Insecticidal, acaricidal and herbicidal 1-H-3-aryl-pyrrolidine-2,4-dione derivatives

The invention relates to new 3-aryl-pyrrolidine-2,4-dione derivatives, to a plurality of processes for their preparation, and to their use as insecticides, acaricides and herbicides.
Pharmaceutical properties have previously been described for 3-acyl-pyrrolidine-2,4-diones (S. Suzuki et al. Chem. Pharm. Bull. 15, 1120 (1967)). Furthermore, N-phenyl-pyrrolidine-2,4-diones were synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985 1095). However, a biological activity of these compounds was not described.
EP-A 0,262,399 discloses compounds of a similar structure (3-aryl-pyrrolidine-2,4-diones), but it has not emerged that they have herbicidal, insecticidal or acaricidal action.
DE-A 3,525,109 discloses 1-H-3-arylpyrrolidine-2,4-diones of a similar structure which are used as intermediates in the syntheses of dyes.
New 3-aryl-pyrrolidine-2,4-dione derivatives which are outlined by the formula (I) ##STR2## in which X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or halogenalkyl,
Z represents alkyl, halogen or alkoxy,
n represents a number from 0-3,
R represents hydrogen, or represents the groups --CO--R.sup.1, --CO--O--R.sup.2 or E.sup..sym.
in which
R.sup.1 represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl which can be interrupted by hetero atoms, each of these substituents being optionally substituted by halogen, or represents optionally substituted phenyl, optionally substituted phenylalkyl, substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl and
R.sup.2 represents alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or optionally substituted phenyl, each of these substituents being optionally substituted by halogen,
A represents hydrogen, or alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl or cycloalkyl which is optionally interrupted by hetero atoms, each of these radicals being optionally substituted by halogen, or represents aryl, arylalkyl or hetaryl each of which is optionally substituted by halogen, alkyl, halogenoalkyl, alkoxy or nitro,
B represents hydrogen, alkyl or alkoxyalkyl,
or where
A and B together with the carbon atom to which they are bonded form a carbocycle and
E.sup..sym. represents a metal ion equivalent or an ammonium ion, and the pure enantiomeric forms of compounds of the formula (I)
have now been found.
The following sub-groups may be defined below:
(Ia): compounds of the formula (I) where R=hydrogen,
(Ib): compounds of the formula (I) where R=COR.sup.1,
(Ic): compounds of the formula (I) where R=COOR.sup.2,
(Id): compounds of the formula (I) where R=E.sup..sym. represents a metal ion equivalent or an ammonium ion.
Furthermore, it has been found that 3-arylpyrrolidine-2,4-diones or their enols of the formula (Ia) ##STR3## in which A, B, C, X, Y, Z and n have the abovementioned meanings, are obtained when
(A) N-acylamino acid esters of the formula (II) ##STR4## in which A, B, X, Y, Z and n have the abovementioned meanings and
R.sup.3 represents alkyl,
are subjected to intramolecular condensation in the presence of a diluent and in the presence of a base.
(B) Furthermore, it has been found that compounds of the formula (Ib) ##STR5## in which A, B, X, Y, Z, R.sup.1 and n have the abovementioned meanings, are obtained when compounds of the formula (Ia) ##STR6## in which A, B, X, Y, Z and n have the abovementioned meanings, are reacted
.alpha.) with acid halides of the general formula (III) ##STR7## in which R.sup.1 has the abovementioned meaning and
Hal represents halogen, in particular chlorine and bromine,
if appropriate in the presence of a diluent and
if appropriate in the presence of an acid-binding agent, or
.beta.) with carboxylic anhydrides of the general formula (IV)
R.sup.1 --CO--O--CO--R.sup.1 (IV)
in which
R.sup.1 has the abovementioned meaning,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
(C) Furthermore, it has been found that compounds of the formula (Ic) ##STR8## in which A, B, C, X, Y, Z, R.sup.2 and n have the abovementioned meanings, are obtained when compounds of the formula (Ia) ##STR9## in which A, B, X, Y, Z and n have the abovementioned meanings, are reacted with chloroformic esters of the general formula (V)
R.sup.2 --O--CO--Cl (V)
in which
R.sup.2 has the abovementioned meaning,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid-binding agent.
D) Furthermore, it has been found that compounds of the formula (I) ##STR10## in which X, Y, Z, A, B and n have the abovementioned meanings, are obtained when compounds of the formula (Ia) ##STR11## in which X, Y, Z, A, B and have the abovementioned meanings, are reacted with metal hydroxides or amines of the general formulae (VI) and (VII) ##STR12## in which Me represents monovalent or divalent metal ions,
s and t represent the numbers 1 and 2 and
R.sup.4, R.sup.5 and R.sup.6 independently of one another represent hydrogen and alkyl,
if appropriate in the presence of a diluent.
Surprisingly, it has been found that the new 3-arylpyrrolidine-2,4-dione derivatives of the formula (I) are distinguished by outstanding insecticidal, acaricidal and herbicidal actions.
Preferred 3-aryl-pyrrolidine-2,4-dione derivatives of the formula (I) are those in which
X represents C.sub.1 -C.sub.6 -alkyl, halogen or C.sub.1 -C.sub.6 -alkoxy,
Y represent hydrogen, C.sub.1 -C.sub.6 -alkyl, halogen or C.sub.1 -C.sub.6 -alkoxy or C.sub.1 -C.sub.3 -halogenoalkyl,
Z represents C.sub.1 -C.sub.6 -alkyl, halogen or C.sub.1 -C.sub.6 -alkoxy,
n represents a number from 0-3,
R represents hydrogen (Ia), or represents the groups of the formula ##STR13## in which R.sup.1 represents C.sub.1 -C.sub.20 -alkyl, C.sub.2 -C.sub.20 -alkenyl, C.sub.1 -C.sub.8 -alkoxy-C.sub.2 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -alkylthio-C.sub.2 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -polyalkoxy-C.sub.2 -C.sub.8 -alkyl or cycloalkyl which has 3-8 ring atom sand which can be interrupted by oxygen and/or sulphur, each of these substituents being optionally substituted by halogen, or represents optionally halogen-, nitro-, C.sub.1 -C.sub.6 -alkyl-, C.sub.1 -C.sub.6 -alkoxy-, C.sub.1 -C.sub.6 -halogenalkyl-or C.sub.1 -C.sub.6 -halogenalkoxy-substituted phenyl; or represents optionally halogen-, C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy-, C.sub.1 -C.sub.6 -halogenalkyl- or C.sub.1 -C.sub.6 -halogenalkoxy-substituted phenyl-C.sub.1 -C.sub.6 -alkyl, or represents optionally halogen- or C.sub.1 -C.sub.6 -alkyl-substituted hetaryl, or represents optionally halogen- or C.sub.1 -C.sub.6 -alkyl-substituted phenoxy-C.sub.1 -C.sub.6 -alkyl, or represents optionally halogen, amino or C.sub.1 -C.sub.6 -alkyl-substituted hetaryloxy-C.sub.1 -C.sub.6 -alkyl,
R.sup.2 represents C.sub.1 -C.sub.20 -alkyl, C.sub.2 -C.sub.20 -alkenyl, C.sub.1 -C.sub.8 -alkoxy-C.sub.2 -C.sub.8 -alkyl or C.sub.1 -C.sub.8 -polyalkoxy-C.sub.2 -C.sub.8 -alkyl each of which is optionally substituted by halogen, or represents optionally halogen-, nitro-, C.sub.1 -C.sub.6 -alkyl-, C.sub.1 -C.sub.6 -alkoxy- or C.sub.1 -C.sub.6 -halogeno-alkyl-substituted phenyl,
A represents hydrogen or represents straight-chain or branched C.sub.1 -C.sub.12 -alkyl, C.sub.3 -C.sub.8 -alkenyl, C.sub.3 -C.sub.8 -alkynyl, C.sub.1 -C.sub.10 -alkoxy-C.sub.2 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -polyalkoxy-C.sub.2 -C.sub.8 -alkyl, C.sub.1 -C.sub.10 -alkylthio-C.sub.2 -C.sub.8 -alkyl, cycloalkyl which has 3-8 ring atoms and which can be interrupted by oxygen and/or sulphur, each of these substituents being optionally substituted by halogen, or represents aryl, hetaryl or aryl-C.sub.1 -C.sub.6 -alkyl each of which is optionally substituted by halogen, C.sub.1 -C.sub.6 -alkyl-C.sub.1 -C.sub.6 -haloalkyl, C.sub.1 -C.sub.6 -alkoxy or nitro,
B represents hydrogen or straight-chain or branched C.sub.1 -C.sub.12 -alkyl or C.sub.1 -C.sub.8 -alkoxyalkyl,
or where
A and B together with the carbon atom to which they are bonded form a 3 to 8-membered ring,
E.sup..sym. represents a metal ion equivalent or an ammonium ion,
and the pure enantiomeric forms of compounds of the formula (I).
Particularly preferred compounds of the formula (I) are those in which
X represents C.sub.1 -C.sub.4 -alkyl, halogen, or C.sub.1 -C.sub.4 -alkoxy,
Y represents hydrogen, C.sub.1 -C.sub.6 -alkyl, halogen, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.2 -halogenoalkyl,
Z represents C.sub.1 -C.sub.4 -alkyl, halogen or C.sub.1 -C.sub.4 -alkoxy,
n represents a number from 0-3,
R represents hydrogen (Ia) or represents the groups of the formula ##STR14## in which R.sup.1 represents C.sub.1 -C.sub.16 -alkyl, C.sub.2 -C.sub.16 -alkenyl, C.sub.1 -C.sub.6 -alkoxy-C.sub.2 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkylthio-C.sub.2 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -polyalkoxy-C.sub.2 -C.sub.6 -alkyl or cycloalkyl which has 3-7 ring atoms and which can be interrupted by 1-2 oxygen and/or sulphur atoms, each of these substituents being optionally substituted by halogen, or represents optionally halogen-, nitro-, C.sub.1 -C.sub.4 -alkyl-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1 -C.sub.3 -halogenoalkyl-or C.sub.1 -C.sub.3 -halogenoalkoxy-substituted phenyl, or represents optionally halogen-, C.sub.1 -C.sub.4 -alkyl-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1 -C.sub.3 -halogenoalkyl- or C.sub.1 -C.sub.3 -halogenoalkoxy-substituted phenyl-C.sub.1 -C.sub.4 -alkyl, or represents optionally halogen- or C.sub.1 -C.sub.6 -alkyl-substituted hetaryl, optionally represents halogen- or C.sub.1 -C.sub.4 -alkyl-substituted phenoxy-C.sub.1 -C.sub.5 -alkyl, or represents optionally halogen, amino or C.sub.1 -C.sub.4 -alkyl-substituted hetaryloxy-C.sub.1 -C.sub.5 -alkyl,
R.sup.2 represents C.sub.1 -C.sub.16 -alkyl, C.sub.2 -C.sub.16 -alkenyl, C.sub.1 -C.sub.16 -alkoxy-C.sub.2 -C.sub.6 -alkyl or C.sub.1 -C.sub.6 -polyalkoxy-C.sub.2 -C.sub.6 -alkyl each of which is optionally substituted by halogen, or represents optionally halogen, nitro-, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.3 -alkoxy- or C.sub.1 -C.sub.3 -halogeno-alkyl-substituted phenyl,
A represents hydrogen or straight-chain or branched C.sub.1 -C.sub.10 -alkyl, C.sub.3 -C.sub.6 -alkenyl, C.sub.3 -C.sub.6 -alkynyl, C.sub.1 -C.sub.8 -alkoxy-C.sub.2 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -polyalkoxy-C.sub.2 -C.sub.6 -alkyl, C.sub.1 -C.sub.8 -alkylthio-C.sub.2 -C.sub.6 -alkyl, or cycloalkyl which has 3-7 ring atoms and which can be interrupted by 1-2 oxygen and/or sulphur atoms, each of these substituents being optionally substituted by halogen, or represents aryl, hetaryl or aryl-C.sub.1 -C.sub.4 -alkyl each of which is optionally substituted by halogen-, C.sub.1 -C.sub.4 -alkyl-, C.sub.1 -C.sub.4 -haloalkyl-C.sub.1 -C.sub.4 -alkoxy- or nitro,
B represents hydrogen or straight-chain or branched C.sub.1 -C.sub.10 -alkyl or C.sub.1 -C.sub.6 -alkoxyalkyl,
or where
A and B together with the carbon atom to which they are bonded form a 3 to 7-membered ring,
E.sup..sym. represents a metal ions equivalent or an ammonium ion,
and the pure enantiomeric forms of compounds of the formula (I).
Very particularly preferred compounds of the formula (I) are those in which
X represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine, methoxy or ethoxy,
Y represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert.-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,
Z represents methyl, ethyl, i-propyl, butyl, i-butyl, tert.-butyl, fluorine, chlorine, bromine, methoxy or ethoxy,
n represents a number from 0-3,
R represents hydrogen (Ia) or represents the groups of the formula ##STR15## in which R.sup.1 represents C.sub.1 -C.sub.14 -alkyl, C.sub.2 -C.sub.14 -alkenyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.2 -C.sub.6 --alkyl, C.sub.1 -C.sub.4 -alkylthio-C.sub.2 -C.sub.6 -alkyl, C.sub.1 -C.sub.4 -polyalkoxy-C.sub.2 -C.sub.4 -alkyl and cycloalkyl which has 3-6 ring atoms and which can be interrupted by 1-2 oxygen and/or sulphur atoms, each of these substituents being optionally substituted by fluorine or chlorine, or represents optionally fluorine- chlorine-, bromine-, methyl-, ethyl-, propyl, i-propyl-, methoxy-, ethoxy-, trifluoromethyl-, trifluoromethoxy-or nitro-substituted phenyl, or represents optionally fluorine-, chlorine-, bromine-, methyl-, ethyl-, propyl-, i-propyl-, methoxy-, ethoxy-, trifluoromethyl- or trifluoromethoxy-substituted phenyl-C.sub.1 -C.sub.3 -alkyl, or represents pyridyl, pyrimidyl, thiazolyl or pyrazolyl each of which is optionally substituted by fluorine-, chlorine-, bromine-, methyl- or ethyl-, or represents optionally fluorine-, chlorine-, methyl- or ethyl-substituted phenoxy-C.sub.1 -C.sub.4 -alkyl, or represents pyridyloxy-C.sub.1 -C.sub.4 -alkyl, pyrimidyloxy-C.sub.1 -C.sub.4 -alkyl or thiazolyloxy-C.sub.1 -C.sub.4 -alkyl each of which is optionally substituted by fluorine-, chlorine-, amino-, methyl- or ethyl-,
R.sup.2 represents C.sub.1 -C.sub.14 -alkyl, C.sub.2 -C.sub.14 -alkenyl, C.sub.1 -C.sub.4 -alkoxy-C.sub.2 -C.sub.6 -alkyl or C.sub.1 -C.sub.4 -polyalkoxy-C.sub.2 -C.sub.6 -alkyl each of which is optionally substituted by fluorine or chlorine, or represents phenyl which is optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,
A represents hydrogen, or straight-chain or branched C.sub.1 -C.sub.8 -alkyl, C.sub.3 -C.sub.4 -alkenyl, C.sub.3 -C.sub.4 -alkynyl, C.sub.1 -C.sub.6 -alkoxy-C.sub.2 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -polyalkoxy-C.sub.2 -C.sub.4 -alkyl, C.sub.1 -C.sub.6 -alkylthio-C.sub.2 -C.sub.4 -alkyl, cycloalkyl which has 3-6 ring atoms and which can be interrupted by 1-2 oxygen and/or sulphur atoms, each of these substituents being optionally substituted by halogen, or represents aryl, pyridine, imidazole, pyrazole, triazole, indole, thiazole or aryl-C.sub.1 -C.sub.3 -alkyl each of which is optionally substituted by fluorine-, chlorine-, bromine-, methyl-, ethyl-, propyl-, iso-propyl-, methoxy-, ethoxy-, trifluoromethyl- or nitro,
B represents hydrogen or straight-chain or branched C.sub.1 -C.sub.8 -alkyl or C.sub.1 -C.sub.4 -alkoxyalkyl,
or where
A and B together with the carbon atom to which they are bonded form a 3 to 6-membered ring,
E.sup..sym. represents a metal ion equivalent or an ammonium ion, and the pure enantiomeric forms of compounds of the formula (I).
If, according to process (A), N-2,6-dichlorophenylacetyl-alanine ethyl ester is used, the course of the process according to the invention can be outlined by the following equation: ##STR16##
If, according to process (B) (variant .alpha.), 3-(2,5,6-trimethylphenyl)-5-isopropyl-pyrrolidine-2,4-dione and pivaloyl chloride are used as starting substances, the course of the process according to the invention can be outlined by the following equation: ##STR17##
If, according to process B (variant .beta.), 3-(2,4,6-timethylphenyl)-5-cyclopentyl-pyrrolidine-2,4-dione and acetic anhydride are used, the course of the process according to the invention can be outlined by the following equation: ##STR18##
If, according to process C, 3-(2,4,6-trimethylphenyl)-5-phenyl-pyrrolidine-2,4-dione and ethoxyethyl chloroformate are used, the course of the process according to the invention can be outlined by the following equation: ##STR19##
If, according to process D, 3-(2,4-dichlorophenyl)-5-(2-indolyl)-pyrrolidine-2,4-dione and methylamine are used, the course of the process according to the invention can be outlined by the following equation: ##STR20##
Some of the compounds of the formula (II) ##STR21## in which A, B, X, Y, Z, n and R.sup.3 have the abovementioned meanings, and which are required as starting substances in the above process (A) are known or can be prepared in a simple manner by methods known in principle. For example, acyl-amino acid esters of the formula (II) are obtained when
a) amino acid derivatives of the formula (VIII) ##STR22## in which R.sup.7 represents hydrogen (VIIIa) or alkyl (VIIIb) and
A has the abovementioned meanings, are acylated with phenylacetic halides of the formula (IX) ##STR23## in which X, Y, Z and n have the abovementioned meanings and
Hal represents chlorine or bromine, (Chem. Reviews 52 237-416 (1953));
or when acylamino acids of the formula (IIa) ##STR24## in which A, B, X, Y, Z and n have the abovementioned meanings and
R.sup.7 represents hydrogen,
are esterified (Chem. Ind. (London) 1568 (1968)).
The following compounds of the formula (II) may be mentioned by way of example:
1. N-2,4-dichlorophenyl-acetyl-glycine ethyl ester
2. N-2,6-dichlorophenyl-acetyl-glycine ethyl ester
3. N-(2,6-dichlorophenyl-acetyl)-alanine ethyl ester
4. N-(2,6-dichlorophenyl-acetyl)-valine ethyl ester
5. N-(2,6-dichlorophenyl-acetyl)-leucine ethyl ester
6. N-(2,6-dichlorophenyl-acetyl)-methionine ethyl ester
7. N-(2,6-dichlorophenyl-acetyl)-phenylanine ethyl ester
8. N-(2,6-dichlorophenyl-acetyl)-tryptophane ethyl ester
9. N-(2,6-dichlorophenyl-acetyl)-isoleucine ethyl ester
10. N-(2,4,6-trimethylphenyl-acetyl)-glycine methyl ester
11. N-(2,4,6-trimethylphenyl-acetyl)-alanine ethyl ester
12. N-(2,4,6-trimethylphenyl-acetyl)-valine ethyl ester
13. N-(2,4,6-trimethylphenyl-acetyl)-leucine ethyl ester
14. N-(2,4,6-trimethylphenyl-acetyl)-isoleucine ethyl ester
15. N-(2,4,6-trimethylphenyl-acetyl)-methionine ethyl ester
16. N-(2,4,6-trimethylphenyl-acetyl)-phenylalanine ethyl ester
17. N-(2,4,6-trimethylphenyl-acetyl)-tryptophane ethyl ester
18. N-(2,4,6-trimethylphenyl-acetyl)-(4-chlorophenyl)-alanine ethyl ester
19. N-(2,4,6-trimethylphenyl-acetyl)-S-methyl-cysteine ethyl ester
20. N-(2,4,6-trimethylphenyl-acetyl)-S-benzyl-cysteine ethyl ester
21. N-(2,4,6-trimethylphenyl-acetyl)-O-methyl-threonine ethyl ester
22. N-(2,4,6-trimethylphenyl-acetyl)-tert.-butyl-alanine ethyl ester
23. N-(2,4,6-trimethylphenyl-acetyl)-histidine ethyl ester
24. N-(2,4,6-trimethylphenyl-acetyl)-O-methyl- tyrosine ethyl ester
25. Methyl N-(2,4,6-trimethylphenyl-acetyl)-1-aminocyclopropane-carboxylate
26. Methyl N-(2,4,6-trimethylphenyl-acetyl)-1-aminocyclopentane-carboxylate
27. Methyl N-(2,4,6-trimethylphenyl-acetyl)-1-aminocyclohexane-carboxylate
28. Methyl N-(2,4,6-trimethylphenyl-acetyl)-1-amino-isobutyrate
29. Methyl N-(2,4,6-trimethylphenyl-acetyl)-2-ethyl-2-amino-butyrate
30. Methyl N-(2,4,6-trimethylphenyl-acetyl)-2-methyl-2-amino-butyrate
31. Methyl N-(2,4,6-trimethylphenyl-acetyl)-2-methyl-2-aminovalerate
32. Methyl N-(2,4,6-trimethylphenyl-acetyl)-2,3-dimethyl-2-aminovalerate
The following compounds of the formula (IIa) may be mentioned by way of example:
1. N-2,4-dichlorophenyl-acetyl-glycine
2. N-2,6-dichlorophenyl-acetyl-glycine
3. N-(2,6-dichlorophenyl-acetyl)-alanine
4. N-(2,6-dichlorophenyl-acetyl)-valine
5. N-(2,6-dichlorophenyl-acetyl)-leucine
6. N-(2,6-dichlorophenyl-acetyl)-methionine
7. N-(2,6-dichlorophenyl-acetyl)-phenylalanine
8. N-(2,6-dichlorophenyl-acetyl)-tryptophane
9. N-(2,6-dichlorophenyl-acetyl)-isoleucine
10. N-(2,6-trimethylphenyl-acetyl)-glycine
11. N-(2,6-trimethylphenyl-acetyl)-alanine
12. N-(2,6-trimethylphenyl-acetyl)-valine
13. N-(2,6-trimethylphenyl-acetyl)-leucine
14. N-(2,6-trimethylphenyl-acetyl)-isoleucine
15. N-(2,6-trimethylphenyl-acetyl)-methionine
16. N-(2,6-trimethylphenyl-acetyl)-phenylalaine
17. N-(2,6-trimethylphenyl-acetyl)-tryptophane
18. N-(2,6-trimethylphenyl-acetyl)-(4-chlorophenyl)-alanine
19. N-(2,6-trimethylphenyl-acetyl)-S-methyl-cysteine
20. N-(2,6-trimethylphenyl-acetyl)-S-benzyl-cysteine
21. N-(2,6-trimethylphenyl-acetyl)-O-methyl-threonine
22. N-(2,6-trimethylphenyl-acetyl)-tert.-butyl-alanine
23. N-(2,6-trimethylphenyl-acetyl)-histidine
24. N-(2,6-trimethylphenyl-acetyl)-O-methyl -tyrosine
25. N-(2,6-trimethylphenyl-acetyl)-1-amino-cyclopropane-carboxylic acid
26. N-(2,6-trimethylphenyl-acetyl)-1-amino-cyclopentanecarboxylic acid
27. N-(2,6-trimethylphenyl-acetyl)-1-amino-cyclohexanecarboxylic acid
28. N-(2,6-trimethylphenyl-acetyl)-1-amino-isobutyric acid
29. N-(2,6-trimethylphenyl-acetyl)-2-ethyl-2-amino-butyric acid
30. N-(2,6-trimethylphenyl-acetyl)-2-methyl-2-aminobutyric acid
31. N-(2,6-trimethylphenyl-acetyl)-2-methyl-2-amino-valeric acid
32. N-(2,6-trimethylphenyl-acetyl)-2,3-dimethyl-2-amino-valeric acid
Compounds of the formula (IIa) can be obtained, for example, from the phenylacetic halides of the formula (IX) and amino acids of the formula (VIIIa) by the method of Schotten-Baumann (Organikum [Practical Organic Chemistry], 9th edition, 446 (1970) VEB Deutscher Verlag der Wissenschaften, Berlin).
Compounds of the formula (VIIIa) and (VIIIb) are known or, alternatively, can be prepared with ease by processes known in principle from the literature.
Process (A) is characterized in that compounds of the formula (II) in which A, B, X, Y, Z, n and R.sup.3 have the abovementioned meanings are subjected to an intramolecular condensation reaction in the presence of bases.
Diluents which can be used in process (A) according to the invention are all customary inert organic solvents. The following can preferably be used: hydrocarbons such as toluene and xylene, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and furthermore polar solvents such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone.
Deprotonating agents which can be employed for carrying out the process (A) according to the invention are all customary proton acceptors. The following can preferably be used: alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides and alkaline earth metal carbonates such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, all of which can also be employed in the presence of phase-transfer catalysts such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (methyl tri-C.sub.8 -C.sub.10 -alkyl-ammonium chloride) or TDA 1 (tris-(methoxyethoxyethyl)-amine). Other substances which can be employed are earth metal amides and alkaline earth metal hydrides such as sodium amide, sodium hydride and calcium hydride, and furthermore also alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tert.-butylate.
When carrying out process (A) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between 0.degree. C. and 250.degree. C., preferably between 50.degree. C. and 150.degree. C.
Process (A) according to the invention is generally carried under atmospheric pressure.
When carrying out process (A) according to the invention, the reactants of the formulae (II) and the deprotonating bases are generally employed in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 moles).
Process (B.alpha.) is characterized in that compounds of the formula (Ia) are reacted with carboxylic acid halides of the formula (III).
When the acid halides are used, then the diluents which can be employed in process (B.alpha.) according to the invention are all inert solvents which are inert towards these compounds. The following can preferably be used: hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones as acetone and methyl isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, in addition dimethyl sulphoxide and sulpholane. If the stability of the acid halide to hydrolysis permits, the reaction can also be carried out in the presence of water.
If the corresponding carboxylic acid halides are used, then acid-binding agents which are suitable for the reaction by process (B.alpha.) according to the invention are all customary acid acceptors. The following can preferably be used: tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hunig base and N,N-dimethyl-aniline, furthermore alkaline earth metal oxides such as magnesium oxide and calcium oxide, and in addition alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate.
When carrying out process (B.alpha.) according to the invention, the reaction temperatures can also be varied within a substantial range when carboxylic acid halides are used. In general, the process is carried out at temperatures between -20.degree. C. and +150.degree. C., preferably between 0.degree. C. and 100.degree. C.
When carrying out the process (B.alpha.) according to the invention, the starting substances of the formula (Ia) and the carboxylic acid halide of the formula (III) are generally used in approximately equivalent amounts. However, it is also possible to employ the carboxylic anhydride in a larger excess (up to 5 moles). Working-up is carried out by customary methods.
Process (B.beta.) is characterized in that compounds of the formula (Ia) are reacted with carboxylic anhydrides of the formula (IV).
If, in process (B.beta.) according to the invention, carboxylic anhydrides are used as reactant of the formula (IV), then the preferred diluents which can be used are those diluents which are also preferably suitable when halides are used. Apart from that, a carboxylic acid anhydride which is employed in excess can also act simultaneously as diluent.
The reaction temperatures in process (B.beta.) according to the invention, too, can also be varied within a substantial range when carboxylic anhydrides are used. In general, the process is carried out at temperatures between -20.degree. C. and +150.degree. C., preferably between 0.degree. C. and 100.degree. C.
When carrying out the process according to the invention, the starting substances of the formula (Ia) and the carboxylic anhydride of the formula (IV) are generally used in approximately equivalent amounts. However, it is also possible to employ the carboxylic anhydride in a larger excess (up to 5 moles). Working-up is carried out by customary methods.
In general, a procedure is followed in which the diluent and carboxylic anhydride which is present in excess, as well as the carboxylic acid which is formed, are removed by distillation or by washing with an organic solvent or with water.
Process (C) is characterized in that compounds of the formula (Ia) are reacted with chloroformic esters of the formula (V).
If, in the reaction of process (C) according to the invention, the corresponding chloroformic esters are used, then the acid-binding agents which are suitable are all customary acid acceptors. The following can preferably be used: tertiary amines such as triethylamine, pyridine, DABCO, DBC, DBA, Hunig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate.
When the chloroformic esters are used, then suitable diluents are all solvents which are inert towards these compounds. The following can preferably be used: hydrocarbons such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, in addition ketones such as acetone and methyl isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic esters such as ethyl acetate and also strongly polar solvents such as dimethyl sulphoxide and sulpholane.
When the chloroformic esters are used as carboxylic acid derivatives of the formula (V), the reaction temperatures can be varied within a substantial range when carrying out process (C) according to the invention. If the process is carried out in the presence of a diluent and of an acid-binding agent, the reaction temperatures are generally between -20.degree. C. and +100.degree. C., preferably between 0.degree. C. and 50.degree. C.
Process (C) according to the invention is generally carried out under atmospheric pressure.
When carrying out process (C) according to the invention, the starting substances of the formula (Ia) and the corresponding chloroformic ester of the formula (V) are generally used in approximately equivalent amounts. However, it is also possible to employ one or the other component in a larger excess (up to 2 moles). Working-up is then carried out by customary methods. In general, a procedure is followed in which salts which have precipitated are removed and the reaction mixture which remains is concentrated by stripping off the diluent.
Process (D) is characterized in that compounds of the formula (Ia) are reacted with metal hydroxides (VI) or amines (VII).
Diluents which can be employed in the process according to the invention are preferably ethers such as tetrahydrofuran, dioxane or diethyl ether, or, alternatively, alcohols such as methanol, ethanol or isopropanol, and also water. In general, process (D) according to the invention is carried out under atmospheric pressure. In general, the reaction temperatures are between -20.degree. C. and 100.degree. C., preferably between 0.degree. C. and 50.degree. C.
When carrying out process (D) according to the invention, the starting substances of the formula (Ia) or (VI or (VII) are generally employed in approximately equimolar amounts. However, it is also possible to employ one or the other component in a larger excess (up to 2 moles). In general, a procedure is followed in which the reaction mixture is concentrated by stripping off the diluent.

PREPARATION EXAMPLES
Example 1 ##STR25##
124.9 g (0.428 mol) of N-(2,4,6-trimethylphenylacetyl)-valine methyl ester are suspended in 430 ml of absolute toluene. 51.6 g of potassium tert.-butylate (95%) are added, and the mixture is then refluxed while TLC checks are carried out. The mixture is stirred into 500 ml of ice-water, the toluene is removed, and the aqueous phase is added dropwise at 0.degree.-20.degree. C. to 600 ml of 1N HCl. The precipitate is filtered off with suction, dried and recrystallized from chloroform/methyl tert.-butyl ether/n-hexane.
Yield: 51.5 g (=46.4% of theory) of the illustrated compound M.p. 126.degree. C.
Example 2 ##STR26##
5.46 g (20 mmol) of 5-isobutyl-3-(2,4,6-trimethylphenyl)-pyrrolidine-2,4-dione are suspended in 70 ml of methyl tert.-butyl ether, and 3.4 ml (20 mmol) of Hunig base are added. 2.52 ml (20 mmol) of pivaloyl chloride in 5 ml of methyl tert.-butyl ether are added dropwise at 0.degree.-10.degree. C., and stirring is subsequently continued while carrying out thin-layer chromatography checks. The precipitate is filtered off with suction and rinsed, and the filtrate is evaporated on a rotary evaporator. Column chromatography on silica gel with cyclohexane/ethyl acetate 1:1 and crystallization from methyl tert.-butyl ether/n-hexane gave 2.14 g (29.9% of theory) of the illustrated compound of melting point 154.degree. C.
Example 3 ##STR27##
4.19 g (20 mmol) of 5-isopropyl-3-(2,4,6-trimethylphenyl)-pyrrolidine-2,4-dione are suspended in 70 ml of methyl tert.-butyl ether, and 3.4 ml (20 mmol) of Hunig based are added. 1.92 ml (20 mmol) of ethyl chloroformate in 5 ml of methyl tert.-butyl ether are added dropwise at -70.degree. C., and the mixture is allowed to come to room temperature. It is evaporated on a rotary evaporator, and the residue is then taken up in methylene chloride, and the mixture is washed with water, dried and again evaporated on a rotary evaporator. Crystallization from methyl tert.-butyl ether/n-hexane gives 2.6 g (=39.3% of theory) of the illustrated compound of melting point 190.degree. C.
The following compounds of Tables 1, 2 and 3 can be prepared similarly to Examples 1, 2 and 3, respectively:
TABLE 1______________________________________ ##STR28## (Ia)Ex.-No. X Y Z.sub.n A B Mp .degree.C.______________________________________ 4 Cl Cl H H H 5 Cl Cl H CH.sub.3 H 6 Cl Cl H CH(CH.sub.3).sub.2 H 7 Cl Cl H CH.sub.3 CH.sub.3 8 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 9 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.510 Cl Cl H C.sub.3 H.sub.7 CH.sub.311 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.312 Cl Cl H (CH.sub.2).sub.213 Cl Cl H (CH.sub.2).sub.414 Cl Cl H (CH.sub.2).sub.515 Cl Cl H C.sub.2 H.sub.5 H16 Cl Cl H C(CH.sub.3).sub.3 H17 Cl Cl H CH.sub.2 CH(CH.sub.3).sub.2 H18 Cl Cl H ##STR29## H19 Cl Cl H CH.sub.2CH.sub.2SCH.sub.3 H20 Cl Cl H CH.sub.2SCH.sub.3 H21 Cl Cl H CH.sub.2SCH.sub.2C.sub.6 H.sub.5 H22 Cl Cl H CH.sub.2C.sub.6 H.sub.523 Cl Cl H ##STR30## H24 Cl Cl H ##STR31## H25 Cl H 6-Cl H H26 Cl H 6-Cl CH.sub.3 H27 Cl H 6-Cl CH(CH.sub.3).sub.2 H28 CH.sub.3 CH.sub.3 H H H29 CH.sub.3 CH.sub.3 H CH.sub.3 H30 CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 H31 CH.sub.3 CH.sub.3 6-CH.sub.3 H H32 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H >23033 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 22334 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.335 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.536 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.337 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.338 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2 22539 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.440 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.541 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 H42 CH.sub.3 CH.sub.3 6-CH.sub.3 C(CH.sub.3).sub.3 H43 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H >22044 CH.sub.3 CH.sub.3 6-CH.sub.3 ##STR32## H45 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2CH.sub.2SCH.sub.3 H46 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2SCH.sub.3 H47 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2SCH.sub.2C.sub.6 H.sub.5 H48 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2C.sub.6 H.sub.549 CH.sub.3 CH.sub.3 6-CH.sub.3 ##STR33## H50 CH.sub.3 CH.sub.3 6-CH.sub.3 ##STR34## H______________________________________
TABLE 2__________________________________________________________________________ ##STR35## (Ib)Ex.-No. X Y Z.sub.n A B R.sup.1 Mp .degree.C.__________________________________________________________________________51 Cl Cl H H H CH.sub.352 Cl Cl H CH.sub.3 H CH.sub.353 Cl Cl H CH.sub.3 H C(CH.sub.3).sub.354 Cl Cl H CH.sub.3 CH.sub.3 CH.sub.355 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.2 CH56 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 C57 Cl Cl H CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.358 Cl Cl H CH.sub.3 CH.sub.3 ##STR36##59 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.260 Cl Cl H CH.sub.3 CH.sub.3 ##STR37##61 Cl Cl H CH.sub.3 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.862 Cl Cl H CH.sub.3 CH.sub.3 ##STR38##63 Cl Cl H CH.sub.3 CH.sub.3 ##STR39##64 Cl Cl H CH.sub.3 CH.sub.3 ##STR40##65 Cl Cl H CH.sub.3 CH.sub.3 ##STR41##66 Cl Cl H CH.sub.3 CH.sub.3 ##STR42##67 Cl Cl H CH.sub.3 CH.sub.3 ##STR43##68 Cl Cl H CH.sub.3 CH.sub.3 H.sub.3 CSCH.sub.269 Cl Cl H CH.sub.3 CH.sub.3 ##STR44##70 Cl Cl H CH.sub.3 CH.sub.3 ##STR45##71 Cl Cl H CH.sub.3 CH.sub.3 ##STR46##72 Cl Cl H CH.sub.3 CH.sub.3 ##STR47##73 Cl Cl H CH.sub.3 CH.sub.3 ##STR48##74 Cl Cl H CH.sub.3 CH.sub.3 ##STR49##75 Cl Cl H CH.sub.3 CH.sub.3 ##STR50##76 Cl Cl H CH.sub.3 CH.sub.3 ##STR51##77 Cl Cl H CH.sub.3 CH.sub.3 ##STR52##78 Cl Cl H CH.sub.3 CH.sub.3 ##STR53##79 Cl Cl H CH.sub.3 CH.sub.3 ##STR54##80 Cl Cl H CH.sub.3 CH.sub.3 ##STR55##81 Cl Cl H CH.sub.3 CH.sub.3 ##STR56##82 Cl Cl H CH.sub.3 CH.sub.3 ##STR57##83 Cl Cl H CH.sub.3 CH.sub.3 ##STR58##84 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 CH.sub.385 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.2 CH86 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 C87 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 (CH.sub.2).sub.388 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR59##89 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.290 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR60##91 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.892 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR61##93 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR62##94 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR63##95 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR64##96 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR65##97 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR66##98 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 H.sub.3 CSCH.sub.299 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR67##100 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR68##101 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR69##102 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR70##103 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR71##104 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR72##105 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR73##106 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR74##107 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR75##108 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR76##109 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR77##110 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR78##111 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR79##112 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR80##113 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR81##114 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3115 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CH116 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 C117 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 (CH.sub.2).sub.3118 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR82##119 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 CCH.sub.2120 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR83##121 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.2).sub.8122 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR84##123 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR85##124 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR86##125 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR87##126 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR88##127 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR89##128 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H.sub.3 CSCH.sub.2129 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR90##130 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR91##131 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR92##132 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR93##133 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR94##134 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR95##135 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR96##136 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR97##137 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR98##138 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR99##139 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR100##140 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR101##141 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR102##142 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR103##143 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR104##144 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 CH.sub.3145 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH146 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C147 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 (CH.sub.2 ).sub.3148 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR105##149 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2150 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR106##151 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.8152 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR107##153 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR108##154 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR109##155 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR110##156 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR111##157 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR112##158 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 H.sub.3 CSCH.sub.2159 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR113##160 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR114##161 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR115##162 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR116##163 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR117##164 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR118##165 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR119##166 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR120##167 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR121##168 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR122##169 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR123##170 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR124##171 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR125##172 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR126##173 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR127##174 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3175 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH176 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C177 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 (CH.sub.2).sub.3178 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR128##179 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2180 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR129##181 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.8182 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR130##183 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR131##184 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR132##185 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR133##186 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR134##187 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR135##188 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 H.sub.3 CSCH.sub.2189 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR136##190 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR137##191 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR138##192 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR139##193 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR140##194 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR141##195 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR142##196 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR143##197 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR144##198 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR145##199 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR146##200 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR147##201 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR148##202 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR149##203 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR150##204 Cl Cl H (CH.sub.2).sub.4 CH.sub.3205 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.2 CH206 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.3 C207 Cl Cl H (CH.sub.2).sub.4 CH.sub.3 (CH.sub.2).sub.3208 Cl Cl H (CH.sub.2).sub.4 ##STR151##209 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.3 CCH.sub.2210 Cl Cl H (CH.sub.2).sub.4 ##STR152##211 Cl Cl H (CH.sub.2).sub.4 CH.sub.2 CH(CH.sub.2).sub.8212 Cl Cl H (CH.sub.2).sub.4 ##STR153##213 Cl Cl H (CH.sub.2).sub.4 ##STR154##214 Cl Cl H (CH.sub.2).sub.4 ##STR155##215 Cl Cl H (CH.sub.2).sub.4 ##STR156##216 Cl Cl H (CH.sub.2).sub.4 ##STR157##217 Cl Cl H (CH.sub.2).sub.4 ##STR158##218 Cl Cl H (CH.sub.2).sub.4 H.sub.3 CSCH.sub.2219 Cl Cl H (CH.sub.2).sub.4 ##STR159##220 Cl Cl H (CH.sub.2).sub.4 ##STR160##221 Cl Cl H (CH.sub.2).sub.4 ##STR161##222 Cl Cl H (CH.sub.2).sub.4 ##STR162##223 Cl Cl H (CH.sub.2).sub.4 ##STR163##224 Cl Cl H (CH.sub.2).sub.4 ##STR164##225 Cl Cl H (CH.sub.2).sub.4 ##STR165##226 Cl Cl H (CH.sub.2).sub.4 ##STR166##227 Cl Cl H (CH.sub.2).sub.4 ##STR167##228 Cl Cl H (CH.sub.2).sub.4 ##STR168##229 Cl Cl H (CH.sub.2).sub.4 ##STR169##230 Cl Cl H (CH.sub.2).sub.4 ##STR170##231 Cl Cl H (CH.sub.2).sub.4 ##STR171##232 Cl Cl H (CH.sub.2).sub.4 ##STR172##233 Cl Cl H (CH.sub.2).sub.4 ##STR173##234 Cl Cl H (CH.sub.2).sub.5 CH.sub.3235 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.2 CH236 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.3 C237 Cl Cl H (CH.sub.2).sub.5 CH.sub.3 (CH.sub.2).sub.3238 Cl Cl H (CH.sub.2).sub.5 ##STR174##239 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.3 CCH.sub.2240 Cl Cl H (CH.sub.2).sub.5 ##STR175##241 Cl Cl H (CH.sub.2).sub.5 CH.sub.2 CH(CH.sub.2).sub.8242 Cl Cl H (CH.sub.2).sub.5 ##STR176##243 Cl Cl H (CH.sub.2).sub. 5 ##STR177##244 Cl Cl H (CH.sub.2).sub.5 ##STR178##245 Cl Cl H (CH.sub.2).sub.5 ##STR179##246 Cl Cl H (CH.sub.2).sub.5 ##STR180##247 Cl Cl H (CH.sub.2).sub.5 ##STR181##248 Cl Cl H (CH.sub.2).sub.5 H.sub.3 CSCH.sub.2249 Cl Cl H (C.sub.2 H.sub.2).sub.5 ##STR182##250 Cl Cl H (CH.sub.2).sub.5 ##STR183##251 Cl Cl H (CH.sub.2).sub.5 ##STR184##252 Cl Cl H (CH.sub.2).sub.5 ##STR185##253 Cl Cl H (CH.sub.2).sub.5 ##STR186##254 Cl Cl H (CH.sub.2).sub.5 ##STR187##255 Cl Cl H (CH.sub.2).sub.5 ##STR188##256 Cl Cl H (CH.sub.2).sub.5 ##STR189##257 Cl Cl H (CH.sub.2).sub.5 ##STR190##258 Cl Cl H (CH.sub.2).sub.5 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C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 (CH.sub.2).sub.3422 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR293##423 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2424 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR294##425 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.8426 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR295##427 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR296##428 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR297##429 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR298##430 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR299##431 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR300##432 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 H.sub.3 CSCH.sub.2433 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR301##434 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR302##435 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR303##436 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR304##437 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR305##438 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR306##439 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR307##440 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR308##441 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR309##442 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR310##443 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR311##444 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR312##445 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR313##446 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR314##447 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR315##448 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3449 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH450 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C451 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3 (CH.sub.2).sub.3452 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR316##453 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2454 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR317##455 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.2 CH(CH.sub.2).sub.8456 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR318##457 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR319##458 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR320##459 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR321##460 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR322##461 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR323##462 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 H.sub.3 CSCH.sub.2463 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR324##464 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR325##465 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR326##466 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR327##467 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR328##468 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR329##469 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR330##470 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR331##471 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR332##472 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR333##473 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR334##474 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR335##475 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR336##476 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR337##477 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 H ##STR338##478 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 CH.sub.3479 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.2 CH480 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.3 C481 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 CH.sub.3 (CH.sub.2).sub.3482 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR339##483 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.3 CCH.sub.2484 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR340##485 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 CH.sub.2 CH(CH.sub.2).sub.8486 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR341##487 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR342##488 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR343##489 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR344##490 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR345##491 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR346##492 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 H.sub.3 CSCH.sub.2493 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR347##494 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR348##495 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR349##496 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR350##497 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR351##498 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR352##499 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR353##500 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR354##501 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR355##502 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR356##503 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR357##504 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR358##505 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR359##506 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR360##507 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR361##508 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 CH.sub.3509 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.2 CH510 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.3 C511 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 CH.sub.3 (CH.sub.2).sub.3512 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR362##513 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.3 CCH.sub.2514 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR363##515 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 CH.sub.2 CH(CH.sub.2).sub.8516 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR364##517 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR365##518 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR366##519 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR367##520 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR368##521 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR369##522 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 H.sub.3 CSCH.sub.2523 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR370##524 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR371##525 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR372##526 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR373##527 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR374##528 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR375##529 CH.sub. 3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR376##530 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR377##531 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR378##532 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR379##533 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR380##534 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR381##535 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR382##536 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR383##537 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR384##__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR385## (Ic)Ex.-No. X Y Z.sub.n A B R.sup.2 Mp .degree.C.__________________________________________________________________________538 Cl Cl H CH.sub.3 CH.sub.3 CH.sub.3539 Cl Cl H CH.sub.3 CH.sub.3 C.sub.2 H.sub.5540 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.2 CH541 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2542 Cl Cl H CH.sub.3 CH.sub.3 ##STR386##543 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 C544 Cl Cl H CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2545 Cl Cl H CH.sub.3 CH.sub.3 ##STR387##546 Cl Cl H CH.sub.3 CH.sub.3 ##STR388##547 Cl Cl H CH.sub.3 CH.sub.3 ##STR389##548 Cl Cl H CH.sub.3 CH.sub.3 ##STR390##549 Cl Cl H CH.sub.3 CH.sub.3 ##STR391##550 Cl Cl H CH.sub.3 CH.sub.3 ##STR392##551 Cl Cl H CH.sub.3 CH.sub.3 ##STR393##552 Cl Cl H CH.sub.3 CH.sub.3 ##STR394##553 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3554 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5555 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3 ).sub.2 CH556 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2557 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR395##558 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 C559 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2560 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR396##561 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR397##562 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR398##563 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR399##564 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR400##565 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR401##566 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR402##567 Cl Cl H C.sub.2 H.sub.5 CH.sub.3 ##STR403##568 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3569 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5570 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CH571 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CHCH.sub.2572 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR404##573 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 C574 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 CCH.sub.2575 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR405##576 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR406##577 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR407##578 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR408##579 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR409##580 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR410##581 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR411##582 Cl Cl H C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR412##583 Cl Cl H C.sub.3 H.sub.7 CH.sub. 3 CH.sub.3584 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 C.sub.2 H.sub.5585 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH586 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2587 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR413##588 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C589 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2590 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR414##591 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR415##592 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR416##593 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR417##594 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR418##595 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR419##596 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR420##597 Cl Cl H C.sub.3 H.sub.7 CH.sub.3 ##STR421##598 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3699 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 C.sub.2 H.sub.5600 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH601 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2602 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR422##603 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C604 Cl Cl H i-C.sub.3 H.sub.7 CH.sub. 3 (CH.sub.3).sub.3 CCH.sub.2605 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR423##606 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR424##607 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR425##608 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR426##609 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR427##610 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR428##611 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR429##612 Cl Cl H i-C.sub.3 H.sub.7 CH.sub.3 ##STR430##613 Cl Cl H (CH.sub.2).sub.4 CH.sub.3614 Cl Cl H (CH.sub.2).sub.4 C.sub.2 H.sub.5615 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.2 CH616 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.2 CHCH.sub.2617 Cl Cl H (CH.sub.2).sub.4 ##STR431##618 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.3 C619 Cl Cl H (CH.sub.2).sub.4 (CH.sub.3).sub.3 CCH.sub.2620 Cl Cl H (CH.sub.2).sub.4 ##STR432##621 Cl Cl H (CH.sub.2).sub.4 ##STR433##622 Cl Cl H (CH.sub.2).sub.4 ##STR434##623 Cl Cl H (CH.sub.2).sub.4 ##STR435##624 Cl Cl H (CH.sub. 2).sub.4 ##STR436##625 Cl Cl H (CH.sub.2).sub.4 ##STR437##626 Cl Cl H (CH.sub.2).sub.4 ##STR438##627 Cl Cl H (CH.sub.2).sub.4 ##STR439##628 Cl Cl H (CH.sub.2).sub.5 CH.sub.3629 Cl Cl H (CH.sub.2).sub.5 C.sub.2 H.sub.5630 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.2 CH631 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.2 CHCH.sub.2632 Cl Cl H (CH.sub.2).sub.5 ##STR440##633 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.3 C634 Cl Cl H (CH.sub.2).sub.5 (CH.sub.3).sub.3 CCH.sub.2635 Cl Cl H (CH.sub.2).sub.5 ##STR441##636 Cl Cl H (CH.sub.2).sub.5 ##STR442##637 Cl Cl H (CH.sub.2).sub.5 ##STR443##638 Cl Cl H (CH.sub.2).sub.5 ##STR444##639 Cl Cl H (CH.sub.2).sub.5 ##STR445##640 Cl Cl H (CH.sub.2).sub.5 ##STR446##641 Cl Cl H (CH.sub.2).sub.5 ##STR447##642 Cl Cl H (CH.sub.2).sub.5 ##STR448##643 Cl Cl 6-Cl H H CH.sub.3644 Cl Cl 6-Cl CH.sub.3 H CH.sub.3645 Cl Cl 6-Cl CH.sub.3 H CH(CH.sub.3).sub.2646 Cl Cl 6-Cl CH.sub.3 H CH.sub.2 C(CH.sub.3).sub.3647 CH.sub.3 CH.sub.3 H H H CH.sub.3648 CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.3649 CH.sub.3 CH.sub.3 H CH.sub.3 H CH(CH.sub.3).sub.2650 CH.sub.3 CH.sub.3 H CH.sub.3 H CH.sub.2 C(CH.sub.3).sub.3651 CH.sub.3 CH.sub.3 6-CH.sub.3 H H CH.sub.3652 CH.sub.3 CH.sub.3 6-CH.sub.3 H H C.sub.2 H.sub.5653 CH.sub.3 CH.sub.3 6-CH.sub.3 H H CH(CH.sub.3).sub.2654 CH.sub.3 CH.sub.3 6-CH.sub.3 H H ##STR449##655 CH.sub.3 CH.sub.3 6-CH.sub.3 H H CH.sub.2C(CH.sub.3).sub.3656 CH.sub.3 CH 6-CH.sub.3 H H (CH.sub.2).sub.2 OC.sub.2 H.sub.5657 CH.sub.3 CH.sub.3 6-CH.sub.3 H H ##STR450##658 CH.sub.3 CH.sub.3 6-CH.sub.3 H H ##STR451##659 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H CH.sub.3660 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H C.sub.2 H.sub.5661 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2662 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H ##STR452##663 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H CH.sub.2 C(CH.sub.3).sub.3664 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H (CH.sub.2).sub.2 OC.sub.2 H.sub.5665 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H ##STR453##666 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 H ##STR454##667 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3668 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H C.sub.2 H.sub.5669 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2670 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H ##STR455##671 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.2 C(CH.sub.3).sub.3672 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H (CH.sub.2).sub.2 OC.sub.2 H.sub.5673 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH.sub.3).sub.2 H ##STR456##674 CH.sub.3 CH.sub.3 6-CH.sub.3 CH(CH).sub.2 H ##STR457##675 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H CH.sub.3676 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H C.sub.2 H.sub.5677 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H CH(CH.sub.3).sub.2678 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H CH.sub.2 CH(CH.sub.3).sub.2679 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H ##STR458##680 CH.sub. 3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H CH.sub.2 C(CH.sub.3).sub.3681 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H (CH.sub.2).sub.2 OC.sub.2 H.sub.5682 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H ##STR459##683 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2 H ##STR460##684 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H CH.sub.3685 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H C.sub.2 H.sub.5686 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H CH(CH.sub.3).sub.2687 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H ##STR461##688 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H CH.sub.2 C(CH.sub.3).sub.3689 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H (CH.sub.2).sub. 2 OC.sub.2 H.sub.5690 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H ##STR462##691 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.2SCH.sub.3 H ##STR463##692 CH.sub.3 H 6-CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3693 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 140694 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.3).sub.2 CH 161-163695 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2696 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR464## 98697 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 C698 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2699 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR465##700 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR466##701 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR467##702 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR468##703 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR469##704 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR470##705 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR471##706 CH.sub.3 CH.sub.3 6-CH.sub.3 CH.sub.3 CH.sub.3 ##STR472##707 CH.sub.3 H 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3708 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5709 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.2 CH710 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2711 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR473##712 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 C713 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2714 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR474##715 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR475##716 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR476##717 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR477##718 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR478##719 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR479##720 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR480##721 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 ##STR481##722 CH.sub.3 H 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3723 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5724 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CH725 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CHCH.sub.2726 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub. 5 C.sub.2 H.sub.5 ##STR482##727 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 C728 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.3).sub.3 CCH.sub.2729 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR483##730 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR484##731 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR485##732 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR486##733 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR487##734 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR488##735 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR489##736 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR490##737 CH.sub.3 H 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 CH.sub.3738 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 C.sub.2 H.sub.5739 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH740 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2741 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR491##742 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C743 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2744 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR492##745 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 C.sub.2 H.sub.5 ##STR493##746 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR494##747 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR495##748 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR496##749 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR497##750 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR498##751 CH.sub.3 CH.sub.3 6-CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 ##STR499##752 CH.sub.3 H 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 CH.sub.3753 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 C.sub.2 H.sub.5754 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CH755 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2756 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR500##757 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 C758 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 (CH.sub.3).sub.3 CCH.sub.2759 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR501##760 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR502##761 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR503##762 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR504##763 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR505##764 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR506##765 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR507##766 CH.sub.3 CH.sub.3 6-CH.sub.3 i-C.sub.3 H.sub.7 CH.sub.3 ##STR508##767 CH.sub.3 H 6-CH.sub.3 (CH.sub.2).sub.4 CH.sub.3768 CH.sub.3 CH.sub.3 6-CH.sub. 3 (CH.sub.2).sub.4 C.sub.2 H.sub.5769 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.2 CH770 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.2 CHCH.sub.2771 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR509##772 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.3 C773 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 (CH.sub.3).sub.3 CCH.sub.2774 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR510##775 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR511##776 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR512##777 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR513##778 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR514##779 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR515##780 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR516##781 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.4 ##STR517##782 CH.sub.3 H 6-CH.sub.3 (CH.sub.2).sub.5 CH.sub.3783 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 C.sub.2 H.sub.5784 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.2 CH785 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.2 CHCH.sub.2786 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR518##787 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.3 C788 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 (CH.sub.3).sub.3 CCH.sub.2789 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR519##790 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR520##791 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR521##792 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR522##793 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR523##794 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR524##795 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR525##796 CH.sub.3 CH.sub.3 6-CH.sub.3 (CH.sub.2).sub.5 ##STR526##__________________________________________________________________________
Example (II1) ##STR527##
138 g (0.5 mol) of N-(2,4,6-trimethylphenyl-acetyl)-valine are suspended in 500 ml of methanol, 73 ml (0.55 mol) of dimethoxypropane are added, 4.75 g (25 mmol) of p-toluenesulphonic acid monohydrate are added, and the mixture is then refluxed while thin-layer chromatography (TLC) checks are carried out.
After the solvent has been removed by evaporation on the rotary evaporator, the residue is taken up in methylene chloride, and the mixture is washed with sodium hydrogen carbonate solution, dried and evaporated on a rotary evaporator.
Yield: 127.6 g (=88% of theory).
Example (IIa1) ##STR528##
10 g (0.25 mol) of NaOH tablets are added to 58.8 g (0.5 mol) of L-valine in 720 ml of water. Thereafter, 30 g (0.75 mol) of NaOH tablets in 150 ml of water and 98.2 g (0.5 mol) of mesityleneacetyl chloride are synchronously added dropwise in such a way that the temperature, does not exceed 40.degree. C. After 1 h, the mixture is acidified with concentrated hydrochloric acid at 0.degree.-20.degree. C., the product is filtered off with suction and dried in vacuo at 70.degree. C. over diphosphorus pentoxide.
Yield: 138 g (=100% of theory) m.p. 140.degree. C.
The active compounds of the formula (I) according to the invention are suitable for combating animal pests, in particular of the class of the Arachnida and the order of the mites (Acarina) which occur in agriculture, in forestry, in the protection of stored goods and materials, and in the hygiene field, these active substances being well tolerated by plants and having a favourable toxicity towards warm-blooded species. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Acarina, for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp..
The active substances according to the invention are not only active against pests of plants, the hygiene field and of stored goods, but also in the veterinary medicine sector against parasites of animals (ectoparasites) such as scaly ticks, argasidae, scab mites and trombedae.
They are active against normally-sensitive and resistant species and strains and against all parasitizing and non-parasitizing development stages of the ectoparasites.
The active substances according to the invention are distinguished by a high acaricidal activity. They can be employed with particularly good success against mites which are injurious to plants, such as, for example, against the common spider mite (Tetranychus urticae).
The active compounds according to the invention can furthermore be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
It is characteristic of the compounds according to the invention that they have a selective activity against monocotyledon weeds when used pre- and post-emergence, while being well tolerated by crop plants.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
In this context, the active compounds according to the invention show, besides an outstanding action against harmful plants, a good tolerance by important crop plants such as, for example wheat, cotton, soya beans, citrus fruit and sugar beet, and they can therefore be employed as selective weed killers.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with active compounds, very fine capsules in polymeric substances and in coating compositions for seed, furthermore in formulation with burning equipment such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold-mist and warm-mist formulations.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents, liquefied gases under pressure and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at room temperature and atmospheric pressure, for example aerosol propellants, such as halogenohydrocarbons and also butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations as a mixture with other active substances such as insecticides, attractants, sterilants, acaricides, nematicides, herbicides or fungicides. The insecticides include, for example, phosphates, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
Furthermore, the active substances according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations as a mixture with synergists. Synergists are compounds by which the action of the active substances is increased without it being necessary for the synergist added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
The active substances according to the invention are also suitable for combating mites, ticks, etc. in the sectors of animal keeping and cattle breeding; better results, for example higher milk production, greater weight, more attractive animal pelt, longer life, etc., can be achieved by combating the pests.
The application of the active compounds according to the invention occurs in this sector in a known fashion, such as by oral application in the form of, for example, tablets, capsules, potions, granules, by means of dermal or external application in the form of, for example, dipping, spraying, pouring-on, spotting on and dusting, as well as by means of parenteral application in the form of, for example, injection and, furthermore, by means of the feed-through process. In addition, application as moulded articles (collar, ear tag) is also possible.
In the biological examples listed below, the following compounds were used as comparison substances: ##STR529## disclosed in DE-A 2,361,084 and U.S. Pat. No. 4,632,698 ##STR530## disclosed in DE-A 2,361,084 and U.S. Pat. No. 4,632,698 ##STR531## disclosed in DE-A 2,361,084 and U.S. Pat. No. 4,632,698
Example A
Phaedon larvae test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of the active compound of the desired concentration and are infested with mustard beetle larvae (Phaedon cochleariae), while the leaves are still moist.
After the desired time, the destruction in % is determined. 100% means that all the beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of the Preparation Examples: (1), (2), (32), (40), (278), (280), (290), (299).
Example B
Plutella test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are infested with caterpillars of the diamond-back moth (Plutella maculipennis) while the leaves are still moist.
After the desired time, the destruction in % is determined. 100% means that all the caterpillars have been killed; 0% means that none of the caterpillars have been killed.
In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of the Preparation Examples: (1), (32), (283), (299).
Example C
Nephotettix test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Rice seedlings (Oryza sativa) are treated by being dipped into the preparation of active compound of the desired concentration and are infested with larvae of the green rice leaf-hopper (Nephotettix cincticepa) while the seedlings are still moist.
After the desired time, the destruction in % is determined. 100% means that all the leaf-hoppers have been killed; 0% means that none of the leaf-hoppers have been killed.
In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of the Preparation Examples: (1), (32), (43), (290), (292), (299), (301).
Example D
Pre-emergence test
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in standard soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0%=no action (like untreated control)
100%=total destruction
In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of the Preparation Examples: (32), (281), (283).
Example E
Post-emergence test
Solvent: 7 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 l of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote:
0%=no action (like untreated control)
100%=total destruction
In this test, a superior activity compound with the prior art is shown, for example, by the following compounds of the Preparation Examples: (32), (281), (283).
Example F
Tetranychus test (OP resistant)
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water containing emulsifier to the desired concentration.
Bean plants (Phaseolus vulgaris) which are heavily infested with all development stages of the common spider mite or greenhouse red spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration until dripping wet.
After the desired time, the action in % is determined. 100% means that all the spider mites have been killed; 0% means that none of the spider mites have been killed.
In this test, a superior activity compared with the prior art is shown, for example, by the following compounds of the Preparation Examples: (281), (283).
It is understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.

Number	Date	Country	Kind
4014941	May 1990	DEX
4107394	Mar 1991	DEX

Number	Name	Date	Kind
3272842	Easton et al.	Sep 1966
4632698	Wheeler	Dec 1986

Number	Date	Country
0377893	Dec 1989	EPX
0415185	Aug 1990	EPX
0423482	Sep 1990	EPX
2361084	Dec 1973	DEX
8804652	Dec 1987	WOX

Insecticidal, acaricidal and herbicidal 1-H-3-aryl-pyrrolidine-2,4-dione derivatives

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