U.S. patent application number 10/644298 was filed with the patent office on 2004-02-26 for process for the preparation of pesticides.
Invention is credited to Farooq, Saleem, Trah, Stephan, Ziegler, Hugo, Zurfluh, Rene.
Application Number | 20040039220 10/644298 |
Document ID | / |
Family ID | 4256517 |
Filed Date | 2004-02-26 |
United States Patent
Application |
20040039220 |
Kind Code |
A1 |
Farooq, Saleem ; et
al. |
February 26, 2004 |
Process for the preparation of pesticides
Abstract
The invention relates to a process for the preparation of
compounds of the formula 1 or, if appropriate, a tautomer thereof,
in each case in the free form or in salt form, in which A, X, Y, Z,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.7, R.sub.9 and n are as
defined in claim 1 and the C.dbd.N double bond marked with E has
the E configuration, which comprises a1) reacting either a compound
of the formula (II) mentioned above with a compound of the formula
(III) mentioned above, in which X.sub.1 is a leaving group, or a2)
a compound of the formula (IV) mentioned above, if appropriate in
the presence of a base, with a compound of the formula (V)
mentioned above, or b1) reacting a compound of the formula (VI)
mentioned above with a compound of the formula R.sub.7-A-X.sub.2
(VII), in which X.sub.2 is a leaving group, and either further
reacting the compound thus obtainable, of the formula (IV), for
example according to method a2), or b2) reacting it with
hydroxylamine or a salt thereof, if appropriate in the presence of
a basic or acid catalyst, and further reacting the compound thus
obtainable, of the formula (II), for example according to method
a1), or c) reacting a compound of the formula (VIII), mentioned
above with a C.sub.1-C.sub.6alkyl nitrite and further reacting the
compound thus obtainable, of the formula (VI), for example
according to method b), the E isomers of the compounds of the
formulae (II), (IV) and (VI), a process for their preparation and
their use for the preparation of compounds of the formula (I).
Inventors: |
Farooq, Saleem; (Arisdorf,
CH) ; Trah, Stephan; (Freiburg, DE) ; Ziegler,
Hugo; (Witterswil, CH) ; Zurfluh, Rene;
(Basle, CH) |
Correspondence
Address: |
BAYER POLYMERS LLC
100 BAYER ROAD
PITTSBURGH
PA
15205
US
|
Family ID: |
4256517 |
Appl. No.: |
10/644298 |
Filed: |
August 19, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10644298 |
Aug 19, 2003 |
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09670147 |
Sep 26, 2000 |
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6646151 |
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09670147 |
Sep 26, 2000 |
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08762217 |
Dec 6, 1996 |
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6156923 |
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Current U.S.
Class: |
558/12 ; 558/390;
560/35 |
Current CPC
Class: |
C07C 249/12 20130101;
C07C 251/60 20130101; C07C 251/48 20130101 |
Class at
Publication: |
558/12 ; 558/390;
560/35 |
International
Class: |
C07C 331/08; C07C
255/61; C07C 251/44 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 7, 1995 |
CH |
3464/95 |
Claims
What is claimed is:
1. A process for the preparation of a compound of the formula
13and, where appropriate, their tautomers, in each case in the free
form or salt form, in which either X is CH or N, Y is OR.sub.1 and
Z is O, or X is N, Y is NHR.sub.8 and Z is O, S or S(.dbd.O);
R.sub.1 is C.sub.1-C.sub.4alkyl; R.sub.2 is H,
C.sub.1-C.sub.4alkyl, halogeno-C.sub.1-C.sub.4alkyl,
C.sub.3-C.sub.6cycloalkyl or C.sub.1-C.sub.4alkoxymethyl; R.sub.3
and R.sub.4 independently of one another are H,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, OH, CN, NO.sub.2, a
(C.sub.1-C.sub.4alkyl).sub.3-Si group, where the alkyl groups can
be identical or different, halogen,
(C.sub.1-C.sub.4alkyl)S(.dbd.O).s- ub.m,
(halogeno-C.sub.1-C.sub.4alkyl)S(.dbd.O).sub.m,
halogeno-C.sub.1-C.sub.4alkyl or halogeno-C.sub.1-C.sub.4alkoxy;
R.sub.5 is C.sub.1-C.sub.6alkyl, halogeno-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkoxy, halogeno-C.sub.1-C.sub.6alkoxy,
C.sub.1-C.sub.6-alkylthio, halogen-C.sub.1-C.sub.6alkylthio,
C.sub.1-C.sub.6alkylsulfinyl,
halogeno-C.sub.1-C.sub.6-alkylsulfinyl,
C.sub.1-C.sub.6alkylsulfonyl,
halogeno-C.sub.1-C.sub.6alkylsulfonyl,
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkox- y-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkylthio-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkylthio-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkylsulfinyl-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6-alkylsulfinyl-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6-alkylcarbonyl,
halogeno-C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl,
halogeno-C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.4-alkoxyiminomethyl;
di(C.sub.1-C.sub.6alkyl)-aminocarbonyl, where the alkyl groups can
be identical or different; C.sub.1-C.sub.6-alkylaminothiocarbonyl;
di(C.sub.1-C.sub.6alkyl)-aminothiocarbonyl, where the alkyl groups
can be identical or different; C.sub.1-C.sub.6-alkylamino,
di(C.sub.1-C.sub.6alkyl)-amino, where the alkyl groups can be
identical or different; halogen, NO.sub.2, CN, SF.sub.5, thioamido,
thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted
C.sub.1-C.sub.4alkylenedioxy group, where the substituents are
selected from the group consisting of C.sub.1-C.sub.4alkyl and
halogen; or QR.sub.6, where, if n is greater than 1, the radicals
R.sub.5 can be identical or different; R.sub.6 is
C.sub.2-C.sub.6alkenyl or C.sub.2-C.sub.6 alkynyl, which are
unsubstituted or substituted by 1 to 3 halogen atoms;
(C.sub.1-C.sub.4alkyl).sub.3Si, where the alkyl groups can be
identical or different; CN; or an unsubstituted or mono- to
pentasubstituted C.sub.3-C.sub.6cycloalkyl, aryl or heterocyclyl
group, where the substituents are selected from the group
consisting of halogen, C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
halogeno-C.sub.1-C.sub.6alkoxy, phenoxy, naphthoxy and CN; A either
is a direct bond, C.sub.1-C.sub.6akylene, --C(.dbd.O)--,
--C(.dbd.S)-- or halogeno-C.sub.1-C.sub.10alkylene and R.sub.7 is a
radical R.sub.10, or is C.sub.1-C.sub.10alkylene, --C(.dbd.O)--,
--C(.dbd.S)-- or halogeno-C.sub.1-C.sub.10alkylene and R.sub.7 is
OR.sub.10, N(R.sub.10).sub.2, where the radicals R.sub.10 can be
identical or different, or --S(.dbd.O).sub.qR.sub.10; R.sub.8 is H
or C.sub.1-C.sub.4alkyl; R.sub.9 is methyl, fluoromethyl or
difluoromethyl; R.sub.10 is H; an unsubstituted or substituted
C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl or
C.sub.2-C.sub.6alkynyl group, where the substituents are selected
from the group consisting of halogen;
(C.sub.1-C.sub.4alkyl).sub.3Si, where the alkyl groups can be
identical or different; Cs-C.sub.6cyclo-alkyl, which is
unsubstituted or substituted by halogen;
C.sub.1-C.sub.6alkoxycarbonyl, which is unsubstituted or
substituted by halogen; unsubstituted or substituted aryl, where
the substituents are selected from the group consisting of halogen,
halogeno-C.sub.1-C.sub.4alkyl and CN; a (C.sub.1-C.sub.4alkyl).s-
ub.3Si group, where the alkyl groups can be identical or different;
C.sub.3-C.sub.6cycloalkyl, which is unsubstituted or substituted by
halogen; C.sub.1-C.sub.6alkoxycarbonyl which is unsubstituted or
substituted by halogen; or an unsubstituted or substituted aryl or
heterocyclyl group, where the substituents are selected from the
group consisting of halogen and halogeno-C.sub.1-C.sub.4alkyl; Q is
a direct bond, C.sub.1-C.sub.8alkylene, C.sub.2-C.sub.6alkenylene,
C.sub.2-C.sub.6alkynylene, O, O(C.sub.1-C.sub.6alkylene),
(C.sub.1-C.sub.6alkylene)O, S(.dbd.O).sub.p,
S(.dbd.O).sub.p(C.sub.1-C.su- b.6alkylene) or
(C.sub.1-C.sub.6alkylene)S(.dbd.O).sub.p; m is 0, 1 or 2; n is 0,
1, 2, 3, 4 or 5; p is 0, 1 or 2; and q is 0, 1 or 2, and the
C.dbd.N double bond marked with E has the E configuration, which
comprises a1) reacting either a compound of the formula 14in which
A, R.sub.2, R.sub.5, R.sub.7 and n are as defined for formula (I)
and the C.dbd.N double bond marked with E has the E configuration,
or a possible tautomer thereof, in each case in the free form or in
salt form, with a compound of the formula 15in which X, Y, Z,
R.sub.3, R.sub.4 and R.sub.9 are as defined for formula (I) and
X.sub.1 is a leaving group, or a tautomer thereof, in each case in
the free from or in salt form, or a2) reacting a compound of the
formula 16in which A, R.sub.2, R.sub.5, R.sub.7 and n are as
defined for formula (I) and the C.dbd.N double bond marked with E
has the E configuration, or a possible tautomer thereof, in each
case in the free form or in the salt form with a compound of the
formula 17in which X, Y, Z, R.sub.3, R.sub.4 and R.sub.9 are as
defined for formula (I), or, if appropriate, a tautomer thereof, in
each case in the free form or in salt form, or b1) reacting a
compound of the formula 18in which R.sub.2, R.sub.5 and n are as
defined for formula (I) and the C.dbd.N double bond marked with E
has the E configuration, or a possible tautomer thereof, in each
case in the free form or in salt form with a compound of the
formula R.sub.7-A-X.sub.2 (VII), in which A and R.sub.7 are as
defined for formula (I) and X.sub.2 is a leaving group, and either
further reacting the compound thus obtainable, of the formula (IV),
for example according to method a2), or b2) reacting it with
hydroxylamine or a salt thereof and further reacting the compound
thus obtainable, of the formula (II), for example according to
method a1), or c) reacting a compound of the formula 19in which
R.sub.2, R.sub.3 and n are as defined for formula (I), or a
possible tautomer thereof, in each case in the free form or in salt
form with a C.sub.1-C.sub.6alkyl nitrite and further reacting the
compound thus obtainable, of the formula (VI), for example
according to method b).
2. A process according to claim 1 for the preparation of a compound
of the formula (I), which comprises reacting a compound of the
formula (II) with a compound of the formula (III).
3. A process according to claim 2, wherein a compound of the
formula (III) in which X.sub.1 is halogen is used.
4. A process according to claim 2, wherein a compound of the
formula (III) in which X.sub.1 is chlorine is used.
5. A process according to claim 2, wherein the reaction is carried
out in the presence of a base.
6. A process according to claim 5, wherein the reaction is carried
out in the presence of a base selected from the group consisting of
alkali metal and alkaline earth metal hydroxides hydrides, amides,
alkanolates, acetates, carbonates, dialkylamides and
alkylsilylamides.
7. A process according to claim 6, wherein the base is sodium
hydride.
8. A process according to claim 2, wherein the reaction is carried
out in the presence of a solvent or diluent or of a mixture
thereof.
9. A process according to claim 8, wherein the solvent is selected
from the group consisting of N,N-dimethylformamide,
N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone
and hexamethylphosphoric acid triamide.
10. A process according to claim 9, wherein the solvent is
N,N-dimethylformamide.
11. A process according to claim 2, wherein the reaction is carried
out in a temperature range from about 10.degree. to about
30.degree..
12. A process according to claim 2, wherein the reaction time is
between about 0.5 and about 2 hours.
13. A process according to claim 1 for the preparation of a
compound of the formula (I), which comprises reacting the compound
of the formula (IV), with a compound of the formula (V).
14. A process according to claim 13, wherein the reaction is
carried out in the presence of a base.
15. A process according to claim 14, wherein the reaction is
carried out in the presence of a base selected from the group
consisting of alkali metal and alkaline earth metal hydroxides,
hydrides, amides, alkanolates, acetates, carbonates, dialkylamides
and alkylsilylamides.
16. A process according to claim 15, wherein the base is sodium
hydroxide.
17. A process according to claim 13, wherein the reaction is
carried out in the presence of a solvent or diluent or of a mixture
thereof.
18. A process according to claim 17, wherein the solvent is
selected from the group consisting of methanol, ethanol, propanol,
isopropanol, butanol, ethylene glycol and glycerol.
19. A process according to claim 18, wherein the reaction is
carried out in methanol.
20. A process according to claim 13, wherein the reaction is
carried out in a temperature range from about 10.degree. to about
30.degree..
21. A process according to claim 13, wherein the reaction time is
between about 0.5 and about 2 hours.
22. A process according to claim 1 for the preparation of a
compound of the formula (I), which comprises reacting the compound
of the formula (VI), with a compound of the formula (VII), and
either reacting the compound thus obtainable, of the formula (IV),
according to the process according to claim 13, or reacting it with
hydroxylamine or a salt thereof, if appropriate in the presence of
a basic or acid catalyst, and further reacting the compound thus
obtainable, of the formula (II), according to the process according
to claim 2.
23. A process according to claim 22, wherein a compound of the
formula (VII) in which X.sub.2 is halogen is used.
24. A process according to claim 22, wherein a compound of the
formula (VII) in which X.sub.2 is chlorine is used.
25. A process according to claim 22, wherein the reaction of the
compound of the formula (VI) with the compound of the formula (VII)
is carried out in the presence of a base.
26. A process according to claim 25, wherein the reaction is
carried out in the presence of a base selected from the group
consisting of alkali metal and alkaline earth metal hydroxides,
hydrides, amides, alkanolates, acetates, carbonates, dialkylamides
and alkylsilylamides.
27. A process according to claim 26, wherein the base is potassium
carbonate.
28. A process according to claim 22, wherein the reaction of the
compound of the formula (VI) with the compound of the formula (VII)
is carried out in the presence of a solvent or diluent or of a
mixture thereof.
29. A process according to claim 28, wherein the solvent is
selected from the group consisting of acetonitrile and
propionitrile.
30. A process according to claim 29, wherein the reaction is
carried out in acetonitrile.
31. A process according to claim 22, wherein the reaction of the
compound of the formula (VI) with the compound of the formula (VII)
is carried out in a temperature range of about 10.degree. to about
80.degree..
32. A process according to claim 22, wherein the duration of the
reaction of the compound of the formula (VI) with the compound of
the formula (VII) is between about 0.5 and about 2 hours.
33. A process according to claim 1 for the preparation of a
compound of the formula (I), which comprises reacting the compound
of the formula (VIII), with a C.sub.1-C.sub.6 alkyl nitrite and
further reacting the compound thus obtainable, of the formula (VI),
according to the process according to claim 22.
34. A process according to claim 33, wherein the reaction is
carried out in the presence of a base.
35. A process according to claim 34, wherein the reaction is
carried out in the presence of a base selected from the group
consisting of alkali metal and alkaline earth metal hydroxides,
hydrides, amides, alkanolates, acetates, carbonates, dialkylamides
and alkylsilylamides.
36. A process according to claim 35, wherein the base is sodium
methanolate.
37. A process according to claim 33, wherein the reaction is
carried out in the presence of a solvent or diluent or of a mixture
thereof.
38. A process according to claim 37, wherein the solvent is
selected from the group consisting of methanol, ethanol, propanol,
isopropanol, butanol, ethylene glycol and glycerol.
39. A process according to claim 38, wherein the reaction is
carried out in methanol.
40. A process according to claim 33, wherein the reaction is
carried out in a temperature range from about 0.degree. C. to about
60.degree. C.
41. A process according to claim 33, wherein the reaction time is
between about 0.5 and about 3 hours.
42. A process for the preparation of a compound of the formula 20in
which A, R.sub.2, R.sub.5, R.sub.7 and n are as defined for formula
(I) and the C.dbd.N double bond marked with E has the E
configuration, which comprises reacting the compound of the formula
21in which R.sub.2, R.sub.5 and n are as defined for formula (I)
and the C.dbd.N double bond marked with E has the E configuration,
with a compound of the formula R.sub.7-A-X.sub.2 (VII), in which A
and R.sub.7 are as defined for formula (I) and X.sub.2 is a leaving
group.
43. A process according to claim 42, wherein a compound of the
formula (VII) in which X.sub.2 is halogen is used.
44. A process according to claim 43, wherein a compound of the
formula (VII) in which X.sub.2 is chlorine is used.
45. A process according to claim 42, wherein the reaction is
carried out in the presence of a base.
46. A process according to claim 45, wherein the reaction is
carried out in the presence of a base selected from the group
consisting of alkali metal and alkaline earth metal hydroxides,
hydrides, amides, alkanolates, acetates, carbonates, dialkylamides
and alkylsilylamides.
47. A process according to claim 46, wherein the base is potassium
carbonate.
48. A process according to claim 47, wherein the reaction is
carried out in the presence of a solvent or diluent or of a mixture
thereof.
49. A process according to claim 48, wherein the solvent is
selected from the group consisting of acetonitrile and
propionitrile.
50. A process according to claim 49, wherein the reaction is
carried out in acetonitrile.
51. A process according to claim 42, wherein the reaction is
carried out in a temperature range from about 10.degree. to about
80.degree..
52. A process according to claim 42, wherein the reaction time is
between about 0.5 and about 2 hours.
53. A process for the preparation of a compound of the formula 22in
which A, R.sub.2, R.sub.5, R.sub.7 and n are as defined for formula
(I) and the C.dbd.N double bond marked with E has the E
configuration, which comprises reacting the compound of the formula
23in which A, R.sub.2, R.sub.5, R.sub.7 and n are as defined for
formula (I) and the C.dbd.N double bond marked with E has the E
configuration, with hydroxylamine or a salt thereof.
54. A process according to claim 53, wherein the reaction is
carried out with hydroxylamine hydrochloride.
55. A process according to claim 53, wherein the reaction is
carried out in the presence of a solvent or diluent or of a mixture
thereof.
56. A process according to claim 55, wherein the solvent is
selected from the group consisting of methanol, ethanol, propanol,
isopropanol, butanol, ethylene glycol and glycerol.
57. A process according to claim 56, wherein the reaction is
carried out in ethanol.
58. A process according to claim 53, wherein the reaction is
carried out in a temperature range from about 20.degree. to about
100.degree..
59. A process according to claim 53, wherein the reaction time is
between about 0.5 and about 2 hours.
60. A process for the preparation of a compound of the formula 24in
which R.sub.2, R.sub.5 and n are as defined for formula (I) and the
C.dbd.N double bond marked with E has the E configuration, which
comprises reacting the compound of the formula 25in which R.sub.2,
R.sub.5 and n are as defined for formula (I), with a
C.sub.1-C.sub.6alkylnitrite.
61. A process according to claim 60, wherein the reaction is
carried out in the presence of a base.
62. A process according to claim 61, wherein the reaction is
carried out in the presence of a base selected from the group
consisting of alkali metal and alkaline earth metal hydroxides,
hydrides, amides, alkanolates, acetates, carbonates, dialkylamide
and alkylsilylamides.
63. A process according to claim 62, wherein the base is sodium
methanolate.
64. A process according to claim 60, wherein the reaction is
carried out in the presence of a solvent or diluent or of a mixture
thereof.
65. A process according to claim 64, wherein the solvent is
selected from the group consisting of methanol, ethanol, propanol,
isopropanol, butanol, ethylene glycol and glycerol.
66. A process according to claim 65, wherein the reaction is
carried out in methanol.
67. A process according to claim 60, wherein the reaction is
carried out in a temperature range from about 0.degree. to about
40.degree..
68. A process according to claim 60, wherein the reaction time is
between about 0.5 and about 2 hours.
69. A compound of the formula 26in which A, R.sub.2, R.sub.5,
R.sub.7 and n are as defined in claim 1 for formula (I) and the
C.dbd.N double bond marked with E has the E configuration, or if
appropriate a tautomer thereof, in each case in the free form or in
salt form.
70. A compound of the formula 27in which A, R.sub.2, R.sub.5,
R.sub.7 and n are as defined in claim 1, for formula (I) and the
C.dbd.N double bond marked with E has the E configuration, or if
appropriate a tautomer thereof, in each case in the free form or in
salt form.
71. A compound of the formula 28in which R.sub.2, R.sub.5 and n are
as defined for formula (I) and the C.dbd.N double bond marked with
E has the E configuration, or if appropriate a tautomer thereof, in
each case in the free form or in salt form.
Description
[0001] The invention relates to a process for the preparation of
compounds of the formula 2
[0002] and, where appropriate, their tautomers, in each case in the
free form or salt form, in which either
[0003] X is CH or N, Y is OR.sub.1 and Z is 0,
[0004] or
[0005] X is N, Y is NHR.sub.8 and Z is O, S or S(.dbd.O);
[0006] R.sub.1 is C.sub.1-C.sub.4alkyl;
[0007] R.sub.2 is H, C.sub.1-C.sub.4alkyl,
halogeno-C.sub.1-C.sub.4alkyl, C.sub.3-C.sub.6cycloalkyl or
C.sub.1-C.sub.4alkoxymethyl;
[0008] R.sub.3 and R.sub.4 independently of one another are H,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, OH, CN, NO.sub.2, a
(C.sub.1-C.sub.4alkyl).sub.3--Si group, where the alkyl groups can
be identical or different, halogen,
(C.sub.1-C.sub.4alkyl)S(.dbd.O).sub.m,
(halogeno-C.sub.1-C.sub.4alkyl)S(.dbd.O).sub.m,
halogeno-C.sub.1-C.sub.4a- lkyl or
halogeno-C.sub.1-C.sub.4alkoxy;
[0009] R.sub.5 is C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
halogeno-C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6-alkylthio,
halogen-C.sub.1-C.sub.6alkylthio, C.sub.1-C.sub.6alkylsulfinyl,
halogeno-C.sub.1-C.sub.6-alkylsulfinyl,
C.sub.1-C.sub.6alkylsulfonyl,
halogeno-C.sub.1-C.sub.6alkylsulfonyl,
C.sub.1-C.sub.6alkoxy-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkox- y-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkylthio-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkylthio-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6alkylsulfinyl-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6-alkylsulfinyl-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6-alkylsulfonyl-C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.6-alkylcarbonyl,
halogeno-C.sub.1-C.sub.6-alkylcarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl,
halogeno-C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylaminocarbonyl,
C.sub.1-C.sub.4-alkoxyiminomethyl;
di(C.sub.1-C.sub.6alkyl)-aminocarbonyl, where the alkyl groups can
be identical or different; C.sub.1-C.sub.6-alkylaminothiocarbonyl;
di(C.sub.1-C.sub.6alkyl)-aminothiocarbonyl, where the alkyl groups
can be identical or different; C.sub.1-C.sub.6-alkylamino,
di(C.sub.1-C.sub.6alkyl)-amino, where the alkyl groups can be
identical or different; halogen, NO.sub.2, CN, SF.sub.5, thioamido,
thiocyanatomethyl; an unsubstituted or mono- to tetrasubstituted
C.sub.1-C.sub.4alkylenedioxy group, where the substituents are
selected from the group consisting of C.sub.1-C.sub.4alkyl and
halogen; or QR.sub.6, where, if n is greater than 1, the radicals
R.sub.5 can be identical or different;
[0010] R.sub.6 is C.sub.2-C.sub.6alkenyl or C.sub.2-C.sub.6 alkynyl
which are unsubstituted or substituted by 1 to 3 halogen atoms;
(C.sub.1-C.sub.4alkyl).sub.3Si, where the alkyl groups can be
identical or different; CN; or an unsubstituted or mono- to
pentasubstituted C.sub.3-C.sub.6cycloalkyl, aryl or heterocyclyl
group, where the substituents are selected from the group
consisting of halogen, C.sub.1-C.sub.6alkyl,
halogeno-C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy,
halogeno-C.sub.1-C.sub.6alkoxy, phenoxy, naphthoxy and CN;
[0011] A either is a direct bond, C.sub.1--C.sub.10alkylene,
--C(.dbd.O)--, --C(.dbd.S)-- or halogeno-C.sub.1-C.sub.10alkylene
and R.sub.7 is a radical R.sub.10,
[0012] or is C.sub.1-C.sub.10alkylene, --C(.dbd.O)--, --C(.dbd.S)--
or halogeno-C.sub.1-C.sub.10alkylene and
[0013] R.sub.7 is OR.sub.10, N(R.sub.10).sub.2, where the radicals
R.sub.10 can be identical or different, or
--S(.dbd.O).sub.qR.sub.10;
[0014] R.sub.8 is H or C.sub.1-C.sub.4alkyl;
[0015] R.sub.9 is methyl, fluoromethyl or difluoromethyl;
[0016] R.sub.10 is H; an x unsubstituted or substituted
C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl or
C.sub.2-C.sub.6alkynyl group, where the substituents are selected
from the group consisting of halogen;
(C.sub.1-C.sub.4alkyl).sub.3Si, where the alkyl groups can be
identical or different; C.sub.3-C.sub.6cyclo-alkyl, which is
unsubstituted or substituted by halogen;
C.sub.1-C.sub.6alkoxycarbonyl, which is unsubstituted or
substituted by halogen; unsubstituted or substituted aryl, where
the substituents are selected from the group consisting of halogen,
halogeno-C.sub.1-C.sub.4alkyl and CN; a
(C.sub.1-C.sub.4alkyl).sub.3Si group, where the alkyl groups can be
identical or different; C.sub.3-C.sub.6cycloalkyl, which is
unsubstituted or substituted by halogen;
C.sub.1-C.sub.6alkoxycarbonyl which is unsubstituted or substituted
by halogen; or an unsubstituted or substituted aryl or heterocyclyl
group, where the substituents are selected from the group
consisting of halogen and halogeno-C.sub.1-C.sub.- 4alkyl; Q is a
direct bond, C.sub.1-C.sub.8alkylene, C.sub.2-C.sub.6alkenylene,
C.sub.2-C.sub.6alkynylene, O, O(C.sub.1-C.sub.6alkylene),
(C.sub.1-C.sub.6alkylene)O, S(.dbd.O).sub.p,
S(.dbd.O).sub.p(C.sub.1-C.sub.6alkylene) or
(C.sub.1-C.sub.6alkylene)S(.d- bd.O).sub.p;
[0017] m is 0, 1 or 2;
[0018] n is 0, 1, 2, 3, 4 or 5;
[0019] p is 0, 1 or 2; and
[0020] q is 0, 1 or 2,
[0021] and the C.dbd.N double bond marked with E has the E
configuration,
[0022] which comprises
[0023] a1) reacting either a compound of the formula 3
[0024] in which A, R.sub.2, R.sub.5, R.sub.7 and n are as defined
for formula I and the C.dbd.N double bond marked with E has the E
configuration, or a tautomer thereof, in each case in the free form
or in salt form, if appropriate in the presence of a base, with a
compound of the formula 4
[0025] which is known or can be prepared by methods known per se
and in which X, Y, Z, R.sub.3, R.sub.4 and R.sub.9 are as defined
for formula I and X.sub.1 is a leaving group, or a tautomer
thereof, in each case in the free from or in salt form, or
[0026] a2) reacting a compound of the formula 5
[0027] in which A, R.sub.2, R.sub.5, R.sub.1 and n are as defined
for formula I and the C.dbd.N double bond marked with E has the E
configuration, or a tautomer thereof, in each case in the free form
or in the salt form, if appropriate in the presence of a base, with
a compound of the formula 6
[0028] which is known or can be prepared by methods known per se
and
[0029] in which X, Y, Z, R.sub.3, R.sub.4 and R.sub.9 are as
defined for formula I, or a tautomer thereof, in each case in the
free form or in salt form, or
[0030] b1) reacting a compound of the formula 7
[0031] in which R.sub.2, R.sub.5 and n are as defined for formula I
and the C.dbd.N double bond marked with E has the E configuration,
or a tautomer thereof, in each case in the free form or in salt
form, if appropriate in the presence of a base, with a compound of
the formula
R.sub.7-A-X.sub.2 (VII),
[0032] which is known or can be prepared by methods known per se
and
[0033] in which A and R.sub.7 are as defined for formula I and
X.sub.2 is a leaving group, and either further reacting the
compound thus obtainable, of the formula IV, for example according
to method a2), or
[0034] b2) reacting it with hydroxylamine or a salt thereof, if
appropriate in the presence of a base or acid catalyst, and further
reacting the compound thus obtainable, of the formula II, for
example according to method a1), or
[0035] c) reacting a compound of the formula 8
[0036] which is known or can be prepared by methods known per se
and
[0037] in which R.sub.2, R.sub.3 and n are as defined for formula
I, or a tautomer thereof, in each case in the free form or in salt
form, if appropriate in the presence of a base, with a
C.sub.1-C.sub.6alkyl nitrite, and further reacting the compound
thus obtainable, of the formula VI, for example according to method
b),
[0038] the E isomers of the compounds of the formulae II, IV and
VI, or a tautomer thereof, in each case in the free form or in salt
form, a process for their preparation and their use for the
preparation of compounds of the formula I.
[0039] The compounds of the formula I are known pesticides. The
processes known to date for their preparation give mixtures of E
and Z isomers in respect of the C.dbd.N double bond marked with E
in formula I of different composition, depending on the process.
Since the biological properties of the E isomers are in each case
found to be superior to those of the mixtures and of the Z isomers,
there is a need to develop preparation processes for compounds of
the formula I haying the isomerically pure E configuration. This
object is achieved by the preparation process according to the
invention.
[0040] Unless defined differently, the general terms used above and
below are defined as follows.
[0041] Carbon-containing groups and compounds in each case contain
1 up to and including 8, preferably 1 up to and including 6, in
particular 1 up to and including 4, especially 1 or 2, carbon
atoms.
[0042] Alkyl--as a group per se and as a structural element of
other groups and compounds, such as of halogenoalkyl, alkoxy,
alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl,
alkoxycarbonyl, halogenoalkoxycarbonyl,
alkylaminocarbonyl,alkoxyiminomethyl, alkylaminothiocarbonyl and
alkylamino--is, in each case taking into due consideration the
number, included from case to case, of carbon atoms contained in
the corresponding group or compound, either straight-chain, i.e.
methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for
example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl,
neopentyl or isohexyl.
[0043] Alkenyl--as a group per se and as a structural element of
other groups and compounds, such as of halogenoalkenyl--is, in each
case under due consideration of the number, included from case to
case, of carbon atoms contained in the corresponding group or
compound, either straight-chain, for example vinyl, 1-methylvinyl,
allyl, 1-butenyl or 2-hexenyl, or branched, for example
iso-propenyl.
[0044] Alkynyl--as a group per se and as a structural element of
other groups and compounds, such as of halogenoalkynyl--is, in each
case under due consideration of the number, included from case to
case, of carbon atoms contained in the corresponding group or
compound, either straight-chain, for example propargyl, 2-butynyl
or 5-hexynyl, or branched, for example 2-ethynylpropyl or
2-propargylisopropyl.
[0045] C.sub.3-C.sub.6cycloalkyl is cyclopropyl, cyclobutyl,
cyclopentyl or cyclohexyl.
[0046] Alkylene--as a group per se and as a structural element of
other groups and compounds, such as of O(alkylene), (alkylene)O,
S(.dbd.O).sub.p(alkylene), (alkylene)S(.dbd.O).sub.p or
alkylenedioxy--is, in each case under-due consideration of the
number, included from case to case, of carbon atoms contained in
the corresponding group or compound, either straight-chain, for
example --CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2-- or
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2--, or branched, for example
--CH(CH.sub.3)--, --CH(C.sub.2H.sub.5)--, --C(CH.sub.3).sub.2--,
--CH(CH.sub.3)CH.sub.2-- or --CH(CH.sub.3)CH(CH.sub.3)--.
[0047] Alkenylene is, in each case under due consideration of the
number, from case to case, of carbon atoms contained in the
corresponding compound, either straight-chain, for example
vin-1,2-ylene, all-1,3-ylene, but-1-en-1,4-ylene or
hex-2-en-1,6-ylene, or branched, for example
1-methylvin-1,2-ylene.
[0048] Alkynylene is, in each case under due consideration of the
number, from case to case, of carbon atoms contained in the
corresponding compound, either straight-chain, for example
propargylene, 2-butynylene or 5-hexynylene, or branched, for
example 2-ethynylpropylene or 2-propargylisopropylene.
[0049] Aryl is phenyl or naphthyl, in particular phenyl.
[0050] Heterocyclyl is a 5- to 7-membered aromatic or non-aromatic
ring having one to three heteroatoms, which are selected from the
group consisting of N, O and S. 5- and 6-membered rings which
contain a nitrogen atom as a heteroatom and, if appropriate, a
further heteroatom, preferably nitrogen or sulfur, in particular
nitrogen, are preferred.
[0051] Halogen--as a group per se and as a structural element of
other groups and-compounds, such as of halogenoalkyl,
halogenoalkenyl and halogenoalkynyl--is fluorine, chlorine, bromine
or iodine, especially fluorine, chlorine or bromine, in particular
fluorine or chlorine, very especially fluorine.
[0052] Halogen-substituted carbon-containing groups and compounds,
such as halogenoalkyl, halogenoalkenyl or halogenoalkynyl, can be
partly halogenated or perhalogenated, and in the case of
polyhalogenation, the halogen substituents can be identical or
different. Examples of halogenoalkyl--as a group per se and as a
structural element of other groups and compounds, such as of
halogenoalkenyl are methyl which is mono- to trisubstituted by
fluorine, chlorine and/or bromine, such as CHF.sub.2 or CF.sub.3;
ethyl which is mono- to pentasubstituted by fluorine, chlorine
and/or bromine, such as CH.sub.2CF.sub.3, CF.sub.2CF.sub.3,
CF.sub.2CCl.sub.3, CF.sub.2CHCl.sub.2, CF.sub.2CHF.sub.2,
CF.sub.2CFCl.sub.2, CF.sub.2CHBr.sub.2, CF.sub.2CHClF,
CF.sub.2CHBrF or CClFCHClF; propyl or isopropyl which is mono- to
heptasubstituted by fluorine, chlorine and/or bromine, such as
CH.sub.2CHBrCH.sub.2Br, CF.sub.2CHFCF.sub.3,
CH.sub.2CF.sub.2CF.sub.3 or CH(CF.sub.3) 2; and butyl or one of its
isomers which is mono- to nonasubstituted by fluorine, chlorine
and/or bromine, such as CF(CF.sub.3)--CHFCF.sub.3 or
CH.sub.2(CF.sub.2).sub.2CF.sub.3. Halogenoalkenyl is, for example,
CH.sub.2CH.dbd.CHCl, CH.sub.2CH.dbd.CCl.sub.2,
CH.sub.2CF.dbd.CF.sub.2 or CH.sub.2CH.dbd.CHCH.sub.2Br.
Halogenoalkynyl is, for example, CH.sub.2C.ident.CF,
CH.sub.2C.ident.CCH.sub.2Cl or
CF.sub.2CF.sub.2C.ident.CCH.sub.2F.
[0053] Some compounds I to VI and VII can be present as tautomers,
as is familiar to the expert, in particular if AR.sub.7 is H.
Compounds I above and below are therefore also to be understood as
meaning corresponding tautomers, even if the latter are not
mentioned specifically in each case.
[0054] Compounds I to VI and VIII which contain at least one basic
centre, can form, for example, acid addition salts. These are
formed, for example, with strong inorganic acids, such as mineral
acids, for example perchloric acid, sulfuric acid, nitric acid,
nitrous acid, a phosphoric acid, or a hydrogen halide acid, with
strong inorganic carboxylic acids, such as
C.sub.1-C.sub.4alkanecarboxylic acids which are unsubstituted or
substituted, for example by halogen, for example acetic acid, such
as dicarboxylic acids which are saturated or unsaturated, for
example oxalic, malonic, succinic, maleic, fumaric or phthalic
acid, such as hydroxycarboxylic acids, for example ascorbic,
lactic, malic, tartaric or citric acid, or such as benzoic acid, or
with organic sulfonic acids, such as C.sub.1-C.sub.4alkane- or
arylsulfonic acids which are unsubstituted or substituted, for
example by halogen, for example methane- or p-toluenesulfonic acid.
Compounds I with at least one acid group can furthermore form salts
with bases. Suitable salts with bases are, for example, metal salts
such as alkali metal or alkaline earth metal salts, for example
sodium, potassium or magnesium salts, or salts with ammonia or an
organic amine, such as morpholine, piperidine, pyrrolidine, a
mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-,
triethyl- or dimethyl-propyl-amine, or a mono-, di- or
trihydroxy-lower alkylamine, for example mono-, di- or
triethanolamine. Furthermore, where appropriate, corresponding
inner salts can be formed. Agrochemically advantageous salts are
preferred in the context of the invention; however, salts which
have disadvantages for agrochemical uses, for example salts which
are toxic to bees or fish, which are employed, for example, for
isolation or purification of free compounds I or agrochemically
usable salts thereof, are also included. Compounds of the formulae
I to VI and VIII in the free form and in the form of their salts
are also to be understood above and below as meaning the
corresponding salts or the free compounds I to VI and VIII. The
same applies to tautomers of compounds of the formulae I to VI and
VIII and salts thereof. In general, the free form is in each case
preferred.
[0055] The reactions described above and below are carried out in a
manner known per se, for example in the absence or usually in the
presence of a suitable solvent or diluent or a mixture thereof, the
reaction being carried out, as required, with cooling, at room
temperature or with heating, for example in a temperature range
from about -80.degree. C. up to the boiling point of the reaction
medium, preferably from about 0.degree. C. up to about 150.degree.
C., and, if necessary, in a closed vessel, under pressure, in an
inert gas atmosphere and/or under anhydrous conditions.
Particularly advantageous reaction conditions can be seen from the
examples.
[0056] The starting materials mentioned above and below, which are
used for the preparation of the compounds I, in each case in the
free form or in salt form, are known or can be prepared by methods
known per se, for example in accordance with the following
statements.
[0057] Variants a1/a2)
[0058] Suitable leaving groups X.sub.1 in compounds III are, for
example, hydroxyl, C.sub.1-C.sub.8alkoxy,
halogeno-C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkanoyloxy,
mercapto, C.sub.1-C.sub.8alkylthio,
halogeno-C.sub.1-C.sub.8alkylthio,
C.sub.1-C.sub.8alkanesulfonyloxy,
halogeno-C.sub.1-C.sub.8alkanesulfonyloxy, benzenesulfonyloxy,
toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy,
trifluoromethanesulfonyloxy and halogen, in particular halogen.
[0059] Suitable bases for facilitating the reaction are, for
example, alkali metal or alkaline earth metal hydroxides, hydrides,
amides, alkanolates, acetates, carbonates, dialkylamides or
alkylsilylamides, alkylamines, alkylenediamines, N-alkylated or
non-alkylated, saturated or unsaturated cycloalkylamines, basic
heterocyclic compounds, ammonium hydroxides and carbocyclic amines.
Examples are sodium hydroxide, hydride, amide, methanolate, acetate
and carbonate, potassium tert-butanolate, hydroxide, carbonate, and
hydride, lithium diisopropylamide, potassium
bis(trimethylsilyl)amide, calcium hydride, triethylamine,
diisopropyl-ethyl-amine, triethylenediamine, cyclohexylamine,
N-cyclohexyl-N,N-dimethyl-amine, N,N-diethylaniline, pyridine,
4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine,
benzyl-trimethyl-ammonium hydroxide and
1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).
[0060] The reaction partners can be reacted with one another as
such, i.e. without addition of a solvent or diluent, for example in
the melt. However, the addition of an inert solvent or diluent or
of a mixture thereof is usually advantageous. Examples of such
solvents or diluents are: aromatic, aliphatic and alicyclic
hydrocarbons and halogenohydrocarbons, such as benzene, toluene,
xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene,
bromobenzene, petroleum ether, hexane, cyclohexane, methylene
chloride, chloroform, carbon tetrachloride, dichloroethane,
trichloroethene or tetrachloroethene; esters, such as ethyl
acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl
ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol
monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane;
ketones, such as acetone, methyl ethyl ketone or methyl isobutyl
ketone; alcohols, such as methanol, ethanol, propanol, isopropanol,
butanol, ethylene glycol or glycerol; amides, such as
N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,
N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles
such as acetonitrile or propionitrile; and sulfoxides, such as
dimethyl sulfoxide. If the reaction is carried out in the presence
of a base, bases employed in excess, such as triethylamine,
pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve
as the solvent or diluent.
[0061] The reaction is advantageously carried out in a temperature
range from about 0.degree. C. up to about 180.degree. C.,
preferably from about 10.degree. C. up to about 80.degree. C., in
many cases in the range between room temperature and the reflux
temperature of the reaction mixture.
[0062] The reaction is preferably carried out under normal
pressure.
[0063] The reaction can be carried out without an inert gas
atmosphere; preferably, however, it is carried out under an inert
gas atmosphere, for example nitrogen or argon, in particular
nitrogen.
[0064] The reaction time is not critical; a reaction time of about
0.1 to about 24 hours, in particular about 0.5 to about 2 hours, is
preferred.
[0065] The product is isolated by customary methods, for example by
filtration, crystallization, distillation or chromatography or any
suitable combination of these processes.
[0066] In a preferred embodiment of variants a1/a2), a compound II
is reacted with a compound III at 0.degree. C. to 80.degree. C.,
preferably 10.degree. C. to 30.degree. C., in an inert solvent,
preferably an amide, in particular N,N-dimethylformamide in the
presence of a metal hydride, preferably sodium hydride.
[0067] Particularly preferred conditions for the reaction are
described in Examples H1 d) and H 3f).
[0068] The compounds of the formula III are known or can be
prepared analogously to known compounds.
[0069] The compounds I are known. However, their preparation
according to the prior art has a large number of serious
industrial, ecological, economic and other disadvantages.
[0070] Thus, in the preparation processes according to the prior
art, as a rule E/Z isomer mixtures with respect to the C.dbd.N
double bond marked with E in formula I are obtained. Since the
biological properties of the E isomers are in each case found to be
superior to those of the mixtures and of the Z isomers in each
case, the processes according to the prior art have the significant
disadvantage that products are produced which are either
significantly less active as E/Z mixtures or from which the Z
isomers must be removed in order to increase their biological
activity, which means that many unnecessary handling operations
must be carried out for separation of isomers, which has the effect
of being very time-consuming, blocks valuable production lines for
a long time and is associated with high additional energy costs.
The removal of the less active Z isomer also leads to additional
enormous losses in yield, which in turn not only is problematic and
ecologically disadvantageous, but also renders the process
according to the prior art much more expensive and consequently
economically of no interest. The industrial, ecological, economic
and other disadvantages of the processes according to the prior art
are not limited to those described above, these latter being
intended to serve only as a few examples of the large number of
disadvantages of the processes according to the prior art. The
disadvantages of the processes according to the prior art cause
serious problems even when the processes are carried out on a
laboratory scale. When the processes are carried out on a larger
scale, these disadvantages intensify considerably. In the end,
however, the aim is to carry out a specific process on an
industrial scale if this process is to be suitable for preparing
products for agrochemical purposes.
[0071] According to the process of the present invention, the
compounds I are prepared by reaction of the compound II with a
compound III or by reaction of the compound IV with a compound V.
These processes according to the invention have extremely
surprising industrial, ecological, economic and other advantages
compared with the processes from the prior art. Since the compounds
II or, respectively, IV are present in the preparation process
according to the invention as pure E isomers in respect of the
C.dbd.N double bond marked with E, only the E isomer of the
compounds I is produced in the present process, which has the
effect of an enormous saving in time and at the same time a high
saving in cost and energy, since no valuable production lines are
blocked for a long time for separation of the isomers, and at the
same time the amount of biologically more active E isomer produced
by per unit time is much higher than in the processes according to
the prior art. The resources such as starting products and energy
are consequently utilized to the optimum in the present process,
which not only very greatly simplifies the process and renders it
ecologically advantageous, but consequently renders it cheaper and
therefore of greater economic interest. This means that all the
disadvantages of the processes according to the prior art which can
be attributed to the formation of E/Z isomers are avoided. The
industrial, ecological, economic and other advantages of the
process according to the invention are not limited only to those
described above, these latter being intended to serve only as a few
examples of the large number of advantages inherent in this
process. Due to all the abovementioned advantages of the present
process, the serious problems which occur in the processes
according to the prior art are avoided even at the stage of a
laboratory process. If the present process is used on a larger
scale, these advantages prove to be even much more significant,
which has the effect that these advantages first allow the process
to be used on an industrial scale.
[0072] For this reason, all the industrial, ecological, economic
and other disadvantages of the processes according to the prior art
are surprisingly advantageously overcome in the preparation of
compounds I by the present process.
[0073] Variant b)
[0074] The process according to variant b) is carried out by first
reacting compound VI with compound VII, if appropriate further
reacting the resulting product IV, if appropriate after isolation,
with hydroxylamine or a salt thereof, and further reacting the
resulting products 11 or, respectively, IV, if appropriate after
isolation, in accordance with variants a1/a2), for example in the
manner described above, to give the compounds I.
[0075] Suitable leaving groups X.sub.2 in the compounds VII are,
for example, those which are mentioned as examples for X.sub.1 in
variants a1/a2).
[0076] Suitable bases for facilitating the reaction are, for
example, those which are mentioned in variants a1/a2).
[0077] The reaction partners can be reacted with one another as
such, i.e. without addition of a solvent or diluent, for example in
the melt. However, the addition of an inert solvent or diluent or
of a mixture thereof is usually advantageous. Examples of such
solvents or diluents are those mentioned in variants a1/a2).
[0078] The reaction is advantageously carried out in a temperature
range from about 0.degree. C. to about 180.degree. C., preferably
from about 10.degree. C. to about 80.degree. C., in many cases in
the range between room temperature and the reflux temperature of
the reaction mixture.
[0079] The reaction is preferably carried out under normal
pressure.
[0080] The reaction can be carried out without an inert gas
atmosphere; preferably, however, it is carried out under an inert
gas atmosphere, for example nitrogen or argon, in particular
nitrogen.
[0081] The reaction time is not critical; a reaction time of about
0.1 to about 24 hours, in particular about 0.5 to about 5 hours, is
preferred.
[0082] The product is isolated by customary methods, for example
filtration, crystallization, distillation or chromatography or any
suitable combination of these processes.
[0083] In a preferred embodiment of variant b), a compound VI is
reacted with a compound VII at 0.degree. C. to 80.degree. C.,
preferably 10.degree. C. to 60.degree. C., in an inert solvent,
preferably a nitrile, in particular acetonitrile, in the presence
of a metal carbonate, preferably potassium carbonate, and the
compound IV thus obtainable is then further reacted, preferably in
accordance with method a2).
[0084] Particularly preferred conditions for the reaction are
described in Examples H 1b) to 1d) and H 3d) to 3f).
[0085] The compounds of the formula VII are known or can be
prepared analogously to known compounds.
[0086] The present process according to the invention of variant
b), which in principle is an advantageous combination of an
O-alkylation reaction with process variants a1/a2) according to the
invention, has all the great advantages compared with the prior art
which have already been discussed above for the process according
to the invention of variants a1/a2). In particular, the process of
variant b) ensures that the E configuration of the C.dbd.N double
bond marked with E in compound VI is retained. Furthermore,
however, the process according to the invention of variant b) also
has further industrial, ecological, economic and other advantages
which are connected with the specific property that the
intermediate product IV initially formed is not purified but is
directly further processed as the moist crude product, in the case
of intermediate isolation, or in situ in the reaction mixture, if
it is not isolated. This missing purification step on the
intermediate product mentioned is of advantage, for example, in as
much as it is not necessary to dry it, which not only saves energy
and further resources, but also enormously increases the safety of
the preparation process, since the possible danger of a dust
explosion of the dry intermediate product is averted completely.
The savings in resources are even greater if the intermediate
product is further reacted without purification, since, for
example, no additional solvents are consumed for the
recrystallization. The process of variant b) is of particular
advantage compared with the individual process steps of the
alkylation reaction of variants a1/a2) carried out in that the
total reaction time in the process of variant b) is much shorter,
which consequently leads to a much higher production of reaction
product I per unit time and therefore to a much more efficient
utilization of the valuable production lines. Furthermore, the
total yield of reaction product I is surprisingly good when the
process of variant b) is employed, and, compared with the combined
yields of the individual process steps of the alkylation reaction
and variants a1/a2) carried out, is in the same percentage range or
even better. The industrial, ecological, economic and other
advantages of the process according to the invention of variant b)
are not limited to those described above, these latter being
intended to serve only as a few examples of the large number of
advantages inherent in the process according to the invention of
variant b).
[0087] By using process variant b) according to the invention for
preparation of the compounds I, a large number of industrial,
ecological, economic and other advantages can therefore
surprisingly be utilized efficiently.
[0088] Variant c)
[0089] The process according to variant c) is carried out by first
reacting compound VIII with an alkylnitrite and further reacting
the resulting product VI, if appropriate after isolation, in
accordance with variant b), for example in the manner described
above, to give the compounds I.
[0090] Suitable bases for facilitating the reaction are, for
example, those which are mentioned in variants a1/a2).
[0091] The reaction partners can be reacted with one another as
such, i.e. without addition of a solvent or diluent, for example in
the melt. However, the addition of an inert solvent or diluent or
of a mixture thereof is usually advantageous. Examples of such
solvents or diluents are those mentioned in variants a1/a2).
[0092] The reaction is advantageously carried out in a temperature
range from about 0.degree. C. to about 180.degree. C., preferably
from about 0.degree. C. to about 60.degree. C., in many cases in
the range between room temperature and the reflux temperature of
the reaction mixture.
[0093] The reaction is preferably carried out under normal
pressure.
[0094] The reaction can be carried out without an inert gas
atmosphere; preferably, however, it is carried out under an inert
gas atmosphere, for example nitrogen or argon, in particular
nitrogen.
[0095] The reaction time is not critical; a reaction time of about
0.1 to about 24 hours, in particular about 0.5 to about 3 hours, is
preferred.
[0096] The product is isolated by customary methods, for example
filtration, crystallization, distillation or chromatography or any
suitable combination of these processes.
[0097] In a preferred embodiment of variant c), a compound VIII is
reacted with an alkyl nitrite at 0.degree. C. to 80.degree. C.,
preferably 0.degree. C. to 40.degree. C., in an inert solvent,
preferably an alcohol, in particular methanol, in the presence of a
metal alcoholate, preferably sodium methanolate, and the compound
VI thus obtainable is then further reacted, preferably in
accordance with method b).
[0098] Particularly preferred conditions for the reactions are
described in Examples H 3d) to 3f).
[0099] The compounds of the formula VIII are known or can be
prepared analogously to known compounds.
[0100] The present process according to the invention of variant
c), which in principle is an advantageous combination of an
oximation reaction with process variants a1/a2) and b) according to
the invention, has all the great advantages compared with the prior
art which have already been discussed above for the processes
according to the invention of variants a1/a2) and b). Furthermore,
the present oximation process for the preparation of the compounds
VI surprisingly result exclusively in the E configuration of the
C.dbd.N double bond marked with E in formula VI. It is thus ensured
that the particular starting products II, IV or, respectively, VI
in the subsequent processes according to the invention for the
preparation of the compounds I, for example in process variants
a1/a2) and b), are pure E isomers.
[0101] A large number of industrial, ecological, economic and other
advantages can therefore surprisingly be utilized efficiently by
using process variants c) according to the invention for the
preparation of the compounds of the formula I.
[0102] The E isomers of the compounds of the formulae II, IV and VI
and tautomers thereof, in each case in the free form or in salt
form, are novel and the present invention likewise relates to
them.
[0103] The present invention furthermore relates to a process for
the preparation of the E isomers of a compound of the formula VI or
of a tautomer thereof, in each case in the free form or in salt
form, according to the abovementioned process c),
[0104] a process for the preparation of the E isomers of a compound
of the formula IV, or of a tautomer thereof, in each case in the
free form or in salt form, according to the abovementioned process
b1), and
[0105] a process for the preparation of the E isomers of a compound
of the formula II, or of a tautomer thereof, in each case in the
free form or in salt form, according to the abovementioned process
b2).
[0106] The process conditions for the preparation of these
intermediate products can be seen from the abovementioned processes
a), b) and c).
PREPARATION EXAMPLES
Example H1
Methyl
2-[[[(1-methyl-2-phenyl-2-E-[(2-propynyl)oxyimino]-ethylidene)amino-
]oxy]methyl].alpha.-(methoxymethylene)-phenylacetate (Compound
1.16)
[0107] H1a) 1-Phenyl-1,2-propanedione 1-E-oxime
[0108] 69.7 g of a 30% solution of sodium methylate in methanol are
added dropwise to a solution of 40.2 g of 1-phenyl-2-propanone and
36.1 g of isopentyl nitrite in 460 ml of methanol at 20-25.degree.,
while cooling. The reaction mixture is then further stirred at room
temperature for 1 hour. After the solution has been concentrated in
vacuo, the residue is dissolved in 600 ml of water, the solution is
acidified with 10% hydrochloric acid, the product which
precipitates out is filtered off and dissolved in ethyl acetate and
the organic phase is washed twice with water, dried with sodium
sulfate and evaporated in vacuo. The residue is stirred up in
hexane and filtered. The title product is thus obtained with a
melting of 168-70.degree. C.
[0109] H1b) 1-Phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime]
[0110] A mixture of 14 g of 1-phenyl-1,2-propanedione 1-E-oxime,
11.9 g of 1-bromo-2-propyne, 13.8 g of potassium carbonate and 0.5
g of potassium iodide in 170 ml of acetonitrile is stirred at
50.degree. for 2 hours, the solvent is then distilled off in vacuo
and the residue is dissolved again in ethyl acetate. The organic
phase is washed in each case twice with water and saturated sodium
chloride solution, dried with sodium sulfate and evaporated in
vacuo. After recrystallization of the residue from hexane,
1-phenyl-1,2-propanedione 1-E-[(2-propynyl)oxime] is obtained with
a melting point of 54-56.degree. C.
[0111] H1d) 1-Phenyl-1,2-propanedione
1-E-[(2-propynyl)oxime]-2-oxime
[0112] A mixture of 14.3 g of 1-phenyl-12-propanedione
1-E-[(2-propynyl)oxime], 10.3 g of hydroxylamine hydrochloride and
11.7 g of pyridine in 230 ml of ethanol is boiled under reflux for
1 hour and then concentrated in vacuo, and 800 ml of water are
added to the residue. The product which has precipitated out is
filtered off and dissolved in ethyl acetate and the solution is
washed three times with water, dried with sodium sulfate and
evaporated in vacuo. The residue is suspended in hexane and
filtered. The title product is thus obtained with a melting point
of 163-165.degree. C.
[0113] H1e) Methyl
2-[[[(1-methyl-2-phenyl-2-E-[(2-propynyl)oxyimino]ethy--
lidene)amino]oxy]-methyl]-.alpha.-(methoxymethylene)-phenylacetate
[0114] A solution of 5 g of 1-phenyl-1,2-propanedione
1-E-[(2-propynyl)oxime]-2-oxime in 24 ml of N,N-dimethylformamide
is added dropwise to a suspension of 1.16 g of sodium hydride
(about 55% in oil) in 45 ml of N,N-dimethylformamide at room
temperature and the mixture is further stirred for 10 minutes. 6.5
g of methyl
2-(bromomethyl)-.alpha.-(methoxymethylene)-phenylacetate in 24 ml
of N,N-dimethylformamide are then added dropwise and the reaction
mixture is further stirred at room temperature for 1 hour.
Thereafter, the mixure is acidified with acetic acid and evaporated
in vacuo. The residue is dissolved in ethyl acetate and the
solution is washed three times with water and twice with saturated
sodium chloride solution, dried with sodium sulfate and evaporated
in vacuo. After recrystallization of the residue from hexane/ethyl
acetate, the title compound is obtained with a melting point of
82-84.degree..
Example H2
Methyl
2-[[[(1-methyl-2-(4-fluorophenyl)-2-E-[(2-propynyl)oxyimino]ethylid-
ene)amino]oxy]methyl]-.alpha.-(methoxymethylene)-phenylacetate
(compound 1.44)
[0115] The title compound with a melting point of 91-93"-can be
prepared in a manner analogous to that described in Example H1,
starting from 1-(4-fluorophenyl)-2-propanone.
Example H3
Methyl 2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-phenyl)
2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-.alpha.-(methoxyme-
thylene)-phenylacetate (compound 1.240)
[0116] H3a) 1-(4-Hydroxyphenyl)-2'-propanone
[0117] A mixture of 82 g of 1-(4-methoxyphenyl)-2-propanone, 500 ml
of acetic acid and 500 ml of aqueous hydrobromic acid is boiled
under reflux for 2 hours and then evaporated in vacuo. The oily
residue is extracted four times with 700 ml of hexane/ether (5:2)
each time, the extract is evaporated and the residue is
chromatographed over silica gel using hexane/ethyl acetate (3:1).
1-(4-Hydroxyphenyl)-2-propanone is thus obtained with a melting
point of 40-41.degree..
[0118] H3b)
1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-2-propanone
[0119] A mixture of 5.8 g of 1-(4-hydroxyphenyl)-2-propanone, 61.6
g of potassium carbonate, 72.3 g of
1-(chloromethyl)-3-(trifluoromethyl)-benze- ne, and 1 g of
potassium iodide in 800 ml of acetone is boiled under reflux for 5
hours. Thereafter, the reaction mixture is filtered and the
filtrate is evaporated in vacuo. The residue is then dissolved in
diethyl ether and the ethereal phase is washed three times with
water, dried with sodium sulfate and evaporated. The
1-[4-(3-trifluoromethylphenylmethoxy)-- phenyl]-2-propanone thus
obtainable is employed in the next reaction stage without further
purification.
[0120] H3c)
1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione
1-E-oxime
[0121] 45 g of a 30% solution of sodium methanolate in methanol are
slowly added dropwise to a solution of 59.6 g of
1-[4-(3-trifluoromethylphenylme- thoxy)-phenyl]-2-propanone and
23.4 g of isopentyl nitrite in 300 ml of methanol such that the
temperature does not exceed 20-25.degree.. The reaction mixture is
then further stirred at room temperature for 1 hour and thereafter
evaporated in vacuo. The residue is dissolved in 600 ml of water
and the solution is acidified with 10% hydrochloric acid. The
precipitate which separates out is filtered off and dissolved in
ethyl acetate and the organic phase is washed twice with water,
dried with sodium sulfate and evaporated. After the crude product
has been suspended in hexane and filtered,
1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1,2- -propanedione
1-E-oxime is obtained with a melting point of 134-136.degree..
[0122] H3d)
1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione
1-E-[(2-propynyl)oxime]
[0123] A mixture of 6 g of
1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]-1- ,2-propanedione
1-E-oxime, 2.4 g of 1-bromo-2-propyne, 2.6 g of potassium carbonate
and 0.5 g of potassium iodide in 40 ml of acetonitrile is boiled
under reflux for 1 hour and then evaporated in vacuo and the
residue is dissolved in ethyl acetate. The organic phase is washed
twice with water and once with saturated sodium chloride solution,
dried with sodium sulfate and evaporated. The crude
1-[4-(3-trifluoromethylphenylmet- hoxy)-phenyl]-1,2-propanedione
1-E-[(2-propynyl)oxime] thus obtainable is further processed
without further purification.
[0124] H3e)
1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione
1-E-[(2-propynyl)oxime]-2-oxime
[0125] A mixture of 5.9 g of
1-[4-(3-trifluoromethylphenylmethoxy)-phenyl]- -1,2-propanedione
1-E-[(2-propynyl)oxime], 2.3 g of hydroxylamine hydrochloride and
2.6 g of pyridine in 60 ml of ethanol is boiled under reflux for 1
hour and then concentrated in vacuo, and 200 ml of water are added
to the residue. The product which has precipitated out is filtered
off and dissolved in ethyl acetate, and the solution is washed
twice with water and once with saturated sodium chloride solution,
dried with sodium sulfate and evaporated in vacuo. The residue is
suspended in hexane and filtered.
1-[4-(3-Trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedione
1-E-[(2-propynyl)oxime]-2-oxime is thus obtained with a melting
point of 114-115.degree..
[0126] H3f) Methyl
2-[[[(1-methyl-2-(4-(3-trifluoromethylphenylmethoxy)-ph-
enyl)-2-E-[(2-propynyl)oxyimino]ethylidene)amino]oxy]methyl]-.alpha.-(meth-
oxymethylene)-phenylacetate
[0127] A solution of 5.5 g of
1-[4-(3-trifluoromethylphenylmethoxy)-phenyl- ]-1,2-propanedione
1-E-[(2-propynyl)oxime]-2-oxime in 25 ml of N,N-dimethylformamide
is added dropwise to a suspension of 0.7 g of sodium hydride (about
55% in oil) in 25 ml of N,N-dimethylformamide and the mixture is
further stirred at room temperature for 10 minutes. 4 g of methyl
2-(bromomethyl)-.alpha.-(methoxymethylene)-phenylacetate in 15 ml
of N,N-dimethylformamide are then added dropwise and the reaction
mixture is further stirred at room temperature for 1 hour.
Thereafter, the mixture is acidified with acetic acid and
evaporated in vacuo at 50.degree.. The residue is dissolved in
ethyl acetate and the solution is washed twice with water and once
with saturated sodium chloride solution, dried with sodium sulfate
and evaporated in vacuo. After purification by chromatography
(silica gel, ethyl acetate/hexane 1:3), the title compound is
obtained as a resin.
Example H4
Methyl
2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxyimin-
o]ethylidene)amino]oxy]methyl]-.alpha.-(methoxymethylene)-phenylacetate
(compound 1.366)
[0128] H4a) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione
1-E-oxime
[0129] 16.7 g of a 30% solution of sodium methylate in methanol are
added dropwise to a solution of 22.5 g of
1-[4-(4-chlorophenoxy)-phenyl]-2-prop- anone and 10.3 g of
isopentyl nitrite in 120 ml of methanol at 20-25.degree., while
cooling. The reaction mixture is then further stirred at room
temperature for 1 hour. After the solution has been concentrated in
vacuo, the residue is dissolved in 300 ml of water and the solution
is acidified with 10% hydrochloric acid, the product which
precipitates out is filtered off and dissolved in ethyl acetate and
the organic phase is washed twice with water, dried with sodium
sulfate and evaporated in vacuo. The residue is stirred up in
hexane and filtered. The title product is thus obtained with a
melting point of 154-155.degree. C.
[0130] H4b) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione
1-E-[(2-ethyl)oxime]
[0131] A mixture of 6 g of)
1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedion- e 1-E-oxime, 3.3 g
of ethyl bromide, 3.5 g of potassium carbonate and 0.5 g of
potassium iodide in 30 ml of acetonitrile is stirred at 50.degree.
for 2 hours, the solvent is then distilled off in vacuo and the
residue is dissolved again in ethyl acetate. The organic phase is
washed in each case twice with water and saturated sodium chloride
solution, dried with sodium sulfate and evaporated in vacuo. After
recrystallization of the residue from hexane, the title product is
obtained with a melting point of 77-78.degree. C.
[0132] H4c) 1-[4-(4-Chlorophenoxy)-phenyl]-1,2-propanedione
1-E-[(2-ethyl)oxime]-2-oxime
[0133] A mixture of 5.5 g of
1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedio- ne
1-E-[(2-ethyl)oxime], 2.4 g of hydroxylamine hydrochloride and 2.7
g of pyridine in 50 ml of ethanol is boiled under reflux for 1 hour
and then concentrated in vacuo, and 800 ml of water are added to
the residue. The product which has precipitated out is filtered off
and dissolved in ethyl acetate and the solution is washed three
times with water, dried with sodium sulfate and evaporated in
vacuo. The residue is suspended in hexane and filtered. The title
product is thus obtained in a pure form with a melting point of
176-177.degree. C.
[0134] H4d) Methyl
2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-e-
thyl)oxyimino]ethylidene)amino]oxy]methyl]-.alpha.-(methoxymethylene)-phen-
ylacetate.
[0135] A solution of 4.7 g of
1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedi- one
1-E-[(2-propynyl)-oxime]-2-oxime in 25 ml of N,N-dimethylformamide
is added dropwise to a suspension of 0.65 g of sodium hydride
(about 55% in oil) in 20 ml of N,N-dimethylformamide and the
mixture is further stirred at room temperature for 10 minutes. 4 g
of methyl 2-(bromomethyl)-.alpha.-
-(methoxymethylene)-phenylacetate in 15 ml of N,N-dimethylformamide
are then added dropwise and the reaction mixture is further stirred
at room temperature for 1 hour. Thereafter, the mixture is
acidified with acetic acid and evaporated in vacuo at 50.degree..
The residue is dissolved in ethyl acetate and the solution is
washed twice with water and once with saturated sodium chloride
solution, dried with sodium sulfate and evaporated in vacuo. After
purification by flash chromatography (silica gel, ethyl
acetate/hexane 1:3), the title compound is obtained with a melting
point of 87-89.degree. C.
Example H5
Methyl
2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxy-imi-
no]ethylidene)amino]oxy]methyl]-.alpha.-(methoxyimino)-phenylacetate
(compound 2.366)
[0136] The title compound with a melting point of 90 to 93.degree.
C. is obtained in a manner analogous to that described in Example
H4 from 1-[4-(4-chlorophenoxy)-phenyl]-1,2-propanedione
1-E-[(2-propynyl)oxime]-2- -oxime and methyl
2-(bromomethyl)-.alpha.-(methoxyimino)-phenylacetate.
Example H6
2-[[[(1-Methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E-[(2-ethyl)oxy-imino]ethy-
lidene)amino]oxy].sub.m!ethyl]-.alpha.-(methoxyimino)-phenytacetic
acid methylamide (compound 3.366)
[0137] 13,3 g of methyl
2-[[[(1-methyl-2-(4-(4-chlorophenoxy)-phenyl)-2-E--
[(2-ethyl)oxyimino]ethyliene)amino]oxy]methyl]-.alpha.-(methoxyimino)-phen-
ylacetate are left to stand together with 80 ml of
dimethylformamide and 9.2 ml of an 8 molar solution of methylamine
in ethanol at room temperature for two days. The mixture is
concentrated at 50.degree. C., n-hexane is added and the mixture is
cooled to room temperature and filtered. The residue is dried under
a high vacuum. The title compound is obtained with a melting point
of 126-129.degree. C.
Example H7
[0138] The other compounds listed in Tables 1 to 3 can also be
prepared in a manner analogous to that described in Examples H1 to
H6. In the "physical data" column of the tables, the temperatures
stated in each case designate the melting point of the compound in
question c.propyl is cyclopropyl.
1TABLE 1 Compounds of the general formula 9 I.1,
[0139] in which X is CH and Y is oxygen and the combination of
substituents R.sub.2, (R.sub.5).sub.x and A-R.sub.7 for a compound
in each case corresponds to a line in Table A. The compound numbers
of the following table correspond to the particular numbers in
Table A.
2 TABLE 2 Compound No. Phys. Data(Melting point .degree. C.) 1.14
75-77.degree. 1.16 82-84.degree. 1.22 111-113.degree. 1.42 Resin
1.44 91-93.degree. 1.50 Resin 1.70 Resin 1.72 Resin 1.78 Resin
1.225 102-103.degree. 1.226 81-83.degree. 1.227 Resin 1.233 Resin
1.234 73-75.degree. 1.238 Resin 1.240 Resin 1.241 Resin 1.242 Resin
1.244 Resin 1.245 Resin 1.294 Resin 1.296 112-114.degree. 1.366
87-89.degree.
[0140] Compounds of the general formula I.1, in which
[0141] X is nitrogen and
[0142] Y is oxygen
[0143] and the combination of substituents R.sub.2, (R.sub.5).sub.n
and A-R.sub.7 for a compound in each case corresponds to a line in
Table A.
3 TABLE 3 Compound No. Melting point (.degree. C.) 2.198 75-77
2.254 80-82 2.309 106-108 2.310 102-104 2.366 90-93
[0144] Compounds of the general formula I.1, in which
[0145] X is nitrogen and
[0146] Y is NH and
[0147] the combination of substituents R.sub.2, (R.sub.5).sub.n and
A-R.sub.7 for a compound in each case corresponds to a line in
Table A.
4 Compound No. Melting point (.degree. C.) 3.198 75-77 3.254
112-114 3.309 89-91 3.310 88-90 3.366 126-129
[0148]
5TABLE A Com- pound No. R.sub.2 (R.sub.5).sub.n A-R.sub.7 1
CH.sub.3 H CH.sub.3 2 CH.sub.3 H C.sub.2H.sub.5 3 CH.sub.3 H
n-C.sub.3H.sub.7 4 CH.sub.3 H i-C.sub.3H.sub.7 5 CH.sub.3 H
n-C.sub.4H.sub.9 6 CH.sub.3 H n-C.sub.6H.sub.13 7 CH.sub.3 H
CH.sub.2F 8 CH.sub.3 H CHF.sub.2 9 CH.sub.3 H CH.sub.2CF.sub.3 10
CH.sub.3 H CH.sub.2CH.dbd.CH.sub.2 11 CH.sub.3 H
CH.sub.2CH.dbd.CHCH.sub.3 12 CH.sub.3 H CH.sub.2CH.dbd.C(CH.sub.3)-
.sub.2 13 CH.sub.3 H CH.sub.2CH.dbd.CHCl 14 CH.sub.3 H
CH.sub.2CH.dbd.CCl.sub.2 15 CH.sub.3 H CH.sub.2C(CH.sub.3).dbd.CH.-
sub.2 16 CH.sub.3 H CH.sub.2C.ident.CH 17 CH.sub.3 H
CH.sub.2Si(CH.sub.3).sub.3 18 CH.sub.3 H CH.sub.2-c.propyl-2,2-Cl.-
sub.2 19 CH.sub.3 H CH.sub.2CN 20 CH.sub.3 H
CH.sub.2COOC.sub.2H.sub.5 21 CH.sub.3 H CH(CH.sub.3)COOC.sub.2H.su-
b.5 22 CH.sub.3 H CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 23 CH.sub.3 H
CH.sub.2C.sub.6H.sub.4-4-F 24 CH.sub.3 H CH.sub.2C.sub.6H.sub.4-3-F
25 CH.sub.3 H CH.sub.2C.sub.6H.sub.4-2-- F 26 CH.sub.3 H
C(.dbd.O)OC.sub.2H.sub.5 27 CH.sub.3 H C(.dbd.O)NHCH.sub.3 28
CH.sub.3 H C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.- 5 29 CH.sub.3 4-F
CH.sub.3 30 CH.sub.3 4-F C.sub.2H.sub.5 31 CH.sub.3 4-F
n-C.sub.3H.sub.7 32 CH.sub.3 4-F i-C.sub.3H.sub.7 33 CH.sub.3 4-F
n-C.sub.4H.sub.9 34 CH.sub.3 4-F n-C.sub.6H.sub.13 35 CH.sub.3 4-F
CH.sub.2F 36 CH.sub.3 4-F CHF.sub.2 37 CH.sub.3 4-F
CH.sub.2CF.sub.3 38 CH.sub.3 4-F CH.sub.2CH.dbd.CH.sub.2 39
CH.sub.3 4-F CH.sub.2CH.dbd.CHCH.sub.3 40 CH.sub.3 4-F
CH.sub.2CH.dbd.C(CH.sub.- 3).sub.2 41 CH.sub.3 4-F
CH.sub.2CH.dbd.CHCl 42 CH.sub.3 4-F CH.sub.2CH.dbd.CCl.sub.2 43
CH.sub.3 4-F CH.sub.2C(CH.sub.3).dbd.C- H.sub.2 44 CH.sub.3 4-F
CH.sub.2C.ident.CH 45 CH.sub.3 4-F CH.sub.2Si(CH.sub.3).sub.3 46
CH.sub.3 4-F CH.sub.2-c.propyl-2,2-C- l.sub.2 47 CH.sub.3 4-F
CH.sub.2CN 48 CH.sub.3 4-F CH.sub.2COOC.sub.2H.sub.5 49 CH.sub.3
4-F CH(CH.sub.3)COOC.sub.2H.- sub.5 50 CH.sub.3 4-F
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 51 CH.sub.3 4-F
CH.sub.2C.sub.6H.sub.4-4-F 52 CH.sub.3 4-F
CH.sub.2C.sub.6H.sub.4-3-F 53 CH.sub.3 4-F CH.sub.2C.sub.6H.sub.4--
2-F 54 CH.sub.3 4-F C(.dbd.O)OC.sub.2H.sub.5 55 CH.sub.3 4-F
C(.dbd.O)NHCH.sub.3 56 CH.sub.3 4-F C(.dbd.O)C(.dbd.O)OC.sub.2H.su-
b.5 57 CH.sub.3 4-OCH.sub.3 CH.sub.3 58 CH.sub.3 4-OCH.sub.3
C.sub.2H.sub.5 59 CH.sub.3 4-OCH.sub.3 n-C.sub.3H.sub.7 60 CH.sub.3
4-OCH.sub.3 i-C.sub.3H.sub.7 61 CH.sub.3 4-OCH.sub.3
n-C.sub.4H.sub.9 62 CH.sub.3 4-OCH.sub.3 n-C.sub.6H.sub.13 63
CH.sub.3 4-OCH.sub.3 CH.sub.2F 64 CH.sub.3 4-OCH.sub.3 CHF.sub.2 65
CH.sub.3 4-OCH.sub.3 CH.sub.2CF.sub.3 66 CH.sub.3 4-OCH.sub.3
CH.sub.2CH.dbd.CH.sub.2 67 CH.sub.3 4-OCH.sub.3
CH.sub.2CH.dbd.CHCH.sub.3 68 CH.sub.3 4-OCH.sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 69 CH.sub.3 4-OCH.sub.3
CH.sub.2CH.dbd.CHCl 70 CH.sub.3 4-OCH.sub.3
CH.sub.2CH.dbd.CCl.sub.2 71 CH.sub.3 4-OCH.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 72 CH.sub.3 4-OCH.sub.3
CH.sub.2C.ident.CH 73 CH.sub.3 4-OCH.sub.3 CH.sub.2Si(CH.sub.3).su-
b.3 74 CH.sub.3 4-OCH.sub.3 CH.sub.2-c.propyl-2,2-Cl.sub.2 75
CH.sub.3 4-OCH.sub.3 CH.sub.2CN 76 CH.sub.3 4-OCH.sub.3
CH.sub.2COOC.sub.2H.sub.5 77 CH.sub.3 4-OCH.sub.3
CH(CH.sub.3)COOC.sub.2H.sub.5 78 CH.sub.3 4-OCH.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 79 CH.sub.3 4-OCH.sub.3
CH.sub.2C.sub.6H.sub.4-4-F 80 CH.sub.3 4-OCH.sub.3
CH.sub.2C.sub.6H.sub.4-3-F 81 CH.sub.3 4-OCH.sub.3
CH.sub.2C.sub.6H.sub.4-2-F 82 CH.sub.3 4-OCH.sub.3
C(.dbd.O)OC.sub.2H.sub.5 83 CH.sub.3 4-OCH.sub.3
C(.dbd.O)NHCH.sub.3 84 CH.sub.3 4-OCH.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 85 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.3 86 CH.sub.3 4-OC.sub.2H.sub.5 C.sub.2H.sub.5 87 CH.sub.3
4-OC.sub.2H.sub.5 n-C.sub.3H.sub.7 88 CH.sub.3 4-OC.sub.2H.sub.5
i-C.sub.3H.sub.7 89 CH.sub.3 4-OC.sub.2H.sub.5 n-C.sub.4H.sub.9 90
CH.sub.3 4-OC.sub.2H.sub.5 n-C.sub.6H.sub.13 91 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2F 92 CH.sub.3 4-OC.sub.2H.sub.5 CHF.sub.2
93 CH.sub.3 4-OC.sub.2H.sub.5 CH.sub.2CF.sub.3 94 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2CH.dbd.CH.sub.2 95 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2CH.dbd.CHCH.sub.3 96 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 97 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2CH.dbd.CHCl 98 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2CH.dbd.CCl.sub.2 99 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 100 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2C.ident.CH 101 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2Si(CH.sub.3).sub.3 102 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2-c.propyl-2,2-Cl.sub.2 103 CH.sub.3 4-OC.sub.2H.sub.5
CH.sub.2CN 104 CH.sub.3 4-OC.sub.2H.sub.5 CH.sub.2COOC.sub.2H.sub.-
5 105 CH.sub.3 4-OC.sub.2H.sub.5 CH(CH.sub.3)COOC.sub.2H.sub.5 106
CH.sub.3 4-OC.sub.2H.sub.5 CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 107
CH.sub.3 4-OC.sub.2H.sub.5 CH.sub.2C.sub.6H.sub.4-4-F 108 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2C.sub.6H.sub.4-3-F 109 CH.sub.3
4-OC.sub.2H.sub.5 CH.sub.2C.sub.6H.sub.4-2-F 110 CH.sub.3
4-OC.sub.2H.sub.5 C(.dbd.O)OC.sub.2H.sub.5 111 CH.sub.3
4-OC.sub.2H.sub.5 C(.dbd.O)NHCH.sub.3 112 CH.sub.3
4-OC.sub.2H.sub.5 C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 113 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.3 114 CH.sub.3 4-O-n-C.sub.3H.sub.7
C.sub.2H.sub.5 115 CH.sub.3 4-O-n-C.sub.3H.sub.7 n-C.sub.3H.sub.7
116 CH.sub.3 4-O-n-C.sub.3H.sub.7 i-C.sub.3H.sub.7 117 CH.sub.3
4-O-n-C.sub.3H.sub.7 n-C.sub.4H.sub.9 118 CH.sub.3
4-O-n-C.sub.3H.sub.7 n-C.sub.6H.sub.13 119 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2F 120 CH.sub.3 4-O-n-C.sub.3H.sub.7
CHF.sub.2 121 CH.sub.3 4-O-n-C.sub.3H.sub.7 CH.sub.2CF.sub.3 122
CH.sub.3 4-O-n-C.sub.3H.sub.7 CH.sub.2CH.dbd.CH.sub.2 123 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2CH.dbd.CHCH.sub.3 124 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 125 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2CH.dbd.CHCl 126 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2CH.dbd.CCl.sub.2 127 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2C(CH.sub.3).dbd.CH.sub.2 128 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2C.ident.CH 129 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2Si(CH.sub.3).sub.3 130 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2-c.propyl-2,2-Cl.sub.2 131 CH.sub.3
4-O-n-C.sub.3H.sub.7 CH.sub.2CN 132 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH.sub.2COOC.sub.2H.sub.5 133 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH(CH.sub.3)COOC.sub.2H.sub.5 134 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 135 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH.sub.2C.sub.6H.sub.4-4-F 136 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH.sub.2C.sub.6H.sub.4-3-F 137 CH.sub.3 4-O-n-C.sub.3H.sub.7
CH.sub.2C.sub.6H.sub.4-2-F 138 CH.sub.3 4-O-n-C.sub.3H.sub.7
C(.dbd.O)OC.sub.2H.sub.5 139 CH.sub.3 4-O-n-C.sub.3H.sub.7
C(.dbd.O)NHCH.sub.3 140 CH.sub.3 4-O-n-C.sub.3H.sub.7
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 141 CH.sub.3 2-CH.sub.3 CH.sub.3
142 CH.sub.3 2-CH.sub.3 C.sub.2H.sub.5 143 CH.sub.3 2-CH.sub.3
n-C.sub.3H.sub.7 144 CH.sub.3 2-CH.sub.3 i-C.sub.3H.sub.7 145
CH.sub.3 2-CH.sub.3 n-C.sub.4H.sub.9 146 CH.sub.3 2-CH.sub.3
n-C.sub.6H.sub.13 147 CH.sub.3 2-CH.sub.3 CH.sub.2F 148 CH.sub.3
2-CH.sub.3 CHF.sub.2 149 CH.sub.3 2-CH.sub.3 CH.sub.2CF.sub.3 150
CH.sub.3 2-CH.sub.3 CH.sub.2CH.dbd.CH.sub.2 151 CH.sub.3 2-CH.sub.3
CH.sub.2CH.dbd.CHCH.sub.3 152 CH.sub.3 2-CH.sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 153 CH.sub.3 2-CH.sub.3
CH.sub.2CH.dbd.CHCl 154 CH.sub.3 2-CH.sub.3
CH.sub.2CH.dbd.CCl.sub.2 155 CH.sub.3 2-CH.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 156 CH.sub.3 2-CH.sub.3
CH.sub.2C.ident.CH 157 CH.sub.3 2-CH.sub.3 CH.sub.2Si(CH.sub.3).su-
b.3 158 CH.sub.3 2-CH.sub.3 CH.sub.2-c.propyl-2,2-Cl.sub.2 159
CH.sub.3 2-CH.sub.3 CH.sub.2CN 160 CH.sub.3 2-CH.sub.3
CH.sub.2COOC.sub.2H.sub.5 161 CH.sub.3 2-CH.sub.3
CH(CH.sub.3)COOC.sub.2H.sub.5 162 CH.sub.3 2-CH.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 163 CH.sub.3 2-CH.sub.3
CH.sub.2C.sub.6H.sub.4-4-F 164 CH.sub.3 2-CH.sub.3
CH.sub.2C.sub.6H.sub.4-3-F 165 CH.sub.3 2-CH.sub.3
CH.sub.2C.sub.6H.sub.4-2-F 166 CH.sub.3 2-CH.sub.3
C(.dbd.O)OC.sub.2H.sub.5 167 CH.sub.3 2-CH.sub.3
C(.dbd.O)NHCH.sub.3 168 CH.sub.3 2-CH.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 169 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.3 170 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 C.sub.2H.sub.5 171 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 n-C.sub.3H.sub.7 172 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 i-C.sub.3H.sub.7 173 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 n-C.sub.4H.sub.9 174 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 n-C.sub.6H.sub.13 175 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2F 176 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CHF.sub.2 177 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CF.sub.3 178 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CH.dbd.CH.sub.2 179 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CH.dbd.CHCH.sub.3 180
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 181 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CH.dbd.CHCl 182 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CH.dbd.CCl.sub.2 183 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2C(CH.sub.3).dbd.CH.s- ub.2
184 CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2C.ident.CH 185
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2Si(CH.sub.3).su- b.3
186 CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3
CH.sub.2-c.propyl-2,2-Cl.sub.2 187 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2CN 188 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2COOC.sub.2H.sub.5 189
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3
CH(CH.sub.3)COOC.sub.2H.sub.5 190 CH.sub.3
4-OCH.sub.2Si(CH.sub.3).sub.3 CH.sub.2C.sub.6H.sub.4-3-CF.- sub.3
191 CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3
CH.sub.2C.sub.6H.sub.4-4-F 192 CH.sub.3 4-OCH.sub.2Si(CH.sub.3).su-
b.3 CH.sub.2C.sub.6H.sub.4-3-F 193 CH.sub.3
4-OCH.sub.2Si(CH.sub.3)- .sub.3 CH.sub.2C.sub.6H.sub.4-2-F 194
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3 C(.dbd.O)OC.sub.2H.sub.5 195
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3 C(.dbd.O)NHCH.sub.3 196
CH.sub.3 4-OCH.sub.2Si(CH.sub.3).sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 197 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.3 198 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 C.sub.2H.sub.5 199 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 n-C.sub.3H.sub.7 200 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 i-C.sub.3H.sub.7 201 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 n-C.sub.4H.sub.9 202 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 n-C.sub.6H.sub.13 203 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2F 204 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CHF.sub.2 205 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CF.sub.3 206 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 207
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2CH.dbd.CHCH.sub.3 208 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-
-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 209 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CHCl 210
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2CH.dbd.CCl.sub.2 211 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 212 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2C.ident.CH 213
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2Si(CH.sub.3).sub.3 214 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.sub.2
215 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CN 216
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2COOC.sub.2H.sub.5 217 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub-
.5 218 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 219 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 220
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
CH.sub.2C.sub.6H.sub.4-- 3-F 221 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 CH.sub.2C.sub.6H.sub.4-2-F 222
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-- 4-CF.sub.3
C(.dbd.O)OC.sub.2H.sub.5 223 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3 C(.dbd.O)NHCH.sub.3 224
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-CF.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H- .sub.5 225 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.3 226 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 C.sub.2H.sub.5 227 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 n-C.sub.3H.sub.7 228 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 i-C.sub.3H.sub.7 229 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 n-C.sub.4H.sub.9 230 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 n-C.sub.6H.sub.13 231 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2F 232 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CHF.sub.2 233 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CF.sub.3 234 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 235
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2CH.dbd.CHCH.sub.3 236 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-
-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 237 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CHCl 238
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2CH.dbd.CCl.sub.2 239 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 240 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.ident.CH 241
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2Si(CH.sub.3).sub.3 242 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.sub.2
243 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CN 244
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2COOC.sub.2H.sub.5 245 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub-
.5 246 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 247 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 248
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C.sub.6H.sub.4-- 3-F 249 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.sub.6H.sub.4-2-F 250
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-- 3-CF.sub.3
C(.dbd.O)OC.sub.2H.sub.5 251 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 C(.dbd.O)NHCH.sub.3 252
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H- .sub.5 253 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.3 254 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 C.sub.2H.sub.5 255 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 n-C.sub.3H.sub.7 256 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 i-C.sub.3H.sub.7 257 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 n-C.sub.4H.sub.9 258 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 n-C.sub.6H.sub.13 259 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2F 260 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CHF.sub.2 261 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CF.sub.3 262 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 263
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2CH.dbd.CHCH.sub.3 264 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-
-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 265 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CHCl 266
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2CH.dbd.CCl.sub.2 267 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 268 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2C.ident.CH 269
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2Si(CH.sub.3).sub.3
270 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2-c.propyl-2,2-Cl.sub.2 271 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CN 272 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2COOC.sub.2H.sub.5 273
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH(CH.sub.3)COOC.sub.2H.sub- .5 274 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 275 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 276
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
CH.sub.2C.sub.6H.sub.4-- 3-F 277 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 CH.sub.2C.sub.6H.sub.4-2-F 278
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-- 2-CF.sub.3
C(.dbd.O)OC.sub.2H.sub.5 279 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3 C(.dbd.O)NHCH.sub.3 280
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-2-CF.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H- .sub.5 281 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.3 282 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F C.sub.2H.sub.5 283 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F n-C.sub.3H.sub.7 284 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F i-C.sub.3H.sub.7 285 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F n-C.sub.4H.sub.9 286 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F n-C.sub.6H.sub.13 287 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2F 288 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CHF.sub.2 289 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CF.sub.3 290 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CH.sub.2 291 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CHCH.sub.3 292
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 293 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CHCl 294 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CCl.sub.2 295 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2C(CH.sub.3).dbd.CH.s- ub.2
296 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2C.ident.CH 297
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2Si(CH.sub.3).su- b.3
298 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F
CH.sub.2-c.propyl-2,2-Cl.sub.2 299 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2CN 300 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2COOC.sub.2H.sub.5 301
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F
CH(CH.sub.3)COOC.sub.2H.sub.5 302 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-F CH.sub.2C.sub.6H.sub.4-3-CF.- sub.3
303 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F
CH.sub.2C.sub.6H.sub.4-4-F 304 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4--
4-F CH.sub.2C.sub.6H.sub.4-3-F 305 CH.sub.3
4-OCH.sub.2C.sub.6H.sub- .4-4-F CH.sub.2C.sub.6H.sub.4-2-F 306
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F C(.dbd.O)OC.sub.2H.sub.5 307
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F C(.dbd.O)NHCH.sub.3 308
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-F
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 309 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.3 310 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 C.sub.2H.sub.5 311 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 n-C.sub.3H.sub.7 312 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 i-C.sub.3H.sub.7 313 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 n-C.sub.4H.sub.9 314 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 n-C.sub.6H.sub.13 315 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2F 316 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CHF.sub.2 317 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CF.sub.3 318 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 319 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 320 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 321
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CHCl 322
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CCl.sub.2 323
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.- 2 324 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.ident.CH 325 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2Si(CH.sub.3).sub.3 326
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.su-
b.2 327 CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CN 328
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2COOC.sub.2H.sub.5 329
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub.5
330 CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-C- F.sub.3 331 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 332
CH.sub.3 4-OC.sub.6H.sub.4-3-CF.sub- .3 CH.sub.2C.sub.6H.sub.4-3-F
333 CH.sub.3 4-OC.sub.6H.sub.4-3-CF.s- ub.3
CH.sub.2C.sub.6H.sub.4-2-F 334 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 C(.dbd.O)OC.sub.2H.sub.5 335 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 C(.dbd.O)NHCH.sub.3 336 CH.sub.3
4-OC.sub.6H.sub.4-3-CF.sub.3 C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 337
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.3 338
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 C.sub.2H.sub.5
339 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
n-C.sub.3H.sub.7 340 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 i-C.sub.3H.sub.7 341
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF- .sub.3
n-C.sub.4H.sub.9 342 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.-
4-3-CF.sub.3 n-C.sub.6H.sub.13 343 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2F 344 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CHF.sub.2 345 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CF.sub.3 346
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2CH.dbd.CH.sub.2 347 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub-
.4-3-CF.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 348 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 349 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CH.dbd.CHCl 350
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3- -CF.sub.3
CH.sub.2CH.dbd.CCl.sub.2 351 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 352 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.ident.CH 353
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-- CF.sub.3
CH.sub.2Si(CH.sub.3).sub.3 354 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.sub.2
355 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2CN
356 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2COOC.sub.2H.sub.5 357 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub.5
358 C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 359 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 360
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-F 361 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 CH.sub.2C.sub.6H.sub.4-2-F 362
C.sub.2H.sub.5 4-OC.sub.6H.sub.4-3-CF.sub.3
C(.dbd.O)OC.sub.2H.sub.5 363 C.sub.2H.sub.5
4-OCH.sub.2C.sub.6H.sub.4-3-CF.sub.3 C(.dbd.O)NHCH.sub.3 364
C.sub.2H.sub.5 4-OCH.sub.2C.sub.6H.sub.4-3- -CF.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 365 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.3 366 CH.sub.3 4-OC.sub.6H.sub.4-4-Cl
C.sub.2H.sub.5 367 CH.sub.3 4-OC.sub.6H.sub.4-4-Cl n-C.sub.3H.sub.7
368 CH.sub.3 4-OC.sub.6H.sub.4-4-Cl i-C.sub.3H.sub.7 369 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl n-C.sub.4H.sub.9 370 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl n-C.sub.6H.sub.13 371 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2F 372 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CHF.sub.2 373 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CF.sub.3 374 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CH.sub.2 375 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CHCH.sub.3 376 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.C(CH.sub.3).sub.2 377
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CHCl 378 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CCl.sub.2 379 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2C(CH.sub.3).dbd.CH.sub.2 380
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl CH.sub.2C.ident.CH 381 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2Si(CH.sub.3).sub.3 382 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2-c.propyl-2,2-Cl.sub.2 383 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2CN 384 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2COOC.sub.2H.sub.5 385 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH(CH.sub.3)COOC.sub.2H.sub.5 386 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 387
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-4-F 388
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-3-F 389
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-2-F 390
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl C(.dbd.O)OC.sub.2H.sub.5 391
CH.sub.3 4-OC.sub.6H.sub.4-4-Cl C(.dbd.O)NHCH.sub.3 392 CH.sub.3
4-OC.sub.6H.sub.4-4-Cl C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 393
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.3 394 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl C.sub.2H.sub.5 395 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl n-C.sub.3H.sub.7 396 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl i-C.sub.3H.sub.7 397 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl n-C.sub.4H.sub.9 398 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl n-C.sub.6H.sub.13 399 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2F 400 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CHF.sub.2 401 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CF.sub.3 402 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CH.dbd.CH.sub.2 403 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CH.dbd.CHCH.sub.3 404 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CH.dbd.C(CH.sub.3).sub.2 405
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.2CH.dbd.CHCl 406 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CH.dbd.CCl.sub.2 407 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2C(CH.sub.3).dbd.CH.sub.2 408
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.2C.ident.CH 409 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2Si(CH.sub.3).sub.3 410 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2-c.propyl-2,2-Cl.sub.2 411 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2CN 412 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2COOC.sub.2H.sub.5 413 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH(CH.sub.3)COOC.sub.2H.sub.5 414 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 415
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.2C.sub.6H.sub.4-4-F 416
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.2C.sub.6H.sub.4-3-F 417
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl CH.sub.2C.sub.6H.sub.4-2-F 418
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl C(.dbd.O)OC.sub.2H.sub.5 419
CH.sub.3 4-OC.sub.6H.sub.4-3-Cl C(.dbd.O)NHCH.sub.3 420 CH.sub.3
4-OC.sub.6H.sub.4-3-Cl C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 421
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.3 242 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl C.sub.2H.sub.5 423 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl n-C.sub.3H.sub.7 424 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl i-C.sub.3H.sub.7 425 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl n-C.sub.4H.sub.9 426 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl n-C.sub.6H.sub.13 427 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2F 428 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CHF.sub.2 429 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CF.sub.3 430 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CH.dbd.CH.sub.2 431 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CH.dbd.CHCH.sub.3 432 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CH.dbd.C(CH.sub.3).sub.2 433
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.2CH.dbd.CHCl 434 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CH.dbd.CCl.sub.2 435 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2C(CH.sub.3).dbd.CH.sub.2 436
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.2C.ident.CH 437 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2Si(CH.sub.3).sub.3 438 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2-c.propyl-2,2-Cl.sub.2 439 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2CN 440 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2COOC.sub.2H.sub.5 441 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH(CH.sub.3)COOC.sub.2H.sub.5 442 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 443
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.2C.sub.6H.sub.4-4-F 444
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.2C.sub.6H.sub.4-3-F 445
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl CH.sub.2C.sub.6H.sub.4-2-F 446
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl C(.dbd.O)OC.sub.2H.sub.5 447
CH.sub.3 4-OC.sub.6H.sub.4-2-Cl C(.dbd.O)NHCH.sub.3 448 CH.sub.3
4-OC.sub.6H.sub.4-2-Cl C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 449
CH.sub.3 4-OC.sub.6H.sub.4-4-F CH.sub.3 450 CH.sub.3
4-OC.sub.6H.sub.4-4-F C.sub.2H.sub.5 451 CH.sub.3
4-OC.sub.6H.sub.4-4-F n-C.sub.3H.sub.7 452 CH.sub.3
4-OC.sub.6H.sub.4-4-F i-C.sub.3H.sub.7 453 CH.sub.3
4-OC.sub.6H.sub.4-4-F n-C.sub.4H.sub.9 454 CH.sub.3
4-OC.sub.6H.sub.4-4-F n-C.sub.6H.sub.13 455 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2F 456 CH.sub.3 4-OC.sub.6H.sub.4-4-F
CHF.sub.2 457 CH.sub.3 4-OC.sub.6H.sub.4-4-F CH.sub.2CF.sub.3 458
CH.sub.3 4-OC.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CH.sub.2 459 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CHCH.sub.3 460 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2CH.dbd.C(CH.sub.3).sub.2 461 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CHCl 462 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2CH.dbd.CCl.sub.2 463 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2C(CH.sub.3).dbd.CH.sub.2 464 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2C.ident.CH 465 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2Si(CH.sub.3).sub.3 466 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2-c.propyl-2,2-Cl.sub.2 467 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2CN 468 CH.sub.3 4-OC.sub.6H.sub.4-4-F
CH.sub.2COOC.sub.2H.sub.5 469 CH.sub.3 4-OC.sub.6H.sub.4-4-F
CH(CH.sub.3)COOC.sub.2H.sub.5 470 CH.sub.3 4-OC.sub.6H.sub.4-4-F
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 471 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2C.sub.6H.sub.4-4-F 472 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2C.sub.6H.sub.4-3-F 473 CH.sub.3
4-OC.sub.6H.sub.4-4-F CH.sub.2C.sub.6H.sub.4-2-F 474 CH.sub.3
4-OC.sub.6H.sub.4-4-F C(.dbd.O)OC.sub.2H.sub.5 475 CH.sub.3
4-OC.sub.6H.sub.4-4-F C(.dbd.O)NHCH.sub.3 476 CH.sub.3
4-OC.sub.6H.sub.4-4-F C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 477
CH.sub.3 4-OC.sub.6H.sub.4-3-F CH.sub.3 478 CH.sub.3
4-OC.sub.6H.sub.4-3-F C.sub.2H.sub.5 479 CH.sub.3
4-OC.sub.6H.sub.4-3-F n-C.sub.3H.sub.7 480 CH.sub.3
4-OC.sub.6H.sub.4-3-F i-C.sub.3H.sub.7 481 CH.sub.3
4-OC.sub.6H.sub.4-3-F n-C.sub.4H.sub.9 482 CH.sub.3
4-OC.sub.6H.sub.4-3-F n-C.sub.6H.sub.13 483 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2F 484 CH.sub.3 4-OC.sub.6H.sub.4-3-F
CHF.sub.2 485 CH.sub.3 4-OC.sub.6H.sub.4-3-F CH.sub.2CF.sub.3 486
CH.sub.3 4-OC.sub.6H.sub.4-3-F CH.sub.2CH.dbd.CH.sub.2 487 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2CH.dbd.CHCH.sub.3 488 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2CH.dbd.C(CH.sub.3).sub.2 489 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2CH.dbd.CHCl 490 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2CH.dbd.CCl.sub.2 491 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2C(CH.sub.3).dbd.CH.sub.2 492 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2C.ident.CH 493 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2Si(CH.sub.3).sub.3 494 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2-c.propyl-2,2-Cl.sub.2 495 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2CN 496 CH.sub.3 4-OC.sub.6H.sub.4-3-F
CH.sub.2COOC.sub.2H.sub.5 497 CH.sub.3 4-OC.sub.6H.sub.4-3-F
CH(CH.sub.3)COOC.sub.2H.sub.5 498 CH.sub.3 4-OC.sub.6H.sub.4-3-F
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 499 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2C.sub.6H.sub.4-4-F 500 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2C.sub.6H.sub.4-3-F 501 CH.sub.3
4-OC.sub.6H.sub.4-3-F CH.sub.2C.sub.6H.sub.4-2-F 502 CH.sub.3
4-OC.sub.6H.sub.4-3-F C(.dbd.O)OC.sub.2H.sub.5 503 CH.sub.3
4-OC.sub.6H.sub.4-3-F C(.dbd.O)NHCH.sub.3 504 CH.sub.3
4-OC.sub.6H.sub.4-3-F C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 505
CH.sub.3 4-OC.sub.6H.sub.4-2-F CH.sub.3 506 CH.sub.3
4-OC.sub.6H.sub.4-2-F C.sub.2H.sub.5 507 CH.sub.3
4-OC.sub.6H.sub.4-2-F n-C.sub.3H.sub.7 508 CH.sub.3
4-OC.sub.6H.sub.4-2-F i-C.sub.3H.sub.7 509 CH.sub.3
4-OC.sub.6H.sub.4-2-F n-C.sub.4H.sub.9 510 CH.sub.3
4-OC.sub.6H.sub.4-2-F n-C.sub.6H.sub.13 511 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2F 512 CH.sub.3 4-OC.sub.6H.sub.4-2-F
CHF.sub.2 513 CH.sub.3 4-OC.sub.6H.sub.4-2-F CH.sub.2CF.sub.3 514
CH.sub.3 4-OC.sub.6H.sub.4-2-F CH.sub.2CH.dbd.CH.sub.2 515 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2CH.dbd.CHCH.sub.3 516 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2CH.dbd.C(CH.sub.3).sub.2 517 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2CH.dbd.CHCl 518 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2CH.dbd.CCl.sub.2 519 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2C(CH.sub.3).dbd.CH.sub.2 520 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2C.ident.CH 521 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2Si(CH.sub.3).sub.3 522 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2-c.propyl-2,2-Cl.sub.2 523 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2CN 524 CH.sub.3 4-OC.sub.6H.sub.4-2-F
CH.sub.2COOC.sub.2H.sub.5 525 CH.sub.3 4-OC.sub.6H.sub.4-2-F
CH(CH.sub.3)COOC.sub.2H.sub.5 526 CH.sub.3 4-OC.sub.6H.sub.4-2-F
CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 527 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2C.sub.6H.sub.4-4-F 528 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2C.sub.6H.sub.4-3-F 529 CH.sub.3
4-OC.sub.6H.sub.4-2-F CH.sub.2C.sub.6H.sub.4-2-F 530 CH.sub.3
4-OC.sub.6H.sub.4-2-F C(.dbd.O)OC.sub.2H.sub.5 531 CH.sub.3
4-OC.sub.6H.sub.4-2-F C(.dbd.O)NHCH.sub.3 532 CH.sub.3
4-OC.sub.6H.sub.4-2-F C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 533
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.3 534 CH.sub.3
4-OC.sub.6H.sub.4-4-Br C.sub.2H.sub.5 535 CH.sub.3
4-OC.sub.6H.sub.4-4-Br n-C.sub.3H.sub.7 536 CH.sub.3
4-OC.sub.6H.sub.4-4-Br i-C.sub.3H.sub.7 537 CH.sub.3
4-OC.sub.6H.sub.4-4-Br n-C.sub.4H.sub.9 538 CH.sub.3
4-OC.sub.6H.sub.4-4-Br n-C.sub.6H.sub.13 539 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2F 540 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CHF.sub.2 541 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CF.sub.3 542 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CH.dbd.CH.sub.2 543 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CH.dbd.CHCH.sub.3 544 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CH.dbd.C(CH.sub.3).sub.2 545
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.2CH.dbd.CHCl 546 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CH.dbd.CCl.sub.2 547 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2C(CH.sub.3).dbd.CH.sub.2 548
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.2C.ident.CH 549 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2Si(CH.sub.3).sub.3 550 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2-c.propyl-2,2-Cl.sub.2 551 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2CN 552 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2COOC.sub.2H.sub.5 553 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH(CH.sub.3)COOC.sub.2H.sub.5 554 CH.sub.3
4-OC.sub.6H.sub.4-4-Br CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 555
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.2C.sub.6H.sub.4-4-F 556
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.2C.sub.6H.sub.4-3-F 557
CH.sub.3 4-OC.sub.6H.sub.4-4-Br CH.sub.2C.sub.6H.sub.4-2-F 558
CH.sub.3 4-OC.sub.6H.sub.4-4-Br C(.dbd.O)OC.sub.2H.sub.5 559
CH.sub.3 4-OC.sub.6H.sub.4-4-Br C(.dbd.O)NHCH.sub.3 560 CH.sub.3
4-OC.sub.6H.sub.4-4-Br C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 561
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.3 562 CH.sub.3
4-OC.sub.6H.sub.4-3-Br C.sub.2H.sub.5 563 CH.sub.3
4-OC.sub.6H.sub.4-3-Br n-C.sub.3H.sub.7 564 CH.sub.3
4-OC.sub.6H.sub.4-3-Br i-C.sub.3H.sub.7 565 CH.sub.3
4-OC.sub.6H.sub.4-3-Br n-C.sub.4H.sub.9 566 CH.sub.3
4-OC.sub.6H.sub.4-3-Br n-C.sub.6H.sub.13 567 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2F 568 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CHF.sub.2 569 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CF.sub.3 570 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CH.dbd.CH.sub.2 571 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CH.dbd.CHCH.sub.3 572 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CH.dbd.C(CH.sub.3).sub.2 573
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.2CH.dbd.CHCl 574 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CH.dbd.CCl.sub.2 575 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2C(CH.sub.3).dbd.CH.sub.2 576
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.2C.ident.CH 577 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2Si(CH.sub.3).sub.3 578 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2-c.propyl-2,2-Cl.sub.2 579 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2CN 580 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2COOC.sub.2H.sub.5 581 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH(CH.sub.3)COOC.sub.2H.sub.5 582 CH.sub.3
4-OC.sub.6H.sub.4-3-Br CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 583
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.2C.sub.6H.sub.4-4-F 584
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.2C.sub.6H.sub.4-3-F 585
CH.sub.3 4-OC.sub.6H.sub.4-3-Br CH.sub.2C.sub.6H.sub.4-2-F 586
CH.sub.3 4-OC.sub.6H.sub.4-3-Br C(.dbd.O)OC.sub.2H.sub.5 587
CH.sub.3 4-OC.sub.6H.sub.4-3-Br C(.dbd.O)NHCH.sub.3 588 CH.sub.3
4-OC.sub.6H.sub.4-3-Br C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 589
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.3 590 CH.sub.3
4-OC.sub.6H.sub.4-2-Br C.sub.2H.sub.5 591 CH.sub.3
4-OC.sub.6H.sub.4-2-Br n-C.sub.3H.sub.7 592 CH.sub.3
4-OC.sub.6H.sub.4-2-Br i-C.sub.3H.sub.7 593 CH.sub.3
4-OC.sub.6H.sub.4-2-Br n-C.sub.4H.sub.9 594 CH.sub.3
4-OC.sub.6H.sub.4-2-Br n-C.sub.6H.sub.13 595 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2F 596 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CHF.sub.2 597 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CF.sub.3 598 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CH.dbd.CH.sub.2 599 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CH.dbd.CHCH.sub.3 600 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CH.dbd.C(CH.sub.3).sub.2 601
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.2CH.dbd.CHCl 602 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CH.dbd.CCl.sub.2 603 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2C(CH.sub.3).dbd.CH.sub.2 604
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.2C.ident.CH 605 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2Si(CH.sub.3).sub.3 606 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2-c.propyl-2,2-Cl.sub.2 607 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2CN 608 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2COOC.sub.2H.sub.5 609 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH(CH.sub.3)COOC.sub.2H.sub.5 610 CH.sub.3
4-OC.sub.6H.sub.4-2-Br CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 611
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.2C.sub.6H.sub.4-4-F 612
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.2C.sub.6H.sub.4-3-F 613
CH.sub.3 4-OC.sub.6H.sub.4-2-Br CH.sub.2C.sub.6H.sub.4-2-F 614
CH.sub.3 4-OC.sub.6H.sub.4-2-Br C(.dbd.O)OC.sub.2H.sub.5 615
CH.sub.3 4-OC.sub.6H.sub.4-2-Br C(.dbd.O)NHCH.sub.3 616 CH.sub.3
4-OC.sub.6H.sub.4-2-Br C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 617
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.3 618 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 C.sub.2H.sub.5 619 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 n-C.sub.3H.sub.7 620 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 i-C.sub.3H.sub.7 621 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 n-C.sub.4H.sub.9 622 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 n-C.sub.6H.sub.13 623 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2F 624 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CHF.sub.2 625 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CF.sub.3 626 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CH.dbd.CH.sub.2 627 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CH.dbd.CHCH.sub.3 628
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2
CH.sub.2CH.dbd.C(CH.sub.3).su- b.2 629 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CH.dbd.CHCl 630 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CH.dbd.CCl.sub.2 631
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub- .2
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 632 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2C.ident.CH 633 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2Si(CH.sub.3).sub.3 634
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2
CH.sub.2-c.propyl-2,2-Cl.sub.2 635 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2CN 636 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2COOC.sub.2H.sub.5 637
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2
CH(CH.sub.3)COOC.sub.2H.sub.5 638 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-3-CF.sub.3
639 CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2
CH.sub.2C.sub.6H.sub.4-4-F 640 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-3-F 641
CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-2-F
642 CH.sub.3 4-OC.sub.6H.sub.3-2,4-Cl.sub.2
C(.dbd.O)OC.sub.2H.sub.5 643 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 C(.dbd.O)NHCH.sub.3 644 CH.sub.3
4-OC.sub.6H.sub.3-2,4-Cl.sub.2 C(.dbd.O)C(.dbd.O)OC.sub.- 2H.sub.5
645 CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.3 646 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 C.sub.2H.sub.5 647 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 n-C.sub.3H.sub.7 648 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 i-C.sub.3H.sub.7 649 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 n-C.sub.4H.sub.9 650 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 n-C.sub.6H.sub.13 651 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2F 652 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CHF.sub.2 653 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CF.sub.3 654 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CH.dbd.CH.sub.2 655 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CH.dbd.CHCH.sub.3 656
CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2CH.dbd.C(CH.sub.3).su- b.2 657 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CH.dbd.CHCl 658 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CH.dbd.CCl.sub.2 659
CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub- .2
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 660 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.ident.CH 661 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2Si(CH.sub.3).sub.3 662
CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2-c.propyl-2,2-Cl.sub.2 663 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CN 664 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2COOC.sub.2H.sub.5 665
CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2
CH(CH.sub.3)COOC.sub.2H.sub.5 666 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-3-CF.sub.3
667 CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2C.sub.6H.sub.4-4-F 668 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-3-F 669
CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-2-F
670 CH.sub.3 4-OC.sub.6H.sub.3-3,4-Cl.sub.2
C(.dbd.O)OC.sub.2H.sub.5 671 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 C(.dbd.O)NHCH.sub.3 672 CH.sub.3
4-OC.sub.6H.sub.3-3,4-Cl.sub.2 C(.dbd.O)C(.dbd.O)OC.sub.- 2H.sub.5
673 CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.3 674 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br C.sub.2H.sub.5 675 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br n-C.sub.3H.sub.7 676 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br i-C.sub.3H.sub.7 677 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br n-C.sub.4H.sub.9 678 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br n-C.sub.6H.sub.13 679 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2F 680 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CHF.sub.2 681 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CF.sub.3 682 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CH.dbd.CH.sub.2 683 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CH.dbd.CHCH.sub.3 684 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CH.dbd.C(CH.sub.3).sub.2 685
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CH.dbd.CHCl 686
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CH.dbd.CCl.sub.2 687
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 688 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2C.ident.CH 689 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2Si(CH.sub.3).sub.3 690 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2-c.propyl-2,2-Cl.sub.2 691
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2CN 692 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2COOC.sub.2H.sub.5 693 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH(CH.sub.3)COOC.sub.2H.sub.5 694
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br
CH.sub.2C.sub.6H.sub.4-3-CF.sub.- 3 695 CH.sub.3
4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2C.sub.6H.sub.4-4- -F 696
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2C.sub.6H.sub.4-- 3-F
697 CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br CH.sub.2C.sub.6H.sub.4-2-F
698 CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-B- r C(.dbd.O)OC.sub.2H.sub.5
699 CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br C(.dbd.O)NHCH.sub.3 700
CH.sub.3 4-OC.sub.6H.sub.3-2-Cl,4-Br
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 701 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.3 702 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) C.sub.2H.sub.5 703 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) n-C.sub.3H.sub.7 704
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) i-C.sub.3H.sub.7
705 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
n-C.sub.4H.sub.9 706 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) n-C.sub.6H.sub.13 707
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2F 708
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CHF.sub.2 709
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2CF.sub.3
710 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH.sub.2CH.dbd.CH.sub.2 711 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.-
sub.2O--) CH.sub.2CH.dbd.CHCH.sub.3 712 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 713 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2CH.dbd.CHCl 714
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.- 2O--)
CH.sub.2CH.dbd.CCl.sub.2 715 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(-
--OCH.sub.2O--) CH.sub.2C(CH.sub.3).dbd.CH.sub.2 716 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2C.ident.CH 717
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH.sub.2Si(CH.sub.3).sub.- 3 718 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH.sub.2-c.propyl-2,2-Cl.sub.2 719 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2CN 720 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2COOC.sub.2H.sub.5
721 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH(CH.sub.3)COOC.sub.2H.sub.5 722 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(-
--OCH.sub.2O--) CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 723 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) CH.sub.2C.sub.6H.sub.4-4-F
724 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
CH.sub.2C.sub.6H.sub.4-3-F 725 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--O-
CH.sub.2O--) CH.sub.2C.sub.6H.sub.4-2-F 726 CH.sub.3
4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) C(.dbd.O)OC.sub.2H.sub.5 727
CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--) C(.dbd.O)NHCH.sub.3
728 CH.sub.3 4-OC.sub.6H.sub.3-3,4-(--OCH.sub.2O--)
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 729 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.3 730 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 C.sub.2H.sub.5 731 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 n-C.sub.3H.sub.7 732 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 i-C.sub.3H.sub.7 733 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 n-C.sub.4H.sub.9 734 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 n-C.sub.6H.sub.13 735 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2F 736 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CHF.sub.2 737 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CF.sub.3 738 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CH.dbd.CH.sub.2 739 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 740
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 741 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CH.dbd.CHCl 742 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CH.dbd.CCl.sub.2 743 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2C(CH.sub.3).dbd.CH.s- ub.2
744 CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2C.ident.CH 745
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2Si(CH.sub.3).su- b.3
746 CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3
CH.sub.2-c.propyl-2,2-Cl.sub.2 747 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2CN 748 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2COOC.sub.2H.sub.5 749
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3
CH(CH.sub.3)COOC.sub.2H.sub.5 750 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH.sub.3 CH.sub.2C.sub.6H.sub.4-3-CF.- sub.3
751 CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3
CH.sub.2C.sub.6H.sub.4-4-F 752 CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.su-
b.3 CH.sub.2C.sub.6H.sub.4-3-F 753 CH.sub.3
4-OC.sub.6H.sub.4-4-SCH- .sub.3 CH.sub.2C.sub.6H.sub.4-2-F 754
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3 C(.dbd.O)OC.sub.2H.sub.5 755
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3 C(.dbd.O)NHCH.sub.3 756
CH.sub.3 4-OC.sub.6H.sub.4-4-SCH.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 757 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.3 758 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 C.sub.2H.sub.5 759 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 n-C.sub.3H.sub.7 760 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 i-C.sub.3H.sub.7 761 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 n-C.sub.4H.sub.9 762 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 n-C.sub.6H.sub.13 763 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2F 764 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CHF.sub.2 765 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CF.sub.3 766 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CH.dbd.CH.sub.2 767 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 768
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 769 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CH.dbd.CHCl 770 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CH.dbd.CCl.sub.2 771 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2C(CH.sub.3).dbd.CH.s- ub.2
772 CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2C.ident.CH 773
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2Si(CH.sub.3).su- b.3
774 CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3
CH.sub.2-c.propyl-2,2-Cl.sub.2 775 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2CN 776 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2COOC.sub.2H.sub.5 777
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3
CH(CH.sub.3)COOC.sub.2H.sub.5 778 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH.sub.3 CH.sub.2C.sub.6H.sub.4-3-CF.- sub.3
779 CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3
CH.sub.2C.sub.6H.sub.4-4-F 780 CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.su-
b.3 CH.sub.2C.sub.6H.sub.4-3-F 781 CH.sub.3
4-OC.sub.6H.sub.4-4-OCH- .sub.3 CH.sub.2C.sub.6H.sub.4-2-F 782
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3 C(.dbd.O)OC.sub.2H.sub.5 783
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3 C(.dbd.O)NHCH.sub.3 784
CH.sub.3 4-OC.sub.6H.sub.4-4-OCH.sub.3
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 785 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.3 786 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl C.sub.2H.sub.5 787 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl n-C.sub.3H.sub.7 788 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl i-C.sub.3H.sub.7 789 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl n-C.sub.4H.sub.9 790 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl n-C.sub.6H.sub.13 791 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2F 792 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CHF.sub.2 793 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CF.sub.3 794 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CH.dbd.CH.sub.2 795 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CH.dbd.CHCH.sub.3 796 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CH.dbd.C(CH.sub.3).sub.2 797
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CH.dbd.CHCl 798
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CH.dbd.CCl.sub.2 799
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 800 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2C.ident.CH 801 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2Si(CH.sub.3).sub.3 802 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2-c.propyl-2,2-Cl.sub.2 803
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2CN 804 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2COOC.sub.2H.sub.5 805 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH(CH.sub.3)COOC.sub.2H.sub.5 806
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl
CH.sub.2C.sub.6H.sub.4-3-CF.sub.- 3 807 CH.sub.3
4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2C.sub.6H.sub.4-4- -F 808
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2C.sub.6H.sub.4-- 3-F
809 CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl CH.sub.2C.sub.6H.sub.4-2-F
810 CH.sub.3 4-OC.sub.6H.sub.4-4-t-buty- l C(.dbd.O)OC.sub.2H.sub.5
811 CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl O(.dbd.O)NHCH.sub.3 812
CH.sub.3 4-OC.sub.6H.sub.4-4-t-butyl
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 813 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.3 814 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 C.sub.2H.sub.5 815 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 n-C.sub.3H.sub.7 816 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 i-C.sub.3H.sub.7 817 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 n-C.sub.4H.sub.9 818 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 n-C.sub.6H.sub.13 819 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2F 820 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CHF.sub.2 821 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CF.sub.3 822 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 823 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 824 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 825
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CHCl 826
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CH.dbd.CCl.sub.2 827
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.- 2 828 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2C.ident.CH 829 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2Si(CH.sub.3).sub.3 830
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.su-
b.2 831 CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2CN 832
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2COOC.sub.2H.sub.5 833
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub.5
834 CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-C- F.sub.3 835 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 836
CH.sub.3 4-OC.sub.6H.sub.4-4-CF.sub- .3 CH.sub.2C.sub.6H.sub.4-3-F
837 CH.sub.3 4-OC.sub.6H.sub.4-4-CF.s- ub.3
CH.sub.2C.sub.6H.sub.4-2-F 838 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 C(.dbd.O)OC.sub.2H.sub.5 839 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 C(.dbd.O)NHCH.sub.3 840 CH.sub.3
4-OC.sub.6H.sub.4-4-CF.sub.3 C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 841
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.3 842 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 C.sub.2H.sub.5 843 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 n-C.sub.3H.sub.7 844 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 i-C.sub.3H.sub.7 845 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 n-C.sub.4H.sub.9 846 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 n-C.sub.6H.sub.13 847 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2F 848 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CHF.sub.2 849 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CF.sub.3 850 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CH.sub.2 851 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CHCH.sub.3 852 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.C(CH.sub.3).sub.2 853
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CHCl 854
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CH.dbd.CCl.sub.2 855
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3
CH.sub.2C(CH.sub.3).dbd.CH.sub.- 2 856 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2C.ident.CH 857 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2Si(CH.sub.3).sub.3 858
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2-c.propyl-2,2-Cl.su-
b.2 859 CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2CN 860
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2COOC.sub.2H.sub.5 861
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3 CH(CH.sub.3)COOC.sub.2H.sub.5
862 CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub.3
CH.sub.2C.sub.6H.sub.4-3-C- F.sub.3 863 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 CH.sub.2C.sub.6H.sub.4-4-F 864
CH.sub.3 4-OC.sub.6H.sub.4-2-CF.sub- .3 CH.sub.2C.sub.6H.sub.4-3-F
865 CH.sub.3 4-OC.sub.6H.sub.4-2-CF.s- ub.3
CH.sub.2C.sub.6H.sub.4-2-F 866 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 C(.dbd.O)OC.sub.2H.sub.5 867 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 C(.dbd.O)NHCH.sub.3 868 CH.sub.3
4-OC.sub.6H.sub.4-2-CF.sub.3 C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5 869
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.3 870 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl C.sub.2H.sub.5 871 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl n-C.sub.3H.sub.7 872 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl i-C.sub.3H.sub.7 873 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl n-C.sub.4H.sub.9 874 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl n-C.sub.6H.sub.13 875 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2F 876 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CHF.sub.2 877 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CF.sub.3 878 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CH.sub.2 879 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CHCH.sub.3 880
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl
CH.sub.2CH.dbd.C(CH.sub.3).su- b.2 881 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CHCl 882 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CH.dbd.CCl.sub.2 883
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-- Cl
CH.sub.2C(CH.sub.3).dbd.CH.sub.2 884 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2C.ident.CH 885 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2Si(CH.sub.3).sub.3 886
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl
CH.sub.2-c.propyl-2,2-Cl.sub.2 887 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2CN 888 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2COOC.sub.2H.sub.5 889
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl
CH(CH.sub.3)COOC.sub.2H.sub.5 890 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-3-CF.sub.3
891 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl
CH.sub.2C.sub.6H.sub.4-4-F 892 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-3-F 893
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl CH.sub.2C.sub.6H.sub.4-2-F
894 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.4-4-Cl
C(.dbd.O)OC.sub.2H.sub.5 895 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl C(.dbd.O)NHCH.sub.3 896 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.4-4-Cl C(.dbd.O)C(.dbd.O)OC.sub.- 2H.sub.5
797 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.3 898
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 C.sub.2H.sub.5 899
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 n-C.sub.3H.sub.7
900 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub- .2
i-C.sub.3H.sub.7 901 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.s-
ub.2 n-C.sub.4H.sub.9 902 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl- .sub.2 n-C.sub.6H.sub.13 903
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4- -Cl.sub.2 CH.sub.2F 904
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.s- ub.2 CHF.sub.2 905
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CF.sub.3
906 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub- .2
CH.sub.2CH.dbd.CH.sub.2 907 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3-
,4-Cl.sub.2 CH.sub.2CH.dbd.CHCH.sub.3 908 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2CH.dbd.C(CH.sub.3).sub.2 909 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CH.dbd.CHCl 910
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.- sub.2
CH.sub.2CH.dbd.CCl.sub.2 911 CH.sub.3 4-OCH.sub.2C.sub.6H.sub-
.3-3,4-Cl.sub.2 CH.sub.2C(CH.sub.3).dbd.CH.sub.2 912 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.ident.CH 913
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2Si(CH.sub.3).sub.- 3 914 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2-c.propyl-2,2-Cl.sub.2 915 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2CN 916 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2COOC.sub.2H.sub.5
917 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
CH(CH.sub.3)COOC.sub.2H.sub.5 918 CH.sub.3 4-OCH.sub.2C.sub.6H.sub-
.3-3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-3-CF.sub.3 919 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-4-F
920 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
CH.sub.2C.sub.6H.sub.4-3-F 921 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3--
3,4-Cl.sub.2 CH.sub.2C.sub.6H.sub.4-2-F 922 CH.sub.3
4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 C(.dbd.O)OC.sub.2H.sub.5 923
CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2 C(.dbd.O)NHCH.sub.3
924 CH.sub.3 4-OCH.sub.2C.sub.6H.sub.3-3,4-Cl.sub.2
C(.dbd.O)C(.dbd.O)OC.sub.2H.sub.5
[0149] In Tables 2.1 and 2.2, the .sup.13C-NMR data of the
compounds
1-[4-(3-trifluoromethyl-phenylmethoxy)-phenyl]-1,2-propanedione
1-E-[methyloxime]-2-oxime and
1-[4-(3-trifluoromethylphenylmethoxy)-pheny- l]-1,2-propanedione
1-Z-[methyloxime]-2-oxime (which was prepared by one of the known
processes and from which the E/Z isomer mixture formed in the
preparation was isolated) or, respectively, methyl
2-[[[(1-methyl-2-(4-(3-trifluormethylphenylmethoxy)-phenyl)-2-E-[methoxyi-
mino]ethylidene)amino]oxy]methyl]-.alpha.-(methoxymethylene)-phenylacetate
(compound A225 in Table 1) are shown. The similar chemical shifts
of atoms 1 and 4 of compound A in Table 2.1 and those in Table 2.2
confirm the E configuration of the compounds of the formula I.
[0150] Table 2.1: .sup.13C-NMR shifts and .sup.1J.sub.CC coupling
constants of
1-[4-(3trifluoromethylphenylmethoxy)-phenyl]-1,2-propanedion- e
1-E-[methyloxime]-2-oxime (A) and
1-[43(3-trifluoromethylphenylmethoxy)-- phenyl]-1,2-propanedione
1-Z-[methyloxime]-2-oxime (B)
6 10 A 11 B Compound Atom No. Shift .delta. (ppm) Coupling
.sup.1Jcc (Hz) A 1 125.6 J.sub.12 = 56.0 3 155.0 J.sub.23 = 72.0 4
10.1 J.sub.34 = 43.0 B 1 127.8 J.sub.12 = 69.0 3 152.1 J.sub.23 =
56.5 4 14.4 J.sub.34 = 41.5
[0151] Table 2.2: .sup.13 C-NMR shifts of methyl
2-[[[(1-methyl-2-(4-(3-tr-
ifluoromethylphenylmethoxy)-phenyl)-2-E-[methoxyimino]ethylidene)amino]oxy-
]methyl]-.alpha.-(methoxymethylene)-phenylacetate (compound
0.225)
7 12 Atom No. Shift .delta. (ppm) 1 124.9 2 155.1 3 155.0 4
11.1
* * * * *