JPS63216869A - N-(2-(pyridyl)propen-3-yl)-n-substituted-sulfonamides - Google Patents

Abstract

NEW MATERIAL:The N-[ 2-( pyridyl )propen-3-yl ]-N-substituted-sulfonamides of formula I [J is phenyl which may be substituted or benzo-condensed; A is direct bond, -CH2-, -CH=CH-, -O- or -N(r)- (r is alkyl); R is alkyl, alkenyl, alkynyl, alkoxy, fluoroalkyl or formyl; V is (substituted) pyridyl]. EXAMPLE:3-[ N-methyl-N-(p-toluenesulfonyl)amino ]-2-(6-methylpyrid-in-2-yl)pro pene. USE:An intermediate for the production of herbicide. PREPARATION:The compound of formula I can be produced e.g. by reacting sulfonamides of formula II with a compound of formula III (Z is halogen or sulfonyloxy) in the presence of a base.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides novel N-[co(pyridyl)propene-3-
yl]-N-[substituted sulfonamides. More specifically, N- is an intermediate for producing N-[co(pyridyl)propyl]-M-substituted sulfonamides useful as herbicides.
C-(pyridyl)flopen-J-yl]-11-substituted sulfonamides.

[Prior art]

It has been known that various N-@substituted benzenesulfonamides have herbicidal activity.

For example, JP-A-I8sg-/J/9? ? N-(J,J-eboxyglovir)-N- as a selective herbicide.
α-Methylbenzyl-Hiro-propylbenzenesulfonamide is shown, and the compound is.

It is prepared by oxidizing N-allyl-N-α-methylbenzyluda-propylbenzenesulfonamide.

Furthermore, JP-A-57-3 Coco-6ri and JP-A-6-12gbJbb disclose certain sulfonamides containing a pyridyl group as compounds having herbicidal or fungicidal activity. .

[Problem that the invention seeks to solve]

The present invention provides a novel intermediate for producing N-[co(pyridyl)propyl)-N-ftllll sulfonamides, which are more useful as herbicides than conventionally known sulfonamide compounds.

[Means to solve the problem]

The gist of the present invention is the general formula (1) (wherein J represents a phenyl group which may be substituted or benzodilated; A represents a direct bond, or -aH, +, - 〇) 1 seal 0) 1+, -o-1 or -N
It represents a group represented by (r)-, and r represents an alkyl group of 01 to C1. R represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a fluoroalkyl group or a formyl group. (2) represents an optionally substituted pyridyl group. ) represented by N−(
Co(pyridyl)propen-3-yl]-N-substituted sulfonamides. The present invention will be explained in more detail below.

The compound of the present invention represented by the general formula (I) is a compound of the present invention represented by the general formula (I).
l) D (wherein J represents a phenyl group which may be substituted or benzo-fused; A is a direct bond, or -OH, -1-CH-0H-, -0- or −N(r)
- represents a group, and r represents a C9-C4 alkyl group. R represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a fluoroalkyl group or a formyl group. D represents an aqueous group, and E represents a halogen atom, an alkylsulfonyloxy group, or an optionally substituted benzenesulfonyloxy group. vl represents an optionally substituted pyridyl group. ) It is a heavy intermediate in the production of N-[-1(pyridyl)propyl]-N-substituted sulfonamides.

The compound of the present invention is represented by the general formula (1) shown above, and in the general formula (1), preferably, J is xO [wherein X is the same or different, a halogen atom, preferably a fluorine atom,
Chlorine atom, bromine atom; alkyl group, preferably C8-c
6 alkyl group, more preferably 0.6 alkyl group. -C4 alkyl group; haloalkyl group, preferably 01-c2 haloalkyl group, more preferably trihalomethyl group of fluorine atom, chlorine atom or bromine atom; alkoxy group, preferably haC
, ~ No. 0 alkoxy group; alkylthio group.

Preferably a C1-04 alkylthio group; an alkylsulfinyl group, preferably a 01-C1 alkylsulfinyl group; alkylsulfonyl X, preferably tt, <U
a, ~C4 alkylsulfonyl group; cycloalkyl group, preferably 0. ~C0 cycloalkyl group; nitro group; I! or a cyano group, m is Ol or an integer from 1 to 3, or adjacent Xs are bonded to each other to form -o
1÷10→r-w Knee I- or 10H-OH-OH-O
Indicates a group represented by H-. W is acid: IA atom or E
Indicates a group represented by +(0)p.

p is 0. /''!! or ko. rl and rl each represent a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or a methyl group. 1 and 1'' each represent 0 or l, and 1' represents 1 to d , and 1,1'
and 1'', the sum of which is 3 or more.] represents a phenyl group.

A is a direct bond or -0H, -, -0H-OH-.

-〇-1 or -N(r)-, r
is C3~0. represents an alkyl group, preferably a direct bond. P is an alkyl group of 01 to c3; an allyl group preferably 0. ~c4 allyl group; propargyl &; 01~C
1 alkoxy group; 0. ~0. fluoroalkyl group,
Preferably 0. 〜C1 fluoroa′ [wherein Y is the same −
te is a halogen atom.

Preferably a chlorine atom, an odor atom, or an alkyl group.

Preferably 01 to C4 alkyl group, more preferably C
2-C2 alkyl group: haloalkyl group, preferably C2
1-C8 haloalkyl group, more preferably trifluoromethyl group; alkoxy group, preferably C3-C4 alkoxy group, more preferably C5-C! alkoxy group; an alkylthio group, preferably an alkylthio group of at to C8; an alkylsulfinyl group, preferably 01 to 0
．． an alkylsulfthenyl group; or an alkylsulfonyl group, preferably < represents a C1-C2 alkylsulfonyl group, and n is 0. / or ko.

The compound represented by general formula (1) of the present invention is:

For example, it can be synthesized according to the following reaction formula.

(1) (IV) (In the above reaction formula, 2 represents a halogen atom or various sulfonyloxy groups such as tosyloxy group, J, A,
R and V indicate the ranges defined above. ) (V) (Vl) (Ia) (In the formula, zl represents a halogen atom, Bl has the same meaning as F except for alkoxy groups and formyl groups, and J, A, and V have the same meanings as above.) Above +1) The reaction represented by (2) is with a sulfonamide represented by general formula (1) or (V).

The reaction is carried out by reacting halides or sulfonates represented by the general formula (IV) or (Vl) in a cophase system of an alkali metal hydroxide 7X solution and an organic solvent in the presence of a phase transfer catalyst. The phase transfer catalyst used in this reaction can be selected from a wide range, but examples include benzyltrialkylammonium halides, tetraalkylammonium halides, methyltrialkylammonium halides, alkyltrimethylammonium halides, and alkyltrimethylammonium hydroxide halides. Examples include class 1 tetraalkylammonium bisulfates. Specifically, benzyltrimethyl(ethyl)ammonium chloride (promide), tetra n-butylammonium chloride (promide, iosito), methyl) IJ
Examples include octyl (decyl) ammonium chloride. The amount of catalyst added is the raw material sulfonamide (n)
A range of 175 molar equivalents to 17210 molar equivalents,
Preferably from 1710 molar equivalents to /// 00 molar equivalents f
jtfi & used.

As an aqueous alkali hydroxide solution, for example, hydroxide)
IJum aqueous solution and potassium hydroxide aqueous solution are mentioned, and the concentration thereof is preferably 35 to 60%. An example of an organic solvent is benzene.

Examples include aprotic solvents such as toluene, xylene, cyclohexane, cycloheptane, and dichloromethane.

The reaction temperature is in the range of 10 to 10 OC, preferably 30 to tOC, and the reaction time is in the range of Q, j to 1, preferably 1
~6 hours.

Also, one reaction is 1. For example, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, tetrahydrofuran, dioxane, 1.2
- Sodium hydride in an aprotic solvent such as dimethoxyethane.

In the presence of bases such as potassium hydride, sodium metal, potassium metal, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc., in the temperature range of -10 to 100°C, preferably 17°C to 7°C. , 0.2
It can also be carried out by reacting for ~2 hours, usually for ~6 hours.

(■) (Vjll) (In the formula, % J% A, Z', R and V have the same meanings as above.) This reaction is carried out using 1, for example, N, N-dimethylformamide, N-
Methylpyrrolidone, dimethylsulfoxide, acetonitrile, tetrahydrofuran, dioxane, 7,2-dimethoxyethane, benzene, toluene, ethyl acetate, acetone, ethylmethane, f-ketone, methanol, ethanol, cope 1. Lovanol, hydroxylated in a solvent such as water)
IJium, potassium hydride, metallic sodium, potassium gold, sodium hydroxide, potassium hydroxide.

In the presence of bases such as sodium carbonate, potassium carbonate, triethylamine, pyridine, etc., in the temperature range of -10 to /00 C, preferably 1/θ to 0.0 C, preferably 1/θ to 0.5 OC, at O,S to Coda hours 1 normal os-r hours. It is done by reacting.

In addition, in reaction formula (1) to (3), intermediate (IV), (
V) and (Vllll) (ib) (wherein J and vb are groups represented by J and V, respectively, which contain at least an alkylthio group or an alkylsulfinyl group as a substituent, and J vo
is a ゛-゛ group containing at least an alkylsulfinyl group or an alkylsulfonyl group as a substituent among the groups represented by J and V, respectively, and A and R have the same meanings as above. ) The above oxidation reaction uses chloroform, dichloromethane, carbon tetrachloride, methanol, and ethanol.

In solvents such as acetonitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, water, etc.

This is done by applying an oxidizing agent.

Examples of the oxidizing agent include metachloroperbenzoic acid, peracetic acid, aqueous peroxide, N-halogenosuccinimides, and alkali metal salts of primary hypohalous acids. The reaction is usually −koθ
It is carried out at a temperature range of ~/30°C, preferably from 10 to 10°C, for l-coda hours, preferably /%/2 hours.

[Effect]

1 The compound of the present invention is converted into N-[ni(pyridyl)propyl)-4-substituted sulfonamides useful as herbicides represented by general formulas (]a) to (lie) according to the reaction formula shown below. can lead.

(lIt+) (■)(
In the formula, T, A, R, V, V' and zl represent the same as above, pi and El combine with each other to represent 10-, D2 represents a hydroxyl group, f represents a halogen atom, p2
3 represents an alkylsulfonyl group or an optionally substituted benzenesulfonyl group. ) General formula (na) ~ obtained from the compound of the present invention by 7 steps to several steps K
The compound represented by (Inc) is used as a herbicide. It is particularly useful as a herbicide for paddy fields, and while it exhibits sufficient herbicidal activity even when applied at any time during the long period up to the advanced stage of main growth in paddy rice cultivation, it is almost harmless to rice. It has an extremely excellent property of being.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.
The present invention is not limited to the number of ships by the following examples.

Example/Synthesis of J-(N-methyl-N-(p-)luenesulfonyl)amino]--(6-)tyllhyricin-choyl)flopene I1gy to N-me + loop p-toluenesulfonamide −
, -1chloro6-(/-chloromethylvinyl)pyridine octaor, -itized tetra-n-butylammonium o
, o , ty and hydrene lS- in a mixture of go
% hydroxide) IJum aqueous solution da, 3? Add and go℃
The mixture was stirred for 30 hours.

The reaction mixture was washed successively with water and saturated brine, then dried over anhydrous potassium carbonate. After completely distilling off the solvent, the residue was subjected to silica gel column chromatography (*: open solvent system;
Dream by making a shrine with benzene-ethyl acetate ts:i)! Compound Mu30 1,! I got f.

Engineering R spectrum (neat) crn-': iz shoes, /1113. /333゜//Art, 1017'H-NMR7, Vector (CC14-TMS) δ: U11.7 (jH, 8), UjO (JH,S), U6ri (
, 7H, El), IAIJ (CoB, 13).

Yotako(/)I,br,S,)e”riCiH,br,s
, ), 7o-y, gCriJm) Example---(6-chloropyricin-choyl)-J-[:N-methoxy-N-
(p-toluenesulfonyl)ami/ ] 7'.

Synthesis of pen 0.049-41 in a mixture of 0.049- and benzene it-
Add 11.11 f of IJium aqueous solution (o% hydroxide).

The mixture was stirred at 0.degree. C. for an hour. Water the reaction mixture.

Wash sequentially with saturated saline, then dry with hot water magnesium sulfate. After distilling off the solvent and fc, the residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate 2O:t) to remove the compound described above.36. Obtained.

XPVl, vector (Ksr)an-': /sg
O,/! r! /, /1ta2゜IJA;'I, /Jll
i, //39. //30'H-NMRX vector CCJ
O] 4-TMEI) δ: Yu! 0(JH,B), J, bs
<JH, 8), 3. tri(JH,s-)wμ! (/H,
t+r, Sm), Mudako (zn, a), z coke 9 (
H, m) Example 3 Synthesis of co(6-chlorobiricin-coyl)-J-(N-methyl-N-p-)lyloxysulfonylamino)propene jo-Oily sodium hydride o, s t After washing y- with petroleum ether, drying l, unimethoxyethane/Q
- was added. p-)lyl N-methylsulfamate,
O/P and dry l--dimethoxyethane! - Add the mixture gradually while stirring at room temperature. Then, this was cooled on ice and converted into cochloromethane (b-Ci-chloromethylvinyl).
Hirisinko, 0ri? And dry! , a mixture of coco-methoxyethane S- was added for 7 hours. After stirring at room temperature for 1 hour, the solvent was distilled off. A saturated aqueous ammonium chloride solution was added to the residue, and the mixture was extracted with 1 L ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent system: vinegar-drinking ethyl-n-hexane 1:3), and compound A listed in Table 1 was purified. Obtained.

Engineering 1 spectrum k (neat) cm-': /! rt!
r,/! r! r! r, 1300°/17440. /J'
IO, //90. //ri0. //4IAr, 140. I
JO, 9j'H-NMR spectrum (0014-7M
8) δ:u? (JH, 8,),! 9J (JII, 8.)
, IAJj(J)f, Obs, L).

g40,1. -〇(each /H, oba, 8.)
, 2/7 (111, Sun,).

Kuko 0 (/H, cud,), 'ZZ＄ff-'Z Kuko (-
H, m,) Example Synthesis of N-(co(6-chlorobiricin-coyl)propen-J-yl)-N-difluoromethyl-5,6,tert-tetrahydronaphthalene-cosulfonamide N-(J-C6-/rolobiridine-coyl)propen-3-yl)-jeL, S-tetrahydronaphthalene-cosulfonamide 0. ! Of and N,N-dimethylformamide! After adding 0.0 Eff of bovb oily sodium hydride to the mixture of - and stirring for S minutes, it was cooled to - Lycium celisius and chlorodifluoromethane was introduced for a minute. After sealing the reaction vessel, return it to room temperature and then / 00℃
I kept it for S hours. After cooling to room temperature, insoluble materials were separated.

The filtrate was poured into water. This was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography (developing solvent system;
Ethyl acetate-n-hexane/: 1I) Purified by K and P/
The described compound A7S is Q, YuO? I got it.

1 spectrum (KBr) cln-': /! ;
10. /! r! ;0. /17170°13g! , /80
, 1 piece 10. //40. /10! , 100! 'H-NM
R spectrum (ODO'l, -TMS) δ: 11.0-
2 osctaH, m, ), xbs-a, θ! (#H
, m, ), auocko H9°, b8.8. ), 4
<,j:qg(each JH,obs,s,).

JH,v? 15 (JH, t, u40H2), lθ-xtao
c3H,m, ) *74Lj-21(,7H,m,) Example 5N-(ni(6-chloropyridine-niyl)
Propen-3-yl]-N-formyl-! ,6. ri, j
-Synthesis of Tetrahydronaphthalene-Nice Sulfonamide Acetic anhydride 6- was added to a mixture of ni(/-aminomethylvinyl)-4-/rolobiridine 1ilL and 9S% formic acid it- with stirring under water cooling. 3Q at room temperature
After stirring for a minute, the mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent system: ethyl acetate-n
- Purified with hexane (U:l), ni(6-chlorobilicin-niyl)-3-formamidopropenco, 0?
(mp, fO~g3°C) was obtained.

The thus obtained ny(6-chloropyricin-nyyl)-3-formamidopropene/,/6? and/or 2
-Dimethoxyethane IO- in a mixture of 60% oily sodium hydride 0. After 9 minutes of gradually adding lI2 f, ! ,4.
7J-tetrahydronaphthalene-6-sulfonyl chloride yielded 1.3 Sff. After stirring at .go.degree. C. for 6 hours, the insoluble matter was removed by a furnace, and the P solution was concentrated under reduced pressure. After adding water to the residue, extract with ethyl acetate and dilute with anhydrous sulfuric acid)
The solvent was distilled off after drying. The residue was purified by silica gel column chromatography (developing solvent system: ethyl acetate-n
- hexane l:ψ) to obtain the compound Tori 6 listed in Table 1.

Engineering R spectrum (xBr)cyn-': /70
0. /1t3s, /3rs.

／／! ! , / /J(7, 10!!'H-NMF
l, X vector ((3DO1,-TMS)δ:140-
200 (Hiro H, m,), Yu4O-100c da a, m,)
s4G&? (koIf, o be, 8e) eyo4
1j, yotza (each JH, obs, s,).

'zos-'zriOCA'E, m, ), 9 It (JH
, e, ) Example 6 Synthesis of N-methyl-N-C(6-methylsulfinylpyridin-niyyl)propen-3-yl]-'*L-tetrahydronaphthalene-ni-sulfonamide N-methyl- N-[ni(6-methylthioviricin-niyl)propene-J-i/l/]-s.

b, 'y, g-tetrahydronaphthalene-neesulfonamide o, q o y, tetrahydrofuran/1 m.

N-bromosuccinimide It,/9- was added to the mixture of dimethyl sulfoxide It- and Water Day with stirring, and the mixture was stirred at room temperature for S hours. After adding 70% aqueous sodium thiosulfate solution to the reaction mixture, extraction with benzene,
First washed with water and saturated saline, then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate J:/) to obtain the compound Atl listed in Table 7. J co? Good idea.

Engineering F spectrum k (KBr) cm-': /s
'71. , /sus, 1tlu2.

1331I, //! 110 dat') I-NMR spectrum (CDOl, -TMS) δ:
l Kuyu 0(ea, m,) * Yu AII(,7H,8,)
Iyuto (3H, e,).

Yuku, 3. o(IIH, m,), 3. va(lH,
a,) , <t3b(tm, d,).

! Ljri(iH,br,e,)smutsciH,br,
a, ), 7. Knee gl (xn, m,) example Knee (
Synthesis of Z-(a-chloropyridin-niyl)-3-( N-
Methyl-N-(3-methyl-der-methylthiobenzenesulfonyl)amine]flopen O,co0? and methanol
N-bromosuccinimide o,tt in the mixture of
Add y and stir at room temperature for an hour. 70 to the reaction mixture
% aqueous sodium thiosulfate solution was added, extracted with chloroform, washed successively with water and saturated brine, and then dried over magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system: chloroform-ethyl acetate z:i) to obtain compound A described in fi/, t90.10).

Engineering R spectrum (neat)z-”: /stl, /
! rlaO,IIIJ&.

/31Icoμist, 10qs, iobri, io, yri'H-NMR spectrum (aDcl, -7M8) δ:
Yu1Is(3)T+s-)+ariO(,71(,
8,), Yuku, 7 (JH, 1) I3.9 & (IH, d,
), even/f(IH, d, ),! &'7(IH,br
, B, )t&/,7(IH,br, s, ),2
Co-g Co(an, m,) Example IN-Methyl-H-(ni(6-methylsulfonylpyricinyl)flopen-3-yl)-jsAs, S-tetrahydronaphthalene-nii-sulfonamide Synthesis N-Methyl-N-(-1(6-methylthiopyricin-niyl)propene-,7-(ru)-t.

6. W, l-tetrahydronaphthalene-neesulfonamide I, aot-sodium acetate J hydrate O, C3? ,
A mixture of 40 ml of peracetic acid and chloroform/J was stirred to room temperature for 1000 ml and 500 ml of peracetic acid. Add carbon tetrachloride/Jtptl into the reaction mixture.

It was washed successively with water, a 10% aqueous sodium thiosulfate solution, and saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, it was crystallized and washed with a mixed solvent of ethyl acetate and n-hexane to obtain the compound muco2 listed in Table 7.
/, Jo y-obtained.

IR spectrum k (KBr) cln-I H co9.
1. #! 3; , /II! T2.

13 pieces! ! ,//! ! ! , //ko0'H-NMI'l spectrum (ODOI, -τMI3)
δ: l Kuyu o (aHem,) + Yu AJ (JH@8@
)ayu'l-3,0CIIH,m,).

J, ko9 (3H, a,), IAIA (ko■, s,), yo60 (IH, br, s, ).

A/ri (la, br, a,) s7. Knee zl (6H, m
,) Other compounds included in the above general formula (I) can also be synthesized by any of the above-mentioned methods.

Examples of synthesized compounds are shown in Table 1, and the corresponding synthesis method'f
: Shown in the Example S column.

The structures of all the compounds listed in Table 1 were confirmed by E-R and 'H-NMR spectra. In particular, for those obtained as amorphous solids, their 'H-NMR spectrum data are shown in Table 1.

Table C [Effects of the Invention] Below 1.
1 shows synthesis examples, formulation examples, and herbicidal effects of mono(pyridyl)propyl]-N-substituted sulfonamides.

Reference Example / Synthesis of -[N-(1-chlorobenzenesulfonyl)-N-methylaminoco-1-(6-chloropyridine-nyyl)-co,3-epoxypropane J -(N-(4(-/lolobenzene) sulfonyl)-
N-Methylamine]---(6-chlorobiricin-yl)propene (compound '#IJA/A)/,! ), 7(
A mixture of 796methacoo perbenzoate rRi, o'ip and chloroform 30- was stirred at 60C for S hours.

After cooling to room temperature, add 3Q-carbon tetrachloride to the reaction mixture, add -N sodium hydroxide aqueous solution, 10qb sulfite solution, and wash sequentially with IJium water bath solution, CON sodium hydroxide aqueous solution, water, and saturated brine. First, it was dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate is:i) to obtain compound 214 listed in Table 3. If I got it.

Engineering R spectrum (KBr) crn-”: tst
Ko, /luriJ, 14IQ! .

13 dao, ttst, iogi 'H-NMR spectrum (ODOI, -7M8) δ: Yui3<,yH,e,), :Ls:r<tH9rx,),
,Zkoo(ta*a-)e” shoes(/H,tl,),2
90(/H,d,),? --γg(riH0melon) Reference Example /-Synthesis of epoxy-5-(N-methyl-N-styrylsulfonylaminyl)-λ-(6-dolifluoromethylpyridinyl)propane, 7- (N-methyl-N-styrylsulfoheramino)
-2-(6-dolifluoromethylpyridinyl)
Propene (compound 1flyA u /, /?, sodium acetate trihydrate 0.0%, da 0% peracetic acid'co, /9f
, and chloroform was stirred at 60° C. for S hours. After cooling to room temperature, 10 tdf of carbon tetrachloride was added to the reaction mixture.

It was washed successively with water, a 10% sodium bisulfite aqueous solution, an aqueous solution of sodium bisulfite, water, and saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate) to obtain the compounds listed in Table 3. Obtained.

XR spectrum (neat) Crn-': J! rb
O, ko9koA, /jri7゜IO'l/'H-loss α spectrum (CDCI, -7M8) δ: Yut
Ko(,yH,a,)*Yu90(/H,d,),,2.7
riCig,a,),4AoJ(zH,a,)e@Ori(
zu,a,)mIhriJ(/H,d,),2g-&0(
9H.

m, ) Reference Example 3 Synthesis of ni(6-chloropyricin-niyl)-no,ni epoxy, 7-[N-(dermethanesulfonylbenzenesulfonyl)-N-methylaminocopropane 1-(6-chloropyricin-niyl) -3-(N-methyl-N-(l-methylthiobenzenesulfonyl)amine]furopene (compound A, ?&)/, Q g-1 Sodium acetate trihydrate 0./97%.

II (7% peracetic acid 2.6? and chloroform 10mt
The mixture was stirred at 60°C for several hours. After cooling to room temperature, add 10% carbon tetrachloride to the mixture, add water and 10%
sulfite solution) IJium aqueous solution.

The mixture was washed successively with a 2N hydroxide aqueous solution, water, and saturated saline, and then dried with anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate s:i).
Purify the compound listed in Table 3 to obtain 0.3.7
? Obtained.

Engineering R Spect/l/ (KBr) c'r11-t
: 13 zako, /! 40. /3412゜71za,/
Kogs, ii Da9'H-NMR spectrum (CDCI, -TMS) δ: Yuza4e (lH,a,), Yu90CJH,8,), J,1
0(JH,e,).

3 pieces 1H1d,), 3riq(tH,d,)*'AOda(zH,a,).

22-Zayu (RiJm,) Reference example da l-Bromo-j-(N-(Leak claw 3-
Synthesis of 7-(N-(<c-chloro-3-methylbenzenesulfonyl)-N-methylamino ]-λ-(6-chlorobiricin-niyl)propene (compound AII?) /
, Of, N-bromosuccinimide in a mixture of tetrahydrofuran 2°- and water iomt, 79? was added and stirred at room temperature for 3 hours. An IO% sodium thiomCd aqueous solution was added to the reaction mixture, which was extracted with benzene, washed with saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent thread: benzene-ethyl acetate-〇=7) to obtain the compounds listed in Table 3 &2
j 'I o, q s? Obtained.

Engineering R spectrum (neat) cm-': , 71 koo, Jqso, 1ssq.

qs, y, g'yri'H-NMR spectrum (QC''L, -TMS) δ:
Yutaku (JH, 8,) I Yu6J (ja, s,), a3g
(la, a,) + 3, go (lH, a,), Zza0 (koH * BJ + 6.77 (lH, θ,).

2 pieces 2g (6H, m,) Reference fL! /-promony(6-chloropyridine-nyyl)-nihydroxy-,7-[N-methy/I/-N-(s, 5t, t-
Synthesis of ni(6-chlorobiricin-niyl)-J-[N-methyl-N-(!r,in,?,t-tetrahydronaphthalene-ni-sulfonyl)amine]furovn(!r,in,?,t-tetrahydronaphthalene-ni-sulfonyl)amine) Compound A
7 II) 1. Of, tetrahydrofuran 1otr
t, dimethyl sulfoxide lo- and Ninobi water! 6.0 l of N-bromosuccinimide was added to the mixture with stirring, and the mixture was stirred using a trap for several hours. The reaction mixture was diluted with water, filtered with benzene, and washed sequentially with water and saturated brine.

It was then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was subjected to silica gel column chromatography (
Developing solvent system: benzene-ethyl acetate, 2O: t) was used to purify the compound Oboro 213 listed in Table 3. ! I got Jf.

Engineering R spectrum (neat) crn-': 314
! ko, irgl, 1srq.

Noda 0! , /311I'H-NMR spectrum (co14-TMS) δ:l
Ku, 2.0 (IH, m,),! A (JH,a,)9
．． l Ku, 3.0 (QI(,m,).

jJj(lH,d,),yuku,y(lH,a,),y,
tOckoL8-)t4LtJ(lH,8,),'Z/-
riy(Aa, m,)alflJ&/-Promony-
(6-chloropyricin-nyyl)-1-hydroxy-
Synthesis of 3-[N-(II-methanesulfinylbenzenesulfonyl)-N-methylamine]propane ni(6-chlorobilicin-niyl)-3-[N-methyl-N-(lI-methylthiobenzenesulfonyl)amine]flopen (Compound 't'llJ i16.jg)
To 3? , tetrahydrofuran λOnt, and 10 d of water were added N-bromosuccinimide 6 and If with stirring, and the mixture was stirred at room temperature for 2.5 hours. The reaction mixture was diluted with water, extracted with benzene, washed successively with water and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off and after 7'C, the residue was purified by silica gel column chromatography (developing solvent system: chloroform-ethyl acetate 2:1) to obtain compound A listed in Table 3 as mffL.
9 is O1S Yu? Obtained.

XR spectrum (neat)rrn-': 34I
Here, lSS waku/! 1,0゜DaSri'H-NMR spectrum (ODOL, -TMS) δ: Yuk0 (3a, s,), a7g<JH,8,), 2<<
&(lH,d,),21! :0()I(,a,),JJ
6 (YuH, 8,), 1Aj (lH, br, a,), 2k & 0 (7H, m,) Reference example /-CM-(Hiro-chloro 3-methylbenzenesulfonyl)-N-methylamino ]-! Synthesis of -(4-chloropyridine-niyl)-nihydroxy-5-(p-toluenesulfonyloxy)furopane a) t-acetoxy-J -(N-(darkrolow,7-methylbenzenesulfonyl)-Pi-methylaminoco -1-(Hiro-/Colo-3-methylbenzenesulfonyl)-N-methylamino ]-ni(6-chloroviricin-niyl)-2,3
-Nipokinguropunk, 0? , anhydrous sodium acetate3.
A mixture of 7Of and acetic acid 6Q- was stirred at 700°C for 12 hours. The reaction mixture was concentrated under reduced pressure, and 100w1" of water was added.
f and extracted with ethyl acetate and water.

The mixture was washed successively with a saturated sodium bicarbonate solution and a saturated saline solution, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (developing solvent system;
ff1-f', Z ethyl-n-hexane/2J) to give the title compound @5-ry9-. mp92~?
jC'■-loss α spectrum (apel, -TMS) δ:
Yuoocss,e,), Yudaku(,7H,a,),! 6
Ri (JH, s,).

3!3CkoL8. ), 4L2ri (JH9B, ), 1Aj
j(lH,s,).

2-1f(AH,m,) N/-[N-(guchloro-3-methylbenzenesulfonyl)-N-methylamino]-ni(6-chlorobiricin-niyl)-1,J-dihydroxy Preparation of propane l-acetoxy-,7-[N-(cuchloro-3-methylbenzenesulfonyl)-N-methylamino]-2-(
6-Chloropyricin-niyl)-1-hydroxypropane1. ! f.

A mixture of triethylamine/d, water and methanol was stirred at room temperature for a period of time.

1 mL of the reaction mixture was left overnight, and 1k crystals were precipitated.
P was removed and washed with aqueous methanol to obtain the title compound/,/
? I got an F.

mp /J/-/, 72C'H-NMR spectrum (CDCI, ・CD, OD-T
MS) δ: yu*i(, yu, a,)e yuwako (JJa,
), Nidoyuba jB, br, 5-) eslIo(tH,
d, ) ,,z4<<(lH,a,) ,a,*ci
m, br, a, ).

s,gu(sm,a, )s2kozr(6n,m,)
c)/-[N-(guchloro-3-methylbenzenesulfonyl)-N-methylamino]-ni(6-chlorobiricin-niyl)-nihydroxy-5-(1)-)luenesulfonyloxy)propane Preparation of 1-CM-(Darklow J-Methylbenzenesulfonyl)-N-,11-methyl-Cl-/rolobiridine-coyl)-1,3-dihydroxypropane 0.
3; 0? , p-) luenesulfonyl chloride 0.
A mixture of 31 f and 1 sjm of pyridine was dissolved in S at room temperature.
Stir for hours. Add benzene to the reaction mixture, add water, /
The mixture was washed successively with N hydrochloric acid and water% saturated brine, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel chromatography (developing solvent system: benzene-ethyl acetate) to obtain compounds listed in Table 3. Obtained.

XR spectrum (KBr) crn-”: 3zoo,
133s, tisq.

109ri f712'H-NMR spectrum (CDCI3-7M8) δ:2dak(iHta-)*yuas(3aws-)evlI9
(ia*a-)+a! rl: (/'H, d,), Hiroko9
()H, (1,), disease 33 (In, a,).

倶5ri(/H,br,s,)17ko-qgcioH,m
,) Reference example! r/-(N-(French-chloroJ-methylbenzenesulfonyl)-N-methyl]aminoney(6-
Reference example for the synthesis of chloropyridine-(niyl)-1-hydroxy-3-methanesulfonyloxypropane? b) l-[N-(I
I-R-3-Methylbenzenesulfo, Nitol J Loviridine-niyl)-1,3-dihydroxyfuropane o. Go y. , 11thanesulfonyl chloride 0
, 3! ;P. and a mixture of pyridine and pyridine
The mixture was stirred at C for 6 hours. Benzene was added to the reaction mixture, and the mixture was washed successively with water, /N hydrochloric acid, water, and saturated saline. It was then dried over anhydrous magnesium sulfate. After distilling off the solvent,
The residue was purified by silica gel column chromatography (developing solvent system: benzene-ethyl acetate to:i) to obtain the compound SS listed in Table 3. b 0 9-obtained.

Engineering R spectrum (K13r)ffi-': 311t
o, tsset, i33o.

7 no 6/,? AA'H-NMR spectrum (ODO'l, -TM8) δ:
QII'lC3H. a. ), LIIICJH, a. >,
IOQcJH, a. ), Yua.

(II(,d.),,2ri0(/Jd.),IA!JC
Koh H, B. ), l-'Zff Synthesis of toluenesulfonyl)amino]-X-(6-methylpyricinyl)propane l-promonyhydroxy-3-[N-methyl-N- (p-)luenesulfonyl)
Amino〇〇〇〇 to propane , anhydrous potassium carbonate 3? and methanol-
The mixture of 〇- was stirred in DaOC for 1 hour. Solvent tl-
After evaporation, add water and extract with ethyl acetate.

It was washed successively with saturated brine, and then dried over anhydrous magnesium sulfate. solvent? After evaporation, the residue was purified by silica gel column chromatography (developing solvent system: benzene-acetic acid /j:/) to obtain compound A listed in Table 3.
2 j O t-0. &l.

? Obtained.

Engineering R spectrum (KBr) m-': /r92,I
II! r9, 1.311/.

//4ri,iisr'H-NMR spectrum k (CDCI,-TMS)
δ: Lu2C3H, s. ), Yujko(,?)T,8. )
I-2, Ri? (,?H,8.)*Yuza6(/H,(1.
), 1.1g(/H,d.),,2? q(/
H, d. ), 744 (/H.

d. ), 70-'Zff (riH, m.) Similarly, other compounds listed in Table 3 were synthesized according to the method described in Reference Example M. In each case, the entire structure was confirmed by R spectrum and 'H-NMR spectrum. In particular, for those obtained as amorphous solids, the 'H-NMR spectrum data is shown in ff4 (.

Reference Example 10 Formulation Example C Granules) Part of the compound listed in Table 3 or comparative agent, 4 IJ parts of clay (manufactured by Nippon Merck Co., Ltd.), bentonite (manufactured by Toyojun Yoko Co., Ltd.) j1
1 part, 7 parts of a succinate surfactant Airol 0T-i (Toho Chemical Co., Ltd., trade name) were mixed and pulverized, and then 10 parts of water was added and kneaded. Furthermore, this was extruded through a hole with a diameter of 0411 m using an extrusion granulator, dried at 60C for one hour, and then cut into pieces of 1 to 10 cm.

Granules containing -% of the active ingredient were obtained.

Reference example/l (Flooded soil treatment test) Fill a resin pot with a soo volume of IR with rice paddy alluvial clay loam, and after fertilizing, add an appropriate amount of water and plow it to collect weed seeds of Japanese wild grass, Japanese cypress, and firefly. was sown.

The seeds were mixed well in the soil surface layer 1crII, and then paddy rice seedlings at the 7-leaf stage C product S: Akinishiki, plant height: q, z
cm, seedling quality: good) T-pot #) J stock was soaked at a depth of approximately 1 saw. After that, the water depth was maintained at 3.3 cm.

On this soil surface, 93 tubers of Cyperus japonica were placed in a T-pot.

Next, a predetermined amount of granules containing the compound listed in Table 3 as an active ingredient was dropped onto the flooded surface on the seventh day and the seventh pewter after transplantation.

The leaf age of weeds in each treatment was as follows.

Treatment plot the next day after transplantation; All weeds did not appear I. Treatment plot 7 days later; Novies I to 8! tTamagayatsuri,
Firefly it Watermelon 3~j"1m Chemically treated body, - day JCrn 1 day water leakage.

We carefully investigated the herbicidal effect and the degree of chemical damage to paddy rice.
The results are shown in Table 5.

Furthermore, the evaluation of the herbicidal effect is was determined and expressed as a herbicidal effect coefficient based on the following criteria.

In addition, the degree of chemical damage to paddy rice was evaluated according to the following criteria.

Table 5 *1 Comparative agent A: Compound OH described in JP-A No. 5r-i, yiq-ri No. 7.

*2 Comparative agent B: Compound described in JP-A-Sho SK-/3/97'Z Applicant Mitsubishi Chemical Corporation agent Patent attorney Hase - 1 other person

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, J represents a phenyl group that may be substituted or benzo-fused. A is a direct bond, or -CH_2-, -CH=CH-, -O- or -N(r
)- represents a C_1 to C_4 alkyl group. R represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a fluoroalkyl group or a formyl group. V represents an optionally substituted pyridyl group. ) N-[2-(pyridyl)propen-3-yl]-N-substituted sulfonamides. (2) In the formula (I) described in claim 1, J is ▲ a mathematical formula, a chemical formula, a table, etc. ▼ [in the formula,
are the same or different and represent a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, a cycloalkyl group, a nitro group, or a cyano group, and m is 0 or an integer of 1 to 3. or two adjacent X's are bonded to each other ▲There is a mathematical formula, chemical formula, table, etc.▼ or -CH=OH-C
Indicates a group represented by H=CB-. W represents an oxygen atom or a group represented by S(O)_p, and p represents 0, 1 or 2. r^1 and r^2 each represent a hydrogen atom or a lower alkyl group. 1 and 1'' represent 0 or 1, respectively, and 1' represents 1 to 1.
is an integer of 4, and the sum of 1, 1' and 1'' is 3 or 4], and V is ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is the same or different and represents a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, an alkylthio group, an alkylsulfinyl group, or an alkylsulfonyl group, and n is 0 or 1
or 2) represented by N-[2-(pyridyl)
Propen-3-yl]-N-substituted sulfonamides. (3) In the formula (I) described in claim 1, J is ▲ a mathematical formula, a chemical formula, a table, etc. ▼ [in the formula,
are the same or different; fluorine atom, chlorine atom, bromine atom, C_1 to C_
6 alkyl group, C_1 to C_2 haloalkyl group, C
_1 to C_4 alkoxy group, C_1 to C_4 alkylthio group, C_1 to C_4 alkylsulfinyl group,
C_1 to C_4 alkylsulfonyl group, C_3 to C_
6 cycloalkyl group, nitro group or cyano group, m is 0 or an integer of 1 to 3, or 2 adjacent
Two X's are bonded to each other ▲ There is a mathematical formula, chemical formula, table, etc. ▼ or one CH=CH
Indicates a group represented by -CH=CH-. W represents an oxygen atom or a group represented by S(O)_p, and p represents 0, 1 or 2. r^1 and r^2 each represent a hydrogen atom or a methyl group. 1 and 1'' represent 0 or 1, respectively, and 1' represents 1
~4, and the sum of 1, 1' and 1'' is 3
or 4], R is an alkyl group of C_1 to C_3, an allyl group, a propalkyl group, an alkoxy group of C_1 to C_2, a fluoroalkyl group or a formyl group of C_1 to C_3, and V is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is the same or different, chlorine atom, bromine atom, alkyl group of C_1 to C_2, trifluoromethyl group, alkoxy group of C_1 to C_2, Alkylthio group, C_1~
C_2 alkylsulfinyl group or C_1 to C_2
N-[2-(pyridyl)propene-]
3-yl]-N-substituted sulfonamide group.