JPS6058961A - Herbicidal composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention relates to the field of herbicides, and more particularly to the field of herbicides.
or 6-fluorinated methyl-dihydropyridine-3,5-
Concerning the field of dicarboxylic acid esters.

Various dihydropyridines are known in the art and have been utilized for various purposes. For example, U.S. Pat.
No. 69,359 discloses 6,5-dicyano-1,4-dihydropyridine, which is commercially useful in scintillation applications as a detection agent for radioactive radiation.

Dihydropyridines have been utilized for pharmaceutical purposes, as exemplified by US Pat. No. 5,441,648, which published a number of 1,4-dihydropyridines. Of particular interest are 3,5 with 2.6 substituents
- dicarboxylate compounds. Such compounds may be used to lower blood pressure when administered internally. The most active compounds appear to be those substituted at the 4-position by an aryl or heterocyclic group (the heteroatoms being nitrogen, sulfur, and also Vi oxygen). Also 4
The trifluoromethylphenyl group in position appears to be highly active in lowering blood pressure in animals.

More relevant here is 2j6-bis(trifluoromethyl)-3,5-dicarpoethoxylj4
- A method for producing 4-substituted rust conductors of dihydropyridine was disclosed in Borland Patent No. 89 by BaliCki et al.
, 493.

According to the Borland patent specification, these compounds have not yet been reported in the literature and the metals thus prepared have valuable pharmacological properties, including cytotoxicity and cytotoxic properties.
It has bacteriostatic and antihypertensive applications, and is also an intermediate in the synthesis of novel substituted heterocyclic compounds. According to this patent, such a compound is prepared by converting an alkyl group, substituted or unsubstituted aryl group or heterocyclic group (heteroatoms are (representing nitrogen, oxygen or sulfur)] with ethyl trifluoroacetoacetate. The equivalent of 1 mole of aldehyde is reacted with the equivalent of 2 moles of 6-kedoester in aqueous ammonia in the presence of an organic solvent, preferably a lower aliphatic alcohol.

The compounds thus obtained have been identified only by their melting points.

However, Singh et al.
Ourna'l Of 1 (eterocycxic
Chemistry, Volume 17, 1109 and 11
On page 10, it was further reported that the compound actually prepared by Balikai et al. was actually dihydroxypiperidine, which is the least dihydropyridine. Singh et al. reported that they conclusively showed that the product formed by reacting ethyl trifluoroacetoacetate with a concentrated aqueous solution of an aromatic aldehyde and ammonia does not have a dihydropyridine structure but is rather a substituted piperidine. ing.

Singh reported that Barikai et al.'s oxidation of the reaction product with nitric acid and several other reagents was unsuccessful in converting the reaction product to the corresponding pyridine. As pointed out in the publications of Singh et al., this oxidation method has 1,
Although commonly used to convert 4-dihydropyridine to the corresponding pyridine, the fact that such a conversion did not occur indicates that the reaction products 75f1,4-dihydropyridines of the process described by Balikai were not. This shows that

Balikai et al. reported that 2,6-bis-trifluoromethyl-4-
To further demonstrate the lack of success in teaching the preparation of substituted-1j4-dihydropyridine-6°5-dicarboxylic acid esters, we provide a series of compounds with structure 1 and Tested to determine melting point. The melting points of compounds 1 and 2 prepared by the inventors were compared to the melting points reported by Balikai et al. and the compounds made as reported by them.

The results are shown in Table ■ below.

Table ■ 1 λ 5 1 2 Reported value c) 13 1.4394 133-135 163-1
34O,,H51,4441129-131131-1
3203H Fu 1.4427' 140-142 1 Roro 2-1 Roro 2-Frill 1.4721 129-130
128-1292-chenyl 1.434 103-
1054-pyridyl 171-172 179 177
-178 Phenyl 42-45 99-101 92-
93a-r]D The data in Table 1 provide evidence that the compound reported by Balikai et al. is in fact a dihydroxypiperidine and not a dihydropyridine.

Barikai etc. are from later publications (polish Journal).
of QbemiStr 712439, 1981), the structural assignment of the product derived from ethyl trifluoroacetate, aldehyde v1 and aqueous ammonia has been corrected as compound 2.

Dihydroxypiperidine 2 made by the method described by Balikai et al. has structure A (72
isomer) and B (trans isomer), consisting of a mixture of cis and trans isomers. The structure of the compound prepared by Balikai's method was further confirmed to be dihydroxypiperidine by X-ray crystallography. The isomer mixture prepared by the method of Balikai et al. can be further purified by recrystallization, yielding predominantly one isomer. Generally, the products currently obtained by the method of Balikai et al. have melting points higher than the reported melting points. What about this?
This is because a more careful purification of the isomer mixture yielded a single cis isomer.

00Et Δ Ha U.S. Pat. No. 4,145,432 discloses 1,4-dihy V-mouth lysines useful as pharmaceutical compositions for the treatment of cardiovascular disease and hypertension in humans.

The active compound is a 3,5-dicarboxylic acid ester, but the 4-position is occupied by an aryl or heterocyclic group. Moreover, the 2- and 6-positions of the dihydropyridine ring
The position is occupied by a group selected from a wide variety of groups, including lower alkyl and substituted lower alkyl groups. Published intermediate compounds contain 2,6-halo(lower)alkyl substitutions. Furthermore, German Patent No. 2.659.665 describes 1 containing 5-cyano, 3-carboxylate substitution and 2,6-dialkyl substitution as a coronary vasodilator.
, 4-dihydropyridine derivatives have been reported. The 4-position of these compounds is occupied by a nitrophenyl group.

1 containing anilide in the specification of European Patent No. 44,262
, 4-dihydropyridine have been reported.

However, among these reported compounds, the 4-position also contains hanmushipo) 14 ri/r'rshit-
) None contain a heptal group.

Summary of the Invention The present invention relates to herbicidally active compounds, intermediates for producing herbicidally active compounds, processes for producing the compounds, herbicidal compositions containing these compounds, and herbicidal uses of the compositions using agricultural millet crop traps. It is. [wherein R is phenyl, alkyl, 03-c6 cycloalkyl, haloalkyl, lower alkoxyalkyl, aralkoxyalkyl, aryloxyalkyl, lower alkylthioalkyl, lower alkylcarbonyloxyalkyl, hydroxyalkyl, cycloalkanylalkyl, selected from the group consisting of heterocyclic groups (having 3 to 6 atoms in the ring, 1 to 3 of which are selected from nitrogen, sulfur, and oxygen), and each R1 is selected from 01 to 4 alkyl groups; independently selected and each R2 is independently selected from fluorinated methyl, R3
selected from alkyl and fluorinated methyl groups].

"Alkyl" herein refers to both straight-chain and branched chains.
6F/L4 and includes, for example, ethyl, methyl, propyl, n-butyl, pentyl, hexyl, isobutyl, isozorovir, 1-methylpropyl, neopentyl and 1-ethylpropyl. "03~
6 Cycloalkynoyl is cyclopropyl, cyclobutyl,
Refers to cycloalkyl groups such as cyclopentyl and cyclohexyl. Typical lower alkoxyalkyl groups include methoxymethyl, ethoxymethyl and ethoxyethyl. Typical aralkoxyalkyl groups include phenylmethoxymethyl. Typical aryloxyalkyl groups include phenoxyalkyl. Lower alkylthioalkyl groups include the thio equivalents of the lower alkoxyalkyl groups described above.

Typical heterocyclic groups include furyl, pyridyl, and chenyl.

"Haloalkyl" means an 01-6 alkyl group substituted with one or more halodane atoms. Typical columns include fluoromethyl, chloromethyl, difluoromethyl,
difluoroethyl, bromomethyl, iodomethyl, dichloromethyl, dichloroethyl, and dibromomethyl,
Trifluoromethyl, 2-()lifluoromethyl)propyl and chlorofluorinated alkyl groups are combined.

"Cycloalkanylalkyl" means an alkyl substituted with a cycloalkyl group.

"Fluorinated methyl" means a methyl group with one or more fluorine atoms attached, including replacement of all hydrogen atoms by fluorine. The term is also intended to include methyl groups in which one or more hydrogen atoms have been replaced by chlorine atoms, provided that the methyl group has one or more fluorine atoms attached to it. Typical examples include fluoromethyl, difluoromethyl, and trifluoromethyl groups, chlorodifluoromethyl, dichlorofluoromethyl, and the like.

"1,2-dihydropyridine" herein means a dihydropyridine having a ring nitrogen and a hydrogen atom attached to an adjacent carbon atom, and in chemical nomenclature is 1,6
It refers to a common dihydropyridine called dihydropyridine.

The dihydropyridine of the present invention having the above formula 3j or 4 is prepared by converting the corresponding dihydroxypiperidine into a suitable dehydrating agent such as, but not limited to, (1) sulfuric acid, (2)
It can be obtained by dehydration with toluenesulfonic acid or (3) trifluoroacetic anhydride. Typical dihydroxypiperidines are obtained from the corresponding tetrahydrobilanes by treatment with aqueous ammonia or gas. To obtain the desired dihydroxypiperidine, a suitable aldehyde is reacted with a suitable 3-ketoester and a catalytic amount of piperidine in a suitable reaction medium. This reaction gives tetrahydrobyran, from which piperidine is obtained, which in turn gives dihydropyridine upon dehydration as described above. This production method will be further explained by the following reaction scheme.

When preparing a dihydropyridine compound in which the 4-position is substituted with arylmethyl, phenylmethoxymethyl, or a heterocyclic group (where the petro atom is oxygen or sulfur), a catalytic amount may be used instead of a common inorganic acid as a dehydrating agent. It is best to use organic acids. Typical VCs, such as toluenesulfonic acid in a reaction medium of toluene, have been found to be suitable for this purpose. This reaction is generally carried out at reflux temperature. Higher amounts of 3.4- from the corresponding piperidine
Trifluoroacetic anhydride is a particularly suitable dehydrating agent for obtaining dihydropyridine isomers. The reaction medium in such processes is typically a chlorinated hydrocarbon such as methylene chloride.

Although the reaction diagram above includes several consecutive reactions, the method of the present invention allows dihydropyridine to be produced in a single reaction mixture. In this manufacturing method,
As described in detail below, the reaction products are processed sequentially until the desired product is finally isolated from the reaction mixture. The improved one-vessel reaction provides the desired product in higher yields than the convergence possible with multi-step processes.

According to the novel process according to the invention, a suitable 6-keto ester of the formula %, where R1 and R2 are as defined above, can be converted into a suitable 6-ketoester of the formula
R is defined above)
react first. This reaction occurs under atmospheric pressure and at a temperature generally within the range of about 4,000 to about 10,000 degrees Celsius. Optionally, an aprotic solvent such as methylene chloride or toluene or any suitable solvent for the initial reaction can be used. For example, ammonia gas or ammonium hydroxide is added to the reaction mixture when the reaction between the ro-keto ester and the aldehyde is complete, as shown by NMR analysis. If a solvent was not used previously, add it prior to the ammonia gas. It is common to use an approximately two to ten times excess of ammonia over the amount required for the conversion of tetrahydrobyran. After the addition of ammonia or ammonium hydroxide to the reaction mixture is complete, the ammonia may be removed from the reaction mixture or excess ammonium hydroxide may be flushed from the reaction mixture. Although this purging step is not necessary, it will eliminate the possibility of reaction between the ammonia and the dehydrating agent. The final step in nature is the addition of a suitable dehydrating agent to the reaction mixture, thereby converting the dihydroxy 2-veridine to the corresponding dihydropyridine. A particularly suitable dehydrating agent when the 4-position of the dihydroxy 2-veridine is alkyl is sulfuric acid, although any suitable dehydrating agent can be used. Sulfuric acid is particularly good because it has a high reaction rate. Other suitable dehydrating agents are described above.

After dehydration to form the desired dihydropyridine from dihydroxy and piperidine, the product is isolated from the reaction mixture by conventional methods.

The 1,2 dihydropyridine of formula 5 above is prepared by reduction of a correspondingly substituted pyridine. The pyridine compounds can be prepared from the 1,4- and 6,4-dihydrobiridines described above, using sodium nitrate in acetic acid, if the desired pyridine must have the same number of fluorine atoms on each R2 as in the starting dihydropyridine, or 2.3-dichloro-5,
It is made by oxidation with any oxidizing agent such as 6-dicyano-1,4-benzoquinone, dichromic oxide in acetic acid, and the like. If one of the fluorinated methyl groups must have one less fluorine atom than R2 in the original dihydrogiridine, the conversion to pyridine can be carried out using an organic base, such as 1,8-cyazubicyclo-[5, 4,0]-Undec-7-ene, trialkylamine, pyridine, mono-, di- and trialkyl-substituted pyridine in pure form or in a suitable solvent at elevated temperatures in the range of 65-1600C. This is done with hydrogen chloride.

To make the 1j2 dihyroviridine compound of formula 5, a correspondingly substituted pyridine is reduced. To this reaction! !
A suitable reducing agent for j is sodium borohydride in a suitable solvent such as N,N-dimethylformamide.

DETAILED DESCRIPTION OF THE INVENTION The usual starting material in the preparation of the dihydropyridines of the invention having the above formula is dihydroxypiperidine (2), as indicated above.

A particularly suitable method for making the dihydroxypiperidines described above involves the reaction of ammonia with the appropriate tetrahydrofyrane and passing ammonia gas through the reaction mixture containing the tetrahydrofyrane.

The dihydroxypiperidine starting material for the preparation of the compounds of this invention is prepared either by the particularly suitable methods described above or by prior art methods exemplified by Balikai et al., Borland Patent No. 89,493.

Table■? Engineering nine late b month. Melting point °C A 0H(OH3)2 0F3 0H2pH385-8
9B n-butyl CF30H20H377-80
00H20H(OH3)2 0F3' 0H20H36
9-73Dbenzyl CF30H20H3137-
140EOH200H2Q C! ? 30H20H3'
102-109F 0H200H30F30H20H3
122-123a 0H20H200H213aF”,
, cl(2cl(31,4269aH0H20H2S
OH30F3 CH20H355-73 engineering 0H2SC
! H3CF30H20H3102゜5-103.5J
0H(OH'2CH3) 2 (3F30H20H38
6-89K 0H20H(OH3)2 0F30H31
02-106L 0H20H(OH3)2 0F2H0
H20H39B-100a:n25 Example 1 aH, CJ24007! Medium ethyl trifluoroacetoacetate 368.9 (2.0 mol), propionaldehyde 5
A mixture of El (1.0 mol) and piperidine 1-
Stir at 0°C for 1 hour, then at 50°C for 1 hour, and finally reflux for 1 hour. Then add another 16.0 g to the above mixture
(0,289 mol) of propionaldehyde was added,
The mixture is held at reflux for 2 hours, then the heating mantle is removed. 108.9' (6,35
mol) of ammonia gas. ``F n'mr means that this reaction mixture is 77% cis and trans isomers.
It was shown to contain a pure mixture (1:1).

Other 2,6-dihydroxy 3°5-piperidine dicarboxylates can be made using the above procedure and are the starting materials for the preparation of dihyP loviridine compounds according to the present invention.

Example 2 48.7 g (0,115 mol) of 2,6-bis-(
Add dimethyl (trifluoromethyl)-2,6-cyhydroxy-4-ynbutyl-3,5-Vpelj diadicarboxylate all at once. Stir the reaction mixture for 20 minutes, then add 1 L
Pour into ice water. The methylene chloride layer is separated, washed once with 100-saturated sodium bicarbonate, dried, and concentrated to yield 28 g (C64,6%) of crude product (1,4-dihydro isomer only). A portion of this product (5,0 g)
was distilled in a bulb tube at 0.5 torr (pot temperature 120°G),
4.8 g of the desired product are obtained as an oil, nD 1.4391. This one is 1j4-dihydro and 6°4-
Contains a 2=1 mixture of dihiP isomers.

Analysis Calculation for 015H17F6N104: 0.4
6,28; a, 4.40; N, 3.60 Actual measurement: 0,46.39; H, 4,44; N j' 3
．． Methyl trifluoroacetoacetate made in a 60° oven 340. ! il+(2,
0 mol), toluene 100- and piperidine 0.86-
90.5 g (1.05 mol) of isovaleraldehyde are added in 20 minutes to the mixture of g. The reaction mixture is kept at 80 °C for 3 hours and diluted with 125 °C of toluene. Ammonia gas (47.3 g, 2.78 mol) is passed in for 1.5 hours. The mixture is diluted with 1 oo of toluene. Excess ammonia and 200% toluene are removed under reduced pressure. The reaction mixture is diluted with 100 °C of toluene, cooled to 5 °C and treated with 548 g (5,59 mol) of sulfuric acid. The reaction mixture is stirred for 1.5 hours and poured into 21 °C of ice water. The toluene layer is Separate. The aqueous layer is drained into a 500° solution of toluene. The combined toluene solution is washed successively with 500° water, 500° saturated sodium bicarbonate, and 500° brine, and concentrated in vacuo to give 59% pure Product 363
．． 6 g (corresponding to a total yield of 831) are obtained.

Example 3 Production of diethyl 2.6-bis-(trifluoromethyl)-1,4-dihydro-4-(4-gylydyl)-3,5-pyridinedicarboxylate. Add concentrated sulfuric acid. Place the flask in an ice water bath, stir, and cool. To this acid 30 g (0,063 S mol) of 2.
Add diethyl 6-bis-(trifluoromethyl)-2,6-cyhydroxy-4-(4-pyridyl)-3,5-piperidinedicarboxylate and continue stirring for 1 hour. Pour the acidic mixture onto crushed ice and extract twice with a needle. Wash the M layer with saturated aqueous sodium bicarbonate, dry over anhydrous magnesium sulfate, and remove the solvent.

Five grams of the resulting residue is dissolved in 40 Vc of water and washed again with a saturated sodium bicarbonate water bath. The organics are extracted with ether and dried over anhydrous magnesium sulfate. Stripping off the solvent left 3.01 L of white powder, l
i' (60.8%) occurs.

Melting point 171-172°C0 Analysis Calculation for 019H16F6N204: C!
#A 9.31; H, 3-65; N, 6.39 Actual measurement: 0.49.33; H, 72; III;
6.39° Example 4 Add 100-ml concentrated sulfuric acid to a 500 rnl flask and cool in a water bath. To this Shun, 49 (0,0088 mol) of 2.64 varnish-(trifluoromethyl)-4-butyl-
Add diethyl 2,6-dihyProxy 3,5-piperidinedicarboxylate. Stir the mixture for 1 hour. Pour the acidic mixture over crushed ice and stir. Extract the organics with ethyl ether.

The ether extract was washed with saturated aqueous sodium bicarbonate, dried over MgSO, and concentrated to 2.34 g (63
, 9%) product nD 1.4419 is obtained.

Analysis Calculation for C1F H2104NIF6: 0,
4B, 92; H5,03; N, 3.35 Actual measurement: a, 4B, 95; H5,09; N,
3.36゜Example 5 Pour 250ml of concentrated sulfuric acid into a 500ml flask.

Cool the acid in an ice water bath. 25 to this. ! i/(0,0
569 mol) of 2,6-bis-(trifluoromethyl)
-2,6-dihyroxyl-improvir-6゜5-
Add diethyl piperidine dicarboxylate and continue stirring for 90 minutes. Pour the mixture over crushed ice and stir. Extract the organics twice with ethyl ether. Wash the ethereal extract with saturated aqueous sodium bicarbonate, dry over MgSO4, and concentrate.

The crude material is chromatographed using 10% ethyl acetate/cyclohexane to give 6.87 g (30%) of product, np 1-444.

Analysis Calculation for o41JIF'5 from 016H:
cj 47.64; H, 4,71; N, 3.47 Actual measurement: a, 48.95; H, 5,09; N, 3.3
6゜Example 5 Pour 250-ml concentrated sulfuric acid into a 500-ml flask.

Cool the acid in an ice water bath. To this 259 (0,0569
mol) of 2,6-bis-(trifluoromethyl)-2,
Add diethyl 6-cyhydroxy-4-ingrobi-maru 5-piperidinedicarboxylate and continue stirring for 90 minutes. Pour the mixture over crushed ice and stir. Extract the organics twice with ethyl ether. Wash the ethereal extract with saturated aqueous sodium bicarbonate, dry over MgSO4, and concentrate.

The crude material was chromatographed with 10% ethyl acetate/cyclohexane to yield 6.879 (60%) product, n
Dl, 444 is obtained.

Analysis C'16H1904NIP6 Calculation for K: c
, 47.64; H, 4,71; N, 3.47 Actual measurement: a, A7.69; H, 4,75; N
, 3.46°U6 Pour 250-600 ml of concentrated sulfuric acid into a 500-ml flask. Cool the flask in an ice water bath and stir. To this mixture was added 28.9 (0,0618 mol) of 2,6-bis-(
Add diethyl (trifluoromethyl)-2,6-dihydroxy-4-ynbutyl-3,5-piperidinedicarboxylate with stirring. After stirring for 1 hour, pour the acidic mixture over crushed ice and stir. The organics are extracted twice with ethyl ether, combined, washed with a saturated aqueous sodium bicarbonate bath, dried over Mg5O, and concentrated.

Chromatography with 20% ethyl acetate and cyclohexane yielded 9.28 fI (36%) product, nD
Get 1.4420.

0@017H2104JFal'l vs. 6 total 3! :a
j48,92; H, 5,03; N, 3.35 Actual measurement: 0.48.94; H, 5,08; N, 3.3
To a mixture of 368 g of ethyl trifluoroacetoacetate (C2.0 mol), 0.9 g of piperidine and 100 g of hydrene is added 90.5.9 (1.05 mol) of isovaleraldehyde in 20 minutes. The reaction mixture was heated to 80°C VC 1.5
Keep time. A further 4.5 g (0.05 mol) of isovaleraldehyde are added. Reaction mixture to 8000 to 35
Hold for a minute and cool to 50°. Add 30g (1
, 76 mol) of ammonia gas for 1 hour, followed by nitrogen gas for 1.5 hours.

The reaction mixture was diluted with 200° of toluene, cooled to 8°C, then 566,! i' (5,78 mol) of sulfuric acid. The reaction mixture was stirred for 45 minutes at 5-10°C,
．． 5 Pour over ice. Separate the toluene layer and add 500 g of brine.
-1 saturated sodium bicarbonate water bath solution 500 -2 and water 5
00-, dried (Mg5O,) and concentrated to give 394 g of product, which had a purity of 90.
%, corresponding to an overall yield of 85%.

U7 500m7! Pour 100-150 sulfuric acid into the flask. Place the flask in a water bath and stir the acid for about 15 minutes. 9 g (0,0205 mol) of 2,6-
Bis-[trifluoromethyl]-2° Continue stirring.

The acidic bath liquid is poured onto crushed ice and the resulting aqueous layer is extracted twice with ethyl ether. The organics were washed with saturated aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, filtered, and concentrated to 2.63. ! A product of iJ (31,78%), nD 1.4427 is obtained.

! Calculation for milk C16Hlfu04NIF6: Oj
47.88; H+4.26; N, 3.49 Actual measurement: 0.47.92; H, 4,28; N j 3.
47° Row 8 2.6-bis-(trifluoro)fl)-2°6-dihyroxy4-phenyl-3,5-bipericin diethyl dicarzoate i, o, p, toluenesulfonic acid 0.1.
A mixture of 9 and toluene 30 is kept under reflux for 4 hours and this amount of water is removed azeotropically.

Wash the toluene solution with saturated sodium bicarbonate, dry (MgSO4) and concentrate in vacuo. This residue was purified on a silica sol using ether-petroleum ether (1:
9 V/V). The first fraction (eluent 500-) is 0.70 &
gives an oily substance. 1H nmr analysis of this material indicates that it is 2,6-bis-(trifluoromethyl)-dihyro(1
, 4 and ro, 4)-4-phenylubiridine-. 3.
It shows that it is a mixture of diethyl 5-dicarboxylate.

This material was transferred to a silica sol plate (2000μ, 20×
Chromatography was performed on 0.6611
(71%) oil, nD 1.4887, which solidifies to give 2,6-bis-(trifluoromethyl)-1,4-dihydro-4-phenyl-
Give diethyl 3,,5-16 lysine dicarboxylate.

Analysis Calculation for 019H17F6NO4K: a, 52
．． 18; H, 3,92i lJ, 3.20 Actual measurement: 0,52. Roro; H, 3,95; N, 3.2
0° Example 9 A single-headed 250-ml flask is charged with 100 to 150 ml of strained sulfuric acid, and the acid is cooled in an ice-water bath. To this 30g (0,06
36 mol) of 2,6-bis-(trifluoromethyl)-
2,6-dihyProxy4-(4-pyridyl)-3,5
-Add diethyl piperidinedicarboxylate. Continue stirring for 1 hour. Pour the acidic solution onto crushed ice, stir and extract twice with ether. The crystals formed in the aqueous layer are filtered and recrystallized from acetone. Melting point 140-142°C0
Analysis Calculation for 018H1808N2SIF6: 0
．． 40.29; H, 3,35; N, 5.22; s, 5.97 Actual measurement: c -40-27; IH, 3-38; N,
5.18; S, 5.98° Example 10 60-ml concentrated sulfuric acid is placed in a 200rn1 single-necked flask and cooled in an ice water bath. Diethyl 2,6-bis-(trifluoromethyl)-2,6-cyhydroxy-4-methyl-3,5-piperidinedicarboxylate 5.9 (0
, 123 mol). Continue stirring for 15 minutes and pour the acidic solution onto crushed ice.

The bath is extracted twice with ether and then washed with a saturated aqueous sodium bicarbonate bath. Dry the organics over anhydrous magnesium sulfate and strip the solvent. The resulting semi-solid is mixed with petroleum ether and filtered. When the filtrate is concentrated, it becomes 0.
．． 9 g of product, nDl, 4377 are obtained.

Analysis 0141 (:1504 Calculation for NIF6: c
j 44.81; H, 4,03; N, 3.73 Actual measurement: a, 44.98: Hs 4.06;
N, 3.67° □ Example 11 Toluene (250 m) is refluxed using a Dean/Stark trap to remove water. 15g in cooled toluene
(0,0608 mol) of diethyl 2,6-bis-(trifluoromethyl)-2,6-dihydroVroxy-4-phenylmethyl-3,5-piperidinedicarboxylate and 2 g
Add (0,0105 mol) of toluenesulfonic acid.

Heat the solution to reflux and reflux for 2 hours. 2g in length (
0.0105 mol) of P-toluenesulfonic acid is added and the mixture is refluxed for 18 hours, during which time water is removed using a Dean/Stark trap.

Cool the mixture, filter and concentrate. Ethyl ether is added to the concentrate and the organics are washed with saturated aqueous sodium bicarbonate, separated, dried over MgSO4 and concentrated.

The residue is chromatographed on silica sol with eluent and 1D% ethyl acetate/cyclohexane to give 1 g (7.2%) of the desired product, 5 nDl-4820.

Analysis Calculation for C20H2104NIF6 K: 0.
52.98; H, 4, 6 ro; N, 3.09 Actual measurement: C, 5 ro, 24; Hj 4.27; N
, 3.090 Example 12 250 - Place 150 rnl of toluene in a single-headed flask. Reflux the toluene and remove water using a Dean/Stark trap. Cool toluene to 10'F C.
0,0217 mol) of 2,6-bis-(trifluoromethyl)-2,6-cyhydroxy-4-(2-furyl)-
diethyl 3,5-giveridinedicarboxylate and 1. f
Add i' (0,005 mol) of Σ-toluenesulfonic acid. The reaction mixture is heated to reflux for 4 hours with water removed through a Dean/Stark trap. The toluene was distilled off and the crude product was chromatographed on silica sol using 20% ethyl acetate-cyclohexane to give 2.48 g (26.8%) product, n; 51
．． Get 4720.

Analysis Calculation for 017H15F6N Engineering 05: a, 4
7.77; H, 3, 51; N, 3.27 Real d1: a, 47.83; H, ro, 51; N, 3.2
5゜Example 1ro about 100I7+7! Reflux the toluene using a Dean/Stark trap to remove water. To cooled toluene 2
．． Diethyl 6-bis-()IJfluoromethyl)-2,6-dihyproxy-4-(2-chenyl)-3,5-piperidinedicarboxylate 20 & (0,0418 mol) and Up-toluenesulfonic acid 2.0,9 (0,010
5 mol). Heat the mixture to reflux, 5-1
/ Reflux for 2 hours. Cool the solution and filter. The solvent was stripped and the product was chromatographed using 20% ethyl acetate/cyclohexane as eluent, yielding 2.459 (13.23%) product, nD 1
．． Get 4937.

Analysis Calculation for 017H1504NIF6SI K:
a, 46. []41(,3,38; N, 3.16; S, 7.22 Actual measurement: 0, 46.1 1; H, 244;
N , 3.12 i S , 7.16° Example 14 37.0 g (0.41 mol) of fluoromethyl)-1,4-dihyroviridine-methylthioacetaldehyde and 16 El of ethyl trifluoroacetoacetate (0.90 mol) ]
1.0, d (0.01 mol) to the stirred mixture with
Add Nogi Verizin. When the reaction mixture is heated to 80° C., an exothermic reaction occurs and the temperature rises to D1050G.

After cooling to 9D'C, the reaction mixture is kept at this temperature for 2 hours. The cooled intermediate is stripped and poured into 200°C of tetrahydrofuran, and excess ammonia is passed into the solution. An exotherm occurs and the reaction temperature rises to 40'O. After the exotherm reached the maximum, the reaction temperature was raised to 6000℃.
Keep at this temperature for 4 hours. Stripping of the intermediate yields 180.3 g of oil.

After the ice-water cooling addition of 209 parts of this intermediate in 50 parts of methylene chloride and 20 parts of concentrated sulfuric acid in 100 parts of methylene chloride, stirring of the two-phase reaction mixture is continued for 5 minutes. Pour the reaction mixture into a 600-mL ice/water mixture. After mixing well, the phases are separated and the aqueous phase is extracted with 50-methylene chloride. The combined cyclized methylene phases were dissolved in 1% sodium chloride solution 600
- and a solution of 1% sodium chloride and 5% sodium bicarbonate 600-, dried over magnesium sulfate, filtered and stripped. The liquid residue is extracted from the original tube (
KugelrOhr) When distilled, 13o~150℃1
0. An oil IL8.9 is obtained which is collected in 1 L torr.

Purification of the product by HPLO on silica gel using 10% ethyl acetate in cyclohexane as the eluting solvent gives a yellow oil after solvent removal. Bulk distillation gives a yellow oil with a boiling point range of 125-135°C (10,08) liters (yield 2%), nD 1.46B6.

This material contains 89% 1,4-dihydropyridine isomer and 11% 6,4-dihydropyridine isomer.

f) @C15H17F6No4s yc vs. -r i
x: 0, 42.76; H, 4, Q 7 iN,
3.32 Actual measurement: a, 42.72; H, 4,24; N, 3.
07° Example 15 Diethyl 2.6-bis-(trifluoromethyl)-2°6-cyhydroxy-4-phenylmethoxymethyl-6,5-piperidinedicarboxylate 8.6,! il' (0,
0166 mol), ) n, x y 5 Q ml Oyohi 1) A mixture of 1.5 g of toluenesulfonic acid hydrate is kept under reflux [19 hours, during which time water is removed by azeotropic distillation. Wash the toluene solution with 100ml of water and 10ml of saturated sodium bicarbonate and dry.
Mg5O,), concentrate. The residue is distilled in two tubes. Discard the first fraction (pot temperature 110-125°C). Second fraction (pot temperature 13 [111-140°
C) gives 6.4 g of oil, which is chromatographed using a Waters preparative 500-A silica gel column using 5% acetic acid-ethylcyclohexane as eluent (flow rate 250 d/min). The first fraction (retention time 5-9 minutes) is 2.019 (25%) of desired product, 5 nDl, 4845.

Analysis Calculation for C21H21F6N105: 0,
52.40; H, 4,40; N, 2.91 Actual measurement: 0,52.48; H, 4, d2iN I 2
．． 92゜Example 16 (a) VC100-120-concentration in 250-Jl neck 79 SC @
Inject acid. Cool the acid in an ice/water bath and stir. To this, 2.5 g (0,0
058 mol) and stir the solution for 15 minutes. Pour the acidic solution onto crushed ice and extract with ethyl ether. Wash all organics with saturated sodium bicarbonate, dry, and concentrate. The crude product was chromatographed on silica gel using 20% ethyl acetate-cyclohexane and 1 g
Obtain the product (product 442 based on dihydroxypiperidine), nD 1.4441.

Analysis Calculation for C15H1'FF6NIO4: c
, 46.27; H, 4-37; N, 3.59 Real d4li: a, 46.41; H, 4, 19; 11
．． 3.62゜(B) (Improved synthesis method) Add the dihydroxypiperidine dicarboxylic acid ester (cis isomer only) of the above (a) to a well-stirred mixture of 200% of concentrated fi acid and 200% of methylene chloride.
0,208 mol) is added. Stir the reaction mixture for 45 minutes and pour slowly onto 600 g of crushed ice. The methylene chloride layer was separated, dried (Mg5O,) and concentrated to 76.7
g (94.7% based on dihydroxypiperidine VC)
of the product is obtained.

As mentioned above, the 1,4-dihyropyridine of the present invention can be prepared directly from the reaction of a suitable monoketoester with an aldehyde. In this example, such a procedure is described.

368 g (2.0 mol) of ethyl trifluoroacetoacetate in 400 methylene chloride, 58 g of propionaldehyde
(1,0 mol) and 1 ml of piperidine! a mixture of 2
Stir for 1 hour at 0°C, then 1 hour at 60°C, then reflux for 1 hour, and cool. Add 16. to the above mixture.
Add 8 g (0,289 moles) of propionaldehyde and continue refluxing for 2 hours.

Next, remove the heating mantle. 108.9 to the reaction mixture
(6.35 mol) of ammonia gas is passed in over 2 hours.

The reaction mixture is stirred at 20° C. for 40 hours and then cooled in an ice-water bath. To the cooled reaction mixture was carefully added 100 ml of concentrated sulfuric acid over 20 minutes, followed by further addition of 500 ml of concentrated sulfuric acid over 10 minutes. Pour the reaction mixture onto 600 g of crushed ice in a 41 beaker. The methylene chloride layer is separated, dried (Mg5o4) and concentrated to yield the desired product and its 3.
686 g of oil containing a mixture with the 4-dihydro isomer are obtained.

This oil was mixed with 300rnIV of concentrated sulfuric acid and 300ml of methylene chloride.
Add to the vigorously stirred mixture with 1. mix 30
Stir for a minute and pour over 1 yuan of ice. Separate the methylene chloride layer, dry (MgSO4) and concentrate to 648 ml.
g of an oil is obtained which is triturated with 400 g of petroleum ether to remove 9.5 g of insoluble solid. Concentrate the petroleum ether filtrate. Bulk distillation of the residue at 0.4 torr gives 290 g (74.5% based on ethyl trifluoroacetoacetate) of an oil. This oil contains the desired product (84%) and its 3,4-dihydro isomer (16%).
It was determined by 19F nmr analysis that it was a mixture of

Ga1-2,6-bis-(trifluoromethyl)-3,4cis-
9 g (0,0174 mol) of diethyl 2,6-bis-(trifluorometerne-2,6-cyhydroxy-4-benzyloxymethyl-3,5-piperidine dicarboxylate) and 50 g (0,238 mol) of trifluoroacetic anhydride. )
The mixture was stirred for 40 hours and concentrated. The residue is bathed in 50 mVC of ether. The ethereal solution was washed with saturated sodium bicarbonate, dried over JSO, concentrated and
Diethyl 2,6-bis-(trifluoromethyl)-3,4-dihydro-4-benzyloxymethyl-3j5-pyridinedicarboxylate and 2,6-bis-(trifluoromethyl)-1,4-dihydro-4 -2.7 with diethyl benzyloxymethyl-6,5-pyridinedicarboxylate
: 8.7 g of a brown oil containing 1 mixture are obtained.

40-〇H2CJ! Dissolve in 2, 16.
7I titanium tetrachloride. Stir the resulting bath liquid for 1 hour, 50m7! Pour into cold 6N HCL. 50% of the mixture. Extract twice with CB2 (J2) of d. The combined CH3CL2 extracts are dried over MgSO4 and concentrated. The residue is chromatographed on silica dal using 20 ethyl thiacetate-cyclohexane as eluent. .

Discard the first fraction. The second fraction is 2,6-bis-(trifluoromethyl) as an oil.
-3,4-7hirro4-hiroxymeter-3,5-
Die-F-yl pyridinedicarboxylate 3.1.9 (45
%), nL51.4-66.

Analysis Calculation for 014H15F6N Engineering 05: a, 4
2.9; 7; H, 3,86; N, 3.58 Actual measurement: c, 42.98; H, 90; N, 3
．． 56.

Example 18 2.6-bis-(trifluoromethyl)-2゜6-dihydroxy4-ethyl-3,5-pipe, diethyl lysine dicarboxylate 10. ! A mixture of i' (0.0235 mol), 29.65 g (0.141 mol) of trifluoroacetic anhydride and 230 tnl of 0H2Ci is stirred for 2 days and concentrated. The residue was dissolved in ether, washed with saturated sodium bicarbonate, dried over Mg804, and concentrated to give 2.72.9 (+0%) of 2,6-bis-(trifluoromethyl)-3, 4-dihydro-4-ethyl-3
, 5-pyridinedicarboxylic acid zoethyl is an oily substance, nD
Obtained as 1.4186.

Analysis 015'(17F6N' Calculation for 104 K:
a, 46.28; H, a, 40; N, 3.5
0 actual measurement" C546-12r H-4, 42pN, 3.
46. Other dihydropyridines made from the corresponding piperidines in Table 1 above are also obtained by a method analogous to that described in Example 16(b). The dihydropyridines obtained are listed in Table 2 below. The groups listed for R, R1 and R2 refer to structures 3 and 4 above.

Table ■ 1q cl (2oa) I3alF,, 0H20H31
,443644,4544,26200H20H200
M20H3ay3OH20H2001,441947,
12116,9621,0H20H=80H3ay,0
H20) T, 1.468B 44.14 Ad, 12
22 0H(OH20H3)2 0F3 0H3CH3
1,44335 [], ]1 50.15230T (20
H(OH3)2 0F2H0H20H31,47165
3,5453,38HN 1.4- 3.4-,! 1.23 4.4'0 3.463. '22 92
B4.88 4.693.23 3.02 85 1
54.40 a, 19 3.22 3.05 86 1
45.37 4.99 3.25 3.22 10[]
6.0B 6.40 3.67 3.25 10012
4 Ethyl difluoroacetoacetate 50.09 (0,299
mole) and butyraldehy-13,2m/(0,1
50 mol) of piperidine are added to the stirred mixture. The temperature of the reaction mixture rises spontaneously to 100'C. After the temperature subsides, the reaction mixture is diluted with TI(F (
ID Oml), refluxed for 1.5 hours, and stirred at room temperature for 18 hours. The reaction mixture is then concentrated to give 6
0.8 g of oil is obtained. THF filtration 〇-Medium-medium extracted oily substance 55.8. NH3 is passed into the bath solution of fi' (0,138 mol). The temperature of the reaction mixture is naturally 410
It goes up to 0. After the temperature subsides, the reaction mixture is concentrated to an oil. This stuff solidifies if left alone. Recrystallization from this solid hexane yielded 27.6 g of a yellow solid, identified as the diethyl rinse isomer of 2j6-bis-(difluoromethyl)-2,6-cyhydroxy-4-propyl-6,5-piperidinedicarboxylate, C49°7%.
) is obtained.

A 5.0 g (0.012 mole) portion of this is mixed with 20-glue fluoroacetic acid. The reaction temperature increases to . After the temperature has subsided, the reaction mixture is concentrated. Dissolve the residue in ether, wash with saturated sodium bicarbonate and dry.
Mg5O,) and concentrated to give 3.48 g of an oil. This was distilled twice at 0.2 Torr (pot temperature 85°C) to yield 2.84 g (51.5%) of 2.6-bis-(difluoromethyl)-4-propyl-1,4- Diethyl dihyro6,5-pyridinedicarboxylate is obtained as a yellow oil, nDl, 4726.

Analysis C16H2m Calculation for C16H2: c, 52
．． 32; H, 5,76; N, 3.81 actual measurement; a, 51.98; a, 5.86; Example 25 N,
3.66° 2.60 Hequindeka This material is prepared from ethyl hashifluoroacetoacetate and cyclohexanecarboxaldehyde according to the procedure described in Example 24. The crude product is purified by apLc using 1% ethyl acetate-cyclohexane as eluent.

Discard the first fraction. The second fraction is diethyl 2,6-bis-(difluoromethyl)-4-cyclohexane-1°4-dihyro-6,5-pyridinedicarboxylate, melting point 40-44°C.

Analysis C engineering Q) Calculation for 125F4N04; 0j5
6.02; H, 6,18; N, 3.44 Actual measurement: 0.56.16; H, 6,42; N, 3.4
2. The material of Example 2 is prepared from ethyl trifluoroacetoacetate and cyclohexanecarboxaldehyde following the procedure of Example 16 (--c), but without distilling the crude product, which is isolated as an oil, nDl-4586. It will be done.

Analysis “Calculation for 19H23F6N104: a,
51.47; H, 5,23:N, 3.16 Actual measurement S0, 50.15; H, 5,381M, 3.2
4゜Example 27 198.5 g (0,385
268 g (1.28 mol) of trifluoroacetic anhydride are added to a solution of 0H2CJ-2500 ml (mol) in 0H2CJ-2500 ml. The reaction mixture is stirred for 18 hours and concentrated in vacuo. The residue is dissolved in 500 Y of ether and stirred with saturated sodium bicarbonate, with constant addition of 100 Y of sodium bicarbonate until all residual trifluoroacetic acid has been neutralized. The ether layer is dried (Mg5O,) and concentrated to give 178 g of oil. A solution of the above oil in 0H2C42500- was cooled to -78°C and then i'c140,9 ((1
, 740 mol) of titanium tetrachloride are added all at once. -78
After stirring for 60 min at °C, the reaction mixture was warmed to room temperature.
Then pour into a mixture of concentrated H (4,500 m) and ice water (500 m). Filter the resulting mixture through Celite. ca2
cJ, 2'l is separated, dried (Mg5O4) and concentrated to a mixture of oil and gum. The mixture is treated with 500 me of ether and filtered to remove gums. The ether filtrate was concentrated to give 149 g of an oil, which was chromatographed in four portions on silica sol using 20% ethyl acetate-cyclohexane as eluent. Combine similar fractions. Discard the first fraction (retention time 6-8.5 minutes).

The second fraction (retention time 9.5-26 min) was crystallized from petroleum ether and 61 g (41%) of 2,6-
Diethyl bis-(trifluoromethyl)-1,4-lysinedicarboxylate is obtained as a white solid, melting point 65-66°C.

Analysis Calculation for 014H15F6N105: c,
4'1.97; Hj3.86i N, 3.58 Actual measurement: a, 42.97; H, 3,87; N, 3.58° Row 28 Triphenylphosphine 2. ．． 84 g, 1MJ27 product 3.91 g (0.01 mol) and cc1430
The ml mixture is kept at reflux for 18 hours, cooled and filtered. Concentrate the filtrate. The residue was dissolved in hot petroleum ether (1
00m), filter, and concentrate. Residue (3,0
,! i') on silica gel as eluent and 0H2 (J2
Perform chromatography using From the first fraction (eluent 1.!M) 2. Og's oil gauze material strength 11 - Any silica gel melted carp 11. Rechromatography using 5% ethyl acetate-petroleum ether gives three components. The first two fractions (retention time 6-8 minutes) contained the oil 1,5i, 2,6-bis-(trifluoromethyl)-4-chloromethyl-1,
13 g (7.3%) of diethyl 4-dihyro-3,5-pyridinedicarboxylate.

Analysis “Calculation for 14H14OLIF6N104:
C! , 1.04; a, ro, 44; N, 3.42; ci 8.65 Actual measurement: 0.41.02; H, 3,47; N, 3.
39; CJ, 8.65° Example 29 Acetic anhydride 20. d 3.91 g of the product of Example 27 (0,
01 mol) and acetyl chloride 5.0 g (0,0
637 mol) was stirred for 1 hour and concentrated to give an oil which crystallized. The resulting solid was recrystallized from 50% petroleum ether (60-75°C) to give 3.84%
g (88,7%) of 4-acetoxymethyl-2,6-bis-(trifluoromethyl)-1,4-dihydro-6,
Diethyl 5-girijindicarboxylate, melting point 101-10
Obtain 6°C.

Analysis “Calculation for 16H17F6N106: c, 4
4. 5iH,3,96i N, 3.23 Actual measurement: O,,714,19;H,3,98iN j
3.18゜Example 30 Preparation of doloisomer 78% pure 6,6-dimethylbutyraldehy)'62
g (0.50 mol), ethyl trifluoroacetoacetate 1
849 (1, D mole), piperidine 1- and THF
The 300 - mixture was kept at reflux for 62 hours at 50°C.
K Cool. 1009 (6.47 mol) of ammonia is passed into the above solution over a period of 10 hours.

Concentrate the reaction mixture. The residue is dissolved in 500 ml of ether. Wash the solution twice with 600-ml water and dry.
MgSO4) and concentrate. This residue (179 g) was added slowly over 15 minutes to an ice-cold, mechanically stirred mixture of concentrated sulfuric acid 400- and an2c12400-. Pour the mixture over 2 tablespoons of crushed ice and stir well.

Separate the 082012 layer and dry it (Mg5o4)
, concentrate.

The residue is stock distilled at 0.5 Torr. Throw away the first fraction. Second fraction (pot temperature 91-130'Q) l-
! '122. ! i' liquid, which is fractionally distilled at 1 torr. The fraction with a boiling point of 121-160 °C is the pure desired product as a yellow oil (nDl -4588), which is composed of the 1,4-dihydro isomer and the 6,4-
A 3=1 mixture of dihydroisomers is assembled.

Analysis Calculation of 018H23F6N104: (1!',
50.12; H, 5,37; N, 3.25 territory? 111 ・ρ AOO/)□p Chitsuchi・N, 3
．． 65 Example 61 -1,4-dihydro-4-(1-methylpropyl) This material was prepared for 2 by a procedure similar to that used for 1HJ30.
-Produced from methyl-butyraldehyde and ether trifluoroacetoacetate. No battery, nD 1.441
7 was obtained.

Analysis Calculation of C1F H21F5N Engineering 04: as 48.
92; a, 5.07; N, 3.36 Actual measurement: a, 49.05; as5.10; N, 3.3
With the exception of the products 4°1+u17 and 27, the dihydropyridines mentioned above can be used as intermediates in the process to provide the herbicidally active corresponding pyridines. To convert the above dihydropyridine to the corresponding pyridine, convert the dihydropyridine into 1,8-diazobicyclo-[5,4,
0)-undec-7-ene (DBU). The following example shows how DihiV loviridine can be used as an intermediate for the production of herbicidally active pyridine.

Example 32 Product of column 7 31.05 (0.07A 2 mol), D
BU11,052 (0, [l 742 mol) and T
The mixture of HF200- is kept under reflux for 18 hours and concentrated.

The residue is stirred with water and extracted with ether.

The ether extracts are dried (MgSO4) and concentrated.

The residue is Kvgelrohr distilled at 1 Torr. Chromatographed on silica gel using 6% ethyl acetate-cyclohexane as eluent to give diethyl 2-(difluoromethyl)-4-propyl-6-(11 fluoromethyl).
-3,5-pyridinedicarboxylate, oil nDl
-4436.23.9 g (80.9 inches) was obtained.

Analysis Calculation of C16H1BF5NO4: 0, 50.
13; H, 4,74; N, 3.66 Actual measurement: c, 49.74; n, 4.66; N, 3.
55 Row 63 70.0 g (0,152 mol) of the product of Example 26, DB[
723,15 (El, 152 mol) and THF 25
The mixture of Q- is kept under reflux for 18 hours and concentrated. Pour the residue into water and extract with ether. The ether extract was washed with dilute hydrochloric acid, dried (Mg5o4) and concentrated.

The residue was Kugelhohr distilled to yield diethyl 4-cyclohexyl-2-(difluoromethyl)-6-()-lifluoromethyl)-3j5-pyridinedicarboxylate, oil nD 1.4614.31.9.9 (49,4
%] was obtained.

Analysis Calculation of 019H22F5N104: a, 53.9
0; H, 5, 25; N, 3.31 Actual measurement: c, 54.19; Hj5.33; N, 3.5
1° Example 34 23.0 g (0,0591 mol) of the product of Example 2, 96%
A mixture of pure BU 12.29 (0,077 mol) and THF 100 was kept under reflux for 6 days and 2
Pour into 50-3N HCL. The precipitated oil is extracted with ether (2X100m). Dry the ether extract (MgSO4) and concentrate to 14.4. 5'
Get some oil. This oil contained the desired product and an acidic product according to IHNMH. The oil is dissolved in ether and extracted with 100 ml of saturated sodium bicarbonate. The ether layer was dried (Mg504) and concentrated to give 8.9 g of an oil, which was obtained by acidifying the 71% pure sodium bicarbonate extract with concentrated HCl to give an oil, which was extracted with ether. Dry the ether layer (MgSO4)
, and concentrated to obtain 4.8 g of residue. This contained monocarboxylic and dicarboxylic acids (9:1) derived from the desired product. This residue was mixed with 3.0 g (0,0217 mol) of potassium carbonate and 20-1 mol of methyl iodide.
and acetone 50fnI! Process with. The mixture is kept under reflux for 42 hours and concentrated. Treat the residue with water,
Extract with ether (2X100+ng). Dry the ether layer and concentrate. When this material is distilled in the original tube at 1 torr (pot temperature iso'c), it is 5.19 (from Example 2 to 26.
4%) of the desired product is obtained as an oil, nDl, 447B. The product crystallized on standing, melting point 66
~37°C0 Analysis Calculation for 015H16'5N104: C14
8°79; Hj4.37; N, 3.79 Actual measurement: c, 413.751 (,4,39; N, 3
．． 77°6 with the previously mentioned 71% pure desired product as eluent.
Chromatography was performed by HPLOK using % ethyl acetate/cyclohexane and the first fraction (0.79
g, retention time 7-8.5 minutes). This one is 6-(
It was identified as methyl difluoromethyl)-4-(inbutyl)-2-(trifluoromethyl-5-pyridinecarboxylate).

The second portion (retention time 8.5-18.5 minutes) contained an additional 6.4 g (29.4%) of pure desired product, nD
It is 1.4474.

As previously explained, the 1,2-dihyroviridines according to the invention are prepared by reduction of a correspondingly substituted pyridine compound with a reducing agent, such as sodium borohydride. This procedure is illustrated in Examples 65-67 below.

Example 37 Preparation of dimethyl 1,2-dihydro-4-ynbutyl-2,6-bis(trifluoromethyl)-3,5-pyridinedicarboxylate In a 250 ml flask, 65 g of glacial acetic acid and 13.89 g of the product of Example 6 Add (0,0354 mol).

Sodium nitrite is added in an amount of 3 & (0,0434 mol) and the mixture is stirred under nitrogen for 72 hours.

Pour the solution onto ice/water and stir. The organics are extracted with ether and washed with saturated aqueous sodium bicarbonate. The product was then dried over anhydrous magnesium sulfate, filtered, and concentrated to yield 4.93 gm of diethyl 2,6-bis(trifluoromethyl)-4-isobutyl-5-pyridinedicarboxylate. It will be done.

This pyridine compound is hydrolyzed and re-esterified as shown below to produce dimethyl ester, 31.8! i' (0,076 mol), 10%
Sodium hydroxide 150tn1. (,38 mol), and ethanol 75rn1. Heat at reflux for 72 hours.

The reaction mixture was partially concentrated and diluted with water to 250-
Heat under reflux again for 24 hours. The cooled mixture is acidified with excess concentrated hydrochloric acid and extracted with ether (200+d- times, 100-3 times). The combined ether extracts were dissolved in MgSO
4, filter, and concentrate to give 2.85 g of residue. A portion (2.2 g) of this residue was mixed with 200v of dimethylformamide (dimethylformamide) and 16.59 g of potassium carbonate (
0.12 mol) and methyl hydriodide 25.5 gC0,
18 mol) and stir at room temperature for 24 hours. Mixture 17
Add to 2% hydrochloric acid.

The product is extracted with methylene chloride (200 m-times, 10
1] rnl three times). The combined extracts are washed with 30 [] of dihydrochloric acid/1% sodium chloride, dried over Mg5o4, filtered, and concentrated. When distilled using a raw tube, 16
．． 2g pale yellow oil, boiling point 100-110°G10.
1) A solid is obtained. Recrystallization from hexane/ether gives 12.0 g (49%) of a white solid, mp 80.5-82.5° C. 8.65 g of the above solid in dimethylformamyl 80-
,022 mol) to a stirred solution of 0.83. F(0,
22 mol) of sodium borohydride are added. The reaction mixture is stirred at room temperature for 1 hour, then warmed to 50° G for 15 minutes and cooled to room temperature. The reaction mixture was diluted with 600ml of 2% hydrochloric acid.
7! and 100v of methylene chloride. The phases are separated and the aqueous phase is extracted with 50 methylene chloride.

The combined extracts are washed with 1% hydrochloric acid/1% sodium chloride, dried over Mg5O, filtered and concentrated.

Purification by silica dal Hprac (cyclohexa 791% ethyl acetate) followed by stock tube distillation6.
79 g (79%) yellow oil, boiling point 115-125
°C/0.15) le, nD 1.4584 is obtained.

I] Calculation for 015H17NO4F6: a, 46
．． 2B; H, 4,40; N, 3.60 Actual measurement: 0.46. AO; H, 4, 42; N, ro, 36
゜kai 3B Aberhart and Li
v),,TOC! 1981.374917, 1 procedure to prepare 52.7 liters of ethyl 6-amino-4-methyl-2-pentenoate from 98 g of ethyl (2-methylpriobionyl)acetate. has 5 nD 1.4914 and a boiling point of 92°/6B.
, 2. , methyl 2-trifluoroacetoacetate 21.6
g and 6 g of acetaldehyde. A spontaneous isotherm to 60° was observed upon addition of 2 drops of piperidine.

The mixture is then heated with stirring at about 70° (just below reflux temperature) for 11/2 hours. The mixture is refluxed for 5 hours while monitoring with FDInr and then left in the chamber overnight. Stripping the THF from the mixture yields 46.
A crude product of 1& is obtained, of which 40 g are dried using trifluoroacetic anhydride 25- and 0H2Cj4 approx. 100-. An exotherm was observed up to 4DO, and the material was refluxed for approximately 1 hour, followed by stripping to yield 4g of crude product, which was subjected to bulk distillation (100-160°
10.15), nHa = 1.4804° Analysis Calculation for 015H20F304: c, 5
3.75; H, 6,01rN, 4.18 Actual measurement: (3j54.20; H, 6,08; N,
3.95゜Example 39 Isovaleraldehyp1s, og (,2omol), methyl trifluoroacetoacetate 30.8g (,20mol),
Ethyl 6-amino-2-pentenoate 28.6g (,20
mole), tetrahyrhoroalane 60- and piperidine 6-
The stirred mixture of drops is heated and kept under reflux for 18 hours. The cooled reaction mixture is concentrated and the residue partially crystallizes on standing at room temperature. The solid was filtered from an 8.0 g sample, washed with hexane, and recrystallized from tetrahydrofuran/hexane to yield 1.7211C22.
%) of a white solid is obtained.

72 g of the crude solid prepared above (18 moles of trifluoroacetic anhydride (30+d, 21 moles) and 150 m of methylene chloride are heated and kept under reflux for 2 hours. The washed reaction mixture is concentrated to 88.0 .9 oil is obtained.

Purification of a portion by HPLO yields pure product; nD
== 1-4785 is obtained.

Calculation for 0111H231'3NO4: 0 # 5
6.19; H# 6.66; Nj 3.85 Actual measurement: 0, 56.27; H, 6,77; N, 3
．． 600 Further compounds according to the invention were made using manufacturing techniques similar to those shown in the examples above.

These are shown in Table A below, along with their respective physical properties.

As indicated above, the compounds of the present invention have been found to be effective as herbicides, particularly as pre-emergent herbicides. Wheat culm and ■ summarize the results of tests conducted to determine the pre-emergence herbicidal activity of compounds of the invention.

The pre-emergence test is carried out as follows: Good surface soil is placed in an aluminum pan and filled to a depth of 0.95-1.27 crIL from the top of the pan.

A predetermined number of seeds or viable axillary buds of various plant species are placed on top of the soil. After sowing or adding viable axillary buds, enough soil is weighed into the pan to fill it evenly. A known active ingredient, applied in a solvent or as a wettable powder suspension system, is thoroughly mixed with the soil and used as a covering layer for the prepared dish. In Table IV below, the active ingredient content is equal to a ratio of 11.2/hectare. After treatment, the dishes are transferred to greenhouse pliers where they are watered from below as needed to provide sufficient moisture for germination and growth.

Approximately 2 to 6 weeks after sowing and treatment, observe the plants;
Record the results. Table IV below summarizes these results. Weed control evaluation is damage percentage of each plant species)
obtained using a fixed scale based on K. This rating is defined as follows: 0-24 0 25-49 1 50-74 2 75-100 3 The plant species used in one set of tests, for which the data presented in Table V Lettered by 131: A Canada Th1stle
, B Oock'1ebur, C VelvetleafJ, D MorninggglOr7, E Lambsquarters, F Smartweed, G Yellow Hu tsedge)
H quackgrass A J Johnson grass J Downy Brome K Barnyardgrass Growth chart from axillary bud with growth capacity ■ 2 32333 - 3 6 3 6 63 -010
2100023 4 00023300033 5 -000000000 1 6 -1333003133 7 31333303333 8 000 1 0000003 9 -0002000203 10 -0133303133 11 , -0000000002 ! 12 30333301033 13 0-013100033 14 0 0 0 2 3 0 0 0 0 3 31
5 - 0 0 0 0 0 0 0 0 0 216
3 1 3 3 3 - 0 3 3 3 318
-1333313”+33 19 3 0 0 33102033 20 0.1 1 1 3-3303621 1 0
CI2 3 - 0 0 0 2 322 000.0
0-00011 Table■ (Continued) Plant type Row number compound ABOD]nFGHIJK23 3
0 3 3 3 - 0 2 0 3 324 3 0
1.3 3 - 0 0 0 3 328 0 1
0 1 2 0 0 0 0 1 029 0 0 0
0 3 0 0 0 0 0 030 0 0 0
0 0 0 0 0 0 3 331 0011000
0zu6 32 3 1 3 3 3 3 3 3 3 3.33
3 1 0 0 2 Ro 30033334 3 3
3 3 3 3 3 3 3 3 335 3 3 3
3 3 3. 15 5 3 3 336 3 3
3 3 3 3 3 3 3 3 337 3 13
3 3 3 3 3 5 3 340 0 N 0 0
1 1 0 2 N 3 3, N 3 1 3 8
3 3 0 3 - 3 342 0 0 D 3 0
0 0 0 0 2 343 3 3 3 3 3
3 5 3 3 3 344 3 0 5 3 5 3
1 3 3 3 345 3 1 5 3 3 3
1 3 3 3 346 3 3 3 3 3 3 0
1 2 3 3 The compounds of the invention were further tested on the following plant species using the above procedure: L Soybean, M Sugarbeet, N Wheat.
heat), 0 Ine (Rlce), P Corian (8orghum), B Onamomi Q Wile V Buckwheat (Wi:Ld Buck
wheat ), D Hemp 5esbania
, E Rum Quarters, F Smart Rye-r1 C Velvet Leaf, J Downy Plume, S Panicum, K Barnyard r Grass, T Orabgrass The results are summarized in Table V.

I+I (I) (I) (I) to (I) (I) - (I) (
A) (A) (A) 1 (A)”O11+ + 關1 (A)
N') (a) - (i) sentinel - (a) (a) (a) (a) (
A) Go to dumb 10 (A) (A).

To No. 1 (a) (i) - (a) -. Watch (a) (a)
Mouth “ Se .0 (I) (I) 0 Mouth h1 (I) (
A) (A) Se (A) oO (A) to (A) 00 (A) Oo
(A) (A) To 00 mouth 10 r OFo To 0 C1-CI
CI CI CI C1-v-OC)Nr-(a) N to O ri cheer N) n y C)] 0 (a) 00 to 0 1 0 0] -mer-l OF y c+ Hro -N' lo 6 0
00 o 0 K? y O
O To Kozue N1 (A) (A) To (A) (A) Darkness (A) (A)
(A) N (A) - to 00 (A) (A) to (A) (A)
i (I) i (I) Kozue (I) to 豐 -. O.C.I.
CI MI N') OK-)00 N') K K
I-to. 〇00 y v-() to OCN-N')
? -CI OOOC10-〇 (a) (a) Q I l
l l l ■ 11111 豐OO(I)(I)O
(I) Hehe (I) He (I) (I) - To. 0 ``〒 (I) to (I) 0 (I) -- to. (I) to y CI CI
OOC) 00 (I) (I) to 0 O-ce 0 (I) to -〇〇〇 豐〇00 (N N'l C1l'Ov-CI
N') C1ffi NI KI 0000000 C
I O-000CI C) OO000CI C) 00
(A) (A) 0 (A) (A) - (A) 0 (A) (A) (
A) “ −〇 oooo to (A) (N (A) (A)
-Hehe (I) (I) v-CI to 0 CI Cl0-
He Kozue Or OC1se. (b) Watch “0-.000
C10N"l 01fl v-hehe FflN-hehe0 N') N"l Oy to C1rN? 00C)
10 to C100000 The herbicide composition according to the present invention is
They may contain at least one active ingredient and auxiliary agents in liquid or solid form, including concentrates that require dilution before application.

The compositions are prepared by mixing the active ingredient with auxiliary agents such as diluents, fillers, carriers and conditioning agents to obtain compositions in the form of finely divided granular solids, granules, pellets, solutions, dispersions, or emulsions. It can be manufactured by Thus, the active ingredient can be used in conjunction with auxiliary agents such as finely divided solids, liquids of organic origin, water, wetting agents, dispersing agents, emulsifying agents, or suitable combinations thereof.

The compositions of the present invention, especially solutions and irrigation agents, can be used as conditioning agents.
More than one surfactant can be present in an amount sufficient to enable a given composition to be readily dispersed in water or oil. The addition of surfactants to such compositions typically greatly enhances their efficacy. The term "surfactant" is understood to include wetting agents, dispersing agents, suspending agents, and emulsifying agents. Anionic, cationic, and nonionic agents can be used as well.

Typical wetting agents are alkylbenzenes and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amines, long chain acid esters of sodium isothionate, esters of sodium sulfoconolate, sulfated or sulfonated fatty acid esters. , petroleum sulfonate,
Sulfonated vegetable oil, tertiary acetylenic glycol,
polyoxyethylene derivatives of alkylphenols (especially inoctylphenol and nonylphenol),
and polyoxyethylene derivatives of monohigher fatty acid esters of hexitol anhydride (eg sorbitan). Particularly suitable dispersants are methylcellulose, polyvinyl alcohol, sodium lignin sulfonate, polymerizable alkyls, naphthalene sulfonate, sodium naphthalene sulfonate, and polymethylene bisnaphthalene sulfonate.

Irrigation agents are water-dispersible compositions that include one or more active fractions, an inert solid filler, and one or more wetting and dispersing agents. Inert solid fillers are usually of mineral origin, such as natural clays, diatomaceous earths, and synthetic minerals derived from silica. Examples of such fillers include kaolinite, attapulgite clay, and synthetic magnesium silicates. The hydrating powder composition according to the present invention usually contains 0.5 to 60 parts (preferably 5 parts).
~20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1 to 15 parts) of wetting agent, about 0.25 to 25 parts (preferably 1 liter to 1 liter: 1.0 to 15 parts) of dispersion. The composition contains from 5 to about 95 parts (preferably from 5 to 50 parts) of an inert solid filler (all parts by weight of the total composition). If desired, about 0.1 to 2.0 parts of the inert solid filler may be replaced with a corrosion inhibitor or antifoam agent or both.

For other compositions, from 0.1 to 60% by weight on a suitable filler.
powder concentrates consisting of active ingredients.

These powders can be diluted for application in concentrations ranging from about 0.1 to 10% by weight.

Aqueous suspension or emulsion systems are prepared by stirring an aqueous mixture of water-insoluble active ingredient and emulsifier until homogeneous and then homogenizing to obtain a very fine-grained stable emulsion system. The resulting concentrated aqueous suspension system is characterized by its extremely small particle size, so that when diluted and sprayed, the coverage is very uniform. Suitable concentrations of these compositions include 0.1 to 60% by weight of active ingredients;
The solvent preferably contains from 5 to 50% by weight, with the upper limit determined by the solubility limit of the active ingredient in the solvent.

In another type of aqueous suspension system, the water-immiscible herbicide is encapsulated to form a microcapsule phase dispersed in the aqueous phase. - In a specific series, the water-immiscible compound and the polymethylene polyphenylisocyanate are combined with the aqueous phase that meets the lignin sulfonate emulsifier, the water-immiscible phase is dispersed in the aqueous phase, and then the polyfunctional Microcapsules are formed by adding the amine. The incyanate and the amine compound react to form a solid bulk shell wall around the water-immiscible compound, thus creating its microcapsules. Typically the concentration of microencapsulated material is 48% of the total composition.
0 to 70 D fl/l, preferably 480 to 6
00g/lVc.

Concentrates are solutions of the active ingredient in a water-immiscible or partially water-immiscible solvent, usually together with a surfactant. Suitable solvents for the active ingredients according to the invention include dimethylformamide, dimethylsulfoxide, domethylpyrolyne, hydrocarbons and water-immiscible ethers, esters or ketones. However, other highly concentrated liquid concentrates can also be formulated by dissolving the active ingredient in a solvent and then diluting, for example with kerosene, to a spray strength.

Concentrated compositions generally contain about 0.1 to 95 parts (preferably 5
~60 parts) of active ingredient, about 0.25 to 50 parts (preferably 1 to 25 parts) of surfactant, and, if necessary, about 4 to 94 parts of solvent.

All parts are 1 part by weight based on a full cap of emulsifiable oil.

Granules are physically stable particulate compositions containing the active ingredient attached to or distributed within a basic amount of an inert, finely divided particulate filler. Surfactants, such as those listed above, may be present in the composition to aid in leaching of the active ingredient from the particles. Natural clay, phyllite, illite and vermiculite are a list of possible classes of particulate mineral fillers.

Particularly suitable fillers are preformed porous absorbent particles, such as preformed and sieved granular attapulgite, or thermally expanded granular vermiculite and finely ground clays, such as kaolin clay, hydric attapulgite. Or bentonite clay. These bulking agents are sprayed or compounded with the active ingredient to form herbicide granules.

The granule composition of the present invention contains about 0 active ingredients per 100 parts by weight of clay.
．． It may contain from 1 to about 30 parts by weight and from 0 to about 5 parts by weight of surfactant per 100 parts by weight of granular clay.

The compositions of the invention may also contain other additives, such as fertilizers, other herbicides, other pest control agents, mildew agents, and similar additives used as adjuvants or in combination with any of the foregoing adjuvants. It may also include substances. Compounds useful in combination with the active ingredients of the invention are, for example, triazines, ureas, carbamates, acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiol carbamates, triazoles, benzoic acids, nitriles, biphenyl ethers, and the like, for example: 2-chloro-4-ethylamino-6-inzolobylaminone triazine 2-chloro-4,6-bis-(inpropylamine)-
8-triazine 2-chloro-4,6-bis-(ethylamino)-s-
) riazine 6-inzorogyru IH-2,1,3-benzothiadiazin-4-(3H)-one 2,2.dioxide 6-amino-1,2,4-) riazole 6,7-dihydrodipi IJ ￥ (1,9-a?Z), 1-c)-Pyrazidinium salt 5-promo 3-isozorobyl-6-methyluracil 1,1'-dimethyl-4,4'-bipyridinium ureas N'-(4- Chlorophenoxy)phenyl-N,N-dimethylurea N, N-dimethyl-N'-(3-chloro-4-methylphenyl)urea ro-(3,4-dichlorophenyl)-1,1-dimethylurea 1.3 -dimethyl-6-(2-benzothiazolyl)urea 3-CP-/lorophenyl) -1,1-dimethylurea 1-butyl-3-(3,4-dichlorophenyl)-1-
Methylurea 2-chloroallyl diethyldithiocarbamate 5-(
4-chlorobenzyl)-N,N-diethylthiol carbamate isopropyl N-,(3-chlorophenyl)carbamate S-2,6-dichloroallyl-N,N-diisopropylthiol carbamate ethyl N,N-dibutylthiol carbamate S-propyl dipropylthiol carbamate 2-chloro-
N,N-diallylacetamide N,N-dimethyl-2,
2-diphenylacetamide N-(2,4-dimethyl-5-C(()lifluoromethyl)sulfonyl]amine]phenyl)acetamide N-isopropyl-2-chloroacetanilyr2',
6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-6'-ethyl-N-(2-methoxy-2
-7'rovir)-2-10roacetanilide α, α, α
-Trifluoro2,6-sinitroN,N-dipropyl-p-)luidineN-(1,1-dimethylpropynyl)-3,5-dichlorobenzamic acid/ester/alcohols2.2-Dichloropropionic acid 2- Methyl-4-chlorophenoxyacetic acid 2.4-dichlorophenoxyacetate Methyl-2-(4-(2,,71-dichlorophenoxy)phenoxifropionate 6-amino-2,5-dichlorobenzoic acid 2-methoxy-
6,6-dichlorobenzoic acid 2.3.6-)dichlorophenylacetic acid N-1-naphthylphthalamic acid 5-[2-chloro-4-(trifluoromethyl)phenoxif-2-ditrobenzoic acid sodium 4 .6-Sinitro-4-butylphenol N-(phosphonomethylfuglycine and its 016 monoalkylamines and alkali metal salts and their combination ethers 2, 4-dichlorophenyl-4-nitrotrinylether 2-chloro-α, α,α-triff oro p-)zyl-
6-Ethoxy-4-nitrodiphenyl ether miscellaneous 2.6-cyclopendenitrile acid methanalsonate sodium methanalunate disodium Fertilizers useful in combination with the above ingredients include, for example, ammonium nitrate, urea, potassium carbonate, and superphosphate. Contains acid salts. Other useful additives include substances in which plants take root and grow, such as compost, compost, humus, and sand.

Herbicidal compositions of the type described above are illustrated in some representative examples below.

■ Emulsifiable Concentrate A6 Example No. 5 Compound 1.0 Free acid of aromatic or aliphatic hydrophobe-based complex M phosphate [e.g., GAFAORE-610, GAF
C0rp, ) registered trademark] 5.59 Polyoxyethylene/polyoxypropylene block copolymer with pthal (e.g. Tergitol XH, registered trademark of Union Carbide Corp.) 1.11 Phenol 5 .34 Monochlorobenzene 86.96 100.00 Compound of B1 Example No. 16 25.00 Polyoxyethylene/hollyoxypropylene block copolymer of aromatic or aliphatic hydrophobe-based complex organic phosphate with free acid butanol ( For example, Terditol 5 Sodium N-methyl-n-oleyltaurine 2.0 Water 67.7 100.0 Compound of B1 Example No. 17 45.0 Methylcellulose,! 1 Silica airgel 1.5 Sodium lignosulfonate 3.5 N-methyl-N-oleyltauri 2.0 Disodium water 47.3 100.0 ■, Wettable powder weight percent person 1 Example number 5 compound 25.0 Sodium lignosulfonate 6.O N-Methyl-N-oleyl-tau 1.0 Sodium phosphorus amorphous silica (synthesis) 71.0 100.0 Compound of B0 Example No. B 80.0 Sodium dioctyl sulfosuccinate 1.25 Ligno Calcium sulfonate 2.75 amorphous silica (synthetic)
16.00 100.00 1=Italy 4 To 4 Don C1 Compound of Example No. 6 10.0 Sodium lignosulfonate 6. O N-Methyl-N-oleyl-tau 1.0 Sodium Phosphorus Kaolinite Clay 86.0 100.0 Sodium, Water Soluble Powder Weight Percent A1 Compound of Example No. 1 10.0 Sodium Dioctylsulfosuccinate 2.0 Um Silica Aero Gel 5.0 Methyl Violet 0.1 Sodium Bicarbonate 82.9 100.0 B0 Compound of Example No. 17 90.0 Ammonium Phosphate 10.0 ■, Powder Weight Percent A1 Compound of Example No. 2 2.11 Attapulgite 98 .0 i o o,.

Compound of B1 example number 9 60.0 Montmorillonite 40.0 100.0 Compound of C3 example number 7 30.0 Ethylene glycol 1+0 Bentonite 69. .

100, O Compound of D0 example number 16 1.0 Keinu± 99.0 i　o　o,.

■, Granules Compound of A0 example number 8 15.0 Granular attapulgite 8.0 (20/40 mesh) I　D　O,O B1 example number 9 compound 30.0 Keiso ± (20/40) 70. Oi　o　o,.

C1 Example No. B compound i.

Ethylene glycol 5.0 Methylene blue 0.1 Pyrophyllite 93.9 100.0 Compound of D1 column number 16 5.0 Qin pyrolite (2CI/40) 95.0100.0 When operated according to the present invention, the compound of the present invention Apply an effective amount of the compound to the soil containing the plants in a convenient manner.

Application of the liquid and granular solid compositions to the soil can be carried out by conventional methods, such as dust spreaders, overhanging rods and manual atomizers, and spray spreaders. The composition can also be applied from an airplane as a powder or spray since it is effective at low doses.

Application of an effective amount of the compound of the present invention to the location of unwanted weeds is essential and particularly important to the application of the present invention. The exact amount of active ingredient to be used will depend on a variety of factors, including the type of plant and its stage of development, soil type and conditions, rainfall and the particular compound used. In selective pre-emergence applications to the soil, from 0.1 to about 11.2 to 9/ha, preferably from about 1.12 to about 5.60 kg/ha.
Dosages of up to 100 hectares are usually used. In some cases, a smaller or larger percentage may be required. The person skilled in the art will be able to readily determine from the present specification, including the above phrases, the optimum proportions to be applied in a particular case.

The term "soil" appears in Webster's New International Dictionary (Webster's New International Dictionary).
s New International Dictionary
is used in its broadest sense to include all ordinary "±", as defined in the General Dictionary, 2nd Edition, Encyclopedia (1961). The term therefore refers to any substance or medium in which plants can take root and grow, and includes not only compost but also compost, manure, mud, humus, sand, etc., which are suitable for supporting plant growth. do.

Although the invention has been described with respect to particular variations, the details are not to be construed as limitations except as indicated in the claims.

Agent Akira Asamura Continuation of page 1

Claims (1)

[Scope of Claims] (1) In a herbicide composition, an adjuvant and [wherein R
from phenyl, alkyl, lower haloalkyl, lower alkoxyalkyl, lower alkylthioalkyl, lower alkylcarbonyloxyalkyl, cycloalkanylalkyl, and heterocyclic groups (where the heteroatoms are selected from nitrogen, sulfur, and oxygen) each R1 is independently selected from the group consisting of 01-4 lower alkyl groups;
2 and R3 are independently selected from alkyl and fluorinated methyl groups, with the proviso that one of R2 and R3 must be a fluorinated methyl group. The above composition, characterized in that it consists of: (2) The composition according to claim 1, wherein R is 01-6 alkyl. (The composition according to claim 2, wherein 31J is 01-4 alkyl. (The composition according to claim 6, wherein one of 41R2 and R3 is a trifluoromethyl group. f51 R2 and R3 is a difluoromethyl group. (6) The composition according to claim 1, wherein R is selected from 02-4 alkyl and cyclopropylmethyl. (The composition according to claim 6, wherein 71R1 is 02-4 alkyl.) (The composition according to claim 7, wherein one of 81R2 and R3 is a trifluoromethyl group. (91 The composition of claim 7, wherein one of R2 and R3 is a difluoromethyl group. GO) The composition of claim 7, wherein R2 is fluoroalkyl and R3 is alkyl. [+11 Claim 1 in which R is inbutyl]
Compositions as described in Section. R2) A composition according to claim 11, wherein R1 is methyl. (13) The composition according to claim 12, wherein one of R2 and R3 is a trifluoromethyl group. (The composition according to claim 12, wherein one of 141R2 and UR3 is a difluoromethyl group. 05) The composition according to claim 12, wherein R is a heterocyclic group (provided that the heteroatom is oxygen) The composition according to claim 1. The composition according to claim 1, wherein uOR is frill.
Compositions as described in Section. (The composition according to claim 17, in which 181R is pyridyl. The composition according to claim 1, in which the α→ heteroatom is sulfur. (2■ R is chenyl, The composition according to claim 19. (The composition according to claim 1, in which 211R is methylthiomethyl. (2) The composition according to claim 1, in which R is methoxymethyl. (23) The composition according to claim 1, wherein R is methylthioethyl. (2) The composition according to claim 1, wherein R is ethoxyethyl. (251R The composition according to claim 1, wherein is ethyl. (26) In a method for controlling undesirable plants,
A herbicidally effective amount of [wherein R is phenyl, alkyl, lower], lower alkyl, lower alkoxyalkyl, lower alkylthioalkyl, lower alkylcarbonyloxyalkyl, cycloalkanylalkyl, and heterocyclic group (wherein R is phenyl, alkyl, lower), the heteroatoms are selected from the group consisting of The above-mentioned method comprises applying a compound having a formula selected from [Claim 2], wherein R is Cel6 alkyl.
The method described in Section 6. 128) The method of claim 27, wherein R is Cel4alkyl. 29. The method of claim 28, wherein one of c2glR2 and R3 is a trifluoromethyl group. (to) The method according to claim 28, wherein one of R2 and R3 is a difluoromethyl group. C31) The method of claim 26, wherein R is selected from 02-4 alkyl and cyclopropylmethyl. 62. The method of claim 61, wherein 02R1 is 02-4 alkyl. (33) The method according to claim 62, wherein R2 and one of the formulas is a trifluoromethyl group. 63. The method according to claim 62, wherein one of R2 and R3 is a difluoromethyl group. 62. The method of claim 62, wherein R2 is fluorinated methyl and is of the formula alkyl. 06) The method of claim 26, wherein R is isobutyl. 67. The method of claim 66, wherein t3η R1 is methyl. (38) The method according to claim 37, wherein one of R2 and R3 is a trifluoromethyl group. 38. The method of claim 37, wherein one of 09R2 and R3 is a difluoromethyl group. (40) The method according to claim 26, wherein R is a heterocyclic group (provided that the heteroatom is oxygen). (41) The method according to claim 26, wherein R is a frill. (Claim 2 in which the 421 heteroatom is nitrogen)
The method described in Section 6. (4s The method according to claim 42, wherein R is pyridyl. (44) The method according to claim 2, wherein the heteroatom is sulfur.
The method described in Section 6. (4) The method according to claim 44, wherein R is chenyl. +46) The method according to claim 26, wherein R is methylthiomethyl. (47) The method according to claim 26, wherein R is methoxymethyl. (The method according to claim 26, in which 410R is methylthioethyl. (The method according to claim 26, in which 491R is ethoxyethyl. (50) The method according to claim 26, in which R is ethyl. The method according to Range 26.
-ruoxyalkyl, lower alkoxyalkyl, lower alkylthioalkyl, heroxyalkyl, lower alkylcarbonyloxyalkyl, cycloalkanylalkyl, and heterocyclic groups, provided that the heteroatom is selected from nitrogen, sulfur, and oxygen. each R1 is independently selected from 01-4 lower alkyl groups, and R2 and R3 are independently selected from alkyl and fluorinated methyl groups, with the proviso that one of R2 and R3 is fluorine The condition is that it must be methyl chloride]
A compound having a formula chosen from. (52R is 01-6 alkyl and R1 is ethyl, the compound according to claim 51. (53) R is 01-6 alkyl and R1 is methyl, the compound according to claim 51) The compound according to claim 51. cD4) The compound according to claim 51, wherein one of R2 and R3 is a trifluoromethyl group. C55) The compound according to claim 51, wherein one of R2 and R3 is a difluoromethyl group. (The compound according to claim 51, wherein 561R is selected from C2-4 alkyl and cyclozorobylmethyl. t57) The compound according to claim 56, wherein one of R2 and R3 is a trifluoromethyl group. compound. (5e) The compound according to claim 56, in which one of R2 and R3 is a difluoromethyl group. (59) The compound according to claim 56, in which R2 is fluorinated methyl and R3 is alkyl. (60) Claim 5, wherein R is isobutyl.
Compound according to item 1. (61) R1 is selected from maetel and ethyl;
A compound according to claim 56. (62 Compound I according to claim 51, in which R is a heterocyclic group (provided that the hetero atom is oxygen). (63) Claim 6, in which the heterocyclic group is furyl.
Compound according to item 1. (64) Claim 5 in which the heteroatom is nitrogen
Compound according to item 1. (Claim 6, in which the 69 heterocyclic group is pyridyl)
Compound according to item 4. (66) Claim 5 in which the heteroatom is sulfur
Compound according to item 1. (67) The compound according to claim 62, wherein the heterocyclic group is chenyl. (68) The compound according to claim 51, wherein R is a lower alkylthioalkyl group. (6ω The compound according to claim 68, in which R is a methylthiomethyl group. (70) The compound according to claim 68, in which R is a methylthioethyl group. (7υ R is haloalkyl , claim 5
Compound according to item 1. (72) The compound according to claim 71, wherein R is selected from chloromethyl, trifluoromethyl, and 2-(trifluoromethyl)flovir. (73) The compound according to claim 71, wherein R is lower alkylcarbonyloxyalkyl. (74) The compound according to claim 69, in which R is acetoxymethyl. ff51 The compound according to claim 49, in which R is a lower alkoxyalkyl group. Compound. (76) The compound according to claim 71, wherein R is methoxymethyl. (77) The compound f according to claim 71, wherein R is ethoxyethyl. (78) [:[Medium, Rid phenyl, alkyl, 03-6 cycloalkyl, lower haloalkyl, aralkoxyalkyl, aryloxyalkyl, lower alkoxyalkyl,
each R1u Ca1-
4 lower alkyl groups, and R22 and R311-j are the same fluorinated methyl groups] in a single reaction mixture, comprising the steps of: 1 ), where R, R2, and R3 are as defined above; 2) adding a reactant selected from ammonium hydroxide and ammonia gas into the reaction product of step l) in the presence of an inert valve groton solvent to obtain dihydroxypiperidine; 3) said dihydroxypiperidine Dehydrate with a dehydrating agent,
A method as described above, characterized in that dihydropyridine is obtained. (79I) The method according to claim 78, wherein the lower alkyl 6-kedoester is ethyl trifluoroacetoacetate. (8f) The lower alkyl 6-kedoester is ethyl difluoroacetoacetate and methyl trifluoroacetoacetate. , the method according to claim 78. The method according to claim 78, wherein the aldehyde r is propionaldehye V. The method according to claim 78, wherein the C2 aldehyr r is butylaldehye V. The method described. (83) Aldehyde V is isovaleraldehyde.
A method according to claim 78.