 100 j 4 '-Piethoxy-2-chloroethane sulf inanildd VJl 5 25th 33 43 50 58 68 80 90 100 _w N-Cyclohexyl-2- chloroethanesulfinamide VJi 10 18th 28 43 83 93 93 93 98 100 ^ 2-chloroethanesulfinanilide 3 10 20th 43 60 50 60 75 93 100 100 2-chloro-ct j α, α-trif luorethanesulf in-
3-toluid 15th 25th 43 55 ■ 58 68 90 90 ■ ^9a N? 2,3'-dichloroethanesulfinanilide 3 8th 18th 30th 43 30th 40 55 78 93 100 ^ K "-Ee: cyl-2- chloroethanesulfinaiaid 3 5 13th 18th 25th 85 90 95 100 100 100 *> ? T-Benzyl-2-chloroethanesulfinaniid 3 15th 28 45 70 70 78 83 93 100 ι 100 p li-isopropyl-2-chloro-ethane-suliin-
aniid 3 10 15th 33 53 43 50 55 63 73 ^Q 5 _,
J N-Kexadecyl-2-chloroethane-sulfine-
am.id 3 Λ 10 23 25th 55 55 68 83 98 100 f IT- (2-ethyl thioethyl) -2-chloroethane- 3 3 10 18th 28 45 55 75 90 100 100 ^ 8th 15th 23

(y

sulfinamide

Ports. labeile VII;

Treatment 1 2 Ports . Tabel 18th 4th YII 6th 6th _7th 8th 9 11 10 14th 14th 18th 18th I. T
-fs 3 \ ^r - (2-hydroxyethyl) - 2- chi or- 0
ethanesulfinamide 3 2 3 48 18th 5 38 53 68 73 90 93 100 98 100 - "(Ji
ΓΟ vn H-3utyl-2-chlorath.ansul.fin- 0
amide 15th 3 13th 38 18th 33 68 35 40 58 85 80 90 85 95 98 - I. ° ro
N) ii-ethyl-2-chloroethanesulfine- 0
amide 10 3 8th 55 10 20th 53 · 35 48 53 83 78 83 98 . 93 100 - CO ri-hexyl-2-bromoethanesulfine-3
amide 25th 0 5 38 33 15th 68 83 '83 83 83 83 90 98 98 100 2-bromoethanesulfinamide 3 10 8th 23 28 18th 68 60 2 ⁸ 45 53 73 60 75 85 95 100 - K)
f— \ 1 11 3 10 "25 Λ. 25th 58 JL. 8th 80 86 95 - 1 I '
CD
CO Comparative experiment 3 8th 5j 4 .36 28 48 63 68 65 83 '98 - OO 2-chloroethanesulfinic acid, 13 11 8th 4-3 55 64 73 78 80 92 100 - Ethyl-2-chloroethanesulfinati 0 10 30th 45 65 58 73 80 85 100 J? " 2-propynyl-2-chloro-ath. -8
sulfinate 30th 60 78 80 to
O Isopropyl-2-chloroethane- 8
sulfinate Λ5 53 65 68 Allyl-2-chloroethane- 8
sulfinate 28 42 67 72 Octyl-2-chloroethanesulfinate 8 22nd 35 ^ 3 58 2-butoxyethyl-2-chloro-6
ethane sulfinate 15th 56 73 78 2- (chloroethane-sulfinyl- 5
oxy) -ethyl-2-chloroethane-
sulfinate 19th 48
- rn, 73
ΛΤΎΎ. 75 23

Ports . Tabel 40 YII 6th JZ_ 8th _2 10 14th 2 43 70 78 78 80 83 95 15th 23 23 58 63 78 85 93 93 100 8th 33 18th 55 55 68 " 70 78 88 98 5 18th 18th 33 43 58 63 65 70 90 5 10 13th 35 38 48 50 63 70 88 5 10 20th 33 33 55 63 78 80. . 93 3 8th 30th 15th 45 61 67 70 75 97 3 11 25th 50 58 70 80 85 93 8th 20th 33

Treatment ■ _Y 2 _Y5 4_ _S § Z_ _§ 9 10 14

Butyl 2-chloroethyl sulfinate 5 Hexyl 2-chloroethanesulfinate 5

2-Eth7l-hexyl-2-c3alorethanesulfinate 5

2-CS.thyl thio) -ethyl-2-chloroethanesulfinate 5

Methyl-2-chloroethane and lf inate . 3

Hexadecyl-2-chloroethane

■ sulfinate 3

3odecyl-2-chloroethanesulfinate 0

Sicosyl-2-chloroethanesulfinate 3

I K) VD

'G \ ■ N)

I -A

Example 25 Ripening Fruits

The test was carried out to determine the effectiveness of the compounds according to the invention as ripening agents for fully grown fruits before harvesting, i.e. for fruits that are still attached to the plant. Individual groups of fully grown in the greenhouse green cherry tomatoes were treated with the compound in question while the fruit was growing were still on the stick. The treatment liquid was an Ac et on / V / a s se r solution in which the Compound was contained in a concentration of 1000 ppm. The particular test solution was carefully tailored to each Applied 1 set of 4 groups of tomatoes, each group comprising 4 x to 6 fully grown tomatoes. Mission For comparison purposes, tomatoes were treated with the pure solution without active ingredient. The results are running out Table VIII.

TABLE VIII:

20988A / U20

TABEL

2231483

1A-41 599

¥ 111

treatment

"Comparison attempt
2-chloroethansu: lfinanilide

.IT-Allyl-2-chloroethanesulfinanilide

2-chloroethanesulfinamide

N-benzyl-2-chloroethanesulfinamide

N-hexyl-2-chloroethanesulfinamide

2,2'-dichloroathanesulfinamide Methyl 2-methoxyethanesulfinate Allyl 2-chloroethanesulfinate

Getyl 2-chloroethanesulfinate

Methyl 2-chloroethanesulfinate Lauryl-2-chloroethanesulfinate Eicosyl-2-chloroethanesulfinate

%
5 maturity
8th Tomatoes -
treatment
13 _. Days
16 after
19th 0 0 5 15th 30th 42 53 71 89 . 100 21 30th 36 50 64 33 46 54 74 74

32

60

0 27 36 50 59 0 0 6th 12th 78 6th 17th 39 56 73 0 0 41 4-7 82 0 0 14th 43 64 0 0 15th 34 54 0 0 10 27 58 0 0 11 22nd 58

66.-

2 0 9 8 8 A / H 2 0

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- 66 -

Example 26

Ripe fruits

Picked, green, untreated bananas were sectioned off and divided into treatment groups at random. The treatment consisted of spraying each treatment group except for one withheld for comparison Group with an aqueous solution (1000 ppm) one of the following compounds according to the invention methyl 2-chloroethanesulfinate and hexyl 2-chloroethanesulfinate In all cases the treated bananas turn completely yellow 2 to 5 days earlier than the untreated ones.

Example 2 £

Promote the germination of seeds

Experience has shown that under normal growth conditions, only 40 % of the seeds germinate in the pointed burdock. 50 seeds of the pointed burdock were placed in a mixture of water and acetone which contained 1000 ppm of N-2-chloroethanesulfinanilide for 1 hour. For comparison, another 50 seeds were placed in water-acetone without active ingredient. The treated seeds are sown and allowed to germinate for two weeks. Treatment with the compound according to the invention increased germination by 25% compared to the comparison seeds.

Example 28

Leaf epinasty

Leaf epinasty is a hormonal disorder that occurs in

- 67 -

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Plants thereby, makes noticeable that the upper side of the petiole grows faster than its underside, so that the leaf bends downwards. For the evaluation of the response to leaf epinasty 6 Vochen old tomato plants in groups were divided by three plants each and every group having a different ¹ compound of this invention in a concentration of 2000 ppm in an aqueous solution containing 0.2% surfactant, sprinkles. A non-sprayed group was used for comparison. Table IX shows the observations regarding leaf epinasty which occurred 13 days after treatment. The evaluation of the degree of leaf epinasty is based on four classifications: no epinasty, indicated by normal horizontal growth of the leaves; complete epinasty (90 °), indicated by the fact that the leaves grow vertically downwards around the trunk and 30 or 60 degree epinasty, indicated by a more or less downward leaf growth.

TABLE IX:

- 68 -

209884 / U2Q

TABEL

1A-4-1 599

Tested connection

Comparative experiment N-methyl-2-chloroethanesilfinamide H-isopropyl-2-chloroethanesulfinamide H-tert-butyl-2-chloroethanesulfinamide N-sec-butyl-2-chloroethanesulfinamide M-butyl-2-chloroethanesulfinamide H-hexyl-2-chloroethanesulfinamide N-Oc tyl-2-chloroethansuli'inamide N-2-chloroethanesulfinaniLide 2,2'-dichloroethanesulfinanilide 2,3'-dichloroethanesulfinanilide 2,4'-dichloroethanesulfinamide

2-chloro-a, a, a-trifluoroethanesulfin-3-toluid

2-chloroethanesulfinamide Ethyl 2-chloroethanesulfinate Isopropyl 2-chloroethanesulfinate Hexyl-2-chloroethanesuli'inate Octyl 2-chloroethyl sulfinate Getyl 2-chloroethanesulfinate Diethyl 2-chloroethanesulfinate Lauryl 2-chloroethane silfinate Allyl-2-chloroethanesuli'inate Methyl-2-bromoätlian £ iuli'inat degree of

Leaf pinasty

no

60

fully

fully

60

fully

fully

60

fully

30th

fully

fully

fully

30 '

60

- -69 -

209884/1420

599

- 69 -

Example 29

Leaf epinasty ■

A second leaf epinasty test was carried out on tomato plants. The test compounds to be evaluated were sprayed onto three different tomato plants as a foliar spray. Two plants were 37 days as, the third plant 23 days. The older plants were 35> 5 cm high and had 10 leaves, the younger plants had 8 leaves and 25.4 cm high. Plants of different ages were used up because the older plants are usually more sensitive and respond more quickly to hormonal epinasty. The test compounds were dissolved in acetone and diluted to 2500 ppm with water containing 0.4 % of a surfactant. In each case 10 ml of the compound diluted as above was used to spray the leaves of three tomato plants. The treated plants were examined for epinasty (bending of the leaves down towards the base of the stem) 20 hours after treatment. Four days after treatment, the test was reevaluated for both epinasty and phytotoxicity to determine whether the epinasty effects had dissipated. The test results including the compounds used are shown in Table X. The column "Leaves, normal after 4 days" reflects the visual observations that determined whether effects of the epinasty were still left 4 days after treatment.

TABLE Xi

. - 70 209884/1420

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- 70 -

TABLE Σ
% Leaves responding to epinasty

Treatment

no light medium- complete speaking of respondents- star- respondents chen kes anchen norspremal

check

4 _Ta _

gene

Comparative experiment

2-chloroethanesulfinamide

2-chloro-N-methoxy-ethane- sulfiiiamide

2- (methylsulfonyloxy) ethanesulfinamide

2- (Hethylsul f onylοxy) ethanesulfinanilide

Phenyl 2-chloroethanesulfinate

19th

59

15th

12th

no

Phytotoxicity

no

a)
moderate

none none

none none

a) moderate phytotoxicity means that the leaves
were slightly yellowed.

PATENT CLAIMS:

209884/1420

Claims (1)

Claims 1. Means for influencing the plant / axis turn, characterized in that it, in addition to the usual additives, as an active ingredient a compound of the general formula X-CH ₂ CH ₂ -SA contains, where in the formula X and A have the following meaning: X stands for Chlorine, bromine, iodine, alkoxy with up to 3 carbon atoms, aryloxy with up to 10 carbon atoms, alkylthio with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms, acyloxy with up to 4 carbon atoms Atoms, alkylsulphonyloxy, in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy, nitro, monoalkylamino or dialkylamino, v / orin each alkyl group contains up to 6 carbon atoms, or A ¹ R ¹ , in which A ^{1 is} oxygen and R 'is 2- (dimethylcarbamoyl) ~ 1-methylvinyl, 2- (methylcarabomoyl) -1-methylvinyl or 2- (methoxycarbonyl) -1 - methylvinyl stand; A stands for 1. the group -Y-R, wherein Y is oxygen or sulfur, with the proviso that if Y is oxygen, R stands for the following groups: Alkyl with up to 20 carbon atoms, aryl with up to 10 carbon atoms, aralkyl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, alkynyl with up to 4 carbon atoms, 2- (dimethyl- - 72 209884 / IA20 carbamoyl) -1-methylvinyl, 2-methylcarbamoyl) -1-methyl- . p vinyl or 2- (methoxycarbonyl) -I-methylvinyl or ZR, ρ where Z is alkylene with up to 4 carbon atoms and R is alkylthio with up to 3 carbon atoms, alkoxy with up to 4 carbon atoms, aralkoxy with up to 10 carbon atoms, hydroxy or a β-substituted one Äthansulfinyloxyest is in which the ß-substituent with the ß-substituent represented by X of the formula I. is identical; and that, if Y is sulfur, R stands for the following groups: Alkyl with up to 8 carbon atoms, optionally substituted with chlorine or bromine or aralkyl, in which the alkyl group contains up to 4 carbon atoms ₍ and in which R can also stand for hydrogen if Y is oxygen and X is one of the above for X represents mentioned groups except A ¹ R ¹ ; s "5 4 2. the group -N, in which then R and R are the same R ⁴ or can be different, for alkyl with up to 20 carbon atoms or aralkyl with up to 10 carbon atoms, and in which R ^ and R, each can stand for themselves or both and RY ¹ , in which R is alkylene with up to 4 C atoms and Y ^{1 is} hydroxy or β-haloethanesulfinyloxy, in which the β-halogen substituent is chlorine, bromine or iodine, with the proviso that, if Y ^{1 is} hydroxy, X represents one of the radicals mentioned above for X except A'R 'stands, and that, if Y is ß-haloethanesulfinyloxy, X stands for chlorine, bromine or iodine, where, if R is hydrogen, R can also stand for the following groups: aryl with up to 10 carbon atoms, Alkenyl. With up to 8 carbon atoms, cycloalkyl with up to 5 2 5
8 carbon atoms, RT, where R ^ has the above meaning and Y alkylthio with up to 3 carbon atoms or alkoxy with up to to 4 carbon atoms, where, if R * is hydrogen, R also a substituted phenyl of the formula -, 73 -2 U 9 B-ö UI 1 4 2 0 may be, wherein Z ^{1 is} alkyl with up to 3 carbon atoms, alkoxy with up to 3 carbon atoms, alkylsulfonyl with up to 3 carbon atoms, chlorine, bromine, nitro or trifluoromethyl and, if R ^ hydrogen, alkyl or Aryl, R can also stand for hydroxy or alkoxy with up to 4 carbon atoms. 2. Means according to claim 1, characterized in that in the formula of the active ingredient X represents chlorine, bromine or alkoxy with up to 3 carbon atoms and A represents the group -0-R, in which R has the following meaning has: hydrogen, alkyl with up to 20 carbon atoms, aryl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, Alkynyl with up to 4 carbon atoms or ZR, in which Z represents alkylene with up to 4 carbon atoms and R represents alkylthio with up to 3 carbon atoms or for alkoxy with up to 4 carbon atoms or for hydroxyl; and in which, if X is chlorine, 2
R can also represent a ß-Chloräthansulfinyloxyest. 3. Composition according to claim 1, characterized in that in the formula for the active ingredient X Represents alkoxy with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms or acyloxy with up to 4 carbon atoms, and A represents the group -0-R, in which R is hydrogen. 4. Means according to claim 1, characterized in that in the formula for the active ingredient X Represents chlorine, aralkoxy with up to 10 carbon atoms or alkoxy with up to 3 carbon atoms, and A for the group -0-R stands, v / orin R is alkyl with up to 20 carbon atoms, aralkyl with up to 10 carbon atoms or alkenyl with up to 8 carbon atoms 1 0 0 B H '♦ / 1 / ♦ 2 U " ^7h 5 #, agent according to claim 2, characterized in that in the formula for the active ingredient X Represents chlorine and A represents the group -0-R, in which R is alkyl with up to 20 carbon atoms or alkenyl with up to 8 carbon atoms. 6. Agent according to claim 1, characterized in that X represents chlorine or bromine and A represents represents the group -S-R, in which R ß-chloroethyl, ß-bromoethy'l, Is alkyl with up to 5 carbon atoms or benzyl. 7. Composition according to claim 1, characterized in that in the formula for the active ingredient A s 4 represents the group -N _n ^, where R has the following meaning has: hydrogen, aryl with up to 10 carbon atoms, alkyl rait up to 20 carbon atoms, aralkyl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, cycloalkyl with up to 8 carbon atoms, 5 5 Alkoxy with up to 4 carbon atoms or RY !, where R is alkylene with up to 4 carbon atoms and Y ^{1 is} hydroxy or alkylthio 4 are up to 3 carbon atoms; or R can also mean a substituted phenyl of the formula If ' y, wherein Z ^{1 represents} alkyl with up to 3 carbon atoms, alkoxy with up to 3 carbon atoms, alkylthio with up to 3 carbon atoms, alkylsulfonyl with up to 3 carbon atoms, chlorine, bromine, nitro or trifluoromethyl; and that X in the above formula stands for chlorine, bromine, iodine or the alkylsulfonyloxy group in which the alkyl group contains up to 3 carbon atoms, with the proviso that, if X stands for alkylsulfonyloxy, R ^ is hydrogen, alkyl with up to 6 carbon atoms or aryl with up to 10 carbon atoms. - 75 -2Ü ¹ JU ü A / 1 42 0 22.3HB3 8. Composition according to claim 7, characterized in that in the formula for the active ingredient X Means chlorine, bromine or iodine. 9. Composition according to claim 8, characterized in that in the formula for the active ingredient X Chlorine and R for hydrogen, alkyl with up to 8 carbon atoms, cycloalkyl with up to 6 carbon atoms, alkenyl with up to 5 carbon atoms, phenyl, which is optionally substituted is with chlorine, bromine or trifluoromethyl, or for aralkyl with up to 8 carbon atoms. 10. Composition according to claim 9, characterized in that in the formula for the active ingredient R is unsubstituted phenyl _o 11. Means according to claim 9, characterized in that g e k e η η - 4 draws that in the formula for the active ingredient R stands for hydrogen. Compounds of the general formula X-CH ₂ CH ₂ -SA in which A can represent the following groups R ³
(1) for group -N. , in the R and R that are the same or can be different, each for hydrogen, Alkyl with up to 20 carbon atoms or aralkyl with up to 10 carbon atoms; and being either one or both 3 4 5 5 R- ^ and R ^{can stand for RT 1} , in which R is alkylene with up to 4 carbon atoms and Y 'is hydroxy or ß-haloethanesulfinyloxy, in which the ß-halogen substituent is chlorine, bromine or iodine, with the following proviso: if Y ^{1 is} hydroxy, X represents one of the groups mentioned above for X. ') Ü Ά U H /, / Ί /. V fl - 76 - except A'R ¹ and if Y ^{1 is} ß-haloethanesulfonyloxy, 3 X stands for chlorine, bromine or iodine and in which, if R is hydrogen, R - can also represent the following groups: aryl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms or R ⁵ Y ² , where R ^{5 has} the above meaning and Y ^{2 is} alkylthio with up to 3 carbon atoms; and. when R ^{5 is} hydrogen, R is also a substituted phenyl of the formula can represent, wherein Z ^{1 represents} alkyl with up to 3 carbon atoms, Alkylthio with up to 3 carbon atoms, alkoxy with up to 3 carbon atoms, alkylsulfonyl with up to 3 carbon atoms, chlorine, bromine, nitro or trifluoromethyl; and where, if 3 4 R is hydrogen, alkyl or aryl, R can also stand for hydroxy or alkoxy with up to 4 carbon atoms, while X represents: chlorine, bromine, iodine, hydroxy or alkoxy with up to 3 carbon atoms, aryloxy with up to 10 Carbon atoms, alkylthio with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms, acyloxy with up to 4 carbon atoms, alkylsulfonyloxy in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy, nitro, monoalkylamino or Dialkylamino, in which each alkyl group contains up to 6 carbon atoms, or A ¹ R ¹ , in which A ^{1 is} oxygen and R ^{1 is} 2- (dimethylcarbamoyl) -1-methylvinyl, 2- (methylcarbamoyl) -1-methylvinyl or 2- (methoxycarbonyl ) Is -I-methylvinyl; or (2) for the group -Y-R, in which Y is oxygen and R is hydrogen where X then represents: bromine, hydroxy, alkoxy with up to 3 carbon atoms, alkylthio with up to 3 carbon atoms, Acyloxy with up to 4 carbon atoms, aryloxy with up to 10 carbon atoms, alkylsulfonyloxy in which the alkyl group has up to 3 carbon atoms contains, arylsulfonyloxy, aralkoxy with up to 10 carbon atoms, nitro or wonodialkylamino, in which each alkyl group contains up to contains up to 6 carbon atoms; or 2 0 ¹ JUB kl I UI U BAD " ⁷⁷ " 223U63 (3) for the group -Y-R, where Y is oxygen and R represents one of the following groups: alkyl with 6 to 20 carbon atoms, aralkyl with up to 10 carbon atoms., alkynyl with up to 4 carbon atoms, alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms 2- (dirnethylcarbamoyl) -1-methylvinyl, 2- (methylcarbamoyl) -1-methylvinyl, 2- (methoxy- carbonyl) -1-methylvinyl or ZR, where Z is alkylene with ρ
up to 4 carbon atoms and R for alkylthio with up to 3 carbon atoms, alkoxy with up to 4 carbon atoms, aralkoxy with up to 10 carbon atoms, hydroxy or a ß-substituted ethanesulfinyloxy radical (in which the ß-substituent is identical to the ß- represented by X in formula I Substituents) ^! and X is chlorine, bromine or iodine; or (4) for the group -Y-R, in which Y is oxygen and R has the following meaning: alkyl with up to 20 carbon atoms, Aralkyl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, aryl with up to 10 carbon atoms, 2- (dimethylcarbamoyl ) -1-methylvinyl, 2- (methylcarbamoyl) -1-methyl- vinyl, 2- (methoxycarbonyl) -I-methylvinyl or ZR, wherein ρ Z stands for alkylene with up to 4 carbon atoms and R is alkylthio with up to 3 carbon atoms, alkoxy with up to 4 carbon atoms, hydroxy or a ß-substituted ethanesulfino radical (in which the ß-substituent is identical to that through X represented in formula I), while X stands for the following groups: hydroxy, alkoxy with up to 3 carbon atoms, aryloxy with up to 10 carbon atoms, aralkoxy with up to 10 carbon atoms, alkylthio with up to 3 C atoms, acyloxy with up to 4 C atoms, alkylsulfonyloxy in which the alkyl group contains up to 3 C atoms, arylsulfonyloxy, nitro or mono- or dialkylamino (in which each alkyl group contains up to 6 C atoms) or A ¹ R ¹ , wherein A ^{1 is} oxygen and R ^{1 is} 2- (dimethylcarbamoyl) -1-methylvinyl, 2- (methylcarbamoyl) -1-methylvinyl or 2- (methoxycarbonyl)>-1-methylvinyl; or (5) for the group -Y-R, where Y is sulfur and R is an optionally substituted with chlorine or bromine 2U98U4 / I 4 ^ Ü " ^78. ~ Alkyl with up to 8 carbon atoms or for aralkyl, in which the Alkyl group contains up to 4 carbon atoms, while X is chlorine, bromine or hydroxy, alkoxy with up to 3 carbon atoms, aryloxy with up to 10 carbon atoms, alkylthio with up to 3 carbon atoms, aralkoxy with up to 10 carbon atoms, acyloxy with up to 4 carbon atoms, alkylsulfonyloxy, in which the alkyl group contains up to 3 carbon atoms, arylsulfonyloxy, Nitro, mono- or dialkylamino, wherein "any alkyl up to Contains 6 carbon atoms. 13. Compounds according to claim 12, in which X is bromine, chlorine or alkoxy with up to 3 carbon atoms and A represents the group -0-R, in which R can have the following meanings: alkyl with 6 to 20 carbon atoms, alkynyl with up to 4 carbon atoms, alkenyl with up to 8 carbon atoms, aryl ρ
with up to 10 carbon atoms, or ZR, where Z stands for alkylene with up to 4 carbon atoms and R is alkylthio with up to 3 carbon atoms or alkoxy with up to 4 carbon atoms or hydroxy ρ means; and in that, if X is chlorine, R can also represent a ß-chloroethanesulfinyloxy radical " 14. A compound according to claim 12, characterized in that g e k e η η draw t that X stands for bromine and A stands for the group -0-R, in which R is hydrogen. 15. Compounds according to claim 12, characterized draws that in the formula A for the group ' 4 -N is where R can have the following meanings: Hydrogen, aryl with up to 10 carbon atoms, alkyl with up to 20 carbon atoms, aralkyl with up to 10 carbon atoms, alkenyl with up to 8 carbon atoms, cycloalkyl with up to 8 carbon atoms, alkoxy with up to to 4 carbon atoms or RY ', where R represents an alkylene with up to 4 carbon atoms and Y ^{1 represents} hydroxy or alkylthio with up to 3 carbon atoms; and wherein R is also a substituted phenyl of the formula 2 U y ü U 4 / I 4 2 U _ 79. can be, wherein Z ^{1 can} mean: 'Alkyl with bis to 3 carbon atoms, alkylthio with up to 3 carbon atoms, alkoxy with up to 3 carbon atoms, alkylsulfonyl with up to 3 carbon atoms, chlorine, Bromine, nitro or trifluoromethyl; and where X is chlorine, Bromine, iodine or alkylsulfonyloxy (in which the alkyl group can have up to 3 carbon atoms), with the proviso that, if X represents alkylsulfonyloxy, R ¥ hydrogen, alkyl with up to 6 carbon atoms or aryl with up to 10 carbon atoms. 16. Compounds according to claim 15, wherein X is chlorine. 17. Compounds according to claim 16, wherein R can mean: hydrogen, alkyl with up to 8 carbon atoms, cycloalkyl with up to 6 carbon atoms, alkenyl with up to 5 carbon atoms, unsubstituted phenyl, with chlorine, bromine or trifluoromethyl substituted phenyl or aralkyl with up to 8 carbon atoms. 18. The compound of claim 17, wherein R is unsubstituted Is phenyl. 19. The compound of claim 17, wherein R is hydrogen is. 2098 8 4/1420