U.S. patent application number 09/729546 was filed with the patent office on 2001-04-05 for dimethylfurancarboxyanilide derivatives.
This patent application is currently assigned to Sankyo Company, Limited. Invention is credited to Konishi, Kiyoshi, Saito, Akio, Yanai, Toshiaki.
Application Number | 20010000184 09/729546 |
Document ID | / |
Family ID | 24936671 |
Filed Date | 2001-04-05 |
United States Patent
Application |
20010000184 |
Kind Code |
A1 |
Konishi, Kiyoshi ; et
al. |
April 5, 2001 |
Dimethylfurancarboxyanilide derivatives
Abstract
A dimethylfurancarboxyanilide compound of the formula (I): 1
wherein R.sup.1 and R.sup.2 are the same or different and each is
hydrogen, (C.sub.2-C.sub.6)-alkyl, (C.sub.3-C.sub.6)-cycloalkyl,
(C.sub.3-C.sub.6)-alkenyl, (C.sub.2-C.sub.6) alkynyl,
(C.sub.1-C.sub.3)-halogenoalkyl, (C.sub.2-C.sub.6)-alkoxy,
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl, cyano,
substituted amide, (C.sub.1-C.sub.6)-alkoxy-carbonyl, benzoyl which
is unsubstituted or has 1 to 2 substituents, benzoylamino which is
unsubstituted or has 1 to 2 substituents;
(C.sub.2-C.sub.6)-alkanoylamino,
(C.sub.3-C.sub.6)-cycloalkylcarbonylamino, benzyl which is
unsubstituted or has 1 to 2 substituents, phenyl which is
unsubstituted or has 1 to 2 substituents, or
(C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.2-C.sub.5)-alken- ylene;
and R.sup.1 and R.sup.2 do not both represent hydrogen at the same
time. A wood preservative containing the
dimethylfurancarboxyanilide compound as an active ingredient. A
method of preserving wood by applying the
dimethylfurancarboxyanilide compound to wood. A wood preservative
composition in which the dimethylfurancarboxyanilide compound is
combined with at least one of
3-bromo-2,3-diiodo-2-propenylethylcarbamate,
3-iodo-2-propynylbutylcarbamate and
4-chlorophenyl-3-iodopropargylformal.
Inventors: |
Konishi, Kiyoshi; (Tokyo,
JP) ; Yanai, Toshiaki; (Yokohama-shi, JP) ;
Saito, Akio; (Chiba-shi, JP) |
Correspondence
Address: |
FRISHAUF, HOLTZ, GOODMAN,
LANGER & CHICK, P.C.
25th Floor
767 Third Avenue
New York
NY
10017-2023
US
|
Assignee: |
Sankyo Company, Limited
|
Family ID: |
24936671 |
Appl. No.: |
09/729546 |
Filed: |
December 4, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09729546 |
Dec 4, 2000 |
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09306170 |
May 6, 1999 |
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09306170 |
May 6, 1999 |
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08999547 |
Dec 29, 1997 |
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08999547 |
Dec 29, 1997 |
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08730751 |
Oct 15, 1996 |
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08730751 |
Oct 15, 1996 |
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PCT/JP94/00631 |
Apr 15, 1994 |
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Current U.S.
Class: |
549/487 |
Current CPC
Class: |
A01N 43/08 20130101;
B27K 3/343 20130101 |
Class at
Publication: |
549/487 |
International
Class: |
C07D 307/02 |
Claims
We claim:
1. A dimethylfurancarboxyanilide compound of the formula (I):
6wherein R.sup.1 and R.sup.2 are the same or different and each is
a hydrogen atom; an alkyl group having from 2 to 6 carbon atoms; a
cycloalkyl group having from 3 to 6 carbon atoms; an alkenyl group
having from 3 to 6 carbon atoms; an alkynyl group having fro m 2 to
6 carbon atoms; a halogenoalkyl group having from 1 to 3 carbon
atoms; an alkoxy group having from 2 to 6 carbon atoms; an
alkoxyalkyl group having from 1 to 6 carbon atoms in the alkoxy
moiety and from 1 to 6 carbon atoms in the alkyl moiety; a cyano
group; a substituted amide group; an alkoxycarbonyl group having
from 1 to 6 carbon atoms in the alkoxy moiety; a benzoyl group
which may have optionally from 1 to 2 substituents; a benzoylamino
group which may have optionally from 1 to 2 substituents; an
alkanoylamino group having from 2 to 6 carbon atoms; a
cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in
the cycloalkyl moiety; a benzyl group which is unsubstituted or has
from 1 to 2 substituents; a phenyl group which is unsubstituted or
has from 1 to 2 substituents; or an alkoxycarbonylalkenylene group
having from 1 to 6 carbon atoms in the alkoxy moiety and from 2 to
5 carbon atoms in the alkenylene moiety; provided that: (i) R.sup.1
and R.sup.2 do not both represent hydrogen atoms; (ii) one of
R.sup.1 and R.sup.2 does not represent an unsubstituted phenyl
group when the other represents a hydrogen atom; and (iii) one of
R.sup.1 and R.sup.2 does not represent, in the ortho position on
the aniline ring, an alkyl group having from 2 to 6 carbon atoms or
a cycloalkyl group having from 3 to 6 carbon atoms, when the other
is a hydrogen atom.
2. The dimethylfurancarboxyanilide compound of claim 1, wherein
R.sup.1 and R.sup.2 are the same or different and each is a
hydrogen atom; a (C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.- 6)-alkyl group; a cyano
group; a substituted amide group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; a benzoyl group which is
unsubstituted or has 1 to 2 substituents; a benzoyl-amino group
which is unsubstituted or has 1 to 2 substituents; a
(C.sub.2-C.sub.6)-alkanoylami- no group; a
(C.sub.3-C.sub.6)-cycloalkylcarbonylamino group; a benzyl group
which is unsubstituted or has 1 to 2 substituents; or a
(C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.2-C.sub.6)-alkenylene
group; and R.sup.1 and R.sup.2 do not both represent hydrogen atoms
at the same time; and when one of R.sup.1 and R.sup.2 is a hydrogen
atom and the other is a (C.sub.2-C.sub.6)-alkyl group substituent,
the C.sub.2-C.sub.6-alkyl group substituent is not at
position-2.
3. The dimethylfurancarboxyanilide compound of claim 1, wherein
R.sup.1 and R.sup.2 are the same or different and each is a
hydrogen atom; a (C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.- 6)-alkyl group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; or a benzyl group which is
unsubstituted or has 1 to 2 substituents; and R.sup.1 and R.sup.2
do not both represent hydrogen atoms at the same time; and when one
of R.sup.1 and R.sup.2 is a hydrogen atom and the other is a
(C.sub.2-C.sub.6)-alkyl group substituent, the
C.sub.2-C.sub.6-alkyl group substituent is not at position-2.
4. The dimethylfurancarboxyanilide compound of claim 1, wherein the
compound is 2,5-dimethylfuran-3-carboxy(3-isopropylanilide).
5. A wood preservative composition comprising an effective wood
preserving amount of the dimethylfurancarboxyanilide compound of
claim 1 as an active ingredient together with a carrier.
6. The wood preservative composition of claim 5, wherein the
compound is 2,5-dimethylfuran-3-carboxy(3-isopropylanilide).
7. A method of preserving wood comprising applying to the wood a
composition comprising an effective amount of a compound having the
formula (I): 7wherein R.sup.1 and R.sup.2 are the same or different
and each is a hydrogen atom; an alkyl group having from 2 to 6
carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms;
an alkenyl group having from 3 to 6 carbon atoms; an alkynyl group
having from 2 to 6 carbon atoms; a halogenoalkyl group having from
1 to 3 carbon atoms; an alkoxy group having from 2 to 6 carbon
atoms; an alkoxyalkyl group having from 1 to 6 carbon atoms in the
alkoxy moiety and from 1 to 6 carbon atoms in the alkyl moiety; a
cyano group; a substituted amide group; an alkoxycarbonyl group
having from 1 to 6 carbon atoms in the alkoxy moiety; a benzoyl
group which is unsubstituted or has from 1 to 2 substituents; a
benzoylamino group which is unsubstituted or has from 1 to 2
substituents; an alkanoylamino group having from 2 to 6 carbon
atoms; a cycloalkylcarbonylamino group having from 3 to 6 carbon
atoms in the cycloalkyl moiety; a benzyl group which is
unsubstituted or has from 1 to 2 substituents; a phenyl group which
is unsubstituted or has from 1 to 2 substituents; or an
alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in
the alkoxy moiety and from 2 to 5 carbon atoms in the alkenylene
moiety; provided that: R.sup.1 and R.sup.2 do not both represent
hydrogen atoms.
8. The method of claim 7, wherein R.sup.1 and R.sup.2 are the same
or different and each represents a hydrogen atom; a
(C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl group; a cyano
group; a substituted amide group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; a benzoyl group which is
unsubstituted or has 1 to 2 substituents; a benzoyl-amino group
which is unsubstituted or has 1 to 2 substituents; a
(C.sub.2-C.sub.6)-alkanoylamino group; a
(C.sub.3-C.sub.6)-cycloalkylca- rbonylamino group; a benzyl group
which is unsubstituted or has 1 to 2 substituents; or a
(C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.2-C.sub.6)-alk- enylene
group; and R.sup.1 and R.sup.2 do not both represent hydrogen atoms
at the same time; and when one of R.sup.1 and R.sup.2 is a hydrogen
atom and the other is a (C.sub.2-C.sub.6)-alkyl group substituent,
the C.sub.2-C.sub.6 alkyl group substituent is not at
position-2.
9. The method of claim 7, wherein R.sup.1 and R.sup.2 are the same
or different and each represents a hydrogen atom; a
(C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.6)-alkyl group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; or a benzyl group which is
unsubstituted or has 1 to 2 substituents; and R.sup.1 and R.sup.2
do not represent hydrogen atoms at the same time; and when one of
R.sup.1 and R.sup.2 is a hydrogen atom and the other is a
(C.sub.2-C.sub.6)-alkyl group substituent, the C.sub.2-C.sub.6
alkyl group substituent is not at position-2.
10. The method of claim 7, wherein the compound is
2,5-dimethylfuran-3-car- boxy(3-isopropylanilide).
11. A wood preservative composition comprising: (a) at least one
compound selected from the group consisting of
3-bromo-2,3-diiodo-2-propenylethylc- arbamate,
3-iodo-2-propynylbutylcarbamate and 4-chlorophenyl-3-iodoproparg-
ylformal, and (b) at least one dimethylfurancarboxyanilide compound
of the following formula (I): 8wherein R.sup.1 and R.sup.2 are the
same or different and each is a hydrogen atom; an alkyl group
having from 2 to 6 carbon atoms; a cycloalkyl group having from 3
to 6 carbon atoms; an alkenyl group having from 3 to 6 carbon
atoms; an alkynyl group having from 2 to 6 carbon atoms; a
halogenoalkyl group having from 1 to 3 carbon atoms; an alkoxy
group having from 2 to 6 carbon atoms; an alkoxyalkyl group having
from 1 to 6 carbon atoms in the alkoxy moiety and from 1 to 6
carbon atoms in the alkyl moiety; a cyano group; a substituted
amide group; an alkoxycarbonyl group having from 1 to 6 carbon
atoms in the alkoxy moiety; a benzoyl group which is unsubstituted
or has 1 to 2 substituents; a benzoylamino group which is
unsubstituted or has 1 to 2 substituents; an alkanoylamino group
having from 2 to 6 carbon atoms; a cycloalkylcarbonylamino group
having from 3 to 6 carbon atoms in the cycloalkyl moiety; a benzyl
group which has 1 to 2 substituents; a phenyl group which is
unsubstituted or has 1 to 2 substituents; or an
alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in
the alkoxy moiety and from 2 to 5 carbon atoms in the alkenylene
moiety; provided that: R.sup.1 and R.sup.2 do not both represent
hydrogen atoms.
12. The wood preservative composition of claim 11, wherein R.sup.1
and R.sup.2 are the same or different and each is a hydrogen atom;
a (C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.- 6)-alkyl group; a cyano
group; a substituted amide group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; a benzoyl group which is
unsubstituted or has 1 to 2 substituents; a benzoyl-amino group
which is unsubstituted or has 1 to 2 substituents; a
(C.sub.2-C.sub.6)-alkanoylami- no group; a
(C.sub.3-C.sub.6)-cycloalkylcarbonylamino group; a benzyl group
which is unsubstituted or has 1 to 2 substituents; or a
(C.sub.1-C.sub.6)-alkoxycarbonyl-(C.sub.2-C.sub.6)-alkenylene
group; and R.sup.1 and R.sup.2 do not both represent hydrogen atom
at the same time; and when one of R.sup.1 and R.sup.2 is a hydrogen
atom and the other is a (C.sub.2-C.sub.6)-alkyl group substituent,
the C.sub.2-C.sub.6 alkyl substituent is not at position-2.
13. The wood preservative composition of claim 11, wherein R.sup.1
and R.sup.2 are the same or different and each is a hydrogen atom;
a (C.sub.2-C.sub.6)-alkyl group, a
(C.sub.1-C.sub.6)-alkoxy-(C.sub.1-C.sub.- 6)-alkyl group; a
(C.sub.1-C.sub.6)-alkoxycarbonyl group; or a benzyl group which is
unsubstituted or has 1 to 2 substituents; and R.sup.1 and R.sup.2
do not both represent hydrogen atoms at the same time; and when one
of R.sup.1 and R.sup.2 is a hydrogen atom and the other is a
(C.sub.2-C.sub.6)-alkyl substituent, the C.sub.2-C.sub.6 alkyl
substituent is not at position-2.
14. The wood preservative composition of claim 11, wherein the at
least one dimethylfurancarboxyanilide compound is 2,
5-dimethylfuran-3-carboxy(- 3-isopropylanilide).
15. The wood preservative composition of claim 11, wherein the at
least one dimethylfurancarboxyanilide of the formula (I) and the at
least one compound (a) are contained in a ratio of 240:1 to
1:35.
16. The wood preservative composition of claim 11, wherein the at
least one dimethylfurancarboxyanilide compound of the formula (I)
and the at least one compound (a) are contained in a ratio of 30:1
to 1:10.
17. The wood preservative composition of claim 11, wherein the at
least one dimethylfurancarboxyanilide compound of the formula (I)
and the at least one compound (a) are contained in a ratio of 5:1
to 1:5.
18. The wood preservative composition of claim 10, wherein the at
least one compound (a) consists essentially of
3-bromo-2,3-diiodo-2-propenyleth- ylcarbamate.
19. The wood preservative composition of claim 18, wherein the at
least one dimethylfurancarboxyanilide compound of the formula (I)
consists essentially of
2,5-dimethylfuran-3-carboxy(3-isopropylanilide).
Description
1. This is a continuation-in-part application of Ser. No.
08/730,751 filed Oct. 15, 1996, which is a continuation application
of International application PCT/JP94/00631 filed Apr. 15,
1994.
BACKGROUND OF THE INVENTION
2. 1. Technological Field
3. The present invention is concerned with novel
dimethylfurancarboxyanili- de derivatives exhibiting an excellent
antimicrobial effect, a wood preservative containing the
dimethylfurancarboxyanilide derivative as the active ingredient,
and a wood preservative composition in which the
dimethylfurancarboxyanilide derivative as one of the active
ingredients is combined with any commercially available wood
preservative the effect of which has been already confirmed.
4. 2. Background Technology
5. Various kinds of inorganic or organic compounds have previously
been employed to preserve timber against decay due to various
wood-rotting fungi. However, these chemicals have faults such as
affecting the human body because of their high toxicity, showing
environmental polution, requiring a high concentration thereof when
employed and being expensive.
6. As for compounds relating to the dimethylfurancarboxyanilide
derivatives of the present invention, compounds represented by the
formula below have been disclosed in Japanese Patent Kokai
Application Sho 50-10376 as a chemical for preventing plant injury;
in which, however, R is limited to phenyl, nitro-substituted
phenyl, carboxy-substituted phenyl, phenyl-substituted phenyl,
methyl-substituced phenyl, halogen-substituted phenyl or
methoxy-substituted phenyl. In addition, this patent is silent on
the other derivatives, and no activity of these compounds on
wood-rotting fungi has been described. 2
SUMMARY OF THE INVENTION
7. The object of the present invention exists in providing a novel
wood preservative which is safer, and is possible to use
effectively at a low concentration and/or at a low price.
8. In consideration of such situation as mentioned above, the
present inventors considered furancarboxyanilide derivatives, and
studied eagerly. Our study resulted in finding that novel
dimethylfurancarboxyani- lide derivatives represented by the
general formula (I) below are very useful as a wood preservative
and furthermore, if the dimethylfurancarboxyanilide derivative as
the active ingredient is combined with any other commercially
available wood preservative, potentiation effect can be observed
and a wood preservative composition can be prepared.
9. The compounds of the present invention are the
dimethylfurancarboxyanil- ide derivatives represented by the
general formula 3
10. In this formula, R.sup.1 and R.sup.2 are the same or different
and each represents hydrogen atom; an alkyl group having from 2 to
6 carbon atoms; a cycloalkyl group having from 3 to 6 carbon atoms;
an alkenyl group having from 3 to 6 carbon atoms; an alkynyl group
having from 2 to 6 carbon atoms; a halogenoalkyl group having from
1 to 3 carbon atoms; an alkoxy group having from 2 to 6 carbon
atoms; an alkoxyalkylene group having from 1 to 6 carbon atoms in
the alkoxy moiety and having from 1 to 6 carbon atoms in the
alkylene moiety; a cyano group; a substituted amide group; an
alkoxycarbonyl group having from 1 to 6 carbon atoms in the alkoxy
moiety; a benzoyl group which may have optionally from 1 to 2
substituents; a benzoylamino group which may have optionally from 1
to 2 substituents; an alkanoylamino group having from 2 to 6 carbon
atoms; a cycloalkylcarbonylamino group having from 3 to 6 carbon
atoms in the cycloakyl moiety; a benzyl group which may have
optionally from 1 to 2 substituents; a phenyl group which may have
optionally from 1 to 2 substituents; or an alkoxycarbonylalkenylene
group having from 1 to 6 carbon atoms in the alkoxy moiety and
having from 2 to 5 carbon atoms in the alkenylene moiety; and
R.sup.1 and R.sup.2 do not represent hydrogen atoms at the same
time]. The present invention concerns the compounds mentioned
above, a wood preservative and a wood preservative composition each
containing the dimethylfurancarboxyanilide derivative as the active
ingredient.
BRIEF DESCRIPTION OF THE DRAWINGS
11. FIGS. 1A to 1F show the minimum inhibitory concentrations (ppm)
of Compound of Example 1 in combination with various wood
preservatives. FIGS. 2A to 2F show the minimum inhibitory
concentrations (ppm) of Compound of Example 2 in combination with
various wood preservatives.
DETAILED DESCRIPTION OF THE INVENTION
12. In the general formula (I) above, as an alkyl group having from
2 to 6 carbon atoms, which is included in the definitions for
R.sup.1 and R.sup.2, there may be mentioned a straight or branched
chain alkyl group such as ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neo-pentyl,
hexyl, isohexyl or sec-hexyl; particularly preferably an alkyl
group having from 2 to 6 carbon atoms.
13. In the general formula (I) above, as a cycloalkyl group having
from 3 to 6 carbon atoms, which is included in the definitions for
R.sup.1 and R.sup.2, there may be mentioned a cycloalkyl group such
as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; preferably
a cycloalkyl group having from 3 to 6 carbon atoms; and more
preferably a cycloalkyl group having from 5 to 6 carbon atoms.
14. In the general formula (I) above, as an alkenyl group having
from 3 to 6 carbon atoms, which is included in the definitions for
R.sup.1 and R.sup.2, there may be mentioned an alkenyl group such
as allyl, isopropenyl, metallyl, 2-butenyl, 3-butenyl,
1,3-butandienyl, 2-pentenyl, or 2-hexenyl; preferably an alkenyl
group having from 3 to 4 carbon atoms; and more preferably
isopropenyl.
15. In the general formula (I) above, as an alkynyl group having
from 2 to 6 carbon atoms, which is included in the definitions for
R.sup.1 and R.sup.2, there may be mentioned an alkynyl group such
as ethynyl, propargyl, 2-butynyl, 4-pentynyl, or 2-hexynyl;
preferably an alkynyl group having from 2 to 4 carbon atoms; and
more preferably ethynyl.
16. In the general formula (I) above, as a halogenoalkyl group
having from 1 to 3 carbon atoms, which is included in the
definitions for R.sup.1 and R.sup.2, there may be mentioned a
halogenoalkyl group such as trifluoromethyl, trichloromethyl,
pentafluoroethyl, 2,2,2-trichloroethyl or 2,4-dichloropropyl;
preferably a halogenoalkyl group having from 1 to 2 carbon atoms;
and more preferably trifluoromethyl.
17. In the general formula (I) above, as an alkoxy group having
from 2 to 6 carbon atoms, which is included in the definitions for
R.sup.1 and R.sup.2, there may be mentioned a straight or branched
chain alkoxy group such as ethoxy, propoxy, isopropoxy, butoxy,
pentoxy or hexyloxy; preferably an alkoxy group having from 2 to 4
carbon atoms; and more preferably an alkoxy group having from 2 to
3 carbon atoms.
18. In the general formula (I) above, as an alkoxy group having
from 1 to 6 carbon atoms contained in an alkoxyalkyl group having
from 1 to 6 carbon atoms in the alkoxy moiety and having from 1 to
6 carbon atoms in the alkyl moiety, which is included in the
definitions for R.sup.1 and R.sup.2, there may be mentioned a
straight or branched chain alkoxy group such as methoxy, ethoxy,
propoxy, isopropoxy, butoxy, pentoxy, neo-pentoxy or hexyloxy;
preferably an alkoxy group having from 1 to 5 carbon atoms; and
more preferably an alkoxy group having from 1 to 3 carbon atoms or
having 5 carbon atoms.
19. In the general formula (I) above, as an alkylene group
contained in an alkoxyalkylene group having from 1 to 6 carbon
atoms in the alkoxy moiety and from 1 to 6 carbon atoms in the
alkylene moiety which is included in the definitions for R.sup.1
and R.sup.2, there may be mentioned a straight or branched chain
alkylene group such as methylene, ethylene, propylene,
trimethylene, tetramethylene, pentamethylene or hexamethylene;
preferably an alkylene group having from 1 to 2 carbon atoms; and
more preferably methylene.
20. In the general formula (I) above, as a substituted amide group,
which is included in the definitions for R.sup.1 and R.sup.2, there
may be mentioned a monoalkylamide group such as methylamide,
ethylamide, isopropylamide, butylamide, sec-butylamide; a
dialkylamide group such as dimethylamide, diethylamide,
diisopropylamide, dibutylamide, di-sec-butylamide,
methylethylamide, methylisopropylamide, methylbutylamide,
methyl-sec-butylamide, ethylisopropylamide, isopropylbutylamide,
pyrrolidylamide or piperidylamide; an optionally substituted
phenylamide such as phenylamide, 2-chlorophenylamide,
2,4-dichlorophenylamide, 2-methylphenylamide, 2-ethylphenylamide or
4-methoxyphenylamide; preferably methylamide, piperidylamide or
phenylamide.
21. In the general formula (I) above, as an alkoxycarbonyl group
having from 1 to 6 carbon atoms in the alkoxy moiety, which is
included in the definitions for R.sup.1 and R.sup.2, there may be
mentioned a group which is formed from the aforementioned alkoxy
group having from 1 to 6 carbon atoms contained in an alkoxyalkyl
group having from 1 to 6 carbon atoms in the alkoxy moiety and
having from 1 to 6 carbon atoms in the alkyl moiety and from a
carbonyl group, such as methoxycarbonyl, ethoxycarbonyl,
isopropoxycarbonyl, butoxycarbonyl, sec-butoxycarbonyl,
tert-butoxycarbonyl, pentyloxycarbcnyl or hexyloxycarbonyl;
preferably an alkoxycarbonyl group having from 1 to 3 carbon atoms
in the alkoxy moiety.
22. In the general formula (I) above, as a benzoyl group which may
have optionally from 1 to 2 substituents, which is included in the
definitions for R.sup.1 and R.sup.2, there may be mentioned an
optionally substituted benzoyl group such as benzoyl,
2-chlorobenzoyl, 2,4-dichlorobenzoyl, 2-methylbenzoyl,
2,4-dimethylbenzoyl, 4-ethylbenzoyl or 4-methoxybenzoyl; preferably
benzoyl.
23. In the general formula (I) above, as a benzoylamino group which
may have optionally from 1 to 2 substituents, which is included in
the definitions for R.sup.1 and R.sup.2, there may be mentioned an
optionally substituted benzoylamino group which is formed by
substitution of amino group(s) to the aforementioned benzoyl group
which may have optionally from 1 to 2 substituents such as
benzoylamino, 2-chlorobenzoylamino, 2,4-dichlorobenzoylamino,
2,4-dimethylbenzoylamino, 4-methylbenzoylamino, 4-ethylbenzoylamino
or 4-methoxybenzoylamino; preferably benzoylamino.
24. In the general formula (I) above, as an alkanoylamino group
having from 2 to 6 carbon atoms, which is included in the
definitions for R.sup.1 and R.sup.2, there may be mentioned
acetylamino, propionylamino, butyrylamino, isobutyrylamino,
valerylamino, isovalerylamino, caproylamino or isocaproylamino;
preferably acetylamino.
25. In the general formula (I) above, as a cycloalkylcarbonylamino
group having from 3 to 6 carbon atoms in the cycloalkyl moiety,
which is included in the definitions for R.sup.1 and R.sup.2, there
may be mentioned cyclopropylcarbonylamino, cyclobutylcarbonylamino,
cyclopentylcarbonylamino or cyclohexylcarbonylamino; preferably
cyclohexylcarbonylamino.
26. In the general formul (I) above, as a benzyl group which may
have optionally from 1 to 2 substituents, which is included in the
definitions for R.sup.1 and R.sup.2, there may be mentioned benzyl,
2-methylbenzyl, 2,4-dimethylbenzyl, 2-chlorobenzyl, 4-methoxybenzyl
or 4-ethoxybenzyl; preferably benzyl.
27. In the general formula (I) above, as an
alkoxycarbonylalkenylene group having from 1 to 6 carbon atoms in
the alkoxy moiety and having from 2 to 5 carbon atoms in the
alkenylene moiety, which is included in the definitions for R.sup.1
and R.sup.2, there may be mentioned methoxycarbonylvinylene,
ethoxycarbonyl-2-propenylene, methoxycarbonyl-2-butenylene or
ethoxycarbonyl-2-pentenylene; preferably
methoxycarbonylvinylene.
28. Preferred compounds having the general formula (I) above
include ones in which:
29. (1) R.sup.1 and R.sup.2 are the same or different and each
represents a hydrogen atom; an alkyl group having from 2 to 6
carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; an
alkynyl group having from 2 to 4 carbon atoms; a cycloalkyl group
having from 3 to 6 carbon atoms; an alkoxycarbonyl group having
from 1 to 6 carbon atoms in the alkoxy moiety; an alkoxyalkylene
group having from 1 to 6 carbon atoms in the alkoxy moiety and
having from 1 to 2 carbon atoms in the alkylene moiety; a
cycloalkylcarbonylamino group having from 3 to 6 carbon atoms in
the cycloalkyl moiety; an alkoxy group having from 2 to 4 carbon
atoms; a benzoyl group which may have optionally from 1 to 2
substituents; a benzyl group which may have optionally from 1 to 2
substituents; or an alkoxycarbonylalkenylene group having from 1 to
6 carbon atoms in the alkoxy moiety and having from 2 to 5 carbon
atoms in the alkenylene moiety; and R.sup.1 and R.sup.2 do not
represent hydrogen atoms at the same time. More preferred ones
include those in which:
30. (2) R.sup.1 and R.sup.2 are the same or different and each
represents a hydrogen atom; an alkyl group having from 2 to 6
carbon atoms; an alkenyl group having from 3 to 4 carbon atoms; a
cycloalkyl group having from 5 to 6 carbon atoms; an alkoxycarbonyl
group having from 1 to 3 carbon atoms in the alkoxy moiety; an
alkoxymethylene group having from 1 to 6 carbon atoms in the alkoxy
moiety; a cycloalkylcarbonylamino group having from 4 to 6 carbon
atoms in the cycloalkyl moiety; a benzoyl group; a benzyl group
which may have optionally 1 substituent; or an
alkoxycarbonylalkenylene group having from 1 to 3 carbon atoms in
the alkoxy moiety and having from 2 to 4 carbon atoms in the
alkenylene moiety; and R.sup.1 and R.sup.2 do not represent
hydrogen atoms at the same time. Particularly preferred ones
include those in which:
31. (3) R.sup.1 is a 3-alkyl group having from 2 to 6 carbon atoms;
a 3-alkoxycarbonyl group having from 1 to 3 carbon atoms in the
alkoxy moiety; a 3-alkoxymethylene group having from 1 to 3 carbon
atoms in the alkoxy moiety; a cycloalkylcarbonylamino group having
from 4 to 6 carbon atoms in the cycloalkyl moiety; a benzyl group
which may be substituted by a methoxy group; a benzoyl group; or an
alkoxycarbonylalkenylene group having from 1 to 3 carbon atoms in
the alkoxy moiety and having from 2 to 3 carbon atoms in the
alkenylene moiety; and
32. (4) R.sup.2 is a hydrogen atom.
33. Novel dimethylfurancarboxyanilide derivatives which may be used
as an active ingredient of the wood preservative of the present
invention are exemplified in the following table.
34. In Table 1 below, abbreviations are used as follows.
1 Bz Benzyl Bu Butyl Et Ethyl Hx Hexyl Me Methyl Ph Phenyl Pip
Piperidyl Pn Pentyl Pr Propyl iso secondary tertiary cyclo
35.
2TABLE 1 Compound No. R.sup.1 R.sup.2 1 3-CF.sub.3 H 2 4-CF.sub.3 H
3 3-CH.sub.2OMe H 4 4-CH.sub.2OMe H 5 2-Et H 6 3-Et H 7 4-Et H 8
3-C.ident.CH H 9 4-C.ident.CH H 10 3-CH.sub.2OEt H 11 4-CH.sub.2OEt
H 12 2-Et 3-Et 13 2-Et 4-Et 14 2-Et 5-Et 15 2-Et 6-Et 16 3-Et 4-Et
17 3-Et 5-Et 18 3-Et 6-Et 19 3-Pr H 20 4-Pr H 21 2-Pr H 22 3-Pr H
23 4-Pr H 24 3-Pr H 25 4-Pr H 26 3-CH.sub.2OPr H 27 3-CH.sub.2OPr H
28 4-CH.sub.2OPr H 29 3-CH.sub.2C.dbd.CH.sub.2 H 30
4-CH.sub.2C.dbd.CH.sub.2 H 31 3-CH.sub.2C.ident.CH H 32
4-CH.sub.2C.ident.CH H 33 3-Pr 4-Pr 34 2-Pr 4-Pr 35 3-Pr 5-pr 36
3-CH.sub.2OBu H 37 4-CH.sub.2OBu H 38 3-CH.sub.2OBu H 39
4-CH.sub.2OBu H 40 3-CH.sub.2OBu H 41 4-CH.sub.2OBu H 42 3-Bu H 43
4-Bu H 44 3-Bu H 45 3-Bu H 46 3-Bu H 47 4-Bu H 48 3-Bu H 49
3-CH.sub.2CH.dbd.CHMe H 50 3-CH.sub.2C.ident.CMe H 51
3-CH.sub.2MeCH.dbd.CH.sub.2 H 52 4-CH.sub.2MeCH.dbd.CH.sub.2 H 53
3-Pn H 54 4-Pn H 55 3-Pn H 56 3-Pn H 57 3-Pn H 58 3-CH.sub.2OPn H
59 3-CH.sub.2O-Pn H 60 3-Hx H 61 3-Hx H 62 3-Hx H 63 3-CN H 64
3-OEt H 65 3-OPr H 66 3-CONHMe H 67 3-(CO-1-Pip) H 68 3-CONHPh H 69
3-COOMe H 70 3-COOEt H 71 3-COOPr H 72 3-COOPr H 73 3-COOBu H 74
3-COOBu H 75 3-COPh H 76 3-CO(2-MePh) H 77 3-NHCOPh H 78 3-NHCOMe H
79 3-NHCOBu H 80 3-NHCOPn H 81 3-NHCOHx H 82 3-Bz H 83 3-(4-MeOBz)
H 84 3-(4-MeBz) H 85 3-CH.dbd.CHCOOMe H 86 3-Ph H 87 3-(2-MePh)
H
36. Among the compounds above, preferred ones include Compounds
Nos. 3, 4, 5, 6, 7, 8, 10, 11, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29, 31, 33, 35, 36, 38, 40, 42, 43, 44, 45, 46,
48, 49, 50, 51, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 64, 69, 70,
71, 72, 75, 80, 81, 82, 83 and 85; and more preferred ones include
Compounds Nos. 3, 6, 10, 19, 22, 24, 26, 27, 33, 35, 36, 38, 40,
42, 44, 45, 46, 48, 53, 55, 60, 61, 69, 70, 81, 83 and 85.
37. The compounds of the said general formula (I) may be prepared
according to the procedure summarized in either the following
Method A or Method B. 4 5
38. In the above formulae, R.sup.1 and R.sup.2 are as defined
above. R.sup.1' represents a C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
cycloalkyl or benzyl group which may optionally have 1 or 2
substituents. The compound of formula (Ia) is that of a general
formula (I), in which R.sup.1 is R.sup.1' and R.sup.2 signifies a
hydrogen atom. The compound of formula (V) is iodine-substituted
aniline. X signifies a halogen atom such as chlorine, bromine or
iodine, preferably chlorine. X' signifies a halogen atom such as a
chlorine, bromine or iodine, preferably bromine or iodine.
39. The compounds of the present invention may be prepared by
well-known procedure.
40. Step A1 consists of the preparation of a compound of general
formula (I) by reacting a compound of general formula (III) with a
compound of general formula (IV) in an inert solvent in the
presence of a dehydrohalogenating agent.
41. A compound of formula (III) used as a starting material in this
step may be prepared by hydrolyzing
2,5-dimethylfuran-3-carboxylate, which may be prepared by
condensing chloroacetone with acetoacetate, followed by
halogenation.
42. A compound of formula (IV) used as a starting material in this
step is an aniline derivative which is commercially available or
may be prepared by well-known methods.
43. Examples of the inert solvents used include, for example,
ethers such as ether, isopropyl ether, tetrahydrofuran or dioxane;
aromatic hydrocarbons such as benzene, toluene or xylene;
halogenated hydrocarbons such as dichloromethane, chloroform or
carbon tetrachloride; and mixtures of two or more of these
solvents; preferably aromatic hydrocarbons (particularly
toluene).
44. Examples of dehydrohalogenating agents used include, for
example, tertiary amines such as triethylamine,
N,N-dimethylaminopyridine or the like and pyridines. This reaction
can be carried out in the presence or absence of a solvent. In
order to perform the reaction smoothly, using a solvent, the
reaction is carried out at a temperature of 0.degree. C. to reflux
temperature of the solvent used, preferably from room temperature
to 100.degree. C. The time required for the reaction takes
generally from 30 minuts to 5 hours, preferably from 30 minutes to
2 hours.
45. Step B1 consists of the preparation of a compound having
general formula (VI) by reacting a compound having general formula
(III) with a compound having general formula (V) in an inert
solvent in the presence of a dehydrohalogenating agent.
46. A compound of formula (IV) used as a starting material in this
step is an aniline derivative which is commercially available or
may be prepared by well-known methods.
47. The reaction conditions employed in this step are similar to
those employed in Step A1.
48. Step B2 consists of the preparation of a compound having
general formula (Ia) by reacting a compound having general formula
(VI) with a Grignard reagent having general formula: R.sup.1'MgX'
in an inert solvent in the presence of a catalyst.
49. Examples of preferred inert solvents used include, for example,
ethers such as diethyl ether, isopropyl ether, tetrahydrofuran or
dioxane; particularly preferably diethyl ether.
50. As a particularly preferred catalyst there may be used
[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride.
51. The Grignard reagents used in this process are commercially
available or can be prepared by reacting magnesium with an alkyl
halide represented by formula: R.sup.1'X' (wherein R.sup.1' and X'
are as defined above) according to well-known methods.
52. The reaction is normally carried out at a temperature of
0.degree. C. to 50.degree. C., preferably at room temperature.
Although the time required for the reaction varies depending upon
the nature of the solvent and reagent to be used, the reaction is
normally complete within a period of 10 hours to 10 days.
53. The compounds having the said general formula (I) in according
with the invention have potent wood preservative activity at low
concentration, compared with the activity shown by existing wood
preservatives. A composition consisting of a combination of the
foregoing compound (I) with a known wood preservative gives a
synergistic effect, lower concentrations of each compound being
required than would be expected from the activity shown by each
singly, such that the composition shows efficient wood preservative
activity at a low concentration. Therefore, novel
dimethylfurancarboxyanilide derivatives are extremely effective as
a wood preservative in low concentration so as to solve one of the
problems in the quality of life.
54. The following Examples illustrate the preparation and the
formulation of the compound of the invention in more detail. Such
examples are not to be construed as being limitative of the scope
of the invention.
EXAMPLE 1
2,5-Dimethylfuran-3-carboxy(3-acetylaminoanilide)
55. To a solution of 0.50 g of 2,5-dimethylfuran-3-carbonyl
chloride in 10 ml of dichloromethane were added 0.44 ml of
triethylamine and 0.47 g of 3-acetylaminoaniline under ice-cooling,
and the resulting mixture was stirred at room temperature for 2.5
hours followed by heating under reflux for 4.5 hours. After the
reaction mixture was cooled, it was diluted by adding 10 ml of
dichloromethane. The diluted mixture was successively washed with 1
N sodium hydroxide, 1 N hydrochloric acid and a saturated aqueous
solution of sodium chloride and dried over sodium sulfate followed
by distilling off the solvent. The residue was purified by column
chromatography through silica gel and the desired fractions were
recrystallized from ethyl acetate to give 0.51 g of the desired
compound as white crystals in a 59.4% yield.
56. m.p.: 172.0-172.5.degree. C.
57. .sup.1H NMR (CDCl.sub.3+DMSO) .delta. ppm: 8.4 (1H, b), 7.95
(1H, b), 7.88 (1H, m), 7.4 (1H, m), 7.32 (1H, m), 7.25 (1H, t, J=8
Hz), 6.25 (1H, s), 2.55 (3H, s), 2.25 (3H, s), 2.15 (3H, s)
58. IR (KBr) cm.sup.-1: 3306, 1672, 1651, 1086, 781
59. Elemental analysis (%): Calc'd for
C.sub.15H.sub.16N.sub.2O.sub.3: C, 66.16; H, 5.92; N, 10.29. Found:
C, 66.30; H, 5.98; N, 10.32.
60. Following the similar procedure as above, but using an
appropriate aniline derivative instead of 3-acetylaminoaniline,
there were obtained the following compounds.
EXAMPLE 2
2,5-Dimethylfuran-3-carboxy[3-(N-methylcarbamoyl) anilide]
61. Yield: 42.0%
62. m.p.: 212.0-213.0.degree. C.
63. .sup.1NMR (CDCl.sub.3 .delta. ppm: 8.5 (1H, b), 8.05 (1H, m),
7.88 (1H, m), 7.52 (1H, m), 7.38 (1H, t, J=8 Hz), 6.8 (1H, b), 6.35
(1H, s), 2.95 (3H, d, J=1.4 Hz), 2.55 (3H, s), 2.25 (3H, s).
64. IR (KBr) cm.sup.-1: 3293, 1638, 1581, 1074, 689
65. Elemental analysis (%): Calc'd for
C.sub.15H.sub.16N.sub.2O.sub.3: C, 66.16; H, 5.92; N, 10.29. Found:
C, 66.08; H, 6.20; N, 10.28.
EXAMPLE 3
2,5-Dimethylfuran-3-carboxy[3-(1-piperidylcarbonyl)anilide]
66. Yield: 50.0%
67. m.p.: 183.0-185.0.degree. C.
68. .sup.1H NMR spectrum (CDCl.sub.3) .delta. ppm: 7.68 (1H, m),
7.55 (2H, m), 7.35 (1H, t, J=8 Hz), 7.1 (1H, m), 6.15 (1H, s), 3.7
(2H, b), 3.35 (2H, b), 2.55 (3H, s), 2.25 (3H, s), 2.75-1.4 (6H,
m)
69. IR (KBr) cm.sup.-1: 3302, 1663, 1615, 1065, 808
70. Elemental analysis (%): Calc'd for
C.sub.19H.sub.22N.sub.2O.sub.3: C, 69.92; H, 6.79; N, 8.58. Found:
C, 69.52; H, 6.88; N, 8.48.
EXAMPLE 4
2,5-Dimethylfuran-3-carboxy[3-(N-phenylcarbamoyl)anilide]
71. Yield: 53.5%
72. m.p.: 182.5-184.0.degree. C.
73. .sup.1H NMR (CDCl.sub.3+DMSO) .delta. ppm: 8.48 (1H, b), 8.2
(1H, b), 8.1 (1H, s), 7.95 (1H, m), 7.7 (2H, d, J=8 Hz), 7.65 (1H,
d, J=8 Hz), 7.45 (1H, t, J=8 Hz), 7.35 (2H, t, J=8 Hz), 7.15 (1H,
t, J=8 Hz), 6.28 (1H, s), 2.55 (3H, s), 2.25 (3H, s)
74. IR (KBr) cm.sup.-1: 3282, 1646, 1080, 755, 691
75. Elemental analysis (%): Calc'd for
C.sub.20H.sub.18N.sub.2O.sub.3: C, 71.84; H, 5.43; N, 8.38. Found:
C, 71.87; H, 5.64; N, 8.34.
EXAMPLE 5
2,5-Dimethylfuran-3-carboxy(3-tert-butoxycarbonylanilide)
76. Yield: 92.0%
77. m.p.: 117.0-118.0.degree. C.
78. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 8.05 (1H, m) 7.88 (1H, m)
7.75 (1H, m), 7.4 (1H, t, J=8 Hz), 7.35 (1H, b), 6.1 (1H, s), 2.55
(3H, s), 2.25 (3H, s), 1.65 (9H, s)
79. IR (KBr) cm.sup.-1: 3362, 1687, 1672, 1067, 757
80. Elemental analysis (%): Calc'd for C.sub.18H.sub.21 NO.sub.4:
C, 68.55; H, 6.71; N, 4.44. Found: C, 68.04; H, 7.00; N, 4.40.
EXAMPLE 6
2,5-Dimethylfuran-3-carboxy(3-methoxycarbonylanilide)
81. Yield: 77.1%
82. m.p.: 104.0-106.0.degree. C.
83. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 8.05 (1H, m), 7.98 (1H,
m), 7.8 (1H, m), 7.42 (1H, t, J=8 Hz), 7.38 (1H, b), 6.1 (1H, s),
3.92 (3H, s), 2.55 (3H, s), 2.25 (3H, s)
84. IR (KBr) cm.sup.-1: 3437, 1704, 1675, 1070, 759
85. Elemental analysis (%): Calc'd for C.sub.15H.sub.15NO.sub.4: C,
65.92; H, 5.53; N, 5.13. Found: C, 66.02; H, 5.60; N, 5.08.
EXAMPLE 7
2,5-Dimethylfuran-3-carboxy(3-benzoylanilide)
86. Yield: 69.1%
87. m.p.: 137.0-139.0.degree. C.
88. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 8.05 (1H, m), 7.85-7.7
(3H, m), 7.6 (1H, m), 7.55-7.35 (5H, m), 6.1 (1H, s), 2.55 (3H, s),
2.25 (3H, s)
89. IR (KBr) cm.sup.-1: 3386, 1672, 1647, 1069, 707
90. Elemental analysis (%): Calc'd for C.sub.20H.sub.17NO.sub.3: C,
75.22; H, 5.37; N, 4.39. Found: C, 75.38; H, 5.43; N, 4.38.
EXAMPLE 8
2,5-Dimethylfuran-3-carboxy(3-benzoylaminoanilide)
91. Yield: 46.0%
92. m.p.: 194.5-195.0.degree. C.
93. .sup.1H NMR (CDCl.sub.3+DMSO) .delta. ppm: 8.7 (1H, b), 8.1
(1H, m), 7.95 (1H, b), 7.9 (2H, m), 7.6-7.4 (5H, m), 7.3 (1H, t,
J=8 Hz), 6.25 (1H, s), 2.55 (3H, s), 2.25 (3H, s)
94. IR (KBr) cm.sup.-1 3283, 1642, 1074, 791, 705
95. Elemental analysis (%): Calc'd for
C.sub.20H.sub.18N.sub.1O.sub.3: C, 71.84; H, 5.43; N, 8.38. Found:
C, 71.96; H, 5.53; N, 8.28.
EXAMPLE 9
2,5-Dimethylfuran-3-carboxy(3-valerylaminoanilide)
96. Yield: 70.3%
97. m.p.: 104.0-105.0.degree. C.
98. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.9 (1H, b), 7.45-7.1
(5H, m), 6.1 (1H, s), 2.55 (3H, s), 2.35 (2H, t, J=7 Hz), 2.25 (3H,
s), 1.7 (2H, m), 1.4 (2H, m), 0.95 (1H, t, J=7 Hz)
99. IR (KBr) cm.sup.-1: 3250, 1660, 1644, 1074, 781
100. Elemental analysis (%): Calc'd for
C.sub.18H.sub.22N.sub.2O.sub.3: C, 68.77; H, 7.05; N, 8.91. Found:
C, 68.73; H, 7.17; N, 8.90.
EXAMPLE 10
2,5-Dimethylfuran-3-carboxy(3-cyclohexylcarbonylaminoanilide)
101. Yield: 45.1%
102. m.p.: 212.5-213.0.degree. C.
103. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.92 (1H, b), 7.88 (1H,
b), 7.45-7.35 (2H, m), 7.25 (1H, t, J=8 Hz), 6.22 (1H, s), 2.55
(3H, s), 2.25 (3H, s), 2.25-2.2 (1H, m), 2.0-1.2 (10H, m)
104. IR (KBr) cm.sup.-1: 3238, 1651, 1639, 1076, 781
105. Elemental analysis (%): Calc'd for
C.sub.20H.sub.24N.sub.2O.sub.3: C, 70.57; H, 7.11; N, 8.23. Found:
C, 70.56; H, 7.26; N, 8.16
EXAMPLE 11
2,5-Dimethylfuran-3-carboxy(3-methoxymethylanilide)
106. Yield: 73.3%
107. m.p.: 102.5-103.5.degree. C.
108. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.55 (1H, m), 7.52 (1H,
d, J=8 Hz), 7.32 (1H, t, J=8 Hz), 7.32 (1H, b), 6.9 (1H, d, J=8
Hz), 6.1 (1H, s), 4.45 (2H, s), 3.4 (3H, s), 2.55 (3H, s), 2.25
(3H, s)
109. IR (KBr) cm.sup.-1: 3278, 1645, 1237, 1107, 784
110. Elemental analysis (%): Calc'd for C.sub.15H.sub.17NO.sub.3:
C, 69.48; H, 6.61; N, 5.40. Found: C, 69.22; H, 7.02; N, 5.37.
EXAMPLE 12
2,5-Dimethylfuran-3-carboxy(3-ethoxymethylanilide)
111. Yield: 64.4%
112. m.p.: 85.0-85.5.degree. C.
113. 1H NMR (CDCl.sub.3) .delta. ppm: 7.65-7.55 (2H, m), 7.38 (1H,
t, J=8 Hz), 7.35 (1H, b), 7.15 (1H, d, J=8 Hz), 6.15 (1H, s), 4.55
(2H, s), 3.58 (2H, q, J=8 Hz), 2.55 (3H, s), 2.25 (3H, s), 1.3 (3H,
t, J=8 Hz)
114. IR (KBr) cm.sup.-1: 3279, 1646, 1115, 785
115. Elemental analysis (%): Calc'd for C.sub.16H.sub.19NO.sub.3:
C, 70.31; H, 7.01; N, 5.12. Found: C, 70.14; H, 7.27; N, 5.06.
EXAMPLE 13
2,5-Dimethylfuran-3-carboxy(3-isopropyloxymethylanilide)
116. Yield: 92.7%
117. m.p.: 68.0-69.50.degree. C.
118. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.55 (1H, d, J=8 Hz),
7.5 (1H, m), 7.3 (1H, t, J=8 Hz), 7.3 (1H, b), 7.12 (1H, d, J=8
Hz), 6.1 (1H, s), 4.5 (2H, s), 3.7 (1H, m), 2.55 (3H, s), 2.25 (3H,
s), 1.25 (6H, d, J=7 Hz)
119. IR (Liquid film) cm.sup.-1: 3321, 1651, 1072, 785
120. Elemental analysis (%): Calc'd for C.sub.17H.sub.21NO.sub.3:
C, 71.06; H, 7.37; N, 4.87. Found: C, 70.35; H, 7.14; N, 4.91.
EXAMPLE 14
2,5-Dimethylfuran-3-carboxy[3-(4-methoxybenzyl)anilide]
121. Yield: 86.8%
122. m.p.: 100.0-102.5.degree. C.
123. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.35 (1H,
m), 7.25 (1H, t, J=8 Hz), 7.25 (1H, b), 7.1 (2H, d, J=8 Hz), 6.92
(1H, d, J=8 Hz), 6.88-6.75 (1H, m), 6.82 (2H, d, J=8 Hz), 6.05 (1H,
s), 3.9 (2H, s), 3.75 (3H, s), 2.55 (3H, s), 2.25 (3H, s)
124. IR (KBr) cm.sup.-1: 3345, 1656, 1246, 1074, 694
125. Elemental analysis (%): Calc'd for C.sub.21H.sub.21NO.sub.3:
C, 75.20; H, 6.31; N, 4.18. Found: C, 75.28; H, 6.32; N, 4.21.
EXAMPLE 15
2,5-Dimethylfuran-3-carboxy[3-(2-methoxycarbonylvinyl)anilide]
126. Yield: 63.3%
127. m.p.: 159.5-161.5.degree. C.
128. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.82 (1H, m), 7.7 (1H,
d, J=15 Hz), 7.58 (1H, m), 7.38 (1H, b), 7.35 (1H, t, J=8 Hz), 7.28
(1H, m), 6.48 (1H, d, J=15 Hz), 6.12 (1H, s), 3.82 (3H, s), 2.55
(3H, s), 2.25 (3H, s)
129. IR (KBr) cm.sup.-1: 3387, 1685, 1670, 1068, 800
130. Elemental analysis (%): Calc'd for C.sub.17H.sub.17NO.sub.4:
C, 68.22; H, 5.72; N, 4.68. Found: C, 67.55; H, 5.64; N, 4.62.
EXAMPLE 16
2,5-Dimethylfuran-3-carboxy(3-phenylanilide)
131. Yield: 50.0%
132. m.p.: 90.0-92.0.degree. C.
133. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.82 (1H, s), 7.6 (2H,
d, J=8 Hz), 7.55 (1H, d, J=8 Hz), 6.48-6.3 (6H, m), 6.12 (1H, s),
2.55 (3H, s), 2.25 (3H, s)
134. IR (KBr) cm.sup.-1: 3367, 1646, 1074, 755
135. Elemental analysis (%): Calc'd for C.sub.19H.sub.17 NO.sub.2:
C, 78.33; H, 5.88; N, 4.81. Found: C, 78.17; H, 6.00; N, 4.72.
EXAMPLE 17
2,5-Dimethylfuran-3-carboxy(3-neopentyloxymethylanilide)
136. Yield: 50.0%
137. m.p.: 95.5-97.0.degree. C.
138. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.48 (2H, m), 7.32 (1H,
t, J=8 Hz), 7.3 (1H, b), 7.12 (1H, d, J=8 Hz), 4.52 (2H, s), 3.12
(2H, s), 2.55 (3H, s), 2.25 (3H, s), 0.95 (9H, s)
139. IR (KBr) cm.sup.-1: 3324, 1646, 1091, 700
140. Elemental analysis (%): Calc'd for C.sub.19H.sub.25NO.sub.3:
C, 72.35; H, 7.99; N, 4.44. Found: C, 72.38; H, 8.03; N, 4.20.
EXAMPLE 18
2,5-Dimethylfuran-3-carboxy(3-isopropenylanilide)
141. Yield: 50.0%
142. m.p.: 71.0-72.0.degree. C.
143. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.65 (1H, m), 7.5 (1H,
m), 7.3 (1H, b), 7.3 (1H, t, J=8 Hz), 7.22 (1H, m), 6.12 (1H, s),
5.4 (1H, s), 5.1 (1H, s), 2.6 (3H, s), 2.55 (3H, s), 2.25 (3H,
s)
144. IR (KBr) cm.sup.-1: 3275, 1641, 1580, 1078, 790
145. Elemental analysis (%): Calc'd for C.sub.16H.sub.17NO.sub.2:
C, 75.27; H, 6.71; N, 5.49. Found: C, 75.29; H, 6.88; N, 5.48.
EXAMPLE 19
2,5-Dimethylfuran-3-carboxy(3-ethynylanilide)
146. Yield: 50.0%
147. m.p.: 83.0-84.0.degree. C.
148. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.7 (1H, m), 7.6 (1H,
m), 7.32-7.2 (3H, m), 6.1 (1H, s), 3.05 (1H, s), 2.55 (3H, s), 2.25
(3H, s)
149. IR (KBr) cm.sup.-1: 3245, 1644, 1079, 796
150. Elemental analysis (%): Calc'd for C.sub.15H.sub.13NO.sub.2:
C, 75.30; H, 5.48; N, 5.85. Found: C, 75.50; H, 5.46; N, 5.96.
EXAMPLE 20
2,5-Dimethylfuran-3-carboxy(3-ethylanilide)
151. Yield: 91.0%
152. m.p.: 113-115.degree. C.
153. Mass (m/z): 243 (M.sup.+), 123.94
154. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.47-6.95 (4H, m), 6.1
(1H, s), 2.66 (3H, q), 2.60 (3H, s), 2.29 (3H, s), 1.25 (3H, t)
EXAMPLE 21
2,5-Dimethylfuran-3-carboxy(3-isopropylanilide)
155. Yield: 84.0%
156. m.p.: 79-80.degree. C.
157. Mass (m/z): 257 (M.sup.+), 149.135
158. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.47-6.98 (4H, m), 6.11
(1H, s), 2.91 (1H, q,q), 2.60 (3H, s), 2.29 (3H, s), 1.26 (d,
6H)
EXAMPLE 22
2,5-Dimethylfuran-3-carboxy(2,6-diethylanilide)
159. Yield: 85.2%
160. m.p.: 128.0-131.0.degree. C.
161. Mass (m/z): 271 (M.sup.+), 242.228
162. .sup.1NMR (CDCl.sub.3) .delta. ppm: 7.28-7.12 (3H, m), 6.82
(1H, b), 6.16 (1H, s), 2.63 (4H, q), 2.58 (3H, s), 2.31 (3H, s),
1.20 (6H, t)
EXAMPLE 23
2,5-Dimethylfuran-3-carboxy(3-hexylanilide)
163. (Step 1)
164. To a solution of 3.95 g of 2,5-dimethylfuran-3-carbonyl
chloride in 60 ml of dichloromethane were added 3.45 ml of
triethylamine and 2.99 ml of m-iodoaniline under ice-cooling, and
the resulting mixture was stirred at room temperature for 6.5
hours. After the reaction mixture was cooled, it was diluted by
adding 50 ml of dichloromethane. The diluted mixture was
successively washed with 1 N sodium hydroxide, 1 N hydrochloric
acid and a saturated aqueous solution of sodium chloride and dried
over sodium sulfate followed by distilling off the solvent. The
residue was subjected to column chromatography through silica gel
to give 7.64 g of 2,5-dimethylfuran-3-carboxy(3-iodoanilide) as
pale-yellow crystals in a 89.9% yield.
165. (Step 2)
166. To a solution of 0.68 g of the crystals obtained in Step 1 in
8 ml of diethyl ether were added 29.3 mg of
[1,1'-bis(diphenylphosphino)ferrocene- ]palladium(II) chloride and
11 ml of 1 M hexylmagnesium bromide, prepared from hexyl bromide
and magnesium, divided into six equal parts, and the resulting
mixture was stirred at room temperature for 47 hours. After adding
2 N hydrochloric acid to the reaction mixture, the catalyst was
filtered off and the filtrate was extracted with diethyl ether. The
extract was successively washed with an aqueous solution of sodium
bicarbonate and a saturated aqueous solution of sodium chloride and
dried over sodium sulfate. After distilling off the solvent, the
residue was purified by chromatography through silica gel and then
D-ODS-5, YMC-packed column to give 316 mg of the desired compound
as white crystals in a 52.8% yield.
167. m.p.: 71.5-72.0.degree. C.
168. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.35 (1H,
m), 7.25 (1H, b), 7.22 (1H, t, J=8 Hz), 6.95 (1H, d, J=8 Hz), 6.1
(1H, s), 2.65-2.5 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.7-1.5 (2H,
m), 1.4-1.2 (6H, m), 0.85 (3H, t, J=7 Hz)
169. IR (KBr) cm.sup.-1: 3310, 1643, 1077, 788
170. Elemental analysis (%): Calc'd for C.sub.19H.sub.25NO.sub.2:
C, 76.22; H, 8.42; N, 4.68. Found: C, 76.15; H, 8.54; N, 4.55
171. Following the similar procedure as above, but using an
appropriate Grignard reagent instead of hexylmagnesium bromide,
there were obtained the following compounds.
EXAMPLE 24
2,5 -Dimethylfuran-3-carboxy (3-butylanilide)
172. Yield: 36.4%
173. m.p.: 77.0-80.0.degree. C.
174. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.35 (1H,
m), 7.25 (1H, b), 7.22 (1H, t, J=6 Hz), 6.95 (1H, d, J=8 Hz), 6.1
(1H, s), 2.65-2.55 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.6 (2H,
m), 1.35 (2H, m), 0.92 (1H, t, J=7 Hz)
175. IR (KBR) cm.sup.-1: 3285, 1646, 1075, 702
176. Elemental analysis (%): Calc'd for C.sub.17H.sub.21NO.sub.2:
C, 75.25; H, 7.80; N, 5.16. Found: C, 75.13; H, 7.87; N, 5.13
EXAMPLE 25
2,5-Dimethylfuran-3-carboxy(3-sec-butylanilide)
177. Yield: 38.1%
178. m.p.: 80.0-81.0.degree. C.
179. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.4 (1H, m), 7.38 (1H,
m), 7.25 (1H, b), 7.22 (1H, t, J=8 Hz), 6.95 (1H, d, J=8 Hz), 6.1
(1H, s), 2.65-2.5 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 1.68-1.5
(2H, m), 1.25 (3H, d, J=7 Hz), 0.85 (3H, t, J=7 Hz)
180. IR (KBr) cm.sup.-1: 3255, 1647, 1078, 791
181. Elemental analysis (%): Calc'd for C.sub.17H.sub.21NO.sub.2:
C, 75.25; H, 7.80; N, 5.16. Found: C, 75.19; H, 7.68; N, 5.14
EXAMPLE 26
2,5-Dimethylfuran-3-carboxy(3-pentylanilide)
182. Yield: 18.3%
183. m.p.: 97.0-97.5.degree. C.
184. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.35 (1H,
m), 7.28 (1H, b), 7.25 (1H, t, J=8 Hz), 6.95 (1H, d, J=8 Hz), 6.1
(1H, s), 2.65-2.5 (2H, m), 2.55 (3H, s), 2.25 (3H, s), 1.7-1.5 (2H,
m), 1.4-1.2 (4H, m), 0.88 (3H, t, J=7 Hz)
185. IR (KBr) cm.sup.-1: 3304, 1644, 1077, 710
186. Elemental analysis (%): Calc'd for C.sub.18H.sub.23NO.sub.2:
C, 75.76; H, 8.12; N, 4.91. Found: C, 75.77; H, 8.18; N, 5.06
EXAMPLE 27
2,5-Dimethylfuran-3-carboxy-(3-cyclohexylanilide)
187. Yield: 52.7%
188. m.p.: 113.0-114.5.degree. C.
189. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.48 (1H, m), 7.35 (1H,
m), 7.28 (1H, b),7.25 (1H, t, J=8 Hz), 6.98 (1H, d, J=8 Hz), 6.1
(1H, s), 2.55 (3H, s), 2.55-2.45 (1H, m), 2.25 (3H, s), 1.95-1.68
(5H, m), 1.55-1.15 (5H, m)
190. IR (KBr) cm.sup.-1: 3324, 1646, 1230, 1074, 791
191. Elemental analysis (%): Calc'd for C.sub.19H.sub.23NO.sub.2:
C, 76.74; H, 7.80; N, 4.71. Found: C, 76.62; H, 7.78; N, 4.67
EXAMPLE 28
2,5-Dimethylfuran-3-carboxy(3-cyclopentylanilide)
192. Yield: 35.9%
193. m.p.: 92.0-93.0.degree. C.
194. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.35 (1H,
m), 7.25 (1H, b), 7.22 (1H, t, J=8 Hz), 7.00 (1H, d, J=8 Hz), 6.1
(1H, s), 3.08-2.9 (1H, m), 2.55 (3H, s), 2.25 (3H, s), 2.15-1.95
(2H, m), 1.9-1.5 (6H, m)
195. IR (KBr) cm.sup.-1: 3322, 1647, 1232, 1076, 700
196. Elemental analysis (%): Calc'd for C.sub.18H.sub.21NO.sub.2:
C, 76.30; H, 7.47; N, 4.94. Found: C, 76.21; H, 7.56; N, 4.93
EXAMPLE 29
2,5-Dimethylfuran-3-carboxy(3-benzylanilide)
197. Yield: 59.8%
198. m.p.: 123.0-125.0.degree. C.
199. .sup.1H NMR (CDCl.sub.3) .delta. ppm: 7.45 (1H, m), 7.38 (1H,
m), 7.35-7.15 (7H, m), 6.95 (1H, d, J=8 Hz), 3.98 (2H, s), 2.55
(3H, s), 2.25 (3H, s)
200. IR (KBr) cm.sup.-1: 3314, 1640, 1078, 777, 701
201. Elemental analysis (%): Calc'd for C.sub.21H.sub.19NO.sub.2:
C, 78.66; H, 6.27; N, 4.59. Found: C, 77.76; H, 6.28; N, 4.55
REFERENTIAL EXAMPLE 1
Ethyl 2,5-dimethylfuran-3-carboxylate
202. To a suspension of 2.4 g of sodium hydride (60% dispersion in
mineral oil) in 10 ml of N,N-dimethylformamide (hereinafter,
abbreviated as DMF) a solution of 6.5 ml of ethyl acetoacetate in 5
ml of DMF was added dropwise with stirring under ice-cooling, and
5.97 ml of chloroacetone were added dropwise thereto with stirring
under ice-cooling. After stirring at room temperature for 3 hours,
the reaction mixture was poured into water and the aqueous mixture
was extracted with ethyl acetate. The extract was washed with a
saturated aqueous solution of sodium chloride and dried over
anhydrous sodium sulfate. After distilling off the solvent under
reduced pressure, the residue was distilled in vacuo to give 8.01 g
of ethyl .alpha.acetonitrile-acetoacetate having b.p. 105.degree.
C./2 mmHg in a 86% yield.
203. To a solution of the ester thus obtained in 20 ml of ethanol
were added 2 g of p-toluenesulfonic acid, and the resulting mixture
was heated under reflux for 2 hours. The reaction mixture was
allowed to cool to room temperature and the solvent was distilled
off under reduced pressure. The residue was dissolved in ethyl
acetate and the solution was washed with a saturated aqueous
solution of sodium chloride followed by drying over anhydrous
magnesium sulfate. After distilling off the solvent under reduced
pressure, the residue was purified by column chromatography through
silica gel using a 10:1 mixture of n-hexane and ethyl acetate as an
eluent to give 5.14 g of ethyl 2,5-dimethylfuran-3-carboxylate in a
71% yield.
REFERENTIAL EXAMPLE 2
2,5-Dimethylfuran-3-carboxylic Acid
204. A mixture of 3.2 g of ethyl 2,5-dimethylfuran-3-carboxylate,
35 ml of ethanol and 20 ml of 2 N sodium hydroxide was stirred at
room temperature for 1.5 hours followed by heating under reflux for
an hour. After the reaction mixture was allowed to cool to room
temperature, it was concentrated under reduced pressure. The
residue was dissolved in water and acidified with diluted sulfuric
acid. Precipitated crystals were collected by filtration, washed
with water and dried to give 2.27 g of
2,5-dimethylfuran-3-carboxylic acid in a 85% yield.
205. The compound having the general formula (I) mentioned above
and the composition containing the compound (I) as the active
ingredient, with which the present invention are concerned, can be
employed by mixing with carriers or, if necessary, with any other
additives, followed by the preparation of formulations usually
employed such as oil solution, emulsifiable concentrate,
solubilizer, paste, wettable powder, flowable, dry flowable, spray
and paint, and then the formulation can be used according to any
known method for wood preservative treatment. As the additives
which are employed suitably to improve the property of the
formulation and to strengthen the wood preserving effect, there may
be mentioned cationic, anionic and non-ionic surfactants, various
high polymer compounds such as methylcellulose and vinyl acetate
resin and water-repellents such as silicon oil and paraffin. It is
needless to say that combined use may be possible with other wood
preservatives, fungicides and bacteriocides including organic
iodine compounds such as Sanplas, IF-1000 and Troysan, azole
compounds such as Propiconazole and Tebuconazole, Thiabendazole,
Dichlofluanid and quaternary ammonium salt compounds; with
insecticides including pyrethroids such as Permethrin, Etofenprox,
Cypermethrin, Silaneophen, Tralomethrin, organic phosphor compounds
such as Chloropyrifos, Phoxim and Propetamphos, and Imidacroprid;
and with potentiators such as bis-(2,3,3,3-tetrachlorpropyl- )
ether. An increased effect can be expected by combined use in this
manner. In a real case of application, though the content of the
compound of the present invention can be changed within a wide
range depending on the formulation or on the object, it may usually
be suitable to use from 0.1 to 95 weight percent, preferably from
0.2 to 60 weight percent. These formulations are employable in
usual methods for wood treatment: for example, coating, dispersal,
dipping treatment, mixing, impreganation, or mixing treatment with
an adhesive.
206. Several formulation examples of the compound of the present
invention will be shown below, in which it is needless to say that
the combination ratio and the kind of additives can be changed
widely (in the descriptions below, part means weight part in all
cases).
FORMULATION EXAMPLES OF THE WOOD PRESERVATIVES
Formulation Example 1 Emulsifiable Concentrate
207. Twenty parts of the Compound of Example 20 were dissolved in
70 parts of xylene, and then 10 parts of polyoxyethylene nonyl
phenyl ether were added and mixed enough to obtain the emulsifiable
concentrate.
208. Thus obtained emulsifiable concentrate is diluted with a
suitable amount of water at use, and can be applied to a wood
material to be treated by coating, dipping or spraying, and in
addition, employable by mixing with adhesives which are used for
plywood, particle board and hardboard.
Formulation Example 2 Oil Solution
209. Two parts of the Compound of Example 21 were added with 98
parts of kerosene oil to obtain the oil solution.
210. Thus obtained oil solution can be applied to a wood material
to be treated by spraying, coating, dipping or impregantion.
Formulation Example 3 Coating Formulation
211. Ten parts of the Compound of Example 20, 20 parts of Barite
dust, 10 parts of vinyl resin, 25 parts of pine resin and 35 parts
of xylene were mixed homogeneously to obtain the coating
formulation.
Formulation Example 4 Wettable Powder
212. Forty parts of the Compound of Example 22, 56 parts of clay, 3
parts of sodium lauryl alcohol sulfonate and 1 part of polyvinyl
alcohol were mixed homogeneously in a mixer, and pulverized by use
of a hammer-mill to obtain the wettable powder.
TEST EXAMPLES OF WOOD PRESERVATION
213. The effectiveness of the wood preservative of the present
invention will be explained concretely by the following
examples.
214. (1) According to the test method for wood preservation
described in the Japan Industrial Standards [JIS A-9201 (1991)],
each of the test compounds was dissolved to a defined concentration
in methanol. The solution was impregnated under a reduced pressure
into a Sugi (Japanese cedar) sapwood (2.times.2.times.1) cm and
then air-dried. Weathering test was repeated 10 times in which one
cycle of the treatment was stirring in water for 8 hours, and then
heating for 16 hours at 60.degree. C. The test material was placed
on the flora of Serpula lacrymans which had been previously grown
on a guartz sand medium (malt extract 2%, glucose 1%, peptone 0.3%
and yeast 0.2%), and forcedly decayed at 20.degree. C. for 12
weeks. From the difference between the dry weight of the test
material before the test and that after test, the degree of
decrease in weight was obtained. Table 2 shows the results. The
test was carried out by use of 9 samples for each condition, and
the values shown in Table 2 are the mean values calculated from 9
samples.
3 TABLE 2 Sample drugs Impregnant Mean weight decrease
concentration (%) by decay (%) Example 20 0.01 0 0.005 0.1 Example
21 0.01 0 0.005 0 Control compound 1 0.01 9.7 0.005 18.6 Without
treatment 18.4 Control compound 1:
4-Chlorophenyl-3-iodopropargylformal Product of Nagase Co., Ltd.:
IF-1000
215. From the data shown above, the compound having the general
formula (I) prevented decay of the wood samples due to wood-rotting
fungi to a significant extent.
216. (2) Each of 0.1 w/v % methanol solutions of the compound of
the present invention and the control drug was impregnated into the
test material [a Sugi (Japanese cedar) sapwood, 2.times.2.times.0.5
cm] under a reduced pressure and then air-dried. Weathering test
was repeated twice in which one cycle of the treatment was washing
(about 2 liter per minute supply) with water for 5 hours, and then
heating for 19 hours at 60.degree. C. After dry air sterilization,
the test samples were prepared.
217. The test materials were placed on the flora of Coriolus
versicolor which is a lignin-decomposing fungus, and of Tyromyces
palustris which is a cellulose-decomposing fungus, and both of
which are designated fungal species for assay of wood preservating
effect. Both fungi had been previously grown on an agar medium
(malt extract 2%, glucose 1% and peptone 0.5%) After the wood
samples were forcedly deteriorated at 26.degree. C. for 3 weeks,
the effectiveness was determined from the degree of hyphal growth
on the test material and the presence or absence of lowered maximum
crushing strength. Table 3 shows the result.
218. The wood preventive efficacy was judged by the following
criteria.
219. +: No hyphal growth was observed on the test material, and no
difference was found in the maximum crushing strength from the
healthy wood sample.
220. .+-.: A little hyphal growth was observed on the test
material, or a little decrease was found in the maximum crushing
strength.
221. -: Hyphal growth was observed on the test material, or clear
decrease was found in the maximum crushing strength.
4TABLE 3 Test drug Coriolus versicolor Tyromyces palustris Example
1 .+-. - Example 2 - - Example 3 - - Example 4 - - Example 5 - -
Example 6 + + Example 7 + - Example 8 .+-. - Example 9 - - Example
10 + - Example 11 + .+-. Example 12 .+-. .+-. Example 13 + +
Example 14 + + Example 15 + - Example 20 + + Example 21 + + Example
23 + + Example 24 + + Example 25 + + Example 26 + + Control
compound 2 + + Without treatment - - Control compound 2:
3-Bromo-2,3-diiodo-2-propenylethylcarbonate Product of Sankyo Co.,
Ltd.: Sanplas
222. When the composition of the present invention is desired to be
employed, the combination ratio may be suitably selected depending
on the kind of wood and the kind of wood material to be treated
with the wood preservative, or the means for treatment (for
example, coating, dipping, dispersal, impregnation, mixing and
mixing with an adhesive). Usually, the combination ratio of
dimethylfurancarboxyanilide and any other wood preservative may be
from 240:1 to 1:35, preferably from 30:1 to 1:10, and more
preferably from 5:1 to 1:5.
223. The content of the composition of the present invention may be
changed within a wide range depending on the formulation. In
general, the content may be from 0.1 to 95%, preferably from 0.2 to
60%, in the formulation.
224. Several formulation examples of the compound of the present
invention will be shown below, in which it is needless to say that
the combination ratio and the kind of additives can be changed
widely.
FORMULATION EXAMPLES OF THE WOOD PRESERVATIVE COMPOSITION
Formulation Example 1 Emulsifiahle Concentrate
225. Ten parts of the Compound of Example 20 were dissolved in 30
parts of Sanplas and 50 parts of xylene, 10 parts of
polyoxyethylene nonyl phenyl ether were then added and mixed enough
to obtain the emulsifiable concentrate.
226. Thus obtained emulsifiable concentrate is diluted with a
suitable amount of water at the time of use, and can be applied to
a wood material to be treated by coating, dipping or spraying, and
in addition, employable by mixing with adhesives which are used for
plywood, particle board and hardboard.
Formulation Example 2 Oil Solution
227. Two parts of the compound of Example 21 and 1 part of troysan
were dissolved in 96 parts of kerosene oil to obtain the oil
solution.
Formulation Example 3 Wettable Powder
228. Fifteen parts of the compound of Example 22, 25 parts of
IF-1000, 56 parts of clay, 3 parts of sodium lauryl alcohol
sulfonate and 1 part of polyvinyl alcohol were mixed homogeneously
in a mixer, and pulverized by use of a hammer-mill to obtain the
wettable powder.
229. The effect of the wood preservative composition of the present
invention will be explained concretely by the following
examples.
TEST EXAMPLES OF WOOD PRESERVATIVE COMPOSITIONS
230. Assay of minimum inhibitory concentration by the agar dilution
method.
231. According to the agar dilution method, on sterilized media
(potato dextrose agar medium; potato extract powder 0.4%, glucose
2%, agar 1.5%) prepared to contain certain concentrations of a test
sample, flora (about 4 mm in diameter) of wood rotting fungi,
Coriolus versicolor and Tyromyces palustris, which had been
cultured previously on the same kind of medium, were inoculated.
After culture at 25.degree. C. for 5 days, hyphal growth was
observed to determine the minimum inhibitory concentration.
232. Whether there is any potentiation or not has been described in
Applied Microbiology 9, 538-541 (1961) by F. C. Kull et al. The
assay was carried out according to the method usually employed.
233. Table 4 and FIGS. 1A to 1F show the results obtained by
combination of Example 20 with each of Sanplas, Troysan and
IF-1000.
5TABLE 4 MIC (ppm) of Example 20 combined with several other active
agents Test (Combined ratio) fungus Example 20 A Example 20 + A
Example 20:A Coriolus 2.5 15 1.30 + 3.0 (1:2.3) Versicolor 0.8 +
5.0 (1:6.3) 0.4 + 9.0 (1:22.5) Tyromyces 200 25 110.0 + 5.0 (22:1)
Palustris 70.0 + 9.0 (7.8:1) 40.0 + 14.0 (2.9:1) Test (Combined
ratio) fungus Example 20 B Example 20 + B Example 20:B Coriolus 2.5
25 1.25 + 5.0 (1:4) Versicolor 0.8 + 7.5 (1:9.4) 0.4 + 12.5
(1:31.3) Tyromyces 200 2.5 120.0 + 0.6 (200:1) Palustris 80.0 + 1.0
(80:1) 40.0 + 1.5 (26.7:1) Test (Combined ratio) fungus Example 20
C Example 20 + C Example 20:C Coriolus 2.5 6 1.25 + 1.2 (1.0:1)
Versicolor 0.8 + 1.8 (1:2.3) 0.5 + 3.0 (1:6) Tyromyces 200 2 120.0
+ 0.5 (240:1) Palustris 80.0 + 0.8 (100:1) 40.0 + 1.2 (33:1) A:
Sanplas B: Troysan C: IF-1000
234. Then, the same test as above was carried out for Example 21.
Table 5 and FIGS. 2A to 2F show the result.
6TABLE 5 MIC (ppm) of Example 21 combined with several other active
agents Test (Combined ratio) fungus Example 21 A Example 21 + A
Example 21:A Coriolus 10.0 15 6.0 + 3.0 (2:1) Versicolor 3.5 + 5.0
(1:1.4) 2.0 + 8.0 (1:4) Tyromyces 200 25 120.0 + 5.0 (24:1)
Palustris 75.0 + 9.0 (8.3:1) 40.0 + 15.0 (2.7:1) Test (Combined
ratio) fungus Example 21 B Example 21 + B Example 21:B Coriolus
10.0 25 5.5 + 5.0 (1.1:1) Versicolor 3.0 + 8.0 (1:2.7) 1.5 + 12.5
(1:8.3) Tyromyces 200 2.5 120.0 + 0.7 (171.4:1) Palustris 90.0 +
1.0 (90:1) 40.0 + 1.75 (22.9:1) Test (Combined ratio) fungus
Example 21 C Example 20 + C Example 21:C Coriolus 10.0 6 6.0 + 1.6
(3.6:1) Versicolor 4.0 + 2.4 (1.7:1) 2.0 + 3.6 (1:1.8) Tyromyces
200 2 120.0 + 0.5 (240:1) Palustris 90.0 + 1.0 (90:1) 40.0 + 1.4
(28.6:1) A: Sanplas B: Troysan C: IF-1000
235. Each of the minimum inhibitory concentration curves shown in
FIGS. 1A to 1F and FIGS. 2A to 2F lies under the diagonal line
shown by broken line.
236. This data exhibits that the furancarboxyanilide derivative
potentiates the effect of each of Sanplas, Troysan and IF-1000 by
combination.
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