CA2038521A1 - Thieno[2,3-d]pyrimidine derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE: Thieno[2,3-d]-pyrimidine derivatives of thegeneral formula I

(I), where the substituents have the following meanings:
R1 is hydrogen, C1-C5-alkyl, C1-C3-chloroalkyl, C3-C6-cycloalkyl, phenyl or benzyl;
R2 is fluorine, chlorine, bromine, iodine, hydroxy, azido, cyano, thio-cyanato, mercapto, an organic radical not bonded via nitrogen or a radical NR5R6, where R5 and R6 are identical or different and each is hydrogen, amino or organic radicals, or form, together with the nitrogen atom, a heterocyclic radical of 3 to 8 ring atoms, with the proviso that R2 is not phenoxy-C2-C3-alkylamino;
R3 is chlorine, bromine, hydroxy or mercapto, with the proviso that R2 is not hydroxy when R3 is bromine, and that R3 is not hydroxy when R4 is alkoxycarbonyl or carboxy;
R4 is hydrogen, C1-C6-alkyl, C3-C6-mono-, di- or trihaloalkyl, phenyl, cyano, formyl, hydroxyiminomethyl, carboxy, alkoxycarbonyl, aminocarbonyl or a radical of the formula CH=X, where X is a radical, bonded via nitrogen, of a primary amine, or a radical, bonded via carbon, of a methylene-active compound, tautomers thereof, and salts and tautomers thereof tolerated by crop plants.
The compounds I are used as insecticides, growth regulators and herbicides.

Description

2 ~ 2 ~
O.Z. 0050/il488 Thieno r 2,3~dlpyrimidine derivativec The pre~ent invention relate~ to novel thieno-[2,3-d]pyrLmidine derivatives of the fonmula I

R2 (I) R 4~`N~R 1 where Rl is hydrogen, Cl-C5-alkyl, Cl-C3-chloroalkyl, C3-C6-cycloalkyl, phenyl or benzyl, R2 is fluorine, chlorine, bromine, iodine, hydroxyl, azido, cyano, thiocyanato, mercapto, an organic radical which is not bonded via nitrogen or a -:
radical NR5R8 where R5 and Re are each, independently of one another, hydrogen, amino or organic radicals, or they form, together with th~ nitrogen atom, a heterocyclio radical with 3 to 8 ring atoms, ~ith the proviso that R2 i~ not phenoxy-C2-C3-alkylamino, R3 is chlorine, bromine, hydroxyl or mercapto with the proviso that R2 i8 not hydroxyl when R3 is bromine, and R3 i8 not hydroxyl when R~ i~ alkoxycarbonyl or carboxyl, R4 i~ hydrogen, Cl-C~-alkyl, C3-C~-mono-, di- or trihalo-alkyl, phenyl, cyano, formyl, hydroxyiminomethyl, carboxyl, alkoxycarbonyl, aminocarbonyl or CH=X ~ -where X i8 a primary amina radical bonded via nitrogen or a rPdical of an active meth~lene com- -pound bonded via carbon, and the t~utomer~ of thQse thienor2,3-d]pyrimidine : -derivatives and the ~alts of thesQ thienot2,3-d~pyrimi-dine derivatL~es and their tautomer~ which are tolerated by crop plants.
The present invention al~o relates to the pre-paration of ths compounds 1, ~5 agent~ which contain com-pounds I as acti~e in~redi~nts for controlling unwanted plant~ and insect pe~t~ and for controlling the growth of .

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~ 2 ~ O ~ Z ~ 0050/4i4~38 crop plants, and to the use of the compounds I as herbi-cide~, pesticides or growth regulators.
DE-A 26 54 090 and US-A 4,196,207 describe thieno[2,3-d]pyrimidine derivatives which have fungici-dal, bactericidal, antiviral, growth-regulating and insecticidal or acaricidal proper~ies and which can also be halogen-~ubstituted in position 5. However, the only substituent~ in position 5 mentioned in the description and in the examples are hydrogen and methyl. The activi~y of these substances as herbicides, pesticides and grow~h-regula~ors is unsatisfactory. Thieno[2,3-d]pyrimidine derivatives which have hydroxyl in position 4 and bromine in position 5 are di~closed in the papers by M.M. Robba et al. (C.R. Acad. Sc. Paris 267, tl968), 697-700) and N.V. Raplina et al. (Pharm. Chem. Journal 21 (1~87), 126-129). Kaplina et al. te~ted these compound~ for antiviral activity. In addition, S. Kohra et al. (J. Het~ Chem., 2S, (1988), 959-968) deqcribe 4,5-dihydroxy-6-methoxy-carbonyl-2-phenylthieno[2l3-d]pyrimidine. A method for preparing 4-oxo-, 4-thio- or 4-iminothienoC2,3-d]pyrimi-dine~ i~ claimed in IN 151 496.
It is an ob~ect of the present invention to provide novel thieno~2,3-d]pyrimidine derivatives with herbicidal and improved growth-regulating and improved in~acticidal effect~.
We have found that thi~ ob~ect i~ achieved by the thienot2,3-d]pyr~midine derivati~e~ I defined in the first paragraph. ~he compound~ I have remarkable in~ecti-cidal, herbicidal and growth-regulatiny propertie~.
The compounds I where R2 and/or R3 i~ hydroxyl or mercapto form keto-enol tautomers. The invention relates to both forms of the compound3 and to the plant-compat-ible ~alt3, eg. of mineral acid~ ~uch a3 hydrochloric acid, sulfuric acid or pho~phoric acid, or of organic ~5 acid~ ~uch a~ acetic acid, malonic acid, ~uccinic acid or fumaric acid.
~he preferred compound~ I are those in which the ., . - , , . . . ,, . ~ . ~

: ' ' '. ,: ~ ~ ' : ' . :

- 3 - O.Z. 0050/41488 substituents have the following meanings:
Rl i~ hydrogen, Cl-C5-alkyl, Cl-C3-chloroalkyl, c3-C6-cycloalkyl, phenyl or benzyl, R2 is hydroxyl, fluorine, chlorine, bromin~, azido, S cyano, thiocyanato, Cl-Cz0-alkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy, Cl-C4-alkoxy-C2-C6-alkoxy, phenoxy-C2-C6-alkoxy,C3-Cl2-cycloalkoxy,hydroxy-C2-C6-alkoxy, chloro-C2-Ca-alkoxy, phenyloxy or benzyloxy, phenyl-ethoxy, amino-C2-C6-alkoxy, bis(Cl-C4-alkyl)amino-C2~ .
C6-alkoxy, hydroxy-Cl-C4-alkylamino-C2-C~-alkoxy, mercapto, Cl-Cl8-alkylthio, C3-C6-cycloalkylthio, C3-C8-alkenylthio, C3-C6-alkynylthio, hydroxy-C2-C6-alkylthio, bis-Cl-C3-alkylamino-C2-C6-alkylthio, carboxy-Cl-C4-alkylthio, Cl-~3-alkoxycarbonyl-Cl-C2-alkylthio, furylmethylthio, phenylthio or benzyl-thio, Cl-C4-alkoxycarbonylmethyl, carboxymethyl, bis(C1-C4-alkoxy~arbonyl)methyl, ~-C1-C4-alkoxy-carbony~ cyanomethyl~dicyanomethyl~bis(carboxy)-methyl, ~-cyano-~-phenylmethyl, pyrrolidino, piperi-dino, morpholino, hexamethyleneimino, N-methyl-piperazino, N-ethylpiperazino, imidazolyl, pyrazol-yl, triazolyl, tetrazolyl, thiomorpholino, hydra-zino, C1-C3-alkylhydrazino; bi~(Cl-C3-alkyl)hydrazino, phenylhydrazino, hydroxylamino, morpholinoamino, hexam~thyleneiminoamino, NR5R~ wher~ R5 and R6 are each, independently of one another, hydrogen, Cl-C20-alkyl, C3-C2~-alkenyl, C3-C~-alkynyl, C3-C12-cyclo-alkyl, C3-C3-cycloalkyl-Cl-C4-alkyl, hydroxy-C2-C6-alkyl, amino-C2-Cl2-alkyl, bis-CL-C4-alkylamino-C2-C~-alkyl, piperazino-C2-C~-alkyl, morpholino-C2-C4-alkyl, Cl-C3-alkoxy-Cl-C4-alkyl, phenoxy-C~-C6-alkyl, benzyl-oxy-C2-C~-alkyl, ~ydroxy-C2-C3-alkoxy-C2-C~-alkyl, hydroxy-C2-C4-alkylamino-C2-C4-alkyl;C2-C3-allcoxy-C2-C3-alkoxy-C2-C~-alkyl, phenoxy-C2-C4-alkoxy-Cz-C4-alkyl, bis-hydroxymethyl-C1-C3-alkyl, cyano-C2-C~0-alkyl,carboxy-C2-Cl~-alkyl,Cl-C3-alkoxy-C2-C3-alkoxy-C2-C3-alkoxy-C2-C3-al~yl, phenyl, phenyl-Cl-C~-alkyl, ' ' - . -. . . .. . . ~ - . : :.: , . . .. . .

~ 4 ~ O.Z. 0050/41488 C3-Cl2-cycloalkyl, pyridyl, furyl, thienyl, methyl-pyridyl, pyridylmethyl, furylmethyl, thienyl~ethyl or adamantyl, it being posxible, when R~ and/or R2 is or contain~
phenyl, for this phenyl to carry up to 3 identical or different substituents such as Cl-C4-alkyl, Cl-C4-alkoxy, halogen, nitro, amino, hydroxyl, hydroxy-Cl-C4-alkyl, cyano, carboxyl, aminocarbonyl, Cl-C4-alkoxycarbonyl, Cl-C4-acyloxy, C2-C6-acylamino, Cl-C4-alkylamino, Cl-C3-acyl, carboxy-Cl-C2-alkyl, di-C~-C4-alkylamino and trifluoromethyl and, in particular, fluorine, chlorine, bromine, iodine, methyl, ethyl, amino, hydroxyl, methoxy, ethoxy, acetylamino or acetyl, R3 i~ chlorine, bromine or hydroxyl, - R4 i~ hydrogen, methyl, C,-C2-mono- or dichloroalkyl, cyano, carboxyl, Cl-C4-alkoxycarbonyl, aminocarbonyl or CH=X where X i~ Cl-Ca~-alkylimino, phenylimino, carboxymethylene, ~-Cl-C4-alkyl-~-carboxymethylene, ~-phenyl-~-carboxymethylene, dicarboxymethylene, cyanomethylene, ~-C1-C~-alkyl-~-cyanomethylene, ~-phenyl-~-cyanomethylene,dicyanomethylene,formyl-methylene,~-C1-C4-alkyl-~-formylmethylene,~-phenyl-~-formylmethylene, diformylmethylene, Cl-C4-alkoxy-carbonylmethylene, ~-Cl-C4-alkyl-~-Cl-C4-alkoxy-carbonylmethylene, Cl-C4-dialkoxycarbonylmethylene, ~-cyano-~-Cl-C~-alkoxycarbonylmsthylene or ~-phenyl-Q -Cl-C~-alkOX~rCarbOn:ylmethyleIle .
: Compounds preferred for the purpose according to tha invention are listed in Table 1, the particularly pr~ferred compounds being 4,5-dichloro-6-methyl- ~No.
12), 4-n-propylamino-5-chloro- (~o. 144), 4-n-butylamino-5-chloro- (No. 146), 4-~ec-butylamino-S-chloro- (No.
147), 4-n-hexy1-5-chloro- (No. 154), 4-n-heptyl-5-chloro-(No. 155), 4-n-octyl-5-chloro- (No. 156), 4-n-nonyl-5-: chloro- (No. 157), 4-(2-methyl-6-heptyl) 5-chloro- (No.
168), 4-(1-ethoxy-3-propyl)-5-chloro- (No. 185), :~ .

, , ' ' ` ' . ' ' , . " , '' ~ ' , ., ` ' ' ' . ~ ~ ' . ' . . .

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- 5 - O.Z. 0050/41488 4-benzyl-5-chloro- (No. 275), 4-phenylethyl-5-chloro-(No. 282), 4-(3~propynyl)-5-chloro- (No. 293) and 4~(6-heptyl)-5-chlorothieno~2,3-d]pyrLmidine (No. 395).
The novel compound~ I can be prepared, for example, by reacting a thiophene derivative of the formula II
R3 ~ CNN2 (II) with a dialkylamide III
\~_N~T
Rl ~T2 (III) where Tl and T2 are each, independ~n~ly of one another, Cl-C4-alkyl or form, together with the nitrogen, a 5- to 7-membered saturated heterocycle, in the presence of from 2 to 20 mol of phosphoryl chloride or bromide per mol of II to give thieno[2,3-d]pyrimidine derivative~ of the formula Ia R4 ~ ` ~ R1 ~Ia) where R7 is chlorine or bromine, and replacing R7 in these where appropriate by other nucleophilic radicals R2 in a conventional manner.
Example~ of suitable dial~ylamides III are N,N-dim~thylformamide, N,N-dimethylacetamide, N,N-diethyl-form~id~,N,N-diethylacetamide,N,N-dimethylpropionamide and N,N-dimethylbenzamide.
It is important for the novel pro~ess te u~e an exce~s of pho~phoryl chloride or bromidH ba~ed on the thiophene derivativ~ II used. It may al~o be advantageous to carry out the reaction in the suitable pho~phoryl halide a8 solvent. From 2 to 6 mol of phosphoryl halide are preferably used per mol of II.
The molar ratio of thiophene derivative II to :
., ' ~
., ., ~ .

- 6 - O.Z. 0050~41488 N,N-dialkylamide III is normally from 1:1 to l:S.
The reaction is expediently carried out in an inert solvent such as chlorobenzene, nitrobenzene, methyl benzoate, methylene chloride, chlorobenzene, dichloro-benzene, trichlorobenzene, nitrobenzene, ethyl benzoate,chloroform, tetrachloromethane, one of the N,N-dialkyl-amides described above, trichloroethane, hexamethyl-phosphoric triamide (H~PT) or tetrachloroethylene.
Preferred solvents are phosphoryl chloride or bromide or one of the N,N-dialkylamide~ described above.
The reaction rate i~ sufficient above about 20C.
The specificity of the reaction decrea~e~ above 150C.
The reaction i~ preferably carried out at from 50 to 110 C .
The use of catalytic amount~ of a Lewis acid such a~ pota~sium chloride, sodium chloride, iron(III) chlor-ide, aluminum chloride, zinc chloride, tin chloride, antimony pentafluoride, boron trichloride, titanium tetrachloride, or of a ba~ic catalyst such a~ N,N-di-methylaniline or N,N-diethylaniline may increase the reaction rate and improve the yield.
The compounds of the formula I obtained in this way can ~e converted by conventional methods (The Chemis-try of Heterocyclic Compounds, ~The pyrimidines", ed.
D.J. Brown, J. Wiley & Sons, New York, London, Vol. 16, (lg62); Vol. 16, Suppl. 1, (1970); Vol. 16, Suppl. 2 (1985~ into the corre~ponding compound~ I by replacing the halogen in position 4 by other nucleophilic radicals R2, , Another proces~ for preparing the thienopyrimi- -dine derivative~ of the formula I a~ claimed in claim 1 comprise~ reacting compounds of the formula IV

R3 ~ ~ NH2 (IV) R~ `NH2 whese R3 and R~ hav~ the meaning indicate~ in claim 1, in , ~ . ~, . : . -, , .
:, . ~ . : :

2 ~
- 7 - O.Z. 005~41488 a conventional manner with an anhydride which containC at least one Rl-CO- radical, or with a carboxylic acid Rl-COOH, or with an adduct of a carboxylic acid Rl-COOH
and a Lewis acid, where R1 has the stated meaning, to give compounds of the formula Ib OH

R 4~`N~R 1 converting the latter with a phosphoryl halide into compound3 of the formula Ia as claimed in claLm 2, and replacing R~ in the latter where appropriate by other nucleophilic R2 radicals in a conventional manner.
It i~ expedient in certain cases to carry out the conversion of IV into Ib in two step~, ie. to isolate the intermediate compound~ of the formula VI

R3 ~ NH2 (VI) R4 ~ ~ ORl H

lS As a rule, the amount of anhydride or of adduct i~ from 100 to 500, preferably 100 to 300, mol ~ based on the compound~
The anhydrides which contain at lea~t one Rl-CO-radical can be derived from two carboxylic acid~ Rl-COOH
such as pivalic acid, propionic acid or acetic acid, or from one carboxylic acid Rl-COO~ and one oxo acid Quch a~
pho~phoric acid or ~ulfuric acid.
Preferred carboxylic acids R1-COOH are those with 1 to 4 carbon atom~, especially formic acid and acetic acid.
A180 suitable are adducts of a carboxylic acid R1-COOH and a ~ewi~ acid such as zinc chloride, boron trifluoride or titani~m tetrachloride.
The conversion of IV into Ib i8 advantagaou~ly c~rried out in inert ~olvent~ ~uch ~8 N,N-dialkylamides, of which N,N~dimathylformamide and dimethylaceta~ide are '" ~,' . . : , , , . ' . : . : ., ' :, , ' : .

~ ~3 ^~ J .~

- 8 - o.Z. 0050/414~8 particularly preferred, N-methylpyrrolidone, N,N-dimethylpropyleneurea or hexamethylphosphoric triamide at from -10 to 150C, preferably 20 to 120C, in particular 80 to 120C.
In the case where it is wished to isolate the intermediate compounds VI, the reaction is preferably carried out at from -10 to 80C.
As a rule, a base such a~ triethylamine, N-methylpyrrolidone or N,N-dLmethylaniline is added in an excess of from 1 to 10-fold, preferably 1 to 5-fold, ba~ed on the anhydride, the carboxylic acid or the carboxylic acid/Lewi~ acid adduct.
Addition of a water-removing reagent such as dicyclohexylcarbodiimide or of a Vilcmeier reagent may increa~e the reaction rate and improve the yield of Ib.
The hydroxyl in position 4 in compounds Ib can then be replaced by chlorine or bromine by conventional methods using for example phosphoryl chloride or bromide.
The chlorine or bromine in po~ition 4 can be replaced by.other nucleophilic radicals R2 by conventional method~.
The novel thieno~2,3-d]pyrimidine derivatives I
can also be obtained by reacting compounds II with orthoe~ters (V) as claimed in claim 4 to give the thio-phsne derLvativas VI and subsequent cyclization in the presence of a suitable nucleophile.
R3 ~ CN (R80)3C-R~ R3 ~ CN o-R8 R4 NH2 R4 ~ Rl ~II) (V) (vI) R2 ' Nuc . R 3 l~ R4S~Rl (I) - . .

The latter reaction se~uence i~ di~closed in .. . , - . . . . .
:: . . , , .......... : . . .
, ~ - :: , ~: - .

. :

- 9 - O.Z. 0050J41488 DE-A 26 54 090. The thiophene derivatives II and IV can be obtained by the methods described in EP-A1 0193 885.
To prepare plant-compatible salts, the thieno-[2~3-d]pyrimidine derivatives I can be reacted with the agents conventionally used for this purpose, such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid/ dodecylbenzenesulfonic acid, methyl bromide, dimethyl sulfate or diethyl sulfate at from 0 to 150C, preferably 20 to 120C.
The salt is expediently prepared in a solvent or diluent. Suitable examples are aliphatic hydrocarbons ~uch as n-pentane, n-hexane or petroleum ether, aromatic hydrocarbons such a~ benzene, toluene or xylenes, or ethers uch as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, or else ketones such as acetone, methyl ethyl ketone or methyl isopropyl ketone, and halohydrocarbons such a~ chlorobenzene, methylene chloride, ethylene chloride, chloroform and tetrachloro-ethylene. It is also pos~ible to use mixtures of these solvent~.
To prepare the salts of the compounds I, the ~tarting materials are normally employed in the ~toichio-metric ratio. An excess of one of the components may beadvantageous.

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~, - :,; ' ' , ' , ' ' o o.z. 0050/41488 :
The herbicides, growth regulators and pesticides according to the inven- ;
tion may be applied for instance in the for~ of directly sprayable solu~
tions, powders, suspensions (includin~ high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, 5 dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
Examples of inert carriers are mineral oil fractions of medium to high boil~ng point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydro-carbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkyl-15 ated naphthalenes and their derivatives, methanol, ethanol, propanol,butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and ~trongly polar solvents such as N,N-dimethylformamide, N-methylpyrrolid-one, water, etc. are suitable.
20 Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as Such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concen-25 trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing ~ -agent and possibly solvent or oil.
Surfactants facilitate fine distribution. Examples of surfactants are:
30 alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid; alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, salts of sulfated fatty 35 alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, alkylaryl polyglycol ethers such as ethoxylated isooctylphenol, octyl-phenol, nonylphenol, tributylphenyl polyglycol ethers, fatty alcohol 40 ethoxylates, such as isotridecyl ethoxylate and ethoxylated castor oil, condensation products of ethylene oxide and propylene oxide, such as ethoxylated polyoxypropylene, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

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11 O.Z. 0050/41488 Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homo~eneous granules, may be 5 prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earth~ such aS silicic acids, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium 10 sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations generally contain from 0.01 to 99, and preferably 0.1 to 15 70, % by weight of active ingredient. The active ingredients are expediently used in a purity of 80 to 99.9, preferably 90 to to 99, %
(according to the NMR spectra).
Compounds I according to the invention may be formulated for instance as 20 follows:
I. 90 parts by weight of compound no. 431 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 154 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-30 sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dis-persion is obtained containing 0.02% by weight of the active ingredient.
35 III. 20 parts by weight of compound no. 155 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the 40 solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

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12 O.Z~ 0050/41488 IV. 20 parts by weight of compound no. 168 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280c~ and 10 parts by weight of the adduct o-f 40 moles of ethylene oxide and 1 mole 5 of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of compound no. 385 is well mixed with 3 parts by 10 weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained 15 containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 274 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
VII. 30 parts by weight of compound no. 281 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained 25 having good adherence.
VIII. 20 parts by weight of compound no. 292 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ethar, 2 parts of the sodium salt of a phenol--30 sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The herbicidal and growth-regulating agents, or the active ingredients, may be applied pre- or postemergence. If certain crop plants tolerate the 35 active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post directed, lay-by treatment).
In view of the numerous application methods possible, the compounds according to the invention, or agents containing them, may be used in a large number of crops for removing unwanted plants.

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13 O.Z. 0050/41488 To increase the spectrum of action and to achieve synergistic effects, the compounds I may be mixed with each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 5 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cy~lohexane-1,3-dione derivatives, quinolinecarboxylic acids, (het-ero)-aryloxyphenoxypropionic acids and salts, esters, amides thereof, etc.
It may also be useful to apply the compounds I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts 15 used to remedy nutritional or trace element deficiencies. Non-phytoto~ic oils and oil concentrates may also be added.
When the active ingredients are used as herbicides, the application rates depend on the objective to be achieved, the time of the year, the plants 20 to be combated and their growth stage; the rates vary between 0.001 and 5, and preferably 0.01 to 3, kg/ha.
The compounds of the formula I may exercise a variety of influences on practically all plant development stages, and are therefore used as growth 25 regulators. The diversity of action of growth regulators depends especial-ly on a) the type and variety o~ plant;
b) the time applied, with reference to the development stage of the plants and the time of the year;
c) the place and method of application (seed treatment, soil treatment, or application to foliage);
d) climatic factors, e.g., average temperature, amount of precipitation, sunshine and duration;
35 e) soil conditions (including fertilization);
f) the formulation of the active ingredient; and g) the concentration at which the active ingredient is applied.
The growth regulators of the formula I to be used in accordance with the ~ ~-40 invention may be applied both to the seed of crop plants (as a disinfect-ant) and via the soil, i.e., through the roots, and - the method partic-ularly preferred - by spraying the foliage.
As the compounds are well tolerated by plants, the application rates may vary within wide limits.
.

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14 O.Z. 0050/41488 The thieno[2,3-d]-pyrimidine derivatives of the formula 1 are suitable for effectively combating pests such as insects, arachnids and nematodes. They may be used as pesticides in crop protection and in the hygiene, stores protection and veterinary sector.
Examples of injurious insects belonging to the Lepidoptera order are Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, ArgyreSthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, ~apua reticulana, Cheimatobia brumata, Choristoneura 10 fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis 15 zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia Iycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera cofFeella, Leucoptera scitella, Lithocolletis blan-cardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra 20 brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobi-palpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera 25 frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis.
Examples from the Coleoptera order are Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, 30 Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Pruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, 35 Diabrotica 12-punctata, Diabrotica virgifera, Epilachna-varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha 40 hippocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus sulcatus, Ortiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria.

O.Z. 0050/41488 Examples from the Diptera order are Aedes aegypti, Aedes vexans, Anastrepha ludens, AnopheleS maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, 5 Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Hdplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina lO stabulans, Gestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia ~ -antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhago-letis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa.
Examples from the Thysanoptera order are Frankliniella fusca, 15 Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci.
Examples from the Hymenoptera order are Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, 20 Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta.
Examples from the Heteroptera order are Acrosternum hilare, 81issus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, 25 Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor.
Examples from the Homoptera order are Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, 30 Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, 35 Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum and Viteus vitifolii.
40 Examples from the Isoptera order are Calotermes flavicollis, Leucotermes flavipes, Reticuli~ermes lucifugus and Termes natalensis.
,~ ,.
, ', - . . ; . . -.. ~ :, :
' '~
:, , , . . . ' , , .

p ,~ J ~ -16 O.Z. 0050/41488 Examples from the Orthoptera order are Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus 5 spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus.
Examples from the Acarina order are Amblyomma americanum, Amglyomma 10 variegatum, Argas persicus, Boophilus annulatus, BoophiluS decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, 15 Polyphagotarsonemus latus, Psoroptes OYis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, TetranychuS cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae.
20 Examples from the nematodes class are root-knot nematodes, e.g., Meloi-dogyne hapla, Meloidogyne incognita and Meloidogyne javanica, cyst-forming nematodes, e.g., Globodera rostochiensis, Heterodera avenae, Hetrodera glycinàe, ~eterodera schachtii and Heterodera trifolii, and stem and leaf eelworms, e.g., Belonolaimus longicaudatus, DitylenchuS destructor, Dity-25 lenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus,Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylen-chorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.
30 When the compounds I are used as insecticides, the active ingredient concentrations in the finished formulations may vary within wide limits, but are generally from O.01 to 95, and preferably from 0.1 to 70, wt%.
The active ingredients may also be used with good success in the 3~ ultra-low-volume (ULV) method, where it is possible to apply formulations containing more than 95wt% of active ingredient, or even the active ingredient without any additives.
When the active ingredients are applied in the open, the application rates 40 are expediently from 0.001 to 5, and preferably from 0.01 to 3, kg/ha.
Synthesis examples The directions given in the synthesis examples below were employed, after appropriate modifications of the starting materials, to obtain further , , , : . :, . .

- ~ . . : : , :

17 O.Z. 0050/41488 compounds I. The compounds thus obtained are given, with their melting points, in Table I.
Example 1 .
At room temperature, 70 9 of 2-amino-3-cyano-4-oxo-4,5-dihydrothiophene was introduced into 250 ml of phosphoryl chloride (POCl3). Over a period of 20 minutes, 38 ml of dimethylformamide (DMF~ was dripped into this mixture, and the solution was then stirred for 1 hour at room temperature 10 and for 2.5 hours at 75C. The mixture was then poured onto 2.5 kg of ice and the precipitate was suction filtered, washed with water and dried under reduced pressure at 50C. There was obtained 95.8 9 (94% of theory) of the compound of the formula Cl ~`N~
15 of melting point 161-162C. ~ .
Example 2 At room temperature, 69 g of 2-aldoximo-2-amino-3-cyano-4-oxo-4,5-dihydro-20 thiophene was introduced into 135 ml of phosphoryl chloride (POC13). Over a period of 20 minutes, 20 ml of dimethylformamide (DMF) was dripped into this mixture, and the solution was then stirred for 1 hour at 20C and for 3 hours at 75C. The mixture was then poured onto 1 kg of ice, and the precipitate was suction filtered, washed with water and dried under 25 reduced pressure at 50C. There was obtained 50.2 9 (81% of theory) of the :- compound.of the formula Cl NC~`N--!J
of melting point 155-157C.
30 Example 3 .
Variant a: :
2.5 9 of elemental sodium was dissolved in 150 ml of tert-butanol, and 35 10.2 9 of 4,5-dichlorothienot2,3-d]-pyrimidine ~Example 1) was added. The : reaction mixture was stirred for 1 hour at 20C and for 4 hours at 50C.

.: :, ~ ~,' .'J ' ' ' ~J .~
18 O.Z. 0050/41488 The mixture was then stirred into 500 ml of water and the pH was adjusted to 7 with hydrochloric acid. The precipitate was suction filtered, washed with water and dried under reduced pressure at 50C. There was obtained 7.6 9 (37% of theory) of the compound of the formula o c~J H
S N
of melting point 245-248C.
Variant b:
10 20.5 9 of 4,5-dichlorothieno[2,3-d]-pyrimidine (Example 1) was dissolved in 67 ml of DMF. At room temperature, 17.6 9 of 25wt% strength aqueous sodium hydroxide solution was dripped in. A further 17.6 g of 25wt%
strength aqueous sodium hydroxide solution was then dripped in. After the mixture had been stirred for 24 hours at 20C, the reaction mixture was 15 poured into 500 ml of water and the pH was adjusted to 7 with hydrochloric acid. The precipitate suction filtered, washed with water and dried under reduced pressure at 50C. There was obtained 16.4 g (88% of theory) of a compound which is identical to the product obtained according to variant a above.
Example 4 20.5 9 of 4,5-dichlorothieno[2,3-d]-pyrimidine (Example 1) was suspended in 150 ml of methanol, and 13.3 9 of sodium methanolate was added. The 25 reaction mixture was stirred for 1 hour at room temperature and for a further hour at 50-60C. The reaction mixture was then poured onto 500 ml of water, and the precipitate was suction filtered, washed with water and drled under reduced pressure at 50C. There was obtained 15 9 ~75% of theory) of the compound of the formula ~`NJ . . .
of melting point 145-146C.
Example 5 35 5 9 of 5-chloro-4-thio-3,4-dihydrothienoL2,3-d]-pyrimidine was dissolved in 50 ml of DMF and 5 ml of triethylamine. 5.4 9 of bromoethane was then ,. - ~: . .
.:: . . . ~., . ............................. , .~.. . .
. . .~, - ~ , ,: . . : . . . .

19 O.Z. 0050/hl488 dripped in. The reaction mixture was stirred for 4 hours at room tempera-ture and then stirred into 500 ml of water. The precipitate was suction fiItered, washed with water and dried under reduced pressure at 50C.
There was obtained 4.9 9 (85% of theory) of the compound of the formula ~ `~N~!J
of melting point 64-66C.
Example 6 10 10.2 g of 4,5-dichlorothieno[2,3-d]-pyrimidine ~Example 1) was dissolved in 50 ml of DMF and 4.5 g of pyridine. At room temperature, 4.5 g of n-butanethiol was added. rhe reaction mixture was stirred for 1 hour at room temperature and for a further 2 hours at 50-60C. Subsequently, 10 ml of the solvent was distilled off under reduced pressure. The residue was 15 poured into 500 ml of water, and the precipitate was suction filtered, washed with water and dried under reduced pressure at 50C. There was obtained 9 9 (70~0 of theory) of the compound of the formula S-(CH2)3CH3 of melting point 118-120C.
Example 7 20.5 9 of ~,5-dichlorothieno[2,3-d]-pyrimidine (Example 1) was dissolved in 67 ml of DMF. A solution of 12.4 9 of concentrated ammonia in 12 ml of 25 water was dripped in, and the reaction mixture was stirred for 15 hours at 50C. The mixture was then poured into 500 ml of water, and the precipi-tate was suction filtered, washed with water and dried under reduced pressure at 50C. There was obtained 15.5 9 (84% of theory~ of the compound of the formula .

Cl ~ N
~S ~ N~
of melting point 260-262C.

: . . .... .- , :,. .... . ., . . . : ., , ... .. ,.. , . . , - ,. ~.. -. : . :. : . ..... ... ... , ., ... . ,.. .:, ,. , . : , ::: : -: : . . .. . . . . . . . .

`' !' rJ ~
o.Z. 0050/41488 Example 8 At 20C, 15 9 of 4,5-dichlorothieno[2,3-d]-pyrimidine (Example 1) was added to 50 ml of a 40% strength aqueous methylamine solution in 20 ml of 5 DMF, and the reaction mixture was stirred for 4 hours at 20C. ~he mixture was then poured into 500 ml of water and the precipitate was suction filtered, washed with water and dried under reduced pressure. There was obtained 11.5 g (7g% of theory) of the compound of the formula Cl ~ N
~S ~ N~
10 of melting point 211-212C.
Example 9 Gaseous HCI was gassed, for 3 hours at room temperature and for a further 15 6 hours at 100C, into 12.1 f of 4-chtoro-3-cyano-5-formyl-2-dimethyl-aminoformamidinothiophene and 50 ml of chlorobenzene. Excess HCI was then removed with compressed air. 50 ml of water was added to the reaction mixture, and the precipitate which formed was suction filtered, washed with water and dried under reduced pressure. There was obtained 5.6 9 20 (52%) of the compound of the formula ~~ . ,~;,, OHC ~ NJ H

of melting point 212C Idecomposition).
Example 10 33 9 of 2-amino-3-carboxamido-4-oxo-4,5-dihydro-5-phenylthiophene was stirred in 200 ml of formic acid for 14 hours at 100C and refluxed ~or a further 16 hours. After the mixture had cooled, the precipitate was suc-tion filtered, washed with water and dried under reduced pressure. There 30 was obtained 21.8 9 (64%~ of the compound of the formula H~gH

of a melting point in excess of 290C.

- ,, .. . :. . ~ .- : - . . : .

~ ~ rJ, ~j '; ,~ y 21 O.Z. 0050/41488 Example 11 Variant a:
5 19.6 9 of benzoyl morpholide was added in portions to a suspension of 14 9 of 2-amino-3-cyano-4-oxo-4,5-dihydrothiophene and 50 ml of phosphoryl chloride. The reaction mixture was then stirred for 1 hour at room temp-erature and for a further 3 hours at 78C. It was then poured into 500 ml of ice water. The precipitate was filtered, washed with water and dried 10 under reduced pressure. There was obtained 23.3 9 (83%3 of the compound of the formula Cl C 1~
S N Ph of melting point 138-140C.
15 Variant b:
88.5 9 of benzoyl diethylamide was added to a suspension of 70 9 of 2-amino-3-cyano-4-oxo-4,5-dihydrothiophene and 250 ml of phosphoryl chloride. The reaction mixture was then stirred for 30 minutes at 20C and 20 for a further 3 hours at 78C. The reaction mixture was then poured into 500 ml of ice water. The precipitate was filtered, washed with water and dried under reduced pressure. There was obtained 10.7 g (76%) of the compound obtained under variant a.
25 The compounds listed in Table 1 may be obtained analogously.

., , , . ~ . , . :. . . . . .. .

- . ,:, : . . . , , ~ i , . . . . .

890660 ~
22 O.Z. 0050/41488 Table 1 R3 ~ N
R4 ~ S ~ N ~ R1 Ex. R1 R2 R3 R4 Meltin No. point ~C) 12 H Cl Cl CH3 97- 99 13 H 0-C2H5 Cl H 124 14 H o-nC3H7 Cl H 105-107 15 H 0-isoC3H7 Cl H 80- 81 16 H 0-nC4Hg Cl H 94- 95 17 H 0-isoC~Hg Cl H 79- 80 18 H 0-CH2CH(OCH3)CH3 Cl H 66- 67 19 H 0-secC4Hg Cl H oil 20 H o-nCsH11 Cl H 65- 66 21 H O-NeoCsH11 Cl H
22 H O-nC6H13 Cl H oil 23 H o-nc7Hl5 Cl H oil 24 H 0-nC8Hl7 Cl H oil 25 H o-isoc8Hl7 Cl H
26 H O-nCgHl9 Cl H
27 H o-nCloH21 Cl H
28 H O-nCllH23 Cl H
29 H o-nC12H25 Cl H
30 H o-nCl 3H27 Cl H
31 H O-nC14H31 Cl H
32 H O-nC15H31 Cl H
33 H o-ncl6H3l Cl H
34 H o-nC17H33 C1 H
35 H o-nC18H35 Cl H
36 H 0-ncl9H37 Cl H
37 H o-nc2oH3s Cl H
38 H O-CH2-CH=CH2 Cl H 95~ 98 ' ' ~3 O.Z. 0050/41488 Table 1 ~contd.) Ex. Rl R2 R3 R4 Meltin No. point ~C) 39 H O-CH2-C_CH Cl H 154-156 40 H O-Cyclopropyl Cl H
41 H O-Cyclobutyl Cl H
42 H O-Cyclopentyl Cl H 85- 87 43 H O-Cyclohexyl Cl H 90~ 94 44 H O-Cycloheptyl Cl H oil 45 H O-Cyclooctyl Cl H
46 H O-Cyclononyl Cl H
47 H O-Cyclodecyl Cl H .
48 H O-Cyclododecyl Cl H
49 H O-Cyclohexyl-(2)-CH3 Cl H
50 H O-C6H5 Cl H 106-108 51 H O-C6H4-(4)-CH3 Cl H
52 H O-CH2-C6Hs Cl H 99-100 53 H O-CH2-C6H4-(4)-CH3 Cl H
54 H o-CH2-C6H4-(4)-C(CH3)3 Cl H
55 H . O-cH2-cH2-c6H5 Cl H 77- 78 56 H O-CH2CH2-C6H4-(4)-OCH3 Cl H
57 H O-CH2CH2OH Cl H
58 H O-CH2CH2OCH3 Cl H 107-109 59 H O-cH2cH2~c2H5 Cl H 104-105 . .
60 H O-CH2CH2O-nC3H7 Cl H 60- 62 61 H O-CH2CH2O-nC4Hg Cl H
62 H O-cH2cH2-NH-cH2cH2oH Cl H 117-119 63 H O-cH2cH2-N(cH3)2 Cl H 80- 84 .;
64 H O-cH2cH2-N(c2H5)2 Cl H
65 H O-(CH2)30H Cl H ...

66 H O-(cH2)3ocH3 Cl H
67 H O-(cH2)3oc2H5 Cl H
68 H O-CH2CH2O-nC3H7 Cl H
69 H O-CH2CH2O-nC4Hg Cl H ':.:
70 H O-(cH2)3-N(cH3)2 Cl H :.

: .

., ~ . . :

~90660 ~
24 O~Z~ 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4point ~C) 71 H O-(cH2)3-N(c2Hs)2 Cl H
72 H O-CH(CH3)-CH20-nC4Hg Cl H
73 H O-CH(C2Hs)-CH20CH3 Cl H
74 H O-(CH2)5-CH2cl Cl H
75 H O-(CH2)7-cH2cl Cl H
76 H S-H Cl H 264 77 H S-CH3 Cl H
78 H S-n-C3H~ Cl H 271 79 H S-iso-C3H7 Cl H 260 80 H S-iso-C4Hg Cl H153-155 81 H S-sec-c4Hg Cl H148-150 82 H S-tert-C4Hg Cl H160-163 83 H s-n-C6H13 Cl H
84 H S-n-C~H17 Cl H
85 H S-n-Cl 2H25 Cl H
86 H s-n-C16H33 Cl H
87 H S-n-cl8H37 Cl H
88 H S-Cyclohexyl Cl H
89 H S-C6Hs Cl H181-182 90 H s-C6H4-~4~-CH3 Cl H
91 H S-C6H4-~2)-OH Cl H
92 H S-C6H4-t4)-OCH3 Cl H
93 H S-C6H4-(4)-Cl Cl H
94 H S-C6H3-(2,6)-Cl2 Cl H
95 H S-CH2-c6Hs Cl H
96 H S-(CH2)2-OH Cl H :
97 H S-(CH2) rN(c2H5)2 Cl H
98 H S-CH2CH(CH3)-OH Cl H
99 H S-~CH2)2-COOH Cl H . .
100 H S-CH(CH3)-COOH Cl H
101 H S-CH2-COOH Cl H
102 H S-CH2-COOCH3 Cl H105-108 . .

O.Z. 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4point ~C) 103 H S-CH2-COOC2H5 Cl H 105-107 104 H S-CH2-(2~-Furyl Cl H
105 H SCN Cl H 208-210 106 H F Cl H
107 H CN Cl H
108 H N3 Cl H208 decomp 109 H NH-(CH2)4-CH3 Cl CH3 oil 110 H O-CH3 Cl CH3 92- 93 111 H O-C2H5 Cl CH3 74- 75 112 H O-C6Hs Cl CH3108-109 113 H S-H Cl CH3241-243 114 H S-C6H5 Cl CH3131-133 115 H S-CH2-COOC2H5 Cl CH394~ 98 116 H Cl Cl CHC12125-130 117 H Cl Cl CN 155-157 118 H CH2COOC2H5 Cl H 91- 92 119 H CH(COOC2Hs)2 Cl H 112-113 120 H CH(CN)2 Cl H ,:
121 H CH(CN)COOC2H5 Cl H 158-159 122 H CH(CN)COOCH3 Cl H , .
123 H CH(COOCH3)2 Cl H
124 H CH(CN)C6H5 Cl H .
125 H NH-NH-C2H5 Cl H
126 H NH-N~c2H5)2 Cl H
127 H s-n-C5Hll Cl H
128 H S-Neo-C5H11 Cl H .
129 H N(CH3)-NH-CH3 Cl H ~.

132 C2H5 Cl Cl H :~ .
133 nC3H7 OH OH H
134 nC3H7 Cl Cl H
135 jsoC3H7 OH OH H

.:

- ~ , . . . .

890660 ~ ~
26 O.Z. 0050/41488 Table 1 (contd.) E Rl R2 R3 R4point ~C) 136 isoC3H7 Cl Cl H
137 nC4Hg OH OH H
138 nC4Hg Cl Cl H
139 CycloC3Hs OH OH H
140 CycloC3Hs Cl Cl H
141 CycloC6H11 OH OH H
142 CYC10C6H11 Cl Cl H
143 H NH-C2H5 Cl H 134-135 144 H NH-nC3H7 Cl H 71- 75 145 H NH-isoC3H7 Cl H 119-120 146 H NH-nC4Hg Cl H 71- 75 147 H NH-secC4Hg Cl H 54- 58 148 H NH-isoC4Hg Cl H 88- 90 149 H NH-tertC4Hg Cl H 80- 81 150 H NH-ncsHll Cl H 76- 77 151 H NH-sekCsH11 Cl H oil 152 H NH-CH(CH3)-CH(CH3)2 Cl H
153 H NH-NeoCsH11 Cl H 111-114 154 H NH-nc6Hl3 Cl H 50 155 H NH-nc7Hl5 Cl H 64 156 H NH-nc8Hl7 Cl H 54- 56 t57 H NH-nCgHlg Cl H 60- 65 158 H NH-ncloH2l Cl H
159 H NH-nC12H25 Cl H
160 H NH-nC13H27 Cl H
161 H NH-nCl6H33 Cl H
162 H NH-ncl8H37 Cl H
163 H NH-CH(CH3)CH2CH2CH3 Cl H oil 164 H NH-CH(CH3)-(CH2)3CH3 Cl H oil .:
165 H NH-CH(CH3)-(CH2)2-cH(cH3)2 Cl H oil 166 H NH-cH(cH3)-(cH2)5-cH3 Cl H
167 H NH-cH(c2Hs)-(cH2)4-cH3 Cl H
' '.'~

890660 ~ ~., e~
27 O . Z .0050/41 488 Table 1 (contd.) Ex. Rl R2 R3R4 Meltinq No. point lC) 168 H NH-cH(cH3)-(cH2)3-cH(cH3)2 Cl H oil 169 H (R)-(-)-NH-C~(CH3)-Cyclohexyl Cl H
170 H (S)-(+)-NH-CH(CH3)-Cyclohexyl Cl H
171 H NH-CH2CH2-Cyclohexyl ClH 69- 71 172 H NH-(CH2)2-OH ClH 143-145 173 H NH-(cH2~2-o~H3 ClH 115-117 174 H NH-(CH2)2-0C2H5 ClH 80- 83 175 H NH-(CH2)2-0C6H5 ClH ::
176 H NH-lcH2)2-o-(cH2)2-oH ClH
177 H NH-(cH2~2-NH-(cH2)2-oH ClH
178 H NH-(cH2)2-NH2 ClH ...
179 H NH-(cH2)2-N(cH3)2 ClH 146-148 :~
180 H NH-(cH2)2-N(c2H5)2 ClH 67- 70 181 H NH-(CH2)2-N(iso-c3H7)2 ClH
182 H NH-(CH2)2-Piperazin-(1)-yl ClH .'.:
183 H NH-(CH2)3-OH ClH 114-116 184 H NH-(CH2~3-OCH3 ClH
185 H NH-(cH2)3-oc2H5 ClH 80- 83 186 H NH-~cH2)3-ocH(cH3)2 ClH 42- 43 187 H NH-(cH2)3-oc6H5 ClH
188 H NH-(cH2)3-o-cH2c6H5 ClH oil 189 H NH-(CH2)3-0-(cH2)2-o-cH3 ClH
190 H NH-(CH2)3-0-(CH2)2-0-c2H5 ClH
191 H NH-(CH2)3-0-(CH2)2-0-c6H5 ClH oil 192 H NH-(cH2)3-NH2 ClH 228-230 193 H NH-(cH2)3-N(cH3)2 Cl H 112-115 194 H NH-(cH2)3-N(c2H5)2 Cl H 66- 68 H NH-tCH2)3-N(n-C4H9)2 Cl H :~

196 H NH-(CH2)3-Morpholi n- ( 1 ) -y I C 1 H .:
197 H NH-~CH2)4-OH Cl H
198 H NH-(cH2)5-NH2 Cl H
199 H NH-(CH2)6-OH Cl H

,: . . : : . . . .
, - : .. : . ~: ~ :, , :

28 O.Z. 0050/41488 Table 1 (contd.) Ex. Rl R2 R3 R4Meltinq No. point 1C) _ _ 200 H NH-(cH2)6-NH2 Cl H
201 H NH-(CH2)7-NH2 Cl H
202 H NH-(cH2)8-NH2 Cl H
203 H NH-(CH2)g-NH2 Cl H
204 H NH-(cH2)lo-NH2 Cl 205 H NH-(cH2)l2-NH2 Cl H
206 H NH-cH(cH3)-(cH2)3-N(c2H)2 x HCI Cl H 165-170 207 H NH-CH2-CH(CH3)-OH Cl H
208 H NH-CH(CH3)-CH2-OH Cl H
209 H NH-CH2-(2j-Thienyl Cl H
210 H NH-C(cH3)2-cH2-OH Cl H
211 H NH-C(CH3)-(CH2-OH)2 Cl H
212 H NH-CH(C2Hs)-CH2-OH Cl H . .
213 H NH-(CH2)2-COOH Cl H
214 H NH-(CH2)s-COOH Cl H
215 H NH-(CH2)10-COOH Cl H
216H NH-C6Hs Cl H86- 88 217H NH-C6H4-(2)-CH3 Cl H126-128 218H NH-C6H4-(3)-CH3 Cl H116-118 ~.
219H NH-C6H4-~4)-CH3 Cl H162-165 220H NH-c6H4-(2)-c2H5 Cl H 94- 96 221H NH-c6H4-(4)-c2H5 Cl H 71- 73 222H NH-C6H4-(2)-CF3 Cl H
223H NH-C6H4-~3)-CF3 Cl H98-100 224H NH-C6H4-(4)-CF3 Cl H :
225H NH-C6Hs-(2j-OH Cl H218-220 226H NH-C6Hs-(3)-OH Cl H238-241 227H NH-C6Hs-(4)-OH Cl H219-222 228H NH-C6H4-(2)-OCH3 Cl H 167-169 229H NH-C6H4-(3)-OCH3 Cl H 114-115 230H NH-C6H4-(4)-OCH3 Cl H 104-107 231H NH-C6H4-(2)-OC2Hs Cl H 152-153 :' ' .

, " , , ., . . :: :~, : , .. : .

: .

890660 ~ ~d ~ " ' 29 O.Z. 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4Melttn~C~ , .
232 H NH-C6H4-(3)-Oc2Hs Cl H 93- 95 233 H MH-c6H4-(4)-oc2H5 Cl H 128-130 :.
234 H NH-C6H4-(2)-Cl Cl H 126-130 235 H NH-C6H4-(3)-CI Cl H 135-137 , 236 H NH-C6H4-(4)-CI Cl H 191-195 , 237 H NH-C6H4-(2)-F Cl H
238 H NH-C6H4-(3)-F Cl H
239 H NH-C6H4~(4)-F Cl H
240 H NH-C6H4-(2)-Br Cl H . .
241 H NH-C6H4-(3)-Br Cl H
242 H NH-C6H4-(4)-Br Cl H .
243 H NH-C6H4-(2)-I Cl H
244 H NH-C6H4-(3)-I Cl H :
245 H NH-C6H4-(4)-I Cl H
246 H NH-c6H4-(2)-NH2 Cl H 154-156 247 H NH-c6H4-(3)-NH2 C1 H 182-185 248 H NH-c6H4-(4)-NH2 Cl H 184-185 249 H NH-C6H4-(4)-NH-COCH3 Cl H 210-212 250 H NH-C6H4-(2)-CH2OH C1 H :~.
251 H NH-C6H4-(3)-CH2OH C1 H ~
252 H NH-C6H4-(4)-COCH3 Cl H 194-195 .
253 H NH-C6H4-(2)-COOH Cl H
254 H NH-C6H4-(3)-COOH Cl H
255 H NH-C6H4-(4)-COOH Cl H
256 H NH-c6H4-(2)-coNH2 Cl H
257 H NH-C6H4-(4)-CONH2 Cl H
258 H NH-C6H4-(2)-CN Cl H
259 H NH-C6H4-(3)-CN Cl H

260 H NH-C6H4-(4)-CN Cl H 210-213 261 H NH-C6H3-(2,63-(CH3)2 Cl H
262 H NH-C6H3-(3,5)-(CH3)2 Cl H
263 H NH-C6H3-(2)-OH-(5)-CH3 Cl H

"

. ~ , . . . ~ ; . .

8 9 0 6 6 0 ~ r~
O.Z.0050/41~88 Table 1 (contd.) No R2 R3 R4 Meltin~
264 H NH-C6H3-(2)-OH-(4)-CH3Cl H 258 265 H NH-C6H3-(2)-oH-(2)-cH3Cl H
266 H NH-C6H3-(2)-OH-(5)-CICt H
267 H NH-(2)-Pyridyl Cl H 175- 6 268 H NH-(3)-Pyridyl Cl H 138-140 269 H NH-(4)-Pyridyl Cl H
270 H NH-(2)-(4 -Methyl-pyridyl) Cl H
271 H NH-(2)-(5'-Methyl-pyridyl) Cl H
272 H NH-(2)-(6'-Methyl-pyridyl) Cl H
273 H NH-CH2-(3)-Pyridyl Cl H
274 H NH-CH2-(2)-Furyl Cl H
275 H NH-cH2-c6H5 Cl H 98- 99 276 H NH-CH2-C6H4-(2)-OCH3 Cl H ..
277 H NH-CH2-C6H4-(4)-OCH3 Cl H 118-120 278 H NH-CH2-C6H4-(4)-F Cl H
279 H NH-CH2-C6H4-(2)-Cl Cl H
280 H NH-CH2-C6H4-(4)-CI Cl H
281 H NH-CH2-C6H3-(3,4l-(OcH3)2 Cl H
282 H NH-cH2-cH2-c6H5 Cl H 83 283 H NH-CH(CH3~-C6Hs (~/-J Cl H 76- 78 284 H NH-(cH2)3-c6H5 Cl H
285 H NH-CH(CH3)~(CH2)2-c6H5 Cl H
286 H NH-Cyclopropyl Cl H 87 287 H NH-Cyclopentyl Cl H 79- 80 288 H NH-Cyclohexyl Ct H 85- 86 289 H NH-Cycloheptyl Cl H 62- 63 290 H NH-Cyclooctyl Cl H 43- 48 291 H NH-Cyclododecyl Cl H 119-122 292 H NH-CH2-CH=CH2 Cl H 85- 86 293 H NH-CH2-C_CH Cl H 171-173 294 H N(CH3)2 Cl H 108-110 295 H N(c2Hs)2 Cl H 42- 45 ' .

,.

2 ~

31 O.Z. 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4Melnttn~

296 H N(n-c3H7)2 Cl H oil 297 H N(n-C4Hg)2 Cl H oil 298 H N(iso-C4Hg)2 Cl H 69- 72 299 H N(n-c5Hll)2 Cl H oil 300 H N(sec-C4Hg)2 Cl H
301 H N(iso-c5Hll)2 Cl H
302 H N(n-c6Hl3)2 Cl H oil 303 H N(CH(C2Hs)-(CH2)4-cH3)2 Cl H
304 H N(n-c8Hl7)2 Cl H
305 H N(CH2-CH=CH2)2 Cl H oil 306 H N(Cy~lohexyl)2 Cl H il 307 H N(cH3)-nc4Hs Cl H :~ .
308 H N(CH3)-Cyclohexyl Cl H :
309 H N(C2Hs)-Cyclohexyl Cl H oil 310 H N(cH3)-(cH2)2-oH Cl H
311 H N(c2Hs)-cH(cH33-cH(cH3)2 Cl H
312 H N(c2H5)-(cH) 2-OH Cl H
313 H N(C2Hs)-CH2-cH(OH)-cH3 Cl H
314 H N(tert-c4H9)-(cH2) 2-OH Cl H
315 H N(CH3)C6Hs Cl H 165-167 316 H N(C2Hs~-C6Hs Cl H
317 H N(iso-C3H7)-C6Hs Cl H
318 H N(nC4Hg)-C6Hs Cl H
319 H N(cH2c6Hs) 2 Cl H 101-102 320 H N(cH3)-cH2c6Hs C1 H
321 H N(c2Hs)-cH2c6H5 Cl H
322 H N(iso-C3H7)-CH~C6H5 Cl H

323 H N(tert-C4Hg)-CH2C6H5 Cl H
: 324 H N(cH2cBHs)-(cH2) 2-OH Cl H
325 H N(c6Hs)-cH2c6H5 Cl H
326 H N(CH2C6Hs)-((CH2)2-c6H5) Cl H
327 H Pyrrolidino Cl H 110-112 ., . - :
.. - -, : : . .. .
: : .. . . . ~ .. .

~ ' :: ~ ' .,, ' ' , ' ': '' ~ - - '. ,' : , ~

890660 ~ 2 ~ ~
32 O.Z. 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4po~nt ~C) 328 H Piperidino Cl H 102-105 329 H Hexamethylenimino Cl H 255-256 330 H Morpholino Cl H 162-165 331 H N-Methylpiperazino Cl H 116-120 332 H NH-NH2 Cl H 229-230 333 H NH-NH-CH3 Cl H
334 H NH-NH-C6Hs C1 H 134-136 335 H NH-N(CH3)2 Cl H . .
336 H NH-Morpholin-(1)-yl Cl H
337 H NH-Hexamethylenimino-(l)-yl Cl H
338 H NH-OH Cl H
339 CH3 NH-CH3 Cl H 148-150 340 CH3 NH-C2H5 Cl H 208-210 341 CH3 NH-nC3H7 Cl H 150-151 342 CH3 NH-isoC3H7 Cl H
343 CH3 NH-secC4H9 Cl H 187-190 344 CH3 NH-ncsHll C1 H 60- 62 345 CH3 NH-Cyclohexyl Cl H
346 CH3 NH-C6H5 Cl H 109-112 347 CH3 N(c2H5)2 Cl H 208-210 348 CH2Cl NH-CH3 Cl H
349 CH2C1 NH-C2H5 Cl H 93- 97 350 H NH-CH3 Cl CH3186-187 351*) H NH-c2Hs Cl c~3128-130 352*) H NH-nC3H7 C1 CH3 61- 65 353*) H NH-nC4Hg Cl CH3 61- 65 354 H NH-secC4Hg Cl CH3101-102 355 H NH-nC6H13 Cl CH3 43- 44 :
356 H NH-nC7H15 Cl CH3 53- 54 357 H NH-~2H4-~H C1 CH3155-159 358 H NH-C2H4-OCH3 Cl CH387- 88 359 H NH-Cyclohexyl Cl CH3111-112 *) HCI salt .

890660 2 ~ ~ ~ .t ~
33 O . Z . 0050/41 ~88 : .

Table I (contd.) . .
Ex. R1 R2 R3 R4 Meltin~
No. po~nt 360 H NH-C6H5 Cl CH3169-171 361 H NH-C6H4-(3)-CH3 Cl CH3152-~54 362 H NH-CH2-C-CH Cl CH3183-186 363 H N(CH3)2 Cl CH3 60- 64 364 H Pyrrolidino Cl CH3 75- 76 365 H Piperidino Cl CH3128-130 366 H Morpholino Cl CH3105-106 367 H NH-NH2 Cl CH3194-195 368 H NH-nC3H7 Cl CN 99-102 369 H NH-nC4Hg Cl CN 90- 92 370 H NH-secC4Hg Cl CN 82- 84 371 H NH-nCsH11 Cl CN 82- 84 372 H N(c2H5) 2 Cl CN 60- 62 373 H NH-CH3 ClCH=N-CH3 206-208 374 H NH-isoC3H7 ClCH=N-isoC3H7 105-112 375 H (RjS)-NH-CH(CH3)-Cyclohexyl Cl H
376 H NH-(CH2)3-N(n-C3H7) 2 Cl H
377 H NH-(CH2)3-N(isoc3H7)2 Cl H
378 H NH-(+)-CH(CH3)-C6H5 Cl H
379 H NH-(-)-CH(CH3)-C6Hs Cl H
380 H NH-Cyclobutyl Cl H
381 H NH-Adamantyl Cl H
382 H NH-Cyclononyl Cl H
383 H NH-Cyclodecyl Cl H
384 H NH-Metallyl Cl 385 H N~IsoC3H7)2 Cl H
386 H N-Ethylpiperazino Cl H

387 H Thiomorpholino Cl H
388 H NH-NH-C2H5 Cl H
389 H NH-N(C2Hs32 Cl H
390 H N(CH3)-NH-CH3 Cl H
391 H Imidazol-1-yl Cl H

., . , , :
.

34 O.Z. 0050/41488 Table 1 (contd.) Ex. Rl R2 R3 R4Meltin No. point ~C) 392 H Pyrazol-l-yl Cl H
393 H Triazol-l-yl Cl H
394 H Tetrazol-1-yl Cl H
395 H NH-cH(cH3)-(cH2)4cH3 Cl H oil 396 H NH-CH(CH3)-CH2CN Cl H123-125 397 H N(cH3)-cH(cH3)-cH2cN Cl H84- 90 398 H NH-CH(CH3)-(CH2)4cH3 Cl H oil 399 H N(C2H5)2 Cl CH3oil 400 CH3 NH-(CH2)3-OH Cl H150-152 401 H NH - (CH2) 3-COOH Cl H187-190 402 H NH-nC6H13 Cl CN64- 65 403 H SCN Cl CH3162-165 404 H NH-C6H5 Cl CH=N-C6H5180-183 405 H NH-(CH2)2-Cyclohexyl Cl CH373- 7~
406 H NH-nC7H15 Cl CN64- 65 407 H NH-nC3H7 Cl CH=N-nC3H7 77- 83 ~: .
408 H NH-CH2CH2C6H5 Cl CH382- 84 409 H NH-nc8Hl7 Cl CH341- 43 410 H NH-CH(CH3)-C6Hs Cl CH3121-123 411 H NH-CHICH3)-(CH2)4-CH3 Cl CH3 il 412 H NH-CH(CH3)-(CH2)3-CHICH3)2 Cl CH3 oil 413 H NH-(CH2)3-OCH3 Cl CH371- 72 i : ~ 414 H NH-CH2-C6H5 Cl CH3133-134 415 H NH-nCsH19 Cl CH3 oil 416 H NH-C6H2-(4)-NH2-(3,5)-c12 Cl H 242 417 H NH--(CH2)3--0--(CH2)20(CH2)20C2H5 Cl H oil 418 H NH-CH(CH3)-(CH2)2CH(cH3~2 Cl CH3 oil 419 H O-CH(CH3)-CH20CH~ Cl H oil 420 H O-CH(CH3)-CH2Oc6H5 Cl H 80- 82 421 H S-CH2C_CH Cl H 170-172 422 H S-CH2CH=CH2 Cl H 58- 62 423 H NH-C6H4-(4)-COOC2H5 Cl H 158-162 ', ' ~ ' . :. ' ' , ~'' ' ', ' ~ ' ': ' -' :; : . ' '- ~ ' . :: . ' , , : . .' .
. ~ , ' . . .: ' ~,: ' ;, .
.: ,: ~ . . ' " ' , ' . : .

890660 2~ .s O.z. 0050/41488 Table 1 (contd.) Ex. Rl R2 R3 R4 Melting No. point ~C) 424 H NH-nc8Hl7 Cl CN 45- 46 425 H NH-CH2-CH(C2Hs)~(cH2)3cH3 Cl H oil 426 H NH-(cH2)3oc2H5 Cl CN 70- 74 427 H N(cH2cH2oc~l3)2 Cl H oil 428 H 5-nC5H11 Cl H 170-172 429 H S-CH(CH2CH2CH3)-(cH2)3cH3 Cl H oil 430 H NH-(CH2)8-CH=CH-(CH2)7CH3 Cl H il 431 CH3 Cl Cl H 126-130 432 CH2CI Cl Cl H 120-124 433 H Thiomorpholino-S,S-dioxidC Cl H above 300 434 H NH-CH3 Cl CHO
435 H NH-C2Hs Cl CH0 436 H NH-nC3H7 Cl CHO
437 H NH~isoC3H7 Cl CHO
438 H NH-nC4Hg Cl CHO
439 H NH-isoC4Hg Cl CHO
440 H NH-secC4Hg Cl CHO
441 H NH-tertC4Hg Cl CHO
442 H NH-nÇ5H11 Cl CHO
443 H NH-NeoC5Hll Cl CHO
444 H NH-nc6Hl3 Cl CH0 85-87 445 H NH-nC7H15 Cl CHO
446 H NH-nc8Hl7 Cl CHO 49-54 447 H NH-nCgHl9 Cl CHO :
448 H NH-nCloH21 Cl CHO oil 449 H NH-nC11H23 Cl CHO oil 450 H NH-ncl2H25 Cl CHO oil 451 H NH-nC13H27 Cl CHO oil 452 H NH-ncl4H29 Cl CH0 oil 453 H NH-nClsH3l Cl CHO oil 454 H NH-nC16H33 Cl CHO oil 455 H NH-nC17H3s Cl CHO oil ~ '.

~. . :: .::: : . : . -::
: .:. : ~ : - . .. .

:- . . .

~3 36 O.Z. 0~50/41488 Table 1 (contd.) Ex. Rl R2 R3 R4 Meltin No. . point qc) , 456 H NH-nclsH37 Cl CHO oil 457 H NH-nClgH39 Cl CHO oil 458 H NH-nC20H4l Cl C~IO oil 4S9 H NH-CH(CH3)CH2CH2CH3 Cl CHO oil 460 H NH-CH~CH3)-(CH2)3CH3 Cl CHO oil 461 H NH-C6H5 Cl CHO
462 H NH-CH2C6H5 Cl CHO .
463 H NH-CH2CH2C6H5 Cl CHO
464 H NH-CH(CH3)-C6H5 Cl CHO
465 H NH-~cH2)3-c6H5 Cl CHO
466 H NH-CH2-COOH Cl CHO
467 H NH-(CH2)2-COOH Cl CHO
468 H NH-(CH2)3-COOH Cl CHO
469 H CH(CH3)2 Cl CHO oil 470 H NH-~CH2)2-OH Cl CHO
471 H NH-(CH2)3-OH Cl CHO
472 C6H5 Thiomorpholino-S,S-dioxid~ Cl H
473 H NH-(CH2)2-OcH3 Cl CHO
474 H NH-(CH2)2-O~2H5 Cl CHO : :
475 H NH-(CH2)3-OcH3 Cl CHO
476 H NH-(CH2)3-OC2H5 Cl CHO
477 H NH-Cyclopropyl Cl CHO
478 H NH-Cyclopentyl Cl CHO
479 H NH-Cyclohexyl Cl CHO
480 H NH-Cycloheptyl Cl CHO
481 H NH-Cyclooctyl Cl CHO

482 H NH-Cyclododecyl Cl CHO
483 C6H5 NH-CH3 Cl H
484 C6H5 NH-C2Hs Cl H .: -485 C6H5 NH-nc3H7 Cl H
486 C6H5 NH-isoC3H7 Cl H ..
:
:

37 O.z. 0050/41488 Table 1 (contd.) Ex. Rl R2 R3 R4 Melting No. point ~C) 487 C6H5 NH-nC4Hg Cl H 97-98 488 C6H5 NH-isoC4Hg Cl H
489 C6H5 NH-secC4Hg Cl H
490 C6Hs NH-tertC4Hg Cl H
491 C6H5 NH-nC5HIl Cl H 68-70 492 C6Hs NH-NeoCsH11 Cl H
493 C6H5 NH-nC6H13 Cl H
494 C6Hs NH-nc7Hls Cl H
495 C6H5 NH-nC8H17 Cl H
496 C6H5 NH-nCgHl9 Cl H
497 C6H5 NH-ncloH2l Cl H oil 498 C6H5 NH-nC1lH23 Cl H oil 499 C6H5 NH-nC12H25 Cl H oil 500 C6H5 NH-nCl3H27 Cl H oil 501 C6H5 NH-ncl4H29 Cl H oil 502 C6H5 NH-nClsH3l Cl H oil 503 C6H5 NH-nC16H33 Cl H oil 504 C6H5 NH-nC17H35 Cl H oil 505 C6H5 NH-ncl8H37 Cl H oil 506 C6H5 NH-nC1gH3g Cl H oil 507 C6~s NH-nc2oH4l Cl H oil 508 C6H5 NH-CH(CH3)CH2CH2CH3 Cl H oil 509 C6H5 NH-CH~CH3)-(CH2)3CH3 Cl H oil 510 C6H5 NH-C6H5 Cl H
511 C6H5 NH-CH2C6H5 Cl H

513 C6H5 NH-CH(CH3)-C6Hs Cl H
514 C6H5 NH-(CH2)3-C6H5 Cl H
515 C6Hs NH-CH2-COOH Cl H

516 C6H5 NH--(CH2)2--COOH Cl H
517 ~6H5 NH-(CH2)3-COOH Cl H
518 C6H5 NH-CH(~H3)-(CH2)3- Cl H oil . ~ - . :

2 r ~
38 o.Z. 0050/41488 Table 1 (contd.) Ex. R1 R2 R3 R4 Melting No. point ~C) 519 C6H5 NH-~CH2)2~0H Cl H
520 C6H5 NH-(CH2J3-OH Cl H
521 C6H5 NH-(CH2)2-0cH3 Cl H
522 C6H5 NH-(CH2)2-0c2H5 Cl H
523 C6H5 NH-(CH2)3-OCH3 Cl H
524 C6H5 NH-(CH2)3-0c2H5 Cl H
525 C6H5 NH-Cyclopropyl Cl H
526 C6H5 NH-Cyclopentyl Cl H
527 C6H5 NH-Cyclohexyl Cl H
528 C6H5 NH-Cycloheptyl Cl H "
529 C6H5 NH-Cyclooctyl Cl H
530 C6H5 NH-Cyclododecyl Cl H
531 H NH-CH2-CH=CH2 Cl CHO
532 H NH-CH2-C_CH Cl CHO
533 H NH-Methallyl Cl CHO
534 C6H5 NH-CH2-CH=CH2 Cl H
535 C6H5 NH-CH2-C-CH Cl H
536 C6H5 NH-Methallyl Cl H
537 H NH-CH3 Cl coOC2Hs 538 H NH-C2Hs Cl COOC2Hs 539 H NH-nC3H7 Cl COOC2HS
540 H NH-isoC3H7 Cl COOC2Hs 541 H NH-~C4Hg Cl COOC2H5 542 H NH-isoC4Hg Cl COOC2Hs 543 H NH-secC4Hg Cl COOC2Hs 544 H NH-tertC4Hg Cl COOC2Hs 545 H NH-ncsHll Cl COOC2H5 546 H NH-NeoCsHIl Cl COOC2Hs 547 H NH-nc6Hl3 Cl COOC2Hs 548 H NH-nC7H1s Cl cOOC2Hs 549 H NH-nC8H17 Cl coOC2Hs 550 H NH-nCgHl9 Cl COOC2Hs .

~ ?, ,'~ ~, 3 39 0. Z . 0050/41488 Table 1 (contd. ) Ex R 1 R 2 R 3 R 4 Me I t i n~
_ 551 H NH--nClOH2l Cl COOC2H5 oil 552 H NH-nC~1H23 Cl COOC2H5 oil 553 H NH-nC12H2s Cl COOC2~5 oil 554 H NH--nC13H27 Cl COOC2H5 oil 555 H NH-nC14H29 Cl COOC2H5 oil 556 H NH-nC1sH31 Cl COOC2H5 oil 557 H NH-ncl6H33 Cl COOC2H5 oil 558 H NH-ncl7H3s Cl COOC2H5 oil 559 H NH--nC1gH37 Cl COOC2H5 oil 560 H NH--nC1gH3g Cl coOC2Hs oil 561 H NH-nC20H41 Cl COOC2H5 oil 562 H NH--CH(CH3)CH2CH2CH3 Cl COOC2H5 oil 563 H NH--CH(CH3)--(CH2)3CH3 Cl COOC2H5 oil 564 H NH--C6H5 Cl COOC2H5 565 H NH-cH2c6H5 Cl COOC2H5 566 H NH-CH2CH2C6Hg Cl cOOC2Hs 567 H NH - CH(CH3) - C6Hs Cl C00C2Hs 568 H NH-(cH2)3-c6H5 Cl COOC2H5 569 H NH--CH2--COOH Cl COOC2H5 570 H NH - (CH2) 2 - COOH Cl C00C2H5 571 H NH-(CH2)3--COOH Cl cooc2Hs 572 H NH--CH(CH3)--(CH2)3 Cl COOC2H5 oil CHlCH3)2 573 H NH - (CH2) 2 - OH Cl COOC2H5 574 H NH--(CH2)3--OH Cl COOC2Hs 575 H NH - ~CH2i 2 - OCH3 Cl COOC2H5 576 H NH-(cH2)2-oc2H5 Cl cooC2Hs 577 H NH - (CH2) 3 - OCH3 Cl COOC2H5 578 H NH - (CH2) 3 - OC2H5 Cl COOC2Hs 579 H NH--Cyclopropyl Cl COOC2Hs 580 H NH--Cyclop~ntyl Cl cOOC2Hs 581 H NH-Cyclohexyl Cl COOC2Hs - :' ~ ' : :. -' . ' : ' . ..

2 ~ ~J ' ,~ s' rJ . ~.

o.z. 0050/41488 Table 1 (contd.) No R2 R3 R4 Melt1n~
582 H NH-Cycloheptyl Cl COOC2Hs 583 H NH-Cyclooctyl Cl COOC2H9 584 H NH-Cyclododecyl Cl COOC2H5 585 H NH-CH2-CH=CH2 Cl COOC2H5 586 H NH-CH2-C-CH Cl COOC2H5 587 H NH-Methallyl Cl COOC2Hs 588 H NH-CH3 Cl CONH2 589 H NH-C2H5 Cl CONH2 590 H NH-nC3H7 Cl CONH2 591 H NH-isoC3H7 Cl C0NH2 :
592 H NH-nC4Hg Cl CONH2 593 H NH-isoC4Hg Cl CONH2 594 H NH-secC4Hg Cl CONH2 595 H NH-tertC4Hg Cl CONH2 596 H NH-nC5H11 Cl CONHz .. .
597 H NH-NeoC5Hll Cl CONH
598 H NH-nC6H13 Cl CONH2 599 H NH-nc7Hls Cl CONH2 600 H NH-nC8H17 Cl CONH2 601 H NH-nCgH19 Cl CONH2 602 H NH-ncloH2l Cl CONH2 ~
603 H NH-nC11H23 Cl CONH2 oil ~.
604 H NH-ncl2H25 Cl CONH2 oil 605 H NH-nC13H27 Cl CONH2 oil 606 H N~-nC14H29 Cl CONH2 oil 607 H NH-nC1sH31 Cl CONH2 oil 608 H NH-nC16H33 Cl CONH2 oil 609 H NH-nC17H3s Cl CONH2 oil 610 H NH-nC18H37 Cl CONH2 oil 611 H NH-nClgH39 Cl CONH2 oil 612 H NH-nC20H4l Cl CONH2 oil 613 H NH-CH~CH3)CH2CH2CH3 Cl CONH2 il 8 9 0 6 6 0 2 ~
41 O.Z. 0050/41488 Table 1 (contd.) No R2 R3 R4 Meltin~
614 H NH-CH(CH3)-(CH2)3CH3 Cl CONH2 oil 615 H NH-C6H5 Cl CONH2 616 H NH-cH2c6Hs Cl CONH2 617 H NH-CH2CH2C6H5 Cl CONH2 618 H NH-CH(CH3)-C6H5 Cl CONH2 619 H NH-(CH2)3-C6Hs Cl CONH2 620 H NH-CH2-COOH Cl CONH2 621 H NH-(CH2)2-COOH Cl CONH2 622 H NH-(CH2)3-COOH Cl CONH2 623 H NH-CH(CH3)-(CH2)3- Cl CONH2 oil CH(CH3)2 624 H NH (CH2~2-OH Cl CONH2 625 H NH-(CH2)3-OH Cl CONH2 626 H NH-(CH2)2-OCH3 Cl CONH2 627 H NH-(cH2)2-oc2H5 Cl CONH2 628 H NH-(cH2)3-ocH3 Cl CONH2 629 H NH-(cH2)3-oc2H5 Cl CONH2 630 H NH-Cyclopropyl Cl CONH2 631 H NH-Cyclopentyl Cl CONH2 632 H NH-Cyclohexyl Cl CONH2 633 H NH-Cycloheptyl Cl CONH2 634 H NH Cy~looctyl Cl CONH2 635 H NH-Cyclododecyl Cl CONH2 636 H NH-CH2-CH=CH2 Cl CONH2 637 H NH-CH2-C_CH Cl CONH2 638 H NH-Methallyl Cl CONH2 639 H NH-CH3 Cl COOC2Hs 640 H NH-C2Hs Cl COOC2H5 641 H NH-nC3H7 Cl COOC2H5 642 H NH-isoC3H7 Cl COOC2H5 643 H NH-nC4Hg Cl COOC2Hs 644 H NH-isoC4Hg Cl COOC~H5 ,. . . - : .: , , , - ~. :

,. : : .: . : . .. :
;'' . . - ' . , ' ~ , : ::: : :

~ 3~?3~2~

42 O.Z. 0050/41488 Table 1 (contd.) Ex R1 R2 R3 R4 Meltin~

645 H NH-secC4Hg Cl C0OC2Hs 646 H NH-tertC4Hg Cl CO0C2Hs 647 H NH-nCsHIl Cl C00C2Hs 648 H NH-NeoCsH11 Cl COOC2Hs 649 H NH-nC6H13 Cl cooc2Hs 650 H NH-nC7H15 Cl C00C2Hs 651 H NH-nC8H17 Cl C0OC2H5 652 H NH-nCgH19 Cl CoOC2Hs 653 H NH-nCloH2l Cl COOC2H5 oil 654 H NH-nC11H23 Cl C00C2Hs oil 65S H NH-ncl2H2s Cl C0OC2H5 oil 656 H NH-nC13H27 Cl C00C2Hs il 657 H NH-nC14H29 Sl COOC2H5 oil 658 H NH-nclsH3l Cl COQC2Hs oil 659 H NH-nC16H33 Cl COOC2H5 oil 660 H NH-nC17H35 Cl COOC2H5 oil 661 H NH-ncl8H37 Cl COOC2H5 oil 662 H NH-nCIgH39 Cl C00C2Hs oil 663 H NH-nC20H41 Cl C0OC2H5 oil 664 H NH-CH(CH3)CH2CH2CH3 Cl C0OC2Hs oil 665 H NH-CHtCH3)-(CH2~3CH3 Cl C0OC2H5 oil 666 H NH-C6Hs Cl CO0C2Hs '~
667 H NH-CH2C6Hs Cl C00C2Hs 668 H NH-CH2CH2C6Hs Cl C00C2Hs 669 H NH-CH(CH3)-C6Hs Cl C0OC2Hs 670 H NH-(cH2)3-c6H5 Cl COOC2Hs 671 H NH-CH2-COOH Cl coOC2Hs 672 H NH-~CH2)2-COOH Cl CO0C2Hs 673 H NH-(CH2)3-COOH Cl C0OC2H5 674 H NH~CH(C)H3)-(CH2)3- Cl CO0C2Hs oil 675 H NH (CH2)2-OH Cl C00C2H5 ': . : ~ .. . . .

890660 2 ~ g ?

43 O.Z. 0050/41488 Table 1 (contd.) Ex. R1 R2 R3 R4 Meltinq No . po i nt C) 676 H NH-(CH2)3-OH Cl COOC2H5 677 H NH-(cH2)2-ocH3 Cl COOC2H5 678 H NH-(CH2)2-OC2H5 Cl COOC2Hs 679 H NH-(CH2)3-OCH3 Cl COOC2Hs 680 H NH-(CH2)3-OC2H5 Cl COOC2H5 681 H NH-Cyclopropyl Cl COOC2Hs 682 H NH-Cyclopentyl Cl COOC2H5 683 H NH-Cyclohexyl Cl COOC2H5 684 H NH-Cycloheptyl Cl COOC2Hs 685 H NH-Cyclooctyl Cl COOC2H5 686 H WH-Cyclododecyl Cl COOC2H5 687 H NH-CH2-CH=CH2 Cl COOC2Hs 688 H NH-CH2-C_CH Cl COOC2H5 689 H NH-Methallyl Cl COOC2H5 690 H NH-CH3 Cl COOCH3 691 H NH-C2H5 Cl COOCH3 692 H NH-nC3H7 Cl COOCH3 693 H NH-isoC3H7 Cl COOCH3 694 H NH-nC4Hg Cl COOCH3 695 H NH-isoC4Hg Cl COOCH3 696 H NH-secC4Hg Cl COOCH3 697 H N~-tertC4Gg Cl COOCH3 698 H NW-nC5Hll Cl COOCH3 699 H NH-NeoCsUll Cl COOCH3 700 H NH-nC6H13 Cl COOCH3 701 H NH-nC7Hl~ Cl COOCH3 702 H NH-nC8H17 Cl COOCH3 703 H NH-nCgH19 Cl COOCH3 704 H ~H-nCloH21 Cl COOCH3 oil 705 H NH-nC11H23 Cl COOCH3 oil 706 H NH-nC12H25 Cl COOCH3 oil 707 H NH-nC13H27 Cl COOCH3 oil .:

, ,~, ,, , ",.... .. . . . .. ..

' ' - . . . ' ' : , ! ~ .. ' ~ , ,, ,. ' ' ~,.' ' .'. ' ' ~ I, ';.~ ' . . ' ' ' ' 44 o.z. 0050/41488 Table 1 (contd.) Ex Rl R2 R3 R4 polntn~C

708 H NH-nC14H29 Cl COOCH3 oil 709 H NH-nclsH3l Cl COOCH3 oil 710 H NH-ncl6H33 Cl COOCH3 oil 711 H NH-nC17H35 Cl COOCH3 oil 712 H NH-ncl8H37 Cl COOCH3 oil 713 H NH-nClgH39 Cl COOCH3 oil 714 H NH-nC20H4l Cl COOCH3 oil 715 H NH-CH(CH3)CH2CH2CH3 Cl COOCH3 oil 716 H NH-CH(CH3)-(CH2)3CH3 Cl COOCH3 oil 717 H NH-C6H5 Cl COOCH3 :
718 H NH-CH2C6H5 Cl COOCH3 719 H NH-CH2CH2C6H5 Cl COOCH3 720 H NH-CH(CH3)-C6H5 Cl COOCH3 721 H NH-(cH2)3-c6H5 Cl COOCH3 722 H NH-CH2-COOH Cl COOCH3 723 H NH-(CH2)2-COOH Cl COOCH3 724 H NH-(CH2)3-COOH Cl COOCH3 725 H CH(CH3J2 Cl COOCH3 oil 726 H NH-(CH2)2-OH Cl COOCH3 727 H NH-(CH2)3-OH Cl COOCH3 728 H NH-(CH2)2-OCH3 Cl COOCH3 729 H NH-(cH2)2-Oc2H5 Cl COOCH3 730 H NH-(CH2)3-OCH3 Cl COOCH3 731 H NH-(CH2)3-OCHs Cl COOCH3 732 H NH-Cyclopropyl Cl COOCH3 .
733 H NH-Cyclopentyl Cl COOCH3 734 H NH-Cyclohexyl Cl COOCH3 735 H NH-Cycloheptyl Cl COOCH3 736 H NH-Cyclooctyl Cl COOCH3 737 H NH-Cyclododecyl Cl COOCH3 738 H NH-CH2-CH=CH2 Cl COOCH3 739 H NH-CH2-C-cH2 Cl COOCH3 890660 2 F~ ,'7S ~f: ~_ o.z. 0050/41488 Table 1 (contd.) Ex. Rl R2 U3 R4 Meltin No. point ~C) 740 H NH-Me thallyl Ct COOCH3 741 H NH-nC6H13 Cl COOH
742 H NH-nCgH17 Cl COOH
743 H NH-ncloH2l Cl COOH
744 CH3 NH-nc6Hl3 Cl CHO
745 CH3 NH-nC8Hl7 Cl CH0 746 CH3 NH-nCloH21 Cl CH0 747 C6H5 NH-nc6Hl3 Cl CHO
748 C6H5 NH-nc8Hl7 Cl CH0 749 C6H5 NH-nCloH21 Cl CHO .:
750 CH2CI2 Cl Cl H 97-99 751 H CH(cH3)-(cH2)4cH3 Cl CH0 oil 752 H NH-C6H4-(2)-CH3 Cl CHO
753 H NH-c6H4-(2)-c2Hs Cl CH0 754 H NH-C6H4-(2)-CF3 Cl CH0 755 H NH-(CH2)3-isoc3H7 Cl CHO
756 H NH-(cH2)3-cH2c6Hs Cl CH0 757 H N(CH3J2 Cl CH0 758 H N(c2Hs)2 Cl CHO
759 H N(nc3H7) 2 Cl CH0 760 H N(nC4Hg)2 Cl CH0 761 H N(cH2cH=cH2)2 Cl CH0 762 H Pyrrolidino Cl CH0 763 H Piperidino Cl CH0 764 H Hexamethylenimino Cl CH0 765 H Morpholino Cl CH0 766 H N( CH 2cH2ocH3) 2 Cl CH0 oil 767 H S-CH3 Cl CH0 -768 H S-c2H5 Cl CH0 769 H S-nC3H7 Cl CH0 :-770 H S-CH2-CH=CH3 Cl CH0 771 H SCN Cl CH0 - - . :, : - , . . :. .. . .. ~ .. , . : .

890660 ~
46 O.Z. 0050/41~88 Table 1 (contd.) Ex. Rl R2 R3 R4 Melting No. . point ~C) ; .
772 H 0-CH3 Cl CH0 773 H o-c2H5 Cl CH0 774 H o-nc3H7 Cl CH0 775 H O-CH2CH20CH3 Cl CH0 776 H O-CH2CH(CH3)0CH3 CI CH0 777 C6H5 CH(CH3)-(CH2)4c~3 Cl H oil 778 C6H5 NH-C6H4-(2)-CH3 Cl H
779 C6H5 NH-C6H4-(2)-C2H5 Cl H
780 C6H5 NH-C6H4-(2)-CF3 Cl H
781 C6H5 NH-(CH2)3-isoc3H7 Cl H
782 C6H5 NH-(CH2)3-CH2c6H5 Cl H
783 C6H5 N(CH3)2 Cl H
784 C6H5 N(C2Hs)2 Cl H
785 C6H5 N(C2Hs)2 Cl H
786 C6H5 N(nC4Hs) 2 Cl H
787 C6H5 N(cH2cH=cH2)2 Cl H
788 C6H5 Pyrrolidino Cl H
789 C6H5 Piperidino Cl H
790 C6H5 Hexamethylenimino Cl H
791 C6H5 Morpholino Cl H ~ .
792 C6H5 N(CH2CHzOcH3)2 Cl H
793 C6Hs S-CH3 Cl H
794 C6H5 s-c2Hs Cl H
795 C6H5 s-nC3H7 Cl H
796 C6H5 S-CH2-CH=CH3 Cl H
797 C6H5 SCN Cl H
798 C6H5 O-CH3 Cl H

799 C6H5 o-c2Hs Cl H
800 C6H5 o-nc3H7 Cl H
801 C6H5 0--CH2CH20CH3 Cl H
802 C6H5 0-CH2CH(CH3)0CH3 Cl H
803 H NH-CH(CH3)-(CH2)4cH3 Cl CONH2 oil :
:
... ... .. .. . . . . . . . .. . . .

~ . . . : - - .: . - - ,, .- ~ ,. , . ! ` ; -. . .. - ~

890660 ~ L
47 O.z. 0050/41488 Table 1 (contd.) Ex Rl R2 R3 R4 Meltin~

804 H NH-C6H4-(2)-CH3 Cl CONH
805 H NH-c6H4-(2)-c2H5 Cl CONH
806 H NH-C6H4-(2)-CF3 Cl CONH
807 H NH-tcH2)3-isoc3H7 Cl CONH
808 H NH-(cH2)3-CH2C6H5 Cl CONH~
809 H N(CH3)2 Cl CONH
810 H N(C2Hs)2 Cl CONH
811 H N(nc3H7)2 Cl CONH
812 H N(nC4Hg)2 Cl CONH
813 H N(cH2cH=cH2)2 Cl C0NH
814 H Pyrrolidino Cl CONH
815 H Piperidino Cl CONH
816 H Hexamethylenimino Cl CONH
817 H Morpholino Cl CONH
818 H N(cH2cH2ocH3) 2 Cl CONH
819 H S-CH3 Cl CONH
820 H S-C2H5 Cl CONH
821 H s-nC3H7 Cl CONH
822 H S-CH2-CH=CH3 Cl CONH
823 H SCN Cl CONH2 824 H O-CH3 Cl CONH
825 H O-C2Hs Cl CONH
826 H O-nC3H7 Cl CONH
827 H O--CH2CH20CH3 Cl CONH
828 H O-CH2CH(CH3)OCH3 CI CONH2 829 H CH~CH3)-(CH2)4CH3 Cl COOH oil 830 H NH-C6H4-(2)-CH3 Cl COOH
831 H NH-c6H4 (2)-C2H5 Cl COOH
832 H NH-C6H4-(2)-CF3 Cl COOH
833 H NH-(cH2)3-isoc3H7 Cl COOH
834 H NH-(cH2)3-cH2c6H5 Cl COOH
835 H N(cH3)2 Cl COOH
'' ' .', .. .

2 ~ rJ .' ~., r ' ~i ~ 890660 48 O.Z. 0050/41488 Table 1 (contd.) Ex Rl R2 - R3 R4_ - po3nt ~c) 836 H N(C2Hs)2 Cl COOH
837 H N(nC3H7)2 Cl COOH
838 H N(nC4Hg)2 Cl COOH
839 H N(cH2cH=cH2)2 Cl COOH
840 H Pyrrolidino Cl COOH
841 H Piperidino Cl COOH
842 H Hexamethylenimino Cl COOH
843 H Morpholino Cl COOH
844 H N(cH2cH2ocH3)2 Cl COOH :.
845 H S-CH3 Cl COOH
846 H S-C2H5 Cl COOH
847 H S-nC3H7 Cl COOH
848 H S-CH2-CH=CH3 Cl COOH
849 H SCN Cl COOH
850 H O-CH3 Cl COOH
851 H O-C2Hs Cl COOH
852 H o-nC3H7 Cl COOH
853 H O-CH2CH2OCH3 Cl COOH
854 H O-CH2CH(CH3)OCH3 Cl COOH
855 H CH(CH3)-(CH2)4CH3 Cl COOCH3 856 H NH-C6H4-~2)-CH3 Cl COOCH3 857 H NH-c6H4-(2)-c2H5 Cl COOCH3 858 H NH-C6H4-(2)-CF3 Cl COOCH3 859 H NH-(CH2)3-isoc3H7 Cl COOCH3 860 H NH-(cH2)3-cu2c6H5 Cl COOCH3 861 H N(CH3)2 Cl COOCH3 862 M N(c2H5)2 Cl COOCH3 863 H N(nC3H7)2 Cl COOCH3 864 H N(nC4Hg)2 Cl COOCH3 865 H N(cH2cH=cH2)2 Cl COOCH3 866 H Pyrrolidino Cl COOCH3 867 H Piperidino Cl COOCH3 .~
,!
.,~

:
: -. . . .

: .

~ ~3 ~ 2 :~

49 O.Z. 005Q/41488 Table 1 (contd.) Ex. Rl R2 R3 R4 Melting No. point ~C) 868 H Hexamethylenimino Cl COOCH3 869 H Morpholino Cl COOCH3 870 H N(cH2cH2ocH3)2 Cl COOCH3 871 H S-CH3 Cl COOCH3 872 H S-C2H5 Cl COOCH3 873 H S-nC3H7 Cl COOCH3 874 H S-CH2-CH=CH3 Cl COOCH3 875 H SCN Cl . COOCH3 876 H O-CH3 Cl COOCH3 oil 877H CH(CH3)-(CH2)4CH3 Cl cooc2Hs 878H NH-C6H4 ~2)-CH3 Cl COOC2H5 879H NH-C6H4-(2)-C2Hs Cl COOC2H5 880H NH-C6H4-(2)-CF3 Cl COOC2H5 881H NH-(CH2)3-isoC3H7 Cl COOC2H5 882H NH-(cH2)3-cH2c6H5 Cl coOC2Hs 883H N(CH3)2 Cl COOC2H5 884H N(C2H5)2 Cl COOC2H5 885H N(nc3H7)2 Cl COOC2Hs 886~ N(nC4Hg)2 Cl COOC2H5 887H N(CH2CH=CH2)2 Cl COOC2H5 888 H Pyrrolidino Cl COOC2H5 889 H Piperidino Cl COOC2H5 i 890 H Hexamethylenimino Cl COOC2Hs 891 H Morpholino Cl coOC2Hs 892 H N(cH2cH2o~H3)2 Cl cOQC2H5 893 H S-CH3 Cl COOC2H5 . .
894 H S-C2~5 Cl COOC2H5 895 H S-nC3H7 Cl COOC2Hs 896 H S-CH2-CH=CH3 Cl COOC2H5 897 H SCN Cl cOOC2Hs 898 H O-C2Hs CI COOC2H5 899H o-nC3H7 Cl COOnC3H7 ~: - ' i , , ,,, ., :

~ ~3 ~

O.Z. 00~0/4148~
' :
Table 1 (contd.) Ex. Rl R2 R3 R4 Meltin No. point ~C) _ 900 H O-nC4Hg Cl COOnC4Hg 901 H o-nC5HIl Cl cooncsHll 902 H o-nc6Hl3 Cl COOnC6H~3 903 H Cl Cl C6H5262-266 904 CH3 NH2 Cl H
905 CH3 NH-nC4Hg Cl H 37-40 906 CH3 NH-isoC4Hg Cl H
907 CH3 NH-tertC4Hg 908 CH3 NH-isocsHll Cl H
gog CH3 NH-NeocsHll Cl H
910 CH3 NH-nC6H13 Cl H 59-60 911 CH3 NH-nC7Hls Cl H
912 CH3 NH-nc8Hl7 Cl H
913 CH3 NH-nCgHlg Cl H oil 914 CH3 NH-nCIoH2l Cl H oil 915 CH3 NH-nCllH23 Cl H oil 916 CH3 - NH-nCl2H25 Cl H oil 917 CH3 NH-nC13H27 Cl H oil 918 CH3 NH-ncl4H29 Cl H oil 919 CH3 NH-nclsH3l Cl H oil 920 CH3 NH-ncl6H33 Cl H oil 921 CH3 NH-nC17H35 Cl H oil 922 CH3 NH-ncl8H37 Cl H oil 923 CH3 NH-nClgH39 Cl H oil 924 CH3 NH-nC20H41 Cl H oil 925 CH3 NH-CH(CH3)CH2CH2CH3 Cl H oil 926 CH3 NH-CH(CH3)- Cl H oil -(cH2)3-cH3 927 CH3 NH~CH2C6H5 Cl H
928 CH3 NH-CH2CH2C6H5 Cl H
929 CH3 NH-CH(CH3)-C6Hs Cl H
930 CH3 NH-(CH2)3-C6H5 Cl H
: 931 CH3 NH-CH2-COOH Cl H

.- . . . , ~: - -, - ~ : . . , :. . -:, . :. . .
. ...

51 O.Z. 0050/41488 Table 1 (contd.) Ex. Rl R2 R3 R4 Meltin No. . point ~C) 932 CH3 NH-(CH2)2-COOH Cl H ~.
933 CH3 NH-(CH2)3-COOH Ct H .:
934 CH3 NH-CH(CH~)- Cl H
-(cH2)3-cH(cH3)2 935 CH3 NH-(CH2)2-OH Cl H
936 CH3 NH-(CH2)2-OCH3 Cl H ~: -937 CH3 NH-(CH2)2-OC2H5 Cl H . .
938 CH3 NH-(CH2)3-OCH3 Cl H
939 CH3 NH-(CH2)3-Oc2H5 Cl H
940 CH3 NH-Cyclopropyl Cl H
941 CH3 NH-Cyclobutyl Cl H
942 CH3 NH-Cyclopentyl Cl H
943 CH3 NH-Cycloheptyl Cl H
944 CH3 NH-Cyclooctyl Cl H
945 CH3 NH-Cyclononyl Cl H
946 CH3 NH-Cyclodecyl Cl H
947 CH3 NH-Cyclododecyl Cl 948 CH3 N(CH3)2 Cl H
949 CH3 N(nC3H7)2 Cl H
950 CH3 Pyrrol1dino Cl H ; .
951 CH3 Piperidino Cl H
952 CH3 Hexamethylenimino Cl H
953 CH3 Morpholino Cl H
954 CH3 Thiomorpholino Cl H .
955 CH3 Thiomorpholino-S,S-dioxid~ Cl H

.

, . .,, , . ~, . , ,, . :
: . .. . : . ,.

52 O.Z. 0050/41488 Use examples The following examples demonstrate the insecticidal action of compounds I.
5 Example No. 956 Petri dishes (covers and bottoms) were evenly lined with a total of 1 ml of a O.lwt% acetonic solution of the active ingredients. After the solvent ~ -had evaporated, 10 houseflies (Musca domestica) and water-moist absorbent 10 cotton were introduced into each dish, and the covers were placed on the bottoms. The kill rate was assessed after 24 hours by counting the number of dead flies.
Table 2 Ex. no. K i I I rate (%) 155 80 -~

Example 957 Potted bush beans which had devcloped the first pair of true leaves, were heavily infested with alt stages of the spider mite Tetranychus telarius 30 and on which numerous eggs had been laid were uniformly sprayed with 50 ml of aqueous formulations of the active ingredients. After 5 days, during ~I which the plants were kept under usual greenhouse conditions, the kill rate was assessed by means of a microscope.
35 Table 3 : : .
~Ex. no.Active ingredient conc. (ppm) Kill rate (%) ': ~
155 1000 approx. 90 40 156 <1000 100 ~ 157 ~1000 100 ;~ 395 ~1~00 100 '~ .

53 o.z. 0050/41488 Example 958 Young bean plants (Vicia faba) with a large colony of Aphis fab~e were uniformly sprayed with 50 ml of an aqueous solution of the active 5 ingredients. The kill rate was determined after 24 hours.
Table 4 Ex. no.Active ingredient conc. (ppm) Kill rate (%) 154 <looO 100 Example 959 0.5 ml of acetonic solutions of the active ingredients was added to the 20 surface of a nutrient medium (5 ml in plastic Petri dishes 25 mm in dia-meter and 10 mm high). After the acetone had evaporated, the medium was infected with 30 ~1 of E. coli bacteria and 50 ~1 of nematode suspension (Caenorhabditis elegans). After 2.8 hours the contact action was assessed in percentage kill.
Tabte 5 ~-EX. no.Active ingredient conc. (ppm) Kill rate (%) Example 960 5 young ticks (Ornithodorus moubata) were placed in a water-permeable bag which was then dipped for 5 seconds in an aqueous solution of the active : ' , ' -:
. . . ' ' ., : .
. . .

54 o.z. 0050/41488 ingredient. The bags were then suspended ~or 48 hours, after which the kill rate was determined.
Ex. no. Active ingredient conc. (ppm) Kill rate (%) lO 157 1000 100 Example 961 -lS To test the herbicidal action of the active ingredients, seeds of various plants were sown separately, according to species, in plastic pots con-taining loamy sand and 3wt% of humus. The plants were grown to a height of 3 to 15 cm, after which they were treated with suspensions of the active ingredients in water. The application rate was 2.0 kg of active ingredient 20 per hectare.
The plants used in the greenhouse experiments were redroot pigweed (Amaranthus retroflexus, abbreviated AMARE), catchweed bedstraw (&alium aparine, abbreviated GALAP), and henbit (Lamium amplexicaule, abbreviated Z5 LAMAM).
The results were assessed on a 0 to 100 scale, 100 denoting complete destruction and 0 denoting normal growth.
30 Ex. no.Test plants and damage ~%) AMARE GALAPLAMAM

~5 .

~, ', ... : .

: , :. .
.

Claims (10)

1. Thieno[2,3-d]-pyrimidine derivatives of the general formula I

(I), where the substituents have the following meanings:
R1 is hydrogen, C1-C5-alkyl, C1-C3-chloroalkyl, C3-C6-cycloalkyl, phenyl or benzyl;
R2 is fluorine, chlorine, bromine, iodine, hydroxy, azido, cyano, thiocyanato, mercapto, an organic radical not bonded via nitrogen or a radical NR5R6, where R5 and R6 are identical or different and each is hydrogen, amino or organic radicals, or form, together with the nitrogen atom, a heterocyclic radical of 3 to 8 ring atoms, with the proviso that R2 is not phenoxy-C2-C3-alkylamino;
R3 is chlorine, bromine, hydroxy or mercapto, with the proviso that R2 is not hydroxy when R3 is bromine, and that R3 is not hydroxy when R4 is alkoxycarbonyl or carboxy;
R4 is hydrogen, C1-C6-alkyl, C3-C6-mono-, di- or trihaloalkyl, phenyl, cyano, formyl, hydroxyiminomethyl, carboxy, alkoxy-carbonyl, aminocarbonyl or a radical of the formula CH=X, where X is a radical, bonded via nitrogen, of a primary amine, or a radical, bonded via carbon, of a methylene-active compound, tautomers thereof, and salts and tautomers thereof tolerated by crop plants.

2. A process for preparing thieno[2,3-d]-pyrimidine derivatives of the formula I as set forth in claim 1, wherein a compound of the general formula II
(II), where R3 and R4 have the meanings given above, is reacted with a compound of the general formula III

(III), where R1 has the meanings given above and T2 and T3 are identical or different and each is C1-C4 alkyl, phenyl, or, together with the amide nitrogen, denote a 5- to 7-membered saturated heterocycle, in the presence of 1.1 to 20 mol of phosphoryl chloride or phosphoryl bromide, based on 1 mol of II, to give thieno[2,3-d]pyrimidine derivatives of the general formula Ia (Ia), where R7 is chlorine or bromine, and in which R7 is if desired exchanged in conventional manner for other nucleophilic radicals R2.

3. A process for preparing thieno[2,3-d]-pyrimidine derivatives of the general formula I as claimed in claim 1, wherein a compound of the general formula IV

(IV), where the substituents R3 and R4 have the meanings given in claim 1, is reacted in conventional manner with an acid anhydride containing at least one radical R1-CO-, or with a carboxylic acid R1-COOH, or with an adduct of a carboxylic acid R1-COOH and a Lewis acid, R1 having the stated meanings, to give a compound of the general formula Ib (Ib), which is then converted with a phosphoryl halide to give a compound of the general formula Ia as claimed in claim 2, and in which if desired R7 is exchanged in conventional manner for other nucleophilic radicals R2.

4. A process for preparing thieno[2,3-d]pyrimidines of the general formula I as claimed in claim 1, wherein a thiophene of the general formula II
(II), where R3 and R4 have the above meanings, is reacted in conventional manner with an orthoester of the general formula V

(R8O)3C-R1 (V), where R8 is C1-C6-alkyl, to give a compound of the general formula VI
(VI), which is then converted to a corresponding compound I in the presence of a nucleophile containing R2.

5. Herbicidal agents containing a carrier and a herbicidally effective amount of a thieno[2,3-d]-pyrimidine derivative of the general formula I as set forth in claim 1.

6. Pesticides containing a carrier and an effective amount of a thieno[2,3-d]-pyrimidine derivative of the general formula I as set forth in claim 1.

7. Growth-regulating agents containing a carrier and a growth-regulatory amount of a thieno[2,3-d]-pyrimidine derivative of the general formula I as set forth in claim 1.

8. A process for combating the growth of unwanted plants, wherein a herbicidally effective amount of a thieno[2,3-d]-pyrimidine derivative of the-general formula I as set forth in claim 1, or of a salt thereof, is allowed to act on the plants and/or their habitat.

9. A process for combating pests, wherein the pests and/or the areas and/or spaces to be kept free from pests are treated with a pest-effective amount of a thieno[2,3-d]-pyrimidine derivative of the general formula I as set forth in claim 1.

10. A process for regulating plant growth, wherein a regulatorily effective amount of a thieno[2,3-d]-pyrimidine derivative of the formula I as set forth in claim 1 is allowed to act on seeds, plants and/or their habitat.