CA2125570A1 - Pyrimidinyl- or triazinyl-oxy(or thio)aldehyde derivatives and their use as herbicides or plant-growth regulators - Google Patents

Abstract

Abstract of the disclosure:

Pyrimidinyl- or triazinyl-oxy (or thio) aldehyde derivatives, processes for their preparation, and their use as herbicides or plant growth regulators It is known that pyrimidinyloxy(thio)- and triazinyloxy-(thio)-carboxylic acid derivatives have herbicidal and plant-growth-regulating properties. However, some of the prior art active substance with this type of structure have disadvantages in use, such as, for example, insuf-ficient selectivity in important crops. The invention relates to pyrimidinyloxy(thio) and triazinyloxy(thio) aldehyde derivatives of the formula I with advantageous herbicidal properties:

Description

~ ~ WO 93/12094 212 ~ 3 7 0 PCT/~P92/02707 PYRIMIDINYL- OR TRIAZINYL-OX~ (OR T~IO) ALD~HYDE
DERIVATIVES AND THEIR ~SE AS HERBICIDES OR PLANT GROWTH
REGUhA~ORS

Descriptlon Pyrimidinyl- or triazinyl-oxy (or thio) aldehyde deriva-tiv~s, their preparation, and their usa i~ herbicide~ or plant growth regulator~.

It 18 k~own that pyrimidinyloxy(thio)- and triazinyloxy- ~ ~-(thio)-~arboxylic acid derivative~ have herbicidal and plant-growth regulati~g propertie~ (see EP-A-0347811, EP-A-0409369, EP-A-0409368, EP-A-400741). However, ~ome ~
of the prior art active ~ubstance~ with this type o~ :
structure have disadvantage~ in u~e, ~uch aa their insu~ficient selectivity in lmportant Qrop8 . : ::
15 Pyrlmidinyloxy(thio) and triazi~yloxy(thio)aldehyde ~ :
derivative~ with advantageous herbicidal propertie~ have now been Eound. :

The invention relate~ to compounds of the formula (I) :

~ ~ X-A (I) in which ~:: ::: :::~
20 X ia O or S, Y and Z are N or C~, but where the two radical~ Y .,~
and Z are ~ot ~imultaneously C~
Ra and * independently of one a~other ar~ hydrogen, alkyl, alkoxy, alkylthio, halog~n, halo alkoxy, haloalkyl, amino, alkylamino ox dialkylamino, A i~ a radical of the ~ormula 2~ 70 ~ ~ WO 93~12094 - 2 -- PC~/~P92/027~7 - CH - CO - R2 - CH - CH = N - R3 R1 R1 ()n_ (A1 ) (A2) --C = CH - NR4R5 --CH-- CH - x1 R~

(A3) (A4) -- CH _ CH - NR9R10 9 lo :~
1 l3 R8 ~1 NR R
(A~

_ Cl~ CH - S02 - O M ~ --CH - CH - P(= O)R

(A7) (A8) X4_$~
--' CH--~ I (A9) ~ - ~
Rl ~S I~ R13 . ~ .

X1, X2, X3 and X4 ~ndepond0ntly of on~ i~nother are O or S, prsfori~bly O, ~`

R1 i~ an al~phatic or araliphatic radical o~
the formula -~
R14 R17~18 : ~ R1~5 or R16 , ~ ~19 ': ~' .
. .

R2 ie hydroge~ or txialkylsilyl~
R3 i~ alkyl,ialk~nyl, alkynyl, alkoxy, alkenyl-oxy, alkynyloxy, alkylthio '3 7 ~
~. , Wo 93/120g4 - 3 - PCT/EP92/02707 the la~t-m~ntioned Bo~en radical~ in-depen~ently o~ one a~other bei~g u~sub-~t~.tuted or mono- or poly8ub8ti uted by radicals ~elected fro~ the group compri~-ln~ alkoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, cyano, halogen, ph~yl aRd ~ubstitut~d phe~yl, or ~ ~ alkyl~arbonyl, arylGarbonyl ~ub~tituted : arylcarbo~yl, hydroxyl, a radi~al o~ th~
~ormula NR'R", in whl~h R' ~d R" indep~n-dently of one anothor are hydrog~, alkyl, benzyl or phenyl or aminocarbo~yl, a~no-aarbonylumino,~minothioaarbonyl,~inothio-: carbonylamlno or cyaloalkyl, cycloalkenyl, cycloalken~loxy or ph~nyl, the la~t-mention~d four radical~ indepen-dently of one another bQiny un~ub~tituted or mono- or poly~ubs~ltutod by radlaal~
~ele~ted from th~ group ¢omprising alkyl, alkoxy, slkylthio, amino, alkylamino, di-alkylamino, nitro, halog~n, ayano, phenyl and ~ubatltut-d phonyl, R~ and R' lndepond~ntly o~ 0~9 a~other are hydro~en, alkyl, alkenyl, alkynyl, cycloalkyl, phe~yl, : ~ubstituted phonyl, b~zyl, alkylcarbonyl or arylcarbonyl, but where tha two radlcal~ e not simultaneously hydro~en, or R~ and Rs together with tho l~nked ~itrogen atom ara ~ 3- to 7-mambered heterocycllc r~ng which ¢an co~taln furthor het~ro atom~ ~elo~tad ~rom the ~roup co~p~ialng N, 0 and 9 in additlo~ to tha ~trogon atom a~d which c~
be substitut~d by an or:more ~lkyl groupa or 3 5 an oxo group, : R6 and R7 lndepondontly of 0~0 a~othox ar~_hydrog~n, ~lkyl, al~eny~, ~lky~yl, cycloal~yl, phonyl, ~ubatituted phanyl, b~nzyl, alkylcarbonyl or arylcarbonyl or --,~`; 2:12~79 .. wo 93~12n94 _ 4 _ - P~T/RP92/02707 R6 and R7 together with the linkod group -Xl-C~-X2-are a 4- to B-memberad ~eterocyolic r~ng which can contain further het~ro atom~
~elected fro~ tho group compri~ing N, 0 ~d S in addition ts the ~wo h~toro atoms and which can be ~ub~tituted by one or more alkyl group~, ; : R9 i~ hydrogen, alkyl, alk~nyl, 31kynyl, cyclo-alkyl, phenyl, sub~titut~d phenyl, benzyl, alkylcarbony or arylcarbonyl, R9 and R~ independently o one u~other are hydrogen, alkyl, alk~nyl, alkynyl, cycloal~yl, phe~yl, b3titut~d phenyl, b~yl, al~ylcarbony or aryloarbonyl, or 15 R9 and Rl together with he linked nitrogen atom are a 3- to 7-m~mbered heto~ocyclic ring which can contaln further h~ter~ atom~ ~elected from the group compri~g N, O a~d S in addition to the n~trogeu atom a~d whiah can be ~ubstltuted by ono or ~ore alkyl group~
or an oxo group, R~l and R~ independ2ntly of one anoth~r ar~ hydroxyl, alkyl, alkoxy, phenyl, ~ub~tltut~d ph~nyl, ph~noxy or ~ub~titut~d phenoxy, 25 Rl3 i~ hydrog~n or alkyl, R~ hydrogen, halog~n, alkyl which i~ un~u~
~tituted or ~u~stitut~d by one or more radi¢al~ eole¢ted from the group comprisln~
halogen, hydroxyl, alkoxy, alkylthio, phenyl or ~u~titut0d phenyl, or i~ hydroxyl, cya~o, cycloalkyl, aryl, prefer~bly pheD~l, thienyl, naphthyl or di~ydronaphthyl, wlth aryl or cycloAlkyl baing un~uh~t~tuted or ~ub~tituted, Rls and Rl6 independently of one another ar2 hydrogen or alkyl or Rl5 and Rl6 togeth~r with the linked aarbon ato~ ~r2 a 3- to 8-~ambQred r~g w~ich c~ co~tain an oxygen ato~ and whic~ can b~ ~ubttituted by ~ :~2 ~ r3 7 a ~0 93/120~4 - 5 - ~CT/E~P92~027~7 one or more alkyl group~, Rl7 i~ hyslrog~ or allcyl, R18 ind~pe~dently o Rl9 ie hydros~er~ or alkyl, ~Rl9 indep~:~deIl~ly of ~a i~ alkyl, aryl or ~ub-~titu'c~d aryl, or Rl~ and R~9 together with ~h~ li~ked alkenylen~ sroup i~3 a 3- to 8~ nbered ring whlch c~ on'c~in an oxys~n ato~ a~d wh~h can :b0 sub~tltu~ed by one or mor~ alkyl groups, 10 M~ ~ th2 eguival~t c~f ~ ation, pre~erably of a:~ alkal~ metal oat~ on, and n 1~ the Ilu~be3: 0 or 1.

In ~ormula (I) and her~ belowO the rad~ cAl~ alkyl, alkoxy, haloallcyl, haloalkoxy, alky~ amino and allcyl'chio 15 and the corre~porldialg un~atur t~d a~dl/or ~ubst~tuted radicals can be ~n each ca~e ~tsaigh'c-chain or branched.
Unl~ peciflcally l~di~ated, ~ t~e~e r~d~cale, the carbon atom chaln~ or carbo~ etructuree having 1 to 4 carbon ato~, or, 1~ the caue o~ unsaturated groups, 2 to 4 carbon atom~, are preferrad. Alkyl radioals, al~o in the compo~ltD meaning~ auch au alkoxy, h~loal~yl and th~
llke, are m~thyl, ethyl, n- or i-propyl, ~, i-, t- or 2-butyl; all~en~l ~nd ~lkynyl radicale ha~e the ~oanlng~
of the un~atur~ted radical~ wh~ch ars pousibl~ and which aorrDspond to ths alkyl radi~al~, such a~ 2-prop~nyl, 2-or 3-butenyl, 2-pxopynyl, or a- or 3-butynyl. Haloge~ i~
~luorine, chlorl~e, bromine or iodi~e. Haloalkyl ~ alkyl which i~ ~ub~tituted by one or more ato~s ~ele~ted ~om the group com~rislng halog~n; for exampl~, haloal~yl ~8 CF3, CHF2, CHiCF3. The ~me applie~ to haloalkenyl, halo-alkoxy and oth~r halo~n-~ub~tltuted radi~al~. Aryl ~, for ~xamplo, phe~yl, napht~yl, tetrahydronaph~h~l, indenyl, inda~yl, p~talenyl, ~luorenyl and the llke, preferably phenyl; aryloxy iB tha ~rr~ponding ryl radical~ whi h are bonde~ via a~ oxy group, ~ef~r~bl~
phenoxy. ~et~roaryl, or heteroaryl in het~roaryloxy, i~, or ~xample, pyridyl, pyrimidyl, pyridazyl, thle~yl, uryl, pyrrolyl, pyrazolyl a~d imldazolyl, pre~er~bly 2 ~ ~ ~, r~) 7 a ,_~ _ WO 93/12094 - 6 - PCT/~P92/02707 pyridyl and ~hienyl, but alRo bicyclic or polycyclic aromatic or araliphatic ~ompound~.Sub~tituted cycloalkyl iB, for example, cycloalkyl whi~h i~ ~ub~tituted by radical~ selectsd ~rom the group comprising alkyl and alkoxy. Optionally ~ub~tituted aryl, asyloxy, heteroaryl, heteroaryloxy, phe~yl, phenoxy~ ben~yl and benzyloxy and bicyclic radical0 havlng aromatic moletiea are praferably in each aa~e the corre~ponding unsub~ti~uted radical or a nub~tituted radical der~ved therefrom, the substltuent~
bei~g, ~or example, o~e or more, preferably 1, ~ or 3, radical~ ~ele~ted ~rom the ~roup compriBing halog~, alkyl, haloal~yl, alkoxy, haloal~oxy, nitro, cyano, alkoxycarbo~yl, al~ylcarbonyl, alkanoyl, ~arbamoyl, mono~
and dialkylami~ocarbonyl, mono- a~d dialkyla~no, alkyl-sulfinyl and alkylsulfonyl a~d preferred radical~ ~hichha~e sarbon atom~ being those ha~ing 1 to 4 carbo~ atom~
in particular 1 or 2 carbon atoms. Preferred ~ub~titue~te are, as a rule, tho~e selected rom the group compri~ing halogen, ~uch a~ fluorine and chlorine, C1- C4- alkyl, preferably methyl or ethyl, C,-C~-haloalkyl, prefer~bly trifluorome~hyl, Cl-C~-alkoxy, preferably methoxy or ethoxy, Cl-C~-haloalkoxy, nltro and cyano. Particularly preferxed are methyl, methoxy and chlorine.

Another cub~ect of the invention are all ~tareoieomer~
and mixture~ thereo~ which are ambra~ed by t~e formula (I), but not ~pecifically mentioned.

Co~pounds of the ~ormula (I) according to the i~ntion which are oF particular lntere~t are tho~e in which Y i~
a nitrogen atom and Z i~ a ~itrogen atom or a methine group.

Other ~ompounds o~ the ormula (I) accordi~g to ~he in~e~tion which are o~ particular interest are tho~e i~
which R~ and Rb independsntly o~ o~e a~other are hydroge~t C,-C~-al~yl, C1- C4 - alkoxy, ~,- C9 -alkylthio, halogen, C1-C4-halo~lkoxy, C~-C4-haloalkyl, - ~2~7~
~o 93/12094 - 7 - PCT/~P92/D2707 C,-C4-alkyla~i~o or di-(Cl-C4-al~yl)2mino, pre-ferably mothyl, ~ethoxy, chlorine or meth~l-amino, 1~ particular ~ho~e i~ which one o~ the two radical i8 ~ethoxy snd t~e othor radi~al i~ methyl, metho~y, chlorine or methylamino.

Other ~o~pound~ o$ the formula (I) acaording to the in~entio~ whi~h are o~ particular interest are tho~e in which R2 iY hydrogen or tri(C~-C~-alkyl3~ilyl, ~re-~rably hydrogan, R3 i~ Cl-Ci-alkyl, r2-C~ ~lkenyl, C2-C4-alkyQyl, C,-C~-al~oxy, C2-C~-alkenyloxy, C2-C4-alky~yloxy, C~-C4-al~ylthio, the la~t-~t~oned seven radioal~ ind~-pendently o~ o~e anothQr bein~ un~ub~ti-tutod or mo~o- or poly~ub~tituted by radiaal~ ~elected ~rom the group compri0-ing Cl-C~-al~oxy, Cl-C~-alkylthio, a~o, jC,-C~-alkyl)amino, di(C,-C~-alkyl) Emino~
nitro, cyano, halogan, ph~nyl and ~ubski-tuted p}lenyl, or i8 (C~-C4 alkyl)carbonyl, b~nzoyl, sub~titut~d benzoyl, hydroxyl, a r dical o~ the ~onmula NR' R" in whiah R~ and R" ind~pendently of o~e another ar~ hydrogen, C~-C~-al~yl, bsnzyl or ph~nyl, ox ic aminocarbon~l, aminocarbo~yl~mlne, aminothior~rbonyl, aminothlocarbonyla~i~o or C3-CB-ay~iloalkyl, C5 - C~ - cycloalkenyl, C5 - C~ -cycloalkenylo~y or phenyl, the la~t-me~tioned ~our radical~ indepe~-de~tly of on~ ~nother being un~ub~tituted or mo~o- or ~oly~ubetltut~d by radic~l~
~elocted ~om th~ ~roup cio~prislng C,-C~-alkyl, C,-C4-alko~y, ~ alkylth~o, a:~iso, (Cl-C4-alkyl) a~ino, dil (C,,-C~
al~yl)amino, ~itro, haloge~, cya~o, phenyl and aub~tikuted ph~nyl, 2 1 2 r rs~ {~
~0 93/~2094 - 8 - PC~Pg2/02707 R4 and Rs independently o~ one a~other are hydrog~n, ~1- C4 - al~yl, C~- C4 ~ alk~nyl, C2-C~-alkynyl, C3 -C9-cycloalkyl, phenyl, ~ub~tl~ut~d ph~nyl, ben~yl, (C~-C~-alkyl)carbo~y or benzoyl, but wh~re the two radical~ ara not ~imul-taneoualy hydroge~, or R~ and Rs together with the lin~ed ~itro~en atom are a S to 6-membered h~terocyclic ring ~ich can co~tai~ on0 or two furth~r hetero atoms ln ~elected ~rom th~ ~roup ~ompriui~g N, O a~d S in addit~on to the nitro~e~ atom a~d which can be ~ub~tltuted by o~e or ~ore Cl-C~-al~yl groups a~d an oxo group, R6 a~d R7 ind~p3nd~ntly o~ o~a a~other ~re hydro~en, C1-~4 - al~yl, ~2 - C4 - alke~yl, C~-C~-alkynyl, C3 -Ca-cycloalkyl, phe~yl, ~ub~tituted phenyl, benzyl~ (Cl-C~- lkyl)carbonyl or benzoyl or R6 and R7 toyeth~r wi~h the linked ~ro~p -Xl-CH-X7-are a 5- to 6-membered hetero~yclic ring which can co~tai~ a ~urther heter~ atom s21eat~d ~rom the group compri~ing N, 0 and S in addition to the two hetero atom~ ~nd which ca~ be ~ub3titut~d by ons or more Cl - C4 - alkyl group~, 25 ~ i9 hydrogen, Cl~C~-alkyl, C~-C~-alksnyl, C~-C~-alky~yl, C3-C~-cycloalkyl, phenyl, ~ub-~titutod phenyl, b~n~yl, (Cl-C~-~lkyl)-carbonyl or be~oyl, R9 and Rl l~d~p~ndontly of on~ a~other are hydroge~, Cl- C4 - alkyl ~ C2 - C4 - al~enyl, Ca C~-31kynyl, C3 -C8-cycloalkyl, phe~yl, hub~tituted phe~yl, b~nzyl, (Cl-C~-alkyl)carbo~yl or benzoyl or R9 ~nd R10 tossther with the li~ked nitrogen tom are a S- to 6-me~ber~d hetero~yali~ ring whl~h can co~tai~ o~e or two ~urt~er hetoro ato~s ~elected ~rom the group comprising N, 0 a~d S i~ additio~ to the ~itrogen atom and whiah can be subetituted by o~e or more C~-C~-alkyl groups ~nd an oxo group, 23.2~7a WO 93/1:i!094 - 9 - P~/~P92~02707 Rll ~nd Rl2 indepe:~ldantly of o~e another are hydroxyl, Cl-C3-alkyl, Cl-C~-alkoxy, phenyl, ~ubstl-tute~l phenyl, phe~oxy or ~ 3tituted phenoxy, Rl3 i~ hydrogen or C,-C4-alkyl, R14 ia hydroge~, halogen~ C,-Ca-alkyl which i~
un~ tl'cu'c~d or s~ab~tituted by one or mor~
radical~ ~elec~ced ~rom 'chs group co~nprl~ing haloger~, hydroxyl, C~-C~-alkoxy, Cl-C~,-alkylt~io, ph0nyl or ~ub~'citutl3d p~enyl, or i . C3 - C3 - cycloalkyl, C5 - C8 - t:ycloalkenyl, the~
la3t-~ent~oned two radicals being unEl~eti-tut~d or Elubst~ tuted by o~e or more Cl-C~-allcyl 5~3:0Up8~ or i3 hydroxyl, cyano, phenyl, thienyl, ~aph'chyl or dihydronap~thyl, th last-mentlorlQd ~our radioal~ be~ g ur~
tuted or sul:lstitut0d, R~5 and Rl6 isldependenltly o~ one ano~cher are hydrogen or Cl- C8 - al~cyl or 2 0 Rls and R~6 together with the linkQd carbon atom ~:~e a 5- to 6-me~mbered ring which can con~ain an oxygen atom and which can bs su~8ti~uted by ons or more C!l - C4 - alkyl groupEI, Rl7 ia hydrogen or Cl-C,~-alkyl, R15 i~depundently o~ R~ hydrogen or Cl-C4-alkyl, Rl9 ir~d~per~dently o~ Rl~ C1-C,~-alkyl, phenyl or eub~tltuted phenyl or R1~' and Rl9 tog2thcr w~th the linked alkenyles~e group le a 5- or 6-~embered ring which ca~ cos~tain an oxygen atom a~d whlch car~ be ~aub~ti uted by one or ~noro Cl - C~ - alkyl ~roupl3, M~ :18 a sodi~un or potaE~ium ~:atlo~l a~d n i~3 the ~umber 0 or 1, pre~erably 0.
' 35 Pr~3ferred ~ompourlds of the for~ula (3:~ according to the inventio~ are tho~e 1~ which R~ i~ hydrQgen or t:ri (C1-C2-alk~ i.lyl, preferably hydroge~, trime'chyl~3ilyl or 2 :1 2 ~ ~ ,' 3 WO 93/12094 - 10 - P~T/BP92/D2707 triethylsilyl, 1~ part$cular hydrogen, R3 1~ Cl-C~-alkyl, Cl-C~ oxy, the las~-me~tlo~ two radical~ ind~pe~-dently of o~e a~other b~ing un~ub~tituted or mo~o- or polyhalo~e~t~d or mono- or poly~ub~tltuted by C~-C~-alkoxy, Cl-C~-~l~ylthio, amino, (Cl-C~-alkyl)amlno, di(Cl-C4-al~yl~ami~o, nitro, ayano, phenyl and ~ub3t~tut~d ph~nyl, or i~ ^
t~l-Cq-~lk~13carbonyl, bo~zoyl, ~ubstituted be~zoyl, hydro~yl, a ~ad~cal o~ the ~ormul~
NR'R~ in which R' ~Id ~" independently o~
one anoth~r ~re hydrogen, C~-C~-alkyl, benzyl or phenyl, or i~ aminocarbonyl, amlnocarbo~yl~mi~o, ami~oth~ooarbo~yl, ~ othiocarbo~ylamino, cyclop~tyl, cyclo-hexyl, phenyl or sub~tl~u~ed phe~yl, R4 a~d ~5 independently o one anoth~r are h~drogen, Cl-C~-alkyl, cyclopentyl, cyclohe~yl, phe~yl, sub~tituted phenyl, be~zyl, (C~-C4-alkyl)~arbcny or b~zoyl, but wher~ th~ two radical~ are not ~imulta~eously hydroge~, or R~ and R5 togQther wlth the link3d nitrogen atom are a 5- or 6-~e~bQred hetQrocyclic ring w~ich can contain a urther hetero atom selected f ro~l the group compri~ing N a~d O 1 addit~o~ to tha ~itrog0n atom and which can be ~ub~titu~ed by o~e or more me~hyl srou~s, R6 and R7 indepondently o~ one anothor are hydroge~, C1-C~-alkyl, C~-C4~alke~yl, C2-C~-alky~yl, ~yclopentyl, cyclohexyl, ph~nyl, ~ub~tituted phe~yl, b~zyl~ (Cl-C4-alkyl)carbo~l or be~zoyl or R6 and R7 tog~th~r wit~ the li~k~d ~roup -X~-C~-X~ ~re a 5- to 6-m~mbored hcteroGyclic ring whic~
~a~ be aubstituted by o~ or ~or~ m~ hyl :
group~, .
R~ is hydrogen, C1-C~-al~yl, C2-C~-alke~
C2-C~-al~y~yl, cyclop~tyl, cycloh~yl, r~ r ~
t~
Wt) 93/12094 ~ P~ P92/027~7 phe~ylr ~ tit~at~d phenyl, be~zyl, (Cl-C~-alkyl) carbonyl or benzoyl, R9 and Rl lndependently o~ one a~other are hydrogen, C1-C~-allcyl, ~ycloperltyl, cycloh~xyl, phenyl, ~titut~d phenyl, benzyl, (C~-C~-alkyl) carbonyl or benzoyl or R~ and R10 to~eth0r with the l~n~edl nitrogen atom are a 5- to 6-membered heterocy~lic r~g which aan co~tain a ~urther he~tero ats;m ~lected fro~ the group compri~i~g N and S) in addi-tion to the ~itrogen atom and whi ch Y~all be t$tut~3d by or~e or ~ore ~ethyl group~3 r R11 and ~ depende~tly o~ osle ~other are }lydroxyl y C3-alkyl, Cl-C~-al~oxy, phenyl, ~ ti-tuted phes~yl, pherlQxy or ~ titutsd phenoxy and Rl3 i~ hydrogen or C,-C~-alkyl.

Other pre~erred s:ompound.~ o~ the ~o~mula (I) according to the invention are tho~e iIl which 2 O Rl ia an aliphatic or araliph~tic r~dicEll o~
the f ormula - CRl~R'sR'6 in which Rl~ i~ hydrogen, halogen, Cl~C~c-alkyl which i~
un~ titut~d or 3ub~tituted by on~ ox mor0 radical~ ~eleatad f ro~n the gxoup c:ompri~ g halo~3n, hydroxyl, S:~l-C,~-alkoxy, in par-ticular methoxy or ethoxy, or Cl-C~-alkyl-thio, ph~r~yl or ~ubstituted ph~r~yl, or i~
C3-C6-cyclc)alkyl, cs-c6-cyaloallceIlyl~ the la~t-x~ention0d two radical~ bsing ~ at~-tut0d or ~ tituted by one or more Cl C"-alkyl groupB, or le hydroxyl, cya~o, p~e~yl, thienyl, naphthyl or dihydronaphthyl, ch~3 3 5 la~t -me~ti oxled ~our radical~ b~ing urlaub~
tuted or sub~tituted by ~3'chyl, ethyl, methoxy, athoxy, txifluoromethyl or halogan, Rls and R~6 independar~'cly of olle another are hydroge~ or 2:~2 3~7 ~
~0 93/1209~ - 12 - PCT/BP92/02707 Cl-C4-alkyl or Rls and R~6 together with the linked carbon atom are a 5- or 6-~mbered ri~y whiah can conta~n a~
oxyge~ atom and whi~h c8~ be sub~titut~d by one or more C1 C4-alkyl group~.

R~ i~ particularly preferably Cl-C4-alkyl which i~ un~ub-~tituted or ~ub~tituted by methoxy or phenyl, or C3-C6-cycloalkyl which i~ un~ubstituted or 3ubstituted by one to thrae methyl ~roup~, in partioular i~opropyl~ tert-butyl or ayclope~tyl.

Other pre$erred co~pou~d~ of th2 0r~13 (I) accordi~g tothe invent~o~ ar~ tho~e in which A ia a ra~ical of khe ~bov~mentioned ormula (A1) or (~2).

Other pre~erred compou~ of the formula (I) ~ccording to the invention are tho~e in which the individual radical~
and groups contain two or mor~ radical~ or groups which are given ~B being preerred.

Another uubject of the present in~en ion i8 the proce~
for the preparation of compounds o~ th~ abov~entioned formula (I), which aompri~e~, a) in the ev~nt that A ha~ the ~e~ni~g o~ ~orm~la (Al~
and R~ , reacting a ~ompouud o$ ~he ~ormula (II) with a compound of the formul~ (III) Ra ~N
:Z (~--X - H N~ CH - CHO
~ y~ R1 .`
Rb ~ :
(llj (111~ : ~

212 )a7~
WO 93/12099~ - 13 - P~iBP~2/02707 where, in the formulae (II) aud (III), R', Rb, X, Y, Z and Rl axe deflned aa in ~ormula (I) and Nu~l iB a nucleo~uglc leavirlg ~roup, ~or ~xa~ple 0elected 4rom the g~oup s:ompri~ing the radical~ hals~gen, me~ylate and p- ar~d m-to~3ylate, or, b) in the event that A ha~ the meaIli~g of ~ormula (Al) and R2 1~ ~, r~a~ting a compound of th;3 ~ormula (IV) wi~h a aompou~d o~ th~ ~ormula (V) Ra \~N
z ,0~ Nuc2 t I - X - C~l - CHO
R
Rb (1~ 0 1 0 wherQ , in f ormulae ( IV) and (V), R~ , Rb , X , Y , Z and Rl are deflned au irl for~ula (I) and ~Uf2 i~3 a nucleofugic loaving group, lEor example aele~cted froan the group compri~i:ng the radlc~ls halogen, allcyl-~ulo~yl and benzyllYulonyl, or 15 c) reacting a compound of the formula (VI) Ra ~\ H CHO (~/1) Z J~X-C -Y R1 ~
Rb in which R~, Rb, X, Y, Z a~d R' are de~ined a~ in forInula (~), cl) ln the ~ nt that ~ i~ (A2) ~Lnd R2 i~ H, 20 with a com~ound oiE the formula ~H- (O)nNEI-R3 ': ::: , ' ,'` . :~:: ; -`. . -` : `' , ` '~.::' ' :':`'` :': :' .: : . : :, ' ':

2 12 3 ~ l ~
WO 93/12094 - 14 - PCT/E~P92/02707 ~n which n i~ de~inesl a~ ~ n ~ormula (A2 ), c2) in 'ch~ event th~t A 1~ (A3), with a compound of the ~ormula EINR4R5, c3) irl the event that A ~ (A4~, with a compound of the formula }IX1-R6---R7-X2~, c4) in th~ eveslt tha'c A i~ (~5), ~irst with a compound o~ thc f ormula ~R9R10 to give a cosnpound of the ormula (I), ln whic:h A i~
A6, and the;l with a compou~d o~ the ~onnula ClC}I2X3Ra, c5, in the event tha'c A 1~ (A6), with ~ compound o~ the f or~Lula ~ NR9R10 6) in che ovent that A ~ ~ (A7), with a cv~npourld o~ th~ ~osmula ~![8O3~I, c7) in the even'c that A ~ (A8), with a c:ompourld of the ~ormula :E~P ~=0~ RllRl2 and c8) in t~a event that A i~ (A9), with a co~pound o~ the ~or~ula HX4-~:o-C~ (SI~) R13, or d) converting a compound o~ the ormula (VI) given under c~ in a multi-~tep proce~, which include~
r~actlon with the compound of the~ formula HS- (C}~2) 3-S}I, a ~ ec~ent reaction with lithium alkyl a~d trialkylsiliac)n halida and reaction wi't:h mercury halide, into the compound of the formula (I3 in which A i~ (A2) and R2 i~ trialkyl~ilyl.

~ompou~d~ o:E the formula (V) 1I1 Yari.ant b) a1BO ~brace dimera of the formula (V' ) .
HC) ~ X
R~
X~
OH

whic:h are ~n o~uilibr~um with th~ re~pect~1~e monomers or which carl readily ibe t:orlvertQd iI~tO the~a mono~era u~der 30 the raaction c:03~dit~ ons .

.,3~
WO 93/l~Og~ - 15 - P~T~2P92/~707 The reaction~ o~ variants a) and b) are prefer~bly carried out in the presence of an inorganic or organic ba~e. Suitable ba~e~ are, ~or example, lnorganic ba~e~
~elected from the group o the al~ali metal carbonate~, ~uch a~ Na2CO3, ~2C03~ Na~CO3 or ~C03, alkali metal hydride~ and alkallne earth metal hydride~, ~uch a~ NaH
and RH, alkali metal~, such a3 80dium a~d pota~ium, and al~ali metal hydroxide~ ~uch a~ aodium hydroxid2 and potaa~iu~ hydroxido, or orga~ic ba~ea, ~uch aa triethylamine or D~ (1,8-diazabicyclo[5.4.0]u~dec-7-sne) .

As a rule, it i~ a~ped~ent to carry out the~e reactio~
in the pre~ence o~ a ~olvent whlch i8 inert under the reaction condition~, for example using a solve~t ~elected ~rom the group o~ the aliphatic or aromatic, optionally halogenated hydrocarbo~, ~uch a~ n-hept ~e, benzene, toluene, xyle~e, dichloromethane, tri~hloromethane and tetrachloromethane, or alcohol~, such a~, for exa~ple, methanol, ethanol and i~opropanol, or ethers, ~uch ae, ~or example, diethyl ether, diglyme, monogl~me, tetra-hydrofuran and dioxane, or ketonec, ~uch a~, for exampla, acetone and me~hyl etkyl ketone, or e~ter~, ~uch as ethyl acetate, or other aprotlc polsr ~olv~nt~, ~uch a~, for examplel dimethylformamide, N,N-dlmethylacetamide, dimethyl sulfexide and acetonitrile, or el~e water and m~xture~ of two or more of the abovemsntioned ~olve~t~.

The rsaction~ of variantu cl) to c8) can ~e carried out analogou~ly to cu~tomary method~ ~or the reactio~ of aldehyde~ with nucleophile~ and for the preparation o~
acetal~, ~or example without cataly~t or wi~h lkali~e or acidic cataly~is, pref~rably, as a rule~ under weakly acidic conditio~. The two-~tep rea~tio~ i~ accordanc~
with C4) can be carried out by, or analogou~ly to, the proce~se~ for the preparation of ~ixed acetal~, ~ox example in ~ccordance with Chem. Ber. 103 (1970) 3913 et seq.

212~0 WO 93/12~94 - 16 - PCT/~P92/027~7 The reaction~ of variant d) can be carried out analo-gously to austomary method~ for exchangi~g th~ aldehyde hydrog~n atom for 8ilyl group~, for example a~ they are described in ~. Am. Ch~m. Soc. 89 (1967) 434.

The compound~ of the formulae (II) a~d (III) re known or commercially available or can be ~ynthe~ized analogously to known proce~e~ (cf. publi~hed ~urop~a~ Patent Application ~P-A-3~7811 and J. Ch~m~ Research 1986 (5), 428 and re ere~ce~ cit~d ther~in).

~h~ compounds of the formulae (VI~ ar~ ~ovel ~nd al~o a ~ubject o~ the in~e~tio~.

The compound~ of the form~la (I) accordi~ to the inv~-tion ha~e an txcellent herbicidal acti~ity agai~t a broad range of economically important monocotyledonou~
lS and dicotyl~donouc harmful plant~. The active ~ub~tance~
al80 act e$ficiently on peren~lal weed~ which produce ~hoot~ from rhixome~, root ctock~ or other per n~ial organE and which are d~icult ~o control. ~n thi~
context, it doe~ ~ot matter wheth~r the ~ubstan~e~ are applied by pre-plant ineorpora~ion or by the pre- or post-~mergence m~thod. Speci~ic example8 may be mentioned of some represer~tativ3~ o~ the ~onoaotyl~donous and dicotyledonou~ w~ed ~lora which can be controlled by the compou~d~ according to the invention without the o~umeration h2ing lntended a~ a restriction to certain npecie~.

Exampla~ of we~d ~pecies on which the aati~e ~ubsta~e0 a~t ef~iciently are, ~rom amo~g~t the ~onocotyledo~s, Avena, ~olium, Alopecuru~, Phal~ri~, ~chi~ochloa, Digitaria, Sataria and Cyporu~ ~pecie~ ~rom th2 ann~al eector and, ~rom among~t the perennial ~pecio~, Agropyron, Cynodon, I~perata and Sorghum, and al~o perennial Cyperu~ ~pecios.

In the ca~e of the dicotyledonou~ wead ~pecies, the ~. ,, . . ~ . . . . .

., ., , ,, .~.

2~2~7a ,~
WO 93/1209~ - 17 - P~I~P9~/02707 ~pectrum of action axtend~ to ~peclaa ~uch a~, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, ~;inapi~, Ipomoea, Matri~aria, Abu'cilon asld Sida amonggt the aDnuals, and Convolvulu~, Cirsi~m, Rumex 5 and Artemi~ia in tha c~e of the perenslial weeds.

The acti~e 3ubstancen accordi~g to the in~en'cionL al~o sf ~sct an out~tandi~g con'crol of weed~ whiah occur u~der the specific ~onditio~ o~ r~ ce growing, ~uch a~, for example, Sagittari;~, Ali~ma, Eleocharis, Scirpul3 a~sd 10 CyperuH.

I~ the co~pourld~ ~ccording to 'che i~re~tio~ are pplied to the ~oil sur~aoe be rore ge~mination, then l:he waed seedling~ ars sither prev~3nted eomplately ~rom emerging, or the weads grow until 'chey ha~e reached th~ cotyledor 15 staS~e, :but then their grow'ch ~top~ ar~d, aver~tually, after three to four week~ h~ve elap~ed, they die of~
completely.

I the active sub~tance~ are applied post-~mergence ~o the green parts of the plants, growth likowi~e stop~
dra~tically a very 3hort time after the trea~me~t, a~d the w~ed plants r~main at the growth stage pertaining at the time of application, or die o~$ complet~ly ater certain tlme, ~o that, in thi~ manner, competltion by tha w~ed~ which i~ harmful to the cro~ pla~ts, i8 eliminated at a very early poi~t in time and in a ~usta~ned ~anner.

Even though the compound~ accoxding to the l~e~tion have an excellent hexbicidal aativity againat monocotyl~dono~s and dicotyl~donoua wead~, ~rop plant~ of economically important cropa ~uch aa, ~or exa~le, wheat, barl~y, ry~, rice, mai~e, ~ugar b~et, aotton and ~oya bea~, ar~
damaged not at all, or only to an in~ig~i~icant ~xtent.
For these reason~, the prescnt compou~d ar0 highly ~uitable ~or selec ivoly controlling u~d~irsd plant growth in pla~ting~ for agricultural uae.

, ~ - ~ , ~ : ,:

~ 93/1209 ~ 5 rl ~l Moreover, the ~ubstance~ according to the ~n~ention have out~tanding growth-regulating propertie~ in crop plants.
Th~y interven~ in the i2herent plant m~tabolism in a regulating manner and can therefore ba ~mployed Por ~pecifiaally in~luencing pla~t con~ti~u~nts and for fac~litating t~e harv~t~ a~, for ex~mple, by triggerlng de~iccation and growth ~tu~ting. ~oreover, they are al~o ~uitable ~or gan~rally controlling and inhibiting undes red vegetative growth without d~stroying the plants. Inhibition of th~ vegetati~e growth iB highly important in a large number o~ mono~otyledonou~ and dicotyledonou~ ~rop~ ~ince lodging aan be red~ced, or preven~ed completsly, in this man~er.

The co~pound~ o~ the formula (I~ a~cording to the inYen-tion can be used in the cu~tomary preparation~, for~xample ln the ~orm of w~ttable powdar~, ~mul8i~iabl~
concentrates, ~prayabla ~olution~, ~u~ts or ~ranulea.
Another ~ub~ect of the invention are therefore h~rbicidal and plant-growth regul~tlng co~po~it.ions which aontain compound~ o~ the formula (I).

The choic0 o~ a ~e~tain ~ormulation dep~nds on the application method de~lred and on the prevailing bio-logical and/or phy~icoche~ical param~ter~, the optimi-zation of the component~ in the ormulation generally xe~uiring ~yst~matic ser~al t~st~. Exampl~a of typ~ o~
~or~ulation~ are w~ttable powders ~WP), water-~oluble powder~ (SP), water-aolubl~ concentrate~, e~ul~iiab1e concentrate~ ), ~muleion~ (EW), ~uch as oll-in~water and water-~n-oil emul~lon~, eprayabla ~olution~, ~uspan-aion concentrat~s (SC), oil- or water-ba~ed disper~ion~, oil~m~scible ~olutiona, oap~ule 3usp~n~ion~ (C~), du~t~
(DP), ~eed-dre~sing product~, ~ranulea ~or broadca~ting and 80il ~pplication, granulea (GR) i~ the ~orm o~
microgranule~, ~pray granule~, aosted granul~ and adaorption granule~, water-diapersible gra~ule~ (WG), water-soluble gra~ule~ (SG), U~V fonmulation~, micro-cap~ule~ and waxes. The~e lndividual typen . , , .. . . . . - - .

A

.''' ' ~ ' ' ' ' ' ~ 21~ i 7 -i~
93/12094 - 19 PCT~l~P92/02707 f ormulation~ are k~owsl in pri~ciple and ar2 de~cribed, for example, ln: Wirmacker-}~uchl0r, "Chemi che Technologi~" [C!hemiaal Eng~ n~ring], Volum~ 7 , C . Hauser Verlag Nunic}l, 4th ~d. 1986, Wade ~ran ValkeDbury 5 "Pe~ticide Formulations", Marcel Dekl~er, N.Y., 1973; ~C.
Martens "Spray Drying~ ~Iandbook, 3rd Ed. 1979, G. ~oodwin Ltd. London.

The ormulatio~ auaciliarie~ r~quired, euch ?8 inart mat~rial~ urfactante, ~olvent~ and othsr additi~res are 0 al30 knOWIl and ar~ de~3crib~d, ~or ~3xample, ~n: ~atki~, "Elandboolc o4 In~cticide Dust I: ilue~t and Carr~ex~", 2nd ~3d., Darland Boolc~, Calds~sll N.~ I.v. Olph~n n Introduotion to Clay Colloid C~asnist2y"; 2nd Ed., ~ .
Wil~y ~ Sc)ns, N.Y. J C. Marnden, "Sol~re~t~ Guide" 7 2nd 15 ~Sd., Inter~cienae, N.Y. 1963; McCutcheon'8 "Det~rgent~
and E~ulsi~i~r~ Annual", MC Publ. Corp.~ Ridg~wood N.J.;
Si~ley a~d Wood, "Encyclop~dia o~ Surfac~ Acti~e Age~to", Chem. Publ. ~o. Inc., N.Y. l9Ç4; 8chonfeldt, "~ren~flachenaktiv3 Athylenoxidaddukte" tSurace-acti~e ~thylene Oxide ~dduct31, Wi8~. Verlagsgesell., ~tuttgart 1976; Winnacker-~chler, "Ch~mi~che Technologie"
~Ch~mical Engineeri~g], Vol~e 7, C. ~au~r Verlag Munich, 4th Ed. 1986.

Ba~ed on the~e ormulation~, it 1~ also po0~ible to prepare combinationu with other pe~ticidally aati~e ~ub~tance~ 8uch ~ or example, in~ectiaidee, acaricidss, herbia~de~, ~ungicide~, ~afeners, fertilizer~
and/or growth regulators, for example in the form o~
readymix or as a tank mix.

Wettable powder~ are preparation~ which are uni~ormly di~per~ible in water a~d whiah contai~, ~eside~ the acti~e ~ub~ta~ce, ionic and~or no~-ionic surfac~ant~
(wetti~g ~g~ts, di~per~ant~), or e~a~pl~ polyoxy-ethylated alkylphe~ol~, polyoxethylated F~tty alcohol~, polyoxethylated ~atty amine3~ ~atty alcohol polyglyaol ~ulfate~, alkane~ulfonates, alkylbenzene~ulfonates, , :. :: : . .

. . : , ~ .

Wo 93312094 20 2~ 7~T/~P92/o27o7 sodium lig~in ~ulfonate, ~odium 2,2'-dinaphthylmetha~-6,6'-di~ulfonate, ~od~um dibutylnaphthalan~ulfonate or ~odium oleoylmethyltaurinate, i~ addlti~n to 2 dilu~nt or inart ~ub~tance. To pTepare th0 wettabl~ powder~, the herbicidal active ~ubata~ce~ are ground finely, ~o~
example in custn~ary apparatu~e~, ~uch a~ hammer mill~, blow~r mill3 and air-jet mill~, and mixed with th~
formulation aux$1iarie~, either ~imultaneou~ly or ~ub~eguently.

~mul~ifiable concentrate~ are preparad by di~olvlng the activ~ ~ubstance ~n an organic eol~e~t, ~or ex~mple butanol, cyclohexano~, di~ethylformamld~ or xylene, or el~e high~r-bolli~g ~romatio~ or hydrocarbo~ ~r mixture~
of the orga~ic ~ol~ent~, with addition of one or more ionic and/or non-ionic surfactant~ ul~ifier~).
Exa~les of ~mulsifier~ which can be used ara: calcium alkylaryle~lfo~ates, ~uch as calcium dsdecylbenze~e-~ulfonate, or non-ionic ~mul~i~ier~, ~uch a~ atty acid polyglycol e~ter~, alkylaryl polyglycol ether~, fatty alcohol polyglycol ether~, propylene oxide/~thyl~ne oxlde condensation product~, alkyl polyethers, uorbitan eetQr~, ~uch a~, ~or example, ~orbita~ $atty ac~d e~ter~ or polyoxethylene ~orbitan e~ter~ ~uch ag, ~or example, polyoxyethylene ~orbltan ~atty acid ester~.

Du~ta are obtained by grindi~g the aative ~ub~tance with inely div~ded ~olid 0ub~t~ce~, or ~x~mple talc, natural clay~ ~uch a~ kaolln, bentonite a~d pyrophyllite, or diatomaceou~ earth.

Suspen~ion concentrates can be water or oil-ba~ed. They can bs pr~pared, ~or e~ample, by w~t grindi~s by mea~ of co~mercially avail~ble bead mill~ and, ~ appropriate, the addition o 3urfaca~t~ as they have alrsady bee~ m~n-tio~ed for axample above in the ca~e o~ the other type3 of or~ulatio~s.

Emulsions, or e~ple oil-in-water amulsion~ (~W), ~an , . ~

2 ~ rl ~
WQ 93/12094 - 21 - PCT~RP92/02707 be prepared, for exam~le, by meang o stirrer3, colloid mill3 and/or ~tatlc mixera u~ing aguaou~ organic ~ol~ent~
and, if a~propriat~, ~ux~act~ta, a0 they have already bee~ ~ention~d ~or example above in the ca~e of the other 5 type8 of or~ulationa.

Granules can be prepared either by ~pray~ng the active ~b~tance onto ad~orptive, granulated iner~ m~terial or by apply~g active ~ubsta~ce concentrates to t~e ~uraca of carriera, auch a~ ~a~d, ~oli~ite~ sr granulated l~ert material by means o~ binder~, ~or example polyvinyl alcohol~ ~odium polyacryl~te or ~ni~ral oil~. Suitabla active sub~tan~e~ ~an al~o b~ gra~ulated i~ the m~nner which i~ cu~tomary or ~e ~reparation o~ fer~ilizer granuleB~ i~ de~ired in the fo~m of a mixture with 15 fertilizar~. :

A~ a ~ula, water-di~persibl~ gra~ules ar~ prepared by the cu~tomary processe~, such a3 ~pray drying, fluidized bed granulation, diec granul~tio~, mixi~g u~ing high-~peed mixers and extru~ion without ~olid ~nert mat~rial. ~or 20 the preparation of di~ granulo~, fluidlzed bed granul~, extruder grAnules and 3pray granule~ ~ee, for ax~mple, the procea~e3 in "Spray-Drylng ~andbook" 3rd ed. 1979, G. ~oodwin Ltd., ~ondon7 ~.~. Browning, "Agglomar~tion", Chemical and En~ine3rin~ 1967, page~ 1~7 et ~8q., "Parry's Ch~mical Enginaer' ~ ~an~book", 5~h ~d., McGraw-Hill, New York 1973, pp. 8-57.

For further detalls o~ the ~ormul~tion o~ pla~t ~rotec-tion produat~ ~e~, for ~x~mple, ~.C. Xli~gman, ~Weed Control a~ a Science", John Wiley and Sons, Inc., N~w 30 York, 1961, pag~s 81-96 a~d ~.D. Froy~x, S.A. ~va~, "Weed Control ~andbook~, 5th ~d., Blackwell ~cien~i~lc Publicatione, Ox~ord, 1968, paga~ 101-103~

As a rul~, the agrocha~ical preparatio~ ~ontain 0.1 to 99~ by weight, i~ p~rt~cular 0.1 to 95% by w~ight, o~
acti~a ~ub~tanc0 o~ the ~or~ul~ (I). In w~ttable powdar~, -, - , . , :. , : ,: ~ : : ::: ~: :, :
. . . -. . .. ~ . .. .

. . .: , -: ., :: :, . ,, . : :~ . . :

,, -` 2~^3~7a ~o 93/12~4 - 22 - PCT/~P92/02707 the acti~e Bub~tan~e concentration i~, fox example, approxim~tely 10 t~ 90 by w~iyht, the rsmainder to lOD%
being oompo~ed of cue~omary ~ormulation compon~nt~. In the C~Be of emul~ifiable co~o2ntrate~, the acti~e eub-5 ~tanc~ conc~ntr~tion can be approximately 1 to 90,pre~erably S to 80, % by weight. Fo~ulations in the ~orm of dust~ ~o~tain 1 to 30, preferably in mo8t ca~es 5 to 20, % by weight of acti~e ~ubsta~a, prayable ~o~utions approximately 0.05 to 8U, pref~rably 2 to 50, % ~y we~ght of a~tive GUb8t~nC~. In th~ ca~e of water-di~p~r~ible granule~, the active ~ub~tance oontent dsp~nds partly on whethor the active oompound i8 iIl liguid or ~olid ~or~
and on wh~h ~ranulatlo~ auxlliarie~, ~iller~ ~nd the like are used. In the ca~e o~f the watar-disper ibla granule~, the acti~e ~ub~ta~ce co~tent i~, for ~x~mple, between 1 a~d 95~ by wsight, preferably between 10 and 80% by we~ght.

In addition, the abov~mentioned formulationa of active 6ub~tance contai~, i$ appropriate, the adhe~iva~, wetti~g agents, di3pers~nts, ~mulslfiers, penetrant~, pre-~ervatlv~, antifr~eze agents, ~olvent~, fillsr~, carrier~, colorants, antifoams, evaporation i~hibitors and p~ and vi~co~ity regulator~ which are cu~tomary in each ca~e.

Ba~ed on these formul~tions, lt i~ al~o po~ible to prepar~ aombination~ with other pe~ticidally ~ctive ~ub~tance~, fer~lizer~ and/or growth regulator~, $or example i~ the fo~m of a readymix or a~ a tank mix. Com-pound~ which can be u~ed in aombinatio~ with the active ~ubstances accordi~g to t~e i~e~tio~ are, for ~ample, ~nown acti~e ~ub~ta~c~ a~ they are de~cr~bed ~, for example, Weed R~oarch 26, 441-445 (1986), or ~The Pestlcide Manual", 9th ed~tion, The Briti~h Crop Protection Council, 1990/9i, Bracknell~ ~ngland, and ~n the llterature cited thereinO Examplea w~iah may b~
mantioned of herbiclde~ w~ich are known ~rom the ll~e~
rature and which can be combl~ed wit~ the compound~ o~

, . ~ ~. , :
.,.... . ~ ; ~ .

-` 2 1 2 ~ ~ l O
~0 93~12094 - 23 - P~T/~P92/02707 the fon~ula (I) are ~he following active ~ubatance~
(note: ths name3 of the compound~ gi~en are either the common name~ of the International Orga~izatio~ ~or Standardization (IS0) vr the ~h~cal ~ame~, ~f appro-priate together with a cu~tomary code numb~r)$

ace~o~hlor; aci~luorfen; aclonifen; AR~ 7088, i.e.l~[l-t5-[2-~hloro-4-(trifluoromethyl)phenoxy~-2-nltro-phenyl]-2-metho~yethylidene]a~no~o~y~acetic acid and it~
me~hyl e3ter; alachlor; alloxydim; ametry~; ~mido-~ul~uron; amitrol; A~ . ~mmo~um sul~amate;anilo~o~; a~ulam; atra~i~s; az~protryn; barban, BAS 516 ~, i.e. 5-fluoro-2-ph~nyl-4~-3~1-b~zo~azin-4-one; benazolin; benfluralin; ben~ure~ate; be~ulfuron-methyl; be~sulide; bentazone; be~zofenap; b~nzo luor;
benzoylprop-othyl; benzthlazuron; bialaphos; bifenox;
bromacil; bromobutide; bromofe~oxim; bromo~y~il;
bromuron; buminafo~; busoxino~e; butaahlor; butami o~;
but~nachlor7 buthidazole; butrali~; butylate; carbet-amide; CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamid~;
CDEC, i.e. 2-chloroallyl diethyldithiocarbamate; CG~
1~4927, i.~. 2-~4-~(5-chloro-3-fluoro-2-pyridinyl)oxy]-phono~y]propanoic aaid and 2-prop~nyl e~ter;
chlomethoxy~en; chloramben; chlorazlfop-butyl, ~iri~enop-butyl; chlorbromuron; chlorbu~am; chlor~e~a~;
chlorflurecol-methyl; ahloridazon~ chlorimuro~-ethyl;
chlornitro~n; chlorotoluron; chloroxuron; ~hlorpropham;
chlor~ulfuron; chlorthal-di~ethyl; chlorthiamid; ci~-methylinz cino~ulfuron; clethodim; ~lo~azone; clomep~op;
cloproxydim; clopyralid; cyanazi~e; cycloate; cycloxydim;
cycluron; cyperquat; ayprazine; yprazole; 2,4-DB;
dalapon; d~s~l~diphan; de~metryn; di-allatQ: diaamba;
dichlobenil; dichlorprop; di~lo~op-meth~l; di~thatyl;
di~enoxuron; dif~zoquat; diflufenican; di~efuro~;
dim~tha~hlor; dim~thametryn; di~0thazone, clomazone7 damethlpin; dimetraaulfuron; ci~o~ul~uron; dinitramine;
dinoeeb; dinoterb; diphenamid; dipropetryn diguat;
dithiopyr; diuron; DNOC; eglinazi~e-ethyl; EL 177, i.e.
5-cya~o~ di~athyl~thyl)-N-methyl-3H-pyra2O1e-4-.. -,- . -. .

~ : :

~0 33/12094 - 24 - PCT/~P92/027D7 ~arboxamide; a~dothal; EPTC; eBprocarb; ethalfluralin;
ethamet~ulfuron-m~thylt ethidi~ursn; ethiozi~; 0tho-fume~ate; F5231; i.e. N-l2-~hloro-4-1uoro-5-l4-l3-fluoropropyl)-4,5-dihydro-5-oxo-1~-t~trazol-1-yl]ph~yl]-5 ethane~ulfo~amide; F6285, i.e. 1-~5-~N-mat~ylsul$onyl)-amino-2,4-dichlorophenyl~-3-mQthyl-4-difluoromethyl-1,2~4-triazol-S-one fenopxop; fenoxan, ~. ~loma~one;
fenoxaprop-ethyl; fenuron, 1amprop-methyl; flaza-~ulfuron: fluazi op and it~ eater deri~ati~es: fluchlo-rali~; flumet~ulam; N-~2,6-di luorophe~yl]-5-methyl-(1,2,4)-triazolotl,5a]pyri~idine-~-sul~onam~ e; flume-turo~; fIumiprop~n; fluorodi~onr fluoroglycofen-~thyl;
fluridone; flurochlorido~e; ~luroxypyr; 1urt~mo~e;
foma~afe~; fo~ami~; furyloxyen; glufo~inat~; ~ly-lS pho~at~; halo~ate~; haloxy~op and ~ tB ~0t~r d~rivative~;
hexazinone; ~w 52, i.2. N-(2,3-dichlorophenyl)-4-(akho~y-methoxy)-benzamide; imaza~ethabe~z-~eth~l; imazapyr;
imazaquin; imazethamethapyr; lma~ethapyr; imazosulfuro~;
ioxyn$1; i~ocarbamide; i~opropalin; i~oproturon; i~ouron;
i~oxaben; isoxapyrifop; karbutilate; lacto~n; lena~il;
linuron; MCPA; MCPB, mecoprop; mefe~acet; me~luldide;
metam~trol; metazachlor; methabenzthiazuron~ metham;
methazole; ~ethoxyphenons; ~othyld~mron; metobromurons metolachlor; metoxuron; metribuzin; m2t~ulfuro~-methyl;
MH; molinate; mo~al~de; monocarbami~e dihydrogen ~ulfa~e;
monolinuxon; monuron; MT 1~8, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazlnamine; MT 5950, i.e. N-~3~chloro-4-(1-methylethyl)phenyl~-2-methylpent~n~
amide; naproanilids; napropamide; ~aptallm; NC 310, ~ue.
30 4-(2,4-dichlorobe~zoyl)-1-methyl-5-benzyloxypyrazole;
n~buron; nicoaulfuro~; ~ipyraclophen; nitralin; ~itro~
nitrofluorfGn; norflurazon; orbe~carb; oryæalin;
oxadiazon; oxyfluor~0~J paraguat; pe~ulate; pe~di-methali~; per~luidon~; ph~nmedipham; phe~isopham; ph~-m~dipham; pi~lora~; piperopho~; pi~ibuti~arb; piri~e~op-butyl; pretilachlor; primisul~uron-methyl; procyazi~e;
prodia~ine; proflural~n; proglinazins-ethyl; prom~to~;
prometryn~ propachlor; propanil; propaquiza~op and it~
e~tor derlvative~; pxopaztne; propham; propyz~mide;

. :.: . , ~ : : .

2 :~ 2 ~ a W~ g3/12~9~ - 25 - P~T/~P92/02707 proeul$alin; prosulfoaarb; prynachlor; pyrazoly~ate;
pyrazon; pyrazo~ulfuron-ethyl; pyrazoxy~e~; pyridate;
guinclorac; qui~merac; gui~ofop ~nd its s~t~r deriva-tive~, ~uizalo op and lt~ ester derlvati~e~; ~uizalofop-ethyl; qui~alofop-P-tefuryl; re~riduron; dy~ron; S 275, i.eO 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; S 48~, i.e. 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2~prop~nyl)-2H~1,4-banzoxazi~-6-yl)-4,5,6,7-~etrahydro-1~-i0Oindole-1,3(2~-dione;
~e~bum~to~; ~0thoxydi~; ~duron; ~i~azine; 3im~tryn; SN
106279, i.e. 2-[17-t2-chlo~o-4 ~ri~luoro-~thyl)-pheDoxy~-2-naphthalenyl~oxr]prop~nolc a~id and lt~ ~et~yl e~ter; ~ul~o~eturon-~et~yl; 8ul azuron; ~laza3ul uro~;
TCA; tebutam; tebuthiuron; tQrbacil; ter~u~arb;
terbuchlor; terbumeton; t~rbuthylazi~e; terbutryn, TFH 450, l.e. N,N-diethyl-3-t(2-ethyl-6-methylphanyl)-~ul~onyl]-1~-1,2,4-triazole-1-carboxamide; thiaza~luron;
th$f~nsulfuron-m~thyl; thiob~ncarb; tiocarbazil; tral~-oxydim; tri-allate; triasul~uron, tria~ofenam~de; tri-benuron-methyl; trlclopyr; tridipha~e; trietazins;
trifluralin; trlmeturon; vernolate; WL 110547, i.e.
5-phenoxy-1-[3-(tri~luoromethy~)phenyl3-1~-tetrazole.

For U3~, ~he formul~tion~ which are i~ commercially available form, ~re, i~ appropriate, dilut~d ln the cu3tomary manner, ~or example u~ng water in ~he ca~e o~
wettable powder~, ~mul8i~iabl~ concentrate~, di~per~ion~
and water-di~per~ible granule~. Preparation~ in the ~orm of du~t, ~ranul~s ~or 90il application or for broadca~t-ing and sprayable solution~ are convent~onally not diluted any further with othsr inert sub~tance~ be~ore u0e. The compound~ of tha ~o~ula (I) are applied, for example, poct-~mergoncs by top dre~s~ng the plant~, part~
of the plant~ and/or the ~oil on whlch, or i~ ~hich, they are growing, or pre-~mergenca onto tha 30il a~d/or the ~eeds o the plant~. I they are use~ a~ harbicidea, the~e plant~ are the~ harm~ul plant~ or the ~ed~ o theee pla~t~, and the aompound~ aecor~ing to the inven-tio~ ~an be applied in the preeence of crop ~lant~ ~ince 212~7~
WO 93~12094 - 2~ - PCT/~P92/02707 they are ~elective. If they are u~ed a~ pla~t growth regulator~, the plants then mean the crop plants, and th~
~oil i8 the araa under cultivation. The application rate re~uirad of the com~ound~ of the formula (I) ~arie as a 5 fu~ction of the e~t2rnal cond~t~on~ 3uch a~, inter alia, t2mperature, hu~idity and natur2 of the herbicide used.
It can vary wlthin wide limit~, ~or example between 0.001 and 10.0 kg/ha or ~ore o~ active i~gredie~t, but it i~
pre erably between 0.005 and 5 kg/ha.

A. Formulat~o~ ex~mple~

a) A dust i~ obtai~ed by mixi~g 10 parto by weight of a compound o~ the formula (I) a~d 90 part~ by weight of tala a~ insrt sub~tance a~d comminuti~g the mixture i~ a hammer mill.
b) A wettable powder which l~ readily disper~ible in water i8 obtained by mixing 25 parts by weight of a compound of the formula (I)~ 64 parts by weigh~ o~
kaolin-containing guartz a3 inert ~ubatance, 10 part~ by weight of potaa~ium lignln sulo~ate and 1 part by weight o~ sodium ol~oylmethyltaurlnate aa wetting and dl~p~r~ing agent and gri~d~ng the mix-ture in a pinned-di~ mill.
c) A dlap~r~ion concentrat~ whi~h i8 readily diaper-sible in water ic obtained by mixing 20 part~ by 2S weight of a compound o~ the ~ormula (I) with 6 part0 by weight of alkylphenol polyglycol ether (~Trlton X 207), 3 parts by we~ght o$ laotrideca~ol polyglycol ~ther (8 EO) a~d 71 part~ by weig~t o~
para~finic mineral oil (boiling range, ~or example, approximataly 255 to abovs 277~C) and yrinding ~he mixtur~ ln a ball mill to a ~inene~s of b~low 5 micron~.
d) ~n ~m~l~i~iablo concentrate i~ v~tai~ed from 15 parts by weight of a com~ou~d of the ~ormula ~I), 75 parts by weight o~ cycloh~xanono a~ colve~t and 10 part~ by w~ight of oxethylat~d nonylphe~l a~
emulaifier.

~ 2~ 3 ~a ~0 g3~12094 - 27 - PCT/~P92~02707 e) Water-disperuible granule~ ~re obtained by mixing 75 part~ by weight o~ a compound o~ the fonmula (I), 10 n ~alcium l~gnin ~ul~onat~, 5 n ~odium l~uryl ~ul~ate, 3 " poly~i~yl alcohol and 7 n kaolin, gr~ndi~g the mixtu~e on ~ pinned-di~ mill and granulati~g the powder in a fluidiz2d bed by spray-ing o~ water a~ gra~ulatio~ liquid.
f) Water-di~per~ible gra~ules are al~o obtalned by ho~cgenizi~g ~d pre~o~lnuti~g 25 ~arts by weigth o~ a co~pc~und o~ the on~ula (I), 5 " eodlum 2,2' di~aphthyl-~ethane-6,6'-di~ulfonate, 2 n ~odiu~ oleolymethyl-t~uriaate, 1 part by WQight 0. poly~inyl alcohol, 17 par~ by weight o~ calc~um oarbonate and 50 parts by welghts o wat0r o~ a collo~d mill, ~ub~que~tly grinding the mixture on a bead mill and atomizing and drying the re~ult~
ing ~u~pe~8io~ in a ~pray tower by mean~ o~ a singlo-subst~ce nozzl~.

B. Ch~mical example~

~-(4,6-Dlmethoxypyr~midinyl-2-oxy)-3-~ethylbuta~al (~ee Tabla 1, Bx. 1) . . .
9.1 g (66 mmol) of pot~ium carbo~at~ ar~ add~d wlth ~tirring at 25C to a 301utlon o~ 10 g (60 mmol) of 2-bromo-3-methylbuta~al, 9.4 5 ~0 mmol) o~ 4,6-di-~ethoxy-2-hydroxypyrl~idine and a ~patula-tlpfull o~ P~
2000 (PEG ~ poly~thyle~a gly~ol). AEtor the ~ea~tion ~olutio~ ha~ been ~tirred ~or 6 hours at 90C, it i~
pou~d into ~ce-wator, t~e p~ ~ brought to 5-6, and t~a mixture i~ extra~t~d u~ing dichlorom~thane. Th~ ~olutio~
35 i3 dried over ~agnosiu~ ~ul~ate and thsn co~cenkrat~d u~der reduced pres~ure; ths r~idu~ ia tak~n up ln WO 93~12094 212~ rl 3 n-heptane a~d deca~tad, and th~ clear ~olution i~
re~oncentrated. Thiu give~ 10.4 g (72% o~ theory) of 2-(4,6-dim~thoxypyrimidi~yl-2-oxy)-3-m~thylbutanalinthe form of a yallow oil of refractiva indax ~ 1.4977.

2-(4,6-Dlm0thoxypyr~idi~yl-2-oxy)-3~mathylbutanaldoxime (~ee Table 2, ~x. 25) 1 g (10 mmol) o sod~um hydroga~ carbo~ate i~ added at 25C with etlræi~g to a ~olutiv~ o 2 g ~8 ~mol~ o~
2-(4,6-dlmet~oxypyri~idl~1-2-oxy~-3-mathylbutanal ~nd 0.6 g ~8 mmol) o~ ~ydroxylamin0 hydroc~lorlde i~ 40 ~1 of methanol. The reaction oolutlon ~8 ~irrod ~or ~ hour~ at room t~mporaturs and then poured ~nto ice-water and axtracted u~ing athyl ~cetata, and tha organic pha~e is conce~rated u~dar rad~ced pra~ura. Column chro~a-tography (athyl aaetate/n-h~ptane 3:7) ~lves 1.7 g (85%
o~ th~ory) of 2-(4,6-dimethoxypyri~idi~yl-2-oxy)-3-methylbutanaldoxime in the ~onm o~ a colorle~ wax.

The remaini~g compound~ in Table 1 below are obtained analogously to th~ above-de~cribed example8 and proce~
~ariant~.

--`` 2~2~57~
~: ~10 93~12094 - 29 - E~ P~2/02707 T3ble 1: Compou~d0 o~ e ~or~ula (I~
Ra ~N
X--t:H - C~ - R2 (la) Rb Ex . R1 R2 X Y Z Ra Rb m . p . ( C ) No. or tnD ~

i-Propyl H O N CH ~3 ~3 2 ~ " u 3 u ~ u ;. ~I N~IGH3 u 4 " ~ CH3 ~ 1l r r N t:CH3 S n u a n 7 '~ n CH n n 8 " ~ " Gl 9 ~ a 1~ 1~ N ::H3 u " CH3 ù
11 t-Butyl ~ o a Y t:~CH3 " 69-71 12 " ~ Cl 13 " ~ a t t NHCH3 14 ~ CH3 ~ `:
" u J ~ N t:)C;H3 17 " ~ ~ ~ CH
18 " ~ Cl 19 r n u r NCH3 ~ ~
" ~ u 1l t ~ H3 - :

f~fJ~J~'a ~0 93/12094 ~ 30 - P~T~BP92/02707 Ex . Rl R~ X Y Z R" Rb m . p . ( C ) No. or 21 Cyclohexyl H O N CH OCH3 OCH3 23 " u ~. ,. ., NHCH3 a 24 ~ u ~ a ~ CH3 23 ~ ~1 A ~ N Ot:H3 u 26 n ~I S A D 11 27 " ~ , a CH ~ ~
2B " a n n u Cl u 29 ~ n . a ~ ~ NCH3 3!~ ~ n 1l u n CH3 31 1-Phenylethyl ~ o n ~1 oCH3 32 ~ u u a Cl u ~ 2:~2~7~
WO 93~120g~ - 31 - PCr~P92/~2707 Ex . Rl R2 X Y ~ R^ }~ m . p . ( C ) No. or ~r~D ]
.
33 1 Phenyl-ethyl H O N t::H NHCH3 OC~3 3~ u " CH3 '':, " " ~I ~I N O~ H3 u 3~ S
37 ~ H u ..
38 " " .. .. u Cl "
39 1 ~ u u n NCH3 4~ 3 41 Cyclopentyl ~l O .. n O~H3 42 n n ~ Cl u 43 ~ ~. u " " NHCH3 44 ~ ~ ,. L " ~H3 ~ N OCH
46 ~ S ~ u 47 ~ .. u " CH ~ u :.
48 " " " ~ ~ Cl "
~9 ~ .. .. u u NCH3 ~ ~ 2 3 rj 7 a WO 93/120g4 - 32 - Pt~T/13P92/02707 Ex . Rl R2 ~ Y Z R'' R~ m . p . ( C ) No. or t~

50 Cyclopentyl H S N C:~l CHq OCH3 51 3,3-Dimethyl-cyclohexyl ~ o ~ " OCH3 52 u ., ., ~, ., Cl 53 N U ~ NHCH
~4 ~ u ~. u ~ ~H3 ~1 u a 1~ N C)Cff3 ~i6 1 ~I S u ~1 u ~7 ~ .. ù " CH u u ~8 " " " ù u t~l u ~9 ~ u u ~. " N~:H3 u ~ u " " CH3 61 Cyclobutyl ~ o ~ ~ OC:H3 62 1l ~I n u Cl u - ~ 2~3~3 WO 93~12094 - 33 - Pc~ eP92/02707 Ex . Rl R2 X y Z R' Rb ~ . p .
No. or [nD20]

63 Cyclobutyl H O N CH N~C~13 O~H3 ~4 ., ~ CH3 6~ ~ ., u u N O~ H3 u 66 S u ~ n ~
67 ~ C~ ~ u B9 " u u " a INCH3 ~
u 1~ ~ R
71 2,2,3-~rimethyl-cyclopent 3-enyl ~ 0 ^ ~ 01 H3 a ~2 u u - ;- R ~1 a 73 ~ n NHC1 13 r 74 ~l u u u 3 ~ ~' u u N Ot::H3 u 76 " " S ~ ~ ~ u 77 ~ u " ~ ~H u u '~ ~ 2 ~
WO 93~1;!0g4 - 34 - PCl'/~P92/OZ707 Ex . R~ Ra X Y Z R~ Rb m . ~p ~ ( C ) No. or [nD ]

78 2,2,3-Trimethyl- H S N CH OCH3 OCH3 cyclopent-3-enyl 79 ~ ~ g ~ ~ NCH3 ~1 u ~ a r CH3 81 Cyclopropyl ~ o ~ ~1 OC:H3 82 ' " " Cl 83 " ~ u " NHC:H3 ~
84 " " " " " CH3 "
8 5 L N C~3 87 " " C~ u 83 Cl 89 " " u u .. NCH3 "
~ I N " CH

2~2~X~ ;~
WO 93/121~9~ - 35 - Pt~T~/13Pg2JO;~7~)7 13:x. Rl ~a X Y Z R~ Rb m.p. (C) No . o~ [I~"30]

91 4,4~Dimethyl-pent-2-enyl H o N t::H OeH3 OC H3 g2 " ~ Cl 3 ~ r NHC:~t3 94 ~ CH3 " " " " N C)CH3 97 u r a ~ CH a 98 ~ ~ Y ~ CH3 gg u ~ I NC}13 1 01~ h a CH3 a 1 01 2,2-Dimethyl-2-phenylethyl ~ o ~ a OCH3 r ~ u ~ Cl 103 " " ~ " " NHCH3 "
104 ~ u "

~~- 2~2l~s7a ~0 93/12094 _ 3~ _ PCT/~P92/02707 Ex. Rl ~ X Y Z R~ R~ m.p. (C) No. or [nD~~
_ 105 2,2-Dimethyl 2-phenylethyl H o N N QCH3 C)CH3 1 0~ S R
1D7 " ~ ~ ~ CH
n n H CH3 0~ I J ~ R NC:H3 111 2-Butyl . " ~ " C)CH3 "
112 u Cl 113 " R NHCH3 114 ~ ~ ~ u " CH3 11~ " u N OCH3 :
11 D . N S ~ U
1 17 N n ~ ;~ n 118 " " " '' ~ CH3 "
119 ~1 ~I N ~ NCH3 1 20 N ~ " " Ctl3; u 121 2-Methoxy-pr~p 2-yl " O " " OCH3 "
1 22 " " u " Cl 123 " u ~ ~ NHCH3 u 124 " ~ CH3 125 R ~ N OCH3 12 6 ~ S ~ ~ n D
127 u .. C~ ' u 128 '' " " ~ ~ CH3 129 " " " ~ " NCH3 "
1 3D " n n u ~ CH3 - 2 1 ~ ~ 3 7 ~
W~3 93/1209~L - 37 - PC~/BP92/02707 Table 2: Compou3ldn o:E 'chs formula (Ib) p~a ~0)~ X--CH - CH - N - R3 (Ib) Rb Ex. Rl R~ X Y 2: R~ Rb ~-P- ~C) No. or ln i-Propyl C:H~ O N C:H C~CH ~ I:iGtl 3 2 ~ N A ~I
3 S L ~1 ~1 A
4 ~ ~ ., u CH ~ "
t Butyl CH3 C) N CH OE:H3 ~CH3 6 ~ r u N ~ ., CH "
9 Cyclopentyl CH3 O N CH OCH3 OCH3 ~I ~, u ~ N
11 " " S

~-~ 2~2`~7~
WO ~3/12094 - 38 - PCT/~3P92/0~707 Ex. Rl R~ X Y Z R^ ~b m.p. ( C) No. or klD ]

Cycl~pentyl CH~ S N CH OC:H3 O ::H3 13 i Prr~pyl C2H~; O N GH OCH3 OCH3 14 ~ N
" ~ S ~ r 16 " u ~ Cll " ~1 17 t-Butyl C2H~; O N CH OCH3 OCH3 18 " " N ' 19 ~ n ,~ ~, u u ~ " CH n ~1 21 Cyclopentyl C2Hs N C;ll OC~13 OCH3 22 ~ N
23 S R U i 24 " ~ a CH ~ c~
25 i-Propyl OH O N CH O:::H3 O :H3 Wax 2 6 u .. ..
27 ~' ~; a R a a 28 " u u ~ CH a ~
29 t-Butyl a O N C:H C:)C:H3 ~H3 98-10D
" r ù u N ~ "
3 1 ~' u S R ~ u 32 '' " " '' CH ~ u :

2 ~
~0 93/12094 _ 39 _ PCT/EP92/02707 Ex. Rl R2 X Y Z R~ Rb m.p. ( C) ~ - or [ nD20]
33 GYCIOPentYI ~ O N CH OCH3 OCH3 34 ~ " N u n 37 ;-PrOPYI OC~3 N CH OCI~i3 OCH3 ~ 4964 38 ~1 ~ u n N n u 39 n S u ~ ~ n ~ ~ ., U CH ~ ~
41 t-BUtYI ~ O N CH D :;H3 C)CH3 ~-52 42 ~ r ~ ~ N
43 n S
44 r ~ C~
4~ CYCIDPentYI O~H3 O N ~H ~CH3 CH3 46 U ,. ., .. N ~ ., 47 ~ " S U ~ U ., 48 ~I ~ / " CH U ..

49 ;-PrO~VI OC2H5 O N CH ocH3 Ot:l 13 1.4924 S I
52 ~ ~ .. U CH
53 t-BUt,Vl U o N CH OCH3 OCH3 49-51 N
S
5~ Ctl 57 CYCkJPentYI ~l O N OH OCH3 ~H3 " " U ., N
~;9 n S
" " " ~ CH ~ u 61 i-Propyl C)CH2Ph O N CH OCtl3 OCH3 1,~32û

~ ~2 ~ S ~ ~) ro 93/12094 - 40 - PCT/BP92/02707 ~5x. Rl R2 X Y Z R~ Rb m.p. (C) No. or [nD ]

62 i-Propyl OCH2Ph O N N C)C:H3 OCH3 63 n S ~ rl ~ u 64 " " ~ " CH ~ " -6~ t-Butyl ~ o N CH OC~13 0C~3 r ~ ~ N
1;7 n S
6B '' u ~ CH n ~
69 Cyclopentyl. CH2Ph O N C;l I OC;H3 OCtl3 N ~ c 71 r ~ S r~ a rl r 72 r ~ CH ~ ~
72 i-Propyl NHCH3 O N CH OCH3 C)CH3 7~ H ~ I
76 t-Butyl " O N CH OCH3 OCH3 77 " ~ N ~ ~:

78 t-ButylNHCH3 S N N C)CH3 OCH3 79 ~ ~ C ~ r "
Cyclopenty. ~ C) N CH OCH3 Oc;H3 81 ~ N n D
82 " ~ S
83 " ~ ;H "
~4 i-Propyl N(CH3)2 ~ N CH QCH3 OCH3 : .
8~ " " " " N ~ "

2 1 ~
WO 93/~209~ - 41 - P~Pg2~02707 Ex . R1 R2 3~ Y Z Rl Rb m . p . ( C ) No. or [~D ]
__ 87 i-Propyl N(C:H3)2 0 S CH OCH ~ OCH3 88 t-Bu~yl O N CH 0~3 OC:H3 89 u ~ ~ N
S ~ u 9 ~ CH ~ ~
92 ::yclopentyl " C) N CH OCH3 OC~13 93 ~ N ~ , ~
94 CyclopentylN(CH3)2 S N N OCI~13 OCH3 5 ~ ., u ~. CH

~bre-~iations:
Ph = phenyl ~:~2aj ~
. ~ WO 93/12094 - ~2 - PCT/33P92/02707 Tabl0 3: Compou~d0 of th~s formula (Ic) R~ .

X CH - CH ~ R3 (Ic) ~y p~1 b Rb Ex. Rl R2 X Y Z R' Rb m.p. ~C) N~. or tsD~l i-Pr~pyl C1 13 N CH Ot:;H3 OCH3 149151 2 ~ ., c " N u u 3 " " S
4 ~ " u " CH ~
t-Butyl CH3 O N CH Ot:;H3 OCH3 129-131 , 6 ~ .. u " N
7 ' S u " ,. "
8 " " ~ " CH ~
9 Cyclop~ntyl CH3 O N CH OCH3 OCH3 " " N u u :
S ~ ~ a 12 ~ n CH
13 i~Propyl t::2H6 t:) N CH OCH3 OCH
14 " ~ ~ N
1a " ~ S
16 `' ~ " ~ CH

`

f~f~^~S ~
WO 93/1209d5 - ~3 - PC~P92/02707 :~x .Rl R2 X 'Y Z R~ Rb m . p . ( C ) No. or [nD~]

17 t~B~yi ~2~ ~ ) N CH ~C~3 0 t~3 18 " " " " N "
19 "
2D ~ n ~
21 Cyclopentyl C2H~, 0 N C:H O~ H3 ~3 22 ~ N
~3 ~, a ~; u ~ u ~

2~ i-Propyl n-Pr :) IN CH OCH3 OCH3 26 ~ r 27 ~ a S~ r a L a 28 r 1~ 4 CH L
29 t ~utyl " O N Cll OCH3 ~3 N ~ a 31 " " S " ~ ~ b 32 ~ " " " CH ~ ~

~ ~ 2~2 J 3 1 3 WO 93J120g4 - 44 - Pt~T/33P92/0270~
Ex. Rl R2 X ~r Z }2~ * m.p. (C) No. or 1~D ]

33 Cyclopentyl n Pr o N CH OCH3 OCtt3 34 ~ r ~ N
~5 ~ r 36 " " " C~H n ~
37 i-Propyl i-Pr O N CH OCH ~ C)C:J-13 38 " u N u u 39 ~ u S u ~. ,.
~' n u u CH " n 41 t-Butyl " a N C:H QCH ~ OGH~
42 u ~ ~ ~ u 43 " ~ S
44 u .. ~ .. CH ~ ~
4~ Cyclopentyl ~ O N CH OCH3 OCH3 4B " " ~ " N
47 ~ u S u h U
48 " u u ~;H
~9 i~Propyl n~Bu O N CH O ::H3 OCH ~ .
51 u S
~ u - " CH ~
S3 t-Butyl u O N CH OCH~ OCH3 54 ~ u u u N
S
~i6 ~ u ~ n 57 Cyclopentyl ~ O N Cl-l OCH3 C)C~3 ~E3 " " " " N u ~. :
~g " " S u u ..
~ u ~ CH "
61 i-Propyl CH2Ph N eH Ot:;~33 C~H3 i .. , ., . . ~ , , . . ~ .. ... . . . . .

% ~ 2 ~
WO 93/12090~ - 45 - PCT/~P9;!/02707 Ex. Rl R~ X Y Z ga R~ m.p . ( C) ~ or [nD20]

62 i-Propyl CH2Ph O N N t)C;H3 O~ H3 6 3 ~ ~ u " "
6~ 1~ n u u CH ~ ~
66 t-Butyl ~ Q N CH OCH3 C)C~l3 66 " ~ " " N "
67 " S u .. u ,.
63 u C~l u ~ -69 Cycl~pentyl ~ o N CH Oi:;tl3 OCH3 ~ u , ~ N D
71 a S
72 u ~ Ct~
72 2-Butyl CH3 C) N CH OCH3 OCH3 73 1~ a N
74 S ~' 7~ " " " " CH ~ l~
76 i Butyl '' O N CH t)CH3 OCH3 77 1l 1~ 1l 1l N " "

25-)7~
93/1209~ - 46 - ~1?~/~P92~27~7 ~x. Rl R2 ~ y Z R~ R~ m.p. (C) No. or [~~
.
78 i-Butyl CH3 S N N l:K:I-13 ~C~3 79 " u ~ C~l 80 C:yclohexyl ~ O N CH OCH3 C:~CH3 B1 " ~ " ~ N ~ ~
82 ~ n ~ O
E33 ~ C~
B4 Ethyl C:H3 O N t;l l OCH3 OCH3 ~ u u 5~ "
~6 ~1 ~ u 1~ u r 87 ~ A ~H ~ u 88 n-Propyl N O N CH OCH3 C )C~3 u ~ ~ N "
S
91 ~ " " u CH u 92 n-Propyl C2H~ N C:H OCH3 OCH3 93 " " " " N " ~ :
94 " " S N N ~CH3 O~tl3 9~i " " u ~ C H n u Abbreviations:
Pll '- phenyl Pr a propyl Bu = butyl . ,.. .. . ... , . , . ~ .. . .

2 12 ~
93/~2094 - 47 - ~CT/~P9~/02707 Biological example~

The damage to the weed plants, or the oompatability with the crop plantQ, was ~cored usi~g a key ln which the effecti~enes~ i~ expres~ed by ~alue~ 0 to 5~ Tha ~alues denote:

0 - ~o effeck - O to 20% efff~ct or d~mage 2 ~ 20 to 40% e~fect or d~mage 3 = 40 to 60% effect or damaga 4 ~ 60 to 80% eff~ct or damage = 80 to 100% ef~e~t or da~age 1. Pre-~mergence ~ffect on weeds Seed~ or rhizome piece o~ monocotyledonou~ and dicotyledonouQ weed plant~ were pla~ed in ~andy loam eoil in plastic pota and covered with soil. The compounds according to the invention which wers formulated in the form of wettable powdern or emul~ion conc~trat~s were then applied to the 3urface of the 00il cover ln he ~orm of aqueou~ ~u~pen3ions or emul~iona ~t a~ application rate of 600 to 800 1 of water/ha (~onverted), i~ ~ariou~
dosages.

After the traatment, the pots were placed in ~ grse~house and kept under good growth conditio~a ~or th~ wee~aO
After the ~eat plants had ~merg~d, the damage to the planta or the ~egati~e ~ffect o~ the ~mergenoe waa ~cored ~isually a~t~r a test period of 3 to 4 WeekQ by com-pari~o~ with untreated co~rol~. AB ~hown by the ~ost re~ults, the co~pounds accordi~g to the i~ve~tio~ hav~ a good herbiGidal pre-2mergence aati~ity again0t a broad ra~ge o~ grasR weeds and broad-leaved we~da. For exampl~, the compounds (Ia) of Examples 1 and 11 of Table 1, the compound~ (Ib) o Bxampl~ 25, 29, 37, 41, 49, 53 and 61 o Tabla 2 and the co~pound~ (Ic) of Example~ 1 a~d 5 of Table 3 ha~e a very good h~rbicidal actl~ity again~t 2~ ~3 )7~
, WO 93/1209~1 - 4~ - PC~ P9;!/02707 harmful plant~3 ~uch a~ Sl~api~ alba, Stellaria m~dia, Echir~ochloa cru~ galli, Loliu~ ~multif lorum and ~vena fatua when u~2d pre-emerg0rlce.

2. Po~t-emergence e~fact on weeds 5 Seeds or rhizome pt ~e~ of monoc~oty:Lcdonou~ and dicotyledonou~ weeds were plac~d i~ ~andy loam 80il in plastic pot~, oovered w~th ~oil a~d growrl $n the greenhou~e ~dax good growth conditlon~. Threa w2~k~
af tar ~owing, the te~t pla~ were tx~3ated i~ the three-10 loaf ~tag~.

Th~ compour~d~ ac~ording 'co the inven~cion which wers~ormula'ced a~ wettable powder0 or a~ emul~ion co~cen-trE~tl3s were ~prayed in variou~ do~age~ on~o the green parts o~ the pla~t~ at am applica'clor~ rate of 600 to 15 800 1 of wat~r/ha (con~rerted) and, a~r th~3 te~ plant~
had r0mained in the greenhou~3e ~or about 3 to 4 weekR
und~3r ideal growth conditlorls, the ef ~ect of the pre-par~tion3 waF~ Mcored vi~ually by compari~on with untreated controla. The compo~itions according to th~
in~ention al~o have a good herbicidal po~t-~merge~c~
a¢t~vity aga~n~t a broad rangs o~ e~onomically important gras~ weed~ a~d broad-l~aved w~ed~. For ~xampl~, the compound~ ~Ia) o~ l~xample~ 1 a~d 11 o$ Tabl~s 1, th~
compound~ (Ib) of Ex~mples 25, 2~, 37, 41, 49, 53 and 61 2 5 o~ Table 2 arld the compound~ ( Ic ) o Examples 1 and 5 of Table 3 ha~re a very yood herbicidal activity agai:slst harmful plant~ ~uch 3L~ Sinapis alba, Stellaria media, Echinochloa cru~-galli, ~oliu~ ~ulti~lor~n and ~vena fatua when appl~ ed post-emer~ence.

Claims (11)

Patent claims

1. A compound of the formula (I) (I) in which X is O or S, Y and Z are N or CH, but where the two radicals Y and Z are not simultaneously CH, Ra and Rb independently of one another are hydrogen, alkyl, alkoxy, alkylthio, halogen, haloalkoxy, haloalkyl, amino, alkylamino or dialkylamino, is a radical of the formulae (A1) to (A9), (A1) (A2) (A3) (A4) (A5) (A6) (A7) (A8) (A9) X1, X2, X3 and X4 independently of one another are O or S, R1 is an aliphatic or araliphatic radical of the formula or R2 is hydrogen or trialkylsilyl, R3 is alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, the last-mentioned seven radicals independently of one another being unsubstituted or mono- or polysubsti-tuted by radicals selected from the group comprising alkoxy, alkylthio, amino, alkylamino, dialkylamino, nitro, cyano, halogen, phenyl and substituted phenyl, or is alkylcarbonyl, arylcarbonyl substi-tuted arylcarbonyl, hydroxyl, a radical of the formula NR'R", in which R' and R" independently of one another are hydrogen, alkyl, benzyl or phenyl or aminocarbonyl, aminocarbonylamino, aminothiocarbonyl, aminothiocarbonyl-amino or cycloalkyl, cycloalkenyl, cycloalkenyl-oxy or phenyl, the last-mentioned four radicals independently of one another being unsubstituted or mono-or polysubsti-tuted by radicals selected from the group comprising alkyl, alkoxy, alkylthio, amino, alkylamino, di-alkylamino, nitro, halogen, cyano, phenyl and substituted phenyl, R4 and R5 independently of one another are hydro-gen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbony or arylcarbonyl, but where the two radicals are not simultaneously hydrogen, or R4 and R5 together with the linked nitrogen atom are a 3- to 7-membered heterocyclic ring which can contain further hetero atoms selected from the group compris-ing N, O and S in addition to the nitrogen atom and which can be sub-stituted by one or more alkyl groups or an oxo group, R6 and R7 independently of one another are hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbonyl or arylcarbonyl or R6 and R7 together with the linked group -X1-CH-X2- are a 4- to 8-membered heterocyclic ring which can contain further hetero atoms selected from the group comprising N, O and S in addition to the two hetero atoms and which can be substituted by one or more alkyl groups, Ra is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbony ro arylcarbonyl, R9 and R10 independently of one another are hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl, benzyl, alkylcarbony or arylcarbonyl, or R9 and R10 together with the linked nitrogen atom are a 3- to 7-membered heterocyclic ring which can contain further hetero atoms selected from the group compris-ing N, O and S in addition to the nitrogen atom and which can be substi-tuted by one or more alkyl groups or an oxo group, R11 and R12 independently of one another are hydroxyl, alkyl, alkoxy, phenyl, sub-stituted phenyl, phenoxy or substituted phenoxy, R13 is hydrogen or alkyl, R14 is hydrogen, halogen, alkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, alkoxy, alkylthio, phenyl or substituted phenyl, or is hydroxyl, cyano, cyclo-alkyl, aryl, with aryl or cycloalkyl being unsubstituted or substituted, R15 and R16 independently of one another are hydrogen or alkyl or R15 and R16 together with the linked carbon atom are a 3- to 8-membered ring which can contain an oxygen atom and which can be substituted by one or more alkyl groups, R17 is hydrogen or alkyl, R18 independently of R19 is hydrogen or alkyl, R19 independently of R18 is alkyl, aryl or substituted aryl, or R18 and R19 together with the linked alkenylene group is a 3- to 8-membered ring which can contain an oxygen atom and which can be substituted by one or more alkyl groups, M+ is the equivalent of a cation, and n is the number 0 or 1.

2. A compound as claimed in claim 1, wherein Ra and Rb independently of one another are hydro-gen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, C1-C4-haloalkoxy, C1-C4-haloalkyl, C1-C4-alkylamino or di-(C1-C4-alkyl)amino.

3. A compound as claimed in claim 1 or 2, wherein R2 is hydrogen or tri(C1-C4-alkyl)silyl, R3 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, the last-mentioned seven radicals independently of one another being unsubstituted or mono- or polysubsti-tuted by radicals selected from the group comprising C1-C4-alkoxy, C1-C4-alkylthio, amino, (C1-C4-alkyl)amino, di(C1-C4-alkyl)amino, nitro, cyano, halogen, phenyl and substituted phenyl, or is (C1-C4-alkyl)carbonyl, benzoyl, substi-tuted benzoyl, hydroxyl, a radical of the formula NR'R" in which R' and R"
independently of one another are hydrogen, C1-C4-alkyl, benzyl or phenyl, or is aminocarbonyl, aminocarbonyl-amino, aminothiocarbonyl, aminothio-carbonylamino or C3-C8-cycloalkyl, C5-C8-cycloalkenyl, C5-C8-cycloalkenyloxy or phenyl, the last-mentioned four radicals independently of one another being unsubstituted or mono- or polysubsti-tuted by radicals selected from the group comprising C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, amino, (C1-C4-alkyl)amino, di(C1-C4-alkyl)amino, nitro, halogen, cyano, phenyl and substituted phenyl, R4 and R5 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbony or benzoyl, but where the two radicals are not simultaneously hydrogen, or R4 and R5 together with the linked nitrogen atom are a 5- to 6-membered heterocyclic ring which can contain one or two further hetero atoms selected from the group comprising N, O and S in addition to the nitrogen atom and which can be substituted by one or more C1-C4-alkyl groups and an oxo group, R6 and R7 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl or R6 and R7 together with the linked group -X1-CH-X2- are a 5- to 6-membered heterocyclic ring which can contain a further hetero atom selected from the group comprising N, O and S in addition to the two hetero atoms and which can be substituted by one or more C1-C4-alkyl groups, R8 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl, R9 and R10 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl or R9 and R10 together with the linked nitrogen atom are a 5- to 6-membered heterocyclic ring which can contain one or two further hetero atoms selected from the group comprising N, O and S in addition to the nitrogen atom and which can be substituted by one or more C1-C4-alkyl groups and an oxo group, R11 and R12 independently of one another are hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, substituted phenyl, phenoxy or substituted phenoxy, R13 is hydrogen or C1-C4-alkyl, R14 is hydrogen, halogen, C1-C8-alkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, phenyl or substituted phenyl, or is C3-C8-cyclo-alkyl, C5-C8-cycloalkenyl, the last-mentioned two radicals being unsubsti-tuted or substituted by one or more C1-C4-alkyl groups, R15 and R16 independently of one another are hydrogen or C1-C8-alkyl or R15 and R16 together with the linked carbon atom are a 5- to 6-membered ring which can contain an oxygen atom and which can be substituted by one or more C1-C4-alkyl groups, R17 is hydrogen or C1-C4-alkyl, R18 independently of R19 is hydrogen or C1-C4-alkyl, R19 independently of R18 is C1-C4-alkyl, phenyl or substituted phenyl or R18 and R19 together with the linked alkenylene group is a 5- or 6-membered ring which can contain an oxygen atom and which can be substituted by one or more C1-C4-alkyl groups, M+ is a sodium or potassium cation and n is the number 0 or 1.

4. A compound as claimed in any of claims 1 to 3, wherein R2 is hydrogen or tri(C1-C2-alkyl)silyl, R3 is C1-C4-alkyl, C1-C4-alkoxy, the last-mentioned two radicals inde-pendently of one another being unsub-stituted or mono- or polyhalogenated or mono- or polysubstituted by C1-C4-alkoxy, C1-C4-alkylthio, amino, (C1-C4-alkyl)amino, di(C1-C4-alkyl)amino, nitro, cyano, phenyl and substituted phenyl, or is (C1-C4-alkyl)carbonyl, benzoyl, substi-tuted benzoyl, hydroxyl, a radical of the formula NR'R" in which R' and R"
independently of one another are hydrogen, C1-C4-alkyl, benzyl or phenyl, or is aminocarbonyl, aminocarbonyl-amino, aminothiocarbonyl, aminothio-carbonylamino, cyclopentyl, cyclohexyl, phenyl or substituted phenyl, R4 and R5 independently of one another are hydrogen, C1-C4-alkyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbony or benzoyl, but where the two radicals are not simultaneously hydrogen, or R4 and R5 together with the linked nitrogen atom are a 5- or 6-membered heterocyclic ring which can contain a further hetero atom selected from the group comprising N and O in addition to the nitrogen atom and which can be substituted by one or more methyl groups, R6 and R7 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl or R6 and R7 together with the linked group -X1-CH-X2 are a 5- or 6-membered heterocyclic ring which can be substituted by one or more methyl groups, R8 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl, R9 and R10 independently of one another are hydrogen, C1-C4-alkyl, cyclopentyl, cyclohexyl, phenyl, substituted phenyl, benzyl, (C1-C4-alkyl)carbonyl or benzoyl or R9 and R10 together with the linked nitrogen atom are a 5- to 6-membered heterocyclic ring which can contain a further hetero atom selected from the group comprising N and O in addition to the nitrogen atom and which can be substituted by one or more methyl groups, R11 and R12 independently of one another are hydroxyl, C1-C2-alkyl, C1-C4-alkoxy, phenyl, substituted phenyl, phenoxy or substituted phenoxy and R13 is hydrogen or C1-C2-alkyl.

5. A compound as claimed in any of claims 1 to 4, wherein R1 is an aliphatic or araliphatic radical of the formula in which R14 is hydrogen, halogen, C1-C6-alkyl which is unsubstituted or substituted by one or more radicals selected from the group comprising halogen, hydroxyl, C1-C4-alkoxy, in particular methoxy or ethoxy, or C1-C4-alkylthio, phenyl or substituted phenyl, or is C3-C6-cyclo-alkyl, C5-C6-cycloalkenyl, the last-mentioned two radicals being unsubsti-tuted or substituted by one or more C1-C4-alkyl groups, or is hydroxyl, cyano, phenyl, thienyl, naphthyl or dihydronaphthyl, the last-mentioned four radicals being unsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, trifluoromethyl or halogen, R13 and R16 independently of one another are hydrogen or C1-C4-alkyl or R15 and R16 together with the linked carbon atom are a 5- or 6-membered ring which can contain an oxygen atom and which can be substituted by one or more C1-C4-alkyl groups.

6. A process for the preparation of compounds of the formula (I) as claimed in any of claims 1 to 5, which comprises a) in the event that A has the meaning of formula (A1) and R2 is H, reacting a compound of the formula (II) with a compound of the formula (III) (II) (III) where, in the formulae (II) and (III), Ra, Rb, X, Y, Z and R1 are defined as in formula (I) and Nuf1 is a nucleofugic leaving group, or, b) in the event that A has the meaning of formula (A1) and R1 is H, reacting a compound of the formula (IV) with a compound of the formula (V) (IV) (V) where, in the formulae (IV) and (V), Ra, Rb, X, Y, Z and R1 are defined as in formula (I) and Nuf2 is a nucleofugic leaving group, or c) reacting a compound of the formula (VI) (VI) in which Ra, Rb, X, Y, Z and R1 are as defined in formula (I), c1) in the event that A is (A2) and R2 is H, with a compound of the formula H-(O)nNH-R3 in which n is defined as in formula (A2), c2) in the event that A is (A3), with a compound of the formula HNR4R5, c3) in the event that A is (A4), with a compound of the formula HX1-R6---R7-X2H, c4) in the event that A is (A5), first with a compound of the formula HNR9R10 to give a compound of the formula (I), in which A is A6, and then with a compound of the formula ClCH2X3R8, c5) in the event that A is (A6), with a compound of the formula H-NR9R10, c6) in the event that A is (A7), with a compound of the formula MSO3H, c7) in the event that A is (A8), with a compound of the formula HP(=O)R11R12 and c8) in the event that A is (A9), with a compound of the formula HX4-CO-CH(SH)R13, or d) converting a compound of the formula (VI) given under c) in a multi-step process, which includes reaction with the compound of the formula HS-(CH2)3-SH, a subsequent reaction with lithium alkyl and trialkylsilicon halide and reaction with mercury halide, into the compound of the formula (I) in which A is (A2) and R2 is tri-alkylsilyl.

7. A compound of the formula (VI), (VI) in which Ra, Rb, X, Y, Z and R1 are defined as in formula (I) as claimed in any of claims 1 to 5.

8. A process for the preparation of compounds of the formula (VI) as claimed in claim 7, which comprises reacting a compound of the formula (II) with a compound of the formula (III) (II) (III) where, in the formulae (II) and (III), Ra, Rb, X, Y, Z and R1 are defined as in formula (VI) as claimed in claim 7 and Nuf1 is as nucleofugic leaving group, or reacting a compound of the formula (IV) with a compound of the formula (V) (IV) (V) where, in the formulae (IV) and (V), Ra, Rb, X, Y, Z
and R1 are defined as in formula (VI) and Nuf2 repre-sents a nucleofugic leaving group.

9. A herbicidal and plant-growth regulating com-position, which comprises a compound of the formula (I) as claimed in any of claims 1 to 5 and customary formulation auxiliaries.

10. The use of the compounds of the formula (I) as claimed in any of claims 1 to 5 as herbicides or plant-growth regulators.

11. A method of controlling harmful plants or for regu-lating the growth of plants, which comprises apply-ing one or more compounds of the formula (I) as claimed in any of claims 1 to 5 to the plants, the seeds of the plants or the soil on or in which the plants grow.