Queen substance synthesis

Quaternary ammonium compounds biocidal activity mechanism, 1, 401 toxicity, 1, 124 Quaternization heterocyclic compounds reviews, 1, 73 ( )-Quebrach amine synthesis, 1, 490 Queen substance synthesis, 1, 439 4, 777 Quercetin occurrence, 3, 878 pentamethyl ether photolysis, 3, 696 photooxidation, 3, 695 Quercetrin hydrolysis, 3, 878 Quinacetol sulfate as fungicide, 2, 514 Quinacridone, 2,9-dimethyl-, 1, 336 Quinacridone pigments, 1, 335-336 Quinacrine... 

In one synthesis of the queen substance of honey bees (9) (cf p ) the double bond is derived from an... 

Interest in the vitamin B12 catalyzed light assisted electrolysis directed to the preparation of fine chemicals has been well illustrated in the synthesis of some natural products. One typical example is the synthesis of the Queen substance of Apis mellifera which involves two efficient electrochemical C,C-bond-forming steps by addition to conjugated double and triple bonds (Scheme 4) [63]. 

Scheme 4. Synthesis of the Queen substance of Apis melHfera...

Hi) Carboxylic acids and derivatives. The haloform reaction on thienyl methyl ketones leads to thiophenecarboxylic acids, which can be treated with Raney nickel to produce the open-chain acids. This method has been used for the five-carbon homologation of carboxylic acids and to produce dicarboxylic acids (Scheme 51). Long-chain carboxylic acids may also be prepared by using dicarboxylic acid derivatives for the acylation of thiophenes (Scheme 52). In the synthesis of Queen substance, the precursor (213) has been generated by Raney nickel desulfurization of the appropriate thiophene-2-acetic acid derivative (79T329). 

Callow R. K. and Johnson N. C. (1960) The chemical constitution and synthesis of queen substance of honeybees (Apis mellifera L.). Bee World 41, 152-153. 

The consecutive addition of alkyl halide to activated olefins by photoelectrocatalysis (PEC) of hydroxocobalamin hydrochloride allows the construction of extended carbon chains as shown for the synthesis of pheromone queen substance 9. The mild conditions of the B12/PEC reaction are suited for the addition of primary alkyl halides 10 containing a potential leaving group. This is illustrated in the synthesis of endo- and exo-brevicomin (11) (Scheme 4). 

Arylation of allylic alcohols (7, 274). This reaction has been applied in a synthesis of queen substance (5), in which the thiophene nucleus was used as a source of four methylene groups. Thus thienylation of -methallyl alcohol with... 

Butler, C.G., Callow, R.K. and Johnston, N.C. (1961). The isolation and synthesis of queen substance, 9-oxodec-fra s-2-enoic acid, a honeybee pheromone. Proc. R. Entomol. Soc. 155,417-432. 

The dimerization of butadiene is a useful method for the synthesis of various natural products. Pellitorine, which is an insecticidal compound isolated from Amcydkm pyrethrum roots, queen substances, which are well-known honey bee pheromones, ds-dvetone, which is a naturally occurring unique symmetric 17-manbered cyclic ketone, and recifeiolide, which consists of a 12-membered lactone firamwork, can readily be synthesized from butadiene dimers. 

A synthesis of a Queen substance [35] and of the pheromone of Monarch butterfly [36] are additional examples of applications of this particularly useful process. 

The same telomer was used by Baker et al. to synthesize the dimethyl-pentadecari 2-ol, the pheromone of the pine sawfly [16]. Also the queen substance, a well-known honey bee pheromone, is formed starting from the malonate telomer, which has exactly the right carbon number and a suitable functionality for a facile synthesis of this natural product (Equation 16) [17]. 

Less Usual Elements.—Reviews have covered the applications of silicon/ selenium, and mercury in synthesis. Some specific examples of syntheses involving less usual elements have been queen substance (30) (palladium ), (+)-cataline (31) (vanadium ), ibogamine (32) (silver, palladium ), terpenoids chiral cobalt catalyst ), and prostaglandins (zirconium ). 

Tsuji, J., K. Masaoka, and T. Takahashi Simple synthesis of queen substance from the butadiene telomer. Tetrahedron Lett. 1977, 2267—2268. 

Tamaru, Y., Y. Yamada, and Z. Yoshida Palladium catalyzed thienylation of oc-methallyl alcohol with 5-substituted 2-bromothiophenes and its application to synthesis of queen substance. Tetrahedron Letters 1978, 919—922. 

This reaction provides a useful way of introducing a double bond next to a carbonyl group. Here it is in a synthesis by Barry Trost of the Queen Bee Substance (the compound fed by the workers to those bee larvae destined to become queens). The compound is also a pheromone of the termite and is used to trap these destructive pests. Trost started with the monoester of a dicarboxylic acid, which he converted to a methyl ketone by reacting the acyl chloride with a cuprate. The ketone was then protected as a dioxolane derivative to prevent it enolizing, and the sulfur was introduced by reacting the enolate of the ester with the sulfur electrophile MeSSMe. 

Dicarboxylic esters are used to prepare polyesters and polyamides. The residual double bonds permit cross-linking of the polymer chains. Cross metathesis of methyl oleate with excess ethene affords methyl 9-decenoate, a key intermediate in the synthesis of queen bee substance , a honey bee pheromone. 

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