HERBICIDAL AMIDES

Abstract

The present invention relates to amides of formula (I), wherein the variables are defined according to the description, process for preparation, their use as herbicides, i.e. for controlling harmful plants, and also a method for controlling unwanted vegetation which comprises allowing a herbicidal effective amount of at least one amide of formula (I) to act on plants, their seed and/or their habitat.

##STR00001##

Claims

1. Amides of formula (I) ##STR00025## wherein the variables have the following meanings: R.sup.1 OH, ═O or O(CO)R.sup.6, wherein R.sup.6 is H or C.sub.1-C.sub.6-alkyl; R.sup.2 H or (CO)R.sup.7; wherein R.sup.7 is H or C.sub.1-C.sub.6-alkyl; R.sup.3 H or (CO)R.sup.8; wherein R.sup.8 is H or C.sub.1-C.sub.6-alkyl; or R.sup.2 and R.sup.3 together form -CR.sup.9R.sup.10-, wherein R.sup.9 and R.sup.1° independently of one another are H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy; R.sup.4 H; R.sup.5 C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-haloalkenyl, C.sub.3-C.sub.6-alkynyl or C.sub.3-C.sub.6-haloalkynyl; or R.sup.4 and R.sup.5 together form a 5- to 6-membered saturated heterocycle, which is substituted with one carbonyl group, optionally has in addition to the N-atom one ring member selected from the group consisting of —N—, —O— and —S—, and optionally is substituted with one or two substituents selected from C.sub.1-C.sub.3-alkyl and C.sub.1-C.sub.3-haloalkyl.

2. Amides of formula (I) according to claim 1, wherein R.sup.1 is OH or ═O.

3. Amides of formula (I) according to claim 1 or 2, wherein R.sup.1 is OH.

4. Amides of formula (I) according to any of claims 1 to 3, wherein R.sup.2 and R.sup.3 are independently of one another H, (CO)H or (CO)CH.sub.3, or together form —CR.sup.9R.sup.10—, wherein R.sup.9 is C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy; and R.sup.10 is H or C.sub.1-C.sub.6-alkyl.

5. Amides of formula (I) according to any of claims 1 to 4, wherein R.sup.5 is C.sub.2-C.sub.6-haloalkyl, C.sub.3-C.sub.6-haloalkenyl or C.sub.3-C.sub.6-alkynyl, or R.sup.4 and R.sup.5 together form a 5-membered saturated heterocycle, which is substituted with one carbonyl group, optionally has in addition to the N-atom one ring member selected from the group consisting of —N—, —O— and —S—, and optionally is substituted with one or two substituents selected from C.sub.1-C.sub.3-alkyl and C.sub.1-C.sub.3-haloalkyl.

6. Amides of formula (I) according to claim 1, wherein the amide is the amide of formula (I.1) ##STR00026## wherein the variables R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined in claim 1.

7. Process for the preparation of amides of formula (I) as defined in claim 1, wherein an acid of formula (III) ##STR00027## wherein R.sup.1, R.sup.2 and R.sup.3 are as defined in claim 1; are reacted with an amine of formula (II)
HNR.sup.4R.sup.5  (II) wherein R.sup.4 and R.sup.5 are as defined in claim 1.

8. A herbicidal composition comprising an herbicidally active amount of at least one amide of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substance.

9. A process for the preparation of herbicidal compositions, which comprises mixing an herbicidally active amount of at least one amide of formula (I) as claimed in claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surface-active substance.

10. A method of controlling undesired vegetation, which comprises allowing an herbicidally active amount of at least one amide of formula (I) as claimed in claim 1 to act on plants, their environment or on seed.

11. The use of amides of formula (I) as claimed in claim 1 as herbicides.

Description

A PREPARATION EXAMPLES

Example 1 (Table 1 Compound 26)

(E)-4-[(2S,3R,4R,5S)-3,4-dihydroxy-5-[[(2S,3S)-3-[(1S,2S)-2-hydroxy-1-methyl-propyl]oxiran-2-yl]methyl]tetrahydropyran-2-yl]-3-methyl-N-prop-2-ynyl-but-2-enamide

[0310] ##STR00016##

[0311] Modified procedure from U.S. Pat. No. 4,237,161:

[0312] To a solution of pseudomonic acid (CAS 12650-69-0; 20 g, 40 mmol) in HC(OEt).sub.3 (100 mL) was added TsOH*H2O (5mg) at 15° C. The mixture was stirred at 15° C. for 12 h. The mixture was concentrated in vacuum to give the corresponding ortho-ester (crude in HC(OEt).sub.3). The crude product was used directly for the next step.

[0313] To a solution of the ortho-ester (crude in HC(OEt).sub.3) in H2O (400 mL) was added NaOH (16 g, 0.4 mol) in H2O at 0° C. dropwise. The mixture was stirred at 65° C. for 24 h under N2. The mixture was adjusted to pH=8 with 1N H.sub.2SO.sub.4 and concentrated to give the monic acid ortho ester (80 g, crude).

[0314] To a solution of the crude monic acid ortho ester (150 g, 300 mmol) was added propargylamine (33 g, 600 mmol), HATU (228 g, 600 mmol) and Na.sub.2CO.sub.3 (63.6 g, 600 mmol) in DMF (2 L) and stirred at 15° C. for 12 h. The mixture was poured into ice water, extracted with EtOAc, washed with brine, dried, filtered and evaporated to give the corresponding amide (90 g, crude). The solution of the crude amide (40 g, 74.2 mmol) in MeOH (400 mL) and H.sub.2O (200 mL) was adjusted to pH=2 with 1N HCl. The mixture was stirred at 0° C. for 1 h. Then the mixture was adjusted to pH=9 with aqueous Na.sub.2CO.sub.3 and stirred for 3 h at 0° C. and adjusted to pH=8 with 1N HCl. The resulting mixture was concentrated at 20° C. to give the crude product. It was purified by preparative HPLC (neutral, MeCN—H.sub.2O) to give (E)-4-[(2S,3R,4R,5S)-3,4-dihydroxy-5-[[(2S,3S)-3-[(1S,2S)-2-hydroxy-1-methyl-propyl]oxiran-2-yl]methyl]tetrahydropyran-2-yl]-3-methyl-N-prop-2-ynyl-but-2-enamide (10.1 g,35.7%) as a white solid.

[0315] .sup.1HNMR (400 MHz, methanol-d4): δ (ppm) 5.74 (s, 1H), 3.96 (d, J=2.5 Hz, 2H), 3.89-3.84 (m, 2H), 3.82-3.70 (m, 2H), 3.55 (dd, J=1.6, 11.5 Hz, 1H), 3.35 (dd, J=3.1, 9.0 Hz, 1H), 2.81 (dt, J=2.2, 5.8 Hz, 1H), 2.71 (dd, J=2.2, 7.6 Hz, 1H), 2.60 (br d, J=13.9 Hz, 1H), 2.55 (t, J=2.5 Hz, 1H), 2.20-2.13 (m, 4H), 1.96 (dt, J=4.1, 6.7 Hz, 1H), 1.68 (t, J=6.6 Hz, 2H), 1.44-1.37 (m, 1H), 1.20 (d, J=6.5 Hz, 3H), 0.95 (d, J=7.2 Hz, 3H)

Example 2 (Table 1 Compound 35)

3-[(E)-4-[(2S,3R,4R,5S)-3,4-dihydroxy-5-[[(2S,3S)-3-[(1S,2S)-2-hydroxy-1-methyl-propyl]oxiran-2-yl]methyl]tetrahydropyran-2-yl]-3-methyl-but-2-enoyl]-5,5-dimethyl-oxazolidin-2-one

[0316] ##STR00017##

[0317] To a mixture of the crude monic acid ortho ester (procedure see above; 5 g, 10 mmol) in THF (150 mL) was added DMAP (1.22 g, 10 mmol) and HATU (11.4 g, 30 mmol) and stirred at 15° C. for 48 h to give suspension A.

[0318] To a mixture of NaH (60%, 1.6 g, 40 mmol) in THF (150 mL) was added 5,5-dimethyloxazolidin-2-one (5.75 g, 50 mmol) and stirred at 60° C. for 3 h to give suspension B.

[0319] The suspension B was added to suspension A and the resulting mixture was stirred at 15° C. for 12 h. The mixture was poured into ice water, extracted with MTBE, washed with brine, dried, filtered and concentrated to give the crude amide (5 g, crude) as a yellow solid.

[0320] To a solution of crude amide (5 g, 8.3 mmol) in THF (50 mL) and H.sub.2O (25 mL) was added 1N HCl adjust to pH=2. The mixture was stirred at 0° C. for 1 h. Then the mixture was adjusted to pH=9 with aqueous Na2CO3 and stirred for 3 h at 0° C. and adjusted to pH=8 with 1N HCl. The resulting mixture was concentrated at 15° C. to give the crude product. The product was purified by preparative HPLC (neutral, MeCN—H.sub.2O) to give 3-[(E)-4-[(2S,3R,4R,5S)-3,4-dihydroxy-5-[[(2S,3S)-3-[(1S,2S)-2-hydroxy-1-methyl-propyl]oxiran-2-yl]methyl]tetrahydropyran-2-yl]-3-ethyl-but-2-enoyl]-5,5-dimethyl-oxazolidin-2-one (450 mg, 12%) as a white solid.

[0321] .sup.1H NMR (400 MHz, methanol-d4): δ (ppm) 7.00 (s, 1H), 3.94-3.84 (m, 2H), 3.83-3.75 (m, 4H), 3.55 (br d, J=13.1 Hz, 1H), 3.40 (dd, J=3.0, 8.9 Hz, 1H), 2.81 (dt, J=2.2, 5.8 Hz, 1H), 2.74-2.66 (m, 2H), 2.34-2.26 (m, 1H), 2.19 (s, 3H), 1.96 (br d, J=3.4 Hz, 1H), 1.73-1.62 (m, 2H), 1.48 (s, 6H), 1.41-1.38 (m, 1H), 1.23-1.18 (m, 3H), 0.95 (d, J=7.2 Hz, 3H)

[0322] The compounds listed below in tables 1 to 3 can be prepared similarly to the examples mentioned above:

##STR00018##

TABLE-US-00002 TABLE 1 m/z R.sub.t no. R.sup.2 R.sup.3 R.sup.4 R.sup.5 [M + H] [min] 1 H H H CH.sub.2CH.sub.2F 389.9 0.664 2 H H H CH.sub.2CHF.sub.2 408.0 0.706 3 H H H CH.sub.2CF.sub.3 425.9 0.770 4 H H H CH.sub.2CH.sub.2CHF.sub.2 422.0 0.732 5 H H H CH.sub.2CH.sub.2CF.sub.3 440.0 0.788 6 H H H CH.sub.2CF.sub.2CH.sub.3 422.0 0.748 7 H H H CH.sub.2CF.sub.2CHF.sub.2 458.0 0.795 8 H H H CH.sub.2CF.sub.2CF.sub.3 476.0 0.869 9 H H H CH.sub.2CF.sub.2CF.sub.2CF.sub.3 526.0 0.954 10 (CO)H H H CH.sub.2CHF.sub.2 11 (CO)H (CO)H H CH.sub.2CHF.sub.2 463.9 0.810 12 (CO)H (CO)H H CH.sub.2CF.sub.3 482.0 0.938 13 —C(CH.sub.3).sub.2— H CH.sub.2CH.sub.2F 430.1 0.956 14 —C(CH.sub.3).sub.2— H CH.sub.2CHF.sub.2 448.1 0.959 15 —C(CH.sub.3).sub.2— H CH.sub.2CF.sub.3 466.1 1.069 16 —C(CH.sub.3).sub.2— H CH.sub.2CF.sub.2Br 526 1.114 17 —C(CH.sub.3).sub.2— H CH.sub.2CF.sub.2CH.sub.3 462.2 1.020 18 —C(CH.sub.3).sub.2— H (S)—CH(CH.sub.3)(CF.sub.3) 480.1 1.117 19 —C(CH.sub.3).sub.2— H CH.sub.2CF.sub.2CF.sub.2CF.sub.3 566 1.213 20 —CH(OC.sub.2H.sub.5)— H CH.sub.2CF.sub.3 482.0 0.834 21 H H H CH.sub.2CH═CCl.sub.2 451.9 0.859 22 H H H CH.sub.2CF═CH.sub.2 401.9 0.726 23 —C(CH.sub.3).sub.2— H CH.sub.2CF═CH.sub.2 442.1 0.987 24 —C(CH.sub.3).sub.2— H CH.sub.2CCl═CH.sub.2 458.1 1.027 25 —C(CH.sub.3).sub.2— H CH.sub.2CBr═CH.sub.2 502.1 1.042 26 H H H CH.sub.2C≡CH 382.0 0.679 27 H H H CH.sub.2C≡CCH.sub.3 396.0 0.735 28 H H H CH(CH.sub.3)C≡CH 396.0 0.734 29 H H H CH.sub.2C≡CC(CH.sub.3).sub.3 438.1 0.931 30 H H H CH.sub.2CH.sub.2C≡CH 396.0 0.709 31 —C(CH.sub.3).sub.2— H CH.sub.2C≡CH 422.0 0.939 32 —C(C.sub.2H.sub.5).sub.2— H CH.sub.2C≡CH 450.1 1.068 33 —CH(OC.sub.2H.sub.5)— H CH.sub.2C≡CH 438.1 0.743 34 H H —(CO)OCH.sub.2CH.sub.2— 414.0 0.716 35 H H —(CO)OC(CH.sub.3).sub.2CH.sub.2— 442.0 0.833 36 H H —(CO)OCH(CF.sub.3)CH.sub.2— 482.0 0.867 37 H H —(CO)SCH.sub.2CH.sub.2— 429.9 0.798 38 H H —(CO)N(CH.sub.3)CH.sub.2CH.sub.2— 427.0 0.718 39 —C(CH.sub.3).sub.2— —(CO)SCH.sub.2CH.sub.2— 469.9 1.075 40 —C(CH.sub.3).sub.2— —(CO)N(CH.sub.2CF.sub.3)CH.sub.2CH.sub.2— 535.3 0.917 41 —C(CH.sub.3).sub.2— —(CO)N(CH.sub.3)CH.sub.2CH.sub.2— 466.9 0.974

##STR00019##

TABLE-US-00003 TABLE 2 m/z R.sub.t no. R.sup.2 R.sup.3 R.sup.4 R.sup.5 [M + H] [min] 42 H H H CH.sub.2CHF.sub.2 405.9 0.732 43 H H H CH.sub.2CF.sub.3 423.9 0.800 44 (CO)H (CO)H H CH.sub.2CHF.sub.2 45 —C(CH.sub.3).sub.2— H CH.sub.2CHF.sub.2 445.0 1.018 46 —C(CH.sub.3).sub.2— H CH.sub.2CF.sub.3 463.9 1.075 47 (CO)CH.sub.3 (CO)CH.sub.3 H CH.sub.2C≡CH 508.1 1.120 48 —CH(OC.sub.2H.sub.5)— H CH.sub.2C≡CH 436.1 0.793

##STR00020##

TABLE-US-00004 TABLE 3 m/z R.sub.t no. R.sup.2 R.sup.3 R.sup.4 R.sup.5 [M + H] [min] 49 (CO)H (CO)H H CH.sub.2CHF.sub.2 492.0 0.986 50 (CO)H (CO)H H CH.sub.2CF.sub.3 509.9 1.040

B USE EXAMPLES

[0323] The herbicidal activity of the amides of formula (I) was demonstrated by the following greenhouse experiments:

[0324] The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

[0325] For the pre-emergence treatment, the active ingredients, which had been suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover caused uniform germination of the test plants, unless this had been impaired by the active ingredients.

[0326] For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment.

[0327] Depending on the species, the plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

[0328] Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. A good herbicidal activity is given at values of at least 80 and a very good herbicidal activity is given at values of at least 90.

[0329] The plants used in the greenhouse experiments were of the following species:

TABLE-US-00005 Bayer code Scientific name ABUTH Abutilon theophrasti ALOMY Alopercurus myosuroides AMARE Amaranthus retroflexus AVEFA Avena fatua CHEAL Chenopodium album ECHCG Echinocloa crus-galli RAPRA Raphanus raphanistrum SEBEX Sesbania exaltata SETFA Setaria faberi SETVI Setaria viridis

[0330] At an application rate of 500 g/ha, compound 29 applied by the pre-emergence method, showed good herbicidal activity against SETFA.

[0331] At an application rate of 500 g/ha, compounds 8, 9 and 27 applied by the pre-emergence method, showed good herbicidal activity against ECHCG.

[0332] At an application rate of 500 g/ha, compound 33 applied by the pre-emergence method, showed good herbicidal activity against AMARE.

[0333] At an application rate of 500 g/ha, compounds 34 and 43 applied by the pre-emergence method, showed very good herbicidal activity against ECHCG.

[0334] At an application rate of 500 g/ha, compounds 1, 3, 4, 5, 6, 7, 8, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26, 27, 31, 32, 33, 34, 35, 38, 50, 45, 46, 47 and 48 applied by the post-emergence method, showed very good herbicidal activity against ECHCG, SETVI, ABUTH and AMARE.

[0335] At an application rate of 500 g/ha, compounds 2, 21, 28, 29 and 40 applied by the post-emergence method, showed very good herbicidal activity against SETVI, ABUTH and AMARE, and good herbicidal activity against ECHCG.

[0336] At an application rate of 500 g/ha, compounds 11 and 49 applied by the post-emergence method, showed very good herbicidal activity against SETVI, ABUTH and AMARE, and good herbicidal activity against ALOMY.

[0337] At an application rate of 500 g/ha, the compounds 36 and 41 applied by the post-emergence method, showed very good herbicidal activity against SETVI, ABUTH and AMARE.

[0338] At an application rate of 500 g/ha, compound 9 applied by the post-emergence method, showed very good herbicidal activity against SETVI and AMARE, and good herbicidal activity against ECHCG.

[0339] At an application rate of 500 g/ha, compound 19 applied by the post-emergence method, showed very good herbicidal activity against AMARE.

[0340] At an application rate of 500 g/ha, compound 20 applied by the post-emergence method, showed very good herbicidal activity against ECHCG, ABUTH and AMARE.

[0341] At an application rate of 500 g/ha, compound 37 applied by the post-emergence method, showed very good herbicidal activity against SETVI and ABUTH, and good herbicidal activity against ECHCG and AMARE.

[0342] At an application rate of 500 g/ha, compound 39 applied by the post-emergence method, showed very good herbicidal activity against SETVI and ABUTH.

[0343] At an application rate of 500 g/ha, compound 43 applied by the post-emergence method, showed very good herbicidal activity against SETVI, ABUTH and AVEFA.

[0344] Tables 4 and 5: Comparison of the herbicidal activity of example 1 (compound 26) of the present invention

##STR00021##

and compound no. 77 known from WO 93/19599

##STR00022##

TABLE-US-00006 TABLE 4 (post-emergence application; greenhouse) compound example 1 (cmpd 26) cmpd 77 (WO 93/19599) application rate [g/ha] 500 500 damages unwanted plants ALOMY 95 70 AVEFA 98 50 SETVI 100 85

TABLE-US-00007 TABLE 5 (post-emergence application; greenhouse) compound example 1 (cmpd 26) cmpd 77 (WO 93/19599) application rate [g/ha] 8 8 damages unwanted plants CHEAL 100 75 RAPRA 100 85 SEBEX 100 65

[0345] The replacement of the —CH.sub.2OH group by a C≡CH group at the side chain leads to a better herbicidal activity, not only at higher, but also at lower application rates compared to the results achieved by the compound 77 known from WO 93/19599.

[0346] Tables 6 and 7: Comparison of the herbicidal activity of compound 1 of the present invention

##STR00023##

and compound no. 77 known from WO 93/19599

##STR00024##

TABLE-US-00008 TABLE 6 (post-emergence application; greenhouse) compound cmpd 1 cmpd 77 (WO 93/19599) application rate [g/ha] 500 500 damages unwanted plants ALOMY 100 70 SETVI 100 85

TABLE-US-00009 TABLE 7 (post-emergence application; greenhouse) compound cmpd 1 cmpd 77 (WO 93/19599) application rate [g/ha] 8 8 damages unwanted plants CHEAL 100 75 RAPRA 100 85

[0347] The replacement of the —CH.sub.2OH group by a CH.sub.2F group at the side chain leads to a better herbicidal activity, not only at higher, but also at lower application rates compared to the results achieved by the compound 77 known from WO 93/19599.

[0348] Consequently, the data in tables 4, 5, 6 and 7 clearly demonstrate the superior herbicidal activity of the inventive compounds of formula (I) of the present invention over the compounds known from the prior art.