United States Patent (19) 11 Patent Number: 4,528,126 Bruns Et Al

United States Patent (19) 11 Patent Number: 4,528,126 Bruns et al. (45) Date of Patent: Jul. 9, 1985

54) 2,4-DIOXA-7,10-METHANO-SPIRO 5,5) 4,331,569 5/1982 Inoue et al...... 252/522 R UNDECANES AND THEIR USE IN 4,331,570 5/1982 Klemarczyk et al...... 252/522 R PERFUMERY COMPOSITIONS OTHER PUBLICATIONS (75) Inventors: Klais Bruns; Thuy N. Dang, both of Krefeld-Traar, Fed. Rep. of Kasper et al., "Chem. Abst.", vol. 92 (1980) 75936t. Germany Primary Examiner-Anton H. Sutto 73) Assignee: Henkel Kommanditgesellschaft auf Attorney, Agent, or Firm-Hammond & Littell, Aktien, Disseldorf-Holthausen, Fed. Weissenberger & Dippert Rep. of Germany 57 ABSTRACT 21 Appl. No.: 538,938 2,4-dioxa-7,10-methano-spiro 5,5) undecanes having 22 Filed: Oct. 4, 1983 the formula Related U.S. Application Data 63 Continuation of Ser. No. 271,605, Jun. 8, 1981, aban doned. 30 Foreign Application Priority Data Jul. 3, 1980 DE Fed. Rep. of Germany ...... 30251 87 51 Int. Cl...... A61K 7/46; CO7D 319/06 wherein R is a member selected from the group consist 52 U.S. Cl...... 252/522 R; 549/336 ing of hydrogen, alkyl having from 1 to 4 carbon atoms, 58) Field of Search ...... 549/336; 252/522 R vinyl and propenyl and their isomeric mixtures; its syn thesis, its use as a perfumery agent and as an olefactant 56) References Cited component in perfumery compositions and as an odor U.S. PATENT DOCUMENTS ant for technical products. 4,113,664 9/1978 Conrad et al...... 252/522 R 4.294,727 10/1981 Conrad et al...... 252/522 R 4. Claims, No Drawings 4,528,126 1. 2 7,10-methano-spiro5,5undecanes and the remainder 2,4-DIOXA-7,10-METHANO-SPIRO 5,5) customary constituents of perfumery compositions. UNDECANES AND THEIR USE IN PERFUMERY A yet further object of the present invention is the COMPOSITIONS development of a method of imparting a pleasant odor to a product comprising adding a sufficient amount of BACKGROUND OF THE INVENTION the above perfumery composition to provide the de This application is a continuation of co-pending U.S. sired degree of odor, patent application Ser. No. 271,605, filed June 8, 1981, These and other objects of the invention will become now abandoned. more apparent as the description thereof proceeds. This invention relates to 2,4-dioxa-7,10-methanos DESCRIPTION OF THE INVENTION piro5,5undecanes having the formula The above objects have been achieved by the novel 2,4-dioxa-7,10-methano-spiro5,5undecanes having the formula 15

wherein R is a member selected from the group consist ing of hydrogen, alkyl having from 1 to 4 carbon atoms, vinyl and propeny and their isomeric mixtures. These compounds are excellent new odorants for the produc wherein R is a member selected from the group consist tion of valuable composition for perfuming cosmetic ing of hydrogen, alkyl having from 1 to 4 carbon atoms, preparations and cleansers. 25 vinyl and propenyl and their isomeric mixtures. The manufacture of the new compounds of the inven OBJECTS OF THE INVENTION tion is effected by known methods of organic synthesis An object of the present invention is the obtaining of is several stages, where in the first step cyclopentadiene 2,4-dioxa-7,10-methano-spiro5,5undecanes having the is reacted with acrolein to give norborn-5-ene-2-car baldehyde, the latter is subjected in the second step to formula 30 methylolization according to Canizzaro in an alkaline medium to give 2,2-di-hydroxymethylnorborn-5-ene, the double bond is catalytically hydrogenated in a third step, and the spirocetal of the invention is obtained in a fourth step by subsequent acetalization with appropriate 35 aldehydes. The reaction takes place according to the following reaction scheme:

7 y CHO 21 NoHo G Cy 1st Step Af CHO/OH-)2nd Step G

R O 7 O

CHOH H2/Cat. RaCHO CH 2 OH-3rd Step Ge. 4th Step

N R where R has the above assigned values, wherein R is a member selected from the group consist 60 The new 2,4-dioxa-7,10-methano-spiro5,5undecanes ing of hydrogen, alkyl having from 1 to 4 carbon atoms, are obtained as a mixture of stereo-isomeric forms and vinyl and propenyl and their isomeric mixtures. are used as such as perfumes and employed as a compo Another object of the present invention is the devel nent in perfume compositions. opment of a process for the production of said 2,4-diox As new perfumes according to the invention are men a-7, 10-methano-spiro5,5undecanes. 65 tioned, for example, 2,4-dioxa-7,10-methano-spiro5,- A further object of the present invention is the devel 5undecane, 2,4-dioxa-3-methyl-7,10-methano-spiro5,- opment of a perfumery composition containing essen 5undecane, 2,4-dioxa-3-ethyl-7,10-methano-spiro5,- tially of from 1% to 50% by weight of said 2,4-dioxa 5undecane, 2,4-dioxa-3-isopropyl-7,10-methano 4,528,126 3 4 spiro5,5-undecane, 2,4-dioxa-3-vinyl-7,10-methano was obtained in the form of colorless crystals with a spiro5,5undecane, 2,4-dioxa-3-propenyl-7, 10 yield of 77.6% of the theory, and had the following methano-spiro5,5undecane, etc. characteristics: The new perfumes of the invention are characterized Mp 113.5°-115° C. by their intensive, interesting different scents of high 5 IR (KBr): 3300/cm (OH); 1037, 1018/cm (prim. OH); olfactory quality and richness. Another advantage of 3060, 715/cm (cis-HC=CH-). the new perfumes is their very good ability to combine 1H-NMR(d6-DMSO): 6.16 ppm, (m, 2H) to give novel odor nuances. The new perfumes of the invention can be mixed with (HC=CH): 4.40 ppm (2t, 2H) (OH); 3.40 ppm (m, 4H) other fragrances in a variety of ratios to form new per 10 (CH2OH); 0.59 ppm (2d, 1H) (C7-H). fumery compositions. Generally, however, the propor 3rd Step: Preparation of tion of the new odorants in the perfume compositions 2,2-di-hydroxymethyl-norbornane will range from 1% to 50% by weight, related to the total composition. 155 gm of 2,2-dihydroxyethyl-norborn-5-ene (1.0 Such compositions can be used directly as perfumes 15 mol) were dissolved in 400 ml of methanol in an auto or for perfuming cosmetic preparations such as soaps, clave, mixed with 14.2 gm of Raney nickel, and hydro etc. They also may be used to improve the smell of genated at 45 C. and 70 bar hydrogen pressure for 5 technical products such as washing and cleaning agents, hours until saturation of the double bond. After remov disinfectants, and agents for the treating of textiles. For ing the catalyst and the solvent, 2,2-di-hydroxymethyl the scenting of the various products, the compositions norbornane remained in a quantitative yield in the form generally are added to the former in concentrations of of colorless crystals with the following characteristics: 0.05% to 5% by weight, related to the total product. Mp 97-98 C. The following examples illustrate the subject matter IR(KBr) 3330/cm (OH), 1020/cm (prim. OH) of the invention in more detail without limiting it, how H-NMR (CDCl3): 3.65 ppm (2m, 5H) (CH2OH): ever, to these examples. 25 0.72 ppm (2d, 1H) C7-H). EXAMPLES 4th Step: Preparation of First the manufacture of the new odorants are de 2,4-dioxa-3-methyl-7,10-methano-spiro5,5undecane scribed. A mixture of 90.8 gm of 2,2-di-hydroxymethyl-nor EXAMPLE 1. bornane, 86.1 gm of triethylorthoformate and 25.6 gm of acetaldehyde (molar ratio 1:1:1) was mixed with 0.1 2,4-Dioxa-3-methyl-7, 10-methano-spiro5,5undecane gm of p-toluene-sulfonic acid with slight heating. After 1st Step: Preparation of norborn-5-en-2-carbaldehyde stirring over night at room temperature, ethyl formate 33.05 gm of freshly distilled cyclopentadiene, ob and ethanol were distilled off. The residue was taken up tained by distillation of bicyclopentadiene over a 50 cm 35 in ether, washed with 2N-sodium carbonate solution Vigreux column at normal pressure, were charged and and water, and dried over Sodiurn sulfate. After distill then 28.03 gms of acrolein were added in drops over a ing off the solvent, the residue was distilled under the period of 30 minutes under stirring. As soon as the water jet vacuum. The 2,4-dioxa-3-methyl-7, 10 temperature exceeded 55 C., the reaction vessel was methano-spiro5,5undecane was obtained with a 90% cooled in ice water. After the addition was completed, 40 yield as a colorless liquid had the following characteris the stirring was continued for another 3 hours at 60° C. t1CS: The mixture was subsequently distilled under a water Bp17 110° C.; GC 78.4/21.1%; no.20 1.4822. jet vacuum. The intermediate product, norborn-5-en-2- IR (film): 1150, 1100, 1025/cm (-O-C-O); carbaldehyde was obtained with a yield of 73.8% of the theory, and had the following characteristics. 45 1405/cm (CH3) Bp17 61° C.; GC: 89.3/10.6% 1H-NMR (CDCl3): 4.60 ppm (q, 1H) (C3-H), 3.68 IR (film): 2710, 1720/cm (CHO); 3060, 720/cm (ci ppm (2m, 4H) (CH2-O-CH(CH3)-O-CH2); 0.63 s-HC-CH). ppm (2d, 1H) (C12-H). 1H-NMR(CDCl3): 9.47 ppm (d. 1H) (CHO); 6.18 The product, which is a mixture of two stereoiso ppm (doubled, 2H) (HC=CH) 50 mers, has a rhubarb-galbanum odor. 2nd Step; Preparation of EXAMPLE 2 2,2-dihydroxymethyl-norborn-5-ene 2,4-Dioxa-7,10-methano-spiro5,5undecane 25gm of norborn-5-en-2-carbaldehyde were added in The preparation was similar as in Example 1, but drops to a mixture of 42 ml of 37% formalin and 12.3 gm 55 instead of acetaldehyde the acetalization was effected in of sodium hydroxide, dissolved in 36.9 ml of water, the 4th step directly with the corresponding amounts of under stirring under a nitrogen atmosphere and water paraformaldehyde in ethylene chloride. The end prod cooling over a period of 25 minutes. The temperature of uct obtained as a coloress liquid had the following char the reaction mixture rose to 30° C. Subsequently the acteristics: Stirring was continued for another hour at 55 C., and 60 Bp17 104° C.; nD20 14932, MW: 168 (MS homoge then the reaction mixture was extracted with 50 ml of methylisobutyl ketone. The organic phase was washed nous); odor minty, methone-scent. with 50 ml of water, and the aqueous phase with 50 ml EXAMPLE 3 of methylisobutylketone. The combined organic phases 2,4-Dioxa-3-ethyl-7,10-methano-spiro5,5undecane were washed neutral, dried over sodium sulfate, and the 65 Solvent was distilled off. The residue was recrystallized The preparation was similar as in Example 1, but from petroleum-ether (60–95)/toluene (1:1). The inter instead of acetaldehyde a corresponding amount of mediate product, 2,2-di-hydroxymethyl-norborn-5-ene, propionaldehyde was used in the 4th step. The end 4,528, 126 5 6 product obtained as a colorless liquid had the following -continued characteristics: Hyacinth composition Bp17 120° C., nD20 1.4813, MW: 196 (GC/MS: 2 ste Phenylacetaldehyde-dimethylacetal i0 parts by weight reoisomers) odor: woody, flowery, sweet, artificial Citronello l0 parts by weight honey, boysenberry scent. 5 Trans-2-hexenal (10% i.DEP) 10 parts by weight Hexenyl benzoate 5 parts by weight EXAMPLE 4 Rose oxide 5 parts by weight Cyclamen aldehyde 5 parts by weight 2,4-Dioxa-3-i-propyl-7,10-methano-spiro5,5undecane Methyloctynylcarbonate 5 parts by weight (10% i. DEP) The preparation was similar as in Example 1, but O N-methyl-methylanthranilate 5 parts by weight instead of acetaldehyde, a corresponding amount of 1000 parts by weight isobutyraldehyde was used in the 4th step. The end product obtained is a colorless liquid with the following characteristics: EXAMPLE 8 Bp17 128° C., nD20 1.4783, MW: 210 (GC/MS: 2 ste 15 reoisoners) odor: earthy, woody, sweet. Honey-flower-variant EXAMPLE 5 2,4-Dioxa-3-vinyl-7,10-methano-spiro- 100 parts by weight 5,5 undecane 2,4-Dioxa-3-vinyl-7,10-methano-spiro5,5undecane 2O Phenylethyl alcohol 350 parts by weight Phenylethyl phenylacetate 150 parts by weight The preparation was similar as in Example 1, but Cinnanyalcohol 100 parts by weight instead of acetaldehyde, the corresponding amount of Hydroxycitromellal 60 parts by weight Heliotropine 50 parts by weight acrolein was used in the 4th step. The end product Propylphenyl acetate 50 parts by weight obtained in a colorless liquid with the following charac Phenylethyl salicylate 35 parts by weight teristics: 25 Linaolool 30 pparts by weightg Methyl phenylacetate 30 parts by weight Bp184° C., np.201.4955, MW: 194 (GC/MS: 2 stereo p-methylquinoline 20 parts by weight isomers) odor; flowery, honey, diphenylether scent. Methyleugenol 5 parts by weight Waniliin 5 parts by weight EXAMPLE 6 Cournarin 5 parts by weight 0 Ethyl pelargonate 5 parts by weight 2,4-Dioxa-3-propenyl-7,10-methano-spiro5,5undecane Citroneo 5 parts by weight The preparation was similar as in Example i, but 1000 parts by weight instead of acetaldehyde a corresponding amount of crotonaldehyde was used in the 4th step. The end prod The preceding specific embodiments are illustrative uct obtained is a colorless liquid with the following 35 of the practice of the invention. It is to be understood, characteristics: however, that other expedients known to those skilled Bp0,893 C., nD20 1.4956, MW: 208 (GC/MS: 4 ste in the art or disclosed herein, may be employed without reoisomers), odor; oily, sweet, sandalwood scent. departing from the spirit of the invention or the scope of The compounds mentioned in the foregoing examples the appended claims. are suitable for the production of the various perfume 40 We claim: compositions, which are used for perfuming various 1. 2,4-dioxa-7, 10-methano-spiro5,5undecanes hav products, like cosmetics, detergents, soaps, but also ing the formula technical products in concentrations of 0.05 to 2% by weight. Here are other examples of perfume composi 45 tions containing compounds according to the invention: EXAMPLE 7

50 Hyacinth composition wherein R is a member selected from the group consist 2,4-dioxa-3-methyl-7,10-methano-spiro- 150 parts by weight ing of hydrogen, alkyl having from 1 to 4 carbon atoms, 5.5 undecane vinyl and propenyl and their isomeric mixtures. Benzyl acetate 50 parts by weight 2. A perfumery composition consisting essentially of Linalool 150 parts by weight Cinnamyl alcohol 100 parts by weight 55 from 1% to 50% by weight of the 2,4-dioxa-7,10 Phenylethyl alcohol 90 parts by weight methano-spiro5,5undecane of claim 1 and the remain Hydroxycitronellal 90 parts by weight der customary constituents of perfumery compositions. Heliotropine 50 parts by weight 3. The method of imparting a pleasant odor to a prod Benzyl alcohol 40 parts by weight uct comprising the step of adding a sufficient amount of Phenylacetaldehyde 30 parts by weight 60 the perfumery composition according to claim 2 to Ylang-Ylang oil 25 parts by weight Dimethylbenzycarbinyl acetate 20 parts by weight provide the desired degree of odor. Eugenol 15 parts by weight 4. The method of claim 3 wherein the effective Cinnamyl acetate 15 parts by weight amount consists of from 0.05% to 5% by weight of the lsoeugenol 10 parts by weight composition of claim 2. ot-irone 10 parts by weight 65 k k k k k