Terpinyl formate

Terpinyl Formate.—The formic acid ester of terpineol, CjeHj-OOCH, occurs naturally in Ceylon cardamom oil. It is prepared artificially by... 

Formic acid methyl ester. See Methyl formate Formic acid 1-methyl-1-(4-methyl-cyclohex-3-enyl) ethyl ester. See Terpinyl formate Formic acid, neryl ester. See Neryl formate Formic acid octyl ester. See Octyl formate Formic acid, oxydi-, diethyl ester. See Diethyl pyrocarbonate... 

Methyl 2-methylcrotonate Methyl (E)-2-methylcrotonate. See Methyl tiglate 1-Methyl-1-(4-methyl-3-cyclohexen-1-yl) ethyl butanoate Methyl methylcyclohexenyl ethyl butrate 1-Methyl-1-(4-methyl-3-cyclohexen-1-yl) ethyl butyrate. See Terpinyl butyrate (Z)-1 -Methyl-1 -(4-methyl-3-cyclohexen-1 -yl) ethyl cinnamate. See Terpinyl cinnamate 1 -Methyl-1 -(4-methylcyclohex-3-enyl) ethyl ethanoate. See Terpinyl acetate 1-Methyl-1-(4-methylcyclohex-3-enyl) ethyl methanoate. See Terpinyl formate... 

Terpinyl formate Terpinyl isobutyrate Terpinyl isovalerate Terpinyl propionate 4,5,6,7-Tetrahydro-3,6-dimethylbenzofuran Tetrahydrofurfuryl acetate Jetrahydrofurfuryl alcohol Tetrahydrofurfuryl butyrate Tetrahydrofurfuryl cinnamate Tetrahydrofurfuryl propionate Tetrahydrolinalool Tetrahydro-4-methyl-2-(2-methyl-1 -propenyl)-2H-pyran Tetrahydro-pseudo-ionone Tetramethyl ethylcyclohexenone 2,3,5,6-Tetramethylpyrazine... 

Rhodinyl phenylacetate Rhodinyl propionate Salicylaldehyde Santalol Santalyl acetate Santalyl phenylacetate Skatole Styrene a-Terpinene y-Terpinene a-Terpineol Terpineol anhyd. P-Terpineol Terpinolene Terpinyl acetate Terpinyl anthranilate Terpinyl butyrate Terpinyl cinnamate Terpinyl formate Terpinyl Isobutyrate... 

Santalyl acetate Skatole Spearmint (Mentha spicata) extract Stearoptenes Styrene Styryl acetate Tagetes oil a-Terpinene y-Terpinene a-Terpineol Terpinyl acetate Terpinyl butyrate Terpinyl formate Terpinyl isobutyrate Terpinyi propionate... 

Diaminodiphenic acid 2136-71-2 Ceteth-1 2142-94-1 Neryl formate 2150-54-1 Direct blue 25 2153-26-6 Terpinyl formate 2153-28-8 Terpinyl butyrate... 

Benzoylbiphenyl p-Phenylbenzophenone Trigonal 12 Xincure PBZ 218-373-5 Ceteth-1 218-401-6 Neryl formate 218-444-0 Terpinyl formate 218-445-6 Terpinyl butyrate 218-463-4 Lauryl acrylate Photomer 4812 SR 335 218-487-5... 

Decahydro-3-naphthyl formate Ethyl 2-nonynoate Geranyl formate Isobornyl formate Linalyl formate Neryl formate Terpinyl formate (CiiHi805)n... 

Selective conversion of pinene, 3-carene, and limonene or dipentene to terpineol, without terpin hydrate formation, is also used. Addition of organic acids (weak acids require catalytic amounts of mineral acids) produces terpinyl esters, which are subsequently hydrolyzed to terpineol, sometimes in situ. 

Esters, as has already been seen, are formed by the combination of alcohols and acids with the elimination of water. The reverse reaction, which is one of hydrolysis, can also occur under certain conditions, such as the presence of acid or alkali in an aqueous base. Not all esters are equally susceptible to this type of breakdown, but it only requires the formation of traces of a free acid such as butyric acid, totally to spoil a compound. Even an acetate such as linalyl acetate can cause problems by giving rise to free acetic acid. In alkaline media progressive breakdown of the ester may occur as the acid becomes neutralized. In products where this is likely to be a problem terpinyl acetate is often used to replace linalyl acetate. 

Hexyl butanoate Butyl hexanoate Fenchyl acetate Menthyl acetate a-Terpinyl acetate Bornyl acetate Isobornyl acetate Linalyl acetate Citronellyl isobutyrate Phenethyl formate Anisyl formate Ethyl salicylate Pentyl salicylate isoamyl Salicylate hexyl Salicylate... 

C]-mevalonic acid (56a) in Pinus palustris or P. sylvestris showed that the Relabeling is predominantly at (4) . Namely, the C(4) of the monoterpene is derived from C(2) of mevalonic acid (56) rather than C(4) as had been assumed and therefore, the cyclopropane ring formation must be accompanied by a double bond migration if a-car-3-ene (61) is indeed dervied from a-terpinyl ion (62) or its biosynthetic equivalents. 

H,14C]MVA was incorporated into la,2a,3p-trihydroxy-p-menthane by a Fusicoccum sp., and the labelling pattern suggested that p-menth-2-en-l-ol was generated from an a-terpinyl cation by a 1,3-hydride shift, followed by formation of the a-epoxide and cleavage.896 Ips beetles converted [2H]myrcene (the isotopically normal substrate being obtained in nature from Pinus spp.) into ipsdienol and... 

Figure 1. Postulated ionic mechanism for the formation of monoterpenes via the a-terpinyl cation (a) and the terpinen-4-yl cation (b). Regular (head-to-tail) structures are divided into isoprene units and the labeling patterns from Cl-labeled acyclic precursor are illustrated.

When geraniol reacts with phenols in the presence of acid, the common products are usually cyclized the use of 1 % oxalic acid has now been found to minimize cyclization in the reaction between orcinol and geraniol. Nerol has been labelled with deuterium in various positions [a, b, c, and d in (32)] and then converted into the chloride (33). Kinetic isotope effects on hydrolysis of (33) were measured, and 7r-participation in the cationic intermediate (34) leading to the cyclized terpinyl derivatives is discussed. Schwartz and Dunn proposed to use the complex (35), from geranyl methyl ether, as a model for a farnesol cyclization. They were not able to isolate this complex (although there was some evidence for its formation), the main complex (36%) being a dimeric a-complex (36), together with 39 % of the ketone (37), but no cyclized material. The cyclization of the acid chloride (38) to menthone and the C9 hydrocarbon (39) with tributyltin hydride, and also the optimum conditions for the cyclization of (-i-)-citronellal... 

Fig. 5. Postulated ionic mechanisms for the formation of monoterpenes via the a-terpinyl...

LPP to undergo the 1,6-ring closure to the (5)- or (f )-a-terpinyl cation (40). A hypothetic antf-Markovnikov 1,7-cyclization has never been reported as it would imply the formation of a less stable secondary cycloheptenyl cation. 

A remarkable feature of the cyclizations of linaloyl derivatives is the high stereoselectivity in the formation of a-terpineol. Thus, the hydrolysis of ( —) linaloyl phosphate (33-OP) affords (-h )-a-terpineol with an optical purity of 40% (79). The cyclization of linalool to optically active a-terpineol may also be carried out with sulfuric acid in acetic acid (81) and aqueous sulfuric acid (82). The a-terpinyl j9-nitrobenzoate produced in the hydrolysis of linaloyl /7-nitrobenzoate is obtained with an optical purity as high as 87% (80). These results require that cyclization occurs, at least in part, from an asymmetric transition state. 

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