FR2542734A1 - PROCESS FOR THE PREPARATION OF (E) -3,7-DIMETHYL-2,7-OCTADIEN-1-YLE PROPANOATE - Google Patents

Abstract

PROCESS FOR PREPARING THE (E) -3,7-DIMETHYL-2,7-OCTADIEN-1-YLE PROPANOATE OF FORMULA I, BY REACTING (E) -3,7-DIMETHYL-2,6-OCTADIEN-1 -OL OF FORMULA II: EITHER WITH A PROPIONATING AGENT SUCH AS PROPANOIC CHLORIDE, THEN A TERTIARY BUTYL HYPOHALOGENITY; - FIRST WITH HYPOHALOGENITE, THEN WITH A REDUCING AGENT AND FINALLY WITH THE PROPIONATION AGENT; EITHER FIRST WITH AN ACYLANT AGENT, THEN WITH HALOGENITE AND FINALLY WITH THE PROPIONATION AGENT. APPLICATION OF THIS COMPOUND OF FORMULA I ESPECIALLY FOR THE TREATMENT OF FRUIT TREES.

Description

The present invention relates to a new

  process for the preparation of the (E) -3,7-propanoate

dimethyl-2,7-octadien-1-yl.

  It is known that (E) -3,7-dimethylpropanoate

  2,7-octadien-1-yl represented by formula (I) below: ## STR2 ## produces a substantially strong stimulation reaction on the

  louse of male San Jose (Quadraspidiotus perniciosus, Comstock).

  The San José louse is a serious pest that spreads everywhere, attacking all parts of the host trees, including fruits. Serious and widespread infections, especially fruit trees (such as apple and pear trees) give this pest economic importance. multiplies rapidly and due to the short reproductive period (three generations per year),

  new infections spread quickly.

  Roelofs et al., JG Gieselman, R E Rice, R A Jones and W L Roelofs: J Chem Ecol, 5, 891 (1979) 7 have demonstrated that the pheromone of this pest consists of

  to a 2: 3 mixture of (Z) -3,7-dimethyl-2,7-propanoate

  octadien-1-yl and 7-methyl-3-methylene propanoate

  7-octen-1-yl A biotitration in sefre and field tests have shown that either the two compounds independently, or their mixture, produce a strong stimulating reaction on

  As a result, these derivatives may

  may be applied to combat this pest, to indicate the beginning of swarming or to obtain information

concerning his appearance.

  Anderson and Henrick showed that the stereo-

  isomer of the pheromone component, the propanoate of (E) -3,7-

  dimethyl-2,7-octadien-1-yl has a higher activity

  than that of natural sexual bait, so it can be applied profitably in plant protection

(US Patent No. 4,223,012).

  Henrick et al synthesized the compound of

  Formula (I) The starting material is 2-methyl-2-

  propen-1-ol The reaction of 2-methyl-2-propen-1-ol with triethyl orthoacetate in the presence of propanoic acid gave, via a Claisen type rearrangement, the 4- ethyl 4-pentanoate which is reduced

  with alumino-lithic hydride 4-methyl-4-pentene

  1-ol thus obtained is treated with the dibrominated compound of triphenylphosphine; the 5-bromo-2-methyl-1-pentene thus obtained is converted with lithium metal to the corresponding lithic compound, which is treated with cuprous iodide in the presence of tetramethylethylenediamine to give di (4-methyl-4-pentene) -1-yl) cuprous iodide The reaction of the latter compound with methyl 2-butynoate in ether gave (E) -3,7-dimethyl-2,7-octadienoate

  of methyl, which is reduced with diisobutyl hydride

  aluminum to obtain (E) -3,7-dimethyl-2,7-octadien-1-ol.

  Finally, an esterification with propanoic anhydride

  presence of pyridine provides the compound of formula (I).

  The above synthesis is not economically attractive because it involves a large number of inconvenient reaction steps and expensive reagents (triphenylphosphine, lithium metal, hydride).

of diisobutylaluminum).

  The present invention aims to provide a more economical process for the preparation of the compound

  of formula (I), which can be more easily achieved

on an industrial scale.

  In accordance with the present invention, the

  (E) -3,7-dimethyl-2,7-octadien-1-yl panoate of formula

  (I) can be prepared by a new simple process, including

  fewer reaction steps than the syn-

  known thesis, characterized in that: a) the (E) -3,7-dimethyl-2,6-octadien-1-ol represented by the following formula (II) is reacted:

-OH (II)

  with a propionation agent, preferably with chlorine

  The propanoate thus obtained is reacted with a tert-butyl hypohalogenite in a moderately polar solvent in the presence of a moderately acidic adsorbent, preferably with a Kieselgel. The halo compound of general formula (III below is reacted with thus obtained,

  o R represents a propionyl radical and Hal a halogen atom

  iogen, with a moderately reactive metal hydride in a polar solvent; or

  b) the (E) -3,7-dimethyl-2,6-octa-

  dien-1-ol with a ter-butyl hypohalogenite in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably kieselgel, the halo compound of the general formula (III), where R is an atom of hydroygene and Hal is as defined above, with a reducing agent, the alcohol thus obtained of formula (IV) below is reacted below:

- << '<OH (IV)

  with a propionation agent preferably propanoic chloride; or

  u) (E) -3,7-dimethyl-2,6-octadiene is converted into

  1-ol of formula (II) with an acylating agent, preferably acetic anhydride to a compound represented by the general formula (V) below:

-OR (V)

  wherein R is a C 14 acyl group, ter-butyl hypohalogenite, preferably tert-butyl hypochlorite, is added to the double bond of the 6-carbon atom thereof in an aprotic solvent , polar moderemen L, in the presence of a moderately acidic adsorbent,

  preferably Keselgel, the compound of general formula is reduced

  (R) thus obtained, wherein R is a C 5 acyl group and Hal is as defined above, with a metal hydride, the alcohol of formula (IV) is reacted as well as

  obtained with a propionation agent, preferably chlorine

  propanoic acid, and the compound of formula

(I) thus obtained.

  (E) -3,7-dimethyl-2,6-octadien-1-ol of

  The mule (II) used as the starting material is a cheap industrial product or can easily be obtained from natural sources.In accordance with variant (a) of the process of the present invention, the (E) 3,7-dimethyl- 2,6-octadien-1-ol is converted to the corresponding propanoyl which is then treated with a ter-butyl hypohalogenite This last

  The reaction is carried out in a moderately polar solvent.

  In this connection, hexane or homogeneous compounds may be used.

  of the latter (eg pentane, heptane).

  The halo compound obtained in this reaction is converted to the desired compound of formula (I), preferably with a borosodium hydride in a polar solvent. The solvent employed may be an alcohol, diethylformamide or dimethylsulfoxide. In accordance with variant b) of the process according to

  (E) -3,7-dimethyl-2,6-octadiene is reacted with

  1-ol with a ter-butyl hypohalogenite, preferably a hypochlorite, in the presence of a moderately acidic adsorbent, in a moderately polar solvent For this purpose, is preferably used hexane or homologous compounds thereof The halo compound of general formula (III) thus obtained is isolated from the reaction mixture and treated with a reducing agent, preferably with aluminio-lithic hydride. The alcohol of formula (IV) is separated from the reaction mixture and converted compound of formula (I) with a propionation agent, preferably chloride

propanoic.

  According to variant (c) of the process according to the present invention, (E) -3,7-dimethyl-2,6-octadien-1-ol is treated with an acylating agent, preferably acetic anhydride. (V) thus obtained is then

  treated with ter-butyl hypohalogenite, preferably

  In this connection, it is possible to use hexane or homologous compounds thereof. The reaction is carried out in the presence of a moderately acidic adsorbent. The compound of general formula (III) thus obtained is then reduced with

  a metal hydride, preferably the aluminum hydride

  The latter compound is then separated from the reaction mixture and converted into a compound.

  of formula (I) with the aid of a propionate agent

  preferably propanoic chloride.

  In addition to the foregoing, the invention

  tion still contains other provisions which will emerge

of the following description.

  The invention will be better understood by means of

  additional description which follows, which refers to

  examples of implementation of the method, object of the present invention. It should be understood, however, that these examples of implementation are given solely by way of illustration of the subject of the invention, of which they

  in no way constitutes a limitation.

Example 1

  at. Preparation of (E) -3,7-dimethyl-2,6-propaniloate

  octadien-1-yl - (V): R = CO-CH 2 -CH 3 - 7

  30.8 g (35 ml, 0.2 mole) of (E) -3,7-dimethlyl;

  2,6-octadien-1-ol and 23.1 g (32 ml, 0.23 mole) of triethyl

  are dissolved in 100 ml of anhydrous ether and 20.4 g (19 ml, 0.22 mole) of propanol chloride are added dropwise to the solution over one hour, with mixing and cooling at 0 ° C. The reaction mixture is stirred for an additional hour at 00 ° C., poured onto

  crushed ice; the upper ethereal phase is separated

  washed with water and saturated sodium chloride solution and dried over magnesium sulfate. The solution is filtered, the solvent is distilled off and

residue is distilled under vacuum.

  Yield: 39.0 g (86%) mp: 76-78 ° C / 0.3 mm, 40 Pa GC: t R = 5.40 (capillary column, 15 mx 0.2 mm, stationary phase, SE 54, t = -99, Packard chromatography

in capillary gas phase).

  TLC (TLC): Rf = 0.55 (petroleum ether-acetone 5: 0.1).

  IR (film): 1735 (CO), 1660 (CO), 1460, 1380, 1360, 1270, -11170, 1080, 1040, 1010, 940, 890 cm H NMR (CDCl3): 1.0 ( 3H, t, J = 7Hz, CH 3), 1.2-2.2 (13H, m 3 CH 3, 2CH 2), 2.3 (2H, q, J = 7Hz, COCH 2), 4.45 (2H, d, J = 7Hz, CH 2 -O), 4.95 (1H, m, C = CH at C 6), 5.25 (1H, t, J). = 6 Hz, C = CH to C 2)

  MS: M + 210 (<1), 136 (25), 121 (30), 107 (9), 93 (55),

  81 (13), 80 (17), 69 (100), 57 (63), 41 (75).

  b. Preparation of (E) -6-chloro-3,7-dimethyl-propanoate

  2,7-octadien-1-yl / - (III): R = CO-CH 2 -CH 3, Hal = Cl 7 A suspension of 30.0 g (0.142 mol) of propanoate of (E) -3.7 2,6-octadien-1-yl dimethyl and 60 g of Kieselgel 60 in anhydrous hexane is

  cooled to 0 ° C and 18.5 g (19.3 mlt 0.170 mol) of hypochlorite

  tert-butyl rite are added dropwise over a period of 5 minutes, with vigorous stirring. The mixture is

  first stirred at 0 C for half an hour, then at

  magnetizing temperature for one hour I 1 is filtered; the filtrate is washed successively with a 10% solution

  of sodium sulphite and 50 ml of water, then dried over

  Magnesium fate The solvent is distilled by vacuum distilla and the residue is purified by chromatography on

  column (Kieselgel 60, petroleum ether-acetone: 5: 0.1).

Yield: 28.5 g (82%)

  TLC (TLC): Rf = 0.36 (petroleum ether-acetone 5: 0.1).

  IR (film); 1735 (CO), 1670, 1645 (C = C), 1460, 1380, 1360, 1270, 1-70, 1085, 1010, 960, 905, 805 cm, 1270, 1170, 1085, 1010, 960, 905, 805 cm. NMR for H (CC 14): δ 1.1 (3H, t, J = 7Hz, CH 3), 1.8 (6H, br s 2 CH 3), 1.8-2.55 ( 6 H, m, 3 CH 2), 4.3 (2H, m, CH 2 -O), 4.85 (3H, m, CH 2 = C and CH-C 1), 5.25 (1 H, m, CH = C).

  MS: M 244 (<1), 172 (7), 170 (20), 135 (54), 121 (27),

  119 (56), 107 (28-), 93 (71), 91 (44), 81 (100),

  79 (52), 74 (72), 68 (67), 57 (81), 38 (24),

36 (77).

  c Preparation of (E) -3,7-dimethyl-2,7-propanoate

  octadien-1-yl 6.1 g (0.164 mol) of borosodium hydride and 12.7 g (0.098 mol) of lithium iodide are dissolved in ml of anhydrous dimethylformamide and a solution of

  20.0 g (0.082 mol) of (E) -6-chloro-3,7-dimethylpropanoate

  thyl-2,7-octadien-1-yl in 10 ml of dimethylformamide

  Anhydrous is added dropwise over 45 minutes.

  The reaction mixture is stirred at 60 ° C. for 3 hours, cooled, diluted with 500 ml of ether and poured into a cold solution containing 5% hydrochloric acid. The organic phase is separated, the aqueous phase is extracted three times with With a total amount of 20 ml of ether, the ethereal solutions are combined, washed successively with a saturated solution of sodium hydrogen carbonate and water and then dried over

  magnesium sulphate -The solvent is distilled off

  The main fraction (p: 76-85 ° C. / 0.3 mm, 40 Pa) is purified by evaporation and the residue is distilled under vacuum.

  column chromatography (Kieselgel 60, petroleum ether-

acetone 5: 0.1).

Yield: 6.5 g (37.7%).

TLC: Rf = 0.65 (benzene)

  GC: t R = 5.25 (capillary column, 15 m × 0.2 -im phase sta-

  tion, SE 54, t = 99 Packard chromatography

in capillary gas phase).

  IR (film): 1730 (CO), 1660, 1640 (C = C), 1450, 1380, 1355, 1260, 1200, 1160, 1075, 1000, 940, 890 cm NMR for 1 H (CDCl 3): 6 1 , (3H, t, J = 7Hz, CH), 1.7 (6H, m, 2CH 3), 1.7-2.3 (6H, m, 3CH 2), 2, 45 (2H, q, J = 7Hz, CH 2), 4.6 (2H, d, J = 7Hz, CH 2 -O), 4.65 (2H, m, CH 2 = C) , 5.35

(1H, m, C = CH).

  MS: M + 210 (<1), 136 (19), 121 (31), 107 (15), 93 (58),

  81 (29), 80 (19), 69 (58), 57 (70), 41 (100).

Example 2

  at. Preparation of (E) -6-chloro-3,7-dimethyl-2,7-octadiene

-1-O 01 (III): R = H, Hal = Cl 7.

  A suspension of 3.4 g (3.9 ml, 0.022 mol) of (E) -3,7-dimethyl-2,6-octadien-1-ol and 9.0 g of Kieselgel in 60 ml of anhydrous hexane is cooled to 0 ° C and 2.9 g (3 ml, 0.026 mole) of tert-butyl hypochlorite are added over 5 minutes. The Lionel reaction mixture is stirred for half an hour, filtered; the filtrate is diluted with 100 ml of ether and poured into 50 ml of a solution

  cold 10% sodium sulphite The higher ether phase

  The top is separated, washed with water, dried over magnesium sulfate, the solvent is distilled off in vacuo and the residue is purified by column chromatography.

  (Kieselgel 60, petroleum ether-acetone: 5: 1.5).

Yield: 2.65 g (63%).

  TLC (TLC): Rf = 0.38 (petroleum ether-acetone 5: 1).

  IR (film): 3300 (OH), 1670, 1645 (C = C), 1460, 1380, 1100, 1000, 905 cm NMR for 1H (CDCl3): δ 1.7 (3H, s, CH 3 in C 3), 1.8 (3 H, s, CH 3 in C 7), 2.05 (4H, mo, 2 CH 2), 4.15 (2H, d, J = 7 Hz , CH 2 -O), 4.7 (1H, m, CH-Cl), 4.95 (2H, d, J = 7Hz, CH 2 = C),

5.4 (1H, m, CH = C).

  S Mt M 188 (4), 152 (8), 135 (13), 134 (14), 109 (31)

  (30), 71 (94), 68 (100), 41 (81).

  b. Preparation of (E) -3,7-dimethyl-2,7-octadien-1-ol (Iv) A suspension of 1.85 g (0.048 mol) of alumino-iithium hydride in 50 ml of anhydrous tetrahydrofuran is

  added with a solution of 6.0 g (0.032 mol) of (E) -6-

  chloro-3,7-dimethyl-2,7-octadien-1-ol in 10 ml of tetracycline

  hydrofuran anhydrous in the space of half an hour and the

  The mixture is refluxed for 3 hours with stirring.

  Ethyl acetate and water are then added, the mixture is extracted three times with a total amount of 200 ml of ether; the ethereal phases are combined, washed with a saturated solution of sodium hydrogen carbonate and water, then dried over magnesium sulfate. The solvent is distilled off under vacuum and the residue is purified by column chromatography (Kieselgel 60,

petroleum ether-acetone 5: 0.1).

Yield: 3.04 g (62%).

  TLC (TLC): Rf = 0.47 (petroleum ether-acetone 5: 1).

  IR (film): 3300 (OH), 1670, 1650 (C = C), 1460, 1380, 1100, 005, 895 cm 1 NMR for H (CDCl 3): at 1.65-2 (12H, m.p. m, 2 CH 3, 3 CH 2), 4.05 (2H, d, J = 7Hz), 4.6 (2H, s,

CH 2 = C), 5.35 (1H, m, CH = C).

  MS: M 154 (4), 136 (16), 123 (16), 121 (20), 109 (17),

  107 (13), 96 (37), 83 (36), 81 (41), 71 (40),

69, 100), 55 (47), 41 (94).

  c Preparation of (E) -3 7-dimethyl-2-propanoate

octddien-l-yl (I)

  A solution of 2.4 g (0.015 mole) of 3.7-

  dimethyl-2,7-octadien-1-ol and 1.73 g (2.4 ml, 0.017 mol) triethylamine in 20 ml anhydrous ether is cooled to OC and 1.56 g (1.5 ml, 0.017 mol) of propanoic chloride is added dropwise over a period of one hour. The reaction mixture is stirred for one hour, then poured into ice water and extracted with ether; the ethereal solution is washed successively with water and saturated sodium chloride solution, then dried over magnesium sulphate. The solvent is distilled off and the residue is purified by column chromatography.

  (Kieselgel 60, 5: 0.1 petroleum ether-acetone).

  Yield: 1.87 g (57%), the product is identical to that

  which is prepared according to Example 1.

Example 3

  at. Preparation of (E) -3,7-dimethylacetate

  2,6-octadien-1-yl f V): R = COCH 3 J

  0 g (11.4 ml, 0.065 mole) of (E) -3.7-

  dimethyl-2,6-octadien-1-ol and 7.2 g (10 ml, 0.07 mole) of triethylamine are dissolved in 50 ml of anhydrous ether and 9 g (0.075 mole) of acetic chloride are added dropwise. The reaction mixture is stirred for an additional hour at 0 ° C. on a crushed ice; the upper ether phase is separated, the ethereal solution is washed successively with water and saturated sodium chloride solution and then dried over magnesium sulfate. The solvent is distilled off and

iesidu is distilled under vacuum.

Yield: 11.85 g (93%).

  mp 64-68 ° C / 0.3 mm, 40 Pa TLC: Rf = 0.72 (benzene) IR (film): 1730 (CO), 1650 (C = C), 1460, 1380, 1360, 1260 , 1150, 1060, 940, 890 cm 1

  b. Preparation of (E) -6-chloro-3,7-acetate

  dimethlyl-2,7-octadien-1-yl (III): R = COCH 3, Hal = Cl 7 A suspension of 11.8 g (0.06 mole) of (E) -3,7-dimethyl acetate -2.6-octadien-1-yl and 25 g of Kieselgel in 300 ml of anhydrous hexane are cooled to 0 ° C. and 8.1 g (8.7 ml, 0.074 mole) of tert-butyl hypochlorite are added. drip within 5 minutes, under

  The mixture is stirred at 0 ° C. for one half

  hour, then filtered; the filtrate is washed successively with a 10% solution of sodium sulphite and water and then dried over magnesium sulphate. The solvent is distilled off under vacuum and the residue is purified by column chromatography.

  (Kieselgel 60, 5: 0.1 petroleum ether-acetone).

  Yield: 10.6 g (76%) TLC: Rf = 0.44 (5: 0.1 petroleum ether-acetone) IR (film): 1730 (CO), 1660, 1640 (C = C) , 1460, 1380, -1 1260, 1150, 1080, 945, 900 cm

  c Preparation of (E) -3,7-dimethyl-2,7-octadiene

  1-ol (IV) A suspension of 2.46 g (0.062 mol) of aluminolithic hydride in 50 ml of anhydrous tetrahydrofuran is treated with a solution of 4.87 g (0.021 mol) of acetate of (E) 6-chloro-3,7-dimethyl-2,7-octadien-1-yl in 10 ml of anhydrous tetrahydrofuran in the course of half an hour and the mixture is refluxed for 2 hours,

  with stirring Then the reaction is quenched with acetylene

  With ethyl acetate and water, the mixture is extracted three times with a total of 300 ml of ether; the ethereal solutions are combined, washed successively with a saturated solution of sodium hydrogen carbonate and

  water and then dried over magnesium sulphate.

  The residue is distilled off and the residue is purified by column chromatography (Kieselgel 60, Ether

petroleum-acetone 5: 0.1).

  Yield: 1.68 g (52%), the product is identical to the compound which is prepared according to the procedure of Example 2 b); it can be converted into the desired compound

  of formula (I), according to the procedure of Example 2c).

  As is apparent from the foregoing, the invention is in no way limited to those of its modes of

  implemented, realized Lion and the application that came from

  to be described more explicitly; on the contrary, it embraces all the variants that may come to the mind of the technician in the field, without departing from the

  within the scope of the present invention.

Claims (4)

  1 process for the preparation of (E) -3,7-dimethyl-2,7octadien-1-yl propanoate represented by the formula (I), hereinafter: ## STR2 ## in that: a) (E) -3,7-dimethyl-2,6-octadien-1-ol represented by the following formula (II) is reacted: OH (II)   with a propionation agent, preferably propanoic chloride, the propanoate thus obtained is reacted with   ter-butyl hypohalogenite, preferably hypo-   tert-butyl chlorite in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, the halo compound thus obtained, of general formula (III) below, is reacted in which R is a propionyl radical and Hal a halogen atom, with a moderately active metal hydride in a polar solvent; or b) (E) -3,7-dimethyl-2,6-octadien-1-ol of formula (II) is reacted with a ter-butyl hypohalogenite, preferably hypochlorite in a moderately polar solvent in the presence of a moderately polar adsorbent, preferably Kieselgel, the halo compound of general formula (III) is treated, R is a hydrogen atom and Hal is as defined above, with a reducing agent,   the alcohol represented by the formula (IV) after: ) W <OH (IV)   with a propionation agent, preferably propanol chloride or c) (E) -3,7-dimethyl-2,6-octadien-1-ol is converted   of formula (II) with an acylating agent, preferably anhy-   acetic acid, to a compound of the general formula (V) after: J \ "), OR 4-   (V) where R is a C 5 acyl group, a hypohalogenite of terbutyl, preferably tert-butyl hypochlorite, is added to the double bond carried by the carbon atom at the 6-position thereof, in a aprotic polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, the compound of general formula (III) thus obtained, in which R is a C 1 to 5 'acyl group with a metal hydride, is reduced; the alcohol of formula (IV) thus obtained is reacted with a propionation agent, preferably   propanoic chloride; and separating from the reaction mixture   niel the compound of formula (I) thus obtained.   2 Process according to variant a) of the claim   cation, characterized in that the propanol is reacted   (3,7-dimethyl-2,6-octadien-1-yl) ate with a   tert-butyl halogenite in hexane or in a compound counterpart of it.   Process according to variant (a) of claim 1, characterized in that hydride is used   borosodium as a moderately reactive metal hydride.   4 Process according to any one of variants b) or c) of claim 1, characterized in that a reduced halo compound of formula (III) in alcohol   of formula (IV), with alumino-lithic hydride.