Note: Descriptions are shown in the official language in which they were submitted.
3 ~
~ , BA-8592-A--\
HERBICIDAL PY~IDINESUk~A~
Back~round of the I en_ion
Herbicidal pyridine~ulfonamides of the ~ormula
Rl X
O N ~
E~2~S02t~HCN~Oz
where
Rl i8 H. Cl. ~r, F, Cl-C~ alkyl, Cl-C~
alkoxy, Cl-C~ alkylthio, N02 or C02R5;
and
R2 is H. Cl, Br or CH3:
are disclo6ed in European Patent Application (EP-A)
13,~0.
EP-A-35,893 discloses herbicidal pyridinesulfon-
amide6 of formula
X
o N
Z ~ sOzUHCNH
where
Rl is S50)nR3; and
R2 i~ H, Cl, F, Br, CH3, OCH3, C~3,
N02, CN or NH2.
EP-A-B3,975 and ~P-A 85,476 dis~lofie herbicidal
benzene~ulfonamides of for~ula
~1 ~ 502NHCN~ ~ z
a N
where
Q is variou~ ~aturated and unsaturated 5- and
6-membered he~erocycle~.
~''
!
U.S. 4,378,991 di~loses herbicidal b~n~ene-
~ulfonamides of formula
~ R
5 ~1 ~ "
N
where
R is, among other va:Lue~, phenyl: and
Rl i8 H, F, Cl, B~, N02, CF3, Cl-C~
alkyl, OCF3 or Cl--C4 alkoxy.
EP-A-g7,122, publi~h~d December 28, 1983, dis-
closes herbicidal sulfonamide~ of formula
R N Rl
Z3 ~ S02NHCZNH ~ ~ E
3 YCHF2
where
X i~ 0, S, NR4 or CR5=N: and
~2 i~ H, Cl-C3 alkyl, haloalkyl. alkoxy,
alkylthio, alkyl~ulfinyl or alkylsul-
phonyl, halogen, NO~, ~WR8, S02NR6R7
~r CORg.
South African Patent Application 836,639
di~clo~e~ herbicidal sulfonamide~ of formula
N ~ 2
R1~ S0;2NHCONH~OE
2~A R3
where
~ i8 O, S, SO, S02 or ~A may ~orm an a~ino
radical NR6P.7: and
R.l i5 H, halogen, Cl-C4 alkylO Cl-C4 alkoxy,
Cl-C~ ~aloalkyl, Cl-C4 haloalkoxy, C2-C5
alkoxyalkoxy, Cl-C5 alkylthio, Cl-C5 alkyl-
sulfinyl or Cl-C5 alkylfiulfonyl.
Summarv_of th~_Invention
This invention relate6 to compounds of Formulae
I and II, agriculturally suitable compo~ition& con-
taining them and their method of use as preemergent
and/or postemergent herbicides or plant growth regulants.
W
~1 ~ S02NHCNA ~1 ~ (CH2)n-Q
(CH2)n Q N S02NHCNA
R
I II
wherein
R is H oe CH3,
Rl i8 H, Cl, Br, SCH3 o~ CH3;
n is 0, 1 or 2;
W i8 0 or S;
Q i8 phenyl optionally subs~i~uted wi~h Cl,
OC~3, or CH3, a saturated 5- or 6-membered
ring containing one heteroatom selected from 0,
S, or N, or an unsaturated 5- or 6-membered ring
containing 1 to 3 heteroatoms selected from 0-1
S, 0-1 0 or 0-3 N and when Q is an unsaturated
5- or 6-membered ring, it may optionally be
3 substituted by one or more groups selected
from Cl-C4 alkyl, halogen, C3-C~ alkenyl
Cl-C3 alkoxy, Cl-C3 alkylthio, C3-C4 alkenyl~
~hio, Cl-C2 haloalkoxy or Cl-C2 haloalkyl~hio:
~5
N ~ ~1 N ~1
A i6 ~ O z ,
A-l A-2 -3
~ ~1 /Y3 OCH3
~ O ~ or -cHz~oN
A-4 A-5 A-6
X i8 CH3, OCH3, OCH2CH3, Cl, F, Br, I, OCF2H,
CH2F, OCH2CH2F, OCH2CHF2, OCH2CF3 or
CF3;
Y is H, Cl-C2 alkyl, OCH3, OC2H5, C~20CH3,
3~ ~(OCH3~CH3~ N(C~I3)2' CF3, 3
OCH2CH-CH2, 0CH2C_CH, CH20CH2CH3,
OCH2CH20CH3' CH~SCH3, ~ Rz, ,~
R2L2R4
~ L ~ / 1-~ 3
'~ L ~CH2)m, C\2 ~ , OCF2H, SCF2H
or cyclopropyl:
m i~ 2 or 3;
Ll and L2 are independently O or S:
~2 i~ H or CH3;
R3 and R4 are independently Cl-C2 alkyl;
Z is CH or ~;
Yl is 0 or C~2;
~1 i8 CH3, OCH3, OC2H5 or OCF2~;
Y2 i8 H or CH3
~ ,r~
X2 ~ OCH3 SCH3 or CH3
Y3 i~ CH3, ~2H5 Gr ~H2~F3 and
3 i CH3 o~ OCH3
provided ~ae
a~ when ~ is Cl, ~, Br or I, then Z ~ CH and Y
3~ 2H5, N(OCH3)CH3, ~HCH3, N(CH )
NH2 or OCF2H;
b) when Y i~ cyclopropyl, ~ iG other t~an C1, F,
Br or I;
c) when Q iB lH-1,2,4~-triazol-1-yl, then
Z il3 C~:
d) when ~ or Y i8 OCF2R, then Z ~ CH;
e) when Q i~ a saturat:ed 5- or 6-membered ring
containing one nitrogen a~o~, ~t is bonded to
Che pyridine ring theough carbon; and
f~ wh@n W i~ S, then ~ i~ H, A is A-l, and ~ i~
3~ ~3~ 0~2H5, CR20CH3, C2H5, CF3, SC~3,
O~H2CH=CH2, OCH2C-CH, OCH2CH20CH3, CH(OCH3)2
/o~
or CH
\O~
and ~heir agricul~urally suitable 5alt~.
Preferred for reasons vf grea~er ease of synthe-
6iS and/or yreater h~rbicidal efficacy are:
1~ Compounds of Formulae I and II wherein
R i6 El:
~ iS O;
is ~elected from the group consisting oE
,~R6 ~R6 ~ ~
o,N N~0 ~ o
R6
Q~l Q-2 Q-3
3S
r~ ~
/ ~N N~C ' ~ ' ~ \N
CH3 R6
Q~ Q- 5 - 6
/ )~ a7 (V~ 5 /~
Q- 7 Q~8 ~_ 9
~ N~
Q-10 Q-ll Q-12
~ , R5
5~
.Q~ ~ Q- 1 5
2 5 R6 6 ~\R6
Q-lS Q-17 Q-18
~5 ~5 ~ 6
CH3 7
~ Q-20 Q-21
o~
R5~R7 ~;R~ It5 5 R7
.Q-23 Q~4 Q-?5 Q-26
~R6 '~R6 ~ II5~R6 .,~
(O)n' (o)n~ (O)n'
Q~:Z Q-28Q-29 0-30
~10 ~Rlo ' ,~ (~R5
~-31 0-32 Q-33
N~R5 ~ l,~
_3,~ Q~ Q-36
~L5 ~5 R5
~0 ~S ~N
N~( ~N= ( ~S~ and phenyl;
R6 R6 R6
Q-37 Q~ Q-39
n' i8 0 01 1:
R5, R6 and R7 a~e independently H or CH3;
~5 iB H, CH3. C2H5, Cl-C3 alky~thio.
SCH2~H~CH2~ SC~2H~ OC~3 or OCH2CH3
~8 ifi H or Cl:
a9 and Rlo are indep~ndently H, CH3 or
OCH3
~11 aQd R12 are i~dependentiy CH3 or
~H3;
I ; 8 OD 8 Or NR13; and
~13 is H, Cl-C3 alkyi or CH2CH=CH2;
2) Compound~ o Pcefer!red 1 wh~re ~ is A~
is H. ~' i8 0 and Q i~ ~elected fro~ the
group consi~ting ol Q-l, Q-2, Q-3, Q-4, Q-7,
Q~8, Q-9, Q-10, Q-ll. Q-14, ~-16, Q-17. Q 18,
~-21, ~-22, ~-2~, 52-~7, ~-30. Q-33 Q-37, Q-38
and phenyl:
3) Compound~ of Prefeered 2 where ~ is CH3,
OCH3, OCH2CH3 or Cl. and Y i~ CH3,
~H2CH3, OC~3, OCF2~1, CH~OCH3)2 o~
CH20CH3;
4) Compounds of Pceferred 3 where n i6 0;
5) Compounds o ~E~ r~ where Y is CH3,
CH2CH3, OCH3 or OCF2H;
6) Compounds of Preferred 5 of Focmula I;
7) Compounds of Preferced 5 o~ ~ormula II;
8) Compounds of Pref erled 6 ~ere Q i8 Q-l;
9) Compounds o~ Preferred 6 where ~ i~ Q-2;
10) Compound6 of Preferred 6 where Q i6 Q-3:
11) Compounds of PreferEed 6 where Q i~ Q-4:
12) Compound6 of Preferred 6 whers Q is Q-7;
13) Compounds ~ ~~~EE~ where Q is Q-8:
14) Compound6 nf P~ E~ where Q i6 Q-9;
15) Compounds of Preferred~6 where Q is Q-10:
16~ Compounds of Preferred 6 where Q is Q-ll;
1~ Co~pound~ f ~s~~LL~ where Q i~ Q-14:
18~ Compound~ of Pceferred 6 where Q i~ ~-16;
1~) Compounds of Preferce,d 6 where Q i~ Q-17;
20) Compounds of ~Preferred 6 where Q i6 ~-18:
21) Compound~ of Preferred 6 where Q i6 Q-21;
22) Compound~ of Preferred_6 where Q is Q-2Z;
23) Compounds of Preferred 6 where Q i8 Q-2~;
24~ Compounds of Preferred 6 where Q i8 Q-27;
25) Compounds of P ferr,ed 6 where Q i~ Q-30;
26) Compounds of Preferred 6 where Q i~ Q-33;
27) Compounds of Preferred 6 where Q is Q-37;
28) Compcunds of P ferred 6 where Q ifi Q-38;
29) Compoundfi of Preferred 6 where Q i8 phenyl;
30) Compounds of Prefe~red 7 where Q i~ Q-l:
31) Compounds of Preferred 7 where Q is Q-2;
32) Compound6 of Preferred 7 whe~e Q is Q-3:
33) Compounds of Preferred 7 where Q is Q-4;
3~) Compounds of Preferred 7 where Q is Q-7;
35) Compound~ of Preferred 7 where Q is Q-8;
36) Compounds of Preferred 7 where Q i~ Q-9;
37) Compounds of Pr,eferred 7 where Q i~ Q-10;
33) Compound~ of Preferred ? where Q is Q-ll:
39) Compounds of Preferred 7 where Q is Q-14:
40) Compounds of Preferred 7 where Q i6 Q-16;
41) Compounds of Preferred 7 where Q i~ Q-17;
42) Compounds of Preferred 7 where Q i~ Q-18;
43) Compound6 of Preferred 7 where Q is Q-21:
49) Compound~ of Preferred 7 where Q i~ Q-22:
45) Compound~ of ~referred 7 where Q is Q-24;
~6) Compound~ of Preferred ? where Q i~ Q-27;
47) Compound~ of PrefeLred 7 where Q is Q-30;
4~) Compounds of Preferred 7 where Q i8 Q-33;
49) Compound~ of Preferred 7 where Q i~ Q-37;
50) Compound~ of Preferred 7 where Q i~ Q-38;
51) Compounds of Preferred 7 where Q i~ phenyl:
An exemplary compound within the scope of this
invention is N-t(4,6-dimetho~ypyrimidin-2-yl)aminocar-
bonyl]-2-(lH-1,2,4-triazol-1-yl)-3-pyridine~ul~onamide,
m.p. 235-238~C.
g
Deta~led De~criPtion~ of the Invention
Synthe~i 6
The compound~ of Formulae I and II can ~e
prepared by one or ~ore of the methodg ~hown below in
Equation6 1, 2 and 3.
A~ ~hown in Equation 1 below, the compound~ of
Formulae I and II Swherein ~ is 0~ can be prepared by
treating 2~heterocyclic-3-pyridine~ulfonamide~ or
3-heterocyclic-2-pyridinesulfonamide~ of Fo~ula III
with the methyl e~ter of a pyrimidine or triazine-
carbamic acid of Formula IV in the pre6ence of an
equimolar quantity of trimethylaluminum.
Equation 1
Rl ~ S02NHz + CH30CN-A ~
N R II
III IV
wherein
A, R, Rl, n and Q are as previously defined.
The reaction of Equ~tion 1 i~ bes~ carried out
at temperature~ between 23 and 83C in an inelt ~ol-
ven~ e.~. methylene chlo~ide or 1.2-dichloroethane
for 12 t~ 96 hour6 under an inert atmosphere. The
produc~ can be i~olated by the addition of an aqueou~
acetic a~id or hydrochloric a~id ~olution followed by
extraction of the product into methylene chloride or
direct filtration of a product of low ~olubility. The
product can ordina~ily be purified by tri~uration wi~h
solvents 6uch a8 n-butyl chloride, ethyl acetate or
diethyl ether o~ by chromatography procedures. The
methyl carbamates, IV, can be conveniently prepared by
treat~ent of the corr*~ponding heteroaromatic a~ine~
of For~ula VII with dimethyl carbona~e or ~ethyl
11
c~loroformate in the presence of ~ base, ~.g. ~odium
hydride or pyridine.
Fu~ther detail~ of thi6 reaction an~ the prepa-
eation of ~he carbamate6 of ~ormula IV can be ~ound in
5 unexamined European Patene Application (EP-A) No.
83,975 (publi~hed July 20, l9B3).
Alternatively, compound6 of Formulae I and II
(wherein W is 0) can be prepared by the ceaction of
! 6ulfonamide~ of Formula III with the phenyl ester of
10 the appropriate carbamic acid, V, in the presence of
an equimolar quantity of a tertiary amine ba~e, e.g.
1,8-dia~abicyclo[5.4.0]unaec-7-ene (DBU), as ~hown
below in Equation 2.
Equaeion 2
15 0 1) DBU
III ~ C6H OCN-A
5 R ) H30 ~ II
V
wherein
A and R are as previou~ly defined.
The reaction of Equation 2 i~ carried out at 20
to 30C in an inert ~olvent, e.g. dioxane or aceto-
ni~rile. Aqueou~ acid workup afford~ the de~iredproduc~s, according to the teac~ings of EP-A No.
70,804 (published January 26, 1983) and South African
Patent Application~ 825042 and 839441. The phenyl
carbamate~, V, can be prepared by treating ~he
corre~ponding heteroaromatic a~ine~ of For~ula VII
with diphenyl ~arbonate or phenyl chloroforma~e in the
pLe~ence of a base , e.gO 60dium hydride or pyridine.
Alfio~ compound6 of For~ulae I and II (wherei~
is 0 or S) ~ay be prepared by reacting an appropriate
2-heterocy~lic-3-pyridine~ulfonyl i60cyanate or
3-heterocyclic-2-pyriaine6ul~onyl i~ocyanate of
i~ . ~.~ .. D ~
Fo~ula VI with t~e appropri~tely ~ub~t~tuted amino-
heterocycle. VII, as 6hown below in E~uation 3.
Equation 3
5~ H2)nQ
N a II
VI VII
wherein
A, R, Rl, n and Q are a~ previou~ly defined,
and ~ is 0 or S.
The ~eaction i6 be~t performed in an inert
~olvent , e.g. methylene chloride, tetrahydrofuran,
acetonitrile or toluene at 23 to 100C for one to 24
hourfi. In ca6es w~ere the products are insoluble in
the reaction 601vent, they may ~e i~olat~d by simple
filtration. When the product~ are 601uble, they may
be isolated by evaporation of the solvent and tri-
turation of the re~idue with an inert solvent , e.g.l-chlorobutane, diethyl ether or ethyl ac~tate and
filtration. The products may be further purified by
column chromatography procedules or ~ecrystallization.
Sulfonyl i~ocyanate~ of Formula VI aboYe may be
2 prepared, although often times in low yields, from
cor~e~ponding ~ulfonamide6 of Formula II by ~ethod~
analogou~ to those de~cribed in V.S. ~,238,621 and
EP-A No. a3,975 (published July 20, 1983). Thu~, by a
prefe~ed method, sulfonamides are reacted with pho~-
gene, in the presence of n-butyl isocyanate and a
tertiary amine cataly~t, at reflux in an inert ~olvent
e.g. xyle~e~. A preferred cataly~t i~ 1,4-diaza-
bicyclo[2.2.2~octan~ (DABC0). Alternatively, iso-
cyanate6, VI, may be prepaled by ~1) reacting 6ulfon-
amide6, III, with n-butyl i~ocyanate and a ba~e , e-g.
I
12
13
potassium carbonate at reflux in an inert solvent,
e.g. as 2-butanone to form a n-butylsulfonylurea; and
(2) reactin~ thi6 ~ompound with pho6gene and DABC0
catalyst at ~eflux in x~lene~ solvent.
Sulfonyl isothiocyanate6 can be prepared by
treatment of sulfonamide~ of Formula III with carbon
disulfide and pota6sium hydroxide followed by reaction
of the dipotas~ium 6alt with phosgene according to
R. Hartke, Arch. Pharm., 299, 174 (1966).
2- and 3-Pyridinesulfonamide~ of Formula lII
above are impoctant intecmediate~ for the preparatio~
of the compound~ of thi~ invention, and can be pre-
pared by method~ known in the literature, or simple
modification~ thereof, by tho6e 6killed in the art.
Eor example, 3-pyridine6ulfonamide~ of Formula
III, ~ubstituted in the 2-position with a pyrazol-l-
yl, l,2,4-triazol-1-yl or imidazol-l-yl group (Q i~
Q-7, Q-16 oc Q-21) may be prepared by ~he sequence of
reactions shown in Equation 4 below.
Equation 4
R ~ 2 a) Reductio ~ R ~ S02C
1 1 1 b) MEER~EIN 1 l ~
~ N ( H~)nQ ~N (CH2)nQ
VIII
S0 NH
I~ ) NH3 or NH40~ Rl ~ 2 2
N (CH2)nQ
~0
IIIa
wherein
Rl is a~ originally defined:
Q 1~ Q-7, Q-16 or Q-21; and
n i~ 0, 1 or 20
.~ f~ O ~
14
Reaction 4(a)
In this reaction 3-nitropyridine~, VIII, ar~
reduced to corre&ponding 3-aminopyridine~, fo~
example, by reaction wlth stannou6 chloride in hydro-
chloric acid by conventiollal method6. Details andrefe~ences for thi~ and ol:her method~ for reducing
nitropyridine~ to corre~ponding aminopyridines ~an be
found in "Pyridine and Derivative~", Chapter IX, pp.
~-10, E. K].ing~berg, Ed., a part of the 6eLies "The
Chemi~try of Heterocyclic Compound6~', A. ~eis~erger,
Ed. The 3-nitropyridine~l, VIII, are prepared by
reacting appropriate 2-ch:loro-3-nitropyridine6 with
60dium ~alt6 of appropriate pyrazole6, 1,2,4-triazole~
or imiazole~ in an inert so1vent, e.g. N,N-dimethyl-
formamide (DMF), according to the teaching~ of U.S.3,489,7~1.
Reaction 4(b2
In thi~ ~eaction 3-pyEidine6u1fony1 ~hlorides,
I~, are prepared by the ~eerwein ~eaction by diazo-
tizing corre~ponding 3-aminopyridi~e~ with sodium
nitrite in hydLochloric acid and acetic a~id, and
reacting the diazonium salt~ with exceEs 6ulfur
dioxide in acetic acid in the pre~ence of copper(I)
~h10ride or ~opper(II) chlorid~ cataly~. For
details, refer to ana10gou~ reaction~ de~cribed in
Y. ~ori~awa et al., J. Med. Chem., 23, 1376 (1980),
EP-A-83,975 and H. L. Hale and F. Sowinski, ~_Q~g~
Chem., 25, 1824 (1960~.
Rea~tion 4(c~
And in this reaction, 6u1fony1 ch10rides, I~,
are tran~formed to 6ulfonamide6, IIIa, by rea~tion
with ~nhydrou~ ammonia in an ine~t ~olvent, e.g.
tetrahydrofuran, or by reac~ion with aqueou6 am~onium
hydroxide in an iner~ ~olvent, e.g. te~rahydrofuran
by ~onv~entiona1 ~et~od6. For details, ~eer ~o
14
analogous reactions described in references cited
above for Reaction 4(b).
2- and 3-Pyridinesulfonamide6 of Formula III,
BUbB~ituted in the 3- and 2-po~tions respe~tlvely
with 5-thio-oxadiazol-2-yl srouPS (Q i8 Q-8), ~ay be
p~epared ~rom corresponding 2- and 3-~ercap~opyridyl
carboxylic a~ids, X, by t~e ~equen~e of re~ction~
shown below i~ Equation 5.
Equation 5
lQ 5(a)
C02H - ( i ) C12-HC:1 02CH3
Rl ~ ~ SH (ii) NH90H ~~~~~ l ~ S2NH2
) CH30H H2S04 ~ N
_ ~I
5(b~ 0
C~HNH2
~I H NNH H O ~
-- 2 ? 2 _~ Rl~ S02NH2
N
5(~) N-N
// \~
O~-`SR"
~II (i) KOH, CS ; H O ~
_ _ _ _ 2 ~ ~ R.-~ ~ ~So NH
(ii) ~OH. R5~ 1 ~ ~N~ 2 2
t ;~.E~
wherein
Rl i~ a~ p~eviously defined;
i~ Cl-C3 alkyl, C~2CH~CH or
CF2H; and
~ i Cl, Br or I.
16
Reaction~ 5~a)
In these reactions pyridine~ulfona~ide6, ~1, are
prepared by analogy wieh the teachings o~ Y. ~orisawa
et al., J. ~ed. Chem., 23, 1376 (1990). The method
compri~e6 (i) chlorinating appropriate 2-carboxy-3-
~ercaptopyridines or 3-carboxy-2-mercaptopyridine6 in
concentrated hydrochloric acid and water at about -25
to 5C to form corresponding carboxypyridyl 6ulfonyl
c~loride~: (ii) aminating the i601ated ~ulfonyl chlor-
ide6 with concentrated ammonium hydroxide to form thecorre~ponding carboxypyridy~l6ulfonamide~; and (iii)
esterifying the6e compound~ by refluxing in methanol
with ~ulfuric acid catalyst to form sulfonamide6, XI.
Alterna~ively, mercaptopyridine~, ~, may be
chlorinated in the presence of pota~sium hydrogen
difluoride in an inert fiolvent , e.g. water and
methanol at about -30 to 0C to ~orm the corre-
sponding carboxypyridyl sulfonyl fluoride6. Subse-
quent reaction of these compounds with ammonia can
provide the corre6ponding sulfonamide6. For fur~her
detail6 cefer to analogous ceaction6 described in
D. J. Brown and J. A. Ho6kins, J. Chem. So~. Perkin
Tran6 I, 522 ~1972).
Reaction 5(b)
Thi6 reaction i~ also run by analogy with the
teaching6 of ibid. The method compri~es reacti~g
pyridyl e~ter~, ~1, with exce66 hydrazine monohydr~te
in ~ethanol a~ reflux for 6everal hours. Under cer-
tain conditions 6ulfonamide6, ~I, may ring-clo~e ~o
sacc~arin-like 6tructure~, ei~her during their prepa-
ration in Reaction 5(a) or ~uring reflux with hydra-
zine in ~eaction 5(b). In either case, sub~equen~
reac~ion with hydrazine as de6cribed above may pcovide
hydrazide~, XII.
16
.~5~
17
eaction 5~L
The conver6ion of ~ydrazlde~ to 5-~ercapto-
oxadia201e~ ia well-known in the liteLature, e.g.,
R. W. Young and K. H. Wood, J. Am. Chem. Soc., 77~ 400
~1955). In a typical procedu~0, hydrazide~, ~II, are
heated at ~eflux with equimolar amount6 of potas6ium
hydroxide and an exce~ of carbon di~ul~ide in
methanol or ethanol ~olvent until the evolution of
hydrogen ~ulfide has nsarly ~topped. Oxadiazole6,
IIIb ~R5=H), are isolated by concent~ation oP the
~olvent, addition of water to the re~idue, filtration
of the aqueou6 6u6pen~ion to remove in~oluble impuri-
tie6, acidificatio~ of the aqueou~ filtrate with
hydrochloric acid and filtration.
Alkylation of 5-mercaptoo~adiazvles i~ al~o
well-known in the literature, e.g., S. Giri et al.,
Aqr. Biol._Chem., 40, 17 (1976). Typically, oxadi-
azole~, IIlb (R5=H), are reacted with an equimolar
amount of base , e.g. pota~sium hydroxide and exces~
alkylating agent, R5M, at reflux in an inert ~olvent
e.g. methanol or ethanol for 0.5 to 24 hours.
Sulfonamides, IlIb, are i~olated by concen~ration of
the ~olvent, addition of water to the re&idue and
fil~ration. Fo~ the ca6e where R5=CF2H, the reaction
25 i8 p~eferably run in DMF ~olvent at 60-90C with
exce6~ pota~ ium carbonate as ba~e. Following addi-
tion of water, ~ulfonamides, IIIb, are isolated by
filtration.
2- and 3-~yridine6ulfona~ide6 of Formula XII,
~ub~tituted in the 3- and 2-po6ition~ respec~fully
wi~h a p~enyl group, may be prepared from corre-
6ponding 3-phenyl-2-pyridinol~ and 2-p~enyl-3-
pyridinol6, ~III, by the ~equen~e of reactio~ ~hown
below in ~qua~ion 6.
17
1~1
~ .
~(a~
OH S ~H
Rl ~ ~ > ~ ~ ~ Rl
(iii) base
IV
SO NH
(i) C12, HCl, ~ 2 2
XIV C12, X~F R
~ J
(ii) NH~OH; ' ` N~
or NH3
IIIc
wherein
Rl is as previously defined.
ReactiQn 6~2
In theQe reactions mercaptopyridine~, ~IV, are
prepared by analogy with the tea~hing6 of B. Blank et
al., J. Med Chem., 17, 1065 (1974). The method com-
prizes (i) reacting pyridinol6. ~III, with dimethyl-
thiocarbamoyl chloride and a base, e.g. 1,4-diaza-
bicy~lo[2.2.2]octane tDABCO) in D~F to form the ~orre-
6ponding N,N-dime~hyl-O-thiocarbamate6: sii) hea~ing
ths6e compound~ at elevated eemperature~ e.g.,
1~0-210~C to form the corre~ponding N,N-dimethyl-
S-carbamates; and (iii) heating the~e compound~ with a
ba6e , e.g. ~odium carbonate or 60dium hydroxide in
an inert 601vent, e.g. methanol to form ~ercapto-
py~idine6, ~IV.
Reaction 6~k~
These reaction~ are run by procedurs~ analogou~
to tho~e de~ribed ~bove for the preparation 3f ~I
(Equation sa).
13
19
2- and 3-Pyridinesulfonamid~3 of For~ula III,
6ub6tituted in t~e 3- and 2-po6ition6 re6pe~tively
with pyridinyl, py~imidinyl, pyrazinyl. pyridazinyl or
triazinyl group~ Q-27 to Q-3fi) may be prepared
by the sequence of reaction~ shown in Equation 7 below.
Equ~t~on 7
7(a~
~r Li
10 Rl ~ S~2~HC(CH3)3 - L ~ Rl ~ S02NC(C~3)3
N N Li
~V XV I
7(b~ Q
XVI 1) CuI ~1 ~ S02NHC(CH3)3
~VII
~VIII
20 7(c) Q
~VIII CF3CO?H Rl ~ S2NH2
IIId
wherein
Rl ifi H or CH3; and
Q i~ ~-27 to ~-36.
T~e ~ompound~ of Formula III(d) are prepared
by analogy with ~he teaching6 of EP-A No. 85,476
~publi~hed December 13, 1983).
Reaction 7~a,b)
An appropriate 2-bro~o-3-(N-~-bu~yl)pyridine-
~ulfonamide or 3-bromo-2-(N-t-butyl)pyridi~e~ulfon-
amide i6 dis~olvad in an ethereal 601vent, e~g~
19
,,~ r"~ )r.-~
te~rahyd~o~u~an, and two equivalent~ o~ n-butyllithiu~
ln hexanes are added at about ~70~C. After 1-5 hours
at about -70C, the corre6ponding co~pound of Formula
~VI is formed. This is not i601ated. but one equiva-
lent of copper(I) iodide i6 added at about -70C,
followed by 1-1.5 equivalents of an appropriately
substitu~ed heteroaromatic iodide of Formula XVII.
The reaction mixture i8 stirred at 0 to 70C for 1 3
day~, concentrated and poured onto aqueou~ ammonia.
Co~pounds of Formula ~VIIX are isolatad by filtration
i~ solid~, or by extraction with methylene ehloride
and concentration i~ oil~" The compound6, XVIII, may
be further purified by recry6tallization or chromato-
graphy procedures. The compounds of Formula XV and
~VII may be prepared by methods known to those skilled
in the art. Pertinent references for the peeparation
of iodocompounds, XVII, are described in EP-A No.
85,476.
Reaction 7(c~
This reaction is conducted by ~tirring a
compound of Formula ~VIII with 2-10 equivalents of
~rifluoroacetic acid or aqueou~ HBr wath or without an
inert solvent at 30-70C for 1-3 day~. The product,
IIId, may be i~ola~ed as a trifluoroaceta~e or hydro-
bromide salt by evapo~ation of solvent and excess acid
and trituration with ether. The free base may be
obtained by neutralization of the salt with aqueous
base, extraction into an organic solvent, and concen-
tration of ~h~ organi~ e~tract~.
2- and 3-Pyridine6ul0na~ide6 of For~ula IIIe
can be prepared as ~hown in Equation 8 by procedures
analogou~ to the preparation of Co~pounds IIIb
described in Equation 5.
Rl~CH3 _-BuLi ~R ~ 2Li
N SO2NHC(CH3)3 L N SO2NLiC(CH3~3J
XXVI I T XVIa
2 TFA ~ ~C~Iz;C02H
~XI~
N-N
1. CH3OH~H2SO4 CEI~O~SP~"
2. NH2NH2oH?O Rl~ 2 5
3. KOH/CS2/H20 ~ S2NH2
4 . KOH, R 5M
IIIe
20wherein
Rl is as previously defined;
R5 is Cl-C3 alkyl or CF2H; and
. M is Cl, E~r or I .
Compounds of Formula I I If in Equation 9a can be
prepared from ehe lithium salt I~VIa by procedure~
described for the p~eparation of similar compounds in
Equation 7 and Compound IIIg can be prepared as shown
in Equation 9b.
t~ r,
22
~~
~./Ia ~ ~ C~2-Q
~ 502NE~C ~ CH3 ) 3
TF~ _3, l~ CH2-Q
N S2NHZ
wherein
Rl is H; and
Q i~ Q-27 ~ Q-36.
Equa~ion 9b
21~ Rl~/~
2 ~ TFA S2~2
l'he dilithio ~alt ~VIa call be prepared by
25 li~chia~cion o the ~ppropriate picollneRulfonamide6
a~cording to the teachi~g8 o~ R. E. Smitht S. Boatman
and C. R. Hauser; J. Or~, 33, 2083 (1968).
2~ieropy~idi~e6 o~ Fo~mula ,~h ~on~aini~ an
30 o-alkylfuran or ~hiophelle group (Q is Q-22 to Q-25 3,
can be prepared by analogy with the teachings in EP-P~
No. 85,476, and referen~es clted thereill as illustrat~d
in Equatioll lO.
r~ r ~
~3
E.quation lQ
(CH~)n-I ( 2)n Q
R~ CU~
N No2 ~X~I N N02
X~ IIIh
wherein
Rl and n are a~ originally de~ined; and
Q is ~-22 ~o Q-25.
Thus, a furyl- or thienylcopper compound of
Formula ~I is ~eacted witlh an o-(iodoalkyl)nitro-
pyridine of For~ula ~ in ,an in~rt 801vent,~e.g.
pyridine or guinollne at 0 to 60C for 1-3 day~. The
product, IIIh, i8 i~olated by addition of acid , e.g.
aceti~ acid and water, axtraction ~ith methylene
chloride, stripping of ~olvent and chromatog~aphing
the crude product. The ~opper compound~ of Formula
~XI are prepared by reacting the corresponding
lithium compounds with cuprou~ iodide or cuproufi
bromide in an inert ~olvent e.g. : ~thyl ether. The
detailed procedure~ for analogous type~ of reaction~
are de6cribed in the following re~erence6: ~. Nil~on
and C. Ulleniu~, A~ta. Che~m. Scand., 24, 2379-2388
(1970); C. Ulleniu6, Acta. Che~. Scand., 26, 3383-3386
(1972).
2- and 3-Pyridine~ulfonamides of Formula III
~ubsti~uted in the 3- and 2 posi~ion~, re6pectively,
with a tet~ahydrofuran group (Q iB Q-26) may be pre-
pared a~ shown in Equation 11.
23
t, ~ Hz ) n~
S02NHC(CH3)3
~I~
ll(b)
I~ CF3CO~H Rl ~ (CH2~ o
IIIe
whecein
Rl is H or CH3; and
n i6 0 or 1.
The compound~ of Formula IIIe are peepa~ed
by analogy with the teaching~ in EP-A No. 85,476
(published August 10, 19833.
Reaction ll(a~
In thi6 reaction d~lithio salt, ~YI or ~VIa,
in tatra~yd~ofu~an is treated wit~ one equi~alent of
4-chloro- or 4-bcomobutyraldehyde at -70C to -80C.
25. ~fteE ~tirring a~ about 25C for 1-3 days, ~e c~ac-
tion i~ quenc~ed by the addition of an acid e.g.
ace~i~ acid, and the product, ~ i601ated and
purifi~d by ~tripping t~e ~olvent and ~hromato~raphing
the residue.
eaction_llrb~
Thi~ reaction i6 run by proceduces analogous to
tho~e de~ccibed above in Eguation 7(~).
24
3 Py~idine~ulfonamide6 of Formula lIIi. ~ubsti-
tuted in the 2-pvsition by a furan or ~chiophene group
(Q is ~ 22 to Q-25 ) ~oay be prepar*d a~ ~hown below in
Equatlon 12.
5 E~uation l?
2(a) R7
P~l~(N2 , ~ R:I~No2
N Cl ~Br ) N Q
~XI
XX X~ I I
12(b)
XXI I ~ i ) Reduction R ~ S~NH2
( ii ) MEERWEIN '' ~ ~
(iii) NH3 o~ NH40~1 N Q
IIIi
wherein
R~ 5, R6 and R7 a~e a~ originally defined;
Q i6 Q-2~ to Q-25: and
N il; 0 or S.
Reaction~ 12 (a, b2
In Reaction 12~a) a furyl- or thienylcopper com-
pound of Formula XXI i8 reacted with an appropria~e
chloro- or bromonitropyridine of Formula ~ in a ~ol-
vent , e.g. pyridine or quinoline. The copper com-
pounds of Formula ~I are prepared by ~eacting the
~orre~ponding li~hium compound~ with cuprou~ iodide or
cuprous bromide in a solvent , e.g. diethyl ether.
T~e detailed procedure~ for analogous ~ype~ of reac-
tion6 ar~ de6cribed in the following referen~e~:
M. Nil6~0n ~nd C. Ulleniu6, cta. Chem. Scand., 24,
2379-238~ (19703; C. Ullenius, Acta. Chem. Scand., 2S.
3383-33B6 (19723.
26
2-Pyridine~ulona~ide~ of Fo~mula IIIj, substi-
tuted in the 3-position by a furan or thiophene group
(Q iB Q-22 to ~-25) may be prepared by the sequence of
reaction6 ~hown in Equation 13 below.
5 Equation 13
13(a) ~7 R6
Rl ~ Cl(R~ V > 1 ~ Cl(R~)
XXIII X~V
13(b)
X~V KSR14 ~X
N 5R14
XXVI
13(c)
XXVI (. ). C12~ H20, CH3C02H ~ Q
(ii~ NH40H ~ N'l~S02NH2
wherein
Rl, R5, R~ and R7 are a~ originally defined;
1~ i6 CH2CH~CH3 o~ CH2C~H5;
Q i~ Q-22 to Q-Z5; and
i6 0 or S.
26
J~ `r~ ~
Reactlon 13fa~
-
In thi~ reaction a 2-halo-3 pyridyl diazonium
6ale i~ ~oupled with an appropeiately 6ubstituted
thiophene or furan in the presence of a cataly6t, e.g.
cupric chloride. This reaction may be r~n by
procedure6 analogous to tho&e de~ceibed ln Gomberg and
Bachman, J. Am. Chem. Soc.. 46, 2339 (1924); J. John-
fion, J. Ch _. Soc., 895 ~1946); and in 3. Pharm. Soc.
(Japan), 90, 1150-1155 ~1970), or simple modifications
~0 theceof, by those skilled in the art. In ca~eE where
both the a- and the B-po~ition of the thiophene or
furan are available for couplinq, both i~ome~s are
usually obtained with the la-coupled product being
~he predominant isomer. These i~omers may be 6epa-
rated by fractional ~rystallization or chromatography
procedure6.Reaction 13~b3
I~ thi~ reaction thiopyridine~ of Fo~ula ~VI
are prepared by conventional method6 by treating
2-halopyridine6. XXV, ~ith potas6ium benzyl or propyl-
mercaptan in an inert 601ven~ e.g. DMF at abou~ 25
to 130C for one to 24 hours. ~ollowing i~olation by
u~ual method~, the product, X~VI, may be purified by
chromatography p~o~edures.
_eaction l~Lc3
And in ~his reaction the product~ of Reac~ion
13(b) are oxidatively chlorinated in a ~uitable inert
~olvent, e.g. chloro~orm, methylene chloride or
acetic acid, in the presence of water, to pLoduce the
cocrefiponding sulfonyl chloride~. The reaction i8
carried out in the pre~ence of at lea~t 2.5 molar
equivalent~ of water and at least three molar equiva-
lent~ of chlorine at about -30 eo 5C for l-S hours.
~ollowing isolation of the 6ulfonyl chlo~ide~, the
sul~oRyl chloride~ a~e reacted with ammonia or
ammonium hyd~oxide by conventional methods.
j~ "~"
28
Other 2- and 3-pyridinesulfonamide~ of Fo~mula
III may also be prepared by oxidatively chlorinating
appropriate 3-heterocyclic-2-thiopyridines and 2-
heterocyclic-3-thiopyridine6 of Foemula ~VII to
coree~ponding sulfonyl chlorides, followed by
amination to corresponding 6ulfonamides, a~ shown
below in Equation 14.
Equation 14
10 Q
Xl ~ SR (i) C12, H20, inert fiolvent IIIk
N ~ (ii) NH3 or NH40H
XXVII
wherein
Rl i6 as originally defined; and
R15 is H- C2Hs or CH2 6 5
The r~actions of Equation 14 are carried out by
methods analogous to those described above in Equation
13(c) and for the preparation of XI (Eguation 5a~. The
compounds of Formula XXVII may be prepared by those
skilled in the art by the application of appropriate
~ethod~ ~elected from the va~iety of known literature
procedures for preparing ~ubstituted aromatic hetero-
cycles. See, for example, ~P-A No. 83,975 Ipubli6hed
July 20, 1983) t a~d references cited therein, which
desccibe method~ for tran~focming various o-(substi-
tuted)nitrobenzene~ to corresponding o-(he~erocyclic)-
nitrobenzenes, in which the o-heterocyclic groups are
Q~l to Q-Zl. By carrying out similar reactions on
appropriately ~ubstituted pyridine~, or simple modifi-
cations thereof, tho6e ~killed in the art may prepare
many of the compound~ of For~ula XXVII above.
r~" ~ o~ i r~
29
The~e exist ~ va~lety of kno~wn ~ethod~ fo~
incorporating a ~ercapto oc alkylthio group into the
2- or 3~po~ition of a pyrldine ring, ~ethods which ace
u6eful for the preparation of the compound6 of the
general Formula ~VlI de6cribed above in Equation 14.
The choice of met~od6 used depends in part on the
reaction 6equences u~ed to prepare compounds X~VII,
which would be obviou~ to tho~e ~killed in the art.
These method~ include (i) reactin~ 3-pyridyl diazonium
lQ 6alts with potas~ium ethyl xanthat~ to for~ corre-
~ponding 3-~ercaptopyridine6, which can be alkylated
to 3-benzyl- or 3-pcopylthiopyridines by obviou6
method6; for details, refer to analogous reactions
described in J. Pha~m. Belq., 22, 213 (1967); ibid.,
29, 2Bl (1974) and J. Orq. Chem., 23, 1924 tl958);
(ii) ~aponifying N,N-dimethyl-S-carbamates, prepared
from 2- or 3-pyridinols, to form co~responding 2- or
3-mercaptopyridines: for general detail~ ~ee Eguation
6(a) above; (iii) reac~ing 3-halopyridines, containing
an ac~ivating ortho-group su~h a6 aldehyde, ketone,
carboxylic ester, amide, nitrile or nitro group, wit~
potazsium propanethiol or benzylthiol in an inert
~olvent, e.g. DMF or hexamethylphosphoramide by
~nown method~ to for~ co~esponding 3-benzylthiol- or
3-propanethiolpyridine6; (iv) di~placing a 2-halogen
on a pyridine ring by ~ulfu~ nucleophile6, e.g.
potas~ium o~ 60dium hydro~ul~ide, thiourea or po~as-
sium benzylthiol or propanethiol to form 2-thio~ub-
6ti~uted pyridines; for detail~, see analogou~
reaction~ described in J. Het. Chem., 3, 27 (1966);
ibid., 17, 149 (1980), ibid., 5, 6~7 ~1958); J. Am.
~hem. Soc., 6B, 342 (1946) and ibid., 70, 3908 [194B);
and (v) diazotizing and converting Z-aminopyridine~ to
2-pyridinols which may be converted to 2-pyridin~-
thiol~ with P4S~; ~or detail6 6ee analogous ~eactionsde~cribed in ar~aco Edo Sçi~ 22~ 1069 (1967)~
29
f~ J~
The preparation oP pyridine~thiol~ i8 alBO
reviewed in "Pyridine ænd It~ Deriv~tives", Part 4,
1964, by ~. L. Hale, a part of the ~erie~ "The
Chemi~tr~ o~ HeterocYclic Com~ , A. ~ei~berger,
Ed., publiEhed by Interfi~ience Publ., Ne~ York and
London.
The heterocyclic amine6 of Formula YII in
Equation 3 are also important in~ermediate~ for the
preparation of t~e compound~ of this invention, and
~an be prepared by ~e~hod~; known in the literature, or
6imple modification~ thereof, by eho~e ~killed in the
art. For detailç, see, for example, EP-A No. B4, 224
(publi~hed July 27, 1983) and W. Braker et al., J. Am.
Chem. Soc., 69, 3072 [1947), which describe the 6yn-
ttlesi~ of pyrimidine- and triazineamines ~ubstituted
by acetals and thioacetals, e.g. dialkoxyme~hyl or
1,3-dioxolan-2-yl. See al~o, for example, South
African Patent Application Nos. 825,045 and 825,671
which de6cribe the ~ynthesi~ of aminopyrimidines and
triazi~e~ ~ub6tituted by such group~ as haloalkoxy or
haloalkylthio group~, e.g., OCH~CH2F, OCHzCF3~ OCF2H
or SCF2H. Al~o, South African Patent Application No.
S37~434 (published October 5, 1983~ de~cribes ~ethod~
for the 6ynthe~i~ of cyclopropylpyrimidines and tri-
azines 6ubstituted by ~uch groups as alkyl, haloalkyl,alkoxy, haloalkoxy, alkylamino, dialkylamino or
alkoxyalkyl.
Al~o, the 5,6-dihydrofuro[~,3-d]pyrimidin-
2-amine6, the cyclopenta~d]pyrimidin-2-amines (VII.
A=A-2) and the ~.7-dihydro-5H-pyrano[2,3-d]pyrimidin-2-
amine6 (VII, A=A-3) ~an be prepared as de~cYibed in
EP~A No. 15,683. Also, the furo[2,3-d~pyrimidin-2-
amines (VII, A-A-4) are de~cribed in EP-A ~o. 460677.
Compounds of Formula VII, where A is A-5, are
de~ribed in EP-A No. 73,562. Compounds of Formula
YII, whe,ce ~ i5 A-6, are de~cribed in EP-A No. 94,250.
31
ln addition, general methodE~ Por preparin~
aminopyrimidine~ and t~iaz~nes have been reviewed in
the following ~ublication~:
~ "The Chemistry of Heterocyclic Compounds", a
secie~ published by Interscience Publisher6, Inc., NQW
Yor~ and London:
o "Pyrimidines", Vol. 16 of the sa~e series, by
D. J. BLown.
~ "s-Triazines and Derivative6", Vol. 13 of the
6a~e series, by E. M. Smolin and L. RappapoLt; and
~ F. C. Schaefer, U.S. 3,154,547 and K. R.
Huffman and F. C. Schaefer~ J. Orq. Chem., 23, lB12
(1963) wh;ch describe the ~ynthe~i6 of triazines.
Agriculturally suitable salts of compounds of
Formulae I and II are al60 useful herbicide6 and can
be prepared in a number of way6 known ~o the art. For
example. meeal ~al~s can be made by contacting com-
pounds of Formulae I or II with a ~olution of an
alkali or alkaline earth metal salt having a suffi-
ciently ba~ic anion (e.g., hydroxide, alkoxide,cacbonate or hydroxide). Quaternary amine ~alt~
can be made by similar techniques.
Salts of compounds of Formulae I and II can al60
be prepared by exchange of one cation for another.
Cationic exchange can be effected by direct contact of
an aqueous solution of a salt of a compound o For-
mulae I o~ II (e.g., alkali or guaternary amine ~lt)
wi~h a solution containing the cation to be exchan~ed.
Thi~ me~hod i~ most effeceiYe when the desired 6alt
con~aining the exchanged cation i~ in~oluble in water
and can be separated by filtration.
Exchange may also b~ effected by pas~ing an
aqueou~ ~olution of a 6alt of a compound of Formulae I
or II ~a.g., an alkali metal or quaternary a~ine 6alt)
through a column packed with a cation exchange re~in
31
,,~ r ~ ,2~ r~J,
3 !
containing the cation to be exchanged ~OL that o~ the
original ~alt and the de~ired product i8 eluted fro~
the column. This method i~ particularly useful when
the de6ired salt ~ 6 water-~oluble, e.g., a pota~ium,
sodium or calcium salt.
Acid addition ~alt6, u~eful in this invention,
can be obtained by reacting a compound of Focmulae I
or II with a sui~able acid, e.g., p-toluene~ulfonic
acid, trichloroacstic acid o~ the li~e.
' The preparation of t'he compound6 of ~his
invention i6 further illu~trated by the following
specific examples. Unle~ otherwise indicated,
~emperatures are in degree6 centigrade.
ExamPle 1
Nitro-2-(lH-1.2,,4~triaz 1-l_y~2pyridine
A solution of 10 g of 2-chloro-3-nitropy~idine
di~solved in 30 ml of dry D~' was added dropwise to a
6u~pension containin~ 6.9 g of 1,2,4-triazole 60dium
~alt (90~, Aldri~h Chemical Co.) in 40 ml of dry DMF.
After a Elow exotherm had subsided, the 6u~pension was
heated at 60 for three hours, then cooled to 25C and
poured onto S00 ml of ice-watel to yield a precipitate.
After the mixture was filtered, the isolated 601id was
~5 wa~hed 2x50 ml of water and ~uction-dried to yield 12
g of crude produc~. The product was recry~tallized
from 2-propanol to yield 8 g of the ~ubject compound;
m.p. 131-133~.
Anal. calc. for C7H5N502: C, 43.9; H, 2.7; N, 36.6;
Found: C, 44.6: ~, 2.7; N, 36.7.
32
33
ExamPle 2
3-Amino-2-(lH-1.2,4-tr~azol-1-y~p~ridine
To ~ suspension containing 35.4 g of stannoug
chloride dihydrate in 100 ml of concentlated hydro-
S chloric acid wa~ added portionwi~e 10 g of the com-
pound prepared in Example 1 over a 0.25 hou~ period.
After the re~ulting exotherm (23-79) slowed, the
6u~pension was heated at 85-90 ~o~ one hour, then
cooled to 0. The mixture was poured onto excess
ice-water (about 700 ml), and the su~pen~ion wa6 made
st~ongly basic to litmus by addition of 50~ aqueou6
NaOH to yield a precipitate. After filtering the
mixture, the isolated 601id was washed with water,
suction-dried, then recry6tallized ~rom ethyl ace-
tate-hexanes to yield 3 g of the 6ubject compound;
m.p. 103-105~.
Anal. calc. for C7H7N5: C, 52.2; H, 4.4; N. 43.4;
Found: C, 52.4; H, ~.3; N, 41.6.
~o Exam~le 3
2-(lH-1,2,4-Triazol-1 yl2-3-pvridinesulfonyl chloride
A diazonium salt was p~epared by adding a ~olu-
tion o 9 g of ~odium nitrite in 30 ml of water to a
suspen6ion of 20 g of the compound prepared by the
procedure of Example 2 in 45 ~1 of concentrated hydro-
chloric acid and 127 ml of glacial acetic acid at
0-25. After stirring about 0.4 hour, ~he diazonium
ru~pen~ion was poured slowly into a mixtu~e con~i~ting
of 93 ml of aceti~ acid, ~.3 g of cupric chlolide
dihydrate and 37 ml of 6ulfur dioxide while cooling
the reaction flask at 10-20 in a dry ice-acetone
bath. During the addi~ion a delayed vigo~ous gas
evolution with foal~ing occurred and was controlled by
cooling and decreasing the rate of addition of the
diazonium ~uspen6ion. After addition was comple~e,
$;~7J..')~
34
the cooling was csmoved and the 6u~pension was ~tirred
at ambient temperature for four houc6. The su6pension
wa~ pou~ed into ice-water (about 800 ~1) and stirred
~o yield a solid. After the ~ixture wa~ filtersd, the
i~olated 601id wa6 wa~hed 2x50 ml of water and suction-
dried overnight to yield 17 g of the sub3ect compound:
m.p. 12B-132~
Anal. calc. for C7H5ClN~02S: C, 34.4; H, 2.1; N, 22.g;
Found: C, 34.4: H, 2.1; N, 23.2.
Exclmple 4
2-(lH-l,Z,4-Tliazol-l-Yl~-3-Pyri-din~Qg~ a~
To a suspension containing 15 g of the compound
pLepared in Example 3 in 125 ml of tetrahydrofuran was
added dropwise 23 ml of concen~rated aqueous ammonium
hydroxide while maintaini~g the reaction te~peratu~e
at 10-20 with external ice-water cooling. After
stirrin~ at room tempecature for three hours, the
suspen~.ion was concentrated in vacuo to a water
su~pension. The suspension waF. poured into ice-water
(about 200 ml) and stir~ed to yield a solid. The
mixture wa~. filtered to yield 12 g of crude product,
which was recry6tallized from acetonitrile to yield
8 g of the subjec~ compound; m.p. 185-188~.
Anal. calc. for C7H7N502S: C, 37.3; H, 3.2; N, 31.0;
Found: C, 37.4, H, 3.0; N, 30.9.
Example 5
N-[~4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-
2~ 1,2,4-triazol-1-Yl)-3-Pyridine~ulfonamide
To a su~pen~ion containing 0.5 g of the ~ulfon-
amide prepared in Example 4 in 10 ml of p-dioxane wa~
added 0.6 g of phenyl(4,6-dimethoxypyrimidin-2-yl)-
carbamate followed by 0.33 g of l,~-diazabicyclo-
[5.4.0]undec-7~ene ~DBU). The ~u6pen~ion wa~ stirred
~fqr~ "~?)5;
at room temperature fo~ about two hours then diluted
with about 75 ml of water to for~ a ~olution. Afte~
acidifying the 801ution with conc. hydrochloric acid
(red to litmus) and 6tirri.ng 0.5 hour, a precipitate
formed. The mixture wa~ filtered and the i601at,ed
~olid wa~ wa6hed with 10 ml water and suction-dried
for 24 hour~ to ~ield 0.7 g of the 6ubject compound:
m.p. 226-Z30.
Anal. calc. for C14H14N805S: C, 41.4; H, 3.5: N, 27.6;
Found: C, 41.3; H, 3.7; N, Z7.~.
IR (nujol): 1715 cm-l (C=O).
U~ing the techniques described in Equations 1-14
and Examples 1-5, or ~imple modifications thereof, the
following compounds in Tables Ia-IIg can be made by
tho~e skilled in ~he art.
36
T~ble Ia
~1 ~ R ~
O n R aI X Y Z m p.C
Q-l(R5,R6=H) 0 CH3 H OCH3 OCH3 CH
Q-l(R5,R6=H) 0 HH CH 3 ~H3 CH
Q-l(R5,R6_H) 0 HH CH3 OCH3 CH
Q ( 5'R6 H) HH OCH3 OCH3 CH
Q-l~R5,R~=H) 0 HH Cl OCH3 C~l
Q-l(R5=H,R6= CH3) 0 H H OCH3 OCH3 CH
Q (R5 CH3'~6 H) o H H OCH3 OCH3 CH
Q-2 (R5 'R6=H) 0 HH CH3 CH3 CH
Q-2(R5,R6=H) 0 HH OCH3 OCH3 CH
20 Q ( 5~ 6 ) HH CH3 OC~3 CH
Q-2(R5,R6=H) 0 HH Cl O~H3 CH
Q-2(R5=CH3,R6=H) 0 HH OCH3 OCH3 CH
Q-2(R5=~,R6=~H3) 0 HH OCH3 OCH3 CH
Q-3(R5.R6=H) 0 HH CH3 ~3 CH
Q-3(~5,R6=H) 0 HH CH3 OC~3 CH
Q (R5,Rh H) 0 HH OCH3 OCH3 CH
Q-3(R5,a6=H~ 0 HH Cl O~H3 CH
Q-3(R5=CH3:~=H) 0 H H OCH3 OCH3 CH
Q ( 5'R6 H~ 0 HH CH3 CH3 CH
30 Q ~ 5' 6 H~ o HH OCH3 CH3 ~
Q-4(R5.R6=H) 0 HH OCH3 OCH3 CH
Q-4(R5.R6=H) 0 HH Cl OC~3 CH
~-5rR5'R6=H) 0 HH OCH3 OCH3 CH
Q-5(R5.RS=H) O H3 CH3 CH
Q-5(R5.R6=H) 0 HH CH3 ~C~3 C~
Q-5~R5'R6=H~ 0 HH Cl OCH3 CH
36
37
~Ea~ /~A~ d
~ y ;!~ C
4~chloropherlyl O H OCH3 OC:H3 CH
3-alsthoxypbenyl O H H OCH3 OCH3 C~
3-D~ethylphenyl O H H OCH3 OCH3 CH
Q-6 (E~5-H) O H OCEI3 OC~13 CEI
Q~ 6 ( R5 ~H ) O H H C}13 OC~3 CH
Q-6 (~5~H) O H CE~3 C}s3 CH
Q~ 5~) H Cl ~3 CH
Q-7(R5~R~ 7-H) O E~ C~3 C~H3 CH
Q-7(R5~R6~R73~I) O H OCH3 OCH3 C~I
Q-7(R5,E16~R7-H) O H H CH3 OCH3 C~
Q-7 (P~5, R6 ~ El7-H) O H H Cl OCH3 CH
Q-7(L~5,~71~CH3 ~6~H) O H H OCE13 OCH3 CH 204~207
Q-0 (R5 ' ~H) O E~ El CH3 CH3 CH
Q-E~ (R5 ~ 2H~ O H E~ OCH3 OCH3 CH
Q-8 (R5 ~ -H) O H H CH3 OC~3 CH
Q-B tR5 ' =H) O H H Cl OCH3 CH
~;!-B (R5 ' =CH3 ) O lH H OCH3 OCH3 CH
Q-8 (R5 ' =CH3 ) O EI H CH3 O(:H3 CH
Q ~ ( R5 H3 ) H H CH3 ~H3 CH
Q-8 (R5 ' ~CH3 ) O H H Cl OCE13 CH
2 5 Q ( 5 3 ) O CEI3 H OCH3 OCH3 ClH
Q-8 (P~ ' ~C lH ) O H H CH3 c~3 CEI
Q 8 (R5 C2E~5 ~ O H H OCE13 OClH3 C~H
Q-8 (R ' ~C H ) O H ~I CH3 OCH3 ~H
Q-- 8 ( ~5 ~ ~cC2H5 ~ O ~ l OCH?~
Q-8 (R5 ~ SCH3 ~ O E~ H OCH3 OCH3 CEI
Q (R5 SCH3 ) O H 1H CH3 C~3 CH
Q-8 (R5 ~ 8S~E~3 ) O H 3 CH3 CH
Q-8 SP~5 ~ -SCH3 ) O H H Cl OCH3 CH
Q-~ 5 ~SC2H5 ) O H 3 3 CH
Q- 8 ( R~ SC2H5 ) O El H OCE~3 OCH3 CH
Q ( 5 2 5 ) t) H H CH3 5:~CH3 CH
'1~ /'3~ .q~
3~
~ gLlg-c~æ~ ued
_Q_n R Rl ~ y Z m.p.oC
Q-8(R5'=SC2~5) H H Cl OCH3 CH
Q-8(R~'=SCH2CH3CH2) O H H OCH3 OCH3 CH
Q-8(R5'=SCH2CH=CH2) O H H CH3 OCH3 CH
Q-8(R5'=SCH2CH=CH2) O H H CH3 CH3 CH
Q-8(R5'=SCH~CH=CH2) O H H Cl H3 CN
Q-8(R5'aSCF2H)CH3 OCH3 CH
10 Q-8(R '=SCF H)O H H CH3 CH3 CH
Q-~(R5'=SCF2H)o H H OCH3 CH3 CH
~-h(R5'=~C~2H)O H H Cl OCH3 CH
Q-8~R5'=SC3~7)H3 OCH3 CH
15 Q (R5 SC3H7)~H3 OCH3 C~
Q-8(R5'=SC3H7)O H H Cl OCH3 C~
Q-8(R5'-OCH3)o H H OCH3 OCH3 CH
Q-8(R5'=OC2~5)H3 OCH3 CH
Q-9(R5=H)O H H OCH3 OCH~ CH
Q-9(R5=H)O H H CH3 OCH3 CH
Q-9(R5=H)O H H CH3 CH3 CH
Q-9(R5=H)O H H Cl OC~3 CH
Q-9(~5=CH3)O H H OCH3 OCH3 CH
Q (R5 CH3)O H H CH3 OCH3 CH
Q-9(R5=CH3)O H H CH3 CH3 CH
Q-9(R5=CH3)O H H Cl OCH3 ~H
Q-lO(R5=H)O H H CH3 CH3 CH
Q-lO(R5=H~H3 OCN3 CH
Q-lO(R5=H)CH3 OCH3 CH
Q-lO~R5=HO H H Cl OCH3 CH
Q-10-(R5=CH3)o H R CH3 CH3 CH
Q-10-(R5=CH3)O H H OCH3 OCH3 CH
Q-10-(R5=CH3)O H H CH3 OCH3 CH
Q-10-(R5-CH3~o H H Cl OCH3 CH
Q-ll(R5=H)O H H OCH3 OCH3 CH
Q-12(R~='H3O H H OCH3 OCH3 OEl
3~
39
~able Ia Continued
Qn lR Rl ~ Y Z P.C
2(R8=cl)OCH3 OCH3 CH
Q-13~R5-CH3)1 ~ O~H3 OCH3 CH
Q-14(R5=H) 3 3
Q-14(R5=EI)3 CH3 C~
Q-l~(R5=H)0 H H Cl OC~3 CH
Q-15(~5=H)l~ H OCH3 OCH3 CH
Q 16(R5,R6 H) 0 H H CH3CH3 CH 240-243
Q-16(R5,R~=H) 0 IR H OCH3 OCH3 CH 235-23B
Q-16(R5,RS=H) O 'H H CH3OCH3 CH 225-228
Q-16(R5,R6=H) 0 H H ClOCH3 CH
Q-17(R5=CH3.R6=CH3) H H OCH3 OCH3 CH
Q-17(R5=CH3,R6=CH3) H H CH3 OCH3 CH
Q-17(R5=H,R6=CH3) 3 CH3 CH
Q-17~R5=H,R6=CH3) 0 H H Cl OCH3 CH
Q-l8~R5=H~R6=cH3~ 3 3
Q-18(R5=CH3oR6=cH3) 3 3
Q-lB(~5=H~R6=CH3) 33 CH
Q-18(R5=H,R~=CH3) O H H Cl OCH3 CH
Q-l9(R5=CH3,R6=H) H3 OCH3 CH
Q-20~R5,Rfi=CH3) H H OCH3 OC~3 CH
Q-21(~5~6~R7=H) 3 C~3 C~
~-22(R5,R6,R7=H3 H H OCH3 OCH3 ~H
Q-23(a5~R6~R7=H) 3 CH3 CH
Q-~4~R5~6.~7 )O H H O~H3 CH3 CH
Q-25(R5,R6,R7=H)H H ~CH3 OCH3 CH
Q-26(W'=O~ 3 3 CH
Q-27(R5.R6=H~n'=) 3 3
Q-28(R5~R~-H~n~=o) 3 3
Q-29~R5,R6=H,n'=O) o H H OCH~ OCH3 CH
Q-30(R5=H;Rg~Rlo=OCH3) 0 H H OCH3 OCH3 CH
Q-30(R5=H Rg~Rlo=CH3) 0 H H OCH3 OCH3 CH
Q-31(Rg,RlOaH) o H ~1 OCH3 OC~3 CH
~9
Table Ia Continued
~ n R ~1 ~ Y ~ P.~
5 Q 32 (R9 ~Rlo H) o H H OCH3 OCH3 CH
Q-33(R5,R6=H) O H H OCH3 OCH3 CH
Q 34(~5'R6 ~) O H H OCH3 OCH3 CH
Q ( 11~ 12 3) H H OCH3 OCH3 CH
Q 6(Rl1~R12 CH3) O H H OCH3 OCH3 CH
C6H5 O H H CH3 CH3 CH
C6H5 O H H OCH3 CH3 CH
C6~I5 O H H OCH3 OCH3 CH
C6H5 0 H EI Cl OCH3 CH
Q-l(R5,R6=H) o H H CH3 OCH3 N
15 Q 2(R5~R6 H) O H H OCH3 OCH3 N
Q-3(~5=CH3,R6=H) O H H OCH3 OCH3 N
Q-8(R5'-CH3) o H H CH3 OCH3 N
Q-8(R~'=SCH3) O H H OCH3 OCH3 N
~ ( 5 3) O H H CH3 OCH3 N
Q-lO(R5=CH3) O H H CE13 OCH3 N
Q-12(R8-Cl) O H H CH3 OCH3 N
Q-17(R5=H,R~=CH3) O H H OCH3 ~H3
~-18(R5-H,R6=CH3) o H H CH3 OCH3 N
Q-18(R5=H,R~=CH3) O ~ H OCH3 OCH3 N
25 Q 2(R5~6,R7 H) O H H CH3 OCH3 N
Q-26(~'=0~ O H H CH3 OCH3 N
Q-27(R5,R6=H,n-~-O) O H H CH3 OCH3 N
Q-27~R5,Rs=H,n~=O) O H H OCH3 OCH3 N
Q-30(R5~Rg~Rlo=H) O H H CH3 OCH3
Q-30(R5~Rg~Rlo=H) O H H OCH3 OCH3 N
Q-33~5'R6=H~ O H H CH3 OCH3 N
C6H5 O H H CH3 OCH3 N
C6H5 O H H OCH3 OCH3 N
6H5 H H CH3 CH3 N
Q-2(R5'R6=K~ o H 5-Cl OCH3 OCH3 CH
Q-16(R5=F~,R6=CH3) O H 6-Br OCH3 OC~3 CH
~0
~."~ 3.`~
~1
T~ble Ia Continued
Q n a ~1 x Y z m P.C
Q-8(R5'=SCH3) O H 5-CH3 ~CH3 OCH3 CH
5 Q-8(R '=SCH ) O H 5-Cl OCH3 3
Q-l(R5~R6=H~ o H 3 3 3
Q ( 5' 6 ) O CH3 H OCU3 CH3 U
Q-8(R5'=SCH3) O H H OC2H5 CH3 CH
Q-l(R5,R6=H) O H H F OCH3 CH
Q ( 5' 6 ) O H H Br OCH3 CH
Q-3(R5,R6=H) O H H I OCH3 CH
Q-8(R5'=SCH3) O H H OCF2H OCH3 CH
Q-10(R5=CH3) O H H CH2F OCH3 CH
Q-18(R5=H,R6=CH3) O H H OCH2CH2F CH3 CH
Q-17(R5=H,R6=CH3) O H H OCH2CHF2 CH3 CH
Q-8(R5'=SCH3) O H H OCH2CF3 OCH3 CH
Q-lO(R5=CH3) O H H CF3 OCH3 CH
Q-2(R5,R6=H) O H H OCH2CH3 OCH3 U
Q-1(R5'R6=H~ o H H OCH2CH2F CH3
Q 5 3 O H H OCH2CF3 OC~3
Q ( 5 3) H H OCH3 H CH
Q-16(R5=H,R6=CH~) O H H CH3 OC2H5 CH
Q-8(R5'=SCH3) O H R CH3 CH20CH3 CH
Q-8tR5'=CH3) O H H OC2H5 ~HCH3
Q-17(R5=H,R6=CH3) O H H OCH3 ( 3) 3
a-8(R5'=SCH3) O H H OC}13 3)2
Q-18(R5=H,R6=CH3) 0 H H OCH3C2H~ CH
Q-12(R8=Cl) O H H OCH3 CF3 CH
Q-11(R5=CH3) O H H OCH3 SCH3
Q-18(R5=H,R6=CH3~ O H H CH3 OCH2CH=CH2
Q-lO(R5=H) O H H CH3 OCH C-CH
Q-13(R5=CH3) O H H OCH3 CH20CH2CH3 CH
Q-17(R5=H,R6=CH3) O H H CH3 2 2 3
Q-14(~5=H) O H H CH3 CH2SCH3 CH
Q ( 5' 6 ) 0 H H OC~3 3 7 CH
.b ~
42
Table Ia_Continued
_Q_ n R ~l ~ Y Z m.p.C
O O
5 Q-lO(R5=C~3) o H H CH3 CH CH
o
Q~ 5,R6=H) O H H CH3 CCH3 CH
Q-8(R '=SCH ) 0 H H OCH3 CH(OCH3)2 CH
Q-l(R5,X6=H) O H H CH3 CH(OCH3)2 N
lO Q~8(R5=SCH3) o H H OCH3 CH(OC2H5)2 CH
Q~2(R5,R6=H) O H H OCH3 CH(SCH3)2 CH
Q-3~R5'R6=H~o H H OCH3 C(CH3)~OCH3)2 CH
Q-8(R5'=SC~3)H H OCH3 CHo~ CH
O
Q-l8(R53H.R6=CH3) 0 H H CH3 CH ~ CH
o
~0~
Q-17(R5=H,R6_CH3) 0 H H OCH3 CH 1 CH
~O_ -CH
Q-8(R5'=CH3) 0 H R OCH3 CH CH
Q-lO~R5=H) 0 H H OCH3 OCF~H CH
Q-l4 3 2 CH
/ CH2
Q-8(R5'=SCH33 0 H H OCH3 CH ¦ N
~2
,~CH2
Q-l(~5'R6=H~ O H H OCH3 CH ¦ CH
CH2
~ CH2
C~H5 0 H H OCH3 CH ¦ N
\CH2
/ CH2
C6H5 0 H H OCH3 C ¦ CH
CHz
42
43
Table Ia_Continued
Q n R Rl ~ Y Z m.P~oc
Q l(R5'R6 H) 1 CH3 H OCH3 OCH3 CH
Q-l(R5,R6=H) 1 H H CH3 CH3 CH
Q-l(R5,R6_H~ 1 H H CH3 OCH3 CH
Q-l(R5,R6=H) 1 H H OCH3 OCH3 CH
Q ( 5~R6 H) 1 H H Cl OCH3 CH
Q~ 5=H,R6=CH3) 1 H H OCH3 OCH3 CH
Q-l(R5=H~cH3~R6=H) 1 H H OCH3 OCH3 CH
Q-2(R5.R6=H) 1 H H CH CH CH
Q (R5,R6 ~I) 1 H H OCH3 OCH3 CH
Q-2(R5,R6=H) 1 H H CH3 O~H3 C~I
15 Q ( 5'R6 H) 1 H H Cl OCH3 CH
Q-2(R5=CH3,R6=H) 1 H H OCH3 OCH3 CH
Q-2(R5_H,R6=C~3) 1 H H OCH3 OCH3 CH
Q (R5'~6 H) 1 H H CH3 CH3 CH
Q-3(R5,R6-H) 1 H H CH3 OCH3 CH
Q-3(R5,R6=H) 1 H H OCH3 OCH3 CH
Q-3(R5,R6=H) 1 H H Cl OCH3 CH
Q-3(R5aCH3;R6=H) 1 H H OCH3 OCH3 CH
Q-4(~5,R6=H) 1 H H CH3 CH3 CH
Q-4(R~,R6=H) 1 H H OCH3 CH3 CH
Q-4~R5'R6=H~ 1 H H OCH3 OCH3 CH
Q-4(R5,R6=H~ .1 H H Cl OC~3 CH
Q ( 5'~6 H) 1 H H OCH3 OCH3 CH
Q (R5'~6 El) 1 H H CH3 CH3 CH
Q-5(R5,R~=H) 1 H H CH3 OCH3 CH
30 Q-5(R5,R6=~] 1 H H Cl OCH3 CH
Q-6(R5=H) 1 H H OCH3 OCH3 CH
Q-6(R5=H) 1 H H CH3 OCH3 CH
Q-S(R5=H) 1 H H CH3 CH3
Q-6(R5=H) 1 H H Cl OCH3 C~
Q-8(R5'=H) 1 H 3 CH3 CH
Q-8~R5'=H) 1 H H OCH3 OCH3 CH
43
44
Table Ia Continued
Q n R 1 X Y Z P.4C
Q-8(~5'=H) l H H CH3 OCH3 C~
Q (R5 H) l H H Cl OCH3 CH
Q-9~R5=H) l H H OCH3 OCH3 CH
Q-9(R5a~) l H H CH3 CH3 CH
Q-l0(R5=H) l H H OCH3 OCH3 CH
Q-l0(R5=~) l H H CH3 OCH3 CH
Q-l0(R5aH) l H H Cl OC~3 CH
Q-ll(R5=H) l H H OCH3 OCH3 CH
Q-ll(R5=H) l H H c~3 OCH3 CH
Q-12(R8=H) CH3 CH3 CH
Q-12(R8=H) l H H Cl H3 CH
Q-13(R5=CH3)l H H OCH3 OCH~ CH
Q-l4(R5=H) l H H CH3 CH3 CH
Q-14(R5=H) l H H OCH3 OCH3 CH
Q-l4(R5=H) l H H CH3 OCH3 CH
Q-14(R =H) l H H Cl OCH CH
Q-15(R5=H) l H H OCH3 OCH3 CH
Q-l~(R5=H,R6-EI)l H H CH3 O~H3 CH
Q-16(R5=~,R~=H)l H H CH3 CH3 CH
Q-16(R5=H,R~=H)l H H Cl OCH3 CH
25 Q ~ 5 ~ 6 )l H H CH3 CH3 CH
Q-17(R5=H,R6=H)l H H OCH3 OCH3 CH
Q 18(R5=~,~6=H)l H H CH3 C~3 CH
! Q-18(R5=H~R6=~'l H H Cl OCH3 CH
Q-l8(R5=H.R~=H)CH3 OCH3 CH
Q-19(R -CH R =H)l H H OCH3 OCH3 CH
Q-20~S,R6=CH3)l H H OCH OCH CH
Q-22(R5,~6,R7=H)H3 OCH3 CH
Q-24(R5,R6,R7=H)l H H OC~3 CH3 CH
~-28(R~,R6=H,n'=0~ l H H OCH3 OCH3 CH
Q-30(R5=H~Rg~Rlo=CH3) l H H OCH3 OCH3 CH
~-33(R~,R~=H~O 3 OCH3 CH
Table Ia Continued
~ n R Rl ~ y z m.~.C
Q-35(Rll,Rl2=OCH3) l H H OCH3 OC~3 CH
C6H5 l H H OCH3 OCH3 CH
C6H5 l H H OCH3 CH3 CH
Q-37(R5=H l H H OCH3 OCH3 C~
Q-38(R5=H) l H H OCH3 OCH3 CH
Q-39(R5,R$=H) l H H OCH3 OCH3 CH
Q-l(~5'R6-H) l H H OCH3 OCH3 N
Q-2(R5,R6=H) l H H CH3 OCH3 N
Q-8(R5'=CH3) l H H CH3 OCH3 N
Q-8(R5~,=CH3) l H H OCH3 OCH3
Q-12(R8=Cl) l H H OCH3 OCH3 N
Q-~7(R5=H.R6-CH3) l H H OCH3 OCH3 N
Q-l8(R5=H~6=C~3) l H H OCH3 OCH3 N
Q-22(R5,R6,R7=H) l H H OCH3 CH3 N
Q-26(W~=S) l H 3 OCH3 N
Q-27~R5,R6=H~n~=l) l H H OCH3 OCH3 N
Q-30(R5,Rg,Rlo=H) l H H OCH3 OCH3 N
Q-33~R5'~6=H~ l H H OCH3 OCH3 N
C6H5 l H H CH3 OC~3 N
C6H5 l H H OCH3 O~H3
25 Q ( 5~ 6 H) l H 5-Cl OCH3 OCH3 N
Q-l6(R5=H,R6=CH3~ l H 3 CH3 CH
Q-3(R5'=SCH3) l H 5 CH3 OCH3 OCH3 C~
Q ( 5 H3) l H 5-Cl OCH3 CH3 N
Q-l(R5,R6=H) l CH3 5-C~13 OCH3 c~3
Q-l~R5~R6=H~ l CH3 H OCH3 CH3 N
Q-8(R5'-SCH3) l H H OC2H5 CH3 CH
Q-l(~5,R6=H) l H H F OCH3 CH
Q-2(R5,~6=H) l H H B~ OCH3 C~
Q-3(R5'R6=H) l H H I OC~3 CH
35 Q ( ~ ,R SCH3) l H H OCF2H OCH3 CH
Q-l0(R5=CH3~ l H H CH2F ~C~3 CH
;~ r~ r~
46
Q n R 1 ~ Y 2 ~ p-C
Q-18~R5=H,~6=CH3) 1 H H OCH2C~2 3
Q-17(R5=H,~6=C~3) 1 H H 2 2 3 CH
Q-8tR5'=SCH3) 1 H H ~H2GF3 OCH3 CH
Q-lO(a5=CH3) 1 H H CF3 OCH3 CH
Q-2(R5,R6=H) 1 H H CH2cH3 OCH3
0-l(R5~R6=H) 1 H H OCH2CH2F CH3
Q ( 5 3) 2 3 3
Q-9(R5=CH3) 1 H H oc~3 H CH
Q-16(R5,R6=H) 1 H H CH3 OC2}l5 CH
Q-8(R5'=SC}13) 1 H H CH3 CH~OCH3 CH
Q-8(R5'=CH3) 1 H H OC2H5 ~HCH3 U
Q-17 1 H H OCH3 3 3
Q-8(R5'=SCH3) 1 H H OCH3 U(CH3)2
Q-18(R5=H,R6=CH3) 1 H H OC~3 C2H5 CH
Q-12(R8=Cl) 1 H H OCH3 CF3 CH
Q-ll(R5=CH3~ 1 H H OCH3 SCH3
Q-18(R5-H,R6=CH3) 1 H H CH3 OCH2CH=CH2
-lOtR5=CH3) 1 H H CH3 OCH C-CH
Q-13(R5=CH3) 1 H H OCff3 CH20CH2CH3 CH
Q-17(R5~H,R6=CH3) 1 H H CH3 OCH2CH20CH3 CH
Q-14(R5=H) 1 H H CH3 CN2SCH3 CH
Q 5' 6 1 H H OCH3 i-C3}l7 CH
Q-lOtR5=CH3) 1 H H C~13 CH CH
o
Q-l~R5,R6=H) 1 H H Cff3 CC~3 CH
Q 5 3 1 H H O~H3 CH(OCH3)2 CH
Q-l(R5,R6=H) 1 H H CH3 CH(OCH3)2
Q-8(R5=SCH3) 1 H H OCH3 CH(OC2H5~2 CH
Q-2(R5,R6=H) 1 H H OCH3 CH(SCH3)2 CH
Q-3~R5'R6=H~ 1 H H OCH3 C(CH3)(0CH3~2 CH
k~
'~ r7' ~
~7
~Table Ia Continu~d
O ~ R Rl ~1 Y Z m. P . C
S Q-8 (R5 ~ =SC~13 ) 1 H H OCH3 CH ~ CH
Q~ R5=H~ p~6=cH3 ) 1 H H C~3 CH ~ CH
Q-l7(R5=H,R6=CEI3) 1 H H OCH3 C'H ~
~o CH
Q-8 (R5 ' =CH3 ) 1 H H OCH3 CH ~~ 3 CH
Q-lO (R5=H) H OCH3 OCF2H CH
Q-14 (R5=H) OCH3 5CF2H CH
/ CE~2
Q-8 (R5 -SCH3 ) 1 EI H OCH3 CH ¦ N
CH2
- / CH;~
Q-l(R5,R6=H) l H H OCH3 C ¦ CH
~H2
/ CEI2
C6~5 l H HOCH3CH ¦ N
2 5 CEI;2
~ CH2
~6H5 3C~ ¦H CH
Q 35 ~R11=R12=CH3 ) 1 H ~OC~3 ~ CH CH
~ CH2
Q~39 (R5=R6=H) l H HOCH3 CH ¦ CH
CH2
47
r;~" ~/D~ `s~r
~8
~sd
QA al ~ y
Q~ 5~a6~OC~3 O~H3 ~H
Q-5~,a6-H)H3 OCH3 CH
Q-0(~5'-H)2 ~ H OCH3 OC~3
Q-14~5n~)2 H ~ OCH3 OC~3 CH
Q-16(~5~H.~fi-CH3) 2 H H OCH3 3
10 Q l(RS'~6 H)2 ~ H OCH3 OC~3
Q-lO~R5=H)2 ~ H OCH3 OCH3
Q-12(R8~H)2 H H C~3 OC~3
Q-13(R~'~,R6~CH3) 2 H H O~H3 OCH~ N
Q-24(~5,R6,R7~H) 2 H H OCH3 ~CH3 N
Q-27(~5.R6~H,n'~l) 2 ~ H 3 ~H3 N
Q-33(R5,~6,3H) 2 H H OC~3 OCH3
Q-371~5.R6-H) H OCH3 ~C~13 CH
Q-7(R5,R7=CH3,R6=H) O H H CH3 OCH3 CH 220-224
Q-7(R5,R7=CH3,R6=H) O H H CH3 CH3 CH 212-216
Q-7(R5,R7=CH3,R6=H) O H H Cl OCH3 CH 193-195
20 Q-7(R5,R7=CH3,R6=H) O H H OCH3 OCH3 N 190-193
4a
49
rabl~ Ib
~1 1
~ SO2NHCON
~CH2)n ~2 Yl
--Q n R 1 1 1 m.p.oc
Q~ 5,R6=H) O H H CH3 O
Q-2(R5,R6a~) 0 H H CH3 O
Q-3(R5,R6=H) O H H CH3 O
Q-4(R5,R6=H) 0 H H CH3 O
15 Q-7(R5~R6~R7=H) 0 H H CH3 O
Q-B(R5'=SCH3) 0 ~ H CH3 O
Q-8(R '=CH ) 0 H H CH3 O
Q-8(R5'=H) O H H CH3 O
Q-9(R5=CH3) o H H CH3 O
20 Q~1(R5=C~3) 0 H H CH3 O
Q-14~R5=H) O H H CH3
Q-l~(R5,R6.,H) O H H CH3 o
Q-17(R5,R6=H) O H H CH3 O
~ ( 5' 6 ~1) 0 H H CH3 O
25 Q-2l(R5~R6~R7=H) O H H CH3 o
Q-22(R5,R6,R7=H~ O H H CH3 O
Q-24(~5,R6,R7=H) O H H CH3 O
Q-27(R5,R6=H,n'-o) O H H CH3 O
Q ( 5~ 9~ 10 H) O H H 3
30 Q-33(R5~R6=H) o H H CH3 o
Q-8(R5'-SCH3) 0 H H OCH3 O
Q-l(R5,R~=H) o H 2H5
Q ( 5 3) H H OCF2H O
Q ( 5 3) H H CH3 CH2
35 Q-~R5 =SCM3) 0 H H OCH3 CH2
~g
~, r r~ ~ ~ 2~ r"~
T_~lq Ib Continlled
Q n ~ R
Q ( 5 ' 6 H) 1 H H CH3
Q-2(R5,R6=H) 1 H H CH3 0
Q-~ (R~ ' =SCH3 ) 1 H H CH3 o
Q 8(R5 C~3~ 1 H H CH3 0
Q-14 (P55=H) 1 H H CH3 0
Q-16(R5,R6=H) 1 H H CH3 0
Q-17(R5,R6=H) ~ H H CH3 0
Q-18(R5,R~=H) 1 H H CH3 0
Q-33(R5,R6=H) 1 H H CH3 0
Q-l~F~5'R6=H~ 1 H C2H5 0
Q~~ (R5 ' =CH3 ) 1 H H OCF2H O
Q-8 (R5 ' =SCH3 ) 1 H H OCH3 C~2
Q-B (R5 ' =CH3 ) 2 H H CH3 o
Q-14 (R5-EI) 2 H H CH3 0
Q-8 (R5 ' =SCH3 ) 2 H C2HS 0
20 Q 33 ~ ~R5,R6 H) 2 H H CH3 0
~.,, f~ ~ `f~
5-1
able Ic
N X
5 ~ 502NHCO~
N' (CH2)nQ
_Q_ n R al 1 m.p.C
Q-l(R5,R6=H) O H H CH3
Q-2(R5,R6=~) 0 H H OCH3
Q-3(R5,R6~H) o H H 2 5
Q-4(R5,R6=H) O H H CH3
15 Q-7(R5,R6,R7=H) O H H CH3
Q-~(R5'=SCH3) 0 H H OCH3
Q-8(R5'=CH3) 0 H H OCH3
Q-8(R5'=H) O H H CH3
Q-9~R5=CH3) 0 H H OCF2H
20 Q-lO(R5=CH3) 0 H H CH3
Q-14(R5=H) o H H OCH3
Q-16(R5=H,R6=C~3) 0 H H CH3
Q-17(R5=H,R6=~H3) 0 H H OCF2H
Q-l~(R5=H,R6=CH3) 0 H H OCH3
Q ( 5,~6,R7 H) O H ~ ~CH3
Q-22(R5,R6~R7=H) O H H CH3
Q-24(R5,R6,~7=H) O H H CH3
Q-Z7(R5,R6=H,n'=o) o H H O~H3
Q-30(R5,R6,Rlo=H) O H H OCH3
30 Q-33(R5,R6=H) H H OCH3
Q~l(R5,~6=H) 1 H H CH3
Q-2(R5,R6=H) 1 H H CCH3
Q ~(R5 CH3) 1 H H OCH3
Q-8~R5'=SCH3) 1 H H CH3
35 Q-lO(R5=CH3) 1 H H OC2H5
51
;~
s~
Ta_1e Ic Con~nued
Q n R Rl Xl ~. p . C
Q-14 (P~5=H) 1 H H OCH3
Q-17 (R5=H, R6=~3 ) 1 H H OCF2EI
Q-~l(R5,R6,R7=EI) 1 H IH OCH3
Q-33 (R5.P~6=H) 1 H H OCH3
~2-8 (R5 ' -CH3 ) 2 H H C~3
Q-27(R,R6=H,n'=1) 2 H H OC~13
Q-24~R5,E~6=H) 2 H H OCH3
Q-l(R5,P~6=H) 2 H H CH3
Q-4 (R~,,, R6=H) 2 H C2EI5
53
Table Id
N X
~ S02NHCON ~ O-- S
N (CH2)nQ Y2
--Q n R 1 1 2 m.p.oC
Q-l(R~,R6=H) 0 H H CH3 CH3
Q-2(R5,R6=H) o H H OCH3 CH3
Q-3(R5.R6~H) 0 H HC2H5 H
Q-4(R5,R6=H) 0 H H CH3 CH3
15 Q-7(R5.~6.R~=H) 0 H H CH3 C~3
Q-8(R5~zSCH3) o H H CH3 ~H3
Q (R5 CH3) o H H CH3 CH3
Q-8(R5'=H) 0 H H CH3 C~3
Q-9(R5=C~3) o H HOCF2H CH3
20 Q~1(a5=CH3) 0 H HCH3 CH3
Q-14(R5=H) 0 H HCH3 CH3
Q-16(R5,R6=H) o H HCH3 CH3
~-17(R5,R6=H) o H H2 CH3
Q-1~3(R5,R$=H) O H H~H5 CH3
25 Q-2l(R5~R~R7=~) 0 H H CH3 C~3
Q-22(R5,R6,R7~H) o H H OCH3 H
Q-24(~5,R6,R7-H) o H H OCF2H CH3
Q-27(R5,R6=H,n'=o) o H H CH3 CH3
Q-30(R5,Rg,Rlo-H) H H 3 ~3
30 Q-33(R5,R~-H) o H H CH3 CH3
Q-1(R5,R6=H) 1 H ~ C~3 c~3
Q-25R5,R6=H~ 1 H H OCH3 CH3
Q-3(R5,R6-H) 1 H 2H5 H
Q-8(R5'=SCH3) 1 H H CH3 CH3
35 Q-8~R5~ 3~ 1 H H CH3 c~3
~q
Ta bl e I d Cont 1 nued
Q n R Rl Xl 2 m. P. C
Q-14 (R5=H) 1 H H CE13CH3
Q-16 (R5, R6=E~) 1 H H CH3 CH3
Q-18 (R5 . R6=H) 1 H H OC2H5 CH3
Q-21(R5,R6,R~=H) 1 H H CH3 CH3
Q-27(R5,R6=H) 1 H H CH3 CH3
10 Q ( 5 . R6 ~I~ 1 H H CH ~CH3
Q-3B(R5,R6=H) 1 H H CH3 CH3
Q-l(R5.P(6=E~) 2 H H CH3 CH3
Q-~ (R ' -SCE~ ) 2 H H CH3 CH3
Q-8 (R5 ' -CH3 ) 2 H H CH3 CH3
Q- 14 2 H H OCEI3 CH
Q-33(R5,E~6=H) 2 H H CH3C,H33
54
T~
al~ S02N~CON~
N (CH2)mQ
Q ~ a ~1 ~2 Y3 ~C
Q-l(a50R6-~) ~ E~ CH3 ~H3
Q-2(R5,Rt; ~H) O H E~ OCH3 CH3
Q-3 (R5 .P~6.R~ 0 H H OCH3 C~2~5
Q 4t~5'R6 ) O H ~ CH3 C~3
Q ( 5 ' 6 ' 7 ) O H El CH3 ~H3
Q-B (R5 ' JSCH3 ) o El H C~13 CH2CF3
Q-8 (R5 ' 8CH3 ~ O H H CH~ CE12CF3
Q-~(a5l=H~ O H H CE~3 CH3
Q 9 ( X5 CH3 ~ o H H OCH3 CH3
Q 10 (P~5 CE13 ~ O H H CH3 CH3
Q-14 (R5eH) O H H CH3 C2H5
Q-lij~R5=~,R6 ~EI3) 1~ H ~II3 ~H3
Q-l?(R5~H,B~=C~3) H H OC 3 2 3
Q-18 (RS-H, R6-CE~3 ) O H H OC~3 CH3
Q-21(R5,R6,R75H) O H H CH3 c~3
2 Q tR5,R6,R7 E~) O ~ E~ OCH3 C2~5
Q-24(R5,R6,R7=H) O H H OCE~3 CH3
S;?-27~5,R6'H, ~ l) 0 ~ H CH3 C~3
9 ' 10 H) o iH H CH3 CE13
Q-33 (R5 .P~6~H) O H H CH3 CH3
Q 1 (R5, R6 E~ 1 H H CH3 CEI3
Q-2~R5,~6~R~ 1 H 3 c~3
Q-8 (E~5 ' ~`CH3 ) 1 M 8 CH3 C2E~5
Q-8 (R5 ' ~SCH3 ) 1 H H CH3 ~EI2CF3
Q 9 (E~5 CH3 ~ 1 H H OCH3 CH3
3 5 Q- 10 ( R5 ~CH3 ) 1 El IH C}13 3
56
Tab_ e Ie Continued
Q n ~ P~l X2 3 m.p.C
Q-14 (a5~H) 1 H H CH3 C2H5
Q-16 (R5aH, R6=C~13 ) 1 H H CE~3 c~3
Q-27 (P~5, R6=H) 1 H H ~H3 c~3
Q-33(R5,R6=H) 1 H H CH3 CH3
Q ( 5, R 6 H ) 2 H H CH3 CH3
Q-a (R5 ~ =~CH3 ~ 2 H ~ ~3 CH3
Q-14 2 H H CH3 CH3
Q-10 Z H H OCH3 C~12CF3
56
Table~If
OCH3
R1 ~ SO~NHCON_~H2~
N (CH2) nQ 3
~ R 1 3 m. p . oC
Q-l(R5,R6=H) O H H CH3
Q-2(R5,R~=H) O H H CH3
Q-3(R5,R6.H) o H H CH3
Q-4(R5,R6=H) 0 H H OCH3
15 Q~7(R5~R6~R7=~) o H ~ OCH3
Q-9(R5'=CH3) 0 H H CH3
Q-8(R5~-SCH3) o H H OCH3
Q-8(R5'=C~3) 0 H H CH3
Q-9(R5=CH3) o H H CH3
20 Q~1(R5=C~3) 0 H H OCH3
Q-14(R5=~) 0 H H OCH3
Q-16(R5,R6=H) o H H CH3
Q-17(R5.R~=H) H H CH3
Q-18(R5,R6=H) 0 H H OCH3
25 Q-21(R5,R6,R7=H) O H H ~H3
Q-2~R5~R6~R7-H) o H H OCH3
Q-24(R5,R6,R7=H~ o H H CH3
Q-27(R5~R~ n'=O) H H C~3
Q-30~R5.Rg.Rlo=H) O H H OCH3
30 Q-33(R5.R6=H) O ~ H CH3
Q-38(R5,R6=H) O H H CH3
Q-l(R5,R6=H) 1 H H OCH3
Q-2(R5,R6~) 1 H H CH3
Q ( 5 3) 1 H H CH3
35 Q~~(R5~=SCH3) 1 H H OCH3
57
/
58
Table T Continued
~ n R Rl X3
Q-lO(F~5=CH3~ 1 H H CH3
Q-14 (R5-H) 1 H H CH3
Q-16(R5,R6-~1) 1 H H OCH3
Q-18(R5,R6=H) 1 H H OCH3
Q-Z7(R5,R6=H) 1 H H CH3
10 Q-3~tR5~R6=H) 1 H H OCH3
Q-l(R5,P~6=H) 2 H E~ OCH3
~--8 (R5 ' =CH3 ) 2 H H OCH3
s~
. N
Rl ~ SO~NHCSN~
N (C~{~)nQ
_Q_ n R R1 X Y Z
Q-l(R5.R6=~) 3 H3 CH
Q-l(R5,R6=H)H OCH3 OCH3 CH
Q-2(R5,R6=H)o H H OCH3 C~3 CH
Q-3~R5,R6=H)H OC~3 OCH3 CH
Q-4(R5,R6-H)0 H H OCH3 OCH3 CH
15 Q-l(R5'R6=H) H H CH3 OCH3 N
Q-8(R5'=CH3)O H H 3 CH3 CH
Q-9(R5-CH3)O H H OCH3 ~CH3 CH
Q-lO(R5=CH3)O H H CH3 OCH3 CH
Q-14(R5=H)H H OCH3 OCH3 CH
Q-16(R5,R6=H)0 H H OCH3 OCH3 CH
Q-17(R5=H,R~=CH3) O H H OCH3 OCH3 CH
Q-21(R5,R6.R7=H) O H H OCH3 OCH3 CH
Q-22(R$,R6.R7=H) O H H OCH3 OCH3 CH
Q-24(R5,R6.R~=H) O H H OCH3 OCH3 CH
Q-33(R5,R6=~H OCH3 OCH3 CH
Q ( 5 3)1 H H OCH3 O~H3 CH
Q-8(R5'=CH3)1 H H OCH3 CH3 N
Q-8(R5'=CH3) ~ ~ CH3 OCH3
Q-8~5'=CH3)H OCH3 OCH3 CH
59
Table_IIa
R 1~ 802NHCON -<~
R N ~
Q n R Rl X Y Z m P.C
Q l(R5,R6 H) O CH3 H OCH3 OCH3 CH
Q-l(R5~R~=H) o HH CH 3 CH3 CH
Q-l(R5,R6=H) O HH CH3 OCH3 CH
Q-l(R5,R6=H) O HH OCH3 OCH3 CH
Q-l(R5,R6=H) O HH Cl OCH3 CH
15 Q-l(R5=H,R6= CH3) 0 H H OCH3 OCH3 CH
Q-l(R5=CH3,R6=H) ~ H H OCH3 OCH3 CH
Q-2(R5,R6=H) O H H CH3 ~H3 CH
Q-2(R5,R6=H) O H H OCH3 OCH3 CH
Q ( 5' 6 ) O H H CH3 ~CH3 C~I
Q-2~R5'R6=H~ O H H Cl OCH3 CH
Q-2(R5=CH3,R6=H) O H H OCH3 OCH3 CH
Q-2(R5=H,R6=CH3) 0 H H OCH3 OCH3 CH
Q ~ 5' 6 ) O HH CH3 CH3 CH
Q-3(R~,R6=H) O HH CH3 OCH3 CH
Q ( 5~ 6 H) O HH OCH3 OCH3 CH
Q-3(R5,R6=H~ O HH Cl OCH3 CH
Q-3(R5=CH3,R6_H) O H H OCH3 OCH3 CH
Q-4(R5'R6-H~ O HH CH3 CH3 CH
Q-4(R5,R~_H) o H3 3 CH
30 Q-4(R5,R6=H) O HH OCH3 OCH3 C~
~-q(R5'R6=H) 0 HH Cl OCH3 CH
Q-5(R5,R6=H) O HH OCH3 OCH3 CH
Q-5~R5,R6=H) O HH CH3 CH3 CH
Q-5(R5,R6=H~ O HH CH3 OCH3 C~I
35 Q-5(R5,R6=H) O HH Cl OCH3 CH
6~
r P ~ r~
61
Table I~a Continued
_Q_ n R Rl ~ y Z m.p.oC
Q-6~R5=H) O H H OCH3 OCH3 CH
Q-6(R5-H) O H H CH3 OCH3 CH
Q-6(R5--H) O H H CH3 CH3 CH
~-6(R5=H) 0 H H Cl OCH3 CH
Q-7(R5,R6,R7=H) O H H CH3 CH~ CH
Q-7(~5,R6,R7=H) O H H OCH3 OCH3 CH
Q-7(R5,R6.R7=H) O H H CH3 OCH3 CH
Q-7(R5,~6,R7=H) O H H Cl OCH3 CH
Q-7(R5,~7=CH3;R6=H) o H El OCH3 OCH3 CH
Q-8(R5'=H) H H CH3 CH3 CH
~-a (R5'=H) O H ~1 OC~3 OCH3 CH
Q-8(R5'=H) O H H H3 OCH3 CH
Q-8(R5'=H) O H H Cl OCH3 CH
Q-8(R5~=CH3) O H H OCH3 OCH3 CH
Q-8(R5'=CH3) O H H CH3 OC~3 C~
Q-~(R5'=CH3~ O H H CH3 CH3 CH
Q-8(R5'=CH3) O H H Cl OCH3 CH
Q-8(R5~=CH3) CH3 H OCH3 OCH3 CH
Q ( 5 C2HS) O H H CH3 CH3 CH
Q-8(R5'=C~H5) o H H OCH3 OCH3 CH
Q-B(~5'=C2~5) o H H CH3 OCH3 CH
Q-8(R5'=C2H~ H H Cl OCH3 CH
Q-8(~5'=SCH3) O H H OCH3 OCH3 CH
Q-8(R5'=SCH3) O H H CH3 OCH3 ~H
Q-8(~'=SCH3) O H H CH3 C~I3 CH
Q-8(R5~=SCH3) O H H Cl OCH3 CH
Q ( 5 SC2H5) O H H CH3 CH3 CH
Q-8(R5'=SCzH5) O H H OCH3 OCH3 CH
Q-8(R5~=SC2~5) O H H CH3 OCH3 CH
Q-B(R5~SC2~5) O H H Cl OC~3 ~H
Q-8(R5~=SCH2CH=CH2) o H H OCH3 OCH3 CH
i~. fio ..~ .
6Z
~d
Q n R Rl ~ y Z ~.P C
Q-g(~$'~SCH2CH~CH2) 0 H H CH3 3
Q-8(R5'~SCH2CH3CH2~ H H ~H3 CH3
Q-8(~5'~scH2cH~cH2~ 0 N ~ Cl 3
Q-8(R5'~SCF2H)O H3 OC~3 CH
Q-8~R5'~S~F2~)3 CH3 C~
Q-8(R ~ nSCF H)O H H OCH3 CH3 CH
~-~(R5'aSCF2H)O ~ H Cl ~CH3 CH
Q-~3 (R5 ~ ~SC 3H7 ) O H Hl OCH3 OCE~3
Q-8(a5'-SC3H7)H3 OCH3 CH
Q-8(R5~SC3H7) H H. Cl OCH3 CH
~ 5'sOCH3)H3 OCH3 ~
Q-8(R5~-OC2H5)0 H H OCH3 OCH3 CH
Q-9(R5-H)O H H OCH3 OCH3 CH
Q-9(R5~H)O H H CH3 OCH3 C~l
Q-9(R5=H)CH3 CH3 CH
Q-9(R5=H)O H H Cl OCH3 CH
Q-9(R5=CH3)0 H H OCH3 OCH3 CH
Q t 5 3)o H H CH3 OCH3 CH
Q (R5 CEI3)3 CH3 CH
( 5 CH3)0 H H Cl OCH3 C~
Q-lO(R5=H)3 CH3 CH
Q-10(~5=~) ~3 CH3 CH
Q-10 (R5~H) H H CH3 OCH3 CH
Q-lO(R5aHO H H Cl 3 CH
Q-lO(.R5=CH3)o H H CH3 ~H3 CH 160-165
~-lO(R5=CH3~0 H H OC83 OCH3 CH 169-173
Q lO(R5 C~3)0 H H ~H3 OCR3 CH
Q-lO(R5=CH3)o H H Cl OCH3 CH 162-166
Q-ll(R5~H)O H H OCH3 OCH3 CH
Q-12~8=H' 3 3
Q-12(R85Cl)O H H OCH3 OCH3 CH
62
63
TabL~ IIa Contirlued
Qn R R 1 ;K Y Z g~
Q 13(R55CH3)H3 OCH3 CH
Q-14(R5=H)O H H OCH3 OCH3 CH
~-14(R5=H)O H H CH3 OCH3 CH
Q-14(R5=H)O H H Cl OCH3 CH
Q-15(R5=H)O H H OCH3 OCH3 CH
Q-16(R5~R6=H)O H H C~13 C~3 CH
Q-16(R5,R6=H)H3 OCH3 CH
Q-16(R5~R6=H)O H H C~3 VCH3 CH
Q-16(Rs,R6=H)O H H Cl OCH3 CH
Q-17(R5~R6=H)O H H OCH3 OCH3 CH
Q~17(Rs~R6=H~3 OCH3 CH
Q-17(R5~R6=~o H H CH3 CH3 C'H
Q-17(Rs,R6=H)O H H Cl OCH3 CH
Q ( 5' 6 )O H H OCH3 OCH3 CH
Q~13~5~R6=H)3 OCH3 CH
Q-18(R5,R6=H)o H H CH3 CH3 CH
Q-18 (R5, R6=H)O H H Cl OCH3 CH
Q l9(R5=CH3~R6=H) 3 3 CH
Q-20(R5,R6=CH3) OCH3OCH3 CH
~-21~R5~a6~R7=H~ 3 3
Q-22(R5,R6,R7=H) O H HOCH3OCH3 CH
25 Q-23~R5~R6~R7=H~ H3 OCH3 CH
Q-24(R5,R6,R7=H) O H HOCH3CH3 CH
Q-25(R5,R6,R7-H~ 3 OCH3 CH
Q-26(W~=0) 3 OCH3 CH
Q-27~R5~R6_H,n~=O)O H H OCH3 OCH3 CH
Q-28(R5,R6=H,n~=O)O H H OCH3 OCH3 CH
Q-29(R5~R6=H,n~-O)O H H OCH3 OCH3 CH
Q-30(R5=H;Rg,Rlo=oCH3) 0 H H OCH3 OCH3 CH
Q-30[R5=H;Rg~Rlo-CH3) O H H OCH3 OCH3 CH
Q ( 9' 10 ) O H H OCH3 OCH3 CH
63
J--~r~ ~ ~ F ~
64
Table IIa_Contirlued
~ r. p~ a1 B Y z m. P . oc
Q 32(R9'RlO H) O H H OCH3 OCH3 CH
Q-~3(R~,R6-H) O H H OCH3 OCH3 CH
Q-34(R5,R6=H~ O H H OCH3 OCH3 CH
Q-35(Rll'Rlz=CH3~ H T1 OCH3 OCH3 CH
Q-36(Rll,Rl2=CH3) o H H OCH3 OCH3 CH
C6H5 O H H CH3 CH3 CH
~6H5 0 H H OCH3 CH3 CH
C6H5 O H H OCH3 OCH3 CH
C6H5 0 H H Cl OCH3 CH
Q (R5.R6 ~) O H H CH3 OCH3 N
Q-2(R5.R6=H) o H H OCH3 OCH3 N
Q-3(R5=CH3,R6=H) o H H OCH3 OCH3 N
Q-8(R5'=CH3) o H H CH3 OCH3 N
Q-8(R5'=SCH3) 0 H H OCH3 OCH3 N
Q 9(R5=CH3) o H H CH3 OCH3 N
Q-lO(R$=CH3) O H H CH3 OCH3
Q-l2(R8=Cl) ~ H H CH3 OCH3 N
Q-~7 0 H H OCH3 CH3 N
Q-l8 O H H CH3 OCH3 N
Q-l8 O H H OCH3 ~CH3
Q-22~R5,R6,R7--H) o H H CH3 OCH3 N
Q-26(~'=S) O H H CH3 OCH3
Q-27(R5,Rs=H,n'=o) O H H CH3 OCH3 N
Q-27(R5,R6=H,n'=O) O H H OCH3 OCH~ N
Q-30(R5,Rg,Rl~=H~ o H H CH3 OCH3 N
Q-30~R~,R~,Rlo=H) O H H OCH3 OCH3 N
Q-33(R5,R6=H) o H H C~I3 OCH3
C6H5 O H H CH3 OCH3 N
C6H5 0 H H OCH3 OCH3 N
C6~5 O H H C~3 CH3
Q-2(R5'R6=H~ O H S-Cl OCH3 OCH3 CH
64
~ o~L~
Tubl~ Cont~nued
~Q_ n R 1 ~ Y Z m p.~C
Q 16~R5,R~=H) O H 6 ~r OCH3 OCH3 CH
5 Q-8(R '-SCH ) O H 5-CH3 OCH3 OC~3 ~l
Q-3(R '=SCH ) O H 5-Cl OCH3 3
Q-1(R5,R6=H) O H 5-CH3 OCH3 3
Q-1(R5,R6=H) O CH3 H OCH3 CH3 D
10 Q ( 5 3) H H OC2HS CH3 CH
Q-1(~5,~6=H) O H H F OCH3 CH
Q-2(R5,R~=H) O H M Br OCH3 CH
Q-3(R5,R6=H) O H H I OCH3 CH
Q-8(R5'=SCH3) 0 H H OCF~H OCH3 CH
Q-10(R5=CH3) 0 H H CH2F OCH3 CH
Q-18(R5=H,R6-CH3) 0 H H OCH2CH2F CH3 CH
Q-17(R5=H,R6=CH3) 0 H H OCH2CHF2 CH3 CH
Q-8~a5~=SCH3) 0 H H CH2cF3 OCH3 CH
Q-10(R5=CH3) 0 H H CF3 OCH3 CH
Q-2(R5,R6=H) O H H OCH2CH3 OCH3
Q-1(R5,R6=H) O H H 2 2 8
Q-3(R5'=SCH3) 0 H H OCH CF OCH
Q 5 3) 0 H H OCH3 H CH
Q-16 0 H H CH3 C2H5 CH
Q-8(R '-SCH ) O H H CH3 CH20CH3 CH
Q 5 3) 0 H H OC2H5 ~HCH3
Q-17(~5=H,~6=CH3) 0 H H OCH3 3) 3
Q-8(R5'=SCH3) 0 H H OCH3 3 2
Q-1B~R5=H,R6=CH3) 0 H H OCH3 C2H5 CH
Q-12(R8=Cl) O H H OCH3 CF3 CH
Q~ 5=C~3) 0 H H OCH3 SCH3
Q-18(R5=H,R6=CH3) 0 H H CH3 OCH2CH=CH2 U
Q-1~(~5=H) O H H CH3 OCH C-CH
Q-13(R5=CH3) 0 H H OCH3 CH20CH2CH3 CH
Q-17(R5=H,R6=CH3) 0 H H CH3 2 2 3
.av.~ 3
6fi
Tabl~ Ila Coneinued
Q n R Rl X Y Z m.p.~C
Q-14 0 H H CH3 CH2SCH3 CH
o
Q-lO(R5=CH3) o H H CH3 CH CH
Q-l(R5,R6=H3 o H H CH3 CCH3 CH
Q-8(R5~=SCH3) 0 H H OCH3 CH(OCH3)2 CH
Q-1(R5 R6=H) O H H CH3 CH(OCH3)2 N
Q-8(R5=~C~3) O H H OCH3 CH(OC2E~5)2 CH
Q-2(R5 R6=H) O H H OCH3 CE~(SCH3)2 CH
Q-3(R5,R6=H) Q H H OCH3 C(C~3) (OCH3)2 CH
Q-8 (R5 ~ =SCH3 ) O H H OCH3 CH ~ CH
,o~
Q 18 O H El CEI3 CEI ~> CH
/o-~
Q 17 O H H OC~3 CH ~ CH
,0 CH3
Q-B (R5 ~ =CH3 ) O H E~ OCH3 CE~ ~ CH
Q-10 (R5=H~ O H H OCH3 OCF2H CH
Q-140 H H OCH3 SCF2H CH
Z 5 / CH~
Q ~(R =SCH3) O H H OCH3 ~ IH2 N
~ CH2
Q-1~R5 R6=H) O H H OCH3 CH ¦ CH
3 O CH2
~ CH2
C6~5 O H H OCH3 CH I ~
CH2
/ C~l~
35 C6H50 H H OCH3 C\ ¦ CH
CH2
66
67
Table II~ Continued
Q n R Rl ~ y z m.~.C
Q-ltR5.R6SH) 1 CH3 H OCH3 OCH3 CH
5 Q~l(R5 R6~H) 1 H H CH3 CH3 CH
Q l~R5,~6~H) 1 H H CH3 OCH3 CH
Q-l(R5,R6=H) 1 H H OCH3 OCH3 CH
Q-1(~5,a6=H) 1 H H Cl OCH3 CH
Q-l(R5=H,R6=CH3) 1 H H OCH3 OCH3 CH
10 Q-l(R5=CH3.R6=H) 1 H H OCH3 OCH3 CH
Q-2 (R5, R6=H) 1 H H CH3 CH3 CH
Q-~(R5,R6=H) 1 H H OCH3 OCH3 CH
Q-2(R5,R6=H) 1 H H CH3 OCH3 CH
Q-2(~5,R6=H) 1 H H Cl OC~3 C~
lS Q~2(R5=CH3~a6-~) 1 H H OCH3 OCH3 CH
Q-2(R5=H,R6=CH3) 1 H H OCH3 OCH3 CH
Q-3(R5,R6=H~ 1 H H CH3 CH3 CH
Q-3(R5,R6=H) 1 H H CH3 OCE13 C~I
Q-3(R5,R6=H) 1 H H OCH3 OCH3 CH
20 Q-3(~5.R6=H) 1 H H Cl OCH3 CH
Q-3(R5=CH3: R6=H) 1 H H OCH3 OCH3 CH
Q~4(R5,R6=H) 1 H H CH3 CH3 CH
Q-4(R5,R6=H) 1 H H OCH3 CH3 CH
Q-4(R5,R6=H) 1 H H OCH3 OCH3 CH
25 Q~4(R5~R6=~) 1 H H Cl 3 C
Q-5(R5,R~=H) 1 H H OCH3 OCH3 CH
Q 5(R5,R6 H) 1 H H CH3 CH3 CH
Q-S(R5,R~=H) 1 H H CH3 OCH3 CH
Q 5(R5,R6=H) 1 H H Cl CH3 CH
30 Q-6(R5=H) 1 H OCH3 OCH3 CH
~-6(R5=H) 1 H H CH3 OCH3 CH
Q-6(R5=H) 1 H H CH3 CH3 CH
Q-6(~5=H) 1 H H Cl OCH3 ~H
Q-8(R5'=H) 1 H H ~H3 c~3 CH
35 Q~3(R5'=H) 1 H ~ OCH3 OCH3 CH
6~
Table ~Ta Continued
_Q_n ~ Rl X Y Z m.P~oc
Q-8(~5'=H~1 H H C~3 O~H3 CH
5 Q-8(R5'=H)1 H H Cl OCH3 CH
Q-9(R5=H)1 H H OCH3 OCH3 CH
Q-9(R5=H)1 H H CH3 CH3 CH
Q-10(R5=H)1 H H OCH3 OCH3 CH
Q~10(R5=H)1 H H CH3 OCH3 CH
10 Q-lo(Rs=H)1 H H Cl OCH3 CH
Q-ll(R5=H) H3 OCM3 CH
Q-ll(R5=H)1 H H C~3 OCH3 C~l
Q-12(R8=H) CH3 CH3 CH
Q-12(R8=H)1 H H Cl OCH3 C~
15 Q-l3~R5=cH3)H3 OCH3 CH
Q-14(R5=H)1 H H CH3 CH3 CH
Q-14(R5=H)1 H H OCH3 OCH3 CH
Q-14(R5=H)1 H H CH3 OCH3 CH
Q-14(R5=H)1 H H Cl 3
20 Q-15(R5=~)1 H H OCH3 OCH3 CH
Q-16(R5,R6=H)1 H H CH3 OCH3 CH
Q-16(R5,R6=H)H CH3 ~H3 CH
Q-16(R5,R6=H) 1 H H Cl OCH3 CH
Q-17(R5,R6=H) 1 H H CH3 CH3 CH
25 Q-l6(R5~R6=H) 1 H H OCH3 OCH3 CH
Q-18tR5.R6=H~ 1 H H CH3 OCH3 CH
Q-13(R5,R6=H) 1 H H Cl OCH3 ~H
Q-18~R5,R6=H)OCH3 OCH3 CH
Q-19(R5=C~3,R6=~) 3 OCH3 CH
30 Q-2otR5~R6=cH3) OCH3 OCH3 CH
Q-22(R5,R6,R7=H) 1 H HOCH3 OCH3 CH
Q-24(R5,R6,R7=H) 1 H HOCH3 C~3 CH
Q-28(R5~R6=H,n'=1) 1 H HOCH3 OCH3 CH
Q-30(R5=H,Rg,Rl~=CH3) 1 H H OCH3 OCH3 CH
35 Q 33(R5.R6=H) 1 H HOCH3 5CEI3 CH
68
~9
Table_lIa Continued
- Q e ~ Y z ~.oc
Q ( 11~ R12 OCH3 ) ~ ~ H OCH3 OCH3 CH
C6H5 1 H H OCH3 OCH3 CH
~6H5 1 H H OCH3 CH3 CH
Q t 5 ~ ~6 H~ 1 H H OCH3 OCH3 CE~
5;?-3a(R5.R6~H) 1 E~ H OCH3 OCH3 CH
Q-39(1~5,R6sH) 1 H H OC~3 OC~3 ~E~
10 Q-l(~5~l~6~ H OCH3 OCH3 N
Q-2 (R5, R6~H) 1 H H CH3 OCH3 N
Q~ 5 C~3 ) 1 H H CE13 OCH3 N
Q- 8 ( R5 ' ,C~ ~ ) 1 H H OCH3 OCH3 N
Q-12 (R8-Cl ~ 1 H H O~H3 OCH3 N
15 Q-17(R5.R6=H) 1 H H CCH3 OCE~3 N
Q-18(El5,R6sH) 1 H 3 OCE~3 N
Q-22 (R5, R6 ~ R7=H) 1 H H OCH3 CH3 N
Q-26 (W'=O) 1 E~ H ~CH3 OCH3 N
Q-27 (R5, R6aH) 1 H H3 OCH3 N
20 Q-30(R5~E~g~Rlo~H3 1 H H OCH~ OCH3 N
Q-33(R5,R~=H3 1 H H OCH3 OCH3 N
~6R5 1 H H CH3 OCH3 N
C6H5 1 H H OCH3 OCH3 N
Q-2(R5,Rg=EI) 1 H 5-Cl OCE13 OCH3 N
25 Q-16 (R5,R6=H) 1 lH 5-Br OCH3 OCH3 CH
Q-8 (R5 ' ~SCH3 ) 1 EI 3 O~H3 OCH3 CH
Q ( 5 SCE~3 ) 1 H 5-Cl C;CH3 CH3
Q-l(R50R6~H3 1 H 3 OCE13 CH3 N
Q ( 5 ~ R6 H~ 1 CH3 EI OCH3 CH3 N
30 Q-8 (R5 ' ~SCE13 ) 1 7I ~ OC2~5 CH3 CH
Q-l (P~5 ~ a6~E~) 1 H H F OCH3 CH
Q-2(R5,R6-H) 1 El H Br OCH3 C~
Q ~ 5 ~ 6 H ) 1 H H I OCH3 CH
Q-~ (R5 ' SCH3 ) 1 H H OCF2H OCE~3 CH
35 ~ (R5sC~13) 1 H H CH2F OCH3 CH
69
Tabl~ T~l C~on~tlnu~a
_Q n a ~1 ~ y z m p.C
Q ~ 5 ' 6 1 H H OCH2CH2F 3
5 ' 6 ) 1 H IX C~12C~lF2 CH3
~8t~ 8CH ) 1 ~l ~1 OCH2cF3 OC~{3 CH
~10(E~5~CH3) 1 H H CE'3 OCH3
Q-2(~5,E~6~1f) 1 H H OCH;!~H3 OCH3 N
~ ( 5 .a6 ) 1 H 1{ OCH2CH2Y CH3
Q-R~R5'~SCH3) 1 H H OCH~!cF3 OCH3
~9~5~Cli3) 1 H H OCH~I H CH
Q ~ 5 ' 6 3 ) 1 11 H CH3 OC2~15 CH
~8 (~ ' 5SCH ) 1 H U C}13 CH20CH3 CH
L 5 ~ ~ 5 3 ) 1 H H OC2N5 ~IHCH3
s~l7~R5~H,a6DCH3) 1 H H OC~3 ( 3) 3 U
Q-8 ~ .SCH ) 1 H H OCH3 ~ 3 ) 2 11
Q ~ 5 ' 6 3 ) 3 ~2HS CH
Q-12(R8~Cl) 1 H H OCH3 3
Q-ll(R5.CH3) 1 H H OCH3 SCH3
Q-18tRs~H~6aCH3) 1 H H CH3 OCH2~=CH2 U
Q-lO~R5~ CH3) 1 H H CH3 OCH C--CH l~l
Q-13(R5=CH3) 1 H 11 OCH3 2 2 3 CH
Q-17(Rs-H~R6~CH3) 1 H H ~!{3 OC312CH20CH3 CH
Q-14(~5-11) 1 H H ~H3 CH2SCH3 CH
Q ( 5 ~ 6 ) 1 11 ~ OC}~3 ~3 7
Q-lO(R5=CH3) 1 H H CH3 CHO CH
Q 5 ~ 6 1 M H CH3 COCH3 C}{
Q-3tR5~5SCH3] 1 H H OCI{3 CH(OCH3)2 ~{
Q--l ( Rs ~ lR6 aH) 1 H H CH3 CH ( OCH3 ) 2 El
Q-8(Rs~3scH3l 1 H H OCH3 ( 2 5)2 CH
Q-2(E~5~R6~-H) 1 il H OCH3 CH(SCH3~2 CH
Q~3(E~5~ 5=H) 1 H H t~H3 C (C2{3)(OCH3~2 C}l
~inued
~ R ~1 X ~r Z
Q 8 (E~5 S~H3 ~ 1 H }IOCEI3 C!H~ CH
Q 1~ 5 E~6 E~) 1 H H~H3 CH ~ CH
Q- 17 ~ R5 ~RS H ) 3 CE~S ~ CH
O C~
~-8 ~a5 ' -C~3 ) 1 H HOCH3 Chor 3 CH
Q-lO(R5~H) CH3 OCF2H CH
Q-14 tR5=~l) OCH3 SCF2EI CH
~ CH2
~-B(R5'~SCH3) H HOC~3 CH¦H N
~-1(R~"R6=H) OCH3 CHIH CH
Q l(R5'~6 H) 1 IH HOCH3 CH¦ 2 CH
'~H2
~6H5 1 lH HOCH3 Ci~
25 C6H~ 1 H HOCE13 eE~ I 2 CH
Q- 3 5 ~ R l l ~ R l ~ -CH3 ) 1 ~ 3 ~H2 CH
30 Q39(E'~5,E~53H) 1 ~ HOCR3 CE~¦ 2 C~3
Q- ~ 5 ' R6 ~ ~ 2 H HOCH3 OCE~3 CH
Q-5(E~,a6~ 2 H HOCH3 OCH3 CH
Q-~ (R5 ' =H) 2 E~ HOCH3 OCH3 CH
Q-14 (R5=H) 2 R HOCH3 OCE~3 CH
~a.~ t i nu ed
Q ~ Y Z . p .
Q-16 (:R5 ~ P~6.H) 2 El H OCH3 ~CE~3 CH
Q 1 (a5 ~ %6 H) 2 H H O~H3 OCH3 N
Q-10(E~5~H) 2 E~ H OCH3 OCH3 N
Q-12 (E18-.H) 2 ~ H CH3 0~3
C?-18 tE~5-H. 1~6~CH3 ) 2 H H OCH3 OCH3 N
Q- 2 4 ( R5, E~6 ~ E~7 ~H ) 2 El H OCH3 OCH3 N
Q 27 (E~5 . R63EI) 2 1~ H O~H3 ~H3 N
$;!-33t~5,R6~H) 2 H H OCH3 3 N
Q-37~R5,R6~) 2 H H OCH3 OC~3 CH
Q-l(R5,R63H) 2 H H F OCW3 CH
Q-8 (R5 ' ~SCH3 ) 2 H H OCF2H OCH3 CH
Q-17(R5=H,R63CH3) 2 H H OCH2CH2F CH3 CH
Q-~(R5,R6=H) 2 H H OCE~2CH3 OCH3 N
Q-8 (R5 ' =SCH3 ) 2 H H CH2c~3 OCH3 N
Q- 8 ( R5 ' =CH3 ) 2 H H OC2H5 NHCH~ N
Q ( R$ SCH3 ) Z H H OCH3 CH~ CH
Q-lB(!~s=H~p~6=cH3) 2 H E~ CH3 CH ~ CE~
o
,CH
Q-8 (R5 ' 3CH3 3 2 H El OCH3 ~CH~
~H2
Q-l (R5 . R~EI3 2 H H OCH3 ~CH2
3 0
C6~15 2 H H OCH3 ~c~2
~6E~5 2 H H OCEI3 ~ CH
35 Q-10 (R5=CH3) O H H OCH3 OCH3 N 185-188
3~ 3~r~
73
Table IIb
( H~ ) Q
Yl
~) n ~ 1 1 Yl m.P.~C
Q ( 5 ' 6 ~1 ) H H CH3 o
Q-2(R5,R6=H) O R H CM3 o
Q-3(R5,R6=H~ O H H CH3 o
Q-4(R5,R,j=H) O H H CH3 o
15 Q-7(R5~R6~R7=H) O H H CH3 o
Q-8 (R5 ' YSCH3 ) o H H CH3 o
Q-8 (R5 ~ -~H3 ) o H H CH3 o
5;?-8 (R5 ~ ) o H H CH3 o
Q-9 (R~;,=CH3 ) o H H CH3 o
zO Q-l0(R5=CH3) 0 H H CH3 o
Q-14 (R5=H) O H H CH3 o
Q-16(R5,R6=H) O H H CH3
Q-l7(R~j"R~,=H) o H H CH3 o
Q-lB (R5, R6=H) O H El CH3 o
25 Q~~l~R5~R6.R7=H) o H H CH3 o
Q-22 (R5, R6 ~ R7=H) O H H 5H3 O
Q-Z4(R~,R6~R7=H) O H H CH3 o
Q-27~R5,R6=H,n~=0) o H H CH3 o
Q-30(R5,P~9,Rlo=H) O H E~ CH3 C)
30 Q-33(R5~a6=H) o H H CH3 o
Q-~ (R5 ' =SCH3 3 O H H OCH3 o
Q-1(E(5,R~ ) o H H 2~15 O
Q-9 (R5=CE13 ) O H H OCF2H o
Q-8 (R5 ~ =CH3 ) O H H CH3 CH~
35 Q-EI(R5 =';CE~3) o H El OCH3 CH2
~,~, D L~ r
74
Table_ITb Continued
-Q- n R Rl X
Q~ 5~R6=H) 1 H H CH3 o
Q-2(R5.R6=H) 1 H H CH3 o
Q-8(R5'=SCH3) 1 H H CH3 o
Q-8(R5~=CH3) 1 H H CH3 o
Q-14(R5=H) 1 H H CH3 o
10 Q 16(R5-R6 H) 1 H H CH3 o
Q-17(R5,R6=H) 1 H H CH3 o
Q-18(R5.R6=H) 1 H H OEl3 o
Q-33(R5.R6~EI) 1 H H CH3 o
Q-l(R~.R67H) 1 H C2H5 o
lS Q-8(RS -CH3) 1 H H OCF2H
Q-8(R5'=SCH3) 1 H H OCH3 CH2
Q-8(R5~=CH3) 2 H H CH3 o
Q-14(R5=H) 2 H H CH3 o
Q-B(R5'=SCH3) 2 H OC2H5 o
20 Q ( 5~ 6 ) 2 H H CH3 o
74
Table I I
Rl~507NliCON~
R N
~ n R R
Q 1 (R5 . P~6 H) 0 H H CH3
Q-2~R5.R6=H) O H H OCH3
Q- 3 ( R5, R6 =H ) O H H OC2H5
52-4(R5'~6=H) O H E~ CH3
Q-7(F~5,R6,R7=H) o H H C~3
Q-8 (R5 ~ =~CH3 ) o H H OCH3
Q-8 (R ' -CH ) O H H OCH3
Q-8 (P15 ' =E~) H H CH3
Q-9 (R5=CH3 ) O H H OCF2H
Q-lO(RS=CH3) 0 H H CH3
Q-14 (R5=H) O H H OCH3
Q-l~ (R5=H, ~6=CH3 ) O H H CH3
Q-17(R5=EI,R6=CH3) 0 H H OCF2E~
Q-lB(R~j,=H,R6=CH3) 0 H H OCH3
Q-21(R5,R6,R7=H~ O H H OCH3
Q-22(P(5,R6,R7=H) O H H CH3
Q-24(R5,R6,R~=H) O H H CE13
Q-27(R5.R~=H.Q'=O) O H H OCH3
Q-3(R5~R~,~Rlo=H~ O H H QCH3
3 0 S~ ~ 5, 6 H ) H H OCH3
Q-l(R5,R~ ) 1 H H CH3
Q ( 5 ' 6 ) 1 H H OCH3
Q ( 5 3 ) 1 H H OCH3
Q-8 (~5 ~ =SCH3 ~ 1 H H CEI3
Q-l~(R5=CH3) 1 H H OC2H5
~,r;~ 7,~'
7~
Table I Iç _C~ontinued
R 1 3~ 1 m . p . C
Q-14 (P~5-H) 1 R H OCH3
Q- 17 ( R5 -E~, R6 =CH3 ~ 1 Hl !E~ OCF2H
Q-?l~R5=H,R6=CH3~ 1 H H OCH3
Q-33(R5,R6=H) 1 H H OCH3
Q 8 ~R5 ' =CH3 ) 2 H H CH3
Q-27(R,R6=H,n'=0~ 2 H H OCEI3
Q-28(R5.R6=HOn'=1) 2 H H OCH3
Q ( 5 ' 6 ) 2 H H CH3
Q-4(R5,R6=H) 2 H 2E15
76
77
Table I Id
P' 1
R ~
O Y2
SL n R 1 ~1 Y2
Q ( 5 ' 6 ) H H CH3 CH3
Q-2 (R5, R~=H) O H H OCH3 CH3
Q-3 (R5 ~ ~6=H) O H 2 5
Q-4 (R5, R6=H) 0 H H CH3 CH3
Q-7(R5,R6,R7=H) 0 H H CH3 CH3
Q-~ ~R5 ~ =SCH3 ) o H H CH3 CH3
Q-8 (R5 ~ =CH3 ) O H H CH3 CH3
Q-B (~5 ' =H) H H CH3 CH3
S2 ( 5 3 ) El H OCF2H CH3
;2-lO(R5=CH3) O H H CH3 CH3
Q-14 (R5=H) 0 H H CH3 C~3
Q-16(R5,R6=H~ O H H CH3 C~3
Q-17(~5,R6=H) O E~ H OCF2H CH3
Q-18(R5,R6=H) O El H OC2H5 CH3
Q-21(~5,R6,P~7=H) 0 E~ H CH3 CH3
Q-22(R5,R~,,R7=H~ o H H O~H3 H
Q-24(R5,R6,a7=E~) O H H OCF2H CH3
Q-27(R5,R62H,n'=o~ O H H CH3 CH3
Q-30(R5~EIg~Rlo=H) O H H C~3 c~3
3 O Q ( 5 t 6 ) H H s:~3 CH3
;2 ( 5 ~ 6 ) 1 H H CH3 CH3
Q-2(R5,R~-H) 1 M H OCH3 CH3
Q-3(~5,R6=H) 1 H 2 5
Q-8 (R5 ' =SCH3 ) 1 H H CH3 ~H3
Q-8 (R5 ~ =CH3 ~ H3 CH3
Q-14 (P~5=H) 1 H H CH3 CH3
7B
Table IId C~o~ntinued
~2_ n R 1 1 2 m. D. C
Q-l6~R5~H,R6~CH3) l H H CH3 CH3
Q-lg(R5=~R6=CH3) 2H5 C~13
Q-21(R5,R6,R7=H~ 1 H H ~H3 CH3
Q-Z7(R5,a6=H,n'=O) 1 H H CH3 CH3
Q-33(R5,R zH) l H H CH3 CH3
Q ( 5 ' 6 1 H H CH3 CH3
O-l(R5'R6=H) 2 H H CH3 CH3
Q-a (F~5 ' =SCH3 ) 2 H H CH3 CH3
Q-~ (R =CH ) 2 H H CH3 CH3
Q-l4 (R5=H) 2 H H OCH3 CH3
Q-33(R5,R6=H) 2 H H CH3 CH3
79
Table I Ie
P~1~502NHcoN_<f ``N 3
R N X2
Q n a Rl X2 Y3 m. p . C
10 Q 1 (R5 ,R6 H) H H CH3 CH3
Q-2(R5,R6=H) O H H OCH3 CH3
Q-3(R5,R6=H) O H C~13 C2H5
Q ( 5 ~ 6 H) H H ~H3 CH3
Q-7(R5,R6,R7=H) O H H CH3 CH3
15 Q ( 5 3 ) O H H CH3 CH2CF3
Q 3 (R5 H3 ~ H H CH3 C~2CF3
Q-a (R5 ' =H) O H H CH3 CH3
Q 9 (R5 H3 ) o H 3 CH3
Q-10 (R5=CH3 ) o H H CH3 CH3
Q-14 (R5=~) O H H CH3 ~2H5
Q-16(R5=H.R6=CH3) 0 H H CH3 CH3
Q-17(R5=H,R$=CH3) 0 H H OCH3 CH2CF3
Q-18 (R5=H. R6=CH3 ) O H 3 3
Q-21(R5'R6'~7=H) ~ ~ CH3 CH3
~;?-22 (R5, R6 ~ R7=E~) O H o H3 C2H5
Q-24(R5~R6~R7=H) ~ 3 3
Q-27(R5,R6=H,r~ =O) O H H CH3 CH3
Q-30(R5,Rg,Rlo=H) O h H C~3 CH3
Q-33(R5,R6=H) O H H CH3 CH3
30 Q ~ 5 ' ~ ) 1 H H CH3 CH3
Q-2 (R5 ~RS=H) 1 H H H3 CH3
Q ( 5 3 ) 1 ~ H CH3 C2H5
Q-8 (R5 ' - SCH3 ) 1 H ll CH3 CH2CF3
Q ~ 5 3 ) 1 H 3 3
Q-10 (R5 CE~3 ) 1 H H CH3 CH3
5;?-14 (R5 H) 1 H H CH3 C2~5
~ r, r~- ,r J, , ~
~10
~ mled
Q n R Rl X2 Y3 p. C
Q 16(P(5=H,R6=CH3)1 H H CH3 CH3
Q-27 (R5 ~ R6=EI)1 H E~ CH3 C~3
S?-33 (R5,R6=H) 1 H E~ CH3 CH3
Q-l(R5,R6=H) 2 H H CH3 c~3
Q ( 5 3 ) 2 H 3 3
;2-14 (R5=H) 2 H H CH CH
1" 3 3
Q-18(R5=H,R6=CH3)2 H H OCH3 CH2CF3
2~
~0
1~1
~.~
~ C~2 ) nQ OCH
5 ~N)150~NE~CON-CH2~N
El N~
~g3
~ n p~ .P.C
Q-l(R5,R6~1) O H H CH3
Q-2(~5,~6~H) O M El ~H3
Q-3 (R5, ~6~H) o H H CH3
~-4 ~R5, P~6.}1) o H H OCH3
15 Q-7(~5~R6~E~73H) O H H OCH3
Q-3IR5~ H3~ o H H CH3
Q-8 (R5 ' ~KSCE13 ) o H ~i ~CH3
Q-8(P(5'~H) 0 H H CH3
Q-9 (R ~CE~ ) O H H CH3
20 Q-lC~(R5'CH3) o H H OCH3
Q-14 tEa5DlH~ O El H OCH3
Q-l~R5DH,R6YCH3) 0 H H CH3
Q-17(R5~H,P~6~CH3) 0 H H CH3
Q-18(R5~EI,R6~CH3) 0 H H OCE~[3
25 ~-21(~,a6,1R7.~) 0 ~ EI CE~
Q~22~R~ 6,R~=H~ O H H OCH3
Q-24(F~5,E16.P~7=H) O lH ~ ~H3
Q-27(R~"R~ ) O E~ H CH~
Q-30(P~5~P~g~a~ ) E~ H OCH3
30 Q-33tp~5oR~i~H) o H H C~3
Q-3a ~ ,5.H) C H H CH3
Q-l tR5 ~ 1 lH H OCH3
Q-2 ~ 5, R~ -~H~ 1 H H CH3
Q~ sCH ) 1 H H ~H3
35 Q-~ (a5 ' SC'E13 ) 1 H ~ oc~3
81
.3
82
able I~I~ Con~inued
Q n ~ Rl ~3 m. P . C
Q-10(R5=CH3) 1 El H CH3
Q-14 (R5=H) 1 H H CH3
Q-16(R5=H,R6=CH3~ 1 H 11 OCH3
Q-18(R5,H,R6=CH3) 1 H H OCH3
Q-27~R5,R6=H,n'Q0) 1 H H CH3
Q-3B(R5,R6=H~ 1 H EI OCH3
10 Q-l(R5,Rs=H) 2 R H OCH3
Q ( 5 H3 ) 2 H H OCH3
Z5
ez
~ J~3
83
Table II~
~f ~ CH2 ) nQ 2~
N S02NHCSN ~ ~ (Z
R N ~
Q n R ~l ~ Y Z ~p ~C
l0 Q-l~R5'R6=H~ H H OCH3 OCH3 CH
Q-l~R5,R6=H~13 OCH3 CH
Q ( 5~ 6 H)O H H OCH3 c~3 CH
Q-3(~5,R6=~)O H H OCH3 OCH3 CH
Q-4(R5,R~=H)0 H H OCH3 OC~3 CH
Q l(R5,R6 H)O H H CH3 OCH3 N
Q-8(R5'=CH3)O H O H3 CH3 CH
Q ( 5 ~3)OCH3 OCH3 CH
Q-lO(R5=CH3)O H H CH3 OCH3 CH
Q-l4(R5=H) H H OCH3 OCH3 CH
~O Q-l6~R5'R6=H~ H H OCH3 OCH3 CH
Q-l7(R5=H,R6=CH3) O H H OCH3 O~H3 CH
Q-2l(R5,R6,R7=H) O H H OCH3 OCH3 CH
Q-22(R5,R6,R7=H) O H H OCH3 OCH3 CH
Q-24(~5,R6,R7=H) O H H OCH3 OCH3 ~
25 Q-33(R5,R6=H)O H H OCH3 O~H3 CH
Q (R5 CH3)l H H OCH3 oc~3 CH
Q ( 5 3)l H H 3 H3 N
Q-8(R5'=CH3)O H H CH3 OCH3 N
Q-8(R5'=CH3)3 OCH3 Cff
83
~'1
Formulaeions
U~e~ul formulation~ of the compound~ of For-
mulae I and II can be prepared in conventional ways.
They include dusts, granule&, pellet6, ~olutions,
su6pension6, wettable powders, emulsifiable concen-
trates and the like. ~any of these may be applied
directly. Sprayable formulation6 can be extended in
suitable media and used at ~pray volume~ of from a few
pints to several hundred gallon6 per~acre~ High
strength composition~ are primarily used a~ interme-
diates for further ~ormulation. The formulation~,
broadly, contain about 1% to 99% by weight of active
ingredient(s) and at least one of (a) about 0.1% to
20~ surfactant~s) and (b) about 1% to 99.9% solid or
liquid diluent(~). ~ore specifically, they will con-
tain these ingredients in the following approximate
proportions:
Percent b~ Welg~
Active
Inqredient Diluent(s~ Surfactant(s1
Weteable Powder~20-90 0-74 1-10
Oil Su~pen~ions 1-50 40-99 0-15
and Solutions
(including Emulsifiable
Concentrates)
~queous Suspension5-50 40-~4 1-20
Dusts 1-25 70-99 0-5
Granule6 and Pellets 1-95 5-99 0-15
High Streng~h 90-99 0-10 0-2
Compo6ition6
Lower or higher levels of active ingredient can,
of cour6e, be pre~ent depending on the intended use
and the physical propereies of the compound. Higher
ratio6 of surfactant to active ingredient are some-
~imes desirable, and are achieved by incorpora~ioninto the formulation or by tank mixing.
84
B5
~ ypi~al ~oli~ fliluen~ are ~ ceibed in Watkln~
et al.~ "Handbook of In~ecticide Dust Dlluent6 and
Cacrier~", 2n~. Ed., Dorland Book6, Caldwell, NJ. The
~ore ab60rptive diluents are prefecred for wettable
powder6 and the denser one~ ~o~ dusts. Typical liquid
diluents and 601ventfi are de~cribed in Mar6den, "Sol-
vent6 Guide", 2nd. Ed., Inter~cience, New Yo~k, 1950.
Solubility under 0.1% is preferred for ~u~pen~ion
concentratefi: 601ution concentrate~ are preferably
6table again~t p~a6e separation at 0C. "McCutcheon's
Detergent~ and Emul6ifier~ Annual", Allured Publ.
Corp., Ridgewood, NJ, as well as Si6ely and Wood,
"Encyclopedia of Surface Active Agent~", Che~ical
Publ. Co., Inc., New York, 1964, li~t ~ur~actant~ and
reco~mended u~e~. All formulation~ can contain minor
amount~ of additives to reduce foam, corrozion, micro-
biological growth, etc. Preferably, ingredients
6hould be approved by the appropriate governmental
bodies for the use intended.
The methods of making such compo~i~ions are well
known. Solution~ are prepared by simply mixing the
ingredient~. Fine 601id ~ompo~ition6 are made by
blending and, usually, grinding a~ in a hammer or
fluid en~rgy mill. Suspen~ions are prepared by wet
~illing (fiee, ~or example, Littler, U.S. Patent
3,060,084~. Granules and pellet~ may be made by
6praying the active ma~erial upon preformed granular
carrier~ or by agglomeration technique6. (6ee J. ~.
~rowning, "Agglomeration", Chemical En~in e~
December 4, 1967, pp 1~7ff. and "Perry'~ Che~ical
~ngineer'6 Handbook", 4th Ed., McGraw-Hill, NY, 19~3,
~P ~-5g~
~ r.~ r~'
~361
Exam~le_6
ettable Powder
N-~(4,6-dimethoxypyrimidin-2-yl)aminocacbonyl]-2-(lH-
1~2,4-tLiazol-l-yl)-3-pyridine6ulfonamide 80
sodium alkylnaphthalene~ulfonate 2
sodium lignin6ulfonate 2~
synthetic amorphous silica 3%
kaolinite 13%
The ingredient~ are thoroughly blended and
hammer-milled or air-milledl to produce particles
averaging below 20 micron~ in diamete~. The product
is reblended before packaging.
Example 7
Oil ~usPen6ion
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonYl]-2-(lH-
1,2,4-triazol-1-yl)-3-pyridinesulfona~ide 35%
blend of polyalcohol carboxylic e6ters
and oil soluble petroleum ~ulfonatefi 6%
Xylene 59%
The ingredient6 are combined and ground together
in a ~and mill to produce particles e~entially all
below 3 microns. The product can be used directly,
extended ~ith oil~, or emulsified in water.
Example 8
Oil Suspension
N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl~ (lH-
1,2,4-triazol-1-yl)-3-pyridine~ulfona~ide 25~
polyoxyethylene ~orbitol hexaoleate 53
highly aliphatic hydrocarbon oil 70%
The ingredient~ are ground together in a ~and
mill un~il the 601id particle~ have been reduced ~o
unde~ about 5 ~icrons. The re~ulting thick suspen~ion
may be applied directly, but preferably after being
extended ~ith oil~ or emul~ified in water.
~6
~ r ~ `3 r~
~ 7
xamp.le 9
Solution
N-[(4,6-dimethoxypyri~idin-2-yl)aminocarbonyl]-2-(lH-
1,2,4-triazol-l-yl)-~-pyridine6ulfonamide 5~
dimethylfor~amide 95%
The ingredients are combined and ~tirred to
produce a ~olu~ion which can be u~ed for low volume
application6.
ExamPle 10
Emul~ifiable Concentrate
N-[~4,6-dimethoxypyrimidin.-2-yl~aminocarbonyl]-2-(lH-
1,2,4-tria~ol-1-yl)-3-pyridinesulfonamide 5.0%
blend of oil soluble sulfonAtes
and polyoxyethylene ethers 4.0%
N-methyl pyrrolidone ~5.5%
xylene 45-5%
The active ingredient6 are combined and ~tirred
until dissolved. A fine screen filter is included in
packaqing operation to insure the ab6ence of any
extraneous undissolved material in the product.
Exam~le 11
Aqueous Suspen~niorl
~-[(4,6-dimethoxypyri~idin-2-yl)aminocarbonyl]-2-(lH-
1,2,4-tria201-l-yl)-3-pyridine6ulfonamide 50.0%
dodecylp~enol polyethylene glycol ether 0.5%
crude calciu~ ligninsulfonate 5.0%
xanthan gum thickener 0.2~
paraformaldehyde 0.2%
water 44.1
The ingredien~ are ground toge~her in a 6and
ball or roller mill to produce particle6 essen~ially
all under five microns in ~ize.
87
/ ~ t - r ,~ ~3 r~ e-
88
Exa~le 12
Du~t
N-~4.6~dimethoxypyrimidin-2-yl)am~nocarbonyl]-2-(lH-
1,2~4-tciazol-1-yl)-3-pyridinesul~onamide (active
ingredient) 20~
attapulgite 10%
talc 70S
The ingredient i~ ble!nded with attapulgite and
then passed through a hammer-mill to produce parti~les
substantially all below 200 microns. The gr~und
concentrate i6 then blendedl with powdered talc until
homogeneous.
Example 13
Dust
lS wettable powder of Example 6 5%
pyrophyllite (powder) 95%
The wettable powder and the pyrophyllite diluent
are thoroughly blended and then packaged. The product
i8 suitable for use as a du6t.
ExamPle 14
Granule
wettable powder of Example 6 84%
~ugar 16%
The ingredients are blended i~ a rotating or
fluid bed mixer and water ~prayed on to acco~plish
granulation. ~hen mo~ of the material ha6 reached
the de~ired range of 1.0 to 0.52 mm. (U.S.S. ~18 to
40 ~ieves), the granule~ are removed, dried, and
6creened. Over~ize material i~ crushed to produce
additional material in the desired range.
~8
~`1 r~ f ~ D,~ r~
as
ExamPle 15
Granule
wettable powder of Example 6 10%
attapulgite g~anules
(U.S.S. #20-40: O.B4-0.42 mm) 90
A ~lurry of wettable powder containing 50%
601id6 is 6praysd on the su~face of attapulgite
granule~ in a double-cone blender. The granules are
dried and packaged.
Example 16
Extruded Pellet
N-[(4,~-dimethoxypyrimidin-2-yl)aminoca~bonyl]--2-(lH-
1,2,4-triazol-1-yl)-3-pyridine~ulfonamide 25~
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5~
~odium alkylnaphthalenesulfonate 1%
calcium/magnesium bentonite 59%
The in~Ledient~ are blended, hammer-milled and
then moistened with water. The mixture is extruded as
cylinders about 3 mm diameter which are cut ~o produce
pellets about 3 mm long. These may be used directly
after dlying, or the d~ied pellets may be crushed to
pas& a U.S.S. ~20 sieve (0.84 mm opening6). The
granules held on a U.S.5. #40 fiieve (0.42 ~m openings)
may be packaged for u~e and ~he fines recycled.
ExamPle 17
Hiqh Strenqth Concentrate
N-~(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-~-(lH-
1,204-triazol-l-yl)-3-pylidinesulfonamide 98.5%
gilica aerogel 0.5%
synthetic amorphous fine silica 1.0%
The ingr~dient~ are blended and ground in ~
hammer-mill to produce a high strength concen~rate
essen~ially all pas6ing a U.S.S. ~50 sieve (0.3 mm
opening63. This material may then be formula~ed in a
varie~y of way6.
B9
--~ f~ 3""
Utilit~
Te~t re6ulta indicate that the compounds o~ the
present invention are highly active preemergent or
postemecgent herbicide6 or plant growth regulant6.
~any of them have utility for broad-spectrum pre- and
or post-emergence weed control in area6 where complete
con~rol of all vegetation i~ desired, ~uch a~ around
fuel storage tanks, ammunition depo~, industrial
stoIage areas, pa~king lot~, drive-in theaters,
around billboards, highway and railroad structures.
Some of the compound~ have utility for selective weed
control in crops such as rice, wheat, barley and cocn.
Alternatively, the zubject compound~ are useful to
modify plant grow~h.
The rates o~ application ~or the compounds of
the invention are de~ermined by a number of factor6,
including ~heir use as plant growth modifiers or as
herbicide~, the crop species involved, the types of
weed6 to be controlled, weather and climate, formu-
lation6 selected, mode of appllcation, amount of
foliage present, etc. In general term~, the subject
compound~ should be applied a~ levels of around 0.05
to 10 kg/ha, the lower rate~ being ~ugge~ted for u~e
on lighter 60ils and/or those having a low organic
matter content, for plant growth modification or for
situations where only shor~-term persi6tence is
requiled .
The compounds of ~he invention may be used in
combination wi~h any other commercial herbicide, exam-
ple6 of which are tho~e of ~he triazine, triazole,uracil, urea, amide, diphenylether, carbamate and
bipyridylium type6.
The herbicidal p~operties of the sub~ect com-
pounds were discovered in a number of greenhouse
te~ts. The test procedure6 and re~ults follow.
91
Com~ound 8
Compound 1
OCH3
[~ SOzNHCONH~
N N OCH 3
N~
Compound 2
OCH
N
~, S02NHCONH~O~
15~ N ~ N'^~N CH3
N
Compound 3
CH3
N -t
J
N
91
2 i~
92
Test A
Seeds of crabgrass (~g~__ria ~pp-), barnyard-
gra~s (Echinochloa g~y~q~ , wild oat~ (Avena
fatua), sicklepod ~Cassia obtusifolia), morningglory
(Ipomoea 8pp. ), cocklebur (Xanthium Pen~Ylvanicum),
sorghum, corn, soybean, sugar beet, cotton, rice,
wheat, and purple nutsedge (Cyperus rotundu~) tuber~
were planted and treated pceemergence with the test
chemical6 dis~olved in a non-phytotoxic solvent. At
the game time, these crop and weed ~pecies were
~eated with a soil/foilage application. At the time
of treatment, the plants ranged in height from 2 to 18
cm. Treated plant~ and conl:rol6 were maintained in a
greenhou~e for sixteen day&D after which all ~pecies
weIe compared to control~ and visually rated for
re6ponse to tLeatment. The rating~, sum~arized in
Table A, are bafied on a numerical scale extending from
0 = no injury, to 10 = complete kill. The accompany-
ing descLiptive 6ymbol~ have the ~ollowing meanings:
C = chlorosi~necrosi~;
B - burn:
D = defoliation;
E = emergence inhibition;
G = grow~h retardation,
~ = formative effect:
U = unusual pigmentation;
= axillary stimulation;
S = albini~m; and
6Y = abscised buds or flowe~s~
92
93
Table A
Compound 1 Compound 2
~ate g/ha 2000 400 2000 400
POSTEMERGENCE
Cotton 5C,9G 4C,9G 4C,9G 3C,9H
Sorghum 3C,8H 2C,2G 3C,6G 3C
Corn 3C,8H O 2C,6H O
Soybean 3C,8H 3C,8G 3C,8G 2C,8G
Wheat 5G O 5G 2G
Wild Oats O 0 5G O
Rice 2C,9G 3G 4C,BG 3C,5G
~arnyardgra~6 3C,9H 2G 4C,BH O
Morningglory3C,8H3C,~H 3C,8H 3C,7H
Cocklebu~ 5C,9H 4C,8H 3C,9~ 4C,9
Sicklepod 4C,8H 3C,7G 3C,8H 4C,5G
Nut~edge 2C,9G 2C,9G 3C,9G 3c~aG
Sugar beet 9C 5C,9G 9C 9H
PREEMERGENCE
Cotton 9G 8G 9G 7G
Sorghum 3C,9G 3C,5G 3C,8H 2C,5G
Corn 2C,9G 3C,7H 3C,9H 3C,7G
So~bean 3C,7G 3C,6G 4C,8H 3C,6H
Wheat 2G O 2C,7G 3G
~ild ~ats 0 0 3C,8G O
Rice 9H 5G 4C,8H 2C,5G
Barnyardgrass 8H 3C,6H 3C,8H O
Morningglory9G 9G 9G 3C,8H
Cocklebur 9H 7H - 3C,8H
Sicklepod 8G 4C,8G 4C,9G 3C,5G
25 Nutsedge lOE 5G 10~ 0
Sugar beet4C,9G 5C,9G 5C,9G 3C,9G
93
9g
Table A ~ontinu d~
Compound 3
5 Rate g/ha 2000 ~oo
POSTEMERGENCE
Cotto~ 3C,9H 3C,5H
Sorghu~ o o
Corn 0 o
Soybean o o
10 ~heat 0 0
Wild Oats o
~ice 3C,SG o
Barnyardgrass 0 o
Morningglory o 0
Cocklebur 0 0
Sicklepod o 0
15 Nut~edge 0 0
Sugar beet 0 o
PREEMERGENCE
Cotton 2G o
Sorghum o 0
Corn 2G 0
5Oybean 2C 0
20 Wheat o o
Wild Oats o o
Rice 2C 0
Barnyardgras~ 0 o
Morningglory 2C 0
Cocklebur o o
Sicklepod 2C 0
25 Nutsedge 0 0
Sugar beet 5G O
