Germicidal herbicide for agriculture and horticulture

A germicidal herbicide for agriculture and horticulture, which comprises at least one compound, as an active ingredient having the formula (I); EQU r--x--ch.dbd.ch--cooy (i) wherein R represents an alkyl or alkenyl group having 1 to 20 carbon atoms, X represents S, SO or SO.sub.2, and Y represents a hydrogen atom, an alkali metal, an alkaline earth metal, NH.sub.4, an alkyl or alkenyl group having 1 to 20 carbon atoms, a polyalcohol residue which may have therein ether bonds formed by intramolecular or intermolecular dehydration, an acetal glycerol residue, or an oxyethylene (1 to 20 units) or oxypropylene group (1 to 20 units) terminated by an alkyl group having 1 to 20 carbon atoms.

BACKGROUND OF INVENTION 
1. Field of the Invention 
This invention relates to a novel germicidal herbicide for agriculture and 
horticulture and, particularly relates to a germicidal herbicide for 
agriculture and horticulture comprising one or more compounds, as active 
ingredients, having formula (I); 
EQU r--x--ch.dbd.ch--cooy (i) 
wherein R represents an alkyl or alkenyl group having 1 to 20 carbon atoms, 
X represents S, SO or SO.sub.2, and Y represents a hydrogen atom, an 
alkali metal, an alkaline earth metal, NH.sub.4, an alkyl or alkenyl group 
having 1 to 20 carbon atoms, a polyalcohol residue which may have therein 
ether bonds formed by intramolecular or intermolecular dehydration, an 
acetal glycerol residue, or an oxyethylene (1 to 20 units) or oxypropylene 
group (1 to 20 units) terminated by an alkyl group having 1 to 20 carbon 
atoms. 
2. Description of the Prior Art 
Recently, the field of agricultural chemicals has made considerable 
progress and as a result a number of new germicides and herbicides have 
been produced. However, some of these agricultural chemicals or either 
harmful to man and animals or, pollute the environment., and moreover 
their effects are unstable. These deficiencies, therefore, often pose 
social problems. 
In view of the above circumstances, there continues to be a need for 
germicidal herbicides for agriculture and horticulture having stable 
effects and higher safety. 
In order to provide germicidal herbicides for agriculture and horticulture 
meeting the above demands, the present inventors examined a number of 
compounds and as a result found that alkylsulfenyl acrylic acid, 
alkylsulfinyl acrylic acid and alkylsulfonyl acrylic acid derivatives 
represented by formula (I) exhibit excellent germicidal effects on a plant 
virus and exhibit herbicidal effects on various weeds. Based on this 
finding, the present invention has been accomplished. 
SUMMARY OF THE INVENTION 
Accordingly, an object of this invention is to provide a germicidal 
herbicide for agriculture and horticulture possessing both germicidal and 
herbicidal effects. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
When the compounds of the present invention are used as germicides, they 
eliminate a wide variety of ill effects of plant diseases and are less 
phototoxic than other germicides. On the other hand, when they are used as 
herbicides, they show a long-lasting effects, exhibit a stable potency 
without changing their effects and potencies according to various 
conditions such as the soil to which they are applied, and present a 
negligible toxicity to human beings, animals and fish. 
These compounds possess excellent spreadability, wetting ability and 
dispersability characteristics on plants because of their surface-active 
potency, and therefore, they may be used without any particular adjuvant. 
"Suitable polyalcohols which may have therein ether bonds formed by 
intramolecular or intermolecular dehydration" and are within the scope of 
group Y of formula (I) include ethylene glycol, propylene glycol, 
glycerol, erythritol, xylitol, pentaerythritol, sorbitol, mannitol, and 
polyoxyalkylene glycols having diglycerine, dipentaerythritol, xylitan, 
sorbitan, mannitan and oxyethylene groups or oxypropylene groups having 2 
to 20 units. 
Suitable compounds within the scope of formula (I) include 
__________________________________________________________________________ 
1 .beta. -alkylsulfenyl acrylic acids or salts 
n-C.sub.4 H.sub.9SCHCHCOONa, n-C.sub.8 H.sub.17SCHCHCOONa, 
n-C.sub.12 H.sub.25SCHCHCOONa, n-C.sub.16 H.sub.33SCHCHCOONa 
n-C.sub.4 H.sub.9SCHCHCOOH (mp86.about.88.degree. C) n-C.sub.12 
H.sub.25HCHCOOH (mp92.about. 94.degree. C) 
n-C.sub.8 H.sub.17SCHCHCOOH, n-C.sub.10 H.sub.21SCHCHCOOH, n-C.sub.14 
H.sub.29SCHCHCOOH 
2 .beta. -alkylsulfinyl acrylic acids or salts 
n-C.sub.4 H.sub.9SOCHCHCOONa, n-C.sub.10 H.sub.21SOCHCHCOONa, 
n-C.sub.12 H.sub.25SOCHCHCOONa 
n-C.sub.4 H.sub.9SOCHCHCOOH (mp58.about.62.degree. C) n-C.sub.12 
H.sub.25SOCHCHCOOH (mp62.about.65.degree. C) 
n-C.sub.8 H.sub.17SOCHCHCOOH 
3 .beta. -alkylsulfonyl acrylic acids or salts 
n-C.sub.4 H.sub.9SO.sub.2CHCHCOOH (mp102.about.104.degree. C) 
n-C.sub.12 H.sub.25 SO.sub.2CHCHCOOH (mp105.about.108.degree. C) 
n-C.sub.12 H.sub.25SO.sub.2CHCHCOONa 
4 .beta. -alkylsulfenyl acrylic acid alkyl esters 
n-C.sub.4 H.sub.9SCHCHCOOCH.sub.3 (mp44.about.46.degree. C) n-C.sub.12 
H.sub.25 SCHCHCOOCH.sub.3 (mp48.about.50.degree. C) 
n-C.sub.8 H.sub.17SCHCHCOOCH.sub.3, n-C.sub.18 H.sub.37SCHCHCOOCH.sub.3 
5 .beta. -alkylsulfinyl acrylic acid alkyl esters 
n-C.sub.4 H.sub.9SOCHCHCOOCH.sub.3 (mp53.about.55.degree. C) 
n-C.sub.12 H.sub.25SOCHCHCOOCH.sub.3 (mp55.about.58.degree. C) 
n-C.sub.8 H.sub.17SOCHCHCOOCH.sub.3, n-C.sub.3 H.sub.7SOCHCHCOOCH.sub.3, 
n-C.sub.5 H.sub.11SOCHCHCOOC.sub.2 H.sub.5, n-C.sub.18 H.sub.37SOCHCHCOO 
CH.sub.3 
6 .beta. -alkylsulfonyl acrylic acid alkyl esters 
n-C.sub.4 H.sub.9SO.sub.2CHCHCOOCH.sub.3 (mp83.about.85.degree. C) 
n-C.sub.12 H.sub.25SO.sub.2CH CHCOOCH.sub.3 (mp85.about.88.degree. C) 
n-C.sub.8 H.sub.17SO.sub.2CHCHCOOCH.sub.3, n-C.sub.18 H.sub.37SO.sub.2CH 
HCOOCH.sub.3, 
n-C.sub.8 H.sub.17SO.sub.2CHCHCOOC.sub.2 H.sub.5 
7 .beta. -alkylsulfenyl acrylic acid methylcarbityl esters 
n-C.sub.4 H.sub.9SCHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
(n.sub.D.sup.20 1.5130) 
n-C.sub.12 H.sub.25SCHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 
OCH.sub.3 (n.sub.D.sup.20 1.5210) 
8 .beta.-alkylsulfinyl acrylic acid methylcarbityl esters 
n-C.sub.4 H.sub.9SOCHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
(n.sub.D.sup.20 1.5010) 
n-C.sub.12 H.sub.25SOCHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 
OCH.sub.3 (n.sub.D.sup.20 1.5120) 
9 .beta.-alkylsulfonyl acrylic acid methylcarbityl esters 
n-C.sub.4 H.sub.9SO.sub.2CHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 
OCH.sub.3 (n.sub.D.sup.20 1.5115) 
n-C.sub.12 H.sub.25SO.sub.2CHCHCOOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 
OCH.sub.3 (n.sub.D.sup..sup.20 1.5210) 
10 
.beta.-alkylsulfenyl acrylic acid glyceryl esters 
##STR1## 
##STR2## 
##STR3## 
##STR4## 
11 
.beta.-alkylsulfinyl acrylic acid glyceryl esters 
##STR5## 
##STR6## 
12 
.beta.-alkylsulfonyl acrylic acid glyceryl esters 
##STR7## 
##STR8## 
13 
.beta.-alkylsulfenyl acrylic acid glyceryl acetal esters 
##STR9## 
##STR10## 
14 
.beta.-alkylsulfinyl acrylic acid glyceryl acetal esters 
##STR11## 
##STR12## 
15 
.beta.-alkylsulfonyl acrylic acid glyceryl acetal esters 
##STR13## 
##STR14## 
16 
.beta.-alkylsulfenyl acrylic acid polyoxyalkylene esters 
n-C.sub.4 H.sub.9SCHCHCOO(CH.sub.2 CH.sub.3 O).sub.15 H (n.sub.D.sup.20 
1.5030) 
n-C.sub.12 H.sub.25SCHCHCOO(CH.sub.2 CH.sub.2 O).sub.15 H 
(n.sub.D.sup.20 1.5230) 
n-C.sub.4 H.sub.9SCHCHCOO(CH.sub.2 CH.sub.2 O).sub.2 H 
17 
.beta.-alkylsulfinyl acrylic acid polyoxyalkylene esters 
n-C.sub.4 H.sub.9SOCHCHCOO(CH.sub.2 CH.sub.2 O).sub.15 H 
(n.sub.D.sup.20 1.5210) 
n-C.sub.12 H.sub.25SOCHCHCOO(CH.sub.2 CH.sub.2 O).sub.15 H 
(n.sub.D.sup.0 1.5121) 
n-C.sub.14 H.sub.29SOCHCHCOO(CH.sub.2 CH.sub. 2 O).sub.15 H 
n-C.sub.14 H.sub.29SOCHCHCOO(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.5 H 
18 
.beta.-alkylsulfonyl acrylic acid polyoxyalkylene esters 
n-C.sub.4 H.sub.9 SO.sub.2CHCHCOO(CH.sub.2 CH.sub.2 O).sub.15 H 
(n.sub.D.sup.20 1.5180) 
n-C.sub.12 H.sub.25SO.sub.2CHCHCOO(CH.sub.2 CH.sub.2 O).sub.15 H 
(n.sub.D.sup.20 1.5189) 
19 
.beta.-alkylsulfenyl acrylic acid sorbityl esters 
##STR15## 
##STR16## 
20 
.beta.-alkylsulfinyl acrylic acid sorbityl esters 
##STR17## 
##STR18## 
21 
.beta.-alkylsulfonyl acrylic acid sorbityl esters 
##STR19## 
##STR20## 
__________________________________________________________________________ 
The compounds of formula (I) in the present invention can be produced, for 
example, as follows. 
(a) Mercaptans of the formula; 
EQU RSH 
wherein R is defined as in formula (I) are reacted with proprolic acid 
derivatives in alkaline aqueous solution to obtain the compounds of 
formula (I) wherein X is S and Y is a hydrogen atom, alkali metal, 
alkaline earth metal or NH.sub.4. 
(b) Acids obtained in process (a), or acid halides thereof, are reacted 
with various alcohols in the presence of an acid or base catalyst in a 
conventional manner to obtain the compounds of formula (I) wherein X is S, 
and Y is an alkyl or alkenyl group having 1 to 20 carbon atoms, a 
polyalcohol residue which may have therein ether bonds formed by 
intramolecular or intermolecular dehydration, an acetal glycerol residue 
or, an oxyethylene (1 to 20 units) or oxypropylene (1 to 20 units) 
terminated by an alkyl group having 1 to 20 carbon atoms. 
(c) The compounds thus obtained in processes (a) and (b) may be oxidized 
with an inorganic or organic peroxide such as sodium metaperiodate, 
hydrogen peroxide, perbenzoic acid, m-chloroperbenzoic acid and peracetic 
acid to obtain the corresponding compounds of formula (I) wherein X is SO 
or SO.sub.2 according to the methods of (Japanese Patent Applications Nos. 
82372/1975, 83242/1975 and 84707/1975. 
The compounds of formula (I) may be used singly as germicides for 
agriculture and horticulture without any other adjuvants. They can also be 
used in the form of wettable powders or solutions or in other forms 
applicable to general agricultural chemicals, such as dissolving, 
suspending or emulsifying them in or mixing them with conventional 
carriers. 
The compounds of formula (I) may be used as a germicide in a concentration 
ranging from 300 to 1,000 ppm, preferably 500 ppm. 
The present compounds can exterminate plant diseases by spraying them on 
growing plants. Moreover, they can be used as an antiseptic by immersing 
seeds and bulbs therein. 
The compounds of formula (I) according to the present invention possess a 
particularly strong herbicidal potency to gramineae weeds such as 
barnyardgrass, Cyperus microiria, Henry crabgrass, goosegrass and green 
foxtail; broad-leaved weeds such as Polygonum blumei, livid amaranth, 
common purslane and common lambsquarters; and perennial weeds such as 
purple nutsedge and Rumex japonicus. They can be used singly and also in 
the conventional forms of a powder, granules, wettable powder, emulsions 
and the like by dissolving, suspending or emulsifying them in carriers, or 
by mixing them with carriers. The compounds of formula (I) may usually be 
used as a herbicide in a concentration ranging from 3,000 to 6,000 ppm, 
preferably 4,000 ppm. 
Suitable solid carriers include mineral powder such as clays, for example, 
kaolin, bentonite and terra abla; talcs, for example, talcum powder; 
silicates, for example, diatomaceous earth, vermiculite, slaked lime and 
mica powder; and alumina, silica gel and the like. Suitable liquid 
carriers include, for example, water, alcohols, ketones, benzene, xylene, 
toluene and cyclohexane. 
Since compounds of the formula (I) possess surface-active potency by 
themselves, particular surface-active agents are not necessarily required. 
However, conventional surface-active agents, such as spreaders, 
emulsifiers, penetrants, dispersants and solublizers may be used as needed 
for example, soaps, higher alcohol sulfates, alkyl sulfonates, alkylaryl 
sulfonates, quaternary ammonium salts, polyalkylene oxides, higher fatty 
acid esters and the like. 
Germidical herbicides for agriculture and horticulture according to the 
present invention may be used, if necessary, in combination with other 
herbicides, insecticides, fertilizer components, soil-improving agents or 
germicides. 
The invention is illustrated below in further detail with reference to the 
following Examples.