Process for the preparation of 3-aryluracils

The present invention relates to a novel process for the preparation of 3-phenyluracils and to the use of certain aromatic amino compounds as intermediates in the preparation of those 3-phenyluracils.

3-Phenyluracils can be prepared, for example, by formation of the uracil ring from open-chained aniline derivatives that already have the desired substitution pattern. For example, it is known from US-A-5 183 492 to prepare 3-phenyluracils of formula VIII

wherein, inter alia,

R ₁₀ is C _r C ₄ alkyl, C ₃ -C ₄ alkenyl or C ₃ -C alkynyl;

Rj j is C _r C ₄ alkyl or C _r C ₄ haloaιkyl;

R ₁₃ is hydrogen, halogen, C _r C ₃ alkyl, C _r C ₃ alkoxy, C _r C ₃ haloalkyl, C _r C ₃ haloalkoxy, cyano or hydroxy; R ₁₂ is hydrogen, fluorine or chlorine; and R ₁₄ is (C ₃ -C ₆ alkenyloxy)carbonyl-C _r C ₄ alkyl, by.

A) in the case of compounds of formula VIII wherein R is C _r C ₄ alkyl, converting a compound of formula IX

H ₂ N

wherein R ₁₂ , R ₁₃ and R ₁₄ as are defined for formula VIII, with a compound of formula X

wherein R _{j l} is C _j ^alkyl and R ₁₅ is C _r C ₄ alkyl, into the compound of formula XI

wherein R _n is C _j -C ₄ alkyl and R ₁₂ , R _]3 , Rj ₄ and R _I5 are as defined above, subjecting that compound to cyclisation under basic conditions and then alkylating the 1 -position of the resulting 3-phenyluracil, or

B) in the case of compounds of formula VIII wherein RJ J is C _r C ₄ haloalkyl, converting a compound of formula XII

wherein R _j • and R _]5 are as defined above, with a compound of formula XIII

wherein R ₁₂ , R _]3 and R ₁₄ are as defined above, or with a compound of formula Xllla

(Xllla), wherein R ₁₂ and R ₁₃ are as defined above, into the compound of formula XI

wherein R _π is C _r C ₄ haloalkyl and R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are as defined above, subjecting that compound to cyclisation under basic conditions, and then alkylating the 1 -position of the resulting 3-phenyluracil.

It has been found in accordance with the present invention that 3-phenyluracils can be prepared in an especially advantageous manner by using as starting compound, instead of an aminocarbonylaminophenyl derivative of formula IX or an isocyanatophenyl derivative of formula XIII or an alkyloxycarbonylaminophenyl derivative of formula Xllla, an aniline compound obtained by reduction of a corresponding nitrophenyl derivative, and converting that aniline compound with a β-keto ester or a β-ketocarboxylic acid halide into an acetoacetanilide which is then converted with an ammonium salt into an enamine, from which the compound of formula I is obtained after cyclisation and alkylation.

It is therefore proposed according to the invention to prepare compounds of formula I

wherein

R is the group -(Y-Q) _m -[C(O)] _n -X-R ₂ ;

R _j is C _j -C ₄ alkyl, C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl;

R ₂ is C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl, C ₃ -C ₈ cycloalkenyl, C ₆ -C ₈ bicycloalkenyl or

C ₃ -C ₆ haloalkenyl; R ₃ is hydrogen, halogen, C,-C ₃ alkyl, C _r C ₃ alkoxy, C _r C ₃ haloalkyl, C _r C ₃ haloalkoxy, cyano or hydroxy; or R ₃ and R together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; R is hydrogen, fluorine or chlorine; R ₅ is C,-C ₄ alkyl, C _r C ₄ haloalkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl;

Y is oxygen, sulfur, N-R ₆ or C(O)-X _j ;

X is oxygen, sulfur or N-R ₇ ;

X _j is oxygen, sulfur or N-R ₈ ;

R ₆ , R ₇ and R ₈ are each independently of the others C _r C ₄ alkyl, Cj-C ₄ haloalkyl,

C -C ₆ alkenyl or C ₃ -C ₆ alkynyl; m is 0 or 1 ; n is 0 or 1 ; Q is a C _j -C ₁₀ alkylene group the carbon atoms of which are capable of forming a 1,1- or 1,2-linked C -C ₈ cycloalkyl ring; n- is 0 or 1;

X ₃ is oxygen or sulfur; and R ₁₇ is C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl, with the proviso that m is 0 when n is 0, by

a) reducing a compound of formula VII

wherein R, R ₃ and R ₄ are as defined for formula I, in the presence of a catalyst containing platinum modified by lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver or gold, to a compound of formula VI

wherein R, R ₃ and R ₄ are as defined for formula I,

b) reacting that compound with a compound of formula V

O

R. Λ _π (V),

wherein R ₅ is as defined for formula I and R ₉ is chlorine or C _j -C alkoxy, in an aprotic solvent, to form a compound of formula IV

wherein R, R ₃ , R ₄ and R ₅ are as defined for formula I,

c) converting that compound in the presence of an enaminating agent, such as ammonia, but preferably in the presence of an ammonium salt of a carboxylic acid, into the compound of formula III

wherein R, R ₃ , R ₄ and R ₅ are as defined for formula I,

d) reacting that compound in the presence of a base and an inert solvent with a compound of formula Ilia

Y ¹ (Ilia),

wherein L ₁ and L ₂ are each independently of the other halogen, C _r C ₄ alkoxy, imidazol-1-yl or 1,2,4-triazol-l-yl, to form the compound of formula II

wherein R, R , R ₄ and R ₅ are as defined for formula I, and

e) converting that compound in an inert solvent in the presence of a base with a compound of formula Ha

R1-L3 (Ha),

wherein L ₃ is halogen or OSO ₂ OR _j and R _j is as defined for formula I, into the compound of formula I.

Within the scope of the present invention, alkyl is, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec -butyl or tert-butyl.

Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl or pentafluoroethyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl or dichlorofluoromethyl.

Alkenyl is to be understood as being straight-chained or branched alkenyl, such as allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl or 2-hexenyl.

The alkynyl groups mentioned in the definitions of the substituents may be straight- chained or branched, such as propargyl, 3-butynyl, 1-methylpropargyl, 1-pentynyl or 2-hexynyl.

Alkoxy is, for example, methoxy, ethoxy, propyloxy or isopropyloxy.

In the above definitions, halogen is to be understood to be fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Cycloalkenyl is, for example, cyclobutenyl, cyclopentenyl, 3-methylcyclopentenyl or cyclohexenyl.

Q as a C _r C ₁₀ alkylene group is, for example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -C__ι -CH ₂ -CH ₂ -CH , -CH ₂ -CH ₂ -CH ₂ -CH -CH ₂ , -CH ₂ -CH -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH(CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH(CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, -C(CH ₂ CH ₂ CH ₃ ) ₂ - or -C(CH ₂ CH ₂ CH ₂ CH ₃ ) ₂ -.

Q as a C _j -C _]0 alkylene group the carbon atoms of which form a 1,1- or 1,2-linked

C ₃ -C ₈ cycloalkyl ring is, for example, V , \ , ^ , J -

In those cases where R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _n ι-X ₃ -, that group is linked in such a manner that -N(R ₁₇ )- occupies the 3-position of R and -X ₃ - the 4-position of R ₃ on the phenyl ring.

The fact that at least one asymmetric carbon atom may be present in the compounds of formula I, for example compounds of formula I wherein R is the group -(Y-Q) _m -[C(O)] _n -X-R ₂ and Q is a branched C _j -C ₁₀ alkylene group, for example -CH(CH ₃ )- or -CH(CH ₃ )-CH ₂ -, and/or R ₂ is a branched C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl group, means that the compounds can occur both in the form of optically active individual isomers and in the form of racemic mixtures. The optically active compounds of formula I can be obtained from the racemic mixtures by known separating methods, such as fractional crystallisation. In the present invention, the compounds of formula I are to be understood to include both the pure optical antipodes and the racemates or diastereo- isomers. Unless specific reference is made to the individual optical antipodes, the formula indicated is to be understood to represent the particular racemic mixtures that are obtained by the preparation process indicated.

There are preferably prepared by the process according to the invention those compounds of formula I wherein R ₅ is C _r C ₄ haloalkyl; especially those wherein R ₅ is difluoromethyl, trifluoromethyl, difluorochloromethyl, trichloromethyl or pentafluoroethyl.

There are preferably prepared by the process according to the invention also those compounds of formula I wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; < is 0; and X ₃ is sulfur.

There are likewise preferably prepared by the process according to the invention those compounds of formula I wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; nj is 1; and X ₃ is oxygen.

The process is important for the preparation of compounds of formula I wherein R and R ₃ together form the group -N(R _{] 7} )-C(O)-(CH ₂ ) _n ι-X ₃ -; Rj ₇ is allyl, methallyl, propargyl or 1 -methylpropargyl.

The process is also important for the preparation of compounds of formula I wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nr X ₃ -; Rj is methyl; R ₄ is hydrogen or fluorine; and R ₅ is C _j -C ₄ haloalkyl; especially those wherein R ₅ is trifluoromethyl, trichloromethyl, difluorochloromethyl, difluoromethyl or pentafluoroethyl.

Also of advantage is the preparation of those compounds of formula I wherein R is hydrogen or fluorine.

The process according to the invention is especially suitable for the preparation of compounds of formula I wherein R ₃ is halogen.

Special mention should be made of the preparation of compounds of formula I wherein R _j is Cj-C ₄ alkyl.

Very special preference is given to the preparation of compounds of formula I wherein R _j is methyl, R ₃ is chlorine, R ₄ is hydrogen or fluorine and R ₅ is trifluoromethyl, and m and n are preferably 1.

Also advantageous is the preparation of those compounds of formula I wherein Q is -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(C ₂ H ₅ ) ₂ -,

-C(CH ₂ CH ₂ CH ₂ ) ₂ -, -C(CH ₂ CH ₂ CH ₂ CH ₂ ) ₂ , -2_ . _£_ . _Q_ .

A , or _. especially those wherein Q is -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-,

<S>-CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-CH ₂ -, <S>-CH(CH ₃ )-CH ₂ -, -C(C ₂ H ₅ ) ₂ - or V .

Special mention should be made of the preparation of compounds of formula I wherein Y is C(O)X _j , n is 1 and X _j and X are oxygen.

Special mention should also be made of the preparation of those compounds of formula I wherein X-R ₂ is C ₃ -C ₆ alkenyloxy.

The process according to the invention is especially suitable for the preparation of

2-cyano-5-(3 ,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidinyl)-benzoic acid 1-methylallyl ester;

<S>2-chloro-5-(3 ,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidinyl)- benzoic acid 1-methylallyl ester;

2-chloro-5-(3 ,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidinyl)-4- fluorobenzallylamide;

2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromet hyl-l(2H)-pyrimidinyl)- thiobenzoic acid allylamide;

2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromet hyl-l(2H)-pyrimidinyl)- benzoic acid (l-allylaminocarbonyl-l-methyl)-ethyl ester;

<S>2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-tri fluoromethyl-l(2H)-pyrimidinyl)- benzoic acid (l-allylaminocarbonyl-l-methyl)-methyl ester;

2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromet hyl-l(2H)-pyrimidinyl)- benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester;

2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trichloromet hyl-l(2H)-pyrimidinyl)- benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester;

2-chloro-5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromet hyl-l(2H)-pyrimidinyl)-4- fluorobenzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester; and

<S>2-chloro-5-(3 ,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethy 1- 1 (2H)-pyrimidinyl)- benzoic acid (l-methylallyloxycarbonyl-l-methyl)-ethyl ester.

The use of cobalt sulfide as catalyst in the hydrogenation of nitroaromatic compounds has been proposed, for example, in DE-OS 2 362 780. That catalyst has the serious

disadvantage that sulfur-containing by-products are formed during the hydrogenation, which reduce product quality and severely limit the reusability of the solvents. Also formed during the reaction are volatile sulfur compounds, such as hydrogen sulfide, which, if they escape through leaks in the reactor, especially during industrial synthesis, lead to considerable safety problems.

JP 82 120 553 discloses the preparation of aromatic amines that can be substituted by groups having unsaturated carbon-carbon bonds, by hydrogenating the corresponding nitro compounds in the presence of a palladium catalyst and in the presence of a carboxylic acid, such as dinitrobenzoic acid. The yield of only 85.5 % obtained with that process in the preparation of 2-(3,5-diamino-benzoyloxy)ethyl methacrylate is not very satisfactory, especially for industrial purposes.

In process step a) specially modified platinum catalysts are used. Contrary to expectations, it was found with those catalysts that it is possible to reduce nitroaromatic compounds to the corresponding amino compounds selectively, without simultaneously hydrogenating the side chains of the nitroaromatic compounds containing unsaturated carbon-carbon bonds. The use of those catalysts is a particular advantage of the process according to the invention, since the high yield that is obtainable in the first reaction step has a considerable influence on the yield of compound of formula I obtained after all the reaction steps have been carried out.

DE-OS 2 042 368 and J. Mol. Catal. 71, (1992) 317 describe the preparation and use of platinum catalysts modified by tin, lead, germanium, aluminium, zinc, bismuth and silver for the preparation of aromatic amines substitituted by halogen.

It has been found, surprisingly, that when iron, ruthenium, cobalt or manganese compounds are used in process step a) as additional promotors for the platinum catalysts modified by lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver and by gold, the yields of compound of formula VI can be further increased.

The promotors can either be added to the reaction mixture directly in the form of salts or deposited as an insoluble compound on the surface of the catalysts during the preparation or the modification thereof.

Preferred promotors that can be used in the catalysts are: Fe ²⁺ , Fe ³⁺ , Ru ³⁺ , Mn ²⁺ and Mn ³⁺

in the form of salts with the anions Cl ^" , Br, F ^" , SO ₄ ^2" , NO ₃ \ acetate, citrate, gluconate, lactate, oxalate, benzoate, naphthenate, tartrate and formate, or in the form of a suitable metal complex.

In addition to the mentioned promotors, the hydrogenation can be accelerated using a co-promotor. Suitable as co-promotors are salts or pairs of ions that are generally soluble in organic solvents, especially ionophores known from electrochemistry, for example in the form of a cation (C _r C ₆ alkyl) ₄ N ⁺ or • N ^"* - — c c ₆ aikyi ₀ r in the form of an anion Cl",

Br, F", BF ₄ % PF ₆ ", NO ₃ -, F ₃ CSO ₃ -, BPh ₄ ", PhCOO", SO ₃ ^" , CH ₃ SO ₃ - or F ₃ COO-.

The promotor is preferably used in an amount of from 0.001 to 10 % by weight, based on the compound of formula VII used, there being used as promotor especially an iron salt, most especially FeCl ₂ «4H O.

The use of iron and manganese compounds as promotors for platinum catalysts that are capable of reducing aromatic nitro compounds selectively in the presence of halogen to the corresponding amines is known, for example, from US-A-4 212 824 and 2 823 235.

The modifying metal used for the platinum catalyst is preferably lead, especially in the form of lead acetate, lead nitrate, lead chloride or tetraalkylene lead, such as tetraethyl lead.

The catalyst is used preferably in an amount of from 0.1 to 5 % by weight, based on the compound of formula VII that is used, the ratio by weight of platinum to modifying metal being from 1 : 0.001 to 1 : 1, preferably from 1 : 0.1 to 1 : 0.5.

Preference is given to the use of a catalyst containing from 1 to 10 % by weight of platinum. The platinum to be modified can be used in the form of platinum black, platinum oxide or preferably in metallic or oxidised form applied to a carrier. Carriers that are especially suitable are activated carbon, silicic acid, silica gel, aluminium oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, titanium oxide, magnesium oxide, iron oxide, lead oxide, lead sulfate or lead carbonate, preferably activated carbon, aluminium oxide or calcium carbonate. Platinum applied to the above-

mentioned carrier material is commercially available or can be prepared by methods familiar to a person skilled in the art, such as those disclosed, for example, in DE-OS 2 042 368.

Process step a) of the process according to the invention is carried out under a pressure of from 1 to 100 bar and at a temperature of from +20 to +160°C, preferably under a pressure of from 20 to 40 bar and at a temperature of from +100 to +140°C.

The fact that the choice of solvent is not critical is a particular advantage of process step a) of the process of the invention. It is possible to use solvents having good dissolving power that are not sufficiently inert in the presence of unmodified platinum catalysts, such as ketones. Preferred solvents are water, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, the isomers of butanol and cyclohexanol, ethers, esters and ketones, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, ethyl acetate, butyl acetate, butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, carboxylic acids, such as acetic acid and propionic acid, dipolar aprotic solvents, such as dimethylformamide, N-methyl- pyrrolidone, dimethylacetamide, sulfolane, dimethyl sulfoxide or acetonitrile, non-polar solvents, such as toluene or xylene, chlorinated aromatic hydrocarbons, such as methylene chloride, C ₃ -C ₇ alkanes or cyclohexane.

Those solvents can be used in pure form or as mixtures. In especially preferred forms of the process according to the invention there are used as solvents for process step a) tetrahydrofuran, dimethoxyethane, methyl ethyl ketone, acetone and cyclohexanone, in pure form or as mixtures with alcohols and/or C C ₄ carboxylic acids.

The reaction according to process step a) is preferably carried out in the liquid phase, especially with a pulverulent catalyst, either continuously or discontinuously as a semi-solid-phase hydrogenation, or in a bubble column, or with a shaped catalyst in a trickle bed. The reaction can also be carried out in the gas phase with a pulverulent catalyst in a fluidised bed or with a shaped catalyst in a fixed bed.

Suitable aprotic solvents for process step b) are, for example, aromatic hydrocarbons, such as benzene and toluene, or hydrocarbons, such as hexane, cyclohexane, halogenated hydrocarbons, such as trichloromethane, 1,1,1-trichloroethane or 1 ,2-dichloroethane, or ethers, such as diisobutyl ether, tetrahydrofuran or 1,4-dioxane.

Process steps b) to e) are essentially known per se.

If desired, process step b) can be carried out in the presence of a base. Suitable bases are, for example, oxides, carbonates of an alkali metal or alkaline earth metal, such as sodium carbonate, alkali metal alkoxides, such as potassium tert-butoxide, amines, such as trialkylamines, for example triethylamine or triethanolamine, or pyridine bases, such as dimethylaminopyridine.

The reaction of compounds of formula V wherein R ₉ is C _r C ₄ alkoxy is carried out preferably at temperatures of from 0 to 180°C, preferably at from 60 to 130°C, especially under reflux, it being very especially preferred to remove the resulting alcohol, for example by azeotropic distillation. The reaction of compounds of formula V wherein R ₉ is chlorine is preferably carried out with cooling at temperatures of from -40 to +150°C, preferably from -20 to +80°C. Base-catalysed reactions of β-keto esters wherein R ₅ is other than haloalkyl, in which the resulting alcohol is not, however, removed by azeotropic distillation are described, for example, in Synthesis, 1988, 753.

It has been found that the reaction according to process step b) also leads to a high yield of the desired product of formula IV when R ₅ is a strongly electron-attracting substituent, such as CF ₃ or CC1 ₃ . In the knowledge of the prior art, that course of the reaction was not to be expected.

For example, according to J. Het. Chem. 2, 113, (1965), the reaction of α-naphthylamine with 1,1,1-trifluoroacetoacetic acid ethyl ester in benzene in the presence of catalytic amounts of concentrated acetic acid yields the following products A and B in approx¬ imately equal portions in a yield of 17.2 %:

(B).

US-A-2 857 373 describes the preparation of trifluoroacetoacetanilide in a yield of only 45 % by heating 1,1,1-trifluoroacetoacetic acid ethyl ester with aniline in boiling xylene with simultaneous removal of the alcohol formed.

The starting materials of formulae V and VII are either known or can be prepared in accordance with known methods.

For example, compounds of formula VII wherein m and n are 1 and Y is C(O)-X _j can be prepared in accordance with the following scheme:

H-XjQCOOH (XVI) H®^e.g. H ₂ SO ₄ , HC1) inert solvent

XIV XVa XVHa

Tj and T ₂ are reagents for introducing a leaving group or L ₅ , respectively (e.g. SOCl ₂ ,

Cl

I Me

COCl ₂ , (COCl) ₂ , Ac ₂ O, (imidazol-l'-yl) ₂ CO, ϊv^N - C =< ₀ r cyanuric acid

Ms chloride); and

L and L ₅ are each independendy of the other halogen (esp. Cl), O-COaJLkylC-,^. or imidazol-l'-yl.

The individual reaction steps can be carried out, for example, as follows:

XIV XVa:

The carboxylic acid XTV is converted in an inert solvent at from -20 to +150°C (preferably from 0 to +100°C) with a suitable reagent T ₁ into the activated acid derivative XVa. The chloride (L ₄ = Cl) may be mentioned as preferred acid derivative XV.

XVa ► XVπa:

The compound of formula XVa is reacted in the presence of a base (see below) in an inert solvent at from -10 to +150°C, preferably from 0 to +100°C, with an acid derivative XVI to form XVHa.

When X* _[ is oxygen, the acid XTV can alternatively be reacted with the alcohol XVI by acid-catalysed esterification in an inert solvent at from -10 to +150°C to form XVHa. There may be used as acid catalysts, for example, H ₂ SO , HC1, H ₃ PO ₄ and BF ₃ OEt ₂ . If desired, water of reaction that is formed can be removed continuously from the reaction mixture, for example by azeotropic distillation in a solvent, such as toluene or xylene.

XVIIa ► XVma:

The compound of formula XVIIa thus obtained is reacted analogously to the method described for the compound of formula XTV using T ₂ in an inert solvent (such as toluene, xylene, ethyl acetate, dioxane, tetrahydrofuran or chloroform, ethylene chloride, 1,1,1-trichloroethane or dichloromethane), at a temperature of from -20 to +150°C, preferably from 0 to +100°C, to form XVHIa.

XVIIIa ► Vllb:

Finally, by acylation with the compound of formula XVIIIa, HXR (XIX) is converted in an inert solvent and in the presence of a base at a temperature of from -20 to +150°C (preferably from 0° to +60°C) into the acid derivative of formula Vllb. If desired, a catalyst, such as 4-dimethylaminopyridine, can be added. Instead of a solvent, it is also possible to use an excess of the organic base used, for example pyridine or quinoline, as solvent.

XX

XVa -► Vllb:

Alternatively, the activated acid derivative XVa can be reacted with an intermediate XX directly to Vllb in the presence of a base in an inert organic solvent at a temperature of from -20 to +150°C, preferably from 0° to +60°C, if appropriate with the addition of a catalyst, such as 4-dimethylaminopyridine.

The intermediates of formula XX are known in some cases from US-A 5 183 492 or they can be prepared by analogous methods.

The intermediates of formula VII wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; n- is 0; and X ₃ is sulfur (starting materials that lead to the 5-amino-2(3H)-benzothiazolones of formula Vie in Table 19), are known or can be prepared in accordance with known processes, for example those described in US-A 4 888 428.

The corresponding amines of formula Vie are likewise known or can be prepared in accordance with known processes, for example those described in US-A-4 888 428.

The intermediates of formula VII wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; n _j is 0; and X ₃ is oxygen (starting materials that lead to the 5-amino-2(3H)-benzoxazolones of formula Vic in Table 19) are known or can be prepared in accordance with known processes, for example those described in EP-A-0415 642.

The corresponding amines of formula Vic are likewise known or can be prepared in accordance with known processes, for example those described in EP-A-0415 642.

The intermediates of formula VII wherein R and R ₃ together form the group -N(R ₁₇ )-C(O)-(CH ₂ ) _nl -X ₃ -; n- is 1; and X ₃ is oxygen or sulfur (starting materials that lead to the 6-amino-3(4H)-benzoxazines or -benzothiazines of formula VId in Table 24) are known or can be prepared in accordance with known processes, for example those described in EP-A-0 170 191 or EP-A-0 349 876.

The corresponding amines of formula VId are likewise known or can be prepared in accordance with known processes, for example those described in EP-A-0 170 191 or

EP-A-0 349 876.

Bases

Suitable bases are, for example, alkali metal and alkaline earth metal carbonates (NaHCO ₃ , K ₂ CO ₃ ) or alkaline earth metal oxides, such as CaO, or tertiary amines, such as trialkylamines (NEt ₃ ), and pyridine bases, such as pyridine, collidine or quinoline.

Inert solvents see XVII ► XVIII (example of procedure)

If desired, the reactions can be carried out under the conditions of phase-transfer catalysis.

In process step c), preference is given to the use of ammonium acetate as the ammonium salt, especially in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents. The reaction can, if desired, be carried out in an aprotic solvent, such as ethyl acetate, diisopropyl ether, tetrahydrofuran, dioxane, cyclohexane, toluene or a mixture thereof, under normal pressure or under elevated pressure. If desired, water that is formed can be removed under reflux with a drying agent, such as calcium chloride, or a molecular sieve, or by azeotropic distillation.

Reactions with ammonium acetate in ethanol of compounds that differ from the compound of formula III in that R ₅ is phenyl are described, for example, in US-A-5 116 404. In a preferred form of the process according to the invention, reaction step c) is carried out in the presence of ammonium acetate either in an aprotic solvent or in the melt in the absence of a solvent. The reaction temperatures are dependent on the choice of solvent and are in the range of from 0 to 180°C, preferably from 50 to 140°C; when using ammonium acetate in the melt they are preferably in the range of from 100 to 130°C. Lower melting points can be achieved, for example, by adding small amounts of inert solvents, such as ethyl acetate. The compounds of formula IV and the compounds of formula III prepared there¬ from are novel and the present invention relates also thereto.

If desired, catalytic amounts of organic or inorganic acids, such as hydrochloric acid, sulfuric acid, oxalic acid, benzoic acid or p-toluenesulfonic acid, or sodium hydrogen sulfate or potassium hydrogen phosphate can be added.

In process step d) preference is given to the use of a compound of formula Ilia wherein L _j and L ₂ are chlorine. Suitable bases are especially organic bases, such as triethylamine, quinoline or pyridine, or mixtures, such as pyridine with 4-dimethylaminopyridine or quinoline. Instead of a base, it is also possible to use H-L _j or H-L ₂ scavengers, such as epoxides, for example propylene oxide. Suitable inert solvents are aromatic hydrocarbons, such as benzene and toluene, or halogenated hydrocarbons, such as dichloromethane or 1,1,1-trichloroethane. The use of toluene is preferred. The reaction temperatures are in the range of from -20 to + 160°C, preferably from 0 to 100°C. The reactions can be carried out under normal pressure or under elevated pressure.

Reactions in accordance with process step d) are known, for example, from US-A-5 116404 and US-A-4 941 909.

Suitable inert solvents in process step e) are especially protic solvents, such as C _r C ₄ alcohols, for example ethanol, or aprotic solvents, such as aliphatic or cyclic ethers, such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones, such as acetone, nitriles, such as acetonitrile, amides, such as dimethylformamide, N-methyl- pyrrolidone, or sulfoxides, such as dimethyl sulfoxide. There are used as bases preferably carbonates, such as potassium hydrogen carbonate, potassium carbonate and sodium carbonate, or alkali metal hydroxides, such as sodium or potassium hydroxide, alkaline earth metal oxides, such as calcium oxide or magnesium oxide, alkali metal alcoholates, such as sodium alcoholate, tertiary amines, such as pyridine derivatives, or ethyldiiso- propylamine. The reaction temperatures are in the range from 0°C to the reflux tempera¬ ture of the reaction mixture. If desired, the reaction can be accelerated using catalysts, such as crown ethers.

By optimising the reaction conditions, it is possible to obtain yields of more than 95 %.

The compounds prepared according to the invention can be used, for example, as active ingredients in herbicidal compositions for controlling weeds and grasses in crops of useful plants.

Preparation examples:

Example PI: Preparation of a 5 % Pt-1 Pb-CaCO _? catalyst:

5 g of a 5% Pt-CaCO ₃ catalyst are suspended in 20 ml of water and then at room tempera¬ ture 2 ml of a Pb-tetraacetate solution (0.091 g of Pb(OAc) ₂ » 3H ₂ O; corresponding to 1 % Pb) are slowly added thereto. After stirring for 10 minutes at room temperature, the temperature of the mixture is increased to 80°C for 40 minutes. Filtration, washing with water and drying at a temperature of 80°C in vacuo yields the catalyst having a composition of 4.87 % Pt and 1 % Pb.

Example P2: Preparation of 3-amino-benzoic acid allyl ester (Compound No. 1.91): In a stirred autoclave, 1 g of a catalyst prepared in accordance with Example P 1 is added to a solution of 10.4 g of 3-nitrobenzoic acid allyl ester in 100 ml of tetrahydrofuran and the reaction mixture is hydrogenated for 8 hours at a temperature of 120°C and under a hydrogen pressure of 20 bar. Filtration of the catalyst and removal of the solvent by distillation yields 9.1 g of crude product containing 88.8 % 3-amino-benzoic acid allyl ester in a yield of 91 % of theory.

'H-NMR (CDC1 ₃ , 250 MHz): 3.68 ppm (s, 2H); 4.75 ppm (d, 2H); 5.25 ppm (q, 2H); 5.95 ppm (m, 1H); 7.15 ppm (m, 1H); 7.25 ppm (m, 1H); 7.35 ppm (m, 1H).

Example P3: Preparation of 2-(2-chloro-5-amino-benzoyloxy)-2-methyl-propionic acid allyl ester:

In a stirred autoclave, 0.1 g of a catalyst prepared in accordance with Example PI is added to a solution of 10 g of 2-(2-chloro-5-nitro-benzoyloxy)-2-methyl-propionic acid allyl ester in 80 ml of tetrahydrofuran and 20 ml of n-propanol, and the reaction mixture is hydrogenated for 15 hours at a temperature of 140°C and under a hydrogen pressure of

20 bar. After cooling to room temperature and rendering the stirred autoclave inert with nitrogen, the catalyst is filtered off. 126.8 g of a solution containing 6.58 % 2-(2-chloro-

5-amino-benzoyloxy)-2-methyl-propionic acid allyl ester (yield 92.7 % of theory) are obtained.

'H-NMR (CDCI ₃ , 250 MHz): 1.62 ppm (s, 6H); 3.65 ppm (s, 2H); 4.6 ppm (d, 2H);

5.2 ppm (q, 2H); 5.85 ppm (m, 1H); 6.65 ppm (m, 1H); 7.0 ppm (m, 1H); 7.1 ppm

(m, 1H).

Example P4: Preparation of 2-(2-chloro-5-amino-benzoyloxy)-2-methyl-propionic acid allyl ester:

In a stirred autoclave, 0.1 g of a catalyst prepared in accordance with Example P 1 and, in addition, 6 mg (0.1 mol %) of FeCl ₂ *4H ₂ O are added to a solution of 10 g of 2-(2-chloro- 5-nitro-benzoyloxy)-2-methyl-propionic acid allyl ester in 80 ml of tetrahydrofuran and 20 ml of n-propanol, and the reaction mixture is hydrogenated for 7 hours at a temperature of 140°C and under a hydrogen pressure of 20 bar. After cooling to room temperature and rendering the stirred autoclave inert with nitrogen, the catalyst is filtered off. 117.3 g of a solution containing 7.26 % 2-(2-chloro-5-amino-benzoyloxy)-2-mefhyl-propionic acid allyl ester (yield 94.6 % of theory) are obtained.

1H-NMR (CDC1 ₃ , 250 MHz): 1.62 ppm (s, 6H); 3.65 ppm (s, 2H); 4.6 ppm (d, 2H); 5.2 ppm (q, 2H); 5.85 ppm (m, 1H); 6.65 ppm (m, 1H); 7.0 ppm (m, 1H); 7.1 ppm (m, 1H).

The compounds of formula Via listed in Table 1 below can be prepared analogously.

In Tables 1 to 10 below, Y ₃ is the group X _r Q-C(O)-X-R ₂ or -X-R ₂ , wherein X _l5 Q, X and R ₂ are as defined for formula I.

Table 1 : Compounds of formula Via:

Table 1

Comp. R ₃ RΛ phys. No. data

1.1 Cl Cl -OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

22

1.2 Cl F -OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂ n _D 1.5132 ;

^! H-NMR (see Table lb)

<rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂

-OC(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂ n _D ³³ 1.5435

-OC(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂

-OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

-OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

<rac>OCH(CH ₃ )COO-CH ₂ -CH=CH ₂

<S>-OCH(CH ₃ )-COO-CH ₂ -CH=CH ₂

<rac>OCH(CH ₃ )-COO-CH ₂ -CH=CH ₂

<S>-OC(CH ₃ ) ₂ -COO-CH(CH ₃ )-CH=CH ₂ rac-O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )-CH=CH ₂

<S>-O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

<S>-O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

<rac>O-C(CH ₃ ) ₂ -COOCH(CH ₃ )CH=CH ₂

0 *^COOCH ₂ -CH=CH ₂ <rac>OCH(C ₂ H ₅ )COOCH ₂ CH=CH ₂ -OC(C ₂ H ₅ ) ₂ COOCH ₂ CH=CH ₂ <R>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

Comp. R ₃ R. phys. No. data

-O-C(CH ₃ ) ₂ CONH-CH ₂ -CH=CH ₂

-O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂

<S>-O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂

<R>O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂ <S>-O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂

1.25 Cl H -0*^- CONH-CH ₂ -CH=CH ₂

(S)- O -^CONH-CH(CH ₃ )-CH=CH ₂

-NHCH ₂ CH=CH ₂

-O-C(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ 1H-NMR (see

Table lb)

-O-CH ₂ CONHCH ₂ CH=CH ₂

-O-CH(CH ₃ )CH=CH ₂

<S>-O-CH(CH ₃ )CH=CH ₂

<S>O-C(CH ₃ ) ₂ -COO-CH(C ₂ H ₅ )-CH=CH ₂

<S>-O-C(CH ₃ ) ₂ -COOCH(C ₂ H ₅ )-CH=CH ₂

-O-C(C ₂ H ₅ ) ₂ -COO-CH ₂ -CH=CH ₂

-O-CH(C ₄ H ₉ -n)-COO-CH ₂ -CH=CH ₂

-OC(C ₄ H ₉ -n) ₂ -COOCH ₂ -CH=CH ₂

-OC(C ₃ H ₇ -n) ₂ -COOCH ₂ -CH=CH ₂

-OCCH(C ₃ H ₇ -i)-COOCH ₂ -CH=CH ₂

-O-C(CH ₃ ) ₂ -CONH-CH(C ₄ H ₉ -n)-CH=CH ₂

<S>O-C(CH ₃ ) ₂ -CONH-CH(C ₃ H ₇ -i)-CH=CH ₂

-O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ -CH=CH ₂

-O-CH(CH ₃ )-CH ₂ -COO-CH ₂ -CH=CH ₂

<S>-O-CH(CH ₃ )-CH ₂ COO-CH ₂ CH=CH ₂

<S>-O-CH(CH ₃ )-CH ₂ CONH-CH ₂ CH=CH ₂

-O-CH(C ₂ H ₅ )-CH ₂ COOCH ₂ -CH=CH ₂

-OCH(C ₄ H ₉ -s)-CH ₂ -COOCH ₂ CH=CH ₂

-O-CH ₂ -CH(C ₄ H ₉ -n)-COOCH ₂ -CH=CH ₂ -O-CH ₂ -C(CH ₃ ) ₂ -COO-CH ₂ CH=CH ₂

Comp. R ₃ RΛ phys.

No. data

1.49 Cl H <S>-O-CH ₂ -C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

1.50 Cl H -0*^^ CONHCH ₂ -CH=CH ₂

1.51 Cl H -0^ COOCH ₂ CH=CH ₂

1.54 Cl Cl -OCH ₂ CH=CH ₂ 1.55 Cl F -OCH ₂ CH=CH ₂

22

1.56 CN -OCH ₂ CH=CH ₂ n 1.5621

D

1.57 Br Br -OCH(CH ₃ )CH=CH ₂ 1.58 J H -OC(CH ₃ ) ₂ CH=CH ₂ 1.59 OCF, H -OC(CH ₃ ) ₂ CH=CH ₂ 1.60 OCHF ₂ F -OC(CH ₃ ) ₂ CH=CH ₂ 1.61 Cl H -OC(CH ₃ ) ₂ CH=CH ₂ 1.62 Cl H -OCH(CH ₃ )CH=CH ₂ MS: m/e 225 1.63 Cl H -OCH ₂ -CH=CH ₂ 'H-NMR (see Table lb) 1.64 CN H -OC(CH ₃ ) ₂ CH=CH ₂ 1.65 Cl H (S-)-OCH(CH ₃ )CH=CH ₂

1.66 Cl - 0 -^- CH=CH ₂

-NH-CH ₂ -CH=CH ₂ 'H-NMR (see Table lb) -NH-CH(CH ₃ )CH=CH ₂

Comp. R ₃ RΛ phys.

No. data

1.71 Cl H -NH-CH(C ₄ H ₉ -n)CH=CH ₂

1.72 Cl F -NH-CH ₂ CH=CH ₂

1.75 Cl H -° ^C ( ^CH 3)2 -^COOCH ₂ CH=CH ₂

1.76 CN F -OCH(CH ₃ ) -^COOCH(CH ₃ )CH=CH ₂

1.77 Cl Cl ^"0CH 2 -^-COOCH ₂ CH=CH ₂

1.78 Cl Br " ^0CH 2 ^■ ^- CONHCH ₂ CH=CH ₂

1.79 OCF ₃ F -OCH(CH ₃ ) -VL _C ONHCH ₂ CH=CH ₂

1.80 OCHF ₂ H -° ^CH 2 *^-COOCH ₂ CH=CH ₂

1.81 Cl Cl ^"OCH 2 COOCH ₂ CH=CH ₂

1.82 OCHF ₂ H (S)-O^COOCH(CH ₃ )CH=CH ₂

1.83 OCF ₃ H (S)-O^COOCH(CH ₃ )CH=CH ₂

1.84 CN H (rac)-0*^-COOCH(CH ₃ )CH=CH ₂

1.85 J J -O -^COOCH ₂ CH=CH ₂

1.86 J F -OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

Comp. R ₃ R_, phys. No. data

Table lb: NMR data for compounds from Table 1:

Comp. No. ^! H-NMR (300 MHz, CDC1 ₃ )

1.2 7.30 ppm (m, IH), 7.08 ppm (m, IH), 6.64 ppm (m, IH),

5.94 ppm (m, IH), 5.31 ppm (m, 2H), 4.70 ppm (d, 2H), 4.17 ppm (broad signal, 2H), 1.71 ppm (s, 6H).

1.28 7.15 ppm (m, IH), 7.05 ppm (m, IH), 6.77 ppm (m, 2H),

5.84 ppm (m, IH), 5.17 ppm (m, 2H), 4.14 ppm (m, 2H), 3.92 ppm (m, 2H), 1.81 ppm (s, 6H).

1.55 7.35 ppm (d, IH), 7.08 ppm (d, IH), 6.01 ppm (m, IH),

5.35 ppm (q, 2H), 4.77 ppm (d, 2H), 3.86 ppm (s, 2H).

1.63 7.16 ppm (d, IH), 7.10 ppm (d, IH), 6.69 ppm (dxd, IH),

6.01 ppm (m, IH), 5.84 ppm (q, 2H), 4.80 ppm (d, 2H), 3.87 ppm (broad signal, 2H).

1.69 7.10 ppm (d, IH), 6.96 ppm (d, IH), 6.62 ppm (dxd, IH),

6.49 ppm (broad signal, IH), 6.02 ppm (m, IH), 5.25 ppm (q, 2H), 4.08 ppm (m, 2H), 3.81 ppm (broad signal, 2H).

Example P5: Preparation of 2-chloro-5-(4,4,4-trifluoro-3-oxo-butyrylamino)-benzoic acid 1-allyloxy-l -methyl-ethyl ester (Compound No. 2.14): Variant A (without the addition of a base):

At a maximum temperature of 25°C, a solution prepared from 0.065 mol of trifluoroacetyl chloride and ketene (the preparation is described, for example, in GB-931 689) of 4,4,4-trifluoroacetoacetyl chloride in 13 ml of toluene is added dropwise to 15.5 g (0.05 mol) of 5-amino-2-chloro-benzoic acid 1-allyloxycarbonyl-l -methyl-ethyl ester in 130 ml of toluene. After stirring for 4 hours at room temperature, a further small amount of trifluoroacetoacetyl chloride is added and the reaction mixture is heated at a tempera¬ ture of 70°C (for approx. 90 minutes) until the aniline used has reacted completely. The reaction mixture is then concentrated by evaporation and the residue is purified by chromatography on silica gel (hexane/ethyl acetate 7:3). 13.6 g (63 % of theory) of 2-chloro-5-(4,4,4-rrifluoro-3-oxo-butyrylamino)-benzoic acid 1 -ally loxy- 1 -methyl-ethyl ester (Compound No. 2.14) are obtained in the form of crystals having a melting point of from 75 to 77°C. After recrystallisation from diethyl ether/petroleum ether the melting point is from 80 to 82°C.

Variant B (with the addition of a base):

669 mg of trifluoroacetoacetyl chloride in 0.8 ml of toluene are added dropwise with stirring and cooling with ice-water at a temperature of from 10 to 15°C to a suspension of 0.73 g (2.45 mmol) of 5-amino-2-chloro-benzoic acid 1-allyloxycarbonyl-l -methyl-ethyl ester and 0.38 g of solid sodium carbonate in 8 ml of toluene. After stirring for 15 hours at room temperature, the reaction mixture is filtered over silica gel and the filtrate is concentrated by evaporation and dried. 1 g (quantitative yield based on the aniline used) of 2-chloro-5-(4,4,4-trifluoro-3-oxo-butyrylamino)-benzoic acid 1-allyloxy- 1 -methyl-ethyl ester (Compound No. 2.14) is obtained in the form of a viscous resin. After trituration with n-hexane and diethyl ether 2-chloro-5-(4,4,4-trifluoro-3-oxo-butyrylamino)-benzoic acid 1-allyloxy-l-methyl-ethyl ester (Compound No. 2.14) is obtained in the form of a white solid having a melting point of from 76 to 78°C.

Example P6: Preparation of 2-chloro-5-(4,4,4-trifluoro-3-oxo-butyroylamino)-benzoic acid 1-allyloxy-l-methyl-ethyl ester (Compound No. 2.14): In an apparatus having a distillation column (height 20 cm), 7.44 g (0.025 mol) of 5-amino-2-chloro-benzoic acid 1-allyloxycarbonyl-l -methyl-ethyl ester are added to a solution of 4.86 g of 1,1,1-trifluoroacetoacetic acid ethyl ester in 450 ml of toluene and the reaction mixture is heated for 3 hours with continuous removal of the ethanol formed

during the reaction in the form of an ethanol/toluene azeotrope (total of 250 ml) until reaction is complete. The reaction mixture is then concentrated by evaporation and the residue is treated with a small amount of a diethyl ether/n-hexane mixture. After filtering off and drying the white precipitate obtained 9.7 g (89 % of theory) of 2-chloro- 5-(4,4,4-trifluoro-3-oxo-butyroylamino)-benzoic acid 1-allyloxy-l -methyl-ethyl ester (Compound No. 2.14) having a melting point of from 76 to 78°C are obtained.

Cyclohexane can be used analogously instead of toluene.

Example P7: Preparation of 2-chloro- 5-(4,4,4-trifluoro-3-amino-but-2-enoylamino)- benzoic acid l-allyloxycarbonyl-l -methyl-ethyl ester (Compound No. 3.14): A mixture of 2.7 g of 2-chloro-5-(4,4,4-trifluoro-3-oxo-butyroylamino)-benzoic acid 1-allyloxy-l -methyl-ethyl ester and 4.78 g of anhydrous ammonium acetate is heated to melting at a bath temperature of from 115 to 130°C until the reaction is complete. After 3 hours the reaction mixture is cooled, and ethyl acetate is added at a temperature of 50°C, excess ammonium acetate is filtered off, and the precipitate is washed. The resulting filtrate is filtered over silica gel and concentrated by evaporation and the resulting solid is dried in vacuo. 2.63 g (97.4 % of theory) of 2-chloro-5-(4,4,4-trifluoro-3-amino-but-2-en- oylamino)-benzoic acid l-allyloxycarbonyl-l -methyl-ethyl ester (Compound No. 3.14) having a melting point of from 94 to 98°C are obtained.

Similar results are obtained when, for example, 3 equivalents of ammonium acetate in an aprotic solvent, for example ethyl acetate, are used.

Example P8: Preparation of 2-chloro-5-(3-oxo-4,4,4-trichloro-butyrovIamino)-benzoic acid (l-allyloxycarbonyl-l-methyD-ethyl ester (Compound No. 4.12): In an apparatus having a distillation column (height 20 cm), 25.9 g (0.087 mol) of 5-amino-2-chloro-benzoic acid l-allyloxycarbonyl-l -methyl-ethyl ester are dissolved in 650 ml of toluene, 21.3 g (0.095 mol) of 1,1,1-trichloroacetoacetic acid ethyl ester are added thereto and the reaction mixture is heated. The ethanol formed during the reaction is distilled off in the form of an azeotrope while the total amount of liquid is kept constant by the addition of toluene. When the reaction has ceased, the reaction mixture is concentrated by evaporation in vacuo and the resulting residue is crystallised by the addition of small amounts of hexane and diethyl ether. The crystals are then filtered, washed with hexane and dried. 33.3 g (79 % of theory) of 2-chloro-5-(3-oxo-4,4,4-trichloro-butyroylamino)- benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester (Compound No. 4.12) having a

melting point of from 107 to 108°C are obtained.

Example P9: Preparation of 2-chloro-5-(4,4,4-trichloro-3-amino-but-2-enoylamino)- benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester (Compound No. 5.12): In a three-necked flask with an A4 molecular sieve in the reflux attachment, 212 g (2.75 mol) of ammonium acetate are suspended in 500 ml of ethyl acetate and freed from water by heating under reflux. Then, when the reaction mixture has cooled, 26.9 g (0.055 mol) of 2-chloro-5-(4,4,4-trichloro-3-hydroxy-but-2-enoylamino)-benz oic acid l-allyloxycarbonyl-l -methyl-ethyl ester are added thereto. After heating again and slowly distilling off the condensate that has formed over a distillation column (duration approx. 5 hours), the reaction mixture is concentrated by evaporation and the residue is purified by chromatography on silica gel (hexane/ethyl acetate 9 : 1). 10.4 g (39 % of theory) of 2-chloro-5-(4,4,4-trichloro-3-amino-but-2-enoylamino)-benzoi c acid (l-allyloxycarbonyl- l-methyl)-ethyl ester (Compound No. 5.12) having a melting point of from 99 to 100°C and 9.2 g (56 %) of 5-amino-2-chloro-benzoic acid l-allyloxycarbonyl-l -methyl-ethyl ester are obtained.

Example P10: Preparation of 2-chloro-5-(3,6-dihvdro-2,6-dioxo-4-trifluoromethyl- l(2H)-pyrimidinyl)-benzoic acid (l-allyloxycarbonyl-l-methyD-ethyl ester (Compound No. 6.28):

A solution of 1.43 ml of phosgene (20 %) in toluene is added dropwise at a temperature of 40°C to a solution of 1.08 g (2.5 mmol) of 2-chloro-5-(4,4,4-trifluoro-3-amino-but-2- enoylamino)-benzoic acid 1-allyloxycarbonyl-l-methyl-ethyl ester, 0.5 ml of pyridine and 25 mg of 4-dimethylaminopyridine in 40 ml of toluene and the reaction mixture is then stirred for approx. 4.5 hours at the same temperature until the reaction is complete. After cooling and the addition of a small amount of ethyl acetate, the reaction mixture is washed with ice-water. The organic phase is then dried over sodium sulfate, filtered and concen¬ trated by evaporation. 1.1 g (95.6 % of theory) of 2-chloro-5-(3,6-dihydro-2,6-dioxo-4-tri- fluoromethyl-l(2H)-pyrimidinyl)-benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester (Compound No. 6.28) is obtained in the form of a white solid having a melting point of from 53 to 56°C in sufficient purity for further reaction; after chromatographic purification on silica gel (hexane/ethyl acetate 8:2) the melting point is from 57 to 59°C.

Example PI 1 : Preparation of 2-chloro-5-(3,6-dihvdro-2,6-dioxo-4-trichloromethyl- l(2H)-pyrimidinyl)-benzoic acid (l-allyloxycarbonyl-l-methyD-ethyl ester

(Compound No. 8.12):

A solution of 9.3 g (19.2 mmol) of 2-chloro-5-(4,4,4-trichloro-3-amino-but-2-enoyl- amino)-benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester, 3.9 ml of pyridine

(48 mmol) and 0.23 g of 4-dimethylaminopyridine in toluene is heated to a temperature of

40°C and then a solution of 11 ml (21.2 mmol) of phosgene (20%) in toluene is added dropwise thereto. After stirring for 15 hours at a temperature of 40°C, cooling and filtering on a small amount of silica gel, the reaction mixture is concentrated by evaporation. After purification of the residue by chromatography on silica gel (hexane/ethyl acetate 7:3), 3.7 g (38 % of theory) of 2-chloro-5-(3,6-dihydro-2,6-dioxo-4-trichloromethyl-

1 (2H)-pyrimidinyl)-benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester (Compound

No. 8.12) are obtained in the form of a colourless resin.

¹ H-NMR (CDC1 ₃ , 100 MHz): 1.7 ppm (s, 6H), 4.68 ppm (d, 2H), 5.19-5.37 ppm (m, 2H),

5.82-5.99 ppm (m, IH), 6.51 ppm (s, IH), 7.35 ppm (dd, IH), 7.60 ppm (d, IH), 7.87 ppm

(d, IH), 8.63 ppm (s, broad).

Example P12: Preparation of 2-chloro-5-(3,6-dihvdro-2,6-dioxo-3-methyI-4-trichloro- methyl-l(2H)-pyrimidinyl)-benzoic acid (l-alryloxycarbonyl-l-methyP-ethyl ester (Compound No. 9.12):

0.65 ml of methyl iodide is added to a suspension of 2.6 g (5 mmol) of 2-chloro-5-(3,6-di- hydro-2,6-dioxo-4-trichloromethyl- 1 (2H)-pyrimidinyl)-benzoic acid ( 1 -allyloxycarbonyl- l-methyl)-ethyl ester, 66 mg of 18-crown-6 ether and 1 g (10 mmol) of potassium hydrogen carbonate in 125 ml of acetone and the reaction mixture is then stirred for 15 hours at a temperature of 35°C. The reaction mixture is then concentrated by evaporation, the residue is taken up in ethyl acetate and washed with water, and the resulting extract is dried over sodium sulfate. After concentration by evaporation and purification by chromatography on silica gel (hexane/ethyl acetate 7 : 3), 2-chloro- 5-(3,6-dihydro-2,6-dioxo-3-methyl-4-trichloromethyl-l(2H)-py rimidinyl)-benzoic acid (l-allyloxycarbonyl-l-methyl)-ethyl ester (Compound No. 9.12) is obtained in the form of a colourless resin.

•H-NMR (CDC1 ₃ , 100 MHz): 1.7 ppm (s, 6H), 3.82 ppm (s, 3H), 4.65 ppm (d, 2H), 5.19-5.38 ppm (m, 2H), 5.82-5.98 ppm (m, IH), 7.35 ppm (dd, IH), 7.58 ppm (d, IH), 7.76 ppm (d, IH).

The compounds listed in the Tables below can be prepared analogously:

Table 2:

Compounds of formula IVa

Comp. R ₃ R. Phys. data No.

^z COOCH ₂ CH=CH ₂ <rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ O-C(C ₃ H ₇ -n) ₂ COOCH ₂ -CH=CH ₂ O-C(C ₄ H ₉ )COOCH ₂ -CH=CH ₂ <rac>O-CH(C ₄ H ₉ )COOCH ₂ -CH=CH ₂ O-C(C ₂ H ₅ ) ₂ COOCH ₂ -CH=CH ₂ <S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂ <S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

O — ^— COOCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

2.29 Cl <s> o ΣL CONHCH(CH ₃ )CH=CH ₂

2.30 Cl H <R> ₀ _Λ _ CONHCH(CH ₃ )CH=CH ₂

^{2 1 C1 H <S>} 0 — ^- CONHCH(CH ₃ )CH=CH ₂

2.32 Cl H o-SZ ■ CONHCH ₂ CH=CH ₂ <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <R>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <rac>OCH(CH ₃ )CONHCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OCH(C ₃ H ₇ -i)COOCH ₂ CH=CH ₂ OCH ₂ CH(C ₄ H ₉ -n)-COOCH ₂ CH=CH ₂ OCH ₂ CH(n-C ₄ H ₉ )-COOCH ₂ CH=CH ₂ OCH ₂ C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ <S>OCH ₂ C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ O-CH(C ₂ H ₅ )-CH ₂ COOCH ₂ CH=CH ₂ <S>O-CH(CH ₃ )CH ₂ CONHCH ₂ CH=CH ₂

Comp. R, R. Phys. data

No.

2.45 Cl H <S>O-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

2.46 Cl H <rac.)O-CH(CH ₃ )-CH ₂ COOCH=CH ₂

2.47 Cl H <rac>O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ CH=CH ₂

2.48 Cl H <S>O-C(CH ₃ ) ₂ CONHCH(C ₃ H ₇ -i)-CH=CH ₂

2.49 Cl F <rac>O-C(CH ₃ ) ₂ CONHCH(C ₄ H ₉ -n)CH=CH ₂

2.50 Cl H /

O -^-— CONHCH ₂ CH=CH ₂

2.51 Cl H O —^^— COOCH ₂ CH=CH ₂

2.55 Cl H 0-CH(CH ₃ ) COOCH ₂ CH=CH ₂

² -56 Cl H 0-C(CH ₃ ) ₂ — ^— COOCH ₂ CH=CH ₂

2.57 CN F 0-CH(CH ₃ ) ^"^ COOCH(CH ₃ )CH=CH ₂

2.58 Cl Cl 0-CH ₂ — ^^— COOCH ₂ CH=CH ₂

2.59 Cl Br 0-CH ₂ ^- ^X CONH-CH ₂ -CH=CH ₂

2.60 OCF ₃ F ₀ -CH(CH ₃ )

Comp. R ₃ R ₄ Y ₃ Phys. data

No.

2.61 OCHF ₂ H 0-CH _? — ^x— ^■ COOCH ₂ CH=CH ₂

2.62 Cl Cl OCHc COOCH ₂ CH=CH ₂ 2.63 Cl Cl OCH ₂ CH=CH ₂ 2.64 Cl F OCH ₂ CH=CH ₂ 2.65 CN F OCH ₂ CH=CH ₂ 2.66 Br Br OCH(CH ₃ ) ₂ CH=CH ₂ 2.67 I H OC(CH ₃ ) ₂ CH=CH ₂ 2.68 OCF ₃ H OC(CH ₃ ) ₂ CH=CH ₂

.70 OCHF ₂ F OC(CH ₃ ) ₂ CH=CH ₂ 2.71 Cl H OC(CH ₃ ) ₂ CH=CH ₂ 2.72 Cl H OCH(CH ₃ )CH=CH ₂ 2.73 Cl H OCH ₂ CH=CH ₂ 2.74 CN H OC(CH ₃ ) ₂ CH=CH ₂ 2.75 Cl H <S>O-CH(CH ₃ )CH=CH ₂

2.76 Cl 0—^- CH=CH ₂

2.77 OCF ₃ H <rac>OCH(CH ₃ )COOCH ₂ CH=CH ₂ 2.78 OCF ₃ F <S>OCH(CH ₃ )COOCH ₂ CH=CH ₂ 2.79 OCF ₃ F <rac>OCH(CH ₃ )COOCH ₂ CH=CH ₂

2.80 OCF ₃ H <S>o-SZ COOCH(CH ₃ )CH=CH ₂

2.81 OCHF ₂ H <S> ₀ ΣL COOCH(CH ₃ )CH=CH ₂

2.82 I I NHCH ₂ CH=CH ₂ 2.83 OCF ₃ H <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ 2.84 Cl H <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ 2.85 Cl F <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

R_t Y-, Phys. data

<rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ <rac> o -V_ COOCH(CH ₃ )CH=CH ₂

<trans> ^ COOCH ₂ CH=CH ₂

Comp. R ₃ RΛ Phys. data

No.

OCH ₂ -COOCH ₂ C≡CH

<rac>O-CH(CH ₃ )COOCH ₂ C≡CH

OCH ₂ C≡CH

OCH ₂ G≡CH

OCH ₂ C≡C-CH ₃

OCH(CH ₃ )C=CH

OC(CH ₃ ) ₂ -C≡CH

OC(CH ₃ ) ₂ -G=CH SCH ₂ C≡CH <rac>S-CH(CH ₃ )C≡CH N(CH ₃ )-CH ₂ CH=CH ₂ <rac>N(CH ₃ )-CH(CH ₃ )C≡CH <rac>O-CH(CH ₃ )-CH ₂ COOCH ₂ C≡CH <rac>S-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂ <rac>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂ <S>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂ <S>SCH(CH ₃ )CH ₂ COOCH=CH ₂ SC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ SCH ₂ CONHCH ₂ CH=CH ₂

Table 3:

Compounds of formula Illb

Comp. R ₃ R ₄ Y ₃ Phys. data

No.

3.18 Cl H _o ^Z COOCH ₂ CH=CH ₂

<rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

O-C(C ₃ H ₇ -n) ₂ COOCH ₂ -CH=CH ₂

O-C(C ₄ H ₉ )COOCH ₂ -CH=CH ₂

<rac>O-CH(C ₄ H ₉ )COOCH ₂ -CH=CH ₂

O-C(C ₂ H ₅ ) ₂ COOCH ₂ -CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH _{2 o} ^Z COOCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

³ - ^{29 C1 F <S>} 0 -^- CONHCH(CH ₃ )CH=CH ₂

3.31 Cl H <S> ₀ X7 CONHCH(CH ₃ )CH=CH ₂

3.32 Cl H O — ^— CONHCH ₂ CH=CH ₂

3.33 Cl F <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

3.34 Cl H <R>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

3.35 Cl H <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

3.36 Cl H <rac>OCH(CH ₃ )CONHCH ₂ CH=CH ₂

3.37 Br H OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

3.38 CN F OCH(C ₃ H ₇ -i)COOCH ₂ CH=CH ₂

3.39 ⁴ C1 H OCH ₂ CH(C ₄ H ₉ -n)-COOCH ₂ CH=CH ₂

3.40 Br H OCH ₂ CH(n-C ₄ H ₉ )-COOCH ₂ CH=CH ₂

3.41 Cl F OCH ₂ C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

3.42 Cl H <S>OCH ₂ C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

3.43 Cl F O-CH(C ₂ H ₅ )-CH ₂ COOCH ₂ CH=CH ₂

3.44 Cl H <S>O-CH(CH ₃ )CH ₂ CONHCH ₂ CH=CH ₂

Comp. R, R, Phys. data No.

<S>O-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

<rac.)O-CH(CH ₃ )-CH ₂ COOCH=CH ₂

<rac>O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ CH=CH ₂

<S>O-C(CH ₃ ) ₂ CONHCH(C ₃ H ₇ -i)-CH=CH ₂ <rac>O-C(CH ₃ ) ₂ CONHCH(C ₄ H ₉ -n)CH=CH ₂

3.51 Cl H O —**^ — COOCH ₂ CH=CH ₂

³ - ⁵ 6 Cl H 0-C(CH ₃ ) ₂ - - COOCH ₂ CH=CH ₂

3.57 CN F 0-CH(CH ₃ ) —^-^— COOCH(CH ₃ )CH=CH ₂

3.58 Cl Cl 0-CH ₂ — -^ ^y X— COOCH ₂ CH=CH ₂

3.59 Cl Br 0-CH ₂ *— -^- — CONH-CH ₂ -CH=CH ₂

CONHCH ₂ CH=CH ₂

Comp. R ₃ R ₄ Y ₃ Phys. data

No.

3.61 OCHF ₂ HH 00--CCHH ₂₂ - ^^^x — COOCH ₂ CH=CH ₂

3.63 Cl Cl OCH ₂ CH=CH ₂

3.64 Cl F OCH ₂ CH=CH ₂

3.65 CN F OCH ₂ CH=CH ₂

3.66 Br Br OCH(CH ₃ ) ₂ CH=CH ₂

3.67 I H OC(CH ₃ ) ₂ CH=CH ₂

3.68 OCF ₃ H OC(CH ₃ ) ₂ CH=CH ₂

3.70 OCHF ₂ F OC(CH ₃ ) ₂ CH=CH ₂

3.71 Cl H OC(CH ₃ ) ₂ CH=CH ₂

3.72 Cl H OCH(CH ₃ )CH=CH ₂

3.73 Cl H OCH ₂ CH=CH ₂

3.74 CN H OC(CH ₃ ) ₂ CH=CH ₂

3.75 Cl H <S>O-CH(CH ₃ )CH=CH ₂

3-76 Cl F ₀ -5Z_- CH=CH ₂

3.77 OCF ₃ H <rac>OCH(CH ₃ )COOCH ₂ CH=CH ₂

3.78 OCF ₃ F <S>OCH(CH ₃ )COOCH ₂ CH=CH ₂

3.79 OCF ₃ F <rac>OCH(CH ₃ )COOCH ₂ CH=CH ₂

3.80 OCF ₃ H <S> o -^- COOCH(CH ₃ )CH=CH ₂

3.81 OCHF ₂ H <S> o-SZ cOOCH(CH ₃ )CH=CH ₂

3.82 I I NHCH ₂ CH=CH ₂

3.83 OCF ₃ H <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

3.84 Cl H <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

3.85 Cl F <S>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

Comp. R, R_* Ύ. Phys. data

No.

3.86 CN F <rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

3.87 CN H <rac> o--V_ cθOCH(CH ₃ )CH=CH ₂

3.88 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

3.89 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

3.90 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡C-CH ₃

3.91 Cl H -OC(CH ₃ ) ₂ COSCH ₂ C≡CH

3.92 Cl H -OC(C ₂ H ₅ ) ₂ COSCH ₂ C≡CH

3.93 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

3.94 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡C-C ₂ H ₅

3.95 Cl F <rac>OCH(CH ₃ )COOCH ₂ C≡CH

3.96 Cl F <S>OCH(CH ₃ )COOCH ₂ C≡CH

3.97 Cl F <rac>OCH(CH ₃ )COOCH(CH ₃ )C≡CH

3.98 Br H <rac>OCH(C ₂ H ₅ )COOCH ₂ C=C-CH ₃

3.99 CN F OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

3.100 OCF ₃ H OC(CH ₃ ) ₂ -COOCH ₂ C=CH

3.101 CH ₃ F OC(CH ₃ ) ₂ COOCH ₂ C=CH

3.102 Cl H OC(CH ₃ ) ₂ CONH-CH ₂ C=CH

3.103 Cl H OC(CH ₃ ) ₂ CON(CH ₃ )-CH ₂ C≡CH

3.104 Cl F <rac>OC(CH ₃ ) ₂ -CON(CH ₃ )-CH(CH ₃ )C≡CH

3.105 Cl F OC(CH ₃ ) ₂ -COS-CH ₂ CH=CH ₂

3.106 Cl H OC(CH ₃ ) ₂ -COSCH ₂ C=CH

3.107 Cl H SC(CH ₃ ) ₂ -COOCH ₂ C≡CH

3.108 CH ₃ H SC(CH ₃ ) ₂ -COSCH ₂ C≡CH

3.109 Cl H <rac>SCH(CH ₃ )-CH=CH ₂

3.110 Cl H SCH ₂ -CH=CH ₂

3.11 1 cl H -O- CH ₂ — ^- CONH- CH ₂ C≡ CH

3.1 12 CN F OCH ₂ -COOCH ₂ C≡CH

3.113 Cl F <rac>O-CH(CH ₃ )COOCH ₂ C≡CH

3.1 14 Cl F OCH ₂ C≡CH

3.1 15 Cl H OCH ₂ C≡CH

Comp. R ₃ R ₄ Y ₃ Phys. data

No.

3.116 CN H OCH ₂ C≡C-CH ₃

3.117 CH ₃ H OCH(CH ₃ )C≡CH

3.118 Cl H OC(CH ₃ ) ₂ -C≡CH

3.120 Cl F OC(CH ₃ ) ₂ -C≡CH

3.121 Cl H SCH ₂ C≡CH

3.122 Cl H <rac>S-CH(CH ₃ )C≡CH

3.123 Cl H N(CH ₃ )-CH ₂ CH=CH ₂

3.124 Cl F <rac>N(CH ₃ )-CH(CH ₃ )C≡CH

3.125 Cl H <rac>O-CH(CH ₃ )-CH ₂ COOCH ₂ C≡CH

3.126 Cl H <rac>S-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

3.127 Cl H <rac>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂

3.128 Cl H <S>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂

3.129 Cl H <S>SCH(CH ₃ )CH ₂ COOCH=CH ₂

3.130 Cl H SC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

3.131 Cl H SC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

3.132 Cl H SCH ₂ CONHCH ₂ CH=CH ₂

Table 4

Compounds of formula IVb:

Phys. data

m.p. 107-108°C

4.15 Cl H o O -A^Z— COOCH ₂ CH=CH ₂

Comp. R ₃ R. Phys. data

No.

Table 5:

Compounds of formula Hie:

Phys. data

m.p. 99-100°C

Comp. R ₃ RΛ Phys. data No.

5.16 Cl F O-^^— COOCH ₂ CH=CH ₂

5.18 Cl H <rac>OCH(C ₄ H ₉ ) _n COOCH ₂ CH=CH ₂

5.19 ci F 0-CH ₂ -- — COOCH ₂ CH=CH ₂

5.20 Cl F <S> 0-CH(CH ₃ ) COOCH ₂ CH=CH ₂

5.21 Cl H <S>O-CH(CH ₃ )CH ₂ COOCH=CH ₂

5.22 Cl H <S>OCH(CH ₃ )CH ₂ CO-NHCH=CH ₂

5.23 Cl H OCH ₂ C=CH

5.24 Cl F NHCH ₂ C≡CH

5.25 Cl H OC(CH ₃ ) ₂ C≡CH

5.26 Cl F OC(CH ₃ ) ₂ C=C-CH ₃

5.27 Cl H OC(CH ₃ ) ₂ COOCH ₂ C≡CH

5.28 CN F OC(CH ₃ ) ₂ COSCH ₂ C=CH

5.29 Cl H OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ C≡CH

5.30 CH ₃ F O-SZ cOOCH C≡ CH

5.31 Cl H <rac>OCH(CH ₃ )-COOCH ₂ C=CH

5.32 Cl H SC(CH ₃ ) ₂ -COOCH ₂ C=CH

5.33 Cl F SCH ₂ CH=CH ₂

5.34 Cl H <rac>SCH(CH ₃ )CH=CH ₂

5.35 Cl F SCH ₂ C≡CH

5.36 Cl H <rac>SCH(CH ₃ )C=CH

5.37 Cl H <S>SCH(CH ₃ )C≡CH

5.38 Cl H SC(CH ₃ ) ₂ C≡CH

5.39 Cl H SCH ₂ C≡CH

Table 6:

Compounds of formula lib

Phys. data

Comp. R. RΛ Phys. data No.

6.19 Cl H <rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.20 OCF ₃ F O-C(C ₃ H ₇ -n) ₂ COOCH ₂ -CH=CH ₂

6.21 Cl Cl O-C(C ₄ H ₉ -n) ₂ COOCH ₂ -CH=CH ₂

6.22 Cl F <rac>O-CH(C ₄ H ₉ )COOCH ₂ -CH=CH ₂

6.23 Br Br O-C(C ₂ H ₅ ) ₂ COOCH ₂ -CH=CH ₂

6.24 Cl H <S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

6.25 Cl H <S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

6.26 I I O -^— COOCH ₂ CH=CH ₂

6.27 I F OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

6.28 Cl H OC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ m.p. 57-59°C

6.29 Cl F <S> 0-^- CONHCH(CH ₃ )CH=CH ₂

6.30 Cl H <R> 0 -^- CONHCH(CH ₃ )CH=CH ₂

6.31 Cl H <S> 0 -^- CONHCH(CH ₃ )CH=CH ₂

O — -— CONHCH ₂ CH=CH ₂ <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <R>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <S>OCH(CH ₃ )CONHCH ₂ CH=CH ₂ <rac>OCH(CH ₃ )CONHCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OCH(C ₃ H ₇ -i)COOCH ₂ CH=CH ₂ OCH ₂ CH(C ₄ H ₉ -n)-COOCH ₂ CH=CH ₂ OCH ₂ CH(n-C ₄ H ₉ )-COOCH ₂ CH=CH ₂ OCH ₂ C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ <S>OCH ₂ C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ O-CH(C ₂ H ₅ )-CH ₂ COOCH ₂ CH=CH ₂ <S>O-CH(CH ₃ )CH ₂ CONHCH ₂ CH=CH ₂ <S>O-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

Comp. R ₃ R-t -Y, Phys. data No.

<rac>O-CH(CH ₃ )-CH ₂ COOCH=CH ₂ <rac>O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ CH=CH ₂ <S>O-C(CH ₃ ) ₂ CONHCH(C ₃ H ₇ -i)-CH=CH ₂ <rac>O-C(CH ₃ ) ₂ CONHCH(C ₄ H ₉ -n)CH=CH ₂

6.52 Cl OOCH(CH ₃ )CH=CH ₂

6.53 Cl Cl CONCH(C ₂ H ₅ )CH=CH ₂

6.54 Cl O-CHo COOCH ₂ CH=CH ₂

6.55 Cl H 0-CH(CH ₃ ) COOCH ₂ CH=CH ₂

6.56 Cl H 0-C(CH ₃ ) ₂ - v^— COOCH ₂ CH=CH ₂

6.58 Cl Cl 0-CH ₂ • COOCH ₂ CH=CH ₂

6.59 Cl Br 0-CH ₂ CONH-CH ₂ -CH=CH ₂

6.60 OCF ₃ F 0-CH(CH ₃ )

Comp. Ri RΛ Phys. data

No.

6.70 Cl Cl O-C(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂

6.71 OCF ₃ H <S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.72 OCF ₃ H <rac>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.73 Cl H <S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.74 Cl F <S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.75 CN F <rac>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

6.76 Cl H 0 -^ COOCH ₂ CH=CH ₂

6.77 CN H <rac.> 0-^- COOCH(CH ₃ )CH=CH ₂

6.78 OCF ₃ H <S> 0 -^ COOCH(CH ₃ )CH=CH ₂

Comp. R ₃ R, Phys. data No.

6.79 OCHF ₂ H <S> O -^- COOCH(CH ₃ )CH=CH ₂

6.80 I H O-C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

6.81 OCHF ₂ F OC(CH ₃ ) ₂ CH=CH ₂

6.82 Cl H <rac>OCH(CH ₃ )CH=CH ₂

6.83 Cl H OC(CH ₃ ) ₂ CH=CH ₂

6.84 Cl H OCH ₂ CH=CH ₂

6.85 CN H OC(CH ₃ ) ₂ CH=CH ₂

6.86 Cl F θ -^- CH=CH ₂

6.87 Cl H <rac>NHCH(C ₄ H ₉ -n)CH=CH ₂

6.88 Cl H <rac>NHCH(CH ₃ )CH=CH ₂

6.90 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

6.91 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

6.92 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C=C-CH ₃

6.93 Cl H -OC(CH ₃ ) ₂ COSCH ₂ C≡CH

6.94 Cl H -OC(C ₂ H ₅ ) ₂ COSCH ₂ C≡CH

6.95 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

6.96 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡C-C ₂ H ₅

6.97 Cl F <rac>OCH(CH ₃ )COOCH ₂ C=CH

6.98 Cl F <S>OCH(CH ₃ )COOCH ₂ C=CH

6.99 Cl F <rac>OCH(CH ₃ )COOCH(CH ₃ )C≡CH

6.100 Br H <rac>OCH(C ₂ H ₅ )COOCH ₂ C≡C-CH ₃

6.101 CN F OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

6.102 OCF ₃ H OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

6.103 CH ₃ F OC(CH ₃ ) ₂ COOCH ₂ C≡CH

6.104 Cl H OC(CH ₃ ) ₂ CONH-CH ₂ C≡CH

6.105 Cl H OC(CH ₃ ) ₂ CON(CH ₃ )-CH ₂ C≡CH

6.106 Cl F <rac>OC(CH ₃ ) ₂ -CON(CH ₃ )-CH(CH ₃ )C≡CH

6.107 Cl F OC(CH ₃ ) ₂ -COS-CH ₂ CH=CH ₂

Phys. data

Table 7:

Compounds of formula la

-Y ₃ Phys. data

<rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ m.p. 122-124°C

O-C(C ₃ H ₇ -n) ₂ COOCH ₂ -CH=CH ₂

O-C(C ₄ H ₉ -n) ₂ COOCH ₂ -CH=CH ₂

<rac>O-CH(C ₄ H ₉ )COOCH ₂ -CH=CH ₂

O-C(C ₂ H ₅ ) ₂ COOCH ₂ -CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(C ₂ H ₅ )CH=CH ₂

O -^— COOCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ m.p. 95°C

7.30 Cl H <R> 0-^- CONHCH(CH ₃ )CH=CH ₂

7.31 Cl H <S> 0 -^ C0NHCH(CH ₃ )CH=CH ₂

O -^— CONHCH ₂ CH=CH ₂ <S>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <R>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

<S>OCH(CH ₃ )CONHCH ₂ CH=CH ₂ m.p. 148-149°C

<rac>OCH(CH ₃ )CONHCH ₂ CH=CH ₂ m.p. 122-125°C

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ OCH(C ₃ H ₇ -i)COOCH ₂ CH=CH ₂ OCH ₂ CH(C ₄ H ₉ -n)-COOCH ₂ CH=CH ₂ OCH ₂ CH(n-C ₄ H ₉ )-COOCH ₂ CH=CH ₂ OCH ₂ C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ <S>OCH ₂ C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ O-CH(C ₂ H ₅ )-CH ₂ COOCH ₂ CH=CH ₂ <S>O-CH(CH ₃ )CH ₂ CONHCH ₂ CH=CH ₂ <S>O-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

Comp. R, RA Phys. data No.

<rac>O-CH(CH ₃ )-CH ₂ COOCH=CH ₂ <rac>O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ CH=CH ₂ <S>O-C(CH ₃ ) ₂ CONHCH(C ₃ H ₇ -i)-CH=CH ₂ <rac>O-C(CH ₃ ) ₂ CONHCH(C ₄ H ₉ -n)CH=CH ₂

7.51 Cl H £2 COOCH ₂ CH=CH ₂

7.52 Cl OOCH(CH ₃ )CH=CH ₂

7.53 Cl Cl o CONCH(C ₂ H ₅ )CH=CH ₂

7.54 Cl O-CH, COOCH ₂ CH=CH ₂

7.56 Cl H 0-C(CH ₃ ) ₂ -z— COOCH ₂ CH=CH ₂

7.57 CN F 0-CH( COOCH(CH ₃ )CH=CH ₂

7.58 Cl Cl 0-CH CH ₂ CH=CH ₂

7.59 Cl Br 0-CH ₂ CONH-CH ₂ -CH=CH ₂

7.60 OCF ₃ F 0-CH(CH ₃ )

Comp. R. R, Phys. data No.

O CH, COOCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂

OCH(CH ₃ )CH=CH ₂

OC(CH ₃ ) ₂ CH=CH ₂

OC(CH ₃ ) ₂ CH=CH ₂ O-C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ resin; ^! H-NMR (300 MHz, CDC1 ₃ : 7.85 ppm (d, IH), 7.38 ppm (d, IH), 6.36 ppm (s, IH), 5.89 ppm (m, IH), 5.34 ppm (q, 2H), 4.62 ppm (m, 2H), 3.57 ppm (s, 3H), 1.70 ppm (s, 6H).

O-C(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

<rac>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

<S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ m.p. 120-122°C

<S>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂ <rac>O-C(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

7.76 Cl H COOCH ₂ CH=CH ₂ resin

7.78 OCFα H <S> _o ^Z COOCH(CH ₃ )CH=CH ₂

Comp. R, RA -Yi Phys. data

No.

7.79 OCHF ₂ H <S> .o O -^*Z— COOCH(CH ₃ )CH=CH ₂

7.80 I H O-C(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

7.81 OCHF ₂ F OC(CH ₃ ) ₂ CH=CH ₂

7.82 Cl H <rac>OCH(CH ₃ )CH=CH ₂

7.83 Cl H OC(CH ₃ ) ₂ CH=CH ₂

7.84 Cl H OCH ₂ CH=CH ₂

7.85 CN H OC(CH ₃ ) ₂ CH=CH ₂

7.86 Cl F 0 -^- CH=CH ₂

7.87 Cl H <rac>NHCH(C ₄ H ₉ -n)CH=CH ₂

7.88 Cl H <rac>NHCH(CH ₃ )CH=CH ₂

7.90 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

7.91 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C=CH

7.92 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡C-CH ₃

7.93 Cl H -OC(CH ₃ ) ₂ COSCH ₂ C≡CH

7.94 Cl H -OC(C ₂ H ₅ ) ₂ COSCH ₂ C=CH

7.95 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

7.96 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡C-C ₂ H ₅

7.97 Cl F <rac>OCH(CH ₃ )COOCH ₂ C≡CH

7.98 Cl F <S>OCH(CH ₃ )COOCH ₂ C≡CH

7.99 Cl F <rac>OCH(CH ₃ )COOCH(CH ₃ )C≡CH

7.100 Br H <rac>OCH(C ₂ H ₅ )COOCH ₂ C≡C-CH ₃

7.101 CN F OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

7.102 4OCF ₃ H OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

7.103 CH ₃ F OC(CH ₃ ) ₂ COOCH ₂ C≡CH

7.104 Cl H OC(CH ₃ ) ₂ CONH-CH ₂ C≡CH

7.105 Cl H OC(CH ₃ ) ₂ CON(CH ₃ )-CH ₂ C=CH

7.106 Cl F <rac>OC(CH ₃ ) ₂ -CON(CH ₃ )-CH(CH ₃ )C≡CH

7.107 Cl F OC(CH ₃ ) ₂ -COS-CH ₂ CH=CH ₂

Comp. R. R. Phys. data No.

OC(CH ₃ ) ₂ -COSCH ₂ C≡CH SC(CH ₃ ) ₂ -COOCH ₂ C≡CH SC(CH ₃ ) ₂ -COSCH ₂ C≡CH <rac>SCH(CH ₃ )-CH=CH ₂ S CH ₂ -CH ⁼ CH ₂

-O- CH ₂ -^- CONH- CH ₂ C≡ CH

OCH ₂ -COOCH ₂ C≡CH

<rac>O-CH(CH ₃ )COOCH ₂ C≡CH

OCH ₂ C≡CH

OCH ₂ C≡CH

OCH ₂ C≡C-CH ₃

OCH(CH ₃ )G≡CH

OC(CH ₃ ) ₂ -C=CH

OC(CH ₃ ) ₂ -C≡CH SCH ₂ C=CH <rac>S-CH(CH ₃ )C≡CH N(CH ₃ )-CH ₂ CH=CH ₂ <rac>N(CH ₃ )-CH(CH ₃ )C≡CH <rac>O-CH(CH ₃ )-CH ₂ COOCH ₂ C≡CH <rac>S-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂ amorphous <rac>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂ oil

<S>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂ <S>SCH(CH ₃ )CH ₂ COOCH=CH ₂ SC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂ oil

SC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂ resin SCH ₂ CONHCH ₂ CH=CH ₂ m.p. 137-138°C

Table 8:

Compounds of formula

Phys. data

resin ( ^! H-NMR)

Comp. R. RA -Y, Phys. data

No.

g 17 ci H O -^— CONHCH ₂ CH=CH ₂

8.18 Cl H <rac>OCH(C ₄ H ₉ ) _n COOCH ₂ CH=CH ₂

8 19 ci F 0-CH ₂ - - COOCH ₂ CH=CH ₂

Table 9:

Compounds of formula

Phys. data

resm

Comp. R, R. -Y, Phys. data

No.

Example PI 3: Preparation of 2-(2-chloro-4-fluoro-5-amino-benzoyloxy-2-methyl- propionic acid allyl ester (Compound No. 10.2)

0.033 g of 4-dimethylaminopyridine is added to a solution, prepared at room temperature, of 130 ml of 2-hydroxy-2-methylpropionic acid allyl ester in 42.2 ml of pyridine and 300 ml of toluene. With stirring, 20.1 g of 2-chloro-4-fluoro-5-nitrobenzoyl chloride are added thereto and the reaction mixture is heated at 45-55°C for 7 hours. The reaction mixture is then cooled, ice-water is added thereto and extraction is carried out with toluene. The extracts are washed in succession with dilute hydrochloric acid (2N) and aqueous sodium hydrogen carbonate solution and water, dried over sodium sulfate and concentrated by evaporation. Filtration on silica gel with hexane/ethyl acetate 7:3 as eluant yields the desired compound in the form of an oil.

¹ H-NMR (300 MHz, CDC1 ₃ ): 7.73 ppm (d, IH), 7.40 ppm (d, IH), 5.90-6.04 ppm (m, IH), 5.28-5.41 ppm (m, 2H), 4.75 ppm (d, 2H), 1.68 ppm (s, 6H).

The desired compound No. 10.2 is also obtained without adding 4-dimethylaminopyridine, for example by reaction in pyridine as solvent at temperatures of from 0° to 100°C, preferably from 35° to 60°C.

Table 10:

Compounds of formula Vila

Comp. R, RA Phys. data

No.

10.1 Cl Cl OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

10.2 Cl F OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂ oil; (Example P13)

10.3 Cl H <rac>OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂

10.4 Cl H OC(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂ m.p. 44-45°C

10.5 CN H OC(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂

10.6 Br H OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

10.7 Br F OC(CH ₃ ) ₂ COO-CH ₂ -CH=CH ₂

10.8 OCF ₃ F <rac>OCH(CH ₃ )COO-CH ₂ -CH=CH ₂

10.9 OCF ₃ F <S>OCH(CH ₃ )-COO-CH ₂ -CH=CH ₂

10.10 OCF ₃ H <rac>OCH(CH ₃ )-COO-CH ₂ -CH=CH ₂

10.11 OCF ₃ H <S>OC(CH ₃ ) ₂ -COO-CH(CH ₃ )-CH=CH ₂

10.12 OCF ₃ H <rac>O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )-CH=CH ₂

10.13 Cl H <S>O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

10.14 Cl F <S>O-C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

10.15 CN F <rac>O-C(CH ₃ ) ₂ -COOCH(CH ₃ )CH=CH ₂

10.16 Cl H ΣZ COOCH ₂ -CH=CH ₂

o- Z • COOCH(CH ₃ )-CH=CH ₂ <rac>OCH(C ₂ H ₅ )COOCH ₂ CH=CH ₂ O(C ₂ H ₅ )COOCH ₂ CH=CH ₂ O-C(CH ₃ ) ₂ CONH-CH ₂ -CH=CH ₂

Phys. data

O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂ <S>O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂ <R>O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂ <S>O-CH(CH ₃ )CONH-CH ₂ -CH=CH ₂

10.25 Cl H O-^— CONH-CH ₂ -CH=CH ₂

10.26 Cl H <S> 0-^- CONH-CH(CH ₃ )-CH=CH ₂

10.27 Cl H <R> 0-^ CONH-CH(CH ₃ )-CH=CH ₂

<S> O -^— CONH-CH(CH ₃ )-CH=CH ₂

OC(CH ₃ ) ₂ COOCH ₂ -CH=CH ₂

O-C(CH ₃ ) ₂ -CONH-CH ₂ -CH=CH ₂

O —^— COO-CH ₂ -CH=CH ₂

<S>O-C(CH ₃ ) ₂ -COO-CH(C ₂ H ₅ )-CH=CH ₂

<S>O-C(CH ₃ ) ₂ -COOCH(C ₂ H ₅ )-CH=CH ₂

<R>OC(CH ₃ ) ₂ COOCH(CH ₃ )CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

O-CH ₂ -CONHCH ₂ CH=CH ₂

<S>OCH(CH ₃ )CH=CH ₂

<R>OCH(CH ₃ )CH=CH ₂

O-C(CH ₃ ) ₂ -CONH-CH(C ₄ H ₉ -n)-CH=CH ₂

<S>O-C(CH ₃ ) ₂ -CONH-CH(C ₃ H ₇ -i)-CH=CH ₂

O-CH(CH ₃ )-CH(CH ₃ )COOCH ₂ -CH=CH ₂

O-CH(CH ₃ )-CH ₂ -COO-CH ₂ -CH=CH ₂

<S>O-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

<S>O-CH(CH ₃ )-CH ₂ CONH-CH ₂ CH=CH ₂

OCH(C ₂ H ₅ )-CH ₂ COOCH ₂ -CH=CH ₂ OCH(C ₄ H ₉ -s)-CH ₂ -COOCH ₂ CH=CH ₂

-Y-, Phys. data

O-CH ₂ -CH(C ₄ H ₉ -n)-COOCH ₂ -CH=CH ₂

O-CH ₂ -C(CH ₃ ) ₂ -COO-CH ₂ -CH=CH ₂ <S>O-CH ₂ -C(CH ₃ ) ₂ -COO-CH(CH ₃ )CH=CH ₂

10.51 Cl H O— ^^- COOCH ₂ CH=CH ₂

10.52 Cl F O COOCH(CH ₃ )CH=CH ₂

10.54 Cl Cl OCH ₂ CH=CH ₂

10.55 Cl F OCH ₂ CH=CH ₂

10.56 CN F OCH ₂ CH=CH ₂

10.57 Br Br OCH(CH ₃ )CH=CH ₂

10.58 I H OC(CH ₃ ) ₂ CH=CH ₂

10.59 OCF ₃ H OC(CH ₃ ) ₂ CH=CH ₂

10.60 OCHF ₂ F OC(CH ₃ ) ₂ CH=CH ₂

10.61 Cl H OC(CH ₃ ) ₂ CH=CH ₂

10.62 Cl H OCH(CH ₃ )CH=CH ₂

10.63 Cl H OCH ₂ -CH=CH ₂

10.64 CN H OC(CH ₃ ) ₂ CH=CH ₂

10.65 JC1 H <S>-OCH(CH ₃ )CH=CH ₂

10.66 Cl F 0 --^- CH=CH ₂

10.67 Cl H O — ^- CH=CH ₂

Comp. R. R, Phys. data No.

NH-CH ₂ -CH=CH ₂ NH-C(CH ₃ )CH=CH ₂ NH-CH(C ₄ H ₉ -n)CH=CH ₂ NH-CH ₂ CH=CH ₂

10.75 Cl H OC(CH ₃ ) ₂ — ^ UZ— COOCH ₂ CH=CH ₂

10.76 CN OCH(CH ₃ ) ^^ COOCH(CH ₃ )CH=CH ₂

10.77 Cl Cl OCH, COOCH ₂ CH=CH ₂

10.78 Cl Br OCH ₂ ^^ CONHCH ₂ CH=CH ₂

10.80 OCHFn H OCH ₂ COOCH ₂ CH=CH ₂

10.81 Cl Cl 0-CH ₂ COOCH ₂ CH=CH ₂

10.82 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C=CH

10.83 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

Comp. R, RA -Y, Phys. data

No.

10.84 Cl H -OC(CH ₃ ) ₂ COOCH ₂ C≡C-CH ₃

10.85 Cl H -OC(CH ₃ ) ₂ COSCH ₂ C≡CH

10.86 Cl H -OC(C ₂ H ₅ ) ₂ COSCH ₂ C≡CH

10.87 Cl F -OC(CH ₃ ) ₂ COOCH ₂ C≡CH

10.88 Cl F -OC(CH ₃ ) ₂ COOCH ₂ G≡C-C ₂ H ₅

10.89 Cl F <rac>OCH(CH ₃ )COOCH ₂ C≡CH

10.90 Cl F <S>OCH(CH ₃ )COOCH ₂ C≡CH

10.91 Cl F <rac>OCH(CH ₃ )COOCH(CH ₃ )C≡CH

10.92 Br H <rac>OCH(C ₂ H ₅ )COOCH ₂ OC-CH ₃

10.93 CN F OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

10.94 OCF ₃ H OC(CH ₃ ) ₂ -COOCH ₂ C≡CH

10.95 CH ₃ F OC(CH ₃ ) ₂ COOCH ₂ C≡CH

10.96 Cl H OC(CH ₃ ) ₂ CONH-CH ₂ C≡CH

10.97 Cl H OC(CH ₃ ) ₂ CON(CH ₃ )-CH ₂ C≡CH

10.98 Cl F <rac>OC(CH ₃ ) ₂ -CON(CH ₃ )-CH(CH ₃ )C=CH

10.99 Cl F OC(CH ₃ ) ₂ -COS-CH ₂ CH=CH ₂

10.100 Cl H OC(CH ₃ ) ₂ -COSCH ₂ C≡CH

10.101 Cl H SC(CH ₃ ) ₂ -COOCH ₂ C≡CH

10.102 CH ₃ H SC(CH ₃ ) ₂ -COSCH ₂ C≡CH

10.103 Cl H <rac>SCH(CH ₃ )-CH=CH ₂

10.104 Cl H SCH ₂ -CH=CH ₂

10.105 Cl H -O- CH ₂ -^- CONH- CH ₂ C≡ CH

10.106 CN F OCH ₂ -COOCH ₂ C≡CH

10.107 Cl F <rac>O-CH(CH ₃ )COOCH ₂ C≡CH

10.108 Cl F OCH ₂ C=CH

10.109 Cl H OCH ₂ C≡CH

10.110 CN H OCH ₂ C≡C-CH ₃

10.111 CH ₃ H OCH(CH ₃ )C≡CH

10.112 Cl H OC(CH ₃ ) ₂ -G≡CH

Comp. R ₃ RA Phys. data

No.

10.114 Cl F OC(CH ₃ ) ₂ -C≡CH

10.115 Cl H SCH ₂ C≡CH

10.116 Cl H <rac>S-CH(CH ₃ )C≡CH

10.117 Cl H N(CH ₃ )-CH ₂ CH=CH ₂

10.118 Cl F <rac>N(CH ₃ )-CH(CH ₃ )C≡CH

10.119 Cl H <rac>O-CH(CH ₃ )-CH ₂ COOCH ₂ C≡CH

10.120 Cl H <rac>S-CH(CH ₃ )-CH ₂ COOCH ₂ CH=CH ₂

10.121 Cl H <rac>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂

10.122 Cl H <S>SCH(CH ₃ )CONH-CH ₂ CH=CH ₂

10.123 Cl H <S>SCH(CH ₃ )CH ₂ COOCH=CH ₂

10.124 Cl H SC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

10.125 Cl H SC(CH ₃ ) ₂ COOCH ₂ CH=CH ₂

10.126 Cl H SCH ₂ CONHCH ₂ CH=CH ₂

Table 1 1

Compounds of formula XVΗ

Phys. data

Phys. data

11.32 Cl H 2

11.37 Cl H C(CH ₃ ) ₂ V

11.38 CN CH(CH ₃ )

11.39 Cl Cl -CH, σ

Comp. R, R -Q- Phys. data No.

11.43 Cl H -C(C ₂ H ₅ ) ₂ -

Table 12

Compounds of formula XVIII

Phys. data

Phys. data

12.32 Cl H Q

C(CH ₃ ) ₂ ^Z

CH(CH ₃ ) Ώ. -CH, .

Comp. R ₃ RA -Q- Phys. data

No.

12.43 Cl H -C(C ₂ H ₅ ) ₂ -

In Tables 13 to 18 below, Y ₀₃ is the group -Y-Q-C(O)-X-R ₂ or -X-R ₂ wherein Y is oxygen, sulfur or NR ₆ ; and Q, X, R and R are as defined for formula I.

Table 13

Compounds of formula VIb

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

<rac>OCH(CH ₃ )C≡CH

<S>OCH(CH ₃ )C≡CH

OCH ₂ C≡CH m.p. 60-62°C

OCH(CH ₃ )C=CH

<rac>SCH(CH ₃ )C≡CH

<S>SCH(CH ₃ )C=CH

<rac>SCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₄ H ₉ -n)CH=CH ₂

<rac>OCH(C ₄ H ₉ -n)C≡CH

<rac>OCH(C ₄ H ₉ -s)C≡CH-CH ₃

<S>OCH(C ₄ H ₉ -s)C=CH-C ₂ H ₅

<rac>OCH(C ₂ H ₅ )CH=CH ₂

<S>OCH(C ₂ H ₅ )CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₂ H ₅ )C=CH

<S>OCH(C ₂ H ₅ )C=CH

<rac>OCH(C ₂ H ₅ )C≡C-CH ₃

<rac>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

<S> OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(C ₂ H ₅ ) ₂ CONHCH ₂ CH-=CH ₂

<rac>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<S>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<rac>OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH-CH ₃

OC(CH ₃ ) ₂ CONHCH ₂ C≡CH

OC(CH ₃ ) ₂ CONHCH ₂ C≡C-CH ₃ OC(CH ₃ )CON(CH ₃ )CH ₂ CH=CH-C ₃ H ₇ -(i)

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

SC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂

SC(CH ₃ ) ₂ COSCH ₂ -CH=CH ₂

SC(CH ₃ ) ₂ COSCH(CH ₃ )-C≡CH

OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂

SC(CH ₃ ) ₂ CONHCH(CH ₃ )-CH=CH ₂

N(CH ₃ )CH ₂ CH=CH ₂

N(CH ₃ )CH ₂ CH=CH ₂

N(C ₂ H ₅ )CH ₂ CH=CH-CH ₃

N(CH ₃ )C≡CH ^'

N(C ₂ H ₅ )OC-CH ₃ N(CH ₃ )CH ₂ -CH=CH ₂

Table 14:

Compounds of formula IVc

Comp. No. R-. R_ι ^■ o ₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

<S>OCH(CH ₃ )C≡CH

OCH ₂ C=CH m.p. 105-106°C

OCH(CH ₃ )C≡CH

<rac>SCH(CH ₃ )C=CH

<S>SCH(CH ₃ )C≡CH

<rac>SCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₄ H ₉ -n)CH=CH ₂

<rac>OCH(C ₄ H ₉ -n)C≡CH

<rac>OCH(C ₄ H ₉ -s)C≡CH-CH ₃

<S>OCH(C ₄ H ₉ -s)C≡CH-C ₂ H ₅

<rac>OCH(C ₂ H ₅ )CH=CH ₂

<S>OCH(C ₂ H ₅ )CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₂ H ₅ )C=CH

<S>OCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₂ H ₅ )C=C-CH ₃

<rac>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

<S> OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(C ₂ H ₅ ) ₂ CONHCH ₂ CH=CH ₂

<rac>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<S>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<rac>OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH-CH ₃

OC(CH ₃ ) ₂ CONHCH ₂ C=CH

OC(CH ₃ ) ₂ CONHCH ₂ C≡C-CH ₃ OC(CH ₃ )CON(CH ₃ )CH ₂ CH=CH-C ₃ H ₇ -(i)

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

OC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ S CH ₂ CH=CH ₂ SCH ₂ CH ⁼ CH SCH ₂ CH=CH-CH ₃ SCH ₂ C=CH SCH ₂ C=CH SCH ₂ C≡CH S-CH ₂ OCH

<rac>S-CH(CH ₃ )-CH=CH ₂ <S>S-CH(C ₂ H ₅ )-CH=CH ₂ <S>S-CH(CH ₃ )C≡CH <rac>S-CH(CH ₃ )C=C-C ₂ H ₅ <S>S-CH(C ₃ H ₇ -n)CH=CH ₂ <rac>SCH(CH ₃ )COOCH ₂ CH=CH ₂ SCH ₂ COOCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COOCH ₂ C≡CH SC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COSCH ₂ -CH=CH ₂ SC(CH ₃ ) ₂ COSCH(CH ₃ )-C=CH OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂ SC(CH ₃ ) ₂ CONHCH(CH ₃ )-CH=CH ₂ N(CH ₃ )CH ₂ CH=CH ₂

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Table 15:

Compounds of formula Hid

Comp. No. R-i RA o ₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

<S>OCH(CH ₃ )C≡CH

OCH ₂ C≡CH m.p. 101-102°C

OCH(CH ₃ )C=CH

<rac>SCH(CH ₃ )C≡CH

<S>SCH(CH ₃ )C≡CH

<rac>SCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₄ H ₉ -n)CH=CH ₂

<rac>OCH(C ₄ H ₉ -n)C≡CH

<rac>OCH(C ₄ H ₉ -s)C≡CH-CH ₃

<S>OCH(C ₄ H ₉ -s)C≡CH-C ₂ H ₅

<rac>OCH(C ₂ H ₅ )CH=CH ₂

<S>OCH(C ₂ H ₅ )CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)C=CH

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₂ H ₅ )C≡CH

<S>OCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₂ H ₅ )C≡C-CH ₃

<rac>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

<S> OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(C ₂ H ₅ ) ₂ CONHCH ₂ CH=CH ₂

<rac>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<S>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<rac>OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH-CH ₃

OC(CH ₃ ) ₂ CONHCH ₂ C≡CH

OC(CH ₃ ) ₂ CONHCH ₂ C≡C-CH ₃ OC(CH ₃ )CON(CH ₃ )CH ₂ CH=CH-C ₃ H ₇ -(i)

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

OC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ SCH ₂ CH=CH ₂ SCH ₂ CH=CH ₂ SCH ₂ CH=CH-CH ₃ SCH ₂ C≡CH SCH ₂ C=CH SCH ₂ C=CH S-CH ₂ C≡CH

<rac>S-CH(CH ₃ )-CH=CH ₂ <S>S-CH(C ₂ H ₅ )-CH=CH ₂ <S>S-CH(CH ₃ )C=CH <rac>S-CH(CH ₃ )C≡C-C ₂ H ₅ <S>S-CH(C ₃ H ₇ -n)CH=CH ₂ <rac>SCH(CH ₃ )COOCH ₂ CH=CH ₂ SCH ₂ COOCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COOCH ₂ C≡CH SC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COSCH ₂ -CH=CH ₂ SC(CH ₃ ) ₂ COSCH(CH ₃ )-C≡CH OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂ SC(CH ₃ ) ₂ CONHCH(CH ₃ )-CH=CH ₂ N(CH ₃ )CH ₂ CH=CH ₂

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Table 16:

Compounds of formula lid

Comp. No. R-. R ₄ ^■ 03 Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

16.53 CN H o —*^— COOCH(CH ₃ )CH=CH ₂

OC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ SCH ₂ CH=CH ₂ SCH ₂ CH=CH ₂ SCH ₂ CH=CH-CH ₃ SCH ₂ C≡CH SCH ₂ C≡CH SCH ₂ C≡CH S-CH ₂ C≡CH

<rac>S-CH(CH ₃ )-CH=CH ₂ <S>S-CH(C ₂ H ₅ )-CH=CH ₂ <S>S-CH(CH ₃ )C≡CH <rac>S-CH(CH ₃ )C≡C-C ₂ H ₅ <S>S-CH(C ₃ H ₇ -n)CH=CH ₂ <rac>SCH(CH ₃ )COOCH ₂ CH=CH ₂ SCH ₂ COOCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COOCH ₂ C≡CH SC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂ SC(CH ₃ ) ₂ COSCH ₂ -CH=CH ₂ SC(CH ₃ ) ₂ COSCH(CH ₃ )-C≡CH OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂ SC(CH ₃ ) ₂ CONHCH(CH ₃ )-CH=CH ₂ N(CH ₃ )CH ₂ CH=CH ₂

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Table 17:

Compounds of formula Ic

Comp. No. R*** RA ^■ o ₃ Phys. data

OCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂ m.p.94-95°C

OCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂

OCH ₂ CH=CH ₂

O-C(CH ₃ ) ₂ -COOCH ₂ CH=CH ₂ m.p.85-86°C

O-C(CH ₃ ) ₂ -COOCH ₂ CH=CH ₂ m.p.85-87°C

O-C(C ₂ H ₅ ) ₂ COOCH ₂ CH=CH ₂

O-C(C ₂ H ₅ ) ₂ COOCH ₂ CH=CH ₂

<rac>OCH(CH ₃ )CH=CH ₂

<S>OCH(CH ₃ )CH=CH ₂

<S>OCH(CH ₃ )CH=CH ₂

<rac>OCH(CH ₃ )-C=CH

<S>OCH(CH ₃ )-C=CH

<rac>OCH(CH ₃ )C=CH m.p.124-125°C

<S>OCH(CH ₃ )C≡CH

<S>OCH(CH ₃ )C≡CH

<rac>OCH(CH ₃ )C≡CH <S>OCH(CH ₃ )C≡CH

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

OCH ₂ C=CH m.p. 120-121 °C

OCH(CH ₃ )C≡CH

<rac>SCH(CH ₃ )C≡CH

<S>SCH(CH ₃ )C≡CH

<rac>SCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₄ H ₉ -n)CH=CH ₂

<rac>OCH(C ₄ H ₉ -n)C=CH

<rac>OCH(C ₄ H ₉ -s)C≡CH-CH ₃

<S>OCH(C ₄ H ₉ -s)C=CH-C ₂ H ₅

<rac>OCH(C ₂ H ₅ )CH=CH ₂

<S>OCH(C ₂ H ₅ )CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₃ H ₇ -n)C=CH

<rac>OCH(C ₂ H ₅ )C≡CH

<S>OCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₂ H ₅ )G≡C-CH ₃

<rac>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

<S> OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(C ₂ H ₅ ) ₂ CONHCH ₂ CH=CH ₂

<rac>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<S>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<rac>OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH-CH ₃

OC(CH ₃ ) ₂ CONHCH ₂ C≡CH

OC(CH ₃ ) ₂ CONHCH ₂ C≡C-CH ₃ OC(CH ₃ )CON(CH ₃ )CH ₂ CH=CH-C ₃ H ₇ -(i)

17.51 Cl H CH= CH _C

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

17.80 CN H N(C ₂ H ₅ )C≡C-CH ₃

17.81 Br F N(CH ₃ )CH ₂ -CH=CH ₂

The nitro compounds of formula Vlld required for the preparation of the uracil derivatives of formula Ic mentioned in Table 17

wherein R ₂ , R ₃ , R ₄ , X, Y, Q, m and n are as defined for formula I, are known or can be obtained in accordance with known methods, either

a) by alkylating correspondingly substituted nitrophenols (Y is oxygen), nitrothiophenols (Y is sulfur) or nitroanilines (Y is NRg) of formula VIIc

wherein R ₃ , R ₄ and Y are as defined for formula I, with the compound of formula XXI

L ₄ -Q _m -[C(O)] _n -X-R ₂ (XXI),

wherein R ₂ , X, Q, m and n are as defined for formula I and L ₄ is a leaving group, or correspondingly substituted nitrobenzoyl derivatives of formula Vlld

wherein R ₃ , R ₄ and X are as defined for formula I, with the compound of formula XXII

R ₂ -L ₄ (xxπ),

wherein R ₂ is as defined for formula I and L ₄ is a leaving group, in an inert solvent, such as a chlorinated alkane, for example dichloromethane or chloroform, a ketone, for example acetone, a nitrile, for example acetonitrile, N,N-dimethylformamide, N-methyl- pyrrolidone or dimethyl sulf oxide, the reaction temperatures being from -10°C to 150°C, preferably from 0° to 100°C; as alkylating agents of formulae XXI and XXII there may be used, for example, corresponding halides or sulfonyloxy-substituted reagents, such as tosylates or mesylates, where appropriate with the addition of crown ethers or phase-transfer catalysts, or

b) the alkylation can be carried out analogously to Org. React. 42, 335 (1992), Editor D.L. Hughes, starting from the corresponding nitrophenols or nitrothiophenols of formula VIIc

wherein R ₃ and R ₄ are as defined for formula I and Y is oxygen or sulfur, by reaction with an alcohol or thiol of formula XX

R,-XH (XX),

wherein R ₂ is as defined for formula I and X is oxygen or sulfur, in the presence of a trialkylphosphine, such as tributylphosphine or triphenylphosphine, and a suitable azodicarboxylic acid dialkyl ester, such as azodicarboxylic acid diethyl ester, or an azodicarboxylic acid diamide, such as azodicarboxylic acid dimorpholide, in an inert solvent, such as dioxane or tetrahydrofuran, at temperatures of from -20° to 140°C, or by esterification of the nitrobenzoyl derivatives of formula Vlld

wherein R ₃ and R ₄ are as defined for formula I and X is oxygen or sulfur, with an alcohol or thiol of formula XX

R ₂ -XH (XX),

wherein R ₂ is as defined for formula I and X is oxygen or sulfur.

The reactants and reagents can be used in equimolar amounts or in excess (from 1 to 5 equivalents).

Example P14: Preparation of 2-(2-chloro-4-fluoro-5-nitrophenoxy)-2-methyl-propionic acid allyl ester (Compound No. 18.7)

A solution of 48.4 g of azodicarboxylic acid diethyl ester in 50 ml of dioxane is added dropwise at room temperature to a solution of 35 g of 2-chloro-4-fluoro-5-nitrophenol, 63 g triphenylphosphine and 25.9 g of 2-hydroxy-2-methyl-propionic acid ethyl ester in 300 ml of dioxane, the temperature of the solution rising to 39°C. When the reaction has subsided, the reaction mixture is heated and boiled under reflux until the phenol has disappeared (TLC monitoring). The reaction mixture is then concentrated by evaporation, the residue is taken up in a small amount of ethyl acetate and most of the triphenylphos¬ phine oxide formed is precipitated by the addition of hexane and is filtered off. The precipitate is washed thoroughly with hexane/ethyl acetate 1: 1 and the filtrate is washed with water, dried and concentrated by evaporation. The residue is filtered on silica gel using ethyl acetate/hexane 2:8 as eluant. After concentration by evaporation the desired compound is obtained in the form of a yellow-orange oil.

1H-NMR (300 MHz, CDC1 ₃ ): 7.73 ppm (d, IH), 7.40 ppm (d, IH), 5.90-6.04 ppm (m, IH), 5.28-5.41 ppm (m, 2H), 4.75 ppm (d, 2H), 1.68 ppm (s, 6H).

Table 18:

Compounds of formula Vlld

Comp. No. R-i R ^L o ₃ Phys. data

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

O-C(C ₂ H ₅ ) ₂ COOCH ₂ CH=CH ₂

O-C(C ₂ H ₅ ) ₂ COOCH ₂ CH=CH ₂

<rac>OCH(CH ₃ )CH=CH ₂

<S>OCH(CH ₃ )CH=CH ₂

<S>OCH(CH ₃ )CH=CH ₂

<rac>OCH(CH ₃ )-C≡CH

<S>OCH(CH ₃ )-C≡CH

<rac>OCH(CH ₃ )C=CH m.p. 89-90°C

<S>OCH(CH ₃ )OCH

<S>OCH(CH ₃ )C≡CH

<rac>OCH(CH ₃ )C=CH

<S>OCH(CH ₃ )C=CH

OCH ₂ C≡CH m.p. 89-90°C

OCH(CH ₃ )C≡CH

<rac>SCH(CH ₃ )C≡CH

<S>SCH(CH ₃ )C≡CH

<rac>SCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₄ H ₉ -n)CH=CH ₂

<rac>OCH(C ₄ H ₉ -n)C=CH

<rac>OCH(C ₄ H ₉ -s)C≡CH-CH ₃

<S>OCH(C ₄ H ₉ -s)C≡CH-C ₂ H ₅

<rac>OCH(C ₂ H ₅ )CH=CH ₂

<S>OCH(C ₂ H ₅ )CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -i)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)CH=CH ₂

<rac>OCH(C ₃ H ₇ -n)C≡CH

<rac>OCH(C ₃ H ₇ -n)C=CH

<rac>OCH(C ₂ H ₅ )C≡CH

<S>OCH(C ₂ H ₅ )C≡CH

<rac>OCH(C ₂ H ₅ )C≡C-CH ₃

<rac>OCH(CH ₃ )CONHCH ₂ -CH=CH ₂ <S> OCH(CH ₃ )CONHCH ₂ -CH=CH ₂

Comp. No. R ₃ R ₄ Y ₀₃ Phys. data

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CONHCH ₂ CH=CH ₂

OC(C ₂ H ₅ ) ₂ CONHCH ₂ CH=CH ₂

<rac>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<S>OC(CH ₃ ) ₂ CONH-CH(CH ₃ )CH=CH ₂

<rac>OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH ₂

OC(CH ₃ ) ₂ CON(CH ₃ )CH ₂ CH=CH-CH ₃

OC(CH ₃ ) ₂ CONHCH ₂ C≡CH

OC(CH ₃ ) ₂ CONHCH ₂ C≡C-CH ₃ OC(CH ₃ )CON(CH ₃ )CH ₂ CH=CH-C ₃ H ₇ -(i)

Comp. No. R? R Y o ₃ Phys. data

<S>S-CH(C ₃ H ₇ -n)CH=CH ₂

<rac>SCH(CH ₃ )COOCH ₂ CH=CH ₂

SCH ₂ COOCH ₂ CH=CH ₂

SC(CH ₃ ) ₂ COOCH ₂ C≡CH

SC(CH ₃ ) ₂ COSCH ₂ CH=CH ₂

SC(CH ₃ ) ₂ COSCH ₂ -CH=CH ₂

SC(CH ₃ ) ₂ COSCH(CH ₃ )-C=CH

OC(CH ₃ ) ₂ COOCH(CH ₃ )-CH=CH ₂

SC(CH ₃ ) ₂ CONHCH(CH ₃ )-CH=CH ₂

N(CH ₃ )CH ₂ CH=CH ₂

N(CH ₃ )CH ₂ CH=CH ₂

N(C ₂ H ₅ )CH ₂ CH=CH-CH ₃

N(CH ₃ )C=CH

N(C ₂ H ₅ )C≡C-CH ₃ N(CH ₃ )CH ₂ -CH=CH ₂

Table 19: Com ounds of formula Vic

Table 20: Com ounds of formula IVd

Table 21: Com ounds of formula Hie

Table 22: Compounds of formula He

Table 23: Compounds of formula Id

- llO-

Table : Com ounds of formula VId

Table 25: Compounds of formula IVe

Table 26: Com ounds of formula Illf

Table 27: Com ounds of formula Ilf

Table 28: Compounds of formula le

Comp. RA X, R 17 Phys. data No.

Η-NMR (300 MHz, CDC1 ₃ ): 7.06 ppm (d,lH), 6.93 ppm (d,lH), 6.38 ppm (s, IH), 4.69 ppm (s,2H), 4.64 ppm (s, 2H), 3.57 ppm (s, 3H), 2.29 ppm (m, IH).

28.5 F O CH ₂ C≡C-CH ₃

28.6 H O CH ₂ C≡CH

28.7 H O <rac>CH(CH ₃ )-C=CH

28.8 F O <rac>CH(CH ₃ )-OCH

28.9 F O <rac>CH(C ₂ H ₅ )-C=CH

28.10 F O <S>CH(CH ₃ )-C≡CH

28.11 ^ H O CH ₂ C=C-CH ₃

28.12 Cl O CH ₂ C≡CH

28.13 F S CH ₂ -C≡CH

28.14 H S CH ₂ C≡CH

28.15 F S CH ₂ CH=CH ₂

28.16 F S <rac>CH(CH ₃ )C≡C-CH ₃

Comp. R ₄ X ₃ R ₁₇ Phys. data

No.

28.17 F S <rac>CH(CH ₃ )C≡CH

Example P15: Preparation of a 5 % Pt-1 % Pb-SiO catalyst

5.0 g of a commercially available Pt-Siθ ₂ catalyst is suspended in 40 ml of deionised water and 2 ml of a lead acetate solution (0.091 g of Pb(Ac) ₂ «3H ₂ O, corresponding to 1 % Pb) are slowly added thereto at room temperature. The reaction mixture is stirred at room temperature for 10 minutes and then heated in a water bath to approximately 80°C. That temperature is maintained for approximately 40 minutes. The catalyst suspension is then left to stand overnight at room temperature. With stirring, 0.182 g of Na ₃ PO ₄ --12 H ₂ O in 25 ml of water is slowly added thereto. The suspension is stirred for a further 30 minutes and then the modified catalyst is filtered off. The catalyst that has been filtered off is washed with 0.5 litre of deionised water per gram of catalyst and dried overnight at 80°C in vacuo.

Example P16: Preparation of 2-(2-chloro-5-amino-benzoyloxy)-2-methylpropionic acid allyl ester

The hydrogenation is carried out analogously to Example P3, but with the catalyst prepared in accordance with Example P21. The allyl ester/propyl ester selectivity according to GC (unit area %) is 99 %.

The process according to the invention is distinguished by a surprisingly uniform reaction and thus - under mild conditions - leads to high yields of the desired end products. Special mention should be made of the very high yields in process steps a), b) and c). In process step b) in particular, the compounds of formula IV wherein R ₅ is a strongly electron- attracting substituent, such as CF ₃ or CC1 ₃ , would have been expected to react in different directions- resulting in a non-uniform reaction and low yields of the desired end products.