CN100488940C - Oxalate for preparing ambrox or releasing ambrox in cigarette smoke and its use - Google Patents
Oxalate for preparing ambrox or releasing ambrox in cigarette smoke and its use Download PDFInfo
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- CN100488940C CN100488940C CNB2004100232965A CN200410023296A CN100488940C CN 100488940 C CN100488940 C CN 100488940C CN B2004100232965 A CNB2004100232965 A CN B2004100232965A CN 200410023296 A CN200410023296 A CN 200410023296A CN 100488940 C CN100488940 C CN 100488940C
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- Prior art keywords
- ambrox
- tetramethyl
- hydroxyl
- base
- barkite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YPZUZOLGGMJZJO-UHFFFAOYSA-N ambrofix Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OCC2 YPZUZOLGGMJZJO-UHFFFAOYSA-N 0.000 title claims description 51
- YPZUZOLGGMJZJO-LQKXBSAESA-N ambroxan Chemical compound CC([C@@H]1CC2)(C)CCC[C@]1(C)[C@@H]1[C@]2(C)OCC1 YPZUZOLGGMJZJO-LQKXBSAESA-N 0.000 title claims description 51
- 235000019504 cigarettes Nutrition 0.000 title abstract description 49
- 239000000779 smoke Substances 0.000 title abstract description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title abstract description 14
- -1 sec.-propyl Chemical group 0.000 claims description 32
- 241000208125 Nicotiana Species 0.000 claims description 17
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ATFMBPMKXYTHNH-UHFFFAOYSA-N 1,2,3-trimethyl-2H-pyrazine Chemical compound C1(N(C=CN=C1C)C)C ATFMBPMKXYTHNH-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 28
- AIALTZSQORJYNJ-UHFFFAOYSA-N 1-(2-hydroxyethyl)-2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydro-1h-naphthalen-2-ol Chemical compound OCCC1C(C)(O)CCC2C(C)(C)CCCC21C AIALTZSQORJYNJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 24
- 230000001476 alcoholic effect Effects 0.000 description 24
- 229960004756 ethanol Drugs 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 239000003205 fragrance Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001149 thermolysis Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012496 blank sample Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- XVULBTBTFGYVRC-HHUCQEJWSA-N sclareol Chemical compound CC1(C)CCC[C@]2(C)[C@@H](CC[C@](O)(C)C=C)[C@](C)(O)CC[C@H]21 XVULBTBTFGYVRC-HHUCQEJWSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZAZVCYBIABTSJR-UHFFFAOYSA-N (+)-Abienol Natural products CC1(C)CCCC2(C)C(CC=C(C=C)C)C(C)(O)CCC21 ZAZVCYBIABTSJR-UHFFFAOYSA-N 0.000 description 1
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SJRWAGBQZRSZEQ-UHFFFAOYSA-N 2,5,5,8a-tetramethyl-3,4,4a,6,7,8-hexahydro-1h-naphthalen-2-ol Chemical class C1C(C)(O)CCC2C(C)(C)CCCC21C SJRWAGBQZRSZEQ-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- ZAZVCYBIABTSJR-KOQQBVACSA-N Abienol Chemical compound CC1(C)CCC[C@]2(C)C(CC=C(C=C)C)[C@](C)(O)CC[C@H]21 ZAZVCYBIABTSJR-KOQQBVACSA-N 0.000 description 1
- 235000005241 Cistus ladanifer Nutrition 0.000 description 1
- 240000008772 Cistus ladanifer Species 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- XVULBTBTFGYVRC-UHFFFAOYSA-N Episclareol Natural products CC1(C)CCCC2(C)C(CCC(O)(C)C=C)C(C)(O)CCC21 XVULBTBTFGYVRC-UHFFFAOYSA-N 0.000 description 1
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000004869 Labdanum Substances 0.000 description 1
- LAEIZWJAQRGPDA-UHFFFAOYSA-N Manoyloxid Natural products CC1(C)CCCC2(C)C3CC=C(C)OC3(C)CCC21 LAEIZWJAQRGPDA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KKTBXRFTXPLJNN-UHFFFAOYSA-N ent-labd-8beta-ol-14-ene Natural products CC(CCC1C(C)(O)CCC2C(C)(C)CCCC12C)C=C KKTBXRFTXPLJNN-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Abstract
An application of the oxalate in preparing norambrether or releasing the norambrether to the smoke of cigaretter is disclosed. Said oxalate may be decahydro-2-hydroxy-2,5,5,8a-tetramethyl-naphthal eneethanol or 2-hydroxy-2,5,5,9-tetramethyl decalyl ethanol. It can be proportionally added to cigarette, or can be decomposed to obtain norambrether.
Description
Technical field
The present invention relates to barkite from ambrox to cigarette smoke and application thereof that novel being used to prepares ambrox or discharge.
Background technology
Labdanum class material is the key aroma component of Turkish tobaccos, and ambrox is wherein to act on especially outstanding a kind of spices, and the flue gas of blended type cigarette is played important contribution.Ambrox also is widely used in Virginian-type cigarette and makes perfume.Because little, the high volatility of ambrox molecular weight, boiling point has only 122-124 ℃, and threshold value is low, easily loses in the processing storage process, causes the cigarette quality instability.
Ambrox is widely used in the blending of the flavoring and casing and the household chemicals of cigarette industry, in particular for making perfume.Its preparation method has much.What have is raw material with the jononeionone, and what have is raw material with sclareol or abienol.But most of method is that (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol (structural formula is seen formula III) is intermediate with glycol all, prepares with dehydrations such as beta-naphthalenesulfonic-acid or zinc chloride or SULPHURYL CHLORIDE.
U.S. Pat 5671756 discloses i.e. (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) the alcoholic acid carbonic ether of this glycol, and such carbonic ether is used for discharging ambrox to cigarette smoke.But we think that though it discharges ambrox to cigarette smoke, its release efficiency is not very effective, and reason is that the thermostability of carbonic ether is still higher, is higher than the thermostability of barkite, and its thermolysis efficient is not as barkite thermolysis efficient.
Summary of the invention
Purpose of the present invention aims to provide a kind of new being used to and prepares ambrox or discharge the barkite of ambrox to cigarette smoke, and uses.
The objective of the invention is to realize by following manner:
Be used to prepare ambrox or discharge the barkite of ambrox, have structure shown in formula (I) or the formula (II) to cigarette smoke,
Described R is that carbonatoms is the aliphatic alkyl of 1-20, contains the substituting group of alicyclic ring, or contains the heterocyclic substituting group, perhaps is hydrogen atom.
Wherein R is that wherein R is that carbonatomss such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl are the aliphatic alkyl of 1-20; Or (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethyl, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-3-butene-1-Ji, (2,6,6-trimethylammonium-4-oxo-1-cyclohexenyl)-3-butene-1-Ji, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-carbonatoms such as 1-butylene-3-base, (2,6,6-trimethylammonium-4-oxo-1-cyclohexenyl)-1-butylene-3-base, cyclohexyl is the substituting group that 6-20 contains alicyclic ring; Or be 2-methylpyrazine base, 2,3, carbonatomss such as 4-trimethylpyrazine base, 2-picolyl are that 5-20 contains the heterocyclic substituting group; Or be hydrogen atom.Wherein be hydrogen atom, methyl, ethyl, (2-hydroxyl-2,5,5 with R, 8a-tetramethyl--naphthane base) ethyl, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-3-butene-1-Ji, (2,6,6-trimethylammonium-4-oxo-1-cyclohexenyl)-3-butene-1-Ji is excellent.Particularly be that hydrogen atom, ethyl, (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethyl are optimum with R.
Described application mode then is to add the barkite with formula (I) or formula (II) constitutional features to tobacco.
Add the barkite with formula (I) or formula (II) structure in tobacco, its adding mode is for adding fragrant, the reinforced or thin slice perfuming of table, and wherein tobacco can be the finished product of mixed type or fire-cured tobacco type, or the product formula integral part.
The barkite of described another kind of application mode for having formula (I) or formula (II) constitutional features makes ambrox by decomposition.Its principle is to contain adjacent carboxylic carbonyl in the barkite molecular structure, and is similar to oxalic acid, decarboxylic reaction easily takes place when heating, thereby generate ambrox.The preparation ambrox can be realized as follows: synthetic earlier barkite with formula (I) or formula (II) structure, the pure product that obtain after head product or the separation are heated to more than 162 ℃, and barkite decomposes the back and obtains ambrox by distillation or crystallization.Optimum way obtains crystalloid pure barkite for separating earlier, then 250 ℃ of thermolysiss.The separation of being convenient to ambrox is like this purified.
The invention discloses the barkite that a class is used to prepare ambrox or discharges ambrox to cigarette smoke, The compounds of this invention is i.e. (the 2-hydroxyl-2 of glycol, 5,5,8a-tetramethyl--naphthane base) ethanol (decahydro-2-hydroxy-2,5,5, oxalate diester 8a-tetramethyl-naphthaleneethanol) or monoesters.These barkites can be synthetic by the monoesters or the oxalic acid reaction of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol and oxalyl chloride or oxalyl chloride, or synthetic by transesterification reaction with the oxalate diester of lower aliphatic alcohols.These barkites have as structural formula I or the represented structure of II.One or more compounds of these barkites are joined in the cigarette in modes such as perfuming, reinforced, thin slice perfumings according to a certain percentage, make it discharge the ambrox aroma component to cigarette smoke.Also can obtain these barkites, not separate or separate the back and prepare ambrox by decomposing barkite by reaction.The invention is intended to disclose a class is used for discharging ambrox or being used to prepare the oxalic acid ester precursor compound of ambrox to cigarette smoke.This compounds has advantages such as fusing point height, volatility are low, light fragrance, and being used for cigarette has good flue gas flavouring effect.
This class barkite can prepare by the synthetic method of logical ester, as glycol and oxalyl chloride are carried out esterification; Or the barkite of glycol and lower aliphatic alcohols carries out esterification by transesterify; Or with the preparation that in solvent, refluxes of glycol and oxalic acid.
Utilize such barkite to discharge ambrox, directly utilize ambrox to the existing deficiency of perfuming cigarette to solve to cigarette smoke.Add such barkite to tobacco, the adding mode can be and adds fragrant, the reinforced or thin slice perfuming of table, and wherein tobacco can be the finished product of mixed type or fire-cured tobacco type, or the part of its product formula composition.Additional proportion be cigarette prop up tobacco weight 3/1000ths to 1,000,000/.
Barkite of the present invention can be used to prepare ambrox.Behind synthetic such barkite, the pure product that obtain after unseparated thick product or the separation are obtained ambrox by decomposition.
(2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) the alcoholic acid barkite has overcome the shortcoming of ambrox: promptly molecular weight is little, volatility is high, threshold value is little, Wen Xiangchong, easily loss in the processing storage process, and cigarette props up in the aspiration procedure fragrance and discharges irregularly, causes the inconsequent of taste.(2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid barkite molecular weight is big, can not discharge aroma component incombustible the time, does not run off so do not have fragrance basically, and can not lose at the processing storage process, can discharge uniform fragrance and prop up in the aspiration procedure at cigarette.
Description of drawings
The heat analysis of Fig. 1 (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester
The thermolysis sample gas chromatogram of Fig. 2 (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester
Fig. 3 tests the gas chromatogram of cigarette smoke components
The gas chromatogram of the blank sample cigarette smoke of Fig. 4 composition
Embodiment
Now with the routine preparation that this compounds is described of being prepared as of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester and (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol ethyl oxalate.
The preparation of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol oxalate diester
0.02mol (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol is dissolved in 30 milliliters of THF, adds the 3.2mL pyridine, the frozen water cooling is stirred and is dripped the 0.04mol oxalyl chloride down.Stirring at room is 24 hours then.Add 10mL ethanol, stirred 30 minutes, add trash ice and 40mL2NHCl, with ether (200mL * 3) extraction, the combined ether layer is with 2NHCl, water and NaHCO
3The aqueous solution washs respectively, dried over sodium sulfate, and decompression desolventizes, and gets white crystal, suction filtration, vacuum-drying promptly gets (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester, productive rate about 80%.
Proton nmr spectra
1HNMR (400MHz, CDCl
3): δ 0.788 (s, 12H, 4CH
3), 0.874 (s, 6H, 2CH
3), 1.191 (s, 6H, 2CH
3), 0.899-1.692 (m, 26H), 1.876-1.924 (m, 2H), 3.415-3.806 (m, 4H), 3.18-4.10 (br, 2H, 2OH).Proton nmr spectra illustrates that its molecule contains 8 methyl, and two hydroxyls contain 58 hydrogen atoms altogether, meet the represented constitutional features of structural formula II.
On Bruker Daltonics.Inc.APEX II.FT-ICRMS, record quasi-molecular ion m/z=585.4130 (M+Na)
+, (P-SIMS-Gly+NaCl), calculating its molecular formula is C
34H
58O
6Na (theoretical formula weight is 585.4125), then the molecular formula of synthetic barkite is C
34H
58O
6, the structure represented with formula II meets, and synthetic product is a 2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) the alcoholic acid oxalate diester.
Ir data IR (cm
-1): 3263,2920,1740,1735,1388,1055, hydroxyl in the molecule, methylene radical, ester group are described, the structure represented with formula III meets, synthetic product is a 2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) the alcoholic acid oxalate diester.
Embodiment 2
The preparation of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol ethyl oxalate
0.02mol (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol adds 0.1 gram sodium methylate and 50 milliliters of oxalic acid diethyl esters, removes the ethanol that generates 80 ℃ of underpressure distillation.Reaction is finished after the column chromatography chromatographic separation gets (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol ethyl oxalate.Mass-spectrometric data m/z (abundance): 354 (M+,＜1), 236 (2), 221 (100), 195 (20), 177 (18), 151 (90), 123 (25), 95 (60), 69 (40).Confirm that by resolving its main mass-spectrometric data this material is (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethanol ethyl oxalate.
Embodiment 3
Now the thermal analysis experiment with (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester illustrates the chemical property that the low volatility of this compounds extremely easily decomposes fully when heating.
The thermal analysis experiment of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester
Accurately take by weighing about 10 milligrams (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diesters, on NETZSH-STA 449C thermal analyzer, record TG and DSC curve.
The thermal analysis curve of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester is seen Fig. 1.Recording its fusing point is 129.0-131.4 ℃, illustrates that its volatility is low.This compound decomposes between 162-211 ℃ fully, and rate of weight loss is 98.2%, illustrates that it almost completely decomposes when heating, can change other compositions into during heating very effectively.
Embodiment 4
Now test and easily decompose the chemical property that generates ambrox when the heating of this compounds is described fully with the thermolysis of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester.
The thermolysis experiment of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester
Take by weighing 0.5 gram (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester, place the flask that reflux is housed, 300 ℃ of reflux of oil bath 1 hour, the GC-MS analysis is carried out in sampling, and color atlas is seen Fig. 2.Wherein retention time is that the chromatographic peak of 24.113min is confirmed as ambrox through the mass spectrum library searching.This explanation (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester almost completely is decomposed into ambrox under heating condition.
Embodiment 5
Now testing with (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester perfuming cigarette can be to flue gas ambrox aroma component when the heating of this compounds is described.
(2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester discharges the ambrox aroma component to cigarette smoke.
Take by weighing a certain amount of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester, behind dissolve with ethanol, make an addition to certain tobacco shred on, roll into the experiment cigarette.With same pipe tobacco, the ethanol of interpolation and last same ratio rolls into blank sample cigarette.
Above-mentioned made blank sample cigarette and experiment cigarette are burnt and sucked respectively, allow flue gas by a spinner-type flowmeter and an absorption bottle that contains the 10mL dehydrated alcohol, the control flue gas flow is 48L/h, collects the chemical ingredients of main flume.Every 10mL dehydrated alcohol absorbs the smoke components of 8 cigarettes.
The above-mentioned ethanolic soln that has absorbed experiment cigarette smoke and blank sample cigarette smoke composition is detected on the HP6890/HP5973 gas chromatograph-mass spectrometer respectively.Gas chromatogram is seen Fig. 3 and Fig. 4 respectively
In the gas chromatogram of the blank sample cigarette smoke of Fig. 4 composition, two very significantly chromatographic peaks are arranged, its retention time is respectively 13.95min and 14.08min, confirms as glycerine triacetate and Nicotine respectively through the mass spectrum library searching, and this is two higher components of content in the cigarette mainstream flue gas.
Fig. 3 tests in the gas chromatogram of cigarette smoke components, and retention time 24.113min chromatographic peak is confirmed as ambrox through the mass spectrum library searching.Join the solution similarity condition with the ambrox standard model and on the HP6890/HP5973 gas chromatograph-mass spectrometer, detect, find that the chromatographic peak retention time of ambrox standard specimen is 24.113min.
The main mass-spectrometric data of Fig. 3 retention time 24.113min chromatographic peak is (m/z): 236 (M
+, 1.8), 221 (100), 203 (1.7), 191 (0.3), 177 (2.2), 165 (1.3), 151 (1.7), 137 (20.6), 121 (3.6), 109 (5.1), 97 (18.4), 81 (7.7), 69 (7.0), 67 (5.9), 55 (6.3), 43 (7.3), 41 (7.2)
The mass-spectrometric data of the ambrox of mass-spectrometric data storehouse NIST#:109688 is (m/z): 236 (M
+, 4.4), 221 (100), 203 (1.1), 191 (0.1), 177 (2.0), 165 (1.1), 151 (2.2), 137 (29.8), 121 (3.8), 109 (5.9), 97 (30.4), 81 (11.2), 69 (14.2), 67 (7.1), 55 (10.5), 43 (18.2), 41 (1.2)
Embodiment 6
Now smoke panel test to test and illustrate that this compounds improves cigarette smoke fragrance with (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester perfuming cigarette.
(2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester improves the cigarette smoke odour characteristics.
Take by weighing a certain amount of (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester, behind dissolve with ethanol, by 0.03% make an addition to certain tobacco shred on, roll into the experiment cigarette.With same pipe tobacco, the ethanol of interpolation and last same ratio rolls into blank sample cigarette.Contrast is smoked panel test and is shown, and to compare in the same old way, the experiment cigarette has significantly cypress fragrance, can soft flue gas.
Can infer that by above data scission reaction takes place (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) alcoholic acid oxalate diester that experiment sample cigarette contains, and discharges the ambrox aroma component to cigarette smoke when burning and sucking:
Equally, scission reaction also can take place in other barkite when burning and sucking, and discharges the ambrox aroma component to cigarette smoke.
Embodiment 7
Preparation ambrox: with synthetic (2-hydroxyl-2 among the embodiment 2,5,5,8a-tetramethyl--naphthane base) head product of ethanol ethyl oxalate or separate after the pure product that obtain with 200 ℃ of oil bath reflux, barkite decomposes the back by distilling or crystallization obtains ambrox.Optimum way obtains purified barkite for separating earlier, then 250 ℃ of thermolysiss.The separation of being convenient to ambrox is like this purified.
In sum, the invention discloses a class and discharge the oxalate of ambrox for the preparation of ambrox or to cigarette smoke, Can be used for discharging the ambrox fragrance component to cigarette smoke, also can be for the preparation of ambrox. This compounds has molten The advantages such as boiling point height, volatility are low, light fragrance, being used for cigarette has good flue gas flavouring effect. Hence one can see that, institute of the present invention Its release falls in the oxalate that adds (2-hydroxyl-2,5,5,8a-tetramethyl-decahydronaphthalenes base) ethanol in the cigarette that relates to The method of dragon saliva ether fragrance component is successfully effective.
Claims (6)
1, a kind of barkite has structure shown in the general formula (I),
Described R is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl; Or (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethyl, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-3-butene-1-Ji, (2,6,6-trimethylammonium-4-oxo-1-cyclohexenyl)-3-butene-1-Ji, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-1-butylene-3-base, (2,6,6-trimethylammonium-4-oxo-1-cyclohexenyl)-and 1-butylene-3-base, cyclohexyl or be 2-methylpyrazine base, 2,3,4-trimethylpyrazine base, 2-picolyl or be hydrogen atom.
2, a kind of barkite according to claim 1, wherein R is (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethyl, (2,6,6-trimethylammonium-3-oxo-1-cyclohexenyl)-3-butene-1-Ji, cyclohexyl.
3, a kind of barkite according to claim 1, R are (2-hydroxyl-2,5,5,8a-tetramethyl--naphthane base) ethyls, and described barkite has formula (II) structure
4, according to the purposes of claim 1 or 2 or 3 each described compounds, be used for adding tobacco.
5, the purposes of compound according to claim 4, the adding mode that adds in the tobacco is shown fragrant, reinforced or thin slice perfuming for adding, and described tobacco is the finished product of mixed type or fire-cured tobacco type, or the product formula integral part.
6, according to the purposes of claim 1 or 2 or 3 each described compounds, be used for making ambrox by decomposition.
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| CN105968009B (en) * | 2016-07-20 | 2018-04-20 | 郑州轻工业学院 | 5 isopropyl, 9 hydroxyl, 8 methyl, 6 nonene, 2 ketone oxalic acid dibasic acid esters and its synthetic method and application |
| CN112625018A (en) * | 2020-12-10 | 2021-04-09 | 河南中烟工业有限责任公司 | 2, 3-dihydro-3-hydroxy-6-methyl-4H-pyran-4-one-5-O-linalyl carbonate and application thereof |
| CN113480432A (en) * | 2021-08-05 | 2021-10-08 | 四川三联新材料有限公司 | Perilla alcohol ambroxol carbonate latent aroma, and preparation method and application thereof |
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