FI88798B - Pyrrolopyridinecarboxylic acid derivative substituted with the (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group, method for production thereof, and application of said compounds as herbicides - Google Patents

Description

Pyrrolopyridinecarboxylic acid derivatives substituted with (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group, process for their preparation and use of said compounds as herbicides

Separated from patent application 865081 (Patent 86730)

The invention relates to pyrrolopyridinecarboxylic acid derivatives of formula II substituted by (4-isopropyl-4-methyl-10-oxo-2-imidazolin-2-yl) group

- ^ C00Re 15 (II) / ^ XH (CH3)? H X 0 where A is 20 H .NR3- H. ^ CH2- NR1 - / CR7-

X X "X« ·· "X

H CH2-, H NR3-, xCR7- NR3-; R 3 is C 1-4 alkyl, C 1-4 alkoxy or C 3-6 alkenyloxy; R 4 is hydrogen, C 1-6 alkyl or phenyl; R 7 is hydrogen, halogen or C 1-4 alkoxy, and R 8 is hydrogen; C 1-4 alkyl optionally substituted with furyl; or propynyl; . . and their agriculturally acceptable acid addition salts and optical isomers.

·; F1 Patent 86730 relates to novel pyranopyridinecarboxylic acid derivatives substituted with a (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group,

of formula I

2 88798 y ^^ T ~ C00Rg

./ H

V N

5 ^ r N- | _CH3 CH (CH3) 2 where A is 10 ch3 i vx tcc 15 (1.1) (1.2) (1.3) (1.4) (1.5) ^ r ° rk, k or and 20 (2.1) (2.2 ) (2.6) R 8 is hydrogen; lower alkyl optionally substituted with furyl; or propynyl.

Certain herbicidal imidazolinylbenzoic acid 25 esters, esters and salts, their preparation and use are described in U.S. Patent 4,188,487 and U.S. Patent 4,297,128. Various pyridine and quinoline imidazolinone compounds are known. In addition, the herbicidal (2-imidazolin-2-yl) thieno and furo [2,3-b] and [3,2-b] pyridines, their preparation and use as well as the (2-imidazolin-2-yl) -2-yl) thieno and furo [3,4-b] pyridine compounds and a process for their preparation are known in the art.

EP-A-95 104 and 95 105 also describe (2-imidazolin-2-yl) condensed pyridine derivatives useful as herbicides.

3 88798

Applicant's EP patent 142,718 relates to a process for the preparation of intermediates useful in the preparation of imidazolinyl herbicides. In addition, the the patent discloses imidazolinylbenzoic acids. Haki-5 EP patent 41 623 and FI patent 76 082 describe 2- (2-imidazolin-2-yl) pyridines and quinolines useful as herbicides.

However, the novel compounds of the formula II are more selective than the known compounds useful as herbicides and, in addition, are significantly more effective herbicides at low doses than the known herbicidal compounds both when used before and after germination.

The invention further relates to a method for controlling the growth of monocotyledonous and dicotyledonous, annual, perennial and aquatic plant species, which comprises applying to the press or soil or water of said plants containing seeds or other propagation-promoting organs of said plants an herbically effective amount of formula II. a herbicidal pyranopyridinecarboxylic acid derivative according to the invention, and a process for the preparation of herbicidal compounds of the formula II.

The compounds of formula II also include their tautomers, their agriculturally acceptable acid addition salts and other addition compounds, and their optical isomers.

In the compounds of formula II, Re is preferably hydrogen, methyl, ethyl, 2-propynyl or furfuryl.

R3 is preferably methyl, methoxy or allyloxy; R 4 is preferably hydrogen, methyl or phenyl and R 7 is preferably hydrogen, chlorine or methoxy.

The most preferred group of structures are those wrists of formula 35 II wherein R 3 is CH 3 or OCH 3 and R 8 is H

4 8879S

as well as agriculturally acceptable salts and esters of these acids.

The compounds of the present invention can be prepared from suitably substituted condensed heteropyridine dicarboxylic acids and esters which can be represented by the following general formula: s'0-co2r 10 V 1 xxxi ^) -co2r

OF

wherein D-E forms part of a 5-membered ring marked A in connection with formula II above.

Thus, diesters of general formula XXXI above can be hydrolyzed to the corresponding heteropyridine-2,3-carboxylic acids of formula XXXIa and reacted with a strong base such as potassium hydroxide or sodium hydroxide. Acid anhydrides of formula XXXII can then be prepared by treating heteropyridinecarboxylic acids of formula XXXIa with, for example, acetic anhydride. Reaction of anhydrides of formula XXXII with an appropriately substituted aminocarboxamide described by formula XXXIII yields carbamoyl heteropyridine acids of formula XXX. Treatment of the resulting carbamoyl-heteropyridine acids of formula XXX with about 2-10 molar equivalents of aqueous sodium or potassium hydroxide or aqueous alcoholic solution, preferably under an inert gas such as a nitrogen blanket, is cooled and acidified to pH 2-4 with a strong mineral acid. , such as hydrochloric acid or sulfuric acid, to give herbicidally effective (4,4-disubstituted-5-oxo-2-imidazolin-3-yl) -condensed heteropyridine nicotinic acids of formula XXIXa as described in the following Scheme I, wherein R 3 is CH 3, R 2 is CH (CH3) 2 and W are O.

5 88798

Flow chart I

1. Aqueous ethanolic NaOH

5 / -D — r ^ \ - COOR solution / 'O —— COOH

C 1 --Δ- (I

VC -) - COOR 2. HCl VC— / 1 — COOH

N N

XXXI XXXI a 10

Ac 2O

15 \ (1 0> v 0

| l XXXII

20 NH2— (j: —cw — nh2 R2 _XXXIII_ 25

^ - ^ N-COOH r, / -D-r ^ N-COOH

(1 I - (1 1 m R1 VC — k> -CONH — c — CW— nh2 V —- L N — R?

N I N

30 2 Ϊ-

B

XXX XXIXa 6 88798

Fused (2-imidazolin-2-yl) fused heteropyridine esters of general formula XXIXb, wherein R e is other than hydrogen and R 1 (R 2 and W are as defined above, can be prepared by reacting a new fused imidazopyrrolo-heteropyridine dione represented by general formula XXV or XXVI hereinafter in Scheme II, with a suitable alcohol or corresponding alkali metal alkoxide at a temperature between about 20 ° C and about 50 ° C.

The novel condensed imidazopyrroloheteropyridinediones of formula XXVI can be conveniently prepared from acids of formula XXIXa by treating with one equivalent of dicyclohexylcarbodiimide in an inert solvent such as methylene chloride as described in Scheme II below.

Imidazopyrroloheteropyridine diones of formula XXV can be prepared from compounds of formula XXIXa by treatment with one to three equivalents of acetic anhydride in pyridine.

20 and 7 88798

Flowchart II ✓Ό —— COOH rx 5 CE_1 ^ -f-R2

N tjJ-t = W

B

XXIXa___ 10 DCC Ac2 O pyridine / - »VN- ^ R1 (I N-j = W ('N- ^ 2

M N - R2 N N-t = W

rl

20 XXVI XXV

r8o ~ m * r8o “w + _ ^ {W ^ V-COORg Rl _ wl) - <^ r: 2 N ^

B

XXIXb 8 88798

Many heteropyridine esters of general formula XXXI above are known in the art or can be prepared by reacting an amino- or amino-heterocycle with oxalic acetic esters, acetylenedicarboxyl-5-ylate ester.

An amino-substituted heterocycle having at least one unsubstituted ortho-carbon can be condensed with oxalacetic acid esters or can be coupled to acetylenedicarboxylic acid esters to give intermediate enamine 10. This can then be treated with one or two equivalents of Vilsmeier's reagent to give the desired diester.

Certain -o-amino heterocyclic aldehydes can be reacted with DMAD or oxalic acetic esters as described by P. Caluwe [Tetrahedron 36, 2359 (1980)] to give the desired diesters directly.

Certain diester compounds are prepared from enamines, which in turn are prepared from heterocyclic rings containing carbonyl functionality by reacting them with an ethoxymethylene compound. The product initially obtained is not isolated but is treated directly with a source of ammonia such as ammonium acetate to give the diester.

These reactions are described in Scheme III below, wherein D-E together with the carbons to which they are attached represents a 5-membered heterocyclic ring as defined above; R is methyl or ethyl; R 'is hydrogen or CHO; R "and R" 'are each hydrogen, C1-C6 alkyl or, taken together with the nitrogen atom to which they are attached, may form a 5- or 6-membered saturated ring having up to two heteroatoms in total.

i 9 88798

Flow chart III

H'R '

5 XE-C-NR "R

P R '= H F R' = CH0 R '= H J R' = H J

1Q R ", R '" = N or R "R'" = H R ", R" '= H R ", R'" ^ H

G G

15

—Ί r — G02R / -D— <jj — CH = Cj — CO2 R

^ E— ^ y ~ CO 2 R Ve-C C-CO 2 R

N I 11 I NR "R 0

B

20

Vilsmeier A NH4 + X "t— CTV ° 2 * k J — co2r -

OF

25 CO2C2H5 XXXI

F = O = icH 2 CO 2 C 2 H 5 G = CH 3 O 2 -C — C = C — co 2 CH 3 J = C 2 H 5 OCH = ^ - CO 2 C 2 H 5 O = C — CO 2 C 2 H 5 30 10 88793

Many condensed heteropyridine esters of general formula XXXI can be obtained by cleavage of oxidatively appropriately substituted heteroquinoline compounds which can be prepared by the method of 0. Meth-Cohn [J. Chem. Soc., Perkin I, 2509 (1981)] directly or by cleavage and subsequent reaction with amines as described in Scheme IV below:

Schedule IV

10 Γ3

Cl (CH 2) n

ci — L X J

N Y

15 0CH3

R3NH2 or (R3) 2NH

Oxidation 20 0CH3

✓ * (CH2) n —— (CH2) n —— ^ 02R

25 MNR3) m ^ x / Cl-J-CO2R

N Y N

OCH3 R3NH2 or Oxidation (R3) 30 Y —— co2r Ve-X j co2r

OF

XXXI

35 11 88792 wherein D-E together with the aromatic carbons to which it is attached means the aforementioned 5-membered fused heterocyclic ring containing one nitrogen atom; m is an integer 1; n is an integer of 2 and 5 R is hydrogen, CH 3 or C 2 H 5 and R 3 is as defined in connection with formula II.

Another general means of obtaining condensed hetero-pyridine diesters useful as intermediates for the preparation of the novel compounds of formula II of the invention is ring closure of 5-nitro-6-di-substituted pyridine-2,3-dicarboxylic acid esters which can be prepared by reacting la ethoxymethylene oxal acetate ester with nitroacetone.

For example, pyrrolopyridines can be prepared by condensing 5-nitro-6-methylpyridine-2,3-dicarboxylates with Ν, Ν-dialkylcarboxylamide diacetal followed by reduction and simultaneous cyclization depending on the reaction conditions. Alkylation of product 20 gives a mixture of two NR 3 compounds wherein R 3 is alkyl or alkoxy, as described in Scheme V below, wherein R 3 and R 4 are as defined above for Formula II.

Flow chart V

12 88798 5 H5C20HC = ^ - CO2C2H5 0 = C — CO2C2H5 it 10 1. NO2-CH2-C-CH3

2. NH4X

15 2, CH3 -) - CO2C2H5

OF

20-4 (alkyl) 2N-C (OCH3) 2Φ25

N (alkyl)? / X

N. NO2 - \\ - CO 2 C 2 H 5

\ I

C - —CH — x y — CO2C2H5 / 30 R4 h2 Ψ

Flow chart V (continued) 13 88798 5 Λ Λ R4— (Η Υι-002 ^ 5 ί -> - C02C2H5 10 Ν

R3i

ί3 15 VrV-C02C2H5 -J — C02C2H5

OF

+:: 20 R4 ^ R4 — Ν —co2c2h5 L- ^> -CO2C2H5

OF

: ·: 25 30 14 88792 6-Pyridone-2,3,5-tricarboxylic acid esters can be prepared by condensing the ester amide with ethoxymethylene oxalacetate ester and then converting the resulting compound to the 6-chloro compound. The latter chlorine compound can then be used in the synthesis of pyrrolopyridine diesters by reacting with an N-substituted amino acid ester while adding a base, followed by cyclization using an alkoxide as described in Scheme VI10 below. The resulting pyrrolopyridine compounds can further be alkylated, selectively decarboxylated, reduced and / or dehydrated to various substituted compounds.

i

Flow chart VI

is 38798 5 ^ η2 — CQ2C2H5 C2H50CH == (j: —CO2C2H5 CONH2 + O = C — co2c2h5 10 C2H5O2C - CO2C2H5 0 = ^ —CO2C2H5 SO2

B

15 c2h5o2c —— co2c2h5 I R3NHCH2CO2R ’

Cl-J-CO2C2H5 - 'N (R * = Et, t-Bu) base R'02CCH2 — N — J — CO2C2H5

I N

25 r3 0 = 3-

r, o2c — l Λ J

N N

V 30 R3 alkylation, decarboxylation, reduction: · and dehydration yields substituted ____: pyrrolo- and dihydropyrrolopyridines

ie 8879G

Other diester compounds are prepared by a novel reaction using the thermal Diels-Alder reaction of an appropriately substituted asymmetric triazine diester followed by nitrogen removal. An example of a reaction sequence of this type 5 is given by G.

Seitz and S. Dietrich, Arc. Pharm., 317, 379 (1984). Asymmetric triazine diesters useful in this reaction are prepared from substituted open-chain precursors containing one or more heteroatoms in the chain by reaction with a dialkyl-2,3-dioxosuccinate. Open chain precursors can be prepared, for example, from methylthiosemicarbazide and ω-alkynylamine. Triazine does not need to be isolated; heating can therefore be continued until the product taken up is formed.

This reaction is described in the following Scheme VII.

17 88798

Flow chart VIII = C H 1 (—N H 2 (CH2) n *

5 QH CH3S - <- NHZ

n = 2, Q = NH,

10 ^ C = CH

- (CH2) n ^ -NH2 ό — c — nh2 + O = C — CO2CH -s

15 T

0 = C — CO 2 CH 2 «4 ?, Λ *" * ·· 20 QH CH 3 S-1 ^ / LcO 2 CH 3

OF

yC = CH

(CH2) n n / NV-co2ch3 - 25 \ 1 '° ^ n ^ - <02CH3; . triazine - .: 30 j CK2) r, - CO2CH3 ^ -xQ— ^, · —CO2CH3

OF

n = 2, Q = NH or NR3 35

18 8 8 7 9 G

The (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group-substituted pyrrolopyridinecarboxylic acid derivatives of formula II of the present invention are highly effective herbicidal agents useful in controlling exceptional a wide range of plant-like and woody annuals and perennials, monocotyledons and dicotyledons. In addition, these compounds are herb-sidally effective in controlling weeds that thrive in both dry and moist soils. They are also useful as water-based herbicides and are unique in their effectiveness in controlling the above plants when applying substances to their press or to soil or water containing seeds or other organs that promote the spread of said plants, such as tubers, rhizomes and roots. agents from about 0.016 to 4.0 kg / ha and preferably at rates between about 0.032 and 2.0 kg / ha.

It is, of course, clear that amounts in excess of 4.0 kg / ha can be used to effectively kill unwanted plant varieties; however, levels of toxins greater than those necessary to destroy unwanted plants should be avoided, as the use of excessive amounts of toxins is expensive and of no benefit to the environment.

Among the plants that can be controlled by the compounds of this invention are the following plants: Elatine triandra, Sagittaria pygmaea,

Scirpus hotarui, Cyperus serotinus. Ecllpta Alba, Cyperus dif ormis. Rotala indica, Lindernia pyridonoria, Echino-chloa crus-Galli, Digitaria sanguinalls, Setaria viridis, Cyperus rotundus. Convolvulus arvensis, Agropyron repens, 35 Datura stramonium, Alopercurus myosuroides, Ipomoea spp., Slda spinosa, Ambrosia artemisiifolia. Eicbornia crassi-pes, Xanthlum pensylvancium, Sesbania exaltata, Avena fa-tua, Abutilon theophrasti, Bromus tectorum. Sorghum hale- 19 88790 pense, Lollum spp., Panlcum dichoromlflorum, Matricaria spp., Amaranthus retroflexus, Clrsium arvense and Rumex iaponicus.

It has been found that pyrrolopyridinecarboxylic acid derivatives of the formula II (4-isopropyl-5'-4-methyl-5-oxo-2-imidazolin-2-yl) group-substituted pyrrolopyridinecarboxylic acid derivatives are generally selective herbicides, in particular effective in controlling undesirable weeds in legumes, such as soybeans, and in the presence of cereals such as veh-10, barley, oats, and rye. However, some compounds are less selective than others in this series.

It has also been found that several compounds of formula II are effective anti-fouling agents in the field of cultivation when used at about 0.5 to 2000 g per hectare. When these substances are applied in an amount not exceeding about 2000 g per hectare, it has also been found that some of these compounds are effective in increasing the branching of legumes and the protrusion of the root crops of cereals. When applied in amounts of less than 2000 g per hectare, some of these compounds are useful in inhibiting peat growth.

Compounds of formula II which are water soluble may simply be dispersed in water and applied as a dilute water spray to the plant press or to soil containing plant propagation promoting organs. These compounds are also suitable for the preparation of flowable condensates.

In contrast, other compounds of formula II which are insoluble in water are suitable for the preparation of emulsifiable concentrates, which means a wide variety of preparation options for specific purposes.

The compounds of formula II can also be formulated as hydrophilic powders, flowable concentrates, granular preparations and the like.

Hydrogenable powders can be prepared by grinding together about 20-45% by weight of finely divided carriers.

20 9 8 7 9 G

such as kaolin, bentonite, diatomaceous earth, attapulgite or the like, 45-80% by weight of active compound, 2-5% by weight of dispersant such as sodium ligosulfonate and 2-3% by weight of non-ionizable surface ac -5 dense substance such as octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol or the like.

A typical fluid can be prepared by mixing together about 40% by weight of the active ingredient, about 2% by weight of a gelling agent such as bentonite-10, 3% by weight of a dispersant such as sodium lignosulfonate, 1% by weight of polyethylene glycol and 54% by weight. -% water.

A typical emulsifiable concentrate can be prepared by dissolving about 5-25% by weight of the active ingredient with about 65-90% by weight of N-methylpyrrolidone, isophorone, butylcellosolve, methyl acetate, or the like, and dispersing about 5% by weight thereof. -10% by weight of a non-ionizable surfactant such as alkylphenoxypolyethoxy alcohol. This concentrate 20 is dispersed in water to be applied as a liquid jet.

If the compounds of the invention are to be used as soil treatment herbicides, the compounds can be prepared as granular products and applied as such. The granular product can be prepared by dissolving the active compound in a solvent such as methylene chloride, N-methylpyrrolidone or the like and spraying the solution thus prepared onto a granular carrier such as corn cob, sand, attapulgite, kaolin or the like.

The granular product thus prepared generally contains about 3 to 20% by weight of active ingredient and about 97 to 80% by weight of granular carrier.

To further facilitate an understanding of the invention, the following reference examples and examples are provided to illustrate specific specific details of the invention. Unless otherwise stated, all parts are by weight.

Reference Example 1

Preparation of dimethyl 5- (2-chloroethyl) -6-chloro-2,3-pyridine dicarboxylate

2i 3879G

5 f ”3

C-CH2CH2-, "the Y / Y ^ // ^ S |

Cl- \ /) N Y 0CH3 10 03 15 ci-CH2CH2 -— CO2CH3

Cl- ^ J — CO2CH3 N

Ozone gas is bubbled into a solution containing 22.0 g of 2-chloro-3- (2-chloroethyl) -5,8-dimethoxyquinoline; 20 (O. Meth-Cohn, J. Chem. Soc., Perkin I, 1537-1543), 80 ml of trimethyl orthoformate and 2 ml of H 2 SO 4 in 1.0 liter of methanol, 5 hours and 45 minutes. The mixture is concentrated in vacuo and the residual oil is dissolved in ether and washed with saturated sodium bicarbonate solution. The aqueous layer is extracted with additional ether. The combined ether extracts are washed with 5% sodium bisulfite solution and then with saturated sodium chloride solution.

The organic layer is dried over anhydrous magnesium sulfate and evaporated in vacuo to give 16.5 g (71%) of dimethyl 5- (2-chloroethyl) -6-chloro-2,3-pyridinedicarboxylate as an orange oil.

22 8 8790

Reference Example 2

Preparation of dimethyl 1-methyl-2,3-dihydro-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate 5 Cl-CH2CH2-^-^ - 002083

Cl-J-CO2CH3 N

(ch3) 2nh 10 ^ co2ch3 N-s —CO2CH3 I. N ch3 7.5 g (166.6 mol) of dimethylamine are bubbled into a solution of 20.0 g (66 mmol) of dimethyl 5- (2-chloroethyl) -6-chloro-2,3-pyridinedicarboxylate in 400 ml. in methanol, for three hours. The resulting solution is stirred for 20 to 64 hours at room temperature and then heated to reflux for four and a half hours. After cooling, the mixture is evaporated in vacuo and the crude product is chromatographed on 250 g of silica using hexanes / ethyl acetate (2: 1) as eluent and then 25 hexanes / ethyl acetate (1: 1) to give 2.32 g (14%) of dimethyl -1-methyl-2,3-dihydro-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate, which is recrystallized from methylene chloride / hexanes to give a melting point of 132-133 ° C.

Reference Example 3

Preparation of dimethyl 1-methyl-1H-pyrrolo [1,3-b] pyridine-5,6-dicarboxylate

23 8 8 7 9 G

5 -r ^ V-CO 2 Me N ——CO 2 ^ ®

I N

Me jQ DDQ dioxon> -co2Me V 'N -— CO2Oe

I N

Me 1 5

To a solution of 2.53 g (0.010 mol) of dimethyl 2,3-dihydro-1-methyl-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate in 40 ml of dioxane is added 2.64 g (0.011 mol) 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. The resulting solution is stirred for 17 hours at 25 ° C and then heated for 3 hours using a reflux condenser. The dioxane is evaporated off: V in vacuo and the residue is partitioned between 100 ml of CH2Cl2 and 100 ml of NaHCO3 and filtered. The layers are separated and the aqueous fraction is extracted using 2 x 75 ml. CH2Cl2 <The combined CH2Cl2 solutions are dried over MgSO4 and evaporated in vacuo. The crude product is chromatographed using 50 g of silicic acid and hexanes / ethyl acetate (2: 1) as eluent. This gives 1.90 g of: - 30 (75%) of dimethoxy-1-methyl-1H-pyrrolo [2,3-b] pyrimidine-5,6-dicarboxylate as a yellow solid, ./·.·; mp: 132-133 ° C.

Reference Example 4

Preparation of triethyl 1,6-dihydro-6-oxo-2,3,5-pyridine tricarboxylate

24 8 8 7 9 G

5? C2 »5 c2h5 ° 2c - ^» 2 + HC = C — CO2C2H5 ° == c — nh2 0 = C — CO2C2H5

10 NaOAC Et OH

Δ co2c2h5 — co2c2h5 0 == \ y — C02C2H5 Ϊ

B

A solution of 23.6 g (0.18 mol) of ethyl malonamate in 300 ml of absolute ethanol is added to a stirred solution of 44.0 g (0.18 mol) of diethyl ethoxymethylene oxalacetate in 200 ml of ethanol and at 0 ° C, after which 14.72 g (0.18 mol) of solid sodium acetate are added.

After stirring for 10 minutes at 0 ° C, the mixture is heated and stirred at reflux for 13.5 hours. After cooling, the ethanol is removed in vacuo and the residue is diluted with water and acidified to pH 2 with concentrated hydrochloric acid. The aqueous solution is extracted with methylene chloride (2 x 200 ml) and the organic layer is washed with 300 ml of saturated sodium chloride solution, then dried over anhydrous magnesium sulphate and evaporated in vacuo to give 45.0 g of the title product as an orange oil.

Reference Example 5

Preparation of triethyl 6-chloro-2,3,5-pyridine tricarboxylate

25 8 8 7 9 G

5 C2H5O2C —— CO2C2H5 0 = 1 ^ Ϊ

B

10 POCl 3 ^ 2 ^ 502 ^ —— CO2C2H5 1

Cl— \ —CO2C2H5

OF

15

A solution of 39.7 g of triethyl 1,6-dihydro-6-oxo-2,3,5-pyridine tricarboxylate in a mixture of 300 ml of phosphorus oxychloride and 0.5 ml of dimethylformamide is stirred at 1 ° C 4 hours and 20 to 15 minutes. After cooling, the excess phosphorus oxychloride is removed in vacuo. The residue is taken up in 200 ml of methylene chloride and the solution is poured into 500 ml of ice water and the layers are separated. The aqueous layer, which has been basified with concentrated ammonium hydroxide and ice, is extracted with 25 to 150 ml of methylene chloride. The combined methylene chloride extracts are dried over magnesium sulphate, filtered and evaporated in vacuo and the crude product obtained is chromatographed using nitric acid and hexanes / ethyl acetate (5: 1) as eluents and then hexanes / ethyl •; 30 acetate (4: 1) to give 26.5 g of the title product (47 "0)" · "as an oil.

26 8 8 7 9 G

Reference Example 6

Preparation of tetraethyl 6- [~ (carboxymethyl) methylamino] -2,3,5-pyridine tricarboxylate 5 C2H5O2C-CO2C2H5

Cl-J CO2C2H5

OF

10 CH3NHCH2CO2C2H5 · HCl 2 eq. Et 3 N

THF

C2H5O2C —— CO2C2H5 C2H502C — CH2 — J — CO2c2h5 λ c In 15 ch3 13.91 g (0.090 mol) of sarcosine ethyl ester hydrochloride are added to a stirred solution containing 26.2 g (0.075 mol) of triethyl-6-chloro-2.3 , 5-pyridine tri-20 carboxylate in 200 ml of tetrahydrofuran (THF) containing 23 ml (0.166 mol) of triethylamine at a temperature of 0 ° C. The resulting solution is stirred for 24 hours at room temperature. The triethylamine hydrochloride is removed by filtration and washed with 100 ml of ether. The filtrate is evaporated in vacuo and the crude product is chromatographed on silica using hexanes / ethyl acetate (4: 1) as eluent to give 21.1 g (60%) of tetraethyl-6 - ((carboxymethyl) methylamino) -2.3, 5-pyridine tricarboxylate as a yellow oil.

i

Reference Example 7

Preparation of triethyl 3-hydroxy-1-methyl-1H-pyrrolo [2,3-b] pyridine-2,5,6-tricarboxylate 27 8 8 798 (j) C2H5O2O-CO2C2c2h502c — ch2-l * -4 ^ j — CO2C2H5 IN CH3 10

NaOC2H5 ethanol J-I-V-CO2c2h5

15 c2h5o2c - <^ I

N 2 - (CO 2 C 2 H 5)

I N

ch3 0.3 g (0.73 iranol) of tetraethyl 6 - [(carboxymethyl) methylamino] -2,3,5-pyridine tricarboxylate in 20 ml of ethanol are added to a freshly prepared solution containing 2.1 mmol of sodium ethoxide in ethanol, at room temperature. The resulting orange solution is stirred for 2 hours at room temperature, then poured into 200 ml of water and the pH is adjusted to 8 with saturated. 25 with aqueous sodium bicarbonate solution. The aqueous solution is extracted with methylene chloride (3 x 100 mL). Combined methylene. . The chloride extracts are dried over anhydrous magnesium sulphate, filtered and evaporated under reduced pressure to give 0.28 g (100%) of triethyl-3-hydroxy-1-methyl-1H-30 pyrrolo / 2,3-h / pyridine-2,5,6- tricarboxylate, which •! melting point from methylene chloride / hexanes; after recrystallization is 129-130 ° C.

Reference Example 8

Preparation of diethyl 3-methyl-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate 28 8 8 79

?B

5) -Γ NT "CO2C2H5

C2H5O2C-I

N -) - CO2C2H5

I N

CH3

10 NaOH H +, CH 3 OH

Δ Δ J — VV-C ° 2C2H5 N-k, J — CO2C2H5

15 I N

CH3

A solution of 9.2 g (0.025 mol) of triethyl 3-hydroxy-1-methyl-1H-pyrrolo [2,3-b] pyridine-2,5,6-tricarboxylate in 75 ml of 2N sodium hydroxide was heated At 60 ° C for 21 hours. After cooling to 0 ° C, the reaction mixture is acidified to pH 3 with concentrated hydrochloric acid. Most of the water is removed by azeotropic distillation with toluene and the remaining solution (25 ml) is diluted with 300 ml of methanol. To this solution is added 3 ml of concentrated sulfuric acid and the resulting solution is heated at reflux for 64 hours. After cooling, the reaction mixture is evaporated in vacuo and the residue is partitioned between aqueous sodium bicarbonate solution (500 ml, 5%) and methylene chloride (300 ml). The layers are separated and the aqueous solution is extracted with additional methylene chloride (200 mL).

The combined organic extracts are washed with 200 ml of saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated in vacuo. The crude product is chromatographed on silica using hexane / ethyl acetate (2: 1) as eluent to give

29 3 8 79G

2.04 g (29%) of diethyl 3-methoxy-1-methyl-1H-pyrrolo [2,3-t] pyridine-5,6-dicarboxylate, m.p. 73-74 ° C. Reference Example 9

Preparation of diethyl 5-acetyl-1,6-dihydro-6-oxo-2,3-pyridine-5-carboxylate S-ofrsin

S

CH3''CYi? V: 02C2H5 0 = 1> ^ 02C2H5 10 Ijl

B

NH 2 OH · HCl NoOCH 3 EtOH

15 X "CH3> ^ Y> N-CO2C2H5

OrJs. J — CO2C2H5 N

20 |

B

4.94 g (0.0711 mol) of hydroxylamine hydrochloride: V and 7.68 g (0.1422 mol) of sodium methoxide are added under a N2 atmosphere to a solution containing 20.00 g (0.0711 mol) of diethyl-5- acetyl 1,6-dihydro-6-oxo-2,3-pyridinedicarboxylate dissolved in 450 ml of absolute ethanol. The reaction mixture is heated to reflux for 40 minutes and then ... stir at room temperature overnight. The mixture is then acidified to pH 4-5 with glacial acetic acid and diluted with water (200 mL). Removal of ethanol in vacuo results in the precipitation of an off-white solid which is collected by filtration, washed with water and air dried to give diethyl 5-acetyl-1,6-dihydro-6-35 oxo-2,3-pyridinedicarboxylate, 5 oxime with a melting point is 140-142 ° C.

30 8 8798

Reference Example 10

Preparation of diethyl 5-acetamido-1,6-dihydro-6-oxo-2,3-pyridine di-carboxylate and diethyl-2-methyl-oxathi [4-b] pyridine-5,6-dicarboxylate 5 5 CH3-C— —CO2C2H5 0 = LJ — CO2C2H5 10 fj *

B

SOCO12 CHCl3 15 cH3-i / MWe0iCiHs o 0 = <J-CO2c2h5

V

20 I

B

+ 25 —CO2C2H5 ch3-110 -— CO2C2H5

OF

35.5 ml (0.486 mol) of thionyl chloride and 3 drops of 30 N, Ν-dimethylformamide are added under a N-atmosphere to a solution of 47.99 g (0.162 mol) of diethyl 5-acetyl-1,6-dihydro-6-oxo -2,3-pyridinedicarboxylate, 5-oxime dissolved in 800 ml of chloroform. The reaction mixture is stirred at room temperature for one hour, then stirred at room temperature overnight.

3i 88798

The solution is evaporated in vacuo and the residue is partitioned between methylene chloride and water. The 2-phase system is neutralized with 2N sodium hydroxide solution and the aqueous layer is separated and extracted with methylene chloride. The combined organic solutions are dried over anhydrous sodium sulfate, evaporated in vacuo and chromatographed on silica gel with 1-30% ethyl acetate in methylene chloride to give a 58% yield of diethyl 5-acetamido-1,6-dihydro-6-oxo-2, 3-pyridine di-10 carboxylate having a melting point of 149-151 ° C after crystallization from methylene chloride / hexane.

The fractions enriched in 2-methyloxazolopyridine are chromatographed on silica gel using hexane / ethyl acetate (3: 1) as eluent. Recrystallization of the product from methylene chloride / hexane gives a 17% yield of diethyl 2-methyloxazolo [5,4-b] pyridine-5,6-dicarboxylate as pale yellow crystals with a melting point of 101-103 ° C.

32 8 8 798

Reference Example 11

Preparation of diethyl 5-amino-1,6-dihydro-6-oxo-2,3-pyridinedicarboxylate f CHi-irN'T ^ VCO2C2H5 ° 0 = L J — CO2C2H5 Ϊ

B

10

HCl HtOH

15 H2N —— CO2C2H5 0 = 1, j-CO2C2H5 f

B

Hydrogen chloride gas is bubbled into a solution of 5.2 g (0.018 mol) of diethyl 5-acetamido-1,6-dihydro-6-oxo-2,3-pyridinedicarboxylate dissolved in 400 ml of absolute ethanol until the solution is saturated at 20 ° C. The reaction mixture is stirred at room temperature overnight and then evaporated in vacuo. The residue obtained is dissolved in water, the solution is neutralized with solid sodium bicarbonate and extracted into methylene chloride. The combined organic extracts are dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to give a quantitative yield of diethyl 5-amino-1,6-dihydro-6-oxo-2,3-pyridinedicarboxylate as a yellow solid.

i 33 8 8 7 9 8

Reference Example 12

Preparation of diethyl 2-ethyloxazolo [1,4-b] pyridine-5,6-dicarboxylate 5 H2N-C00C2H5O = s J-C00C2H5 f

B

10

TEOP pTSOH

- / ^ S — C00C2H5 C2H5 - <^ '15 o-J — cooc2h5

OF

7.57 g (0.030 mol) of diethyl 5-amino-1,5-dihydro-6-oxopyridine-2,3-dicarboxylate are suspended in 60 ml of triethyl orthopropionate (TEOP, 0.30 mol). A minimum of 20 p-toluenesulfonic acid is added and the mixture is heated to reflux for 65 hours. The triethyl orthopropionate is removed in vacuo and the resulting oil is purified by column chromatography. The fractions containing pure desired product are combined and evaporated to a honey-colored oil weighing 7.38 g, yield 84.8%.

34 β 8 7 9 G

Reference Example 13 Preparation of 2-methyl-oxazolo [4,4-b] pyridine-5,6-dicarboxylic acid 5H3N- {N2O2C2H5 O- ^ ^ -CO2C2H5

OF

278.3 10

NoOH MeOH

15 / N-ί '^ Ν — COOH

CH3 I

0- ^ /) - COOH

OF

To a solution of 5.42 g (0.0195 mol) of diethyl 2-methyloxazolo [5,4-b] pyridine-1,6-dicarboxylate dissolved in 160 ml of absolute methanol is added 10% aqueous sodium hydroxide solution (36 , 1 mL, 0.0974 mol). In this case, a white precipitate slowly forms. The reaction mixture is stirred at room temperature for one hour, diluted with 20 ml of water to dissolve the precipitate and evaporated in vacuo. The residue is dissolved in water and acidified to pH 2-3 with concentrated HCl. The white precipitate formed is collected by filtration, washed with water and air-dried to give 61% yield of 2-methyloxazolo [1,4-b] pyridine-5,6-dicarboxylic acid, m.p. 235-236 ° C (decomposes).

i 35 8 8 790

Reference Example 14 Preparation of 2-methyloxazolo [5,4-b] pyridine-5,6-dicarboxylic anhydride

3 \ n-1 /} - COOH

OF

A suspension containing 4.84 g (0.0218 mol) of 2-methyloxazolo [5,4-b] pyridine-5,6-dicarboxylic acid in 150 ml of acetic anhydride, 222.1 10 ac20. slowly heated to 70 ° C, by which time all solids dissolve to form a yellow solution. The reaction mixture is heated at 70 ° C overnight, cooled to room temperature and evaporated in vacuo. Xylene is added to remove excess acetic anhydride by distillation. 2-Methyloxazolo - [5,4-h] pyridine-5,6-dicarboxylic acid: anhydride is obtained in 97% yield as a pale yellow solid with a melting point of 194-196 ° C.

Reference Example 15 Preparation of 2-methyloxazolo [5,4-b] pyridine-5,6-dicarboxylic acid 6-diamide

36 β 8 79G

5 S

y — f ”3 CH3-1 + nh2 — C — CONH2 ° CH (CH3) 2 10 o f3 15 Nt- * s —CONH — C — CONH2 NT,, CH (CH3) 2 4.33 g of anhydride are dissolved in 150 ml in acetonitrile and the solution is cooled in an ice bath and 3.03 g of aminoamide are added. A white precipitate immediately forms. The reaction mixture is warmed to room temperature and stirred overnight. The solid product is filtered off, washed with acetonitrile and dried under vacuum in an oven to give 6.3 g of product, 89%, m.p. 193-196 ° C.

Other acid diamides are prepared in a manner similar to that described above and are shown in Table I below.

37 8 8 790

Table I

(1-Carbamoyl-1,2-dimethylpropyl) carbamoylheteropyridinylcarboxylic acids 5 E 2 x -C 0 N H C-C O - -N H ·)

N I

CH (CH3) 2 10

Heteropyrldllnl sp. 8C

<j) CH 3 15 I-k 4

OF

(j) CH 2 CH = CH 2 - ax

OF

CH30 ---

„K A

25 γ N

CH3 <j) CH3 ch3-yny ^ V- 30 1 1

OF

k A.

- Ok

OF

38 ft 8 7 9 α

Table I (continued)

Heteropvr ldlinl —— fjl N CH3

10 / X

nft fjl N CH3 15 (JH3

Cft - ^ / n 20 <j> CH3 JXt

25 N

ci — j — t ^ y-I I

v A ^ -

γ N

ch3 30 (j) CH3

35 N

Reference Example 16

Preparation of ethyl 4-amino-1-methyl-2-pyrrolecarboxylate 39 88798 <[”3

5 H5C202C— / NN

• -i-no2

107. Pt / C

10 H2 EtOH

16.0 g (0.081 mol) of ethyl 1-methyl-4-nitro-3-pyrrolecarboxylate (M.J. Weiss, J.S. Webb and J.M.

Smith, J. Amer.Chem. Soc., 79, 1266 (1957)) is dissolved. To 20,200 ml of ethanol is added 1.60 g of a catalyst containing 10% of platinum on carbon. Mixture ____: shake for 16 hours in a Parr hydrogenator. Kataly- ... the receiver is removed by filtration through a pad of Celite and the filtrate is concentrated in vacuo to a yellow oil, the oil is used directly without further purification.

Reference Example 17 Preparation of 5-ethyl, dimethyl [(5-carboxy-1-methylpyrrol-3-yl) amino] maleate

40 8 8 7 9 S

5 H5C202C-rN2l L_J-NH2 0 ether'H2 °

DMAD

NoOAc H 5 C 2 0 2 C-HC-CO 2 CH 3 L- / Z-CO 2 CH 2 f

B

0.081 mol of crude ethyl 4-amino-1-methyl-2-pyrrolecarboxylate is added to a mixture of 50 ml of anhydrous ether and 50 ml of water, and the mixture is cooled to 0 ° C. 10.95 ml (0.089 mol) of dimethylacetylene dicarboxylate (DMAD) are dissolved in 25 ml of anhydrous ether and the solution is added dropwise to the stirred solution so that the reaction temperature remains below 15 ° C. After stirring in the cold for 5 minutes, sodium acetate is added portionwise until the pH of the aqueous layer is 9. The 2-phase red mixture is then allowed to warm to room temperature and stirred for 15 hours. The layers are separated and the ether layer is concentrated in vacuo to give the product as a red oil which is used without further purification.

Reference Example 18 Preparation of 2-ethyl-dimethyl-1-methylpyrrolo [3,2-b] pyridine-2,5,6-carboxylate 4i 88798 5 f3

H 2 CO 2 C 2 -CH-CO 2 CH 3 I-X-CO 2 CH 3 f

B

10 P0C13

DM F

DC E

15 Ϊ ”3 H5C2O2C- / N Y ^ V-CO2CH3 1! - \ ^ _co2CH3

OF

0.089 mol of dimethylformamide is dissolved in 100% dichloroethane and the solution is cooled to 0 ° C in an acetone / ice bath. 8.3 ml (0.089 mol) of phosphorus oxychloride are added dropwise over 5 minutes. The clear colorless solution is allowed to slowly warm to room temperature, whereupon it gradually turns yellow. 0.081 mol of purified 5-ethyldimethyl / (5-carboxy-1-methylpyrrol-3-yl) amine / maleate is dissolved in 50% of dichloroethane and the solution is added dropwise to the cooled reagent so that - the reaction temperature remains below 5 ° C. . The mixture is allowed to cool to room temperature and then stirred for 6 hours. The solution is cooled with ice and the layers formed are separated. The organic layer is concentrated in vacuo to a brown solid which is recrystallized from ethyl acetate to give 21.3 g (82.1%) of a tan solid with a melting point of 161.5-163 ° C.

42 88798

Reference Example 19

Preparation of diethyl 6-methyl-5-nitro-2,3-pyridinedicarboxylate 5 K f2 "5 O2NCH2CCH3 * HC = CH-CO2C2H5 0 = CH-CO2C2H5

ΝαOAC NH4OAC

10 O2N— “CO2C2H5 H3C — L J-CO2C2H 5

OF

150.4 g (0.616 mol, 1 eq.) Of diethyl ethoxymethylene oxaleacetate are dissolved in 300 ml of absolute ethanol under a nitrogen atmosphere and the mixture is cooled to -10 ° C in an ice / acetone bath. Crude 1-nitro-20 2-propanone (prepared according to the method of D. Baker and S. Putt, Synthesis, 1978, 478-9, presumably contains 63.448 g, 0.616 mol), dissolved in 100 ml of absolute ethanol , is then added to the stirred solution. 101.06 g (1.232 mol) of sodium acetate are then added portionwise so that the temperature of the reaction mixture remains below 10 [deg.] C., after which 94.6 g (1.232 mol) of ammonium acetate are added. The P.eak thio mixture is allowed to warm to room temperature and then stirred for 16 hours. The mixture is filtered through two layers of silica gel, which are then eluted with methylene chloride. The filtrate is evaporated in vacuo to a thick dark oil which is chromatographed using hexanes as eluent to give 18.2% yield of product (31.4 g) with a melting point of 90-91.5 ° C.

43 88798

Reference Example 20

Preparation of Dietvy 11-6- [2- (dimethylamino) vinyl] -5-nitro-2,3-pyridinedicarboxylate 02N-T2N-CO2C2H5 f0 ”3

1 ♦ (CH3) 2N — CH

H3C njs,> -CO2c2h5 I

N 0CH 3 10 / v O 2 N-j "| -CO 2 C 2 H 5 (ch 3) 2 nch = ch- \ CO 2 C 2 H 5

OF

18.38 ml (0.138 mol) of N, N-dimethylformamide dimethyl-acetal are mixed with 30.0 g (0.106 mol) of diethyl 6-methyl-5-nitro-2,3-pyridinedicarboxylate. The solid mixture is heated to 55 ° C over two hours and then the resulting red solution is cooled to room temperature. The solid formed on cooling is treated with anhydrous ether and the product. collected by filtration to give a 94% yield ’and a melting point of 128-129.5 ° C.

... In a similar manner, a 93% yield of diethyl 6- [2- (dimethylamino) propenyl] -5-nitro-2,3-pyridine di-carboxylate with a melting point of 112-113.5 ° C, N, N-·. · Dimethylacetamide dimethylacetal and diethyl 6-methyl-5-nitro-2,3-pyridinedicarboxylate.

Diethyl 6- [2- (dimethylamino) styryl] -5-nitro-2,3-pyridinedicarboxylate is also prepared using. By the above procedure from N, Ν-dimethylbenzamide-diethyl acetal and diethyl 6-methyl-5-nitro-2,3-pyridinedicarboxylate. The modification in the latter method is such that, after cooling, the dark red solution is partitioned between ether and water. The Eette-35 sulfur crude is separated and concentrated in vacuo to a dark red oil which is used without further purification.

44 88798

Reference Example 21

Preparation of diethyl β-hydroxypyrrolo [3,2-t] pyridine-2,3-dicarboxylate 5 N, N - (N, N

OF

NaH 2 PO 2 * H 2 O 10% Pd / C

10 Γ / nY ^ Y_c ° 2C2H5 I-L —CO2C2 »5

15 N

30.9 g (0.092 mol) of diethyl 6- [2- (dimethylamino) vinyl] -5-nitro-2,3-pyridinedicarboxylate are dissolved in 500 ml of tetrahydrofuran under a nitrogen atmosphere and 3.1 parts of a red solution are added in one portion. g of catalyst with 10% palladium on carbon. Dissolved in water, 121.00 g (1.375 mol) of sodium hypophosphite are then added dropwise to the solution over a period of 3 hours, and the evolution of hydrogen gas is observed during this time. 500 ml of ether are added to the pale gel reaction mixture and the biphasic mixture is filtered through a pad of Celite. The ether layer is separated and evaporated in vacuo to give a 98% yield of a pale yellow solid with a melting point of 154-158 ° C.

In a similar manner, a 95% yield of diethyl 1-hydroxy-2-methylpyrrolo [3,2-b] pyridine-5,6-dicarboxylate having a melting point of 178-179 ° C, 6- [2- (dimethylamino) propenyl] From 5-nitro-2,3-pyridine di-35 carboxylate.

i

Ί5 8879G

Using the above procedure, diethyl 1-hydroxy-2-phenylpyrrolo [3,2-h] pyridine-5,6-dicarboxylate having a melting point of 179-182.5 ° C, 6- [2- (dimethylamino) styryl] -4- From 5-nitro-2,3-pyridine di-5 carboxylate. The pale yellow solid is purified by chromatography and recrystallized from ethyl acetate.

Reference Example 22

Preparation of diethyl 1-methoxypyrrolo [2,3-b] pyridine-5,6-dicarboxylate and diethyl 1-methylpyrrolo [3,2-h] pyridine-5β-dicarboxylate T-RN1-C ° 2C2H5

OF

CH 3 I

DM F

. 20 BuOK

CH3 ^ 3 L- \ J — CO2C2H5 '- \ J — CO2C2H5

; · 25 N N

25.2 g (0.091 mol) of diethyl 1-hydroxypyrrolo [3,2-b] pyridine-5,6-dicarboxylate are dissolved in 100 ml of dimethylformamide and the solution is cooled to 0 [deg.] C. under a nitrogen / atmosphere. 20.42 g (0.182 mol) of potassium t-butoxide. : 30 is added over 15 minutes so that the reaction temperature "... does not rise above 15 ° C. The red solution is stirred for 15 minutes and then 11.33 ml" (0.182 mol) of methyl iodide are added dropwise over 15 minutes so that the temperature does not rise above 15 ° C. The mixture 35 is allowed to warm to room temperature and then

«8879G

stir for 16 hours. The resulting suspension is filtered and the mother liquors are concentrated in vacuo. The resulting oil is partitioned between ethyl acetate and water (pH 8) and the organic layer is separated and evaporated in vacuo.

The oil obtained, which contains a mixture of diethyl 1-methoxypyrrolo [3,2-b] pyridine-5,6-dicarboxylate, is chromatographed using a hexane / ethyl acetate (9: 1) mixture and increasing the polarity and then the hexane / ethyl acetate ratio. 2: 1. Fractions containing methoxy product (confirmed by NMR) were combined and evaporated in vacuo to give 53.2% yield of a pale yellow solid, mp 87.5-89 ° C. The methyl product-containing fractions were combined and evaporated to give a 23.8% yield of a tan solid, mp 97-100 ° C.

47 8 8 798

Reference Example 23

Preparation of diethyl 1-methoxy-2-phenylpyrrolo [3,2-b] pyridine-5,6-dicarboxylate

5 (? H

^ "YyoftHS

L — t CO2C2H5

OF

10 CH3I DMF

Γ ^ Ί Γ3, s ^ Nrt ° 2C2H5 I — t <J-co2c2h5

OF

1.3 g (0.0037 mol) of 1-hydroxy-2-phenylpyrrolo [3,2-b] pyridine-5,6-dicarboxylate are dissolved in 50 ml of dimethylformamide and the solution is cooled to -30 ° C. under the atmosphere. 0.85 g (0.007 mol) of potassium t-butoxide are added over a period of 10 minutes so that the reaction temperature does not rise above -24 ° C. The red solution is stirred for 5 minutes and then 0.87 ml (0.014 mol) of methyl iodide are added dropwise over 5 minutes; . so that the reaction temperature does not rise above -20 ° C. The mixture is then allowed to warm to room temperature and stirred for 16 hours. The suspension is concentrated in vacuo. The oil obtained is partitioned between ethyl acetate and water (pH 30). The organic layer is separated and concentrated in vacuo. The resulting yellow oily solid is flash chromatographed using hexane / ethyl acetate (9: 1). The product is obtained in the form of a pale yellow solid weighing 1.0 g (yield 35 73.5 ° C) and having a melting point of 95-96.5 ° C.

48 88798

In a similar manner, 95% yield of diethyl 1-hydroxy-2-methylpyrrolo [3,2-b] pyridine-5,6-dicarboxylate was prepared from diethyl 1-methoxy-2-methylpyrrolo [3,2-b] pyridine. 5,6-dicarboxylate having a melting point of δ 4.5-96.5 ° C.

Reference Example 24

Preparation of diethyl 1- (allyloxy) pyrrolo [2,3-b] pyridine-5,6-dicarboxylate 10 λ Γ i Y "C ° 2C2H5 L - ^ 4-CO2C2H5

OF

15 H2C = CHCH2Br

THF

NaH

(j) CH2CB = CH2 / nv ^ y_co2c2h5 L-J-CO2C2H3

OF

6.2 g (0.022 mol) of diethyl 1-hydroxypyrrolo-25 (N-2-pyridine-5,6-dicarboxylate) are dissolved in 200 ml of dry tetrahydrofuran and cooled to 0 [deg.] C. under a nitrogen atmosphere. g (0.033 mol) of sodium hydride are added portionwise over 10 minutes and the reaction mixture is stirred for 30 minutes at 0. 2.01 ml (0.024 mol) of allyl bromide are all added in one portion to the suspension and the mixture is allowed to warm to room temperature and then stirred. The mixture is filtered and the filtrate is evaporated in vacuo to give an oil which is chromatographed using hexanes / ethyl acetate (4: 1) and then increasing the polarity to a hexanes / ethyl acetate ratio of 2: 1 to give the product as a yellow oil. 89% yield.

49 P, 8 7 9 G

Reference Example 25

Preparation of diethyl 1- (difluoromethoxy) pyrrolo [3,2-b] pyridine-5,6-dicarboxylate and diethyl pyrrolo [3,2-b] pyridine-5,6-dicarboxylate

5 <JH

rYVc ° 2C2H5 L- ^ CO2CO2H5

OF

10

NaOCH 3

EtOH

CF2C1H

(j) CHF2 • j1 15 co2c2h5 co2c2h5 L \ X- co2c2h5 -L —co2c2h5

N N

8.1 g (0.15 mol) of sodium methoxide are slowly added over a period of 15 minutes to a suspension of 6.94 g (0.025 mol) of diethyl 1-hydroxypyrrolo [3,2-h] pyridine-5,6-dicarboxylate suspended in 100 ml of absolute water. Ethanol, under a nitrogen atmosphere at 0 ° C. The mixture is then heated to reflux and 25 Freon 22 gases are bubbled through the reaction suspension for 6 hours. Additional sodium methoxide (8.1 g, 0.15 mol) is added portionwise at reflux temperature and the addition of freon is stopped after a total of 8 hours. Heating using the return cooler is left. ··. 30 is continued for 16 hours. Additional sodium methoxide (8.1 g, 0.15 mol) is added and Freon 22 gas is again bubbled through the suspension while heating and refluxing with cooling.

so 8 8 798

The addition of Freon gas is then stopped and the mixture is heated at reflux for 72 hours. The mixture is cooled to room temperature and ethanolic HCl solution is added until a pH range of 4-5 is reached. The solid suspension is filtered and the filtrate is evaporated in vacuo to a yellow oil which is chromatographed using hexane / ethyl acetate (4: 1) to give 16.2% yield of the title product as a yellow oil. The main collected by-product is diethyl pyrrolo [3,2-b] pyridine-5,6-dicarboxylate obtained in 52% yield and as a pale yellow solid, m.p. 109-111 ° C.

Reference Example 26

Preparation of diethyl 1-methoxy-3-chloropyrrolo [3,2-b] pyridine-5,6-15 dicarboxylate (CH3 / N γ'5Ν-co_2C2h5 20 LA N Aco.2c2h5 NCS ccn benzoyl percoxide γ-Οθ2θ2Η5

Cl-1-L <jL-C0.2C2H5

OF

0.91 g (0.037 mol) of benzoyl peroxide are added to a solution of 1.0 g (0.003 mol) of diethyl 1-methoxypyrrolo [3,2-b] pyridine-5,6-dicarboxylate dissolved in 40 ml of carbon tetrachloride. , under a nitrogen atmosphere: · '35 and stir the suspension for 10 minutes.

si B 8 7 9 8 0.84 g (0.0063 mol) of N-chlorosuccinimide are then added and the reaction mixture is heated at 60 ° C for 4 hours. The mixture is cooled to room temperature and the inorganics are removed by filtration. The organic mother liquors 5 are washed with water and sodium bisulfite and concentrated in vacuo to an orange oil, the oil is flash chromatographed using hexanes followed by hexanes / ethyl acetate (4: 1) to give a 51% yield of the title product as an off-white solid. 148 ° C.

The ethereal mother liquors are evaporated in vacuo and the residue is dissolved in 100 ml of acetic acid. 0.44 g of a catalyst comprising 5% palladium on carbon is added and the mixture is shaken for 16 hours in a Parr hydrogenator at a pressure of 3.5 kg / cm 3. The reaction is quenched and the dark solution is filtered through a pad of Celite and evaporated in vacuo. The resulting oil is chromatographed using hexane / ethyl acetate (7: 1) followed by hexane / ethyl acetate (3: 1) to give 31% yield of the title product as a pale yellow solid, m.p. 109-111 ° C.

52 88798

Reference Example 27

Preparation of diethyl Pvrrolo [3,2-b] pyridine-5,6-dicarboxylate 5 02N - [? Y-CO2C2H5 (CH3) 2NCH = CH-1, co2c2h5

OF

H2 107. Pd / C 10 Ij V ^ v-CO2 <: 2H5 -— \ J — co2cZH5

OF

20.9 g (0.059 mol) of diethyl 6- [2- (dimethylamino) vinyl] -5-nitro-2,3-pyridinedicarboxylate are partially dissolved in 200 ml of acetic acid and then 0.6 g of catalyst are added in one portion, containing 5% palladium on carbon. The mixture is shaken for 20 to 16 hours under a hydrogen atmosphere in a Parr hydrogenator. The reaction is stopped and the suspension is diluted with ethanol and filtered through a pad of Celite. The mother liquors are evaporated in vacuo to a dark red oil. Trituration with ether gives a 40% yield of the N-hydroxy compound as a white solid with a melting point of 154-158 ° C.

The ethereal mother liquors are evaporated in vacuo and the residue is dissolved in 100 ml of acetic acid. 0.44 g of catalyst containing 5% palladium on carbon is added and the whole mixture is shaken for 16 hours in a Parr hydrogenator. The reaction is quenched and the dark solution is filtered through a pad of Celite and evaporated in vacuo.

· - The oil obtained is subjected to gravity chromatography using a hexane / ethyl acetate (7: 1) mixture and increasing the polarity and then the hexane / ethyl acetate ratio to 3: 1. The pale yellow solid is collected. Yield: 31%, melting point 109-111 ° C.

53 88798

Reference Example 28

Preparation of dimethoxy-3-chloro-1-methyl-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate 5 | R / 5V "CO 2 CH 3 Λ J-CO 2 CH 3

Ijl N CH3 10

NCS

Ci-R 2 -CO 2 CH 3 15 kwA -CO 2 CH 3

OF

CH3

To a solution of 1.74 g (0.0070 mol) of dimethoxymethyl 1H-pyrrolo [2,3-h] pyridine-5,6-dicarboxylate in 50 ml of CCl 4 is added a mixture containing 0 .98 g (0.0073 mol) of N-chlorosuccinimide and 0.18 g (0.00073 mol) of benzyl peroxide. The resulting solution is stirred at reflux for 4 hours and at 60 ° C for 15 hours. The solution is cooled to room temperature, diluted with 100 mL and washed with 5% Na 2 S 2 O 3.

The aqueous layer is extracted with a further 50 ml of Cl 2 Cl 2 and the combined organic solutions are dried over MgSO 4 and evaporated in vacuo. The crude product is chromatographed using 50 g of silicic acid and hexanes / ethyl acetate (3: 1) - /. mixture to give 0.87 g (44%) of dimethoxy-3-chloro-1 '- methyl-1H-pyrrolo [2,3-b] pyridine-5,6-dicarboxylate

··· 'as a yellow solid, m.p. 1 29-137 ° C

54 8879ο

Reference Example 29 Preparation of 6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1H-1-methylpyrazolo [3,4-b] pyridine-5-carboxylic acid

N \ ^ ✓ C02Et γ N

CH3 10, 1st base 2. acetic anhydride 3. H2N— (J1-CONH2 15 CH (CH3) 2 4. base '

I - C02H

20 1'I ί ”3 N -—CH (CH3) 2 (njj rj) - * = o ch3 h 25 24 g of diethyl-1-methyl-1H-pyrazolo [3,4-b] pyridine-5,6- the dicarboxylate is heated in 200 ml of an ethanol / water (1: 1) mixture under reflux overnight, after which it is evaporated on a rotary evaporator. The residue is acidified to pH 16 with 6N HCl, cooled and filtered to remove solid diacid product, which is then washed with cold water and air dried. The yield is 32% of crude acid, m.p. 228-229 ° C (decomposes).

55 g of the diacid are stirred in 40 ml of acetic anhydride at 85-90 ° C for 2 hours. The reaction mixture is filtered hot and the filtrate is evaporated under reduced pressure to give the crude anhydride as a resin. The product is dissolved in 50 ml of tetrahydrofuran, then 2-amino-2,3-dimethylbutyramide is added and the mixture is stirred while heating at 40 [deg.] C. for 1.5 hours and then heated under reflux for 16 hours. When the reaction is complete, the mixture is cooled to room temperature and evaporated in vacuo. The residue is dissolved in 100 ml of NaOH solution (10 g / 100 ml) and the resulting solution is stirred at 75-85 ° C for 4 hours. After cooling to room temperature, the reaction mixture is cooled to 10 ° C and acidified to pH 2 with concentrated hydrochloric acid.

The precipitate formed is collected by filtration, dried and purified by column chromatography on silica gel using ethyl acetate / ethanol as eluent to give the title product as a tan solid, m.p. 239-243 ° C.

56 88790

Reference Example 30 7- (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -4H-2,3-dihydro-4-methylpyrrano, [2,3-b] pyridine-6 preparation of carboxylic acid 5 CH3

/ ^ V ^ V-COOH

111 CH3 0 n ^ Y / Nn — CH (CH3) 2 10 HN - * = ° 57. Pd / C, H2

EtOH / K 2 CO 3 back distillation lap 15 ° C

-COOH

I II 1 CH3 O n'Y'Nn-CH (CH3) 2 20 HN -! = 0

The crude 2H-pyranopyridine-imidazolinecarboxylic acid is suspended in 10 ml of water and 10 ml of 15% aqueous potassium carbonate solution are added to this suspension. The substance dissolves to form a bright tan solution. 40 ml of 95% ethanol are slowly added to the solution so that the layers do not separate. To this solution is added 100 mg of 5% / Pd / C and the mixture is stirred in a Parr hydrogenator overnight. The mixture is filtered and evaporated to dryness. The residue is taken up in 50 ml of water and washed with two 25 ml portions of methylene chloride, which are discarded. The aqueous layer is acidified with concentrated HCl to a lead value of 1 while cooling in an ice bath and extracting with five 50 mL portions of methylene chloride.

The combined methylene chloride extracts are dried over anhydrous sodium sulfate, filtered and the solvent is removed under reduced pressure. This gives the product as a glossy, slightly yellowish flocculent solid, m.p. 95-99 ° C.

57 3 8 798

Reference Example 31 3-Isopropyl-3-methyl-7,8-dihydro-5H-pyrano [4,3-b] imidazo] ', 1 1: 5, 1,7pyrrolo [3,4-e] pyridine-2 (2H), preparation of 5-dione N - CH (CH3) 2 10 CH3 ac3o pyridine DM E 15 0Γΐ ^ Ητ ”'“ "! N / n XN-5 = 0 20

To a suspension of 1.17 g (3.75 mmol) of 6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -7,8-dihydro-5H-pyrano / 4,3-b7-pyridinecarboxylic acid in 20 ml of dimethoxyethane (DME), 1.0 ml of acetic anhydride and 0.5 ml of pyridine are added, and after stirring for 24 hours at room temperature, the mixture is filtered: solids and washed with ether and the mother liquor evaporated by the addition of xylene to remove pyridine The residue is triturated with ether and combined with the first crop to give 1.10 g (100%) of product as a solid.

·. ·: Using essentially the same procedure and using an appropriately substituted imidazolinylheteropyridine -...: carboxylic acid, other substituted imidazolopyrroloeteropyridine-2,5-diones or 2-thion-5-ones are obtained.

ss 8879S

Reference Example 32

Preparation of methyl -2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -7,8-dihydro-5H-pyrano [4,3-b] pyridine-3-carboxylate 5 -S CH3? I% - CH (CH3) 2 N '-1 = 0 10 ch3o- ch3oh co2ch3 is y

ο T I

U! y N - (= 0

^) - <N

N N - CH (CH3) 2 ch3 20 To a suspension containing 2.0 g of 2-isopropyl-2-methyl-7,8-dihydro-5H-pyrano [4,3-b] imidazo [2 ', 1 1: 5.1 N-pyrrolo [3,4-b] pyridine-2 (2H), 5-dione in 100 ml of absolute methyl alcohol, 0.2 g of sodium methoxide are added over 5 minutes. The reaction temperature is kept below 30 ° C by keeping the reaction vessel immersed in an ice bath.

After the addition is complete, the reaction mixture is kept at room temperature for 24 hours and acidified with 3 drops of acetic acid and evaporated in vacuo. The product is chromatographed on silica gel using methylene chloride / ethyl acetate as eluent to give 1.55 g of ester product. After recrystallization from methylene chloride / hexane, the product m.p. is 208-220 ° C.

59 8 879ο

Example 1

Following the procedure of Reference Examples 13, 14, 15, 29 and 30 and substituting the appropriate condensed heteropyridine dicarboxylic acid and aminoamide 5, the (imidazolin-2-yl) condensed heteropyridine compounds listed in the following table are obtained.

Table II

(Imidazolin-2-yl) -condensed heteropyridinecarboxylic acids C0ZH γη3 --CH (CH3) 2 15 N f- = °

B

Condensed heteropyridine m.p. ° C

20 (j) CH 3 ·. · '("YS - 170.0 - 173.0

Air * 3H20

OF

CH2CB = CH2 - 164.0 - 166.0

swim

30 N

CH3O- | ^ N— I I 155.0-167.0 \ sK V— ,,. .

- 3s γ N (decomposes) CH3 6α 88798

Table II (continued)

Condensed heteropyridyl m.p. ° C_ 5 <^ H3 215.5 - 218.0 U £

OF

10 I | 264.0 - 266.0 \ A. ^ - y n ch3 15 I 215.0 - 221.0 \ A ^ - y n 20 ch3 <JH3 en

OF

y CH 3

30 ✓ N \ A

f X I 209.0 - 210.0

I-C

OF

35 6ΐ 8 8 79ο

Table II (continued)

Condensed heteropyrldilnl sp. ° C

5 ci —— / 'N— I I 272.0 - 284.0

s A - fjj N

CH3 10 och3 >> - r - 208.0 - 210.0

\ - = - / I I

—K # -

OF

15

Example 2 Using essentially the same procedure as in Reference Example 32 and using an appropriately substituted condensed heteroimidazopyrrolopyridine-2,5-dione and an alcohol, the substituted (imidazolin-2-yl) condensed heteropyridinecarboxylate shown in Table III below is obtained.

62 8879C

Table III

(Imidazolin-2-yl) -condensed heteropyridinecarboxylate 5 H-CO 2 R 8 CH 3 V.E_ (J-N-CH (CH 3) 2 N Y-1 = O

B

10

Condensed heteropyrldine Re_sp. ° C

Jch3 (Xt

OF

Experimental Example 1

Experimental combination of herblsidaallne review using -20 in them after plant seedling emergence

The herbicidal activity of the compounds of the present invention when applied to plants after emergence is demonstrated by the following experiments in which various monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in mixtures of water and acetone. In the experiments, seedlings grown from seed are grown in culture cups (jiffy flats) for about two weeks. The test compounds are dispersed in acetone / water (50:50) mixtures containing 0.5% 30 TWEEN R 20, polyoxyethylene sorbitan monolaurate of the trade name Atlas Chemical Industries, in an amount corresponding to about 0.016 kg to 10 kg of active compound per hectare. applied to the plants at a predetermined time through a spray nozzle operating at a pressure of 2.8 to 35 kg / cm2. After spraying, the plants are placed on l 63 8 8 79ο greenhouse benches and treated in the manner customary in greenhouse cultivation practice. 4-5 weeks after treatment, seedlings grown from seed are examined and graded according to the grading-5 system below. The results obtained are summarized in Table IV below.

In addition, Table IVa shows the experimental results obtained by studying some known compounds (compounds 1-4) as well as some compounds of the invention 10 (compounds 5-7).

Based on the experimental results presented, it can be stated that the compounds according to the invention are much more selective when applied to plant seedlings when used than the known reference compounds.

15

Percentage difference in growth compared to control

Rating system 0 0 0 - no effect 0 1 - possible effect 1-10 2 - weak effect 11-25 3 - moderate effect 26 - 40 5 - clear damage 41 - 60 25 6 - herbicidal effect 61 - 75 7 - good herbicidal effect 76 - 90 8 - effect approaching complete death 91 - 99 9 - complete death 100 4 - abnormal growth, that is, a clear physiological malformation although the overall effect is less than the grade 5 on the rating scale.

In most cases, the results have been obtained from a single experiment, but in many cases they are averages obtained from more than one experiment.

64 8879S

Plant species used

Barnyardgrass (Echinochloa crusgalli)

Green hay (Setaria viridis)

Purple Nutsedge (Cyperus rotundus L.) 5 Wild oats (Avena fatua)

Common wheat (Agropyron repens)

Field rotation (Convolvulus arvensis L.)

Bile grass (Xanthium pensylvanicum) My day (Ipomoea purpurea) 10 Ambrosia artemisiifolia

Velvetleaf (Abutilon theophrasti)

Ohra (Hordeum vulgare)

Maize (Zea mays)

Rice (Oryza sativa) 15 Soybean (Glycine max)

Sunflower (Helianthus annus)

Wheat (Triticum aestivum) i 65 88798 h

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5 Compound * no Amount A ** B C D E

1 0.250 9.0 8.7 9.0 9.0 9.0 0.125 9.0 8.4 9.0 8.9 9.0 2 0.250 9.0 8.5 9.0 8.5 7.5 0.125 9.0 8.3 9.0 7.0 6.3 10 3 0.250 9.0 9.0 9.0 9.0 7.0 0.125 9.0 8.5 9.0 9.0 7.5 4 0.250 9.0 9.0 9.0 9.0 9.0 0.125 9.0 8.3 9.0 9.0 8.0 5 0.250 9.0 6.0 9.0 7.0 1.0 15 0.125 7.0 6.0 9.0 5.0 1.0 6 0.250 9.0 7.0 9.0 8.0 1.0 0.125 9.0 7.0 9.0 7.0 0.0 7 0.250 9.0 8.0 9.0 9.0 0.0 0.125 9.0 8.0 9.0 9.0 0.0 20 * Test compound: 1: 2- (4-isopropyl-4-methyl- 5-Oxo-2-imidazolin-2-yl) nicotinic acid 2: 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-25 yl) -5-methylnicotinic acid 3: 2- (4- Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -6-methylnicotinic acid 4: 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- methoxynicotinic acid 5 5: 3-chloro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2,3-b] pyridine- 5-carboxylic acid 6: 2,3-dihydro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2,3-b ] pyridine-35 5-carboxylic acid 7: 6- (4-isoprop yl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2,3-b] pyridine-5-carboxylic acid ** Experimental plant: 40 A = Panta grass C = Wild Oats E = Soybeans B = Purple Nutsedge D = Downy Wheat

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Experimental Example 2

Herbicidal evaluation of test compounds when used prior to plant seedling growth

The herbicidal activity of the compounds of the present invention when used prior to plant seedling growth is exemplified by the following experiments in which the seeds of several monocotyledonous and dicotyledonous plants are mixed separately with loose soil and sown on the surface of a layer of soil about 10 inches thick. liter cups. After sowing, the cups are sprayed with a selected aqueous acetone solution containing the test compound in an amount corresponding to about 0.016 to 10 kg of test compound per hectare. The treated cups are then placed in plant-15 room benches, watered, and treated according to standard greenhouse care practices. 4-5 weeks after treatment, the experiments are stopped and each cup is examined and graded according to the grading system described above. The herbicidal efficacy of the active agents of the present invention is evident from the experimental results summarized in Table V below. In the event that more than one experiment has been performed with a particular compound, the results are the mean.

In addition, Table Va shows the experimental results obtained by studying some known compounds (compounds 1-4) as well as some compounds of the invention (compounds 5-7). In Table Va, the test compounds and test plants are the same as in Table IVa.

Based on the experimental results presented, it can be stated that the compounds according to the invention are much more selective when used before plant seedling growth than the known reference compounds.

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- Γ0-— - f \ Jio - X5 - o C

'I i liiOL l - - rtj- O >> - «O-OOUio - in + jo --ίλ + j tji C- .5 -o 1 ^ o)> iiy dj>, ii,, χ tD o ΕΞ ex to o ί ~ ex to oo oo e

77 O 8 7 9 O

Table Va

Addition of substances before germination - amounts in kg / ha

5 Compound * no Amount A ** B C D E

1 0.250 9.0 9.0 9.0 9.0 9.0 0.125 9.0 9.0 9.0 9.0 8.7 2 0.250 9.0 9.0 9.0 9.0 8.0 0.125 9.0 9.0 9.0 9.0 7.0 10 3 0.250 9.0 9.0 9.0 9.0 8.5 0.125 9.0 9.0 9.0 9.0 9.0 4 0.250 9.0 9.0 9.0 9.0 8.0 0.125 9.0 9.0 9.0 9.0 8.0 5 0.250 6.0 9.0 9.0 8.0 1.0 15 0.125 6.0 6.0 9.0 6.0 1.0 6 0.250 9.0 9.0 9.0 9.0 1.0 0.125 9.0 9.0 9.0 9.0 0.0 7 0.250 9.0 7.0 9.0 9.0 1.0 0.125 9.0 8.0 9.0 9.0 0.0 20 * Test compound: see Table IVa ** Test plant: see Table IVa

Claims (16)

1. With the (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group substituted pyrrolopyridinecarboxylic acid derivatives of formula II <XC00R8 (II, H A is H 1 R 3 is C 1-6 alkyl, C 1-4 alkoxy or C 3-6 alkenyloxy; R 4 is hydrogen, C 1-6 alkyl or phenyl; R 7 is hydrogen, halogen or C 1-4 alkoxy and R 8 is hydrogen; C 1-4 alkyl optionally substituted with furyl; or propynyl; And acid-acceptable salts and optical isomers thereof in agriculture. A compound according to claim 1 which is 2,3-dihydro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2, 3-b] pyridine-5-carboxylic acid. 30 A compound according to claim 1, which is 1-methoxy-5- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1H-pyrrolo [3,2-b] pyridine 6-carboxylic acid. The compound of claim 1, which is 1-allyloxy-5- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1H-pyrrolo [3,2-b] pyridine -6-carboxylic acid. 84 38798 A compound according to claim 1, which compound is 3-chloro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2,3- b] pyridine-5-carboxylic acid. The compound of claim 1, which compound 5 is 3-chloro-5- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methoxy-ΙΗ-pyrrolo [3.2 b] pyridine-6-karboxy1syra. The compound of claim 1, which is 5- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methoxy-2-methyl-1H-pyrrolo [3, 2-b] pyridine-6-carboxylic acid. 10 The compound of claim 1, which is 6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [2,3-b] pyridine-5-carboxylic acid. The compound of claim 1, which is 5- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-1H-pyrrolo [3,2-b ] pyridine-6-carboxylic acid. A process for controlling the growth of monocotyledons and dicotyledons, the growth of annuals, perennials and aquatic plants, characterized in that the foliage of the plants or in the soil or in water containing seeds of said plants or other organs which promote their spread is propagated. herbicidally effective amount of a compound of formula II <RTI ID = 0.0> R8 (II) </RTI> ch (ch3) 2H0 and A and R8 are the same as in claim 1. 11. A process according to claim 10, characterized in that the compound of formula II is 2,3-dihydro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl -LH-pyrrolo [2,3-b] pyridine-5-carboxylic acid. i 85 n 8 7 9 s Process according to claim 10, characterized in that the compound of formula II is 3-chloro-6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl -LH-pyrrolo [2,3-b] pyridine-5-carboxylic acid. 5 Process according to claim 10, characterized in that the compound of formula II is 6- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -1-methyl-ΙΗ-pyrrolo [ 2,3-b] pyridine-5-carboxylic acid. A process for the preparation of herbicidal, 10 with (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) group substituted pyrrolopyridinecarboxylic acid derivatives of formula II Wherein H and R8 are the same as in claim 1, characterized in that a compound of formula XXII <f "VC00H CH3-CONH C-C0NH2 (xxii) ch (ch3) wherein A is the same as above, with an aqueous solution of sodium or potassium hydroxide or with an aqueous C1-6 alcohol solution using 2-20 moles of this per one mole of the compound of formula XXII, at a temperature of 25 - 110 ° C, by acidifying the reaction mixture formed there to a pH of 2-4 with hydrochloric or sulfuric acid, by extracting the acidified reaction mixture with an organic solvent and by separating the solvent from the reaction mixture to obtain an acid product of formula II wherein R is H; and, if desired, the thus-obtained acid product of formula II, wherein R l X, \ CK3 AJ N -— CH (CHj) 2 NXmX- (VI) - (= o where A denotes the same as above, or with an equivalent of dicyclohexylcarbodimide in an inert solvent to form an imidazopyrroloheteropyridine dione of formula XIV xVA 25. in N n (xiv) N ---- CH ACH (CH3) Jri where A is the same as above, reacting the thus obtained imidazopyrroloheteropyridine dione of formula VI or XIV with an alcohol or corresponding alkali metal alkoxide at a temperature of between about 20 ° C to about 50 ° C. to obtain an ester of formula II, wherein R 8 represents nothing but hydrogen.