CN1244527A - Cyclic cedrene aldehyde acetal, its preparation and its use - Google Patents
Cyclic cedrene aldehyde acetal, its preparation and its use Download PDFInfo
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Abstract
The cyclocedrene acetals as novel compounds have the odor similar to ambergris and can strengthen other aromatics and prolong their aromatic effect. Therefore, they can be used as perfume or component of perfume compound aor as aromatic oil to aromatize cosmetics and industrial products. The compounds are prepared easily by obtaining cedrene epoxide from cedrene, converging cedrene epoxide into the mixture of isomerized cedrene and diols or diastereomer cedrene and diols, and the reaction of the mixture with aliphatic carboxy compound in the presence of acid catalyst and the absence of diluent or in the aprotic solvent with hydrated reagent.
Description
The secretory product of animal, gland and other organ-tissue intensive odor characteristics attracted people several thousand deeply.From ancient times, when the fragrance of dispersing is to interrelate with magic originally, and thereby when being used for the purpose of religion and culture, had multiple other application, for example as medicine.In the beginning of this century, Long Yanxiang, Moschus and civet are to occur as composition valuable in the perfume.Therefore, nineteen twenty for the middle period, carried out measuring the analytical work first that dragon prolongs the structure of fragrant main fragrance matter.Then, early thirties has been seen synthetic its work of preparation of technical scale for the first time.Product natural, the plant and animal source can not satisfy for the ever-increasing demand of spices again.Satisfy the ever-increasing demand of high quality spices, smell quality, the stability in technology is used, skin-friendliness, environment protection Harmony toughness also for example can only be by the chemosynthesis of spices.
In order to reach stable environmental balance, wish product on the one hand, if may, constitute by reproducible raw material, on the other hand, be biodegradable.A kind of such natural matter that can obtain in a large number is a cedrene, and it is present in various types of cdear forests.
Before 20 years, prepared a series of (α)-cedrene (1) secondary products and described aromatic property.At its works " spices and sense of smell " (" Riechstoff und Geruchsinn ") [Fragrance and Sense of Smell] (Springer-Verlag, Berlin 1990, ISD-N3-540-52560-2, page 170-172) in, G.Ohloff sums up a series of commercial spices and is derived out by α-Xue Songxi (1).In " spices and seasoning chemistry " (" Perfume andFlavor Chemicals ") (No.593-600,602), S.Arctander has described several by cedrene deutero-spices.
By epoxidation, allylation, esterification and etherificate, the derivative that can be obtained by α cedrene (1) is warm woody odor type (warm-woody odor type) spices from sense organ, has some also to have the effect that dragon prolongs odor type.
According to above-mentioned prior art, in depth studied this field of flavor chemistry especially.Except some had the cedrene derivative of spices character, known had the derivative of large quantities of above-mentioned sesquiterpenes not have or do not have substantially the sense of smell characteristic.For this reason, wondrous especially part is, in this cedrene derivative field, (wherein wave molding is represented α-and β-conformation, R might to have found the compound of the novelty of general formula A as described herein
1And R
2Be hydrogen or methyl, ethyl, propyl group, butyl, isobutyl-, amyl group, isopentyl, hexyl, isohexyl, cyclopentyl and cyclohexyl), they have fairly individual odor characteristics, the known spices that exceeds significantly and be better than being prepared by α-Xue Songxi (1).The cedrene derivative of general formula A has dragon and prolongs the odor type odor characteristics, also has the strong effect of the various different flavors of dispersing of enhancing, and has prolonged its spices action effect.
The compound for preparing general formula A, adopt known method the epoxide (2) that (-)-α-Xue Songxi (1) is converted into (-)-α-Xue Songxi (to be seen that organic chemistry puts into practice (Organileum substantially with peracetic acid treatment, Organisch-Chemisches Grundpraktikum[BasicPractical Organic Chemistry]), VEB Deutscher Verlag derWissenschaften, Berlin, 1986, Order No.5714576, page 568).The epoxide (2) that will be obtained by cedrene is converted into the mixture of epimerization glycols (3) with known method (Houben-Weyl) then, and according to different working conditions, this diol mixture has different isomeric distribution and odor effect.Its structure is determined according to the result of NMR.
The ring acetal of the novelty of general formula A, prepared by reacting with aliphatic aldehyde and ketone and acid catalyst use all kinds of SOLVENTS with a kind of known method itself by the glycol (3) that occurs with purified or the form that is rich in or occur as equilibrium mixture, solvent for example is toluene, hexanaphthene, naphtha fraction or diethyl ether.
Fig. 1
Epoxide 2a that these epimers are pure and 2b can be converted into non-mapping glycol 3a-f separately or as mixture (depending on working condition).Depend on selected reaction conditions, therefore epimerization epoxide 2a can obtain diastereomeric glycol 3a/b/c/d/e/f/g/h by different amounts than producing with 2b after opening epoxide, and they equally also are different amount ratios.Still constant substantially with aldehyde and reactive ketone neutral body chemistry ratio, therefore the mixing acetal of the novelty of this general formula A is the form of non-enantiomer mixture in this case.
The novelty of these general formulas A is mixed acetal, no matter be respective pure form or as stereoisomer mixture, each all has primary spices character, and can use as spices and perfume oil composition with purified form or as mixture of diastereomers valuably.
Fig. 2
The preparation of embodiment 1 (-)-α-Xue Songxi epoxide (2)
With (-)-α-Xue Songxi (1) of 500g (2.00mol) (82%, according to GC[α]
D=-75.8 °), 500ml diethyl ether and 100g sodium acetate add and assembled in 21 mixing tanks of reflux exchanger, thermometer and dropping funnel, then at 20-25 ℃, added the peracetic acid of 430g (2.20mol) 40% in 1 hour.After being added dropwise to complete, stirred this mixture 2 hours, then handle.Isolate organic phase, end when using soda solution and water washing, also under reduced pressure distill solvent, obtain the crude product (78.2%, GC mensuration) of 526.5g with dried over sodium sulfate to neutrality.
Gas-chromatography (HP 5970 B, DBWAX-60N, 60m, 60 ℃-240 ℃, 4 ℃/min)
On 15cm Vigreux post, distill the crude product of 100g, obtain the thick product 2 of 95g; B.p.:115 ℃ of-138 ℃/2mmHg, GC2 (80.2%).D20/4：1.0009n20/D：1.4965[α]20/D：-72.4
Embodiment 22 β-, preparation-Fig. 2 of 3 beta epoxide cedrenes (2a)
With the trimethyl carbinol of 50ml, water and 14gAD-mix-the β (=0.01mol alkene equivalent of 50ml; Fa.Aldrich) join in the 250ml mixing tank that has assembled reflux exchanger, thermometer and dropping funnel and at room temperature stirred 2 hours.
After this, form clearly isolating each other two-phase.Following is light yellow mutually.Add 0.95g (0.01mol) Toluidrin in the solution of this stirring this moment.Mixture is cooled to 0 ℃ then.After original a kind of dissolved salt is precipitated out, under 0 ℃ of accompanied by intense stirs, drips (-)-α-Xue Songxi (2) (82%, GC measures) of 2.55g (0.01mol), and under this temperature, stirred this mixture whole 60 hours.Then sodium sulfite aqueous solution is joined in the reaction mixture, this reaction mixture can rise to room temperature and under this temperature restir 1 hour whole.After joining ether in the mixture, organic phase is separated, will contain water and divide three extractions with the 50ml ether at every turn, till the blended organic phase uses 10%KOH and water washing successively when neutrality.Also under reduced pressure distill solvent with dried over sodium sulfate then, obtain the crude product of 1.9g.GC2a(78％)。
Embodiment 32 α-, preparation-Fig. 2 of 3 α-epoxy cedrene (2b)
With the trimethyl carbinol of 50ml, water and 14gAD-mix-the α (=0.01mol alkene equivalent of 50ml; Fa.Aldrich) join in the 250ml mixing tank that has assembled reflux exchanger, thermometer and dropping funnel and at room temperature stir 1 hour whole.After this, formed two-phase.Following is light yellow mutually.Then 0.95g (0.01mol) Toluidrin is added in the solution of this stirring.Mixture is cooled to 0 ℃ then.After a kind of dissolved salt was precipitated out, (-)-α-Xue Songxi (2) (82.0%, GC measures) that stirs 2.55g (0.01mol) 0 ℃ of accompanied by intense joined in this suspension, and under this temperature whole 72 hours of continuously stirring.Then sodium sulfite aqueous solution is joined in the reaction mixture, this reaction mixture can rise to room temperature and at room temperature restir 1 hour is whole, finishes then.After joining ether in the mixture, organic phase is separated, will contain water and divide three extractions with the 50ml ether at every turn, till the blended organic phase uses 10%KOH and water washing successively when neutrality.The reaction mixture that generates with dried over sodium sulfate also under reduced pressure distills solvent then, obtains the crude product of 1.8g.GC2b(84.1％)。
Preparation-Fig. 1 of embodiment 4 cdear diol mixtures (3)
2000g 10% sulfuric acid and 3g Aliquat R 336 are joined in 41 three-necked bottles that assembled reflux exchanger, dropping funnel and thermometer.Accompanied by intense agitation and dropping 300g (1.09mol) is from (-)-α-Xue Songxi epoxide (2) (80.2%, GC measures) of embodiment 2 in 10 minutes then, and mixture was put in order 20-25 ℃ of violent stirring in 48 hours then.Then sedimentary organic product is filtered out, and with till 2% soda water and water washing are when the neutrality.Isolate the diol mixture (3) of 120g, then recrystallize from 21 hexanaphthene.Go out solvent with suction filtration, obtain 98g crystallization cdear glycol 3 (theoretical yield 37.6%).M.p.167-168 ℃ of GC: condition is seen embodiment 1.
3a，e，c，g：49,3％
3b，f，d，h：32,0％
GC/MS：HP?5970?B，DBWAX-60N，60m，60℃-240℃，4℃/min.
3a，e，c，g：R
t＝55,60
MS：m/e(％)＝238(10，M
+)，223(45)，205(34)，193(30)，167(46)，121(46)，107(61)，
99(66)，81(58)，43(100).
3b，d，f，h：R
t＝55,97
MS：m/e(％)＝238(10，M
+)，223(38)，205(29)，193(20)，167(34)，121(44)，109(37)，
107(40)，81(46)，43(100).
The reaction of embodiment 5 cdear diol mixtures 3 (Fig. 1) and acetone
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 23.3g (0.4mol) acetone, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred whole 24 hours in the 250ml mixing tank that has assembled dropping funnel, thermometer and reflux exchanger.After this, product is used dried over sodium sulfate, and is under reduced pressure distilled solvent till using 10% soda solution of 10ml and 50ml water washing successively when neutrality, obtains the crystallization crude product of 10.7g.
This crystallization crude product recrystallize from the 100ml acetylacetic ester.Go out solvent with suction filtration, obtain 5.6g white crystals product.The GC:(condition is seen embodiment 1) 95.6%.M.p.157-158 ℃ of GC/MS: condition is seen embodiment 2
R
t＝41,43
MS：m/e(％)＝278(5，M
+)，263(49)，221(100)，203(48)，161(10)，147(21)，133(41)，
119(73)，105(36)，69(35)，43(51).
13C-NMR(CDCl
3)，Varian?VXR?300：δ[ppm]＝15.42，27.56，28.74，29.67，30.26，31.12(CH
3)
25.42，35.88，38.51，41.00(CH
2)，41.92，57.39，58.58，78.79(CH)，42.43，52.38，84.99，108.87
(C).
The reaction of embodiment 6 cdear diol mixtures 3 (Fig. 1) and methylethylketone
At 20-25 ℃, cdear diol mixture 3 (from embodiment 4), 28.8g (0.4mol) methylethylketone, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) stirred whole 48 hours in the 250ml mixing tank that has assembled dropping funnel, thermometer and reflux exchanger.After this, product is used dried over sodium sulfate, and is under reduced pressure distilled solvent till using 10% soda solution and water washing successively when neutrality, obtains the crude product of 10.5g.The GC:(condition is seen embodiment 1) R
t=44.5=15.1%
R
t=45.4=19.1%GC/MS:(condition is seen embodiment 2)
R
t＝44,57
MS：m/e(％)＝292(3，M
+)，277(4)，263(34)，221(100)，203(49)，133(45)，119(82)，
105(40)，69(40)，43(50).
R
t＝45,20
MS：m/e(％)＝292(2，M
+)，277(2)，263(35)，221(100)，203(52)，133(43)，119(76)，
105(38)，69(37)，43(50).
The reaction of embodiment 7 cdear diol mixtures 3 (Fig. 1) and methyl propyl ketone
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 34.4g (0.4mol) methyl propyl ketone, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred whole 24 hours in the 250ml mixing tank that has assembled dropping funnel, thermometer and reflux exchanger.After this, product once washs and once washes with water with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the lurid crystallization crude product of 10.2g.The GC:(condition is seen embodiment 2) R
t=44.10=9.2%
R
t=44.68=17.7%GC/MS: condition is seen embodiment 2
R
t＝45,20
MS：m/e(％)＝306(2，M
+)，291(3)，263(33)，221(100)，203(41)，147(19)，133(38)，
119(68)，105(34)，69(35)，43(52).
R
t＝44,68
MS：m/e(％)＝306(1，M
+)，291(1)，263(31)，221(100)，203(45)，147(19)，133(39)，
119(70)，105(34)，69(34)，43(50).
The reaction of embodiment 8 cdear diol mixtures 3 (Fig. 1) and diethyl ketone
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 34.4g (0.4mol) diethyl ketone, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred whole 24 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once washs and once washes with water with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the crystallization crude product of 10.8g light brown.The GC:(condition is seen embodiment 1): the 29.5%GC/MS:(condition is seen embodiment 2)
R
t＝44,61
MS：m/e(％)＝306(4，M
+)，291(1)，277(15)，221(39)，203(21)，177(31)，159(37)，119(44)，91
(48)，69(100)，41(85).
The reaction of embodiment 9 cdear diol mixtures 3 (Fig. 1) and cyclopentanone
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 33.6g (0.4mol) cyclopentanone, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred 24 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once washs and once washes with water with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains 10.5g xanchromatic crystallization crude product.The GC:(condition is seen embodiment 1): the 49.8%GC/MS:(condition is seen embodiment 2)
R
t＝49,92
MS：m/e(％)＝304(15，M
+)，275(22)，221(100)，205(88)，133(46)，119(90)，105(48)，
69(54)，55(69)，41(54).
The reaction of embodiment 10 cdear diol mixtures 3 (Fig. 1) and pimelinketone
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 39.2g (0.4mol) pimelinketone, 100ml first and the 0.2g tosic acid of 10.1g (0.04mol) were stirred 24 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product with till 10% soda solution and water washing are when being neutrality, is used dried over sodium sulfate, and is under reduced pressure distilled solvent successively, obtains the lurid crude product of 11.3g.The GC:(condition is seen embodiment 1): the 73%GC/MS:(condition is seen embodiment 2)
R
t＝53,22
MS：m/e(％)＝318(22，M
+)，275(24)，221(100)，203(63)，147(25)，133(52)，119(91)，
105(49)，69(68)，55(66)，41(61).
13C-NMR(CDCl
3)，Varian?VXR-300：δ[ppm]＝15.45，28.10，28.71，31.20(CH
3)，24.11，24.25，
25.17，25.37，35.78，38.48，38.92，39.57，41.71(CH
2)，41.87，57.40，58.66，78.21(CH)，42.83，
52.42，84.36，109.83(C).
The reaction of embodiment 11 cdear diol mixtures 3 (Fig. 1) and acetaldehyde
At 20-25 ℃, with cdear diol mixture 3 (Fig. 1 is from embodiment 4), 17.6g (0.4mol) acetaldehyde, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) in having assembled the 250ml mixing tank of reflux exchanger and thermometer, stir 3 hours whole.After this, product once washs and once washes with water with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the crude product of 10.3g light color.The GC:(condition is seen embodiment 1): 37.8%, the 60.08%GC/MS:(condition is seen embodiment 2)
R
t＝41.29
MS：m/e(％)＝264(19，M
+)，249(43)，221(18)，203(77)，177(65)，119(100)，105(61)，
95(58)，69(71)，43(100).
R
t＝40.91
MS：m/e(％)＝264(36，M
+)，249(49)，221(24)，203(83)，177(30)，119(91)，105(57)，
95(60)，69(69)，43(100).
The reaction of embodiment 12 cdear diol mixtures 3 (Fig. 1) and propionic aldehyde
At 20-25 ℃, with cdear diol mixture 3 (Fig. 1 is from embodiment 4), 23.2g (0.4mol) propionic aldehyde, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) in having assembled the 250ml mixing tank of reflux exchanger and thermometer, stir 4 hours whole.After this, product once washs and once washes with water with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the crystallization crude product of 11.2g light color.The GC:(condition is seen embodiment 1): 25.7%, the 62.3%GC/MS:(condition is seen embodiment 2)
R
t＝42,49
MS：m/e(％)＝278(20，M
+)，249(31)，203(100)，161(15)，147(32)，133(63)，119(97)，
105(53)，91(24)，69(54)，43(37).
R
t＝42,94
MS：m/e(％)＝278(4，M
+)，249(33)，203(100)，161(15)，147(33)，133(64)，119(98)，
105(54)，91(24)，69(54)，41(42).
The reaction of embodiment 13 cdear diol mixtures 3 (Fig. 1) and butyraldehyde
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 28.8g (0.4mol) butyraldehyde, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred 6 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once with washing of 10% soda solution and the water washing of once using 50ml, is used dried over sodium sulfate, and is under reduced pressure distilled solvent, obtains the crude product of 13.4g light color.The GC:(condition is seen embodiment 1) 26.3%, the 63.7%GC/MS:(condition is seen embodiment 2)
R
t＝44,14
MS：m/e(％)＝292(1，M
+)，249(28)，203(100)，161(14)，147(31)，133(64)，119(98)，
105(51)，69(55)，43(42)。
R
t＝44,69
MS：m/e(％)＝292(3，M
+)，249(29)，203(100)，161(13)，147(31)，133(59)，119(89)，
105(47)，69(54)，41(44)。
The reaction of embodiment 14 cdear diol mixtures 3 (Fig. 1) and isobutyric aldehyde
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 28.8g (0.4mol) isobutyric aldehyde, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred 5 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once washs with 10% soda solution and once uses the 50ml water washing, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the crude product of 10.2g light color.The GC:(condition is seen embodiment 1): 30.68%, 61.32% GC/MS:(condition is seen embodiment 2)
R
t＝42,29
MS：m/e(％)＝292(1，M
+)，249(31)，203(100)，161(13)，147(29)，133(55)，119(87)，
105(43)，91(17)，69(42)，41(29)。
R
t＝42,82
MS：m/e(％)＝291(5，M
+)，249(28)，203(100)，161(13)，147(29)，133(57)，119(89)，
105(46)，91(17)，69(43)，41(32)。
The reaction of embodiment 15 cdear diol mixtures 3 (Fig. 1) and valeral
At 20-25 ℃, cdear diol mixture 3 (Fig. 1 is from embodiment 4), 34.4g (0.4mol) valeral, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) were stirred 7 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once washs with 10% soda solution and once uses the 50ml water washing, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the crude product of 10.6g light color.The GC:(condition is seen embodiment 1): 43.91%, the 16.67%GC/MS:(condition is seen embodiment 2)
R
t＝46,39
MS：m/e(％)＝306(1，M
+)，249(27)，203(100)，147(31)，133(59)，119(85)，105(47)，
91(24)，69(52)，41(46).
R
t＝47,11
MS：m/e(％)＝306(3，M
+)，249(31)，203(100)，147(26)，133(53)，119(77)，105(38)，
91(16)，69(42)，41(34).
The reaction of embodiment 16 cdear diol mixtures 3 (Fig. 1) and isovaleric aldehyde
At 20-25 ℃, cdear diol mixture 3 (not re-crystallization), 34.4g (0.4mol) isovaleric aldehyde, 100ml toluene and the 0.2g tosic acid of 10.1g (0.04mol) stirred 4 hours in having assembled the 250ml mixing tank of reflux exchanger and thermometer.After this, product once with washing of 10% soda solution and the water washing of once using 50ml, is used dried over sodium sulfate, and is under reduced pressure distilled solvent, obtains the colourless crude product of 11g.The GC:(condition is seen embodiment 1) 16.4%, 19.5%, 12.2%, 9.2%, the 9.5%GC/MS:(condition is seen embodiment 2)
R
t＝44,49
MS：m/e(％)＝306(1，M
+)，249(26)，203(100)，161(13)，147(28)，133(59)，119(88)，
105(43)，69(49)，41(41).
R
t＝45,1
MS：m/e(％)＝306(3，M
+)，249(30)，203(100)，147(26)，133(54)，119(79)，105(40)，
69(43)，41(37).
R
t＝46,60
MS：m/e(％)＝306(8，M
+)，291(11)，263(41)，220(90)，203(30)，177(45)，150(100)，
121(39)，69(54)，43(94).
R
t＝48,47
MS：m/e(％)＝306(7，M
+)，291(10)，263(14)，220(81)，203(30)，177(42)，150(100)，
121(39)，69(49)，43(85).
R
t=48,80
MS：m/e(％)＝306(10，M
+)，291(11)，263(11)，220(77)，203(18)，177(40)，150(100)，
121(41)，69(44)，43(85).
The reaction of embodiment 17 cdear diol mixtures 3 (Fig. 1) and formaldehyde
At 20-25 ℃, p-formaldehyde, 200ml gasoline and the 3g vitriol oil elder generation in being provided with the 250ml mixing tank of reflux exchanger and thermometer of 30g (1mol) was stirred 10 minutes.After this, the cdear glycol 3 (Fig. 1 is from embodiment 4) that in 5 minutes, in batches adds 5g (0.019mol).Mixture stirred 3 hours at 20-25 ℃.After p-formaldehyde filtered out, reaction mixture washed once and washes with water once with 10% soda solution, uses dried over sodium sulfate, and under reduced pressure distills solvent, obtains the colourless crude product of 5.4g.The GC:(condition is seen embodiment 1) 41.5%, the GC/MS:(condition is seen embodiment 2)
R
t＝42,20
MS：m/e(％)＝250(31，M
+)，235(37)，204(37)，161(47)，149(50)，119(48)，107(59)，
100(100)，69(63)，43(96).
Embodiment 18
Lily of the valley odor type (Accord Muguet)
Acetonide (from embodiment 5) 2
C11 olefine aldehydr (Aldehyd Cllen) 1% 10
Geraniol acetate 10
Florindal(a) 10
Cis-acetate 3-hexene ester 10% 10
Phenylethyl isobutyrate 15
Cis-3-hexenol 1% 15
C10 aldehyde 1% 15
Indoles 10% 20
Phenylethyl dimethylcarbinol 25
Sandranol(a) 25
Geraniol 35
C9 aldehyde 1% 40
Hedione
(b) 60
Linalool 60
Phenylethyl ethanoate 60
Lyral
(c) 70
Jasmal 80
Geraniol 120
Phenylethyl alcohol 140
Jasmonal H 178
1000
(a)＝DRAGOCO
(b)＝Firmenich
(c)＝IFF
Use has improved the dispersivity and the freshness of main smell (Kopfnote) from the acetonide of embodiment 5, and has increased the weather resistance (Haftung) of back smell (Nachgeruch).
Embodiment 19
Jasmine fragrance (Accord Jasmin)
Acetonide (from embodiment 5) 1
Methyl caprylate (methyloctincarbonate), 1% 5
C16 aldehyde 10% 5
Methoxycresol 10% (a) 5
O-amino benzoyl dimethyl phthalate 10% 5
Cis-3-hexenol 10% 5
Indoles 5
C18 aldehyde 5
Isopropylformic acid ethyl phenoxy 5
P-methylphenol 10% 10
Voitol 1% 10
Oxymethoxyallylbenzene 10
Cis-3-hexenol acetic ester 10% 10
C14 aldehyde 1% 10
Laurate ethyl 10
Methyl o-aminobenzoate 10% 10
Hedione
(b) 15
Hexyl-benzoate 15
Cyloamylone(a) 20
Linalool 30
Benzylalcohol 50
Lactoscaton(a) 60
Peruscabin 149
Jasmonal H 250
Jasmal 300
1000
(a)＝DRAGOCO
(b)＝Firmenich
Use has strengthened (animalisch) of the typical animal perfume (or spice) of jasmine from the acetone solvate of embodiment 5, the indoles smell (Indolnote) of the fragrance of a flower, and improved disperse and back smell weather resistance.
Claims (3)
1, the cyclic cedrene aldehyde acetal of general formula A, wherein wave molding is represented α-and β-conformation, R and R
1Be following group:
R=R
1=HR=H, R
1=Me/R=Me, R
1=HR=H, R
1=E1/R=Et, R
1=HR=H, R
1=Pr/R=Pr, R
1=HR=H, R
1=Bu/R=Bu, R
1=HR=H, R
1=Iso-Bu/R=Iso-Bu, R
1=HR=H, R
1=amyl group/R=amyl group, R
1=HR=H, R
1=isopentyl/R=isopentyl, R
1=HR=H, R
1=hexyl/R=hexyl, R
1=HR=R
1=Me (α, β) R=Me, R
1=Et/R=Et, R
1=MeR=R
1=Et (α, β) R=Me, R1=Pr/R=Pr, R1=MeR=Et, R1=Pr/R=Pr, R=EtR=R1=cyclobutyl R=R1=cyclopentyl R=R1=cyclohexyl
2, the preparation method of the compound of general formula A, wherein, cedrene epoxide by the cedrene preparation, according to selected reaction conditions, be converted into the mixture of epimeric cedrene glycol, or individually be converted into the mixture of non-mapping cedrene glycol (3a/b), and itself and aliphatic carbonyl compounds under the acid catalysis condition without thinner or in aprotonic solvent, adding under the condition of entry binding reagents and react.
3, the compound of general formula A makes makeup or mechanicals send out fragrant application as the composition of spices or spice mixt or as perfume oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981178189A CN1142156C (en) | 1998-08-07 | 1998-08-07 | Cyclic cedrene aldehyde acetal, its preparation and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981178189A CN1142156C (en) | 1998-08-07 | 1998-08-07 | Cyclic cedrene aldehyde acetal, its preparation and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1244527A true CN1244527A (en) | 2000-02-16 |
| CN1142156C CN1142156C (en) | 2004-03-17 |
Family
ID=5225732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981178189A Expired - Lifetime CN1142156C (en) | 1998-08-07 | 1998-08-07 | Cyclic cedrene aldehyde acetal, its preparation and its use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142156C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134228A (en) * | 2011-01-30 | 2011-07-27 | 北京安胜瑞力科技有限公司 | Method for preparing scostus-ambrein perfume |
| CN106458959A (en) * | 2014-05-21 | 2017-02-22 | 西姆莱斯有限公司 | New mixtures |
| CN108191813A (en) * | 2017-12-20 | 2018-06-22 | 帕潘纳(北京)科技有限公司 | A kind of preparation method of ketal |
| CN108785136A (en) * | 2017-05-04 | 2018-11-13 | 伽蓝（集团）股份有限公司 | The application of deodar essential oil |
| CN111050855A (en) * | 2017-08-25 | 2020-04-21 | 西姆莱斯有限公司 | Mixtures comprising enantiomerically pure Ambrocenide |
| CN111183136A (en) * | 2017-11-28 | 2020-05-19 | 弗门尼舍有限公司 | Amber odorant |
-
1998
- 1998-08-07 CN CNB981178189A patent/CN1142156C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134228A (en) * | 2011-01-30 | 2011-07-27 | 北京安胜瑞力科技有限公司 | Method for preparing scostus-ambrein perfume |
| CN106458959A (en) * | 2014-05-21 | 2017-02-22 | 西姆莱斯有限公司 | New mixtures |
| US10526563B2 (en) | 2014-05-21 | 2020-01-07 | Symrise Ag | Mixtures having (4aR,5R,7aS,9R)-octahydro-2,2,5,8,8,9a-hexamethyl-4H-4a,9-methanoazuleno(5,6-d)-1,3-dioxole)(Ambrocenide®) |
| CN106458959B (en) * | 2014-05-21 | 2020-03-06 | 西姆莱斯有限公司 | Mixtures with (4aR,5R,7aS,9R) -octahydro-2, 2,5,8,8,9 a-hexamethyl-4H-4 a, 9-methyleneazuleno (5,6-d) -1, 3-dioxole |
| CN108785136A (en) * | 2017-05-04 | 2018-11-13 | 伽蓝（集团）股份有限公司 | The application of deodar essential oil |
| CN108785136B (en) * | 2017-05-04 | 2022-08-09 | 伽蓝（集团）股份有限公司 | Application of cedar essential oil |
| CN111050855A (en) * | 2017-08-25 | 2020-04-21 | 西姆莱斯有限公司 | Mixtures comprising enantiomerically pure Ambrocenide |
| CN111050855B (en) * | 2017-08-25 | 2024-04-26 | 西姆莱斯有限公司 | Mixtures comprising enantiomerically pure Ambrocenide DEG C |
| CN111183136A (en) * | 2017-11-28 | 2020-05-19 | 弗门尼舍有限公司 | Amber odorant |
| CN111183136B (en) * | 2017-11-28 | 2024-05-28 | 弗门尼舍有限公司 | Amber odorant |
| CN108191813A (en) * | 2017-12-20 | 2018-06-22 | 帕潘纳(北京)科技有限公司 | A kind of preparation method of ketal |
| CN108191813B (en) * | 2017-12-20 | 2020-01-17 | 帕潘纳(北京)科技有限公司 | Preparation method of ketal |
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| Publication number | Publication date |
|---|---|
| CN1142156C (en) | 2004-03-17 |
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