Esters of jasmorange oxime

Article abstract of DOI:10.1007/s10600-007-0140-z

The aldehyde jasmorange (1) was converted to the oxime (2), acylation of which by alkylcarboxylic acid anhydrides in the presence of HClO₄ or by acid chlorides in the presence of pyridine synthesized esters of jasmorange oxime 3-24 in 82-91% yi

Full text of DOI:10.1007/s10600-007-0140-z

Chemistry of Natural Compounds, Vol. 43, No. 4, 2007
ESTERS OF JASMORANGE OXIME
E. A. Dikusar,1 N. A. Zhukovskaya,1
K. L. Moiseichuk,1 and O. G. Vyglazov2
UDC 547.362
1
2
The aldehyde jasmorange ( ) was converted to the oxime ( ), acylation of which by alkylcarboxylic acid
anhydrides in the presence of HClO or by acid chlorides in the presence of pyridine synthesized esters of
4
3 24
jasmorange oxime -
3 24
in 82-91% yields. Refluxing - in hexane converted them quantitatively into
25
nitrile
.
Key words: jasmorange, oxime, carboxylic acids, anhydrides, acid chlorides, esters, nitrile, chemical modification.
The aldehyde jasmorange [2-methyl-3-(4-tolyl)propanal, 1] has a sharp fruity-balsamic fragrance with hints of
watermelon and greens and is used in perfumes and fragrances [1]. Oximes of several natural compounds act as convenient
synthons for preparing fragrances and biologically active compounds based on them [2, 3].
The goal of our work was to prepare a series of new esters from jasmorange oxime (2). Esters of jasmorange oxime
3-24 were synthesized byreacting 2 with anhydrides ofalkylcarboxylic acids in the presence ofcatalytic amounts ofHClO (3-6)
4
or with aklyl- and arylcarboxylic acid chlorides in the presence of pyridine (7-25). The yields of 3-24 were 82-91%.
CH NOH
CH NOC(O)R
CHO
1
2
3 - 24
R = Me (3); Et (4); Pr (5); Me2CH (6); Me(CH2)3 (7); Me2CHCH2 (8); Me3C (9); Me(CH2)4 (10); Me(CH2)5 (11); Me(CH2)6 (12);
Me(CH2)7 (13); Me(CH2)8 (14); Me(CH2)11 (15); Me(CH2)16 (16); cycle-C6H11 (17); C6H5 (18); C6H5CH2 (19); C6H5(CH2)2 (20);
C6H5CHMeCH2 (21); trans-C6H5CH=CH (22); MeO (23); EtO (24)
The prepared esters 3-24 are derivatives of an aldehyde and are sensitive to heating, in contrast with esters based on
ketone oximes [3]. Refluxing solutions of 3-24 in hexane converted them quantitatively into 1-(4-tolyl)-2-cyanopropane (25)
in 98-100% yield via loss of the corresponding carboxylic acids.
The structures of 2-25 were confirmed by elemental analysis; PMR, IR, and UV spectra; and cryoscopic molecular-
weight determination. According to PMR spectra, the products were 98 ± 1% pure. Elemental analyses and molecular-weight
determinations of all synthesized compounds agreed with those calculated.
The aromas of 2, esters 3-24, and nitrile 25 were assessed for organoleptic value bythe Taste Council of the Accredited
Monitoring Analytical Laboratory of OOO Tereza-Inter (Moscow). Table 1 lists the mean statistical taste data for the aromas
of the products.
Table 1 shows that all prepared compounds are highly interesting for potential use in perfumes and food production.
The hint of fresh watermelon and fruit found in most of the synthesized compounds was important and promising for modern
trends in perfume development.
1) Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 220072, Minsk, ul. Surganova,
13, e-mail: evgen_58@mail.ru; 2) OOO Tereza Inter, Russia, 129110, Moscow, Olimpiiskii prosp., 22, e-mail:
ilb_chuiko@mail.ru. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 307-310, July-August, 2007. Original article
submitted April 9, 2007.
0009-3130/07/4304-0369 ©2007 Springer Science+Business Media, Inc.
369

TABLE 1. Organoleptic Assessment of Aromas of 2-25
Compound
Odor
2
Light, fruity-berry, hints of pear, cherry, and jasmine
3
4
5
Fruity-flowery, hints of watermelon, cherry, and lilac on a powdery background
Fruity, fresh, hints of watermelon, banana, and pineapple on an anise background
Fruity, heavy, hint of butter on a cheesy background
6
Oily-spicy, hints of melted butter, cheese, and cumin
7
Fruity-spicy with a hint of cream
8
Fruity-berry, hints of pineapple and strawberry
9
Berry-flowery, hints of gardenia, rose, and strawberry on a cosmetic background
Berry-fruity, hints of ripe apple, watermelon, sea buckthorn, and cranberry
Berry-fruity on a flowery background, hints of currant, forest berry, green apple, and geranium
Berry-fruity on a wine-spice background with a hint of anise-watermelon
Berry-spicy with a hint of sour wine
Weak, berry, hints of red wine and raspberry with a hint of metallic powder
Weak with a light aroma of watermelon seeds
Weak, flowery-fruity with a hint of woody iris
Fruity, aldehyde, watermelon-pear with a hint of wine
Fruity, spicy, watermelon with a hint of balsam
Fruity-honey, watermelon with a hint of myrrh and civet
Sweet, spicy with a chemical background
Fruity-spicy, hints of anise and honey on a cucumber background
Watermelon-spicy, hints of ozone and balsam
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Flowery-fruity, hint of cyclamen, watermelon, and anise
Flowery-watermelon with a hint of milk and cheese
Woody-fruity with a spicy hint of benzoic resin and cinnamon on a sweet honey background
EXPERIMENTAL
IR spectra in thin layers or KBr were recorded on a Protege-460 IR-Fourier spectrophotometer (Nicolet); UV spectra
in MeOH (1·10 −4 M solutions), on a Specord UV-Vis instrument. PMR spectra in CDCl (5% solutions) were obtained on a
3
BS-587A spectrometer (100 MHz, Tesla). Chemical shifts were determined relative to TMS internal standard. Molecular
weights were determined cryoscopically in benzene. Column chromatography used silica gel L 5/40 µm with hexane eluent.
Jasmorange Oxime (2). Jasmorange (1, 0.21 mol), hydroxylamine hdyrochloride (0.27 mol), sodium bicarbonate
(0.28 mol), and ethanol (75 mL, 96%) were refluxed for 1 h. The reaction mixture was poured into a beaker with water
(300 mL), cooled to 5°C, and left for 10-12 h. The resulting crystalline precipitate was filtered on a porous glass filter, washed
with a small quantity of water, and dried in air to afford 2, 95% yield, mp 33-34°C, C H NO.
11 15
IR spectrum (ν, cm −1): 3264 (OH); 3094, 3075, 3020, 3004 (=CHand CH ); 2966, 2923, 2872 (CH ); 1640 (C=N);
Ar
Alk
1515, 1455, 1377 (Ar); 959, 943 (N–O); 860, 840, 803, 750, 720 (CH ). UV spectrum (λ , nm, ε): 216 (5000).
Ar
max
PMR spectrum (δ, ppm): 1.06 (m, CH ), 2.35 (s, CH ), 2.50-2.95 (m, CH and CH), 6.95-7.20 (m, C H ), 7.39 (d, HC=N).
3
3
2
6 4
Jasmorange Oxime Esters 3-6 (General Method). Jasmorange oxime (2, 0.01 mol) and the appropriate acid
anhydride (0.011 mol) were dissolved in hexane (30 mL), treated with HClO (47%, one drop), shaken, left at 20-23°C for
4
24-36 h, and diluted with water. The product was extracted with hexane. The organic layer was separated, washed with water
and NaHCO solution (5%), and dried over CaCl . Solvent was removed at reduced (30-45 mm Hg) pressure keeping the
3
2
temperature below 25-30°C. The product was purified by column chromatography over silica gel with elution by hexane.
The following compounds were prepared by this method.
20
20
2-Methyl-3-(4-tolyl)-propanal-O-acetyloxime (3). Yield89%, d
1.0637, n
1.5120. C H NO . IRspectrum
13 17 2
20
D
(ν, cm −1): 3090, 3040, 3021, 3004 (=CH and CH ); 2980, 2925, 2878, 2862 (CH ); 1763 (C=O); 1631 (C=N); 1516, 1456,
Ar
Alk
1370 (Ar); 1244, 1208 (C–O); 875, 845, 803, 765, 745 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 1.32 (m, CH ), 2.35 (s, CH and CH ), 2.60-3.00 (m, CH and CH), 6.95-7.20 (m, C H ), 7.58 (d, HC=N).
3
3
3
2
6 4
370

20
20
2-Methyl-3-(4-tolyl)-propanal-O-propionyloxime (4). Yield 88%, d
1.0470, n
1.5105. C H NO .
14 19 2
20
D
IR spectrum (ν, cm −1): 3090, 3040, 3021, 3003 (=CH and CH ); 2979, 2939, 2925, 2879, 2870 (CH ); 1766 (C=O); 1631
Ar
Alk
(C=N); 1515, 1460, 1380 (Ar); 1145, 1070 (C–O); 865, 804, 745 (CH ). UV spectrum (λ , nm, ε): 216 (5000).
Ar
max
PMR spectrum (δ, ppm): 1.05-1.40 (m, CH and CH ), 2.31 (s, CH ), 2.10-3.05 (m, CH , CH and CH), 6.95-7.15 (m, C H ),
3
3
3
2
2
6 4
7.58 (d, HC=N).
20
20
2-Methyl-3-(4-tolyl)-propanal-O-butyryloxime (5). Yield87%, d
(ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2967, 2933, 2875 (CH ); 1766 (C=O); 1631 (C=N); 1515, 1458, 1380
0.9771, n
1.5115. C H NO .IRspectrum
15 21 2
20
D
Ar
Alk
(Ar); 1149, 1080 (C–O); 850, 803, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum (δ, ppm): 0.85-1.30
Ar
max
(m, CH and CH ), 1.77 (q, CH ), 2.32 (s, CH ), 2.15-3.08 (m, CH , CH and CH), 6.90-7.15 (m, C H ), 7.58 (d, HC=N).
3
3
2
3
2
2
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-isobutyryloxime (6). Yield 90%, d
1.0630, n
1.5080. C H NO .
20
D
15 21
2
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2975, 2933, 2876 (CH ); 1764 (C=O); 1631 (C=N); 1516,
Ar
Alk
1458, 1385 (Ar); 1121, 1098 (C–O); 854, 830, 802, 757 (CH ). UV spectrum (λ , nm, ε): 216 (5000).
Ar
max
PMR spectrum (δ, ppm): 1.12 (m, CH ), 1.20 [d, (CH ) C], 2.30 (s, CH ), 2.45-3.05 (m, CH , CH and CH), 6.90-7.15
3
3 2
3
2
(m, C H ), 7.58 (d, HC=N).
6
4
Jasmorange Oxime Esters 7-24 (General Method). Jasmorange oxime (2, 0.01 mol) was dissolved in hexane
(50 mL), treated with absolute pyridine (0.01 mol), cooled to 15°C, stirred bycarefullyshaking, and treated with the appropriate
acid chloride (0.01 mol). The mixture was left at 20-23°C for 24-36 h and diluted with water. The product was extracted with
hexane. The organic layer was separated, washed with water and NaHCO solution (5%), and dried over CaCl . Solvent was
3
2
removed at reduced (30-45 mm Hg) pressure keeping the temperature below 25-30°C. The product was purified by column
chromatography over silica gel with elution by hexane.
The following compounds were prepared by this method.
2-Methyl-3-(4-tolyl)-propanal-O-valeryloxime (7). Yield 88%, d
20
20
1.0334, n
1.5100. C H NO .
16 23 2
20
D
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2961, 2931, 2873 (CH ); 1765 (C=O); 1631 (C=N); 1516,
Ar
Alk
1457, 1379 (Ar); 1148, 1092 (C–O); 877, 855, 802, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum (δ,
Ar
max
ppm): 0.89 (t, CH ), 1.12 (m, CH ), 1.20-1.80 [m, (CH ) ], 2.32 (s, CH ), 2.00-3.02 (m, CH , CH and CH), 6.90-7.20 (m,
3
3
2 2
3
2
2
C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-isovaleryloxime (8). Yield 89%, d
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2962, 2931, 2873 (CH ); 1765 (C=O); 1631 (C=N); 1516,
1.1073, n
1.5075. C H NO .
16 23 2
20
D
Ar
Alk
1457, 1379 (Ar); 1154, 1090 (C–O); 876, 855, 802, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum (δ,
Ar
max
ppm): 0.92 [d, (CH ) C], 1.12 (m, CH ), 1.20-1.40 (m, CH ), 2.32 (s, CH ), 1.90-3.05 (m, CH , CH and CH), 6.90-7.15 (m,
3 2
3
2
3
2
C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-pivalyloxime (9). Yield86%, d
(ν, cm −1): 3090, 3040, 3021, 3003 (=CH and CH ); 2976, 2932, 2875 (CH ); 1754 (C=O); 1631 (C=N); 1516, 1457, 1379
0.9121, n
1.4960. C H NO . IRspectrum
20
D
16 23
2
Ar
Alk
(Ar); 1150, 1111 (C–O); 876, 855, 802, 755 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum (δ, ppm): 1.10
Ar
max
(m, CH ), 1.28 [s, (CH ) C], 2.34 (s, CH ), 2.55-3.02 (m, CH and CH), 6.90-7.15 (m, C H ), 7.60 (d, HC=N).
3
3 3
3
2
6 4
1.0088, n
20
20
2-Methyl-3-(4-tolyl)-propanal-O-caproyloxime (10). Yield 91%, d
1.5070. C H NO .
17 25 2
20
D
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2958, 2930, 2872, 2861 (CH ); 1766 (C=O); 1631 (C=N);
Ar
Alk
1516, 1458, 1379 (Ar); 1149, 1093 (C–O); 871, 855, 803, 755 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMRspectrum
Ar
max
(δ, ppm): 0.90 (t, CH ), 1.12 (m, CH ), 1.15-1.90 [m, (CH ) ], 2.32 (s, CH ), 2.10-3.00 (m, CH , CH and CH), 6.90-7.20 (m,
3
3
2 3
3
2
2
C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-enanthyloxime (11). Yield 92%, d
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2957, 2930, 2872, 2859 (CH ); 1766 (C=O); 1631 (C=N);
0.9936, n
1.5065. C H NO .
18 27 2
20
D
Ar
Alk
1516, 1458, 1379 (Ar); 1149, 1096 (C–O); 871, 855, 803, 755 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 0.91 (t, CH ), 1.12 (m, CH ), 1.10-1.90 [m, (CH ) ], 2.32 (s, CH ), 2.10-3.00 (m, CH , CH and CH), 6.90-7.20 (m,
3
3
2 4
3
2
2
C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-caprylyloxime (12). Yield 88%, d
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3003 (=CH and CH ); 2956, 2928, 2870, 2857 (CH ); 1766 (C=O); 1631 (C=N);
0.9820, n
1.4980. C H NO .
19 29 2
20
D
Ar
Alk
1516, 1458, 1378 (Ar); 1142, 1096 (C–O); 877, 855, 802, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 0.89 (t, CH ), 1.13 (m, CH ), 1.08-1.90 [m, (CH ) ], 2.32 (s, CH ), 2.10-3.05 (m, CH , CH and CH), 6.90-7.20 (m,
3
3
2 5
3
2
2
C H ), 7.58 (d, HC=N).
6
4
371

20
20
2-Methyl-3-(4-tolyl)-propanal-O-pelargonyloxime (13). Yield 90%, d
0.9750, n
1.4850. C H NO .
20 31 2
20
D
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3002 (=CH and CH ); 2955, 2926, 2870, 2856 (CH ); 1766 (C=O); 1631 (C=N);
Ar
Alk
1516, 1458, 1378 (Ar); 1143, 1099 (C–O); 880, 855, 802, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 0.89 (t, CH ), 1.13 (m, CH ), 1.02-1.90 [m, (CH ) ], 2.32 (s, CH ), 2.08-3.05 (m, CH , CH and CH), 6.90-7.20
3
3
2 6
3
2
2
(m, C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-capryloxime (12). Yield 92%, d
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3002 (=CH and CH ); 2955, 2926, 2870, 2855 (CH ); 1767 (C=O); 1631 (C=N);
0.9916, n
1.4970. C H NO .
20
D
21 33
2
Ar
Alk
1516, 1458, 1378 (Ar); 1141, 1101 (C–O); 878, 855, 802, 754 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 0.89 (t, CH ), 1.13 (m, CH ), 1.00-1.88 [m, (CH ) ], 2.33 (s, CH ), 2.08-3.04 (m, CH , CH and CH), 6.90-7.18 (m,
3
3
2 7
3
2
2
C H ), 7.58 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-tridecanoyloxime (15). Yield 86%, d
IR spectrum (ν, cm −1): 3090, 3040, 3020, 3002 (=CH and CH ); 2953, 2924, 2852 (CH ); 1767 (C=O); 1631 (C=N); 1516,
0.9845, n
1.4860. C H NO .
24 39 2
20
D
Ar
Alk
1459, 1378 (Ar); 1140, 1104 (C–O); 876, 850, 804, 745, 720 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum
Ar
max
(δ, ppm): 0.88 (t, CH ), 1.12 (m, CH ), 1.00-1.90 [m, (CH ) ], 2.32 (s, CH ), 2.06-3.04 (m, CH , CH and CH), 6.90-7.20 (m,
3
3
2 10
3
2
2
C H ), 7.58 (d, HC=N).
6
4
2-Methyl-3-(4-tolyl)-propanal-O-stearyloxime (16). Yield 89%, mp 37-38°C. C H NO . IR spectrum (ν, cm −1):
29 49
2
3090, 3040, 3020, 3002 (=CH and CH ); 2954, 2918, 2850 (CH ); 1752 (C=O); 1631 (C=N); 1516, 1459, 1378 (Ar); 1472
Ar
Alk
(CH ); 1145, 1102 (C–O); 876, 845, 802, 750, 720 (CH ). UV spectrum (λ , nm, ε): 216 (5000). PMR spectrum (δ, ppm):
2
Ar
max
0.88 (t, CH ), 1.12 (m, CH ), 1.00-1.92 [m, (CH ) ], 2.32 (s, CH ), 2.06-3.04 (m, CH , CH and CH), 6.90-7.20 (m, C H ),
3
3
2 15
3
2
2
6 4
7.58 (d, HC=N).
20
20
2-Methyl-3-(4-tolyl)-propanal-O-cyclohexanemethanoyloxime (17). Yield 89%, d
1.1037, n
1.5245.
20
D
−1
C H NO . IR spectrum (ν, cm ): 3090, 3040, 3020, 3002 (=CH and CH ); 2931, 2856 (CH ); 1762 (C=O); 1631
18 25
2
Ar
Alk
(C=N); 1515, 1451, 1379 (Ar); 1151, 1107 (C–O); 876, 848, 803, 755, 720 (CH ). UV spectrum (λ , nm, ε): 216 (5000).
Ar
max
PMR spectrum (δ, ppm): 0.80-2.10 (m, C H ), 1.12 (m, CH ), 2.33 (s, CH ), 2.45-3.10 (m, CH and CH), 6.90-7.22 (m, C H ),
6
11
3
3
2
6 4
7.61 (d, HC=N).
20
20
2-Methyl-3-(4-tolyl)-propanal-O-benzoyloxime (18). Yield 84%, d
IR spectrum (ν, cm −1): 3090, 3070, 3045, 3033, 3020, 3004 (=CH and CH ); 2981, 2935, 2926, 2876, 2856 (CH ); 1720
1.0845, n
1.5185. C H NO .
18 19 2
20
D
Ar
Alk
(C=O); 1631 (C=N); 1516, 1479, 1454, 1380 (Ar); 1276, 1110 (C–O); 855, 817, 792, 775, 755, 730, 715, 682 (CH ).
Ar
UV spectrum (λ , nm, ε): 207 (15,000), 218 (13,000), 250 (8000). PMR spectrum (δ, ppm): 1.20 (m, CH ), 2.36 (s, CH ),
max
3
3
2.60-3.05 (m, CH and CH), 7.00-8.15 (m, C H and C H ), 7.60 (d, HC=N).
2
6
5
6 4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-phenylacetyloxime (19). Yield 87%, d
1.0838, n
1.5265. C H NO .
19 21 2
20
D
IR spectrum (ν, cm −1): 3090, 3070, 3045, 3033, 3020, 3004 (=CH and CH ); 2981, 2935, 2926, 2876, 2856 (CH ); 1720
Ar
Alk
(C=O); 1631 (C=N); 1516, 1479, 1454, 1380 (Ar); 1276, 1110 (C–O); 855, 817, 792, 775, 755, 730, 715, 682 (CH ). UV
Ar
spectrum (λ , nm, ε): 210 (6000), 216 (6000). PMR spectrum (δ, ppm): 1.20 (m, CH ), 2.36 (s, CH ), 2.60-3.05 (m, CH
max
3
3
2
and CH), 3.84 (s, CH ), 7.05-7.55 (m, C H and C H ), 7.60 (d, HC=N).
2
6
5
6 5
20
20
2-Methyl-3-(4-tolyl)-propanal-O-(3-phenylpropionyl)oxime (20). Yield 88%, d
1.1314, n
1.5375.
20
D
C H NO . IR spectrum (ν, cm −1): 3090, 3048, 3026, 3002 (=CH and CH ); 2978, 2925, 2872, 2860 (CH ); 1764 (C=O);
20 23
2
Ar
Alk
1631 (C=N); 1601, 1516, 1498, 1454, 1379 (Ar); 1181, 1121 (C–O); 877, 855, 803, 752, 700 (CH ). UV spectrum
Ar
(λ , nm, ε): 212 (9000). PMR spectrum (δ, ppm): 1.30 (m, CH ), 2.35 (s, CH ), 2.55-3.15 [m, (CH ) , CH and CH], 6.90-
max
3
3
2 2
2
7.35 (m, C H and C H ), 7.59 (d, HC=N).
2-Methyl-3-(4-tolyl)-propanal-O-(3-phenylbutyryl)oxime (21). Yield90%, d
IR spectrum (ν, cm −1): 3090, 3049, 3024, 3003 (=CH and CH ); 2979, 2925, 2876, 2865 (CH ); 1764 (C=O); 1631 (C=N);
6
5
6 4
20
20
1.0650, n
1.5260. C H NO .
20
D
21 25
2
Ar
Alk
1516, 1497, 1454, 1380 (Ar); 1120 (C–O); 845, 814, 792, 770, 765, 730, 701 (CH ). UV spectrum (λ , nm, ε): 213 (9000).
Ar
max
PMR spectrum (δ, ppm): 1.30 (m, CH ), 1.43 (d, CH ), 2.35 (s, CH ), 2.50-3.60 (m, 2×CH and 2×CH), 6.90-7.30 (m, C H
3
3
3
2
6
5
and C H ), 7.59 (d, HC=N).
6
4
20
20
2-Methyl-3-(4-tolyl)-propanal-O-(trans-cinnamyl)oxime (22). Yield 85%, d
IR spectrum (ν, cm −1): 3090, 3049, 3024, 3003 (=CH and CH ); 2979, 2925, 2876, 2865 (CH ); 1738 (C=O); 1636 (C=C);
1.1045, n
1.5510. C H NO .
20 21 2
20
D
Ar
Alk
1631 (C=N); 1516, 1497, 1454, 1380 (Ar); 1120 (C–O); 845, 814, 792, 770, 765, 730, 701 (CH ). UV spectrum
Ar
(λ , nm, ε): 206 (24,000), 220 (30,000), 280 (28,000). PMR spectrum (δ, ppm): 1.22 (m, CH ), 2.36 (s, CH ), 2.60-3.05 (m,
max
3
3
CH and CH), 6.80-7.90 (m, CH=CH, C H and C H ), 7.60 (d, HC=N).
2
6
5
6 4
372

20
20
2-Methyl-3-(4-tolyl)-propanal-O-(methylcarbonate)oxime (23). Yield90%, d
1.1037, n 1.5140. C H NO .
D 13 17 3
20
IR spectrum (ν, cm −1): 3090, 3040, 3021, 3003 (=CH and CH ); 2978, 2960, 2925, 2876, 2862 (CH ); 1778 (C=O); 1631
Ar
Alk
(C=N); 1516, 1454, 1380 (Ar); 1244 (C–O); 879, 845, 804, 780, 745 (CH ). UV spectrum (λ , nm, ε): 216 (5000).
Ar
max
PMR spectrum (δ, ppm): 1.32 (m, CH ), 2.34 (s, CH ), 2.55-3.00 (m, CH and CH), 3.87 (s, CH ), 6.95-7.20 (m, C H ), 7.58
3
3
2
3
6 4
(d, HC=N).
20
20
2-Methyl-3-(4-tolyl)-propanal-O-(ethylcarbonate)oxime (24). Yield91%, d
IR spectrum (ν, cm −1): 3090, 3040, 3019, 3002 (=CH and CH ); 2980, 2929, 2875 (CH ); 1775 (C=O); 1631 (C=N); 1516,
1.0948, n
1.5030. C H NO .
14 19 3
20
D
Ar
Alk
1456, 1369 (Ar); 1236 (C–O); 843, 804, 779, 755 (CH ). UV spectrum (λ , nm, ε): 216 (5000) PMR spectrum (δ, ppm):
Ar
max
1.32 (m, CH ), 1.40 (t, CH ), 2.34 (s, CH ), 2.55-3.00 (m, CH and CH), 4.30 (q, CH ), 6.95-7.16 (m, C H ), 7.58 (d, HC=N).
3
3
3
2
2
6 4
1-(4-Tolyl)-2-cyanopropane (25). A solution of jasmorange oxime ester (3-24, 0.005 mol) in hexane (50 mL) was
refluxed for 1 h, diluted with water, and extracted with hexane. The organic layer was separated, washed with water and
NaHCO solution (5%), and dried over CaCl . Solvent was removed at reduced (60-75 mm Hg) pressure. The product was
3
2
20
20
purified by column chromatography over silica gel with elution by hexane. Yield 98-100%, d
C H N. IR spectrum (ν, cm −1): 3090, 3049, 3022, 3003 (=CH and CH ); 2979, 2925, 2877, 2865 (CH ); 2239 (C≡N);
1.0163, n
1.5225.
20
D
11 13
Ar
Alk
1516, 1455, 1380 (Ar); 855, 816, 792, 745 (CH ). PMR spectrum (δ, ppm): 1.35 (m, CH ), 2.35 (s, CH ), 2.65-3.05 (m, CH
2
Ar
3
3
and CH), 7.15 (s, C H ).
6
4
REFERENCES
1.
S. A. Boitkevich, 865 Frangrances for Perfume and Household Chemistry [in Russian], Pishchevaya Promyshlennost′,
Ufa (1994).
2.
3.
E. A. Dikusar, N. G. Kozlov, N. A. Zhukovskaya, and K. L. Moiseichuk, Khim. Prir. Soedin., 154 (2002).
N. A. Zhukovskaya, E. A. Dikusar, K. L. Moiseichuk, and O. G. Vyglazov, Zh. Prikl. Khim., 79, 642 (2006).
373