BE714007A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 
 EMI1.1
 



  G; r.: R1; '. / Qa 'tsgfiil! t! é34-'f2OP rp: a ..: os' dsi,: 1 # i13 tt1: 11.11-F} iôee disubet: 1t \ i {} a <@ at the asete.

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   The present invention relates to novel amino acid derivatives having useful herbicidal properties, to processes for their preparation, to compositions containing them and to a process for controlling the growth of unwanted plants using these derivatives.



   In modern methods of agricultural industry; it has been found possible to leave the cereals standing until the ears are completely ripe. This was not the case previously when the harvest was more dependent on weather conditions and lasted longer. Unfortunately, wild oats ripen faster than cereals and, when this weed is present, its seeds are now widespread. part in the ground before harvest;

   in this way, a serious infestation of the arable land by wild oats occurred. In addition, it is very difficult to separate the seeds of wild oats from the kernels of other cereals3 and the presence of wild oats in a sample of seed wheat, for example, seriously reduces its commercial value. Chemical control of this noxious plant has already been attempted, but these attempts have not been completely successful.

   It has now been discovered that derivatives of amino acids of a new class have useful selective herbicidal properties, and in particular make it possible to better control wild oats.



   The novel amino acid derivatives of the invention are nitrogen disubstituted amino acid derivatives of the formula

 <Desc / Clms Page number 3>

 
 EMI3.1
 
 EMI3.2
 wherein R represents a tl1aloOne atom, preferably Qno9, a chlorine atom, or an alkyl or alkoxy group; n represents 0 or an integer from 1 to 5, and when n this
 EMI3.3
 greater than 1, the groupoments R can be ldontiquos and}. ! '% le reprôsonte MK gr () t \ pcmnt alcoylèl.1o, de j..rôi? ±:? - anae un gï = cupeB! oa' '<éihylidànàj ù>' uit gruesn '!:

   alsoyl cisoxy aryl or had r, c; Jrdcinte a group! E3nt of corresponding salts or esters. oii ux g #% cupenent -a = ba # ùùj #], i àvon-u-1l- # ùiùan # saoAo-'or di8Mb & tA: mM 1 az <#fe LeE'; .me talcoylec.t a3.syl & C3 and "alcox -7çt are used 1 # Ji d # nc their meaning pF, ui 1, ii = ge, -ùùiprennn% 'tg ;. ip: xin% 1 # ce; zc?, Iqz: = # 1 # [to chàsno Ei , ai; .l; ùi-% e G ".I'5 rauifl: iri $ c-5 oj; ci qi # es ùoe = ces #; yinez> and, <: n.lcs4> of 1 o r .; ; roupzments qUfi4; ' 1 o <5iea "on ';' 0 ;: s; iôz ;; iti: iniz, 'sosEO ..2 (:. ::' Rtosics d'hal & gë'o or dc.sc =; zui; cn = oen; zs i <ij les De z & xie> lo tcirùzo ': aryls "encompasses gpoupcxant.c nrqli = / e & Rtermat does such as !! /': 'O1S d lcg0Í;, \?; :: J Cil'. dcu gi? Gup * ùicnt- sit, s'o or alkyls.



  Boa eoMpccêo pr :: fér-C3 cant ui # ce <in which B represents a chlorine atom or an alkyl of 1 to 6 carbon atoms, preferably a methyl or butyl group, or such a group when it is substituted by halogen atoms, especially a trifluoromethyl group, or an alkoxy group of 1 to 6 carbon atoms, preferably methoxy; R 'represents an alkylene group of 1 to 6 carbon atoms, preferably methylene or @

 <Desc / Clms Page number 4>

 ethylidene;

   R "represents an alkyl group of 1 to 6 carbon atoms - preferably methyl, ethyl or cyclopropyl, or an alkoxy group of 1 to 6 carbon atoms such as an ethoxy group, a phenyl ring or a halogenated phenyl ring, such as a halogenated phenyl ring. , chlorophenyl group, or a substituted phenoxyalkylene group as a group
 EMI4.1
 methyl-ehlorophenoxyr.ethylene;

   Y represents a carboxy group or an alkoxycarbonyl group in which the alkoxy portion contains from 1 to 10 carbon atoms, preferably a
 EMI4.2
 thoxycarbon71Q group or a group9mont oarb moylo substituted by an alkyl group of 1 to 6,; carbon atoms
 EMI4.3
 preferably n N'-methyl '*' sarbss3yl {group and n has a value of Oe 1 or 2.



  Some comvos6c p, -> tixmi, 1.4rznent pr. ± T4;% ôs; loe leirive-1tion are Al- (benzo; vl, -lI; (-, lF-Qi; ii10iuopliéiày'l)? Lanin o% son ethyl ester.



  It is necessary to do! 1tab q'3 serves.pim içBiposés de .l '"fi = ont1on eomionmr't': R a '; q #> z d0 GbnJ a7triquG cpe" 4. lî 4oM exist 2 "ur de!}.: -; forMes i <" i <., f> g.icGm'.r * oei The jib, -raes stereo-'iae'aroSj, aiasi qm their al.ajBS Bout cOlnp1oeG in the cadrî3 nén ±. = al Il'3 la pr <5i-tn '; c. i.ntioRt Solon a peculiarity of 1.'inve # t /, o ;;, we can, prepare, the nitrogen-disubstituted cinino-aeide derivatives of the present invention by heating an amina derivative. nitrogen monosubstituted acid of the formula:
 EMI4.4
 with an acyl compound of the formula:

   

 <Desc / Clms Page number 5>

   R "COQ III in which R, R ', R @, Y and n are as defined above and Q represents a halogen atom or an acyloxy moiety of the formula R" COO. Preferably, we con. the reaction with heating under reflux in an inert solvent, such as bensene or an alkanol, while
 EMI5.1
 Common acyl compounds include anhydrides such as acetyl aNhydride and acyl chlorides such as bensoyl chloride and ethyl chloroformate.



   Alternatively, when Y represents a group
 EMI5.2
 #Ja? .Coyl-aa #> bamoyl, the desired product can be obtained by treating the corresponding derivative in which Y is an alkoxycarbonyl orpcment with the appropriate alkylamino ** "* 'L1 & mino-acidû aonosubstitud with the nitrogen of the ia : .-,, mule II can be prepared by any convenient method, but it has been found that a particularly useful method for preparing compounds in which R 'represents an ethylidene moiety is the reaction of a derivative.
 EMI5.3
 do 1 aniline do la:!: 'orliluli3:
 EMI5.4
 with a composa of! in formula:

   
 EMI5.5
 
 EMI5.6
 in which 11, Y in n are such that dófn1a d "de88 As this reaction is advantageous with the elimination of hydrochloric acid: it is preferably carried out in the presence of a base to absorb this by-product. a usable type of base being provided by the bicarbonates

 <Desc / Clms Page number 6>

 of alkaline metals. When it is desired to prepare a compound of formula II where I represents an alkoxycarbonyl group, it may be advantageous to carry out the reaction two times using a compound of formula V where Y represents a carboxy group and then esterifying the acid product. carboxylic.



   Thus, when used for the preparation of the particularly preferred compound N-bensoyl- ethyl ester
 EMI6.1
 N (3.4-dichlrophenyl) alanine, the synthetic method pr6. fair includes:
1) the reaction of dq, 3,4-dichloro-aniline and 2-chloroproplonic acid in the presence of sodium bicarbonate
2) esterification of the product of 1) with ethanol,
3) benzoylation by benzoyl chloride.



  When free acid is the desired product, it can be obtained by omitting time 2).
 EMI6.2
 



  The new drugs d-Qino-ac1dee diaubstîtuda based on the invention p3U "1011t 4tre used alone or in the form of a composition which comprises at least one compound of general formula 1 indicated together with a vehicle or a surfactant, or both a vehicle and a surfactant.



   The term "vehicle" as used herein refers to a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or compounded to facilitate its application to, the plant, grain, soil or other object to be treated, or its storage, transport or handling. The vehicle can be a solid or a fluid.

   Any of the usual materials

 <Desc / Clms Page number 7>

   used for the preparation of pesticides can be used as a vehicle
Examples of solid vehicles which can be used are silicates, clays, eg kaolinite clay, synthetic hydrated silicon oxides, synthetic calcium alicates, elements such as eg carbon and sulfur, natural and synthetic resins. . such as, for example, coumarone resins, rosin. copal, shellac, dammar, polyvinyl chloride.

   and polymers and copolymers of styrene, solid polychlorophenols, bitumen, asphaltite, waxes such as for example beeswax, paraffin wax, lignite wax and chlorinated mineral waxes, and fertilizers. solids, for example superphosphates.



   Examples of fluid vehicles that can be used are water, alcohols, such as isopropanol,
 EMI7.1
 c6tonea such as for example aceto nep sthylethyl ketons and methylisobutyl ketons and ethers, aromatic hydrocarbons such as for example benzene and toluene petroleum fractions such as for example kerosene, chlorinated cases such as for example carbon tetrachloride, y including gas compasses or
 EMI7.2
 nC !! 'malem'3nt at 3.!' state of liquefied iz7ptur. Dao mixtures of different liquids are often suitable.



     The surfactant can be a wetting agent, an emulsifying agent or a dispersant; it can be nonionic or ionic. Any of the surface active agents conventionally used for the preparation of herbicides can be used.

   Examples of surfactants which can be used are the sodium or calcium salts of polyacrylic decides, the condensation products of fatty acids or of aliphatic amines or amides containing at least 12

 <Desc / Clms Page number 8>

 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; partial esters of the above fatty acids with glycerol, sorbitan, sucrose or pentaerythritol; condensation products of alkylphenols, for example p-octylphenol or -octylcresol, with ethylene oxide and / or propylene oxide; sulfates or sulfonates of these condensation products;

   and alkali metal salts, preferably sodium salts, sulfuric acid esters or dibasic sulfonic acids containing at least 10 carbon atoms in the molecule, for example
 EMI8.1
 example sodi-ura lauryl sulphate, sodium socalcoyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as sodium dodecylbenzene sulphonate.



   The compositions of the invention can be prepared in the form of wettable powders $ dust, granules, solutions ;; do emulsifiable concentrates, emulsions and pastes. Wettable powders are ha-
 EMI8.2
 Usually, prepare so that they contain 25s 50 or 75% toxic and they usually contain, in addition to the solid carrier, 3 to 10% of a dispersing agent and, when necessary, 0 to 10% of the substance. one or more stabilizers and / or other additives such as penetrants or glues.

     Dusts are usually prepared in the form of a dust concentrate having a composition similar to that of a wettable powder, but blood dispersing agent and are diluted in place of use with a liquid. additional solid vehicle to give a composition usually containing 0.5-10% tonic. The granules are usually prepared so that they are between 0.152 and 1.676 mm in size.

 <Desc / Clms Page number 9>

 
 EMI9.1
 and we can produce them by.% cchnJ.q% ea do t igglOD1 '.. ton O dt1mpr6gtion8 In # 6nér61 leu rrsnulon will contain 0 to 24e; % of toyique and at 25 dadd11te tol. q! te of '.'-'.-;

   st.abiliaaat.s de @ mod1f1cat1 agents @ n pure 11bératio leata; '' back binder. etc .. The '' 'S3'r': sf'tt: 3G cont1enntn s "âP '<,; .. 3d.' ':' lm pJ.1X3 di, 301iiflk1.t 0til, i? SSz'st ' eet aéecGeaâ? 9 $>;> '5ta 9030 Ivs & tf 10 10 Q 50 on of â9.'d' E if. 20 S in rm1, dD / v; 1.m :; t1 iJmj,?; J! '). [\ nt, f. '' f. i "0 fi t '; fi cd .. "'' 2i'5ifs appropriate: joJ, P quo es :); 11b: '. lio [mt ;: des pên6t &' cnt8: .. des ..ÍJ1.ibi t: t1.7: C 1s (1t "\ tDCJ: 1.Q OIT'd ps" Spo?. '' O .9 !.};? T1tOQ do, qo iß ebtoair "K 1.} (Dd (2: ... tt2bl.c Gf .1tJ ::,! J '.:>' :.) (Jc; -! Fa, "# s5 (y? F'9, ',::

   J i.ÛÇ ébiE3Gun u $ = i?. '.. r'-'. a: '! 3' La '".. E; from 10 @ 0 to, t :: ptC1 from 30 2": r1'aE' t.? 9, '3 "-.ppE'cpyis and coRna iJ'01o'10 f.'. Cl ltêt1t1 4 '' 'd' '-:> r' Jlfr1i..ide Ol" ('"rI?: T (! 1C; 1 .- ?! î "AG .'k eo.'9 lo t (J;! F1t !: 31 na =% not \ ôo - '. 1 insolubioe jG1 (; (HllpfJCt:,"); n8 de J:.; '! Cnl1.1} 3v.lent Ot1tOiû.l, Í'Q: t \ (1 ::; 8, "1 [: clicn (, 8 [pei? - é: f.:> 4. .E18 .î ... a 'des (41J: .c ,, 1: {1eo f; r'3ct (rtO /' - '6? CFa',.: ^ "¯ la L,, 'to,. F.3 t the 'j "" 1 "" "" "," "" ",,,> eoc, ..,"', "." And 1 \ .1 ,, ",] 5r;:, ' .,. <H!;:) ..; ..: .....:, l.tj.i ";" ,, 0. C: "<:.", ";, ..... '- <- "o.:. <'" '"" OL' ,, "';" iEf [,. "H"' 'JIio1 c ..'. "'> sea" "?. <cocl â: â.4: '3'y'ā .g, .. qe des püJ..Y'pt.opll (rG0 v) -E: back ét, 11G: ôs cGl11t.1Ds "crL! C: 2 stabilizers tt1r: l:! S laeide 61jhftUG éai: 'S. ¯;:;, -' i'.a ', "' t. <r, Â:

   ë Q; P 8.tJ'ï; .G \ C l3, cs'bie: lc98 eu pf1t: i.eidoEJ t des exiles ;, by z rzr oils aoa'Gl?



  Arrangements and eBUlsiens 0üB '' {nQS des sos! "C: .4": i: ...: s.âW ': obteaues e :: S â ç:: f. Eouilic.bio ot? 3 ..'.'-. Y ;;;. N ::: icnK1 obt, G; zmGs 'Ó;? 1 1: "' 1.1: 'v;' lEf: - PC, U (h, "O! J1frtl :: UJ.t, ble J., Ct; .ï.Ce, lti" '$] 6klllJ.fJioml ±: Ó1G:' sl.c #! w 9. Û4ça.fh 3 f gL â¯. .AS.t.3É f.4'i6 '..' $ .. sen'6 cfilpri3e5 also d & r ::; lo Ced'0 # & lÔS "! L 'Je; la pr6se1 ?: a. il'lVe7 ..! t, im1a Ces' Fit2.6.R; .a psuvenh t,: r (1 of the type water dens'. 'or of the type oil in ltea \ 1! ot allas pauvent have a thick consistency such as an "amycnaise" * The compounds of the invention exhibit an act1.
 EMI9.2
 rapid regulation of plant growth on

 <Desc / Clms Page number 10>

 
 EMI10.1
 Mpeeea other than wild oats.

   For example, when used for pre-emergence spray application, the N-ethyloxycarbo-3 ethyl ester was found to diclate 10 days after spraying. % of 801tiê the growth of the 11nj of 1s dwré3; "'' and ao the b0ttcravc at auspe at a dose of applicationl1- Q {ltior, Q4 '; 0oÍ; o; <dant t \ a @) Ó1G ëe os 56 l: r ; / hilc De? ëy 'quanri, oi l \ lt: 1J "; ,, fJ ::' p1: 'l' # 7 UKO npi; jl1c [ril, by m3: trrisation fà'31 '"' g àoz F f: o- ë1 ea JOl \ 10 qu <3 1,? = 30? J?> z? d <JÓt1jrlt) da! JIYII61j} '1 <.. p -5' i '->> a ß ^, fiï , 9 the tRMBC laps do t3 E.an ": 6d1j de.,: É., 3r .... '.. 4: la :::: JtJt1nGC t; lCj trais i) pèOGH il doses -111", r ",, '11 11" ,, - "' <1" '70, r'c; - ';;. o "r ,,,", - y1'î "> to 31., 6 2' f ^ '1'1' "lig> Jha o 8 p% km # / hA 3 ..- k." m's, -d '. s' ^ k IdmJ2 .;

   3 x ''. ¯ ûz sasé & Cgm31'1d also a T ',', of û 1 eeatrc- the bad ones. & 'f¯''c3 qi, at. a f ¯ aa to apply? zur les Fe? f7h G P. "'^ 3' 9 or aâ ... ',. 3i habitat Ma compose eëlon} .I: tl & l. <r.: @: tl1 Q111r: 8 composition J0 COnOlf1 ± l [j and tla5; L 'l1:' E, c :: paus' iic: ", 'ap loo yields, cuimpcs in a lee which am1s:', '' ;, C to eppliaucr [i this place a COiilpOS9 da l 7iil '.rGfM.o: a or uno' 53 ': 23' .. T7¯ 1-3 containing Los coEip9Si5s' s.QS.en J- "1 #; # ve = a.àfl.; 5n, their pz" µ #; - 'roà # o #! {} 3 CCf: 1PQfJ uS fJCJ..on Il: ln, \! 0'c: 1) jn :; @UZ 'p'1e113ra l.QV 2.es e'; Qr.lpositior <8 containing them and their & 1G'Í:,: 'i.7it1 herbicide smells encara illastrôs by the examples fu: e .... 5 4 S :: eE9ls:

   <. ., 't.:it9ic:itf.â.c"â,:; 0 Pc: st; ::: "cF6tlr.r: L0 of 5Aû r'e mâ za = --- .. :: ;;; =: J '<M.4: If: .... :: ;; ç ..., [$ g 1>, - dS.c hiorc Dhén% -1) alani #: s Us mlnmG0 CP0Btcr d' " 6thyle of ià- (3,!;, - ± lic hl.ore. Phêyllsine (1; 1 g) and benzoyl chloride (?; 0) in ben: .1èno (50 cm.3) is heated to reflux while
 EMI10.2
 6 hours, period during which 1% hydrochloric acid
 EMI10.3
 beggar, emerges. The solvent is removed under pressure
 EMI10.4
 reduced and the residual oil is purified by chromatography

 <Desc / Clms Page number 11>

 
 EMI11.1
 on an alumina column using ethyl ether as the eluting solvent, to give a product having a scuff number, nO of 1.568sa. abaadcsme to luî-meze, gives crystals having a melting point of 50-52.
 EMI11.2
 Analysis
 EMI11.3
 Found s C 57 :.

   H 4.1 39 Cl 19.8, $ C7HrHO) Cl? requirements 5 57.6 JI Ib; 8 N 1 "90 01 20 #: 1.% flygple TI 11'1J.: J \ 2. !! ¯ l ... !!. wàY. y; caé,? 'É3 'Lb..r gE t.St ¯.i.ÉiÉ' ^ ti "Ê" E '. & "?. '"ri! d D.} û =':> an: r .G kf., c alsc3,: rr To a solution of 3>. .a 6a6 gs; j <. -" .., 6 th) l. Q 1 #g propano 1 (, - 400) c "03-.à-di? E 166 1 \;.: 0>, - '" in lisopycpaûal .l "" 400 Oh :.

   Gjcm ',;, c da 1 r, em. \ (Μ00 ffi "' and de 1 t c.1Ae 2.ochlorQprl) vi, =, & $, m: '(3 6GO 69 .y T = k3 341Û uE , 'y' NJe'3 û 3ûh, s.af: a On. ;; hr: m2i'e ce Méltuirj0 ô. i 1.06 # Vaf9 we add'3 du t4eE.!.: m u. "'. '.i.'r.'s do "Ae9GaaWY .'.'- 5 (5 6co 1, F> telJ: .k3 w 66f soles) p2T portions 8cceQives nvont 40 C! -i.1: ü: ZC ;: ç nu: i: 08;, :: 11l :; peiaàùn t 11, bag ft: '.'> (8 1.0r: "Jidisr :: m @ nt" oa voE-ao lo -7.ç;.,. 4, .ib 4ï do "': 5 (."' '::' '' '"1," ,,,,, 1f'C \ t, (lD0 "J.'0> vor'>" '\ <<5 Aa ... "-," '1 ""! "" ...... ,,., .. ,,,, -, r1J'j ",.



  'il (lY [ir;:; l: 48 e E-%: G'1 01.tf; f; Hê0 pur .kw.'., afî 'et. "> e <Re t111t: Z:' # ' 1 ;.



  8 4.â '.:, R.z :. .n Dl y> il d = '". C.3 3. help:': 4.A'- b-.r olùà <rÉ: igà = 0Wiqu; <4-i # oeoe OGm? 6 c ':. : û.r7 Caù i = FEiial.1a <n.1 is rV.1: .. r {:;} filtretioo 1 h: fr.a ;; 2r ". p5t l ßdawF .- 'x & a .'vC3RA..rkr..à .'... s, w ".% (2 l5 g? cOS \ J' '' 2 = # :. l.> ';:; 3.0r. <À múlo!.; 1 pa liit (le; fusion 148'- '1l; 9 ce 1
 EMI11.4
 'iitCi1v ±. C48 3.3 0130e 0H110G1 cxigs! C 46.3 n, 8 01 30.5%
 EMI11.5
 aFa; io de esr gle de ..1-dchlor, -. ,., not

 <Desc / Clms Page number 12>

   'We pass lucid hydrochloric gas
 EMI12.1
 in a solution of K- {3.4 * dichlorophyllaniRe (247%, i.e. 10.6 moles) in absolute ethanol (10 liters) while heating at reflux for 6 hours.

   After leaving the mixture to itself overnight, most of the ethanol (about 8 liters) is removed under reduced pressure and the residual solution is poured into water (10 liters).



   This solution is aqueous. neutralized with bicar-
 EMI12.2
 bonate de sodi'u'a and treated pap crsetitm with 1 '! 1 ethylene chicruro (3: o 1 lX. "; rù)' ': s is l; v &., dried over E9ga6oiu sulfate! a cnhdrew t le colvant is removed under pressure:. "é \ '. h.'!: ';,;.; p'J1J ,; ' Isieccr ballast d t 6'thylo de a.; Di.hlooi.3.x.xgiao 8QUO la fenao è. \? an oil ây'pâ2 '' sfiAC .. 'e The ¯0¯ "9â, sd gbt8U of sstto 5'.,. ' eat 7üi'i. fied by St 'â. ÉS with fie 1hei? cti; e TJ' 6 un Gisse paux * d "rH19 uao preductica i'.na10 due 2 176 g, cest ..,.: l. ..



  <ii? - 8) CSôe, .e, .â of the desired Gcatposê ;; melting point 37-38 0! 1! ')!:, lvse ito?:' 14 f4t 5 "36 Il 5 pi Cl 27? 9 fifl,) [qgj ,,, ±, jiq> gg qQ, / ,, j.µ L. .Bō bzz c â.;. '' ?; '.? S.'v 4âû. rr -, .. "' T. '- ".'. 'v' s; ' ed Câ Via'c't, ii LiëSE = .2iâ ichloroDnufi'il Í aloilin0 Un 1: llnL'.t111 d (J, -, 0 :. d ;: &th.:; rl8 de il-a- 13; 1 : pooe-iùhl-xrù pi :: enl1) alG: rd.ii1: Q i -: 16 g, -t3, d î ... i ..... 11,, 13 zo3.cfl :), from ehic '* bcnsoyie rure (1 450 & 1' a 3r> -: â.

   J, 0> 1 ,, molos) and de- bonzn9 âse% '{5 litrec) is iu \ i1 a's. "Ë? X..â:' '" ". T.pè8 hours, or add UR3 portion or, p20montairo of benzoyl chloride (290 g, agosw. ', r; a 21 mol)' 3t the heating under reflux is continued for a further 20 hours. After cooling, the solvent is removed.

 <Desc / Clms Page number 13>

 we reduced pressure to let the ethyl ester of
 EMI13.1
 N-benzoyl-N (3,4-dllorophen11) alanine in the lafun4 'form. , dark brown oil. The product obtained in this way is
 EMI13.2
 pupified by t.-Ititration with ltheyans on an ice bath to give a final production of 2220 g, i.e.
 EMI13.3
 say 601 moles of cmp @ z6 desires fusion pogni; 00) 2C ..

   Analysis
 EMI13.4
 Treuf <3 e C 58a M 4, ill 19.4 C .. # ;! 117NO? Ol -: ;; ezigc 'tè S9, (Il lî7 Cl 19.4 il
 EMI13.5
 
<tb>
<tb> @
<tb>
   ion
 EMI13.6
 ii => Î 3 n 1. <; li chlo z = o h é> i <zl. i a l, àùs, iùJ -> x ---- 0J2 iù fià, ù; ; xgz at '<3 G ï 1? d 'ô liî] à3,13 do ÎÎ / Ù) * 1 :. "OÎI $. <± iU) &' ry? .- lo.inc.! 13 s} c'ë â 3 sÉtz 'd ... .:. ", n ù; #; 1.qr; i 1 110 or # 'don? 'i.! :: 4> "a5 #i;>: i; u, io = r, 1 (51: Yùùi.3 c3'M Eh & Îvé ± ± ù,': U t" ùlî & 1 pure, -, 33 .'c.: i * "; jj> gx x ...: 3kac Cy = ¯w.4 E'GMg6 1? o> cfi e.é5tà, â.tJC3. <. ea3 .3bn.oR3 1;

   QiF, 1?. * IéX <.2 pcaësa'ë <jfi.t "Z, p -.-, n G131.%> R rr ^ efb ù'ôo <r 1 z" ùgn- ± <j: =) at = a .: â.a '' ... zg gléici] J; <; r 37i: QùÔ.iii: 1¯jQ ¯1> Q. <ùusii ixlxGOÔ0 m;.:, w :. m 8,, ;; ==,. * '<' '' '' * '., j, * t12 ,,: 1? . # j ,::; <- '' '' '-'t'3' 0 3.'U '*
 EMI13.7
 fl ap g <:; g j.:. :( .. y <gi] c gj r # 'i 1, fl. j,: 1 1? (, lll (i'> .- ';.' 2: '' fi;? ±: '. "> 21?: Jj!; 'N: 1) - .µç Z: c -': o1;:, n! .CJ <.} [.;:.,., (: .. fr.h.2 ,: x, -) I} 1: l1} '(:; at1 $ J''Z: 1 ±?) 1' $. to $ 3 63
 EMI13.8
 ljÇ: 1. {1} f t '.3: Y: -Jl: i.JL.l 14? 1QOQ ;; oU ± Oo4 SE CO l; G'> Analysis
 EMI13.9
 t}; GV :, 'Ji; 5 fI? Y ii> î, -, 11 A,. r '' J1'1 [.;, ...- r "", '' ''. 'tr'n'.: .. r, '.:

   1 1,., -. - "1 '{}' -" "L 1 4;>, 4à j
 EMI13.10
 jÇjçpg: .µ..j :: ¯¯jqi gj> <1 # gg.ig; ij = iā% ¯3¯) ± cgéjg.:, = jzij ± .i) j; jz cia, li-Qkoiggt = jgg,; ùgagz3 <± jo (¯1., à- = égg # g %% = ziìizi, ha? .a # ;; irn Sa 5! 'nrgs dstes' d? -µ. &% iijria de 1; 1 = <13, Y = dichloropii6nzti) ai.ani.izz (26pf; g) and de chloiNoòz # ù: 1, ine dethyl (lleS in the b! 1Zên # J (BO eu% 3 is chaie4'C, at refluy. for 6 hours, time during which gaseous hydrochloric acid is released.

   Distillation of the reaction mixture under reduced pressure affords N-ethoxycarbonyl- ethyl ester.

 <Desc / Clms Page number 14>

 
 EMI14.1
 I, $ 3ah.araphrrl.aine l 1.5271, point obéili% ion 15090 oua $ 0.3 mm de Zig.
 EMI14.2
 Analysis
 EMI14.3
 Found t ù 50, lp H. 9 N 4 ,? ci 21.6% C141t11U04C12 requires C 50'3 1: 1 5.1: 3 4.2 Cl 21.2%
 EMI14.4
 E le V -: ttç.L,: to do lA-bn! 5? It ..:; U-à;: - dichlqtr:.:.



  ÉË2-lââ3BS.



  N-beMQyl ethyl Instar is stirred.



  {) 4-dichlorophnyl) alanin0 (l gg prepare as in LOXOMPIZ 1À) ave # uni followed by tloliydroiiyù ± do zo <ià.1: ù (12 d, .7LG 1'omi (120 # o le m6it1anQl 0 C: 1. J; 60 th pendaat 3 h;% roa $. #? Sui,; tiqn>? Yfisui, 'to <nnt> s #s ± 1,1? Ôr (. Where 6'mpaE'ue pe' <51iB $. iBàt: 1Cl 'd E.tha.' 3t a ± 5 = iÎ11 J.6;> r Lo pi '±> ci, jùi' jH soliec f # 'E: ê osf,' 3asc JLm # 7, é F> J .ôùi ;; i and 'sis.llise from & 8Bsë) nQ / o: -: aao pmuip .ùoiz ## i? Â "aeAd-3 lic? .3., p * S,> x = #la fi. zi.on 153-1.5 'fl., AK-3.7SO
 EMI14.5
 ("" "\" '' '', 2 5 Ô *; 1 nn 0 "\ zo, c '<.' 3:!, F ().? '4'!> T: '1 r <y: 3 .. \ 't'!. Jp ;;:

   J "'.9f, a..a É;:'. Wheat5 = '* 1'.%" "Μi" - "µQ 1 î: '(,, -'.;, 0 '' A 21l! 1%
 EMI14.6
 1 ::: 9-li - .. 1J :,,., .. n.,,> N,.>, Fl, -,, "fl i> 'i?. -; .. = ..> < "'? ->, 1 '; k.1.çúQ z ¯ ¯ .Sa. ^ + "Ml -"' "1". iifil t4 21f-1; l% to} "J> '.lQd1') i! i ie'z ± éz- + at T # 3 # ¯¯ .. .. <.... ¯¯ .-. ¯¯., 'H * '' '
 EMI14.7
 
 EMI14.8
 , l, (; lSGf: rt do 1? ùs # e>; uîl. "*. i- do bessayl" ". nsa3.M '.? ay..lsnine 15 3 piopnx.ù like i'a> iw - plc II) dane <iu.mé = hanol (30 cn *) and then aôthylamine dissolved in 1 (2) cm3) is added.

   After having been left to himself, pondanû 3 joui-si la mixture

 <Desc / Clms Page number 15>

 is evaporated to dryness and the resulting oil is extracted with petroleum ether to give a solid loom which, after crystallization from benzene / hexane, gives the desired product, melting point 163-165 C, Analysis
 EMI15.1
 
<tb>
<tb> Found <SEP>: <SEP> C <SEP> 58.3 <SEP> H <SEP> 4.3 <SEP> C1 <SEP> 20.2%
<tb> Calculated <SEP> for <SEP> C17H16N2O2C12 <SEP>: <SEP> C <SEP> 58.1 <SEP> H <SEP> 4.6 <SEP> Cl <SEP> 20.2 <SEP>% <SEP>
<tb>
 
 EMI15.2
 xm '! i 'r ra.n r3w dalnine Using reod::.;. a.re:

   those described in Examples 1 to VI, the other iniquitous compounds are prepaid in Table 1.

 <Desc / Clms Page number 16>

 
 EMI16.1
 



  .,. t1 tp C
 EMI16.2
 No of the cocposê Analysis
 EMI16.3
 
<tb> physical <SEP> Found <SEP> Calculated
<tb> Index <SEP> do
<tb> refraction
<tb>
 
 EMI16.4
 N-benzoyl-N 'ethyl ester - (4' "21 # jyl) rmali.ne 1.5620 C 65.0j H 5.71 N 4.1; Cl 11,% jE C 65.2; H 5.4; N 4.2; Cl 10.7% ethyl ester of tl-bùnoyrl-1; -13-, ..t, chlorophél1yl) alaninc re: 1-, 5588 C 61.7; il ,, 6; II 4, C 65.2; H 5.4; N 4e2% Ethyl ester of qrxisay. 2 21 3a-d $ hlc hyaâ.i .. '1 n- 21 N., 5307 C a0's H 5 , 2; N zus Cl 22.7% C 52.8; H 5.3s N 4.4; Cl 22, µ $ Ethyl ester of N = bG11c, .Jrl j,] # .-,.,! - phenylalanine '' nIT 1955J6 c 72.7; H 6.6j.1 72.7; H bzz Ethyl ester of: .R.4; ga: - :; F methylpheno} .7é? tcét;. <t ) J "" 3 3 l ..... 21 dichlorophenyl) wool,. 'Â 1.5650 G 5, S; H 4.4; N 2.9; Cl 23.4% C 0 H 4 N 3, 1;

   Cl 2%, 0 $ Ethyl ester of n "benoyl (3 .'--. #. -. M- Ester dethyl-e ': a" n' - 5'13e> 57., 3Î 1. 'l , 4; li 3s7; 20.4, loe 57.0; 4.3; 4.0; Cl-2Os2% dichlorophênyDgIyc-iac n ±%: iL, 5'Î3e> C 51j1); a 1;, & 1 N 3.7; Cl 20.1 $ C 57.0; H 4.3; N 4.0; Cl 20.2% .-- .. v - .., .., .. ,,, ..-.-..-...- .. ¯ .. "....,. Yx. .. ".¯ .... d .. p \ 8.11" 111 Ester dtdtliyle de eyc7.cpropaMyl * '.; 3, ri'al4rcph: my.' !. rn: s: n- l, 5 / 3U c 53.5; H 5e '; il 4sie; Cl 23.0% C ts3: H 5.2; N 4.2; Cl 21.5%, t. TI "' '' 'MiIIII! II'-¯I > ..- * '' '¯I¯¯ ---. Ç; qw.¯ & - ..... j "' dI: - .. J1> .- ... a ... -. ..., r; U-ben ethyl ester ::; ojtl-U ". {J, 5 '"' '' ":> J '., ...-,.,. c. ,, , dichlorophenyl) alanine gas 1.5661 C 58.8; H 4.6; N 3.4% c 59, i; H 4.6; N 3, rw * - w, 4 "" "" "10., ± ..........., wc¯ --.----" "" "-" "- "" ..II!: - "" '-' '' III "IIL ..... 11'111.



  Ethyl ester of N-benoylt4-DIchioro-2-methyiphenyl) alain Dn 1,550 & e 65; g H 6, O C 66.0; It 5.8% ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯

 <Desc / Clms Page number 17>

       
 EMI17.1
 C) 4a
 EMI17.2
 laughed
 EMI17.3
 ! 1) - i, 5! Zr 4ta .'e 1 j t, 0 ::, ", j
 EMI17.4
 
 EMI17.5
 Name of the compound '".' "f'- '>.', ':; -! -.:, .. Anp.lyss" p é' "" "'' '' Y. '' '' '...",., - ¯ .. ,,. "..., .. ¯, ...., .....,. ¯-" '- "-"' '' --- '' '' ..., T ' <'' '' t '..'! '"3R ***',. # t.,. ,,,, ... ,, ... ,,,,,,,. ,,,, ##,. #, ##,. ## ,,, ######## ¯¯¯.¯ ..., ..., ¯ ........... 1. ...; .. \ t1: t1 \ zur, Calculate iiÂlûT ^ SY "^ '4C.r. (W $ ...! sr" y ..,: $$ .'....'. b ' r.,;.,.,. L?. ". L .. erl, d, ac ......, - ........

    .... ,,, ......! "" "" '"-" ""' '' '' 'h' '' '' '' 'J.d' ':.' '': r '' '' '' '' '' '-' '"' '' '...'.-. rr --..... ¯' '' '' '', .. ,,,, ,,,,,, -.!> ¯ ,,, ¯, ¯, ¯ YlT bon '"Y1 N (1" 1'i -'l ""' ", .." '",;, l . <, -, u: 1;.:. r <;: 1; +.,, "-:., i., ,,,., ...,., .., VJ i, S '' P, '', 1 rr.,; .. i. If "--0--00 ----." -Oxo, o ....., .0 .-- 0 -.



  -''--- "" --- "'b" "' ''" ,,,, = -, 'c ".> t,." ..:, \':.:; ";": :( "';;' \!" "'' '' '' '' '': c" '- "" "1 <' '-." ","' -j ...-., "h - '' '' '' '' '' '' .. \, ",,,, '' '3.>'" ,,, '- ""' '' YII't.Ii '' iII .. iz:.,>: "" '""' "" '' '"' Ester t s. ', bri ^ 7.9..C4 de.;? .- lw: .1; ...>, ¯' ' '.,:.



  D \ hy pl D} .... a.¯ .-- 1.1 .. <', i ", ..' ,. 1., ', .. nr,"'. R, '"1;', '".. .i.,, 13 dl 1 ±'. T 1 #, 'z "---- k% -' 0-oo.o" OPÔ + 0- ... "" "- ',,'. /" '; "-0 o.,,. .. 0, ',,! ....' '' '"' '' '' r. '' '. J' ''! 'I' .. J.'I. \ - or- '' '' '' -r'¯'Ir., ';' '' - '' '' i '<":! IW' '' '' - 'P [¯ ..-. 4.



  ± 1-hi # *; # .;>; l = ethyl ester. ., 'U e h 1 o r o - 2 -h pi .r ... :: .-.: -; .. 3' ;. z.6 '; \ ,: 1 0 ..... -m.¯l1v "- ,." khtv ..:.; I .. "..!". '. J', ......,. , .7 4 l ".m .., ....., .., ',) ::.':,. C: .4i". ', ""'. ,, ",,", < -. , ¯:, N ,, "- ',: J ......; 1", H' 4; ., il "9, 8fi -'-" "-" ---- "" "" '¯ .-- "---" ",", ... ",. ::'" f, "" '"' '" ,, "' -" "" "'1 ....,.,' 7" '' '' '' '' '..., ...,' '¯' '*' .- 'e -. #.' <- u.?on 4! 0! 9o8% y8 Ethyl ester of sL ;; ¯ ;, 'w¯r. t.> :, ,, '; ..? "'###.



  ) jI ",, - O ..... Cl.¯ \ JJ.tt) nt> .1.t¯ .., ..,: .. '..' ,, '' ', .... L, .sG. = ';;' û4 ',>.,' ,. ;;.,,; y - .. .. '. 1 ..... ";.' ,,,, a; . ' v \ He 5.0; N 3, 8 j Cl 18.7% "V0--00 + o ---- # o --'--, @ o. J lf: 3.'t. ('::,;'.!. , ... ";, - ',. M.,", "V' $ j" <J ,, "C" 't' ..., .....%. ¯, r., "- '. ,, "...' '' '' ''! -IO," - "'8"? "' '' '¯ -'''-' '' '\, T, ¯: S ier ï , I: V ': - /' :::), - 'Ethyl ester of: Y "' I ;. ":,:.:,;, 'è." ::::; :::; ::,'; \ 1 N (3 J, d. ::

   J "l ',';" '' ''; ',' 1 '' '' '' ':' ', .. "' ''; .1,.: 5?,>.;, F '= # i = .. "" '")" "Í; 7 T" ",, / #lx 3 9 ..' A '6 oA - ftfTaJ> oLCg. oroi: J11ë.H..7J.Gr "1!, ..: .. t .. ':" - .:'; '1'; '' '-' J '::,. 1J ±.,. ., .. 1; q: ... {, .. J .1.;, <.) T'JJ '> -'> "i" 5, *, 3 9 N? ...-.> arm "s., .- s .. -¯ ¯ .... ¯. '' '' '' '' ':>:>' bzz ...- 8" '¯ .- ., ... U: .., -,., ... ".. J..t -" - '' '' '' <'': '' '' '' '' '' '' ' '... r' '' '' '' '' '' '' '' '-' '' '¯r ",' ''", ",.: rn = - ::., r" ' - "" "" '.... "S .-" "} -" ";:"' '' '"' '' '' '' =, - \;:, -. :: o.- -¯1I1 fez 5! "I WI> P3.-benzo3.i µ.: Âa-, '' '; .nl, -:' 1:.", "'' '' X '**'" " "" "am: L110-1-rne.: 1 p: opJ.P>? ê> :: J. '' ':, - ,:' '; ::.; #,> Ji 1 =: lm. "<';.' i '#' = <.; ;,. ; d :: ;;, t; '.. ", d; v, j. -.... J.,) â8 J, if a15 Y $ sè's cil 1o 7% - ,, o ,, Wo- --o = - Ww o, o .. 0;,. "H." '; I "o:

   .., ',, -. -! / tif r, ', ............., .. ,, r "" "" "' '' - ''. '' '' N'1Jo ... ...--- ,,, -a- .W- Ethyl ester d (! ÉWâ.ar "-,:. [; t '!' J '., 1 N- / 3 4-dini +'" onhq, n,. "';,' ij .....:". ',.,.,. "v, .." .., -N ....... ¯:.,. ¯ s W: a ¯5 CI 26.5% Ethyl ester of lJ'-Cj .. "cl:" ": J <" i., .. \ ,: ç "j!: i,!, j,> \ : \}; J ';;' l '' ± <,. 6./l; '53 9 H (,!' Cl 26 5% lY 3i Lil E'ïl (1r'i ': 1 .ln.. a. ,, a .: j.:1.:, :: 12i ... "-.-..... lL., L ', ill] ,.

   S c 53.9, 4.0; 26.5% Ethyl ester of: s - sure $ Mb ': "., ,, .... chloro-3-trifluoromethyJ.T. \ {. {I: i,}.) Lar¯ire. , .., ..., ..> <..., ... ,, ...., .¯> ¯.., ........,. .¯- "ar .. ., .. ud Ôôjs "10, 1 + oO ¯ c * x,. 2 C. 8 alanine Ci 41'2; CI" 8- F 1

 <Desc / Clms Page number 18>

 
 EMI18.1
 µx, Qg]; ¯¯iI ± 1 Dénnn6trà% iog, dē1ãjtizi ± µ¯, herbicidf
To demonstrate their herbicidal activity, the compounds of the invention are tested by spraying the leaves of young plants of the following representative species: Etala (Zea mays), oats (Avena saliva), ryegrass
 EMI18.2
 (1t9lJu.'T.I reindeer) peas (Pisum sati-vum), Flax (I, inum¯ua3ti simum), mustard (Sinspsis alba) and sugar beet (Beta vulgarie).
 EMI18.3
 



  The prôpara%: 1. # n3 u'ë? .Liê '? S co> mi: Jten% in 50 pert: 1, c oa vel'e d "aêt.9HOg 50 par-tics c volu5.9 ci t water $ 0,, 5 p ,, trî4i, -, ;; # i poif.p ers. Pr'66it- de ocnnica ai.coyvZiJÀàiiol / o; yd & çj, /. <;%, J * ij ;;;> x . diGpc'MbI? <=: j; ¯, =; jj;> d. '' dG'i'3R <r, 1., n X-'3.55e ez>
 EMI18.4
 ': n.: - co3?'. "" 3 ëc '' 'l:' *: -: '' * t, Ao. it is .n''it6 &; Î, = r m,>; .> ù <= These coin-.



  ??. c.nm.-. F * 7 "ù. A '-:' pliacc 11L" '<? 1' = itfiici <ài] iiil? I.iÀ, étk% à ÔÔ "3" iT.rsc r + .o,, Î. - fl> a., = -; fi de'3 '-3? .e & .rr-TSG'dr'.n' Ô <10 a% T? n .. - [.. ::! 1 ::::. 1 0J} 1.Y?, 'there, 1:? "éi: ¯1t3 :-( O, -ça p ± P Éi? Î211.i "1? Fl 1.? '' '' * '"' / '', '-' 'r-' 'fQ # 1 .. I.> lt: É.' ". Î, 1 .. éé Ià2 éJfi ± Î ,, '9 Z Qà ± Î.

   I 2d) r: "'" "' I .-,: .- ¯; 1? Q- '± %% 1) i'J ;;) J: .Ô-1] li]. R: 1:" ¯l: .. "; .. -c:, 1 (: t1 4; '<! :('! Les Ú: 1: YÍc.;! J 'to <;). <", -; ¯,, ¯ ¯ '¯. -.--. "- -, -." ".V. ± ;, Ct *'. 3.3, '-.> 1." 1 -. <, 0' 1 ...-Cé "É E> / J¯é ';. J ;; WU # h <toµ> 0" .. =. I = - = ::' - \: = ', t-;' J; -2, r> '::': '- .. i': ':.:; C ..: -; ri. l ± c> x: iiù d. \ Jall1ûs "7".' "-: J.: \": f -:; '-' o "- ','?" l yji "B ''"] 2io? 1 .i "<o-7 5.") :; ' -] llT: tG 1.eJ: t '"<" q- fl,?,: t. "; gJôil5 0:, -;"; l :: ¯ ;: t '::' - -..-; -: "" 1tl'ù?> F "Î '? ±) <." <# ± nr¯ = z ±, q; == c ::?.? c '.:. ;.!,/CC. ; ';.'. / '..'. 'l.:cc- ..' He # n ;; nato- <ie 2 oy "q> <¯>". g; j; .jtjj> jj¯t> '> ;, "1j; i iq, ï.fl¯.? # i *, 3Y =. 1; "': -'. ?. "É" lii # Î:, 1: 5à dfloZ Ô, ù p {& i (1 ";? 2x: 1> X ii'l '± ofl.µ'? = #" 'B' Ô <1t ' ¯.) ,: lol? "Iiôi .-? ..". H 1:

   J-.àiÉ'µ.'Ù12 d '.. 2µ c .oeç> g.; G; # "ig <ji ec". 'ccoud iàn;> #. # itl.2nI: :: ,, <'> 1: P-ù-i ?; 1. '..'! ...; 3 z * µ <ueiioii of paic-s àr. 5j gl c: .ù 'me ",> 4," ..; J .: e 5 1> e i'165ùtd.oii of 95% weight.



   The results obtained in these tests are given in Table 2.

 <Desc / Clms Page number 19>

 
 EMI19.1
 



  --'''' - '--------' '' '-' '' '' '' '' '' '' '' '' '' <'- "' '' '' '-'1' '' '' '' ..........,., ........., - .. \ ".. ,,, -> .... .... ,,, .., .- .. "" '".>" "", .........,. - .. "" ........- '.- "... .." ", ..--" "---" ",," "-, o.-"' '' '' '' '' '' '' '' 'f "' I. .. 1 t-! î ...) 3 ('Jo. bt, c phytotoxi-ci'tê .ii" 1; .7' '' '' "1} ''," "rIt7 '".' :, * "<" '' '' '",' '' a, ¯ ...,." "., .., .. .? F ..., ..., .. 'ta3 ... ¯¯¯¯ ..., ..., ¯¯ ,,. ,, .., .. .... ::; â :. '' '""'.? '"ifll'µ s Li Mou- Beetroot te rt N? - .. ¯ .....' '" ""' "'" *' .., ... '0' .. 'h ".. ,,,,", .., "" "" ",,.,., ....,., A .. n, ¯ ..,.., .? '' SiSS ¯¯¯ t3ï * <i6 àsuCï * 6 t # kiini? .Th> .i? <I = 1 =. <.. = .....-; .. = .... ......: ....... '..I .. = - .. ..., ".

   I ...; ..> ....... "'*" I "--.-; i --. - .-- / t 4µ r ± ...- alaniaa -v' .. ? # -,.; -...--. "------- .... - ,. - .. r = .r-. ",, .. ¯ l :.,: 2" .e'rs alaaâne -.-'... A # éthylphëuyDalan-L, ',' .. '1 ... "............. ja., '. ::' 1 ... =.; -.... ¯, ¯¯¯ '"', ', ¯. , "Ù. 0 Q Yll" (4E ± lÉ! <:: 1? 'OtLli1ii, 1'>. ±, '"." H "¯, ..... 3 ... x,:.,. ..., ',. ".., ...". ,,,' - <M '' '' '' '¯¯ -, - "" "", - t! Enzoy 1ojo-¯LJ. "..." ".." ",,. J" d '"!' '' '' '' '' '' '' FMl.

   L. - 'J ;;. 1. 6 3 2
 EMI19.2
 
<tb> @
<tb>
 

 <Desc / Clms Page number 20>

 Example IX - Demons% ration of Growth Regulatory Inactivity Against Wild Oats
The ethyl ester of N-benzoyl-N- (3,4-
 EMI20.1
 d1chlorophenyl) slanine in a 50:50 mixture, by volume, of acetone and water containing 0.5% of an alkyl-aryl-polyether-alcohol and 1% of glycerol. Using a log sprayer, this solution is applied to the cultivated oat leaves of wild oats and barley growing in John Innes pot medium under greenhouse conditions.



   The compesé is sprayed at 7 doses included
 EMI20.2
 between 10 '5t (1 t:!, p. C ekFt ,. en la R: r4 JS; Céw., a, g d. 6s' i: 33t recorded' -:; 1U "a êshells>:; =% iJi% i? ai.1 = ± 10 days;! 'p1 "0 :;' 20. pulvêï'i5a * 6iQaa Qfiû noten (ie 7 * '.' '' '' '' '''.'- 8Ç ,: 'l:'.:; 'l2i: "G: .fhC; Z t ..: b É..ii-.:, viGf, tnei.



  : nhi1) ii; or de t ;;: ow.2nGc que oa: 1; 9pC (j in, J: .s4osS.br des (} () i0es in iii, 1 :: ci>. ": i ; i:; :: [. {1:. '111 .:' t; 1 '.'i) i .: 11tJ .7 ré6 \? l' ;;, pt: l. 3y.:. where? i ', at # 1i.si; 1 <.:. Q: -: vt, rj: l ;;' 1d n5py * 9 '30. "i =' Ag 4; a> = z 3?) l; 1 -f. ::. j: t "lIlLU.: T¯è6-éw [fS.iYi = TY: '.: ¯. == X'3; A¯L7m ^ ¯xl.r¯ ¯¯.-s., .... - .. s.:r-.2-cW a - ,. ^ f = s - '. vW jfDilaYJUG. ¯b5¯r.L3:.: 2¯ "..
 EMI20.3
 



  C, .p0SjJ "to to, 1 ÎIÎ, Îà /. -.! S:" '"'" '"*" "T! Vgs * 3." toi- = Z: Ei. t? <tJ, ùf <Qàà'àÉ 'flti' "\ 1".:; - r '"- ,, -. :: - 1.'ffiY" - - "-"' .. J'- - .., .-- y (.L ..: f -'- ": ¯1 ± fiÉ, flÉàùùlù2 ± == r: r-. * -r.::.¯-,-::-- ': -¯ - "", "-:' 12 :: lr; r- ... :::;: ;;, t" Q; .- l.?. T; c. / .É?: µ 1 #? '* <* 1. c <E j ±> 7,0 On. ï.5 ..b; 3 theretcs]? fl, k. É b <O g 3, É,; == f; ; 0 ù, Îi C i.2
 EMI20.4
 
<tb>
<tb> alnaine
<tb>
 
 EMI20.5
 :, T¯: '. Ple li: fii1JJiz, éiù:;. Ir.niii, .. iii.; I :: s.à ± .zii: .al -.? I? # Zàakà ---- ,. .



  ] j = ## iJ.Jj: <gµza =] = z 0n jjz = çi =.> ,; j ,, ce ";,; * x: i> git = *, J .ii: iiil; 1.Ji .; 5 = Jî> 3.e cp. Dissl
 EMI20.6
 vax% les Ç; QZlGt: ttj; -: -: 1: ir31tG d.2.î ... das; s.>: S.d6xâ mixt5) 8 de p6tolc and OR G i ', - v s..L '' 4 's filter 1 resulting solution.



  Ester dêth113 cle? L-bexsoyi-? 1-
 EMI20.7
 
<tb>
<tb> (3,4-di @ hlorophenyl) alanine <SEP>. <SEP> 50 <SEP> g
<tb> Emcol <SEP> H <SEP> 702 <SEP> 10 <SEP> g
<tb> Xylenes <SEP> sixtes <SEP> of <SEP> petroleum <SEP> Complement <SEP> to <SEP> 100 <SEP> because
<tb>
<tb>
 

 <Desc / Clms Page number 21>

 
 EMI21.1
 ttEmcol I 702 EmoeS-eat a trademark) "1/1 is a surfactant. which can be supplied by Emu1101" Chem1cal CorporQt1on 75S Wacker Dïvoâ Chicago, Etata-Un1 $. :. '!!! 1ple ..xt ....! Xparat.i9! L dnē¯c8io
 EMI21.2
 with water ...
 EMI21.3
 



  We have one, 2 ecmpcsitian nseats'6 mi8c1bl ve .'can clx to $.> Cil.; Ant; the ennti #;> an <; s in the lI-ni% hys> w.



  ;, jjr, rc] ./. dcno cr azEtniz <: where we filtM; la olioa ysltao ..



  À # ù ± 1 of et-h-lc {l0 Îi <ÀlÙù ± j¯1]; "l
 EMI21.4
  r n, .-, F1: state '., ^^, ..F ° ;; F:. ¯¯s:. Se rot it <>. <, S.05? R. #:. t ià,! 't.i-. '¯ <<.. r-. :::; i% -; -'.- 'C ...; - ¯ ..> -.:-' 7 ::. AT,: . / ¯) '": -;.: (: :( :; l1 ,: Z.: ,,'! ;;,> ..- 2
 EMI21.5
 'ir t7;. :: r ;. -:.:. /'.f: O1.C., ::; :). <,; > c> - ,; i.r; r "1f1} rie;: cl) ::, t; .., j; r ::: C :; - ::: .. C- .¯f ';' - t:;, Sort ,, ': 0: '. "" 1 t. "{L, .. \, -':; 6tJ ;::,;) ;, .. (1:; i tofj j0¯; '¯ É 0 j, -': '-, "'.:" 'to 1 ,. -i =' To; '' [fl '' i> InJ'jCJ. ::: 1. "/ rs 3rd ',,! ..": ". r 1'.SIÙ (';; J, =. "! J"' ..:, .. '..': '; # 1 E3ri': i \\ CJ 1 ± ¯ i ", yi * j" ¯:.: .-, ::,., <''! 'I "? -; -r # ,,' .F: .-": -i'-: 1 J '4 p) fd ¯. Ll ;: I1 ">. L-: r; .. t1 a.>). ; Jt :.



  : ".;. ::, 1 ...." - ::., ..>. ::.,: ":,] j # fl] $ ga ± giàggÇ 1]) ¯ .- .. 2-::. '" :. ':,;: -', ë'i: ".; - {,,". 2q:) .. (1.,; {>: ";" 1): ..--. ;; - [- 9 (1ZÛ "'J ::; fi.2
 EMI21.6
 .1:, - "'" "5
 EMI21.7
 in 1.3'gig3,3, çi R.epc-éscsëc m QÏ <'>% µ d'13àl, # ù (] Éàmà oh Un ftÔàp0' "meni oit <; 1 <Q;: yjn repz? ésen, ie Q 1 ',)' 1), V4% i number ent11 "of Si 5; and when n is greater than 1 the R groups may be the same or different; Rt represents an alkylene group, 1 Rn represents an alkyl group, a! CO% ye aryl or aryloxyalkylene and Y represents a c8rboxy grog.psment or cor- ## '# - #### salts or esters

 <Desc / Clms Page number 22>

 
 EMI22.1
 roopondantop or a carbomoyl group optionally mono- or d1aubst1tuê with nitrogen.
 EMI22.2
 



  2.- derivatives according to claim 1, characterized
 EMI22.3
 in that R represents the chlorine atom or an alkyl, halo-alkyl or alkoxy group of 1 to 6 carbon atoms. Rt rem. * A-senses an alkyl group of 1 to due 8obonfl Rn -an alkyl lu do 1 6 tcm0 <àf # e .-. ': Saao oi, g ua &1; :) Y.tll. ahôRyle ôz? ntigmlorJs "F haJ ooJoi # 3 '9; .in. àj>.:.; rp # = soi? sx phài; #,> q?, = * igo> iiùn,; J:; hz.ti, t? txù i ii ix gtr <izena <-? -; '., 9.'. xi:;> ;;> /: 1.? or. aun Epope. i .-. eir'i ace.:? " 3.:.-nrlc cc .... c 1-.iiqtl <'?.

   F.z FJ; 1: 1!; ; ùJ, ooig # jonij, <oggyà .0 û> m% - <:. = ".;: i C / 1 oa #?> #> noe, n T.1> .iii. ià # ni:> pe :; # 21iii '2SE'BÛS9ylQ - # E # s.> Fl: 1: = 1; 1; .n;: -.; Q <, Î.> .. i;> # ix.ù; ii, " '1-30', ;;, -: from f. a.Bae3 d; '3aoe'oôi' fi 11> 'àiµ1 "': ¯.C'r; z ... ::,; 2) '? To cV <. I" "2g'l: 16 <' 2l'i%. 'I' ": '; I # "1 <: 17i" '' 'c'.)? Li.; Ô ?? "l ''? 1" 2 fiii? '' Àp'iliiù%. r; so ??: É # 1] ii] 'ù. <J j .i Î.ÎEµ1.lElE p' 3 fli 5 <: l ll. '= ,.' i = y. [ri;

    = éà ',> Î 3, <]> 11 [/ p gîlLàlllµ93> Q "?;' -:?:,? 1c: * 1 :: fl. = 5 1. #>, - ': 1-'; Il:., ¯ii i: ii # .i>. P?> L:. <. =. '....? J, ii';,;: Ç "Drfl () j: Q [)! 5 ; -; 1:.:! Qc Î.ùôl.lµfÎ.fillÉ (1 "lÙ <;;: ¯ -...:" Ùléà ± 1 '12) ";:";}):;, J: 2 (o (lù¯ BlqOnL? ') ro = Ç0' - '.: -; <. e2-: y-.3c.rc.': i @; =;; - - ç-o%; oOo oo m 0 ; .. "; - &; hyZ ¯, o Q? - ç0, qo? /. h'0-W Îù <À ±? fl.l?: 1: ± ± ??. *. Téiiiil la] * '? 1'L. <], I = P? # 1:' 4 $ ,: tù, fi 2acaCtài? Iés e? '?. se que zep ==: às:; = #. Ar. -I "a .ii> * 1 <: de> iil ">: ir <., gi. m; #;> oupez i; se-.:." j, -, 3 "CEt ;; -. -. <,;. .; = ,, m, m ... t, ";: a:; o;, o = .., û '& hy'lideno.% t% es-ë" n gzm? u; pi = # icnià iÈiliµ9Àe ;: .à.i; hy? 'e, cyalo-ppyl' .-. 'or Gth01 a ggi- o> psnex% ph.ànyl = - an un gi =? i; p- * i # ieni Môthyl-chloro -phêny- 'êylône and. It is.i; a group'35: 3at tboxysarbenyle.



  5, - N-Benzoyl-N- (3.l.-di-chloropbenyl) ethyl ester -
 EMI22.4
 alanine
 EMI22.5
 6.eN-benzoyl.N- (3,4mdichlorophenyl} alanine.

 <Desc / Clms Page number 23>

 



  7, - Derivatives of amino acids disubstituted with the tele asote that defais above, in particular in the examples, and tolu that mentioned especially here.



  8.- Process for the preparation of compounds according to one or the other of claims 1 to 7, characterized in that it
 EMI23.1
 consists in heating an arn derivative:!. nc "'ac: i.Üe aonosubstimë A, 1" asote of the formula ,.
 EMI23.2
 
 EMI23.3
 c.?o'- l :: I} 5n: Fes''3.-cylu J? the . . $ '$ r.É% .3 a a: "? <5:" z rl [.' .. i $ .'-, n:. ' ,. .¯'t. r ..

   Y 0 ': - .. r ,, "'. J ç,." Bwc: que .r¯ '; 3: r,'.;: 6:.: 3 c & '- ssus.j, Mw i :: tl) :: "i;: 1i.0 ua E.âaâYY.> d.'jl1:) gnQ .4 ͯ ', ll :; ljO; 0: ,, (Jl acyS.6K'y do tr:; :: ': J} l! 10 0 S;' jC; a'Ft: r; i: <=: r¯ "a's:.: Fa la: '.' 3T '.: -:', cn i3F a, .v: àié., "a N: 3 r: t0.-1 '0 :; q.' / <a ..., ai,: i 'a: ^. 3¯ <3 ô' ß4's- .o s50j1C.; 1-e <sxi ..: '¯4 tÚ (:' k'j ::? 1 ['eu 7G., ";; B -t1: r!,: :( ;; c' 'Ei1 S (11 [1ê.: Tl (;:}'!.;. 1 .3.t ¯ '? Ros'd6 3V.:'L"Tr:;.1.t la! A0 ;;.: .:!. Gt # (;: ç (r :, '.,' 6 ea? As ?: -3 os. J (: 11.O 1 '". A..L¯? Y" ¯.tcZ: : t: ri :: Ic> "0 ':; ï.' '4 l'-3 D0r; ftH :: 1. .PccJ'. 3 '1? ilO OR 33':}; - '<::, --jp ï "3n.a & '.' M. '.".



  ...; - ...., '; ¯'t' ¯ r '.', 4i:,. ¯ .. <.. / lUod le ..f'¯5: s y r'Q ;. ''! Cfit the -iâicsz! '-, <<, r --j 1S ..--.>,. ûE = ¯'s. Cb¯1L -..- c-: 'J: tU1. f)). : rL11tt. 'dss lcven {ic (\' t: 1.cv "fH P ': - ;. c & ae-i.su' - '' OH prpae deriva t'aMiReaeiëe" [ngüout ± titu6 1030G0 de 1 & farsele IX éïc.3 rtï 03 ': w3ar "W a
 EMI23.4
 g "O'l,! pGmofJ.'i :.: '. .F9 by making;:' 6th. {; ii" '! ln der:!.' width of ± â3 "t." d .. of the formula
 EMI23.5
 

 <Desc / Clms Page number 24>

 with a compound of the formula CH3-CH-Y
CL V in which R, n and! are as defined in claim 1.



  13, - A method according to claim 12, characterized in that the aniline derivative of formula IV is reacted with the compound of formula V in the presence of a base * 14.- Process according to claim 13, characterizes
 EMI24.1
 in that the base '33 1, e b; lea'lfion # it, e of sodims, J> 5 z =? cé; tli # l, # m # i <tx?, ôci; a:;) 1. fgnAtre des reveHd & ea <- '-M <5ns 3.3 J.i;. = .J: n1 => <ae!; xbr; is.5 es. ci # ".uo la 4 <J; DF, i-9L of aniline {1e In òr # vl, e D7 aïs a # ?, 5a3;: li; a: <. c; * lucid a-chl ' 3ropx'eiJ5, Oni, ÇjlJ 01; J 1 '.:; Produce C0>? ZMliÉE "1,2i. ± J.>: I / 10 tI = j,, ,,,, a ,,,;,, - :. g - - ,. 3,?. ,; p .. des x'8veEd: sat: Lona f) ii 1? -> àx% a #> <# Jiflf.!:> 5 one in <: ;;? i, # ip # "lp, n # <1 ' 'csE' <=. é. "ilJ, jri <3 of: j¯i ,,,,, o- o = ,,;? tj¯ j = 1, ¯ <# ",; 1" 1 r; .. * ..:

   , y-:., - t / o 1 - pi "-," x é + '. .1 0 nr d'ôti # i :), e 60 1; µ <> (I:, f ;; =. ELF. L 1, -J <=. Jpl: 1, ij.?) J = ī aizj, iz.> ci? g;> .le 121ozr {wi '# benseyio-' '.7 3-' 1? z "tf & à4 5; ii: luan? à lm'-i Jri 1? nu%; <n des l-f3oiJenr1: tcatiïït: 1 1? - & 2,6p cc! -c: ac: iw90 = z ce> i <xp: <:;. =. # 1es1.je ;: "from é.u: nyi; a (lE].: "'beas9y.".;. i3lJ.?-.-'c..?hKyl!&'!.ainc? j: jj, lo? t-.4 "' ichl '? Fec.il:!ae e 'Y>? Àoié c.; Ho% fl = W -;.% =.> 31 = ov>' ox <, ni- eu - .. J. ", R; '.. ..... -, - <; - "", "- ,,, -., .. I" I ................-., V "' -J- '.:> <. "' 1 ...:" on DftJ..tlt; J "" On llqt] .0ueo Cft iù ?? àr ± G.Xé:. ± ì.C ii, µ¯ , #, ai, 13mi: X? 1.c ùi9 lùGdi1, lil ?, QS "Let $: <.> ficaitiooe, <iu product.; = i, = # 3." And, ii # .iùoll e be- aKoyIetica a7> ec 1 <a iiensoyl chloride 3-.

   P;? Oed; µ 4 => pr-6pcu. "'/ J.tif.m 4> ù eospocs .SHivant one or Ilaiatre-claims 1 to 7, in substance, as described above, notably in the examples.



  19. A compound according to any one of claims 1 to 7. prepared by the process according to any one of claims 8 to 18.

 <Desc / Clms Page number 25>

 20.- Herbicidal compositions comprising a derivative
 EMI25.1
 <t'Mino <-disuba% 1% ue with nitrogen as specified in any one of claims 1 to 7 and 19 together with a vehicle or a surfactant or at the liver a vehicle and a surfactant.



   21. A composition according to claim 20 which takes the form of wettable powder, dust, granules. a solution, an emulsifiable concentrate, a conventional emulsion, an inverse emulsion or an encapsulated material,
22.- Herbicidal composition, in substance, as described above, in particular in the examples.



   23.- Method for controlling weeds, characterized in that it consists in treating the weeds or their habitat with a compound according to one or the other. of claims 1 to 7 and 19 or a composition according to any of claims 20 to 22.



   24.- Process for increasing the yields of crops in a place, characterized in that it consists in applying to this place a compound according to either of the claims
1 to 7 and 19 or a composition according to any one of claims 20 to 22.