SI8111555A8 - Process for producing quinoxalinyl oxy ethers - Google Patents

Description

PROCEDURE FOR THE PRODUCTION OF QUINOXALINYLOXY ETHERS

Technical field

The invention is in the field of the production of agents for the destruction and control of undesirable vegetation and relates to a process for the production of quinoxalines 1oxy ether, which is used as a reagent for selective weed control (MKP C 070 241/40; A 61K 31/496).

Technical problem

Since the presence of undesirable vegetation causes permanent damage to useful plants, and especially to plants that represent basic human food and satisfy the needs for fibers such as cotton, soybeans, beans, etc., there is a constant need for more effective herbicides. Therefore, it is a technical problem to be solved by the present invention in towers to find an efficient process that would allow the production of a new compound that would effectively destroy the weeds without damaging the useful plants.

The state of the art

Today, a wide range of means of destruction or control of undesirable vegetation (herbicides) are available, which are more or less effective or more or less harmful to useful plants.

The compound produced by the process according to the invention is brand new ie. the applicant is not aware that it has been manufactured so far, and therefore the process for its production, which is the subject of this finding, is new. '

Description of a solution to a technical problem with examples of execution

The invention relates to a process for the production of quinoxalinyloxy ethers of the following general formula

L j

O-Q- (Q) - ?? ! ⁿ D

A «H iii G ₁ -C _< alkyl, ³ - ^H - * · ^as r CHj iii OCHj G« H iii Cl,.

D * H, CHj or CO ₂ Bg,

L _c H, CHj ill C ₂ Hj _t

Q «-CH« CH— iii -CI ^ CHg n «= O iU 1, I« CS iii C (O) R ill

R »Cl, XR _lf KT ^ Rj, OH ill Ott,

M It is suitable for agriculture,

1.0 or 3,

Εχ «^ 1 ^ 18 benzene, phenyl, Cj-Οθ cycloalkyl,

CHgCHgOCHj, C ^ CI ^ OC ^ CHj, CHgCHjCHgOCHj, ctt ^ + * 4i * ^ RgR ^ g Cj * ^ » ₄ alkenyl.

_Cj-C4 alkynyl ill Cj-C * alkenyl iii alkynyl koji Yes axle necessary enjan aa aa cores "Blerim,

2a.

R is H. C-C.alkyl, C_-C_cycloalkyl, benzyl 14 5 8

OCH ₃ , C ₃ -C ₄ alkenyl, Ch ₂ CH ₂ NR ₄ R ₅

R ₃ is H or C ₁ '-C ₄ alkyl; iii R ₂ and R ₃ may be taken together

iii - (ch ₂ ) ₂ -n (ch ₃ ) - (ch ₂ ) ₂ - _;

R. and R_ are independently CH_ or C_H _c ;

3 25 '

R ₆ is H, C ₁ -C ₄ alkyl or SR ₄ ;

is H, C1-C6 alkyl; iii Rg and R? may be taken together to be - (CH ₂ ) -iii - (CH ₂ ) ₄ -;

Rg and Rg are independently C1-C6 alkyl; V is F, Cl, Br, C 1-4 alkoxy C ₁ -C ₄ alkyl, CF ₃ , NC> _{2 or} C ₁ -C ₄ alkylthio; M is 0.1, 2 or 3;

Y and Z are n dependent N iii Ν-οφ except that when D = ^c ° 2 ^R q ^{ta <} ^ ^a is N = 0 (zero) and L is CH ₃ ; when R ^ -4J = CRgR ^, then X = 0; that one of R, and R_ is not equal to H; and when E is different from H or Cl, then G = H; when W = CN iii then A = H; when E iii G is different from H then A = H iii CH3 / when W then n = 0 (zero) and D is H; when m = 3 then

V = C1, Br, F or CH ₃ ; when R ₂ = SC> ₂ CF ₃ then R ₃ = H, being the alkali metal salt of the compounds of formula

HO o-c-w

D

2b where D = H or CH ^; W is CN or COOR ¹ , R is C ¹ -C 4 alkyl, and L, Q in are the same as above, reacted with 2-haloquinoxaline of formula

o where A, E and G are the same as defined above in a solvent such as dimethylformamide, dimethylsulfoxide and methylethyl ketone, and at a temperature between 25 ° and 13 ° C.

- JR ₂ = H, alkyl, C 1 -C 6 cycloalkyl, benzene.

00¾, ^c 3 ° 4 alkenyl, -0¾ ^^ ¾, -SC ^ CF ^, 1100¾ ^ ¾, ClGHgCI ^ iii Br 0¾¾,

R ^ = H iii alkyl iii and leg be taken together to be hi - (CE ^ -MCH ^ -, - ((¾ -, (CF ^) g- lli

- <^) ₂ -H (C ^) - ((^) ₂ - _t

R ₄ and Rg are independently 0¾ iii,

Rg = H, O _χ -ύ ₄ alkyl or 3R ₉ ,

Βγ «H, C _x -C ₄ alkyl iii

Rg and Ηγ aoga be «harvested together to ee get 4 (¾) ^ - iii - (^ ¾) 4“ ·

Rg and Ηθ aa independently alkyl, V «= ?, Cl

Br, C ₁ -C _<alkokai, C-C * alkyl, CF, 1¾ iii C ^ -C ^ alkylthio "-0, 1, 2, 3 III,

Y and 2 au independently of each other N or K - * 0, provided that:

(a) when D - COgRg, n is 0 (nala) and L «CHg, (b) when« - »« GRgR? , then X * 0, (e) iii Rg lli H? I i d, I (d) when S is not H or Cl then 0 is H, (e) when Jo is W - CI or

B when I A - a, (f) when E Ul G are not H, then A - H Ill Cfl ^, (g) when Jo w - V>

s then js n · O (nola) and C H, (h) when Jo a-3 »then V - Cl. Nr. F or CH ^, (i) when Jo Bg SOgCP ^ then Jo - H.

Preferred compounds wherein Jo has increased activity and / or is increased iinteea aptitude. oa compounds of Pomile I. in which J · «(1) A - H, (2) Favorable compounds (l) he those in which Jo fi | o H.

Cl. P or CP ^. the axis of both «bed yen is that when G« Cl. E nora be Cl on d- and 7- pesleijl.

(3) Advantageous compounds (2) are those where Jo G «H and E« H, Cl.

P or cp ₅ , (4) Compounds (3), which are advantageous and have E at 6- posieijl, (3) Favorable compounds (<) with those in which D «CH ^ i

L - H.

(6) Favorable compounds (5) for which Jo Y and Z «H,

- 5 (7) Porous compounds (6) of eu in which R -ORj,

OH iii OU, (8) Porous compounds (7) are those in which R ^ ^e ° ι “% alkyl, (9) Porous compounds (8) are those in which n = O (zero). Specifically aa porous compounds, for example, high activity and / or light synthetic

Ustil 2- / 4- (6 or 7-chloro * 2-quinoxalinyloxy) - (phonoxy / propanoate (saoSa 6-chloro 17-chloro compounds) ,.

Motyl 2- / 4- {2-quinocaalinyloxy) phonecal / propanoate,

Motyl 2- / 4- (6,7-dichloro-2-quinoxalinyloxy) phenoxy] -propanoate,

Motyl 2- / 4- (6-yl or 7-pheloro-2-cycloalkenyl) phenoxy / -propanoate, N-oxide,

Methyl 2- [4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy] -2-oethylpropano.

Motyl 2- [4- (6-yl-7-fluoro-S-cycloalkenyl-alkaloyl) phonoxy / propanoate, Methyl 4- [4- (6- or 7-chloro-2-quinoxalinyloxy)] enoxy] -pentanoate, Betll 2- [4- (6-yl or 7-chloro-2-quinoxalinyloxy) phenoxy] -acetate, Methyl 2- [4- (6 or 7-trifluoroethyl) -noxoxy] ethoxy] propane.

2- / 4- (ill 7-Chloro o -2-quinoxalinyloxy) phenyloxy] -K-trifluoro-phenylsulfonyl) propanoide, 1-methylethylethylidene 2- (4- (6 or 7-chloro-2-quinocayloinyloxy) phonoxy / propanoate 1 iii 7-chloro-2- (4 - / - 1- (4 &apos; 5 * &lt; / RTI &gt; hydroxyazol-2-yl) isoxy-phthinoxy / quinoxaline,

-6 This invention relates to a compound of Formula 1, i.e., n * herbicide composts, containing a compound of Formula I and to a method of their application, as well as to the control of raat * undesirable vegetation ·

The compounds of Formula I can be prepared in several ways, which are greater than the defaults of L, D, Q, n and V.

a «Compounds of Formula 1, wherein D - H or CH ^, n« OH and 2 «K

i) There are several ways to prepare these compounds. "Compounds wherein I · COR, RXO 1" is ^C 1-4 alkyl, represented by * the formula Ila, and can be obtained by combining, preferably in equimolar amounts of 2-haloquinocalin and alkali. the metal salts of alkyl 2- {4-hydroxyferboxy) alkanoate, as illustrated by Reakel 1 ·

-1 Reaction * 1

alkali aetal hydride

-

L t

OC-COOR, f ¹ S where D * H or CHj, · Cj-C * alkyl and A, E _t G and L au as previously defined ·

Odgorarajudl dissolve with or «reaction au dlnetllforaadid, dlnetllsulfokald, dlglln laetiletllketon. The reaction of Theoma gave birth at a temperature of about 25 to 150 ° C. · As a starting material, the esters of the Raised Ha are used to obtain other compounds of the invention.

- β 2-chlorochloxalinin, which JI β · uses in this reakei age j * s a poetupkon known in the art · Glyoxalic acid, a chased gliocetic acid or some alkyl ester of glloxalic acid combine with the enriched n o-phenylenediaaino in ethanol to give gave 2-hydroxy-quinoxaline as described in JACS 71 6 (1949) · 2-hydroxylquinoxaline treated ee with phosphorous oxychloridone as described in JCS, 519 (1948) · lli Buli, 3oe.C5hee · France, 356 (1963) to obtain Salt 2-chloroquinoxalin. Ora refsrenea is included here.

The alkyl 2- (4-hydroxyphenoxy) alkanoates used in the reaction are driven in this area 1 foot ss obtained in a two-step process from a compound which will be purchased commercially ·

First the salt is 4-benzyloxyphenol and alkylated with nokin br ornoalkanoate. · The product salt is subjected to hydrogen alloy in the presence of palladium via a carbon catalyst to give the desired compound.

- 9 ii) Compounds wherein W is OCR and R is OH, represented in Formula (R) Ilb, and the leg is obtained by hydrolysis of the r.ec.ther of Formula Ila.

Ilb where Je D e H iii CH ^ i A, S, G, and 1 w as earlier defii i * eano.

Yields of Formula Ilb acids give ee iii hydrolysis of acids, for example hydrochloric acid dissolved or sulfuric acids or hydrolyzed bases with for example sodium hydroxide or potassium hydroxide, using saplings with reflux acid · iii) acids thionyl chloride to give the acid chloride of Formula

cartoon.

Alternatively, the sodium salt of Formula Ilb may be treated with oxalyl chloride to obtain the acid chlorides of Formula Ilc.

Iv) Compounds where j · J e OCR 13 «· are represented

The formula Ud, which may be obtained by combining the acid chloride of the formula Ilc ea with two moles, corresponds to the amines in question:

cartoon.

Sour! chloride and amine are best corroborated on lli under arabia ntne teraeratur * · in a solution such as tetrahydrofuran or methylene chloride,

Compounds of Formula Ud where P - ₂ = CF2 SOg and 1H can be obtained from the amine urea moiety (compound IId _f where I is from trifluoroethanesulfonyl chloride in the presence of an acidic aceptor such as pyridine.

v) Compounds η which is COR> COR 12 «= represented by eu in formula Ile, and are obtained by combining some acid log chloride of Formula Ile with the corresponding alcohol, thiol, phenol, thiophenol or oxia and the presence of an equimolar amount of an acid acceptor where D« H iii GH ^ and A, E, G, L, and em as previously defined ·

Suitable klseel aceptors include but do not exclude plrldlne and N, N ^ iaethylaniline «The reaction ee is best performed in an atmosphere of asot at a temperature of about 0 C to about <0 C ·

Alternatively, some compounds of Formula II · may be obtainable by reacting them with the appropriate acids of Formula Ilb with the corresponding halo compounds under the catalyst phase · vi) Compounds where f * CN represented by Formula Ilf and the leg will be recovered by condensation of the corresponding 2-haloquinoxalines aa aol of alkali metal 2-O-hydroxyphenoxyalkyl anenitrile.

Ilf where D = H iii CH ^, A «H 1 E, G, and 1 as As previously refined.

Bimethylformadide Is an example of a suitable solvent. Alternatively, compounds of Formula Ilf leg are obtained by condensation of the corresponding 2- (4-hydroxyphenoxy) quinoxaline with 2-ha3onitrile and the presence of potassium carbonate. Acetone! trli Je Jed ar. of the many delayed salts.

- 13 vv) Salts for example in agriculture ea eoli acids of Formula Ilb and are used as herbicides and include but do not exclude eaorium, sodium, lithium Jur., Potassium®, potassium, magnesium®, bari jura and quaternary eaoni juaore eoli. These eoli may be represented generally by formula® lig, wherein D = H or CE ^, and may be obtained by known methods.

UfL.

where A, E, G, or X are as previously defined is = 1 or 2 Ka priaer, the aetal salts of the legs will be treated with the compound of Forsula Ilb «and a solution of some alkali or alkali metal salts with sufficient base ions (e.g. », Hydroxide, alkoxide, carbonate, or hydride). The more amine », amine, and quaternarnd aaor.ijm salts may be obtained by similar t ^ hnikaa & a.

- in the villa) Compounds where Is

.. I can get this as illustrated in Reaction 2.

i where eu E, G, and L kae As previously defined.

- 15 Corresponds to the aaaenes of 2- (4-hydroxyphenoxy) chloroxyroxaliE being brought into contact with 2-brao-N- (2Oxoethyl) alkane®idone to preserve potassium carbonate. The foranil compound is obtained ochlodihydrohalogenool by the product of this reaction in the presence of an acidic aceptor, for example, on the trio of Ali potassium hydroxide.

b) Compounds of Poraule I, where B «H ill CH ^, Q«

-CH-CH-, n * l, Ϊ and Z - N.

These compounds will also be prepared in accordance with a variety of procedures, in addition to the definition of V.

Compounds with W C CK, B * XH ^, χ · 0, and Rj * ^ ΐ “^ 4 alkyl, are represented by Poruulra IH, and they are obtained as Reacted by reaction j.

- 16 Reaction 5

alkali aetal hydride or carbonate

XIII where D - H or C 1-6 alkyl, and A, E, G and 1 en are as previously defined.

2Myloroquinoxaline is condensed with 4-benzyloxyphenol or 4-non-toxophenolo in the presence of sodium aetokeide or an alkaline aetal hydride. Further, it removes the ee netil 111 benzene group of poetupkon known in the art, for example, the one described in Belgian Patent 868,875 or Tetrahedron 24, 2289 (1968), which have been taken herein as references, to yield 2- ( 4-hydroxyferoxy) quinokealin. The reaction of these products is said alkyl chromoalkanoaton, in the presence of an alkaline aetal hydride or carbonate, the desired amount of ether is obtained.

The esters of formula III may be used to obtain the acids, acid chlorides, amides, and other esters of the present invention as in the salts of the compounds, 1 which is identical to the one prepared by the corresponding compounds of Formula I-b and Ile and lig.

il) Compounds of the formula III wherein 7 is CR, but may be obtained by reaction of the alkali metal or 2- (4-hydroxyphenocei) quinacalin ea or 4-broao2-alkenitriloa alloys.

C7 Compounds of Foraule I, where L «COgRg» ¹ n * 0 and Ϊ and Z »K.

Because of the two basic routes to prlprerau of these compounds, Forauloe IV was introduced.

where eu A, s, G, D, Rg I V as before definiear.o

- is Compounds of Formulas IT where n T * COR IR «IS ^ R 1 or C 1 -C 4 alkoxy extends to the combining of conjugated 2-chloroquinoxalines and alkali metal salts of the corresponding phenols, at a temperature of about 25 C and 130 C, rasrarad is DMP. The phenol may be recovered by the process as described below to obtain alkyl 2- (4-hydroxy-phenyl) alkanoates.

Alternatively, the compounds of Overgrowth IT where S is NO ^ R 1 or C 1 -C 4 alkoxy aoga will retrieve the contact aa corresponds to the iodine 2 (4-hydrocaifenok8l) quinoxalino and aa derivative of laa halogenated aalonoic acid, Hal-C (CH *) (CO ^) (CGR).

The compounds obtained, when R 1 is C 1 -C 6 alkoxy, may be used as a starting medium for the production of acids, such as the hydrochloride 1 of dear ethers of the present invention, and salts of these compounds 1, by a process similar to that of , which is used a prepare «! of the compounds of Formula Ilb, IIo, Ile 1 lig.

d) Compounds of Formula 1, where D H iii CH ^, Q a - CRgCHg, n * 1, I and Z «S ·

Ora compounds may be represented by Formula T:

- 19 Compounds of Formula V, wherein W is ^C 1 iii COR, R 1 XR 4 X 0 and ^E 1 ^C 1-4 alkyl legs are recovered by the reaction of equiolar amounts corresponding to 2-chloroxyroxalir and ea to the corresponding alky 4 "(4-hydr. ocaiphenoxy) alkanoate or with 4- (4-hydroxyphenoxy) alkenes three Ισα in the presence of potassium carbonate. Suitable solutions of euoetonitrile, dlaethylforaadidl or aethylene ketones. This reaction step is illustrated by reaction 4.

I

Alkyl 4- (4-hydrocaiphenoxy) alkanoates and the corresponding three or more can be obtained by alkylation of the corresponding 4-benzyloxyphene olo 1 with alkylbroaoalkanoates with catalytic hydrogenation to recover the unsaturated and remove the benzene group.

The compounds prepared in this way are used as a half-life battery! to give the corresponding compounds of Formula Ilb-Ile and lig.

e) Yodir. of Formula I where au one 111 both Y 1 Z «= -► 0.

Many K-oxide compounds can be prepared by combining the corresponding clnoxalinyl ocel ether (where eu Y 1 Z * li) ea porkls e lino®, such as perbenzene acid, in the corresponding solution, such as phyto is methylene chloride. The Ska perklsellne mixture with high temperature gives as a result di -K -oxides.

The following examples illustrate the preparation of the compounds of the present invention.

Example 1

Methyl-g - / 4- (2-clnoxalloxyloxy) f enokai / propanoate

To a solution of 5.9 g (0.04 mol) of ethyl 2- (4-hydroxypheroxy) propanoate, under a atmosphere of asot 1 in 20 oo dlmethylfornadide was added a dropwise drop of about 15 C to 1.5 g (0.05 mol) of 57 l sodium hydride in 20 ee dimethylforaadide. When hydrogen develops, 4.9 g (0.03 sol) of 2-chloroquinoxaline 1 are added to the reaction mixture, then the saeSa is heated to 150 C for 4 h, while the mixture is left to stand overnight at room temperature, and then the reaction mixture is poured in about 100 ee of cold water. airplane * one solid filter filtered ae 1 crystallized from methanol to give 4.2 find the heat of the compound, m.p. 110-115 C.

HE (0130) 81 1.5 (4, J “7He, JH),

J.7 (», 5H),

♦ .9 (e, J * TH », IH),

7.15 (ABo.J. 9H "," H),

7.5-e.J (a, 4H),

8.9 (·, 1H).

Pr la er -2

Ketll 2- / 4- (6,7-dichloro-1-chloro-cycloalkyl) fer-oxy / propanoate

To a solution of 3.9 g (0.02 aol &lt; RTI ID = 0.0 &gt; of &lt; / RTI &gt; nyl 2/4-hydrocaifer.oxl) proparoate in 20 cc dlmethylforaadide under nitrogen atmosphere, a suspension of 0.8 g of sodium hydride ra 15 C. was added dropwise. . When it begins to separate hydrogen into the reaction medium, it adds 4.7 g (0.02 rolls) of 2,6,7-trichloroquinococcal and heats it for 5 myrtles of 130 C. Filtration of the reaction mixture yields the fat of non-solvent 2: 0g as a material. The filtrate ee eatin poured into approximately 200 ee of ice water «Then ae adds sodium chloride, which will then extract aa 1200 octa ether (4 x 500). The ether ae is then removed under vacuum and the solid product ae is crystallized from CH2OH. Prinoa is titled compound 2.8 g, m.p. 100-105 C.

miCDCl ^ f: 1.7 (d _t J «7Hz, 3H),

3.8 (a,? H),

4.75 (e, J «7%, 1H),

7.15 (ABr, J «9Hz, 4H), (a, 1H),

8.3 (a, 1H) ·

8.8 (a, 1H).

- 22 *

The following compounds of the ee also receive the addition of the basic procedures, which are described in the στοά process, i.e., the patent.

Methyl 2- / 4- (6 111 7 chloro-2-quinoxalloyl) phenoxy] -propanoate, (mixture of 6- and 7- laoer), m.p. Ιθβ-lll C.

1XR (CBCl ^: 1.6 (d, J «7Hz, 33),

3.7 (β, 3H),

4.7 (e. J «7 HZ, IH),

7.1 (A3p, J - 932, 43),

7.6-7.7 (a, 2H),

8-8.1 (a, 1H),

8.7 (s, 12).

Methyl 2- / 4- (6 or 7-chloro-2-chiroxalir.yloxy) ferroxy / acetate, m.p.

94-98 C.

® £ R (CDC ^: 3.7 (β, 3H),

4.6 (s, 2H),

7.1 (ABn, J «9Hs, 43),

7.3-8.1 (K, 33),

8.7 (s, 12).

Methyl 2- [4- (6-111 7-chloro-2-chloroxals; yloxy) phenoxy] -2-ethylpropanoate, m.p. 83-87 C.

(CDCl ^ S: 1.6 (c, 63),

3.73 (s, 33),

7.2 (ABc, J · shs, 42),

7.8- <7.9 <a, 2H)

8.2-8.3 (a, 13) · (s, 1H).

Methyl 2 - / 4-4 trifluoroaethyl-2-quinocaalinyloxy) phenocai / proparoar 1 his 7-trifluoroaethyl isoaer.

ΪΦΕΪ (CBCl ^) S s 1.7 (d, j * 73s, 33),

3.8 (s, 33)

4.75 (r, J 7 HZ, 1H),

7.15 (ASc, 932, 42),

7.4-6.5 (a, 3H),

8.85 and 8.95 (2 einglets, 12).

Lylethyl 2- / 4- (6 or 7-fluoro-2-quinocalaryloyl) phenyl / propanecet * m.p. 113-116 C.

Rffi (CDCl 2 S: 1.65 (d, J - 7Ha, 3H),

3.75 (·, 3Η)

4.7 (o, J “7 HZ, IH)

7.15 (ABo, J «9112, 4H),

7.35-8 (a, 3Π),

8.85 (o, 1H).

The compounds listed in Table I may obtain the procedure indicated in Examples 1 and 2 and aaeno of the corresponding 2-chloroquinoxaline and alkyl 2- (4-biprocaifenoke) alkanoates,

TABLE ι

A E Mr D L H 6-CF, H H H CH ₃ ch ₃ 6-F H H ch ₃ ch ₃ H 7-F H H H H 6-No H H ch ₃ CH ₃ H 6-OCH ₃ H H ch ₃ , CH ₃ H 6-CH ₃ H ch ₃ ch ₃ ch ₃ ch ₃ H H H ch ₃ ch ₃ H 6-C1 H H ^C 2 ^H s and ' ^C 3 ^H H 6-C1 7-C1 H ch ₃ ^C 2 ^H 5 H 7-C1 H H ch ₃ nC ₄ H H 6-F H ^CK 3 ^ch 3 'nC ₃ ^H H H H H H ch ₃ ch ₃ 6-C1 H H ch ₃ - ch ₃ ch ₃ 6-CF ₃ H H H ^C 2 ^H 5 ^C 2 ^H 5 H H H ch ₃ ch ₃ ^C 3 ^H 7 H H H ch ₃ CH ₃ ^C 4 ^H 9 H H H ch ₃ ^C 2 ^H 5 H 6-C1 8-C1 H ch ₃ CH ₃ H 5-C1 7-C1 H ch ₃ ^CH 3

- 25 ZClMC-I / 4- (2-quinocalloxyloxy) phenoxy / proxylamine klsellra

Winter ee 3.2 g (0.01 mol) of Methyl 2 - / (4-2-quinoceinyloxy) phenoxy) proparoate and it was added with a solution of 0.07 g (0.01 mol) of potassium hydroxide in 5cc of water and 60 ec of methanol. The mixture was then stirred at room temperature overnight and then filtered to remove a small amount of non-destructive materials. Methanol is then slaughtered under raccoons. When pH 2 is reached, ice and hydrochloric acid are added to the mixture. The precipitated acid is separated by filtration and purified by re-dissolution in saturisar.oa sodium bicarbonate solution.Prino «. is 0.7 g »m.p. 137-141 C.

Kffi (CDCl 2 -OcSO) S: 1.7 (d, J * 7 HZ, 3H),

4.7 (r, J «7 HZ, LH),

7.15 (ABr, J- 9hZ, 4H).

7.45-6.4 (m, 4H) and 8.8 (s, 1H).

By using similar procedures, such as the compounds listed in Table II can be obtained.

TABLE II

A E Mr D L "· H 6-CF- H H H ch ₃ 6-F H H ^CH 3 H 7-F H H H H 6-No H H ^CH 3 H 6-OCH ₃ H H ch ₃ H 6-CH ₃ H ch ₃ ch ₃ ch ₃ H H H ch ₃ H 6-CI H H ^C 2 ^H H 6-CI 7-C1 H CH ₃ H 7-C1 H H ch ₃ H 6-F H ch ₃ ch ₃ H H H H H ch ₃ 6-CI H H ch ₃ ^CH 3 6-CF ₃ H H H ^C 2 ^H 5 H H H ch ₃ ^C 3 ^H 7 H H H ch ₃ ^C 4 ^H 9 H H H CH ₃ H 6-CI 8-C1 H ^CH 3 H 5-C1 7-C1 H CH,

-27 Example 4

N, N-1ethyl-2 - / - 4- (6- or 7-chloro-1-quinoxalinyloxy) -phenoxy / propanoid

Diethylaina (5e) was added dropwise to a protsharon rah to form 1.5 g (0.004 mol) of 2 - / - (4- (6-111 7-chloro-2-chiroxalyryloxy) phenoxy / propionyl chloride and 5 ° eo ether. When the addition of ammonia is complete, the mixture is stirred at aabIentroJ temperature for 1 h. The precipitated diethylain hydrohlorld aclar. By filtration 1, the filtrate is concentrated under reduced pressure to give the solid a solid product.

Purification of the solid product of crystallization of Joti from nbatyl chloride gives 1.4 g of the title compound, m.p., 121-124 C.

(CDCl3) Gi 1.1 (t, J Hz, 6H),

1.6 (d, J «7 HZ, JH),

3.5 (n «J« 7 Hz, 4H),

5.0 (q, J = 7 Hz, 1H),

7.1 (ABq, J - 6 Ha, 4H),

7.6-β (a, JH),

8.6 (a, 1Π).

Priaar 5

2 - / (4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy) f enoxy / -2 '- (trifluoroethylsulfonyl) propanaldehyde 0.8 with trifluoromethanesulfonyl chloride in 5 cc pyridine was added dropwise 0.7 g (0.002 sol) 2- / 4- (6 or 7-chloro-2-quinocaalinylethyl) fenoxy / propanamide au 25 cc pyridine at aobic temperature. When the additives are perfect, the mixture is stirred and heated to 60 C for 3 h. The shielding cools to room temperature and evaporates the substance and removes it by evaporation at the desired pressure. The ee residue was dissolved in methylene chloride 1 and the resulting solution was washed stepwise with IOjC hydrochloric acid. The methylene chloride solution was dried over magnesium sulfate 1 methylene chloride was removed by lapping at the desired pressure to give 0.25 g of the precipitated compound.

The amides of Table III may be prepared or treated with the corresponding kiael chloride with an amine using the procedure described in Example 4 or by reaction of the corresponding amides aa trifluoromethanesulfonyl chloride id on, as exemplified in Example 5 ·

TABLE III

A E Mr D L H 6-CF ₃ H 'H H ch ₃ 6-F H H ch ₃ H 7-F H H H H 6-No H H. ch ₃ H 6-OCH ₃ H H ch ₃ H 6-CH ₃ H ch ₃ ch ₃ ch ₃ H H H ch ₃ H 6-C1 H H ^C 2 ^H 5 H 6-C1 7-C1 H ch ₃ H 7-C1 H H ch ₃ H 6-F H ch ₃ ch ₃ H H H H H ch ₃ 6-C1. H H ch ₃ ch ₃ 6-CF ₃ H H H ^C 2 ^H 5 H H H ch ₃ C ₃ ^h ? H H H ch ₃ ^C 4 ^H 9 H H H ch ₃ H 6-C1 8-C1 H ch ₃ H 5-C1 7-C1 H ch ₃ H H H H CH ₃ H 6-C1 H H H

^ 2 b H H H ch ₃ cyclohexyl H ^C 6 ^H 5- H ^C 6 ^H 5 ^CH 2 ' H H (ch ₃ ) ₂ ch- t- ^c 4 ^H 9 H CH ₃ ^CH 3. n- ^c 4 ^H 9 ch ₃ - (CH ₂ ) ₂ -0- (CH ₂ ) ₂ - - ⁽ c ^h 2) ₄ - - (c ^h 2) ₆ - A- ^C 4 ^H 9 H CH ₃ ch ₃ o- ^C 2 ^H 5 H H cyclopenty1 - < ^ch 2) ₂ - n (ch ₃ ) - (ch ₂ ) ₂ -

H CH ₂ -CH = CH ₂

H CH ₂ CH ₂ N (CH ₃ ) ₂

F

TABLE III. (continued) A E Mr D L h H 6-F H H ch ₃ - (5) -f CH ₃ H i 6-CF ₃ H H ch ₃ - ^ 0> -no ₂ H H 6-CI 7- • Cl H ch ₃ ch ₇ ch ₇ oh H H H H H ^C 2 ^H 5 CH ₇ CH _? Nr H CH, \ 2 H 7-C1 H H H Vo) - ^CH 3 H / ch ₃ / ^och 3 H 6-Cl H H H H Cl ' H H H H ChLj -S0 ₂ CF ₃ H H 6-CF H H ch ₃ -S0 ₂ CF ₃ H H 6-F H H ch ₃ -S0 ₂ CF ₃ H H 6-Cl H H ch ₃ - (5} -sch ₃ H H 6-Cl H H ch ₃ - (θ) - ^ε 4 ^Η 9 H

η prtoatl

Allyl 2- [4- (6-yl or 7-chloro-2-quinolinyllocal) phenoxy-propanoate

It takes up 5 ec of allyl bromide and is added at once to a mixture of 2 g (0.0058 aoia) 2- / 4- (6 or 7- * loro-2-4firoxalinyloxy) phenoxy / propacic acid, 0.2 g of tetrabutylamine and hydrogen sulfate and 1 g (0.025 nola) of sodium hydroxide in 30 oc water and 85 ec chlorophore.

Saefia ae aefia 6 pm. The chlorophore layer is separated and the volatile liquid is removed at reduced pressure. The residue was evaporated in ether 1 layer of ether with &quot; sul &lt; 1 &gt; over magnesium sulfate, &quot; agnesiumBB sulfate ae removed filtration &quot;, and the ether evaporated under vacuum to give a solid product. The solid product is poured into dissolved ether hexane (3 * 1) in a sachet and filtered through a layer of silica and washed with n-hexano.

Concentraelion of filtrate 1 crystallized from the residue from n-hexane ether (l &lt; 4 &gt;) gave 1.3 g of the desired product, m.p. 6469 Ce

KUR (CDCl ^ S J 1.6 (d, J «7Hz, 3H) ^

4.5-6.1 (η · 6H),

6.9-e.1 (a, 7H).

-32 ZeIsseJL

AHl 2 - / 4- (2-chloroxylniloxyl) phenocal / proparoate

To obtain the decomposed compound no5, the following procedure is followed ·

To a solution of 1 * 2 g (0.021 aoles) of allyl alcohol 1 1.6 g (0.02 aoles) of pyridine in 5 ° ee »ethylene chloride was added 6.6 g (θβ2 mol) of 2 - / 4- (2-chirocaalinyloxy) phenoxy / propionyl chloride in 60 oo »ethylene chloride. Aofia is planted at room temperature over night. It is washed with ethylene chloride solution and the water 1 solution is suctioned over sulphate aagnesium 1 and it is crystallized to give the appropriate amount of allyl 2- / 4- (2-roxo lyloxy) phenoxy / propanoate.

- 33 Example 8 1-ethylethyl-thylidene 2- / 4- (6 or 7-chloro-2-quinaquinolloxy) phenoxyl / propanoate

With the addition of 6.9 g (0.019 sol) of 2- / 4- (6- or 7-chloro-2-chlorooxalir. Crystals) fer.oxy) propionyl chloride, and 25 g of tetrahydrofurate added 2 g (0.027 sol) of drops dropwise. acetone oxide at room temperature 1 2.5 g (0.0 J2 aola) of pyridine and 75 ce of tetrahydrofuran. When added, stir the mixture for 24 h at room temperature. The pyridine hydrochloride precipitate was removed by * filtration 1 filtrate with a &quot; concentrated under vacuum to give a solid product. A solid product, water (200 oe) and jayethylene chloride were then added. A layer of methylene chloride * · was isolated and washed with 5 ^ hydrochloric acid, 10 pounds of sodium bicarbonate, and the water was filtered and dried over magnesium sulfate. A pure solution of methylene chloride is concentrated in vacuo to give 5 g of the petroleum compound in an oil,

KMR (CDClg)? »1.8 (d, J - 7 Hz, 3 * 0

I. 9 (o, 1H)

2.05 (a, 1H)

7.15 (ABr, 9Hz, 4H),

J. 4-8.15 (b, 3H),

8.75 (o, 1H).

One of the methods described can be obtained because I listed in Table IV.

TABLE IV

A E Mr D L Χϊ ^ · “” H 6-CF ₃ H H H 0-cyclohexyl ch ₃ 6-F H H- ^CH 3 o (ch ₂ ) ₂ o (ch ₂ ) ₂ oc ₂ h H 7-F H H H OCH ₂ C = C-CH ₂ C1 H 6-No H H ch ₃ ° c ₆ h ₅ H 6-OCH ₃ H H ^CH 3 OCH ₂ ^c 6 ^h 5 H 6-CH ₃ H ch ₃ ^CH 3 OCH ₂ CH ₂ CH ₂ OCH ₃ ch ₃ H H H ^CH 3 ° ' ^C 18 ^H 37 H 6-C1 H H ^C 2 ^H 5 o-ch ₂ c = ch- H 6-C1 7-C1 H ^CH 3 he = c (ch ₃ ) ₂ H 7-C1 H H ch ₃ O-N = <J H 6-F H ch ₃ ch ₃ ON = C (CH ₃ ) (SCH ₃ ) H H H H H ON = CH (C ₄ H ₉ ) ch ₃ 6-C1 H H CH ₃ S-cyclohexyl ch ₃ 6-CF ₃ H H H S-benzyl ^C 2 ^H 5 H H H ch ₃ sch ₂ ch = ch ₂ c ₃ h ₇ H H H ch ₃ sch ₃ c ₄ h ₉ H H H ch ₃ sc ₄ h ₉ H 6-C1 8-C1 H ch ₃ ^SC 6 ^H 5 H 5-CI 7-C1 H ch ₃ SCH ₂ CH = CH ₂ H 6-C1 H H ch ₃ ^SC 12 ^H 25

-55 Example 8

- / 4- (2-quinocayinyloxy) phenocal / proplonyltrl

To a solution of 1.5 g of sodium hydride (0.05 mol) in 20 cc of diethyl ethyl foraadd was added a solution of 4.9 g (0.03 aol) of 2- (4-hydroxyferoxy) propionitrile in 20 ee of dimethylformadide. When hydrogen separation begins, ae 4.9 g (0.03 aol) of 2-chlorochloxalane is added. "Heating is approximately 13θ C until the ae reaction is complete. The mixture was then boiled and water 1 was extracted with ether. Pure extract of ether 1 concentrate yields the desired nitrile.

Example 9

2- / 4- (6-yl or 7-chloro-2-yl-quinaxyloxy) phenoxyl / propionyltr (g) (0.067 aola) 2-chloro-propionyl trillate was added in the snow 5 g (0.01B mol) of 2- (4 'hydroxycycloalkal (6 iii 7) -chloro-chlorooxaline and 3 g (0.022 aol) of potassium carbonate in 50 cc acetonitrile. 3 The mixture was stirred and rectified for 18 h. A solution of 1 excess chloropropionrl trill was removed in vacuo The residue was washed with water (200 ee ) 1 the insoluble portion of ae heats aa 500 eo ether, Removing the ether in a vacuum gives ae a solid product which purifies crystallization «from methanol, The yield is 2.6 g tt, 117-125 0.

KUR (CDCl 3 S 1.8 (d, J 7 Hz, 3 * 0,

4.9 (r, J - 7 Ha, 1H),

6.9-8.3 (m, 7H) and 8.85 (a, 1H).

• 5

Prinine prana 3 and 9 hours. the use of the corresponding 2-chloroquioxinalin and 2- (4 ~ hydroxyphenoxy) quinoxialin and halonitrile can be obtained from the compounds of Table V,

Table V

E Mr D L 6-CF ₃ H H H 6-No H H ^CH 3 6-OCH ₃ H H ch ₃ 6-CH ₃ H ch ₃ ch ₃ 6-C1 H H c ₂ h 6-cr 7-C1 H ch ₃ 6-F H ^CH 3 ch ₃ H H H H 6-C1 8-C1 H CH- 5-C1 7-C1 H CH _O

-π Priaer 10

Katri Jun 2 - / <- (2-Quinoxalinyloxy) phenoxy / propanoate

Use the following synthetic procedure to obtain sodium salts of arya,

3.1 g (0.01 aole) of 2? - / - quinoxalinyloxy (1-phenoxy) propionic acid are added to a solution of 0.06 g (0.01 aole) of astrium aetoxide in 50 ee of "ethanol" 3aeffe oe aft at room temperature for 2 h 1 removes the solution at of the Vaktar in order to obtain the principles of hunting us a compound.

Treatment of the appropriate carboxylic acids aa with the appropriate baron (aa priaer, fruit strong, some saln, quaternary aaoni jua hydroxide, some alkali metal or some hydroxide of alkaline morals, hydride, carbonate or bicarbonate) may yield the carboxylic acid salts listed in Table VI .

TABLE VI

A E Mr D L s M H 6-CF ₃ H H H 1 On ch ₃ 6-F H H ch ₃ 1 On H 7-F H H H 1 On H 6-No H H ch ₃ 1 K H 6-OCH ₃ H H ch ₃ 1 K H 6-CH ₃ H ch ₃ ch ₃ 1 Li ch ₃ H H H ch ₃ 1 Li H 6-C1 H H ^C 2 ^H 5 1 ^NH 4 H 6-C1 7-C1 H ch ₃ 1 nh ₄ H- 7-C1 H H ch ₃ 1 ch ₃ nh ₃ H 6-F H ^CH 3 CH ₃ 1 (HOCH ₂ CH ₂ ) ₂ nh H H H H H 1 (ch ₃ ) ₂ nh ₂ ch ₃ 6-C1 H H ch ₃ 1 (C ₂ H ₅ ) ₃ NH ch ₃ 6-CF ₃ H H H 1 (HOCH ₂ CH ₂ ) ₃ NH ^C 2 ^H 5 H H H ch ₃ 1 (HOCH ₂ CH ₂ ) ₃ NH ^C 3 ^H 7 H H H ch ₃ 1 c ₄ h ₉ nh ₃ ^C 4 ^H 9 H H H ch ₃ 2 Ca H 6-Č1 8-C1 H CH ₃ 2 Ca H 5-CI 7-C1 H CH ₃ 2 Mg

- 59 Priaer 11

111 7-chloro-2- / 4- / 1- (4 »5-dihydroaeol-2-yl) stokal / -fer.okei / quinoxaline

Smog 5.5 g (0.02 nol) and 4-hydroxy-phenyl 6 111 7 chlorochloxalia, 4.5 g (0.02 aola) 2-chromo-fc- (2-chloroethyl) proparamide 1 5.5 g (0.04 mol) of potassium carbonate powder in 100 eemetllethyl ketone, and it was heated at rectifica tion 18.5 h. Effortless reaction snow was filtered off 1 conoentrile in vacuo to give solid fc- (2-chloroethyl) -2V <* (h or 7-chloro-2-quinocaneinyloxy / propar. Aaid. Orrstl aaid was dissolved in 75 sc of methylene chloride 1 1.1 g of tetrabutylammonium hydrogen sulfate 1 was added

1.1 g (0.028 aoles) of sodium Yua hydroxide in 1θ will be water, so it is strongly n <~ ga for 2 h. The methylene chloride layer was separated, washed with water and afei over sulphate aagnesium. The control of the filtrate gave a solid product, which was overcome by crystallization from isopropanol to give 5 * 4 g of yield, m.p. 170-172 C.

NOt (CDCl ^ St 1.65 (d, J «7Hs, 5 * 0,

5.5-4.5 (m, <H),

4.95 (c, JHs, 1H),

7.1 (ABe, J «9Hs, 4 * 0;

7.45-6.25 (a, 5 «).

8.65 (s, IB).

Cyclicsalcohol of the corresponding 2-haloethyl amide, which will be obtained by dihydrooxasols, and Table TU.

TABLE VII

E Mr D L 6-CF ₃ H H ' H 6-No H, H ^CH 3 6-OCH ₃ H H ch ₃ 6-CH ₃ H ch ₃ · CH ₃ 6-C1 H H c ₂ h 6-C1 7-C1 H ch ₃ 6-F H ch ₃ CH ₃ H H H H 6-C1 8-C1 H CH ₃ 5-C1 7-C1 H CH ₃

• 41 2- (Benzylocaifecoxl) -5-n> triflunoalkyl; tn

A solution of 28.0 g (0.014 sol) of 4-benzoxyphenol in 5θ of dimethylformadide in an acetic atmosphere was added dropwise at about 15 C 6.0 g (0.14 sol) of 57 l of sodium Jus hydride in 25 ml of dimethylformadide. Now, until hydrogen is extracted, 25.0 g (0.14 nol) of 2-chloro-3- "ethylquinoxaline are added and the rakeion of saefia ae is heated to 125 C for about 2 h". then raakeiona saefia poured into ice water (500 oc). The solid product ss was filtered and crystallized from aethanol to give 56 3 g of the title compound, m.p. 99-102 C.

Mffi (HOUSE) S t 2.75 (s, 5H)

4.95 (β, 2H),

6.85-8.1 (s, 2H).

Other useful quinoxaline intermediate may also be obtained by this process ·

- 42 žrffoff. 12

2- (i-Hydroxylphenoxy) -3-methylquinoxalone

A solution of 12.5 g (0.05 mol) of borosulfonated bromide a 100 ee of netile chloride was added with <0 min, well stirred, cold (-62 C) solution of 17.1 g of 2-C4-benzolocaiphenoxy) -3-methylquinocaine (0.05 aola ) a <00 oo methylene chloride, When the addition is complete, the mixture stirs to stand so that its temperature will drop to room temperature after reaction (2h) · The reaction mixture is poured over 1 hour · of water · 1 is added 500 oo methylene of chloride. The mixture was stirred sharply for 40 min. , and the insoluble mass is separated by filtration. · Crystallization from ethanol-water (lil) stirred 6.4 g of the title product, m.p. 175-178 C.

BUR? s 2.8 (a, 3H),

7.05 (ABr, J «7 Ηβ, 4H),

7.5-6.5 (m, 4H),

9.8 (β, XH).

Other 2- (4-hydrocaiphenoxy) quinoxalines can also be obtained by the use of this method, spiked with (2- (4-hydroxy-phenyl-4-or 7-chloroquinocaaline · m.p .: 185-194 C.).

WR (CTClj - MS0) $ t 7 (ABr, J - 9Hs, 4H),

7.6-8.2 (m. 3H),

8.7 (·. IB).

-43 Motu 4- / 4- <6- or 7-chloro-2-quinoxalinyloxy) phenoxy / -2per tanoate

A mixture of 16.0 g (0.059 mol) of 2- (4-hydroxy-ethoxy) - N - or 7-chloroquinocaaline, 15 g (0.078 sol) of methyl 4-broco-2-pertaroate 1 11 g (0.0797 mol of potassium carbonate in 200 oe acetonitrile was dried at rectification 24 h Zatia ae the reaction mixture is poured into 500 co water and ice 1 the aqueous solution is extracted once with ether (350 co) The ether extract Batin is washed with water, saturated with aa a sodium bicarbonate, bromine and dried over aggression. The removal of magnesium sulfate is accomplished by filtration, and the conoentralia of the ether solution in vacuo gives a solid product which is purified in a column of chromatography (silica gel-methylane chloride as a diluent) to give 13 ° g of the title compound as a crude oil. .

NAME (CDC1) S t 1.55 (d, 3H, J 6 Ha),

3.80 (s, 3H),

4.70-6.15 («.IH),

5.95-6.30 (*, 1H),

6.90-6.15 (m, 8H), s.90 (s 1H).

The compounds of formula XIX 'listed in the following table may be prepared by a similar procedure as 1 2- (4-hydroxyferoxy) quinoxaline 1 alkyl 4-bromo-2-alkanoate <

TABLE VIII

A E Mr D L b ·· H 6-CF ₃ H H H CH ₃ ch ₃ 6-F H H ch ₃ ^CH 3 H 6-F H H H t-C.H H 6-No H H ch ₃ CH / H 6-OCH ₃ H H ch ₃ ^CH 3 H 6-CH ₃ H ch ₃ ch ₃ ^CH 3 ch ₃ H H H ch ₃ ch ₃ H 6-C1 H H c ₂ h ₅ 1 ” ^C 3 ^H H 6-C1 7-C1 H ch ₃ ^C 2 ^H 5 H 6-CF ₃ S H ch ₃ nC ₄ H H 6-F H ch ₃ CH ₃ nC ₃ H H H H H H ch ₃ ^CH 3 6-C1 H H ch ₃ ch ₃ ch ₃ 6-CF ₃ H H H ^C 2 ^H 5 ^C 2 ^H 5 H H H ch ₃ CH ₃ C ^? H H H ch ₃ CH ₃ ^C 4 ^H 9 H H H ch ₃ ^C 2 ^S 5 H 6-C1 8-C1 H ch ₃ ch ₃ H * 5-C1 7-C1 H CH ₃ ch ₃

- <5 Priaer 15

4- / 4- (6- or 7-chloro-2-quinoxalinyloxy) ferroxyl-S-pentanoic acid

A solution of 7.5 g (0.02 sol) ethyl 4- [4- (6-yl-7-chloro-2quinoxalinyloxy) phenoxy] -N-pentanoate in 20 ml of 10% diaethylfornadide was added in 2.0 g of 50% sodium hydroxide. 4,0 al water decolorization, the sachet is left to stay at a constant temperature. After 1.5 h, water (200 oo) was added. 1 lb. was neutralized with glacial hydrochloric acid 1 extracted with ethyl acetate (150 al), the ethyl acetate solution was evaporated with water, dried over sulphate and concentrated in vacuo to afford the Salt product, yield 5.5. Mr Rücker

Bffi (CDCl3) # and 1.55 (d, 3H, 6.5 Hz),

4.70-5.15 (a, 1H),

5.95-6.50 (n, 1H),

6.9θ-β.5Ο (β · 9H)

8.90 (s, 1H).

Hydrolysis of the corresponding leg osterates yields the compounds of formula lil, which are listed in Table IX.

TABLE IX

A E Mr D L "" - H 6-CF ₃ H H H ch ₃ 6-F H H ch ₃ H 6-CF ₃ H H H 15 H • 6-No H H hh ₃ H 6-OCH ₃ H H ^CH 3 H 6-CH ₃ H ch ₃ ch ₃ ch ₃ H H H ch ₃ H 6-CI H H c ₂ n. 20 H 6-CI 7-Cl H CH ₃ H 7-CI H H ^CH 3 H 6-F H ch ₃ ch ₃ H H H H H ch ₃ 6-CI H H ch ₃ 25 ch ₃ 6-CF ₃ H H H c ₂ h ₅ H H Ξ ch ₃ ^C 3 ^H 7 H H H · ch ₃ ^C 4 ^H 9 H H H ch ₃ H 6-CI 8-C1 S ch ₃ 30 H 5-C1 7-CI H ch ₃

-r? Example 16

N-Nethyl-4- / 4- (6- or 7-chloro-2-chloroqualinyloxy) -phenoxy / -2-pentanarald

The title of the compound clearly prepares ss as a yield of 71% Ib of the corresponding acid by step, which I described in Priaer 4, and iaa m.p. 199-201 C (daa).

ras (CDCljli and 1.50 (d, JH, J «7 HZ),

2.90 (d, 3H, J * 5 H) ·

4.70-5.15 (a, 1H),

5.95-6.30 (m, 1H),

6.80-8.20 (n, 9H),

3.90 (s, 1H).

The tertiary of the corresponding corresponding chlorides with some aiains, using the procedure of Example 4, or the corresponding strains with trifluoromethanesulfonyl chloride, may, with the use of the procedure of Example 5, yield the Formula III as listed in Table X.

TABLE X

10 A E Mr D L ^R 2 k - ” H 6-CF H H H H H ^CH 3 6-F H H ch ₃ H ^CH 3 H 6-CF ₃ H H H cyclohexyl H 15 H 6-No H H ch ₃ ^C 6 ^H 5- H H 6-OCH ₃ H H ch ₃ C ₆ H ₅ ^ch 2- H H 6-CH ₃ H ch ₃ CH ₃ H (ch ₃ ) ₂ ch- ch ₃ H H H CH ₃ - 4 9 H H 6-CI H H ^C 2 ^H 5 ch ₃ ch ₃ · 20 H 6-CI 7-C1 H ch ₃ nC ₄ H _g CH ₃ H 6-CI H H ch ₃ - (ch ₂ ) ₂ -o- (ch ₂ ) ₂ - H 6-F H ^CH 3 ch ₃ - (ch ₂ ) ₄ - H H H H H - <ch ₂ ) ₆ - ch ₃ 6-CI H H CH ₃ 1- ^C 4 ^H 9 H 25 ch ₃ 6-CF ₃ H H H ^CH 3 CH ₃ O- c ₂ h ₅ H H H ch ₃ ^C 2 ^H 5 H ^C 3 ^H 7 H H H CH ₃ H cyclopentyl ^C 4 ^H 9 H H H CH ₃ - (ch ₂ j ₂ - N (CH ₃ ) - (ch ₂ ) ₂ - H 6-CI 8-C1 H CH ₃ H CH ₂ -CH = CH ₂ 30 H 5-C1 7-C1 H ch ₃ H F \ _ CH ₂ CH ₂ N {CH ₃ H H H H CH ₃ / oVci H

6-CI H

H

A E Mr TABLE D X (continued) L * _2 h H 6-F H H CH ₃ - <° Δ CH ₃ H 6-CF ₃ H H ch ₃ - {o> -no ₂ H H 6-Cl 7-C1 H ch ₃ ch ₇ ch ₇ oh H H H H H ^C 2 ^H 5 CH ₉ CH ₇ Art . H H 6-Cl H H H ch ₃ _ / q) -ch ₃ H H 6-Cl H H H / CH ₃ OCH, H H H H H ch ₃ cr -so ₇ cf ₃ H H 6-CF ₃ H H ch ₃ - ^s ° ₂ čf ₃ H H 6-F H H ch ₃ -so ₂ cf ₃ H H 6-Cl H H ch ₃ - (o> -sch ₃ H H 6-Cl H H ch ₃ -® ^ ^C A ^H 9 H

- 50 - Allyl 4- / 4- (6- iii 7- Jfrhaer 17 • chloro-2-wide or ryl oxy) phenoxy / - 2 * pertar.oata

The titled sail and the r.aveder sailor in Tayx »li M can ae obtained by the procedure which is ar.alogar, or.on description & r.on ui ^J rhymes of rhymes 6, 7 and S.

TABLE XI

A E Mr D L XR ₁ H 6-CF H H H O-cyclohexyl ch ₃ 6-F H H ch ₃ o (ch ₂ ) ₂ o (ch ₂ ) ₂ oc ₂ h H 6-CF ₃ H H H och ₂ c = c-ch ₂ ci H 6-No H H ch ₃ ^OC 6 ^H 5 H 6-OCH ₃ H H ch ₃ OCH ₂ CgH ₅ H 6-CH ' ₃ H · ch ₃ ch ₃ och ₂ ch ₂ ch ₂ och ₃ ^CH 3 H H H ch ₃ ° - ^C 18 ^H 37 H 6-C1 H H ^C 2 ^H 5 o-ch ₂ c = ch H 6-C1 7-C1 H ch ₃ ON = C (CH ₃ ) ₂ H 6-C1 H H CH ₃ H 6-F H ch ₃ ch ₃ ON = C (CH ₃ ) (SCH ₃ ) H H H H H ON = CH (C ₄ H ₉ ) CH- 6-C1 'H H ch ₃ S-cyclohexyl ch ₃ 6-CF ₃ H H H S-benzyl C H H H H ch ₃ sch ₂ ch = ch ₂ c ₃ H ₇ H H H ch ₃ sch ₃ C.H- H H H CH- SC.H- 4 9 3 4 9 H 6-C1 8-C1 H ch ₃ sc ₆ h ₅ H 5-C1 7-C1 H ch ₃ SCH ₂ CH = CH ₂ H 6-C1 H H ch ₃ ^SC 12 ^H 25

Pr la er 18

4- / 4- (6- 111 7-chloro-1-chloro-8-yl-cyclohexyl) -benzoyl-1-methyl-1-yl

Yield of 3.0 g (0.01 mol) of 2- (4 "hydroxy-phenoxy (-6- or 7-chloroquinoxalir. A, 4 g (0 · 025 mol) of 4-b roaoperteraitrile, 3 g (C.0217 mol) of potassium carbonate was mixed. The reaction mixture is poured into 15θ cc of ice-water and extracted once with ether (200 cc). The ether extract is washed with water, saturated with rhodium bicarbonate. salted with water and dried over raagnesum sulphate, ttagnesium sulphate is removed by filtration and the filtrate concentration gives an ee solid, which is purified by column chromatography to give 2.5 g of the desired product as a yellow oil.

KMR (CDCl3) J 1.45 (d, 3H, J 7 Hz),

4.60-5. 10 (a, 1H),

5.25-5.90 (π, 1H),

6.4O-e.00 (m, 8H).

The chiroxalin compounds listed in Table XII may be obtained by weight in an analogous manner.

TABLE XII

E Mr D L 6-CF ₃ H H H 6-CF ₃ H H H 6-No H H ch ₃ 6-OCH ₃ H H ch ₃ 6-CH ₃ H cn ₃ ch ₃ 6-C1 H H c ₂ h 6-C1 7-C1 H ch ₃ 6-F H cn ₃ CH ₃ H H . H H 6-C1 8-C1 H ch ₃ 5-C1 7-C1 H ch ₃

25.

Priner 19

Patrijun 4- (4- (6 or 7-chloro-2-quinoxyloxy) phenoxy) 2-nertaroate

The title compounds and the compounds of Table XIII can be prepared using a procedure analogous to that in Example 10.

TABLE XIII

A E Mr D L s M H 6-CF- H H H 1 On ch ₃ 6-F H H ch ₃ 1 On H 6-F H H H 1 On H 6-No H H ch ₃ 1 K H 6-OCH ₃ H H ch ₃ 1 K H 6-CH ₃ H ch ₃ ch ₃ 1 Li ^CH 3 H H H ch ₃ 1 Li H 6-C1 H H c ₂ a 1 nh ₄ H 6-C1 7 _r Cl H ch ₃ 1 nh ₄ H 7-C1 H H. ch ₃ 1 CH ₃ NH ₃ H 6-F H ch ₃ CH ₃ 1 (HOCH ₂ CK ₂ ) H H H H H 1 (ch ₃ ) ₂ nh ₂ ch ₃ 6-C1 H H ch ₃ 1 (C ₂ h ₅ ) ₃ nh CH ₃ 6-CF ₃ H H H 1 (HOCH ₂ CH ₂ ) ^C 2 ^H 5 H H H ch ₃ 1 (HOCH ₂ CH ₂ ) c ₃ h ₇ H H H ch ₃ 1 ^C 4 ^H 9 ^NH 3 ^C 4 ^H 9 H H H CH ₃ 2 Ca H 6-C1 8-C1 H CH ₃ 2 Ca H 5-C1 7-C1 H CH ₃ 2 Mg

- 55 Example 20

Synthesis of Nethyl 2- (4-hydrochalphenoxy) proparoate

An amount of 42 g (0.25 mol) of methyl 2-bromopropiorate added ee in 0.25 mol of the sodium salt of p-benzoxyphenol (obtained from 1J.5 g of sodium methoxide and 50 g of p-benzyloxy) in 70 cc D&F.

The reaction mixture was then warmed to approximately 80 C for 14.5 h. The cold reaction mixture is suppressed by pouring it into 1 liter of ice water. The product was quenched by separating the crystallizer from methanol to give 45.2 g of methyl 2- (4-benzoxyphenoxy) propanoate, m.p.

58-42 C.

124R (CDCl3) δ 1.6 (d, J = 7Hz, 3H),

5.7 (a, JH),

4.6 (f ', J' Hz, 1H),

4.9 (β, 2H),

6.8-7 (m, 4H),

7.2-7.6 (m, 5H).

By catalytic hydrogenator at about 45 p.s.i. 4θ g of methyl 2- (4-benzoxyfenoxy) propanoate in 200 co HIP in the presence of 1 g of 10 $ Pd / c gives ae 2- (4 "hydroxyphenoxy) propanoate in near quantitative yield. The material obtained is pure enough to give could be used in the preparation of the compounds of the present invention.

RMR (CDCl 3): 1.6 (d, J 7 Hz, JH),

3.7 (β, 3H),

4.6 (r, J 7 Hz, 1H),

6.7-6.9 (ra, 4H), (s, 1H).

- 56 Synthesis of Methyl 2- (4-Hydroxyphenoxy) acetate

The title compound was obtained by alkylation of the sodium salts of p-benzoxyphenol with methyl bronoacetate, P * yielded netil 2- (4-benzoxyphenoxy) acetate (m.p. 71-75 θ), and debenzolation then gave the title compound, mp. 108-111 C.

Μ.ΊΡ, (IKSOp t 3.6 (β, 3 ^H ),

4.5 (β, 2H),

6.6-6.9 (n, 4H),

9.05 (β, 1H).

Example 22

Purification of Nethyl 2- (4-hydroxyphenoxy) -2-methyl proparoate

The title compound is obtained by alkylation of the sodium salt of p-benzoxyphenol with methyl 2-brorao-2-methylpropanoate · Methyl 2- (4-benzoxyphenoxy) -i-ethylpropanoate (tt 45- ^ θ C) is subjected to the removal of the benzene group of catalytic acid by hydrogenation got the desired semiconductor, mp 135 / 0.25.

? sm (PMSO> j Ϊ 5 (s, 6H),

3.7 (β, 3Π),

6.75 (a, 4H) _#

9.1 (β, 1H).

By using balononic acid derivatives in place of methyl -2-bronoalkanoates in the process of Example 20, numerous intermediate products can be obtained to obtain the compounds of Formula IV.

- 57 Example 23

Dimethyl 2-methyl-2- / 4- (2-quinoxalirdloxy) phenoxy / propanate

Under a nritsr nitrogen atmosphere, a mixture of 50 co dimethylformadide in 0.8 g (0.02 mol) of a 57 g of sodium hydride solution of 4.8 g (0.02 mol) of 2-C4-hydroxyphenoxy) chlorooxaline in 30 cc of dimethylformadide was added. When hydrogen separation begins, a drop by drop is added

4.8 g (0.021 mol) of diethyl 2-bromo-2-nethylpropanedioate, When complete, the mixture was stirred overnight at a clear temperature. The reaction mixture was poured into ice water and the aqueous solution was extracted with ether (3 X 150) to give a solid dry extract extract to obtain a solid product which was purified by a gel gel in a chromatographic column (methylene chloride-metarol mixture as a clarifier) and crystallized from ethyl acetate 4exane oa would give up to 1.2 g of the title compound, mp 87-93 О.

W (CDC1 ₅ ) t 1.8 (s, 3 «), 3.8 (β, 6H),

6.9-7.3 (a, 4II),

7.5-7.8 (m, 3H),

7.9 -8.2 (m, III),

8.7 (s, 1H).

- 58 Example 24

Methyl 2- (diethylaninocarbonyl) -2- / 4 ~ (2-quinocealinyloxy) fer.oxy / propanoate

The following procedure may be used to obtain the compound found.

Rectification of a mixture of 5.9 g (0.02 mol) of methyl 2 - / (dimethylanir.o) carboryl / -2- (4-hydroxyphenoxy) propar.oate, 3.3 g (0.02 mol) of 2-chloroxyroxalin and 5.5 g (0.04 mol) ) of potassium carbonate in 100 oc methyl ethyl ketone in time.B of 18 h. The hot solution is filtered to give you the desired Compound.

The compounds of Formula IV listed in Table XIV can be prepared by the above procedure.

TABLE XIV

A E Mr «8 w * " ¹ CH ₃ 6-C1 H CH ₃ -CONHC ₄ Hg H H H ^C 2 ^H 5 CN H 7-F H ··· - ♦ CH ₃ CO ₂ CH ₃ H 6-C1 7-C1 C ₂ ^h 5 ^CO 2 ^C 2 ^H 5 H 6-C1 H ch ₃ CO ₂ CH ₂ C _g H ^C 3 ^H 7 H H ch ₃ conh ₂ ^C 4 «9 H H CH ₃ CONHC _g H ₅ H 6-CF H ^CH 3 conhoch ₃ H 6-F H ^C 4 ^H 9 con (c ₂ h ₅ ) H 6-CH ₃ H ^C 3 ^H ? ^CO 2 ^C 2 ^H 5 H 6-C1 H ^CH 3 CN H 6-OCB ₃ H CH ₃ co ₂ ch ₃ H 6-No H CH ₃ ^CO 2 ^C 3 ^H 7

Example 25 Ylethyl 2-Nethyl-2 - »(4-2-quinoxaliroxy) phenoxy propanedioate

The procedure described in Example 5 mo * will be used to prepare the acids described. By hydrogenation of the corresponding diester, the compounds of formula IV shown in Table XV can be prepared.

TABLE XV

A E Mr ^R 8 f ch ₃ 6-C1 H CH ₃ H H . H ^C 2 ^H 5 H 6-F H ch ₃ H 6-C1 7-C1 ^C 2 ^H 5 H 6-C1 H ch ₃ ^C 3 ^H 7 H H ch ₃ ^C 4 ^H 9 H H ch ₃ H 6-CF ₃ H ch ₃ H 6-F H ^C 4 ^H 9 H 6-CH ₃ H C3H7 H 7-C1 H CH ₃ H 6-OCH ₃ H ch ₃ H 6-No H ch ₃

Example 26

Katrium is methyl 2-methyl-2- (4- (2-quinoxalyryloxy) phenoxy) propanedioate _______

The procedure described in Example 10 can be used to prepare the sodium salts;

A E Mr S M H 6-C1 H ^CH 3 1 Na «; H 7-C1 H ^c H. ₃ 1 Ha H 6-C1 7-C1 ^CH 3 1 · R H H H ch ₃ 1 K H ' 6-F H c ₂ h ₅ 1- Li H 7-CF ₃ H ^C 2 ^H 5 • 1 nh ₄ H 5-C1 H ^C 2 ^H 5 1 (HOCH ₂ CH) ₂ nh fc 8-No H ^C 2 ^H 5 1 (C ₂ h ₅ ) ₃ nh: ch ₃ 6-F H ch ₃ 1 tc ₄ H ₉ NH ₃ ^CH 3 7-C1 H ^CH 3 2 Ca ^CH 3 6-C1 7-C1 ^CH 3 2 Mg

Example 27

Methyl 2-nethyl-3- (raethylthio) -3oxo 2 / 4- (2-chloro-alinyloxy) pheroxyl propanoate

The acid chlorides may be obtained by the addition of the pure sodium salt of the acids of Example 25 (0.1 mol) in raspberry in amounts of oxalyl chloride (0.12 mol in 200 ° ether). After 4-5 h of standing at room temperature, the sodium chloride is removed by filtration and the ether and excess oxalyl chloride is removed in vacuo. Jvic acid chlorides can be used without further purification,

The procedure outlined in Example 7 may? will be used for the purpose of the title Compound.

In a similar manner, the compounds of Formula XV listed in the following table can be obtained from acid chlorides, appropriate alcohols, thiol ^ phenols, thiophenols or oximes.

TABLE XVII

A E Mr ^R s H 6-C1 H CH ₃ Q 6-CF ₃ H ^C 2 ^H 5 H 6-F H ^C 2 ^H 5 H 7-F H c ₂ h ₅ H 7-CF ₃ H ch ₃ H 6-C1 H ch ₃ H 6-C1 7-C1 CH ₃ ch ₃ H H ^C 2 ^H 5

Χ ^

-on = c (ch ₃ ) ₂

-sc ₆ k ₅ ^SC 4 ^H 9

-OCH ₂ C _g H ₅

-o (ch ₂ ) ₂ o (ch ₂ ) ₂ oc ₂ h ₅

-OCH ₂ CSC-CH ₂ C1

- ° ^C 6 ^H 5

-OCH ₂ -CH = CH ₂

- 64 Example 28

Synthesis of methyl 4- (4-hydroxyphenoxy) pentanoate g (0.19 mol) of methyl i-bro-but-ch-per.tarotate sample was added to a mixture of 30 g (0.15 mol) of p-benzoxyphenol and 25 g (0.18 mol) of potassium of carbonate in 200 cc methyl ethyl ketone. The mixture was stirred and rectified for approximately 18 h. The cold reaction mixture was poured into 400 cc of ice water and the aqueous solution was extracted once with ether (350 cc). The ethereal solution was then washed with water, saturated with sodium bicarbonate, saturated saturated sodium chloride and dried over magnesium sulphate. C.

BIR (CDCl3) j.45 (d, J = 6 Hz, 3H),

3.75 (s, 3H),

4.55-5.15 (m, HI),

5.0 (s, 2H),

5.85-6.25 (m, 1H),

6.7-7.6 (m, 10H),

The catalytic hydrogenation of methyl 4- (4-benzoxy-oxy) pertar.oate in ethanol in the presence of 1θ $ Pd / c gives the title compound as a yellow oil which was purified with silica gel in a chromatographic column.

KMR (CDCl 2)? 1.25 (d, 3H, J * 6 Hz),

1.7-2.7 (m, 4H),

3.65, (B, 3H),

3.9-4.4 (m, 1H),

6.5 (s, 1H),

6.78 (s, 4H).

- 65 Priaer 29 & ethyl 4- / 4- (6- or 7-chloro-2-quinoxalyryloxy) pheroxy / pertanoate

2.5 g (0.0115 mol) of sample 2.6 or 7-dichloroquinocalaric acid added 1.5 g (0.0109 moles of potassium carbonate and 2.5g (0.0115 aola) methyl 4- (4-hydroxyphenoxy) pentar.oate in 45 cc acetonitrile. The reaction mixture is poured into 500 cc of water aa ice and precipitated in an ailika gel column (methylene chloride serves as dilution) to hi 1.7 g of the title compound as a yellow oil.

Pjffi (ODClj)? 1.57 (d, J 6 Hz, 3H)

2.05 (t, 6 Hz, 2H),

2.5-2.7 (α, 2H),

5.65 (s, 5H),

4.05-4.7 (n, 1H), β.8-6.05 (m, 7H),

8.8 (a, 1H).

According to Example 29, I will be able to get a cinema caliper. unions listed in Table XVIII.

66 TABLE XVIII *, • A • » 5 γ ** tb M L G ^ '0- <0> -0-H-CH ₂ ^CH 2 ^CO 2 ^R 1 - 'D 10 · A E Mr D L ^R 1 - - - H 6-CF ₃ H H H CH ₃ ^CH 3 6-F H H ch ₃ CH ₃ H 7-F H H H tC ₄ Hg 15. H 6-No H H CH ₃ CH ₃ H 6-OCH ₃ H H ch ₃ ch ₃ H 6-CH ₃ H ch ₃ CH ₃ ch ₃ ch ₃ H H H ch ₃ ch ₃ , H 6-CI H H. ^C 2 ^H 5 i- ^C 3 ^H 7 20 H 6-CI 7-CI H ch ₃ ^C 2 ^H 5 H 6-CI H H ^CH 3 n- ^c 4H ₉ H 6-F H ch ₃ CK ₃ n- ^c 3 ^H 7 H H H H H ch ₃ ch ₃ 6-CI H H ch ₃ ch ₃ 25 ch ₃ 6-CF ₃ H H 'H ^C 2 ^H 5 ^C 2 ^H 5 H H H CH ₃ CH ₃ ^C 3 ^H 7 H H H ch ₃ ch ₃ ^C 4 ^H 9 H H H CH ₃ ^C 2 ^H 5 H 6-CI 8-C1 H CH ₃ CH ₃ 30 H 5-C1 7-CI H CH, CH,

⁶⁷

Example 50

4- (4- ($ or 7-chloro-2-quinoxyloxy) phenoxy) pentaric acid The compounds of the title, as well as the compounds of formula V, listed in the following table, may be prepared by a method analogous to that described. in Example 3.

Zabela XIX

A E Mr D L H t 6-CF ₃ H H H . CH ₃ 6-F H H ch ₃ 20 H 7-F H H H H 6-No H H ch ₃ H 6-OCH ₃ H H ch ₃ H 6-CH ₃ H ch ₃ ch ₃ ch ₃ H H H ch ₃ 25 'H 6-C1 H H c ₂ h H 6-C1 7-C1 H ch ₃ H 6-C1 H H CH ₃ H 6-F H ch ₃ ch ₃ H H H H H 30 CH- 6-C1 H H CH ₃ ch ₃ 6-CF ₃ H H H c ₂ h ₅ H H H ch ₃ • ^C 3 ^H 7 H H H ch ₃ c ₄ h ₉ H H H ch ₃ 35 H 6-C1 8-C1 H CH H 5-C1 7-C1 H ch ₃

Priner 31

7, N -diethyl-4- (4- (6 or 7 chloro-2-quinoxaryloxy) -phenoxy) pentamide_

The procedure described in Printer 4 can be used to prepare the compounds of the title and quinoxalines of Formula V, which are given in Table XX.

Table XX

/ ^R 2 ^X R.

H ch ₃

H

H

H

H

CH,

H

H

H

H

H

CH.

CH.

c ₂ h ₅ c ₃ h _? hc ₄ H ₉ h

6-CF ₃

6-F

6-F «

6-No

6-OCH.

6-CH ₃

H

6-C1

6-C1

6-C1

6-F

H

6-C1

6-CF ₃

H

6-C1

H

H

H

H

H

H

H

H

7- C1 H

H

H

H

H

H

H

H.

8- C1

H

H

H

H

H

CHH

H

H

H

CH.

H

H

H

H

H

H

H

H ch ₃

H ch ₃ ch ₃ ch ₃ ch ₃ c ₂ h ₅ ch ₃ ch ₃ ch ₃ h

ch ₃

H

CH ₃

CK.

J

CH,

CH.

j

H

H cyclohexyl ^C 6 ^H 5 ^C 6 ^H 5 ^CH 2H tC ₄ H ₉

CH ₃ nC ₄ H ₉

H ch ₃

H

H

H (CH ₃ ) ₂ chH ch ₃

CH.

- (CH ₂ ) ₂ -o- (ch ₂ ) ₂ - (ch ₂ ) ₄ - (CH,). IC ₄ H ₉

CH, '2 ^λ 5

C.H.

6 H

CH ₃ OH cyclopentyl - (ch ₂ ) ₂ -n (ch ₃ ) - (ch ₂ ) ₂ H CH ₂ -CH-CH ₂

A E Mr TABLE 69 XX (continued) ^ 3 D L ^ 2 H 5-C1 7-C1 H ck ₃ H CH ₇ CH ₅ N (CH ₃ ) ₇ 5 F \ _ H H H H -®- ^cl H 10 H 6-Cl H H H / u ~ <2> H H 6-F H H ch ₃ CH ₃ H 6-CF ₃ H H ch ₃ - © ~ ⁰ 2 H 15 H 6-Cl 7-C1 H CH ₃ ch ₇ ch ₇ oh H H H H H ^C 2 ^H 5 CH ₇ CH ₇ Art H CH- \ 2 H · 6-Cl H H H HO / - CHj H 20. • / CH ₃ ncn ₃ H 6-Cl H H H H 25 Cl H 6-Cl H H ch ₃ - <0> -sch ₃ H • U 4 ^ 6-Cl H H ch ₃ \ o) -c ₄ h ₉ H

- 7ο Example 52

Allyl 4- / 4- (6- iii 7 * ^, chloro ^ - 4clnoalkylaryloxyphenoxy / pentanoate

The title compound and compounds of Formula V, which are listed in Table XXI, will be obtained by a procedure analogous to that described in Example 7.

TABLE XXI

M ^A gfoX / - Λ 'τ ° G ^X ) yU3-C-CH ₂ CH ₂ -C-XR ₁ \ _2 - / D

A E Mr D L ™ 1 H '6-CF ₃ H H H 0-cyclohexyl ch ₃ 6-F H H ch ₃ O (CH ₂ ) ₂ O (CH ₂ ) ₂ OC ₂ H H 7-F H H H och ₂ csc-ch ₂ ci H 6-No H H ch ₃ ° c ₆ h ₅ H 6-OCH ₃ H H ch ₃ och ₂ c ₆ h ₅ H 6-CH ₃ H ch ₃ ch ₃ OCH ₂ CH ₂ CH ₂ OCH ₃ ch ₃ H H H ch ₃ ° ' ^C 18 ^H 37 H 6-C1 H H ^C 2 ^H 5 o-ch ₂ c = ch H 6-C1 7-C1 H CH ₃ ON »C (CH ₃ ) ₂ / —i H 6-C1 H H ch ₃ O-N = / J H 6-F H ch ₃ ch ₃ ON = C (CH ₃ ) (SCH ₃ ) H H H H H ON = CH (C ₄ H ₉ ) ch ₃ 6-C1 H H ch ₃ S-cyclohexyl ch ₃ 6-CF ₃ H H H S-benzyl ^C 2 ^H 5 H H H ch ₃ sch ₂ ch-ch ₂ = 3 * 7 H H H ch ₃ sch ₃ = 4 * 9 H H H ch ₃ sc ₄ h ₉ H 6-C1 8-C1 H ch ₃ SC.He about 5 H 5-C1 7-C1 H ch ₃ sch ₂ ch »ch ₂ H 6-C1 H H ch ₃ SC, «H-e 12 25

- 72 Example 33

4- / 4- (6- or 7-chloro-2-quinoxalinyloxy) phenoxy / penta-nitride

The title compound of the compounds of Formula V, which are listed in Table XXII, can be obtained on the rally described in Example 29 using 4-hydroxyphenoxy) pentanenyltril instead of methyl 4- (4hydroxyphenoxy) pentaroate.

TABLE XXII

E Mr D L «» 6-CF ₃ H H H 6-C1 H H H 6-No H H ch ₃ 6-OCH ₃ H H ch ₃ 6-CH ₃ H ch ₃ ch ₃ 6-C1 H H c ₂ h 6-C1 7-C1 H ch ₃ 7-C1 H ^H ch ₃ 6-F H ch ₃ ch ₃ H H H H 6-C1 8-C1 H CH ₃ 5-C1 7-C1 H ch ₃

Example 34

Sodium 4- (4- (6 or 7-chloro-2-chiroxalyloxy) phenoxy) pentanoate ___

The compounds of the title and the compounds of Table XXIII can be prepared as described in Example 9.

<? ♦

TABLE XXIII

A E Mr D L s M H 6-CF ₃ H δ δ 1 On ch ₃ 6-P H δ CH ₃ 1 On H 7-F H δ δ 1 On H 6-No H δ Οδ ₃ 1 K H 6-OCH ₃ H δ Οδ ₃ 1 K H 6-CH ₃ H ch ₃ Οδ ₃ 1 Li ch ₃ H H H ' Οδ ₃ 1 Li H 6-C1 H δ C ₂ ^h s 1 nh ₄ H 6-C1 7-C1 Η ch ₃ 1 nh ₄ H 6-C1 H δ ^CH 3 1 ch ₃ nh ₃ H 6-F H ch ₃ Οδ ₃ 1 (HOCH ₂ CH ₂ ) ₂ nh. H H δ δ δ 1 (ch ₃ ) ₂ nh ₂ ^CH 3 6-C1 H δ ^CH 3 1 (C ₂ h ₅ ) ₃ nh ch ₃ 6-CF ₃ H δ δ 1 (HOCH ₂ CH ₂ ) ₃ NH c ₂ h ₅ H. H δ CH 1 (HOCH ₂ CH ₂ ) ₃ NH c ₃ H ₇ H δ Η ch ₃ 1 c ₄ h ₉ nh ₃ ^C A H δ δ ch ₃ 2 Ca H 6-C1 8-C1 δ ch ₃ 2 Ca H 5-C1 7-C1 Η ch ₃ 2 Mg

- 75 Example 56

Methyl 2- / 4- (6- or 7-chloro-S-chloro-oceinyloxyphenoxyl / propanoate, N-oxide

A solution of 0.7 g of m-chloroperoxyberzole kieelir.eu 10 cc raetilers of chloride is added dropwise to a solution of 1.1 g (0.003 mol) of methyl 2- / 4- (6- ill 7- chloro-2- chloro-oloxyloxy pheroxy / propar.oate in 10 cc of methylene chloride The temperature is kept below 35 0 at the time of addition When the addition is complete, the mixture is stirred at ambient temperature overnight, then the methylene chloride is washed with 5 ^ sodium carbonate and dried over magnesium esium sulfate. The concentration of the pure solution results in a solid product in the form of an oil which solidifies with n-hexar and the oil is separated, the solid filtered off is washed with ether and purified by column chromatography over silica gel with methylene chloride to give 0.15 g. of the title compound, mp 137-142 C.

The process described can be used to obtain the N-oxide and pentant protected chiroxalinoxy ethers of the present invention, wherein C = CH = CH.

-76 Formulations of the compounds of Formula I may be obtained in the usual manner, ie powders, granules, pellets, solutions, emulsion suspensions, wet powders, emulsifiable concentrates and 3l. Many of them can be used directly. The spray formulations can be dissolved in a suitable medium, and will then be used as a basis for volume trapping, which will chalk from a few liters to several hundred liters per acre. High-strength compositions can be used primarily as semi-finished products for further formulations. Formulations, Cheeses defonantly contain about 0.1 $ to 99 $ weight percent of active ingredient (sj and at least one of (a) about 0.1 $ to 20 $ surfactant (s) and (b) about 1 $ to 99.9 $ solid ill Liquid diluent (s). More precisely defined, they will contain cocoons in the following approximate proportions of J an:

Table XXV

Weight percentages

Active Surface Actuator Dehumidifier (s)

Wet dust 20-90 0-74 1-10 Oil suspensions, emulsions, solutions, (including emulsifiable concentrates) 10-50 40-64 1-20 Water suspensions 3-50 40-95 0-15 Dusty 1-25 Ϊ0-99 The scoreboard changes to 0-5 Granules and pellets 0.1-95 5-99.9 0-15 High-strength compositions 90 -99 0 -10 The scoreboard is now 0-2

The percentages by weight of the active ingredients plus at least one of the surfactants or diluent are 100.

Depending on the intended use and the physical properties of the kidney, lower or higher levels of active teats may be present. Higher surfactant ratios relative to the active ingredient are sometimes desirable, and are achieved by being introduced into the reservoir,

Typical solid diluents are described in "Fatkins et al., Handbook of Insecticide Dust Dlluent and Carriers," 2nd Edition, Borland Books, Caldvell, I> ew Jersev, but other materials must be used. Wet dusts and dusters require dampening agents aa great ability to absorb. Typical liquid diluents and solutions are described in Karden, Solvents Guide Second Edition, Interscience, New York, 1950. For suspension concentrates, a solubility below 0.1% is preferable, the conoerate solution should be stable at phase separation at 0 C. The list of surfactants recommended for use is found in ^{, r} McCutcheon's Detergente and Smulsifiers Annual MC Puhlishing Cjrp, Ridgewood, Kew Jersey, as well as in Sisely and '70od, Encyclopedia of Surface Active Agents, Chemical Publishirg Co. ., Inc., New York, 1964. All formulations contain small amounts of foam smelting additives, cake formation, corrosion inhibitors, microbial growth, etc.,

The process of obtaining such compositions is well known. The solution is obtained by simple mixture by mixing the ingredients. The fine solid composition is made by mixing, usually by grinding in a Hammer mill or a fluid mill. The suspensions are obtained by wet milling (see, for example, Littler, D.S. Patent 3, θ60,084). Granules and pellets can be obtained by spraying the active substance by a perforated grajular carrier or by agglomeration technique. See J.2. Browr.ing, Aglomeration, Chemical Engineering, Dec. 4, 1967, p.

147 and ”Perry * s Chemical 2ngineer Handbook Fifth Edition., I.icGraw Hill, New York, 1973, atr 8257.

For more information, see the following examples

H.M Loux, U.S. Patent 3,235,361, Feb 15, 1966, line 6, line 7, line 19, and Examples 10 to 41.

R, W. Luckenbaugh, U.S. Patent 3.3 ° 9.192, March 14, 1967, col

5, line 43 to col 7, line 62 Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182.

H.Gyein and E. Knueli, U ^ S. Patent 2,891,855,23 jin, 1959, col. 3, row 66 to col. 5, line 17 and Examples 1-4.

G.C. Klingmau, Weed Control ae a Science ”, John Wilev and bona, Inc., New York, 1961, p. 81-96, i

J.P. Pryer and S.A, Bvans, ”Ffeed Control Handbook Fifth Edition., Blackvell Sointific Publioations, 0xford, 1968, pp. 101-103

In the following examples, all parts are given unless otherwise emphasized.

Example 37

Wet dust

Methyl 2- / 4- (6- or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, N-oxide 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2, "synthetic amorphous silicon 3% kaolinite 13%

The ingredients are mixed, ground in a hammer mill until particles below 50 microns are obtained, then the pores are then stirred and packaged.

- 79 Example 38

Wet brownies

Methyl 2- / 4- (6 or 7-fluoro-2-chiroxalinyloxy) phenoxy / propanoate 5 °% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2, soil impurity 466

The ingredients are mixed, ground in a hammer mill, and mixed in a vase mill to obtain particles less than 10 microns in diameter * The product is mixed again before packing »

Example 59

Granules! Iocra powder from Example 38 5% atapulgit granules 95% (U.S.S *. 2o-40 blends, 0.84-0.42 mm)

The wet powder mixture contains approximately 25% solids and is sprayed onto the surface of the atapulgit granules in a double blender. The granules are dried and packaged.

Example 40

Extruded pellets

Hetyl 2- / 4- (6,7-dichloro-2-quinoxalinyloxy) phenoxy and / -

propanoate 25% sodium sulfate anhydride 10% solid calcium ligninsulfonate « 5 < sodium alkylnaphthalenesulfonate V ' calcium% magnesium bentonite 59%

The ingredients are mixed, ground in a hammer mill and then quenched with 13% water. The mixture is extruded into cylinders of about 3 in diameter, which are then cut to give pellets about 3 m long. They may be used directly, or may be dried and broken into a v31 that passes through a sieve of U.S.S. ho. 40 (0.42 mm openings) so they can then be packaged for prime and fine recycling.

- 80 Example 41

Ul suspension

Methyl 2- / 4- (3- "ethyl-2-quinoxaline ± loksi) phenoxy / ~ propar.oate 25% polyoxyethylene sorbitol hexaoleate 5% high aliphatic hydrocarbon oils 70%

The ingredients are ground in a grinder until the solids are below 5 microns, the lobby's thick suspension can be compared directly, but it is even better to break it up and make an emulsion in water with soil.

7 »

Example 42

Kokra praživa

Methyl 2- / 4 .- (6- or 7-chloro-2-chiroxalyryloxy) phenoxy / acetate 20% sodium alkylnaphthalenesulfonate.at 4> .naturia ligninsulfonate 4% low-viscosity methylcellulose 3% atapulgite 69%

The ingredients are ground and ground in a hammer mill to give particles that are generally below 100 microns. The material is then stirred and passed through a sieve of U.S.S. Lo, 50 (open 0.5 mm) and then pack.

Example 45

Rice granules Hardness

Ethyl 2 - [- 4- (6- or 7-chloro-2-chloroxalyryloxy) phenoxy / propanoate IA

K, N-dimethylformadide 9g atapulgit granules 9θ> (U.S.S. 20-40 screen)

The active ingredients dissolve in solution and the solution does not spray on the dust-removing granules. After solution sprayer □ put the mixture to work for a short period and or.the granules are packed.

Example 44

Water suspensions

Methyl 2- / 4- (6- or 7-chloro-2-quinoxalir.yloxy) phenoxy / 2-methylpropanoate 40? »Polyacrylic acid 0.3J dodecylphenol polyethylene glycol ether θ.5 · * disodium phosphate 1>» monosodium phosphate 0.5 / ^? polyvinyl alcohol 1. '' · water 56.7 / '

The ingredients are mixed and ground together in a pedestrian mill to obtain Sostice which is generally below 5 microns.

Example 45

Rice strength granules

Methyl 2- / 4- (6 or 7-trifluoroethyl-2-chlorooxalnyloxy) f eroxy / proparate 0.1>

atapulgit granules 99.9. * (U.S.S.20 -40 meshes)

The active ingredients dissolve in solution 1 sprayed ra grar.ule ^v ez the dust in a double swirler. After spraying, the material is heated until the solution evaporates. KateriJal is left to cool and then packed.

Example 46

Granules

Methyl 4- / 4- (6 or 7-chloro-e-chlorooxalyloxy) phenoxy / pentanoate wetting reagent 14 solid with liginsulphorate (contains 5 "20 ^ natural gases) 10 <, atapugit clay 9: ^

The ingredients are cut and ground enough to undergo a 100 match game. This material is then added to the fluid container with the griller, and the air flow is adjusted so that Maga fluidizes the material, and then the water is finely dissolved, the fluidization and spraying is continued until the granules are desired. size. Then the sprinkler stops but the fluidization continues, in the heat of heating, until the water content decreases to ^y eljer.l r.ivo, which is generally below $ 1. The material is then taken out of the bathroom and brought to a * cellar size, which is about 14-Ιθθ mixes (1410-K9 microns), pc orda is returned packing for use.

- 83 Example 47

High strength concentrates

Netil 2- / 4- (6-yl 7-chloro-2-chloro-oxoalloxy) ferroxypropanoate, R-ocean 99% aerosol ailicon o.5% synthetic amorphous silicon 0.5%

The ingredients are mixed and ground in a hammer mill to obtain material! which generally pass through the sieve of the U.S.S.bo. 5® (0.3 mm openings). Concentrates ee can still be formulated if necessary.

Example 48

Kokra dusty

Cotyl 2- / 4- (2-quinocaalinoxy) phenoxy / propanoate 90% dioctyl sodium eulphoeuclate 0.1% synthetic fine silicon 9.9%

Saatojs also mix the grinder in a hammer mill to obtain Particles that have an uglsma of less than 100 microns. Which fir is passed through a sieve U.S.S. Ro. 50 and then ee packs.

Example 49

Wet dust

Methyl 2- / 4- (6 or 7-chloro-2? ^ Cinokealinok8i) phenocai / -pentar.oate

4 ^% sodium lignin sulfonate 20% montmorillonite clay 40%

The ingredients were mixed and ground in a deciduous mill and then in an air mill to obtain particles generally below 10 microns. The material will repackage and pack again.

Example 50

Praziva

Methyl 2- / 4- / 6,7 -dichloro or o-2-quinoxalinyloxy) phenoxy / propanoate 10% atapulgite 1θ% pyrophyllite 80%

The active ingredients are mixed with atapulgite and then passed through a hammer mill to form particles that are generally below 200 microns. The concentrate was further mixed with the pyrophyllite powder until it became homogeneous.

Example 51 Ethyl 2- / 4- (6 or 7-chloro-2-chiroxalinoxy) phenoxy / propanoate 20% concentrates ^with chlorobenzene 74% sorbitan monostear and polyoxyethylene condensate 6%

Saetojoi are combined and mixed to form a solution that can become an emulsion in water for further use.

The following test results indicate that the compounds of the present invention may be used for treatment. before and after the report on the broad spectrum of weed control in industrial areas, land around aagacin, in addition to fences and buildings, in addition to railways and roads. Additionally, it can be seen that these compounds can be used to control weeds in other plants, such as soybeans, cotton, sugar beets and beans,

The test compounds are particularly useful for the control of grass weeds as well as their removal, including in maize, low-leaved plants, such as soybean, arachnid, turnip beans, beans, flax, cabbage, tomatoes, potatoes, peanuts, eargare, er. diva etc. Grass weeds are acid grass (Digitaria sp,), manure (Echinochloa crusgalli), wild oats (Avena fatua), etc. The i-eka of these compounds can be used to control broadleaf weeds, and some can be used for grass weeds in plants such as wheat and rice. Tests indicate that the compounds of the present invention generally exhibit an unexpected degree of safety for gyros and common phytotoxicity in grass weeds before the plants and weeds appear, and may be used before or after emergence. including spraying weeds and herbs. Additional compounds can be used in the treatment of pre- and post-emergence j Ivan I myself Hi in combination with other herbicidins or surfactants.They have substances for a wide range of control of various types of weeds in growth for industrial areas, warehouse land and rising fences, in addition to buildings, railways and roads, etc.

The exact amounts of Compounds of the present invention to be used in particular situations depend on the bleached results. Factors affecting r.a optimum application ratio include the individual compounds used, the types of plants to be controlled, the type of soil, the formulation used, the previous weather conditions, the density of the leaves, the duire and the time of activity, which is not required. Broadly speaking, compounds are used from about 0.005 to 20 kg per hectare, and a more advantageous range is from 0.02 to 10 kg / ha, and all the compounds of this invention are active in bulk quantities. Vifii relationships are generally advantageous in application, so the range for appropriate conditions will be chosen as needed.

Herbicides effectively control grass weeds, as demonstrated by the examples, but they generally do not control broadleaf weeds when applied in rice relations. In order to obtain control for the broader spectrum of both broadleaf and grass weeds, a combination of compounds of the present invention with other herbicides that are effective in controlling broadleaf weeds is used. Iiombinators of the treatment of the compounds are mixed iii in the tank or an appropriate formulation is prepared.

The following examples illustrate possible combinations of J Compounds of the present invention with Brugl herbicides Application of bentazone (post-) strain

2.4 - DB (post-) peanuts, soybeans, clover

Simazln (pre-) pyrazone (pre-, immediately after-) gray dichloroprop (after-) herbs, lemon, peach, clover sugar beet past fences, and SiblJe roads, evergreen

Other herbicides Application ::. CxB (right after) peas dikamba (pre-) lar and hemp desraedifara (after-) šederr.a beets proraetrin (pre-) celery and spider fair.edifam (after-) the shader of the tail acifluorfen (Blazer) (after-) soybeans 2-] yllopo-N - [(4-raethoxy-6-ethyl] 1,3,5-triazin-2-yl) aminocarbonyl / benz olsulfonamide lan 1-raethylethyl 2 // (4,6-dimethoxymethoxy-l, 3,5-iriaiin-e-l) - aminocarbonyl // aminosulfonyl // benzgate lan 1-raethylethyl 2 // (<- inethoxy-45-flethyl- 1,3,5-triazin-2-yl) -eminocarbonyl / aminosulfonyl // - benzoate lan diroseb (post-) soybeans lenaoil (pre-) beetroot bronoxinil (poet-) wheat and. oats fluorometuron (pre-) cotton l - / ((/ 4,6-cimethoxypyrimidine- 2-yl) aminocarbonyl / aminosulfonyl) benzol) pyrrolidine soybeans 2-propenyl (2 - // (/ 4,6-dimethoxy- pyrimidin-2-yl) aminocarbonyl / aminosulfonyl // benzoate soybeans pyrazolate rice naproanilide rice

The compound

Methyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, mp · 108-111 C

Methyl 2- / 4- (2-quinocaalinyloxy) phenoxy / -propanoate, mp · 110-115 C

Methyl 2- / 4- (6-chloro-2-chloro-oleinyloxy) phenoxy / propanoate, K-ocaid, m.p. 137-142 C

Methyl 2- [4- (6-chloro-2-phenynocealinyloxy) phenoxy / 2-methylpropanoate, m.p. 83-87 C

Methyl 4- / 4- (6 or 7-chloro-2-quinocalyloxy) phenoxy / pentanoate, oil

Methyl 2- / 4- (6 or 7-trifluoromethyl-2-quinoxalinyloxy) phenoxy) propanoate, oil

KatriJun 2- / 4- (6 or 7-chloro-2-quinocaalinyloxy) phenoxy / propanoate

Methyl 2- / 4- _(6-f 7 dihloro- £ -kinoksalinilok8i) phenoxy) phenoxy / propanoate, m.p. 100-105 C.

Allyl 2- [4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, m.p. 64-69 O

2- / 4- (2-quinocaalinyloxy) phenoxy / propanone kiaelin, m.p. 137-111 «

Style 2- / 4- (6 or 7-chloro-2-flunoxalinyloxy) phenoxy / propanoate, mp 65- ^ 5 ^c

Butyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, m.p. 64-72 C

Methyl 4- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / pent-2-enoate, oil

Methyl 2- [4- (3 * ethyl-2-chloroOxalinyloxy) -phenoxy / propanoate, m.p. 83.5-88 C

Methyl 2- / 4- (7-chromo-quinoxalinylnoxy) phenoxypropanoate, m.p. 93-95 C

2- / 4- (6 or 7-chloro-2-quinocaalinyloxy) -phenoxy) propanoic acid, m.p. IO4-IO7 C

Compound Compound

Methyl 2- / 4- (6 or 7-fluoro-2-quinoxalinoxy) phenoxy / propanoate, m.p. 113-116 C

Methyl / 4- (6 or 7-chloro-2-chiroxalinoxy) phenoxyacetate, mp, 94-98 ^c

M _e til 2- / 4- (6 iii 7- N-ethyl-2-kinoksaliniloksi) phenoxy / propanoate, tt103-111 C

Methyl 2- / 4- (6,8-dichloro-2 111 3-quinoxalinyloxy) phenoxy) propanoate, m.p.

Benzyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, m.p. 77-83 C

- S-cyclohexyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxyphenoxy / propanethioate, oil

Cyclohexyl 2- / 4- (6 or 7-chloro-2-quinoxalinyl) oxyphenoxy / propanoate, m.p. 92-102 C

2-Methoxyethyl 2- [4- (6 or 7-chloro-2-quinoxalinyloxy)] phenoxy / propanoate, m.p. 64-72 C

Isopropyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) propanoate, m.p. 91-96 C

Octadecyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, m.p. 57-61 C

4-chloro-2-butynyl 2- / 4- (6 or 7-chloro-2-quinox-linyloxy) phenoxy / propanoate, oil

2- (2-ethoxyethoxy) ethyl 2- / 4- (6 or 7-chloro-2quinoxalinyl oxy) phenoxy / propanoate, oil

1-Methylethylidenamino 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoate, oil

N, N-diethyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxyl / propanamide, m.p. 121-124 C

N-Cyclopentyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanaide, m.p. 148-152 C

N-phenyl · 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanamide, m.p. 167-169 C

- 90 Compound

K-benzene 2- / 4- (6 or 7-chloro-2-quinocaneinyloxy) phenoxy / propanoid, m.p. 129-137 0

2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanoid, m.p. 171-174 C

N, N - dimethyl 2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / propanamide, m.p. 122-125 C

N- (4-chloro-2-fluorophenyl) 2- [4- (2-quinoxalinyloxy) phenoxy] propanamide, m.p. 125-129 C

4- (6,9-Dichloro-2-quinox allyloxy) fenox and acetic acid, m.p. 2333-238 C

2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxypropanenitrium, m.p. 117-123 C

2- / 4- (6,7-dichloro-2-quinox allylloxyl) phenoxy] propanenitrile, mp 151-153 ^{c or} 7-chloro-2- [4- / 1- (4,5-dihydrooxazole- 2-yl) ethoxy / phenoxy / quinoxaline, mp 170-172 C

K-Trifluoromethylsulfonyl 2- / 4- (6 or 7-chloroquinoxalinyloxy) phenoxy / propanoid, m.p. 95-l ° l C

4- / 4- (6 or 7-chloro-2-chloro-oxalinyloxy) phenoxy] -pent-2-enolic acid, mp.55- ^ 5 θ

Sodium June 4- / 4- (6 or 7-Fluoro-2-quinoxalinyloxyphenoxy / pent-2-enoate, mp 197-202 ^c

Potassium 4- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / psnt-2-enoate, mp 1885 -2O8c (dec.) '

Ammonium 4- (4- (6 or 7-chloro-2-quinoxalinyloxy) phenocai / pent-2-enoate, m.p. 140-150 C (dec.)

4- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / pent-2-enoic, mp 135 * 145 C (dee.)

N-methyl 4- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / pent-2-enamide, m.p.199-201 C

- 91 Compound Compound

4- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy / pent-2-enenitrile, oil

Methyl 4- / 4- (2-quinoxalinyloxy) phenocai / pent-2enoate, oil

Methyl 4- / 4- (6 _t ^ 7- ihloro-2-kir.ok8alinilok8i) feroksi / pent-2-enoate, m.p. 112-115 ^c

Methyl 4- / 4- (6- or 7-chloro-2-chloro, oxalinyloxy) phenoxy / hex-2-erooate, oil

Ethyl 4- [4- (6 or 7-chloro-2-quinocaleinyloxy) phenoxy] but-2- 2- buto, m.p. 80-95 θ

Dimethyl 2- ethyl-2- / 4- (2-chlorooxalyryloxy) phenoxy / propanedioate, m.p. 87-92 C

Dimethyl 2-methyl-2- / 4- (6 or 7-chloro-2-quinoxalinyloxy) phenoxy] propanedioate, mp 134-139 ^c

Diethyl 2-methyl -2- / 4- (6 or 7-chloro-2-hyroxalinyloxy) phenoxy / propanedioate, oil. ·

Test A

Seeds of sour grass (Bigitaria spp.), Barn grass (Echinochloa omagali), wild oats (arena fatua), cinnamon (Cassia tora), shipworms (Ipomea app «), weed bottles (Xanthium spp.), Soybeans, corn of wheat reeds, wheatgrass, wheat, and rush (Cyperus rotundus). At the same time a five-leaf spider (including cotyledon) is taken, Sbunastl beans that develop a third leaf, sour two-leaf grass, manure with two leaves, wild oats with one leaf, cinnamon with three leaves (including cotyledon). four-leaf husk and weed (including cotyledon, soybean and three-leaf corn, sugarcane two cotyledon leaves, two-leaf rice, one-leaf wheat, three-leaf to five-leaf rush and spraying. 1 control is returned in a glass barrel after 16 days All samples are compared and visually controlled to hear response to treatment performed seven and 16 days ago. completely decayed plant The descriptive symbols used have the following meanings: ·

S «albinizap G« = growth arrest C «chlorosis / necrosis E« essential inhibitory H «= formative effect

U «unusual pigmentacja B * Burnt

X «armpit stimulation and« absence of buds and flowers.

Tested for the compounds tested, this test procedure shows Table A for 16 days of treatment. One can see that some compounds can be used as selective herbicides in crops such as soybeans, spiders, wheat rice and beans.

Table A

Compound * kg / ha

After the appearance of the beans us uk linoleum weed bottle cinnamon rush grass creeper cereal grass wild oats wheat corn

*. soybean rice

2Q. sugarcane

Before Appearance 'weed bottle cinnamon rush grass creeper 25 * whole grass wild oat wheat corn soybean rice sugar cane

3b

2 0.1 0.1 IS 0 0 2C 0 0 2C 0 0 5G, 1C 0 0 0 0 0 0 0 0 10C 10C 10C 10C 10C 10C 10C 10C 10C 9C 10C 10C 10C 10C 10C 3G, 1C 0 0 .10C 10C 10C 10C 10C 10C

0 0 0 4G 0 0 0 0 0 0 0 0 10E 9H 10E 10E 10E 10E 9G, 5C 7G 8G, 10E 9G 10E 10H 9H, 5U 9G, 7C 0 0 0. 10E 9H, 5C 10E 10Ξ 30 10C

Table A (continued) .5

The compound

15.

2 3 4 i kg / ha 2 0.4 d; i After appearing • beans 9G, 6C, 6Y 0 0 · cotton 9G, 3C 0 0 shipwreck 9G, 2C 0 0 weed bottle 0 0 0 cinnamon 0 0 0 rush 0 0 0 creeper grass 10C 10C 8C cereal grass 10C 10C 10C wild oats IC 9C 8G, 3C wheat 9G, SC 10C 10C corn 10C 10C 9G, 4C soybeans 3G, 1C, 5X 0 0 rice 9C 10C SG, 1C With the cod 10C • ioc 10C Before appearing shipwreck 8G 0 0 weed bottle 6G 0 - cinnamon 0 0 0 rush 0 0 0 creeper grass 10E 10E 3G, 1C cereal grass 10E 10E 10E wild oats 7G, 1C 9G 5G wheat 9H, 2C 9G, 5C 6G kulcuruz 9G, 2U 9G, 5C 8G, 2C soybeans 3G 0 0 pirirad 10E 10E 7G, 2C With the cod 10E 9G, 5C 8G, 2C

Table A (listed)

Compound *

6 7 kg / ha ¹⁰ After emergence beans cotton weed bottle weed bottle cinnamon rush grass creeping cereals wild oats wheat corn soybean rice Cones cane

Before the advent of weaning weed bottle cinnamon rush grass creeping _ Tiny grass ²⁵ wild this «wheat corn soybean rice Cones cane

0.4 0.1 0. 0. 2G 0 0 0 0 0 0 0 0 0 0 0 0 0 0 IC 0 9C 9C IC 10C 10C 10C 6C 6C 0 9C 9C 0 10C 10C 6C IC IC 0 9C 9G, 1C IC 10C 10C 9C 0 0. 0 ' 0 0 0 0 0 0 0 0 0 10C 0 2G 10C 10C 2C, 7G 9G, 1C 4G 10C 9G, 1C 2C, 9G, 7U 8G, 1C 7G, 0 0 0 10E 3G 5G, 10C 8G, 1C 7G

Table A (continued)

Compound *

9 10 kg / ha ¹⁰ After emergence of pasvJLj? C ~ I ± seafood weed bottle cinnamon regoa herb puaavica cereal grass wild yeast phenies cortex sow pie

2θ black strip

Before the appearance of the weed, the weed bottle of cir ^ et horned grass weed 25 * itr <a grass, wild bw p: monkey

Irclrurus soybean pyrir & č uccercfi cod

3.0

0.4 0.1 0. 0 0 0 1C 0 0 0 0 0 0 0 0 IB 0 0 0 0 0 10C 9C 5C 10C 10C 10C 10C 6C, 9G 2C 9C 9C 5C 9C 10C 10C IB 0 0 9C 9C 9C 10C 10C 10C

0 0 0 0 0 0 0 0 0 0 0 0 10E 10E 3G 10E 10E 10E 8G 8G 0 2C, 9G 2C, 9G 6G 9G, 2U 5U.9G 7G, 0 0 0 2C, 8G 10E 8C 9C 3C, 9H 9G _r

Table A (extension)

Jedirjonjo *

11 12 13 kg / ha 0.1 0.1 0.1 After appearing Λ A fl beans 0 0 U 0 in 0 <· * -. «- icholei 0 0 10C A weed bottle 0 0 0 ci: ot 0 0 2G rush 0 0 0 grass grass 10C 10C 10C cereal grass 10C 10C 7C, 5G wild oats 9C 5C, 9G 0 wheat 9C 9C. 2C, 3G k ^ gjruz 10C 10C 0 w w- ^ S * · 0 0 0 pirir.ač 10C 9C 7C, 6G šoccrr.a reed 10C 10C 10C Before the advent of John l; u'olez 0 0 0 weed bottle 1C, 8H 0 2G ciaot 0 0 IG rush 0 0 0 the horn of the pasavlca 9G 3C, 9G 7C, 5G Tiny grass 10E 10E 10C uivl.il cva3 1C, 9G 7G 0 wheat 2C, 9G 9G 7C, 6G k ^ wuUr uz 3C, 9G 3C, 9G 6G, 6C soybeans 0 3G 0 pirinaS 2C, 9G 10E 7C, 8G sheeer reed 3C, 9G 2C, 9H ' 7G, 7C

Table A (breakup)

Jedlr.jer.je _ *

15 16

0.1 kg / ha 2

Post- impressions of beans ρη? '. «5ζ' 0 2G 0 1C shipwreck 2G 2B kcrcrv hoea .0 IB eiir.ct 2G IB rcfos 0 0 grass weed 1C 0 Tiny grass 3C, 8H IB wild this3 0 0- 2S 0 ^ zukorus 2S, 8H 2C, 6H of tea 3G 1C piercer 2G 0 čechorr.s cod 2H, 9G 2C, 7H

10C

10C

9C

9C

10C

10C

10C

ir e announcements5Terms 1.2 school © 3 0 0 0 weed bottle 0 0 0 cinnamon 2C 0 0 ro ~: »s 0 0 0 weed grass 2G 0 2G lira grass 10H 3C 2C, 9G wild sheep 2G 0 8G: ? N * r.ica 5S, 8G 2G 9G 1C, 7G 1C, 5G 5C, 9G coja 0 0 0 piercer 1C 1C 10C redfish 9H 1C, 5G 10C

100

Table A (rantsvak) kg / ha:> e javljlvasa i ^ šlel • .orov hoca civit roHOa grass puaavica it on grass chi / 131 oats of.orica - ·> ¹

113 j a pirlraS Cocherr.a cane

Pre ^Ύ ^ ο, 1 Aug j John

Piorcv fcoca ciaet trw. bird Citea grass wild yeast pPurJca kefarrus * · Λ * 1

M V «J * - * pirirao A cone of reeds

Jedtirjenjg *

17 18 19 0.1 0.1 0.1

0 0 0 0 0 0 0 0 1C 0 0 0 0 0 0 0 0 0 2C, 9G 10C 1C, 2G 10C 10C 10C 4C, 9G 3C, 7G 0 2C, 9G 2C, 7G 1C 10C 10C 10C 0 0 0 10C 1C, 9G 5C, 9G 10C 10C 3H, 9H 0 0 0 0 0 0 0 0 0 0 0 2G 2C, 6G 0 0 10C 2G 10C 5G 1C 0 2C, 9G 2S 1C, 8G 4C, 9G 2G 1C, 8G 0 0 0 10E 0 1C, 5G 9C 2G 8G

101

Table A (freight)

Jcdirionje *

20 21 22 kg / ha 2 0.1 0.1 10 After appearing A A A ' beans 0 U A U A ϊ pam-uk • 0 o · _A t shipwreck 2G 0 0 weed bottle 0 0 0 · cinnamon 0 0 0 rush ¹⁵ grass creeper! 0 0 0 9C 0 9C cereal grass' 1C, 6H 10C 10C wild oats 0 6C, 9G 3C, 5G wheat 0 9C 9C corn 2C 10C 9C soybeans IH 0 0 rice 0 9C 9C 2Q sugar cane 5C, 7G 10C 10C Before appearing shipwreck 2C 0 0 weed bottle 0 0 0 cinnamon 0 0 0 rush 0 0 0 creeper grass 2G 9H 2C, 9G 25 Cereal grass 4C, 8G 10E 9C wild oats 1C 7G 2C, 7G wheat 2G 3C, 9G 3C, 9G corn 2C, 7G 4C, 9G 4C, 8G soybeans IH 0 0 rice 1C, 4G 9H 9C chechery cod 1C, 6G 3C, 9G 3C, 8G

102

Table A (continued)

Compound *

24 25

kg / ha 0.1 0.1 0.1 After appearing A beans 0 A 0 0 cotton 0 0 0 shipwreck 0 0 0 weed bottle * 0 0 0. cinnamon 0 0 0 rush 0 0 0 creeper grass 9C 9C 9C cereal grass 10C 10C 10C wild oats 9C 5C, 9G 3C, 9H wheat 9C 9C 9C corn 10C 9C 9C soybeans 0 0 0 rice 9C 9C 9C sugar cane 10C 10C ' 10C Before appearing, shipwreck 0 0 0 weed bottle 0 0 0 cinnamon 0 0 0 rush! 0 0 0 creeper grass 8G 7G 9C cereal grass j 10C 10C 10E wild oat wheat j 8G -8G 9G 9C 6C, 9G 3C, 9G corn 3C, 9G 2U, 9G 3C, 9G soybeans 0 0 0 rice 5C, 9G 10E 10E yesterday on cod 5C, 9G 5C, 9G 3C

103

Tabla A (extension) kg / ha of wildflowersIvan beans spider ladle weed bottle cinnamon rush grass pur / aviea cereals wild sheep pfconiea corn soybean rice chccnia cane

Trs pop wrap weed bottle weed bottle oiiiot rush grass put it ^x it ra grass live oats diaper Iruruso soybean rice black tape

Jc & l.jepje *

27 28

0.1 0.1 0.1 0 0 1C 0 0 IB 0 0 0 0 0 0 0 0 • 0 0 0 0 8C 10C 10C 1C 10C 10C 0 2C, 6G 9C 0 10C 9C 0 10C 10C 0 0 0 0 10C 9C 0 10C 10C

/

0 0 0 0 0 0 0 0 0 0 0 3G 4C, 8G 2C, 8G 9C 10E 10C 10E 1C, 7G 7G 1C, 9G 6C, 9G 3C, 9G • 5C, 9G 4C, 9G 30,9H 50,9G 0 0 0 10E 10E 10E 3C, 9G 4C, 9G 3C, 9H

104

Table Λ (continued) kg / ha

After appearing beans cotton shipyard weed bottle cinnamon rush grass creeper cereal grass wild oats wheat soybean rice sugar cane and

Before appearing - shipworm weed bottle cinnamon rush grass creeper cereal grass oat wheat corn soybean rice sugar cane j

Compound *

30 31

0.1 0.1 0.1 0 0 0 0 0 0 0 0 2G 0 0 0 0 0 3G 0 0 0 9C 9C 8C 10C 9C 8C 5C, 8G 3C 0 9C 4C, 8G 3G 10C 4C, 6G 2C, 3G 0 2G 1C 10C 2C, 6G . 5C, 9G 10C 9C 9C

0 IH 0 0 0 3G 0 3H IH 0 0 • 5G 5C, 9G 9G 2C, 9G 10E 2C, 8G 9C 2C, 8G 8H 6G 7C, 9G 7G 8G 4U, 9G 3G 3C, 9G 0 0 0 10E 5G 2C, 8G 5C, 9G 7G 3C, 9H

105

Table λ (continued)

Compound *

33 34 kg / ha

After appearing ^! beans and spiders And weed weed bottle cinnamon rush!

grass creeper cereal grass wild oats wheat corn soybean rice ·

2Q sugar cane

Before the advent of weeds bottle weed 'cinnamon rush grass creeper 25 cereal grass wild oats wheat • corn soybean rice sugar cane

30.

0.1 0.1 0.1 0 2G 0 0 0 0 5G 0 0 0 0 0 3G 0 0 0 0 0 9C 9C 9C 9C 10C 10C 0 1C, 7G 2C, 7G 4C 9C 9C 1C 5C, 8G 9C 0 0 0 9C 4C, 8G • 10C 2C 9C 10C 0 0 0 0 0 0 0 0 0 0 0 0 3C, 9G 8G 3C, 9G 9C 9C 10E 8G 7G 1C, 8G 2C, 8G 3C 5C, 9G 2C, 7G 3C 5U / 9H 0 0 0. 9G 9G 10E 8G 3C 5C, 9H

106

Table A (continued)

Compound * 35 36 37 kg / ha o.i - 0.4 2.0 After appearing beans 0 0 0 cotton 0 0 0 shipwreck 0 0 0 weed bottle IH 0 0 cinnamon 0 0 0 rush 0 0 0 creeper grass IH 4G 5C cereal grass IH 10C 0 wild sheep 0 0 0 wheat 0 0 0 corn IH 3S, 7H 0 soybeans 0 0 • 0 rice 0 5C, 9G '0 chechery cod 2G 9C 0. Tre impressions shipwreck 0 0 0 weed bottle 0 0 0 ' cinnamon 0 0 0 rush 0 0 0 creeper grass 5G · 2C, 5G 5C, 9G cereal grass [6C 10C 4C, 9G wild sheep and ^4G 2G 2G wheat 2C, 5G 4C, 9G 3C, 8G corn 2C 3C, 9G 2C, 7G soybeans ⁰ 0 0 rice ⁰ 10E 3C, 6G With the cod 5G 2U, 9G 7G

107

Table A (continued) kg / ha

After the appearance of beans cotton hawthorn weed bottle cinnamon rush grass creep cereal wild oats wheat corn soya riceS cane

Before the advent of weaning weed bottle cinnamon rush grass creep tiny grass grows wheat corn soybean rice hay

Compound *

39 40

0.1

2.0

0.4 o

o o

o o

o

5C

2C

9C

IC

4G

2G

9C 10C 9C 10C 10C

IB

10C

10C

3C10E 9G, 2C 6C, 9G 30.9G 0

10E

5C, 9G

0 0

5G

3G

2G

2G

4G о

10E

10E

5C, 9G

9C

8U, 9G

10E

5C, 9H

108

T & bola A (continued) kg / ha ^ iosle pojaja paculj punk beetle weed bottle cinnamon rush grass creeper cereal grass wild sheep wheat corn coja plrirad tehera l l re re logging weed bottle bottle ciiiet rush grass cuckoo weed corn cereal pirir & č cderca third

Is & lrnc *

42 43

0.4 0.4 0.4 0 1C 3C 0 0 0 2B, 6G 2C 0 0 0 0 2G 0 0 0 0 0 10C 9C 9C 10C 10C 10C 9C 5C, 9G 3C, 7G 10C 3S, 7G 3C, 7G 10C 9C 9C 0 0 . 0 10C 9C 9C 10C 9C 9C

0 0 0 0 0 0 0 0 0 0 0 0 10E 10E 10E 10E 10E • 10E 3C, 9G 2C, 9G 1C, 9G 3C, 9H 50,9G 5C, 9G 7tJ, 9G 6C, 9G 5C, 9G 0 0 0 10E 10E 10E 3U, 9H 6C, 9G 6C, 9G

109

Table A (Continue?)

Compound «*

45 46 kg / ha

Gone is the emergent bean cotton wagon. · ~ Kgrov bottle cinnamon rush ¹⁵ grass pussvica cereal wild oats wheat ku & jruz coja rice

2 _Q checorra cod

T

Before the advent of weaning weed bottles cinnamon rush grass creep 25 cereal wild sheep wheat: corn soybean rice Bar strip

0.4 0.1 * 0.4 IC 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 9C 9C 9C 10C 9C 9C 3G 0 0 2C, 6G 0 1C, 3G 50.9C IC 2C, 7G 0 0 0 6C, 9G 2C . 9C 9C 9C 9C

2G 0 0 0 0 0 0 0 0 0 0 0 10E 5C, 9G 5C, 9G 10E 10C 10C 2C, 9G 1C, 8G 2C, 9G 9C 5C, 9G 4C, 9G 50,9G 5C, 9G 30,9G 0 0 0 10E 10E 10E 5C, 9G 5C, 9G 3C, 9G

110

48 49 kg / ha 10 I-freed av av j Ivanjo, paml j pasuk ladolcS weed bottle cinnamon rush poison creeper tiny grass wild oats p & etaec Irukuriis eoja pirirad _2Q flowing tape

Pojavτο impressions of ladoleS weed bottle cinnamon rush grass creeper 25 cereal wild erves. diaper kukuras eoja rice ecdcrca reed

0.4 0.4 0.4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5C 9C 5C 0 0 6C 0 0 0 0 0 0 IC 0 5C 0. 0 0 0 0 • 2C, 8G 0 0 2C, 9G 0 0 0 0 0 0 0 . 0 0. 0 0 0 9C 9G 0 9C 6C, 9G 10C 1C, 5G 1C, 9G IC 1C, 8G. 2C, 9G 8G 6C ' 2C, 8G 3C, 9G 0 IH 0 7C 2C, 9G 2C, 8H 8G 9G 1C, 8G

111 «f ohola A (ractcvok) kg / ha

After appearing beans parvuk lcdoleage Poison bottle ci ^ et rush grass creeper 'cereal grass wild yeast ku'ijjr «2z • SSj * rice Dinner run

Before the appearance of the shipwreck fertilizer bottle ciaet rush grass creep cereal wild oats j wheat corn soybean rice checra cane

Jcdlrjonjc *

51 52

0.1 0.4 0.4 0 0 0. 0 0 0 0 0 2C 0 0 0 0 0 0 0 0 0 0 2C, 7G 10C 0 1C 10C 0 4C, 9G 8C 0 2G 9C 0 1C 10C 0 0 0 0 0 • 9C 0 0 10C

0 0 0 0 0 0 0 0 . 0 0 0 0 1C 5G 10E 6G 9C 10E 2G 6G 1C, 6G 2C, 5G 8G 9C 3C 2U _r 5G 2C, 8G 0 0 0 0 2C, 8G 2C, 9G 2G 1C, 9G 9C

112

Table Λ (continued)

Compound * 53 54 55 kg / ha 0.4 0.4 2 After appearing. 1C beans 0 0 . steamer ·· 0 0 shipwreck 1B, 5G 0 IB weed bottle 2G 0 0 cinnamon j IB 0 0 rush 0 0 0 creeper grass 9C 0 0 cereal grass • ioc 1C 0 wild oats 2C 0 0 wheat 4C, 9G 2G 0 kpkuruz 10C 2C 0 soybeans IB IB 0 rice 10C 2G Ό sugarcane 10C. 2G 0 iPre impressions' shipwreck 1C · 0 3G Tcorov bottle 0 0 ' o cinnamon -tc 0 1C rush 1C 0 10E creeper grass 2C, 5G 1C 3G cereal grass 10E »2 C, 8G 2C, 6G wild oats 1C, 4G 0 1C, 4G wheat 1C, 9G 2C, 5G 3G : corn 2C, 9G IG · 6G soybeans 0 n n rice 10Ξ IG 3G sugarcane 10E 3G 2C, 8G

113 Test B

It is taken in two plastic containers and filled with a Palaington lime clay ounce. 0 one pot of corn, Sugarcane, Kentucky - blue grass A variety of weeds,

Cotton, soybean, purple rush (Cvperus rotund us) and various types of broad-leaved weeds are planted in another container. The following grass and broadleaf weeds are planted: pickled grass (Digitaria aanguiralis), farm grass (Eohinoehloa crusgali), wild oats (Avena fatua), jonson grass (Sorghum halepense), dalis grass (Paspalum dllatatum), gin (Setinaria fabaria) Cereal cockroach (chromus secalinus), dessert (Brassica arvensis), weed bottle (Xanthuim pen sjlvanlcum), pork weed (Anaranthua retroflekus), shipworm (Ipomea hederacea), cinnamon (Caasia tora), tea weed (Sida spinosa), velvet (leaf) Abutilon theophrasti) and jimson weeds (Datura atramonium). An 11.0 cm diameter dish is also taken and filled with prepared zera 1 j, and rice and wheat are planted there.

A sugar beet is planted in another bowl of diameter 11.0 om. All of the above vessels are filled in the above manner and are subjected to pre-conceptualization, days after the treatment, the plants will develop and perform a visual assessment in order to obtain a response to the performed heraic treatment using the evaluation eisteaa, which is listed in Test A. The data obtained are shown in Table B.

114

Table B

Before appearing on Palsington Soil

The compound

g / ha 0.06 0.25 Creeper grass 0 10E Cereal grass 3H 10C Medicinal cane 0 · 10C Wild oats 0 6C Johnson grass 8C 8C Dalis grass 6C 7C Fox 6C 10C K. blue grass 6C 10C Cereal corn 0 5C Even tails 0 0 Kultur uz 4G 3C Slatica 0 0 Weed-bo ca 0 0 Pork cows 0 5G Rogoz 0 0 Panulc 0 0 Shipwreck 0 3G Cinnamon 0 0 Tea weed 0 0 Velvet leaf 0 0 Johnson's weed 0 0 Soybeans 0 0 Rice 5C 9C Wheat 0. 9C

115 'Table B (summary).

Pro Impressions on FaLsinston Soil · 5

The compound

kg / ha 0.12 0.5 Creeper grass 0 0 Grains of grass 3H 10H Lečorra. reed 0 9H Wild oats 0 0 DSorson grass 3H 9H jbilis grass 3H 9H Fox 0 0 K. Blue grass 6H 8H 'jitri Jnicolj 0 0 and a black tail 0 0 Kufotros 0 4H Sweetie 0 0 Sorcv-hooa 0 0 Pork cows 0 0 Soges 0 0 iasufc 0 - • 0 Shipwreck 0 0 Cinct 0 0 . Tea weed 0 0 Esrcer.asti list 0 0 LSisssos weeds 0 0 Soybeans 0 2G Rice 5G, 3H 6G, P Sorica . 0 0

¹¹⁶

Table B (continued) Before appearing on Palsington Tl «

Compound kg / ha

0.25

3G

Leaf grass 4 C

Cereal grass 0 ioder race 0

Wild this 0

Well he grass

Stick of grass 0

Lisicina 5C

v. blue grass 0 clear lrocoli 0

2C black beet:. Knknruz, 0

Slatica · o

Kcrov-bottle 0

Pork .cattle. 0 ₂₀ Rogoz 0

Sand 0

Shipwreck 0

Cicot 0

Tea weed ₀ .crčuaacti list Jjšinaon weed Soybean

Wheat Planer

- 117 Test c;

A 25 cm diameter plastic container is taken and filled with Falsington lime clay and soybean, clover, corn, rice, wheat, soybean, velvety leaf (Abutilon theophrasti) sesbania (Sesbania exaltata), cinnamon (Cassia tora) are planted. hippopotamus (Ipomea hederaoea), jimson weed (Datura stramonium), weed bottle (Xanthium pensjlvanicum), acid grass (Digitaria spp.) rush (Cyperus rotundus), stallion grass (Echinochloa crusgalli), gin (Setus foliar oval) avena fatua). Approximately 2-1 / 2 weeks after planting, young blots and thio around them are treated with test chemicals that are dispersed or not in non-phytotoxic solution. Two weeks after treatment, all samples were compared with untreated and a visual response to treatment was performed. The method of proowing is described in Test A. The data are given in Table C. Some of the compounds tested can be used to control the after-emergence of weeds in some major crops.

118

Table C

Surface treatment Soil / leaf «

Compound &

kg / ha 0.500 0.125 0.063 o.o: soybeans 0 0 0 Λ 0 Λ barunchas.list 0 0 0 U A sesbanija 0 0 0 0 Λ cinnamon 0 0 0 U A p & wolf 0 0 0 0 : shipwreck 0 0 0 0 clover 0 0 0 0 d ^ iason weeds 0 0 0 0 weed-bottle 0 0 0 0 corn 10C 10C 10C 10C creeper grass 10C 10C 8C 6C rice 10C 10C 10C 8C rush 0 0 0 0 cereal grass 10C 10C 10C 10C j wheat 10C 10C 10C 10C '· Handcuffs 10C 10C 10C 10C wild oats 10C 10C 10C 7C With the cod 10C 10C 10C 10C

¹¹⁹

Table c (summary)

Surface treatment Soil / leaf

Compound B

kg / ha 0.031 0.016 0.008 soybeans 2G 0 2G barŠunas.list 3G 0 0 sesbanija IG 0 2G cinnamon 0 0 «K cotton 0 0 0. shipwreck 2G, 2C 0 0 clover 2G 0 0 dschimson weeds 2G 0 0 weed-bottle 3G 0 0 corn 10C 10C . 10C creeper grass 9G, 9C 8G, 3C 5G rice 9C 10G, 5C ' 10C rush 0 0 IG cereal grass 10C 10C 9C wheat .10C 10C 10C handcuff 5G, 4C wild oats 2C 8C 6G, 3C sugarcane 10C 9C. 6G, 7C

120

Table C (continued)

Surface treatment Soil / leaf

Compound £

kg / ha 1,000 0.250 Soybeans Barsunas.list 0 ! 7G 0 • 7G, 3C Sesbania Cinnamon '4G 6G, 3C 7G, IC 10G, 7C Cotton 4G, 2C 4G, 2C Ladoleš 4G 9G, 3C Flight 3G 3G Jimson weeds 3G 3G A weed-bottle 3G 3G, 2C Corn 10G, 9C 10G, 6C Creeper grass 10G 3G Rice 10C 8G, 5C : Rogoz 3G 2G Cereal grass . 10C 10C Wheat ¹ 3G 10C Fox 10G, 7C 7G, 3C Wild oats 3G IG : sugarcane 10C 9G / 4C

121

Table C (extension)

Surface treatment Soil / leaf

Compound -

kg / ha 0.125 0.500 1,000 soybeans 0 0 0 velvet, leaf 2G 2G 0 sesbanija 0 0 0 cinnamon 0 0 0 panuk 0 0 0 shipwreck 0 IG 0 clover 0 0 θ • Jimson weeds - - - weed-bottle 0 - 0 corn 10C 10C • 10C creeper grass 8G, 8C 10C 10C rice 5G, 4C 7G, 7C 9G, 9C rush 0 0 4G Cereal grass 5G, 5C 10C 10C wheat 0 IC 10C ^; handcuff 2C 10C 10C 'wild oats 0 0 IG Sugarcane IC 8C 10C

122

Table C. (continued)

Surface treatment Soil / leaf

Compound &

.8 kg / ha

0.500 0.125 0.063

0.016

soybeans velvet, leaf 2G, 3C 1G 0 0 0 0 0 0 sesbanija cinnamon 5G 3G 0 0 0 0 0 0 pa-nuk 3G 0 0 0 shipwreck 0 0 0 0 thickness 0 0 0 0 Jim3on weeds 0 0 0 0 weed-bottle 3G, 2C 0 0 0 corn 10C 10C IG 10C creeper grass 7G, 4C • 8G, 3C 5G, 1C 2G pirir.ač 5G 10G, 5C 0 4G, .2C rush IG 0 0 - cereal grass 10C 10C 3G _r lC 10C wheat 9C 10C 7G 9G, 8C handcuff - - - 9G, 9C wild oats 7G, 7C 8C 3C 6G, 2C sugar cane 10C 9C 3C 10C

I

123

Table C (continued)

Surface treatment Soil / leaf

Compound &

kg / ha '

0.5

0.125

0.031

Soybeans

Velvet.list Sesbania Cinnamon Pamul:

3G

IG

5G

IG

5G

6G

3G

IG

Betelina IG IG 0 Bimson weed 2G 2G 2G A weed-bottle 4G, 2B 4G, 2B IB Corn 10C 7G, 6H 7G, 6H Creeping grass 0 0 0 Rice 10C 7G, 5C 3G Rogoz 2G 2G 0 Cereal grass 10C 9C 9C Wheat 2G 2G, 3C 2G, 3C Fox - 8C 4G 4G Wild oats IG 0 0 Leeer reed 9C 2G, 5C 0

124

Table C (breakup)

Surface treatment Soil / leaf 5

The compound

11 12 kg / ha ' 0.5 0.125 0.016 soybeans 3G IG 0 velvet.list 0 0 0 sesbanija IG 5G 0 cinet 0 6G 0 spider 0 0 0 shipwreck 5G 0 0 clover 0 5G 0 Jimson weeds IG IG 0 weed-bottle 0 0 0 corn 10C 10C 10C grass creeping 10C '10C • IG rice 10Ч 10C 10C rush $ G 0 0 Tiny grass ; og 10C 10C wheat 10C 10C 5G, 4C handcuff 10C 10C 9G, 9C wild oats 10C 5G, 2C 3G sugarcane 10C 9G, 9C 9G, 9C

125

Table C (continued)

Surface treadmill Soil / deprived

Compound · &

• kg / ha

0.250 0.500 1.000

Soybeans

Shun bar .Hat Sesbania

Cinnamon Paauk Ladolež Detelina Džiason KOROV KOROV-bottle Corn, _Λ Grass puzavioa ²⁰ Rice

Rogoz

Cereal wheat Wheat Fox Wild yeast Sugar cane

2G 2G 2G 3G 0 0 2G 2G- 2G 2G 3G 0 0 0 3G 2C 2C 2C 4G 0 0 IG 2G 0 0 0 0 10C 10C 10C 9C 10C 10C 8C 2G 10C 0 0 0 5G, 6C 10C 10C 0 4C 10C 4C 5G, 5C 10C 0 2G 3G, 3C 9C 10C 10C

126

Surface treatment Soil / l ± Sde kg / ha s o «« a

La? £ * jsas «llot cinat

ΪγΪοΪο2 apiary f acorn.nor weed-bottle weeds

VmZ «grass ptsgavica pirir.ač rocos itna grass spit linini divi her CT7CU3 Sodem hook

Table C (continued)

0.500

3G

3G

3G

IG

2C

2G

5G

IG o

2C

The compound of fe

0.500

2G

IG

1C

2G

IG

0.500

2G

2G

3G

6G

10C

10C

10C

10C

10C

10C

8G, 7C

10C

Surface tratoan Soil / leaves

127

Table C (continued)

The compound

17 18 kg / ha 0.500 0.500 aoja barchus «list IG IG 3G 0 scsbanija 4G 2G cirast 0 IG par.uk 0 0 ladoleS 3G 10C thickness 0 0 jinson weeds 4G 0 weed-bottle 0 0 corn 10C 10C Creeper grass 10C 10C rice 10C 8C rush 0 0 cereal grass 10C 10C wheat 10C ^with 10C handcuff 10C 10C wild sheep 8G, 7C 8G, 6C Chechnya cod 10C 10C

128

Table C (pen)

Surface Tretoan Soil / lifts

Compound A kg / ha '.0156

coja 0 0 Sesbanlja 0 ^^ * i * A ^ * 0 * 7 '' · '·' '' it * '* 0 I & £ gXc2 0 “JcteliTft 0 iSir ^ on weeds 0 Korcv- ^ ca 0 rtkuros 10C The shotgun trirm 9G, 8C - .. - * * - ** . «W, v * \» j- CLm. - * t 6G, 6C . * · 0 'a itr.a' cr ^ vu 10C Pvonica 5G, 3C LlcUlca 8G, -1C Beer oats 2G topper reed 10C

- 129

Test D

They take e · two 10 inch diameters made of polyethylene film in full ea prepared with Falaington lime clay. One pot is planted with wheat seeds (Triticum aestivum), barley (Hordeum vulgare), wild oats (Arena fatua), (Broraus tectorum), cereal hens (Ikomua secalinua), black grass (Alopeourua Myoeuroides), annual grass (blue ana blue). ), giant fox (Setaria viridis), herb chef (agropyron repens) and Italian roger with herbs (Loliua nuitiflorum) and solid oats (JEkomua rigidua), The second bowl is planted with Russian oat (Salsola kali) seeds, licorice (Descuutima pinnata) weed (Polygonum penaplvanicum), marshmallow- (Sisvmhrium altissium), koc & iom (Kochia sooparia), marshmallow (Capsella bursa-pastoris), Matrioaria onodora, black scallop (Solanum rigrum), 5 lilac (cabbage) Braichegar vulceridae (Barbarea) 1 wild buckwheat (Polygonum convolvulua). These two phenomena are treated pre-emergence. ”The same two such occurrences are treated in the same way, and these plants exacerbate after-emergence. The silence of the plant at the time of treatment is from 1 to 15 cm, which depends on the type of plant.

Compounds ae applied diluted with a non-phytotoxic solution and sprayed over vessels. Comparison trays are comparatively ee observed by untreated specimens. All treatments are performed in a glass garden after 20 days and visual inspection is performed. Entries presented in Tables D.

130

Table D

Before the appearance of Wheat Barley

Wild oat flakes.ovas Cereal Jcukolj Black grass C-blue grass Green fox Grass cheat Italian weed P .. oats Russian weed T.weed Angry weed Skiweed Kochia Tarčužak.

IJatrlcaria inodora Black helper Yellow lilac Divica handgun Divj buckwheat

Compound £

0.06

3G

3G

2G

4G

2G

3G

9C, 8G

131

Tn.hela D (paragraph).

Jedlrjonjo fe

0.02 0.06 Prior to reporting 10C 10C Flush Jccari 10C 10C Wild oats 9C 10C blow the j .ovas 10C 10C cereals 10C 10C Black grass 10C 10C Year. Blue grass 0 2G Bolera fox 10C 10C A real cheater 10C 10C Ital.raž. Grass 10C 10C R.OV-iS 10C 10C Pumpkin weeds 0 2G T.slaSiea 0 8G Angry weed - - Svuu.slanica 4G 7G Boc £ i £ Tarouzak 7G 2G 8G 3G and · 'atricaria ir of or a 0 7G Cfrna pohoTsica Yellow lilac 0 o - 2G 6G Beer ivory 3G 7G Animal car 0 0

Patent claims

Claims (1)

A process for the production of quinoxalines 1-oxy ethers of the following formula wherein A is H or C 1 -C 4 -alkyl; E is H, C1, Br, F, CF ₃ , CH _{3 or} OCH ₃ ; G is H or Cl; D is H, CH _{3 or} CO 2; L is H, CH _{3 or} CgHgj Q is -CH = CH- or -CH ₂ CH ₂ ~; n is 1 or 0; W is CN or C (O) R il i N ^x R is Cl, XR _p NR ₂ R ₃ , OH or OM; M is an alkali metal, alkaline earth metal, ammonium, ammonium, di-or three ethanol ammonium; X is 0 or S; R ^ is C ^ “C, | _g alkyl 1, benzyl, phenyl, Cs-Cgaikloalki 1 CH ₂ CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ 0CH ₂ CH ₂ 0C ₂ H ₅ , -N = CR ₆ R ₇ , C ₃ -C ₄ alkenyl mono-, di- or tri ^ lower alkyl, ch ₂ ch ₂ och ₃ , ch ₂ ch ₂ och ₂ ch ₃ ,, C 1 -C 4 alkynyl, or C 1 -C 6 alkynes nyl or alkynyl optionally substituted with one Cl; < ^v V nil, -Ch ₂ CH ₂ NR ₄ R ₅ , - SO ₂ CF _3> H0CH ₂ CH _2> C1CH ₂ CH _{2 or} BrCH ₂ CH ₂ ; R ₃ is H or C 1 -C ₄ alkyl; iii R ₂ and R ₂ may be taken together (CH ₂ ) ₂ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - iii - (CH ₂ ) ₂ -N ( CH ₃ ) - (CH ₂ ) ₂ -; R ₄ and R 8 are independently CH _{3 or} C ^; R 8 is H, C 1 -C 6 alkyl or SR _g ; R 1 is H, C 1 -C 4 alkyl; iii R ~ is H, Cj-C ₄ alki 1, -CgCycloalkyl benzyl 0CH ₃ , C ₃ -C ₄ alkenes being - (CH ₂ ) ₂ -0Rg and Ry may be taken together to be - (CHg) g - iii Rq and Rg are independently C1-C6 alkyl; V is F, Cl, Br, C 1 -C 4 alkoxy, C 1 -C 6 alkyl, CFg, NOg iii C ₁ -C ^ al ki 1 ti o; M is 0.1, 2 or 3; Y and Z are independently N or N -? - O; with that when D = CO ^ Rg then N = 0 (zero) and L is CH ^; when R ^ = -N = CRgRy, then X = 0; that one of R _a and R ₇ is not equal to H; and when E is different from H or Cl, then G = H; when W = CN then A = H; when E iii G is other than H then A = H iii CH ^; when / ° \ is W = - ^ J then n = 0 (zero) and D is H; when m = 3 then V = Cl, Br, F or CH ₃ ; when Rg = SOgCFg then Rg = H, wherein the alkali is a metal salt of a compound of the formula wherein D = H or CH2; W 'is CN or COOR', R 'is C 1 -C 4 alkyl, and L, Q in are the same as above, reacting with 2-haloquinoxaline of the formula where A, E and G are the same as defined above in the solvent such as dimethylformamide, dimethylsulfoxide and methylethyl ketone, at a temperature of between 25 ° and 130 ° C.