Organic compounds

Abstract

An aryl-substituted alkanal compound having a molecular weight of less than 300 g/mol and which bears a substituent on the aryl ring ortho to a substituent bearing the aldehyde functionality. Said compounds are useful as perfume ingredients in personal care and household care products.

Claims

1. An aryl-substituted alkanal compound having a molecular weight of less than 300 g/mol and which bears a substituent on the aryl ring ortho to a substituent bearing the aldehyde functionality, and is represented by Formula 1 ##STR00045## wherein, R.sub.1, R.sub.2, R.sub.3, R.sub.6 and R.sub.7 each independently may represent H or methyl; R.sub.4 is H, or when R.sub.5 is H, R.sub.4 is a C.sub.1-C.sub.7 branched or linear, saturated or unsaturated, unsubstituted or substituted, optionally with cyclopropyl groups, alkyl radical; R.sub.5 is H, or when R.sub.4 is H, R.sub.5 is a C.sub.1-C.sub.7 branched or linear, saturated or unsaturated, unsubstituted or substituted, optionally with cyclopropyl groups, alkyl radical; or R.sub.4 and R.sub.5 together with the carbon atoms to which they are attached, form a substituted or unsubstitued 5-membered ring; n=0, 1, 2; the dotted line represents an optional single bond, with the proviso that when the dotted line represents a single bond R.sub.4 or R.sub.5 are sec-butyl, iso-butyl or a C.sub.5-C.sub.7 branched or linear, saturated or unsaturated alkyl residue; and wherein the compounds are not selected from 5-(tert-butyl)-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde, 5-(tert-butyl)-2,3-dihydro-1H-indene-2-carbaldehyde, 5-isopropyl-2,3-dihydro-1H-indene-2-carbaldehyde, 5-isopropyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde, 5-ethyl-2,3-dihydro-1H-indene-2-carbaldehyde, 5-ethyl-2-methyl-2,3-dihydro-1H-indene-2-carbaldehyde, 5-methyl-2,3-dihydro-1H-indene-2-carbaldehyde, 2,5-dimethyl-2,3-dihydro-1 H-indene-2-carbaldehyde, 3-(5-(tert-butyl)-2-methylphenyl)propanal, 3-(5-(tert-butyl)-2-methylphenyl)-2-methyl propanal, 3-(5-isopropyl-2-methylphenyl)propanal, 3-(5-isopropyl-2-methylphenyl)-2-methylpropanal, 3-(5-ethyl-2-methylphenyl)propanal, 3-(5-ethyl-2-methylphenyl)-2-methylpropanal, 3-(4-(tert-butyl)-2-methylphenyl)propanal, 3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal, 3-(4-isopropyl-2-methylphenyl)propanal, 3-(4-isopropyl-2-methylphenyl)-2-methylpropanal, 3-(4-ethyl-2-methylphenyl)propanal, 3-(4-ethyl-2-methylphenyl)-2-methylpropanal or a compound of formula 3 ##STR00046## wherein R.sub.1 through R.sub.5 is independently H or methyl.

2. A method of utilizing the compound according to claim 1 as a perfume ingredient exhibiting muguet odour characteristics to a personal care or household care composition comprising the step of adding to said composition the compound or a perfume composition containing said compound.

3. A perfume composition comprising the compound as defined in claim 1, which composition is free of any aryl-substituted alkanal, optionally free of any aryl-substituted propanal, odourants that are unsubstituted on the aryl ring at a position ortho to the substituent bearing the aldehyde functionality, and optionally free of 3-(4-tert-butylphenyl)-2-methypropanal.

4. A personal care or household care composition perfumed with an aryl-substituted alkanal compound according to claim 1.

5. A personal care or household care composition according to claim 4 containing enzymes.

6. The personal or household care composition according to claim 5 characterised in that it is a textile treatment product.

7. The personal or household care composition according to claim 5 characterised in that it is a detergent composition.

8. A method of imparting muguet odour characteristics to a fine fragrance or consumer product comprising the step of adding thereto an aryl-substituted alkanal compound defined in claim 1, and selectively excluding from said fine fragrance or consumer product any aryl-substituted alkanal compounds, which are unsubstituted on the ring at the position ortho to the substituent containing aldehyde functionality, said selective addition or exclusion being based on the susceptibility of said compounds to enzymatically-mediated degradation to their benzoic acid derivatives when incubated with hepatocytes isolated from rats, said compounds being suitable for addition on the basis that they do not degrade to their benzoic acid derivatives, whereas said compounds being excluded on the basis that they do degrade to their benzoic acid derivatives.

9. An aryl-substituted alkanal compound having a molecular weight of less than 300 g/mol and which bears a substituent on the aryl ring ortho to a substituent bearing the aldehyde functionality, represented by Formula 2 ##STR00047## wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.6 each independently may represent H or methyl; R4 is H, or when R.sub.5 is H, R.sub.4 is a C.sub.1-C.sub.7 branched or linear, saturated or unsaturated, unsubstituted or substituted, optionally with cyclopropyl groups, alkyl radical; R.sub.5 is H, or when R.sub.4 is H, R.sub.5 is a C.sub.1-C.sub.7 branched or linear, saturated or unsaturated, unsubstituted or substituted, optionally with cyclopropyl groups, alkyl radical; or R.sub.4 and R.sub.5 together with the carbon atoms to which they are attached, form a substituted or unsubstitued 5-membered ring; and wherein the compounds are not 3-(5-(tert-butyl)-2-methylphenyl)propanal, 3-(5-(tert-butyl)-2-methylphenyl)-2-methylpropanal, 3-(5-isopropyl-2-methylphenyl)propanal, 3-(5-isopropyl-2-methylphenyl)-2-methylpropanal, 3-(5-ethyl-2-methylphenyl)propanal, 3-(5-ethyl-2-methylphenyl)-2-methylpropanal, 3-(4-(tert-butyl)-2-methylphenyl)propanal, 3-(4-(tert-butyl)-2-methylphenyl)-2-methylpropanal, 3-(4-isopropyl-2-methylphenyl)propanal, 3-(4-isopropyl-2-methylphenyl)-2-methylpropanal, 3-(4-ethyl.-2-methylphenyl)propanal, 3-(4-ethyl-2-methylphenyl)-2-methylpropanal, or a compound of formula 3 ##STR00048## wherein R.sub.1 through R.sub.5 is independently H or methyl.

10. A method of utilizing the compound according to claim 9 as a perfume ingredient exhibiting muguet odour characteristics to a personal care or household care composition comprising the step of adding to said composition the compound or a perfume composition containing said compound.

11. A perfume composition comprising the compound as defined in claim 9, which composition is free of any aryl-substituted alkanal, optionally free of any aryl-substituted propanal, odourants that are unsubstituted on the aryl ring at a position ortho to the substituent bearing the aldehyde functionality, and optionally free of 3-(4-tert-butylphenyl)-2-methylpropanal.

12. A personal care or household care composition perfumed with an aryl-substituted alkanal compound according to claim 9.

13. A personal care or household care composition according to claim 12 containing enzymes.

14. The personal or household care composition according to claim 12 characterised in that it is a textile treatment product.

15. The personal or household care composition according to claim 12 characterised in that it is a detergent composition.

16. A method of imparting muguet odour characteristics to a fine fragrance or consumer product comprising the step of adding thereto an aryl-substituted alkanal compound defined in claim 9, and selectively excluding from said fine fragrance or consumer product any aryl-substituted alkanal compounds, which are unsubstituted on the ring at the position ortho to the substituent containing aldehyde functionality, said selective addition or exclusion being based on the susceptibility of said compounds to enzymatically-mediated degradation to their benzoic acid derivatives when incubated with hepatocytes isolated from rats, said compounds being suitable for addition on the basis that they do not degrade to their benzoic acid derivatives, whereas said compounds being excluded on the basis that they do degrade to their benzoic acid derivatives.

Description

EXAMPLE 1

(1) Synthesis of 3-(4-isobutyl-2-methylphenyl)propanal

(2) ##STR00014##

(3) A) 1-Isobutyl-4-(3-(methoxymethoxy)propyl)benzene:

(4) To a solution of 3-(4-isobutylphenyl)propan-1-ol (641.0 g, 3.33 mol) in 1.5 L of dimethoxymethane was added lithium bromide (14.5 g) and p-toluene sulfonic acid (10.0 g). The mixture was stirred for 20 h at room temperature and then poured with stirring into aqueous sodium hydroxide (200 ml, 2M). The organic phase was washed neutral with a diluted solution of NaCl, dried (MgSO.sub.4) and evaporated in vacuo to yield 1-isobutyl-4-(3-(methoxymethoxy)propyl)benzene (721.0 g, 91.5%) as a colourless oil. .sup.1H-NMR (400 MHz, CDCl3): =7.17-7.08 (m, 4H), 4.68 (s, 2H), 3.59 (t, J=6.4 Hz, 2H), 3.42 (s, 3H), 2.74 (t, J=7.8 Hz, 2H), 2.49 (d, J=7.1 Hz, 2H), 2.0-1.84 (m, 3H), 0.95 (d, J=6.6 Hz, 6H) ppm. .sup.13C-NMR (400 MHz, CDCl3): =139.5 (s), 139.4 (s), 129.5 (d, 2C), 128.5 (d, 2C), 96.9 (t), 67.6 (t), 55.6 (q), 45.5 (t), 32.5 (t), 31.9 (t), 30.7 (d), 22.8 (q, 2C) ppm. GC/MS (EI): 236 (M.sup.+), 204 (29), 161 (65), 147 (59), 131 (100), 117 (49), 105 (37), 104 (26), 91 (46), 57 (29), 45 (64).

(5) B) 8-Isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine:

(6) To a cooled solution (0 C.) of AlCl.sub.3 (10.33 g) in dichlormethane (80 ml) was added dropwise a solution of 1-isobutyl-4-(3-(methoxymethoxy)propyl)benzene (13.9 g, 55.36 mmol) in dichloromethane (40 ml). After the addition was complete, the mixture was stirred for 1.5 h at 5 C. and poured into an aqueous sodium hydroxide solution (80 ml, 2M). The mixture was extracted with MTBE and the organic phases were washed with after and brine, dried (MgSO.sub.4) and evaporated in vacuo to afford a clear yellowish oil (11.91 g) which was first distilled in kugelrohr (125 C., 0.12 mbar) and then purified by chromatography to yield 8-isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine (6.95, 61%) as a colourless oil. Odor: .sup.1H NMR (400 MHz, CDCl.sub.3): =7.11 (d, J=7.33 Hz, 1H), 7.01-6.97 (m, 2H), 4.66 (s, 2H), 4.09-4.06 (m, 2H), 3.02-2.98 (m, 2H), 2.46 (d, J=7.33 Hz, 2H), 1.93-1.82 (m, 1H), 0.94 (d, J=6.8 Hz, 6H) ppm. .sup.13C-NMR (400 MHz, CDCl.sub.3): =140.3 (s), 140.05 (s), 139.9 (s), 129.8 (d), 129.3 (d), 128.8 (d), 76.1 (t), 75.6 (t), 45.3 (t), 35.5 (t), 30.9 (t), 30.6 (d), 22.8 (q, 2C) ppm. GC/MS (EI): 204 (M.sup.+, 33), 161 (100), 147 (44), 143 (58), 131 (31), 129 (28), 119 (61), 115 (34), 105 (43), 91 (34).

(7) C) 3-(4-Isobutyl-2-methylphenyl)propan-1-ol

(8) A catalytic amount of borontriflouride etherate (0.3 g) was added to a suspension of Pd/C (10%, 0.5 g) and 8-isobutyl-1,3,4,5-tetrahydrobenzo[c]oxepine (50.0 g, 244.7 mmol). The mixture was hydrogenated in an autoclave for 2 h at 9 bar and 50 C. The suspension was filtered and thin film distilled (160 C., 0.11 mbar) to yield 3-(4-isobutyl-2-methylphenyl)propan-1-ol (45.4 g, 89.9%) as a viscous colourless oil. Odour: .sup.1H-NMR (400 MHz, CDCl.sub.3): =7.10 (d, J=7.6 Hz, 1H), 6.99-6.94 (m, 2H), 3.75 (t, J=6.6 Hz, 2H), 2.74-2.68 (m, 2H), 2.47 (d, J=7.3 Hz, 2H), 2.34 (s, 3H), 2.19 (s, 1H, OH), 1.95-1.84 (m, 1H), 0.96 (d, J=6.6 Hz, 6H) ppm. .sup.13C-NMR (400 MHz, CDCl3): =139.7 (s), 137.6 (s), 135.9 (s), 131.5 (d), 128.9 (d), 127.1 (d), 63.0 (t), 45.4 (t), 33.5 (t), 30.6 (d), 29.5 (t), 22.9 (q), 19.7 (q) ppm. GC/MS (EI): 206 (M.sup.+, 25), 163 (100), 161 (27), 145 (84), 119 (53), 117 (33), 115 (32), 105 (41), 91 (40), 41 (23).

(9) D) 3-(4-Isobutyl-2-methylphenyl)propanal

(10) Pyridinium chlorochromate (PCC, 37.6 g, 174.49 mmol) was added portionwise to a solution of 3-(4-isobutyl-2-methylphenyl)propan-1-ol (30.0 g, 145.41 mmol) in dichloromethane (300 ml); the temperature rose to 35 C. The mixture was stirred for 1 h and another portion of PCC (10 g, 46.4 mmol) was added and stirring was continued for another 15 min. The reaction mixture was filtered over Florisil and silica gel. The filtrate was evaporated in vacuo (23.2 g) and distilled in kugelrohr (143 C., 0.08 mbar) to yield 3-(4-isobutyl-2-methylphenyl)propanal (19.01 g, 64%) as a colorless oil. Odor: floral, aldehydic, green, Lilial, watery. .sup.1H-NMR (400 MHz, CDCl3): =9.88 (t, J=1.5 Hz, 1H), 7.07 (d, J=7.6 Hz, 1H), 7.0-6.95 (m, 2H), 2.98-2.93 (m, 2H), 2.79-2.74 (m, 2H), 2.46 (d, J=7.1 Hz, 2H), 2.33 (s, 3H), 1.95-1.82 (m, 1H), 0.95 (d, J=6.6 Hz, 6H) ppm. .sup.13C-NMR (400 MHz, CDCl3): =202.2 (d), 140.2 (s), 136 (s), 135.9 (s), 131.6 (d), 128.6 (d), 127.3 (d), 45.4 (t), 44.6 (t), 30.6 (d), 25.5 (t), 22.9 (q), 19.7 (q) ppm. GC/MS (EI): 204 (M.sup.+, 23), 161 (100), 147 (26), 143 (49), 119 (84), 118 (34), 117 (33), 115 (33), 105 (59), 91 (36).

(11) The following compounds were prepared according to the sequence described in Example 1

EXAMPLE 2

(12) ##STR00015##

(13) 3-(4-Isobutyl-2,6-dimethylphenyl)propanal

(14) Odor: floral, aldehydic, fruity, slightly rosy

(15) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.91-9.89 (t, J=1.5 Hz, 1H), 6.84 (s, 2H), 2.99-2.93 (m, 2H), 2.67-2.61 (m, 2H), 2.42-2.39 (d, J=7.1 Hz, 2H), 2.32 (s, 6H), 1.94-1.80 (m, 1H), 0.96-0.92 (d, J=6.57, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.1 (d), 139.9 (s), 136.0 (s, 2C), 134.5 (s), 129.6 (d, 2C), 45.4 (t), 43.6 (t), 30.5 (d), 22.9 (q, 2C), 22.1 (t), 20.1 (q, 2C) ppm. GC/MS (EI): 218 (M.sup.+), 175 (81), 162 (31), 157 (55), 133 (71), 132 (29), 119 (100), 117 (29), 115 (37), 105 (31), 91 (47).

EXAMPLE 3

(16) ##STR00016##

(17) 3-(4-Isobutyl-2-methylphenyl)-2-methylpropanal

(18) Odor: fatty, watery, floral, green, aldehydic

(19) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.75 (d, J=1.8 Hz, 1H), 7.03 (d, J=7.6 Hz, 1H), 6.99-6.92 (m, 2H), 3.09 (dd, J=6.1 Hz, 13.9 Hz, 1H), 2.73-2.73 (m, 1H), 2.61-2.54 (m, 1H), 2.44 (d, J=7.1 Hz, 2H), 2.32 (s, 3H), 1.94-1.81 (m, 1H), 1.14 (d, J=6.8 Hz, 3H), 0.93 (d, J=6.6 Hz, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =204.9 (d), 140.3 (s), 136.1 (s), 134.6 (s), 131.7 (d), 129.8 (d), 127.1 (d), 47.3 (d), 45.4 (t), 34.0 (t), 30.6 (d), 22.8 (q), 19.9 (q), 13.9 (q) ppm. GC/MS (EI): 218 (M.sup.+), 161 (100), 119 (62), 118 (24), 117 (23), 115 (23), 106 (16), 105 (81), 91 (31), 43 (27), 41 (25).

EXAMPLE 4

(20) ##STR00017##

(21) 3-(4-Isobutyl-2-methylphenyl)butanal

(22) Odor: floral, green, watery, fatty

(23) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.74 (t, J=1.8 Hz, 1H), 7.10 (d, J=7.8 Hz, 1H), 6.01-6.95 (m, 2H), 3.64-3.55 (m, 1H), 2.77 (ddd, J=1.8 Hz, 6.7 Hz, 16.7 Hz,1H), 2.67 (ddd, J=2.2 Hz, 8.1 Hz, 16.5 Hz, 1H), 2.43 (d, J=7.3 Hz, 2H), 2.37 (s, 3H), 1.92-1.82 (m, 1H), 1.30 (d, J=6.8 Hz, 3H), 0.93 (d, J=6.8 Hz, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.5 (d), 141.1 (s), 139.9 (s), 135.0 (s), 131.8 (d), 127.5 (d), 125.4 (d), 51.7 (t), 45.4 (t), 30.6 (d), 29.5 (d), 22.9 (q), 22.6 (q), 19.8 (q) ppm. GC/MS (EI): 218 (M.sup.+),175 (100), 161 (25), 133 (43), 131 (28), 119 (22), 117 (28), 115 (25), 105 (16), 105 (61), 91 (28), 41 (21).

EXAMPLE 5

(24) ##STR00018##

(25) 3-(4-(sec-Butyl)-2-methylphenyl)propanal

(26) Odor: green, floral, marine, Lilial-like

(27) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.89 (t, J=1.5 Hz, 1H), 7.08 (d, J=7.3 Hz, 1H), 7.02-6.98 (m, 2H), 2.98-2.93 (m, 2H), 2.80-2.74 (m, 2H), 2.56 (m, J=7.1 Hz, 1H), 2.34 (s, 3H), 1.67-1.56 (m, 2H), 1.26 (d, J=6.8 Hz, 3H), 0.87 (t, J=7.5 Hz, 3H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.2 (d), 146.3 (s), 136.1 (s), 136.0 (s), 129.6 (d), 128.7 (d), 125.2 (d), 44.5 (t), 41.6 (d), 31.6 (t), 25.5 (t), 22.2 (q), 19.8 (q), 12.7 (q) ppm. GC/MS (EI): 204 (M.sup.+), 175 (100), 147 (14), 133 (16), 131 (54), 119 (32), 117 (26), 115 (27), 105 (27), 91 (35), 77 (14).

EXAMPLE 6

(28) ##STR00019##

(29) 3-(2-Methyl-4-(tert-pentyl)phenyl)propanal

(30) Odor: floral, green, weak

(31) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.89 (t, J=1.5 Hz, 1H), 7.16-7.07 (m, 3H), 2.99-2.93 (m, 2H), 2.80-2.74 (m, 2H), 2.35 (s, 3H), 1.67 (q, 3=7.6 Hz, 2H), 1.30 (s, 6H), 0.74 (t, J=7.6 Hz, 3H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.2 (d), 148.1 (s), 135.6 (s), 128.4 (d, 2C), 124.2 (d), 44.5 (t), 37.9 (s), 37.2 (t), 28.8 (q, 2C), 25.4 (t), 20.1 (q), 9.6 (q) ppm. GC/MS (EI): 218 (M.sup.+), 190 (15), 189 (100), 145 (42), 131 (15), 129 (10), 128 (11), 115 (16), 105 (16), 91 (18), 41 (12).

EXAMPLE 7

(32) ##STR00020##

(33) 3-(4-Isopentyl-2-methylphenyl)propanal

(34) Odor: aldehydic, floral, green, watery

(35) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.87 (t, J=1.5 Hz, 1H), 7.06 (d, J=7.8 Hz, 1H), 7.02-6.97 (m, 2H), 2.96-2.91 (m, 2H), 2.78-2.72 (m, 2H), 2.60-2.54 (m, 2H), 2.32 (s, 3H), 1.67-1.55 (m, 1H), 1.54-1.46 (m, 2H), 0.96 (d, J=6.6, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.2 (d), 141.7 (s), 136.1 (s), 135.9 (s), 130.9 (d), 128.8 (d), 126.5 (d), 44.6 (t), 41.3 (t), 33.7 (t), 28.1 (d), 25.5 (t), 22.9 (q, 2C), 19.7 (q) ppm. GC/MS (EI): 218 (M.sup.+), 119 (37), 118 (100), 117 (23), 115 (22), 106 (31), 105 (36), 91 (28), 43 (22), 41 (29), 29 (20).

EXAMPLE 8

(36) ##STR00021##

(37) 3-(5-Isopropyl-2-methylphenyl)butanal

(38) Odor: floral fruity, slightly rosy, slightly green

(39) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.77 (dd, J=1.8 Hz, 2.2 Hz, 1H), 7.13 (d, J=7.8 Hz, 1H), 7.09-7.02 (m, 2H), 3.69-3.59 (m, 1H), 2.92 (sp, J=6.8 Hz, 1H), 2.81 (ddd, J=1.7 Hz, 6.2 Hz, 16.6 Hz, 1H), 2.72 (ddd, J=2.2 Hz, 8.3 Hz, 16.7 Hz, 1H), 2.38 (s, 3H), 1.34 (d, J=6.8 Hz, 3H), 1.29 (d, J=6.8 Hz, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =202.3 (d), 147.4 (s), 143.8 (s), 132.8 (s), 130.9 (d), 124.5 (d), 123.9 (d), 51.6 (t), 34.3 (d), 29.8 (d), 24.5 (q), 21.9 (q), 19.4 (q) ppm. GC/MS (EI): 204 (M.sup.+), 161 (54), 147 (27), 145 (38), 119 (100), 117 (25), 115 (32), 105 (43), 91 (42), 43 (31), 41 (31).

EXAMPLE 9

(40) ##STR00022##

(41) 5-Isobutyl-2,3-dihydro-1H-indene-2-carbaldehyde

(42) Odor: aldehydic, marine, watery, floral

(43) .sup.1H NMR (400 MHz, CDCl.sub.3): =9.80 (d, J=1.8 Hz, 1H), 7.15 (d, J=7.6 Hz, 1H), 7.04 (s, 1H), 6.98 (d, J=7.3 Hz, 1H), 3.34-3.25 (m, 3H), 3.24-2.96 (m, 2H), 2.47 (d, J=7.1 Hz, 2H), 1.93-1.73 (m, J=6.82, 1H), 0.93 (d, J=6.6H, 6H) ppm. .sup.13C NMR (400 MHz, CDCl.sub.3): =203.4 (d), 141.5 (s), 140.9 (s), 138.7 (s), 128.2 (d), 125.7 (d), 124.5 (d), 51.3 (d), 45.7 (t), 33.3 (t), 33.0 (t), 30.7 (d), 22.8 (q, 2C) ppm. GC/MS (EI): 202 (M.sup.+ 35), 159 (100), 145 (32), 141, (47), 131 (17), 129 (91), 128 (70), 127 (23), 115 (43), 41 (21).

EXAMPLE 10

(44) Synthesis of 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal

(45) ##STR00023##

(46) E) (E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde:

(47) To a solution of 2-methyl-4-(4-methylpent-3-en-1-yl)benzaldehyde (3.0 g, 14.8 mmol) and trimethylorthoformate (2.36 g, 22.3 mmol) in methanol (2 ml) at 0 C., was added acetyl chloride (0.05 g, 0.64 mmol). The mixture was stirred at room temperature for 30 min and then aqueous sodium bicarbonate (2.0 ml) was added. The organic layer was separated, concentrated and dissolved again in diethyl ether (2.0 ml). Borontrifluoride etherate (0.11 g, 0.74 mmol) was added dropwise followed by ethoxyethene (1.40 g, 19.3 mmol). The reaction mixture was stirred at room temperature for 30 min, aqueous sodium bicarbonate (2.0 ml) was added, and the organic layer was separated. The organic layer was dried (MgSO.sub.4). The solvent was evaporated in vacuo and aqueous HCl solution (7.4%, 5.0 ml) was added to the residue. The mixture was heated to reflux for 5 h and then cool to room temperature. The reaction was diluted by water (15 ml) and then extracted by MTBE (215 ml). The organic layers were dried over MgSO.sub.4 and evaporated in vacuo. The crude product was purified by column chromatography to yield (E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde (1.1 g, 32.5%) as a colourless oil. .sup.1H-NMR (300 MHz, CDCl.sub.3): =9.70 (d, J=7.7 Hz, 1H, CHO), 7.75 (d, J=15.7 Hz, 1H, ArCHCH), 7.57-7.50 (m, 1H, ArH), 7.12-7.03 (m, 2H, ArH), 6.65 (dd, J=7.7 Hz, 15.7 Hz, 1H, CHCHO), 5.15 (t, J=6.4 Hz, 1H), 2.62 (t, J=7.8 Hz, 2H), 2.46 (s, 3H, ArCH.sub.3), 2.33-2.25 (m, 2H), 1.69 (s, 3H, CH.sub.3), 1.57 (s, 3H, CH.sub.3) ppm. .sup.13C-NMR (300 MHz, CDCl3): =193.9 (d), 150.4 (d), 146.1 (s), 137.9 (s), 132.5 (s), 131.2 (d), 130.3 (s), 128.7 (d), 126.9 (d), 126.8 (d), 123.3 (d), 36.0 (t), 29.7 (t), 25.7 (q), 19.8 (q), 19.7 (q) ppm. GC/MS (EI): 228 (22, M.sup.+), 213 (22), 200 (1), 185 (2), 171 (4), 160 (100), 145 (34), 131 (28), 115 (27), 103 (4), 91 (20), 79 (8), 69 (75), 53 (6), 41 (36).

(48) F) 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal

(49) In a 100 mL round-bottomed flask was added (E)-3-(2-methyl-4-(4-methylpent-3-en-1-yl)phenyl)acrylaldehyde (1.0 g, 2.9 mmol) in ethyl acetate (15 ml) to give a colorless solution. The solution was de-gassed and purged with argon. Palladium on charcoal (0.1 g, Pd content of 10%) was added. The reaction was stirred under hydrogen atmosphere for 2 h until completion of the conversion (confirmed by GC). The reaction mixture was filtered through a small pad of silica gel and the solid was rinsed with ethyl acetate. The filtrate was collected and concentrated. The residue obtained was distilled by Kugelrohr to give 0.8 g of 3-(2-Methyl-4-(4-methylpentyl)phenyl)propanal as a colorless liquid. Odor: floral, green, watery. .sup.1H NMR (CDCl.sub.3): =9.85-9.80 (m, 1H, CHO), 7.09-6.80 (m, 3 H, ArH), 2.89 (t, J=7.3 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.71 (t, J=7.3 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.51 (t, J=7.8 Hz, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 2.28 (s, 3 H, ArCH.sub.3), 1.70-1.50 (m, 3 H, (CH.sub.3).sub.2CHCH.sub.2CH.sub.2), 1.32-1.15 (m, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 0.87 (d, J=6.5 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =201.8 (d), 141.1 (s), 135.7 (s), 135.6 (s), 130.5 (d), 128.4 (d), 126.1 (d), 44.2 (t), 38.8 (t), 35.8 (t), 29.5 (t), 27.9 (d), 25.1 (t), 22.6 (q), 19.3 (q). MS: m/z (%)=232 (89) [M.sup.+], 214 (80), 204 (4), 189 (100), 176 (21), 161 (68), 147 (84), 129 (40), 119 (87), 105 (90), 91 (44), 77 (15), 65 (7), 55 (15), 43 (27).

EXAMPLE 11

(50) Synthesis of 3-(2-Methyl-5-(4-methylpentyl)phenyl)propanal

(51) ##STR00024##

(52) G) (E)-2-Bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene:

(53) Preparation of the Grignard Reagent:

(54) In a 250 mL three-necked flask was added magnesium turnings (2.44 g, 100 mmol), and 10 mL of anhydrous ether. Under argon atmosphere, with vigorous stirring was added 1-bromo-3-methylbutane (15.2 g in 50 mL ether) dropwise. Initially, 5 mL was added in order to initiate the reaction and the reaction temperature increased from RT to 40 C. Then the reaction mixture was cooled to 5 degree by an ice-water bath. With vigorously stirring, the rest of 1-bromo-3-methylbutane was added dropwise in half an hour. After compl5etion of the addition, the reaction was refluxed for half an hour.

(55) The Grignard Addition and Dehydration:

(56) In a 250 mL three-necked flask was added 3-bromo-4-methylbenzaldehyde (10 g, 50 mmol) in ether (25 mL). Under argon atmosphere, the reaction mixture was cooled to 5 degree in an ice-water bath. The Grignard reagent prepared above was transferred into a 250 mL dropping funnel and was slowly added to the reaction mixture with vigorous stirring. The addition took 60 min during which time the reaction temperature was kept below 15 C. After completion of the addition, the reaction was heated to reflux for 10 min. The reaction mixture was cooled to 5 degree again. Then sat. NH.sub.4Cl (aq. 75 mL) was added dropwise to quench the reaction. The organic layer was separated and the aqueous layer was extracted by ether (50 mL). The combined organic layers were washed once with brine (25 mL) and then dried with MgSO.sub.4. The Solvent was evaporated to give a light yellow liquid which was transferred to a 250 mL round-bottomed flask and dissolved in toluene (100 ml). Then 4-methylbenzenesulfonic acid hydrate (0.87 g, 5.0 mmol) was added. Under argon atmosphere, the reaction mixture was refluxed via a Dean-Stark to remove water (oil bath temperature 135 degree). After 2 h, all water had been removed. GC analysis indicated completion of the conversion. The reaction was allowed to cool to room temperature. Then a slurry of NaHCO.sub.3 salts (4.0 g) in water was added with vigorous stirring. After 10 min, the reaction was filtered and the solid was rinsed twice with toluene. The filtrate was collected and concentrated to give a yellowish liquid (39.8 g). The yellow liquid was further purified by Kugelrohr distillation to give 11.6 g of (E)-2-bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene as a colorless liquid. .sup.1H NMR (CDCl.sub.3): =7.43 (s, 1 H, ArH), 7.15-7.01 (m, 2 H, ArH), 6.21-6.02 (m, 2 H), 2.27 (s, 3H, ArCH.sub.3), 1.99 (dd, J=6.6 Hz, 6.6 Hz, 2 H, CH.sub.2), 1.72-1.56 (m, 1 H), 0.84 (d, J=6.6 Hz, 6 H, 2CH.sub.3). .sup.13C NMR (CDCl.sub.3): =137.5 (s), 136.0 (s), 130.7 (d), 130.5 (d), 129.6 (d), 129.3 (d), 125.1 (s), 124.8 (d), 42.4 (t), 28.6 (d), 22.6 (q), 22.4 (q). MS: m/z (%)=252 (15) [M.sup.+], 209 (12), 196 (15), 130 (100), 115 (22), 77 (4), 63 (3), 51 (3), 41 (3).

(57) H) (E)-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid:

(58) To a solution of (E)-2-bromo-1-methyl-4-(4-methylpent-1-en-1-yl)benzene (11.6 g, 46 mmol) in THF (50 mL) which was cooled to 78 C. in an acetone-dry ice bath was added n-BuLi (32 mL, 1.6 M in hexane, 51 mmol) dropwise. During the addition, the reaction temperature was kept below 60 degree. After completion of the addition, the reaction was stirred at 78 C. for 30 min. Then a solution of trimethyl borate (5.2 g, 51 mmol) in THF (12 ml) was added dropwise to the reaction mixture at 78 C. After completion of the addition, the reaction temperature was raised to 0 C. in 1 h and then quenched by 2N aqueous HCl (45 mL, 90 mmol). The organic layer was separated and the aqueous layer was extracted with 250 mL MTBE. The combined organic layers were washed once with brine and then dried over MgSO.sub.4. The solvent was evaporated and the residue was dried under vacuum to give 13.5 g yellow solid. The solid was re-crystallized in iso-hexane and MTBE to give 8.1 g of (E)-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid as a white solid. .sup.1H NMR (CDCl.sub.3): =8.23 (s, 1H, ArH), 7.43-7.05 (m, 2H, ArH), 6.42-6.15 (m, 2H), 2.80 (s, 3H, ArCH.sub.3), 2.09 (dd, J=6.4 Hz, 6.4 Hz, 2 H), 1.79-1.66 (m, 1 H, (CH.sub.3).sub.2CH), 0.96 (d, J=6.4 Hz, 6 H, 2CH.sub.3). .sup.13C NMR (CDCl.sub.3): =144.8 (s), 134.9 (d), 134.7(s), 130.9 (d), 130.5 (d), 129.2 (d), 125.8 (d), 42.5 (t), 28.7 (d), 22.4 (q).

(59) I) (E)-3-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal

(60) To a 250 mL round-bottomed flask was added [RhCl(cod)].sub.2 (0.0026 g, 0.0058 mmol), cycloocta-1,5-diene (0.062 g, 0.58 mmol), and potassium phosphate (2.45 g, 11.6 mmol) in dioxane (20 ml) and water (3.0 mL) to give a yellowish solution. (E)-(2-Methyl-5-(4-methylpent-1-en-1-yl)phenyl)boronic acid (2.52 g, 11.6 mmol) and acroleine (0.97 g, 17.3 mmol) were added. The reaction mixture was heated to 85 C. under argon atmosphere for 4 h. The mixture was cooled to room temperature and was diluted with water (15 mL). The reaction mixture was extracted with 250 mL MTBE. The combined organic layers were washed once with brine and then dried over MgSO.sub.4. The solvent was evaporated and the crude product was purified by column chromatography (iso-hexane/MTBE=20:1) and Kugelrohr distillation to give 0.8 g of (E)-3-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal as a colorless liquid. .sup.1H NMR (CDCl.sub.3): =9.95-9.82 (m, 1H, CHO), 7.20-7.04 (m, 3H, ArH), 6.30 (d, J=15.8 Hz, 1 H, ArCHCH), 6.23-6.09 (m, 1 H, ArCHCHCH.sub.2), 2.91 (t, J=7.6 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.80-2.70 (m, 2H, ArCH.sub.2CH.sub.2CHO), 2.28 (s, 3 H, ArCH.sub.3), 2.08 (dd, J=6.7 Hz, 2 H, (CH.sub.3).sub.2CHCH.sub.2CH), 1.75-1.69 (m, 1 H, (CH.sub.3).sub.2CH), 0.93 (d, J=6.7 Hz, 6 H, 2CH.sub.3). .sup.13C NMR (CDCl.sub.3): =201.6 (d), 138.5 (s), 136.0 (s), 134.4 (s), 130.6 (d), 130.5 (d), 129.2 (d), 126.3 (d), 123.9 (d), 44.1 (d), 42.4 (t), 28.6 (d), 25.5 (t), 22.4 (q), 19.0 (q). MS: m/z (%)=230 (22) [M.sup.+], 187 (3), 169 (5), 156 (5), 143 (100), 128 (21), 115 (8), 105 (1), 91 (4), 77 (3), 65 (2), 51 (1), 41 (3).

(61) J) 3-(2-Methyl-5-(4-methylpentyl)phenyl)propanal

(62) To a 100 mL round-bottomed flask was added (E)-3-(2-methyl-5-(4-methylpent-1-en-1-yl)phenyl)propanal (0.50 g, 2.2 mmol) in ethyl acetate (10 ml) to give a colorless solution. The solution was de-gassed and purged with argon. Palladium on charcoal (0.05 g, Pd content of 10%) was added. The reaction was stirred under hydrogen atmosphere for 2 h until completion of the conversion (confirmed by GC). The reaction mixture was filtered through a small pad of silica gel and the solid was rinsed with ethyl acetate. The filtrate was collected and concentrated. The residue obtained was distilled by Kugelrohr to give 0.45 g of 3-(2-methyl-5-(4-methylpentyl)phenyl)propanal as a colorless liquid. Odor description: green, anisic, aldehydic, fatty. .sup.1H NMR (CDCl.sub.3): =9.86-9.83 (m, 1H, CHO), 7.06 (d, J=8.0 Hz, 1H, ArH), 6.95 (d, J=8.0 Hz, 1H, ArH), 6.94 (s, 1H, ArH), 2.92 (t, J=7.7 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.73 (t, J=7.8 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.52 (t, J=7.8 Hz, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 2.27 (s, 3 H, ArCH.sub.3), 1.63-1.52 (m, 3 H, (CH.sub.3).sub.2CHCH.sub.2CH.sub.2), 1.26-1.16 (m, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 0.87 (d, J=6.6 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =201.8 (d), 140.9 (s), 138.2 (s), 132.9 (s), 130.3 (d), 128.7 (d), 126.4 (d), 44.2 (t), 38.7 (t), 35.8 (t), 29.5 (t), 27.9 (d), 25.5 (t), 22.6 (q), 18.9 (q). MS: m/z (%)=232 (50) [M.sup.+], 214 (64), 204 (4), 188 (14), 176 (23), 161 (42), 143 (57), 129 (32), 119 (100), 105 (75), 91 (40), 77 (7), 65 (5), 55 (7), 43 (18).

(63) The following compounds were prepared according to the sequence described in Example 11.

EXAMPLE 12

(64) ##STR00025##

(65) 3-(5-Isobutyl-2-methylphenyl)propanal

(66) Odor: aldehydic, floral, pungent

(67) .sup.1H NMR (CDCl.sub.3): =9.86-9.83 (m, 1H, CHO), 7.05 (d, J=8.0 Hz, 1 H, ArH), 6.91 (d, J=8.0 Hz, 1 H, ArH), 6.90 (s, 1 H, ArH), 2.92 (t, J=7.6 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.73 (t, J=7.6 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.41 (d, J=7.1 Hz, 2 H, ArCH.sub.2CH(CH.sub.3).sub.2), 2.28 (s, 3 H, ArCH.sub.3), 1.88-1.74 (m, 1H, (CH.sub.3).sub.2CH), 0.88 (d, J=6.6 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =201.8 (d), 139.6 (s), 137.9 (s), 132.9 (s), 130.1 (d), 129.4 (d), 127.2 (d), 45.0 (t), 44.2 (t), 30.2 (d), 25.5 (t), 22.4 (q), 18.8 (q). MS: m/z (%)=204 (37) [M.sup.+], 186 (32), 161 (83), 143 (62), 129 (17), 119 (100), 105 (36), 91 (32), 77 (11), 65 (5), 55 (4), 41 (9).

EXAMPLE 13

(68) ##STR00026##

(69) 3-(5-Isopentyl-2-methylphenyl)propanal

(70) Odor: floral, aldehydic, watery, metallic

(71) .sup.1H NMR (CDCl.sub.3): =9.86-9.82 (m, 1H, CHO), 7.05 (d, J=8.1 Hz, 1 H, ArH), 6.95 (d, J=8.1 Hz, 1 H, ArH), 6.94 (s, 1 H, ArH), 2.91 (t, J=7.6 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.73 (t, J=7.6 Hz, 2 H, ArCH.sub.2CH.sub.2CHO), 2.54 (t, J=8.0 Hz, 2 H, ArCH.sub.2CH.sub.2CH(CH.sub.3).sub.2), 2.27 (s, 3 H, ArCH.sub.3), 1.64-1.52 (m, 1H, (CH.sub.3).sub.2CH), 1.51-1.41 (m, 2 H, ArCH.sub.2CH.sub.2CH(CH.sub.3).sub.2), 0.92 (d, J=6.4 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =201.8 (d), 141.0 (s), 138.2 (s), 132.9 (s), 130.3 (d), 128.7 (d), 126.4 (d), 44.2 (t), 41.0 (t), 33.4 (t), 27.7 (d), 25.1 (t), 22.6 (q), 18.9 (q). MS: m/z (%)=218 (44) [M.sup.+], 200 (20), 175 (5), 161 (27), 144 (80), 131 (23), 118 (100), 105 (48), 91 (41), 77 (12), 65 (5), 55 (5), 41 (14).

EXAMPLE 14

(72) ##STR00027##

(73) 3-(5-Isopentyl-2-methylphenyl)-2-methylpropanal

(74) Odor: watery, aldehydic

(75) 5 .sup.1H NMR (CDCl.sub.3): =9.75-9.69 (m, 1H, CHO), 7.06 (d, J=7.6 Hz, 1 H, ArH), 6.95 (d, J=8.0 Hz, 1 H, ArH), 6.92 (s, 1 H, ArH), 3.06 (dd, J=5.8 Hz, 13.6 Hz, 2 H, ArCH.sub.2CH(CH.sub.3)CHO), 2.69-2.58 (m, 1H, CHCHO), 2.54 (t, J=7.4 Hz, 2 H, ArCH.sub.2CH.sub.2CH(CH.sub.3).sub.2), 2.27 (s, 3 H, ArCH.sub.3), 1.65-1.51 (m, 1H, (CH.sub.3).sub.2CH), 1.50-1.41 (m, 2 H, ArCH.sub.2CHCH(CH.sub.3).sub.2), 1.11 (d, J=6.9 Hz, 3 H, CH.sub.3), 0.92 (d, J=6.4 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =204.5 (d), 140.7 (s), 136.9 (s), 133.1 (s), 130.4 (d), 129.8 (d), 126.5 (d), 46.9 (d), 41.0 (t), 33.9 (t), 33.3 (t), 27.7 (d), 22.6 (q), 19.1 (q), 13.5 (q). MS: m/z (%)=232 (25) [M.sup.+], 214 (21), 199 (5), 175 (34), 158 (33), 143 (14), 131 (15), 119 (100), 105 (38), 91 (25), 77 (8), 65 (4), 55 (3), 41 (10).

EXAMPLE 15

(76) ##STR00028##

(77) 3-(5-Isobutyl-2-methylphenyl)-2-methylpropanal

(78) Odor: green, fatty, aldehydic, bisabolene-like

(79) .sup.1H NMR (CDCl.sub.3): =9.73-9.70 (m, 1H, CHO), 7.06 (d, J=7.7 Hz, 1 H, ArH), 6.91 (d, J=7.7 Hz, 1 H, ArH), 6.88 (s, 1 H, ArH), 3.11-3.03 (m, 1 H, ArCH.sub.2CH(CH.sub.3)CHO), 2.70-2.49 (m, 2 H, ArCH.sub.2CH(CH.sub.3)CHO), 2.41 (d, J=7.1 Hz, 2 H, ArCH.sub.2CH(CH.sub.3).sub.2), 2.28 (s, 3 H, ArCH.sub.3), 1.86-1.77 (m, 1H, (CH.sub.3).sub.2CH), 1.10 (d, J=6.6 Hz, 3 H, CH.sub.3), 0.88 (d, J=6.6 Hz, 6H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =204.6 (d), 139.3 (s), 136.6 (s), 133.2 (s), 130.6 (d), 130.3 (d), 127.3 (d), 46.9 (d), 45.0 (t), 33.9 (t), 30.3 (d), 22.4 (q), 22.3 (q), 19.0 (q), 13.4 (q). MS: m/z (%)=218 (35) [M.sup.+], 200 (47), 185 (7), 175 (46), 161 (86), 147 (29), 129 (15), 119 (100), 105 (72), 91 (32), 77 (12), 67 (4), 57 (7), 41 (13).

EXAMPLE 16

(80) ##STR00029##

(81) 2-Methyl-3-(2-methyl-5-(4-methylpentyl)phenyl)propanal

(82) Odor: watery, aldehydic, metallic, sharp, citrus, mandarin

(83) .sup.1H NMR (CDCl.sub.3): =9.73-9.70 (m, 1H, CHO), 7.06 (d, J=7.6 Hz, 1H, ArH), 6.95 (d, J=7.6 Hz, 1H, ArH), 6.92 (s, 1H, ArH), 3.11-3.03 (m, 1 H, ArCH.sub.2CH(CH.sub.3)CHO), 2.66-2.48 (m, 4 H), 2.27 (s, 3 H, ArCH.sub.3), 1.63-1.48 (m, 3 H, (CH.sub.3).sub.2CHCH.sub.2CH.sub.2), 1.25-1.16 (m, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 1.10 (d, J=6.9 Hz, 3 H, CH.sub.3), 0.86 (d, J=6.6 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =204.4 (d), 140.6 (s), 136.9 (s), 133.2 (s), 130.4 (d), 129.9 (d), 126.6 (d), 46.9 (d), 38.7 (t), 35.8 (t), 33.9 (t), 29.5 (t), 27.9 (d), 22.6 (q), 19.1 (q), 13.4 (q). MS: m/z (%)=246 (38) [M.sup.+], 228 (73), 213 (13), 203 (5), 189 (53), 176 (31), 157 (32), 147 (32), 131 (22), 119 (98), 105 (100), 91 (37), 77 (12), 65 (5), 55 (9), 43 (24).

EXAMPLE 17

(84) ##STR00030##

(85) 3-(2-Methyl-5-(4-methylpentyl)phenyl)butanal

(86) Odor: weak, green, watery, floral

(87) .sup.1H NMR (CDCl.sub.3): =9.73-9.69 (m, 1H, CHO), 7.05 (d, J=7.7 Hz, 1H, ArH), 6.98 (s, 1H, ArH), 6.93 (d, J=7.7 Hz, 1H, ArH), 3.63-3.51 (m, 1 H, ArC/CH.sub.3)CH.sub.2CHO), 2.79-2.60 (m, 2 H, CHCH.sub.2CHO), 2.53 (t, J=7.8 Hz, 2 H, ArCH.sub.2), 2.32 (s, 3 H, ArCH.sub.3), 1.63-1.49 (m, 3 H, (CH.sub.3).sub.2CHCH.sub.2CH.sub.2), 1.27 (d, J=6.9 Hz, 3 H, CH.sub.3), 1.26-1.16 (m, 2 H, ArCH.sub.2CH.sub.2CH.sub.2), 0.87 (d, J=6.6 Hz, 6 H, 2 CH.sub.3). .sup.13C NMR (CDCl.sub.3): =204.4 (d), 143.3 (s), 141.0 (s), 132.2 (d), 130.5 (d), 126.2 (d), 125.4 (d), 51.2 (d), 38.7 (t), 36.0 (t), 29.5 (t), 29.3 (d), 27.9 (d), 22.6 (q), 21.6 (q), 19.0 (q). MS: m/z (%)=246 (89) [M.sup.+], 228 (42), 213 (14), 203 (100), 189 (14), 175 (31), 161 (34), 143 (26), 133 (90), 119 (55), 105 (78), 91 (35), 77 (11), 65 (5), 55 (9), 43 (31).

EXAMPLE 18

(88) In this floral perfume formulation 3-(4-isobutyl-2-methylphenyl)propanal increases the floral signature and makes this chypre fresher with a nice floral vibration, emphasizing the softness of the woods while maintaining the fruity spicy tonality

(89) TABLE-US-00001 ETHYL PHENYL ALCOHOL 60-12-8 20.00 ALD C 11 UNDECYLENIQUE at 10% in BB 9.00 AMBERMAX 10%/TEC 3.00 BENZYL BENZOATE 120-51-4 93.00 BERGAMOTE ESS ITALIE ORPUR 8007-75-8 75.00 CASHMERAN 33704-61-9 9.00 CHENE EXTRAIT CO2/ETHANOL 8.00 CITRON ESS ITALIE SFUMATRICE ORPUR 8008-56-8 45.00 DIHYDRO ISOJASMONATE METHYLE 37172-53-5 100.00 GALBANUM ESS CONCENTREE 10% in DPG 25.00 GERANIOL 980 106-24-1 15.00 GIVESCONE 57934-97-1 100.00 GRAPEFRUIT ESS COSMOS 8016-20-4 30.00 JASMIN ABS COMMUNELLE 8022-96-6 10.00 JAVANOL 198404-98-7 2.00 KOHINOOL 862107-86-6 20.00 NONADIENOL-2,6 10%/TEC at 1% in BB 15.00 OENANTHATE ALLYLE at 10% in BB 8.00 PATCHOULI ESS FRACTION INDONESIE 8014-09-3 20.00 ORPUR PECHE PURE 104-67-6 3.00 PEPPERWOOD 67643-70-3 55.00 SYLKOLIDE 676532-44-8 70.00 VERTOFIX COEUR 32388-55-9 120.00 3-(4-ISOBUTYL-2- 45.00 METHYLPHENYL)PROPANAL 900.00

EXAMPLE 19

(90) In vitro metabolism study. A comparison of compounds of the present invention and Lilial.

(91) Cryopreserved hepatocytes from male rats (Sprague Dawley; Lifetechnologies) were defrozen, washed in Cryopreserved Hepatocytes Recovery Medium (CHRM; Lifetechnologies) and suspended in Williams E Medium (WEM; Lifetechnologies). Lilial, or the compounds of the present invention (final concentration: 100 M) were added to the cells (110.sup.6 viable cells/ml) and suspensions were incubated up to 4 hours at 37 C. on a shaker in duplicate. Metabolism of testosterone was monitored as positive control. Decrease of the test compounds and formation of the corresponding benzoic acid derivative was determined by GC-MS analysis of methyl esters formed after derivatisation with trimethylsilyl diazomethane (Sigma-Aldrich) in methanol. The test compounds react with diazomethane yielding a methyl ketone which was used for the quantification of Lilial and the compound of formula (I). Metabolism was stopped with ice cold 1 M HCl, samples were extracted with tert-butyl methyl ether (MTBE) and analysed by GC-MS. Incubations containing testosterone as control were also stopped with ice cold 1 M HCl, centrifuged to separate the cells, filtrated and the decrease of testosterone analysed by LC-MS. To quantify decrease of the test substances and formation of benzoic acid metabolites, calibration curves of reference materials (Lilial and the compounds of the present invention, tert-butyl benzoic acid (Fluka) was prepared in hepatocyte incubation medium and analysed like the hepatocyte samples.

(92) A rapid decrease of testosterone as positive control was observed indicating that the hepatocytes were metabolically active. The compounds of the present invention and Lilial were metabolised rapidly in rat hepatocytes and no residual compound except for 2% with one compound was measured after 4 h. Whereas tert-butyl benzoic acid was detected as metabolite of Lilial (3.4-3.9 M) no benzoic acid derivatives were formed from compounds of the present invention (Table 1). Limit of detection was <1 M.

(93) Table 1 (below), shows the concentrations of Lilial and compounds of the present invention as well as corresponding benzoic acid metabolites in rat hepatocytes within 4 hours incubation. Initial test concentration at 0 hours incubation was 100 M.

(94) It is clear from the data presented in Table 1 that the ortho substituent at the benzene ring of the compounds of the present invention prevents the formation of the corresponding benzoic acid derivative in vitro. Since benzoic acid derivatives such as tert-butyl benzoic acid from Lilial cause reproductive toxicity in male rats, these toxic effects in male rats are prevented by the ortho-substituent of the compounds of the present invention.

(95) TABLE-US-00002 Residual concentration Benzoic acid Concentration Test compound (M) derivative (M) 0 3.5-3.9 M 0 not found 0 not found 0 not found 0 0 not found 0 not found 2.4 M not found