Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
.
: ' ~ . . , : ,. ... , : . ' . . . . . ` ' . ~ . . . : . .
~ 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),
:~ .
, , ' ' ` ' . ' ' , . " , '' ~ ' ,
., ` ' ' ' . ~ ~ ' . ' . . .
. .
- 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
R7
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.
- , . ~ .: - i ; - . . . ..
~, - :,; ' ' , ' , ' '
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.
,
. ~ : , ~ :, - , : :
.
.
2 ~ ,i ;J ~..
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.
~ ~.,"
: ., . - .. .. . . ........ : - . . . .
- . ,, ~ ,, . .~ . . : , . :
~ ~ r~
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.
. : . .: :: . :
-
- , ::
, - . ~ : : . :
:. . . .: .
2 ~ J ~
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.
.
.: ' ' :.:, : . , . ::
', '~ ' ~ .' , .' , ' .' '' ' ~
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
O-CH3
~`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
S--C2H5
~ `~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 .
NH2
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
HN-CH3
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
R2
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
' '
890660
~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
. .
890660
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 ~.
130 H OH OH H
131 C2H5 OH OH 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
,: . . : : . . . .
, - : .. : . ~: ~ :, , :
890660
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 ~
- 890660
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
., . , , :
.
890660
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
890660
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 ..
:
:
890660
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
512 C6H5 NH-CH2CH2C6H5 C1 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
890660
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 . ~.
890660
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~
890660
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, ';.~ ' . . ' ' '
'
890660
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 :~
890660
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 ~
890660
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
.- . . . , ~: - -
,
- ~ : . . , :. . -
:, . :. . .
. ...
890660
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 (%)
12 100
147 100
20 157 80
155 80 -~
156 100
168 100
395 100
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
155 1000 100
156 1000 100
185 1000 100
15 395 1000 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 (%)
147 100 100
154 4 80
155 4 80
156 10 100
157 10 100
168 100 100
275 100 100
282 10 100
293 100 100
395 100 100
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 (%)
147 400 100
154 40 100
1S5 1000 100
156 400 80
lO 157 1000 100
168 20 80
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
144 100 100 90
146 100 90 70 -
~5
.
~,
', ... : .
: , :. .
.
