CA1053231A - Pyrazole amides and thioamides - Google Patents
Pyrazole amides and thioamidesInfo
- Publication number
- CA1053231A CA1053231A CA240,263A CA240263A CA1053231A CA 1053231 A CA1053231 A CA 1053231A CA 240263 A CA240263 A CA 240263A CA 1053231 A CA1053231 A CA 1053231A
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- Prior art keywords
- alpha
- acetamide
- compound according
- phenylpyrazole
- methyl
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Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of the formula:
Formula I
wherein R1 and R2 are the same or different and are hydrogen.
halogen, alkyl of from 1 to 6 carbon atoms, inclusive, halo-alkyl of from 1 to 6 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrolidine or piperi-dine. A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halo-gen, cyano, nitro or trifluoromethyl and when adjacent can be joined to form a ring of from 5 to 7 carbon atoms, inclu-sive; 2 is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl, or alkoxy of from 1 to 3 carbon atoms, inclusive, and n is 0, 1, or 2; W is selected from the group consisting of oxygen and sulfur; or an acid addition salt thereof formed with a strong acid. Methods for preparing the compounds and agricultural compositions comprising the compounds with carriers for use as herbi?ides by application to follage, soil or ponds for the control of unwanted vegetation are disclosed.
-1?
Compounds of the formula:
Formula I
wherein R1 and R2 are the same or different and are hydrogen.
halogen, alkyl of from 1 to 6 carbon atoms, inclusive, halo-alkyl of from 1 to 6 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrolidine or piperi-dine. A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halo-gen, cyano, nitro or trifluoromethyl and when adjacent can be joined to form a ring of from 5 to 7 carbon atoms, inclu-sive; 2 is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl, or alkoxy of from 1 to 3 carbon atoms, inclusive, and n is 0, 1, or 2; W is selected from the group consisting of oxygen and sulfur; or an acid addition salt thereof formed with a strong acid. Methods for preparing the compounds and agricultural compositions comprising the compounds with carriers for use as herbi?ides by application to follage, soil or ponds for the control of unwanted vegetation are disclosed.
-1?
Description
105;~Z31 BR I ~ r [)I- ~ CR ! ~r I ()N_OI^ T~IE INVr:Nl!ON
This invcntion conc~rns novel ~o~ )oLIl1cls of thc Fo~ ul.
I which arc uscful in the agricultul-al arts as h~rbici~lcs, The compourlds are rormulatcd with carriers to prepal-c COlllpO-'> sitions whictl can be appli ed as pre- and post-emergent hcrbicides.
DETA I LED DESCR I PT I ON OF THE l NVE Nl I ON
The invention relates to substi tuted pyrazo1es, which are use~ul in agriculture-as hcrbicides, of ~he formula:
Rz W
Rl - C ~ C-- C - N
. ~ 1 \ N
A ~ ~ ~ ~
. -.
wherein R1 and R2 are the same or different and are selected . from the yroup consisting of hydrogen, alkyl of 1 to ~ car-bon atoms, inclusive, haloalkyl of 1 to 6 carbon atoms, - 20 inclusive, phenyl, or togcther Rl and R2 can be joined to form a cycloalkyl ring of ~ to ~ carbon atoms; R3 is selected from the group consisting oF hydrogenJ alkyl of `~ from 1 to 8 carbon atoms, incl~sive, phenyl or benzyl; R"
.
is selected from the group consisting of hydrogen or alkyl of from 1 to 6 carbon atoms, inclusive, or together R3 and R4 can be ~oined to form a heterocyclic ring se!ected From the group consistin3 o~ morpholine~ pyrrolidine or piper-- ~dine. A and B are the same or differcnt and are selected : from the group consi.sting of hydrogen~ alkyl ot Irom 1 to 6 carbon atoms~ inclusive, phenyl, halogen, cyano, nitro or ..~
~ " ' . ' , ' ' ' ''~:
- ~, ~ ' ', .
.
~229 1:`
trifluoromethyl or A and e when on adjacent positions (3~ 4 or 4, ~) can be joined to form a cycloalkyl ring of -From ~ to 7 carbon atoms, inclusive; Z is selected from the group consisting of S ~~Xn ~ n ~ :
,' 1 0 S
~.' ~ X n ". O
wherein X is selected from the group consisting of halogen, nitro, alkyl of from 1 to 3 carbon atoms, haloalkyl of from ;~; 1 to 3 carbon atoms, inclusive or alkoxy in which the alkyl moiety is from 1 to 3 carbon atoms, inclusive; n is selected from 0, 1, or 2; W is selected from oxygen and sulfur.
The configuration of the formulae:
: C~ C
,~N
`: 25 indicates that the R2 group can be attached to either the ~ - a or ~ carbon and that the pyrazole moiety can also be attached to either the a or ~ carbon.
The preferred compounds, i.e., those having greater activity can be represented by the following formulae ll -3- ::~
. , ~
lOS3~3~
.
tl)rou(ll~ Vl 1, incllJsive. Tl\es~ f~rm~ r~)r~.<;~nt th~ r~-~erre~ co~pounds basecl upon sLructure-ac~ivi~y r~lation-ships.
Formula ll W
R~ - C1~ ~C - C - N
~ a R~
~-- X
n wherein R1, R2, R3, R4, A, B, X, W, and n are as defined for Formula 1, or an acid addition sal~ thereof.
- Forrnula lla H W
. - R1 C ~ C C - N
; A\ / N
B ~
~' Xn ' wherein B is alkyl of from 1 to 3 carbon atoms, inclusive, or halogen and R" R3, R~, A, X, W, and n are as defined for Formula 1, or an acid addition salt thereof.
:: :
. .
. .' , ' :
. :~
, .
.
~ ~2~(~
:~053Z31 Formula l!l I ll ~ R3 Rl- C - C N~
A ~ Z
wherein R1 and R2 are alkyl of from 1 to ~ carbon atoms, inclusive, and R3, R4, A, B, W and Z are as defined for Formula 1, or an acid addition salt thereof.
~ Formula IV
:', : H W
l ll , R3 Rl- l C - N
~ ~
N
A - ~ Z
B
. , .
wherein R3 and R4 are methyl or ethyl and Rl, A, B) W and Z -are as defined for Formula I, or an acid addition salt thereof.
. ' Formula V
R2 W ~ .
Rl - C ~ C - C ~ \ -;~
: / N ~
A ~ Z
~0 B
, ~ ~',''3 ~OS 3 ~ 3 1 wherein R3 and R4 are hydrogen or alkyl of from 1 to ~ car-bon atoms, inclusive, and R1, R2, A, B, W, and Z are as defined for Formula 1, or an acîd addition salt thereof.
Formula Vl R1 C ~ C C N~
1 O B~L~
wherein X is halogen, methyl, or ethyl and R~, R~, R3, R4, A, B, and W are as defined for Formula 1, or an acid addi-tion salt thereof.
.~ 15 Formula Vll Rl2 ll /R3 Ri-- C -- C N~
/ N ~
B ~ ~ ~, wherein Rl and R2 are hydrogen, methyl, ethyl, or propyl;
R3 and R4 are methyl or ethyl; B is halogen or alkyl of from
This invcntion conc~rns novel ~o~ )oLIl1cls of thc Fo~ ul.
I which arc uscful in the agricultul-al arts as h~rbici~lcs, The compourlds are rormulatcd with carriers to prepal-c COlllpO-'> sitions whictl can be appli ed as pre- and post-emergent hcrbicides.
DETA I LED DESCR I PT I ON OF THE l NVE Nl I ON
The invention relates to substi tuted pyrazo1es, which are use~ul in agriculture-as hcrbicides, of ~he formula:
Rz W
Rl - C ~ C-- C - N
. ~ 1 \ N
A ~ ~ ~ ~
. -.
wherein R1 and R2 are the same or different and are selected . from the yroup consisting of hydrogen, alkyl of 1 to ~ car-bon atoms, inclusive, haloalkyl of 1 to 6 carbon atoms, - 20 inclusive, phenyl, or togcther Rl and R2 can be joined to form a cycloalkyl ring of ~ to ~ carbon atoms; R3 is selected from the group consisting oF hydrogenJ alkyl of `~ from 1 to 8 carbon atoms, incl~sive, phenyl or benzyl; R"
.
is selected from the group consisting of hydrogen or alkyl of from 1 to 6 carbon atoms, inclusive, or together R3 and R4 can be ~oined to form a heterocyclic ring se!ected From the group consistin3 o~ morpholine~ pyrrolidine or piper-- ~dine. A and B are the same or differcnt and are selected : from the group consi.sting of hydrogen~ alkyl ot Irom 1 to 6 carbon atoms~ inclusive, phenyl, halogen, cyano, nitro or ..~
~ " ' . ' , ' ' ' ''~:
- ~, ~ ' ', .
.
~229 1:`
trifluoromethyl or A and e when on adjacent positions (3~ 4 or 4, ~) can be joined to form a cycloalkyl ring of -From ~ to 7 carbon atoms, inclusive; Z is selected from the group consisting of S ~~Xn ~ n ~ :
,' 1 0 S
~.' ~ X n ". O
wherein X is selected from the group consisting of halogen, nitro, alkyl of from 1 to 3 carbon atoms, haloalkyl of from ;~; 1 to 3 carbon atoms, inclusive or alkoxy in which the alkyl moiety is from 1 to 3 carbon atoms, inclusive; n is selected from 0, 1, or 2; W is selected from oxygen and sulfur.
The configuration of the formulae:
: C~ C
,~N
`: 25 indicates that the R2 group can be attached to either the ~ - a or ~ carbon and that the pyrazole moiety can also be attached to either the a or ~ carbon.
The preferred compounds, i.e., those having greater activity can be represented by the following formulae ll -3- ::~
. , ~
lOS3~3~
.
tl)rou(ll~ Vl 1, incllJsive. Tl\es~ f~rm~ r~)r~.<;~nt th~ r~-~erre~ co~pounds basecl upon sLructure-ac~ivi~y r~lation-ships.
Formula ll W
R~ - C1~ ~C - C - N
~ a R~
~-- X
n wherein R1, R2, R3, R4, A, B, X, W, and n are as defined for Formula 1, or an acid addition sal~ thereof.
- Forrnula lla H W
. - R1 C ~ C C - N
; A\ / N
B ~
~' Xn ' wherein B is alkyl of from 1 to 3 carbon atoms, inclusive, or halogen and R" R3, R~, A, X, W, and n are as defined for Formula 1, or an acid addition salt thereof.
:: :
. .
. .' , ' :
. :~
, .
.
~ ~2~(~
:~053Z31 Formula l!l I ll ~ R3 Rl- C - C N~
A ~ Z
wherein R1 and R2 are alkyl of from 1 to ~ carbon atoms, inclusive, and R3, R4, A, B, W and Z are as defined for Formula 1, or an acid addition salt thereof.
~ Formula IV
:', : H W
l ll , R3 Rl- l C - N
~ ~
N
A - ~ Z
B
. , .
wherein R3 and R4 are methyl or ethyl and Rl, A, B) W and Z -are as defined for Formula I, or an acid addition salt thereof.
. ' Formula V
R2 W ~ .
Rl - C ~ C - C ~ \ -;~
: / N ~
A ~ Z
~0 B
, ~ ~',''3 ~OS 3 ~ 3 1 wherein R3 and R4 are hydrogen or alkyl of from 1 to ~ car-bon atoms, inclusive, and R1, R2, A, B, W, and Z are as defined for Formula 1, or an acîd addition salt thereof.
Formula Vl R1 C ~ C C N~
1 O B~L~
wherein X is halogen, methyl, or ethyl and R~, R~, R3, R4, A, B, and W are as defined for Formula 1, or an acid addi-tion salt thereof.
.~ 15 Formula Vll Rl2 ll /R3 Ri-- C -- C N~
/ N ~
B ~ ~ ~, wherein Rl and R2 are hydrogen, methyl, ethyl, or propyl;
R3 and R4 are methyl or ethyl; B is halogen or alkyl of from
2~ 1 to 3 carbon atoms; and Y and W are oxygen or sul fur, or an acid addition salt thereof.
The term alkyl of 1 to 6 carbon atoms, or 1 to 8, inclusive, denotes a straight or branched chain hydrocarbon ; group as exemplified by methyl, ethyl, propyl, isopropyl, ~:
butyl, isobutyl, tertiary butyl, pentyl, isopentyl, 3-methyl-- . .. ~ . .
1O 5 3 ~ 3 1 butyl, hexyl, isohexyl/ a~ mQThYIp~TY/~ 3-methylpentyl, heptyl, octyl, and the like.
Ilaloalkyl includes the term alkyl as defined above, ior example chloromethyl, dichloromethyl, triflyoxomethyl, 2-chloropropyl, 3 chloropropyl, 4-chlorobutyl, 3-chlorobutyl, 5-chloropentyl, 3-chloropentyl, 6-chlorohexyl, 4-chlorohexyl, 2-chlorohexyl, and the like.
Cycloalkyl of 3 to 6 carbon atoms is exemplified by cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Halogen is exemplified by fluorine, chlorine, bromine, and iodine.
Alk~xy is exemplified by methoxy, ethoxy, propoxy, and isopropoxy.
The compounds of Formulae 1, ~1, lla, 111, lV, V, Vi and Vii are prepared acco ~ ng to processes illustrated by the following reaction schemes: -.. _ .. . . .
~ - Process A
tt 0 ~ Rl-C-C-N
A ~ ~ Z +R~-C-C-N \ ~
Halogen ~ Z
wherein Rl,- R3, R4, A, B, and Z are as previously described, and Halogen is chlorine or bromine. The process is carried out by reacting a 2-haloalkanoamide with an appropriately substituted pyrazole in the presence of a base such as sodium hydride, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, or the like. The reaction cbr/
1~532J~
can be carried oul in ~b~;cnc~ Or a(kle(l ~olven~ or in a solvcn~, such as ben7erle~ ctllcr, tetlally(lloflllal7, In~tl~allol, '- ethanol, acctoneJ dH~ hylforlllanli~e, or ~he lik(. Wl~el-potassium carbonate or anhydro-ls sodium mctlloxide is uscd no solvent is necessary. The reaction is carried out at teoperatures of 0 to 200 C. The reaction product is isolated by convcntional tcchniqu~s, sucl- as chromatograpl~
crystallization, etc, Wl-en tllis procedure is used a n~ixture of isomers is formed at positions 3 and 5, and these isomet-s are easily separated. Th,s process is illus~rated in ex~mples 1-48 and 1~8-14~.
.
Process B
lCH3ll Rl-CH2- C- C - OR5 Halogen CIH3l IH~lOl RrlCH-CH C--OR5 + Rl CH2l-C-Rs A ~ Z B
Minor B MaJor CH3~ CH30 CH30 ~ /R9 ~rCH2-CI~ C-~ Rl-CH2-C- C-Cl RrCH2-l -C-OH
A ~ Z A - ~ Z A ~ ~ Z
B B B
wherein A, B, ~, R1, R3, and R4 are de~ined as above, halo-gen Ts chlorine or bromlnei and Rs is an alkyl yroup of 1 to . .
~0S32~1 G carl)orl a~ ls. rl~c ~irst st~) invo~ves tl~e re~ tion Df ~
~-haloallcanoic acid cstcr Wittl tlle I)yrazolc to give a nlajor and minor prodlJc~. Thc major prodllc~ is casily ~)uririe~ if desir~d by convcntional techniques such as chromatograplly.
The rcaction is carricd out usin~ a hase at t~rnpcratures of ~0 to 150 C. Thc basc can be sodium hydride, sodium methoxide or ethoxide and the like. The reaction can be carried out ir- absence o~ added solvel)t or in a solvent such as benzene, teLrahydrorul-an, dirlletllyl~ornlartHde and the like.
~0 To obtain the amide, the major product c~n be treated in conventional ways. The ester is hydrolyzed to the acid which is converted to the acid chloride wi th thionyl chlo- -ride and the like. Treating ~.he acid chlol-ide with an amine a~fords the product. When the crude ester mixture is trea~ed in the above manner, both major and minor ester products are converted into the corresponding amides. This process is illustrated by examples 49-67 and 144-145.
. ` Process C
O
H O R1-CHl-OR5 ~ N~ ~ R,-CH-C-OR5 ~ N ~
A- ~ Z Halo9en A ~ ~-Z
~, B B
i `1, , .
O
¦¦ ~ R3 Rl fH-~ N~R
"N
B
_g , .
" , " .
"
j2~'3 l(~S3;231 wherein A, BJ Z~ R1, R3, R~J and R5 are as described previously, and Halogen is chlorine or bromine. The reac-tion is carried out by reacting the pyrazole with an a-halo carboxylic acid ester in the presence of a base such as sodium hydride, sodium alkoxide, potassium carbonate and the like, to give a pyrazole-1-acetic acid ester. The reaction can be carried out in absence of added solvent or in a sol-vent such as ether, tetrahydrofuran, benzene, alcohol and the like. The ester is then hydro1yzed to the corresponding pyrazole-1-acetic acid. The acid is converted to the amide via an acid chloride using conventional techniques. The product is separated by crystallization, chromatography or ~ other suitable means known in the art. This process is ; illustrated in examples 68-93.
in a related procedure, the ester products initially formed in Processes B and C may be directly converted to the amide by reaction with the appropriate amine in a sealed reaction vessel at temperatures of ~0 to 200 C. The one step amidation reaction can be carried out in absence of added solvent, or in presence of a solvent, such as benzene, methanol, and the like.
Process D
25 Rl C ~ C C N\ ~ Rl C ~ N<
Br ~ Z NC ~ ~ Z
~(A) B(A) ^
. , - . . . : .. :
. . . - - .
,, ~ .
ll~S3Z3~
whereill Rl~ R2, R3, R~, ~, and Z are as defined abovc.
This process is used to prepare compounds of the Formula 1, wherein ~ or B is cyano. The process is carried out by reacting the pyrazole in a solvent, such as dimethylform-amide, with cuprous cyanide under reflux conditions for 2-24 hours. The product is separated using conventional methods, such as crystallization. This process is illus-trated in example 94.
Process E
HC-C-N~ Rl - C- I:-N~R
R~ ogen > A~ ~ z B B
- .
wherein A, B~ Z, Rl, R2, R3, and R4 are defined as above, and Halogen is preferably iodine or bromine. This process enables the addition of various alkyl groups to the parent pyrazole. The reaction is carried out by adding a solution of n-butyl lithium in hexane to the pyrazole in an inert atmosphere, such as nitrogen, in a solvent such as ether or tetrahydrofuran. Other strong bases, such as tert-butyl lithium and lithium diisopropylamide may be used in place of n-butyl lithium. An alkyl halide is added to this and the reaction is allowed to stir for 1-2 hours. The product is separated and isolated using conventional techniques.
This process is illustrate' in examples 95-107.
~11-cbr/
.
-. :
~'2'~, 53~31 Process F
Rz 0 R2 0 - ~C ~Il_ /R 3 l l l R3 Rl C I C N \ Rl- C ~ C- C ~R
N ~ ~ N
Agent Halogen wherein Al B, Z, R1, R2, R3, and R4 are defined as above provided that A or B or both are hydrogen. The halogenating agent, e.g., bromine, chlorine, tert-butyl hypochlori~e, ~r sulfuryl chloride, is added to the pyrazole in a solvent, such as chloroform, carbon tetrachloride, acetic acidJ and the product isolated using conventional techniques. Thi~
process is illustrated in examples 108-120 and ~46-148 , Process G
:
` CH30 :i I 11 / R3 .:
~ R CH C -C N
-~ 20 H Halogen CH30 + R~-fH-IH-e-N
A ~ z or Rl-CH=C -C-N \
,, ~ .
wherein AJ BJ Rl, R3, R4, and Z are as described previously and Halogen is chlorine or bromine. The reaction is carried out by reacting the pyrazole with an a-haloalkanoamide or an '~ 30 acrylamide at a temperature of 50 to 200 C. The reaction -'~ .
.. . .
- 1053Z3~
can ~e carri~d out in absence of added solvent, or in an inert solvent such as toluene, dimethyl ~ormamide and thc like. When the ~-haloalkanoamide is used, addition of 1 equivalent of a base such as sodium methoxide, sodium car-bonate and the like is advantageous; in this reaction, the ~-haloalkanoamide is first converted to the acrylamide which then reacts with the pyrazole. This-process is illustrated in examples 121-126 and example 149.
Proccss H
R2 l R2 S
Rl C~¦-C--C--N\ R~ C-b-l--~N\
A~ PeSs > A--k ~Z
~: . B
wherein Rl, R2, R3, R4, A, B, and Z are defined as before ~, for compounds of Formula 1. This process is carried out by adding phosphorus pentasulfide to the pyrazole in a solvent. This is heated over a period of 1-6 hours and the product separated by extraction, crystallization or other conventional techniques. Suitable solvents are pyridine, ~- benzene, dimethyl formamide, xylene, dioxane and the like.
This process is illustrated in examples 127-137.
The compounds of the Formula 1 of this invention have been found to be active as herbicides both pre- and post- emergent. The compounds of the Formula 1 can be used to prevent damage to field crops due to weed competition, and they can be used to prevent unsightly and deleterious growths of weeds on home lawns, golf courses, cemeteries, . . .
I
, 13 - cbr/
l(~S;~Z31 railroad rights-of-way, wa~erways, rice paddies ancl parks.
Compounds of the Formula l have been found to be highly ac~ive against both broadleaf and grassy weeds. Illus-tratively, against various weeds, e.g., crabgrass t ~ itaria sanyuinalis L.), yellow foxtail (Setaria glauca L.), wild oat (Avena fatua L.), bindweed (Convolvulus arvensis L.~, Johnson grass (Sorghum h epense L.), buckhorn plantain (Plantaqo lanceolata L.), curly dock (Rumex crispus L.), wild mustard (Brassica kaber DG.), pwrslanc (Portulaca oleracea L.), barnyard-grass (Echinochloa crusqalli L.), yellow nutsedge (cyperus esculentus), and purple nutsedge (Cyperus rotundus).
Illustratively, control and significant growth retardation of the foregoing weed species has been achieved using the compounds of this invention at rates of from 0.01 to 12.5 lbs. per acre. Depending upon the kinds of weeds to - be controlled, the stage of weed development, the degree of infestation, and the presence or absence of aesthetic or crop plants, the compounds of this invention can be applied to soil, germinating weed seeds, weed seedlings, plant growth media, growing plants, or any other selected situs for control ; of weeds at rates ranging from about 1/16 to 1/8 lb. per acre up to about 50 lbs. per acre. Ordinarily, the situs will be soilj but this term is used in the broad sense -- anywhere where weed growth might be a problem, e.g., gravel driveways, i railroad beds, flat built-up roofs, ponds, lakes, streams, and canals. Aquatic applications effectively use about 2 to about 10,000 or more, parts per million (ppm), by weight.
The compounds of Formula l can be applied to a situs .~ ' .
.~ ' - .
.~ .
~ ~ 14 -. . .
~. . ~ , . , - . :
105;~2;~
in a dispersible pure form, but dispersiblc rormulaliorls for hcrl)icidal use are prercrlcd. The ~ispcrsibl~ rorn~ul.1-tions or this inven~ion comprise a compound Or th~ For-r)ula I in a homo~encous, dispersiblc ~orm wi~h a Ilonlogeneous dispersiblc carricr. Adjuvan~s such as slIrfactants, hl~mec~
- tan~s, dispersantsJ adIlesive or s~icking or sprea~
agents, corrosion inhibitors, and anti-foanling agents can be included.
A homogeneous disperslble carrier comprehends a par~
culate solid carrier or a liquid carrier diluent. rhe compound can be dispersed in a liquid carrier diluent as a ; so1ute or as finely divided particles (suspension).
The term "dispersible", as used in this specification ` and in the claims, means matter in a liquid or particulate ; 15 state such that it can be evenly distributed over a given area or metered into a body of water. A "liquid" state includes true solutions as well as dispersions of particu-late solids in a liquid. Emulsions of one liquid in another, e.g.~ oil-in-water, are also contemplated. The active com^
pound can be in either the dispersed phase, the continuous phase, or partitioned between them both. In general, tne active compound will be preponderantly in the dispersed phase when emulsions are used. A "particulate" state includes the general concept of finely divided separate particles, and granular particles as large as 10 mesh (U.S.) or even somewhat lar~er when appropriate herbicidal prac-tice indicates an advantage in using larger granules.
- The granular particles could be included in what is termed an "interstitial" state, which contemplates the depos;tion sr entrapment o~ the active compaund within ~he . .
~15~
, ,- ; ;
~053Z~l inter-i~ices or a pornlJs body. ror ~xaml)l~, lh~ com~)olin(ls can be mixed with an elastolller, e.(J., natlJral rubber, chloroprcne, buLyl rubbcr, poly~tll~r and polycs~er uret~ les and the like, which may be ~urther pr~cessed according to - 5 conventional techniques in the elastomeric art. The latter elastomeric matrices as well as'c~nventional granules pro-vide a slow, sustained release of the active herbicide so that herbicidal concentrations of the active compound can be obtained over a prolonged interval ~or the contro1 oF
weeds.
Illustrative of the adjuvants named above, humec~-ants include glycerol, diethylene glycol, solubilized lignins (such as calcium ligninsul~onate), and the like. Disper-sants include bentonite, sodium, ammonium, calcium or 15 aluminum ligninsulfonate, condensed naphthalene sulfonate ~ and the like. Adhesive or sticking agents include vege~able j oils, naturally occurring gums, casein, and the like. A
. ~ . .' suitable c~rrosion inhibitor is epichlorohydrin, and suit-able anti-foamin~ agents such as fatty acids, e.g., sodium 20 stearate; and silicones.
Representative surfac-ants include alkyl sulfates and sult'onates, alkyl aryl sulfonates, sulfosuccinate esters, i polyoxyethylene sulfates, polyoxyctllylene-sorbitan esters, f, e.g.g monolaurate, alkyl aryl polyether sulfates, alkyl aryl polyether al'cohols, alkyl naphthalene sulfonates, ~' alkyl quaternary ammonium salts, sul~ated fatty acids and ' ' esters, sulfated fatty acid amides, glycerol mannitan J ` laurate, polyalkylether condensates o~ fatty acids or 1 alcoho1s, and the like.
30 Suitable surfactants include ~lends of alkyl aryl ~
.'',.' . ' ~;
. . .
-16- :
- .
' ;. ' ' .. :
r ~ ' :
~22') su1fonates ~r~d polyalcobol carboxylic clcid ~s~rs (Elllcol H-77), blen~s of polyoxyethylene et!lers and oil-soluble - sulfonates (Emcol H-400), blends of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Tritons X-151, X-161, and X-171), e.g., about equal parts of sodium aryl or alkyl-benzene sulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl aryl sulfonates and polyethoxylated vegetable oils (Agrimul N4S). It will be understood, of cour~e, that the sulfate and sulfonate surfactants suggested above will preferably be used in the form of their soluble salts, for example, their sodium salts. All of these surfactants are capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1~ or less. The dispersible powder formulations can be prepared with a mixture of surfactants of the types indicated if desired.
The concentration of the active compound of the Formula I according to this invention, in the new herbicidal formu- ;
lations of this invention is not usually a critical, limit-ing factor in achieving a desired herbicidal effect. The most important factor is how much compound is applied to an area of weeds to be controlled. It is readily apparent that one can apply a large amount of a formulation having ~ low concentration of active compound or a relatively small amount of a formulation having a high concentration. Whether - a low or high concentration should be used depends upon the mode of application, the amount and kinds of vegetation, and the thoroughness of coverage desired. The total amount to be applied depends upon the kinds of weeds and crop, if - _ :
~ ' ' ' . ~, . . , . , ., . . ~,.. , . ~ ...... . ..... . . ... . . . . . . .
~229 1~)53Z3~
:
any, the severity of infestation, the stage of plant develop-ment, and the season of the year.
Representative homogeneous dispersible formulations according to tnis invention include sprays, dusts, and granular formulations. Spray formulations are preferred for foliar applications and for uniformly controlled appli-~tions to a soil. Granular formulations are usually applied i~ bands spanning the seeded row, a1though broadcast distribution is advantageous when soil incorporation is practiced and a prolonged effect is desired.
The spray formulations in accordance with the invention can be aqueous solutions, aqueous suspensions, water-in-oil emulsions, oil-in-water emulsions , and oil solutions. The spray formulations will conveniently comprise from about 0.1% or lower to about 50% by weight or even higher, a vol~me of spray being applied so that a herbicidally effec-tive amount of compound of Formula I is distributed over the treated area. Sprays containing about 0.25 ounce to about 16 lbs. of compound of Formula I in a 20 gal. to 40 2Q gal. volume are applied to foliage or soil for effective herbicidal action.
Concentrates for preparing spray formulations are advantageously prepared by dissolving the active compounds of the invention in a solvent, or by dispersing the active 25 compounds in aidispersible solid or liquid carrier diluent.
IllustrativelyJ the herbicidally active compound of Formula I of this invention is dissolved or dispersed in water or a suitable water-miscible or water-immiscible inert organic liquid. Representative water-miscible organic liquids include acetone, methyl ethyl ketone, dimethylformamide, :3229 l~S3Z31 alcohols, monoalkyl ethers of ethylene glycol, ethyl acetate, and the like. Representative substan~ially water-immiscible organic liquids (i.e., a so1vent carrier which is soluble in water to the extent of less that 2.5~ by volume at tem-pera~ures of the order of 20 to 30 C.~ for preparingemulsifiabTe concentrates include petroleum oils, distil-lates, toluene, xylene, cumene, and like aromatic hydro-carbons, isoparaffin oil, mineral oil, and the like.
Advantageously, the concentration of active ingredient in the emulsifiable concentrates (~ith or without surfac-tant) can range from about 5~ to about 90%by weight, preferably from about 10~to about 40%. A concentrate comprising 20% (by weight) of the compound dissolved in a water-immiscible solvent of the kind noted above can be ~5 admixed with an aqueous medium in the proportions of 1~ ml.
of concentrate with 1 gal. of medium to give a mixture containing 700 parts of active ingredient per million parts of liguid carrier. Similarly, 1 qt. of a 20~ concentrate mixed with 40 gals. of water provides about 1200 ppm (parts per million) of active ingredient. In the same mannær, more concentrated solutions of active ingredient can be prepared.
Dùst formulations in accordance with the invention are readily prepared by dispersing the active compound in a dispersible solid by grinding a mixture of the compound and a pulverulent solid carrier in the presence of each other.
Grinding is conveniently accomplished in a ball mill, a hammermill, or by air-blast micronization. These dust compositions can also be prepared by dissolving the compound ~0 of Formula I in a volatile solvent such as methylene chlo-. . - , . .
1053~3~ ` ~
ride, mixing the solution with a pulverulent solid carrier, evaporating the solvent, and pulverizing the impregnated carrier. A suitable ultimate particle size is less than 60 microns. Preferabl YJ 95% of the particles are less than 50 microns, and about 75~ are 5 to 20 microns. Dusts of this degree of comminution are conveniently free-flowing.
Representative suitable pulverulent solid carriers include the natural clays such as China, Georgia, Barden, Attapulgus, kaolin, and Montmorillonite clays; minerals in their natural forms as they are obtained from the earth such as talc, pyrophyllite, quartz, diatomaceous earth, fuller's earth, chalk, rock phosphates and sulfates, calcium carbonates, sulfur, silica and silicates; chemically modi-fied minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, precipitated calcium silicate, synthetic magnesium silicate, and colloidal silica; and organic flours such as wood, walnut shell, soy-bean, cottonseed~ and tobacco flours, and free-flowing hydrophobic starches.
The proportions of pulverulent carrier and compound of Formu'a I can vary over a wide range depending upon the plants to be controlled, rates of application according to ; equ7pment available, and the conditions of treatment. In general, dust formulations can contain up to about 90% (on a weight basis) of the active ingredient. 3usts having as little as 0.001~ of the active ingredient can be used, but a generally preferred proportion is from about 0.50% to about 20% of active ingredient.
Advantageously, a dust formulation as described above ~0 includes a surfactant, because about 0.1~ to about 12~ of a 322~) ~ (~53Z3~
surfactant prol--otes dispersibility of a dust in w~ter and facilitates formulation of aqueous sprays or di~persibility of a dust l~orrnulation appl ied di rectl y to water surfaces or a~uatic weeds. Dust formu1atior~s cornprising a surfactant 5 are known as dispersible or wett:able powders. As indicated, dispersible or wettable powders can be admixed wi th water to obtain any desired concentration up to about 50,~ w/v of active ingredient. The dispersible or wettable powders can conveniently comprise frorn about: 10,~ to about 90,~ active 10 i ngredient, preferabl y about ~iO% to about 80%.
A suitable dispersible powder formulation is obtained by blending and milling 327 lbs. of Georgia Clay, 4.5 lbs.
olF calcium alkyl aryl benzene çulfonate (NeKal BA77) as a wetting agent, 9 lbs~ of a polymerized sodium salt of sub-15 stituted benzoid long-chain sulfonic acid (Daxad 27) as a d i spers i ng agent, and 113 1 bs . of the act i ve i ngred i ent .
The resul t i ng formul at i on has the fol l ow i ng percentage cornposi tion (parts herein are by weight unless otherwise specified):
Active ingredient 25%
Calcium alkyl aryl benzene sul fonate 1,g Pol yme r i zed sod i um sa 1 t of s ub -st i tuted benzoi d l ong-cha i n sul fonic acid 2~
Georgia Clay 72,¢
This formulationJ when dispersed in water a~ the rate of 10 lbs. per 100 gals., gives a spray formulation contain Ing about 0.~% (~000 ppm) active ingredient which can be 30 appl ied to weeds at the rate of 40 gal s. per acre to give a '; .
~ , . , ~
~053;~31 total application of act;ve ingredient of 1 lb. per acre Fur~her in accordance wi th this invention, formulations of the compounds of the Formula I with oil are particularly efficacious, and herbicidal action of the conpound is im-proved. Any petroleum oil can be used s~ long as it is nots~ viscous as to be too difficult ~o disperse. A non-phytotoxic oil is satisfactory.
Advantageously, a 50% wettable powder of the herbicidal active ingredient is mixed with about 38 gals. water and 2 gals. oil for spray application.
The following examples are illustrative of the process and products of the present invention but are not to be construed as limiting.
Exam~le 1 N,N,a,4-Tetramethyl-3-phenylpyrazole-1-acet-amide and N,N,~,4-tetramethyl-5-phenylpyrazole-1-acetamide To a solution of the sod;um salt of 4-methyl-3-phenyl-pyrazole, prepared by addition of sodium hydride (3.G 9., 57~ in oil, 0.071 mole) to 4-methyl-~-phenylpyrazole (10.5 f 20 9.~ 0.066 mole~ in THF (100 ml.), was added 10.0 9. (0.075 m~le) of N,N-dimethyl-2-chloropropionamide. After 18 hours, the solution was evaporated and the residue was partitioned between chloroform and water The residue obtained on ~ evaporation o~ the chloroform phase was chromatographed on `~ 25 sll iGa gel us ing benzene.ethyl acetate as eluant to give, as the first product eluted from the column, N,N,,4-tetra-;~ methyl-3-phenylpyrazole-1-acetamide (17 7 9.). Two ;; recrystallizations from cyclohexane gave the analytical sample as fine needles, m.p. 74.5-76.5 C.: nmr (C~Cl9) ~0 8 1.63 tdJ 3, CH3-CH), 2.20 (s, 3, ArCHg~, 2.92 (s, 3J
-22~
:~229
The term alkyl of 1 to 6 carbon atoms, or 1 to 8, inclusive, denotes a straight or branched chain hydrocarbon ; group as exemplified by methyl, ethyl, propyl, isopropyl, ~:
butyl, isobutyl, tertiary butyl, pentyl, isopentyl, 3-methyl-- . .. ~ . .
1O 5 3 ~ 3 1 butyl, hexyl, isohexyl/ a~ mQThYIp~TY/~ 3-methylpentyl, heptyl, octyl, and the like.
Ilaloalkyl includes the term alkyl as defined above, ior example chloromethyl, dichloromethyl, triflyoxomethyl, 2-chloropropyl, 3 chloropropyl, 4-chlorobutyl, 3-chlorobutyl, 5-chloropentyl, 3-chloropentyl, 6-chlorohexyl, 4-chlorohexyl, 2-chlorohexyl, and the like.
Cycloalkyl of 3 to 6 carbon atoms is exemplified by cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Halogen is exemplified by fluorine, chlorine, bromine, and iodine.
Alk~xy is exemplified by methoxy, ethoxy, propoxy, and isopropoxy.
The compounds of Formulae 1, ~1, lla, 111, lV, V, Vi and Vii are prepared acco ~ ng to processes illustrated by the following reaction schemes: -.. _ .. . . .
~ - Process A
tt 0 ~ Rl-C-C-N
A ~ ~ Z +R~-C-C-N \ ~
Halogen ~ Z
wherein Rl,- R3, R4, A, B, and Z are as previously described, and Halogen is chlorine or bromine. The process is carried out by reacting a 2-haloalkanoamide with an appropriately substituted pyrazole in the presence of a base such as sodium hydride, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, or the like. The reaction cbr/
1~532J~
can be carried oul in ~b~;cnc~ Or a(kle(l ~olven~ or in a solvcn~, such as ben7erle~ ctllcr, tetlally(lloflllal7, In~tl~allol, '- ethanol, acctoneJ dH~ hylforlllanli~e, or ~he lik(. Wl~el-potassium carbonate or anhydro-ls sodium mctlloxide is uscd no solvent is necessary. The reaction is carried out at teoperatures of 0 to 200 C. The reaction product is isolated by convcntional tcchniqu~s, sucl- as chromatograpl~
crystallization, etc, Wl-en tllis procedure is used a n~ixture of isomers is formed at positions 3 and 5, and these isomet-s are easily separated. Th,s process is illus~rated in ex~mples 1-48 and 1~8-14~.
.
Process B
lCH3ll Rl-CH2- C- C - OR5 Halogen CIH3l IH~lOl RrlCH-CH C--OR5 + Rl CH2l-C-Rs A ~ Z B
Minor B MaJor CH3~ CH30 CH30 ~ /R9 ~rCH2-CI~ C-~ Rl-CH2-C- C-Cl RrCH2-l -C-OH
A ~ Z A - ~ Z A ~ ~ Z
B B B
wherein A, B, ~, R1, R3, and R4 are de~ined as above, halo-gen Ts chlorine or bromlnei and Rs is an alkyl yroup of 1 to . .
~0S32~1 G carl)orl a~ ls. rl~c ~irst st~) invo~ves tl~e re~ tion Df ~
~-haloallcanoic acid cstcr Wittl tlle I)yrazolc to give a nlajor and minor prodlJc~. Thc major prodllc~ is casily ~)uririe~ if desir~d by convcntional techniques such as chromatograplly.
The rcaction is carricd out usin~ a hase at t~rnpcratures of ~0 to 150 C. Thc basc can be sodium hydride, sodium methoxide or ethoxide and the like. The reaction can be carried out ir- absence o~ added solvel)t or in a solvent such as benzene, teLrahydrorul-an, dirlletllyl~ornlartHde and the like.
~0 To obtain the amide, the major product c~n be treated in conventional ways. The ester is hydrolyzed to the acid which is converted to the acid chloride wi th thionyl chlo- -ride and the like. Treating ~.he acid chlol-ide with an amine a~fords the product. When the crude ester mixture is trea~ed in the above manner, both major and minor ester products are converted into the corresponding amides. This process is illustrated by examples 49-67 and 144-145.
. ` Process C
O
H O R1-CHl-OR5 ~ N~ ~ R,-CH-C-OR5 ~ N ~
A- ~ Z Halo9en A ~ ~-Z
~, B B
i `1, , .
O
¦¦ ~ R3 Rl fH-~ N~R
"N
B
_g , .
" , " .
"
j2~'3 l(~S3;231 wherein A, BJ Z~ R1, R3, R~J and R5 are as described previously, and Halogen is chlorine or bromine. The reac-tion is carried out by reacting the pyrazole with an a-halo carboxylic acid ester in the presence of a base such as sodium hydride, sodium alkoxide, potassium carbonate and the like, to give a pyrazole-1-acetic acid ester. The reaction can be carried out in absence of added solvent or in a sol-vent such as ether, tetrahydrofuran, benzene, alcohol and the like. The ester is then hydro1yzed to the corresponding pyrazole-1-acetic acid. The acid is converted to the amide via an acid chloride using conventional techniques. The product is separated by crystallization, chromatography or ~ other suitable means known in the art. This process is ; illustrated in examples 68-93.
in a related procedure, the ester products initially formed in Processes B and C may be directly converted to the amide by reaction with the appropriate amine in a sealed reaction vessel at temperatures of ~0 to 200 C. The one step amidation reaction can be carried out in absence of added solvent, or in presence of a solvent, such as benzene, methanol, and the like.
Process D
25 Rl C ~ C C N\ ~ Rl C ~ N<
Br ~ Z NC ~ ~ Z
~(A) B(A) ^
. , - . . . : .. :
. . . - - .
,, ~ .
ll~S3Z3~
whereill Rl~ R2, R3, R~, ~, and Z are as defined abovc.
This process is used to prepare compounds of the Formula 1, wherein ~ or B is cyano. The process is carried out by reacting the pyrazole in a solvent, such as dimethylform-amide, with cuprous cyanide under reflux conditions for 2-24 hours. The product is separated using conventional methods, such as crystallization. This process is illus-trated in example 94.
Process E
HC-C-N~ Rl - C- I:-N~R
R~ ogen > A~ ~ z B B
- .
wherein A, B~ Z, Rl, R2, R3, and R4 are defined as above, and Halogen is preferably iodine or bromine. This process enables the addition of various alkyl groups to the parent pyrazole. The reaction is carried out by adding a solution of n-butyl lithium in hexane to the pyrazole in an inert atmosphere, such as nitrogen, in a solvent such as ether or tetrahydrofuran. Other strong bases, such as tert-butyl lithium and lithium diisopropylamide may be used in place of n-butyl lithium. An alkyl halide is added to this and the reaction is allowed to stir for 1-2 hours. The product is separated and isolated using conventional techniques.
This process is illustrate' in examples 95-107.
~11-cbr/
.
-. :
~'2'~, 53~31 Process F
Rz 0 R2 0 - ~C ~Il_ /R 3 l l l R3 Rl C I C N \ Rl- C ~ C- C ~R
N ~ ~ N
Agent Halogen wherein Al B, Z, R1, R2, R3, and R4 are defined as above provided that A or B or both are hydrogen. The halogenating agent, e.g., bromine, chlorine, tert-butyl hypochlori~e, ~r sulfuryl chloride, is added to the pyrazole in a solvent, such as chloroform, carbon tetrachloride, acetic acidJ and the product isolated using conventional techniques. Thi~
process is illustrated in examples 108-120 and ~46-148 , Process G
:
` CH30 :i I 11 / R3 .:
~ R CH C -C N
-~ 20 H Halogen CH30 + R~-fH-IH-e-N
A ~ z or Rl-CH=C -C-N \
,, ~ .
wherein AJ BJ Rl, R3, R4, and Z are as described previously and Halogen is chlorine or bromine. The reaction is carried out by reacting the pyrazole with an a-haloalkanoamide or an '~ 30 acrylamide at a temperature of 50 to 200 C. The reaction -'~ .
.. . .
- 1053Z3~
can ~e carri~d out in absence of added solvent, or in an inert solvent such as toluene, dimethyl ~ormamide and thc like. When the ~-haloalkanoamide is used, addition of 1 equivalent of a base such as sodium methoxide, sodium car-bonate and the like is advantageous; in this reaction, the ~-haloalkanoamide is first converted to the acrylamide which then reacts with the pyrazole. This-process is illustrated in examples 121-126 and example 149.
Proccss H
R2 l R2 S
Rl C~¦-C--C--N\ R~ C-b-l--~N\
A~ PeSs > A--k ~Z
~: . B
wherein Rl, R2, R3, R4, A, B, and Z are defined as before ~, for compounds of Formula 1. This process is carried out by adding phosphorus pentasulfide to the pyrazole in a solvent. This is heated over a period of 1-6 hours and the product separated by extraction, crystallization or other conventional techniques. Suitable solvents are pyridine, ~- benzene, dimethyl formamide, xylene, dioxane and the like.
This process is illustrated in examples 127-137.
The compounds of the Formula 1 of this invention have been found to be active as herbicides both pre- and post- emergent. The compounds of the Formula 1 can be used to prevent damage to field crops due to weed competition, and they can be used to prevent unsightly and deleterious growths of weeds on home lawns, golf courses, cemeteries, . . .
I
, 13 - cbr/
l(~S;~Z31 railroad rights-of-way, wa~erways, rice paddies ancl parks.
Compounds of the Formula l have been found to be highly ac~ive against both broadleaf and grassy weeds. Illus-tratively, against various weeds, e.g., crabgrass t ~ itaria sanyuinalis L.), yellow foxtail (Setaria glauca L.), wild oat (Avena fatua L.), bindweed (Convolvulus arvensis L.~, Johnson grass (Sorghum h epense L.), buckhorn plantain (Plantaqo lanceolata L.), curly dock (Rumex crispus L.), wild mustard (Brassica kaber DG.), pwrslanc (Portulaca oleracea L.), barnyard-grass (Echinochloa crusqalli L.), yellow nutsedge (cyperus esculentus), and purple nutsedge (Cyperus rotundus).
Illustratively, control and significant growth retardation of the foregoing weed species has been achieved using the compounds of this invention at rates of from 0.01 to 12.5 lbs. per acre. Depending upon the kinds of weeds to - be controlled, the stage of weed development, the degree of infestation, and the presence or absence of aesthetic or crop plants, the compounds of this invention can be applied to soil, germinating weed seeds, weed seedlings, plant growth media, growing plants, or any other selected situs for control ; of weeds at rates ranging from about 1/16 to 1/8 lb. per acre up to about 50 lbs. per acre. Ordinarily, the situs will be soilj but this term is used in the broad sense -- anywhere where weed growth might be a problem, e.g., gravel driveways, i railroad beds, flat built-up roofs, ponds, lakes, streams, and canals. Aquatic applications effectively use about 2 to about 10,000 or more, parts per million (ppm), by weight.
The compounds of Formula l can be applied to a situs .~ ' .
.~ ' - .
.~ .
~ ~ 14 -. . .
~. . ~ , . , - . :
105;~2;~
in a dispersible pure form, but dispersiblc rormulaliorls for hcrl)icidal use are prercrlcd. The ~ispcrsibl~ rorn~ul.1-tions or this inven~ion comprise a compound Or th~ For-r)ula I in a homo~encous, dispersiblc ~orm wi~h a Ilonlogeneous dispersiblc carricr. Adjuvan~s such as slIrfactants, hl~mec~
- tan~s, dispersantsJ adIlesive or s~icking or sprea~
agents, corrosion inhibitors, and anti-foanling agents can be included.
A homogeneous disperslble carrier comprehends a par~
culate solid carrier or a liquid carrier diluent. rhe compound can be dispersed in a liquid carrier diluent as a ; so1ute or as finely divided particles (suspension).
The term "dispersible", as used in this specification ` and in the claims, means matter in a liquid or particulate ; 15 state such that it can be evenly distributed over a given area or metered into a body of water. A "liquid" state includes true solutions as well as dispersions of particu-late solids in a liquid. Emulsions of one liquid in another, e.g.~ oil-in-water, are also contemplated. The active com^
pound can be in either the dispersed phase, the continuous phase, or partitioned between them both. In general, tne active compound will be preponderantly in the dispersed phase when emulsions are used. A "particulate" state includes the general concept of finely divided separate particles, and granular particles as large as 10 mesh (U.S.) or even somewhat lar~er when appropriate herbicidal prac-tice indicates an advantage in using larger granules.
- The granular particles could be included in what is termed an "interstitial" state, which contemplates the depos;tion sr entrapment o~ the active compaund within ~he . .
~15~
, ,- ; ;
~053Z~l inter-i~ices or a pornlJs body. ror ~xaml)l~, lh~ com~)olin(ls can be mixed with an elastolller, e.(J., natlJral rubber, chloroprcne, buLyl rubbcr, poly~tll~r and polycs~er uret~ les and the like, which may be ~urther pr~cessed according to - 5 conventional techniques in the elastomeric art. The latter elastomeric matrices as well as'c~nventional granules pro-vide a slow, sustained release of the active herbicide so that herbicidal concentrations of the active compound can be obtained over a prolonged interval ~or the contro1 oF
weeds.
Illustrative of the adjuvants named above, humec~-ants include glycerol, diethylene glycol, solubilized lignins (such as calcium ligninsul~onate), and the like. Disper-sants include bentonite, sodium, ammonium, calcium or 15 aluminum ligninsulfonate, condensed naphthalene sulfonate ~ and the like. Adhesive or sticking agents include vege~able j oils, naturally occurring gums, casein, and the like. A
. ~ . .' suitable c~rrosion inhibitor is epichlorohydrin, and suit-able anti-foamin~ agents such as fatty acids, e.g., sodium 20 stearate; and silicones.
Representative surfac-ants include alkyl sulfates and sult'onates, alkyl aryl sulfonates, sulfosuccinate esters, i polyoxyethylene sulfates, polyoxyctllylene-sorbitan esters, f, e.g.g monolaurate, alkyl aryl polyether sulfates, alkyl aryl polyether al'cohols, alkyl naphthalene sulfonates, ~' alkyl quaternary ammonium salts, sul~ated fatty acids and ' ' esters, sulfated fatty acid amides, glycerol mannitan J ` laurate, polyalkylether condensates o~ fatty acids or 1 alcoho1s, and the like.
30 Suitable surfactants include ~lends of alkyl aryl ~
.'',.' . ' ~;
. . .
-16- :
- .
' ;. ' ' .. :
r ~ ' :
~22') su1fonates ~r~d polyalcobol carboxylic clcid ~s~rs (Elllcol H-77), blen~s of polyoxyethylene et!lers and oil-soluble - sulfonates (Emcol H-400), blends of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Tritons X-151, X-161, and X-171), e.g., about equal parts of sodium aryl or alkyl-benzene sulfonate and isooctylphenoxy polyethoxy ethanol containing about 12 ethoxy groups, and blends of calcium alkyl aryl sulfonates and polyethoxylated vegetable oils (Agrimul N4S). It will be understood, of cour~e, that the sulfate and sulfonate surfactants suggested above will preferably be used in the form of their soluble salts, for example, their sodium salts. All of these surfactants are capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1~ or less. The dispersible powder formulations can be prepared with a mixture of surfactants of the types indicated if desired.
The concentration of the active compound of the Formula I according to this invention, in the new herbicidal formu- ;
lations of this invention is not usually a critical, limit-ing factor in achieving a desired herbicidal effect. The most important factor is how much compound is applied to an area of weeds to be controlled. It is readily apparent that one can apply a large amount of a formulation having ~ low concentration of active compound or a relatively small amount of a formulation having a high concentration. Whether - a low or high concentration should be used depends upon the mode of application, the amount and kinds of vegetation, and the thoroughness of coverage desired. The total amount to be applied depends upon the kinds of weeds and crop, if - _ :
~ ' ' ' . ~, . . , . , ., . . ~,.. , . ~ ...... . ..... . . ... . . . . . . .
~229 1~)53Z3~
:
any, the severity of infestation, the stage of plant develop-ment, and the season of the year.
Representative homogeneous dispersible formulations according to tnis invention include sprays, dusts, and granular formulations. Spray formulations are preferred for foliar applications and for uniformly controlled appli-~tions to a soil. Granular formulations are usually applied i~ bands spanning the seeded row, a1though broadcast distribution is advantageous when soil incorporation is practiced and a prolonged effect is desired.
The spray formulations in accordance with the invention can be aqueous solutions, aqueous suspensions, water-in-oil emulsions, oil-in-water emulsions , and oil solutions. The spray formulations will conveniently comprise from about 0.1% or lower to about 50% by weight or even higher, a vol~me of spray being applied so that a herbicidally effec-tive amount of compound of Formula I is distributed over the treated area. Sprays containing about 0.25 ounce to about 16 lbs. of compound of Formula I in a 20 gal. to 40 2Q gal. volume are applied to foliage or soil for effective herbicidal action.
Concentrates for preparing spray formulations are advantageously prepared by dissolving the active compounds of the invention in a solvent, or by dispersing the active 25 compounds in aidispersible solid or liquid carrier diluent.
IllustrativelyJ the herbicidally active compound of Formula I of this invention is dissolved or dispersed in water or a suitable water-miscible or water-immiscible inert organic liquid. Representative water-miscible organic liquids include acetone, methyl ethyl ketone, dimethylformamide, :3229 l~S3Z31 alcohols, monoalkyl ethers of ethylene glycol, ethyl acetate, and the like. Representative substan~ially water-immiscible organic liquids (i.e., a so1vent carrier which is soluble in water to the extent of less that 2.5~ by volume at tem-pera~ures of the order of 20 to 30 C.~ for preparingemulsifiabTe concentrates include petroleum oils, distil-lates, toluene, xylene, cumene, and like aromatic hydro-carbons, isoparaffin oil, mineral oil, and the like.
Advantageously, the concentration of active ingredient in the emulsifiable concentrates (~ith or without surfac-tant) can range from about 5~ to about 90%by weight, preferably from about 10~to about 40%. A concentrate comprising 20% (by weight) of the compound dissolved in a water-immiscible solvent of the kind noted above can be ~5 admixed with an aqueous medium in the proportions of 1~ ml.
of concentrate with 1 gal. of medium to give a mixture containing 700 parts of active ingredient per million parts of liguid carrier. Similarly, 1 qt. of a 20~ concentrate mixed with 40 gals. of water provides about 1200 ppm (parts per million) of active ingredient. In the same mannær, more concentrated solutions of active ingredient can be prepared.
Dùst formulations in accordance with the invention are readily prepared by dispersing the active compound in a dispersible solid by grinding a mixture of the compound and a pulverulent solid carrier in the presence of each other.
Grinding is conveniently accomplished in a ball mill, a hammermill, or by air-blast micronization. These dust compositions can also be prepared by dissolving the compound ~0 of Formula I in a volatile solvent such as methylene chlo-. . - , . .
1053~3~ ` ~
ride, mixing the solution with a pulverulent solid carrier, evaporating the solvent, and pulverizing the impregnated carrier. A suitable ultimate particle size is less than 60 microns. Preferabl YJ 95% of the particles are less than 50 microns, and about 75~ are 5 to 20 microns. Dusts of this degree of comminution are conveniently free-flowing.
Representative suitable pulverulent solid carriers include the natural clays such as China, Georgia, Barden, Attapulgus, kaolin, and Montmorillonite clays; minerals in their natural forms as they are obtained from the earth such as talc, pyrophyllite, quartz, diatomaceous earth, fuller's earth, chalk, rock phosphates and sulfates, calcium carbonates, sulfur, silica and silicates; chemically modi-fied minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, precipitated calcium silicate, synthetic magnesium silicate, and colloidal silica; and organic flours such as wood, walnut shell, soy-bean, cottonseed~ and tobacco flours, and free-flowing hydrophobic starches.
The proportions of pulverulent carrier and compound of Formu'a I can vary over a wide range depending upon the plants to be controlled, rates of application according to ; equ7pment available, and the conditions of treatment. In general, dust formulations can contain up to about 90% (on a weight basis) of the active ingredient. 3usts having as little as 0.001~ of the active ingredient can be used, but a generally preferred proportion is from about 0.50% to about 20% of active ingredient.
Advantageously, a dust formulation as described above ~0 includes a surfactant, because about 0.1~ to about 12~ of a 322~) ~ (~53Z3~
surfactant prol--otes dispersibility of a dust in w~ter and facilitates formulation of aqueous sprays or di~persibility of a dust l~orrnulation appl ied di rectl y to water surfaces or a~uatic weeds. Dust formu1atior~s cornprising a surfactant 5 are known as dispersible or wett:able powders. As indicated, dispersible or wettable powders can be admixed wi th water to obtain any desired concentration up to about 50,~ w/v of active ingredient. The dispersible or wettable powders can conveniently comprise frorn about: 10,~ to about 90,~ active 10 i ngredient, preferabl y about ~iO% to about 80%.
A suitable dispersible powder formulation is obtained by blending and milling 327 lbs. of Georgia Clay, 4.5 lbs.
olF calcium alkyl aryl benzene çulfonate (NeKal BA77) as a wetting agent, 9 lbs~ of a polymerized sodium salt of sub-15 stituted benzoid long-chain sulfonic acid (Daxad 27) as a d i spers i ng agent, and 113 1 bs . of the act i ve i ngred i ent .
The resul t i ng formul at i on has the fol l ow i ng percentage cornposi tion (parts herein are by weight unless otherwise specified):
Active ingredient 25%
Calcium alkyl aryl benzene sul fonate 1,g Pol yme r i zed sod i um sa 1 t of s ub -st i tuted benzoi d l ong-cha i n sul fonic acid 2~
Georgia Clay 72,¢
This formulationJ when dispersed in water a~ the rate of 10 lbs. per 100 gals., gives a spray formulation contain Ing about 0.~% (~000 ppm) active ingredient which can be 30 appl ied to weeds at the rate of 40 gal s. per acre to give a '; .
~ , . , ~
~053;~31 total application of act;ve ingredient of 1 lb. per acre Fur~her in accordance wi th this invention, formulations of the compounds of the Formula I with oil are particularly efficacious, and herbicidal action of the conpound is im-proved. Any petroleum oil can be used s~ long as it is nots~ viscous as to be too difficult ~o disperse. A non-phytotoxic oil is satisfactory.
Advantageously, a 50% wettable powder of the herbicidal active ingredient is mixed with about 38 gals. water and 2 gals. oil for spray application.
The following examples are illustrative of the process and products of the present invention but are not to be construed as limiting.
Exam~le 1 N,N,a,4-Tetramethyl-3-phenylpyrazole-1-acet-amide and N,N,~,4-tetramethyl-5-phenylpyrazole-1-acetamide To a solution of the sod;um salt of 4-methyl-3-phenyl-pyrazole, prepared by addition of sodium hydride (3.G 9., 57~ in oil, 0.071 mole) to 4-methyl-~-phenylpyrazole (10.5 f 20 9.~ 0.066 mole~ in THF (100 ml.), was added 10.0 9. (0.075 m~le) of N,N-dimethyl-2-chloropropionamide. After 18 hours, the solution was evaporated and the residue was partitioned between chloroform and water The residue obtained on ~ evaporation o~ the chloroform phase was chromatographed on `~ 25 sll iGa gel us ing benzene.ethyl acetate as eluant to give, as the first product eluted from the column, N,N,,4-tetra-;~ methyl-3-phenylpyrazole-1-acetamide (17 7 9.). Two ;; recrystallizations from cyclohexane gave the analytical sample as fine needles, m.p. 74.5-76.5 C.: nmr (C~Cl9) ~0 8 1.63 tdJ 3, CH3-CH), 2.20 (s, 3, ArCHg~, 2.92 (s, 3J
-22~
:~229
3~
N-CH~), 3.02 (s, 3, N-CH3), 5.43 (9, 1, CH3CH), 7.3G-7.50 (m, 4, ArH) and 7.56-7.80 (m, 2, ArH).
Calc'd. for C1sHlgN30:
C, 70.00; H, '7.44; N, 16.33.
Found: C, 70.08; H, 7.46; N~ 16.62.
Continued elution of the column gave N,N,a,4-tetra-methyl-5 phenylpyra~ole-1-acetamide (2.4 9.). Recrys-tallization from benzene:Skellysolve B followed by ethyl acetate gave the analytical sample, m.p. 88-go C.:
nmr (CDCl3) ~ 1.67 (d, 3, CH3CH), 1.97 (s, ~, ArCH3~, 2.57 (s, ~, N-CH3), 2.83 (s, 3, N-CH3), 5.02 (q, 1, CH3CH) and 7.15-7.55 (m, 6, ArH).
Analysis:
Calc'd. for C15H1gN30:
C, 70.00; HJ 7.44; N, 16.33.
Found: C, 70.13; HJ 7.51; N, 16.49. --Alternative Synthesis for N,~,a,4-tetrameth~-3-phen~ -A mixture of 4-me~hyl-3-phenylpyrazole ~3.65 9., 0.02~ mole) N,N-dimethyl-2-chloropropion-amide (3.78 9., 0.027 mole) and anhydrous potassium ~rbonate (4.4 g., 0.032 ~ole) was heated with stirring at 130 C. for 6 hours. The reaction mixture was cooled and crystallized from 50~ aqueous methanol to give 4.5 9. of N,N,a,4-tetramethyl-3-phenyl-pyrazole-1-acetamide as large rods, m.p. 87-89 C.
N,N,a-Trimethyl-~-phenylpyrazole-1-acetamide and N,N,a-trimethyl-5-phenylpyrazole-1-acetamide Using the procedure of Example 1, but substituting .
` 3229 .
~ 105;~;231 5-phenylpyrazole for 4-methyl-3-phenylpyrazol~ there was obta i ned N,N, a-tr imethyl -3-phenyl pyrazole-l -acetamide w i th a melting point of 79.5-80 C.
5Calc'd. for C~4Hl7N3Q:
C, 69.11; H, 7.04; N, 17.27.
Found: C, 69.42; H, 7.03; N, 17.52.
and N~N~a-trimethyl-5-phenylpyrazole-1-ace~amide as an oil.
Anal~sis 10Calcld. for C14H17N30:
C, 69.11 i HJ 7.04; N, 17.27.
Found: C, 67.86; H, 7.18; N, 16.62.
Example ~ N~NJaJ5-Tetramethyl-3-phenylpyrazole-l-acetamide and N,N,a,3 tetramethyl-5-phenylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained NJNJaJ5-tetramethyl-3-phenylpyrazole 1-acetamide with a melting point of 98-99 C. I
.' I
.. 20 Calc'd. for C15H~9N30: `
C, 70.00; H, 7.44; N, 16.33 Found: C, 70.03; H, 7.51; N, 16.53. ,l --and N,N,a,3-tetramethyl-5-phenylpyrazole-1-acetamide with ;.~ a melting point of 91-9~ C
,, .
Ana ~ :
`~: Calc'd. for Cl5H1~N
'! C, 70-00; ~, r.44; N, 16.3~.
, ~ I
Found: C, 70. 05; Il, 7.38; N, 16.39. I
,: . ; :,
N-CH~), 3.02 (s, 3, N-CH3), 5.43 (9, 1, CH3CH), 7.3G-7.50 (m, 4, ArH) and 7.56-7.80 (m, 2, ArH).
Calc'd. for C1sHlgN30:
C, 70.00; H, '7.44; N, 16.33.
Found: C, 70.08; H, 7.46; N~ 16.62.
Continued elution of the column gave N,N,a,4-tetra-methyl-5 phenylpyra~ole-1-acetamide (2.4 9.). Recrys-tallization from benzene:Skellysolve B followed by ethyl acetate gave the analytical sample, m.p. 88-go C.:
nmr (CDCl3) ~ 1.67 (d, 3, CH3CH), 1.97 (s, ~, ArCH3~, 2.57 (s, ~, N-CH3), 2.83 (s, 3, N-CH3), 5.02 (q, 1, CH3CH) and 7.15-7.55 (m, 6, ArH).
Analysis:
Calc'd. for C15H1gN30:
C, 70.00; HJ 7.44; N, 16.33.
Found: C, 70.13; HJ 7.51; N, 16.49. --Alternative Synthesis for N,~,a,4-tetrameth~-3-phen~ -A mixture of 4-me~hyl-3-phenylpyrazole ~3.65 9., 0.02~ mole) N,N-dimethyl-2-chloropropion-amide (3.78 9., 0.027 mole) and anhydrous potassium ~rbonate (4.4 g., 0.032 ~ole) was heated with stirring at 130 C. for 6 hours. The reaction mixture was cooled and crystallized from 50~ aqueous methanol to give 4.5 9. of N,N,a,4-tetramethyl-3-phenyl-pyrazole-1-acetamide as large rods, m.p. 87-89 C.
N,N,a-Trimethyl-~-phenylpyrazole-1-acetamide and N,N,a-trimethyl-5-phenylpyrazole-1-acetamide Using the procedure of Example 1, but substituting .
` 3229 .
~ 105;~;231 5-phenylpyrazole for 4-methyl-3-phenylpyrazol~ there was obta i ned N,N, a-tr imethyl -3-phenyl pyrazole-l -acetamide w i th a melting point of 79.5-80 C.
5Calc'd. for C~4Hl7N3Q:
C, 69.11; H, 7.04; N, 17.27.
Found: C, 69.42; H, 7.03; N, 17.52.
and N~N~a-trimethyl-5-phenylpyrazole-1-ace~amide as an oil.
Anal~sis 10Calcld. for C14H17N30:
C, 69.11 i HJ 7.04; N, 17.27.
Found: C, 67.86; H, 7.18; N, 16.62.
Example ~ N~NJaJ5-Tetramethyl-3-phenylpyrazole-l-acetamide and N,N,a,3 tetramethyl-5-phenylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained NJNJaJ5-tetramethyl-3-phenylpyrazole 1-acetamide with a melting point of 98-99 C. I
.' I
.. 20 Calc'd. for C15H~9N30: `
C, 70.00; H, 7.44; N, 16.33 Found: C, 70.03; H, 7.51; N, 16.53. ,l --and N,N,a,3-tetramethyl-5-phenylpyrazole-1-acetamide with ;.~ a melting point of 91-9~ C
,, .
Ana ~ :
`~: Calc'd. for Cl5H1~N
'! C, 70-00; ~, r.44; N, 16.3~.
, ~ I
Found: C, 70. 05; Il, 7.38; N, 16.39. I
,: . ; :,
4-Bromo-N,N,a-trimethyl-3-phenylpyrazole~
1-acetamide and 4-bromo-N,N,a-trimethyl-. ~ ~ . , .
,: ' ' . . . .
:, ~3S3Z;~l
1-acetamide and 4-bromo-N,N,a-trimethyl-. ~ ~ . , .
,: ' ' . . . .
:, ~3S3Z;~l
5-phenylpyrazole-1-acetamide Using the procedure of Example 1, t~ut substituting 4-brorno-:~i-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained 4-bromo-N,N,a-trimethyl-3-phenylpyra zole-1-acetamide with a melting point of 90.5-91.5 C.
~!~:
Calc'd. for C14H1ffBrN30:
C, 52.18; H, 5. 04; N, 13. 04; Br, 24.80.
Found: C, 51.82; H, 4.90; N, 13.12; Br, 24.73.
10 and 4-bromo-NJN~a-trimethyl-5-phenylpyrazole-l-acetamide having a melting point of 117.5-119 C.
Analysis:
Calc'd. for Cl4Hl6BrN30:
C, 52.18; H, 5.o4; N, 13.04; Br, 24.80.
15 Found: C, 52.42; H, 4.98; N, 13.10; Br, 24.61.
Example 5 4-Chloro-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide and 4-chloro-N,N,a-trimethyl-5-phenylpyra~ole-1-acetamide Using the procedure of Example 1, but substituting 20 4-chloro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole - there were obtained 4-chloro-N,N,c~-trimethyl-3-phenylpyra-zole-l-acetamide with a melting point of 73.5-75 C.
Ana!ys~;s:
Calcld, for C14tl1~ClN91~:
- .
C, 60.54; H, 5.81, N, 15.13; Cl, 12.77. !:
Found: C, 60.62; H, 5.8~; N, 15.09; Cl, 12.72.
and 4-chloro-N,N,a-trimethyl-5-phenylpyrazole-1 acetamide witha melting point of 100.5-102 C. I
~: l 30 Calc'd. for C,4Hl8ClN30:
1' .
- . -. . . . .. .
~229 ~V532~3~
C, 60.54; H, 5.81; N, 15.1~; Cl, 12.77.
Found: C, 60.80; H, 5.95; N, 15.49; Cl, 12r91~
Example 6 4,5-~ibromo-N,N,~-trimethyl-3-phenylpyrazole-1-acetamide and 3,4-dibro~o-N,N,a-trimethyl 5-phenyl pyrazol e-1 -acetam i de Using the procedure of Example 1, but substitu~ing 3,4-dibromo-5-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained 4,5-dibromo-N,N,a-trimethyl-3-phenyl pyrazole-1-acetamide having a melting point of 132-134 C.
'; 10 ~
Calc'd. for C14Hl5Br2N30:
C, 41.9~; H, 3.77; N, 10.47; Br, ~i9.85.
- Found: C, 42.24; H, ~.82; N, 10.66; Br, 39.63.
and ~5,4-dibromo-N,N~a-trimethyl-5-phenylpyrazole-1-acetamide 15 having a melting point of 115-118 C.
Analysis:
Calc'd. for C1 4 H15Br2N30:
C, 41.92; H, :3.77; N, 10.47; Br, 39.~5.
Found: C, 41.92; H, 3.8}; N, 10.76; Br, 39,5~.
Ex~p e r N,N,a-Trimethyl-3,4-diphenylpyrazole-1-acetamide and N,N,a-trimethyl-4,5-diphenylpyrazole-1Oacetamide Using the procedure of Example 1, but substituting 3,4-diphenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3,4-diphenylpyrazole-1-acet-~mide having a melting point of 122-124 C.
Analysis:
Calc'd. ~or C20HzlN30:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.1~; H, 6~49; N, 13.54.
;50 and N,N,a-trimethyl-4,5-diphenylpyrazole-1-acetamide ~aving . .
~)5 ~;31 3 melting p~int of 151-15~ C.
~: ' Calc'd~ for CzoH21N30:
C, 75.21; H, 6.6~; N, 1~.16.
Found: C, 75.~0; H, 6.62; N, 1~.46.
Example 8 4-Ethyl-N,N,a-trimethyl-3-phenylpyrazole-1-acet-amide Using the procedure of Example 1, but substituting 4-ethyl-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained 4-ethyl-N,N,a-trimethyl-3-phenylpyrazole 1-acetamide having a melting point of 73.5-75 C.
Analysis:
Calc'd. for Cl~H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.88; H, 7.75; N, 15.75.
4,5,6,7-Tetrahydro-N,N,a-trimethyl-3-phenyl-lH-indazole-1-acetamide Using the procedure of Example 1, but substituting ;~;
3-phenyl-4,5,6,7-tetrahydroindazole for 4-methyl-3-phenyl- I ~-pyrazole there was obtained 4,5,~,7-tetrahydro-N,N,a-tri-methyl-3-phenyl-lH-indazole-1-acetamide having a melting point of 101-10~ C~
- Calc~d. for Cl8H29N~0:
C, 72.69; H, 7.80; N, 14.13.
Found: C, T2.77; H, 7.73; N, 14.24.
~ N,N,a-Trimethyl-~,5-diphenylpyrazole-1-acetamide ;~ Using the procedure of Example 1, but substituting 3J5.dlphenylpyraz~le for 4-methyl-~-phenylpyrazole5 there ~0 was obtained N,N,a-trimethyl-3,5-dipheny1pyrazole-1-aceta--~7-I,: , 1` -~ .
~229 1~ 5 ~ 3~
mide having a melting point oF 133-135 C.
Analysis:
Calc'd. for C20H2lN30:
~ C, 75.21; H, 6~6~; N, 1~.16.
; 5 Found: C, 75.31; H, 6.71; N~ 13.51 N,N,a,3,5-Pentamethyl-4-phenylpyrazole-1-acet-amide Vsing the procedure of Example 1, but substituting - 3,5-dimethyl-4-phenylpyrazole for 4-methyl-~-phenylpyrazole there was obtained N~N~a~3~5-pentamethyl-4-phenylpyrazole 1-acetamide having a melting point of 122-12~.5 C.
.Analysis: ;
Calc'd. For C1~HzlN90: -C, 70.82; ~, 7.80; N, 15.49.
Found: C, 70.8~; H, 7.71; N, 15.79.
;, ~ Nr N, a, 4, 5-Pentamethyl-~-phenylpyrazole-1-acet-amide Using the procedure of Exa~ple 1, but substituting .:
3,4-dimethyl-5-phenylpyrazole ~or 4-methyl-~-phenylpyrazole ~-there was obtained N,N,a,4,5-pentamethyl-~-phenylpyrazole-etamide having a melting point of 76_79 C.
Analysis: :
Calc'd. for Cl~Hz~N30:
C, 70.82; ~, 7.80; N, 15.49.
Found: C, 70.64; H, 7.75; N, 15.55.
N,N,a-Trimethyl-~-(o-tolyl)pyrazo1e-1-acetamide and N,N,a-~rimethyl-5-(o-tolyl)pyrazole-1-acetamide l -~ Using the procedure of Example 1.. but substituting : ~-(o-tolyl)pyrazole f~r 4-methyl-3-phenylpyrazole there was ~0 o~tained N,N,a-trimethyl-3-~o-tolyl)pyrazole 1-acetamide I, ...
lV53~31 3229 having a boili ng point of 164-174~0.3 mm.
~;
Calc'd. for C15H1gN30:
C, 70. 00; H, 7.44; N, 16.33.
Found: C, 69.60; H, 7.50; N, 16.22.
and N,N,a-trimethyl-5-~o-tolyl)pyrazole-1 -acetami de having ; a melting point of 84.5-86.5 C0 Ana ! ys i s :
~.
Calc'd. for C15H19N30:
C, 70. 00; H, 7.44; N, 16.33.
Found: C, 69.94; H, 7.32; N, 16.23.
Example 14 N,N,~,4-Tetramethyl-3-(o-methoxyphenyl)pyra-zole-1-acetamide and N,N,a,4-tetramethyl-5-(o-methoxyphenyl)pyrazole-1-acetamide ; 15 Using the procedure of Example 1, but substit~ing 4-methyl ~-(o-methoxyphenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-3-(o-methoxyphenyl)-pyrazole-1-acetamide having a boiling point of 180/0.5 mm.
Calc'd. for C1~H21N302:
C, 66.87; H, 7.~7; N, 14.62.
Found: C, 66.13; H~ 7.42; N, 14.50~
and N,N,a,4-tetramethyl-5-(o-methoxyphenyl)pyrazole-1-acet-amTde having a melting point of 118-120 C.
,, ~
Calc'd. for Cl~H21N902:
C, 66.87; H, 7.37; N, 14.62.
Found: C, 66.62; H, 7.27; N, 14063.
Examp!e 15 3-(o-Chlorophenyl)-N,N~a-trimethylpyrazole-1-acetamide and 5-(o-chlorophenyl)-N,N,a-tri-. . .
~ -29-;
~229 1053'~
methylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-(o-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained 3-(o-chlorophenyl)-N,N,a-trimethyl-5 pyrazole-1-acetamide having a boiling point of 176-178/.1 mm.
Calc'd. for C14HI6ClN30.
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.17; H, 5.82; N, 14.96; Cl, 12.58. ;
and 5-(o-chlorophenyl )-N,N,~-trimethylpyrazole-1-acetamide having a melting point of 83-86 C.
Analysis:
Calc'd. for C,4Hl6ClN30:
15 C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.89; H, 5.82; N, 15.06; Cl, 12.38.
3-(p-Chlorophenyl)-N,N,a-trimethylpyrazole-1-acetamide and 5-(p-chlorophenyl )-N,N,a-tri-methylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-~p-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained 3-(p-chlorophenyl~-N,N,a-trimethylpyra-~',; zole-l-acetamide having a melting point of 95-99 C.
.
Calc'd. for Cl4Hl~iClN30:
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.57; H, 5.84; N, 15.20; Cl, 12.83.
and 5-(p-chlorophenyl)-N~N~a-trimethylpyrazole-l-acetamide having a melting point of 96-97 C.
~:
. .
~~~
; ' . .
~C~53Z3~
Calc'd. for C14H16ClN30:
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77. ~ -Found. C, 60.~2; H~ 5.74; N, 15~07; Cl~ 12.96.
~ 3-(p~Chlorophenyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(p-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-pyrazole there was obtained 3-(p-chlorophenyl)-N,N,a,4-tetra-methylpyrazole-1-acetamide having a melting point of 99.5-101 C. ~ -Analysis:
Calc'd. for C15HI8ClN30:
C, 61.74; H, 6.22; N, 14.41; Cl, 12.15.
Found: CJ 61.55; H, 6.o4; N, 14.41; Cl, 12.19.
- 15 ~ 3-(o-Methoxyphenyl)-N,N,~-trimethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting ~;
~ 3-(o-methoxyphenyl)pyrazole for 4-methyl-3-phenylpyrazole Y~ there was obtalned 3-(o-methoxyphenyl)-N,N,a-trimethylpyra- ~ -20~ zole-1-acetamide havin3 a melting point of 92-94 C.
Analysis;
Calc'd. for C15H1gN3C2:
, C, 65.91; H, 7.01; N, 15.37.
!~ Found: C, 65.63; H, 6.96; N, 15.33.
i~ 25 ~ 3-(o-Chlorophenyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting ~ 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-i ~ pyrazole there was obtained ~-(o-chlorophenyl)-N,N,a,4-tetra-~ 30 methylpyrazole-1-acetamide having a melting point of -3229 ,l 1~5~231 98.5-100.5 C
Analysis:
Calc'd. for C15H18ClN30:
C, 61.74; H, 6.22; N~ 14,40; Cl~ 12.15.
Found: C, 61.98; H, 6.35; N, 14.39; Cl, 12.22.
3-(m-Chlorophenyl)-N,N,a,4-tetramethylpyra-zole-1-acetamide Following the procedure of Example 1, but substituting 3-(m-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-pyrazole there was obtained 3-(m-chlorophenyl)-N~N~a~4-tetra methylpyrazole-1-acetamide having a melting point of 7~ 75 C.
Analysis:
Calc'd. for C15Hl8ClN30: -C~ 61.74; H~ 6.22; N, 14.40; Cl, 12.15.
Found: CJ 61.90; ~ 6.20; N, 14.30; Cl, 12.21.
3-(m-Chlorophenyl)-N,N,~-trimethylpyrazole-1-acetamide Following the procedure of Example 1~ but substituting 3-(m-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole ~; there was obtained 3-(m-chlorophenyl)-NJN,a-trimethylpyra-zole-1-acetamide having a boiling point of 175/0.08 mm.
Ana l ys 7 s :
Calcld. for C14H1aClN30:
C~ 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.24; H, 5.92; N, 15.39; Cl, 17.12.
3-(2,5~Dichlorophenyl)-NJN,a-trimethylpyrazole-~ 1-acetamide - Following the procedure of Example 1, but substituting 3-(2,5-dichlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole ;, , . . - .
1~S323~
there was obtained ~-(2,5-dichlorophen~ NrN,~-trimethyl-pyrazole-1-acetamide having a melting point of 73.5-76.5 C.
Analysi~s:
Calc'd. for C14H15Cl2N30: :
C, 53.86; H, 4.8~; N, 13.4~; Cl, 22.71.
Found: C, 54.04; H, 4.92; N, 1~.65; Cl, 22.73.
N,N,a,4-Tetramethyl-3-(o-tolyl)pyrazole-1-acet-amide :~
Following the procedure of Example 1~ but substituting 4-methyl-3-(o-tolyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N~N~a~4-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide having a boiling point of 178-182/0.7 mm. :::
N,N,a-Trimethyl-3-(p-tolyl)pyrazole-1-acetamide ` Following the procedure of Example 1, but substituting t 15 ~-(p-tolyl)pyrazole for 4-methyl-3-phenylpyrazole there was : obtatned N,N~-trimethyl-3-(p-tolyl)pyrazole~1-acetamide :
, having a melting point of 79-82 C.
. . .
: ~ Calc'd. for C15~19N30:
C, 70.00; H, 7.44; N, 16.33.
` Found: C, 70.2~; H, 7.29; N, 16.60.
N,N,a-Trimethyl-3-(m-nitrophenyl)pyrazole-acetamide ~ : ~ Following the procedure of Example 1, but substituting '~: 25 3-(m-nitrophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a-trimethyl-3-(m-nitrophenyl)pyra-: zole~l-3cetamide having a melting poi nt of 117-119 C.
Analysis:
.:
~: Calc'd. for Cl4Hl~NgO3:
~0 C, 58.32; H, 5.59; N, 19.44.
-33~
~.. .. . . . . .. . . . .
1~ 5 ~
Found: CJ 59. o6; H, 5.68; N, 19.72.
Example 26 N,N,~-Trimethyl-3-(276-dichlorophenyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(2,6-dichlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a-trimethyl-3-(2,6-dichlorophenyl~ -: pyrazole-1-acetamide having a melting point of 88-go C.
Analysis:
Calc'd. for C14H1sCl2N30:
C, 53.86; H, 4.84; NJ 13.46; Cl, 22.71.
Found: C, 53.78; H, 5.02; N, 13.41; Cl, 22.73.
Example 27 4-Chloro-N,N-diethyl-a-methyl-3-phenylpyrazole-1-acetamide and 4-chloro-N,N-diethyl-a-methyl-5-phenylpyrazole-1-acetamide 15 Using the procedure of Example 1, but substituting 2-chloro-N,N-diethylpropionamide for 2-chloro-N,N-dimethyl-propionamide and 4-chloro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained 4-chloro-N~N-diethyl-~-methyl-3-phenylpyrazole-1-acetamide having a boiling point of 191-192 /0.74 mm.
~:
Calc'd. for Cl~H20ClN30:
C, 62.84; HJ 6.59; N, 13.74; C1J 11.59.
Found: C, 62.50; H, 6.74; N, 13.48; Cl, 11.58.
and 4-chloro-N,N-diethyl-~-methyl-5-phenylpyrazole-1-acet-amide having a meltîng point of 85 87 C.
~ Analysis:
-! Calc'd. for C1~H20ClN30:
C, 62~84; H~ 6.59; N~ 13-74; C1~ 11-59-Found: C, 62.92; H, 6.71; N) 13.62; Cl, 11.58.
, , , . ,, :
~22g 1 0 5 ~Z 31 ~-Ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acet-amide and a-ethyl-N,N~-trirnethyl-5-phenylpyra-zole-1^acetamide Using the procedure of Example 1, but substituting 2-chloro-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-~ propionamide there were obtained a-ethyl-N,N,4-trimethyl-- 3-phenylpyrazole-1-acetamide having a melting point of 86-88 C.
Analysis:
Calc'd. for C~6H21N30: -C, 70.82; H, 7.80; NJ 15.49.
Found: CJ 70.91; HJ 7.9~; NJ 15.73.
and ~-ethyl-N,N,4-trimethyl-5-phenylpyrazole-1-acetamide having a melting point of 88-go c.
~ :
Calctd. for Cl6H2lN30:
CJ 70.82; H, 7.80; N, 15.49.
Found: C, 70.83; HJ 7.82; N, 15.56.
Alternate Synthesis for ~ ;~
, , ~
Sodium methoxide powder (216 g., 4.0 mole) was added over 10 minutes to a stirred solution of 4-methyl-3-phenyl-pyrazole (632 g.~ 4.0 mole) in tetrahydrofuran (1.0 liter) at 10 C. 2-Bromo-N,N-dimethylbutyramide (911 9., 4.7 mole) was added dropwise over 30 minutes while maintaining ; the temperature of the reaction solution below 30 C. by external cooling. The solution was stirred for an addition-al 30 minutes at room temperature, and the THF was then re-- moved under reduced pressure. The residual oil was parti-tioned between chloroform and water. The chloroform layer ' ' .. ..
.
.: .
~53Z3~
i was evaporated and the residual oil was recrystallized from benzene:Skellys~lve B to give 772 g. of a-ethyl-N~N~4-tr methyl~3-phenylpyrazole-1-acetamide, m.p. 85.5-87.5 C.
Evaporation of the crystallization mother liquors gave 365 9. of oil containing additional product.
Example 29 N,N,a-Trimethyl-3-(2-thienyl)pyrazole-1-acet-amide and N,N,a-trimethyl-5-(2-thienyl)pyra-zole-1-acetamide Following the procedure of Example 1, but substituting 3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3-(2-thienyl)pyrazole-1-acet-amide having a melting point of 95-97 C.
Analysis:
Calc'd. for C12H15N30S:
C, 57.80; H, 6.o6; N, 16.85; S, 12.85.
Found: C, 57.52; H, 5.98; N, 16.76; S, 13.17.
- and N,N,a-trimethyl-5-(2-thienyl)pyrazole-1-acetamide having a melting point of 80 82 C.
.' ~:
,~
Calc'd. for C12H1sN90S: -C, 57.80; H, 6.Q6; N, 16.85; S, 12.85.
, .
Found: C, 58.10; H, 5.95; N, 16~87; S, 13.05.
; ~ N,N,aJ4-Tetramethyl-3-(2-thienyl)pyrazole-1-acetamide and N,N,a,4-tetramethyl-5-(2-thi- -~
`~ 25 enyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 4-methyl-~-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,~,4-tetramethyl-3-(2-thienyl)pyra-- zole-1-acetamide having a melting point of 100-102 C.
Analysis:
- .
:
~229 1~5;~231 Calcld. for Cl3H17N30S:
C, 59.29; H, 6.51; N, 15.96; S, 12.17. ~-Found: C, 59. 09; H, 6~ 52; N, 15.86; S, 11.99.
and N,N,a,4-tetramethyl -5- (2-thienyl )pyrazole-1-acetamide having a melting point of 77-80 C.
Analysis:
Calc'd. ~or Cl9Hl7N30S:
C, 59.29; H, 6.51; N, 15.96; S~ 12.17.
Found: C, 59.02; H, 6.27; N, 15.87; S, 12.29.
Example 31 ~-Ethyl~,N,4-trimethyl-3-(2-thienyl)pyrazole-1-acetamide and a-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example 1, but subs~ituting 4.methyl-3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyra : 15 zole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-; dlmethylpropionamide there were obtained a-ethyl-N,N,4-tri-methyl-3-(2-thienyl)pyrazole-1-acetamide having a melting point of 83-85 C. -Analysis:
~; . . . .
Calcld. for C14H1gN305:
C, 60.62; H, 6.90; N~ 15.15; S, 11.56.
Found: ~, 60.61; H, 6.76; N, 15.14; S, 11.49.
a~d a-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acet-amlde hav7ng a boiling point of 170/0.7 mm.
; ~ 25 Ana! ys ~ s: :-Calc'd. for CI~Hl~N30S~
C, 60.62; H, 6.90; N~ 15.15; S, 11.56.
Found: C, 60.31; H, 6.97; N, 15.07; S, 11.23.
E~ampl~ N,N,a,4-Tetramethyl-3-(5-chloro-2-thienyl)-pyrazole^1-acetamide ':
3~29 5;~Z3~
Following the procedure of Example 1, but substituting 4-methyl-3-(5-chloro-2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-3-(5-chloro-2-thienyl)pyrazole-1-acetamide having a melting point of 111. 5~114 C .
Ana!Ysis Calc'd. for C13Hl6ClN30S:
C, 52.43; H, 5.42; N, 14.11, Cl, 11.91;
S, 10.77.
Found: C~ 52.44; H, 5.59; N, 14.19; Cl, 11~68;
S, 10.85.
N,N,4-Trimethyl-a-propyl-3-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example 1~ but substituting 4-methyl-3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole ~ ;
and 2-bromo-N,~ dimethylvaleramide for 2-chloro-N,N-dimethyl-propionamide there was obtained N,N,4-trimethyl-a-propyl-3-(2-thienyl)pyrazole-1-acetamide having a melting point of 85-87.5 C.
Calc'd for C15H21N30S:
5J 61.82; HJ 7.26; N, 14.42; S, 11. 00.
Found: C, 61.70; H~ 7.40; N, 14.40; S, 11. 05.
~ 3-(2-Furyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(2-furyl)-4-methylpyrazole for ~-methyl-4-phenylpyrazole there was obtained 3-(2-fwryl)-N,N,a,4-tetramethylpyrazole-1-acetamide having a melting point of 93-95 C.
:50 Ana l ys i s:
-~8-.
.
10S~231 Calc'd. for C1 3Hl 7N302:
C, 63.14; H, 6.93; N~ 16.99.
Found: C, 63~17; H, 7.13i N, 17.07.
Example 35 a-Ethyl-3-(2~furyl)-NJN~4-trimethylpyrazole-1-acetamide Foll~winy the procedure of Ex3mple 1, but substituting 3- (2-furyl)-4-methylpyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-di-methylpropionamide there was obtained a-ethyl-3-~2-furyl) N,N,4-trimethylpyrazole-1-acetamide having a melting point of 115-117 ~.
Analysis:
Calc'd. for C14H1gN302:
Cg 64.34; H, 7.3~; N, 16.08.
` 15Found: C, 64.46; H, 7.26; N, 15.89. -Example 36 3- (2-Furyl)-N,N,4-trimethyl-a-propylpyrazole-l-acetamide :
Following the procedure of Example 1, but substituting 3- (~-furyl)-4-me~hylpyrazole for 4-methyl-3.phenylpyrazole 20 and 2-bromo-N,N-dimethylvaleramide for 2-chloro-N,N-dimethyl- ~
propionamide there was obtained 3-(2-furyl)-N,N,4-trimethyl- ~ -o~-propylpyrazole-1-acetamide having a melting point of 107-109 C.
.' ~,:
25Calc'd. for C15H21N30-C, 65,43, H, 7.69; N, 15.26.
Found: C, 65 61; Il, 7.78; N, 15.21.
~e~:Z N,N,~,~J4-Pentamethyl-5-phenylpyrazole-1-pro-propionamide and N,N,a,ag4-pentamethyl-3-phenyl-;~50 pyrazole-1-propionamide .~ - -Following the procedure of Example 1, but substituting 3-chloro-N,N,2,2-tetramethylpropionamide for 2-chloro-N,N-dimethylpropionamide there were obtained N,N,a,a,4-pen-tamethyl-5-phenylpyrazole-1-propionamide having a melting point of 59-60 C.
Analysis:
Calc'd. for Cl7H23N30:
C, 71.54;~, 8.12; N, 14.73.
Found: C, 71.61; H, 8.31; N, 14.65.
and NJNJaJa94-pentamethyl-3-phenylpyrazole-l-propionamide having a boiling point of 175 /0.03 mm.
Analysis:
Calc'd. for C17Hz3N30:
C, 71.54; H~ 8.12; N, 14.73 Found: C, 71.43; H, 8.45; N, 14.79.
Example 38 N,N,~-Trimethyl-3-(o-nitrophenyl)pyrazole-1-acetamide Following the procedure of Example 1, but substitut-ing 3-(o-nitrophenyl)pyrazole for 4-methyl-3-phenylpyra-~20 zole there was obtained NJN,a-trimethyl-3-(o-nitro-;phenyl)pyrazole-1-acetamide, as a brown liquid.
3-(o-Chlorophenyl)-~-ethyl-N,N-dimethyl-pyrazole-1-acetamide Following the procedure of Example 1J but substitut-5 ing 3-(o~chlorophenyl)pyrazole for 4-methyl-3-phenyl- ~ -pyrazole and 2-bromo-NJN-dimethylbutyramide for 2-chloro-N,N-dimethylpropionamide there was obtained 3-(o-chloro- -phenyl)-a-ethyl-N,N-dimethylpyrazole-1-acetamide having a melting point of 38.5-40 C.
Ana!~sis:
.. .
~229 ~S3~Z3~
Calcrd. for Cl5H18ClN30:
C, 61.74; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.99; H, 6.22; N, 14.38; Cl, 12.31.
~ ~-Ethyl-N,N-dirnethyl-3-(o-tolyl)pyrazole-1-acetamide Following the procedure of Example 1, but substitut-ing 3-(o tolyl)pyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-di-methylpropionamide there was obtained ~-ethyl-N,N-dimethyl-3-(o-tolyl~-pyrazole-1-acetamide having a melting point of 48-51Q C.
Calc'd. for C16H21N30-C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.66; H, 7.74; N, 15.32.
~ ,.~-(o-Chlorophenyl)-a-ethyl-N,N,4-trimethyl-.
pyrazole~ acetamide Following the procedure of Example 1, but substi-tuting 3~(o-chlor~phenyl)-4 methylpyrazole for 4-methyl-3-phenylpyrazo7e and 2-bromo-N,N-dimethylbutyramide for 2-chloro-NJN-dimethylpropionamide there was obtained 3-(v~chlorophenyl~-~-ethyl-N,N,4-trimethyl-pyrazole-1-acetamTde having a boiling point of 180~0.15 mm.
Analysis:
Calc'd. for C1~H20ClN30:
C, 62.84; H, 6.59; N, 13.74; Cl, 11.59.
Found: C, 62.69; H, 6.81; N, 13.73; Cl, 11.52.
~ ~-(3-Bromopropyl)-N,N~4-trimethyl-3-phenyl-pyrazole-1-acetamide .
. , - , .
-, . . .
1053Z;3~
Following the procedure of Example 1, but substituting 2,5-dibromo-N,N-dNnethylvaleramide for 2-chloro-N,N-dimethyl-propionamide there was obtained ~-(3-bromopropyl)-N,N,4-tri-methyl-3-phenylpyrazole-1-acetamide as a liquid.
Example 4~ a-(4-Bromobutyl)-N~N~4~trimethyl-3-phenylpyra- ~-zole-1-acetamide Following the procedure of Example 1, but substituting 2,6-dibromo-N,N-dimethylcaproamide for 2-chloro-N,N-dimethyl-propionamide there was obtained ~-(4-bromobutyl)-N,N,4-tri-methyl-3-phenylpyrazole-l-acetamide as a liquid.
a-Ethyl-N,N,4-trimethyl-3-(o-tolyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 4-methyl-3-(o-tolyl)pyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-; propion3mide there was obtained a-ethyl-N,N,4-trimethyl- -~
3-(o-tolyljpyrazole~1-acetamide having a boiling point of ` 155-157/0.05 mm.
, ! Y . :, .
Calc'd. for Cl7H23N30:
C, 71.$5; H, 8.12; N, 14.72.
Found: C, 71.18; H, 8.27; N, 14.65.
Example 45 a-(2-chloroethyl)-N~N~4-trimethyl-3-phenylpyra zole-1-acetamide Following the procedure of Example 1, but substituting , 2-bromo-4-chloro-N,N~dimethylbutyramide for 2-chloro-N,N-dlmethylpropionamide there was obtained a t2-chloroethyl)-N,NI4-trimethyl-~-phenylpyrazole-1-acetamide as a liquid.
a-Cyclohexyl-N,N,4-trimethyl-3-phenylpyrazole-~0 1-acetamide -. . .. .
: - . . : . .
~0~3Z3~
Following the procedure of Example 1, but substituting ~-bromo-N,N-dimethyl-1-cyclohexaneacetamide for 2-chloro-N,N-dimethylpropionamide there was obtained a-cyclohexy N,N,4-trimethyl-3-phenylpyrazole-1-acetamide having a melting point 102.5-104.5 C.
- -:
Calc'd. for C20H27N~0:
C, 73.81; H, 8.36; N, 12.91.
Found: C, 73.70; H, 8.44; N, 12.69.
Example 47 a-cyclohexyl-NJN-dimethyl-3-phenylpyrazole 1-acetamide Following the procedure of Example 1, but substituting a brom~-N~N-dlmethy~ cyclohexaneacétamide for 2-chl~ro N,N-dimethylpropionamide and 3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained ~-cyclohexyl-N,N-di-me~hyl-3-phenylpyrazole-1-acetamide having a melting point of 87.5-go C.
Calc'd. for C1gH25N30:
~i 20 C, 73.28; H, 8.o~; N, 13.49.
Found: C, 7~.~6; H, 8.o8; N, 13.39.
a-Butyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 2-bromo-N,N-dimethylcaproamide for 2-chloro-N,N-dimethylpro-pionamide there was obtained ~-butyl-N,N,4-trlmethyl-3- ~ -phenylpyrazole-1-acetamide having a boiling point of 189/0.1 mm.
Analysis:
Calç'd. for Cl8H25N30-:
~l~53Z31 C, 72.20; H, 8.42; N, 14.04.
Found: C, 71.76; H, 8.~o; N, 13.89.
Examp1e 49 N,~,a,4-Tetramethyl-3-phenylpyrazole-1-aceta-mide, N,~,a,4-tetramethyl-5-phenylpyrazole-1-acetamide,and N,a,4-trimethyl-~-phenylpyra-zole-1-propionamide Sodium hydride (25.0 9. of 57~ dispersion in oil~ o 6 mole) was added to a stirred solution of 4-methyl-3-phenyl-pyrazole (7g.0 g., 0.5 mole) in tetrahydrofuran. Ethyl-2-bromoisobutyrate (136.0 9., 0.7 mole) was added and the $olution was refluxed for 4 hours. The solvent was removed by evaporation and the residual ester mixture was hydrolyzed by refluxing with methanolic sodium hydrbxide solution (40 g. sodium hydroxide in 600 ml. of 30~ methanol-water).
After cooling, the alkaline reaction solution was extracted with ether and the aqueous phase was acidified with concen-trated hydrochloric acid. The solution was extracted with chloroform, and the chloroform layer was evaporated to give a crude acid mixture in which a,~,4-trimethyl 3-phenylpyra-zole-1-acetic acid was the major isomer.
The crude acid was dissolved in benzene (1 liter), and thionyl chloride (59.5 g., 0.5 mole) was added and the so1u-tion was refluxed for 3 hours After cooling, the solution was added slowly to a stirred solu~ion of 40% aqueous methyl-amine (200 ml.) containing ice (500 9.). After 10 minutes, the benzene layer was separated, washed with water, and evaporated to afford 100 9. of mixed methylamides.
Chromatography on silica gel afforded 64 g. of N,a,~,4-tetramethyl-3-phenylpyrazole-1-acetamide, which was ~0 recrystallized from cyclohexane; m.p. 84-88 C.
.
, ~
3229 ~ ;
l~S3Z31 Calc'd. for C1sH~9N30:
Cl 70.00; H, 7.44; N, 16.33.
Found: C, 69.95; H, 7.61; N, 16.40.
Further elution of the column afforded 4.1 9. of N,~,~,4-tetramethyl~5-phenylpyrazole-1-acetamide, which was ; recrystallized twice from ethyl acetate for analysis; m.p.
; 119-120 C.
Analys ! 5 Calc'd. for C15H1~N30:
CJ 70. 00; H, 7.44; N, 16.33.
Found: C, 70.25; H, 7.64; N, lÇ.55.
Further elution of the column afforded 6.6 9. of N,a,4-trimethyl-3-phenylpyrazole-1-propionamtde, which ~as recrystallized twice from ethyl acetate for analysis; m.p.
123-124 C.
Analysis:
Calc'd. for C15H19N30:
C, 70.00; H, 7.44; N, 16.33.
Found. C, 70.18; H, 7.41; N, 16.52.
,a,4 Trimethyl.3-phenylpyra201e-1-acetamide Following the procedure of Example 49, but substituting aqueous ammonia for aqueous methylamine there was obta;ned ~,a,4-trimethyl-~-pheny1pyrazole-1-acetamide having a melt-ing point of 105-1~6 C.
Analysis Calc'd. for C14H17N~0:
C, 69.11; H, 7.Q4; N, 17.27.
Found: C, 69.01; H, 7.02; N, 17.37.
3Q ~ N-~thyl-aJa~4-trimethyl-3-phenylpyrazole-l-acet . . , : .
322g 1~)53231 amide and N-ethyl-aJ4-dimethyl-3-phenylpyrazole-1-propionamide F~llowing the procedure of Example 49, but substituting aqueous ethylamine for aqueous methylamine there was obtained N-ethyl-a,~,4-trimethyl-3-phenylpyrazole-1-acetamide having a bqiting point of 150/0.2 mm.
Analysi_s:
Calc'd. for C18H2~N30:
.
C, 70.82; H, 7.80; N, 15.49;
10 Found: C, 70.65; H, 7.80; N, 15.3C).
and N-ethyl-~J4-dimethyl-3-phenylpyrazole-1-propionamide hav7ng a melting point of 110.5-112.5 C.
Analysis:
Calc'd. for C16H2lN30:
15 C, 70.82; H, 7.Bo, N, 15.49.
Found: C, 70.33; H, 7~64; N, 15032.
Exame!e_52 c~a~4-~rimethyl-3-phenyl-N-isopropylpyrazole 1-acetamide and a~4-dimethyl-~-phenyl-N-isopr pylpyrazole-1-propionamide 20 Following the procedure of Example 49, but substituting Isopropylamine for aqueous methylamine there were obtained a,a,4-trimethyl-~-phenyl-N-isopropylpyrazole-1-acetamide having a boiling point of 160~/0.25 mm.
Analysis:
~ .
- 25 Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73. -- ~ , Found: C, 71.73; H, 8.20; N, 14.74.
and aJ4-dtmethyl-3-phenyl-N-isopropylpyrazole-l-propionamide having a melting point of 104-107 C.
:
30 Analysis:
'''' :
,: ... -, , .. . , . . .,, . : . .
~229 1~)53~31 Calc'd. fcr C17Hz3N30:
C~ 71.54; HJ 8.12; N~ 14.7~
Found: C, 70.6g; H, 7.79; N, 14.38.
~ a,~J4-Trimethyl-3-phenyl~N-propyl pyrazole-1-acetamide and a,4-dimethyl-3-phenyl-N-propyl-pyrazole-1-propionamide Following the procedure of Example 49, but substituting propylamine for aqueous methylamine there were obtained ~,a,4-trimethyl-3-phenyl-N-propylpyrazole-1-acetamide having a melting point of 47-50 C.
Ana~ s~s:
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.7~.
Found: C, 71.62; H, 8.03; N, 14.37.
~nd a,4-dlmethyl-~-phenyl-N-propylpyrazole~1-propionamide havlng a melting point of 96-98 C.
Calc'd. for C17H23N30:
C, 71.54; Hj 8.12; N, 14.73.
20Found: C, 71.51; H, 7.97; N, 14.39.
Example 54 N-Buty~ J4-trimethyl-3-phenylpyrazole-l-acet amide , :~
Followlng the procedure of Example 49, but substituting butylamTne for aqueous methylamine there ~as obtained N-buty~ 4-trimethyl-3-phenylpyrazole-l-acetamide having a melting point of 5~-57 C.
~i ~, , Calc d. for ClaH~5N30:
C, 72.20; H, 8.42, N, 14.04.
Found: C, 72.47; HJ 8.62; N, 14.26.
- . ~
1~53~31 N-tert-Butyl-~,a,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 49, but substitutillg tert-butylamine for methylamine, there was obtained N-tert-butyl-a,a,4-trimethyl-3-phenylpyrazole-1-acetamide having a melting point of 71-75 C.
Analysis:
Calc'd. for C18H25N30:
C, 72.20; H, 8.42; N, 14.04.
lQ Found: C, 71.99; H, 8.78; N, 13.820 a,a,4-Trimethyl-3-phenylpyrazole-1-acetanilide Following Example 49, but substituting aniline for aqueous methylamine there was obtained ~,a,4-trimethyl-: 3-phenylpyrazole~1-acetanilide having a melting point of 1~6~119 C.
Calc'd. for C20HzlN30:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.04; H, 6.54; N, 1~.04.
20 ~ NJaJa~4-Tetramethyl-3-phenylpyrazole-l-acet- . ~ :
anilide Following the procedure of Example 49, but subs~ituting N-methylaniline for aqueous methylamine there was obtained - N,a,a,4-tetramethyl-3-phenylpyrazole-1-acetanilide having a ::
melting point of 152-154 C.
Calc'd. for C2~H29N30:
C, 75.64; H, 6.95; N, 12.60.
Found: C, 75.66; HJ 7.09; N, 12.79.
~ N-Benzy7 a,a,4-trimethyl-3-phenylpyrazole-; ~
l~)S3Z3~
1-acetamide Following the procedure of Example 49, but subs~it~ting benzylamine for aqueous methylamine there was obtained N-benzyl-a,a,4-trimethyl-~-phenylpyrazole-1-acetamide having a melting point of 87-go C~
Calc'd. for C21H23N30:
C, 75.64; H, 6.95; NJ 12.60.
Found: C, 75.40; H, 6.96; N, 12.28.
Example 59 N,N,~,~,4-Pentamethyl-3-phenylpyrazole-1-acet-amide and N,N,a,4-tetramethyl-3-phenylpyrazole~
1-propionamide ` Following the procedure of Example 49, but substituting aqueous dime~hylamine for aqueous methylamine, there were obtalned N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide having a melting point of 107-109 C.
Analysis: , Galcid. for C1eH2lN30:
C, 70.82; H, 7.80; N, 15.49.
; 20~ound: C, 70.98; H, 7.90; NJ 15.73.
and N~NJaJ4-tetramethyl-3-phenylpyrazole-l-propionamide ~ . :
having a melting pofnt of 51-54 C.
Analysls:
. - - .
Calc'd. for C~eH2~N30: .
~5CJ 70,82; H~ 7~80; N, 15.49.
Found~ C, 71.03; H, 7.79; N, 15.42.
! Alterna~e ~ of N?N~ ,4~pentamethyl-3-phenylpyra zole-l-acetamide Sodium methoxtde powder (65 9., 1.2 mole) was added 30 slowly So a sti rred mixture of 4-methyl -3-phenylpyrazole -4g~
. :' 11~5323~
(158 9.J 1.0 mole) and ethyl-2-bromoisobutyrate (238 9., 1.2 mole) at 100 C. After a~dition was complete the reac-tlon was cooled slightly, 80 9. sodium hydroxide in 400 ml.
of water, 100 ml. ethanol was added, and the solution was heated under reflux for 1 hour. After cooling the solution was extracted with ether to remove unchanged 4-methyl-3-phenylpyrazole (ca 20 9.). The aqueous phase was care-fully acidified with concentrated hydrochloric acid and the pyra~ole acid was extracted into chloroform.
The chloroform was removed under reduced pressure J the residue was dissolved in benzene ~500 ml.), thionyl chloride (140 9., 1.1 mole) added, and the mixture was stirred under-reflux for 3 hours. After cooling the solution was added to a stirred solution of 25~ aqueous dimethylamine (600 ml.) containing ice, the temperature was heid below 30 C. during the addition. The benzene layer was separated, washed with water and evaporated. The dark brown residual oil was crystallized from methanol (ca 200 ml.) at -10 C. and then from benzene:Skellysolve B to give 110 9. of N,N,a,a,4-pen-tamethyl-3-phenylpyrazole-1-acetamide, m.p. lP9-111 C.
Additional product was obtained by chromatography of the mother liquors.
N,N-Diethyl-a,a,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 49J but substitut-ing dlethylamine for aqueous methylamine, there was -obtained N~N-diethyl-a,a,4-trimethyl-~-phenylpyrazole-1-acetamide having a melting point of 50-52 C.
~ ,~,. .
Calc'd. for C~8H25N30 -5o-- . .
, 322g ~53Z31 C, 72.20; H, 8.42; N, 14.04 Found: C, 72.28; H, 8.44; N, 140 07.
N,a,a,4-Tetramethyl-N-octyl-3-phenylpyrazole-1-acetamide Foll~ing the procedure of Example 49, but substituting N-methyloctylamine for aqueous methylamine, there was obtained N,a,a,4-tetramethyl-N-octyl-3-phenylpyrazole-1-acetamide having a melting point of 75-78 C.
Analysis- -~
Calc'd. for C23H35N30~
C, 74.75; H, 9.55; N, 11.37.
Found: C, 74.74; H, 9.43; N, 11.12.
Example 62 N,N,a,a-Tetramethyl-3-phenylpyrazole-1-acetamide and N,N~a-trimethyl-3-phenylpyrazole-1-propionamide ~ 15 Following the procedure of Example 49, but substitut-.~ ing 3-phenylpyrazole for 4-methyl-3-phenylpyrazole and aqueous dimethylamine for aqueous methylamine there were obtained N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide having a melting point of 99.5-102~ C.
Analysis:
Calc'd. for Cl5H1gN~0: ~ -C, 70.00; H, 7.44; N, 16.33.
Found: CJ 69. 83; H, 7.47; N, 16.16.
and N,N,a-trimethyl-3-phenylpyrazole-1-propionamide having a melting point of 69-71.5 CO
Analysis: ~
Calc'd. for C~5H19N30:
., .
C, 70.00; H, 7.44; N, 16.33.
Found: C, 69.97; H, 7.55; N, 15.90.
~0 ~ N,N-Diethyl-3-(2-furyl) a,a,4 trimethylpyrazole .
,, 3~29 l~S~Z31 1-acetamide Following the procedure of Example 49, but substitutin~
3-(2-furyl)-4-methylpyrazole for 4-rnethyl-3-phenylpyrazo1e and diethylamine for aqueous methylamine there was obtain~d 5 NJN-diethyl-3-(2-furyl)-a~a~4-trimethylpyrazole-l-aceta~ e having a melting point of 73-76 C~
Ana!ysis^ :
Calc'd. for C16H23N302.
C, 66.41; H, 8.01; N, 14.52 Found: C, 66.19; H, 7.83; N, 14.24.
Example 64 ~-(2-Furyl )-NJ a, a~4-tetramethylpyrazole-l-ace~
amide ; Following the procedure of Example 49J but substituting ~-(2-furyl)-4-methylpyrazole for 4-methyl-3-pheny1pyrazole 15 there was obtained 3-(2-furyl)-N,a,cl.,4-tetramethylpyra~ole , 1-acetamide having a melting point of 101-103 CO
!
; Analysis:
Calc'd. for C13H~7N
~i .
CJ 63.14; H~ 6.93; N~ 16.99.
~- 20 Found: CJ 61.58; H~ 6.69; N, 16.48. -3-(o-Chlorophenyl)-N,N,c~., a-tetramethylpyrazole-1-acetamide Follawing the procedure of Example 49, but substituting ~- (o-chlorophenyl)pyrazole for 4-methyl-~-phenylpyra~ole 25 and dimethylamine for aqueous methylamine there was obtaine~
3- (o-chlorophenyl)-NJN,a,a-tetramethylpyrazole-1-acetamide having a melting point of 751-80.5 C.
Analys!s~
Calc'd. for C15Hl8ClN30:
- 30 C, 61.74; H, 6.22; N, 14.40; C1J 12.15.
, . .
. ... .. , . , . .,, ., .. ~ : , .
~i229 ~05;~3~
Found- C, 62. 00, H, 6.45; N, 14~46; Cl, 12. o6.
Example 66 N,N,a,~,Tetramethyl -3-(o-tol yl)pyrazole-1-acetamide Following the procedure of Example 49, but substituting ~- (o-tol yl )pyrazole for 4-methyl 3-phenyl pyrazole and 5 dimethylamine for aqueous methylamine there was obtained N,N,a,c~-tetramethyl-3- (o-tolyl )pyrazole-1-acetamide having a melting point of 78.5-81 C.
Ana l ys i s :
Calc' d. for Cl~3H2~N30:
10C, 7~.82; H, 7.80; N, 15.49.
Found: C, 70062; H, 7088; N, 15.69. -Example 67 N,N,a,a,4-Pentamethyl-3-(o-tolyl )pyrazole-1 -a ce tam i de Following the procedure of Example 499 but substituting 15 4-methyl-3-(o-tolyl )pyrazole for 4-methyl-3-phenylpyrazole and dimethylamine for methylamine there was obtai ned N.N, a) a,4-pentamethyl -3- (o-tol yl )pyrazole-1-acetamide havi ng a melting point of 145-147 C.
Ana l ys i s:
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73.
Found: C, 71.51; H, 8.50; N, 14.83.
. ~e~ .
Part A - a,4-Dimethy~-3_phenylpyrazole 1-acetic acid .
Sodium hydride (50.0 g., 57,~ in oil, 1.2 mole) was added over 20 minutes to a stirred solution of 4-methyl-3-phenylpyrazole (158 g., 1.0 mole) in THF (1.0 l.) maintair,ed at 10-20 C. Ethyl 2-bromopropionate (235 g., 1.3 mole) was added and the solution stirred for 18 hours, after which t ime ethanol was added and the solvent was rernoved by evapor-;
~229 ~C~S3Z3~
ation at reduced pressure. The residue was treated at 90 C.
with sodium hydroxide (100 y., 2.5 mole) in 800 ml~ 60%
aqueous methanol for ~0 minutes. After cooling, the solution was extracted with ether (3 x 200 ml.)g and ~he aqueous phase was acidified with concentr3ted hydrochl~ride acid to give 148 9. of crude aJ4-dimethyl-3-phenylpyrazole-l-acetic acid, m.p. 151-162 C. Recrystallization from aqueous methanol gave 111 g. of product, m.p. 168-172 C. The analytical sam-ple was recrystallized from ethyl acetate; m.p. 170-172 C.
Analysis~
Calc'd. for Cl3H1~NzOz CJ 67.81; H, 6O13; N, 12.17.
Found: C, 68~32; H, 6.14; N, 12~06.
Part B - a,4-Dimethyl 3-phenylpyrazole-1-acetamide A mixture of a,4-dimethyl 3-phenylpyrazole 1 acetic acid (11.5 g., 0.05 mole), thionyl chloride (7.5 g., oOo6 mole) and benzene (300 ml.) was heated under reflux for 1 hour and cooled. Ammonia (30 ml. of 25~ aqueous solution) '~
was added rapidly with stirring to one-half of the above sol-;~ 20 ution. The benzene layer was separated, washed with water, and the benzene evaporated. The residual oil (8.3 9.) was re-j .
crystallized twice from benzene:Skellysolve B to give 4.2 g.
of a,4-dimethyl-3-phenylpyrazole-1-acetamide, m.p 99-101 C.
Calc'd. for C13H15N30:
C, 68.10; H, 6.59; Ng 18.33.
Found: C, 69.og; H, 6~74; N, 18.47.
. .
~ ~,a,4-Trimethyl-3-phenylpyrazole-1-acetamide j ~ Following the procedure of Example 68, but substitu~ing .
aqueous methylamine for aqueous ammonia~ there was obtained ''' ' ' ' . . : , ~ . .: . . :
/
1~53Z3~
N,a,4-trimethyl-3~phenylpyrazole-1 acetamide having a melting point of 111-112 C.
!
Calc'd. For C14H17N30-C, 69.11; H, 7.~4; N, 17.27.
Found: C, 69.1û; H, 7.37; N, 17.29.
N-Ethyl-a~4-dimethyl-3-phenylpyrazole-l-acetarride Following the procedure of Example 68, but substituting aqueous ethylamine for aqueous ammonia, there was obtained 10 N-ethyl-c~,4-dimethyl-3-phenylpyrazole-1-acetamide having a melting p~int of 78-79 C.
Analysis:
Calc'd. for C15HlgN30:
i C, 700 00; H, 7.44; N, 16.33.
15Found: C, 70.14; H, 7.30; N, 16.49.
Example 71 N-Butyl-aJ4-dimethyl-3-phenylpyrazole-l-acetamide .. . .
Following the procedure of Example 68, but substituting butylamine for ~queous ammonia, there was obtained N-butyl-a,4 dimethyl-3-phenylpyrazole-1-acetamide having a melting 20 point of 82-84 C.
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73.
Found: C, 72.42; H, 8.01; N, 14.91.
:~ 25 ~e~ N-Ethyl-N,a,4-trimethyl-~-phenylpyrazole-1-acet-amide . -~: Followin~ the procedure of Example 68, but substituting N-methyl ethylamine for aqueous ammonia, there was obtained -: N-ethyl-NJaJ4-trimethyl-3-phenylpyrazole-l-acetamide having 30 a melting point of 5~-61 C.
- . , . , . ~ :
- : . . . .
16)S~Z31 Anal~
Calo'd. for C16H21N30 ~-C, 70.82; 1-l, 7~0; N. 15.49~
: Found: C, 71.15i H, 7.46; N, 15.71.
- Fxample 7~ N,N-Diethyl-a~4-dimethyl-3-phenylpyrazole-1-acetamide ~ ollowing the procedure of Example 68, but substituting diethylamine for aqueous ammonia there was obtained N,N-di-ethyl-~,4-dimethyl-~-phenylpyrazol e-1 -acetamide having a ; melting point of 55-57 C.
Analysis:
Calc'd. for C17H23N3b:
C, 71.54; H, 8.12; NJ 14.73.
, Found: C, 71.54; H, 8.07; N, 14.82.
~ a,4-Dimethyl-3-phenylpyrazole-1-acetanilide Y Following the procedure of Example 68, but substituting aniline for aqueous ammonia, there was obtained a~4-dimeth 3-phenylpyrazole-1-acetanilide having a melting point of 79-82 C.
~: ', Calc'd. for C~91~ N300 C, 74.73; H, 6.27; N, 13.76.
Found: C, 75.97; H, 6.39; NJ 13.17 ,~ ~ NJ a, 4- Trimethyl-~-phenylpyrazole-1-acetanilide Following the procedure of Example 68~ but substituting N-methylaniline for aqueous ammonia, there was obtained N,aJ4-trimetilyl-3-phenylpyrazole-1 acetanilide having a melt-. ,.
ing point o~ 111. $-114 . 5 C~
Calc'd. for C20H21N~0~
~!~:
Calc'd. for C14H1ffBrN30:
C, 52.18; H, 5. 04; N, 13. 04; Br, 24.80.
Found: C, 51.82; H, 4.90; N, 13.12; Br, 24.73.
10 and 4-bromo-NJN~a-trimethyl-5-phenylpyrazole-l-acetamide having a melting point of 117.5-119 C.
Analysis:
Calc'd. for Cl4Hl6BrN30:
C, 52.18; H, 5.o4; N, 13.04; Br, 24.80.
15 Found: C, 52.42; H, 4.98; N, 13.10; Br, 24.61.
Example 5 4-Chloro-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide and 4-chloro-N,N,a-trimethyl-5-phenylpyra~ole-1-acetamide Using the procedure of Example 1, but substituting 20 4-chloro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole - there were obtained 4-chloro-N,N,c~-trimethyl-3-phenylpyra-zole-l-acetamide with a melting point of 73.5-75 C.
Ana!ys~;s:
Calcld, for C14tl1~ClN91~:
- .
C, 60.54; H, 5.81, N, 15.13; Cl, 12.77. !:
Found: C, 60.62; H, 5.8~; N, 15.09; Cl, 12.72.
and 4-chloro-N,N,a-trimethyl-5-phenylpyrazole-1 acetamide witha melting point of 100.5-102 C. I
~: l 30 Calc'd. for C,4Hl8ClN30:
1' .
- . -. . . . .. .
~229 ~V532~3~
C, 60.54; H, 5.81; N, 15.1~; Cl, 12.77.
Found: C, 60.80; H, 5.95; N, 15.49; Cl, 12r91~
Example 6 4,5-~ibromo-N,N,~-trimethyl-3-phenylpyrazole-1-acetamide and 3,4-dibro~o-N,N,a-trimethyl 5-phenyl pyrazol e-1 -acetam i de Using the procedure of Example 1, but substitu~ing 3,4-dibromo-5-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained 4,5-dibromo-N,N,a-trimethyl-3-phenyl pyrazole-1-acetamide having a melting point of 132-134 C.
'; 10 ~
Calc'd. for C14Hl5Br2N30:
C, 41.9~; H, 3.77; N, 10.47; Br, ~i9.85.
- Found: C, 42.24; H, ~.82; N, 10.66; Br, 39.63.
and ~5,4-dibromo-N,N~a-trimethyl-5-phenylpyrazole-1-acetamide 15 having a melting point of 115-118 C.
Analysis:
Calc'd. for C1 4 H15Br2N30:
C, 41.92; H, :3.77; N, 10.47; Br, 39.~5.
Found: C, 41.92; H, 3.8}; N, 10.76; Br, 39,5~.
Ex~p e r N,N,a-Trimethyl-3,4-diphenylpyrazole-1-acetamide and N,N,a-trimethyl-4,5-diphenylpyrazole-1Oacetamide Using the procedure of Example 1, but substituting 3,4-diphenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3,4-diphenylpyrazole-1-acet-~mide having a melting point of 122-124 C.
Analysis:
Calc'd. ~or C20HzlN30:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.1~; H, 6~49; N, 13.54.
;50 and N,N,a-trimethyl-4,5-diphenylpyrazole-1-acetamide ~aving . .
~)5 ~;31 3 melting p~int of 151-15~ C.
~: ' Calc'd~ for CzoH21N30:
C, 75.21; H, 6.6~; N, 1~.16.
Found: C, 75.~0; H, 6.62; N, 1~.46.
Example 8 4-Ethyl-N,N,a-trimethyl-3-phenylpyrazole-1-acet-amide Using the procedure of Example 1, but substituting 4-ethyl-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained 4-ethyl-N,N,a-trimethyl-3-phenylpyrazole 1-acetamide having a melting point of 73.5-75 C.
Analysis:
Calc'd. for Cl~H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.88; H, 7.75; N, 15.75.
4,5,6,7-Tetrahydro-N,N,a-trimethyl-3-phenyl-lH-indazole-1-acetamide Using the procedure of Example 1, but substituting ;~;
3-phenyl-4,5,6,7-tetrahydroindazole for 4-methyl-3-phenyl- I ~-pyrazole there was obtained 4,5,~,7-tetrahydro-N,N,a-tri-methyl-3-phenyl-lH-indazole-1-acetamide having a melting point of 101-10~ C~
- Calc~d. for Cl8H29N~0:
C, 72.69; H, 7.80; N, 14.13.
Found: C, T2.77; H, 7.73; N, 14.24.
~ N,N,a-Trimethyl-~,5-diphenylpyrazole-1-acetamide ;~ Using the procedure of Example 1, but substituting 3J5.dlphenylpyraz~le for 4-methyl-~-phenylpyrazole5 there ~0 was obtained N,N,a-trimethyl-3,5-dipheny1pyrazole-1-aceta--~7-I,: , 1` -~ .
~229 1~ 5 ~ 3~
mide having a melting point oF 133-135 C.
Analysis:
Calc'd. for C20H2lN30:
~ C, 75.21; H, 6~6~; N, 1~.16.
; 5 Found: C, 75.31; H, 6.71; N~ 13.51 N,N,a,3,5-Pentamethyl-4-phenylpyrazole-1-acet-amide Vsing the procedure of Example 1, but substituting - 3,5-dimethyl-4-phenylpyrazole for 4-methyl-~-phenylpyrazole there was obtained N~N~a~3~5-pentamethyl-4-phenylpyrazole 1-acetamide having a melting point of 122-12~.5 C.
.Analysis: ;
Calc'd. For C1~HzlN90: -C, 70.82; ~, 7.80; N, 15.49.
Found: C, 70.8~; H, 7.71; N, 15.79.
;, ~ Nr N, a, 4, 5-Pentamethyl-~-phenylpyrazole-1-acet-amide Using the procedure of Exa~ple 1, but substituting .:
3,4-dimethyl-5-phenylpyrazole ~or 4-methyl-~-phenylpyrazole ~-there was obtained N,N,a,4,5-pentamethyl-~-phenylpyrazole-etamide having a melting point of 76_79 C.
Analysis: :
Calc'd. for Cl~Hz~N30:
C, 70.82; ~, 7.80; N, 15.49.
Found: C, 70.64; H, 7.75; N, 15.55.
N,N,a-Trimethyl-~-(o-tolyl)pyrazo1e-1-acetamide and N,N,a-~rimethyl-5-(o-tolyl)pyrazole-1-acetamide l -~ Using the procedure of Example 1.. but substituting : ~-(o-tolyl)pyrazole f~r 4-methyl-3-phenylpyrazole there was ~0 o~tained N,N,a-trimethyl-3-~o-tolyl)pyrazole 1-acetamide I, ...
lV53~31 3229 having a boili ng point of 164-174~0.3 mm.
~;
Calc'd. for C15H1gN30:
C, 70. 00; H, 7.44; N, 16.33.
Found: C, 69.60; H, 7.50; N, 16.22.
and N,N,a-trimethyl-5-~o-tolyl)pyrazole-1 -acetami de having ; a melting point of 84.5-86.5 C0 Ana ! ys i s :
~.
Calc'd. for C15H19N30:
C, 70. 00; H, 7.44; N, 16.33.
Found: C, 69.94; H, 7.32; N, 16.23.
Example 14 N,N,~,4-Tetramethyl-3-(o-methoxyphenyl)pyra-zole-1-acetamide and N,N,a,4-tetramethyl-5-(o-methoxyphenyl)pyrazole-1-acetamide ; 15 Using the procedure of Example 1, but substit~ing 4-methyl ~-(o-methoxyphenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-3-(o-methoxyphenyl)-pyrazole-1-acetamide having a boiling point of 180/0.5 mm.
Calc'd. for C1~H21N302:
C, 66.87; H, 7.~7; N, 14.62.
Found: C, 66.13; H~ 7.42; N, 14.50~
and N,N,a,4-tetramethyl-5-(o-methoxyphenyl)pyrazole-1-acet-amTde having a melting point of 118-120 C.
,, ~
Calc'd. for Cl~H21N902:
C, 66.87; H, 7.37; N, 14.62.
Found: C, 66.62; H, 7.27; N, 14063.
Examp!e 15 3-(o-Chlorophenyl)-N,N~a-trimethylpyrazole-1-acetamide and 5-(o-chlorophenyl)-N,N,a-tri-. . .
~ -29-;
~229 1053'~
methylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-(o-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained 3-(o-chlorophenyl)-N,N,a-trimethyl-5 pyrazole-1-acetamide having a boiling point of 176-178/.1 mm.
Calc'd. for C14HI6ClN30.
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.17; H, 5.82; N, 14.96; Cl, 12.58. ;
and 5-(o-chlorophenyl )-N,N,~-trimethylpyrazole-1-acetamide having a melting point of 83-86 C.
Analysis:
Calc'd. for C,4Hl6ClN30:
15 C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.89; H, 5.82; N, 15.06; Cl, 12.38.
3-(p-Chlorophenyl)-N,N,a-trimethylpyrazole-1-acetamide and 5-(p-chlorophenyl )-N,N,a-tri-methylpyrazole-1-acetamide Using the procedure of Example 1, but substituting 3-~p-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained 3-(p-chlorophenyl~-N,N,a-trimethylpyra-~',; zole-l-acetamide having a melting point of 95-99 C.
.
Calc'd. for Cl4Hl~iClN30:
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.57; H, 5.84; N, 15.20; Cl, 12.83.
and 5-(p-chlorophenyl)-N~N~a-trimethylpyrazole-l-acetamide having a melting point of 96-97 C.
~:
. .
~~~
; ' . .
~C~53Z3~
Calc'd. for C14H16ClN30:
C, 60.54; H, 5.81; N, 15.13; Cl, 12.77. ~ -Found. C, 60.~2; H~ 5.74; N, 15~07; Cl~ 12.96.
~ 3-(p~Chlorophenyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(p-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-pyrazole there was obtained 3-(p-chlorophenyl)-N,N,a,4-tetra-methylpyrazole-1-acetamide having a melting point of 99.5-101 C. ~ -Analysis:
Calc'd. for C15HI8ClN30:
C, 61.74; H, 6.22; N, 14.41; Cl, 12.15.
Found: CJ 61.55; H, 6.o4; N, 14.41; Cl, 12.19.
- 15 ~ 3-(o-Methoxyphenyl)-N,N,~-trimethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting ~;
~ 3-(o-methoxyphenyl)pyrazole for 4-methyl-3-phenylpyrazole Y~ there was obtalned 3-(o-methoxyphenyl)-N,N,a-trimethylpyra- ~ -20~ zole-1-acetamide havin3 a melting point of 92-94 C.
Analysis;
Calc'd. for C15H1gN3C2:
, C, 65.91; H, 7.01; N, 15.37.
!~ Found: C, 65.63; H, 6.96; N, 15.33.
i~ 25 ~ 3-(o-Chlorophenyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting ~ 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-i ~ pyrazole there was obtained ~-(o-chlorophenyl)-N,N,a,4-tetra-~ 30 methylpyrazole-1-acetamide having a melting point of -3229 ,l 1~5~231 98.5-100.5 C
Analysis:
Calc'd. for C15H18ClN30:
C, 61.74; H, 6.22; N~ 14,40; Cl~ 12.15.
Found: C, 61.98; H, 6.35; N, 14.39; Cl, 12.22.
3-(m-Chlorophenyl)-N,N,a,4-tetramethylpyra-zole-1-acetamide Following the procedure of Example 1, but substituting 3-(m-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-pyrazole there was obtained 3-(m-chlorophenyl)-N~N~a~4-tetra methylpyrazole-1-acetamide having a melting point of 7~ 75 C.
Analysis:
Calc'd. for C15Hl8ClN30: -C~ 61.74; H~ 6.22; N, 14.40; Cl, 12.15.
Found: CJ 61.90; ~ 6.20; N, 14.30; Cl, 12.21.
3-(m-Chlorophenyl)-N,N,~-trimethylpyrazole-1-acetamide Following the procedure of Example 1~ but substituting 3-(m-chlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole ~; there was obtained 3-(m-chlorophenyl)-NJN,a-trimethylpyra-zole-1-acetamide having a boiling point of 175/0.08 mm.
Ana l ys 7 s :
Calcld. for C14H1aClN30:
C~ 60.54; H, 5.81; N, 15.13; Cl, 12.77.
Found: C, 60.24; H, 5.92; N, 15.39; Cl, 17.12.
3-(2,5~Dichlorophenyl)-NJN,a-trimethylpyrazole-~ 1-acetamide - Following the procedure of Example 1, but substituting 3-(2,5-dichlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole ;, , . . - .
1~S323~
there was obtained ~-(2,5-dichlorophen~ NrN,~-trimethyl-pyrazole-1-acetamide having a melting point of 73.5-76.5 C.
Analysi~s:
Calc'd. for C14H15Cl2N30: :
C, 53.86; H, 4.8~; N, 13.4~; Cl, 22.71.
Found: C, 54.04; H, 4.92; N, 1~.65; Cl, 22.73.
N,N,a,4-Tetramethyl-3-(o-tolyl)pyrazole-1-acet-amide :~
Following the procedure of Example 1~ but substituting 4-methyl-3-(o-tolyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N~N~a~4-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide having a boiling point of 178-182/0.7 mm. :::
N,N,a-Trimethyl-3-(p-tolyl)pyrazole-1-acetamide ` Following the procedure of Example 1, but substituting t 15 ~-(p-tolyl)pyrazole for 4-methyl-3-phenylpyrazole there was : obtatned N,N~-trimethyl-3-(p-tolyl)pyrazole~1-acetamide :
, having a melting point of 79-82 C.
. . .
: ~ Calc'd. for C15~19N30:
C, 70.00; H, 7.44; N, 16.33.
` Found: C, 70.2~; H, 7.29; N, 16.60.
N,N,a-Trimethyl-3-(m-nitrophenyl)pyrazole-acetamide ~ : ~ Following the procedure of Example 1, but substituting '~: 25 3-(m-nitrophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a-trimethyl-3-(m-nitrophenyl)pyra-: zole~l-3cetamide having a melting poi nt of 117-119 C.
Analysis:
.:
~: Calc'd. for Cl4Hl~NgO3:
~0 C, 58.32; H, 5.59; N, 19.44.
-33~
~.. .. . . . . .. . . . .
1~ 5 ~
Found: CJ 59. o6; H, 5.68; N, 19.72.
Example 26 N,N,~-Trimethyl-3-(276-dichlorophenyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(2,6-dichlorophenyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a-trimethyl-3-(2,6-dichlorophenyl~ -: pyrazole-1-acetamide having a melting point of 88-go C.
Analysis:
Calc'd. for C14H1sCl2N30:
C, 53.86; H, 4.84; NJ 13.46; Cl, 22.71.
Found: C, 53.78; H, 5.02; N, 13.41; Cl, 22.73.
Example 27 4-Chloro-N,N-diethyl-a-methyl-3-phenylpyrazole-1-acetamide and 4-chloro-N,N-diethyl-a-methyl-5-phenylpyrazole-1-acetamide 15 Using the procedure of Example 1, but substituting 2-chloro-N,N-diethylpropionamide for 2-chloro-N,N-dimethyl-propionamide and 4-chloro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there were obtained 4-chloro-N~N-diethyl-~-methyl-3-phenylpyrazole-1-acetamide having a boiling point of 191-192 /0.74 mm.
~:
Calc'd. for Cl~H20ClN30:
C, 62.84; HJ 6.59; N, 13.74; C1J 11.59.
Found: C, 62.50; H, 6.74; N, 13.48; Cl, 11.58.
and 4-chloro-N,N-diethyl-~-methyl-5-phenylpyrazole-1-acet-amide having a meltîng point of 85 87 C.
~ Analysis:
-! Calc'd. for C1~H20ClN30:
C, 62~84; H~ 6.59; N~ 13-74; C1~ 11-59-Found: C, 62.92; H, 6.71; N) 13.62; Cl, 11.58.
, , , . ,, :
~22g 1 0 5 ~Z 31 ~-Ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acet-amide and a-ethyl-N,N~-trirnethyl-5-phenylpyra-zole-1^acetamide Using the procedure of Example 1, but substituting 2-chloro-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-~ propionamide there were obtained a-ethyl-N,N,4-trimethyl-- 3-phenylpyrazole-1-acetamide having a melting point of 86-88 C.
Analysis:
Calc'd. for C~6H21N30: -C, 70.82; H, 7.80; NJ 15.49.
Found: CJ 70.91; HJ 7.9~; NJ 15.73.
and ~-ethyl-N,N,4-trimethyl-5-phenylpyrazole-1-acetamide having a melting point of 88-go c.
~ :
Calctd. for Cl6H2lN30:
CJ 70.82; H, 7.80; N, 15.49.
Found: C, 70.83; HJ 7.82; N, 15.56.
Alternate Synthesis for ~ ;~
, , ~
Sodium methoxide powder (216 g., 4.0 mole) was added over 10 minutes to a stirred solution of 4-methyl-3-phenyl-pyrazole (632 g.~ 4.0 mole) in tetrahydrofuran (1.0 liter) at 10 C. 2-Bromo-N,N-dimethylbutyramide (911 9., 4.7 mole) was added dropwise over 30 minutes while maintaining ; the temperature of the reaction solution below 30 C. by external cooling. The solution was stirred for an addition-al 30 minutes at room temperature, and the THF was then re-- moved under reduced pressure. The residual oil was parti-tioned between chloroform and water. The chloroform layer ' ' .. ..
.
.: .
~53Z3~
i was evaporated and the residual oil was recrystallized from benzene:Skellys~lve B to give 772 g. of a-ethyl-N~N~4-tr methyl~3-phenylpyrazole-1-acetamide, m.p. 85.5-87.5 C.
Evaporation of the crystallization mother liquors gave 365 9. of oil containing additional product.
Example 29 N,N,a-Trimethyl-3-(2-thienyl)pyrazole-1-acet-amide and N,N,a-trimethyl-5-(2-thienyl)pyra-zole-1-acetamide Following the procedure of Example 1, but substituting 3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3-(2-thienyl)pyrazole-1-acet-amide having a melting point of 95-97 C.
Analysis:
Calc'd. for C12H15N30S:
C, 57.80; H, 6.o6; N, 16.85; S, 12.85.
Found: C, 57.52; H, 5.98; N, 16.76; S, 13.17.
- and N,N,a-trimethyl-5-(2-thienyl)pyrazole-1-acetamide having a melting point of 80 82 C.
.' ~:
,~
Calc'd. for C12H1sN90S: -C, 57.80; H, 6.Q6; N, 16.85; S, 12.85.
, .
Found: C, 58.10; H, 5.95; N, 16~87; S, 13.05.
; ~ N,N,aJ4-Tetramethyl-3-(2-thienyl)pyrazole-1-acetamide and N,N,a,4-tetramethyl-5-(2-thi- -~
`~ 25 enyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 4-methyl-~-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there were obtained N,N,~,4-tetramethyl-3-(2-thienyl)pyra-- zole-1-acetamide having a melting point of 100-102 C.
Analysis:
- .
:
~229 1~5;~231 Calcld. for Cl3H17N30S:
C, 59.29; H, 6.51; N, 15.96; S, 12.17. ~-Found: C, 59. 09; H, 6~ 52; N, 15.86; S, 11.99.
and N,N,a,4-tetramethyl -5- (2-thienyl )pyrazole-1-acetamide having a melting point of 77-80 C.
Analysis:
Calc'd. ~or Cl9Hl7N30S:
C, 59.29; H, 6.51; N, 15.96; S~ 12.17.
Found: C, 59.02; H, 6.27; N, 15.87; S, 12.29.
Example 31 ~-Ethyl~,N,4-trimethyl-3-(2-thienyl)pyrazole-1-acetamide and a-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example 1, but subs~ituting 4.methyl-3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyra : 15 zole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-; dlmethylpropionamide there were obtained a-ethyl-N,N,4-tri-methyl-3-(2-thienyl)pyrazole-1-acetamide having a melting point of 83-85 C. -Analysis:
~; . . . .
Calcld. for C14H1gN305:
C, 60.62; H, 6.90; N~ 15.15; S, 11.56.
Found: ~, 60.61; H, 6.76; N, 15.14; S, 11.49.
a~d a-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acet-amlde hav7ng a boiling point of 170/0.7 mm.
; ~ 25 Ana! ys ~ s: :-Calc'd. for CI~Hl~N30S~
C, 60.62; H, 6.90; N~ 15.15; S, 11.56.
Found: C, 60.31; H, 6.97; N, 15.07; S, 11.23.
E~ampl~ N,N,a,4-Tetramethyl-3-(5-chloro-2-thienyl)-pyrazole^1-acetamide ':
3~29 5;~Z3~
Following the procedure of Example 1, but substituting 4-methyl-3-(5-chloro-2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-3-(5-chloro-2-thienyl)pyrazole-1-acetamide having a melting point of 111. 5~114 C .
Ana!Ysis Calc'd. for C13Hl6ClN30S:
C, 52.43; H, 5.42; N, 14.11, Cl, 11.91;
S, 10.77.
Found: C~ 52.44; H, 5.59; N, 14.19; Cl, 11~68;
S, 10.85.
N,N,4-Trimethyl-a-propyl-3-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example 1~ but substituting 4-methyl-3-(2-thienyl)pyrazole for 4-methyl-3-phenylpyrazole ~ ;
and 2-bromo-N,~ dimethylvaleramide for 2-chloro-N,N-dimethyl-propionamide there was obtained N,N,4-trimethyl-a-propyl-3-(2-thienyl)pyrazole-1-acetamide having a melting point of 85-87.5 C.
Calc'd for C15H21N30S:
5J 61.82; HJ 7.26; N, 14.42; S, 11. 00.
Found: C, 61.70; H~ 7.40; N, 14.40; S, 11. 05.
~ 3-(2-Furyl)-N,N,a,4-tetramethylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 3-(2-furyl)-4-methylpyrazole for ~-methyl-4-phenylpyrazole there was obtained 3-(2-fwryl)-N,N,a,4-tetramethylpyrazole-1-acetamide having a melting point of 93-95 C.
:50 Ana l ys i s:
-~8-.
.
10S~231 Calc'd. for C1 3Hl 7N302:
C, 63.14; H, 6.93; N~ 16.99.
Found: C, 63~17; H, 7.13i N, 17.07.
Example 35 a-Ethyl-3-(2~furyl)-NJN~4-trimethylpyrazole-1-acetamide Foll~winy the procedure of Ex3mple 1, but substituting 3- (2-furyl)-4-methylpyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-di-methylpropionamide there was obtained a-ethyl-3-~2-furyl) N,N,4-trimethylpyrazole-1-acetamide having a melting point of 115-117 ~.
Analysis:
Calc'd. for C14H1gN302:
Cg 64.34; H, 7.3~; N, 16.08.
` 15Found: C, 64.46; H, 7.26; N, 15.89. -Example 36 3- (2-Furyl)-N,N,4-trimethyl-a-propylpyrazole-l-acetamide :
Following the procedure of Example 1, but substituting 3- (~-furyl)-4-me~hylpyrazole for 4-methyl-3.phenylpyrazole 20 and 2-bromo-N,N-dimethylvaleramide for 2-chloro-N,N-dimethyl- ~
propionamide there was obtained 3-(2-furyl)-N,N,4-trimethyl- ~ -o~-propylpyrazole-1-acetamide having a melting point of 107-109 C.
.' ~,:
25Calc'd. for C15H21N30-C, 65,43, H, 7.69; N, 15.26.
Found: C, 65 61; Il, 7.78; N, 15.21.
~e~:Z N,N,~,~J4-Pentamethyl-5-phenylpyrazole-1-pro-propionamide and N,N,a,ag4-pentamethyl-3-phenyl-;~50 pyrazole-1-propionamide .~ - -Following the procedure of Example 1, but substituting 3-chloro-N,N,2,2-tetramethylpropionamide for 2-chloro-N,N-dimethylpropionamide there were obtained N,N,a,a,4-pen-tamethyl-5-phenylpyrazole-1-propionamide having a melting point of 59-60 C.
Analysis:
Calc'd. for Cl7H23N30:
C, 71.54;~, 8.12; N, 14.73.
Found: C, 71.61; H, 8.31; N, 14.65.
and NJNJaJa94-pentamethyl-3-phenylpyrazole-l-propionamide having a boiling point of 175 /0.03 mm.
Analysis:
Calc'd. for C17Hz3N30:
C, 71.54; H~ 8.12; N, 14.73 Found: C, 71.43; H, 8.45; N, 14.79.
Example 38 N,N,~-Trimethyl-3-(o-nitrophenyl)pyrazole-1-acetamide Following the procedure of Example 1, but substitut-ing 3-(o-nitrophenyl)pyrazole for 4-methyl-3-phenylpyra-~20 zole there was obtained NJN,a-trimethyl-3-(o-nitro-;phenyl)pyrazole-1-acetamide, as a brown liquid.
3-(o-Chlorophenyl)-~-ethyl-N,N-dimethyl-pyrazole-1-acetamide Following the procedure of Example 1J but substitut-5 ing 3-(o~chlorophenyl)pyrazole for 4-methyl-3-phenyl- ~ -pyrazole and 2-bromo-NJN-dimethylbutyramide for 2-chloro-N,N-dimethylpropionamide there was obtained 3-(o-chloro- -phenyl)-a-ethyl-N,N-dimethylpyrazole-1-acetamide having a melting point of 38.5-40 C.
Ana!~sis:
.. .
~229 ~S3~Z3~
Calcrd. for Cl5H18ClN30:
C, 61.74; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.99; H, 6.22; N, 14.38; Cl, 12.31.
~ ~-Ethyl-N,N-dirnethyl-3-(o-tolyl)pyrazole-1-acetamide Following the procedure of Example 1, but substitut-ing 3-(o tolyl)pyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-di-methylpropionamide there was obtained ~-ethyl-N,N-dimethyl-3-(o-tolyl~-pyrazole-1-acetamide having a melting point of 48-51Q C.
Calc'd. for C16H21N30-C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.66; H, 7.74; N, 15.32.
~ ,.~-(o-Chlorophenyl)-a-ethyl-N,N,4-trimethyl-.
pyrazole~ acetamide Following the procedure of Example 1, but substi-tuting 3~(o-chlor~phenyl)-4 methylpyrazole for 4-methyl-3-phenylpyrazo7e and 2-bromo-N,N-dimethylbutyramide for 2-chloro-NJN-dimethylpropionamide there was obtained 3-(v~chlorophenyl~-~-ethyl-N,N,4-trimethyl-pyrazole-1-acetamTde having a boiling point of 180~0.15 mm.
Analysis:
Calc'd. for C1~H20ClN30:
C, 62.84; H, 6.59; N, 13.74; Cl, 11.59.
Found: C, 62.69; H, 6.81; N, 13.73; Cl, 11.52.
~ ~-(3-Bromopropyl)-N,N~4-trimethyl-3-phenyl-pyrazole-1-acetamide .
. , - , .
-, . . .
1053Z;3~
Following the procedure of Example 1, but substituting 2,5-dibromo-N,N-dNnethylvaleramide for 2-chloro-N,N-dimethyl-propionamide there was obtained ~-(3-bromopropyl)-N,N,4-tri-methyl-3-phenylpyrazole-1-acetamide as a liquid.
Example 4~ a-(4-Bromobutyl)-N~N~4~trimethyl-3-phenylpyra- ~-zole-1-acetamide Following the procedure of Example 1, but substituting 2,6-dibromo-N,N-dimethylcaproamide for 2-chloro-N,N-dimethyl-propionamide there was obtained ~-(4-bromobutyl)-N,N,4-tri-methyl-3-phenylpyrazole-l-acetamide as a liquid.
a-Ethyl-N,N,4-trimethyl-3-(o-tolyl)pyrazole-1-acetamide Following the procedure of Example 1, but substituting 4-methyl-3-(o-tolyl)pyrazole for 4-methyl-3-phenylpyrazole and 2-bromo-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-; propion3mide there was obtained a-ethyl-N,N,4-trimethyl- -~
3-(o-tolyljpyrazole~1-acetamide having a boiling point of ` 155-157/0.05 mm.
, ! Y . :, .
Calc'd. for Cl7H23N30:
C, 71.$5; H, 8.12; N, 14.72.
Found: C, 71.18; H, 8.27; N, 14.65.
Example 45 a-(2-chloroethyl)-N~N~4-trimethyl-3-phenylpyra zole-1-acetamide Following the procedure of Example 1, but substituting , 2-bromo-4-chloro-N,N~dimethylbutyramide for 2-chloro-N,N-dlmethylpropionamide there was obtained a t2-chloroethyl)-N,NI4-trimethyl-~-phenylpyrazole-1-acetamide as a liquid.
a-Cyclohexyl-N,N,4-trimethyl-3-phenylpyrazole-~0 1-acetamide -. . .. .
: - . . : . .
~0~3Z3~
Following the procedure of Example 1, but substituting ~-bromo-N,N-dimethyl-1-cyclohexaneacetamide for 2-chloro-N,N-dimethylpropionamide there was obtained a-cyclohexy N,N,4-trimethyl-3-phenylpyrazole-1-acetamide having a melting point 102.5-104.5 C.
- -:
Calc'd. for C20H27N~0:
C, 73.81; H, 8.36; N, 12.91.
Found: C, 73.70; H, 8.44; N, 12.69.
Example 47 a-cyclohexyl-NJN-dimethyl-3-phenylpyrazole 1-acetamide Following the procedure of Example 1, but substituting a brom~-N~N-dlmethy~ cyclohexaneacétamide for 2-chl~ro N,N-dimethylpropionamide and 3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained ~-cyclohexyl-N,N-di-me~hyl-3-phenylpyrazole-1-acetamide having a melting point of 87.5-go C.
Calc'd. for C1gH25N30:
~i 20 C, 73.28; H, 8.o~; N, 13.49.
Found: C, 7~.~6; H, 8.o8; N, 13.39.
a-Butyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 1, but substituting 2-bromo-N,N-dimethylcaproamide for 2-chloro-N,N-dimethylpro-pionamide there was obtained ~-butyl-N,N,4-trlmethyl-3- ~ -phenylpyrazole-1-acetamide having a boiling point of 189/0.1 mm.
Analysis:
Calç'd. for Cl8H25N30-:
~l~53Z31 C, 72.20; H, 8.42; N, 14.04.
Found: C, 71.76; H, 8.~o; N, 13.89.
Examp1e 49 N,~,a,4-Tetramethyl-3-phenylpyrazole-1-aceta-mide, N,~,a,4-tetramethyl-5-phenylpyrazole-1-acetamide,and N,a,4-trimethyl-~-phenylpyra-zole-1-propionamide Sodium hydride (25.0 9. of 57~ dispersion in oil~ o 6 mole) was added to a stirred solution of 4-methyl-3-phenyl-pyrazole (7g.0 g., 0.5 mole) in tetrahydrofuran. Ethyl-2-bromoisobutyrate (136.0 9., 0.7 mole) was added and the $olution was refluxed for 4 hours. The solvent was removed by evaporation and the residual ester mixture was hydrolyzed by refluxing with methanolic sodium hydrbxide solution (40 g. sodium hydroxide in 600 ml. of 30~ methanol-water).
After cooling, the alkaline reaction solution was extracted with ether and the aqueous phase was acidified with concen-trated hydrochloric acid. The solution was extracted with chloroform, and the chloroform layer was evaporated to give a crude acid mixture in which a,~,4-trimethyl 3-phenylpyra-zole-1-acetic acid was the major isomer.
The crude acid was dissolved in benzene (1 liter), and thionyl chloride (59.5 g., 0.5 mole) was added and the so1u-tion was refluxed for 3 hours After cooling, the solution was added slowly to a stirred solu~ion of 40% aqueous methyl-amine (200 ml.) containing ice (500 9.). After 10 minutes, the benzene layer was separated, washed with water, and evaporated to afford 100 9. of mixed methylamides.
Chromatography on silica gel afforded 64 g. of N,a,~,4-tetramethyl-3-phenylpyrazole-1-acetamide, which was ~0 recrystallized from cyclohexane; m.p. 84-88 C.
.
, ~
3229 ~ ;
l~S3Z31 Calc'd. for C1sH~9N30:
Cl 70.00; H, 7.44; N, 16.33.
Found: C, 69.95; H, 7.61; N, 16.40.
Further elution of the column afforded 4.1 9. of N,~,~,4-tetramethyl~5-phenylpyrazole-1-acetamide, which was ; recrystallized twice from ethyl acetate for analysis; m.p.
; 119-120 C.
Analys ! 5 Calc'd. for C15H1~N30:
CJ 70. 00; H, 7.44; N, 16.33.
Found: C, 70.25; H, 7.64; N, lÇ.55.
Further elution of the column afforded 6.6 9. of N,a,4-trimethyl-3-phenylpyrazole-1-propionamtde, which ~as recrystallized twice from ethyl acetate for analysis; m.p.
123-124 C.
Analysis:
Calc'd. for C15H19N30:
C, 70.00; H, 7.44; N, 16.33.
Found. C, 70.18; H, 7.41; N, 16.52.
,a,4 Trimethyl.3-phenylpyra201e-1-acetamide Following the procedure of Example 49, but substituting aqueous ammonia for aqueous methylamine there was obta;ned ~,a,4-trimethyl-~-pheny1pyrazole-1-acetamide having a melt-ing point of 105-1~6 C.
Analysis Calc'd. for C14H17N~0:
C, 69.11; H, 7.Q4; N, 17.27.
Found: C, 69.01; H, 7.02; N, 17.37.
3Q ~ N-~thyl-aJa~4-trimethyl-3-phenylpyrazole-l-acet . . , : .
322g 1~)53231 amide and N-ethyl-aJ4-dimethyl-3-phenylpyrazole-1-propionamide F~llowing the procedure of Example 49, but substituting aqueous ethylamine for aqueous methylamine there was obtained N-ethyl-a,~,4-trimethyl-3-phenylpyrazole-1-acetamide having a bqiting point of 150/0.2 mm.
Analysi_s:
Calc'd. for C18H2~N30:
.
C, 70.82; H, 7.80; N, 15.49;
10 Found: C, 70.65; H, 7.80; N, 15.3C).
and N-ethyl-~J4-dimethyl-3-phenylpyrazole-1-propionamide hav7ng a melting point of 110.5-112.5 C.
Analysis:
Calc'd. for C16H2lN30:
15 C, 70.82; H, 7.Bo, N, 15.49.
Found: C, 70.33; H, 7~64; N, 15032.
Exame!e_52 c~a~4-~rimethyl-3-phenyl-N-isopropylpyrazole 1-acetamide and a~4-dimethyl-~-phenyl-N-isopr pylpyrazole-1-propionamide 20 Following the procedure of Example 49, but substituting Isopropylamine for aqueous methylamine there were obtained a,a,4-trimethyl-~-phenyl-N-isopropylpyrazole-1-acetamide having a boiling point of 160~/0.25 mm.
Analysis:
~ .
- 25 Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73. -- ~ , Found: C, 71.73; H, 8.20; N, 14.74.
and aJ4-dtmethyl-3-phenyl-N-isopropylpyrazole-l-propionamide having a melting point of 104-107 C.
:
30 Analysis:
'''' :
,: ... -, , .. . , . . .,, . : . .
~229 1~)53~31 Calc'd. fcr C17Hz3N30:
C~ 71.54; HJ 8.12; N~ 14.7~
Found: C, 70.6g; H, 7.79; N, 14.38.
~ a,~J4-Trimethyl-3-phenyl~N-propyl pyrazole-1-acetamide and a,4-dimethyl-3-phenyl-N-propyl-pyrazole-1-propionamide Following the procedure of Example 49, but substituting propylamine for aqueous methylamine there were obtained ~,a,4-trimethyl-3-phenyl-N-propylpyrazole-1-acetamide having a melting point of 47-50 C.
Ana~ s~s:
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.7~.
Found: C, 71.62; H, 8.03; N, 14.37.
~nd a,4-dlmethyl-~-phenyl-N-propylpyrazole~1-propionamide havlng a melting point of 96-98 C.
Calc'd. for C17H23N30:
C, 71.54; Hj 8.12; N, 14.73.
20Found: C, 71.51; H, 7.97; N, 14.39.
Example 54 N-Buty~ J4-trimethyl-3-phenylpyrazole-l-acet amide , :~
Followlng the procedure of Example 49, but substituting butylamTne for aqueous methylamine there ~as obtained N-buty~ 4-trimethyl-3-phenylpyrazole-l-acetamide having a melting point of 5~-57 C.
~i ~, , Calc d. for ClaH~5N30:
C, 72.20; H, 8.42, N, 14.04.
Found: C, 72.47; HJ 8.62; N, 14.26.
- . ~
1~53~31 N-tert-Butyl-~,a,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 49, but substitutillg tert-butylamine for methylamine, there was obtained N-tert-butyl-a,a,4-trimethyl-3-phenylpyrazole-1-acetamide having a melting point of 71-75 C.
Analysis:
Calc'd. for C18H25N30:
C, 72.20; H, 8.42; N, 14.04.
lQ Found: C, 71.99; H, 8.78; N, 13.820 a,a,4-Trimethyl-3-phenylpyrazole-1-acetanilide Following Example 49, but substituting aniline for aqueous methylamine there was obtained ~,a,4-trimethyl-: 3-phenylpyrazole~1-acetanilide having a melting point of 1~6~119 C.
Calc'd. for C20HzlN30:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.04; H, 6.54; N, 1~.04.
20 ~ NJaJa~4-Tetramethyl-3-phenylpyrazole-l-acet- . ~ :
anilide Following the procedure of Example 49, but subs~ituting N-methylaniline for aqueous methylamine there was obtained - N,a,a,4-tetramethyl-3-phenylpyrazole-1-acetanilide having a ::
melting point of 152-154 C.
Calc'd. for C2~H29N30:
C, 75.64; H, 6.95; N, 12.60.
Found: C, 75.66; HJ 7.09; N, 12.79.
~ N-Benzy7 a,a,4-trimethyl-3-phenylpyrazole-; ~
l~)S3Z3~
1-acetamide Following the procedure of Example 49, but subs~it~ting benzylamine for aqueous methylamine there was obtained N-benzyl-a,a,4-trimethyl-~-phenylpyrazole-1-acetamide having a melting point of 87-go C~
Calc'd. for C21H23N30:
C, 75.64; H, 6.95; NJ 12.60.
Found: C, 75.40; H, 6.96; N, 12.28.
Example 59 N,N,~,~,4-Pentamethyl-3-phenylpyrazole-1-acet-amide and N,N,a,4-tetramethyl-3-phenylpyrazole~
1-propionamide ` Following the procedure of Example 49, but substituting aqueous dime~hylamine for aqueous methylamine, there were obtalned N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide having a melting point of 107-109 C.
Analysis: , Galcid. for C1eH2lN30:
C, 70.82; H, 7.80; N, 15.49.
; 20~ound: C, 70.98; H, 7.90; NJ 15.73.
and N~NJaJ4-tetramethyl-3-phenylpyrazole-l-propionamide ~ . :
having a melting pofnt of 51-54 C.
Analysls:
. - - .
Calc'd. for C~eH2~N30: .
~5CJ 70,82; H~ 7~80; N, 15.49.
Found~ C, 71.03; H, 7.79; N, 15.42.
! Alterna~e ~ of N?N~ ,4~pentamethyl-3-phenylpyra zole-l-acetamide Sodium methoxtde powder (65 9., 1.2 mole) was added 30 slowly So a sti rred mixture of 4-methyl -3-phenylpyrazole -4g~
. :' 11~5323~
(158 9.J 1.0 mole) and ethyl-2-bromoisobutyrate (238 9., 1.2 mole) at 100 C. After a~dition was complete the reac-tlon was cooled slightly, 80 9. sodium hydroxide in 400 ml.
of water, 100 ml. ethanol was added, and the solution was heated under reflux for 1 hour. After cooling the solution was extracted with ether to remove unchanged 4-methyl-3-phenylpyrazole (ca 20 9.). The aqueous phase was care-fully acidified with concentrated hydrochloric acid and the pyra~ole acid was extracted into chloroform.
The chloroform was removed under reduced pressure J the residue was dissolved in benzene ~500 ml.), thionyl chloride (140 9., 1.1 mole) added, and the mixture was stirred under-reflux for 3 hours. After cooling the solution was added to a stirred solution of 25~ aqueous dimethylamine (600 ml.) containing ice, the temperature was heid below 30 C. during the addition. The benzene layer was separated, washed with water and evaporated. The dark brown residual oil was crystallized from methanol (ca 200 ml.) at -10 C. and then from benzene:Skellysolve B to give 110 9. of N,N,a,a,4-pen-tamethyl-3-phenylpyrazole-1-acetamide, m.p. lP9-111 C.
Additional product was obtained by chromatography of the mother liquors.
N,N-Diethyl-a,a,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 49J but substitut-ing dlethylamine for aqueous methylamine, there was -obtained N~N-diethyl-a,a,4-trimethyl-~-phenylpyrazole-1-acetamide having a melting point of 50-52 C.
~ ,~,. .
Calc'd. for C~8H25N30 -5o-- . .
, 322g ~53Z31 C, 72.20; H, 8.42; N, 14.04 Found: C, 72.28; H, 8.44; N, 140 07.
N,a,a,4-Tetramethyl-N-octyl-3-phenylpyrazole-1-acetamide Foll~ing the procedure of Example 49, but substituting N-methyloctylamine for aqueous methylamine, there was obtained N,a,a,4-tetramethyl-N-octyl-3-phenylpyrazole-1-acetamide having a melting point of 75-78 C.
Analysis- -~
Calc'd. for C23H35N30~
C, 74.75; H, 9.55; N, 11.37.
Found: C, 74.74; H, 9.43; N, 11.12.
Example 62 N,N,a,a-Tetramethyl-3-phenylpyrazole-1-acetamide and N,N~a-trimethyl-3-phenylpyrazole-1-propionamide ~ 15 Following the procedure of Example 49, but substitut-.~ ing 3-phenylpyrazole for 4-methyl-3-phenylpyrazole and aqueous dimethylamine for aqueous methylamine there were obtained N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide having a melting point of 99.5-102~ C.
Analysis:
Calc'd. for Cl5H1gN~0: ~ -C, 70.00; H, 7.44; N, 16.33.
Found: CJ 69. 83; H, 7.47; N, 16.16.
and N,N,a-trimethyl-3-phenylpyrazole-1-propionamide having a melting point of 69-71.5 CO
Analysis: ~
Calc'd. for C~5H19N30:
., .
C, 70.00; H, 7.44; N, 16.33.
Found: C, 69.97; H, 7.55; N, 15.90.
~0 ~ N,N-Diethyl-3-(2-furyl) a,a,4 trimethylpyrazole .
,, 3~29 l~S~Z31 1-acetamide Following the procedure of Example 49, but substitutin~
3-(2-furyl)-4-methylpyrazole for 4-rnethyl-3-phenylpyrazo1e and diethylamine for aqueous methylamine there was obtain~d 5 NJN-diethyl-3-(2-furyl)-a~a~4-trimethylpyrazole-l-aceta~ e having a melting point of 73-76 C~
Ana!ysis^ :
Calc'd. for C16H23N302.
C, 66.41; H, 8.01; N, 14.52 Found: C, 66.19; H, 7.83; N, 14.24.
Example 64 ~-(2-Furyl )-NJ a, a~4-tetramethylpyrazole-l-ace~
amide ; Following the procedure of Example 49J but substituting ~-(2-furyl)-4-methylpyrazole for 4-methyl-3-pheny1pyrazole 15 there was obtained 3-(2-furyl)-N,a,cl.,4-tetramethylpyra~ole , 1-acetamide having a melting point of 101-103 CO
!
; Analysis:
Calc'd. for C13H~7N
~i .
CJ 63.14; H~ 6.93; N~ 16.99.
~- 20 Found: CJ 61.58; H~ 6.69; N, 16.48. -3-(o-Chlorophenyl)-N,N,c~., a-tetramethylpyrazole-1-acetamide Follawing the procedure of Example 49, but substituting ~- (o-chlorophenyl)pyrazole for 4-methyl-~-phenylpyra~ole 25 and dimethylamine for aqueous methylamine there was obtaine~
3- (o-chlorophenyl)-NJN,a,a-tetramethylpyrazole-1-acetamide having a melting point of 751-80.5 C.
Analys!s~
Calc'd. for C15Hl8ClN30:
- 30 C, 61.74; H, 6.22; N, 14.40; C1J 12.15.
, . .
. ... .. , . , . .,, ., .. ~ : , .
~i229 ~05;~3~
Found- C, 62. 00, H, 6.45; N, 14~46; Cl, 12. o6.
Example 66 N,N,a,~,Tetramethyl -3-(o-tol yl)pyrazole-1-acetamide Following the procedure of Example 49, but substituting ~- (o-tol yl )pyrazole for 4-methyl 3-phenyl pyrazole and 5 dimethylamine for aqueous methylamine there was obtained N,N,a,c~-tetramethyl-3- (o-tolyl )pyrazole-1-acetamide having a melting point of 78.5-81 C.
Ana l ys i s :
Calc' d. for Cl~3H2~N30:
10C, 7~.82; H, 7.80; N, 15.49.
Found: C, 70062; H, 7088; N, 15.69. -Example 67 N,N,a,a,4-Pentamethyl-3-(o-tolyl )pyrazole-1 -a ce tam i de Following the procedure of Example 499 but substituting 15 4-methyl-3-(o-tolyl )pyrazole for 4-methyl-3-phenylpyrazole and dimethylamine for methylamine there was obtai ned N.N, a) a,4-pentamethyl -3- (o-tol yl )pyrazole-1-acetamide havi ng a melting point of 145-147 C.
Ana l ys i s:
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73.
Found: C, 71.51; H, 8.50; N, 14.83.
. ~e~ .
Part A - a,4-Dimethy~-3_phenylpyrazole 1-acetic acid .
Sodium hydride (50.0 g., 57,~ in oil, 1.2 mole) was added over 20 minutes to a stirred solution of 4-methyl-3-phenylpyrazole (158 g., 1.0 mole) in THF (1.0 l.) maintair,ed at 10-20 C. Ethyl 2-bromopropionate (235 g., 1.3 mole) was added and the solution stirred for 18 hours, after which t ime ethanol was added and the solvent was rernoved by evapor-;
~229 ~C~S3Z3~
ation at reduced pressure. The residue was treated at 90 C.
with sodium hydroxide (100 y., 2.5 mole) in 800 ml~ 60%
aqueous methanol for ~0 minutes. After cooling, the solution was extracted with ether (3 x 200 ml.)g and ~he aqueous phase was acidified with concentr3ted hydrochl~ride acid to give 148 9. of crude aJ4-dimethyl-3-phenylpyrazole-l-acetic acid, m.p. 151-162 C. Recrystallization from aqueous methanol gave 111 g. of product, m.p. 168-172 C. The analytical sam-ple was recrystallized from ethyl acetate; m.p. 170-172 C.
Analysis~
Calc'd. for Cl3H1~NzOz CJ 67.81; H, 6O13; N, 12.17.
Found: C, 68~32; H, 6.14; N, 12~06.
Part B - a,4-Dimethyl 3-phenylpyrazole-1-acetamide A mixture of a,4-dimethyl 3-phenylpyrazole 1 acetic acid (11.5 g., 0.05 mole), thionyl chloride (7.5 g., oOo6 mole) and benzene (300 ml.) was heated under reflux for 1 hour and cooled. Ammonia (30 ml. of 25~ aqueous solution) '~
was added rapidly with stirring to one-half of the above sol-;~ 20 ution. The benzene layer was separated, washed with water, and the benzene evaporated. The residual oil (8.3 9.) was re-j .
crystallized twice from benzene:Skellysolve B to give 4.2 g.
of a,4-dimethyl-3-phenylpyrazole-1-acetamide, m.p 99-101 C.
Calc'd. for C13H15N30:
C, 68.10; H, 6.59; Ng 18.33.
Found: C, 69.og; H, 6~74; N, 18.47.
. .
~ ~,a,4-Trimethyl-3-phenylpyrazole-1-acetamide j ~ Following the procedure of Example 68, but substitu~ing .
aqueous methylamine for aqueous ammonia~ there was obtained ''' ' ' ' . . : , ~ . .: . . :
/
1~53Z3~
N,a,4-trimethyl-3~phenylpyrazole-1 acetamide having a melting point of 111-112 C.
!
Calc'd. For C14H17N30-C, 69.11; H, 7.~4; N, 17.27.
Found: C, 69.1û; H, 7.37; N, 17.29.
N-Ethyl-a~4-dimethyl-3-phenylpyrazole-l-acetarride Following the procedure of Example 68, but substituting aqueous ethylamine for aqueous ammonia, there was obtained 10 N-ethyl-c~,4-dimethyl-3-phenylpyrazole-1-acetamide having a melting p~int of 78-79 C.
Analysis:
Calc'd. for C15HlgN30:
i C, 700 00; H, 7.44; N, 16.33.
15Found: C, 70.14; H, 7.30; N, 16.49.
Example 71 N-Butyl-aJ4-dimethyl-3-phenylpyrazole-l-acetamide .. . .
Following the procedure of Example 68, but substituting butylamine for ~queous ammonia, there was obtained N-butyl-a,4 dimethyl-3-phenylpyrazole-1-acetamide having a melting 20 point of 82-84 C.
Calc'd. for C17H23N30:
C, 71.54; H, 8.12; N, 14.73.
Found: C, 72.42; H, 8.01; N, 14.91.
:~ 25 ~e~ N-Ethyl-N,a,4-trimethyl-~-phenylpyrazole-1-acet-amide . -~: Followin~ the procedure of Example 68, but substituting N-methyl ethylamine for aqueous ammonia, there was obtained -: N-ethyl-NJaJ4-trimethyl-3-phenylpyrazole-l-acetamide having 30 a melting point of 5~-61 C.
- . , . , . ~ :
- : . . . .
16)S~Z31 Anal~
Calo'd. for C16H21N30 ~-C, 70.82; 1-l, 7~0; N. 15.49~
: Found: C, 71.15i H, 7.46; N, 15.71.
- Fxample 7~ N,N-Diethyl-a~4-dimethyl-3-phenylpyrazole-1-acetamide ~ ollowing the procedure of Example 68, but substituting diethylamine for aqueous ammonia there was obtained N,N-di-ethyl-~,4-dimethyl-~-phenylpyrazol e-1 -acetamide having a ; melting point of 55-57 C.
Analysis:
Calc'd. for C17H23N3b:
C, 71.54; H, 8.12; NJ 14.73.
, Found: C, 71.54; H, 8.07; N, 14.82.
~ a,4-Dimethyl-3-phenylpyrazole-1-acetanilide Y Following the procedure of Example 68, but substituting aniline for aqueous ammonia, there was obtained a~4-dimeth 3-phenylpyrazole-1-acetanilide having a melting point of 79-82 C.
~: ', Calc'd. for C~91~ N300 C, 74.73; H, 6.27; N, 13.76.
Found: C, 75.97; H, 6.39; NJ 13.17 ,~ ~ NJ a, 4- Trimethyl-~-phenylpyrazole-1-acetanilide Following the procedure of Example 68~ but substituting N-methylaniline for aqueous ammonia, there was obtained N,aJ4-trimetilyl-3-phenylpyrazole-1 acetanilide having a melt-. ,.
ing point o~ 111. $-114 . 5 C~
Calc'd. for C20H21N~0~
6 -,' ~ .
.-~ - . , ~ .. . . ~
~053Z31 C, 75.21; H, 6~63; N, 1~.16.
Found: CJ 75 115; H, 6.50; N~ 1;3.29.
1-[2- (4-Methyl-3-phenylpyrazol -1- yl) prOpionyl ]^
pyrrolidine Following the procedure of Example 68~ but substituting pyrrolidine for aqueous ammonia, there was obtained 2-(4-methyl-3-phenylpyrazol-1-yl )propionyl]pyrrolidine having a melting point of 72-74 C.
Analysis:
Calc'd. for C17H21N30~
CJ 72. 05; H, 7.47; N, 14.83.
found: Cl 72.37; H, 7.62; N, 14.68.
Example 77 4-~2-~4-Methyl-3-phenylpyrazol-1-yl)propionyl]
morpholine Fsllowing the procedure of Example 68, but substituting morpholine for aqueous ammonia, there was obtained 4-~2-(4-methyl-~-phenylpyrazol-1-yl)propionyl]morpholine having a ~ melting point of 84-96 C.
.. ~ ~ ';
: 20 Calc'd. for C17H2lN302~
~: C, 68.20; H, 7.07; N, 14.04.
~ Found: C, 67.78; H, 7.11; N~ 13.69. : :
.: : Exam;~le 78 aJ4-D;methyl-3-phenyl-NJN-dipropylpyrazole 1-acetamide Folla~ing the procedure of Example S8, but substituting ~: dipropylamine for aqueous ammonia, there was obtained a,4-di-methyl-3-phenyl-N~N-dipropylpyrazole-1-acetamide having a ~: boiling point of 176 /o.6 mm.
- 30 Calc'd. for Cl9H27N30:
.
. . . . .
:~229 C, 72.80; H. 8~68; N, 13.41 F~und~ C. 72.80; H, 8.75; N, 1~.32.
- ~79 4~Me~hyl-3-phenyl~a-propylpyrazole-1-acetamide Following ~he procedure of Exarnple 68, bu~ substi~uting 5 4-methyl-3-phenyl-a-propylpyrazole-1-acetic acid for a,4 di methyl-3-phenylpyrazole-1-acetic acid, there was ~btained 4-methyl-3-phenyl-~-propylpyrazole-1-acetamide having a melting point of 116-118 C.
~ '.
Calc'd. for Cl5HlgN30:
C, 70.00; H, 7.44; N, 16.33.
Found: C, 70.11; H, 7.71; N, 16.60.
Example 80 N,4-Dimethyl-3-phenyl-a-propylpyrazole-1-acet-amide Following the procedure of Example 6~37 but substituti ng aqueous methylamine for aqueous ammonia, and 4-methyl-3-phenyl-~x-propylpyrazole-1-acetic acid for a,4-dimethyl-3 ` phenylpyrazole-1.acetic acid, there was ob~ained N,4-di-methyl-3-phenyl-c~-propylpyrazole-1-acetamide having a melt-Z0 ing point of 84-86 C.
~_1 s:
Calc'd. for C16H2~N30:
, 70.82; H, 7.80; N, 15.49.
Found: C, 70.42; HJ 7.98; N, 15.52.
25 ~e~ N,N,4-Trimethyl-3-phenyl-a-propylpyrazole-1-acetamide Folla~ing the procedure of Example 68, but substituting dirnethylamine for aqueous ammonia and 4-methyl-3-phenyl-~pro-pylpyrazole-1~cetic acid for ~x,4-dimethyl-3-phenylpyrazole-30 1-acetic acîdJ there was obtained N,N,4-trimethyl-3-phenyl- -..
~229 10532~1 a-propylpyrazole-1-acetamide having a melting point of 84-86 C.
Calc'd. for C17H23N30:
C, 71.54; H~ 8.12; N, 14~7~.
Found: Cl 71.47; HJ 8.22; N, 14.91.
~xample 82 N,N-Diethyl-4-methyl-3-phenyl-a-propylpyrazole-1-acetamide Following the procedure of Example 68, but substituting diethylamine for aqueous ammonia and 4-methyl-3-phenyl-~-propylpyrazo1e-1-acetic acid for a,4-dimethyl-1phenylpyrazole-1-acetic acid, there was obtained N,N-diethyl-4-methyl-3-phenyl-a-propylpyrazole-1-acetamide having a melting point ~- of 65-67 C.
~ :
,' -:
Calcld. for C13H27N30:
C, 72.80; H, 8.68; N) 13.41.
Found: C, 73.00; H, 8.73; N, 13.59.
N,N-Diethyl-a-methyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting methyl-3-phenylpyrazole-1-acetic acid For a,4-dimethyl-;~ 3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous ammonia there was obtained N,N-diethyl-a-methyl-3-phenylpyra-zole-1-acetamide having a boiling point of 178/0.2 mm.
Analysis:
Calc'd. for Cl~H2lN30:-~; C, 70.82; H, 7.80; N, 15.49 Found: C, 70.60; H, 7.74; NJ 15051.
Example 84 a-~ethyl-3-phenyl-N,N-dipropylpyrazole-1-acet-~ :
amide -:
-5g-., .
,, . . . . ,, ::
. .. ~ . '~-', , ; . . ~ , - . . : , , - . .
~22g ~OS323~
Following the procedure of Exam~le 68, but substituting dipropylamine for aqueous ammonia and ~-methyl-3-phenylpyra-zole-1^acetic acid fo. ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, there was obtained ~-methyl-3-phenyl-N,N-dipropylpyr-azole-L-acetamide having a boiling point of 181/0.4 mm.
Analys~s:
Calc'd. for C1aH2sN30O
C, 72.20; H, 8.42; N, 14.04.
Found: C, 72.03; H, 8.69; N, 13.90.
~ ~-Ethyl-N,N-dimethyl-3-phenylpyrazole-1 acetamide Following the procedure of Example 68, but substituting ; a ethy1-3-phenylpyra~ole-1-acetic acid for ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for :-aqueous ammonia, there was obtained a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide having a melting point of ~01-103 C.
Analysis:
Calc'd. for C15Hl~N30:
C, 70.00; ~, 7.44; N, 16.33 .: 20 Found: C, 70.16; H, 7.48; N, 16.140 ~: ~ ~ N,N,a-Trlethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting ,~
.a-ethyl 3-phenylpyrazole-1-acetic acid for a,4-dimethyl~
3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous : .
ammonia, there was obtained N,N,a-trtethYl-3-phenylpyrazole-~ acetamide having a meltTng point o~ 63-66~ C.
:~ Calc'd. for C17H23N90:
, 71.54; H, 8.1~; N, 14.73.
Found: C~ 71.85; H, 8.12; N, 14.71.
' - ,~: ' ' : , ' , , 322g Ex~7 N,Ngtx-Triethyl-4-methyl-3-phenylpyrazole-1-acet-.
amide Following the procedure of Example 68, but subst;tut;ng a-ethyl-4-methyl-~-phenylpyrazole-1-acetic acid f~r a,4-di-methyl-3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous ammonia, there was obtained N,N,a-triethyl-4-methyl-3-phenylpyrazole-1-acetamide having a melting point of 80_82 C.
Calc'd. for C18H25N30.
C, 72.20; H, 8.42; N, 14.01.
Found: C, 7~.34; H, 8.73; N, 14.47.
a-lsopropyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting a isopropyl~4-methyl-3-phenylpyrazole-1-acetic acid for a,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethyl- ;~
amine for aqueous ammonia, there was obtained a-isopropyl-~ N,N,4-trimethyl-3-phenylpyrazole-1-acetamide having a melt-s~ 20 ing point of 66.5-68.5 C. ~ :
Analysis:
Calc'd. for Cs7H23N30: -, ~ C, 71.54; H, 8.12; N, 14.73.
-~Found: C, 71.67; H, 8.15; N, 14.63.
!~5 ~ 4-Chloro-a-ethyl-N,N-dimethyl-3-phenylpyrazole-.
,~
1-acetamide Following the procedure of Example 68, but substituting .
~4-chloro-a-ethyl-3-phenylpyrazole-1-acetic acid for a,4-di-'~
methyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for aqueous ammonia, there was obtained 4-chloro-a-ethyl-, , ~ , ~ , , ., . - . - ...... .:
- ~,. ~ , . . : , . . :
- , ~ , . . .
;3 c 2 g 11~53Z31 N~N-dimethyl-~-phenylpyrazole-1-acetarnide having a melting point o~ ~4-~6.5 C.
Anal x,s i s.
Calc'd. for Cl5H1~ClN30:
C, 61.74; H, 6.22; N, 14.40j Cl, 12.15.
Found: C, 62.22; H~ 6.26; NJ 14.29; C1~ 12. 07.
Alternate Synthesis of 4- oro-a-ethyl-N,N-dimethyl-:; :
3-phenylpyrazole-1-acetamide a-Ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide (51.4 g., 0.2 mole) was dissolved in chloroform (200 ml.).
A so1ution of potassium carbonate (28.0 9.) in water (100 ml.) was added. The two-phase reaction mixture was stirred vigorously at 10 C. during the addition of chlorine (10 ml., 14.7 9., 0.2 mole). After addition was complete, the organic phase was separated, washed with water, and the solvents were removed under reduced pressure. The residue was dissolved in benzene (60 ml~) and Skellysolve B (300 ml.) was added. The solution was cooled to -10 C. and filtered ~o afford 56.7 9. of 4-chloro-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide, m.p. 95-97 C.
2~ 4-Chloro-N, NJ a-tr7ethyl-3-phenylpyrazole 1-acetamide Following the procedure of Example 68, but substituting 4-chloro-~ ethyl-3-phenylpyrazole-1-acetic acid for a,4 di-methyl-~-phenylpyrazole-1-acetic acid and diethylamine for aqueous ammonia there was obtained 4-chloro-N,N,a-triethyl-3-phenylpyrazole-1-acetamide having a melting point of 47-49 C.
Analvsis , ~ 30 Calc'd. for C17H22ClN30: ~
j2~9 53i231 C, 63.84; H, 6.93; N! 1~.14; Cl, ~ 9.
Folind: C, 63.~7; H, ~97; N, l2.94; Cl, 11.01.
~e~ 91 4-Chloro-a-ethyl-3~pl-1enyl-N,N-dipropylpyrazole-1-acetamide Following the procedure of Example 68, but substituting 4-chloro-a-ethy7-3-phenylpyrazole-1-acetic acid for a,4-di-methyl-3-phenylpyrazole-1-acetic acid, and dipropylamine for aqueous ammonia, there was obtained 4-chloro-a-ethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide having a boiling point of 184 /0.25 mm.
Analysis:
; Calc'd. for C19H26ClN30:
C, 65.59; H, 7.53; N, 12.03; Cl, 10.19.
Found: C, 66.5~; H, 7.99; N, 12.25; Cl, 10.52.
Examp_e 92 N,N-Dimethyl-3-phenyl-a-propylpyrazole-1-aceta-mide Following the procedure of Example 68, but substituting 3-phenyl-a-propylpyrazole-1-acetic acid for a,4-dimethyl 3-phenylpyrazole-1-acetic acid and aqueous dimethylamine for aqueous ammonia there was obtained N,N-dimethyl-3-phenyl-~-propylpyrazole-1-acetamide having a boiling point of 180-181/0.1 mm.
~:
Calc~d. for Cl~H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.53; H, 7.86; N, 15.67.
N,N,4-Trimethyl-aJ3-diphenylpyrazole-1-acetamide ':
Following the procedure of Example 68, but substituting 4-methyl-a,3-diphenylpyrazole-1-acetic acid for a,4-dimethyl-3-phenylpyrazole-1-acetic acid and dimethylamine for aqueous :
.. . -.- - - . ~: . . . . . . .
~ ~ . . .
~ lOS~Z31 amrnonia, there was ob.ained N,N,4-trimethyl-~,3-diphenyl-pyrazole-1-3cetamide havin3 a melting point of 135.5-138 SO
Anal~
Calc'd. for C20H2~N90:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.37; H) 6.76; N, 13.28.
Example 94 4-Cyano-NyN,a-trimethyl-~-phenylpyrazole- t~
.. . .
1-acetamide A mixture of 4-bromo-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide (8.o 5., 0.025 mole) cuprous cyanide (25.0 9., 0.28 mole) and dimethylformamide (200 ml.) was heated under reflux for 18 hours. Water was added and the solution was repeatedly extracted with chloroform. Evaporation of the chloroform gave a residue (7O5 g.), which was recrystallized from benzene:Skellysolve B to give 6.5 9. of 4-cyano-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide, m.p. 132-146 C.
Two recrystallizàtions from ethyl acetate gave the analytical sample, m.p. 144-146 C.
Analysis:
Calc'd. for C15H~N40:
C, 67.14; H, 6.01; N, 20.88.
Found: C, 67.12; H, 6.12; N, 21.18.
a-Ethyl N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide n-Butyl lithium (40 ml. of 1.6 M solution in hexane, I
o.c5 mole~ was added under nitrogen to a stirred solution of N,N,~,4-tetramethyl-3-phenylpyrazo!e-1-acetamide (12.8 g., ~. i 0.05 mole) in THF (150 ml.). Ethyl iodide (30 9.) was added. The solvent was removed after 30 minutes and the residue was partitioned between chloroform and wa~er. The 16~S3231 chloroform was evaporated and the residual oil was chroma-tographed on si l ica gel usi ng benzene:ethyl acetate (9:1 ) as eluant. a-Ethyl-NJN~a~4-tetramethyl-3-phenylpyrazole-1-acetamide (4.9 9.) was the second ma30r band to be eluted from the column. Recrystallization from methanol followed by cyclohexane gave the analytical sample, m.p. 102-104 C~
Analysis:
Calc'd. for C17Hz9N30.
C, 71.54; H, 8.12; N, 14.73.
Found: C, 71.59; H, 7.75; N, 14.91.
N,N,a,4-Tetramethyl-3-phenyl-a-propylpyrazole-1-acetamide Following the procedure of Example 95, but substituting propyl bromide for ethyl iodide, there was obtained N,N,a,4-tetramethyl-3-phenyl-a-propylpyrazole-l-acetamide having a melting point of 90-92 C.
Analysis:
Calc.~d. for C18H25N30:
C~i72~20; H, 8.42; N, 14.01.
Found: C, 72.17; H, 8.39; N, 13 97.
; ~ Example 97 aJ~-Diethyl-NlN~4-trimethyl-3-phenylpyrazole ~ 1-acetamide ; Following the procedure of Example 95, but substituting a-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide for N~N~a~4-tetramethyl-3-phenylpyrazole-l-acetamide~ there was obtained a~a-dlethyl-N~N~4-trimethyl-3-phenylpyrazole-l-acet amide having a melting point of 135-1~6.5 C.
Ana!ysis:
Calcld. for Cl8H25N30: ; -C, 72.20; H, 8.42; N, 14.01.
~: :
.. . . , , . .. . ~.
1~53~31 Found: C, 72~40i H, 8.27; ~ 14~17.
a-Ethyl-N,N,4-trimethyl-3-phenyl-a-propylpyra- :
zole-l-acetamide Following the procedure of Example 95, but substituting a-ethyl-N,N,4-trimethyl-3-phenyl pyrazol e-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and propyl bromide for ethyl iodide, there was obtained a-ethyl-NJN~4-trimethyl-3-phenyl-a-propylpyrazole-l-acetamide having a melting point of 147-148 C.
10 ~.
:. ~
Calc'd. for Cl9H27N30:
C, 72.80; H, 8.68, N, 13.41.
Found: ~, 72.85; ~, 8.44; N, 13.75.
Example 99 N,N,a,a,4-Pentamethyl-5-phenylpyrazole-1-acet-; 15amide Following the procedure of Example 95, but substitut-ing NJN,a,4-tetramethyl-5-phenylpyrazole-1-acetamide for . N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide, there was obtained N,N,a,a,4-penta-:~20 methyl-5-phenylpyrazole-1-acetamide having a melting point o~ 1~6-139 C.
Calc'd. for C1~H2lN30:
C, 70.82; H, 7.80; N, 15.49.
25Found: C, 71.03; H, 7.98; N, 15.74.
N,N,a,4-Tetramethyl-a,3-diphenylpyrazole-. 1-acetamide Following the procedure of Example 95, but substitut-ing N,N,4-trimethyl-a,3-d7phenylpyrazole-1-acetamide for ~0 N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl ~2~9 ~53~31 iodide for ethyl iodide, there was obtained N,N,~,4-~etra-methyl-~,~-diphenylpyrazole-1-acetamide having a meltin3 point of 107~109 C.
Calcld. for C21H23N30~
C, 75.64; H, 6.95; N, 12.60.
Found: C, 75.61; H, 7.o8; N~ 12.46.
Exampl__101 NJN,a,a,4-Pentamethyl-3-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example g5, but substitut-ing N,N,a,4-tetramethyl-3-(2-thienyl)pyrazole-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide there was obtained N,N,a,a,4-pentamethyl-3-(2-thienyl)pyrazole-1-acetamide having a 15 melting point of 116-119 C.
:j Calc'd. for C14H19N30S: ~ i C, 60.62; H, 6.90; N, 15.15; S, 11.56.
- Found C, 60.82; H, 6.88i N, 14.92; S, 11.78. ~
20 ~ 3-(2-Furyl)-N,N,a,a,4-pentamethylpyrazole- ~ :
1-acetamide Following the procedure of Example ~5, but substitut- ~
~ ing 3-(2-furyl)-N,N,a,4-tetramethylpyrazole-1-acetamide for .
~ N,N,a,4-tetramethyl-~-phenylpyrazole-1-acetamide and methyl iod;de for ethyl iodide there was obtained ~-(2-furyl)-N,N,a,aJ4-pentamethylpyrazole-1-acetamide having a melting point of 131-134 C.
Calc'd~ for Cl4H19N302:
C, 64.34; H, 7.33i N, 16. o80 : -67 .
^ - - - .. . ,, ~ : . . . . .
~- - : . ... . . . . .
.: , . .
3~29 10~
Found: C, 62.90; ~ 7.03; N, 15.87.
03 N,N-Dimethyl~ metllyl-~-phenylpyrazol~l-yl~-cyclopropaneearboxamide f`o~iowlng the procedure of Example 9~, ~ut subs~ltuting ~-(2-chloroethyl)-NJN,4-trimethyl-~-phenylpyrazole-1-aceta-mide ~prepared in Example 45) for N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide and ~ithout addition of ethyl iodide there was obtained N,N-dimethyl-1-(4-methyl-3-phenyl-pyrazol-1-yl)cyclopropanecarboxamide, m.p. ~2-55 C.
Analysis:
Calc'd. for Cl6H19N30:
; C, 71.34i H, 7.11; N, 15.~0. :~
Found: C, 71.23; H, 7.13; N, 15.67.
Examp!e 104 N,N-Dimethyl-1-(4-methyl-~-phenylpyrazol-1-yl)-cyclo~utanecarboxamide .` Following the procedure of Example 95J but substituting a-(3-bromopropyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acet-amide for N,N,aJ4-tetramethyl-3-phenylpyrazole-1-acetamide and without the addition of ethyl iodide there was obtained N,N-dimethyl-1-(4-methyl-3-phenylpyrazol 1-yl)cyclobutane-~ carboxamide having a melting point of 87-8~ C.
- Analysis:
: I .
Calc~d. for Cl7H2lN30:
~: C, 72.05; H, 7.47; N, 14.83 Found: CJ 71.83; H, 7.82; N, 14.89.
I ~ N,N-Dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)- 1 -cyclopentanecarboxamide Following the procedure of Example 95, but substitut-ing a-(4-bromobutyl)-N,N,4-trimethyl-~-phenylpyrazole-~0 1-acetamide (prepared in Example 4~) for N,N,a,4-tetra-~8- :
; I
1053Z3~ `
methyl-~-phenylpyrazole-1-acetamide and without addition or ethyl iodide there was obtained N~N-dimetilyl-1-(4-methyl-3 phenylpyrazol-1~yl)cyclopentanecarboxamide ~ N,N-D~methyl-1-(3-phenylpyrazol-1-yl)cyclopro-pa neca rboxam i de Following the procedure of Example 95, but substitut-ing a-(2-chloroethyl)-N,N-dimethyl -3-phenyl pyrazole-1-acet-amide for N,N,a,4-tetramethyl-~-phenylpyrazole-1-acetamide and without addition of ethyl iodide there was obtained N~N-dimethyl-l-(3-phenylpyrazol-l-yl)cyclopropanecarb amide having a melting point of 96-99 C.
Analysis:
Calc'd. for C1sH17N30:
C, 70.56; H, 6.71; N, 16.48.
Found: C, 70.19; H, 6.68; NJ 16.46.
N, N-D imethyl-1-(3-phenylpyrazol-1-yl)cyclo butanecarboxamide Following the procedure of Example 95, but substitut-; Ing ~-(3-br~m~propyl)-N, N-dimethyl-~-phenylpyrazole~1-ace~-amide for NJNJaJ4-tetramethyl-3-phenylpyrazole-l-acetamide and without addition of ethyl iodide there was obtained N,N-dlmethyl-1-(~ phenylpyrazol-1-yl)cyclobutanecarboxamide ha~ing 2 boilTng point of 170/0.1 mm.
~,.
::
Calc'd. for C1~H~9N30:
C~ 71.~4; HJ 7.11; N/ 15.60.
Found~ CJ 71.42; H~ 7,19; N~ 14.63.
4-Bromo-N,N~,5-tetramethyl-~-phenylpyrazole- -1-acetamlde - 30 Bromine (3.68 9., .o46 moleJ was added to a solution :
... .
. . ..
.
~2~9 ~53Z31 of N,N,a,5- tetramethyl -3-pheny1pyrazole-1-acetamide (5.~) 9., .OIg mole) in acetic acid~ At~ter 1 hour, the solutiQrl ~as dilueed with water to give 6.3 9. of 4-br~no-NJN~G~J5-tetramethyl-~-phenytpyrazole-l-acetamide7 m.p.
88-89.5 C. Recrystallization from benzene-Skellysolve B
and finally ether gave the analytical sample~ m.p.
88-8~.5 C.
Calc'd. for C15Hl8BrN30: :
C, 53.58i H, 5.40; Br, 23.77; N, 12.50.
Found: C, 53.69; H, 5.54; Br, 23.69; N, 12.30.
4-Bromo-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-ace~amide - Following the procedure of Example 108, but substitut-Ing a-ethyl-NsN-dimethyl-~-phenylpyrazole-1-acetamide for ' N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, there was -~ obtained 4-bromo-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide hav7ng a melting point of 97-100 C. I
Calc'd. for Cl5H18BrN30: , - -- C, 53.58; H, 5.40; N, 12.48; Br, 23.77.
Found C, 53.75; H, 5.45; N, 12.68; Br, 2~.75.
4-Chloro-~-(p-chlorophenyl)-N,N,a-trimethyl-pyrazole-1 acetamide ~ : 25 Fol1Owing the procedure of Example 108, but substitut-~ - ing 3-(p-chl~rophenylj-N,N,~-trimethylpyrazole-1-acetamide for N,NJa,5-tetramethyl-~-phenylpyrazole-1-acetamide and sulfuryl chloride for bromine, there was obtained 4-chloro-3-(p-chlorophenyl)-N~N,~-trimethylpyrazole-1-acetamide having a melting point of 92-93 5 C.
' -,, . . . , ~ , .
, 322~3 ~OS3231 ~nal l~is Calc~d. for C14HlSCI2N30:
C, 5~.86; H, 4.84; N, 1~.46; Cl, 22.71.Found: C, 54.00; H~ 4.88; NJ ~13.4L, ~t, 22.~4.
5 ~ 4-Chloro-3-(o-chlorophenyl)-N,N~a-trimethyl- :
. .
pyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing 3-(o-chlorophenyl)-N,N,a-trimethylpyrazole-1-acetamide for N,NJa,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachloridefor acetic acld as the reaction solvent, there was obtained ,, 4-chloro-3-(o-chlorophenyl)-N,N,a-trimethylpyrazole-1-acet-amide hav',ng a melting point of 108-111 C.
~: ;.
: 15 Calc'd. for C~H~5Cl2N30~
C, 53.86; ~, 4.84; N, 22.71; Cl, 13.46. -Found: C, 53.77; H, 4.89; N, 22.87; Cl, 1~.29.
4-Chloro-N,N,a-trimethyl-3-(o-tolyl)pyrazole-1~acetamide Following the procedure of Example 108, but substi,ut-; Ing N,N,a-trimethyl-~-(o-tolyl)pyrazole-1-acetamide for ,~ N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachloride for acetlc acid as the reaction solvent, there was obtained 4-chloro-N,N,a trimethyl-~-(o-tolyl)pyrazole-1-acetamide ~ . havIng a melting point of 6~-71.5 C.
J: .. . .
Calc'd. for C15H~8ClN30:
- C, 61.7~; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.59; ~, 6.32; N3 14.32; Cl, 12.17.
~053;23~
Exam ~ 4-Chloro-N,N,~-trimethyl-~-(o methoxyphenyl3-pyrazole-1-ace~amide Follcwing the procedure of xample 108, but substitut-;ng N,N,~-trimethyl-3-(o-methoxyphenyl)pyrazole-1-acetamide for N5N,~,5-tetramethyl-~-phenylpyrazole-1-aceta~;de, tert-butyl hypochlorite for bromine, and carbon tetrachloride for acetic acid as the reaction solvent, there was obtained 4-chloro-N,N,a trimethyl-3-~o-methoxyphenyl)pyrazole-1-acet-; amide having a me1ting point of 74-77 C.
Analys- s:
Calc'd. for C15H18ClN30z:
C, 58.53; H, 5.89; N, 11.52; Cl, 13.65.
Found: C, 58.70; HJ 5.95; N, 11.48; Cl, 13.88.
4-Chloro-N~N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide Follcwing the procedure of Example 103, but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl ~ hypochlorite for bromine, and carbon tetrachloride for ; ?O acetic acid as the reaction solvent, there was obtained 4-chloro-N,N,a,a tetramethyl-3-phenylpyrazole-1-acetamide ha~ing a melting point of 117-113 C.
Calc'd. for C1sH18ClN~0:
C, 61.74; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.53; H, 6.33; N, 14.36; Cl, 12.15.
~ 4-Chloro-N,N-dimethyl-3-phenyl-a-propylpyrazole-; 1-acetamide Following the procedure of Example 108, but substitut-ing N,N-dimethyl-3-phenyl-a-propylpyrazole-1-acetamide for .
3'229 ~ ~ S ~Z 3 ~
N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for br~line, and c~rbon tetrachloride for acetic acid as the reaction solvent, there was obtained 4-chloro-N,N-dimethyl-3-phenyl-a-propylpyrazole-1-acetamide having a meltin~ point of 85-87 C.
Analysis:
; Calc'd. for C1~H20ClN30:
C, 62.~4; H, 6.59; N, 13.74; C1J 11.59.
Found: C, 62.95; H, 5.84; N, 13.83; Cl, 11.68.
10 Exam~le 116 4-Chloro-N,N,a-trimethyl-3-(2,6-dichlorophenyl)-- pyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing N,N,a-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acet-amide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachlo-ride for acetic acid as the react~on solvent, there was obtained 4-c~oro-N,N,a-trimethyl^3-(2,6-dichlorophenyl)-pyrazole~1-acetamide having a melting point of 126-128 C.
A n? l ys i s:
Calcld. for C14H14Cl3N30:
C, 48.51; H, 4.07; N, 12.12; Cl, 30.69.
Found: Cg 4g.o6; H, 4.15; N, 12.0~; Cl, 30.59.
4-Chloro-N,N,a-trimethyl-3-phenylpyrazole-., .
1-propionamide Following the procedure of Example 108, but substitut-ing N,N,a-trimethyl-3-phenylpyrazole-1-propionamide for N,N,~,5-tetramethyl-3-phenylpyrazole-1-acetamide, and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-N,N,~-trimethyl-~-phenylpyrazole-1-propionamide having a b~iling point of 190/0.3 mm.
.
.,, ' ~ .
~29 lC~S3Z3~
Analysi~:
Calc'd. for C15HlBC1N30~
C, 61.74; H~ 6.22; N~ 1~.40; Cl, 12.15.
Found: C, 61.~2; H, 6.48; N, 14.57; Cl~ 12.39.
~ 4-Chloro-3-(o-chlorophenyl)-a-ethyl-N,N-di-methylpyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing 3-(o-chlorophenyl) a-ethyl-N,N-dimethylpyrazole-1-acet-amide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, `
and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-3-(o-chlorophenyl)-a-ethyl-N,N-dimethylpyrazole-1-acetamide.
Analysis-' Calc'd. for C15H17Cl2N30-C~ 55.22; H~ 5.26; N~ 12.88; C1, 21.74.
Found: CJ 55.23; HJ 5.26; N, 12.93; C1, 21.4~.
Examp!e 119 4-Chloro-~-(o-chlorophenyl)-N,N,a,a-tetramethyl-pyrazole-1-acetamide Following the procedure of Example 108, but substitut-~` 20 ing 3-(o-chlorophenyl)-N,N,a,a-tetramethylpyrazole-1-acet-amide for N,N3a~5-tetramethyl-3-phenylpyrazole-l-acetamide~
and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-3-(o-chlorophenyl)-N,N,a,~-tetramethylpyrazole-1-acetamide.
~ 4-Chloro-N,N,a,a-tetramethyl-3-(o-tolyl)pyra-zole-1-acetamide Following the procedure of Example 1oB, but substitut-~ ing N,N,a,~ tetramethyl-3-(o-tolyl)pyrazole-1-acetamide for ;~ N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-~ 30 butyl hypochlorite for bromine, there was obtained 4-chloro-t, . , .
: . . ,- , . . . .
1~53Z3~ 3229 ,:
N,NJa~a tetramethyl-3-(o-tolyl)pyrazole-1-acetaTnide having a melting point of 1~4.5 136 C.
Calc'd. for Cl6H20ClN30:
C, 62.84; H, 6.59; N~ 13.74; Cl, 11.59.
Found: C, 62.77; H, 6.73; N, 13~67; Cl, 11. 58. ~ :
Example 121 Alternate synthesis for N,N,~-trimethyl-3-phenylpyrazole^1-propionamide A mixture of 14.4 9. (0.1 mole) of 3-phenylpyrazole-20.8 9. (0.15 mole) of anhydrous potassium carbonate and 29.1 9. (0.15 mole) of 2-bromo-N,N,2-trimethylpropionamide was stirred at 140 C. for 1. 5 hour. The mixture was ` diluted with water and extracted with benzene. Evaporation ~ -? of the benzene gave an oil which was crystallized from cyclohexane to give 7.8 g. of N,N,~-trimethyl-~-phenylpyra-zole-1-propionamide, m.p. 68-71 C.
! Example 122 N,N,~,4-Tetramethyl-3-phenylpyrazole-1-propion-.j .
; amide Following the procedure of Example 1?1, but substitut-2C Ing 2-bromo-N,N-dimethylbutyramide for 2-bromo-N,N,2-tri-methylpropionamide, and 4-methyl-3-phenylpyrazole for 3-phenylpyrazoleJ there were obtained the already described a-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide and ~; N,N,~,4-tetramethyl-3-phenylpyrazole-1-propionamide having a boiling point of 170/0.2 mm.
Calc'd. for C1~H21N
~, C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.87; H, 7.92; N, 15084.
~ ~-Ethyl-N,N-dimethyl-3-phenylpyrazole-1-propionamide ,~, .
,-., .. . , ~ .. .
~29 1~53Z3~
Fol l ow i ng the procedure of E~iampl e ~21, but subst i tut-ing 2-b,omo-N,N-dimethylvalera~nide -For 2-bromo-N,N92-tri-methylpropionamide~ there were obtained the already des-cribed NJN-dinlethyl-3-phenyl-a~propylpyrazole-l-acetamide and ~-et,lyl-N~N-dimethyl-3-phenylpyrazole-1 propionamide hav i ng a melt î ng point of 97-99 C.
- Anal ~s is:
~ Calc'd. for Cl6HzlN30:
: C, 70.82; H, 7.80; NJ 15.49.
Found: C, 70.75; H, 7~84; NJ 15.56.
~ Example 1?4 N,N-Dimethyl-3-phenylpyrazole-1-propionamide : Foll~ing the procedure of Example 121, but substitut-ing 2-bromo-N,N-dimethylpropionam7de for 2-brcmo-N,N,2-tri-methylpropionamide there were obtained the already described NJN,~-trimethyl-~-phenylpyrazole-1-acetamide and N,N-di-! methyl-3-phenylpyrazole-1-propionamide having a melting point of 103-105 C.
.J . ~,~ .
., .
Calcrd. for C14H17N30:
C, 69.11; H, 7.04; N, 17.27.
4 Found: C, 68.98; H, 6.92; N, 17.00.
~.' Example 125 N,N,~-Trimethyl-3-phenylpyrazole-1-propionamide -. Follow;ng the procedure of Example 121, but substitut-ing 2-bromo-N,N-dimethylbu~yramide for 2-bromo-N,N,2-tri-?5 methylpropionamide there was obtained the already described a-ethyl-NJN-dimethyl-3-phenylpyrazole-l-acetamide and ~' N,N,~-trimethyl-~-phenylpyrazole-1-propionamide having a !
~ melting point of 65-67 C.
., ~:
~0 Ca l c ' d O for Cl 5H1 9N90 .
.
76- :
.
.. . .
~229 lQS3Z31 c~ ro ooi ~1, 7.~4; I~IJ ~6.3:~.
Found: C, 69.94; H, 7.47; N, 16.56.
~-Bromo-N,N,4-trime~hyl-3-phen,vlpyrazole-1-propionamide ; 5 Following the procedure of Example 121~ but substitut-ing 2,3-dibromo-N,N-dimethylpropionamide for 2-bromo-N,N,2- ~ -trimethylpropionamide and ~-methyl-3-phenylpyrazole for 3-phenylpyrazole there was obtained ~-bromo-N,N,4-trimethyl-~-phenylpyrazole-1-propionamide having a melting point of 104-107 C.
'. ~y~: :
Calc'd. for C15H1 8 BrN30:
C, 53.58; H, 5.39; N) 12.50; Br, 2~.77.
Found: C, 53.99; H, 5.51; N, 1~.63; Br, 23.43.
Example 127 N~NJa~aJ4-pentamethyl-3-phenylpyrazole 1-thioacetamide i N~N~a~a~4-pentamethyl-3-phenylpyrazole-l-acetamide J (2.71 g., 0.01 mole) was dissolved in 10 ml. of pyridine with s~irring~ To this solution was added phosphorous penta5ulfide (3.33 g., 0.015 mole) and the mixture heated ~t reflux for one hour. The reaction mixture was parti-tloned Tn water-benzene, the benzene layer separated and washed with water. Evaporation of the benzene gave 2.75 9.
of crude material which was chromatographed on silica gel.
Elution with 10~ ethyl acetate in benzene gave 2.65 gm. of ' : NJN~ J4-pentamethyl-3-phenylpyrazole-l-thioacetamide J whlch was recrystallized from ethyl ac2tate:Skellysolve B
to give 2.0 9. having a melting point of 115-117 C.
Analysis: -Calc'd. for ClaH21N3S:
~ .
~29 lQ53231 C, 66.86; H, 7.37i N, 14.62; S~ 11.15.
Found: C, 66.82; H, 7O5~; N, 14~53; S, 11.27.
128 a-(n-Butyl)-N,N,4~trimethyl-3-phenylpyraz~le 1-thioacetamide Following the procedure of Example 127, but substitut-i ng a- (n-butyl~-N,N,4-trimethy1-3-phenylpyrazole-1-acet-amide for N,N,a,,4-pentamethyl-3-phenylpyrazole-1-acet-amide there was obtained a-(n-butyl)-NJN,4-trimethyl-~-phenylpyrazole-1-thioacetamide having a melting point ~f 93-g5 C.
Calctd. for Cl8H25N3S:
C, 68.53; H, 7.99; N, 13.32; S, 10.16.
Found: C, 68.31; HJ 8.27; N~ 13.39; S~ 10.24. 5 ~ N,N,a,a-Tetramethyl-3-phenylpyrazole-1-thio-acetamide Following the procedure of Example 127, but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide for N,N,a,a,4-pentamethyl-~-phenylpyrazole-1-acetamide there was ob~ained N,N,a,a~tetramethyl-3-phenylpyrazole-1-thio-acetam1de having a melting point of 124-127 C.
Calc'd. for C15H19N3S:
C, 65.90; H, 7.00; N, 15.37; S~ 11.73.
Found: C, 65.70; H~ 7.17; N, 15.45; S, 11.68.
N,N-Diethyl-~,4-dimethyl-3-phenylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitùt-ing N,N^diethyl-,4-dimethyl-3-phenylpyrazole-1-acetamide for NJN,a,a-4-pentamethyl-3-phenylpyrazole-1-acetamide ~78-, ' lQ53231 there was obtained N,N-diethyl-a.4-dimethyl-~-phenylpyrazole-1-thioacetan~ide having a melting point of 76-79 C.
Calc~d~ for C17H23N~S:
C, 67.73; H3 7.69; N, 13.94; S, 10.64.
Found: C, 67.54; H, 7.59; N, 14.16; S~ 11.61.
a-Ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitut~
ing o~ethyl-N,N,4-trimethyl-~-phenylpyrazole-1-acetamide for N,N,a,~,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained ~-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide having a melting point of 107-110 C.
- bnalysis Calc'd. for C16H21N3S:
C, 66.85; H, 7.37; N, 14.62; S, 11.15.
Found: C, 66.76; H, 7.56; N, 14.70; S, 11.02.
4-Chloro-N,N,~-trimethyl-~-phenylpyrazole-` 1-thioa~etamide ; 20 Following the procedure of Example 127, but substitut-ing 4-chloro-N,N,~-trimethyl-~-phenylpyrazole-1-acetamide for N,N,,~,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained 4-chloro N,N,a-trimethyl-3-phenylpyrazole- -1-thToacetamide having a melting point of 80-83 C.
~5 ~ :
Calc'dO for C14Hl~ClN3S:
C, 57.23; H, 5.47; N, 14.30; Cl, 12.07;
S, 10.91.
Found: C, 57.13; H, 5.60; N, 14.44; Cl, 12.14;
~` 30 S, 11. 03.
~ -79-~229 ~053Z31 NJN,a-Trin-ethyl-3-phenylpyrazole-1-thioacet-amide Following the procedure of Example 127, but sUbstitut ing N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,~a,4-pentamethyl-3-phenylpyrazole-1-acetanlide there was obtained NJN,a-trimethyl-3-phenylpyrazole-1-thioacet-amide having a melting point of 56-58 C.
Calc'd. for C14H17N3S:
~ 10 C, 64.83; H, 6.61; N, 16.21; S, 12.36.
`; Found: C, 64.76; H, 6~72; N, 16.32; S, 12.50.
; Example 134 N,N,a,4-Tetramethyl-3-phenylpyrazole-1-thio-acetamide Following the procedure of Example 127, but substitut-ing N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide for N,N~a~aJ4-pentamethyl-3-phenylpyrazole-l-acetamide there was obtained N,N,a,4-tetramethyl-3-phenylpyrazole-1-thio-acetamide having a melting point of 87-89 C.
Analysis:
~ 20 Calc'd. for Cl5H19N3S.
- C, 65.90; H, 7.00; N, 15.38; S, 11.73.
Found: C, 65.68; H, 7.10i N~ 15.05; S, 11.93.
Example 135 3-(o-Chlorophenyl)-N,N,a-tri~ethylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitut-ing 3-(o-chlorophenyl)-N,N~a-trimethylpyra20le-1-acetamide for N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained 3-(o-chlorophenyl)~N,N,a-trimethylpyra-zole-1-thioacetamide having a melting point of 68-69.5 C.
Analysis-- . : . .
.
~29 l.l)53231 Calc'd. for C1~Hl~ClN3~o C, 57.23; H, 5.49, Cl, 12.07; N, 14.30; S,10.9 Found: C, 57.27; ~1, 5.53; Cl, 12~00; N, 1~.50; S,ll 0 ~ N,~ Trimethyl-~-phenylpyrazole-1- t hioacet-amide Following the procedure of Example 127, but substitut-ing N,a,4-trimethyl-~-phenylpyrazole-1-acetamide for N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained N,a,4-trimethyl-3-phenylpyrazole-1-thioacet-amide having a melting point of 97-99 C.
Analysis.
Calc'd. for C1 4 H17N3S:
C, 64.8~; H, 6.61; N, 16.20; S, 12.36.
Found: C, 64.72; H, 6.74; N, 16.23; S, 12.64.
15Example 137 N,~,a,4-Tetramethyl-3-phenylpyrazole-1-thiO-acetamide Following the procedure of Example 127, but substitut-ing N,~,~,4-tetramethyl-3-phenylpyrazole-1-acetamide For N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there ;
was obtained N~a,a,4-tetramethyl-3-phenylpyrazole-1-thio-acetamide having a melting point of 75-77 C.
Analysis:
Calc'd. for C15HlgN3Ss C, 65.30; H, 7.00; N, 15.~7; S, 11. 73.
25Found: C, 65.55; H) 7.02; N, 15.11; S, 11.64.
N,N,4-Trimethyl-3-phenylpyrazole-1-propionamide Following the procedure of Example 1, but substituting 3-chloro-N,N-dimethylpropionamide for 2-chloro-N,N-dimethyl-propionamide there was obtained N,N,4-trimethyl-3-phenyl-30pyrazole-1-propionamide having a melting point of 60-63 C.
~229 1~53Z31 Calc'd. for Cl5HIgN30:
C, 70. 00; H, 7.44; N~ 16.330 Found: C, 70.01; H, 7.45; N, 16.52.
5 ~ 3-(o-Ethoxyphenyl)-N,N,a,4-tetraniethylpyrazole-1 -ace tam i de Fol lowing .he procedure of Example 1, but substituting 3- (o-ethoxyphenyl )pyrazole for 4-methyl -~S-phenylpyrazole there was obtained 3- (o-ethoxyphenyl )-N,N,~,4-tetramethyl-1 0pyrazole-1-acetamide having a melting point of 96-~7.5 C.
Analysis:
Cal c' d. for C1 7H23N30z:
C, 67.75; H, 7.69; N, 1~.94.
Found: C, 67.74; H, 7.66; N, 13.71.
1 5 ~e~ 4 - I odo- N , N , a t r i me t hy 1 - 3- phe n y 1 p y razo 1 e -1-acetami de Following the procedure of Example 1, but substituting 4-iodo-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained 4- iodo-N,N,~-trimethyl -3-phenylpyrazole-201-acetamide having a melting point of 108-111 CO
i~ Analysis:
Calcld. for Cl4H1~IN30:
C, 45.54; H, 4.37; N, 11.38; I, 34.37.
Found: C, 45.93; H, 4.92; N, 11. 02; 1, 34. 51.
25 ~ a Ethyl-N,N,5-trimethyl-3-phenylpyrazole-1 -ace tam i de Following the procedure of Example 1, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole and 2-b~omo-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-30 propionamide there was obtained a-ethyl-N3N~5-trimeth ' :, 3~29 1C~53Z3~
3-phenylpyrazole-l-acetamide having a mel~ing point of .~ O
117-llg. 5 c.
~,~
Calcld. for C1~H2~N30:
C, 70.82; H, 7.80; N, 15.49. - -Found: C, 70.61; H, 7.57; N, 15.64.
Examp!e 142 Following the procedure of Example ~, but substituting 3-(o-fluorophenyl)pyrazole, 3-(o-fluorophenyl)-4-methylpyra-zole, 3-(o-bromophenyl)pyrazole, 3-(o-bromophenyl)-4-methyl-`~ pyr~zole, 3-(o-trifluoromethylphenyl)pyrazoleJ 3-(o-tri-fluoromethylphenyl)-4-methylpyrazole, and 3-(o-ethylphenyl)-pyrazo1e for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3-(o-fluorophenyl)pyrazole-1-acetamide, N~N~a~4-tetramethyl-3-(o-fluorophenyl)pyrazole-l-acetamide~
,. . .
N,N,a-trimethyl-3-(o-bromophenyl)pyrazole-1-acetamide, N~N~a~4-tetramethyl-3-(o-bromophenyl)pyrazole-l-acetamide~
N~NJ~-tri~ethyl-3-(o-trifluoromethylphenyl)pyrazole-l-acet-amide, N,N,~4-tetramethyl-3-(o-trifluoromethylphenyl)pyra-zole-1-acetamide, and 3-(o-ethylphenyl)-N,N,a-trimethylpyra zole-1-acetamide.
Example 143 NJNJal4-Tetramethyl-5-nitro-3-phenylpyrazole 1-acetamide Following the procedure of Example 1, but substituting 5-nitro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-5-nitro-3-phenylpyr azole-1-acetamide having a melting point of 141-143 C.
Calc'd. ~or C15Hl8N403:
C, 59.59; H, 6.oo; N, 18.53.
:
~(~S 3Z ~
Found: C, 59.62i H, 6.02; N, 18.53.
Example 144 3-(o-Chlorophenyl)-N,N,~,~,4~pentamethyl-pyrazole-1-acetamide Following the procedure of Example 49, but substituting 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3 phenyl-pyrazole and dimethylamine for aqueous methylamine there was obtained ~-(o-chlorophenyl)-N,N,a,a,4-pentamethylpyra-zole-1-acetamide having a melting point of 175-176 C.
Analysis:
Calc'd. for Cl6HzoClN30:
C, 62.84; H, 6.59; Çl, 11.60; N, 13.74.
Found: C, 62.90; H, 6.52; Cl, 11.66; N, 13.54.
~Example 145 N,N,a,a,5-Pentamethyl-3-phenylpyrazole-1-acet-amide Following the procedure of Example 49, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole and O
aqueous dimethylamine for aqueous methylamine there was obtained N~N~a~a~5-pentamethyl-3-ph~enylpyrazole-l-acetamide having a melting point of 123-125 C.
.~:
Analysis;
Calc~d. for C18H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 71.01; H, 7.76; N, 15.74.
4-Chloro-a-ethyl-N,N-dimethyl-3-(o-tolyl)pyra-.
zole~1-acqt~mide F~llowing the procedure of Example 108, but substituting a ethyl N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-butyl hypochlorite for bromine there was obtained 4-chloro-a-ethyl-N,N-dimethyl-~(o-tolyl)pyrazole-1-acetamide having ::
-8~-32~9 lOS;~'~3~
a melting point of 49.5-52 C.
Analysis:
Calc~d. for Cl~H20ClN30:
C, 62.84; H, 6.59; Cl, 11.59; N, 13.74.
Found: C, 62.90; H, 6.~4; Cl, 11.82; N, 13.88.
Example 147 5-Chloro-N~N.a,a,4-pentamethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 1O3J but substitut-ing N,N,a,~,4-pentamethyl-3-phenylpyrazole-1 acetamide ~or N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-; butyl hypochlorite for bromine there was obtained 5-chloro-N,N, a, a, 4-pentamethyl-3-phenylpyrazole-1-acetamide having a melting point of 96-99 C.
Analysis:
Calc'd. for C1ffH20ClN30:
C, 62.84; H, 6.59; Cl, 11.59; N, 13.74.
Found: CJ 63.oo; HJ 6.64; C~ .74; NJ 1~.98.
~ Example 148 4-Fluoro-NJN,~,a-te~ramethyl-3^phenylpyrazole-; 1-acetamide '~ 20 Following the procedure of Example 10BJ but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1~cetamide for ~ N~N~a~5-tetra~ethyl-3-phenylpyrazole-l-acetamide~ trifluoro-,~ methyl hypofluorite for bromine, and carbon tetrachloride for acetic acid as the reaction solvent there was obtained 4-fluoro-NJN~a~-tetramethyl-3-phenylpyrazole-l acetamide.
-Bromo-N,N-dimethyl-3-phenylpyrazole-1-pro-pionamtde Followlng the procedure of Example 121, but substitut-7ny 2,3~dibromo-N,N-dimethylpropionamide for 2-bromo-N,N,2-trimethylpropionamide there was obtained ~-bromo-N,N-, ~" : . . .
, ,~2?9 1053;~ 3~
dimethyl-3-phenylpyrazole-1-acetamide having a melting point of 93-94 C.
Analys ~-Calc'd. for C14H16BrN30:
5C, 52.18; H~ 5. 01; Br, 24.80; N, 13.04. -Found: C, 52.34; H, 5.10; Br, 24.59; N, 1~.20.
Example 150 Hydrochloride salt of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide Hydrogen chloride was passed into a stirred solution 10 of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide (2.53 9., 0.01 mole) in carbon tetrachloride (50 ml.). The precipi-tated salt was filtered off and was recrystallized from ethyl acetate; m.p. 170-172 C.
Example 151 p-Toluenesulfonate salt of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetarnide A solution of p-toluenesulfonic acid (1.9 g., 0.03 mole) in chloroform was added to a solution of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide (2.5 9., 0.01 mole) in chloro-;; form. Evaporation of the chloroform gave the p-toluenesul-20 fonate salt of N,N,a,4-tetramethyl-3-phenylpyrazole having .
a melting point of 131-1~4 C.
:!
A dispersible powder concentrate having the following percentage composition:
~; 25 N,N,~,4-tetramethyl-3-phenyl-pyrazole-1-acetamide 45.8,9 Polymerized sodium salt of sub-.
;~ stituted benzoid long-chain sulfonic acid (Daxad 27) 9.2 30 Kaolinite 45.
.. .
.`-' ' 322g ~053231 was prepared by mixing 250 g. of N,N,~,4-te~ramethyl 3-phenylpyrazole-1 acetamide, ~0 g. of a polymerized sodium salt of substituted benozid long-chain sulfonic acid (Daxad 27), and 245 9. of kaoli ni te. The m;xture was milled to a particle size averaging 5 to 30 microns. It was suspended in 10 gals. of water, giving an aqueous spray containing about 6500 parts per million of active ingredient.
Example 15~
A fine granular formulation having the following per-centage composition:
N,N,a,4-tetramethyl-~-phenyl-pyrazole-1-acetamide 3.7 Vermiculite (30~ 0 mesh) 96.3~
was prepared by spraying a solution of 220 9. of ~,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide in 1000 ml. of chloroform onto 5780 g. of vermiculite (~0 to 60 mesh) while the vermiculite was being tumbled and stirred so as to assure even distribution. The chloroform was then evaporated, leaving the active compound adsorbed on the , 20 vermiculite, and the vermiculite was pulverized.
~e~ ~
An emulsifiable concentrate having the following per-centage composition:
NJ NJ ~ 4-tetramethyl-~-phenyl-pyrazole-1-acetamide 15.0%
Technlcal alkyl naphthalene .... . .
boiling at 238 to 293 C.
(VelsIcol AR50) 19.7%
Xylene 17.4 30 Acetone 17.4 . .
~ 3~3~ ~
Etilylene dichloride 25~4%
Blend of alkyl aryl sullfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.1%
was prepared by mixing 15.0 lbs. of N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide~ 19.7 lbs. cf Velsicol AR50, 17.4 lbs. of xylene, 17.4 lbs. of acetone, 25.4 lbs~ of ethylene dichlorideJ and 5.1 lbs. of Triton X-151.
6.67 Lbs. of the concentra~e mixed with 10 gals. of water gave a spray emulsion containing about 11JOOO ppm of active ingredient.
Example 155 An emulsifiable concentrate having the following per-centage composition.
N,N,~,4-tetramethyl-3-phenyl-pyrazole-1-acetamide 40.0~ 1 Technical alkyl naphthalene boiling at 238 to 293 C.
- (Velsicol AR50) 1307~
`~ 20 Xylene 12.3% ~-: Acetone 11. 3%
Ethylene dichloride 17.7 ; Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.0%
- was prepared by mixing 40.0 lbs. of N,N,~,4-tetramethyl-3-phenylpyrazole 1-acetamide, 13~7 lbs. of Velsicol AR50J
12.3 lbs. of xylene, 11.3 lbs. of acetone, 17.7 lbs. of ethylene dichloride, and 5.0 lbs. of Triton X-151.
1.57 Lbs. of the concentrate mixed with 10 gals. of , ., ,~
~- 8~3 ~229 lOS3Z3~
water gave a spray emulsion containing about 8,ooo ppm of active ingredient.
Exampl_e 156 A dispersible powder concentrate having the following percentage compositior-:
J N,N,a,4-tetramethyl-3-phenyl `' pyrazole-1-acetamide 50 Kaolinite clay (finely divided) 46%
Sodium salt of condensed mono-naphthalene sulfonic acid (Lomar D) 4 .;. . .
~i was prepared by mixing 50 9. of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide, 46 9. of the kaolinite clay, and 4 g. of Lomar D. The mixture was milled to an average particle size of 5 to 30 microns.
1 Example 157 '~s, ', A granular formulation having the following percentage composition:
; N,N,~,4-tetrametHyl-3-phenyl-~v~ ~ 20 pyrazole-l-acetamide 1~
` ~ - Pyrophyllite (30/60 mesh) 99%
~j~ was prepared by dissolving 1.0 lb. of the N,N,a,4-tetra-d~ methyl-~-phenylpyrazole-1-acetamide, in 10.0 1. of ethylene d1chloride and spraying the solution on 9g.0 lbs. of pyro-phylllte. The granules were dried and then packaged for a use.
Example 1~8 - An emulsifiable concentrat~ havtng the following per-centage composit1~n:
j N~N,~,4-tetramethyl-3-phenyl--~ J
32~9 lOS~Z31 pyrazole-l-acetamide 25,~
Tridecylsulfonic acid 25%
Xylene was prepared by mixing 250 g. of N,N,a~4-te~ramethyl~
3-phenylpyrazole-1-acetamide, 250 9. of tridecylsulfonic acid, and 500 g. of xylene. The emulsifiable concentrate containing the tridecylsulfonate salt of N,N,a,4-tetra-methyl-3-phenylpyrazole-1-acetamide was mixed with 10 gals.
of water to give a spray emulsion containing about 6500 ppm of active ingredient.
Example 159 Following the procedure of the preceding Examples 152 through 157, inclusive, compositions are similarly prepared substituting each of the compounds prepared in Examples 2 through 151, inclusive, for the N,N,a,4-tetramethyl-3-phenyl-pyrazole-1-acetamideO
'~
.
. . .
,..~
. ~ 9 lOS~Z~l SUPPLEMENTARY DISCLOSURE
Certain physical and chemical data, inherent in compounds already provided by examples in the principal disclosure, are set out as follows:
N,N,~-trimethyl-3-(o-nitrophenyl)pyrazole-1-acetamide:
NMR (CDC13 - 1% TMS) 1.63, 2.98, 5.34, 6.43, 7.2-7.8 ~.
a-(3-Bromopropyl)-N~N~4-trimetllyl-3-phenylpyrazole-l-acetamide: NMR (CDC13 - 1~ TMS) 1.80-2.40, 2.20, 3.05, 3.43.
5.37, 7.2-7.8 ~.
~ -(4-Bromobutyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide: NMR (CDC13 - 1% TMS) 2.20, 2.50, 3.03, 3.52, 5.58,
.-~ - . , ~ .. . . ~
~053Z31 C, 75.21; H, 6~63; N, 1~.16.
Found: CJ 75 115; H, 6.50; N~ 1;3.29.
1-[2- (4-Methyl-3-phenylpyrazol -1- yl) prOpionyl ]^
pyrrolidine Following the procedure of Example 68~ but substituting pyrrolidine for aqueous ammonia, there was obtained 2-(4-methyl-3-phenylpyrazol-1-yl )propionyl]pyrrolidine having a melting point of 72-74 C.
Analysis:
Calc'd. for C17H21N30~
CJ 72. 05; H, 7.47; N, 14.83.
found: Cl 72.37; H, 7.62; N, 14.68.
Example 77 4-~2-~4-Methyl-3-phenylpyrazol-1-yl)propionyl]
morpholine Fsllowing the procedure of Example 68, but substituting morpholine for aqueous ammonia, there was obtained 4-~2-(4-methyl-~-phenylpyrazol-1-yl)propionyl]morpholine having a ~ melting point of 84-96 C.
.. ~ ~ ';
: 20 Calc'd. for C17H2lN302~
~: C, 68.20; H, 7.07; N, 14.04.
~ Found: C, 67.78; H, 7.11; N~ 13.69. : :
.: : Exam;~le 78 aJ4-D;methyl-3-phenyl-NJN-dipropylpyrazole 1-acetamide Folla~ing the procedure of Example S8, but substituting ~: dipropylamine for aqueous ammonia, there was obtained a,4-di-methyl-3-phenyl-N~N-dipropylpyrazole-1-acetamide having a ~: boiling point of 176 /o.6 mm.
- 30 Calc'd. for Cl9H27N30:
.
. . . . .
:~229 C, 72.80; H. 8~68; N, 13.41 F~und~ C. 72.80; H, 8.75; N, 1~.32.
- ~79 4~Me~hyl-3-phenyl~a-propylpyrazole-1-acetamide Following ~he procedure of Exarnple 68, bu~ substi~uting 5 4-methyl-3-phenyl-a-propylpyrazole-1-acetic acid for a,4 di methyl-3-phenylpyrazole-1-acetic acid, there was ~btained 4-methyl-3-phenyl-~-propylpyrazole-1-acetamide having a melting point of 116-118 C.
~ '.
Calc'd. for Cl5HlgN30:
C, 70.00; H, 7.44; N, 16.33.
Found: C, 70.11; H, 7.71; N, 16.60.
Example 80 N,4-Dimethyl-3-phenyl-a-propylpyrazole-1-acet-amide Following the procedure of Example 6~37 but substituti ng aqueous methylamine for aqueous ammonia, and 4-methyl-3-phenyl-~x-propylpyrazole-1-acetic acid for a,4-dimethyl-3 ` phenylpyrazole-1.acetic acid, there was ob~ained N,4-di-methyl-3-phenyl-c~-propylpyrazole-1-acetamide having a melt-Z0 ing point of 84-86 C.
~_1 s:
Calc'd. for C16H2~N30:
, 70.82; H, 7.80; N, 15.49.
Found: C, 70.42; HJ 7.98; N, 15.52.
25 ~e~ N,N,4-Trimethyl-3-phenyl-a-propylpyrazole-1-acetamide Folla~ing the procedure of Example 68, but substituting dirnethylamine for aqueous ammonia and 4-methyl-3-phenyl-~pro-pylpyrazole-1~cetic acid for ~x,4-dimethyl-3-phenylpyrazole-30 1-acetic acîdJ there was obtained N,N,4-trimethyl-3-phenyl- -..
~229 10532~1 a-propylpyrazole-1-acetamide having a melting point of 84-86 C.
Calc'd. for C17H23N30:
C, 71.54; H~ 8.12; N, 14~7~.
Found: Cl 71.47; HJ 8.22; N, 14.91.
~xample 82 N,N-Diethyl-4-methyl-3-phenyl-a-propylpyrazole-1-acetamide Following the procedure of Example 68, but substituting diethylamine for aqueous ammonia and 4-methyl-3-phenyl-~-propylpyrazo1e-1-acetic acid for a,4-dimethyl-1phenylpyrazole-1-acetic acid, there was obtained N,N-diethyl-4-methyl-3-phenyl-a-propylpyrazole-1-acetamide having a melting point ~- of 65-67 C.
~ :
,' -:
Calcld. for C13H27N30:
C, 72.80; H, 8.68; N) 13.41.
Found: C, 73.00; H, 8.73; N, 13.59.
N,N-Diethyl-a-methyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting methyl-3-phenylpyrazole-1-acetic acid For a,4-dimethyl-;~ 3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous ammonia there was obtained N,N-diethyl-a-methyl-3-phenylpyra-zole-1-acetamide having a boiling point of 178/0.2 mm.
Analysis:
Calc'd. for Cl~H2lN30:-~; C, 70.82; H, 7.80; N, 15.49 Found: C, 70.60; H, 7.74; NJ 15051.
Example 84 a-~ethyl-3-phenyl-N,N-dipropylpyrazole-1-acet-~ :
amide -:
-5g-., .
,, . . . . ,, ::
. .. ~ . '~-', , ; . . ~ , - . . : , , - . .
~22g ~OS323~
Following the procedure of Exam~le 68, but substituting dipropylamine for aqueous ammonia and ~-methyl-3-phenylpyra-zole-1^acetic acid fo. ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, there was obtained ~-methyl-3-phenyl-N,N-dipropylpyr-azole-L-acetamide having a boiling point of 181/0.4 mm.
Analys~s:
Calc'd. for C1aH2sN30O
C, 72.20; H, 8.42; N, 14.04.
Found: C, 72.03; H, 8.69; N, 13.90.
~ ~-Ethyl-N,N-dimethyl-3-phenylpyrazole-1 acetamide Following the procedure of Example 68, but substituting ; a ethy1-3-phenylpyra~ole-1-acetic acid for ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for :-aqueous ammonia, there was obtained a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide having a melting point of ~01-103 C.
Analysis:
Calc'd. for C15Hl~N30:
C, 70.00; ~, 7.44; N, 16.33 .: 20 Found: C, 70.16; H, 7.48; N, 16.140 ~: ~ ~ N,N,a-Trlethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting ,~
.a-ethyl 3-phenylpyrazole-1-acetic acid for a,4-dimethyl~
3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous : .
ammonia, there was obtained N,N,a-trtethYl-3-phenylpyrazole-~ acetamide having a meltTng point o~ 63-66~ C.
:~ Calc'd. for C17H23N90:
, 71.54; H, 8.1~; N, 14.73.
Found: C~ 71.85; H, 8.12; N, 14.71.
' - ,~: ' ' : , ' , , 322g Ex~7 N,Ngtx-Triethyl-4-methyl-3-phenylpyrazole-1-acet-.
amide Following the procedure of Example 68, but subst;tut;ng a-ethyl-4-methyl-~-phenylpyrazole-1-acetic acid f~r a,4-di-methyl-3-phenylpyrazole-1-acetic acid, and diethylamine for aqueous ammonia, there was obtained N,N,a-triethyl-4-methyl-3-phenylpyrazole-1-acetamide having a melting point of 80_82 C.
Calc'd. for C18H25N30.
C, 72.20; H, 8.42; N, 14.01.
Found: C, 7~.34; H, 8.73; N, 14.47.
a-lsopropyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 68, but substituting a isopropyl~4-methyl-3-phenylpyrazole-1-acetic acid for a,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethyl- ;~
amine for aqueous ammonia, there was obtained a-isopropyl-~ N,N,4-trimethyl-3-phenylpyrazole-1-acetamide having a melt-s~ 20 ing point of 66.5-68.5 C. ~ :
Analysis:
Calc'd. for Cs7H23N30: -, ~ C, 71.54; H, 8.12; N, 14.73.
-~Found: C, 71.67; H, 8.15; N, 14.63.
!~5 ~ 4-Chloro-a-ethyl-N,N-dimethyl-3-phenylpyrazole-.
,~
1-acetamide Following the procedure of Example 68, but substituting .
~4-chloro-a-ethyl-3-phenylpyrazole-1-acetic acid for a,4-di-'~
methyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for aqueous ammonia, there was obtained 4-chloro-a-ethyl-, , ~ , ~ , , ., . - . - ...... .:
- ~,. ~ , . . : , . . :
- , ~ , . . .
;3 c 2 g 11~53Z31 N~N-dimethyl-~-phenylpyrazole-1-acetarnide having a melting point o~ ~4-~6.5 C.
Anal x,s i s.
Calc'd. for Cl5H1~ClN30:
C, 61.74; H, 6.22; N, 14.40j Cl, 12.15.
Found: C, 62.22; H~ 6.26; NJ 14.29; C1~ 12. 07.
Alternate Synthesis of 4- oro-a-ethyl-N,N-dimethyl-:; :
3-phenylpyrazole-1-acetamide a-Ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide (51.4 g., 0.2 mole) was dissolved in chloroform (200 ml.).
A so1ution of potassium carbonate (28.0 9.) in water (100 ml.) was added. The two-phase reaction mixture was stirred vigorously at 10 C. during the addition of chlorine (10 ml., 14.7 9., 0.2 mole). After addition was complete, the organic phase was separated, washed with water, and the solvents were removed under reduced pressure. The residue was dissolved in benzene (60 ml~) and Skellysolve B (300 ml.) was added. The solution was cooled to -10 C. and filtered ~o afford 56.7 9. of 4-chloro-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide, m.p. 95-97 C.
2~ 4-Chloro-N, NJ a-tr7ethyl-3-phenylpyrazole 1-acetamide Following the procedure of Example 68, but substituting 4-chloro-~ ethyl-3-phenylpyrazole-1-acetic acid for a,4 di-methyl-~-phenylpyrazole-1-acetic acid and diethylamine for aqueous ammonia there was obtained 4-chloro-N,N,a-triethyl-3-phenylpyrazole-1-acetamide having a melting point of 47-49 C.
Analvsis , ~ 30 Calc'd. for C17H22ClN30: ~
j2~9 53i231 C, 63.84; H, 6.93; N! 1~.14; Cl, ~ 9.
Folind: C, 63.~7; H, ~97; N, l2.94; Cl, 11.01.
~e~ 91 4-Chloro-a-ethyl-3~pl-1enyl-N,N-dipropylpyrazole-1-acetamide Following the procedure of Example 68, but substituting 4-chloro-a-ethy7-3-phenylpyrazole-1-acetic acid for a,4-di-methyl-3-phenylpyrazole-1-acetic acid, and dipropylamine for aqueous ammonia, there was obtained 4-chloro-a-ethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide having a boiling point of 184 /0.25 mm.
Analysis:
; Calc'd. for C19H26ClN30:
C, 65.59; H, 7.53; N, 12.03; Cl, 10.19.
Found: C, 66.5~; H, 7.99; N, 12.25; Cl, 10.52.
Examp_e 92 N,N-Dimethyl-3-phenyl-a-propylpyrazole-1-aceta-mide Following the procedure of Example 68, but substituting 3-phenyl-a-propylpyrazole-1-acetic acid for a,4-dimethyl 3-phenylpyrazole-1-acetic acid and aqueous dimethylamine for aqueous ammonia there was obtained N,N-dimethyl-3-phenyl-~-propylpyrazole-1-acetamide having a boiling point of 180-181/0.1 mm.
~:
Calc~d. for Cl~H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.53; H, 7.86; N, 15.67.
N,N,4-Trimethyl-aJ3-diphenylpyrazole-1-acetamide ':
Following the procedure of Example 68, but substituting 4-methyl-a,3-diphenylpyrazole-1-acetic acid for a,4-dimethyl-3-phenylpyrazole-1-acetic acid and dimethylamine for aqueous :
.. . -.- - - . ~: . . . . . . .
~ ~ . . .
~ lOS~Z31 amrnonia, there was ob.ained N,N,4-trimethyl-~,3-diphenyl-pyrazole-1-3cetamide havin3 a melting point of 135.5-138 SO
Anal~
Calc'd. for C20H2~N90:
C, 75.21; H, 6.63; N, 13.16.
Found: C, 75.37; H) 6.76; N, 13.28.
Example 94 4-Cyano-NyN,a-trimethyl-~-phenylpyrazole- t~
.. . .
1-acetamide A mixture of 4-bromo-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide (8.o 5., 0.025 mole) cuprous cyanide (25.0 9., 0.28 mole) and dimethylformamide (200 ml.) was heated under reflux for 18 hours. Water was added and the solution was repeatedly extracted with chloroform. Evaporation of the chloroform gave a residue (7O5 g.), which was recrystallized from benzene:Skellysolve B to give 6.5 9. of 4-cyano-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide, m.p. 132-146 C.
Two recrystallizàtions from ethyl acetate gave the analytical sample, m.p. 144-146 C.
Analysis:
Calc'd. for C15H~N40:
C, 67.14; H, 6.01; N, 20.88.
Found: C, 67.12; H, 6.12; N, 21.18.
a-Ethyl N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide n-Butyl lithium (40 ml. of 1.6 M solution in hexane, I
o.c5 mole~ was added under nitrogen to a stirred solution of N,N,~,4-tetramethyl-3-phenylpyrazo!e-1-acetamide (12.8 g., ~. i 0.05 mole) in THF (150 ml.). Ethyl iodide (30 9.) was added. The solvent was removed after 30 minutes and the residue was partitioned between chloroform and wa~er. The 16~S3231 chloroform was evaporated and the residual oil was chroma-tographed on si l ica gel usi ng benzene:ethyl acetate (9:1 ) as eluant. a-Ethyl-NJN~a~4-tetramethyl-3-phenylpyrazole-1-acetamide (4.9 9.) was the second ma30r band to be eluted from the column. Recrystallization from methanol followed by cyclohexane gave the analytical sample, m.p. 102-104 C~
Analysis:
Calc'd. for C17Hz9N30.
C, 71.54; H, 8.12; N, 14.73.
Found: C, 71.59; H, 7.75; N, 14.91.
N,N,a,4-Tetramethyl-3-phenyl-a-propylpyrazole-1-acetamide Following the procedure of Example 95, but substituting propyl bromide for ethyl iodide, there was obtained N,N,a,4-tetramethyl-3-phenyl-a-propylpyrazole-l-acetamide having a melting point of 90-92 C.
Analysis:
Calc.~d. for C18H25N30:
C~i72~20; H, 8.42; N, 14.01.
Found: C, 72.17; H, 8.39; N, 13 97.
; ~ Example 97 aJ~-Diethyl-NlN~4-trimethyl-3-phenylpyrazole ~ 1-acetamide ; Following the procedure of Example 95, but substituting a-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide for N~N~a~4-tetramethyl-3-phenylpyrazole-l-acetamide~ there was obtained a~a-dlethyl-N~N~4-trimethyl-3-phenylpyrazole-l-acet amide having a melting point of 135-1~6.5 C.
Ana!ysis:
Calcld. for Cl8H25N30: ; -C, 72.20; H, 8.42; N, 14.01.
~: :
.. . . , , . .. . ~.
1~53~31 Found: C, 72~40i H, 8.27; ~ 14~17.
a-Ethyl-N,N,4-trimethyl-3-phenyl-a-propylpyra- :
zole-l-acetamide Following the procedure of Example 95, but substituting a-ethyl-N,N,4-trimethyl-3-phenyl pyrazol e-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and propyl bromide for ethyl iodide, there was obtained a-ethyl-NJN~4-trimethyl-3-phenyl-a-propylpyrazole-l-acetamide having a melting point of 147-148 C.
10 ~.
:. ~
Calc'd. for Cl9H27N30:
C, 72.80; H, 8.68, N, 13.41.
Found: ~, 72.85; ~, 8.44; N, 13.75.
Example 99 N,N,a,a,4-Pentamethyl-5-phenylpyrazole-1-acet-; 15amide Following the procedure of Example 95, but substitut-ing NJN,a,4-tetramethyl-5-phenylpyrazole-1-acetamide for . N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide, there was obtained N,N,a,a,4-penta-:~20 methyl-5-phenylpyrazole-1-acetamide having a melting point o~ 1~6-139 C.
Calc'd. for C1~H2lN30:
C, 70.82; H, 7.80; N, 15.49.
25Found: C, 71.03; H, 7.98; N, 15.74.
N,N,a,4-Tetramethyl-a,3-diphenylpyrazole-. 1-acetamide Following the procedure of Example 95, but substitut-ing N,N,4-trimethyl-a,3-d7phenylpyrazole-1-acetamide for ~0 N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl ~2~9 ~53~31 iodide for ethyl iodide, there was obtained N,N,~,4-~etra-methyl-~,~-diphenylpyrazole-1-acetamide having a meltin3 point of 107~109 C.
Calcld. for C21H23N30~
C, 75.64; H, 6.95; N, 12.60.
Found: C, 75.61; H, 7.o8; N~ 12.46.
Exampl__101 NJN,a,a,4-Pentamethyl-3-(2-thienyl)pyrazole-1-acetamide Following the procedure of Example g5, but substitut-ing N,N,a,4-tetramethyl-3-(2-thienyl)pyrazole-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide there was obtained N,N,a,a,4-pentamethyl-3-(2-thienyl)pyrazole-1-acetamide having a 15 melting point of 116-119 C.
:j Calc'd. for C14H19N30S: ~ i C, 60.62; H, 6.90; N, 15.15; S, 11.56.
- Found C, 60.82; H, 6.88i N, 14.92; S, 11.78. ~
20 ~ 3-(2-Furyl)-N,N,a,a,4-pentamethylpyrazole- ~ :
1-acetamide Following the procedure of Example ~5, but substitut- ~
~ ing 3-(2-furyl)-N,N,a,4-tetramethylpyrazole-1-acetamide for .
~ N,N,a,4-tetramethyl-~-phenylpyrazole-1-acetamide and methyl iod;de for ethyl iodide there was obtained ~-(2-furyl)-N,N,a,aJ4-pentamethylpyrazole-1-acetamide having a melting point of 131-134 C.
Calc'd~ for Cl4H19N302:
C, 64.34; H, 7.33i N, 16. o80 : -67 .
^ - - - .. . ,, ~ : . . . . .
~- - : . ... . . . . .
.: , . .
3~29 10~
Found: C, 62.90; ~ 7.03; N, 15.87.
03 N,N-Dimethyl~ metllyl-~-phenylpyrazol~l-yl~-cyclopropaneearboxamide f`o~iowlng the procedure of Example 9~, ~ut subs~ltuting ~-(2-chloroethyl)-NJN,4-trimethyl-~-phenylpyrazole-1-aceta-mide ~prepared in Example 45) for N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide and ~ithout addition of ethyl iodide there was obtained N,N-dimethyl-1-(4-methyl-3-phenyl-pyrazol-1-yl)cyclopropanecarboxamide, m.p. ~2-55 C.
Analysis:
Calc'd. for Cl6H19N30:
; C, 71.34i H, 7.11; N, 15.~0. :~
Found: C, 71.23; H, 7.13; N, 15.67.
Examp!e 104 N,N-Dimethyl-1-(4-methyl-~-phenylpyrazol-1-yl)-cyclo~utanecarboxamide .` Following the procedure of Example 95J but substituting a-(3-bromopropyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acet-amide for N,N,aJ4-tetramethyl-3-phenylpyrazole-1-acetamide and without the addition of ethyl iodide there was obtained N,N-dimethyl-1-(4-methyl-3-phenylpyrazol 1-yl)cyclobutane-~ carboxamide having a melting point of 87-8~ C.
- Analysis:
: I .
Calc~d. for Cl7H2lN30:
~: C, 72.05; H, 7.47; N, 14.83 Found: CJ 71.83; H, 7.82; N, 14.89.
I ~ N,N-Dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)- 1 -cyclopentanecarboxamide Following the procedure of Example 95, but substitut-ing a-(4-bromobutyl)-N,N,4-trimethyl-~-phenylpyrazole-~0 1-acetamide (prepared in Example 4~) for N,N,a,4-tetra-~8- :
; I
1053Z3~ `
methyl-~-phenylpyrazole-1-acetamide and without addition or ethyl iodide there was obtained N~N-dimetilyl-1-(4-methyl-3 phenylpyrazol-1~yl)cyclopentanecarboxamide ~ N,N-D~methyl-1-(3-phenylpyrazol-1-yl)cyclopro-pa neca rboxam i de Following the procedure of Example 95, but substitut-ing a-(2-chloroethyl)-N,N-dimethyl -3-phenyl pyrazole-1-acet-amide for N,N,a,4-tetramethyl-~-phenylpyrazole-1-acetamide and without addition of ethyl iodide there was obtained N~N-dimethyl-l-(3-phenylpyrazol-l-yl)cyclopropanecarb amide having a melting point of 96-99 C.
Analysis:
Calc'd. for C1sH17N30:
C, 70.56; H, 6.71; N, 16.48.
Found: C, 70.19; H, 6.68; NJ 16.46.
N, N-D imethyl-1-(3-phenylpyrazol-1-yl)cyclo butanecarboxamide Following the procedure of Example 95, but substitut-; Ing ~-(3-br~m~propyl)-N, N-dimethyl-~-phenylpyrazole~1-ace~-amide for NJNJaJ4-tetramethyl-3-phenylpyrazole-l-acetamide and without addition of ethyl iodide there was obtained N,N-dlmethyl-1-(~ phenylpyrazol-1-yl)cyclobutanecarboxamide ha~ing 2 boilTng point of 170/0.1 mm.
~,.
::
Calc'd. for C1~H~9N30:
C~ 71.~4; HJ 7.11; N/ 15.60.
Found~ CJ 71.42; H~ 7,19; N~ 14.63.
4-Bromo-N,N~,5-tetramethyl-~-phenylpyrazole- -1-acetamlde - 30 Bromine (3.68 9., .o46 moleJ was added to a solution :
... .
. . ..
.
~2~9 ~53Z31 of N,N,a,5- tetramethyl -3-pheny1pyrazole-1-acetamide (5.~) 9., .OIg mole) in acetic acid~ At~ter 1 hour, the solutiQrl ~as dilueed with water to give 6.3 9. of 4-br~no-NJN~G~J5-tetramethyl-~-phenytpyrazole-l-acetamide7 m.p.
88-89.5 C. Recrystallization from benzene-Skellysolve B
and finally ether gave the analytical sample~ m.p.
88-8~.5 C.
Calc'd. for C15Hl8BrN30: :
C, 53.58i H, 5.40; Br, 23.77; N, 12.50.
Found: C, 53.69; H, 5.54; Br, 23.69; N, 12.30.
4-Bromo-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-ace~amide - Following the procedure of Example 108, but substitut-Ing a-ethyl-NsN-dimethyl-~-phenylpyrazole-1-acetamide for ' N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, there was -~ obtained 4-bromo-a-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide hav7ng a melting point of 97-100 C. I
Calc'd. for Cl5H18BrN30: , - -- C, 53.58; H, 5.40; N, 12.48; Br, 23.77.
Found C, 53.75; H, 5.45; N, 12.68; Br, 2~.75.
4-Chloro-~-(p-chlorophenyl)-N,N,a-trimethyl-pyrazole-1 acetamide ~ : 25 Fol1Owing the procedure of Example 108, but substitut-~ - ing 3-(p-chl~rophenylj-N,N,~-trimethylpyrazole-1-acetamide for N,NJa,5-tetramethyl-~-phenylpyrazole-1-acetamide and sulfuryl chloride for bromine, there was obtained 4-chloro-3-(p-chlorophenyl)-N~N,~-trimethylpyrazole-1-acetamide having a melting point of 92-93 5 C.
' -,, . . . , ~ , .
, 322~3 ~OS3231 ~nal l~is Calc~d. for C14HlSCI2N30:
C, 5~.86; H, 4.84; N, 1~.46; Cl, 22.71.Found: C, 54.00; H~ 4.88; NJ ~13.4L, ~t, 22.~4.
5 ~ 4-Chloro-3-(o-chlorophenyl)-N,N~a-trimethyl- :
. .
pyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing 3-(o-chlorophenyl)-N,N,a-trimethylpyrazole-1-acetamide for N,NJa,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachloridefor acetic acld as the reaction solvent, there was obtained ,, 4-chloro-3-(o-chlorophenyl)-N,N,a-trimethylpyrazole-1-acet-amide hav',ng a melting point of 108-111 C.
~: ;.
: 15 Calc'd. for C~H~5Cl2N30~
C, 53.86; ~, 4.84; N, 22.71; Cl, 13.46. -Found: C, 53.77; H, 4.89; N, 22.87; Cl, 1~.29.
4-Chloro-N,N,a-trimethyl-3-(o-tolyl)pyrazole-1~acetamide Following the procedure of Example 108, but substi,ut-; Ing N,N,a-trimethyl-~-(o-tolyl)pyrazole-1-acetamide for ,~ N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachloride for acetlc acid as the reaction solvent, there was obtained 4-chloro-N,N,a trimethyl-~-(o-tolyl)pyrazole-1-acetamide ~ . havIng a melting point of 6~-71.5 C.
J: .. . .
Calc'd. for C15H~8ClN30:
- C, 61.7~; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.59; ~, 6.32; N3 14.32; Cl, 12.17.
~053;23~
Exam ~ 4-Chloro-N,N,~-trimethyl-~-(o methoxyphenyl3-pyrazole-1-ace~amide Follcwing the procedure of xample 108, but substitut-;ng N,N,~-trimethyl-3-(o-methoxyphenyl)pyrazole-1-acetamide for N5N,~,5-tetramethyl-~-phenylpyrazole-1-aceta~;de, tert-butyl hypochlorite for bromine, and carbon tetrachloride for acetic acid as the reaction solvent, there was obtained 4-chloro-N,N,a trimethyl-3-~o-methoxyphenyl)pyrazole-1-acet-; amide having a me1ting point of 74-77 C.
Analys- s:
Calc'd. for C15H18ClN30z:
C, 58.53; H, 5.89; N, 11.52; Cl, 13.65.
Found: C, 58.70; HJ 5.95; N, 11.48; Cl, 13.88.
4-Chloro-N~N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide Follcwing the procedure of Example 103, but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl ~ hypochlorite for bromine, and carbon tetrachloride for ; ?O acetic acid as the reaction solvent, there was obtained 4-chloro-N,N,a,a tetramethyl-3-phenylpyrazole-1-acetamide ha~ing a melting point of 117-113 C.
Calc'd. for C1sH18ClN~0:
C, 61.74; H, 6.22; N, 14.40; Cl, 12.15.
Found: C, 61.53; H, 6.33; N, 14.36; Cl, 12.15.
~ 4-Chloro-N,N-dimethyl-3-phenyl-a-propylpyrazole-; 1-acetamide Following the procedure of Example 108, but substitut-ing N,N-dimethyl-3-phenyl-a-propylpyrazole-1-acetamide for .
3'229 ~ ~ S ~Z 3 ~
N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for br~line, and c~rbon tetrachloride for acetic acid as the reaction solvent, there was obtained 4-chloro-N,N-dimethyl-3-phenyl-a-propylpyrazole-1-acetamide having a meltin~ point of 85-87 C.
Analysis:
; Calc'd. for C1~H20ClN30:
C, 62.~4; H, 6.59; N, 13.74; C1J 11.59.
Found: C, 62.95; H, 5.84; N, 13.83; Cl, 11.68.
10 Exam~le 116 4-Chloro-N,N,a-trimethyl-3-(2,6-dichlorophenyl)-- pyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing N,N,a-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acet-amide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, tert-butyl hypochlorite for bromine, and carbon tetrachlo-ride for acetic acid as the react~on solvent, there was obtained 4-c~oro-N,N,a-trimethyl^3-(2,6-dichlorophenyl)-pyrazole~1-acetamide having a melting point of 126-128 C.
A n? l ys i s:
Calcld. for C14H14Cl3N30:
C, 48.51; H, 4.07; N, 12.12; Cl, 30.69.
Found: Cg 4g.o6; H, 4.15; N, 12.0~; Cl, 30.59.
4-Chloro-N,N,a-trimethyl-3-phenylpyrazole-., .
1-propionamide Following the procedure of Example 108, but substitut-ing N,N,a-trimethyl-3-phenylpyrazole-1-propionamide for N,N,~,5-tetramethyl-3-phenylpyrazole-1-acetamide, and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-N,N,~-trimethyl-~-phenylpyrazole-1-propionamide having a b~iling point of 190/0.3 mm.
.
.,, ' ~ .
~29 lC~S3Z3~
Analysi~:
Calc'd. for C15HlBC1N30~
C, 61.74; H~ 6.22; N~ 1~.40; Cl, 12.15.
Found: C, 61.~2; H, 6.48; N, 14.57; Cl~ 12.39.
~ 4-Chloro-3-(o-chlorophenyl)-a-ethyl-N,N-di-methylpyrazole-1-acetamide Following the procedure of Example 108, but substitut-ing 3-(o-chlorophenyl) a-ethyl-N,N-dimethylpyrazole-1-acet-amide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide, `
and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-3-(o-chlorophenyl)-a-ethyl-N,N-dimethylpyrazole-1-acetamide.
Analysis-' Calc'd. for C15H17Cl2N30-C~ 55.22; H~ 5.26; N~ 12.88; C1, 21.74.
Found: CJ 55.23; HJ 5.26; N, 12.93; C1, 21.4~.
Examp!e 119 4-Chloro-~-(o-chlorophenyl)-N,N,a,a-tetramethyl-pyrazole-1-acetamide Following the procedure of Example 108, but substitut-~` 20 ing 3-(o-chlorophenyl)-N,N,a,a-tetramethylpyrazole-1-acet-amide for N,N3a~5-tetramethyl-3-phenylpyrazole-l-acetamide~
and tert-butyl hypochlorite for bromine, there was obtained 4-chloro-3-(o-chlorophenyl)-N,N,a,~-tetramethylpyrazole-1-acetamide.
~ 4-Chloro-N,N,a,a-tetramethyl-3-(o-tolyl)pyra-zole-1-acetamide Following the procedure of Example 1oB, but substitut-~ ing N,N,a,~ tetramethyl-3-(o-tolyl)pyrazole-1-acetamide for ;~ N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-~ 30 butyl hypochlorite for bromine, there was obtained 4-chloro-t, . , .
: . . ,- , . . . .
1~53Z3~ 3229 ,:
N,NJa~a tetramethyl-3-(o-tolyl)pyrazole-1-acetaTnide having a melting point of 1~4.5 136 C.
Calc'd. for Cl6H20ClN30:
C, 62.84; H, 6.59; N~ 13.74; Cl, 11.59.
Found: C, 62.77; H, 6.73; N, 13~67; Cl, 11. 58. ~ :
Example 121 Alternate synthesis for N,N,~-trimethyl-3-phenylpyrazole^1-propionamide A mixture of 14.4 9. (0.1 mole) of 3-phenylpyrazole-20.8 9. (0.15 mole) of anhydrous potassium carbonate and 29.1 9. (0.15 mole) of 2-bromo-N,N,2-trimethylpropionamide was stirred at 140 C. for 1. 5 hour. The mixture was ` diluted with water and extracted with benzene. Evaporation ~ -? of the benzene gave an oil which was crystallized from cyclohexane to give 7.8 g. of N,N,~-trimethyl-~-phenylpyra-zole-1-propionamide, m.p. 68-71 C.
! Example 122 N,N,~,4-Tetramethyl-3-phenylpyrazole-1-propion-.j .
; amide Following the procedure of Example 1?1, but substitut-2C Ing 2-bromo-N,N-dimethylbutyramide for 2-bromo-N,N,2-tri-methylpropionamide, and 4-methyl-3-phenylpyrazole for 3-phenylpyrazoleJ there were obtained the already described a-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide and ~; N,N,~,4-tetramethyl-3-phenylpyrazole-1-propionamide having a boiling point of 170/0.2 mm.
Calc'd. for C1~H21N
~, C, 70.82; H, 7.80; N, 15.49.
Found: C, 70.87; H, 7.92; N, 15084.
~ ~-Ethyl-N,N-dimethyl-3-phenylpyrazole-1-propionamide ,~, .
,-., .. . , ~ .. .
~29 1~53Z3~
Fol l ow i ng the procedure of E~iampl e ~21, but subst i tut-ing 2-b,omo-N,N-dimethylvalera~nide -For 2-bromo-N,N92-tri-methylpropionamide~ there were obtained the already des-cribed NJN-dinlethyl-3-phenyl-a~propylpyrazole-l-acetamide and ~-et,lyl-N~N-dimethyl-3-phenylpyrazole-1 propionamide hav i ng a melt î ng point of 97-99 C.
- Anal ~s is:
~ Calc'd. for Cl6HzlN30:
: C, 70.82; H, 7.80; NJ 15.49.
Found: C, 70.75; H, 7~84; NJ 15.56.
~ Example 1?4 N,N-Dimethyl-3-phenylpyrazole-1-propionamide : Foll~ing the procedure of Example 121, but substitut-ing 2-bromo-N,N-dimethylpropionam7de for 2-brcmo-N,N,2-tri-methylpropionamide there were obtained the already described NJN,~-trimethyl-~-phenylpyrazole-1-acetamide and N,N-di-! methyl-3-phenylpyrazole-1-propionamide having a melting point of 103-105 C.
.J . ~,~ .
., .
Calcrd. for C14H17N30:
C, 69.11; H, 7.04; N, 17.27.
4 Found: C, 68.98; H, 6.92; N, 17.00.
~.' Example 125 N,N,~-Trimethyl-3-phenylpyrazole-1-propionamide -. Follow;ng the procedure of Example 121, but substitut-ing 2-bromo-N,N-dimethylbu~yramide for 2-bromo-N,N,2-tri-?5 methylpropionamide there was obtained the already described a-ethyl-NJN-dimethyl-3-phenylpyrazole-l-acetamide and ~' N,N,~-trimethyl-~-phenylpyrazole-1-propionamide having a !
~ melting point of 65-67 C.
., ~:
~0 Ca l c ' d O for Cl 5H1 9N90 .
.
76- :
.
.. . .
~229 lQS3Z31 c~ ro ooi ~1, 7.~4; I~IJ ~6.3:~.
Found: C, 69.94; H, 7.47; N, 16.56.
~-Bromo-N,N,4-trime~hyl-3-phen,vlpyrazole-1-propionamide ; 5 Following the procedure of Example 121~ but substitut-ing 2,3-dibromo-N,N-dimethylpropionamide for 2-bromo-N,N,2- ~ -trimethylpropionamide and ~-methyl-3-phenylpyrazole for 3-phenylpyrazole there was obtained ~-bromo-N,N,4-trimethyl-~-phenylpyrazole-1-propionamide having a melting point of 104-107 C.
'. ~y~: :
Calc'd. for C15H1 8 BrN30:
C, 53.58; H, 5.39; N) 12.50; Br, 2~.77.
Found: C, 53.99; H, 5.51; N, 1~.63; Br, 23.43.
Example 127 N~NJa~aJ4-pentamethyl-3-phenylpyrazole 1-thioacetamide i N~N~a~a~4-pentamethyl-3-phenylpyrazole-l-acetamide J (2.71 g., 0.01 mole) was dissolved in 10 ml. of pyridine with s~irring~ To this solution was added phosphorous penta5ulfide (3.33 g., 0.015 mole) and the mixture heated ~t reflux for one hour. The reaction mixture was parti-tloned Tn water-benzene, the benzene layer separated and washed with water. Evaporation of the benzene gave 2.75 9.
of crude material which was chromatographed on silica gel.
Elution with 10~ ethyl acetate in benzene gave 2.65 gm. of ' : NJN~ J4-pentamethyl-3-phenylpyrazole-l-thioacetamide J whlch was recrystallized from ethyl ac2tate:Skellysolve B
to give 2.0 9. having a melting point of 115-117 C.
Analysis: -Calc'd. for ClaH21N3S:
~ .
~29 lQ53231 C, 66.86; H, 7.37i N, 14.62; S~ 11.15.
Found: C, 66.82; H, 7O5~; N, 14~53; S, 11.27.
128 a-(n-Butyl)-N,N,4~trimethyl-3-phenylpyraz~le 1-thioacetamide Following the procedure of Example 127, but substitut-i ng a- (n-butyl~-N,N,4-trimethy1-3-phenylpyrazole-1-acet-amide for N,N,a,,4-pentamethyl-3-phenylpyrazole-1-acet-amide there was obtained a-(n-butyl)-NJN,4-trimethyl-~-phenylpyrazole-1-thioacetamide having a melting point ~f 93-g5 C.
Calctd. for Cl8H25N3S:
C, 68.53; H, 7.99; N, 13.32; S, 10.16.
Found: C, 68.31; HJ 8.27; N~ 13.39; S~ 10.24. 5 ~ N,N,a,a-Tetramethyl-3-phenylpyrazole-1-thio-acetamide Following the procedure of Example 127, but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide for N,N,a,a,4-pentamethyl-~-phenylpyrazole-1-acetamide there was ob~ained N,N,a,a~tetramethyl-3-phenylpyrazole-1-thio-acetam1de having a melting point of 124-127 C.
Calc'd. for C15H19N3S:
C, 65.90; H, 7.00; N, 15.37; S~ 11.73.
Found: C, 65.70; H~ 7.17; N, 15.45; S, 11.68.
N,N-Diethyl-~,4-dimethyl-3-phenylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitùt-ing N,N^diethyl-,4-dimethyl-3-phenylpyrazole-1-acetamide for NJN,a,a-4-pentamethyl-3-phenylpyrazole-1-acetamide ~78-, ' lQ53231 there was obtained N,N-diethyl-a.4-dimethyl-~-phenylpyrazole-1-thioacetan~ide having a melting point of 76-79 C.
Calc~d~ for C17H23N~S:
C, 67.73; H3 7.69; N, 13.94; S, 10.64.
Found: C, 67.54; H, 7.59; N, 14.16; S~ 11.61.
a-Ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitut~
ing o~ethyl-N,N,4-trimethyl-~-phenylpyrazole-1-acetamide for N,N,a,~,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained ~-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide having a melting point of 107-110 C.
- bnalysis Calc'd. for C16H21N3S:
C, 66.85; H, 7.37; N, 14.62; S, 11.15.
Found: C, 66.76; H, 7.56; N, 14.70; S, 11.02.
4-Chloro-N,N,~-trimethyl-~-phenylpyrazole-` 1-thioa~etamide ; 20 Following the procedure of Example 127, but substitut-ing 4-chloro-N,N,~-trimethyl-~-phenylpyrazole-1-acetamide for N,N,,~,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained 4-chloro N,N,a-trimethyl-3-phenylpyrazole- -1-thToacetamide having a melting point of 80-83 C.
~5 ~ :
Calc'dO for C14Hl~ClN3S:
C, 57.23; H, 5.47; N, 14.30; Cl, 12.07;
S, 10.91.
Found: C, 57.13; H, 5.60; N, 14.44; Cl, 12.14;
~` 30 S, 11. 03.
~ -79-~229 ~053Z31 NJN,a-Trin-ethyl-3-phenylpyrazole-1-thioacet-amide Following the procedure of Example 127, but sUbstitut ing N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,~a,4-pentamethyl-3-phenylpyrazole-1-acetanlide there was obtained NJN,a-trimethyl-3-phenylpyrazole-1-thioacet-amide having a melting point of 56-58 C.
Calc'd. for C14H17N3S:
~ 10 C, 64.83; H, 6.61; N, 16.21; S, 12.36.
`; Found: C, 64.76; H, 6~72; N, 16.32; S, 12.50.
; Example 134 N,N,a,4-Tetramethyl-3-phenylpyrazole-1-thio-acetamide Following the procedure of Example 127, but substitut-ing N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide for N,N~a~aJ4-pentamethyl-3-phenylpyrazole-l-acetamide there was obtained N,N,a,4-tetramethyl-3-phenylpyrazole-1-thio-acetamide having a melting point of 87-89 C.
Analysis:
~ 20 Calc'd. for Cl5H19N3S.
- C, 65.90; H, 7.00; N, 15.38; S, 11.73.
Found: C, 65.68; H, 7.10i N~ 15.05; S, 11.93.
Example 135 3-(o-Chlorophenyl)-N,N,a-tri~ethylpyrazole-1-thioacetamide Following the procedure of Example 127, but substitut-ing 3-(o-chlorophenyl)-N,N~a-trimethylpyra20le-1-acetamide for N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained 3-(o-chlorophenyl)~N,N,a-trimethylpyra-zole-1-thioacetamide having a melting point of 68-69.5 C.
Analysis-- . : . .
.
~29 l.l)53231 Calc'd. for C1~Hl~ClN3~o C, 57.23; H, 5.49, Cl, 12.07; N, 14.30; S,10.9 Found: C, 57.27; ~1, 5.53; Cl, 12~00; N, 1~.50; S,ll 0 ~ N,~ Trimethyl-~-phenylpyrazole-1- t hioacet-amide Following the procedure of Example 127, but substitut-ing N,a,4-trimethyl-~-phenylpyrazole-1-acetamide for N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there was obtained N,a,4-trimethyl-3-phenylpyrazole-1-thioacet-amide having a melting point of 97-99 C.
Analysis.
Calc'd. for C1 4 H17N3S:
C, 64.8~; H, 6.61; N, 16.20; S, 12.36.
Found: C, 64.72; H, 6.74; N, 16.23; S, 12.64.
15Example 137 N,~,a,4-Tetramethyl-3-phenylpyrazole-1-thiO-acetamide Following the procedure of Example 127, but substitut-ing N,~,~,4-tetramethyl-3-phenylpyrazole-1-acetamide For N,N,~,a,4-pentamethyl-3-phenylpyrazole-1-acetamide there ;
was obtained N~a,a,4-tetramethyl-3-phenylpyrazole-1-thio-acetamide having a melting point of 75-77 C.
Analysis:
Calc'd. for C15HlgN3Ss C, 65.30; H, 7.00; N, 15.~7; S, 11. 73.
25Found: C, 65.55; H) 7.02; N, 15.11; S, 11.64.
N,N,4-Trimethyl-3-phenylpyrazole-1-propionamide Following the procedure of Example 1, but substituting 3-chloro-N,N-dimethylpropionamide for 2-chloro-N,N-dimethyl-propionamide there was obtained N,N,4-trimethyl-3-phenyl-30pyrazole-1-propionamide having a melting point of 60-63 C.
~229 1~53Z31 Calc'd. for Cl5HIgN30:
C, 70. 00; H, 7.44; N~ 16.330 Found: C, 70.01; H, 7.45; N, 16.52.
5 ~ 3-(o-Ethoxyphenyl)-N,N,a,4-tetraniethylpyrazole-1 -ace tam i de Fol lowing .he procedure of Example 1, but substituting 3- (o-ethoxyphenyl )pyrazole for 4-methyl -~S-phenylpyrazole there was obtained 3- (o-ethoxyphenyl )-N,N,~,4-tetramethyl-1 0pyrazole-1-acetamide having a melting point of 96-~7.5 C.
Analysis:
Cal c' d. for C1 7H23N30z:
C, 67.75; H, 7.69; N, 1~.94.
Found: C, 67.74; H, 7.66; N, 13.71.
1 5 ~e~ 4 - I odo- N , N , a t r i me t hy 1 - 3- phe n y 1 p y razo 1 e -1-acetami de Following the procedure of Example 1, but substituting 4-iodo-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained 4- iodo-N,N,~-trimethyl -3-phenylpyrazole-201-acetamide having a melting point of 108-111 CO
i~ Analysis:
Calcld. for Cl4H1~IN30:
C, 45.54; H, 4.37; N, 11.38; I, 34.37.
Found: C, 45.93; H, 4.92; N, 11. 02; 1, 34. 51.
25 ~ a Ethyl-N,N,5-trimethyl-3-phenylpyrazole-1 -ace tam i de Following the procedure of Example 1, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole and 2-b~omo-N,N-dimethylbutyramide for 2-chloro-N,N-dimethyl-30 propionamide there was obtained a-ethyl-N3N~5-trimeth ' :, 3~29 1C~53Z3~
3-phenylpyrazole-l-acetamide having a mel~ing point of .~ O
117-llg. 5 c.
~,~
Calcld. for C1~H2~N30:
C, 70.82; H, 7.80; N, 15.49. - -Found: C, 70.61; H, 7.57; N, 15.64.
Examp!e 142 Following the procedure of Example ~, but substituting 3-(o-fluorophenyl)pyrazole, 3-(o-fluorophenyl)-4-methylpyra-zole, 3-(o-bromophenyl)pyrazole, 3-(o-bromophenyl)-4-methyl-`~ pyr~zole, 3-(o-trifluoromethylphenyl)pyrazoleJ 3-(o-tri-fluoromethylphenyl)-4-methylpyrazole, and 3-(o-ethylphenyl)-pyrazo1e for 4-methyl-3-phenylpyrazole there were obtained N,N,a-trimethyl-3-(o-fluorophenyl)pyrazole-1-acetamide, N~N~a~4-tetramethyl-3-(o-fluorophenyl)pyrazole-l-acetamide~
,. . .
N,N,a-trimethyl-3-(o-bromophenyl)pyrazole-1-acetamide, N~N~a~4-tetramethyl-3-(o-bromophenyl)pyrazole-l-acetamide~
N~NJ~-tri~ethyl-3-(o-trifluoromethylphenyl)pyrazole-l-acet-amide, N,N,~4-tetramethyl-3-(o-trifluoromethylphenyl)pyra-zole-1-acetamide, and 3-(o-ethylphenyl)-N,N,a-trimethylpyra zole-1-acetamide.
Example 143 NJNJal4-Tetramethyl-5-nitro-3-phenylpyrazole 1-acetamide Following the procedure of Example 1, but substituting 5-nitro-3-phenylpyrazole for 4-methyl-3-phenylpyrazole there was obtained N,N,a,4-tetramethyl-5-nitro-3-phenylpyr azole-1-acetamide having a melting point of 141-143 C.
Calc'd. ~or C15Hl8N403:
C, 59.59; H, 6.oo; N, 18.53.
:
~(~S 3Z ~
Found: C, 59.62i H, 6.02; N, 18.53.
Example 144 3-(o-Chlorophenyl)-N,N,~,~,4~pentamethyl-pyrazole-1-acetamide Following the procedure of Example 49, but substituting 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3 phenyl-pyrazole and dimethylamine for aqueous methylamine there was obtained ~-(o-chlorophenyl)-N,N,a,a,4-pentamethylpyra-zole-1-acetamide having a melting point of 175-176 C.
Analysis:
Calc'd. for Cl6HzoClN30:
C, 62.84; H, 6.59; Çl, 11.60; N, 13.74.
Found: C, 62.90; H, 6.52; Cl, 11.66; N, 13.54.
~Example 145 N,N,a,a,5-Pentamethyl-3-phenylpyrazole-1-acet-amide Following the procedure of Example 49, but substituting 3-methyl-5-phenylpyrazole for 4-methyl-3-phenylpyrazole and O
aqueous dimethylamine for aqueous methylamine there was obtained N~N~a~a~5-pentamethyl-3-ph~enylpyrazole-l-acetamide having a melting point of 123-125 C.
.~:
Analysis;
Calc~d. for C18H21N30:
C, 70.82; H, 7.80; N, 15.49.
Found: C, 71.01; H, 7.76; N, 15.74.
4-Chloro-a-ethyl-N,N-dimethyl-3-(o-tolyl)pyra-.
zole~1-acqt~mide F~llowing the procedure of Example 108, but substituting a ethyl N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide for N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-butyl hypochlorite for bromine there was obtained 4-chloro-a-ethyl-N,N-dimethyl-~(o-tolyl)pyrazole-1-acetamide having ::
-8~-32~9 lOS;~'~3~
a melting point of 49.5-52 C.
Analysis:
Calc~d. for Cl~H20ClN30:
C, 62.84; H, 6.59; Cl, 11.59; N, 13.74.
Found: C, 62.90; H, 6.~4; Cl, 11.82; N, 13.88.
Example 147 5-Chloro-N~N.a,a,4-pentamethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 1O3J but substitut-ing N,N,a,~,4-pentamethyl-3-phenylpyrazole-1 acetamide ~or N,N,a,5-tetramethyl-3-phenylpyrazole-1-acetamide and tert-; butyl hypochlorite for bromine there was obtained 5-chloro-N,N, a, a, 4-pentamethyl-3-phenylpyrazole-1-acetamide having a melting point of 96-99 C.
Analysis:
Calc'd. for C1ffH20ClN30:
C, 62.84; H, 6.59; Cl, 11.59; N, 13.74.
Found: CJ 63.oo; HJ 6.64; C~ .74; NJ 1~.98.
~ Example 148 4-Fluoro-NJN,~,a-te~ramethyl-3^phenylpyrazole-; 1-acetamide '~ 20 Following the procedure of Example 10BJ but substitut-ing N,N,a,a-tetramethyl-3-phenylpyrazole-1~cetamide for ~ N~N~a~5-tetra~ethyl-3-phenylpyrazole-l-acetamide~ trifluoro-,~ methyl hypofluorite for bromine, and carbon tetrachloride for acetic acid as the reaction solvent there was obtained 4-fluoro-NJN~a~-tetramethyl-3-phenylpyrazole-l acetamide.
-Bromo-N,N-dimethyl-3-phenylpyrazole-1-pro-pionamtde Followlng the procedure of Example 121, but substitut-7ny 2,3~dibromo-N,N-dimethylpropionamide for 2-bromo-N,N,2-trimethylpropionamide there was obtained ~-bromo-N,N-, ~" : . . .
, ,~2?9 1053;~ 3~
dimethyl-3-phenylpyrazole-1-acetamide having a melting point of 93-94 C.
Analys ~-Calc'd. for C14H16BrN30:
5C, 52.18; H~ 5. 01; Br, 24.80; N, 13.04. -Found: C, 52.34; H, 5.10; Br, 24.59; N, 1~.20.
Example 150 Hydrochloride salt of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide Hydrogen chloride was passed into a stirred solution 10 of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide (2.53 9., 0.01 mole) in carbon tetrachloride (50 ml.). The precipi-tated salt was filtered off and was recrystallized from ethyl acetate; m.p. 170-172 C.
Example 151 p-Toluenesulfonate salt of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetarnide A solution of p-toluenesulfonic acid (1.9 g., 0.03 mole) in chloroform was added to a solution of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide (2.5 9., 0.01 mole) in chloro-;; form. Evaporation of the chloroform gave the p-toluenesul-20 fonate salt of N,N,a,4-tetramethyl-3-phenylpyrazole having .
a melting point of 131-1~4 C.
:!
A dispersible powder concentrate having the following percentage composition:
~; 25 N,N,~,4-tetramethyl-3-phenyl-pyrazole-1-acetamide 45.8,9 Polymerized sodium salt of sub-.
;~ stituted benzoid long-chain sulfonic acid (Daxad 27) 9.2 30 Kaolinite 45.
.. .
.`-' ' 322g ~053231 was prepared by mixing 250 g. of N,N,~,4-te~ramethyl 3-phenylpyrazole-1 acetamide, ~0 g. of a polymerized sodium salt of substituted benozid long-chain sulfonic acid (Daxad 27), and 245 9. of kaoli ni te. The m;xture was milled to a particle size averaging 5 to 30 microns. It was suspended in 10 gals. of water, giving an aqueous spray containing about 6500 parts per million of active ingredient.
Example 15~
A fine granular formulation having the following per-centage composition:
N,N,a,4-tetramethyl-~-phenyl-pyrazole-1-acetamide 3.7 Vermiculite (30~ 0 mesh) 96.3~
was prepared by spraying a solution of 220 9. of ~,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide in 1000 ml. of chloroform onto 5780 g. of vermiculite (~0 to 60 mesh) while the vermiculite was being tumbled and stirred so as to assure even distribution. The chloroform was then evaporated, leaving the active compound adsorbed on the , 20 vermiculite, and the vermiculite was pulverized.
~e~ ~
An emulsifiable concentrate having the following per-centage composition:
NJ NJ ~ 4-tetramethyl-~-phenyl-pyrazole-1-acetamide 15.0%
Technlcal alkyl naphthalene .... . .
boiling at 238 to 293 C.
(VelsIcol AR50) 19.7%
Xylene 17.4 30 Acetone 17.4 . .
~ 3~3~ ~
Etilylene dichloride 25~4%
Blend of alkyl aryl sullfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.1%
was prepared by mixing 15.0 lbs. of N,N,~,4-tetramethyl-3-phenylpyrazole-1-acetamide~ 19.7 lbs. cf Velsicol AR50, 17.4 lbs. of xylene, 17.4 lbs. of acetone, 25.4 lbs~ of ethylene dichlorideJ and 5.1 lbs. of Triton X-151.
6.67 Lbs. of the concentra~e mixed with 10 gals. of water gave a spray emulsion containing about 11JOOO ppm of active ingredient.
Example 155 An emulsifiable concentrate having the following per-centage composition.
N,N,~,4-tetramethyl-3-phenyl-pyrazole-1-acetamide 40.0~ 1 Technical alkyl naphthalene boiling at 238 to 293 C.
- (Velsicol AR50) 1307~
`~ 20 Xylene 12.3% ~-: Acetone 11. 3%
Ethylene dichloride 17.7 ; Blend of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151) 5.0%
- was prepared by mixing 40.0 lbs. of N,N,~,4-tetramethyl-3-phenylpyrazole 1-acetamide, 13~7 lbs. of Velsicol AR50J
12.3 lbs. of xylene, 11.3 lbs. of acetone, 17.7 lbs. of ethylene dichloride, and 5.0 lbs. of Triton X-151.
1.57 Lbs. of the concentrate mixed with 10 gals. of , ., ,~
~- 8~3 ~229 lOS3Z3~
water gave a spray emulsion containing about 8,ooo ppm of active ingredient.
Exampl_e 156 A dispersible powder concentrate having the following percentage compositior-:
J N,N,a,4-tetramethyl-3-phenyl `' pyrazole-1-acetamide 50 Kaolinite clay (finely divided) 46%
Sodium salt of condensed mono-naphthalene sulfonic acid (Lomar D) 4 .;. . .
~i was prepared by mixing 50 9. of N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide, 46 9. of the kaolinite clay, and 4 g. of Lomar D. The mixture was milled to an average particle size of 5 to 30 microns.
1 Example 157 '~s, ', A granular formulation having the following percentage composition:
; N,N,~,4-tetrametHyl-3-phenyl-~v~ ~ 20 pyrazole-l-acetamide 1~
` ~ - Pyrophyllite (30/60 mesh) 99%
~j~ was prepared by dissolving 1.0 lb. of the N,N,a,4-tetra-d~ methyl-~-phenylpyrazole-1-acetamide, in 10.0 1. of ethylene d1chloride and spraying the solution on 9g.0 lbs. of pyro-phylllte. The granules were dried and then packaged for a use.
Example 1~8 - An emulsifiable concentrat~ havtng the following per-centage composit1~n:
j N~N,~,4-tetramethyl-3-phenyl--~ J
32~9 lOS~Z31 pyrazole-l-acetamide 25,~
Tridecylsulfonic acid 25%
Xylene was prepared by mixing 250 g. of N,N,a~4-te~ramethyl~
3-phenylpyrazole-1-acetamide, 250 9. of tridecylsulfonic acid, and 500 g. of xylene. The emulsifiable concentrate containing the tridecylsulfonate salt of N,N,a,4-tetra-methyl-3-phenylpyrazole-1-acetamide was mixed with 10 gals.
of water to give a spray emulsion containing about 6500 ppm of active ingredient.
Example 159 Following the procedure of the preceding Examples 152 through 157, inclusive, compositions are similarly prepared substituting each of the compounds prepared in Examples 2 through 151, inclusive, for the N,N,a,4-tetramethyl-3-phenyl-pyrazole-1-acetamideO
'~
.
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. ~ 9 lOS~Z~l SUPPLEMENTARY DISCLOSURE
Certain physical and chemical data, inherent in compounds already provided by examples in the principal disclosure, are set out as follows:
N,N,~-trimethyl-3-(o-nitrophenyl)pyrazole-1-acetamide:
NMR (CDC13 - 1% TMS) 1.63, 2.98, 5.34, 6.43, 7.2-7.8 ~.
a-(3-Bromopropyl)-N~N~4-trimetllyl-3-phenylpyrazole-l-acetamide: NMR (CDC13 - 1~ TMS) 1.80-2.40, 2.20, 3.05, 3.43.
5.37, 7.2-7.8 ~.
~ -(4-Bromobutyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide: NMR (CDC13 - 1% TMS) 2.20, 2.50, 3.03, 3.52, 5.58,
7.20-7.50, and 7.50-7.80 ~.
-N,N-Dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)-cyclopentane-carboxamide: m.p. 99-101C. Anal. calcd. for C18H23N3O:
C, 72.69; H, 7.80; N, 14.13.
Found: C, 72.67; H, 7.65; N, 14.21.
4-Chloro-3-(o-chlorophenyl)-N,N~ ,~- tetramethylpyrazole-l-!~ acetamide: m.p. 161-163C. Anal. calcd. for C15H17C12N3O:
C, 55.22; H, 5.25; N, 12.88; C1, 21.74. -~
.: :
; Found: C, 54.95; H, 5.07; N, 12.76; Cl, 21.23.
The following additional Examples are illustrative of the process and products of the present invention:
. j .
~j 3-(o-Bromophenyl)-N,N-diethyl~ ,4-dimethyl-pyrazole-1-..~
~ 30 acetamide ;- Using the procedure of Example 1, but substituting 2-chloro-~; N,N-diethylpropionamide for 2-chloro-N,N-dimethylpropionamide and . . .
~ 3-(o-bromophenyl)-4-methylpyrazole for 4-methyl-3-phenylpyrazole, '.
~ ~ sl: - 91 -- .
..
. . .
1(153~3~
there is obtained 3-(o-bromophenyl)-N,N-diethyl-a,4-dimethyl-pyrazole-1-acetamide, b.p. 187-190C./0.15 mm.
nalysis: Calcd. for C17H22BrN3O
C, 56~05; H, 6.09; Br, 21.94; N, 11.53.
Found: C, 56.42; H, 6.45; Br, 21.85; N, 11.57.
EXAMPLE 161 4-Ethyl-N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 95, but substituting 4-ethyl-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,~,a 4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide, there was obtained 4-ethyl-N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide, m.p. 108.5-111C.
. . .
Analysis: Calcd. for C17H23N3O:
C, 71.54; H, 8.12; N, 14.73 Found: C, 71.31; H, 7.96; N, 14.69.
EXAMPLE 162 3-(o-Chlorophenyl)-4-ethyl-N,N,a,~-tetramethyl-.
pyrazole-l-acetamide ; Following the procedure of Example 95, but substituting 3-(o-chlorophenyl~-4-ethyl-N,N,a-trimethylpyrazole-l-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl .-, .
iodide for ethyl iodide, there was obtained 3-(o-chlorophenyl)-4-ethyl-N,N,a,a-tetramethylpyrazole-1-acetamide. m.p. 101.5-104.5C.
Analysis: Calcd. for C17H22ClN3O:
....
C, 63.84; H, 6.93; Cl, 11.09; N, 13.1~4.
Found: C, 63.83; H, 7.03; Cl; 10.92; N, 13.01.
EXAMPLE 163 4-Bromo-N,N,a,~-tetramethyl-3-phenylpyrazole-1-acetamide Following the proceduré of Example 95, but substituting 4-bromo-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for -~ ethyl iodide, there was obtained 4-bromo-N,N,a,~-tetramethyl-3-phenylpyrazole-1-acetamide, m.p. 122.5-124C.
' - 92 -"' ~ sl:
': , ' . :-` 1053231 Analysis: Calcd. for C15H18BrN3O:
C, 53.58; H, 5.39; Br, 23.77; N, 12.50 Found: C, 53.79; H, 5.45; Br, 23.54; N, 12.51.
EXAMPLE 164 3-(o-Fluorophenyl)-N,N,~,~,~pentamethylpyrazole-l-acetamidQ
Following the procedure of Example 68, but substituting 3-(o-fluorophenyl)-~,~,4-trimethyhpyrazole-1-acetic acid for ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for aqueous ammonia, there was obtained 3-(o-fluorophenyl)-N,N,~-4-pentamethylpyrazole-1-acetamide, m.p. 112.5-114C.
Analysis: Calcd for Cl6H20FN3O-C, 66.41; H, 6.97; F, 6.57; N, 14.52.
Found: C, 66.52; ~I, 6.92; F, 6.58; N, 14.64.
EXAMPLE 165 3-(o-Chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-1-` thioacetamide Following the procedure of Example 127, but substituting 3-(o-Chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-1-acetamide for N,N,~,~,4-pentamethyl-3-phenylpyrazole-l~acetamide, there was obtained 3-(o-chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-l-thioacetamide, m.p. 146.5-148C.
Analysis: Calcd. for C16H20ClN2S
C, 59.70; H, 6.26; Cl, 11.01; N, 13.05; S, 9.99 ` Found: C, 59.68; H, 6.16; Cl, 11.31; N, 13.03; S, 10.11.
EXAMPLE 166 3-(o-Chlorophenyl)-N,N-diethyl-a,4-dimethylpyraæole-l-acetamide ,.~ ~ , . .
Using the procedure of Example 1, but substituting 2-chloro-N,N-diethylpropion~de for 2-chloro-N,N-dimethyl-propionamide and 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-.:
~ pyrazole there is obtained 3-(o-chlorophenyl)-N,N-diethyl-~,4-r~ 30 dimethylpyrazole-l-acetamide, b.p.l78-182C./0.4 mm.
. . .
s 1:
~ .
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1~)53Z3~
Analysis: Calcd- for C17H22ClN3 C, 64.04; H, 6~64; Cl, 11.12; N, 13.18.
Found: C, 64.02; H, 6.76; C1, 1].10; Nl 12.91.
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-N,N-Dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)-cyclopentane-carboxamide: m.p. 99-101C. Anal. calcd. for C18H23N3O:
C, 72.69; H, 7.80; N, 14.13.
Found: C, 72.67; H, 7.65; N, 14.21.
4-Chloro-3-(o-chlorophenyl)-N,N~ ,~- tetramethylpyrazole-l-!~ acetamide: m.p. 161-163C. Anal. calcd. for C15H17C12N3O:
C, 55.22; H, 5.25; N, 12.88; C1, 21.74. -~
.: :
; Found: C, 54.95; H, 5.07; N, 12.76; Cl, 21.23.
The following additional Examples are illustrative of the process and products of the present invention:
. j .
~j 3-(o-Bromophenyl)-N,N-diethyl~ ,4-dimethyl-pyrazole-1-..~
~ 30 acetamide ;- Using the procedure of Example 1, but substituting 2-chloro-~; N,N-diethylpropionamide for 2-chloro-N,N-dimethylpropionamide and . . .
~ 3-(o-bromophenyl)-4-methylpyrazole for 4-methyl-3-phenylpyrazole, '.
~ ~ sl: - 91 -- .
..
. . .
1(153~3~
there is obtained 3-(o-bromophenyl)-N,N-diethyl-a,4-dimethyl-pyrazole-1-acetamide, b.p. 187-190C./0.15 mm.
nalysis: Calcd. for C17H22BrN3O
C, 56~05; H, 6.09; Br, 21.94; N, 11.53.
Found: C, 56.42; H, 6.45; Br, 21.85; N, 11.57.
EXAMPLE 161 4-Ethyl-N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide Following the procedure of Example 95, but substituting 4-ethyl-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,~,a 4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for ethyl iodide, there was obtained 4-ethyl-N,N,a,a-tetramethyl-3-phenylpyrazole-1-acetamide, m.p. 108.5-111C.
. . .
Analysis: Calcd. for C17H23N3O:
C, 71.54; H, 8.12; N, 14.73 Found: C, 71.31; H, 7.96; N, 14.69.
EXAMPLE 162 3-(o-Chlorophenyl)-4-ethyl-N,N,a,~-tetramethyl-.
pyrazole-l-acetamide ; Following the procedure of Example 95, but substituting 3-(o-chlorophenyl~-4-ethyl-N,N,a-trimethylpyrazole-l-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl .-, .
iodide for ethyl iodide, there was obtained 3-(o-chlorophenyl)-4-ethyl-N,N,a,a-tetramethylpyrazole-1-acetamide. m.p. 101.5-104.5C.
Analysis: Calcd. for C17H22ClN3O:
....
C, 63.84; H, 6.93; Cl, 11.09; N, 13.1~4.
Found: C, 63.83; H, 7.03; Cl; 10.92; N, 13.01.
EXAMPLE 163 4-Bromo-N,N,a,~-tetramethyl-3-phenylpyrazole-1-acetamide Following the proceduré of Example 95, but substituting 4-bromo-N,N,a-trimethyl-3-phenylpyrazole-1-acetamide for N,N,a,4-tetramethyl-3-phenylpyrazole-1-acetamide and methyl iodide for -~ ethyl iodide, there was obtained 4-bromo-N,N,a,~-tetramethyl-3-phenylpyrazole-1-acetamide, m.p. 122.5-124C.
' - 92 -"' ~ sl:
': , ' . :-` 1053231 Analysis: Calcd. for C15H18BrN3O:
C, 53.58; H, 5.39; Br, 23.77; N, 12.50 Found: C, 53.79; H, 5.45; Br, 23.54; N, 12.51.
EXAMPLE 164 3-(o-Fluorophenyl)-N,N,~,~,~pentamethylpyrazole-l-acetamidQ
Following the procedure of Example 68, but substituting 3-(o-fluorophenyl)-~,~,4-trimethyhpyrazole-1-acetic acid for ~,4-dimethyl-3-phenylpyrazole-1-acetic acid, and dimethylamine for aqueous ammonia, there was obtained 3-(o-fluorophenyl)-N,N,~-4-pentamethylpyrazole-1-acetamide, m.p. 112.5-114C.
Analysis: Calcd for Cl6H20FN3O-C, 66.41; H, 6.97; F, 6.57; N, 14.52.
Found: C, 66.52; ~I, 6.92; F, 6.58; N, 14.64.
EXAMPLE 165 3-(o-Chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-1-` thioacetamide Following the procedure of Example 127, but substituting 3-(o-Chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-1-acetamide for N,N,~,~,4-pentamethyl-3-phenylpyrazole-l~acetamide, there was obtained 3-(o-chlorophenyl)-N,N,~,~,4-pentamethylpyrazole-l-thioacetamide, m.p. 146.5-148C.
Analysis: Calcd. for C16H20ClN2S
C, 59.70; H, 6.26; Cl, 11.01; N, 13.05; S, 9.99 ` Found: C, 59.68; H, 6.16; Cl, 11.31; N, 13.03; S, 10.11.
EXAMPLE 166 3-(o-Chlorophenyl)-N,N-diethyl-a,4-dimethylpyraæole-l-acetamide ,.~ ~ , . .
Using the procedure of Example 1, but substituting 2-chloro-N,N-diethylpropion~de for 2-chloro-N,N-dimethyl-propionamide and 3-(o-chlorophenyl)-4-methylpyrazole for 4-methyl-3-phenyl-.:
~ pyrazole there is obtained 3-(o-chlorophenyl)-N,N-diethyl-~,4-r~ 30 dimethylpyrazole-l-acetamide, b.p.l78-182C./0.4 mm.
. . .
s 1:
~ .
~: , -- '; : ' ..
1~)53Z3~
Analysis: Calcd- for C17H22ClN3 C, 64.04; H, 6~64; Cl, 11.12; N, 13.18.
Found: C, 64.02; H, 6.76; C1, 1].10; Nl 12.91.
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Claims
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
A compound of the formula:
Formula 1 wherein R1 and R2 are the same or different and are hydrogen, halogen, alkyl of from 1 to 6 carbon atoms, inclusive, halo-alkyl of from 1 to 6 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrolidine or piperidine;
A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halogen, cyano, nitro or trifluoromethyl; Z is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl, or alkoxy of from 1 to 3 carbon atoms, inclusive, n is 0, 1 or 2, and W is selected from oxygen and sulfur; or a herbicidally active acid addition salt thereof.
A compound according to claim 1 which is N,N,.alpha., 4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 4-tetramethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 5-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 3-tetramethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-N, N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-N, N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4,5-dibromo-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 3,4-dibromo-N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3,4-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-4,5-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-ethyl-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4,5,6,7-tetra-hydro-N,N,.alpha.-trtmethyl-3-phenyl-1H-indazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3,5-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,3,5-pentamethyl-4-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4,5-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-5-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 5-(o-chloro-phenyl )-N,N-.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(p-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 5-(p-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(p-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-methoxy-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(m-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(m-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2,5-di-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trtmethyl-3-(p-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(m-nitrophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-diethyl-.alpha.-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-diethyl-.alpha.-methyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is a ethyl-N,N,4-trimethyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-(5-chloro-2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-tri-methyl-.alpha.-propyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is a ethyl 3-(2-furyl)-N,N,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,4-trimethyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-5-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(o-nitrophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-.alpha.-ethyl-N,N-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-.alpha.-ethyl-N,N,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(3-bromo-propyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(4-bromo-butyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl N,N,4-trimethy1-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(2-chloro-ethyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-cyclohexyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-cyclohexyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-butyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenyl-N-isopropylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N-isopropylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenyl-N-propylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N-propylpyrazole-1-propionamide.
A compound according to claim 1 which is N-butyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-tert-butyl .alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N-benzyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-N-octyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetra-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-diethyl-3-(2-furyl)-.alpha.,.alpha.,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,.alpha.,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,.alpha.-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetra-methyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N-ethy1-.alpha.,4-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-butyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-N,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is 1-[2-(4-methyl-3-phenylpyrazol-1-yl)propionyl]pyrrolidine.
A compound according to claim 1 which is 4-[2-(4-methyl-3-phenylpyrazol-1-yl)propionyl]morpholine.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,4-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-tri-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-4-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-methyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-ethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-ethyl-4-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-isopropyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-triethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-trimethyl-.alpha.,3-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-cyano-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-pheny1-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.-diethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-.alpha.,3-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclopropanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclobutanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclopentanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(3-phenylpyrazol-1-yl)cyclopropanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(3-phenylpyrazol-1-yl)cyclobutanecarboxamide.
A compound according to claim 1 which is 4-bromo-N,N,.alpha.,5-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-.alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(p-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-.alpha.-ethyl-N,N-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-N,N,.alpha.,.alpha.-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.,.alpha.-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.beta.,4-tetra-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .beta.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.beta.-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.-bromo-N,N,4-trimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is .alpha.-(n-butyl)-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N-di-ethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 3-(o-ethoxy-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-iodo-N,N,-.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,5-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,5-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 5-chloro-N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-5-nitro-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the hydro-chloride salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the p-toluenesulfonate salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the tri-decylsulfonate salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamtde.
A method for controlling weeds or undesirable vegeta-tion which comprises applying to the locus thereof a herbi-cidally effective amount of a compound of the formula:
Formula I
wherein R1 and R2 are the same or different and are hydro-gen, halogen, alkyl of from 1 to 6 carbon atoms, inclusive, haloalkyl of from 1 to 5 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrol-idine or piperidine, A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halogen, cyano, nitro or trifluoromethyl; Z is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl or alkoxy of from 1 to 3 carbon atoms, inclusive, n is 0, 1, or 2, and W is oxygen or sulfur; or a herbicidally active acid addition salt thereof.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
A compound according to claim 1, which is:
3-(0-Bromophenyl)-N,N-diethyl-.alpha.,4-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is:
4-ethyl-N,N,.alpha.,.alpha.,-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-4-ethyl-N,N,.alpha.,.alpha.,-tetramethylpyrazole-1-acetamide.
A compound according to claim 1, which is:
4-bromo-N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-fluorophenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-thioacetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-N,N-diethyl-.alpha.,4-dimethylpyrazole-1-acetamide.
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
A compound of the formula:
Formula 1 wherein R1 and R2 are the same or different and are hydrogen, halogen, alkyl of from 1 to 6 carbon atoms, inclusive, halo-alkyl of from 1 to 6 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrolidine or piperidine;
A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halogen, cyano, nitro or trifluoromethyl; Z is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl, or alkoxy of from 1 to 3 carbon atoms, inclusive, n is 0, 1 or 2, and W is selected from oxygen and sulfur; or a herbicidally active acid addition salt thereof.
A compound according to claim 1 which is N,N,.alpha., 4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 4-tetramethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 5-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha., 3-tetramethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-N, N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-N, N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4,5-dibromo-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 3,4-dibromo-N,N,.alpha.-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3,4-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-4,5-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-ethyl-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4,5,6,7-tetra-hydro-N,N,.alpha.-trtmethyl-3-phenyl-1H-indazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3,5-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,3,5-pentamethyl-4-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4,5-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-5-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 5-(o-chloro-phenyl )-N,N-.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(p-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 5-(p-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(p-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-methoxy-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(m-chloro-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(m-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2,5-di-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trtmethyl-3-(p-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(m-nitrophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-diethyl-.alpha.-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-diethyl-.alpha.-methyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is a ethyl-N,N,4-trimethyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-5-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-(5-chloro-2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-tri-methyl-.alpha.-propyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is a ethyl 3-(2-furyl)-N,N,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,4-trimethyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-5-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-(o-nitrophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-.alpha.-ethyl-N,N-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-.alpha.-ethyl-N,N,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(3-bromo-propyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(4-bromo-butyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl N,N,4-trimethy1-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-(2-chloro-ethyl)-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-cyclohexyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-cyclohexyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-butyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenyl-N-isopropylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N-isopropylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenyl-N-propylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N-propylpyrazole-1-propionamide.
A compound according to claim 1 which is N-butyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-tert-butyl .alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N-benzyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetra-methyl-N-octyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetra-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-diethyl-3-(2-furyl)-.alpha.,.alpha.,4-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,.alpha.,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,.alpha.-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetra-methyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N-ethy1-.alpha.,4-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-butyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N-ethyl-N,.alpha.,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is N,.alpha.,4-tri-methyl-3-phenylpyrazole-1-acetanilide.
A compound according to claim 1 which is 1-[2-(4-methyl-3-phenylpyrazol-1-yl)propionyl]pyrrolidine.
A compound according to claim 1 which is 4-[2-(4-methyl-3-phenylpyrazol-1-yl)propionyl]morpholine.
A compound according to claim 1 which is .alpha.,4-dimethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,4-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-tri-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-4-methyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-diethyl-.alpha.-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-methyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-ethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.-tri-ethyl-4-methyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-isopropyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-triethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-3-phenyl-N,N-dipropylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,4-trimethyl-.alpha.,3-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-cyano-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-3-pheny1-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.,.alpha.-diethyl-N,N,4-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-5-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetra-methyl-.alpha.,3-diphenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-(2-thienyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 3-(2-furyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclopropanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclobutanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(4-methyl-3-phenylpyrazol-1-yl)cyclopentanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(3-phenylpyrazol-1-yl)cyclopropanecarboxamide.
A compound according to claim 1 which is N,N-dimethyl-1-(3-phenylpyrazol-1-yl)cyclobutanecarboxamide.
A compound according to claim 1 which is 4-bromo-N,N,.alpha.,5-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-bromo-.alpha.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(p-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-N,N,.alpha.-trimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(o-methoxyphenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-(2,6-dichlorophenyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-.alpha.-ethyl-N,N-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-3-(o-chlorophenyl)-N,N,.alpha.,.alpha.-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.,.alpha.-tetramethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is N,N-dimethyl-3-phenyl-.alpha.-propylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.beta.,4-tetra-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .beta.-ethyl-N,N-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N-dimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.beta.-tri-methyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is .alpha.-bromo-N,N,4-trimethyl-3-phenylpyrazole-1-propionamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is .alpha.-(n-butyl)-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 4-chloro-N,N,.alpha.-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,4-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N-di-ethyl-.alpha.,4-dimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.-trimethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is N,.alpha.,.alpha.,4-tetramethyl-3-phenylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.-trimethylpyrazole-1-thioacetamide.
A compound according to claim 1 which is 3-(o-ethoxy-phenyl)-N,N,.alpha.,4-tetramethylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-iodo-N,N,-.alpha.-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is .alpha.-ethyl-N,N,5-trimethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 3-(o-chloro-phenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,.alpha.,5-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is 4-chloro-.alpha.-ethyl-N,N-dimethyl-3-(o-tolyl)pyrazole-1-acetamide.
A compound according to claim 1 which is 5-chloro-N,N,.alpha.,.alpha.,4-pentamethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is N,N,.alpha.,4-tetramethyl-5-nitro-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the hydro-chloride salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the p-toluenesulfonate salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1 which is the tri-decylsulfonate salt of N,N,.alpha.,4-tetramethyl-3-phenylpyrazole-1-acetamtde.
A method for controlling weeds or undesirable vegeta-tion which comprises applying to the locus thereof a herbi-cidally effective amount of a compound of the formula:
Formula I
wherein R1 and R2 are the same or different and are hydro-gen, halogen, alkyl of from 1 to 6 carbon atoms, inclusive, haloalkyl of from 1 to 5 carbon atoms, phenyl or R1 and R2 can be joined to form a cycloalkyl ring of from 3 to 6 carbon atoms; R3 is hydrogen, alkyl of from 1 to 8 carbon atoms, inclusive, phenyl or benzyl; R4 is hydrogen, or alkyl of from 1 to 6 carbon atoms, inclusive, and R3 and R4 can be joined together to form a heterocyclic ring selected from the group consisting of morpholine, pyrrol-idine or piperidine, A and B are the same or different and are hydrogen, alkyl of from 1 to 6 carbon atoms, inclusive, phenyl, halogen, cyano, nitro or trifluoromethyl; Z is selected from the group consisting of or wherein X is halogen, nitro, alkyl, haloalkyl or alkoxy of from 1 to 3 carbon atoms, inclusive, n is 0, 1, or 2, and W is oxygen or sulfur; or a herbicidally active acid addition salt thereof.
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
A compound according to claim 1, which is:
3-(0-Bromophenyl)-N,N-diethyl-.alpha.,4-dimethylpyrazole-1-acetamide.
A compound according to claim 1 which is:
4-ethyl-N,N,.alpha.,.alpha.,-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-4-ethyl-N,N,.alpha.,.alpha.,-tetramethylpyrazole-1-acetamide.
A compound according to claim 1, which is:
4-bromo-N,N,.alpha.,.alpha.-tetramethyl-3-phenylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-fluorophenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-acetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-N,N,.alpha.,.alpha.,4-pentamethylpyrazole-1-thioacetamide.
A compound according to claim 1, which is:
3-(0-chlorophenyl)-N,N-diethyl-.alpha.,4-dimethylpyrazole-1-acetamide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52423174A | 1974-11-15 | 1974-11-15 | |
| US05/686,548 US4072498A (en) | 1974-11-15 | 1976-05-14 | Pyrazole amides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1053231A true CA1053231A (en) | 1979-04-24 |
Family
ID=27061423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA240,263A Expired CA1053231A (en) | 1974-11-15 | 1975-11-24 | Pyrazole amides and thioamides |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1053231A (en) |
| PH (1) | PH14320A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281571A (en) * | 1990-10-18 | 1994-01-25 | Monsanto Company | Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles |
| CN103772283A (en) * | 2014-01-17 | 2014-05-07 | 怀化学院 | Pyrazole compound containing aromatic ring and dihalide substituent as well as preparation method and use thereof |
| WO2019081477A1 (en) | 2017-10-26 | 2019-05-02 | Bayer Cropscience Aktiengesellschaft | Substituted pyrazoles, salts thereof and use thereof as herbicidal agents |
| WO2019081485A1 (en) | 2017-10-26 | 2019-05-02 | Bayer Cropscience Aktiengesellschaft | Substituted pyrazoles, salts thereof and use thereof as herbicidal agents |
| EP3858811A4 (en) * | 2018-09-28 | 2022-05-11 | Shenzhen EDK Pharmaceutical Technology Co., Ltd. | N-aromatic amides compound and preparation method and use thereof |
-
1975
- 1975-11-24 CA CA240,263A patent/CA1053231A/en not_active Expired
-
1977
- 1977-11-23 PH PH20470A patent/PH14320A/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281571A (en) * | 1990-10-18 | 1994-01-25 | Monsanto Company | Herbicidal benzoxazinone- and benzothiazinone-substituted pyrazoles |
| US5489571A (en) * | 1990-10-18 | 1996-02-06 | Monsanto Company | Herbicidal substituted aryl-haloalkylpyrazoles |
| CN103772283A (en) * | 2014-01-17 | 2014-05-07 | 怀化学院 | Pyrazole compound containing aromatic ring and dihalide substituent as well as preparation method and use thereof |
| WO2019081477A1 (en) | 2017-10-26 | 2019-05-02 | Bayer Cropscience Aktiengesellschaft | Substituted pyrazoles, salts thereof and use thereof as herbicidal agents |
| WO2019081485A1 (en) | 2017-10-26 | 2019-05-02 | Bayer Cropscience Aktiengesellschaft | Substituted pyrazoles, salts thereof and use thereof as herbicidal agents |
| EP3858811A4 (en) * | 2018-09-28 | 2022-05-11 | Shenzhen EDK Pharmaceutical Technology Co., Ltd. | N-aromatic amides compound and preparation method and use thereof |
| US11760727B2 (en) | 2018-09-28 | 2023-09-19 | Shenzhen Edk Pharmaceutical Technology Co., Ltd. | N-aromatic amide compounds, preparation methods and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PH14320A (en) | 1981-05-27 |
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