CN103601752B - A kind of sila-β-imperial court's ketone and preparation method thereof - Google Patents
A kind of sila-β-imperial court's ketone and preparation method thereof Download PDFInfo
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- CN103601752B CN103601752B CN201310639756.6A CN201310639756A CN103601752B CN 103601752 B CN103601752 B CN 103601752B CN 201310639756 A CN201310639756 A CN 201310639756A CN 103601752 B CN103601752 B CN 103601752B
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Abstract
The invention provides the sila-β shown in formula I-imperial court's ketone, is also 1-(3-sila-3,3-dimethyleyelohexane-1-thiazolinyl) penta-4-alkene-1-ketone.This compound is a kind of flavor compounds with strong pineapple perfume (or spice).The present invention adopts under palladium chtalyst effect, and terminal alkyne is to the insertion ring expansion of silacyclobutane, and high yield prepares this sila-β-imperial court's ketone.The method raw material is easy to get, applied widely, high isolated yield, experimental installation and operation is simple, is convenient to industrialization.
Description
Technical field
The invention belongs to flavor chemistry field, particularly a kind of sila-β-imperial court's ketone compound and general synthetic method thereof.
Background technology
Essence and flavoring agent industrial expansion depends on the constant new high-quality perfume material found.Compared with natural perfume material, synthesis perfume material not only has the composition determined, stable supply and moderate price, does not also have seasonal dependence simultaneously.β-imperial court ketone (Dynascone, IV) is that one has fruital, the perfume material of fragrance as pineapple, is the patented product (US4264467A) of Firmenich & Cie.In recent years, being replaced with a Siliciumatom by a quaternary carbon atom in natural perfume material structure and design and synthesize a kind of method that flavor compounds has become exploitation perfume material newly, is also Si/C substitution method.2010, Givaudan disclosed the patent (US008182781B2) of a kind of α with patchouli oil feature-silica-based alcohol (V).In patchouli oil, crucial aroma component be (
-)-Patchoulicalcohol, content up to 40%, but due to complex structure, is difficult to by synthetic method commercialization.By contrast, with α-silica-based alcohol that three cyclopropyl replace, not only have strong natural patchouli feature, fragrance threshold value is only 1/3rd of Patchoulicalcohol, and easily a large amount of synthesis.Gem-dimethyl tetrahydrobenzene skeleton is present in a large amount of synthesis and natural perfume compound, but is not also replaced the novel perfume material exploitation of the silicon analogue synthesized containing gem-dimethyl tetrahydrobenzene skeleton by Si/C at present.
Sila-β-imperial court ketone β-imperial court ketone α-silica-based alcohol
Summary of the invention
Object of the present invention provides a kind of sila-β with pineapple perfume (or spice)-imperial court's ketone compound based on above-mentioned prior art situation just.Another object of the present invention is to provide a kind of universal method of synthesizing this compound.
The object of the invention is to be achieved through the following technical solutions:
A kind of sila-β-imperial court's ketone, is characterized in that: be also 1-(3-sila-3,3-dimethyleyelohexane-1-thiazolinyl) penta-4-alkene-1-ketone, have such as formula the structure shown in I:
This sila-β-imperial court's ketone has the fragrant feature of strong pineapple.
Sila-β of the present invention-imperial court's ketone is under palladium chtalyst effect, and be made up the insertion ring expansion of the silacyclobutane of formula II of the terminal alkyne of formula III, the primitive reaction formula of preparation process institute foundation is as follows:
R in formula III represents hydrogen, aldehyde radical, ketone group, alkoxyl group, acetal radical, ketal group, ester group, phosphate.III specifically can be 6-heptene-1-alkynes-3-ketone, Methyl propiolate, ethyl propiolate, propynoic acid allyl ester, the propynoic acid tert-butyl ester, propynoic acid, propine acid amides etc.
Concrete reaction process is one of following two kinds of modes:
The first: be mixed in organic solvent by the 6-heptene-1-alkynes-3-ketone shown in the silacyclobutane shown in formula II and formula III, reacting by heating under palladium catalyst catalysis, reaction product can obtain sila-β-imperial court's ketone through concentrated, purifying;
The second: other terminal alkyne in the silacyclobutane shown in formula II and formula III except 6-heptene-1-alkynes-3-ketone is mixed in organic solvent, reacting by heating under palladium catalyst catalysis, then obtains sila-β-imperial court's ketone by the reaction product that concentrated, purifying obtain through derivatize or chemically modified.
Described ketone group represents-COR, and wherein R represents methyl, ethyl, propyl group, butyl or phenyl; Described alkoxyl group represents-OR
1 , wherein R
1 represent methyl, ethyl, propyl group, butyl or allyl group; Described ester group represents-COOR
2 , wherein R
2 represent methyl, ethyl, propyl group, the tertiary butyl, allyl group or trimethyl silicon based.
Described silacyclobutane is such as formula shown in II, and useful commercial reagent, without the need to special processing.Described terminal alkyne is such as formula shown in III, and useful commercial reagent, without the need to special processing.The input ratio of silacyclobutane and terminal alkyne is 10:1-0.8:1.
Described organic solvent is benzene, toluene, tetrahydrofuran (THF), hexane or dimethyl formamide (DMF); Organic solvent needs the degassed process of drying in advance.
Described palladium catalyst is (PPh
3)
4pd, (PPh
3)
2pdCl
2, Pd (OAc)
2+ 2PPh
3or Pd (dba)
2+ 2PPh
3, the injected volume of palladium catalyst is the 0.5%-10% of silacyclobutane mole number.
The ratio of the inventive method to silacyclobutane and solvent is not particularly limited, as long as can make reaction solution uniform stirring, the silacyclobutane of preferred 1mmol uses the solvent (as toluene) of 2-5mL.
Reaction times is slightly different according to different raw materials, detects disappearance and is as the criterion, general 1-40 hour with raw material.Heat-processed can adopt oil bath (such as silicone oil, paraffin wet goods) or other modes to heat, as long as temperature of reaction can be kept to be 25-200 DEG C.
Sila-β-imperial court's ketone of design and synthesis of the present invention has strong pineapple perfume.Present invention employs under palladium chtalyst effect, terminal alkyne is to the insertion ring expansion of silacyclobutane, utilize commercial silacyclobutane, high yield prepares the universal method of sila-β-imperial court's ketone, the method raw material is easy to get, applied widely, high isolated yield, experimental installation and operation is simple, is convenient to industrialization.
Embodiment
The present invention is further described below in conjunction with embodiment, but the scope do not limited the present invention in any way.
Treat different things alike synthesis sila-β-imperial court ketone I
embodiment 1
1, the 1-dimethylsilacyclobutane II of 1mol is added, the 6-heptene-1-alkynes-3-ketone of 1mol, the Pd (PPh of 1% equivalent in the round-bottomed flask of 10L
3)
4with 5L benzene solvent, be heated to 80 DEG C, magnetic agitation reacts 4 hours.Concentrated after reaction, silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product sila-β-imperial court ketone I(purity >98%, colourless liquid), isolated yield 57%.Nuclear-magnetism and the high resolution mass spectrum data of this compound are as follows:
1hNMR (CDCl
3) δ=6.78 (s, H), 5.89-5.79 (m, H), 5.06-4.96 (m, 2H), 2.82-2.78 (t,
j=5.5Hz, 2H), 2.37-2.32 (m, 4H), 1.82-1.76 (m, 2H), 0.70-0.67 (m, 2H), 0.135 (s, 6H).
13cNMR (CDCl
3) δ=201.47,156.24,137.58,136.69,114.92,36.22,28.53,27.99,20.96,11.17 ,-2.31.HRMS:
m/z: calcdforC
12h
20oSi [M+H]
+: 209.1356, found209.1352.
Reaction formula is as follows:
Two-step reaction synthesis sila-β-imperial court ketone I
embodiment 2
1, the 1-dimethylsilacyclobutane II of 1mol is added, the Methyl propiolate of 1mol, the Pd (OAc) of 10% equivalent in the round-bottomed flask of 10L
2+ 2PPh
3with 5L tetrahydrofuran solvent, be heated to boiling, magnetic agitation reacts 5 hours.Concentrated after reaction, silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=5:1, obtains straight product 1,1-dimethyl-3-methoxycarbonyl-sila tetrahydrobenzene, analytical data see document (
bull.Chem.Soc.Jpn., 1991,64,1461).
1 of 10mmol is added in the round-bottomed flask of 250mL, the THF of 1-dimethyl-3-methoxycarbonyl-sila tetrahydrobenzene and 150mL, is then cooled with an ice bath to 0 DEG C, under magnetic stirring, the high allyl bromine of slow dropping 10mmol and 50mg magnesium chips, time for adding is 1 hour.React with the dilute hydrochloric acid solution cancellation of 1M, gained solution extracted with diethyl ether three times, rotary evaporation is except desolventizing, and silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product sila-β-imperial court ketone I.Nuclear-magnetism and high resolution mass spectrum data are shown in embodiment 1.
Reaction formula is as follows:
embodiment 3
1, the 1-dimethylsilacyclobutane II of 1.5mol is added, the ethyl propiolate of 1mol, the Pd (PPh of 10% equivalent in the round-bottomed flask of 5L
3)
4with 2L toluene solvant, be heated to 90 DEG C, mechanic whirl-nett reaction 2 hours.Concentrated after reaction, silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product 1,1-dimethyl-3-ethoxycarbonyl-sila tetrahydrobenzene (purity >95%, colourless liquid), isolated yield 64%.Nuclear-magnetism and the high resolution mass spectrum data of this compound are as follows:
1hNMR (CDCl
3): δ=6.98 (s, 1H), 4.22-4.15 (m,
2h), 2.41-2.37 (t, 2H), 1.86-1.78 (m, 2H), 1.33-1.28 (t, 4H), 0.70-0.66 (m, 2H), 0.12 (s, 6H);
13cNMR (CDCl
3): d=167.17,148.26,1137.75,60.60,29.18,21.16,14.22,11.07 ,-2.37; HRMS:
m/z: calcdforC
10h
18o
2si [M+H]
+: 199.1149, found199.1145.
1 of 10mmol is added in the round-bottomed flask of 250mL, the THF of 1-dimethyl-3-ethoxycarbonyl-sila tetrahydrobenzene and 150mL, is then cooled with an ice bath to 0 DEG C, under magnetic stirring, the high allyl bromine of slow dropping 10mmol and 50mg magnesium chips, time for adding is 1 hour.React with the dilute hydrochloric acid solution cancellation of 1M, gained solution extracted with diethyl ether three times, rotary evaporation is except desolventizing, and silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product sila-β-imperial court ketone I.Nuclear-magnetism and high resolution mass spectrum data are shown in embodiment 1.
Reaction formula is as follows:
embodiment 4
1, the 1-dimethylsilacyclobutane II of 1.5mol is added, the propynoic acid tert-butyl ester of 1mol, the Pd (PPh of 10% equivalent in the round-bottomed flask of 5L
3)
2cl
2with 2L benzene, be heated to 90 DEG C, mechanic whirl-nett reaction 6 hours.Concentrated after reaction, silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product 1,1-dimethyl-3-tertbutyloxycarbonyl-sila tetrahydrobenzene (purity >97%, colourless liquid), isolated yield 73%.Nuclear-magnetism and the high resolution mass spectrum data of this compound are as follows:
1hNMR (CDCl
3): δ=6.86 (s, 1H), 2.36-2.32 (m, 2H), 1.84-1.76 (m, 2H), 1.49 (s, 9H), 0.67-0.63 (m, 2H), 0.11 (s, 6H);
13cNMR (CDCl
3): d=166.57,149.72,136.52,80.22,29.20,28.03,21.19,11.06 ,-2.28.HRMS:
m/z: calcdforC
12h
22o
2si [M+H]
+: 227.1462, found227.1463.
1 of 10mmol is added in the round-bottomed flask of 250mL, the THF of 1-dimethyl-3-tertbutyloxycarbonyl-sila tetrahydrobenzene and 150mL, is then cooled with an ice bath to 0 DEG C, under magnetic stirring, the high allyl bromine of slow dropping 10mmol and 50mg magnesium chips, time for adding is 1 hour.React with the dilute hydrochloric acid solution cancellation of 1M, gained solution extracted with diethyl ether three times, rotary evaporation is except desolventizing, and silicagel column decolouring is separated, with sherwood oil: eluent made by the mixed solvent of ether=10:1, obtains straight product sila-β-imperial court ketone I.Nuclear-magnetism and high resolution mass spectrum data are shown in embodiment 1.
Reaction formula is as follows:
Claims (7)
1. sila-β-imperial court's ketone, is characterized in that: also i.e. 1-(3-sila-3,3-dimethyleyelohexane-1-thiazolinyl) penta-4-alkene-1-ketone, has pineapple fragrant, have such as formula
ishown structure:
。
2. sila-β according to claim 1-imperial court's ketone
ipreparation method, it is characterized in that: be under palladium chtalyst effect, by formula
iIIterminal alkyne to formula
iIsilacyclobutane insertion ring expansion and make, the primitive reaction formula of preparation process institute foundation is as follows:
Formula
iIIin R represent hydrogen, aldehyde radical, ketone group, alkoxyl group, acetal radical, ketal group, ester group, phosphate;
Concrete reaction process is one of following two kinds of modes:
The first: is by formula
iIshown silacyclobutane and formula
iIIshown 6-heptene-1-alkynes-3-ketone is mixed in organic solvent, reacting by heating under palladium catalyst catalysis, and reaction product can obtain sila-β-imperial court's ketone through concentrated, purifying;
The second: by formula
iIshown silacyclobutane and formula
iIIin other terminal alkyne except 6-heptene-1-alkynes-3-ketone be mixed in organic solvent, reacting by heating under palladium catalyst catalysis, then obtains sila-β-imperial court's ketone by the reaction product that concentrated, purifying obtain through chemically modified.
3. the preparation method of sila-β according to claim 2-imperial court's ketone, is characterized in that: the input molar ratio of silacyclobutane and terminal alkyne is 10:1-0.8:1.
4. the preparation method of sila-β according to claim 2-imperial court's ketone, is characterized in that: described organic solvent is benzene, toluene, tetrahydrofuran (THF), hexane or dimethyl formamide DMF; Organic solvent needs the degassed process of drying in advance.
5. the preparation method of sila-β according to claim 2-imperial court's ketone, is characterized in that: described palladium catalyst is (PPh
3)
4pd, (PPh
3)
2pdCl
2, Pd (OAc)
2+ 2PPh
3or Pd (dba)
2+ 2PPh
3.
6. the preparation method of the sila-β according to claim 2 or 5-imperial court's ketone, is characterized in that: the injected volume of palladium catalyst is the 0.5%-10% of silacyclobutane mole number.
7. the preparation method of sila-β according to claim 2-imperial court's ketone, is characterized in that: reacting by heating temperature is 25-200 DEG C.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284845A (en) * | 2007-04-10 | 2008-10-15 | 北京大学 | Polysubstituted silacyclohexadiene and synthetic method thereof |
-
2013
- 2013-12-04 CN CN201310639756.6A patent/CN103601752B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284845A (en) * | 2007-04-10 | 2008-10-15 | 北京大学 | Polysubstituted silacyclohexadiene and synthetic method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Palladium Catalyzed Reaction of Silacyclobutanes with Acetylenes;Yoshihiro TAKEYAMA等，;《Bull. Chem. Soc. Jpn.》;19910531;第64卷(第5期);第1461-1466页，尤其是第1461页方案1，第1463页右栏倒数第1段至第1464页左栏第1段 * |
| Silylating Reagents: A Powerful Tool for the Construction of Isosteric Analogs of Highly Branched Odorants;Leszek Doszczak等，;《CHEMISTRY & BIODIVERSITY》;20041222;第1卷(第12期);第1921-1935页，尤其是第1923页图3化合物13，第1924页图4 * |
| 硅杂六元环化合物的合成;刘俊辉等，;《化学进展》;20090831;第21卷(第7/8期);第1475-1486页 * |
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