Claims:1. A process for preparation of a sex attractant pheromone (Z, E)-7,9,11-dodecatrienyl formate (I) using Oct-7-yn-1-ol (II) comprising the steps of:
a. reacting a starting material Oct-7-yn-1-ol (II) in THF solvent and a weak base n-butylamine under nitrogen atmosphere in the presence of Palladium acetate and triphenylphosphine with (E)1-chlorobuta 1,3-diene (III) to yield 9E, 11-Dodecadien-7-yn-1-ol (IV);
b. reduction of 9E, 11-Dodecadien-7-yn-1-ol (IV) to (7Z, 9E)-dodeca-7,9,11-trien-1-ol (V) in presence of methanol using Zinc dust and ammonium chloride;
c. formylation of (7Z, 9E)-dodeca-7,9,11-trien-1-ol (V) in acetic anhydride and formic acid under nitrogen atmosphere in presence of triethyl amine in ether to yield (7Z, 9E)-dodeca-7,9,11-trienyl formate (I).
2. The process for preparation as claimed in claim 1, wherein the preparation of 9E, 11-Dodecadien-7-yn-1-ol in step a) is carried out using Oct-7-yn-1-ol (II) in THF solvent and a weak base n-butylamine in presence Cuprous iodide granules with (E)1-chlorobuta 1,3-diene (III).
3. The process for preparation as claimed in claim 1, wherein the preparation of (7Z, 9E)-dodeca-7,9,11-trienyl formate from (7Z, 9E)-dodeca-7,9,11-trien-1-ol (I) in step c) is carried out using hexane solvent for extraction.
4. The process for preparation as claimed in claim 1, wherein the (7Z, 9E)-dodeca-7,9,11-trienyl formate (I) is sex attractant insect pheromone for carob moth.
, Description:Technical Field of the Invention
The present invention relates to a process for the preparation of Pheromone, (Z, E)-7,9,11-dodecatrienyl formate (I) starting from Oct-7-yn-1-ol for Carb moth.

Background of the Invention
In the desert valleys of southern California, the carob moth, Ectomyelois ceratoniae (Zeller), is a serious pest of dates (Warner, 1988). If its range in this state expands northward towards the Central valley, economically important nut crops such as almonds and pistachios may be threatened, as the carob moth is a pest of these crops in other parts of the world (Dhouibi, 1982; Gothilf, 1984).

The likelihood of decomposition of the carob moth trienal in the field over periods of days or weeks prompted us to examine a potentially more stable mimic of this component that would successfully attract males when placed in traps. In the present study, we report the results of wind-tunnel bioassays and field-trapping studies that compare the attractiveness of (Z,E)-7,9,ll-dodeca-, trienyl formate (formate) with that of the trienal. A formate compound was chosen as the trienal mimic because Mitchell et al. (1975) suggested that formates may be more stable under field conditions than unsaturated aldehyde pheromones, and because formates have been shown to disrupt mating communication in some moth species whose pheromones consist of blends of aldehydes (Mitchell et al., 1975, 1976). We also describe the single-cell responses of male carob moth olfactory neurons to the three sex pheromone components and to the formate, in order to determine if the formate is an effective mimic of the trienal at the antennal receptor cell level.

In Journal of Chemical Ecology, Vol. 18, No. 12, 1992 discloses The behavioral and electrophysiological activity of a mimic [(Z,E)- 7,9,11 -dodecatrienyl formate] of the major sex pheromone component [(Z,E)-9,11,13 -tetradecatrienal] of carob moth was assessed.

(IE)-1-Chloro-dec-1-en-3-yn-10-ol (3). 7-Octyn-1-ol (2) was prepared from 3-octyn-1-ol (1) in 84% yield by the modified acetylene zipper reaction (Abrams and shaw, 1988). A dry 2 liter flas was loaded with bis(triphenyl phosphine)palladium II chloride and CuI (1 g each) and flushed with Ar. Alkynol (2) (20 g 159 mmol), freshly distilled trans-1,2-dichloro-ethylene (31g, 356 mmol), and THF 200 ml, were added to the reaction flask via a 5-cm column of 3 A activated molecular sieve. To the stirred mixture were added dropwise 40 ml of diisopropylamine (distilled from CaH2), and the initially pale yellow solution rapidly turned brown then black. The mixture was stirred overnight at room temperature after which time the reaction was ca. 50% complete. A further 1 g each of CuI and bis(triphenyl phosphine)palladium II chloride was added and stirring was continued until the reaction was complete. Hexane 400 ml was then added and the mixture was stirred a further 10 min before filtering with suction. The filtrate was extracted with saturated aqueous NH4Cl (3X100 ml) dired and passed through a column of a coarse silica gel (70-230 mesh), eluting with 40% EtOAc in hexane. The elute was concentrated and distilled, bp 1000C. yielding 25.2g (85%) of chloroalchol.

To the best of knowledge known at the time of this patent application, the improved methods herein for creating a synthetic composition of the carob moth pheromone for use in pest management have not been described.

Brief Summary of the Invention
Main object of the present invention is to provide a process for preparation of a sex attractant pheromone (Z, E)-7,9,11-dodecatrienyl formate (I) using Oct-7-yn-1-ol (II) to yield 9E, 11-formylation to yield (7Z, 9E)-dodeca-7,9,11-trienyl formate (I).

Brief Description of the Drawings

The present invention will be more readily understood from the detailed description of embodiments thereof made in conjunction with the accompanying drawings of which:

Fig. 1 shows step wise synthetic scheme 1 of (Z, E)-7,9,11-dodecatrienyl formate (I).

Detailed Description of the invention

An embodiment of the present invention is to provide a process for preparation of a sex attractant pheromone (Z, E)-7,9,11-dodecatrienyl formate (I) using Oct-7-yn-1-ol (II) comprising the steps of:
a. reacting a starting material Oct-7-yn-1-ol (II) in THF solvent and a weak base n-butylamine under nitrogen atmosphere in the presence of Palladium acetate and triphenylphosphine with (E)1-chlorobuta 1,3-diene (III) to yield 9E, 11-Dodecadien-7-yn-1-ol (IV);
b. reduction of 9E, 11-Dodecadien-7-yn-1-ol (IV) to (7Z, 9E)-dodeca-7,9,11-trien-1-ol (V) in presence of methanol using Zinc dust and ammonium chloride;
c. formylation of (7Z, 9E)-dodeca-7,9,11-trien-1-ol (V) in acetic anhydride and formic acid under nitrogen atmosphere in presence of triethyl amine in ether to yield (I).

The process for preparation of 9E, 11-Dodecadien-7-yn-1-ol in step a) is carried out using Oct-7-yn-1-ol (II) in THF solvent and a we(7Z, 9E)-dodeca-7,9,11-trienyl formate a base n-butylamine in presence Cuprous iodide granules with (E)1-chlorobuta 1,3-diene (III), step b) reduction of 9E, 11-Dodecadien-7-yn-1-ol (IV) to (7Z, 9E)-dodeca-7,9,11-trien-1-ol (V) in presence of methanol using Zinc dust and ammonium chloride, and the preparation of (7Z, 9E)-dodeca-7,9,11-trienyl formate from (7Z, 9E)-dodeca-7,9,11-trien-1-ol (I) in step c) is carried out using hexane solvent for extraction, which is sex attractant insect pheromone for carob moth.

The synthesis of (7Z, 9E)-dodeca-7,9,11-trienyl formate is a component of the sex pheromone of the carob moth, was synthesized by a short and efficient route, with a high degree of stereoselectivity. Key steps included the Pd-catalyzed construction of a diene-yn-ol intermediate from (E)1-chlorobuta 1,3-diene, and stereo- and regiospecific reduction of the diene-yn-ol with activated zinc in methanol.

The present invention discloses a process for the preparation of (7Z, 9E)-dodeca-7,9,11-trienyl formate is a component of the sex pheromone of the carob moth, was synthesized by a short and efficient route, with a high degree of stereoselectivity. Preparation includes the starting material as Oct-7-yn-1-ol, with the key steps included the Pd-catalyzed construction of a diene-yn-ol intermediate from (E)1-chlorobuta 1,3-diene, and stereo- and regiospecific reduction of the diene-yn-ol with activated zinc in methanol. The synthetic process for the preparation of (7Z, 9E)-dodeca-7,9,11-trienyl formate pheromones are efficient, and environmentally benign steps and procedures that are used as a sex attractant pheromone which modify insect behavior.

The carob moth, Ectomyelois ceratoniae, is a worldwide pest of fruit and nut crops. It infests dates, 1 ,2) almonds, 3) pistachios,4) pecans (personal observation) and pomegranates. 5) Carob moths have also been reported to accentuate losses in crops such as apples, peaches, pears and apricots, where primary damage has been caused by another insect pest or by fungi. 2) The carob moth was first reported in southern California in 1982,6) and since then has become a major pest in date gardens. There is also considerable concern that the insect will spread to other parts of the state, and in particular, into the multimillion-dollar almond crop. There is a pressing need both for sensitive and selective tools to monitor the spread of this pest, and to time insecticide applications.

The female-produced sex pheromone of this species has very recently been identified 7) as a blend of three unsaturated aldehydes, 9Z,11E,13-tetradecatrienal (1), 9Z,11E-tetradecadienal (2), and 9Z-tetradecenal (3).

A synthesis based on the first of these disconnections was attempted, via Pd-catalyzed coupling of a (E)1-chlorobuta 1,3-diene fragment with an alkenyl fragment, to assemble the conjugated triene in one step.

Experimental details:

Example 1. Synthesis of 9E, 11-Dodecadien-7-yn-1-ol (III):
In RBF charge THF (500ml), n-butylamine (176gr) and added Cuprous iodide (15gr), Palladium acetate (4.4gr) and triphenylphosphine (10.4gr) under Nitrogen atmosphere. Further added 7-octynol under stirring for 30 minutes and then added 1-chlorobutadiene to the reaction mixture. Reflux the reaction mass under stirring till oct-7-yn-1-ol is consumed, cool the reaction mass to room temperature followed by the addition hexanes (200 ml), ice (1 kg) and water (1lt) to the mass. Acidified the reaction mixture using sulfuric acid, followed by separation of organic layer, which is basified with caustic soda, concentrated to yield 9E, 11-Dodecadien-7-yn-1-ol analyzed by GC.
Yield: 105 g (74.4%)
Purity: 95 %

Example 2. Synthesis of (7Z, 9E)-dodeca-7,9,11-trien-1-ol (IV):
Charge methanol (1.0 lt) & 9E, 11-Dodecadien-7-yn-1-ol (100gr) into the RBF and added Zinc dust (220gr) and ammonium chloride (180gr) at a temperature of 25-30°C. Further raise the temperature to 60-65°C, under stirring for about 16 hours. Cool the reaction mixture to 30°C, carried out filtration under vacuum. Further wash the filtrate with methanol (200ml), followed by distillation of methanol under vacuum below 55°C. Added water (400ml) and Hexane (200ml) to the reaction mixture at 25-30°C under stirring for 20 minutes. Separate both organic and aqueous layer where hexane (200ml) is used to extract aqueous layer and wash the organic layer with water (200ml and brine solution (200ml) followed by distillation organic layer under reduced pressure at below 55°C. and dried over anhydrous sodium sulphate (20gr) to yield (7Z, 9E)-dodeca-7,9,11-trien-1-ol analyzed by GC.
Yield: 90 g (90%)
Purity: 90 %

Example 3. Synthesis of (Z, E)-7,9,11-Dodecatrienyl formate (I):
Charge acetic anhydride (162gr) to the RBF under nitrogen atmosphere, and cool to 0ºC, followed by slow addition of formic acid (91gr). Further raise the temperature of reaction mixture to 50ºC for about 20-30 minutes. Again, cool down the reaction mixture to 0ºC, followed by slow addition of Ether (500ml). Then dissolve (7Z, 9E)-dodeca-7,9,11-trien-1-ol (100gr) & Triethyl amine (100gr) in Ether (100ml) by slow addition to the reaction mixture at O°C. Allow the temperature of the reaction mixture to rise to 20-25°C under stirring. Followed by the addition of 0.5M NaOH solution to maintain the PH ~7, under stirring for 10 minutes. Separate aqueous and organic layers, where the aqueous layer is extracted with hexane. Wash the organic layer with brine solution and distill off the organic layer under reduced pressure at below 55°C, dried the organic layer over anhydrous sodium sulphate, to yield (Z, E)-7,9,11-Dodecatrienyl formate analyzed by GC.
Yield: 105 g (86.9%)
Purity: 90 %