GB2143820A - 4-substituted-2-indanols - Google Patents

4-substituted-2-indanols Download PDF

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GB2143820A
GB2143820A GB08418419A GB8418419A GB2143820A GB 2143820 A GB2143820 A GB 2143820A GB 08418419 A GB08418419 A GB 08418419A GB 8418419 A GB8418419 A GB 8418419A GB 2143820 A GB2143820 A GB 2143820A
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phenyl
mole
stirred
mixture
water
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John Francis Engel
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FMC Corp
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FMC Corp
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Priority claimed from US06/042,372 external-priority patent/US4263319A/en
Priority claimed from GB8105715A external-priority patent/GB2093831B/en
Priority to GB8105715A priority Critical patent/GB2093831B/en
Priority to DE19813108203 priority patent/DE3108203A1/en
Priority to NL8101116A priority patent/NL8101116A/en
Priority to BE0/204079A priority patent/BE887884A/en
Priority to LU83208A priority patent/LU83208A1/en
Priority to FR8104776A priority patent/FR2501674A1/en
Priority to FR8121908A priority patent/FR2516917B1/en
Priority to GB08418419A priority patent/GB2143820B/en
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Abstract

Alcohols of the formula <IMAGE> in which R<1> is phenyl, optionally substituted with halogen or C1-4 alkyl are novel. They can be used in preparing insecticides of the pyrethroid type.

Description

4-Substituted-2-indanols The present invention is concerned with novel alcohols useful in preparing cyclopropanecarboxylate and related insecticides. The process for converting these alcohols to insecticides is described, and the novel insecticides so obtained are described and claimed, in the specification of our copending Application No.
8105715 (GB-2 093 831-A).
Pyrethrins, naturally occurring extracts of chrysanthemum flowers, have long been of interest as insecticides. Since elucidation of the structures of these compounds, synthesis efforts have been directed towards preparation of related compounds having enhanced insecticidal activity and improved stability toward air and light. Since a prerequisite for insecticidal activity of pyrethroids is the presence in one molecule of an appropriate acid residue and an appropriate alcohol residue, research has been directed towards novel acid and/or alcohol radicals. Noteworthy advances in the area of alcohol research were the discovery of 5-benzyl-3-furylmethyl alcohol, then of the more photostable 3-phenoxybenzyl alcohol. Similarly significant advances have been made in pyrethroid acid research.The commercial insecticide permethrin, the common name for 3-phenoxyphenylmethyl 3-(2,2-dichloroethenyl)-2, 2-dimethylcyclopropanecarboxylate, exemplifies use of both newer acid and alcohol residues in a single compound.
In this application, the term "lower" as applied to an aliphatic hydrocarbon group means having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. The term "halo" or "halogen" means bromine, chlorine or fluorine. The term "haloalkyl" means an alkyl group of 1 to 3 carbon atoms substituted with 1 or more halogen atoms. The term "insecticide" is used in its broadest sense, and includes compounds possessing activity against true insects, acarids, and other household, veterinary or crop pests of the phylum Arthropoda. These definitions are applicable throughout the specification and claims except where a contrary meaning is clearly indicated.
The novel compounds of this invention have the general formula
in which RI is phenyl, optionally substituted with halogen or C14 alkyl.
The novel alcohols of this invention may be prepared in a number of ways. The scheme below for 4phenyl-2-indanol is illustrative of methods by which the alcohols can be prepared.
This method of preparation (Method A) is described in yreater detail in Example 1. Other methods include the hydroboration/oxidation (Method B) and the epoxidation/reduction (Method C) of an appropriate indene, such as compound H in the scheme above. These additional methods are described in detail in Examples 2 and 3 respectively.
The examples, which follow, illustrate preparation of the novel alcohols in accordance with the general method described above. In the examples all temperatures are in degrees centigrade, all pressures are in Pascals, and reduced pressure for concentrations of liquid was produced by a water aspirator unless otherwise specified.
Example 1 Synthesis of 4-phenyl-2-indanol (Method Aj A. Preparation of2-(bromomethyllbiphenyl A stirred solution of 58.9 g (0.319 mole) of 2-biphenylmethanol and 6 ml of concentrated sulfuric acid in 67 ml of aqueous 48% hydrobromic acid was heated under reflux for 5 hours. The reaction mixture was cooled to ambient temperature and poured into ice-water, and the resulting mixture was extracted with three 100-ml portions of diethyl ether. The combined extracts were washed with 50 ml of a satu rated aqueous solution of sodium bicarbonate, then with 50 ml of water. The organic layer was dried with magnesium sulfate and filtered, and the filtrate concentrated under reduced pressure to give 76.8 g of 2-(bromomethyl)biphenyl as a residual oil.The nmr and and ir spectra were consistent with the pro posed structure.
B. Preparation of diethyl 62-phenylbenzylJmalonate A stirred mixture of 12.5 g (0.54 mole) of sodium hydride (25 g of a 50% dispersion in mineral oil) in 300 ml of dimethylformamide and 900 ml of benzene was placed under a nitrogen atmosphere and cooled to 0 C. To this mixture, 104.3 g (0.9 mole) of diethyl malonate was added dropwise during a 5 minute period and the mixture was stirred until hydrogen evolution ceased. 2-(Bromomethyl)biphenyl (117 g, 0.47 mole) was then added at OOC. Upon complete addition the reaction mixture was stirred at 0 C for 30 minutes, then was allowed to warm to ambient temperature with stirring for one hour.The reaction mixture was poured into 500 ml of water, the layers separated, and the aqueous layer washed with two portions of 250 ml each of diethyl ether. The organic layer was combined with the ether washings, and the whole was washed with one portion of 500 ml of aqueous 5% hydrochloric acid, one portion of 500 ml of water, one portion of 300 ml of a solution saturated with sodium bicarbonate, and finally, one portion of 500 ml of water. The organic layer was dried with magnesium sulfate, filtered and the filtrate concentrated under reduced pressure to an oil residue. The oil was distilled under reduced pressure to give 149.0 g of diethyl (2-phenylbenzyl)malonate; b.p. 175-180"C/107-120 Pa. The nmr spectrum was consistent with the proposed structure.
C. Preparation of (2-phenylbenzyl)malonic acid A stirred solution of 149.0 g (0.456 mole) of diethyl (2-phenylbenzyl)malonate and 56.1 g (1.0 mole) of potassium hydroxide in 50 ml of water and 500 ml of ethanol was heated under reflux for 3 hours. The reaction mixture was allowed to cool to ambient temperature and stand for 60 hours. The ethanol was removed by distillation and the residue slurried in 400 ml of water. The mixture was extracted with one portion of 250 ml of diethyl ether. The aqueous phase was separated and acidified with concentrated hydrochloric acid, then extracted with two portions of 250 ml each of diethyl ether. The two extracts of the acidified aqueous phase were combined, dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to give (2-phenylbenzyl)malonic acid as a pale yellow oil.The oil was used directly in the next step of this reaction sequence.
D. Preparation of3-(2-hiphenyl)propionicacid A solution of 124.2 g (0.46 mole) of the oil from C of this Example in 500 ml of water was heated under reflux for 16 hours. The reaction mixture was cooled, and the product was collected by filtration to give, after recrystallization from ethanol-water, 92.9 g of 3-(2-biphenyl)propionic acid. The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C,5H1402: C 79.62, H 6.24 Found: C 79.84, H 5.98 E. Preparation of 4-phenyl- 1-indanone A solution of 92.9 g (0.41 mole) of 3-(2-biphenyl)propionic acid in 100 ml of thionyl chloride was stirred at ambient temperature for 16 hours. The excess thionyl chloride was removed by distillation followed by co-distillation with three 50 ml portions of benzene.
The residue was dissolved in 150 ml of benzene was added dropwise at 100C over 15 minutes to a stirred mixture of 71.0 (0.53 mole) of aluminum chloride in 900 ml of benzene. Upon complete addition the reaction mixture was stirred at 10"C for 110 minutes then poured into 1000 ml of ice-water and stirred until the ice melted. The aqueous phase was separated and extracted with two portions of 100 ml each of diethyl ether. The ether extracts and the organic phase were combined and washed with a 10% aqueous solution of sodium hydroxide, then with two portions of water. The combined extracts were dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure to give, as a brown crystalline solid, 85.4 g of 4-phenyl-1-indanone, m.p. 85-90"C. The product was used without further purification.
A sample was recrystallized for analytical purposes. The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C,5H20O: C 86.50, H 5.81 Found: C 86.63, H 5.74.
F. Preparation of 4-phenyl- 1-indanol To a stirred solution of 20.8 (0.10 mole) of 4-phenyl-1-indanone in 150 ml of ethanol was added portionwise 2.0 g (0.06 mole) of sodium borohydride. During the addition the reaction temperature rose to 33"C. Upon complete addition the reaction mixture was allowed to cool to ambient temperature and was stirred for 16 hours. The reaction mixture was mixed in water and concentrated under reduced pressure.
A precipitate, which developed during concentration of the aqueous solution, was collected, dried, then recrystallized from toluene-hexane to give 17.3 g of 4-phenyl-1-indanol; m.p. 80.5-81.5"C. The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for ClsH14O: C 85.68, H 6.71 Found: C 85.63, H 6.70.
G. Preparation of 7-phenyl-1H-indene A stirred solution of 16.7 g (0.08 mole) of 4-phenyl-1-indanol and 0.1 g of p-toluenesulfonic acid in 180 ml of benzene was heated under reflux for one hour as by-product water was collected in a Dean-Stark trap. The reaction mixture was washed with two portions of 50 ml of a 5% aqueous solution of sodium bicarbonate, then with one portion of 50 ml of water. The organic phase was dried with magnesium sulfate, filtered, and the filtrate concentrated under reduced pressure, keeping the temperature under 50"C., to give 14.8 g of 7-phenyl-1H-indene. The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C,5H,2: C 93.71, H 6.29 Found: C 93.47, H 6.31.
H. Preparation of 4-phenyl-2-indanone A stirred solution of 53.2 ml of formic acid and 10.5 ml of 30% hydrogen peroxide was heated to 35"C, and 14.5 g (0.075 mole) of 7-phenyl-1H-indene was added dropwise causing the reaction mixture temperature to rise to 41"C. Upon complete addition the reaction mixture was allowed to cool to ambient temperature and was stirred for 16 hours. The reaction mixture was concentrated under reduced pressure to give a residual semi-solid which was subjected to steam distillation in the presence of aqueous dilute sulfuric acid. The steam distillates were filtered to give 1.84 g of 4-phenyl-2-indanone; m.p. 133-136"C.
The nmr and the ir spectra were consistent with the proposed structure.
I. Preparation of 4-phenyl-2-indanone To a stirred mixture of 0.30 g (0.0014 mole) of 4-phenyl-2-indanone in 10 ml of ethanol was added portionwise 0.03 g (0.0008 mole) of sodium borohydride. The resulting yellow colored solution was stirred at ambient temperature for 1.5 hours, then concentrated, and 50 ml of water was added. The mixture was extracted with two portions of 50 ml each of diethyl ether. The extracts were combined, dried with sodium sulfate, filtered and the filtrate concentrated under reduced pressure to give, after recrystallization from hexane, 0.13 g of 4-phenyl-2-indanol. The nmr and ir spectra were consistent with the proposed structure.
Example 2 Synthesis of 4-phenyl-2-indanol (Method B) Under a dry argon atmosphere, a stirred solution of 32.9 g (0.391 mole) of 2,3-dimethyl-2-butene in 250 ml of tetrahydrofuran was cooled to 0 to -5 C. To this was added during 30 minutes 372.5 ml of a 1.05M solution of borane (0.391 mole) in tetrahydrofuran, and the mixture was stirred for 1 3/4 hours. A solution of 168.2 g (0.355 mole) of 7-phenyl-1H-indene (which may be prepared as in Example 1G) in 250 ml of tetrahydrofuran was added over 30 minutes with continued cooling, and the mixture was stirred for 1 1/2 hours. The mixture was cooled to -15 C, and 71 ml of water was added over 30 minutes.A 3N aqueous solution of sodium hydroxide (213 ml) and 213 ml of a 30% aqueous solution of hydrogen peroxide were added dropwise in sequence, and the mixture was stirred at 0" for 30 minutes, then filtered through a pad of diatomaceous earth. The aqueous phase of the two-phase filtrate was separated and extracted with diethyl ether. The extracts were combined with the organic phase of the filtrate, and the whole was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous potassium carbonate, and filtered. The filtrate was concentrated under reduced pressure to give 79.6 g of a yellow-green oil, which was shown by gas chromatographic analysis to contain 90% 4-phenyl-2-indanol and 8.4% 4-phenyl-1-indanol.
A solution of the 79.6 g of oil and 0.1 g of p-toluenesulfonic acid in 350 ml of toluene was heated at reflux for 15-20 minutes during which a toluene/water azeotrope collected in a Dean-Stark trap. The mixture was cooled, placed on a silica gel chromatography column, and eluted first with toluene, then with 1:1 toluene/ethyl acetate. Appropriate fractions were combined and concentrated to give, after crystallization from toluene, 44.5 g of 4-phenyl-2-indanol, mp 71" -73"C. The nmr spectrum was consistent with the proposed structure.
Example 3 Synthesis of 4-phenyl-2-indanol (Method C) A. Preparation of 1,2-epoxy-4-phenylindane A stirred solution of 47.5 g (0.234 mole) of m-chloroperbenzoic acid (85- purity) in 390 ml of chloroform was cooled to 0"C. To this was added dropwise a solution of 45 g (0.234 mole) of 7-phenyl-1H-indene (which may be prepared as in Example 1G) in 110 ml of chloroform. After complete addition, the mixture was stirred for 2 1/2 hours, then was allowed to stand for 21 hours at 0"C. With the temperature in the range of 0" -5 C, 100 ml of a 10% aqueous solution of sodium hydroxide, then 50 ml of a 10% aqueous solution of sodium sulfate, were added dropwise with stirring. After complete addition the two-phase mixture was stirred for 30 minutes.The organic phase was separated, washed first with a dilute aqueous solution of sodium bicarbonate, then with water, dried over anhydrous sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to give 47.7 g of 1,2-epoxy-4-phenylindane as a pale yellow oil, 97% purity by gas chromatographic analysis.
B. Preparation of 4-phenyl-2-fndanol Under a dry argon atmosphere, a stirred solution of 9 g (0.067 mole) of aluminum chloride in 225 ml of anhydrous diethyl ether was cooled to 0"C. To this was added portionwise 9.4 g (0.245 mole) of lithium aluminum hydride. The cooling bath was removed, and the mixture stirred for 15 minutes. With the temperature being maintained at 25"C, a solution of 47.7 g (0.229 mole) of 1,2-epoxy-4-phenylindane in 175 ml of anydrous diethyl ether was added dropwise. After complete addition, the mixture was heated at reflux for 18 hours, then cooled to 0"C. Water and an aqueous solution of sodium hydroxide were added to decompose the excess lithium aluminum hydride, and the mixture was filtered. The filter cake was washed with diethyl ether, and the filtrate and washes were combined and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate concentrated under reduced pressure to give an oil. The oil was subjected to column chromatography on silica gel, eluting with 98:2 toluene/ethyl acetate followed by 90:10 toluene/ethyl acetate to give 62.1 g of 4-phenyl-2-indanol, mp 72" -76"C. The nmr spectrum was consistent with the proposed structure.

Claims (3)

1. Acompound oftheformula
in which Ri is phenyl, optionally substituted with halogen or C1 4 alkyl.
2. 4-Phenyl-2-indanol.
3. A compound as claimed in Claim 1 when prepared by a method substantially as hereinbefore described in any one of Examples 1 to 3.
GB08418419A 1979-05-24 1984-07-19 4-substituted-2-indanols Expired GB2143820B (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
GB8105715A GB2093831B (en) 1981-02-24 1981-02-24 4-substituted-2-indanols and insecticidal ester derivatives
DE19813108203 DE3108203A1 (en) 1981-02-24 1981-03-04 4-substituted 2-indanols, insecticidal ester derivatives thereof, compositions containing them, and their use
NL8101116A NL8101116A (en) 1981-02-24 1981-03-09 4-SUBSTITUTED-INDAAN-2-OLES AND INSECTICIDE ESTER DERIVATIVES.
BE0/204079A BE887884A (en) 1981-02-24 1981-03-10 NOVEL 4-SUBSTITUTED 2-INDANOLS, DERIVATIVE ESTERS, AND INSECTICIDE COMPOSITION CONTAINING THESE ESTHERS
LU83208A LU83208A1 (en) 1981-02-24 1981-03-10 NOVEL 4-SUBSTITUTED 2-INDANOLS, DERIVATIVE ESTERS THEREOF, INSECTICIDE COMPOSITION CONTAINING SUCH ESTERS, AND METHODS FOR CONTROLLING INSECTS USING THE SAME
FR8104776A FR2501674A1 (en) 1981-02-24 1981-03-10 NOVEL ESTERS DERIVING FROM 2-INDANOLS-4-SUBSTITUTED, PROCESS FOR PREPARING THESE ESTERS, INSECTICIDAL COMPOSITIONS CONTAINING THESE ESTERS, AND METHOD OF CONTROLLING INSECTS USING THE SAME
FR8121908A FR2516917B1 (en) 1981-02-24 1981-11-23 NEW SUBSTITUTED 2-INDANOLS-4 AND PREPARATION OF CORRESPONDING ESTERS
GB08418419A GB2143820B (en) 1979-05-24 1984-07-19 4-substituted-2-indanols

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US06/042,372 US4263319A (en) 1978-01-20 1979-05-24 4-Substituted-2-indanol insecticidal ester derivatives
GB8105715A GB2093831B (en) 1981-02-24 1981-02-24 4-substituted-2-indanols and insecticidal ester derivatives
DE19813108203 DE3108203A1 (en) 1981-02-24 1981-03-04 4-substituted 2-indanols, insecticidal ester derivatives thereof, compositions containing them, and their use
NL8101116A NL8101116A (en) 1981-02-24 1981-03-09 4-SUBSTITUTED-INDAAN-2-OLES AND INSECTICIDE ESTER DERIVATIVES.
BE0/204079A BE887884A (en) 1981-02-24 1981-03-10 NOVEL 4-SUBSTITUTED 2-INDANOLS, DERIVATIVE ESTERS, AND INSECTICIDE COMPOSITION CONTAINING THESE ESTHERS
LU83208A LU83208A1 (en) 1981-02-24 1981-03-10 NOVEL 4-SUBSTITUTED 2-INDANOLS, DERIVATIVE ESTERS THEREOF, INSECTICIDE COMPOSITION CONTAINING SUCH ESTERS, AND METHODS FOR CONTROLLING INSECTS USING THE SAME
FR8104776A FR2501674A1 (en) 1981-02-24 1981-03-10 NOVEL ESTERS DERIVING FROM 2-INDANOLS-4-SUBSTITUTED, PROCESS FOR PREPARING THESE ESTERS, INSECTICIDAL COMPOSITIONS CONTAINING THESE ESTERS, AND METHOD OF CONTROLLING INSECTS USING THE SAME
FR8121908A FR2516917B1 (en) 1981-02-24 1981-11-23 NEW SUBSTITUTED 2-INDANOLS-4 AND PREPARATION OF CORRESPONDING ESTERS
GB08418419A GB2143820B (en) 1979-05-24 1984-07-19 4-substituted-2-indanols

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GB8418419D0 GB8418419D0 (en) 1984-08-22
GB2143820A true GB2143820A (en) 1985-02-20
GB2143820B GB2143820B (en) 1985-10-02

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1982002321A1 (en) * 1980-12-31 1982-07-22 Corp Fmc (+)-4-substituted-2-indanols and insecticidal ester derivatives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1982002321A1 (en) * 1980-12-31 1982-07-22 Corp Fmc (+)-4-substituted-2-indanols and insecticidal ester derivatives

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GB2143820B (en) 1985-10-02

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