CN105837536A - Solanesol bromide furan perfume and synthetic method thereof - Google Patents

Solanesol bromide furan perfume and synthetic method thereof Download PDF

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Publication number
CN105837536A
CN105837536A CN201610335993.7A CN201610335993A CN105837536A CN 105837536 A CN105837536 A CN 105837536A CN 201610335993 A CN201610335993 A CN 201610335993A CN 105837536 A CN105837536 A CN 105837536A
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Prior art keywords
compound
class
eggplant
pranoprofenum
alkyl
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CN201610335993.7A
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Chinese (zh)
Inventor
李保健
周斌华
汪子玉
邵明非
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Shenzhen Dawu Technology Co Ltd
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Shenzhen Dawu Technology Co Ltd
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Priority to CN201610335993.7A priority Critical patent/CN105837536A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
    • A24B15/26—Use of organic solvents for extraction

Abstract

The invention relates to a solanesol bromide furan perfume and a synthetic method thereof. The solanesol bromide furan perfume adopts a parent structure similar to that of solanesol bromide furan and has the fragrance similar to that of the solanesol bromide furan, and main functional groups include a furan ring and acetyl. A solanesol bromide furan compound can be synthesized only through two-step reaction. A synthetic route is that after being dehydrogenized by a deprotonation reagent, a furan compound reacts with olefin with a leaving group to generate an intermediate; then, Wacker oxidation reaction is performed to obtain the solanesol bromide furan type compound.

Description

Class eggplant Pranoprofenum spice and synthetic method thereof
Technical field
The invention belongs to organic chemistry, synthetic perfume and technical field of tobacco；Be specifically related to class eggplant Pranoprofenum spice and Synthetic method.
Background technology
An important deficiency of cigarette substitute (such as electronic cigarette) and smoking cessation product is just difficult to the mouth of simulated cigarette at present Sense and abnormal smells from the patient, some important spice that its major reason has just been the absence of in Nicotiana tabacum L..Eggplant Pranoprofenum be in Nicotiana tabacum L. one important Perfume compound, is present in cured tobacco leaf, burley tobaccos Nicotiana tabacum L., Turkish tobaccos Nicotiana tabacum L..Its chemical synthesis process is seldom seen at present Report.On market, the spice about eggplant Pranoprofenum class is the most rare.Develop a kind of perfume (or spice) similar with eggplant Pranoprofenum precursor structure Material and synthetic method thereof, enable large-scale production, and the popularization to cigarette substitute and smoking cessation product plays an important role, and then Of great advantage to the health of numerous smokers.
Summary of the invention
The present invention relates to class eggplant Pranoprofenum compound.Can serve as electronic cigarette spice, it is possible to as the perfume (or spice) of other article of everyday use Material.
The invention solves the problems that another problem is that the simple and effective synthesis providing a kind of described class eggplant Pranoprofenum compound Method, in order to the follow-up safety evaluatio work carrying out this compounds and industrial applications.
Class eggplant Pranoprofenum compound of the present invention has a formula as shown in Figure 1:
Wherein R1、R2、R3For H or C1-10Alkyl；
In formula 1: R4、R5For H or C1-10Alkyl, but compound (R1、R2、R3、R4And R5It is H simultaneously) and compound (R1For Methyl；R2、R3、R4And R5It is H simultaneously) except；
In formula 2: R6、R7、R8For H or C1-10Alkyl, but compound (R1、R2、R3、R6 、R7And R8It is H simultaneously) and chemical combination Thing (R1For methyl；R2、R3、R6 、R7And R8It is H simultaneously) except；
In formula 3: R9、R10、R11For H or C1-10Alkyl, Z is C1-10Alkyl.
Above-mentioned class eggplant Pranoprofenum compound can be synthesized (as shown in Figure 2) by step A and step B two-step reaction: figure formula of 4 Middle R1、R2、R3For H or C1-10Alkyl；In formula 5, X is Cl, Br, I, OMs or OTs substituent group；Y is C1-30Alkyl.
(step A), in ether organic solvent, adds deprotonation reagent to furfuran compound (formula 4) under low temperature (such as n-BuLi), then heats to room temperature and continues stir about 2 hours.Again it is cooled to low temperature, adds alkene 5, the most slowly It is warming up to room temperature and stirs some hours.After saturated aqueous ammonium chloride cancellation, add petroleum ether dilution, layering also separatory, Organic phase washed with water twice, then washed once with saturated aqueous common salt.Filtering after organic facies desiccant dryness, decompression distillation removes Go solvent to obtain intermediate 6 crude product, can be directly used for next step reaction.
(step B) by mantoquita (such as CuCl) and palladium class catalyst (such as PdCl2) be dissolved in water and organic solvent (such as DMF, DMSO), in mixed solvent, at room temperature it is passed through the slow bubbling of oxygen one hour, is subsequently adding intermediate 6.Heating, slowly leads to Enter bubble oxygen, and stir one day.It is subsequently adding water dilution, extracts three times with ether.Merge organic facies, use saturated chlorination successively Aqueous ammonium and saturated aqueous common salt washing.Filtering after organic facies desiccant dryness, decompression is distilled off solvent and obtains crude product.Subtract Pressure distilation i.e. obtains class eggplant Pranoprofenum pure compounds 7.
The class eggplant Pranoprofenum compound prepared according to above step has the fragrance being similar to eggplant Pranoprofenum, can be as eggplant Buddhist nun The succedaneum of furan.
Accompanying drawing explanation
Fig. 1: the general structure of the eggplant Pranoprofenum compound synthesized by the present invention.
Fig. 2: the synthetic route of class eggplant Pranoprofenum compound.
Fig. 3: class eggplant Pranoprofenum compou nd synthesis specific embodiment.
Detailed description of the invention
Below in conjunction with embodiment (Fig. 3), the present invention is further described, but the invention is not restricted to these embodiments.
Embodiment a-1: furan (5.4mL) is dissolved in THF(120mL) in, it is cooled to 0 DEG C.It is slowly added dropwise while stirring N-BuLi (1.6M, 46mL), then heats to room temperature, continues stirring two hours.It is cooled to about-20 DEG C, is slowly added dropwise 4- Bromo-1-butylene (6.5mL, 5a), is then to slowly warm up to room temperature and is stirred overnight.After saturated aqueous ammonium chloride cancellation, add Enter petroleum ether dilution, layering separatory, organic phase washed with water twice, then washed once with saturated aqueous common salt.Use anhydrous slufuric acid Magnesium filters after drying, and decompression is distilled off solvent and obtains crude product 6a, can be directly used for next step reaction；
Characterize: light yellow liquid；Rf=0.56 (normal hexane)；1H NMR (400MHz, CDCl3) δ7.33-7.31 (m, 1H), 6.30-6.28 (m, 1H), 6.03-6.01 (m, 1H), 6.02-5.85 (m, 1H), 5.10 (d, J = 17.1 Hz, 1H), 5.03 (d, J = 10.2 Hz, 1H), 2.76 (t, J = 7.6 Hz, 2H), 2.47-2.42 (m, 2H) ppm; 13C NMR (100MHz, CDCl3) δ155.7, 140.9, 137.6, 115.2, 110.1, 105.0, 34.9, 27.8 ppm; DEPT NMR (100MHz, CDCl3) δ140.9 (CH), 137.6 (CH), 115.2 (CH2), 110.1 (CH), 105.0 (CH), 34.9 (CH2), 27.8 (CH2) ppm。
Embodiment a-2: by CuCl(9.5g) and PdCl2(2.6g) it is dissolved in DMF/H2O(280mL/40mL) in, in room temperature Under be passed through the slow bubbling of oxygen one hour, be subsequently adding crude product 6a.It is heated to 45 DEG C, is slowly introducing bubble oxygen, and stirs one My god.It is subsequently adding water dilution, extracts three times with ether.Merge organic facies, successively with saturated aqueous ammonium chloride and saturated common salt Water washs.Filtering after drying with anhydrous magnesium sulfate, decompression is distilled off solvent and obtains crude product；Decompression distilation i.e. obtains class eggplant Buddhist nun Furan compound sterling 7a(6.5g, two step gross production rates 74%)；
Characterize: colourless liquid；Rf=0.45 (20% ethyl acetate/normal hexane)；There is the strong pungent perfume (or spice) being similar to eggplant Pranoprofenum Abnormal smells from the patient；1H NMR (400MHz, CDCl3) δ7.28-7.26 (m, 1H), 6.44-6.18 (m, 1H), 6.00-5.98 (m, 1H), 2.91 (t, J = 7.3 Hz, 2H), 2.78 (t, J = 7.3 Hz, 2H), 2.16 (s, 3H) ppm; 13C NMR (100MHz, CDCl3) δ207.4, 154.6, 141.2, 110.3, 105.3, 41.8, 30.0, 22.2 ppm; DEPT NMR (100MHz, CDCl3) δ141.2 (CH), 110.3 (CH), 105.3 (CH), 41.8 (CH2), 30.0 (CH3), 22.2 (CH2) ppm。
Embodiment b-1: furan (1.4mL) is dissolved in THF(20mL) in, it is cooled to 0 DEG C.Just it is slowly added dropwise while stirring Butyl lithium (1.6M, 14.4mL), then heats to room temperature, continues stirring two hours.It is cooled to about-20 DEG C, is slowly added dropwise 6- Bromo-1-hexene (2mL, 5b), is then to slowly warm up to room temperature and is stirred overnight.After saturated aqueous ammonium chloride cancellation, add Petroleum ether dilutes, layering separatory, organic phase washed with water twice, then washed once with saturated aqueous common salt.Use anhydrous magnesium sulfate Dried filtration, decompression is distilled off solvent and obtains 6b crude product, can be directly used for next step reaction；
Characterize: light yellow liquid；Rf=0.43 (normal hexane)；1H NMR (400MHz, CDCl3) δ7.33-7.31 (m, 1H), 6.31-6.29 (m, 1H), 6.02-6.00 (m, 1H), 5.91-5.79 (m, 1H), 5.06 (d, J = 17.1 Hz, 1H), 5.00 (d, J = 10.2 Hz, 1H), 2.68 (t, J = 7.5 Hz, 2H), 2.16-2.11 (m, 2H), 1.75-1.68 (m, 2H), 1.53-1.46 (m, 2H) ppm; 13C NMR (100MHz, CDCl3) δ 156.3, 140.7, 138.7, 114.5, 110.1, 104.7, 33.6, 28.5, 27.9, 27.6 ppm; DEPT NMR (100MHz, CDCl3) δ140.7 (CH), 138.7 (CH), 114.5 (CH2), 110.1 (CH), 104.7 (CH), 33.6 (CH2), 28.5 (CH2), 27.9 (CH2), 27.6 (CH2) ppm。
Embodiment b-2: by CuCl(2.5g) and PdCl2(0.68g) it is dissolved in DMF/H2O(70mL/10mL) in, in room temperature Under be passed through the slow bubbling of oxygen one hour, be subsequently adding crude product 6b.It is heated to 45 DEG C, is slowly introducing bubble oxygen, and stirs one My god.It is subsequently adding water dilution, extracts three times with ether.Merge organic facies, successively with saturated aqueous ammonium chloride and saturated common salt Water washs.Filtering after drying with anhydrous magnesium sulfate, decompression is distilled off solvent and obtains crude product.Decompression distilation i.e. obtains class eggplant Buddhist nun Furan compound sterling 7b(1.9g, two step gross production rates 78%)；
Characterize: colourless liquid；Rf=0.30 (10% ethyl acetate/normal hexane)；Slightly class eggplant Pranoprofenum is fragrant and sweet；1H NMR (400MHz, CDCl3) δ7.27-7.25 (m, 1H), 6.30-6.19 (m, 1H), 5.96 (d, J = 2.6 Hz, 1H), 2.61 (t, J = 6.6 Hz, 2H), 2.42 (t, J = 6.7 Hz, 2H), 2.10 (s, 3H), 1.68- 1.47 (m, 6H) ppm; 13C NMR (100MHz, CDCl3) δ208.7, 155.8, 140.8, 110.1, 104.9, 43.3, 29.8, 27.7, 27.5, 23.2 ppm; DEPT NMR (100MHz, CDCl3) δ140.8 (CH), 110.1 (CH), 104.9 (CH), 43.3 (CH2), 29.8 (CH3), 27.7 (CH2), 27.5 (CH2), 23.2 (CH2) ppm。

Claims (6)

1. class eggplant Pranoprofenum compound, has a following structural formula:
Wherein R1、R2、R3For H or C1-10Alkyl；
R in formula 14、R5For H or C1-10Alkyl, but compound (R1、R2、R3、R4And R5It is H simultaneously) and compound (R1For first Base；R2、R3、R4And R5It is H simultaneously) except；
R in formula 26、R7、R8For H or C1-10Alkyl, but compound (R1、R2、R3、R6、R7And R8It is H simultaneously) and (R1For methyl； R2、R3、R6 、R7And R8It is H simultaneously) except；
R in formula 39、R10、R11For H or C1-10Alkyl, Z is C1-10Alkyl.
2. the method preparing class eggplant Pranoprofenum compound as claimed in claim 1, including following two step:
(step A) furfuran compound (formula 4), by after deprotonation reagent dehydrogenation, generates intermediate 6 with alkene 5 reaction；
(step B) intermediate 6 and oxygen occur Wacker to react generation class eggplant Pranoprofenum compound under palladium class catalyst action 7。
The preparation method of class eggplant Pranoprofenum compound the most according to claim 2, however it is not limited to described in preparation claim 1 Class eggplant Pranoprofenum compound；The preparation method of class eggplant Pranoprofenum compound described in claim 2, is characterized in that:
R in formula 41、R2、R3For H or C1-10Alkyl；
In formula 5, X is Cl, Br, I, OMs or OTs substituent group, and Y is C1-30Alkyl.
The most according to claim 2, the preparation method of class eggplant Pranoprofenum compound, in step A, deprotonation reagent used is alkane The double silylation of base lithium, aromatic radical lithium, grignard reagent, lithium dialkyl amides, dialkyl amido sodium, dialkyl amido potassium, six alkyl The double silylation sodium of lithium, six alkyl or the double silylation potassium of six alkyl；Solvent for use is ether, oxolane, methyl tertiary butyl ether(MTBE) or 1,4-dioxane.
The most according to claim 2, the preparation method of class eggplant Pranoprofenum compound, in step B, oxidant used is oxygen, double Oxygen water, tert-Butanol peroxide or m-CPBA；Used catalyst is that bivalence palladium salt is (such as PdCl2 、Pd(OAc)2Or Pd (OTf)2) and CuCl(or CuCl2)；Solvent for use is water and organic solvent (DMF, N,N-dimethylacetamide, dimethyl Sulfoxide, oxolane, methanol or ethanol) mixed solvent.
The most according to claim 1, class eggplant Pranoprofenum compound can be used as but is not limited to electronic cigarette fragrance material.
CN201610335993.7A 2016-05-20 2016-05-20 Solanesol bromide furan perfume and synthetic method thereof Pending CN105837536A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673949A (en) * 2017-01-02 2017-05-17 深圳市大物科技有限责任公司 Method for preparing neophytadiene compounds from fatty acid

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL188286B1 (en) * 1997-10-17 2005-01-31 Politechnika Lodzka Novel compound - furane derivative

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL188286B1 (en) * 1997-10-17 2005-01-31 Politechnika Lodzka Novel compound - furane derivative

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAWAI, YASUSHI ET AL.: "Stereochemical control in microbial reduction. 27. Asymmetric reduction of α,β-unsaturated ketones with bakers" yeast", 《TETRAHEDRON: ASYMMETRY 》 *
全晶晶等: "加工温度对鲣鱼挥发性成分的影响", 《中国食品学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673949A (en) * 2017-01-02 2017-05-17 深圳市大物科技有限责任公司 Method for preparing neophytadiene compounds from fatty acid

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Application publication date: 20160810