US2017101392A1PendingUtilityA1
Processes for the preparation of pesticidal compounds
Est. expiryOct 17, 2033(~7.3 yrs left)· nominal 20-yr term from priority
Inventors:Qiang YangBeth LorsbachGregory T. WhitekerGary RothCarl DeamicisDaniel I. KnueppelAnn M. BuysseKaitlyn GrayXiaoyong LiJoseck M. MuhuhiRonald Ross, Jr.David E. PodhorezYu Zhang
C07D 401/04A01N 47/40A01N 43/56
63
PatentIndex Score
0
Cited by
0
References
0
Claims
Abstract
The present application provides processes for making pesticidal compounds and compounds useful both as pesticides and in the making of pesticidal compounds.
Claims
exact text as granted — not AI-modified1 . A process comprising:
(a) reacting 3-hydrazinopyridine dihydrochloride with methyl acrylate, under basic conditions, to yield 1-(pyridin-3-yl)pyrazolidin-3-one; and (b) chlorinating 1-(pyridine-3-yl)pyrazolidin-3-one with phosphoryl chloride (POCl 3 ) to yield dihydropyrazole chloride (5a)
2 . (canceled)
3 . A process comprising nitrating 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b) to yield 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c)
4 . A process comprising reducing 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d)
5 . A process comprising reacting 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d) with an activated carbonyl thioether of formula X 1 C(═O)C 1 -C 4 -alkyl-S—R 1 to yield pesticidal thioether (3b)
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl, and
X 1 is selected from the group consisting of Cl, OC(═O)C 1 -C 4 alkyl, and a group that forms an activated carboxylic acid.
6 .- 7 . (canceled)
8 . A process comprising
(a) reacting 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-amine (5d) with 3-chloropropionyl chloride to yield 3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide (5e);
(b) reacting compound (5e) with HSR 1
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl
to yield pesticidal thioether (5f)
9 . A process comprising:
(a) nitrating 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b)
to yield 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c)
(b) reducing 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d)
(c) reacting 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d) with an activated carbonyl thioether of formula X 1 C(═O)C 1 -C 4 -alkyl-S—R 1 to yield pesticidal thioether (3b)
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl, and
X 1 is selected from the group consisting of Cl, OC(═O)C 1 -C 4 alkyl, and a group that forms an activated carboxylic acid; and
(d) alkylating pesticidal thioether (3b) with R 2 —X 2 to yield pesticidal thioether (3c),
wherein,
X 2 is a leaving group, and
R 2 is selected from the group consisting of C 1 -C 4 -alkyl and C 2 -C 4 -alkynyl.
10 . A process comprising:
(a) reacting 3-hydrazinopyridine dihydrochloride with methyl 2-acetamidoacrylate to yield N-(3-oxo-1-(pyridin-3-yl)pyrazolidin-4-yl)acetamide
(b) chlorinating/eliminating N-(3-oxo-1-(pyridin-3-yl)pyrazolidin-4-yl)acetamide to yield 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b)
(c) nitrating 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b) to yield 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c)
(d) reducing 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d)
(e) reacting 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d) with an activated carbonyl thioether of formula X 1 C(═O)C 1 -C 4 -alkyl-S—R 1 to yield pesticidal thioether (3b)
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl, and
X 1 is selected from the group consisting of Cl, OC(═O)C 1 -C 4 alkyl, and a group that forms an activated carboxylic acid; and
(f) alkylating pesticidal thioether (3b) with R 2 —X 2 to yield pesticidal thioether (3c),
wherein,
X 2 is a leaving group, and
R 2 is selected from the group consisting of C 1 -C 4 -alkyl and C 2 -C 4 -alkynyl.
11 . A process comprising:
(a) nitrating 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b)
to yield 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c)
(b) reducing 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d)
(c)
(1) reacting 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-amine (5d) with 3-chloropropionyl chloride to yield 3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide (5e);
(2) reacting compound (5e) with HSR 1
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl
to yield pesticidal thioether (5f)
and
(d) alkylating pesticidal thioether (5f) with R 2 —X 2 to yield pesticidal thioether (5g),
wherein,
X 2 is a leaving group, and
R 2 is selected from the group consisting of C 1 -C 4 -alkyl and C 2 -C 4 -alkynyl.
12 . A process comprising:
(a) reacting 3-hydrazinopyridine dihydrochloride with methyl 2-acetamidoacrylate to yield N-(3-oxo-1-(pyridin-3-yl)pyrazolidin-4-yl)acetamide
(b) chlorinating/eliminating N-(3-oxo-1-(pyridin-3-yl)pyrazolidin-4-yl)acetamide to yield 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b)
(c) nitrating 3-(3-chloro-1H-pyrazol-1-yl)pyridine (5b) to yield 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c)
(d) reducing 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (5c) to yield 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (5d)
(e)
(1) reacting 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-amine (5d) with 3-chloropropionyl chloride to yield 3-chloro-N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethylpropanamide (5e);
(2) reacting compound (5e) with HSR 1
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl to yield pesticidal thioether (5f)
and
(f) alkylating pesticidal thioether (5f) with R 2 —X 2 to yield pesticidal thioether (5g),
wherein,
X 2 is a leaving group, and
R 2 is selected from the group consisting of C 1 -C 4 -alkyl and C 2 -C 4 -alkynyl.
13 . A compound 1-(pyridin-3-yl)pyrazolidin-3-one
14 . A compound N-(3-oxo-1-(pyridin-3-yl)pyrazolidin-4-yl)acetamide
15 . A compound 3-chloro-N-(3-chloro-1-(pyridine-3-yl)-1H-pyrazol-4-yl)propanamide (5e)
16 . A compound 3-(3-chloro-4,5-dihydro-1H-pyrazol-1-yl)pyridine (5a)
17 .- 20 . (canceled)
21 . A process according to claim 11 , wherein thioether (5g)
is prepared by alkylating thioether (5f) with R 2 —X 2
wherein R 2 is selected from the group consisting of C 1 -C 4 -alkyl and C 2 -C 4 -alkynyl,
wherein X 2 is a leaving group,
in the presence of a base, in the presence of a polar aprotic solvent, and in the presence of an additive.
22 .- 28 . (canceled)
29 . A process according to claim 5 , wherein X 1 C(═O)C 1 -C 4 -alkyl-S—R 1 ,
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl, and
X 1 is selected from the group consisting of Cl, OC(═O)C 1 -C 4 alkyl, and a group that forms an activated carboxylic acid
is prepared from
which is prepared by the photochemical free-radical coupling of 3-mercaptopropionic acid and esters thereof with 3,3,3-trifluoropropene in the presence of 2,2-dimethoxy-2-phenylaceto-phenone initiator and long wavelength UV light in an inert organic solvent.
30 . A process according to claim 5 , wherein X 1 C(═O)C 1 -C 4 -alkyl-S—R 1 ,
wherein,
R 1 is selected from the group consisting of C 1 -C 4 -haloalkyl and C 1 -C 4 -alkyl-C 3 -C 6 -halocycloalkyl, and
X 1 is selected from the group consisting of Cl, OC(═O)C 1 -C 4 alkyl, and a group that forms an activated carboxylic acid
is prepared from
which is prepared by the low temperature free-radical initiated coupling of 3-mercaptopropionic acid with 3,3,3-trifluoropropene in the presence of 2,2′-azobis(4-methoxy-2,4-dimethyl) valeronitrile (V-70) initiator at temperatures of about −50° C. to about 40° C. in an inert organic solvent.
31 . (canceled)Cited by (0)
No later patents cite this yet.
References (0)
No backward citations on record.