JPH11292720A - Herbicide containing condensed imidazolinone derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a herbicide having excellent herbicidal activities by including a specific condensed imidazolinone derivative as an active ingredient. SOLUTION: This herbicide contains a condensed imidazolinone derivative of formula I [Q and T are each C-X (X is H, a 1-4C alkyl or the like) or nitrogen; R<1> is H, a 1-6C alkyl or the like; R<2> and R<3> are each H or a 1-4C alkyl; W is oxygen or sulfur; (m) is 0-3; (n) is 0-2; Ar is a group of formula II (R<4> is H or a halogen; R<5> is H, a halogen or the like; R<6> is H or a 1-6C alkyl; R<11> is H or chlorine) or the like] as an active ingredient. The compound of formula I is obtained by reacting a compound of formula III with various electrophilic reagents of the formula R<1> -L (L is a leaving group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pesticide, particularly a herbicide, containing a condensed imidazolinone derivative as an active ingredient.

[0002]

2. Description of the Related Art JP-A-51-143696, JP-A-4-305568 and JP-A-9-50.
No. 7249 discloses that certain fused imidazolinone derivatives have analgesic, antipyretic, anti-inflammatory, anti-hypertensive and anti-asthmatic effects. However, it does not disclose its use as a pesticide.

[0003]

The present inventors have conducted intensive studies on the herbicidal action of the condensed imidazolinone derivative, and as a result, have found that the compound represented by the following formula has an excellent herbicidal action, thereby completing the present invention. Reached. That is, the present invention provides a compound of the formula (I):

[0004]

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[Wherein Q and T are the same but different
And represents a CX or nitrogen atom;¹ Is hydrogen field
Child, C₁-C₆Alkyl group, C₁-C₆Haloalkyl
Group, C_Three-C₆Cycloalkyl group, C_Two-C₆Alkene
Group, C_Two-C₆Haloalkenyl group, C_Three-C₆Cyclo
Alkenyl group, C_Two-C₆Alkynyl group, C_Two-C₆C
Loalkynyl group, C_Three-C₆Cycloalkynyl group, C₁
-C_Four Alkoxy C₁-C_FourAlkyl group, substituted with A
Phenyl C₁-C_FourAlkyl group (A is halo
Gen atom, C₁-C_Four Alkyl group, C₁-C_FourHaloal
Kill group, C₁-C_FourAlkoxy group, C₁-C_FourHaloal
Coxy group, C₁-C_FourAlkoxycarbonyl group, C₁−
C_Four Alkoxycarbonyl C₁-C_Four Alkoxy group, C
₁-C_Four Alkoxycarbonyl C₁-C_Four Haloalkyl
Group, C₁-C_Four Alkoxycarbonyl C ₁-C_Four Archi
Ruamino group, carbamoyl C₁-C_Four Alkoxy group,
Ruboxy C₁-C_Four Alkoxy, nitro or shea
One or more substituents, the same or different, selected from
Represents ), A phenyl group optionally substituted by A
(A represents the same as defined above.)
Good phenyl C_Two-C_FourAlkenyl group (A is as defined above
Represents ), C₁-C_FourAn alkoxy group, substituted with A
Phenyl C₁-C_FourAlkoxy group (A is before
Represent the following. ), C₁-C_FourHaloalkoxy group,
C₁-C₆Alkoxycarbonyl C₁-C_FourAlkyl
Group, phenyl C optionally substituted with A₁-C_FourAl
Koxy C₁-C_FourAlkyl group, C₁-C_Four Alkyl cal
Bonyl group or C₁-C_Four Represents an alkylsulfonyl group
Then R^Two And R^ThreeMay be the same or different,
Hydrogen atom or C₁-C_FourRepresents an alkyl group, and W is an acid
X represents a hydrogen atom, a C atom or a sulfur atom;₁
-C_FourAlkyl group, C₁-C_FourHaloalkyl group, C₁−
C _FourAlkoxycarbonyl group, halogen atom, cyano
Group, C₁-C_FourAlkoxy group or C₁-C_FourAlkyl
Represents a thio group, m represents an integer of 0 to 3, and n represents
Ar represents an integer of 0 to 2, and Ar represents the following formula (a):
Groups selected from (b) and (c)

[0006]

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, And R^FourIs a hydrogen atom or halogen
R^FiveIs a hydrogen atom, a halogen atom, C₁
-C_FourAlkyl group, C₁-C_FourHaloalkyl group, nitro
Group, cyano group, phenyl C optionally substituted with A₁
-C_FourAn alkoxy group (A represents the same as defined above);
Droxy group or C₁-C_FourRepresents a haloalkoxy group
Then R⁶Is a hydrogen atom, C₁-C₆Alkyl group, C_Three-C
₆Cycloalkyl group, C₁-C₆Haloalkyl group, C_Two
-C₆Alkenyl group, C_Two-C₆Haloalkenyl group, C
_Two-C₆Alkynyl group, C_Two-C₆Haloalkynyl group,
A phenyl group which may be substituted with A (A is as defined above
Represents ), Formyl group or A
Phenyl C₁-C_FourAlkyl group (A is as defined above)
You. ), Phenyl C optionally substituted with A_Two-C_Four
Alkenyl groups (A represents the same as defined above), carboxy
Sil group, C₁-C₆Alkoxycarbonyl group, C₁-C
₆Alkoxycarbonyl C₁-C_FourAlkyl group, C₁−
C₆Alkoxycarbonyl C₁-C_FourHaloalkyl group,
C₁-C₆Alkoxycarbonyl C_Two-C_FourAlkenyl
Group, C₁-C₆Alkoxycarbonyl C_Two-C_FourHaloa
Lucenyl group, -YR⁷Group (Y is oxygen atom or sulfur
Represents an atom, R⁷Is a hydrogen atom, C₁-C₆Alkyl
Group, C_Three-C₆Cycloalkyl group, C₁-C₆Haloal
Kill group, C_Two-C₆Alkenyl group, C_Two-C₆Haloal
Kenyl group, C_Two-C₆Alkynyl group, C_Two-C₆Haloa
Rukinyl group, C₁-C_Four Alkoxy C₁-C_Four Alkyl
A phenyl group optionally substituted by A (A is
Represents a thing. ), Phenyl optionally substituted with A
C₁-C_FourAn alkyl group (A represents the same as described above),
Phenyl C optionally substituted with A_Two-C_FourAlkene
(A represents the same as defined above), C₁-C₆Arco
Xycarbonyl C₁-C_FourAlkyl group, C₁-C₆Al
Coxycarbonyl C₁-C_FourHaloalkyl group, C₁-C
₆Alkoxycarbonyl C_Two-C_FourAlkenyl group or
C₁-C₆Alkoxycarbonyl C_Two-C_FourHalo arche
Represents a nyl group. ), -N (R⁸) R⁹Base ｛R⁸Is hydrogen
Atom, C₁-C₆Alkyl group, C₁-C₆Haloalkyl
Group, C_Two-C₆Alkenyl group, C_Two-C₆Alkynyl
Group, C₁-C₆Alkoxycarbonyl group, C₁-C₆A
Alkylcarbonyl group, formyl group, C₁-C₆ Alkyl
Sulfonyl group, phenyl C optionally substituted with A₁
-C_FourAlkylcarbonyl group (A is as defined above)
You. ) Or phenylcarbo optionally substituted with A
A phenyl group (A represents the same as defined above);⁹Is
Hydrogen atom, C₁-C₆Alkyl group, C₁-C₆Haloal
Kill group, C_Two-C₆Alkenyl group, C_Two-C₆Alkini
Group, C₁-C₆Alkoxycarbonyl group, C₁-C₆
An alkylcarbonyl group,
A carbonyl group (A represents the same as defined above);₁
-C₆Alkoxycarbonyl C₁-C_FourAlkyl group, C
₁-C₆Alkylsulfonyl group or C₁-C₆Gials
Represents a killsulfamoyl group. ｝, Cyano group, nitro
Group, cyano C ₁-C_FourAlkyl group or halogen atom
And R^TenIs a hydrogen atom, C₁-C₆Alkyl group, C
₁-C₆Haloalkyl group, C_Three-C₆Cycloalkyl
Group, C_Two-C₆Alkenyl group, C_Two-C₆Haloalkene
Group, C_Two-C₆Alkynyl group, C_Two-C₆Haloalk
Nyl group, C₁-C₆Alkylcarbonyl group, C₁-C₆
Alkylcarbonyl C₁-C_FourAlkyl group, C₁-C₆
Alkoxycarbonyl C₁-C_FourAlkyl group, substituted with A
Phenyl C which may be₁-C_FourAlkyl carboni
(A represents the same as defined above.) Cyano C ₁-C_FourA
Alkyl group, phenyl C optionally substituted with A₁-C
_FourAn alkyl group (A represents the same as defined above), C₁-C
_FourAlkoxy C₁-C_FourAlkyl group, C₁-C_Four Archi
Rusulfonyl group or C₁-C_FourAlkylthio C₁-C
_FourR represents an alkyl group;¹¹Is a hydrogen or chlorine atom
And Z represents an oxygen atom, a sulfur atom or NH.
And P represents 0 or 1, and E represents an integer of 0 to 2.
Express. ] The condensed imidazolinone derivative represented by
It is called an imidazolinone compound. ) As active ingredient
Pesticides, especially herbicides
is there.

[0008]

DETAILED DESCRIPTION OF THE INVENTION In the formula (I), Q represents CH or a nitrogen atom, preferably a nitrogen atom. T includes CH or a nitrogen atom, preferably CH. R ¹ As a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, trifluoromethyl group, difluoromethyl group, difluorochloromethyl group, difluorobromomethyl group,
2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-fluoropropyl group, 3-chloropropyl group, cyclopropyl group, cyclopentyl group, allyl group, crotyl group, 3-chloroallyl Group, cyclopentenyl group, propargyl group, 1-methyl-propargyl group, 3-chloropropargyl group, methoxymethyl group, ethoxymethyl group, benzyl group, 4-chlorobenzyl group, 3-chlorobenzyl group, 2-chlorobenzyl group ,
2,3-dichlorobenzyl group, 2,4-dichlorobenzyl group, phenethyl group, cinnamyl group, methoxy group, ethoxy group, benzyloxy group, difluoromethoxy group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, benzyloxycarbonyl group Acetyl group or methanesulfonyl group, preferably trifluoromethyl group, difluoromethyl group, difluorochloromethyl group, difluorobromomethyl group, 3-fluoropropyl group or allyl group.

R ² And R ³ As a hydrogen atom, a methyl group or an ethyl group, and preferably a hydrogen atom. W is an oxygen atom or a sulfur atom, preferably an oxygen atom. X represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group,
Examples thereof include a methoxycarbonyl group, a chlorine atom, a bromine atom, a cyano group, a methoxy group and a methylthio group, and preferably a hydrogen atom or a chlorine atom.

M is an integer of 0, 1, 2, or 3, and preferably 0 or 1. n is an integer of 0, 1 or 2, and preferably 0. R ⁴ includes a hydrogen atom, a fluorine atom or a chlorine atom, and preferably a fluorine atom.

R ⁵ includes a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a nitro group, a cyano group, a benzyloxy group, a difluoromethyl group or a trifluoromethyl group, preferably a chlorine atom or a cyano group. Can be R ⁶ Are a hydrogen atom, a methyl group, an allyl group, 3
-Chloroallyl group, propargyl group, phenyl group, formyl group, styryl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonyl-2-chloroethyl group, 2-ethoxy A carbonyl-2-chlorovinyl group, a cyano group, a nitro group, a cyanomethyl group, a chlorine atom or a fluorine atom, preferably a hydrogen atom, a 2-ethoxycarbonyl-2-chloroethyl group or a 2-ethoxycarbonyl-2-chloro group; And vinyl groups.

[0012] Examples of Y include an oxygen atom and a sulfur atom. R ⁷ represents a hydrogen atom, a methyl group, an isopropyl group, a cyclopentyl group, a 2-chloroethyl group, an aryl group, a crotyl group, a 3-chloroallyl group, a propargyl group, a 1-methylpropargyl group, a methoxymethyl group, an ethoxymethyl group, Phenyl, benzyl, styryl, methoxycarbonylmethyl, ethoxycarbonylmethyl, pentyloxycarbonylmethyl, 2
-Ethoxycarbonyl-2-chloroethyl group, 2-ethoxycarbonylvinyl group or 2-ethoxycarbonyl-2-chlorovinyl group, preferably methyl group, isopropyl group, cyclopentyl group, propargyl group, methoxycarbonylmethyl group, ethoxy group. Examples thereof include a carbonylmethyl group and a pentyloxycarbonylmethyl group.

R ⁸ represents a hydrogen atom, a methyl group, 2-
Chloroethyl group, allyl group, propargyl group, methoxycarbonyl group, ethoxycarbonyl group, acetyl group, propionyl group, pivaloyl group, formyl group, methanesulfonyl group, ethanesulfonyl group, benzoyl group or para-methoxybenzoyl group, preferably Represents a hydrogen atom, a pivaloyl group or a para-methoxybenzoyl group.

R ⁹ is a hydrogen atom, a methyl group, 2-
Chloroethyl group, allyl group, propargyl group, methoxycarbonyl group, ethoxycarbonyl group, acetyl group, benzoyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methanesulfonyl group, ethanesulfonyl group or dimethylsulfamoyl group, Preferably, a methanesulfonyl group or an ethanesulfonyl group is used.

R ¹⁰ is a hydrogen atom, methyl, ethyl, propyl, trifluoroethyl, cyclopentyl, allyl, 3-chloroallyl, propargyl, 1-methylpropargyl, acetyl, methoxycarbonyl Methyl group, ethoxycarbonylmethyl group, 1
-Ethoxycarbonylethyl, benzoyl, cyanomethyl, benzyl, methoxymethyl, ethoxymethyl or methylthiomethyl, preferably methyl, allyl, propargyl or cyanomethyl.

R ¹¹ is a hydrogen atom or a chlorine atom, preferably a hydrogen atom. Z includes an oxygen atom, a sulfur atom or NH, preferably an oxygen atom or a sulfur atom. P is 0 or 1.

E is 0, 1, or 2, and preferably 0 or 1. Some of imidazolinone compound upland, as a non-arable land herbicide, soil treatment, even in the one of the processing method of the foliage treatment, Inuhouzuki (Solanum nigrum), Datura (Datura
Solanaceae weeds represented by stramonium, etc .; Malutilaceae represented by Maltese ( Abutilon theophrasti ), American deer ( Sida spinosa ) etc.
eae) weeds, morning glory ( Ipomoea purpurea ) and other morning glory ( Ipomoea spps.) and convolvulus ( Calystegia s)
pps.) family Convolvulaceae represented by such (Convolvulaceae) weeds, Amaranthus lividus (Amaranthus lividus), slender amaranth (Amar
Amaranth (Amaranth) represented by anthus retroflexus
aceae) Weeds, Anemone fir ( Xanthium pensylvanicum ), Ragweed ( Ambrosia artemisiaefolia ), Sunflower ( Heli )
anthus annuus) , pikeweed ( Galinsoga ciliata) ,
Atlantic thistle ( Cirsium arvense ), wild croak ( Senecio vulgaris ), burdock ( Erigeron annus )
Asteraceae (Compositae) weeds, such as Asteraceae ( Rorippa indica ), and agaric ( Sinapis arvensi )
s ), Cruciferae weeds such as Capsella Bursapastoris , and Polygonu
m Blumei ), Polygonaceae weeds represented by Polygonum convolvulus, etc., Portulacaceae weeds represented by purslane ( Portulaca oleracea ), Chenopodium album ,
Kookasa ( Chenopodium ficifolium ), Butterfly ( Koch )
ia scoparia) and other red crabs (Chenopodiacea)
e) Weeds, Caryophyllaceae weeds such as Stellaria media, Scrophulariaceae weeds such as Veronica persica, etc., Commelina comm
Laminaceae (Commelinaceae) weeds such as unis ), Labiatae ( Lamium amplexicaule) , Laminariaceae (Labi purpureum ) and the like represented by Lami purpureum
atae) weed, Euphorbia supina , Euphorbia maculata and other Euphorbiaceae weeds, and Galium ( Galium )
spurium ), Rubiaceae weeds such as Rubia akane, Violaceae weeds such as violet ( Viola mandshurica) , Sesbania exaltata , and Cassia o.
btusifolia) legume that typified by (Leguminosae) broad-leaved weeds such as weeds (Broad-leaved weeds), wild sorghum (Sorgham bicolor), fall panicum (Panicum dichotom
iflorum) , Johnsongrass ( Sorghum halepense) , Barnyardgrass ( Echinochloa crus-galli var. crus-galli ),
Echinochloa crus-galli var. Praticol
a) , cultivated flies ( Echinochloa utilis ), crabgrass ( Digi )
taria adscendens ), oats ( Avenafatua ), hawksbill ( Eleusine indica) , enokorogosa ( Setaria viri )
dis) , various weeds (Croplandous weeds) such as Graminaceous weeds such as sparrows ( Alopecurus aegualis) and Cyperaceous weeds such as Cyperus rotundus and Cyperus esculentus. It has high herbicidal activity at low dose.

[0018] In addition, as a herbicide for paddy fields, in any of soil treatment and foliage treatment under flooded conditions, a hermit mosquito ( Alisma canaliculatum ) and a squid ( Sagittar ) are used.
ia trifolia) , Urikawa ( Sagittaria pygmaea ), and other weeds (Alismataceae), weeds ( Cyperus difformis) , and Cyperus sero
tinus) , fireflies ( Scirpus juncoides) , kuroguwai ( Eleocharis kuroguwai) and other Cyperaceae weeds, and zenah ( Lindernia pyxidari)
a) Scrothulariacea (Scrothulariacea)
e) Weeds, Potenderiaceae weeds such as Monochoria vaginalis, weeds, Potamogetonaceae weeds such as Potamogeton distinctus , Rotary indica ( Rotala ind)
ica), etc., Lysraceae weeds, Echinochloa oryzicola , Echinochloa crus-galli var. formosensis , Echinochloa crus-galli var. crus-galli weeds, etc. Weeds (Paddy weeds) have high herbicidal activity at low dose.

Further, some of the imidazolinone compounds have high safety against important crops such as rice, wheat, barley, sorghum, peanuts, corn, soybean, cotton, beet and the like. The compound represented by the general formula (I) can be synthesized, for example, by the methods shown in Schemes 1 and 2. R ¹ , R ² , R ³ ,
Q, T, X, m, n and Ar each have the same meaning as described above, and L represents a leaving group.

[0020]

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(Scheme 1) The compound (II) is reacted with various electrophilic reagents (III) to give the imidazolinone compound (1:
W = 0). Solvents that can be used in the synthesis reaction from compound (II) to imidazolinone compound (I) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene and xylene. , Acetonitrile, polar aprotic solvents such as N, N-dimethylformamide, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, and preferably N, N-dimethylformamide and dioxane Or use acetone.

Examples of usable bases include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate; metal hydrides such as sodium hydride;
Organic bases such as pyridine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene, and alkoxides such as sodium methoxide;
Preferably, sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate or sodium carbonate is used.

The reaction temperature may be selected from the range of -10 ° C. to the boiling point of the solvent, and preferably from room temperature to 120 ° C. The reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours, preferably 30 minutes to 5 hours. The desired product can be purified by an isolation means such as extraction, recrystallization, distillation, or column chromatography, if necessary.

Compound (II) is described, for example, in JP-A-51-14.
3696, JP-A-4-305568, or J. Heterocycl. Chem., (1983), 20 (5), 1
339-1349 and the like.

[0025]

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(Scheme 2) Compound I of the present invention (W = S) is obtained by reacting imidazolinone compound (I) (when W = 0) with diphosphorus pentasulfide or Lawesson's reagent.
Can be synthesized. Examples of the solvent that can be used in the reaction from compound (I) (W = 0) to compound (I) (W = S) include ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as benzene, toluene, and xylene. And halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride. Dioxane, tetrahydrofuran, dichloromethane or chloroform is preferably used.

The amount of the phosphorus pentasulfide or Lawesson reagent to be used is based on the compound (I) (W = 0).
The phosphorus or Lawesson reagent can be used in 0.5 mole to excess mole. Preferably from 0.5 mol,
It is preferable to use 0.75 mol. The reaction temperature may be selected from the range of −10 ° C. to the boiling point of the solvent, and preferably from room temperature to 80 ° C. The reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours, preferably 30 minutes to 5 hours. The desired product can be purified, if necessary, by an isolation means such as extraction, recrystallization distillation, and column chromatography.

[0028]

The synthesis examples of the imidazolinone compounds and intermediates are specifically described below by way of examples, but the invention is not limited thereto. (Example 1) (1-1) 2- (2-fluoro-4-chlorophenylamino) -3
-Synthesis of nitropyridine

[0029]

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2-fluoro-4-chloroaniline 5.5
g and 3 g of 2-chloro-3-nitropyridine in neat
The mixture was heated and stirred at 50 ° C. After 2 hours, cool to room temperature, water,
80 ml of a mixed solution of acetic acid (water: acetic acid = 3: 1) was added, and the precipitated solid was washed. 2. The solid was collected by filtration, dried and dried.
81 g of the desired product was obtained. Melting point 96-99 ° C (1-2) Synthesis of 3-amino-2- (2-fluoro-4-chlorophenylamino) -pyridine

[0031]

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3.7 g of 2- (2-fluoro-4-chlorophenylamino) -3-nitropyridine was dissolved in 50 ml of dehydrated tetrahydrofuran, and 10% Pd was used as a catalyst.
Catalytic reduction was performed using -c. After completion of the reaction, the catalyst was removed by filtration through Celite, and the solvent was distilled off under reduced pressure. The obtained solid was washed with hexane and dried to obtain 2.88 g of the desired product. 124-126 ° C (1-3) Synthesis of 1,3-dihydro-3- (2-fluoro-4-chlorophenyl) imidazo [4,5-b] pyridin-2-one

[0033]

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2.7 g of 3-amino-2- (2-fluoro-4-chlorophenylamino) -pyridine and 3 g of urea were neatly heated and stirred at 160 ° C. for 30 minutes. After completion of the reaction, water was added and the precipitated solid was collected by filtration, washed with hexane,
After drying, 3 g of the desired product was obtained. 238-241 ° C (1-4) 1-difluoromethyl-1,3-dihydro-3- (2-
Fluoro-4-chlorophenyl) imidazo [4,5-
b] Synthesis of pyridin-2-one (Compound No. 1-14)

[0035]

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1,3-dihydro-3- (2-fluoro-
0.4 g of 4-chlorophenyl) imidazo [4,5-b] pyridin-2-one was dissolved in 30 ml of dehydrated N, N-dimethylformamide, and 0.63 g of potassium carbonate was added thereto.
Stirred at 0 ° C. Further, chlorodifluoromethane was blown into this solution for 40 minutes and allowed to cool to room temperature. Thereafter, water was added, and the mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by thin layer chromatography (developing solvent: chloroform),
0.3 g of the desired product was obtained as a solid. 88-90 ° C (Example 2) (2-1) Synthesis of 7-fluoro-6-formylamino-4-propargyl-1,4-benzoxazin-3-one

[0037]

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6 ml of formic acid and 13 ml of acetic anhydride were added at 70 ° C. for 10 minutes.
After heating for minutes, the mixture was cooled with ice water. Next, 7-fluoro-6
6 g of -amino-4-propargyl-1,4-benzoxazin-3-one was dissolved in 32 ml of pyridine and slowly added dropwise. After the final solution was stirred at room temperature, the solution was distilled off under reduced pressure, water was added, and the solid was collected by filtration. After washing with water and hexane, the residue was dried to obtain 6.2 g of the desired product as a solid. This was used for the next reaction as it was. (2-2) Synthesis of 2- (7-fluoro-4-propargyl-1,4-benzoxazin-3-one-6-amino) -3-nitropyridine

[0039]

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3.84 of 2-chloro-3-nitropyridine
g, 7-fluoro-6-formylamino-4-propargyl-1,4-benzoxazin-3-one in 6 g of N,
It was dissolved in 50 ml of N-dimethylformamide, and 1 g (60% in oil) of sodium hydride was slowly added under ice cooling. After stirring the final solution at room temperature, ice water was added, extracted with ethyl acetate, washed with dilute hydrochloric acid, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 8.18 g of the desired product. (2-3) Synthesis of 2- (7-fluoro-4-propargyl-1,4-benzoxazin-3-one-6-amino) -3-aminopyridine

[0041]

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3.3 g of iron powder was added to 2.5 ml of acetic acid and 25 ml of water.
And stirred at 70 ° C. with a mechanical stirrer. Next, 2- (7-fluoro-4-propargyl-1,4-benzoxazin-3-one-6-amino)
4 g of -3-nitropyridine was dissolved in a mixed solution of 10 ml of ethyl acetate and 2.5 ml of acetic acid and added dropwise. After heating and refluxing for 3 hours, the mixture was immediately filtered through celite, added with water, and extracted with ethyl acetate.

The extract was washed with a saturated aqueous solution of sodium hydrogen carbonate and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3.6 g of the desired product as a solid. Melting point 174-1
78 ° C. (2-4) 1,3-dihydro-3- (7-fluoro-4-propargyl-1,4-benzoxazin-3-one-6-yl) imidazo [4,5-b] pyridine-2 -On synthesis

[0044]

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2- (7-fluoro-4-propargyl-
1,4-benzoxazin-3-one-6-amino)-
3.4 g of 3-aminopyridine and 3 g of urea are neat
The mixture was heated to 0 ° C and stirred for 1 hour. After the completion of the reaction, water was added, the mixture was washed well, further washed with hexane, and dried with a pump. As a result, 3.8 g of the target product was obtained as a crude product. (2-5) 1-difluoromethyl-1,3-dihydro-3- (7-
Synthesis of Fluoro-4-propargyl-1,4-benzoxazin-3-one-6-yl) imidazo [4,5-b] pyridin-2-one (Compound No 3-1)

[0046]

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1,3-dihydro-3- (7-fluoro-
4-propargyl-1,4-benzoxazin-3-one-6-yl) imidazo [4,5-b] pyridin-2-
1 g was dissolved in 30 ml of N, N-dimethylformamide, and 1.24 g of potassium carbonate was added thereto, followed by heating to 90 ° C.
Next, chlorodifluoromethane was blown for 30 minutes. After completion of the reaction, the reaction solution was allowed to cool to room temperature, added with water, and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to thin layer chromatography (developing solvent;
Purified with chloroform / ethyl acetate = 10/1). The obtained solid was washed with diisopropyl ether to obtain 0.4 g.
Was obtained as a solid. 237-238 ° C (Example 3) 1- (3-Fluoropropyl) -1,3-dihydro-3
-(7-Fluoro-4-propargyl-1,4-benzoxazin-3-one-6-yl) imidazo [4,5-
b] Synthesis of pyridin-2-one (compound No3-2)

[0048]

Embedded image

1,3-dihydro-3- (7-fluoro-
4-propargyl-1,4-benzoxazin-3-one-6-yl) imidazo [4,5-b] pyridin-2-
On 1 g, 1-bromo-3-fluoropropane 0.42
g was dissolved in 30 ml of N, N-dimethylformamide, and 0.41 g of potassium carbonate was further added, followed by stirring at room temperature for the final solution. After completion of the reaction, water was added, the mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product.

The obtained crude product was purified by thin layer chromatography (developing solvent: chloroform / ethyl acetate = 10 /
1) Then, 0.6 g of the desired product was obtained as a solid. Melting point 169-1
72 ° C. (Example 4) 1-Difluoromethyl-1,3-dihydro-3- (2-fluoro-4-chloro-5-methoxyphenyl) imidazo [4,5-b] pyridin-2-one (Compound No. 1) Synthesis of -22)

[0051]

Embedded image

1,3-dihydro-3- (2-fluoro-
4-chloro-5-methoxyphenyl) imidazo [4,5
-B] 2 g of pyridin-2-one was dissolved in 50 ml of N, N-dimethylformamide, 2.83 g of potassium carbonate was added, and the mixture was heated and stirred at 90 ° C. Next, chlorodifluoromethane was blown in for 30 minutes and allowed to cool to room temperature. After adding water, the mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by thin-layer chromatography (developing solvent: chloroform) to obtain 1.3 g of the desired product as a solid. Melting point: 147-149 ° C. Table 1 shows the structural formula and physical properties of the imidazolinone compound synthesized according to the above Examples, including those of the above Examples.

[0053]

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Table 1

[0055]

[Table 1] ──────────────────────────────────── Compound No. R ¹ R ² n R ⁴ R ⁶ physical properties ──────────────────────────────────── 1-1 H-0 HH mp 266- 267 ℃ 1-2 Me - 0 HH mp 154-157 ℃ 1-3 Ph (2,4-Cl 2) CH 2 - 0 HH mp 172-173 ℃ 1-4 Ph (2,3-Cl 2) CH 2 -0 HH mp 193-194 ° C 1-5 Me H 1 HH mp 123-126 ° C 1-6 Ph (2,4-Cl ₂ ) CH ₂ H1 HH mp 135-136 ° C 1-7 Ph (2,4 -Cl ₂ ) CH ₂ -0 FH mp 134-137 ° C 1-8 Ph (2-Cl) CH ₂ -0 FH mp 143-147 ° C 1-9 PhCH ₂ CH ₂ -0 FH n ^19.8 _D 1.5662 1-10 _{Ph (3-Cl) CH 2} - 0 FH n 20.7 D 1.5963 1-11 Ph (4-Cl) CH 2 - 0 FH mp 104-108 ℃ 1-12 Me - 0 FH mp 137-138 ℃ 1-13 H - 0 FH mp 238-241 ℃ 1-14 CHF 2 - 0 FH mp 88-90 ℃ 1-15 HC≡CCH 2 H 1 HH mp 142-147 ℃ 1-16 Pr H 1 HH mp 64-66 ℃ 1- 17 CHF ₂ Me 1 HH n ^21.4 _D 1.5602 1-18 CH ₂ = CHCH ₂ H 1 HH mp 92-94 ℃ 1-19 CH ₂ = CHCH ₂ Me 1 HH mp 113-114 ℃ 1-20 PhCH = CH-CH ₂ H 1 HH mp 175-176.5 ℃ 1-21 H-0 F MeO mp 268-272 ℃ _{1-22 CHF 2 - 0 F MeO mp} 147-149 ℃ 1-23 CHF 2 - 0 F OCH 2 C≡CH mp 158-161 ℃ ────────────────── ──────────────────

[0056]

[Table 2] 化合物 Compound No. R ¹ R ² n R ⁴ R ⁶ physical properties _{──────────────────────────────────── 1-24 CHF 2 - 0 F OCH} 2 C≡CH mp 107-109 ℃ ────────────────────────────────────

[0057]

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Table 2

[0059]

[Table 3] 化合物 Compound No. R ¹ R ² n R ⁴ R ⁶ physical property value ──────────────────────────────────── 2-1 CHF ₂ H 1 HH mp 152 -153 ℃ ────────────────────────────────────

[0060]

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Table 3

[0062]

[Table 4] ──────────────────────────────────── Compound No. R ¹ R ¹⁰ Physical properties ─ ─────────────────────────────────── 3-1 CHF ₂ HC≡CCH ₂ mp 237-238 ℃ 3 -2 FCH ₂ CH ₂ CH ₂ HC≡CCH ₂ mp 169-172 ℃ 3-3 CH ₂ = CHCH ₂ HC≡CCH ₂ mp 236-238 ℃ ──────────────── ────────────────────

[0063]

Embedded image

Table 4

[0065]

[Table 5] Compound No. R ¹ R ² n R ⁴ R ⁶ physical property value ４− 4-1 Et H 1 HH mp 62- 65 ℃ 4-2 FCH ₂ CH ₂ CH ₂ -OF-mp 106-107 ℃ 4-3 Et-OF-mp 126-128 ℃ ───────────────────を The imidazolinone compound group synthesized according to the scheme or the examples, including the compounds synthesized in the examples, is listed in Tables 5 to 13. However, the present invention is not limited to these. Table 5

[0066]

Embedded image

In the group of compounds represented by

[0068]

[Table 6] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OH H Me OH CH ₂ CH (Cl) CO ₂ Et Me OH CH = C (Cl) CO ₂ Et Me OH OMe Me OH Oi-Pr Me OH Oc-Pen Me OH OCH ₂ CF ₃ Me OH OCH ₂ CH = CH ₂ Me OH OCH ₂ CH = CH (Cl) Me O H OCH 2 C≡CH Me O H OCH (Me) C≡CH Me O H OPh Me O H OCH 2 Ph Me O H OCH 2 CH = CH-Ph Me O H OCH 2 CO 2 Me Me OH OCH ₂ CO ₂ Et Me OH OCH ₂ CO ₂ Pen Me OH SH Me OH SMe Me OH Si-Pr Me OH Sc-Pen Me OH SCH ₂ CH = CH ₂ Me OH SCH ₂ CH = CHCl ────────────────────────────────────

[0069]

[Table 7] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OH SCH ₂ C≡CH Me OH SCH (Me) C≡ CH Me OH SPh Me OH SCH ₂ Ph Me OH SCH ₂ CO ₂ Me Me OH SCH ₂ CO ₂ Et Me OH SCH ₂ CO ₂ Pen Me OH F Me OH Cl Me OH Br Me OH NH ₂ Me OH NHMe Me OH NHCO ₂ Et Me OH NHCOMe Me OH NHCOPh Me OH NHCH ₂ CO ₂ Et Me OH NHSO ₂ Me Me OH NHSO ₂ Et Me OH NHSO ₂ NMe ₂ Me OH N (CO-t-Bu) SO ₂ Me Me OH N (CO-p-MeO-Ph) SO ₂ Me Me OH CN Me OH NO ₂ ────────────── ──────────────────────

[0070]

[Table 8] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OH CH ₂ CN Me OH CHO Me OH CO ₂ H Me OH CO ₂ Et Et OH H Et OH CH ₂ CH (Cl) CO ₂ Et Et OH CH = C (Cl) CO ₂ Et Et OH OMe Et OH Oi-Pr Et OH Oc-Pen Et O H OCH ₂ CF ₃ Et O H OCH ₂ CH = CH ₂ Et O H OCH ₂ CH = CH (Cl) Et O H OCH ₂ C≡CH Et O H OCH (Me) C≡CH Et O H OPh Et O H OCH ₂ Ph Et O H OCH ₂ CH = CH-Ph Et OH OCH ₂ CO ₂ Me Et OH OCH ₂ CO ₂ Et Et OH OCH ₂ CO ₂ Pen Et OH SH Et OH SMe ──── ────────────────────────────────

[0071]

[Table 9] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OH Si-Pr Et OH Sc-Pen Et OH SCH ₂ CH = CH ₂ Et OH SCH ₂ CH = CHCl Et OH SCH ₂ C≡CH Et OH SCH (Me) C≡CH Et OH SPh Et OH SCH ₂ Ph Et OH SCH ₂ CO ₂ Me Et O H SCH ₂ CO ₂ Et Et OH SCH ₂ SO ₂ Pen Et OH F ET OH Cl Et OH Br Et OH NH ₂ Et OH NHMe Et OH NHCO ₂ Et Et OH NHCOMe Et OH NHCOPh Et OH NHCH ₂ CO ₂ Et Et OH NHSO ₂ Me Et OH NHSO ₂ Et Et OH NHSO ₂ NMe ₂ ──────────────────────── ────────────

[0072]

[Table 10] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OH N (CO-t-Bu) SO ₂ Me Et OH N (CO-p-MeO-Ph) SO ₂ Me Et OH CN Et OH NO ₂ Et OH CH ₂ CN Et OH CHO Et OH CO ₂ H Et OH CO ₂ Et Pr OH FF Pr O H NHCO ₂ Et Pr OH NHSO ₂ Me Pr OH NHSO ₂ Et Pr OH CO ₂ Et Pr OH H Pr OH CH ₂ CH (Cl) CO ₂ Et Pr OH CH = C (Cl) CO ₂ Et Pr O H OMe Pr O H Oi-Pr Pr O H Oc-Pen Pr O H OCH ₂ C {CH Pr O H OCH ₂ CO ₂ Et Pr O H OCH ₂ CO ₂ Pen Pr O H SMe} ──────────────────────────────

[0073]

[Table 11] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr OH Si-Pr Pr OH SCH ₂ C ≡CH Pr OH _{SCH 2 CO 2 Et Pr O H} SCH 2 CO 2 Pen CHF 2 O H H CHF 2 O H CH 2 CH (Cl) CO 2 Et CHF 2 O H CH = C (Cl) CO 2 Et CHF 2 O H OMe CHF ₂ O H Oi-Pr CHF ₂ O H Oc-Pen CHF ₂ O H OCH ₂ CF ₃ CHF ₂ O H OCH ₂ CH = CH ₂ CHF ₂ O H OCH ₂ CH = CH (Cl) CHF ₂ O H OCH ₂ C ≡CH CHF ₂ O H OCH (Me) C≡CH CHF ₂ O H OPh CHF ₂ O H OCH ₂ Ph CHF ₂ O H OCH ₂ CH = CH-Ph CHF ₂ O H OCH ₂ CO ₂ Me CHF ₂ O H OCH ₂ CO ₂ Et CHF ₂ OH OCH ₂ CO ₂ Pen CHF ₂ OH SH CHF ₂ OH SMe ─────────────────────────── ─────────

[0074]

[Table 12] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OH Si-Pr CHF ₂ OH Sc-Pen CHF ₂ O _{H SCH 2 CH = CH 2 CHF} 2 O H SCH 2 CH = CHCl CHF 2 O H SCH 2 C≡CH CHF 2 O H SCH (Me) C≡CH CHF 2 O H SPh CHF 2 O H SCH 2 Ph CHF 2 _{O H SCH 2 CO 2 Me CHF} 2 O H SCH 2 CO 2 Et CHF 2 O H SCH 2 CO 2 Pen CHF 2 O H F CHF 2 O H Cl CHF 2 O H Br CHF 2 O H NH 2 CHF 2 O H _{NHMe CHF 2 O H NHCO 2 Et} CHF 2 O H NHCOMe CHF 2 O H NHCOPh CHF 2 O H NHCH 2 CO 2 Et CHF 2 O H NHSO 2 Me CHF 2 O H NHSO 2 Et CHF 2 O H NHSO 2 NMe 2 ─ ───────────────────────────────────

[0075]

[Table 13] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ O H N (CO-t-Bu) SO ₂ Me CHF ₂ O H N (CO-p- MeO-Ph) SO 2 Me CHF 2 O H CN CHF 2 O H NO 2 CHF 2 O H CH 2 CN CHF 2 O H CHO CHF 2 O H CO 2 H CHF 2 O H CO ₂ Et F (CH ₂ ) ₃ OH H F (CH ₂ ) ₃ OH CH ₂ CH (Cl) CO ₂ Et F (CH ₂ ) ₃ OH CH = C (Cl) CO ₂ Et F (CH ₂ ) ₃ O H OMe F (CH ₂ ) ₃ O H Oi-Pr F (CH ₂ ) ₃ O H Oc-Pen F (CH ₂ ) ₃ O H OCH ₂ CF ₃ F (CH ₂ ) ₃ O H OCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OHCH ₂ CH = CH (Cl) F (CH ₂ ) ₃ OHCH ₂ C≡CH F (CH ₂ ) ₃ OHCH (Me) C≡CH F (CH ₂ ) ₃ O H OPh F (CH ₂ ) ₃ O H OCH ₂ Ph F (CH ₂ ) ₃ O H OCH ₂ CH = CH-Ph F (CH ₂ ) ₃ O H OCH ₂ CO ₂ Me ────── ─────────────────────────────

[0076]

[Table 14] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ O H OCH ₂ CO ₂ Et F (CH _{2 ) 3 O H OCH 2 CO 2} Pen F (CH 2) 3 O H SH F (CH 2) 3 O H SMe F (CH 2) 3 O H Si-Pr F (CH 2) 3 O H Sc-Pen F (CH ₂ ) ₃ OH SCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OH SCH ₂ CH = CHCl F (CH ₂ ) ₃ OH SCH ₂ C≡CH F (CH ₂ ) ₃ OH SCH (Me ) C≡CH F (CH ₂ ) ₃ OH SPh F (CH ₂ ) ₃ OH SCH ₂ Ph F (CH ₂ ) ₃ OH SCH ₂ CO ₂ Me F (CH ₂ ) ₃ OH SCH ₂ CO ₂ Et _{F (CH 2) 3 O H} SCH 2 CO 2 Pen F (CH 2) 3 O H F F (CH 2) 3 O H Cl F (CH 2) 3 O H Br F (CH 2) 3 O H NH 2 F (CH ₂ ) ₃ OH NHMe F (CH ₂ ) ₃ OH NHCO ₂ Et F (CH ₂ ) ₃ OH NHCOMe F (CH ₂ ) ₃ OH NHCOPh ──────────── ────────────────────── ─

[0077]

[Table 15] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OH NHCH ₂ CO ₂ Et F (CH ₂ ) ₃ OH NHSO ₂ Me F (CH ₂ ) ₃ OH NHSO ₂ Et F (CH ₂ ) ₃ OH NHSO ₂ NMe ₂ F (CH ₂ ) ₃ OH N (CO-t-Bu) SO ₂ Me F _{(CH 2) 3 O H N} (CO-p-MeO-Ph) SO 2 Me F (CH 2) 3 O H CN F (CH 2) 3 O H NO 2 F (CH 2) 3 O H CH 2 CN F (CH ₂ ) ₃ OH CHO F (CH ₂ ) ₃ OH CO ₂ HF (CH ₂ ) ₃ OH CO ₂ Et CH ₂ = CHCH ₂ OH H CH ₂ = CHCH ₂ OH CH ₂ CH (Cl ) CO ₂ Et CH ₂ = CHCH ₂ O H CH = C (Cl) CO ₂ Et CH ₂ = CHCH ₂ O H OMe CH ₂ = CHCH ₂ O H Oi-Pr CH ₂ = CHCH ₂ O H Oc-Pen CH ₂ = CHCH ₂ O H OCH ₂ CF ₃ CH ₂ = CHCH ₂ O H OCH ₂ CH = CH ₂ CH ₂ = CHCH ₂ O H OCH ₂ CH = CH (Cl) CH ₂ = CHCH ₂ O H OCH ₂ C≡CH CH ₂ = CHCH ₂ O H OCH (Me) C≡CH ───────────── ───────────────────────

[0078]

[Table 16] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ = CHCH ₂ O H OPh CH ₂ = CHCH ₂ O H OCH ₂ Ph CH ₂ = CHCH ₂ O H OCH ₂ CH = CH-Ph CH ₂ = CHCH ₂ O H OCH ₂ CO ₂ Me CH ₂ = CHCH ₂ O H OCH ₂ CO ₂ Et CH ₂ = CHCH ₂ O H OCH ₂ CO ₂ Pen CH ₂ = CHCH ₂ OH SH CH ₂ = CHCH ₂ OH SMe CH ₂ = CHCH ₂ OH Si-Pr CH ₂ = CHCH ₂ OH Sc-Pen CH ₂ = CHCH ₂ OH SCH ₂ CH = CH _{2 CH 2 = CHCH 2 O H SCH} 2 CH = CHCl CH 2 = CHCH 2 O H SCH 2 C≡CH CH 2 = CHCH 2 O H SCH (Me) C≡CH CH 2 = CHCH 2 O H SPh CH 2 = CHCH ₂ OH SCH ₂ Ph CH ₂ = CHCH ₂ OH SCH ₂ CO ₂ Me CH ₂ = CHCH ₂ OH SCH ₂ CO ₂ Et CH ₂ = CHCH ₂ OH SCH ₂ CO ₂ Pen CH ₂ = CHCH ₂ OH F _{CH 2 = CHCH 2 O H Cl} CH 2 = CHCH 2 O H Br CH 2 = CHCH 2 O H NH 2 ────────────── ─────────────────────

[0079]

[Table 17] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ = CHCH ₂ OH NHMe CH ₂ = CHCH ₂ OH NHCO _{2 Et CH 2 = CHCH 2 O H} NHCOMe CH 2 = CHCH 2 O H NHCOPh CH 2 = CHCH 2 O H NHCH 2 CO 2 Et CH 2 = CHCH 2 O H NHSO 2 Me CH 2 = CHCH 2 O H NHSO 2 Et CH ₂ = CHCH ₂ OH NHSO ₂ NMe ₂ CH ₂ = CHCH ₂ OH N (CO-t-Bu) SO ₂ Me CH ₂ = CHCH ₂ OH N (CO-p-MeO-Ph) SO ₂ Me CH ₂ = CHCH ₂ OH CN CH ₂ = CHCH ₂ OH NO ₂ CH ₂ = CHCH ₂ OH CH ₂ CN CH ₂ = CHCH ₂ OH CHO CH ₂ = CHCH ₂ OH CO ₂ H CH ₂ = CHCH ₂ OH CO ₂ Et HC≡CCH ₂ O H H HC≡CCH ₂ O H CH ₂ CH (Cl) CO ₂ Et HC≡CCH ₂ O H CH = C (Cl) CO ₂ Et HC≡CCH ₂ O H OMe HC≡CCH ₂ O H Oi-Pr HC≡CCH ₂ O H Oc-Pen HC≡CCH ₂ O H OCH ₂ C≡CH ────────────────── ──────────────────

[0080]

[Table 18] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── HC≡CCH ₂ O H OCH ₂ CO ₂ Et HC≡CCH ₂ OH OCH ₂ CO ₂ Pen HC≡CCH ₂ OH SMe HC≡CCH ₂ OH Si-Pr HC≡CCH ₂ OH SCH ₂ C≡CH HC≡CCH ₂ OH SCH ₂ CO ₂ Et HC≡CCH ₂ OH SCH ₂ CO ₂ Pen HC≡CCH ₂ O HF HC≡CCH ₂ OH NHCO ₂ Et HC≡CCH ₂ OH NHSO ₂ Me HC≡CCH ₂ OH NHSO ₂ Et HC≡CCH ₂ OH CO ₂ Et PhCH ₂ O H H PhCH ₂ O H CH ₂ CH (Cl) CO ₂ Et PhCH ₂ O H CH = C (Cl) CO ₂ Et PhCH ₂ O H Oc-Pen PhCH ₂ O H OCH ₂ C≡CH PhCH ₂ O H OCH _{2 CO 2 Et PhCH 2 O H Si} -Pr PhCH 2 O H SCH 2 C≡CH PhCH 2 O H SCH 2 CO 2 Et PhCH 2 O H NHSO 2 Me PhCH 2 O H NHSO 2 Et ──────── ────────────────────────── ──

[0081]

[Table 19] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── PhCH ₂ OH CO ₂ Et Ph (2-Cl) CH ₂ OH H Ph (2-Cl) CH ₂ O H CH ₂ CH (Cl) CO ₂ Et Ph (2-Cl) CH ₂ O H CH = C (Cl) CO ₂ Et Ph (2-Cl) CH ₂ O H Oc -Pen Ph (2-Cl) CH 2 O H OCH 2 C≡CH Ph (2-Cl) CH 2 O H OCH 2 CO 2 Et Ph (2-Cl) CH 2 O H Si-Pr Ph (2-Cl _{) CH 2 O H SCH 2 C≡CH} Ph (2-Cl) CH 2 O H SCH 2 CO 2 Et Ph (2-Cl) CH 2 O H NHSO 2 Me Ph (2-Cl) CH 2 O H NHSO 2 Et Ph (2-Cl) CH ₂ OH CO ₂ Et Ph (3-Cl) CH ₂ OH H Ph (3-Cl) CH ₂ OH CH ₂ CH (Cl) CO ₂ Et Ph (3-Cl) CH ₂ O H CH = C (Cl) CO ₂ Et Ph (3-Cl) CH ₂ O H Oc-Pen Ph (3-Cl) CH ₂ O H OCH ₂ C≡CH Ph (3-Cl) CH ₂ O _{H OCH 2 CO 2 Et Ph (} 3-Cl) CH 2 O H Si-Pr Ph (3-Cl) CH 2 O H SCH 2 C≡CH Ph (3-Cl) CH 2 O H SCH 2 CO 2 Et Ph (3-Cl) CH ₂ O H NHSO ₂ Me ─── ─────────────────────────────────

[0082]

[Table 20] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (3-Cl) CH ₂ OH NHSO ₂ Et Ph (3- Cl) CH ₂ OH CO ₂ Et Ph (4-Cl) CH ₂ OH H Ph (4-Cl) CH ₂ OH CH ₂ CH (Cl) CO ₂ Et Ph (4-Cl) CH ₂ OH CH = C (Cl) CO ₂ Et Ph (4-Cl) CH ₂ O H Oc-Pen Ph (4-Cl) CH ₂ O H OCH ₂ C≡CH Ph (4-Cl) CH ₂ O H OCH ₂ CO ₂ Et Ph (4-Cl) CH 2 O H Si-Pr Ph (4-Cl) CH 2 O H SCH 2 C≡CH Ph (4-Cl) CH 2 O H SCH 2 CO 2 Et Ph (4-Cl) CH ₂ OH NHSO ₂ Me Ph (4-Cl) CH ₂ OH NHSO ₂ Et Ph (4-Cl) CH ₂ OH CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OH H Ph (2 , 3-Cl ₂ ) CH ₂ OH CH ₂ CH (Cl) CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OH CH = C (Cl) CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ O H Oc-Pen Ph (2,3-Cl ₂ ) CH ₂ O H OCH ₂ C≡CH Ph (2,3-Cl ₂ ) CH ₂ O H OCH ₂ CO ₂ Et Ph (2,3-Cl _{2) CH 2 O H Si-} Pr Ph (2,3-Cl 2) CH 2 O H SCH 2 C≡C H Ph (2,3-Cl ₂ ) CH ₂ O H SCH ₂ CO ₂ Et ─────────────────────────────── ─────

[0083]

[Table 21] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (2,3-Cl ₂ ) CH ₂ OH NHSO ₂ Me Ph (2,3-Cl ₂ ) CH ₂ OH NHSO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OH CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OH H Ph (2,4 -Cl ₂ ) CH ₂ OH CH ₂ CH (Cl) CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OH CH = C (Cl) CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ O H Oc-Pen Ph (2,4-Cl ₂ ) CH ₂ O H OCH ₂ C≡CH Ph (2,4-Cl ₂ ) CH ₂ O H OCH ₂ CO ₂ Et Ph (2,4-Cl ₂ ) _{CH 2 O H Si-Pr Ph} (2,4-Cl 2) CH 2 O H SCH 2 C≡CH Ph (2,4-Cl 2) CH 2 O H SCH 2 CO 2 Et Ph (2,4-Cl ₂ ) CH ₂ OH NHSO ₂ Me Ph (2,4-Cl ₂ ) CH ₂ OH NHSO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OH CO ₂ Et PhCH = CHCH ₂ OH H PhCH = CHCH ₂ O H CH ₂ CH (Cl) CO ₂ Et PhCH = CHCH ₂ OH CH = C (Cl) CO ₂ Et PhCH = CHCH ₂ O H Oc-Pen PhCH = CHCH ₂ O H OCH ₂ C≡CH PhCH = CHCH ₂ O H OCH ₂ CO ₂ Et _{PhCH = CHCH 2 O H Si-} Pr PhCH = CHCH 2 O H SCH 2 C≡CH ────────────────────────────── ──────

[0084]

[Table 22] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── PhCH = CHCH ₂ OH SCH ₂ CO ₂ Et PhCH = CHCH ₂ OH NHSO ₂ Me PhCH = CHCH ₂ OH NHSO ₂ Et PhCH = CHCH ₂ OH CO ₂ Et PhCH ₂ CH ₂ OH H PhCH ₂ CH ₂ OH CH ₂ CH (Cl) CO ₂ Et PhCH ₂ CH ₂ OH CH _{= C (Cl) CO 2 Et} PhCH 2 CH 2 O H Oc-Pen PhCH 2 CH 2 O H OCH 2 C≡CH PhCH 2 CH 2 O H OCH 2 CO 2 Et PhCH 2 CH 2 O H Si-Pr PhCH 2 _{CH 2 O H SCH 2 C≡CH PhCH} 2 CH 2 O H SCH 2 CO 2 Et PhCH 2 CH 2 O H NHSO 2 Me PhCH 2 CH 2 O H NHSO 2 Et PhCH 2 CH 2 O H CO 2 Et MeO O H H MeO OH CH ₂ CH (Cl) CO ₂ EtMeO OH CH = C (Cl) CO ₂ Et MeO OH Oc-Pen MeO OH OCH ₂ C≡CH MeO OH OCH ₂ CO ₂ Et MeO OH Si-Pr ──────────────────────────── ───────

[0085]

[Table 23] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── MeO OH SCH ₂ C≡CH MeO OH SCH ₂ CO ₂ Et MeO O H NHSO ₂ MeMeO OH NHSO ₂ Et MeO OH CO ₂ Et Me O Cl H Me O Cl CH ₂ CH (Cl) CO ₂ Et Me O Cl CH = C (Cl) CO ₂ Et Me O Cl OMe Me O Cl Oi-Pr Me O Cl Oc-Pen Me O Cl OCH 2 CF 3 Me O Cl OCH 2 CH = CH 2 Me O Cl OCH 2 CH = CH (Cl) Me O Cl OCH 2 C≡CH Me O Cl OCH (Me) C≡CH Me O Cl OPh Me O Cl OCH ₂ Ph Me O Cl OCH ₂ CH = CH-Ph Me O Cl OCH ₂ CO ₂ Me Me O Cl OCH ₂ CO ₂ EtMe O Cl OCH ₂ CO ₂ Pen Me O Cl SH ────────────────────────────────────

[0086]

[Table 24] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me O Cl SMe Me O Cl Si-Pr Me O Cl Sc-Pen Me O Cl SCH ₂ CH = CH ₂ Me O Cl SCH ₂ CH = CHCl Me O Cl SCH ₂ C≡CH Me O Cl SCH (Me) C≡CH Me O Cl SPh Me O Cl SCH ₂ Ph Me O Cl SCH ₂ CO ₂ Me Me O Cl SCH ₂ CO ₂ Et Me O Cl SCH ₂ CO ₂ Pen Me O Cl F Me O Cl Cl Me O Cl Br Me O Cl NH ₂ Me O Cl NHMe Me O Cl NHCO ₂ Et Me O Cl NHCOMe Me O Cl NHCOPh Me O Cl NHCH ₂ CO ₂ Et Me O Cl NHSO ₂ Me Me O Cl NHSO ₂ Et ─────────────────────────── ─────────

[0087]

[Table 25] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me O Cl NHSO ₂ NMe ₂ Me O Cl N (CO-t-Bu ) SO ₂ Me Me O Cl N (CO-p-MeO-Ph) SO ₂ Me Me O Cl CN Me O Cl NO ₂ Me O Cl CH ₂ CN Me O Cl CHO Me O Cl CO ₂ HMe O Cl CO ₂ Et Et O Cl H Et O Cl CH ₂ CH (Cl) CO ₂ Et Et O Cl CH = C (Cl) CO ₂ Et Et O Cl OMe Et O Cl Oi-Pr Et O Cl Oc-Pen Et O Cl OCH ₂ CF ₃ Et O Cl OCH ₂ CH = CH ₂ Et O Cl OCH ₂ CH = CH (Cl) Et O Cl OCH ₂ C≡CH Et O Cl OCH (Me) C≡CH Et O Cl OPh Et O Cl OCH ₂ Ph Et O Cl OCH ₂ CH = CH-Ph ────────────────────────────────────

[0088]

[Table 26] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et O Cl OCH ₂ CO ₂ Me Et O Cl OCH ₂ CO ₂ Et Et O Cl OCH ₂ CO ₂ Pen Et O Cl SH Et O Cl SMe Et O Cl Si-Pr Et O Cl Sc-Pen Et O Cl SCH ₂ CH = CH ₂ Et O Cl SCH ₂ CH = CHCl Et O Cl SCH ₂ C ≡CH Et O Cl SCH (Me) C≡CH Et O Cl SPh Et O Cl SCH ₂ Ph Et O Cl SCH ₂ CO ₂ Me Et O Cl SCH ₂ CO ₂ Et Et O Cl SCH ₂ CO ₂ Pen Et O Cl F Et O Cl Cl Et O Cl Br Et O Cl NH ₂ Et O Cl NHMe Et O Cl NHCO ₂ Et Et O Cl NHCOMe ─────────────────────── ─────────────

[0089]

[Table 27] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et O Cl NHCOPh Et O Cl NHCH ₂ CO ₂ Et Et O Cl NHSO ₂ Me Et O Cl NHSO ₂ Et Et O Cl NHSO ₂ NMe ₂ Et O Cl N (CO-t-Bu) SO ₂ Me Et O Cl N (CO-p-MeO-Ph) SO ₂ Me Et O Cl CN Et O Cl NO ₂ Et O Cl CH ₂ CN Et O Cl CHO Et O Cl CO ₂ H Et O Cl CO ₂ Et Pr O Cl F Pr O Cl NHCO ₂ Et Pr O Cl NHSO ₂ Me Pr O Cl NHSO ₂ Et Pr O Cl CO ₂ Et Pr O Cl H Pr O Cl CH ₂ CH (Cl) CO ₂ Et Pr O Cl CH = C (Cl) CO ₂ Et Pr O Cl OMe Pr O Cl Oi-Pr ───────── ───────────────────────────

[0090]

[Table 28] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr O Cl Oc-Pen Pr O Cl OCH ₂ C≡CH Pr O Cl OCH ₂ CO ₂ Et Pr O Cl OCH ₂ CO ₂ Pen Pr O Cl SMe Pr O Cl Si-Pr Pr O Cl SCH ₂ C≡CH Pr O Cl SCH ₂ CO ₂ Et Pr O Cl SCH ₂ CO ₂ Pen CHF ₂ O Cl H CHF ₂ O Cl CH ₂ CH (Cl) CO ₂ Et CHF ₂ O Cl CH = C (Cl) CO ₂ Et CHF ₂ O Cl OMe CHF ₂ O Cl Oi-Pr CHF ₂ O Cl Oc-Pen CHF ₂ O Cl OCH ₂ CF ₃ CHF ₂ O Cl OCH ₂ CH = CH ₂ CHF ₂ O Cl OCH ₂ CH = CH (Cl) CHF ₂ O Cl OCH ₂ C≡CH CHF ₂ O Cl OCH (Me) C≡CH CHF ₂ O Cl OPh CHF ₂ O Cl OCH ₂ Ph CHF ₂ O Cl OCH ₂ CH = CH-Ph ────────────────────────────── ──────

[0091]

[Table 29] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ O Cl OCH ₂ CO ₂ Me CHF ₂ O Cl OCH ₂ CO ₂ Et CHF ₂ O Cl OCH ₂ CO ₂ Pen CHF ₂ O Cl SH CHF ₂ O Cl SMe CHF ₂ O Cl Si-Pr CHF ₂ O Cl Sc-Pen CHF ₂ O Cl SCH ₂ CH = CH ₂ CHF ₂ O Cl SCH ₂ CH = CHCl CHF ₂ O Cl SCH ₂ C≡CH CHF ₂ O Cl SCH (Me) C≡CH CHF ₂ O Cl SPh CHF ₂ O Cl SCH ₂ Ph CHF ₂ O Cl SCH ₂ CO ₂ Me CHF ₂ O Cl SCH ₂ CO ₂ Et CHF ₂ O Cl SCH ₂ CO ₂ Pen CHF ₂ O Cl F CHF ₂ O Cl Cl CHF ₂ O Cl Br CHF ₂ O Cl NH ₂ CHF ₂ O Cl NHMe CHF ₂ O Cl NHCO ₂ Et CHF ₂ O Cl NHCOMe ────────────────────────────────────

[0092]

[Table 30] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ O Cl NHCOPh CHF ₂ O Cl NHCH ₂ CO ₂ Et CHF ₂ O Cl NHSO ₂ Me CHF ₂ O Cl NHSO ₂ Et CHF ₂ O Cl NHSO ₂ NMe ₂ CHF ₂ O Cl N (CO-t-Bu) SO ₂ Me CHF ₂ O Cl N (CO-p-MeO-Ph) SO ₂ Me CHF ₂ O Cl CN CHF ₂ O Cl NO ₂ CHF ₂ O Cl CH ₂ CN CHF ₂ O Cl CHO CHF ₂ O Cl CO ₂ H CHF ₂ O Cl CO ₂ Et F (CH ₂ ) ₃ O Cl HF (CH ₂ ) ₃ O Cl CH ₂ CH (Cl) CO ₂ Et F (CH ₂ ) ₃ O Cl CH = C (Cl) CO ₂ Et F (CH ₂ ) ₃ O Cl OMe F (CH ₂ ) ₃ O Cl Oi- Pr F (CH ₂ ) ₃ O Cl Oc-Pen F (CH ₂ ) ₃ O Cl OCH ₂ CF ₃ F (CH ₂ ) ₃ O Cl OCH ₂ CH = CH ₂ F (CH ₂ ) ₃ O Cl OCH ₂ CH = CH (Cl) F (CH ₂ ) ₃ O Cl OCH ₂ C≡CH ───────────────────────────────── ───

[0093]

[Table 31] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ O Cl OCH (Me) C≡CH F ( CH ₂ ) ₃ O Cl OPh F (CH ₂ ) ₃ O Cl OCH ₂ Ph F (CH ₂ ) ₃ O Cl OCH ₂ CH = CH-Ph F (CH ₂ ) ₃ O Cl OCH ₂ CO ₂ Me F (CH ₂₎ ) ₃ O Cl OCH ₂ CO ₂ Et F (CH ₂ ) ₃ O Cl OCH ₂ CO ₂ Pen F (CH ₂ ) ₃ O Cl SH F (CH ₂ ) ₃ O Cl SMe F (CH ₂ ) ₃ O Cl Si- Pr F (CH ₂ ) ₃ O Cl Sc-Pen F (CH ₂ ) ₃ O Cl SCH ₂ CH = CH ₂ F (CH ₂ ) ₃ O Cl SCH ₂ CH = CHCl F (CH ₂ ) ₃ O Cl SCH ₂ C ≡CH F (CH ₂ ) ₃ O Cl SCH (Me) C≡CH F (CH ₂ ) ₃ O Cl SPh F (CH ₂ ) ₃ O Cl SCH ₂ Ph F (CH ₂ ) ₃ O Cl SCH ₂ CO ₂ Me F (CH ₂ ) ₃ O Cl SCH ₂ CO ₂ Et F (CH ₂ ) ₃ O Cl SCH ₂ CO ₂ Pen F (CH ₂ ) ₃ O Cl FF (CH ₂ ) ₃ O Cl Cl F (CH ₂ ) ₃ O Cl Br ────────────────────────────────── ─

[0094]

[Table 32] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ O Cl NH ₂ F (CH ₂ ) ₃ O Cl NHMe F (CH ₂ ) ₃ O Cl NHCO ₂ Et F (CH ₂ ) ₃ O Cl NHCOMe F (CH ₂ ) ₃ O Cl NHCOPh F (CH ₂ ) ₃ O Cl NHCH ₂ CO ₂ Et F (CH ₂ ) ₃ O Cl NHSO ₂ Me F (CH ₂ ) ₃ O Cl NHSO ₂ Et F (CH ₂ ) ₃ O Cl NHSO ₂ NMe ₂ F (CH ₂ ) ₃ O Cl N (CO-t-Bu) SO ₂ Me F (CH ₂ ) ₃ O Cl N (CO-p-MeO-Ph) SO ₂ Me F (CH ₂ ) ₃ O Cl CN F (CH ₂ ) ₃ O Cl NO ₂ F (CH ₂ ) ₃ O Cl CH ₂ CN F ( CH ₂ ) ₃ O Cl CHO F (CH ₂ ) ₃ O Cl CO ₂ HF (CH ₂ ) ₃ O Cl CO ₂ Et CH ₂ = CHCH ₂ O Cl H CH ₂ = CHCH ₂ O Cl CH ₂ CH (Cl) CO ₂ Et CH ₂ = CHCH ₂ O Cl CH = C (Cl) CO ₂ Et CH ₂ = CHCH ₂ O Cl OMe CH ₂ = CHCH ₂ O Cl Oi-Pr CH ₂ = CHCH ₂ O Cl Oc-Pen ──── ───────────────────────────────

[0095]

[Table 33] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ = CHCH ₂ O Cl OCH ₂ CF ₃ CH ₂ = CHCH ₂ O Cl OCH ₂ CH = CH ₂ CH ₂ = CHCH ₂ O Cl OCH ₂ CH = CH (Cl) CH ₂ = CHCH ₂ O Cl OCH ₂ C≡CH CH ₂ = CHCH ₂ O Cl OCH (Me) C≡CH CH ₂ = CHCH ₂ O Cl OPh CH ₂ = CHCH ₂ O Cl OCH ₂ Ph CH ₂ = CHCH ₂ O Cl OCH ₂ CH = CH-Ph CH ₂ = CHCH ₂ O Cl OCH ₂ CO ₂ Me CH ₂ = CHCH ₂ O Cl OCH ₂ CO ₂ Et CH ₂ = CHCH ₂ O Cl OCH ₂ CO ₂ Pen CH ₂ = CHCH ₂ O Cl SH CH ₂ = CHCH ₂ O Cl SMe CH ₂ = CHCH ₂ O Cl Si-Pr CH ₂ = CHCH ₂ O Cl Sc -Pen CH ₂ = CHCH ₂ O Cl SCH ₂ CH = CH ₂ CH ₂ = CHCH ₂ O Cl SCH ₂ CH = CHCl CH ₂ = CHCH ₂ O Cl SCH ₂ C≡CH CH ₂ = CHCH ₂ O Cl SCH (Me) C≡CH CH ₂ = CHCH ₂ O Cl SPh CH ₂ = CHCH ₂ O Cl SCH ₂ Ph CH ₂ = CHCH ₂ O Cl SCH ₂ CO ₂ Me CH ₂ = CHCH ₂ O Cl SCH ₂ CO ₂ Et ───── ──── ──────────────────────────

[0096]

[Table 34] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ = CHCH ₂ O Cl SCH ₂ CO ₂ Pen CH ₂ = CHCH ₂ O Cl F CH ₂ = CHCH ₂ O Cl Cl CH ₂ = CHCH ₂ O Cl Br CH ₂ = CHCH ₂ O Cl NH ₂ CH ₂ = CHCH ₂ O Cl NHMe CH ₂ = CHCH ₂ O Cl NHCO ₂ Et CH ₂ = CHCH ₂ O Cl NHCOMe CH ₂ = CHCH ₂ O Cl NHCOPh CH ₂ = CHCH ₂ O Cl NHCH ₂ CO ₂ Et CH ₂ = CHCH ₂ O Cl NHSO ₂ Me CH ₂ = CHCH ₂ O Cl NHSO ₂ Et CH ₂ = CHCH ₂ O Cl NHSO ₂ NMe ₂ CH ₂ = CHCH ₂ O Cl N (CO-t-Bu) SO ₂ Me CH ₂ = CHCH ₂ O Cl N (CO-p-MeO-Ph) SO ₂ Me CH ₂ = CHCH ₂ O Cl CN CH ₂ = CHCH ₂ O Cl NO ₂ CH ₂ = CHCH ₂ O Cl CH ₂ CN CH ₂ = CHCH ₂ O Cl CHO CH ₂ = CHCH ₂ O Cl CO ₂ H CH ₂ = CHCH ₂ O Cl CO ₂ Et Me O F H Me OF Me ────────────────────────────────────

[0097]

[Table 35] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OF CHO Me OF PhCH ₂ Me OF PhCH = CHCH ₂ Me _{O F CO 2 H Me O F} CO 2 Me Me O F CO 2 Et Me O F CH 2 CO 2 Me Me O F CH 2 CO 2 Et Me O F CH 2 CH (Cl) CO 2 Me Me O F CH 2 _{CH (Cl) CO 2 Et Me} O F CH = CHCO 2 Me Me O F CH = CHCO 2 Et Me O F CH = C (Cl) CO 2 Me Me O F CH = C (Cl) CO 2 Et Me O F OH Me OF OMe Me OF OEt Me OF Oi-Pr Me OF Oc-Pen Me OF OCH ₂ CF ₃ Me OF OCH ₂ CH = CH ₂ Me OF OCH ₂ CH = CH (Cl) Me O F OCH ₂ C≡CH ────────────────────────────────────

[0098]

[Table 36] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ─────────────────────────────────Me OF OCH (Me) C≡CH Me OF OPhMe OF OCH ₂ Ph Me OF OCH ₂ CH = CH-Ph Me OF OFCH ₂ CO ₂ Me Me OF OCH ₂ CO ₂ Et Me OF OFCH (Me) CO ₂ Me Me OF OCH (Me) CO ₂ Et Me OF OCH ₂ CO ₂ Pen Me OF SH Me OF SMe Me OF SEt Me OF Si-Pr Me OF Sc-Pen Me OF SCH ₂ CF ₃ Me OF SCH ₂ CH = CH ₂ Me OF SCH ₂ CH = CH (Cl) Me OF SCH ₂ C≡CH Me OF SCH (Me) C≡CH Me OF SPh Me OF SCH ₂ Ph Me OF SCH ₂ CH = CH-Ph Me OF SCH ₂ CO ₂ Me ────────────────────────────────────

[0099]

[Table 37] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OF SCH ₂ CO ₂ Et Me OF SCH (Me) CO ₂ Me Me O F SCH (Me) CO 2 Et Me O F SCH 2 CO 2 Pen Me O F NH 2 Me O F NHMe Me O F NHCH 2 CH = CH 2 Me O F NHCH 2 C≡CH Me O F NHCH 2 CF ₃ Me OF NHCO ₂ Me Me OF NHCO ₂ Et Me OF OF NHCOMe Me OF NHCOPh Me OF OF NHCH ₂ CO ₂ Me Me OF NHCH ₂ CO ₂ Et Me OF OF NHSO ₂ Me Me OF NH NH ₂ Et _{Me O F NHSO 2 NMe 2 Me} O F N (CO-t-Bu) SO 2 Me Me O F N (CO-p-MeO-Ph) SO 2 Me Me O F CN Me O F NO 2 Me O F CH ₂ CN ────────────────────────────────────

[0100]

[Table 38] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OF F Me OF Cl Me OF Br Me OF I Et O F H Et O F Me Et O F CHO Et O F PhCH 2 Et O F PhCH = CHCH 2 Et O F CO 2 H Et O F CO 2 Me Et O F CO 2 Et Et O F CH 2 CO 2 Me Et _{O F CH 2 CO 2 Et Et} O F CH 2 CH (Cl) CO 2 Me Et O F CH 2 CH (Cl) CO 2 Et Et O F CH = CHCO 2 Me Et O F CH = CHCO 2 Et Et O F CH = C (Cl) CO ₂ Me Et OF CH = C (Cl) CO ₂ Et Et OF OH Et OF OMe Et OFE t ───────────────────

[0101]

[Table 39] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OFF Oi-Pr Et OFF Oc-Pen Et OFF OCH _{2 CF 3 Et O F OCH 2 CH} = CH 2 Et O F OCH 2 CH = CH (Cl) Et O F OCH 2 C≡CH Et O F OCH (Me) C≡CH Et O F OPh Et O F OCH 2 Ph _{Et O F OCH 2 CH = CH} -Ph Et O F OCH 2 CO 2 Me Et O F OCH 2 CO 2 Et Et O F OCH (Me) CO 2 Me Et O F OCH (Me) CO 2 Et Et O F OCH ₂ CO ₂ Pen Et OF SH Et OF SMe Et OF SEt Et OF Si-Pr Et OF Sc-Pen Et OF SCH ₂ CF ₃ Et OF SCH ₂ CH = CH ₂ Et OF SCH ₂ CH = CH (Cl) ────────────────────────────────────

[0102]

[Table 40] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ─────────────────────────────────Et OF SCH ₂ C≡CH Et OF SCH (Me) C≡ CH Et OF SPh Et OF SCH ₂ Ph Et OF SCH ₂ CH = CH-Ph Et OF SCH ₂ CO ₂ Me Et OF SCH ₂ CO ₂ Et Et OF SCH (Me) CO ₂ Me Et OF _{SCH (Me) CO 2 Et Et} O F SCH 2 CO 2 Pen Et O F NH 2 Et O F NHMe Et O F NHCH 2 CH = CH 2 Et O F NHCH 2 C≡CH Et O F NHCH 2 CF 3 Et O F NHCO ₂ Me Et OF OF NHCO ₂ Et Et OF NHCOMe Et OF NHCOPh Et OF NHCH ₂ CO ₂ Me Et OF OF NHCH ₂ CO ₂ Et Et OF NHSO ₂ Me Et OF NHSO ₂ Et ──── ────────────────────────────────

[0103]

[Table 41] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OF NHSO ₂ NMe ₂ Et OF N (CO-t-Bu ) SO ₂ Me Et OFN (CO-p-MeO-Ph) SO ₂ Me Et OF CF CN Et OF NO ₂ Et OF CH ₂ CN Et OF F Et OF Cl Et OF Br Br OF I Pr OF H Pr OF CH ₂ CH (Cl) CO ₂ Et Pr OF CH = C (Cl) CO ₂ Et Pr OF OMe Pr OF F Oi-Pr Pr OF F Oc-Pen Pr OF F OCH _{2 CF 3 Pr O F OCH 2 CH} = CH 2 Pr O F OCH 2 CH = CH (Cl) Pr O F OCH 2 C≡CH Pr O F OCH (Me) C≡CH Pr O F OPh Pr O F OCH 2 Ph ────────────────────────────────────

[0104]

[Table 42] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr OFCH ₂ CH = CH-Ph Pr OF CH ₂ CO _{2 Me Pr O F OCH 2 CO 2} Et Pr O F OCH 2 CO 2 Pen Pr O F NH 2 Pr O F NHMe Pr O F NHCO 2 Et Pr O F NHCOMe Pr O F NHCOPh Pr O F NHCH 2 CO 2 Et Pr O _{F NHSO 2 Me Pr O F NHSO} 2 Et Pr O F NHSO 2 NMe 2 Pr O F CN Pr O F NO 2 Pr O F CO 2 H Pr O F CHO Pr O F CO 2 Et Pr O F SH Pr O F SMe Pr OF Si-Pr Pr OF Sc-Pen Pr OF SCH ₂ CH = CH ₂ ───────────────────────────── ───────

[0105]

[Table 43] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr OF SCH ₂ C≡CH Pr OF SPh Pr OF SCH ₂ Ph Pr OF SCH ₂ CO ₂ Et Pr OF SCH ₂ CO ₂ Pen Pr OF F Pr OF Cl CHF ₂ OF H CHF ₂ OF Me CHF ₂ OF CHO CHF ₂ OF PhCH ₂ CHF ₂ OF PhCH = CHCH ₂ CHF ₂ OF CO ₂ H CHF ₂ OF OF CO ₂ Me CHF ₂ OF CO ₂ Et CHF ₂ OF CH ₂ CO ₂ Me CHF ₂ OF CH ₂ CO ₂ Et CHF ₂ OF CH ₂ CH (Cl) CO ₂ Me CHF ₂ OF CH ₂ CH (Cl) CO ₂ Et CHF ₂ OF CH = CHCO ₂ Me CHF ₂ OF CH = CHCO ₂ Et CHF ₂ OF CH = C (Cl) CO ₂ Me CHF ₂ OF CH = C (Cl) CO ₂ Et ────────────────────────────────────

[0106]

[Table 44] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF OH CHF ₂ OF F OMe CHF ₂ OF OEt CHF _{2 O F Oi-Pr CHF 2 O} F Oc-Pen CHF 2 O F OCH 2 CF 3 CHF 2 O F OCH 2 CH = CH 2 CHF 2 O F OCH 2 CH = CH (Cl) CHF 2 O F OCH 2 C≡ _{CH CHF 2 O F OCH (Me} ) C≡CH CHF 2 O F OPh CHF 2 O F OCH 2 Ph CHF 2 O F OCH 2 CH = CH-Ph CHF 2 O F OCH 2 CO 2 Me CHF 2 O F OCH 2 _{CO 2 Et CHF 2 O F OCH} (Me) CO 2 Me CHF 2 O F OCH (Me) CO 2 Et CHF 2 O F OCH 2 CO 2 Pen CHF 2 O F SH CHF 2 O F SMe CHF 2 O F SEt CHF ₂ OF Si-Pr CHF ₂ OF Sc-Pen ────────────────────────────────────

[0107]

[Table 45] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF SCH ₂ CF ₃ CHF ₂ OF SCH ₂ CH = CH ₂ CHF ₂ OF SCH ₂ CH = CH (Cl) CHF ₂ OF SCH ₂ C≡CH CHF ₂ OF SCH (Me) C≡CH CHF ₂ OF SPh CHF ₂ OF SCH ₂ Ph CHF ₂ OF SCH ₂ CH = CH-Ph CHF ₂ OF SCH ₂ CO ₂ Me CHF ₂ OF SCH ₂ CO ₂ Et CHF ₂ OF SCH (Me) CO ₂ Me CHF ₂ OF SCH (Me) CO ₂ Et CHF ₂ OF _{SCH 2 CO 2 Pen CHF 2 O} F NH 2 CHF 2 O F NHMe CHF 2 O F NHCH 2 CH = CH 2 CHF 2 O F NHCH 2 C≡CH CHF 2 O F NHCH 2 CF 3 CHF 2 O F NHCO 2 Me CHF ₂ OF NHCO ₂ Et CHF ₂ OF NHCOMe CHF ₂ OF NHCOPh CHF ₂ OF NHCH ₂ CO ₂ Me ────────────

[0108]

[Table 46] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF NHCH ₂ CO ₂ Et CHF ₂ OF NHSO ₂ Me CHF ₂ OF NHSO ₂ Et CHF ₂ OF NHSO ₂ NMe ₂ CHF ₂ OF N (CO-t-Bu) SO ₂ Me CHF ₂ OF N (CO-p-MeO-Ph) SO ₂ Me CHF ₂ OF CN CHF ₂ OF NO ₂ CHF ₂ OF CH ₂ CN CHF ₂ OF F CHF ₂ OF Cl CHF ₂ OF Br CHF ₂ OF IF (CH ₂ ) ₃ OF HF (CH ₂ ) ₃ O F Me F (CH ₂ ) ₃ OF CHO F (CH ₂ ) ₃ OF PhCH ₂ F (CH ₂ ) ₃ OF PhCH = CHCH ₂ F (CH ₂ ) ₃ OF CO ₂ HF (CH ₂ ) ₃ O F CO ₂ Me F (CH ₂ ) ₃ OF CO ₂ Et F (CH ₂ ) ₃ OF CH ₂ CO ₂ Me F (CH ₂ ) ₃ OF CH ₂ CO ₂ Et ───────── ───────────────────────────

[0109]

[Table 47] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF CH ₂ CH (Cl) CO ₂ Me F (CH ₂ ) ₃ OF CH ₂ CH (Cl) CO ₂ Et F (CH ₂ ) ₃ OF CH = CHCO ₂ Me F (CH ₂ ) ₃ OF CH = CHCO ₂ Et F (CH ₂ ) ₃ O F CH = C (Cl) CO ₂ Me F (CH ₂ ) ₃ OF CH = C (Cl) CO ₂ Et F (CH ₂ ) ₃ OF H O F (CH ₂ ) ₃ OF F OMe F (CH ₂ ) ₃ OFEt F (CH ₂ ) ₃ OF Oi-Pr F (CH ₂ ) ₃ OF Oc-Pen F (CH ₂ ) ₃ OF OCH ₂ CF ₃ F (CH ₂ ) ₃ OF OCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF F OCH ₂ CH = CH (Cl) F (CH ₂ ) ₃ OF F OCH ₂ C≡CH F (CH ₂ ) ₃ OF F OCH (Me) C≡CH F (CH ₂ ) ₃ OF OPh F (CH ₂ ) ₃ OF OCH ₂ Ph F (CH ₂ ) ₃ OF OCH ₂ CH = CH-Ph F (CH ₂ ) ₃ OF OCH ₂ CO ₂ Me F (CH ₂ ) ₃ OF OCH ₂ CO ₂ Et F (CH ₂ ) ₃ OF OCH (Me) CO ₂ Me F (CH ₂ ) ₃ OF OCH (Me) CO ₂ Et ─────────────────────────

[0110]

[Table 48] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF F OCH ₂ CO ₂ Pen F (CH _{2 ) 3 O F SH F (CH} 2) 3 O F SMe F (CH 2) 3 O F SEt F (CH 2) 3 O F Si-Pr F (CH 2) 3 O F Sc-Pen F (CH 2) ₃ OF SCH ₂ CF ₃ F (CH ₂ ) ₃ OF SCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF SCH ₂ CH = CH (Cl) F (CH ₂ ) ₃ OF SCH ₂ C≡CH F (CH ₂ ) ₃ OF SCH (Me) C≡CH F (CH ₂ ) ₃ OF SPh F (CH ₂ ) ₃ OF SCH ₂ Ph F (CH ₂ ) ₃ OF SCH ₂ CH = CH-Ph F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Me F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Et F (CH ₂ ) ₃ OF SCH (Me) CO ₂ Me F (CH ₂ ) ₃ OF SCH (Me) CO ₂ Et F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Pen F (CH ₂ ) ₃ OF NH ₂ F (CH ₂ ) ₃ OF NHMe F (CH ₂ ) ₃ OF NHCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF NHCH ₂ C≡CH ──────────────────── ────────────────

[0111]

[Table 49] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF NHCH ₂ CF ₃ F (CH ₂ ) ₃ OF NHCO ₂ Me F (CH ₂ ) ₃ OF NHCO ₂ Et F (CH ₂ ) ₃ OF NHCOMe F (CH ₂ ) ₃ OF NHCOPh F (CH ₂ ) ₃ OF NHCH ₂ CO ₂ Me F ( CH ₂ ) ₃ OF NHCH ₂ CO ₂ Et F (CH ₂ ) ₃ OF NHSO ₂ Me F (CH ₂ ) ₃ OF NHSO ₂ Et F (CH ₂ ) ₃ OF NHSO ₂ NMe ₂ F (CH ₂ ) _{3 O F N (CO-t} -Bu) SO 2 Me F (CH 2) 3 O F N (CO-p-MeO-Ph) SO 2 Me F (CH 2) 3 O F CN F (CH 2) 3 OF NO ₂ F (CH ₂ ) ₃ OF CH ₂ CNF (CH ₂ ) ₃ OF F F (CH ₂ ) ₃ OF Cl F (CH ₂ ) ₃ OF Br F (CH ₂ ) ₃ OF I CH ₂ CH = CH ₂ OF H CH ₂ CH = CH ₂ OF Me CH ₂ CH = CH ₂ OF CHO CH ₂ CH = CH ₂ OF PhCH ₂ ──────────── ────────────────────── ──

[0112]

[Table 50] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF PhCH = CHCH ₂ CH ₂ CH = CH _{2 O F CO 2 H CH 2} CH = CH 2 O F CO 2 Me CH 2 CH = CH 2 O F CO 2 Et CH 2 CH = CH 2 O F CH 2 CO 2 Me CH 2 CH = CH 2 O F CH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF CH ₂ CH (Cl) CO ₂ Me CH ₂ CH = CH ₂ OF CH ₂ CH (Cl) CO ₂ Et CH ₂ CH = CH ₂ OF CH = CHCO ₂ Me CH ₂ CH = CH ₂ OF CH = CHCO ₂ Et CH ₂ CH = CH ₂ OF CH = C (Cl) CO ₂ Me CH ₂ CH = CH ₂ OF CH = C (Cl) CO ₂ Et CH _{2 CH = CH 2 O F OH CH} 2 CH = CH 2 O F OMe CH 2 CH = CH 2 O F OEt CH 2 CH = CH 2 O F Oi-Pr CH 2 CH = CH 2 O F Oc-Pen CH 2 CH = CH ₂ OF OCH ₂ CF ₃ CH ₂ CH = CH ₂ OF OFCH ₂ CH = CH ₂ CH ₂ CH = CH ₂ OF OFCH ₂ CH = CH (Cl) CH ₂ CH = CH ₂ OF OFCH ₂ C _{≡CH CH 2 CH = CH 2 O} F OCH (Me) C≡CH CH 2 CH = CH 2 O F OPh ── ─────────────────────────────────

[0113]

TABLE 51] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OFCH ₂ Ph CH ₂ CH = CH _{2 O F OCH 2 CH = CH-} Ph CH 2 CH = CH 2 O F OCH 2 CO 2 Me CH 2 CH = CH 2 O F OCH 2 CO 2 Et CH 2 CH = CH 2 O F OCH (Me) CO 2 Me _{CH 2 CH = CH 2 O F} OCH (Me) CO 2 Et CH 2 CH = CH 2 O F OCH 2 CO 2 Pen CH 2 CH = CH 2 O F SH CH 2 CH = CH 2 O F SMe CH 2 CH = CH ₂ OF SEt CH ₂ CH = CH ₂ OF Si-Pr CH ₂ CH = CH ₂ OF Sc-Pen CH ₂ CH = CH ₂ OF SCH ₂ CF ₃ CH ₂ CH = CH ₂ OF SCH ₂ CH _{= CH 2 CH 2 CH = CH} 2 O F SCH 2 CH = CH (Cl) CH 2 CH = CH 2 O F SCH 2 C≡CH CH 2 CH = CH 2 O F SCH (Me) C≡CH CH 2 CH = CH ₂ OF SPh CH ₂ CH = CH ₂ OF SCH ₂ Ph CH ₂ CH = CH ₂ OF SCH ₂ CH = CH-Ph CH ₂ CH = CH ₂ OF SCH ₂ CO ₂ Me CH ₂ CH = CH _{2 O F SCH 2 CO 2 Et} CH 2 CH = CH 2 O F SCH (Me) CO 2 Me ───────────────────────────────────

[0114]

[Table 52] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF SCH (Me) CO ₂ Et CH ₂ CH = CH ₂ OF SCH ₂ CO ₂ Pen CH ₂ CH = CH ₂ OF NH ₂ CH ₂ CH = CH ₂ OF NHMe CH ₂ CH = CH ₂ OF NHCH ₂ CH = CH ₂ CH ₂ CH = CH ₂ OF NHCH ₂ C≡CH CH ₂ CH = CH ₂ OF NHCH ₂ CF ₃ CH ₂ CH = CH ₂ OF NHCO ₂ Me CH ₂ CH = CH ₂ OF NHCO ₂ Et CH ₂ CH = CH ₂ OF NHCOMe CH ₂ CH = CH ₂ OF NHCOPh CH ₂ CH = CH ₂ OF NHCH ₂ CO ₂ Me CH ₂ CH = CH ₂ OF NHCH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF NHSO ₂ Me CH ₂ CH = CH ₂ OF NHSO ₂ Et CH ₂ CH = CH ₂ OF NHSO ₂ NMe ₂ CH ₂ CH = CH ₂ OF N (CO-t-Bu) SO ₂ Me CH ₂ CH = CH ₂ OF N (CO- p-MeO-Ph) SO ₂ Me CH ₂ CH = CH ₂ OF CN CN CH ₂ CH = CH ₂ OF NO ₂ CH ₂ CH = CH ₂ OF CH ₂ CN CH ₂ CH = CH ₂ OF F CH ₂ CH = CH ₂ O F Cl ────── ─────────────────────────────

[0115]

[Table 53] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF Br CH ₂ CH = CH ₂ OF I HC≡CCH ₂ OF H HC≡CCH ₂ OF CH ₂ CH (Cl) CO ₂ Et HC≡CCH ₂ OF CH = C (Cl) CO ₂ Et HC≡CCH ₂ OF F OMe HC≡CCH ₂ O F Oi-Pr HC≡CCH ₂ OF F Oc-Pen HC≡CCH ₂ OF F OCH ₂ CF ₃ HC≡CCH ₂ OF F OCH ₂ CH = CH ₂ HC≡CCH ₂ OF F OCH ₂ CH = CH (Cl) HC _{≡CCH 2 O F OCH 2 C≡CH HC≡CCH} 2 O F OCH (Me) C≡CH HC≡CCH 2 O F OPh HC≡CCH 2 O F OCH 2 Ph HC≡CCH 2 O F OCH 2 CH = CH -Ph HC≡CCH ₂ OF F OCH ₂ CO ₂ Me HC≡CCH ₂ OF F OCH ₂ CO ₂ Et HC≡CCH ₂ OF F OCH ₂ CO ₂ Pen HC≡CCH ₂ OF SH HC≡CCH ₂ OF SMe HC ≡CCH ₂ OF Si-Pr HC≡CCH ₂ OF Sc-Pen ─────────────────────────── ─────────

[0116]

[Table 54] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── HC≡CCH ₂ O F SCH ₂ CH = CH ₂ HC≡CCH ₂ O F SCH ₂ CH = CHCl HC≡CCH ₂ OF SCH ₂ C≡CH HC≡CCH ₂ OF SCH (Me) C≡CH HC≡CCH ₂ OF SPh HC≡CCH ₂ OF SCH ₂ Ph HC≡CCH ₂ OF SCH ₂ CO ₂ Me HC≡CCH ₂ OF SCH ₂ CO ₂ Et HC≡CCH ₂ OF SCH ₂ CO ₂ Pen HC≡CCH ₂ OF F HC≡CCH ₂ OF Cl Cl HC≡CCH ₂ OF Br HC≡CCH ₂ OF NH ₂ HC≡CCH ₂ OF NHMe HC≡CCH ₂ OF NHCO ₂ Et HC≡CCH ₂ OF NHCOMe HC≡CCH ₂ OF NHCOPh HC≡CCH ₂ OF NHCH ₂ CO ₂ Et HC ≡CCH ₂ OF NHSO ₂ Me HC≡CCH ₂ OF NHSO ₂ Et HC≡CCH ₂ OF NHSO ₂ NMe ₂ HC≡CCH ₂ OF N (CO-t-Bu) SO ₂ Me HC≡CCH ₂ OF N (CO-p-MeO- Ph) SO 2 Me ───────────────────── ──────────────

[0117]

[Table 55] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── _{───────────────────────────────── HC≡CCH 2 O F CN HC≡CCH 2} O F NO 2 HC≡ CCH ₂ OF CH ₂ CN HC≡CCH ₂ OF CHO HC≡CCH ₂ OF CO ₂ H HC≡CCH ₂ OF CO ₂ Et PhCH ₂ OF H PhCH ₂ OF CH ₂ CH (Cl) CO ₂ Et _{PhCH 2 O F CH = C (} Cl) CO 2 Et PhCH 2 O F Oc-Pen PhCH 2 O F OCH 2 C≡CH PhCH 2 O F OCH 2 CO 2 Et PhCH 2 O F Si-Pr PhCH 2 O F SCH _{2 C≡CH PhCH 2 O F SCH 2} CO 2 Et PhCH 2 O F NHSO 2 Me PhCH 2 O F NHSO 2 Et PhCH 2 O F CO 2 Et Ph (2-Cl) CH 2 O F H Ph (2-Cl ) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (2-Cl) CH ₂ OF CH = C (Cl) CO ₂ Et Ph (2-Cl) CH ₂ OF F Oc-Pen Ph (2- Cl) CH ₂ OF F OCH ₂ C≡CH ────────────────────────────────────

[0118]

[Table 56] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (2-Cl) CH ₂ OF F OCH ₂ CO ₂ Et Ph ( _{2-Cl) CH 2 O F} Si-Pr Ph (2-Cl) CH 2 O F SCH 2 C≡CH Ph (2-Cl) CH 2 O F SCH 2 CO 2 Et Ph (2-Cl) CH 2 O F NHSO ₂ Me Ph (2-Cl) CH ₂ OF NHSO ₂ Et Ph (2-Cl) CH ₂ OF CO ₂ Et Ph (3-Cl) CH ₂ OF H Ph (3-Cl) CH ₂ O F CH ₂ CH (Cl) CO ₂ Et Ph (3-Cl) CH ₂ OF CH = C (Cl) CO ₂ Et Ph (3-Cl) CH ₂ OF F Oc-Pen Ph (3-Cl) CH _{2 O F OCH 2 C≡CH Ph (3} -Cl) CH 2 O F OCH 2 CO 2 Et Ph (3-Cl) CH 2 O F Si-Pr Ph (3-Cl) CH 2 O F SCH 2 C≡CH Ph (3-Cl) CH ₂ OF SCH ₂ CO ₂ Et Ph (3-Cl) CH ₂ OF NHSO ₂ Me Ph (3-Cl) CH ₂ OF NHSO ₂ Et Ph (3-Cl) CH ₂ O F CO ₂ Et Ph (4-Cl) CH ₂ OF H Ph (4-Cl) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (4-Cl) CH ₂ OF CH = C (Cl) CO ₂ Et Ph (4-Cl) CH ₂ OF F Oc-Pen ── ──────────────────────────────────

[0119]

[Table 57] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (4-Cl) CH 2 O F OCH 2 C≡CH Ph ( _{4-Cl) CH 2 O F} OCH 2 CO 2 Et Ph (4-Cl) CH 2 O F Si-Pr Ph (4-Cl) CH 2 O F SCH 2 C≡CH Ph (4-Cl) CH 2 O F SCH ₂ CO ₂ Et Ph (4-Cl) CH ₂ OF NHSO ₂ Me Ph (4-Cl) CH ₂ OF NHSO ₂ Et Ph (4-Cl) CH ₂ OF CO ₂ Et Ph (2,3 -Cl ₂ ) CH ₂ OF H Ph (2,3-Cl ₂ ) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF CH = C (Cl) _{CO 2 Et Ph (2,3-Cl} 2) CH 2 O F Oc-Pen Ph (2,3-Cl 2) CH 2 O F OCH 2 C≡CH Ph (2,3-Cl 2) CH 2 O F _{OCH 2 CO 2 Et Ph (2,3} -Cl 2) CH 2 O F Si-Pr Ph (2,3-Cl 2) CH 2 O F SCH 2 C≡CH Ph (2,3-Cl 2) CH 2 OF SCH ₂ CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF NHSO ₂ Me Ph (2,3-Cl ₂ ) CH ₂ OF NHSO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF H Ph (2,4-Cl ₂ ) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF CH = C (Cl) CO ₂ Et ────────────── ──────────────────────

[0120]

[Table 58] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (2,4-Cl ₂ ) CH ₂ OF F Oc-Pen Ph (2,4-Cl ₂ ) CH ₂ OF F OCH ₂ C≡CH Ph (2,4-Cl ₂ ) CH ₂ OF F OCH ₂ CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF Si Pr Ph (2,4-Cl ₂ ) CH ₂ OF SCH ₂ C≡CH Ph (2,4-Cl ₂ ) CH ₂ OF SCH ₂ CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF NHSO ₂ Me Ph (2,4-Cl ₂ ) CH ₂ OF NHSO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF CO ₂ Et PhCH ₂ CH ₂ OF H PhCH ₂ CH ₂ OF CH _{2 CH (Cl) CO 2 Et PhCH} 2 CH 2 O F CH = C (Cl) CO 2 Et PhCH 2 CH 2 O F Oc-Pen PhCH 2 CH 2 O F OCH 2 C≡CH PhCH 2 CH 2 O F OCH 2 _{CO 2 Et PhCH 2 CH 2 O} F Si-Pr PhCH 2 CH 2 O F SCH 2 C≡CH PhCH 2 CH 2 O F SCH 2 CO 2 Et PhCH 2 CH 2 O F NHSO 2 Me PhCH 2 CH 2 O F NHSO _{2 Et PhCH 2 CH 2 O F} CO 2 Et PhCH = CHCH 2 O F H PhCH = CHCH 2 O _{CH 2 CH (Cl) CO 2} Et ────────────────────────────────────

[0121]

[Table 59] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── PhCH = CHCH ₂ OF CH = C (Cl) CO ₂ Et PhCH = _{CHCH 2 O F Oc-Pen PhCH} = CHCH 2 O F OCH 2 C≡CH PhCH = CHCH 2 O F OCH 2 CO 2 Et PhCH = CHCH 2 O F Si-Pr PhCH = CHCH 2 O F SCH 2 C≡CH PhCH = CHCH ₂ OF SCH ₂ CO ₂ Et PhCH = CHCH ₂ OF NHSO ₂ Me PhCH = CHCH ₂ OF NHSO ₂ Et PhCH = CHCH ₂ OF CO ₂ Et MeO OF H MeO OF CH ₂ CH (Cl) _{CO 2 Et MeO O F CH =} C (Cl) CO 2 Et MeO O F Oc-Pen MeO O F OCH 2 C≡CH MeO O F OCH 2 CO 2 Et MeO O F Si-Pr MeO O F SCH 2 C≡ CH MeO OF SCH ₂ CO ₂ Et MeO OF NHSO ₂ Me MeO OF NHSO ₂ Et MeO OF CO ₂ Et CHF ₂ SF H ────────────────── ──────────────────

[0122]

[Table 60] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF Me CHF ₂ SF CHO CHF ₂ SF PhCH ₂ CHF ₂ SF PhCH = CHCH ₂ CHF ₂ SF CO ₂ H CHF ₂ SF CO ₂ Me CHF ₂ SF CO ₂ Et CHF ₂ SF CH ₂ CO ₂ Me CHF ₂ SF CH ₂ CO ₂ Et CHF ₂ SF CH ₂ CH (Cl) CO ₂ Me CHF ₂ SF CH ₂ CH (Cl) CO ₂ Et CHF ₂ SF CH = CHCO ₂ Me CHF ₂ SF CH = CHCO ₂ Et CHF ₂ SF CH = C (Cl) CO ₂ Me CHF ₂ S F CH = C (Cl) CO ₂ Et CHF ₂ S F OH CHF ₂ S F OMe CHF ₂ S F OEt CHF ₂ S F Oi-Pr CHF ₂ S F Oc-Pen CHF ₂ S F OCH ₂ CF ₃ CHF ₂ SF OCH ₂ CH = CH ₂ CHF ₂ SF OCH ₂ CH = CH (Cl) ───────────────────────── ───────────

[0123]

[Table 61] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF OCH ₂ C≡CH CHF ₂ SF OCH (Me) _{C≡CH CHF 2 S F OPh CHF 2} S F OCH 2 Ph CHF 2 S F OCH 2 CH = CH-Ph CHF 2 S F OCH 2 CO 2 Me CHF 2 S F OCH 2 CO 2 Et CHF 2 S F OCH ( _{Me) CO 2 Me CHF 2 S} F OCH (Me) CO 2 Et CHF 2 S F OCH 2 CO 2 Pen CHF 2 S F SH CHF 2 S F SMe CHF 2 S F SEt CHF 2 S F Si-Pr CHF 2 S _{F Sc-Pen CHF 2 S F} SCH 2 CF 3 CHF 2 S F SCH 2 CH = CH 2 CHF 2 S F SCH 2 CH = CH (Cl) CHF 2 S F SCH 2 C≡CH CHF 2 S F SCH (Me ) C≡CH CHF ₂ SF SPh CHF ₂ SF SCH ₂ Ph CHF ₂ SF SCH ₂ CH = CH-Ph ─────────────

[0124]

[Table 62] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF SCH ₂ CO ₂ Me CHF ₂ SF SCH ₂ CO ₂ Et CHF ₂ SF SCH (Me) CO ₂ Me CHF ₂ SF SCH (Me) CO ₂ Et CHF ₂ SF SCH ₂ CO ₂ Pen CHF ₂ SF NH ₂ CHF ₂ SF NHMe CHF ₂ SF NHCH ₂ CH _{= CH 2 CHF 2 S F NHCH} 2 C≡CH CHF 2 S F NHCH 2 CF 3 CHF 2 S F NHCO 2 Me CHF 2 S F NHCO 2 Et CHF 2 S F NHCOMe CHF 2 S F NHCOPh CHF 2 S F NHCH 2 CO ₂ Me CHF ₂ SF NHCH ₂ CO ₂ Et CHF ₂ SF SF NHSO ₂ Me CHF ₂ SF NHSO ₂ Et CHF ₂ SF NHSO ₂ NMe ₂ CHF ₂ SF N (CO-t-Bu) SO ₂ Me CHF _{2 S F N (CO-p} -MeO-Ph) SO 2 Me CHF 2 S F CN CHF 2 S F NO 2 ─────────────────────── ─────────────

[0125]

[Table 63] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── _{───────────────────────────────── CHF 2 S F CH 2 CN} CHF 2 S F F CHF 2 S F Cl CHF ₂ SF Br CHF ₂ S FI Me OF N (CHO) SO ₂ Me Me OF OCH (Me) C≡CH CHF ₂ OF N (CHO) SO ₂ Me CHF ₂ OF OCH (Me) C ≡CH F (CH ₂ ) ₃ OF N (CHO) SO ₂ Me F (CH ₂ ) ₃ OF F OCH (Me) C≡CH CH ₂ = CHCH ₂ OF N (CHO) SO ₂ Me CH ₂ = CHCH ₂ O F OCH (Me) C {CH}. Table 6

[0126]

Embedded image

In the group of compounds represented by

[0128]

[Table 64] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OFH Me OF Me Me OF CHO Me OF PhCH ₂ Me OF PhCH = CHCH ₂ Me OF CO ₂ H Me OF CO ₂ Me Me OF CO ₂ Et Me OF CH ₂ CO ₂ Me Me OF CH ₂ CO ₂ Et Me OF CH ₂ CH (Cl) CO ₂ Me Me OF CH ₂ CH (Cl) CO ₂ Et Me OF CH = CHCO ₂ Me Me OF CH = CHCO ₂ Et Me OF CH = C (Cl) CO ₂ Me Me OF CH = C ( Cl) CO ₂ Et Me OF OH Me OF OFeMeMe OF OEtMe OF Oi-Pr Me OF Oc-Pen Me OF OCH ₂ CF ₃ Me OF F OCH ₂ CH = CH ₂ ───── ───────────────────────────────

[0129]

[Table 65] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OFCH ₂ CH = CH (Cl) Me OF CH ₂ C ≡CH Me OF OCH (Me) C≡CH Me OF OPh Me OF OFCH ₂ PhMe OF OCH ₂ CH = CH-Ph Me OF OCH ₂ CO ₂ Me Me OF OFCH ₂ CO ₂ Et Me O F OCH (Me) CO ₂ Me Me OF F OCH (Me) CO ₂ Et Me OF OCH ₂ CO ₂ Pen Me OF SH Me Me OF SMe Me OF SEt Me OF Si-Pr Me OF Sc-Pen Me OF SCH ₂ CF ₃ Me OF SCH ₂ CH = CH ₂ Me OF SCH ₂ CH = CH (Cl) Me OF SCH ₂ C≡CH Me OF SCH (Me) C≡CH Me OF SPh Me OF SCH ₂ Ph ────────────────────────────────────

[0130]

[Table 66] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OF SCH ₂ CH = CH-Ph Me OF SCH ₂ CO _{2 Me Me O F SCH 2 CO 2} Et Me O F SCH (Me) CO 2 Me Me O F SCH (Me) CO 2 Et Me O F SCH 2 CO 2 Pen Me O F NH 2 Me O F NHMe Me O F NHCH _{2 CH = CH 2 Me O F} NHCH 2 C≡CH Me O F NHCH 2 CF 3 Me O F NHCO 2 Me Me O F NHCO 2 Et Me O F NHCOMe Me O F NHCOPh Me O F NHCH 2 CO 2 Me Me O F NHCH ₂ CO ₂ Et Me OF NHSO ₂ Me Me OF OF NHSO ₂ Et Me OF NH NH ₂ NMe ₂ Me OF N (CO-t-Bu) SO ₂ Me Me OF N (CO-p-MeO- Ph) SO ₂ Me Me OF CN ────────────────────────────────────

[0131]

[Table 67] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Me OF NO ₂ Me OF CH ₂ CN Me OF F Me O F Cl Me O F Br Me O F I Et O F H Et O F Me Et O F CHO Et O F PhCH 2 Et O F PhCH = CHCH 2 Et O F CO 2 H Et O F CO 2 Me Et O F CO _{2 Et Et O F CH 2 CO} 2 Me Et O F CH 2 CO 2 Et Et O F CH 2 CH (Cl) CO 2 Me Et O F CH 2 CH (Cl) CO 2 Et Et O F CH = CHCO 2 Me _{Et O F CH = CHCO 2 Et} Et O F CH = C (Cl) CO 2 Me Et O F CH = C (Cl) CO 2 Et Et O F OH ────────────── ──────────────────────

[0132]

[Table 68] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OF OMe Et OF OEt Et OF Oi-Pr Et OF Oc-Pen Et OF F OCH ₂ CF ₃ Et OF F OCH ₂ CH = CH ₂ Et OF F OCH ₂ CH = CH (Cl) Et OF F OCH ₂ C≡CH Et OF F OCH (Me) C≡CH Et O F OPh Et OF F OCH ₂ Ph Et OF F OCH ₂ CH = CH-Ph Et OF F OCH ₂ CO ₂ Me Et OF F OCH ₂ CO ₂ Et Et OF F OCH (Me) CO ₂ Me Et OF F OCH (Me ) CO ₂ Et Et OFCH ₂ CO ₂ Pen Et OF SH Et OF SMe Et OF SE T Et Et OF Si-Pr Et OF Sc-Pen Et OF SCH ₂ CF ₃ ─────── ─────────────────────────────

[0133]

[Table 69] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OF SCH ₂ CH = CH ₂ Et OF SCH ₂ CH = CH _{(Cl) Et O F SCH 2} C≡CH Et O F SCH (Me) C≡CH Et O F SPh Et O F SCH 2 Ph Et O F SCH 2 CH = CHPh Et O F SCH 2 CO 2 Me Et O F SCH ₂ CO ₂ Et Et OF SCH (Me) CO ₂ Me Et OF SCH (Me) CO ₂ Et Et OF SCH ₂ CO ₂ Pen Et OF NH ₂ Et OF NHMe Et OF NHCH ₂ CH = CH _{2 Et O F NHCH 2 C≡CH Et} O F NHCH 2 CF 3 Et O F NHCO 2 Me Et O F NHCO 2 Et Et O F NHCOMe Et O F NHCOPh Et O F NHCH 2 CO 2 Me Et O F NHCH 2 CO ₂ Et ────────────────────────────────────

[0134]

[Table 70] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Et OF NHSO ₂ Me Et OF NHSO ₂ Et Et OF NHSO _{2 NMe 2 Et O F N (CO} -t-Bu) SO 2 Me Et O F N (CO-p-MeO-Ph) SO 2 Me Et O F CN Et O F NO 2 Et O F CH 2 CN Et O F F Et OF Cl Et OF Br Et OF FI Pr OF F H Pr OF CH ₂ CH (Cl) CO ₂ Et Pr OF CH = C (Cl) CO ₂ Et Pr OF F OMe Pr OF F Oi− Pr Pr O F Oc-Pen Pr O F OCH ₂ CF ₃ Pr OF F OCH ₂ CH = CH ₂ Pr OF OCH ₂ CH = CH (Cl) Pr OF F OCH ₂ C≡CH Pr OF F OCH (Me) C ≡CH ────────────────────────────────────

[0135]

[Table 71] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr OF OPh Pr OF OCH ₂ Ph Pr OF OCH ₂ CH = CHPh Pr O F OCH ₂ CO ₂ Me Pr F OCH ₂ CO ₂ Et Pr OF F OCH ₂ CO ₂ Pen Pr OF NH ₂ Pr OF NHMe Pr OF OF NHCO ₂ Et Pr OF OF NHCOMe Pr OF NH NHCOPh Pr O F NHCH ₂ CO ₂ Et Pr OF NHSO ₂ Me Pr OF NHSO ₂ Et Pr OF NHSO ₂ NMe ₂ Pr OF CN Pr OF NO NO ₂ Pr OF CO ₂ H Pr OF OF CHO Pr OF CO ₂ Et Pr OF SH Pr OF SMe Pr OF Si-Pr ────────────────────────────────────

[0136]

[Table 72] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Pr OF Sc-Pen Pr OF SCH ₂ CH = CH ₂ Pr O F SCH ₂ C≡CH Pr OF SPh Pr OF SCH ₂ Ph Pr OF SCH ₂ CO ₂ Et Pr OF SCH ₂ CO ₂ Pen Pr OF FF Pr OF Cl CHF ₂ OF H CHF ₂ OF Me CHF ₂ OF CHO CHF ₂ OF PhCH ₂ CHF ₂ OF PhCH = CHCH ₂ CHF ₂ OF CO ₂ H CHF ₂ OF CO ₂ Me CHF ₂ OF CO ₂ Et CHF ₂ OF CH ₂ CO ₂ Me CHF _{2 O F CH 2 CO 2 Et} CHF 2 O F CH 2 CH (Cl) CO 2 Me CHF 2 O F CH 2 CH (Cl) CO 2 Et CHF 2 O F CH = CHCO 2 Me CHF 2 O F CH = CHCO ₂ Et ────────────────────────────────────

[0137]

[Table 73] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF CH = C (Cl) CO ₂ Me CHF ₂ OF CH = C (Cl) CO ₂ Et CHF ₂ OF OH CHF ₂ OF F OMe CHF ₂ OF OEt CHF ₂ OF Oi-Pr CHF ₂ OF Oc-Pen CHF ₂ OF OCH ₂ CF ₃ CHF ₂ OF _{OCH 2 CH = CH 2 CHF 2} O F OCH 2 CH = CH (Cl) CHF 2 O F OCH 2 C≡CH CHF 2 O F OCH (Me) C≡CH CHF 2 O F OPh CHF 2 O F OCH 2 Ph CHF ₂ OF OCH ₂ CH = CH-Ph CHF ₂ OF OFCH ₂ CO ₂ Me CHF ₂ OF OCH ₂ CO ₂ Et CHF ₂ OF OCH (Me) CO ₂ Me CHF ₂ OF OCH (Me) CO ₂ Et CHF ₂ OF OCH ₂ CO ₂ Pen CHF ₂ OF SH CHF ₂ OF SMe CHF ₂ OF SEt ───────────────────────── ───────────

[0138]

[Table 74] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF Si-Pr CHF ₂ OF Sc-Pen CHF ₂ O _{F SCH 2 CF 3 CHF 2 O} F SCH 2 CH = CH 2 CHF 2 O F SCH 2 CH = CH (Cl) CHF 2 O F SCH 2 C≡CH CHF 2 O F SCH (Me) C≡CH CHF 2 O F SPh CHF ₂ OF SCH ₂ Ph CHF ₂ OF SCH ₂ CH = CHPh CHF ₂ OF SCH ₂ CO ₂ Me CHF ₂ OF SCH ₂ CO ₂ Et CHF ₂ OF SCH (Me) CO ₂ Me CHF ₂ O F SCH (Me) CO ₂ Et CHF ₂ OF SCH ₂ CO ₂ Pen CHF ₂ OF NH ₂ CHF ₂ OF NHMe CHF ₂ OF NHCH ₂ CH = CH ₂ CHF ₂ OF OF NHCH ₂ C≡CH CHF ₂ O F NHCH ₂ CF ₃ CHF ₂ OF NHCO ₂ Me CHF ₂ OF NHCO ₂ Et CHF ₂ OF NHCOMe ────────────────────────── ──────────

[0139]

[Table 75] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ OF NHCOPh CHF ₂ OF NHCH ₂ CO ₂ Me CHF ₂ O F NHCH ₂ CO ₂ Et CHF ₂ OF NHSO ₂ Me CHF ₂ OF NHSO ₂ Et CHF ₂ OF NHSO ₂ NMe ₂ CHF ₂ OF N (CO-t-Bu) SO ₂ Me CHF ₂ OF N (CO -p-MeO-Ph) SO ₂ Me CHF ₂ OF CN CHF ₂ OF NO ₂ CHF ₂ OF CH ₂ CN CHF ₂ OF F CHF ₂ OF Cl ClF ₂ OF OF Br CHF ₂ OF IF ( _{CH 2) 3 O F H F} (CH 2) 3 O F Me F (CH 2) 3 O F CHO F (CH 2) 3 O F PhCH 2 F (CH 2) 3 O F PhCH = CHCH 2 F (CH ₂ ) ₃ OF CO ₂ HF (CH ₂ ) ₃ OF CO ₂ Me F (CH ₂ ) ₃ OF CO ₂ Et ───────────────────── ───────────────

[0140]

[Table 76] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF CH ₂ CO ₂ Me F (CH ₂ ) ₃ OF CH ₂ CO ₂ Et F (CH ₂ ) ₃ OF CH ₂ CH (Cl) CO ₂ Me F (CH ₂ ) ₃ OF CH ₂ CH (Cl) CO ₂ Et F (CH ₂ ) ₃ O F CH = CHCO ₂ Me F (CH ₂ ) ₃ OF CH = CHCO ₂ Et F (CH ₂ ) ₃ OF CH = C (Cl) CO ₂ Me F (CH ₂ ) ₃ OF CH = C (Cl) _{CO 2 Et F (CH 2)} 3 O F OH F (CH 2) 3 O F OMe F (CH 2) 3 O F OEt F (CH 2) 3 O F Oi-Pr F (CH 2) 3 O F Oc -Pen F (CH ₂ ) ₃ OF F OCH ₂ CF ₃ F (CH ₂ ) ₃ OF F OCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF F OCH ₂ CH = CH (Cl) F (CH ₂ ) _{3 O F OCH 2 C≡CH F (CH} 2) 3 O F OCH (Me) C≡CH F (CH 2) 3 O F OPh F (CH 2) 3 O F OCH 2 Ph F (CH 2) 3 O F _{OCH 2 CH = CH-Ph F} (CH 2) 3 O F OCH 2 CO 2 Me F (CH 2) 3 O F OCH 2 CO 2 Et ──────────── ───────────────────────

[0141]

[Table 77] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF F OCH (Me) CO ₂ Me F ( CH ₂ ) ₃ OF OCH (Me) CO ₂ Et F (CH ₂ ) ₃ OF OCH ₂ CO ₂ Pen F (CH ₂ ) ₃ OF SH F (CH ₂ ) ₃ OF SMe F (CH ₂ ) ₃ OFSEt F (CH ₂ ) ₃ OF Si-Pr F (CH ₂ ) ₃ OF Sc-Pen F (CH ₂ ) ₃ OF SCH ₂ CF ₃ F (CH ₂ ) ₃ OF SCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF SCH ₂ CH = CH (Cl) F (CH ₂ ) ₃ OF SCH ₂ C≡CH F (CH ₂ ) ₃ OF SCH (Me) C≡CH F (CH ₂ ) ₃ OF SPh F (CH ₂ ) ₃ OF SCH ₂ Ph F (CH ₂ ) ₃ OF SCH ₂ CH = CHPh F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Me F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Et F (CH ₂ ) ₃ OF SCH (Me) CO ₂ Me F (CH ₂ ) ₃ OF SCH (Me) CO ₂ Et F (CH ₂ ) ₃ OF SCH ₂ CO ₂ Pen F (CH ₂ ) ₃ OF NH ₂ F (CH ₂ ) ₃ OF NHMe ────────────────

[0142]

[Table 78] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── F (CH ₂ ) ₃ OF NHCH ₂ CH = CH ₂ F (CH ₂ ) ₃ OF NHCH ₂ C≡CH F (CH ₂ ) ₃ OF NHCH ₂ CF ₃ F (CH ₂ ) ₃ OF NHCO ₂ Me F (CH ₂ ) ₃ OF NHCO ₂ Et F (CH ₂ ) _{3 O F NHCOMe F (CH 2)} 3 O F NHCOPh F (CH 2) 3 O F NHCH 2 CO 2 Me F (CH 2) 3 O F NHCH 2 CO 2 Et F (CH 2) 3 O F NHSO 2 Me F (CH ₂ ) ₃ OF NHSO ₂ Et F (CH ₂ ) ₃ OF NHSO ₂ NMe ₂ F (CH ₂ ) ₃ OF N (CO-t-Bu) SO ₂ Me F (CH ₂ ) ₃ OF N (CO-p-MeO-Ph ) SO 2 Me F (CH 2) 3 O F CN F (CH 2) 3 O F NO 2 F (CH 2) 3 O F CH 2 CN F (CH 2) 3 O F F F (CH ₂ ) ₃ OF Cl F (CH ₂ ) ₃ OF Br F (CH ₂ ) ₃ OF I CH ₂ CH = CH ₂ OF H CH ₂ CH = CH ₂ OF Me ──── ───────────────────────── ──────

[0143]

[Table 79] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF CHO CH ₂ CH = CH ₂ OF _{PhCH 2 CH 2 CH = CH 2} O F PhCH = CHCH 2 CH 2 CH = CH 2 O F CO 2 H CH 2 CH = CH 2 O F CO 2 Me CH 2 CH = CH 2 O F CO 2 Et CH 2 CH = CH ₂ OF CH ₂ CO ₂ Me CH ₂ CH = CH ₂ OF CH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF CH ₂ CH (Cl) CO ₂ Me CH ₂ CH = CH ₂ OF CH ₂ CH (Cl) CO ₂ Et CH ₂ CH = CH ₂ OF CH = CHCO ₂ Me CH ₂ CH = CH ₂ OF CH = CHCO ₂ Et CH ₂ CH = CH ₂ OF CH = C (Cl) CO ₂ Me CH ₂ CH = CH ₂ OF CH = C (Cl) CO ₂ Et CH ₂ CH = CH ₂ OF OH CH ₂ CH = CH ₂ OF F OMe CH ₂ CH = CH ₂ OF OEt CH ₂ CH = CH ₂ OF Oi-Pr CH ₂ CH = CH ₂ OF F Oc-Pen CH ₂ CH = CH ₂ OF F OCH ₂ CF ₃ CH ₂ CH = CH ₂ OF F OCH ₂ CH = CH ₂ CH ₂ CH = CH ₂ OF _{OCH 2 CH = CH (Cl)} CH 2 CH = CH 2 O F OCH 2 C≡CH ───── ───────────────────────────────

[0144]

[Table 80] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF F OCH (Me) C≡CH CH _{2 CH = CH 2 O F OPh CH} 2 CH = CH 2 O F OCH 2 Ph CH 2 CH = CH 2 O F OCH 2 CH = CH-Ph CH 2 CH = CH 2 O F SH CH 2 CH = CH 2 O F SMe CH ₂ CH = CH ₂ OF SEt CH ₂ CH = CH ₂ OF Si-Pr CH ₂ CH = CH ₂ OF Sc-Pen CH ₂ CH = CH ₂ OF SCH ₂ CF ₃ CH ₂ CH = CH _{2 O F SCH 2 CH = CH 2} CH 2 CH = CH 2 O F SCH 2 CH = CH (Cl) CH 2 CH = CH 2 O F SCH 2 C≡CH CH 2 CH = CH 2 O F SCH (Me) C ≡CH CH ₂ CH = CH ₂ OF SPh CH ₂ CH = CH ₂ OF SCH ₂ Ph CH ₂ CH = CH ₂ OF SCH ₂ CH = CHPh CH ₂ CH = CH ₂ OF SCH ₂ CO ₂ Me CH ₂ CH = CH ₂ OF F OCH ₂ CO ₂ Me CH ₂ CH = CH ₂ OF F OCH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF F OCH (Me) CO ₂ Me CH ₂ CH = CH ₂ OF F OCH (Me _{) CO 2 Et CH 2 CH =} CH 2 O F OCH 2 CO 2 Pen ──── ───────────────────────────────

[0145]

[Table 81] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF SCH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF SCH (Me) CO ₂ Me CH ₂ CH = CH ₂ OF SCH (Me) CO ₂ Et CH ₂ CH = CH ₂ OF SCH ₂ CO ₂ Pen CH ₂ CH = CH ₂ OF NH ₂ CH _{2 CH = CH 2 O F NHMe} CH 2 CH = CH 2 O F NHCH 2 CH = CH 2 CH 2 CH = CH 2 O F NHCH 2 C≡CH CH 2 CH = CH 2 O F NHCH 2 CF 3 CH 2 CH = CH ₂ OF NHCO ₂ Me CH ₂ CH = CH ₂ OF NHCO ₂ Et CH ₂ CH = CH ₂ OF NHCOMe CH ₂ CH = CH ₂ OF NHCOPh CH ₂ CH = CH ₂ OF OF NHCH ₂ CO ₂ Me CH ₂ CH = CH ₂ OF NHCH ₂ CO ₂ Et CH ₂ CH = CH ₂ OF NHSO ₂ Me CH ₂ CH = CH ₂ OF NHSO ₂ Et CH ₂ CH = CH ₂ OF NHSO ₂ NMe ₂ CH ₂ CH = CH ₂ OF N (CO-t-Bu) SO ₂ Me CH ₂ CH = CH ₂ OF N (CO-p-MeO-Ph) SO ₂ Me CH ₂ CH = CH ₂ OF CN CH ₂ CH = CH ₂ OF NO ₂ CH ₂ CH = CH ₂ OF CH ₂ C N ────────────────────────────────────

[0146]

[Table 82] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CH ₂ CH = CH ₂ OF F CH ₂ CH = CH ₂ OF Cl CH ₂ CH = CH ₂ OF Br CH ₂ CH = CH ₂ OF I HC≡CCH ₂ OF H HC≡CCH ₂ OF CH ₂ CH (Cl) CO ₂ Et HC≡CCH ₂ OF CH = C (Cl) CO ₂ Et HC≡CCH ₂ OF F OMe HC≡CCH ₂ OF F Oi-Pr HC≡CCH ₂ OF F Oc-Pen HC≡CCH ₂ OF F OCH ₂ CF ₃ HC≡CCH ₂ OF OFCH ₂ CH _{= CH 2 HC≡CCH 2 O F OCH} 2 CH = CH (Cl) HC≡CCH 2 O F OCH 2 C≡CH HC≡CCH 2 O F OCH (Me) C≡CH HC≡CCH 2 O F OPh HC≡ CCH ₂ OF F OCH ₂ Ph HC≡CCH ₂ OF F OCH ₂ CH = CHPh HC≡CCH ₂ OF F OCH ₂ CO ₂ Me HC≡CCH ₂ OF F OCH ₂ CO ₂ Et HC≡CCH ₂ OF F OCH ₂ CO ₂ Pen HC≡CCH ₂ OF SH HC≡CCH ₂ OF SMe ──────────────────────────── ────────

[0147]

[Table 83] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── HC≡CCH ₂ OF Si-Pr HC≡CCH ₂ OF Sc- _{Pen HC≡CCH 2 O F SCH 2 CH} = CH 2 HC≡CCH 2 O F SCH 2 CH = CHCl HC≡CCH 2 O F SCH 2 C≡CH HC≡CCH 2 O F SCH (Me) C≡CH HC≡ CCH ₂ OF SPh HC≡CCH ₂ OF SCH ₂ Ph HC≡CCH ₂ OF SCH ₂ CO ₂ Me HC≡CCH ₂ OF SCH ₂ CO ₂ Et HC≡CCH ₂ OF OF SCH ₂ CO ₂ Pen HC≡CCH _{2 O F F HC≡CCH 2 O F} Cl HC≡CCH 2 O F Br HC≡CCH 2 O F NH 2 HC≡CCH 2 O F NHMe HC≡CCH 2 O F NHCO 2 Et HC≡CCH 2 O F NHCOMe HC ≡CCH ₂ OF NHCOPh HC≡CCH ₂ OF NHCH ₂ CO ₂ Et HC≡CCH ₂ OF NHSO ₂ Me HC≡CCH ₂ OF NHSO ₂ Et HC≡CCH ₂ OF NHSO ₂ NMe ₂ ───── ───────────────────────── ─────

[0148]

[Table 84] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── HC≡CCH ₂ OFN (CO-t-Bu) SO ₂ Me _{HC≡CCH 2 O F N (CO-} p-MeO-Ph) SO 2 Me HC≡CCH 2 O F CN HC≡CCH 2 O F NO 2 HC≡CCH 2 O F CH 2 CN HC≡CCH 2 O F CHO HC≡CCH ₂ OF CO ₂ H HC≡CCH ₂ OF CO ₂ Et PhCH ₂ OF H PhCH ₂ OF OF CH ₂ CH (Cl) CO ₂ Et PhCH ₂ OF CH = C (Cl) CO ₂ Et PhCH _{2 O F Oc-Pen PhCH 2} O F OCH 2 C≡CH PhCH 2 O F OCH 2 CO 2 Et PhCH 2 O F Si-Pr PhCH 2 O F SCH 2 C≡CH PhCH 2 O F SCH 2 CO 2 Et PhCH ₂ OF NHSO ₂ Me PhCH ₂ OF NHSO ₂ Et PhCH ₂ OF CO ₂ Et Ph (2-Cl) CH ₂ OF H Ph (2-Cl) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (2-Cl) CH ₂ OF CH = C (Cl) CO ₂ Et ─────────────────────────────── ── ──

[0149]

[Table 85] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (2-Cl) CH ₂ OF F Oc-Pen Ph (2- _{Cl) CH 2 O F OCH 2} C≡CH Ph (2-Cl) CH 2 O F OCH 2 CO 2 Et Ph (2-Cl) CH 2 O F Si-Pr Ph (2-Cl) CH 2 O F SCH ₂ C≡CH Ph (2-Cl) CH ₂ OF SCH ₂ CO ₂ Et Ph (2-Cl) CH ₂ OF NHSO ₂ Me Ph (2-Cl) CH ₂ OF NHSO ₂ Et Ph (2-Cl ) CH ₂ OF CO ₂ Et Ph (3-Cl) CH ₂ OF H Ph (3-Cl) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et Ph (3-Cl) CH ₂ OF CH = _{C (Cl) CO 2 Et Ph} (3-Cl) CH 2 O F Oc-Pen Ph (3-Cl) CH 2 O F OCH 2 C≡CH Ph (3-Cl) CH 2 O F OCH 2 CO 2 Et _{Ph (3-Cl) CH 2} O F Si-Pr Ph (3-Cl) CH 2 O F SCH 2 C≡CH Ph (3-Cl) CH 2 O F SCH 2 CO 2 Et Ph (3-Cl) CH ₂ OF NHSO ₂ Me Ph (3-Cl) CH ₂ OF NHSO ₂ Et Ph (3-Cl) CH ₂ OF CO ₂ Et Ph (4-Cl) CH ₂ OF H Ph (4-Cl) CH ₂ OF CH ₂ CH (Cl) CO ₂ Et ─── ─────────────────────────────────

[0150]

[Table 86] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (4-Cl) CH ₂ OF CH = C (Cl) CO _{2 Et Ph (4-Cl)} CH 2 O F Oc-Pen Ph (4-Cl) CH 2 O F OCH 2 C≡CH Ph (4-Cl) CH 2 O F OCH 2 CO 2 Et Ph (4-Cl _{) CH 2 O F Si-Pr} Ph (4-Cl) CH 2 O F SCH 2 C≡CH Ph (4-Cl) CH 2 O F SCH 2 CO 2 Et Ph (4-Cl) CH 2 O F NHSO 2 Me Ph (4-Cl) CH ₂ OF NHSO ₂ Et Ph (4-Cl) CH ₂ OF CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF H Ph (2,3-Cl ₂ ) _{CH 2 O F CH 2 CH (} Cl) CO 2 Et Ph (2,3-Cl 2) CH 2 O F CH = C (Cl) CO 2 Et Ph (2,3-Cl 2) CH 2 O F Oc- Pen Ph (2,3-Cl ₂ ) CH ₂ OFCH ₂ C≡CH Ph (2,3-Cl ₂ ) CH ₂ OF F OCH ₂ CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF Si-Pr Ph (2,3-Cl ₂ ) CH ₂ OF SCH ₂ C≡CH Ph (2,3-Cl ₂ ) CH ₂ OF SCH ₂ CO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF NHSO ₂ Me Ph (2,3-Cl ₂ ) CH ₂ OF NHSO ₂ Et Ph (2,3-Cl ₂ ) CH ₂ OF CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF H ──────────────────────────── ────────

[0151]

[Table 87] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── Ph (2,4-Cl ₂ ) CH ₂ OF CH ₂ CH ( Cl) CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF CH = C (Cl) CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF F Oc-Pen Ph (2,4-Cl ₂ ) CH ₂ OFCH ₂ C≡CH Ph (2,4-Cl ₂ ) CH ₂ OF F OCH ₂ CO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF Si-Pr Ph (2,4 _{-Cl 2) CH 2 O F SCH} 2 C≡CH Ph (2,4-Cl 2) CH 2 O F SCH 2 CO 2 Et Ph (2,4-Cl 2) CH 2 O F NHSO 2 Me Ph (2 , 4-Cl ₂ ) CH ₂ OF NHSO ₂ Et Ph (2,4-Cl ₂ ) CH ₂ OF CO ₂ Et PhCH ₂ CH ₂ OF H PhCH ₂ CH ₂ OF CH ₂ CH (Cl) CO _{2 Et PhCH 2 CH 2 O F CH} = C (Cl) CO 2 Et PhCH 2 CH 2 O F Oc-Pen PhCH 2 CH 2 O F OCH 2 C≡CH PhCH 2 CH 2 O F OCH 2 CO 2 Et PhCH 2 CH _{2 O F Si-Pr PhCH 2} CH 2 O F SCH 2 C≡CH PhCH 2 CH 2 O F SCH 2 CO 2 Et PhCH 2 CH 2 O F NHSO 2 Me PhCH 2 CH 2 OF NHSO ₂ Et PhCH ₂ CH ₂ OF CO ₂ Et ────────────────────────────────────

[0152]

[Table 88] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── _{───────────────────────────────── PhCH = CHCH 2 O F H} PhCH = CHCH 2 O F CH 2 CH ( _{Cl) CO 2 Et PhCH = CHCH} 2 O F CH = C (Cl) CO 2 Et PhCH = CHCH 2 O F Oc-Pen PhCH = CHCH 2 O F OCH 2 C≡CH PhCH = CHCH 2 O F OCH 2 CO 2 _{Et PhCH = CHCH 2 O F Si} -Pr PhCH = CHCH 2 O F SCH 2 C≡CH PhCH = CHCH 2 O F SCH 2 CO 2 Et PhCH = CHCH 2 O F NHSO 2 Me PhCH = CHCH 2 O F NHSO 2 Et _{PhCH = CHCH 2 O F CO 2} Et MeO O F H MeO O F CH 2 CH (Cl) CO 2 Et MeO O F CH = C (Cl) CO 2 Et MeO O F Oc-Pen MeO O F OCH 2 C≡ _{CH MeO O F OCH 2 CO 2} Et MeO O F Si-Pr MeO O F SCH 2 C≡CH MeO O F SCH 2 CO 2 Et MeO O F NHSO 2 Me MeO O F NHSO 2 Et ─────── ─────────────────────────────

[0153]

[Table 89] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── MeO OF CO ₂ Et CHF ₂ SF H CHF ₂ SF Me CHF _{2 S F CHO CHF 2 S F} PhCH 2 CHF 2 S F PhCH = CHCH 2 CHF 2 S F CO 2 H CHF 2 S F CO 2 Me CHF 2 S F CO 2 Et CHF 2 S F CH 2 CO 2 Me CHF 2 _{S F CH 2 CO 2 Et CHF} 2 S F CH 2 CH (Cl) CO 2 Me CHF 2 S F CH 2 CH (Cl) CO 2 Et CHF 2 S F CH = CHCO 2 Me CHF 2 S F CH = CHCO 2 Et CHF ₂ SF CH = C (Cl) CO ₂ Me CHF ₂ SF CH = C (Cl) CO ₂ Et CHF ₂ SF OH CHF ₂ SF OMe CHF ₂ SF OEt CHF ₂ SF Oi-Pr CHF ₂ SF Oc-Pen CHF ₂ SF OCH ₂ CF ₃ ────────────────────────────────────

[0154]

[Table 90] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF OCH ₂ CH = CH ₂ CHF ₂ SF OCH ₂ CH _{= CH (Cl) CHF 2 S} F OCH 2 C≡CH CHF 2 S F OCH (Me) C≡CH CHF 2 S F OPh CHF 2 S F OCH 2 Ph CHF 2 S F OCH 2 CH = CH-Ph CHF 2 SF OCH ₂ CO ₂ Me CHF ₂ SF OCH ₂ CO ₂ Et CHF ₂ SF OCH (Me) CO ₂ Me CHF ₂ SF OCH (Me) CO ₂ Et CHF ₂ SF OCH ₂ CO ₂ Pen CHF ₂ S F SH CHF ₂ SF SMe CHF ₂ SF SEt CHF ₂ SF SF Si-Pr CHF ₂ SF Sc-Pen CHF ₂ SF SCH ₂ CF ₃ CHF ₂ SF SCH ₂ CH = CH ₂ CHF ₂ SF SCH ₂ CH = CH (Cl) CHF ₂ SF SCH ₂ C≡CH CHF ₂ SF SCH (Me) C≡CH CHF ₂ SF SPh ─────────────────── ─────────────────

[0155]

[Table 91] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF SCH ₂ Ph CHF ₂ SF SCH ₂ CH = CH- Ph CHF ₂ SF SCH ₂ CO ₂ Me CHF ₂ SF SF SCH ₂ CO ₂ Et CHF ₂ SF SCH (Me) CO ₂ Me CHF ₂ SF SCH (Me) CO ₂ Et CHF ₂ SF SCH ₂ CO ₂ Pen _{CHF 2 S F NH 2 CHF 2} S F NHMe CHF 2 S F NHCH 2 CH = CH 2 CHF 2 S F NHCH 2 C≡CH CHF 2 S F NHCH 2 CF 3 CHF 2 S F NHCO 2 Me CHF 2 S F NHCO _{2 Et CHF 2 S F NHCOMe CHF} 2 S F NHCOPh CHF 2 S F NHCH 2 CO 2 Me CHF 2 S F NHCH 2 CO 2 Et CHF 2 S F NHSO 2 Me CHF 2 S F NHSO 2 Et CHF 2 S F NHSO 2 NMe ₂ CHF ₂ SF N (CO-t-Bu) SO ₂ Me CHF ₂ SF N (CO-p-MeO-Ph) SO ₂ Me ──────────────── ────────────────────

[0156]

[Table 92] ^{──────────────────────────────────── R 1 W R 4 R 6} ─── ───────────────────────────────── CHF ₂ SF CN CHF ₂ SF NO ₂ CHF ₂ SF CH ₂ CN CHF ₂ SF F CHF ₂ SF Cl CHF ₂ SF Br CHF ₂ S FI Me Me OF N (CHO) SO ₂ Me Me OF OCH (Me) C≡CH CHF ₂ OF N (CHO) SO ₂ Me CHF ₂ OF OCH (Me) C≡CH F (CH ₂ ) ₃ OF N (CHO) SO ₂ Me F (CH ₂ ) ₃ OF OCH (Me) C≡CH CH ₂ = CHCH ₂ OF N (CHO) SO ₂ Me CH ₂ = CHCH ₂ OF F OCH (Me) C≡CH ───────────────────────────── A compound that is ───────. Table 7

[0157]

Embedded image

In the group of compounds represented by

[0159]

[Table 93] ──────────────────────────────────── R ¹ R ⁶ ────── ────────────────────────────── CHF ₂ H CHF ₂ CH ₂ CH (Cl) CO ₂ Et CHF ₂ CH = C ( Cl) CO ₂ Et CHF ₂ Oc-Pen CHF ₂ OCH ₂ C≡CH CHF ₂ OCH ₂ CO ₂ Et CHF ₂ Si-Pr CHF ₂ SCH ₂ C≡CH CHF ₂ SCH ₂ CO ₂ Et CHF ₂ NHSO ₂ Me CHF ₂ NHSO ₂ Et CHF ₂ CO ₂ Et CHF ₂ CF ₃ CHF ₂ Cl ─────────────────────────────────── A compound that is ─. Table 8

[0160]

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In the group of compounds represented by

[0162]

[Table 94] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CHF ₂ H CHF ₂ Me CHF ₂ Et CHF ₂ Pr CHF ₂ CH ₂ CF ₃ CHF ₂ c-Pr CHF ₂ CH ₂ CH = CH ₂ CHF ₂ CH ₂ C≡CH CHF ₂ COMe CHF ₂ CH ₂ CO ₂ Me CHF ₂ CH ₂ CO ₂ Et CHF ₂ CH ₂ COMe CHF ₂ CH ₂ COPh CHF ₂ CH ₂ CN CHF ₂ CH ₂ Ph CHF ₂ CH ₂ CH ₂ Ph CHF ₂ CH ₂ OMe CHF ₂ CH ₂ OEt CHF ₂ CH ₂ SMe CHF ₂ CH ₂ SEt F (CH ₂ ) ₃ H F (CH ₂ ) ₃ Me F (CH ₂ ) ₃ Et ────────────────────────────────────

[0163]

[Table 95] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── F (CH ₂ ) ₃ Pr F (CH ₂ ) ₃ CH ₂ CF ₃ F (CH _{2) 3 c-Pr F (} CH 2) 3 CH 2 CH = CH 2 F (CH 2) 3 CH 2 C≡CH F (CH 2) 3 COMe F (CH 2) 3 CH 2 CO 2 Me F (CH ₂ ) ₃ CH ₂ CO ₂ Et F (CH ₂ ) ₃ CH ₂ COMe F (CH ₂ ) ₃ CH ₂ COPh F (CH ₂ ) ₃ CH ₂ CN F (CH ₂ ) ₃ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ OMe F (CH ₂ ) ₃ CH ₂ OEt F (CH ₂ ) ₃ CH ₂ SMe F (CH ₂ ) ₃ CH ₂ SEt CH ₂ = CHCH ₂ H CH ₂ = CHCH ₂ Me CH ₂ = CHCH ₂ Et CH ₂ = CHCH ₂ Pr CH ₂ = CHCH ₂ CH ₂ CF ₃ CH ₂ = CHCH ₂ c-Pr ────────────────── ──────────────────

[0164]

[Table 96] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CH ₂ = CHCH ₂ CH ₂ CH = CH ₂ CH ₂ = CHCH ₂ CH ₂ C≡ CH CH ₂ = CHCH ₂ COMe CH ₂ = CHCH ₂ CH ₂ CO ₂ Me CH ₂ = CHCH ₂ CH ₂ CO ₂ Et CH ₂ = CHCH ₂ CH ₂ COMe CH ₂ = CHCH ₂ CH ₂ COPh CH ₂ = CHCH ₂ CH ₂ CN CH ₂ = CHCH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ OMe CH ₂ = CHCH ₂ CH ₂ OEt CH ₂ = CHCH ₂ CH ₂ SMe CH ₂ = CHCH ₂ CH ₂ Compounds that are SEt────────────────────────────────────. Table 9

[0165]

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In the group of compounds represented by

[0167]

[Table 97] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CHF ₂ H CHF ₂ Me CHF ₂ Et CHF ₂ Pr CHF ₂ CH ₂ CF ₃ CHF ₂ c-Pr CHF ₂ CH ₂ CH = CH ₂ CHF ₂ CH ₂ C≡CH CHF ₂ COMe CHF ₂ CH ₂ CO ₂ Me CHF ₂ CH ₂ CO ₂ Et CHF ₂ CH ₂ COMe CHF ₂ CH ₂ COPh CHF ₂ CH ₂ CN CHF ₂ CH ₂ Ph CHF ₂ CH ₂ CH ₂ Ph CHF ₂ CH ₂ OMe CHF ₂ CH ₂ OEt CHF ₂ CH ₂ SMe CHF ₂ CH ₂ SEt F (CH ₂ ) ₃ H F (CH ₂ ) ₃ Me F (CH ₂ ) ₃ Et ────────────────────────────────────

[0168]

[Table 98] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── F (CH ₂ ) ₃ Pr F (CH ₂ ) ₃ CH ₂ CF ₃ F (CH _{2) 3 c-Pr F (} CH 2) 3 CH 2 CH = CH 2 F (CH 2) 3 CH 2 C≡CH F (CH 2) 3 COMe F (CH 2) 3 CH 2 CO 2 Me F (CH ₂ ) ₃ CH ₂ CO ₂ Et F (CH ₂ ) ₃ CH ₂ COMe F (CH ₂ ) ₃ CH ₂ COPh F (CH ₂ ) ₃ CH ₂ CN F (CH ₂ ) ₃ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ OMe F (CH ₂ ) ₃ CH ₂ OEt F (CH ₂ ) ₃ CH ₂ SMe F (CH ₂ ) ₃ CH ₂ SEt CH ₂ = CHCH ₂ H CH ₂ = CHCH ₂ Me CH ₂ = CHCH ₂ Et CH ₂ = CHCH ₂ Pr CH ₂ = CHCH ₂ CH ₂ CF ₃ CH ₂ = CHCH ₂ c-Pr ────────────────── ──────────────────

[0169]

[Table 99] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CH ₂ = CHCH ₂ CH ₂ CH = CH ₂ CH ₂ = CHCH ₂ CH ₂ C≡ CH CH ₂ = CHCH ₂ COMe CH ₂ = CHCH ₂ CH ₂ CO ₂ Me CH ₂ = CHCH ₂ CH ₂ CO ₂ Et CH ₂ = CHCH ₂ CH ₂ COMe CH ₂ = CHCH ₂ CH ₂ COPh CH ₂ = CHCH ₂ CH ₂ CN CH ₂ = CHCH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ OMe CH ₂ = CHCH ₂ CH ₂ OEt CH ₂ = CHCH ₂ CH ₂ SMe CH ₂ = CHCH ₂ CH ₂ Compounds that are SEt────────────────────────────────────. Table 10

[0170]

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In the group of compounds represented by

[0172]

[Table 100] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CHF ₂ H CHF ₂ Me CHF ₂ Et CHF ₂ Pr CHF ₂ CH ₂ CF ₃ CHF ₂ c-Pr CHF ₂ CH ₂ CH = CH ₂ CHF ₂ CH ₂ C≡CH CHF ₂ COMe CHF ₂ CH ₂ CO ₂ Me CHF ₂ CH ₂ CO ₂ Et CHF ₂ CH ₂ COMe CHF ₂ CH ₂ COPh CHF ₂ CH ₂ CN CHF ₂ CH ₂ Ph CHF ₂ CH ₂ CH ₂ Ph CHF ₂ CH ₂ OMe CHF ₂ CH ₂ OEt CHF ₂ CH ₂ SMe CHF ₂ CH ₂ SEt F (CH ₂ ) ₃ H F (CH ₂ ) ₃ Me F (CH ₂ ) ₃ Et ────────────────────────────────────

[0173]

[Table 101] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── F (CH ₂ ) ₃ Pr F (CH ₂ ) ₃ CH ₂ CF ₃ F (CH _{2) 3 c-Pr F (} CH 2) 3 CH 2 CH = CH 2 F (CH 2) 3 CH 2 C≡CH F (CH 2) 3 COMe F (CH 2) 3 CH 2 CO 2 Me F (CH ₂ ) ₃ CH ₂ CO ₂ Et F (CH ₂ ) ₃ CH ₂ COMe F (CH ₂ ) ₃ CH ₂ COPh F (CH ₂ ) ₃ CH ₂ CN F (CH ₂ ) ₃ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ CH ₂ Ph F (CH ₂ ) ₃ CH ₂ OMe F (CH ₂ ) ₃ CH ₂ OEt F (CH ₂ ) ₃ CH ₂ SMe F (CH ₂ ) ₃ CH ₂ SEt CH ₂ = CHCH ₂ H CH ₂ = CHCH ₂ Me CH ₂ = CHCH ₂ Et CH ₂ = CHCH ₂ Pr CH ₂ = CHCH ₂ CH ₂ CF ₃ CH ₂ = CHCH ₂ c-Pr ────────────────── ──────────────────

[0174]

[Table 102] ──────────────────────────────────── R ¹ R ¹⁰ ────── ────────────────────────────── CH ₂ = CHCH ₂ CH ₂ CH = CH ₂ CH ₂ = CHCH ₂ CH ₂ C≡ CH CH ₂ = CHCH ₂ COMe CH ₂ = CHCH ₂ CH ₂ CO ₂ Me CH ₂ = CHCH ₂ CH ₂ CO ₂ Et CH ₂ = CHCH ₂ CH ₂ COMe CH ₂ = CHCH ₂ CH ₂ COPh CH ₂ = CHCH ₂ CH ₂ CN CH ₂ = CHCH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ CH ₂ Ph CH ₂ = CHCH ₂ CH ₂ OMe CH ₂ = CHCH ₂ CH ₂ OEt CH ₂ = CHCH ₂ CH ₂ SMe CH ₂ = CHCH ₂ CH ₂ Compounds that are SEt────────────────────────────────────. Table 11

[0175]

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In the group of compounds represented by

[0177]

[Table 103] ──────────────────────────────────── R ¹ R ⁶ ────── ────────────────────────────── CHF ₂ H CHF ₂ CH ₂ CH (Cl) CO ₂ Et CHF ₂ CH = C ( Cl) CO ₂ Et CHF ₂ Oc-Pen CHF ₂ OCH ₂ C≡CH CHF ₂ OCH ₂ CO ₂ Et CHF ₂ Si-Pr CHF ₂ SCH ₂ C≡CH CHF ₂ SCH ₂ CO ₂ Et CHF ₂ NHSO ₂ Me CHF ₂ NHSO ₂ Et CHF ₂ CO ₂ Et CHF ₂ Cl CH ₂ = CHCH ₂ H CH ₂ = CHCH ₂ CH ₂ CH (Cl) CO ₂ Et CH ₂ = CHCH ₂ CH = C (Cl) CO ₂ Et CH ₂ = CHCH ₂ Oc-Pen CH ₂ = CHCH ₂ OCH ₂ C≡CH CH ₂ = CHCH ₂ OCH ₂ CO ₂ Et CH ₂ = CHCH ₂ Si-Pr CH ₂ = CHCH ₂ SCH ₂ C≡CH CH ₂ = CHCH ₂ SCH ₂ CO ₂ Et CH ₂ = CHCH ₂ NHSO ₂ Me ────────────────────────────────────

[0178]

Table 104] ──────────────────────────────────── R ¹ R ⁶ ────── ────────────────────────────── CH ₂ = CHCH ₂ NHSO ₂ Et CH ₂ = CHCH ₂ CO ₂ Et CH ₂ = CHCH Compounds that are ₂ Cl ────────────────────────────────────. Table 12

[0179]

Embedded image

In the compound group represented by

[0181]

[Table 105] ──────────────────────────────────── R ¹ R ⁴ R ⁶ ──── ──────────────────────────────── CHF ₂ F H CHF ₂ F CH ₂ CH (Cl) CO ₂ Et CHF ₂ F CH = C (Cl) CO ₂ Et CHF ₂ F Oc-Pen CHF ₂ F OCH ₂ C≡CH CHF ₂ F OCH ₂ CO ₂ Et CHF ₂ F Si-Pr CHF ₂ F SCH ₂ C≡CH CHF ₂ F SCH ₂ CO ₂ Et CHF ₂ F NHSO ₂ Me CHF ₂ F NHSO ₂ Et CHF ₂ F CO ₂ Et CHF ₂ F Cl CH ₂ = CHCH ₂ F H CH ₂ = CHCH ₂ F CH ₂ CH (Cl) CO ₂ Et CH ₂ = CHCH ₂ F CH = C (Cl) CO ₂ Et CH ₂ = CHCH ₂ F Oc-Pen CH ₂ = CHCH ₂ F OCH ₂ C≡CH CH ₂ = CHCH ₂ F OCH ₂ CO ₂ Et CH ₂ = CHCH ₂ F Si-Pr CH ₂ = CHCH ₂ F SCH ₂ C≡CH CH ₂ = CHCH ₂ F SCH ₂ CO ₂ Et CH ₂ = CHCH ₂ F NHSO ₂ Me ────────────────────

[0182]

[Table 106] ──────────────────────────────────── R ¹ R ⁴ R ⁶ ──── ──────────────────────────────── CH ₂ = CHCH ₂ F NHSO ₂ Et CH ₂ = CHCH ₂ F CO ₂ Et CH ₂ = CHCH ₂ F Cl F (CH ₂ ) ₃ F H F (CH ₂ ) ₃ F CH ₂ CH (Cl) CO ₂ Et F (CH ₂ ) ₃ F CH = C (Cl) CO ₂ Et F (CH ₂ ) ₃ F Oc-Pen F (CH ₂ ) ₃ F OCH ₂ C≡CH F (CH ₂ ) ₃ F OCH ₂ CO ₂ Et F (CH ₂ ) ₃ F Si-Pr F (CH ₂ ) ₃ F SCH ₂ C≡CH F (CH ₂ ) ₃ F SCH ₂ CO ₂ Et F (CH ₂ ) ₃ F NHSO ₂ Me F (CH ₂ ) ₃ F NHSO ₂ Et F (CH ₂ ) ₃ F CO ₂ Et F (CH ₂ ) A compound that is ₃ FCl────────────────────────────────────. Table 13

[0183]

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In the group of compounds represented by

[0185]

[Table 107] ──────────────────────────────────── R ⁴ R ⁶ ────── ────────────────────────────── H H H CO ₂ Me H CO ₂ Et H COMe H OMe H OEt H CH = CH -CO ₂ Et H CHO H Me H Et F H F CO ₂ Me F CO ₂ Et F COMe F OMe F OEt F CH = CHCO ₂ Et F CHO F Me F Et ──────────── A compound that is ────────────────────────. Table 14

[0186]

Embedded image

In the group of compounds represented by

[0188]

[Table 108] ──────────────────────────────────── R ¹ ──────── Ｍ Me, Et, Pr, CHF ₂ , CH ₂ ＣＨCHCH ₂ , F (CH ₂ ) ₃ or A compound that is MeSO ₂ ────────────────────────────────────.

In Tables 5 to 14, "Me" represents a methyl group, "Et" represents an ethyl group, "Pr" represents a propyl group,
“Pen” represents a pentyl group, “Ph” represents a phenyl group,
“Bu” represents a butyl group, and “i” represents iso to “t”.
"T" represents tertiary, and "c" represents cyclo. In applying the imidazolinone compound as a herbicide, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, urea, ammonium sulfate, walnut powder, diatomaceous earth, white carbon or water, alcohols (isopropanol, butanol, Ethylene glycol, benzyl alcohol, furfuryl alcohol, etc.), aromatic hydrocarbons (toluene,
Xylene, methylnaphthalene, etc.), ethers (anisole, etc.), vegetable oils (soybean oil, cottonseed oil, etc.), ketones (cyclohexanone, isophorone, etc.), esters (butyl acetate, etc.), acid amides (N-methylpyrrolidone, etc.) Or a mixture with a liquid carrier such as a halogenated hydrocarbon (chlorobenzene or the like), and if desired, a surfactant, an emulsifier, a dispersant, a penetrant, a spreading agent, a thickener, an antifreezing agent, A caking inhibitor, a stabilizer, etc. are added, and the composition can be put to practical use in any form such as a liquid, emulsion, wettable powder, dry flowable, flowable, powder, and powder.

The imidazolinone compound may be added to other herbicides, various insecticides, acaricides, nematocides, fungicides, plant growth regulators, synergists, fertilizers or the like as needed when preparing or spraying. You may mix and apply with a soil improving agent etc. In particular, by mixing and applying other pesticides, it can be expected that the cost can be reduced by reducing the amount of applied chemical, the spectrum can be expanded by the synergistic action of the mixed chemical, and a higher herbicidal effect can be expected. At this time, a combination with a plurality of known agricultural chemicals is possible at the same time. Examples of the types of pesticides to be mixed and used with the compound of the present invention include, for example, Farm Chemicals Handbook (Farm Chemicals Han
dbook) 1997 edition.

The amount of the imidazolinone compound to be applied varies depending on the application scene, application time, application method, weather conditions, formulation form, soil conditions, cultivated crops, and the like, but generally the amount of the effective ingredient is 0.1 per hectare (ha). 0001-10k
g, preferably about 0.001 to 5 kg. Next, a formulation example of a preparation in the case of using an imidazolinone compound will be specifically described. However, the composition examples of the present invention are not limited to these. In the following formulation examples, "parts" means parts by weight. [Wettable powder] Imidazolinone compound {0.1-80 parts Solid carrier} 10-90 parts Surfactant {1-10 parts Others} ───────1 to 5 parts Others include, for example, an anti-caking agent. [Emulsion] Imidazolinone compound 0.1 to 30 parts Liquid carrier 30 to 95 parts Surfactant 5 to 15 parts Flowable agent Imidazolinone Compound ──0.1-70 parts Liquid carrier ─────────15-65 parts Surfactant ────────5-12 parts Others────────── 5 to 30 parts Others include, for example, an antifreezing agent and a thickener. [Granular wettable powder (dry flowable)] imidazolinone compound {0.1-90 parts solid carrier} 10-70 parts surfactant {1} 20 parts [Granule] imidazolinone compound ──0.0001 to 10 parts Solid carrier ─────────90 to 99.99999 parts Others ──────────0.1 to 10 Part [Formulation Example 1] wettable powder imidazolinone compound No. 3-1 50 parts Sieglite PFP 43 parts (Kaolin based clay: trade name of Geek Light Industry Co., Ltd.) Solpol 5050 2 parts (anionic surfactant: Toho Chemical Industry Co., Ltd.) Lunox 1000C 3 parts (anionic surfactant: Toho Chemical Industry Co., Ltd.) Trade name) Carplex # 80 (anti-caking agent) 2 parts (white carbon: trade name of Shionogi & Co., Ltd.) The above ingredients are uniformly mixed and pulverized to obtain a wettable powder. [Formulation Example 2] Emulsion Imidazolinone Compound No. 3-1 3 parts Xylene 76 parts Isophorone 15 parts Solpol 3005X # 6 parts (mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) The above are uniformly mixed to form an emulsion. [Formulation Example 3] Flowable agent imidazolinone compound No. 3-1 {35 parts Agrisol S-711 {8 parts (nonionic surfactant: trade name of Kao Corporation) Lunox 1000C} 0.5 parts (anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) 1% rhodopol water 20 parts (thickener: Lone Poulin Company name) Ethylene glycol (antifreeze) ─────8 parts Water────────────────────28.5 parts , A flowable agent. [Compounding Example 4] Granular wettable powder (dry flowable agent) 3-1 # 75 parts Isoban No. 1─────────────10 parts (anionic surfactant: Kuraray Isoprene Chemical Co., Ltd.) Vanirex N──────────────5 parts (Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd.) Carplex # 80 10 parts (White carbon: Shionogi & Co., Ltd.) The mixture is finely pulverized to obtain a dry flowable agent. [Formulation Example 5] Granules Imidazolinone compound No. 3-1 {0.1 part bentonite} 50.0 part talc 44.9 parts Toxanone GR-31A 5 parts (anionic surfactant: trade name of Sanyo Chemical Industries, Ltd.) After uniformly mixing and pulverizing the above, a small amount of water was added. In addition, the mixture is kneaded with stirring, granulated by an extrusion granulator, and dried to form granules.

For use, the above-mentioned wettable powder, emulsion, flowable and granular wettable powder are diluted 50 to 1000 times with water to give an active ingredient of 0.000 per hectare (ha).
Spray to 1 to 10 kg. Next, the usefulness of the herbicide of the present invention will be specifically described in the following test examples. [Test Example-1] Herbicidal effect test by weed generation pretreatment under flooded conditions After placing alluvial soil in a cylindrical plastic cup with an inner diameter of 3.2 cm and a depth of 9 cm, water was added and mixed, and the water depth was 4
cm. Rice at the two leaf stage was transplanted to the above pot, and seeds of Nobie, Firefly and Konagi were mixed and sown. The pot was grown in a greenhouse at 25 to 30 ° C., and the herbicide of the present invention prepared according to the formulation example was treated on the water surface on the first day after sowing so as to have a predetermined dose. Three weeks after the treatment, the herbicidal effect on various weeds and the effect on rice were visually examined according to the following criteria. 0 is no effect and 5 is a 5-point scale showing complete withering. The results are shown in Table 15.

It should be noted that in each table, No. Is the compound No. described in the examples. And the symbols have the following meanings. A: Nobie, B: Firefly, C: Onion, a: Rice Judgment criteria 5: Herbicidal rate 90% or more (almost completely withered) ... Herbicidal rate 20% or more and less than 40% 1 ... Herbicidal rate 5% or more and less than 20% 0 ... Herbicidal rate less than 5% (almost no effect) [Test Example-2] Herbicidal effect test by treatment after weed emergence in flooded conditions After putting alluvial soil into a 3.2 cm, 9 cm deep cylindrical plastic cup, add water and mix to obtain a water depth of 4 cm.
cm. The above pots were mixed with soybean, firefly and corn seeds. The pot was grown in a greenhouse at 25 to 30 ° C., and on the 14th day after sowing, the herbicide of the present invention prepared according to the formulation example was treated so as to have a predetermined dose on the water surface. Three weeks after the treatment, the herbicidal effect on various weeds was visually inspected according to the criteria of Test Example 1. The results are shown in Table 16. In addition, No. in each table. Is the compound No. described in the examples. And the symbols have the following meanings. A: Nobie, B: Firefly, C: Eel [Test Example-3] Herbicidal Effect Test by Soil Treatment Put sterilized flood soil in a plastic box 33 cm long, 33 cm wide and 8 cm deep, , Black grass, strawberry, ragweed,
Blue-eyed totoro, shiroza, oak, oinu-nofuguri,
After mixing seeds of chickweed, corn, soybean, cotton, wheat and beet, and covering about 1.5 cm, the herbicide of the present invention prepared according to the formulation example was uniformly applied to the soil surface so as to have a predetermined amount. Sprayed. Three weeks after spraying the chemical solution, the herbicidal effect on various weeds and the effect on crops were visually inspected in accordance with the criteria of Test Example-1. 0 is no effect and 5 is a 5-point scale showing complete withering. The results are shown in Table 17.

[0194] In each table, No. Is the compound No. described in the examples. And the symbols have the following meanings. D: Meishishiba, E: Enokorogosa, F: Oats,
G: black grass, H: strawberry, I: ragweed, J:
Blue stalk, K: Shiroza, L: Inadeta, M: Pseudocarpus, N: Scallop, b: Maize, c: Soybean, d: Cotton, e: Wheat, f: Beet [Test Example-4] Herbicidal effect test by foliage treatment Vertical Put the sterilized flood soil in a plastic box of 33cm, 33cm in width and 8cm in depth, and add crabgrass, enokorogusa, oats, blackgrass, ibis, ragweed,
Blue-eyed totoro, shiroza, oak, oinu-nofuguri,
Mixed seeds of chickweed, corn, soybean, cotton, wheat, beet, and covered about 1.5 cm, then 25 to 30 ° C
The plants were grown in a greenhouse for 14 days, and the herbicide of the present invention prepared according to the formulation example was evenly applied to the foliage so as to have a predetermined amount. Test example on herbicidal effects on various weeds and effects on crops 3 weeks after application of chemical solution-
It was visually inspected according to the criteria of 1. 0 is no effect and 5 is a 5-point scale showing complete withering. First result
The results are shown in Table 8.

Note that in each table, No. Is the imidazolinone compound No. described in the examples. And the symbols have the following meanings. D: Meishishiba, E: Enokorogosa, F: Oats,
G: black grass, H: strawberry, I: ragweed, J:
Blue-toed, K: White, L: Blue-nosed, M: Big-leaf, N: Hawk-be, b: Maize, c: Soybean, d: Cotton, e: Wheat, f: Beet [Table 15]

[0196]

[Table 109] 化合物 Compound dose No. g / a ABCa ───────────────────────────────── 1-14 10 55 5 50 3- 1 20 55 55 55 3-2 2.52 5 15 15 3-3 2.525 55 51} ───────── [Table 16]

[0197]

[Table 110] 化合物 Compound dose No. g / a ABC ───────────────────────────────── 1-14 10 40 3-1 20 5 0 5 3-2 2.52 5 2 5 3-3 2.52 5 25 5} ──── [Table 17]

[0198]

[Table 111] 化合物 Compound dose No. g / a DEFGHIJKLMN bcdef ───────────────────────────────── 1-14 6.3 5 5 0 0 0 2 5 5 5 5 0 0 0 0 0 0 3-1 50 5 5 5 5 5 5 5 5 5 5 5 5 0 5 5 5 3-2 6.3 5 5 0 1 4 4 5 5 5 5 1 0 0 0 0 1 3- 3 6.3 5 5 3 4 4 4 5 5 5 5 0 2 0 0 0 5 ──────────────────────────────── ─ [Table 18]

[0199]

[Table 112] 化合物 Compound dose No. g / a DEFGHIJKLMN bcdef ───────────────────────────────── 1-14 6.3 4 5 2 2 4 2 5 4 5 5 2 2 0 4 0 4 3-1 50 5 5 5 5 5 5 5 5 5 5 5 5 2 5 5 2 3-2 6.3 5 5 2 4 5 5 5 5 5 5 2 5 3 5 1 5 3- 3 6.3 5 5 5 5 5 4 5 5 5 5 3 2 2 4 1 5 ──────────────────────────────── ─

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeomi Watanabe 1470, Shirooka, Shirooka-cho, Minami-Saitama-gun, Saitama Nissan Kagaku Kogyo Co., Ltd. (72) Inventor: Toru Oki, 1470, Shirooka, Shiraoka-cho, Minami-Saitama-gun, Saitama

Claims (4)

[Claims] 1. A compound of formula (I):[Wherein Q and T may be the same or different, and C-
X or a nitrogen atom;¹ Is a hydrogen atom, C₁-C₆Alkyl group, C₁-C₆C
Loalkyl group, C_Three-C₆Cycloalkyl group, C_Two-C
₆Alkenyl group, C_Two-C₆Haloalkenyl group, C_Three−
C₆Cycloalkenyl group, C_Two-C₆Alkynyl group, C
_Two-C₆Haloalkynyl group, C_Three-C₆Cycloalkini
Group, C₁-C_Four Alkoxy C₁-C_FourAlkyl group, A
Optionally substituted phenyl C₁-C_FourAlkyl group
(A is a halogen atom, C₁-C_Four Alkyl group, C₁-C
_FourHaloalkyl group, C₁-C_FourAlkoxy group, C₁-C
_FourHaloalkoxy group, C₁-C_FourAlkoxycarbonyl
Group, C₁-C_Four Alkoxycarbonyl C₁-C_Four Arco
Xy group, C₁-C_Four Alkoxycarbonyl C₁-C_Four C
Loalkyl group, C₁-C_Four Alkoxycarbonyl C ₁−
C_Four Alkylamino group, carbamoyl C₁-C_Four Arco
Xy group, carboxy C₁-C_Four Alkoxy group, nitro group
Or one or more of the same or different selected from cyano groups
Represents the above substituent. ), A group which may be substituted with A
Enyl group (A represents the same as defined above),
Phenyl C_Two-C_FourAlkenyl group (A is before
Represent the following. ), C₁-C_FourAn alkoxy group, A
Optionally substituted phenyl C₁-C_FourAlkoxy group
(A represents the above.), C₁-C_FourHalo alco
Xy group, C₁-C₆Alkoxycarbonyl C₁-C_FourA
Alkyl group, phenyl C optionally substituted with A₁-C
_FourAlkoxy C₁-C_FourAlkyl group, C₁-C_Four Alkyl
Carbonyl group or C₁-C_Four An alkylsulfonyl group
Represents, R^Two And R^ThreeMay be the same or different, and hydrogen
Atom or C₁-C_FourX represents an alkyl group; W represents an oxygen atom or a sulfur atom; X represents a hydrogen atom;₁-C_FourAlkyl group, C₁-C_FourHalo
Alkyl group, C₁-C _FourAlkoxycarbonyl group, halo
Gen atom, cyano group, C₁-C_FourAlkoxy group or C
₁-C_FourRepresents an alkylthio group, m represents an integer of 0 to 3, n represents an integer of 0 to 2, and Ar is selected from the following formulas (a), (b) and (c).
RU groupAnd R^FourRepresents a hydrogen atom or a halogen atom;^FiveIs a hydrogen atom, a halogen atom, C₁-C_FourAlkyl
Group, C₁-C_FourHaloalkyl group, nitro group, cyano group,
Phenyl C optionally substituted with A₁-C_FourAlkoki
A group (A represents the same as defined above), a hydroxy group or
Is C₁-C_FourRepresents a haloalkoxy group, R⁶Is a hydrogen atom, C₁-C₆Alkyl group, C_Three-C₆Shi
Chloroalkyl group, C₁-C₆Haloalkyl group, C_Two-C
₆Alkenyl group, C_Two-C₆Haloalkenyl group, C_Two−
C₆Alkynyl group, C_Two-C₆Haloalkynyl group, at A
A phenyl group which may be substituted (A is as defined above;
I forgot. ), Formyl group, and
Nil C₁-C_FourAlkyl group (A is as defined above)
You. ), Phenyl C optionally substituted with A_Two-C_Four
Alkenyl groups (A represents the same as defined above), carboxy
Sil group, C₁-C₆Alkoxycarbonyl group, C₁-C
₆Alkoxycarbonyl C₁-C_FourAlkyl group, C₁−
C₆Alkoxycarbonyl C₁-C_FourHaloalkyl group,
C₁-C₆Alkoxycarbonyl C_Two-C_FourAlkenyl
Group, C₁-C₆Alkoxycarbonyl C_Two-C_FourHaloa
Lucenyl group, -YR⁷Group (Y is oxygen atom or sulfur
Represents an atom, R⁷Is a hydrogen atom, C₁-C₆Alkyl
Group, C_Three-C₆Cycloalkyl group, C₁-C₆Haloal
Kill group, C_Two-C₆Alkenyl group, C_Two-C₆Haloal
Kenyl group, C_Two-C₆Alkynyl group, C_Two-C₆Haloa
Rukinyl group, C₁-C_Four Alkoxy C₁-C_Four Alkyl
A phenyl group optionally substituted by A (A is
Represents a thing. ), Phenyl optionally substituted with A
C₁-C_FourAn alkyl group (A represents the same as described above),
Phenyl C optionally substituted with A_Two-C_FourAlkene
(A represents the same as defined above), C₁-C₆Arco
Xycarbonyl C₁-C_FourAlkyl group, C₁-C₆Al
Coxycarbonyl C₁-C_FourHaloalkyl group, C₁-C
₆Alkoxycarbonyl C_Two-C_FourAlkenyl group or
C₁-C₆Alkoxycarbonyl C_Two-C_FourHalo arche
Represents a nyl group. ), -N (R⁸) R⁹Base ｛R⁸Is hydrogen
Atom, C₁-C₆Alkyl group, C₁-C₆Haloalkyl
Group, C_Two-C₆Alkenyl group, C_Two-C₆Alkynyl
Group, C₁-C₆Alkoxycarbonyl group, C₁-C₆A
Alkylcarbonyl group, formyl group, C₁-C₆ Alkyl
Sulfonyl group, phenyl C optionally substituted with A₁
-C_FourAlkylcarbonyl group (A is as defined above)
You. ) Or phenylcarbo optionally substituted with A
A phenyl group (A represents the same as defined above);⁹Is
Hydrogen atom, C₁-C₆Alkyl group, C₁-C₆Haloal
Kill group, C_Two-C₆Alkenyl group, C_Two-C₆Alkini
Group, C₁-C₆Alkoxycarbonyl group, C₁-C₆
An alkylcarbonyl group,
A carbonyl group (A represents the same as defined above);₁
-C₆Alkoxycarbonyl C₁-C_FourAlkyl group, C
₁-C₆Alkylsulfonyl group or C₁-C₆Gials
Represents a killsulfamoyl group. ｝, Cyano group, nitro
Group, cyano C ₁-C_FourAlkyl group or halogen atom
Represents, R^TenIs a hydrogen atom, C₁-C₆Alkyl group, C₁-C₆
Haloalkyl group, C_Three-C₆Cycloalkyl group, C_Two−
C₆Alkenyl group, C_Two-C₆Haloalkenyl group, C_Two
-C₆Alkynyl group, C_Two-C₆Haloalkynyl group, C
₁-C₆Alkylcarbonyl group, C₁-C₆Alkylka
Rubonil C₁-C_FourAlkyl group, C₁-C₆Alkoxy
Carbonyl C₁-C_FourAn alkyl group, substituted with A
Also good phenyl C₁-C_FourAlkylcarbonyl group (A is
Represents the above. ) Cyano C ₁-C_FourAlkyl group,
Phenyl C optionally substituted with A₁-C_FourAlkyl
A group (A represents the same as defined above), C₁-C_FourAlkoki
C₁-C_FourAlkyl group, C₁-C_Four Alkylsulfoni
Group or C₁-C_FourAlkylthio C₁-C_FourAlkyl
R represents a group¹¹Represents a hydrogen atom or a chlorine atom, Z represents an oxygen atom, a sulfur atom or NH, P represents 0 or 1, and E represents an integer of 0 to 2. A compound represented by
Pesticides contained. 2. A herbicide containing the compound according to claim 1. 3. Q represents a nitrogen atom, T represents CH, R¹ Is C₁-C_FourHaloalkyl group or C_Two-C_FourAl
Represents a phenyl group;^TwoAnd R^Three Represents a hydrogen atom, W represents an oxygen atom, X represents a hydrogen atom, a halogen atom or C₁-C₆Alkyl
M represents 0 or 1; n represents 0 or 1; Ar represents formula (a) or (b);^Four Represents a hydrogen atom, a fluorine atom or a chlorine atom;^Five Is chlorine, bromine, cyano, trifluoro
Represents a tyl group or a difluoromethoxy group,⁶ Is -YR⁷Group, N (R⁸) R⁹Group, C₁-C₆A
Lucoxycarbonyl C ₁-C_FourHaloalkyl group or C
₁-C₆Alkoxycarbonyl C₁-C_FourHaloalkene
R represents a group^TenIs a hydrogen atom, C₁-C₆Alkyl group, C_Two-C₆A
Lucenyl group, C_Two-C ₆Alkynyl group, C₁-C₆Al
Coxycarbonyl C₁-C_FourAlkyl group, cyano C₁−
C_FourAlkyl group, C₁-C₆Alkoxy C₁-C_FourAl
Kill group or C ₁-C₆Alkylthio C₁-C_FourArchi
Z represents an oxygen atom; P represents 1; and E represents 1. The compound according to claim 1, which is represented by the formula:
Herbicide containing a substance. [Claim 4] [R ¹ Represents a difluoromethyl group, a 3-fluoropropyl group or an allyl group, n represents 0, R ⁴ represents a fluorine atom, R ⁵ represents a chlorine atom or a cyano group, and R ⁶ represents a C ₁ -C ₆ alkoxy. Carbonyl C ₁ -C ₄ haloalkyl group or C ₁ -C ₆ alkoxycarbonyl C ₁
It represents -C ₄ haloalkenyl group, R ⁷ is C ₁ -C ₆ alkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₄ alkynyl or C ₁ -C ₆ alkoxycarbonyl C ₁ -C ₄ alkyl R ⁸ represents a hydrogen atom, a C ₁ -C ₄ alkylcarbonyl group,
₁ -C ₄ alkoxycarbonyl group, an unsubstituted or substituted by even a phenyl group or A optionally phenyl C ₁ -C ₄ alkylcarbonyl group A, R ⁹ is C ₁ -C ₆ alkylsulfonyl Group or C ₁ -C
It represents ₆ dialkylsulfamoyl group, R ¹⁰ represents a C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group or a cyano C ₁ -C ₄ alkyl group. ] The herbicide containing the compound of Claim 3 shown by these.