CA1122225A - N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides - Google Patents
N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicidesInfo
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Abstract
Abstract of the Disclosure N-cyano- and N-alkynyl-2-(substituted phenoxy) butyramide compounds having the formulas:
1) in which X is selected from the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, ethyl, and methoxymethyl; and 2)
1) in which X is selected from the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, ethyl, and methoxymethyl; and 2)
Description
i22225 -1- PR-51Ç4/5164A
N-CYAN0- AND N-ALKYNYL-2-~SUBSTITUTED PHENO.YY) BUTYRAMIDES AND THEIR USE AS MILDEWICIDES
Back~round of the Invention N-dimethylacetonitrilo-C~-(substituted phenoxy) alkyl amides and their use as miticides are disclosed in the prior art in U.S. Patent No. 4,001,427, which was issued to Don R. Baker and Francis H. Walker on January 4, 1977.
These compounds differ substantially from the compounds of the present invention in both their utility and substitution of the phenoxy moiety. Such substitution or change in SU'D-stitutions would r.ot be expected from the disclosure of applicants' prior patent. A further disclosure of c~mpounds simllar to applicants' no-~el ccmpounds is that of U.S. Patent No. 3,557,209 to Sydney B. Richter et al. That disclosure ag~in fails, as applicants' own prior disclosure fails, to disclose the novel utility of applicants' compounds or applicants' specific substituted phenoxy moiety.
Brief Description of the Invention ~his invention relates to N-cyano- and N-alkynyl-
N-CYAN0- AND N-ALKYNYL-2-~SUBSTITUTED PHENO.YY) BUTYRAMIDES AND THEIR USE AS MILDEWICIDES
Back~round of the Invention N-dimethylacetonitrilo-C~-(substituted phenoxy) alkyl amides and their use as miticides are disclosed in the prior art in U.S. Patent No. 4,001,427, which was issued to Don R. Baker and Francis H. Walker on January 4, 1977.
These compounds differ substantially from the compounds of the present invention in both their utility and substitution of the phenoxy moiety. Such substitution or change in SU'D-stitutions would r.ot be expected from the disclosure of applicants' prior patent. A further disclosure of c~mpounds simllar to applicants' no-~el ccmpounds is that of U.S. Patent No. 3,557,209 to Sydney B. Richter et al. That disclosure ag~in fails, as applicants' own prior disclosure fails, to disclose the novel utility of applicants' compounds or applicants' specific substituted phenoxy moiety.
Brief Description of the Invention ~his invention relates to N-cyano- and N-alkynyl-
2-(substîtuted phenoxy) butyramides having the formulas:
1) X ~ -CHCN~C-CN
~ C2HS R
c~3 in which X is selected fro~ the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, ethyl, and methoxymethyl; ar.d ..
d~e l~ZZZZS
C~3 0 ~H
2) X- ~ -O-CXCNHC-C~R
CH3 C2H5 C-~3 in which X is bromine or methyl and R is hydrogen or methyl, _ and to their-utility as mildewicides for controlling the growth of mildew when used in a mildewicidally effective amount. The compounds of this invention are prepared b-~
conventional reactions using the properly selected starti~materials and can be applied ~y con~entional techniques.
Detailed Description of the Invention This invention relates to N-cyano- and ~-al~ynyl-2-(substituted phenoxy) butyramides having the formulas:
CH~ 0 CH3 1) X-~ ~ O-CHCNH~-C~
C~3 C2H5 R
in which X is selected frcm the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, et~yl and methoY.ymethyl, X is preferably selected from the group consisting of chlorine, br3mine and methyl and most prefera~ly selected frcm the group consisting of chlorine and methyl. R is prefe-abl~
selected from the grou~ con~isting of methyl and methox~J--methyl 2) X ~ -CHCNHC-C~CR
C~H5 R
in which X is bromine or ~ethyl and R is hydrogen or ~ethyl, X is preferably bromine and R i~ preferably methyl and to t~eir utility as mildewicides for controlling the grcwth of mildew when used in a mildewicidally efecti~e a.mount.
The ter~ "mildewicide" ~s used herein refers ~o 2 compound which is useful for controlling the growth of fungi, referred to as mildew. Controlling the grow~h of mildew b;~ -
1) X ~ -CHCN~C-CN
~ C2HS R
c~3 in which X is selected fro~ the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, ethyl, and methoxymethyl; ar.d ..
d~e l~ZZZZS
C~3 0 ~H
2) X- ~ -O-CXCNHC-C~R
CH3 C2H5 C-~3 in which X is bromine or methyl and R is hydrogen or methyl, _ and to their-utility as mildewicides for controlling the growth of mildew when used in a mildewicidally effective amount. The compounds of this invention are prepared b-~
conventional reactions using the properly selected starti~materials and can be applied ~y con~entional techniques.
Detailed Description of the Invention This invention relates to N-cyano- and ~-al~ynyl-2-(substituted phenoxy) butyramides having the formulas:
CH~ 0 CH3 1) X-~ ~ O-CHCNH~-C~
C~3 C2H5 R
in which X is selected frcm the group consisting of chlorine, bromine, thiocyano and methyl and R is selected from the group consisting of methyl, et~yl and methoY.ymethyl, X is preferably selected from the group consisting of chlorine, br3mine and methyl and most prefera~ly selected frcm the group consisting of chlorine and methyl. R is prefe-abl~
selected from the grou~ con~isting of methyl and methox~J--methyl 2) X ~ -CHCNHC-C~CR
C~H5 R
in which X is bromine or ~ethyl and R is hydrogen or ~ethyl, X is preferably bromine and R i~ preferably methyl and to t~eir utility as mildewicides for controlling the grcwth of mildew when used in a mildewicidally efecti~e a.mount.
The ter~ "mildewicide" ~s used herein refers ~o 2 compound which is useful for controlling the growth of fungi, referred to as mildew. Controlling the grow~h of mildew b;~ -
-3-applying the compounds described herein can be ac~omplished by applying a mildewicidally effective amount to the environment in which the growth of mildew fungi is encouraged.
The compounds may be applied to any environmental area which supports the growth and development of mildew furgi. By __ "controlling" is meant the prevention of the growth or the mildew fungi to be controlled.
The novel compounds of this invention may generally be prepared as follows:
1. Preparation of a 3~4~5-trisu~stituted phenoxy alkanoic acid. A 3,4,5-trisubstituted phenol is reacted with a halo-sub$tituted aliphatic acid of the fo ~ula H R
X c -c -~'~
in which X is Cl or Br in the presenc~ of sodium hydroxide at a te~perature of from about 40 to about 110C to produce the corresponding 2-(3,4,5-trisubstituted) ph~nox~ alkanoic acid.
2. Preparation of a 3~4~5-trisubstituted phenoxY
alkanoic acid chloride. The acid prepared in step 1 above is reacted with phosgene at a temperature of from about 40~C
to abou, 70C in the presence of dimethyl formamide as a catalyst to produce the corresponding 3,4,5-trisu~sti~uted phenoxy alkanoic acid chloride.
3. PreParation of the 3,4~5-trisubstituted Phenoxy alkanoic amides of this invention. ~he acid chloride pre-pared in step 2 above is reacted with an amine of the formula ~ 3 H2N /~ C~
R
wherein R is methyl, ethyl, methoxymethyl or an amine of theformula ~Z2;~2S
The compounds may be applied to any environmental area which supports the growth and development of mildew furgi. By __ "controlling" is meant the prevention of the growth or the mildew fungi to be controlled.
The novel compounds of this invention may generally be prepared as follows:
1. Preparation of a 3~4~5-trisu~stituted phenoxy alkanoic acid. A 3,4,5-trisubstituted phenol is reacted with a halo-sub$tituted aliphatic acid of the fo ~ula H R
X c -c -~'~
in which X is Cl or Br in the presenc~ of sodium hydroxide at a te~perature of from about 40 to about 110C to produce the corresponding 2-(3,4,5-trisubstituted) ph~nox~ alkanoic acid.
2. Preparation of a 3~4~5-trisubstituted phenoxY
alkanoic acid chloride. The acid prepared in step 1 above is reacted with phosgene at a temperature of from about 40~C
to abou, 70C in the presence of dimethyl formamide as a catalyst to produce the corresponding 3,4,5-trisu~sti~uted phenoxy alkanoic acid chloride.
3. PreParation of the 3,4~5-trisubstituted Phenoxy alkanoic amides of this invention. ~he acid chloride pre-pared in step 2 above is reacted with an amine of the formula ~ 3 H2N /~ C~
R
wherein R is methyl, ethyl, methoxymethyl or an amine of theformula ~Z2;~2S
-4-H2~1-C -C=C~
wherein R is hydrogen or methyl in the presence of sodium hydroxide or an organic base such as triethyl aminë in a ~ -~~
~solvent such`as methylene chloride at a temperature of fr~m about -15 to about 35C to produce the desired amide.
An alternative method of preparation is to react an Z~\-halosubstituted aliphatic acid of the formula O
XC~C-OH
~2H5 in which X is Cl or Br with phosgene and dimethyl form2mide catalyst to produce the corresponding acyL chloride of the formula R
XCHCCl C2H~
in which X is Cl or Br ~hich in turn is reacted -~th an amine of the formula C~3 ~12NC -C~
R
wherein R is methyl, ethyl, methoxymethyl or an amine of the rormula H2~-C-=CR
wherein R is hyd_ogen or methyl in the presence of an organic base such as triethylamine to produce .he corr~s-ponding ~ -haloalkylamide.
This ~ide is reacted with the sodiu~ 3alt of a phenol of the formula ,. ~
- X ~ H
. CH3 - _ 112~25 whereln X is hydrogen, chlorine, bromine, thiocyano or methyl prepared by the reac~ion of this phenol and sodium hydride in tetrahydrofuran as solvent to give the subject amides.
S - T~e follow;ng ex2mples demonstrate preparation of the novel compounds and util ty in controlling milde fungi.
EXAMPLE I
N-DI~THYLACETONITRILO-2-(4-CHLORO-3,~-DIMETHYLPH~OXY) BUTYRAMIDE
.
a. 50 grams (0.32 mole) of 4-chloro-3~s-dimeth phenol were mixed with 58.5 grams (0.35 mole) of 2-bromo-butyric acid in a 500 milliliter flask equipped withstirring equipment maintained at a temperature of 15C.
60.8 grams (0.76 mole) of 50% aqueous sodium hydroxide were added to the mixtu e with rapid stirr-ng. The temper-ature rose to 45C over the course of the addition and was held below 45C ~ith a cold bath. After all the sodi~m hydrox de had been added, cooling uas terminated and the mixture was heated at 110C for 15 minutes. Then some water, 80 milliliters of perchloroethylene and 65 milli-liters of concentrated HCl were added with s irring, the mixture was heated to 85C, phase-separated and the orgsnic layer was cooled. The product, which was identified by analysis of nuclear magnetic resonance spectra as 2-(4-chloro-3,5-dimethyl phenoxy) butyric acid, separated as a solid which was removed by filtration and air dried to give 60.7 grams (78% yield) of product having a mel.ing po nt of 99-102C.
b. 57 4 grams (0.24 mole) of the ~cid produced in step a. above were slurried in 150 milliliters of toluene in a 500 millili.er flask fi~ted with a gas-inlet tube, stirrer, thermometer, and dry ice/isopropyl alcohol conden-ser. ~.2 milliliter of dimethyl formamide was added and the mixture.~as heated to ~0C. Phosgene was ?assed-into ---~i2~Z25 the mixture at a moderate rate until 30 grams (0. 31 mole) had been added. At the conclusion of the phosgene addition, the d.y ice condenser was removed and replaced with a water-cooled condenser. Excess phosgene and hydrogen chloride were removed by purging with argon at 60C. 60.7 grams -(96% yield) of a product, which was identified by analysis of nuclear magnetic resonance spectr~ as 2-l4-chloro-3,5-dimethyl phenoxy3 butyryl chloride, was recovered as an oil from the solution by cooling the solution and removing the solvent under vacuum.
c. 8 grams (0.03 mole) of the acyl chloride pre-pared in step b. above were added dropwise to ~ 300 milli-liter flask containing a stirred solution of 2.9 grams (0.04 mole) ~ -aminoisobutyronitrile and 3.5 grams (0.04 ~ole) triethylamine in 100 milliliter of methylene chloride at 10-15C. Some cooling was necessary to maint2in the temperature. After all the acyl chlo~ide was added, the mixture was allowed to come to room temperature and the product was isolated by sequentially washing with 100 milli-liters each of water, dilute HCl, 5% Na2CO3 solution and water. The organic phase was dried over magnesium sulfate and the sol~ent was removed in vacuum to leave 9.0 grams (97% y~eld) of a solid having a melting point of 108-110C.
The prod~ct was identified as the title compound ~y analysis of nuclear magnetic resonance spectra.
~ XAMP~E II
N~ CYANO-l-METHYL-2-METHOXYMETHYL)-2-(4-CHLORO-3,5-DI~Th'YL
8.0 grams (0.03 mole) of the acyl chloride prepared as in Exampl e Ib was added dropwise, as in Example ~C, to a stirred mixture of 4.5 grams (0.03 mole) of l-cyano-l-~ methyl-2-methoxy ethyl amine hydrochloride, 4.8 grams (0.06 mole) 50% aqueous sodium hydroxide, 15 milliliters water nd 90 milliliters me~hylene chloride at 10-15~C. The mix-ture was allowed to come to room temperature after addi~,on was complet.e, The maserial was isolated as in Example Ic to give 2.0 grams of a solid, which w~.en recrystallized from ;.
:
ethanol, had a melting point of melting ?oir.t of 120-127C.
The product was identified as the title compound by analysis of nuclear magnetic resonance spectra. The yiel~ was ~0%.
EXAMPLE III
N-DI~æTH~-L~CETO~IT~ILO-2-(4-BROM0 3,5-DIMETHYL PHENOXY) BUTYRAMIDE
a. 4-bromo-3,5-dimethylphenoxy butyric acid, which was identified by analysis of nuclear magnetic resonance spectra, was pre?ared as in Example I but using:
18 Orams (0.09 mole) 4-brcmo-3,5-dimethylphenol, 18 grams (0.11 ~ole) 2-~romobutyric acid and 18.4 gra~s (0.23 mole) 50% Na~H
The only difference in the work-up was that 20 milliliters of water, 50 milliliters of perchloroethyl2ne and 20 ~illi-liters of concentrated HCl were used. 21.3 grams of the acid having a melting point of 78-85C was produced. Yield was 82% of theory.
lS b. 4-bromo-3,5-d:.methylphenoxy buty.yl chloride W2S prepared as in ~xa~ple Ib but using:
21.3 grams acid (0.07 mole), 10.0 gram~ phosgene (0.10 mole), 50 milliliters of toluene, and 0.~ milliliter of dimethyl formamide to yield 21.3 grams of the butyryl chloride as ar oil.
e. N-dimethylacetonitriio-2-(4-bromo-3,5-d~methyl phenoxy) butyramide, which was identified ~y analysl~ of nuclear magnetic rescnance spectra, was then prepared as in Example Ic, but using ~G grams acyl chloride (0~03 mole), 4.0 grams ~ -aminoisobutyronitrile> 85% pure ~0.04 mole) and 4.0 gr~.~s triethylamine (0.04 mole) in 100 milliliters of benzene as the rea~t~on solvent ~o yield 6.5 g-ams of a solid having a melting poin_ o~ 83-87C. The yield was 61% of theory.
~2ZZ2S
E ~MPLE IV
N-DI~THYLA~ETONITRIL0-2-(3,4,5-TRIMrTHYLPHENOXY) BUTYR~IDE
a. 2-(3,4,5-trimethylphenoxy) butyric acid, which was identified by analysis of nuclear magnetic resonance spectra, was prepared as in Example-Ia only using~
- ~ 50 gra~s (0.37 mole) 3,4,5-trimethylphenol, 74 grams (0.44 mole) 2-br~no~utyric acid, and 76.1 grams (0.95 mole) 50% aqueous sodiu~
hydroxide.
The product was wor~ed up in the same manner with:
90 milliliters H20, 90 milliliters perchloroethylene and 90 milliliters concentrated HCl 51.0 grams of the acid havir.g a melting point of 55-64C
W2S produced. The yi2l d was 62% of theory.
b. 2-(3,4,5-~rimethylphenoxy) butyryl ~hloride, which was identified by analysis of nu~lear magnetic resonance spectra, was prepared as in Exam~le Ib only using:
51 grams ac~d (0.23 mole), 27 grams phosgene ~0.28 mole), 150 milliliters toiuene and 2 milliliters dry dimethylformamide to giv~ acyl chloride, 52.0 grams (94% yield) to 7ield 52.0 grams of the butyryl chloride.
c. N-dimethglacetonitrilo-2-(3,4,5-trimethyl-2~ phenoxy) b~tyramide, w~ich was identified by analysis or nuclear magnet,c resonance spec~ra, was prepared as in Example Ic but using:
7.2 grams (0.03 mole) acid chloride, 2.5 grams ~0.03 mole) ~ -aminoisG~utyro-nitrile, 3.0 grams ~0.03 mole) triethylamine, a~d 100 milliliters t~l~ene as a reaction solvent to yield 5.1 grams of a solid having a melting point o~ 94-98~C. The yield w~s ~8% of theory.
11~2ZZ5 EXAMPLE V
N-(1,1-DIMETHYL-2'-BUTYRYL)-2-(4-BROMO-3,5-DIMETHYLPHENOXY) BUTYRAMIDE
a. 18 grams (0.09 mole) 4-bromo-3,5-dimethylphenol were mixed with 18 grams (0.11 mole) 2-bromobutyric acid to a 500 milli-liter flask equipped with stirring equipment maintained at a temperature of 15C. 18.4 grams (0.23 mole) of 50% aqueous sodium hydroxide were added to the mixture with rapid stirring. The temperature rose to 45C over the course of the addition and was held below 45C with a cold bath. After all the sodium hydroxide had been added, cooling was terminated and the mixture was heated at 110C for 15 minutes. Then 20 milliliters of water, 50 milli-liters of perchloroethylene and 20 milliliters of concentrated HCl were added with stirring, the mixture was heated to 85C, phase-separated and the organic layer was cooled. The product, which wasidentified by analysis of nuclear magnetic resonance spectra as 2-(4-bromo-3,5-dimethylphenoxy) butyric acid, separated as a solid which was removed by filtration and air dried to give 21.3 grams (82% yield) of product having a melting point of 78-85C.
b. 21.3 grams (0.07 mole) of the acid produced in step a.
above were slurried in 50 milliliters of toluene in a 500 millilit-er flask fitted with a gas-inlet tube, stirrer, thermometer, and dry ice isopropyl alcohol condenser. 0.2 milliliter of dimethyl formamide was added and the mixture was heated to 60C. Phosgene was passed into the mixture at a moderate rate until 10.0 grams (0.10 mole) had been added. At the conclusion of the phosgene addition, the dry ice condenser was removed and replaced with a water-cooled condenser. Excess phosgene and hydroqen chloride were removed by purging with argon at 60C. 21.3 grams ~12~225 (99. 6%yield) of the product identified by analysis of nuclear magnetic resonance spectra as 2-(4-bromo-3,5-dimethyl phenoxy) butyryl chloride was recovered as an oil from the solution by cooling the solution and removing the solvent under vacuum.
c. 8 grams (0.03 mole) of the acyl chloride produced in step b. above were added dropwise to a 300 milliliter flask containing a stirred solution of 3.9 grams (0.04 mole) 4-amino-4-methyl-2-butyne and 4.0 grams (0.04 mole) triethylamine in 100 milliliters of methylene chloride at 10-15C. Some cooling was necessary to maintain the temperature- After all the acyl chloride was added the mixture was allowed to come to room temperature and the product was isolated by sequentially washing with 100 milli-liters each of water, dilute HCl, 5% Na2CO3 solution and water.
The organic phase was dried over magnesium sulfate and the solvent was removed in vacuum to leave 6.8 grams (62~ Yield) of a solid having a melting point of 81.5-92.5C. The product was identified as the title compound by analysis of nuclear magnetic resonance ~pectra, In the following tables the above five examples are listed together with four additional examples which were prepared in a manner analogous to that described above, starting with the appropriate materials. The compounds in the table are representa-tive of those embodied in the present invention. Compound numbers are assigned to each and are used through the remainder of the application.
112~225 -TABLE I
~_~ O CH3 X~O -CHCNHO -CN
. CH3 Compound Physical Number X R Properties 1 -Cl -CH3 m.p. 108-110C
2 -Cl -CH20C~3 m.p. 120-127 C
3 -Br -CH3 m.p. 83-87C
4 -CH3 -CH3 , ~ p 94-980C
-Cl CH2C~3 m.p. 89-93C
6 -SCN -CH3 m.p. 127-132C
,TABLE II
X ~ -~HCNHC-C~C?.
C 3 C2~5 CH3 Compound Physic21 _Number _ X R Properties 7 -3r -H ~.p. 104-lQ6C
8 -Br -CH3 m.p. 81.5-32.5C
9 -CH3 -H m.p. 100-lD2C
l~lZZ225 Foliar Fungicide Evaluation Tests Evaluation for Preventive Action on Bean Powdery Mildew A candidate chemical is dissolved in an appropriate solvent and diluted with water containing several drops of Tween 20 ~, a polyoxyethylene sorbitan monolaurate wetting agent. Test concentrations, ranging from lO00 parts per million downward, are sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.). After the plants are dry, the leaves are dusted with spores of the powdery mildew fungus (Erysiphe polygoni De Candolle) and the plants are retained in the greenhouse until the fungal growth appears on the leaf surface. Effectiveness is recorded as the lowest concentration, in parts per million, which will provide 50% reduction in mycelial formation as compared to untreated, inoculated plants. These values are recorded in Table III.
TABLE III
Preventive Action Compound Bean Powdery Number Mildew l 25 6 lO00 7 lO0 The compounds of this invention are generally embodied l~Z;~Z2S
into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal compositions which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these composi-tions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petro-leum, etc.; water; emulsifying agents; surface active agents;
talc; pyrophyllite; diatomite; gypsum; clays, propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc., upon which these pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connec-tion with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.
The precise manner in which the pesticidal compositions 2~ of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid co~position; for Pxample, an emulsion, suspension, or . , ~122225 aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to about 1.0% by weight of the active pesticide compound.
-13a-.'~ `I
wherein R is hydrogen or methyl in the presence of sodium hydroxide or an organic base such as triethyl aminë in a ~ -~~
~solvent such`as methylene chloride at a temperature of fr~m about -15 to about 35C to produce the desired amide.
An alternative method of preparation is to react an Z~\-halosubstituted aliphatic acid of the formula O
XC~C-OH
~2H5 in which X is Cl or Br with phosgene and dimethyl form2mide catalyst to produce the corresponding acyL chloride of the formula R
XCHCCl C2H~
in which X is Cl or Br ~hich in turn is reacted -~th an amine of the formula C~3 ~12NC -C~
R
wherein R is methyl, ethyl, methoxymethyl or an amine of the rormula H2~-C-=CR
wherein R is hyd_ogen or methyl in the presence of an organic base such as triethylamine to produce .he corr~s-ponding ~ -haloalkylamide.
This ~ide is reacted with the sodiu~ 3alt of a phenol of the formula ,. ~
- X ~ H
. CH3 - _ 112~25 whereln X is hydrogen, chlorine, bromine, thiocyano or methyl prepared by the reac~ion of this phenol and sodium hydride in tetrahydrofuran as solvent to give the subject amides.
S - T~e follow;ng ex2mples demonstrate preparation of the novel compounds and util ty in controlling milde fungi.
EXAMPLE I
N-DI~THYLACETONITRILO-2-(4-CHLORO-3,~-DIMETHYLPH~OXY) BUTYRAMIDE
.
a. 50 grams (0.32 mole) of 4-chloro-3~s-dimeth phenol were mixed with 58.5 grams (0.35 mole) of 2-bromo-butyric acid in a 500 milliliter flask equipped withstirring equipment maintained at a temperature of 15C.
60.8 grams (0.76 mole) of 50% aqueous sodium hydroxide were added to the mixtu e with rapid stirr-ng. The temper-ature rose to 45C over the course of the addition and was held below 45C ~ith a cold bath. After all the sodi~m hydrox de had been added, cooling uas terminated and the mixture was heated at 110C for 15 minutes. Then some water, 80 milliliters of perchloroethylene and 65 milli-liters of concentrated HCl were added with s irring, the mixture was heated to 85C, phase-separated and the orgsnic layer was cooled. The product, which was identified by analysis of nuclear magnetic resonance spectra as 2-(4-chloro-3,5-dimethyl phenoxy) butyric acid, separated as a solid which was removed by filtration and air dried to give 60.7 grams (78% yield) of product having a mel.ing po nt of 99-102C.
b. 57 4 grams (0.24 mole) of the ~cid produced in step a. above were slurried in 150 milliliters of toluene in a 500 millili.er flask fi~ted with a gas-inlet tube, stirrer, thermometer, and dry ice/isopropyl alcohol conden-ser. ~.2 milliliter of dimethyl formamide was added and the mixture.~as heated to ~0C. Phosgene was ?assed-into ---~i2~Z25 the mixture at a moderate rate until 30 grams (0. 31 mole) had been added. At the conclusion of the phosgene addition, the d.y ice condenser was removed and replaced with a water-cooled condenser. Excess phosgene and hydrogen chloride were removed by purging with argon at 60C. 60.7 grams -(96% yield) of a product, which was identified by analysis of nuclear magnetic resonance spectr~ as 2-l4-chloro-3,5-dimethyl phenoxy3 butyryl chloride, was recovered as an oil from the solution by cooling the solution and removing the solvent under vacuum.
c. 8 grams (0.03 mole) of the acyl chloride pre-pared in step b. above were added dropwise to ~ 300 milli-liter flask containing a stirred solution of 2.9 grams (0.04 mole) ~ -aminoisobutyronitrile and 3.5 grams (0.04 ~ole) triethylamine in 100 milliliter of methylene chloride at 10-15C. Some cooling was necessary to maint2in the temperature. After all the acyl chlo~ide was added, the mixture was allowed to come to room temperature and the product was isolated by sequentially washing with 100 milli-liters each of water, dilute HCl, 5% Na2CO3 solution and water. The organic phase was dried over magnesium sulfate and the sol~ent was removed in vacuum to leave 9.0 grams (97% y~eld) of a solid having a melting point of 108-110C.
The prod~ct was identified as the title compound ~y analysis of nuclear magnetic resonance spectra.
~ XAMP~E II
N~ CYANO-l-METHYL-2-METHOXYMETHYL)-2-(4-CHLORO-3,5-DI~Th'YL
8.0 grams (0.03 mole) of the acyl chloride prepared as in Exampl e Ib was added dropwise, as in Example ~C, to a stirred mixture of 4.5 grams (0.03 mole) of l-cyano-l-~ methyl-2-methoxy ethyl amine hydrochloride, 4.8 grams (0.06 mole) 50% aqueous sodium hydroxide, 15 milliliters water nd 90 milliliters me~hylene chloride at 10-15~C. The mix-ture was allowed to come to room temperature after addi~,on was complet.e, The maserial was isolated as in Example Ic to give 2.0 grams of a solid, which w~.en recrystallized from ;.
:
ethanol, had a melting point of melting ?oir.t of 120-127C.
The product was identified as the title compound by analysis of nuclear magnetic resonance spectra. The yiel~ was ~0%.
EXAMPLE III
N-DI~æTH~-L~CETO~IT~ILO-2-(4-BROM0 3,5-DIMETHYL PHENOXY) BUTYRAMIDE
a. 4-bromo-3,5-dimethylphenoxy butyric acid, which was identified by analysis of nuclear magnetic resonance spectra, was pre?ared as in Example I but using:
18 Orams (0.09 mole) 4-brcmo-3,5-dimethylphenol, 18 grams (0.11 ~ole) 2-~romobutyric acid and 18.4 gra~s (0.23 mole) 50% Na~H
The only difference in the work-up was that 20 milliliters of water, 50 milliliters of perchloroethyl2ne and 20 ~illi-liters of concentrated HCl were used. 21.3 grams of the acid having a melting point of 78-85C was produced. Yield was 82% of theory.
lS b. 4-bromo-3,5-d:.methylphenoxy buty.yl chloride W2S prepared as in ~xa~ple Ib but using:
21.3 grams acid (0.07 mole), 10.0 gram~ phosgene (0.10 mole), 50 milliliters of toluene, and 0.~ milliliter of dimethyl formamide to yield 21.3 grams of the butyryl chloride as ar oil.
e. N-dimethylacetonitriio-2-(4-bromo-3,5-d~methyl phenoxy) butyramide, which was identified ~y analysl~ of nuclear magnetic rescnance spectra, was then prepared as in Example Ic, but using ~G grams acyl chloride (0~03 mole), 4.0 grams ~ -aminoisobutyronitrile> 85% pure ~0.04 mole) and 4.0 gr~.~s triethylamine (0.04 mole) in 100 milliliters of benzene as the rea~t~on solvent ~o yield 6.5 g-ams of a solid having a melting poin_ o~ 83-87C. The yield was 61% of theory.
~2ZZ2S
E ~MPLE IV
N-DI~THYLA~ETONITRIL0-2-(3,4,5-TRIMrTHYLPHENOXY) BUTYR~IDE
a. 2-(3,4,5-trimethylphenoxy) butyric acid, which was identified by analysis of nuclear magnetic resonance spectra, was prepared as in Example-Ia only using~
- ~ 50 gra~s (0.37 mole) 3,4,5-trimethylphenol, 74 grams (0.44 mole) 2-br~no~utyric acid, and 76.1 grams (0.95 mole) 50% aqueous sodiu~
hydroxide.
The product was wor~ed up in the same manner with:
90 milliliters H20, 90 milliliters perchloroethylene and 90 milliliters concentrated HCl 51.0 grams of the acid havir.g a melting point of 55-64C
W2S produced. The yi2l d was 62% of theory.
b. 2-(3,4,5-~rimethylphenoxy) butyryl ~hloride, which was identified by analysis of nu~lear magnetic resonance spectra, was prepared as in Exam~le Ib only using:
51 grams ac~d (0.23 mole), 27 grams phosgene ~0.28 mole), 150 milliliters toiuene and 2 milliliters dry dimethylformamide to giv~ acyl chloride, 52.0 grams (94% yield) to 7ield 52.0 grams of the butyryl chloride.
c. N-dimethglacetonitrilo-2-(3,4,5-trimethyl-2~ phenoxy) b~tyramide, w~ich was identified by analysis or nuclear magnet,c resonance spec~ra, was prepared as in Example Ic but using:
7.2 grams (0.03 mole) acid chloride, 2.5 grams ~0.03 mole) ~ -aminoisG~utyro-nitrile, 3.0 grams ~0.03 mole) triethylamine, a~d 100 milliliters t~l~ene as a reaction solvent to yield 5.1 grams of a solid having a melting point o~ 94-98~C. The yield w~s ~8% of theory.
11~2ZZ5 EXAMPLE V
N-(1,1-DIMETHYL-2'-BUTYRYL)-2-(4-BROMO-3,5-DIMETHYLPHENOXY) BUTYRAMIDE
a. 18 grams (0.09 mole) 4-bromo-3,5-dimethylphenol were mixed with 18 grams (0.11 mole) 2-bromobutyric acid to a 500 milli-liter flask equipped with stirring equipment maintained at a temperature of 15C. 18.4 grams (0.23 mole) of 50% aqueous sodium hydroxide were added to the mixture with rapid stirring. The temperature rose to 45C over the course of the addition and was held below 45C with a cold bath. After all the sodium hydroxide had been added, cooling was terminated and the mixture was heated at 110C for 15 minutes. Then 20 milliliters of water, 50 milli-liters of perchloroethylene and 20 milliliters of concentrated HCl were added with stirring, the mixture was heated to 85C, phase-separated and the organic layer was cooled. The product, which wasidentified by analysis of nuclear magnetic resonance spectra as 2-(4-bromo-3,5-dimethylphenoxy) butyric acid, separated as a solid which was removed by filtration and air dried to give 21.3 grams (82% yield) of product having a melting point of 78-85C.
b. 21.3 grams (0.07 mole) of the acid produced in step a.
above were slurried in 50 milliliters of toluene in a 500 millilit-er flask fitted with a gas-inlet tube, stirrer, thermometer, and dry ice isopropyl alcohol condenser. 0.2 milliliter of dimethyl formamide was added and the mixture was heated to 60C. Phosgene was passed into the mixture at a moderate rate until 10.0 grams (0.10 mole) had been added. At the conclusion of the phosgene addition, the dry ice condenser was removed and replaced with a water-cooled condenser. Excess phosgene and hydroqen chloride were removed by purging with argon at 60C. 21.3 grams ~12~225 (99. 6%yield) of the product identified by analysis of nuclear magnetic resonance spectra as 2-(4-bromo-3,5-dimethyl phenoxy) butyryl chloride was recovered as an oil from the solution by cooling the solution and removing the solvent under vacuum.
c. 8 grams (0.03 mole) of the acyl chloride produced in step b. above were added dropwise to a 300 milliliter flask containing a stirred solution of 3.9 grams (0.04 mole) 4-amino-4-methyl-2-butyne and 4.0 grams (0.04 mole) triethylamine in 100 milliliters of methylene chloride at 10-15C. Some cooling was necessary to maintain the temperature- After all the acyl chloride was added the mixture was allowed to come to room temperature and the product was isolated by sequentially washing with 100 milli-liters each of water, dilute HCl, 5% Na2CO3 solution and water.
The organic phase was dried over magnesium sulfate and the solvent was removed in vacuum to leave 6.8 grams (62~ Yield) of a solid having a melting point of 81.5-92.5C. The product was identified as the title compound by analysis of nuclear magnetic resonance ~pectra, In the following tables the above five examples are listed together with four additional examples which were prepared in a manner analogous to that described above, starting with the appropriate materials. The compounds in the table are representa-tive of those embodied in the present invention. Compound numbers are assigned to each and are used through the remainder of the application.
112~225 -TABLE I
~_~ O CH3 X~O -CHCNHO -CN
. CH3 Compound Physical Number X R Properties 1 -Cl -CH3 m.p. 108-110C
2 -Cl -CH20C~3 m.p. 120-127 C
3 -Br -CH3 m.p. 83-87C
4 -CH3 -CH3 , ~ p 94-980C
-Cl CH2C~3 m.p. 89-93C
6 -SCN -CH3 m.p. 127-132C
,TABLE II
X ~ -~HCNHC-C~C?.
C 3 C2~5 CH3 Compound Physic21 _Number _ X R Properties 7 -3r -H ~.p. 104-lQ6C
8 -Br -CH3 m.p. 81.5-32.5C
9 -CH3 -H m.p. 100-lD2C
l~lZZ225 Foliar Fungicide Evaluation Tests Evaluation for Preventive Action on Bean Powdery Mildew A candidate chemical is dissolved in an appropriate solvent and diluted with water containing several drops of Tween 20 ~, a polyoxyethylene sorbitan monolaurate wetting agent. Test concentrations, ranging from lO00 parts per million downward, are sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.). After the plants are dry, the leaves are dusted with spores of the powdery mildew fungus (Erysiphe polygoni De Candolle) and the plants are retained in the greenhouse until the fungal growth appears on the leaf surface. Effectiveness is recorded as the lowest concentration, in parts per million, which will provide 50% reduction in mycelial formation as compared to untreated, inoculated plants. These values are recorded in Table III.
TABLE III
Preventive Action Compound Bean Powdery Number Mildew l 25 6 lO00 7 lO0 The compounds of this invention are generally embodied l~Z;~Z2S
into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal compositions which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these composi-tions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petro-leum, etc.; water; emulsifying agents; surface active agents;
talc; pyrophyllite; diatomite; gypsum; clays, propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc., upon which these pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connec-tion with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.
The precise manner in which the pesticidal compositions 2~ of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid co~position; for Pxample, an emulsion, suspension, or . , ~122225 aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to about 1.0% by weight of the active pesticide compound.
-13a-.'~ `I
Claims (8)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound having the formula in which X is selected from the group consisting of bromine and methyl and R is selected from the group consisting of hydrogen and methyl.
2. The compound of Claim 1 in which X is bromine and R
is hydrogen.
is hydrogen.
3. The compound of Claim 1 in which X is bromine and R
is methyl.
is methyl.
4. The compound of Claim 1 in which X is methyl and R
is hydrogen.
is hydrogen.
5. A method of controlling the growth of mildew compris-ing applying to the locus thereof a mildewicidally effective amount of a compound having the formula in which X is selected from the group consisting of bromine and methyl and R is selected from the group consisting of hydrogen and methyl.
6. The method of Claim 5 in which X is bromine and R
is hydrogen.
is hydrogen.
7. The method of Claim 5 in which X is bromine and R is methyl.
8. The method of Claim 5 in which X is methyl and R
is hydrogen.
is hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000373982A CA1122225A (en) | 1977-10-26 | 1981-03-26 | N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/845,513 US4154849A (en) | 1977-10-26 | 1977-10-26 | N-Cyano-2-(substituted phenoxy) butyramides and their use as mildewicides |
| US845,513 | 1977-10-26 | ||
| US05/845,514 US4168319A (en) | 1977-10-26 | 1977-10-26 | N-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides |
| US845,514 | 1977-10-26 | ||
| CA000314405A CA1117961A (en) | 1977-10-26 | 1978-10-26 | N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides |
| CA000373982A CA1122225A (en) | 1977-10-26 | 1981-03-26 | N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122225A true CA1122225A (en) | 1982-04-20 |
Family
ID=27426114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000373982A Expired CA1122225A (en) | 1977-10-26 | 1981-03-26 | N-cyano-and n-alkynyl-2-(substituted phenoxy) butyramides and their use as mildewicides |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1122225A (en) |
-
1981
- 1981-03-26 CA CA000373982A patent/CA1122225A/en not_active Expired
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