Textiles: spinning – twisting – and twining
Reexamination Certificate
1999-05-21
2001-03-13
Padmanabhan, Sreeni (Department: 1621)
Textiles: spinning, twisting, and twining
C512S027000, C568S338000, C568S375000, C568S343000
Reexamination Certificate
active
06200254
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to novel macrocyclic diene ketone compounds having unique fragrance qualities. These compounds are suitable for use in fragrance applications.
Some macrocyclic ketones (ring sizes of 15-17) are used quite extensively in the field of perfumery as musk odorants. For example, a fully saturated macrocyclic ketone, exaltone (cyclopentadecanone), is reported in S. Arctander, “Perfume and Flavor Chemicals, Vol. I,” sec. 813, (1969). Similarly, muscone (3-methylcyclopentadecanone) is reported in S. Arctander, “Perfume and Flavor Chemicals, Vol. II,” sec. 2276, (1969). Several mono-unsaturated macrocyclic ketones are also known in the field of perfumery. Some examples include civetone (cycloheptadec-9-en-1-one) as reported in S. Arctander, “Perfune and Flavor Chemicals, Vol. I,” sec. 700, (1969); and ambretone (cyclohexadec-5-en-1-one), reported in T. Kato et al., “Bull. Chem. Soc. Jpn.,” vol. 53 p. 2958 (1980) and 3-methylcyclopentadec-5-en-1-one as disclosed by E. Demole et al., U.S. Pat. No. 5,354,735.
In contrast, doubly unsaturated macrocyclic ketones (cycloalkadienones) are not extensively used in the creation of fragrances for perfumes and consumer products. Several reports describing the syntheses and the potential use in fragrances of a few examples of cycloalkadienones have appeared in the literature but synthetic and other practical considerations have precluded their use in commercial fragrance applications. All examples of cycloalkadienones pertinent to a discussion of the prior art related to this invention are illustrated below:
Most examples include the &agr;,&bgr;-unsaturated enone moiety (not present in the materials of this invention) prepared via a variety of techniques including phosphonate Wittig reactions. See, for example, H. J. Bestmann and H. Luetke, “Tetrahedron Lett.” vol. 25, pp. 1707-10 (1984). See also, K. C. Nicolaou et al. “J. Org. Chem.” vol. 44, pp. 4011-13 (1979). Additional references showing phosphonate Wittig reactions include G. Buchi and H. Wuest, “Helv. Chim. Acta.” vol 62, pp. 2661-72 (1979), G. Buchi and H. Wuest, U.S. Pat. No. 4,346,023, G. Buchi and H. Wuest, U.S. Pat. No. 4,302,607, G. Buchi and H. Wuest, European Patent No. 15,412, G. Buchi and H. Wuest, Japanese Patent No. JP 55,111,438 and K. C. Nicolaou et al. “J. Am. Chem. Soc.” vol. 120, pp. 5132-5133 (1998). Other methods for preparing cycloalkadienones via ring expansion techniques have also been reported. See J. Tsuji et al. “J. Org. Chem.” vol. 45, pp. 5209-11 (1980). See also Japanese Patent No. JP 59,029,687 A2 and S. Sakane et al. “Tetrahedron Lett.” vol. 24, pp. 943-6 (1983). In addition, see Bluthe et al. “Tetrahedron” vol.42, pp. 1333-44 (1986), N. Bluthe et al. European Patent No. EP 127536 A1, N. Bluthe et al. “Tetrahedron Lett.” vol. 25(27), pp. 2873-6(1984). Other miscellaneous methods are also reported. See, for example, B. D. Mookherjee et al. “J. Org. Chem.” vol. 36, pp. 3266-70 (1971), Japanese Patent No. JP 06092894 A2 (1994), R. N. Majee et al. “Indian Perfum.” vol. 35, pp. 239-40 (1991) and T. Ikuta and Y. Mizoe, Japanese Patent No. JP 52118447 (1977). Both the structures and the methods of preparation of all of these materials clearly differentiate this prior art from the materials and processes encompassed by the present invention.
The present invention also relates to novel synthesis pathways for obtaining macrocyclic diene ketones as well as saturated and mono-unsaturated macrocyclic ketones. Individual reaction steps used in the processes of the present invention have been previously disclosed. Grignard reactions are reported, for example, in D. A. Shirley, “Organic Reactions” vol. 8 p. 28 (1954); C. Blomberg and F. A. Hartog, “Synthesis” p. 18 (1977) and R. G. Woolford, “J. Org. Chem.” vol. 23, p. 2042 (1958). Claisen rearrangements are reported, for example, in S. J. Rhoads, “Organic Reactions” vol. 22, p. 1 (1975) and G. B. Bennett, “Synthesis” p. 539 (1977). Acyloin condensations are reported, for example, in J. J. Bloomfield and D. C. Owsley, “Organic Reactions” vol.23, p.259 (1976); K. T. Finley, “Chem. Revs.” vol. 64, p. 573 (1964), K. Ruhlmann, “Synthesis” p. 236 (1971), U.S. Pat. No. 2,529,825 and U.S. Pat. No. 2,228,268. Dieckman cyclizations are reported, for example, in P. S. Pinkney, “Org. Syn. Coll.” vol. 2, p. 116 (1943), J. P. Schaefer and J. J. Bloomfield, “Organic Reactions” vol. 15, p. 1 (1967) and N. J. Leonard and C. W. Schimelpfenig Jr., “J. Org. Chem.” vol. 23, p. 1708 (1958). However, it is the novel sequence ofreactions as well as the unique nature of the substrate materials upon which they act, that comprises the novel processes of the invention.
Herein we describe a previously undisclosed group of cycloalkadienones, which we have shown to have unique fragrance qualities suitable for use in fragrance applications. In addition, we also disclose novel, practical synthetic routes to these materials in Examples 1-4. Additionally, we disclose novel, practical synthetic routes to saturated and mono-unsaturated macrocyclic ketones in Example 5.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide novel compounds of the general Formula (I):
wherein R
1
, R
2
, R
3
and R
4
are independently a hydrogen atom or a C
1
to C
4
alkyl, a is the integer 1 or 2 and b is an integer in a range from 1 to 6. Preferably, R
1
, R
2
, R
3
, and R
4
are independently H or CH
3
. Preferably, a is the integer 1 or 2, and b is an integer in a range from 2 to 5.
It is a further object of the present invention to provide previously undisclosed cycloalkadienones, which we have shown to have unique fragrance qualities suitable for use in fragrance applications.
It is a further object of the present invention to provide fragrance compositions using novel cycloalkadienones.
It is a further object of the present invention to provide novel, practical synthetic routes to cycloalkadienones.
It is a further object of the present invention to provide novel, practical synthetic routes to saturated and mono-unsaturated macrocyclic ketones.
The term “C
1
to C
4
alkyl” is defined to include straight or branched, saturated or unsaturated carbon chains having from 1 to 4 carbon atoms. Examples of a C
1
to C
4
alkyl group include methyl, ethyl, allyl, propyl, iso-propyl, butyl, iso-butyl, and tert-butyl.
REFERENCES:
patent: 3778483 (1973-12-01), Becker et al.
patent: 4346023 (1982-08-01), Buchi et al.
patent: 5354735 (1994-10-01), Demole et al.
S.Arctander, Perfume and Flavor Chemicals, vol. 1, Section 700, 1969.
Aida Takashi
Caldwell John
Green Carter B.
Lankin Michael E.
Lupo, Jr. Andrew T.
Morrison Law Firm
Padmanabhan Sreeni
Takasago International Corporation
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