DE2402416C3 - Sublimable composition containing fragrances - Google Patents

Description

Formula for trioxane:

O-

The present invention relates to a sublimable composition containing fragrances.

Heretofore, various kinds of sublimable aromatic compositions have been made by blending of non-sublimable materials such as perfume, dye, pigment, deodorant and the like made with sublimable substances such as camphor, naphthalene, p-dichlorobenzene and the like, one or more substances of these groups was contained in the mixture. The manufactured products enclose room fragrances, toilet deodorants, insecticides, animal repellants, Telephone receiver fragrances and the like.

However, these conventional sublimable substances have the disadvantage that they are unpleasant in themselves rie-hen and depending on the amount of perfume contained lei'-ht melt, with their melting point leaps and bounds If more than a minimal amount of perfume is contained in it, p-dichlorobenzene falls as sublimable Substance, for example, only allows a perfume content of at most 1% by weight, otherwise the aforementioned disadvantageous Effect occurs.

The object of the present invention is the use of certain sublimable compositions with odor properties. According to the invention, this object is achieved by sublimable fragrances Composition in tablet form containing triisopropyl-s-trioxane or tritert-butyls-trioxane. The two substances mentioned have been found to be sublimable aromatic compositions proven to be well suited, which are mixed with non-sublimable materials. (Below will be the two substances are called trioxane (1) and (2) in the order mentioned.)

The present invention resulted from a thorough study of trioxane (1) and (2) in a series of experiments which confirmed that these substances are sublimable and odorless and can contain perfuming oil in large quantities without lowering their melting point. The experiments showed that trioxane, the formula of which is given below, is rapidly sublimed but has an odor when R = H, while it is a smelling liquid when R = methyl or ethyl, and only when R = isopropyl or tertiary Butyl group, it is an odorless, sublimable crystal. Therefore, the trioxane (1) and (2), which is artificially produced by _{cyclizing and trimerizing the corresponding aldehyde through mineral acids, halogens, ZnCl 2} , PCl ₆ and the like, proved to be the suitable substance to overcome the disadvantages of the conventional sublimable x5 Because they are odorless, trioxane (1) and (2) can be used for any aromatic substance, and their scope is wider than that of conventional sublimable substances. In addition, trioxane (1) and (2) are chemically stable from others

ao chemicals cannot be influenced, especially not decomposable, and they also do not influence their additives. The sublimability of these fabrics was tested as follows:
Trioxane (1) and (2) each as a tablet with a diameter of 3.0 cm and a thickness of 0.23 cm was left for seven days in a thermostat at different temperatures and a humidity of 65% - ± 5 % , resulting in the following ( in Table I) indicated the percentage sublimation values, and what proved that these substances are quite suitable for the production of sublimable aromatic compositions.

35

Table I.

temperature
CC)

U)

(2)

20 ± 1 42.2 16.9 30 ± 1 73.3 29.3 37 ± 1 98.8 39.5

40 As already mentioned, the conventional sublimable substances, which themselves smelled unpleasant, required a large perfume content in order to mask their odor. The permissible perfume content was between 0.5 and 1.0% when p-dichlorobenzene was used as a sublimable substance.

As a countermeasure, polyvinyl alcohol, CMC, cellulose, diatomaceous earth and the like have already been used (see JP-PS 47 29 536) or gelling agents are used, the former as additives to the ones mentioned sublimable substances and the latter instead of the sublimable substances mentioned, both parts led to a falling melting point. In the state of the finished compositions they proved however, it turns out to be disadvantageous, since these additives cannot be sublimated when the first-mentioned group is used and deformed or shrunk when gelling agent was applied.

Compared to the sublimable substances described above, the melting point of trioxane drops (1) and (2) very little, i.e. H. never below 50 ° C, even with a perfume content of 15% with trioxane (1)

or 65 ° C with a perfume content of 20% for trioxane (2). As a result, with trioxane (1) and (2) the content of perfume and other additives as required and depending on the intended use of the composition to be chosen.

For the experiment, an agent was added to the trioxane (1) and (2) in any proportions consisted mainly of benzyl acetate, jasmine, and benzyl alcohol. This mixture was heated until it loosened, and then cooled down again. The ratio of perfume content to melting point for Tri-5 oxane (1) and (2) resulted in those shown in Table II compared to p-dichlorobenzene Results.

Table II

Fabrics

Perfume content (% by weight)
0 0.5 1

15th

20th

(1) SP, ⁰ C 62.5

(2) SP, ⁰ C 92.0

p-dichlorobenzene 53.0 49.0

-51.0-47.0-42.0 (Note: S.P. means: melting point).

61.0 58.0 56.0 54.0 52.5 51.0 66.0 -62.0 -60.0 -58.5 -57.0 -55.5 -54.0 -76.0 87.5 82.0 71.0 68.5 -90.0 -87.0 -80.0 -78.0 45.0 38.0

As can be seen from Table II, trioxane (1) can have a perfume content of 10% - 15% and trioxane (2) have up to 15% -20%.

The following test examples for trioxane (1) and (2) are intended to illustrate the present invention:

Example I.

50Gew.-parts of sulfuric acid in 50% concentration were at 0 ⁰ C - 3 ° C cooled, and dropwise 15 parts by weight of isobutyraldehyde was added thereto under stirring, and 30 minutes later 30 parts by weight of petroleum ether added to the resulting deposited crystal, extract. The petroleum ether layer was deposited and washed with 5% sodium bicarbonate solution and then with water until the layer became neutral. The organic layer was dried over anhydrous magnesium sulfate and then filtered to recover the petroleum ether. The residue was cooled to 10 parts by weight of solid crude triisopropyl-s-trioxane, which were again crystallized by methanol to give 9.5 parts by weight of pure, white odorless product with a melting point of 62.5 ° C. According to the test results, the product turned out to be equivalent to the products already in use.

The following further experiments were carried out with this crystal:

Example II

100 parts by weight of triisopropyl-s-trioxane were added to 10 parts by weight of perfume and mixed thoroughly, and the resulting mixture was compressed into tablets. These tablets turned out to be as a sublimable aromatic composition; for use as a room deodorant.

Example IH

To 5.0 g of refined triisopropyl-s-trioxane, 0.5 g of perfume was added and mixed well, and the resulting mixture was formed into disk-shaped tablets 3.0 cm in diameter and 0.76 cm in thickness. The tablets produced showed no sign of melting or deformation during storage in a thermostat, the temperature of which was kept at 50 ° C ± 1 ° C for an extended period of time. The tablets were so effective that they ^{filled a room of 26.29 m 3} with a pleasant fragrance.

B e i s ρ i e I IV

10 parts by weight of deodorant were added to 100 parts by weight of purified triisopropyl-s-trioxane added and mixed thoroughly, resulting in the manufacture of commercially available sublimable aromatic tablets resulted in various forms.

Example V

To 3.0 g of purified triisopropyl-s-trioxane, 0.45 g of deodorant was added and thoroughly mixed, and this mixture became 1 liter of sublimable aromatic deodorant 3.0 cm in diameter and 0.47 cm thick. This product was on the wall of a Flush toilet installed, one meter above the floor of the toilet room, 0.8 m wide, 1.15 m in length and 2.38 m in height, and left there at temperatures between 8 and 12 ° C for twenty days, whereby a group of 10 test persons take turns checking the odor state of the toilet during checked all the time. The test subjects agreed that the product included the toilet filled with a pleasant scent.

Example VI

100 parts by weight of 70% strength were added dropwise to 20 parts by weight of trimethyl acetaldehyde with stirring Sulfuric acid added for two hours at temperatures between 5 and 10 ° C. The resulting The mixture was left to stand for another hour, then 60 parts by weight of petroleum ether added, which resulted in the extraction of the deposited crystal. After the petroleum ether

layer was deposited, the mixture was neutralized by an aqueous sodium carbonate mixture, and dried with anhydrous magnesium sulfate. After filtration, the petroleum ether was withdrawn therefrom and the mixture gave 13 parts by weight of crude crystal. By recrystallizing this crude crystal with methanol, 12 parts by weight of pure, white, odorless sublimable crystal were produced as desired. The product, which had a melting point of 92 ⁰ C, proved by the IR, NMR and mass spectral studies to be completely identical with pure tri-t-butyl-s-trioxane. The further experiments were carried out with this substance.

Example VII

2 g of perfume were added to 20 g of purified tri-tert-butyl-s-trioxane and mixed. The mixture was formed into a disk tablet 6.0 cm in diameter and 0.8 cm thick of sublimable aromatic. The tablet was stored in a thermostat at 60 ± 1 ° C for a long period of time without being melted or deformed. The tablet was found to be effective enough ^{to fill a room of 26.2 m 3} with a pleasant fragrance.

Example VIII

To 100 parts by weight of purified tri-tert-butyls-trioxane 15 parts by weight of deodorant was added and mixed. The mixture turned to a piece of toilet deodorant that has an elevated melting point and a pronounced had a pleasant fragrance by making the tablet a process of mixing, melting and solidifying was subjected.

Example IX

To 0.5 g of purified tri-tert-butyl-s-trioxane were 0.75 g aromatic deodorant added and mixed. The mixture then became a Sublimable aromatic deodorant tablet 3.0 cm in diameter and 0.78 cm thick shaped. The tablet was placed one meter above the floor of a 1.00 meter long toilet room, 2.38 m high and 0.8 m wide and the temperature for twenty days between 15 ° C and Maintained 25 "C. A group of 10 test persons took turns checking the odor and was themselves ίο agreed that the tablet was so effective that the Toilet room was filled with a pleasant smell during the entire test period.

Example X

To 3.0 g of triisopropyl-s-trioxane, 0.2 g were added in each case Linalool, linalool oxide, anethole, cinnamic aldehyde, cinnamon oil, menthol, menthyl acetate, eugenol and thymol, added and mixed well. Each of these mixtures became a 3.0 cm tablet Diameter and 0.47 cm thick.

Twenty pieces of 50-day-old larvae of Tinnea pellionella with an average weight of 4.5 mg per head, which were added at 20 ± TC and a humidity of 65 ± 5%, were used for the tests. The larvae were placed in a petri dish along with 500 mg of dried bonito fish flakes, with a mesh of stainless wire separating the dish itself, allowing the larvae to breathe through the cover. The mixtures were placed separately from one another in the center of the bowl, the bowl being 8.5 cm inside diameter. The effect of testing at a temperature of 20 ± 1 ° C and a humidity of 65 ± 5% for 20 days was that the mixtures drove away the insects as shown in Table III. Not only did these mixtures have a remarkable effect in killing or reducing the weight of the insects, but they were also found not to deform or melt.

Table III After 20 days ^
Rate of sublimation
of the tablet
(%) / duration of the request
Consumption
crowd
(mg) Consumption rate
(%) Weight changes
tion in 20 larvae
of tinea pellionella
(mg) Number of destroyed
Larvae of tinea
pellionella / 20 pcs. Chemicals 12.5 0 0 -47.2 20th Linalool 11.2 20.6 4.1 -45.9 17 - Linalool oxide 12.2 3.0 0.6 -47.6 20th Anethole 12.3 4.5 0.9 -35.8 20th Cinnamic aldehyde 10.8 6.2 1.2 -24.6 20th Cinnamon oil 11.8 82.6 16.5 - 8.2 19th menthol 12.1 13.1 2.6 -45.6 20th Menthyl acetate 12.6 5.2 1.4 -46.0 20th Eugenol 12.3 4.1 0.8 -48.5 20th Thymol 7.6 325.0 65.0 + 58.2 0 Control (triisopropyl
s-trioxane alone) - 302.9 60.6 + 54.2 0 control
(no chemicals)

Example XI

A floral perfume, which by mixing 15 parts by weight of linalool, 10 parts by weight of linalool oxide, 1 part by weight of cinnamon oil, 5 parts by weight of methyl ethyl acetate, 3 parts by weight of anethole and 66 parts by weight Perfume blend made from natural and synthetic aromatic substances was made with in three different proportions of the mixture, d. H. 3%, 5%

and 10% mixed with triisopropyl-s »trioxane. 3 g of this mixture were each made into a tablet of Molded 3 cm in diameter. The effectiveness in repelling insects was similar to Example X tested, the larvae being raised with 500 mg of pure white, non-moth-proof wool. The test result shown in Table IV shows that this sublimable aromatic composition has a strong insecticidal effect.

Table IV

Perfume content OG-401

Number of larvae of Tinea Pellionella destroyed / consumption amount Consumption rate

20pcs (mg) (%)

after 6 days after 15 days after 23 days after 33 days after 23 days

0.0 (control) 0 pieces 0 pieces 0 pieces 251.0 50.2 3.0 3 pieces 15 pieces 20 piece 15.0 3.0 5.0 6 pieces 20 piece 20 piece 3.5 0.7 10.0 12 pieces 20 piece 20 piece 1.2 0.2 example XII Table V

Mixed chemicals

crowd

Terpinol 1.50 Phenyl acetate 0.20 Cinnamic acid 0.20 Eugenol 0.05 Thymol 0.05 Phenoxyethyl alcohol 3.00 Perfume 5.00 Triisopropyl-s-trioxane 90.00

Total: 100.00

A composition was found to be effective sublimable aroma in a 30-day test in one of the chemicals, as shown in Table V above, ^{as an effective sublimable aroma of 20 0} C, with 2.5 g of the composition to a 50 table sterilizer for a composition by mixing Telephone receiver that does not show a ring-shaped tablet 4.0 cm in outer diameter showing signs of melting, deformation, or unangular and 2.0 cm inner diameter. The tablet showed a bad odor.

709 636/276

Claims (1)

Claim: Sublimable composition containing ribbons in tablet form, containing triisopropyl-s-trioxane or tritert-butyl-s-trioxane. To work materials, the melting point of trioxane (1) 62.5 ° C and at trioxane (2) 92.0 ⁰ C.