PL156651B1 - Method of obtaining novel aromatic ethers-derivatives of camphene - Google Patents

Abstract

1. Method of producing new camphene derivatives aromatic ethers with general formula 1, where R signifies either p- methylphenoxy, p-ethylphenoxy, p-chlorophenoxy, p-bromophenoxy or 3,4-methylendioxyphenoxy group; is characterised in that 3-methylo-5-/8-camphenylo/-1-penten-3-ol, obtained in reaction between 4-/8camphenylo/-2-butanon and vinyl magnesium bromide in tetrahydrofurane, is subjected to re-grouping by phosphor tribromide in mixture of n-pentane, diethyl ether and pyridine, then re-grouped product, in the form of 1-bromo-3-methylo-5-/8-camphenylo/3-pentone, is subjected to reaction with potassium phenolate with general formula 2, with R signifying the above meaning, in organic solvent environment and boiling temperature of the reaction mixture.<IMAGE>

Description

The invention relates to a process for the preparation of new camphene er-matic-h-derivative-h ethers of the general formula I, in which R is p-Ttylphynoxyl, p-tylphenoxyl, p-broocphenokyl, p-chlorophenoxy or 3,4-oβtyl-nodiacyphenoxy.

The compounds according to the invention are analogs of the intestinal insect hormones and are useful as insecticides.

The method according to the invention consists in that 3-Mtyl-5- / 8-camoonyl / -1-pβι: tθn-3-ol, obtained as a result of 4- (S-camphenyl - / - 2-bιltanone with vinyl magnesium bromide in furun, it undergoes the rearrangement of ^^ μι-Ιθο phosphorus in a mixture of n-pentane, diethyl ether and pyridine. The rearrangement product in the form of 1-bΓomo ---- lotyl - / 8-kaimonyl / -2-pentene is subjected to potassium Ο ^^ μο of the general formula 2, where R has the above meaning, in an organic solvent medium at 1 temperature the boiling point of the reactionary oil. Acetone is preferably used as the organic solvent.

The subject process is distinguished by the simplicity of carrying out the individual reaction steps and their satisfactory yields.

The process of the invention is illustrated by the following examples.

Example 1 To a reaction flask containing a solution of vinyl-orgilzium bromide, cooled to 279 K, prepared from 6.3 g of imgnesium and 0.0211 dm of vinyl bromide in 0.2 dm of tetrahydrofuran, 37.0 g of 4% 4% were added dropwise. 8 ^ - ^ k ^ 2 ^ mfan ^^ o / - ^ 2-t ^ ut ^^ nonu. The mixture is stirred at room temperature for 48 hours, then cooled to 273 K, and then a 20% ammonium chloride solution is poured into the mixture of lactic acid to dissolve the precipitate of magnesium salts. The organic layer was separated and the aqueous layer was extracted with ether diltyOo · s _l, m · combined organi-frien ds and various solutions were washed with water and dried over anhydrous siarozanem mignezowym. After distilling off the solvents, the residue was fractionated under reduced glare, obtaining 27.0 g (64.2% of theory) of 3-olyl-5- (8-cam ^, θnyl) -1-β-ntβn-3-ol with a boiling point of 389 -393 K under a pressure of 0.9 hPa and a refractive index of n = 1.4981. Then 10.0 g of 3-μ1υ1ο-5- / / 8-ka ^o 'ony ^l o / -I1-pentene-3-o ^{l at 0,} 1 ⁸ da? pentanes ^0, 12 ^ e ^ ru ^ di-ethyl ester and ^0, 32 °° da 'teojpratury pyridine cooled to 268 K, is added dropwise phosphorus 0,003- dn trbbromku dissolved in 0.070 liter of ether diltylowlg-. The reaction mixture was kept at this temperature for ² dB ^{and g-ny,} poured into a ^0, 27 and dm ^ water and extracted with n ^ ntanem. The combined extracts are washed with biconcons-% sulfuric acid solution, water, saturated sodium bicarbonate solution and again with water. After drying over anhydrous magnesium sulfosate, the solvent was obtained under reduced pressure, yielding 11 g / 90.5% of theoretical output (crude 1-broIoo-3-ethyl --- (8-kaI] monyl) -I2- peitenu. In the butt

156 651 of the reaction mixture a solution of Ί. G of p-cresol in 0.015 ^d ®? The aoetone was 4 g of potassium carbonate and the salt was heated for 0.5 hours under reflux.

Then 2.0 g of 1-bromo-33iM-yl-5- (8-camenyl) -2-penteeu are added and the mixture is stirred at reflux for 15 hours. After this time, the reaction mixture was poured ai ^{E D} of ^{0.050 dm} ^ ekatrahuja water and n-pentane. The combined EKA Rakt ^{t y} ^ ^ RAS important to water ^± 0 10% sodium hydroxide liquors 1 again with water. After drying over anhydrous sodium sulfonate, the n-pentane was distilled off and the residue was fractionated in vacuo to give 1.5 g of 1.5 g (^ 7% in theoretical / 3-methyl-1- / p-Mtylphenoxy / -53 / 8-kaffifsny3A-ppentane with a boiling point of 433-437 K under a glare of 2.7 hPa and a re-allocation factor n ²⁰ »1.5315.

¹ H NMR spectrum / CDCl ^ ^{TM /} CT p ^{p 0} ms, 86 s / 3H / ^0, 89 s / 3ΗΛ 1 ^»0 1.75 m / ^1OH; CH ° in position

C-3: 1.60 cT - narrow mltiplet /, 1.99 m / 4H /, 2.15 s / 3iH /, 2.78 m / 1H /, 4.39 dm / 2H /,

4.78 m (18), 5.44 m (1H), 6.63-7.15 m (4H).

IR / film / among others .: 2900, 167 °, 161O, 158 (0, 1505, 145 °, 137 °, 1290, 1170, 1100, 10 (05, 810, 800 cm ¹ .

Example II. 1.2 g of p-ethylphenol 14 g of K are stirred in the reaction flask₂° 0 in^0,015 dm⁰ acetone^and everything is warmed up by strabismus^0.5 hourjr^pabout^d cooling tower. 2.0 g of 1-bromoc-33-β-yl-C5- (8-ka-mfιnlo) -2-panthene prepared as in Example 1 are then added. Following further steps as in Example 1, 1.6 g / 70.% of the theoretical yield / 1- / 1-ethylphnoxy / -3-mβ-ethyl-5- / 3-cavpentene O ° / -2l pentene is obtained, boiling point 436-440 K at a pressure of 1.3 hPa and a refractive index n «1.5326.

Wid ^m ° ¹ H NMR / CDD ^-, TM / ^c ppms 0 "9 ⁶ s / 3H / ^0, 94 and / 3HA 1.19 t / 3H, J = 7Hz /, 1,05-2,50 YU6 H; CH3 as calculated from C-3: C-1.71), 2.89 m (1H), 2.580 (2H); J = 7Hz), 4.86 tm (14), 5.50 tm (1H), 6.71-7.23 m (4H).

IR / fiW, among others: 2800, 1680, 1610, 1580, 145 °, 1380, 129 °, 123 °, 1180, 1155, 1005, ⁸ 2d 80 ⁰ cm ¹ .

Example III. In the reaction flask are mixed 1.4 g of 3,4-mβtyOenodiokθyfθn ° ol and 4 ^g ^ ^{0 3} 0 °, 15 ° ^d m ³ of acetone and heated squint ^ ^{0, p} 5 hours of ^{d ±} Refrigeration Reply Address. 2.0 g of 1-bromo333-methyl-5- (8-camphnyl) -panthane prepared as in Example 1 are then added. Further as in Example 1, 1.5 g (60.6% of theoretical yield) (1- (3,4-methylenedioxyphenoxy) -3-thiO ° -5- (8-camphenyl)> 2-pentenyl at a temperature of boiling point 479-483 K at a pressure of 1.3 hPa and the coefficient of fracture n = 1.5442.

¹ H NMR spectrum / CDCl ^- TM / c ^pp m: ^0, 94 s / ^3H / 0.9 ⁶ s / 3HA 1,08-1,90 m / 1 ° Hj CH ^- w ^p ozycji 0-3 : C = 1.67. 2.09 m (4H), 2.88 m (1H), 4.40 dm (2H), 4.84 tm (1H), 5.43 tm (1H),

5.84 a (2H), 6.23-6.71 m (38).

IR / fim / among others: 290 (0, 1670, 1620, 1605, 1490, 1380, 1350, 1240, 1120, 1090,

1040 ^, 1005, 930 ^, 835 ^, 8 ^ 780 ohm ¹ .

Example IV. 1.3 g of p-chlorolene and 4.0 g of O are mixed in the reaction flask

K-CO ^- in 0.015 dm of acetone and the whole is heated for 0.5 hours under reflux. Then 2.0 g of 1-bromoo3-3® tydo-5- / 8-camθnyido / 32-lentenl, prepared as in Example 1, are added, further as in Example 1, 1.7 g / T1% of theoretical yield are obtained / 1- / p-ehlorofθnokjy / -3-methyl ° -5-83-aamphenyl ° / -2-pβntene with a boiling point of 445-449 K at a pressure of βm 1.3 hPa and a refractive index n = 1.5407.

¹ H NMR (CDCl ^- , TM) spectrum: 0.90 s (3H), 0.91 s (3H), 1.00 µ, 88 m (10H; CH ^- in the C-3 position ^: C = 1.61 //, 2.03 m (4H), 2.78 m (1H), 4.35 dm / 2, 4.78 tm (1H), 5 , 32 tm (1H), 6.63-7.25 m (4H).

IR / FIM / copper ^y others: 167 °, 159 ^5, 149 ^ 1370, ^1230, 1165, 1090, 10 no ^5, 820 cm ^-1.

EXAMPLE 5 1.7 g of 1-bromophenol and 4 g of KgO are mixed in a reaction flask at 0.015 dm^P. ^ etom and ° el ° ś^ex he warms himself up;^0.5 hours ^^pfrom ch^dThread^and feedback.

2.0 g of 1-bromo-3-methyl-5- (8-camβnyl) 32-lentene, prepared as in Example 1, are then added. Proceeding as in Example 1, 1.8 g (66% of theory) are obtained. / l-mo br ° ° ° βno EYD-3-meylo-5/8-kamfenylo / -2-pentane having a boiling point of 475-479 ^{K p d} ^ m of difference of 1.3 mbar and a refractive refralccji ²⁰ η 1 n "55 ⁰ 4.

156 651

¹ H NMR spectrum (CDCl? TM) (1 0.95 β (3H), 0.96e (3H), 0.88-1.92 B (10H {CHj in position. C-3s CT- 1.0 /, 2.10 m / 4H /, 2.88 m / 1H /, 4.46 da / 2H /, 4.85 m / 1H /, 5.44tm / 1H /, 6 , 75-7.40 m (4H).

IR / film / between issymi: ^{1670, 159O,} 14 ^ 1380, 1230, ^{1170, 1100, 1060,} 1000, 820 m ^{of -1.}

MODEL 1

RK

PATTERN 2

Department of Publishing of the UP RP. Circulation of 90 copies

Price PLN 5,000.

Claims (2)

Patent Claims 1. A method for the production of new ether <O aromatic camphene derivatives of general ozone 1, where R is p-methylphanoxyl, p-ethylphanoxy, p-chlorophenoxyl, p-bromophenoxyl, or 3,4-methylenedioxyOenoxyl, characterized in that 3-TOeyl-5- / 8-kaimonnli / -1 "penten-3-ol, obtained from the reaction of 4- (E - camPelyl) -2 - batanone with vinylmagnesium bromide in tetrahydrofuran, is subjected to tribromkieo phosphorus rearrangement in a mixture of n-pentane, dlethyl ether and pyridine, then the rearrangement product in the form of 1-bromo-inethyl-(8-fcaimornlo) -2-pentene is reacted with potassium phenate of general formula 2, where R is as defined above, in an organic solvent medium and at the temperature of the reaction mixture. 2. The method according to p. A process as claimed in claim 1, characterized in that acetone is preferably used as the organic solvent. * ♦ *