Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
  • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
  • C07C35/36—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system being a [4.4.0] system, e.g. hydrogenated naphthols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
  • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0069—Heterocyclic compounds
  • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
  • C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• 'It is the purpose of the present application to disclose a series of compounds with an odor of the amber type which can be produced in a simple way, starting from readily available, inexpensive materials.
• cyclisations may be realized conveniently by any suitable dehydrating agent such as aryl-' or alkanesulphonic acids, sulphuric acid, phosphoric acid, oxalic ocid, maleic anhydride or similar anhydrides, potassium hydrogen-sulphate or similar acid salts, alumina, chromous oxide, silica or alum, in the liquid as well as in the vapor phase.
• suitable dehydrating agent such as aryl-' or alkanesulphonic acids, sulphuric acid, phosphoric acid, oxalic ocid, maleic anhydride or similar anhydrides, potassium hydrogen-sulphate or similar acid salts, alumina, chromous oxide, silica or alum, in the liquid as well as in the vapor phase.
• a large number t 3 of such agents have been described by W. Reppe c.s. (Ann. 596 (1955) 81).
• a second convenient method for the preparation of ethers of type XII is the cyclisation of unsaturated diols of type )GV according to one of the methods mentioned above, followed by hydrogenation of the double bond.
• Diols of types XIII and XIV in which the symbol R has the meaning mentioned above may be prepared conveniently by condensation of myrcene with either citra- 2 conic anhydride and withpyrocinchonic anhydride followed by cyclisation and reduction steps, the sequence of which is of minor importance.
• lactones of types XVII and XVIII which can also be prepared conveniently from myrcene.
• Both types of intermediates may be converted into diols of types XIII and XIV by 1-3 steps, illustrated by the following flowsheet (the groups R are either both methyl or hydrogen and methyl) 1
• the groups R are either both methyl or hydrogen and methyl
• Some of the steps involved, irrespective of the chosen sequence, give rise to the formation of more than one isomer. This isomerism may have two causes. 1st, the position of the methyl group in case one of the substituents R is hydrogen. 2nd, conformational factors. Since the final product contains three saturated rings a number of conformational isomers is possible.
• Example 1 224 g. (2 moles of citraconic anhydride in dry xyleneare heated to reflux temperature (150 C.) and 327 g. of redistilled commercial myrcene (containing about 1.9 moles of pure myrcene) are added dropwise in the course of 25 mins., maintaining reflux without external heating. The mixture is stirred for an additional hour at reflux temperature which at the end of that period is 170 C.
• the product undoubtedly consists of morethan one isomer and/or stereoisomer, as is shown by the inconstant relative densities and relative viscosities throughout the fractionation.
• One of the constituents is characterized by means of a tetrabromide C H O Br with melting point 149.7-l50.5 C.
• the diol XlVa is obtained as a viscous oil (mixture of isomers and/or stereoisomers) which is used without purification. Yield 90%, 77 (approx) 1516-1519.
• Trimethyldecahydron-aphthofuran (2,3-c) XXa is obtained as a mixture of isomers and stereoisomers, boiling range 74- 80 C. at 0.05 mm., n 1.502-1.510. All fractions possess a characteristic but relatively weak odor of the amber type.
• Trimethyl-dodecahydronaphthofuran (2,3-c) XIIa boiling range 100-110 C. at 0.25 mm. 11 1.499-1.495-1.500 is obtained in 96% yield.
• the completemixture shows the following constants 11 1.4980, 41 0.9816.
• G.L.P.C. analysis indicates the presence of at least seven components, four of which occur in minor amounts 5% of the total mixture), and three of which are major components, A, B, and C, constituting about 27%, 42% and 18% of the total mixture respectively.
• Example 2 850 g. (3.6 moles) of a mixture of lactones XVIIa and XVIIIa are treated with 340 g. (14.8 gram-atoms) of finely dispersed sodium in 1800 g. of toluene and 1150 g. (8.7 moles) of dlisobutyl carbinol for-4 hrs. 30 mins. at reflux temperature (1l0-1l5 C.). After working up, a 90% yield of a mixture of isomers of the diol XIIIa is obtained as a viscous oil, hydroxyl assay which is used without purification.
• the pressure is decreased to 3 mm. Hg and the product is flash distilled; residue 220 g.
• the material obtained has a residual hydroxyl assay of 0.2%, and is fractionated through a Vigreux column of 28 theor. plates.
• the total mixture has 21 1.4986, d fi 0.9824, and shows a strong and lasting amber odor.
• n (const.) 1.4990 the constituent A occurs for about 70%, at least four minor peaks showing up in the chromatogram.
• the component B is enriched in a group of fractions with boiling point lO0-l0l C. at 0.2 mm., 11 1.4968, of which it constitutes about 70%. It may be isolated by recrystallization from acetone to yield a crystalline isomer of M.P. 49.1 -49.9 C. which proves identical with the corresponding material described in Example 1 (no depression of mixed melting point).
• Example 3 42 g. (0.16 mole) of adduct XV are refluxed with 200 ml. of 20% hydrochloric acid for 15 hrs. After recrystallization from ethyl acetate a pure compound, M.P. 224.8- 225.5 C. is obtained. 'No depression is caused by admixture With the compound described in the preceding section.
• the crystalline unsaturated ether cannot be hydrogenated with Adams catalyst slightly above atmospheric pressure, but after treatment with hydrogen at an initial pressure of 1400 p.s.i. at 160 C. in a stainless steel rocking autoclave, with Ruthenium on carbon catalyst, for 6 hrs., trimethyl-dodecahydronapththofuran (2,3-c) of M.P. 49.7-50.2 C., identical to the corresponding compound described in Examples 1 and 2, is obtained. This compound has a pronounced amber odor.
• Example 4 From the tricyclic anhydride XlXa, obtained as described in Example 1, a crystalline isomer M.P. 150.4- 150.7 C. can be isolated. Upon recrystallization from aqueous acetic acid the corresponding bicyclic dicarboxylic acid, M.P. l90.8192.5 C. (dec.) is obtained.
• Example 6 By saponification of 60 g. (0.24 mole) of adduct XV with 200 ml. of 10% sodium hydroxide, for 1 hr. at reflux temperature, working up in the usual way and recrystallization of the product from l-nitropropane, ethyl formate and acrylonitrile a pure isomer of the corresponding dicarboxylic acid melting point 140.7141.7 C. is obtained.
• a slow stream of boron trifluoride is introduced from a cylinder. After several minutes the reaction starts suddenly and the temperature rises to 45 C. The intro duction of BF is interrupted to allow the mixture to cool to 25 C., and is then resumed until the mixture is saturated, total weight increase 24.5 g. The mixture is stirred for another 2 hrs. at room temperature, water is added and the mixture is processed in the usual way.
• the unsaturated ether thus obtained is hydrogenated with Adams catalyst, in acetic acid at room temperature.
• the hydrogenation is complete in 11 hrs. 30 mins.
• the trimethyLdOdecahydronaphthofuran (2,3-c) Xlla is obtained as an oil, 11 1.4960.
• G.L.P.C. analysis of this oil indicates the presence of at least four of the seven isomers referred to in Examples 1 and 2.
• Example 7 163 g. (1.2 moles) of commercial myrcene are heated with 126 g. (1 mole) of pyrocinchonic anhydride in g. of propionic acid for 16 hrs. at 143 C. The reaction product is purified by distillation. About 50 g. of pyrocinchonic anhydride are recovered and a product of structure XVI is obtained in nearly quantitative yield. Boiling point 114-117 C. at-0.05 mm.; 115 (const.) 1.4933.
• the reaction mixture is processed and the product is again carefully fractionated.
• Tetramethyldodecahydronaphthofuran (2,3-c), XIIb, boiling point 120124 C. at 0.6 mm., 12 1.4970-1.4990 has a distinct amber odor, weaker but more tenacious than the trimethyl analogue Xlla.

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• 1959
  • 1959-01-22 GB GB2366/59A patent/GB881535A/en not_active Expired
• 1960
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