US3173955A - Aryl-alkenones - Google Patents

Aryl-alkenones Download PDF

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Publication number
US3173955A
US3173955A US214063A US21406362A US3173955A US 3173955 A US3173955 A US 3173955A US 214063 A US214063 A US 214063A US 21406362 A US21406362 A US 21406362A US 3173955 A US3173955 A US 3173955A
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US
United States
Prior art keywords
parts
phenyl
methyl
odour
dimethyl
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Expired - Lifetime
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US214063A
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English (en)
Inventor
Muus G J Beets
Wilhelmus J Wiegers
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International Flavors and Fragrances Inc
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International Flavors and Fragrances Inc
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    • 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
    • C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0888—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using transparant moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/006—Degassing moulding material or draining off gas during moulding

Definitions

  • FIGA FRE UENCY ma squame manina www umu una (cugopospo I so 80o fao m leo UG UJ Y u z gm E nm gne Y 1 z s l'. s e 7 a s 1o n 12 m 5 WAVELENGTH (MICRONS) FREQUENCY (cw) Fl G .2 1,0m wqm 1...@ n Q00 .n 7
  • FIG. 3 lomaqotmooo zn Koo (am magna@ Y AasoRANcE c 7 Q 9 m f! i! wAvELENGTH (MlcRoN s) 05617 INVENTORS March 16, 1965 M. G. J. BEETs ETAL 3,173,955
  • the compound (il) represents a new material of extraordinary intensive and valuable odour.
  • H3 Ri Rn (IX) This can be realized either by direct dehydration oi the carbinol (XZOH) under the inuence of catalysts such as sulphuric acid, toluene sulphonic acid, acid salts, boric anhydride, boric acid or by pyro-lysis of the corresponding esters such as acetates, propionates, stearates, metaborates, xanthates or sulphites.
  • catalysts such as sulphuric acid, toluene sulphonic acid, acid salts, boric anhydride, boric acid or by pyro-lysis of the corresponding esters such as acetates, propionates, stearates, metaborates, xanthates or sulphites.
  • the product is stabilized with a small amount of one" of the usual Vinhibitors such as hydroquinone.
  • Vinhibitors such as hydroquinone.
  • unsta-- bilized formiit'sh'ows a tendency to dimerize.
  • the dimer dissociates easily: and the monomer can always be recovered in nearly quan.- titative yield.
  • the crude reaction product was washed and fractionated through a 16-plate YVigreux column.
  • the yield was 65% of theory. 111320 15220-15223.
  • reaction product was stirred with a solution of 400 g. of potassium .carbonate in 600 g. of Water, Worked up and fractionated in vacuo. Yield of 2-tetrahydropyranyloxy-Z-cyanobutane 83 of the theory. B.P.3 mm 78, 1:1320 14432-14456.
  • a solution of neophylmagnesiumchloride was prepared from 228.4 g. (9.4 moles) of magnesium in 850 g. of dry ethyl-butylether and from 1516.5 g. (9.0 moles) of neophylchloride in 1516 g. of ethylbutylether in the usual Way.
  • the pyrolysis was carried out according to Example 1 at 450-470 at 190 mm. in nitrogen atmosphere. A mixture of two isomers was obtained in a ratio of 3:2 which could be separated by fractionation at 3 mm. through a l6-plate Vigreux column.
  • the odour of the first mentioned compound has a strong rose-like character, shaded to a green, rue like quality, that of the latter is similar, but more green and twiggy.
  • the aminoketone (1313 g., 113320 1.5233) was extracted with benzene and converted into the hydrochloric acid salt with an ethereal solution of hydrochloric acid. Melting point, after recrystallisation from acetone 1232-1240".
  • 2-methyl-2phenyl-heptanone4 was converted into the Mannich salt according to Example 10. After decomposition according to the same example the reaction product was fractionated through a 17plate Vigreux column.
  • Neophylmagnesiumchloride prepared in ethyl-butylether, was condensed with methacrolein at 0-10".
  • the reaction-product was fractionated through a saddle column of 25 cm. at 3 mm. Yield of 2,5-dirnethyl5phenyl hexene-l-ol-3 60%; B.P.3 mm, 115; nDzO 1.5208, :142 0.9675.
  • Some 2,5-dimethyl-5phenylhexanal (formed by 1,4 addition) was obtained as a byproduct.
  • Neophylmagnesiumchloride was condensed in ethylbutylether with crotonic aldehyde. 2methyl2phenyl heptene--ol-4 was obtained in a yield of 60%.
  • a solution of 448.5 g. (2.2 moles) of the unsaturated alcohol obtained in 1100 ml. of acetone a solution of 440 g.V (1.48 moles) of sodiumbichromate 2 aq. and 580 g. (5.68 moles) of concentrated sulphuric acid in 2200 ml. of Water were added in 2 hours at 0-5 C.
  • 2-methyl2-phenylheptene-5-one-4 is a colourless liquid with strong odour reminescent of jasmin absolute and of rhum.
  • the LR. spectrum is shown in FIG. 6.
  • the desired ketone was obtained as a colourless liquid; B.P.0 6 mm. 10ft-110; 111320 15250-15260.
  • the odour is Vsuggestive of jasmin.
  • Jasmin-type compositionl 25 parts 5 parts 5 parts 5 parts 5 parts 20 parts 10 parts 2 parts 3 parts 20 parts of benzylacetate of benzylpropionate of linalool of linalylacetate of hydroXydihydrocitronellal of -arnylcinnarnc aldehyde of phenyl ethyl alcohol of ylang ylang oil of heliotropin of Z-methyI-Z-phenyl-heptene-5-one-4 100 parts Comparison of the composition before and after addition of the compound according to the invention shows that the latter imparts to the composition a smooth, sweet jasmin effect.
  • the first mentioned composition After 20 hours on the smelling strip the first mentioned composition has a rough odour Whereas ⁇ the latter shows a natural jasmin character.
  • Nerol-type composition 25 parts of terpeneless petitgrain oil 5 parts of linalool 10 parts of linalyl acetate 1 part of methyl anthranilate 5 parts of geraniol Y 10 parts of phenyl ethyl alcohol 10 parts of terpeneless bergamotte oil 2 parts of bitter orange Voil 2 parts of methyl-pianaphthylketone 30 parts of 2,5dimethyl-2-phenyl-heptene-Sone4 100 parts
  • TheY addition of the compound according to the invention has an extremely favourable effect, especially on the backnote of the composition.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
US214063A 1961-08-09 1962-08-01 Aryl-alkenones Expired - Lifetime US3173955A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB28740/61A GB941143A (en) 1961-08-09 1961-08-09 New arylalkenones

Publications (1)

Publication Number Publication Date
US3173955A true US3173955A (en) 1965-03-16

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Family Applications (1)

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US214063A Expired - Lifetime US3173955A (en) 1961-08-09 1962-08-01 Aryl-alkenones

Country Status (3)

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US (1) US3173955A (de)
CH (1) CH419404A (de)
GB (1) GB941143A (de)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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Also Published As

Publication number Publication date
GB941143A (en) 1963-11-06
CH419404A (de) 1966-08-31

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