CA1125764A - Insect repellent compounds - Google Patents
Insect repellent compoundsInfo
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- CA1125764A CA1125764A CA338,929A CA338929A CA1125764A CA 1125764 A CA1125764 A CA 1125764A CA 338929 A CA338929 A CA 338929A CA 1125764 A CA1125764 A CA 1125764A
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- pyridine ring
- ester moiety
- compound
- chch3
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Abstract
Abstract of the Disclosure Compounds having the formula
Description
INSECT REPELLENT COMPOUNDS
Back~round of the Invention This invention relates to novel compounds having the formula ~ (CH2)n - ~ -R
in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3. The terms "alkyl" and "alkenyl" in-clude both straight and branched chain groups. In a pre-ferred embodiment, n is 3 and R is 2-methyl-l-propenyl, -CH=C(CH3)2o A preferred compound of this type is gamma-(3-p~ridyl)--propyl-3-methyl-2-butenoate (nG3, R=2-methyl-1-propenyl, and the ester moiety is substituted at the 3-position on the pyridyl ring). Other compounds include the 2-pyridyl and 4-pyridyl isomers o~ this preferred com-pound, the methyl analog (n=l, R=2-methyl-l-propenyl, sub~titution at the 3-position on the ring) and ga~ma-(3-pyridyl)-propyl isovaLerate (n~3, R=isobutyl, ~ubstitu~ion at the 3-pvsition on the ring).
The compounds of this type can be prepared by reaction o~ an appropriate pyridyl alkanol with an acyl chloride:
(~H2)nOH + R~Cl >
(CH2)nO - ~ -R + HCl 'S7~'~
The reaction is generally conducted at tempera-tures of about 5-15C., in the presence of a solvent such as methylene chloride, chloroform, other chloro-carbon solvents or ethers, and a hydrogen chloride acceptor, For preparation of compounds in which R is alkyl, suitable hydrogen chloride acceptors include pyridine, triethylamine and sodium hydroxide. For compounds in which R is alkenyl, pyridine is used. The product is recovered by conventional extraction, washing and filtration steps.
Preparation of such compounds is illustrated by the following example.
Example 1 Preparation of Gamma-(3-PyridYl)-Propyl-3-Methyl-2-Butenoate Into a flask was introduced a solution of 5.00 grams (0.036 mole) of 3-(3-pyridyl)-1-propanol and 3.16 grams (0.040 mole) pyridine ~reagent grade) in 50 milli-liters of methylene chloride (reagent grade). A clear brown solution was formed which was then cooled to 0C.
with an ice-water bath. There was then added 4.74 grams (0.040 mole) of 3,3-dimethylacryloyl chlorid~ (97% pure), dropwise, over a period of 10 minutes~ the temperature being maintained between 5 and 15C. The solution be-came deep red. Following the addition, the solution was stirred at 0C. for one hour; the cooling bath was removed and the solut~on stirred at room temperature for three additional hours.
The solution was then diluted with 50 milli-liters of methylene chloride and poured into 50 milli-liters of water; the organic layer was separated and washed with 10 milliliters of a saturated sodium bi-carbonate solution and three portions each of 10 milliliters of wa~er until the pH of the solution was measured at 7, followed by washing with 10 milliliters of sodium chloride and drying ~ver sodium sulfate. The dried organic solution was filtered through sodium sulfate and the solvent was removed under vacuum to yield 8.08 grams (101.3% o~ theoretical) of the desired compound, a crude clear orange oil, n30 1.5153. The structure of the compound was confirmed by Infrared and nuclear magnetic resonance spectra.
Insect Repellent Test The compound prepared according to Example 1 was tested for insect repellency by the following pro-cedures:
Mosquito Repellent Evaluation: A paper cup f~lled with pupae of the mosquito Culex pipiens quinquefasciatus ~Say) W8S placed in a screen cage and the pupae allowed to emerge into adults. Sugar cubes were then saturated with 0.8 milliliters of acetone containing the test compound and, for a control, with the same amount of acetone alone Concen-trations o~ the test compound were utilized beginning at 1% and proceeding to lower concentrations. After the cubes dried, they were put into the screen cage~ Repellency was determined by the number o~ mosquito adults lighting and feeding on the sugar cubes, with observations being made daily. New adult mosquitos were periodically added to the cages until all sugar cubes became non-repellent.
The number of days of complete repellency of mosquitos from the sugar cubes were recorded. Comparative tests were similarly conducted using the compound N,N-diethyl-m-toluamide, commercially manufactured and employed as an insect repellent, and generally known by the generic name "deet". The results of the ~ests of deet and the compound of Example 1 are shown in the follcwing Table I, the num-bers of each colul~n represen.ing the number o~ days of complete repellency observed using the speclfied concentra-tion.
Table I
~ CONCENTRATION~ %
1 0.5 G.3 0.1 0 (acetone only~
Example 1 ,-æ~ ~~7 2~ 5 0 deet 11-13 6.7 5 5 0 Thus, at a concentration as low as 0.1%, the new compound was as effective as deet in repelling mos-quitos. At higher concentrations, it was more effective than deet. At a concentration of 1% of the new com~ und in the solution, after 60 days the mosquitos were still repelled from the sugar cube and the tests were t~rminated.
Houseflies: The insect utilized for this test was housefly, Musca domestica (L.) One hundred (100) houseflies of mixed sexes were placed in test cages. Each test cage consisted of a 16 ounce cupg covered with tulle netting, and having two 3/4 ounce cups s~apled on opposite sides of the upper, interior perimeter. One of the small cups con-tained a sugar cube saturated with 0.8 milliliters of acetone containing a specific concentration of the test compound. The cube was dried and weighed before being placed in the cup. The other small cup contained a water-saturated cotton plug. The test cages were placed on a turntable and rotated at 1.5 revolutions per minute to keep the flies randomly distributed inside the cages.
After 72 hours the flies in each cage were anesthetized with carbon dioxîde. The sugar cubes were removed and re-weighed and the percentage weight loss (due to consumption by the flies) recorded. The cubes with the least weight loss are considered to show the greatest repellency. Test concentrations of the compound ranged from 1% down to 0.1%. The weight losses of the sug~r in percent, is shown in the following Table II.
Table II
CONCENTRATION, %
1 0 r 5 0.3 0 1 0 (Acetone onl ) Example 1 4~ 5.91 ~3 ~ 12.7 Y
deet 7.09 7.12 9.69 11.0 12.7 The novel compounds of this invention may be used as insect repellents i~ di}uted or undiluted form.
When used in a diluted form, the compounds may be embodied into compositions containing a relatively high or relatively low concentration of the active compound. For example, the active compound can be incorpora~ed into relatively high concentration compositions such as wet sprays or solutions in alcohol or other suitable solvents. Such compositions may contain, in addition to the active compound, adjuvants such as emulsifying agents, surface active agents, antioxidants, and propellants, which may be found normally in insect repellant preparations. The active compounds of this invention may be employed as the sole active com-ponent of such compositions or can be used in admixture with other compounds having sLmilar or dif~erent utility. For example, the novel compounds may be incorporated into creams, lotions, powders, suntan oils, insecticides and other preparations, which may contain pesticidal or other useful substances, as well as to compositions of various ~ypes used for treating fabrics or articles of clothing to render them insect repellent. In general~ compositions for repellent use may contain from 0.5 to as high as 80 weight %, preferably from 2 to about 40 weight %, or the novel compound.
SUPPLEMENTARY DISCLOSURE
In accordance with the teachings of the Principal Disclosure there is provided insect repellent compounds of the formula ¢~ (CH2 ) n~~C~R
wherein in the preferred embodiment R is 2-methyl-1-propenyl n is 3, and the ester moiety is substituted at the 3-position on the pyridine ring.
With the teachings now presented in the Supplementary Disclosure there is provided insect repellent compounds of the formula o ~ ( 2)n C R
wherein R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
These compGunds may readily be prepared as outlined in the Principal Disclosure by the reaction of an appropriate pyridyl alkanol with an acyl chloride under the conditions previously discussed.
m e following compounds were prepared:
TABLE III
(Invention) ~ ~H2~30CR
Compound Ring No. _ Position R
1 3- -CH--C(CH3)2
Back~round of the Invention This invention relates to novel compounds having the formula ~ (CH2)n - ~ -R
in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3. The terms "alkyl" and "alkenyl" in-clude both straight and branched chain groups. In a pre-ferred embodiment, n is 3 and R is 2-methyl-l-propenyl, -CH=C(CH3)2o A preferred compound of this type is gamma-(3-p~ridyl)--propyl-3-methyl-2-butenoate (nG3, R=2-methyl-1-propenyl, and the ester moiety is substituted at the 3-position on the pyridyl ring). Other compounds include the 2-pyridyl and 4-pyridyl isomers o~ this preferred com-pound, the methyl analog (n=l, R=2-methyl-l-propenyl, sub~titution at the 3-position on the ring) and ga~ma-(3-pyridyl)-propyl isovaLerate (n~3, R=isobutyl, ~ubstitu~ion at the 3-pvsition on the ring).
The compounds of this type can be prepared by reaction o~ an appropriate pyridyl alkanol with an acyl chloride:
(~H2)nOH + R~Cl >
(CH2)nO - ~ -R + HCl 'S7~'~
The reaction is generally conducted at tempera-tures of about 5-15C., in the presence of a solvent such as methylene chloride, chloroform, other chloro-carbon solvents or ethers, and a hydrogen chloride acceptor, For preparation of compounds in which R is alkyl, suitable hydrogen chloride acceptors include pyridine, triethylamine and sodium hydroxide. For compounds in which R is alkenyl, pyridine is used. The product is recovered by conventional extraction, washing and filtration steps.
Preparation of such compounds is illustrated by the following example.
Example 1 Preparation of Gamma-(3-PyridYl)-Propyl-3-Methyl-2-Butenoate Into a flask was introduced a solution of 5.00 grams (0.036 mole) of 3-(3-pyridyl)-1-propanol and 3.16 grams (0.040 mole) pyridine ~reagent grade) in 50 milli-liters of methylene chloride (reagent grade). A clear brown solution was formed which was then cooled to 0C.
with an ice-water bath. There was then added 4.74 grams (0.040 mole) of 3,3-dimethylacryloyl chlorid~ (97% pure), dropwise, over a period of 10 minutes~ the temperature being maintained between 5 and 15C. The solution be-came deep red. Following the addition, the solution was stirred at 0C. for one hour; the cooling bath was removed and the solut~on stirred at room temperature for three additional hours.
The solution was then diluted with 50 milli-liters of methylene chloride and poured into 50 milli-liters of water; the organic layer was separated and washed with 10 milliliters of a saturated sodium bi-carbonate solution and three portions each of 10 milliliters of wa~er until the pH of the solution was measured at 7, followed by washing with 10 milliliters of sodium chloride and drying ~ver sodium sulfate. The dried organic solution was filtered through sodium sulfate and the solvent was removed under vacuum to yield 8.08 grams (101.3% o~ theoretical) of the desired compound, a crude clear orange oil, n30 1.5153. The structure of the compound was confirmed by Infrared and nuclear magnetic resonance spectra.
Insect Repellent Test The compound prepared according to Example 1 was tested for insect repellency by the following pro-cedures:
Mosquito Repellent Evaluation: A paper cup f~lled with pupae of the mosquito Culex pipiens quinquefasciatus ~Say) W8S placed in a screen cage and the pupae allowed to emerge into adults. Sugar cubes were then saturated with 0.8 milliliters of acetone containing the test compound and, for a control, with the same amount of acetone alone Concen-trations o~ the test compound were utilized beginning at 1% and proceeding to lower concentrations. After the cubes dried, they were put into the screen cage~ Repellency was determined by the number o~ mosquito adults lighting and feeding on the sugar cubes, with observations being made daily. New adult mosquitos were periodically added to the cages until all sugar cubes became non-repellent.
The number of days of complete repellency of mosquitos from the sugar cubes were recorded. Comparative tests were similarly conducted using the compound N,N-diethyl-m-toluamide, commercially manufactured and employed as an insect repellent, and generally known by the generic name "deet". The results of the ~ests of deet and the compound of Example 1 are shown in the follcwing Table I, the num-bers of each colul~n represen.ing the number o~ days of complete repellency observed using the speclfied concentra-tion.
Table I
~ CONCENTRATION~ %
1 0.5 G.3 0.1 0 (acetone only~
Example 1 ,-æ~ ~~7 2~ 5 0 deet 11-13 6.7 5 5 0 Thus, at a concentration as low as 0.1%, the new compound was as effective as deet in repelling mos-quitos. At higher concentrations, it was more effective than deet. At a concentration of 1% of the new com~ und in the solution, after 60 days the mosquitos were still repelled from the sugar cube and the tests were t~rminated.
Houseflies: The insect utilized for this test was housefly, Musca domestica (L.) One hundred (100) houseflies of mixed sexes were placed in test cages. Each test cage consisted of a 16 ounce cupg covered with tulle netting, and having two 3/4 ounce cups s~apled on opposite sides of the upper, interior perimeter. One of the small cups con-tained a sugar cube saturated with 0.8 milliliters of acetone containing a specific concentration of the test compound. The cube was dried and weighed before being placed in the cup. The other small cup contained a water-saturated cotton plug. The test cages were placed on a turntable and rotated at 1.5 revolutions per minute to keep the flies randomly distributed inside the cages.
After 72 hours the flies in each cage were anesthetized with carbon dioxîde. The sugar cubes were removed and re-weighed and the percentage weight loss (due to consumption by the flies) recorded. The cubes with the least weight loss are considered to show the greatest repellency. Test concentrations of the compound ranged from 1% down to 0.1%. The weight losses of the sug~r in percent, is shown in the following Table II.
Table II
CONCENTRATION, %
1 0 r 5 0.3 0 1 0 (Acetone onl ) Example 1 4~ 5.91 ~3 ~ 12.7 Y
deet 7.09 7.12 9.69 11.0 12.7 The novel compounds of this invention may be used as insect repellents i~ di}uted or undiluted form.
When used in a diluted form, the compounds may be embodied into compositions containing a relatively high or relatively low concentration of the active compound. For example, the active compound can be incorpora~ed into relatively high concentration compositions such as wet sprays or solutions in alcohol or other suitable solvents. Such compositions may contain, in addition to the active compound, adjuvants such as emulsifying agents, surface active agents, antioxidants, and propellants, which may be found normally in insect repellant preparations. The active compounds of this invention may be employed as the sole active com-ponent of such compositions or can be used in admixture with other compounds having sLmilar or dif~erent utility. For example, the novel compounds may be incorporated into creams, lotions, powders, suntan oils, insecticides and other preparations, which may contain pesticidal or other useful substances, as well as to compositions of various ~ypes used for treating fabrics or articles of clothing to render them insect repellent. In general~ compositions for repellent use may contain from 0.5 to as high as 80 weight %, preferably from 2 to about 40 weight %, or the novel compound.
SUPPLEMENTARY DISCLOSURE
In accordance with the teachings of the Principal Disclosure there is provided insect repellent compounds of the formula ¢~ (CH2 ) n~~C~R
wherein in the preferred embodiment R is 2-methyl-1-propenyl n is 3, and the ester moiety is substituted at the 3-position on the pyridine ring.
With the teachings now presented in the Supplementary Disclosure there is provided insect repellent compounds of the formula o ~ ( 2)n C R
wherein R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
These compGunds may readily be prepared as outlined in the Principal Disclosure by the reaction of an appropriate pyridyl alkanol with an acyl chloride under the conditions previously discussed.
m e following compounds were prepared:
TABLE III
(Invention) ~ ~H2~30CR
Compound Ring No. _ Position R
1 3- -CH--C(CH3)2
2 2- -CH=C(CH3)2
3 4~ -CH=C(CH3)2
4 3- -CH2-CH(CH3)2 57~; ~
Compound Ring No. Position R
3- -CH=CHCH3 7 3_ -CH(CH3)CH2CH3 8 4- -CH(CH3)CH2CH3 9 2- -CH(CH3)CH2CH3 4- -CH2CH(CH3)2 11 2- -CH2CH~CH3)2 13 2- -C(CH3)3 14 3- -C(CH3)3 4- -C(CH3)3 16 2- -C(CH3~=CHCH3 17 3- -C(cH3)=cHcH3 18 4- -C(CH3)=CHCH3 19 3- ( 3) 2 3- -CH(CH3)2 The novel compounds of the present invention may be used as insect repellents in diluted or undiluted form. The following were conducted employing the compounds.
Mosquito Repellency Test A paper cup filled with pupae of the mosquito Culex pipiens quinquefasciatus (Say) was placed in a screened cage and the pupae allowed to emerge into adults. Sugar cubes were then saturated with 1~0 milliliters (ml.) of an acetone solution containing 0.1 weight ~ of a test compound, and for a control, with the same amount of acetone alone. After the cubes dried, they were put into the screened cage. R~pellency was determined by the number of mosquito adults lighting and feeding on the sugar cubes, with observations being made daily for fi~e days after treatment. The num~er of days of complete 6 ~
repellency of mosquitos from the sugar cubes was recorded.
Housefly Repellency Test:
One hundred (100) houseflies of the species Musca domestica (L.) of mixed sexes were placed in test cages. In each cage was placed a sugar cube saturated with 1.0 ml. of acetone containing 1 weight % of the test compound. The cubes were dried and weighed before being placed in the cages. Each cage also contained a water-saturated cotton plug to provide moisture. The cages were placed on a turntable and rotated at 1.5 revolutions per minute to keep the flies randomly distri-buted inside the cages. After 48 hours, the flies in each were anesthetized with carbon dioxide. The sugar cubes were removed and reweighed and the percentage weight loss (due to consumption by the flies) was recorded. A repellency ratio, calculated as the ~ weight loss of the treated sugar cube divided by the percent weight loss of controlled sugar cube treated with acetone only, was calculated. The lower the repellency ratio, the greater the repellency of the test compound.
The following table IV provides the results of the test of the compounds previously listed for repellency for mosquitos (Mos) and houseflies (HF). In many cases the housefly data represents an average of several replications.
TABLE IV
HF
CompoundMos., days repellency No. repelled ratio 1 >5 0.48 2 >5 0.38 3 >5 0.43 4 >5 0.49 3 0.73 6 3 0.69 7 >5 0.42 i'57~ ~
Compound Mos., days HF
No. repelled repellency _ ratio 8 4 0.54 9 1 0.71 3 0.44 11 1 0.44 12 1 0.70 13 1 0.53 14 2 0.36 2-3 0.11 16 >5 0.40 17 >5 0.47 18 >5 0.54 19 4 0.47 3 0.47 ~ -SD 9-; ~ ~
Compound Ring No. Position R
3- -CH=CHCH3 7 3_ -CH(CH3)CH2CH3 8 4- -CH(CH3)CH2CH3 9 2- -CH(CH3)CH2CH3 4- -CH2CH(CH3)2 11 2- -CH2CH~CH3)2 13 2- -C(CH3)3 14 3- -C(CH3)3 4- -C(CH3)3 16 2- -C(CH3~=CHCH3 17 3- -C(cH3)=cHcH3 18 4- -C(CH3)=CHCH3 19 3- ( 3) 2 3- -CH(CH3)2 The novel compounds of the present invention may be used as insect repellents in diluted or undiluted form. The following were conducted employing the compounds.
Mosquito Repellency Test A paper cup filled with pupae of the mosquito Culex pipiens quinquefasciatus (Say) was placed in a screened cage and the pupae allowed to emerge into adults. Sugar cubes were then saturated with 1~0 milliliters (ml.) of an acetone solution containing 0.1 weight ~ of a test compound, and for a control, with the same amount of acetone alone. After the cubes dried, they were put into the screened cage. R~pellency was determined by the number of mosquito adults lighting and feeding on the sugar cubes, with observations being made daily for fi~e days after treatment. The num~er of days of complete 6 ~
repellency of mosquitos from the sugar cubes was recorded.
Housefly Repellency Test:
One hundred (100) houseflies of the species Musca domestica (L.) of mixed sexes were placed in test cages. In each cage was placed a sugar cube saturated with 1.0 ml. of acetone containing 1 weight % of the test compound. The cubes were dried and weighed before being placed in the cages. Each cage also contained a water-saturated cotton plug to provide moisture. The cages were placed on a turntable and rotated at 1.5 revolutions per minute to keep the flies randomly distri-buted inside the cages. After 48 hours, the flies in each were anesthetized with carbon dioxide. The sugar cubes were removed and reweighed and the percentage weight loss (due to consumption by the flies) was recorded. A repellency ratio, calculated as the ~ weight loss of the treated sugar cube divided by the percent weight loss of controlled sugar cube treated with acetone only, was calculated. The lower the repellency ratio, the greater the repellency of the test compound.
The following table IV provides the results of the test of the compounds previously listed for repellency for mosquitos (Mos) and houseflies (HF). In many cases the housefly data represents an average of several replications.
TABLE IV
HF
CompoundMos., days repellency No. repelled ratio 1 >5 0.48 2 >5 0.38 3 >5 0.43 4 >5 0.49 3 0.73 6 3 0.69 7 >5 0.42 i'57~ ~
Compound Mos., days HF
No. repelled repellency _ ratio 8 4 0.54 9 1 0.71 3 0.44 11 1 0.44 12 1 0.70 13 1 0.53 14 2 0.36 2-3 0.11 16 >5 0.40 17 >5 0.47 18 >5 0.54 19 4 0.47 3 0.47 ~ -SD 9-; ~ ~
Claims (4)
1. A compound having the formula
2. A method of repelling insects from a locus to be protected therefrom, comprising applying to said locus an effective insect repelling amount of a compound having the formula:
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
S.D. 3. A compound having the formula in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
S.D. 4. The compound of Claim S.D. 3 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 5. The compound of Claim S.D. 3 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 6. The compound of Claim S.D. 3 wherein R is -CH2-CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 7. The compound of Claim S.D. 3 wherein R is -CH=CHCH3, n is 3 and the ester moiety is substituted at the
CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE
S.D. 3. A compound having the formula in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
S.D. 4. The compound of Claim S.D. 3 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 5. The compound of Claim S.D. 3 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 6. The compound of Claim S.D. 3 wherein R is -CH2-CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 7. The compound of Claim S.D. 3 wherein R is -CH=CHCH3, n is 3 and the ester moiety is substituted at the
3-position on the pyridine ring.
S.D. 8. The compound of Claim S.D. 3 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 9. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 10. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 11. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 12. The compound of Claim S.D. 3 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 13. The compound of Claim S.D. 3 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 14. The compound of Claim S.D. 3 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 15. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 16. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 17. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the
S.D. 8. The compound of Claim S.D. 3 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 9. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 10. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 11. The compound of Claim S.D. 3 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 12. The compound of Claim S.D. 3 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 13. The compound of Claim S.D. 3 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 14. The compound of Claim S.D. 3 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 15. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 16. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 17. The compound of Claim S.D. 3 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the
4-position on the pyridine ring.
S.D. 18. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 19. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 20. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 21. The compound of Claim S.D. 3 wherein R is -C(CH3)=CH2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 22. The compound of Claim S.D. 3 wherein R is -CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 23. A method of repelling insects from a locus to be protected therefrom, comprising applying to said locus an effective insect repelling amount of a compound having the formula in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
S.D. 24. A method according to Claim S.D. 23 in which the compound is applied in an amount effective to repel mosquitos.
S.D. 25. The method according to Claim S.D. 23 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 26. The method according to Claim S.D. 23 wherein R is CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 27. The method according to Claim S.D. 23 wherein R is -CH2-CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 28. The method according to Claim S.D. 23 wherein R is -CH=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 29. The method according to Claim S.D. 23 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 30. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 31. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 32. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 33. The method according to Claim S.D. 23 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 34. The method according to Claim S.D. 23 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 35. The method according to Claim S.D. 23 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 36. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 37. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 38. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 39. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 40. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 41. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 42. The method according to Claim S.D. 23 wherein R is -C(CH3)=CH2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 43. The method according co Claim S.D. 23 wherein R is -CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 18. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 19. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 20. The compound of Claim S.D. 3 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 21. The compound of Claim S.D. 3 wherein R is -C(CH3)=CH2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 22. The compound of Claim S.D. 3 wherein R is -CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 23. A method of repelling insects from a locus to be protected therefrom, comprising applying to said locus an effective insect repelling amount of a compound having the formula in which R is C3-C5 alkyl or C3-C5 alkenyl and n is an integer from 1 to 3.
S.D. 24. A method according to Claim S.D. 23 in which the compound is applied in an amount effective to repel mosquitos.
S.D. 25. The method according to Claim S.D. 23 wherein R is -CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 26. The method according to Claim S.D. 23 wherein R is CH=C(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 27. The method according to Claim S.D. 23 wherein R is -CH2-CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 28. The method according to Claim S.D. 23 wherein R is -CH=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 29. The method according to Claim S.D. 23 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 30. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 31. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 32. The method according to Claim S.D. 23 wherein R is -CH(CH3)CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 33. The method according to Claim S.D. 23 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 34. The method according to Claim S.D. 23 wherein R is -CH2CH(CH3)2, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 35. The method according to Claim S.D. 23 wherein R is -CH2CH2CH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 36. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 37. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 38. The method according to Claim S.D. 23 wherein R is -C(CH3)3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 39. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 2-position on the pyridine ring.
S.D. 40. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 41. The method according to Claim S.D. 23 wherein R is -C(CH3)=CHCH3, n is 3 and the ester moiety is substituted at the 4-position on the pyridine ring.
S.D. 42. The method according to Claim S.D. 23 wherein R is -C(CH3)=CH2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
S.D. 43. The method according co Claim S.D. 23 wherein R is -CH(CH3)2, n is 3 and the ester moiety is substituted at the 3-position on the pyridine ring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA338,929A CA1125764A (en) | 1979-11-01 | 1979-11-01 | Insect repellent compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA338,929A CA1125764A (en) | 1979-11-01 | 1979-11-01 | Insect repellent compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1125764A true CA1125764A (en) | 1982-06-15 |
Family
ID=4115507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA338,929A Expired CA1125764A (en) | 1979-11-01 | 1979-11-01 | Insect repellent compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1125764A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579850A (en) * | 1985-02-25 | 1986-04-01 | Stauffer Chemical Company | Halogenated esters of pyridine alkanols and their amine salts as insect repellents |
| US8691340B2 (en) | 2008-12-31 | 2014-04-08 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
| US9878464B1 (en) | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
-
1979
- 1979-11-01 CA CA338,929A patent/CA1125764A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579850A (en) * | 1985-02-25 | 1986-04-01 | Stauffer Chemical Company | Halogenated esters of pyridine alkanols and their amine salts as insect repellents |
| US8691340B2 (en) | 2008-12-31 | 2014-04-08 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
| US9314938B2 (en) | 2008-12-31 | 2016-04-19 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
| US9878464B1 (en) | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
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